HRP921113A2

HRP921113A2 - Hydrochlorination catalytic system and a process for the production of vinyl chloride by the acetylene and hydro chloride reaction

Info

Publication number: HRP921113A2
Application number: HR921113A
Authority: HR
Inventors: Michel Strebelle; Andre Devos
Original assignee: Solvay
Priority date: 1991-06-20
Filing date: 1992-10-23
Publication date: 1994-12-31
Also published as: HRP921113B1

Description

Prikazani izum se odnosi na jedan tekući katalitički sustav hidrokloriranja na bazi jednog spoja metala iz skupine VIII i na postupak za proizvodnju vinilklorida hidrokloriranjem acetilena u prisustvu tog katalitičkog sustava. The presented invention relates to a liquid catalytic hydrochlorination system based on a group VIII metal compound and to a process for the production of vinyl chloride by hydrochlorination of acetylene in the presence of this catalytic system.

Proizvodnja vinilklorida reagiranjem acetilena i vodik klorida klasično se odvija u plinovitoj fazi, u reaktoru sa nepokretnim slojem, u prisustvu čvrstog heterogenog katalizatora na bazi klorida žive na podlozi. Prvenstveno zbog toksičnosti, postoji povećano zanimanje za katalitičke sustave bez spojeva žive. Razvijeni su razni katalizatori koji trebaju zamijeniti postojeće katalizatore u postupku sa plinovitom fazom. Tako, na primjer, japanska patentna prijava 52/136104, koja je u fazi ispitivanja, opisuje postupak hidrokloriranja acetilena u plinovitoj fazi u prisustvu nepokretnog sloja katalizatora koji se sastoji od halogenida plemenitih metala postavljenih na aktivni ugljen. Do danas je, međutim, vijek trajanja alternativnih katalizatora namijenjenih za postupke sa plinovitom fazom znatno kraći u odnosu na katalizatore na bazi spojeva žive. The production of vinyl chloride by reacting acetylene and hydrogen chloride classically takes place in the gaseous phase, in a reactor with a fixed bed, in the presence of a solid heterogeneous catalyst based on mercuric chloride on a substrate. Primarily due to toxicity, there is increased interest in mercury-free catalytic systems. Various catalysts have been developed to replace existing catalysts in the gas phase process. Thus, for example, Japanese patent application 52/136104, which is under examination, describes the process of hydrochlorination of acetylene in the gaseous phase in the presence of a fixed catalyst bed consisting of noble metal halides placed on activated carbon. To date, however, the service life of alternative catalysts intended for gas-phase processes is significantly shorter than that of catalysts based on mercury compounds.

