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Патент USA US2106973

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Feb. 1, 1938.
Filed April 13, 1931
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L 1 GW/ '75
H2 —-—~——-~ HYDROGENA T/ON
Patented F55. '1, 1938
2,106,973 '
mnoennnnon 0F men OXYGEN (span
- Carleton ‘Ellis, Montclair, N. 3.,‘ assignor to
\ Standard-I. G. Company
‘Application- April 13, 1931, Serial No. 529,897
1 Claim. an. 196-53)
the formation of great quantities of methane
Anthracite coal is extremely di?lcult'to hydro
and is thus a dehydrogenation.
genate. .ilt is highly deficient in hydrogen as
compared with the hydrogen content of 'liquid ' It' is an object of the present invention to uti
hydrocarbons and is ‘very-dense, hence dif?cult lize the solid fuel which has passed from the peat
5 for hydrogen to penetrate the ground coal during stage and before it has entered into the bitumi- 5
the hydrogenation process. Bituminouscoal is nous stage to such a degree that substantial con
much less di?icult to hydrogenate, nevertheless .version to- fusain and durain has occurred. The
it contains certain components which are resist-v raw material of the preferred ‘form of the in
ant to hydrogenation. One of these is fusain. vention therefore is lignite in its various forms,
ranging from the near-peat stage to the begin- l0
ning of the bituminous stage or at least to the
point of incipient bituminization. It is an object,
10 Proposals have been offered to reduce ‘the fusain}
content of bituminous coal by grinding and sep
arating the ?nest portion or dust, the latter be
ing somewhat richer in fusain than the balance
however, to treat the lignite prior to hydrogena- '
tion in such a manner as to eliminate a consider
of the coal. This method of separation is, how
15 ever, incomplete. Durain is also diihcult to hy-‘
able part of its oxygen content, such oxygen con- 15*
tent being not that part which comes of! as water
‘but the oxygen which is otherwise combined,
such as that which appears during bituminization
as carbon dioxide. It will be understood that the
- drogenate, although not ' quite so resistant as
fusain. It has been proposed however, to re
move durain from coal by hand picking opera
tion, since the durain has a dull appearance and
20 the content of durain in the coal feed stock may
quantity of oxygen eliminated will depend largely 20
upon the temperature of the treatment and the.
time. to which the lignite is exposed to this tem
perature, as will be explained more fully below.
be considerably reduced by this treatment.
These methods of pretreatment, however, are
rather costly. Lignite, on the other hand, is
The deoxidation step according to; the present
quite readily hydrogenated to yield liquid prod
invention is carried’ out by heating the lignite 25
25 ucts. Owing to itshigh content of oxygen which
to eliminate first water and then oxygen as car
usually will exceed 15, percent, and frequently 20
bon dioxide or possibly in some cases or to some I
extent at- least .as carbon monoxide. Various _
percent or higher, the consumption of hydrogen
used in the liquefaction process is excessive.
proposals have been made for drying‘ lignite and -
Since hydrogen is costly to produce, this results
present time appears to be prohibitive.
carbonizing it more orless, but such‘ proposals 30
do not disclose a feature of my invention which
In the United States the lignite deposits con
stitute perhaps one-third of the‘total resources
tion of a substantial content of carbonized bodies
30 in a cost‘ for the entire treatment which at the
in solid fuels.
is rapid heating to deoxygenate without forma
0f thisamount of lignite, for . di?lcuit of hydrogenation.- In other words, I _
seek to eliminate a considerable part of the oxy- 35
alt-example, some six hundred billion tons are lo=
cated in deposits in the State of North Dakota.
Many of these deposits ca'n'be mined by the strip
ping ‘or pit method and the mining dost there
fore should be relatively low. Being more amen
40 able to reactionby hydrogen than solid fuels more
advanced in carbonization, the problem of com
mercial hydrogenation of lignite appears simpler
gen of lignite without applying heatin such a '
sustained manner that the slower stages, of car
bonization occur and material diil‘lcult to hydro
In, carrying out the invention lignite may be 40
ground and dried using, for example, a continu- ‘
ous drying method brought about by passing a
than that of similar treatment of bituminous or‘ stream of the lignite material through a drying "
anthracite ‘coal. However, the presence git/so
745 much oxygen in lignite constitutes, as indicated,
a drawback through undue consumption of the
costly element hydrogen.
It may be noted in connection with the forego
ing that the formation of lignite from peat-is
50 accompanied by the evolution mainly of water
and is thus a dehydration. The formation of
bituminous coal from lignite is accompanied by
the evolution of great quantities of carbon di
oxide and is thus a deoxidation, while the con
55 version of bituminous coal to anthracite involves
chamber which may be of the rotatable type.'
