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CHAPTER – 3

MATERIALS AND METHODS

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CHAPTER – 3

MATERIALS AND METHODS

3.1 Sustainability Initiatives:

The developing countries and the countries that are undergoing transition are

facing problems related to their waste management. In several countries, discharged

of waste water to public sewers and burning of hazardous waste and solid waste

within the company premises, illegally dumping the waste at low laying areas are not

succeed in meeting the fundamental necessities of scientific waste disposal. Due to

this there will be contamination of land, ground water and air which leads to the

deterioration of basic living condition and there by affecting the entire population.

Due to this pollution or contamination, the poisonous materials entering to the

ecosystem and finally entering to the food chain of living organisms. Due to the

industrial pollution and their emissions the Greenhouse gases emitting to the

atmosphere and causing global warming. Hence, the efficient use of fossil fuels, lethal

residues and the contamination of water and soil resources are at the front position of

environmental concerns and public deliberations. Cost saving initiatives in the

business, competition in the global market and productivity are the main concerns of

almost all businesses.

The proven and possible solution to the waste management is co-processing of

waste in a suitable industry like cement. In the cement industry the rotary kiln can

offer an environmentally sound and economically efficient treatment for several of

wastes generated in the society. These wastes can be used as Alternative Fuels and

Raw Materials (AFR) in cement a kiln, which in tern reduces the environment

pollution. This method of co-processing of waste in cement kiln will help out in

achieving the targets set in Agenda 21 of the ―Earth Summit‖ in Rio de Janeiro (1992)

and the Johannesburg Declaration on Sustainable Development (2002).

The cement manufacturing process consumes a considerable quantity of

natural resources and energy. The manufactured cement contributes to the overall

development and modernization of cities and its infrastructure. As the Coprocessing

uses waste material as a fuel, in its manufacturing process it conserves energy and

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therefore it is one of the best method in waste management across the world. By this

possible method, Best Available Technology (BAT) is being used in cement

manufacturing which usually achieves major reductions in energy consumption.

Substitution of fossil fuel and virgin raw material by waste indirectly reduce the CO2

emissions to the atmosphere, if the wastes are not being used in co-processing, it

could have been incinerated elsewhere.

This Co-processing refers to processing of waste materials in industries, such

as cement, lime, or steel and power stations in which the energy and material value of

the waste is fully recovered. Globally the co-processing of wastes has been

recognized as safest, most economical and environmentally sustaining option for

wastes management. It ranks higher in the waste management hierarchy, when

compared to other disposal options like incineration and landfill. Co-processing does

not generate any ash like incineration, thus, co-processing is an ecologically

sustainable solution for waste management.

Co-processing also results in a complete thermal destruction of waste and also

recovering the heat part of the waste as fuel and it will not generate any slags, if

generated that could have been disposed off through landfill, it has been promoted as

an alternative way to the waste disposal problem and involves no risks to the

ecosystem or to the quality of cement manufactured (Global Sustainability Initiative,

2005).

3.2 Cement Manufacturing and Co-processing of Industrial Wastes

3.2.1 Cement Industry Overview:

India ranks second in world cement producing countries after china. It took long

eight decades to reach the first 1000 Lakh metric tonne capacity, the second

1000

Lakh metric tonne was just added in just ten years. Since the demand of cement is

seasonal in nature, declines during the monsoon (July-Sept) quarter and increases

during Jan-March quarter. Figure 3.1 shows annual cement production percentage

change. As seen in Figure 1, lesser increases in all India cement production numbers

(Mar-08, Mar-09, and Mar-10) indicate lower demand for cement. While from late

2007 to early 2009, the decrease in percentage increase of cement production numbers

can be attributed to the global crisis, due to which commercial and housing real-estate

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industry saw a decrease in demand, the capacity utilization levels also declined to

85% level signaling supply constraints exercised by cement manufacturers. In 2011,

the capacity utilization has gone up to 92% which could be on the back of very less

increase cement capacities on the back of declining increases in cement demand.

Fig.3.1 Comparison of Cement production and its Utilisation – Indian Scenario

(Source: Sumit Pal Singh, 2011.Assessment of Competition in Cement Industry in

India).

The cement industry relies heavily on fossil fuels and account for five percent

of current carbon dioxide (CO2) emissions worldwide. Demand for Cement and its

production are increasing; The yearly world cement production is expected to increase

from 2,540 million tonnes (Mt) in 2006 to between 3,680 Mt (low estimate) and 4,380

Mt (high estimate) in 2050. The major share of this growth will take place in China,

India, and also other developing countries on the Asian continent (Figure 3.2)

(WBCSD/IEA 2009). This major increase in cement production is significantly

increase the energy consumption and emits CO2. Use of waste as alternative fuels will

help reduce depletion of fossil fuel resources and indirectly reduces the CO2

emissions also.

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Figure 3.2 Annual World Cement Production

(World Business Council for Sustainable Development (WBCSD)/International

Energy Agency (IEA), 2009)

In addition to the energy use and CO2 emissions challenges facing the cement

industry, the problem of increasing waste generation is facing countries around the

world. This problem is particularly significant in developing countries where major

urbanization is taking place. Municipalities and governments in many countries face

problems finding safe and environmentally sensitive means to dispose of growing

amounts of municipal solid waste (MSW) and sewage sludge. Finally, the ashes from

waste co-processing are be integrated into the clinker which can result in saving the

virgin raw materials.

Cement utilization is rising, particularly in developing countries and countries

in transition. Global cement production during 2003 was 1.94 billion metric tons

which increases from1.69 billion tonnes in 2001, with an estimated increase of 3.6%

due to the strong demand in developing countries and countries in transition (Source:

Cembureau1).

During the past 20 years, the cement industry in European countries has

reduced its energy consumption by about 30%, equivalent to saving approximately 11

million tonnes of coal per year. Substituting fossil fuel and virgin raw material by

waste (Alternative Fuels and Raw material - AFR) will further reduce overall CO2

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emissions, if the waste material being used would instead have been burned or

disposed without energy recovery.

There is an urgent need to improve waste management, and different solutions

are being discussed. Waste avoidance, cleaner production, producer responsibility,

and supply chain management are only a few of the strategies being promoted. In

spite of technological progress and an increasing social and political awareness, the

problem of growing waste streams persists. Modern incineration plants and secure

landfills are common disposal options in OECD countries, but have high investment

and operating costs and need qualified personnel. An efficient cement kiln can

provide an environmentally sound treatment/recovery option for a number of waste

fractions.

3.2.2 Cement Production Process in Brief:

Mining process: The key raw material Limestone is mined from the quarries by

using compressed air drilling machines and then blasting with explosives materials in

the mines. After wards, the mined limestone is being transported through dumpers or

through ropeways to the production site. Gradually the surface mining is gaining

popularity because of its eco friendliness.

Fig.3.3 Mining the key raw materials.

Crushing process: The mined limestone is fed into primary and secondary

crushers where the size is reduced as per requirement. Now a day‘s even a tertiary

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crusher is also being used to further reduce the inlet size to the mill. The above

crushed limestone material is stored in the stockpile through stacker conveyors. The

crushed limestone along with bauxite and ferrite are stored in feed hoppers from

where they are taken to the raw mill via feeder in the requisite ratio.

Fig.3.4 Lime Stone Crusher

Preparation of Raw Materials: Raw material are being prepared to

manufacture cement by grinding the said materials in Roller mills and separators or

classifiers also being used to separate ground particles, these are the two important

equipments consuming more energy in cement manufacturing. If the dry-process is

being followed in manufacturing cement then the raw materials require being ground

into a flowable powder before entering the kiln. For this purpose ball mills and

vertical roller mills are being used.

