Note: Descriptions are shown in the official language in which they were submitted.
~4~1Z5
A promising technique for recovering hydrocarbons from carbonaceous
materials is a process called dense fluid extraction. Separation by
dense fluid extraction at elevated temperatures is a relatively un-
explored area. The basic principles of dense fluid extraction nt .
elevated temperatures are outlined in the monograph "The Principles of
Gas Extraction" by P. F. M. Paul and W. S. Wise, published by Mills and
Boon Limited in London, 1971, Chapters 1 through 4. The
dense i-luid can Se either a liquid or a dense gas having
a liquid-like density.
Dense fluid extraction depends on the changes in the properties
of a flllid - in p~rticular, the density of the fluid - due to chanr~as In
the pressure. ~t temperatures below its critical temperature, thc
density of a fluid varies in step functional fashion with changes in the
pressure, Such sharp trsnsitions ln the density are associated with
vapor-liquid transitions. At temperatures above the critical temper~ture
of a fluid, the density of the fluid increases almost linearly with
pressure as requlred by the Ideal Gas Law, although deviations from
linearity are noticeable at higher pressures. Such deviations are more
marked as the temperature of the fluid is nearer, but still above, its
critical temperature.
If a fluid is maintained at a temperature below its critical tem-
perature and at its saturated vapor pressure, two phases will be in
I
~ )125
equilibrium with each other, liquid X of density C and vapor Y of
density D. The :Liquid of density C will possess ~ certain solvent power.
If the same fluid were then maintained at a particular temperature above
its critical temperature and if it were compressed to density C, then
the compressed fluid could be expected to possess a solvent power
similar to that of liquid X o:f density C. A similar solvent power could
be achieved at an even higher temperature by an even greater compression
of the fluid to density C. However, because of the non-ideal behavior
of the fluid near its critical temperature, a particular increase in
pressure will be more effective in increasing the density of the fluid
when the temperature is slightly above the critical temperature than
when the temperature is much above the critical temperature of the flu:Ld.
These r,impl.e cons:Lderations lead to the suggest:Lon that at a g,Lven
pressure and at a temperature above the crit:Lcal temperature of a com-
pressed .~lu:Ld, the sol~ent power oE the compressed fluid should be
greater the :Lower the temperature; and that, at a given temperature
above the critical temperature of the compressed fluid, the solvent
power of the compressed fluid should be greater the higher the pressure.
Although such useful solvent effects have been found above the
critical temperature of the fluid solvent, it is not essential that the
; solvent phase be maintained above its critical temperature. It is only
essential that the fluid solvent be maintained at high enough pressures
so that its density is high. Thus, liquid fluids and gaseous fluids
which are maintained at high pressures and have liquid-like densities
are useful solvents in dense .Eluid extractions at elevated temperatures.
The basis oE separatlons by dense fluid extraction at elevated
temperatures is that a substrate is brought into contact with a dense,
compressed fluid at an elevated temperature, material from the substrate
is dissolved in the fluid phase, then the fluid phase containing this
dissolved material is isolated, and finally the isolated fluid phase is
10401Z5
decompressed to a point where the solvent power of the fluid is destroyed
and where the dissolved materi~l is separated as a solid or liquid.
Some general conclusions based on empirical correlations have been
drawn regarding the conditions Eor achieving high solubility of sub-
strates in dense, compressed fluids. For example, the solvent effectof a dense, compressed fluid depends on the physical properties of the
fluid solvent and of substrate. This suggests that fluids of different
chemical nature but similar physical properties would behave similarly
as solvents. An example is the discovery that the solvent power of com-
pressed ethylene and carbon dioxide is similar.
In addltion, it has been concluded that a more ef~icient dense
fluid extraction should be obtained with a solvent whose critical tem-
perature is nearer the extraction temperature than with a solvent whose
critical temperature is farther from the extraction temperature. Further
since the solvent power of the dense, compressed fluic1 should be greater
the lower the temperature but since the vapor pre~sure o~ the materlal
to be extracted shotlld be greater the higher the temperature, ~he choLce
o~ extraction temperature should be a compromlse between these opposing
effects.
Various ways of making practical use of dense fluid extraction are
possible following the analogy of conventional separation processes.
For example, both the extraction stage and the decompression stage afford
considerable scope for making separations of mixtures of materials.
Mild conditions can be used to extract first the more volatile materials,
and then more severe conditions can be used to extract the less volatile
materials. The decompression stage can also be carried out in a single
stage or in several stages so that the less volatile dissolved species
separate first. The extent of extraction and the recovery of product on
decompression can be controlled by selecting of an appropriate fluid
solvent, by ad~justing the temperature and pressure of the extraction or
1~46~1Z5
¦ dccompre.ssioll, alld hy alter~n~ the rnt~o Or .~uh.~tr;lte-to-flul(l .~olvent
¦ whicll ls chllrged to the extraction ves.4eL.
In general, dense flu~d extraction nt elevaeed temperatures can
s be considered as an alternative, on the on~ hand, to diseillation and,on the other hand, to extraction with llquid solvents at lower tempera-
tures. A considerable advantage of dense fluid extraction over distil-
lation i9 that it enables substrates oE low volatility to be processed.
Dense fluid extraction even offers an aleernative to molecular distll-
lation, but with such high concencrations in the dense fluid phase
0 that a marked advantage in throughput should result. Dense fluid
extraction would be of particular use where heat-liable substrates have
~ to be processed since extraction into the dense fluid phase can be
; effected at témperatures well below those required by distllation.
A con~iderable advantage of dense flui~ extraction at elevate~
~5 tempera~urcs over liquld extractlon at lower temperatures ls that the
solvent power of the compressed fluld solverlt can be continuously con-
trolled by adjusting the pressure instead of the temperature. Having
available a means of controlling solvent power by pressure changes gives
;~ a new approach nnd scope to .solvent extraction processes.
Zhuze was apparently the Eirst to apply dense fluid extraction to
chemical engineering operations in a scheme ~or de-asphalting petroleum
fractions using a propane-propylene mixture as gas, as reported in
Vestnik Akad. Nauk S.S.S.R. 29 ~11), 47-52 (1959) and in Petroleum
2s (London) 23, 298-300 (1960~.
Apart from Zhuze's work, there have been ~ew detailed reports of
attempts to apply dense fluid extraction techniques to substrates of
commercial interest. British Patent No. 1,057,911 (1964) describes the
principles of gas extraction in general terms, emphasizes its use ,lS a
separation technique complementary to solvent extraction and distillation,
and outlines multi-stage operation. British Patent No. 1,111,422 (1965)
refers to the use of gas extraction techniques for working up heavy
petroleum fractions. A feature of particular interest is the separation
of materials ir.to residue and extract products, the latter being free
5 from objectionable inorganic contaminants such as vanadium. The advantag
is also mentioned in this patent of cooling the gas solvent at sub-
crltical temperatures before recycling it. This converts it to the
liquid form which requires less energy to pump it against the hydro-
static head in the reactor than would a gas. French patents 1,512,060
(1967) and 1,512,061 (1967) mention the use of gas extraction on
lo petroleum fractions. In principle, these seem to follow the direction
of the earlier Russian work.
In addition, there are other reEerences to recovery o~ upgraded
hydrocarbon Eractions ~rom carbonaceous materlals by processes utillzLng
water. For example, Friedman et al.~ U.S. Patent No. 3,051,644 (1962)
discloses a process ~or the recovery of oil from oil shale which involves
sut~ecting oil shale particles dispersed In steam to treatment with
steam at a temperature in the range o-f from 700F. to 900F. and at a
pressure in the range of from 1000 to 3000 pounds per square inch gauge.
Oil from the oll shale ls withdrawn in vapor form admixed with steam.
Truitt et al., U.S. Patent No. 2,665,238 (1954) discloses a method
of recovering oil from oil shale which involves treating the shale with
water in a large amount approximating the weight of the shale, at a
temperature in excess of 500F. and under a pressure in excess of 1000
pounds per square inch. The amount of oil recovered increases generally
as the temperature or pressure is further increased, but pressures as
high as about 3000 pounds per sguare inch gauge and temperatures at
least approximately as high as 700F. are required to effect a sub-
stantially complete recovery of the oil.
