By : Khaled Mahmoud Mohamed Supervision :DR .

Said Khater

1.1 abstract
1) Processes in the manufacture of paper and paperboard can, in general terms, Be split into three steps: pulp making, pulp processing, and paper production
2) a stock pulp mixture is produced by digesting a material into its fibrous constituents via chemical, mechanical, or a combination of chemical and mechanical means 3) the most common pulping material, chemical pulping actions release cellulose fibers by selectively destroying the chemical bonds in the glue-like substance (lignin) that binds the fibers together 4) After the fibers are separated and impurities have been removed, the pulp may be bleached to improve brightness and processed to a form suitable for papermaking equipment

5) At the papermaking stage, the pulp can be combined with dyes, strength building resins, or texture adding filler materials, depending on its intended end product. 6) the mixture is dewatered, leaving the fibrous constituents and pulp additives

7) The fibers bond together as they are carried through a series of presses and heated rollers. The final paper product is usually spooled on large rolls for storage
8) the pulp and paper making industry is a very water intensive industry and ranks third in the world, after the primary metals and chemical industries, in terms of

fresh water consumption

9) Historically, the pulp and paper industry has been considered to be a major consumer of natural resources (wood, water) and energy (fossil fuels, electricity) and a significant contributor of pollutant discharges to the environment

1.2 process description

The Kraft process (also known as Kraft pulping or sulfate process) describes a
technology for conversion of wood into wood pulp consisting of almost pure cellulose fibers. The process entails treatment of wood chips with a mixture of sodium hydroxide and sodium sulfide , known as white liquor , that break the bonds that link lignin to the cellulose.

History: The Kraft process was invented by Carl F. Dahl in 1879 in Danzig, Prussia,
Germany , U.S. Patent 296,935 was issued in 1884, and a pulp mill using this technology started (in Sweden) in 1890. The invention of the recovery boiler by G.H.Tomlinson in the early 1930s

cooking
1) Woodchips are fed into vessels called digesters impregnated with the cooking liquors. 2) The cooking liquors consist of warm black liquor and white liquor. The warm black liquor is the spent cooking liquor coming from the blowing. White liquor is a mixture of sodium hydroxide and sodium sulfide, produced in the recovery process.

3) Typically delignification requires several hours at 130 to 180 C (266 to 356 F). Under these conditions lignin and some hemicelluloses degrade to give fragments that are soluble in the strongly basic liquid.
4) The solid pulp (about 50% by weight based on the dry wood chips) is collected and

washed. At this point the pulp is quite brown and is known as brown stock
5) The combined liquids, known as black liquor (so called because of its color), contain lignin fragments, carbohydrates from the breakdown of hemicelluloses, sodium carbonate, sodium sulfate and other inorganic salts.

Blowing
The finished cooked wood chips are blown by reducing the pressure to atmospheric pressure. This releases a lot of steam and volatiles. The steam produced can then be used to heat the pulp mill and any excess used in district heating schemes or to drive a steam turbine to generate electrical power. The volatiles are condensed and collected, in the case of northern softwoods this consists mainly of raw turpentine.

Screening
1) Screening of the pulp after pulping is a process whereby the pulp is separated from large shives, knots, dirt and other debris. The accept is the pulp. The material separated from the pulp is called reject.
2) The screening section consists of different types of sieves (screens) and centrifugal cleaning 3) The fiber containing shives and knots is separated from the rest of the reject and reprocessed either in a refiner and/or is sent back to the digester

Washing
1) The brown stock from the blowing goes to the washing stages where the used

cooking liquors are separated from the cellulose fibers.

2) Normally a pulp mill has 3-5 washing stages in series. Washing stages are also placed after oxygen delignification and between the bleaching stages as well.

3) Lower dilution factor reduces energy consumption, while higher dilution factor normally gives cleaner pulp. Thorough washing of the pulp reduces the chemical oxygen demand (COD).
4) Several types of washing equipment are in use:
Pressure diffusers Atmospheric diffusers Vacuum drum washers Drum displacers Wash presses

Bleaching
1) to improve brightness, purity and processed to a form suitable for papermaking

equipment
2) In a modern mill, brown stock (cellulose fibers containing approximately 5% residual lignin), produced by the pulping is first washed to remove some of the dissolved organic material and then further delignified by a variety of bleaching

stages
3) Bleaching decreases the mass of pulp produced by about 5%, decreases the strength of the fibers and adds to the cost of manufacture.

