SE199842C1

SE199842C1 -

Info

Publication number: SE199842C1
Authority: SE
Publication date: 1965-01-01

Description

Prioritet begard frdn den 13 pit 1961 (Italign) Foreliggande uppfinning hanfor sig till ett salt for framstallning av klorerade kolvaten, narmare bestamt klormetaner och kloretaner. The present invention relates to a salt for the preparation of chlorinated hydrocarbons, more particularly chloromethanes and chloroethanes.

Det är fOrut kant att vid halogenisering av kolvaten genom substitution med klor endast halften av kloret later sig flirenas under bildande av klorderivat, medan en ungefarligen lika stor del omvandlas till klorvate. En dylik omvandling, som nara sammanhanger med det normala forloppet vid halogenisering genom substitution fororsakar i speciella fall, som exempelvis vid kolvaten med lag molekylvikt sasom metan, ett avsevart spill av klor per viktenhet av kolvatet och medfor salunda det besvarliga problemet med forvaring och atervinning av i avsevarda mangder bildat klorvate. Manga forslag hava gjorts for att antingen reducera olagenheten med en dylik bildning genom en fordelaktig regenerering eller fOr undvikande av denna bildning sa mycket som mOjligt anlita oxidationsreaktioner samtidigt med en halogeniseringsreaktion. It is a foregone conclusion that when halogenating the hydrocarbons by substitution with chlorine, only half of the chlorine is allowed to flirenase to form chlorine derivatives, while an approximately equal proportion is converted to chlorine. Such conversion, which is closely related to the normal process of halogenation by substitution, causes in special cases, such as low molecular weight hydrocarbons such as methane, a significant waste of chlorine per unit weight of the hydrocarbon and thus causes the problem of storage and recovery of in considerable quantities formed chlorine. Many suggestions have been made to either reduce the illegality of such formation by advantageous regeneration or to avoid this formation as much as possible to engage in oxidation reactions simultaneously with a halogenation reaction.

Atervinning av klorvate genom klorgenerering är forenad med ett problem av mer all-man karaktar, satillvida som atervinningen maste omfatta inte bara det klorvate, vilket erhalles genom halogenisering, utan ocksa det klorvate, vilket som biprodukt vid andra reaktioner sasom dehydroklorering, kondensationsprocesser etc. Det mest utforskade systemet är det, som baseras ph det forst av Deacon foreslagna Hilda fOrfarandet, som vasentligen bestar av en oxidation av klorvate med luft eller syre i narvaro av en katalysator vid temperaturer mellan 200 och 600° C. Recovery of chlorvate by chlorine generation is associated with a problem of a more general nature, insofar as the recovery must include not only the chlorvate, which is obtained by halogenation, but also the chlorvate, which as a by-product of other reactions such as dehydrochlorination, condensation processes, etc. The most explored system is the one based on the first Hilda method proposed by Deacon, which essentially consists of an oxidation of hydrogen chloride with air or oxygen in the presence of a catalyst at temperatures between 200 and 600 ° C.

Trots att detta fOrfarande blivit forbattrat och modifierat atskilligt har det icke kommit till anvandning i industrin. Orsaken torde vara att fOrfarandet nodvandiggor anvandfling av kraftiga overskottsmangder av syre eller luft och en hog temperatur, om den storsta omvandlingen av HC1 till klor skall kunna erhallas. Foljaktligen hr den slutliga separeringen av kloret, som erhalles i Mahallandevis raga koncentrationer, frail en blandning bestaende av en icke omvandlad syra eller med andra gaser som deltagit i eller alstrats vid reaktionen, synnerligen besvarlig, om man onskar utfa en produkt med den specifika renhetsgrad, som fOreskrives som kommersiell standard. Although this procedure has been significantly improved and modified, it has not been used in industry. The reason is probably that the process necessitates the use of large amounts of excess oxygen or air and a high temperature, if the greatest conversion of HCl to chlorine is to be obtained. Consequently, the final separation of the chlorine obtained in Mahallandevi's straight concentrations, from a mixture consisting of an unconverted acid or with other gases which participated in or generated in the reaction, is particularly difficult if one wishes to produce a product of the specific degree of purity. which is prescribed as a commercial standard.

