TW202421606A - Process and plant for producing vinyl chloride from 1,2-dichloroethane - Google Patents
Process and plant for producing vinyl chloride from 1,2-dichloroethane Download PDFInfo
- Publication number
- TW202421606A TW202421606A TW112131734A TW112131734A TW202421606A TW 202421606 A TW202421606 A TW 202421606A TW 112131734 A TW112131734 A TW 112131734A TW 112131734 A TW112131734 A TW 112131734A TW 202421606 A TW202421606 A TW 202421606A
- Authority
- TW
- Taiwan
- Prior art keywords
- transfer medium
- heat transfer
- heating device
- hydrogen
- heat
- Prior art date
Links
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 52
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 title claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 96
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 38
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 239000012429 reaction media Substances 0.000 claims abstract description 13
- 238000002485 combustion reaction Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000004227 thermal cracking Methods 0.000 claims description 33
- 238000005868 electrolysis reaction Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000000446 fuel Substances 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 239000003345 natural gas Substances 0.000 claims description 4
- 239000010795 gaseous waste Substances 0.000 claims description 3
- 239000010808 liquid waste Substances 0.000 claims description 3
- 238000003776 cleavage reaction Methods 0.000 abstract 4
- 230000007017 scission Effects 0.000 abstract 4
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000005336 cracking Methods 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 13
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000002918 waste heat Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000002737 fuel gas Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- -1 chlorine hydrocarbons Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
本發明係有關於用於藉由1,2-二氯乙烷之觸媒熱裂解製造氯乙烯的方法,其中需要用於該熱裂解之熱係透過一液體熱傳送介質或冷凝熱傳送介質供給。本發明另外地提供用於藉由1,2-二氯乙烷之觸媒熱裂解製造氯乙烯的設備,其中需要用於該熱裂解之熱係透過一液體熱傳送介質或冷凝熱傳送介質供給,該設備包括:至少一反應器,該至少一反應器中發生觸媒熱裂解;至少一第一加熱裝置,該熱傳送介質係藉由該至少一第一加熱裝置的方式加熱;及一管道系統,用於供給該經加熱之熱傳送介質(4)至該反應器(1)。該至少一第一加熱裝置係藉由一燃料的方式操作,該燃料在未形成二氧化碳之情形下燃燒且宜係氫、氨或氫與氨之一混合物,更佳係氫,即該熱傳送介質係藉由透過氫或在未形成二氧化碳之情形下燃燒之另一燃料的氧化產生的熱能的方式在該至少一第一加熱裝置中加熱。 用以製造特別地需要用於製造聚氯乙烯之氯乙烯的1,2-二氯乙烷之熱裂解係遵照以下所示反應方程式: C 2H 4Cl 2→C 2H 3Cl+HCl (1) The present invention relates to a method for producing vinyl chloride by catalytic thermal cracking of 1,2-dichloroethane, wherein the heat required for the thermal cracking is supplied by a liquid heat transfer medium or a condensed heat transfer medium. The present invention further provides an apparatus for producing vinyl chloride by catalytic thermal cracking of 1,2-dichloroethane, wherein the heat required for the thermal cracking is supplied by a liquid heat transfer medium or a condensed heat transfer medium, the apparatus comprising: at least one reactor in which the catalytic thermal cracking occurs; at least one first heating device by which the heat transfer medium is heated; and a pipeline system for supplying the heated heat transfer medium (4) to the reactor (1). The at least one first heating device is operated by means of a fuel which burns without forming carbon dioxide and is preferably hydrogen, ammonia or a mixture of hydrogen and ammonia, more preferably hydrogen, i.e. the heat transfer medium is heated in the at least one first heating device by means of heat energy generated by oxidation of hydrogen or another fuel which is burned without forming carbon dioxide. The thermal cracking of 1,2-dichloroethane for the production of vinyl chloride, in particular for the production of polyvinyl chloride, follows the reaction equation shown below: C 2 H 4 Cl 2 →C 2 H 3 Cl+HCl (1)
這是一吸熱反應,其中該熱解可在氣相中在1至3MPa之高壓下及450至600℃之一溫度在沒有觸媒的情形下或在容許該熱解在較低溫度實行之催化程序中實行。This is an endothermic reaction, wherein the pyrolysis can be carried out in the gas phase at high pressures of 1 to 3 MPa and at a temperature of 450 to 600° C. in the absence of a catalyst or in catalytic processes that allow the pyrolysis to be carried out at lower temperatures.
例如,EP 0 264 065 A1揭示用於藉由1,2-二氯乙烷之無觸媒熱裂解製造氯乙烯的一方法,其中在一第一容器中加熱1,2-二氯乙烷,接著在比該第一容器低之壓力下未進一步加熱之情形下藉由使它蒸發及將該氣態1,2-二氯乙烷送入發生裂解成為氯乙烯及氯化氫之一裂解爐中而傳送至一第二容器。離開該第二容器時之1,2-二氯乙烷的溫度係220℃至280℃。在該裂解爐中,藉由一化石燃料的方式加熱該1,2-二氯乙烷進行熱裂解之管。在該裂解爐之輻射區域中該氣體1,2-二氯乙烷分別被加熱至525℃及533℃。For example, EP 0 264 065 A1 discloses a process for producing vinyl chloride by the catalystless thermal cracking of 1,2-dichloroethane, wherein the 1,2-dichloroethane is heated in a first container and then transferred to a second container by evaporating it at a lower pressure than in the first container without further heating and feeding the gaseous 1,2-dichloroethane into a cracking furnace where the cracking takes place into vinyl chloride and hydrogen chloride. The temperature of the 1,2-dichloroethane leaving the second container is 220° C. to 280° C. In the cracking furnace, the tubes for the thermal cracking of the 1,2-dichloroethane are heated by means of a fossil fuel. In the radiation zone of the cracking furnace the gaseous 1,2-dichloroethane is heated to 525° C. and 533° C., respectively.