U literaturi postoje, između ostalog, neki primjeri hidrokloriranja acetilena u prisustvu tekuće katalitičke sredine. U njemačkom patentu br. 709.000 opisan je postupak za pripremu halogenida vinila dovođenjem u dodir na povišenoj temperaturi acetilena sa otopinom soli halogenohidrata u organskim bazama koje sačinjavaju uobičajeni katalizator. Kao organske baze predviđeni su alifatički, aromatički ili heterociklički amini i njihove mješavine. U primjeru 1, vinilklorid se dobiva dispergiranjem vodik klorida i acetilena u mješavini koja sadrži 350 volumenskih dijelova piridina, 350 volumenskih dijelova dietilamina i 100 masenih dijelova klorida žive, održavanoj na 220-225ºC. Rusko autorsko uvjerenje SU-237116 opisuje primjenu vodene otopine kiseline koja sadrži 46% mas. bakar klorida i 14 do 16% mas. klorhidrata metil, dimetil ili trietilamina. U japanskoj patentnoj prijavi 52/136103, koja nije ispitivana, prikazan je postupak za pripremu vinilklorida reagiranjem acetilena vodik kloridom u prisustvu katalizatora pripremljenog suspendiranjem u vodi ili u nekom organskom otapalu jednog binarnog sustava biranog između klorida zlata, klorida platine i klorida paladija, eventualno modificiranog kloridom nekog prelaznog metala promjenljive valencije. U patentnoj prijavi EP-A-0340416 objavljen je jedan postupak za pripremu vinilklorida reagiranjem acetilena vodik kloridom u prisustvu jednog spoja paladija kao katalizatora u otopini koju sačinjava jedan alifatični ili cikloalifatični amid, na temperaturi višoj od temperature okolne sredine. Mada omogućava postizanje veće produktivnosti, ovaj postupak ipak ima nekih važnih nedostataka: očigledno je da će se u uvjetima reakcije tekući katalitički sustav postupno razlagati, pri čemu će se oblikovati crnkasti proizvodi, slični ugljenu. In the literature, there are, among other things, some examples of hydrochlorination of acetylene in the presence of a liquid catalytic medium. In the German patent no. 709,000 describes a procedure for the preparation of vinyl halides by bringing acetylene into contact at an elevated temperature with a solution of halogenohydrate salts in organic bases that make up the usual catalyst. Aliphatic, aromatic or heterocyclic amines and their mixtures are envisaged as organic bases. In Example 1, vinyl chloride is prepared by dispersing hydrogen chloride and acetylene in a mixture containing 350 parts by volume of pyridine, 350 parts by volume of diethylamine and 100 parts by weight of mercuric chloride, maintained at 220-225ºC. Russian author's certificate SU-237116 describes the application of an aqueous acid solution containing 46% by weight. copper chloride and 14 to 16% wt. methyl, dimethyl or triethylamine hydrochloride. In Japanese patent application 52/136103, which was not examined, a process for the preparation of vinyl chloride by reacting acetylene with hydrogen chloride in the presence of a catalyst prepared by suspending in water or in an organic solvent a binary system selected from gold chloride, platinum chloride and palladium chloride, possibly modified, is presented with the chloride of a transition metal of variable valency. In patent application EP-A-0340416, a process for the preparation of vinyl chloride by reacting acetylene with hydrogen chloride in the presence of a palladium compound as a catalyst in a solution consisting of an aliphatic or cycloaliphatic amide, at a temperature higher than the ambient temperature, is published. Although it makes it possible to achieve higher productivity, this process still has some important drawbacks: it is obvious that under the reaction conditions, the liquid catalytic system will gradually decompose, whereby black products, similar to coal, will be formed.

Zbog toga je cilj izuma ostvariti stabilan katalitički sustav hidrokloriranja bez živinih spojeva. Izum isto tako ima za cilj dati postupak za sintezu vinilklorida hidrokloriranjem acetilena u prisustvu takvog jednog tekućeg katalitičkog sustava koji je posebno aktivan, koji se neće razlagati u uvjetima reakcije i koji omogućava, između ostalog, dobivanje vinilklorida sa velikom selektivnošću i sa jakim smanjenjem nusproizvoda koje treba ukloniti. Za razliku od sustava na bazi živinih spojeva, katalitički sustav prema izumu ima dodatnu prednost da je izbjegnuto isparavanje metalnih soli u instalaciji. Therefore, the goal of the invention is to realize a stable catalytic hydrochlorination system without mercury compounds. The invention also aims to provide a process for the synthesis of vinyl chloride by hydrochlorination of acetylene in the presence of such a liquid catalytic system which is particularly active, which will not decompose under the reaction conditions and which enables, among other things, obtaining vinyl chloride with high selectivity and with a strong reduction of by-products that should be removed. In contrast to systems based on mercury compounds, the catalytic system according to the invention has the additional advantage of avoiding the evaporation of metal salts in the installation.

Izum se odnosi na jedan tekući katalitički sustav hidrokloriranja, posebno hidrokloriranja acetilena. Ovaj katalitički sustav sadrži najmanje jedan spoj metala iz skupine VIII i jedan klorhidrat masnog amina čija je točka topljenja viša ili jednaka 25ºC i jedno organsko otapalo. Kao masni amini dolaze u obzir svi amini ili mješavine amina koji sadrže povećan broj atoma ugljika, na primjer više od 8 atoma ugljika, koji imaju molekularnu strukturu malo ili nimalo razgranatu. Pogodni su amini koji sadrže 10 do 20 atoma ugljika. Ovakve molekularne strukture, malo ili nimalo razgranate, omogućuju laku kristalizaciju klorhidrata oblikovanog pri reagiranju masnog amina vodik kloridom i imaju točke topljenja više od klorhidrata u svojim spojevima. Amini koji odgovaraju navedenoj definiciji masnih amina su, na primjer, decilamin, undecilamin, dodecilamin, 3-metildodecilamin. The invention relates to a liquid catalytic system for hydrochlorination, especially hydrochlorination of acetylene. This catalytic system contains at least one group VIII metal compound and one fatty amine hydrochloride with a melting point greater than or equal to 25ºC and one organic solvent. Fatty amines include all amines or mixtures of amines which contain an increased number of carbon atoms, for example more than 8 carbon atoms, which have a molecular structure that is little or not at all branched. Amines containing 10 to 20 carbon atoms are suitable. Such molecular structures, with little or no branching, enable easy crystallization of the hydrochloride formed during the reaction of a fatty amine with hydrogen chloride and have higher melting points than the hydrochloride in their compounds. Amines corresponding to the above definition of fatty amines are, for example, decylamine, undecylamine, dodecylamine, 3-methyldodecylamine.

