NO158621B - PROCEDURE FOR THE PREPARATION OF 1,2-DICHLORETHANE. - Google Patents
PROCEDURE FOR THE PREPARATION OF 1,2-DICHLORETHANE. Download PDFInfo
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- NO158621B NO158621B NO824108A NO824108A NO158621B NO 158621 B NO158621 B NO 158621B NO 824108 A NO824108 A NO 824108A NO 824108 A NO824108 A NO 824108A NO 158621 B NO158621 B NO 158621B
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- dichloroethane
- mixture
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- catalyst
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 22
- 239000003054 catalyst Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000005260 corrosion Methods 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 239000003570 air Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000007306 turnover Effects 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Description
Fremstillingen av 1,2-dikloretan ved omsetning The production of 1,2-dichloroethane by reaction
av etylen med klor i 1,2-dikloretan som oppløsningsmiddel og reaksjonsmedium er kjent. Som hovedsaklig biprodukt frem-kommer ved denne reaksjon 1,1, 2-trik.loretan ved substitusjon av dikloretan. Til undertrykkelse av denne substitusjons-reaksjon anvender man, eventuelt, nærvær av oksygen, som katalysatorer ved siden av kloridene av elementene fra det periodiske systems grupper IV til VI, fremfor alt vannfritt jern-III-klorid, da jern-III-klorid er lett tilgjengelig og prigsgunstig. of ethylene with chlorine in 1,2-dichloroethane as solvent and reaction medium is known. 1,1,2-trichloroethane is the main by-product produced by this reaction by substitution of dichloroethane. To suppress this substitution reaction, one uses, if necessary, the presence of oxygen as catalysts alongside the chlorides of the elements from groups IV to VI of the periodic system, above all anhydrous iron III chloride, as iron III chloride is light available and affordable.
Det dannede rå katalysatorholdige dikloretan fjernes vanligvis fra reaksjonskaret og behandles for fjerning av katalysatoren og det i råproduktet inneholdte klorhydrogen med vann resp. vandig alkalioppløsninger og opparbeides deretter desti1lativt, etter kjente fremgangsmåter. The formed crude catalyst-containing dichloroethane is usually removed from the reaction vessel and treated to remove the catalyst and the hydrogen chloride contained in the crude product with water or aqueous alkali solutions and is then worked up by distillation, according to known methods.
Anvendelsen av FeCl^ som katalysator ved addi-sjonsklorering av etylen er forbundet med visse ulemper. Således bevirker FeCl^ korrosivt i nærvær av vann overfor The use of FeCl3 as a catalyst in the addition chlorination of ethylene is associated with certain disadvantages. Thus, FeCl^ acts corrosively in the presence of water opposite
de metalliske materialer av reaktorer, kolonner- eller varme-utvekslere, såvidt disse kommer i berøring med katalysatoren. Det til klorering normalt anvendte klor med teknisk renhets-grad inneholder alltid spor av fuktighet samt klorhydrogen fra uønskede bireaksjoner. the metallic materials of reactors, columns or heat exchangers, insofar as these come into contact with the catalyst. The technically pure chlorine normally used for chlorination always contains traces of moisture and hydrogen chloride from unwanted side reactions.
Såvidt den ved klorering fra etylen frigjorte varmeenergi skal nyttiggjøres, må reaksjonen gjennomføres ved temperaturer over dikloretanets kokepunkt ved normal-trykk. Da korrosjonsgraden øker betraktelig med økende temperatur, må apparaturen for kloreringsreaksjonen utrustes med korrosjonsfaste materialer, hvilket påvirker den an- If the heat energy released by chlorination from ethylene is to be utilised, the reaction must be carried out at temperatures above the boiling point of dichloroethane at normal pressure. As the degree of corrosion increases considerably with increasing temperature, the apparatus for the chlorination reaction must be equipped with corrosion-resistant materials, which affects the
vndte fremgangsmåtes økonomi. flipped method economics.
