i

ii

EXECUTIVE SUMMARY
i. The industrial wastes generated from fertilizer, sugar, paper, metallurgical, mining and petroleum industries were characterised and evaluated for compatibility of their utilization in the manufacture of cement and related building materials. The industrial wastes, in general, are disposed off in wet form into open area, which not only occupy vast tracts of valuable cultivable land but also create environmental pollution and ecological problems. Flyash is a waste generated from coal based thermal power plants. In India ~ 115 million tones of flyash is generated annually. Chemical composition of flyash broadly indicates the presence of 45 60 % SiO2, 1530 % Al2O3, 5 10 % Fe2O3 and small amounts of CaO, MgO, alkalies and unburnt carbon. The Blaines fineness of Indian flyash varies between 300 to 600 m2/kg. R&D investigations have revealed that flyash can be used as raw mix component upto 3 percent for the manufacture of cement clinker and as a blending component in the range of 15 to 35 percent depending upon the quality of flyash for the manufacture of Portland Pozzolana Cement (PPC). Granulated blast furnace slag is a latently hydraulic material and is glassy in nature. Its glass content varies from 90 to 95 percent. Around 10.0 million tonnes blast furnace slag is currently generated in our country from Iron & Steel industry. Depending upon the quality, the slag is used in the range of 25-70 % in the manufacture of Portland Slag Cement (PSC). BOF slag commonly known as steel slag is another waste from iron and steel industry. It is non-hydraulic and crystalline in nature and is rich in Fe2O3 content (20-30 percent). It can be used as a raw mix component upto 10 percent in the manufacture of cement clinker. Steel slag can also replace granulated blast furnace slag upto 10 percent in the manufacture of Portland Slag Cement (PSC). Red mud is a by-product generated from aluminum industry. An estimated quantity of 3.75 million tones of red mud is generated per annum. It is a fine grained material. The chemical composition of red mud broadly indicates the presence of 20-30 % Fe2O3, 15-20 % Al2O3, 12-16 % CaO, 10-13 % TiO2 and 3-5 % alkalies. Around 8 percent of it can be gainfully utilized as a raw mix component in the manufacture of cement clinker. Red mud can also be used for making bricks/ blocks and tiles.

ii.

iii.

iv.

v.

vi.

iii

vii.

Lime sludge is generated from paper, acetylene, sugar, fertilizer, sodium chromate and soda ash industries. Approximately 4.5 million tones of sludges in total are generated annually from these industries. All the lime sludges other than carbide sludge contain lime as calcium carbonate. The carbide sludge from acetylene industry mainly contains lime as calcium hydroxide. These sludges essentially contain lime as major constituent, however, their chemical compositions vary considerably depending upon the composition of limestone used in the parent process. All sludges contain some deleterious constituents/ contaminants, which come from the process through which they are generated, e.g. the phospho-chalk from fertilizer industry contains 5-9 percent SO3, upto 1.5 percent P2O5 and upto 2 percent fluoride as major contaminants. Similarly paper, sugar and chromium sludges contain free alkalies upto 2 percent. The chromium sludge and carbide sludge in addition also contain chromium upto 10 percent and chloride upto 2 percent respectively. The presence of these deleterious constituents/ contaminants restricts their bulk utilization in making cement and related building materials. Detailed investigations were carried out on the utilization of lime sludges from various industries. The study has revealed that sludge from paper industry can be utilized upto 74 percent (dry basis) as a component of raw mix for the manufacture of cement clinker. In addition to it around 30 percent (dry basis) lime sludge can also be utilized for the manufacture of Masonry cement. Due to the presence of deleterious constituents in higher quantities carbide sludge can be used only upto 30 percent where as level of utilization for other sludges could reach to only 10 percent in the manufacture of cement clinker.

viii.

Lead-zinc slag is a waste generated from zinc industry. Approximately 0.5 million tones of lead-zinc slag generated annually. Due to the presence of high iron and zinc oxides only 6 percent of this slag could be utilized as a raw mix component for the manufacture of cement clinker. This slag can also be used upto 45 percent as a blending component for the manufacture of Portland Slag Cement (PSC). Phospho-gypsum is a by-product waste generated from fertilizer industries. Approximately 6 million tones of phospho-gypsum is generated annually. It contains more than 90 percent CaSO4.2H2O along with the presence of deleterious constituents viz. P2O5, fluoride and free phosphoric acid. It can be gainfully utilized as a set retarder in the manufacture of cement after beneficiation. Mine rejects from limestone mining near to cement plant can be utilized as low grade raw material along with other additives for the manufacture of special cements viz. belite cement etc.

ix.

x.

iv

xi.

Jerosite is a waste obtained from zinc industry. Approximately 0.6 million tones of Jerosite is generated annually. It has potential of utilization as a set retarder in the manufacture of cement. Kimberlite is a waste obtained in the process of mining diamonds. Approximately 0.6 million tones of Kimberlite is generated annually. It is siliceous in nature and ~10 percent of it can be gainfully utilized as a component of raw mix for the manufacture of cement clinker. The Hazardous waste is to be dealt as per the provision of Hazardous Waste (Management and Handling) Amendment Rules 2003. The major problems associated with bulk utilization of industrial wastes are: a) their availability in wet condition b) large variation in their quality and c) collection, handling and transportation of these wastes from generating source to utilization end. Promotional efforts for bulk utilization of industrial wastes in cement and building materials such as availability of the wastes in dry state, variation in the quality of the wastes to the minimum level and a package of measures such as tax relief and waste utilization subsidy will go a long way in promoting their utilization.

xii.

xiii. xiv.

xv.

1.0

INTRODUCTION The rapid industrialization has resulted in generation of large quantities of wastes. Most of the wastes do not find any effective use and create environmental and ecological problems apart from occupying large tracts of valuable cultivable land. It has been observed that some of these wastes have high potential and can be gainfully utilized as raw mix / blending component in cement manufacturing. The utilization of the industrial solid wastes in cement manufacture will not only help in solving the environmental pollution problems associated with the disposal of these wastes but also help in conservation of natural resources ( such as limestone) which are fast depleting. The other benefits to cement industry include lower cost of cement production and lower green house gas emission per tonne of cement production. This may also enable cement industries to take benefits of carbon trading. The present study deals with utilization of industrial wastes viz. flyash (from thermal power plants), blast furnace slag and steel slag (from iron & steel industries), phospho gypsum (from fertilizer plants), red mud (from aluminium industries), lime sludges (from sugar, paper, calcium carbide industries), leadzinc slag (from zinc industries) and kimberlite (from mining) for manufacture of cement and related building materials. Scientists, technologists, environmentalists and cement researchers have to play their due role in managing such wastes for the good of the society.

2.0

OBJECTIVES OF THE STUDY The major objectives of this study were: 1. 2. 3. 4. 5. To identify various industrial wastes suitable for utilization in cement manufacture Physico-chemical and mineralogical characterization of industrial wastes. To assess the compatibility of industrial solid waste as raw material/ blending material/ admixture To examine the constraints related to utilization of industrial waste To make recommendations to promote utilization of industrial waste

3.0

IDENTIFICATION OF INDUSTRIAL WASTES FOR UTILIZATION IN CEMENT MANUFACTURE. In view of their availability in large quantities, the following industrial wastes have been identified for the present investigations i) ii) iii) iv) v) Flyash Granulated Blast Furnace Slag Steel Slag Red Mud Lime Sludges a) b) c) d) e) f) vi) vii) viii) ix) x) xi) Paper Sludge Sugar Sludge Carbide Sludge Chromium Sludge Phospho-chalk Soda Ash Sludge

Phospho Gypsum Jerosite Lead-Zinc Slag Phosphorus Furnace Slag Kimberlite Mine Rejects

4.0

QUANTIFICATION OF INDUSTRIAL WASTE GENERATED IN INDIA AND THEIR UTILIZATION Industrial and mineral wastes from mineral processing industries, such as metallurgy, petrochemicals, chemicals, paper and pulp account for nearly 150 million tonnes per annum. The more important wastes from these industries from the view point of building materials are fly ash from thermal power plants, slag from steel industry, press mud from sugar industry, paper sludge from pulp and paper industry, phospho- chalk and phospho-gypsum from fertilizer industry, carbide sludge from the acetylene industry, calcium carbonate sludge from soda ash and chrome sludge from sodium chromate industry, red mud from aluminium industry and metallurgical slags from non-ferrous industry. Data on the availability of these wastes and their areas of utilization are given in Table 1.

