Патент USA US2403735код для вставки
July 9, 1946. R. B.IMAS_ON ETAL ' 2,403,735 HYDROGEN CHLORIDE MANUFACTURE‘ Filed Nov. 26, 1942 43 '45 25- ; #7 t ?vpnocanzaorv 87-258" \ v ' 27— 25a 2 . __-_-> I 3 I I7 7 (P5 75 ' 1.9 $722: AM 6 a 2/ :37 ‘ ‘ sr'ozn oz‘ PRESSURE c‘: plum I /9 ——' REACTOR 4/ ' /7 —-> ® 7 c Yl. IALDER '~ . 4 ) 23v I ‘ _ a 59. ' \ O1 raecm/v-Aroz 2,403,735 Patented July 9, 1946 ‘UNITED STATES PATENT OFFICE 2,403,735 HYDROGEN CHLORIDE MANUFACTURE Ralph Burgess Mason and Jerry A. Pierce, Baton Rouge, La., assignors to Standard Oil Develop ment Company, a corporation of Delaware Application November 26, 1942, Serial No. 467,054 (01. 23-156) s 4 Claims. 1 2 It is an object, therefore, of the present in This invention concerns a continuous method vention to prepare hydrogen chloride in a high for the preparation of hydrogen chloride. The ' invention relates in particular to the preparation degree of purity fromvchlorine and gaseous hy drocarbons in the absence of air. and thus to pre oi! hydrogen chloride by the intercombustion of pare hydrogen chloride suitable for immediate use in reactions requiring this compound in the chlorine and the readily available gaseous hydro °carbons such as are present in oil ?eld and pe anhydrous condition troleum refinery locations. The preparation of hydrogen chloride by the ' Another object of the invention is to prepare I hydrogen chloride in a high degreeof purity and reaction of chlorine and methane in the pres free from contamination with organic halides by . ence of air has been known for some time. .When 10p the intercombustion of chlorine and easily avail air is used to assist or support the combustion of chlorine and methane the product is diluted with a large amount of inert gases. These dilu ents have to be removed for the more important commercial uses of hydrogen chloride. Absorp tion of the reaction product in water toremove the diluents is disadvantageous since the scrub bing system has to be constructed of relatively costly materials in order’ to be resistant to cor; able normally gaseous hydrocarbons.’ A further object of the invention is to prepare hydrogen chloride in a high degree of concen 15 tration without employing water to effect con centration of the hydrogen chloride. Other objects will be apparent from the, fol lowing description and illustrations of the inven tion: According to. the invention, chlorine and any rosion; Furthermore, absorption of hydrogen 20 one, or a mixture, of the normally gaseous hy chloride in water is particularly undesirable when drocarbons are separately heated to a tempera the anhydrous compound has to be prepared, such ture between 1200° F. and 2000“ F., and then as is necessary in the preparation of organic hal brought together in a con?ning space or chamber. ides .by the reaction of hydrogen chloride with The gases ignite spontaneously and a continuous unsaturated compounds; and when hydrogen 25 flame is established at the point of physical un > chloride is employed as a catalyst promoter with ion, giving as the products of combustion essen aluminum chloride in reactions, such as isomer tially hydrogen chloride and carbon. The re ization, alkylation, polymerization, and the like. action products are held for a short period of To effect the intercombustion of chloride and 30 time within a con?ning space or chamber at gaseous hydrocarbons burners modeled after about the reaction temperature. During this pe those commonly employed to prepare hydrogen riod any small amounts of chloro-hydrocarbons chloride by the combustion of hydrogen and chlo formed in the combustion are decomposed to hy rine were found to be unsatisfactory. With such drogen chloride, carbon, and hydrogen. ‘ The hy burners substantial quantities of chloro-hydro drogen chloride is then conducted from the com 35 carbons and other by-products were formed and bustion chamber and collected as conveniently Im- in general intercombustion was incomplete. suitable. The carbon formed in the reaction is proved, but still unsatisfactory, functioning was partly deposited on the burner and such parts of obtained with a burner in which the reactants the preheating equipment as occur in the reac were mixed by impingement. Satisfactory inter tiorr chamber. Anotherportion of the carbon is combustion was found to occur only when the entrained in the product gases and removed from reactants were preheated ‘and then brought to-5 gether at the burner preferably, by impingement, the reactor. and then the combustion products held at tem peratures between 1200° F. and 2000° F. for a short period of time. Under these conditions it was conditions, especially when e?ected at substan