April 11, 1950 J. ?. GRA?A?

E
SYNTHESIS OF HYDROCARBONS
2,503,724
2. Sheets-Sheet
Filed April 16, 1947
April 11, 1950 J. H. GRAHAME 2,503,724
SYNTHESIS OF HYDROCARBONS
2 Sheets-Sheet 2
Filed April 16, 1947

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INVENTOR.
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BY

772AAva 21
Patented Apr. 11, 1950 2,503,724

UNITED STATES PATENT OFFICE

s 2,503,724
SYNTHESIS OF HYDROCARBONs
James E. Grahame, Mount vernon, N. Y., as
signor to Texaco Development Corporation,
New York, N.Y., a corporation of Delaware
Application April 16, 1947, Serial No. 741,867
9 Clams. (C. 260-449.6)
1 2
The present invention is concerned with the hydrogen for the production largely or essen
production of hydrocarbons, oxygenated, hydro tially, of isoparaffins.
carbons, and the like by the catalytic reduction This isoparaffin synthesis process employs ap
of carbon monoxide with hydrogen, and more paratus which is generally equivalent to that
specifically involves the correlated and predeter usually employed in the first mentioned process
mined production and use of inevitable accom and depends upon the action of somewhat dif
panying gaseous products of reaction, to improve ferent catalysts which have a specific selective
and supplement the production of liquid hydro action in promoting the formation of the afore
carbons, particularly those boiling in the motor mentioned isoparaffins. Typical isoparaffin syn
gasoline boiling range. 10 thesis catalysts are a composite alumina-thoria,
In accordance with the present invention, hy catalyst or a zinc oxide-alumina catalyst, which
drogen and carbon monoxide are converted cata are Operable usually under characteristic ele
lytically in a primary reaction zone in which op wated temperatures in the range of about 750
erating conditions are directed for the produc 900' F. or more specifically in the range of about
tion of branched chain aliphatic hydrocarbons 5 785 F. to 840 F. Operating pressure is usually
together with relatively large amounts of by substantial, usually in the range of from 50 to
product carbon dioxide. Normally liquid frac 500 atmospheres, and preferably about 300 to
tions are recovered as a product stream and the 500 atmospheres.
residual gases, such as carbon dioxide and un The present invention, however, is not con
reacted hydrogen, are supplied to a secondary 20 cerned, per se, with the specific catalyst or re
synthesis reaction zone where they are mixed action conditions, and contemplates all equiva
with additional hydrogen and carbon monoxide lent catalysts. actively effective to promote the
and catalytically treated under typical reaction selective formation of isoparaffins when operat
conditions adapted to produce predominantly ing under appropriate reaction conditions.
liquid hydrocarbons largely or essentially of ole 25 The isoparaffin synthesis process normally re
finic character. Gaseous olefins accompanying Sults in the production of relatively large amounts
the reaction product, together with isobutane of by-product carbon dioxide with correspond
and if desired isopentane from the first reaction ing loss of yield of hydrocarbons on the basis of
zone are submitted to alkylation for the produc carbon. Supplied to the system. Substantial for
tion of a high quality motor gasoline fraction. 30
mation of carbon dioxide is moreover accom
Typical processes for the synthesis of hydro plished with a relatively low consumption of
carbons currently proposed, involve passage of a hydrogen.
synthesis gas comprising hydrogen and carbon
monoxide in contact with a synthesis catalyst at În accordance with the present invention prod
elevated temperature and usually at elevated 35 duct gases from the primary reaction zone, par
pressure with recovery of the desired hydrocar ticularly the by-product carbon dioxide and hy
bons from the gasiform reaction products. The drogen, are supplied to the secondary reaction
usual process employs a catalyst comprising a zone, together with the fresh feed synthesis gas
metal of the iron group or ruthenium, together therein reacted, to control the reaction and effect
with small additions of an activator and promoter 40 a desirable consumption of these constituents in
such as Oxides of alkali metal or alkaline earth the formation of additional hydrocarbon product.