Fig.3.5 Roller Mill

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Milling of Coal: Majority of plants using coal in cement manufacturing and coal

mills are the integral part of the system to provide grounded dry coal to kiln and

precalciner. Coal from backyard is crushed in a hammer crusher and taken to the coal

mills. The coal mills either air swept ball mill or vertical roller mill where the coal

particles are collected in the bag filter through a grit separator. Hot air generated in

the furnace or hot air from clinker cooler or preheater exhaust is being used in drying

of coal in the coal mill.

Fig.3.6 Coal Mill

Pyro processing: The main functions of the kiln in the cement production is to

convert calcium carbonate to calcium oxide and then it reacts with Silica, Aluminum

Oxide, Ferric Oxide, and Calcium Oxide with the free lime to form clinker

compounds. This mixed raw material enters the kiln at the elevated end, and the

combustion fuels generally are introduced into the lower end of the kiln in a

countercurrent manner. The materials are continuously and slowly moved to the lower

end by rotation of the kiln. Usually pulverized or grounded coal, gas and pet coke are

the main fuels generally being used. This system converts the raw mix into clinkers.

The chemical reactions and physical processes which constitute the

transformation are quite complex. The following chronological events are taking

place while manufacturing the cement clinker: Water content present in the raw

material start evaporating as the temperature increases to 1000C, As the Dehydration

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starts the material temperature increases from 1000C to approximately 430

0C to form

oxides of silicon, aluminum, and iron and during Calcination carbon dioxide is

evolved, between 9000C and 982

0C and it forms calcium oxide and finally reaction of

the oxides in the hot zone of the rotary kiln and form cement clinker at temperature of

approximately 15100C.

Fig.3.7 Pyro processing

Pre heater and Pre calciner: The Preheaters and cyclones are set

perpendicularly, in sequence, and are supported by a structure called as the preheater

tower. Hot exhaust gases from the rotary kiln pass counter currently through the

downward-moving raw materials in the preheater vessels. The main purpose of this is

to intimate contact of the solid particles with the hot gases. The better heat transfer

allows the length of the rotary kiln to be reduced which increases the production.

Additional thermal efficiencies and increased productivity can be achieved by

deviating some fuel to a calciner vessel at the base of the preheater tower. This system

is called the preheater precalciner process. Up to 95 % of the raw meal gets calcined

before entering the kiln. From pre-heater and pre-calciner, 60 % of flue gases travel

towards raw mill and 40 % to conditioning tower where water injection is used to

condition the gases. These gases are finally passed through electrostatic precipitator

for the maximum removal of suspended particulate matters present in the flue gas.

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Fig.3.8 Pre Calciner

Clinker Cooler: The hot clinker generated from the process is cooled from 11000C

to 900C in the grate cooler provided with a sequence of fans. The cooler performs two

important works, it recover as much heat as possible from hot clinker and returns the

same into the process and it will also reduce the clinker temperature, which finally

helps the down streams equipments to handle this clinker. The hot air from

recuperation zone is used for main burning air and precalciner fuel. The left over air is

sent to the stack through multiclones or ESP after removing particulate matters. After

clinker comes out from kiln it must be cooled quickly to make sure the highest yield

for the compound which finally contributes to the hardening properties of cement.

Fig.3.9 Clinker Cooler

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Finish Milling: In this final process, previously cooled clinker is mixed with

additives to make cement and it will be grounded using the milling method. Clinkers

mixed with additives are then sent through mills for grinding. This process is

performed in a closed system with an air separator which separates the cement

particles according to their size. Material which is not completely grounded is sent

back to the system again. Finish milling will grind the clinker into a fine grey powder.

Gypsum is blended with the grounded clinker, along with other materials, to produce

finished cement. Gypsum controls the rate of hydration of the cement in the

cement-setting process. The cement produced is then collected in the bagfilter and

taken to cement silos through a vertical pneumatic pump.

Cement obtained is an inorganic, non-metallic substance with hydraulic

binding properties, and is used as a bonding agent in building materials. It is a fine

powder, usually gray in color that consists of a mixture of the hydraulic cement

minerals to which one or more forms of calcium sulfate have been added (Greer et al.,

1992). Mixed with water it forms a paste, which hardens due to formation of cement

mineral hydrates. Cement is the binding agent in concrete, which is a combination of

cement, mineral aggregates and water. Concrete is a key building material for a

variety of applications.

3.2.3 Co-processing of Hazardous Waste in the Cement Industry:

The use of different types of waste as alternative fuels and raw materials

(AFR) in cement kilns or similar plants has been successfully used in Europe, Japan,

USA, Canada and Australia successfully since the beginning of the 1980s.Table.3.1

gives an overview of energy substitution through AFR in the cement industry in

selected countries.

Table 3.1 Overview of Energy Substitution through AFR in Cement Industry

Country

% of Thermal Energy

Substituted by AFR

Year

USA 25 2003

France 32 2003

Germany 35 2002

Norway 45 2003

Switzerland 47 2002

GTZ/Holcim (2006)

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Developed countries are having more than twenty years of experiences in the

field of hazardous waste co-processing. If this method was implemented in developed

countries the questing comes here is why this is not implemented in developing

countries and why this co-processing not been promoted as it ecologically beneficial

and also energy and material recovery can be made in this process. It is main because

of limited knowledge of the potential use of AFR in cement plant and of statutory

rules and regulation requirements related to co-processing and concerns of the public

and NGOs over environmental and health issues. Co-processing of hazardous waste in

cement production has been recognized in Basel Convention as an environmentally

sound disposal method.

India generates about 6.2 Million tonnes of hazardous wastes is annually, in

that around 3.1 Million tonnes is recyclable, 2.7 Million tonnes is land-fillable and 0.4

Million tonnes is incinerable. The hazardous waste classified is based on the hazard

potential and its characteristics which is in accordance with the Hazardous wastes

(Management and Handling & Transboundary Movement) Rules, 2008. As per above

information most of these hazardous wastes have suitable to utilize either as resource

material for recovery of energy or as a materials. Hence a new mind-set developed to

treat above hazardous waste as a resource material rather than a difficult disposable

material is the need of the hour.

The cost of putting up new incinerator is costly and even ashes generated

from the incinerator have to be disposed off to the secured landfill facility and again

cost will incurred in disposal, apart from this there are lot indirect cost for land and

its monitoring comes extra. If incinerator not operated properly it may emit toxic

gases like Dioxins and Furans. But Coprocessing is a resource conservation method

and it will reduced carbon emissions to the atmosphere, considering all these

advantages co-processing as a sound and better alternative for hazardous wastes

disposal.

Hence, the co-processing of hazardous wastes in cement kilns is much

beneficial option, there by hazardous wastes are not only disposed scientifically at a

higher temperature and with longer residence time, but the inorganic content gets

fixed with the clinker apart from using the energy content of the wastes. In this

process, no residues are left, which in case of incineration still requires to be land

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filled as incinerator ash. Further the acidic gases generated during co-processing get

neutralized, since the raw material is alkaline in nature. Thus utilization of Hazardous

wastes for co-processing makes a better option when compared to incineration and

landfills are considered.

If we consider production of cement in Indian scenario which is about 200

Million Tonnes per annum, for this an estimated coal and lime stone requirement are

40 Million Tons per annum and 320 Million Tons per annum, respectively. Therefore,

India has a potential to utilize entire hazardous waste generation, if found suitable

otherwise, for co-processing.

Apart from Cement Industry, Thermal Power Plant, Iran and Steel Industry are

other potential industries for co-processing which consist necessary inbuilt infra

structures. Figures 3.10 and 3.11 show the locations of Cement, Thermal Power and

Steel Industry along with existing location of Common Hazardous Waste Treatment

& Disposal Facility (TSDF).

