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0d. l5; 1946.
H. v. A'rwELL A
2,409,235
CONTINUOUS PROCESS FOR BFFECTING CATALYTIG -RBAGTIOHS
Filed nec. 18,. 194s'
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HAROLD V. ATWELL
HIS ATTORNEY
l
Patented Oct. 15, 1946
_ 2,409,235
UNITED STATES PATENT OFFICE
2,409,235
con'rmnousrrnocnss Fon EFFEcTmG
cA'rALmc REACTIONS
Harold V. Atwell, Beacon, N. Y., assignor, by
mesne assignments, to The Texas Company,
New York. N. La corporation oi Delaware
Application December 18, 1943, Serial No. 514,768
14 Claims. (ci. 2st-67s)
This invention relates to a continuous- process
for effecting catalytic reactions, and more par
ticularly for eiîecting catalytic conversion of
gaseous reactants by the action of a solid catalyst
- in ñnely divided or powdered form for the pro
duction of normally liquid carbonaceous com
pounds.
2
the process. Additional methane may be ob
tained from an outside source. Instead of meth
ane, a methane fraction may thus be obtained
from the hydrocarbon products and used for re
acting with the carbon dioxide. The gaseous
hydrocarbon so used for this purpose may com
»
prise methane, ethane, propane, butane, or a
mixture thereof.
A feature of the invention involves conduct
the action of a solid hydrogenating catalyst con 10 ing the two steps of the conversion process in
taining a carbide forming metal, such as, cobalt,
separate reaction zones with provision for the
\ iron, or nickel. More specifically, the invention
continuous circulation of the catalyst from one
‘ contemplates a two-stage continuous process, in
zone to the other, and this catalyst circulation
the first stage of which the catalyst is subjected
may be eiîected by suspension in gas or liquid
to contact with a volatile carbon compound under 15 or by other mechanical means.
`
The invention contemplates forming normally
liquid compounds from carbon and hydrogen by
conditions adapted to form metallic carbide, and
A further feature involves synthesizing hydro
carbons from carbon and hydrogen without the
taining metallic carbide is separately subjected
formation of water. Avoiding the formation oi
to contact with hydrogen under conditions adapt
water greatly reduces the complexity and energy
ed to produce normally liquid carbonaceous com 20 requirements. Also, as already intimated, a fur
pounds, such as hydrocarbons.
ther feature involves utilizing carbon dioxide
In accordance with the invention, a volatile
formed in the primary stage for reaction with a
carbon compound, such as carbon monoxide is
normally gaseous hydrocarbon at elevated tem
subjected to contact with a solid catalyst con
perature to produce carbon monoxideand hy
taining cobalt, iron, or nickel at a temperature 25 drogen required in the conversion reactions.
in the range about 350 to 425° F., whereby for
Advantageously, 1the reaction in the primary
mation of the carbide of cobalt occurs to a sub
stage is conducted in the substantial absence of
stantial extent in accordance with the following
hydrogen; while the reaction in the secondary
chemical equation:
stage is carried out in the substantial absence of
30 the carbon monoxide or other volatile carbon
in the second stage of which the catalyst con
compound.
The catalyst containing the carbide of cobalt or
other metal is then passed to a separate treating
zone wherein it is treated with hydrogen at a
somewhat lower temperature in the range about
200 to 400° F. and under conditions such that
the carbide undergoes decomposition, the liber
ated carbon reacting with hydrogen to form hy
drocarbon products mainly heavier than methane.
The catalyst of decreased carbidecontent is
withdrawn and returned to the primary zone
for further treatment with carbon monoxide.
,
Other volatile carbon compounds useful in ef
fecting the primary reaction comprise normally
gaseous oleñns and parañins, and vaporizable
5 metallic compounds, such as iron carbonyl. Un
der certain conditions carbon dioxide may be
eiîective.
-
In order to illustrate the invention, referenc
`will now be made to the accompanying drawing,
comprising a diagram of flow for effecting syn
theses of hydrocarbons having two> or more car
bon atoms per molecule, including normally liquid
Carbon dioxide produced in the primary stage
hydrocarbons, from hydrogen and carbon mo
is discharged therefrom and may be reduced to
noxide.
carbon monoxide by contact with carbon or may 45 As indicated in the drawing, the numeral I
be reacted with methane to produce carbon mo
designates a primary reaction vessel, while the
noxide and hydrogen by conventional methods.
numeral 2 designates a secondary reaction vessel.
