NO174846B - Process and catalyst for oxychlorination in the preparation of 1,2-dichloroethane - Google Patents
Process and catalyst for oxychlorination in the preparation of 1,2-dichloroethane Download PDFInfo
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- NO174846B NO174846B NO912463A NO912463A NO174846B NO 174846 B NO174846 B NO 174846B NO 912463 A NO912463 A NO 912463A NO 912463 A NO912463 A NO 912463A NO 174846 B NO174846 B NO 174846B
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- catalyst
- copper
- oxychlorination
- hydrocarbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000008569 process Effects 0.000 title claims abstract description 4
- 238000002360 preparation method Methods 0.000 title description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title description 4
- 239000005749 Copper compound Substances 0.000 claims abstract description 19
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 19
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 26
- 239000010949 copper Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 14
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
- C07C19/043—Chloroethanes
- C07C19/045—Dichloroethanes
-
- 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
- B01J27/122—Halides of copper
-
- 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
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- 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)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Steroid Compounds (AREA)
- Lubricants (AREA)
Abstract
Description
Foreliggende oppfinnelse angår en fremgangsmåte og en katalysator for oksyklorering samt deres anvendelse ved fremstilling av 1,2-dikloretan. The present invention relates to a method and a catalyst for oxychlorination and their use in the production of 1,2-dichloroethane.
1,2-dikloretan (D 12) er et produkt som fremstilles indu-strielt i en mengde av flere millioner tonn pr. år, og som ved pyrrolyse gir vinylklorid monomer (VCM) og saltsyre (HC1). VCM polymeriseres til polyvinylklorid (eller PVC) materiale som finner utstrakt anvendelse. Den ved pyrolysen oppnådde HCL separeres fra VCM og bringes derefter i kontakt med etylen og oksygen i nærvær av en katalysator for derved å oppnå D12, det vil si oksykloreringsreaksjonen. 1,2-Dichloroethane (D 12) is a product that is produced industrially in a quantity of several million tonnes per year. years, and which by pyrolysis gives vinyl chloride monomer (VCM) and hydrochloric acid (HC1). VCM is polymerized into polyvinyl chloride (or PVC) material which finds extensive use. The HCL obtained by the pyrolysis is separated from the VCM and then brought into contact with ethylene and oxygen in the presence of a catalyst to thereby obtain D12, i.e. the oxychlorination reaction.
Denne reks jon er meget generell og kan gjennomføres med de fleste hydrokarboner. Oksykloreringen er beskrevet i tallrike patenter, særlig FR-PS 2 063 365, FR-PS 2 260 551, FR-PS 2 213 259 og FR-PS 2 125 748. Katalysatoren består av et kobbersalt avsatt på et aluminiumoksydpulver. EP søknad 58 644 beskriver fremstilling av en katalysator gjennomført ved å bringe en kobber-(II)-oppløsning inn i et hvirvelsjikt av aluminiumoksydpulver ved en temperatur på maksimum 50°C. Denne operasjon følges av en tørking i varmluft i hvirvelsjiktet og uten å gå ut over 140°C. This reaction is very general and can be carried out with most hydrocarbons. The oxychlorination is described in numerous patents, in particular FR-PS 2 063 365, FR-PS 2 260 551, FR-PS 2 213 259 and FR-PS 2 125 748. The catalyst consists of a copper salt deposited on an aluminum oxide powder. EP application 58 644 describes the production of a catalyst carried out by bringing a copper (II) solution into a fluidized bed of aluminum oxide powder at a temperature of a maximum of 50°C. This operation is followed by drying in hot air in the fluidized bed and without going above 140°C.
