US2258839A - Motor fuel production - Google Patents

Description

Oct. 14,- 1941. H. v`. ATwELL MOTOR FUEL PRODUCTION Filed oct. so. 1937 Patented Oct, 14,! 1941 UNITED STATES PATENT OFFICE f i 2,253,839 f l Moron rum. rnonuc'rxox umm v. mwen, wma mms, N. Y., mimora goa-c. mation of Delaware Appuunn october 3o, 1937, serai No. 171,919 o 4 claims. (ci: 19e-s) This invention relates to the production of normally liquid hydrocarbons from a gaseous mixture consisting essentially of carbon monoxide and hydrogen. More particularly, the invention relates to the production of normally liquid hydrocarbons from carbon monoxide and hydrogen and the treatment thereof to produce a gasoline of high anti-knock value.

mm, Inc., New

tion of the resulting products to' form aromatics,

alkylation reactions between. gaseous constitu- The normally liquid hydrocarbons produced by the reaction of carbon monoxide and hydrogen ordinarily include substantial proportions of hydrocarbons in the gasoline boiling range. However, the fraction corresponding to the vgasoline boiling'range recovered from the synthesis reaction products is very low in anti-knock value and therefore Agenerally unsuitable as such; as, The treatment of this niagasoline motor fuel. terial by application'of elevated conditions of temperature and pressure to improve its antiknock value results in the production of large quantities of gas and accompanying low recovery of useful products. The improvement inI antiknock value by this means may not justify the losses involved in the process. This may be caused by the relative absence of aromatic constituents in the reaction products of carbonr monoxide and hydrogen, this condition being alsoresppnsible, in part at least, for the initial low anti-knock value of the motor fuel fraction.

It is an object of the' present invention to provide a means for treating normally liquid prod-`v ucts obtained by the reaction of carbon monoxide and hydrogen to produce therefrom a gasoline motor fuel of high anti-knock value, with maximum recovery of useful products.

The invention contemplates the separation of a gasoline fraction from the reaction products of ents and between gaseous and normallyiiquid constituents, etc., although the invention is not to be limited by such theoretical considerations. The reaction products are treated to separate therefrom a gasoline fraction and a normally gaseous fraction predominating in C3 and C4 hydrocarbons which are in part at least admixed with the normally liquid fraction undergoing conversion treatment as described. Cz hydrocarbons and lighter products may be recovered and converted to a carbon monoxide-hydrogen mixture by suitable4 catalytic oxidation. The accompanying drawing is a diagrammatic view in elevation of apparatus suitable for carrying out the present invention. The invention will be further described with reference to the specific embodiment illustrated by the drawing, but it is to'be understood that the invention is not limited thereby but is capable of other embodiments which may be beyond the'physical limitations of the apparatus illustrated.

In the embodiment of the invention as illustrated in the drawing the carbon monoxide-hydrogen mixture is produced by the catalytic oxidation of hydrocarbon gases, particularly methane and C: hydrocarbons, it being understood that the invention is not limited to the treatment of hydrocarbons produced by the reaction of a mixture of carbon monoxide and hydrogen obtained in any particular manner. Referring to the drawing, a stream of gaseous hydrocarbons predominatingv in methane and Cz hydrocarbons provided with valve 2. A second pipe line 3 pro'- carbon monoxide and hydrogen and the subjection of thegasoline fraction to elevated conditions of temperature and pressure in the presence v of a substantial proportion of convertible vnormally gaseous hydrocarbons produced in ther process, having three and four carbon atoms per molecule, hereafter referred to as Cs and C4 hytor fuel of high anti-knock value. tions of temperature and pressure preferably are vided vwith valve 4 is provided for the introduc-l tion of'oxygen. Lines I and. 3 join to form line 5, and the mixture of oxygen and hydrocarbon gases suitable to produce the desired mixture of carbon monoxide and hydrogen is produced by suitable manipulations of valves 2 and 4. Line 5 connects with a catalytic oxidation chamber 6 which may consist of al plurality of tubes arranged in parallel between suitable headers and containing a mixture of 90 parts nickel oxide and 10 parts of a promoter such as thoria on a suitsufliciently drastic to effect cracking of normally liquid constituents, and the reactions which result in the production of high anti-knock motor fuel probably are, in addition to cracking, polymerization of normally gaseous constituents, dehydrogenation of parailinic constituents, cyclization of aliphatic constituents and dehydrogena- 55 temperature byl a suitable insulation of the reacbe in the range of 900 to 1500* F. Ordinarily able carrier such as fire clay or magnesia. The temperature for maximum oxidation will vary with the catalyst employed but ordinarily should atmospheric pressure is employed. The oxidation reaction is only slightly exothermic so that it. may be necessary to maintain the reaction,