The carbon monoxide so obtained is thus avail
Both vessels advantageously comprise towers
able for recycling to the primary reaction stage.
adapted for eiïecting contact between the gaseous
Likewise, hydrogen obtained by reacting methane
reactants and the catalyst While the catalyst is
with carbon dioxide is available for recycling to
suspended or dispersed in powdered form in the
the secondary stage of the process.
gaseous reactants during their passage through
The methane used for reaction with carbon
the reaction vessels.
dioxide advantageously includes that obtained
Referring now to the primary reactor I, carbon
by separation from the hydrocarbon products of 55 monoxide is continuously withdrawn from a suit
2,409,235
~ i
4
3
able source through a conduit 3 by a compressor
.
through a pipe I1 leading to a dust separator I8,
which may be of the cyclone type. The efiluent
product stream from the separator I8 is passed
through pipe I9 to a secondary separator 20,
4, which discharges it into the bottom or lower
portion of the primary reactor. The carbon mo
~ noxide gas stream thus flows upwardly through
the reactor and is converted to CO2 which escapes
therefrom through a conduit 5.
which may be of the electrical type wherein re
sidual dust is removed. The catalyst dust so re
The catalyst enters the top or upper portion of
_ moved in the separators I8 and 20 is discharged
the reactor from the hopper 6 through a pipe 1.
According to one modiñcation, the pipe 1 may
through the conduits 2| and 22 respectively which
also return the reacted catalyst powder to the
'
communicate with the discharge pipe of the com 10 hopper 6.
The hydrocarbon products including hydrogen,
pressor 4, in which case the catalyst powder is
normally gaseous, and normally liquid hydrocar
forced into the bottom of the reactor by jet ac-'
bons, are passed through the pipe 25 to a frac»
tion of the entering carbon monoxide stream.
In any case the catalyst in finely powdered
tionation unit 26. 'I'his unit may comprise one
or more individual towers arranged to permit
form, the particle size ranging from 50 to about
separating the products into their diñerent con
500 microns, is introduced and the rate of gas
ñow through the reactor adjusted, so that the
stituent parts or fractions.
catalyst powder is suspended in the gas body
lHydrogen and light gases such as methane and
ethane are thus separated from the products in
within the reactor.
,
.
A quantity of the catalyst powder accumulates
the fractionation unit and discharged therefrom
in the lower portion of the reactor behind a suit- f ïthrough a pipe 21. The hydrogen and light gases
>may be passed, all or in part, through a pipe 30
able baffle `8, from which point a stream of cat
alyst powder is continuouslywithdrawn from the
to a. conversion unit, referred to later, wherein
reactor through a conduit 9.v The catalyst so
withdrawn contains metal carbide formed _within
the reactor as a result >of'contact with`carbon
-
monoxide.
`
Thus. for example, 'the catalyst contained in
2
the ‘gaseous hydrocarbons are used in the pro
duction of carbon monoxide.
As indicated, a normally liquid fraction com
prising naphtha hydrocarbons may be removed
through a pipe 3|. Higher boiling hydrocarbons
the hopper 6 comprises cobalt deposited on a
may be withdrawn through a pipe 32.
suitable solid supporting material, such as silica 30 As previously mentioned, the gas stream in
gel, or other solid absorptive material. A tem- ' troduced to the primary reactor I escapes there
perature of about 390 to 400° F. is maintained
from through a conduit 5. This conduit comwithin the reactor, and this can be accomplished
municates With a separator 40 wherein provi
by suitable heating of the entering gas stream
sion is made for separating ent-,rained catalyst
in conventional heating means not shown in the 35 powder from the gas. The separated catalyst
drawing. The flow of gas through the reactor
which will contain some cobalt carbide is ad
vantageously passed through conduit 4I, which
and the rate of catalyst removal therefrom may
communicates with the previously mentioned
be controlled so that the residence time of the
catalyst in the reactor is of the order of about 1
conduit 9.
