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PLANNING A CENTRAL HAZARDOUS WASTE TREATMENT AND DISPOSAL

FACILITY :

ANALYSIS OF TECHNOLOGY ALTERNATIVES

by

Rahul Datar

A thesis submitted in partial fulfillment of the requirements for the degree of Master of

Engineering

Examination Committee Dr. C. Visvanathan (Chairman)

Prof. Chongrak P.

Prof. Fujiwara O.

Nationality Indian

Previous Degrees Bachelor of Civil Engineering

University of Poona, Maharashtra,

India

Scholarship Donor Working Student (EEP)

Asian Institute of Technology

School of Environment, Resources and Development

Bangkok, Thailand

December 1998

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Ackowledgement

I wish to express my deepest gratitude and thanks to my advisor, Dr. C. Visvanathan.

Knowing the dual responsibilities for a work student his understanding and forgivances madeit possible for me to continue on my thesis work without giving unjustice to my

responsibilities as a project employee. I am thankful to him for his constant encouragement,

guidance and perservance.

To my committee members, Prof. Chongrak Polprasert and Prof. O. Fujiwara, I owe myprofound thanks for sparing time for their advice and support with valuable suggestions.

I wish to extend my sincere gratitude to the French project on Energy-EnvironmentEngineering Management, which supported my studies and made it possible for me to

complete my thesis.

I owe special thanks to my friend Mahesh Patankar, for his valuable comments and

suggestions from time to time. I also wish to thank my other friends Shabbir, Dhanshree,Rajesh for their valuable support and help.

Without the help and suggestions from Dr. Yaaron from GENCO, Thailand it would have

been impossible for me to gain insight on the practical aspects involved in my studies.

To Dr. Prasad Modak, EMC, India, I owe my sincere thanks and appreciation for his valuable

suggestions and time to time support in this study.

To my beloved parents, my heartfelt thanks for the love, encouragement and immense moral

support they have always given me and continue to do so.

Last but not the least I would like to thank and pay tributes to all the faculty and teachers that Ihave had the fortunate opportunity to learn from.

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Abstract

Treatment of Hazardous wastes involves complex sequences and meticulous planning to

ensure adequate and proper achievement of desired objectives of stabilisation, detoxificationand secured disposal. Dedicated industrial treatment can achieve more success in these terms

considering the advantages of consistent waste compositions, minimum transportation risk,

better control and modifications in treatment. However, one significant issue, that is the capitaland operating costs of hazardous waste management makes it an impractical and non-feasible

and mostly undesired option.

Central Hazardous Waste Treatment and Disposal Facility (CHWTDF) has attempted to solve

this precise problem, by using the economies of scale. However, it has simultaneously invitedother problems like optimum technology selection to maximise treatment objectives, planning

and management aspects to economise the operations.

This study attempts to address the issue of appropriate technology selection by studying the

interactions in the waste compositions from certain typical industrial sectors and the rationalselection and sequencing of the technologies to achieve maximum benefit, lower costs, better

material recovery potential and better monitoring control on hazardous waste treatment.

It was found that Analytical Hierarchy Process can be efficiently used to compare technology

alternatives on the basis of various criteria. An in-depth sensitivity analysis can also beperformed to appraise the variations in the technology selection rankings with respect to

changes in the criteria.

An Excel based spreadsheet presents the technology selection with emphasis to waste

segregation, waste generation variance factors and selection of technology options. A case

study has been developed to demonstrate the feasibility of the framework.

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Table of Contents

Chapter Title Page

Title Page iAcknowledgement ii

Abstract iii

Table of Contents ivList of Figures vi

List of Tables viiList of Abbreviations viii

1 Introduction 11.1 Background Information 1

1.2 Objectives of the Study 3

1.3 Scope of the Study 3

2 Literature Review 52.1 Definitions of Hazardous Wastes 5

2.2 Inventorisation and Characterisation of Hazardous Wastes 82.3 Problems Associated with Hazardous Waste Management 9

2.3.1 Lack of Technology and Funding Expertise 9

2.3.2 Lack of Inventorisation and Characterisation ofWastes 9

2.4 Treatment / Disposal Technology Selection 11

2.4.1 Disposal Standards 112.4.2 Treatment of Hazardous Wastes 11

2.4.3 Individual Industrial Hazardous Waste Stream

Treatment 13

2.4.4 Centralised Hazardous Waste Treatment and 15Disposal Facility (CHWTDF)

2.4.5 Analytical Hierarchy Process as a Means to Select

Optimal Alternatives of Technology Schemes 192.5 Effect of Waste Minimisation (WM) Programmes in the

Industry 20

2.6 Waste-Waste Compatibility 212.7 Pricing Structure of CHWTDFs 24

3 h d l 2

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Chapter Title Page

4 Framework, Results and Discussion 32

4.1 Information Procured (Knowledge Base) 324.1.1 Definitions of Hazardous Waste 32

4.1.2 Standards on Effluent and Sludge Disposal 34

4.1.3 Hazardous Waste Inventory for Selected Industries 354.1.4 Waste Generation Variance Factors 43

4.1.5 Waste Treatment and Disposal Technologies forHazardous Wastes 45

4.1.6 Cost Estimations and Assumptions for Treatment

and Disposal 564.2 Conceptual Framework 57

4.2.1 Rationale for Waste Mixing / Segregation 58

4.2.2 Waste Generation Variance Factors 62

4.2.3 Selection of Unit Operations 63

4.2.4 Rationale and Rules for Selection of Technologiesin Unit Operations and Routing 65

4.2.5 Use of Analytical Hierarchy Process (AHP) forTechnology Selection 73

4.2.6 Development of Pricing Model for Charging

Member Industries 76

5 Conclusions and Recommendations 80

5.1 Conclusions 805.2 Recommendations 81

References 82

Appendix A Case Study Example using AHP and Excel Spreadsheet

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List of Figures

Figure Title Page

2.1 Comparison of Developed and Developing Regions in Termsof Hazardous Waste Generation 10

2.2 Annual Hazardous Waste Generation in the USA 10

2.3 Influence of Basic Characteristics (% moisture and organics)on the Choice of Particular Treatment Methods 13

2.4 A Typical Conventional Treatment for Electroplating Industry 14Wastewater

2.5 A Typical Waste Technology Flowsheet for CHWTDFs 16

2.6 Waste-Waste Compatibility 233.1 Schematic of Framework Approach 28

4.1 Sedimentation / Floatation Unit 48

4.2 Schematic of Framework 74

4.3 Schematic of a Closed Loop 754.4 A Typical for AHP Structure for Solvent Recovery

Technology Selection 75

4.5 Sensitivity Analysis Screen for Solvent RecoveryTechnology Selection 76

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List of Tables

Table Title Page

2.1 Summary of Definitions 72.2 Possibilities of Treatment and Disposal of Industrial Wastes 12

2.3 Hazardous Waste Treatment Technologies 14

2.4 Unit Process Removal Efficiencies and Costs 192.5 Potential for WM Opportunities in Industries 21

4.1 Form-based Classification 324.2 Size-based Classification 33

4.3 Waste Category-wise Classification 33

4.4 Effluent Standards (Surface Waters) 344.5 Hazardous Waste Incinerator Emission Standards 34

4.6 Typical Leather Manufacturing Operations: Materials Used

and Hazardous Wastes 35

4.7 Leather Products Manufacturing Waste Descriptions 36

4.8 Typical Paper Industry Operations: Materials Used andHazardous Wastes 37

4.9 Typical Metal Manufacturing Operations Materials andHazardous Wastes 39

4.10 Typical Chemical Manufacturing Operations Materials Used

and Hazardous Wastes Generated 404.11 Typical Pharmaceutical Industry Operations Materials and

Hazardous Wastes 42

4.12 Typical Agrochemical Industry Operations Materials Used andHazardous Wastes 42

4.13 Summary of Hazardous Waste Characterization from Selected

Industries 43

4.14 Waste Minimisation Potential in Various Selected Industries 444.15 Applicability of Incinerator Systems 54

4.16 Cost Estimations of Selected Technologies 56

4.17 Waste Waste Compatibility 604.18 Waste Generation Variance Factors 63

4.19 Applicability of Treatment / Disposal Technologies to Specific

Hazardous Waste Contaminants / Classes 66

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List of Abbreviations

AHP Analytical Hierarchy ProcessBOD Biochemical Oxygen Demand

C Carbon Adsorption

CETP entral Effluent Treatment PlantCHWTDF Central Hazardous Waste Treatment and Disposal Facility

CN CyanidesCOD Chemical Oxygen Demand

D Dewatering

ED ElectrodialysisF Filtration

I Ion Exchange

L Secure Landfill

M Membrane Processes

N NeutralizationP Chemical Precipitation

PCB Polychlorinated BiphenylsPOHC Principle Organic Hazardous Constituent

PPP Pollution Pays Principle

RO Reverse OsmosisSCF Super Critical Fluid Oxidation

SF Sedimentation / Floatation

SS Solvent Stripping or Suspended Solids (as specified)ST Chemical Stabilization

T Thermal Technology

UF Ultrafiltration

VOC Volatile Organic CompoundsWM Waste Minimization

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Chapter 1

Introduction

1.1 Background Information

Industrialisation and Urbanisation has given rise to the production of a wide variety of

industrial and consumer products, by-products and wastes. A major fraction of the wastesgenerated constitute the Special or Hazardous wastes. Hazardous wastes are wastes, which

possess certain specific properties with respect to their impacts on the environment and theliving world on the planet. As the name suggests hazardous wastes clearly pose a threat or

hazard to the environment. Till the mid seventies hazardous waste was referred to special

industrial waste or chemical waste (LaGrega et al, 1994). The degree of hazard posed might bedifferent for different wastes, but it is not the only criteria to evaluate the impact of the hazard.