tion chamber. Preferably, however, the catalyst is suitably maintained in tubes 8 through which sage of heating or cooling uids as necessary on the outside of the tubes to maintain the desired reaction temperature and toI obtain maximum contact of the catalyst and gaseous mixture the reaction mixture is passed to permit the pasthrough the subdivision of the gaseous stream in the plurality of tubes 8 of the oxidation chamber. Preheating of the gaseous mixture entering oxidation chamber 6 as desired may be effected by the provision of heater 'I in line 5.

The oxidation reaction products emerge from chamber B by means of line 9 and may be treated to remove undesirable components such as sulphur compounds and to adjust the ratio of carbon monoxide to hydrogen, by means not shown. The oxidation reaction products suitably may pass through a heat exchanger I0 located in line 9 wherein they pass in indirect contact with a hydrocarbon stream produced in the system to effect cooling of the oxidation reaction products and heating of the hydrocarbon stream. If necessary they may be further cooled to the exact temperature required for the succeedingoperation by passage through cooler II, also located in line 9.

After emerging from cooler II the oxidation reaction products, which consist essentially of carbon monoxide and hydrogen in the desired ratio, are passed through a synthesis chamber l2 for the production of hydrocarbons by the reaction of carbon monoxide and hydrogen.

Synthesis chamber I2 suitably consists of a plurality of tubes I3 arranged in parallel between suitable headers and maintained in a fluid bath cross sectional dimension greatly in excess of the other whereby a relatively narrow passageway is .provided in each. The tubes I3 are provided with a suitable catalyst for the conversion of the carbon monoxide and hydrogen to hydrocarbons of greater molecular weight. For example, the catalyst may consist of metallic cobalt deposited on a carrier such as kieselguhr together with a promoter such as thoria. The gases should be maintained at a temperature of approximately 365 to 415 F. at atmospheric pressure for maximum conversion. The reaction is exothermic, and the tubes I3 are immersed in a bath of oil or other suitable fluid which serves. to remove thegexothermic heat of reaction. Means not shoiki are provided. to circulate and cool the bath of oil, etc. to maintain the desired temperature.

The rate of this reaction is relatively low whereby it is necessary to provide a relatively long time of contact to secure complete conversion of the carbon monoxide and hydrogen. This may be done by providing a single large chamber or, preferably, by providing aplurality of chambers with removal of liquids formed from the stream after passage through each chamber. For purposes of illustration the present drawing includes two such chambers, but it is to be understood that any suitable number may be employed without departing from the method of operation illustrated.

The reaction products from synthesis chamber I2 may be withdrawn therefrom through line I4 which connects with a fractionator I5. In fractionator I5 conditions of temperature and pressure may be maintained to effect condensation of normally liquid hydrocarbons and a desired portion of the normally gaseous hydrocarbons. To facilitate fractionation superatmospheric pressure may be maintained in fractionator I5, In this case a compressor I6 is provided in line I4 to force the gases therein into the fractionator I5. Heating means such as a heating coil I1 and cooling means such as cooling coil I8 maybe provided in the bottom and top, respectively, of fractionator I5 to effect the desired separation.

