CA1040125A - Process for recovering upgraded hydrocarbon products - Google Patents
Process for recovering upgraded hydrocarbon productsInfo
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- CA1040125A CA1040125A CA227,671A CA227671A CA1040125A CA 1040125 A CA1040125 A CA 1040125A CA 227671 A CA227671 A CA 227671A CA 1040125 A CA1040125 A CA 1040125A
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- water
- containing fluid
- solids
- oil
- oil shale
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Abstract
ABSTRACT OF THE DISCLOSURE
This invention involves a process for recovering upgraded hydro-carbon products from a carbonaceous material selected from the group 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 externally supplied hydrogen and in the presence of a sulfur-resistant catalyst.
This invention involves a process for recovering upgraded hydro-carbon products from a carbonaceous material selected from the group 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 externally supplied hydrogen and in the presence of a sulfur-resistant catalyst.
Description
~4~1Z5 A promising technique for recovering hydrocarbons from carbonaceous materials is a process called dense fluid extraction. Separation by dense fluid extraction at elevated temperatures is a relatively un-explored area. The basic principles of dense fluid extraction nt .
elevated temperatures are outlined in the monograph "The Principles of Gas Extraction" by P. F. M. Paul and W. S. Wise, published by Mills and Boon Limited in London, 1971, Chapters 1 through 4. The dense i-luid can Se either a liquid or a dense gas having a liquid-like density.
Dense fluid extraction depends on the changes in the properties of a flllid - in p~rticular, the density of the fluid - due to chanr~as In the pressure. ~t temperatures below its critical temperature, thc density of a fluid varies in step functional fashion with changes in the pressure, Such sharp trsnsitions ln the density are associated with vapor-liquid transitions. At temperatures above the critical temper~ture of a fluid, the density of the fluid increases almost linearly with pressure as requlred by the Ideal Gas Law, although deviations from linearity are noticeable at higher pressures. Such deviations are more marked as the temperature of the fluid is nearer, but still above, its critical temperature.
If a fluid is maintained at a temperature below its critical tem-perature and at its saturated vapor pressure, two phases will be in I
~ )125 equilibrium with each other, liquid X of density C and vapor Y of density D. The :Liquid of density C will possess ~ certain solvent power.
If the same fluid were then maintained at a particular temperature above its critical temperature and if it were compressed to density C, then the compressed fluid could be expected to possess a solvent power similar to that of liquid X o:f density C. A similar solvent power could be achieved at an even higher temperature by an even greater compression of the fluid to density C. However, because of the non-ideal behavior of the fluid near its critical temperature, a particular increase in pressure will be more effective in increasing the density of the fluid when the temperature is slightly above the critical temperature than when the temperature is much above the critical temperature of the flu:Ld.
These r,impl.e cons:Lderations lead to the suggest:Lon that at a g,Lven pressure and at a temperature above the crit:Lcal temperature of a com-pressed .~lu:Ld, the sol~ent power oE the compressed fluid should be greater the :Lower the temperature; and that, at a given temperature above the critical temperature of the compressed fluid, the solvent power of the compressed fluid should be greater the higher the pressure.
Although such useful solvent effects have been found above the critical temperature of the fluid solvent, it is not essential that the ; solvent phase be maintained above its critical temperature. It is only essential that the fluid solvent be maintained at high enough pressures so that its density is high. Thus, liquid fluids and gaseous fluids which are maintained at high pressures and have liquid-like densities are useful solvents in dense .Eluid extractions at elevated temperatures.
The basis oE separatlons by dense fluid extraction at elevated temperatures is that a substrate is brought into contact with a dense, compressed fluid at an elevated temperature, material from the substrate is dissolved in the fluid phase, then the fluid phase containing this dissolved material is isolated, and finally the isolated fluid phase is decompressed to a point where the solvent power of the fluid is destroyed and where the dissolved materi~l is separated as a solid or liquid.
Some general conclusions based on empirical correlations have been drawn regarding the conditions Eor achieving high solubility of sub-strates in dense, compressed fluids. For example, the solvent effectof a dense, compressed fluid depends on the physical properties of the fluid solvent and of substrate. This suggests that fluids of different chemical nature but similar physical properties would behave similarly as solvents. An example is the discovery that the solvent power of com-pressed ethylene and carbon dioxide is similar.
In addltion, it has been concluded that a more ef~icient dense fluid extraction should be obtained with a solvent whose critical tem-perature is nearer the extraction temperature than with a solvent whose critical temperature is farther from the extraction temperature. Further since the solvent power of the dense, compressed fluic1 should be greater the lower the temperature but since the vapor pre~sure o~ the materlal to be extracted shotlld be greater the higher the temperature, ~he choLce o~ extraction temperature should be a compromlse between these opposing effects.
Various ways of making practical use of dense fluid extraction are possible following the analogy of conventional separation processes.
For example, both the extraction stage and the decompression stage afford considerable scope for making separations of mixtures of materials.
Mild conditions can be used to extract first the more volatile materials, and then more severe conditions can be used to extract the less volatile materials. The decompression stage can also be carried out in a single stage or in several stages so that the less volatile dissolved species separate first. The extent of extraction and the recovery of product on decompression can be controlled by selecting of an appropriate fluid solvent, by ad~justing the temperature and pressure of the extraction or 1~46~1Z5 ¦ dccompre.ssioll, alld hy alter~n~ the rnt~o Or .~uh.~tr;lte-to-flul(l .~olvent ¦ whicll ls chllrged to the extraction ves.4eL.
In general, dense flu~d extraction nt elevaeed temperatures can s be considered as an alternative, on the on~ hand, to diseillation and,on the other hand, to extraction with llquid solvents at lower tempera-tures. A considerable advantage of dense fluid extraction over distil-lation i9 that it enables substrates oE low volatility to be processed.
Dense fluid extraction even offers an aleernative to molecular distll-lation, but with such high concencrations in the dense fluid phase 0 that a marked advantage in throughput should result. Dense fluid extraction would be of particular use where heat-liable substrates have ~ to be processed since extraction into the dense fluid phase can be ; effected at témperatures well below those required by distllation.
A con~iderable advantage of dense flui~ extraction at elevate~
~5 tempera~urcs over liquld extractlon at lower temperatures ls that the solvent power of the compressed fluld solverlt can be continuously con-trolled by adjusting the pressure instead of the temperature. Having available a means of controlling solvent power by pressure changes gives ;~ a new approach nnd scope to .solvent extraction processes.
Zhuze was apparently the Eirst to apply dense fluid extraction to chemical engineering operations in a scheme ~or de-asphalting petroleum fractions using a propane-propylene mixture as gas, as reported in Vestnik Akad. Nauk S.S.S.R. 29 ~11), 47-52 (1959) and in Petroleum 2s (London) 23, 298-300 (1960~.
Apart from Zhuze's work, there have been ~ew detailed reports of attempts to apply dense fluid extraction techniques to substrates of commercial interest. British Patent No. 1,057,911 (1964) describes the principles of gas extraction in general terms, emphasizes its use ,lS a separation technique complementary to solvent extraction and distillation, and outlines multi-stage operation. British Patent No. 1,111,422 (1965) refers to the use of gas extraction techniques for working up heavy petroleum fractions. A feature of particular interest is the separation of materials ir.to residue and extract products, the latter being free 5 from objectionable inorganic contaminants such as vanadium. The advantag is also mentioned in this patent of cooling the gas solvent at sub-crltical temperatures before recycling it. This converts it to the liquid form which requires less energy to pump it against the hydro-static head in the reactor than would a gas. French patents 1,512,060 (1967) and 1,512,061 (1967) mention the use of gas extraction on lo petroleum fractions. In principle, these seem to follow the direction of the earlier Russian work.
In addition, there are other reEerences to recovery o~ upgraded hydrocarbon Eractions ~rom carbonaceous materlals by processes utillzLng water. For example, Friedman et al.~ U.S. Patent No. 3,051,644 (1962) discloses a process ~or the recovery of oil from oil shale which involves sut~ecting oil shale particles dispersed In steam to treatment with steam at a temperature in the range o-f from 700F. to 900F. and at a pressure in the range of from 1000 to 3000 pounds per square inch gauge.
Oil from the oll shale ls withdrawn in vapor form admixed with steam.
Truitt et al., U.S. Patent No. 2,665,238 (1954) discloses a method of recovering oil from oil shale which involves treating the shale with water in a large amount approximating the weight of the shale, at a temperature in excess of 500F. and under a pressure in excess of 1000 pounds per square inch. The amount of oil recovered increases generally as the temperature or pressure is further increased, but pressures as high as about 3000 pounds per sguare inch gauge and temperatures at least approximately as high as 700F. are required to effect a sub-stantially complete recovery of the oil.
30Pevere, et al., U.S. Patent No. 2,665,390 (1948) describes in general terms a process for dissolving coal in liquid solvents at high ~.~46~25 temperatures and then atomizing the solution into a carbonizer but does not mention the use of supercritical conditlons. U.S. Defensive Publi-cation 700,485 (filed January 25, 1968) refers to the use of a gas extractant to recover, from a solution of coal in a liquid solvent a fraction suitable as a feedstock for hydrocracking to gasoline.
Seitzer, U.S. Paetnt No. 3,642,607 (1972) discloses a process for dissolving bituminous coal by heating a mixture of bituminous coal, a hydrogen donor oil, carbon monoxide, water, and an alkali metal hydroxide or its precursor at a t2mperature oE about 400-450C. and under a total pressure of a~ lea~st about 4000 pounds per square inch gauge.
Seitzer, U.S. Patent No. 3,687,838 (1972) discloses the same process as disclosed in U.S. Patent No. 3,642,607 (1972) but employs an al~ali metal or ammonium molybdate instead oE an alkali metal hydroxlde Or lts precursar.
Urban, U.S. Patent No. 3,796,650 (1974) dlscloses a process Eor de-ashlng and llqueeyln~ coal which comprlses contacting comminuted coal with water, at least a port:Lon oE whlch 1.8 :Ln the liquid phase, ~ln exterually supplied reduc-lng gas and a compo~md selected from nmmonin and carbonates and hytlroxides of alkali metals, at liquefaction con-ditions, including a temperature of 200-370C. to provide a hydro-carbonaceous product.
There have been numerous references to processes for cracking, desulfurizing, denitrifying, demetalating, and generally upgrading hydrocarbon fractions by processes involving water. For example, Gatsis, U.S. Patent No, 3,453,206 (1969) discloses a multi-stage process for hydrorefining heavy hydrocarbon fractions for the purpose oE eliminating and/or reducing the concentratlon oE sulfurous, nitrogenotls, organo-metallic, and asphaltenic contaminants therefrom. The nitrogenous and sulfurous contamlnants are converted to ammonia and hydrogen sulflde.
The stages comprise pretreating the hydrocarbon fraction in the absence 1040~Z5 of a catalyst, with a mixture of water and externally supplied hydrogen at a temperature above the critical temperature of water and a pressure of at least lO00 pounds per square inch gauge and then reacting the liquid product from the pretreatment stage with externally supplied hydrogen at hydrorefining conditions and in the presence of a catalytic composite. The catalytic composite comprises a metallic component composited with a refractory inorganic oxide carrier material of either synthetic or natural origin, which carrier material has a medium-to-o high surface area and a well-developed pore structure. The metallic component can be vanadlum, niobium, tantalum, molybdenum, tungsten, chromium, iron, cobalt, nickel, platinum, palladium, iridlum, osmium, rhodium, ruthenium, and mixtures thereof.
Gntsi~, U.~. Patent No. 3,501,396 (1970) discloses a process ~or desulfurlzlng ancl clen:LtrLfylllg oi~ whieh comt)rlses mLxlng the oLl wLth water at a temperatu~e above the critical temperatllre o~ water llp ~o abouk 800F. ancl at a pressure in the range of from ahout 1000 to nbout 25~0 pounds per square lnch gat~ge and reacting the resulting mixture with externally supplied hydrogen in contact with a cataLytic composite. The catalytic composite can be characteri~ed as a dual function catalyst comprising a metallic component such as iridium, osmium, rhodium, ruthenium and mixtures thereof and an acidic carrier component having cracking activity. An essential feature of this method is the catalyst being acidic in nature. Ammonia and hydrogen sulfide are produced in the conversion of nitrogenous and sulfurous compounds, respectively.
Pritchford et al., U.S. Patent No. 3,586,621 (1971) discloses a method for converting heavy hydrocarbon oils, residual hydrocarbon fractions, and solid carbonaceous materials to more useful gaseous ancl liquld products by contacting the material to be converted with a nickel spinel catalyst promoted with a barium salt of an organic acid in the 1~34~)1Z5 ¦ presence of steam. ~ temperature in the range of from 600F. to about ¦ 10~0F. and a pressure in the range of from 200 to 3000 pounds per ¦ square inch gauge are employed.
l Pritchford, U.S. Patent No. 3,676,331 (1972) discloses a method for ¦ upgrading hydrocarbons and thereby producing materials o-f low molecular ¦ weight and of reduced sulfur content and carbon residue by in~roducing ¦ water and a catalyst system containing at least two components into the ¦ hydrocarbon fraction. The water can be the natural water content of the ¦ hydrocarbon fraction or can be added to the hydrocarbon fraction from an ¦ external source. The water-to-hydrocarbon fraction volume ratio is ¦ preferably in the range from about 0.1 to about 5. At least the first ¦ of the components of the catalyst system promotes the generation of ¦ hydrogen by reaction of water in the water gas shift reaction and at ¦ least the second o~ the components oE the catalyst system promotes reaction hetween the hydrogen generated and the constituents of the hydrocarbon fraction. Sultnb:Le materials ~or use as the ELr9t component of the catalyst system are the carboxylic ncid salts o~ barium, calcium, stronLlllm, and magneslum. Suitable materials for use as the second component of the catalyst system are the carboxylic acid salts of nickel, cobalt, and iron. The process is carried out at a reaction temperature in the range of from about 750F. to about 850F. and at a pressure of from about 300 to about 4000 pounds per square inch gauge in order to maintain a principal portion of the crude oil in the liquid -` 25 state.
; Wilson et al., U.S. Patent No. 3,733,259 (1973) discloses a process for removing metals, asphaltenes, and sulfur from a heavy hydrocarbon oil. The process comprlses dispersing the oil with water, maintaining this dlspersion at a temperature between 750F. and 850F. and at a pressure between atmospheric and 100 pounds per square inch gauge, cooling the dispersion after at least one-half hour to form a stable -zs water-asphaltene emulsion, sepa~ating the emulsion from the treated oil9 adding hydrogen, and contacting the resulting treated oil with a hydro-genation ca~alys~ at a ~emperature between 500F. and 900F. and at a pressure between about 300 and 3000 pounds per square inch gauge.
It has also been announced that the semi-governmèntal Japan Atomic Energy Research In~titute~ working with the Chisso Engineering Corpora-tlon, has developed what is called a "simple, low-cost, hot-water, oil desulfurization process" said to have "sufficient commercial appli-cability to compete with the hydrogenation process." The process itself consists of passing oil through a pressurized boiling water tank in which water i~ heated up to approximately 250C., under a pressure of about lO0 atmospheres. Sulfides in oil are then separsted when the water tempera~ure is reduced to less than 100C.
Thus far, no one has dlsclosed the method of this invention for recovering and upgrading hydrocarbon fractions from carbonaceous materials, which permits operation in a single step at lower than conventional temperatllres, without an external source of hydrogen, and wlthout preparation ~r pretreatment, such as, desalting or demetalatlon, I
prior to upgrading the recovered hydr~carbon fraction.
Thus the present invention provides a process for recovering upgraded hydrocarbon products from a carbonaceous material selected from the group consisting of oil shale solids, tar sands solids, coal solids, and a hydrocarbon fraction containing paraffins, olefins, olefin-equivalents, .
or acetylenes, as such or as substituents on ring compounds, comprising contacting the carbonaceous material with a water- I
containing fluid at a temperature in the range of from about 600F. to about 900F,, ln the absence of externally supplied hydrogen, and in the presence of an ~xternally supplied, sulfur-resistant catalyst, selected from the group consisting _ g_ Z~
of at least one basic metal carbonate, basic metal hydroxide, txansition metal oxide, ox~de-forming transition metal salt, and co~binations thereof, wherein the density of water in the water-containing fluid is at least 0.10 gram per milliliter and sufficient water is present in the water-containing fluid to serve as an effective solvent for the recovered hydrocarbons.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graph showing the correlation of the calcination weight loss of oil shale solids with the results of the Fischer assay of such solids.