30Pevere, et al., U.S. Patent No. 2,665,390 (1948) describes in
general terms a process for dissolving coal in liquid solvents at high
- 5 -
~.~46~25
temperatures and then atomizing the solution into a carbonizer but does
not mention the use of supercritical conditlons. U.S. Defensive Publi-
cation 700,485 (filed January 25, 1968) refers to the use of a gas
extractant to recover, from a solution of coal in a liquid solvent a
fraction suitable as a feedstock for hydrocracking to gasoline.
Seitzer, U.S. Paetnt No. 3,642,607 (1972) discloses a process for
dissolving bituminous coal by heating a mixture of bituminous coal, a
hydrogen donor oil, carbon monoxide, water, and an alkali metal hydroxide
or its precursor at a t2mperature oE about 400-450C. and under a total
pressure of a~ lea~st about 4000 pounds per square inch gauge.
Seitzer, U.S. Patent No. 3,687,838 (1972) discloses the same
process as disclosed in U.S. Patent No. 3,642,607 (1972) but employs
an al~ali metal or ammonium molybdate instead oE an alkali metal
hydroxlde Or lts precursar.
Urban, U.S. Patent No. 3,796,650 (1974) dlscloses a process Eor
de-ashlng and llqueeyln~ coal which comprlses contacting comminuted
coal with water, at least a port:Lon oE whlch 1.8 :Ln the liquid phase, ~ln
exterually supplied reduc-lng gas and a compo~md selected from nmmonin
and carbonates and hytlroxides of alkali metals, at liquefaction con-
ditions, including a temperature of 200-370C. to provide a hydro-
carbonaceous product.
There have been numerous references to processes for cracking,
desulfurizing, denitrifying, demetalating, and generally upgrading
hydrocarbon fractions by processes involving water. For example, Gatsis,
U.S. Patent No, 3,453,206 (1969) discloses a multi-stage process for
hydrorefining heavy hydrocarbon fractions for the purpose oE eliminating
and/or reducing the concentratlon oE sulfurous, nitrogenotls, organo-
metallic, and asphaltenic contaminants therefrom. The nitrogenous
and sulfurous contamlnants are converted to ammonia and hydrogen sulflde.
The stages comprise pretreating the hydrocarbon fraction in the absence
1040~Z5
of a catalyst, with a mixture of water and externally supplied hydrogen
at a temperature above the critical temperature of water and a pressure
of at least lO00 pounds per square inch gauge and then reacting the
liquid product from the pretreatment stage with externally supplied
hydrogen at hydrorefining conditions and in the presence of a catalytic
composite. The catalytic composite comprises a metallic component
composited with a refractory inorganic oxide carrier material of either
synthetic or natural origin, which carrier material has a medium-to-
o high surface area and a well-developed pore structure. The metallic
component can be vanadlum, niobium, tantalum, molybdenum, tungsten,
chromium, iron, cobalt, nickel, platinum, palladium, iridlum, osmium,
rhodium, ruthenium, and mixtures thereof.
Gntsi~, U.~. Patent No. 3,501,396 (1970) discloses a process ~or
desulfurlzlng ancl clen:LtrLfylllg oi~ whieh comt)rlses mLxlng the oLl
wLth water at a temperatu~e above the critical temperatllre o~ water llp
~o abouk 800F. ancl at a pressure in the range of from ahout 1000 to
nbout 25~0 pounds per square lnch gat~ge and reacting the resulting
mixture with externally supplied hydrogen in contact with a cataLytic
composite. The catalytic composite can be characteri~ed as a dual
function catalyst comprising a metallic component such as iridium,
osmium, rhodium, ruthenium and mixtures thereof and an acidic carrier
component having cracking activity. An essential feature of this method
is the catalyst being acidic in nature. Ammonia and hydrogen sulfide are
produced in the conversion of nitrogenous and sulfurous compounds,
respectively.
Pritchford et al., U.S. Patent No. 3,586,621 (1971) discloses a
method for converting heavy hydrocarbon oils, residual hydrocarbon
fractions, and solid carbonaceous materials to more useful gaseous ancl
liquld products by contacting the material to be converted with a nickel
spinel catalyst promoted with a barium salt of an organic acid in the
- 7 -
1~34~)1Z5
¦ presence of steam. ~ temperature in the range of from 600F. to about
¦ 10~0F. and a pressure in the range of from 200 to 3000 pounds per
¦ square inch gauge are employed.
l Pritchford, U.S. Patent No. 3,676,331 (1972) discloses a method for
¦ upgrading hydrocarbons and thereby producing materials o-f low molecular
¦ weight and of reduced sulfur content and carbon residue by in~roducing
¦ water and a catalyst system containing at least two components into the
¦ hydrocarbon fraction. The water can be the natural water content of the
¦ hydrocarbon fraction or can be added to the hydrocarbon fraction from an
¦ external source. The water-to-hydrocarbon fraction volume ratio is
¦ preferably in the range from about 0.1 to about 5. At least the first
¦ of the components of the catalyst system promotes the generation of
¦ hydrogen by reaction of water in the water gas shift reaction and at
¦ least the second o~ the components oE the catalyst system promotes
reaction hetween the hydrogen generated and the constituents of the
hydrocarbon fraction. Sultnb:Le materials ~or use as the ELr9t component
of the catalyst system are the carboxylic ncid salts o~ barium, calcium,
stronLlllm, and magneslum. Suitable materials for use as the second
component of the catalyst system are the carboxylic acid salts of
nickel, cobalt, and iron. The process is carried out at a reaction
temperature in the range of from about 750F. to about 850F. and at a
pressure of from about 300 to about 4000 pounds per square inch gauge in
order to maintain a principal portion of the crude oil in the liquid
-` 25 state.
; Wilson et al., U.S. Patent No. 3,733,259 (1973) discloses a process
for removing metals, asphaltenes, and sulfur from a heavy hydrocarbon
oil. The process comprlses dispersing the oil with water, maintaining
this dlspersion at a temperature between 750F. and 850F. and at a
pressure between atmospheric and 100 pounds per square inch gauge,
cooling the dispersion after at least one-half hour to form a stable
-
zs
water-asphaltene emulsion, sepa~ating the emulsion from the treated oil9
adding hydrogen, and contacting the resulting treated oil with a hydro-
genation ca~alys~ at a ~emperature between 500F. and 900F. and at a
pressure between about 300 and 3000 pounds per square inch gauge.
It has also been announced that the semi-governmèntal Japan Atomic
Energy Research In~titute~ working with the Chisso Engineering Corpora-
tlon, has developed what is called a "simple, low-cost, hot-water, oil
desulfurization process" said to have "sufficient commercial appli-
cability to compete with the hydrogenation process." The process itself
consists of passing oil through a pressurized boiling water tank in
which water i~ heated up to approximately 250C., under a pressure of
about lO0 atmospheres. Sulfides in oil are then separsted when the
water tempera~ure is reduced to less than 100C.
Thus far, no one has dlsclosed the method of this invention for
recovering and upgrading hydrocarbon fractions from carbonaceous
materials, which permits operation in a single step at lower than
conventional temperatllres, without an external source of hydrogen, and
wlthout preparation ~r pretreatment, such as, desalting or demetalatlon, I
prior to upgrading the recovered hydr~carbon fraction.
Thus the present invention provides a process for
recovering upgraded hydrocarbon products from a carbonaceous
material selected from the group consisting of oil shale
solids, tar sands solids, coal solids, and a hydrocarbon
fraction containing paraffins, olefins, olefin-equivalents, .
or acetylenes, as such or as substituents on ring compounds,
comprising contacting the carbonaceous material with a water- I
containing fluid at a temperature in the range of from about
600F. to about 900F,, ln the absence of externally supplied
hydrogen, and in the presence of an ~xternally supplied,
sulfur-resistant catalyst, selected from the group consisting
_ g_
Z~
of at least one basic metal carbonate, basic metal hydroxide,
txansition metal oxide, ox~de-forming transition metal salt,
and co~binations thereof, wherein the density of water in the
water-containing fluid is at least 0.10 gram per milliliter
and sufficient water is present in the water-containing fluid
to serve as an effective solvent for the recovered hydrocarbons.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graph showing the correlation of the calcination
weight loss of oil shale solids with the results of the Fischer assay
of such solids.