Det er nå funnet at den på grunn av FeCl^ som katalysator ved fremstillingen av 1.2-dikloretan forårsakede korrosjon av ikke korrosjonsfaste reaktorer kan nedsettes betraktelig når man tilfører FeCl^-katalysatoren bestemte tilsetninger. Dessuten ble det fastslått at disse tilsetninger ligger også fordelaktig på biproduktdannelsen som deretter nedsettes. It has now been found that the corrosion of non-corrosion-resistant reactors caused by FeCl^ as a catalyst in the production of 1.2-dichloroethane can be considerably reduced when certain additives are added to the FeCl^ catalyst. Furthermore, it was established that these additions are also advantageous in terms of by-product formation, which is then reduced.
Oppfinnelsen vedrører en fremgangsmåte til fremstilling av 1,2-dikloretan ved omsetning av etylen med klor i et oppicsningsmiddel i nærvær av en katalysatorblanding av vannfritt jern-III-klorid, og en ytterligere blandingskomponent, samt eventuelt en inhibitor til å hindre biproduktdannelse ved en temperatur på 20 til 200°C og normalt-eller overtrykk, og adskillelse av 1,2-dikloretanet fra klor-er ingsblandingen ved destillering, idet fremgangsmåten er karakterisert ved at det anvendes en katalysatorblanding hvori, The invention relates to a method for the production of 1,2-dichloroethane by reacting ethylene with chlorine in a cutting agent in the presence of a catalyst mixture of anhydrous iron-III chloride, and a further mixture component, as well as an inhibitor to prevent by-product formation at a temperature of 20 to 200°C and normal or positive pressure, and separation of the 1,2-dichloroethane from the chlorination mixture by distillation, the method being characterized by the use of a catalyst mixture in which,
a) en ytterligere blandingskomponent er en nitrogenbase, valgt fra gruppen ammoniakk, primært, sekundært eller a) a further mixture component is a nitrogen base selected from the group ammonia, primary, secondary or
tertiært alkylamin, som eventuelt er substituert i alkyl-kjeden med hydroksy- eller aminogrupper, eller et salt av en av disse baser, og b) den ytterligere blandingskomponent foreligger i blandingen i omtrent ekvivalent mengde til jern-III-kloridmeng-den, og c) konsentrasjonen av jern-III-kloridet utgjør 0,005 til 0,5 vekt-% referert til oppløsningsmiddelmengden. tertiary alkylamine, which is optionally substituted in the alkyl chain with hydroxy or amino groups, or a salt of one of these bases, and b) the further mixture component is present in the mixture in an approximately equivalent amount to the amount of iron III chloride, and c ) the concentration of the iron III chloride amounts to 0.005 to 0.5% by weight referred to the amount of solvent.
Ifølge en foretrukket utførelsesform av fremgangsmåten ifølge oppfinnelsen, anvendes som oppløsningsmiddel 1,2-dikloretan, og som inhibitor oksygen. According to a preferred embodiment of the method according to the invention, 1,2-dichloroethane is used as solvent, and oxygen as inhibitor.
I detalj er det til fremgangsmåten ifølge oppfinnelsen dessuten å bemerke følgende: Den i fremgangsmåten ifølge oppfinnelsen anvendte katalysator oppløses resp. suspenderes vanligvis i oppiøs-ningsmidlet i reaktoren. Det kan imidlertid også tilberedes utenfor reaksjonsoppløsningen, idet det vannfrie FeCl^ suspenderes sammen med de ytterligere katalysatorkompo-nenter i eksempelvis 1,2-dikloretan, og suspensjonen inn-føres i reaktoren. Det er videre mulig å beskikke det i reaktoren ifylte oppløsningsmiddel med vannfritt FeCl^In detail, the following should also be noted about the method according to the invention: The catalyst used in the method according to the invention is dissolved resp. is usually suspended in the solvent in the reactor. However, it can also be prepared outside the reaction solution, the anhydrous FeCl3 being suspended together with the additional catalyst components in, for example, 1,2-dichloroethane, and the suspension introduced into the reactor. It is also possible to coat the solvent filled in the reactor with anhydrous FeCl^
og NH^ eller et amin. Ved den etterfølgende reaksjon opp-står da tilstrekkelig klorhydrogen til dannelse av det tilsvarende ammoniumsalt. and NH 3 or an amine. In the subsequent reaction, sufficient hydrogen chloride is then produced to form the corresponding ammonium salt.
