DE1568679C3 - Process for the production of 1,2-dichloroethane - Google Patents
Process for the production of 1,2-dichloroethaneInfo
- Publication number
- DE1568679C3 DE1568679C3 DE1568679A DE1568679A DE1568679C3 DE 1568679 C3 DE1568679 C3 DE 1568679C3 DE 1568679 A DE1568679 A DE 1568679A DE 1568679 A DE1568679 A DE 1568679A DE 1568679 C3 DE1568679 C3 DE 1568679C3
- Authority
- DE
- Germany
- Prior art keywords
- acetylene
- hydrogen chloride
- dichloroethane
- ethylene
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 4
- 238000004519 manufacturing process Methods 0.000 title description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 29
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 29
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 29
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 28
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000005336 cracking Methods 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
1,2-Dichloräthan kann bekanntlich bei erhöhten Temperaturen gekrackt werden, wobei hauptsächlich Vinylchlorid und Chlorwasserstoff gebildet werden. Der gebildete Chlorwasserstoff wird zweckmäßig für die Oxychlorierung von Äthylen zu neuem 1,2-Dichloräthan durch Kreislaufführung verwendet. Bei der Krackung werden jedoch geringe Acetylenmengen durch Entfernung von 2 Mol Chlorwasserstoff vom 1,2-Dichloräthan gebildet, und dieses Acetylen wird mit dem Chlorwasserstoff im Kreislauf geführt. Bei der Oxychlorierung kann Acetylen sowohl mit dem Chlorwasserstoff als auch mit dem Chlor unter Bildung von Tri- und Tetrachloräthanen und auch etwas Trichloräthylen reagieren. Diese stark chlorierten Verbindungen von Äthan und Äthylen sind in 1,2-Dichloräthan unerwünscht, da sie schwierig zu entfernen sind und beim Krackprozeß Derivate bilden, die der Polymerisation von Vinylchlorid abträglich sind.It is known that 1,2-dichloroethane can be cracked at elevated temperatures, mainly vinyl chloride and hydrogen chloride are formed. The hydrogen chloride formed is useful for the oxychlorination of ethylene to new 1,2-dichloroethane used by recycling. When cracking however, small amounts of acetylene are obtained by removing 2 moles of hydrogen chloride from 1,2-dichloroethane and this acetylene is recycled with the hydrogen chloride. In oxychlorination can acetylene with both hydrogen chloride and chlorine with the formation of tri- and tetrachloroethanes and also some trichlorethylene react. These strongly chlorinated compounds of ethane and Ethylenes are undesirable in 1,2-dichloroethane because they are difficult to remove and derivatives in the cracking process which are detrimental to the polymerization of vinyl chloride.
Die Konzentration des Acetylens im Chlorwasserstoff aus der Krackung von 1,2-Dichloräthan liegt gewöhnlich bei 0,2 bis 4 Molprozent. Dies ist zu niedrig für eine wirtschaftliche Gewinnung oder für eine wirtschaftliche Umwandlung und Abtrennung aus dem Chlorwasserstoff, bevor dieser der Oxychlorierungsstufe für die Herstellung von 1,2-Dichloräthan zugeführt wird.The concentration of acetylene in the hydrogen chloride from the cracking of 1,2-dichloroethane is usually higher at 0.2 to 4 mole percent. This is too low for an economical extraction or for an economical one Conversion and separation from the hydrogen chloride before it goes to the oxychlorination stage for the production of 1,2-dichloroethane is supplied.
