2

TABLE OF CONTENTS

1 INTRODUCTION AND OBJECTIVES ............................................................................. 4

2 AFR SUITABLE FOR CO-PROCESSING IN CEMENT KILNS...................................6
3 WASTE PRE-PROCESSING TO AFR............................................................................. 14
3.1 General ......................................................................................................................... 14
3.2 Pre-processing of waste for co-processing in cement kilns ...........................................15
3.2.1 General ............................................................................................................ 15
3.2.2 Pre-processing before co-processing as AFR ................................................. 15
4 PROCEDURES FOR PRE-PROCESSING WASTE DERIVED AF ............................. 17
4.1 General ......................................................................................................................... 17
4.2 Analyses of wastes ......................................................................................................... 17
4.3 Transport of waste .......................................................................................................... 18
4.4 Arrival of waste .............................................................................................................. 18
4.5 Unloading waste ............................................................................................................. 19
4.6 Waste storage units......................................................................................................... 20
4.7 Health and safety handling waste................................................................................... 20
4.7.1 Fire and explosion protection..........................................................................20
4.7.2 Workers protection.......................................................................................... 24
5 PRODUCTION PROCESSES OF AFR BASED ON WASTE ....................................... 26
5.1 Solid alternative fuel (SAF) ...........................................................................................26
5.2 Liquid alternative fuel (LAF) as such ............................................................................28
5.3 LAF by fluidification .....................................................................................................29
5.4 LAF by emulsification ................................................................................................... 30
5.5 Pre-processing plant examples .......................................................................................32
5.5.1 Energis, Holcim Group, in Albox, Spain ........................................................32
5.5.2 Ecoltec, Mexico............................................................................................... 34
5.5.3 Recent waste deal between Shanks and SRM of Castle cement, UK .............36
6 ENVIRONMENTAL ISSUES ............................................................................................ 37
6.1 Consumption of resources ..............................................................................................37
6.2 Emissions to air .............................................................................................................. 37
6.3 Volatile organic carbon (VOC) and smell......................................................................38
6.4 Impact on surface and ground water .............................................................................. 39
6.5 By-products and wastes generated ................................................................................. 40
6.6 Noise ......................................................................................................................... 40
7 TECHNIQUES TO INCLUDE IN BAT DETERMINATIONS......................................41
7.1 Preventive measures and reduction techniques for dust.................................................41
7.2 Preventive measures and reduction techniques for VOC and smell ..............................42
7.3 Preventing pollution of surface and ground water .........................................................45
7.4 By-product recovery and waste treatment......................................................................46
8 BEST AVAILABLE TECHNOLOGIES (BAT) ............................................................... 47
8.1 General ......................................................................................................................... 47
8.2 Preventive measures for dust, VOC and smell emissions ..............................................47
8.3 VOC emission capture and treatment.............................................................................47
8.4 Water emission prevention and treatment ......................................................................48
8.5 Used packaging .............................................................................................................. 48
 3

9 HEALTH AND INDUSTRIAL HYGIENE....................................................................... 49

9.1 General ......................................................................................................................... 49
9.2 Industrial hygiene (IH) ...................................................................................................49
9.2.1 Terminology ....................................................................................................49
9.2.2 Recognizing factors and stressors ...................................................................49
9.2.3 Evaluations ...................................................................................................... 50
9.2.4 Control measures.............................................................................................50
9.3 Chemical hazards and controls.......................................................................................50
9.3.1 General ............................................................................................................ 50
9.3.2 Chemicals and compounds..............................................................................50
9.3.3 Air contaminants .............................................................................................54
9.3.4 Chemical hygiene plan .................................................................................... 59
9.3.5 Hazard communication ...................................................................................59
9.3.6 Respiratory protection .....................................................................................59
9.4 Physical hazards and controls ........................................................................................61
9.4.1 General ............................................................................................................ 61
9.4.2 Noise and hearing conservation ......................................................................61
9.4.3 Pressure extremes............................................................................................64
9.4.4 Radiation and control ...................................................................................... 64
9.4.5 Thermal hazards ..............................................................................................65
9.5 Ergonomic hazards and control......................................................................................67
9.5.1 General ............................................................................................................ 67
9.5.2 Body systems at risk........................................................................................ 67
9.5.3 Evaluation ....................................................................................................... 68
9.5.4 Controls ...........................................................................................................68
9.5.5 Training ...........................................................................................................68
9.6 Biological hazards and controls .....................................................................................68
9.6.1 General ............................................................................................................ 68
9.6.2 Bio-aerosols..................................................................................................... 69
9.6.3 Blood borne pathogens (BBP) ........................................................................70
9.6.4 Zoonotic diseases ............................................................................................ 70
10 AFR FEED POINTS IN CEMENT KILNS ...................................................................... 72
11 CONCLUSIONS .................................................................................................................. 74
12 REFERENCES.....................................................................................................................75
ABBREVIATIONS .....................................................................................................................77
APPENDIX 1: LIST OF WASTE MATERIALS SUITABLE FOR AFR............................. 79
APPENDIX 2: MATERIAL SAFETY DATA SHEET OF LINDANE.................................. 86
APPENDIX 3: MATERIAL SAFETY DATA SHEET (MSDS) OF DDT............................. 92
APPENDIX 4: RISK PHRASES................................................................................................ 94
APPENDIX 5: SAFETY PHRASES.......................................................................................... 98
 4

1 INTRODUCTION AND OBJECTIVES

This report is a part of the Sino-Norwegian project “Environmentally Sound Management of

Hazardous and Industrial Wastes in Cement Kilns” running from 2007 through 2009 (Karstensen
and Justnes, 2007). The project comprises co-processing of waste in cement kilns. It has two
major advantages; the society gets rid of waste in a safe manner and the cement industry save
energy if the waste has a calorific value (alternative fuel, AF) or save raw material (alternative
raw material, AR) if the waste has a fraction that remains solid after burning (Justnes and
Engelsen, 2007). Sometimes it is difficult to distinguish the two latter benefits since many wastes
have a calorific value and a remaining solid component. Waste for co-processing is, therefore,
often referred to as alternative fuel and raw material (AFR). Another aspect of the project is to use
cement kilns to destruct hazardous waste in a safe manner.

The objective of the present report is to elucidate operational health and safety issues when
handling hazardous waste for destruction or when pre-processing industrial waste to make AFR
for co-processing in cement kilns, but also to inform about technology for pre-processing
operations transforming waste to AFR.

Some terms are important to define and definitions 1-5 are taken from the GTZ-Holcim
“Guidelines on co-processing waste materials in cement production” (2006):

1) Waste: The EC Framework Waste Directive 75/442/EEC, Article 1 defines waste as “any
substance or object, which (a) the holder discards or intends or is required to discard or (b) has to
be treated in order to protect the public health or the environment.” Waste material can be solid,
liquid, or pasty. Any waste material can be defined by its origin (industry, agriculture, mining
etc.), hence a proper list should always be established at national level to help create a common
understanding and define a legal framework. Where no specific list has been defined, the EC
Waste Catalogue might serve as a reference.

2) Hazardous and non-hazardous waste: The EC Directive 91/689/EC on Hazardous Waste

defines hazardous waste by reference to two Annexes that evaluate the level of danger of a
material (harmful, irritating, combustible etc.). However, legislation can vary greatly between
countries (except within the EU), leading to differences in determining whether a waste is
hazardous or not. For countries where no classification of waste exists, either the Waste List of the
Basel Convention 1 or the EC Waste Catalogue 2 is recommended.

3) Co-processing: This refers to the use of waste materials in industrial processes, such as
cement, lime, or steel production and power stations or any other large combustion plants. Even
though the EU calls this process co-incineration, for the purpose of this report, co-processing
means the substitution of primary fuel and raw material by waste. Co-processing is a recovery of
energy and material from waste. Waste recommended for co-processing is listed in Appendix 1
(GTZ, 2006).

4) AFR (Alternative Fuel and Raw Materials): This refers to (pre-processed) waste materials
used for co-processing. Such wastes typically include plastics and paper/card from commercial
and industrial activities (e.g. packaging waste or rejects from manufacturing), waste tires, waste
oils, biomass waste (e.g. straw, untreated waste wood, dried sewage sludge), waste textiles,
residues from car dismantling operations (automotive shredder residues), hazardous industrial
1
http://www.basel.int/text/con-e-rev.pdf
2
http://www.vrom.nl/get.asp?file=/docs/milieu/eural_engelse_versie.pdf
 5

waste (e.g. certain industrial sludges, impregnated sawdust, spent solvents) as well as obsolete
pesticides, outdated drugs, chemicals and pharmaceuticals.

5) Pre-processing: Transforming waste to AFR requires certain standards. AFR does not always
consist of a specific waste stream (such as tires or solvents) but must be prepared from different
waste sources before being used as fuel or raw material in the cement plant. The preparation
process is needed to produce an AFR stream that complies with the technical and administrative
specifications of cement production and to guarantee that environmental standards are met.

Cement is one of the most widely used substances on earth. Making cement is an energy and
resource intensive process with both local and global environmental, health and safety impacts.
Recognizing these facts, several cement companies initiated the Cement Sustainability Initiative
(CSI) as a member-sponsored program of the World Business Council for Sustainable
Development (WBCSD). Currently, sixteen cement companies, who together represent more that
half the worldwide industry outside China, sponsor the Initiative. Recently the CSI Conference
Board (http://www.conference-board.org/aboutus/about.cfm) published a research report: R-1334-
03-RR, ‘Driving Toward “0”’, Best Practices in Corporate Safety and Health, in which it collated
Best Practice gems of wisdom from a wide range of industries. The findings can be found in the
full document at the URL: http://www.conference-board.org/publications/describe.cfm?id=724

For more general information concerning “Safety Management and Organization” as well as
“Effective Safety Practices” in the cement industry, that also are relevant for waste processing
plants or any other process industry, it is referred to Kirk (2004a) and Kirk (2004b), respectively.

This report focuses on the more specific hazard and health aspects of waste handling and pre-
processing, as that this often is done by another company than the cement plant. The waste pre-
processing plant will then deliver ready AFR to the cement plant.
 6

2 AFR SUITABLE FOR CO-PROCESSING IN CEMENT KILNS

Although waste suitable for alternative fuel (AF) is treated in a separate report by Karstensen in
this project and alternative raw materials (AR) recently was reported in detail by Justnes and
Engelsen (2007), overviews of the utilization of alternative fuels (AFs) in the European and AFR
in the Japanese cement industry are given in Table 1 and 2 respectively, while utilization of
alternative raw materials (ARs) in the European cement industry is listed in Table 3. The
recommended exclusion of certain waste materials (GTZ, 2006) grouped 1-8 from co-processing
can be justified as follows (also summarized in Table 4):

1. Electronic waste
Electronic waste is composed of computer and accessories, entertainment and communication
electronics, toys but also white goods such as kitchen devices or medical apparatus. A recent
study 3 of the Swiss environment agency BAFU reveals that average electronic scrap consists of
45% of metals in terms of weight, with the highest portion on heavy metals and rare metals. With
23%, plastic ranges second in the composition, and compounds of picture tubes are at 20%.

The average composition shows that electronic scrap contains on one hand substances harmful to
health and the environment such as Cl, Br, P, Cd, Ni, Hg, PCB and brominated flame retardants in
high concentration, often higher than threshold limit values as fixed in the permits.

On the other hand, the scrap contains so much scarce precious metals that all efforts have to be
undertaken to recycle it. Co-processing of the plastic parts of the electronic waste would be an
interesting option, but requires disassembling and segregation first.

Table 1 Utilization of AF in the European Cement Industry in 2002

Alternative fuels (AFs) Amount Energy Substitution
(1,000 ton/year) (1012J) rate (%)
Animal meal / bone meal /animal fat 760 15,000 2.0
Tires 500 13,200 1.8
Other hazardous waste 360 6,500 0.9
Plastic 210 5,000 0.7
Paper / cardboard /wood / PAS 180 2,800 0.4
Impregnated sawdust 165 1,900 0.3
Coal slurries / distillation residues 110 1,650 0.2
Sludges (paper, fibre, sewage) 100 970 0.1
Fine /anodes / chemical coke 90 1,600 0.2
Refuse Derived Fuel (RDF) 40 530 0.1
Shale / Oil shale 15 130 < 0.1
Packaging waste 12 260 < 0.1
Agricultural & organic waste 10 170 < 0.1
Other non-hazardous waste 730 14,100 1.9
Subtotal solid AF (75%) 3,282 63,810 8.5
Waste oil and oiled water 380 13,500 1.8
Solvents and other organic liquids 260 3,900 0.5
Other hazardous liquid AF 170 4,300 0.6
Subtotal liquid AF (25%) 810 21,700 2.9
Total AF 4,092 85,510 11.4

3
Schriftenreie Umwelt Nr. 374, BUWAL, 2004
 7

Table 2 Utilization of waste for AFR in the Japanese cement industry (2001)
Type of waste Use at cement plant Mass (1,000 tons)
Blast furnace slag Raw material, mixing material 11,915
Coal ash Raw material, mixing material 5,822
By-product gypsum Raw material (additive) 2,568
Low quality coal from mine Raw material, Fuel 574
Non-iron slag Raw material 1,236
Revolving furnace slag Raw material 935
Sludges etc Raw material, Fuel 2,235
Soot and dust Raw material, Fuel 943
Foundry sand Raw material 492
Used tires Fuel 284
Waste oils Fuel 353
Spent activated carbon Fuel 82
Waste Plastics Fuel 171
Others Raw material, Fuel 450
Total AFR 28,061

2. Entire Batteries
Batteries can be classified as automotive batteries, industrial batteries and portable (consumer)
batteries. Automotive batteries are mainly lead-acid batteries; industrial batteries comprise both
lead-acid batteries and nickel-cadmium batteries. The portable battery consists of general purpose
batteries (mainly zinc-carbon and alkaline manganese batteries), button cells (mainly mercury,
zinc-air, silver oxide, manganese oxide and lithium batteries) and rechargeable batteries (mainly
nickel-cadmium, nickel-metal hydride, lithium ion and sealed lead-acid batteries). Most of these
substances are harmful to health and the environment. Co-processing of batteries would lead to an
undesirable concentration of pollutants in the cement and the air emissions. Also, some battery
contents, such as mercury, nickel or cadmium, exceed any limit value for AFR (see Table 5, 6 and
7). In addition, commercially viable battery recycling plants have been successfully introduced.

Table 3 Utilization of AR in the European cement industry (2002)

Main clinker Alternative Amount Substitution
substitution raw material (1,000 tons/year) rate (%)
Silicon (Si) Foundry sand 131 2.2
Sand 93 1.6
Calcium (Ca) Ca-sources 396 6.7
Waste limestone 438 7.4
Iron (Fe) Fe-containing materials 699 11.8
Blastfurnace & converter slag 215 3.6
Pyrite ash 438 7.4
Aluminium (Al) Al-containing materials 150 2.5
Industrial sludge 137 2.3
Si-Al-Ca Other Si-Al-Ca rich materials 247 4.2
Fly ash 1,140 19.3
Others 1,823 30.8
All Total 5,907 -
 8

3. Infectious and biologically active medical wastes

Infectious and biologically active hospital wastes are generated in the hospitals, in veterinary care
and in research. Examples are used blood transfusion bags, blood contaminated bandages, dialysis
filters, injection needles, and also parts of the body and organs. Biologically active hospital wastes
include pharmaceuticals. The disposal requires special hygienic and work safety requirements on
handling, packaging and transportation. See also Chapter 9 on Health and Industrial Hygiene.

The conditions in the cement kiln would be appropriate to treat infectious and biologically active
hospital wastes, but would require special precautions on occupational health and safety (OH&S)
in the supply chain of this type of waste. As the required OH&S conditions can not be fully
assured, co-processing is presently not recommended. However, the problem of inadequate
handling of medical waste has persisted for years, especially in developing countries. Although it
is well known that segregating waste at the source is the most important step in managing medical
waste, this principle is not yet sufficiently applied. Even less attention is given to the ultimate safe
storage and final treatment (sterilization or microwave) of infectious waste.

Small medical waste incinerators have been promoted and introduced in the past in many
countries as a decentralized solution. However, experience that this technology in many cases is
not appropriate due to absence of qualified personnel and high costs associated with building,
operating, maintaining and monitoring such facilities. As a consequence, the release of unwanted
emissions (such as Polychlorinated dibenzodioxins (PCDDs) and Poly-chlorinated dibenzofurans
(PCDFs), hydrochloric acid or heavy metals) in relatively high concentration must be considered.

As the problem persists and might become even more severe with a wider spread of infectious
diseases (such as AIDS, SARS, Bird flu, Ebola etc.) co-processing might become part of the
solution for final treatment, but only if defined pre-conditions in hospitals and health care centres
have been introduced. Future cooperation and research between international organizations such
as the WHO and the cement industry could result in joint activities, such as the definition of
standardized handling procedures.

Table 4 Overview of waste materials not recommended for co-processing and reasons why
Enrichment Emission OH&S Recycling Landfilling Negative impact on
of clinker values potential better kiln operation
pollutants option
Electronic x x x
waste
Entire x x x x
batteries
Infectious and x
biological
active
medical waste
Mineral acids x x x
and corrosives
Explosives x x x
Asbestos x x
Radioactive x x
waste
Unsorted x x x x
municipal
waste
 9

4. Mineral acids and corrosives

Mineral acids are derived from inorganic minerals. Examples are hydrochloric acid, nitric acid,
phosphoric acid and sulphuric acid (e.g. automotive batteries). The inorganic minerals such as S
and Cl that are the main component of the acid have a negative impact on the clinker process (also
P if P2O5 > 0.5% of clinker) and product quality and may lead to unwanted waste gas emissions.
Acid may corrode and damage the production facilities.

Beside mineral acids, substances that can cause severe damage by chemical reaction to living
tissue, or freight, or the means of transport are prohibited, as are all corrosive substances. Well
known examples are aluminium chloride; caustic soda; corrosive cleaning fluid; corrosive rust
remover/preventative; corrosive paint remover. These types of materials should be excluded from
co-processing due to the upstream collection, transport risks and handling hazards.

5. Explosives
Explosives are any chemical compound, mixture or device capable of producing an explosive-
pyrotechnical effect, with substantial instantaneous release of heat and gas. Examples are nitro-
glycerine, fireworks, blasting caps, fuses, flares, ammunition, etc. Reasons to exclude them from
co-processing are occupational safety due to the risk of uncontrolled explosions during pre-
processing activities such as transportation, handling, shredding etc. Explosive reactions in the
cement kiln would have a negative impact on process stability.

6. Asbestos
Asbestos is a name given to a group of minerals that occur naturally as masses of long silky
fibers. Asbestos is known for its unique properties of being resistant to abrasion, inert to acid and
alkaline solutions, and stable at high temperatures. Because of these attributes, asbestos was
widely used in construction and industry. Asbestos fibers are woven together or incorporated
within other materials to create many products.

Airborne asbestos fibres are small, odourless and tasteless. They range in size from 0.1 to 10
microns in length (a human hair is about 50 microns in diameter). Because asbestos fibres are
small and light, they can be suspended in the air for long periods. People whose work brings them
into contact with asbestos may inhale fibers. Once inhaled, the small, inert asbestos fibers can
easily penetrate the body‘s defences. They are deposited and retained in the airways and tissues of
the lungs and can cause cancer. Due to this negative health impact, the use of asbestos has been
forbidden for around 25 years.

Asbestos-containing materials can be classified into one of three types: Sprayed or trowelled-on
material (e.g. ceilings or walls), thermal system insulation (e.g. plaster cement wrap around
boilers, on water and steam pipe elbows, tees, fittings, and pipe runs), or miscellaneous materials
(e.g. floor tile, sheet rock, ceiling tiles, automotive friction products). Millions of tons of asbestos
products will become waste material in the future, especially in developing countries, and not all
countries have national regulation on handling and final disposal of this significant waste stream.

Asbestos-containing products could be treated in specially equipped rotary kilns at a temperature

> 800°C for a certain time. The asbestos minerals would be transformed into other minerals like
Olivine or Forsterite. Therefore co-processing could be, from a technical point of view, an option
for treatment of asbestos waste. However, sanitary landfilling must be regarded as the most
appropriate way of final disposal as the material can be disposed undisturbed and does not
provoke the release of unwanted fibers into the air. Once safely dumped, the asbestos waste does
not have further negative environmental impacts. As the availability and new installation of
sanitary landfill become more and more a problem, requests for co-processing asbestos might
arise in the future. However before cancelling asbestos from the banned list, detailed
 10

investigations are required in particular on OH&S in the whole supply chain. Further, asbestos-
specific regulations have to be introduced and enforced by the national authorities.

7. Radioactive waste
Radioactive waste is normally excluded from “classical” waste management, and therefore
specific regulations have to be applied according to international agreements. This means that
radioactive waste can not be treated under the regulations of municipal and household waste and
special permissions for its treatment are required. The procedure is normally stipulated in national
nuclear laws. Cement plants are not suited to handle radioactive waste.

However, there is a borderline case for low radioactivity wastes (e.g. waste from research,
cleaning devices or in medical entities). Following the recommendations from the International
Atomic Energy Agency and other organizations, many countries define waste as low radioactive if
the radiation of this material to humans does not exceed 10 μSv (micro Sievert) per year. For this
case a restricted or even an unrestricted clearance for handling this waste within an integrated
waste management scheme could be given. At the international level, there is still a big
discrepancy on procedures for clearance, and no uniform levels are given. As it is very difficult
for most companies and/or authorities to guarantee that the threshold limit value (TLV) of 10 μSv
could be assured at any time, co-processing of any kind of radioactive waste is not recommended.

8. Unsorted municipal waste

Municipal waste is a heterogeneous material and consists in developing countries mainly of native
organic (e.g. kitchen refuse), inert (e.g. sand) and post-consumer (e.g. packing material) fractions.
Valuable recycling goods such as cardboard, plastic, glass or metal are often sorted out by the
informal (waste pickers) or formal (cooperatives) sector.

Despite recent efforts by local authorities in keeping their cities cleaner, the problems persist with
the final disposal of the waste if no sanitary landfill sites can be made available due to protests by
citizens or the high costs of the transport to a suitable site. In order to escape from this bottleneck,
local and national decision makers opt for co-processing of the collected mixed waste material
and to shift the responsibility of final treatment to the cement industry.

However, from an ecological, technical and financial point of view, the co-processing of unsorted
municipal waste is not recommended. Mixed municipal waste must be sorted in order to obtain
defined waste streams of known quality. For selected materials, co-processing should be regarded
as an integrated part of municipal solid waste management.

There are a number of limitations in different countries for wastes to be used in co-processing and
for AFR. These are listed in Tables 5, 6 and 7.
 11

Table 5 Limit values in different permits and regulations for waste for co-processing in
Austria, Switzerland and Germany

Austria Switzerland Germany

General High Solvents, General Other High Solvents,
combustible calorific spent oil, combustible waste for calorific spent oil
waste1 fraction of waste waste 2
disposal fraction of
common lacquers common
waste waste3
Maximum values (mg/kg)
As 15 15 20 15 - 13 15
Sb 5 20 (200)4 100 5 800 120 20
Be 5 - - 5 - 2 2
Pb 200 500 800 200 500 400 150
Cd 2 27 20 2 5 9 4
Cr 100 300 300 100 500 250 50
Cu 100 500 500 100 600 700 180
Co 20 100 25 20 60 12 25
Ni 100 200 - 100 80 160 30
Hg 0.5 2 2 0.5 55 1.2 1
Tl 3 10 5 3 - 2 2
V 100 - - 100 - 25 10
Zn 400 - - 400 - - -
Sn 10 70 100 10 - 70 30
Cl- 10,000 20,000 - - - 15,000 -
PCB 50 - 100 - - - -
1 2 3 4
Net calorific value 25 MJ/kg. Net calorific value 18 MJ/kg. PET. PET, polyester.
5
Special case, flue gas cleaning for Hg
 12

Table 6 Examples of limit values for AF for different countries based on individual permits

Parameter Unit Spain1 Belgium2 France2

Calorific value MJ/kg - - -
-
Halogens (given as Cl ) % 2 2 2
Cl % - - -
F % 0.2 - -
S % 3 3 3
Ba mg/kg - - -
Ag mg/kg - - -
Hg mg/kg 10 5 10
Cd mg/kg 100 70 -
Tl mg/kg 100 30 -
Hg + Cd + Tl mg/kg 100 - 100
Sb mg/kg - 200 -
Sb + As + Co + Ni + Pb + Sn + V + mg/kg 5,000 2,500 2,500
Cr
As mg/kg - 200 -
Co mg/kg - 200 -
Ni mg/kg - 1,000 -
Cu mg/kg - 1,000 -
Cr mg/kg - 1,000 -
V mg/kg - 1,000 -
Pb mg/kg - 1,000 -
Sn mg/kg - - -
Mn mg/kg - 2,000 -
Be mg/kg - 50 -
Se mg/kg - 50 -
Te mg/kg - 50 -
Zn mg/kg - 5,000 -
PCBs mg/kg 30 30 25
PCDDs / PCDFs mg/kg - - -
Br + I mg/kg - 2,000 -
Cyanide mg/kg - 100 -
1
Limit values set by authorities for individual permits for cement plants in Spain
2
Voluntary self-commitment of the cement industry with authorities and concerned ministry
 13

Table 7 Examples of limit values for waste to be used as AR in different countries

Parameter Unit Spain1 Belgium2 France2 Switzerland3

TOC mg/kg 20,000 5,000 5,000 -
Halogens (given as Cl) % 0.25 0.5 0.5 -
F % 0.1 - - -
S % 3 1 1 -
Hg mg/kg 10 - - 0.5
Cd mg/kg 100 - - 0.8
Tl mg/kg 100 - - 1
Hg + Cd + Tl mg/kg 100 - - -
Sb mg/kg - - - 1
Sb + As + Co + Ni +Pb + Sn +V + mg/kg 5,000 - - -
Cr
As mg/kg - - - 20
Co mg/kg - - - 30
Ni mg/kg - - - 100
Cu mg/kg - - - 100
Cr mg/kg - - - 100
V mg/kg - - - 200
Pb mg/kg - - - 50
Sn mg/kg - - - 50
Mn mg/kg - - - -
Be mg/kg - - - 3
Se mg/kg - - - 1
Te mg/kg - - - -
Zn mg/kg - - - 400
PCBs mg/kg 30 - - 1
pH - - - - -
Br + I mg/kg - - -
Cyanide mg/kg - - - -
1
Limit values set by authorities for individual permits for specific cement plants in Spain
2
Voluntary self-commitment of the cement industry with authorities and concerned ministry
3
Limit values for AR, BUWAL 1998. Guidelines disposal of wastes in cement plants, Table 1
 14

3 WASTE PRE-PROCESSING TO AFR

3.1 General

Waste recovery and disposal treatment often need a pre-processing step. This may be a single
operation or the combination of several processes (grouping/reconditioning, pre-processing).
These operations may be processed on the waste production site, on specific dedicated locations
or integrated with the final process.