EP-søknad 29 143 beskriver fremstilling av en oksykloreringskatalysator omfattende i et hvirvelsjikt for oksykloreringsreaksjonen å blande den allerede fremstilte katalysator, det vil si aluminiumoksydpulvere inneholdende en kobberforbindelse og kun bæreren, det vil si aluminiumoksydpulveret som ikke inneholder kobberforbindelser. Man beskriver også tilsetningen av kun bæreren til oksykloreringsreaksjons-hvirvelsjiktet som først var chargert med katalysator. Denne metode angis som fordelaktig for å unngå sammenklebing (eller agglomerering) av katalysatorkorn under drift. Denne søknad beskriver en migrering av kobberforbindelsen fra aluminiumoksyd inneholdende kobber til den nakne bærer. Det er klart at resultatet av denne metode er en reduksjon av kobber-mengden på katalysatoren mens man øker mengden bærer uten å tilføre kobber. Søknaden presenterer både problemet og resultatet: "undertrykning eller reduksjon av sammenklebing" er ikke kun forbundet med reduksjonen av mengden kobber men også av migreringen av en kobberforbindelse fra aluminiumoksyd inneholdende kobberforbindelsen og mot den nakne bærer. Denne EP-søknad 29143 beskriver også et middel for å fremstille en katalysator in situ ved å chargere reaktoren med naken bærer, å fluidisere den med reaksjonsgassen og å tilsette fast kobber-(II)-klorid. Denne måte angis som en erstatning for den konvensjonelle fremstilling av katalysator ved impregnering utenfor reaktoren. Imidlertid er denne fremstilling ikke foreslått annet enn i laboratoriemålestokk, i virkeligheten er denne fremstillingsmetode ikke industriell fordi ved begynnelsen av fremstillingen inneholder hvirvelsjiktet ikke egentlig katalysator, det vil si en kobberforbindelse på en bærer, det foreligger således ingen oksy-kloreringsreaksjon, det er nødvendig å oppvarme, og hvis man oppvarmer uten at det foreligger noen katalysator befinner man seg ved utløpet av hvirvelsjiktet i en eksplosiv sone fordi det ikke er noen reaksjon og derfor ingen omdanning. EP application 29 143 describes the production of an oxychlorination catalyst comprising mixing in a fluidized bed for the oxychlorination reaction the already prepared catalyst, i.e. aluminum oxide powders containing a copper compound and only the carrier, i.e. the aluminum oxide powder which does not contain copper compounds. It also describes the addition of only the carrier to the oxychlorination reaction fluidized bed which was initially charged with catalyst. This method is stated to be advantageous in order to avoid sticking together (or agglomeration) of catalyst grains during operation. This application describes a migration of the copper compound from aluminum oxide containing copper to the bare support. It is clear that the result of this method is a reduction of the amount of copper on the catalyst while increasing the amount of carrier without adding copper. The application presents both the problem and the result: "suppression or reduction of bonding" is not only associated with the reduction of the amount of copper but also with the migration of a copper compound from aluminum oxide containing the copper compound and towards the bare support. This EP application 29143 also describes a means of preparing a catalyst in situ by charging the reactor with bare support, fluidizing it with the reaction gas and adding solid copper (II) chloride. This method is indicated as a substitute for the conventional production of catalyst by impregnation outside the reactor. However, this preparation is not proposed except on a laboratory scale, in reality this preparation method is not industrial because at the beginning of the preparation the fluidized bed does not actually contain a catalyst, i.e. a copper compound on a support, there is thus no oxy-chlorination reaction, it is necessary to heating, and if you heat without the presence of any catalyst, you find yourself at the outlet of the fluidized bed in an explosive zone because there is no reaction and therefore no transformation.
EP-søknad 119 933 beskriver også en oksygeneringskatalysator i henhold til samme prinsipp som ovenfor, det vil si kobber som impregnerer et aluminiumoksydpulver men som ikke har mangelen ved klebing fordi man, slik det sies, i denne søknad har mindre kobber på overflaten enn idet indre av kataly-satorkornene. EP application 119 933 also describes an oxygenation catalyst according to the same principle as above, i.e. copper which impregnates an aluminum oxide powder but which does not have the deficiency of adhesion because, as it is said, in this application there is less copper on the surface than in the interior of the catalyst grains.
