Standard Operating Procedure and Checklist of Minimal Requisite

Facilities for utilization of hazardous waste under Rule-9 of the

Hazardous and Other Wastes (Management and Transboundary
Movement) Rules — 2016

Utilization of the Process residue containing Ethanol >30 %

[generated during the manufacturing of Glufosinate - Technical
Pesticide] for recovering Ethanol (93%) and Sodium Acetate (30%)

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CPCB
January, 2024

Central Pollution Control Board

(Ministry of Environment, Forest & Climate Change,
Government of India)
Parivesh Bhawan, East Arjun Nagar,
Shahdara, Delhi — 110032
Utilization of the Process residue containing Ethanol >30 % [generated during the manufacturing of
Glufosinate - Technical Pesticide] for recovering Ethanol (93%) and Sodium Acetate (30%)

Procedure for grant of authorization by State Pollution Control Board (SPCBs)/Pollution

Control Committee (PCCs) for utilization of Hazardous waste

1) While granting authorization for utilization of hazardous wastes, SPCBs/PCCs shall

ensure that authorization is given only to those wastes for which Standard Operating
Procedures (SoPs) for utilisation have been circulated by CPCB ensuring the following:
a. The waste (intended for utilization) belongs to same source of generation as
specified in SoP.
b. The utilization shall be same as described in SoP.
c. End-use/ product produced from the waste shall be same as specified in SoP.
d. Authorization shall be granted only after verification of details and minimum
requisite facilities as given in SoP.
e. Issuance of passbooks (similar to passbooks issued for recycling of used oil,
waste oil, non-ferrous scraps, etc.) for maintaining records of receipt of
hazardous waste for utilization.
f. Monitor closely the quantity of Process residue containing Ethanol being sent by
generators and the quantity being utilized by the authorized industries.
2) After issuance of authorization, SPCBs/PCCs shall verify the compliance of checklist
and SoP on quarterly basis for initial 1 year; followed by random checks during
subsequent period for atleast once a year. The compliance reports may be submitted to
CPCB.
3) In-case of lack of requisite infrastructures with the SPCBs/PCCs, they may engage 3"
party institutions or laboratories having EPA/NABL/ISO 17025
accreditation/recognition for monitoring and analysis of prescribed parameters in SoPs
for verification purpose.
4) | SPCBs/PCCs shall provide half yearly updated list of units permitted under Rule 9 of
Hazardous & Other Wastes (Management & Transboundary Movement) [HOWM]
Rules, 2016 to CPCB and also upload the same on SPCB/PCC website, periodically.
Such updated list shall be sent to CPCB.
5) Authorization for utilisation shall not be given to the units located in the State/Union
Territory where there is no Common TSDF, unless the unit ensures authorised captive
disposal of the hazardous waste (if any generated during utilisation) or its complete
utilisation or arrangement for transfer to authorised disposal facility.
6) Incase of the utilization proposal is not same with respect to source of generation or
utilization process or end-use as outlined in this SoP, the same may be referred to CPCB
for clarification /conducting trial studies and developing SoPs thereof.
7) The source and work zone standards suggested in the SoP are based on E(P)A notified
and OSHA/NAAQ standard, respectively. However, SPCBs/PCCs may impose more
stringent standards based on the location or process specific conditions.
8) | SPCBs/PCCs shall ensure that the utiliser of Process residue containing Ethanol shall
maintain daily records on National Hazardous Waste Tracking System (NHWTS).

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Waste Management-II Division, CPCB, Delhi {ot = | 1| Page
Utilization of the Process residue containing Ethanol >30 % [generated during the manufacturing of
Glufosinate - Technical Pesticide] for recovering Ethanol (93%) and Sodium Acetate (30%)

97.0 Utilization of hazardous waste (H.W.):

Type of HW Source of generation Recovery/ Product

Process residue containing | Generated during | Recovery of Ethanol
Ethanol >30 % (Category: | manufacturing of |(93%) and Sodium
29.1 of Schedule I of | Glufosinate (Technical | Acetate (30%)
HOWM Rules, 2016) Pesticide)

97.1 Source of Waste:

Process residue containing Ethanol >30 % generated during manufacturing of Glufosinate

(Technical Pesticide) is categorized as hazardous waste under Category: 29.1 of Schedule I of
HOWM Rules-2016 which is required to be disposed in an authorized disposal facility in
accordance with condition, when not utilized as resource recovery.
Table 1. Typical Characteristics of Process residue

