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    Hazardous Waste Management - Implications Of The Basel Convention In Indian Context*
Implications Of The Basel Convention In Indian Context*

(e)Annexure I(f)
(g)ENVIRONMENTALLY SOUND MANAGEMENT CAPACITIES IN INDIA FOR RE(h)CYCLING / REPROCESSING OF HAZARDOUS WASTES :
LEAD, ZINC AN(i)D USED OIL
   
1.
Elements of environmentally sound management
  The extent to which wastes can be treated to obtain specific products
  Potential of harm to human health and the environment
  Economic balance and market opportunities
  Location of treatment facilities
  Processing of the hazardous wastes and by-products of the process itself
  Worker safety
2. Criteria for environmentally sound reuse or recycling options
  Feedstock (upstream) quality : degree and nature of contamination and environmental/health risks association with handling and processing, volumes and types.
  Treatment processes for getting appropriate quality feedstock for downstream industries or users, impacts on resource conservation, percentage of the product recovered, energy savings.
  Impacts of treatment processes on public health and environment.
  Final disposal of end-of-the-pipe output of treatment processes in the framework of environmentally sound management of hazardous wastes.
  Economics (economic viability/sustainable market and commercial feasibility; product value).
  Technology and techniques (treatment capacity, feedstock capability) and their potential impacts on the environment.
  Location of existing or planned facilities.
  Infrastructure for clean and efficient collection, storage and transport of used lube oils.
  Public perception
  Legislation (i.e. on air emissions).
  Socio-economic benefits (i.e. employment opportunities).
  Knowledge of cases or processes which have gone wrong in the past.
  Availability of cleaner production methods and clean technologies.
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3. Recycling Of Lead
  3.1 Secondary Lead
   

In India, secondary lead production has jumped from 14,100 to about 29,000 tonnes in the 1996-97 period, as industrial infrastructure and automotive market expanded. At present, lead acid battery accounts for about 75% of the lead consumption. The overall contribution of the secondary lead industry in the country is same as that of primary producers. There are about seven medium size secondary lead plants (total capacity 55,000 tonnes/year), 40 small operations (combined capacity of 15,000 tonnes/year) and more than 250 tiny/backyard plants (estimated combined capacity 25,000 tonnes/year). The main source of lead in these plants is scrap batteries.

One major problem in India is that of low technology and the pollution caused by the smaller secondary plants in unorganized sector. Current secondary lead refining practices are mainly batch processing based on the traditional pyrometallurgical methods. Batch refining is carried out in hemispherical vessels usually stirred to mix in the reactants. The stirring is not necessary where injecting air does oxidation or oxygen enriched air through lances. The metal is then held molten while the reaction products float out and are recovered from the surface.

In backyard/unorganized smelters, lead scraps and wastes in several forms are smelted first in open receptacles, and then refined to chemically pure (99.99%) lead and also in manufacture of various lead alloys. The backyard smelters, dispersed widely have no pollution controlling system

  3.2 Traditionally the processing of lead acid batteries is carried out using pyrometallurgy. Flow diagram of a typical plant is given below (figure:1):
      Figure 1: Manufacturing process flow diagram of secondary lead smelter
  3.3 Emission control system provided in a secondary smelter plant is given below (figure: 2).
    Figure 2: Emission control system at secondary lead smelter
   

India's primary lead production comes entirely from the public sector company, M/s. Hindustan Zinc Ltd (HZL). The lead production capacity at its Vishakhapatnam plant stands at 22,000 tonnes per annum. With commissioning of HZL's new lead smelter, at Chanderiya in Rajasthan with an annual capacity of 35,000 tonnes, the primary lead production capacity in India, all by HZL only has gone up to 65,000 tonnes. In addition to this, the country currently has around 52,000 tonnes secondary lead production capacity in the organized private sector. However, only about 30,000 tonnes from this sector are available in the open market since the remaining part is for captive consumption. Out of this, Indian Lead Ltd. (ILL) with a capacity of 24,000 tonnes per annum is gradually shifting to concentrate route due to the low availability of scrap. There is also a significant 15,000 tonnes secondary lead production capacity in the unorganized sector, generally known as the backyard furnace.