Dylika forfaranden, vilka erfordra mycket dyra anlaggningar till foljd av den starka aggressiviteten av reagenserna ferdyra sa mycket atervinningskostnaden fOr kloret, att desamma ej vunnit insteg i praktiken. Such processes, which require very expensive plants due to the strong aggressiveness of the reagents, increase the cost of chlorine recovery so much that they have not gained a foothold in practice.

Den andra mojligheten ater, som principiellt gar ut pa en begransning eller fullstandig eliminering av Hel-bildningen genom samtidigt foretagna oxidationsreaktioner, galler speciellt halogeniseringsreaktioner. Forskningen Mom detta omrade liar a ena sidan till andamal att astadkomma de hogsta halogenutbytena genom att som utgangsreagenser anvanda klor och syre eller luft och a den andra sidan att anvanda som kloreringsmedel bara det klorvdte, som har molekylar association med syre eller luft. Ocksâ dylika forfaranden hava samband med Deacons reaktion, med vilken de hava katalysatom gemensamt, minstone satillvida som jamviktsforhallandet av oxidationen av HC1 till C12 i narvaro av kolvate är i fraga. I dylika fall bar emellertid temperaturen vara tillrhckligt hog for att motverka syrets inhiberande inverkan pa substitutionsreaktionen och pa samma gang tillrackligt lag for att astadkomma en gynnsam jamvikt i oxidationsreaktionen. Harav framgar betydelsen av en noggrann kontroll av de anvanda temperaturerna, vilken gores sped.- svar genom totalreaktionens starka termiska effekter, sora beror pa halogeniserings- 2— -- varmet och varmet av oxidationen av klorvate till klor, vilka bada reaktioner aro av starkt exotermisk natur. Sadan kontroll erfordrar speciellt dyr apparatur pa grund av reagensernas haftigt aggressiva natur. Vidare nedsatter en del storande forbranningsreaktioner vid de for genomforande av kloreringen genom substitution nodvandiga temperaturer, som for metan och etan ligga mellan 350 och 500° C, avsevart utbytet av klorderivat. Undantag harifran aro de reaktioner, vilka kunn.a genomforas -yid en relativt lag temperatur sasom vid klorering av bensen, eten och likn.ande foreningar, vilka genom att snabbt reagera med det bildade kloret tillàta anvandning av temperaturer mellan 150 och 250° C. The second possibility, which in principle involves a limitation or complete elimination of the Hel formation by oxidation reactions carried out simultaneously, applies in particular to halogenation reactions. This research focused on the one hand to achieve the highest halogen yields by using chlorine and oxygen or air as starting reagents and on the other hand to use as chlorinating agent only the chlorine, which has molecular association with oxygen or air. Such processes are also related to Deacon's reaction, with which they have the catalyst in common, at least as far as the equilibrium ratio of the oxidation of HCl to C12 in the presence of carbonate is in question. In such cases, however, the temperature should be sufficiently high to counteract the inhibitory effect of oxygen on the substitution reaction and at the same time sufficiently lawful to achieve a favorable equilibrium in the oxidation reaction. This shows the importance of a careful control of the temperatures used, which is accelerated by the strong thermal effects of the total reaction, which is due to the halogenation heat and the heat of the oxidation of hydrochloric acid to chlorine, both of which are strongly exothermic. nature. Such control requires particularly expensive equipment due to the highly aggressive nature of the reagents. Furthermore, some major combustion reactions at the temperatures necessary for carrying out the chlorination by substitution, which for methane and ethane are between 350 and 500 ° C, reduce the yield of chlorine derivatives considerably. Exceptions to this are those reactions which can be carried out at a relatively low temperature such as in the chlorination of benzene, ethylene and the like compounds which, by reacting rapidly with the chlorine formed, allow the use of temperatures between 150 and 250 ° C.

Ett andamal med foreliggande uppfinning ar att astadkomma ett forfaringssatt for framstallning av klorderivat genom substituerande halogenisering av kolvaten genom att sasom klorkalla anvanda klorvate enbart eller klorvate och klor. An object of the present invention is to provide a process for the preparation of chlorine derivatives by substituting halogenation of the hydrocarbons by using chlorvate alone or chlorvate and chlorine.

Ett annat andamal med foreliggande uppfinning Ur att astadkomma ett forfaringssatt for framstallning av klorderivat genom att praktiskt taget eliminera forekomsten av klorVale som biprodukt genom att aterfora sjalva klorvatet direkt som klorkalla. Another object of the present invention is to provide a process for the preparation of chlorine derivatives by practically eliminating the presence of chloroVale as a by-product by recycling the chlorine water itself directly as chlorine cold.