'I'he gases uncondensed in fractionator I5 are withdrawn from the upper portion of fractionator I5 through line I9 provided with control valve 20. Heating means 2l is interposed in line I8 to raise the gaseous mixture in line I9 to the desired reaction temperature, e. g., 365 to 415 F. Be-

yond heating means 2| line I 9 connects with a second synthesis chamber 22 which n ay be identical in construction with synthesis chamber I2 including the same type of catalyst in a plurality of tubes so that no detaileddescription of this chamber will be given. Synthesis chambers I2 and 22 represent the rst and last of a series of such chambers which may exceed two in number, the additional chambers being connected in series between chambers I2 and 22 with provision for removal of liquid products after each chamber in the manner illustrated in connection` with chamber I2.

The reaction products are withdrawn from chamber 22 through line 23 and consist of any unreacted hydrogen and carbon monoxide,` normally liquid hydrocarbons formed in chamber '22, normally gaseous hydrocarbons formed in chamber 22 and normally gaseous hydrocarbons formed in chamber I2 and not removed by Vcondensation in fractionator I5. Line 23 connects with a fractionator 24, and the reaction products from chamber 22 are introduced therein for separation as desired. Superatmospheric pressure may be employed in fractionator 24 to facilitate the desired separation, and in this case a compressor. 25 is provided in line 23 to force the reaction products from line 23 into fractionator 24. Line 26 provided with a pump 21 connects the bottom of fractionator I5 with an intermediate point in fractionator 24 whereby the liquid fraction separated in fractionator I5 is introduced into fractionator 24 for further treatment therein.

In contrast with the conditions obtaining in fractionator I5 .fractionator 24 is maintained under conditions of temperature and pressure suitable to effect separation and collection of a. liquid fraction consisting of those reaction products boiling above the boiling range of the fraction desired for further treatment in the process to produce a high anti-knock motor fuel. For example, fractionator 24 may be operated under conditions, suitable to eiect condensation and 'separation of constituents boiling substantially above 400 F., or the fractionator may be operated to eil'ect the passage overhead of a gaseous and vaporous mixture including an appreciable proportion of constituents boiling above 400 F. In any case, however, the mixture of vapors and gases passing overhead from fractionator 24 should be limited in the amount of material higher boiling than 400 F. whereby a normally liquid condensate produced therefrom contains at most a minor proportion of constituents boiling above the gasoline boiling range. To eiect the desired fractionation of the reaction products introduced into fractionator 24 through lines 23 and 2E, heating means such as heating coil 28 and cooling means such as cooling coil 29 may be provided in the lower and upper portions, respectively, of fractionator 24. The liquid condensate which collects in the bottom of frac- Ationator. 24 maybe withdrawnl therefrom and from the system for further treatment elsewhere through line 30 provided with valve 3l.

The vaporous and gaseous fraction passing i overhead from fractionator 24 is withdrawn therefrom through line 32 provided with control valve 33. Line 32 connects with a fractionator 34 wherein the said gaseous and vaporous fraction is treated to effect the separation and collection therein of a normally liquid fraction desired for further treatment in accordance with the process of the invention. Ordinarily the liquid fraction condensed in fractionator 34 will include substantially all the constituents introtionator 43 are withdrawn overhead therefrom through-line 4B provided with control valve 41. These gases may be withdrawn kfrom the system for use elsewhere, for example, as fuel; or all or a portion thereof may be returned to the process through line 39 as described above b ydiversion through line 43 which is provided with a valve 49 and connects lines 46 and 39.