The demand and supply gap would work to about 41,700 tonnes by the end of 9th plan and would further increase to 114,500 and 192,200 tonnes by the end of 10th and 11th plans respectively. Demand-supply details are given in Table 1.

  Table 1: Demand-supply balance with existing capacities-Lead
 
Year Demand with
7% Growth
(Tonnes)
Supply of Lead
(HZL + ILL)
(Tonnes)
Deficit
(Tonnes)
Satisfaction
%
9th Plan        
1997-1998 91,900 78,500 13,200 85.6
1998-1999 98,100 78,500 19,600 80.00
1999-2000 105,000 78,500 26,500 74.80
2000-2001 112,300 78,500 33,800 69.90
2001-2002 120,200 78,500 41,700 65.30
10th Plan        
2006-2007 193,000 78,500 114,500 40.70
11th Plan        
2011-2012 270,700 78,500 192,200 29.00
  A good deal of difficulty in meeting the demand of primary lead can partially be solved by encouraging recycling of lead scrap for production of secondary lead by ensuring centralized collection of old/used lead-acid batteries and processing of the same by the organized sector with environmentally sound management and also by import to augment the remaining gap in demand, if any.
  3.4 Code of practice for environmentally sound management of lead-acid batteries
  1. The application of the user industry for obtaining ESM registration shall be accompanied by the following permission/authorisation and report on compliance of conditions thereof from the concerned State Pollution Control Board/Committee.
  (a) Authorisation under Rule 5 of Hazardous Waste (Management & Handling) Rules, 1989, and amendments thereof notified under the Environment (Protection) Act, 1986, from the concerned State Pollution Control Board/Committee regarding collection, treatment, storage and disposal of hazardous waste.
  (b) Consent under Section 25/26 of Water (Prevention & Control of Pollution) Act, 1974, from the State Pollution Control Board/Committee.
  (c) Consent under Section 21 of Air (Prevention & Control of Pollution) Act, 1981, from the State Pollution Control Board/Committee.
  (d) Analysis report from the State Pollution Control Board/Committee or any recognised testing laboratory regarding the compliance of emission control system and effluent treatment provided/installed by the user to meet the standards.
  2. The transport of waste to the user’s site shall be in accordance with the Hazardous Waste (Management & Handling) Rules, 1989, and amendment thereof notified under the Environment (Protection) Act, 1986.
  3. The storage of the waste at the processing site shall be such that the material will not come in contact with water.
  4. The waste shall be processed for recovery of lead by reduction process in furnace with proper optimization of process.
  5. The slag produced after the recovery of lead shall be reprocessed atleast twice so as to bring down the lead content in the slag that will become due for disposal.
  6. Disposal of slag shall be done at the dedicated landfill facility as per the design approved by the State Pollution Control Board or as given in the guidelines under Hazardous Waste (Management & Handling) Rules, 1989 and amendments thereof notified under the Environment (Protection) Act, 1986.
  7. The leachate collection system shall be integral part of the disposal/landfill facility and the leachate shall be further treated so as to meet the tolerance limit of heavy metals as under given in the schedule VI, under the Environment (Protection) Act, 1986
 
Heavy Standard, µg/l.
metals Inland surface water Marine coastal areas
Cadmium 2 2.0
Lead 0.1 2.0
Nickel 3 5.0
 
8.


Air pollution control system for reprocessing of lead acid batteries shall include Furnace ? Settling chamber ? Cyclone(s) ? bag filter(s) ? Agglomerator ? Stack height (as stipulated) so as to meet the emission standard of 10 µg/N.cu.m for lead and 50 µg/N.cu.m for total particulate matter.