metals, titanium, zirconium, thorium, alumina The invention has the valuable advantage of
and many others. Temperatures vary with the permitting the direct production of isoparaffins
specific catalyst selected and are usually about without the disadvantage of excessive loss of feed
400 F. or above in the case of the cobalt catalyst. 45 carbon to carbon dioxide. This follows because
Many advantages, however result from the use of the fact that the excess carbon dioxide will
of an iron catalyst preferably in a condition of SuppreSS formation of carbon dioxide in the cata
fluidization and at temperatures from about 550 lytic Synthesis of olefinic and paraffinic hydro
to 700 F., preferably about 600 F. and under an carbons, as disclosed in the co-pending applica
elevated pressure from 150 to 300 pounds per 50 tion, Serial No. 630,521, filed November 23, 1945
Square inch gauge. The products tend to be ole in the name of Claude W. Watson. Moreover,
finic in character and thus the appropriate frac as further shown in this co-pending application,
tions provide a good motor gasoline fuel. an actual predetermined net consumption of
On the other hand, it is possible to carry out carbon dioxide may be effected in the production
he catalytic reduction of carbon monoxide and 65 of additional hydrocarbons. Reference is made
 2,508,724.
3 4.
to this co-pending application for all details of tion with a stream of suitable lean oil from pipe
the process in question. 2. The downflow of lean oil absorbs C4 hydro
The invention has the further advantage of pro carbons and is ultimately withdrawn as at 29 to
viding a correlated feed of isoparaffins and olefins stripping tower 30 from which the stripped hy
containing four carbon atoms or thereabout, suit drocarbon gases pass overhead as at 3, and the
able for an alkylation charge stock. The normally stripped lean oil is returned to pipe 28 by pump
liquid products of reaction are usually accom 2.
panied by such fractions in quite substantial ex Additional C4 hydrocarbons are recovered from
cess of over the amount which may be used to stabilizer 34 which receives the normally liquid
pressure the motor gasoline fractions; that is, O fraction of pipe 2 aforementioned and delivers
which may be included in the commercial motor the C4 fractions thereof through overhead pipe
gasoline product as a desirable component, con 35. The residue discharged to 36 comprises the
tributing to volatility, and anti-knock properties, higher hydrocarbons and any included normally
and correspondingly swelling the volume produc liquid oxygenated hydrocarbons which may be
tion. The present invention segregates normal 15 Subjected to any desired further treatment or
butane for this purpose, whereby C4 hydrocarbons Se,
suitable for alkylation, are so utilized, and only The light hydrocarbons rich in isoparaffins in
the normal butane becomes a blending agent in conduit 3 are combined with those in conduit
the product gasoline. Additionally, the return of 35 and pass to a fractionation tower 38 from
normal light gaseous hydrocarbons Selectively to 20 which a separation is made between normal
the synthesis reaction zone or zones in substan paraffins discharged as at 39, and an overhead
tial quantity tends to restrict and suppress net of essentially light isoparaffins, together with
formation thereof to usable quantities. any contained olefins discharged as at 40. Pipe
In Order to more clearly describe the invention 40 leads to an alkylation system to be hereinafter
with reference to One specific embodiment there 25 referred to in greater detail.
of, reference is had to the accompanying draw The off gases or overhead from the absorp
ing wherein Figure 1 represents more or less dia tion tower 27 comprising essentially carbon di
grammatically one preferred arrangement, and oxide, light hydrocarbon gases, and unreacted
Figure 2 discloses an alternative preferred process. carbon monoxide and hydrogen, pass through
Referring to Figure 1 of the drawing, the nu 30 pipe or conduit 43 to a carbon dioxide recovery
meral to designates an inlet line supplying a System, including an absorption tower 45 and
fresh feed synthesis gas from any suitable source, a stripper 46. This gas recovery unit, the de
not shown, and comprising essentially hydrogen tails of which form, per se, no part of the pres
and carbon monoxide in suitable relative propor ent invention, may comprise any conventional
tions. This stream passes into a header where 35 means for the separation of carbon dioxide, such
it is split, the upper flow passing by way of a pump as the Girbotol System wherein an absorbent
2, and a branch pipe 3 to the lower portion or Such as triethanolamine passes downwardly
inlet of a primary reaction zone designated by through the absorption tower, is removed as at
the numeral 4. 47, stripped of carbon dioxide in the tower 46,
The reaction zone 4 has been designated only 40 and returned to the absorption tower by way
symbolically because of the wide variety of con of pump 48 and conduit 49. Separated carbon
ventional forms it may take. Most advantageous dioxide comes overhead by way of pipe 50.