When fractionator 34 is operated to effect con densation and collectionv of a liquid consisting substantially essentially of the relatively high boiling constituents of the motor fuel fraction, for

' example, those boiling above 300 F., the unconduced therein which are in the motor fuel boiling range and may include normally gaseous hydrocarbons such as C3 and C4 hydrocarbons in substantial proportions. However, if desired, the

liquid condensate separated in fractionator 34 may be limited to liquids in the upper portion of For example, the

the gasolineboiling range. liquid condensate may be limited to exclude substantially all constituents boiling below 300 F. To effect the desired separation heating means such as heating coil 35 and cooling means such as cooling coil 36 may be provided in the bottom and top, respectively, of fractionator 34.

The disposal of the uncondensed fraction from Yfractionator 34 will depend upon Athe conditions of operation of fractionator 34. The uncondensed gases and any accompanying uncondensed vapors are withdrawn from fractionator 34 through line 31 provided with control valve 38. When the conditions of operation of fractionator 34 are controlled to effect inclusion in the liquid fraction of substantially all convertible normally gaseous hydrocarbonssuch as Cs and C4 hydrocarbons the remaining gases taken overhead through line 31 may be withdrawn from the system for use elsewhere, for example, as fuel; or since these vgases consist essentially of methane and C2 hydrocarbons and may include.

unreacted carbon monoxide and hydrogen all or a portion thereof may be diverted from line 31 through line 39 provided with v alve 40. Line 39 connects withline 5 whereby the mixture of hydrocarbon gases and carbon monoxide and hv-A drogen are admixed with the oxygen-hydrocarbon -mixture in line 5 for passage to oxidation chamber 6." Suitable adjustment of the proportions of hydrocarbon gases and oxygen introduced through lines I and 3, respectively, may be efdensed portion withdrawn through line 31 will contain a substantial proportion of the motor fuel product of the process. To provide Separate recovery-of this portion of the motor fuel product a separate fractionator 50 is provided. Fractionator 50 is connected with line 31 by means of line 5| which is provided with a valve 52. Line 5I connects with fractionator 50 at a middle point thereof and with line 4| at a point between valve 42 and line 31. By closing valve 42 and opening valve 52 the overhead product from fractionator 34 passing through line 4l is diverted to fractionator 50. In fractionator 50 conditions of Vtemperature and pressure are maintained to fected by means of .valves 2 and 4 to maintain together with any desired proportion of the C2 hydrocarbons. To effect the desired fractionation heating means such as heating coil 44 and cooling or liquefaction means such as cooling coil 45 may be provided in the bottom and top, respectively,. `of fractionator 43. Gases uncondensed in frac-k effect the separation of that portion of the vapors desired in the motor fuel product. Fractionator 50 may be provided with heating means such as heating coil 53 and cooling means such as cooling coil 54 in the bottom and top, respectively, thereof to effect the desired fractionation. Gasesv uncondensed in fractionator 50 are withdrawn therefrom through line 55 provided with valve 56. Line 55 connects with line 4| between valve 42 and fractionator 43 whereby the latter may be used to effect separation in the manner described above of convertible gaseous hydrocarbons from' the mixture passing through line 55.v The gasoline constituents collected as liquid in the bottom of fractlonator 50 are withdrawn therefrom through'lne 51 provided with a valve 58.

The liquid motor fuel fraction collected in the bottom of fractionator 34 is withdrawn therefrom through line 59 `by means of pump 60 located in line 5 9 for further treatment in-accordance with the process of the invention. Line 59 includes heat .exchanger I0 whereby thegnormally liquid fraction is preheated by heat exchange with the` hot oxidation reaction products from charn-y ber 6. Line 59 connects with the inlet of aheating coil 6| located in a furnace 62. If desired a heat exchanger 63 may be provided in line 59 whereby the material 4passing therethrough is further 'preheated by heat exchange with the hot reaction products passing from coil 6I.' Pref'-,

