DK151007B - FLUIDIZABLE POWDER-SHAPED CONTACT MASS USED BY OXYHALOGENATION OF IN-GAS PHASE CARBON MONOXIDE AND CARBON HYDROIDES - Google Patents
FLUIDIZABLE POWDER-SHAPED CONTACT MASS USED BY OXYHALOGENATION OF IN-GAS PHASE CARBON MONOXIDE AND CARBON HYDROIDES Download PDFInfo
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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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/32—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with introduction into the fluidised bed of more than one kind of moving particles
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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
- 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
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- 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
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Description
151007151007
Den foreliggende opfindelse angår en fluidiserbar pulverformet kontaktmasse til anvendelse ved oxyhalogenering i gasfase af carbonmonoxid og de i krav l's indledning nævnte carbonhydrider indeholdende en fluidiserbar oxyhalogeneringskatalysator.The present invention relates to a fluidizable powder contact mass for use in carbon monoxide gas phase oxygenation and the hydrocarbons mentioned in the preamble of claim 1 containing a fluidizable oxyhalogenation catalyst.
Det er kendt f.eks. at fremstille 1,2-dichlorethan ved oxychlo-rering af ethylen i gasfase i nærværelse af et fluidiseret katalysatorleje, der i reglen er på basis af kobberchlorider og -oxychlorider, der er afsat på en bærer, såsom aktiveret aluminiumoxid, siliciumdioxid, magnesia, kiselgur og diatoméjord.It is known e.g. preparing 1,2-dichloroethane by gas phase oxychlorination in the presence of a fluidized catalyst bed which is generally based on copper chlorides and oxychlorides deposited on a support such as activated alumina, silica, magnesia, silica and diatomaceous earth.
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Da oxyhalogeneringsreaktionerne af halogenerede eller ikke-halo-generede carbonhydricLer er stærkt exotherme, så har fremgangsmåden under anvendelse af fluldiseret leje teoretisk set den fordel, at man kontinuerligt sikrer en perfekt isothermi i reaktionszonen og en særdeles god kontakt mellem de forskellige reaktanter - halogenerede eller ikke-rhålogenerede carbonhydrider, hydrogen- eller ammoniumhalogenider samt gassen indeholdende oxygen -og dette takket være den intense omrøring af katalysatoren, der holdes i fluidiseret tilstand. Det er således det fluidiserede katalysatorlejes homogene struktur, der er en væsentlig faktor som muliggør en god selektivitet med hensyn til det ønskede produkt og som følge deraf høje udbytter.Since the oxyhalogenation reactions of halogenated or non-halogenated hydrocarbons are highly exothermic, the process using flulized bed has, theoretically, the advantage of continuously ensuring perfect isothermia in the reaction zone and a very good contact between the various reactants - halogenated or not. -rough allogeneic hydrocarbons, hydrogen or ammonium halides, and the gas containing oxygen, and this thanks to the intense stirring of the catalyst which is kept in a fluidized state. Thus, it is the homogeneous structure of the fluidized catalyst bed that is a major factor enabling a good selectivity with respect to the desired product and, consequently, high yields.
Ved den kontinuerte fremgangsmåde, som man foretager i industriel skala, d.v.s. med store rumfang fluidiseret katalysatorleje, forstyrrer imidlertid visse forhold reaktorens funktion, og især lejets hydrodynamik, således at fremgangsmåden gøres uanvendelig. Man har f.eks. iagttaget at de foretrukne passager af gasformige reaktanter gennem lejet medfører et fald i den termiske udvekslingskoefficient i nærheden af væggene, og sommetider endog en nedgang i lejets isothermi og dets reaktivitet. Man har konstateret dannelse af meget store bobler af de reagerende gasser eller ubevægelige katalysatorzoner i det fluidiserede leje, hvilket ligeledes nedsætter lejets reaktivitet og kan forstyrre funktionen af de fast-stof-gas-separatorer, der i reglen er anbragt efter det fluidiserede leje i reaktoren, samt retur- eller recirkuleringsorganerne, samt indførings- og udtagningsorganerne for katalysatorpartiklerne. Man har yderligere iagttaget en tendens til at visse af katalysatorpartiklerne, især de fineste, klæber sammen indbyrdes eller på reaktorens metalvægge og de tilstødende områder, og således medfører et katalysatortab, en permanent ændring af katalysatorpartiklernes granulometrifordeling samt et fald i varmeudvekslings-koefficienten. Det er således særdeles vanskeligt at opretholde en stabil granulometrifordeling under driften. Især vil katalysatortabene, der er særlig udtalte for de fineste partikler, ved medrivning af disse fra lejet til faststof-gas-separeringsorganerne kontinuerligt