The aim of waste pre-processing before recovery or disposal (i.e. including use as AFR) is to:

1. Facilitate a recovery access or to improve dedicated treatment for wastes such as

stabilisation for landfilling (in order to decrease long term impact of the hazardous waste),
homogenisation for an incinerator feed (used in order to improve combustion conditions)
etc.
2. Improve safety for waste treatment (decrease hazardous characteristics, facilitation of
handling etc.)
3. Rationalise the logistic cost

The combination of treatments used in waste preparation and in pre-processing operations

depends on the specifications of final treatment. At the end of the pre-processing, the pre-
processed waste has to comply with chemical and physical specifications that are fixed by the end
users.

Most of the operation linked with waste treatment may be divided into regrouping / reconditioning
and pre-processing. In regrouping / reconditioning the aim is to group wastes in small or medium
quantities, when they have the same nature, and when they are compatible. The resulting waste
has still to be processed. The vocation of regrouping is to have more important and homogeneous
volumes. In pre-processing the aim is to adapt the waste to the type of recovery and/or disposal
final treatment. Pre-processing may develop several aspects. It can be defined as the operations
that lead to homogenisation of chemical composition and/or physical characteristics of the wastes.
Pre-processing produces an adapted waste, which is different from the initial ones, but not from
the regulatory point of view. This adapted waste has still to be treated in a recovery and/or in a
disposal plant.

The main processes used in waste preparation activities are

• Re-grouping / re-conditioning
• Homogenisation and blending
• Crushing
• Sieving
• Fluidification
• Sorting for solid wastes
• Phase separation for liquid wastes: settling, centrifugation, extraction etc.
• Drying
• Washing

Pre-processing activities are integrated in the treatment of wastes. So, they have both to comply
with waste regulations (knowledge of wastes, traceability, follow up of wastes stream etc.),
industrial and environmental regulations (environmental impact assessment and public
 15

consultation, permit with adapted specifications such as risk prevention, specifications for soil,
water and air protection etc.), as well as related health and safety regulations.

3.2 Pre-processing of waste for co-processing in cement kilns

3.2.1 General

The history of the co-processing (mainly co-incineration in cement kiln) started in the mid
seventies when the petroleum crisis had increased drastically the cost of the fuel oil and when, in
different countries, new regulation was issued on waste disposal. As a large amount of energy rich
waste (mainly solvents) were available, the co-processing of waste in cement kilns was the most
logical answer to the situation on both environmental and economical points of view. Then, in
order to increase the energy saving, more and more sophisticated pre-processes have been
developed, first to produce liquid alternative fuel (LAF) and in the nineties to produce solid
alternative fuel (SAF). Alternative fuel is sometimes referred to as “substitution fuel”.

The use of waste derived fuel in European cement kilns saves fossil fuels. This represented in
2003 3.15 million tons of coal per year. In addition to energy recovery, there is a corresponding
greenhouse gas saving, mainly CO2 emissions (7.4 million tons CO2) not released to the
atmosphere. This waste may contain mineral components that will be recovered in the kiln as
alternative (also referred to as “substituted”) raw material. The advantages of utilizing a cement
kiln for treatment of hazardous wastes can be summarised as follows:

• high flame temperature (1,800-2,000°C)

• 5 to 6 seconds of residence time above 1,200°C
• excess of oxygen during and after the combustion
• complete destruction of organic compounds
• neutralisation of acid gases, sulphur oxides and hydrogen chloride, by the active lime in
the kiln load, in large excess to the stoechiometry
• embedding of the traces of heavy metals in the clinker structure with very stable bonds
• no production of by-products such as ashes or liquid residues from gas cleaning
• reduction of fossil fuel and/or raw material uses
• total recovery of energy and mineral content of the wastes (raw material and fossil fuel
saving)

3.2.2 Pre-processing before co-processing as AFR

The aim of the pre-processing is to adapt the waste to enable fuel and raw material recovery by
means of co-processing.

The basic principles of waste derived fuel production are the following:

• The chemical and physical quality of the fuel shall meet regulatory specifications and/or
standards ensuring environmental protection, cement kiln process and cement quality.
• Energy and mineral contents must remain stable to allow optimal feed in the kiln.
• The physical form must allow safe and proper handling, storage and feeding.

Several derived fuels can be prepared according to the different waste markets:
• Solid alternative fuel (SAF) based on absorbents, solid and pasty wastes.
 16

• Liquid alternative fuel (LAF) based on solvents, oils, emulsions or other organic liquids.
• Sludges.

Note that some hazardous wastes, produced in stable processes, may comply without any
preparation with the requirements of the co-processing plant. Due to that, they are often delivered
directly to the co-processing plant (e.g. used oils, used solvents etc), these streams, their control
modalities and their storage specifications are not integrated in this document.

Data for SAF based on pre-processing plants production in 2001 in France, Belgium, Holland,
Germany, Italy, Switzerland, Spain, Portugal, Poland, Norway and Slovakia: The average size of
a SAF pre-processing plant is 18,000 tons/year, with capacities ranging from 2,000 tons/year to
70,000 tons/year. The total production of SAF was 465,000 ton/year in 26 plants.

Data for LAF (excluding oils) based on regrouping and pre-processing plants in France, Belgium,
Holland, Germany, Italy, Switzerland, Spain, Portugal, Ireland, England, Sweden, Norway, Czech
Republic and Slovakia: The size of a LAF pre-processing plant varies widely, from 5,000 tons to
100,000 tons/year. For regrouping facilities, the typical size of a plant ranges from 1,000 tons to
20,000 tons/year. The total production of LAF was 806,000 ton/year in 117 plants.
 17

4 PROCEDURES FOR PRE-PROCESSING WASTE DERIVED AF

4.1 General

This chapter is about all operations which are common to all types of alternative fuel (AF)
production.

4.2 Analyses of wastes

Each step of the hazardous waste management (and not only waste recovered fuel production)
requires knowledge and control of the waste. The aim of this sub-chapter is to present the
different types of controls and analyses which are carried out, during the waste recovered fuel
process, from the waste production to the final treatment.

Acceptance analyses
When a waste producer contacts a waste management company (WMC) in order to treat his
wastes, a very complete and preliminary analysis will be done by the WMC. Based on the results
of these analyses, and according to the permit and the technical specifications (pre-processing
facilities and final users), the WMC decides to accept (or reject) the waste on its pre-processing
facility and delivers «an acceptance certificate». This certificate is regularly reviewed (one to five
years). The main parameters which are analysed in order to prepare a waste useful for energy
recovery in co-processing are listed in Table 8. A sample is taken under the responsibility of the
producer by himself or by the WMC commercial representative.

Reception analyses
For each reception of wastes on the pre-processing site, analyses are done in order:
• to be sure that the waste complies with the permit requirements,
• to define as well as to decide if pre-processing is possible,
• to provide a stable quality of the prepared fuel,
• to ensure compliance with internal OH&S requirements (employee’s protection),
• to keep records for (potential) future requests, inquiries or allegations

The main parameters which are analysed at reception are listed in Table 8. In specific cases, some
sites may develop simplified procedures for regular wastes with constant quality. This particular
procedure may be developed under quality procedure and with the agreement of the authorities.

The procedure of sampling before unloading is made by dedicated personnel. Adequate sampling
equipment must be available at each sampling station. The sampler must receive extensive
training in occupational health & safety aspects and preventive / protective measures, in addition
to training in the regular sampling procedures.

Recommended sampling tools are the following:

• For liquids use standard aluminium or copper sampling tubes (2.5 and 1.2 m length,
around 20-30 mm diameter) with ball valves at one end.
• For solids and pasty materials use an aluminium shovel (capacity around 0.5-1 litre) or
drilling devices.
 18

Automatic sampling of liquids during unloading of trucks enables higher accuracy and reduced
OH&S risk for the sampler. If the sample is not available prior to unloading, the waste has to be
unloaded in a separate buffer tank and analysed prior to further treatment.

The samples can be stored in glass or plastic bottles (PE or PTFE) of different volumes (250, 500,
1,000 ml), in plastic bags (various size) or in metallic cans.

Written instructions (sampling procedures) must be available for the sampler taking into
consideration:
• The physical nature (liquid, solid, pasty) and the volume of the material.
• The containment of the waste deliveries (trucks, containers, drums, cans etc.).
• OH&S risk of the material.

When the pre-processing unit is separated from the co-processing facilities, new analysis, with or
without adapted procedure, can be requested and will be similar to the preceding reception
analyses.

Process analyses
During the waste pre-processing, specific analyses are undertaken to monitor the quality of the
processed wastes. The main parameters which are analysed are listed in Table 8. Sampling is
according to the type of processes and installations.

Expedition analyses
At the completion of the pre-processing, analyses are made in order to ensure compliance with
respect to all parameters and specifications which are necessary (regulatory or technical
parameters) for the final treatment. The main parameters which are analysed are listed in Table 8.
Sampling is according to the type of alternative fuel produced.

External analyses
Supplementary analyses can be done under the control of the authorities.

4.3 Transport of waste

• Wastes are conditioned in trucks, container, drums or other types of containers.

• Transport of drums or containers has to be done properly, especially in case of hazardous
wastes: They must be in good state, closed, and the content has to be identified.
• Transport of hazardous wastes has to comply with the relevant Regulations on the
Transportation of hazardous substances, so called ADR: Special equipped trucks have to
be used, transport documents have to be in order and the driver must be properly trained
for this type of transport.
• Usually wastes are brought to the pre-processing plants by trucks. Ship and rails transport
should be promoted whenever economically and environmentally feasible.

4.4 Arrival of waste

• At the arrival on the plant, the driver has to give all the administrative required documents,
such as:
o Certificate of acceptance
 19

o Administrative document which follows the waste way, from the producer to the
plant, via the collectors or transport companies
o Transport authorisations, according to national regulations
o Waste analyses from the producers in some cases
• If these administrative requirements are not met (after checking with a producer), the truck
is sent back to the producer, and local authorities will be informed.
• A control of the aspect of the truck and its loading is made by the personnel of the plant. If
some non-conformity is noticed, the producer/collector is immediately informed.
• After these controls of both administrative documents and loading, the truck is weighed,
and sampled. The reception analysis follows (see chapter 4.1). In the case of packaged
wastes, trucks are unloaded before analysis.

Table 8 Recommended parameters for different analyses of waste

Parameters Acceptation Reception AF preparation Expedition

process*
Density Yes Optional Optional Optional
Viscosity Optional Optional Optional Optional
Flash point Yes Yes Optional Yes
Low calorific value (LCV) Yes Yes Yes Yes
Vapour pressure Optional Optional Optional Optional
Water content Yes Yes Optional Yes
pH Yes Yes Optional Yes
Ash content Yes Optional Optional Yes
Ash composition Optional Optional Optional Optional
Chlorine Yes Yes Yes Yes
Fluorine Optional Optional Optional Optional
Bromine Optional Optional Optional Optional
Iodine Optional Optional Optional Optional
Volatile heavy metals (Hg, Tl, Cd) Yes Yes Optional Yes
Other heavy metals Yes Yes Optional Yes
Polychlorinated biphenyl (PCB) Yes Yes Optional Yes
PCP Optional Optional Optional Optional
Sulphur Yes Optional Optional Optional
Alkalis Optional Optional Optional Optional
Corrosion test Optional Optional Optional Optional
Compatibility test Yes Yes - -
Radioactivity Optional Yes - Optional
* function of the type of production.
Optional: Function of type of wastes, operating processes (liquid or solid alternative fuel preparation) and according
to requirements specifications of the final users.
Parameters in italic characters: Minimum controls required in standard procedure.

4.5 Unloading waste

After the laboratory has given its approval for unloading, the truck will proceed to the unloading
area. Wastes delivered in bulk are unloaded:
• In pits for solid and pasty wastes,
• On sealed concrete floors for solid and pasty wastes
• In tanks for liquid wastes.
 20

Wastes delivered in drums, containers or other types of conditioning are unloaded on a specific
area, dedicated to conditioned wastes. Each load which is clearly identified by the laboratory has
to be properly and separately stored, per producer, type of waste, etc.

4.6 Waste storage units

Storage capacities have to be designed to ensure a continuous service to the waste producers, in
case of shutdown of the co-processing facilities which use the pre-processed wastes as an
alternative fuel.

Sludges and solid wastes can be stored in a closed building in pits or on a sealed concrete floor
according to the physical aspect and flash point. The installations have to be waterproof and
resistant to the waste composition (notably corrosion and abrasion). Appropriate ventilation is
required.

Packed wastes are stored on a covered concrete area, with retention.

Liquid wastes are stored inside closed tanks.

Sawdust and/or waste which may be used as adsorbents are stored in a closed area with concrete
floor, in silos, containers, hoppers or big bags. Note that some installations are equipped to
produce their own sawdust by shredding waste wood. Sawdust comes from the first use of wood
(sawmill or furniture production), but also from the recycling of waste wood (tiny particles that
can not be reused in the wooden panel industry).

Surfactant products may be used in some alternative fuel production (e.g. to make emulsions).
They are stored in separate tanks.

4.7 Health and safety handling waste

This sub-chapter presents standardised procedures applied for all types of treatment or pre-
processing of hazardous wastes, being for co-processing or for incineration.

4.7.1 Fire and explosion protection

Since wastes generally are transformed to AFR for their calorific value (combustible), and wastes
for simple destruction often is of organic nature, fire and explosive risks are highly relevant
issues.

Fire prevention measures are an appropriate combination of the following points:

• Waste knowledge (to detect potentially exothermic reactions)

• The plant have to be protected from direct and indirect lightning impacts
• Prevention of electrostatic electricity discharges (e.g. establish equipotential connections
between metallic masses and trucks)
• A fire permit has to be established for all works which request a flame
• Adapted and regular electricity controls are requested
 21

• Workers training against fire in order to know how to use protection measures
• Development of an adapted plant control with cameras, temperature and flame detection,
etc
• Use of technical measures such as firebreak wall, water curtain, etc

According to Kirk (2004b) safe storage and handling practices of waste will minimize hazards and
the likelihood of fire. Best practices for handling flammable and combustible materials include:

1. Storing flammable gases away from oxidizers

2. Storing combustible and flammable liquids in labelled safety cans with a spring-closing
lid, spout cover and flame arrestor screen
3. Storing safety cans and aerosol cans in approved, designated storage cabinets
4. Storing solid fuels in compacted piles to reduce the chance of spontaneous combustion
5. Posting warning signs prohibiting smoking, flames and open lights wherever flammables
or combustibles are used, stored or handled
6. Controlling and promptly cleaning up spills, leaks and waste before large quantities
accumulate
7. Turning OFF internal gasoline-powered internal combustion engines when refuelling
8. Using hot-work permits and fire watches when welding or oxy-fuel burning near
combustible materials
9. Providing fire suppression sprinklers in critical work and storage areas.

Kirk (2004 b) emphasises further that gases, oils, greases, paper products and other flammable or
combustible materials should not be stored or allowed to accumulate in:

1. Pyro-processing areas or other locations where high temperatures or open flames are
common or likely
2. Areas where spillage of hot dust may occur
3. Near potential electrical ignition sources.

Automatic sprinklers or fire suppression systems are recommended in storerooms or warehouses

where large quantities of combustible materials are stored. Belt conveyors used for transporting
hot materials, such as clinker, should be rated for high temperature use, monitored by remote
sensors and protected by sprinklers.

Explosions release tremendous amounts of energy in the form of heat, light, sound and pressure.
Pressure waves can rise at the rate of 13,800 kPa/sec to reach 620-760 kPa with air velocities in
excess of 320 km/h. Potential explosion damages include:

1. Human injury or fatality

2. Secondary explosions
3. Fires
4. Damage to equipment or building structures
5. Damage to or interruption of process systems, utilities or communications systems.

Explosion prevention measures are an appropriate combination of the following points:

• Closed areas with canalisation of exhaust air with effective ventilation

• If necessary, development of spraying measures or use of inert nitrogen atmosphere (in
mixers, crushers, etc.)
 22

• Definition of explosion risk areas in order to put signals on and to equip them with adapted
detection means
• Use of anti sparks equipment
• Avoid any sources that could cause local heat release

Catalytic and infrared detectors are used to spot explosive atmospheres. The calibration of the
detector needs particular attention.

According to Kirk (2004b), explosions can occur only when the following five factors exist
together simultaneously:

1. Finely divided fuel

2. An ignition source
3. Oxygen
4. Suspension
5. Confinement.

Best practice is to prevent explosions by eliminating or controlling one or more of the preceding
five factors. Immediate repair of flammable and combustible materials leaks is advised, such as
when coal-handling systems leak in a cement plant. Good housekeeping will minimize the
quantity of fuel that could be involved in a secondary explosion. Other control methods include
use of oxy-fuel burning and welding gases with a narrower explosive range, less volatile solid
fuels (such as coke instead of coal), limiting heat or eliminating ignition sources, reducing oxygen
or using inert process gases, etc.

According to Kirk (2004b) explosion protection methods include:

1. Containment; relying on the strength of process equipment to retain the post-explosion

atmosphere
2. Isolation; stopping the spread of the explosion from the point of origin
3. Suppression; minimizing the destructive ability of an explosion by injecting pressurized
nitrogen or powdered agents such as mono-ammonium phosphate or sodium hydrogen
carbonate into the incipient explosion area
4. Venting; reducing pressure to a safe level by releasing the burning process material and
excessive pressure into a safe area (Chatrathi and Siwek, 1996.) Redundant systems are
recommended.

In a cement plant (Kirk, 2004b), explosion and fire potential exists in kiln fuel preparation, dust
collection and firing systems (especially those using gas or stored pulverized coal), and in
electrostatic precipitators of the kiln exhaust cleaning system where combustible gases like carbon
monoxide (CO) or combustible pulverized coal particulates may accumulate. Written procedures
should be prepared and followed regarding fuel preparation and safe operating parameters of
precipitator. Particular attention should be given to periods of non-standard operating activities
such as start-up, shut-down, equipment malfunctions and equipment maintenance periods. These
are the times of highest probability of sparking or collection of oxygen-rich gases in the system.
Gases used for heating, drying and ground fuel transport in coal mills should be inert, having
oxygen levels incapable of supporting combustion, certainly less than 12%, preferably less than
8%. Rising temperature and incipient explosion sensors and analyzers for oxygen and combustible
gases should be tied to automatically acting control systems. When oxygen-displacing materials
such as liquid or vapour CO2, or N2 gas, are used to control combustion or explosion, best
practices are to:
 23

1. Protect the inert gas storage tanks from damage and subsequent unintentional leakage into
the work environment
2. Add an odour that personnel can sense if leakage does occur
3. Employ gas detection devices to sense concentrations that might be of immediate danger
to life and health, and couple them with visible and audible warning alarms
4. Provide lockable valves in the gas piping and delivery systems to prevent unintended
discharge into equipment or vessels occupied by persons performing inspections or
maintenance
5. Consistently use lockout and confined space entry procedures.

Where explosion rupture vents are used, they should be located away from areas where personnel
travel or congregate and away from critical equipment, preferably directed to the outside of
buildings. Workers should not be permitted near explosion vents during operation.

Explosions could potentially involve vehicles transporting or discharging flammable or

combustible liquids or gases (gasoline, fuel oil, oxy-fuel burning gases). Procedures should,
therefore, be developed to control these activities in the plant. Explosion of accumulated hydrogen
gas at battery charging stations may be prevented by collecting the gas and venting it safely
outside, and by eliminating sparks or open lights in the vicinity.
Typical principles of fire detection equipment are listed in Table 9.

Table 9 Principles of fire detection

Signal Fire Detection Equipment

Temperature Thermo-fusibles, sprinklers with fusible heads, temperature probes, linear
increase detection of temperature
Smoke Optical smoke detector, laser detector
CO (carbon CO detection is only actual when active carbon is used for gas treatment
monoxide)
Flame Three wavelength infra-red detector
Incandescent Detector with infra-red principle
particles

According to Kirk (2004b), fire fighting facilities should: 1) provide strategically located
hydrants, hoses and extinguishers of appropriate size and rating, and inspect and test them at
intervals at least as frequently as specified by regulatory agencies, 2) maintain clear access in
front of extinguishers, hydrants and hose reels, and 3) train employees on proper use of fire
fighting equipment. Emphasis should be placed on procedures to be followed when a fire is
discovered. Best practices include exercising these steps in this order to: 1) rescue any persons at
risk, 2) alarm or alert others to the fire, 3) contain the fire by closing doors and windows, and 4)
extinguish the fire, in a safe manner. The first letters of this procedure spells RACE. Combustion
produces intense heat and toxic gases, so fire fighting should be attempted only when personal
safety is not at-risk. Specially trained and experienced fire fighting teams, protective clothing and
special equipment should be used as conditions warrant. Typical principles of fire extinguishing
equipment depending on location in a waste processing plant are given in Table 10.
 24

Table 10 Principles of fire extinguishing

Location - Fire extinguishing equipment

part of the plant
Liquid waste storage Injection box of foam inside storage, cooling ring system
(foam or water) on storage circumference,
foam diffusers inside retentions capacity
Drum storage Adapted sprinkler systems (foam solution, powder or
CO2-systems depending on waste stored)
Pasty waste reception pit Foam diffusers
Solid alternative fuel Foam diffusers
final storage
Conveyer belts Sprinkler system with foam
Crushers Powder or foam injection
Dust filters CO2 or nitrogen injection
Active carbon treatment CO2 or nitrogen injection
Rotary screener Sprinkler systems

4.7.2 Workers protection

a) Identification of the properties of the waste

It is requested to get the Material Safety Data Sheet (MSDS) or all available information on the
hazards (corrosive, flammable, toxicity, etc.) of the waste presented for treatment. These can be
obtained from the producer of the waste or by analysis of the physico-chemical properties of the
waste and can be compared with data on industrial toxicology.

b) Compliance of the properties of the waste with the installations

Some properties as corrosion effects, flammability and possibility of dust emission, reaction with
other components, etc have to be checked before formal acceptance of the waste in the
installation.

c) Separation of workers and waste

The concept of the installation and the organisation of storage and handling of the waste have to
be planned in order to limit the workers exposure to the waste, vapours or dust (keep the hazard
far from the worker).

d) Storage and treatment in closed area

In order to limit emissions and dispersions, storage and treatment of the waste should occur as far
as possible in closed buildings, with appropriate ventilation. Keeping the waste in closed areas
reduces drastically the risk of contact, inhalation or absorption by the workers.

e) General safety rules

Due to the variety of waste and hazard properties, it is necessary to simplify as far as possible the
safety instructions and safety rules for the workers. This is why it is recommended to have general
safety instructions such as the obligation to wear individual protections e.g. helmets, safety shoes,
gloves and glasses, as well as masks for dust or organic vapours (for this last element, depending
of the kind of waste which is handled). Specific instructions and adapted procedure have to be
applied only for some wastes presenting special hazard characteristics.
 25

f) Personal information and training

- The workers have to be trained for fire intervention and for first aid action if requested.
- Appropriate emergency plans have to be set up, explained to the workers and training for
emergency situations has to be enforced.
- Each time that a new risk occurs due to a new waste, special information is requested for the
workers.
- Workers must not work alone in isolated parts of a plant and must always be equipped with
appropriate communication tool to report any problem.

g) Personal protection
Individual protections have to be always available and have to be changed each time that a
contamination is identified (overall, gloves, mask-filters, etc.)

h) Controls of
• Atmosphere
Controls of the atmosphere to which the workers could be exposed should be done once a
year or more regularly if the levels of contaminants are near a MAC limit value.
Appropriate ventilation or filter systems can be added.

• Quality of the waste

Analyses are always requested to ensure that the qualities of the delivered waste
correspond to the specifications of a former acceptation. Adaptation in the processing
method, safety rules or rejection of the waste has to be examined when a deviation is
detected.
• Safety requirements
The composition and the risk of waste received are presented to the doctor who is in
charge of the health of the workers. He will identify what appropriate tests have to be done
to control their health. He will eventually recommend protection measures.
• Health of the workers
In the case of exposure to hazardous components, a medical check-up of the worker is
done every 6 month by the doctor. The examination is done on general health aspects, but
also on the research of components or metabolites in blood and urine.
 26

5 PRODUCTION PROCESSES OF AFR BASED ON WASTE

5.1 Solid alternative fuel (SAF)

The goal of SAF preparation is to prepare a tailor-made, homogeneous, and free flowing
alternative fuel to be used in co-processing. The following list (a-d) is an indicative one and
should not be considered as exhaustive:

a) Pasty wastes: High viscosity solvents, oil sludges, distillation residues, sludges from the
treatment of industrial sludges (mechanical industry, chemical industry, pharmaceutical industry,
etc), paints and varnishes sludges, ink sludges, polyol, glues, resins, grease and fats and other
pasty wastes.

b) Powder wastes: Carbon black, toner powder, paints, spent catalysts, surfactants and other
powders.

c) Solid wastes: Polluted polymers, impregnated sawdust, sludges from waste water treatment,
resins, paints, glues, spent activated carbon, polluted soils, hydrocarbon sludges, polluted
absorbents, organic residues from the chemical and pharmaceutical industries, spent plastic
packaging, waste woods and other solid wastes.

d) Liquid wastes that are not suitable for Liquid Alternative Fuel (LAF) production (due to
polymerisation risks, etc.).