Batstone et al (1989) reports that a true distinction is between those wastes which pose a

potentially high risk to human health and those wastes, where the hazard is much less, but the

quantities are perhaps much greater.

Typical examples of hazardous wastes as reported by LaGrega et al (1994) would include

heavy metals such as chromium, mercury or nickel, solvents, cyanide wastes, pesticides orpolychlorinated biphenyls (PCBs) or oil and grease laden wastes with toxic metals (e.g. sludge

from leaded petrol storage tanks).

Generation of Hazardous or special wastes, as often called, has been on the rise since the last

two decades, with increased industrialisation and urbanisation. Since 1950, there has been a

tremendous increase in the production of organic chemicals to satisfy our demand forconsumer goods, as well as an increased demand for valuable metals. It is reported in the US,

a per capita generation rate of 2400 pounds (1200 kg) per annum (Wentz, 1989). As many as

100,000 chemical substances are used commercially around the world, and for many produced

in high volumes (10,000 metric tons per year), no data on toxicity and characteristics isavailable (Shen, 1998). Newer chemicals continue to be produced at an amazing rate and little

data is available for characterizing the hazardous components or wastes from the manufacture

of consumption of these chemicals.

Obtaining reliable information on the quantities or types of hazardous wastes generated in the

world, is extremely difficult (Batstone et al, 1989). This inventorisation of the hazardous wastegenerated is a function of many parameters such as, the basic definition of hazardous waste,

industrial manufacturing technologies, material inputs etc.

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There are several options to the treatment approach schemes, from the point of view of

feasibility as well as policy. One approach is to impose onsite treatment and emission control

for the industries as is done in the case of conventional wastewater treatment. Anotherapproach is to go for a common or central treatment plant for a cluster of industries in an

industrial zone. These are commonly called as Central Hazardous Waste Treatment and

Disposal Facilities (CHWTDFs)

The first approach has proved economically better for conventional non-hazardous waste but

for hazardous wastes, it involves substantially high capital and operational expenditures fromindividual industries for complete onsite treatment. Secondly, temporary onsite storage of

waste increases the hazard risk considerably for the industry. For the regulatory authorities, itseems to be an easy alternative however, monitoring for regulatory control will become

cumbersome and unmanageable for them.

The second approach of CHWTDFs is many times preferred, primarily because it absorbs all

the hurdles of hazardous waste treatment in one time, thereby greatly reducing the individual

efforts and risks. Centralised facilities are desirable because of opportunities for efficient

administrative and environmental regulatory control as well as to capture the economies of

scale (Ellis et. al., 1985). However, this requires an integrated approach to design of treatmentoptions. The obvious reason being the large variety and complexity of waste quantum and

characteristics of a combined waste from a cluster of different industries. Industrial estates orzones are of two types viz. Dedicated to a particular industrial sector (e.g. a conglomeration of

electroplaters) or Mixed industrial sector. In the former case planning and design of treatment

facility is relatively easier in terms of capacities and type of treatment / disposal. Suchfacilities would show a fairly consistent efficiency of treatment. This is due to the fact that the

incoming waste characteristics are consistent over time. In the latter case however, the design

of a facility involves a careful estimation and prediction of waste characteristics and itsvariability, optimal technology selection to accommodate all possible waste types and long

term disposal options so as to sustain the facility over a longer period.

This integrated approach involves the selection of technologies in the CHWTDFs based onoptimisation against various waste characteristics, availability and feasibility of technology

and economics, etc.

Other equally important issues requiring detailed investigations in the planning and design are

feasibility of the industrial belt organisational framework, financing the facility, operational

setup of the facility.

This study is aimed primarily at investigating the issues involved in the technology selection

f h C d d l i l f k f h l i / i i i

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1.2 Objectives of the Study

1. To develop a conceptual framework for the Treatment Technology Selection in the designof CHWTDFs. A Microsoft Excel / Visual Basic for Applications (VBA) based

application will be developed based on the theoretical framework. The spreadsheet wouldpresent a casestudy example based on the framework developed in the study.

2. To develop a basic pricing model for distribution of the CHWTDFs costs, based on thePolluter Pays Principle (PPP).

1.3 Scope of the Study

As is discussed in Chapter 2, waste inventorisation and characterisation are two importantprecursors to designing any treatment facility for hazardous wastes and themselves,necessitate a detailed study of various estimation methods, their pros and cons and

applicability. Hence, uncertainties caused in inventorisation and characterisation of

hazardous wastes are not within the scope of this work. It is assumed that the input wastedata from industries is complete and accurate.

Hazardous substances produced in industrial activities include a large list of raw materials,byproducts, wastes, spent materials etc. Suitable technologies and their scales of operation

differ for many of these substances and consideration of all hazardous substances iscumbersome and impractical within this study. It will be attempted to arrive at a wastes /

contaminant list that addresses the maximum industrial hazardous waste generation.

Hence, the framework will be focussed only on the industry types and certain typicalhazardous wastes as indicated in the Chapter 3.

The focus of this study is to prepare a knowledge base necessary for selecting appropriatetreatment technologies for a CHWTDF as a function of the incoming waste characteristics.Screening rules for selection and sequencing of technologies shall be studied in detail, but

optimisation and mathematical techniques for actual selection algorithm will not be

covered under this study. However, an attempt will be made to check the applicability ofAnalytical Hierarchy Process (AHP) as a means to compare alternatives rationally on the

basis of several criteria and arrive at an optimal selection of technology. The details of the

approach used are covered in Chapter 3.

As discussed in EPAV (1985) and Batstone et al (1989), a CHWTDF is prone to several

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of risk mitigation would be incorporated as certain percentages of the technology operating

costs.

It is proposed to procure real data from industries for developing the knowledge base, butin case of non-availability of adequate data, hypothetical data (for industry details and

treatment costs) shall be assumed.

Pricing of hazardous waste treatment facilities presents several complexities in terms ofcriteria and basis for charge, willingness to pay, risk evaluations etc. Several models have

been developed which try to incorporate all issues involved and bring out an empirical

relation between them, as presented in Chapter 2. Polluter Pays Principle (PPP), has beenone of the common concepts for charging in many cases. Such a PPP based simple user

charge pricing model will be prepared under this study.

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Chapter 2

Literature Review

2.1Definitions of Hazardous Wastes

The complexity involved in Hazardous Waste Management aggravates due to the large

variance found in its definitions accepted from region to region. Definition and classificationof hazardous wastes are crucial points, which govern the course and nature of the hazardous

waste management (Biswas and Sutter, 1989).

UNEP states the definition as: wastes other than radioactive wastes which by reason of their

chemical reactivity or toxic, explosive, corrosive or other characteristics causing danger orlikely to cause danger to health or the environment, whether alone or when coming into

contact with other wastes, are legally defined as hazardous in the state in which they are

generated or in which they are disposed of or through which they are transported (Batstone et

al, 1989).

US EPA definition of hazardous waste:

1. It exhibits characteristics of ignitability, corrosivity, reactivity and/or toxicity2. Is a generic waste from industrial process

3. Is a specific commercial product or intermediate or a mixture containing a listed

hazardous waste4. Is a substance not excluded for regulation under the Resource Conservation and

Recovery Act

The Resource Conservation and Recovery Act formulated in 1976 in the USA, defines

hazardous wastes to be a solid waste or a combination thereof, because of its quantity,

concentration or physical / chemical characteristics may cause mortality or serious irreversible

illness or pose a substantial present or potential hazard to human health or environment whenimproperly treated, stored, transported or disposed.

Hazardous waste is defined in the Indian context (MoE&F, 1991) on the other hand, withexclusion of wastewater (only solid and semisolid waste is included) and no specific mention

of the four criteria of corrosivity, ignitability, reactivity or toxicity. A list based standard is

enforced for compliance.

Thailand, at present does not have a formal definition for hazardous waste (preparation of

id li f d i i ) i id

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German definition follows suit closely with further exclusions of mining and agricultural

wastes, and considers toxicity as a criteria.

Philippines definition states that materials which are inherently dangerous to the human body

or animals, including but not limited to, materials that are toxic or poisonous ; corrosive,

irritants; strong sensitizes; flammable; explosive.

Table 2.1 summarises the various definitions and the components thereof as regulated by

various nations.

