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Vinyl Chloride and Polyvinyl Chloride 3 Vinyl chloride and polyvinyl chloride Our new name is ThyssenKrupp Industrial Solutions www.thyssenkrupp-industrial-solutions.com ThyssenKrupp Uhde 2 Table of contents 1. Company profi le 3 2. The Vinnolit VCM process 4 2.1 General process description 5 2.2 Direct chlorination 6 2.3 Oxychlorination 8 2.4 EDC distillation 10 2.5 EDC cracking 11 2.6 VCM distillation 12 2.7 Measures to recover by-products and to protect the environment 13 2.7.1 HCl recycling with waste gas heat recovery 13 2.7.2 Waste water treatment 13 2.7.3 Liquid and waste gas collection systems 13 2.8 Cumulated capacity of reference plants 14 3. The Vinnolit S-PVC process 16 3.1 Description of the S-PVC process 17 3.2 Advantages of the S-PVC process 18 3.3 The new Vinnolit High-Performance Reactor for suspension PVC 19 3.4 The Vinnolit MST Cyclone Drier 20 3.5 Products and applications 21 4. References 22 3 1. Company profi le With its highly specialised workforce of more than 5,600 employees Vinnolit is one of Europe’s leading EDC, VCM and PVC producers and its international network of subsidiaries and branch offi ces, Uhde, with a capacity of 780,000 t/year of PVC, 665,000 t/year of VCM a Dortmund-based engineering contractor, has to date successfully and upstream chlorine plants. They enhance and optimise their completed over 2,000 projects throughout the world. process technology on a permanent basis. Vinnolit was founded in 1993 as a 50/50 joint venture between Hoechst AG and Wacker Uhde’s international reputation has been built on the successful Chemie GmbH. The new company drew on the experience of its application of its motto Engineering with ideas to yield cost-effective two founders, both active in the vinyl sector for almost 60 years. high-tech solutions for its customers. The ever-increasing demands In 2000 Advent International acquired Vinnolit. Advent is one of placed upon process and application technology in the fi elds of the world’s largest and most experienced private equity invest- chemical processing, energy and environmental protection are met ment fi rms. through a combination of specialist know-how, comprehensive service packages, top-quality engineering and impeccable punctuality. Since 1964 the licensor has granted licences for a capacity of more than 14 million tonnes of EDC, approx. 6.5 million tonnes Uhde and Vinnolit – Partners for vinyl chloride and polyvinyl chloride of VCM and about 2.9 million tonnes of S-PVC. Our licensor for the Ethylene Dichloride (EDC), Vinyl Chloride Mono- The cooperation between the licensor and Uhde has been success- mer (VCM) and for the Polyvinyl Chloride (PVC) process is Vinnolit ful for some 40 years. Uhde is the sole basic engineering partner for GmbH & Co. KG. Vinnolit’s EDC, VCM and PVC processes. 4 2. The Vinnolit VCM process Knapsack (Cologne), which have a com- bined capacity of 665,000 t/year, as well as at many other plants worldwide. The modern Vinnolit process for the pro- duction of VCM has the following major distinctive features: High operational reliability: • Reliable reaction control • Time-proven materials and equipment • State-of-the-art process control system High economic effi ciency: • Low energy consumption due to the utilisation of reaction and waste gas heat and integration with PVC or caustic soda plants • High yields • Optimised reaction conditions and Qatar Vinyl Company (QVC), V inyl chloride (VCM), which is made from reaction control Mesaieed, Qatar ethylene and chlorine, is used as feedstock • Utilisation of by-products containing in the production of the standard plastic Cl along with the recycling of HCl gas Capacities of the complex: 2 360,000 t/year of DC-EDC material PVC. • High on-stream factor 175,000 t/year of Oxy-EDC • Low personnel requirement 230,000 t/year of VCM The market for PVC and hence VCM has • Low maintenance costs continued to grow, thus dispelling the fore- • High flexible, wide range of load casts made in the 80s, according to which PVC would be substituted by other plastics. Extremely low pollution levels: • ≤ 0.01 ppm VCM (annual average) The reasons for this were not only the mani- in working areas fold applications and properties of PVC, but • Extremely low VCM emissions also the progress made in limiting emissions • Small waste water quantities and by-products during production. PVC pro- with EDC/VCM contents ≤ 1 ppm duction capacity attained growth rates of • In-plant disposal of low-boiling approx. 6% per year, accounting for approx. and high-boiling constituents in conjunc- 47 million tonnes worldwide in 2010. For the tion with HCl gas recycling and steam next few years, growth rates in the order of generation 4% per year are again expected. • Special facilities for preventing emissions when the plant is shut down As a chemical engineering contractor, Uhde • Thermal waste gas treatment added VCM to its range of processes some 40 years ago and has to date designed and Expected consumption figures for raw constructed plants with a total nominal ca- materials and utilities per 1,000 kg VCM pacity of approx. 