DE2206971A1 - Process for the isomerization of dichlorobutenes - Google Patents
Process for the isomerization of dichlorobutenesInfo
- Publication number
- DE2206971A1 DE2206971A1 DE19722206971 DE2206971A DE2206971A1 DE 2206971 A1 DE2206971 A1 DE 2206971A1 DE 19722206971 DE19722206971 DE 19722206971 DE 2206971 A DE2206971 A DE 2206971A DE 2206971 A1 DE2206971 A1 DE 2206971A1
- Authority
- DE
- Germany
- Prior art keywords
- dichlorobutene
- copper
- isomerization
- chlorine
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 16
- 238000006317 isomerization reaction Methods 0.000 title claims description 12
- UAZUEJTXWAXSMA-UHFFFAOYSA-N 1,1-dichlorobut-1-ene Chemical class CCC=C(Cl)Cl UAZUEJTXWAXSMA-UHFFFAOYSA-N 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 19
- XVEASTGLHPVZNA-UHFFFAOYSA-N 3,4-dichlorobut-1-ene Chemical compound ClCC(Cl)C=C XVEASTGLHPVZNA-UHFFFAOYSA-N 0.000 claims description 15
- FQDIANVAWVHZIR-OWOJBTEDSA-N trans-1,4-Dichlorobutene Chemical compound ClC\C=C\CCl FQDIANVAWVHZIR-OWOJBTEDSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 claims description 5
- 239000005749 Copper compound Substances 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 claims description 3
- PEVZEFCZINKUCG-UHFFFAOYSA-L copper;octadecanoate Chemical compound [Cu+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O PEVZEFCZINKUCG-UHFFFAOYSA-L 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 3
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- DADSZOFTIIETSV-UHFFFAOYSA-N n,n-dichloroaniline Chemical compound ClN(Cl)C1=CC=CC=C1 DADSZOFTIIETSV-UHFFFAOYSA-N 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000009835 boiling Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- AVYGCQXNNJPXSS-UHFFFAOYSA-N 2,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC=C1Cl AVYGCQXNNJPXSS-UHFFFAOYSA-N 0.000 description 3
- 150000001448 anilines Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- SWSOIFQIPTXLOI-HNQUOIGGSA-N (e)-1,4-dichlorobut-1-ene Chemical compound ClCC\C=C\Cl SWSOIFQIPTXLOI-HNQUOIGGSA-N 0.000 description 1
- BRPSAOUFIJSKOT-UHFFFAOYSA-N 2,3-dichloroaniline Chemical compound NC1=CC=CC(Cl)=C1Cl BRPSAOUFIJSKOT-UHFFFAOYSA-N 0.000 description 1
- KQCMTOWTPBNWDB-UHFFFAOYSA-N 2,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C=C1Cl KQCMTOWTPBNWDB-UHFFFAOYSA-N 0.000 description 1
- JDMFXJULNGEPOI-UHFFFAOYSA-N 2,6-dichloroaniline Chemical compound NC1=C(Cl)C=CC=C1Cl JDMFXJULNGEPOI-UHFFFAOYSA-N 0.000 description 1
- FCDOETBDFXHVJZ-UHFFFAOYSA-N 2-aminobenzoic acid;4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1.NC1=CC=CC=C1C(O)=O FCDOETBDFXHVJZ-UHFFFAOYSA-N 0.000 description 1
- MZZATKZTTVRCNA-UHFFFAOYSA-N 2-chloroaniline;3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1.NC1=CC=CC=C1Cl MZZATKZTTVRCNA-UHFFFAOYSA-N 0.000 description 1
- 241001026509 Kata Species 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 aniline compound Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000010936 titanium Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011701 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
PATENTANWÄLTEPATENT LAWYERS
dr. W.Schalk · dipl.-ing. P.^irth · dipl.-ing. G. Dannewberg DR.V.SCHMIED-KOWARZIK · DR. P. WE I N HOLD · DR. D. G U DE Ldr. W.Schalk dipl.-ing. P. ^ irth dipl.-ing. G. Dannewberg DR.V.SCHMIED-KOWARZIK DR. P. WE I N HOLD DR. D. G U DE L
6 FRANKFURT AM MAIN CR. ESCHiNHElMEIl STKASSE6 FRANKFURT AM MAIN CR. ESCHINHElMMEIL STKASSE
Case Cl 3041 Wd/CW 608 Case Cl 3041 Wd / CW 608
BP CHEMICALS INTERNATIONAL LIMITED Britannic House, Moor Lane, London E.C.2, England.BP CHEMICALS INTERNATIONAL LIMITED Britannic House, Moor Lane, London E.C. 2, England.