Dessa och andra andamal, vilka klarare komma att framgá av foljande beskrivning uppnas enligt foreliggande uppfinning vasentligen genom en serie reaktioner, vilka Ora det mojligt att genomfOra oxidationen av klorvatet och kloreringen av kolvatet i tva skilda steg och under sadana forhallanden, att det ena steget Sr beroende av det andra, varigenom en avsevard reduktion erhalles och i vissa fall en fullstandig eliminering av de olagenheter, som aro fOrknippade med bade regenerationen av klorvatet till klor enligt Deacons forfarande och i halogeniseringen av kolvaten enligt de hittills utvecklade och anvanda forfarandena. These and other objects, which will become more apparent from the following description, are achieved according to the present invention essentially by a series of reactions, which make it possible to carry out the oxidation of the chlorate and the chlorination of the carbonate in two different steps and under such conditions that one step Sr depending on the second, thereby obtaining a substantial reduction and in some cases a complete elimination of the irregularities associated with both the regeneration of the hydrochlorate to chlorine according to Deacon's procedure and in the halogenation of the hydrocarbons according to the processes hitherto developed and used.

Uppfinningen hanfor sig till ett salt for substituerande klorering av kolvaten, spedellt metan och etan, for framstallning av klorerade kolvaten genom att som kloreringsmedel anvanda klorvate och syrgas eller syre innehallande gaser, varvid kolvatet bringas att reagera direkt med en gasblandning som erMints genom oxidation av klorvate pa en kataIytisk badd med en kvantitet syre i underskott med avseende pa klorvatet under sh Tang tid att syreomvandlingen uppgar till minst 80 % och foretradesvis mellan 90 och 100 %. Reaktionen kan ocksa ske i narvaro av utiffan tillfort klor. The invention relates to a salt for substituting chlorination of the hydrocarbons, especially methane and ethane, for the preparation of chlorinated hydrocarbons by using chlorvate and oxygen-containing or oxygen-containing gases as chlorinating agent, the carbonate being reacted directly with a gas mixture which is oxidized by hydrochloric acid. on a catalytic bath with a quantity of oxygen in deficit with respect to the hydrogen chloride during sh Tang time that the oxygen conversion amounts to at least 80% and preferably between 90 and 100%. The reaction can also take place in the presence of chlorine.

Specient har man funnit att om oxidationsreaktionen av klorvate genomfOres p5 en katalysator i underskott ph syre ph ett sadant salt, att i det narmaste en total omvandling av syrgasen astadkommes, vilka betingelser ej forefunnits vid analoga forfaranden, kan en gasblandning bildas, vilken utan nagon vidare behandling Sr i stand att genomfora en efterfoljande klorering av kolvaten, speeiellt me-tan, under sarskilt gynnsamma betingelser, sarskilt de termiska, och med mycket hoga utbyten i synnerhet med avseende pa hogre klormetaner. Specifically, it has been found that if the oxidation reaction of chlorine hydrogen is carried out on a catalyst in excess of oxygen with such a salt, that almost a total conversion of the oxygen gas is effected, which conditions were not present in analogous processes, a gas mixture can be formed. treatment It is possible to carry out a subsequent chlorination of the hydrocarbons, especially methane, under particularly favorable conditions, especially the thermal ones, and with very high yields, in particular with respect to higher chloromethanes.

Genom att lata Deacons reaktion forsigga utan att taga hansyn till vare sig att erhalla de hogsta mojliga utbytena vid HC1-omvandlingen, dvs. genom att arbeta med underskott pa syre och icke vid overdrivet hoga temperaturer, och utan att behOva avskilja det erhallna kloret, minskas svarigheterna i totalforloppet av dylika forfaranden avsevart. By letting Deacon's reaction proceed without taking into account either obtaining the highest possible yields in the HCl conversion, ie. by working with a deficit of oxygen and not at excessively high temperatures, and without having to separate the obtained chlorine, the responsibilities in the overall process of such procedures are considerably reduced.