Fremgangsmåte ifølge oppfinnelsen må sees på som et typisk fremskritt, da den ved den kjente fremgangsmåte til fremstilling av 1,2-dikloretan opptredende og uheldige korrosjon ved anvendelse av ikke korrosjons-bestandige metalliske reaktorer tilbaketrenges i betraktelig grad. Videre ble det fastslått at med unntak av mindre mengder av første substitusjonsprodukt 1,1,2-trikloretan og en tilsvarende liten mengde klorhydrogen, dannes under fremgangsmåtebetingelsene ifølge oppfinnelsen så godt som ingen ytterligere biprodukter. Reaksjons-oppløsningen forblir også lys ved lengere reaksjonsvarighet når tilsetningen ifølge oppfinnelsen foreligger i den til nærværende jernklorid tilnærmet ekvivalent mengde i reaksjonsoppløsningen. Endelig er det å fastslå at ved fremgangsmåten ifølge oppfinnelsen er omsetningen omtrent kvantitativt med høyt rom/tidsutbytte. The method according to the invention must be seen as a typical advance, as the undesirable corrosion occurring in the known method for the production of 1,2-dichloroethane when using non-corrosion-resistant metallic reactors is reduced to a considerable extent. Furthermore, it was established that, with the exception of small amounts of the first substitution product 1,1,2-trichloroethane and a correspondingly small amount of hydrogen chloride, virtually no further by-products are formed under the process conditions according to the invention. The reaction solution also remains light with a longer reaction duration when the additive according to the invention is present in the amount approximately equivalent to the ferric chloride present in the reaction solution. Finally, it must be established that with the method according to the invention, the turnover is roughly quantitative with a high space/time yield.
Fremgangsmåten ifølge oppfinnelsen kan eksempelvis utføres i den i DE-OS 24 27 045 omtalte slyng-reaktor eller i enhver annen for gjennomføring av fremgangsmåten egnet reaktor. The method according to the invention can, for example, be carried out in the loop reactor mentioned in DE-OS 24 27 045 or in any other reactor suitable for carrying out the method.
Oppfinnelsens gjenstand skal forklares nærmere ved hjelp av følgende eksempler: The object of the invention shall be explained in more detail by means of the following examples:
Eksempel 1 Example 1
I en slyngereaktor med en opptaksevne på ca. 2 liter ble det fylt 2,0 kg 1,2-dikloretan så vel som 4 g vannfritt jern-III-klorid. I denne blanding ble det innført 0,42 g ammoniakk i form av en 0,67 vekt% oppløsning i dikloretan ved 30-^0uC. Den oppstigende del av reaktorslyngen inneholder et fyll-1 egemesjikt. Under fyll-1egemesjiktet befant det seg innføringsrør i reaktoren for etylen, klor og luft, hvori-gjennom hver ca. 60 liter/time klor og etylen samt 15 liter/ time luft ble innmatet. Reaksjonsvæsken ble sirkulert i reaktorsystemet etter Mammutpump eprins ippet, og derved ble katalysatorblandingen suspendert jevnt i den flytende fase. Under reaksjonen innstilte det seg i reaksjonsblandingen en reaksjonstemperatur på ca, 77°G. Konsentrasjonen av den i reaktorvæsken oppløste katalysatorblanding bestemt som FeCl^, utgjorde etter forløp av flere dager 0,13 vekt$. In a loop reactor with an absorption capacity of approx. 2 liters were filled with 2.0 kg of 1,2-dichloroethane as well as 4 g of anhydrous ferric chloride. 0.42 g of ammonia was introduced into this mixture in the form of a 0.67% by weight solution in dichloroethane at 30-40°C. The ascending part of the reactor loop contains a fill-1 layer. Under the filling layer there were introduction pipes in the reactor for ethylene, chlorine and air, through which each approx. 60 litres/hour of chlorine and ethylene as well as 15 litres/hour of air were fed in. The reaction liquid was circulated in the reactor system after Mammutpump eprins ipp, and thereby the catalyst mixture was suspended uniformly in the liquid phase. During the reaction, a reaction temperature of approx. 77°G was established in the reaction mixture. The concentration of the catalyst mixture dissolved in the reactor liquid, determined as FeCl^, after several days amounted to 0.13% by weight.