ly, operation is carried out with an upstand The remainder of the synthesis gas in the
ing tubular reactor in which an isoparaffin syn header passes into secondary reactor 5 oper
thesis catalyst is held in the form of a powder 45 ating for the production of largely and predomi
maintained in a state of dense phase fluidization nantly olefin hydrocarbons. The form and ar
by the upflowing reactants. Temperature con rangement of this reaction zone may be substan
trol may be maintained by means of suitable cool tially identical with that disclosed in connection
ing surfaces immersed in the catalyst mass in the with the primary reactor 4 or alternatively it
usual manner and held by means of a suitable 50 may take the form of any other conventional
coolant at an appropriate temperature level. hydrocarbon synthesis reactor. Herein the fresh
The effluent gasiform reaction products, after synthesis gas is passed, for example, upwardly
appropriate contact with the catalyst emanate through a fluidized mass of catalyst in the sec
from the upper pseudo-liquid level of the fluid ondary reactor, at an elevated pressure and tem
ized mass and pass through filter 5 or any other 55 perature, and the reaction products are with
suitable separator of the cyclone, electrostatic or drawn through conduit 52 to condenser 53 and
other type through outlet conduit f6. Throttle separator 54.
valve T in conduit 6 permits pressure reduction Attention is particularly directed to the fact
from the high pressures prevailing in the reac that the recovered carbon dioxide from pipe 50 is
tion zone 4. The products, at a lower preselected 60 directed through branch pipe 56 to the inlet of
pressure, as for example 200 pounds per square the reactor 5 as a supplementary feed. So also
inch, pass through condenser 8 to separator 9 it is particularly important to note that valved
from which condensed water vapor is removed as conduit 58 connects the aforementioned pipe 43
at 20 and normally liquid hydrocarbon fractions and pipe 56 so that stripped, normally gaseous
are withdrawn as at 2. Normally gaseous over 85 reaction products from the primary or isoparaffin
head from the separator is withdrawn through Synthesis step can be included in the pipe 56
pipe 22 and may be recycled, in part, to the re stream to the secondary reactor in any desired
action zone inlet by way of branch pipe 23, and proportion. Obviously this affords a convenient
pump 24. means for adjusting the total feed to the last
The residual overhead gases are conducted by 70 named reactor to the desired relative proportion
branch pipe 25 to a further recovery means, of carbon dioxide; hydrogen, gaseous hydrocar
which, in the present instance, takes the form bons, and the like, so that the reaction occurs
of an absorption system effective to recover C4 under conditions favorable to the desired utiliza
fractions. To this end, the gaseous stream enters tion of hydrogen and carbon dioxide in the forma
a stripping tower 27 supplied at its upper por 75 tion of olefinic type liquid hydrocarbons, and the
 2,308,784
maximum suppression of light hydrocarbon gas action at the temperature prevailing in that re
formation. action Zone, where:
By-product water is discharged from separator A is the fraction of the carbon monoxide
54 as at 60 the liquid hydrocarbon layer passing which will be converted in that stage. Such frac
by way of pipe 6 to stabilizer 62. The overhead tion may range from 0.90 to 0.995 for example.
