CA1199293A - Two-stage hydroprocessing of heavy oils with recycle of residua - Google Patents
Two-stage hydroprocessing of heavy oils with recycle of residuaInfo
- Publication number
- CA1199293A CA1199293A CA000429277A CA429277A CA1199293A CA 1199293 A CA1199293 A CA 1199293A CA 000429277 A CA000429277 A CA 000429277A CA 429277 A CA429277 A CA 429277A CA 1199293 A CA1199293 A CA 1199293A
- Authority
- CA
- Canada
- Prior art keywords
- process according
- boiling above
- effluent
- reaction zone
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for hydroprocessing a heavy hydrocarbonaceous oil feed in two stages in which residual components boiling above 500°C are recycled from the second stage to the first. The heavy oil can contain added solids such as porous metal getter particles, dispersed hydrogenation catalysts, and/or coal or coal-containing particles.
A process for hydroprocessing a heavy hydrocarbonaceous oil feed in two stages in which residual components boiling above 500°C are recycled from the second stage to the first. The heavy oil can contain added solids such as porous metal getter particles, dispersed hydrogenation catalysts, and/or coal or coal-containing particles.
Description
TWO~STAGE HYDROPROCESSING OF HEAVY OILS
WITH RECYCLE OF RESIDUA
~5 BACKGROUND OF THE INVENTION
This invention relates to the hydroprocessing of heavy hydrocarbonaceous oils and more particularly to the hydroprocessing of oils containing signiEicant quantities of components boiling above 500C.
A number of heavy oil hydrogenation processes have been pr~posed which involve recycle of hydrogena~ed fractions. U.S. Patent 3,147,206 discloses a process wherein a heavy oil feed is reacted with a hydrogen-donor solvent in a first stage and a gas-oil fraction of the first stage product is hydrocracked in a second stage~ A
heavy portion of the first stage product is recycled to the first stage. U.S. Patent 3,238,118 discloses a pro-cess wherein a gas-oil fraction separated from a crude oil feed is hydrocracked and ~he hydrocrackate bottoms are used as a hydrogen~donor for thermal conversion o~ a resi~
dual fraction. U~Sr Patent 4,028,221 discloses a coal liqueaction process wherein low-rank coal is heat-soaked at low pressure in a pasting solvent prior to liquefac tion. A portion of residual produ_t is recycledO U~S.
Patent 4,083,769 discloses a two~stage coal liquefaction process wherein solids-containing oil is withdrawn from a high temperature dissolver and recycled. British Patent 1l551,177 discloses a two-stage coal liquefaction process 3~ wherein a product oil containing heavy components is recycled fro~ a second catalytic stage, U.S, Patent 3,839,187 discloses a heavy oil treatment process employing a recycled hydrogen-donor gas-oil fraction and particulate solids. U.5. Patent 4~090,947 discloses a hydroyen-donor diluent cracking process employing a premium coker gas-oil as the hydroyen-donor diluent. U.S. Patent 4~ 787 discloses conversion of coal/oil mixtures utilizing an oil-soluble catalyst~
~0 o ~1 .
UOS. Patents 3,183,180~ 3,412,010 and 4,116,819 disclose single stage processes employing bottoms recycle, and U.S. Patent 3,635,814 discloses a one-stage coal-liquefaction process employing recycle of a whole boiling product.
SUMMARY OF THE IN~ENTION
1 In the present invention, heavy oil is hydro-treated in a two-stage process, and residual components, i.e. components boiling above 500C, are recycled from the second stage product to the first stage~ It is believed that certain of the 500C~ components are hydrogenated in the second stage, and t~e presence of recycled residual components in the first stage enhances hydrogen transfer to the fresh feed components. In addition, recycle of residual components provides further opportunity for their conversion to lower boiling components.
