1. business and industrial
2. energy
3. oil

May 1,
IANUFACTURE. O1"` GARBURETING
»E AL PRUDHQM'ME
LIQUl-'DS- SIlILAR T0 PETROL
Filed Jan, zo. 192s
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änuentoz ,
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' A, 1,711,855,
Patented May 7, 1929.
UNITED STATES PATENT OFFICE.
EUGENE ALBERT PRUDHOMME, or NEUILLY-sUE-SEINE, rRANçE, AssIeNoE To so’
OIETE INTERNATIONALE .DES PEocEDEs PRUDHOMME (s. I. 1’. n), or PARIS,
FRANCE, A lJOINT-erom: COMPANY. '
MANUEACTUEE _or eAnBUEETING LIQU'IDS smrLAE To PETROL. .
t,
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Appneatioamed January 2o, 1925, serialNo. 3,655, and 11i-Trance nay-19, 1924.
process 150° C. and products such as tar vapors,
which condense only at very much higher
burants, using solid fuel, orl hydrocarbon temperatures, in -accordance with the inven- Í
fuel, of inferior grade as the Starting mate tion,-this` integral massfis conducted to the
5 rials, and converting the same into stable apparatus in which itis subjected y_to cata 55
liquid fuel enriched inA hydrogen.
l lytic treatment, and it has not given oíf its
The process comprises, in known manner, content ‘of heavy hydrocarbon, either as the
distillation at lowl temperature ofthe start ', result of an intentional condensing action or
ing materials (lignites, peats or .other mate of any stron , cooling action in the course of
10 rials) in a suitable apparatus (gas producer, its travel.
his- means, the intentional vre-V
`retort, distillation furnacel and the like)_ tention of the heavy hydroparbons in the
wherein the said materials, suitably heated, state ofïvapors in the gaseous mass to be,
The present invention relates _to
I ' 'of manufacturing saturated synthetic car
are traversed by a current 0f _hot gas or of
treated, rendered possible .by maintaining
vapors (water gas, steam, residual gases/of an appropriate temperature, is 'far from hav-_
-coking or of the manufacture of industrial lng for its purpose-and for-its exclusive re--
20
liquid fuels), the gas being'subjected to'a 'sult‘prevention of fouling of the catalysts
catalytic operation after it leaves the pro due `to~'c0ndensation of tars, which wouldducing apparatus and after previous purifi >mllitate rather in favor 4of the elimination ,
of the tars byy condensingthe sameI as com'- _ ‘
cation.
The invention>
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concerns certain 'improve-~ pletely as‘possible before 'the entrance of` 70
ments in these known processes, whereby as the gas into the catalyzin apparatus. The'.V "
a result of better utilization of the materials lmeans referred to have, a ove- all, for’their '
treated as well as of the calories, developed object and result the retention of the vapors
in the -course of their conversion into light of the useful tars in the massto be treated,'F products, a more economical and more rapid for the purpose of causing them to enter into l
»manufacture is madepossible; 'these im reaction in the catal sts which, as I have
provements assure, in' brief, an incomparably found7 eminently con uces to the enrichment
higher yield than is possible with existing »in hydrogen of the industrial product which
processes.
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~ .These improvements consistLin principle, '
issues from the catalyzing apparatus.
To state the matter differently, that which
of means which permit lof yintroducing into was heretofore considered an'obstacle'in the
the catalytic apparatusA wherein the V'first in manufacture of `light synthetic hydrocar- -' dustrial stage of transformationl finally’ter bons has been recognized by me as van advan
minates, a gaseous mass as rich as_possible
tage in such manufacture,
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Another essential.- feature ofthe invention,
in carbon, in hydrogen and in calories.
To this end, the gases leaving theproduccr complemental and indispensable to that just
apparatus (gas producer;- retort,I distillation referred to, is the construction of the’cata-l
furnace, and thev like) are integrally con
sa '
lyzer apparatus 4in such manner that ad
ducted `to the catalysts; they reach there vantage may be taken of the presence,- in
`having retained at least all the `useful heavy the mass to be treated,¿.iof the vapors of the aoV '
_ hydrocarbons, this result being'l obtained by". heavy hydrocarbons intentionally conducted;` i
maintaining in the entire-apparatus," includ i_t6 the apparatus.
ing 'the communicating conduits, a' tempera I' lTo this endv thecatalyzer apparatus is di
ture preventing any -condensationyfrom tak
gatherinto
a plurality
series
elements
them
ing place-and consequently preventingthe' -. vided
selves
asin.Well'fas-`
the and,v
communicating
ofthe
elements
joined
conduits-_Ãto- „9'5'j _.".f
o
.