from stabilizer 62, comprising essentially olefins The equilibrium constant K for the water gas
suitable for alkylation, passes by way of pipe 6 shift reaction can be expressed as:
to a fractionator 64 operating to remove normal
butane as at 65, and deliver the olefins and con --- (7350)
tained isoparaffins, if any, to the alkylation unit 10 K =0.0202e0plus400)
42 through pipe . where:
Additional alkylation stock is obtained from the e is the base of Naperian logarithms e.g. 2.7183,
gaseous overhead of separator 54 withdrawn and T is the reaction temperature in degrees F.
through pipe 70 to an absorption system identical The value of Kranges from 70 fora reaction tem
with that used to treat the normally gaseous perature of about 500 F, to a value of about 16
products from the primary reactor and compris for a reaction temperature of about 700 F. and
ing an absorber 7 and a stripper 72. The frac is about 31 for a reaction temperature of about
tions stripped from the adsorbent liquid com 600°F. P
prise suitable olefin alkylation stock, preferably In general the magnitude of the net consump
butylenes. These are intermingled with the prod 20 tion of carbon dioxide increases with the excess of
uct of pipe 68 and treated to remove normal par the above molar ratio, over the value of K.
affins in the fraction syste. n 64, previously re Under these conditions, it is possible to con
ferred to. Sume all or substantial portions of the carbon
Stripped gas from the absorber 7 is discharged dioxide available.
through pipe 73 for further treatment, recovery 25 It is to be understood that the specific ab
or use as fuel, or conversion to additional synthe sorption fractionation and stabilizing arrange
sis gas as may be desired. ments disclosed may be substituted by any
Suitably valved branch pipe 74 connects pipe 70 equivalent means capable of producing an
and header f to permit recycle of wet products equivalent separation. Moreover, the invention
of reaction to the reactor 5 as desired. 3) fully contemplates the treatment of equivalent
From the foregoing, it will be apparent that in streams in a suitable common separation sys
the present process, coordinated reactors, operate tem. For example, the wet product gases from
respectively for the production of isoparaffinic the separators 9 and 54 may be treated by com
and olefinic hydrocarbons from which liquid hy mon absorption or fractionation means, and simi
drocarbon fractions are recovered, and the nor 35 larly the respective liquid streams therefrom may
mally gaseous isoparaffins and olefins are supplied be stabilized in a single stabilizing means, the
in predetermined proportion to an alkylation sys combined alkylation charge stock passing in ad
tem 42 supplying alkylate as at 80. mixture to the alkylation unit.
The invention particularly contemplates opera 40 In addition, the invention contemplates the re
tion of the olefin forming synthesis step under covery of olefins by absorption in a suitable acid
conditions adapted to result in appropriate utili Stream forming a part of the alkylation system.
2ation of excess carbon dioxide as previously men For example, any suitable olefinic fraction from
tioned. While approach to this desirable condi the Secondary reaction Zone may be passed into
tion is afforded simply by supplying the available 45 a suitable stream of sulphuric acid in an absorber
streams of carbon dioxide and hydrogen to the and the withdrawn acid, containing absorbed
reactor, the desired condition may be controllably olefins, passed directly to the alkylation reactor
effected by correlating the various feed streams where it is contacted with the isoparaffin stream,
in the usual manner. So also the product of the
to the reactor 5 as disclosed in aforementioned alkylation Zone may be subjected to separation
copending application Serial No. 630,521, so that 50 and the recovered acid recycled to the absorber
the composition of the total feed meets the con in the usual manner.
ditions specified therein and to which reference It is important also to note that the present in
is hereby made. wention contemplates interexchange of recycle
Essentially however the total feed to the re streams between the two reaction zones in such
actor is adjusted so that the molar ratio of the 55 a manner as to permit additional adjustment
H to CO is 2:1 or preferably greater and the pro of the respective total feeds. To this end, con
portion of CO2 is raised to a value where the de duit 75 and pump 76 direct recycle stock from
sired suppression or consumption of CO2 Occurs. the line 74 to the inlet pipe 3 of reactor f4 as
Preferably the total molar proportion of Ha is not required. Conversely, valved branch pipe 77 per
greater than the sum of twice the molar propor 60 mits recycle stock from line 23 to be controlledly
tion of CO plus three times the molar proportion supplied to reactor 5.