modificere granulometrifordelingen. Nedgangen i mængden af fluidiseret katalysator i form af fine partikler medfører mere eller mindre hurtigt en ødelæggelse af fluidiseringen, der fra tid til anden fuldstændigt kan forstyrre funktionen af frem- 3 151007 gangsmåden under anvendelse af fluidiseret leje.In the continuous process performed on an industrial scale, i.e. however, with large volumes of fluidized catalyst bed, certain conditions interfere with the operation of the reactor, and in particular the hydrodynamics of the bed, making the process unusable. One has e.g. observed that the preferred passages of gaseous reactants through the bed cause a decrease in the thermal exchange coefficient near the walls, and sometimes even a decrease in the isotherm of the bed and its reactivity. Formation of very large bubbles of the reacting gases or motionless catalyst zones in the fluidized bed has been found, which also decreases the reactivity of the bed and can interfere with the operation of the solid-state gas separators, which are usually disposed after the fluidized bed in the reactor. , as well as the return or recycle means, as well as the feed and take-out means for the catalyst particles. A further tendency has been observed for some of the catalyst particles, especially the finest, to adhere to one another or to the metal walls of the reactor and the adjacent areas, thus resulting in a catalyst loss, a permanent change in the granulometry distribution of the catalyst particles, and a decrease in the heat exchange coefficient. Thus, it is extremely difficult to maintain a stable granulometry distribution during operation. In particular, the catalyst losses, which are particularly pronounced for the finest particles, by entraining them from the bed to the solid-gas separation means will continuously modify the granulometry distribution. The decrease in the amount of fluid particles in the form of fine particles more or less quickly results in a destruction of the fluidization which from time to time can completely disrupt the operation of the process using fluidized bed.
En anden årsag til katalysatortabene er slid og knusning af partiklerne på grund af stød indbyrdes og kontakt med væggene. Dette fænomen, som kan benævnes nedslidning, medfører ligeledes en udvikling i katalysatorens partikelstørrelse. På den ene side kan nedslidningsgraden variere afhængigt af granulometriudsnittet, og på den anden side er nedslidningsprodukterne enten ultrafine partikler, der forsvinder fra lejet og ikke kan recirkuleres, eller tilstrækkeligt store partikler til at de forbliver i lejet, og således beriger visse granulometriudsnit. Efter omstændighederne medfører nedslidningen således enten et prohibitivt tab af faste stoffer eller en berigelse med fine partikler, der kan resultere i en til stadighed stigende ekspansion af det fluldisérede -leje, en forstyrrelse i funktionen af faststof-gas-separatorerne, .en klæbning eller.agglomerering af fine partikler og/eller en nedgang i varmeudvekslingskoefficienten ved væggene, hvilket nødvendiggør at man sænker tilførslen til reaktoren og derved dens produktivitet.Another cause of the catalyst losses is wear and crushing of the particles due to shock between them and contact with the walls. This phenomenon, which can be called attrition, also causes a evolution in the particle size of the catalyst. On the one hand, the degree of wear may vary depending on the granulometry section, and on the other hand, the wear products are either ultra-fine particles that disappear from the bed and cannot be recycled, or sufficiently large particles to remain in the bed, thus enriching certain granulometry sections. Thus, according to the circumstances, the attrition results in either a prohibitive loss of solids or an enrichment of fine particles, which may result in an ever-expanding expansion of the fluidized bed, a disturbance in the function of the solid-gas separators, an adhesion or. agglomeration of fine particles and / or a decrease in the heat exchange coefficient at the walls, which necessitates lowering the feed to the reactor and thereby its productivity.
For at .forøge produktiviteten af reaktorer med fluidiseret leje har man foreslået at hæve gasgennemstrømningshastighederne og trykket, og som følge deraf varmeudvekslingskoefficienten. For at bevare det samme nyttige tværsnit for gaspassagen er man nødt til at forøge højden af reaktoren, og således anvende en lejehøjde, der er større end den, der giver det bedste kemiske udbytte af det ønskede produkt.In order to increase the productivity of fluidized bed reactors, it has been proposed to raise the gas flow rates and pressure, and consequently the heat exchange coefficient. In order to maintain the same useful cross-section of the gas passage, it is necessary to increase the height of the reactor, and thus use a bed height greater than that which gives the best chemical yield of the desired product.