Es wurde überraschenderweise festgestellt, daß es möglich ist. Acetylen mit Wasserstoff auch in Gegenwart großer Chlorwasserstoffmengen zu einem Gemisch umzusetzen, das zum größeren Teil aus Äthylen und zum kleineren Teil aus Äthan besteht. Man hätte erwarten können, daß Acetylen und Chlorwasserstoff in Gegenwart des Hydrierkatalysators und des überschüssigen Chlorwasserstoffes reagieren wurden. In diesem Fall würde etwaiges gebildetes Vinylchlorid bei der Oxychlorierungsreaktion unter Bildung von mehrfach chloriertem Produkt reagieren, wenn es nicht abgc trennt wird, was schwierig und kostspielig ist.It has surprisingly been found that it is possible. Acetylene with hydrogen also in the presence to convert large amounts of hydrogen chloride to a mixture, the greater part of ethylene and consists to a lesser extent of ethane. One would have expected that acetylene and hydrogen chloride in The presence of the hydrogenation catalyst and the excess hydrogen chloride would react. In this In this case, any vinyl chloride formed in the oxychlorination reaction would result in the formation of multiple chlorinated product react if not separated, which is difficult and costly.
Das Verfahren gemäß der Erfindung zur Herstellung von 1,2-Dichloräthan ist dadurch gekennzeichnet, dal. manThe method according to the invention for the preparation of 1,2-dichloroethane is characterized in that. man
a) aus einer Mischung von Vinylchlorid und Chlor wasserstoff, die durch Krackung von 1,2-Dichloräthan hergestellt worden ist, den Acetylen enthaltenden Chlorwasserstoff abtrennt,a) from a mixture of vinyl chloride and hydrogen chloride obtained by cracking 1,2-dichloroethane has been prepared, separates the acetylene-containing hydrogen chloride,
b) das in diesem Chlorwasserstoff enthaltene Acetylen mit Wasserstoff (2 bis 5 Mol je Mol anwesendem Acetylen) in Gegenwart von Platin, Palladium und/oder deren Oxiden als Katalysator bei 50 bi> 200° C und einer Raumströmungsgeschwindigkei; von etwa 300 bis 5000 Raumteilen Gas je Raumtei Katalysator je Stunde zum überwiegenden Teil ir Äthylen und zum kleineren Teil in Äthan umsetzt undb) the acetylene contained in this hydrogen chloride with hydrogen (2 to 5 moles per mole present Acetylene) in the presence of platinum, palladium and / or their oxides as a catalyst at 50 bi> 200 ° C and a room flow rate; from about 300 to 5000 parts of gas per part of space The main part of the catalyst per hour is converted into ethylene and the smaller part is converted into ethane and
c) die in b) erhaltene Mischung (Chlorwasserstoff+Äthylen+Äthan) mit Äthylen und einerr Sauerstoff enthaltenden Gas in an sich bekannter Weise in Gegenwart eines Kupfer enthaltender Wirbelschichtkatalysators bei 200 bis 2500C untei Druck zu 1,2-Dichloräthan umsetzt.c) the mixture obtained in b) (hydrogen chloride + ethylene + ethane) with ethylene and an oxygen-containing gas is converted in a manner known per se in the presence of a copper-containing fluidized bed catalyst at 200 to 250 0 C under pressure to 1,2-dichloroethane.
Die Reaktion in Stufe b) kann beim Eigendruck odei bei erhöhten Drücken, die bis zu 210 atü betragen kön nen, durchgeführt werden. Bevorzugt wird ein Drucl· von 1,4 bis 7 atü.The reaction in stage b) can take place at autogenous pressure or at elevated pressures, which can be up to 210 atmospheres to be carried out. A pressure of 1.4 to 7 atm is preferred.
Der Katalysator kann als Trägerkatalysator einge setzt werden oder trägerlos sein. Wegen der niedrigerer
Kosten werden Trägerkatalysatoren bevorzugt. Beliebi ge bekannte Träger können verwendet werden, bei
spielsweise Siliciumdioxyd, Aluminiumoxyd, Kombina tionen von Aluminiumoxyd und Siliciumdioxyd, Kohle
Siliciumcarbid, die verschiedenen Tone, z. B. Kieselgur Kaolin, Fullererde oder Montmorillonit. Bevorzugt al;
Träger wird Aluminiumoxyd. Die Teilchengröße de.' Katalysators kann innerhalb sehr weiter Grenzen lieger
und hängt davon ab, ob Festbett- oder Wirbelschichtsysteme verwendet werden.