.erably coil BI is arranged in the furnace with a preheating section Gla, a radiant heating section lband as oaking section @Ic in order to provide the desired application of -heat to the material passing therethrough. In accordance with the present invention normally gaseous hydrocarbons preferably predominating in C: and C4 hydrocarbons and containing substantial proportions of olenic constituents are admixed with the liquid products of the carbon monoxide-hydrogen reaction before or during Vthe heat treatment,

provided in coil 6I. If desired these gaseous hy,-` drocarbons may be admixed with the liquid material passing through line 59 prior to passage through heat exchanger I0. For example, they may be introduced through line 64 'which connects line 59 with a source to be described below. Or'

the gaseous hydrocarbons may be introduced into norm-ally liquid hydrocarbons in line 59.

line 5I just previous to the passage ofthe liquid hydrocarbons through heat exchanger 83. For example. the gaseous hydrocarbons may be' introduced to line 59 through line 55 which connects line 59 with a source to be described below.

If desired the' gaseous hydrocarbons may be` separately preheated before admixture with the For example, gaseous hydrocarbons may be introduced by means of line 89 to the inlet of a separate heating coil 61 located inv a convection section of furnace 62. The preheated normally gaseous hydrocarbons emerge from the outlet of coil 61 through line 68 which connects with line 59 near the inlet of coil 8|. If desired, all or a portion of the preheated gaseous hydrocarbons from line 68 may be diverted through line 89 which connects line 68 with heating coil 8| at a point between preheater section 8 |c and radiant heating section 8|b. Valves 18 and 1I may be provided in lines l88 and 89, respectively, to aord4 the desired distributionof the preheated gaseous hydrocarbons to line 59 or through line 89. In the passage of the mixture of. normally liquid and normally gaseous hydrocarbons through sections Elband Slo of coil 9| they are heated to a temperature sufficient to eiTect conversion to gasoline motor fuel constituents of high antiknock value. They may be heated to a temperature of 950 to 1200" F., for example i050" F., at a pressure of 400 to 3000 pounds per square inch, for example 1000 pounds per square inch, for a time sumcient to effect the desired conversion.

The outlet of'the soaking section tlc which constitutes the outlet of coil 8| connects to line 12 through which the conversion reaction products from coil 9| are withdrawn. Line 12 includes heat exchanger 93`whereby the hot re'- `action -products are partially cooleed by heat exchange with the fresh feed passing through line 59. Partially cooled reaction products may be further cooled by passage through heat exchanger 13 located in line 12 and also, if necessary, by further means such 'as cooler 14 also located in line 12. It is to be understood. however, that the specific means of cooling the hot reaction products shown are merely for purposes of illustration, and other means such as the injection of cooling liquids directly into line 12 may be employed. Line 12 connects with an evaporator 15 which may be operated at the same pressure as maintained'in coil 8| or at a reduced pressure, control valve 18 being provided in line 12 to effect any desired reduction.

In separator 1I the reaction products are separated into a heavy condensate and uncondensed vapors and gases. 'I'he preliminary cooling of the reaction products and the operation of separator 15 are controlled to 'effect condensation and separation of relatively high-boiling liquids.

For example, the material collected in separator 15 may have an initial boiling point of 600 to 650 F. To assist in the desired separation heating'means such as a heating coll 11 may be provided in the lower portion of separator 15.

Suitable baille means may be provided in the may be provided with control valve 8|. Line 88 connects with a fractionator 82 wherein the mixture of gases and vapors is treated to enect sepaupper portion of separator 1l to remove liquidsy entrained in the uncondensed vapors and gases.

Y The condensate collected in the'bottom of separator 15 is withdrawn therefrom through line 18 which is provided with control valve 19. This material may -be used elsewhere, for example. as fuel. y

vapors and gases uncondensed in separator 15 are withdrawn therefrom through line 88 which ration therefrom of normally liquid constituents higher boiling than the desired motor fuel product and undesired for inclusion therein. This liquid condensate collects in the bottom of fractionator 82 and is withdrawn therefrom through line 83 provided with a valve 84. 'I'his material may be subjected to further treatment elsewhere as desired. For example, it may be subjected to elevated conditions of temperature and pressure to convert it to gasoline motor fuel. Heating means such as heating coil 85 may be provided in the lower portion of fractionator 82 to assist in the desired fractionation. Also cooling means such as the introduction of reflux material in the upper portion of fractionator 82 through line 86 may be provided.