Endvidere er den overskydende del af lejet sæde for parasitreaktionei såsom en efterforbrænding under dannelse af CC^ og CO og en dannelse af efterchlorerede og oxygenerede carbonhydrider, der sænker udbyttet af de nyttige produkter i betydelig udstrækning. Man kan således observere en zone med en højere temperatur i den nederste del af det fluidiserede leje i nærheden af fordelingsorganet for de gasformige reaktanter, især når man opererer under tryk eller med en gas, der er beriget med oxygen i forhold til luft. Dette fænomen udgør en risiko for sikkerheden ved fremgangsmåden og formindsker selektiviteten med hensyn til det nyttige -reaktionsprodukt.Furthermore, the excess portion of the bed is the site of parasite reaction, such as a post-combustion to form CC 2 and CO, and a formation of post-chlorinated and oxygenated hydrocarbons which significantly lowers the yield of the useful products. Thus, a zone of higher temperature can be observed in the lower part of the fluidized bed in the vicinity of the gaseous reactant distributor, especially when operated under pressure or with oxygen-enriched gas with air. This phenomenon poses a risk to the safety of the process and diminishes the selectivity of the useful reaction product.
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Alle de ovenfor beskrevne fænomener, der er forbundet med anvendelsen af fluidiseret leje, er særdeles skadelige for en god drift af et industrielt anlæg, f.eks. til fremstilling af 1,2-dichlorethan, især opnået ved selektiv oxychlorering af ethylen.All of the above-described phenomena associated with the use of fluidized bed are extremely detrimental to the good operation of an industrial plant, e.g. for the preparation of 1,2-dichloroethane, especially obtained by selective oxychlorination of ethylene.
Formålet med den foreliggende opfindelse er i stor udstrækning eller fuldstændigt at råde bod på de ovennævnte ulemper på en meget simpel og effektiv måde, med andre ord muliggøre en betydelig nedgang i nedslidningen, undertrykke klæbning af fine katalysatorpartikler, kraftigt reducere forbruget af disse fine partikler, formindske temperaturforskellen mellem den nedre og øvre del af lejet, samt indstille katalysatorkontaktmassens reaktivitet således at højden af lejet svarer til det bedste udbytte, især med hensyn til 1,2-dichlorethan, når der er tale om oxychlorering i gasfase af ethylen.The object of the present invention is, to a large extent or completely, to remedy the above-mentioned disadvantages in a very simple and effective manner, in other words enabling a considerable reduction in attrition, suppressing the adhesion of fine catalyst particles, greatly reducing the consumption of these fine particles, reduce the temperature difference between the lower and upper part of the bed, and adjust the reactivity of the catalyst contact mass so that the height of the bed corresponds to the best yield, especially with regard to 1,2-dichloroethane in the case of gas phase oxychlorination of ethylene.
Dette opnås ved anvendelse af den fluidiserbare pulverformede kontaktmasse ifølge opfindelsen, der er ejendommelig ved det i krav l's kendetegnede del anførte.This is achieved by using the fluidizable powdered contact mass according to the invention, which is characterized by the characteristic part of claim 1.
Blandt de katalytisk og kemisk inerte stoffer, der kan anvendes som fortyndingsmiddel, men i intet tilfælde som bærer for katalysatoren, kan især nævnes mikrokugler af glas eller si-liciumdioxid,tk-aluminiumoxid, og fortrinsvis kvartssand, som man finder i naturlig tilstand, og hvis granulometrifordeling af partikelstørrelsen er tilpasset til de krav som fluidiserin-gen stiller.Among the catalytically and chemically inert substances which can be used as a diluent, but in no case as a carrier for the catalyst, are in particular microspheres of glass or silicon dioxide, tk-alumina, and preferably quartz sand found in the natural state, and if the particle size granulometry distribution is adapted to the requirements of fluidisation.
Granulometrifordelingen af selve katalysatoren på den ene side og af det katalytisk og kemisk inerte stof på den anden side vælges således, at diameteren og spredningen i partikelstørrelsen· af blandingen er gunstige for en god fluidisering, og er 20-200^um med en middeldiameter på 40-90^um.The granulometry distribution of the catalyst itself on the one hand and of the catalytically and chemically inert substance on the other hand is chosen such that the diameter and particle size distribution of the mixture are favorable for good fluidization and are 20-200 µm with an average diameter of 40-90 ^ um.
Det har vist sig, at det for at opnå de ovennævnte fordele er at foretrække, at de største partikler i blandingen, der skal flui-diseres, for størstedelens vedkommende består af katalysatoren, mens 5 151007 de mere fine partikler for størstedelens vedkommende "består af det inerte faste stof, især kvartssand, hvormed der er opnået særdeles gode resultater.It has been found that in order to obtain the above advantages, it is preferable that the largest particles in the mixture to be fluid consist, for the most part, of the catalyst, while the finer particles for the majority "consist of the inert solid, especially quartz sand, with which excellent results have been obtained.