TABLE 1 : AVAILABILITY AND AREAS OF APPLICATIONS OF MAJOR INDUSTRIAL WASTES

Sl. No. 1. Generation Waste Flyash
(Million Tonnes per Annum)

Areas of Applications Manufacture of portland pozzolana cement (PPC). ii) Manufacture of pozzolana metallurgical cement, slag-flyash cement and low heat cement. iii) Raw material for the manufacture of OPC. iv) Manufacture of oil well cement. sintered flyash lightweight v) Making aggregates. vi) Cement/ silicate bonded flyash/ clay binding bricks and insulating bricks. vii) Pre-cast fly ash concrete building units. viii) Cellular concrete bricks and blocks, limepozzolana mixes and cement flyash concrete. ix) Structural fill for roads, construction on sites, land reclamation, etc. x) As filler in mines, in bituminous concrete xi) As plasticizer xii) As water reducer in concrete and sulphate resisting concrete. xiii) Amendment and stabilization of soil. i) As a blending material for the manufacture of slag cement, super sulphated cements, pozzolana metallurgical cement. ii) Non-portland cement. iii) Manufacture of expansive cement, oil well, coloured cement and high early-strength cement iv) In refractory and in ceramic as sital. v) As a structural fill (air-cooled slag). vi) As aggregate in concrete. i)

115.0

2.

Blast slags

furnace

10.0

Sl. No. 3.

Generation Waste Steel Slag

(Million Tonnes per Annum)

Areas of Applications As structural filler. As a component of cement raw mix. In the manufacture of PSC. Shore protection. Road making. Railway ballast. Paving bases Patching pot holes. High stress applications i.e. storage yard, heavy vehicles parking loads. x) Where native ground is incapable of withstanding heavier loads. xi) Ready mix concrete. xii) Concrete blocks. xiii) Pipe bedding. i) As a component of cement raw mix. ii) As a binder. iii) Manufacture of construction bricks/ blocks. iv) As a cellular concrete additive. v) Coloured composition for concrete. vi) In the formation of aggregate. vii) Manufacture of floor and wall tiles. i) As a raw material for the manufacture of cement. Manufacture of lime pozzolana bricks/ ii) binders. iii) For recycling in parent industry iv) Manufacture of building lime. v) Manufacture of masonry cement. vi) As a raw material for mini cement plant. i) As a raw material for manufacture of OPC. Raw material for manufacture of Slag ii) cement (PSC). As a fluxing agent in the manufacture of iii) cement. i) As a raw manufacture of OPC. ii) As a blending material for manufacture of PSC. iii) Aggregate substitute in hot mix asphalt. iv) Lightweight masonry aggregate. i) ii) iii) iv) v) vi) vii) viii) ix)

4.0

4.

Red Mud

3.75

5.

Lime Sludges a) Paper sludge b) Carbide sludge c) Phospho-chalk d) Sugar sludge e) Soda ash sludge f) Chrome sludge Lead-zinc slag

4.5

6.

0.5

7.

Phosphorus Furnace Slag

0.5

Sl. No. 8.

Generation Waste Phospho-gypsum

(Million Tonnes per Annum)

Areas of Applications i) ii) iii) iv) v) vi) For the manufacture of gypsum plaster, plaster boards and slotted tiles. As set retarder in the manufacture of (OPC). In the manufacture of expansive or nonshrinking cement, super sulphated and anhydrite cement. As a hydraulic binder As mineralizer Simultaneous manufacture of cement and sulphuric acid. As a raw material for manufacture of OPC. As a set controller in manufacture of OPC. In making flyash bricks / blocks In making glass and ceramic products. As a raw material the manufacture of OPC. As a raw material for manufacture of OPC / special cements. As structural filler

6.0

9.

Jerosite

0.6

10. 11.

Kimberlite Mine Rejects

0.6 750

i) ii) iii) i) ii) i) ii)

5.0

METHODS ADOPTED FOR DISPOSAL OF INDUSTRIAL WASTES AND ASSOCIATED ENVIRONMENTAL PROBLEMS Disposal Methods The disposal methods can be broadly classified as follows: i) ii) iii) iv) Open dumps Covered dumps Unscientific Land fills River/ocean dumping

5.1

The methods, for the disposal of wastes, presently followed for individual waste are provided in Table 2.

TABLE 2: METHODS FOR DISPOSAL OF WASTES

Sl. No. 1. Industrial Waste Flyash Physical form of Waste Powder Industry Source Thermal Power Station Method of Present Disposal Pumped in the form of slurry to nearby low lying areas in the wet system of disposal Flyash discharged from the precipitators is conveyed for disposal to the dumps in the dry method. Dumping in open area

i)

ii)

2.

3.

Blast furnace i) Fine ii) granules/ slag Solid lumps i) Granulated ii) Ungranulated Lime sludges Slurry/Paste

4. 5. 6. 7. 8.

Phospho gypsum Red mud Jerosite Kimberlite Mine Reject

Slurry/paste Paste/cake Powder/ Cake Solid lumps Solid Lumps

Metallurgical industries (steel, zinc and phosphorous) Fertilizer, sugar, paper, acetylene and chrome industry Fertilizer Industry Aluminium Industry Zinc Industry Mining Mining

i) ii) iii)

Stored in large outdoor settling water ponds. Back filling. Dry/ wet stacking. Pumped in the form of slurry to the dumping ponds Dumped in open area Dumped in open area Dumped in open area Dumped in open area

5.2

Environmental Problems The environmental problems associated with the disposal of industrial wastes are summarized below:

5.2.1 Problems associated with open dumps i) ii) iii) iv) v) vi) vii) Direct influence by rain, such as leaching Inaccessibility to the area and the surroundings Lack of aesthetics Scar on the terrain Chemical degradation Breeding of Insects etc. causing health problems When wet dumps get dried up, entrainment of dust in the air.

5.2.2 Problems associated with Covered Dumps Buried wastes are subject to: i) Influence by rain through seepage 6

ii) iii)

Pollution of nearby water sources Long term alteration in solid stability, strength etc in the region.

5.2.3 Problems associated with unscientific Land Fills This is a particular aspect of covered dumps in which wastes are used to fill lands which are not used for building purposes because of: i) Poor soil conditions ii) Excess water in soil Land filling in such cases leads to: a) Soil compaction b) Lowering of moisture percent c) Long term decomposition d) Leaching by water and the pollution of nearby water sources. 5.2.4 Problems associated with River/Ocean Dumping This has adverse effect on: i) Marine life ii) Down stream users of river water iii) Change in nature of silt/deposition on river beds leading to soil erosion. 6.0 6.1 PHYSICO CHEMICAL AND MINERALOGICAL CHARACTERISATION OF INDUSTRIAL WASTES Flyash Thermal power stations using pulverised coal as fuel generate large quantities of ash as by-product. There are about 95 thermal power plants in India, which generate about 115 million tones of ash per year posing serious disposal and ecological problems in addition to occupying large tracts of scarce cultivable land. This ash can is classified mainly into two categories; bottom ash and flyash. The latter is potentially more valuable for the construction industry. Despite most of researches establishing its numerous uses, flyash utilization has still remained moderate. 6.1.1 Physical Characteristics Flyash is generally obtained in small predominantly spherical particles, which differ in size and shape significantly due to differences in degree of pulverisation of coal, associated impurities in the coal, boiler type, power load and efficiency of collection systems. In general, the Blaines fineness of Indian flyashes varies between 300-600 m2/kg except in few stray cases where it is coarser. One of the

important parameters, which govern the use of flyash for various applications, is lime reactivity. It has been found that lime reactivity of flyash, as a general rule increases with its fineness. Lime reactivity of Indian flyash samples generally varies between 3.5 to 6.5 N/mm2. Physical characteristics of some selected Indian flyash are presented in Table 3. TABLE 3 : FINENESS AND LIME REACTIVITY VALUES OF SOME TYPICAL INDIAN FLYASH SAMPLES Sl. No. 1. 2. 3. 4. 5. Sample A B C D E Fineness (m2/kg) 301.1 316.9 432.0 344.5 263.0 Lime Reactivity (N/mm2) 4.1 4.5 4.8 4.7 3.5