All denne kjente teknikk angår oksykloreringshvirvelsjikt som benytter en "homogen" katalysator, det vil si pulvere der alle korn er impregnert med kobber. Det foreligger også oksykloreringshvirvelsjikt som benytter en "heterogen" katalysator, det vil si pulvere som består av en blanding av aluminiumoksydkorn impregnert med kobber som tidligere og inerte korn som kvartssand. Disse katalysatorer er beskrevet i FR-PS 2 242 143. Disse "heterogene" katalysatorer oppviser ikke de "homogene" katalysatorers klehing men tvert imot den mangel at det dannes en selvslitende blanding idet sand-kornene fremtvinger en nedsliting av aluminiumoksydkornene. Det finfordelte materialet med høyt kobberinnhold fjernes og det er nødvendig å kompensere dette tap ved tilsetning av ny katalysator. All of this known technology relates to oxychlorination fluidized beds that use a "homogeneous" catalyst, that is to say powders in which all grains are impregnated with copper. There are also oxychlorination fluidized beds that use a "heterogeneous" catalyst, i.e. powders consisting of a mixture of aluminum oxide grains impregnated with copper as before and inert grains such as quartz sand. These catalysts are described in FR-PS 2 242 143. These "heterogeneous" catalysts do not exhibit the wear of the "homogeneous" catalysts but, on the contrary, the defect that a self-wearing mixture is formed as the sand grains force the alumina grains to wear down. The finely divided material with a high copper content is removed and it is necessary to compensate this loss by adding new catalyst.
Man har nu funnet en perfeksjonering i forbindelse med disse "heterogene" oksykloreringskatalysatorer som tillater å opprettholde konstant ytelse med tiden. A perfection has now been found in connection with these "heterogeneous" oxychlorination catalysts which allow constant performance to be maintained over time.
For å forhindre forvirring i forbindelse med de vanlige termer homogen katalyse og heterogen katalyse og for å forbli koherente med termene i FR 2 242 143, kalles de "heterogene" oksykloreringskatalysatorer: fluidiserbar charge eller fluidiserbar katalytisk charge. To prevent confusion in connection with the common terms homogeneous catalysis and heterogeneous catalysis and to remain coherent with the terms in FR 2 242 143, they are called "heterogeneous" oxychlorination catalysts: fluidizable charge or fluidizable catalytic charge.
Foreliggende oppfinnelse angår således en oksyklorerings-prosess for et hydrokarbon for å fremstille et klorert hydrokarbon hvori hydrokarbonet, en gass inneholdende oksygen samt gassformig saltsyre passerer gjennom en fluidiserbar charge omfattende en blanding av en oksykloreringskatalysator og partiklene av minst et katalytisk og kjemisk inert fastoff, og fremgangsmåten karakteriseres ved at man til den fluidiserte charge setter en oppløsning eller en suspensjon av en kobberforbindelse. The present invention thus relates to an oxychlorination process for a hydrocarbon to produce a chlorinated hydrocarbon in which the hydrocarbon, a gas containing oxygen and gaseous hydrochloric acid pass through a fluidizable charge comprising a mixture of an oxychlorination catalyst and the particles of at least one catalytically and chemically inert solid, and the method is characterized by adding a solution or a suspension of a copper compound to the fluidized charge.
Foreliggende oppfinnelse angår også disse katalytiske preparater eller fluidiserbare charger. The present invention also relates to these catalytic preparations or fluidizable chargers.
Oppfinnelsen angår således en fluidiserbar charge som kan benyttes som oksygeneringskatalysator og som karakteriseres ved at det omfatter (i) en blanding av en oksykloreringskatalysator og (ii) partikler av minst et katalytisk og kjemisk inert faststoff hvortil man har satt en oppløsning eller en suspensjon av en kobberforbindelse. The invention thus relates to a fluidizable charge which can be used as an oxygenation catalyst and which is characterized in that it comprises (i) a mixture of an oxychlorination catalyst and (ii) particles of at least one catalytically and chemically inert solid to which a solution or a suspension of a copper connection.