Den fluidiserbare kontaktmasse ifølge opfindelsen anvendes.som angivet ovenfor ved en oxyhalogeneringsreaktion.i gasfase, fortrinsvis oxychlorering af carbonmonoxid, mættede eller umættede alifatiske carbonhydrider med 1-20 carbonatomer, cycloalifatiske carbon-hydrider med indtil 12 carbonatomer og aromatiske carbonhydrider med indtil 4 kondenserede benzenringe samt bromsubstituerede og især chlorsubstituerede derivater deraf, men især af ethylen.The fluidizable contact mass of the invention is used as indicated above in an oxyhalogenation reaction in the gas phase, preferably oxychlorination of carbon monoxide, saturated or unsaturated aliphatic hydrocarbons having 1-20 carbons, cycloaliphatic hydrocarbons having up to 12 carbons and aromatic hydrocarbons having up to 4 condensed rings bromo-substituted and especially chloro-substituted derivatives thereof, but especially of ethylene.
Som gas indeholdende oxygen anvender man oftest luft eller oxygen-beriget luft, og som bæregas for halogen, fortrinsvis chlor eller brom, kan man anvende et hydrogen- og/eller ammoniumhalogenid.As gas containing oxygen, air or oxygen-enriched air is most often used, and as a carrier gas for halogen, preferably chlorine or bromine, a hydrogen and / or ammonium halide can be used.
Om ønsket kan man til supplering af det ved reaktionen mellem oxygen og hydrogen- og/eller ammoniumhalogenid in situ dannede frie chlor indføre yderligere frit chlor i reaktoren sammen med carbonmonoxid eller carbonhydridet.If desired, in addition to the free chlorine formed in situ by the reaction between oxygen and hydrogen and / or ammonium halide, additional free chlorine can be introduced into the reactor together with the carbon monoxide or hydrocarbon.
De generelle betingelser for oxyhalogeneringsreaktionen er for temperaturens vedkommende i reglen 170-500°C og for trykkets vedkommende 1-20 absolutte bar. Molforholdet 02/carbonhydrid og/eller halogeneret carbonhydrid og/eller carbonmonoxid/hydrogen- og/eller ammoniumhalogenid kan variere inden for meget brede rammer efter det ønskede resultat. Hvis man ønsker at være selektiv med hensyn til en specifik forbindelse anvender man således reaktantforhold, der nærmer sig de støkiometriske, mens man hvis man søger at opnå en blanding af halogenerede carbonhydrider, anvender forholdsvis mindre mængder af de carbonholdige udgangsmaterialer.The general conditions for the oxyhalogenation reaction are, for the temperature, usually 170-500 ° C and for the pressure 1-20 absolute bar. The molar ratio of O 2 / hydrocarbon and / or halogenated hydrocarbon and / or carbon monoxide / hydrogen and / or ammonium halide may vary within very wide ranges according to the desired result. Thus, if one wishes to be selective with respect to a specific compound, reactant ratios approaching the stoichiometric approach are employed, whereas if one seeks to obtain a mixture of halogenated hydrocarbons, relatively smaller amounts of the carbonaceous starting materials are used.
Generelt kan man anvende enhver oxyhalogeneringskatalysator, der kan fluidiseres, ved fortyndingen med det inerte faste stof til opnåelse af de fluidiserbare pulverformede kontaJctmasser ifølge opfi: delsen. Hvis man imidlertid foretager en oxychlorering af ethylen foretrækker man katalysatorer, der i det væsentlige består af en bærer af aktiveret aluminiumoxid med en specifik overflade på 150-400 m /g, især 200-350 m /g, hvorpå der er afsat et kobbersalt 6 151007 af en mineralsyre, fortrinsvis kobber (Il)chlorid i mængder på 3-10 vægtpct. kobber i forhold til den færdige katalysator.In general, any fluidizable oxyhalogenation catalyst can be used in the dilution with the inert solid to obtain the fluidizable powdered contact masses of the invention. However, if an oxychlorination of ethylene is preferred, catalysts consisting essentially of a carrier of activated alumina having a specific surface area of 150-400 m / g, in particular 200-350 m / g, upon which a copper salt is deposited 6 151007 of a mineral acid, preferably copper (II) chloride in amounts of 3-10 wt. copper relative to the finished catalyst.
Af de følgende eksempler illustrerer eksempel 1 og 2 opfindelsen.Of the following examples, Examples 1 and 2 illustrate the invention.