6.1.2 Chemical Characteristics The chemical composition of flyash depends largely on the geological and geographic factors related to coal deposit, the combustion conditions and the efficiency of air pollution control devices. Mostly flyash samples consist of SiO2 (45-60 percent), Al2O3 (15-30 percent), Fe2O3 (5-10 percent) besides unburnt carbon and small amounts of calcium, magnesium, alkalies and sulphates, except in flyash from lignite, which contain significant amount of CaO. Chemical analyses of some typical Indian flyash samples are given in Table 4. It is evident that the Indian flyash generally conforms to Indian Standard specification 38121981 for chemical requirements of flyash. TABLE 4 : CHEMICAL ANALYSIS OF SOME SELECTED TYPICAL INDIAN FLYASH SAMPLES Sl. No. 1. 2. 3. 4. 5. 6. 7. 8. 9. Constituents Determined LOI SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O Flyash Sample B 1.10 59.70 25.69 7.31 2.00 2.89 1.02 0.15 0.25

A 4.30 55.59 26.64 9.50 2.30 0.60 0.44 0.23 0.40

C 8.80 37.05 24.06 21.84 1.71 5.25 0.87 0.17 0.28

6.1.3 Mineralogical Characteristics The mineral contents of flyash samples as determined by XRD are characterized by -quartz, mullite, hematite, magnetite and glassy phase (Fig 1). The glass content of Indian flyash samples is indeed low (20-30 percent) compared to flyash samples from USA, Japan and France where the glass content is as high as 80 percent or even more. Consequently, Indian flyash samples are in general intrinsically less pozzolanic. Table 5 shows the mineralogical composition of some of the typical Indian flyash samples. Scanning Electron Micrographs of a typical Indian flyash sample (Plate 1) shows that particles are spherical with smooth surfaces varying from 1-60 microns in size.

LEGEND Q - -quartz H - Hematite M - Mullite

FIG. 1 : X-RAY DIFFRACTOGRAM OF A TYPICAL FLYASH SAMPLE TABLE 5 : MINERALOGICAL CHARACTERISTICS OF SOME INDIAN FLYASH SAMPLES Sl. No. 1 2 3 4 5 Sample A B C D E Major - Quartz - Quartz - Quartz - Quartz - Quartz Minerals Present Predominant Small Amount Mullite Hematite Mullite Mullite Mullite Mullite Hematite Rutile Hematite Glass Content (%) 24 30 25 24 25

PLATE 1 : 6.2

SCANNING ELECTRON MICROGRAPH OF A TYPICAL FLYASH SAMPLE

Granulated Blast Furnace Slag Manufacture of steel consist of three steps (i) conversion of coal to coke (ii) combining coke, iron ore and limestone in a blast furnaces to produce pig iron and (iii) the conversion of pig iron into steel in an open hearth, basic oxygen or electric furnace. Subsequently the steel is subjected to a high vacuum for degassing followed by casting. Silica is the major impurity of iron ore and coke. Limestone works as flux and removes this silica in the furnace. At the high temperature, the lime combines with the silica to form molten slag. The slag floats on the iron and skimmed off periodically. Granulation of the slag is carried out by sprinkling water jets on molten slag and then flung the cooled slag into air by a rotary drum. It transforms the cooled slag into grains upto a size of 4 mm. Generation of blast furnace slag varies considerably depending upon the fluxes and varies from 430-650 kg/tonne of hot metal. The generation of blast furnace slag per tonne of steel has been gradually decreasing and is estimated presently as an average of 450 kg/tonne of hot metal. The slag from the steel melting shops i.e. BOF, LD and Open Hearth furnace constitutes nearly 200 kg/tonne of steel.

6.2.1 Physical Characteristics The size of granules of granulated blast furnace slag varies upto maximum size of 4 mm. In order to determine the energy required for grinding of granulated 10

blast furnace slag while making blended cement (Portland Slag Cement), the bond grindability Index plays an important role. This index varies from 15 to 18 Kwh/t for Indian slags, i.e. higher the index value, harder to grind. Granulated slag has been found to be hydraulic in contrast to un-granulated, which is nonhydraulic in nature. 6.2.2 Chemical Characteristics The composition of slag varies over a wide range depending on the nature of the ore, the composition of the limestone flux and the coke. Indian slags are also characterised by high Al2O3 (17 to 33 percent), MgO (0 to 17 percent, SiO2 (27 to 39 percent) and low CaO (30 to 40 percent). Generally granulated blast furnace slags have low CaO / SiO2 ratios (Table 6). The essential components of slag are similar to those present in OPC but they differ in their proportion. The chemical composition of Indian slags are different from those obtained in Russia, Germany and France where the blast furnaces are operated at higher temperature, which facilitates better granulation and glass formation. 6.2.3 Mineralogical Characteristics When a powdered granulated slag is examined on a microscope slide by transmitted light the glass is seen to consist of clear isotropic transparent grains. In Indian slags glass content varies from 90 to 95 per cent. X-ray diffractogram of the slag shows amorphous material (Fig.2)

LEGEND 1. Ca2Al2SiO7 2. Ca2SiO4 3. KAlSiO4

FIG. 2 : X-RAY DIFFRACTOGRAM OF A TYPICAL GRANULATED BLAST FURNACE SLAG SAMPLE 6.3 Steel Slag Hot metal, obtained from blast furnace, in molten state containing ~90 percent iron is charged into LD converter along with fluxes and oxygen is blown to purify hot metal. Impurities viz. C, P, Si, Mn and a part of Fe are oxidized and

11

separated from the refined liquid in the form of slag. For every tonne of steel production about 200 kg. of LD slag, is generated. 6.3.1 Physical Characteristics Steel Slag is found in the form of big pebbles. It is crystalline in microstructure and non-hydraulic in nature. 6.3.2 Chemical Characteristics Chemical analysis of steel slag indicates the presence of high percentage of CaO and Fe2O3, 35 to 50 and 20 to 30 percent respectively. Apart from these, the steel slag also contains ~15 percent SiO2 and considerable amount of MgO (~10 percent). Chemical analysis of a typical steel slag sample is provided in Table 6. TABLE 6 : CHEMICAL COMPOSITION OF TYPICAL GRANULATED BLAST FURNACE SLAG AND STEEL SLAG SAMPLES Sl. No. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Constituents Determined (%) Gain on Ignition SiO2 Fe2O3 Al2O3 CaO MgO Na2O K2O SO3 TiO2 Granulated BF Slag 0.65 33.41 0.89 20.05 34.24 8.86 0.16 0.82 Nil Nil Steel Slag 2.32 14.21 24.40 4.17 44.32 10.32 0.08 0.07 Nil 1.00

6.3.3 Mineralogical characteristics The x-ray diffraction analysis of steel slag indicates the presence of calcium and iron-based minerals thereby conforming the presence of high CaO and Fe2O3 in the steel slag sample (Fig.3). The glass content of steel slag is very low and varies in the range of 20 to 40 percent only. 12