EP 0 264 065 A1亦提及為了預熱該液態、新1,2-二氯乙烷,可使用一溫度調節介質且該溫度調節介質接著在該裂解爐之對流區域中被由加熱該裂解爐之燃燒器產生的燃料氣體加熱。如礦物油、矽油或熔融聯苯等加熱之高沸點液體適合作為該溫度調節介質。但是,這只達成預熱至150至220℃之一溫度,而該熱解本身係在大約530℃之溫度實行。因此這習知方法未用於200至400℃溫度範圍內之該熱解的實行及藉助在此為必要之一液體熱傳送介質的全部加熱。EP 0 264 065 A1 also mentions that for preheating the liquid, fresh 1,2-dichloroethane, a temperature regulating medium can be used and that the temperature regulating medium is then heated in the convection zone of the cracking furnace by the fuel gas produced by heating the burners of the cracking furnace. Heated high-boiling liquids such as mineral oil, silicone oil or molten biphenyl are suitable as the temperature regulating medium. However, this only achieves preheating to a temperature of 150 to 220° C., while the pyrolysis itself is carried out at a temperature of about 530° C. This known method is therefore not intended for carrying out the pyrolysis in a temperature range of 200 to 400° C. and for the complete heating of a liquid heat transfer medium which is necessary here.
一種用於製造氯乙烯的設備複合體大致包含: 用於由乙烯及氯製造1,2-二氯乙烷(「直接氯化」)之一設備,或 用於由乙烯、氯化氫及氧製造1,2-二氯乙烷(「氧氯化」)之一設備; 用於1,2-二氯乙烷之蒸餾純化的一設備; 用於將該蒸餾純化之1,2-二氯乙烷熱裂解成氯乙烯及氯化氫之一設備;及 用於氯化氫及未反應之1,2-二氯乙烷之蒸餾移除及用於該氯乙烯之純化的一設備。 A complex of equipment for producing vinyl chloride generally comprises: An equipment for producing 1,2-dichloroethane from ethylene and chlorine ("direct chlorination"), or An equipment for producing 1,2-dichloroethane from ethylene, hydrogen chloride and oxygen ("oxychlorination"); An equipment for distillation purification of 1,2-dichloroethane; An equipment for thermal cracking the distilled purified 1,2-dichloroethane into vinyl chloride and hydrogen chloride; and An equipment for distillation removal of hydrogen chloride and unreacted 1,2-dichloroethane and for purification of the vinyl chloride.
藉由該1,2-二氯乙烷之熱裂解製得的氯化氫可返回該氧氯化設備,其中它可再與乙烯及氧反應而形成1,2-二氯乙烷。The hydrogen chloride produced by the thermal cracking of the 1,2-dichloroethane can be returned to the oxychlorination plant, where it can react again with ethylene and oxygen to form 1,2-dichloroethane.
上述設備複合體可另外地包括用於焚化液體及/或氣體氯烴之一設備。這些係在該氯乙烯製程中產生成為副產物且主要地在1,2-二氯乙烷之蒸餾純化中移除。在這些物質之焚化中形成之氯化氫係作成鹽酸水溶液而供給至其他製程或類似地返回該氧氯化設備。來自該焚化之廢熱係使用在現有蒸汽產生程序中。The above-mentioned plant complex can additionally include a plant for incinerating liquid and/or gaseous chlorocarbons. These are produced as by-products in the vinyl chloride process and are mainly removed in the distillation purification of 1,2-dichloroethane. The hydrogen chloride formed in the incineration of these substances is supplied as aqueous hydrochloric acid solution to other processes or similarly returned to the oxychlorination plant. The waste heat from the incineration is used in the existing steam generation process.
在DE 102 52 891 A1中所述之用於將1,2-二氯乙烷裂解成氯乙烯及氯化氫的方法中,使用可降低該吸熱裂解中之操作溫度的一觸媒。但是,在這方法中,該管狀反應器亦藉由如油或氣體等主要能源載體燃燒,該爐被分成一輻射區域及一對流區域。在該輻射區域中,需要用於該熱解之熱主要藉由來自該燃燒加熱爐壁之輻射來傳送至該反應管。在該對流區域中,離開該輻射區域的該熱燃料氣體之能含量係透過對流熱傳送使用,因此可預熱、蒸發或超溫加熱該1,2-二氯乙烷成為該熱解反應中之反應物。In the process for cracking 1,2-dichloroethane to vinyl chloride and hydrogen chloride described in DE 102 52 891 A1, a catalyst is used which reduces the operating temperature in the endothermic cracking. However, in this process, the tubular reactor is also burned by means of a primary energy carrier such as oil or gas, the furnace being divided into a radiation zone and a convection zone. In the radiation zone, the heat required for the pyrolysis is transferred to the reaction tube primarily by radiation from the combustion-heated furnace wall. In the convection zone, the energy content of the hot fuel gas leaving the radiation zone is used by convective heat transfer, so that the 1,2-dichloroethane can be preheated, evaporated or superheated to become a reactant in the pyrolysis reaction.
由習知技術已知在用於製造1,2-二氯乙烷之設備中用於節能及/或熱回收的各種方法。該等方法明顯地降低操作成本且因此明顯地有助於該設備之經濟效益及減少該設備之CO 2排放。這些係例如將該等放熱反應步驟之反應熱用於加熱該設備中之散熱器的方法。WO 2014/108159 A1詳述在用於製造氯乙烯之設備中用於熱回收的各種習知方法且引用對應參考資料。 From the prior art, various methods for energy saving and/or heat recovery in plants for the manufacture of 1,2-dichloroethane are known. These methods significantly reduce the operating costs and thus significantly contribute to the economic efficiency of the plant and to the reduction of the CO 2 emissions of the plant. These are, for example, methods in which the reaction heat of the exothermic reaction steps is used to heat the radiator in the plant. WO 2014/108159 A1 describes in detail various known methods for heat recovery in plants for the manufacture of vinyl chloride and cites corresponding references.