Figure 2 is a series of plots showing the dependence on temperature of the yields of hydrocarbon products from oil shale using the method of this lnvention.
Figure 3 is a series of plots showing the dependence of the yields of oil and bitumen from oil shale upon the particle size of the oil shale and upon the contact time using the method of thls invention.
- 9(a) -e~
~, ~
~403 25 Figllre 4 is <~ series of plots showing the dependence of the oil solecLivlty u~ e particle si%e of the oll .shale nnd upon ~he cf-nt~(t time using the method of this invention.
Figure 5 is a schematic diagram of the flow system used for semi-continuously processing a hydrocarbon fraction.
DETAILED DESCRIPTION
It has been found that hydrocarbons can be recovered from carbonaceo s materials and that the recovered hydrocarbons can be upgraded, cracked, desulfurized, and, if the carbonaceous material is tar sands solids, oil shale solids, or a hydrocarbon fraction containing paraffins, olefins, olefin-equivalents, or acetylenes, as such or as substituents on ring compounds, demetalated by contacting the carbonaceous material with a den~se-water-containlng phase, either gtS or llquicl, at a reactLon temperature ln the range of from about 600F, to a`bout 900F. ln the absence of externally supplied hydrogen, and in the presence of an externally supplied sulfur-resistant transition metal catalyst. When the carbonaceous materisl is coal solids, the solid coal remaining after treatment by the method of th~s invention is desulfurized. This method is applicable to the whole range of hydrocarbon fractions, including both light materials and heavy materials such as gas oil, residual oils, tar sands oil, oil shale kerogen extracts, and liquefied coal products.
We have found that, in order to effect the recovery of hydrocarbons from carbonaceous materials and in order to effect the chemical con-version of the recovered hydrocarbons into lighter, more useful hydro-carbon fractions by the method of this invention - which involves . processes characteristically occurring in solution rather than typical pyrolytic processes - the water in the dense-water-containing fluid phase must have a high solvent power and liquid-like densities - for example, at least 0.1 gram per milliliter - rather than vapor-like ~ 1Z5 ¦ densities. Maintenance of the water in the dense-water-containing phase ¦ at a relatively high density, whether at temperatures below or above the critical temperature of water, is essential to the method of this ¦ invention. The density of the water in the dense-water-containing phase ¦ must be at least 0.1 gram per milliliter.
¦ The high solvent power of dense fluids is discussed in the monograph ¦ "The Principles of Gas Extraction" by P. F. M. Paul and W. S. Wise, ¦ published by Mills and Boon Limited in London, 1971. For example, the ¦ difference in the solvent power of steam and of dense gaseaus water ¦ maintalned at a temperature Ln the region oE the critical temperature ¦ of water and at an elevated pressure is substantial. Even normally ¦ insoluble inorganic materials, such as silica and alumina, commence to dlssolve apprecltlbLy Ln "supercrLtlcnl water" - that ls, water maintained lS Mt a temperature above the crLtlcaL temperuture of water - so Long as a high wuter ~lenslty is maLntained.
Enough water must be employed so that there ls sufflcient water in the dense-water-containing phase to serve as an effective solvent for the recovered hydrocarbons. The water in the dense-water-containing phas~
can be in the form either of liquid water or of dense gaseous water.
The vapor pressure of water in the dense-water-containing phase must be ma~ntained at a sufficiently high level so that the density of water in the dense-water-containing phase is at least 0.1 gram per milliliter.
We have found that, with the limitations imposed by the size of the reaction vessels we employed in this work, a weight ratio of the hydro-carbon fraction-to-water in the dense-water-containing phase in the range of from about 1:1 to about 1:10 is preferable, and a ratio in the range of from about 1:2 to about 1:3 is more preferable. Similarly, a weight ratio oE the oil shale, tar sands, or coal solids-to-water in the water-containing phase in the range of from about 3:2 to about 1:10 is preferable, and a ratio in the range of from about 1:1 to about 1:3 is more preferable.
~ particularly useful water-containing fluid contains water in combination with an organic compound such as biphenyl, pyridine, a partly hydrogenated aromatic oil, or a mono- or polyhydric compound such as methyl alcohol. The use of such combinations extends the limits of solubility and rates of dissolution so that cracking, desulfurization, and demetalation can occur even more readily. Furthermore, the component other than water in the dense-water-containing phase can serve as a source of hydrogen, for example, by reaction with water.
The catalyst employed in the method of thls invention is effective when added in an amount equlvalent to a concentration in the water of the water-containing Eluid in the range of ~rom about 0.01 to about 3.0 welgllt percent and preerably in the ran~e of From about 0,lO to about 0.5() weight percen~.
The cataly~t may be ad(1ed as a ~ol:Ld and sl~trr:Led ln the renctlon mlxture or as a water-soluble salt, for example manganese chlorlde or potassium perman~anate, which procluces the corresponding oxlde under the conditions employed in the method of this inventlon. Alternately, the catalyst can be deposited on a support and used as such ln a flxed-bed flow configuration or slurried in the water-containing fluid.
This process can be performed either as a batch process or as a continuous or semi-continuous flow process. Contact times between the carbonaceous materlal and the dense water-containlng phase -that ls, resldence tlme ln a batch process or inverse solvent space velocity in a ; 25 flow process - of from the order of minutes up to about 6 hours are satisfactory for effectlve cracklng, desulfuriæation, and demetalation of the recovered hydrocarbons.
In the method oE this invention, the water-containing fluid and the oil shale, tar sands~ or coal sollds are contacted by maklng a slu~ry oF
~ t olids in the t~ter-c ntainLng tluld.
1ai4~1z5 l When the method oE this invention is performed above ground with ¦ mined oil shale, tar sands or coal, the hydrocarbons can be recovered ¦ more rapidly if the mined solids are ground to a particle size preferably ¦ of 1/2-inch diameter or smaller. Alternately, the method of this ¦ invention could also be performed in situ in subterranean deposits by ¦ pumping the water-containing fluid into the deposit and withdrawing ¦ hydrocarbon products for separation or further processing.
¦ RXAMPLES 1-37 ¦ Examples 1-37 involve batch processing of oil shale and tar sands lo ¦ Eeeds Imder a vnrlety oE conditLons cmd Lllustrate that hydrocarbons ¦ are recovered, cracked, desIllfurize(I, ~md demetalate(I in the method of ¦ this invention. Unless otherwise speciEied, the following procedIlre ¦ wns used ln eactI ~ase. The oil shale or tar sancls Eeed, wnter, and, L~
¦ used, components oE the catalyst system were loaded at ambLent tem-¦ perature into a 300-mllllllter }Iastelloy alloy C Mngne-Drive batch ¦ autoclave in whlch the reaction mlxture was to be mixed. The components of the catalyst system were added as solutes in the water or as solids in slurries in the water. Unless otherwise specified, sufficient water was added in each Rxample so that, at the reaction temperature and prexsure and In the reaction volIlme used, the denxity of the water wnx at least 0.1 gram per milliliter.
; The autoclave was flushed with inert argon gas and was then closed.
Such inert gas was also added to raise the pressure of the reaction system. The contribution of argon to the total pressure at ambient temperature is called the argon pressure.
The temperature of the reaction system was then raised to the desired level and the dense-water-containing Eluid phase was formed.
Approximately 28 minutes were required to he~t the autoclave from ambient temperature to 660F. Approximately 6 minutes were required to 30 j ralte the t eraeure from 660F. eO 700F. ~pproxlmately another 6 lU401Z5 minutes were required to raise the temperature from 700F. to 750F.
When the desired final temperature was reached, the temperature was held constant for the desired period of time. This flnal constant temperature and the period of time at ~his temperature are defined as the reaction temperature and reaction time, respectively. During the reaction time, the pressure of the reaction system increased as the reaction proceeded. The pressure at the start of the reaction time is defined as the reaction pressure.
After the desired reaction time at the desired reaction temperature o and pressure, the dense-water-containing fluid phase was de-pressurized and was flash-distilled Erom the reaction vessel, removing the gas, water and "oil", and leaving the "bitumen," inorganic resLdue, and catalyst, lf present, Ln the reactlon vessel. The "oil" was the llqlllcl hyclro-carbon fraction boillng at or below the reactlon temperature and the"bitumen" was the hydrocarbon Eractlon bolling above the reaction temperat~re. The lnorganlc residue was spent shale or spent tar sands.
The gas, water, and oll were trapped ln a pressure vessel cooled by liquid nitrogen. The gas was removed by warming the pressure vessel to room temperature and then was analyzed by mass spectroscopy, gas chromato graphy, and infra-red. The water and oil were then purged from the préssure vessel by means of compressed gas and occasionally also by heating the vessel. Then the water and oil were separated by decantation The oil was analyzed for its sulfur and nitrogen content using x-ray fluorescence and the Kjeldahl method, respectively, and for its density and API gravlty.
The bltumen, inorganic residue, and catalyst, if present, were washed from the reaction vessel with chloroform, and the bitumen dissolved in this solvent. The solid residue was then separated from the solution containing the bltumen by filtration. The bitumen was analyzed for its sulfur and nitrogen contents using the same methods as 1(~4V125 in the analysis of the oil. The solid residue was analyzed for its inorganic carbonate content.
In regard to the recovery o hydrocarbons from oil shale, several samples of oil shale were obtained from oil shale deposits in Colorado.
These samples were obtained in the form of lumps, which were then ground and sieved to obtain fractions of various particle sizes. In order to esttm.~to tl-e korogenic contont of these fraction~, portions of eacl1 sclmp1e were calc:Lned in air nt 1()00l~. ~or 30 minute~ to remove wnter and kerogenic carbonaceous matter without decomposing inorganlc carbonate The particle size of the samples of oil shale used in this work and the percent of weight loss during calclnation for each of these samples are presented in Table l.
Examples l-36 involve batch recovery of hydrocarbons from the oil shale sa~ple~ ~hown in 'rable 1 using the. method described above. T'hese r~tns were per~ornl~d in a 300-mLll~llter ~ta8telloy a~loy C Magne~l)rlve nu~oclnve. Tlle axperlmental conditlon~ an~ the re~ults determLned In tllese ~xam~Le~ nre presented ln ~'ables 2 and 3, respectlvely.
Tn these l~'~amples, the liquid hydrocarbon products were classified either as oils or as bitumens depending on whether or not such liquid products could be flashed from the autoclave upon depressurization of the autoclave at the run temperature employed. Oils were those liquid ~ products which flashed over at the run temperature, while bitumens were ; those liquid products which remained in the autoclave. The oil fractions had densities in the range of from about 0.92 to about 0.94 grams per milliliter and had API gravities in the range of between about 19API.
to about 23API. The bitumen fractions had densities of about l.Ol grams per milliliter and API gravities of about lO. Oil shale sample A
contained 0.7 weight percent of sulfur, l.7 weight percent of nitrogen.
Use oE a catalyst in Example 36 caused a substantial increase in the amount of the oil fraction produced relative to the amount of the bitumen fraction produced.
TABLE l Oil Shale 1 Percent Weight Loss Sample Particle Size during Calcination A 60-80 32.2 B 14-28 26.8 (: 8-14 36. h D 1/4-l/82 22. 3 ootnotes 1 mesh si~e, except where otherwlse indicated.
elevated temperatures are outlined in the monograph "The Principles of Gas Extraction" by P. F. M. Paul and W. S. Wise, published by Mills and Boon Limited in London, 1971, Chapters 1 through 4. The dense i-luid can Se either a liquid or a dense gas having a liquid-like density.
Dense fluid extraction depends on the changes in the properties of a flllid - in p~rticular, the density of the fluid - due to chanr~as In the pressure. ~t temperatures below its critical temperature, thc density of a fluid varies in step functional fashion with changes in the pressure, Such sharp trsnsitions ln the density are associated with vapor-liquid transitions. At temperatures above the critical temper~ture of a fluid, the density of the fluid increases almost linearly with pressure as requlred by the Ideal Gas Law, although deviations from linearity are noticeable at higher pressures. Such deviations are more marked as the temperature of the fluid is nearer, but still above, its critical temperature.
If a fluid is maintained at a temperature below its critical tem-perature and at its saturated vapor pressure, two phases will be in I
~ )125 equilibrium with each other, liquid X of density C and vapor Y of density D. The :Liquid of density C will possess ~ certain solvent power.
If the same fluid were then maintained at a particular temperature above its critical temperature and if it were compressed to density C, then the compressed fluid could be expected to possess a solvent power similar to that of liquid X o:f density C. A similar solvent power could be achieved at an even higher temperature by an even greater compression of the fluid to density C. However, because of the non-ideal behavior of the fluid near its critical temperature, a particular increase in pressure will be more effective in increasing the density of the fluid when the temperature is slightly above the critical temperature than when the temperature is much above the critical temperature of the flu:Ld.
These r,impl.e cons:Lderations lead to the suggest:Lon that at a g,Lven pressure and at a temperature above the crit:Lcal temperature of a com-pressed .~lu:Ld, the sol~ent power oE the compressed fluid should be greater the :Lower the temperature; and that, at a given temperature above the critical temperature of the compressed fluid, the solvent power of the compressed fluid should be greater the higher the pressure.
Although such useful solvent effects have been found above the critical temperature of the fluid solvent, it is not essential that the ; solvent phase be maintained above its critical temperature. It is only essential that the fluid solvent be maintained at high enough pressures so that its density is high. Thus, liquid fluids and gaseous fluids which are maintained at high pressures and have liquid-like densities are useful solvents in dense .Eluid extractions at elevated temperatures.
The basis oE separatlons by dense fluid extraction at elevated temperatures is that a substrate is brought into contact with a dense, compressed fluid at an elevated temperature, material from the substrate is dissolved in the fluid phase, then the fluid phase containing this dissolved material is isolated, and finally the isolated fluid phase is decompressed to a point where the solvent power of the fluid is destroyed and where the dissolved materi~l is separated as a solid or liquid.
Some general conclusions based on empirical correlations have been drawn regarding the conditions Eor achieving high solubility of sub-strates in dense, compressed fluids. For example, the solvent effectof a dense, compressed fluid depends on the physical properties of the fluid solvent and of substrate. This suggests that fluids of different chemical nature but similar physical properties would behave similarly as solvents. An example is the discovery that the solvent power of com-pressed ethylene and carbon dioxide is similar.
In addltion, it has been concluded that a more ef~icient dense fluid extraction should be obtained with a solvent whose critical tem-perature is nearer the extraction temperature than with a solvent whose critical temperature is farther from the extraction temperature. Further since the solvent power of the dense, compressed fluic1 should be greater the lower the temperature but since the vapor pre~sure o~ the materlal to be extracted shotlld be greater the higher the temperature, ~he choLce o~ extraction temperature should be a compromlse between these opposing effects.
Various ways of making practical use of dense fluid extraction are possible following the analogy of conventional separation processes.
For example, both the extraction stage and the decompression stage afford considerable scope for making separations of mixtures of materials.
Mild conditions can be used to extract first the more volatile materials, and then more severe conditions can be used to extract the less volatile materials. The decompression stage can also be carried out in a single stage or in several stages so that the less volatile dissolved species separate first. The extent of extraction and the recovery of product on decompression can be controlled by selecting of an appropriate fluid solvent, by ad~justing the temperature and pressure of the extraction or 1~46~1Z5 ¦ dccompre.ssioll, alld hy alter~n~ the rnt~o Or .~uh.~tr;lte-to-flul(l .~olvent ¦ whicll ls chllrged to the extraction ves.4eL.
In general, dense flu~d extraction nt elevaeed temperatures can s be considered as an alternative, on the on~ hand, to diseillation and,on the other hand, to extraction with llquid solvents at lower tempera-tures. A considerable advantage of dense fluid extraction over distil-lation i9 that it enables substrates oE low volatility to be processed.
Dense fluid extraction even offers an aleernative to molecular distll-lation, but with such high concencrations in the dense fluid phase 0 that a marked advantage in throughput should result. Dense fluid extraction would be of particular use where heat-liable substrates have ~ to be processed since extraction into the dense fluid phase can be ; effected at témperatures well below those required by distllation.
A con~iderable advantage of dense flui~ extraction at elevate~
~5 tempera~urcs over liquld extractlon at lower temperatures ls that the solvent power of the compressed fluld solverlt can be continuously con-trolled by adjusting the pressure instead of the temperature. Having available a means of controlling solvent power by pressure changes gives ;~ a new approach nnd scope to .solvent extraction processes.