'separation of theheavy. hydrocarbons. _'
The integral-mass ,of gases ,_ leaving the therebetweeen are maintained at a. suitable j -'
temperature _to prevent condensation, this `di-- whole of the products, yas .the olefines, which ' Z4vision of the catalyzerapparatus permitting
generator apparatus comprises,’in_,effect,ï'-the50
condense at temperatures Aof _about i100 to yapors of the heavier fractions to act accord
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1,711,855
For-this reason it is necessary to maintain .
`ing to their nature, as well as those which
condense at from' 150 to 200° C. Thus in in the purifiers and the conduits extending
a first catalyzer of the series I produce a to the catalyzer apparatuses a temperature
general hydrogenation, a deoxidation of the somewhat less than the temperature of con
bodies easily hydrogenated in the condition densation of the heavy fractions and in the
in which they issue .from the purifiers ar catalyzers a temperature not exceeding ap
ranged between the generating apparatus
and the catalyzers; the carbon monoxide
proximately 250° C.
’
70
f
.If, in a manner known to the art, instead
(CO) of the non-condensible products gives of treatingbnly the -gases~~of distillation or
10
rise, as is known, to the production of of gasification of fuel or of carbonaceous
meth-ane (CI-I4) ; but, at the same time, the starting material, these industrial materials
75
condensible bodies such as the phenols are treated by causing them to be traversed ,
(CGILOH) ‘lose their oxygen and pass into by a currentof hot gases or of vapors, using
for this purpose residual 'eoking gases or~
the state of benzines (CGHG).
l ' -
In this first preparatory catalysis the de gases evolved in...the industrial production 80
finitive enrichment cannot be- immediately of fuels, ‘either exclusively or otherwise, the
l effected, and for this reason the entire quan maintenance of the` calories and of the use
tity -of gas is conducted (all condensation al-` ful elementsin the mass subjected to catal
-ways being .prevented in the course of ysis is completed, in accordance with the in
20 travel) to a second catalyzer element, where vention, by the fact thatthe current of hot
it is prepared for the definitive enrichment, additional gases (residual gases only, -or
by a preliminary subdivision, or differently added gas such for example as water gas) is '
stated by a breaking of the chain, with re conducted, prior to its passage through the
lation to such bodies as methane (CHQ fresh materials under treatment, through a
which are to _be saturated as well as the sat body o_f hot coke resulting from a previous 90
urated bodies of the same series (decane,
ondeeane, dodecane, etc.) present in the va
30
operation’.
I
To state the action more definitely,` the
,
pors of the entrained tar vapors. This sub generator apparatus is divided, into two ele- '
division will permit, in a third element of ments which are traversed in series by the
the catalyzer series, a new hydrogenation hot aditional gases; one of these elements, 95
by the hydrogen evolved in the second ele-. the admission orentrance element, being the
ment. In the third element there is thus one which has been drained, in large part,
finally produced, simultaneously with poly by a preceding operation and thus contain
merization which is facilitated by the fact ing primarily hot coke, while the second ele
ment of the series is that which is to receive 100
saturation with _hydrogen of all the condensi- i the new charge to be treated, which is then
ble or noncondensible bodies whieh„in view in course of distillation, these two elements
35. that the hydrogen is in a nascent state, the
of this final saturation, were fragmented in alïiernatively acting in one capacity and the
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the second catalyzer apparatus. The fact that ot er.
In this mannerv a reheating of the addi- 105 '
hydrogen in 'the nascent state was prepared
in the second catalyzer apparatus thus fa tionalY gases (residual and others) 'is ob
cilitates the hydrogenation of the condens tained, 4and` consequfutly a recovery ofthe
ible bodies such as phenols. It will thus be calories contained in the coke, at the 'same
time that the carbon content of the addi
tional
-gases is increased; particularly the 11oy c
lyzers, of the condensible elements present
in the tar vapors is closely connected -to 4the carbonio~ acid gas contained in the 'hot' gases .
noted that the passage, up to within the cata
process ofeatalysis in a step by step action, passes into the state of carbon monoxide, a
the combination of these two means being gas which is well suited to promote'the op
one of the important characteristics of the eration of enrichment in hydrogen which oc
A. 50
invention.v
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curs in the catalytic apparatus.