Thus from the above comparisons it is evident that although all nations have a legal definitionof hazardous waste, different wastes in terms of form of existence, hazardous constituent, level

of hazard are considered as hazardous by different regions / nations. Of particular interest is

the information on small generators. A few nations like France, Japan and USA haveexclusions for small quantity generators but others consider all generators. This will clearly

result in less amount of waste generation (according to inventory) for these nations. As regards

the type of definition, most of the nations do not link list of processes, with the corresponding

list of wastes or concentrations, thus making inventorisation and characterisation difficult.

Special rules for mixing and residue exclusion also vary from nation to nation. As a result,only those treatment technologies are encouraged and developed by a country, which treat

wastes falling under its definition.

Moreover, as suggested by NHWMP (1989), the definition formulated during the policy

making stage should not be a constant or permanent function. Based on the levels ofindustrialisation and characteristics of wastes, the definitions should be changed. International

treaties and agreements also tend to modify the national definitions of hazardous wastes. A

rational long term design of treatment facility should incorporate this variability and allowmargins in the design for future changes.

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Table 2.1 Summary of Definitions

Source: Visvanathan (1997)

Canada

Denmark

France

Germany

India

Japan

Netherlands

Sweden

Taiwan

UK

USA

Existence of legaldefinition

Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes

Purpose

TransportTreatment / disposal

YesYes

YesYes

YesYes

YesYes

YesYes

NoYes

YesYes

YesYes

NoYes

YesNo

YesYes

Type of Definition

List of Wastes

List of Substances

List of ProcessesConcentrations

No

Yes

NoYes

Yes

Yes

NoNo

No

Yes

YesNo

Yes

No

NoNo

Yes

No

NoNo

Yes

Yes

YesNo

Yes

Yes

YesYes

Yes

Yes

YesNo

No

Yes

NoYes

No

Yes

NoNo

Yes

Yes

YesYes

Criteria

Toxicity

Toxicity of extractIgnitability /

FlammabilityCorrosiveness

Reactivity

Yes

Yes

NoNo

No

No

Yes

Yes

YesYes

Yes

Yes

Yes

Yes

YesYes

Yes

Yes

Yes

Yes

NoNo

No

No

No

No

NoNo

No

No

Yes

No

YesNo

No

No

No Yes

Yes

NoNo

No

No

Yes

No

NoNo

Yes

No

Yes

No

YesYes

Yes

No

Yes

Yes

YesYes

Yes

Yes

Special Rules

Mixing rule

Residue rule

2

2

Yes

Yes

Yes

Yes

Yes

No

No

No

No

No

Yes

No

No

No

No

No

No

No

Yes

Yes

Exclusions

Small generators1

Wastewater

Sewage SludgeMining Sludge

Agricultural Waste

No

No

NoNo

No

Yes

Yes

NoYes

Yes

No

Yes

NoYes

Yes

No

Yes

NoNo

No

Yes

Yes

YesYes

Yes

No

Yes

NoNo

No

No

No

YesNo

No

No

No

NoNo

No

No

Yes

YesYes

Yes

Yes

NoYes

No

1 Quantity is that per month below which a producer is exempt from regulations

2 Under consideration

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2.2Inventorisation and Characterisation of Hazardous Wastes

The term inventorisation refers to the methodology of estimation of the HW generationpotential for any area, region or country. As mentioned before, since hazardous waste covers

materials emanating from various stages of the industrial process and are a function of various

parameters, it is difficult to estimate the generation potential.

Some types of inventorisation methods

Based on unit level of production in industries (WHO, 1993)

Based on macroeconomic variables such as per unit of GDP, per unit of output insector, per unit of population, etc. (OECD)

Based on number of employees in the industry

Characterisation refers to the classifications and rating systems of the waste. This may be

based on origin of waste, susceptibility to treatment, chemical composition etc. Categorisation

could be on the basis of treatability, transport / storage, toxicity and compatibility of wastes.

Some other factors causing the variation in estimated values are:

Type of Inventorisation method used,

Lack of documentation on industrial production and waste generation in developing

nations

Lack of representative and adequate monitoring to assess characteristics of waste

Sloan (1993) specifies nine categories of waste types, which address almost all the hazardous

wastes from industries. The categories are as follows:

1. Inorganic Aqueous Liquids2. Inorganic Aqueous Liquids with

Organic components

3. Concentrated Organic Liquids4. Organic Solids

5. Inorganic Solids

6. Organic Sludges7. Inorganic Sludges

8. Organic Gases

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Such a characterisation classifies wastes into classes according to the nature (physical and

chemical) but each class will contain an exhaustive list of wastes.

Significant factors in the variance in these definitions could be the level of

industrialisation and the Best Available Technologies (BAT) in the nation. Although it

might be established that a certain element is highly toxic or hazardous, if the currentlyavailable and techno-economically feasible treatment technologies do not address this

element, it will be futile to introduce a regulation on that element. It might be better in

such a case to investigate for material substitution in the industry, instead.

2.3Problems Associated with Hazardous Waste Management

Batstone (1989) reports the specific problems in Hazardous waste management of the

developing countries. General control over pollution and waste disposal is often poor;

Generators are unaware of the hazard of their waste; stockpiles of wastes awaiting

treatment and disposal (bad planning of facilities); limited resources (in terms ofmanpower and financial assistance) and socio-political reasons.

2.3.1 Lack of Technology and Funding Expertise

In addition to the above reasons, one major factor is the lack of expertise on planning and

managing a hazardous waste treatment facility. Foreign consultancy assistance is limitedto individual industrial treatment and is expensive. For central facilities it is necessary to

plan and design a facilitiy suitable to specific conditions of the region and its industries

and it is required to develop a skilled team for the operation and management. Such aneffort requires a multidisciplinary approach to the problem.

2.3.2 Lack of Inventorisation and Characterisation of Wastes

Treatment technologies are a direct function of the waste quantum and characteristics.

The performance of any given treatment scheme shall depend on the influent wasteparameters. Thus it is necessary, in the design of any treatment scheme, to have data on

the volume, characteristics of wastes and frequency of generation.

There is a marked difference observed in the estimated hazardous waste generation

patterns in the developed and the developing countries, or even between two regions in

the same area. Typical values as shown by ERM, 1997 and LaGrega et al, 1994 areillustrated in Figure 2.1, below.

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Figure 2.1 Comparison of Developed and Developing Regions in Terms of

Hazardous Waste Generation

It is clear from the above figure that a city in the USA far exceeds hazardous waste

generation as compared to Sri Lanka. It is possible that since the US regulation includes a

large amount and type of material under hazardous waste, it reports high values. Apartfrom the inventorisation method used, the amount of industrialisation, technology used

etc. also influence the generation potential. Figure 2.2 presents the annual waste

generation in the US. The decrease after 1994 can be largely attributed to new policy

bans, new technologies and waste minimisation programmes.

Figure 2 2 Annual Hazardous Waste Generation in the USA

0

20

40

60

80

100

120

New Jersey (USA) Sri Lanka

Location

Inorganic Organic

0

0.5

1

1.5

2

2.5

1992

1993

1994

1995

1996

Year

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2.4 Treatment / Disposal Technology Selection

Choice and degree of treatment are a function of the desired level of contaminants in thefinal residue to be disposed.

2.4.1 Disposal Standards

For conventional waste treatment, the effluent standards (liquid streams) are basically a

function of the type and carrying capacity of the receiving body. Consequently, standardsvary for coastal, inland water, river, lake effluent disposal. Since most of the solid waste

and sludges under the non-hazardous category can be degraded, they do not pose much ofa threat as regards leachability from landfills.

However, in the case of Hazardous waste, the standards are of two distinct types, viz.

Technology based and Risk based (Blackman Jr., 1993). The former are best described as

those having a rationale as a function of treatment and/or control technologies, gradationsof primitive to sophisticated processes, cost-effectiveness, economic feasibility,

aesthetics and political considerations. Examples could be requirement of Best

Practicable Control Technology on Incinerator emissions or requirement of thermalmethods for pesticide containing hazardous wastes.

The latter are based on a predetermined level of risk to the receptor population and theassociated health impacts. These address the toxic ill effects of the contaminants on the

receptors. Typical examples include standards on toxic air pollutants from industrial

emissions or leachability of heavy metals from landfilled wastes.

LaGrega et al (1994) and Batstone et al (1989) present maximum allowable standards forcertain hazardous waste contaminants such as heavy metals, phenol etc.