I en over reaktoren anordnede vannkjøler ble de fra reaktoren avgående dikloretan-damper kondensert og deretter avgrenet og uttatt en til den produserte mengde svarende del av kondensatet ved hjelp av en kondensatdel er, mens over-skytende kondensat ble tilbakeført til reaksjonssonen. Ved hjelp av en kuldefelle ble en ytterligere dikloretandel ut-skilt fra den overveiende av inertgasser bestående avgass. Etter en driftstid av en kontinuerlig fremgangsmåte på flere dager hadde katalysatorbladningen oppløst seg sterkt i reaktorvæsken og en kolorimetrisk bestemmelse av Fe-innholdet i reaktorvæsken viste et FeCl^-innhold på ca. 0,13 vekt%. Den pr. time dannede mengde av 1,2-dikloretan utgjorde 262 g. Fremgangsmåten ble gjennomført kontinuerlig over 1/+ dager. In a water cooler arranged above the reactor, the dichloroethane vapors leaving the reactor were condensed and then branched off and a part of the condensate corresponding to the amount produced was taken out using a condensate part, while excess condensate was returned to the reaction zone. By means of a cold trap, a further proportion of dichloroethane was separated from the off-gas consisting predominantly of inert gases. After an operating time of a continuous method of several days, the catalyst coating had dissolved strongly in the reactor liquid and a colorimetric determination of the Fe content in the reactor liquid showed an FeCl^ content of approx. 0.13% by weight. The per hourly amount of 1,2-dichloroethane formed amounted to 262 g. The process was carried out continuously over 1/+ days.
Analysen av det i kondensatoren dannede produkt The analysis of the product formed in the condenser
A resp. reaktorvæsken B etter avslutning av reaksjonen ga følgende verdier: A or the reactor liquid B after completion of the reaction gave the following values:
Eksempel 2 Example 2
Det ble gått frem analogt eksempel 1, idet imidlertid i tillegg til den i reaktoren sirkulerte reaksjons-blanding pr. time ble til dryppet 50 ml 1,2-dikloretan med et innhold på 0.4 vekt$ 1, 1, 2-trikloretan ved hjelp av en dryppetrakt. Den pr. time dannede mengde av 1,2-dikloretan utgjorde 326 g. Forsøksvarigheten utgjorde 8 dager. Analysen av det i kondensatoren dannede produkt A resp.reaktorvæsken B etter avslutning av reaksjonen ga følgende verdier: It proceeded analogously to example 1, in that, however, in addition to the reaction mixture circulated in the reactor per hour, 50 ml of 1,2-dichloroethane with a content of 0.4 wt% 1, 1, 2-trichloroethane was dripped using a dropping funnel. The per The amount of 1,2-dichloroethane formed per hour was 326 g. The test duration was 8 days. The analysis of the product A formed in the condenser or the reactor liquid B after completion of the reaction gave the following values:
Eksempel 3 Example 3
Det ble gått frem analogt eksempel 1, idet imidlertid konsentrasjonen av FeCl^ i reaksjonsblandingen samt molforholdet mellom FeCl^ og ammoniakk ble variert. Virk-ningen på innholdet av 1,1,2-ETC og HC1 i produktet som dannes i kondensatoren fremgår av følgende tabell: The procedure was analogous to example 1, with the concentration of FeCl₂ in the reaction mixture as well as the molar ratio between FeCl₂ and ammonia being varied. The effect on the content of 1,1,2-ETC and HC1 in the product formed in the condenser is shown in the following table:
