Trial utilization Study Protocol
Utilization of Spent Bromide to produce Bromine
REQUEST FOR COMMENTS
The public and other institutions including SPCBs/PCCs are invited to provide
comments if any, on draft protocol for conducting a study on trial utilization of
hazardous waste i.e. Spent Sodium Bromide, Potassium Bromide, Ammonium Bromide
and Hydrobromic Acid for manufacturing of Bromine.
The enclosed draft protocol is for utilization of the Spent Sodium Bromide,
Potassium Bromide, Ammonium Bromide and Hydrobromic Acid in producing Bromine.
Comments/views are solicited within a period of one week at
[email protected]
UTILIZATION PROCESS DISCRIPTION
The process relates to utilization of spent Sodium Bromide, Potassium Bromide, Ammonium
Bromide and Hydrobromic Acid generated from following processes:
I.
During the manufacturing of Profenofos, Ortho Chloro Phenol is reacted with elemental
Bromine to produce Bromo Chloro Phenol. The bromine vapours generated during the
process is scrubbed using sodium hydroxide and water. The scrubbed liquid contains
Sodium Bromide (NaBr) and Hydrobromic Acid (HBr).
II.
During the manufacturing of Profenofos, 1,3-Dichloro benzene is reacted with Acetyl
chloride in presence of Aluminum Chloride to get 2,4-Dichloro Acetophenone which is
further reacted with elemental bromine to produce 2,4-Dichloro Phenacyl Bromide.
During Bromination reaction Potassium Bromide (NaBr) and Hydrobromic Acid (HBr) are
generated.
III.
During the manufacturing of Pigment Green 36, Bromine vapours generated from
bromination of monochorobenzene using elemental Bromine. The vapours are scrubbed
using sodium hydroxide and water solution which gives sodium bromide.
IV.
Production of Myclobutanil, KBr and NaBr are generated by scrubbing of bromine
vapours during butylation process.
V.
In production of Meta Phenoxy Benzaldehyde, during third stage Potassium Phenate
(K‐Phenate) is formed by the reaction of Phenol and Potassium Hydroxide (KOH).
K‐Phenate reacts with Meta bromo benzyl acetal (MBBA) to form meta‐Phenoxy Benzyl
HWM Division, CPCB
Trial utilization Study Protocol
Utilization of Spent Bromide to produce Bromine
Acetate (MPBA). Bromine gas is liberated from this process which is scrubbed using KOH
solution. The scrubbed liquid contains KBr.
Spent Bromide solution thus generated has the following characteristics;
Characteristics
Physical State
Sodium Bromide
Potassium Bromide Ammonium Bromide Hydrogen Bromide
Liquid
Liquid
Liquid
Liquid
Color
pH
Colorless
6.5-8.5
Colorless
6.5-8.5
Colorless
6.5-8.5
Colorless
<2
Odor
Odorless
Odorless
Pungent
Odorless
ChemicalComposition
NaBr - 25%, Water
74%, impurities like
NaCl, NaNO3 and
CaCl2 - 1%
- NaBr - 25%,
Water - 74%,
impurities like
NaCl, NaNO3 and
CaCl2 - 1%
NH4Br - 20%,
HBr
- 30%,
Water
79%, Water
69%,
impurities like
impurities like
NaCl, NaNO3 and
NaCl, NaNO3 and
CaCl2 - 1%
CaCl2 - 1%
The aforesaid spent bromide falls under Hazardous waste Class-C2, schedule II of
Hazardous and Other Waste (Management and Transboundary Movement) Rules, 2016.
The unit has proposed to utilize the above waste in production of Bromine. For
production of bromine from above waste, waste is allowed to react with chlorine gas in an
acidified reaction column, where bromine is liberated instantly. The liberated bromine is striped
out of the solution by steam striping. The bromine water vapor and steam leaves the top of the
column and passed through a condenser. Condenser falls on a phase separator. The light phase
(water) from separator returned to the column and heavy phase (Bromine) feed to the
purification column. The purification is achieved by distillation. The uncondensed chlorine
vapor along with traces of bromine escapes from the condenser and enter in to the vent
condenser. The pure bromine is cooled in a product cooler and sent to the product receiver.
Guard condenser is also provided at the top of the receiver to prevent the escape of bromine.
The vent condenser is attached to the scrubber where escaped gasses are scrubed using
acidified solution of spent Sodium Bromide, Potassium Bromide, Ammonium Bromide and
Hydrobromic Acid. The bleed from scrubber is sent back to the reactor.
HWM Division, CPCB
Trial utilization Study Protocol
Utilization of Spent Bromide to produce Bromine
Protocol of Trial Run for Utilization of Spent HBr/KBr/NH4Br
Part – A

Ambient Air Quality Monitoring
Parameters
:
Duration
No. of Samples
:
:
PM10, Ammonia and Benzene (Near
boundary wall, one in upwind and
2 in down wind direction)
24 hrs
2
Results to be compared with National Ambient Air Quality Standard notified by Central
Pollution Control Board vide notification Date 18/11/2009.