3.2.4 Moving towards Sustainable use of Fuels and Raw Materials in

the Cement Industry:

Manufacturing cement is an energy-and resource intensive method. In general

every year the cement industry across the world produces over 1.8 billion tonnes of

cement. To adopt this co-processing method in all the cement plants it is the way the

industry selects and uses fuels and raw materials is an important factor, without

affecting environmental, social, and economic impacts.

Sustainable development means the way of development that meet the

requirements of people living today without compromising the capability of future

generations to meet their own needs. Cement manufactured across the globe helps

people today in many ways by meeting their needs for housing, buildings, and for

much of the infrastructure of civilization; it will do so into the future until a better

material is developed. However, cement production is both energy- and material-

intensive, if we exhaustively use these non-renewable resources for day to day

requirement finally that will not be available for future generations. Emissions

generated from these production processes may affect the quality of air, water, and

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soil today, and also in, future generations. Hence, the cement industry can contribute

to sustainable development by using energy and resources as efficiently and cleanly as

possible by adopting co-processing technology.

Fig 3.10 Locations showing Cement, Steel and Thermal Power Plant of India

(Co-processing Guide lines, 2010)

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Fig.3.11 Locations showing Common Hazardous Waste Treatment, Storage &

Disposal Facility (TSDF), (Co-processing Guide lines, 2010)

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3.2.5 Principles of Co-processing in the Cement Industry:

Co-processing of hazardous and non- hazardous solid wastes in cement kilns

by safer and environmentally friendly manner will be recognized by entire globe for

its environmental benefits. To avoid satiations of poor waste management there by

polluting the environment and to give a importance for best environment management

a set of principles were initially developed by Deutsche Gesellschaft für Technische

Zusammenarbeit (GTZ),(GTZ/Holcim, 2006). These principles will provide a

complete and brief summary of the key considerations for co-processing wastes by the

end users.

The World Business Council for Sustainable Development (WBCSD, 2005)

also come out with similar principles, even Karstensen (2008a, 2009a) has laid out a

sequence of general requirements specific to cement kilns co-processing hazardous

wastes.

Following are some of the definitions frequently being used:

Waste: ―any substance or object, which the user discards or intends or is required to

discard or has to be treated in order to protect the public health or the environment.‖

Waste material can be solid, liquid, or pasty.

Co-Processing: “Use of waste resources in industrial processes, such as cement,

lime, or steel production and power sectors or any other large combustion plants‖. Co-

processing means the substitution of primary fuel and raw material by waste. It

mainly a recovery of energy and material from waste.

AFR (Alternative Fuel and Raw Materials): Waste materials used for

Coprocessing. These wastes include plastics and paper, waste tires, biomass, waste

textiles, residues from automotive plants, hazardous industrial waste such as waste

oils, industrial sludge, impregnated sawdust and spent solvents as well as obsolete

pesticides, out-dated drugs, chemicals and pharmaceuticals.

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Table 3.2 provides the general principles of Co-processing:

Table.3.2 General Principles of Co-processing

Principle Description

The waste management

hierarchy should be

respected

Practiced in cement kilns only if there is no

ecologically and economically better ways of

recovery& reuse.

Adopted as an integrated part of waste management

It should in line with the national & international

requirements

Additional emissions

and negative impacts

on human health must

be avoided

Impact of pollution on the environment and human

health must be prevented or kept at a minimum

Air emissions from cement kilns co-processing

waste is in line statutory requirements

The quality of the

cement must remain

unchanged

The heavy metals content in the product (clinker,

cement, concrete) must within the limits

Product should not have any negative impacts on

the environment

Quality of the product must allow for end-of-life

recovery

Companies that

co-process must be

qualified

Guarantee compliance with all rules and

regulations

Industry should have good environmental and

safety compliance records

Necessary employees, processes, and systems in

place committed to protecting the environment,

health, and safety

Industry should capable of controlling inputs to the

production process

Maintain good relations with public and others

Implementation of

co-processing must

consider national

circumstances

Country specific requirements to be reflected in

regulations and procedures

Detailed implementation allows to build-up

required capacity and the set-up of institutional

arrangements

Introduction of co-processing goes along with other

change processes in the waste management sector

of a country

3.2.6 Hierarchy for Waste Management:

The waste is being co-processed only when the waste cannot be avoided or re-

used in a more environmentally favorable manner. The integration of co-processing

into the waste hierarchy is shown in the figure below.

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Avoidance or prevention: Waste generation can be prevented or avoided by strict

procedures that ensure that that said materials should appear as wastes.

Minimization: Waste can be minimized by adopting cleaner production concepts or

changes in consumer habits.

Recovery: Waste can be recovered by means of recycling and reuse of materials.

Co-processing: It is method recovery of energy and materials from waste as a

substitute for fossil energy and virgin raw materials.

Incineration: Is method of thermal destruction of waste and employed to reduce

waste volumes.

Chemical-physical pre-treatment: Is a method to stabilize waste materials before

final disposal.

Controlled land filling: It is the common method for the final disposal of waste.

Uncontrolled burning and dumping: Open burning or uncontrolled dumping, is still

the most common method of waste disposal in developing countries.

Figure 3.12 Waste Management Hierarchy, GTZ/Holcim (2006)

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In the present study, this waste management scheme or concept of waste hierarchy

shown in Fig 3.12 has been followed.

3.2.7 Considerations for Selection of Wastes:

The basic rule for waste acceptance for cement plant as an alternative fuel or

raw material must give an added value for the cement kiln by means of the heating

value and the material value of the mineral part present in it. Wastes having high

metal content will generally not be suitable for co-processing, because the heavy

metal content may vary the operating characteristics of cement plants.

Pre-processing of heterogeneous nature of waste by means of blending and mixing of

different waste streams may be required to guarantee a homogeneous feed that meets

specifications to use the wastes in a cement kiln.

3.3 Waste Acceptance, Collection and Transport:

3.3.1 Wastes Acceptance for co-processing in cement kilns:

Knowledge of wastes before cement plant accepted and processed is necessary

to facilitate the operator to ensure that the waste is within the desired limits of the

cement plant and will not adversely affect the process. Generators of hazardous waste

should also know the composition, nature and problems associated with their waste

and should ensure that all information about the waste is passed to cement plant for

necessary actions.

Jubilant generates different kinds of wastes during its manufacturing. These wastes

are hazardous as per Hazardous Waste (Management, Handling & Transboundary

Movement) Rules, 2008. These wastes include:

N-Butanol Residues (Process residue)

Solar evaporation Pond Sludge (Sludge generated from waste treatment

facility)

Considering the benefits of co-processing cement Industry and Pharma industry

tougher found the solution for safe and environmentally sound disposal method of the

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wastes generated Jubilant unit, through co-processing in Cement plant. Associated

Cement Company (ACC) conducted the prerequisite tests to evaluate the feasibility of

co-processing of process residue and Sludge generated from waste treatment facility

at its Technical Support Services (TSS) in Thane and offered to co-process the same.

Fig.3.13 shows the procedure that was followed prior to acceptance of the wastes

generated at Jubilant:

Fig.3.13 Flow Chart of procedures adopted before accepting the wastes.

3.3.2 Procedures followed prior to acceptance of the wastes

1. Preliminary Screening of the waste: It was assessed if the wastes fall under any of

the banned wastes as listed below:

Customer meet

No

Yes

Suggest

Alternative

Solution

Clearances from

Authorities

No

Yes Co-processing

Agreement with

Customer

Undertake

Trial Burn

Submit to

Authorities

Approval?