EKSEMPEL 1EXAMPLE 1
Man foretager en oxychlorering i gasfase af ethylen til 1,2-dichlorethan i en cylindrisk reaktor med en diameter på 120 mm og en højde på 7 m. En varmeveksler strækker sig 4 m op fra reaktorens bund, og cykloner forsynet med returrør recirkulerer kontinuerligt de fluidiserede partikler af kontaktmassen, der er medrevet af reaktionsgasserne, til lejets bund. Dette fluidiserede leje består af en blanding af 70 vægtpct. partikler af naturligt kvartssand med en middeldiameter på 50 yum og 30 vægtprocent af en katalysator bestående af aktiveret aluminiumoxid med en middeldiameterA gas phase oxychlorination of ethylene to 1,2-dichloroethane is carried out in a cylindrical reactor with a diameter of 120 mm and a height of 7 m. A heat exchanger extends 4 m up from the bottom of the reactor and cyclones with return pipes continuously recycle the fluidized particles of contact mass entrained by the reaction gases to the bottom of the bed. This fluidized bed consists of a mixture of 70% by weight. natural quartz sand particles having a mean diameter of 50 µm and 30% by weight of a catalyst consisting of activated alumina having a mean diameter
OISLAND
på 95 /um, hvis specifikke overflade er 300 m /g, hvorpå der er afsat 6 vægtpct. kobber i form af CuCl2, 2 ^0.of 95 µm, the specific surface area of which is 300 m / g, on which 6 wt. copper in the form of CuCl2, 2 ^ 0.
Granulometrifordelingen af denne partikelblanding var 20-150 yum med en middeldiameter på 63,5 ^um.The granulometry distribution of this particle mixture was 20-150 µm with a mean diameter of 63.5 µm.
Man leder kontinuerligt reaktanterne HC1, ethylen og luft i de molære forhold O^/C^H^ = 0,60 og HClA^H^ = 2 gennem 30 kg af den. fluidiserede kontaktmasse. Temperaturen i reaktoren var 225°C og trykket 4 absolutte bar-The reactants HCl, ethylene and air are continuously fed in the molar ratios of O 2 / C fluidized contact mass. The temperature of the reactor was 225 ° C and the pressure was 4 absolute bar
Den lineære hastighed for de gasformige reaktanter i reaktoren var 20 cm/ sek.The linear velocity of the gaseous reactants in the reactor was 20 cm / sec.
Efter 1.000 timers kontinuerlig drift har man opnået følgende omdannelsesgrader for ethylen til andre forbindelser: 1.2- dichlorethan 96,8% 1.1.2- trichlorethan 0,8% 1.1.2.2- tetrachlorethan 0,6% cis- og trans-dichlorethylen 0,2% trichlorethylen 0,2% CO + C02 1,2% 7 151007After 1,000 hours of continuous operation, the following conversion rates of ethylene to other compounds have been obtained: 1.2-dichloroethane 96.8% 1.1.2-trichloroethane 0.8% 1.1.2.2-tetrachloroethane 0.6% cis- and trans-dichloroethylene 0.2 % Trichlorethylene 0.2% CO + CO 1.2% 7 151007
Den totale omdannelsesgrad for ethylen er således 99,8%.Thus, the total conversion rate of ethylene is 99.8%.
Efter disse 1.000 timers drift har granulometrifordelingen for katalysatoren praktisk talt ikke varieret, varmeudvekslingskoefficienten er forblevet konstant, og ingen katalysatorpartikler har klæbet sammen, ligesom nedslidningen var ubetydelig.After these 1,000 hours of operation, the granulometry distribution of the catalyst has practically not varied, the coefficient of heat exchange has remained constant, and no catalyst particles have stuck together, just as the wear was negligible.
Der opnåedes reducerede katalysatortab: 0,5 vægtpct. pr. dag ved kontinuerlig drift.Reduced catalyst losses were achieved: 0.5% by weight. per. day of continuous operation.
Sammenligningseksempel 1Comparative Example 1
Man har gentaget eksempel 1, bortset fra at det fluidiserede leje kun indeholdt 30 kg katalysator, der ikke var fortyndet med sand, og havde en middeldiameter på 63,5 /um, ligesom blandingen i eksempel 1.Example 1 was repeated except that the fluidized bed contained only 30 kg of non-sand diluted catalyst and had a mean diameter of 63.5 µm, as was the mixture of Example 1.
