EFFECT OF CATALYSTS ON HYDROGENATION OF COALS AND OTHER HIGH-MOLECULAR PRODUCTS, WITH PARTICULAR ATTENTION TO USSR CRUDE MATERIALS AVAILABLE FOR HYDROGENATION

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80-00809A000600400289-7
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 15
• Document Creation Date: December 22, 2016
• Document Release Date: August 25, 2011
• Sequence Number: 289
• Publication Date: July 13, 1951
• Content Type: REPORT

Sanitized Copy Approved for Release 2011/08/25 :CIA-RDP80-00809A000600400289-7
SUBJECT
HOW
PUBLISHED
WHERE
PUBLISHED
DATE
PUBLISHED
INFORMATION FROIA
FOREIGN DOCUMENTS OR RADIO BROADCASTS
~0~!~~DEN~'~Al.
CLASSIFICATION CONr IDE:VTIAL
Scientific - Chem~,sil~r~ synthetic liquid
fuels i rice::
Book
Moscow~Leningrad
1949
co r:o.
DATE OF
REPORT
nor oocunrr eorr~ur urorunor ~rnairo rrr rrnore~ omrsr
or rxr urino Iona nmr rxi ruruo or unor~e~ rv re
r. r. e.. ii ?ro n. As ~rrreao. m nerrrumor or rxr rrnunor
m m cornrn it Arr urru ro ?r ur~urxouao rumor it no?
rumu n ur. ^rnoournor or rx~r rorr a rroxu~no.
Iskusstvennoye Zhidkoye Toplivo, I, Gidrogenizatsiya Topliv, (Synthetic
Liquid Freels, Vo'_ I; ?.hydrogenation of Fuels) Gostop*ekk.~.izdat, 1949,
332 pp, (LC TP 343? R34) pp 128-140 and 244-24b??
EFFECT OP CATALYSTS ON HYDROG)iNATION OF COALS
AND OTHER HIGH-MOLECULAR PRODUCTS, WITH PARTICiTLAR ATTENTION
TO USSR ~CRLTDE MATERIALS A'IAILABLE FOR TIYDROGENATION
LThe following in.?ormation is taken from t:~+o ::h.rDters ~,a +,_r_< book indicated
under Source Identification.l
Effect of Catalysts (Chapter be, pp 128-140)
Bergius, in hie early work, paid no attention to the effect of catalysts,
which was a serious mistake. It has now been demonstrated th4t F.yd_regenation
is a catalytic process
1. Catalysts which are effective at atmospheric pressure end low tempera-
tures Ind, Pt, Ni). These catalysts are easily poisoned by sulfur compounds
and cons^quently are not suitable for the hydrogenation of cosls and tars. '
2. Catalysts which are effective at high pressures anfl temperatures and
are resistant to the !~.ction of sulfur compounds (Mo, W). These are used for
the hydrogenation of coals and tars.
Recent investigations have shown that iron catalysts or Ni-Mo an3 Ni-W
catalysts can be successfully used in individual phases of the hydrogenation
process after preliminary sulfurization. Mo and W catalysts are used either in
the form of oxides or sulfides of these metals.
- 1 -
CLASSIFICATION CONFIDENTIAL _c~~~~DE~r~
STATE NAW NSRa I DISTRIBUTION _
(ARMY AIR FBI - --
-.-.._ _.----.. __..__.. .. _. __. ._.. i
Sanitized Copy Approved for Release 2011/08/25 :_CIA-RDP80-00809A000600400289-7 r
 Sanitized Copy Approved for Release 2011/08/25: CIA-RDP80-00809A000600400289-7
1
U~1`i~a~~~ l l~~
CGNF IDE.NTIAL
In the hydrogenation of aromatic hydrocarbons which., for e:~taizsple, is carried
out over MoS2 at 420?r, at, a l~vdrog:n pressure of lOC atmospheres, the reaction
rate increases in tb.e folloviz;g sequence'
~6xF, < c6~3(cx3); C c6a~(c~3)2 < c6a5c~3 < ?108
The reJ.ativa activity of ::a.tai.yste is illustra.te~? in Table 1 (all tables are
appendedi. W7zile for liquid-phasa hyc'arogenatioa both stationary and floating
catalysts car. be used, stationary rztalysts would net be suitable for the hydro-
genation of coal. T'.e +nf luen:.e e-' the gain sire of dispersed catalysts on
liquid-phase ~vdrogeration, has been investigated by i. E. itapoport and G. Grit-
sevich. The results of ttis investigation are sumn~rized.c.n Table 2.
From the data in czizestion, it..follows that it is possible to xork with
small quantities of a colloidal catalyst which has bera homogeneously embodied
into the tar. When. such catalysts are used, it is necessary to stir the catalyst
paste continuously. In industrial practice,-iron catalysts are used for hydro-
genation, and their coucentr.at.ion in the oil often reaches a. value of 20-2596.