The vapors and liquids uncondensed in fractionator 82 are withdrawn therefrom through line 81 which is provided with control valve 88. Line 81 contains a cooler 89 and connects with a collector 98. In cooler 89 the gases and vapors are cooled to effect llquefactlon of constituents desired for inclusion in the motor fuel product of the process. In collector 90 separation of liquids and uncondensed material is effected, the latter being'withdrawn through line 9| provided with control valve 92 and the liquids being withdrawn through line 93 provided wlh control i valve 98. A portion of the liquids in line 93 may be diverted'therefrom forreturnl as reflux to frac' C: and lighter hydrocarbons as well as some C4 V hydrocarbons. 'I'hese gases preferably are treated to eff ct separation therefrom of convertible constituents for further treat-ment in accordance with the process of the invention. For example, all or |a portion thereof may be diverted fromline 9| through line 95 provided with valve 95; or al1 or a portion thereof may be diverted from line 9| through line 91 provided with a valve 98. Line 91 connects with line 5 whereby the gaseous hydrocarbons passing therethrough are admixed with the oxygen-hydrocarbon stream passing through line 5 to oxidation reaction chamber 8. ilSuitable adjustment of the proportions of hydrocarbon gases and oxygen introduced throughlinesli and 3, respectively, may be eilected by meansof valves 2 and 4 to maintain the proper ratio desired in the oxidation reactants.

Line 95 connects with the mid-point of a fractionator 89 wherein temperature and pressure conditions are maintained to effectv separation of a condensate consisting of convertible normally` gaseous hydrocarbons auch as C: and C4 hydrocarbons. If necessary a compressor |88 may be Vprovided in line 95 to transfer the gases smesso' r f 5 from the system for use elsewhere, for example,

as fuel: or all or a portion thereof may be diverted from line |03 through line l|05 provided with valve |06. Line |06 connects line |09 with line '91 whereby the uncondensed gases from fractionator 99 may be passed to admixture with the oxidation reactants in line 6 as described above. v

The condensate which collects in the bottom of fractionator 99 will consist for the most part of normally gaseous convertible hydrocarbons suchv as C: and C4 hydrocarbons and will include subf Y stantial proportions of oleilns-Zormed as a result y of the reactions occurring in coil 6I. This material is withdrawn from fractionator -99 through line |01 providedwith control valve |08. Line 66 which connects with the inlet lof coil 61 and includes heat exchanger 18 connects at its other end with line |01 between fractionator 99 and valve |08. Line 66 is provided with a control valve |09 and a pump H0 whereby, by manipulation of valves |08 and |09, any desired proportion of the condensate. from -fractionator 99 may be diverted through line 06 for passage'through heat exchanger 13 and coil 61 as described above.

Line 64, which connects with line 59, connects at its otherend with line |01 between valve |08 and iractionator 99. Line 64 is provided with a control valve whereby all or a portion of the condensate from fractionator 99 may be admixed with the condensate from fractionator 34, as dev scribed above.

The condensate` from fractionator 99, withdrawn therefrom through line |01, and undesired for passage through line 64 or line 66 may be withdrawn from the system for use elsewhere, for

example, as fresh feed to a thermal or catalytic polymerization process. This material is par--v ticularly vuseful for such a process or for processes involving alkylation reactions sinceit includes substantial proportions of oleiinic` constituents. The decomposition of normally liquid paraillnic l hydrocarbons incidental to the treatment of such Y material in coil 6| promotes the decomposition b of normally gaseous paraiilnic hydrocarbons admixed therewith whereby the resulting reaction as heating coil H3 and cooling means in-the upper portion thereofsuch as cooling coil Ii@ to effect fractionation of the motor fuel productl introduced through line 93 and produce amotor fuel containing the desired proportion of light ends and normally-gaseous constituents. The stabilized gasoline collected in the bottom thereof is withdrawn throughline H5 provided with valve H6 andmay be withdrawn to storage. If desired, this material may'be blended with the motor fuel productwithdrawn from fractionator 50 through line 51 by means oi' line I I1 which is provided with a` suitable control valve H8 and connects line H5 and line 61.