No Yes

Initiate

Regular

Co-processing

Trial Burn

Required?

Yes No

Customer

Interaction

Sample

Evaluations

Co-

processable?

Finalize

Usage

Plan

Approval?

Explosives

High-concentration Cyanide Wastes

Mineral Acids

Radioactive Wastes

Unsorted Municipal Garbage

Anatomical Hospital Wastes

Asbestos-containing Wastes

Bio-hazardous Wastes

Electronic Scrap

Entire Batteries

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2. Survey of the industry to get Industry and Waste Profile Details: The industry

details were obtained w.r.t. type of the industry, the rate of generation of wastes,

characteristics of the wastes, process of generation, safety data of the wastes etc

3. Assessment of Co-processibility of the Wastes: Representative waste samples were

collected and sample analysis carried out for the variability of the material quality was

understood and the impact of the physical and chemical properties on cement quality

was estimated using the Fuel Mix Optimizer model (Fig.3.14). It was re-assured that

the waste does not contain any of the banned wastes

Fig.3.14 Assessment of Co-processibility of the Wastes

4. Technical Assessment and Baseline Monitoring: Thermal characteristics of the kiln

system were assessed and the point of feeding of the wastes into the kiln system was

established. The baseline emission monitoring of the kiln stack at kiln was conducted

when no waste or waste materials are used. It formed the basis for assessing the

incremental emissions from co-processing wastes in the subsequent years.

5. Commercial Proposal, negotiation and legal agreement: The commercial terms and

conditions were discussed and finalized on the basis of a nominal value of the services

being offered. An agreement was entered with deliberating the roles and

responsibilities of both the parties.

6. Hazard Identification, Risk Assessment and Control: On the basis of the safety

data provided and other safety related information, both the industries are jointly

developed the Risk Assessment Procedure (RAP) and formulated the action points for

implementation of the necessary controls. The workplace label, which summarizes the

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different hazards and controls, is being displayed at the site of co-processing in both

English and the local language.

7. Transportation of the Trade Rejects and Receipt of the trade rejects at ACC Wadi

Cement Works: A pre-delivery inspection is done to ensure that only the agreed

material is delivered. A delivery schedule is worked out. It is ensured by industry that

the risks as well as the requirements and precautions for safe handling, transportation

and storage are clearly understood by transporter.

The technical person in the cement plant conducts an inspection of the

delivery and wastes Laboratory analyst conducts sampling for fingerprint analysis of

the waste. The truck is weighed at the plant weighbridge and the weighbridge operator

records information on the delivery receipt, date and time of delivery and the gross

weight. Transporter unloads the wastes at the designated unloading area.

8. Protocols for Sampling and Testing of Delivered wastes: A state of art laboratory at

cement plant analyzes the parameters for delivery acceptance criteria like moisture,

CV, Cl and S analysis is done. The cement works accept the consignment, only if, the

variation in the trade rejects is within the range as agreed between the parties.

9. Protocols prior to feeding of wastes: The feed rate of the wastes is established

during the trial run where the material feed to the kiln is optimized and the emissions

(monitored by a CPCB approved ISO 17025 certified third party) and the other

operational parameters are closely monitored. On a regular basis, the schedule for

feeding of wastes is determined by wastes coordinators and quality control people in

the plant (headed by chief manager-production) after assessing the kiln conditions.

The feeding of wastes is done through a specialized starter kit solution and the feeding

of the wastes in the kiln systems may only start after the all the safety precautions are

in place and the workers handling the materials are well trained and equipped with

applicable PPEs.

10. Protocols for Feeding of wastes and Monitoring: Before the waste materials are

fed into the kiln, kiln stable conditions, in terms of operations, has to be assured. The

clinker samples drawn 2-3 times in every shift and the analysis of the clinker samples

acts as a feedback for wastes feeding into the kiln systems.

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The N – Butanol residue is generated from the manufacturing of product called

Carbamazepine an antiepiliptic drug. Jubilant had forwarded the sample of the

n – Butanol residue to ACC for the evaluation of co-processing feasibility shown in

Table 3.3. The waste was analyzed at the R&D of ACC Limited located at Thane. The

analysis result of the N – Butanol is shown in Table-3.4. Based on the analysis, ACC

confirmed to Jubilant that the N- Butanol waste can be disposed by co-processing at

cement kiln in ACC Wadi Works.

The SEP Sludge is generated from the Solar Evaporation Pond existing at

Jubilant. The SEP Sludge is collected over a period of time for natural concentration

in the elevated tanks for evaporation purposes. Mainly contains distillation bottom

residues. Jubilant had forwarded the sample of the SEP Sludge to ACC for the

evaluation of co-processing feasibility. The waste was analyzed at the R&D of ACC

Limited located at Thane. The analysis result of the SEP Sludge is shown in

Table-3.4.

Table 3.3 Details of Waste Considered for Co-processing

Type of Hazardous

Waste Category Source of Generation

N - Butanol residue 36.4 Manufacturing of product called

Carbamazepine (an antiepiliptic drug)

SEP Sludge 34.3 Solar Evaporation Pond

Evaluation of the n – Butanol residue & SEP Sludge Sample Received From M/s

Jubilant Life Sciences Limited: The sample received was evaluated for the

proximate analysis and calorific value. The analysis results are given below:

Table-3.4 Proximate Analysis of the wastes

Sample Details

Proximate Analysis CV

Cal / Gm

(GOD)

% S % Moisture

(As recd.)

% VM

(ODB)

% ASH

(ODB)

%Fixed C

(ODB)

N – Butanol

Residue 4.5 73.5 26.5 - 5584 3.4

SEP Sludge 10.2 94.0 5.9 0.1 7238 0.8

The sample was converted into ash by firing it in a furnace at 8500 C

temperature for three hours with natural air draft. The chemical analysis of the ashes

66

so obtained was carried out. The chemical composition of the ashes is shown in

table 3.5.

Table 3.5 Chemical analysis of the ashes obtained from wastes

Constituents N- Butanol Waste Ash SEP SLudge Ash

SiO2 0.8 ND

Al2O3 0.43 ND

Fe2O3 1.3 ND

CaO 0.57 ND

MgO 0.26 ND

LOI (10000C) 7.0 ND

SO3 36.7 ND

Total.Cl 0.08 ND

Na2O 1.63 ND

K2O 50.59 ND

P2O5 0.05 ND

TiO2 0.02 ND

Mn2O3 0.02 ND

Cr2O3 - ND

NiO - ND

ZnO - ND

BaO - ND

WO3 0.2 ND

Ta2O5 0.2 ND

PbO - ND

Br - ND

SnO2 - ND

67

3.4 CONSIDERATIONS FOR SELECTION OF WASTES:

Waste storage and handling and pre-processing:

After passing the criteria of waste acceptance by the cement plant operator, the

has to be sent to cement plant for co-processing, the operator should have in place

systems and procedures to ensure that wastes are transferred to appropriate storage

safely.

Storage area should be adequately bunded and sealed, which are impermeable

and resistant to the stored materials, should be provided to prevent spills from

spreading and seeping into the soil. If the any spillage occurs during storage and

handling all spills should be collected, placed in a suitable container, and stored for

disposal in the kiln. Waste compatibility should be checked and incompatible wastes

should be prevented from mixing in case of a spill. If the waste material is liquid in

nature and should be collected tanks then, all connections between tanks should be

capable of being closed through proper valves, and overflow pipes are to be connected

to a contained drainage system, leak proof equipments to be installed wherever

possible.

Leak detecting measures are to be provided for necessary corrections,

contaminated runoff to be prevented from entering storm drains and any water bodies

nearby. It is better provide alarm system for any abnormalities.Containerised wastes if

any should be stored under proper cover, protected from heat and direct sunlight.