Hydrokarbonet kan være en blanding av flere hydrokarboner, valgt blant Ci_20alifatiske hydrokarboner, opp til C^<g>-cykloalifatiske hydrokarboner og aromatiske slike med opp til 4 kondenserte benzenkjerner samt deres klorerte substitu-sjonsderivater. De kan velges for eksempel blant metan, propan, etylen og propylen. Oppfinnelsen er spesielt brukbar for etylen. Gassen inneholdende oksygen er i enkleste tilfellet luft men man kan også benytte oksygenfattig eller The hydrocarbon can be a mixture of several hydrocarbons, selected from C1-20 aliphatic hydrocarbons, up to C1<g>-cycloaliphatic hydrocarbons and aromatic ones with up to 4 condensed benzene nuclei as well as their chlorinated substitution derivatives. They can be chosen, for example, from methane, propane, ethylene and propylene. The invention is particularly applicable to ethylene. The gas containing oxygen is in the simplest case air, but you can also use oxygen-poor or
-anriket luft. -enriched air.
Oksykloreringskatalysatorene som kan benyttes ifølge oppfinnelsen kan være hvilke som helst oksykloreringskatalysatorer som selv kan benyttes uten blanding med et kjemisk og katalytisk inert stoff. Fortrinnsvis benyttes pulvere i det vesentlige på basis av aluminiumoksyd med en granulometri mellom 20 og 200 ytm og et overflateareal mellom 90 og 450 m<2>/g, fortrinnsvis mellom 30 og 90 yim og mellom 250 og 400 m<2>/g. Disse pulvere impregneres med kobber eller et kobbersalt i en mengde som kan gå helt opp i 10 $> , men som fortrinnsvis ligger mellom 3 og 10 #, beregnet som vekt-# kobber i forhold til den ferdige katalysator. The oxychlorination catalysts that can be used according to the invention can be any oxychlorination catalysts that can themselves be used without mixing with a chemically and catalytically inert substance. Preferably, powders are used essentially on the basis of aluminum oxide with a granulometry between 20 and 200 ytm and a surface area between 90 and 450 m<2>/g, preferably between 30 and 90 yim and between 250 and 400 m<2>/g. These powders are impregnated with copper or a copper salt in an amount which can go up to 10 $>, but which is preferably between 3 and 10 #, calculated as weight-# of copper in relation to the finished catalyst.
Som katalytisk og kjemisk inert stoff som spiller rollen som fortynningsmiddel (men ikke i noe tilfelle som katalysator-bærer) skal spesielt nevne mikro-kuler av glass eller silisiumdioksyd, oc-aluminiumoksyd eller fortrinnsvis kvartssand slik man finner den i naturlig tilstand og hvis granulometriske fordeling av partikkelstørrelsen er tilpasset fluidiseringskravene. As a catalytic and chemically inert substance that plays the role of a diluent (but not in any case as a catalyst carrier) special mention should be made of micro-spheres of glass or silicon dioxide, oc-alumina or preferably quartz sand as it is found in its natural state and whose granulometric distribution of the particle size is adapted to the fluidization requirements.
Den granulometriske fordeling for den egentlige katalysator på den ene side og den til det katalytiske og kjemiske inerte materialet på den annen side, velges slik at diameteren og skalaen for partikkelstørrelsen i blandingen som enhet gir en god fluidisering. The granulometric distribution for the actual catalyst on the one hand and that of the catalytic and chemically inert material on the other hand is chosen so that the diameter and scale of the particle size in the mixture as a unit provides good fluidization.
Fortrinnsvis er dimensjonene for de inerte partikler mellom 20 og 200 pm. Preferably, the dimensions of the inert particles are between 20 and 200 pm.
Mengden inert materiale kan variere innen vide grenser. Fortrinnsvis kan mengden inert materiale utgjøre 1 til 20 ganger vekten av katalysatormengden. The amount of inert material can vary within wide limits. Preferably, the amount of inert material can amount to 1 to 20 times the weight of the catalyst amount.