LEGEND 1. Ca2SiO4 2. Ca2(AlFe)2O5 3. Ca2SiO4-Syn 4. Ca2MgFe2O6

FIG. 3 : X-RAY DIFFRACTOGRAM OF A TYPICAL STEEL SLAG SAMPLE 6.4 Red Mud Red mud is generated from aluminium metallurgical industry as a by-product waste. Bauxite is used as ore in the metallurgical extraction process. Alumina Oxide (Al2O3), alumina is the compound extracted from the ore bauxite. Bauxite is a hydrated aluminium oxide combined with impurities including iron oxide, various silicates and quartz. The Bayers process or the combination process dissolves the impure alumina of the ore in caustic soda (NaOH) to form soluble sodium aluminate. The solution is cooled, diluted and hydrolyzed to precipitate aluminium hydroxide, which is filtered and calcined to alumina. The reactions involved are: Al2O3 . H2O + (mono hydrate) Al2O3 . 3H2O + (trihydrate) 2 NaOH 2 NaOH 2 Na AlO2 + 2H2O

2 Na AlO2 + 4H2O

The Bayers process generates a slurry containing NaAlO2 as aqueous solution and undissolved solids known as red mud. 6.4.1 Physical Characteristics Red mud is found to be a brownish red coloured fine-grained material, as evident from its sieve analysis (Table 7). It has 97.1 percent fraction passing through 45 sieve and the rest 2.9 percent is distributed between 212 and + 45 sieves. 6.4.2 Chemical Characteristics

13

Chemical composition of the red mud is largely dependent on the chemical characteristics of the parental bauxite ore. The mud, red in colour because of its iron content, contains undissolved alumina, alkali insoluble oxides like Fe2O3, TiO2 and minor amount of vanadium. The chemical composition of red mud broadly indicates the presence of 20-30 % Fe2O3, 15-20 % Al2O3, 12-16 % CaO, 10-13 % TiO2 and 3-5 % alkalies. The chemical composition of a typical red mud sample obtained from an Indian aluminium plant is presented in Table 8. TABLE 7: SIEVE ANALYSIS OF A TYPICAL RED MUD SAMPLE Sl. No. 1. 2. 3. 4. 5. 6. 7. 8. Sieve Size - 212 - 212 + 106 - 106 + 90 - 90 + 75 - 75 + 63 - 63 + 63 - 53 + 45 - 45 Percentage Nil 0.2 0.3 0.3 0.50 0.90 0.45 97.1

TABLE 8 : CHEMICAL ANALYSIS OF A TYPICAL RED MUD SAMPLE Sl. No. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Constituents Determined LOI SiO2 Fe2O3 Al2O3 CaO MgO Na2O K2O TiO2 Mn2O3 Percent 13.45 9.60 26.65 18.60 15.44 0.80 3.09 0.09 12.03 Traces

6.4.3 Mineralogical characteristics The mineralogical characteristics of red mud depend upon the origin of the bauxite ore. Various proportions of hematite, goethite, hydroxylsodalith, rutile, diaspore, boehmite and gibbsite have been identified in red mud (Fig.4). 14

LEGEND H - Hematite R - Rutile G - Gibbsite Go - Goethite B - Boehmite T - Tremolite

FIG. 4 : X-RAY DIFFRACTOGRAM OF A TYPICAL RED MUD SAMPLE 6.5 Lime Sludges Limestone is the most widely used mineral in the chemical industry and generally one of the by-products/ wastes from these chemical industries is a lime bearing sludge. The main sources of the lime sludge are sugar, paper, acetylene, fertilizer, sodium chromate and soda ash industries. It is estimated that approximately 4.5 million tonnes of these sludges are generated in the organised sectors of these industries. The sludges are disposed off wet in the form of slurry/ filter cake into lagoons/ settling tanks and are considered potential health and environmental hazards. 6.5.1 Process of Generation 6.5.1.1 Paper sludge The principal process for producing chemical pulps in paper industries is the Kraft process; where the mixtures of sodium sulfide and sodium hydroxide are used as pulping chemicals. In the process, calcined lime is used for regeneration of caustic soda by conversion of soda ash (green liquor) leaving behind calcium carbonate sludge as a waste. Na2CO3 + CaO +
Green Liquor

H2O

NaOH
Castic Soda

+ CaCO3
Sludge

Calcium carbonate thus produced is washed with water and filtered to recover alkalies. 6.5.1.2 Sugar Sludge

15

Sugar sludge commonly known as press mud, a by-product from the sugar industries is obtained during the carbonation process as calcium carbonate. In the sulphate process, the sludge mainly contains calcium sulphate and is generally used as a fertilizer. The carbonate sludge is disposed off wet with solid content ~10 percent. 6.5.1.3 Carbide Sludge

Calcium carbide is manufactured by the interaction of limestone and carbon as a starting material for the manufacture of acetylene gas in acetylene industries. Most carbide acetylene processes are wet processes from which hydrated lime, Ca(OH)2, commonly known as a sludge is obtained as a byproduct.
Calcium Carbide

CaC2

2H2O

Acetylene Sludge

Ca(OH)2

C2H2

6.5.1.4

Chromium Sludge

Chrome ore (chromite FeO.Cr2O3 i.e. 68% Cr2O3, 32% FeO) is calcined with limestone and soda ash and digested with water to extract soluble chromium salts and the resultant residue is rejected as the carbonated sludge. The sludge generally contains soluble chromium salts and is considered deleterious for the environment and therefore it is generally converted to insoluble salts before disposal. 6.5.1.5 Phospho-Chalk

Calcium carbonate sludge, generally known as phospho-chalk is a by-product waste obtained in the process of manufacture of ammonium sulphate, through the reaction of carb liquor and phospho-gypsum (a byproduct from the phoshoric acid manufacture) in the fertilizer industries. (NH4)2CO3 6.5.1.6 + CaSO4.2H2O CaCO3 + 2H2O + (NH4)2SO4
Phospho-chalk

Soda Ash Sludge

Lime bearing sludges is also generated from soda ash manufacturing industry. The soda ash sludge essentially contains calcium carbonate with associated impurities of sulphide and chloride depending upon the process of manufacture. 6.5.2 Characterization of Lime Sludges 6.5.2.1 Physical Characteristics

16

Lime Sludges as discharged from the various industries are in the form of sediment with a moisture content of 20-90% (Table 9). These sludges on drying change into fine dusty powders. TABLE 9 : PHYSICAL PROPERTIES OF LIME SLUDGES Sl. No. 1 2 3 4 5 6 Sludge Source Paper Sludge Phospho Chalk Carbide Sludge Sugar Sludge Chromium Sludge Soda Ash Sludge Physical State Cake Cake / Slurry Slurry Cake Cake Slurry Moisture Content (%) 40-50 20-65 60-80 40-50 35-45 80-90

The particle size distribution of some of the sludges is given in Table 10. The slurries from the various industries have different dewatering and sedimentation characteristics depending upon the fineness and particles size distribution and to some extent on their chemical contaminants.
TABLE 10 : PARTICLE SIZE DISTRIBUTION OF INDIAN LIME SLUDGES Particle Size (Microns) Paper Sludge Fertilizer Sludge Carbide Sludge Sugar Sludge % Chrome Sludge Soda Ash Sludge

+ 90 90 + 45 45 + 30 30 + 10 10 + 5 5 6.5.2.2

2 8 10 72 8 -

2 60 20 12 4 2

8 62 20 6 4

6 8 40 24 16 6

4 12 12 60 8 4

6 16 42 26 6 4

Chemical Characteristics

Chemical composition of the lime sludges from various industries has been presented in Table 11. From the Table it is clear that 1. All the sludges have essentially lime as a major constituent and its content varies from 35-70% on dry basis. All the sludges other than from carbide industry contain lime as calcium carbonate. The sludge from carbide industry essentially contains calcium hydroxide. Lime bearing sludges also contain MgO, Al2O3, Fe2O3 and SiO2 as associated constituents and their contents vary considerably depending upon the occurrence of these constituents in the limestone used in the parent process.

