CA1040124A - Process for recovering upgraded hydrocarbon products - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
This invention involves a process for recovering upgraded hydro-carbon products from a carbonaceous material selected from the class consisting of oil shale solids, tar sands solids, coal solids and a hydrocarbon fraction by contacting the carbonaceous material with a dense-water-containing fluid at a temperature in the range of from about 600°F. to about 900°F. in the absence of supplied hydrogen and in the presence of a sulfur- and nitrogen-resistant catalyst.

Description

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A promising technique for recovering hydrocarbons from carbonaceou9 mater~als is a proce~s oalled dense ~luid extraction. Separation by dense fluid extraation at elevated temperatures is a relatively unexplored area. The basic principles of dense fluld extraction at eievated temperatures are outlined in the monograph "The Principles of Gas Extraction"
by P. F. M. Paul and WO S. Wise, published by Mills and Boon Limited in London, 1971, Chapters l through 4. The dense ~luid can be either a liquid or a dense gas having a liquid-like density.
Dense fluid extraction depends on the changes in the properties of a fluid - in particular, the density of the fluid -due to changes in the pressure. At temperatures below its critical temperature, the density of a fluid varies in step functional fashion with changes in the pressure. Such sharp transitions in the density are associated with vapor-liquid transitions. At temperatures above the critical temperature of a fluid, the density of the fluid increases almost linearly with pressure as required 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 temperature and at its saturated vapor pressure, two phases will be in 1~`4~'~2~ 1 , ~ qu1l~br~11m wlth cnch other~ }Iql1ld X Or d~n~ty C 1lnd vnpor Y ~
¦ density ~. The llquid o~ c1ensity C wtll 1-osse~s a certain solvent power.
¦ If the same fluid wera then maintained at ~I partlcular temper~ture above ¦ lts critical temperature nnd 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 of density C. A similar solvent power could be achieved at an even hi~her temperature by an even greater co~pression of the fluid to density C~ However, because of the non-ideal behavior oE the fluid near its critical temperature, a particular increase in 0 pressure will be more effective in increaslng the density of the fluid w11en the temperature is sllghtly above the critical temperature than when the temperature is much above the critlcal temperature of the fluid.
These simple considerations lead to the suggestion that at a given pressure and at a temperature above the critical temperature of a com-pressed fluid, the solvent power of the compressed fluid should be ~reater 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 ~ritical temperature of the fluid solventj it is not essential that the ¦ solvent phase be maintained above it~ critical temperature. It is only ¦ essential that the fluid solvent be maintained at high enou~h pressures ¦ so that its density is high. T~ss, liquid fluids and gaseous fluids 1 which are maintained at high pressures and have liquid~l~ke densities 2s ¦ are useful solvents in dense fluid extractions at elevated temperatures.

¦ The basis of separations 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 decompressed to a point where the solvent power of the fluid ls desLroyed and where the dis601ved material ls separated as a solid or liquid.
Some general conclusions based on empirical correlatlons have been drawn regarding the conditions for 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 addition, it has been concluded that a more efficient 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 fluid should be greater the lower the temperature but since the vapor pressure of the material to be extracted should be greater the higher the temperature, the choice of extraction temperature should be a compromise between these opposing effects.
Vario~ls ways of making practical use of dense fluid extraction are po~ssible 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 an appropriate fluid solvent, by adjusting the temperature and pressure of the extraction or decompresslon, and by altering the ratio o~ substrate-~o-fluld solvent wllich is charged to the extraction vessel.
Tn general, dense Eluid extractlon at elevated temperatures can be considered as an alternntive, on the one hand, to distillation and, on the other hand, to extraction with liquid solvents at lower tempera-tures. A considerable advantage of dense fluid extraction over distil-lation is that it enables substrates of low volatility to be processed.
Dense fluid extraction even offers an alternative to molecular distil-lation, but with such high concentrations in the dense fluid phase lo 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 temperatures well below those required by distllation.

A considerable advantage of dense fluid extraction at elevated temperatures over llquid extraction at lower temperatures is that the solvent power of the compressed fluid solvent 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 and scope to solvent extraction processes.
Zhuze was apparently the first to apply dense fluid extraction to chemical engineering operations in a scheme for de-asphalting petroleum fractions using a propane-propylene mixture as gas, as reported in Vestnik Akad. Nau~ S.S.S,R. 29 (11), 47-52 (1959) and in Petroleum (London) 23, 298-300 (1960).
Apart from Zhuze's work, there have b~en few 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 as 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 oE gas extraction techniques for worklng up heavy ¦ pe~roleum fractions. A feature of particular interest is the separation ¦ of materials into residue and extract products, the latter being ~ree ¦ from ob~ectionable lnorganic contaminants such as vanad-lum. The advantage ¦ is also mentioned in this patent of cooling the gas solvent at sub-¦ critical 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 ¦ petroleum Eractions. In principle, these seem to follow the direction ¦ of the earlier Russian work.
¦ In addition, there are other references to recovery of liquid ¦ hydrocarbon fractions from carbonaceous materials by processes utilizing ¦ water. For example, Friedman et al., U.S. Patent No. 3,051,644 ~1962) ¦ discloses a process for the recovery of oil from oil shale which involves ¦ sub~ecting oil shale particles dispersed ln steam to treatment with ¦ steam at a temperature in the range of from 700F, to 900F. and at a ¦ pressure in the range of from 1000 to 3000 pounds per square inch gauge.

¦ Oil from the oil shale is 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 500~F. 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 square inch gauge and temperatures at least approximately as high as 700F. are required to effect a sub-stantially complete recovery of the oil.
Pevere, et al., U.S. Patent No. 2,665,390 (1948) describes in ; 30 ~¦ general te : a process ~or dlssolvlng coal ln llquld solv~nts at hlgh j _ 5 _ temp~ratllres and then atomiz-lng the solutloll into a carbonLzer but does not mentio-n the use of supercritical conditions. U.S. DeEensive Publi-catlon 700,~85 (filed January 25, 1968) re~ers to the use of a gas extractant to recover, from a solution oE coal in a liquid solvent a ~raction suitabl.e as n ~eedstock Eor hydrocrackLng to gasol-Lne.
Seitzer, U.S. Patent No. 3,642,607 (1972) discloses a process for dissolving bituminous coal by heating a mixture oE bituminous coal, a hydrogen donor oil, carbon monoxide, water, and an alkali metal hgdroxide or its precursor at a temperature of about 400-450C. and under a total pressure of at least about 4000 pounds per square inch guage.

Seitzer, U.S. Ratent No. 3,687,838 (1972) discloses the same process as disclosed in U.S. Patent No. 3,642,607 (1972) but employs ¦ an alkali metal or ammonium molybdate instead of an alkali metal hydroxide ¦ or l~s precll~sor, ¦ Urban, U.S. Patent No. 3,796,650 (1974) discloses a process for ¦ de-ashing and liquefying coal which comprises contacting comminuted ¦ coal with water, at least a portion of which is in the liqu~d phase, an ¦ externally supplied reducing gas and a compound selected from ammonia ¦ and carbonates and hydroxides 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, deslJIrurl~.itlg~ denltrl~yLng, demetalating~ and generally upgrading hydrocarboll Fractlons hy processes involvlng water. For example, Catsis, U.S. Patent No. 3,453,206 (1969) discloses a multi-stage process for hydrorefining heavy hydrocarbon fractions for the purpose of eliminating and/or reducing the concentration of sulfurous, nitrogenous, organo-metallic, and asphaltenic contaminants therefrom. The nitrogenous and sulfurous contaminants are converted to ammonia and hydrogen sulfide.
l The stages comprise pretreating the hydrocarbon fraction in the absence

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¦ of ~ cnenIy~t, wleh n mixture o~ water and e~t~rn~ y supplled hydrogen ¦ at ~ ~mpcratur~ nhovI~ the crlttc~l tempcrature of wuter and a pres~ure of nt lea~t lO()O po~md~ per squIlrc lnch gaugo nnd then reactlng the ¦ llquld producc from ehe pretre~Icment ~t~ge wleh externally supplied s ¦ hydrogen at hydroreflnlng condlttons and in the presence o~ a ca~alytlc I compo~lte. The catalytic composLte comprises a metallic component ¦ composited with a refractory lnor~anic oxide carrier material of either synthetic or natural origin, which carrier material has a medium-to-¦ hlgh sur~ace area and a well-developed pore structure. The metallic IO I component can be vanadium, niobium, tantalum, molybdenum, tungsten9 ¦ chromlum, iron~ cobalt~ nickel~ platinum~ palladium~ iridium~ osmium, ¦ rhodium, ruthenium~ and mixtures thereof. .
I (.atsis, V.S. Patent No. 3,501,396 (1970) discloses a process for ¦ de~ulfuri~ing and denitrifying oil ~ich compriseY mixing the oil I wlth water at a temperature above the critical temperature of water up to about 800F. and at a pressure in the range of from about 1000 to about 2500 pounds per square inch gauge and reacting the resulting mixture with externally supplied hydrogen in contact with a catalytic composite. The catalytic composite can be characterized 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 o~ this method ls the cataly9t belng acidic in nature. Ammonia and hydrogen sulfide are 2s produced in the conversion of nitrogenous and sulEurous 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 and liquid products by contacting the material to be converted with a nickel spinel catalyst promoted with a barium salt of an organic acid in the `~