tially atmospheric pressure, proceeded smoothly iv ' . apparatus to preheat the reactants to the desired temperature. The chlorine and hydrocarbon gas, found that the normally gaseous hydrocarbons and chlorine reacted to form hydrogen chloride and carbon almost quantitatively. Furthermore, it was found that the intercombustion under such " In the preferred form of the invention the heat of reaction of the chlorine and hydrocarbon gas is utilized by means of suitable heat exchange for example, natural gas comprising essentially‘ methane,’ are heated 50 and without hazard provided feed rates and 're- 1 action conditions were adjusted to prevent sub separately’ by passing " through tubular (Fcoil type heat exchangers dis. posed in the space where the intercombustion occurs. The tubes or coils terminate at a com mon point where the reaction occurs with evolu tion of large amounts of heat. Since carbon is stantial quantities of unreacted chlorine being 55 formed as a product of the reaction and is de present in the exit gases. 2,408,785 Q 3 V , posited to some extent within the reactor and on the elements or the heat exchanger, it be 4 be heated to the same or difierent temperatures, should be in the approximate range or comes necessary at regular intervals to discon- - v but 1200*’ F. to 2000s F. The chlorine and the gaseous tinue processing and to remove the deposited hydrocarbon react to form hydrogen chloride and carbon. Consequently, it is desirable to operate carbon. The reaction products pass upward in the reactor l, and are withdrawn through line 25 and cooler 21 to the carbon recovery system 29. pairs 01’ reactors so that one may be in operation while the other is being cleaned of carbon, and continuous production or hydrogen chloride thus maintained. A common recovery system for the While part of the carbon is withdrawn in susa hydrogen chloride may be used for each pair of 10 pended form along with the gaseous hydrogen chloride, another portion of the carbon is de reactors. posited on the walls of the reactor i and on the The method commonly employed for collecting coils ‘I and I1, and may be eventually removed as the hydrogen chloride is to pass the reactant will be described hereinafter. A suitable carbon gases through a series of ?lters or a Cottrell pre system comprises several bag filters in cipitator for removing the entrained carbon and 15 recovery series followed by a Cottrell precipitator. How then to a compression system for liquefying the ever, other known types 01’ recovery equipment hydrogen chloride. The carbon collected in the may be used. reaction zone, in addition to that entrained in The ?ltered reactionproducts are compressed the hydrogen chloride, may be recovered from the reaction system by the use of scrapers, and 20 in compressor 3! to a su?icient pressure to liquefy the hydrogen chloride which is passed to collection 01' the carbon black made in a hopper a storage drum or pressure cylinder 33 from below the burner equipment after the reaction which non-condensible gases ‘ are vented through has been terminated and the equipment cooled. line 5. . Carbon still adhering onto the burner equipment As mentioned previously,‘ some of the carbon can be removed by subsequently burning in air 25 produced in the reaction deposits within the re and utilized as an auxiliary source of heat ior actor. When this carbon deposit is sumcient to preheating reactants or for other purposes, if so interfere with the reaction in any way, such as desired. However, the reaction of-chlorine with by causing an excessive pressure drop through hydrocarbon gases is so highly exothermic that the reactor. or retarding the rate of heat ex more than sumcient heat is ordinarily available 30 change between products and reactants, ?ow oi’ in the combustion zone for preheating the re reactants is terminated in the system described actants. In fact, in some cases coolers may be while a. ?ow of reactants is started in a similar required to prevent overheating of the reactor. parallel reactor system. The same product re An important feature‘ of the invention is the particular manner in which the chlorine and the 85 covery system may be used for both reactors. Part of the carbon may be removed from tE-Je gaseous hydrocarbons are brought into contact oil-stream reactor by tapping the equipment with a hammer 31, thus dislodging most oi.’ the carbon adhering to the sides 01' the reactor and from 50 as to effect their mutual combustion at the point of physical union in a con?ned space in the absence of other gaseous materials. Many types of apparatus may be devised as embodi 40 ments of the inventio . some portions of the coils ‘I and IT. This