of CO2 in the total feed. Formularized, this In accordance with a modified process shown
means that the ratio of Ha to 2CO plus 3CO2 is in Figure 2, a primary reaction zone 80 which
less than about 1:1. Advantageously it is not may be the same as above, is supplied with syn
below about 0.6:1. 65 thesis gas through inlet pipe 8, branch pipe 82
In addition for net carbon dioxide consumption and pump 83, and the products of reaction pass,
in the secondary reaction zone, it is contemplated preferably at a lower pressure, through condens
maintaining the molar ratio: er 84 and Separator 85. The liquid hydrocarbon
layer passes by way of pipe 36 to stabilizer 87.
70 Tail gas from the separator 85, subject to recycle
CO2(H2-2COA) of any portion and to venting through branch
COXHO
pipe 88, as desired for purposes of control, is
of the reactants passing to the reaction zone sub passed directly through pipe 90 into the inlet of
stantially greater than the numerical value of the the secondary reaction zone 9, together with ad
equilibrium constant for the water gas shift re 75 ditional Synthesis gas from inlet manifold 8.
 2,308,724
7
Reaction products from the secondary reactor ture of about 600 . This stream is admixed:
are thereafter condensed as at 92 and separated with additional fresh synthesis gas in the ratio
as at 93, the liquid oily layer passing by Way of of about one part of synthesis gas to two parts
pipe 94 to the aforementioned pipe 86 and the of tail gas from the primary reaction zone.
stabilizer 87. Return line 95 permits recycle of The withdrawn gasiform reaction products
any desired portion of the separated normally from the secondary reactor are similarly con
gaseous products of reaction to the reactor. Re densed and separated with the recovery of an ad
sidual tail gas from pipe 96 flows to a separation ditional stream of essentially motor gasoline frac
system of the character described above, compris tions. The separated gases are recycled te the
ing am absorber 87, in which a suitable liquid ab secondary reaction zone at a recycle rate of about
sorbent takes up C hydrocarbons, and is stripped 2:1 on the basis of admixed synthesis gas. The
in tower 98. The of gas from the absorber 8 unrecycled portion is treated for the recovery of
comprises any residual unreacted feed gas, inerts, C. hydrocarbons and this stream, combined with
light hydrocarbon gases and the like, and may : the other Ca hydrocarbon stream is fractionated
be returned, if necessary, to control the feed to 5 for the removal of normal butane and then sup
either or both of the reaction zones. The stripped plied directly to an alkylation system for the pro
gases pass through pipe 99 to a fractionation Sysis duction of a high grade alkylate.
tem 80 operating to remove normal butane as at The composition of the combined feed to the
O and deliver a stream of isobutane and butyl Secondary reaction zone, excluding recycle, is
ene through, pipe 62 to the alkylation unit 42. 30 Substantially free of water vapor and contains
Stabilizer 8 delivers through outlet 5 a nOra hydrogen and carbon monoxide in the molar ratio
mally liquid stream which may be a motor gaSO Substantially in excess of 3:1, and slightly under
line product. It also delivers an overhead strean 40 mol percent of carbon dioxide on the basis
of C hydrocarbons thru pipe 06, to the alkyla of the total reactant content.
tion plant as shown. Alternatively this strean The carbon dioxide supplied to the secondary
may pass through valved branch line 0 to the reaction Zone is largely consumed in the produc
inlet 99 of the fractionator O). tion of additional liquid hydrocarbons.
