UNITED STATES PATENT OFFICE. FRED BEDFORD 4ND ED. WILLIAMS,.OF SLEAFORD, ENGLAND, ASSIGNORS TO GEDFORD GAS PROCESS COMPANY LIMITED, OF LONDON, ENGLAND. cA'r’A‘LYTIc SYNTHESIS or . 989,755. Speci?cation of Letters Patent. Patented Apr. 18, 1911. No Drawing. Original application flu-led February 25; 1910, Serial No. 546,016. Divided and this applica tion ?led December 19, 1910. ‘Serial No. 598,228.

To all whom it may concern: ’ cooling. of (the gases to a degree sutlicient Be it known that we, FRED Bnor‘ono and only to liquefy them with a view to the sepa CHARLES EDWARD' \VILLIAMB, subjects of ‘the ration of certain of the constituents. But King of Great Britain and Ireland, and none of these processes have been so far com 5 residents of Sleaford, in the county of Lin mercially successful. coln, England, have invented certain new The object of this invention is to provide a 60 and useful Improvements in and Connected ; process by which the sulfur impurlt'i'es may with the Catalytic Synthesis of Methane, of be effectually removedv and at the same time which the following is a speci?cation. the cheapest of the commercial gases of the 1O This invention relates to an im roved type of Mond gas andDu?' gas and the‘ like process for‘ the catalytic synthesis 0 meth may be commercially treated for the produc 65 ane or” a mixture of 'methane with, other C/ti0n of methane, without there being any gases and is the complement of the invention need to modify their process ofemanufacture. set out-in speci?cation to our corpending In carrying out this process the mixture 15 application‘ Serial No. 546,016. of gases (which should be ?rst-freed from The value of ordinary gas is due to carbon dioxid) is cooled to the degree neces 70 the large percentage of methane contained sary in order to get the sulfur impurities therein, and attempts have been ‘made to into a solid form having little or no vapor produce methane synthetically from carbon ‘tension, the passing off as a gas oxide ‘by the action of hydrogen .in the pres and being collected while the carbon mo ence of ?nely divided nickel, they function noxid, , and methane will be liquid 75 of the latter being simply catalytic. The or solid. On allowing this latter mixture to reactions which-take ‘place may be repre evaporate carbon monoxid and nitrogen dis sented‘ by the equations :— til o? ?rst and are effectually separated from 25 the sulfur impurities. After this distilla- . tion process a certain quantity of the carbon 80 monoxid obtained is mixed with the hydro: This catalytic reaction proceeds smoothly gen so that the hydrogen and carbonmonoxid provided the reacting gases are pure, and are in the required proportions and this mix 30 provided also that hydrogen is present in ture is passed over nickel in-the known ‘man su?icient quantity as demanded by the above ner. There should always be an excess of equations. If, however, the reacting gases ‘hydrogen over the theoretical quantity in contain certain substances -— hereinafter order to prevent local heating .of the metal. termed impurities-such as sulfureted hy-C The amount of this excess depends on va 35 .'drogen,.carbon disul?d, mercaptan and sul rious circumstances, , such as‘the speed at fur compounds in; general, even if only'in which the gaseous mixture is passed over 90 very minute quantities, the nickel very soon the metal, and if nitrogen is present this acts - loses its activity. In order, therefore, to as a di'luent'a-ndO assists in preventin local preserve the activity of the nickel, it is essen heating, and a smaller excessof hy rogen ~40 tial'that the impurities invariably present in may be used than would otherwise be neces- . . commercial gases be carefully removed-be sar . . _ , 95 fore the latter are allowed‘ to come in contact ‘ 'lzo illustrate one mode of carrying out the {with the catalytic nickel. Various processes invention, suppose it be requlred to prepare have been proposed for the removal of the‘ methane synthetically-from, a Mond gas of '45 impurities. Again'all commercial gases ob the .following approximate compos1t1on:—, .tained by gasif'ying coal and containing hydrogen 28 per cent, carbon monoxid 11" I00 hydro en and carbon monoxid are de?cient per CGIlt+_, carbon dioxid 16 per cent., meth ‘ .injhy rogen. .Variousmethods have been ane 2 per cent., nitrogen 43 per cent. 'The proposed for the removal of the sulfur im carbon dioxid is ?rst removed in any known 50 ,.pur1ties, and for-obtaining carbon .‘lOIlOXld manner, for example, by absorption 'in a‘ and hydrogen in the proper relative quanti ’ solution of sodium carbonate, such removal 10 5 ties, either by varying ~the mode of manu being desirable toyplrevent the clogging of , facture of the gases or by adding hydrogen. the apparatus by ti e carbon dioxl . The Some'of these methods have depended on the residual mixture ispassed through a cool 2 989,756

ing apparatus adapted to cool it to a tem __it is present or not during the catalytic re perature of about ~190° C. -A cooling ap~ action. paratus of the well~known type used in the Having noW described our invention what fractionable abstraction method of obtain we claim as new and desire to secure by ing oxygen from the air may be, employed Letters Patent is:-—--' ’ 40 for this purpose. After this cooling proc 1. A process for the catalytic synthesis of ess the hydrogen passes off as a gas carry methane from a ‘commercial gas containing ing with it small quantities only of carbon hydrogen ‘and carbon monoxid comprising monoxid and nitrogen but ‘leaving behind cooling the commercial gas- to such a de~ , 10 it the bulk of these gases with the methane gree that ytheimpurities separate out in the 45 and all the sulfur impurities in the solid solid form possessing little or no vapor form that were present in the commercial tension, separating the puri?ed gas into its ' gas. The hydrogen may be collected in a constituents, mixing the carbon monoxid suitable tank or holder while the mixture thus obtained with hydrogen, and passing 15 which is left behind in the cooling apparatus the mixture into contact with a heated is evaporated so that the carbon monoxid catalytic substance for the purpose‘ set forth. 50 ' and nitrogen distil oil’ ?rst, and these may 2. A process for theic‘atalytic synthesis of be separated by known'means, for example, by absorption of the carbon monoxid by methane from a commercial gas containing 20 hydrogen and‘ carbon monoxid comprising means of cuprous chlorid solution from cooling the commercial gas to such a degree '55 which carbon monoxid'may be again ob that the impurities separate out in the'solid tained by‘ evaporation. ‘In this Way the form possessing little or no vapor tension, puri?ed gas is separated into its constituents separating the puri?ed gas into its con: and a certain quantity of‘ the carbon mo 25 stituents, mixing the ‘carbon monoxid thus noxid thus obtained is mixed with the hy-_ obtained with hydrogen in the required 60 drogen so that. these two gases are present quantity and passing the mixture into con in the required quantities, and the miature, tact with a heated catalytic substance for entirely freed from the impurities which the purpose set forth. _ were present in the commercial gas, is passed In testimony wherdo?'we a?ix our signa over heated and ?nely divided nickel in turesin presence of two wit-ne'sses._ order that it may be converted into methane. ' FRED - BEDFORD. It is to be noted that nitrogen is not'an im~ CHAS. ED. WILLIAMS, purity in the sense hereinbefore referred to, lVitnesses: - and it is immaterial, .so far as the catalytic W. WARREN Tmoos, 35 activity of the nickel is concerned, whether P. A. OUTHWAITE.