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presen(e Or steam. A tempernture in the range o~ from 600F. to about 1()()()l~`. and n preAs~lre In tlle range Or from 200 to 300n pounds per sqllnre Lnch ~nuge are employed Prltchrord, U.S. Patent No. 3,676,331 (1972) discloses a method for upgrading hydrocarbons and thereby producing materials of low molecular weight and oE reduced sulfur content and carbon residue by introducing 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 of the components of the catalyst system promotes reaction between the hydrogen generated and the constituents of the hydrocarbon fraction. Suitable materials for use as the first component of the catalyst system are the carboxylic acid salts of barium, calcium, strontium, and magnesium. 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 750~F. to about 850F. and at a pressure of from about 300 to about 4000 pounds per square inch gauge in order to maintain a prlncipal portion of the crude oil in the liquid ¦ state.
¦ Wilson et al. 3 U.S. Patent No. 3,733,259 (1973) discloses a process I for removing metals, asphaltenes, and sulfur from a heavy hydrocarbon ¦ oil. The process comprises dispersing the oil with water, maintaining ¦ this dispersion at a temperature between 750F. and 850F. and at a ¦ pressure between atmospheric and 100 pounds per square inch gauge, I cooling the dispersion after at least one-half hour to form a stable Z-~

r-~phalt~n~ em~ n, ~epllrntln~ tho emu~ton rr~-m the tr~nted ~11, ~ddlng hydro~en, and contacting the re~ultlng tre~ted oil wlth a hydro-~nation cataly~t at a temperatllre between 500F. and 900F. and at a pressure between about 300 and 3000 pounds per ~quare inch gauge.
It has also been announced that the semi-governmental Japan Atomic Energy Research Institute, working with the Chisso Engineering Corpora-tion, has developed what is called a "simple, low-c~st, hot-water, oil desulfurization process" said to have l'sufficient commercial appli-cabillty to compete with the hyd~ogenation process." The process itself consifits of passing oil through a pressurized boiling water tank in whicll water is heated up to approximately 250C., under a pressure of about 100 atmospheres. Sulfides in oil are then separated when the water temperature i6 reduced to le~s than 100C.
Thus far, no one has disclosed the method of this invention for recovering and upgrading hydrocarbon fractlons from carbonaceous materials, which permits operatlon in a single step at lower than conventional temperatures, without an external source of hydrogen, and without preparatlon or pretreatment, such as, desaltlng or demetalation, prior to upgrading the re overed hydr~carbon fraction.
Thus the present invention provides a process for `. recovering upgraded hydrocarbon produ~ts from a carbonaceous material selected from the group consisting of oil shale solids, tar sands solids, coal solids, and a hydrocarbon fraction con-taining parafflns, olefins, olefin-equivalents~ or acetylenes, as such or as substituents on ring compounds, comprising contact-` ing the carbonaceous material with a water-containing fluid at a temperature in the range of from about 600F.- to about 900F., in the absence of externally supplied hydrogen, and in the presence of an externally supplied catalyst system containing a sulfur- and nitrogen-resistant catalyst selected from the group 'I
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consisting of at least one ~oluble ox insoluble transition metal compound, a transition metal deposited on a support, and com~
b~nations th~raof, wherein the density o~ water in the water-containing ~luid is at least 0.10 gram per milliliter ana sufficient water is present in the water-containing fluid to serve as an effective solvent for the recovered hydrocarbons.
In a preferred embodiment the hydrogen is generated in situ.
BRIEF DESCRIPTION OF ll~E DRAWINGS
Figure 1 is a graph showing the correlation of the calcination weight loss of oil shale wlth the results of the Fischer assay of such solids.
Figure 2 is a ser~es of plots sh~wing the dependence on te~perature of the yields of hydrocarbon product from oil shale using the method of this invention.
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 this invention.

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_ 9(a) -- ~,, I~-lgure 4 Ls <l ~e~les of plots showln~ the dependence of the o-LI
selèctlvity upon the particle size oE the oil shale and upon the contact time using the n~ethod of thls inventLon.
Figure 5 is a series of plots showing the effect on the ~ormation of hexane from l~hexene of varying amounts of a catalyst in the presence of a fixed amount of a promoter.
Figure 6 is a plot showing the effect on the formation of hexane Erom l-hexene of varying amounts of a promoter in the presence of a fixed amount of a catalyst.
0 Figure 7 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 carbonaceol 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 paraEfins, olefins olefin-equivalents, or acetylenes, as such or as substituents on ring compounds, hydrogenated, demetalated, and denitrified by contacting the carbonaceous material with a dense-water-containing phase, either gas or liquid, at a reaction temperature in the range of from about 600F. to about 900F. in the absence of externally supplled hydrogen, and in the presence of an externally supplied catalyst system. When the carbonaceou material is coal solids, the solld coal remaining after treatment by the method of this invention is desulfurized. This method is applicable to the whole range of hydrocarbons 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 cafbonaceous 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 flu~d phase must have a high solvent power and liquid-like densities - for s example, at least 0.1 gram per milliliter - rather than vapor-like 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 gaseous water 1s ma:Lntained at a temperature in the region of the critical temperature o~ water and at an elevated pressure is substantial. Even normally insoluble inorganic materials, such as silica and alumina, commence to dissolve appreciably in "supercritical water" - that is, water maintained at a temperature above the critical temperature of water - so long as a high water density is maintained.

Enough water ~ust be employed so that there is sufficient 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 maintained 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 ratlo in the range ¦ of Erom about 1:2 to about 1:3 ls more preferable. Slmllarly, a welght ratlo of the oil shale, tar sands, or coal sollds-to-water in the dense-water-contaLnLng phase ln the range of from about 3:2 to a~out 1:10 is s ¦ pre~erable, and a ratio in the range of from about 1:1 to about 1:3 is ¦ more preferable.
¦ A particularly useful water-containing fluid contains water in ¦ combination with an organic compound such as biphenyl, pyrldine, a partly hydrogenated aromatic oil, or a mono- or polyhydric compound such as lo ¦ methyl alcohol. The use of such combinations extends the limits of ¦ solubillty and rates of dissolution so that cracking, hydrogenation, ¦ desulfurizatlon, demetalation and denitrification 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 this invention is effective ¦ when added in an amount equivalent to a concentration in the water of the water-containing fluid in the range of from about 0.02 to about 1.0 weight percent and preferably in the range of from about 0.05 to about ¦ 0.15 weight percent.

¦ If the catalyst is not soluble in the water-contalning fluld, then -Lt may be ad~ed as a solid and slurried ln the reactlon mixture.
~lternately, the catalyst can be deposited on a support and slurrLed ln the water-containing fluid. Charcoal, actlve carbon, alundum~ and oxides such as silica, alumina, manganese dioxide, and titanium dioxide have been used successfully as supports for insoluble catalysts. ~ow-ever, high surface-area silica and alumina have only been satisfactory supports at reaction temperatures lower than the critical temperature of water.

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Any sultable conventional method for depositlng a catalyst on a support known to tllose in the art can be used. One suitable method :lnvo1ve~s immersillg the support in a solution contain:Lng the desired ¦ ~elght Or cataLyst d-Lssolved ln a sultable so1vent. The solv~nt Is ~hen removed, and the support with the catalyst deposlted thereon is dried.
The support and catalyst are then calcined ln an lnert gas stream at about 500C. for from 4 to 6 hours. The catalyst can then be reduced or oxidlzed as deslred.

This process can be performed elther as a batch process or as a lo contlnuous or seml-continuous flow process. Contact times between the carbonaceous material and the dense water-containlng phase -that is, resldence time ln a batch process or lnverse solvent space veloclty ln a r1ow process - oE from the order of minutes up to about 6 hours are sntisfactory for eEfectlve cracking, hydrogenation, desulfurizatlon, demetalatlon, and denitriflcatlon of the recovered hydrocarbons.

In the method of this invention, the water-contalnlng fluid and the oll shale, tar sands, or coal sollds are contacted by maklng a slurry of the oil shale, tar sands, or coal solids in the water-containing fluid.

When the method of this lnventlon is performed above ground with mined oll shale, tar sands or coal, the hydrocarbons can be recovered more rapidly if the mined solids are ground to a particle size preferably of l/2-inch diameter or smaller. Alternately, the method of this invention could also be performed in situ ln subterranean deposlts by pumplng the water-containing fluid into the deposit and withdrawing hydrocarbon products for separation or further processing.
l Examnles 1-37 I ._ ¦ Examples 1-37 involve batch processing of oil shale and tar sands ¦ feeds under a variety of conditions and illustrate that hydrocarbons lZ4 are recovered, cracked, hydrogenated, desulfurized, demetalated, and denitrified in the method of this lnvention. ~nless otherwise specified, the Eollowing procedure was used in each case. The oll shale or tar sands feed, water, and, if used, components of the catalyst system 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 or as solids in slurries in the water. Unless otherwise specified, 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 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-contalning fluid phase was Eormed.
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. Approxlmately another 6 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 final constant temperature and the period of time at this temperature are defined as the reactlon temperature and reaction time, respectively. ~uring the reaction time, the pressure of the reaction system increased as the reaction proceeded. The pressure at the start of the reaction time is

3~ ~ detined he reaction pres:~re.