  9. The industry shall maintain records of collection, treatment, transport, storage and disposal of hazardous waste in Form 3 and submit return to SPCB/PCC in the Form 4 of HW (M&H) Rules, 1989 and amendments thereof notified under the Environment (Protection) Act, 1986.
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4.0 Recycling Of Zinc
  4.1 Secondary Zinc
  15-20% of zinc demand in India is met through secondary production. There are 20 secondary zinc units (with a production capacity of about 3000 tonnes of zinc ingot per month) and more than 200 zinc chemical units (zinc oxide, zinc sulphate, zinc chloride etc.). These play an important zinc supply-demand-balancing role in the country. Most of the secondary zinc units use both mechanical and electrolytic methods while some units recover metallic zinc from zinc ash by mechanical method and sell-out fines (mainly oxide with 50-60% zinc) to zinc chemical manufacturer. One pilot scale unit in Gujarat is also reported to be using a plasma process for zinc. The small size of secondary zinc units has restricted the use of advanced technology.
  4.2 Electrolytic Process for Zinc Ash:
    The process of extraction of zinc, using zinc ash as raw material, constitutes mainly following stages:
    (A) Material preparation
    (B) Leaching
    (C) Purification
    (D) Electrolysis & Melting
    (E) Bleed-off
    (F) Effluent Treatment
  (A) Material Preparation
  Zinc ash is generally available in the form of lumps and chips. It is, therefore, first crushed and then pulverized to separate out zinc metallic from fine ash. On melting and casting this metallic, zinc is obtained.

Fine ash is first subjected to calcination in an oil fired rotary kiln at 900oC. Particle retention time in the kiln is decided by the percentage of chloride present in the ash. The rotary kiln is associated with cyclones, settling chamber, and water & lime scrubbers. All the evolved chlorine is absorbed in lime or NaOH scrubber. Calcined ash lumps are pulverized again to get particle size of (-) 100 mesh.

  (B) Leaching
 

The calcined fine ash is then treated with sulphuric acid and / or spent electrolyte, generated during electrolysis for leaching operation. Zinc is rendered soluble according to the following reaction, using agitated reactors:
ZnO + H2SO4 ? ZnSO4 + H2O

During this operation, compressed air and pyrolusite (MnO2) are added to oxidize ferrous iron to ferric state. Small quantity of steam, if required, is also added to leach zinc at about 60oC to get better extraction. Leaching is continued till pH of the slurry reaches 4.5 to 5 where the oxidized impurity of iron is hydrolyzed to ferric hydroxide precipitate and is thus removed from the solution:

3ZnO + Fe2(SO4)3 + 3H2O ? 3ZnSO4 + 2 Fe(OH)3
The slurry is then discharged to a thickener for solid-liquid separation. For quicker settling, suitable flocculent is added to slurry at the time of discharge. The thickener, overflow, which is a clear solution of ZnSO4, is sent for purification.

The thickener underflow is pumped to another reactor, where it is subjected to water washing. The pulp is filtered in a drum filter to get soluble zinc.

The residual cake is discarded to secured landfill facility and the filtrate goes to effluent treatment plant for making zinc hydroxide.

  (C) Purification
  The primary object of purification is to prepare the solution for electrolysis by removing all those impurities, which are harmful to the process of electrolysis. This operation is done in three stages.
  First Stage
  In first stage, copper is cemented out with the addition of zinc dust/powder. The resultant pulp is filtered in filter press (FP) to recover copper as copper cement and the filtrate is taken to second stage of purification.
  Second Stage
  Solution is treated with stoichiometric requirement of DMG to remove the impurity of nickel. Addition of excess quantity of DMG is avoided as it increased chemical oxygen demand (COD). Once the nickel removal is achieved the solution is filtered through a FP and is sent to third stage of purification.
  Third Stage
  To absorb organic impurities, activated charcoal is added here. This purification stage is also considered as the polishing stage. Any unwanted impurity, escaping through 1st & 2nd stage will be removed here. It is thus ensured that ZnSO4 solution going for electrolysis is purified properly.
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  (D) Electrolysis & Melting
 

