(BAT) Reference Document for the Production of Chlor-alkali ...

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Chapter 4 Storage tank hazards - External corrosion - Low temperature thermal stress - Pump failure Main achieved risk levels Examples of preventative measures - All stock tanks operated at temperatures below zero insulated; fully watertight lagging where freeze/thaw conditions exist - Tanks have to be stress-relieved to prevent failure from high induced stress - Prohibit excessive physical force on valves - Use of steel resilient at low temperature (-40 °C) - The pump shall be equipped with high temperature alarm - Pump should be bunded - Pump design specifications respected Examples of corrective or emergency measures - Pressure vessel inspections include selective removal of insulation to permit inspection of external surfaces - Chlorine detectors close to the pump This level should tend to zero. Methodologies such as HAZOP (Hazard and Operability Study), HAZAN and QRA are designed to ensure that the operation of a chlorine installation poses a negligible risk to employees, the neighbouring public and the natural environment. The use of checklists is also a useful methodology to reduce the risk; an example is [Gest 92/175, 1993]. Cross-media effects Note that storage at low temperature requires deep cooling with CO2, HCFCs/HFCs or ammonia. Thus, fugitive emissions of the employed cooling agent may occur. Furthermore, low-temperature storage requires more energy than ambient storage. Reference plants Safety measures are well implemented in all chlorine producing plants in Europe. The options chosen by the operator will differ, depending on the plant location (proximity of residential areas for example), stored quantities on site and/or chlorine directly consumed in situ. Economics Examples are given for some applied safety measures. The choices made are of course dependent on the specific activity: General Electric Plastics in Bergen op Zoom (Netherlands) where chlorine is used for the synthesis of phosgene. Cryogenic storage of chlorine includes: WORKING DRAFT IN PROGRESS 1. 1 tank of 58 tonnes currently in use, 1 full tank of 58 tonnes and 1 emergency tank. All tanks are kept at -34 °C and atmospheric pressure. The whole storage is contained inside a building of 8000 m3. The chlorine absorption unit is 11 m high and 1.8 m in diameter. A fan allows a continuous venting of 5000 m3/h. The cost of the storage built in Bergen op Zoom in 1988 is estimated at about 4.3 million euros (10 million NLG, exchange rate 1998) and the maintenance cost at about 2% of the building cost. 2. ICI in Wilhelmshaven (Germany), a large quantity chlorine storage: 2 tanks of 1600 tonnes each and 1 emergency tank. Chlorine is stored in steel tanks enclosed within a shell constructed of a steel/polyurethane/aluminium sandwich material. This storage was built in the 1970s and cost about 7.7 million euros (about 15 million DEM). This storage 222 December 2011 TB/EIPPCB/CAK_Draft_1
Chapter 4 was the solution at that time to a specific situation; today it might not have been built for such large quantities. 3. ATOCHEM in Jarrie (Isère, France), loading area: Containment of a separated loading area (2 x 58 tonnes railway tanks), chlorine destruction unit and water spray equipment. The cost was approximately 1.5 million euros (September 1998). The cost can vary, depending on adaptations needed to existing installations. References [Gest 87/130, 1996], [Gest 92/175, 1993], [J. Loss Prev. Proc. Ind., March/94], [Mason, 1995] 4.3.5.1.2 The chlorine absorption unit Description This technique consists in reducing channelled emissions of chlorine to air by using a chlorine absorption unit containing a caustic soda solution and using either packed towers or ejector systems. Technical description The purpose of the chlorine destruction unit is to avoid large emissions of chlorine gas to the environment during irregular plant operation and/or emergencies, and to take care of all chlorine-containing waste gases during normal operation. The most common way to destroy the chlorine is to absorb it in weak caustic soda to produce sodium hypochlorite. The chemical reactions taking place are described in Section 2.6.12.2. The absorption system can make use of packed towers or venturi ejectors. However, packed columns, even though more complex, are better in case of emergency if electricity supply fails. They can continue to absorb chlorine from a pressure relief system using caustic soda stored in a gravity-fed head tank. The concentration of caustic soda should not exceed 22% NaOH because of the risk of salt deposition, causing blockages in the absorption plant, and freezing. The absorption system can make use of batch or continuous systems as well as of packed columns or ejectors [ 192, Euro Chlor 2011 ]: Packed columns are usually based on a counter-current flow with the chlorine gas entering the bottom of the column and the scrubbing solution entering the top. They have the advantage of larger caustic retention volumes and good mass transfer. In case of emergency, they can continue to absorb chlorine from a pressure relief system using caustic soda stored in a gravity-fed head tank even if electricity supply fails. However, packed columns require an additional fan for sucking the chlorine vent and are more susceptible to plugging. Ejectors based on the Venturi principle use a high-pressure liquid stream to create a vacuum which sucks the chlorine into the eductor where it reacts with the scrubbing solution. They have the advantage of being simple as only one pump is needed for the caustic transport and gas suction. In addition, they remain effective at low and high chlorine concentrations in the vent gases and are less sensitive to salt deposition. However, ejectors show high power consumption and the mass transfer is limited to a single stage per unit so that multiple stages or a combination with packed columns are usually required to provide adequate chlorine removal. WORKING DRAFT IN PROGRESS The design of an absorption system requires clear specifications of: the maximum quantity of chlorine; the composition of the gas stream; the maximum instantaneous flow. TB/EIPPCB/CAK_Draft_1 December 2011 223
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EUROPEAN COMMISSION JOINT RESEARCH
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PREFACE 1. Status of this document
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Reference Document on Best Availabl
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3.4.7 Emissions of noise ..........
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4.3.6.3.3 Chemical reduction ......