Formålet med oksykloreringen er i det vesentlige å benytte saltsyre som klorkilde. Man justerer således mengden av oksygen og hydrokarbon for å oppnå noe nær støkiometrisk mengde klorert hydrokarbon ved å forbruke maksimal mengde EC1 og hydrokarbon. The purpose of oxychlorination is essentially to use hydrochloric acid as a source of chlorine. One thus adjusts the amount of oxygen and hydrocarbon to achieve something close to the stoichiometric amount of chlorinated hydrocarbon by consuming the maximum amount of EC1 and hydrocarbon.
Under driften av et oksykloreringshvirvelsjikt fastslår man en aktivitetsreduksjon som gir seg utslag i en manko når det gjelder hydrokarbonomdanningen. During the operation of an oxychlorination fluidized bed, a reduction in activity is determined, which results in a lack of hydrocarbon conversion.
Denne reduksjon skyldes en nedslitning av katalysatoren. I tillegg til denne slitasje som fører til en aktivitetsreduksjon, kommer et fysisk tap på grunn av medføring av utløps-gassen fra hvirvelsjiktet og en utilstrekkelig effektivitet for midlene for separering av medført katalysator fra gassen. Denne separering gjøres vanskelig ved transformering av en del av katalysatoren til et pulver på grunn av slitasje. Generelt kompenserer man for reduksjonen av katalysatormengde og reduksjonen av aktiviteten ved tilsetning av ny katalysator. Søkeren har med forbauselse fastslått at man kan kompensere for denne aktivitetsreduksjon ved til hvirvelsjiktet å tilsette en oppløsning av en suspensjon av en kobberforbindelse. This reduction is due to wear and tear of the catalyst. In addition to this wear which leads to a reduction in activity, there is a physical loss due to entrainment of the outlet gas from the fluidized bed and an insufficient efficiency of the means for separating entrained catalyst from the gas. This separation is made difficult by the transformation of part of the catalyst into a powder due to wear. In general, one compensates for the reduction in catalyst quantity and the reduction in activity by adding new catalyst. The applicant has determined with astonishment that one can compensate for this reduction in activity by adding to the fluidized bed a solution of a suspension of a copper compound.
Blant disse kobberforbindelser kan man benytte kloridet og oksykloridet. Man foretrekker å benytte kobber-(II)-klorid. Among these copper compounds, one can use the chloride and the oxychloride. It is preferred to use copper (II) chloride.
Oppløsningen kan være en suspensjon hvis konsentrasjonen er høy eller hvis kobberforbindelsen er lite oppløselig. Oppløsningen av kobberforbindelsen kan være en vandig oppløsning. Oppløsningen eller suspensjonen settes kontinuer-lig til oksykloreringsreaktoren eller diskontinuerlig men under driften av oksykloreringen. Man kan innføre oppløs-ningen eller suspensjonen via en forstøvningsdyse. The solution may be a suspension if the concentration is high or if the copper compound is poorly soluble. The solution of the copper compound may be an aqueous solution. The solution or suspension is added continuously to the oxychlorination reactor or discontinuously but during the operation of the oxychlorination. The solution or suspension can be introduced via a spray nozzle.
Mengden kobber som innføres i form av oppløsning er en funksjon av den ytelse man tilstreber. Operasjonen kan gjentas så mange ganger det er nødvendig. Man kan i tillegg til denne oppløsning av en kobberforbindelse tilsette pulverformig kobber, en kobberforbindelse i pulverform eller ny katalysator inneholdende kobber. The amount of copper that is introduced in the form of a solution is a function of the desired performance. The operation can be repeated as many times as necessary. In addition to this solution of a copper compound, you can add powdered copper, a copper compound in powder form or a new catalyst containing copper.