Efter 300 timers drift var katalysatoren stærkt nedslidt, og lejet var kontinuerligt blevet beriget med partikler, der var mindre end 40^/um, hvorfor middeldiameteren var faldet fra 63,5 til 40 ^,um.After 300 hours of operation, the catalyst was severely worn and the bed had been continuously enriched with particles smaller than 40 µm, which is why the mean diameter had dropped from 63.5 to 40 µm.
Ekspansionskoefficienten for det fluidiserede leje (forholdet mellem den fluidiserede højde og højden af lejet i hvile) er forøget, og varmeudvekslingskoefficienten er faldet stærkt.The coefficient of expansion of the fluidized bed (the ratio of the fluidized height to the height of the bed at rest) is increased and the heat exchange coefficient is greatly decreased.
Omdannelsesgraderne for ethylen til andre forbindelser var følgende: 1.2- dichlorethan 89% CO + C02 7% 1.1.2- trichlorethan 1,35% 1.1.2.2- tetrachlorethan 0,75% cis- og trans-dichlorethylen 0,4% trichiorethylen 0,5%The conversion rates of ethylene to other compounds were as follows: 1.2- dichloroethane 89% CO + CO2 7% 1.1.2- trichloroethane 1.35% 1.1.2.2- tetrachloroethane 0.75% cis- and trans-dichloroethylene 0.4% trichloroethylene 0, 5%
Den totale omdannelsesgrad for ethylenen var således 99%.Thus, the total conversion rate of ethylene was 99%.
Katalysatortabene efter de 300 timers drift var 15 kg, svarende til 4 vægtpct. pr. dag, hvilket er et betydeligt tab.The catalyst losses after 300 hours of operation were 15 kg, corresponding to 4% by weight. per. day, which is a significant loss.
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Driften måtte afbrydes på grund af den hurtige ændring af gra-nulometrien, der medførte talrige forstyrrelser på grund af den betydelige berigelse med katalysatorpartikler, med størrelser på under 40 yum.Operation had to be interrupted due to the rapid change of the granulometry, which caused numerous disruptions due to the significant enrichment with catalyst particles, with sizes of less than 40 µm.
EKSEMPEL 2EXAMPLE 2
Man foretager en oxychlorering af ethylen til 1,2-dichlorethan i en reaktor i industriel skala med en diameter på 2 m og en højde på 15 m.An oxychlorination of ethylene to 1,2-dichloroethane is carried out in an industrial scale reactor with a diameter of 2 m and a height of 15 m.
Den fluidiserbare kontaktmasse bestod af 20 t af den blanding af katalytisk og kemisk inert sand og katalysator, der er beskrevet i eksempel 1The fluidizable contact mass consisted of 20 t of the mixture of catalytically and chemically inert sand and catalyst described in Example 1
Cykloner med returrør recirkulerede kontinuerligt de medrevne partikler.Cyclones with return tubes continuously recycle the entrained particles.
Reaktanterne C2H^, HC1 og oxygen (i form af luft) i et molært forhold 1/2/0,65 indførtes ved reaktorens bund gennem det fluidi-serede leje. Den lineære hastighed for de gasformige reaktanter var 30 cm/ sek.The reactants C 2 H 2, HCl and oxygen (in the form of air) at a molar ratio 1/2 / 0.65 were introduced at the bottom of the reactor through the fluidized bed. The linear velocity of the gaseous reactants was 30 cm / sec.
Temperaturen i reaktoren var 230°C og trykket 4,5 absolutte bar. Omdannelsesgraderne for ethylen til andre forbindelser var følgende: 1.2- dichlorethan 97,0 % 1.1.2- trichlorethan 0,3 % 1.1.2.2- tetrachlorethan 0,1 % trichlorethylen 0,15 % cis- og trans-dichlorethylen 0,15% CO + C02 0,93%The temperature of the reactor was 230 ° C and the pressure was 4.5 absolute bar. The conversion rates of ethylene to other compounds were as follows: 1.2- dichloroethane 97.0% 1.1.2- trichloroethane 0.3% 1.1.2.2- tetrachloroethane 0.1% trichloroethylene 0.15% cis- and trans-dichloroethylene 0.15% CO + CO 2 0.93%
Den totale omdannelsesgrad for ethylen var således 98,63%.Thus, the total conversion rate of ethylene was 98.63%.
Efter 8.000 timers kontinuerlig drift var granulometrien, ekspansionskoefficienten for det fluidiserede leje samt varmeudvekslingskoefficienten praktisk talt ikke ændret.After 8,000 hours of continuous operation, the granulometry, fluid coefficient expansion coefficient, and heat exchange coefficient had practically not changed.