The gas stream flowing from the top of the
minute to 60 minutes. Pressure prevailing in the 40
separator 40 through a pipe 42 comprises a mix
reactor may range from about 1 atmosphere to
several atmospheres.
ture of carbon monoxide and carbon dioxide, the
The catalyst containing cobalt carbide being y latter being a by-product of the reaction in the
primary reactor. This gaseous mixture is then
drawn oif through the conduit 9 is passed to the
secondary reactor 2, as indicated in the drawing. 45 passed to an absorption zone 43 wherein it is
Hydrogen gas is advantageously injected from a
subjected to contact with a suitable absorption
pipe l0 into the conduit 9 so as to force the cat
liquid such as triethanolamine, whereby the car
alyst into the secondary reactor. The hydrogen
bon dioxide is absorbed and thus removed from
the carbon monoxide. The latter is discharged’
gas may be heated prior to introduction by con
ventional means not shown in the drawing.` The 50 from the top of the absorber 43 through a pipe
sensible heat of the entering hydrogen gas as
44 and, all or in part, returned through a pipe
well as that of the catalyst flowing through the
45 to the primary reactor.
The absorption liquid containing carbon di
conduit 9 is utilized to maintain the required
oxide is drawn off through a pipe 46 to a regen
reaction temperature within thesecondary re
actor. As in the case of the primary reactor, the 55 erator 41 wherein it is subjected to sufficiently
elevated temperature to strip out the carbon di
secondary reactor operation is such that the cat
oxide. Carbon dioxide is discharged through a
alyst is maintained suspended in the body of gas
pipe 48, which communicates with a pipe 49 and
moving 'through the reactor, for the requisite
amount of time to effect decomposition of co
by which means all or a portion of the carbon di
balt carbide and reaction between carbon and hy 60 oxide is passed to the conversion unit 50.
The regenerated absorption liquid is passed to
drogen for the production of hydrocarbon corn
pounds. A temperature of about 300 to 325° F.
tank 5I from which it is returned through pipe
52 to the absorber 43.
is advantageously maintained in the secondary
It is contemplated that a portion of the gas
reactor; while the rate of gas iiow therethrough
and catalyst removal therefrom is such as to per 65 stream flowing through the previously mentioned
pipe 5 may be passed through a pipe 53 com
mit a residence time of the catalyst within the
municating with the pipe' 45 for recycling directly
reactor ranging from a few seconds to about 5
minutes. The major portion of the catalyst is
to the primary reactor.
drawn ofi' from the baiiled section at the bottom
In the conversion unit 50 the carbon dioxide is
of the reactor, and a. stream thereof is continu 70 reacted with methane or other normally gaseous
hydrocarbon material at a temperature of about
ously withdrawn through a conduit I 5, communi
eating with the hopper 6.
.
1800“ F. or in the range about 1500 to 2000° F.
A portion of the catalyst powder is carried out
so as to convert these materials into carbon mon
of the reactor with the gaseous hydrocarbon
oxide and hydrogen. The hydrocarbon reactant,
products of reaction which are discharged4 .75 such as methane or a methane fraction, is advan
2,409,235
5
6
tageously that removed from the fractionator unit
well head pressure may be passed through the
primary reaction zone and an eil‘iuent stream of
26 and obtained through the previously men
tioned pipe 30 leading to the conversion unit 50.
unreacted hydrocarbons, or other gaseous mate
The gaseous products of the reaction formed in
rial from the process may be returned, without
the unit 50 are passed through a pipe 60 to an` 5 substantial reduction in pressure, to an inlet well
absorber 6| wherein they may be scrubbed with
of a subterranean reservoir from which the gases
cuprous chloride or other suitable liquid adapted
are originally obtained.
.
to effect removal of carbon monoxide from hy
While mention has been made of producing hy
drogen. The hydrogen is removed from the ab
drocarbon products it is also contemplated that
sorber through a pipe 62, which also communi
the process may be employed for the production
cates with the pipe l 0 for return to the secondary
of oxygenated hydrocarbon compounds includ
reactor.
ing alcohols, aldehydes, etc.
i
.
The cuprous chloride mixture containing car- -
Obviously, many modifications and variations
bon monoxide is drawn off through a pipe 63 to
may be made in the invention as herein set forth
a regenerator 64 wherein suitable temperature 15 without departing from the spirit and scope
and pressure conditions are maintained to effect
thereof, and therefore only such limitations
stripping of the carbon monoxide from the cu
should beimposed as are indicated in the ap
prous chloride. The stripped carbon monoxide
pended claims.
is conducted through a pipe 65, communicating
I claim:
with the pipe 3.
