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Additives involved in cement industry

Contents

 Introduction

 History
i. All over
ii. In Pakistan
 Present
i. Historical Analysis of Cement Production Capacity &
Dispatches
ii. Pakistan cement Production
 Additives Used in Cement Manufacturing
i. Major Additives
ii. Cement Additives (Function and Definition)
 Types of cement

 Cement manufacturing process flow sheet diagram

 Future plan

 Conclusion

 References

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Additives involved in cement industry

Additives Involved in Cement Industry


 Introduction:

 What is Cement?

Definition:
Defined as a product material obtained by calcination of calcareous (a
material containing lime) and argillaceous (a material which contain silica) materials.

 Uses and Economics.


Before concrete was relatively little used because the manufacture of Portland
cement was an expensive process. Cement is now low in cost and is applied
everywhere in the construction of homes, public buildings, roads ,dams, industrial
plants and many others structures. In 1980 there were 142 plants in the United
States producing Portland cement. It is interesting that the 10 largest plants
produced 48% of the total[1].

 History
Cement dates back to antiquity, and one can only speculate as to its discovery[2] . A
cement was used by the Egyptians in constructing the pyramids. The Greeks and
Romans used volcanic tuff mixed with lime for cement, and a number of these
structures are still standing . In 1824 an Englishman, Joseph Aspdin, patented an
artificial cement made by the calcination of an argillaceous limestone. He called this
‘Portland’ because concrete made from it resembled a famous building stone
obtained from the Isle of Portland near England. This was the start of the Portland
cement industry of today. The hard clinker resulting from burning a mixture of clay
and limestone or similar materials is known by the term Portland cement to
distinguish it from natural or pozzolan and other cements. Concrete and cements
are not synonymous terms. Concrete is artificial stone made from a carefully
controlled mixture of cement , water, and fine and coarse aggregate (usually sand
and coarse rock).

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Additives involved in cement industry

 In Pakistan:
Cement industry is one of the few industries that existed in Pakistan before the
partition of the sub-continent. The major reason for the existence of this industry is
the availability of the raw materials. Pakistan has inexhaustible reserves of limestone
and clay, which can support the industry for another 50-60 years. The annual
production of the cement at the time of the creation of Pakistan was only 300000
tons per year. By 1954 the production increased to 660000 tons per annum against
a demand of 1000000 tons per annum. At this time PIDC took initiative and
established two cement factories Zealpak (240,000 tons) and Maple Leaf (100,000
tons) having a capacity of 340000 tones, thereby increasing the production to
1000000 tons per annum. Since then besides expansion of the existing plants, new
plants have also established. Besides producing OPC, the Pakistani cement industry
also started producing SRC, Slag cement and white cement.
In 1921 the first cement plant was established at WAH. At the time of independence
in 1947 there were four cement factories with an installed capacity of 470,000 tons
per annum. These units were located at Karachi, Rohri, Dandot and WAH. In 1956
PIDC established two plants at Daudkel and Hyderabad and subsequently more
plants were established in the private sector.

 Present


Historical Analysis of Cement Production Capacity & Dispatches
(Operational Units Data)[3]

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Additives involved in cement industry

 Pakistan cement production


Cement Production in Pakistan increased to 3074 Thousands of Tons in February
from 2947 Thousands of Tons in January of 2017. Cement Production in Pakistan
averaged 2228.54 Thousands of Tons from 2003 until 2017, reaching an all-time high
of 3469 Thousands of Tons in November of 2016 and a record low of 864 Thousands
of Tons in May of 2003
At present a 50kg bag of cement costs from around PKR500 (US$4.77) in Pakistan,
whereas the same 50kg bag costs from around PKR292 (US$2.80) in neighboring
India.

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Additives involved in cement industry

Additives Used in Cement Manufacturing


 Major Additives
 Lime stone
Lime stone on calcinations gives CaO which is an essential component of all the
complexes (silicates, aluminates and alumino ferrites) present in cement. Lime stone
is available in two lime forms
i. High Lime
ii. Low Lime
 Clay
The complexes such as silicates, aluminates & alumino ferrites all contain SiO2, &
Al2O3.These are added into O.P.C by clay
 Gypsum
The flash setting in cement is retarded by the addition of Gypsum which forms the
following complex (3CaOAl2O3.3CaSO4.31H2O).