Zhuze was apparently the Eirst to apply dense fluid extraction to chemical engineering operations in a scheme ~or de-asphalting petroleum fractions using a propane-propylene mixture as gas, as reported in Vestnik Akad. Nauk S.S.S.R. 29 ~11), 47-52 (1959) and in Petroleum 2s (London) 23, 298-300 (1960~.
Apart from Zhuze's work, there have been ~ew detailed reports of attempts to apply dense fluid extraction techniques to substrates of commercial interest. British Patent No. 1,057,911 (1964) describes the principles of gas extraction in general terms, emphasizes its use ,lS a separation technique complementary to solvent extraction and distillation, and outlines multi-stage operation. British Patent No. 1,111,422 (1965) refers to the use of gas extraction techniques for working up heavy petroleum fractions. A feature of particular interest is the separation of materials ir.to residue and extract products, the latter being free 5 from objectionable inorganic contaminants such as vanadium. The advantag is also mentioned in this patent of cooling the gas solvent at sub-crltical temperatures before recycling it. This converts it to the liquid form which requires less energy to pump it against the hydro-static head in the reactor than would a gas. French patents 1,512,060 (1967) and 1,512,061 (1967) mention the use of gas extraction on lo petroleum fractions. In principle, these seem to follow the direction of the earlier Russian work.
In addition, there are other reEerences to recovery o~ upgraded hydrocarbon Eractions ~rom carbonaceous materlals by processes utillzLng water. For example, Friedman et al.~ U.S. Patent No. 3,051,644 (1962) discloses a process ~or the recovery of oil from oil shale which involves sut~ecting oil shale particles dispersed In steam to treatment with steam at a temperature in the range o-f from 700F. to 900F. and at a pressure in the range of from 1000 to 3000 pounds per square inch gauge.
Oil from the oll shale ls withdrawn in vapor form admixed with steam.
Truitt et al., U.S. Patent No. 2,665,238 (1954) discloses a method of recovering oil from oil shale which involves treating the shale with water in a large amount approximating the weight of the shale, at a temperature in excess of 500F. and under a pressure in excess of 1000 pounds per square inch. The amount of oil recovered increases generally as the temperature or pressure is further increased, but pressures as high as about 3000 pounds per sguare inch gauge and temperatures at least approximately as high as 700F. are required to effect a sub-stantially complete recovery of the oil.
30Pevere, et al., U.S. Patent No. 2,665,390 (1948) describes in general terms a process for dissolving coal in liquid solvents at high ~.~46~25 temperatures and then atomizing the solution into a carbonizer but does not mention the use of supercritical conditlons. U.S. Defensive Publi-cation 700,485 (filed January 25, 1968) refers to the use of a gas extractant to recover, from a solution of coal in a liquid solvent a fraction suitable as a feedstock for hydrocracking to gasoline.
Seitzer, U.S. Paetnt No. 3,642,607 (1972) discloses a process for dissolving bituminous coal by heating a mixture of bituminous coal, a hydrogen donor oil, carbon monoxide, water, and an alkali metal hydroxide or its precursor at a t2mperature oE about 400-450C. and under a total pressure of a~ lea~st about 4000 pounds per square inch gauge.
Seitzer, U.S. Patent No. 3,687,838 (1972) discloses the same process as disclosed in U.S. Patent No. 3,642,607 (1972) but employs an al~ali metal or ammonium molybdate instead oE an alkali metal hydroxlde Or lts precursar.
Urban, U.S. Patent No. 3,796,650 (1974) dlscloses a process Eor de-ashlng and llqueeyln~ coal which comprlses contacting comminuted coal with water, at least a port:Lon oE whlch 1.8 :Ln the liquid phase, ~ln exterually supplied reduc-lng gas and a compo~md selected from nmmonin and carbonates and hytlroxides of alkali metals, at liquefaction con-ditions, including a temperature of 200-370C. to provide a hydro-carbonaceous product.
There have been numerous references to processes for cracking, desulfurizing, denitrifying, demetalating, and generally upgrading hydrocarbon fractions by processes involving water. For example, Gatsis, U.S. Patent No, 3,453,206 (1969) discloses a multi-stage process for hydrorefining heavy hydrocarbon fractions for the purpose oE eliminating and/or reducing the concentratlon oE sulfurous, nitrogenotls, organo-metallic, and asphaltenic contaminants therefrom. The nitrogenous and sulfurous contamlnants are converted to ammonia and hydrogen sulflde.
The stages comprise pretreating the hydrocarbon fraction in the absence 1040~Z5 of a catalyst, with a mixture of water and externally supplied hydrogen at a temperature above the critical temperature of water and a pressure of at least lO00 pounds per square inch gauge and then reacting the liquid product from the pretreatment stage with externally supplied hydrogen at hydrorefining conditions and in the presence of a catalytic composite. The catalytic composite comprises a metallic component composited with a refractory inorganic oxide carrier material of either synthetic or natural origin, which carrier material has a medium-to-o high surface area and a well-developed pore structure. The metallic component can be vanadlum, niobium, tantalum, molybdenum, tungsten, chromium, iron, cobalt, nickel, platinum, palladium, iridlum, osmium, rhodium, ruthenium, and mixtures thereof.
Gntsi~, U.~. Patent No. 3,501,396 (1970) discloses a process ~or desulfurlzlng ancl clen:LtrLfylllg oi~ whieh comt)rlses mLxlng the oLl wLth water at a temperatu~e above the critical temperatllre o~ water llp ~o abouk 800F. ancl at a pressure in the range of from ahout 1000 to nbout 25~0 pounds per square lnch gat~ge and reacting the resulting mixture with externally supplied hydrogen in contact with a cataLytic composite. The catalytic composite can be characteri~ed as a dual function catalyst comprising a metallic component such as iridium, osmium, rhodium, ruthenium and mixtures thereof and an acidic carrier component having cracking activity. An essential feature of this method is the catalyst being acidic in nature. Ammonia and hydrogen sulfide are produced in the conversion of nitrogenous and sulfurous compounds, respectively.
Pritchford et al., U.S. Patent No. 3,586,621 (1971) discloses a method for converting heavy hydrocarbon oils, residual hydrocarbon fractions, and solid carbonaceous materials to more useful gaseous ancl liquld products by contacting the material to be converted with a nickel spinel catalyst promoted with a barium salt of an organic acid in the 1~34~)1Z5 ¦ presence of steam. ~ temperature in the range of from 600F. to about ¦ 10~0F. and a pressure in the range of from 200 to 3000 pounds per ¦ square inch gauge are employed.
l Pritchford, U.S. Patent No. 3,676,331 (1972) discloses a method for ¦ upgrading hydrocarbons and thereby producing materials o-f low molecular ¦ weight and of reduced sulfur content and carbon residue by in~roducing ¦ water and a catalyst system containing at least two components into the ¦ hydrocarbon fraction. The water can be the natural water content of the ¦ hydrocarbon fraction or can be added to the hydrocarbon fraction from an ¦ external source. The water-to-hydrocarbon fraction volume ratio is ¦ preferably in the range from about 0.1 to about 5. At least the first ¦ of the components of the catalyst system promotes the generation of ¦ hydrogen by reaction of water in the water gas shift reaction and at ¦ least the second o~ the components oE the catalyst system promotes reaction hetween the hydrogen generated and the constituents of the hydrocarbon fraction. Sultnb:Le materials ~or use as the ELr9t component of the catalyst system are the carboxylic ncid salts o~ barium, calcium, stronLlllm, and magneslum. Suitable materials for use as the second component of the catalyst system are the carboxylic acid salts of nickel, cobalt, and iron. The process is carried out at a reaction temperature in the range of from about 750F. to about 850F. and at a pressure of from about 300 to about 4000 pounds per square inch gauge in order to maintain a principal portion of the crude oil in the liquid -` 25 state.
; Wilson et al., U.S. Patent No. 3,733,259 (1973) discloses a process for removing metals, asphaltenes, and sulfur from a heavy hydrocarbon oil. The process comprlses dispersing the oil with water, maintaining this dlspersion at a temperature between 750F. and 850F. and at a pressure between atmospheric and 100 pounds per square inch gauge, cooling the dispersion after at least one-half hour to form a stable -zs water-asphaltene emulsion, sepa~ating the emulsion from the treated oil9 adding hydrogen, and contacting the resulting treated oil with a hydro-genation ca~alys~ at a ~emperature between 500F. and 900F. and at a pressure between about 300 and 3000 pounds per square inch gauge.
It has also been announced that the semi-governmèntal Japan Atomic Energy Research In~titute~ working with the Chisso Engineering Corpora-tlon, has developed what is called a "simple, low-cost, hot-water, oil desulfurization process" said to have "sufficient commercial appli-cability to compete with the hydrogenation process." The process itself consists of passing oil through a pressurized boiling water tank in which water i~ heated up to approximately 250C., under a pressure of about lO0 atmospheres. Sulfides in oil are then separsted when the water tempera~ure is reduced to less than 100C.
Thus far, no one has dlsclosed the method of this invention for recovering and upgrading hydrocarbon fractions from carbonaceous materials, which permits operation in a single step at lower than conventional temperatllres, without an external source of hydrogen, and wlthout preparation ~r pretreatment, such as, desalting or demetalatlon, I
prior to upgrading the recovered hydr~carbon fraction.
Thus the present invention provides a process for recovering upgraded hydrocarbon products from a carbonaceous material selected from the group consisting of oil shale solids, tar sands solids, coal solids, and a hydrocarbon fraction containing paraffins, olefins, olefin-equivalents, .
or acetylenes, as such or as substituents on ring compounds, comprising contacting the carbonaceous material with a water- I
containing fluid at a temperature in the range of from about 600F. to about 900F,, ln the absence of externally supplied hydrogen, and in the presence of an ~xternally supplied, sulfur-resistant catalyst, selected from the group consisting _ g_ Z~
of at least one basic metal carbonate, basic metal hydroxide, txansition metal oxide, ox~de-forming transition metal salt, and co~binations thereof, wherein the density of water in the water-containing fluid is at least 0.10 gram per milliliter and sufficient water is present in the water-containing fluid to serve as an effective solvent for the recovered hydrocarbons.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graph showing the correlation of the calcination weight loss of oil shale solids with the results of the Fischer assay of such solids.
Figure 2 is a series of plots showing the dependence on temperature of the yields of hydrocarbon products from oil shale using the method of this lnvention.
Figure 3 is a series of plots showing the dependence of the yields of oil and bitumen from oil shale upon the particle size of the oil shale and upon the contact time using the method of thls invention.
- 9(a) -e~
~, ~
~403 25 Figllre 4 is <~ series of plots showing the dependence of the oil solecLivlty u~ e particle si%e of the oll .shale nnd upon ~he cf-nt~(t time using the method of this invention.
Figure 5 is a schematic diagram of the flow system used for semi-continuously processing a hydrocarbon fraction.
DETAILED DESCRIPTION
It has been found that hydrocarbons can be recovered from carbonaceo s materials and that the recovered hydrocarbons can be upgraded, cracked, desulfurized, and, if the carbonaceous material is tar sands solids, oil shale solids, or a hydrocarbon fraction containing paraffins, olefins, olefin-equivalents, or acetylenes, as such or as substituents on ring compounds, demetalated by contacting the carbonaceous material with a den~se-water-containlng phase, either gtS or llquicl, at a reactLon temperature ln the range of from about 600F, to a`bout 900F. ln the absence of externally supplied hydrogen, and in the presence of an externally supplied sulfur-resistant transition metal catalyst. When the carbonaceous materisl is coal solids, the solid coal remaining after treatment by the method of th~s invention is desulfurized. This method is applicable to the whole range of hydrocarbon fractions, including both light materials and heavy materials such as gas oil, residual oils, tar sands oil, oil shale kerogen extracts, and liquefied coal products.
We have found that, in order to effect the recovery of hydrocarbons from carbonaceous materials and in order to effect the chemical con-version of the recovered hydrocarbons into lighter, more useful hydro-carbon fractions by the method of this invention - which involves . processes characteristically occurring in solution rather than typical pyrolytic processes - the water in the dense-water-containing fluid phase must have a high solvent power and liquid-like densities - for example, at least 0.1 gram per milliliter - rather than vapor-like ~ 1Z5 ¦ densities. Maintenance of the water in the dense-water-containing phase ¦ at a relatively high density, whether at temperatures below or above the critical temperature of water, is essential to the method of this ¦ invention. The density of the water in the dense-water-containing phase ¦ must be at least 0.1 gram per milliliter.
¦ The high solvent power of dense fluids is discussed in the monograph ¦ "The Principles of Gas Extraction" by P. F. M. Paul and W. S. Wise, ¦ published by Mills and Boon Limited in London, 1971. For example, the ¦ difference in the solvent power of steam and of dense gaseaus water ¦ maintalned at a temperature Ln the region oE the critical temperature ¦ of water and at an elevated pressure is substantial. Even normally ¦ insoluble inorganic materials, such as silica and alumina, commence to dlssolve apprecltlbLy Ln "supercrLtlcnl water" - that ls, water maintained lS Mt a temperature above the crLtlcaL temperuture of water - so Long as a high wuter ~lenslty is maLntained.
Enough water must be employed so that there ls sufflcient water in the dense-water-containing phase to serve as an effective solvent for the recovered hydrocarbons. The water in the dense-water-containing phas~
can be in the form either of liquid water or of dense gaseous water.
The vapor pressure of water in the dense-water-containing phase must be ma~ntained at a sufficiently high level so that the density of water in the dense-water-containing phase is at least 0.1 gram per milliliter.
We have found that, with the limitations imposed by the size of the reaction vessels we employed in this work, a weight ratio of the hydro-carbon fraction-to-water in the dense-water-containing phase in the range of from about 1:1 to about 1:10 is preferable, and a ratio in the range of from about 1:2 to about 1:3 is more preferable. Similarly, a weight ratio oE the oil shale, tar sands, or coal solids-to-water in the water-containing phase in the range of from about 3:2 to about 1:10 is preferable, and a ratio in the range of from about 1:1 to about 1:3 is more preferable.
~ particularly useful water-containing fluid contains water in combination with an organic compound such as biphenyl, pyridine, a partly hydrogenated aromatic oil, or a mono- or polyhydric compound such as methyl alcohol. The use of such combinations extends the limits of solubility and rates of dissolution so that cracking, desulfurization, and demetalation can occur even more readily. Furthermore, the component other than water in the dense-water-containing phase can serve as a source of hydrogen, for example, by reaction with water.
The catalyst employed in the method of thls invention is effective when added in an amount equlvalent to a concentration in the water of the water-containing Eluid in the range of ~rom about 0.01 to about 3.0 welgllt percent and preerably in the ran~e of From about 0,lO to about 0.5() weight percen~.
The cataly~t may be ad(1ed as a ~ol:Ld and sl~trr:Led ln the renctlon mlxture or as a water-soluble salt, for example manganese chlorlde or potassium perman~anate, which procluces the corresponding oxlde under the conditions employed in the method of this inventlon. Alternately, the catalyst can be deposited on a support and used as such ln a flxed-bed flow configuration or slurried in the water-containing fluid.
This process can be performed either as a batch process or as a continuous or semi-continuous flow process. Contact times between the carbonaceous materlal and the dense water-containlng phase -that ls, resldence tlme ln a batch process or inverse solvent space velocity in a ; 25 flow process - of from the order of minutes up to about 6 hours are satisfactory for effectlve cracklng, desulfuriæation, and demetalation of the recovered hydrocarbons.
In the method oE this invention, the water-containing fluid and the oil shale, tar sands~ or coal sollds are contacted by maklng a slu~ry oF
~ t olids in the t~ter-c ntainLng tluld.
1ai4~1z5 l When the method oE this invention is performed above ground with ¦ mined oil shale, tar sands or coal, the hydrocarbons can be recovered ¦ more rapidly if the mined solids are ground to a particle size preferably ¦ of 1/2-inch diameter or smaller. Alternately, the method of this ¦ invention could also be performed in situ in subterranean deposits by ¦ pumping the water-containing fluid into the deposit and withdrawing ¦ hydrocarbon products for separation or further processing.