EP 0 225 617 A1揭示用於藉由熱裂解1,2-二氯乙烷製造氯乙烯的一方法,其中提及實行這方法在某些情形中可用於透過產生蒸汽自一燃燒裂解爐的燃料氣體回收廢熱。但是,比較低燃料氣體溫度表示該等方法不是非常經濟。在這方法中1,2-二氯乙烷之熱裂解亦發生在比較高之溫度。首先,將該反應物預熱至大約243℃,接著部份地透過壓力釋放及部份地藉由用蒸汽加壓蒸發,且接著在435℃與497℃間之一裂解爐中在未使用一觸媒之情形下熱裂解。藉由一熱傳送油的方式來加熱未說明且在這些溫度亦不可能。EP 0 225 617 A1 discloses a process for producing vinyl chloride by thermal cracking of 1,2-dichloroethane, wherein it is mentioned that the implementation of this process can in certain cases be used to recover waste heat from the fuel gas of a combustion cracker by generating steam. However, the relatively low fuel gas temperatures mean that these processes are not very economical. In this process, the thermal cracking of 1,2-dichloroethane also takes place at relatively high temperatures. First, the reactants are preheated to about 243° C., then evaporated partly by pressure release and partly by pressurization with steam, and then thermally cracked in a cracking furnace at between 435° C. and 497° C. without the use of a catalyst. Heating by means of a heat transfer oil is not described and is also not possible at these temperatures.
EP 0 002 021 A1揭示用於使用經一路易士酸處理之沸石觸媒將1,2-二氯乙烷觸媒脫鹵氫成氯乙烯的一方法。當使用該等觸媒時,該反應可在高壓及200℃至400℃之範圍內的溫度且因此在比1,2-二氯乙烷之習知裂解中明顯低的溫度實行。EP 0 002 021 A1 discloses a process for the catalytic dehalogenation of 1,2-dichloroethane to vinyl chloride using zeolite catalysts treated with Lewis acid. When using such catalysts, the reaction can be carried out at high pressure and at temperatures in the range of 200° C. to 400° C. and thus at significantly lower temperatures than in the conventional cracking of 1,2-dichloroethane.
本發明之目的係提供達成操作成本減少之用於藉由1,2-二氯乙烷之熱裂解製造氯乙烯的一改良方法。本發明之另一目的係改良用於製造氯乙烯之一製造方法的CO 2平衡。 The object of the invention is to provide an improved process for the production of vinyl chloride by thermal cracking of 1,2-dichloroethane which achieves a reduction in operating costs. Another object of the invention is to improve the CO2 balance of a production process for the production of vinyl chloride.
上述目的係藉由具有在導論中所述之本質且具有請求項1之特徵的用於藉由1,2-二氯乙烷之觸媒熱裂解製造氯乙烯的一方法達成。The above objects are achieved by a process for producing vinyl chloride by catalytic thermal cracking of 1,2-dichloroethane, having the nature described in the introduction and having the features of claim 1.
依據本發明,至少部份地藉由在氫、氨或一氨-氫混合物之氧化中產生的熱能的方式來至少暫時地加熱該液體或冷凝熱傳送介質。該操作模式係CO 2中和的。使用用於1,2-二氯乙烷之熱裂解的觸媒可將該反應發生之溫度範圍轉移至較低溫度,特別地至大約200℃至大約400℃之範圍,使得該反應器可藉由一熱傳送介質而非用在現有方法中使用之化石燃料直接燃燒的方式來加熱。不使用一管狀裂解爐,可使用例如一殼管式熱交換器作為該反應器,在該殼管式熱交換器中填裝一觸媒床且該熱傳送介質較佳地在一迴路中流動通過該殼空間。 According to the invention, the liquid or condensed heat transfer medium is heated at least temporarily at least partly by means of the heat energy generated in the oxidation of hydrogen, ammonia or an ammonia-hydrogen mixture. The operating mode is CO2 -neutral. The use of a catalyst for the thermal cracking of 1,2-dichloroethane makes it possible to shift the temperature range in which the reaction takes place to lower temperatures, in particular to a range of about 200° C. to about 400° C., so that the reactor can be heated by means of a heat transfer medium instead of by means of direct combustion of fossil fuels used in prior art processes. Instead of using a tubular cracking furnace, for example a shell-and-tube heat exchanger can be used as the reactor, in which a catalyst bed is filled and the heat transfer medium preferably flows in a circuit through the shell space.
依據本發明之方法的一較佳發展,在一上游電解單元中產生至少某些或全部該欲氧化之氫。該電解單元可較佳地設置用於實行一氯-鹼電解。亦產生之氯氣可在用於氯乙烯之製造方法中用以直接氯化。或者,亦可設置該電解單元用於水電解。在這情形中,產生之氧可用於氧氯化。最後,亦可設置該電解單元用於氯化氫電解。較佳地,1,2-二氯乙烷之熱裂解中產生的氯化氫進行電化學裂解及/或形成之氯氣在該製造方法中被再使用於乙烯之氯化。According to a preferred development of the method according to the invention, at least some or all of the hydrogen to be oxidized is produced in an upstream electrolysis unit. The electrolysis unit can preferably be arranged to carry out a chlorine-alkali electrolysis. The chlorine gas also produced can be used for direct chlorination in the process for the production of vinyl chloride. Alternatively, the electrolysis unit can also be arranged for water electrolysis. In this case, the oxygen produced can be used for oxychlorination. Finally, the electrolysis unit can also be arranged for hydrogen chloride electrolysis. Preferably, the hydrogen chloride produced in the thermal cracking of 1,2-dichloroethane is subjected to an electrochemical cracking and/or the chlorine gas formed is reused in the production process for the chlorination of ethylene.
此外,有利的是需要用於該反應之熱可部份地透過藉由氫及/或氨之燃燒加熱該熱傳送介質來至少暫時地獲得。需要用於該反應之熱在此可完全透過氫及/或氨之氧化來獲得。Furthermore, it is advantageous that the heat required for the reaction can be obtained at least temporarily in part by heating the heat transfer medium by combustion of hydrogen and/or ammonia. The heat required for the reaction can here be obtained completely by oxidation of hydrogen and/or ammonia.