Cement Additives (Function and Definition)


% BWOC it means “percentage by weight of dry cement”. One sack of cement is
94lbs.

 Accelerators
 Function
Accelerators may be added to the mix water to reduce the thickening and setting
times of the slurry, with the purpose of avoiding unnecessary time spent waiting on
cement.
Calcium Chloride is the most common type of accelerator used. Other, less
frequently used accelerators are Sodium Chloride and Potassium Chloride.
Additive Formula Concentration Comments
Calcium Chloride CaCl2 - 2 % BWOC High gels may form
(Accelerator) at higher
concentrations.

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Additives involved in cement industry

Flash setting may


occur above 3 %.
Sodium Chloride NaCl Up to 20 lbs./bbl. Acts as an
(Accelerator) of mix water accelerator and
adversely affects
other additives at
higher
concentrations
than 20 lbs./bbl.
Sea Water Use as mix water Contains NaCl in
(Accelerator) the correct
concentration
range. Main
application is
shallow depth
cementation
offshore.
Potassium
Chloride KCl As required Equivalent to NaCl
and CaCl2 but
more expensive.

Note:
In general accelerators increase the viscosity of the cement slurry and decrease the
effectiveness of most other additives
Calcium Chloride can cause skin burns and sever irritation to eyes, nose and lungs.
Gloves, goggles and respirators shall be used during mixing. Calcium Chloride is
available in 50lb sacks.
 Retarders
 Additive
 Lignin
 Organic Acids
 Function
As the temperature increases, the chemical reaction between cement and water is
accelerated which, in turn, reduces the pump able time. Increased depths and

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formation temperatures may require the use of retarders in order to extend the pump
able time of the cement.
Thixotropic slurries may require retarders at shallow depths and low temperatures.
 Effects on Viscosity
Most retarders affect the viscosity of the cement as follows:
Type of Retarder Effect on Viscosity
Lignin Derivatives (HR 5, HR 6 etc) Reduce
Organic Acids Organic Acids
Cellulose Derivatives (CMC) Cellulose Derivatives (CMC)

The combined use of retarders and accelerators in the same mix should be avoided
 High Density Additives
 Additives
 sintered bauxite
 silicon carbide,
 Function
There are two main methods of increasing the gradient of the cement slurry:
 reducing the water/cement ratio

 addition of a weighting material.

 Reducing the Water/Cement Ratio


This is the preferred method of increasing cement gradient, particularly when
cementing across gas zones. A maximum gradient of approximately 17.0 ppg can be
attained by this method.
 Addition of a Weighting Material
The preferred material is hematite (iron oxide) but barite may also be used. It is
preferable to batch mix the cement and the weighting material rather than to use pre-
blended cement since weighting materials additive in pre-blended cement may settle
out during storage. Furthermore, handling different blends of cement on one rig may
result in operational mistakes.

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Additives involved in cement industry

Note: When drilling with a mud gradient of 14.8 ppg or more, a batch mixing unit and
sufficient weighting material must be on site as a contingency. If very large volumes
need to be mixed, batch mixing is not achievable

 Low Density Additives (Extenders)


 Additive
Physical Extenders
 Perlite
 Gilsonite
 Ground coal
 Ground rubber
Chemical Extenders
 Sodium silicate
 gypsum
 Function
Low gradient slurries are used for cementing weak formations or when there is a
possibility that the casing could collapse or float if a heavier slurry was used.
Compressive Strength
As a result of the decreased cement concentration of extended slurries, the
compressive strength of the hardened cement will be lower than that of neat
slurries.

 Friction Reducers (dispersants or Thinners)


 Liquiment® 1641 F
 Liquiment® 5581 F
 Function
Friction reducers are dispersing agents which can be added to the slurry to reduce
its viscosity and thus the frictional pressure losses in the system while displacing (or

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Additives involved in cement industry

squeezing) the cement. As a result, higher pumping rate are possible and higher
displacement efficiencies may be achieved.