2.4.2 Treatment of Hazardous Wastes

LaGrega et al (1994) have classified the basic treatment methodologies for Hazardous

Wastes into the following categories:

1. Phase Separation (e.g sedimentation, stream stripping, air stripping)

2 Component Separation (e.g. ion exchange, electrodialysis)

3 Chemical Transformation (e.g. chemical oxidation, incineration)4 Biological Transformation (e.g. fixed film aerobic treatment)

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Table 2.2 Possibilities of Treatment and Disposal of Industrial Wastes

Contaminants Recovery Incineration Treatment

(physico-

chemical,

biological)

Immobilisation/

solidification

Controlled

Landfill

Effluents /

washwaters9

Acids and

alkalis9

Heavy metals 9 9 Residues

ToxicInorganics

9 9 Residues

Reactive

Wastes9

Non-toxic

inorganics9 9

Solvents, oils 9 9

Resins, paints,

organic sludge9 9

Organic

chemicals9 9 9

Pesticides 9 9

PCBs,

chlorinatedhydrocarbons 9 9

Putrescible,

biodegradable

wastes9

General suitability of various treatment methods compared to physicochemical

characteristics of waste as reported by LaGrega, 1994 presents the influence of basic

characteristics (% moisture and organics) on the choice of particular treatment methods(Figure 2.3). Such a nomogram however, limits to only the solids and organics present

and gives only a broad technology selection criteria. A rational selection, say for examplefor thermal treatment, would depend on the specific waste contaminant, combustion

byproducts, air pollution control necessary and the landfill potential of the ash residue.

High organics and low water content would only indicate the potential suitability of

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Brunner (1993) presents the type of incineration technologies, their applications for

various industrial hazardous wastes and relative merits of each. Air pollution control

systems which form an integral part of the incineration package, are also covered. It alsopresent some criteria for selection of incineration systems and their types for specific

contaminants.

Blackman Jr. (1993) present several treatment technologies for individual waste

contaminants. Physico-chemical, thermal and other technologies are covered.

Figure 2.3 Influence of Basic Characteristics (% moisture and organics) on the

Choice of Particular Treatment MethodsSource: LaGrega et al (1994)

2.4.3 Individual Industrial Hazardous Waste Stream Treatment

Design of such treatment schemes are relatively much easier since the waste volumes and

characteristics are known and the treatment facility could be designed as a sequence ofindividual treatment technologies, so as to comply with the discharge or disposal

standards.

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Figure 2.4 A Typical Conventional Treatment for Electroplating Industry Wastewater

(Biswas and Sutter, 1989)

Hazardous waste treatment alternatives as reported by Salcedo et al, (1989) indicatetechnologies for individual contaminant removal or reduction. A sample matrix ispresented in Table 2.3.

Table 2.3 Hazardous Waste Treatment Technologies

Technology Description Application

Ultrafiltration Low pressure membrane

filtration (10-100 psi) to drivecolloidal molecular weight

matter

Paint waste from

electrocoating, concentratecutting oil

Dechlorination Removal of chlorine atoms Removal of PCBs from

transformer oil

Solvent extraction Solvent extracts organics from Phenol from coke industry

Acid

Caustic

NEUTRALIZATION

CYANIDE

OXIDATION

Cyanide waste

Caustic

Chrome waste

Acid

CHROMIUM

REDUCTION

SLUDGE

STORAGE

PolymerAcid alkaline waste

MIXER

CLARIFIER

Caustic

Wastewater

Discharge

Solid

Waste

Disposal

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Individual treatment by industries requires substantial investment and repeats some of the

basic treatment units for small waste flows. Almost every industry would have aneutralisation unit to neutralise acids / alkalis, sludge separation and drying also would be

a part of many treatment processes, chemical precipitation processes would be a must for

all industries having heavy metals in their waste.

2.4.4 Centralised Hazardous Waste Treatment and Disposal Facility (CHWTDF)

An industry specific treatment as shown above, involves considerable capital andoperating cost, as well as substantial land use within the industry premises. Central

treatment systems cater to waste treatment needs of a complete industrial estate(conglomerate of various industries) and harness the advantage of economies of scale.Criteria to be used to select individual treatment processes and their sequencing for a

centralised facility are far from obvious. Conventional selection processes may not yield

cost effective solutions so optimisation is required (Ellis, 1985).

As outlined in Chapter 1, the central facilities can be of two types viz. Dedicated

industrial sector or Mixed industrial sectors, and the design and technology selection

rationale would change accordingly.

The concept of CHWTDF can be expected to differ from one region to another based on

the quantities and types of hazardous wastes. As an example, one of the largest industrialcities in the world (Shanghai) found it necessary as a result of a World Bank hazardous

waste feasibility study, to only establish a CHWTDF that consisted of a landfill, along

with a leachate stabilisation plant, laboratory and storages. Destruction of the particulartypes and quantities of hazardous wastes in Shanghai was achieved by disposal in a

cement kiln (HWMP, 1996).

Figure 2.5 presents a partial waste technology flowsheet, specifying application ranges of

technologies. However, the technologies are presented on a one-to-one basis. Alternatives

and common options need to be developed, along with estimates of removal efficienciesof each technology for waste contaminants. It is obviously impractical to include all

these technologies in a CHWTDF. A rational selection of technologies that would

accommodate all incoming waste types should be conducted and designed.

GENCO is a centralised treatment and disposal facility in Thailand catering to the major

industrial estates in Thailand (Authors Communication, 1998). GENCO accepts wasteafter pre-feasibility studies and waste consistency certification. Treatment consists of a

phased sequence of chemical stabilisation, secured landfilled, fuels blending for cement

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HalogenatedNon-halogenated

Solvents

Mineral Oil

Fuel Oil

Oil-Water Mixtures

Paint Waste

Printing Waste

Tank Cleaning Sludges

Treatment Plant Sludges

Pharmaceautical products

Mixed Organic Compounds

Tar, Bitumen, Asphalt, Pitch

AcidsAlkalis

Metal Salts

Tannery Waste

Cyanide Waste

Chromic Acid Waste

Heavy Metal

Plating Bath Sludge

Toxic Metal

Hazardous Metal Oxide

Oil Waste Recovery

Incineration

Physico-Chemical

Treatment

Co-disposal

Regeneration

Solvent Extraction

Distillation

Vacuum Distillation

Non recoverable

Residue, still bottoms

Oil Fraction

Recovery Products

Gas

Scrubbing

Slag to landfill

Scrubber Waste

Neutralisation / Precipitation

Controled Landfill

Clarified

effluent

Sludge

Detoxification

Solidification

Aqueousfraction

Exhaust gas

Rotary

Kiln

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Components of a typical hazardous waste recovery, treatment and disposal facility are

provided in LaGrega et al, 1994. A sequence of recovery, treatment and final disposal ishighlighted.

Environmental Resources Management (1997) presents the design rationale for a Central

Hazardous Waste Treatment Facility. It outlines conceptual basis for selection and alsoprovides certain cost estimates.

Selecting the treatment scheme or options for a centralised waste treatment plant is one ofthe primary hurdles and can be overcome by optimisation techniques using if-then rules

from a knowledge base with waste-technology compatibility matrix.

Evenson and Baetz (1994) have used an object-oriented knowledge based modelling

system for the selection and sequencing of appropriate unit treatment processes for a

given waste stream.

15 contaminants were chosen for consideration and a knowledge base of 10 treatment

processes was used to achieve treatment objectives from influent concentrations to

desired effluent concentrations. A three phased approach was employed, viz. identify listof possible treatment trains for given waste stream, bench scale testing of selected

technologies to assess applicability and selecting preferred option and performing

detailed engineering design for implementing the selected option.

A preliminary list of waste contaminants used was as follows:

Oil and Grease

BOD COD

Suspended Solids

Dissolved Solids

Total Solids

Phenols

Cyanides

Chromium

Lead Nickel

Zinc

Aluminium

Cadmium

Mercury

The corresponding treatment processes modelled were:

Activated Sludge

Settling

Ion Exchange

Neutralisation/ Precipitation

Filtration

Ultrafiltration

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A critical review of Evenson and Bates, 1994 indicates a limitation as regards the waste

contaminants selected and treatment technologies. Parameters such as BOD, COD, TS,

TDS do not necessarily and completely characterise hazardous waste and are notappropriate indicators of hazardous waste contaminants. Some of the heavy metals, volatile

organics, pesticides etc. have been neglected. pH, which indicates the acidity or alkalinity

of the waste needs to be included so that extent of neutralisation can be ascertained. Also,the treatment technologies indicated largely address conventional waste treatment methods.

Treatment methods such as thermal treatment, solidification / stabilisation, and disposal

methods such as incineration, secured landfills etc. have not been considered as technologyoptions at the CHWTDFs. The authors have mentioned that the contaminant list and the

technologies were considered suitable only for demonstrating the modelling approachdeveloped, and need not be essentially complete for a facility design.

Ellis et al (1985) presents a Stochastic Optimisation / Simulation of Centralised LiquidIndustrial Waste Treatment. The objective is to delineate cost effective treatment sequences

for a centralised treatment facility. Dynamic Programming (DP) forms the basis of the

optimisation process. The model is structured to permit the following user determined

choices: 1) waste types and respective volumes in the waste inventory; 2) specific

contaminants within each waste type; 3) contaminant specific density functions for wastestrength; 4) unit treatment processes (efficiencies and costs) and 5) individual contaminant

effluent standards.

The waste inventory is comprised of l waste types. Each type contains m contaminants.