Vidare liar det visat sig, att de gaser, som erhallas i blandningen, som sadana mojligOra att genomfora kolvatenas efterfoljande klorering genom att i sig sjalva skapa en termisk stabilisering, vilken Sr tillrackligt saker att forhin.dra farliga temperaturhojningar utan att anordningar for kylning utifran behoves, med avseende ph vilka driftsvarigheter och -kostnader redan aro kanda. Furthermore, it has been found that the gases obtained in the mixture as such make it possible to carry out the subsequent chlorination of the hydrocarbons by creating in itself a thermal stabilization, which is sufficient to prevent dangerous temperature rises without the need for external cooling devices. , with regard to ph which operating durations and costs are already aro kanda.

A andra sidan inses Mt de fordelar, som aro forknippade med oxidationsklorering grund av de enklare forhallandena sarskilt med avseende ph termisk kontroll, elasticitet i reaktionsforloppets styrning, hoga utbyten till f5ljd av franvaro av icke onskade hi- och forbranningsreaktioner. Bland de atskilliga vagarna for oxidationskloreringens genomforande her enligt uppfinningen anvants antingen en reaktor bestaende av tva sektioner eller tva separata reaktorer, sasom Sr sehematiskt antytt i den medfoljande ritningen, som icke shall begransa uppfinningen. Beak-torn arbetar ph foljande sat: I den nedre sektionen A, som innehaller en katalysator enligt Deacons forslag tillfores genom ett inlopp 1 en blandning av klorvate °eh syre eller annan syre innehallande gas i molforhallan.de HCl/02 mellan 20:1 och 4:1 och foretradesvis mellan 12:1 och 6:1 i pa forhand upphettat tillstand, som Sr beroende pa det anvanda molforhallandet HCl/02, dvs. vid en sadan temperatur att det varm.e, som utvecklats under den foretradesvis under adiabatiska forhallanden genomforda reaktionen Sr tillrackligt hog att bringa temperaturen i ugnen till ett onskat temperaturvarde, som foretradesvis ligger mellan 350 och 550° C. On the other hand, the advantages associated with oxidation chlorination due to the simpler conditions, especially with respect to thermal control, elasticity in the control of the reaction process, high yields due to the absence of undesired hi- and combustion reactions, will be appreciated. Among the several vagaries for carrying out the oxidation chlorination here according to the invention, either a reactor consisting of two sections or two separate reactors is used, as Sr seematically indicated in the accompanying drawing, which should not limit the invention. The reactor operates as follows: In the lower section A, which contains a catalyst according to Deacon's proposal, a mixture of hydrochloric acid or other oxygen or other oxygen-containing gas is fed through an inlet into the molar ratio of HCl / O2 between 20: 1 and 4: 1 and preferably between 12: 1 and 6: 1 in a preheated state, which is dependent on the molar ratio HCl / O2 used, i.e. at such a temperature that the heat evolved during the preferably adiabatic conditions to carry out the reaction Sr is sufficiently high to bring the temperature in the oven to a desired temperature value which is preferably between 350 and 550 ° C.

Beroende pa katalysatorns inverkan genomfares reaktionen under en kontakttid, vilken är tillrackligt lang for att astadkomma en syreomvandling uppgaende till Over 80 % och faretradesvis mellan 90 % och 100 %. Depending on the action of the catalyst, the reaction is carried out during a contact time which is sufficiently long to achieve an oxygen conversion of more than 80% and preferably between 90% and 100%.

De gaser, vilka komma fran den forsta zonen i reaktorn och besta av Overskottet av det anvanda klorvatet, klor och reaktionsvatten med en liten halt av oreaggerat syre, blandas med det kolvate, som skall kloreras, och som intra.der genom inloppet 2 och, darest liven. klor anvandes, med denna gas i onskade — —3 mangder och reaktionsblandningen infores in i den andra zonen B av reaktorn, dar ocksa, beroende pa temperaturen, som varierar melIan 150 och 750° C och den typ av kolvatet som skall kloreras, en kontakttid är uppratt- som hr tillraekligt lang for att forena alit klor i befintlig form vid reaktorns utlopp J. Ehuru temperaturer upp till 750° C kunde nyttiggoras i praktiken, är det mojligt att h5ja temperaturen till 900° C. I zonen A kan kataIysatorn anyandas i form av en fast eller vatskeformig badd, av vilka former den senare är att foredraga pa grund av sin fordelaktiga egenskap av termisk homogenitet. I detta fall bdr emellertid ett avskiljarorgan, t. ex. en cyklon vara placerad mellan reaktorns forsta och andra zon sâ att katalysatorpartiklarna joke kunna na zonen B. The gases coming from the first zone of the reactor and consisting of the excess chlorine water used, chlorine and reaction water with a small content of unreacted oxygen are mixed with the hydrocarbon to be chlorinated, which is introduced through the inlet 2 and, darest liven. chlorine is used, with this gas in the desired amounts and the reaction mixture is introduced into the second zone B of the reactor, there also, depending on the temperature, which varies between 150 and 750 ° C and the type of carbonate to be chlorinated, a contact time is established - which is long enough to combine all chlorine in its existing form at the reactor outlet J. Although temperatures up to 750 ° C could be utilized in practice, it is possible to raise the temperature to 900 ° C. In zone A, the catalyst can be in the form of a solid or liquid bath, the forms of which the latter is to be preferred because of its advantageous property of thermal homogeneity. In this case, however, a separator means, e.g. a cyclone be placed between the first and second zones of the reactor so that the catalyst particles can joke reach the zone B.