Gewöhnlich wird in Stufe b) bei. 100 bis 2000C, ζ. Β
bei 125 bis 195° C, gearbeitet.The catalyst can be used as a supported catalyst or it can be unsupported. Supported catalysts are preferred because of their lower cost. Any ge known carrier can be used, for example silicon dioxide, aluminum oxide, Kombina functions of aluminum oxide and silicon dioxide, carbon silicon carbide, the various clays, eg. B. kieselguhr kaolin, fuller's earth or montmorillonite. Preferably al; The carrier becomes aluminum oxide. The particle size de. ' Catalyst can lie within very wide limits and depends on whether fixed bed or fluidized bed systems are used.
Usually in stage b) at. 100 to 200 0 C, ζ. Β worked at 125 to 195 ° C.
Die als Raumteile Gas bei 15,60C und 1 Atm pro Vo lumeinheit Katalysator pro Stunde definierte Raumströ mungsgeschwindigkeit des Dämpfestroms im Reaktoi kann variiert werden. Es wurde gefunden, daß mit 3OC bis 5000 Raumteilen Gas pro Raumteil Katalysator prc Stunde gearbeitet werden kann. Bessere Selektivitä! hinsichtlich der Reduktion zu Äthylen wird jedoch be kurzen Kontaktzeiten und Raumströmungsgeschwin digkeiten von etwa 1500 bis 3500 erzielt. Eine ausgezeichnete gegenseitige Abstimmung hinsichtlich der Reduktion von Acetylen und Erzielung eines hohen Verhältnisses von Äthylen zu Äthan wird bei Raumströmungsgeschwindigkeiten von etwa 2000 bis 3500, Reaktionstemperaturen von etwa 125 bis 175° C und Molver hältnissen von Wasserstoff zu Acetylen von etwa 2,5 bi; 3,5 erhalten.The Raumströ defined as parts by volume of gas at 15.6 0 C and 1 atm per Vo lumeinheit catalyst per hour flow velocity of the vapor stream in the Reaktoi can be varied. It has been found that it is possible to work with 30 to 5000 parts by volume of gas per part by volume of catalyst per hour. Better selectivity! with regard to the reduction to ethylene, however, short contact times and Raumströmungsgeschwin speeds of about 1500 to 3500 are achieved. Excellent mutual coordination with regard to the reduction of acetylene and achieving a high ratio of ethylene to ethane is obtained at room flow rates of about 2000 to 3500, reaction temperatures of about 125 to 175 ° C and molar ratios of hydrogen to acetylene of about 2.5 bi; 3.5 received.
Der für die Reaktion mit dem Acetylen verwendete Wasserstoff muß nicht rein sein. Inerte Verdünnung«; mittel, wie Methan und andere gesättigte gasförmige Kohlenwasserstoffe, oder Stickstoff können in einei Menge bis zu 50 Volumprozent anwesend sein.The hydrogen used to react with the acetylene need not be pure. Inert Dilution "; agents, such as methane and other saturated gaseous hydrocarbons, or nitrogen can be converted into one Quantity up to 50 percent by volume be present.
Die Reaktion kann in Festbettsystemen oder Wirbel Schichtsystemen durchgeführt werden.The reaction can be carried out in fixed bed systems or fluidized bed systems.