The purified solution, mixed with spent electrolyte, and cooled in atmospheric cooler to a temp. of 35?C is electrolyzed in electrolytic cells, using lead anodes and aluminum cathodes. Zinc metal deposits on cathodes, whereas oxygen is given off at anodes. During electrowinning of zinc, sulphuric acid is generated as per the reaction given below:
ZnSO4 + H2O ? H2SO4 + Zn + ½O2

Zinc so deposited on aluminum cathodes is stripped-off manually after every 24 hours and is melted in oil fired crucible furnace. Molten Zinc metal is cast as zinc ingots. Spent acid is pumped to leaching section for reuse.

  (E) Bleed-Off
  Even with the removal of maximum amount of chlorides and other impurities from zinc ash, there will always be build-up of impurities in the system. To lower down the level of impurities in the system some solution need to be removed from it. Bleed-off solution is used to manufacture zinc sulphate crystals.
  (F) Effluent Treatment
  The only waste in the system would be solid cake containing mainly silica, gypsum etc. which is disposed-off in secured landfill facility. Wash solution is converted into zinc hydroxide, which is reused in the system.
  4.3 Process for Zinc Sulphate :
    Manufacturing processes flow-chart for zinc sulphate is given below (figure:3) :
  Figure 3: Manufacturing processes flow-chart for zinc sulphate
  4.4 Code of practice for environmentally sound management for zinc ash/skimmings
  1. For obtaining ESM registration, the industrial units shall have “consent” and “authorisation” for disposal of hazardous wastes from respective State Pollution Control Board/Committee.
  2. During transportation, processing for recovery of zinc and production of zinc oxide/zinc sulphate, the following measures will be taken for environmental safeguards :
  . (a) To avoid dust emissions during handling and transport, properly covered containers should be used.
    (b) In the rotary furnaces, the industry should install properly designed bag filter followed by a scrubber. The emission of lead and total particulate matter should not be more than 10 µg/Nm3 and 50 µg/Nm3 respectively.
    (c) The effluent from scrubber should be properly treated and disposal of the same, as may be required, shall meet the standards stipulated by the concerned State Board/Committee.
    (d) In the refining section, the solid waste generated from drum filter cake which may contain lead, cadmium etc., shall be properly neutralised and disposed in a secure landfill to be provided as per the guidelines issued by MoEF for implementation of Hazardous Waste (Management & Handling) Rules, 1989 and amendments thereof. The design of secure landfill shall be approved by SPCB/PCC. The leachate collection system shall be provided and leachate shall be treated so as to conform the standards stipulated by the SPCB/PCC.
    (e) In the electrolysis section, the fugitive emission generated by electrolysis process, i.e. acid fumes, should be properly controlled. The industry should install canopy hood for channelisation of emission and it should be connected to a properly designed scrubber before discharging through a stack, as may be necessary.
    (f) The industry should utilise the solid waste as far as possible under intimation to the SPCB/PCC.
    (g) The container of zinc ash/skimming (after taking the material) should be properly cleaned and the washing, if any, should be treated in the effluent treatment plant as directed by the SPCB/PCC.
    (h) Analysis report (from the State Pollution Control Board or any recognised testing laboratory) regarding the compliance of emission control system and effluent treatment equipment provided by the user to meet the standards.
    (i) Treated wastewater from the industry should be fully recycled.
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5.0 Used lube oil / waste oil
  5.1 Waste oil as hazardous wastes is listed in Annex VIII (list-a) in the Basel. However, this entry does not clearly illustrate the different types of waste oils generating from various processes and sources. Therefore an attempt has been made to separately define used lube oil and waste oil in the Indian context. This is in consideration with the level of contamination, content of Annex I material exhibiting Annex III hazard characteristics, toxicity upon disposal and environmentally sound management of wastes. For this purpose there is a need to create a new entry of used lube oil at Annex IX (List B) of Basel.
  5.2

C.C.M.E. (Canadian Council of Minister for Environment) has defined used oils in code of practice for used oil management in Canada (it is important to refer to this definition since it has been adopted by the Basel Convention), as an oil from industrial and non-industrial Source which has been acquired for lubricating and other purposes and has become unsuitable for its original purposes due to the presence of impurities or the loss of original properties.