2.

17

3.

These sludges also contain specific contaminants associated with the process through which they are generated. Most of the problems regarding the utilization of these sludges are attributed to the presence of these contaminants. Sludge from the carbide and the soda ash industry contaminant chloride, most of it is in the soluble form as a major content. Phospho-chalk contains 5-9% of SO3, upto 1.5% of P2O5 and upto 2% of fluoride as major contaminants. Paper, Sugar and chromium sludges contain free alkalies up to 2%. The chromium sludge in addition, contains chromium upto 10 percent. TABLE 11 : CHEMICAL COMPOSITION OF INDIAN LIME SLUDEGS
Phosphochalk Soda Ash

Constituents Determined

Paper

Carbide %

Sugar

Chromium

LOI CaO Al2O3 Fe2O3 SiO2 SO3 P2O5 FClMgO Na2O/ K2O Cr2O3 6.5.2.3

35-40 45-50 2-5 1-1.5 4-6 1.5-2.0 0.5-1.5 -

34-38 45-50 0.3-0.5 0.3-0.5 3-5 5-9 1-1.5 1-2 -

25-30 60-70 1-3 0.1-0.25 4-6 0.2-0.3 Trace 0.2 0.2-0.5 0.02-0.2 -

40-50 42-50 2-2.5 2-2.5 1.5-4.5 1-2 4-10 1-2 -

20-35 35-40 3-5 4-6 3-6 1-1.8 8-10

34-38 44-48 1.5-3.0 1-2 4-7 6-10 1-2 -

Mineralogical Characteristics

The mineral composition of the sludges has been determined and is reported in Table 12. It is evident from the Table that: 1. 2. 3. 4. All the sludges other than carbide sludge contain calcium carbonate as calcite. However, carbide sludge contains lime as calcium hydroxide. The sludges also contain silicates of magnesium and R2O3 formed during the calcination of Limestone. Almost all the sludges contain quartz as minor mineral. Depending upon the sources of the sludge they may also contain chromite, magnesite, ferrite and soluble salts like chloride and alkalies.
TABLE 12 : MINERALOGICAL COMPOSITION OF INDIAN LIME SLUDEGS Sl. No. 1. 2. Sludge Paper Sludge Phospho-chalk Mineralogical Composition Major Minor Phase Phase Calcite -quartz, Silicate Calcite -quartz, Silicate Deleterious Constituents Present Phosphates, Fluorides, Ammonia Alkalies, Chloride

18

3. 4. 5. 6.

Carbide Sludge Sugar Sludge Chromium Sludge Soda Ash Sludge

Calcium hydroxide Calcite Calcite Calcite

-quartz, Silicate -quartz, Silicate Chromium, Ferrite -quartz, Silicate

Alkalies, Chloride Sulphite, Organic Matter Chromium, Alkalies Chloride

6.6

Phospho Gypsum In the process of manufacture of phosphoric acid from rock phosphate, phospho gypsum is obtained as a by-product. It is obtained in one of the three forms, anhydrite, hemi-hydrate or gypsum depending upon process used for the manufacture of phosphoric acid. The process of generation of phospho gypsum can be represented by the following equation: 75-80C Ca3(PO4)2.CaF2 + 10H2SO4+ 20H2O 6H3PO4+ 10CaSO4.2H2O + 2HF
Phosphoric acid Phospho gypsum

Phospho gypsum can be gainfully utilized in cement and building materials industries. It needs beneficiation before use because of the presence of deleterious constituents like P2O5 and fluoride. 6.6.1 Physical Characteristics Phospho gypsum is generally found in wet powder form with moisture content ranging from 10 to 25 percent. Its pH varies from 2.7 to 6.4. 6.6.2 Chemical Characteristics Phospho gypsum in dihydrate form, generally contain more than 90% CaSO4.2H2O and contain impurities like P2O5, residual fluoride and free acid. P2O5 content varies from 0.5 to 1.0%, fluoride from 0.61 to 1.15%, the residual acid contents corresponds to pH 2.7 to 6.4. The small amount of soluble impurities in phospho gypsum (traces of free acids, acidic phosphates and silico flouride; 0.1 to 1.0%) affect the quality of gypsum much more strongly than the insoluble impurities in natural gypsum (clay, carbonates, silica, iron oxides), which may be as high as 10%. The compositional comparison of phospho gypsum with that of natural gypsum is presented in Table 13. TABLE 13: AVERAGE COMPOSITION OF TYPICAL PHOSPHO- GYPSUM AND NATURAL GYPSUM
S. No. Constituents Phospho gypsum Natural Gypsum

19

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12.

CaO SO3 Crystal Water Total P2O5 Water Soluble P2O5 Total FWater Sulphate FNa2O Al2O3 Fe2O3 Organic impurities Hg

31.06 44.3 20.1 1.0 0.2 1.0 0.14 0.23 0.22 0.08 0.15 0.1

30.6 43.5 20.1 0.2 0.2 -

The nature and purity of phospho gypsum obtained from various plants varies due to the difference in the nature of rock phosphate and operational parameters. Indian plants use rock phosphate containing fluoride impurities and operate on dihydrate process, which yield phospho gypsum containing both soluble and lattice bound impurities. 6.6.3 Mineralogical Characteristics X-ray diffractogram of a typical phospho-gypsum presented in Fig. 5 revealed the presence of gypsum (CaSO4.2H2O) as a major mineral. The impurities present as minor minerals are Calcium hydrogen phosphate and hydrogen fluoride along with quartz and calcite.

LEGEND 1. Gypsum 2. Calcite 3. -quartz

FIG. 5 : X-RAY DIFFRACTOGRAM OF A TYPICAL PHOSPHO GYPSUM SAMPLE

6.7

Jerosite It is a brown coloured waste generated as a by-product from zinc metallurgical industries. During the roasting of zinc sulphide to zinc oxide, iron present in the ore forms zinc ferrite (ZnO.Fe2O3), which is insoluble under normal conditions. In order to get leaching to break down this trapped zinc, the complex in broken

20

down by sulphuric acid. The liberated iron sulphate reacts with added ammomium sulphate forming Jerosite. 3 ZnO.Fe2O3 + 12 H2SO4 3 Fe2 (SO4)3 + (NH4)2 SO4 6.7.1 Physical Characteristics It is a brown coloured fine powder with a gravity of 2.98 gm/cm2. The pH of the Jerosite is in the range of 8.7 to 9.7 (basic in nature) after lime neutralization. The sieve analysis of the Jerosite indicates that maximum number of particles lie in the range of 10 to 18 size. 6.7.2 Chemical Characteristics The results of Chemical analysis of a typical Jerosite indicate that it contains SO3, Fe2O3 and CaO as major constituents (29.75, 25.56 and 11.34 percent respectively) with other constituents in minor amount. It also contains 4.73 percent ZnO (Table 14). TABLE 14 : CHEMICAL COMPOSITION OF A TYPICAL JEROSITE SAMPLE Sl. No. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. Constituents determined Loss on Ignition (LOI) SiO2 Fe2O3 Al2O3 CaO MgO SO3 Na2O K2O PbO ZnO Percent 16.65 5.59 25.56 2.94 11.34 Traces 29.75 0.32 0.21 3.20 4.73 3 Fe2 (SO4) 3 + 3 ZnSO4 + 12 H2O 2 NH4 [Fe3 (SO4)2.(OH)6] + 6H2SO4
Jerosite

6.7.3 Mineralogical Characteristics X-ray diffraction analysis of Jerosite revealed the presence of ammonium jerosite mineral as major mineral NH4Fe3(SO4)2(OH)6 and gypsum in considerable amount (Fig. 6).