1,2-Dichloräthan wird unter Druck in einem,Röhrenofen pyrolysiert, um ein Gasgemisch von Vinylchlorid, Chlorwasserstoff, Äthylendichlorid und kleineren Mengen von Verunreinigungen einschließlich Acetylen zu erhalten. Die Gasmischung wird in einem Kühlturm vom Typ des Flüssigkeitskondensors gekühlt, und; die Dämpfe verlassen, den Kühlturm bei ihrem.Taupunkt. Die Dämpfe werden dann weiter durch Kondensation in einer Kondensationsapparatur gekühlt, in eine Destillierkolonne bei einem Druck von etwa 12 Atmosphären gebracht, worin Chlorwasserstoff und Acetylen entfernt werden und das so entfernte Gasgemisch.einem Reaktor zugeführt, um das Acetylen in Äthylen und Äthan umzuwandeln. Der Reaktor enthält, einen Platinkatalysator von etwa 0,1% Platin auf. Aluminiumoxydkügelchen von 3,2 mm mit einem Schüttgewicht von 1041,3 kg/m3 und; einer Oberfläche von 6 bis 10m2/g. Der Acetylen enthaltende, aus der Destillationskolonne ausströmende Chlorwasserstoff wird in den Reaktor bei etwa.2,5.;atü eingeführt. Das Molverhältnis von Chlorwasserstoff; zu. Acetylen betrug 200 :1; Die Raumströmungsgeschwindigkeit, berechnet bei Normaltemperatur und Normaldruck, betrug etwa 1350 Raumteile Gas pro Räumteil Katalysator pro Stunde. Die Reaktionstemperatur betrug etwa 146° C. Das Molverhältnis von Wasserstoff zu Acetylen betrug 2. Die aus.dem Reaktor austretenden Gase wurden durch Gaschromatographie analysiert. Das austretende Gas enthielt kein Acetylen, und das. Molverhältnis von Äthylen zu Äthan betrug 8 :1. Die Analysenwerte zeigen ferner, daß praktisch keine Reaktion zwischen dem Acetylen und dem Chlorwasserstoff stattgefunden hatte, obwohl der verwendete Katalysator bekanntlich für die Bildung von Vinylchlorid aus Acetylen und Chlorwasserstoff aktiv ist. Es ist überraschend; daß die Hydrierung von Acetylen die bevorzugte Reaktion auch dann ist, wenn die Molverhältnisse von Chlorwasserstoff zu Acetylen, erheblich höher sind als die Molverhältnisse von Wasserstoff zu Acetylen. Ein Gemisch von Luft und Chlorwasserstoff, wenn nötig, wird im Molverhältnis von etwa 0,5 :1. Mol Sauerstoff.je.2 Mol Chlorwasserstoff und 1 Mol Äthylen in einen weiteren Reaktor eingeführt, der einen KupferchloridrTrägerkatalysator als Wirbelschicht enthält. Die Temperatur beträgt 190 bis 2500C, die Kontaktzeit etwa 10 bis 40 see und der Druck 1,05 bis 3,15 atü. Die· aus dem Reaktor austretenden Gase bestehen im wesentlichen aus nicht umgesetztem Chlorwasserstoff und 1,2-Dichloräthan, das mit Wasser gewaschen und destilliert wird. Die Reinheit des erhaltenen 1,2-Dichloräthans lag bis zu 0,5% oder um einen noch höheren Betrag über der Reinheit des 1,2-Dichloräthans, das unter Verwendung von Kreislaufchlorwasserstoff erhalten wurde, dessen Acetylengehalt nicht verringert oder beseitigt worden war.1,2-dichloroethane is pyrolyzed under pressure in a tube furnace to obtain a gas mixture of vinyl chloride, hydrogen chloride, ethylene dichloride and minor amounts of impurities including acetylene. The gas mixture is cooled in a cooling tower of the liquid condenser type, and; the vapors leave the cooling tower at their dew point. The vapors are then further cooled by condensation in a condensation apparatus, brought into a distillation column at a pressure of about 12 atmospheres, in which hydrogen chloride and acetylene are removed and the gas mixture thus removed is fed to a reactor in order to convert the acetylene into ethylene