該熱傳送介質亦可部份地藉由透過氫及/或氨之氧化產生的熱能的方式且部份地藉由燃燒與這些燃料不同之一燃料來至少暫時地加熱。利用該方法之這較佳變型,需要用於該反應之熱大部份透過可藉由氫及/或氨的方式加熱之一第一加熱裝置來提供,但提供且可暫時地使用藉由與上述燃料不同之一燃料的方式操作之至少一第二加熱裝置。在這些情形中,該第一加熱裝置可被節制或,如有必要的話,完全地停用一段時間,或可引導該熱傳送介質使得其流動繞過該第一加熱裝置。The heat transfer medium can also be heated at least temporarily partly by means of thermal energy generated by oxidation of hydrogen and/or ammonia and partly by burning a fuel different from these fuels. With this preferred variant of the method, the heat required for the reaction is provided mostly by a first heating device which can be heated by means of hydrogen and/or ammonia, but at least one second heating device which operates by means of a fuel different from the abovementioned fuels is provided and can be used temporarily. In these cases, the first heating device can be throttled or, if necessary, completely deactivated for a period of time, or the heat transfer medium can be directed so that its flow bypasses the first heating device.
例如,該至少一第二加熱裝置可設計成用於焚化如在一氯乙烯製造設備中產生成為副產物者等液體及/或氣體氯烴的一焚化設備。For example, the at least one second heating device can be designed as an incineration plant for incinerating liquid and/or gaseous chlorine hydrocarbons such as those produced as by-products in a vinyl chloride production plant.
使用用於提供需要用於該1,2-二氯乙烷之熱解裂解之全部反應熱的一液體或冷凝熱傳送介質可藉由在存在容許相較於無催化作用之習知方法大幅降低反應溫度的適當觸媒來達成。當使用該等觸媒時,該反應溫度可例如由在習知方法中常見之大約430℃至大約530℃之數量級的溫度降低至在特別地大約200℃至400℃之範圍內的溫度。例如當使用一熱傳送油或任選之一熔融鹽時,可加熱至這範圍內之溫度。適當觸媒包括例如如在上述EP 0 002 021 A1中列舉者等物質。The use of a liquid or condensed heat transfer medium for providing all the reaction heat required for the pyrolytic cracking of the 1,2-dichloroethane can be achieved by the presence of suitable catalysts which allow a significant reduction in the reaction temperature compared to the known processes without catalysis. When using such catalysts, the reaction temperature can be reduced, for example, from temperatures of the order of about 430° C. to about 530° C., which are common in known processes, to temperatures in the range of, in particular, about 200° C. to 400° C. For example, when using a heat transfer oil or, optionally, a molten salt, heating to a temperature in this range is possible. Suitable catalysts include, for example, substances such as those listed in the above-mentioned EP 0 002 021 A1.
一種用於純熱(在一熱解爐中未催化)或熱觸媒EDC裂解(供給熱且使用一觸媒)的方法通常由下列子步驟構成: 在預定壓力預熱液體1,2-二氯乙烷達到蒸發溫度; 蒸發該預熱之1,2-二氯乙烷; 選擇地超溫加熱該1,2-二氯乙烷到達該反應溫度之範圍(若在該反應溫度之範圍內未先發生蒸發); 藉由供給熱(純熱地,或利用一觸媒熱性地)實行該裂解反應。 A method for purely thermal (uncatalyzed in a pyrolysis furnace) or hot catalytic EDC cracking (supplying heat and using a catalyst) generally consists of the following sub-steps: Preheating liquid 1,2-dichloroethane at a predetermined pressure to a vaporization temperature; Vaporizing the preheated 1,2-dichloroethane; Optionally superheating the 1,2-dichloroethane to the reaction temperature range (if vaporization does not occur within the reaction temperature range); Carrying out the cracking reaction by supplying heat (purely or thermally using a catalyst).
本發明提供一方法,該方法除了藉由一液體或冷凝熱傳送介質的方式加熱用於觸媒熱裂解反應以外,亦可藉由該熱傳送介質加熱用於該1,2-二氯乙烷之上游預熱、蒸發或超溫加熱。不是全部這些步驟都絕對必須藉由該熱傳送介質的方式加熱。本發明之方法包含上述子步驟之至少一至任一期望組合的加熱,該等個別子步驟又可(藉由器具)再分成多個個別步驟。The present invention provides a method which, in addition to heating by means of a liquid or condensed heat transfer medium for catalytic thermal cracking reactions, can also be used for upstream preheating, evaporation or superheating of the 1,2-dichloroethane by means of the heat transfer medium. Not all of these steps absolutely have to be heated by means of the heat transfer medium. The method of the present invention comprises heating of at least one to any desired combination of the above sub-steps, which individual sub-steps can be further divided (by means of apparatus) into a plurality of individual steps.
用於達成本發明之目的之「加熱」表示藉由一熱傳送介質將熱傳送至該起始材料1,2-二氯乙烷及/或至該反應混合物。這可加熱、蒸發及/或超溫加熱該起始材料1,2-二氯乙烷。熱可用一固定溫度值(等溫反應控制)供給至該反應器中之反應混合物。該反應混合物亦可被進一步加熱,且該熱係藉由部份地用以達成該反應之熱需要量及部份地用於該反應混合物之進一步加熱的加熱來供給。最後,可調整藉由該加熱對該反應混合物之熱供給使得該反應混合物之顯熱含量至少部份地用以達成該反應之熱需要量且該反應器中之反應混合物相較於該反應器入口溫度降溫。對該起始材料1,2-二氯乙烷之加熱及熱傳送係藉由伴隨冷卻該熱傳送介質/減少其顯熱含量之一液體熱傳送介質的方式及/或藉由已先被一加熱裝置蒸發之一冷凝熱傳送介質的方式來實現。"Heating" for the purposes of the present invention means transferring heat to the starting material 1,2-dichloroethane and/or to the reaction mixture by means of a heat transfer medium. This can heat, evaporate and/or superheat the starting material 1,2-dichloroethane. Heat can be supplied to the reaction mixture in the reactor at a fixed temperature value (isothermal reaction control). The reaction mixture can also be further heated and the heat is supplied by heating which is partly used to achieve the heat requirement of the reaction and partly used for further heating of the reaction mixture. Finally, the heat supply to the reaction mixture by the heating can be adjusted so that the sensible heat content of the reaction mixture is at least partly used to achieve the heat requirement of the reaction and the reaction mixture in the reactor is cooled compared to the reactor inlet temperature. The heating and heat transfer of the starting material 1,2-dichloroethane is achieved by means of a liquid heat transfer medium with concomitant cooling of the heat transfer medium/reduction of its sensible heat content and/or by means of a condensed heat transfer medium which has previously been evaporated by a heating device.