De. Parameters Unit Results*

No.
l. pH - 0.58
2 Appearance - Transparent
3 Purity as Ethanol % > 30
4. Water Content % 18.47
5. Ammoniacal Nitrogen mg/L 1506.4
6. TOC % < 44
7. COD % < 8.5
8. Chloride mg/L < 8218 |
D, Sulphate mg/L < 350
10. | Phosphate mg/L = 2.5
11. | Iron (as Fe) mg/L <1.5
Shall not contain heavy metals Zn/
12. | Cd / Pb /Ni/ As / He / Cn /Mn/ Cr i lass
13. | Cyanide (as Cn) mg/L <0.01
14. | Pesticides as Glufosinate Ammonium mg/L 1.06

97.2 Utilization of Process residue containing Ethanol at Production Stage:

Process residue is reacted with caustic and hypo in a reactor to precipitate the salts of inorganic
compounds. The resulting clear solution is transferred to a storage tank for further process and
salt sludge from the bottom of reactor are retained through Agitated Nutsche Filter (ANF) by
filtration process where the recovered Mother Liquor is recycled to the reactor and the salt
sludge is disposed of in TSDF.
The above clear solution undergoes another reaction with caustic, followed by distillation. The
first cut from the distillation is Organic liquid waste, which is disposed of in the Common
Hazardous Waste Incineration Facility (CHWIF) or for Co-processing; second cut with 93%
ethanol is recovered as product and remaining mass containing sodium acetate is processed
further.

Waste Management-II Division, CPCB, Delhi 2|Page

Ss——
Utilization of the Process residue containing Ethanol >30 % [generated during the manufacturing of
Glufosinate - Technical Pesticide] for recovering Ethanol (93%) and Sodium Acetate (30%)

The remaining mass containing sodium acetate is treated with water and carbon to remove
impurities and further filtered to obtain Sodium acetate solution as product. Filtered carbon
sludge is disposed of in the CHWIF or through co-processing.
Vent

t
Alkali Scrubber t

PROCESS ESO Ue " > Agitated Nutsche filter

NaOH |—> Reaction |
Mother
Sodium Hypo Chloride oI liquor Salt for
TSDF

NaOH —| , te 1“ Cut Distillation

Reaction and Organic liquid waste to CHWIF/
Distillation Co-processing

Washing and |
Carbon 2™ Cut Distillation
treatment (Product 1: Ethanol)

Water |—> ! -
Filtration |—») Residue to CHWIF/ Co-
Carbon |—* processing

|!
Product 2: Sodium Acetate

Figure: 1-Process flow diagram for utilization of Process residue

97.3. Product Usage / Utilization

1) Recovered Ethanol shall be reused back into the manufacturing of Glufosinate

(Technical pesticide) and the recovered Sodium acetate shall be used for industrial
purposes only.
2) The Product Sodium Acetate shall comply with Bureau of Indian Standards (BIS), for
further respective utilization.

Waste Management-II Division, CPCB, Delhi \o—— 3|Page

Utilization of the Process residue containing Ethanol >30 % [generated during the manufacturing of
Glufosinate - Technical Pesticide] for recovering Ethanol (93%) and Sodium Acetate (30%)
SS
aE Sa a

3) | Ethanol and Sodium acetate recovered by utilizing said hazardous waste shall NOT be
used in food & beverages, pharma, healthcare industries or as additive in automobile
fuel.

4) The unit shall label its product i.e. Ethanol and Sodium Acetate prepared by utilizing
aforesaid Waste Stream as “This Ethanol and Sodium Acetate has been prepared by
Utilization of the Process residue containing Ethanol >30 % [generated during the
manufacturing of Glufosinate - Technical Pesticide]”.

97.4 Standard Operating Procedure for utilization of Process residue containing

Ethanol >30 “%:

This SoP is applicable only for Utilization of the Process residue containing Ethanol >30 %
[generated during the manufacturing of Glufosinate - Technical Pesticide] for recovering
Ethanol (93%) and Sodium Acetate (30%).

1) The utilizer shall procure the Process residue with Ethanol content of more than 30%
by weight, in SPCB/PCC authorized barrels/closed tanks mounted over vehicles fitted
with requisite safeguards ensuring no spillage.

2) Process residue shall be stored in Polypropylene (PP)/ Fibreglass reinforce plastic

(FRP)/ Polypropylene Fibre Glass Reinforced Plastic(PRV)/ suitable dedicated storage
tanks in acid proof brick lined dyke under covered storage shed within the premises as it
is highly acidic. Further, storage sheds shall have proper slope and seepage collection
pit to collect seepage / floor washing. The collected spillage/ seepage / floor washing
shall be channelized to Effluent Treatment Plant for further treatment.