As indicated diagrammatically, the normal bus It is to be noted that the isoparaffin synthesis
tane in line G may be used to pressure the reaction operates best at relatively low fresh feed
motor gasoline fractions which Constitute or are 30 ratios of hydrogen to carbon monoxide in the
included in the hydrocarbon stream of pipe O5. neighborhood of about 1:1 to about 1.5:1, prefer
Moreover, it is important to note that any ex ably about 1.2:1. On the other hand, the sec
cess or desired portion of the normal butane in Ondary reactor is most advantageously operated
the pipe to may be conveyed by branch pipe O2 With a synthesis gas containing hydrogen and
to the inlet line 82 of the isoparaffin synthesis 35 carbon monoxide in a ratio greater than about
reactor 80. The stream of normal butane thus 2:1. As clearly shown above the present inven
Supplied to the reactor is isomerized within the tion afords an excess of hydrogen, typical of the
reaction Zone, by the isoparaffin synthesis ca first reaction, to supplement the feed to the sec
talyst, to form additional isobutane for alkyla ond reactor, thus permitting use of a common
tion. In addition, any substantial proportion of O Supply of synthesis gas which is relatively low in
normal butane so added tends to suppress the hydrogen. In short an overal ratio of less than
overall formation of paraffin hydrocarbons in this about 2:1 in the fresh feed may be satisfactory.
stage, thereby permitting the net production of On the other hand, an Ha:CO ratio of 2:1 or
normal butane to be held at a level approxi greater in the fresh feed to the second reactor
mating the actual requirements of the final motor may result in better consumption of CO, and the
gasoline. The embodiment of Figure may be process is therefor even better controlled where
similarly modified. separate feeds of synthesis gas are available,
The foregoing embodiment accordingly directs namely, a relatively low ratio of carbon monoxide
unaltered wet tail gas from the isoparaffin syn to the first reactor and a higher one for the
thesis step to the secondary reaction zone, sub 50 Second.
ject to the controls indicated, whereby the con While the isoparaffin synthesis catalyst has
tained isoparaffins, carbon dioxide and hydro been hitherto mentioned in terms of the alumina
gen limit normal gaseous paraffin production thoria, or the zinc oxide-alumina complexes, the
therein, and the carbon dioxide formed by the present invention contemplates the substitution
isoparaffin Synthesis step is consumed in increas 55 of any suitable catalyst active for the production
ing the yield of liquid hydrocarbons. of a largely isoparaffinic hydrocarbon product,
In accordance with one specific example, a syn
thesis gas containing essentially hydrogen and
particularly one wherein the major portion of
the C4 hydrocarbons is in the form of isobutane.
carbon monoxide in approximately the molar Therefor, other catalysts may be employed where
ratio of i.5:1 is passed through a primary re 600 in the thoria or zinc oxide, above, are substituted
action Zone containing fluidized alumina-thoria by other suitable material capable of effecting
catalyst, containing about 20% alumina and about the catalytic production of hydrocarbons, such
80% thoria, at a pressure of about 300 atmos for example as zirconia, molybdenum oxide and
pheres and a temperature of about 805 F. The the oxides of ruthenium, and others of the transi
gasiform reaction products are removed from con 65 tion elements.
tact with the catalyst, reduced in pressure to The invention, moreover, contemplates use of
about 200 pounds per square inch guage, and the mixtures of hydrocarbon synthesis catalysts with
stream condensed and separated at about 70° F. typical butane isomerization catalysts which are
with the recovery of a liquid product essentially effective to isomerize butane under the pressure
in the motor gasoline boiling range. C4 fractions 70 and temperature conditions at which the syn
are recovered from this gas, and the residue thesis catalyst is also effective to synthesize hy
passed to a secondary reaction zone containing drocarbons by the reduction of carbon monoxide
a fluidized iron catalyst promoted with alumina With hydrogen; in short, where the synthesis
and potassium oxide at a pressure of about 200 catalyst effects hydrocarbon formation and the
pounds per Square inch gauge, and at a tempera- 6 isomerizing catalyst effects concurrent isomerica.