Figure 2 is a series of plots showing the dependence on temperature
of the yields of hydrocarbon products from oil shale using the method of
this lnvention.
Figure 3 is a series of plots showing the dependence of the yields
of oil and bitumen from oil shale upon the particle size of the oil
shale and upon the contact time using the method of thls invention.
- 9(a) -
e~
~, ~
~403 25
Figllre 4 is <~ series of plots showing the dependence of the oil
solecLivlty u~ e particle si%e of the oll .shale nnd upon ~he cf-nt~(t
time using the method of this invention.
Figure 5 is a schematic diagram of the flow system used for semi-
continuously processing a hydrocarbon fraction.
DETAILED DESCRIPTION
It has been found that hydrocarbons can be recovered from carbonaceo s
materials and that the recovered hydrocarbons can be upgraded, cracked,
desulfurized, and, if the carbonaceous material is tar sands solids,
oil shale solids, or a hydrocarbon fraction containing paraffins,
olefins, olefin-equivalents, or acetylenes, as such or as substituents
on ring compounds, demetalated by contacting the carbonaceous material
with a den~se-water-containlng phase, either gtS or llquicl, at a reactLon
temperature ln the range of from about 600F, to a`bout 900F. ln the
absence of externally supplied hydrogen, and in the presence of an
externally supplied sulfur-resistant transition metal catalyst. When
the carbonaceous materisl is coal solids, the solid coal remaining
after treatment by the method of th~s invention is desulfurized. This
method is applicable to the whole range of hydrocarbon fractions,
including both light materials and heavy materials such as gas oil,
residual oils, tar sands oil, oil shale kerogen extracts, and liquefied
coal products.
We have found that, in order to effect the recovery of hydrocarbons
from carbonaceous materials and in order to effect the chemical con-
version of the recovered hydrocarbons into lighter, more useful hydro-
carbon fractions by the method of this invention - which involves
. processes characteristically occurring in solution rather than typical
pyrolytic processes - the water in the dense-water-containing fluid
phase must have a high solvent power and liquid-like densities - for
example, at least 0.1 gram per milliliter - rather than vapor-like
-10-
~ 1Z5
¦ densities. Maintenance of the water in the dense-water-containing phase
¦ at a relatively high density, whether at temperatures below or above the
critical temperature of water, is essential to the method of this
¦ invention. The density of the water in the dense-water-containing phase
¦ must be at least 0.1 gram per milliliter.
¦ The high solvent power of dense fluids is discussed in the monograph
¦ "The Principles of Gas Extraction" by P. F. M. Paul and W. S. Wise,
¦ published by Mills and Boon Limited in London, 1971. For example, the
¦ difference in the solvent power of steam and of dense gaseaus water
¦ maintalned at a temperature Ln the region oE the critical temperature
¦ of water and at an elevated pressure is substantial. Even normally
¦ insoluble inorganic materials, such as silica and alumina, commence to
dlssolve apprecltlbLy Ln "supercrLtlcnl water" - that ls, water maintained
lS Mt a temperature above the crLtlcaL temperuture of water - so Long as a
high wuter ~lenslty is maLntained.
Enough water must be employed so that there ls sufflcient water in
the dense-water-containing phase to serve as an effective solvent for
the recovered hydrocarbons. The water in the dense-water-containing phas~
can be in the form either of liquid water or of dense gaseous water.
The vapor pressure of water in the dense-water-containing phase must be
ma~ntained at a sufficiently high level so that the density of water in
the dense-water-containing phase is at least 0.1 gram per milliliter.
We have found that, with the limitations imposed by the size of the
reaction vessels we employed in this work, a weight ratio of the hydro-
carbon fraction-to-water in the dense-water-containing phase in the
range of from about 1:1 to about 1:10 is preferable, and a ratio in the
range of from about 1:2 to about 1:3 is more preferable. Similarly,
a weight ratio oE the oil shale, tar sands, or coal solids-to-water in
the water-containing phase in the range of from about 3:2 to about 1:10
is preferable, and a ratio in the range of from about 1:1 to about 1:3
is more preferable.
10401ZS
~ particularly useful water-containing fluid contains water in
combination with an organic compound such as biphenyl, pyridine, a partly
hydrogenated aromatic oil, or a mono- or polyhydric compound such as
methyl alcohol. The use of such combinations extends the limits of
solubility and rates of dissolution so that cracking, desulfurization,
and demetalation can occur even more readily. Furthermore, the component
other than water in the dense-water-containing phase can serve as a
source of hydrogen, for example, by reaction with water.
The catalyst employed in the method of thls invention is effective
when added in an amount equlvalent to a concentration in the water of
the water-containing Eluid in the range of ~rom about 0.01 to about 3.0
welgllt percent and preerably in the ran~e of From about 0,lO to about
0.5() weight percen~.
The cataly~t may be ad(1ed as a ~ol:Ld and sl~trr:Led ln the renctlon
mlxture or as a water-soluble salt, for example manganese chlorlde or
potassium perman~anate, which procluces the corresponding oxlde under the
conditions employed in the method of this inventlon. Alternately,
the catalyst can be deposited on a support and used as such ln a flxed-
bed flow configuration or slurried in the water-containing fluid.
This process can be performed either as a batch process or as a
continuous or semi-continuous flow process. Contact times between the
carbonaceous materlal and the dense water-containlng phase -that ls,
resldence tlme ln a batch process or inverse solvent space velocity in a
; 25 flow process - of from the order of minutes up to about 6 hours are
satisfactory for effectlve cracklng, desulfuriæation, and demetalation
of the recovered hydrocarbons.
In the method oE this invention, the water-containing fluid and the
oil shale, tar sands~ or coal sollds are contacted by maklng a slu~ry oF
~ t olids in the t~ter-c ntainLng tluld.
1ai4~1z5
l When the method oE this invention is performed above ground with
¦ mined oil shale, tar sands or coal, the hydrocarbons can be recovered
¦ more rapidly if the mined solids are ground to a particle size preferably
¦ of 1/2-inch diameter or smaller. Alternately, the method of this
¦ invention could also be performed in situ in subterranean deposits by
¦ pumping the water-containing fluid into the deposit and withdrawing
¦ hydrocarbon products for separation or further processing.
¦ RXAMPLES 1-37
¦ Examples 1-37 involve batch processing of oil shale and tar sands
lo ¦ Eeeds Imder a vnrlety oE conditLons cmd Lllustrate that hydrocarbons
¦ are recovered, cracked, desIllfurize(I, ~md demetalate(I in the method of
¦ this invention. Unless otherwise speciEied, the following procedIlre
¦ wns used ln eactI ~ase. The oil shale or tar sancls Eeed, wnter, and, L~
¦ used, components oE the catalyst system were loaded at ambLent tem-
¦ perature into a 300-mllllllter }Iastelloy alloy C Mngne-Drive batch
¦ autoclave in whlch the reaction mlxture was to be mixed. The components
of the catalyst system were added as solutes in the water or as solids
in slurries in the water. Unless otherwise specified, sufficient water
was added in each Rxample so that, at the reaction temperature and
prexsure and In the reaction volIlme used, the denxity of the water wnx
at least 0.1 gram per milliliter.
; The autoclave was flushed with inert argon gas and was then closed.
Such inert gas was also added to raise the pressure of the reaction
system. The contribution of argon to the total pressure at ambient
temperature is called the argon pressure.
The temperature of the reaction system was then raised to the
desired level and the dense-water-containing Eluid phase was formed.
Approximately 28 minutes were required to he~t the autoclave from
ambient temperature to 660F. Approximately 6 minutes were required to
30 j ralte the t eraeure from 660F. eO 700F. ~pproxlmately another 6
lU401Z5
minutes were required to raise the temperature from 700F. to 750F.