~U More specifically, this invention comprises a process for hydroprocessing a heavy hydrocarbonaceous oil containing liquid components boiling above 500C compris-ingo (a) contacting said hydrocarbonaceous oil with hydrogen in a Eirst reaction zone under hydrogenation conditions to produce a first effluent comprising liquid components boiling above 500C~
(b) contacting at least a portion of said firs~
ef~luentl ~aid first effluent portion containing liquid components boiling above 500C, with hydrogen under hydro-processing conditions in the presence of a hydrogenation catalyst to produce a second effluent comprising liquid components boiling above 500C, and (c) recycling at least a portion of said second effluen~, said recycle portion containiny a substa-.,tial quantity o liquid components boiling above 500C. The phrase "liquid components boiling above 500C", includes hydrocarbonaceous components which are in a dissolved or liquid state at the temperature and pressure of the sys-tem, and which do not boil below 500~C at atmospherlc pressure, including non-dLsti]lable components which ~1 .
decompose before reaching their boiling points in vacuum distillation. The heavy oil can contain added solids such ~5 as porous metal getter particles, dispersed hydrogenation catalysts, and/or coal or coal-containing particles BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic flow diagram illustrat-ing the process of this invention when solids are not added~
Figure 2 is a schematic flow diagram illustrat-ing the process of this inven~ion when porous metal getter particles are addedO
Figure 3 is a schematic flow diagram illustrat~
ing the process of this invention when coal or coal-con-taining particles are added.
DETAILED DESCRIPTION
Suitable heavy oil feedstocks for the process of this invention include crude petroleu~, petroleum residua, such as atmospheric and vacuum residua, reduced crudes, deasphalted residua, heavy hydrocarbonaceous oils derived frc,m coal, including bituminous, sub-bituminous, brown coals and lignite, as we]l as hydrocarbonaceous liquids derived from oil shale, tar sands, gilsonite, etc.
Typically, the hydrocarbonaceous liquid feeds will contain more than about 10 or more than about 20 weight percent liquid components boiling above 500C~
Th~ process of this invention is particularly effective for hydroprocessing heavy oil feed which con-tains soluble metals compounds, at least 5 ppmw total Ni+
and V, or even 50 ppmw or more Ni ~ V, which is typical of crude petroleum, petroleum residua and shale oil or shale oil fractions.
3~ Figure 1 depicts the process when no solids or only small quantities of solids are added to the feed.
Referring to Figure 1, heavy oil feed is added in line 5 and mixed with hydrogen added throuyh line 15 and a recycle oil (to be hereinafter described) and hydrogenated in first hydroprocessing zone 20. If desired, entrained catalyst and/or contact particles can be adcled through line 10. Firs~ stage hydroprocessing conditions sui-table for use according -to this invention include a hydrogen partial pressure above 35 atmospheres; a temperature in the xange of 350 to 500C, prefe.rably 400 ~o 455C; a pressure of about 40 to 680 atmospheres, preferably 100 to 340 at.mospheres;
and a hydrogen ga.s rate of 355 to 3550 liters/liter of oil feed, preferably 380 to 1780 liters/liter of oil feed, and a residence time of more than 0.01 hours, preferably 0.1 to 10 hours, more preferably 0.1 to 1 hour. The first stage hydroprocessing zone is preferably operated in the absence of carbon monoxide; however~ small amounts of carbon monoxide may be present, e.g. in internally recycled gas to the hydro-proces.sing zone. If desired, the first stage hydroprocessing zone may be suf~iciently elongated to attain plugflow conditions; however, turbulent flow conditions in the first stage may also be employed. Preferably, the feed will flow upwardly through the first stage hydroprocessing zone. A
suitable feed distribution system is described and commonly assigned Canadian Patent application 377,087 entitled 20 "Gas Pocket Distributor for an Upflow Reactor".
If desired a finely-divided catalyst, to be herein-after described, can be added through line 10. Alternately, the first stage hydroprocessing zone can be operated in the absence of externally-provided catalyst or contact particles.
All or a portion of the product of the first stage reactor 2n is passed through line 25 to catalytic reactor 30.
The feed to catalytic reactor 30 contains at least a portion of the first stage product which boils above 500C, and preferably contains all or at least the major por~ion of the ..~.
-4a-200Cl- first stage product. If desired, light gases and low boiling hydrocarbon fractions, such as a C5-C~ naphtha cut, or a heavier cut, can be removed hefore passage of the remaining first stage product to catalytic stage 30.