Used oil doesn’t include oils derived from animal or vegetable fats nor does it include crude or fuel oil spilled on to land or waters and wastes from petroleum refining operations.

The Basel Technical Guidelines (R9) has used the terms namely used (lube) oil and waste oil separately which clarifies that they are two different yields.

The definition of used oil in (R9) is ambiguous since it mentions used oil meaning thereby any semi solid or liquid used product consisting totally or partially of mineral oil or synthesized hydrocarbons (synthetic oil) only residues from tank oil water mixture and emulsions. These used product arise from industrial and non-industrial resources where they have been used for lubricating, hydraulic, heat transfer, electric insulating or other purposes.

Mineral oil: The term mineral and lubricating oil as defined in the Chemical Dictionary is:

     Mineral
    : A loose and inexact term that may be defined chemically as any elements, inorganic compound or mixtures occurring or originating in the earth crust or atmosphere including all metals and non-metals, their compounds and ores, mineral oil is defined as a liquid petroleum derivative
      Lubricating oil:
    A selected fraction of refined mineral oil used for lubrication of moving surfaces.
   

It is further submitted that Chapter 27 of Harmonized System (HS) of nomenclature further lends support that lubricating oils are obtained by distillation of mineral oils.

Thus it is abundantly clear that lubricating oil has a separate identity and is a product manufactured out of mineral oil when refined in the refineries.

  5.3 Waste oil & emulsions:
      Waste oil:
   

In petroleum technology - oil having characteristics making it unsuitable either for further use or for economic recycling’. Ref ASTM 4175

It is submitted that R-9 has concluded in the end (page 11) that used oil and waste oil are two different products having different specifications and end uses respectively i.e. waste oil can not be re-refined and can only be converted into fuel where as used lube oil can be re-processed/ re-refined to yield lubricating oil suitable for its original use.

It is therefore imperative that a suitable definition is formulated where used lube oil is separately defined, categorized and placed on Annex IX of the Convention.

  5.4 Waste Management for the reprocessing/reclaiming of used lube oil:
   
  Water pollutants  
Source Condensate / filtrate
Quantity depends upon water content in the used lube oil
Treatment Neutralization and traps for removal of oil and grease so as to meet the liquid effluent standards notified under the Environment (Protection) Act, 1986 as below:
pH : 5.5 to 9.0
and
Oil & Grease : 10 µg/l
Treatment (i) Adequate stack height for disposal of gaseous emissions due to burning of LDO used for thermic fluid heating. Stack height is to be calculated as per formula notified under the Environment (Protection) Act, 1986.
  (ii) In case incinerator is provided for filter press cake and acid/clay sludge, then neutralization of waste will be necessary and incinerator would be equipped with gas scrubber and adequate stack height for disposal of gaseous emissions in accordance with the Environment (Protection) Act, 1986.
       
   
Solid (hazardous) wastes (i) Filter press cake and acid-clay sludge is generated as hazardous waste.