'The operation of stabilizer H2 will 'depend upon the results desired and upon the operation of other parts of the process. Ordinarily, it will be operated to eilfect the production ,or a stabilized motor fuel including the desired proportionA V`V of normally gaseous constituents. However, it

'may be desired to include in the gases passing overheadall normally rvgaseous constituents and even a portion of the lower boiling normallyliquid'constituents of the motor fuel product. Thislatter method lis particularly advantageous when the liquid ied to heating coil 6| includes only the heavier portion of the liquid constituents of the -vapors treated' in fractionator 34 and where it is desired to blend the liquid condensate from stabillzer II2 with the condensate from fractionator 60, which latter condensate will ordinarily maintain an excessive proportion of light ends. l c

It may also be advantageous to introduce into stabilizer I|2 allor a portion` of the condensate from fractionator 60 to eiect the production therein of a stabilized motor fuel. For example,

line l I9 provided with valve |20 may be provided 2.0 to connect line 51 with stabilizer H2 at an intermediate point thereof.

The mixture of gases or gases and vapors produced in stabilizer H2 is withdrawn from the y upper portion thereof through line I2| which is provided with a compressor |22. Line |2| connects with line 66 whereby the gases with accompanying vapors may be preheated in coil 81 and introduced into coil 6| as described above; or all ora. portion of the gases and any accompanying vapors passing through line |2I may be diverted therefrom through line 65 which connects'line |2| with line 59 as described above whereby the gases so diverted are admixed with the liquids passing through line 59. Valves .|22-

and |23' are provided in lines |2 and 65, re-

spectively, to provide the desired distribution to c lines 66 and 59.

The normally gaseous hydrocarbons separated as a condensate in fractionator 43 may be employed in the process in addition to those produced in fractionator 99 or stabilizer H2.. For I example, the condensate from fractionator 43 may be Withdrawn therefrom through line |23 provided with valve |24. Line |23 connects with line 66 between pump |I|0`and valve |09 whereby the normally gaseous hydrocarbons from fractionator 63 may be passed through line 66 and coil 61 as described above. If desired all or a. portion of the normally liquid hydrocarbons may be diverted from line |23 through line'l25 which is provided with a valve |26 and connects: with line 59 between pump 60 and fractionator 34 whereby normally liquid hydrocarbons so divetted are admixed with the condensate withdrawn from fractionator 39 for passage through line 59 to coil 6|.

It is to be'understood that the various iractionators i5, 24, 34, 43, 50, 82,99 and II2 are A provided with suitable gas yand liquid contact meansA such las bubble trays to assist in the desired fractionation. It is to be understood, furthermore, that the functions of the fractonator illustrated may be carrled'out in a lesser-number of fractionators -with the provision of suitable trap-out trays for withdrawal of side streams. However, for simplication in presenting the subject matter the present arrangement is adopted for purposes of illustration.

The present invention provides a method forr the treatment of the reaction products of the4 carbon monoxide-hydrogen reaction to produce therefrom motor fuel of high anti-knock value under conditions of maximum emciency vand maximumrecovery of useful products. TheA invention has been described with reference to A.speclc combinations of steps, but itis to be understood that such reference is for the purpose of illustration only, the invention not being necessarily limited thereto. 'I'his application is a continuation-impart of my prior application Serial No. 119,178, filed January 6, 1937.