 8,508,724
10
tion to isoparaffins at the same temperature and Said metal oxide isoparaffin synthesis catalyst
pressure. The isomerizing catalysts which may Comprises zinc oxide and alumina.
be employed in this connection are either Syn 4. The method according to claim 1 wherein
thetic or natural materials, such as diatomaceous the stream of synthesis gas supplied to the first
earth, silica gel, magnesium silicates, aluminum reaction zone contains H2 and CO in a molar
silicates, activated alumina, bauxite, bentonite, ratio below about 2:1.
and may others, and may be promoted with boron 5. The method according to claim 1 wherein
oxide, silicon oxide of hydrofluoric acid. These the stream of synthesis gas supplied to the first
may be effective with catalysts such as thoria reaction zone contains H2 and CO in a molar
and zinc oxide referred to above. They are also 0. ratio within the range of about 1:1 to about
effective as isomerization catalysts at Synthesis 1.5:1.
temperatures below the temperature at which 6. The method according to claim 1 wherein
cracking proceeds at a substantial rate and with the streams of synthesis gas supplied to both
in the range where hydrocarbon synthesis cat the first and second reaction zones contain H2
alysts are effective to cause the reduction of car 5 and CO in a molar ratio below 2:1 and where
bon monoxide by hydrogen with the production in the total feed to the second reaction zone,
of hydrocarbons. Therefor with such combi after injection of said residual hydrogen and
nations, the hydrocarbon synthesis catalyst, may by-product carbon dioxide, contains H2 and CO
include typical catalysts such as cobalt, nickel, or in a molar ratio Substantially above 2:1.
?? 20 7. The method according to claim 1 wherein
Obviously many modifications and variations normal paraffinic hydrocarbons from the effluent
of the invention as hereinbefore set forth, may products are recycled to the first reaction Zone
to effect substantial isomerization thereof.
be made without departing from the spirit and 8. In the production of hydrocarbons of high
scope thereof, and therefore only such limita 25 antidetonation characteristics, in the catalytic
tions should be imposed as are indicated in the hydrogenation of carbon monoxide, the steps
appended claims. which comprise simultaneously passing individual
I claim: streams of synthesis gas comprising hydrogen
1. In the production of hydrocarbons of high and carbon monoxide in the molar ratio less
antidetonation characteristics by the catalytic 30 than about 2:1 through separate first and second
treatment of a synthesis gas comprising essen reaction zones, said first reaction Zone being
tially hydrogen and carbon monoxide, the steps maintained at a temperature in the range of
which comprise passing individual streams of about 750-900° F. and a pressure from about
said synthesis gas respectively through separate 50-500 atmospheres, and containing a metal ox
first and second reaction zones, Said first reac $5 ide, isoparaffin synthesis catalyst effective under
tion zone being maintained at a temperature in such conditions to convert said reactants into an
the range of about 750-900' F., and a pressure effluent product stream containing predominantly
from about 50-500 atmospheres, and containing isoparaffinic hydrocarbons and Substantial quan
a metal oxide isoparaffin synthesis catalyst ef tities of carbon dioxide and hydrogen, the second
fective under said reaction conditions to convert 40 reaction zone being maintained in the range of
said reactants into predominantly isopraffinc hy about 550-700' F. and an elevated pressure, Sub
drocarbons with the formation of substantial stantially below the range prevailing in the first
quantities of by-product carbon dioxide, the sec reaction zone and containing an iron type hydro
ond reaction zone being maintained at a tem carbon synthesis catalyst effective under said re
perature in the range of about 550-700' F., and 5 action conditions to convert the reactants into
an elevated pressure substantially below the an effluent product stream containing predomi
range prevailing in the first reaction Zone, and nantly olefinic hydrocarbons, withdrawing the
containing an iron type hydrocarbon synthesis effluent product stream from contact with the
catalyst effective under said reaction conditions catalyst in the first reaction zone, recovering de
to convert synthesis gas into predominantly ole sired hydrocarbon fractions and included water
finic hydrocarbons, effecting a substantial con vapor therefrom, and injecting residual hydrogen
version of the synthesis gas fed to the first re and byproduct carbon dioxide into the Synthesis
action zone, withdrawing therefrom the effluent gas feed to the second reaction Zone to form a
product stream, recovering from the withdrawn gaseous feed mixture containing hydrogen and
stream desired hydrocarbon fractions and in 5 5 carbon monoxide in a molar ratio above about
cluded water vapor, and injecting residual hy 2:1 and a carbon dioxide content sufficient to
drogen and by-product carbon dioxide into the direct the water-gas shift reaction in that direc
synthesis gas feed to the second reaction zone tion which consumes carbon dioxide and hydro
to form a gaseous feed mixture containing H2 gen to form a substantial quantity of additional
and CO in a molar ratio above about 2:1, and a carbon monoxide at the temperature prevailing
CO2 content sufficient to direct the Water-gas therein, effecting Substantially complete conver
shift reaction in that direction which consumes Sion of carbon monoxide in the Second reaction
CO2 and H2 to form a substantial quantity of zone into said desired products of reaction, and
additional CO at the temperature prevailing reacting isobutane fractions from the hydrocar
therein, effecting substantially complete conver 65 bon product of the first reaction zone with olefins
sion of CO in the Second reaction Zone into de from the hydrocarbon product of the second re
sired products of reaction and reacting isopar action zone to form liquid alkylate.