Kobber eller en kobberforbindelse i pulverform kan foreligge i form av en på kobber meget anriket katalysator. Meget kobberrik vil si at mengden, uttrykt som kobber i vekt-# av den endelige katalysator, er over den til katalysatoren i drift i den fluidiserte charge. Fortrinnsvis er denne verdi 1,2 ganger og fortrinnsvis mellom 1,5 og 3 ganger den til katalysatoren som funksjon av den fluidiserte charge. Copper or a copper compound in powder form can be present in the form of a catalyst highly enriched in copper. Very copper-rich means that the amount, expressed as copper in weight # of the final catalyst, is above that of the catalyst in operation in the fluidized charge. Preferably, this value is 1.2 times and preferably between 1.5 and 3 times that of the catalyst as a function of the fluidized charge.
Hvis for eksempel katalysatoren i drift i fluordiserte charge inneholder mellom 3,5 og 7 vekt-# kobber, tilsetter man katalysator til omkring 12 vekt-# kobber. Man anser at denne mengde på 12 1» , uttrykt som kobber, er meget kobberrik. Videre er det en uvanlig verdi for fremgangsmåten for å oppnå den er meget mer komplisert enn for de vanlige verdier på 3 til 8 %. If, for example, the catalyst in operation in fluoridated charge contains between 3.5 and 7 wt-# of copper, one adds catalyst to around 12 wt-# of copper. It is considered that this quantity of 12 1", expressed as copper, is very rich in copper. Furthermore, it is an unusual value for the method of obtaining it is much more complicated than for the usual values of 3 to 8%.
Fordelen ved oppfinnelsen i forhold til tradisjonell drift som består i kompensere aktivitetsreduksjonen og reduksjonen av mengden katalysator kun ved tilsetning av ny katalysator, er en meget regulær drift idet man unngår aktivitetsstøt, og forbedringen er mer varig. The advantage of the invention in relation to traditional operation, which consists in compensating the activity reduction and the reduction of the amount of catalyst only by adding new catalyst, is a very regular operation while avoiding activity shocks, and the improvement is more lasting.
Oppfinnelsen skal illustreres ved de følgende eksempler. The invention shall be illustrated by the following examples.
Eksempel 1 Example 1
1/ Prøve nr. 1; Referanse til normale driftsbetingelser ( ikke 1/ Sample no. 1; Reference to normal operating conditions (no
ifølge oppfinnelsen). according to the invention).
Til en reaktor med diameter 3 m og for produksjon av 25 tonn pr. time 1,2-dikloretan, er driftsbetingelsene som følger: Temperatur : 245 til 250°C For a reactor with a diameter of 3 m and for the production of 25 tonnes per hour 1,2-dichloroethane, the operating conditions are as follows: Temperature : 245 to 250°C
Trykk : 4 bar Pressure: 4 bar
Oppholdstid : 25 til 30 sekunder. Residence time: 25 to 30 seconds.
Katalytisk system : 8 tonn aluminiumoksyd, impregnert med 60 io kobber (katalysator) + silisiumdioksyd (22 tonn). Aluminiumoksydet har en overflate på 357 m<2>/g, en midlere diameter på 53 pm, et porevolum på 33 cm5 /100 g og en volumvekt på 1192 kg/m3 . Silisiumoksydet er et Fontainebleau salt (ren silisiumdioksyd) med en midlere diameter på 50 pm og innenfor området 20 til 300 pm. Catalytic system: 8 tonnes of aluminum oxide, impregnated with 60 io of copper (catalyst) + silicon dioxide (22 tonnes). The aluminum oxide has a surface area of 357 m<2>/g, a mean diameter of 53 pm, a pore volume of 33 cm 5 /100 g and a volume weight of 1192 kg/m 3 . The silicon oxide is a Fontainebleau salt (pure silicon dioxide) with an average diameter of 50 µm and within the range of 20 to 300 µm.
De oppnådde resultater er oppført i tabell I. The results obtained are listed in Table I.
2/ Prøve nr. 2 ifølge oppfinnelsen: Med tilsetning av en 2/ Sample no. 2 according to the invention: With the addition of a
kobber-( II)- kloridoppløsning. copper-(II) chloride solution.