Recovery process
1) The excess black liquor is at about 15 % solids and is concentrated in a multiple effect evaporator. After the first step the black liquor is about 20 - 30 % solids. At this concentration the rosin soap rises to the surface and is skimmed off. The collected soap is further processed to tall oil. Removal of the soap improves the evaporation operation of the later effects.
2) The weak black liquor is further evaporated to 60% or even 80% solids ("heavy black liquor) and burned in the recovery boiler to recover the inorganic chemicals for reuse in the pulping process. Higher solids in the concentrated black liquor increases the energy and chemical efficiency of the recovery cycle, but also gives

higher viscosity and precipitation of solids

The combustion is carried out such that sodium sulfate is reduced to sodium sulfide by the organic carbon in the mixture: Na2SO4 + 2 C Na2S + 2 CO2 The molten salts ("smelt") from the recovery boiler are dissolved in process water known as "weak wash". This process water, also known as "weak white liquor" is composed of all liquors used to wash lime mud and green liquor precipitates and is kept in a tank called "weak wash storage tank". The resulting solution of sodium carbonate and sodium sulfide is known as "green liquor". This liquid is mixed with calcium hydroxide to regenerate the white liquor used in the pulping process through an equilibrium reaction (Na2S is shown since it is part of the green liquor, but does not participate in the reaction): 2. Na2S + Na2CO3 + Ca(OH) 2 Na2S + 2 NaOH + CaCO3

Calcium carbonate precipitates from the white liquor and is recovered and heated in a lime kiln where it is converted to calcium oxide (lime). 3. CaCO3 CaO + CO2 Calcium oxide (lime) is reacted with water to regenerate the calcium hydroxide used in Reaction 2: 4. CaO + H2O Ca(OH)2 The recovery boiler also generates high pressure steam which is fed to turbo generators, reducing the steam pressure for the mill use and generating electricity.

Process chemicals
Process chemicals are added to improve the production process:
1) Impregnation aids. Surfactants may be used to improve impregnation of the wood chips with the cooking liquors.
2) Anthraquinone is used as a digester additive. It works as a red ox catalyst by oxidizing cellulose and reducing lignin. This is protecting the cellulose from degradation and makes the lignin more water soluble. 3) An emulsion breaker can be added in the soap separation to speed up and improve the separation of soap from the used cooking liquors by flocculation.

4)

Defoamers remove foam and speed up the production process. Drainage of washing equipment is improved and gives cleaner pulp. Dispersing agents and complexing agents are keeping the system cleaner and reduce the need for maintenance stops. Fixation agents are fixating finely dispersed potential deposits to the fibers and thereby transporting it out of the process.

5)

6)

Problem 1:The Kraft process is a heavy chemical user and creates pollution problems. problem 2:In recovery process the burning of liquor and evaporation of black liquor In
the furnace, the organic compounds in the liquor generate heat and carbon dioxide which is absorbed by the predominantly alkaline residue to form sodium carbonate. The sulphur containing compounds undergo a series of reaction to produce hydrogen sulphide, sulphur dioxide and sodium sulphide. The sulphur containing compounds comprise a major source of air pollution.

Problem 3: sulpher vapors from delignifying process in the cooking

Problem 4:The pulp and paper making industry is a very water intensive industry .
the pulp and paper industry has been considered to be a major consumer of natural resources (wood, water) and energy (fossil fuels, electricity) and a significant contributor of pollutant discharges to the environment

Problem5 : 1) chlorines used in bleaching process which are hazardous to health and difficult
2) 3)

to handle. the compounds are corrosive to the pipeline and machinery and as such, the cost of construction has been high the major BOD loading in the discharge effluent.