為達成本發明之方法的目的,用於該熱傳送介質之加熱裝置可為可藉由氫、氨或一氨-氫混合物(第一加熱裝置)或藉由一如加熱油或較佳之天然氣等化石燃料(第二加熱裝置) 的方式加熱的多個裝置(結合一加熱器及一蒸發器之功能的加熱器及/或蒸發器或裝置)。或者,它們可為藉由來自用於焚化一化學品設備之副產物的一設備,較佳係來自用於焚化用於氯乙烯製造之一設備複合體之副產物的一設備的廢熱的方式來加熱的一熱傳送裝置(結合一加熱器及一蒸發器之功能的加熱器及/或蒸發器或裝置)。該等裝置對所屬技術領域中具有通常知識者而言是習知的。For the purpose of the method of the present invention, the heating means for the heat transfer medium can be devices (heaters and/or evaporators or devices combining the functions of a heater and an evaporator) that can be heated by means of hydrogen, ammonia or an ammonia-hydrogen mixture (first heating means) or by means of a fossil fuel such as heating oil or preferably natural gas (second heating means). Alternatively, they can be a heat transfer device (heaters and/or evaporators or devices combining the functions of a heater and an evaporator) heated by means of waste heat from a plant for incineration of by-products of a chemical plant, preferably from a plant for incineration of by-products of a plant complex for the manufacture of vinyl chloride. Such devices are known to those having ordinary knowledge in the art.
一般而言,用於1,2-二氯乙烷之觸媒熱裂解的一設備的熱需要量可只部份地藉由焚化用於氯乙烯製造之一設備複合體的副產物來獲得。因此,在一較佳操作模式中,該熱傳送介質藉由來***化副產物之廢熱的方式來初始地加熱且需要之熱的剩餘部份係藉由在該第一加熱單元中燃燒氫、氨或一氫-氨混合物來供給。In general, the heat requirement of a plant for the catalytic thermal cracking of 1,2-dichloroethane can only be partially obtained by incinerating by-products of a plant complex for the manufacture of vinyl chloride. Therefore, in a preferred operating mode, the heat transfer medium is initially heated by means of waste heat from the incineration by-products and the remainder of the required heat is supplied by burning hydrogen, ammonia or a hydrogen-ammonia mixture in the first heating unit.
依據本發明之方法之一較佳發展,該液體或冷凝熱傳送介質係在一迴路中循環,該迴路包括透過氫、氨或一氫-氨混合物之氧化來操作的該至少一第一加熱裝置及用於1,2-二氯乙烷之觸媒熱裂解的一反應器,其中一熱交換發生在該反應器中之一反應介質與該熱傳送介質之間。上述迴路宜亦包括透過燃燒與上述燃料不同之至少一燃料來操作的至少一第二加熱裝置。According to a preferred development of the method according to the invention, the liquid or condensed heat transfer medium circulates in a circuit comprising the at least one first heating device operated by oxidation with hydrogen, ammonia or a hydrogen-ammonia mixture and a reactor for catalytic thermal cracking of 1,2-dichloroethane, wherein a heat exchange takes place between a reaction medium in the reactor and the heat transfer medium. The circuit preferably also comprises at least one second heating device operated by burning at least one fuel different from the fuel.
依據本發明之方法之一較佳發展,至少一第一加熱裝置及少一第二加熱裝置係在該迴路中串聯地連接。在這情形中,該熱傳送介質先在一管道迴路中流動通過該第二加熱裝置且接著通過位於該第二加熱裝置下游之該第一加熱裝置;或者,通過這兩個加熱裝置之流動可反過來發生。或者,該等二加熱裝置亦可配置成一準並聯連接,即包括該等加熱裝置之管道迴路的連接使得該等相關管道可例如透過閥關閉,因此該熱傳送介質可流動通過該第二加熱裝置且未亦流動通過該第一加熱裝置,或在需要之情形下反之亦然。According to a preferred development of the method according to the invention, at least one first heating device and at least one second heating device are connected in series in the circuit. In this case, the heat transfer medium first flows in a pipe loop through the second heating device and then through the first heating device located downstream of the second heating device; alternatively, the flow through the two heating devices can take place in reverse. Alternatively, the two heating devices can also be configured as a quasi-parallel connection, i.e. the connection of the pipe loop including the heating devices is such that the relevant pipes can be closed, for example by means of valves, so that the heat transfer medium can flow through the second heating device and not also through the first heating device, or vice versa if necessary.
依據本發明之方法之一較佳發展,該熱傳送介質係在該迴路中與該反應介質通過該反應器之流動逆流地循環。這變型對於有效率熱傳送是有利的。或者,該熱傳送介質可與該反應介質之流動順流地流動。According to a preferred development of the method according to the invention, the heat transfer medium circulates in the circuit countercurrently to the flow of the reaction medium through the reactor. This variant is advantageous for efficient heat transfer. Alternatively, the heat transfer medium can flow cocurrently with the flow of the reaction medium.
依據本發明之方法之一較佳發展,該第二加熱裝置係藉由來自用於焚化一氯乙烯製造設備之副產物的一設備的廢熱的方式來至少暫時地操作。這變型之優點係使用之廢熱主要來自相同設備複合體內之一設備元件,這表示可改善該方法之能源平衡。According to a preferred development of the method according to the invention, the second heating device is operated at least temporarily by means of waste heat from a plant for incinerating by-products of a monochloroethylene production plant. This variant has the advantage that the waste heat used mainly comes from a plant element within the same plant complex, which means that the energy balance of the method can be improved.