Sufficient ventilation should be provided in deliberation with the applicable work

exposure limits.

A fully fledged fire protection system meeting all standard requirements and

specifications should be installed in consultation with local authorities. An automatic

fire detection system should be used in waste storage areas along with automatic fire

suppression systems.

For solid hazardous waste, storage area water systems with monitors and water

cannons with the option to use water or foam, and even dry powder systems are

commonly used. Foam and carbon dioxide control systems provide for the storage of

flammable liquids.

68

3.4.1Quality Assurance/Quality Control:

Co-processing cement plant should have a complete quality assurance and

quality control department to ensure to check the waste materials that should be co-

processed in cement kiln. By analysing the wastes it ensures that plant operations are

not negatively affected by the use of hazardous wastes and also helps in protecting the

environment and to reduce risks to worker health and safety by selecting the suitable

waste for Coprocessing at cement kiln. These departments should be prepared to help

ensure regular monitoring, sampling, and analysis of wastes. Self monitoring purpose

a laboratory with necessary infrastructure, equipments and instrumentation provided

and maintained to ensure that all required analysis are completed in a timely manner.

Periodically waste can be analysed by thirds party laboratory to evaluate and improve

site laboratory performance. Even during waste analysis employees working in these

departments should follow site specific Safety and health considerations while

conducting sampling. Employees carrying out sampling activities are trained with

respect to the hazards associated with waste and also for handling procedures.

3.4.2 Health and Safety Aspects:

In cement plant where Coprocessing operations are being carried out regularly

should have a proper health and safety programmes, which in turn recognize, assess

and manage safety and health hazards and also provide for emergency response for

hazardous waste operations.

Hazard analysis:

Hazard Identification and Risk assessment should be in place in cement plant to

identify the possible exposures affecting workers, process are determined and plant

should ensure that appropriate control practices and techniques are in place.

3.4.3 Access and hazard control:

To get rid of or manage worker exposure to hazards, the following control methods

should be considered

69

– Engineering controls: Isolating the hazard, e.g., ventilation or use of battery

operated or remotely operated equipments to handle wastes

– Administrative controls: to manage worker entry to hazards storage area, e.g.,

prevent unauthorized or unprotected entry to hazardous wastes storage area.

PPE: It is final method of control only when engineering or administrative controls

are not feasible fails to eliminate the hazard then only it should be used or in

combination.

Table 3.6 Types of PPE & their usage

Necessary waste material safety data sheets are to be prepared and kept ready for

reference.

Sl.

No.

Name of Appliances

/PPE’S

Purpose

1. Dust masks Respiratory protection

2. Double Cartridge Mask for

organic vapor Respiratory protection

3. Acid/ Alkali proof hand

gloves. Hand Protection against Acid / Alkali

4. Surgical hand gloves. Hand Protection against Haz waste

5.

Skin barrier Creams For Hand Protection, Use before wearing

Gloves

6. Face shields.

Face & eye protection against Chemical

splash.

7. PVC aprons. Body Protection against Chemical splash.

8. Eyewash and body wash

fountains. First Aid for chemical splash

9. Safety Goggles. Eye protection

70

Personal Protective Equipment:

Employees, contractors and individuals visiting the installation, are provided with

PPE (Table 3.6). PPE are:

Image 3.1Various types of PPE’s

Training:

An useful training to be imparted to the worker to protect his safety and health.

All the employees are to be trained to a minimum requirement to their job function

and responsibility before they are permitted to handle hazardous waste operations.

Training performance are adequately monitored and recorded.

The training topics should cover the basic safety, health and fire protection

required for the facility, use of personal protective equipment; on the job safety

training. Safe use of fire protection systems and also engineering controls and

equipment present in the site.

71

Image 3.2Training to Employees

Occupational Health Centre:

A detailed medical programme are to be prepared by the cement plant operator

to monitor employee health both prior to employment and during the course of work

and to provide emergency and other treatment as needed. The activities of medical

team at site are:

– Pre-employment medical check, to confirm fitness-for-duty, testing the ability

of worker while wearing PPE, and to provide information to prevent

exposures during work.

– Periodic medical monitoring examinations at least once in six months to

determine biological trends that may shows an early signs of chronic adverse

health effects; and finally

– Requirements for emergency treatment.

72

Image 3.3 Medical Surveillance

Emergency Response:

This Emergency preparedness is established for the protection of the workforce,

public and for finally to protect asset before hazardous waste emergencies. A detailed

on site Emergency Response Plan has been prepared and should be approved by

respective authorities and should be kept in place, to ensure that appropriate measures

are taken to handle possible on-site emergencies and coordinate off-site.

Emergency equipments like fire extinguishers, self-contained breathing

apparatus, sorbents and spill kits, and shower, eye wash stations are located in the

immediate surrounding area of the hazardous waste storage.

As per the Plan requirement, rehearsal are to be carried at regular intervals using

drills and mock situations, and these drills should be reviewed periodically in

connection to new changes in the facility. Emergency contact details in case of

emergency to be explained in the onsite plant.

73

3.5. Hazardous Waste Storage and Handling:

The N-Butanol residue & SEP sludge was packed in HDPE bags with inner

lining of LDPE (approx. weight 15 kg) with inner lining of LDPE in Jubilant‘s waste

storage yard. The waste was transported to ACC Wadi Works by an approved or

authorized transporter from State Pollution Control Board. The bags were labeled and

loaded manually on the truck (Image 3.4).

Image.3.4 Hazardous waste Transportation

3.5.1 Temporary Hazardous Waste Storage Shed:

The temporary hazardous waste storage shed at Wadi Works is fully covered

with cement flooring with leachate collection facility. Necessary precautionary boards

displayed at prominent location in the site, safety signs and waste specific workplace

labels for handling hazardous waste material are displayed at strategic locations. Fire

extinguishers - both dry & CO2 type - are available in the storage shed. Risk

Assessment Procedure (RAP) was prepared by ACC safety team in association with

Jubilant safety team for n-Butanol Residue & SEP Sludge before transportation of

waste from Jubilant to Wadi Works (Image 3.5).

Image.3.5 Hazardous Waste Storage Shed

74

3.5.2 Hazardous Waste Handling:

The unloading process was done at ACC Wadi by trained workers equipped

with personal protective equipments. The bags were unloaded manually and stored at

designated place in the storage shed. The workers & supervisors were trained in

handling and safety aspects of hazardous waste well in advance of the trial burn.

Concerned personnel were also trained on precautions to be undertaken, emergency

measures, potential spill abatement, proper use and upkeep of PPEs, etc. The bags

were stacked in the containers under the supervision of AFR coordinator. At the time

of feeding the bags were loaded on Tractor to transport the material from the storage

shed to the hoist. Tarpaulin sheets were spread on the concrete floor of the storage

shed and the bags were placed on the tarpaulin sheets to avoid any problems in case of

leakage/spillage. Leachate collction facility also made for necessary collection

treatment (Image 3.6).

Image 3.6 Boards Displaying Safety Measures at Waste Handling Site

3.6 Waste Pre-processing:

Hazardous wastes used in cement kilns must be uniform in nature with required

particle size well-matched with the operations concerned, and have a steady chemical

composition and energy content, so as not to disturb from regular kiln operation,

quality of product and the environmental performance of the site. For best possible

operation, kilns require very consistent waste material flows in terms of quality and

quantity. For some types of wastes this can only be achieved by their pre-processing,

this includes drying, shredding, grinding or mixing depending on the type of waste.

75

3.7 Environmental Aspects:

3.7.1 Volatile organic compounds, odours, and dust:

Volatile and regular Emission monitoring and reporting should be performed in

accordance with applicable regulations.