When the desired final temperature was reached, the temperature was
held constant for the desired period of time. This flnal constant
temperature and the period of time at ~his temperature are defined as
the reaction temperature and reaction time, respectively. During the
reaction time, the pressure of the reaction system increased as the
reaction proceeded. The pressure at the start of the reaction time is
defined as the reaction pressure.
After the desired reaction time at the desired reaction temperature
o and pressure, the dense-water-containing fluid phase was de-pressurized
and was flash-distilled Erom the reaction vessel, removing the gas, water
and "oil", and leaving the "bitumen," inorganic resLdue, and catalyst,
lf present, Ln the reactlon vessel. The "oil" was the llqlllcl hyclro-
carbon fraction boillng at or below the reactlon temperature and the"bitumen" was the hydrocarbon Eractlon bolling above the reaction
temperat~re. The lnorganlc residue was spent shale or spent tar sands.
The gas, water, and oll were trapped ln a pressure vessel cooled by
liquid nitrogen. The gas was removed by warming the pressure vessel to
room temperature and then was analyzed by mass spectroscopy, gas chromato
graphy, and infra-red. The water and oil were then purged from the
préssure vessel by means of compressed gas and occasionally also by
heating the vessel. Then the water and oil were separated by decantation
The oil was analyzed for its sulfur and nitrogen content using x-ray
fluorescence and the Kjeldahl method, respectively, and for its density
and API gravlty.
The bltumen, inorganic residue, and catalyst, if present, were
washed from the reaction vessel with chloroform, and the bitumen
dissolved in this solvent. The solid residue was then separated from
the solution containing the bltumen by filtration. The bitumen was
analyzed for its sulfur and nitrogen contents using the same methods as
1(~4V125
in the analysis of the oil. The solid residue was analyzed for its
inorganic carbonate content.
In regard to the recovery o hydrocarbons from oil shale, several
samples of oil shale were obtained from oil shale deposits in Colorado.
These samples were obtained in the form of lumps, which were then ground
and sieved to obtain fractions of various particle sizes. In order to
esttm.~to tl-e korogenic contont of these fraction~, portions of eacl1
sclmp1e were calc:Lned in air nt 1()00l~. ~or 30 minute~ to remove wnter
and kerogenic carbonaceous matter without decomposing inorganlc carbonate
The particle size of the samples of oil shale used in this work and the
percent of weight loss during calclnation for each of these samples are
presented in Table l.
Examples l-36 involve batch recovery of hydrocarbons from the oil
shale sa~ple~ ~hown in 'rable 1 using the. method described above. T'hese
r~tns were per~ornl~d in a 300-mLll~llter ~ta8telloy a~loy C Magne~l)rlve
nu~oclnve. Tlle axperlmental conditlon~ an~ the re~ults determLned In
tllese ~xam~Le~ nre presented ln ~'ables 2 and 3, respectlvely.
Tn these l~'~amples, the liquid hydrocarbon products were classified
either as oils or as bitumens depending on whether or not such liquid
products could be flashed from the autoclave upon depressurization of the
autoclave at the run temperature employed. Oils were those liquid
~ products which flashed over at the run temperature, while bitumens were
; those liquid products which remained in the autoclave. The oil fractions
had densities in the range of from about 0.92 to about 0.94 grams per
milliliter and had API gravities in the range of between about 19API.
to about 23API. The bitumen fractions had densities of about l.Ol
grams per milliliter and API gravities of about lO. Oil shale sample A
contained 0.7 weight percent of sulfur, l.7 weight percent of nitrogen.
Use oE a catalyst in Example 36 caused a substantial increase in
the amount of the oil fraction produced relative to the amount of the
bitumen fraction produced.
-15-
TABLE l
Oil Shale 1 Percent Weight Loss
Sample Particle Size during Calcination
A 60-80 32.2
B 14-28 26.8
(: 8-14 36. h
D 1/4-l/82 22. 3
ootnotes
1 mesh si~e, except where otherwlse indicated.
2 diameter mensured in inches.
.
30 1 - 16 -
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s ~ ~ ~ o o o o o o o o o ~\
~DO~OO` ~O~O`OO``D
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~ ~ ~ ooooooooooo
,~ c`
20 ~ 3~
25 ~ D ~~
30 ~
~ o~
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The results of eleme~tal analyses of several samples of oil and
¦ bitumen fractions obtained in several of these Examples are also oil
¦ shale feed, and oil kerogen product obtained using thermal retorting
¦ as r2ported by M. T. Atwood in Chemtech, October, 1973,
s ¦ pages 617-621, are shown in Table 4. These
¦ results indicate that the elemental compositions of oils from different
¦ oil shales are quite similar. The weighted combined results for the oil
¦ and bitumen fractions from Examples 7-11 obtained using the method of
¦ this invention indicate tha~ these fractions combined have a similar
¦ nitrogen content but a lower sulfur content than does the oil obtained
¦ using thermal retorting. The H/C atom ratlos for oils obtained using
¦ the method of this invention are also similar to the ~/C atom ratios for
¦ oils obtained by thermal retorting. However, the ~I/C atom ratio for the
combined oil and bitumen fractions obtained using the method of this
~5 invention is less than that for the oil - that is, total liquid products
¦ obtained by thermal retorting. This may reflec~ a larger total liquld
yield obtained using the method of thls invention than with thermolytic
¦ distillation.
¦ The combined oil fractions obtsined in Examples 7 through 11 were
characterized~ and the results are shown in Table 5, along with com-
¦ parable results reported in the literature for oil fractions obtained
¦ from oil shale by thermal retorting and gas com~ustion retorting. How-
ever, the olefin content of the oil fraction boiling up to 405F. obtaine
2s ¦ by the method of this invention differs from the oil content of the oil
¦ fractions boiling up to 405F. obtained by gas combustion retorting and
by thermal retorting. The olefin content in this fraction obtained by
¦ the method of this invention is about half that in the corresponding
¦ fractions obtained by the thermal and gas combustion retorting processes.
¦ Clearly, while olefins are the primary products in this boiling fraction
¦ obtained by the thermal or gas combustion retortlng of hydrocarbons,
~3
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_ 26 -
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TABLE 5
Compositionl of Liquid from
Method of Thermal Combusti
this Invention Retorting2 Retortin ,
Component
bitumen fraction 38
oil fraction 62
acid in component 3 3 4
base in compo~ent 14 8 8
neutral oil ~ 45
to 405F. 6 15 4
paraEElns and 3 3
naphthenes 48.53 273 273
olefins 20.03 483 513
aromatics31.5 25 22
405 to 600F. 10
pa~aEeins and 3
naphthenes 35.53
oleEins 24,03
aromatlcs40.5
600 ~o 700F. 6
resldlle (above 700F.) 23
l'ootnote
1 weight percent of liquid products except where
otherwise indicated.
2 Results were reported in G. 0. Dinneen, R. A. Van Meter,
J. R Smith, C. W. Bailey~ G. L. Cook, C. S. Allbright,
and J. S. Ball, Bulletin 593, U.S. Bureau of Mines, 1961.
2s 3 volume percent of the particular boiling point fraction.
;
30 ~ - 27 -
1~4~Z5
oils having a reduced oleEin conten~ are obtained by the method of this
invention. Thi~ indicates that hydrogen is generated in sltu in the
method of this invention and that such hydrogen is at least partially
consumed in the hydrogenation of recovered olefins.
We have found that there exists a reasonable correlation of both
the volumetric content of hydrocarbons in oil shale samples and the
weight content of hydrocarbons in such samples with the weight loss of
such samples during calcination in air at 1000F. for 30 minutes. Both
the volumetric and the weight contents o hydrocarbons are based on the
Fischer assay described by L. Goodfellow, C. F. Haberman, and M. T.
Atwood, "Modified Flscher Assay, "Division of Petroleum Chemistry,
Abstracts, page F. 86, American Chemical Society, San Francisco ~leeting,
April 2-5, 1968. Thls correlation i9 9hOWII in Figure 1.