209836/1231209836/1231
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung -von 3,4-Dichlorbuten-1 durch Isomerisierung von 1,4~Dichlorbuten-2, oder 1t4-Dichlorbuten-2 durch Isomerisierung von 3,4-Dichlorbuten-1. The present invention relates to a process for the preparation of 3,4-dichlorobutene-1 by isomerization of 1,4-dichlorobutene-2, or 1 t of 4-dichlorobutene-2 by isomerization of 3,4-dichlorobutene-1.
Das Dichlorbuten, das man durch Chlorierung von Butadien erhält, ist eine Mischung der isomeren Verbindungen, 1,4-Dichlorbuten-2- und 3,4-Dichlorbuten-1, die etwa 60% der ersteren und etwa 40% der letzteren umfaßt. Diese beiden Isomeren sind gewöhnlich im Gleichgewicht in der Mischung vorhanden, wobei die Anteile von den Herstellungbedingungen abhängt.The dichlorobutene obtained by chlorinating butadiene is a mixture of the isomeric compounds, 1,4-dichlorobutene-2 and 3,4-dichlorobutene-1, comprising about 60% of the former and about 40% of the latter. These two isomers are usually present in the mixture in equilibrium, the proportions depending on the production conditions.
Die üblichen Verfahren zur Isomerisierung von 1,4~Dichlorbuten-2 zu 3,4-Dichlorbuten-1- oder 3,4-Dichlorbuten-1 zu 1,4-Dichlorbuten-2 bestehen aus dem Erhitzen der gemischten Isomeren mit einem oder mehreren der Katalysatoren: Metallsalze von Kupfer, Eisen, Zink, Titan, Aluminium, Zirkon und dergl. oder Erhitzen der Isomeren in Abwesenheit von Katalysatoren. Welches Verfahren man zur Isomerisierung auch anwendet, die Umwandlungsgeschwindigkeit ist unzufriedenstellend langsam, wobei hohe Temperaturen erforderlich sind, um eine brauchbare Ausbeute des richtigen Isomeren zu erhalten, und einige unerwünschte Nebenprodukte gebildet werden.The usual processes for isomerizing 1,4 ~ dichlorobutene-2 to 3,4-dichlorobutene-1 or 3,4-dichlorobutene-1 to 1,4-dichlorobutene-2 consist of heating the mixed isomers with one or more of the Catalysts: metal salts of copper, iron, zinc, titanium, aluminum, zirconium and the like, or heating of the isomers in the absence of catalysts. Whichever isomerization process is used , the rate of conversion is unsatisfactorily slow, high temperatures are required to obtain a useful yield of the correct isomer and some undesirable by-products are formed.
Es ist nun gefunden worden, daß die Verwendung von Katalysatoren mit speziellen Zusammensetzungen die Geschwindigkeit der Isomerisierungsreaktionen wesentlich beschleunigt.It has now been found that the use of catalysts with specific compositions significantly accelerates the rate of the isomerization reactions.