Each waste type also has a specific volume Q(l). For a given waste type l, the influentconcentration of contaminant m to unit process j in stage i is written as u (i,j,k,m), where k

is unit treatment process selected in the previous stage, i-1. Similarly effluent concentration

of contaminant m, is described as w (i,j,k,m). Thus, the expression can be denoted as:

w (i,j,k,m) = (Tj Di)j given effluent u (i,j,k,m) Eq. 1

where,Di is a decision variable for choice of unit treatment processes j at stage i, and Tj is a

transition function. The transition function takes care of the selection of filtering rules etc.

Ellis et al (1985) develops a matrix of removal efficiencies of technologies for each wastecontaminant alongwith relative batch treatment cost, as shown in Table 2.4. Here again the

contaminants are the same as in Evenson and Baetz, 1994 and are inadequate. Thetreatment technologies lack some of the significant options like solvent extraction in

addition to those lacking in Evenson and Baetz, 1994. The approach of stochastic

d lli i h b j h f f h d d h

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Table 2.4 Unit Process Removal Efficiencies and Costs

UF IE AS RO CP CA OR CL FL

Batch

Treatment cost3.2 5.2 2.3 3.0 2.0 2.5 1.9 1.6 2.3

Parameter Unit Operations Removal Efficiency %

OGR 90 80 75 99 85 85 85 20 35

BOD 90 85 90 91 63 76 55 30 35

COD 88 84 79 95 48 60 75 40 45

SS 98 95 94 99 85 70 80 65 90

DS 77 84 43 93 2 75 40 2 2TS 87 90 69 96 44 73 60 34 46

Phenol 40 95 93 24 33 99 38 5 10

Pb 98 91 60 99 50 90 10 10 60

Zn 74 99 50 99 50 90 10 10 60

Ni 98 87 17 99 50 90 10 10 60

CrVI 50 99 99 90 95 95 5 10 65

CN 85 95 75 93 90 90 20 10 45

UF Ultrafiltration IE Ion Exchange AS Activated Sludge RO Reverse

Osmosis CP Chemical Precipitation OR Oil Removal CL Clarification

FL - Filtration

Recio (1991) presents another expert decision support system for hazardous wastemanagement. One of the objectives in the expert system is to diagnose potential treatment

technologies for a given waste characterisation. An inference engine with a knowledge base

is used along with if-then rules to select appropriate technologies based on influent wastes.

2.4.5 Analytical Hierarchy Process as a Means to Select Optimal Alternatives of

Technology Schemes

Partovi et al (1990) presents the Analytical Hierarchy Process for selecting the optimal

alternative from a set of options on the basis of comparisons based on various decision

criteria. These criteria are weighted on the basis of the relative significance of that criteria

in selecting a particular alternative.

Mohanty et al (1993) presents a case study example based on AHP for selection of best

CAD-CAM system alternative. In both these papers fall under the broad category of MultiCriteria Decision Making (MCDM) and the basic process of AHP is outlined as under:

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Eq. 2

Best Alternative would be the one with the highest score

2.5 Effect of Waste Minimisation (WM) Programmes in the Industry

Oldenburg and Hirschhorn (1987) state that the best way to protect health and the

environment is to not produce hazardous wastes. They have declared it to be the national

policy wherever possible, generation should be minimised or eliminated.

The different approaches of in-plant waste minimisation in the industry are:

Process modification and optimisation

Raw material and product substitution

In-plant control and house-keeping

Several Governments have followed suit and formulated policies which promote wasteminimisation in the industry. Gardener and Huisingh (1987) have listed successfulapproaches of process modifications to achieve waste minimisation. Although waste

minimisation programmes and centralised treatment facilities are antagonistic to each other,

it is not possible to completely eliminate wastes. Thus, treatment methods would have to bedevised for residues after waste minimisation programmes. The primary caution however,

is to incorporate the waste minimisation effort by the industries in the design of the

CHWTDF, so that overdesign is avoided.

Freeman (1990) outlines the waste minimisation assessment for industries and how they

affect the waste generation.

Martin et al (1994) present a compilation of several case studies on waste minimisation as awith a chemists perspective. The waste minimisation techniques covered basically focus

on the chemical industry.

Authors Communication (1998) reports a novel way of incorporating the wasteminimisation in industries for CETP design, as a factor which alters the waste generation

potential (either reduction in values or elimination of certain contaminants). This factor is

expressed as a function of time, so that it holds good for the total life of the facility. Thefactor is developed for each of the parameters such as Flow, BOD etc. that may be affected

=

=m

k

k

k

ii PLPMP

1

)*(

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Table 2.5 Potential for WM Opportunities in IndustriesSource: Freeman (1990)

Example Industries Operation

changes /

Housekeeping

In-process

recycling

Process

modification

Input

substitution

End

Product

changes

Pharmaceuticals

WeaponsRobotics

Specialty Chemicals

Positive Negative Negative Negative Negative

Rubber

Petroleum

CommodityChemicals

Paper Products

Lumber

Positive Positive Negative Negative Negative

Steel making

Nonferrous metalsTextiles

Positive Positive Positive Negative Negative

Electronic

components

Medical equipment

Positive Positive Positive Positive Negative

ElectroplatingPrinting

Positive Positive Positive Positive Negative

Foundries

Machine shops Positive Positive Negative Positive NegativeAutomobilesAppliances

Consumer

ElectronicsPaints

Positive Positive Positive Positive Positive

2.6 Waste-Waste Compatibility

Another issue of primary importance for onsite waste storage at the CHWTDF is the waste-

waste compatibility. Various types of wastes when mixed together produce different

effects, sometimes adverse and hazardous.

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As a thumb rule, the following chemical classes are not mixed or stored together:

Acids and alkalies

Bleaches

Oxidizing agents

Reducing agents

Solvents and flammables

The following are some examples of specific incompatibilities:

Ammonia with hypochlorite bleach; Nitric acid with acetic acid;

Nitric acid with sulphuric acid;

Ethyl acetate with strong alkalies;

Ethylene Dichloride with oxidizing materials;

Ethylene glycol with sulphuric acid;

1,1,1 Trichloroethane with caustic soda and caustic potash.

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2.7 Pricing Structure of CHWTDFs

A central treatment system for the hazardous wastes emanating from all the industries from

an estate would require a substantial capital and operational cost. The cost of treatment andmanagement of the facility can be recovered in various ways and several models could be

used. The most common model is to make the waste generator pay (Polluter PaysPrinciple). Various models can be used to fix the treatment fees. As reported by

Chemcontrol, 1996, the waste fees should in the initial phases be structured according to

the ability to pay principle, i.e that those categories of industries which experience goodtimes may be charged relatively more than those whose businesses are not running

profitably.

Obviously the charging or treatment fees will be a function of the treatment costs (capital as

well as operating). Thus, the primary need in this regard is to develop benchmarks forvarious individual hazardous waste treatment costs and assign factors per unit load of waste

so that based on the selected technologies a cost function could be evaluated for a particular

treatment train. The other costs (construction, management, contingency, capital loanrepayments etc.) would be based purely on the type and detail of the ownership model of

the CHWTDF and suitable direct assumptions for the same would be made in this study.

ERM (1997) presents the Sri Lankan case of CHWRDF which has been designed with a15% design overhead and 10% contingency. The development cost components of the

facility are as follows:

Site Works

Land acquisition

Civil infrastructure Services

Miscellaneous

Weigh-bridge

Treatment systems

Various technologies (e.g. incineration, solidification, solvent extraction etc.)

Buildings

The operational costs are as follows:

Personnel

Repair and Maintenance

Chemicals / raw materials

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Environmental Resources Management (1997) and NHWMP (1989) present the estimated

treatment costs for various hazardous waste treatment technologies.

HWMP (1996), indicates that the fee to be paid by the individual waste generator, in theend should match the cost of handling, treating and disposing of the particular waste

product or cost of alternative treatment. Four types of models are reported to be commonfor ownership of the CHWTDF. They are:

Government

Private sector

User cooperative Combination of government and private

Several merits and demerits are reported for each model and case specific investigations are

required for decision making. The pricing structure is a direct function of the ownership

model of the CHWTDF and charges to be paid by waste generators using the servicedepends on the agreements and conditions laid down in the ownership model.

As reported by Han (1990), typical components of a treatment cost could be:

Variable operating costs, that is in principle the marginal cost of treating one ton of waste.

In practice, cost of chemicals, utilities and similar costs can be assigned to each main

groups of waste treatment.

Fixed operating costs, that is in principle costs of items needed to handle main groups of

waste. In practice staff and maintenance related to the method of treatment such as

incineration, stabilisation.

Fixed general costs, that is in principle cost of items, which cannot be assigned to anyspecific type or category of waste. In practice, general management and administrative staff

for related expenditures on computer systems, insurance.

Capital costs, that is in principle depreciation on investment and interest. These costs can be

partly allocated to the method of treatment, while the rest to be considered as general costsnot a function of the type of treatment.

The percentage contributions of each of the above will depend on the total investment

costs. For example, if a large incinerator is involved, capital costs could be 50% andoperating costs would be 5% of yearly costs. Thus, a substantial percentage of the yearly

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MagcHPbNHPaNHPBODQeCh +++++= 2148.1852.4arg

well as operation. The costing has been based on parameters such as flowrate, BOD,

population equivalent, solids and removal efficiencies.