Dobri se rezultati dobivaju sustavom koji sadrži klorhidrat dodecilamina. Good results are obtained with a system containing dodecylamine hydrochloride.

Spojevi metala skupine VIII koji se koriste u katalitičkom sustavu prema ovom izumu obično se biraju između spojeva željeza, kobalta, nikla, rutenija, rodija, paladija, osmija, iridija, platine ili njihovih mješavina. Pogodni su kloridi ovih metala VIII skupine, ali se mogu koristiti i svi drugi spojevi koji se mogu prevesti u kloride u prisustvu vodik klorida u tijeku pripreme katalitičkog sustava. Preporučljivo je da se spoj metala skupine VIII koji se koristi kod ovog izuma bira između spoja platine i spoja paladija, kao što je klorid platine (II) ili klorid paladija (II), klorid platine ili klorid paladija alkalnih ili zemnoalkalnih metala, na primjer Na2(PtCl4), Na2(PdCl4), K2(PtCl4), K2(PdCl4), Li2(PtCl4), Li2PdCl4, zatim (NH4)2(PtCl4) i (NH4)2(PdCl4), heksakloroplatinske kiseline i njenih soli, na primjer Na2PtCl6, K2PtCl6, Li2PtCl6, spojevi paladija u kojima paladij ima jednu valenciju više, kao što su Na2PdCl6, K2PdCl6, Li2PdCl6, itd. Također se mogu koristiti kompleksni spojevi metala skupine VIII u kojima je metal sa valencijom 0, kao što su kompleksni spojevi Pt(Pø3)2, Pd(Pø3)2, (Pø3)Pt(CO), itd. Također se mogu koristiti mješavine spojeva metala skupine VIII. The Group VIII metal compounds used in the catalytic system of the present invention are usually selected from compounds of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, or mixtures thereof. The chlorides of these Group VIII metals are suitable, but all other compounds that can be converted into chlorides in the presence of hydrogen chloride during the preparation of the catalytic system can also be used. It is recommended that the Group VIII metal compound used in the present invention is selected from a platinum compound and a palladium compound, such as platinum(II) chloride or palladium(II) chloride, platinum chloride or palladium chloride of alkali or alkaline earth metals, for example Na2 (PtCl4), Na2(PdCl4), K2(PtCl4), K2(PdCl4), Li2(PtCl4), Li2PdCl4, then (NH4)2(PtCl4) and (NH4)2(PdCl4), hexachloroplatinic acid and its salts, on example Na2PtCl6, K2PtCl6, Li2PtCl6, palladium compounds in which the palladium has one more valence, such as Na2PdCl6, K2PdCl6, Li2PdCl6, etc. Complex compounds of group VIII metals in which the metal is 0 valence can also be used, such as complex compounds Pt(Pø3)2, Pd(Pø3)2, (Pø3)Pt(CO), etc. Mixtures of group VIII metal compounds can also be used.

Posebno pogodni spojevi metala skupine VIII su klorid platine (II) i klorid paladija (II). Posebno pogodan spoj metala skupine VIII je klorid paladija (II). Particularly suitable compounds of group VIII metals are platinum (II) chloride and palladium (II) chloride. A particularly suitable compound of group VIII metals is palladium (II) chloride.