Den pr. time dannede mengde av 1,2-dikloretan utgjorde på forsøket med FeCl^-konsentras j on på 0,32 vekti? 260 g og forsøksvarigheten 19 dager. Analysen av det i kondensatoren dannede produkt A resp.reaktorvæsken B etter avslutning av reaksjonen ga følgende verdier: The per The amount of 1,2-dichloroethane formed per hour in the experiment with FeCl^-concentration amounted to 0.32 wt. 260 g and the trial duration 19 days. The analysis of the product A formed in the condenser or the reactor liquid B after completion of the reaction gave the following values:
Eksempel L , Example L,
Det ble gått frem analogt eksempel 1, idet det imidlertid ble anvendt 1,35 kg 1,2-dikloretan og i steden for ammoniakk 1,3 g trimetylamin oppløst i 30 ml 1, 2-dikloretan ved tilsatte reaksjon soppiøsninger. Den pr. time dannede mengde av 1,2-dikloretan utgjorde 2 76 g og forsøksvarig-heten 6 dager. Videre utgjorde det i oppløsningen kolorimetrisk fastslåtte FeCl^innhold gjennomsnittlig 0,13 vekt$. The procedure was analogous to example 1, in that, however, 1.35 kg of 1,2-dichloroethane was used and instead of ammonia 1.3 g of trimethylamine dissolved in 30 ml of 1,2-dichloroethane by added reaction mushroom solutions. The per The amount of 1,2-dichloroethane formed per hour was 276 g and the duration of the experiment was 6 days. Furthermore, the colorimetrically determined FeCl^ content in the solution averaged 0.13% by weight.
Analysen av det i kondensatoren dannede produkt The analysis of the product formed in the condenser
A etter avslutning av reaksjonen ga følgende verdier: A after completion of the reaction gave the following values:
Eksempel 5 Example 5
Det ble gått frem analogt eksempel i, idet imidlertid som katalysator ble det tilsatt til reaksjonsoppiøsningen 1,7 g FeCl^, samt 0,65 g diaminoetan. Det kolorimetriske fastslåtte innhold av FeCl^ i oppløsningen utgjorde gjennomsnittlig 0,07 vekt%. Pr. time ble det dannet 268 g 1,2-dikloretan og forsøket varte i' 3 dager. Analogous to example 1, however, 1.7 g of FeCl 2 and 0.65 g of diaminoethane were added to the reaction solution as a catalyst. The colorimetrically determined content of FeCl^ in the solution averaged 0.07% by weight. 268 g of 1,2-dichloroethane were formed per hour and the experiment lasted 3 days.
Analyse av det i kondesator dannede produkt A ga følgende verdier: Analysis of the product A formed in the condenser gave the following values:
Eksempel 6 Example 6
Det ble gått frem analogt eksempel 1, idet imidlertid det ble anvendt 1,5 kg 1,2-dikloretan og katalysator-mengden utgjorde 3, 3 g FeCl-^ og 3,0 g trietanolamin. Det i reaksjon soppiøsningen kolorimerte fastslåtte FeCl^-innhold utgjorde gjennomsnittlig 0,25 vekt%. Pr. time ble det dannet 268g 1,2-dikloretan og forsøket varte over 6 dager. The procedure was analogous to example 1, except that 1.5 kg of 1,2-dichloroethane was used and the amount of catalyst was 3.3 g of FeCl-^ and 3.0 g of triethanolamine. The determined FeCl^ content, which was colored in the reaction, was 0.25% by weight on average. 268g of 1,2-dichloroethane was formed per hour and the experiment lasted over 6 days.