I claim:

l. 'Ihe method for converting the normally liquid and normally gaseous hydrocarbon products of the reaction of carbon monoxide and hydrogen which comprises separating from the said reaction products a fraction predominating in normally liquid constituents and including at most a minor proportion of vhydrocarbons boiling above the gasoline boiling range, admixing with said fraction a substantial proportion of normally gaseous hydrocarbons from a source set forth below, subjecting the resulting mixture to elegasoline of high anti-knock value, separating from the resulting conversion products gasoline constituents. a normally gaseous fraction predominating in C: and C; hydrocarbons and a iixed gas fraction predominating 4in hydrocarbons containing less than three carbon atoms per vated conditions of temperature and pressure to eii'ect conversion of normally liquid and normally gaseous constituents thereof to gasoline of high antiknock value, separating from the resulting conversion products gasoline constituents and a normally gaseous fraction predominating in C;

and C4 hydrocarbonspcontrolling the separation of the conversion products to etlect inclusion in said normally gaseous fraction of a substantial proportion of therelatively low-boiling normally liquid constituents of the said conversion products and admixing at least a portion of said gaseous fraction with said mst-mentioned fraction as described.

2. The method of producing motor fuel of high anti-knock value which comprises subjecting normally gaseous hydrocarbons consisting essentially of hydrocarbons containing less than three carbon atoms per molecule tocatalytic oxidation to covert said hydrocarbons substantially to carbon monoxide and hydrogen. passing said car- `bon monoxide and hydrogen over a suitable catalyst and under suitable conditions of temperature and pressure to `effect reaction of said carbon monoxide and'hydrogen to form hydrocarbons heavier than methane and/including normally liquid hydrocarbons, separating from the resulting reaction products a fraction predominating in normally liquid constituents and includ ing at most a minor proportion of` hydrocarbons boiling above the gasoline boilingrange, admixing with'said fraction a substantial proportion of normally gaseous hydrocarbons from a source set forth below, subjecting the resulting mixture to elevated conditions of temperature and pressure to effect conversion of normally liquid and normally gaseous constituents thereof to molecule, admixing at least a portion of said A normally gaseous fraction with the fraction separated from the carbon monoxide-hydrogen reaction products as described, and admixing at least a portion of said nxed gas fraction with said first-'mentioned normally gaseous hydrocarbons for processing therewith. v

3. 'I'he method for converting the normally liquid and normally gaseous hydrocarbon products of the reaction of carbon monoxide and hydrogen which comprises separating from the said reaction products a fraction predominating in normally liquid constituents and including at mosta minor proportion of hydrocarbons boil ing in the upper portion of the 'gasoline boiling range and hydrocarbons boiling above the gasoline boiling range, separating from said reaction products a second fraction predominating in the normally liquid constituents and including at most' a minor proportion of hydrocarbons boilingin the lower portion of the-gasoline boil- .ing.range and hydrocarbons boiling above the gasoline bbiling range, admixing with said second fraction asubstantial proportion of normally gasous hydrocarbons from a sourceset forth below, subjecting the resulting mixture to elevated conditions of temperature and pressure to eifect .conversion of normally liquid and normally gaseous constituents thereof to gasoline of high anti-knock value, separatingI from the resulting conversion products a gasoline fraction deficient in constituents boiling in the lower portion of the gasoline boiling range and a vaporous fraction predominating in C: and `C4 hydrocarbons and hydrocarbons boiling in theflower portion of the gasoline boiling range, suitably blending said last-mentioned gasoline fraction and' said first fraction to produce therefrom a stabilized motor fuel of high anti-knock value and admixing at least a 'portion.of said vaporous'fraction with said second fraction prior to said conversion treatment.-

4. 'Ihe method -inraccordance with claim 2 wherein C: and C4 hydrocarbon constituents of the products of the reaction of carbon monoxide and hydrogen are passed to said thermal con.

' version treatment to eil'ect conversion thereof to gasoline of high anti-knock value.

' HAROLD V.l ATWEIL.

Images