6 million tonnes. product The VCM process applied by Uhde is licen- Ethylene (100 %) 459 kg sed by Vinnolit. The current high technologi- Chlorine (100 %) 575 kg cal standard was reached through intensive Oxygen (100 %) 139 kg development work on the part of Vinnolit Steam 250 kg1 in collaboration with Uhde. The process has been successfully applied at Vinnolit’s ex- Fuel gas 2.7 GJ isting plants at Gendorf (Bavaria) and at 1)Combined figure for VCM / PVC plant: 435 kg 5 2.1 General process description Biggest VCM plant in China SINOPEC Qilu Petrochemical Corp. Linzi, Zibo, Shandong Prov., China 400,000 t/year of VCM (balanced) 1st section: C2H4 + Cl2 C2H4Cl2 + 218 kJ/mole 2nd section: C2H4 + 2HCl + ½O2 C2H4Cl2 + H2O + 238 kJ/mole 3rd section: C2H4Cl2 C2H3Cl + HCl - 71 kJ/mole The process for the production of vinyl chlo- ride monomer (VCM) from ethylene proceeds in several process sections. In the first process section, ethylene dichlo- ride (EDC; 1,2 dichloroethane) is produced by direct chlorination, in the second section by oxychlorination. Both reactions are exo- thermal. The EDC produced by direct chlorination is fed straight into the cracking section without In the third process section, the EDC is well as liquid by-products are fed to the HCl any further purification. cracked, and the VCM formed there, as well recovery unit and converted to HCl, CO2 and as the hydrogen chloride and unconverted water. The heat of this exothermic reaction can be EDC, are separated in a VCM distillation unit. used for PVC drying in the PVC plant or for The VCM is temporarily stored in a tank, The recovered HCl is reused in the oxychlo- heating of columns in the EDC distillation while the HCl is returned to the oxychlorina- rination process, which leads to a complete unit depending on the individual plant con- tion unit and the unconverted EDC to the conversion of the input chlorine. figuration. cracking section. The diagram shows the individual sections The EDC formed by oxychlorination passes Any process water obtained undergoes treat- of the overall process which are described through a purification stage (EDC distillation). ment. Waste gases containing pollutants as on the following pages. 1⁄ Schematic diagram of a VCM plant VCM synthesis: 2 C2H4 + Cl2 + 2 O2 2 C2H3Cl + H2O Chlorine Direct EDC VCM Vinyl chloride EDC Cl2 chlorination cracking distillation VCM Cat ΔH C2H4 + Cl2 C2H4Cl2 C2H4Cl2 + 218 k J/mole C2H3Cl + HCl – 71 kJ/mole Ethylene EDC recycle EDC liquid + gaseous C2H4 distillation chlorination by-products HCl Oxygen by-product Oxychlorination HCl O2 recovery 1⁄ Cat C2H4 + 2 HCl + 2 O2 C2H4Cl2 + H2O + 238 k J/mole 6 2.2 Direct chlorination In the direct chlorination process, EDC is Gaseous chlorine is added via an injector The process is particularly produced by means of a highly exothermal nozzle to a relatively small circulating EDC environment-friendly, because: reaction of ethylene and chlorine. side stream withdrawn in the downcomer • The energy recovery options lead to a section of the CNC reactor and cooled to significant reduction of CO2-emissions The main feature of the Vinnolit direct allow the chlorine to be better pre-dissolved. • The formation of high-boiling chlorination process is an innovative boil- This cooling provides another opportunity to constituents is significantly reduced ing reactor with natural convection flow. recover the heat of reaction. • Extremely small quantities of low-boiling Recently, as a result of a joint development constituents are formed (only a few ppm) project of Uhde and Vinnolit, the compact The ethylene solution and the completely • No scrubbing water is required and natural circulation (CNC) reactor was devel- predissolved chlorine are mixed in the reac- • No catalyst is discharged with the product. oped and now is ready for introduction on tion zone of the riser and react to EDC in a the market. In the CNC reactor, the natural fast liquid-phase reaction which significantly The catalyst has no corrosive properties be- circulation is established in an internal loop lowers by-product formation. cause of its complex structure, and therefore consisting of a riser section and a down- the process equipment can be made mainly comer section, leading to a more comact Due to the reduced static pressure head in of ordinary carbon steel. Existing plants can and cost-saving reactor design. the top section of the riser, the EDC starts be converted without any difficulty. boiling. The product amount and some ex- The Vinnolit Direct Chlorination process cess EDC are withdrawn from the upper The advantages of the process can be operates at boiling conditions with a tem- part of the CNC reactor and passed on to summarised as follows: perature of 120°C.
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