Using this correlation, the expected yleld oE hydrocarbons from
the oil shale samples we used was estimated in order to compare the
actual yield of hydrocarbons with the expected total possible yield of
; hydrocarbons from the oil shale samples used. The weight loss duringcalcination of the oil shale samples used and the correlation shown in
Figure 1 indicate that the oil shale samples used would yield liquid
products in the range of approximately 14 to 22 percent by weight of the
-~ oil shale feed.
The actual weight loss during calcination of oil shale sample A,
the expected yield of hydrocarbons in this oil shale sample, and the
actual yields of oil, bitumen, and the gaseous products (carbon dioxide
and Cl to C3 hydrocarbons) recovered in 2-hour batch runs of oil shale
sample A at various temperatures are shown in Figure 2. These runs were
performed using shale-water weight ratios of either 0.56 or 1 When the
ratio was 0.56, 90 grams of water were charged. When the ratio was 1,
60 grams of water were charged. The pressures ranged between 2550 and
4200 pounds per square inch gauge. The data plotted in Figure 2 were
~1 3.L?401Z5
taken from the results shown in Table 3. The liquid selectivity - the
ratio of the total yield of liquid products to the weight loss of the
oil shale sample during calcination - for oil shale sample A at 752F.
is 0.67. The oil selectivity - the ratio of the yield of oil to the
total yield of llquid products - for oil shale sample A at 752F. is
0.61,
The yield of oil recovered from oil shale by the method of this
invention was markedly dependent on the temperature. The total liquid
product yield - oil plus bitumen - was roughly constant at temperatures
lo above 705F. and dropped sharply at temperatures below 705F. At tem-
perntures above 705F., the total liquid product ylelds accounted fortor even sllghtly exGeeded the amountR recoverable eRtlmatecl l)y ~he
Fischer assay. AlthouRIl eRsent:Lnlly all avallable hydrocarbon WaR rcmovec
from the oil shale by the method oE thls invention at a temperature of
at least 705F., the amounts of lighter hydrocarbon fractions recovered
continued to increase as the temperature was increased above 705F.
This is evidenced in Figure 2 by the sharp increase in the oil yield and
decrease in the bitumen yield as the temperature is increased above
705F. Such an increase in the oil yield and decrease in the bitumen
yield is reasonable if cracking - either thermal or catalytic through
the presence of catalys~s intrinsically present in the oil shale - of
the bitumen were occurring.
Similar results, shown in Table 6, were obtained in Examples 1, 2,
15, and 26 - 28 with different contact tlmes and with oil shale samples
of different particle size ranges than those used in obtatning the
results shown in Figure 2. These results indicate that even at a tem-
perature of 698F., slightly below the crltical temperature for water,
the llquid and oll selectlvitles were substantially reduced from the
values obtained at temperatures above the critical temperature of water.
` ~4~1Z5
TABLE 6
Data Oil Reaction Reaction Liquid Oil
from Shale Temperature Time Se- Se-
Example ~ (F.) (hours) lectivity lectivity
2 A 660 2 0.27 0.06
1 A 752 2 0.67 0.61
28 B 716 2 0.63 0.41
B 752 2 0.58 0.68
27 D 698 0.5 0.42 0.47
26 D 752 0.5 0,58 0.50
Footnotes
1 The samples corresponding to the letters are identlfied
~ TEIble 1.
- 30 -
~ s
Results showing the effect of the particle size of the oil shale
substrate on the rate of recovery of hydrocarbons from oil shale are
presented in Figures 3 and 4. The plots in Figures 3 and 4 were obtained
using the results shown in Table 3, for runs involving a shale-to-water
s weight ratio of 0.56. The weight loss during calcination, the expected
yield of hydrocarbons from the oil shale sample, and the measured yield
of liquid hydrocarbon products - all being expressed as weight percent
of the oil shale feed - are shown in Figure 3 as a function of the contac
time and of ~he range of particle sizes of the oil shale feed. Generally
with oil shale Eeed having a partlcle siæe of approximately 1/4-inch
diameter or less, more than 90 weight percent o~ the carbonaceous content
of the oil shale feed was recovered ln less than one-half hour. When
the oil shale feed had a particle size equal to or smaller than 8 mesh,
the ylel~ oE total llquL~ products was ~reate.r after a contac~ time of
one-half hour ~han nter a contact time of two hours, and exceeded the
expected yield Oe hydrocarbons from the oil shale. For such feed, the
decline of total yleld o the liquid hydrocarbon products with increasing
contact time corresponded to increased conversion of the liquid products
to dry gas, for example by cracking the liquid products. Cracking wa.s
also indicated by the plots in Figure 4 showing the oil selectivity as a
function of the contact time and of the range of the particle sizes of
the oil shale feed.
~1hen the oil shale feed had a particle size in the range of from
1/4-inch to 1/8-inch, the rate of recovery was low enough so that the
total yield of liquid products after a contact time of one-half hour was
less than the total yield of liquid products after a contact time of
two hours, This is indicated in Figure 3. Whlle no theory Eor this is
proposed, if the oil shale feed is made up of coarser materials having a
larger particle size, the ratio of surface area to particle volume for
such materials would be lower than that for finer materials, and diffusio
lU4V125
of water into the coarser oil shale particles and the rate of dissolution
of the inorganic matrix in the supercritlcal water may decrease, and,
hence, the rate of recovery may decrease.
There is evidence that efficient recovery of liquids from oil shale
by the method of this invention involves partial dissolution of the
inorganic matrix oE the oil shale substrate. Following complete recovery
of liquids from oil shale feeds having particle sizes in the range of
1/4-inch diameter to 80 mesh, the spent oil shale solids recovered had
substantially smaller particle sizes, generally less than 100 mesh.
lo Further, there was also a decrease in the bulk density from about 2.1
grams per milliliter for the feed to about 1.1 grams per milliliter for
the spent solids. On the other hand, when the liquids were not completel
recovered from the o:Ll shale Eeed, the oil shale particles retained much
of their starting conformation, For example, little apparent confor-
mational change occurred for oil shale feed when only half of the
carbonaceous material was removed from it.
There i8 additional evidence of the decomposition of the inorganic
matrix of the oil shale substrate during recovery of liquid hydrocarbons
by the method of this invention. The high yield of carbon dioxide from
the recovery of liquid hydrocarbons from oil shale, even at the relativel
lo~ temperature of 660F., indicates decomposition of the inorganic
carbonate in the structure of oil shale. The approximate mass balance
of the oil shale feed and of the combined products from the recoveries
in Examples 7-11 of liquid hydrocarbons from the oil shale sample A
demonstrate that carbon dioxide is formed from inorganic carbonate and
is presented in Table 7.
The relationships by which the products were characterized are
presented hereinafter. The total amount, SO, of oil shale feed,
excluding entrained water, is given as follows:
So = S ~ IC + KC
1(~4~)1Z5
TABLE 7
Weight Percent
Component Component Symbol of the Feed
l Oil Shale Feed
5 ¦ Kerogen KC 32
Acid-tltratable
inorganic carbonate IC 19
Inorganic solid, S 49
excluding acid
¦ titratable lnorganlc carbonate
1 100
10 l
I Recovery Product
¦ Dry ga9 KG
¦ Oil and bitumen KOB 23
¦ Carbon dloxide 7
: ls ¦ Kerogen coke YKC 4
¦ Acid-titratable
¦ inorganic carbonate xIc 15
¦ Inorganic solid, S 50
¦ excluding acid-ti~ratable inorganic carbonate
¦ Total
:2o l i00
~'
~' I
` 25 l
I
~ 4U1~5
whereln the symbols used are defined in Table 7.
When the oil shale feed was titrated with acid, the amount of acid-
titratable, inorganic carbonate initially present, IC 9 in the oil shale
feed was determined, and thus the relationship between the measured
amount of acld-titratable inorganic carbonate initially present and the
measured total amount of oil shale feed could be expressed. Such
relationship for oil shale sample A was
IC = 0.187 S0
When the oil shale feed was calcined in air for 30 minutes at 1000F .
lo all organic material was driven off, and the measured weight of total
lnorgan-lc material could be expressed in terms of the total amount of
oil shale feed as follows:
S ~ IC = 0.678 S0
From the last two eqtlations, S was be calculated to be 0.491 S0.