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After the desired reaction time at the desired reaction temperature and pressure, the dense-water-containing fluid phase was de-pressurized and was flash-distllled from the reaction vessel, removing the gas, water and "oil", and leaving the "bitumen", inorganic residue, and components of tl1e catalyst system, if present, in the reaction vessel. The "oil"
was the liquid hydrocarbon fraction boiling at or below the reaction temperature and the "bitumen" was the hydrocarbon fraction boiling above the reaction temperature. The inorganic residue was spent shale or spent tar sands.
The gas, water, and oil 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 pressure 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 gravity.

The bitumen, inorganic residue, and components of the catalyst system, if present, were washed from the reaction vessel with chloro-Eorm, ; and the bitumen dissolved in this solvent. The solid residue was then separated from the solution containing the bitumen by filtration. The bitumen was analyzed for its sulfur and nitrogen contents using the same methods as in the analysis of the oil. The solid residue was analyzed for its inorganic carbonate content.
In regard to the recovery of 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 estimate the kerogenic content of these fractions9 portions of each 1(?41~1Z ~ I
sample were calcined in air at 1000F. for 30 minutes ~o remove water and kerogenic carbonaceous matter withou~ decomposi.ng inorganic carbonate The partlcle si~e of the samples of oil shale used in this work and the percent of weight loss during calcination for each of these sample6 are presented in Table 1.
Examples 1-36 involve batch recovery of hydrocarbons from the oil shale samples shown in Table 1 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 2 and 3, respectively.

In these F.xamples, the llquid 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 ln 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 l9~API.

to about 23API. The bitumen fractions had densities of about 1.01 grams per milliliter and API gravities of about 10. ~il shale sample A

contained 0.7 weight percent of sulfur, 1.7 weight percent of nitrogen.
Use of 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 and a decrease in the sulfur content of the products, The results of elemental analyses of several samples of oil and bitumen ~ractions obtained ln several of these Examples and also oi~

shale feed, and oil kerogen product obtained using thermal retorting as reported by M. T. Atwond in Chemtech, October, 1973, pages 617-621, are shown in Table 4, These B~

011 Shale Percent Weight Loss Sample Particle Sizel d~rln~ Calcination A 60-80 32.2 B 14-28 26.8 C 8-14 36.6 D 1/4-1/82 22.3 Footnot~s 1 mesh size, except where otherwise indicated.
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results indicate that the elemental compositions of oils Erom different oLl shales are quite similar. The weighted comblned results for the oil and bltumen fractions from Examples 7-ll obtained using the method of this lnventlon indicate that these fractions comblned have a similar nitrogen content but a lower sulfur content than does the oil obtalned using thermal retorting. The H/C atom ratios for oils obtained uslng the method of this invention are also similar to the H/C atom ratios for oils obtained by thermal retorting. However, the H/C atom ratio Eor the combined oil and bitumen fractions obtained using the method of this lo invention is less than that for the oil - that ls, total liquid products .

obtained by thermal retorting. This may reflect a larger total liquid yield obtained using the method of this invention than with thermolytic dlstillation.
The combined oil fractions obtained 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 combustion retorting. How-ever, the olefin content of the oil fraction boiling up to 405F. obtaine~
by the method of this invention differs from the oil content of the oil ; fractions bciling 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 2s obtained by the thermal or gas combustion retorting of hydro~arbons, oils having a reduced olefin content are obtained by the method of this invention. This indicates that hydrogen is generated in situ in the method of this invention and that such hydrogen is at least partially consumed in the hydrogemltion of recovered olefins.

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'11 Composition of Liquid from _ Method of Therma2 Combustl 2 this Invent:Lon ~ Retortin , ~ .
bitumen fraction 38 oil fraction 62 acid in component 3 3 4 base in compoent 14 8 8 neutral oil 45 to 405F. 6 15 4 paraffins and 3 3 naphthenes 48.53 27 273 olefins 20.03 4833 513 aromatics 31.53 25 22 405 to 600F. 10 paraffins and naphthenes 35.53 olefins 24.03 aromatics 40.5 600 to 700F. 6 residue (above 700F.) 23 Footnotes 1 weight percent of liquid products except where . otherwise indicated.
2 Results were reported in G. 0. Dinneen, R. A. ~lan 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.
3 voll-me percent of the pa~rticlll3r boillng p~int er3ction.

We have Çound 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 welght loss of such samples during calcination in air at 1000F. for 30 minutes. Both the volumetric and the weight contents of hydrocarbons are based on the Fischer assay described by L. Goodfellow, C. F. Haberman, and M. T.
Atwood9 "Modified Fischer Assay, "Division of Petroleum Chemistry, Abstracts, page F. 86, American Chemical Society, San Francisco Meeting, April 2-5, 1968. This correlation is shown in Figure 1.
lo Using this correlation, the expected yield of 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 1O6s during c~lcina~ion of the oil shale samples used and the correlation shown in Figure l 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 perormed 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 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 TAsLE 6 Data Oil Reaction Reaction Liquid Oil Erom Shale Temperature Time Se- Se-Example Samplel (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 lo 26 D 752 0.5 0.58 0.50 Footnotes 1 The samples corresponding to the letters are identified in Table 1.

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¦ total yield oE liquid products - Eor oll shale sample ~ at 752F. i6 1 0.61.
¦ The yield of oil recovered from oil shale by the method of thiæ
¦ invention was markedly dependent on the temperature. The total liquid ¦ product yield - oil plus bitumen - was roughly constant at temperatures ¦ above 705F. and dropped sharply at temperatures below 705F. At tem-¦ peratures above 705F., the total liquid product yields accounted for, ~ or even slightly exceeded the amounts recoverable estimated by the ¦ Fischer assay. Although essentially all available hydrocarbon was remove 0 ¦ from the oil shale by the method of this 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 catalysts intrinsically present in the oil shale - of ¦ the bitumen were occurring.
¦ Similar results, shown in Table 6, were obtained in Examples 1, 2, 20 ~ 15, and 26 - 28 with different contact times and with oil shale samples ¦ of different particle size ranges than those used in obtaining the ¦ results shown in Figure 2. These results indicate that even at a tem-perature of 698F., sl:Lghtly below the critical temperature for water, ¦ the liquid and oil selectlvities were substantially reduced from the¦ values obtained at temperatures above the critical temperature of water.

¦ 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 ¦ weight ratio of 0.56. The weight loss during calcination, the expected lZ~
yield of hydrocarbons Erom the oil shale sample, and the measured yleld Or liquid hydrocarbon products - all being expressed as welght percent o~ the oil ~hale feed - are .shown ln Flgure 3 as a eunctLon of the contac time nnd oE the range o~ partlcle slzes ol the oll shale ~eed. ('enerally with oll shale Eeed hav:Lng a particle siæe of approximately 1/4--lnch diameter or less, more than 90 welght percent of the carbonaceous content of the oil shale feed was recovered in less than one-half hour, When the oil shale feed had a particle size equal to or smaller than 8 mesh, the yield of total liquid products was greater after a contact ~ime of lo one-half hour than after a contact time of two hours, and exceeded the expected yield of hydrocarbons from the oil shale. For such feed, the decline of total yield of the liquid hydrocarbon products wlth increasing contnct time corresponded to lncrcased conversion of the liquid products to dry gas, for example by cracking the llquid products. Cracking was also indicated by the plots in Flgure 4 showlng the oll selectivity as a function of the contact time and of the range of the partlcle sizes of the oil shale feed.
When the oil shale feed had a particle size in the range of from 2 1/4-inch to 1/8-inch, the rate of recovery was low enough so that the O -total yield of liquid products after a contact time of one-half hour was less than the total yleld of llquld products after a contact tlme of two hours. lhis is indicated in Figure 3. While no theory for this is prop0~4ed, ir tlle oil shale ~eed iS made up of coarser materials havlng a 2s lnrger pMrtlcle size, the ratio ol surface area to particle volume for such materials would be lower than that for finer materials, and dlffusion of water into the coarser oll shale partlcles and the rate of dissolutlon of the lnorganlc matrix in the supercrltical 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 ,11 ~P4~
~ inorganic matrix oE the oil shale substrate. Following complete recovery ¦ of liqulds from oil shale Eeeds having particle sizes in the range of ¦ l/4-inch d-lameter to 80 mesh, the spent oil shale solids recovered had 1 substantially smaller particle sizes, generally less than l00 mesh.
¦ Further, there was also a decrease in the bulk density from about 2 l ¦ grams per mllliliter for the feed to about l.l grams per milliliter for ¦ the spent solids. On the other hand, when the liquids were not completel ¦ recovered from the oil shale feed, the oil shale particles retained much 1 of their starting conformation. For example, little apparent confor-lo ¦ mational change occurred for oil shale feed when only hal~ of the ¦ carbonaceous material was removed from it.
¦ There is 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 ¦ low 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-ll of liquid hydrocarbons from the oil shale sample A
¦ demonstrate that carbon dioxide is formed from lnorganic carbonate and ¦ is presented in Table 7.
¦ The relationships by which the products were characteri~ed are ¦ presented herelnaEter. The total amount, SO, of oil shale feed,