21

LEGEND 1. Ammonio-Jerosite 2. Gypsum

FIG. 6 : X-RAY DIFFRACTOGRAM OF A TYPICAL JEROSITE SAMPLE

6.8

Lead-Zinc Slag Lead-zinc slag is a waste by-product generated from zinc metallurgical industries. During the process of the extraction of zinc metal, the lead-zinc slag is generated as a solid waste produced during pyro-metallurgical treatment of the sulphide ore. The process includes three operations of roasting, smelting and converting. About 200 tonnes of the slag is generated per day of which about 50 tonnes is being reutilized in the process; remaining 150 tonnes per day (about 45000 tonnes / annum) slag remains unutilized.

6.8.1 Physical Characteristics The granulated lead-zinc slag has been found to be in the form of dark brown/black coloured hard nodules. The bond grindability index of the lead-zinc slag has been found to be 16.90 Kwh/T, which is of the same order as obtained for granulated blast furnace slag (15 to 18 Kwh/T) from steel industry. 6.8.2 Chemical Characteristics Chemical analysis of a typical sample of lead-zinc slag indicated the presence of 36.91, 20.85, 15.20 and 8.72 percent Fe2O3, SiO2, CaO and Al2O3 respectively. Apart from the four major constituents mentioned above, the sample of lead-zinc slag also indicated the presence of 12.36, 2.46, 1.33, 1.18 and 0.84 percent ZnO, MgO, PbO, total alkalies expressed as Na2O and sulphide-sulphur respectively. Presence of unusual high insoluble residue (IR), 6.75 percent has also been indicated in the lead-zinc slag. The detailed chemical analysis of the slag is provided in Table 15. TABLE 15 : CHEMICAL ANALYSIS OF A TYPICAL LEAD-ZINC SLAG SAMPLE

22

Sl. No. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13.

Constituents determined Gain on Ignition SiO2 Fe2O3 Al2O3 CaO MgO Na2O K2O Mn2O3 Sulphide-Sulphur Insoluble Residue PbO ZnO

Percent 7.25 20.85 36.91 8.72 15.20 2.46 0.71 0.72 0.60 0.84 6.75 1.33 12.36

6.8.3 Mineralogical Characteristics Lead-zinc slag is reported to be poor in glass content. The slag contains only ~45 percent glass. Presence of FeO and FeAl2O4 has also been indicated as minor minerals. The diffractogram is presented in Fig. 7.

LEGEND 1.

2.

Wuestite Hercynite

FIG. 7 : X-RAY DIFFRACTOGRAM OF A TYPICAL LEAD-ZINC SAMPLE

6.9

Phosphorus Furnace Slag Phosphorus Furnace Slag is by-product obtained in the extraction of phosphorus from rock-phosphate. Rock phosphate admixtured with coke as a reducing agent and silica as a flux is melted in an electric arc furnace. Fluorapatite, the major mineral in rock phosphate is reduced to elemental phosphorous and calcium silicate (slag) contaminated with calcium fluoride and other impurities are obtained as a by-product. The process reactions can be presented as below:

23

When fluorapatite is involved in the reaction 4Ca5F(PO4)3+ 18SiO2 + 30C 18CaO.SiO2 (Slag) + 2CaF2 + 30CO + 3P4
Phosphorus Furnace Slag

and when calcium phosphate is used in the reaction then reaction is as follow : Ca3(PO4)2+ 3SiO2 + 5C 6.9.1 Physical Characteristics Bonds Grindability Index of Granulated Phosphorus furnace slag was found to be 14.0 Kwh/short tonne, which is lower than Bonds Grindability Index for Indian blast furnace slags (15-18 Kwh/short tonne). A typical phosphorus furnace slag contains about 2 percent residue on 8 mm sieve and contains high residue on 500 sieve (35.03 percent). Results also indicated that 73.23 percent fraction lies in between 1 mm and 250 sieve. 6.9.2 Chemical Characteristics Chemical analysis of a typical Granulated Phosphorus furnace slag indicated that CaO and SiO2 are on higher side and Al2O3 content is on lower side as compared to granulated blast furnace slag obtained from steel industry. In addition to the above slag also contains 1.13 percent P2O5. Detailed chemical composition is provided in Table 16. TABLE 16 : CHEMICAL ANALYSIS OF A TYPICAL GRANULATED PHOSPHORUS FURNACE SLAG Sl. No. 1 2 3 4 5 6 7 8 9 Constituents Determined Gain on Ignition SiO2 Fe2O3 Al2O3 CaO MgO Mn2O3 P2o5 Sulphide-Sulphur Percent 0.49 42.37 0.11 3.60 48.00 1.51 0.13 1.13 0.09 3CaSiO3 (Slag) + 2P + 5CO
Phosphorus Furnace Slag

6.9.3 Mineralogical Characteristics X-ray Diffraction analysis of granulated phosphorus furnace slag indicates its amorphous nature. Its glass content was estimated by optical microscopy and found to be 92 percent. 6.10 Kimberlite 24

Kimberlite is a mine waste obtained in the process of mining diamonds from diamond mines. National Mineral Development Corporation at Panna district in Madhya Pradesh is engaged in the above process for the last couple of years and is generating ~2000 tonnes per day kimberlite tailing as a waste. An estimated quantity of ~2.5 million tones of kimberlite is lying unutilized. Kimberlite with two grain sizes is generated during the extraction of diamond crystals from the gangue kimberlite. 6.10.1 Physical Characteristics Kimberlite is dark grey/ black coloured granules of ~90 microns. The bond grindability index of kimberlite varies between 13-15 kwh/ tonne. 6.10.2 Chemical Characteristics The kimberlite samples (fine and coarse) were subjected to chemical analysis and the results are presented in Table 17. Both the kimberlite contain high MgO and SiO2 viz 28.47 & 35.43 in fine grained and 23.99 & 39.17 percent coarse grained sample respectively.
TABLE 17: CHEMICAL COMPOSITION OF TYPICAL KIMBERLITE SAMPLES

S. No. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10.

Constituents Determined Loss on Ignition SiO2 Fe2O3 Al2O3 CaO MgO SO3 Na2O K2O Cl-

Kimberlite (%) Fine Grained 10.16 35.43 11.81 3.41 8.30 28.47 0.26 0.26 0.54 0.015 Coarse Grained 9.48 39.17 10.26 3.68 6.71 23.99 0.28 0.24 0.66 0.021

6.10.3 Mineralogical Characteristics x-ray diffraction analysis of kimberlite samples indicated the presence of Lizardite as major mineral with considerable amount of Smectite/ kaolinite and Muscovite minerals (Fig. 8).

25

LEGEND 1. Anatase 5. Muscovite 2. Lizardite 6. Hematite 3. Hematite 4. Smectite-kaolimite

FIG. 8 : X-RAY DIFFRACTOGRAM OF KIMBERLITE SAMPLE

6.11

Mine Rejects Mining of limestone for cement manufacture, in general, requires removal of upper layer, which is mostly siliceous rocks and or low grade limestone and is not considered suitable for cement manufacture. In addition, while grading limestone for kiln feed preparation, considerable amount of limestone sample is rejected on account of low lime, high MgO, higher minor constituents or granulometric incompatibilities.

6.11.1 Physical Characteristics Physical characteristics are quit similar to that of limestone. Due to the presence of high silica and MgO contents, mine rejects are harder to grind compared to limestone. 6.11.2 Chemical Characteristics The results of chemical analysis of mine reject samples collected from different locations have wide variation. Based on constituent oxide composition i.e. CaO and SiO2, the mine reject samples can be characterised in terms of CaO/SiO2 ratio, which varies from 0.62 to 3.67. The detailed analyses are provided in Table 18. TABLE 18 : CHEMICAL COMPOSITION OF SOME TYPICAL MINE REJECT SAMPLES S. No. Constituents Determined
I Mine Reject Sample (%) II III

26

1. 2. 3. 4. 5. 6. 7. 8. 9.