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From what has been said above it will be
understood
that, inaccordance with the in
temperature to prevent condensation, during
v If care be takenito maintain _a suitable
the purification of the integral body of gas, vention, by following the cycle of operation
during its passage from the generator ap for eonverting'any given starting materials
;paratus, as well as-during the entire travel into synthetic liquid> fuel the maximum yield 120
of the integral .mass of gas from the evapo _is obtained, inasmuch as with `a minimum
ratorv to and- through the catalyzer. appara expenditure of caloriesl a maximum of light
’
-tuses, it will be clearly understood that this synthetic. fuel is produced.` '
_temperature progressively descends as the , For the practical application of the im- ~
60 issueofthe gases and vapors from the third proved process described above, an installa- l125
catalyzer is approached, this being so not tion similar to >that shown in the accompany- `
v only because the mechanical entraining of ing drawing Ina-y b'e >used, wherein Fig".Í 1
the ycondensible products in part prevents shows sehematicallyone. form of installation
their "condensation, but principally because for practicing theßprocess, Fig. 2 is a sche- K
c these 4products become -prog'gressively lighter. matic view of, another installation for prac- 130 4.
..31
1,711,855
ticing the process, and Fig. 3 is a vertical sec
tion of a particular ’arrangement of appara
tus such as shown in Figs. 1 and 2.
1 is a heating coil into which is introduced
the distillation gas which contains, for ex
nadium and nickel, heated to a temperature
varying between 200° and 250° C; the meth
ane is dehydrated with a formation of acet
ylene and hydrogen. As -a matter of fact,
and as above explained, a breaking'up or
ample, hydrogen and _methane in substan dividing iselïected, as to the bodies such as
tial proportlons, carbon monoxlde, azote and` methane which are to be saturated as well
hydrocarbons ofthe (LI-In type in very small _as to the bodies of the 'same series (decane,
proportions.
15
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ondecane, dodecane, etc.) and which have
'
The heated gas traverses downwardly, the been brought to the state of saturation, by' 75
retorts 2 containing a fuel, for example reason of the conservation or retention of
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lignites. In these retorts, -the gas causes the'tar vapors.
distillation at low temperature lof the lig
Finally, the gaseous mixture, which has
nitesp. The gases evolved by this distillation become very rich in acetylenic carbons passes
contain carbon monoxide, hydrogen, and for into' 6`over pumice charged with nickel and 80
example 15‘to 20% of unsaturated gaseous cobalt and heated to about 180° C., thereby
hydrocarbons. 'I thus obtain a complex gas causing polymerization of the aeetylenic
hydrocarbons simultaneously with the satu
eous mixture containing a substantial pro
20
portionof acetylenic hydrocarbons (11H2n~2
' ration lwith hydrogen of all the bodies which
and, in unstable equilibrium, a certain num
ber of those hydrocarbons tending to con
dense to form tar. The temperature in the
retort 2 and in the adjacent passages is main
tained at a degree sufficient toA completely
prevent such condensation.
.had been fragmented in the second catalyzer
apparatus. Therevis thus finally obtained
at the outlet of the catalyst tube 6 a poly»
merized acetylenic mixture of'hydrocarbons
Which may be easily condensed in a cooled
coil 7 and collected in the receptacle 8.
90
The integral gaseous mixture, i. e., the
The residual gases not condensed in the
gaseous mixture which contains at the same receptacle 8 may be either returned to the
time the permanent gases and the._|,read_ily coil 1 if they are sufficiently rich in hydro-V
condensiblevapors, passes into a purifying carbons, or used to heat the apparatus.