1. A continuous cyclic process for catalytically
20
«As an alternative method of preparing carbon
forming normally liquid compounds from carbon
monoxide and hydrogen, methane or other light
and hydrogen by the action of a solid hydrogenat
hydrocarbon may be converted in a regenerative
ing catalyst containing a carbide-forming metal
type of furnace into hydrogen, leaving carbon de
which comprises passing a stream of said catal
posited on the checkerwork of the furnace. The
yst in finely divided form through a primary re
deposited carbon is then separately reacted with
action in the substantial absence of> added free
carbon dioxide to produce carbon monoxide.
hydrogen, subjecting said stream therein to con
'I'he method of ñow and the type Of apparatus
tact, with a volatile carbon compound under ele
employed is subject to modification, for example,
vated temperature conditions such that metallic
each reaction stage may be conducted in a plu 30 carbide is formed on said catalyst in substantial
rality of reactors. 'I‘here may be either concur
amount, passing said catalyst stream containing
rent or countercurrent flow of catalyst powder
resulting metal carbide and while still at elevated
and reactants through the reactors. ,
temperaturer from the primary reaction zone to
The catalyst may be maintained as a fluidized
a secondary reaction zone, subjecting it in said>
mass or as a relatively quiescent mass of solid
secondary _zone to contact with hydrogen under
material continuously moving through the _reac
conditions such that metal carbide is decom- '
tion zone. The catalyst may be introduced to the
posed, the liberated carbon reacting with hy
drogen to form carbonaceous compounds mainly
of higher molecular weight than methane, dis
reaction zones as a suspension of solids in a liquid
medium and the liquid medium may be of such
volatility that it vaporizes within the reaction
zone thereby taking up exothermic heat of reac
40
tion. The vaporized liquid is discharged from the
reaction zones together with the reaction prod
ucts.
"
A portion of the catalyst accumulating in the
hopper 6 may be drawn oil’ continuously through
pipe 10 for treatment with hydrogen in a reac
tivator 80 to remove oily or waxy material that
may have accumulated thereon during the course
of the reactions. Such hydrogen treatment may â
be carried out at a temperature ranging from
about 400 to 800° F. Treated catalyst is then re
turned to the system through pipe 1| for use in
the reactor I.
Mention has already been made of using nor
mally gaseous hydrocarbons such as ethane, pro
pane and butane in place of carbon monoxide as
the treating agent in the primary reactor. The
use of such hydrocarbons is thought to involve
absorption of the hydrocarbons on the surface of
the catalyst to form methylene groups. These
methylene groups are subsequently hydrogenated
in the secondary stage. This adsorption of hy
drocarbons on the surface of the catalyst may be
carried out under relatively high pressure such as
1000-5000 lbs. per square inch while the subse
quent hydrogenation step may be carried out at
relatively low pressure. Adsorption of such hy
drocarbons under elevated pressure is of interest
charging said compounds, withdrawing catalyst
of decreased carbide content from the secondary
' zone and passing it to said primary zone for in
creasing its carbide content.
., 2. The process according to claim l in which
ythe volatile carbon compound is carbon mon
oxide.
3. A continuous cyclic process for catalytically
forming normally liquid hydrocarbons from car
bon and hydrogen by the use of a solid hydro
genating catalyst containing a carbide-forming
metal selected from the group consisting of co
balt, iron and nickel which comprises passing a
stream of said catalyst in powdered form through
a primary reaction zone in the substantial ab
sence of added free hydrogen, subjecting the
stream to contact therein with a volatile carbon
compound at a temperature in the >range about
l 350 to 425° F. such that metallic carbide is formed
in the catalyst in substantial amount, passing the
catalyst stream containing resulting metallic car
bide from the primary zone while still at elevated
temperature to a secondary reaction zone, sub
jecting it therein to contact with hydrogen at a
temperature in the range about `200 to 400° F.