Loss on Ignition SiO2 Fe2O3 Al2O3 CaO MgO Na2O K2O CaO/SiO2

22.63 38.91 4.49 6.16 24.40 2.25 0.16 0.63 0.62

30.25 19.26 6.33 5.54 35.43 1.43 0.36 1.04 1.83

36.35 11.58 1.84 3.28 42.53 3.05 0.32 0.82 3.67

6.11.3 Mineralogical Characteristics The mineralogical analyses by x-ray diffraction of mine reject samples (Fig. 9) reveals the presence of calcareous and argillaceous phases i.e. calcite and quartz respectively and are seen invariably in all the samples. In addition to calcite and -quartz, presence of dolomite, different clay minerals such as kaolinite, lizardite, muscovite, etc are also indicated in mine reject samples.
LEGEND 1. Calcite 2. Dolomite 3. -quartz 4. Anorthite 5. Muscovite, MAG 6. Kaolinite 7. Boehmit

FIG. 9 : X-RAY DIFFRACTOGRAM OF A TYPICAL MINE REJECT SAMPLE

7.0

COMPATIABILITY OF INDUSTRIAL SOLID WASTES AS RAW MATERIAL/ BLENDING MATERIAL / ADMIXTURE IN CEMENT MANUFACTURE The present day cement manufacturing practice throughout the world has been persistently gearing up for large-scale use of industrial and other forms of waste as substitute raw materials. The advantages gained are manifold and have multiplied effect on both the performance of the company as well as in image 27

building of the company through fulfillment of an important social objective of environmental protection through recycling of wastes. Besides reduction in production cost, recycling of wastes provides the financial benefit from lower cost of the inputs and also the credit and acclaim for its role in environmental protection. The raw-meal feed for cement making basically contains four types of compounds: carbonates, aluminosilicates, iron and aluminium compounds (oxides) and minor constituents. Out of these, the first three are very important in the formation of cement clinker, while the fourth effects, the manufacturing process (mainly burning, stabilization of the kiln and preheater performance) depending upon the type and quantity of the minor constituents present. The three main components should satisfy among themselves the compositional compatibility, thermal combinability and physical amenability to production processes (crushing, grinding and homogenization, burning and clinker formation). The calcareous component of the cement raw meal is usually any rock containing CaCO3. Limestone is the most commonly available calcium carbonate rock. The alumino-silicate compounds admixture are clays, shale, bauxite, laterite, marl, quartzite etc. and fine coal has been used as a fuel. 7.1 Use of Industrial Wastes as a Raw Material for the manufacture of Clinker The following industrial wastes have potential and can be gainfully utilized as component of cement raw mix for the manufacture cement clinker. 7.1.1 Flyash R&D investigations have revealed that flyash upto 3 percent can be used as raw mix component for the manufacture of cement clinker. The resultant OPC conforms all the requirements of all the three National Standards on OPC viz IS:269-1989, IS:8112-1989 and IS:12269-1987 for 33, 43 and 53 grade OPC respectively. 7.1.2 Steel Slag Studies have revealed that steel slag can be used upto 10 percent as a raw mix component for the manufacturer of cement clinker (Table 19). The presence of high Fe2O3 (about 25 percent) restricts its bulk utilization. TABLE 19 : PERFORMANCE CHARACTERISTICS OF OPC SAMPLES PREPARED FROM INDUSTRIAL WASTES AS COMPONENT OF CEMENT RAW MIX

28

Sl. No.
1. 2. 3. 4. 5. 6. 7. 8. 9. 1. 2. 3.

Industrial Waste Used in making OPC

Properties of resultant OPC

Fineness m2/kg Setting Time (Min.)

Compressive Strength (MPa) 3 7 28 IST FST Days Days Days Steel Slag 350.0 64 113 23.0 45.0 59.0 Flyash 300.0 95 175 33.0 43.0 65.0 Red Mud 270.0 74 282 40.0 53.0 66.0 Paper Sludge 313.9 47 222 35.0 48.0 58.8 Carbide Sludge 301.1 54 182 33.0 44.0 55.5 Phospho Chalk 315.0 85 130 40.5 44.0 59.2 Lead-Zinc Sal 320.0 65 262 34.5 46.5 69.0 Jerosie 320.1 95 239 36.3 47.7 59.4 Chrome Sludge 301.0 84 135 20.0 31.0 42.5 Requirements of Indian Standard Specifications IS:269-1989 # 225 #30 #600 # 16 # 22 # 33 (Grade 33) IS:8112-1989 # 225 #30 #600 # 23 # 33 # 43 (Grade 43) IS:12269-1987 # 225 #30 #600 # 27 # 37 # 53 (Grade 53)

Soundness
Le-chat. (mm) 1 1 1 2 1 1 1 1 1 *10 *10 *10 Auto. (%) 0.05 0.05 0.15 0.05 0.08 0.08 0.06 0.07 0.14 *0.8 *0.8 *0.8

* not more than # not less than 7.1.3 Red mud R&D investigations have established that ~8 percent Red mud can be gainfully utilized as raw mix component in the manufacture of cement clinker. The presence of high percentage of alkalies (3 to 4 percent) and TiO2 (about 12.0 percent) restricts its bulk utilization. The performance data of OPC provided in Table 19 indicates that OPC conforming to the requirements of all the three National Standards viz IS:269-1989, IS:8112-1989 and IS:12269-can be manufactured from red mud. 7.1.4 Lime sludges 7.1.4.1 Paper Sludge Investigations carried out at NCB on the utilization of lime sludge from paper industry have indicated that the paper sludge can be utilized upto 74 percent (dry basis) as a component of raw mix for the manufacture of Portland cement clinker and this clinker can result in OPC conforming to Indian Standard Specifications IS:269-1989 and IS:8112-1989 (Table 19). 7.1.4.2 Carbide sludge

29

The results of R&D work have revealed that carbide sludge can be used as a source of calcareous component in the raw mix for manufacture of cement clinker. Taking into account of the tolerance limit of chloride content in the cement raw mix, the carbide sludge can be used as high as upto 30 percent in the raw mix for the manufacture of clinker, which yields OPC conforming to all the three National Standard Specifications on cement (Table 19). 7.1.4.3 Phospho-chalk R&D investigations have established that Phospho-chalk can be used as a raw mix component for the manufacture of cement clinker. Presence of impurities viz P2O5, and SO3 restricts its level of utilization to ~8 percent only (Table 19). 7.1.4.4 Sugar Sludge Preliminary investigations carried out have revealed that sugar sludge can be used as a source of calcareous component in the raw mix for manufacture of cement clinker. Detailed study is needed to establish the role of impurities present in sugar sludge on the performance of the cement (OPC) prepared from it (Table 19).

7.1.4.5 Chrome Sludge It has been found that chrome sludge can be used upto 5 percent as mineralizer. Presence of chromium oxide as impurity upto 10 percent restricts its bulk utilization (Table 19). 7.1.5 Lead-zinc slag Lead-zinc slag waste was found suitable as a component in the raw mix for making OPC-clinker upto 6 percent only as it contains high iron-oxide (~40 pecent). The OPC prepared from lead-zinc slag conforms to the Indian Standard Specifications IS:12269-1987 for 53 grade OPC (Table 19). 7.1.6 Phosphorus-Furnace Slag upto 10 percent phosphorous-furnace slag can be gainfully utilized as raw mix component in making OPC-clinker. The performance of the resultant OPC conformed to the Indian Standard Specification, IS:12269-1987 for 53 grade OPC. 7.1.7 Kimberlite waste

30

Kimberlite can be used upto 10 percent only as a component of cement raw mix in making OPC-clinker as it contains high MgO (upto 30 percent) and SiO2 (upto 40 percent). 7.1.8 Mine Rejects Depending on the composition, the mine rejects can be used as the component of the raw mix singly or in combination with other admixtures for the manufacture of cement clinker. 7.2 Use of Industrial Wastes as a Blending Material