Pollution control measures should be in place as required and acoustic and other

appropriate measures for noise and odours should be considered. Bag filters and ESP

should be in place reduce dust.

3.7.2 Drums and ferrous metals:

Waste empty metal drums and other removed by magnetic separators should be

disposed of to authorised drum washers/recyclers.

3.7.3 Wastewater/Leachate handling:

The waste water and leachate generated during waste storage and pre-

processing are to be collected in a separate tank and same has to be disposed as per

the statutory requirements.

3.7.4 Emissions Monitoring and Reporting:

Emissions and air quality monitoring programmes provide information that can

be used to assess the effectiveness of emissions management strategies. A systematic

planning process is recommended to ensure that the data collected are adequate for

their intended purposes. The parameters selected for monitoring should be indicative

of the pollutants of concern from the process, and should include parameters that are

regulated under compliance requirements.

3.8 Co-processing of Hazardous Wastes in Cement Kilns:

The proven and possible solution to the waste management is co-processing of

waste in a suitable industry like cement. In the cement industry the rotary kiln can

offer an environmentally sound and economically efficient treatment for several of

wastes generated in the society. These wastes can be used as Alternative Fuels and

Raw Materials (AFR) in cement a kiln, which in turn reduces the environment

76

pollution. This method of co-processing of waste in cement kiln will help out in

achieving the targets set in Agenda 21 of the ―Earth Summit‖ in Rio de Janeiro (1992)

and the Johannesburg Declaration on Sustainable Development (2002).

The cement manufacturing process consumes a considerable quantity of

natural resources and energy. The manufactured cement contributes to the overall

development and modernization of cities and its infrastructure. As the Coprocessing

uses waste material as a fuel, in its manufacturing process it conserves energy and

therefore it is one of the best method in waste management across the world. By this

possible method, Best Available Technology (BAT) is being used in cement

manufacturing which usually achieves major reductions in energy consumption.

Substitution of fossil fuel and virgin raw material by waste indirectly reduce the CO2

emissions to the atmosphere, if the wastes are not being used in co-processing, it

could have been incinerated elsewhere(Fig 3.15).

This Co-processing refers to processing of waste materials in industries, such as

cement, lime, or steel and power stations in which the energy and material value of

the waste is fully recovered. Globally the co-processing of wastes has been

recognized as safest, most economical and environmentally sustaining option for

wastes management. It ranks higher in the waste management hierarchy, when

compared to other disposal options like incineration and landfill. Co-processing does

not generate any ash like incineration, thus, co-processing is an ecologically

sustainable solution for waste management.

Fig-3.15 The (Cement) Clinker process & its special Characteristics,

GTZ/Holcim (2006)

Dp-062a.dsf / Kma 17.12.04

The (Cement) Clinker Process and its Special Characteristics (Example: Precalciner Kiln)

Clinker cooler

Rotary kiln

Precalciner

Raw meal (cyclone) preheater

Raw mill

Bag filter (or electrostatic precipitator)

Natural and AlternativRaw Materials

Silo

Exhaust gas

Conventional andAlternative Fuels

Clinker

1

2

4 5

6

3

1

2

3

4

5

6

2

3

4/5

6

2000-1050

1200-880

880-100

100-100

All organics burnt, fuel ash =raw mat.,incorporated in clinker

SO2 and HCl trapped dueto presence of CaO

Act as a 5-stage dry scrubber for combustion gases

99.999 % dedusting efficiency

Gas Temp. Special Features

77

Use of substitute fuels present the cement industry with an opportunity to

make a significant contribution to the mission for a sustainable society while, at the

same time, remaining competitive in a difficult cement market. A major benefit is the

recovery of energy from waste materials that would otherwise disposed of by landfill

or incineration (Fig 3.16).

Fig-3.16. Waste as Alternate Fuel / Raw Material – AFR

Co-processing of the waste in cement plant has the following advantage during

the cement production process (Fig 3.17).

– Absorption of volatile components from the gas phase as the alkaline

conditions and the intensive mixing favors process and there will be an

internal gas cleaning results in low emissions acidic gases and heavy metals.

– The high temperature clinker reactions at rotary kiln at 14500C allow the

chemical binding of heavy metals and same will be incorporated to the

clinker.

– The substitution of high calorific waste material gives a higher efficiency on

energy recovery.

78

Fig-3.17. Examples of Waste for Co-processing

3.9 Key Performance Indicators:

3.9.1 Environmental Aspects:

Air emissions:

The emissions from cement plants which cause greatest concern and which need to be

dealt with are dust or particulate matter, NOx and SO2. Other emissions are VOC,

PCDDs, PCDFs, HCl, CO, CO2, HF, ammonia (NH3), benzene, toluene,

ethylbenzene, xylene, polycyclic aromatic hydrocarbons (PAH), heavy metals and

their compounds.

As a standard co-processing should not change the quality of the cement and hence

the cement clinker should not be considered as sink for heavy metals.

Monitoring:

Emission monitoring from the cement plant are to be conducted to allow statutory

bodies to check compliance with the regulatory conditions. Necessary control

measures should be adopted by the operator of the facility in case if monitoring

parameters are more than the requirements..

79

For self-monitoring activities internal lab facility can be used to evaluate performance

of inside lab once in a while a check has to be carried out by third party.

3.10 Waste Feeding Points and Special Arrangements:

3.10.1 Operational Requirements:

Operational Considerations:

Written procedures and instructions are to be prepared and put in place for the

waste unloading, handling, and storage area on the site. One should have the chemical

incompatibilities guide for necessary segregation and storage of waste, same has to be

audited as a part of compliance procedure.

Proper signs boards indicating the nature of hazardous wastes should be

displayed at storage and handling area. Selected routes for vehicles transporting

hazardous wastes should be clearly identified within the facility. Transportation

should be carried out in a manner which minimizes risk to the health and safety of

employees, the public and the environment.

The operator should make sure that vehicles used for waste transportation are fit

for purpose with respect to compliance with relevant regulations. All loads carrying

waste should be properly identified, segregated according to compatibility and

secured to prevent sliding or shifting during transport. The drivers and cleaners of the

trucks are to be trained. In case any exposure for eyes or body of any person with

hazardous wastes, emergency showers and eye wash stations should be provided

within the work area.

Any maintenance work in the waste storage and handling area should be

authorized by plant management, and maintenance work should be carried out under

the supervision.

3.10.2 Feed Point Selection:

Various feeding points are being used to feed waste into the cement production, They

are:

– through main burner at the rotary kiln outlet end;

80

– through feed chute at the rotary kiln inlet end

– through secondary burners to the riser duct;

– through precalciner burners to the precalciner;

In the current study, the wastes were introduced to the rotary kiln inlet.

Before starting the co-processing, the feed rate was estimated, for particular kilns,

keeping in view the following practical impacts on the cement kiln:

o Impact on heat consumption

o Impact on kiln production rate

o Impact on power consumption

o Impact and conclusions on flame temperature

o Impact on clinker quality

The feed rate for both the hazardous wastes was calculated for Kiln inlet and

calculated feed rate of 0.3 tons per hour was maintained, Averagely the coal feed rate

(average net calorific value of 4145 Kcal/Kg) in the kiln during the trial burn was

29.73 tons per hour. The n - Butanol residue has the gross calorific value of 5584

Kcal/Kg. Hence, the thermal substitution rate (TSR) was 1.27 %. The (Solar

Evaporation Pond Sludge waste has the gross calorific value of 7238 Kcal/Kg. Hence,

the thermal substitution rate (TSR) is 1.44 %. (Image 3.8)

81

Image 3.7 Various Components of Waste Feeding System

3.11 Trial Burns and Types of Wastes Used:

Trial burns:

Emissions testing performed for representative compliance with the

destruction and removal efficiency and destruction efficiency performance

requirements and regulatory emission limits, Central pollution control boards,

standards limits for common hazardous waste incinerator is used as the basis for

establishing allowable operating limits.