Problem 6:
Departments like maintenance workshops can have significant environmental impacts (e.g. production of waste oils, leaking petroleum products storage tanks)

Problem 7:
Wastewater discharges arising from pulp and paper processes losses were observed except for saw dust in the wood yard cause high load of BOD

Problem 8:
Poor maintenance and modifying equipment for chipping, screening and delignification lead to increase chemical use and low quality of pulp

Problem 9:
Power Consumption pipeline must be insulated

Problem 10:
Steam from open liquor tank

Pollutants from paper and pulp industry:

Chlorine: form bleaching process and its alternative ozone Sulfur Dioxide: through the burning of fossil fuels (large mills often have their own internal power plants). Dioxins: Dioxin produced by the paper industry is a by-product of the chlorine and chlorine-based bleaching process. (toxic) Hydrogen Sulfide: It is produced during the cooking of the pulp, to help break down the fibers. These are just a few examples of the pollution that comes from the paper manufacturing process. Other pollutants include: carbon monoxide, ammonia, nitrogen oxides, mercury, nitrates, methanol, benzene and more. These chemicals are released into the air and water from most paper mills.

Water usage: recycling of wastewater that used in the operation of the plant and reuse
in the plant to decrease water usage

Waste water: decrease effect of waste water on the environment by recycling this
water remove BOD and micro organisms and reuse in the process.

Energy consumption:
The pipe insulations of the process steam lines were damaged. Proper maintenance of these insulations could reduce the normalized power consumptions
The green liquor in green liquor tank after recovery process emitted steam and voc this steam can be used in steam turbines to generate electricity

Spill control, leakage: maintenance and modifying equipment Consumption of raw material: maintenance and modifying equipment for chipping,
screening and delignification lead to increase chemical use and low quality of pulp

Saw dust in the wood yard: Saw dust that is going to be burnt in hogged fuel boilers
for power and steam generation

Pollution problem associated with chlorine compound: the chlorine compounds

are hazardous to health and difficult to handle only partial replacement of chlorinecontaining compounds are carried out such as oxygen pre delignification ahead of chlorine stage

Sulpher emission:
pollution created by the use of sulphur compounds by delignifying with non-polluting materials. Preferably, the lignocellulosic material is delignified using sodium hydroxide and a catalytic reagent such as Anthraquinone (AQ) followed by oxygen delignification or alternatively, by hydrogen peroxide delignification. This sequence of delignification produces a pulp which has high physical strength properties comparable to Kraft pulp and the same final lignin level while eliminating sulphur in the pulping chemicals and the associated problems

Case study Cleaner Production Opportunity Assessment Study in SEKA Balikesir Pulp and Paper Mill Ankara, Turkey

I. II.

SEKA Balkesir Pulp and Paper Mill. the collected data were compared with international environmental performance indicators from other companies in USA, Canada, Australia, and Europe.

III. This comparison provided the specific opportunities for improvement at different processes in the mill.

IV. SEKA (Turkey Pulp and Paper Mills) It is an integrated mill having steps of wood debarking and chip making, pulp manufacturing, pulp bleaching and paper manufacturing Flow diagram for the overall mill processes is given in (process description).

The adopted audit waste approach comprised of three phases

1) a pre-assessment phase for assessment preparation; a data collection phase to derive material balance
2) material balance(input and out put )

3) a synthesis phase where the findings from the material balance are translated into a waste reduction plan and represents the interpretation of the material balance generated in Phase 2 to identify process areas or components of concern.

The material balance was used to identify the major sources of waste, to observe the deviations from the norms in terms of waste production, to identify areas of unexplained losses

Water Usage:
October 2000 September 2001:Total water consumption for this period was found to be 4,428,900 m3. The normalized water consumption per ton of paper produced is found to be 55.36 m3/ton based on the total production of 79,998 tons of newsprint for the 12-month period investigated.

Based on the data gathered at the pre-assessment step, annual raw material consumption data for individual process steps was determined and tabulated in Table 4. Total news print produced for the study period (12 months; October 2001 September 2001) was 79,998 tons. No significant handling losses were observed except for saw dust in the wood yard. Saw dust that is going to be burnt in hogged fuel boilers for power and steam generation were stored and transported in an open area. This open-air storage and transportation of saw dust results in significant material losses Losses were about 1% of the total wood that makes 2,223 m3 per year

Process input

Process Outputs

Process Outputs

The data obtained in material balance section was compared with EPIs and benchmarks in order to target problem wastes (Table 7) Having tabulated the EPIs and benchmarks from various sources for the three main process sections of the SEKA Balkesir Mill, its performance was compared to the average values of these indicators. (wood yard and chipping operations, CTMP process operations, and paper machine operations) were discussed below