Gegenstand der Erfindung ist ein Verfahren zur Isomerisierung von 1,4-Dichlorbuten-2 zu 3»4-D±chlorbuten-1 oder zur Isomerisierung von 3,4-Dichlorbuten-1 zu 1,4-Dichlorbuten-2, das dadurch gekennzeichnet ist, daß es die Reaktionsstufe umfaßt, bei der die zu isomerisierende Verbindung mit einer eine oder mehrere Verbindungen von Kupfer und ein chlorhaltiges Derivat von Anilin umfassenden Katalysatorzusammensetzung in Berührung gebracht wird. The invention relates to a process for the isomerization of 1,4-dichlorobutene-2 to 3 »4-D ± chlorobutene-1 or for the isomerization of 3,4-dichlorobutene-1 to 1,4-dichlorobutene-2, which is characterized in that it comprises the reaction step in which the compound to be isomerized is brought into contact with a catalyst composition comprising one or more compounds of copper and a chlorine-containing derivative of aniline .
209836/1231209836/1231
Das chlorhaltige Derivat von Anilin in der Katalycatorzusammensetzung kann eine Aniliuverbindv^; sein, die ein oder mehrere Chloratome als Kcrnsubstituentcn ■;■-.:, V-hrlt, wie z.B. Monochloraniline und Dichlor^uiline. Dichlorc:niline,bei denen sich mindestens ein Chlorate·!:! in orlho~Stellung zu der Aminogruppe befindet, v/erden bevorzugt.The chlorine-containing derivative of aniline in the catalyst composition can be an aniline compound; be that one or more chlorine atoms as nucleus substituents e.g. monochloroaniline and dichloroiline. Dichlorc: niline, at which have at least one chlorate ·!:! in orlho ~ position to the Amino group is located, v / earths preferred.
Die Kupferverbindungen, die bei der Durchführung des erfindungsgemäßen Verfahrens verwendet werden können, können nov.'ohl organische als auch anorganische Salze oder Konplcxe von Kupfer sein. Zu geeigneten Beispielen zählen die Stearete, Oler-te und Naphthenate von Kupfer, wie z.B. Kupfer-II-ste^rr-.t, Kupf&r-II-oleat und Kupfer-Il-naphthenat. Von diesen wird Kupfer-Il-naphthenat bevorzugt.The copper compounds used in carrying out the invention Process can be used, nov.'ohl organic as well as inorganic salts or compounds of copper. Suitable examples include the stearetes, olers-te and naphthenates of copper, such as copper-II-ste ^ rr-.t, copper & r-II-oleate and copper-II-naphthenate. Of these, copper-II-naphthenate is used preferred.
Die Menge des in der vorliegenden Katalysa{:cx'zusa::ruonr>etzung anwesenden chlorhaltigen Anilinderivats kann innerhalb eines mäßig weiten Bereiches zwischen etva 0,5 und 10 Ge\-r..-% der Gesamtzusammensetzung bestehend aus Katalysator und Dichlörbuten schwanken.The amount of the chlorine-containing aniline derivative present in the present catalyst can vary within a moderately wide range between about 0.5 and 10 % by weight of the total composition consisting of catalyst and dichlorobutene.
Die erfindungsgemäße Isoraerisierungoreaktion kann bei Temperaturen zwischen etwa 80 und i60°Ct vorzugsweise zwischen etwa 100 und 130°C, bei atmosphärischen» überateοsphärischen oder unteratmosphärischen Drücken durchgeführt werden.The invention can Isoraerisierungoreaktion at temperatures between about 80 and i60 ° C t preferably between about 100 and 130 ° C, at atmospheric überateοsphärischen "or subatmospheric pressures to be performed.