carbon is allowed to drop into a hopper 39 at the bottom of- the reactor from which it may be recovered. Scrapers may also be used to remove carbon from the reactor and heat exchangers. In case the ' As an illustration of the invention and em bodiment thereof the following description and attached drawing are presented: , carbon is to be recovered by scrapers, it will be most convenient to construct the heat ex In the drawing, numeral I indicates a con fining chamber such as. a tower or elongated changers of straight tubes rather than coil~type vessel in which the reaction takes ‘place. The hydrocarbon gas enters through line 3 contain elements. Some carbon will remain in the re actor system, and must be removed by combus ing valve 5 and passes into coil ‘I disposed in reactor I wherein the gases are preheated to the 50 tion with air which is admitted through line 4|. Torch gas may be admitted with the air if nec desired temperature. If it is desired to heat the essary to reach combustion temperatures. Prod hydrocarbon to a lower temperature than results ucts of combustion may be removed through line from passing it through the entire length oi.’ coil 1, 43, and valve 45 by closing valve 41 in line 25. valve 5 may be closed and the hydrocarbon passed through line 9 and valve II, and thus through only a part of coil 1'. By adjusting valves 5 and II, part of the hydrocarbon can be passed through the entire length of the coil, and part through only a fraction of the length of the coil so that temperatures of varying degrees can be obtained. The chlorine is fed through line l3 and valve I 5, and passes into coil l1 disposed similarly in reactor I, to coil 1. As in the case of the hydrocarbon gas, the temperature to which the chlorine is preheated may be regulated by passing all or part of it through line I! and valve 2!. The materials of which coils 1 and I‘! are constructed must be capable oi’ withstanding cor rosive atmospheres at high temperatures, for ex ample, in the range of 1200" F. to 2000° F.. Quartz is a suitable material for these tubes. The coils 1 and I1 terminate in a burner 23 in - which the nozzles are arranged in such a manner as to impinge the two gas streams on to each With the equipment of the type thus described 55 the following results were obtained: Approx. reactor temp., "F _____ _., ............ ._ 1,450 Hours of run ___________ _ . l 700 2,000 1 l 92 92 106 Chlorine feed, parts/min ______________________ _ . 800 850 900 60 Wt. percent excess chlorine (above theoretical)__ Wt. percent excess methane (above theoretical). 2 0 0 4 5 0 Chlorine in exist gas, parts/min _______________ __ Theoretical H01 prod, parts/min_ ._ 0 825 4. 4 840 0 925 Actual HCl prod, parts/min __ ._. 798 823 882 98 0. 5 95 0 Methane feed, parts/min. . _______ .. Percent hydrogen chloride produced (based on chlorine feed) _________________ __' ____________ __ Percent chlorine unreacted ___________________ __ 1 ' 97 O 65 These data indicate that at elevated tempera tures methane and chlorine react to' form hydro gen chloride and carbon almost quantitatively. The extent of the reaction is shown to be ap proximately the same in the temperature range 70 1450° F'. to 2000° F. The carbon black recovered from the reactor, as well as from the ?lters and pfrecipitator, is of a suitable grade for a variety 11888. 0 other. ‘The chlorine and the hydrocarbon may 75 It should be obvious that the disclosure is cap~ able of some variation within the scope of the 5 . inventive concept as set iorth in the previous de scription, and that the invention should‘not be considered limited by the foregoing speci?c em bodiments described for purposes merely of illus- _ tration. The invention on the other hand is to be determined by the following claims. What is claimed is: _ l. A process for preparing hydrogen chloride by the reaction of chlorine with a normally gaseous hydrocarbon which consists in heating sepa - rately chlorine and a normally gaseous hydro carbon by the heat generated by their reaction, bringing said heated gases in separate conduits together to a common point. burning the two 6 gases at the point 01 contact. one supporting the combustion of the other. and recovering the hy drogen chloride thus formed. 2. A process for preparing hydrogen chloride according to claim 1, in which the normally gaseous hydrocarbon is a petroleum ?eld gas. a 3. A process for preparing hydrogen chloride according to claim 1, in which the normally gas eous hydrocarbon ‘is a petroleum re?nery gas. 4. A process for preparing hydrogenchloride according to claim 1, in which the normally gas eous hydrocarbon is methane. ‘ ‘ RALPH BURGESS MASON. JERRY A. PIERCE.