The lignite then is broughtginto a deoxygenating 45
chamber where it is rapidly heated with expul
sion of oxygen as carbon dioxide, the tempera- '
ture varying somewhat with di?erent grades of
lignite, but iirdinarily being- ‘somewhat above U
350° 0., preferably about 360° C.v the foregoing '60
step preferably being conducted at atmospheric
pressure. Higher temperatures than these can
be used in some cases, depending upon the vspeed
ofltravel of the stream of lignite- through the‘
deoxygenating zone, while in other'cases sub-,. 55
stantially lower temperatures may be used, es
pecially if the lignite contains its oxygen in a less
?rmly bound condition.
this phase of the invention is the following. Dis
til shale as noted and separate the distillate into:
1. Shale spirit.
It will thus be understood that there is a time
factor involved which may be utilized for the
2. Shale medium 011.
3. Shale tar.
purpose of deoxygenation without undue carbon
4. Total overhead from liquid phase hydrogen
ation of mixture of lignite and tar, preferably a
mixture of lignite, lignite tar and shale tar.
5. Lignite spirit from operation 4.
uisite temperature rapidly and quickly discharged _
6. Lignite medium oil from operation 4.
7. Lignite tar from operation 4.
therefrom. It is advisable to protect the dis
ization. By arranging .the process so as to have
the lignite, travel through the heating zone as a
continuous stream it may be broughtto the req
charging lignlte from the action of air by cover
ing the discharge end of the reaction chamber‘
and possibly in some cases ?ooding it with an in
ert gas.
Preferably the deoxygenated lignite is allowed
to ?ow into a container which is charged with tar
8. Mix medium oils°2 and 6 and subject to gas
phase hydrogenation.
9. Mix products 1 and 5 and light overhead _ '
product from 8 and hydro?ne or hydroform this
as the case may be to obtain a motor spirit
possessing high anti-knock qualities.
or heavyoil serving as a pasting oil. _ The putty '
' 10. Excess of product 3 and product '7 over the
or pasty material which is obtained in this way.
requirements of pasting oil for the lignite hydro
genation may be subjected to liquid phase hydro 20
after being ground if necessary, is conveyed to the
hydrogenation apparatus. The pasting oil which
is prepared for reception of the deoxygenated
lignite preferably is kept hot so as to be thin
enough to allow rapid submersion of the lignite.
The contents of the container so utilized if de- '
sired may be agitated in a suitable manner.
'Owing to the variation in the properties of lig
nite it will be impossible to lay down any de?nite
conditions for deoxygenation without carboniza
tion, it being desirable to test each grade of lig
nite to determine its facility of deoxygenation
and‘ tendency to carbonization and to carry out
the heating step to accomplish the maximum
.amount of deoxygenation belowthe stage of car- '
- bonization to materials di?lcult of hydrogenation.
A mixture of the deoxygenated lignite and
pasting oil in about equal proportions or varying
more or less according to the density orcompact
ness of the lignite particles may thus be secured.
It is conveyed to an apparatus equipped for by
gena‘tion to obtain lighter products followed by
gas phase hydrogenation to‘ yield light oils, spe
ci?cally motor spirit; the latter preferably being
incorporated with product 9.
while I have given these speci?c illustrations 25
of the invention, the invention may be varied in
aconsiderable number of ways and I believe that
such deviations from the foregoing, as will now
be evident‘to those skilled in the art, should form
a part of the present invention. For example,
some phases of hydrogenolysis do not require
catalysts, whileothers are conducted to very great
advantage byyusing catalytic material, especially
that which is recognized as sulphactive or ‘resist
ant to sulphur poisoning. Among such catalysts 35
molybdenum andz tungsten are particularly use
ful, however, other catalystsless costly may be
used in their stead or‘admixed therewith. In.
the liquid phase hydrogenolysis the catalyst is
preferably ?nely divided and employed in sump
drogenolysis in liquid phase, being introduced
_ oven procedurehwhile in gas phase hydrogenolysis
into the hydrogenator or reactor with hydrogen
at at least 100' atmosphera pressure and pref
the catalyst if used preferably is incorporated
with magnesium oxide, zinc carbonate, and the
erably 200 atmospheres or higher.