Between 20% and 40% of absorbents per ton of SAF produced are used, depending on co-
processing specifications. The kinds of absorbents are fresh sawdust, sawdust from wood
recovery, polyurethane, papers by-product, textile, etc. There is a permanent research for other
absorbents in order to replace the fresh sawdust.

General processes and production steps for SAF can be divided into (a-h):

a) Feeding of the waste from the storage to the production units.

Pre-homogenisation of the incoming wastes is realised based on physical and chemical
characteristics. This step is critical for ensuring the compliance of the SAF with the final users’
specifications. Solid waste and adsorbents (as such or premixed together) can be taken back for
treatment with a bulldozer, a crane, a travelling crane or a walking floor. The transport to the
mixing unit can be done by a conveyor belt, a screw, an elevator, etc. Pasty wastes (as such or
premixed with adsorbents) are handled by a crane or pumped to the mixing unit.
b) Shredding and/or sieving of coarse particles
Wastes that could contain big particles need to be shredded or sieved before introduction into the
mixing unit.

Types of shredders are 1) Slow motion shredder used for flammable and low flash point wastes
(mono-rotor or bi-rotor with large knives), 2) Hammer shredder used for wood pieces, polluted
packaging, and/or plastics, etc. and 3) Dedicated shredders used for specific wastes (e.g.
cryogenic shredder, etc).

Types of sieves used for big particles separation are 1) Vibrating sieve, 2) Static sieve and 3)
Rotary sieve.
 27

c) Feeding of the mixing unit

Concrete pump, endless screw, elevators, bulldozers or conveyor belts are used for the transport
from the shredder to the mixing unit.

d) Mixing operations
These operations are made in closed areas to prevent emissions of dust and volatile organic
compounds (VOC).

Types of mixing systems are: 1) Mixing with a crane in a dedicated pit. 2) Closed mixer with a
range of propellers or screws on a horizontal axis with low speed rotation. This system is efficient
for waste without hard particles bigger than for example 25 cm (e.g. concrete, hard wood, steel,
etc) that could block or damage the propellers or screws. 3) Closed mixer with a “turn-cup” and
an axis with knives.

The safety of the mixing devices can be ensured by using nitrogen as inert atmosphere. The
reduction of oxygen (working conditions between 6 to 8 % of oxygen) by the injection of nitrogen
allows the mixing of waste with flash point lower than 0°C. Materials are fed directly or through a
hopper to stabilise, regulate and control the quantity of waste introduced in the mixing unit.
A conveyor belt is used after the mixing operation to bring the SAF to the sieve.

e) Scrap extraction
Standard magnetic separator on the conveyor belt is used to extract iron and steel particles.
Depending on the desired output, a vibrating sieve can be used to clean the scrap from remaining
sticking residues. In some cases, Foucault current systems could be added to remove non-ferrous
metals.

f) Sieving operations
These operations are made in closed systems to prevent emissions of dust and VOC. The kinds of
sieves are 1) Rotary sieve and 2) Vibrating sieve. The dimensions, as well as the design of the
sieve mesh depend on the granulometry specifications and the off-specification products (different
fractions are possible on some installations, depending on the possibilities of reuse of the big
particles).

Off-specifications fractions can be reprocessed in the production, treated in a dedicated shredder,

and/or treated in incineration or dedicated co-processing units.

g) Storage of SAF before loading

Storage capacities have to be designed to ensure a continuous service. SAF quality is controlled
during the production phase either by automatic or manual sampling before storage. If the quality
does not fulfil the specifications, the product is reprocessed. It is necessary to store the SAF in a
closed area like 1) Closed building with appropriate ventilation and retention where the SAF is
handled with a crane, travelling crane or conveyor belt or 2) Silo (cylindrical or parallel piped)
with a screw or a walking floor to extract the SAF. The type of storage will depend on the need
for homogenisation in the storage unit.

h) Expedition of the SAF

The loading of the trucks (or potentially of train or ships) is done by crane, conveyor belts or
bulldozers.
 28

5.2 Liquid alternative fuel (LAF) as such

These operations can consist of grouping of small quantities and/or pre-processing activities such
as phase separation or settling. The aim of this operation is to blend and homogenise compatible
wastes from several producers and / or sources. The purpose of this operation is to:

• Provide a proximity service to producers having small quantities of organic liquid wastes
• Rationalise the logistic organisation (transports, etc.)
• Develop an adapted solution for packed wastes with several phases (liquid/pasty or solid)
• Separate the different phases (water, organic liquid, sludges or solid) from a composite
waste in order to optimise the recovery
• Prepare homogeneous and stable wastes with specifications in accordance with
environmental protection and co-processing processes or dedicated incineration processes

Wastes suitable for LAF are typically;

• Solvents
• Xylenes, toluenes, white-spirit, acetone
• Cleaning and degreasing solvents
• Petroleum residues
• Distillation residues
• Off specification organic liquid product

General processes and production steps for LAF can be divided into (a-c):

a) Unloading and grouping

1) Liquid wastes in bulk

After filtration and/or settling, organic liquids are sent with a centrifuge or membrane pump to
metallic cylindrical-conical tanks equipped with blending devices in order to avoid settling or
phase separation (pendular mixer or pumping system which blend the top and the bottom of the
tank by continuous circulation). If necessary, storage will be made inert with nitrogen. Each
storage tank is put in a waterproof retention area and equipped with a level indicator. Gas effluent
from events are collected and treated.

2) Packed wastes (drums, etc.).

Before grouping, the packaging is emptied with techniques adapted to their physical-chemical
characteristics. Generally, two phases exist; a liquid and a pasty (and sometimes solid) in the
bottom of the drum. For liquid wastes the drums are put in a ventilated emptying area. After
opening, the liquid phase is pumped to a small buffer tank. A compatibility test is carried out
before transfer to the final storage. Pasty and solid wastes present in the bottom of the drums will
be processed in solid alternative fuel production (see chapter 5.1). This step can be carried out
manually or in an automated emptying station.

b) Preparation
This step can consist as operation such as settling, grinding, filtration and blending. A stirring
propeller or a re-circulation system is used in order to keep the wastes homogeneous. Sometimes,
a grinding system is used with re-circulation technique in order to decrease granulometry of solid
particles which may be in the liquid waste.
 29

c) Expedition
Before loading, the liquid preparation is filtered through a 3 mm mesh. The loading of the trucks
is done with all the security systems needed.

5.3 LAF by fluidification

Fluidification means processes where liquid, pasty and solid wastes are homogenised and
shredded together in order to produce liquid alternative fuel (LAF) for co-processing.

Typical acceptable wastes for fluidification are;

• Pasty organic wastes (ink sludges, paint sludges, adhesives wastes, etc.)
• Oil residues
• Pulverulent wastes such as paint powder
• Filter cakes
• Residues from organic chemical synthesis
• Oil and fat
• Spent ion exchange resins
• Distillation residues
• Wastes from cosmetic industries

The fluidification process is composed of 4 main sections (a-d). In order to prevent emissions into
the environment, the first section of operations are done under controlled ventilation. This
measure allows to trap VOC and dusts and to treat them with air filters. The last 3 sections of the
process are run in closed vessels and pipes. For this part, VOC emissions are very low (exhaust
gas of the vessels and tanks) and are treated with other VOC on a dedicated equipment.

a) “Calibration” of pasty part

This step consists in both shredding coarse particles and extracting of foreign metallic parts
blended accidentally with chemical waste, and transfer of this pasty product into the mixing tank.
Shredders used are 1) Slow motion shredder for flammable and low flash point waste (mono-rotor
or bi-rotor rotary shears) or 2) Dedicated shredders for specific waste (e.g. cryogenic shredder,
etc).

Over-bands are necessary for extracting foreign metallic bodies from chemical waste.
Technologies based on Foucault current are also used for isolating nonferrous metals. Vibrating
sieves and / or static grates can also be used in this conditioning step to remove big particles in
order to facilitate the operation of the shredder.

The product can be transferred by: 1) Endless screw as the cheaper solution. It requires a limited
slope from screw bottom to mixing tank inlet (less than 15° for the screw) and a by-pass for liquid
(from screw bottom to mixing tank). 2) Pump (e.g. a concrete pump).

A simpler design is beneficial for lower investments (small capacity unit) or when the wastes are
prevented by strong by-product (e.g. waste from distillation). In this case, the product may be
transferred into the mixing step by shredding. A rotary filter may be installed to remove large
quantities of by-products.

b) Dissolution and screening

The aim of this step is to dissolve and emulsify pasty parts into a solvent phase to reach a
homogeneous product.
 30

The dissolution of solid organic compounds in the liquid phase composed of solvents and / or
waste water is carried out by special mixers, rotary screens and buffer tanks. The mixers must
respond to the constraints of sticky material containing strong and voluminous solids in
suspension. They pulverise the solids between rotor and stator and blend them into the liquid
phase. Once the dissolution of hydrocarbons is achieved, the liquid mixture is admitted inside a
rotary screen which extracts the pieces of plastic lining fragmented by the shredder of the prior
step. A buffer tank collects the product at the end of this step.

c) Grinding and emulsifying

This step consists in finely grinding the solid particles remaining in suspension in the liquid phase.
It consists also in making a fine emulsion between the aqueous and hydrocarbons phases
constituting the alternative liquid fuel. The stability and the quality of combustion of the fuel
depend directly on both, its homogeneity and the size of fragmentation of the solids in suspension.
Those criteria require high velocity technologies of grinding / emulsifying protected by magnetic
separators and mechanical filters. The equipment must be flexible enough in order to accept
fluctuations of viscosity, density and nature of the solids in suspension.

Risks of fire / explosion inside this section are prevented by a hydraulic guard inside the buffer
tank of the previous section. This guard prevents any penetration of oxygen inside the machinery.

The alternative fuel quality is controlled at this step, during filling up of the buffer tank. Some
parameters such as pH and viscosity can be controlled continuously. Other parameters such as
LCV, composition, flash point, are controlled from samples taken during the production. If the
quality doesn’t meet the specification, the fuel must be reprocessed before being transferred to the
storage unit.

A simpler design is possible for lower investments (small capacity unit) where steps b and c may
be done at the same time. In this case the mixing and buffer tank are the same and the grinding
line runs into the mixing tank.

d) Storage and dispatching

Once a high level is reached inside the buffer tank, the liquid alternative fuel can be transferred by
pump into the final storage. During this transfer, a latter adjustment of the quality of the fuel can
be carried out by means of grinders and filters operating on the transfer line.

The storage capacity is generally composed of vertical cylindrical-conical tanks with blending
equipment. Two technologies of blending are appropriate to homogenise the liquid fuel: 1) A long
marine mixer installed on the roof of the tank, or 2) A pumping system which blends the top and
the bottom of the tank by loop circulation. The technology of a vertical agitator without any
bearing inside the tank is the most efficient.

Dispatching to the cement kilns is carried out by a truck loading station. This loading station is fed
by the storage unit mentioned above.

5.4 LAF by emulsification

The aim of this liquid alternative fuel process is to produce homogeneous and stable products
which comply with environmental protection and co-processing specification. The origin of this
process comes from the theology comportment of pasty preparation for clinker production. The
installations used to produce this type of LAF are similar to those used for the pasty raw meal
 31

preparation for clinker production. This process is based on the control of blending by means of
chemical or surfactants addition.

The following list of wastes suitable for emulsification is indicative and should not be considered
as exhaustive:
• Oils emulsions from mechanical and metallurgy industries
• Wastes and sludges containing oil from petroleum refining, from collection and storage of
oil products
• Wastes from oil distillation and regeneration
• Waste from production failure (off-spec products)
• Pasty wastes such as grease, ink and adhesives wastes
• Pulverulent waste such as paint powder, washing powder wastes etc
• Used bases such as sodium hydroxide
• Used oils

General processes and production steps for LAF by emulsification can be divided into (a-f):

a) Feeding of the waste from the storage to the production units

Before introduction into the production process, wastes are de-conditioned with equipment
adapted to their physical characteristics. Pasty wastes extracted form drums are put in special pits.
They are first handled by mean of a mechanical shovel to a homogenisation pit. Then, they are
transferred to a hopper in order to be introduced to the production process by a screw conveyor or
a concrete pump. Pulverulent wastes such as paint and washing powder are received in big-bags.
They are directly put in the production process with adapted equipment which will capture dust
emissions. Liquid wastes are handled by pump. Pumping technologies (centrifuge pump,
volumetric pump with outer rotor, etc) must be able to accept fluctuation of viscosity and presence
of particles in suspension.

b) Formulation
According physical-chemical characteristics of the waste stored, the laboratory defines
specifications including nature and quantities of wastes which are to be put in the production
processes. Compatibility tests are also developed. Such tests are carried out at every operation, in
order to comply with the LAF co-processing specifications.

c) Production process
The production process is a batch one. It is carried out by special mixers (called “delayers”),
closed in order to prevent VOC emissions. The different components are introduced in the mixer
according to laboratory specifications. An agitator provides a stable emulsion production. During
this step, several parameters are monitored, such as viscosity, pH, temperature and motor
specification. One of the purposes of this monitoring is to detect polymerisation reaction.

d) Screening
Once the emulsion is achieved, it is circulated again with a centrifuge pump to the mixer and
through a curved screen providing particle retention above 4 mm.
 32

e) Sand extraction
When the mixer is emptied and before being sent to the storage capacity, the LAF is pumped to a
concrete pit with a sedimentation area. The aim is to separate through density mineral solid
particles (e.g. sand) which may be present in the LAF production.

f) Storage and dispatching

The LAF is transferred by centrifugal pump to the storage. The capacity of storage is generally
composed of concrete or steel vertical cylindrical tanks with blending equipment. Three
technologies of blending are appropriate to keep the homogeneity; 1) a submerged agitator, 2) a
low agitator with scraper in order to avoid sedimentation and 3) a pumping system which blends
the top and the bottom of the tank with high flow (around 250 m3/hour) loop circulation.

The LAF quality is controlled in order to be sure that its characteristics comply with the cement
kiln specifications. In some specific cases, addition of energetic waste may be done if the calorific
value is considered too low. Dispatching to the co-processing factories is carried out by a truck
loading station. A final screening (through a mesh of 3 mm size) is done whilst loading.

5.5 Pre-processing plant examples

5.5.1 Energis, Holcim Group, in Albox, Spain

Energis was created in 1997 as a subsidiary of Holcim Spain. The purpose of the company is to
add value to Holcim Spain’s cement operations by providing waste management solutions to
industry and communities through co-processing of waste in Holcim cement kilns. To directly
access the waste market, Energis established the pre-processing plant at Albox in 2003. The plant,
located in south-eastern Spain, transforms a wide range of solid, pasty, and liquid wastes into
impregnated sawdust and liquid alternative fuels.

Energis at Albox has two main production lines: (1) a shredding and mixing line in which solid
and pasty waste are mixed with sawdust to produce impregnated sawdust and solid alternative fuel
(SAF), and (2) a liquid storage and blending line for liquid alternative fuels (LAF). The lines are
designed to produce 60,000 tons of SAF and 20,000 tons of LAF per year. Half of the sawdust
used in SAF production must be fresh, and substitutes may be mixed with the sawdust. The main
impregnation substitute material is compressed cellulose. Moisture content varies significantly
among deliveries and suppliers, and greatly affects the impregnation capability of sawdust. This in
turn affects the percentage of sawdust required for SAF production.

About 90% of Energis’ waste is delivered in drums, 10% is transported in bulk by tanker or
container truck, and a small amount is delivered in large bags. Waste for SAF include
contaminated earth and sand, resin, paint, distillation residues, sludges of ink, glue, varnish and
oil, mastic, filter cake, grease, soap, used catalysts and alumina sludge. Waste for LAF includes
waste oil, polluted water and halogenated as well as non-halogenated solvents, etc.

In July 2005 Spain introduced a law banning organic waste in landfills. This gave Energis at
Albox more opportunities to find organic waste on the market. Only waste from authorized
producers or collectors is accepted. To become authorized, the waste producer must submit a
sample for analysis to the on-site laboratory, and permit Energis representatives to visit the
producer and collect information about its manufacturing process. If the producer and the waste
meet Energis’ requirements, Energis at Albox issues a certificate. To prevent contamination, each
delivery undergoes rigorous quality control.
 33

Energis at Albox does not treat wastes such as pressed drums and metal separator residues, which
are sent to a foundry for recycling. Pallets are taken back by the sawdust supplier, non-polluted
scrap metal is sold to a local scrap dealer, and waste that cannot be processed – such as drums that
cannot be shredded – is sent to a third party for treatment. Thanks to preliminary testing, a strong
external communications policy, detailed analysis and a strict refusal policy, the percentage of
refused waste is low.

The plant’s success ensures a sustainable flow of AFR to Holcim Spain offers an innovative and
practical solution to waste producers and, above all, benefits the cement industry as a whole.

The design of the pre-processing plant at Albox (see Fig. 1) is similar to an earlier plant in
Belgium: Scoribel. Energis at Albox profited from the many lessons learned at Scoribel. But
market conditions in Spain and Belgium differ: 90% of the waste in Belgium is transported in
bulk, whereas 90% of the waste in Spain is transported in drums. Each drum must be sampled as
part of the quality assurance program, and properly handled and stored, which increases
operational costs. The plant at Albox faced the problem of shredder fires caused by friction
between the drums, their contents and the machinery during shredding. To reduce this risk,
nitrogen was used as inert gas during the shredding operation, which increased the overall pre-
processing costs. Over the past two years, Energis at Albox has got these problems under control.
It has improved its sourcing of critical spare parts, and developed a special course to teach
workers how to prevent shredder fires.

Fig. 1 Scheme of AFR production at the pre-processing plant of Energis at Albox. The legends
CSSf and CCS g in this case stands for fine and coarse SAF, respectively.
 34

5.5.2 Ecoltec, Mexico

Ecoltec has facilities that process all types of waste. Agreements with the customers regulate the
packaging and the collection/delivery conditions of waste materials. Transport is done in tanks or
barrels or as bulk material by an external company.

Liquid waste (e.g. waste oil, solvents, etc.) is mixed and stored in tanks before being fed into the
cement kiln. Solid waste (e.g. plastic packaging, chipped tires, waste textiles etc.) and sludgy
waste (e.g. paint residues, distillation sludges, oil sludge, etc.) are mixed with clean sawdust (see
Fig. 2) and then shredded. During the sieving process, the fine, solid mix is separated from the
coarse mix and then forwarded via conveyer belt to the storage building. The AFR is now ready to
be transported by truck to the cement plant. A sketch of the pre-processing plant for SAF is
reproduced in Fig. 3.

Quality control is an essential part of pre-processing activities. First, clinker production requires
that the used AFR fulfils certain requirements concerning calorific value, pH-value, humidity,
chlorine and sulphur content. Second, accumulation of pollutants in the cement and excessive air
emissions must be avoided. Quality control takes place in the internal laboratory, where test
samples of incoming waste and of AFR are held ready to be fed into the cement kiln. The test
samples and records of the results of the analysis are stored for security and reference purposes.
The results are reported to the authorities on a regular basis.

Fig. 2 Handling impregnated saw dust at Ecoltec, Mexico. Note worker protection.

The pre-processing activities are organized by Holcim Apasco’s pre-processing subsidiary,

Ecoltec. It offers complete waste disposal solutions to customers, independent of whether the
waste is suitable for co-processing or not. Waste not suitable for co-processing is forwarded to
companies with adequate treatment facilities. For the transport of certain wastes, plastic or steel
barrels are used. The plastic barrels are shredded and used as AFR. The steel barrels are
forwarded for recycling once waste is removed. The barrels are squeezed flat with a special
machine before recycling.
 35

The mixing process of sludgy waste with solid waste is done in an open building. The Volatile
Organic Compound (VOC) emissions from the sludge must be drawn away to protect
occupational health. A monitoring program assesses environmental impacts so managers can
decide if further measures are required. VOC emissions are involved in the formation of summer
smog. Common reduction techniques are nitrogen traps and biological treatment.

The many different types of customers and the analysis of their different wastes require attention.
Problems encountered in the transformation process from waste to AFR and in the clinker
production due to unexpected pollutants in the waste, can be avoided by a frequent analysis of
waste samples and securing the traceability of the waste from the customer to the cement kiln.
The installation and running of pre-processing facilities requires development of strong relations
with local communities. Their worries and fears about the negative effects of waste treatment
need to be overcome, so Ecoltec held a series of open days for the public that included a plant
tour. Beside general rules for pre-processing, special regulations are required for certain wastes
(e.g. persistent organic pollutants, POPs). Although not critical from a technical point of view,
public concerns remain about the formation of dioxins and furans during the combustion of POPs.

Sieving

Fig. 3 Sketch of the SAF production at Ecoltec, Mexico.

 36

5.5.3 Recent waste deal between Shanks and SRM of Castle cement, UK

The waste firm Shanks (www.shanks.co.uk/shanks/ ) has recently (February 2008) secured its
second contract to supply solid recovered fuel (SRF) to the AFR pre-processing plant SRM, a
subsidiary of Castle cement, UK. Under the Shanks contract, up to 50,000 tons of solid recovered
fuel produced at mechanical biological treatment plants at Jenkins Lane and Frog Island in East
London and Dumfries in Scotland will be sent to Castle Cement's Ketton works in Rutland. Here,
the material will be shredded and blended by Castle's sister company SRM before being used to
replace fossil fuels as AFR in the main kiln. For further information see
http://www.letsrecycle.com/do/ecco.py/view_item?listid=37&listcatid=217&listitemid=9666
 37

6 ENVIRONMENTAL ISSUES

6.1 Consumption of resources

In terms of energy consumption, the electricity amount required to produce SAF varies from 5-25
kWh/ton, while the range for LAF is 5-20 kWh/t. The fuel consumption is from 0.15-3 litre per
ton produced SAF and 0.05-2 litre per ton produced LAF. These data don’t include energy
consumption for ventilation and air treatment. The large variation in electricity consumption is
due to the different types of wastes, the packaging and the level of automation. For example, in
the case of packaged drums to be shredded, the electricity consumption can reach 25 kWh/ton,
while in the case of bulk wastes in a non-automated process line it will be 5-10 kWh/ton.
Moreover, when the electricity consumption is high, the fuel consumption is usually on the low
side. The fuel consumption is mainly for utilities vehicles and will decrease with the automation
level. The total energy consumption represents less than 5% of the total energy content of the AF.

Water is used for cleaning of installation, trucks and eventually drums, maintenance and spraying
installations for dust abatement. The consumption is typical 5-20 litre per ton AF produced. On a
general base, the water consumption is related to a good housekeeping of the AF production
installation. It varies widely according to the type of wastes, the packaging and the eventual use of
recovered rain water. If drums or containers need to be cleaned or rinsed for further use, an
additional consumption of 2 to 20 l/ton AF can be anticipated.

In some cases, nitrogen is used for making mixers, shredders or liquid storage inert. In such a
case, the consumption of nitrogen may be 1-2.5 m3/ton AF produced.

Other materials may be required for effluent treatment.

6.2 Emissions to air

Dust is typically emitted during production of SAF during unloading and handling of absorbents
and/or pulverulent wastes, processing and loading, but also during production of LAF by
fluidification. Types of dust are absorbents (mainly from sawdust) and powdery wastes (paints,
resins, washing powder, catalysts, etc.).

Dust is monitored for

1. Canalised emissions: One control per year carried out by a certified laboratory
2. Air treatment systems: Follow up of the efficiency of the cyclone and bag filters by
pressure drop or opacity measures
3. Diffuse emissions: Can be followed by measurement with Owen gauge localised at the
site.
Typical obtained values and limits for dust are listed in Table 11.
 38

Table 11 Typical dust emission values during AF production and limits

SAF LAF
After treating canalised emissions (daily average values)
Achieved performance (mg/Nm3) 1-10 1-5
Permit limit (mg/Nm3) 20-50 20-50
Emission from production site (mg/m2/day) 1.5-90 <1
< 100 m from emission source (depend on location of Owen gauge)

6.3 Volatile organic carbon (VOC) and smell

Most accepted wastes contain organic compounds. In certain circumstance, according to vapour
pressure and temperature, they are more or less volatile. These volatile organic compounds (VOC)
could be potentially harmful for the environment and workers and could cause bad smell. This is
why these emissions need a particular attention and follow up.

The level of VOC emissions is a function of the nature of wastes, its flash point, vapour pressure
of wastes components, and their concentration. VOC emissions are also influenced by the type of
process and the climatic conditions.

Emission of VOC and smell occurs during unloading operations (trucks, drums and containers) of
both SAF and LAF, sieving of SAF and sampling of LAF. It can also occur under certain
circumstances during storage of SAF and LAF, as well as during sampling of SAF. The nature
and the concentration of VOC depend on the type of waste received at the site.

Monitoring should be made of

1. Smell: Standardised tests for smell detection can be used to identify the influence of the
process on the neighbours and workers environment. Bag samples may also be made for
qualification and quantification of the pollutants in laboratory.
2. Diffuse emissions: Diffuse emissions are measured inside and outside workshops by
taking samples. Quantitative and qualitative analyses can be carried out.
3. Canalised measures: VOC are measured either continuously by FID system or according
to punctual measurements campaigns. Those conditions are defined in the permit.

Emissions values to ambient air in the working area have to comply with the national regulations.
Canalised emissions after treatment are listed in Table 12.