In the process of studying hydrogenation in the presence of a highly active
molybdenum catalyst, naturally it was of interest to determine the useful life
of the catalyst. There is always a small quantity of carboids deposited on the
surface of the catalyst, end the quantity deposited tends to reach a certain
constp~t value. The results listed in Table 3 were obtained by reusing Moo four
times. It can be seen from the data listed there that tha expenditure of c~ta-
lyst with reference to the amount of treated tar drops with each succeeding
cycle. Judging from the products ~:'~tained, the catalyst does not lose its actin:.
itjls? After the fourth cycle, the specific gravity of the residue did not change,
while the content of carboids amounted to more thy.. 0.1'f;. The content of car-
boids in t. residue after the fifth cycle was 0.12', while 0.4796 of coal dust
was intror' red with the tar. The specific gravity of th.e residue from the reactor
was 1.000v. Increase of the specific gravity of the residue may indicate occur-
rence of a certain amount of polymerization and condensation, but it is more
likely that aromatization proceeded to some extent.
In the opinion of L. S. Ai'tman and M. S. Nemtsov, the difference between
the txo groups of catalysts is due to the fact that the temperature coefficients
(magnitude of the. ohang&tzo.~x~?erofcthencatalysty Figuresppublish,dCbynA1'tmanider-
ably depending on the
and Nemtsov on. the apparent eaergy of activation E for various catalysts and
temperature coefficients calculated for temperatures of from 450 to 460?C indi-
cate that E for Mo catalysts is several times higher than for Pd, Pt, and Ni
catalysts. Thc- temper-~ture coefficient in the range 450-460oC fluctuates for
sulfide catalysts between 1,25 and 1.54 (depending on the catalyst and the sub-
stance being t~,ydrogenated) and fen reduced catalysts (Ni, Cu, Co, and Pd) be-
tween 1.08 and 1.12.
In tY,e course of th.e same investigation, Al'tmaa and Nemtsov have shown, by
calculating the rate of hydrogene.tion of toluene aver two catalysts (Pd and
MoS~), that even if the rate of hydrogenation over the .educe? Pd catalyst at
100 C is assumed to P.xceed the corresponding rate over molybdenum sulfide by a
factor of 100, molybdenum su:i ids at 45U?C will be 13 times mere effectdrr~ than
reduced palladium.
Anot:ner difference between high-temperature hydrogenati.oa catalysts (MoS2,
W52) and low-temperature metg7.:_ic catalysts (Pd; Pt, Ni) is *.hat, with an in-
crease of temperatua-e, the concentration of hydrogen nn the surface of catalysts
of the first type (MoS2, kS2) d.ces not change greatly becauoe of the loxer heat
of adsorption of hydrogen.; while or. r_atalysts of the second type (Pd, Pt, Ni)
Lwhich hgve a high ;neat. of hydLrogen adsorptio] at low pressures and tempera-
tures exceeding 250-300oC, the concentrations of both hydrogen and hydrocarbons
drop sharply, so that a ].ower.ed reaction rate results.
~O~~~QE~dTIA~.
Sanitized Copy Approved for Release 2011/08/25: CIA-RDP80-00809A000600400289-7~
 Sanitized Copy Approved for Release 2011/08/25: CIA-RDP80-00809A000600400289-7
Frgm the results outlined. above, it appears thst it would be possible to
recirculate repeatedly expensive catalysts like MoU~ after their partial with-
drawal from the system subseq~.ier_tly to each complete cycle.
Hydrogenation of coal in the liquid phase, representing the first stage
of hydrogenation, aims to convert the coal as completed as possible into oil.
The product of the first hydrogenstion stage is a mixture of high-molecular
compounds which yields only a small quantity of substances voiling below 200?C.
The hydrogenation of coal proceeds in such a manner that the product is a crude
material which is suitable both for further. conversion in the vapor-phase hydro-
genation stage (fractions boiling at 175-300-320oC) and for production of the
paste (residue boiling above 300-320?C). If the process of hydrogenation is
conducted in such a way that there will be, in eff"ecty only solution of the coal
ar_companied by partial hydrogenation, it will be necessary to interpose a supple-
mentary hydrogenation of the he&.vy oil to obtain a product suitable for further
conversion.
The liquid products obtained from coal resemble closely the high-boiling
fractions of primary tar. Under tiie circumstances, one may assume that molyb-
denum and wolfram compounds, which are the most efficient catalysts for the
hydrogenation of primary tar, cracking residues, and other crude r~.w materials,
xill also be perfectly suitable for the hydrogenation of coal. One drawback
is the high cost of these catalysts. They must be recovered and regenerated.
While the process of recovery after. hydrogenation of liquid nroduc+a is not too
complicated, it becomes highly complicated when treatment of the e.s}: residue
resulting after hydrogenatior. of coal is involved, For th t resson, nwny in-
vestigations have been devoted to the study of cheap catalysts which would not
have to be recovered.