Izbor vrste organskog otapala koji će se koristiti u postupku prema izumu, uvjetovan je, prije svega, potrebom da bude inertan u odnosu na materije koje reagiraju u uvjetima reakcije, da se može miješati sa klorhidratom masnog amina na temperaturi reakcije i koji se može topiti na temperaturi nižoj od njegove točke topljenja. Pored toga, iz sigurnosnih razloga, poželjno je da organsko otapalo bude malo isparljivo. Izbor organskog otapala također je uvjetovan sposobnošću apsorbiranja acetilena. Otapala koja zadovoljavaju razne naprijed navedene kriterije biraju se između alifatičnih, cikloalifatičnih i aromatičnih ugljikovodika i njihovih mješavina, na primjer parafina sa 7 do 15 atoma ugljika, kao i alkilbenzoli, posebno ksilol, propilbenzoli, butilbenzoli, metiletilbenzoli. Iz ekonomskih razloga, pogodno je da se kao otapala koriste komercijalni proizvodi koji predstavljaju mješavine alifatičnih ugljikovodika, kao što je otapalo ISOPAR, tvrtke Esso, ili otapalo SHELLSOL K, tvrtke Shell, ili aromatične mješavine kao što je otapalo SOLVESSO, tvrtke Esso, ili otapalo SHELLSOL AB, tvrtke Shell. The choice of the type of organic solvent to be used in the process according to the invention is conditioned, first of all, by the need to be inert in relation to the substances that react under the reaction conditions, to be able to mix with the fatty amine hydrochloride at the reaction temperature, and to be able to melt at at a temperature lower than its melting point. In addition, for safety reasons, it is preferable that the organic solvent be slightly volatile. The choice of organic solvent is also determined by the ability to absorb acetylene. Solvents that meet the various aforementioned criteria are chosen from aliphatic, cycloaliphatic and aromatic hydrocarbons and their mixtures, for example paraffins with 7 to 15 carbon atoms, as well as alkylbenzenes, especially xylene, propylbenzenes, butylbenzenes, methylethylbenzenes. For economic reasons, it is convenient to use as solvents commercial products that are mixtures of aliphatic hydrocarbons, such as ISOPAR solvent, from Esso, or SHELLSOL K solvent, from Shell, or aromatic mixtures such as SOLVESSO solvent, from Esso, or solvent SHELLSOL AB, a Shell company.

Otapala koja su dala dobre rezultate su otapala od zasićenih alifata, kao što je otapalo SHELLSOL K koje se sastoji od naftnih derivata čija je točka ključanja između oko 190ºC i oko 250ºC. Solvents that have given good results are saturated aliphatic solvents, such as SHELLSOL K solvent which consists of petroleum derivatives with a boiling point between about 190ºC and about 250ºC.

Druga otapala koja se mogu primijeniti na bazi raznih, naprijed iznesenih kriterija, su neki spojevi teških halogena kao što su halogenoalkani, halogenobenzoli i drugi derivati halogenih sa aromatičnim spojevima. Other solvents that can be used on the basis of the various criteria presented above are some compounds of heavy halogens such as halogenoalkanes, halogenobenzenes and other halogen derivatives with aromatic compounds.

Katalitički sustav koji je posebno pogodan sadrži klorhidrat dodecilamina, klorid paladija (II) i jedno alifatsko otapalo kao što je otapalo SHELLSOL K. Takav katalitički sustav ima veliko katalitičko djelovanje i selektivnost vinilklorida koja prelazi 99%. Pored toga, taj se sustav ne razlaže tijekom vremena. A particularly suitable catalytic system contains dodecylamine hydrochloride, palladium(II) chloride and an aliphatic solvent such as SHELLSOL K solvent. Such a catalytic system has a high catalytic activity and vinyl chloride selectivity exceeding 99%. In addition, this system does not decompose over time.

Odnos masa između otapala i klorhidrata masnog amina je obično veći ili jednak oko 0,1. Pogodno je da taj odnos bude veći ili jednak oko 0,5. U posebno pogodnim uvjetima je veći ili jednak oko 0,8. Taj je odnos obično manji ili jednak oko 20. Poželjno je da je manji ili jednak oko 10. U posebno pogodnim uvjetima, on je manji ili jednak oko 8. The mass ratio between solvent and fatty amine hydrochloride is usually greater than or equal to about 0.1. It is convenient for this ratio to be greater than or equal to about 0.5. In particularly favorable conditions, it is greater than or equal to about 0.8. This ratio is usually less than or equal to about 20. Preferably it is less than or equal to about 10. Under particularly favorable conditions, it is less than or equal to about 8.