The solid products obtained in the recovery of hyclrocarbons from
the oll shale ~eed by the method of this invention are glven as follows:
S + X~c + YKC ' 0-686 S0
wherein the symbols used are defined in Table 7. The conditions employed
in this run were a temperature of 752F., a pressure of approxlmately
4000 polmds per square inch gauge, a time of 2 hours, a charge of water
of 60 grams, and a shale-to-water weight ratio of 1Ø
When the spent oil shale solid residue was titrated with acid, the
amount of acid-titratable inorganlc carbonate present in the spent solid
after the run could be determined, and the relationship between the
measured amount of acid-titratable inorganic carbonate present after
removal of the hydrocarbons, xIc, and the measured total amount of oil
shale measured could be expressed as follows
xIc = 0,147 S0
where x iB the Eraction of the amount initially present, Ic, which is
still remaining.
104UlZ5
When the spent oil shale solid was calcined in air for 30 minutes at
1000F., all organic material was driven off~ and the measured weight of
total organic material remaining after removal of the hydrocarbons
could be expressed in terms of the total amount of oil shale as follows:
S + xIc = 0.643 SO
From the last two equations, S was calculated to be 0.496 SO. This
value corresponds closely to the value of S calculated from the analytica
characterization of the oil shale feed.
A very significant result from the analytical characterization
shown in Table 7 is that the amount of acid-titratable inorganic
carbonate in the solid spent oil shale was markedly lower than the amount
of acid-titratable inorganic carbonate in the oil shale feed, and the
difference between such amounts could account for between 50-60 weight
percent of the gaaeous carbon dloxlde produced. Carbon dloxide derived
~rom the kerogen in the oil shale feed could also account for some of
the remainder. Generally, inorganic carbonate in the structure of o:Ll
sllale ~urvLves ~herma] proceff~lng 1~ the temperature i9 kept no hlgher
than 1000F. Thu~, tllermal or gas combustive retorting daes not normally
reduce the amount of acid-titratable inorganic carbonate. On the
contrary, the amount of acid-titratable inorganic carbonate in the
structure of oil shale was reduced by the method of this invention.
Results from 2-hour batch runs at 752F. showing the effect of the
weight ratio of oil shale feed-to-solvent on the total yield of liquid
products and on oil selectivity are presented in Table ~. The recovery
was complete under the conditions employed when the weight ratio of oil
shale feed-to-solvent was in the range oE from about 1:1 to about 1:2. A
weight ratio in this range also permits Eluid transfer and compression
of the oil shale feed-solvent mixture 80 that a continuous slurry pro-
cessing system is possible.
_ 35 _
TABLE 8
Results Oil Oil Shale -to- Expec~ed Weight % of Feed
from Shale W~ter Total Hydro- Recovered as
Example Samplel Weight Ratio carbon Yield Oil Bitumen
1 A 1.0 22 13.2 8.3
3 ~ 0.6 22 13.5 6.5
13 B 1.0 16 11.8 9.0
B 0.6 16 10.5 S.O
12 C 1.0 22 17.8 9.2
lo 14 C 0.6 22 14.4 7.4
Footnotes
1 The samples corresponding to the letters are ldentified
in Table 1.
~5
Example 37 involves a batch recovery of hydrocarbons from raw tar
sands using the method of this invention. The conditions employed were
a reaction temperature of 752F,, a reaction time of 2 hours, a reaction
pressure of ~100 pounds per square inch gauge, and an argon pressure of
250 pounds per square inch guage. The feed was made up of 40 grams of
raw tar sands in 90 grams of water. Thls run was performed in a 300-
milliliter Hastelloy alloy C Magne-Drive autoclave. The products of
this recovery included gas (hydrogen, carbon dioxide, and methane) and
lo oil in amounts equivalent to 2 and 8 weight percent of the feed,
respectively. The oll had an API gravity of about 17.0 and sulfur,
nickel, and vanadium contents of 2.7 weight percent, and 45 and 30 parts
per million, respectively. On the contrary, tar sands oil obtained by
the COFCAW process had an API gravity oE 12.2 and sulfur, nickel, and
vanadium contents of 4.6 weight percent, and 74 and 182 parts per mlllion
respec~vely. ~Icnce, ~he ~ll obtained by the method of thls inventlon
1B upgrAded relnt:Lve to the oll produced by the COFCAW proces~,
Further, the yields of gas, oll, bltumen, and solld products in this
Fxample were 2.5, 3.7, 3.4, and 86.5 weight percent of the tar sands
feed. This represents essentially complete recovery of the hydro-
carbon content of the tar sands feed. The total amount of gas, oil,
bitumen, and solid fractions and of water reco~ered constituted 97.4
weight percent of the tar sands and water feeds.
EXAMPLES 38-51
Examples 38-51 involve batch processing of different types of hydro-
carbon feedstocks under a variety of conditions and illustrate that the
mathod of this invention effectively cracks, desulfurizes, and
demetalates hydrocarbons and therefore that the hydrocarbons recovered
from the oll shale, tar sands, or coal solids are also cracked,
desulfurized, and demetalated in the method of this invention. Unless
otherwise specified, the following procedure was used in each case. The
lV40125
hydrocarbon feed, water, and catalyst, if any, were loaded at ambient
temperature into a 300-milliliter Hastelloy alloy C Magne-Drive auto-
clave in which the reaction mixture was to be mixed. The components of
the catalyst system were added as solutes in the water or as solids in
s slurries in the water.
Unless otherwise speclfied, sufficient water was added in each Example
so that, at the reaction temperature and pressure and in the reaction
volume used, the density of the water was at least 0,1 gram per millil-
iter.
o The autoclave was flushed with inert argon gas and was then closed.
Such inert ga~ was also added to raise the pressure of the reaction
system. The contribution of argon to the total preqsure at ambient
temperature is callecl the argon pressure~
The temperature oE the reaction system wa9 then raised to the
desired level and the dense-water-containing fluld phase was formed.
~pproxlmately 28 minutes were required to heat the autoclave from
ambient temperature to 660F. Approximately 6 minutes were required to
raise the temperature from 660F. to 700F. Approximately another 6
minutes were requlred to raise the temperature from 700F. to 750F.
When the desired final temperature was reached, the temperature was
held constant for the desired period of time. This final constant
temperature and the period of time at this temperature are defined as
the reaction temperature and reaction time, respectively. During the
reaction time, the pressure of the reaction system increased as the
reaction proceeded. The pressure at the start of the reaction time is
defined as the reaction pressure.
After the desired reaction time at the desired reaction temperature
and pressure, the dense-water-containing fluid phase was de-pressurized
and was flash-distilled from the reaction vessel, removing the gas, water
and "light" ends, and leaving the "heavy" ends and other solids, includin
the catalyst, if present, in the reaction vessel. The "light" ends were
ll)40125
the hydrocarbon fraction boiling at or below the reaction temperature
and the "heavy" ends were the hydrocarbon fraction boiling above the
reaction temperature.
The gas, water, and light ends were trapped in a pressure vessel
cooled by liquid nitrogen. The gas was removed by warming the pressure
vessel to room temperature and then was analyzed by mass spectroscopy,
gas chromatography, and infra-red, 'rhe water and llght ends were then
purged from the pressure vessel by means of compressed gas and occasion-
ally also by heating the vessel. Then the water and light ends were
0 separated by decantation. ~lternately, this ~eparation was postponed
until a later stage in the procedure. Gas chromatograms were run onthe light ends.
The heavy ends and solids, lncluding the catalyst, iE pr~sent, were
washed from the reaction vessel with chloroform, and the heavy ends
dissolved in this solvent. The solids were then separated from the
solution containing the heavy ends by filtration.
After separating the chloroform from the heavy ends by distillation,
the light ends and heavy ends were combined. If the water had not
already been separated Erom the light ends, then it was separated from
the combined light and heavy ends by centrifugation and decantation.
The combined light and heavy ends were analyzed for their nickel,
vanadium, and sulfur content, carbon-hydrogen atom ratio (C/H), and API
gravity. The water was analyzed for nickel and vanadium, and the solids
were analyzed for nickel, vanadium, and sulur. X-ray fluoresence was
used to determine nickel, vanadium, and sulfur.