De samme betingelser som for prøve nr. 1 med i tillegg tilsetning av en oppløsning av kobber-(II)-kloridet. Man gjennomfører tilsetningene diskontinuerlig tilsvarende mengder av kobbermetall på 50 til 200 kg. Resultatene er også oppført i tabell I: Man har i tabell I antydet forbruket av katalysator og forbruket av kobber-(II)-kloridoppløsning, uttrykt i g/tonn fremstilt D12. Tilsetningene av katalysator og kobber-(II)-klorid-oppløsning gjennomføres for å oppnå konstante driftsbetingelser. The same conditions as for sample no. 1 with the addition of a solution of the copper (II) chloride. The additions are carried out discontinuously corresponding amounts of copper metal of 50 to 200 kg. The results are also listed in Table I: In Table I, the consumption of catalyst and the consumption of copper (II) chloride solution, expressed in g/tonne D12 produced, have been indicated. The additions of catalyst and copper (II) chloride solution are carried out to achieve constant operating conditions.
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9007932A FR2663629B1 (en) | 1990-06-25 | 1990-06-25 | OXYCHLORATION PROCESS AND CATALYST, THEIR APPLICATION TO THE PRODUCTION OF 1-2 DICHLOROETHANE. |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO912463D0 NO912463D0 (en) | 1991-06-24 |
| NO912463L NO912463L (en) | 1991-12-27 |
| NO174846B true NO174846B (en) | 1994-04-11 |
| NO174846C NO174846C (en) | 1994-07-20 |
Family
ID=9397961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO912463A NO174846C (en) | 1990-06-25 | 1991-06-24 | Process and catalyst for oxychlorination in the preparation of 1,2-dichloroethane |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0463923B1 (en) |
| JP (2) | JP2587550B2 (en) |
| KR (1) | KR960004872B1 (en) |
| CN (2) | CN1026780C (en) |
| AT (1) | ATE102915T1 (en) |
| CA (1) | CA2045187C (en) |
| DE (1) | DE69101403T2 (en) |
| DK (1) | DK0463923T3 (en) |
| ES (1) | ES2062717T3 (en) |
| FI (1) | FI101533B1 (en) |
| FR (1) | FR2663629B1 (en) |
| IE (1) | IE69323B1 (en) |
| NO (1) | NO174846C (en) |
| PT (1) | PT98081B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11506113A (en) * | 1995-06-07 | 1999-06-02 | ザ ダウ ケミカル カンパニー | Oxychlorination catalysts and methods |
| TWI341218B (en) * | 2005-11-14 | 2011-05-01 | Oxy Vinyls Lp | Catalyst compositions and process for oxychlorination |
| CN103664504B (en) * | 2013-12-14 | 2015-10-28 | 济南开发区星火科学技术研究院 | A kind of technique being prepared vinylchlorid by ethane |
| CN108654587B (en) * | 2017-03-28 | 2021-09-07 | 中国石油化工股份有限公司 | Process for preparing halogenated hydrocarbons |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL292415A (en) * | 1962-05-08 | |||
| FR1359016A (en) * | 1962-06-15 | 1964-04-17 | Ici Ltd | Process for the production of halogenated hydrocarbons |
| CH533580A (en) * | 1969-11-14 | 1973-02-15 | Sir Soc Italiana Resine Spa | Procedure for oxychlorination |
| FR2242143B1 (en) * | 1973-09-04 | 1978-03-24 | Rhone Progil | |
| JPS572224A (en) * | 1980-06-06 | 1982-01-07 | Tokuyama Soda Co Ltd | Oxyhalogenation |