Wood Yard and Chipping Operations Recycle of Log Flume Water

1) Log flumes are used at SEKA Balkesir Mill to transport wood from log piles to

debarked and chippers. The water used to convey the logs can be recycled, with fiber and bark being recovered and burned in the hogged fuel boiler for heat recovery. Alternatively, or in addition, treated wastewater can be used as makeup for the log flume.
2) The practice of log flume water recycle is common among mills that use log flumes. Costs of developing an appropriate recycle system may be in the range of $100,000 to $500,000 . Payback period of this investment is 1-2 years . Recycle of log flume water will reduce the discharge of BOD, and TSS, as well as conserve water

Storm Water Management

1) At the wood yard, the runoff from wood and chip storage and processing areas is of greatest concern, as these streams may contribute substantially to BOD5 and TSS loadings

2) Options for reducing storm water impacts on receiving waters include modifying wood yard operations to reduce storm run-off , and installing curbing, diking, and drainage collection for storm water from chip piles and wood processing areas. Storage and treatment of collected storm water would be required 3) estimated up to 4 kg TSS reduction per ton of ADP produced (Table 8).

Wood Yard and Chipping Operations

Raw Material Selection

The most important factor that is affecting the chip quality is the wood itself

Improved Chipping and Screening

1) 2) 3)

Improved chipping would also be a possibility for reducing fiber losses. The purpose of chipping is to reduce the logs to a smaller size suitable for pulping Chip uniformity is extremely important for proper circulation and penetration of the pulping chemicals, hence considerable attention is paid to operational control and maintenance of the chipper Chip thickness screening has become important to extend delignification and reduce bleach plant chemical demands. since the cooking liquor can only penetrate the chip to a certain thickness.

4)

5)

Improved Chipping and Screening

Costs for chip thickness screening and reprocessing of between $0.4 and $2 million have been cited for new installations . Payback period for this investment have been cited to be 2-3 years . Maximum estimated waste reductions for improved chipping and screening option are tabulated in Table 9

Extended Delignification
1) The amount of chemicals required in the bleach plant is directly related to the residual

lignin content of the pulp.

2) The mill can reduce the bleaching chemical demands and subsequent environmental effects by adopting techniques that reduce the residual lignin content

Extended Delignification
1) allow the pulp cooking time to be extended, enabling further delignification to occur before the pulp moves on to the bleach plant

2) the lignin content of the pulp reduced by between 20 and 50 percent compared to conventional digesters.
3) By splitting the addition of cooking liquor and improving liquor circulation and mixing

4) The more uniform cooking of chips throughout the digester helps maintain pulp yield, (fewer under and over cooked chips), and leads to easier bleach ability and reduced bleaching chemical demand
5) Reductions in conventional pollutants such as BOD5, COD, and color have also been widely realized. 6) Total cost of the modification of the CTMP process has been estimated to be between $1.5 and $2 million . Payback period for this modification have been estimated to be 2 years

Ctmp process operation

Additional Vacuum Extraction Tanks

1) Performer application in paper machine uses centrifugal force for dewatering of paper sheet. This is resulting in high fine fiber losses due to the centrifugal force . 2) additional vacuum extraction tanks that would be installed between formation and couch rolls could decrease the fine fiber losses up to 25%, which Results in BOD5 load reduction of 7 kg per ton of paper produced and 8 kg per ton of paper produced in TSS loading 3) cost $0.6 million. Payback period is estimated to be 22 months

Reducing Fresh Water Usage in Felt Showers

1) The best method for handling felt shower water is to minimize through use of high pressure, low volume showers.
2) A reduction of up to 94% in shower water volume is possible.

Replacing of Gland Seals and Collection of Cooling Water 1) Two of the major water consuming items of the paper machine are gland seals and cooling

water. 2) The cooling water is best handled by creating a clear water sewer for the mill in which all uncontaminated cooling water is collected and discharged untreated since it contains only thermal energy as a contaminant. 3) Many gland seals can be replaced by mechanical seals 4) reduction of 1 m3 per ton of paper produced

1) Proper maintenance of these insulations could reduce the normalized power consumptions. 2) energy savings up to 10 percent could be achieved by proper maintenance of hot water and steam pipeline insulations. Such renewal requires $0.1 million with a payback period of 14 months

Thank you