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List of Tables Table 2.1: Main char
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List of Figures Figure 1.1: Share p
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SCOPE WORKING DRAFT IN PROGRESS Sco
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1 GENERAL INFORMATION 1.1 Industria
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Chlorine production in Mt/yr 12 11
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Chapter 1 Figure 1.4 shows the annu
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Share of total capacity in % 70 70%
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1.4 Chlor-alkali products and their
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Total consumption: 9 801 kt Miscell
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1.4.5 Consumption of hydrogen Chapt
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Chapter 1 and hazardous waste incin
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2 APPLIED PROCESSES AND TECHNIQUES
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Chapter 2 WORKING DRAFT IN PROGRESS
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Chapter 2 The main characteristics
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2.2 The mercury cell technique proc
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Chapter 2 Characteristics of the ca
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2.3 The diaphragm cell technique pr
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Source: [ 2, Le Chlore 2002 ] [USEP
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2.4 The membrane cell technique pro
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Chapter 2 (carcinogenic) [ 76, Regu
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Chapter 2 The membranes used in the
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Table 2.2: Typical configurations o
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2.5 Brine supply 2.5.1 Sources, qua
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Chapter 2 centrifuges before dispos
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Source: [ 29, Asahi Glass 1998 ] (p
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Impurity Source Upper limit of brin
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Chapter 2 No such dechlorination tr
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Chapter 2 The cooling water is gene
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Chapter 2 composition of the chlori
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2.6.11 Dealing with impurities 2.6.
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Chapter 2 amount of chlorine, and t
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2.6.12.2 Chemical reactions Chapter
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2.7 Caustic processing production,
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Chapter 2 2.8 Hydrogen processing p
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3 CURRENT PRESENT EMISSION AND CONS
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Chapter 3 Table 3.1: Overview of em
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3.3 Consumption levels of all cell
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3.3.3 Ancillary materials Ancillary
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Further materials and/or further us
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Chapter 3 current) and the efficien
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Chapter 3 distance means a higher f
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3.3.4.3.6 Production of caustic pot
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Chapter 3 hydrogen at low pressure
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28 kg of hydrogen is produced {Thes
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Chapter 3 depleted brine is recircu
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Chapter 3 Table 3.10: Emissions of
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Chapter 3 When measuring chlorine i
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Chapter 3 concentrations of organic
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Chapter 3 3.4.3 Emissions and waste
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Chapter 3 {Please TWG provide infor
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Chapter 3 in process and waste wate
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Chapter 3 produced per year has bee
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Chapter 3 of chlorine capacity. The
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Table 3.23: Mercury emissions from
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Mercury emissions in g Hg/t Cl capa
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Chapter 3 Table 3.24: Mercury emiss
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Chapter 3 KCl are higher than from
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Chapter 3 When concentrated solid c
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Chapter 3 Generally, storage of con
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Chapter 3 recycled brine systems si
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Process Maintenance To solid treatm
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3.5.9.5 Graphite and activated Acti
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Chapter 3 Table 3.31: Yearly waste
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Chapter 3 The fact that the differe
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Chapter 3 3.6 Emissions Emission an
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Reported asbestos concentrations ar
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Chapter 3 3.7 Emissions Emission an
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{A list of techniques used on full
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3.8.3 PCDDs/PCDFs, PCBs, PCNs and P
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Chapter 3 The ‘dioxin’ pattern
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Chapter 4 4 TECHNIQUES TO CONSIDER
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Heading within the sections Cross-m
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4.1 Mercury cell plants 4.1.1 Overv
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Chapter 4 plants at comparable capa
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Chapter 4 Table 4.2: Data from the
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Chapter 4 environment can be expect
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4. Plant size Chapter 4 An increase
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Table 4.6: Comparison of reported c
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Chapter 4 Generally, conversion cos
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4.1.3 Decommissioning 4.1.3.1 Decom
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3. Emptying of the cells and handli
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Chapter 4 Table 4.7: Overview of co
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Table 4.8: Techniques for monitorin
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Chapter 4 Table 4.10: Decommissioni
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Page 191 and 192: Chapter 4 diaphragms [ 31, Euro Chl
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Page 211 and 212: Chapter 4 current density resulting
Page 213 and 214: Chapter 4 modifications to auxiliar
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Page 217 and 218: Chapter 4 membrane lifetimes range
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Page 231 and 232: Chapter 4 Environmental performance
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Page 285 and 286: General considerations In these BAT
Page 287 and 288: 5.2 Decommissioning of mercury cell
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5.3 Environmental management system
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Chapter 5 The BAT-associated enviro
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Chapter 5 6. In order to reduce ene
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5.6 Monitoring of emissions Chapter
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[This BAT conclusion is based on in
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5.9 Generation of waste Chapter 5 1
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5.11 Site remediation Chapter 5 20.
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Chapter 5 inorganic chloramines, di
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6 EMERGING TECHNIQUES 6.1 Introduct
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Chapter 6 cooperation with the Japa
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Chapter 6 In December 1998 a test w
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6.3 Use of fuel cells in chlor-alka
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Chapter 6 hydrogen that is burnt to
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Chapter 7 7 CONCLUDING REMARKS AND
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REFERENCES References [1] Ullmann's
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References [63] Euro Chlor, Euro Ch
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References [112] Santorelli et al.,
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References [161] Germany, 'Verordnu
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[212] Florkiewicz, Long life diaphr
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References [259] Rappe et al., 'Lev
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GLOSSARY OF TERMS AND ABBREVIATIONS
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V. Units · VI. Chemical elements T
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VIII. Acronyms and definitions AC A
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EOX Extractable Organically-bound H
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Glossary Technique Ensemble of both
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ANNEX Annex {The CAK plant capaciti
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Euro Chlor No. Country code Company
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