 Fluid Loss Control Additives


 Additive
 Polytrol ® FL 34
 Function
Fluid loss control additives are added to cement slurries for the following reasons:
 To reduce the possibility of dehydration opposite porous zones and
consequently flash setting of the cement.
 Loss of fluid from the slurry will result in increasing slurry viscosity and
gradient and higher circulating pressures.
 Excessive fluid loss will reduce slurry volume and give less cement fill.
 When squeeze cementing it is desired to get an effective squeeze against the
entire formation and not just squeeze cement filtrate into it.
Most fluid loss additives tend to viscosify the slurry and consequently, dispersants
are often added at the same time to control this effect

 Additives for Thixotropic Slurries


 Additive
 CA-GC1
Liquid, special product which eliminates gas invasion into a cement column
during transition period from liquid to solid, 15% to 20% BWOW optimum
dosage, also provides excellent fluid loss control.
 CA-GS1
Viscous Liquid, special product which eliminates gas invasion into a cement
column during transition period from liquid to solid, 15% to 25% BWOW
optimum dosage, also provides excellent fluid loss control
 CA-GS2, CA-LX2, CA-LX2L ,CA-LX3L etc.

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Additives involved in cement industry

 Function
The main application of thixotropic slurries is cementing in lost circulation
environments.
During pumping the slurry behaves as normal, however, a gel structure develops
rapidly when static. Such slurries also find application in cementing across gas zones.
The major disadvantage of thixotropic slurries is their relatively high viscosity which
may adversely affect displacement efficiency
 Defoamers and Antifoamers
Additive Function
BI-AF1(LIQUID) Liquid anti-foam agent; minimizes air
entrainment in a cement slurry during
mixing; effective at all temperatures;
normal concentration is 0.06
gallons/barrel of mix water.
BI-AF 1P Anti-foam agent; minimizes air
entrainment in a cement slurry during
mixing; effective at all temperatures;
normal concentration is 0.2 to 0.3 lb./sk
of cement.
BI-AF2(LIQUID) Liquid defoamer/anti-foam agent;
minimizes air entrainment in a cement
slurry during mixing; effective at all
temperatures; added to mix water or
can be sprayed into blender tub, normal
concentration is 0.06 gallons/barrel of
mix water.

 Gas blocking Additives


 Additive
 styrene-butadiene lattices
 Paragas® which is a modified polyethylenimine[4]

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Additives involved in cement industry

 Function
During the hardening process, the cement slurry passes through a semi-solid phase
in which the liquid has gelled up. As a result, the overburden pressure will be lost
thus permitting gas migration into, and through, the cement matrix.

.Types of Cement[5]
The types of special cement now being produced can be roughly classified in the
following six categories according to the special purpose for which these have been
designed. These are:

1. Rapid hardening cement.


2. Cement resistant to chemical attack of certain soil and aggregates.
3. Low heat of hydration cement.
4. Better protecting cement for steel reinforcement.
5. Better workability and whether resisting cement.
6. Decorative cement and other special cement.
 Rapid Hardening Cement:
Under this category following two cement have the desired properties of fast
development of strength viz. the Portland Rapid Hardening Cement and High
Aluminum Cement. “Their specific characteristics are as follows:
 Rapid Hardening Cement (Type III of A.S.T.M):
This cement has high early strength, its equal to or better than 3 Days’ strength of
OPC.
 High Aluminum Structural Cement:
This cement is used where very rapid setting and very high early strength are
required. This cement has strength at one day nearly equal to 28 days strength of
O.P.C. Its setting is so fast that it must be put in place within a few minutes of its
mixing. It is generally used in plugging leakage in dams etc. or putting in pile
foundations where limited time is available for setting of cement before the seepage
water build up occurs.
. In this category the following cement can be included:
2-A Highly Sulphate Resistant Cement
2-B Moderately Sulphate Resisting Cement

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2-C Portland Blast France Slag Cement.