依據本發明之方法之一較佳發展,該第二加熱裝置係以全負載永久地操作。需要用於熱裂解之能量的剩餘部份可藉由被氫及/或氨加熱之一第一加熱單元的方式供給至該熱傳送介質。在該方法之這變型中,該第二加熱裝置宜永久地在操作溫度。According to a preferred development of the method according to the invention, the second heating device is permanently operated at full load. The remainder of the energy required for thermal cracking can be supplied to the heat transfer medium by means of a first heating unit heated by hydrogen and/or ammonia. In this variant of the method, the second heating device is preferably permanently at operating temperature.
依據本發明之方法之一較佳發展,該1,2-二氯乙烷之熱裂解係在200℃至400℃之一溫度範圍內實行。這是可藉由例如熱傳送油等液體熱傳送介質輕易地達成的一較佳溫度範圍。According to a preferred development of the method according to the invention, the thermal cracking of 1,2-dichloroethane is carried out in a temperature range of 200° C. to 400° C. This is a preferred temperature range which can be easily achieved by means of a liquid heat transfer medium such as heat transfer oil.
本發明更提供用於藉由1,2-二氯乙烷之觸媒熱裂解製造氯乙烯的一設備,其中需要用於該1,2-二氯乙烷之熱裂解及較佳地亦用於該1,2-二氯乙烷之預熱、蒸發及/或超溫加熱的熱係透過一液體熱傳送介質或冷凝熱傳送介質供給,該設備包括:至少一反應器,在該至少一反應器中發生該熱裂解;至少一第一加熱裝置,該液體熱傳送介質藉由該至少一第一加熱裝置的方式加熱;及一管道系統,用於供給該經加熱之熱傳送介質至該反應器,其中該至少一第一加熱裝置係設計成用於氫及/或氨之氧化,即它可透過上述燃料中之一者的氧化,較佳地藉由燃燒來產生熱。The present invention further provides an apparatus for producing vinyl chloride by catalytic thermal cracking of 1,2-dichloroethane, wherein the heat required for the thermal cracking of the 1,2-dichloroethane and preferably also for preheating, evaporation and/or superheating of the 1,2-dichloroethane is supplied by means of a liquid heat transfer medium or a condensing heat transfer medium, the apparatus comprising: at least one reactor in which the thermal cracking takes place; at least one first heating device by means of which the liquid heat transfer medium is heated; and a piping system for supplying the heated heat transfer medium to the reactor, wherein the at least one first heating device is designed for the oxidation of hydrogen and/or ammonia, i.e. it can generate heat by oxidation of one of the above-mentioned fuels, preferably by combustion.
當該設備包括在該至少一第一加熱裝置上游之至少一電解單元,特別地用於實行一氯-鹼電解、一水電解或一氯化氫電解時在此是特佳的,其中(選擇地亦在混合氨後)產生之氫供給至該至少一第一加熱裝置。It is particularly preferred here when the apparatus comprises at least one electrolysis unit upstream of the at least one first heating device, in particular for carrying out a chlorine-alkali electrolysis, a water electrolysis or a hydrogen chloride electrolysis, wherein the hydrogen produced (optionally also after mixing with ammonia) is fed to the at least one first heating device.
此外,該設備可包括用於加熱該反應介質之至少一第二加熱裝置,其係設計成用於燃燒與氫及氨不同之至少一燃料,例如甲烷、天然氣及/或來自一化學品設備之液體及/或氣體廢棄物。在這情形中,較佳的是該熱傳送介質先流動通過該第二加熱裝置。需要用於該1,2-二氯乙烷之裂解及亦用於其預熱以便蒸發及/或超溫加熱它之熱的剩餘部份可透過該第一加熱單元來供給。該第一加熱單元可較佳地設計成可調節用於達到該熱傳送介質中之一預定最終溫度。Furthermore, the apparatus can comprise at least one second heating device for heating the reaction medium, which is designed for burning at least one fuel other than hydrogen and ammonia, for example methane, natural gas and/or liquid and/or gaseous waste from a chemical plant. In this case, it is preferred that the heat transfer medium first flows through the second heating device. The remainder of the heat required for the cracking of the 1,2-dichloroethane and also for its preheating for evaporation and/or superheating it can be supplied via the first heating unit. The first heating unit can preferably be designed to be adjustable for reaching a predetermined final temperature in the heat transfer medium.
在本發明之一較佳發展中,該管道系統形成該熱傳送介質之一迴路,該迴路包括該反應器及藉由氫、氨或一氫-氨混合物的方式操作之該至少一第一加熱裝置。In a preferred development of the invention, the pipe system forms a circuit of the heat transfer medium, which circuit comprises the reactor and the at least one first heating device operated by means of hydrogen, ammonia or a hydrogen-ammonia mixture.
依據本發明之一較佳變型,該熱傳送介質之該迴路亦包括該至少一第二加熱裝置。在這情形中,流動之順序宜使得該介質先流動通過該第二加熱裝置。因此在此提及之用語「第一」或「第二」加熱裝置只表示功能不同本質之加熱裝置而非界定該熱傳送介質流動通過它們之順序。According to a preferred variant of the invention, the circuit of the heat transfer medium also includes the at least one second heating device. In this case, the order of flow is preferably such that the medium flows through the second heating device first. Therefore, the term "first" or "second" heating device mentioned here only refers to heating devices of different functional nature and does not define the order in which the heat transfer medium flows through them.
在本發明之一較佳發展中,該第一加熱裝置及該第二加熱裝置係串聯地或並聯地配置在該熱傳送介質之該迴路中。In a preferred development of the invention, the first heating device and the second heating device are arranged in series or in parallel in the circuit of the heat transfer medium.
依據本發明之一較佳變型,設置用於將熱由該熱傳送介質傳送至流動通過該反應器或存在該反應器中之一反應介質的裝置。According to a preferred embodiment of the invention, means are provided for transferring heat from the heat transfer medium to a reaction medium flowing through the reactor or present in the reactor.