3) The unloading, storage, transfer and handling of process residue during entire utilization
process shall be carried out through dedicated mechanical transfer pump with fixed
pipeline in closed system. Manual handling shall be strictly prevented.
4) The fumes from the reactors and vacuum pump of distillation column shall pass through
adequate alkali scrubbing system before venting of the same in to the atmosphere.
5) The unit shall ensure system for measurement of saturation of scrubbing bleed for
effective scrubbing of the acidic fumes.
6) The treated gases/fumes shall comply with emission norms prior to dispersion into
atmosphere through stack. The stack height shall be minimum of 30 m from ground
level or as prescribed by the concerned SPCB/PCC, whichever is higher.
7) The unit shall maintain proper ventilation in the work zone and process areas. All
personnel involved in the plant operation shall wear proper personal protective
equipment (PPE) specific to the process operations involved and type of chemicals
handled as per Material Safety Data Sheet (MSDS). The safety precautions of the
worker shall be in accordance with the Factory Act, 1948, as amended from time to
time.

8) | Treatment and disposal of wastewater:

Waste Management-II Division, CPCB, Delhi

Wo 4|Page
Utilization of the Process residue containing Ethanol >30 % [generated during the manufacturing of
Glufosinate - Technical Pesticide] for recovering Ethanol (93%) and Sodium Acetate (30%)

Waste water generated from floor-washings, spillages, reactor washing, scrubber bleed
including the wastewater from filtration, shall be treated Physico-Chemically in an ETP
or may be sent to CETP for final disposal or be treated further in a captive facility to
comply with surface water discharge standards. In case of zero discharge condition by
SPCB / PCC, the treated waste water from ETP shall be managed as per the conditions
stipulated by concerned SPCB / PCC. The treated effluent shall be discharged in
accordance with the conditions stipulated in the Consent to Operate issued by concerned
SPCB / PCC under the Water (Prevention and Control of Pollution) Act, 1974.
9) The hazardous wastes generated shall be collected and temporarily stored in non-
reactive drums/ bags under a dedicated hazardous waste storage area and be sent to
authorized common TSDF or Common Hazardous Waste Incineration Facility
(CHWIF) or Co-processing or other authorized facility within 90 days from generation
of the waste in accordance with the authorization issued by the concerned SPCB/PCC.
The hazardous wastes generated shall be managed as follows:
a) Salt sludge generated from the agitated nutsche filter — To be disposed of in the
common TSDF for disposal after stabilization/encapsulation.
b) Organic liquid waste generated as 1“ cut in the distillation unit — To be
disposed of in the CHWIF or for Co-processing.
c) Carbon sludge generated from the filtration of Sodium acetate — To be disposed
of in CHWIF or for Co-processing.
10) The unit shall ensure that the Process residue is procured from authorized industries as
required under HOWM Rules, 2016.
11) Transportation of Process residue shall be carried out by sender (generator) or receiver
(utilizer) only after obtaining authorization from the concerned SPCB under Hazardous
and Other Wastes (Management and Transboundary Movement) Rules, 2016. Requisite
manifest document shall be followed as laid down under the said Rules.
12) Prior to utilization of Process residue, the unit shall obtain authorization for collection,
storage and utilization of Process residue from the concerned State Pollution Control
Board under Hazardous and Other Wastes (Management and Transboundary
Movement) Rules, 2016.
13) Incase of environmental damages arising due to improper handling of hazardous wastes
including accidental spillage during generation, storage, processing, transportation and
disposal, the occupier (sender or receiver, as the case may be) shall be liable to
implement immediate response measures, environmental site assessment and
remediation of contaminated soil / groundwater / sediment etc. as per the “Guidelines
on Implementing Liabilities for Environmental Damages due to Handling & Disposal of
Hazardous Wastes and Penalty” published by CPCB.
14) During the process of utilization and handling of hazardous waste the unit shall comply
with requirement in accordance with the Public Liability Insurance Act, 1991 as
amended, wherever applicable. The unit shall provide suitable fire safety arrangements
and flame proof electrical fittings.
Waste Management-II Division, CPCB, Delhi / 5|Page
Utilization of the Process residue containing Ethanol >30 % [generated during the manufacturing of
Glufosinate - Technical Pesticide] for recovering Ethanol (93%) and Sodium Acetate (30%)

97.5 Record/Returns Filing

1) The unit shall maintain a passbook issued by concern SPCB/PCC and maintain details of
each procurement of Process residue as mentioned below:
- Address of the sender
- Date of dispatch
- Quantity procured
- Sealand signature ofthe sender
- Dateof Receipt inthe premises

2) A log book with information on source and date of procurement of Process residue,
date wise utilization of the same, hazardous waste generation and its disposal, etc. shall
be maintained including analysis report of fugitive emission monitoring & effluent
discharged, as applicable.

3) The unit shall maintain record of hazardous waste generated, utilized and disposed as
per Form-3 & also file an annual return in Form-4 as per Rule 20 (1) and (2) of HOWM
Rules, 2016, to concerned SPCB/PCC.