Table 12 Canalised emissions after treatment

Daily average value SAF LAF

Achievable performance 4-50 10-110
3
Non-methane VOC (mg/Nm )
Permit value 20-1101 0-1101
Non-methane VOC (mg/Nm3)
1
with water and oxygen content as achieved by the process
 39

6.4 Impact on surface and ground water

Surface water can be contaminated by cleaning water from drum cleaning, truck cleaning,
facilities cleaning and road tankers / ship cleaning and/or by process water from wastes settling
during transport, from drying, etc.

A synthesis of discharge limit values based on permits for 6 AF processing units in France and
Belgium is presented in Table 13. These values have to be considered as examples. They are not
indicative and depend on the water used. In some cases, water effluents are treated in an external
and collective station. Specific values have to be defined from case to case. Waste water must be
monitored before release.

With the exceptions of major accidents, AF activities have no impact on groundwater. A

piezometer network with analysis once or twice a year is generally used for survey.

Table 13 Examples of waste water discharge limit values from 6 plants in France and Belgium

Physio-chemical Limit values

parameters
pH 5.5-9.5
Maximum temperature (°C) 30-45
TSS (mg/l) 30-60
COD (mg/l) 50-300
BOD5 (mg/l) 30-40
N Kjeldahl (mg/l) NA2-40
N global (mg/l) 10-50
Total phosphate (mg/l) 1-10
Cr +VI (mg/l) 0.01-0.1
total Cr (mg/l) 0.02-0.5
free CN (mg/l) 0.1
Cu (mg/l) 0.03-0.5
Cd (mg/l) 0.05-0.2
F (mg/l) 10-15
Zn (mg/l) 0.3-2
Sn (mg/l) 0.01-2
Pb (mg/l) 0.05-0.5
Ni (mg/l) 0.05-0.5
Hg (mg/l) 0.05-0.15
Total metals1 (mg/l) 10-15
Total hydrocarbons (mg/l) 2-10
1
Sb + Co + V + Tl + Pb + Cu + Cr + Ni + Zn + Mn + Sn + Cd + Hg + Se + Te
2
NA = not applicable
 40

6.5 By-products and wastes generated

Generated by-products may be

1) Residues coming from the packaging of the delivered wastes

- « Consigned » IBC, containers or drums
- Metallic containers and drums
- Plastic containers and drums
- Palettes
- Big bags
- Plastic sheet

2) Production Residues
- From the scrap extraction during the production stage: These residues are composed of metallic
parts which can be voluminous and massive
- Rotating, vibrating and static sieve / screen rejects: These residues are composed of blocks of
different solid wastes (such as resins, paintings, glues, tars, bitumen, polluted soils, etc.), pieces
of wood, sand, polluted plastics, lining and piece of textiles sheets.

3) Effluent treatment residues

These residues can for instance be activated carbon from waste water and air effluent treatment.

Generated wastes can be laboratory residues and rejected samples. Typical by-products from
recovery (pallets, iron scrap etc.) can amount to 1.5-20 kg/ton AF. Other wastes for disposal can
be about 0-3 kg/ton AF produced and laboratory residue around 0.015 kg/ton AF. The amount of
by-products is strongly linked with the type of packaging. For example, in the case of small
packaged wastes, the iron scrap fraction can reach up to 150 kg/ton AF. These data should be
reported annually to the authorities.

6.6 Noise

All the process lines and the equipment are designed and realised according to EU noise
regulation for operators inside and for neighbours. Incoming and outgoing transports are the main
source of noise around and inside the plants. Other noise sources can be:

- Handling machines such as mechanical shovel, loader, and hydraulic shovels

- Screeners
- Shredders, grinders
- Pumps
- Agitators
- Motors used for ventilation network
- VOC treatment units

Due to the relatively low noise level, no specific monitoring is usually requested. But, measures
can be done for health and safety of workers and especially for environmental impact evaluation,
notably when new equipment is commissioned.
 41

7 TECHNIQUES TO INCLUDE IN BAT DETERMINATIONS

7.1 Preventive measures and reduction techniques for dust

This list of preventive measures against dust re-groups several measures which exist on the plant.
It’s an indicative list and not an exhaustive one:

• Closing and under-pressure for all the reception, production and storage areas.
• An atmospheric over-pressure at the working places (control room, vehicles cabin, etc)
ensures that no dust reaches the workers.*
• Preparation and mixing operations have to be done in closed areas with canalised exhaust
air.
• Pulverulent wastes have to be handled in closed areas.*
• Dust retention net.*
• Efficiently cover loads of fresh sawdust, pulverulent waste or SAF before transport*
• Use of closed vessels / mixers / filters / screens / magnetic separators / homogenising
equipment.*
• Spray / atomiser systems intended to moisturise ambient and confined air in order to
prevent dust emissions.

Preventives measures marked with * in the above list could be applied on existing facilities
without complete redesign of the facility.

Emission treatment by filtration techniques comprises (a-d):

a) Wet scrubber
Principle:
Gas flow is cleaned in a liquid phase which captures solid particles.
Comments:
This technique is not used in the existing LAF and SAF production plants due to the fact that
some dusts are hydrophobic and that the wet residue cannot be easily reused in SAF production.

b) Bag filter (see characteristics in Table 14)

Principle:
Solid particles are trapped by a woven fabric while gas can flow through it.
Advantages:
- High collection efficiency for both coarse and small particles
- Efficient with a large concentration range
- Collected dust may be reused in the AF process
Disadvantages:
- Explosion risk

c) Cyclofilter
Principle:
Coarse particles are captured by a cyclone. This technique is not commonly used in the AF sector.
The technique may be only used in combination with bag filter.
Advantages:
- Efficient with a large concentration range
- Collected dust may be reused in the process.
Disadvantages:
 42

- Not efficient for small particles

- High wear with abrasive dust
- High electricity consumption

d) Electrostatic filter
Principle:
Dust particles are electrically charged and captured in an electric field.
Comment:
This technique is not suited for organic particles due to high explosion risk.

Table 14 Characteristics of bag filter for dust filtration

Characteristics Value ranges

3
Input gas flow (Nm /h) 1,000 - 50,000
Input dust concentration (mg/Nm3) 100 - 5,000
3
Output dust concentration (mg/Nm ) < 10
Risks explosion
Electricity consumed (kWh/ton SAF) 2.5-3.5
Investment cost (€/ton SAF/year) ≤4
Operational costs (€/ton SAF/year) 0.15
Maintenance cost (€/ton SAF/year) 0.1

7.2 Preventive measures and reduction techniques for VOC and smell

Preventive measures are closed and under-pressurised room for VOC and smelling wastes (see
chapter 7.1 on dust).

Emission captures (grouped a-e) during:

a) Sampling
Packaged wastes must be sampled inside or in closed areas kept in under-pressure or inside
dedicated chamber with extractor hood.

b) Unloading operations
• Liquid: Exhaust gas from vessels and tanks are collected
• Solid and sludge: Depending on the potential of emissions of VOC of the wastes, unloading
should be done in a closed and under-pressurised building.

c) Storage
•Bulk materials: In closed tank or in dedicated area. Containers and drums must not cause VOC
emissions.
• Liquid storage: Exhaust gas must be collected and properly treated.

d) Processing:
The process lines described in chapter 5 have to be kept in confined atmosphere with under-
pressure.

e) Loading:
The loading station must be designed and operated in order to prevent emissions. VOC is
collected in each above mentioned points, as near as possible to the emissions sources. The
 43

collected stream is oriented to the appropriate VOC treatment facilities taking into consideration
that de-dusting is necessary in most cases.

VOC emission treatments can be grouped a-d as below. A comparison overview is given in Table
15:

a) Liquid nitrogen trap

Principle:
Condensation of VOC with liquid nitrogen. Used for relatively small volumes to be treated, when
liquid nitrogen is available and concentration of VOC is high.
Advantage:
- The condensed VOC can be recovered.
Disadvantages:
- The presence of water vapour in the air can block the system by the condensation of ice. A de-
freezing period is then necessary.
- This technology is suitable for stable volumes and compositions.

b) Biological treatment
Principle:
VOC degradation by bacterial beds; biological treatment is used for VOC streams that have a
consistent and biodegradable composition.
Advantages:
- Low cost
- Low energy consumption
Disadvantages:
- Reliable only for some kind of emissions.
- Sensitive to some components / chemicals that can be toxic for the micro-organisms.

c) Activated carbon
Principle:
VOC adsorption through activated carbon filter. The use of activated carbon is efficient for the
capture of VOC mainly in storage facilities. The absorption capacity of the activated carbon
depends on the VOC nature but is limited to maximum 300 g of VOC / kg of activated carbon.
Advantages:
- Low operating cost for low concentrations of VOC
- Usable for a wide range of components
- Simple design
- Stable over time
- Accepts high spot concentrations
- Used activated carbon can be recovered several times or included in the alternative fuel process.
Disadvantages:
- Cost of activated carbon renewal
- In some concentrations with air, the adsorption is exothermic and has to be controlled in order to
avoid fire / explosions.
- Not suitable for high concentrations or small molecules or in presence of dust and not adapted
for some molecules, such as acetone.

d) Thermal treatment (sub-divided 1-3):

1) Combined combustion
Principle:
 44

In some plants where combustion takes place, it is possible to inject polluted air collected in the
workshop in the secondary air circuit of the burner of thermal equipment or the primary air of the
burner. This may involve specific adaptation of the combustion process (modification of gas
cleaning and stability of combustion).

Advantages:
- Synergy with existing combustion facilities.
- Energy recovery of the VOC in the combustion
Disadvantages:
- Not available during maintenance of the burner
- Need prior dilution with air when an explosive concentration can be reached
- Specific instrumentation and valves must be installed to prevent “domino effect” between each
process.
- Adaptation cost can be high
- Fluctuations in quality or quantity of the VOC could cause some troubles in the combustion
system.

2) Catalytic combustion
Principle:
The polluted air is burnt but the combustion temperature is reduced by the use of a catalyst. The
catalyst helps to get the same destruction efficiency of the VOC as at a lower temperature.
Advantages:
- Low fuel consumption
- Complete destruction of VOC
Disadvantages:
- The catalyst is sensitive to some compounds (metal, organic, etc.) and its efficiency can
progressively decrease.
- Cost of investment is relatively high
- Need of a gas treatment in some cases (EP or textile filters, gas scrubber)
- Needs prior dilution with air when explosive concentrations are reached

3) Regenerative Thermal Oxidiser

Principle:
VOC are burnt in combustion chambers at a temperature ranging from 750-950°C. The energy
produced by the combustion of the VOC is used to preheat the polluted air on the ceramic bed
before the combustion. The combustion temperature can be adapted according to the VOC
concentration.
Advantages:
- High VOC destruction rate (> 99%).
- Accepts concentration fluctuations of VOC.
- Reduced use of fossil fuel or waste fuel (high energy efficiency)
- Auto-thermal temperature can be approached, so that the combustion of the VOC is almost
sufficient to maintain the temperature (in that case, the quantity of make-up fuel is minimal)
- Low operation cost
Disadvantages:
- High investment cost
- Needs prior dilution with air when an explosive concentration may be reached
- Needs a de-dusting when dust concentration is higher than 20 mg/Nm3
- High energy consumption in case of low VOC concentration.
 45

7.3 Preventing pollution of surface and ground water

Preventive actions to avoid surface and ground water pollution can be:

- Site waterproof and storage retention.

- Implement regulatory verification procedure for tanks and pits.
- Separated water drainage according to pollution load (roof water, road water, process water).
- Security collection basin
- Piezometers network for ground water monitoring

According to degree and nature of the pollution agents and to the output (surface water, on site
water treatment, collective industrial or urban station, incineration), different techniques may be
used to treat process water alone or combined:
- Settling, hydrocarbons /oils/ sludge separators,
- Activated carbon (should be sufficient for low contaminated water)
- Physico-chemical treatment
- Biological treatment
- Thermal treatment (for highly polluted water)

The by-products of these installations (used activated carbon, sludge, hydrocarbons, oils, etc.) can
been reintroduced in the AF production process or directed to external treatment plants.

Table 15 Comparison of VOC treatment processes

Nitrogen Biological Activated Combined Catalytic Regenerative
trap treatment carbon combustion combustion Thermal ox.
Characteristics
Input gas3 flow < 100 < 100,000 < 50,000 < 50,000 20,000 - 20,000 -
range (m /h) 50,000 80,000
Input VOC 2,000 - < 1,000 < 500 ≈3,000 1,000 - 2,000 - 4,000
concentration 500,000 < explosion 3,000 with peak until
(mg/Nm3) limit 10,000
Output VOC - - 40 - 110 10 - 50 10 - 50 15 - 50
concentration
(mg/Nm3)
Efficiency (%) > 95% < 90% - - - > 99%
Preliminary No No Yes No Yes Yes
de-dusting
Risks - Destruction Quick - Catalyst -
of micro- saturation poisoning
organisms
Residues No Yes No No No No
Consumption (per ton AF produced) a
Electricity 25 15 25 - 75 25 - 75 10 - 50
(kWh) a
Fuel/gas (kWh) - - - 70 - 140 50-200b
AF or biogas - - - - - Yes
Reactant Nitrogen Barks 0.1 - 0.5 kg - Catalyst -
active C/kg VOC
Costs a
Investment 20 - 60 10 - 20 10 - 30 20 - 30 10 - 25
(€/ton capacity)
a
Operational
(€/ton AF)
Electricity 1-3 1-3
Fuel/gas 0 1-2 1-3
Others 2-6
Total 2-6 <1 1.65b
a
Maintenance - - - <1 <1
a b
Depends on each case. According to VOC concentration
 46

7.4 By-product recovery and waste treatment

Treatment of by-products coming from packaging of delivered wastes can be grouped into a-d:

a) Consigned IBC, containers or drums can either be sent back directly to the producer or, after
being emptied, cleaned up with appropriate devices.
b) Metallic containers and drums
• Reuse
• Drum recycling, after eventually cleaning.
• Recovery after cleaning and shredding or crushing, in the process or separately.
• Disposal by incineration with iron recovery

c) Plastic containers and drums

• Reuse
• Drum recycling, after eventually cleaning.
• Recovery after cleaning and shredding or crushing, in the process or separately.
• Co-processing use as an alternative fuel
• Disposal by incineration

d) Palettes
• Reuse if in a large majority of case (no damage)
• Wood recycling, also as absorbents
• Co-processing use as an alternative fuel
• Disposal by incineration

Treatment of by-products from production can be grouped a-c:

a) Residues coming from the scrap extraction

They are collected separately during the fabrication process. After an eventual cleaning step, they
will be sent with the cleaned metallic containers and drums for recovery.

b) Residues coming from rotating and vibrating sieve rejects

They are eventually shredded and sent to the co-processing facilities. If there is no possibility to
co-process them, they have to be brought to a hazardous waste incinerator.

c) Effluent treatment residues

Activated carbon from waste water and air effluent treatment are incorporated in co-process.

Laboratory wastes that are mentioned in the permit of the pre-processing facility can be treated
directly, and used in the production. Those which are banned in the permit have to be properly
disposed off in external dedicated facilities.
 47

8 BEST AVAILABLE TECHNOLOGIES (BAT)

8.1 General

BAT is enforcing multi step traceability (as described in chapter 4.2). BAT is enforcing at least
the minimum control plan as described in Table 8.

8.2 Preventive measures for dust, VOC and smell emissions

BAT is an appropriate combination of following recommendations:

• Closing and establishing under-pressure in all process rooms
• Handling pulverulent wastes in closed areas*
• Before transport, loads of fresh sawdust, pulverulent wastes or SAF have to be covered.*

Preventives measures marked with * in the list above could be applied on existing facilities
without complete redesign of the facility.

BAT for dust treatment is bag filters. Table 16 compares bag filter with wet scrubber.

Table 16 Dust treatment BAT criteria. Legend: - means poor,

+ means acceptable and ++ means well adapted.

BAT criteria Bag filter Wet scrubber

Dust treatment performance + -
Flexibility + +
Consumption ++ -
Costs ++ -
Risks (fire, explosions, etc.) + ++
Cross media effects + -

8.3 VOC emission capture and treatment

For VOC emission capture, BAT is an appropriate combination of following recommendations:

• Sampling of packaged wastes has to be done, at minimum in a covered area and inside.
• Unloading operations for solid wastes and sludges have to be done in a closed area and in
building with under-pressure if the potential of VOC emissions is high.
• In unloading operations for liquid wastes, exhaust air from vessel and tank are collected.
• Storage must be made in closed tanks or buildings for bulk materials. Containers and drums
must not cause emissions of VOC.
• Exhaust gas must be collected and properly treated for liquid storage.
• Process lines described in chapter 5 have to be kept in confined atmosphere with under-pressure.
• Loading station must be designed and operated in order to prevent emissions.
• VOC is collected in each point mentioned above, as near as possible to the emissions sources.
The collected stream is directed to the appropriate VOC treatment facilities taking into
consideration that de-dusting is necessary in most cases.

For VOC emissions treatments BAT are;

 48

- Combined combustion, but only if combustion facilities are available nearby, or

- Regenerative thermal oxidation,
- Activated carbon for low concentration VOC flow (storage etc.).

BAT criteria for VOC emission treatment are compared in Table 17. Other comments to
treatments in Table 17 are for:

• Nitrogen trap: Non-appropriate due to low flow range, high operating cost and sensitivity
to water presence.
• Biological treatment: Appropriate for big volume with low and stable concentration.
Performance sensitive to composition (ammonia, etc.) and weather conditions.
• Activated carbon: Appropriate for low concentration flows (e.g. storage). In this case, low
cost. Performance may be limited because of incomplete capture of some organic
molecules. May also present fire and explosion risks.

Table 17 BAT criteria for VOC emission treatment. Legend: - means poor,
+ means acceptable and ++ means well adapted.
BAT criteria N2 Biological Active Combined Catalytic Regenerative
trap treatment carbon combustion combustion thermal oxidizer
VOC ++ - -/+ + + ++
performance
Consumption - ++ ++/- ++ + +
Cost + ++ ++ ++ - +
Flexibility - - + + - ++
Risks + + - + + +
Cross media - - - + + +
effects

8.4 Water emission prevention and treatment

BAT is an appropriate combination of the following recommendations:

• Preventive actions such as

- Waterproof site and storage retention.
- Regulatory verification procedure has to be done when tank and pits are underground.
- Separated water drainage according to pollution load (roof water, road water, process water).
- Security collection basin

• Water treatment systems

- Activated carbon treatment should be sufficient for low contaminated water
- Thermal treatment should be used for highly polluted water

8.5 Used packaging

BAT is an appropriate combination of the following recommendations:

• Favouring use whenever possible of consigned packaging (drum, container, IBC, palettes, etc.)
• Recycling of drums should be the following option before recovery as fuel or raw material in co-
processing. Disposal by incineration and/or land filling should be avoided whenever possible.
 49

9 HEALTH AND INDUSTRIAL HYGIENE

9.1 General

The objective of chapter 9 is to raise awareness of health and safety issues in the cement industry,
but it will also partly apply for pre-processing plants of alternative fuel and raw materials (AFR).
The chapter also explains some relevant terminology in health and industrial hygiene. Major parts
of the text are collected from Kirk (2004c).

9.2 Industrial hygiene (IH)

Industrial hygiene (IH), also known as occupational hygiene, is the science of anticipating,
recognizing, evaluating and controlling workplace environmental factors and stressors that can
lead to illness or impaired health of workers or those in the surrounding community (American
Industrial Hygiene Association, 1995). Industrial hygiene practice requires detailed knowledge of
a broad array of physical and life sciences, and an organized and analytical approach to problem
solving.

9.2.1 Terminology

In industrial hygiene terminology, toxicity refers to the ability of a substance to injure a bodily
organ or system, interrupt a biochemical process or affect an enzyme system. Hazard refers to the
injurious properties of a substance and the probability of injury. Risk refers to the degree of
hazard and exposure factors such as route of entry into the body, how much of a substance is
released and how easily it is absorbed into the body, length of exposure and effectiveness of
control methods.

9.2.2 Recognizing factors and stressors

Due to the nature of the cement manufacturing process, the industry has its own set of unique IH
hazards that should be recognized and controlled before they become harmful. These hazards can
be divided into four main categories: 1) chemical hazards that can be irritating or toxic to the
body’s organs or systems, 2) physical hazards, such as noise, vibration, radiation, and thermal or
pressure extremes, 3) ergonomic stresses resulting from an improper interface of workers and
workplace machines, tools and procedures that repetitively stress vulnerable areas of the body,
and 4) biological hazards from living organisms that can adversely affect bodily functions. This is
further outlined in Table 18.

Table 18 Summary of industrial hygiene hazards

Chemical Physical Ergonomic Biological
Air contaminants Noise Lifting Blood borne pathogens
Solvents Vibration Posture Viruses
Irritants Heat Static work Bacteria
Corrosives Cold Repetitive motion Fungi
Oxidizers Ionizing radiation Contact with surfaces Animals
Carcinogens Non-ionizing radiation Vibration Insects
Organ/System toxins Pressure extremes Cold
 50

9.2.3 Evaluations

Decisions about the risks industrial hygiene hazards pose to workers must be based on careful
evaluation. Information needed includes: 1) the type and magnitude of each hazard, 2) whether
they are acute (injurious in the short term) or chronic (injurious after long term exposure, usually
many years), 3) degree of worker exposure, and 4) the adequacy of current control measures.
Hazard exposure can be determined qualitatively by examining the work area, its processes and
materials, and quantitatively by measuring worker exposures using area surveys and personal
sampling techniques. Samples should be analyzed at accredited laboratories and results studied
and compared to recommended or permissible exposure levels. Industrial hygiene standards often
require special interpretation and may require the assistance of someone with specialized training.

9.2.4 Control measures

There are three basic types of control measures, listed in order of preference of application: 1)
engineering controls, which remove or reduce the hazard by improving, adding or replacing
equipment that cleans, isolates, encloses or ventilates an area or process, 2) administrative
measures, which include reducing worker exposure time, and training to improve hazard
recognition and exposure avoidance procedures, and 3) personal protective equipment, which
workers wear to limit exposure to the various environmental factors and stressors they encounter
in the workplace.

9.3 Chemical hazards and controls

9.3.1 General

Chemical hazards occur in the cement industry when certain chemicals, compounds and
substances are not properly used or controlled, and when there are excessive concentrations of air
contaminants in the workplace. Toxic effects occur only when a chemical substance reaches a
target receptor in a high enough concentration and for a sufficient time (Doull and others, 1980).

9.3.2 Chemicals and compounds

9.3.2.1 General
Chemical substances may enter the body and possibly affect its systems through inhalation,
ingestion or absorption through the skin. Corrosives, irritants and solvents are examples of
chemical hazards. Certain other substances are considered carcinogens or may affect specific
organs or systems. All chemical substances should be used according to the manufacturers’
instructions, and all recommended precautionary exposure measures should be followed. Some
types of hazardous chemical compound classes are given in alphabetic order in the following sub-
chapters.

9.3.2.2 Carcinogens
Carcinogens are substances that can cause tumours to form or tissues to grow abnormally. There
are few substances employed in the cement manufacturing process that are carcinogenic in nature.
However, certain products used in maintenance operations may contain compounds that are listed
as carcinogens or suspected carcinogens by the International Agency for Research on Cancer
 51

(IARC), the National Toxicology Program (NTP) or other agencies. Facilities should identify
which carcinogenic substances or compounds may be present in the work environment, advise
employees and minimize or prevent exposure. Substitution with alternate substances, application
of engineering or administrative controls and use of personal protective equipment are techniques
that can be employed to reduce risk.

Some cement plants use alternative energy sources (AFR) such as hazardous waste-derived fuels.
These fuels are often blends of many different solvents and may contain varying concentrations of
chemicals or metals known to be carcinogens. Personnel handling such fuels and their by-products
should be made aware of the potential hazards and appropriate controls should be employed. For
instance is hexachloro hexane, 1-3 % present in earth to be co-processed by Beijing cement, listed
as carcinogenic (see its material data safety sheet in Appendix 2).

9.3.2.3 Corrosives
Corrosive substances are strongly acidic or alkaline, and have pH ranges of 0-2 or 12-14,
respectively. Although they are usually found in laboratories, corrosives also include battery acid,
rust removers and drain cleaners. They can cause severe blistering of the skin or burns of up to the
third degree. Corrosives are an eye hazard and may produce irritating or toxic gas if burned or
heated. Tissue damage may be permanent. Corrosives may ignite combustibles such as wood or
paper, and can produce flammable gas on contact with metal.

Best practices for handling corrosives includes use of: 1) rubber gloves, 2) an apron, 3) eye and
face protection, such as indirectly vented splash goggles and a face shield, and 4) a fume hood or
respirator if vapours or mists are present.

Personnel should not: 1) smell or inhale vapours, 2) siphon with one’s mouth, or 3) store or
transport corrosives near flammable solids, oxidizers, ammunition, explosives or reactive
chemicals. Corrosives containers should be labelled clearly. Acids and alkalis (sometimes called
bases) should not be stored together. Spill cleaning and disposal is best accomplished by
neutralizing, not by rinsing down drains. Diluting strong acids and alkalis can reduce: 1) their
hazard when handling, and 2) their potentially harmful effects should a spill or splash occur. Eye
washes and deluge showers should be provided near work and storage areas in case corrosives
contact the eyes or skin.

9.3.2.4 Haematopoietic toxins

Haematopoietic toxins can damage the blood or the body’s ability to form blood. Route of entry
into the body is usually by inhalation. Examples of haematopoietic toxins include carbon
monoxide (automated detector shown in Fig. 4), benzene and epoxies that contain xylol, which in
sufficient doses, can affect the blood’s ability to transport oxygen. Epoxies should only be used
where good ventilation exists.
 52

Fig. 4. Continuously monitoring instruments can alarm if chemical hazards in the workplace
reach action levels. The example is for the haematopoietic carbon monoxide (CO).