7.2.1 Flyash Flyash is a pozzolana and can therefore be used as a blending material for the manufacture of Portland Pozzolana Cement (PPC) in the proportion of 15 to 35 percent depending upon the quality of flyash and clinker. The quality of flyash can be used for the manufacture of PPC should conform to the Indian Standard Specification IS: 3812-1981. Performance of a typical PPC sample prepared with 20 percent flyash, 75 percent clinker and 5 percent gypsum is presented in Table 20. 7.2.2 Granulated blast furnace slag Granulated blast furnace slag can be used as a blending material in the proportion of 25 to 70 percent in the manufacture of Portland Slag cement (PSC) depending upon the quality of slag and clinker used. The quality of the granulated slag, which could be used for the manufacture of PSC, should conform to the Indian Standard Specification IS: 12089-1987. The performance of the resultant PSC should conform to the Indian Standard Specification IS 4551989. The steel slag can replace granulated blast furnace slag upto 10 percent in the manufacture of PSC. Performance of a typical PSC prepared with 45 percent granulated blast furnace slag, 50 percent clinker and 5 percent gypsum is presented in Table 20.
TABLE 20 : PERFORMANCE OF BLENDED CEMENTS PREPARED USING INDUSTRIAL WASTES
Sl. No. Properties Flyash Granulated Blast Furnace Slag Paper Sludge LeadZinc Slag Granulated Phosphorus Furnace Slag

1 2

Fineness (M2/kg) Setting Times (Min) IST FST Compressive

306

350

7.36% (+90) 188 388

350

350

118 221

51 155

200 305

178 323

31

Strength (MPa) 3 days 7 days 28 days Soundness Le-Chatelier (mm) Autoclave (%) 20.5 24.8 49.3 1 0.04 35.0 49.5 68.7 1 0.07 N.D. 6.2 10.0 1 0.048 27.3 42.0 60.8 Nil 0.028 23.5 39.9 61.0 1 0.08

7.2.3 Lime Sludge The lime sludge from paper industry has been found suitable as blending material for manufacture of masonry cement in the proportion of upto 30 percent conforming the Indian Standard specification of IS:3466-1988. Performance of a typical masonry cement prepared with 30 percent paper sludge, 50 percent clinker, 15 percent flyash and 5 percent gypsum is presented in Table 20. 7.2.4 Lead-Zinc Slag R&D investigations at NCB have revealed that lead-zinc slag can be used as blending material for making Portland Slag Cement (PSC). The slag does not conform to the requirements of slag to be used for the manufacture of PSC i.e. IS: 12089-1987 with respect to IR and glass content. However, the PSC prepared from 40 percent granulated lead-zinc slag, 55 percent clinker and 5 percent gypsum conformed to all the requirements of IS: 455-1989 (Table 20). 7.2.5 Phosphorus Furnace Slag The granulated phosphorus furnace slag conforming to Indian Standard Specification IS: 12089-1987 can be used as a blending material for the manufacture of PSC in the proportion of 25 to 70 percent. Performance of a typical PSC sample prepared with 45 percent granulated phosphorous furnace slag, 50 percent clinker and 5 percent gypsum is presented in Table 20. 7.2.6 Phospho Gypsum Phospho gypsum contains deleterious constituents like P2O5, F- and free acid, which hinder its utilization in manufacture of cement. These impurities affect the setting behaviour of OPC adversely when phospho gypsum is used as a set retarder. It can however, be used after beneficiation or in combination with mineral gypsum. Performance of OPC sample prepared with 95 percent clinker, 2 percent phospho gypsum and 3 percent mineral gypsum is presented in Table 20. 7.2.7 Jerosite

32

Characterisation of a typical jerosite has revealed that it contains SO3 in considerable amount (upto 30 percent) and therefore it is likely to be useful as a set-controller in cement manufacture. Detailed investigations are needed, particularly because of the presence of deleterious constituent viz ammonia, before it is considered as a set retarder in the manufacture of cement. 8.0 PROBLEMS RELATED TO COLLECTION, HANDLING, TRANSPORTATION AND STORAGE OF INDUSTRIAL WASTES One of the major factors hindering the utilization of industrial wastes has been an economic system for collection, handling and transportation of the wastes from the source plants and facilities for handling and storage at the user end. Most of the uses of industrial waste envisage collection of waste in dry state whereas system of disposal at most of the plants is wet, which has been established keeping in view the requirements of the existing systems and relatively easy mode of disposal. There is however, a possibility of dry collection of waste by incorporating modifications in the existing systems in most of the plants. Systems of handling and transportations of the waste shall have to take into account the existing facilities of disposal of waste at the source plant, layout of the plant and its future plans, location of the user facility, the distance from the plant and the existing transport infrastructure in the area. Both mechanical and pneumatic conveying system or a combination of the two can be considered for collection, handling and transportation of wastes at the waste generating plants. Pneumatic conveying system though costly is preferable from the viewpoint of dust free operation and economy of space. In the case of the user facility being established within a distance of 2-3 Kms from the source plants, pneumatic conveying system for dry waste can be adopted in preference to transporting by rail or road in bulk carriers. Handling of dry waste at the user end involves pneumatic discharging by the conveying duct of the built-in-blowers of the bulk carrier into the storage silo. Suitable measures are to be taken while handling and transporting wet/semi-wet waste from the dumps. Keeping in view the requirements of providing a unified approach to handling, storage and transportation problems for both the fresh and the dump waste, it is suggested that the sample may be dried at the dumps and fed to the storage silo for having a common system thereafter. The economics of such a proposition need careful examination before coming to a conclusion. The hazardous waste is to be dealt as per the provisions of Hazardous Waste (Management and Handling) Amendment Rules 2003. 9.0 CONSTRAINTS IN UTILIZATION OF INDUSTRIAL WASTES

33

In spite of extensive R&D work having been done in the country even upto the stage of pilot plant trials, the level of waste utilization in India continues to be very low, only approximately 15 percent. Most of Neyveli flyash is being used for the manufacture of PPC and some of the flyash from other thermal power plants is also being used for the manufacture of PPC and making building blocks and bricks. A small percentage of flyash generated in thermal power plants close to big cities finds use in building industry. However, it is estimated that only ~28 percent of the total flyash generated in the country finds use one way or the other in building industry. Lime sludge from paper industry has been partly used by the paper industry itself but still the remaining portion is creating environmental problems and occupying large tracts of cultivable land. Phospho gypsum is also similarly used partly. The lower rate of utilization of industrial wastes in India may be attributed to one or more of the following factors: i) Since bulk of wastes is being disposed off in wet state, arrangements have to be made for extraction and supply of these wastes in dry state, which involves lot of expenditure. Transportation waste in dry form in open wagons results in huge transit losses. Provision of marketing of standard quality flyash/ other wastes in bags or any other packing including drums. Plant engineering of commercial size plants for manufacturing new materials based on industrial wastes. Need for modifications of existing standards and codes consequent upon the acceptance of different uses of flyash and formulation of new standards wherever necessary. Limitation in distance over which the wastes can be economically transported. Variation in the quality of wastes is one of the major problems related to its bulk utilization. Unawareness of consumers towards quality of waste based products alongwith confidence of builders in the use of building materials from unconventional materials. TO PROMOTE UTILIZATION OF

ii) iii) iv) v)

vi) vii) viii)

10.0

RECOMMENDED MEASURES INDUSTRIAL WASTES

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The following actions will go a long way in the promotion of utilization of wastes in national interest. i) ii) iii) iv) v) vi) vii) viii) ix) Arrangement should be made for availability of wastes in dry state. Efforts should be made for minimizing quality variation. The industrial wastes should be beneficiated to remove impurities, if possible, which deteriorate the quality of the clinker. Wide publicity regarding advantages of products based on industrial wastes. Land adjoining the waste generating industry may be acquired, ear marked and offered on lease for setting up of waste based industries. Ban through a legislation on the use of precious top soil for burnt clay brick manufacture within 50 kms radius of flyash brick plant. Arrangements to provide industrial waste to the user pneumatically. A legislation banning use of cement without flyash as an ingredient except where technically it is not advisable. Industrial waste based products should be exempted from excise duty.

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