Sadržaj spojeva metala skupine VIII u katalitičkom sustavu, izrađen u milimolima po litri otopine katalitičkog sustava, obično je veći ili jednak oko 1 mmol/l, poželjno veći ili jednak oko 10 mmol/l. Sadržaj spoja metala skupine VIII u katalitičkom sustavu obično je manji ili jednak oko 200 mmol/l, poželjno manji ili jednak 100 mmol/l. Mada nije neophodno, ipak je pogodno da svi spojevi metala VIII grupe sadržana u katalitičkom sustavu budu u otopljenom obliku. Obično se katalitički sustav priprema otapanjem, ili dispergiranjem, potrebne količine spojevi metala skupine VIII u nekom masnom aminu ili mješavini masnog amina i organskog otapala, zagrijavanjem te otopine do temperature više od temperature topljenja klorhidrata masnog amina, zatim zasićivanjem te otopine vodik kloridom dok se ne izazove oblikovanje klorhidrata masnog amina. Isto je tako moguće da se prvo zasiti masni amin, ili mješavina masnog amina i organskog otapala vodik kloridom dok se ne oblikuje klorhidrat masnog amina, poslije čega se unosi spoj metala skupine VIII u klorhidrat masnog amina, ili u mješavinu ovoga sa organskim otapalom. Obično je količina spoja metala skupine VIII koja se koristi ona koja se u katalitičkom sustavu u cjelini javlja u otopljenom obliku. Također se može staviti spoj metala skupine VIII u takvoj količini, odnosno takve vrste, da se u katalitičkom sustavu nalazi najviše jedan mali dio tog spoja u obliku dispergiranog krutog materijala, a da to ne utječe negativno na izum. The content of group VIII metal compounds in the catalytic system, expressed in millimoles per liter of the catalytic system solution, is usually greater than or equal to about 1 mmol/l, preferably greater than or equal to about 10 mmol/l. The content of the group VIII metal compound in the catalytic system is usually less than or equal to about 200 mmol/l, preferably less than or equal to 100 mmol/l. Although it is not necessary, it is nevertheless convenient that all compounds of Group VIII metals contained in the catalytic system are in dissolved form. Usually, the catalytic system is prepared by dissolving, or dispersing, the required amount of Group VIII metal compounds in a fatty amine or a mixture of a fatty amine and an organic solvent, heating that solution to a temperature higher than the melting point of the fatty amine hydrochloride, then saturating that solution with hydrogen chloride until causes the formation of fatty amine hydrochloride. It is also possible to first saturate a fatty amine, or a mixture of a fatty amine and an organic solvent with hydrogen chloride until the fatty amine hydrochloride is formed, after which a Group VIII metal compound is introduced into the fatty amine hydrochloride, or into a mixture of this with an organic solvent. Usually, the amount of Group VIII metal compound used is that which occurs in dissolved form in the catalytic system as a whole. It is also possible to add a group VIII metal compound in such a quantity, i.e. of such a type, that there is at most one small part of this compound in the form of a dispersed solid material in the catalytic system, without this having a negative effect on the invention.

Izum se također odnosi i na jedan postupak za proizvodnju vinilklorida hidrokloriranjem acetilena u prisustvu jednog tekućeg katalitičkog sustava koji sadrži najmanje jedan spoj metala iz skupine VIII i jednog klorhidrata masnog amina čija je točka topljenja viša ili jednaka 25ºC i jedno organsko otapalo. Priroda i odnosi komponenata katalitičkog sustava koji se primjenjuju u postupku prema izumu su oni koji su naprijed definirani. The invention also relates to a process for the production of vinyl chloride by hydrochlorination of acetylene in the presence of a liquid catalytic system containing at least one group VIII metal compound and one fatty amine hydrochloride with a melting point of 25ºC or higher and one organic solvent. The nature and relationships of the components of the catalytic system used in the process according to the invention are those defined above.