在本發明之一較佳發展中,該反應器包含一殼管式熱交換器,該殼管式熱交換器之管填裝一觸媒床且該殼管式熱交換器較佳地具有在該迴路中循環之該熱傳送介質流動通過的一殼空間。In a preferred development of the invention, the reactor comprises a shell and tube heat exchanger, the tubes of which are filled with a catalyst bed and which preferably has a shell space through which the heat transfer medium circulating in the circuit flows.
以下參照用以更詳細地說明本發明方法之一示範實施例變型的圖。圖1及2中之繪圖示意地大幅簡化且只顯示在本發明之上下文中相關的這些設備組件。該設備包含一反應器1,1,2-二氯乙烷(EDC)之一反應器注入流2例如透過至少一管道供給至該反應器,該1,2-二氯乙烷在熱之作用下在反應器1中裂解成單體氯乙烯(VCM),且氯乙烯之形成伴隨氯化氫之形成。該方法之所述產物在一反應器排出流3中離開反應器1。Reference is made below to the figures which illustrate an exemplary embodiment variant of the process according to the invention in more detail. The drawings in FIGS. 1 and 2 are schematically greatly simplified and only show those plant components which are relevant in the context of the invention. The plant comprises a reactor 1 to which a reactor feed stream 2 of 1,2-dichloroethane (EDC) is fed, for example via at least one pipeline, and which 1,2-dichloroethane is cracked in the reactor 1 under the action of heat to vinyl chloride monomers (VCM), the formation of which is accompanied by the formation of hydrogen chloride. The product of the process leaves the reactor 1 in a reactor outlet stream 3.
該反應器1係整合在由一管道系統8形成的一熱傳送介質4之一迴路18中使得熱透過例如一熱傳送油等該液體熱傳送介質供給至該反應器1,該液體熱傳送介質宜與該反應介質逆流地流動以便加熱流動通過該反應器1(請參見圖2)之反應介質13至在反應器1中發生1,2-二氯乙烷觸媒熱裂解成氯乙烯之例如300℃至400℃的一溫度。The reactor 1 is integrated in a circuit 18 of a heat transfer medium 4 formed by a piping system 8 so that heat is supplied to the reactor 1 via the liquid heat transfer medium, such as a heat transfer oil, which preferably flows countercurrently to the reaction medium in order to heat the reaction medium 13 flowing through the reactor 1 (see FIG. 2 ) to a temperature of, for example, 300° C. to 400° C. at which catalytic thermal cracking of 1,2-dichloroethane to vinyl chloride occurs in the reactor 1.
以下更詳細地說明該熱傳送介質4之迴路18。該熱傳送介質4之迴路18包括用於使該熱傳送介質4在該迴路18中循環之一泵5,其中在該泵5之下游,該熱傳送介質先流動通過依據本發明之教示係可選擇的一第二加熱裝置7,其中若該第二加熱裝置7運轉,可藉由燃燒例如甲烷、天然氣及/或來自一化學品設備之氣體及/或液體廢棄物等與氫及/或氨不同的至少一燃料或藉由例如來自一氯乙烯製造設備等來自一化學品設備之廢熱的熱能來加熱該熱傳送介質4。The circuit 18 of the heat transfer medium 4 is described in more detail below. The circuit 18 of the heat transfer medium 4 comprises a pump 5 for circulating the heat transfer medium 4 in the circuit 18, wherein downstream of the pump 5, the heat transfer medium first flows through a second heating device 7 which is optional according to the teaching of the present invention, wherein if the second heating device 7 is operated, the heat transfer medium 4 can be heated by burning at least one fuel different from hydrogen and/or ammonia, such as methane, natural gas and/or gaseous and/or liquid waste from a chemical plant, or by thermal energy from waste heat from a chemical plant, such as from a monochloroethylene production plant.
在該第二加熱裝置7之下游,該熱傳送介質4流動通過用氫10、氨11或一氨-氫混合物燃燒之一第一加熱裝置6以便加熱該熱傳送介質4。如圖1所示,用於加熱之氫10可例如在一上游電解單元9中產生。該電解單元9可較佳地設置成用於實行一氯-鹼電解、一水電解或一氯化氫電解。Downstream of the second heating device 7, the heat transfer medium 4 flows through a first heating device 6 which burns hydrogen 10, ammonia 11 or an ammonia-hydrogen mixture in order to heat the heat transfer medium 4. As shown in FIG1 , the hydrogen 10 used for heating can be generated, for example, in an upstream electrolysis unit 9. The electrolysis unit 9 can preferably be configured to carry out a chlorine-alkali electrolysis, a water electrolysis or a hydrogen chloride electrolysis.
在該示範實施例中,該第二加熱裝置7及該第一加熱裝置6係在該迴路18之管道系統8中朝流動之方向一個接著一個地配置且因此串聯地連接。或者,該等二加熱裝置亦可互相並聯地連接,即與圖1中不同地,該等二加熱裝置係整合在一管道系統8中使得該熱傳送介質4亦可至少流動通過該等二加熱裝置中之一者或另一者,同時繞過另一加熱裝置。In the exemplary embodiment, the second heating device 7 and the first heating device 6 are arranged one after the other in the direction of flow in the pipe system 8 of the loop 18 and are thus connected in series. Alternatively, the two heating devices can also be connected in parallel with each other, i.e., unlike in FIG. 1 , the two heating devices are integrated in a pipe system 8 so that the heat transfer medium 4 can also flow through at least one or the other of the two heating devices while bypassing the other heating device.