5 ¦ excluding entrained water, is glven as follows:
SO = S + IC + C
wherein 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, inthe oil shale ¦ feed was determined, and thus the relationship between the measured 1 amount of acid-titratable inorganic carbonate initially present and the ___ Weight Percent _nE_nent Component Symbolof the Feed Kerogen KC 32 Acid-titratable inorganic carbonate IC 19 Inorganic solid, S 4 excluding acid titratable inorganic carbonate Total lOO

Dry gas KG 1 Oil and bitumen KOB 23 Carbon dioxide 7 Kerogen coke yK 4 Acid-titratable inorganic carbonate xIc 15 Inorganic solid, S 50 excluding acid-titratable inorganic carbonate : Total _ 2~ 100 ' .11 measured total amount of oil shale feed could be expressed. Such relationship for oil shale sample ~ was IC = 0.187 S0 When the oil shale feed was calcined in air for 30 minutes at 1000F , all organic material was driven o:Ef, and the measured weight of total inorganic 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 equations, S was be calculated to be 0.491 S0.
lo The solid products obtained in the recovery of hydrocarbons from the oil shale feed by the method of this invention are given as follows:
S + XIC + 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 approximately ls 4000 pounds 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 inorganic 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 is the fraction of the amount initially present, Ic, which ls 2s still remalning.
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 0 could be expressed in terms of the total amount of oil shale as follows:
S + xIc = 0.643 S0 ~11 l~roln the last twn e~luat~ alcuLated to be 0.496 ~. ThLs value corresponcls closely to the value of S calculated from the analyt-lca characterization of the oil ~shale feed.
A very significant result Erom the analytical characterizatlon sho~ 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 gaseous carbon dioxide produced. Carbon dioxide derived from the kerogen in the oil shale feed could also account for some of the remainder. Generally, inorganic carbonate in the structure of oil shale survives thermal processlng if the temperature is kept no higher than 1000F. Thus, thermal or gas combustive retorting does 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 8. The recovery was complete under the conditions employed when the weight ratio of oil shale feed-to-solvent was in the range of 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 so that a continuous slurry pro-cessing system is possible.
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 4100 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. This run was performed in a 300-Res~lts Oil Oil Shale -to- Expected Welght ~ of Feed from Shale Water Total Hydro- Recovered as Example Samplel Weight Ratio ~ Oil Bitumen 1 ~ 1.0 22 13.2 8.3 3 A 0.6 22 13.5 6.5 13 B 1.0 16 11.8 9.0 B 0.6 16 10.5 5.0 12 C 1.0 22 17.8 9.2 14 C 0.6 22 14.4 7.4 Footnotes 1 The samples corresponding to the letters are identified in Table 1.

12~
milliliter Hastelloy alloy C Magne-Drive autoclave. The products of this recovery includecl gas (hydrogen, carbon diox-lde, and methane) and oil in amounts equivalent to 2 and 8 welght percent oF the feed, respectively. The oil 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 ~OFCAW process had an API gravity of 1202 and sulfur, nickel, and vanadium contents of 4.6 weight percent, and 74 and 182 parts per million respectively. Hence, the oil obtained by the method of this invention is upgraded relative to the oil produced by the COFCAW process.
Further, the yields of gas, oil, bitumen, and solid products in this Example 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 recovered constituted 97.4 weight percent of the tar sands and water feeds.
EXAMPLRS 38-lgl Rxamples 38-191 involve batch processing of different types of hydrocarbon feedstocks under the conditions employed in the method of this invention and illustrate that the method of this invention ef-fectively cracks, hydrogenates, desulfurizes, demetalates, and denitrifies hydrscarbons and therefore that the hydrocarbons recovered from the oil shale, tar sands or coal solids are also cracked, hydrogenated, desulfurized, demetalated, and denitrified in the method of this invention. Unless otherwise specified, the following procedure was used in each case. The hydrocarbon feed, water-containing fluid, and the components of the catalyst system, if present, were loaded at ambient temperature into a Hastelloy alloy C Magne-Drive or Hastelloy alloy B Magne-Dash autoclave in which the reaction mixture was to be mixed. The components of the catalyst system were added as solutes in . 1 1~4'~Z(~

the water-contalning Fluid or as sollds in slurries ln the water-con-tainlng Fluid. Unless otherwise specified, sufEicient water was added in each Example so that, at the reaction temperature and in the reaction volume used, the density of the water was at least 0.1 gram per milli-liter.
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 temperatllre i6 called the argon pressure.
lo The temperature of the reaction system was then raised to the desired level and the dense-water-containing fluid phase was formed.
Approximately 28 minutes were required to heat the autoclave from ambient temperature to 660F. Approximately 6 more minutes were required to raise the temperature from 660F. to 700F. Approximately, another 6 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 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-containing fluid, and "light" ends, and leaving the "heavy" ends, catalyst, if present, and other solids in the reaction vessel. The "light" ends were the liquid hydrocarbon fraction boiling at or below the reaction temperature, and the "heavy" ends were the hydrocarbon fraction boiling above the reaction temperature.

,.ll " 1~34~3124 'I'hc gas, water-containing fluid, and light ends were trapped in a pressure vc~sseL cooled by l-Lquid nltrogen. The gas was removed by w;~rming the pressure vessel to room temperatllre nnd then was analyzed by mass spectroscopy, gas chromatography, and in-fra-red. The water-con-s taining phase and llght ends were then purged from the pressure vesse]
by means of compressed gas and occasionally by heatlng the vessel. Then the water-containing fluid and light ends were separated by decantation.
Alternately, this separation was postponed until a later stage in the procedure. Gas chromatograms were run on the light ends.
lo The heavy ends and solids, including the catalyst, if present, were washed from the reaction vessel with chloroform, and the heavy ends di~ssolved in this solvent. The solids, including the catalyst, if present, were then separated from the solution containing the heavy ends by filtration.
After separating the chloroEorm from the heavy ends by distillation, the light ends and heavy ends were combined. If the water-containing fluid had not already been separated from 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 2~ 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 sulfur. X-ray fluoresence was used to determine nickel, vanadium, and sulfur.

Examples 38-40 illustrate that the catalysts employed in the method of this invention are not subject to poisoning by sulfur-containing compounds. Three runs were made, each with carbon monoxide in the amount of 350 pounds per square inch gauge in 90 milliliters of water, in a 240-milliliter Magne-Dash autoclave for a reaction time of four hours. Soluble ruthenium trichloride in the amount of 0.1 gram of RuC13 1-3H20 was employed as the catalyst in these Examples. Additionall , ¦ in Example 39, the water contained 1 milliliter of thiophene. The reaction conditions and the compositions oE the products ln each run are shown in Table 9. The presence oE a sulfur-containing compound, thiophene, did not cause poisoning of the catalyst or inhibltion of the water-gas shift~
Example 41 illustrates that the catalyst system operates as a catalyst for the hydrogenation of unsaturated organic compounds. When 15 grams of l-octene was contacted with 30 grams of water in a 100-milliliter Magne-Dash autoclave ~or 7 hours at a temperature of 662F.
at a reaction pressure of 3500 pounds per square inch gauge and an argon pressure of 800 pounds per square inch gauge, in the presence of soluble RuC13 1-3H20 catalyst, carbon dioxide, hydrogen, methane, octane, cis-and trans-2-octene, and paraffins and olefins containing five, six, and seven carbon atoms were found in an analysis of the products. These products indicate that substantial cracking and isomerization of the skeleton and of the location of the site of unsaturation occur. A 40%
yield of octane was obtained when 15 grams of l-octene and 30 grams of water were reacted in the presence of 0.1 gram of RuC13-1-3H20 for 3 hours, in the same reactor and at the same temperature, at a reaction pressure of 2480 pounds per square inch gauge and an argon pressure of 200 pounds per square inch gauge. A 75% yield of octane was obtained from the same reaction mixture3 in the same reactor, and under the same (ondltions, but after a reaction time of 7 hours and at a reaction 2s presslJre of 3470 pounds per square inch gauge and an argon pressure of 800 pounds per square inch gauge.
Examples 42-43 involve runs wherein sulfur-containing compounds, for example, thiophene and benzothiophene, are decomposed to hydrocarbons, carbon dioxide, and elemental sulfur. These Examples illustrate the efficiency of the catalyst system in catalyzing the desulfurization of sulfur-containing organic compounds.

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Reactton Keaction Product Compositlon ~ le Te ~ Pressurel ~i2 C2 CO

6~2 2550 26 22 52 Footnotes 1 pounds per square inch gauge.

t o 2 normalized mole percent of gas.

: 25 ln Example 42, a reaction mlxture of 12 milliliters of thiophene and 90 milliliters of water reacted ln a 240-mil:l:lliter Magne-Dash autoclave ln the presence of 0.1 gram of soluble RuCl3- 1-3~l20 catalyst at a reaction temperature of 662F., under a reaction pressure of 3150 pounds 5 per square inch gauge and an argon pressure of 650 pounds per square inch gauge, and for a reaction ~ime of 4 hours to yield Cl to C4 hydro-carbons and 0.1 gram of solid elemental sulfur but no detectable amounts of sulfur oxides or hydrogen disulfide.