Examples 38-42 involve straight tar sands oil, and Examples 43-46
in~olve topped tar sands oil. Topped tar sands oil is the ~traight tar
sands oil used in Examples 38-42 but from which approximately 25 weight
percent of light material has been removed. Examples 47-50 involve
C vacuum atmospheric residual oil. Example 51 involves C vacuum residual
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- 44-
104()~LZ5
oil. ~he compositions of the hydrocarbon feeds employed are shown in
Table 9~ The experimental conditions used and the results of analyses
of the products obtained in these ~xamples are shown in Tables lO and ll,
respectively. A 300-milliliter Hastelloy alloy C Magne-Drive autoclave
was employed as the reaction vessel in these Examples.
Comparison of the results shown in Table ll indicates that
desulfurization and demetalation of the hydrocarbon feed occurred and
that the hydrocarbon feed was cracked, producing gases, light ends,
heavy ends, and solid residue, even when no catalyst was added from an
externnl source. In such case, the extent of removal of sulfur and
metals increasecl when the reaction time was increased Erom t to 3 hol1rs.
Beyond that time, the extent of desulfuriYntlon decrensec1 wLth -Increnslng
reaction time. Addltion of a catalysc substnntially LncreMsed the
extent of desulfurization and demetalation.
When the water density was at least O.l gram per milliliter - for
example, when the hydrocarbon Eraction-to-water weight ratlo was l:3 -
the sulfur which was removed from the hydrocarbon feed appeared as
elemental sulfur and not as sulEur dioxide or as hydrogen sulfide. ~t
lower water densities - for example~ when the hydrocarbon-to-water
weight ratio was 4:1 - part of the removed sulfur appeared as hydrogen
suifide. Th~s clearly indicates a change in the mechanlsm of de-
sulfurization of organic compounds on contact with a dense-water-con-
taining phase, depending upon the water density of the dense-water-con-
2s taining phase. Further, when the hydrocarbon fraction-to-water weight
ratio was ~I:l, there was an adverse shift in the distrib~1~ion oE hydro-
carbon products and a lesser extent oE desulfurization.
The total weight percent of gases and compositions of the gas
products obtained in several of the Examples are indicated in Table 12.
In all cases, the main component of the gas products was argon which was
used in the pressurization of the reac~or and which is not reported in
l(i'~lZ5
¦ TABLE 12
Composi~ion of the Gas Products2
Total
I Weight
5 I ReaCltin Carbon Percent
Example Time Hydrogen Dioxide Methane of Gas
I ~
39 3 3.3 5.2 6.9 11.2
1 2.8 3.1 3.4 1.3
43 1 1.0 3.8 8.4 1.0
1 44 3 3.0 5.6 7.5 S.9
10 l
l ootnotes
¦ 1 hottr~.
¦ 2 mo:le percent of ~ns.
30 1 - 46 -
¦ Table 12. Generally, increaging the reactlon time resulted in increased
¦ yields of gaseous products.
¦ Successive exposure of the catalysts of this invention to hydro-
¦ carbons containing sulfur contaminants did not cause a decrease in the
s ¦ catalytic efficiency of the catalysts.
¦ EXAMPLES 52-61
¦ Examples 52-61 involve semi-continuous flow processing at 752F. of
¦ straight tar sands oil under a variety of conditions. The flow system
¦ used in these Examples is shown ln Figure 5. To start a run, 1/8-inch
to ¦ diameter inert, spherical alundum balls or lrregularly shaped, catalytlc
¦ titanium oxide chips havlng 2 weight percent oE ruthenium deposited
¦ thereon were loaded into a 21.5-lnch long, l-inch outside diameter, and
¦ 0.25-inch inslde diameter vertical Hastelloy alloy C plpe renctor 16.
¦ The alundum balls served merely to provide an lnert surface on which
metals to be removed from the hydrocarbon feed could deposlt. Top 19
was then closed, and a furnace (not shown) was placed around the length
of pipe reactor 16. Plpe reactor 16 had a total eEfective heated volume
of approximately 12 milliliters, and the packing material had a total
volume of approximately 6 milliliters, leaving approximately a 6-mllli-
liter free effective heated space in pipe reactor 16.
All valves, except 53 and 61, were opened, and the flow system was
flushed with argon or nitrogen. Then, with valves 4, 5, 29, 37, 46, 53,
61, and 84 closed and with Annin valve 82 set to release gas from the
2s flow system when the desired pressure in the system was exceeded, the
flow system was brought up to a pressure in the range of Erom about 1000
to about 2000 pounds per square lnch gauge by argon or nitrogen entering
the system through valve 80 and line 79. Then valve 80 was closed.
Next, the pressure of the Elow system was brought up to the desired
reaction pressure by opening valve 53 and pumping water through Haskel
3~ pUD O and line 51 into water t~nk 54 The water served to Eurther
1~ 5
compress the gas ln the flow system and thereby to further increase the
pressure in the system. If a greater volume of water than the volume of
water tank 54 was needed to ralse the pressure of the flow system to the
desired level, then valve 61 was opened, and additional water was pumped
through line 60 and into dump tank 44. When the pressure of the flow
system reached the desired pressure, valves 53 and 61 were closed.
A Ruska pump 1 was used to pump the hydrocarbon fractian and water
into pipe reactor 16. The Ruska pump 1 contained two 250-milliliter
barrels (not shown), with the hydrocarbon fraction being loaded into
one barrel and water into the other, at ambient temperature and atmos-
pheric pressure. Pistons (not shown) inside these barrels were manuallyturned on until the pressure in each barrel equaled the pressure of the
flow system. When the pressures in the barrels and in the flow system
were equal, check valves 4 and 5 opened to admit hydrocarbon Eraction
and water from the barrels to flow through lines 2 and 3. At the same
time, valve 72 was closed to prevent flow in line 70 between points 12
and 78. Then the hydrocarbon ~ractLon and water ~treams Joined at po-Lnt
10 at nmbient temperature and ut the de~lred pressure, rlowed througl
line 11, and entered the bottom 17 of pipe reactor 16. The reaction
mixture flowed through pipe reactor 16 and exited from pipe reactor 16
through slde ar~ 24 at point 20 in the wall of pipe reactor 16. Point
20 was 19 inches from bottom 17.
With solution flowing through pipe reactor 16, the furnace began
heating pipe reactor 16. During heat-up of pipe reactor 16 and until
steady state conditions were achieved, valves 26 and 34 were closed,
and valve 43 was opened to permit the mixture in side arm 24 to flow
through line 42 and to enter and be stored in dump tank 44. After steady
state conditions were achieved, valve 43 was closed, and valve 34 was
opened for the desired period of time to permit the mixture in side arm
24 to flow through line 33 and to enter and be stored ln product receiver
35. After eoIlcctln~ n batc~ of product In product recelver 35 ~or the
de~Ired p~riod of time, valve 34 was closed, nnd vnlve 26 was opened to
permlt th~ mixture in side arm 24 to flow through llne 25 and to enter
and be stored in product receiver 27 for ano~her period of time. Then
S valve 26 was closed.
The mnterial in side arm 24 was a mixture of gaseous and liquid
phase~. When such mixture entered dump tank 44, product receiver 35,
or product receiver 27, the gaseou~ and l~quid phases separated, and the
ga~es exited from dump tank 44, product receiver 35, and product receiver
o 27 throu~h lines 47, 38, and 30, respectively, and pnssed through line
70 and Annin valve 82 to a storage vessel (not shown).
en more than two batches of product were to be collected, valve
29 and/or valve 37 was opened to remove product from product recelver
27 and/or 35, respectively, to permit the same product receiver and/or
receivers to be used to collect additional batches of product.
At the end of a run - during which the desired number of batches
of product were collected - the temperature of pipe reactor 16 was
lowered to ambient temperature, nnd the flow system was depressurized by
opening vnlve 84, in line 85 venting to the atmosphere.
Diaphragm 76 measured the pressure differential across the length
of pipe reactor 16. No solution flowed through line 85.