¦ RXAMPLES 1-37 ¦ Examples 1-37 involve batch processing of oil shale and tar sands lo ¦ Eeeds Imder a vnrlety oE conditLons cmd Lllustrate that hydrocarbons ¦ are recovered, cracked, desIllfurize(I, ~md demetalate(I in the method of ¦ this invention. Unless otherwise speciEied, the following procedIlre ¦ wns used ln eactI ~ase. The oil shale or tar sancls Eeed, wnter, and, L~
¦ used, components oE the catalyst system were loaded at ambLent tem-¦ perature into a 300-mllllllter }Iastelloy alloy C Mngne-Drive batch ¦ autoclave in whlch the reaction mlxture was to be mixed. The components of the catalyst system were added as solutes in the water or as solids in slurries in the water. Unless otherwise specified, sufficient water was added in each Rxample so that, at the reaction temperature and prexsure and In the reaction volIlme used, the denxity of the water wnx at least 0.1 gram per milliliter.
; The autoclave was flushed with inert argon gas and was then closed.
Such inert gas was also added to raise the pressure of the reaction system. The contribution of argon to the total pressure at ambient temperature is called the argon pressure.
The temperature of the reaction system was then raised to the desired level and the dense-water-containing Eluid phase was formed.
Approximately 28 minutes were required to he~t the autoclave from ambient temperature to 660F. Approximately 6 minutes were required to 30 j ralte the t eraeure from 660F. eO 700F. ~pproxlmately another 6 lU401Z5 minutes were required to raise the temperature from 700F. to 750F.
When the desired final temperature was reached, the temperature was held constant for the desired period of time. This flnal constant temperature and the period of time at ~his temperature are defined as the reaction temperature and reaction time, respectively. During the reaction time, the pressure of the reaction system increased as the reaction proceeded. The pressure at the start of the reaction time is defined as the reaction pressure.
After the desired reaction time at the desired reaction temperature o and pressure, the dense-water-containing fluid phase was de-pressurized and was flash-distilled Erom the reaction vessel, removing the gas, water and "oil", and leaving the "bitumen," inorganic resLdue, and catalyst, lf present, Ln the reactlon vessel. The "oil" was the llqlllcl hyclro-carbon fraction boillng at or below the reactlon temperature and the"bitumen" was the hydrocarbon Eractlon bolling above the reaction temperat~re. The lnorganlc residue was spent shale or spent tar sands.
The gas, water, and oll were trapped ln a pressure vessel cooled by liquid nitrogen. The gas was removed by warming the pressure vessel to room temperature and then was analyzed by mass spectroscopy, gas chromato graphy, and infra-red. The water and oil were then purged from the préssure vessel by means of compressed gas and occasionally also by heating the vessel. Then the water and oil were separated by decantation The oil was analyzed for its sulfur and nitrogen content using x-ray fluorescence and the Kjeldahl method, respectively, and for its density and API gravlty.
The bltumen, inorganic residue, and catalyst, if present, were washed from the reaction vessel with chloroform, and the bitumen dissolved in this solvent. The solid residue was then separated from the solution containing the bltumen by filtration. The bitumen was analyzed for its sulfur and nitrogen contents using the same methods as 1(~4V125 in the analysis of the oil. The solid residue was analyzed for its inorganic carbonate content.
In regard to the recovery o hydrocarbons from oil shale, several samples of oil shale were obtained from oil shale deposits in Colorado.
These samples were obtained in the form of lumps, which were then ground and sieved to obtain fractions of various particle sizes. In order to esttm.~to tl-e korogenic contont of these fraction~, portions of eacl1 sclmp1e were calc:Lned in air nt 1()00l~. ~or 30 minute~ to remove wnter and kerogenic carbonaceous matter without decomposing inorganlc carbonate The particle size of the samples of oil shale used in this work and the percent of weight loss during calclnation for each of these samples are presented in Table l.
Examples l-36 involve batch recovery of hydrocarbons from the oil shale sa~ple~ ~hown in 'rable 1 using the. method described above. T'hese r~tns were per~ornl~d in a 300-mLll~llter ~ta8telloy a~loy C Magne~l)rlve nu~oclnve. Tlle axperlmental conditlon~ an~ the re~ults determLned In tllese ~xam~Le~ nre presented ln ~'ables 2 and 3, respectlvely.
Tn these l~'~amples, the liquid hydrocarbon products were classified either as oils or as bitumens depending on whether or not such liquid products could be flashed from the autoclave upon depressurization of the autoclave at the run temperature employed. Oils were those liquid ~ products which flashed over at the run temperature, while bitumens were ; those liquid products which remained in the autoclave. The oil fractions had densities in the range of from about 0.92 to about 0.94 grams per milliliter and had API gravities in the range of between about 19API.
to about 23API. The bitumen fractions had densities of about l.Ol grams per milliliter and API gravities of about lO. Oil shale sample A
contained 0.7 weight percent of sulfur, l.7 weight percent of nitrogen.
Use oE a catalyst in Example 36 caused a substantial increase in the amount of the oil fraction produced relative to the amount of the bitumen fraction produced.
TABLE l Oil Shale 1 Percent Weight Loss Sample Particle Size during Calcination A 60-80 32.2 B 14-28 26.8 (: 8-14 36. h D 1/4-l/82 22. 3 ootnotes 1 mesh si~e, except where otherwlse indicated.
2 diameter mensured in inches.
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~oooooooooooo ~o ~o P: lo ~ ~ o ~ o o~l . ~ ~ ~ o, cr~ o u~
C~
~ ' u) ~ O ~ c~
~ c~
`I l(l~OlZ5 ~ ~ O ~ D h .C ~
I t~
lS~4VlZ5 The results of eleme~tal analyses of several samples of oil and ¦ bitumen fractions obtained in several of these Examples are also oil ¦ shale feed, and oil kerogen product obtained using thermal retorting ¦ as r2ported by M. T. Atwood in Chemtech, October, 1973, s ¦ pages 617-621, are shown in Table 4. These ¦ results indicate that the elemental compositions of oils from different ¦ oil shales are quite similar. The weighted combined results for the oil ¦ and bitumen fractions from Examples 7-11 obtained using the method of ¦ this invention indicate tha~ these fractions combined have a similar ¦ nitrogen content but a lower sulfur content than does the oil obtained ¦ using thermal retorting. The H/C atom ratlos for oils obtained using ¦ the method of this invention are also similar to the ~/C atom ratios for ¦ oils obtained by thermal retorting. However, the ~I/C atom ratio for the combined oil and bitumen fractions obtained using the method of this ~5 invention is less than that for the oil - that is, total liquid products ¦ obtained by thermal retorting. This may reflec~ a larger total liquld yield obtained using the method of thls invention than with thermolytic ¦ distillation.
¦ The combined oil fractions obtsined in Examples 7 through 11 were characterized~ and the results are shown in Table 5, along with com-¦ parable results reported in the literature for oil fractions obtained ¦ from oil shale by thermal retorting and gas com~ustion retorting. How-ever, the olefin content of the oil fraction boiling up to 405F. obtaine 2s ¦ by the method of this invention differs from the oil content of the oil ¦ fractions boiling up to 405F. obtained by gas combustion retorting and by thermal retorting. The olefin content in this fraction obtained by ¦ the method of this invention is about half that in the corresponding ¦ fractions obtained by the thermal and gas combustion retorting processes.
¦ Clearly, while olefins are the primary products in this boiling fraction ¦ obtained by the thermal or gas combustion retortlng of hydrocarbons, ~3 S El lU4(~125 C~l ~~1~ ~ O `J ~D
t~ ~ 0~~L~ ~ L~ L~
~ ~ ~LLn ~ O CO
10 l ~ ¦ --i o l ~ P
I C~l J-l~Du~ U~ ~ ~ . , , , ,,_~
I ~,~ '~; ,i ,t ,~ o ~ o I ~ P~
l 5 Ic~ P~ ~ ~ u~ I P ~ ~
~ o o l ~ i L)_l p, 2 0 I Ll~ Lr~L~ C) ~ O
~ ~8~
~ ~ ~ o ~ ~ ~
~ o~ c :~ ~1 o o ~o ~ o ~ o ~ O
P, .. ~ ,, o ,, ¢
:: 2 5 h ~ ~ t) ~1 0 C ~ C C~
~3L ~ ¢ ¢ ~ 3 a~
~ ~ o ~ '~
E~ ~ u ~ 3 ~
3 0 L~ ~ `1 ~ d` Ln ~
x~
_ 26 -~ lZ5 Compositionl of Liquid from Method of Thermal Combusti this Invention Retorting2 Retortin , Component bitumen fraction 38 oil fraction 62 acid in component 3 3 4 base in compo~ent 14 8 8 neutral oil ~ 45 to 405F. 6 15 4 paraEElns and 3 3 naphthenes 48.53 273 273 olefins 20.03 483 513 aromatics31.5 25 22 405 to 600F. 10 pa~aEeins and 3 naphthenes 35.53 oleEins 24,03 aromatlcs40.5 600 ~o 700F. 6 resldlle (above 700F.) 23 l'ootnote 1 weight percent of liquid products except where otherwise indicated.
2 Results were reported in G. 0. Dinneen, R. A. Van Meter, J. R Smith, C. W. Bailey~ G. L. Cook, C. S. Allbright, and J. S. Ball, Bulletin 593, U.S. Bureau of Mines, 1961.
2s 3 volume percent of the particular boiling point fraction.
;
30 ~ - 27 -1~4~Z5 oils having a reduced oleEin conten~ are obtained by the method of this invention. Thi~ indicates that hydrogen is generated in sltu in the method of this invention and that such hydrogen is at least partially consumed in the hydrogenation of recovered olefins.
We have found that there exists a reasonable correlation of both the volumetric content of hydrocarbons in oil shale samples and the weight content of hydrocarbons in such samples with the weight loss of such samples during calcination in air at 1000F. for 30 minutes. Both the volumetric and the weight contents o hydrocarbons are based on the Fischer assay described by L. Goodfellow, C. F. Haberman, and M. T.
Atwood, "Modified Flscher Assay, "Division of Petroleum Chemistry, Abstracts, page F. 86, American Chemical Society, San Francisco ~leeting, April 2-5, 1968. Thls correlation i9 9hOWII in Figure 1.
Using this correlation, the expected yleld oE hydrocarbons from the oil shale samples we used was estimated in order to compare the actual yield of hydrocarbons with the expected total possible yield of ; hydrocarbons from the oil shale samples used. The weight loss duringcalcination of the oil shale samples used and the correlation shown in Figure 1 indicate that the oil shale samples used would yield liquid products in the range of approximately 14 to 22 percent by weight of the -~ oil shale feed.
The actual weight loss during calcination of oil shale sample A, the expected yield of hydrocarbons in this oil shale sample, and the actual yields of oil, bitumen, and the gaseous products (carbon dioxide and Cl to C3 hydrocarbons) recovered in 2-hour batch runs of oil shale sample A at various temperatures are shown in Figure 2. These runs were performed using shale-water weight ratios of either 0.56 or 1 When the ratio was 0.56, 90 grams of water were charged. When the ratio was 1, 60 grams of water were charged. The pressures ranged between 2550 and 4200 pounds per square inch gauge. The data plotted in Figure 2 were ~1 3.L?401Z5 taken from the results shown in Table 3. The liquid selectivity - the ratio of the total yield of liquid products to the weight loss of the oil shale sample during calcination - for oil shale sample A at 752F.
is 0.67. The oil selectivity - the ratio of the yield of oil to the total yield of llquid products - for oil shale sample A at 752F. is 0.61, The yield of oil recovered from oil shale by the method of this invention was markedly dependent on the temperature. The total liquid product yield - oil plus bitumen - was roughly constant at temperatures lo above 705F. and dropped sharply at temperatures below 705F. At tem-perntures above 705F., the total liquid product ylelds accounted fortor even sllghtly exGeeded the amountR recoverable eRtlmatecl l)y ~he Fischer assay. AlthouRIl eRsent:Lnlly all avallable hydrocarbon WaR rcmovec from the oil shale by the method oE thls invention at a temperature of at least 705F., the amounts of lighter hydrocarbon fractions recovered continued to increase as the temperature was increased above 705F.
This is evidenced in Figure 2 by the sharp increase in the oil yield and decrease in the bitumen yield as the temperature is increased above 705F. Such an increase in the oil yield and decrease in the bitumen yield is reasonable if cracking - either thermal or catalytic through the presence of catalys~s intrinsically present in the oil shale - of the bitumen were occurring.
Similar results, shown in Table 6, were obtained in Examples 1, 2, 15, and 26 - 28 with different contact tlmes and with oil shale samples of different particle size ranges than those used in obtatning the results shown in Figure 2. These results indicate that even at a tem-perature of 698F., slightly below the crltical temperature for water, the llquid and oll selectlvitles were substantially reduced from the values obtained at temperatures above the critical temperature of water.
` ~4~1Z5 Data Oil Reaction Reaction Liquid Oil from Shale Temperature Time Se- Se-Example ~ (F.) (hours) lectivity lectivity 2 A 660 2 0.27 0.06 1 A 752 2 0.67 0.61 28 B 716 2 0.63 0.41 B 752 2 0.58 0.68 27 D 698 0.5 0.42 0.47 26 D 752 0.5 0,58 0.50 Footnotes 1 The samples corresponding to the letters are identlfied ~ TEIble 1.
~ s Results showing the effect of the particle size of the oil shale substrate on the rate of recovery of hydrocarbons from oil shale are presented in Figures 3 and 4. The plots in Figures 3 and 4 were obtained using the results shown in Table 3, for runs involving a shale-to-water s weight ratio of 0.56. The weight loss during calcination, the expected yield of hydrocarbons from the oil shale sample, and the measured yield of liquid hydrocarbon products - all being expressed as weight percent of the oil shale feed - are shown in Figure 3 as a function of the contac time and of ~he range of particle sizes of the oil shale feed. Generally with oil shale Eeed having a partlcle siæe of approximately 1/4-inch diameter or less, more than 90 weight percent o~ the carbonaceous content of the oil shale feed was recovered ln less than one-half hour. When the oil shale feed had a particle size equal to or smaller than 8 mesh, the ylel~ oE total llquL~ products was ~reate.r after a contac~ time of one-half hour ~han nter a contact time of two hours, and exceeded the expected yield Oe hydrocarbons from the oil shale. For such feed, the decline of total yleld o the liquid hydrocarbon products with increasing contact time corresponded to increased conversion of the liquid products to dry gas, for example by cracking the liquid products. Cracking wa.s also indicated by the plots in Figure 4 showing the oil selectivity as a function of the contact time and of the range of the particle sizes of the oil shale feed.
~1hen the oil shale feed had a particle size in the range of from 1/4-inch to 1/8-inch, the rate of recovery was low enough so that the total yield of liquid products after a contact time of one-half hour was less than the total yield of liquid products after a contact time of two hours, This is indicated in Figure 3. Whlle no theory Eor this is proposed, if the oil shale feed is made up of coarser materials having a larger particle size, the ratio of surface area to particle volume for such materials would be lower than that for finer materials, and diffusio lU4V125 of water into the coarser oil shale particles and the rate of dissolution of the inorganic matrix in the supercritlcal water may decrease, and, hence, the rate of recovery may decrease.
There is evidence that efficient recovery of liquids from oil shale by the method of this invention involves partial dissolution of the inorganic matrix oE the oil shale substrate. Following complete recovery of liquids from oil shale feeds having particle sizes in the range of 1/4-inch diameter to 80 mesh, the spent oil shale solids recovered had substantially smaller particle sizes, generally less than 100 mesh.
lo Further, there was also a decrease in the bulk density from about 2.1 grams per milliliter for the feed to about 1.1 grams per milliliter for the spent solids. On the other hand, when the liquids were not completel recovered from the o:Ll shale Eeed, the oil shale particles retained much of their starting conformation, For example, little apparent confor-mational change occurred for oil shale feed when only half of the carbonaceous material was removed from it.
There i8 additional evidence of the decomposition of the inorganic matrix of the oil shale substrate during recovery of liquid hydrocarbons by the method of this invention. The high yield of carbon dioxide from the recovery of liquid hydrocarbons from oil shale, even at the relativel lo~ temperature of 660F., indicates decomposition of the inorganic carbonate in the structure of oil shale. The approximate mass balance of the oil shale feed and of the combined products from the recoveries in Examples 7-11 of liquid hydrocarbons from the oil shale sample A
demonstrate that carbon dioxide is formed from inorganic carbonate and is presented in Table 7.