(ii) Treatment:

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  5.5 Comparative evaluation of re-refining techniques
    [Source: Y-8, Technical guidelines on hazardous wastes: waste oils from petroleum origins and sources]
   
  Evaluation item Acid/clay Vacuum distillation/
clay
Vacuum distillation/ hydro-treating
1. Lube yield a Low Medium Medium
2. Bright stocks b Recovered Lost Lost
3. Utilities c Low Low Lost
4. Overall energy d High Low Medium
5. Hazardous chemicals e Sulphuric Acid Caustic Caustic
Waste Streams
6. Acid sludge Most None None
7. Oily clay Most Some None
8. Caustic sludge or spent caustic None Some Some
9. Process water Low Medium High
     
    LEGEND:
    a. LUBE YIELD :
      THE OIL YIELD IN THE ACID/CLAY PROCESS IS LOW BECAUSE OF LOSES TO THE ACID SLUDGE. THE TWO DISTILLATION PROCESSES DO NOT RECOVER BRIGHT STOCKS AND THIS IS REFLECTED IN THEIR MODERATE LUBE OIL RECOVERY.
    b. BRIGHT STOCKS:
      BRIGHT STOCKS ARE RECOVERED ONLY IN THE ACID/CLAY PROCESS. THIS PROCESS WOULD BE FAVOURED IN THE UNUSUAL SITUATION WHERE USED OILS CONTAIN EXTREMELY HIGH PROPORTIONS OF BRIGHT STOCKS.
    c. UTILITIES :
      ‘UTILITIES’ REFERS TO THE TOTAL EXTERNAL ENERGY REQUIREMENT (POWER PLUS FUEL).
    d. OVERALL ENERGY:
      THIS IS TOTAL EXTERNAL ENERGY (UTILITIES) PLUS POTENTIAL ENERGY LOST IN NON-RECOVERED OILS.
    e. HAZARDOUS CHEMICALS:
      IN THE ACID/CLAY PROCESS, THE OPERATORS ARE EXPOSED TO THE RISK OF HANDLING SULPHURIC ACID AND THE RESULTING ACID SLUDGE. ALL THREE PROCESSES EXPOSE THE OPERATORS TO POSSIBLE CHEMICALS BURNS.
  5.6 Code of practice for environmentally sound management of used lube oil
  1. Acid/clay process to re-refine used lube oil in small/medium industry in the organized sector can yield Bright Stock in a techno-economically feasible manner and the waste generated by this process can be handled in an environmentally sound manner without exhibiting Annex III hazard characteristics as given in the HW (M&H) Amendment Rules, 2000.
  2. For obtaining ESM registration, the industrial units shall have “consent” and “authorisation” for disposal of hazardous wastes from respective State Pollution Control Board/Committee.
  3. The secondary wastes generated during re-refining process are: bleaching earth, acid tars, slurries and aqueous residues. The disposal of waste generated is required to be done in an environmentally sound manner as under:
    (a) Sediments: It shall go for de-watering and neutralisation and then disposal in landfill or incineration as per authorisation under rule 5 of Hazardous Wastes (Management & Handling) Rules, 1989, and amendments thereof.
    (b) Aqueous phase: This needs to be treated in the effluent treatment plant to meet the standards stipulated under the consent conditions issued under section 25/26 of the Water (Prevention & Control of Pollution) Act, 1974. This would generally include neutralisation and separation of oil & grease.
    (c) Oil slurries: These shall be taken for energy recovery or combustion or incineration after neutralisation, as may be required, in a systematic manner with the approval by the State Pollution Control Board/Committee.
    (d) The incineration process shall meet the emission standards stipulated under the consent conditions issued under section 21 of the Air (Prevention & Control of Pollution) Act, 1981. Waste for incineration shall be neutralised and incinerator shall be provided with air pollution control equipment (such as scrubber, proper stack height etc.).
  4. The industry shall maintain records of collection, treatment, transport, storage and disposal of hazardous waste in Form 3 and submit return in Form 4 of HW (M&H) Rules, 1989 and amendments thereof to the SPCB/PCC.
       
IMPLICATIONS OF
THE BASEL CONVENTION IN INDIAN CONTEXT

Presentation by
D. B. Boralkar & Dilip Biswas
Central Pollution Control Board, Delhi
AT THE
INTERNATIONAL CONFERENCE ON
HAZARDOUS WASTES MANAGEMENT
AT CHENNAI,

January 27, 2000

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