Mellan den forsta och den andra zonen av reaktorn kan ocksa ett gaskylningssystem vara installerat fOr att den for kloreringen lampliga lagre temperaturen skall kunna erhallas. A gas cooling system can also be installed between the first and the second zone of the reactor in order to be able to obtain the lower storage temperature suitable for chlorination.

For att fa tillfredsstallande utbyten hr dot fOrdelaktigt att efterstrava en intim blandning av de friar zon A kommande reaktionsgaserna med kolvatet och eventuellt klor, vilken blandning foretradesvis utfores medelst en blandare, vilken kan hava formen av en ejektor eller annan likvardig, for andamalet lamplig anordning. Reaktorns zon B kan hallas torn eller lampligast innehalla fyllkroppar, sasom Raschigringar av porslin el. dyl. Annu battre hr kiselhaltig sand eller liknande smakornigt material i form av en svavande badd for att astadkomma en fullgod termisk homogenitet. In order to obtain satisfactory yields, it is advantageous to strive for an intimate mixture of the reaction gases coming from the free zone A with the carbonate and possibly chlorine, which mixture is preferably carried out by means of a mixer, which may be in the form of an ejector or other equivalent device. The reactor's zone B can be tilted towers or, most conveniently, contain filling bodies, such as Raschigringar made of porcelain or the like. dyl. Even better, silicon-containing sand or similar granular material in the form of a floating bath to achieve a good thermal homogeneity.

Eftersom klor, som nar kloreringszonen, hr utspadd med klorvate och mojligheterna till pyrolys medelst anga eller antandning aro sma eller obefintliga t. o. m. i handelse av forekomsten av en dartill tillräckligt hog proportion mellan klor och kolvate, kan framstallningen av klorerade kolvaten drivas till en hogre kloreringsgrad an hittills i en enda omgang. Since chlorine reaching the chlorination zone is diluted with chlorine and the possibilities for pyrolysis by means of ignition or ignition are small or non-existent even in the presence of a sufficiently high proportion between chlorine and hydrocarbon, the production of chlorinated hydrocarbons can be driven to a higher degree of chlorination. so far in a single round.

Nagra exempel, vilka givetvis joke skola begransa uppfinningens skyddsomfang, pa reaktioner enligt uppfinningen skola ytterligare illustrera dess vasen. Some examples, which of course joke should limit the scope of the invention, on reactions according to the invention should further illustrate its vase.

Exempel 1. En reaktor liknande den som schematiskt visats 5. ritningen, inneholl i sin lagre zon A, 22,5 1 av en katalysator som lampade sig att arbeta i en svdvande badd hest& ende av en poros barare av silikonaluminiumoxid utgOrande en sikt med en maskvidd mellan 0,3 och 0,15 mm, pa vilken kopparklorid, kaliumklorid och ceriumklorid placerats i proportioner 10 %, 4 % och 2 %, varvid procenttalen aro baserade pa bararens vikt. Example 1. A reactor similar to that schematically shown in the drawing, contained in its storage zone A, 22.5 liters of a catalyst which was allowed to operate in a floating bath of a porous silicon alumina carrier constituting a screen with a mesh size between 0.3 and 0.15 mm, on which copper chloride, potassium chloride and cerium chloride are placed in proportions of 10%, 4% and 2%, the percentages being based on the weight of the carrier.