Fugutive Air Quality Monitoring
HWM Division, CPCB
Parameters
:
Duration
:
PM10, Hydrobromic acid, Chlorine
and HCl.
Not exceeding 8 hrs of operation of
the process unit
Trial utilization Study Protocol
Utilization of Spent Bromide to produce Bromine
No. of Samples
The following OSHA standards may be applicable
PM10
Hydrobromic acid
Chlorine
Hydrogen Chloride
:
3-8
:
-
5 mg/m3 TWA*
10 mg/m3 TWA
0.5 mg/m3 TWA
7 mg/m3 Ceiling
* Time-weighted average

Source Emission Monitoring
Source
Common Stack attached to Reactor
Parameters
:
Duration
No. of Samples
:
:
PM, NH3, HCl vapor and Mist,
Hydrobromic Acid and TOC
30 Minutes
Two in each during and prior to
utilization of spent Bromide
The following standard may be applicable or as prescribed by SPCB, whichever is stringent:
PM
150 mg/Nm3
Hydrobromic Acid
5 mg/Nm3
Chorine
5 mg/Nm3
HCl Vapour & Mist
35 mg/Nm3
TOC
20 mg/Nm3


Analysis of Product
Analysis of product need to be done with and without utilization of spent bromide
i.
pH
ii.
TOC
Analysis of waste generated during process
i. Characteristic of the waste generated from utilization process for each
stream of waste utilization.
ii
Assess the efficiency of the recyclization i.e. number of cycles for
recycling the waste generated from vent condenser and scrubber.
HWM Division, CPCB
Trial utilization Study Protocol
Utilization of Spent Bromide to produce Bromine
iii

Assess the management/handling of waste generated after recycling.
Analysis of liquid effluent generated during the process
Samples to be collected
:
Parameters
:
No. of Samples
:
Waste water as outlet of reactor (for
different input material)
pH, TSS, TDS, COD, Chlorides,
Bromides and NH3-N.
2 for each stream of waste

Chemical/gas handling

Asses the capacity of plant to storage handling and utilization of Spent Sodium
Bromide, Potassium Bromide, Ammonium Bromide and Hydrobromic Acid in terms of
tones per day along with details of such facilities

Chemical Mass Balance during trial utilization of Spent Bromide
i.
Assess the total utilization of spent Sodium Bromide, Potassium Bromide, Ammonium
Bromide and Hydrobromic Acid with Material Balance to check the medium of transfer,
if any.
:
Facilities provided Safety issues and the
measures taken.
Part-B
Information required to be collected during the trial run

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

Note on hazardous waste handling, transportation, storage and feeding
mechanism.
Sources of procurement of raw material i.e. Spent Sodium Bromide, Potassium
Bromide, Ammonium Bromide and Hydrobromic Acid alongwith the process
flow diagram of its generation.
Process flow diagram for utilization of hazardous waste i.e. Spent Sodium
Bromide, Potassium Bromide, Ammonium Bromide and Hydrobromic Acid.
Safety measures for handling, transportation and storage of hazardous waste
.i.e safety gadgets for workers, acid proof floor lining with proper slope and
HWM Division, CPCB
Trial utilization Study Protocol
Utilization of Spent Bromide to produce Bromine
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collection pit, chemical handling and storage area, on site storage of Process
solid waste, manifest data.
Details of fire safety arrangements.
Layout plan.
Copy of consent order (showing prescribed standards).
Copy of the on-site emergency plan as approved from Industrial Health &
Safety department.
Sketch showing locations of ambient air quality stations (with marking of
North, South direction) along with the prevailing wind direction.
Log book copy with information on quantity of hazardous waste utilized,
product manufactured alongwith the quantity of solid waste generated during
the entire trial run operation.
Copy of the TSDF membership.
Details of quantity of wastewater generated and effluent treatment facilities
provided, if any.
The trial run shall be brought to the notice of personnel involved in the
operations.
****
HWM Division, CPCB