Das erfindungsgemäße Verfahren kann unter /-nv.-endung eines ansatzweisen oder kontinuierlichen Verfahrens durchgeführt werden. Das Verfahren wird vorzugsweise kontinuierlich durchgeführt. Möchte man 1,4-Dichlorbuten-2- zu 3,4-Dichlorbuten-1 umwandeln, so wird das erstere oder das bereits beschriebene direkte Chlorierungsprodukt von Butadien, das vorzugsweise von hochsiedenden Anteilen befreit ist, dem Reakticncgefäß, das den Katalysator enthält, zugeführt. Dieses wird erhitzt und reines 3,4-Dichlorbuten-1 durch eine Fraktionierungskolonne pbdestilliert. Die Vorrichtung wird vorzugsweise unter reduziertem Druck gehalten, da es weder notwendig noch zweckmäßig ist, die Reaktion bei nor-The method according to the invention can be carried out using a batch or continuous process. The process is preferably carried out continuously. If you want to convert 1,4-dichlorobutene-2 to 3,4-dichlorobutene-1, so is the former or the direct chlorination product already described of butadiene, which is preferably of high-boiling Fractions is freed, the Reakticncgefäß that the catalyst contains, supplied. This is heated and pure 3,4-dichlorobutene-1 distilled through a fractionation column pb. The device is preferably kept under reduced pressure, since it is neither necessary nor expedient to
209836/1231209836/1231
BAD ORIGINALBATH ORIGINAL
malem Siedepunkt der Dichlorbutene durchzuführen, und die Destillation kann aus dem Reaktionsgefäß selbst stattfinden. Da 3,4-Dichlorbuten-1 einen niedrigeren Siedepunkt als 1,4-Dichlorbuten-2 besitzt, wird das Gleichgewicht der Reaktion zugungsten des ersteren verschoben, 'und das gosewte 1,4-Dichlorbuten-2, das zur Erhaltung eines konstanten Spiegels in dem Reaktionsgefäß zugeführt wird, so zu 3,4-Dichlorbuten~1 umgewandelt. Es sollte beachtet werden, daß bei der Abc'O.stillstion von 3,4-Dichlorbuten-1 kein Verlust an Katalysator auftritt. Da jedoch ein sehr kleiner Anteil an Dichlorbutene!! zu hochsiedenden Materialien umgewandelt wird, ist es notwendig, einen kleinen Strom aus dem Reaktionsgefäß als Flüssigkeit abzuführen, um eine Ansammlung der hochsiedenden Anteile zu verhindern. Dieser Strom wird zur Y/iedergewinnung den Dichlorlruten-Gchalts einer separaten Destillation unterworfen, der dann, zu den Reaktionsgefäß zurückgeführt wird. Bei dieser Verfahrensweise bleibt der Katalysator in dem Strom der hochsiedenden Anteile zurück, und so kann in der Praxis eine sehr kleine Ergänzung en Katalysator in das Reaktionsgefäß zugefügt v/erden. Dien sollte zur Erhaltung der bevorzugten Reaktionsgeschwindigkeit ausreichen.malem boiling point of the dichlorobutenes, and the distillation can take place from the reaction vessel itself. Since 3,4-dichlorobutene-1 has a lower boiling point than 1,4-dichlorobutene-2, the equilibrium of the reaction is shifted in favor of the former, 'and the good 1,4-dichlorobutene-2, which is used to maintain a constant level in is fed to the reaction vessel, so converted to 3,4-dichlorobutene ~ 1. It should be noted that there is no loss of catalyst in the Abc'O.stillstion of 3,4-dichlorobutene-1. However, since a very small proportion of dichlorobutenes !! is converted to high-boiling materials, it is necessary to discharge a small stream from the reaction vessel as a liquid in order to prevent the high-boiling components from accumulating. This stream is subjected to a separate distillation for recovery of the dichloro rod mixture, which is then returned to the reaction vessel. In this procedure, the catalyst in the stream of high-boiling fractions remains, and so in practice a very small addition s catalyst in the reaction vessel can added v / ground. Diene should be sufficient to maintain the preferred rate of reaction.