9.3.2.5 Hepatoxins
Hepatoxins are substances that can cause liver damage. Route of entry into the body is usually by
inhalation. Examples of hepatoxins include propylene glycol, which e.g. is found in some epoxies.
As with other toxic substances, provision of good ventilation is always the first priority when
handling hepatoxins.

9.3.2.6 Irritants
Irritants are substances that can cause an inflammatory response or reaction of the eye, skin or
respiratory system, if it contacts the tissue in sufficient dose. Many substances are considered
irritants, including numerous solids, liquids and gases. Good ventilation, safe handling and storage
practices and use of personal protective equipment are measures that will prevent tissue irritation.
Irritation is usually completely reversible; when the irritant is removed, the inflammation
subsides. Clinker, cement and cement kiln dust (CKD) are alkaline materials that are also
considered irritants. Mildly acidic neutralizing solutions and barrier creams are marketed to
spread on the skin prior to exposure, but using gloves, disposable protective clothing and
practicing good personal hygiene are the best means to achieve injury prevention.

9.3.2.7 Mercury and mercury spill control

Mercury may be used in certain plants for instrumentation and laboratory purposes. It is a heavy
liquid that will vaporize, especially when it contacts hot surfaces. Inhalation of mercury vapours
or contact with the liquid itself can cause eye or skin irritation, weakness, fatigue, chest pain,
coughing, tremors, glandular disorders and more.
 53

Best practice is to store mercury in a closed, high-density polyethylene container. Glass is a

second choice, but it is breakable. Mercury spill kits containing gloves, respirator, mercury
sponges, suction tubes, absorbent powder and detailed use instructions should be placed in key
areas, and employees should be trained to use it properly. Mercury spills should be cleaned up
immediately and spill areas should be ventilated thoroughly. If mercury recycling is not possible,
a reputable firm should be contracted to dispose of the collected waste mercury and used sponges
(National Institute for Occupational Safety and Health, 1997).

9.3.2.8 Mutagens
Mutagens are substances that alter a cell’s genetic information and may lead to undesirable
inherited conditions. The presence of mutagenic substances in cement plants would be considered
unusual, but it may be present in waste to be processed for AFR or hazardous waste to be
destroyed in cement kilns.

For instance is hexachloro hexane, 1-3 % present in earth to be co-processed by Beijing cement,
found to be mutagenic in animals (see Appendix 2 for the complete materials data safety sheet).

9.3.2.9 Nephrotoxins
Nephrotoxins are substances that can cause kidney damage. Lead, such as found in some older
paint products, xylol and propylene glycol, such as used in some epoxies, are examples of
nephrotoxins. Inhalation is the principal route of entry into the body, but ingestion is also possible.

9.3.2.10 Neurotoxins
Neurotoxins are substances that can affect the brain, central nervous system or nerve cells. They
usually enter the body through inhalation, and may produce emotional or behaviour abnormalities,
or interfere with the body’s ability to control certain functions. Examples of neurotoxins include
lead in paint products, or alcohols, petroleum naphtha and ethylene glycols, such as found in some
paint thinners. Substitution with less hazardous alternative substances should be explored. Good
ventilation and the use of protective respiratory equipment are considered to be best practices.

9.3.2.11 Reproductive toxins

Reproductive toxins are substances that affect both male or female reproductive systems and
which may impair one’s ability to have children. The presence of reproductive toxins in cement
plants would be considered unusual, but it may be present in waste to be processed for AFR or
hazardous waste to be destroyed in cement kilns.

9.3.2.12 Sensitizers
Sensitizers are substances, which on first exposure causes little or no reaction, but which on
subsequent or repeated exposure may cause a marked response, not necessarily limited to the
contact point. Sensitizers most commonly affect the skin, but can also affect the respiratory
system. Sensitivity to a substance is usually dependent upon personal characteristics; what may
sensitize one person will not necessarily affect another.
 54

9.3.2.13 Solvents
Solvents are substances that will dissolve another material, such as acetone, metal cleaners, and
paint thinners, even water. Although they are often thought to be hazardous, the degree of hazard
varies from none to high. Solvents may be flammable or toxic through contact or inhalation of
vapours. Substitution of potent products with less hazardous solvents is always a best practice.

Other best practices include: 1) using gloves when handling solvents, 2) storing solvents in clearly
labelled containers that are closed or covered when not in use, 3) providing good ventilation in
work areas, 4) removing and washing clothing that comes in contact with solvents, and 5)
removing solvent-exposed persons to fresh air if overexposure symptoms occur.

9.3.2.14 Systemic poisons

Systemic poisons are substances that spread throughout the body, damaging all organs and bodily
systems. Systemic poisons are rarely found in a cement plant, although certain herbicides or
animal poisons, if used or stored irresponsibly, could possibly cause systemic damage. Substances
that are potentially systemic poisons should be used only when necessary, and then only in
accordance with the manufacturer’s instructions. Systemic poisons may be candidates for
destruction in cement kilns. All recommended precautionary control measures should be
followed. For instance is DDT present in the contaminated soil to be co-processed by Beijing
cement listed as a systemic poison (see Appendix 3 for the complete materials safety data sheet).

9.3.2.15 Teratogens
Teratogens are substances that can cause birth defects in the fetus of a pregnant female. The
presence of teratogens in cement plants would be considered unusual, but it may be present in
waste to be processed for AFR or hazardous waste to be destroyed in cement kilns.

9.3.3 Air contaminants

9.3.3.1 General
Air contaminants include dusts, fibers, fumes, gases, mists and vapours. If inhaled in sufficient
doses, they could be hazardous to workers’ health. Facilities should identify which air
contaminants are present in the workplace and survey employees’ potential and actual exposure
by performing bulk, area and personal sampling. When engineering and administrative controls
are not feasible, or while they are being installed, exposure should be controlled with personal
protective equipment. (See also sub-chapter 9.3.6 Respiratory Protection).

9.3.3.2 Dust
Dusts are solid particles suspended in air. Limestone and Portland cement dust are classified as
“nuisance particulates.” When inhaled or swallowed in small doses, they dissolve, pass through
the kidneys and out of the body without adverse health effects (Holt, 1987). It should be noted,
however, that some scientists believe no dust is completely inert and precautions should be taken
to prevent overexposures even to dusts given the “nuisance” designation.

Calcined limestone and cement kiln dust (CKD), because of their percentage of calcium oxide
(CaO), are considered chemical substances and have permissible respirable dust exposures that
are fractions of those for nuisance particulates. Consult current regulations for exposure limits.
 55

Dusts that include a certain fraction of respirable crystalline silica (SiO2) also have reduced
permissible exposure limits. Silica accumulation in the lungs can cause silicosis, and crystalline
silica has been classified as a known human carcinogen (Group I) by the International Agency for
Research on Cancer (IARC). Permissible dust exposure limits vary according to the jurisdiction of
regulatory agencies and authorities, and the current regulations should be consulted for each
operation. Some agencies incorporate the percentage of crystalline silica into an exposure limit for
respirable dust, while others express the exposure limit in terms of the actual concentration of
silica present.

Dust control best practices include source enclosure, spill and leak prevention, use of air pollution
control devices, moisture addition and vacuuming instead of dry sweeping. Respirator selection
and use should be based on contaminant type and concentration, and on respirator rated protection
factors.

9.3.3.3 Fibres
Fibers are particulates that have an aspect ratio (such as length to width ratio) equal to or greater
than three to one (3:1). Fibers most likely found in cement facilities are naturally occurring
mineral fibers, such as asbestos, or synthetic vitreous fibers (SVF), also known as man-made
vitreous fibers (MMVF) or man-made mineral fibers (MMMF).

Asbestos formerly enjoyed widespread use for insulation purposes, but serious illnesses associated
with inhaling or ingesting friable asbestos have curtailed or ended its use in many portions of the
world. In many locations, regulations do not permit the use or storage of asbestos, and many
facilities have removed asbestos from the workplace. Asbestos is listed by IARC as a Class 1
carcinogen. Those facilities where asbestos is still in use should conduct a plant wide survey to
determine the type, location and quantity of asbestos, and its condition. Surveys can aid in
prioritizing abatement efforts, and in budgeting for systematic removal or encapsulation. Plants
should ensure that friable asbestos does not become airborne, and train employees on asbestos
hazards. The use of certified asbestos inspectors and abatement companies is recommended
because strict environmental and engineering controls are required, including ventilation and use
of high-efficiency particulate air (HEPA) filters and respirators.

Synthetic Vitreous Fibers (SVF) products are insulating materials that include 1) fibre glass, 2)
mineral wools, 3) refractory ceramic fibers (also known as RCF or vitreous alumino-silicate
fibers), and 4) amorphous calcium-magnesium-silicate fibers. Fibre glass and mineral wools have
been classified by IARC as 2B carcinogens (possibly causing cancer in humans). Refractory
ceramic fibers have also been classified by IARC as 2B carcinogens (possibly causing cancer in
humans). As manufactured, calcium-magnesium-silicate fibers and RCF do not contain respirable
crystalline silica, but when they are exposed to sustained, high temperature (>980°C) use, portions
of the material may de-vitrify into crystalline silica, such as Cristobalite or Quartz, Group 1
carcinogens (Unifrax Corporation, 1998, 1999). If used in certain high-temperature cement
applications, they could present a greater lung disease hazard when removed after use.

There are major differences between SVF products and asbestos: 1) SVF does not split
longitudinally as do asbestos fibers, and 2) they are much more quickly dissolved by body fluids
and therefore less durable as a source of acute or chronic irritation (Rauscher, 1990). Durability is
measured by the in-vitro dissolution rate of a fibre in simulated lung fluid, (kdis, laboratory
testing), or in-vivo bio-persistence factor (fibre half-life, T1/2, animal testing.) See Table 19, for a
summary of the results from several studies.
 56

Table 19 Comparison of in-vivo bio-persistence, in-vitro dissolution and chronic lung

disease (fibrosis/tumour) studies in animals.
Fibre material Bio-persistence; t1/2 (days) in-vitro; kdis Chronic lung
fibrosis / tumours
1
Asbestos, crocidolite 817 <1 +/ +
Asbestos, amosite1 418 <1 +/+
RCF - a2 90 8 +/+
1
RCF - b 55 3 +/+
Rock wool - a1 79 17 +/-
1
Fibre glass wool - a 49 12 +/-
Fibre glass wool - b2 11 95 -/-
1
Slag wool 9 400 -/-
Ca, Mg - silicate2 6 150 Not yet reviewed or rated
1
Johns Manville: “Health & Safety Aspects of Fibre Glass,” 1999. 2Zoitos (1999).

For the purpose of comparing the relative hazard of certain fibers, several Year 2000 Permissible
Exposure Levels (PELs) and Recommended Exposure Guidelines (REGs) are listed. Because
these PELs and REGs may not be applicable in all jurisdictions, or because they may change over
time, current regulations should be consulted for each operation. The United States Occupational
Health and Safety Administration’s PEL for asbestos is 0.1 fibers/cubic centimetre (f/cc or f/cm3),
and 1.0 f/cc for fibre glass and mineral wools. The REG for refractory ceramic fibers set by the
Refractory Ceramic Fibre Coalition is 0.5 f/cc.

The European Union has established another set of guidelines to classify SVF products as to their
hazard potential. These guidelines consider fibre respirability, chemistry, and bio-persistence in
animal testing. The Year 2000 regulatory criteria are: if 50% of fibers greater than 20μm long are
cleared from the lungs in less than 10 days (the fibre half-life, T1/2), that fibre is not classified as a
potential carcinogen (Zoitos, 1999). In recent years, several SVF products have seen the European
carcinogenic labelling requirement lifted. In addition, vitreous fibre manufacturers have
developed new products that have low bio-persistence (T1/2) ratings.

SVF manufacturers recommend the following best practices when handling their products: 1)
wearing loose clothing, 2) wearing safety glasses or goggles, 3) preventing dust production, 4)
providing good ventilation, 5) using respiratory protection when fibre concentration exceeds the
PEL value, 6) keeping work and home clothing separate, and 7) rinsing the washing machine after
washing work clothes (Johns Manville, 1999).

9.3.3.4 Fumes

Fumes are airborne solid particles of metal that condense from heated vapours in the air.
Examples of welding fumes are oxides of iron, lead, nickel, chromium, manganese, etc. Fumes, if
inhaled in sufficient quantity, can cause nausea, dizziness, headache, metal fume fever, damaged
body organs or reduce the efficiency of bodily systems. Material safety data sheets (MSDSs)
should be reviewed to determine hazards to which persons are exposed, and exposure limits.
Local exhaust ventilation is a good engineering control because it draws fumes out of workers’
breathing zones. Filtering respirators offer secondary protection.
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9.3.3.5 Gases
Gases are formless fluids that take the shape and size of their container. Their chemistry may pose
health hazards, or they may serve as asphyxiates if they collect and displace oxygen in work areas.
There are many gases to which cement plant employees could be exposed, including numerous
products of the fuel burning process. Preventing and minimizing the release of gas into the air,
ventilation and dilution are preferred control measures. Fixed and portable atmospheric
monitoring equipment are available to detect gases and measure their concentrations. Respirators
should be worn if concentrations exceed permissible limits and cannot be controlled through
engineering controls.

Carbon dioxide (CO2) is odourless, colourless and slightly heavier than air. It is an asphyxiant
(suffocating compound) and a cerebral vasodilator (i.e. agent expanding blood vessels). If inhaled
in large concentrations it can cause CO2 narcosis, a condition marked by rapid circulatory
insufficiency, advanced lung failure, hypoventilation, coma and death. Inhalation in low
concentrations may cause acute increased respiration and headache, but chronic harmful effects
are not known. CO2 is often used as a fire control chemical and may accumulate as a hazard in
process vessels or outside near ground level if it leaks from storage tanks or is discharged from
fire control apparatus. If one must enter such an environment, supplied-air respirators are
required; filtering respirators offer no protection.

Carbon monoxide (CO) is another product of the combustion process. CO is odourless and
colourless, and levels are generally far below conditions immediately dangerous to life and health
(IDLH). Exposure to low concentrations of vented kiln gases or vehicle emissions above safe
levels can interfere with oxygen exchange in the lungs and produce severe headaches. Exhausts
from pyro-processing and vehicles or tools powered by internal combustion engines should be
vented safely out of enclosed work areas. Facility personnel should be aware that entry into
confined spaces requires measuring CO levels, and that filtering respirators offer no protection to
CO. Air should be supplied when concentrations exceed safe levels.

Flammable gases such as acetylene, LPG-MAPP®, natural gas and propane have numerous
applications in the cement industry and are considered serious fire and explosion hazards. In
addition to these physical hazards, flammable gases are simple asphyxiants that, if leaked into the
air, could exclude an adequate supply of oxygen to the lungs. Depending on the concentration and
length of exposure, they could cause symptoms ranging from rapid breathing, fatigue or nausea to
loss of consciousness, coma or death. Filtering respirators do not afford any protection. Use of
monitors that measure flammable and oxygen deficient atmospheres is recommended before
entering an area where leaked gas is suspected.

Hydrogen sulphide (H2S) is generated when organic matter decomposes in anaerobic conditions.
Although it is sometimes called sewer gas, it has been found in wash pits for mobile equipment.
Leaves, dirt and other organic material washed off vehicles and rotting below the water level can
produce H2S. If a thin oil film covers the wash water, H2S can be trapped below the surface, and
then released when the surface is disturbed, such as when solid materials are cleaned from the pit
bottom. H2S gas accumulation can be prevented if the water’s surface is roiled, such as when air is
bubbled through it.

Nitrogen may be found in plant laboratories or used in the headspaces of fuel tanks as inert gas.
Although it makes up roughly 80% of the air we breathe, it is a simple asphyxiant if leaked in
sufficient quantities into the work environment. It could displace oxygen and cause serious injury
or death.
 58

Oxides of nitrogen (such as nitrogen dioxide, NO2) are found in kiln vent gases and diesel
exhaust. Concentrations in process gases are generally dilute, but poorly maintained diesel
engines or exhaust systems, or operation in enclosed or underground areas could overexpose
operators and persons working nearby. Symptoms of overexposure include eye or respiratory tract
irritation, coughing, chest pain, difficulty breathing or drowsiness. Filtering respirators do not
offer protection from oxides of nitrogen; rather, supplied air respirators are required.

Oxides of sulphur (such as sulphur dioxide, SO2) are acidic gases produced when certain fuels are
burned, particularly coal. Kiln exhaust gases are usually safely vented out of the kiln and diluted
in the atmosphere. However, workers may be exposed if unusual meteorological conditions force
exhaust gases down to lower levels, or if leaks develop in process ductwork or air pollution
control devices. If workers are exposed, irritation of the respiratory system can occur. In that case,
injury potential depends on dose. One cannot rely on the sense of smell to measure SO2
concentration, as its odour threshold is only about one-tenth the threshold limit value (TLV).
Monitoring instruments are needed to measure concentrations, and should be deployed with
automatic alarms at key locations if surveys or exposure experience indicates stack height or
location is a problem.

Ozone (O3) is a powerful oxidizer and irritant to the eyes and mucous membranes of the
respiratory tract. It is generated by corona discharges in electrostatic precipitators and can be
recognized by its bleach- or electrical burn-like odour. If kiln precipitators are energized and not
positively vented, ozone can back-draft into the kiln or leak out of open equipment doors. Ozone
causes headache, sore throat, coughing, chest tightness, burning eyes, profuse perspiration, nausea
and fatigue. Best practices to control ozone exposure include hazard training employees, ensuring
precipitators are de-energized, locked out and positively ventilated, and using an ozone monitor
before and during kiln system entries (Sanderson and others, 1999).

9.3.3.6 Mists
Mists are liquid droplets suspended in air. Mixing, stirring, splashing, foaming or spraying liquids,
such as paints or oils, may generate mists. The skin, lungs and eyes are potentially susceptible to
injury if exposed, so mist production should be contained and controlled (National Mine Health
and Safety Academy, 1999). Protective clothing and filtering respirators should be supplied when
required.

9.3.3.7 Vapours
Vapours are the gaseous form of substances that are liquids or solids at room temperature.
Depending upon substance characteristics and physical conditions, they will evolve out of the
substance if containers are not closed. Vapours posing potential human health hazards include
gasoline and other fuels, oils, paints and solvents. Vapours can cause adverse local effects to the
skin, throat or lungs, produce narcotic effects in the central nervous system or cause toxic effects
in the blood or other organs (National Mine Health and Safety Academy, 1999).

Preventing and minimizing vapour release into the air is best accomplished by safe storage and
handling, in particular keeping containers closed. Ventilation or dilution should be considered a
secondary measure, and evaluated for effectiveness. Liquid fuel and additive storage tank vents
should be equipped with chemical cartridges to control “tank breathing” vapour release during
filling and withdrawal processes, or their headspaces provided with a blanket of nitrogen. Safe
fuel and additive delivery and unloading procedures should be developed. Spilled liquids present
the possibility that large quantities of vapours can be released in a relatively small area, therefore
 59

personal protective equipment should be provided and safe work procedures developed in the
event of a spill. Facilities should consider when substitution of any chemical with a less hazardous
substance is appropriate to reduce employee exposure. If engineering and administrative controls
do not maintain vapour concentrations below safe levels, properly fitted respirators with
appropriate chemical filters should be provided.

9.3.4 Chemical hygiene plan

Facilities should adopt a chemical hygiene plan to address and reduce exposure to hazardous
chemicals. Written operating procedures must be formulated to address relevant safety and health
issues. Procedures should specify criteria to be used

1. To determine chemical exposures

2. To determine exposure control methods
3. For use of fume hoods and personal protective equipment
4. In all laboratory operations or activities needing special approvals
5. In provisions for medical consultation and testing
6. For additional protective measures to be used when working with highly hazardous
chemicals
7. In decontamination procedures to be used in the event of a spill

Laboratory employees should be trained about permissible exposure limits, physical and health
hazards, symptoms of overexposure, safe chemical use procedures and use of written reference
materials such as MSDSs. Personal exposure monitoring and medical examinations are required at
certain times.

9.3.5 Hazard communication

Facilities use numerous chemicals and substances that pose potential chemical and physical
hazards to employees using or exposed to them. Compressed gases, explosive and reactive
chemicals, flammable and combustible liquids, solvents, corrosives, irritants, oxidizers, and
substances with adverse toxicological properties are examples of such chemicals. Facilities should
adopt a plan to ensure all hazardous materials are identified, employees informed of potential
hazards to which they may be exposed and trained on safe handling procedures. Hazard
Communication (HazCom) or Workplace Hazardous Materials Information Systems (WHMIS)
should include a written program and provision of hazard reference materials (MSDSs). Labelling
of containers and use of personal protective equipment and procedures should be proscribed and
followed. Note that MSDSs and labelled chemicals often contain numbered risk- and safety-
phrases. These are listed for the user’s convenience in Appendices 4 and 5, respectively.

9.3.6 Respiratory protection

9.3.6.1 General
Best practice for respiratory protection involves identifying air contaminants and controlling them
through engineering and administrative controls. When engineering and administrative controls
are not feasible or completely effective, while they are being installed or during emergencies,
respirators may be used to protect workers.
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9.3.6.2 Respiratory protection program

When respiratory protection is needed, a respiratory control program should be implemented. Key
elements include: 1) exposure assessment through sampling and analysis, 2) central program
control of assessments and respirator selection, record maintenance and program effectiveness
evaluation, 3) adoption of written standard operating procedures regarding respirator issuance and
use policies, 4) medical evaluations of respirator users to assure wearers do not have medical
conditions that would put them at further risk, 5) selection of respirators commensurate with
hazards and exposure, 6) training on respiratory hazards (respirator function, capabilities and
limitations, how to properly fit, wear, and care for a respirator), 7) fit testing to assure a respirator
is correctly sized and properly adjusted to one’s face, and 8) respirator maintenance, including
inspection, cleaning and storage.

9.3.6.3 Respirators
Respirators may be classified as: 1) air purifying, 2) atmosphere-supplying, or 3) combination of
air purifying/atmosphere-supplying. Air purifying respirators remove contaminants from the air
by filtering out dusts, mists and fumes, or by chemically adsorbing gases and vapours. These
include disposable respirators, half mask or full face-piece cartridge or canister models, and
battery powered air-purifying respirators (PAPR). Air-supplying respirators include demand,
pressure demand and continuous flow airline models, and self-contained breathing apparatus
(SCBA). Combination air purifying/atmosphere-supplying respirator provide protection if the air
supply is lost. Combination-type units are restricted to atmospheres that are not IDLH. Respirator
selection should be based upon the type of contaminant; its concentration, work activity, ambient
conditions and respirator wear time. Respirators have been rated according to the level of
protection they afford, such as specifying up to what multiple of permissible exposure particular
respirators are effective. This is commonly referred to as the respirator protection factor.
Respirators are increasingly protective in this order: half mask disposable, half mask air purifying,
half mask air supplying, full face-piece air purifying, full face-piece atmosphere-supplying. Table
20 lists approximate relative protection factors for various respirators.

Table 20 Typical respirator protection factors (PF)

Respirator type PF1

Half mask: disposable or air purifying 10
Half mask: PAPR; atmosphere-supplying air line (pressure demand / continuous flow) 50
Full face-piece: atmosphere-supplying, SCBA or air line (demand) 100
Full face-piece: air purifying, or powered air purifying with dust filter 100
Full face-piece: powered air purifying with cartridge or canister 1000
Full face-piece: atmosphere-supplying air line (pressure demand or continuous flow) 1000
1
Protection factors shown are approximate and are presented for comparison purposes only. Actual protection factors
may vary. Consult the manufacturer’s literature and use instructions for the rated protection factor of a specific
respirator.

New disposable respirator rating systems evaluate the effectiveness of particulate-filtering

respirators according to their filtering efficiency, and whether or not they should be used in the
presence of oil mists. This system uses the numbers 95, 99 or 100 to designate filtering efficiency
(95%, 99% or 99.97%, respectively), and the letters “N,” “R,” and “P” to designate selection
criteria in the presence or absence of oil particles. Oil mists can break down the filtering
effectiveness of respirators, so proper respirator selection is important. “N” stands for “Not
Resistant to Oil,” “R” stands for “Oil Resistant” and “P” stands for “Oil Proof.” The minimal
 61

rating for a cement plant disposable respirator should be N95. If oil mists are present, “R” or “P”
series respirators should be used.

When “N” series respirators are used in dirty environments, they should be used for one work
shift only, and then discarded. When “R” series respirators are used in oily environments, they
should be used for one work shift only. Any respirator should be changed when it becomes
clogged, damaged or breathing becomes difficult.

9.4 Physical hazards and controls

9.4.1 General

Physical hazards include noise, pressure extremes, radiation and thermal hazards.

9.4.2 Noise and hearing conservation

9.4.2.1 General
Cement manufacturing processes generate noise from crushers, screens, mills, blowers, fans,
vibrators, power transmission devices, mobile equipment, tools, laboratory and office equipment
(Kirk, 1998). If persons are exposed to excessive noise, particularly if they are not protected, they
may suffer hearing loss. Best practices include establishing a hearing conservation program,
identifying occupational noise sources and controlling employees’ exposure through engineering
and administrative controls. When such controls are not feasible or completely effective, while
they are being installed or during emergencies, personal protective equipment, also called Hearing
Protection Devices (HPDs), may be used to protect workers.

9.4.2.2 Physics of sound and noise

Sound is any pressure variation that can be detected by the human ear, whereas noise is sound that
is unwanted by the listener. Sound is transmitted by waves, and is measured by amplitude
(intensity), frequency in cycles per second (Hertz or Hz) and duration (time). Other parameters are
sound power and sound pressure. Since these values cover a wide range, it is convenient to
express intensity, power, and pressure in terms of their respective levels, or decibels (dB). As the
value of these properties increases, the potential damaging effect on human auditory system
increases. Decibels are logarithmic values and cannot be added algebraically. As a rule of thumb,
the additive effect of noise sources can be estimated as shown in Table 21.