In Example 43, a mixture of 23 milliliters of a solution of 8 mole lo percent thiophene (that is, about 3 weight percent sulfur) in l-hexene and 90 milliliters of water reacted in a 240-milliliter Magne-Dash auto-clave in the presence of 2 grams of solid alumina support containing 5 weight percent of ruthenium (equivalent to 0.1 gram of RuC13 1-3H2O) at a reaction temperature of 662F., under a reaction pressure of 3500 15 pounds per square inch gauge and an argon pressure of 600 pounds per square inch gauge, and for a reaction time of 4 hours to yield hydro-carbon products containing sulfur in the amount of 0.9 weight percent of the hydrocarbon feed and in the form of thiophene. This decrease in 2 thiophene concentration corresponds to a 70% desulfurization. The o activity of the catalyst was undiminished through 4 successive batch runs.
Examples 44-51 involve the proce~sing of samples of vacuum gas oil and residual fuels and illustrate that the catalyst system effectively z5 catalyzes the desulfurization, demetalation, cracking and upgrading of hydrocarbon fractions. The compositions of the hydrocarbon feeds used are shown in Table 10. The residual oils used in these Examples are designated by the letter "A" in Table 10.
Examples 44-47 involve vacuum gas oil; Examples 48-49 involve C

atmospheric residual oil; and Examples 50-51 involve Kafji residual oil.
30 l 3xample nvolves vscuom ga3 oil vnder slmilar condltlons as those _43_ ll used in Examples 45-47 but in the absence of catalyst, and is presented Eor the purpose of c~mparison. The experimental conditions, product composition, and extent of sulEur, nickel, and vanadium removal in these Examples are shown in Table 11. The liquld products are characterized as lower boil-lng or higher boiling depending whether they boil at or belo the reaction temperature or above the reaction temperature, respectlvely.
The reaction temperature was 715F., and a 300-mi~liliter Hastelloy alloy B Magne-Dash autoclave was used in each Example. Ruthenium, rhodium, and osmium were added in the form of soluble Ru~13 1-3H20, RhC13 3H20, and lo OsC13-3H20, respectively. The percent of sulfur, nickel, and vanadium removal are reported as the percent of the sulfur, nickel, and vanadium content of the hydrocarbon feed removed from the product.
Comparison of the results in Table 11 indicates that even thermal processing without the addition of catalyst from an external source causes considerable cracking and upgrading and a small amount of desulfurization of the hydrocarbon fraction. With a relatively high oil-to-water weight ratio, the compositions of the products obtained from thermal processing and from processing in the presence of a ruthenium catalyst are similar. With a lower oil-to-water weight ratio, analysis of the products reveals more extensive cracking in the presence of a ruthenium catalyst. Moreover, under similar conditions and with a ruthenium or a rhodium-osmium combination catalyst, there is essentially complete conversion of liquid feed into gases and liquid products boiling at temperatures equal to or less than the reaction temperature. The sulfur which was removed by desulfurization was in the form of elemental sulfur when the water density was at least 0.1 gram per milliliter - for example, when the oil-to-water weight ratio was 0.2 or 0.3. However, the removed sulfur was in the form of hydrogen sulfide when the water density was less than 0.1 gram per milliliter - for example, when the oil-to-water weight ratio was 5.4 or 6. This clearly indicates a change -ll o 1~4UlZ~
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Examples 52-53 involve promoters Eor the catalyst system of this invention Basic metal hydroxldes and carbonates and transition metal oxides, preferably oxides of metals in Groups IVB, VB, VIB, and VIIB of the Periodic Chart, do not function as catalysts for the water-reforming process but do effectively promote the activity of the catalysts of this invention which do catalyze water-reforming.
0 The promoter may be added as a solid and slurried in the reaction mixture or as a water-soluble salt, for example manganese chloride or potass1um permanganate, which produces the corresponding oxide under the conditionfi employed in the method of this lnvention. Alternately, the promoter can be deposited on a support and used as such ln a flxed-bed flow configuration or slurried in the water-containing fluld. The ratio of the number of atoms of metal in the promoter to the number of atoms of metal in the catalyst is in the rcmge of from about 0.5 to about 50 and preferably from about 3 to about 5.

The yields of the products of the water-reforming process are good indicators of promotional activity. In the water-reforming process, hydrogen and carbon monoxide are formed in situ by the reactlon of part of the hydrocarbon feed wlth water. The carbon monoxlde produced reacts with water forming carbon dioxide and additional hydrogen in situ. The hydrogen thus generated then reacts with part of the hydrocarbon feed to form saturated materials. Additionally9 some hydrocarbon hydrocracks to form methane. Thus, the yields of saturated product, carbon dioxide, and methane are good measures of the promotional activity when a promoter is present in the catalyst system The yields of hexane obtained by processing l-hexene in ~xamples 52 and 53 are presented in Figures 5 and 6, respectively. The hexane yield ' - 4.~ -Z'~
is shown in terms oE the mole percent of l-hexene feed which is converted to hexane in the product, In Rxamples 52 and 53t a reaction temperature of 662F., a reaction time of 2 hours, 90 grams of water, 17 -~ .5 grams of l-hexene, and a 300-milliliter Hastelloy alloy B Magne-Dash autoclave were employed. In Figure 5, the runs from which points labelled 1 through 5 were obtained employed reaction pressures of 3450, 3400, 2800, 3450, and 3500 pounds per square inch gauge7 respectlvely, and argon pressures of 650, 650, 0, 620, and 620 pounds per square inch gauge, respectively. Runs corre-lo sponding to points labelled 1 through 3 employed 0.2 gram of manganese dioxide as promoter, while runs corresponding to points labelled 4 and 5 employed no promoter. In Figure 6, the runs from which points labelled 1 through 3 were obtained employed reaction pressures of 2800, 3560, and 2900 pounds per square inch gauge, respectively, and argon pressures of s 650 pounds per square inch gauge.

Figure 5 shows the increase of hexane yield with increasing amounts of ruthenium catalyst and with either no promoter added or 0.2 gram of manganese dioxide promoter added. Similarly, Figure 6 shows the increase of hexane yield with increasing amounts of manganese dioxide promoter and 0.1 gram of RuC13 1-3H20 catalyst present. These plots indicate that, in the absence of catalyst, the pro~oter alone showed no water-reforming catalytlc activity, with the hexane yield being less than 2 mole percent of the feed. Also, for a given concentration of catalyst, addition of 0.2 gram of the promoter produced substantially increased yields of hexane in the product.
Examples 54-67 involved 2-hour batch runs in a 300-milliliter Haste-lloy alloy B Magne-Dash autoclave which employed 0.1 gram of RuC13 1-3H20 catalyst and 0 2 gram of various transition metal oxides at 662F. The argon pressure was 650 pounds per square inch gauge in each Example.
The yields of hexane, carbon dioxide, and methane are shown in Table 12.

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l There was an increase in the yield of hexflne with all of the oxides ¦ used except barium oxide. There was only a small lncrease in the yield ¦ of hexane when copper (Il) oxide was used. Thus, oE the promoters shown, ¦ efE~cient promo~ion of catalytic activity in water-reforming is achieved ¦ primarily with transition metal oxides.
The ratio of the yield of methane in moles either to the yield oE
¦ carbon dioxide in moles or to the yield of hexane in mole percent of the ¦ hydrocarbon feed is an indication of the relative extents to which the ¦ competing reactions of hydrocracking and in situ hydrogen formation by 0 ¦ water-reforming proceed. The results shown in Table 12 indicate that a ¦ given promoter catalyzes hydrocracking and hydrogen production to ¦ different degrees. Consequently, by choosing one promoter over another, ¦ it is possible to direct selectivlty toward either hydrocracking or ¦ hydrogen production, as well as to promote the activity of the catalyst.
¦ No theory is proposed for the mechanism by which basic metal ¦ hydroxides and carbonates and transitlon metal oxides promote the ¦ activity of the catalysts in the method of this invention. However, there is evidence to indicate that the promotion of catalytic activity by transition metal oxides at least is a chemical effect and not a surface effect. To illustrate, Example 68 was performed under the same experimental conditions as those used in Example 54, but employed instead a catalyst of 1 gram of high surface area, active carbon chips containing 5~ by weight of ruthenium - that is, 0.5 millimole of ruthenium, which i~s equivalent to 0.1 gram of RuC13-1-3H20 - with no promoter being present. The carbon chlps had a surface area of 500 square meters per gram. The yield of hexane was 12 mole percent, and the yield of carbon dioxide was 0.017 mo~e. Both of these yields were smaller than the corresponding yields found in Example 54 in the absence of a promoter.

Examples 69-75 demonstrate the varying degrees of effectiveness of different combinations of catalysts and promoters in catalyzing cracking, _ 50 -4~12 ~

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¦ hydrogenation, skeletal isomeriæation, and olefin-position isomerization of the hydrocarbon feed. In each case, the hydrocarbon feed was a solution of 3fi mole percent of l-hexene in the diluent benzene, except ¦ Example 73 where the benzene was replaced by ethylbenzene. In each ¦ lxample, the reaction was carried out in a 300-milliliter Hastelloy alloy ¦ T~ MaKne-l)ash autoclave Imder an argon pressure of 650 pounds per ~quare inch gauge at a reaction temperature of 662F. and for a reaction time ¦ of 2 hours. The feed compositions, pressures, catalyst compositions, ¦ product yields, and conversions of the l-hexene feed are shown in Table o 1 13.