9 1510079 151007
Nedslidningen af katalysatoren var ubetydelig, og katalysatortabet var reduceret til størrelsesordenen 0,4 vægtpct. pr. dag.Catalyst wear was negligible and the catalyst loss was reduced to the order of 0.4% by weight. per. day.
De ovenstående eksempler illustrerer klart de betydelige fordele ved anvendelsen af den omhandlede fluidiserbare kontaktmasse, hvoraf de væsentligste er følgende: a) En betydelig forbedring af katalysatorøkonomien i forhold til sammensætningen af den kendte fluidiserbare kontaktmasse og ved forbruget ved kontinuert drift; b) Stabilisering af granulometrien, hvorved man undgår talrige ulemper, som f.eks. tilstopning af cyklonerne og sammenklæbning af katalysatoren, der kan være katastrofale; c) Forbedring af udbyttet ved hovedreaktionen.The above examples clearly illustrate the significant advantages of using the present fluidizable contact mass, the most significant of which are the following: a) a significant improvement in the catalyst economy over the composition of the known fluidizable contact mass and the consumption of continuous operation; b) Stabilization of the granulometry, thereby avoiding numerous disadvantages such as clogging the cyclones and sticking the catalyst which can be catastrophic; c) Improving the yield of the main reaction.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7331837 | 1973-09-04 | ||
| FR7331837A FR2242143B1 (en) | 1973-09-04 | 1973-09-04 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK464874A DK464874A (en) | 1975-05-05 |
| DK151007B true DK151007B (en) | 1987-10-12 |
| DK151007C DK151007C (en) | 1988-02-29 |
Family
ID=9124596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK464874A DK151007C (en) | 1973-09-04 | 1974-09-03 | FLUIDIZABLE POWDER-SHAPED CONTACT MASS USED BY OXYHALOGENATION OF IN-GAS PHASE CARBON MONOXIDE AND CARBON HYDROIDES |
Country Status (21)
| Country | Link |
|---|---|
| JP (1) | JPS5324045B2 (en) |
| AR (1) | AR201883A1 (en) |
| AU (1) | AU7293474A (en) |
| BE (1) | BE819480A (en) |
| BR (1) | BR7407330D0 (en) |
| CA (1) | CA1024998A (en) |
| DK (1) | DK151007C (en) |
| EG (1) | EG11251A (en) |
| ES (1) | ES429752A1 (en) |
| FR (1) | FR2242143B1 (en) |
| GB (1) | GB1474258A (en) |
| IE (1) | IE39884B1 (en) |
| IN (1) | IN143087B (en) |
| IT (1) | IT1019186B (en) |
| NL (1) | NL189855C (en) |
| NO (1) | NO141358C (en) |
| PH (1) | PH12560A (en) |
| PL (1) | PL96475B1 (en) |
| RO (1) | RO72689A (en) |
| SU (1) | SU567397A3 (en) |
| TR (1) | TR18376A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX152427A (en) * | 1979-09-12 | 1985-07-15 | Mexicano Inst Petrol | IMPROVED REACTOR AND PROCEDURE FOR ETHYLENE OXYCHLORATION |
| FR2641779B1 (en) * | 1988-12-26 | 1991-04-19 | Atochem | OXYCHLORATION PROCESS AND CATALYST, THEIR APPLICATION TO THE PRODUCTION OF 1-2 DICHLOROETHANE |
| ES2017452T3 (en) * | 1988-12-29 | 1995-01-01 | Monsanto Co | FLUID BED PROCEDURES. |
| US5079379A (en) * | 1988-12-29 | 1992-01-07 | Monsanto Company | Fluid bed process |
| JPH0414509U (en) * | 1990-05-29 | 1992-02-05 | ||
| US5243111A (en) * | 1990-06-25 | 1993-09-07 | Atochem | Catalytic oxychlorination of hydrocarbons to produce chlorocarbons |
| FR2663629B1 (en) * | 1990-06-25 | 1992-12-18 | Atochem | OXYCHLORATION PROCESS AND CATALYST, THEIR APPLICATION TO THE PRODUCTION OF 1-2 DICHLOROETHANE. |
| TWI341218B (en) * | 2005-11-14 | 2011-05-01 | Oxy Vinyls Lp | Catalyst compositions and process for oxychlorination |