30
apparatus 3 containing a purifying mixture '
such as the Laming mixture, which is a mix
ture of lime Aand oxide of iron rendered po
_These liquidv products _present variable
compositions which render them more or less
analogousy to IAmerican gasoline, Caucasian ~
rous by sawdust and heated to a suitable gasoline or Galician gasoline, of which they
temperature. This mixture frees the gas
have substantially the composition, the odor,
- eous current ofthe major part of the sulphur the appearance and the density. .
y100
which it contains and which results, particu-`
In the operation of the above described
larly, from the distillation of lignites. The process the temperatures of all the passages,
temperature to which the purification appa of the mixture purifier 3 etc., are as above
ratus is heated prevents all condensation of lstated, maintained at such values that yno
40
the vheavy hydrocarbons of the gaseous'mix condensation of the oils or the tars occurs.
i
'I‘he.„n_1__aterial which thus issues from Consequently, these tars cooperate with a
ture.
the purifying apparatus 3 is a'gaseous mix part of the uncondensible gases contained
105
. ture freed of the major part of its noxious in the hot gases of distillation or of gasi
ingredients, of its sulphur particularly, and Vfication to form uncondensible gases and
charged with acetylenic hydrocarbons, the
liquid carburants.
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‘effect of which is'to facilitate the step by -As shown schematically i.. Fig. 2, the y
step or stage operation of catalysis, here installation may comprise a divided genera
inafter described, and to facilitate and reg tor apparatus, for example two distillation
ula-te the conversion of the gaseous mixture retorts Z9 and c, so related as to constitute
50 into liquid carburant.
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alternatively a generator apparatus proper
>The gaseous. mixture issuing from ~the and a coking column serving to reheat
purifying apparatus next passes into 4 over additional gases _which take additional cal
a first catalyzer tube of pumice stone impreg
nated with nickel powder and heated to be
tween 180° and 200° C. I thus cause the
formation of a substantial quantity of meth
ane in the gaseous mixture, while the phenols
,ories' and carbon from the coke.
By feeding the additional gases through '
the conduit a, and assuming then that the
retort b is charged with hot coke vresulting
120
from the partial exhaustion of the starting
pass `over into the state of benzines. In materials which are to be treated, these gases
other words, as stated> above, a general hy passing from >a to b and thence in_to t'. then
drogenation is effected in the first. catalyzer charged with fresh materials, the integral
~
body of gases >from c to- d, thence-through
apparatus.
The mixture thus charged with methane a purifier e into the eatalyzer apparatus f
v and containing nevertheless a certain prom constructedas abovey described.
portion of acetylenic hydrocarbons' passes
into 5 over pumice stone provided with va
i
‘When thea mass c has been converted into
coke by distillation and the retort b emptied
130
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4
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of its vcontents,.the retort is charged with evaporation in a Iseries of catalyzers charged
fresh materials. The additional gases are successively with nickel, with vanadium and
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then .first conducted from a to c, and there nickel, and with nickel and cobalt.
7. A process for manufacturing liquid
fuels
-Which consists in vaporizing hydro
5 f Practically to reduce to the minimum the
~ losses of calories and to assure the appli carbon products, treating the products of
afterv through b, d and f.
cation of the process of catalysis in stages ` evaporation to the catalytic action of nickel
of the integral mass -of purified gas having at a temperature between 180° and 200° C.,
retained the useful heavy hydrocarbons, it is then of nickel and vanadium al a tempera
10 desirable to arrange» in‘heavy masonry the ture between 2006 and 250° C., then of nickel
retorts or distillation l»furnaces 1,-and 2, the and cobalt at a temperature of approximate
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purifying apparatus 3 and the catalysis ap ly 180° C., and condensing fthe resulting
products.
'
paratus in stagesßi, 5 and G (Fig. 3).
8. 4A process for' manufacturing li uid
1,'-A process for manufacturing liquid fuels which comprises d_istilling hydrocar on
fuels which consists in subjecting hydrocar products, passing a current-of hydrogen con
bon vapors to a staged catalysis in a series.: taining gas over said products in course of
of catalyzers which effect in ‘ successive distillation, and treating the combined gas
‘I
claim:
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‘ catalyzers ageneralhydrogenation of said and ydistillation products in a series vof
catalyzers effecting in successive catalyzers a 85
up of said products intoA unsaturated hydro hydrogenation of the combined products, a
carbons, and a saturation and polymerization splitting upinto unsaturated hy rocarbons,
and a saturation and polymerization of said
of said products.