Analysen av det i kondensatet dannede produkt A ga følgende verdier: The analysis of the product A formed in the condensate gave the following values:
Eksempel 7 Example 7
a) I en 2 liters rundkolbe som var utrustet med rørverk, dryppetrakt og tilbakeløpskj øl er, ble det fylt 2 kg a) In a 2 liter round flask that was equipped with piping, a drip funnel and a return line, 2 kg was filled
1, 2-dikloretan med 2, 1 g jern-III-klorid. Blandingen ble oppvarmet under omrøring til koking, og deretter inndryppet 0,2 g ammoniakk oppløst i 58 g 1,2-dikloretan således at det samlede katalysatormengde utgjorde 2,3 g- Etter at blandingen var blitt kokt ytterligere 5 timer under tilbakeløp. ble det kolorimetrisk fastslått et innhold på 0,11 vekt% FeCl^-opp-1øsn ingen. 1,2-dichloroethane with 2.1 g of ferric chloride. The mixture was heated with stirring to boiling, and then 0.2 g of ammonia dissolved in 58 g of 1,2-dichloroethane was added dropwise so that the total amount of catalyst amounted to 2.3 g. After the mixture had been boiled for a further 5 hours under reflux. a content of 0.11% by weight FeCl^-opp-1øsn none was determined colorimetrically.
Blandingen av dikloretan og katalysator ble i-fylt deretter den ifølge eksempel 1 omtalte slyngereaktor og deretter av hver innledet ca. 60 liter/time klor og etylen sammen med ca. 5 liter/time luft i reaktoren. Pr. time ble det dannet 273 g 1,2-dikloretan og forsøket gikk i 8 dager. The mixture of dichloroethane and catalyst was then filled into the loop reactor mentioned according to example 1 and then by each introduced approx. 60 litres/hour of chlorine and ethylene together with approx. 5 litres/hour of air in the reactor. 273 g of 1,2-dichloroethane were formed per hour and the experiment ran for 8 days.
Analysen av det i kondensatoren dannede produkt The analysis of the product formed in the condenser
A ga følgende verdier: A gave the following values:
E k s e mp el 8 Example 8
a) Det ble i første rekke gått frem analogt eksempel 7a), idet imidlertid 1,5 kg 1,2-dikloretan ble oppvarmet til kokning under omrøring med 12 g FeCl^- I blandingen ble det inndryppet en oppløsning av 2,7 g klorhydrogen i 750 g dikloretan, deretter en oppløsning av 1,26 g NH^ i 2 73 g dikloretan. Reaks j onsblandingen ble filtrert etter av^-kjøling og f ilterresiduet tørket. Det ble dannet 14-, 4 g tørr katalysator. b) For fremstilling av 1, 2-dikloretan ble 4- g av den ifølge a) fremstilte katalysator, samt 2 g FeCl^ suspendert i 2,7 kg 1,2-dikloretan og etter inndampning av blandingsvolumet til ca. 2 liter ble blandingen innført i den i eksempel 1 omtalte slyngereaktor. Pr. time ble det i samme slyngereaktor hver gang innført 60 liter klor, og etylen, samt 15 liter luft, og reaksjonen startet under de i eksempel 1 nevnte reaksjonsbetingelser. Det ble dannet 266 g 1,2-dikloretan og forsøket varte i 6 dager. Det i reak-sjonsoppløsningen kolorimetriske fastslåtte FeCl^-innhold utgjorde gjennomsnittlig 0,15 vekt%. a) The procedure was primarily analogous to example 7a), however, 1.5 kg of 1,2-dichloroethane was heated to boiling while stirring with 12 g of FeCl^- A solution of 2.7 g of hydrogen chloride was dripped into the mixture in 750 g dichloroethane, then a solution of 1.26 g NH 2 in 2 73 g dichloroethane. The reaction mixture was filtered after cooling and the filter residue dried. 14.4 g of dry catalyst was formed. b) For the production of 1,2-dichloroethane, 4 g of the catalyst prepared according to a) and 2 g of FeCl^ were suspended in 2.7 kg of 1,2-dichloroethane and after evaporating the mixture volume to approx. 2 liters of the mixture was introduced into the loop reactor mentioned in example 1. Each time, 60 liters of chlorine and ethylene, as well as 15 liters of air, were introduced into the same loop reactor each time, and the reaction started under the reaction conditions mentioned in example 1. 266 g of 1,2-dichloroethane were formed and the experiment lasted 6 days. The colorimetrically determined FeCl^ content in the reaction solution averaged 0.15% by weight.