DETIEM (1997) presents a model for evaluating industrial effluent charges for non-compliance with discharge standards. All parameters are expressed with BOD as base

reference, in terms of cost of treatment required for exceeded value of the parameter.Coefficients have been calculated for each parameter by multiplying cost of treating BOD

with ratio of standard BOD to standard of each parameter. The base BOD treatment cost

has been estimated for a flow of 400 m3/d, BOD of 173 Kg/d. The model equation is as

follows:

Eq. 3

Where,Q flow in m

3/d

NHP1 concentration of nonhazardous pollutants type 1 (pH, temperature etc.)

NHP2 concentration of nonhazardous pollutants type 2 (sulfide, oil and grease, DS etc.)HP concentration of hazardous

a coefficient for NHP1b coefficient for NHP2 (calculated with BOD as base)

c coefficient for HP (calculated with BOD as base)Mag management and miscellaneous costs (10% of the subtotal of rest)

The hazardous waste parameters / contaminants and BOD need different technologies fortreatment, and thus the hazardous waste treatment cost is not a direct function of

conventional BOD removal cost. It would be unrealistic to base the hazardous waste factors

on BOD, as done in this model.

Authors Communication (1998) presents a review of various charging models like Malz

model, Roman formulation, Mogden formulation etc. which have been developed for CETP

waste fees. The apportioning of various costs among the member industries has been triedin various ways and the rationale of these methods is covered. All of the models formulate

an equation on the basis of various polluting parameters from member industries, in

addition to percentage factors for fixed and maintenance costs.

The above discussions imply that pricing for CHWTDF is case specific and should be

devised for individual cases. However, the approach to developing a pricing model couldhave some common features like the components of cost involved in a CHWTDF. Thus, a

framework is necessary to devise the conceptual basis, essential components (fixed and

i bl ) h i i f ll i

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Chapter 3

Methodology

3.1 Overview of the General Methodology

Hazardous Waste Management involves an array of activities starting from estimation of

waste generation to the final disposal of the wastes.

The above factors generate a variety of alternatives in terms of feasible HWM options andthese alternatives have pros and cons which need to be meticulously studied and compared, in

order to arrive at a rational, economical, long term and publicly accepted alternative for

Hazardous Waste Treatment and Disposal Facility.

In lieu of the above, a generic framework is developed in order to appraise a matrix of n

number of industry generators with waste parameters of quantity and concentrations (i, j), m

treatment/disposal options. The primary evaluating parameters for the appraisal are

performance (technology applicability and treatment efficiency) and costs, whereas the othercriteria are pretreatment requirements, input waste acceptance range of the technology etc..

Figure 3.1 presents the schematic of the approach used to develop the framework.

To arrive at suitable technology alternatives, the framework addresses the sequence of

activities necessary, starting from characterization of wastes from member industrial sectors.

The sequence used in the framework is as follows:

Classification of hazardous wastes for the given industrial estate according to Media (liquid, semi-solid and solid) Hazardous contaminants (e.g. heavy metals, organics etc.) Addition and/or segregation of waste on the basis of waste-waste compatibility

Apply waste minimisation factors on waste generation (quantity and concentration) to getfinal values to be considered in framework

Identification of Unit Operations necessary (e.g. solvent recovery etc.)

Identification and comparison of technologies within selected unit operations (e.g.stripping, centrifuging, evaporation, distillation etc. for solvent recovery) on the basis of

i i i

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Comparison of technology alternatives for certain unit operations on the basis of overallcost, performance and certain management issues, using Analytical Hierarchy Process,

ExpertChoice Ver. 9.

To illustrate the applicability of the framework, a spreadsheet based on Microsoft Excel has

been developed using Visual Basic for Applications (VBA).

The user will enter information on the Wastes and Processes and the using the knowledge base

and rules, the spreadsheet shall try to achieve the objectives and output the final alternativesselected.

Figure 3.1 Schematic of Framework Approach

Wastes- Industry Categories

- Initial Waste Volumes and

Concentrations

- Waste Minimisation Factor

Processes- Treatment Technologies

- Removal Efficiencies

- Costs (Capital and O&M)

Objectives- Achieve desired Effluent

concentrations and cost

effective technology

Knowledge Base- Waste-waste compatibility

- Waste-Technology compatibility

- Treatment Technology Selection

Considerations

Output- Treatment Sequences

USE

R

INTERACTION

SCHEMATIC FRAMEWORK FOR TECHNOLOGY SELECTION

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3.2 Components of the Framework

The framework has the following components:

Knowledge base of hazardous wastes according to industry, technologies for treatment,details on the technologies including costs

Rules and criteria for waste mixing / segregation, selection of unit operations andtechnology, waste minimisation factor predicted for the design life of the CHWTDF.

AHP structure and model to compare technology schemes

A knowledge base addressed to the following issues was prepared:

Industrial hazardous wastes and hazardous contaminants for types of industries understudy

Typical desired effluent concentrations and standards Treatment technologies for selected hazardous waste contaminants Generation of matrix of technologies, removal efficiencies and relative treatment costs, as

in Table 2.4 and other criteria of comparison. Screening rules for selecting logical sequence of technologies for combined treatmentThe requirement of a unit operation is decided on the basis of adequacy in terms of waste

requirement for justifying the use of a particular unit operation, the contaminants required to

be removed or treated. For example, the need for incineration shall be a function of thefollowing conditions encountered or satisfied:

Presence of high amount of incinerable organics, with high calorific value Waste is biologically hazardous It is resistant to biodegradation and persistent in the environment It has a flash point below 40C It cannot be safely landfilled Or if it contains organically bound halogens, lead, mercury or other heavy metals

The type of incinerator or incineration system (technology selection for a particular unitoperation) to be used will depend again on the combined waste characteristics, least cost, otherfeatures of operation.

Thus, the finalised influent waste characteristics shall be checked for these conditions and thetechnical viability shall be based on such conditions Similarly there are regulations on

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3.3 Design Rationale of Framework

The framework has been designed for a typical mixed industrial estate, the data of which has

been procured and / or generated wherever necessary and a case example has been prepared toillustrate the framework. The framework has been based on this typical example, so that the

application of the same could be readily evaluated.

Due to constraints of manual analysis, a maximum number of 25 industries are considered in

this study. If mathematical optmisation techniques are employed a much larger number ofindustries could be considered. As mentioned in Chapter 1, a knowledge base based on

individual contaminants list does not provide an industry type approach to the technologyselection. The following categories of industries have been considered for developing the

framework:

Metal Finishing Tannery Petrochemical Chemical (selected sectors) Bulk Drug / Pharmaceuticals Agrochemicals Paper ManufacturingThese industries are the most likely candidate industries producing hazardous wastes, althoughother industries also produce hazardous wastes, those have not been considered in the study.

The framework and the spreadsheet requires primary industrial data which would comprise of

the following:

Type and number of industries in the industrial estate area Production capacities of each industry Media, Quantum and Characteristics of wastes Waste Minimisation activities employed / planned Desired effluent / final concentrations of contaminantsThe analysis will consider the interactions of various options on the basis of:

Waste - Waste compatibility

As mentioned in Chapter 2 mixing / segregation of wastes at the CHWTDF from different

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Waste - Technology Compatibility and Cost

Different wastes require different treatment technologies and various operating conditions. At

the same time several technologies can be used to achieve the same result. The frameworkconceptually and critically compares the scales, technical specifications, costs, other

requirements of these technologies as a function of the incoming categories, quantums andcharacteristics of industrial hazardous waste.

Treatment costs wherever unavailable have been developed based on basic costs involved inthe technology. Finally, a matrix similar to Table 2.4, but more exhaustive has been developed

for the contaminants and treatment technologies considered in this study.

The final output from the framework shall present an appropriate technology scheme for a

facility, on the basis of performance (efficiency of treatment), cost and for a given set of wastecomposites in a given industrial sector with a combination of selected industries. As

mentioned before, an appropriate factor shall be assigned to the quantum and characteristics of

wastes, to compensate for the waste minimisation activities.

Charging Member Industries in the CHWTDF

A model has been developed to address all the costs in the construction, operation andmaintenance of a CHWTDF in terms of the waste volumes and characteristics of the member

industries. Hazardous waste management entails special emphasis on pre-treatment and post-

treatment for technologies. For example, a landfill design and costing has to be accompaniedby marginal costs for post closure activities and cost allocation has to be made to absorb these

costs during the operational period of the landfill. Other important factors like entry and exit

policies have also been addressed in the model.

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Chapter 4

Framework, Results and Discussion

4.1 Information Procured (Knowledge Base)

This section presents the knowledge base prepared based on the literature review conducted asper Chapter 2 and the methodology as presented in Chapter 3.

4.1.1 Definitions of Hazardous WasteAs discussed in Chapter 2, the definitions of Hazardous wastes differ from country to countryand region to region based on various factors. For the purpose of this study, the followingformat of classification was adopted after review of various definitions.