Trial burns are suggested to show obliteration of wastes consisting of,

containing or contaminated with persistent organic pollutants. To verify the capability

of a cement plant to efficiently destruct pollutants in a permanent and sound way, the

destruction and removal efficiency (DRE) or destruction efficiency (DE) should be

determined, as demonstrated in a trial burn.

The trial burn involves selecting a pollutant in the waste feed, and sampling

and analysis to determine input and emission rates of the same pollutant. A trial burn

82

typically consists of a series of tests and there are usually three runs performed for

each test.

The n – Butanol residue is generated from the manufacturing of product

called Carbamazepine an antiepiliptic drug. The SEP Sludge is generated from the

Solar Evaporation Pond existing at Jubilant. The SEP Sludge is collected over a

period of time for natural concentration in the elevated tanks for evaporation

purposes. Mainly contains distillation bottom residues are being used in trial burn.

3.12 Monitoring Plan of Emissions, Products, Analytical Parameters

and Instruments Used:

Emission monitoring conducted to allow authorities to check compliance with

the conditions in operating permits and required regulations, and to help operators

manage and control the process, thus preventing emissions from being released into

the atmosphere.

For self-monitoring activities the use of internal quality management

laboratory systems can be used and periodic check by an external accredited

laboratory to evaluate the internal lab performance.

Table.3.7 List of Emission Parameters monitored during Coprocessing

S. No Parameter Method

1 Particulate Matter USEPA (5/17)

2 SO2 USEPA (6A/B)

3 HCl, HF USEPA 26 (ion chromatography)

4 HBr USEPA 26 (ion chromatography)

5 NOx Instrumental (electrochemical sensor)

7 Hg (particulate & gaseous) USEPA 101 A (cold vapour AAS)

8 Metals (particulate & gaseous) -

Antimony, Arsenic, Cadmium,

Chromium, Cobalt, Copper, Lead,

Manganese, Nickel, Thallium,

Vanadium, Zinc.

USEPA 29 (IP-MS)

83


9 Dioxins & Furans USEPA 23A

10 TOC / Total Hydrocarbon

(continuous monitoring for 24

hours)

USEPA Method 25 A

11 Benzene NIOSH 1503

12 PAH (particulate & gaseous) TO13

13 NH3 Indo phenol

Hourly samples of all raw materials (lime stone, bauxite & iron ore), raw

meal, kiln coal, calciner coal, clinker and n – Butanol residue and SEP sludge were

collected and one composite sample on daily basis was made. The parameters that

were analyzed in all the samples mentioned above are listed in Tables 3.7, 3.8, 3.9 and

3.10.

Table 3.8 Analysis Parameters for Raw Meal and Coal Samples


1 Antimony, Arsenic, Cadmium, Chromium,

Cobalt, Copper, Lead, Manganese, Nickel,

Thallium, Vanadium, Mercury, Zinc.

Microwave digestion &

AAS/ICP MS/APHA

2 Total Organic Carbon NCEA-C-1282

Table 3.9 Analysis Parameters for Clinker Samples

S. No

Parameter Method



Thallium, Vanadium, Mercury, Zinc

Microwave digestion

& AAS/ICP

MS/APHA

84

Table 3.10 Analysis Parameters for n – Butanol residue & SEP Sludge




Thallium, Vanadium, Mercury, Zinc.

Microwave digestion &

AAS/ICP MS/APHA

2 Gross Calorific Value By Bomb Calorimeter

3 Ultimate Analysis (C, H2, N2, O2) By CHNSO Analyzer

4 Proximate Analysis (Moisture, Ash, Volatile

Matter, Fixed Carbon)

By Thermo

Gravimetric Analyzer

5 Total Organic Carbon NCEA-C-1282

6 Total Petroleum Hydrocarbon EPA 1664

7 Organo Chlorine Compound AOAC 8270 C

8 VOCs & Semi VOCs ASTM 3686

9 PCBs EPA 8082

10 PCPs EPA 8270C

To measure and control the relevant compounds of the emission of the

cement kiln different emission measuring devices were installed at the main stack.

These devices are controlled by a so-called calibration measurement (Images 3.9, 3.10

and 3.11).

3.12.1 Dust & other Gaseous Monitoring:

M/S Vayubodhan makes Stack Sampler (Model No. VSS1) to collect sample

manually as per USEPA guideline with valid calibration certificate of Rota meter, Dry

Gas Meter, Sampling Nozzle, Vacuum gauge, Temp indicator, Pitot tube.

• Flue Gas Analyser – Kane 9106 (for grab sampling) with valid calibration

• Certificate from external agencies.

• Kane 9106 : NO, NO2, CO,

• VOC analyzer (FID) TCS Electronica s.r.l.Serial no. 4871-5

• Total Organic Carbon (online GC-FID for 24 hours monitoring)

85

3.12.2 Exhaust Gas volume stream velocity:

The velocity profile was measured using S type Pitot tube according to USEPA

guideline method no.2.

• S Type Pitot tube

• M/s Vayubodhan Upkaran Pvt. Ltd. design

• Validated with calibration certificate

• Dynamic pressure

• Digital manometer

• Calibrated by M/s Vayubodhan Upkaran Pvt. Ltd.

• Ranges: 0 -1300 [mmWC]

• Accuracy: ± 1 [%] of measuring range

• Static pressure

• Digital manometer

• Calibrated by M/s Vayubodhan Upkaran Pvt. Ltd.

• Range: 0 - 1300 [mm WC]


• Ambient pressure

• Aneriod Barometer, Barigo, Germany

• Range: 940 - 1060 [mbar]


3.12.3 Exhaust Gas Temperature:

During the whole measuring period the temperature of the exhaust gas was

measured in one point of the cross section area of the stack with a K type

thermocouple in connection with a display unit.

• Temperature range: 0 - 1300 [°C]

• Accuracy: ± 0.3% + 1°C

86

3.12.4 Dust:

Sample was taken isokinatically as per method given in USEPA 17 by using

M/s. Vayubodhan make Stack Sampler model VSS 1 to collect sample manually.

3.12.5 Nitrogen monoxide (NO):

The measurement of the compounds NO, was carried out with the continuous

multigas-analyzer Quintox 9106 (Kane International Ltd. UK) according to USEPA

7 E

• Quintox Multi-gas-analyzer:

Kane International

Measuring ranges:

• NO: 0 - 5000 [ppm]

• CO2: 0 - 20 [vol-%]

• O2: 0 -25 [vol-%]

Extraction and conditioning of the sample gas:

• Extraction probe: High-grade steel head with connected glass-filtercase.

• Dust filter: Glass fiber thimble

• Sample gas connection tubes: SS 3 [m] length between extraction probe and

analyzer

3.12.6 Carbon dioxide & Oxygen:

The measurement of CO2 & O2 was carried out by using Orsat apparatus as

per

USEPA method No.3B. Fresh absorbing solution (KOH & Potassium

pirogalol solution) was prepared at site and calibrated against oxygen in fresh

air.