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2. A process for manufacturing liquid products.`
9. A process for manufacturing liquid"
25 fuels which consists in subjecting hydrocar
' 2.0 products, a dehydrogenation or a splitting
bon vapors to a staged catalysis in a series fuels which comprises distilling hydrocarbon ' y
of catalyzers -which _ effect in` successive products, passing a current of hydrogen con
catalyzers a general hydrogenation of such taining gas through the residuum of a previ
products, a splitting up of said hydrogenated ous distillation and then' through the prod
ucts in course of distillation, purifying'the
combined
gas and distillationproducts, sub
eration of hydrogen, and~ asaturation and.y
polymerization of said unsaturated bodies. jecting said combined products to a staged->
3o products into‘unsaturated bodies vWith lib
3. A process for manufacturing liquid catalysis effectin in successive catal zers a
fuels which consists lin subjecting hydro _hydrogenation o the -combined r ucts, a>
35 carbon vapors to a“4 staged catalysis in a splitting up' into unsaturated hy rocarbons,
series ofv catalyzers',v effecting in successive and a saturation and polymerization of said
catalyzers a general hydrogenation, a split products, and condensing the hydrogenated
ting up of the hydrogenated roducts into
products.-
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_
unsaturated'hydrocarbons, an a saturation _ 10. A process for manufacturing li uid
fuels which consists in distilling hydrocar on
40- and polymerization of said unsaturated
hydrocarbons, the temperature being ma1n-‘
' tained sufliciently high to avoid condensation
I of the heavy fractions.
4. A process for manufacturing liquid
45 fuels which consists in vaporizing hydrocar
bons and subjecting the products of evapora
'-products, passing a hydrocarbon containing
50 carbons, and then a saturation and polymeri
products While maintaining a temperature
throughout sufliciently high to prevent con
105 .
gas through the residuum of a previous dis
tillation and then over said products in
course of distillation, and treating the 4com
bined- gas -and distillation products in a se
110
ries of successive catalyzers effecting a hydro
tion to a successive catalysis effecting in suc -genation' of the combined products, a split
and _
cessive steps first a general hydrogenation, _ting ~-up into unsaturatedhydrocarbons,
then a splitting up into unsaturated hydro a' saturation and olymerization of said °
' zation of said products.v
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115
densation of the heavy -fractions.
11. In a process for manufacturing liquid 'l
fuels which consists in> vaporizing hydrocar fuels
whichconsists in subjecting hydrocar
' bons and subjecting said vapors to a staged
, 5.A A process for manufacturing `l1quid
»35 _ catalysis in a series of catalyzers,_eifecting in bons to staged catalysis in a series of suc 120 f
successive catalyzers -a gener-al hydrogena cessive* catalyzers, _the steps -of saturating a _.
hydrocarbon of low molecular weight, chang
tion, a splitting up of the
said saturated hydrocarbon _into an un
ucts into unsaturated hy rocarbons, and a ing
saturated
_hydrocarbon of higher molecular-- I
- saturationand polymerization' of said unsat
i
ht,
and
saturating said last named
We
the
temperature
being
C0 urated hydrocarbons,
_
rocarbon
in
successive catalyzers.
. maintained ysufficiently high' to avoid conden
12. A process for manufacturing li uid
hâfdrogenated prod
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.
satioiÄof the
heavier
rocess
lfor -fractions.
manufacturing
_liquid fuels which consists in vaporizing hy ro- _
6.
‘ fuels which> consists in vaporizing hydrocar carbon products, conducting said vaporized
_ 65 bon products and'treating the products of products 'through a purifying element to a
130
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1,711,855
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series of catalyzers,.and effecting in succes- vaporizin apparatus to the catalyzers
sive catalyze/rs a general hydrogenation, a' through t e puri?ylin element being main
'splitting up of the hydrocarbon products tained suíiìciently ig to prevent condensa- 1
¿into unsaturatedhydrocarbons, and a'satu'ra- tion of the heavler fractions.
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5 tion and polymerization" of said unsaturated - 'In testimony whereof I afîìx my signature._
hydrocarbons, the tem erature of the Vapor-
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ized products during-t eil' passage from the - EUGÈN ALBERT PRUDHOMME.
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