| US11059774B2 (en) | 2018-06-28 | 2021-07-13 | Ascend Performance Materials Operations Llc | Processes and systems for using silica particles in fluid bed reactor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1047760B (en) * | 1956-05-31 | 1958-12-31 | Dow Chemical Co | Improved Process for Oxychlorination of Hydrocarbons |
| GB894138A (en) * | 1958-06-24 | 1962-04-18 | Columbia Southern Chem Corp | Process for the production of chlorinated hydrocarbons |
| DE1142161B (en) * | 1958-06-24 | 1963-01-10 | Pittsburgh Plate Glass Co | Process for the oxychlorination of aliphatic saturated hydrocarbons with 1 to 4 carbon atoms |
| DE1285467B (en) * | 1961-07-13 | 1968-12-19 | Pechiney Prod Chimiques Sa | Process for the oxychlorination of ethylenic hydrocarbons |
-
1973
- 1973-09-04 FR FR7331837A patent/FR2242143B1/fr not_active Expired
-
1974
- 1974-09-02 PH PH16230A patent/PH12560A/en unknown
- 1974-09-02 AR AR255423A patent/AR201883A1/en active
- 1974-09-02 GB GB3827274A patent/GB1474258A/en not_active Expired
- 1974-09-03 IE IE1823/74A patent/IE39884B1/en unknown
- 1974-09-03 IN IN1973/CAL/1974A patent/IN143087B/en unknown
- 1974-09-03 IT IT52860/74A patent/IT1019186B/en active
- 1974-09-03 NO NO743162A patent/NO141358C/en unknown
- 1974-09-03 RO RO7479903A patent/RO72689A/en unknown
- 1974-09-03 TR TR18376A patent/TR18376A/en unknown
- 1974-09-03 CA CA208,311A patent/CA1024998A/en not_active Expired
- 1974-09-03 PL PL1974173833A patent/PL96475B1/en unknown
- 1974-09-03 DK DK464874A patent/DK151007C/en not_active IP Right Cessation
- 1974-09-03 AU AU72934/74A patent/AU7293474A/en not_active Expired
- 1974-09-03 NL NLAANVRAGE7411646,A patent/NL189855C/en not_active IP Right Cessation
- 1974-09-03 SU SU7402056282A patent/SU567397A3/en active
- 1974-09-03 BR BR7330/74A patent/BR7407330D0/en unknown
- 1974-09-03 BE BE148159A patent/BE819480A/en not_active IP Right Cessation
- 1974-09-03 JP JP10127774A patent/JPS5324045B2/ja not_active Expired
- 1974-09-04 EG EG386/74D patent/EG11251A/en active
- 1974-09-04 ES ES429752A patent/ES429752A1/en not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1047760B (en) * | 1956-05-31 | 1958-12-31 | Dow Chemical Co | Improved Process for Oxychlorination of Hydrocarbons |
| GB894138A (en) * | 1958-06-24 | 1962-04-18 | Columbia Southern Chem Corp | Process for the production of chlorinated hydrocarbons |
| DE1142161B (en) * | 1958-06-24 | 1963-01-10 | Pittsburgh Plate Glass Co | Process for the oxychlorination of aliphatic saturated hydrocarbons with 1 to 4 carbon atoms |
| DE1285467B (en) * | 1961-07-13 | 1968-12-19 | Pechiney Prod Chimiques Sa | Process for the oxychlorination of ethylenic hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| TR18376A (en) | 1977-05-01 |
| CA1024998A (en) | 1978-01-24 |
| DE2442182A1 (en) | 1975-03-27 |
| AU7293474A (en) | 1976-03-11 |
| AR201883A1 (en) | 1975-04-24 |
| NL189855C (en) | 1993-08-16 |
| IE39884B1 (en) | 1979-01-17 |
| BR7407330D0 (en) | 1975-07-01 |
| BE819480A (en) | 1975-03-03 |
| JPS5070306A (en) | 1975-06-11 |
| NO141358B (en) | 1979-11-19 |
| DK464874A (en) | 1975-05-05 |
| GB1474258A (en) | 1977-05-18 |
| NL7411646A (en) | 1975-03-06 |
| PH12560A (en) | 1979-06-15 |
| IT1019186B (en) | 1977-11-10 |
| RO72689A (en) | 1981-03-30 |
| SU567397A3 (en) | 1977-07-30 |
| PL96475B1 (en) | 1977-12-31 |
| NL189855B (en) | 1993-03-16 |
| ES429752A1 (en) | 1976-11-01 |
| IE39884L (en) | 1975-03-04 |
| NO141358C (en) | 1980-02-27 |
| FR2242143A1 (en) | 1975-03-28 |
| DK151007C (en) | 1988-02-29 |
| NO743162L (en) | 1975-04-01 |
| IN143087B (en) | 1977-10-01 |
| FR2242143B1 (en) | 1978-03-24 |
| EG11251A (en) | 1977-01-31 |
| JPS5324045B2 (en) | 1978-07-18 |
| DE2442182B2 (en) | 1976-06-16 |
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