Postupak prema izumu odvija se na temperaturi do oko 200ºC. Na višoj temperaturi katalitički sustav ima tendenciju brzog razlaganja. Obično je temperatura reakcije ona na kojoj je klorhidrat masnog amina otopljen. Preporučljiva temperatura reakcije, koja pruža najbolji kompromis između produktivnosti, stupnja korisnog djelovanja i stabilnosti katalitičke sredine je viša ili jednaka oko 80ºC. Najbolji se rezultati dobivaju na temperaturama višim ili jednakim oko 120ºC. Poželjno je da temperatura reakcije ne bude viša od oko 180ºC. Temperatura reakcije niža ili jednaka oko 170ºC je posebno pogodna. Postupak prema izumu se obično izvodi na atmosferskom pritisku, ili na pritisku malo višem, koji je u skladu sa sigurnosnim pravilima o rukovanju acetilenom, tj. ne prelazi preko 1,5 bar. The process according to the invention takes place at a temperature of up to about 200ºC. At a higher temperature, the catalytic system tends to break down quickly. Usually the reaction temperature is that at which the fatty amine hydrochloride is dissolved. The recommended reaction temperature, which provides the best compromise between productivity, degree of beneficial action and stability of the catalytic medium, is higher or equal to about 80ºC. The best results are obtained at temperatures higher than or equal to around 120ºC. It is preferable that the reaction temperature is not higher than about 180ºC. A reaction temperature lower than or equal to around 170ºC is particularly suitable. The process according to the invention is usually carried out at atmospheric pressure, or at a slightly higher pressure, which is in accordance with the safety rules for handling acetylene, i.e. does not exceed 1.5 bar.

Postupak za proizvodnju vinilklorida hidrokloriranjem acetilena prema izumu, ostvaruje se dovođenjem u dodir u nekom pogodnom reaktoru plinovitih reaktanata, acetilena i vodik klorida, sa katalitičkim sustavom. Postupak prema izumu se može ostvariti klasičnim putem u svakom uređaju koji omogućava izmjenu tipa plin-tekućina, kao što je stupac sa platoima ili stupac upušten u slojeve. Drugi način za izvođenje postupka koji omogućava dobru izmjenu materije između tekuće i plinovite faze sastoji se u korištenju jednog protustrujnog reaktora, eventualno sa vlažnim slojevima, kod koga se tekući katalitički sustav slijeva preko slojeva u smjeru suprotnom od plinovite struje materija koje reagiraju. The process for the production of vinyl chloride by hydrochlorination of acetylene according to the invention is achieved by bringing the gaseous reactants, acetylene and hydrogen chloride, into contact with the catalytic system in a suitable reactor. The process according to the invention can be carried out in a classical way in any device that enables gas-liquid exchange, such as a column with plateaus or a column immersed in layers. Another way to perform the procedure that enables a good exchange of matter between the liquid and gaseous phases consists in the use of a countercurrent reactor, possibly with wet layers, where the liquid catalytic system flows over the layers in the direction opposite to the gaseous stream of reacting substances.

U postupku prema izumu, molarni odnos između vodik klorida i acetilena koji se unose u reaktor, obično je veći od ili jednak oko 0,5. Pogodno je da je taj odnos veći ili jednak oko 0,8. Obično je taj molarni odnos veći ili jednak oko 3. Dobri se rezultati dobivaju sa molarnim odnosom vodik klorida i acetilena unijetih u reaktor, koji je manji ili jednak oko 1,5. Acetilen i vodik klorid mogu se miješati u reaktoru, ali je pogodnije da se pomiješaju prije unošenja u reaktor. In the process according to the invention, the molar ratio between hydrogen chloride and acetylene fed to the reactor is usually greater than or equal to about 0.5. It is convenient that this ratio is greater than or equal to about 0.8. Usually, this molar ratio is greater than or equal to about 3. Good results are obtained with a molar ratio of hydrogen chloride to acetylene introduced into the reactor, which is less than or equal to about 1.5. Acetylene and hydrogen chloride can be mixed in the reactor, but it is more convenient to mix them before entering the reactor.

U cilju povećanja količine acetilena otopljenog u tekućoj fazi, moguće je da se uvede postupak u kome se acetilen uvodi u reaktor u plinovitom obliku, gdje će reagirati sa vodik kloridom u tekućoj fazi u vidu klorhidrata, pri čemu se klorhidrat masnog amina iz katalitičkog sustava regenerira dovođenjem u dodir masnog amina i vodik klorida u jednoj zatvorenoj posudi izvan reaktora. In order to increase the amount of acetylene dissolved in the liquid phase, it is possible to introduce a procedure in which acetylene is introduced into the reactor in gaseous form, where it will react with hydrogen chloride in the liquid phase in the form of hydrochloride, whereby the fatty amine hydrochloride from the catalytic system is regenerated by bringing the fatty amine and hydrogen chloride into contact in a closed vessel outside the reactor.