affins from the effluent product stream of the 9. In the production of hydrocarbons of high
first reaction zone with olefins from the effluent antidetonation characteristics by the catalytic
product stream of the second reaction zone to 70 treatment of a Synthesis gas comprising essen
form liquid alkylate. tially hydrogen and carbon monoxide, the steps
2. The method according to claim 1 wherein which comprise passing individual streams of said
said metal oxide isoparaffin Synthesis catalyst synthesis gas respectively through Separate first
comprises alumina and thoria. and second reaction zones, Said first reaction Zone
3. The method according to claim 1 wherein 75 being maintained at a temperature in the range
 2,508,784.
2
of about 750-900 F, and a pressure from about vailing therein, effecting substantially complete
50-500 atmospheres, and containing a metal ox conversion of CO in the second reaction Zone
ide, isoparaffin synthesis catalyst effective under into desired products of reaction and recovering
said reaction conditions to convert said reactants desired hydrocarbons from the e?tuent product
into predominantly isoparafiinic hydrocarbons strean hereof.
with the formation of substantial quantities of AMS E, CRAAM.
by-product carbon dioxide, the second reaction
zone being maintained at a temperature in the
range of about 550-700' E., and an elevated pres The following references are of record in the
sure substantially below the range prevailing in flle of this patent:
the first reaction zone, and containing an iron
type hydrocarbon synthesis catalyst effective UNITED STATES PATENTS
under said reaction conditions to convert syn Number Nanne Date
thesis gas into predominantly olefinic hydro 1798,288 Wietzel et al. ------- Mar. 3, 1931
carbons, effecting a substantial conversion of the 5 2,224,043 Herbert ------------- Dec. 3, 1940
synthesis gas fed to the first reaction zone, with 2,253,607 Boyd ei al. ---------- Aug. 26, 1941
drawing therefrom the efituent product stream, 225,074 Goldsby ----------- Sept. 23, 1941
recovering from the withdrawn stream desired 2,257.293 Dreyfus ------------ Sept. 30, 1941,
hydrocarbon fractions and included water vapor, 2,286,814 ?e??p ----------------- June 16, 1942
and injecting residual hydrogen and by-product 2,347,682 Gunness ------ ??? ??? ??? --???? May 2, 1944
carbon dioxide into the synthesis gas feed to the 2,360,463 Arveson ------------ Oct. 17, 1944
second reaction zone to form a gaseous feed mix 2,417,164. Huber ------------- Mar. 11, 1947
ture containing Ha and CO in a molar ratio above 2,436,957 Eastman ------------ Mar. 2, 1948
about 2:1, and a COa content sufficient to direct OTHER REFERENCES
the water-gas shift reaction in that direction 25
which constnes CO2 and Ha to form a substantial Article in "The Oil and Gas Journal,' of Jan
quantity of additional CO 8t the temperature pre uary 19, 1946, pages 86 and 89.