Analysen av det i kondensatoren dannede produkt A resp. reaktorvæsken B etter avslutning :av reaksjonen ga følgende verdier: The analysis of the product A formed in the condenser resp. the reactor liquid B after completion of the reaction gave the following values:
Eksempel 9 Example 9
I en reaktor til teknisk fremstilling av 1,2-dikloretan ble det'på fire steder av reaktoren innsatt korro-sjonsprøver og prøvene utsatt for fremgangsmåtebetingelsene ifølge oppfinnelsen. I tidsrom på 20 dager ble prøvene uttatt fra reaktoren og den i korrosjonen betingede slitasje fastslått. Ved anvendelse av FeCl^/NH^-katalysator ifølge oppfinnelsen og overholdelse av reaksjonstemperatur på 100-.110OC utgjode den gjennomsnittlige korrosjonsgrad for ulegert stål mindre enn 0,05 mm pr. år. Ble derimot fremgangsmåten gjennomført på kjent måte under anvendelse av utelukkende FeCl^ som katalysator,så utgjorde den gjennomsnittlige korrosjonsgrad for ulegert stål 0,4-3 mm pr. år. In a reactor for the technical production of 1,2-dichloroethane, corrosion samples were inserted in four places of the reactor and the samples were exposed to the process conditions according to the invention. During a period of 20 days, the samples were taken from the reactor and the wear due to corrosion determined. When using the FeCl^/NH^ catalyst according to the invention and observing a reaction temperature of 100-110°C, the average corrosion rate for unalloyed steel was less than 0.05 mm per year. If, on the other hand, the method was carried out in a known manner using only FeCl^ as a catalyst, the average degree of corrosion for unalloyed steel was 0.4-3 mm per year.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813148450 DE3148450A1 (en) | 1981-12-08 | 1981-12-08 | CATALYST MIXTURE AND METHOD FOR PRODUCING 1,2-DICHLORETHANE |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO824108L NO824108L (en) | 1983-06-09 |
| NO158621B true NO158621B (en) | 1988-07-04 |
| NO158621C NO158621C (en) | 1988-10-12 |
Family
ID=6148127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO824108A NO158621C (en) | 1981-12-08 | 1982-12-07 | PROCEDURE FOR THE PREPARATION OF 1,2-DICHLORETHANE. |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0082342B1 (en) |
| JP (1) | JPS58104636A (en) |
| AU (1) | AU553255B2 (en) |
| BR (1) | BR8207099A (en) |
| CA (1) | CA1189057A (en) |
| CS (1) | CS235975B2 (en) |
| DD (1) | DD208604A5 (en) |
| DE (2) | DE3148450A1 (en) |
| ES (1) | ES8307529A1 (en) |
| HU (1) | HU193155B (en) |
| IN (1) | IN156063B (en) |
| MX (1) | MX162900B (en) |
| NO (1) | NO158621C (en) |
| SU (1) | SU1250165A3 (en) |
| ZA (1) | ZA828976B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3247988A1 (en) * | 1982-12-24 | 1984-06-28 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING 1,2-DICHLORETHANE |
| DE3347153A1 (en) * | 1983-12-27 | 1985-07-04 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING 1,2-DICHLORETHANE |
| DE3519161A1 (en) * | 1985-05-29 | 1986-12-04 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PURIFYING 1,2-DICHLORETHANE |
| EP0835857A1 (en) * | 1996-03-13 | 1998-04-15 | Caprolactam Joint-Stock Company | Method of obtaining 1,2-dichloroethane |