such that metallic carbide is decomposed and
liberated carbon reacts with hydrogen to form
hydrocarbon compounds mainly of higher mo
lecular weight than methane, discharging the
in connection with the use of normally gaseous 70 hydrocarbon compounds, withdrawing catalyst
hydrocarbons available from distillate well opera
of decreased carbide content from the secondary
tions, such gaseous hydrocarbons being available
zone and passing it to said primary zone for in
at pressures in the range mentioned. Therefore,
creasing its carbide content.
it is contemplated that a stream of these hydro
4. The process according to claim 3 in which
carbons under well head pressure or substantially 75 the carbide-forming metal of the catalyst is co
2,409,235
7
of separate primary and secondary conversion
zones in succession, continuously introducing to
the primary zone gas consisting essentially of
carbon monoxide, maintaining said powder in
contact with carbon monoxide in the primary
bait and the volatile carbon compound is carbon
monoxide.
5. A continuous cyclic process for catalytically
forming normally liquid hydrocarbons from car
bon and hydrogen by the use of a solid hydro
genating catalyst containing a carbide-forming
metal selected from the group consisting of co
balt, iron and nickel which comprises passing a
zone at a temperature of about 390 to 400° F. for
a period of time ranging from about 1 to 60 min
utes s’uch that cobalt is converted to cobalt
carbide in substantial amount in said stream of
stream of said catalyst in powdered form through
a, primary reaction zone in the substantial ab 10 powder, continuously introducing gas consisting
essentially of hydrogen to the secondary zone,
maintaining the powder containing cobalt car
'bide flowing through the secondary zone in con
sence of added free hydrogen, subjecting this
stream to contact therein with carbon monoxide
at a temperature in the range about 350 to 425°
F. such that metallic carbide is formed in sub
stantial amount with formation of carbon diox
tact with said hydrogen at a temperature of
15 about 300 to 325° F. for a time of contact rang
ing from a few seconds to about 5 minutes such
ide, removing said carbon dioxide from the-` pri
that cobalt carbide is reconverted to the metal
mary zone, passing the catalyst stream contain
and resulting liberated carbon is reacted with
ing resulting metallic carbide from the primary
hydrogen to form hydrocarbons mainly of higher
zone while still at elevated temperature to a -sec
ondary reaction zone, subjecting it therein to 20 molecular weight than methane, and continu
ously discharging hydrocarbon products of re
contact with hydrogen at a temperature in the
action from said secondary zone.
range about 200 to 400° F. such that _metallic
8. A continuous cyclic process for catalytically
carbide is decomposed and liberated carbon re
forming normally liquid hydrocarbons from car
acts with hydrogen to form hydrocarbon com
pounds comprising mainly normally liquid and 25 bon and hydrogen which comprises establishing
a continuous cyclic stream of powdered solid ad
normally gaseous hydrocarbons of higher molec
sorptive containing cobalt flowing through a pair
ular weight than methane, discharging the hy
of separate primary and secondary conversion
drocarbon compounds, withdrawing catalyst of
zones in succession, continuously introducing to
decreased carbide content from the secondary
zone, passing it to said primary zone for increas 30 the primary zone gas consisting essentially of
carbon monoxide, maintaining said powder in
ing its carbide content, separating from the dis
contact with carbon monoxide in the primary
charged hydrocarbon products a normally gas
zone at a temperature of about 390 to 400° F. for
eous hydrocarbon fraction, reacting said gaseous
a period of time ranging from about 1 to 60 min
fraction with said carbon dioxide to form carbon
monoxide and hydrogen, passing resulting carbon 35 utes such that cobalt is converted to cobalt car
bide in substantial amount in said stream of
monoxide to the primary reaction zone and pass
powder, continuously introducing gas consisting
ing resulting hydrogen to the secondary reaction
essentially of hydrogen to the secondary zone,
zone.
maintaining the powder containing cobalt car
6. A continuous cyclic process for catalytically
forming normally liquid hydrocarbons from car 40 bide flowing through the secondary zone in
contact wtih hydrogen at a temperature of about
bon and hydrogen by the use of a solid hydro
300 to 325° F. for a time of contact ranging from
genating catalyst containing a carbide-forming
metal selected from the group consisting of co
balt, iron and nickel which comprises continu
ously passing carbon monoxide gas through a .