The API gravity of the liquid hydrocarbon products collected was
measured, and their nickel, vanadium, and iron contents were determined
by x-ray fluorescence.
The properties of the straight tar sands oil feed employed in
Examples 52-61 are shown ~n Table 9. The tar sands oil feed contained
300-500 parts per million of iron, and the amount of 300 parts per
million was used to determine the percent iron removed from the product.
The experimental conditions and charscteristics of the products formed
in these Examples are presented in Table 13. The liquid hourly space
113~LU1~5
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¦ velocity (LHSV) was calculated by dividing the total volumetric flow rate,
¦ in milliliters per hour, of water and oil feed passing through pipe
¦ reactor 16 by the volumetric free space in pipe reactor 16 - that is1 6
I milliliters.
¦ The flow process employed in Examples 52-61 could also be modified
¦ so as to permit pumping a slurry of oil shale solids, tar sands solids,
¦ or coal solids in a water-containing fluid through pipe reaceor 16. In
¦ such case, the alundum balls would not be present in pipe reactor 16,
I and dump tank 44 and product receivers 27 and 35 could be equipped with
¦ some device, for example a screen, to separate the spent solids from the
¦ recovered hydrocarbon product. Thus, continuous and semi-continuous flow
¦ processing could be used in the recovery process itself.
¦ EXAMPLES 62-78
¦ Examples 62-78 involve ba~ch processing of coal Eeeds under a
¦ variety of condltions and illustrate that liquids and gases are
recovered, that the recovered liquids are cracked and desulfurized, and
that the remaining solid coal is desulfurized in the method of this
invention. Unless otherwise specified, the following procedure was used
in each case. The coal feed, water-containing fluid, and components of
the catalyst system, if used, were loaded at ambient temperature into a
~; 300-milliliter Hastelloy alloy C Magne-Drive batch autoclave in which
; the reaction mixture was to be mixed. The components of the catalyst
system were added as solutes in the water-containing fluid or as solids
in slurries in the water-containing fluid. Unless otherwise specified,
sufficient water was added in each Example so that, at the reaction tem-
perature and pressure and in the reaction volume used, the density of the
water was at least 0,1 gram per milliliter~
The autoclave was flushed with inert argon gas and was then closed.
Such inert gas was also added to raise the pressure of the reaction
system. The contribution of argon to the total pressure at amblent
temperature is called the argon pressure.
~ s
'rhe temperature o~ the reactlon system was then rai~ed to the
desired level and the dense-water-containlng fluid phase was formed.
Approximately 28 minutes were required to heat the autoclave from
ambient temperature to 660F. Approximately 6 minutes were required to
raise the temperature from 660F. to 700F. Approximately another 6
minutes were req~lired to raise the temperature from 700F. to 750~F.
When the desired final temperature was reached, the temperature was
held constant for the desired period of time. This final constant
temperature and the period of time at this temperature are defined as
lo the reactlon temperature and reaction time, respectively. During the
reaction time, the pressure of the reaction system increased as the
reaction proceeded. The pressure at the start of the reaction time is
defined as the reaction pressure.
AEter the deslred reaction tlme at the deslred react:Lon temperature
and pressure, ~he dense-water-containlng fluld phase was cle-press~lrl~ed
by flash-dlstillLng from the reactlon vessel, retnoving the argon,
gu~ prodtlcts, wute-r, nnd "oll," Mnd leavlng ~he "bl~umen," soll(l resld~le,
und cntaly~t, Ir pre~cnt, Ln Lllc reuctlon veH~el. 'I'he "olL" W-1.4 the
liquid hydrocarbon fraction boiling at or below the reaction temperature
and the "bitumen" was the liquid hydrocarbon fraction boiling above the
reaction temperature. The solid residue was remaining solid coal.
The argon, gas products, water, and oil were trapped in a pressure
vessel cooled by liquid nitrogen. The argon and gas products were
removed by warming the pressure vessel to room temperature, and then
the gas products were analyzed by mass spectroscopy, gas chromatography,
and infra-red. The water and oil were then purged from the pressure
vessel by means oE compressed gas and occasionally also by heating the
vessel. Then the water and oil were separated by decantation. The oil
was analyzed for its sulfur content using X-ray fluoresence.
4~5
TABLE 14
Coal Part~cle MoistureSulfur 3
Sample Size Content2Content
A 10-40 22.2 0.74
B 10-40 9.7 4.5
C4 ~ 80 2.7 4.9
Footnotes
1 mesh size.
2 weight percent.
3 weight percent, on a moisture-ree ba~is.
~ pre-drled.
.
~:
1041~?~25
The bitumen, solid residue, and catalyst, if present, were washed
from the reaction vessel with chloroform, and the bitumen dissolved in
this solvent. The solid residue and catalyst, if present, were then
separated from the solution containing the bitumen by Eiltration. The
bitumen and solids were analyzed for their sulfur contents using the
same method as in the analysis of the oil.
The weights oE the various components or fractions added and
recovered were determined either directly or indirectly by difference
at various stages during the procedure.
0 Three samples of coal were used in this work. The sa~ples were
obtained ln the Eorm of lumps, which were then ground and sieved to
obtain fractlons of various particle sizes. The partlcle size and
moisture and sulftlr contents oE each sample used nre presented in 'rab1.e
l. Samples A and B were obtalned from Commonwealth Edlson Company,
while sample C was an Illinois number 6 seam coal obtained Erom Hydro-
carbon Research Incorporated. Sample A was a sub-bituminous coal, while
samples B and C were highly volatile bituminous coals. These samples
were stored under 8 blanket of argon until used.
Examples 62-78 involve batch recovery of liquids and gases from the
coal samples shown in Table 14 using the method described above. These
runs were performed in a 300-milliliter Hastelloy alloy C Magne-Drive
autoclave. The experimental conditions and the results determined in
these Examples are presented in Tables 15 and 16~ respectively.
2s In these Examples, the liquid hydrocarbon products were classified
either as oils or as bitumens depending on whether or not such liquid
products could be flashed from the autoclave upon depressurlzation of
the autoclave at the run temperature employed. Oils were those liquid
products which flashed over at the run temperature, while bitumens were
those liquid products which remained in the autoclave.
j _ 55 _
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The weight balance shown in Table 16 was obtained by dividing the
sum of the weights of the gas, liquid, and solid products recovered and
of the weights of the water, argon, and catalyst, if used, recovered by
the sum of the weights of the coal, water, co-solvent, argon, and catalysl ,
if used, initially charged to the autoclave. The product composition,
reported as a weight percent on a moisture-free basis, was calculated by
dividing the weight of the particular product in grams by the difference
between the weight of the coal feed in grams and its moisture content in
grams. ~he percent of coal conversion is 100 minus the weight percent
of solid recovered.
The results shown in Table 16 illustrate that substantial conversion
of coal solids occurred with both bituminous and sub-bituminous coal
using the method of this invention. There was also substantial
desulfurlzation ln each case where the sulEur content of the products
was determ:Lned. AddltLon oE a catalyst ln the method oE thls lnvent:lon
ln E~ample9 77 and 78 resulted :I.n nn :Lncrease :Ln the production of the
oll Eractlon relatLve to tlle gas nnd bitu~en fractlons.
The results of Examples 70, 71, and 73 indicate that the organic
co-solvent made no contribution to the amount of solid product recovered.
Therefore, the amount of solid remaining after processing under the
conditions of the method of this invention is a good measure of the
extent of conversion of solid coal to gas and liquid products, even in
the presence of a co-solvent. Generally, the extent of coal conversion
increased markedly when a saturated, non-aromatic oil or biphenyl was
the co-solvent. No attempt was made to distinguish between the con-
tributions of the coal feed and of the co-solvent to the yields of gas
and liquid products, when a co-solvent was used.
The above examples are presented by way of illustration, and the
~ inventlon 3 ld not be construed t3 li3ited thereto.
lV4(~1Z5
The various components of the catalyst system of the method of this
invention do not possess exactly identical effectiveness. The most
advantageous selection of components and concentrations thereof ln the
particular catalyst system to be used will depend on the particular
carbonaceous material being processed.