3.12.7 Sulphur dioxide (SO2):

For the measurement of the sulfur dioxide (SO2) was absorbed into a medium

containing 6% H2O2 at a sampling rate of 2 L per min for 45-60min using 2 impinges

87

in series. This was transferred to the laboratory under refrigeration. Analysis was

performed as per USEPA 6B

• Sampling Instrument:

• Vayubodhan Make Stack Monitoring Kit (VSS 1)

Measuring range:

• 0 - 10 [ppm] (diluted gas)

• 0 - 1000 [ppm] (exhaust gas)

• Absorption:

• 2 x 2 impingers (repeat determination)

• H2O2-solution, 6 [%], 50 [ml] per impinger

• Transport in closed PE-bottles

3.12.8 Moisture Content:

The moisture content was measured by condensation method as per prescribed

USEPA 4. Condensed moisture in impinger was measured in a calibrated measuring

cylinder and weight difference in silica gel was measured in four digit Metellar

balance.

3.12.9 Hydrogen Chloride & Hydrogen Fluoride:

The used method is described in USEPA 26.



• Analysis:

• By using Ion Chromatograph

• Extraction:


• Dust filter: Glass fiber Thimble

88

• Absorption:

• 2 x 2 impinges (repeat determination)

• 0.1 N Noah & 0.1N H2SO4, 50 [ml] per impinger


• Analysis:

• Analytic determination according EPA26

• Ammonia

The used method is described in USEPA 6A/B modified absorption in dilute H2SO4

• Extraction:

• Extraction probe: Vayubodhan Make Stack Monitoring Kit (VSS 1)


• Absorption:


• 0.1 N H2SO4, 50 [ml] per impinger


3.12.10 Heavy Metals:

Heavy metal concentration was determined according to the method described in

USEPA 29.

• Extraction probe:



Absorption line 1:

• Absorption for As, Cd, Co, Cr, Ni, Pb, Sb, Sn, Tl and Zn

• 2 x 2 fritted impingers, cooled by ice water

• Absorption solution: 4.3 [%] HNO3 + 2.3 [%] H2O2

89

Absorption line 2:

• Absorption for Hg

• 2 x 2 fritted impingers, cooled by ice water

• Absorption solution: 2.0 [%] KmnO4 + 10.0 [%] H2SO4

Analysis

• Made by ICP-MS,

• ICP-MS for Cd, Co, Cr, Ni, Pb, Sb, Sn, Tl and Zn

• ICP-MS for Hg

•

3.12.11 Volatile Organic Compound (VOC):

The measurement of volatile organic compounds was continuously measured with a

online flame ionization detector

• VOC analyzer (FID) TCS Electronica s.r.l.Serial no. 4871-5

• Total Organic Carbon (online GC-FID)

• Extraction and conditioning of the sample gas

• Extraction probe: High-grade steel – heated sampling probe

• Reference gases:

• Zero gas: N2 5.0

• Span gas 82.5 [ppm] propane (C3H8) in N2, (± 2[%])

• Introduction: before the filter of the extraction probe

• Manufacturer: Amith Air Gas, Delhi

• Bottle number: 80534 SL Gas (certified)

• Manufactured 15.04.2004 with a stability guarantee of 12 month

3.12.12 Benzene:

NIOSH method 1501 was used for non-continuous benzene (benzol) measurement in

the plant exhaust gases. This method is based on adsorptive enrichment in activated

carbon followed by liquid desorption.

90

• Adsorption on activated charcoal tube

• Flow of 1.0 [l/min]

• Desorption with CS2

• Gas chromatography with flame ionization detection

3.12.13 Dioxin/Furan:

Dioxins and furans were measured according to USEPA 23

Extraction: SGS

Analysis: SGS, IAC, (Institute for Applied Chromatography), Division of SGS

Belgium N.V. at Antwerp, Belgium

3.12.14 Ammonia:

For the measurement of the ammonia (NH3) was absorbed into a medium

containing 0.1 N H2SO4 at a sampling rate of 2 L per min for 45-60min using 2

impingers in series. This was transferred to the laboratory under refrigeration.

Analysis was performed as per USEPA 6A/B modified method.



Measuring range:

• 0 - 10 [ppm] (diluted gas)

• 0 - 1000 [ppm] (exhaust gas)

• Absorption:


• H2SO4-solution, 0.1 N, 50 [ml] per impinger


• Analysis:

Analytic determination according to USEPA 6A/B modified.

91

Image 3.8 Laboratory Equipments used for Waste Analysis

92

Image 3.9 Instrument for Measuring Dioxin & Furan

Image 3.10 FID TOC Analyzer

93

3.13 Schedule of Observations & Duration of Trial Burns:

The purpose of the co-processing trial is to show that the kiln is able to co-process

hazardous waste in an eco-friendly manner. The emission monitoring results from the

trial burn serves as a basis to show the environmentally sound performance of

co-processing to the authorities and other stakeholders in the waste disposal activity.

The co-processing trial of n – Butanol waste from Jubilant was carried out in three

phases (namely, Pre Co-processing, Co-processing and Post Co-processing) and was

as per the Holcim Guidelines. There was a kiln stabilization period with conventional

fuel for a span of 24 hours before the start of the trial. Table3.11 provides the list of

emission parameters which were monitored during each phase of the trial.

Table 3.11: Emission Monitoring during Each Phase of the Co-processing Trial

S. No Parameter Method No. of

Sample Frequency

1 Particulate Matter USEPA (5/17) 3 Once in each shift

2 SO2 USEPA (6A/B) 3 Once in each shift

3 HCl, HF USEPA 26 (ion

chromatography)

3 Once in each shift

4 HBr USEPA 26 (ion

chromatography)


5 NOx Instrumental

(electrochemical

sensor)


7 Hg (particulate & gaseous) USEPA 101 A

(cold vapour AAS)


8 Metals (particulate &

gaseous) - Antimony,

Arsenic, Cadmium,

Chromium, Cobalt, Copper,

Lead, Manganese, Nickel,

Thallium, Vanadium, Zinc.

USEPA 29 (IP-MS) 3 Once in each shift

9 Dioxins & Furans (I-TEF)* USEPA 23A 1 Once in each

phase

10 TOC / Total Hydrocarbon

(continuous monitoring for

24 hours)

USEPA Method 25

A

1 Once over a

period of 24 hours

11 Benzene NIOSH 1503 3 Once in each shift

12 PAH (particulate &

gaseous)

TO13 1 Once in each

phase

13 NH3 Indo phenol 3 Once in each shift

*Sampling by SGS India & testing by SGS Institute for Applied Chromatography, Belgium, accredited

to ISO 17025 by Beltest.

94

3.14 Process Charts and Measurements:

During the pre co-processing, co-processing and post co-processing phase of

the trial burn, Computer printouts of the hourly process chart of Kiln sections were

taken during the entire period of the co-processing trial. The following parameters

were monitored:

1. Kiln Torque (Kilo Watt - KW)

2. Kiln Feed Rate (tons per hour - TPH)

3. Coal Feed Rate to Kiln (tons per hour - TPH)

4. Coal Feed Rate to Calciner (tons per hour - TPH)

5. Last Cyclone Bottom Temperature (0C) Stream 1

6. Last Cyclone Bottom Temperature (0C) Stream 2

7. Kiln Speed (revolutions per minute - RPM)

8. Pre Heater Outlet Temperature (0C) Stream 1

9. Pre Heater Outlet Temperature (0C) Stream 2

10. Pre Heater Draft (mm WC) String 1

11. Pre Heater Draft (mm WC) String 2

12. Pre Heater Outlet O2 (%) String 1

13. Pre Heater Outlet O2 (%) String 2

14. Pre Heater Outlet CO (%) String 1

15. Pre Heater Outlet CO (%) String 2

16. Kiln Inlet Temperature (0C)

The detailed results of the monitoring carried out during the co-processing trial are

provided and discussed in the next chapter. It is to be noted that the results are the

average values for the number of samples collected at the time of emission monitoring

during the trial.

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