Den ovre zonen B inneholl Raschigringar av keramiskt material. The upper zone B contained Raschigrings made of ceramic material.

Vid bottnen av zonen A inmatades klorvate och syre med stromningshastigheter av 13,8 m3/1im. resp. 1,825 m3/tim., medan temperaturen i reaktionszonen halls vid 430°-4° C. At the bottom of zone A, hydrogen chloride and oxygen were fed at flow rates of 13.8 m3 / 1im. resp. 1,825 m3 / h, while maintaining the temperature in the reaction zone at 430 ° -4 ° C.

I reaktorns mittparti infOrdes metan med en stromningshastighet av 1,4 m3/tim och hopblandades genom en dispersionsanordning med fran zonen A kommande reaktionsgaser. Temperaturen i kloreringszonen. B, dit de hopblandade gaserna uppstego, h011s vid 440°470° C genom kylning medelst insprutade stralar saltsyrelOsning. In the middle part of the reactor, methane was introduced at a flow rate of 1.4 m 3 / h and mixed through a dispersion device with reaction gases coming from zone A. The temperature in the chlorination zone. B, where the mixed gases arose, was heated at 440 ° 470 ° C by cooling by means of injected jets of hydrochloric acid solution.

Kontakttiden i zonen B var 5 sekunder. The contact time in zone B was 5 seconds.

Efter kylning och kondensation erholls en blandning av klormetaner med ett nettoutbyte av 96 % med avseende pa. metanet och 95 % med avseende p5. syret och med omvandlingsvarden av 80 % resp. 94 %. After cooling and condensation, a mixture of chloromethanes is obtained with a net yield of 96% with respect to pa. methane and 95% with respect to p5. oxygen and with the conversion value of 80% resp. 94%.

Klormetanblandningens sammansattning med de olika bestandsdelarna i viktsprocent var foljande: CH3C1 6 CH2C12 12 CH C13 41 C C14 41 Det klorvate i overskott, som separerats frau klormetanblandningen, aterfOrdes till zonen A av reaktorn. The composition of the chloromethane mixture with the various constituents by weight was as follows: CH 3 Cl 6 CH 2 Cl 2 12 CH C13 41 C C14 41 The excess chlorine-hydrogen, separated from the chloromethane mixture, was returned to zone A of the reactor.

Exempel 2. En reaktor, liknande den som beskrevs i foregaende exempel, inneholl i sin lagre zon A 22,5 liter av en katalysator, som lampade sig att arbeta med svavande badd och bestod av keramiskt material med en yi, area av 20 m2/g i bitstorlekar, som utgjorde en sikt med en maskvidd mellan 0,3 och. 0,15 mm, pa vilken kopparklorid, kaliumklorid och ceriumklorid placerades I proportioner av 15 %, 4 % resp. 2 %, varvid procentuppgifterna hanfora sig till bdrarematerialet, medan i den ovre zonen en svavande sandbadd uppratth011s. I den lagre zonen A infordes klorvate och syre med stromningshastigheter av 15 m3/tim. resp. 1,825 m3/tim., medan temperaturen i den lagre zonen var 400°410° C. Example 2. A reactor, similar to that described in the previous example, contained in its storage zone A 22.5 liters of a catalyst, which was suitable for working with floating baths and consisted of ceramic material with a yi, area of 20 m2 / give bit sizes, which constituted a sieve with a mesh size between 0.3 and. 0.15 mm, on which copper chloride, potassium chloride and cerium chloride were placed in proportions of 15%, 4% resp. 2%, the percentage data being fed to the carrier material, while in the upper zone a floating sand bath is maintained. In the lower zone A, hydrogen chloride and oxygen were introduced at flow rates of 15 m3 / h. resp. 1,825 m3 / h, while the temperature in the lower zone was 400 ° 410 ° C.

Efter kylning till 300°-320° C genom utsprutade stralar av vattenlosning av klorvate hlandades reaktionsgaserna med metan och klor, som inmatades med stromningshastigheter av 2 m3/tim. resp. 3,650 m3/tim., och hela blandningen infordes i den andra reaktionszonen B, varvid temperaturen h011s vid 475°-480° C under en kontakttid av 9 sekunder. After cooling to 300 ° -320 ° C by sprayed jets of aqueous hydrogen chloride solution, the reaction gases were charged with methane and chlorine, which were fed at flow rates of 2 m 3 / h. resp. 3,650 m 3 / h, and the whole mixture was introduced into the second reaction zone B, the temperature h011s at 475 ° -480 ° C for a contact time of 9 seconds.