Noise exchange rate is an important term. This means: A reduction of 3 dB in sound intensity
level requires a 50% reduction in sound intensity. When calculating permissible noise exposure,
some regulatory agencies apply a 5 dB exchange rate instead of using the true value of 3 dB. That
is, by regulation, a worker’s noise exposure can be increased by 5 decibels if exposure time is
halved, or, exposure time can be doubled if noise exposure is reduced by 5 decibels. For industrial
hearing protection programs, application of the 5 dB exchange rate is much less stringent than
where the true 3 dB exchange rate used.
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Table 21 Approximate additive effect of sound pressure levels

Numerical sound difference between two sound Amount to be added to the larger sound
pressure levels to be added (dB) pressure level to obtain the sum (dB)
0-1 3
2-4 2
5-9 1
≥ 10 0

9.4.2.3 Effects of noise exposure

One type of hearing loss is sensorineural, i.e. noise induced hearing loss (NIHL), caused by
damage to the hearing cells in the inner ear. This condition is always irreversible. Besides
excessive exposure to noise over a period of time, usually over many months or years, hearing
loss can also be due to aging (presbycusis), or to conductive hearing loss. The latter may be
caused by obstructions in the ear, such as wax build-up, or by certain illnesses or other medical
conditions. Non-auditory effects of excessive noise exposure can include nausea, headache,
vasoconstriction, high blood pressure, equilibrium and visual disturbances. Loss of hearing acuity
can make it difficult for one to understand, often because it becomes hard to distinguish between
consonants. The power of speech is generally contained in the vowel sounds, but intelligibility
comes primarily from the consonants. Occupational hearing loss in the important human speech
frequencies of 2000-4000 Hz may be considered a disability and compensable under workers’
compensation laws.

9.4.2.4 Instrumentation for noise evaluation

Sound level meters (SLMs) measure sound pressure levels in decibels (dBs). Three weighting
networks, A, B, & C, are common to sound level meters and cause meter sensitivity to vary with
frequency. The A scale most closely approximates the range of the human ear and is most
commonly used. Whenever expressing sound levels, the scale must be identified, such as “dBA.”
Octave band analyzers determine sound pressure levels at frequencies ranging from 31.5 Hz to
16,000 Hz. They are usually used in conjunction with SLMs and are necessary when designing
engineering solutions for noise control. Sound level meters with octave band analyzers enable
facility engineering and safety personnel to identify high noise level equipment and select
appropriate materials or equipment to reduce workplace noise levels.

Noise dosimeters worn by workers continuously measure personal exposure to changing sound
levels over the course of a workday. They integrate and record the total sound energy to which
workers are exposed, calculate the daily dose in dBA or percent allowable, and record peak levels.
Sampling individual workers using sound dosimeters can indicate workplace sound exposure for
various tasks and help identify hearing loss risk.

9.4.2.5 Hearing conservation programs

Facilities with high noise levels should implement a comprehensive hearing conservation
program. Program components should include: 1) monitoring to determine task-specific noise
exposure levels, 2) performing area surveys to identify loud equipment, 3) posting workplace
noise levels, 4) using engineering controls and administrative procedures to reduce exposure, 5)
training on the effects of noise exposure, including the benefit and use of HPDs, 6) audiometric
 63

testing of employees’ baseline hearing acuity, 7) audiometric monitoring over the course of
employment, 8) keeping records, and 9) notifying employees of changes in hearing ability.

9.4.2.6 Control methods

Regular maintenance and proper lubrication will solve many noise level problems. When they do
not, engineering controls may be installed. These controls include fan and blower silencers,
acoustical linings, curtains, doors and enclosures to block and absorb sound, substituting loud
equipment like power transmission devices and vibrators with quieter models, relocating or
enclosing loud equipment, and providing mobile equipment cabs and operators’ stations.
Whenever feasible, engineering controls should be specified, purchased and installed with new
equipment during the design and construction process. Replacing or retrofitting existing
equipment is possible, but may be more costly and less effective. Facility operations and
maintenance personnel should be aware that engineering controls must be properly installed and
maintained in order to achieve maximum and continued benefit.

Administrative controls include limiting work times in loud areas, and requiring certain safe work
practices, such as keeping windows closed in air-conditioned mobile equipment cabins.

Personal protective equipment (specifically, HPDs) includes several styles of earplugs and
earmuffs. In order to provide hearing protection, earplugs must be installed properly in the ear
canal, and earmuffs must have a good seal around the ear. Plugs and muffs vary in their
effectiveness according to their design and the materials used in their construction. Noise
Reduction Rating (NRR) measures HPD effectiveness, with higher NRR-rated HPDs affording
more protection. Advertised NRRs reflect protection under optimum conditions. Actual worker
protection is, however, much lower than rated, sometimes only half the NRR or less. Wearing
time is very important; when HPDs are removed, even for a short time, the risk of hearing loss
increases dramatically. Exposure to noise totalling just 15 percent of the time is equivalent to
using little or no protection at all. Table 22 illustrates this point and makes a strong case for
wearing hearing protection all the time, not just when it is convenient (Sterret, 2002).

Table 22 Maximum protection provided by non-continuous use of hearing protection.1

Percentage Maximum
time used protection
50 % 3 dB
60 % 4 dB
70 % 5 dB
80 % 7 dB
90 % 10 dB
95 % 13 dB
99 % 20 dB
99.9 % 30 dB
1
Canadian Centre for Occupational Health and Safety, Hamilton, Ontario, 1997-2002.

At high sound pressure levels, sound can by-pass the ear canal and be conducted through the
skull. This is referred to as “bone conduction” and can also damage a person’s hearing. Ear muff-
type HPDs can lessen this effect. Therefore, for sound levels of 105 dBA or more, dual hearing
protection, such as use of both earplugs and ear muffs, is recommended. Exposure to sound levels
 64

above 115 dBA, as measured by a slow response dosimeter or sound level meter, should not be
allowed, although much higher instantaneous peak levels may be experienced.

9.4.3 Pressure extremes

9.4.3.1 General
Extremes of pressure are found in spray cans, compressed gases and hydraulic fluid systems.
Pressures of 700 kPa (100 psi) can be found in plant compressed air systems, while pressures in
compressed gas cylinders can reach 15,000 kPa (2,200 psi), or more. Hydraulic system pressures
can equal or exceed these figures. Uncontrolled or rapid release of pressure poses an injury hazard
to personnel.

9.4.3.2 Aerosol spray cans

Spray cans have been known to explode when stored in hot areas, even on the dashboards of
vehicles parked in direct sunlight. They should be stored in cool locations. If flammable
propellants are present, spray cans should be stored in flammable storage lockers or caged bins
when not in use. These objects pose a fire hazard, and have been known to spread fire rapidly
throughout a building when heat from an incipient fire causes them to explode and fly to various
locations, simultaneously igniting more fuel.

9.4.3.3 Compressed gas cylinders

Compressed gas cylinder valves should be protected with the screw-on cap whenever they are
stored or transported. A broken valve will allow the pressurized gas inside to escape and cause the
cylinder to fly like a rocket, posing personal injury or property damage risk to anyone or anything
nearby. Cylinders should be stored in clean, dry, well-ventilated areas, with full cylinders
separated from empties. They should be secured in the upright position to prevent them from
falling over and damaging the valve. Compressed gas cylinders should never be stored near high
heat sources, to avoid pressure build-up and possible explosion. Damaged, corroded, or leaking
cylinders should be removed from service, tagged, moved to a secure location and the supplier
notified. Pressure regulators should be employed and maintained in good condition to control the
use of compressed gases according to manufacturers’ instructions. Flammable gas cylinders
warrant special handling.

9.4.3.4 Plant compressed air systems

Compressed air directed at a person can force foreign objects through the skin, create embolisms
in blood vessels, rupture the bowels or remove an eye from its socket. Compressed air should
never be directed at a person.

9.4.4 Radiation and control

9.4.4.1 Ionizing radiation

Ionizing radiation sources in cement plants include laboratory X-ray machines, storage tank level
indicators and mass flow measurement devices. These devices produce gamma and X-rays that
can penetrate the body and damage internal organs. To protect employees against injury or illness
resulting from overexposure to ionizing radiation, facilities should adopt a written radiation
control plan.
 65

Best practices include: 1) licensing, if required, 2) appointing a qualified Radiation Control

Officer, 3) securing radiation sources to prevent unauthorized removal, 4) shielding sources to
prevent radiation from entering non-safe areas, 5) labelling areas where radiation equipment is
used or stored with the standard magenta warning symbol (see Fig. 5), 6) locking source shutters
closed before working on or entering equipment or structures that are radiation equipped, 7)
surveying posted areas with radiation detection equipment, 8) training personnel on radiation
hazards, safe work practices and emergency procedures, 9) monitoring exposure of personnel
likely to receive in excess of 25% of the maximum permissible dose in any calendar quarter, or
who enter high radiation areas, and 10) keeping records of radiation surveys, training, monitoring
and personnel exposures. Notification of any spills, injuries, fires or other incidents involving
radioactive materials should be made to the appropriate authorities.

Fig. 5 Example of instruments using radioactive materials being properly shielded and labelled.

9.4.4.2 Non-ionizing radiation

Non-ionizing radiation sources include lasers, infrared sensors, hot objects and ultraviolet light
sources such as generated by pyro-processing and welding. Because these energies do not
penetrate beyond the body’s surface, overexposure poses burn hazards mainly to the skin or eye.
Injury prevention is accomplished by: 1) reducing energy levels, 2) erecting barriers, 3) reflecting
radiation (such as heat), 4) increasing distance between workers and radiation sources, 5) limiting
time of exposure, and 6) using personal protective equipment.

9.4.5 Thermal hazards

9.4.5.1 General
The human body functions best within a narrow temperature range of 36°C to 38°C (97°F to
100°F), and it regulates itself by generating or losing heat as needed. Factors that influence body
temperature include: 1) air temperature and air movement (convection), 2) contact with heated
and cold surfaces (conduction), 3) transfer of heat through air (radiation), 4) humidity and
perspiration (evaporation), and 5) body heat production (metabolism).
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9.4.5.2 Heated materials and equipment

Because cement manufacturing requires extremes of heat throughout the process, heated materials
are of particular concern, as they may range in temperature from ambient to super-heated. Raw
meal, kiln and preheated feed, clinker and clinker dust, kiln burning zone coating, cement kiln
dust, and refractoriness may look cool, but they can be extremely hot. Hot material or dust
accumulations, piles, spills and coating build-ups may be found in process vessels, dust collectors,
conveyors, elevators, etc., or they may be expelled into the atmosphere, spilled or emptied onto
floors or walkways. Because these materials, especially piles or accumulations, are often self-
insulating or are contained in heated or refractory-lined vessels, they may be cool on the surface,
but very hot inside or at their base. They may remain very hot for many hours or days. To avoid
serious burns, no one should ever pick up, handle or hold materials of unknown temperature. Hot
material piles should be barricaded and/or signed and no one should ever walk on, reach into or
step into any pile or accumulation of material. The unseen burn hazards of heated materials should
be included in task and site-specific hazard training.

Heated equipment includes raw and finish mills, pyro-processing apparatus such as preheated
cyclones, calciners, kilns, burners, furnaces, and hot gas generators, conveyors, electrostatic
precipitators and other dust collectors, engines, motors and equipment that has been welded or cut
with an oxy-fuel torch. Even handrails in certain sections of a plant may be a hot surface hazard.
Hot surfaces should be signed where feasible and no one should ever handle or touch any
potentially hot surface without properly selected personal protective equipment.

9.4.5.3 Heat stress

Heat stress occurs when the total heat load on one’s body from internal and external sources
exceeds the body’s ability to cool itself. High temperatures and radiant heat sources identified
with pyro-processing and grinding processes combine with metabolic heat produced by exercise
to drive the body temperature up. If high humidity limits the body’s ability to evaporate
perspiration and cool itself, heat overload is possible. Although evaporation is usually aided by
increased air velocity, if the surrounding air temperature is greater than the body temperature,
more heat will be transferred to the body than can be removed by evaporation. If the heat rise is
too great, or is sustained for too long, injury can occur. Symptoms range from fatigue to fainting,
and from cramps to exhaustion. In extreme cases, severe symptoms can occur. If failure of the
central nervous system’s sweat regulating centre causes perspiration to cease, the body’s
temperature can rise rapidly and convulsions or coma may result.

Heat stress hazard assessment can be accomplished by measuring the Wet Bulb Globe
Temperature (WBGT). WBGT factors air temperature, radiant heat, humidity and air movement
into one thermal index that can be used to guide work time and exertion. Heat stress prevention
methods include: 1) training, 2) drinking plenty of water, 3) taking rest breaks, 4) wearing loose
fitting clothes, 5) using protective clothing or cooling vests, 6) ventilating work areas, 7) spot
cooling with mists, and 8) installing heat shields (Workers Compensation Board of British
Columbia, 2000). Caffeine, which is a diuretic, alcohol, and metabolism-affecting drugs, such as
diet pills, can inhibit the body’s ability to regulate itself, and should be avoided.

Acclimatization is the body’s process to adjust body functions to be more efficient in hot
circumstances. Over a two-week period of exposure to moderate heat, one’s sweat rate increases
and sweat salt content drops. Oxygen consumption and heart rate decrease, resulting in a lower
body temperature given the same environmental and work exertion conditions.
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9.4.5.4 Hypothermia
Hypothermia can occur when core body temperature drops due to lengthy exposure to cold and/or
wet conditions. Progressive symptoms are: 1) shivering and weakness, 2) disorientation and
slurred speech, 3) heart and breathing rate reduction, 4) drowsiness, 5) unconsciousness and
collapse, and 6) possible death. Prevention methods include: 1) avoiding cold, wet exposure, 2)
insulating against heat loss by dressing in layers, especially using woollen blends, and 3)
depending on co-workers to help recognize danger signs, escape the cold and get the body re-
warmed before it is too late.

9.4.5.5 Frost bites

Frostbite occurs when liquids in the body’s extremities freeze. Relatively large, sharp crystals can
damage flesh, or lack of blood flow through constricted blood vessels can cause tissues to die.
Prevention is best accomplished by limiting exposure to cold conditions, especially when they are
accompanied by wind. The hands, toes, ears and nose are most at-risk and should be protected
when cold weather work is required.

9.5 Ergonomic hazards and control

9.5.1 General
Ergonomics refers to efforts to adapt the workplace to the individuals working in it, and to
eliminate or minimize job task risk factors that can cause physical disorders. Disorders develop
over time due to continued exposure to certain environmental factors or physical stresses. Heavy
weights, excessive force requirements, repetitive motions, contact stresses, adverse postural
stresses, vibration, cold temperatures, and the use of heavy work gloves can lead to ergonomic
problems. At-risk tasks often involve manual material handling. Lifting heavy or bulky objects
from the floor, above shoulder height, while seated or while twisting may place employees at-risk.
Exertion with the joints flexed, extended or rotated, pinch grips, pushing and pulling loads, poor
posture or bending, especially under load, are also influencing factors. Any of these, especially
when multiple factors are involved, or when coupled with work tasks of long duration or short
recovery periods, play a role in determining whether or not an employee will develop disorders.

9.5.2 Body systems at risk

9.5.2.1 General
Body systems subjected to ergonomic disorders are the muscular-skeletal system, the nervous
system and the cardiovascular system.

9.5.2.2 Muscular-skeletal system

Muscular-skeletal system disorders include: 1) joint sprains, caused by twisting or hyper-
extending, 2) muscle strains caused by over-exertion or over-stretching, 3) tendon inflammation
(tendonitis) caused by repetitive motions or excessive force, 4) arthritic conditions of the joints,
perhaps caused by awkward positioning under load, 5) repetitive shock to the spine, such as from
long operation of a haulage truck, and 6) degeneration of spinal discs, often caused by repetitive
lifting with poor posture. These disorders develop over a period of time, ranging from a few hours
to many years.
 68

9.5.2.3 Nervous system

Nervous system conditions include: 1) compression of the median nerve in the wrist (carpal tunnel
syndrome) due to repetitive motions, 2) compression of the ulnar nerve in the arm (cubital tunnel
syndrome), from resting the elbows on hard surfaces, and 3) compression of the nerves at the
shoulder (thoracic outlet syndrome) from working with one’s arms above the head.

9.5.2.4 Cardiovascular system

Cardiovascular system disorders include: 1) obstruction of blood flow to body tissue (compression
ischemia) due to resting one’s limbs on hard or sharp objects, or 2) reduction of blood flow to the
hands or fingers (segmental vibration, white finger) resulting from vibration while using hand
held power tools.

9.5.3 Evaluation
Operations should analyze the work environment for indicators of ergonomic stressors, assess
work tasks for the listed risk factors, review records to determine trends or history of cumulative
trauma or repetitive stress disorders, interview workers and look for adaptations made to
workstations or tools. Videos, slides and photographs are good tools to use when analyzing job
situations.

9.5.4 Controls

To reduce the risk of ergonomic problems, facilities should make efforts to neutralize as many
risk factors as possible. Adaptations of tools, equipment or workstations to avoid reaching,
twisting, pinching or excessive force are often all that are required to improve a condition. New
equipment may be helpful, but is not always indicated, nor is it always ergonomically friendly to
workers unless ergonomic considerations are made in the design phase. Tools are available to
reduce the effort or change the posture required to perform jobs. Consideration should be made as
to whether power tools or manual tools with a different sized or shaped handle are in order.
Likewise, decisions should be made whether lifting problems can be solved with power-assisted
vacuum lifters, power operated tables to lift or position loads, loads with reduced weights or
smaller dimensions, or teaching employees simple techniques like the one-hand assisted lift
method.

9.5.5 Training

It is important to train workers so they know how to care for their bodies and prevent ergonomic
disorders from occurring. Training should include physical limitations, how repetitive stress
injuries develop, how to avoid injury by stretching prior to performing certain tasks, and the
hazards associated with certain postural positions.

9.6 Biological hazards and controls

9.6.1 General
Biological hazards include bio-aerosols, blood-borne pathogens and zoonotic diseases.
 69

9.6.2 Bio-aerosols

9.6.2.1 General
Bio-aerosols are airborne liquid or solid particulates released from a living organism, small
enough to remain dispersed in air for a prolonged period of time. Bacteria and fungi are the most
commonplace bio-aerosols. Most environments contain a wide variety of bacteria and fungi; their
types and concentrations are dictated by the prevailing conditions. Individual aerosolized
particulates range in size from less than 0.1 μm to greater than 100 μm as reported in the
American Conference of Governmental Industrial Hygienists’ guidelines (ACGIH, 1989). Typical
bio-aerosols encountered in the indoor cement environment are bacteria and fungi, and may be
further actualized when pre-processing municipal waste for AFR.

9.6.2.2 Bacteria
Bacteria are microscopic organisms with single-celled or non-cellular bodies that collect in
colonies in soil, water, organic matter, or in the bodies of plants and animals. Bacteria have
pathogenic potential, and can cause adverse chemical effects, especially in food.

9.6.2.3 Fungi
Fungi are microscopic plants that include molds, mildew, mushrooms and yeast, and live or feed
on dead or decaying organic matter. For the average person, exposure to small and moderate
amounts of molds is a fact of daily life, and those with normally functioning immune systems do
not get ill. However, if workers are exposed to high concentrations of molds, especially if over a
long period of time, or if they have existing lung disease or weak or challenged immune systems,
the risk is higher. Potential health effects from toxigenic fungi like Stachybotrys and Aspergillus
range from no effect to mild cold or flu symptoms, diarrhoea, fatigue, allergic reactions or serious
respiratory illnesses like bronchopulmonary aspergillosis.

9.6.2.4 Controls
Fungal molds and bacteria have been found when the right combination of moisture, temperature
and food supply come together, such as in laboratory constant temperature and humidity rooms.
Best practices to prevent fungal or bacterial growth and potential human illness include: 1)
eliminating the fungi’s food supply by constructing the room of non-cellulose-based products (i.e.
not using wood or paper), 2) decreasing the room’s humidity level by installing moisture cabinets
of stainless steel construction, and 3) inspecting exposed surfaces, wall interiors, ceiling spaces or
other hidden areas for evidence of fungal growth. Should minor cleaning be necessary, an
application of 10% household bleach solution (one part household bleach to nine parts water) will
control the hazard, but even the “dead” remains of fungi and their mycotoxins can be toxigenic
and should be removed. Should major fungal colonies be discovered, remediation efforts should
include: 1) removing cellulose-based wall and ceiling materials, 2) using removal, disposal and
worker protection practices similar to those employed in asbestos abatement, and 3) cleaning and
disinfecting all surfaces with a 10% or greater household bleach solution (Rice, 2000). (See also
other fungal hazards discussed in 9.5.4 Zoonotic Diseases.)
 70

9.6.3 Blood borne pathogens (BBP)

Of the large number of types of micro-organisms that inhabit the planet, only a small proportion is
harmful to man (Heinsohn, 1995). Exposure to those biological agents can result in acute and
chronic disease. Blood borne pathogens may pose risk to facility personnel, particularly first
responders, if they are exposed to blood and other body fluids. Such pathogens include viruses,
chlamydiae, rickettsiae, and mycoplasmas. Viruses are sub-microscopic, sub-cellular agents that
range in size from 0.02 to 0.30 μm. There is some question as to whether viruses are actually
living organisms. Chlamydiae are obligate parasites that are similar to bacteria but are much
smaller in size. They have complex developmental cycles and preferentially infect mucous
membrane tissue. Similar to chlamydiae, rickettsiae are obligate parasites that are similar to
bacteria and can survive only within living cells. These agents are transmitted to man by
arthropods, such as ticks, fleas, and lice. Mycoplasmas are the smallest cells that may exist
independently and some are smaller than large viruses. Viruses such as those that cause hepatitis
B (HBV) and human immunodeficiency (HIV) are the blood borne pathogens most likely to be
passed from one person to another.

Although workplace exposure of BBP is rare (unless hospital waste is to be handled for
destruction in the cement kiln), facilities should adopt an exposure control plan that includes: 1)
provision of BBP kits containing personal protection equipment and decontamination solutions, 2)
training on kit use, 3) adopting universal precautions, i.e. considering all blood to be infected and
treating it as if it were, to minimize the possibility of exposure, 4) reporting and recording blood
and bodily fluid exposures, 5) offering exposed persons and all first aid providers the hepatitis B
vaccination, 6) promptly decontaminating all surfaces, clothing and tools, and 7) properly
disposing of waste.

9.6.4 Zoonotic diseases

9.6.4.1 General
Zoonoses are diseases that can be transmitted to humans by animals through contact with bacteria,
rickettsiae, viruses, fungi or parasites. Diseases or illnesses that cement plant workers could
contract include histoplasmosis, tetanus, Lyme disease, Rocky Mountain spotted fever, rabies and
certain dermatoses. The risk is usually small and in many cases largely dependent upon
geographical location and task assignments. Facilities should assess the likelihood of contracting
such diseases and implement preventive measures commensurate with risk, such as controlling or
eliminating populations of small animals and insects such as raccoons, skunks, cats and
mosquitoes, and providing insect repellent and prompt, competent treatment of infections, wounds
or bites.

9.6.4.2 Histoplasmosis
Histoplasmosis is an avian borne fungal illness that can possibly be contracted by cement
workers. The fungus Histoplasma capsulatum is found worldwide, but is particularly endemic in
the eastern half of North America. Fungal spores grow in manure-nourished moist soil and can be
spread by pigeons, blackbirds, chickens and bats. When spores are disturbed, become airborne
and are inhaled, infection of the respiratory system is possible. Although the disease can be life
threatening, most infections are quite mild, no worse than the flu. Testing of human blood or bird
manure samples to determine infection or the presence of spores is expensive, inconclusive and
not recommended.
 71

Best practice is to assume the fungus is present in endemic areas and focus on preventing human
infection by: 1) excluding birds from roosting areas by screening eaves, netting rooftop
ventilators, installing doors and hanging vinyl strips at passageways and around materials
transport systems, 2) minimizing the chance of spores forming and becoming airborne by
regularly removing and disposing of bird droppings using wet clean-up procedures, protective
clothing and respirators, and 3) treating accumulations of manure and contaminated surfaces with
a quaternary ammonium chloride blend that functions as a combination wetting agent,
disinfectant, fungicide and deodorizer (Rhodes et al., 2000).

9.6.4.3 Lyme disease and Rocky Mountain spotted fever

Lyme disease and Rocky Mountain spotted fever are examples of tick-spread diseases that are
potentially harmful to man. Cement plant exposure to ticks depends upon the plant’s geographical
location and an individual’s work assignment. Persons whose job requires them to venture into
grass and woods are much more likely to be exposed to ticks than those working in the mill.
Those who may be at-risk should be trained to: 1) wear light coloured clothing, with pants legs
tucked into boots, 2) check frequently and remove ticks that may attach themselves to clothing or
one’s person, 3) know the symptoms of each disease and seek medical attention if they suspect
they have been bitten by an infected tick. Vaccinations are available for Lyme disease, but should
be administered only if medical personnel consider the risk of contracting the disease to warrant
such intervention.
 72

10 AFR FEED POINTS IN CEMENT KILNS

A short description of adequate feed points of AFR in a cement kiln may be in place at the end
although it is not the main focus of this report. The most common feed points are (see also Fig. 6):

1. via the main burner at the rotary kiln outlet end

2. via a feed chute at the transition chamber at the rotary kiln inlet end (for lump fuel)
3. via secondary burners to the riser duct
4. via precalciner burners to the precalciner
5. via a feed chute to the precalciner (for lump fuel)
6. via a mid kiln valve in the case of long wet and dry kilns (for lump fuel)

Alternative raw materials (ARs) are typically fed to the kiln system in the same way as traditional
raw materials, e.g. via the normal raw meal supply. Alternative raw materials containing
components that can be volatilized at low temperatures (for example, hydrocarbons) have to be
fed into the high temperature zones of the kiln system.