~ The high conversion of l-hexene in Example 69 reflects skeletal ¦ isomerization to methylpentenes and olefin-position isomerization to 2-¦ and 3-hexene, but there was only a 26% yield of hexane w~th the unpromote ¦ c~talyst system. ~dditlon of a trAnsltlon metal oxlde, a trnnsltion l~, ¦ metal salt - for example ~antalum pentachloride - whlch Eormed n trans:Ltl n ¦ metal oxide under the conditions employed, or n baslc meta~ carbonate ¦ caused a substantial increase in the yield of hexane. When the catalyst ¦ system was basic, skeletal isomeriza~ion was completely suppressed, but I olefin-position isomerization still occurred. None Oe the catalyst ¦ systems in Examples 69-75 were effective in cracking or hydrogenating the diluents, benzene and ethylbenzene. When ethylbenzene was used as the diluent, only trace amounts of dealkylated products, benzene and toluene, were produced.

Examples 76-82 demonstrate the relatLvely high efficiency of certain members of the catalys~t system of the method of this invention in catalyzing the cracking of alkyl aromatics. In each Example, the hydrocarbon feed was a solution of 43 mole percent of l-hexane and 57 mole percent of ethylbenzene. In each Example, the hydrocarbon and water were contacted for 2 hours in a 300-milliliter Hastelloy alloy B
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¦ Although all the catalyst systems employed in Examples 76-82 were ¦ effective in cataly~ing water-reforming activity involving l-hexene, ¦ only iridium and rhodium were effective in cleaving ethylbenzene to ¦ ben~ene and toluene. Comparison of the product yields in Examples 1 79-81 indicates that cleavage of alkyl aromatics is effected using a ¦ catalyst system involvlng the combination of either iridium or rhodium 0 ¦ with another one of the catalysts of this invention, but not iridium ¦ or rhodillm alnn~.
¦ l~xample~ 83-85 demon~trate that alkylben~enes are cleaved u~:Lng the ¦ methocl oE thls Ln~ention with the same catalyst system used ln ~xample 79 ¦ even ln the absence of an oleEin ln the llydrocarbon fee~. Each of these ¦ Examples involve 2-hour runs in a 300-milliliter Hastelloy alloy X
¦ Magne-Dash reactor, at a reaction temperature of 662F. and under an ¦ argon pressure oE 650 pounds per square inch gauge. The hydrocarbon ¦ feed compositions, the amounts of water added, the reaction pressures, I and the yields of products from the cracking of the alkyl aromatlcs are ¦ ~hown Ln Table 15.
l Example 86 demonstrates that saturated hydrocarbons can be cracked ¦ in the method ~f this invention using the same catalyst system used in ¦ Example 79. In this Example, 15.9 grams of n-heptane and 92.4 grams of ¦ water were mixed in a 300-milliliter Hastelloy alloy B Magne-Dash auto-¦ clave and heated at a reaction temperature of 662F. under a reaction pressure of 3100 pounds per square :Lnch gauge and an argon pressure of 650 pounds per square inch gauge for a reaction time of 2 hours.
Methane in the amount of 0.67 grams - corresponding to 4.2 weight per-cent of the n-heptane feed - was produced in the reaction. The fact that only traces of products having a higher carbon number than methane ~ 4V~Z4 ~ ~ , o o ~o~ ~ o ~ o o O n ~ ~

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F~amples 87-116 lnvolve processing of tar s~nds oLI feeds in a 300-milliliter Hastelloy alloy C Magne-Drive reactor. ~he properties of the tar sands feeds employed in these Example~ are shown ln Table lO. Topped tar ssnds oil is the straight tar sands oil whose propercles are presentec in Table 10 but from which approximately 25 weight pcrcent of light material has been removed. S~raight tar aands oil was used as feed in Examples 87-102, while topped tar sands oil was used as ~eed in Examples 0 103-116. The experimental conditions used and the results of analyses of the products obtained in these Examples are shown ln Tnbles 16 and 17, respectively. The reaction temperature was 752F, in each Example.
Ruthenium, rhodium, .lnd osmium were added in the ~orm of soluble Il~ t3 1-3H2(), RhC13'3~l20, and OsC13 3~l2n, respectively. F.ach component oE the catalyst system in each Example was added either in the form of its aqueolls solution or as the solid in a solid-water slurry, depending on whether or not ~he component was water-soluble.
Comparison of the results shown in Table 17 shows that the pro-duction of gas and solid residue and the extent of removal of sulfurand metals increased when the reaction time increased from 1 to 3 hours, when no catalyst was added from an external source. Addition of a catalyst from an external source produced small increases in the yield of ~solid residues and in the API gravities of the liquld productl but, unlike with feeds other than tar sands oils, had little effect on yields from hydrocracking and on C/H atom ratios. Further, alteration of the oil-to-water weight ratio from 1:3 to 1:2 generally resulted in a decrease in the extent of removal of sulfur and metals and an adverse shift in the product distribution. With feeds other than tar sands oil, , the shifts were less adverse with increases in the hydrocarbon-to-water weight ratio, until 1:1 was reached.

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The re~ults for the heavier topped ~nr ~ands oil nre sLmllar to tllose for the straight tar sands oll. nn~ d~ference ls that the conversion of heavy ends to light ends ~or ~he topped tar sands oil continued to lncrease as the reaction time increased from 1 to 3 hours, while such conversion was substantially complete in about one hour Eor the stralght tar sands o$1.
The total yields and compositions oE the gns products obtained in a number of the Examples whoss results are shown in Table 17 are indicated in Table 18. In all cases, the main component of the gas products was argon which was used ln pressurizatlon of the reactor and which is not reported in Table 18. Changing the oil-to-water weight ratio from 1:3 to 1:2 and/or increaslng the reaction time resulted in increased yields of ga~s. AddLtLon of a catalyst also cau~ed nn lncrease ln the yield o~
gnseoua products.
~5 The presence of carbon dioxide and hydrogen among the gas products obtained ln Examples 91, 92, 103, and 104 suggests that hydrogen and carbon monoxide were generated even without the addition of catalysts from an external source, probably with metals inherently present in the tar sands oils serving as catalysts.
Comparison of the results shown in Table 17 indicates that addition of catalysts generally resulted in a greater degree of desulfurization than that caused when no catalyst was added from an external source.
Further, addition of a transition metal oxide or a basic metal hydroxide or carbonate either alone or as a promoter in the presence of a water-reforming catalyst markedly improved the degree of desulfuriæation.
However, as with hydrocarbon feeds other thnn tar sands o:Lls, the extent of desulfurization decreased with increasing reaction time. In all cases, the sulfur which was removed from the oil appeared as elemental .

sulfur and not as sulfur dioxide or hydrogen sulfide.

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¦ ~lowever, addition of a catalyst and/or a transition metal oxide or a ¦ basic metal hydroxide or carbonate promoter further lncreased the extent ¦ of demetalation.
¦ Examples 117-170 involve batch runs in a 300-milliliter ~lastelloy ¦ alloy C Magne-Drive reactor using Khafji and C atmospheric residual ¦ oils. The properties of these residual oils are shown in Table 10 and ¦ are designated by the letter "B". Examples 117-134 involve Khafji ¦ atmospheric residual oil, while Examples 135-170 involve C atmospheric ¦ residual oil. The reaction conditions employed ln these Examples is lndlcated in Table L9. ~11 runs were made at 752F , except where ¦ otherwise indlcated in Table 19. ~he experlmentaL resuLts are lndlcated I ln Table 20.
¦ The results Ln Table 20 lndicate that cracking and desulfurization ¦ occurred in runs made in the absence of a catalyst added from an ¦ external source as well as in runs made with an added catalyst. However, addition of a catalyst from an external source significantly enhanced the yields of gases and of light ends, even after a greatly reduced reaction time. ~urther, addition of a promoter to the catalyst system caused an increase both in the absolute yield of gases and in the ratio of yields of gas-to-solid. Use of sufficient water to maintain a water 2s density of at least 0.1 gram per milliliter - that is, use of hydrocarbon feed and water in proportions such that the weight ratio o~ water-to-hydrocarbon feed was relatively high - also caused a greater yield of gases and light ends, and a greater extent of desulfurization than when the weight ratio of water-to-hydrocarbon was relatively low. Addition of l-hexane, a hydrogen donor, to the reaction mixture resulted in a lower yield of solid product and an increased yield of light ends.