The three primary classifications used for arriving at the possible definition structure were:

Ministry of Environment & Forests Guidelines (India)

US EPA Guidelines World Bank WHO Classification

It is proposed that the wastes be divided on four levels of classification.

a. Form based

This categorization is based on the physical form of the waste. This classification is useful

while deciding the waste segregation and mixing rationale alongwith waste-wastecompatibility. Table 4.1 presents the classification.

Table 4.1 Form Based Classification

Form Examples

LiquidAqueous

Concentrated effluentsDilute effluents

Semi-solid

Sludges, solid wastes with maximum moisture content upto which flow isprevented

Note : Liquid and aqueous classification is according to US EPA but, these two can be mixed

(after waste compatibility analysis) prior to treatment. If the dilute fraction amounts to large

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changes in waste characteristics (due to uncontrolled and inconsistent process operations),however the generation volume is not likely to change substantially (it could be high in thefirst place due to unoptimised resource consumption). In the case of large generators on the

other hand, even a small variation in the characteristics of the waste could result in higher totalload of wastes, due to the fact that the volumes generated might be much larger in theseindustries. Table 4.2 presents this categorization.

Table 4.2 Size based Classification

Industry size Criteria

Large generators > 1000 kg/month of hazardous waste

Small generators 1000 kg > Quantity > 100 kg per month ofhazardous waste

Exempt generators < 100 kg per month of hazardous waste

Source: Ministry of Environment and Forests (1991)

c) Hazard Characteristic based

As presented in Chapter 2, the four basic criteria which necessarily define Hazardous Wastes

are presented below. Chapter 2 also presents that leachability and pathogencity have beenrecommended for Thailand. However, inclusion of these parameters is essential only in thecase of partially or untreated disposal of hazardous wastes. In this study, complete treatmenttill disposal has been considered and hence these parameters have been neglected for the sakeof simplicity.

Inflammable (flash point < 60 C) Corrosive (strong oxidants) Reactive Toxic

d) Waste Category

Here the wastes are classified according to the content and type of the contaminants present.Table 4.3 presents the categorywise classification of the same.

Table 4.3 Waste Category-wise Classification

Category Wastes included ExamplesInorganic - Metal wastes

- Acids and AlkalisCr, Ni, Cd, Zn, Cu, Cn etc.Std. Acids and alkalis

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4.1.2 Standards on Effluent and Sludge Disposal

As mentioned in Chapter 2, the standards applicable in hazardous waste treatment are a

function of the intended final disposal of the contaminants. If liquid effluent after treatment isto be discharged in surface water bodies, Table 4.4 presents the required standards. If forexample the technology used is incineration then corresponding hazardous waste incineratoremission standards, as given in Table 4.5 are applicable. For leachate from secure landfills,appropriate groundwater standards have to be applied. Both Table 4.4 and 4.5 have beenarrived at after considering and comparing relevant standards in the Asian countries.

Table 4.4 Effluent Standards (Surface Waters)

Parameter Units Standard

pH - 6-9

Oil and Grease mg/L 10

Petroleum hydrocarbons mg/L 15

Phenols and Cresols mg/L 0.2

Pesticides mg/L 0.01

Organophosphates mg/L 0.5Zinc mg/L 5

Chromium VI mg/L 0.5

Chromium total mg/L 1.5

Arsenic mg/L 0.5

Lead mg/L 0.5

Nickel mg/L 1.0

Copper mg/L 2.0

Cadmium mg/L 0.1Mercury mg/L 0.05

Colour Pcu 200

Source: Laws and Standards on Pollution Control in Thailand (1997)

Table 4.5 Hazardous Waste Incinerator Emission Standards

Parameter Units StandardParticulate mg/Nm3

30

Hydrogen Chloride mg/Nm3 100

Carbon Monoxide mg/Nm3

100

Sulphur Dioxide mg/Nm3

150

Di i & Dib f /N 3 0 2

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4.1.3 Hazardous Waste Inventory for selected industries

The selected industries as listed in Chapter 2, are as follows:

Tanning Paper Manufacturing Metal Finishing Chemical Pharmaceuticals (Formulation) / Bulk Drug Agrochemicals (Fertilizers and Pesticides)

Petrochemicals

This section has been prepared on the basis of LaGrega et al (1994), EnviroSense (1996)

4.1.3.1 Hazardous Wastes from Leather Tanning Products Manufacturing

Manufacturers of leather products are likely to produce spent solvent wastes and wastes fromthe use of lacquers, materials containing lead, dyes, or materials that produce hydrogen

sulfide. Tables 4.6 and 4.7 list the general processes/operations that use hazardous materialsand the resultant generation of hazardous waste.

Tan or finish leather products:

1. Boot and shoe cut stock and findings2. Non-rubber footwear3. Leather gloves and mittens

4. Luggage5. Handbags and other leather goods

Table 4.6 Typical Leather Manufacturing Operations: Materials Used and Hazardous

Wastes

Process/Operation Materials Used General Types of Waste

Generated

Beamhouse/Tanhouse Lime, acids, chromium,Acid/Alkaline salts

Toxic heavy metal wastes(dust and sludge)Other toxic wastes

Finishing/Trimming Chromium, solvents, dyes,lacquers

Toxic heavy metal wastes(dust and sludge)

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Table 4.7 Leather Products Manufacturing Waste Descriptions

Spent Solvents, Solvent Still Bottoms,and Other Ignitable or Toxic Wastes

Containing:

Designations/Trade Names

Trichloroethylene Tri-Clene, Trielene, Tri

Carbon Tetrachloride Perchlommethane, Tetraform, Carbona,Halon 104

Toluene Toluol, Methercid, Methyl Benzene,Methylbenzol, Phenylmcthane, Antisol IA

Methyl Ethyl Ketone Methyl Ethyl Ketone, MEK, MethylAcetone, Meetco, Butanone, Ethyl MethylKetone

Benzene Benzene

White Spirits Mineral Spirits, Naphtha, StoddardSolvent

Kerosene Kerosene, Fuel Oil

Hexachloroethane HexachloroethancEthyl Benzene Ethyl Benzene

Chilorobenzenc Monochlorobenzene, Phenylchloride

Trichloroethylene Trichloroethylene, Ethinyl trichloride, Tri-Clene, Trielene, Tri

4.1.3.2 Hazardous Wastes from Paper Manufacturing Industry

The paper industry is composed of several sectors, including:

Pulp and paper mills. which produce mechanical, thermomechanical and chemical pulps andprocess these pulps to form paper, paperboard, or building papers. Converting operations,which manufacture boxes, tablets, and other finished paper products.

Pulp is made by mechanically or chemically separating the fibers in wood or other cellulosematerials from nonfibrous material. In the kraft pulping process, used to make most chemicalpulp, a solution of sodium hydroxide and sodium sulfide dissolves the nonfibrous materials.The pulp is then bleached if white paper is being produced. Several chemicals can be used forbleaching, including chlorine gas, sodium hydroxide, calcium hypochlorite. chlorine dioxide,hydrogen peroxide. and sodium peroxide. After any filters and coloring materials are added,

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Spent halogenated solvents used in degreasing Corrosive waste generated from the use of strong acids and bases Paint waste containing solvents and paint waste with heavy metals Ink waste, which can include solvents, metals, or ignitable materials Petroleum distillates from cleanup operations.

Table 4.8 lists some typical processes/operations that might produce hazardous waste.

Table 4.8 Typical Paper Industry Operations:

Materials Used and Hazardous Wastes

Process/Operation Materials Used General Types of WasteGenerated

Chemical Pulping Acids/alkalies, lime,sulfurous acid, sodiumhydroxide, sodium sulfide

Acid/alkaline waste

Bleaching Chlorine bleaches, sulfatebleaches, chloroform,

solvents

Toxic wastewater andwastewater treatment

sludge, Acid/alkaline wastePapermaking Pigments Wastewater treatmentsludge

Sizing and Starching Waxes, glues, syntheticresins, hydrocarbons

Toxic waste, includingwastewaters add sludges

Coating, Coloring, andDyeing

Inks, paints, solventsrubbers, dyes

Solvent waste Ink wastePaint waste, Ignitablewaste, Toxic waste

Cleaning and Degreasing Tetrachloroethylene,Trichloroethylene,methylene chloride,trichloroethane, carbontetrachloride

Solvent waste, Toxic rinsewater

4.1.3.3 Hazardous Wastes from Metal Finishing Industry

Metal furniture, shelves, lockers, cabinets and fixtures Primary metal products Fabricated metal products Machinery, including electrical and electronic machinery, equipment, and supplies

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Other metal items such as clocks and watches; costume and precious metal jewelry; needles,pins, and similar notions; signs and advertising displays; burial caskets; silverware or stainlesssteel flatware

Metal manufacturing also includes facilities that are involved in metalworking activities suchas:

Rolling, drawing, and extruding of non-ferrous metals Heat treating Coating, engraving, and allied services

Metal manufacturing industries perform many different processes, including:

Machining, Grinding, Buffing, Polishing, Tumbling, Sand casting, Forming, Rolling,Extruding, Forging, Ironing, Lettering, Enameling, Cleaning, Welding, Finishing, Die sinking,Pickling, Coining, Degreasing, Electrogalvanizing, Electroplating and Painting.