4) The unit shall submit quarterly and annual information on hazardous wastes consumed,
its source, products generated or resources conserved (specifying the details like, type
and quantity of resources conserved) to the concerned SPCB/PCC.

5) The unit shall use NHWTS to manage the manifest, enter daily records of quantity
generated, disposed, etc.

97.6 Standards

1) Source emissions from the stack connected to reactors/ process unit shall comply with
the following Emission standards or as prescribed by the concerned SPCB/PCC,
whichever is stringent:

Parameters Standards
HCl 20mg/Nm*
TOC 20mg/Nm*
2) | Work zone emission in the work zone area shall comply with the following standards:

Parameters Standards
Ethyl alcohol 1900 mg/m?,* TWA
Methyl alcohol 260 mg/m?,* TWA
Acetic acid 25me/m?,* TWA
Sodium Hydroxide 2 mg/m?,* TWA
HCl 7 me/m>,#
*PEL - Permissible Exposure Limit.
*Time-weighted average (TWA)- measured over a period of 8 hours of operation of process.
# - A ceiling limit is one that may not be exceeded for any period of time, and is applied to
irritants and other materials that have immediate effects.
-

3) Monitoring of the above specified parameters for Source emissions and Work zone

Waste Management-II Division, CPCB, Delhi ox 6|Page

Utilization of the Process residue containing Ethanol >30 % [generated during the manufacturing of
Glufosinate - Technical Pesticide] for recovering Ethanol (93%) and Sodium Acetate (30%)

emission shall be carried out quarterly for first year followed by at least annually in the
subsequent year of utilization. The monitoring shall be carried out by ISO 17025
accredited or EPA, 1986 approved laboratories and the results shall be submitted to the
concerned SPCB/PCC on a quarterly basis.
4) Standard for wastewater discharge: Treated effluent shall be discharged in accordance
with the conditions stipulated in Consent to Operate issued by concerned SPCB/PCC
under the Water (Prevention and Control of Pollution) Act, 1974. In case of (i) zero
discharge as per consent or (ii) non-availability of the common Effluent Treatment Plant
(CETP), the unit shall achieve zero discharge by setting up adequate captive treatment
facility.

97.7 Siting of Industry

Facilities for utilization of Process residue shall be preferably located in a notified
industrial area or industrial park/estate/cluster and in accordance with Consent to
Establish issued by the concerned SPCB/PCC.
97.8 Size of Plant and Efficiency of Utilisation
During trial study, the yield of 93% Ethanol and 30% Sodium acetate is 0.395 and
1.0646 respectively. Therefore, requisite facilities of adequate size of storage shed and
other plant & machineries shall be installed accordingly.
97.9 Online detectors/ Alarms/ Analyzers
In case of continuous process operations, online emission Analyzers for HCl and TOC in
the stack shall be installed and the online data be connected to the server of the
concerned SPCB/ PCC.
97.10 Checklist of Minimal Requisite Facilities:

Sl No | Particulars
7 Dedicated Polypropylene (PP)/ Fibreglass reinforce plastic (FRP)/ Polypropylene
Fibre Glass Reinforced Plastic(PRV)/ suitable storage tank for storage of Process
residue with acid proof brick lining and proper slope & seepage collection pit in the
storage tank area and tanker unloading area
2. Cool, dry well-ventilated covered sheds for Process residue storage tanks, product
storage tanks and process activities within premises and dedicated hazardous storage
area for temporary storage of hazardous waste generated during utilization process.
3. Mechanical transfer pumps with fixed pipeline for transportation and handling of
Process residue. Manual handling shall be strictly avoided.
4. Stack to have sampling port, platform, access to the platform etc. as per the
guidelines on methodologies for source emission monitoring published by CPCB
under Laboratory Analysis Techniques LATS/80/2013-14.
5. Alkali scrubber shall be provided to the reactors and the vacuum pump of the
distillation column in the said utilization process.
6. Jacketed reactors, distillation & condensation system, and agitated nutsche filter.

7 Sparkler carbon filter for filtration of sodium acetate.

Waste Management-II Division, CPCB, Delhi \o- 7|Page

~
:
Utilization of the Process residue containing Ethanol >30 % [generated during the manufacturing of
Glufosinate - Technical Pesticide] for recovering Ethanol (93%) and Sodium Acetate (30%)

8 Dedicated storage tank for storing the Salt sludge; Carbon sludge; and first cut from
the distillation process — Organic liquid waste to be sent to CHWIF / Co-processing
for final disposal.
9 Online analyzers for HCl and TOC emission monitoring in the stack, in case of
continuous process operations.
9. ate ate ate of,

Waste Management-II Division, CPCB, Delhi =a ge