2-D pozzolana Cement
2-E Low Alkali Cement
2-A Highly Sulphate Resisting Cement H.F.R.C
The most important and the most widely used chemical resistant cement is H.S.R.C
cement High concentration of sulphate salts is present in seawater and in the soil
near seashores. These salts are sometimes present in soil and in the submit water
even thousands of miles away from the sea.
2-B Moderately Sulphate Resisting Cement (M.S.R.C.)
This cement has been developed as a compromise Cement having the good
properties of sulphate resistance to some extent and of good alkalinity like that of
OPC which useful for reinforcement protection and also of early strength
development better than Highly Sulphate Resisting Cement.
2-C Portland Blast Furnace Slag Cement:
This cement has well to moderate resistance to sulphate attack from soil. This
cement has some other very desirable qualities of stability.
2-D Pozzolana Cement:
This cement has well to moderate resistance to sulphate attack from seawater or
soil containing sulphate.
2-E Low Alkali Cement:
This is a variety of ordinary Portland cement in which the total alkali contents of
cement has been controlled to remain below 0.6%. With this reduced percentage of
alkali contents the danger of alakie of cement attacking the active silica contents of
aggregate is eliminated.
 Low Heat of Hydration Cement:
Normal and Rapid Hardening Cement generate lot of heat during the setting and
hardening process so much so that the structure under concreting can crack. This
can occur specially while poring large messes of concrete in confine spaces like those
of Dam and Bridge pier foundations. In order to avoid this problem cement of low
Heat of hydration have been developed some of which are as listed below:
3-A Low Heat of Hydration Cement (type IV of A.S.T.M.)
3-B Portland blast Furnace Slag Cement
3-C Pozzolana Cement
3-D Super Sulphate Cement
3-A Low Heat of Hydration Cement (type IV of A.S.T.M.):

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This is cement specially meant for the concreting of structures where large masses
of concrete have to be poured at one time. Generally it is specified that heat of
hydration on 7 days will not exceed 250Kg. This is achieved by making this cement
with larger percentage of di-calcium silicates in its contents than normally presents
in OPC.
3-B Slag Cement:
This is another variety of low heat cement. Grinding 35% to 65 % of granulated blast
furnace slag with ordinary Portland cement clinker produces it. The higher the slag
contents, the lower are the 3 and 7 days strengths but better is the resistance to
chemical attack.
3-C Pozzolana:
Grinding various proportions of natural pozzolana, tars or volcanic ash with ordinary
Portland clinker makes this cement. It is very good cement in the sense that it has
good workability properties in addition to having low heat and moderate sulphate
resisting properties.
3-D Super Sulphate Cement:
This is another variety of low heat cement. Its standards exist under B.S but not
under A.S.T.M. it is made by grinding about 70-80% B. F. Slag with about 10% gypsum
and 1-2 % Portland clinker or lime. This cement is also middy resistant to sulphate
attack. It is very finely ground cement and its early strength at 3 day is comparable
to OPC although under the BS its 7 days strength is required to be comparable to at
least the 3 days strength of OPC. This cement is also good masonry cement due to
its good workability but it can be used in RCC and other construction work in the
same manner as OPC is used with excellent results.
Cement For Better Protection of Reinforcement against Corrosion:
The basic steps for the prevention of resulting of steel in concrete is to use such
cement aggregate and mixing water as are basically free from chlorides, maximum
contents of chlorides in concrete being limited to 0.02 % by weight. The following
properties in cement are essential for greater protection of steel:
1. Cement to be with minimum percentage of Chlorides says not exceeding 0.01
per cent.
2. Portland Cement preferably having about 6 to 8 per cent Tricalcium
Aluminates.
3. Cement made with slag as additive.

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Additives involved in cement industry

Cement manufacturing process flow sheet


diagram

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 Future
The cement sector over the last six years and the industry itself has seen a growth
in volume every year something that is also reflected in the huge return on
investment cement stockholders have enjoyed. Considering the heavy
investment the Chinese have made in Pakistan with the China Pak Economic
Corridor (CPEC) and the barriers to entry for new entrants it seems the growth
will continue for few more years to come.
Cement industry comprises 24 cement plants with an annual installed capacity of
producing 44.22 million tons of cement. It is also expected that to add more
cement plants in the industry.

 Conclusion
There are different types of additives which are used in the cement
manufacturing like gypsum, which is used to increase the settling time of cement
, lime, which provide essential component for the manufacturing of cement ,
clay and many other additives are used in the cement manufacturing process ,
each additive has its own function which provide a specific quality to the material.
Some additives also has effects on the materials.
There is also different types of cement like ordinary Portland cement , rapid
hardening cement , low heat of hydration cement etc. Each one is used according
to the requirements.

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 References
[1]
Shreve’s Chemical Process industries,5th ed. , pg., 171
[2]
ECT, 3d ed., vol. 5, 1979, pp. 163-192 (excellent summary);
[3]
(http://www.apcma.com/data-history.htm)
[4]
http://www.oilfield-solutions.basf.com/ev/internet/oilfield-solution
/en_GB/applications/cementing/gas-blocking,
[5]
http://www.apcma.com/cement.html

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