The relationships by which the products were characterized are presented hereinafter. The total amount, SO, of oil shale feed, excluding entrained water, is given as follows:
So = S ~ IC + KC
1(~4~)1Z5 Weight Percent Component Component Symbol of the Feed l Oil Shale Feed
3 ~ o a~ a~ O O O '~
~v ~ ~ O
~ ~ ) 5 t~l ~
z; ol v 3 ~ ~ r 1 0 ~ '~ O ~ o ~ n ~t ~ ol o ~ o ;t ~D oo n O
c~ t~ ~ O ~ cr~ a~ oO
U~ ~
~ ~1 ~ n ~ ~ ~ co 0~ oO ,0~
~ .~
~1 C`~ In Init o~ r-- o ~ o a~ co 2 0 ~ ¦ ~ o ~ o~ u~ ~ ~ n ~D ~t r~
v ~ co o oo r~ r~ ~ oo c~l oQ
~3 E~
c~+l ~o ~ ~i o o 25 P~ a~
t c~ I o o o oo ~ o P~ o o~
c~
~ r~ oo 1 11~401Z5 o o ~ o o ,i ~ a~ I I
o o o o o o o o~ ~
~4 ~
c 81 ~ ~ ~
c~ ~ o ~ o ~1 1~ ~ ~
rl æ
~ Pl U) al ,~ ~ ~ ~O ~
o ~4 o ~ rO ~ O O G o O O O O
~ ~ ~ co U~ o o ~ ~ ~ o o o o o o o o -1 o oo c~ ~ o ~ ~ r~
15 v~ r~ o r~
_ ~a O~ ~ o ~ o o Oo ~ ~ o r~ o ~D o .~ , .~
~ ~ O U~
20 ~ ~ ~ ~
O o~ O I O `D O co a) oo b~
' O . E~
~ +l 25 ~ a~
c~ p~
C~ I o o o o o o o o o o o ~ 1 o o o p~ o o o o o ~ ~ o o ~ o ~1 oo u~
~~
~1 ~ lU4S~125 ,e ~ ~ I` o .~0 ~ O ~ O O o a~ ~ o o o o _i ~ ~ o a~ o o o cr~ o o o o o o 3 ~ ,~
,a a a a ~ o ~ ~ ~ ~ ~ ,~ a~ O
O ~ ~ O ~ 1 0 ~ .~ c~
o[
~o c~ r- co co ~D ~ 0~ 0 ~ O
J~ ~ I~ I O ~ O
Z o ,i ~ i o a C
~ J~ U~ ~D OD ~ u~ u~ ~D ~ ~ ~ u~
1 o ~ ~q o O o O o o o o o o o O
~ ~ 0 0 ,1 ,1 ~ oD o ~ Oo ~
~ o o o ~, o o' o o O o o o o ~1 o ~ ~ o ~ ~ o 1 î O 00 a~ o 0 ~' ~
~ ~ ~ o o u~
~~ I-f4 ~ 1 r~
~ .u ~ ~ O O ~D O In o~
E~ ~ l o ,~ ~ ~ o , C~ E~ O 1~
~ +
~ C~ o : : ~o ~d ~ .
' ~ ~ ~
~oooooooooooo ~o ~o P: lo ~ ~ o ~ o o~l . ~ ~ ~ o, cr~ o u~
C~
~ ' u) ~ O ~ c~
~ c~
`I l(l~OlZ5 ~ ~ O ~ D h .C ~
I t~
lS~4VlZ5 The results of eleme~tal analyses of several samples of oil and ¦ bitumen fractions obtained in several of these Examples are also oil ¦ shale feed, and oil kerogen product obtained using thermal retorting ¦ as r2ported by M. T. Atwood in Chemtech, October, 1973, s ¦ pages 617-621, are shown in Table 4. These ¦ results indicate that the elemental compositions of oils from different ¦ oil shales are quite similar. The weighted combined results for the oil ¦ and bitumen fractions from Examples 7-11 obtained using the method of ¦ this invention indicate tha~ these fractions combined have a similar ¦ nitrogen content but a lower sulfur content than does the oil obtained ¦ using thermal retorting. The H/C atom ratlos for oils obtained using ¦ the method of this invention are also similar to the ~/C atom ratios for ¦ oils obtained by thermal retorting. However, the ~I/C atom ratio for the combined oil and bitumen fractions obtained using the method of this ~5 invention is less than that for the oil - that is, total liquid products ¦ obtained by thermal retorting. This may reflec~ a larger total liquld yield obtained using the method of thls invention than with thermolytic ¦ distillation.
¦ The combined oil fractions obtsined in Examples 7 through 11 were characterized~ and the results are shown in Table 5, along with com-¦ parable results reported in the literature for oil fractions obtained ¦ from oil shale by thermal retorting and gas com~ustion retorting. How-ever, the olefin content of the oil fraction boiling up to 405F. obtaine 2s ¦ by the method of this invention differs from the oil content of the oil ¦ fractions boiling up to 405F. obtained by gas combustion retorting and by thermal retorting. The olefin content in this fraction obtained by ¦ the method of this invention is about half that in the corresponding ¦ fractions obtained by the thermal and gas combustion retorting processes.
¦ Clearly, while olefins are the primary products in this boiling fraction ¦ obtained by the thermal or gas combustion retortlng of hydrocarbons, ~3 S El lU4(~125 C~l ~~1~ ~ O `J ~D
t~ ~ 0~~L~ ~ L~ L~
~ ~ ~LLn ~ O CO
10 l ~ ¦ --i o l ~ P
I C~l J-l~Du~ U~ ~ ~ . , , , ,,_~
I ~,~ '~; ,i ,t ,~ o ~ o I ~ P~
l 5 Ic~ P~ ~ ~ u~ I P ~ ~
~ o o l ~ i L)_l p, 2 0 I Ll~ Lr~L~ C) ~ O
~ ~8~
~ ~ ~ o ~ ~ ~
~ o~ c :~ ~1 o o ~o ~ o ~ o ~ O
P, .. ~ ,, o ,, ¢
:: 2 5 h ~ ~ t) ~1 0 C ~ C C~
~3L ~ ¢ ¢ ~ 3 a~
~ ~ o ~ '~
E~ ~ u ~ 3 ~
3 0 L~ ~ `1 ~ d` Ln ~
x~
_ 26 -~ lZ5 Compositionl of Liquid from Method of Thermal Combusti this Invention Retorting2 Retortin , Component bitumen fraction 38 oil fraction 62 acid in component 3 3 4 base in compo~ent 14 8 8 neutral oil ~ 45 to 405F. 6 15 4 paraEElns and 3 3 naphthenes 48.53 273 273 olefins 20.03 483 513 aromatics31.5 25 22 405 to 600F. 10 pa~aEeins and 3 naphthenes 35.53 oleEins 24,03 aromatlcs40.5 600 ~o 700F. 6 resldlle (above 700F.) 23 l'ootnote 1 weight percent of liquid products except where otherwise indicated.
2 Results were reported in G. 0. Dinneen, R. A. Van Meter, J. R Smith, C. W. Bailey~ G. L. Cook, C. S. Allbright, and J. S. Ball, Bulletin 593, U.S. Bureau of Mines, 1961.
2s 3 volume percent of the particular boiling point fraction.
;
30 ~ - 27 -1~4~Z5 oils having a reduced oleEin conten~ are obtained by the method of this invention. Thi~ indicates that hydrogen is generated in sltu in the method of this invention and that such hydrogen is at least partially consumed in the hydrogenation of recovered olefins.
We have found that there exists a reasonable correlation of both the volumetric content of hydrocarbons in oil shale samples and the weight content of hydrocarbons in such samples with the weight loss of such samples during calcination in air at 1000F. for 30 minutes. Both the volumetric and the weight contents o hydrocarbons are based on the Fischer assay described by L. Goodfellow, C. F. Haberman, and M. T.
Atwood, "Modified Flscher Assay, "Division of Petroleum Chemistry, Abstracts, page F. 86, American Chemical Society, San Francisco ~leeting, April 2-5, 1968. Thls correlation i9 9hOWII in Figure 1.
Using this correlation, the expected yleld oE hydrocarbons from the oil shale samples we used was estimated in order to compare the actual yield of hydrocarbons with the expected total possible yield of ; hydrocarbons from the oil shale samples used. The weight loss duringcalcination of the oil shale samples used and the correlation shown in Figure 1 indicate that the oil shale samples used would yield liquid products in the range of approximately 14 to 22 percent by weight of the -~ oil shale feed.
The actual weight loss during calcination of oil shale sample A, the expected yield of hydrocarbons in this oil shale sample, and the actual yields of oil, bitumen, and the gaseous products (carbon dioxide and Cl to C3 hydrocarbons) recovered in 2-hour batch runs of oil shale sample A at various temperatures are shown in Figure 2. These runs were performed using shale-water weight ratios of either 0.56 or 1 When the ratio was 0.56, 90 grams of water were charged. When the ratio was 1, 60 grams of water were charged. The pressures ranged between 2550 and 4200 pounds per square inch gauge. The data plotted in Figure 2 were ~1 3.L?401Z5 taken from the results shown in Table 3. The liquid selectivity - the ratio of the total yield of liquid products to the weight loss of the oil shale sample during calcination - for oil shale sample A at 752F.
is 0.67. The oil selectivity - the ratio of the yield of oil to the total yield of llquid products - for oil shale sample A at 752F. is 0.61, The yield of oil recovered from oil shale by the method of this invention was markedly dependent on the temperature. The total liquid product yield - oil plus bitumen - was roughly constant at temperatures lo above 705F. and dropped sharply at temperatures below 705F. At tem-perntures above 705F., the total liquid product ylelds accounted fortor even sllghtly exGeeded the amountR recoverable eRtlmatecl l)y ~he Fischer assay. AlthouRIl eRsent:Lnlly all avallable hydrocarbon WaR rcmovec from the oil shale by the method oE thls invention at a temperature of at least 705F., the amounts of lighter hydrocarbon fractions recovered continued to increase as the temperature was increased above 705F.
This is evidenced in Figure 2 by the sharp increase in the oil yield and decrease in the bitumen yield as the temperature is increased above 705F. Such an increase in the oil yield and decrease in the bitumen yield is reasonable if cracking - either thermal or catalytic through the presence of catalys~s intrinsically present in the oil shale - of the bitumen were occurring.
Similar results, shown in Table 6, were obtained in Examples 1, 2, 15, and 26 - 28 with different contact tlmes and with oil shale samples of different particle size ranges than those used in obtatning the results shown in Figure 2. These results indicate that even at a tem-perature of 698F., slightly below the crltical temperature for water, the llquid and oll selectlvitles were substantially reduced from the values obtained at temperatures above the critical temperature of water.
` ~4~1Z5 Data Oil Reaction Reaction Liquid Oil from Shale Temperature Time Se- Se-Example ~ (F.) (hours) lectivity lectivity 2 A 660 2 0.27 0.06 1 A 752 2 0.67 0.61 28 B 716 2 0.63 0.41 B 752 2 0.58 0.68 27 D 698 0.5 0.42 0.47 26 D 752 0.5 0,58 0.50 Footnotes 1 The samples corresponding to the letters are identlfied ~ TEIble 1.
~ s Results showing the effect of the particle size of the oil shale substrate on the rate of recovery of hydrocarbons from oil shale are presented in Figures 3 and 4. The plots in Figures 3 and 4 were obtained using the results shown in Table 3, for runs involving a shale-to-water s weight ratio of 0.56. The weight loss during calcination, the expected yield of hydrocarbons from the oil shale sample, and the measured yield of liquid hydrocarbon products - all being expressed as weight percent of the oil shale feed - are shown in Figure 3 as a function of the contac time and of ~he range of particle sizes of the oil shale feed. Generally with oil shale Eeed having a partlcle siæe of approximately 1/4-inch diameter or less, more than 90 weight percent o~ the carbonaceous content of the oil shale feed was recovered ln less than one-half hour. When the oil shale feed had a particle size equal to or smaller than 8 mesh, the ylel~ oE total llquL~ products was ~reate.r after a contac~ time of one-half hour ~han nter a contact time of two hours, and exceeded the expected yield Oe hydrocarbons from the oil shale. For such feed, the decline of total yleld o the liquid hydrocarbon products with increasing contact time corresponded to increased conversion of the liquid products to dry gas, for example by cracking the liquid products. Cracking wa.s also indicated by the plots in Figure 4 showing the oil selectivity as a function of the contact time and of the range of the particle sizes of the oil shale feed.
~1hen the oil shale feed had a particle size in the range of from 1/4-inch to 1/8-inch, the rate of recovery was low enough so that the total yield of liquid products after a contact time of one-half hour was less than the total yield of liquid products after a contact time of two hours, This is indicated in Figure 3. Whlle no theory Eor this is proposed, if the oil shale feed is made up of coarser materials having a larger particle size, the ratio of surface area to particle volume for such materials would be lower than that for finer materials, and diffusio lU4V125 of water into the coarser oil shale particles and the rate of dissolution of the inorganic matrix in the supercritlcal water may decrease, and, hence, the rate of recovery may decrease.
There is evidence that efficient recovery of liquids from oil shale by the method of this invention involves partial dissolution of the inorganic matrix oE the oil shale substrate. Following complete recovery of liquids from oil shale feeds having particle sizes in the range of 1/4-inch diameter to 80 mesh, the spent oil shale solids recovered had substantially smaller particle sizes, generally less than 100 mesh.
lo Further, there was also a decrease in the bulk density from about 2.1 grams per milliliter for the feed to about 1.1 grams per milliliter for the spent solids. On the other hand, when the liquids were not completel recovered from the o:Ll shale Eeed, the oil shale particles retained much of their starting conformation, For example, little apparent confor-mational change occurred for oil shale feed when only half of the carbonaceous material was removed from it.
There i8 additional evidence of the decomposition of the inorganic matrix of the oil shale substrate during recovery of liquid hydrocarbons by the method of this invention. The high yield of carbon dioxide from the recovery of liquid hydrocarbons from oil shale, even at the relativel lo~ temperature of 660F., indicates decomposition of the inorganic carbonate in the structure of oil shale. The approximate mass balance of the oil shale feed and of the combined products from the recoveries in Examples 7-11 of liquid hydrocarbons from the oil shale sample A
demonstrate that carbon dioxide is formed from inorganic carbonate and is presented in Table 7.
The relationships by which the products were characterized are presented hereinafter. The total amount, SO, of oil shale feed, excluding entrained water, is given as follows:
So = S ~ IC + KC
1(~4~)1Z5 Weight Percent Component Component Symbol of the Feed l Oil Shale Feed
5 ¦ Kerogen KC 32 Acid-tltratable inorganic carbonate IC 19 Inorganic solid, S 49 excluding acid ¦ titratable lnorganlc carbonate 10 l I Recovery Product ¦ Dry ga9 KG
¦ Oil and bitumen KOB 23 ¦ Carbon dloxide 7 : ls ¦ Kerogen coke YKC 4 ¦ Acid-titratable ¦ inorganic carbonate xIc 15 ¦ Inorganic solid, S 50 ¦ excluding acid-ti~ratable inorganic carbonate ¦ Total :2o l i00 ~' ~' I
` 25 l I
~ 4U1~5 whereln the symbols used are defined in Table 7.
When the oil shale feed was titrated with acid, the amount of acid-titratable, inorganic carbonate initially present, IC 9 in the oil shale feed was determined, and thus the relationship between the measured amount of acld-titratable inorganic carbonate initially present and the measured total amount of oil shale feed could be expressed. Such relationship for oil shale sample A was IC = 0.187 S0 When the oil shale feed was calcined in air for 30 minutes at 1000F .
lo all organic material was driven off, and the measured weight of total lnorgan-lc material could be expressed in terms of the total amount of oil shale feed as follows:
S ~ IC = 0.678 S0 From the last two eqtlations, S was be calculated to be 0.491 S0.
The solid products obtained in the recovery of hyclrocarbons from the oll shale ~eed by the method of this invention are glven as follows:
S + X~c + YKC ' 0-686 S0 wherein the symbols used are defined in Table 7. The conditions employed in this run were a temperature of 752F., a pressure of approxlmately 4000 polmds per square inch gauge, a time of 2 hours, a charge of water of 60 grams, and a shale-to-water weight ratio of 1Ø
When the spent oil shale solid residue was titrated with acid, the amount of acid-titratable inorganlc carbonate present in the spent solid after the run could be determined, and the relationship between the measured amount of acid-titratable inorganic carbonate present after removal of the hydrocarbons, xIc, and the measured total amount of oil shale measured could be expressed as follows xIc = 0,147 S0 where x iB the Eraction of the amount initially present, Ic, which is still remaining.