and ethane. The reactor contains a platinum catalyst of about 0.1% platinum. Alumina spheres of 3.2 mm with a bulk density of 1041.3 kg / m 3 and; a surface area of 6 to 10 m 2 / g. The acetylene-containing hydrogen chloride flowing out of the distillation column is introduced into the reactor at about 2.5 atmospheres. The molar ratio of hydrogen chloride; to. Acetylene was 200: 1; The space flow rate, calculated at normal temperature and normal pressure, was about 1350 parts by volume of gas per room part of catalyst per hour. The reaction temperature was about 146 ° C. The molar ratio of hydrogen to acetylene was 2. The gases emerging from the reactor were analyzed by gas chromatography. The exiting gas contained no acetylene and the molar ratio of ethylene to ethane was 8: 1. The analytical values also show that there was practically no reaction between the acetylene and the hydrogen chloride, although the catalyst used is known to be active for the formation of vinyl chloride from acetylene and hydrogen chloride. It's surprising; that the hydrogenation of acetylene is the preferred reaction even when the molar ratios of hydrogen chloride to acetylene are considerably higher than the molar ratios of hydrogen to acetylene. A mixture of air and hydrogen chloride, if necessary, is used in a molar ratio of about 0.5: 1. Mol oxygen. 2 moles of hydrogen chloride and 1 mole of ethylene are introduced into a further reactor which contains a supported copper chloride catalyst as a fluidized bed. The temperature is 190 to 250 0 C, the contact time about 10 to 40 seconds and the pressure 1.05 to 3.15 atmospheres. The gases emerging from the reactor essentially consist of unreacted hydrogen chloride and 1,2-dichloroethane, which is washed with water and distilled. The purity of the 1,2-dichloroethane obtained was up to 0.5% or an even higher amount than the purity of the 1,2-dichloroethane obtained using circulating hydrogen chloride, the acetylene content of which had not been reduced or eliminated.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46272065A | 1965-06-09 | 1965-06-09 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1568679A1 DE1568679A1 (en) | 1970-03-05 |
| DE1568679B2 DE1568679B2 (en) | 1975-11-06 |
| DE1568679C3 true DE1568679C3 (en) | 1985-10-03 |
Family
ID=23837517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1568679A Expired DE1568679C3 (en) | 1965-06-09 | 1966-05-07 | Process for the production of 1,2-dichloroethane |
Country Status (8)
| Country | Link |
|---|---|
| BE (1) | BE680413A (en) |
| CH (1) | CH498792A (en) |
| DE (1) | DE1568679C3 (en) |
| ES (1) | ES325919A1 (en) |
| FR (1) | FR1504480A (en) |
| GB (1) | GB1090499A (en) |
| NL (1) | NL6607714A (en) |
| SE (1) | SE328271B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3009520A1 (en) * | 1980-03-12 | 1981-09-24 | Wacker-Chemie GmbH, 8000 München | METHOD FOR SEPARATING ACETYLENE FROM THE REACTION PRODUCT OF THERMAL 1,2-DICHLORETHANE CLEAVAGE |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4206188A (en) | 1978-12-06 | 1980-06-03 | The Dow Chemical Company | Removal of acetylene from HCl streams |
| JPS5651420A (en) * | 1979-10-04 | 1981-05-09 | Kanegafuchi Chem Ind Co Ltd | Hydrogenation of acetylene contained in hydrogen chloride gas, and preparation of 1,2-dichloroethane |
| DE3043442A1 (en) * | 1980-11-18 | 1982-06-24 | Wacker-Chemie GmbH, 8000 München | METHOD FOR PURIFYING CHLORINE HYDROGEN RECOVERED BY THERMAL 1,2-DICHLORETHANIZATION |