| DE10050315C2 (en) | 2000-10-10 | 2003-08-21 | Uhde Gmbh | Process for dissolving salts in 1,2-dichloroethane by means of ultrasound and device for carrying out the process |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2486379A (en) * | 1946-07-22 | 1949-11-01 | Dow Chemical Co | Manufacture of nuclear halogenated alkenyl-benzene compounds |
| US3723543A (en) * | 1970-12-21 | 1973-03-27 | Olin Corp | Process for preparing 2,4,4,4-tetrachlorobutanol |
| US4058574A (en) * | 1972-07-11 | 1977-11-15 | Rhone-Progil | Process for the oxychlorination of hydrocarbons with ammonium chloride |
| GB1422303A (en) * | 1973-06-11 | 1976-01-28 | Stauffer Chemical Co | Production of ethylene dichloride |
| DE2540291C3 (en) * | 1975-09-10 | 1984-02-23 | Hoechst Ag, 6230 Frankfurt | Process for the continuous production of 1,2-dichloroethane and a catalyst container as part of a device for carrying out the process mentioned |
| AU529847B2 (en) * | 1979-01-10 | 1983-06-23 | Akzo N.V. | Combined chlorinated hydrocarbon-sodium bicarbonate productio |
| US4282165A (en) * | 1980-03-24 | 1981-08-04 | Argus Chemical Corporation | Preparation of trimethyltin chloride from dimethyltin dichloride |
-
1981
- 1981-12-08 DE DE19813148450 patent/DE3148450A1/en not_active Withdrawn
-
1982
- 1982-11-16 ES ES517410A patent/ES8307529A1/en not_active Expired
- 1982-11-17 CA CA000415709A patent/CA1189057A/en not_active Expired
- 1982-11-25 EP EP82110897A patent/EP0082342B1/en not_active Expired
- 1982-11-25 DE DE8282110897T patent/DE3276154D1/en not_active Expired
- 1982-12-06 DD DD82245614A patent/DD208604A5/en not_active IP Right Cessation
- 1982-12-06 JP JP57212830A patent/JPS58104636A/en active Granted
- 1982-12-06 SU SU823520355A patent/SU1250165A3/en active
- 1982-12-07 NO NO824108A patent/NO158621C/en unknown
- 1982-12-07 HU HU823918A patent/HU193155B/en not_active IP Right Cessation
- 1982-12-07 AU AU91615/82A patent/AU553255B2/en not_active Ceased
- 1982-12-07 ZA ZA828976A patent/ZA828976B/en unknown
- 1982-12-07 BR BR8207099A patent/BR8207099A/en not_active IP Right Cessation
- 1982-12-08 IN IN1426/CAL/82A patent/IN156063B/en unknown
- 1982-12-08 CS CS828902A patent/CS235975B2/en unknown
- 1982-12-08 MX MX195509A patent/MX162900B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR8207099A (en) | 1983-10-11 |
| ES517410A0 (en) | 1983-08-16 |
| SU1250165A3 (en) | 1986-08-07 |
| JPS58104636A (en) | 1983-06-22 |
| DD208604A5 (en) | 1984-04-04 |
| CA1189057A (en) | 1985-06-18 |
| ES8307529A1 (en) | 1983-08-16 |
| DE3276154D1 (en) | 1987-06-04 |
| IN156063B (en) | 1985-05-04 |
| HU193155B (en) | 1987-08-28 |
| ZA828976B (en) | 1983-10-26 |
| AU553255B2 (en) | 1986-07-10 |
| DE3148450A1 (en) | 1983-06-16 |
| EP0082342A3 (en) | 1985-09-18 |
| NO158621C (en) | 1988-10-12 |
| MX162900B (en) | 1991-07-08 |
| EP0082342B1 (en) | 1987-04-29 |
| NO824108L (en) | 1983-06-09 |
| AU9161582A (en) | 1983-06-16 |
| JPH0230298B2 (en) | 1990-07-05 |
| EP0082342A2 (en) | 1983-06-29 |
| CS235975B2 (en) | 1985-05-15 |
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