primary reaction zone, introducing to said zone
a stream of said catalyst in powdered form, sus
a few seconds to about 5 minutes such that cobalt
carbide is re-converted to metal and resulting
liberated carbon is reacted with hydrogen to form
normally liquid and normally gaseous hydrocar
bons mainly of higher molecular weight than
pending the introduced powder in the body of
methane, continuously discharging said hydro
carbon monoxide gas moving through the reac
carbon products from the secondary zone, sepa
rating from the discharged products a normally
gaseous hydrocarbon fraction, reacting said
tion zone in the substantial absence of added free .
hydrogen, maintaining the gas and suspended
catalyst powder under elevated temperature con
ditions such that metal carbide is formed in sub
stantial amount in said catalyst, continuously
gaseous fraction with carbon dioxide to form car
bon monoxide and hydrogen, passing resulting
carbon monoxide to the primary reaction zone
withdrawing a stream of powdered catalyst con
and passing resulting hydrogen to the secondary
taining metal carbide, passing the withdrawn
catalyst stream while still at elevated tempera
ture to a secondary reaction zone, suspending it
zone.
within the reaction zone under conditions of ele
said carbon monoxide to contact therein with a
9. A continuous cyclic process for catalytically
forming normally liquid hydrocarbons from car
bon and hydrogen which comprises passing car
therein in a stream of hydrogen gas passing
through said secondary zone, maintaining the 60 bon monoxide in the substantial absence of hy
drogen to a primary reaction zone, subjecting
body of hydrogen gas and suspended catalyst
finely-divided solid synthesis catalyst containing
vated temperature such that metallic carbide is
a carbide forming metal, effecting said contact
decomposed and liberated carbon is reacted with
under conditions of elevated temperature such
hydrogen to form hydrocarbon products mainly
that carbon monoxide reacts with said metal to
of higher molecular weight than methane, dis
charging said products, continuously withdraw
form metal carbide in substantial amount, sep«
ing catalyst powder of decreased carbide content
arately removing catalyst and resulting gaseous
from the secondary zone and returning the with
products from said primary zone, passing re
drawn catalyst to the primary reaction zone.
moved
catalyst at elevated temperature to a sec
70
7. A continuous cyclic process for catalytically
ondary reaction zone, passing hydrogen in the
forming normally liquid hydrocarbons from car
substantial absence of carbon monoxide to said
bon and hydrogen which comprises establishing l secondary zone, subjecting said hydrogen to con
a continuous cyclic stream of powdered solid ad
tact with said hot catalyst containing metal car
sorptive containing cobalt flowing through a pair 75 bide in the secondary zone under predetermined
2,409,235
10
temperature conditions such that metal carbide
content and resulting hydrocarbon products from
is decomposed and resulting liberated carbon is
said secondary zone, recycling removed catalyst
reacted with hydrogen to form hydrocarbons
of decreased carbide content to said primary zone,
mainly of higher molecular weight than meth
separating carbon dioxide from said gaseous
ane, separately removing catalyst of decreased
products removed from the primary reaction zone,
carbide content and resulting hydrocarbon prod
reacting carbon dioxide so separated with a nor
ucts from said secondary zone, and recycling re
mally gaseous hydrocarbon under conditions suc‘i
moved catalyst'. of decreased carbide content to
as to form carbon monoxide and hydrogen, pass
said primary zone.
ing resulting carbon monoxide to the primary
10. A continuous cyclic process for catalytical 10 zone, and passing resulting hydrogen to the sec
ly forming normally liquid hydrocarbons from
carbon and hydrogen which comprises passing
carbon monoxide in the substantial absence of
hydrogen to a primary reaction zone, subjecting
said carbon monoxide to contact therein with a
ñnely-divided solid synthesis catalyst containing
a carbide forming metal, effecting said contact
under conditions of elevated temperature such
that carbon monoxide reacts with said metal to
form metal carbide in substantial amount, sep 20
arately removing catalyst and resulting gaseous
products including carbon dioxide from said pri
mary zone, passing removed catalyst at elevated
temperature to a secondary reaction zone, pass
ing hydrogen in the substantial absencev of car
ondary zone.