| US4482770A (en) * | 1981-03-06 | 1984-11-13 | Wacker Chemie Gmbh | Removal of acetylene from products of 1,2-dichloroethane pyrolysis |
| FR2531695A1 (en) * | 1982-08-13 | 1984-02-17 | Solvay | PROCESS FOR THE PRODUCTION OF ACETYLENE-FREE HYDROGEN CHLORIDE FROM MIXTURES CONTAINING HYDROGEN CHLORIDE, VINYL CHLORIDE AND ACETYLENE |
| US6177599B1 (en) * | 1995-11-17 | 2001-01-23 | Oxy Vinyls, L.P. | Method for reducing formation of polychlorinated aromatic compounds during oxychlorination of C1-C3 hydrocarbons |
| CN105712835A (en) * | 2014-12-03 | 2016-06-29 | 青岛海晶化工集团有限公司 | Method for preparing VCM via balanced oxychlorination |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA695297A (en) * | 1964-09-29 | E. Hodges Charles | Production of vinyl chloride | |
| BE448632A (en) * | 1943-01-06 | |||
| DE1014103B (en) * | 1952-05-09 | 1957-08-22 | Erich Schaeffer | Process for the production of trichlorethylene and / or tetrachlorethylene from acetylene and chlorine |
| GB744081A (en) * | 1952-06-11 | 1956-02-01 | Olin Mathieson | Improvements in or relating to a process for the utilization of acetylene and ethylene mixtures |
| US2830102A (en) * | 1954-01-18 | 1958-04-08 | Kenneth A Kobe | Production of vinyl chloride from cracked hydrocarbon gases containing acetylene |
| US2858347A (en) * | 1954-08-26 | 1958-10-28 | Pure Oil Co | Process for manufacturing aliphatic chlorides |
| BE549468A (en) * | 1955-08-05 | 1900-01-01 | ||
| US3010913A (en) * | 1957-09-23 | 1961-11-28 | Monsanto Chemicals | Catalyst preparation |
| US2946829A (en) * | 1958-07-15 | 1960-07-26 | Chemetron Corp | Selective hydrogenation and palladium catalyst therefor |
| US3116342A (en) * | 1959-07-02 | 1963-12-31 | Ici Ltd | Two-stage selective hydrogenation of acetylenes |
| US3055955A (en) * | 1960-10-12 | 1962-09-25 | Union Carbide Corp | Process for the production of vinyl chloride |
| US3187064A (en) * | 1962-05-09 | 1965-06-01 | Foster Wheeler Corp | Ethylene recovery system |
-
1966
- 1966-04-23 ES ES0325919A patent/ES325919A1/en not_active Expired
- 1966-05-03 BE BE680413A patent/BE680413A/xx not_active IP Right Cessation
- 1966-05-07 DE DE1568679A patent/DE1568679C3/en not_active Expired
- 1966-05-08 SE SE07836/66*A patent/SE328271B/xx unknown
- 1966-05-10 FR FR60936A patent/FR1504480A/en not_active Expired
- 1966-05-12 CH CH693766A patent/CH498792A/en not_active IP Right Cessation
- 1966-06-03 NL NL6607714A patent/NL6607714A/xx unknown
- 1966-06-08 GB GB25434/66A patent/GB1090499A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3009520A1 (en) * | 1980-03-12 | 1981-09-24 | Wacker-Chemie GmbH, 8000 München | METHOD FOR SEPARATING ACETYLENE FROM THE REACTION PRODUCT OF THERMAL 1,2-DICHLORETHANE CLEAVAGE |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1568679B2 (en) | 1975-11-06 |
| CH498792A (en) | 1970-11-15 |
| DE1568679A1 (en) | 1970-03-05 |
| GB1090499A (en) | 1967-11-08 |
| NL6607714A (en) | 1966-12-12 |
| ES325919A1 (en) | 1967-03-01 |
| BE680413A (en) | 1966-10-17 |
| SE328271B (en) | 1970-09-14 |
| FR1504480A (en) | 1967-12-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8225 | Change of the main classification |
Ipc: C07C 19/045 |
|
| 8281 | Inventor (new situation) |
Free format text: CARROLL, RICHARD TOBEY, CUYAHOGA FALLS, OHIO, US |
|
| C3 | Grant after two publication steps (3rd publication) |