| IT1163160B (en) * | 1983-03-22 | 1987-04-08 | Montepolimeri Spa | SUPPORTED CATALYSTS FOR THE SYNTHESIS OF 1-2 DICHLOROETHANE FOR OXYCHLORURATION OF ETHYLENE IN A FLUIDIZED BED |
| DE3522473A1 (en) * | 1985-06-22 | 1987-01-02 | Basf Ag | MOLDED CATALYST, METHOD FOR THE PRODUCTION THEREOF, AND THE USE THEREOF IN OXICHLORATING ETHYLENE TO 1,2-DICHLORETHANE |
| IT1202538B (en) * | 1987-02-13 | 1989-02-09 | Enichem Sintesi | OXYCHLORATION CATALYST AND PROCEDURE FOR ITS PREPARATION |
| FR2641779B1 (en) * | 1988-12-26 | 1991-04-19 | Atochem | OXYCHLORATION PROCESS AND CATALYST, THEIR APPLICATION TO THE PRODUCTION OF 1-2 DICHLOROETHANE |
-
1990
- 1990-06-25 FR FR9007932A patent/FR2663629B1/en not_active Expired - Lifetime
-
1991
- 1991-06-17 EP EP91401608A patent/EP0463923B1/en not_active Expired - Lifetime
- 1991-06-17 AT AT91401608T patent/ATE102915T1/en not_active IP Right Cessation
- 1991-06-17 DE DE69101403T patent/DE69101403T2/en not_active Expired - Fee Related
- 1991-06-17 ES ES91401608T patent/ES2062717T3/en not_active Expired - Lifetime
- 1991-06-17 DK DK91401608.4T patent/DK0463923T3/en active
- 1991-06-21 CA CA002045187A patent/CA2045187C/en not_active Expired - Fee Related
- 1991-06-24 IE IE218691A patent/IE69323B1/en not_active IP Right Cessation
- 1991-06-24 FI FI913066A patent/FI101533B1/en not_active IP Right Cessation
- 1991-06-24 NO NO912463A patent/NO174846C/en not_active IP Right Cessation
- 1991-06-24 PT PT98081A patent/PT98081B/en not_active IP Right Cessation
- 1991-06-24 JP JP3151696A patent/JP2587550B2/en not_active Expired - Fee Related
- 1991-06-25 CN CN91104151A patent/CN1026780C/en not_active Expired - Fee Related
- 1991-06-25 KR KR1019910010614A patent/KR960004872B1/en not_active IP Right Cessation
-
1994
- 1994-03-23 CN CN94103211A patent/CN1046495C/en not_active Expired - Fee Related
-
1996
- 1996-05-02 JP JP8111738A patent/JP2673120B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR920000680A (en) | 1992-01-29 |
| FI101533B (en) | 1998-07-15 |
| FI913066A0 (en) | 1991-06-24 |
| DE69101403D1 (en) | 1994-04-21 |
| DK0463923T3 (en) | 1994-06-27 |
| NO912463L (en) | 1991-12-27 |
| FI913066A (en) | 1991-12-26 |
| ATE102915T1 (en) | 1994-04-15 |
| FR2663629B1 (en) | 1992-12-18 |
| ES2062717T3 (en) | 1994-12-16 |
| NO174846C (en) | 1994-07-20 |
| CN1046495C (en) | 1999-11-17 |
| PT98081A (en) | 1992-03-31 |
| CN1026780C (en) | 1994-11-30 |
| IE69323B1 (en) | 1996-09-04 |
| CA2045187A1 (en) | 1991-12-26 |
| EP0463923B1 (en) | 1994-03-16 |
| EP0463923A1 (en) | 1992-01-02 |
| NO912463D0 (en) | 1991-06-24 |
| CN1101336A (en) | 1995-04-12 |
| IE912186A1 (en) | 1992-01-01 |
| JP2673120B2 (en) | 1997-11-05 |
| CA2045187C (en) | 1999-04-27 |
| PT98081B (en) | 1998-11-30 |
| KR960004872B1 (en) | 1996-04-16 |
| FI101533B1 (en) | 1998-07-15 |
| FR2663629A1 (en) | 1991-12-27 |
| JP2587550B2 (en) | 1997-03-05 |
| JPH04253926A (en) | 1992-09-09 |
| DE69101403T2 (en) | 1994-08-25 |
| JPH0925249A (en) | 1997-01-28 |
| CN1057642A (en) | 1992-01-08 |
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