Izum je ilustriran sljedećim primjerima. Primjeri 1 do 5 izvedeni su prema izumu. Primjeri 6(C) do 8(C) izvedeni su radi usporedbe. The invention is illustrated by the following examples. Examples 1 to 5 were performed according to the invention. Examples 6(C) through 8(C) are performed for comparison.

Primjeri 1 do 3 Examples 1 to 3

Katalitički sustav je pripremljen reagiranjem dodecilamina, klorida paladija i otapala SHELLSOL K. The catalytic system was prepared by reacting dodecylamine, palladium chloride and SHELLSOL K solvent.

Otapalo SHELLSOL K, koje prodaje tvrtka Shell, sastoji se od mješavine ugljikovodika, u suštini alifatičnih. Otapalo koje se koristi u ovim primjerima ima donju točku ključanja od 193ºC i gornju točku ključanja od 245ºC. SHELLSOL K solvent, sold by Shell, consists of a mixture of hydrocarbons, essentially aliphatic. The solvent used in these examples has a lower boiling point of 193ºC and an upper boiling point of 245ºC.

Dodecilamin se prvo miješa sa različitim količinama otapala SHELLSOL K, poslije čega se 4 g klorida paladija (II), odnosno 22,6 mmol, unosi, uz miješanje, u jednu litru otopine. Katalitički sustav se potom priprema za zasićivanje otopine plinovitim vodik kloridom. Dodecylamine is first mixed with different amounts of SHELLSOL K solvent, after which 4 g of palladium chloride (II), i.e. 22.6 mmol, is introduced, with stirring, into one liter of solution. The catalytic system is then prepared to saturate the solution with gaseous hydrogen chloride.

Reakcija između acetilena i vodik klorida ostvaruje se na sljedeći način: The reaction between acetylene and hydrogen chloride is realized as follows:

Reaktor od pireks stakla, unutarnjeg volumena od 45 ml, izveden sa dvostrukim zidovima između kojih cirkulira ulje za prenošenje topline, i naprava za unošenje reaktanata, koja se sastoji od jednog nastavka od kaljenog stakla, namijenjenog za osiguranje disperzije plina u tekućoj sredini, napunjen je sa 30 ml otopine koja se sastojala od dodecilamina, klorida paladija (II) i otapala SHELLSOL K. A reactor made of pyrex glass, with an internal volume of 45 ml, made with double walls between which oil circulates to transfer heat, and a device for introducing reactants, which consists of one extension made of tempered glass, intended to ensure the dispersion of the gas in the liquid medium, is filled with 30 ml of a solution consisting of dodecylamine, palladium (II) chloride and SHELLSOL K solvent.

Otapalo je zagrijano na 150ºC, pa je plinovita struja, koja se sastojala od mješavine vodik klorida i acetilena, sa molarnim odnosom HCl/C2H2 jednakim 1,17, uvedena u reaktor. Prema ispitivanjima, vrijeme zadržavanja plina u reaktoru, to jest odnos između volumena reaktora i volumenskog prinosa reaktanata na temperaturi reakcije je 4,9 s. Plinoviti proizvodi koji su izlazili iz reaktora bili su kromatografski analizirani u plinovitoj fazi. Jedini primijećeni proizvodi reakcije su bili vinilklorid (VC)i 1-kloropren (1CPr). Rezultati su prikazani u Tabeli I. Količina vinilklorida izrađena je u gramima na sat po litri katalitičkog sustava. Selektivnost je definirana kao molarni odnos između proizvedenog vinilklorida (VC) i zbroja [VC + (2 x 1CPr)]. The solvent was heated to 150ºC, and the gaseous stream, which consisted of a mixture of hydrogen chloride and acetylene, with a molar ratio of HCl/C2H2 equal to 1.17, was introduced into the reactor. According to tests, the gas retention time in the reactor, that is, the relationship between the reactor volume and the volume yield of reactants at the reaction temperature, is 4.9 s. The gaseous products leaving the reactor were chromatographically analyzed in the gaseous phase. The only observed reaction products were vinyl chloride (VC) and 1-chloroprene (1CPr). The results are shown in Table I. The amount of vinyl chloride produced is in grams per hour per liter of catalytic system. The selectivity is defined as the molar ratio between the produced vinyl chloride (VC) and the sum of [VC + (2 x 1CPr)].