104UlZ5 When the spent oil shale solid was calcined in air for 30 minutes at 1000F., all organic material was driven off~ and the measured weight of total organic material remaining after removal of the hydrocarbons could be expressed in terms of the total amount of oil shale as follows:
S + xIc = 0.643 SO
From the last two equations, S was calculated to be 0.496 SO. This value corresponds closely to the value of S calculated from the analytica characterization of the oil shale feed.
A very significant result from the analytical characterization shown in Table 7 is that the amount of acid-titratable inorganic carbonate in the solid spent oil shale was markedly lower than the amount of acid-titratable inorganic carbonate in the oil shale feed, and the difference between such amounts could account for between 50-60 weight percent of the gaaeous carbon dloxlde produced. Carbon dloxide derived ~rom the kerogen in the oil shale feed could also account for some of the remainder. Generally, inorganic carbonate in the structure of o:Ll sllale ~urvLves ~herma] proceff~lng 1~ the temperature i9 kept no hlgher than 1000F. Thu~, tllermal or gas combustive retorting daes not normally reduce the amount of acid-titratable inorganic carbonate. On the contrary, the amount of acid-titratable inorganic carbonate in the structure of oil shale was reduced by the method of this invention.
Results from 2-hour batch runs at 752F. showing the effect of the weight ratio of oil shale feed-to-solvent on the total yield of liquid products and on oil selectivity are presented in Table ~. The recovery was complete under the conditions employed when the weight ratio of oil shale feed-to-solvent was in the range oE from about 1:1 to about 1:2. A
weight ratio in this range also permits Eluid transfer and compression of the oil shale feed-solvent mixture 80 that a continuous slurry pro-cessing system is possible.
_ 35 _ Results Oil Oil Shale -to- Expec~ed Weight % of Feed from Shale W~ter Total Hydro- Recovered as Example Samplel Weight Ratio carbon Yield Oil Bitumen 1 A 1.0 22 13.2 8.3 3 ~ 0.6 22 13.5 6.5 13 B 1.0 16 11.8 9.0 B 0.6 16 10.5 S.O
12 C 1.0 22 17.8 9.2 lo 14 C 0.6 22 14.4 7.4 Footnotes 1 The samples corresponding to the letters are ldentified in Table 1.
~5 Example 37 involves a batch recovery of hydrocarbons from raw tar sands using the method of this invention. The conditions employed were a reaction temperature of 752F,, a reaction time of 2 hours, a reaction pressure of ~100 pounds per square inch gauge, and an argon pressure of 250 pounds per square inch guage. The feed was made up of 40 grams of raw tar sands in 90 grams of water. Thls run was performed in a 300-milliliter Hastelloy alloy C Magne-Drive autoclave. The products of this recovery included gas (hydrogen, carbon dioxide, and methane) and lo oil in amounts equivalent to 2 and 8 weight percent of the feed, respectively. The oll had an API gravity of about 17.0 and sulfur, nickel, and vanadium contents of 2.7 weight percent, and 45 and 30 parts per million, respectively. On the contrary, tar sands oil obtained by the COFCAW process had an API gravity oE 12.2 and sulfur, nickel, and vanadium contents of 4.6 weight percent, and 74 and 182 parts per mlllion respec~vely. ~Icnce, ~he ~ll obtained by the method of thls inventlon 1B upgrAded relnt:Lve to the oll produced by the COFCAW proces~, Further, the yields of gas, oll, bltumen, and solld products in this Fxample were 2.5, 3.7, 3.4, and 86.5 weight percent of the tar sands feed. This represents essentially complete recovery of the hydro-carbon content of the tar sands feed. The total amount of gas, oil, bitumen, and solid fractions and of water reco~ered constituted 97.4 weight percent of the tar sands and water feeds.
Examples 38-51 involve batch processing of different types of hydro-carbon feedstocks under a variety of conditions and illustrate that the mathod of this invention effectively cracks, desulfurizes, and demetalates hydrocarbons and therefore that the hydrocarbons recovered from the oll shale, tar sands, or coal solids are also cracked, desulfurized, and demetalated in the method of this invention. Unless otherwise specified, the following procedure was used in each case. The lV40125 hydrocarbon feed, water, and catalyst, if any, were loaded at ambient temperature into a 300-milliliter Hastelloy alloy C Magne-Drive auto-clave in which the reaction mixture was to be mixed. The components of the catalyst system were added as solutes in the water or as solids in s slurries in the water.
Unless otherwise speclfied, sufficient water was added in each Example so that, at the reaction temperature and pressure and in the reaction volume used, the density of the water was at least 0,1 gram per millil-iter.
o The autoclave was flushed with inert argon gas and was then closed.
Such inert ga~ was also added to raise the pressure of the reaction system. The contribution of argon to the total preqsure at ambient temperature is callecl the argon pressure~
The temperature oE the reaction system wa9 then raised to the desired level and the dense-water-containing fluld phase was formed.
~pproxlmately 28 minutes were required to heat the autoclave from ambient temperature to 660F. Approximately 6 minutes were required to raise the temperature from 660F. to 700F. Approximately another 6 minutes were requlred to raise the temperature from 700F. to 750F.
When the desired final temperature was reached, the temperature was held constant for the desired period of time. This final constant temperature and the period of time at this temperature are defined as the reaction temperature and reaction time, respectively. During the reaction time, the pressure of the reaction system increased as the reaction proceeded. The pressure at the start of the reaction time is defined as the reaction pressure.
After the desired reaction time at the desired reaction temperature and pressure, the dense-water-containing fluid phase was de-pressurized and was flash-distilled from the reaction vessel, removing the gas, water and "light" ends, and leaving the "heavy" ends and other solids, includin the catalyst, if present, in the reaction vessel. The "light" ends were ll)40125 the hydrocarbon fraction boiling at or below the reaction temperature and the "heavy" ends were the hydrocarbon fraction boiling above the reaction temperature.
The gas, water, and light ends were trapped in a pressure vessel cooled by liquid nitrogen. The gas was removed by warming the pressure vessel to room temperature and then was analyzed by mass spectroscopy, gas chromatography, and infra-red, 'rhe water and llght ends were then purged from the pressure vessel by means of compressed gas and occasion-ally also by heating the vessel. Then the water and light ends were 0 separated by decantation. ~lternately, this ~eparation was postponed until a later stage in the procedure. Gas chromatograms were run onthe light ends.
The heavy ends and solids, lncluding the catalyst, iE pr~sent, were washed from the reaction vessel with chloroform, and the heavy ends dissolved in this solvent. The solids were then separated from the solution containing the heavy ends by filtration.
After separating the chloroform from the heavy ends by distillation, the light ends and heavy ends were combined. If the water had not already been separated Erom the light ends, then it was separated from the combined light and heavy ends by centrifugation and decantation.
The combined light and heavy ends were analyzed for their nickel, vanadium, and sulfur content, carbon-hydrogen atom ratio (C/H), and API
gravity. The water was analyzed for nickel and vanadium, and the solids were analyzed for nickel, vanadium, and sulur. X-ray fluoresence was used to determine nickel, vanadium, and sulfur.
Examples 38-42 involve straight tar sands oil, and Examples 43-46 in~olve topped tar sands oil. Topped tar sands oil is the ~traight tar sands oil used in Examples 38-42 but from which approximately 25 weight percent of light material has been removed. Examples 47-50 involve C vacuum atmospheric residual oil. Example 51 involves C vacuum residual ~ 5 .~ ~ ~ ~ CO o ~
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104()~LZ5 oil. ~he compositions of the hydrocarbon feeds employed are shown in Table 9~ The experimental conditions used and the results of analyses of the products obtained in these ~xamples are shown in Tables lO and ll, respectively. A 300-milliliter Hastelloy alloy C Magne-Drive autoclave was employed as the reaction vessel in these Examples.
Comparison of the results shown in Table ll indicates that desulfurization and demetalation of the hydrocarbon feed occurred and that the hydrocarbon feed was cracked, producing gases, light ends, heavy ends, and solid residue, even when no catalyst was added from an externnl source. In such case, the extent of removal of sulfur and metals increasecl when the reaction time was increased Erom t to 3 hol1rs.
Beyond that time, the extent of desulfuriYntlon decrensec1 wLth -Increnslng reaction time. Addltion of a catalysc substnntially LncreMsed the extent of desulfurization and demetalation.
When the water density was at least O.l gram per milliliter - for example, when the hydrocarbon Eraction-to-water weight ratlo was l:3 -the sulfur which was removed from the hydrocarbon feed appeared as elemental sulfur and not as sulEur dioxide or as hydrogen sulfide. ~t lower water densities - for example~ when the hydrocarbon-to-water weight ratio was 4:1 - part of the removed sulfur appeared as hydrogen suifide. Th~s clearly indicates a change in the mechanlsm of de-sulfurization of organic compounds on contact with a dense-water-con-taining phase, depending upon the water density of the dense-water-con-2s taining phase. Further, when the hydrocarbon fraction-to-water weight ratio was ~I:l, there was an adverse shift in the distrib~1~ion oE hydro-carbon products and a lesser extent oE desulfurization.
The total weight percent of gases and compositions of the gas products obtained in several of the Examples are indicated in Table 12.
In all cases, the main component of the gas products was argon which was used in the pressurization of the reac~or and which is not reported in l(i'~lZ5 ¦ TABLE 12 Composi~ion of the Gas Products2 Total I Weight 5 I ReaCltin Carbon Percent Example Time Hydrogen Dioxide Methane of Gas I ~
39 3 3.3 5.2 6.9 11.2 1 2.8 3.1 3.4 1.3 43 1 1.0 3.8 8.4 1.0 1 44 3 3.0 5.6 7.5 S.9 10 l l ootnotes ¦ 1 hottr~.
¦ 2 mo:le percent of ~ns.
¦ Table 12. Generally, increaging the reactlon time resulted in increased ¦ yields of gaseous products.
¦ Successive exposure of the catalysts of this invention to hydro-¦ carbons containing sulfur contaminants did not cause a decrease in the s ¦ catalytic efficiency of the catalysts.
¦ EXAMPLES 52-61 ¦ Examples 52-61 involve semi-continuous flow processing at 752F. of ¦ straight tar sands oil under a variety of conditions. The flow system ¦ used in these Examples is shown ln Figure 5. To start a run, 1/8-inch to ¦ diameter inert, spherical alundum balls or lrregularly shaped, catalytlc ¦ titanium oxide chips havlng 2 weight percent oE ruthenium deposited ¦ thereon were loaded into a 21.5-lnch long, l-inch outside diameter, and ¦ 0.25-inch inslde diameter vertical Hastelloy alloy C plpe renctor 16.
¦ The alundum balls served merely to provide an lnert surface on which metals to be removed from the hydrocarbon feed could deposlt. Top 19 was then closed, and a furnace (not shown) was placed around the length of pipe reactor 16. Plpe reactor 16 had a total eEfective heated volume of approximately 12 milliliters, and the packing material had a total volume of approximately 6 milliliters, leaving approximately a 6-mllli-liter free effective heated space in pipe reactor 16.
All valves, except 53 and 61, were opened, and the flow system was flushed with argon or nitrogen. Then, with valves 4, 5, 29, 37, 46, 53, 61, and 84 closed and with Annin valve 82 set to release gas from the 2s flow system when the desired pressure in the system was exceeded, the flow system was brought up to a pressure in the range of Erom about 1000 to about 2000 pounds per square lnch gauge by argon or nitrogen entering the system through valve 80 and line 79. Then valve 80 was closed.
Next, the pressure of the Elow system was brought up to the desired reaction pressure by opening valve 53 and pumping water through Haskel 3~ pUD O and line 51 into water t~nk 54 The water served to Eurther 1~ 5 compress the gas ln the flow system and thereby to further increase the pressure in the system. If a greater volume of water than the volume of water tank 54 was needed to ralse the pressure of the flow system to the desired level, then valve 61 was opened, and additional water was pumped through line 60 and into dump tank 44. When the pressure of the flow system reached the desired pressure, valves 53 and 61 were closed.
A Ruska pump 1 was used to pump the hydrocarbon fractian and water into pipe reactor 16. The Ruska pump 1 contained two 250-milliliter barrels (not shown), with the hydrocarbon fraction being loaded into one barrel and water into the other, at ambient temperature and atmos-pheric pressure. Pistons (not shown) inside these barrels were manuallyturned on until the pressure in each barrel equaled the pressure of the flow system. When the pressures in the barrels and in the flow system were equal, check valves 4 and 5 opened to admit hydrocarbon Eraction and water from the barrels to flow through lines 2 and 3. At the same time, valve 72 was closed to prevent flow in line 70 between points 12 and 78. Then the hydrocarbon ~ractLon and water ~treams Joined at po-Lnt 10 at nmbient temperature and ut the de~lred pressure, rlowed througl line 11, and entered the bottom 17 of pipe reactor 16. The reaction mixture flowed through pipe reactor 16 and exited from pipe reactor 16 through slde ar~ 24 at point 20 in the wall of pipe reactor 16. Point 20 was 19 inches from bottom 17.
With solution flowing through pipe reactor 16, the furnace began heating pipe reactor 16. During heat-up of pipe reactor 16 and until steady state conditions were achieved, valves 26 and 34 were closed, and valve 43 was opened to permit the mixture in side arm 24 to flow through line 42 and to enter and be stored in dump tank 44. After steady state conditions were achieved, valve 43 was closed, and valve 34 was opened for the desired period of time to permit the mixture in side arm 24 to flow through line 33 and to enter and be stored ln product receiver 35. After eoIlcctln~ n batc~ of product In product recelver 35 ~or the de~Ired p~riod of time, valve 34 was closed, nnd vnlve 26 was opened to permlt th~ mixture in side arm 24 to flow through llne 25 and to enter and be stored in product receiver 27 for ano~her period of time. Then S valve 26 was closed.
The mnterial in side arm 24 was a mixture of gaseous and liquid phase~. When such mixture entered dump tank 44, product receiver 35, or product receiver 27, the gaseou~ and l~quid phases separated, and the ga~es exited from dump tank 44, product receiver 35, and product receiver o 27 throu~h lines 47, 38, and 30, respectively, and pnssed through line 70 and Annin valve 82 to a storage vessel (not shown).
en more than two batches of product were to be collected, valve 29 and/or valve 37 was opened to remove product from product recelver 27 and/or 35, respectively, to permit the same product receiver and/or receivers to be used to collect additional batches of product.
At the end of a run - during which the desired number of batches of product were collected - the temperature of pipe reactor 16 was lowered to ambient temperature, nnd the flow system was depressurized by opening vnlve 84, in line 85 venting to the atmosphere.
Diaphragm 76 measured the pressure differential across the length of pipe reactor 16. No solution flowed through line 85.
The API gravity of the liquid hydrocarbon products collected was measured, and their nickel, vanadium, and iron contents were determined by x-ray fluorescence.
The properties of the straight tar sands oil feed employed in Examples 52-61 are shown ~n Table 9. The tar sands oil feed contained 300-500 parts per million of iron, and the amount of 300 parts per million was used to determine the percent iron removed from the product.
The experimental conditions and charscteristics of the products formed in these Examples are presented in Table 13. The liquid hourly space 113~LU1~5 s ~ o o ~ ~ o ~ ,` CO
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¦ The flow process employed in Examples 52-61 could also be modified ¦ so as to permit pumping a slurry of oil shale solids, tar sands solids, ¦ or coal solids in a water-containing fluid through pipe reaceor 16. In ¦ such case, the alundum balls would not be present in pipe reactor 16, I and dump tank 44 and product receivers 27 and 35 could be equipped with ¦ some device, for example a screen, to separate the spent solids from the ¦ recovered hydrocarbon product. Thus, continuous and semi-continuous flow ¦ processing could be used in the recovery process itself.
¦ EXAMPLES 62-78 ¦ Examples 62-78 involve ba~ch processing of coal Eeeds under a ¦ variety of condltions and illustrate that liquids and gases are recovered, that the recovered liquids are cracked and desulfurized, and that the remaining solid coal is desulfurized in the method of this invention. Unless otherwise specified, the following procedure was used in each case. The coal feed, water-containing fluid, and components of the catalyst system, if used, were loaded at ambient temperature into a ~; 300-milliliter Hastelloy alloy C Magne-Drive batch autoclave in which ; the reaction mixture was to be mixed. The components of the catalyst system were added as solutes in the water-containing fluid or as solids in slurries in the water-containing fluid. Unless otherwise specified, sufficient water was added in each Example so that, at the reaction tem-perature and pressure and in the reaction volume used, the density of the water was at least 0,1 gram per milliliter~
The autoclave was flushed with inert argon gas and was then closed.