在該等二加熱裝置6與7串聯地配置的圖1所示之變型中及亦在未圖示之具有並聯連接之變型中,可設置未顯示在圖1中之閥以開啟及關閉該等加熱裝置或在適當地方阻斷該迴路18中之該等管道。此外,可設置一或多個調節裝置(亦未顯示在圖1中)以便依據該反應器1中之反應介質的加熱需求來調節由該第一及/或第二加熱裝置6與7供給之熱輸出。In the variant shown in FIG. 1 in which the two heating devices 6 and 7 are arranged in series and also in a variant with a parallel connection not shown, valves not shown in FIG. 1 may be provided to open and close the heating devices or to block the pipes in the loop 18 where appropriate. In addition, one or more regulating devices (also not shown in FIG. 1 ) may be provided in order to regulate the heat output supplied by the first and/or second heating devices 6 and 7 depending on the heating requirements of the reaction medium in the reactor 1.
圖1所示之本發明的一變型選擇地另外包括可藉由該熱傳送介質4流之熱含量的方式來預熱、蒸發及超溫加熱該反應器注入流2的一裝置19,其中這些選項不一定全部都要實現,而是可以任一組合方式實現。該裝置19係配置在該熱傳送介質之迴路中且宜在該反應器1之下游。A variant of the invention shown in FIG. 1 optionally further comprises a device 19 for preheating, evaporating and superheating the reactor feed stream 2 by means of the heat content of the heat transfer medium 4 stream, wherein these options do not necessarily all have to be implemented, but can be implemented in any combination. The device 19 is arranged in the heat transfer medium circuit and preferably downstream of the reactor 1.
1:反應器 2:反應器注入流 3:反應器排出流 4:熱傳送介質 5:再循環泵 6:第一加熱裝置 7:第二加熱裝置 8:管道系統 9:電解單元 10:氫 11:氨 12:熱傳送裝置 13:反應介質 14:殼管式熱交換器 15:管 16:觸媒床 17:殼空間 18:迴路 19:用於預熱及/或蒸發及/或超溫加熱的裝置 1: Reactor 2: Reactor inlet stream 3: Reactor outlet stream 4: Heat transfer medium 5: Recirculation pump 6: First heating device 7: Second heating device 8: Pipeline system 9: Electrolysis unit 10: Hydrogen 11: Ammonia 12: Heat transfer device 13: Reaction medium 14: Shell and tube heat exchanger 15: Tube 16: Catalyst bed 17: Shell space 18: Loop 19: Device for preheating and/or evaporation and/or superheating
以下依據一示範實施例參照附圖更詳細地說明本發明,其中: 圖1顯示用於藉由1,2-二氯乙烷之觸媒熱裂解製造氯乙烯之依據本發明的一設備的示意簡化設備圖;及 圖2顯示包含一殼管式熱交換器之一反應器的示意圖,該殼管式熱交換器之管填裝一觸媒床。 The present invention is described in more detail below with reference to the accompanying drawings according to an exemplary embodiment, wherein: FIG. 1 shows a schematic simplified apparatus diagram of an apparatus according to the present invention for producing vinyl chloride by catalytic thermal cracking of 1,2-dichloroethane; and FIG. 2 shows a schematic diagram of a reactor comprising a shell-and-tube heat exchanger, the tubes of which are filled with a catalyst bed.
1:反應器 1: Reactor
2:反應器注入流 2: Reactor injection flow
3:反應器排出流 3: Reactor discharge flow
4:熱傳送介質 4: Heat transfer medium
5:再循環泵 5: Recirculation pump
6:第一加熱裝置 6: First heating device
7:第二加熱裝置 7: Second heating device
8:管道系統 8: Pipeline system
9:電解單元 9: Electrolytic unit
10:氫 10: Hydrogen
11:氨 11: Ammonia
18:迴路 18: Loop
19:用於預熱及/或蒸發及/或超溫加熱的裝置 19: Device for preheating and/or evaporation and/or overheating
Claims (21)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102022208894.8 | 2022-08-29 | ||
LULU102998 | 2022-08-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
TW202421606A true TW202421606A (en) | 2024-06-01 |
Family
ID=
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20160002035A1 (en) | Steam methane reformer system and method of performing a steam methane reforming process | |
CN1318798C (en) | Burning method of fuel reforming appts. | |
JP2007084430A5 (en) | ||
US11845706B2 (en) | Method and plant for preparing vinyl chloride from 1,2-dichloroethane | |
KR20240012479A (en) | Ammonia cracking for hydrogen production | |
HU202175B (en) | Process for producing vinyl chloride by splitting 1,2-dichloroethane by heat effect and device for implementing the process | |
WO2017182139A1 (en) | Process and plant for producing hydrogen by means of catalytic steam reformation of a hydrocarbonaceous feed gas | |
EA038145B1 (en) | Process and plant for the production of synthesis gas by means of catalytic steam reformation of a hydrocarbonaceous feed gas | |
TW202421606A (en) | Process and plant for producing vinyl chloride from 1,2-dichloroethane | |
CA2834946C (en) | Heat exchange system | |
US11820722B2 (en) | Method and plant for preparing vinyl chloride from 1,2-dichloroethane | |
RU2784525C1 (en) | Method and unit for producing vinyl chloride from 1,2-dichloroethane | |
RU2785841C1 (en) | Method and unit for producing vinyl chloride from 1,2-dichloroethane | |
JP4643369B2 (en) | Heavy oil reforming system and power generation system | |
BRPI0618102A2 (en) | steam generation method and apparatus | |
KR20170133456A (en) | Method for preheating dehydrogenation reactor feed | |
JPS61122102A (en) | Steam reforming of hydrocarbon | |
LU102998B1 (en) | Process and system for producing vinyl chloride from 1,2-dichloroethane | |
WO2024046801A1 (en) | Process and plant for producing vinyl chloride from 1,2-dichloroethane | |
JPH11323355A (en) | Steam reforming and steam reforming unit | |
JP2023048175A (en) | Method and device of producing mixture of ammonia decomposition products | |
DE102022208894A1 (en) | Process and system for producing vinyl chloride from 1,2-dichloroethane | |
JPH05503571A (en) | Plasma heating with closed circulation system | |
RU2007136610A (en) | REFORMING METHOD FOR PRODUCING SYNTHESIS GAS AND INSTALLATION FOR ITS IMPLEMENTATION | |
NO338230B1 (en) | Fully integrated redox-assisted gasification (RAG) for productive conversion of carbonaceous material |