I. B. Rapoport, M. Sudzilovskaya, and A. Khudyakova tested a number of cata-
lysts on various fossil combustibles which were both of the sapropelitic and
humus types. The experiments were carried out in an sutecisve equipped with a
stirrer (250 rpm). A paste with the composition 1:1 was used and 1$ of catalyst
was added during the preparation of the paste. Some of the results of this work
are cited in Table 4. Accor~i.ig to these results, the mos+, active catalyst is
MoS both in the pure state and with the addition of activators NiO, CaO, RO
~o~ Further identifie], an3 others. Mo03 was also found to be pretty good, al-
ughaceoztiif~g to tla~ 8=?itiah experimental sts+_io~ fcr fuel testing at Gillingham,
Moo 3e a.lesa active catalyst. -The yields of liquid products obtained in hydro-
ge~tion with Sn(OH)2 show that this catalyst is less active than MoS3 a.nd other,
mixed catalysts, This must be due to the method of preparing Sn(0$)~, because
the identical catalyst, when prepared differently, was previously shown to have
an activity practically as high as that of molybdenum catalysts.
Some of the most active catalysts were also tested on other coals, and
analyses of the liquid products were carried out. The results of this check are
shown in 'Fable 5. From these results, it follows that with the most active cata-
lysts MoS3 and MoS~ t RO a higher yield of hydrogenation products results, and
that these product have a lower specific gravity, while containing less asphal-
~tenes,
As far as substitution of molybdenum catalysts with leas expensive materials
is concerned, results based on work carried out in recent years are listed in
Table 6. The results listed there show that when the molybdenum sulfide catalyst
is replaced by a chromium catalyst, corresponding results are obtained only when
a much higher quantity of the latter is used. The use of a mixture of ferrous
oxide and ferric oxide necessitates raising the concentration of the Catalyst to
546, but the result is still inferior to that obtained with eithsr molybdenum
sulfide of a chromium catalyst.
C~~~~~~'hTlA1
_... _
Sanitized Copy Approved for Release 2011/08/25: CIA-RDP80-00809A000600400289-7
 Sanitized Copy Approved for Release 2011/08/25: CIA-RDP80-00809A000600400289-7
? 1
C~~~~~~~~~~1
c ors IDEN'r>;aL
Sulfur-containing iron catalysts have a b.igher activity t:nan iron oxides.
To obtain with the former ar. effect approaching that of McS3, the addition of
a quantity exceeding several times that of McSi is necessa,?y. Raising of the
hydrogen pressure from 200 to 700 atm permits Hydrogenation to be conducted Fitkl
iron catalysts ,just as effer_tivP.ly as with MoS3, under reduction of the expen-
diture of iron catalyst up to s certain Stage.
At German pleats, dispersed iron catalysts were used for hydrogenation in
the liquid phase. Fetros~farric oxide and i. on sulfate have received the widest
acceptance. The first usstance i.s a by-product of aluminum production and con-
tains 3596 of iron. Iron sulfate was used in combination with sodium sulfide.
These catalysts were used in a higY. state of dispersion for the hydrogenation
of tars and coal.
According to K. Gordon (L:nemicai Agt, 'i61-795, 1946), iron catalysts c:Fln-
not be used at pressures of 200-300 atm.. Actually, the answer to the question
as to whether iron catalysts can or cannot be used st 200-300 atm depends on
the chemical composition of the coal, Lignites and recently formed coals
liquefy very well in the presence of iron catalysts at. 200-300 atm. Geologically
older coals, Which require pressures up to 700 atm for ?hydrogenation, liquefy
with great difficulty at 200-300 stm ir_ th? presence of iron catalysts. At
700 atm, however, the process of liquefaction pror_~eds effectively enough even
in the presence of iron ;.atalysts.
At present, iron catalysts are ussa ied.ustrislly in the liquid-phase hydro-
genation of untreated. tars.
In the oth_r stages of industrial bydregenatien (intermediate hydrogenation
and final conversion into gascline), st.sti.onary r?ata.lysts deposited on activated
aluminum oxide and consisting of wolfram su.Lfl3e or wolfram su~ide containing
nickel sulfide are used. Specially prepfired molybdenum catalysis are also in
use.
Fission in Vapor-Phase H~rdrogenstion Stems (Chapter lOc, pp 244-246)
As far as cracking catalysts are ccri:err_=d, they must sh.o:.r the folio;ring
characteristics: (1) high activity, (2) _;. high degrFe ~? stability in prolonged
use, and (3) low sensitivity to poisoning. In regard to the efficiency of this
type of catalysts, N1. S. Nemtsov compiled the data of Tsbie 'i, which were supple-
mented in this instance by adding ~,ts sakes from G~cr'Je:C. industrial practice (the
last two lines of Table 7). Thf~ ~ffic'_ency (volumes of gasoline per volume of
catalyst per hour) of the Standar3 Oil Comg:.ny Lof New Jersey's, Catalysts B and
C is 2.4-2.7 times higher then t"y.t of the same ccmparr's Catalyst .A, The effi-
ciency of Germau industrial catalysts is 1.2-_