There it
like, and made up into small masses such as cubes
‘meetswith a body of oil containing'a catalyzer,. which can be charged into the hydrogenating
- for example one of the molybdenum chroinium reactor. ' Furthermore, the exact order ofvmix
type,‘ and undergoes the liquefying action of by? ‘ ing and treating the various distillates may vary,
drogen, the overhead being taken oi! as a-mixture as will now be evident. Re?ning methods other
of light and heavy oils. This process of treat— than hydro?ning may be used in some cases, in
ment is of the sump oven type.
The overhead from this operationis prefer
cluding sulphuric acid and alkali treatment, and
the like.
ably distilled to yield three fractions, ‘namely, .
The foregoing invention, therefore, in its pre
naphtha, medium oil ahd tar oil or tar. The ferred aspects will be seen to contemplate the
latter preferably forms the basis- of the pasting evaluation and utilization of vast deposits of
oil required as previously noted. The naphtha lignite, especially in conjunction with a similar, 55
is subsequently treated by gas phase hydrogena
evaluation and utilization of shale deposits.
tion to give a hydro?ned product, as will be sub
Were it not for the gumming qualities. of shale
sequently described. The fraction above the oil and the tremendous losses resulting in re
‘naphtha, which is somewhat similar in boiling
.range to a mixture of kerosene and gas oil, pref
?ning'to remove gum-forming constituents, shale
'oil might have come intouse to some extent in 60
erably is separated by ‘fractionation and later the past. as a motor fuel, but always these ob
submitted to gas phase hydrogenation.
stacles have confronted those interested in the
In various parts of the world shale deposits exist‘ exploitation of shale and have proved di?lcult to
in the neghborhood of lignite deposits. As one overcome. The present process provides means
modification of the invention I may utilize shale ' of utilizing the very valuable qualities of shale
oil, combining the treatmentlof shale distillates oil without re?ning losses. The structure'of shale those obtained ‘ from lignite liquefaction. oils is‘ such that their conversion by _ hydro
Thus shale may be distilled in any suitable way genolysis to anti-knock spirit of greatvalue is
' and the distlllateseparated by fractional distilla- '_ feasible and when such stock is incorporated with
tion into naphtha, medium‘ oil and tar oil. All that obtained from the hydrogenolysis of lignite,
of these are ‘very crude products, since shale very valuable motor spirit and even kerosene or
yieldsrhlghly unsaturated and~unstable liquid lubricating oils may be expected. This result,
products that are far from being suitable as vola- , moreover, is obtained from solid fuel deposits
*-Itileliquid fuels.
. _
which heretofore have been considered of a very
> u A schedule of treatmentwhich
illustrate ' low grade character and commercially unworkable
. a
termed an interhydrogenolate. Thus in the
sistant to hydrogenation. In, like‘ manner the
use or the'term deoirygenatedv lignite should not
convey that oxygen has been entirely removed,
since this ordinarily is impossible without carry
ing the reaction too far into the stage of carboni-r
zation. The term deoxygenated, therefore,
means that some part, presumably, a substantial
part of the oxygen of- the lignite has been re
treatment by hydrogen under gas phase condi
so long as an abundance of ordinary petroleumyls
, at hand.
Descriptive of the co-hydrogenation or hydro
genolysis of liquid fuels from different sources, as
for example, from lignite and shale, I prefer to
use the term interhydrogenation or interhydro
genolysis, the product derived thereby being
'10 tions of a mixture of crude spirit derived from
What I claim is:
Process of liquefying lignite to form useful liq
‘ I may, for example, carry out the operation at a .uid hydrocarbon oils, which comprises rapidly
temperature of 1,000" F. and. a hydrogen pressure heating the lignite in the absence of addedreduc
or rather a total pressure of a hydrogen-contain- ' ing gases and at approximately atmospheric pres
15 ing gasvof, say 200-400 atmospheres, whereby
sure to a temperature at least in the lower part 15
cyclicization and other conversions and reactions , of the range normally used for carbonization,
take place with the formation. of anti-knock maintaining the lignite at this temperature fora
bodies in abundance. A product so obtained time su?lcient to remove oxygen combined with
would be termed an interhydrogenolate. In _ carbon of said lignite and insu?icient to cause
20 using the term uncarbonized or substantially un
appreciable carbonization or liquefaction of the 20
‘carbonized, I do not mean to indicate that some I lignite, incorporating the deoxygenated non-car
sintering andpossibly a slight amount of car
bonized material‘ with a pasting oil, and subject
bonization may take place, but have innmind to ing the mixture to the action of hydrogen at high _
convey by the term uncarbonized that the struc
temperature and under high pressure.
ture of the lignite has not been so altered by car
bonization reactions as tobecome materially re
shale distillation and from lignite hydrogenolysis
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