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JlZ4 In general, the extent of desulfurization increased when the reaction temperature was higher, when the reaction time was in a certain range, when the water-to-hydrocarbon feed weight ratio was higher, and when a promoter was added to the catalyst system. Further, use of the promoters even in the absence of a catalyst caused satisfactory desulfuri zation.
The sulfur which was removed from the residual oils appeared in the products as elemental sulfur when the density was at least 0.1 gram per milliliter - that is when a relatively low hydrocarbon-to-water feed tO weight ratio, such as 1:1, 1:2, and 1:3, was employed. When the water density was less than 0.1 gram per millillter - that is, when a relativel high hydrocarbon-to-water weight ratio, such as 4:1, was employed - part of the sulfur removed from the hydrocarbon fead appeared in the products as hydrogen sulfide.
T.n ~enera~, th~ e~t:ent of demetalntion increased when thc water-to-hydrocarbon feed weLE~ht ratlo wns hlgher, when a promoter was added to the catalyst system and ~len the reaction tlme was in a certaln range. Further, u~e of the promoters even in the ab6ence of a catalyst caused satisfactory demetalation.
Examples 171-187 involve batch runs in a 300-milliliter l~astelloy alloy C Magne-Drive autoclave using C vacuum residual oil and Cyrus atmospheric residual oil. The properties of these residual oils are shown in Table 10 and are designated by the letter "B". Examples 171-173 involve C vacuum residual oil, while Examples 174-187 involve 25 Cyrus atmospheric residual oil. The reaction conditions employed in these Examples is indicated in Table 21. All runs were made at 752~F.
The experimental results are indicated in Table 22.
The results ln Table 22 indicate that satisfactory desulfurization and demetalation of C vacuum and Cyrus atmospheric residual oils were 30 ¦ ee tsd. CrscklnL~ o~ the C scaam r sld~al oil tesalted in some ~l L
formation of gases and light ends but not to the extent found with tar sands oils and with Khafji and C atmospheric residual oils.
Cracking oE the Cyrus atmospheric residual oil occurred more readily than cracking of C vacuum residual oil, but the Cyrus atmospheric residual oil appeared to be more refractory than the Khafji or C atmospheric residual oils. Cracking of the Cyrus atmospheric residual oil in the absence of a catalyst added from an external source resulted in a large yield of solid products. Cracking of this hydro-carbon feed in the presence of a ruthenium catalyst or rhodium -osmium lo combination catalyst added from an external source resulted in an increase in the yield of light ends but did not lower the yield of solid product. However, cracking of this hydrocarbon feed in the presence of an lron-manganese or ruthenium-osmium combination catalyst or with a hydrogen-donor, like ethanol or l-hexene, added to the water solvent resulted in a lower yield of solid product and an lncreased yield of light ends.
Example 188 illustrates the denitrification of hydrocarbons by the method of this invention and involves a 2-hour batch run in a 300-milli-liter Hastelloy alloy B Magne-Dash autoclave. In this Example 15.7 grams of l-hexene were processed with 91.4 grams of water containing 1 mLlliliter (0.97 grams) of pyrrole, in the presence of 0.1 gram of soluble RuC13 1-3H2O catalyst, at a reaction temperature of 662F., and under a reaction prPssure of 3380 pounds per square inch gauge and an argon pressure of 650 pounds per square inch gauge. The products included gases in the amount of 10.1 liters at normal temperature and pressure and 14.3 grams of liquid hydrocarbon product. The gas products were made up prLmarily of argon and contained 6.56 weLght percent of carbon dioxide and 1.13 weight percent of methane. The amount of hexane in the product constituted 46.6 weight percent of the l-hexane feed.
The liquid hydrocarbon product contained 888 parts per million of " 11 1(14(1 1Z~

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Examples 189-191 illustrate that the catalyst of the method of this invention is nitrogen-resistant and involve 4-hour batch runs in a 300-mllliliter Hastelloy alloy B Magne-Dash autoclave. In each of these examples, 12.8 grams of l-hexene were processed with 90 grams of water at a reactlon temperature of 662F., under an argon pressure of 650 polmds per square inch gauge and in the presence of 2.0 grams of silicon dioxide containing 5 weight percent of ruthenium catalyst. The supported lo catalyst had been calcined in oxygen for 4 hours at 550C. Examples 189, 190, and 191 were performed under a reaction pressure of 3500, 3500, and 3400 pounds per square inch gauge, respectively. The reaction mixture in Examples 190 and 191 Lncluded addit:lonnlly 1 mi:Lliliter tO.97 grams) of pyrro~e. Example 191 was performed under ident:Lcnl condltlons as ~5 those used in ~xample 190. Additionally, the same catalyst used in Example 190 was re-used in Example 19L. The yields of hexane in Examples 189, 190, and 919 were 16.6, 14.0, and 13.9 weight percent of the 1-hexene feed, respectively. Within the ordlnary experimental error of this work, these yields indicate no nitrogen poisoning.

Examples 192-201 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 in Figure 7. To start a run, either 1/8-inch diameter inert, spherical alundum balls or lrregularly shaped titanium oxide chips having 2 weight percent of ruthenium catalyst deposited thereon were packed through top 19 into a 21.5-inch long, 1-inch outside diameter and 0.25-inch inside diameter vertical Hastelloy alloy C pipe reactor 16. Top 19 was then closed and a furnace (not shown) was placed around the length of pipe reactor 16. Pipe reactor 16 had a total eEfective heated volume of about 12 milliliters, and the pack-ing material had a total effective heated volume of about 6 milli-liters, leavlng approxlmately a 6-milliliter effective heated free 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 flow system when the desired pressure ln the system was exceeded, the Elow system was brought up to a pressure in the range of from about 1000 to about 2000 pounds per square inch gauge by argon or nitrogen entering o the system through valve 80 and line 79. Then valve 80 was closed. Next the pressure of the flow system was brought up to the desired reaction pressure by opening valve 53 and pumping water through ~laskel pump 50 and line 51 into water tank 54. The water served to further compress the gas in the 1OW system and thereby to further increase the pressure in the system. If a greater volume of water than the volume of water tank 51 was needed to raise the pressure of the flow system to the deslred 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 fraction 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 atmospheric pressure. Pistons (not shown) inside these barrels were manually turned 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 fraction 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 fraction and water streams ~oined at point 10 at ll lU4(~124 ambient temperature and at the desired pressure, flowed through 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 ¦ side arm 24 at point 20 in the wall of pipe reactor 16. Point 20 was 19 ¦ inches from bottom 17.
¦ ~ith 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 ¦ condltions were achieved, valve 43 was closed and valve 34 was opened for the desired period of time to permlt the mixture in sLde arm 24 to ¦ ~low through line 33 and to enter and be s~ored ln product recelver 35.

¦ ~ter collecting a batch o~ product in product receiver 35 Eor the desired period of time, valve 34 was closed and valve 26 was opened to ¦ permlt the mlxture in side arm 24 to flow through line 25 and to enter and be stored in product receiver 27 for another period of time. Then valve 26 was closed.

The material in side arm 24 was a mixture of gaseous and liquid phases. When such mixture entered dump tank 44, product receiver 35, or product receiver 27, the gaseous and liquid phases separated, and the gases exited from dump tank 44, product receiver 35, and product receiver 27 through lines 47, 38, and 30, respectively, and passed through line 70 and Annin valve 82 to a storage vessel (not shown).
When more than two batches of products were to be collected, valve 29 and/cr valve 37 was opened to remove product from product receiver 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 and the Elow system was depressuri~ed by ¦ opening valve 84 ln line 85 venting to the atmosphere.
¦ Diaphragm 76 measured the pressure differential across the length ¦ of pipe reactor 16~ No solution flowed through line 74.
¦ The API gravlty of the liquid products collected were measured, and ¦ their nickel, vanadium, and iron contents were determined by x-ray ¦ Eluorescence.
¦ The properties of the straight tar sands oil feed employed in ¦ Examples 192-201 are shown in Table 10. 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 in the product.
¦ The experimental conditions and characteristics of the products formed in ¦ these T~xamples are pre8ented ln Table 23, The liquid hourly space ¦ velocity (~USV) wa~ calculated by divldlng the total volumetric Flow rate in milliliter8 per hour, Oe water and oil feed passing through ¦ pipe reactor 16 by the volumetric free space in pipe reactor 16 - that ¦ ls, 6 milliliters.
The flow process employed in Examples 192-201 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 reactor 16. In such case, the alundum balls would not be present in pipe reactor 16, and dump tank 44 and product recelvers 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.

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lU401Z4 I ~ o .~,j i EXA~PLES 202-223 ~xamples 202-223 involve batch processing of coal feeds under a variety of conditlons 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 ln 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 solvents 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 raaction tem-perature and pressure and :ln the reaction volume used, the density of the water W89 at least 0.1 gram per mllli~iter, 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. 'I'he 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 fluid phase was formed.
~pproximately 28 minutes were required to heat the autoclave from ambient temperature to 660F. Approximately 6 minutes were r~quired to 2 ~ raise the temperature from 660F. to 70QF. Approximately another 6 ¦ 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 Einal constant ¦ temperature and the period o 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 i5 ¦ 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 ¦ by flash-distilling from the reaction vessel, removing the argon, gas ¦ products, water, and "oil", and leaving the "bitumen," solid residue, ¦ and ca~alyst, if present, in the reaction vessel. The "oil" was the ¦ liquid hydrocarbon fraction boiling at or below the reaction temperature 1 ¦ 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 lS ¦ the ga~ product~ were an~lyzed by mass spectro~copy, gas chromato~rnphy, ¦ and infra-red. The water and oil were then purged from the pressure ¦ vessel by means of compressed gas and occasionally also by heating the ¦ vessel. Then the water ànd oil were separated by decantation, The oil was analyzed for its sulfur content using X-ray fluoresence.