Such inert gas was also added to raise the pressure of the reaction system. The contribution of argon to the total pressure at amblent temperature is called the argon pressure.
~ s 'rhe temperature o~ the reactlon system was then rai~ed to the desired level and the dense-water-containlng fluid phase was formed.
Approximately 28 minutes were required to heat the autoclave from ambient temperature to 660F. Approximately 6 minutes were required to raise the temperature from 660F. to 700F. Approximately another 6 minutes were req~lired to raise the temperature from 700F. to 750~F.
When the desired final temperature was reached, the temperature was held constant for the desired period of time. This final constant temperature and the period of time at this temperature are defined as lo the reactlon temperature and reaction time, respectively. During the reaction time, the pressure of the reaction system increased as the reaction proceeded. The pressure at the start of the reaction time is defined as the reaction pressure.
AEter the deslred reaction tlme at the deslred react:Lon temperature and pressure, ~he dense-water-containlng fluld phase was cle-press~lrl~ed by flash-dlstillLng from the reactlon vessel, retnoving the argon, gu~ prodtlcts, wute-r, nnd "oll," Mnd leavlng ~he "bl~umen," soll(l resld~le, und cntaly~t, Ir pre~cnt, Ln Lllc reuctlon veH~el. 'I'he "olL" W-1.4 the liquid hydrocarbon fraction boiling at or below the reaction temperature and the "bitumen" was the liquid hydrocarbon fraction boiling above the reaction temperature. The solid residue was remaining solid coal.
The argon, gas products, water, and oil were trapped in a pressure vessel cooled by liquid nitrogen. The argon and gas products were removed by warming the pressure vessel to room temperature, and then the gas products were analyzed by mass spectroscopy, gas chromatography, and infra-red. The water and oil were then purged from the pressure vessel by means oE compressed gas and occasionally also by heating the vessel. Then the water and oil were separated by decantation. The oil was analyzed for its sulfur content using X-ray fluoresence.
4~5 Coal Part~cle MoistureSulfur 3 Sample Size Content2Content A 10-40 22.2 0.74 B 10-40 9.7 4.5 C4 ~ 80 2.7 4.9 Footnotes 1 mesh size.
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1041~?~25 The bitumen, solid residue, and catalyst, if present, were washed from the reaction vessel with chloroform, and the bitumen dissolved in this solvent. The solid residue and catalyst, if present, were then separated from the solution containing the bitumen by Eiltration. The bitumen and solids were analyzed for their sulfur contents using the same method as in the analysis of the oil.
The weights oE the various components or fractions added and recovered were determined either directly or indirectly by difference at various stages during the procedure.
0 Three samples of coal were used in this work. The sa~ples were obtained ln the Eorm of lumps, which were then ground and sieved to obtain fractlons of various particle sizes. The partlcle size and moisture and sulftlr contents oE each sample used nre presented in 'rab1.e l. Samples A and B were obtalned from Commonwealth Edlson Company, while sample C was an Illinois number 6 seam coal obtained Erom Hydro-carbon Research Incorporated. Sample A was a sub-bituminous coal, while samples B and C were highly volatile bituminous coals. These samples were stored under 8 blanket of argon until used.
Examples 62-78 involve batch recovery of liquids and gases from the coal samples shown in Table 14 using the method described above. These runs were performed in a 300-milliliter Hastelloy alloy C Magne-Drive autoclave. The experimental conditions and the results determined in these Examples are presented in Tables 15 and 16~ respectively.
2s In these Examples, the liquid hydrocarbon products were classified either as oils or as bitumens depending on whether or not such liquid products could be flashed from the autoclave upon depressurlzation of the autoclave at the run temperature employed. Oils were those liquid products which flashed over at the run temperature, while bitumens were those liquid products which remained in the autoclave.
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¦ Oil and bitumen KOB 23 ¦ Carbon dloxide 7 : ls ¦ Kerogen coke YKC 4 ¦ Acid-titratable ¦ inorganic carbonate xIc 15 ¦ Inorganic solid, S 50 ¦ excluding acid-ti~ratable inorganic carbonate ¦ Total :2o l i00 ~' ~' I
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When the oil shale feed was titrated with acid, the amount of acid-titratable, inorganic carbonate initially present, IC 9 in the oil shale feed was determined, and thus the relationship between the measured amount of acld-titratable inorganic carbonate initially present and the measured total amount of oil shale feed could be expressed. Such relationship for oil shale sample A was IC = 0.187 S0 When the oil shale feed was calcined in air for 30 minutes at 1000F .
lo all organic material was driven off, and the measured weight of total lnorgan-lc material could be expressed in terms of the total amount of oil shale feed as follows:
S ~ IC = 0.678 S0 From the last two eqtlations, S was be calculated to be 0.491 S0.
The solid products obtained in the recovery of hyclrocarbons from the oll shale ~eed by the method of this invention are glven as follows:
S + X~c + YKC ' 0-686 S0 wherein the symbols used are defined in Table 7. The conditions employed in this run were a temperature of 752F., a pressure of approxlmately 4000 polmds per square inch gauge, a time of 2 hours, a charge of water of 60 grams, and a shale-to-water weight ratio of 1Ø
When the spent oil shale solid residue was titrated with acid, the amount of acid-titratable inorganlc carbonate present in the spent solid after the run could be determined, and the relationship between the measured amount of acid-titratable inorganic carbonate present after removal of the hydrocarbons, xIc, and the measured total amount of oil shale measured could be expressed as follows xIc = 0,147 S0 where x iB the Eraction of the amount initially present, Ic, which is still remaining.
104UlZ5 When the spent oil shale solid was calcined in air for 30 minutes at 1000F., all organic material was driven off~ and the measured weight of total organic material remaining after removal of the hydrocarbons could be expressed in terms of the total amount of oil shale as follows:
S + xIc = 0.643 SO
From the last two equations, S was calculated to be 0.496 SO. This value corresponds closely to the value of S calculated from the analytica characterization of the oil shale feed.
A very significant result from the analytical characterization shown in Table 7 is that the amount of acid-titratable inorganic carbonate in the solid spent oil shale was markedly lower than the amount of acid-titratable inorganic carbonate in the oil shale feed, and the difference between such amounts could account for between 50-60 weight percent of the gaaeous carbon dloxlde produced. Carbon dloxide derived ~rom the kerogen in the oil shale feed could also account for some of the remainder. Generally, inorganic carbonate in the structure of o:Ll sllale ~urvLves ~herma] proceff~lng 1~ the temperature i9 kept no hlgher than 1000F. Thu~, tllermal or gas combustive retorting daes not normally reduce the amount of acid-titratable inorganic carbonate. On the contrary, the amount of acid-titratable inorganic carbonate in the structure of oil shale was reduced by the method of this invention.
Results from 2-hour batch runs at 752F. showing the effect of the weight ratio of oil shale feed-to-solvent on the total yield of liquid products and on oil selectivity are presented in Table ~. The recovery was complete under the conditions employed when the weight ratio of oil shale feed-to-solvent was in the range oE from about 1:1 to about 1:2. A
weight ratio in this range also permits Eluid transfer and compression of the oil shale feed-solvent mixture 80 that a continuous slurry pro-cessing system is possible.
_ 35 _ Results Oil Oil Shale -to- Expec~ed Weight % of Feed from Shale W~ter Total Hydro- Recovered as Example Samplel Weight Ratio carbon Yield Oil Bitumen 1 A 1.0 22 13.2 8.3 3 ~ 0.6 22 13.5 6.5 13 B 1.0 16 11.8 9.0 B 0.6 16 10.5 S.O
12 C 1.0 22 17.8 9.2 lo 14 C 0.6 22 14.4 7.4 Footnotes 1 The samples corresponding to the letters are ldentified in Table 1.
~5 Example 37 involves a batch recovery of hydrocarbons from raw tar sands using the method of this invention. The conditions employed were a reaction temperature of 752F,, a reaction time of 2 hours, a reaction pressure of ~100 pounds per square inch gauge, and an argon pressure of 250 pounds per square inch guage. The feed was made up of 40 grams of raw tar sands in 90 grams of water. Thls run was performed in a 300-milliliter Hastelloy alloy C Magne-Drive autoclave. The products of this recovery included gas (hydrogen, carbon dioxide, and methane) and lo oil in amounts equivalent to 2 and 8 weight percent of the feed, respectively. The oll had an API gravity of about 17.0 and sulfur, nickel, and vanadium contents of 2.7 weight percent, and 45 and 30 parts per million, respectively. On the contrary, tar sands oil obtained by the COFCAW process had an API gravity oE 12.2 and sulfur, nickel, and vanadium contents of 4.6 weight percent, and 74 and 182 parts per mlllion respec~vely. ~Icnce, ~he ~ll obtained by the method of thls inventlon 1B upgrAded relnt:Lve to the oll produced by the COFCAW proces~, Further, the yields of gas, oll, bltumen, and solld products in this Fxample were 2.5, 3.7, 3.4, and 86.5 weight percent of the tar sands feed. This represents essentially complete recovery of the hydro-carbon content of the tar sands feed. The total amount of gas, oil, bitumen, and solid fractions and of water reco~ered constituted 97.4 weight percent of the tar sands and water feeds.
Examples 38-51 involve batch processing of different types of hydro-carbon feedstocks under a variety of conditions and illustrate that the mathod of this invention effectively cracks, desulfurizes, and demetalates hydrocarbons and therefore that the hydrocarbons recovered from the oll shale, tar sands, or coal solids are also cracked, desulfurized, and demetalated in the method of this invention. Unless otherwise specified, the following procedure was used in each case. The lV40125 hydrocarbon feed, water, and catalyst, if any, were loaded at ambient temperature into a 300-milliliter Hastelloy alloy C Magne-Drive auto-clave in which the reaction mixture was to be mixed. The components of the catalyst system were added as solutes in the water or as solids in s slurries in the water.
Unless otherwise speclfied, sufficient water was added in each Example so that, at the reaction temperature and pressure and in the reaction volume used, the density of the water was at least 0,1 gram per millil-iter.
o The autoclave was flushed with inert argon gas and was then closed.
Such inert ga~ was also added to raise the pressure of the reaction system. The contribution of argon to the total preqsure at ambient temperature is callecl the argon pressure~
The temperature oE the reaction system wa9 then raised to the desired level and the dense-water-containing fluld phase was formed.
~pproxlmately 28 minutes were required to heat the autoclave from ambient temperature to 660F. Approximately 6 minutes were required to raise the temperature from 660F. to 700F. Approximately another 6 minutes were requlred to raise the temperature from 700F. to 750F.
When the desired final temperature was reached, the temperature was held constant for the desired period of time. This final constant temperature and the period of time at this temperature are defined as the reaction temperature and reaction time, respectively. During the reaction time, the pressure of the reaction system increased as the reaction proceeded. The pressure at the start of the reaction time is defined as the reaction pressure.
After the desired reaction time at the desired reaction temperature and pressure, the dense-water-containing fluid phase was de-pressurized and was flash-distilled from the reaction vessel, removing the gas, water and "light" ends, and leaving the "heavy" ends and other solids, includin the catalyst, if present, in the reaction vessel. The "light" ends were ll)40125 the hydrocarbon fraction boiling at or below the reaction temperature and the "heavy" ends were the hydrocarbon fraction boiling above the reaction temperature.
The gas, water, and light ends were trapped in a pressure vessel cooled by liquid nitrogen. The gas was removed by warming the pressure vessel to room temperature and then was analyzed by mass spectroscopy, gas chromatography, and infra-red, 'rhe water and llght ends were then purged from the pressure vessel by means of compressed gas and occasion-ally also by heating the vessel. Then the water and light ends were 0 separated by decantation. ~lternately, this ~eparation was postponed until a later stage in the procedure. Gas chromatograms were run onthe light ends.
The heavy ends and solids, lncluding the catalyst, iE pr~sent, were washed from the reaction vessel with chloroform, and the heavy ends dissolved in this solvent. The solids were then separated from the solution containing the heavy ends by filtration.
After separating the chloroform from the heavy ends by distillation, the light ends and heavy ends were combined. If the water had not already been separated Erom the light ends, then it was separated from the combined light and heavy ends by centrifugation and decantation.
The combined light and heavy ends were analyzed for their nickel, vanadium, and sulfur content, carbon-hydrogen atom ratio (C/H), and API
gravity. The water was analyzed for nickel and vanadium, and the solids were analyzed for nickel, vanadium, and sulur. X-ray fluoresence was used to determine nickel, vanadium, and sulfur.
Examples 38-42 involve straight tar sands oil, and Examples 43-46 in~olve topped tar sands oil. Topped tar sands oil is the ~traight tar sands oil used in Examples 38-42 but from which approximately 25 weight percent of light material has been removed. Examples 47-50 involve C vacuum atmospheric residual oil. Example 51 involves C vacuum residual ~ 5 .~ ~ ~ ~ CO o ~
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Comparison of the results shown in Table ll indicates that desulfurization and demetalation of the hydrocarbon feed occurred and that the hydrocarbon feed was cracked, producing gases, light ends, heavy ends, and solid residue, even when no catalyst was added from an externnl source. In such case, the extent of removal of sulfur and metals increasecl when the reaction time was increased Erom t to 3 hol1rs.
Beyond that time, the extent of desulfuriYntlon decrensec1 wLth -Increnslng reaction time. Addltion of a catalysc substnntially LncreMsed the extent of desulfurization and demetalation.
When the water density was at least O.l gram per milliliter - for example, when the hydrocarbon Eraction-to-water weight ratlo was l:3 -the sulfur which was removed from the hydrocarbon feed appeared as elemental sulfur and not as sulEur dioxide or as hydrogen sulfide. ~t lower water densities - for example~ when the hydrocarbon-to-water weight ratio was 4:1 - part of the removed sulfur appeared as hydrogen suifide. Th~s clearly indicates a change in the mechanlsm of de-sulfurization of organic compounds on contact with a dense-water-con-taining phase, depending upon the water density of the dense-water-con-2s taining phase. Further, when the hydrocarbon fraction-to-water weight ratio was ~I:l, there was an adverse shift in the distrib~1~ion oE hydro-carbon products and a lesser extent oE desulfurization.
The total weight percent of gases and compositions of the gas products obtained in several of the Examples are indicated in Table 12.
In all cases, the main component of the gas products was argon which was used in the pressurization of the reac~or and which is not reported in l(i'~lZ5 ¦ TABLE 12 Composi~ion of the Gas Products2 Total I Weight 5 I ReaCltin Carbon Percent Example Time Hydrogen Dioxide Methane of Gas I ~
39 3 3.3 5.2 6.9 11.2 1 2.8 3.1 3.4 1.3 43 1 1.0 3.8 8.4 1.0 1 44 3 3.0 5.6 7.5 S.9 10 l l ootnotes ¦ 1 hottr~.
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¦ Table 12. Generally, increaging the reactlon time resulted in increased ¦ yields of gaseous products.
¦ Successive exposure of the catalysts of this invention to hydro-¦ carbons containing sulfur contaminants did not cause a decrease in the s ¦ catalytic efficiency of the catalysts.
¦ EXAMPLES 52-61 ¦ Examples 52-61 involve semi-continuous flow processing at 752F. of ¦ straight tar sands oil under a variety of conditions. The flow system ¦ used in these Examples is shown ln Figure 5. To start a run, 1/8-inch to ¦ diameter inert, spherical alundum balls or lrregularly shaped, catalytlc ¦ titanium oxide chips havlng 2 weight percent oE ruthenium deposited ¦ thereon were loaded into a 21.5-lnch long, l-inch outside diameter, and ¦ 0.25-inch inslde diameter vertical Hastelloy alloy C plpe renctor 16.
¦ The alundum balls served merely to provide an lnert surface on which metals to be removed from the hydrocarbon feed could deposlt. Top 19 was then closed, and a furnace (not shown) was placed around the length of pipe reactor 16. Plpe reactor 16 had a total eEfective heated volume of approximately 12 milliliters, and the packing material had a total volume of approximately 6 milliliters, leaving approximately a 6-mllli-liter free effective heated space in pipe reactor 16.