Co-processing has the following characteristics during the production process:

• The alkaline conditions and the intensive mixing favour the absorption of volatile
components from the gas phase. This internal gas cleaning results in low emissions of
components such as SO2, HCl, and, with the exception of mercury and thallium, this is
also true for most of the heavy metals.
• The clinker reactions at 1,450°C allow incorporation of ashes and in particular the
chemical binding of metals to the clinker.
• The direct substitution of primary fuel by high calorific waste material causes a higher
efficiency on energy recovery in comparison to other “waste to energy” technologies

Adequate feed points will be selected according to the physical, chemical, and (if relevant)
toxicological characteristics of the AFR used, as well as the type of kiln (see Fig. 7).

Fig. 6 Clinker process and special characteristics in a pre-calciner kiln

 73

Alternative fuels (AFs) are always fed into the high-temperature combustion zones of the kiln
system. The physical and chemical natures of the fuel determine the exact feed point, i.e. either
the main burner, the precalciner burner, the secondary firing at the preheater, or the mid-kiln (for
long dry and wet kilns). Alternative fuels containing stable toxic components should be fed to the
main burner to ensure complete combustion due to the high temperature and the long retention
time.

Feeding of alternative raw materials containing volatile (organic and inorganic) components to the
kiln via the normal raw meal supply is forbidden unless it has been demonstrated by controlled
test runs in the kiln or by adequate laboratory tests that undesired stack emissions can be avoided.

Fig. 7 Possible feed points for AFR depending on kiln type

 74

11 CONCLUSIONS

A review has been made of the following;

1. Waste materials recommended for co-processing in cement kilns, and of those who are not
deemed suitable.

2. Recommended guidelines and operational aspects of pre-processing waste to alternative

fuel and raw materials (AFRs) for co-processing in cement kilns.

3. Feed point for AFRs into cement kilns

Occupational health and safety (OH&S) for pre-processing waste to AFR in particular, but also
generally for industry like cement plants.
 75

12 REFERENCES

ACGIH, Guidelines for the Assessment of Bio-aerosols in the Indoor Environment, American
Conference of Governmental Industrial Hygienists, Cincinnati, 1989.

American Industrial Hygiene Association, 1994 – 1995 Membership Directory, Fairfax, Virginia,
1995.

Canadian Centre for Occupational Health and Safety (CCOHS), 250 Main Street East, Hamilton,
Ontario, L8N 1H6; Tel: (905) 572-4400; (800) 263-8466; Fax (905) 572-4500; E-mail:
inquiries@CCOHS.ca.

Doull, J., Klassen, C. D. and Amdur, M. O. (editors), Casarett and Doull’s Toxicology: The Basic
Science of Poisons, Second Edition, Macmillan Publishing Co., Inc., New York, 1980.

GTZ - Holcim “Guidelines on co-processing waste materials in cement production”, The GTZ-
Holcim Public Private Partnership, 2006, www.coprocem.com

Heinsohn, P.A., Jacobs, R.R., and Concoby, B.A. (Editors), Biosafety Reference Manual, Second
Edition, American Industrial Hygiene Association, Fairfax, Virginia, 1995.

Holt, P. F., Inhaled Dust and Disease, John Wiley & Sons Ltd., Chichester, England, 1987.

Johns Manville, Health, Safety and Environment Department Bulletin HSE-64C, Health and
Safety Aspects of Fibre Glass, Littleton, Colorado, 1999.

Justnes, H. and Engelsen, C.J.: Environmentally Sound Management of Hazardous and Industrial
Wastes in Cement Kilns - Waste as Alternative Raw Materials, SINTEF Report SBF IN A07322,
December 2007, 121 pp.

Karstensen, K.H. and Justnes, H.: Environmentally sound management of hazardous and
industrial wastes in cement kilns in China Proceedings of the International Symposium on
Sustainability in the Cement and Concrete Industry, Edited by S. Jacobsen, P. Jahren and K.O.
Kjellsen, Lillehammer, Norway, 16-19 September, 2007, pp. 334 - 342.

Kirk, L. H. III, “Engineering Controls for Noise Attenuation in the Cement Industry,” 40th Cement
Industry Technical Conference Record, Institute of Electrical and Electronics Engineers, Inc.,
Piscataway, New Jersey; and Portland Cement Association, Skokie, Illinois, May 1998.

Kirk, L.H. III: “Safety Management and Organization”, Chapter 7.1 in “Innovations in Portland
Cement Manufacturing”, Eds. J. I. Bhatty, F. MacGregor Miller and S. H. Kosmatka, Portland
Cement Association (PCA), Illinois, USA, 2004a, ISBN: 0-89312-234-3.

Kirk, L.H. III: “Effective Safety Practices”, Chapter 7.2 in “Innovations in Portland Cement
Manufacturing”, Eds. J. I. Bhatty, F. MacGregor Miller and S. H. Kosmatka, Portland Cement
Association (PCA), Illinois, USA, 2004b, ISBN: 0-89312-234-3.

Kirk, L.H. III: “Health and Industrial Hygiene”, Chapter 7.3 in “Innovations in Portland Cement
Manufacturing”, Eds. J. I. Bhatty, F. MacGregor Miller and S. H. Kosmatka, Portland Cement
Association (PCA), Illinois, USA, 2004c, ISBN: 0-89312-234-3.
 76

National Institute for Occupational Safety and Health, Pocket Guide to Chemical Hazards, U.S,
Department for Health and Human Services, Public Health Service, Centres for Disease Control,
U.S. Government Printing Office, Washington, DC, June, 1997.

National Mine Health and Safety Academy, Industrial Hygiene: Sampling for Silica and Noise,
U.S. Department of Labour, Mine Safety and Health Administration, 1999.

Rauscher, F. J. Jr. “Asbestos Substitutes are Safe, Effective,” Asbestos Issues, May 1990.

Rhodes, S. W., Kirk, L. H., and Murray, C., Histoplasmosis, etc. – Teaming Up to Protect
Respiratory Health, American Society of Safety Engineers, Cumberland Valley Section,
Chesapeake Chapter, February 2000.

Rice, M., Anticipation, Evaluation and Remediation of a Fungal Amplification Problem

(Biocontamination by Molds), Edmonton, Alberta, Canada, March 2000.

Sanderson, W., Kirk, L. H., and Almaguer D., “Ozone-induced respiratory illness during the
repair of a portland cement kiln,” Scandinavian Journal of Work, Environment and Health, Vol.
25, No. 3, July 1999.

Sterret, M. L., “Keeping an Ear to the Ground: Tech Solutions to Hearing Protection
Compliance,” Professional Safety magazine, American Society of Safety Engineers, Des Plaines,
Illinois, August 2002.
Unifrax Corporation, MSDS Number M0251, Fiberfrax® Ceramic Fibre Products, Niagara Falls,
New York, 1998.

Unifrax Corporation, MSDS Number M4115, Insulfrax™ Thermal Insulation Products, Niagara
Falls, New York, 1999.
 77

ABBREVIATIONS

ADR = Agreement on Dangerous goods by Road

AF = Alternative Fuel
AFR = Alternative Fuel and Raw materials
AR = Alternative Raw materials
BAFU = Bundesamt für Umwelt (Federal office for the environment), www.bafu.admin.ch
BAT = Best Available Technology
BOD = Biochemical Oxygen Demand
BUWAL = Bundesamt für Umwelt, Wald und Landschaft (Swiss Agency for the
Environment, Forest and Landscapes), www.umwelt-schweitz.ch
CKD = Cement Kiln Dust
COD = Chemical Oxygen Demand
CSI = Cement Sustainability Initiative
H&S = Health and Safety
HazCom = Hazard Communication
HCB = hexachlorobenzene
HEPA = High-Efficiency Particulate Air (prefix to filter)
HPD = Hearing Protection Device
IARC = International Agency for Research on Cancer
IBC = International Bulk Container
IDLH = Immediate Danger to Life and Health
IH = Industrial Hygiene
LAF = Liquid Alternative Fuel
LCV = Low Calorific Value
MAC = Maximal Acceptable Concentration
MMMF = Man-Made Mineral Fibres
MMVF = Man-Made Vitreous Fibres
MSDS = Material Safety Data Sheet
NA = Not Applicable
NIHL = Noise Induced Hearing Loss
NRR = Noise Reduction Rating
NTP = National Toxicology Program
OH&S = Occupational Health and Safety
PAPR = Powered Air-Purifying Respirator
PCBs = Polychlorinated biphenyls
PCDDs = Polychlorinated dibenzodioxins
PCDFs = Polychlorinated dibenzofurans
PEL = Permissible Exposure Limit
POPs = Persistent Organic Pollutants
PF = Protection Factor
RCF = Refractory Ceramic Fibers
RDF = Refuse Derived Fuels
REG = Recommended Exposure Guidelines
SAF = Solid Alternative Fuel
SCBA = Self-Contained Breathing Apparatus
SLM = Sound Level Meter
Sv = Sievert (SI unit of equivalent radiation dose)
SVF = Synthetic Vitreous Fibers
TLV = Threshold Limit Value
 78

TOC = Total Organic Carbon

TSS = Total Suspended Solids
VOC = Volatile Organic Carbon
WBCSD = World Business Council for Sustainable Development
WBGT = Wet Bulb Globe Temperature
WHMIS = Workplace Hazardous Materials Information System
WMC = Waste Management Company
 79

APPENDIX 1: LIST OF WASTE MATERIALS SUITABLE FOR AFR

This list is derived from the European Waste Catalogue but is not an exclusive and compulsory
document. Complete catalogue: http://www.vrom.nl/get.asp?file=/docs/milieu/eural_engelse_versie.pdf
This list gives a general overview of possible wastes to be used as AFR in cement kilns.

A. Industrial Wastes

1. 0 Organic Chemical Wastes

1.1 Mineral oils, synthetic oils and fats

05 01 00 oil sludges and solid wastes

05 01 01 sludges from on-site effluent treatment
05 01 03 tank bottom sludges

12 01 00 wastes from shaping (including forging, welding, pressing, drawing, turning,

cutting and filing)
12 01 06 waste machining oils containing halogens (not emulsioned)
12 01 07 waste machining oils free of halogens (not emulsioned)
12 01 08 waste machining emulsions containing halogens
12 01 09 waste machining emulsions free of halogens
12 01 10 synthetic machining oils

13 01 00 waste hydraulic oils and brake fluids

13 01 01 hydraulic oils, containing PCBs or PCTs
13 01 02 other chlorinated hydraulic oils (not emulsions)
13 01 03 non-chlorinated hydraulic oils (not emulsions)
13 01 04 chlorinated emulsions
13 01 05 non-chlorinated emulsions
13 01 06 hydraulic oils containing only mineral oil
13 01 07 other hydraulic oils

13 02 00 waste engine, gear and lubricating oils

13 02 01 chlorinated engine, gear and lubricating oils
13 02 02 non-chlorinated engine, gear and lubricating oils
13 02 03 other engine, gear and lubricating oils

13 03 00 waste insulating and heat transmission oils and other liquids

13 03 01 insulating or heat transmission oils and other liquids containing PCBs (chlorinated waste
and PCB are subject to legal limitations, maximum concentration in input and
maximum T/year allowed)
13 03 02 other chlorinated insulating and heat transmission oils and other liquids
13 03 03 non-chlorinated insulating and heat transmission oils and other liquids
13 03 04 synthetic insulating and heat transmission oils and other liquids
13 03 05 mineral insulating and heat transmission oils and other liquids

13 04 00 bilge oils
13 04 01 bilge oils from inland navigation
13 04 02 bilge oils from jetty sewers
13 04 03 bilge oils from other navigation
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APPENDIX 1: List of waste materials suitable for AFR - Page 2 of 7

13 05 00 oil/water separator contents

13 05 02 oil/water separator sludges
13 05 03 interceptor sludges
13 05 04 desalter sludges or emulsions
13 05 05 other emulsions

13 06 00 oil waste not otherwise specified

13 06 01 oil waste not otherwise specified

1.2. Petrochemical wastes

05 01 00 oil sludges and solid wastes

05 01 01 sludges from on-site effluent treatment
05 01 02 desalter sludges
05 01 03 tank bottom sludges
05 01 04 acid alkyl sludges
05 01 05 oil spills
05 01 06 sludges from plant, equipment and maintenance operations
05 01 99 wastes not otherwise specified

05 05 00 oil desulphurisation waste

05 05 01 waste containing sulphur

05 06 00 waste from the pyrolytic treatment of coal

05 06 01 acid tars
05 06 03 other tars
05 06 04 waste from cooling columns

1.3 Solvents, paints, varnishes, glues (adhesive, sealants), organic rubbers

07 03 00 waste for the MFSU of organic dyes and pigments (excluding 06 11 00)
07 03 01 aqueous washing liquids and mother liquors
07 03 02 sludges from on-site effluent treatment
07 03 03 organic halogenated solvents, washing liquids and mother liquors
07 03 04 other organic solvents, washing liquids and mother liquors
07 03 07 halogenated still bottoms and reaction residues
07 03 09 halogenated filter cakes, spent absorbents

08 01 00 wastes from the MFSU of paint and varnish

08 01 01 waste paints and varnish containing halogenated solvents
08 01 02 waste paints and varnish free of halogenated solvents
08 01 03 waste from water-based paints and varnishes

08 01 06 sludges from paint and varnish removal containing halogenated solvents

08 01 07 sludges from paint and varnish removal free of halogenated solvents
08 01 08 aqueous sludges containing paint or varnish
08 01 09 wastes from paint or varnish (except 08 01 05 and 08 01 06)
08 01 99 wastes not otherwise specified
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APPENDIX 1: List waste materials suitable for AFR - Page 3 of 7

08 03 00 wastes from the MFSU of printing inks

08 03 01 waste ink containing halogenated solvents
08 03 02 waste ink free of halogenated solvents

08 04 00 wastes from the MFSU of adhesives and sealants

(Including waterproofing products)

08 04 01 waste adhesive and sealants containing halogenated solvents

08 04 02 waste adhesive and sealants free of halogenated solvents
08 04 03 waste from water-based adhesive and sealants
08 04 05 adhesive and sealants sludges containing halogenated solvents
08 04 06 adhesive and sealants sludges free of halogenated solvents
08 04 07 aqueous sludges containing adhesive and sealants
08 04 08 aqueous liquid waste containing adhesive and sealants

14 05 00 wastes from solvent and coolant recovery (still bottoms)

14 05 01 chlorofluorocarbons
14 05 02 other halogenated solvents and solvent mixes
14 05 03 other solvents and solvent mixes
14 05 04 sludges containing halogenated solvents
14 05 05 sludges containing other solvents

1.4 Wastes from synthetic materials and rubbers

07 02 00 waste for the MFSU of plastics, synthetic rubber and man-made fibres
07 02 01 aqueous washing liquids and mother liquors
07 02 02 sludges from on-site effluent treatment
07 02 03 organic halogenated solvents, washing liquids and mother liquors
07 02 04 other organic solvents, washing liquids and mother liquors
07 02 07 halogenated still bottoms and reaction residues
07 02 08 other still bottoms and reaction residues

2. 0 Other Chemical Wastes

03 02 00 wood preservation waste

03 02 01 non-halogenated organic wood preservatives
03 02 02 organochlorinated wood preservatives

03 03 00 wastes from pulp, paper and cardboard production and processing

03 03 05 de-inking sludges from paper recycling
03 03 06 fibre and paper sludge

04 01 00 wastes from the leather industry

04 01 03 degreasing wastes containing solvents without a liquor phase

04 02 00 wastes from textile industry

04 02 11 halogenated waste from dressing and finishing
04 02 13 dye stuffs and pigments
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APPENDIX 1: List of waste materials suitable for AFR - Page 4 of 7

07 01 00 waste from the manufacture, formulation, supply and use (MFSU) of basic organic
chemicals
07 01 01 aqueous washing liquids and mother liquors
07 01 02 sludges from on-site effluent treatment
07 01 03 organic halogenated solvents, washing liquids and mother liquors
07 01 04 other organic solvents, washing liquids and mother liquors
07 01 07 halogenated still bottoms and reaction residues
07 01 08 other still bottoms and reaction residues

07 04 00 waste for the MFSU of organic pesticides

07 04 01 aqueous washing liquids and mother liquors
07 04 02 sludges from on-site effluent treatment
07 04 03 organic halogenated solvents, washing liquids and mother liquors
07 04 04 other organic solvents, washing liquids and mother liquors
07 04 07 halogenated still bottoms and reaction residues
07 04 08 other still bottoms and reaction residues

07 05 00 waste for the MFSU of pharmaceuticals

07 05 01 aqueous washing liquids and mother liquors
07 05 02 sludges from on-site effluent treatment
07 05 03 organic halogenated solvents, washing liquids and mother liquors
07 05 04 other organic solvents, washing liquids and mother liquors
07 05 07 halogenated still bottoms and reaction residues
07 05 08 other still bottoms and reaction residues

07 06 00 waste for the MFSU of fats, grease, soaps, detergents, disinfectants and cosmetics
07 06 01 aqueous washing liquids and mother liquors
07 06 02 sludges from on-site effluent treatment
07 06 03 organic halogenated solvents, washing liquids and mother liquors
07 06 04 other organic solvents, washing liquids and mother liquors
07 06 07 halogenated still bottoms and reaction residues
07 06 08 other still bottoms and reaction residues

07 07 00 waste for the MFSU of fine chemical products not otherwise specified
07 07 01 aqueous washing liquids and mother liquors
07 07 02 sludges from on-site effluent treatment
07 07 03 organic halogenated solvents, washing liquids and mother liquors
07 07 04 other organic solvents, washing liquids and mother liquors
07 07 07 halogenated still bottoms and reaction residues
07 07 08 other still bottoms and reaction residues

08 03 00 wastes from the MFSU of printing inks

08 03 03 waste from water-based inks
08 03 05 ink sludges containing halogenated solvents
08 03 06 ink sludges free of halogenated solvents
08 03 07 aqueous sludges containing ink
08 03 08 aqueous liquid waste containing ink
08 03 99 wastes not otherwise specified
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APPENDIX 1: List of waste materials suitable for AFR - Page 5 of 7

09 01 00 wastes from the photographic industries

09 01 01 water based developer and activator solutions
09 01 02 water based offset plate developer solutions
09 01 03 solvent based developer solutions
09 01 04 fixer solution
09 01 05 bleach solutions and bleach fixer solutions

10 03 00 wastes from aluminium thermal metallurgy

10 03 01 tars and other carbon-containing wastes from anode manufacture

14 01 00 waste from metal degreasing and machinery maintenance

14 01 01 chlorofluorocarbons
14 01 02 other halogenated solvents and solvent mixes
14 01 03 other solvents and solvent mixes
14 01 04 aqueous solvent mixes containing halogens
14 01 05 aqueous solvent mixes free of halogens
14 01 06 sludges and solid wastes containing halogenated solvents
14 01 07 sludges and solid wastes free of halogenated solvents

14 02 00 wastes from textile cleaning and degreasing of natural products

14 02 01 halogenated solvents and solvent mixes
14 02 02 solvent mixes or organic liquids free of halogenated solvents
14 02 03 sludges and solid wastes containing halogenated solvents
14 02 04 sludges and solid wastes containing other solvents

14 03 00 wastes from the electronic industry

14 03 01 chlorofluorocarbons
14 03 02 other halogenated solvents and solvent mixes
14 03 03 other solvents and solvent mixes
14 03 04 sludges and solid wastes containing halogenated solvents
14 03 05 sludges and solid wastes containing other solvents

14 04 00 wastes from coolants, foam/aerosols propellants

14 04 01 chlorofluorocarbons
14 04 02 other halogenated solvents and solvent mixes
14 04 03 other solvents and solvent mixes
14 04 04 sludges and solid wastes containing halogenated solvents
14 04 05 sludges and solid wastes containing other solvents

16 03 00 off-specification batches
16 03 02 organic off-specification batches
16 05 00 chemicals and gases in containers
16 05 03 other wastes containing organic chemicals,
e.g. lab chemicals not otherwise specified

17 03 00 asphalt, tar and tarred products

17 03 03 tar and tar products
 84

APPENDIX 1: List of waste materials suitable for AFR - Page 6 of 7

18 02 00 waste from research, diagnosis, prevention of diseases involving animals

18 02 04 discarded chemicals

B. Wastes of Animal and Vegetal Origin

(Except municipal, textile, agricultural and hospital wastes)

1.0 Fats and oils from animal and vegetal origin

02 01 00 primary production waste

02 01 01 sludges from washing and cleaning
02 01 06 animal faeces, urine and manure (including spoiled straw), effluent, collected separately
and treated off-site

02 02 00 wastes from the preparation and processing of meat, fish and other foods of animal
origin
02 02 01 sludges from washing and cleaning
02 02 03 materials unsuitable for consumption or processing
02 02 04 sludges from on-site effluent treatment

02 03 00 wastes from fruit, vegetables, cereals, edible oils, cocoa, coffee and tobacco
preparation, processing; conserve production; tobacco processing
02 03 01 sludges from washing, cleaning, peeling, centrifuging and separation
02 03 02 wastes from preserving agents
02 03 03 wastes from solvent extraction
02 03 04 materials unsuitable for consumption or processing
02 03 05 sludges from on-site effluent treatment

02 04 00 wastes from sugar processing

02 04 03 sludges from on-site effluent treatment

02 05 00 wastes from dairy products industry

02 05 01 materials unsuitable for consumption or processing
02 05 02 sludges from on-site effluent treatment

02 06 00 wastes from backing and confectionery industry

02 06 02 wastes from preserving agents
02 06 03 sludges from on-site effluent treatment

02 07 00 wastes from the production of alcoholic and non-alcoholic beverages

(Excluding coffee, tea and cocoa)
02 07 01 wastes from washing, cleaning and mechanical reduction of the raw material
02 07 02 wastes from spirits distillation
02 07 03 wastes from chemical treatment
02 07 04 materials unsuitable for consumption or processing
02 07 05 sludges from on-site effluent treatment
 85

APPENDIX 1: List of waste materials suitable for AFR - Page 7 of 7

C. Other Wastes
1.0 Disposed, sorted and/or stocked wastes from a waste treatment facility

05 08 00 waste from oil regeneration

05 08 02 acid tars
05 08 03 other tars
05 08 04 aqueous liquid waste from oil regeneration

14 05 00 wastes from solvent and coolant recovery (still bottoms)

14 05 01 chlorofluorocarbons
14 05 02 other halogenated solvents and solvent mixtures
14 05 03 other solvents and solvent mixtures
14 05 04 sludge containing halogenated solvents
14 05 05 sludge containing other solvents

16 07 00 waste from transport and storage tank cleaning (except 05 00 00 & 12 00 00)
16 07 01 wastes from marine transport tank cleaning, containing chemicals
16 07 02 wastes from marine transport tank cleaning, containing oil
16 07 02 wastes from marine transport tank cleaning, containing oil
16 07 03 wastes from railway and road transport tank cleaning, containing oil
16 07 04 wastes from railway and road transport tank cleaning, containing chemicals
16 07 05 wastes from storage tank cleaning, containing chemicals
16 07 06 wastes from storage tank cleaning, containing oil

Wastes from drums and tanks treatment facility, contaminated by one or more
Constituent enumerated in Annex II of Directive 91/689/CEE

19 01 00 wastes from incineration or pyrolysis of municipal and similar commercial,

industrial and institutional waste
19 01 08 pyrolysis wastes

19 06 00 wastes from anaerobic treatment of wastes

19 06 01 anaerobic treatment sludges of municipal and similar wastes
19 06 02 anaerobic treatment sludges of animal and vegetable wastes

19 07 00 landfill leachate
19 07 01 landfill leachate

19 08 00 wastes from waste water treatment plants not otherwise specified

19 08 03 grease and oil mixture from oil/waste water separation

20 01 00 separately collected fractions

20 01 09 oil and fat
20 01 12 paint, inks, adhesive and resins
20 01 13 solvents
20 01 16 detergents
20 01 18 medicines
20 01 19 pesticides
20 03 00 other municipal waste
 86

APPENDIX 2: MATERIAL SAFETY DATA SHEET OF LINDANE

The MSDS can also be found at https://fscimage.fishersci.com/msds/95168.htm

Section 1 - Chemical Product and Company Identification

MSDS Name: 1,2,3,4,5,6-Hexachlorocyclohexane, gamma-isomer
Catalogue Numbers: AC411350000, AC411350030, AC411355000
Synonyms: Benzene hexachloride; gamma-Benzene hexachloride; Viton; Lindane;
Hexachlorocyclohexane; BHC; gamma-BHC.
Company Identification:
Acros Organics N.V.
One Reagent Lane
Fair Lawn, NJ 07410
For information in North America, call: 800-ACROS-01
For emergencies in the US, call CHEMTREC: 800-424-9300

Section 2 - Composition, Information on Ingrédients

CAS# Chemical Name Percent EINECS/ELINCS
58-89-9 Lindane 100 200-401-2

Section 3 - Hazards Identification

EMERGENCY OVERVIEW
Appearance: white crystalline powder crystalline powder.
Danger! May be fatal if absorbed through the skin. Harmful if swallowed. Causes eye and skin
irritation. May cause central nervous system effects. Potential cancer hazard. May cause cancer
based on animal studies. May cause kidney damage. Dangerous for the environment. May cause
reproductive and fatal effects.
Target Organs: Blood, kidneys, central nervous system and liver.
Potential Health Effects
Eye: Causes eye irritation. May cause chemical conjonctivites.
Skin: Causes skin irritation. May be fatal if absorbed through the skin.
Ingestion: Harmful if swallowed. May cause gastrointestinal irritation with nausea, vomiting and
diarrhoea. May cause liver and kidney damage. Human fatalities have been reported from acute
poisoning. Large doses may cause convulsions. May cause central nervous system stimulation.
Inhalation: Causes respiratory tract irritation. May cause liver and kidney damage. Exposure may
result in irritation, excitement, and convulsions. Can produce delayed pulmonary oedema. May
cause central, peripheral, and autonomic nervous system effects.
Chronic: May cause liver and kidney damage. May cause cancer according to animal studies.
May cause reproductive and fatal effects. Effects may be delayed.