Im umgekehrten Fall, bei dem man 3,4-Dichlorbuten-i zu 1,4-Dichlorbuten-2 umwandeln will, v/erden die gemischten Dichlorbutene auch einem Reaktionsgefäß für kontinuierliche Arbeitsweise, wie es oben beschrieben worden ist, zugeführt, aber in diesem Fall wird - um das 1,4-Dichlorbuten~2 abzutrennen - ein flüssiger Strom aus dem Reaktionsgefäß einer geeigneten Stelle in der Nähe des Fußes der Fraktionierungskolonne, die mit dem Reaktion.«:- gefäß nicht verbunden ist und mit einem eigenen Aufkochor ausgestattet ist, zugeführt. 3,4-Dichlorbuten-1 vird vom Kopf der Kolonne entfernt und zu dem Reaktionsgefäß zurückgeführt und 1,4-Dichlorbuten-2-Dampf in der Nähe des Fußes der Kolonne, aber unterhalb des Beschickungspunktes, entfernt. Dor katalysatorhaltige Strom aus dem Aufkocher der Kolonne wird zu dem Reaktionsgefäß' zurückgeleitet, wobei eine geeignete Menge zur getrennten Destillation entfernt wird, um eine Ansammlung an hochsiedenden Anteilen in dem Reaktionsgefäß zu verhindern. Es wird eine regel-In the opposite case, in which 3,4-dichlorobutene-i is converted into 1,4-dichlorobutene-2 want to convert, the mixed dichlorobutenes are also grounded in a reaction vessel for continuous operation, fed as it has been described above, but in this one The case becomes a liquid one in order to separate the 1,4-dichlorobutene ~ 2 Stream from the reaction vessel to a suitable point near the foot of the fractionation column which is responsible for the reaction. ": - vessel is not connected and equipped with its own cooker is fed. 3,4-dichlorobutene-1 is removed from the top of the column and returned to the reaction vessel and 1,4-dichlorobutene-2 vapor removed near the base of the column but below the feed point. Dor containing catalyst Stream from the reboiler of the column is returned to the reaction vessel, an appropriate amount being separated Distillation is removed to prevent high boilers from building up in the reaction vessel. It will be a rule
209836/1231209836/1231
BAD ORIGINALBATH ORIGINAL
mäßige Katalysatorzugabe zu dem Reaktionsgefäß vorgenommen, um denjenigen zu ersetzen, der entfernt worden war, und die Reaktionsgeschwindigkeit zu erhalten.moderate addition of catalyst to the reaction vessel made to to replace the one that was removed and the rate of response to obtain.
Die folgenden Beispiele dienen zur Erläuterung der Erfindung, ohne diese einzuschränken.The following examples serve to illustrate the invention without restricting it.
Kupfer-II-naphthenat ( 3 Teile eines Handelsprodukts, das 5 Gew./Gew.-% Kupfermetall enthält) oder 1,5 Teile Kupfer-II-stearat oder 1,7 Teile Kupfer-II-oleat und 3 Teile eines in der Tabelle unten angegebenen Zusatzes wurden zu 100 Teilen 1,4-Dichlorbuten-2 hinzugefügt. Die Mischung wurde sehr schnell auf 120°C erhitzt und zu verschiedenen Zeiten wurden Proben entnommen und durch Gaschromatographie analysiert. Durch Auftragen der Umwandlung zu 3,4-Dichlorbuten-1 gegen die Zeit wurde R-|0 ( Zeit in Minuten zur Erlangung eines 10?i-igen Umsatzes ) gemessen.Copper (II) naphthenate (3 parts of a commercial product containing 5 w / w % copper metal) or 1.5 parts of copper (II) stearate or 1.7 parts of copper (II) oleate and 3 parts of one in the table The additive indicated below was added to 100 parts of 1,4-dichlorobutene-2. The mixture was heated very quickly to 120 ° C and samples were taken at various times and analyzed by gas chromatography. By plotting the conversion to 3,4-dichlorobutene-1 against time, R- | 0 (time in minutes to achieve a 10% conversion) was measured.