Efter kylning och kondensation genomfordes separationen av klorvate Iran klormetanerna. After cooling and condensation, the separation of chlorine-water Iran chloromethanes was carried out.

Del atervunna klorvatet aterfordes till zonen A. Klormetanerna erhollos med ett utbyte av 97 % med avseende pa inford metan och Erred ett omvandlingsvarde av 90-94 %. Part of the recovered chlorine water was returned to zone A. The chloromethanes were recovered with a yield of 97% with respect to imported methane and Erred a conversion value of 90-94%.

Syreomvandlingen skedde i storleksordningen 99 %. Genom rektifiering av reaktionsblandningen erh011os de olika klormetanerna 4— — i foljande sammansattning med bestandsdelarna uttryckta i viktprocent: CH3C1 0,3 CH2C12 2,9 CH C13 9,8 C C14 87,0 Exempel 3. Till en reaktor, vilken i sin lag-re zon A inneholl 22,5 1 av en katalysator av det slag, som beskrevs i exempel 2, och i den iivre zonen B en svavande sandbadd, inmatades i den lagre zonen A klorvate och syre med stromningshastigheter av 13,8 m3/tina. resp. 1,825 maitim., medan temperaturen i zonen hölls vid 430-440° C. The oxygen conversion took place in the order of 99%. By rectifying the reaction mixture, the various chloromethanes are obtained in the following composition with the constituents expressed as a percentage by weight: CH 3 Cl 0.3 CH 2 Cl 2 2.9 CH C13 9.8 C C14 87.0 Example 3 zone A contained 22.5 l of a catalyst of the type described in Example 2, and in the upper zone B a floating sand bath, chlorine water and oxygen with flow rates of 13.8 m 3 / thina were fed into the lower zone A. resp. 1,825 ° C, while the temperature in the zone was maintained at 430-440 ° C.

Efter kylning till 300° C blandades reaktionsgasen med etan, som inleddes med en stromningshastighet av 1,525 ms/tim. och hela blandningen fOrdes in i den andra reaktionszonen B, som hölls vid 360°-380° C. liontakttiden var 7 sekunder. After cooling to 300 ° C, the reaction gas was mixed with ethane, which was started at a flow rate of 1.525 ms / h. and the whole mixture was fed into the second reaction zone B, which was kept at 360 ° -380 ° C. The lion beat time was 7 seconds.

Omvandlingen av etanet uppgick till 87 % med ett nettoutbyte av 96,5 % klorderivat. The conversion of ethane amounted to 87% with a net yield of 96.5% chlorine derivative.

Claims

Patent claim:

Substituted for substituting chlorination of the hydrocarbons, in particular methane and ethane to obtain chlorinated hydrocarbons, in particular chloromethanes and chloroethanes, characterized in that the carbonate is reacted directly with a gas mixture obtained by oxidizing chlorine water carried out through a catalytic bath with a amount of oxygen 1 deficit with respect to pa. the chlorine water for such a long time that the oxygen conversion rises to at least 80% and preferably between 90 and 100%.

HU according to claim 1, characterized in that the reaction is carried out in the presence of WHOA chlorine from outside.

3. according to claim 1, characterized in that the oxidation of the chlorvate is carried out by causing the chlorvate and the oxygen or the oxygen-containing gases to pass through a catalytic bath, a molar ratio being maintained between the chlorvate and the oxygen amounting to between 20: 1 and 4: 1, preferably between 12: 1 and 6: 1 at a temperature between 350 and 550 ° C and a contact time sufficient to achieve an oxygen conversion Over 80% and preferably Over 95%.

4. A kit according to claims 1-3, characterized in that the gas mixture obtained by the oxidation of the chlorine water and essentially containing chlorine, chlorine water and water is caused to contact the carbonate at a temperature which varies between 150 and 900 ° C. and during a contact time between 10 and 0.1 sec.

5. Provided for the preparation of chlorinated carbon monoxide according to claims 1-4, characterized in that the chlorine hydrogen obtained by the substituting halogenation is returned directly to the oxidation step. Request Publications: U.S. Patent Nos. 2,870,22 5.