20 ¦ 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 filtration. The bitumen and solids were analyzed for thei~ sulfur contents using the same method as in the analysis of the oil.
The weights of the various components or fractions added and recovered were determined either directly or indirectly by dlfference at various stages during the procedure.
Three samples of coal were used in this work. The samples were obtained in the form of lumps, which were then ground and sieved to obtain fr tions oE variou: particl: sizes. ~he particle :ize and Il I

Il 1~4~i12~ l ¦ moisture and sulfur contents of each sample used are presented in Table ¦ 24~ Samples A and B were obtained from Commonwealth Edison Company, whil ¦ sample C was an Illinois number 6 seam coal obtained from Hydrocarbon ¦ Research Incorporated. Sample A was a sub-bituminous coal, while samples ~ B and C were highly volatile bituminous coals. These samples were stored ¦ lmder a blanket of argon until used, ¦ Examples 202-223 involve batch recovery oE liquids and gases from ¦ the coal samples shown in Table 24 using the method described above.

¦ These runs were performed in a 300-milliliter Hastelloy alloy C Magne-o ¦ Drive autoclave. The experimental conditions and the results obtained ¦ in these ~xamples are presented in Tables 25 and 26, respectively.
¦ In these Examples, the liquid hydrocarbon products were classlEied ¦ either as olls or as bitumens depend:Lng on whether or not such liquid product~ could be flAshed from the autoclnve upon clepressur1zatlon o~
the autoclave at the run temperature employed. Oils were those liquid products which ~lashed over at the rtm temperature, while bitumens were those liquid products which remained in the autoclave.
The weight balance shown in Table 26 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 catalyc t, 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 ln grams by the difference between the weight of the coal feed in grams and its moisture content in grams. The percent of coal conversion is lO0 minus the weight percent of solid recovered.
The results shown in Table 26 illustrate that substantial conversio of coal solids occurred with both bituminous and sub-bituminous coal using the method of this invention. There was also substantial 3~

Coal Part~cle Moisture Sulfur 3 l Sample Size Content2Content ¦ A 10-40 22.2 0.74 B 10-40 9.7 4.5 l C4 ? 80 2.7 4.9 ¦ Footnotes lo ¦ l me~h size.
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desulfurization in each case where the sulfur content of the products ¦ was determined. Addition o~ a catalyst in the method of this invention ¦ in Examples 217 through 223 resulted in an increase in the production of ¦ the oil fraction relative to the gas and bitumen fractions.
¦ The results of Examples 210, 211, and 213 indicate that the organic ¦ co-solvent made no contribution to the amount of solid product recovered.
¦ Therefore, the amount of solid remaining a~ter 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 distingulsh between the con-¦ tributions oE the coal feed and of the co-solvent to the y~elds oE gas ¦ and liquid products, when a co-solvent was used.
¦ The above examples are presented only by way oE illustration, and ¦ the Inventlon should not he construed as llmited thereto. The various ¦ components of the catalyst system of the method of this lnvention do not ¦ possess exactly identical effectiveness. The most advantageous selection of these components and their concentrations and of the other reaction conditions will depend on the particular carbonaceous material being processed.

Claims (39)

We Claim:

1. 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-containing fluid at a temperature in the range of from about 600°F. to about 900°F., in the absence of externally supplied hydrogen, and in the presence of an externally supplied catalyst system containing a sulfur- and nitrogen-resistant catalyst selected from the group consisting of at least one soluble or insoluble transition metal compound, a transition metal deposited on a support, and combinations 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.

2. The process of Claim 1 wherein the catalyst is selected from the group consisting of ruthenium, rhodium, iridium, osmium, paladium, nickel, cobalt, platinum, and combinations thereof.

3. The process of Claim 2 wherein the catalyst is selected from the group consisting of ruthenium, rhodium, iridium, osmium, and com-binations thereof.

4. The process of Claim 1 wherein the catalyst is present in a catalytically effective amount which is equivalent to a concentration level in the water-containing fluid in the range of from about 0.02 to about 1.0 weight percent.

5. The process of Claim 4 wherein the catalyst is present in a catalytically effective amount which is equivalent to a concentration level in the water-containing fluid in the range of from about 0.05 to about 0.15 weight percent.

6. The process of Claim l wherein the catalyst system contains additionally a promoter selected from the group consisting of at least one basic metal hydroxide, basic metal carbonate, transition metal oxide, oxide-forming transition metal salt, and combinations thereof, wherein said promoter promotes the activity of the catalyst.

7. The process of Claim 6 wherein the transition metal in the oxide and salt is selected from the group consisting of a transition metal of Group IVB, VB, VIB, and VIIB of the Periodic Chart.

8. The process of Claim 7 wherein the transition metal in the oxide and salt is selected from the group consisting of vanadium, chromium, manganese, iron, titanium, molybdenum, copper, zirconium, niobium, tantalum, rhenium, and tungsten.

9. The process of Claim 8 wherein the transition metal in the oxide and salt is selected from the group consisting of chromium, manganese, titanium, tantalum, and tungsten.

10. The process of Claim 6 wherein the metal in the basic metal carbonate and hydroxide is selected from the group consisting of alkali and alkaline earth metals.

11. The process of Claim 10 wherein the metal in the basic metal carbonate and hydroxide is selected from the group consisting of sodium and potassium.

12. The process of Claim 6 wherein the ratio of the number of atoms of metal in the promoter to the number of atoms of metal in the catalyst is in the range of from about 0.5 to about 50.

13. The process of Claim 12 wherein the ratio of the number of atoms of metal in the promoter to the number of atoms of metal in the catalyst is in the range of from about 3 to about 5.

14. The process of Claim 1 wherein the density of water in the water-containing fluid is at least 0.15 gram per milliliter.

15. The process of Claim 14 wherein the density of water in the water-containing fluid is at least 0.2 gram per milliliter.

16. The process of Claim 1 wherein the temperature is at least 705°F.

17. The process of Claim 1 wherein the carbonaceous material is contacted with the water-containing fluid for a period of time in the range of from about 1 minute to about 6 hours.

18. The process of Claim 17 wherein the carbonaceous material is contacted with the water-containing fluid for a period of time in the range of from about 5 minutes to about 3 hours.

19. The process of Claim 18 wherein the carbonaceous material is contacted with the water-containing fluid for a period of time in the range of from about 10 minutes to about 1 hour.

20. The process of Claim 1 wherein the water-containing fluid is substantially water.

21. The process of Claim 20 wherein the water-containing fluid is water.

22. The process of Claim 1 wherein the carbonaceous material is selected from the group consisting of oil shale solids, tar sands solids, and a hydrocarbon fraction containing paraffins, olefins, olefin-equivalents, or acetylenes, as such or as substituents on ring compounds, wherein the upgraded hydrocarbon products are cracked, hydrogenated, sesulfurized, demetalated, and denitrified and wherein essentially all the sulfur removed from the recovered hydrocarbons is in the form of elemental sulfur.

23. The process of Claim 22 wherein the carbonaceous material is a hydrocarbon fraction containing paraffins, olefins, olefin-equivalents, or acetylenes, as such or as substituents on ring compounds, wherein the weight ratio of the hydrocarbon fraction-to-water in the water-containing fluid is in the range of from about 1:1 to about 1:10.

24. The process of Claim 23 wherein the weight ratio of hydrocarbon fraction-to-water in the water-containing fluid is in the range of from about 1:2 to about 1:3.

25. The process of Claim 22 wherein the carbonaceous material is oil shale or tar sands solids and wherein the weight ratio of the oil shale or tar sands solids-to-water in the water-containing fluid is in the range of from about 3:2 to about 1:10.

26. The process of Claim 25 wherein the weight ratio of oil shale or tar sands solids-to-water in the water-containing fluid is in the range of from about 1:1 to about 1:3.

27. The process of Claim 25 wherein the oil shale solids have a maximum particle size of one-half inch diameter.

28. The process of Claim 27 wherein the oil shale solids have a maximum particle size of one-quarter inch diameter.

29. The process of Claim 28 wherein the oil shale solids have a maximum particle size of 8 mesh.

30, The process of Claim 1 wherein the carbonaceous material is coal solids and wherein the upgraded hydrocarbon products are cracked and desulfurized.

31. The process of Claim 30 wherein the weight ratio of coal solids-to water in the water-containing fluid is in the range of from about 3:2 to about 1:10.

32. The process of Claim 31 wherein the weight ratio of coal solids to-water in the water-containing fluid is in the range of from about 1:1 to about 1:3.

33. The process of Claim 30 wherein the coal solids have a maximum particle size of one-half inch diameter.

34. The process of Claim 33 wherein the coal solids have a maximum particle size of one-quarter inch diameter.

35. The process of Claim 34 wherein the coal solids have a maximum particle size of 8 mesh.

36. The process of Claim 30 wherein the water-containing fluid contains an organic material selected from the group consisting of biphenyl, pyridine, a highly saturated oil, an aromatic oil, a partly hydrogenated aromatic oil, and a mono- or polyhydric compound.

37. The process of Claim 36 wherein the water-containing fluid contains an organic material selected from the group consisting of biphenyl, pyridine, a highly saturated oil, and a mono- or polyhydric compound.

38. The process of Claim 37 wherein the water-containing fluid contains a highly saturated oil.

39. A process as in Claim 1 wherein hydrogen is generated in situ.