Eine Vergleichsisomerisierungsumsetzung von 100 Teilen 1,4-Dichlorbuten-2 unter Zugabe von nur Kupfer-II-naphthenat (3 Teile) oder Kupfer-II-stearat(1,5 Teilender Kupfer-II-oleat(1,7 Teile)wurue auf dieselbe Weise gleichzeitig durchgeführt. Durch Auftragen der Umwandlung gegen die Zeit wurde C10 (Zeit in Minuten zur Erlangung einer 10%-igen Umwandlung zu 3,4-Dichlorbuten-i) gemessen. A comparative isomerization conversion of 100 parts of 1,4-dichlorobutene-2 with the addition of only copper (II) naphthenate (3 parts) or copper (II) stearate (1.5 parts of the copper (II) oleate (1.7 parts) was based on the same By plotting the conversion against time, C 10 (time in minutes to achieve 10% conversion to 3,4-dichlorobutene-i) was measured.
Die Ergebnisse dieser Versuche sind in der Tabelle unten angegeben: The results of these tests are given in the table below:
R10 C 10
R 10
m-Chloranilin
o-Chloranilinp-chloroaniline.
m-chloroaniline
o-chloroaniline
2,00
1,924.36
2.00
1.92
2
31
2
3
Il
ηCopper (II) naphthenate
Il
η
209836/1231209836/1231
Nicht-erfinöungsgemäße Vergleichsversuche:Comparative tests not in accordance with the invention:
Die folgenden Versuche wurden unter denselben Bedingungen wie in Beispiel 1-11 oben durchgeführt, mit der Ausnahme, daß die verwendeten Zusätze die folgenden, unten angegebenen waren:The following experiments were carried out under the same conditions as in Example 1-11 above, except that the The additives used were as follows:
R10 C 10
R 10
Il
IlCopper (II) naphthenate
Il
Il
p-Aminobenzoesäure
keino-aminobenzoic acid
p-aminobenzoic acid
no
0,59
1,000.59
0.59
1.00
209836/1231209836/1231
BAO ORIGINALBAO ORIGINAL
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB471271 | 1971-02-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2206971A1 true DE2206971A1 (en) | 1972-08-31 |
Family
ID=9782373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19722206971 Pending DE2206971A1 (en) | 1971-02-16 | 1972-02-14 | Process for the isomerization of dichlorobutenes |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5613698B1 (en) |
| BE (1) | BE779407A (en) |
| DE (1) | DE2206971A1 (en) |
| FR (1) | FR2125438A1 (en) |
| GB (1) | GB1327983A (en) |
| IT (1) | IT965038B (en) |
| NL (1) | NL7202013A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2004880B (en) * | 1977-09-30 | 1982-07-14 | Denki Kagaku Kogyo Kk | Isomerization of dichlorobutenes |
| JPS5692225A (en) | 1979-12-25 | 1981-07-25 | Denki Kagaku Kogyo Kk | Isomerizing method of dichlorobutene |
| JPS5886399A (en) * | 1981-11-18 | 1983-05-23 | Shinwa Sangyo Kk | Cooling tower |
| JPS6064185A (en) * | 1983-09-16 | 1985-04-12 | Hitachi Reinetsu Jiyuusetsu Kk | Prevention of white smoke in cooling tower |
| JPH0554472U (en) * | 1991-12-26 | 1993-07-20 | 古河機械金属株式会社 | Coil tube winding device |
-
1971
- 1971-02-16 GB GB471271A patent/GB1327983A/en not_active Expired
-
1972
- 1972-02-14 JP JP1550972A patent/JPS5613698B1/ja active Pending
- 1972-02-14 FR FR7204797A patent/FR2125438A1/fr not_active Withdrawn
- 1972-02-14 DE DE19722206971 patent/DE2206971A1/en active Pending
- 1972-02-15 IT IT20600/72A patent/IT965038B/en active
- 1972-02-15 BE BE779407A patent/BE779407A/en unknown
- 1972-02-16 NL NL7202013A patent/NL7202013A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2125438A1 (en) | 1972-09-29 |
| IT965038B (en) | 1974-01-31 |
| NL7202013A (en) | 1972-08-18 |
| GB1327983A (en) | 1973-08-22 |
| BE779407A (en) | 1972-08-16 |
| JPS5613698B1 (en) | 1981-03-30 |
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