l2. A continuous cyclic process for catalytic
conversion of carbon and hydrogen into normally
liquid hydrocarbons which comprises maintaining
a stream of finely-divided solid synthesis catalyst
containing a carbide-forming metal flowing in
succession through a primary and then a Sec
ondary conversion zone in a continuously recur
ring cycle, reacting said catalyst in the primary
zone with at least one volatile carbon compound
supplied to the primary zone substantially free
of hydrogen, under elevated temperature condi
tions such that metallic carbide is formed on said
catalyst in substantial amount, subjecting result
25 ing carbide containing catalyst while in said sec
bon monoxide to said secondary zone, subjecting
ondary zone to contact with hydrogen under con
said hydrogen to contact with said hot catalyst
containing metal carbide in the secondary zone
ditions such that metallic carbide is decomposed,
the liberated carbon reacting with hydrogen .to
form carbon containing compounds mainly of
under predetermined temperature conditions
such that metal carbide is decomposed and re 30 higher molecular weight than methane, and dis
suiting liberated carbon is reacted with hydrogen
charging resulting compounds from the secondary
to form hydrocarbons mainly of higher molecular
reaction zone.
weight than methane, separately removing cat
alyst of decreased carbide content and resulting
13. A continuous cyclic process for catalytic
conversion of carbon and hydrogen into normally
hydrocarbon products from said secondary 35 liquid hydrocarbons, which comprises maintain
zone, recycling removed catalyst of decreased
carbide content to said primary zone, separating
ing a stream of finely-divided solid synthesis cata
lyst containing a carbide-forming metal ñowing
carbon dioxide from said gaseous products re
in succession through a primary and then a sec
ondary conversion zone in a continuously recur
moved from the primary reaction zone, reacting
carbon dioxide so separated with a normally 40 ring cycle, subjecting said catalyst While in the
gaseous hydrocarbon under conditions such as to
primary zone to contact with gas consisting of
form carbon monoxide and hydrogen, passing re
carbon monoxide under elevated temperature
sulting carbon monoxide to the primary zone,
conditions such that metallic carbide is formed
and passing resulting hydrogen to the secondary
on said catalyst in substantial amount, subjecting
zone.
45 resulting carbide containing catalyst while in said
11. A continuous cyclic process for catalytically
secondary zone to contact with hydrogen under
forming normally liquid hydrocarbons from car
conditions such that metallic carbide is decom
bon and hydrogen which comprises passing car
posed, the liberated carbon reacting with hydro
bon monoxide in the substantial absence of hy
gen to form carbon containing compounds mainly
drogen to a primary reaction zone, subjecting 50 of higher molecular Weight than methane, and
said carbon monoxide to contact therein with a.
discharging resulting compounds from the sec
finely-divided solid synthesis catalyst containing
ondary reaction zone.
a carbide forming metal, effecting said contact
14. A continuous cyclic process for catalytic
under conditions of elevated temperature such
conversion of carbon and hydrogen into normally
that carbon monoxide reacts with said metal to 55 liquid hydrocarbons, which comprises maintain
form metal carbide in substantial amount, sepa
ing a stream of finely-divided solid synthesis cat
rately removing catalyst and resulting gaseous
products including carbon dioxide and unreacted
alyst containing a carbide-forming metal ñowing
in succession through a primary and then a sec
ondary conversion zone in a continuously recur
carbon monoxide from said primary zone, sepa
rating carbon dioxide from the carbon monoxide
ring cycle, reacting said catalyst in the primary
in said gaseous products, recycling residual car 60 zone with carbon monoxide supplied to the pri
bon monoxide to the primary zone, passing re
mary zone substantially free of hydrogen, under
moved catalyst at elevated temperature to a sec
elevated temperature conditions such that metal
ondary reaction zone, passing hydrogen in the
lic carbide is formed on said catalyst in substan
substantial absence of carbon monoxide to said 65 tial amount, subjecting resulting carbide contain
secondary zone, subjecting said hydrogen to con
ing catalyst while in said secondary zone to con
tact with said hot catalyst containing metal car
tact with hydrogen under conditions such that
bide in the secondary Zone under predetermined
metallic carbide is decomposed, the liberated car
temperature conditions such that metal carbide
bon reacting with hydrogen to form carbon con
is decomposed and resulting liberated carbon is
taining compounds mainly of higher molecular
reacted with hydrogen to form hydrocarbons 70
mainly of higher molecular Weight than methane,
separately removing catalyst of decreased carbide
weight than methane, and discharging resulting
compounds from the secondary reaction zone.
HAROLD V. ATWELL.
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