The wastes associated with these processes fall into several major categories:

Spent solvent and solvent still bottoms result from cleaning and degreasing operations.The types of solvents used include chlorinated solvents (e.g., methylene chloride,dichlorobenzene, carbon tetrachloride, trichloroethylene) or hydrocarbons (e.g.,gylene, toluene, benzene). Other solvents are kerosene or mineral spirits ("Stoddard"solvents).

Strong acid wastes are generated in considerable quantity wherever any type of metalis formed or processed.

Many pickling solutions are highly acidic; the acid, if not neutralized, might be carriedto subsequent manufacturing operations. Subsequent operations can include drawing,rolling, pressing, electroplating, hot dip galvanizing or hot tinning, anodizing,phosphating, metal coloring, and many others.

Strong alkaline wastes are generated from the use of pickled aluminum and sometimeszinc.

Plating wastes are generated from electroplating operations. These wastes can be acidicor alkaline and contain significant concentrations of heavy metals. Acid platingsolutions generally contain free acids and heavy metals such as copper, nickel, zinc,

d ibl i d i Alk li l i l i i l d i b h d

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battery manufacturing plants. Other sludges can come from grinding, tank clean-outs,dust collectors, and lead pots.

Paint and coating wastes are generated by several segments of the industry. Generally,hazardous paint wastes contain cadmium, chromium, lead and/or mercury. Paints,lacquers, adhesives, and varnishes might contain toxic organic chemicals as well.

Cyanide wastes are generated from cyanide plating solutions and simple cyanidesolutions. Cyanide plating solutions are used in metal plating operations. Simplecyanide solutions are used mainly for hardening and metal cleaning. Cyanide baths arecommonly used in metal finishing and heat treating operations.

Other reactive wastes are generated primarily by the photographic equipment andsupplies industry, although other metal manufacturing industries can also generatereactive wastes. These wastes can include strong oxidizing agents such as chromicacid, perchlorates, and permanganates used in metal finishing, and other reactivecompounds such as hypochlorites, peroxides, sulfides, nitrates, and sodium hydroxide.

In addition to these wastes, most metal manufacturing industry operations will generateused oil. Oils can come from cutting, lubricating, and/or quenching.

Most metal manufacturers also generate scrap metal.

Table 4.9 lists general operations/processes that use hazardous materials and that might resultin the generation of hazardous waste.

Table 4.9 Typical Metal Manufacturing Operations Materials and HazardousWastes

Process/Operation Materials Used General Types of Waste

Generated

Metal Cutting/Machining Oils, solvents, lime, metalcuttings Degreasing Solvents,alkaline wastes, rags

Acid/alkaline wastesToxic heavy metal wastes (dustand sludge)Solvent wastes

Other toxic wastesPickling Pickling acids Acid/alkaline wastes

Heat Treating Quenching oils, cyanide salts,burium salts, alkalinewastes

Acid/alkaline wastesCyanide wastesToxic heavy metal wastes

Metal Finishing and Painting Paints, coatings, cleaning Acid/alkaline wastes

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4.1.3.4 Hazardous Wastes from Chemical Industry

Chemical manufacturers category:

Industrial inorganic chemicals Industrial organic chemicals Pigments Plastics Pesticides Synthetic rubber Explosives Synthetic fibers Gum and wood chemicals.

The many different processes used in the chemical manufacturing industry result in a largenumber of specific wastes. Typical wastes from chemical manufacturing plants include spentsolvents, distillation bottoms and side-cuts, off specification or unused chemicals, wastewater,wastewater treatment sludge, emission control sludges, filter cake, spent catalysts, byproducts,reactor clean out wastes, and container residues. Many wastes from chemical manufacturing(e.g., spent solvents and off-specification chemicals) are listed wastes. Toxicity CharacteristicLeaching Procedure (TCLP) toxic constituents have been detected in many other chemicalmanufacturing wastes.

Table 4.10 provides a general description of chemical manufacturing waste types.

Table 4.10 Typical Chemical Manufacturing Operations Materials Used and HazardousWastes Generated

Process/Operation Materials Used General Types of Waste

Generated

Pigment Manufacturing Acids/alkalies, heavy metals(catalysts andsalts), solvents, petroleumdistillates

Acid/alkaline wastesHeavy metal wastes (dust andsludge)Heavy metal wastes (solutions)

Solvent wastesToxic organic liquidsToxic wastewaters and sludges

Pesticide Manufacturing Pesticides, carriers, dispensingagents, solvents

Pesticide wastesIgnitable wastesSolvent wastes

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brighteners, polymeric materials Toxic heavy metal wastesToxic wastewaters and sludgesOther toxic wastes

Rubber Manufacturing Monomers, solvents, paints.

Catalysts

Toxic heavy metal wastes

Toxic or ignitable paint wastesToxic wastewaters and sludgesOther toxic WastesOily wastesSolvent wastesWaste rubber solids

Other Chemical Manufacturing Solvents, chemicals, catalysts,acids/alkalies, heavy metals

Acid/alkaline wastesToxic heavy metal wastes(dust and sludge)

Other toxic wastesIgnitable wastesReactive wastes (other)Solvent wastesSpent catalystsEmission control dusts andsludges

4.1.3.5 Hazardous Wastes from Pharmaceuticals / Bulk Drug Industry

While the specific chemical constituents of the waste can vary depending on the type ofchemicals formulated, most formulators will have wastes that fall under one of the followingcategories:

Spent or unusable materials such as chemicals and solvents Rinsing solutions from cleaning of containers, mixing vats, and tools Rags and other cleaning implements.

The Pharmaceutical industry can be divided into three subgroups:

i. Manufacturers of bulk drugs, which are prepared by using organic reactions. The product

can be described to be having an activity like a drug and used as an active ingredient in final

pharmaceutical formulations.

ii. Manufacturers of antibiotics, which are prepared by using fermentation process.iii. Manufacturers of final pharmaceuticals formulations, which are prepared using bulk drugs,

antibiotics etc. The products can be described as the final item for sale as tablets, injections,

ointments, capsules syrups, etc.

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Table 4.11 Typical Pharmaceutical Industry Operations Materials and Hazardous

Wastes

Process/Operation Materials Used General Types of Waste

Generated

Pharmaceutical Preparations Formulation Solvents, resins,lubricants, gelatins

Solvent wastesIgnitable wastesToxic wastewaters andwastewater treatment sludgesAcid/alkaline wastes

4.1.3.6Hazardous Wastes from Agrochemicals / Pesticide IndustryThese industries produce substances for pest control. The group can be divided into two

subgroups:

i. Manufacturers of bulk pesticides by use of chemical reactions (organic as well asinorganic). The products can be described by having a special effect on the pest to be

controlled. The products can be described as germicides, weedcides, rodenticides, insecticides,

fungicides, etc.

ii. Manufacturers of final pesticides using bulk pesticides in dilution or reformulation. Theproducts can be described as the final item for sale as powder, liquids, etc.

Pesticide and agricultural chemical formulators mix concentrated pesticides with carriers anddispersing agents for use by pesticide applicators. The formulations can include a number ofcompounds that enhance the properties of the pesticide product, The carriers, dispersingagents. and other compounds might contain hazardous constituents. In general, the wastesfrom pesticide and agricultural formulators are pesticide-contaminated rinse solutionsgenerated from washing and rinsing the drums. vats, and assorted instruments used to mix theformulation.

Table 4.12 presents the typical hazardous wastes generated in the Adgrochemicals formulationindustry.

Table 4.12 Typical Agrochemical Industry Materials Used and Hazardous Wastes

B d th b t i t i ti f th l t d i d t i T bl 4 13 t th

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Based on the above waste inventorisation for the selected industries, Table 4.13 presents thesummary of the waste types and form / streams from these selected industries.

Table 4.13 Summary of Hazardous waste characterization from selected industries

Industry Type Liquids Sludges

Agrochemicals SolventRinse solutions with pesticides

Pesticide residues

Bulk drugs / Pharmaceuticals SolventToxic wastewaterAcid solutions

Treatment plant sludges

Chemical Inorganic solutions (acidic /alkaline)Heavy metal solutionsOily wastewaters

Still bottoms, treatmentplant sludgesInorganic sludges

Metal finishing Heavy metal wastewatersOil and degreasing streamsSolvents from degreasingAcidic and Alkalinewastewaters

Treatment plant sludges,

Paper Manufacturing Acid and alkaline wastesHighly organic wastewatersSolvent wastewaters

Organic sludges

Petrochemical Oil and grease wastewatersTarry wastewater

Oily sludges, tankbottoms, stills

Tannery High organic wastewaters

Heavy metal wastewaters

Metal sludges

Organic residues

4.1.3.7Hazardous Wastes from Petrochemical IndustryThis industry includes the extraction, refining and various product formulations of petroleumproducts. This industry normally produces tarry wastes, oil laden and organic sludge andwastewater.

4.1.4 Wast