All valves, except 53 and 61, were opened, and the flow system was flushed with argon or nitrogen. Then, with valves 4, 5, 29, 37, 46, 53, 61, and 84 closed and with Annin valve 82 set to release gas from the 2s flow system when the desired pressure in the system was exceeded, the flow system was brought up to a pressure in the range of Erom about 1000 to about 2000 pounds per square lnch gauge by argon or nitrogen entering the system through valve 80 and line 79. Then valve 80 was closed.
Next, the pressure of the Elow system was brought up to the desired reaction pressure by opening valve 53 and pumping water through Haskel 3~ pUD O and line 51 into water t~nk 54 The water served to Eurther 1~ 5 compress the gas ln the flow system and thereby to further increase the pressure in the system. If a greater volume of water than the volume of water tank 54 was needed to ralse the pressure of the flow system to the desired level, then valve 61 was opened, and additional water was pumped through line 60 and into dump tank 44. When the pressure of the flow system reached the desired pressure, valves 53 and 61 were closed.
A Ruska pump 1 was used to pump the hydrocarbon fractian and water into pipe reactor 16. The Ruska pump 1 contained two 250-milliliter barrels (not shown), with the hydrocarbon fraction being loaded into one barrel and water into the other, at ambient temperature and atmos-pheric pressure. Pistons (not shown) inside these barrels were manuallyturned on until the pressure in each barrel equaled the pressure of the flow system. When the pressures in the barrels and in the flow system were equal, check valves 4 and 5 opened to admit hydrocarbon Eraction and water from the barrels to flow through lines 2 and 3. At the same time, valve 72 was closed to prevent flow in line 70 between points 12 and 78. Then the hydrocarbon ~ractLon and water ~treams Joined at po-Lnt 10 at nmbient temperature and ut the de~lred pressure, rlowed througl line 11, and entered the bottom 17 of pipe reactor 16. The reaction mixture flowed through pipe reactor 16 and exited from pipe reactor 16 through slde ar~ 24 at point 20 in the wall of pipe reactor 16. Point 20 was 19 inches from bottom 17.
With solution flowing through pipe reactor 16, the furnace began heating pipe reactor 16. During heat-up of pipe reactor 16 and until steady state conditions were achieved, valves 26 and 34 were closed, and valve 43 was opened to permit the mixture in side arm 24 to flow through line 42 and to enter and be stored in dump tank 44. After steady state conditions were achieved, valve 43 was closed, and valve 34 was opened for the desired period of time to permit the mixture in side arm 24 to flow through line 33 and to enter and be stored ln product receiver 35. After eoIlcctln~ n batc~ of product In product recelver 35 ~or the de~Ired p~riod of time, valve 34 was closed, nnd vnlve 26 was opened to permlt th~ mixture in side arm 24 to flow through llne 25 and to enter and be stored in product receiver 27 for ano~her period of time. Then S valve 26 was closed.
The mnterial in side arm 24 was a mixture of gaseous and liquid phase~. When such mixture entered dump tank 44, product receiver 35, or product receiver 27, the gaseou~ and l~quid phases separated, and the ga~es exited from dump tank 44, product receiver 35, and product receiver o 27 throu~h lines 47, 38, and 30, respectively, and pnssed through line 70 and Annin valve 82 to a storage vessel (not shown).
en more than two batches of product were to be collected, valve 29 and/or valve 37 was opened to remove product from product recelver 27 and/or 35, respectively, to permit the same product receiver and/or receivers to be used to collect additional batches of product.
At the end of a run - during which the desired number of batches of product were collected - the temperature of pipe reactor 16 was lowered to ambient temperature, nnd the flow system was depressurized by opening vnlve 84, in line 85 venting to the atmosphere.
Diaphragm 76 measured the pressure differential across the length of pipe reactor 16. No solution flowed through line 85.
The API gravity of the liquid hydrocarbon products collected was measured, and their nickel, vanadium, and iron contents were determined by x-ray fluorescence.
The properties of the straight tar sands oil feed employed in Examples 52-61 are shown ~n Table 9. The tar sands oil feed contained 300-500 parts per million of iron, and the amount of 300 parts per million was used to determine the percent iron removed from the product.
The experimental conditions and charscteristics of the products formed in these Examples are presented in Table 13. The liquid hourly space 113~LU1~5 s ~ o o ~ ~ o ~ ,` CO
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¦ The flow process employed in Examples 52-61 could also be modified ¦ so as to permit pumping a slurry of oil shale solids, tar sands solids, ¦ or coal solids in a water-containing fluid through pipe reaceor 16. In ¦ such case, the alundum balls would not be present in pipe reactor 16, I and dump tank 44 and product receivers 27 and 35 could be equipped with ¦ some device, for example a screen, to separate the spent solids from the ¦ recovered hydrocarbon product. Thus, continuous and semi-continuous flow ¦ processing could be used in the recovery process itself.
¦ EXAMPLES 62-78 ¦ Examples 62-78 involve ba~ch processing of coal Eeeds under a ¦ variety of condltions and illustrate that liquids and gases are recovered, that the recovered liquids are cracked and desulfurized, and that the remaining solid coal is desulfurized in the method of this invention. Unless otherwise specified, the following procedure was used in each case. The coal feed, water-containing fluid, and components of the catalyst system, if used, were loaded at ambient temperature into a ~; 300-milliliter Hastelloy alloy C Magne-Drive batch autoclave in which ; the reaction mixture was to be mixed. The components of the catalyst system were added as solutes in the water-containing fluid or as solids in slurries in the water-containing fluid. Unless otherwise specified, sufficient water was added in each Example so that, at the reaction tem-perature and pressure and in the reaction volume used, the density of the water was at least 0,1 gram per milliliter~
The autoclave was flushed with inert argon gas and was then closed.
Such inert gas was also added to raise the pressure of the reaction system. The contribution of argon to the total pressure at amblent temperature is called the argon pressure.
~ s 'rhe temperature o~ the reactlon system was then rai~ed to the desired level and the dense-water-containlng fluid phase was formed.
Approximately 28 minutes were required to heat the autoclave from ambient temperature to 660F. Approximately 6 minutes were required to raise the temperature from 660F. to 700F. Approximately another 6 minutes were req~lired to raise the temperature from 700F. to 750~F.
When the desired final temperature was reached, the temperature was held constant for the desired period of time. This final constant temperature and the period of time at this temperature are defined as lo the reactlon temperature and reaction time, respectively. During the reaction time, the pressure of the reaction system increased as the reaction proceeded. The pressure at the start of the reaction time is defined as the reaction pressure.
AEter the deslred reaction tlme at the deslred react:Lon temperature and pressure, ~he dense-water-containlng fluld phase was cle-press~lrl~ed by flash-dlstillLng from the reactlon vessel, retnoving the argon, gu~ prodtlcts, wute-r, nnd "oll," Mnd leavlng ~he "bl~umen," soll(l resld~le, und cntaly~t, Ir pre~cnt, Ln Lllc reuctlon veH~el. 'I'he "olL" W-1.4 the liquid hydrocarbon fraction boiling at or below the reaction temperature and the "bitumen" was the liquid hydrocarbon fraction boiling above the reaction temperature. The solid residue was remaining solid coal.
The argon, gas products, water, and oil were trapped in a pressure vessel cooled by liquid nitrogen. The argon and gas products were removed by warming the pressure vessel to room temperature, and then the gas products were analyzed by mass spectroscopy, gas chromatography, and infra-red. The water and oil were then purged from the pressure vessel by means oE compressed gas and occasionally also by heating the vessel. Then the water and oil were separated by decantation. The oil was analyzed for its sulfur content using X-ray fluoresence.
4~5 Coal Part~cle MoistureSulfur 3 Sample Size Content2Content A 10-40 22.2 0.74 B 10-40 9.7 4.5 C4 ~ 80 2.7 4.9 Footnotes 1 mesh size.
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1041~?~25 The bitumen, solid residue, and catalyst, if present, were washed from the reaction vessel with chloroform, and the bitumen dissolved in this solvent. The solid residue and catalyst, if present, were then separated from the solution containing the bitumen by Eiltration. The bitumen and solids were analyzed for their sulfur contents using the same method as in the analysis of the oil.
The weights oE the various components or fractions added and recovered were determined either directly or indirectly by difference at various stages during the procedure.
0 Three samples of coal were used in this work. The sa~ples were obtained ln the Eorm of lumps, which were then ground and sieved to obtain fractlons of various particle sizes. The partlcle size and moisture and sulftlr contents oE each sample used nre presented in 'rab1.e l. Samples A and B were obtalned from Commonwealth Edlson Company, while sample C was an Illinois number 6 seam coal obtained Erom Hydro-carbon Research Incorporated. Sample A was a sub-bituminous coal, while samples B and C were highly volatile bituminous coals. These samples were stored under 8 blanket of argon until used.
Examples 62-78 involve batch recovery of liquids and gases from the coal samples shown in Table 14 using the method described above. These runs were performed in a 300-milliliter Hastelloy alloy C Magne-Drive autoclave. The experimental conditions and the results determined in these Examples are presented in Tables 15 and 16~ respectively.
2s In these Examples, the liquid hydrocarbon products were classified either as oils or as bitumens depending on whether or not such liquid products could be flashed from the autoclave upon depressurlzation of the autoclave at the run temperature employed. Oils were those liquid products which flashed over at the run temperature, while bitumens were those liquid products which remained in the autoclave.
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The weight balance shown in Table 16 was obtained by dividing the sum of the weights of the gas, liquid, and solid products recovered and of the weights of the water, argon, and catalyst, if used, recovered by the sum of the weights of the coal, water, co-solvent, argon, and catalysl , if used, initially charged to the autoclave. The product composition, reported as a weight percent on a moisture-free basis, was calculated by dividing the weight of the particular product in grams by the difference between the weight of the coal feed in grams and its moisture content in grams. ~he percent of coal conversion is 100 minus the weight percent of solid recovered.
The results shown in Table 16 illustrate that substantial conversion of coal solids occurred with both bituminous and sub-bituminous coal using the method of this invention. There was also substantial desulfurlzation ln each case where the sulEur content of the products was determ:Lned. AddltLon oE a catalyst ln the method oE thls lnvent:lon ln E~ample9 77 and 78 resulted :I.n nn :Lncrease :Ln the production of the oll Eractlon relatLve to tlle gas nnd bitu~en fractlons.
The results of Examples 70, 71, and 73 indicate that the organic co-solvent made no contribution to the amount of solid product recovered.
Therefore, the amount of solid remaining after processing under the conditions of the method of this invention is a good measure of the extent of conversion of solid coal to gas and liquid products, even in the presence of a co-solvent. Generally, the extent of coal conversion increased markedly when a saturated, non-aromatic oil or biphenyl was the co-solvent. No attempt was made to distinguish between the con-tributions of the coal feed and of the co-solvent to the yields of gas and liquid products, when a co-solvent was used.
The above examples are presented by way of illustration, and the ~ inventlon 3 ld not be construed t3 li3ited thereto.
lV4(~1Z5 The various components of the catalyst system of the method of this invention do not possess exactly identical effectiveness. The most advantageous selection of components and concentrations thereof ln the particular catalyst system to be used will depend on the particular carbonaceous material being processed.
The weight balance shown in Table 16 was obtained by dividing the sum of the weights of the gas, liquid, and solid products recovered and of the weights of the water, argon, and catalyst, if used, recovered by the sum of the weights of the coal, water, co-solvent, argon, and catalysl , if used, initially charged to the autoclave. The product composition, reported as a weight percent on a moisture-free basis, was calculated by dividing the weight of the particular product in grams by the difference between the weight of the coal feed in grams and its moisture content in grams. ~he percent of coal conversion is 100 minus the weight percent of solid recovered.
The results shown in Table 16 illustrate that substantial conversion of coal solids occurred with both bituminous and sub-bituminous coal using the method of this invention. There was also substantial desulfurlzation ln each case where the sulEur content of the products was determ:Lned. AddltLon oE a catalyst ln the method oE thls lnvent:lon ln E~ample9 77 and 78 resulted :I.n nn :Lncrease :Ln the production of the oll Eractlon relatLve to tlle gas nnd bitu~en fractlons.
The results of Examples 70, 71, and 73 indicate that the organic co-solvent made no contribution to the amount of solid product recovered.
Therefore, the amount of solid remaining after processing under the conditions of the method of this invention is a good measure of the extent of conversion of solid coal to gas and liquid products, even in the presence of a co-solvent. Generally, the extent of coal conversion increased markedly when a saturated, non-aromatic oil or biphenyl was the co-solvent. No attempt was made to distinguish between the con-tributions of the coal feed and of the co-solvent to the yields of gas and liquid products, when a co-solvent was used.
The above examples are presented by way of illustration, and the ~ inventlon 3 ld not be construed t3 li3ited thereto.
lV4(~1Z5 The various components of the catalyst system of the method of this invention do not possess exactly identical effectiveness. The most advantageous selection of components and concentrations thereof ln the particular catalyst system to be used will depend on the particular carbonaceous material being processed.
Claims (33)
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 con-taining 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, sulfur-resistant catalyst, selected from the group consisting of at least one basic metal carbonate, basic metal hydroxide, transition metal oxide, oxide-forming transition metal salt, 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 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.
3. The process of Claim 2 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.
4. The process of Claim 3 wherein the transition metal in the oxide and salt is selected from the group consisting of chromium, manganese, titanium, tantalum, and tungsten.
5. The process of Claim 1 wherein the metal in the basic metal carbonate and hydroxide is selected from the group consisting of alkali and alkaline earth metals.
6. The process of Claim 5 wherein the metal in the basic metal carbonate and hydroxide is selected from the group consisting of sodium and potassium.
7. 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 in the water-containing fluid in the range of from about 0.01 to about 3.0 weight percent.
8. The process of Claim 7 wherein the catalyst is present in a catalytically effective amount which is equivalent to a concentration level in the water in the water-containing fluid in the range of from about 0.10 to about 0.50 weight percent.
9. The process of Claim 1 wherein the density of water in the water-containing fluid is at least 0.15 gram per milliliter.
10. The process of Claim 9 wherein the density of water in the water-containing fluid is at least 0.2 gram per milliliter.
11. The process of Claim L wherein the temperature is at least 705°F.
12. 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.
13. The process of Claim 12 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.
14. The process of Claim 13 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.
15. The process of Claim 1 wherein the water-containing fluid is substantially water.
16. The process of Claim 1 wherein the water-containing fluid is water.
17. The process of Claim 1 wherein the carbonaceous material is selected from the class 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, desulfurized, and demetalated and wherein essentially all the sulfur removed from the recovered hydrocarbons is in the form of elemental sulfur.
18. The process of Claim 17 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.
19. The process of Claim 18 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,
20. The process of Claim 17 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.
21. The process of Claim 20 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.
22. The process of Claim 20 wherein the oil shale solids have a maximum particle size of one-half inch diameter.
23. The process of Claim 22 wherein the oil shale solids have a maximum particle size of one-quarter inch diameter.
24. The process of Claim 23 wherein the oil shale solids have a maximum particle size of 8 mesh.
25. The process of Claim 1 wherein the carbonaceous material is coal solids and wherein the upgraded hydrocarbon products are cracked and desulfurized.
26. The process of Claim 25 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.
27. The process of Claim 26 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.
28. The process of Claim 25 wherein the coal solids have a maximum particle size of one-half inch diameter.
29. The process of Claim 28 wherein the coal solids have a maximum particle size of one-quarter inch diameter.
30. The process of Claim 29 wherein the coal solids have a maximum particle size of 8 mesh.
31. The process of Claim 25 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.
32. The process of Claim 31 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.
33. The process of Claim 32 wherein the water-containing fluid contains a highly saturated oil.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/474,913 US3960708A (en) | 1974-05-31 | 1974-05-31 | Process for upgrading a hydrocarbon fraction |
| US05/474,909 US3948755A (en) | 1974-05-31 | 1974-05-31 | Process for recovering and upgrading hydrocarbons from oil shale and tar sands |
| US05/484,593 US3988238A (en) | 1974-07-01 | 1974-07-01 | Process for recovering upgraded products from coal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1040125A true CA1040125A (en) | 1978-10-10 |
Family
ID=27413300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA227,671A Expired CA1040125A (en) | 1974-05-31 | 1975-05-23 | Process for recovering upgraded hydrocarbon products |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1040125A (en) |
-
1975
- 1975-05-23 CA CA227,671A patent/CA1040125A/en not_active Expired
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