Section 4 - First Aid Measures

Eyes: Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the
upper and lower eyelids. Get medical aid.
Skin: Get medical aid immediately. Flush skin with plenty of water for at least 15 minutes while
removing contaminated clothing and shoes. Wash clothing before reuse.
Ingestion: Get medical aid immediately. Do NOT induce vomiting. If conscious and alert, rinse
mouth and drink 2-4 cupfuls of milk or water.
Inhalation: Get medical aid immediately. Remove from exposure and move to fresh air
immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen.
 87

Appendix 2: Material Safety Data Sheet (MSDS) of Lindane - page 2 of 6

Do NOT use mouth-to-mouth resuscitation. If breathing has ceased apply artificial respiration
using oxygen and a suitable mechanical device such as a bag and a mask. Notes to Physician:
Treat symptomatically and supportively.

Section 5 - Fire Fighting Measures

General Information: As in any fire, wear a self-contained breathing apparatus in pressure-
demand, MSHA/NIOSH (approved or equivalent), and full protective gear. Water runoff can
cause environmental damage. Dike and collect water used to fight fire. During a fire, irritating and
highly toxic gases may be generated by thermal decomposition or combustion. Use water spray to
keep fire-exposed containers cool. Containers may explode when heated. Non-combustible,
substance itself does not burn but may decompose upon heating to produce corrosive and/or toxic
fumes.
Extinguishing Media: Do NOT get water inside containers. Do NOT use straight streams of
water. For small fires, use dry chemical, carbon dioxide, or water spray. For large fires, use water
spray, fog or regular foam. Cool containers with flooding quantities of water until well after fire is
out.
Flash Point: 150°C (302°F)
Autoignition Temperature: Not applicable.
Explosion Limits, Lower: Not available.
Explosion limits, Upper: Not available.
NFPA Rating: (estimated) Health: 2; Flammability: 1; Instability: 0

Section 6 - Accidental Release Measures

General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks: Vacuum or sweep up material and place into a suitable disposal container. Avoid
runoff into storm sewers and ditches which lead to waterways. Clean up spills immediately,
observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation. Do not get water inside containers. Do not let this chemical enter the
environment.

Section 7 - Handling and Storage

Handling: Wash thoroughly after handling. Remove contaminated clothing and wash before
reuse. Minimize dust generation and accumulation. Avoid contact with eyes, skin, and clothing.
Keep container tightly closed. Avoid ingestion and inhalation. Use with adequate ventilation.
Storage: Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from
incompatible substances. Keep away from metals. Poison room locked.

Section 8 - Exposure Controls, Personal Protection

Engineering Controls: Facilities storing or utilizing this material should be equipped with an
eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations
low.
Exposure Limits

OSHA Vacated PELs: Lindane: 0.5 mg/m3 TWA

 88

Appendix 2: Material Safety Data Sheet (MSDS) of Lindane - page 3 of 6

Personal Protective Equipment
Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's
eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin: Wear appropriate protective gloves to prevent skin exposure.
Clothing: Wear appropriate protective clothing to prevent skin exposure.
Respirators: A respiratory protection program that meets OSHA's 29 CFR 1910.134 and ANSI
Z88.2 requirements or European Standard EN 149 must be followed whenever workplace
conditions warrant respirator use.

Section 9 - Physical and Chemical Properties

Physical State: Crystalline powder
Appearance: white crystalline powder
Odour: aromatic odour
pH: Not available.
Vapour Pressure: Negligible
Vapour Density: Not available.
Evaporation Rate: Not available.
Viscosity: Not available.
Boiling Point: 323°C
Freezing/Melting Point: 111.5-114.5 °C
Decomposition Temperature: Not available.
Solubility: Slightly soluble in water.
Specific Gravity/Density: 1.85
Molecular Formula: C6H6Cl6
Molecular Weight: 290.82

Section 10 - Stability and Reactivity

Chemical Stability: Stable at room temperature in closed containers under normal storage and
handling conditions.
Conditions to Avoid: Incompatible materials, dust generation, excess heat, strong oxidants,
powdered metals.
Incompatibilities with Other Materials: Strong oxidizing agents.
Hazardous Decomposition Products: Carbon monoxide, oxides of nitrogen, irritating and toxic
fumes and gases, carbon dioxide.
Hazardous Polymerization: Has not been reported

Section 11 - Toxicological Information

RTECS#:
CAS# 58-89-9: GV4900000
LD50/LC50:
CAS# 58-89-9:
Oral, mouse: LD50 = 44 mg/kg;
Oral, mouse: LD50 = 85.8 mg/kg;
Oral, rabbit: LD50 = 60 mg/kg;
Oral, rat: LD50 = 76 mg/kg;
Skin, rabbit: LD50 = 50 mg/kg;
Skin, rabbit: LD50 = 500 mg/kg;
Skin, rat: LD50 = 414 mg/kg;
.
 89

Appendix 2: Material Safety Data Sheet (MSDS) of Lindane - page 4 of 6

Carcinogenicity:
CAS# 58-89-9:
ACGIH: A3 - Confirmed animal carcinogen with unknown relevance to humans
California: carcinogen, initial date 10/1/89
NTP: Suspect carcinogen
IARC: Group 2B carcinogen (listed as Hexachlorocyclohexane (mixed isomers)).
Epidemiology: Experimental reproductive and teratogenic effects have been reported.
Teratogenicity: No information available.
Reproductive Effects: Adverse reproductive effects have occurred in humans. Adverse
reproductive effects have occurred in experimental animals.
Mutagenicity: Mutagenic effects have occurred in experimental animals.
Neurotoxicity: No information available.

Section 12 - Ecological Information

Ecotoxicity: Fish: Fathead Minnow: 87µg/L; 96H; Fish: Brown trout: 1.7µg/L; 96H; No data
available.
Environmental: Expected to biodegrade and bio concentrate.
Physical: No information available.
Other: For more information, see "HANDBOOK OF ENVIRONMENTAL FATE AND
EXPOSURE DATA." Biodegradable.

Section 13 - Disposal Considerations

Chemical waste generators must determine whether a discarded chemical is classified as a
hazardous waste. US EPA guidelines for the classification determination are listed in 40 CFR
Parts 261.3. Additionally, waste generators must consult state and local hazardous waste
regulations to ensure complete and accurate classification.
RCRA P-Series: None listed.
RCRA U-Series:
CAS# 58-89-9: waste number U129.

Section 14 - Transport Information

Section 15 - Regulatory Information

US FEDERAL
TSCA
CAS# 58-89-9 is listed on the TSCA inventory.
Health & Safety Reporting List
None of the chemicals are on the Health & Safety Reporting List.
Chemical Test Rules
None of the chemicals in this product are under a Chemical Test Rule.
Section 12b
None of the chemicals are listed under TSCA Section 12b.
TSCA Significant New Use Rule
None of the chemicals in this material have a SNUR under TSCA.
 90

Appendix 2: Material Safety Data Sheet (MSDS) of Lindane - page 5 of 6

CERCLA Hazardous Substances and corresponding RQs

CAS# 58-89-9: 1 lb final RQ; 0.454 kg final RQ
SARA Section 302 Extremely Hazardous Substances
CAS# 58-89-9: 1000 lb TPQ (lower threshold); 10000 lb TPQ (upper threshold)
SARA Codes
CAS # 58-89-9: immediate, delayed.
Section 313
This material contains Lindane (CAS# 58-89-9, 100%), which is subject to the reporting
requirements of Section 313 of SARA Title III and 40 CFR Part 373.
Clean Air Act:
CAS# 58-89-9 is listed as a hazardous air pollutant (HAP).
This material does not contain any Class 1 Ozone depletors.
This material does not contain any Class 2 Ozone depletors.
Clean Water Act:
CAS# 58-89-9 is listed as a Hazardous Substance under the CWA. CAS# 58-89-9 is listed as a
Priority Pollutant under the Clean Water Act. CAS# 58-89-9 is listed as a Toxic Pollutant under
the Clean Water Act.
OSHA:
None of the chemicals in this product are considered highly hazardous by OSHA.
STATE
CAS# 58-89-9 can be found on the following state right to know lists: California, New Jersey,
Pennsylvania, Minnesota, and Massachusetts.
California Prop 65
The following statement(s) is (are) made in order to comply with the California Safe Drinking
Water Act:
WARNING: This product contains Lindane, a chemical known to the state of California to cause
cancer.
California No Significant Risk Level: CAS# 58-89-9: 0.6 µg/day NSRL
European/International Regulations
European Labelling in Accordance with EC Directives
Hazard Symbols:
TN
Risk Phrases (see also Appendix 4):
R 23/24/25 Toxic by inhalation, in contact with skin and if swallowed.
R 36/38 Irritating to eyes and skin.
R 50/53 Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic
environment.
Safety Phrases (see also Appendix 5):
S 13 Keep away from food, drink and animal feeding stuffs.
S 45 In case of accident or if you feel unwell, seek medical advice immediately (show the label
where possible).
S 60 This material and its container must be disposed of as hazardous waste.
S 61 Avoid release to the environment. Refer to special instructions/safety data sheets.
WGK (Water Danger/Protection)
CAS# 58-89-9: 3
Canada - DSL/NDSL
CAS# 58-89-9 is listed on Canada's DSL List.
Canada - WHMIS
This product has a WHMIS classification of D1A, D1B, D2A, D2B.
 91

Appendix 2: Material Safety Data Sheet (MSDS) of Lindane - page 6 of 6

This product has been classified in accordance with the hazard criteria of the Controlled Products
Regulations and the MSDS contains all of the information required by those regulations.
Canadian Ingredient Disclosure List
CAS# 58-89-9 is not listed on the Canadian Ingredient Disclosure List.

Section 16 - Additional Information

MSDS Creation Date: 7/08/1999
Revision #4 Date: 10/03/2005
 92

APPENDIX 3: MATERIAL SAFETY DATA SHEET (MSDS) OF DDT

This MSDS can be found at http://www.pcl.ox.ac.uk/MSDS/DD/DDT.html

General
Synonyms: 2,2-bis(p-chlorophenyl)-1,1,1-trichloroethane, 4,4'-DDT, α,α-bis(p-chlorophenyl)-
β,β,β-trichloroethane, dichlorodiphenyltrichloroethane, diphenyltrichloroethane,
chlorophenothane, p,p'-dichlorodiphenyltrichloroethane, 4,4'-dichlorodiphenyltrichloroethane,
1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane,
1,1,1-trichloro-2,2-di(4-chlorophenyl)ethane, numerous trade and other non-systematic names,
including those given below (Note: The use of DDT has been largely discontinued, so most -
perhaps all - of these trade names are no longer used.): anofex, p,p'-DDT, dicophane, didigam,
didimac, ENT 1,506, estonate, genitox, gesafid, gesarol, gyron, ixodex, NCI-C00464, neocid,
pentachlorin, santobane, trichlorobis(4-chlorophenyl)ethane, 1,1,1-trichloro-2,2-bis(p-
chlorophenyl)ethane, zeidane, zerdane, agritan, arkotine, azotox, 1,1'-(2,2,2-
trichloroethylidene)bis(4-chlorobenzene), bosan, supra, boviderm, chlorphenothan,
chlorophenotoxum, citox, clofenotane, dedlo, deoval, detox, detoxan, dibovan, dodat, dykol,
gesafid, gesapon, gesarex, guesapon, havero-extra, hildit, ivoran, kopsol, micro, DDT 75,
mutoxin, NA 2761, OMS 16, parachlorocium, peb1, pentech, ppzeidan
Use: insecticide, formerly one of the most widely used insecticides in the world; now used in only
limited areas because of environmental concerns
Molecular formula: C14H9Cl5
CAS No: 50-29-3
EINECS No:

Physical data
Appearance: colourless to white crystalline powder
Melting point: 108-109°C
Boiling point: 260°C
Vapour density:
Vapour pressure:
Density: 1.56 g/cm3
Flash point: 165°C
Explosion limits:
Autoignition temperature:
Water solubility: very slight

Stability
Stable. Combustible. Incompatible with strong oxidizing agents, iron and aluminium and their
salts, alkalis.

Toxicology
Poison if swallowed. May be harmful if inhaled or absorbed through the skin. Absorption is
considerably enhanced by the presence of oils. Possible human carcinogen. Human mutagenic
effects. May cause reproductive damage. May act as a systemic poison. Unlikely to be fatal on its
own, but the toxic effects of this chemical appear to be enhanced when exposure simultaneously
includes other chemicals. DDT and its degradation products, particularly DDE, are stored in fat in
the body, and this can lead to a total body load of chemical which is potentially much greater than
the fatal dose. This stored material is removed only gradually from the body.
 93

Appendix 3: Material Safety Data Sheet (MSDS) of DDT - page 2 of 2

Toxicity data
(The meaning of any toxicological abbreviations which appear in this section is given here:
http://ptcl.chem.ox.ac.uk/MSDS/toxicity_abbreviations.html)
ORL-RAT LD50 87 mg/kg
SKN-RAT LD50 1931 mg/kg
ORL-HMN LDLO 500 mg/kg (though far lower figures are also quoted)
SCU-RAT LD50 1500 mg/kg
ORL-MUS LD50 135 mg/kg
ORL-RBT LD50 250 mg/kg

Transport information
UN No 2761. Hazard class 6.1. Packing group III.

Environmental information
A serious environmental hazard due to bioaccumulation and transport up the food chain.
Concentrations in animals near the top of the food chain (such as predatory birds) may become
high enough in areas in which DDT has been heavily used, to have devastating effects upon
reproductive ability. Degrades extremely slowly in the environment and is removed very slowly
from animal tissue.

Personal protection
Safety glasses, gloves, good ventilation. Treat as a possible carcinogen.

Other information
Note that use of DDT as an insecticide is banned in most countries.
This information was last updated on March 29, 2005.
 94

APPENDIX 4: RISK PHRASES

RISK PHRASES - R-phrases. (Reproduced from the Approved Supply List (6th edition,
2000) by HSC from Annex 1 of the Dangerous Substances Directive (67/548/EEC), effective
in the European Union from October 2000.

R-phrase references
1: Explosive when dry
2: Risk of explosion by shock, friction, fire or other sources of ignition
3: Extreme risk of explosion by shock, friction, fire or other sources of ignition
4: Forms very sensitive explosive metallic compounds
5: Heating may cause an explosion
6: Explosive with or without contact with air
7: May cause fire
8: Contact with combustible material may cause fire
9: Explosive when mixed with combustible material
10: Flammable
11: Highly flammable
12: Extremely flammable
14: Reacts violently with water
15: Contact with water liberates extremely flammable gases
16: Explosive when mixed with oxidizing substances
17: Spontaneously flammable in air
18: In use may form flammable/explosive vapour-air mixture
19: May form explosive peroxides
20: Harmful by inhalation
21: Harmful in contact with skin
22: Harmful if swallowed
23: Toxic by inhalation
24: Toxic in contact with skin
25: Toxic if swallowed
26: Very toxic by inhalation
27: Very toxic in contact with skin
28: Very toxic if swallowed
29: Contact with water liberates toxic gas
30: Can become highly flammable in use
31: Contact with acids liberates toxic gas
32: Contact with acids liberates very toxic gas
33: Danger of cumulative effects
34: Causes burns
35: Causes severe burns
36: Irritating to the eyes
37: Irritating to the respiratory system
38: Irritating to the skin
39: Danger of very serious irreversible effects
40: Possible risk of irreversible effects
41: Risk of serious damage to eyes
42: May cause sensitisation by inhalation
43: May cause sensitisation by skin contact
44: Risk of explosion if heated under confinement
 95

Appendix 4: Risk phrases - page 2 of 4

45: May cause cancer
46: May cause heritable genetic damage
48: Danger of serious damage to health by prolonged exposure
49: May cause cancer by inhalation
50: Very toxic to aquatic organisms
51: Toxic to aquatic organisms
52: Harmful to aquatic organisms
53: May cause long-term adverse effects in the aquatic environment
54: Toxic to flora
55: Toxic to fauna
56: Toxic to soil organisms
57: Toxic to bees
58: May cause long-term adverse effects in the environment
59: Dangerous for the ozone layer
60: May impair fertility
61: May cause harm to the unborn child
62: Possible risk of impaired fertility
63: Possible risk of harm to the unborn child
64: May cause harm to breastfed babies
65: Harmful: may cause lung damage if swallowed
66: Repeated exposure may cause skin dryness or cracking
67: Vapours may cause drowsiness and dizziness

Combination of particular risks

14/15: Reacts violently with water, liberating extremely flammable gases
15/29: Contact with water liberates toxic, extremely flammable gas
20/21: Harmful by inhalation and in contact with skin
20/21/22: Harmful by inhalation, in contact with skin and if swallowed
20/22: Harmful by inhalation and if swallowed
21/22: Harmful in contact with skin and if swallowed
23/24: Toxic by inhalation and in contact with skin
23/24/25: Toxic by inhalation, in contact with skin and if swallowed
23/25: Toxic by inhalation and if swallowed
24/25: Toxic in contact with skin and if swallowed
26/27: Very toxic by inhalation and in contact with skin
26/27/28: Very toxic by inhalation, in contact with skin and if swallowed
26/28: Very toxic by inhalation and if swallowed
27/28: Very toxic in contact with skin and if swallowed
36/37: Irritating to eyes and respiratory system
36/37/38: Irritating to eyes, respiratory system and skin
36/38: Irritating to eyes and skin
37/38: Irritating to respiratory system and skin
39/23: Toxic: danger of very serious irreversible effects through inhalation
39/23/24: Toxic: danger of very serious irreversible effects through inhalation and in
contact with skin
39/23/24/25: Toxic: danger of very serious irreversible effects through inhalation, in
contact with skin and if swallowed
39/23/25: Toxic: danger of very serious irreversible effects through inhalation and if
swallowed
 96

Appendix 4: Risk phrases - page 3 of 4

39/24: Toxic: danger of very serious irreversible effects in contact with skin
39/24/25: Toxic: danger of very serious irreversible effects in contact with skin and if
swallowed
39/25: Toxic: danger of very serious irreversible effects if swallowed
39/26: Very toxic: danger of very serious irreversible effects through inhalation
39/26/27: Very toxic: danger of very serious irreversible effects through inhalation and
in contact with skin
39/26/27/28: Very toxic: danger of very serious irreversible effects through inhalation,
in contact with skin and if swallowed
39/26/28: Very toxic: danger of very serious irreversible effects through inhalation and
if swallowed
39/27: Very toxic: danger of very serious irreversible effects in contact with skin
39/27/28: Very toxic: danger of very serious irreversible effects in contact with skin
and if swallowed
39/28: Very toxic: danger of very serious irreversible effects if swallowed
40/20: Harmful: possible risk of irreversible effects through inhalation
40/20/21: Harmful: possible risk of irreversible effects through inhalation and in
contact with skin
40/20/21/22: Harmful: possible risk of irreversible effects through inhalation, in
contact with skin and if swallowed
40/20/22: Harmful: possible risk of irreversible effects through inhalation and if
swallowed
40/22: Harmful: possible risk of irreversible effects if swallowed
40/21: Harmful: possible risk of irreversible effects in contact with skin
40/21/22: Harmful: possible risk of irreversible effects in contact with skin and if
swallowed
42/43: May cause sensitisation by inhalation and skin contact
48/20: Harmful: danger of serious damage to health by prolonged exposure through
inhalation
48/20/21: Harmful: danger of serious damage to health by prolonged exposure through
inhalation and in contact with skin
48/20/21/22: Harmful: danger of serious damage to health by prolonged exposure through
inhalation, in contact with skin and if swallowed
48/20/22: Harmful: danger of serious damage to health by prolonged exposure through
inhalation and if swallowed
48/21: Harmful: danger of serious damage to health by prolonged exposure in
contact with skin
48/21/22: Harmful: danger of serious damage to health by prolonged exposure in
contact with skin and if swallowed
48/22: Harmful: danger of serious damage to health by prolonged exposure if
swallowed
48/23: Toxic: danger of serious damage to health by prolonged exposure
through inhalation
48/23/24: Toxic: danger of serious damage to health by prolonged exposure
through inhalation and in contact with skin
48/23/24/25: Toxic: danger of serious damage to health by prolonged exposure
through inhalation, in contact with skin and if swallowed
48/23/25: Toxic: danger of serious damage to health by prolonged exposure
through inhalation and if swallowed
 97

Appendix 4: Risk phrases - page 4 of 4

48/24: Toxic: danger of serious damage to health by prolonged exposure in

contact with skin
48/24/25: Toxic: danger of serious damage to health by prolonged exposure in
contact with skin and if swallowed
48/25: Toxic: danger of serious damage to health by prolonged exposure if
swallowed
50/53: Very toxic to aquatic organisms, may cause long-term adverse effects in the
aquatic environment
51/53: Toxic to aquatic organisms. May cause long-term adverse effects in the
environment
52/53: Harmful to aquatic organism; may cause long-term aquatic
 98

APPENDIX 5: SAFETY PHRASES

SAFETY PHRASES - S-phrases. (Reproduced from the Approved Supply List (6th edition
2000) by HSC from Annex 1 of the Dangerous Substances Directive (67/548/ EEC), effective in
the European Union from October 2000, and from the Merck catalogue.

S-phrase references
1: Keep locked up
2: Keep out of reach of children
3: Keep in a cool place
4: Keep away from living quarters
5: Keep contents under ... (appropriate liquid to be specified by the manufacturer)
6: Keep under.. . (inert gas to be specified by the manufacturer)
7: Keep container tightly closed
8: Keep container dry
9: Keep container in a well ventilated place
12: Do not keep the container sealed
13: Keep away from food, drink and animal feeding stuffs
14: Keep away from ... (incompatible materials to be indicated by the manufacturer)
15: Keep away from heat
16: Keep away from sources of ignition - No Smoking
17: Keep away from combustible material
18: Handle and open container with care
20: When using do not eat or drink
21: When using do not smoke
22: Do not breathe dust
23: Do not breathe gas/fumes/vapour/spray (appropriate wording to he specified by
manufacturer)
24: Avoid contact with skin
25: Avoid contact with eyes
26: In case of contact with eyes, rinse immediately with plenty of water and seek
medical advice
27: Take off immediately all contaminated clothing
28: After contact with skin, wash immediately with plenty of... (to be specified by the
manufacturer)
28.1: After contact with skin, wash immediately with plenty of water
28.3: After contact with skin, wash immediately with plenty of soap and water, if
possible also with polyethylene glycol 400
29: Do not empty into drains
30: Never add water to this product
33: Take precautionary measures against static discharges
35: This material and its container must be disposed of in a safe way
36: Wear suitable protective clothing
37: Wear suitable gloves
38: In case of insufficient ventilation, wear suitable respiratory equipment
39: Wear eye/face protection
40: To clean the floor and all objects contaminated by this material use... (to be
specified by the manufacturer)
41: In case of fire and/or explosion do not breathe fumes
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Appendix 5: Safety phrases - page 2 of 3

42: During fumigation/spraying wear suitable respiratory equipment (appropriate
wording to be specified)
43: In case of fire, use... (indicate in the space the precise type of fire-fighting
equipment. If water increases the risk, add ... Never use water)
43.1: In case of fire, use water
43.2: In case of fire, use water or powder extinguisher
43.3: In case of fire, use powder extinguisher - never use water
43.4: In case of fire, use CO 2 - never use water
43.6: In case of fire, use sand - never use water
43.7: In case of fire, use metal fire powder - never use water
43.8: In case of fire, use sand, CO 2 or powder extinguisher - never use water
45: In case of accident or if you feel unwell, seek medical advice immediately (show
the label where possible)
46: If swallowed seek medical advice immediately and show this container or label
47: Keep at temperature not exceeding . . . °C (to be specified by the manufacturer)
48: Keep wetted with ... (appropriate material to be specified by the manufacturer)
49: Keep only in the original container
50: Do not mix with ... (to be specified by the manufacturer)
50.1: Do not mix with acids
51: Use only in well ventilated areas
52: Not recommended for interior use on large surface areas
53: Avoid exposure - obtain special instruction before use
56: Dispose of this material and its container to hazardous or special waste collection
point
57: Use appropriate containment to avoid environmental contamination
59: Refer to manufacturer/supplier for information on recovery/recycling
60: This material and/or its container must be disposed of as hazardous waste
61: Avoid release to the environment. Refer to special instructions/safety data sheet
62: If swallowed, do not induce vomiting: seek medical advice immediately and show
this container or label
63: In case of accident by inhalation: remove casualty to fresh air and keep at rest
64: If swallowed, rinse mouth with water (only if the person is conscious)

Combination of safety precautions

1/2: Keep locked up and out of reach of children
3/9/14: Keep in a cool, well-ventilated place away from ... (incompatible materials
to he indicated by the manufacturer)
3/9/14/49: Keep only in the original container in a cool, well-ventilated place away
from ... (incompatible materials to be indicated by the manufacturer)
3/9/49: Keep only in the original container in a cool, well-ventilated place
3/14: Keep in a cool place away from ... (incompatible materials to be indicated by
the manufacturer)
3/7: Keep container tightly closed in a cool place
7/8: Keep container tightly closed and dry
7/9: Keep container tightly closed and in a well-ventilated place
7/47: Keep container tightly closed and at a temperature not exceeding . . . °C (to
specified by manufacturer)
20/21: When using do not eat, drink or smoke
24/25: Avoid contact with skin and eyes
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Appendix 5: Safety phrases - page 3 of 3

29/56: Do not empty into drains; dispose of this material and its container to
hazardous or special waste collection point
36/37: Wear suitable protective clothing and gloves
36/37/39: Wear suitable protective clothing, gloves and eye/face protection
36/39: Wear suitable protective clothing and eye/face protection
37/39: Wear suitable gloves and eye/face protection
47/49: Keep only in the original container at temperature not exceeding. . . °C (to be
specified by the manufacturer).