Tablica I Table I

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Primjeri 4 i 5 Examples 4 and 5

Pripremana su dva katalitička sustava na isti način kao i u primjeru 1 sa promjenljivim količinama dodecilamina i otapala SHELLSOL K, ali je klorid paladija zamijenjen sa 15 mmol/l klorida platine (II). Two catalytic systems were prepared in the same way as in example 1 with variable amounts of dodecylamine and solvent SHELLSOL K, but the palladium chloride was replaced by 15 mmol/l platinum (II) chloride.

Hidrokloriranje acetilena vršeno je pod istim uvjetima kao u primjerima 1 do 3. Hydrochlorination of acetylene was carried out under the same conditions as in examples 1 to 3.

Rezultati su prikazani u Tabeli II. The results are shown in Table II.

Tablica II Table II

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Primjer 6(C) Example 6(C)

Katalitički sustav je pripremljen na isti način kao i u primjeru 1, ali bez organskog otapala u otopini. Katalitički sustav dobiven zasićenjem otopine je čvrst, čak i na 150ºC, tako da je nemoguće ostvariti hidrokloriranje acetilena u upotrijebljenom reaktoru. The catalytic system was prepared in the same way as in example 1, but without the organic solvent in the solution. The catalytic system obtained by saturating the solution is solid, even at 150ºC, so it is impossible to achieve hydrochlorination of acetylene in the used reactor.

Primjer 7(C) Example 7(C)

Katalitički sustav pripremljen je na isti način kao i u primjeru 1, ali bez dodecilamina u otopini. The catalytic system was prepared in the same way as in example 1, but without dodecylamine in the solution.

Hidrokloriranje acetilena izvedeno je pod istim uvjetima kao i kod prethodnih primjera. Rezultati su prikazani u Tabeli III. Hydrochlorination of acetylene was carried out under the same conditions as in the previous examples. The results are presented in Table III.

Primjer 8(C) Example 8(C)

Katalitički sustav je pripremljen na isti način kao i u primjeru 1, samo je dodecilamin zamijenjen dimetilformamidom. The catalytic system was prepared in the same way as in example 1, only dodecylamine was replaced by dimethylformamide.

Tablica III Table III

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Claims

1. Catalytic hydrochlorination system, indicated by the fact that it includes at least one group VIII metal compound, one fatty amine hydrochloride whose melting point is higher than or equal to 25ºC and one organic solvent selected from aliphatic, cycloaliphatic and aromatic hydrocarbons and their mixtures.

2. Catalytic system according to claim 1, characterized in that the amine hydrochloride contains 10 to 20 carbon atoms.

3. Catalytic system according to claim 1 or 2, characterized in that the group VIII metal compound is chosen between a palladium compound and a platinum compound.

4. Catalytic system according to one of the claims from 1 to 3, characterized in that the volume ratio between the solvent and the fatty amine hydrochloride changes from about 0.1 to about 20, and the proportion of the group VIII metal compound, made in millimoles per liter of the amine hydrochloride it is greater than or equal to about 1 mmol/l, and less than or equal to about 200 mmol/l.

5. Process for the production of vinyl chloride by reacting acetylene with hydrogen chloride in the presence of a liquid catalytic system, characterized by the fact that this system includes at least one group VIII metal compound and one fatty amine hydrochloride whose melting point is higher than or equal to 25ºC and one organic solvent selected from aliphatic , cycloaliphatic and aromatic hydrocarbons and their mixtures.

6. The method according to claim 5, characterized in that the fatty amine hydrochloride contains 10 to 20 carbon atoms.

7. The method according to claim 5 or 6, characterized in that the group VIII metal compound is chosen between a palladium compound and a platinum compound.

8. The method according to one of claims 5 to 7, characterized in that the volume ratio between the solvent and the fatty amine hydrochloride changes from about 0.1 to about 20, and that the group VIII metal content of the catalytic system expressed in mmol/l ranges from from about 1 mmol/l to about 200 mmol/l.

9. The process according to one of claims 5 to 8, characterized in that the reaction is carried out at a temperature of about 80ºC to about 180ºC.

10. The method according to one of claims 5 to 9, characterized in that hydrogen chloride and acetylene are used in a molar ratio of about 0.5 to about 3.