The catalytic reaction zone 30 is a second hydro-processing zone and contains catalyst in -the form of a fluid-ized, packed or ~ixed bed. The entire liquid feed to the second stage preferably passes upwardly through a packed catalyst bed. A flow distributor, as described in the above Canadian Patent application 377,087, may be used if desired.
The packed bed can move perlodically, if desired, to permit catalyst replacement.
The preferred catalyst for the second stage comprises at least one hydrogenation component selected ~rom Groups VIB
and VIII, of the Periodic Table of the Elements, Handbook o~
Chemistry and Physics, 45th Ed. Chemical Rubber Co. (1964).
The hydrogenation components can be present as metals, oxides or sulfides. The hydrogenation component is supported on a refractory inorganic base, for example, alumina, silica and composites of alumina-silica, alumina~boria, silica-alumina-magnesia, or silica-alumina-titania. Phosphorous promoters Gan also be present in the catalyst. The suitable catalyst can contain, for example, 1 to 10% Co, 1 to 20% Mo, and 0.5 to 5% P on a gamma alumina support. Such a catalyst can be pre-pared according to the teachings of United ~tates Patent 4,113,661 to Tamm.
The second hydrogenatlon zone 30 is operated at a temperature lower than the first hydrogenation zone 20, generally at 315 to 455C, preferably 340 to 425C, more preferably 360 to 400C; a pressure generally 40 to 340 atmospheres, preferably 70 to 210 atmospheres, and more preferab~y 140 to 190 atmospheres; a space velocity of generally 0~1 to 2, preferably 0.2 to 1.5, and more preferably 0.25 to -5a-1 hr. l; a hydrogen feed rate of generally 170 to 3400 liters/
liter of Eeed, and preferably 340 to 2700 liters/liter, and more preferably 550 to 1700 ]iters/liter, The product from the seconcl stage 30 exits through line 35 and passes to high pressure separator 40, where a gaseous fraction is removed through line 50 for recycle ater removal of light hydrocarbon gases, sulfur oxides, carbon oxides, and water~ A light liquid product S can be recovered from the high pressure separator through line 45 and a heavier liquid product fraction is removed through line 55.
At least a portion of the heavy liquid product exiting catalytic reactor 30 is recycled through line 90 to the first hydrogenation 20ne 20. If desired, light liquids, e.g. 200C- can be separated from the liquid of line 55 before recycle of the heavier fraction to zone 20. The recycled portion contains a substantial quantity of liquid components boiling above 500C. By "substantial quantity" is meant more than the carry-over oi heavy fractions to distillate cuts in a distillation or fractionation process. The recycled fraction should con-tain at least 5 percent by weight materials boiling above 500C and generally will contain more than 10 weight per-cent or even more than 20 weight percent materials boiling above 500C. The net liquid product passes through line 60 to fractionator 8S where it is fractionated into prod-uct cuts 86, 87, 88 and 89. If desired, all or a portion of the heavier cuts can be recycled throuyh line 90.
The amount of recycle 500C+ mat.erial will generally range from about 5 to 1000 kilograms per 100 kilo~ram of heavy oil feed to the process, more preferably, 10 to 100 kilograms per 100 kilograms of feed.
Figure 2 depicts an embodiment of this invention wherein contact particles are added to the heavy oil feed to the fiirst stage. In Figures 2 and 3, the elements correspond ~o the like numbered elements in Figure 1, and the process can operate in the same manner as in Figure 1. The solids can be a wide variety of materials, such as coal, oil shale fines, coal treated with a catalyst, such as described in U.S. Patent 4,176,054, fly ash, separated coal ash, or bottom ash particles, coal liquefaction residues or other solid materials. The solid contact particles are preferably porous, i~e. non-glassy, such as coal, alumina, silica gel, clays, etc. and can be Ol -7-totally or substantially free of catalytic transition metals or transition metal compounds added to impart 05 catalytic activity to the solids. Waste catalyst fines which only incidently contain catalytic metals as a result of their prior service are suitable for use, when economically justified. The contact particles can contain added catalytic metal components.
The contact particles are preferably added through line 12 and are suspended in the heavy oil feed;
however, the particles can be present in a bed within the first stage hydroprocessing zone, i desired. When the particles are suspended in the feed to the first stage, they should be added in sufficient quantity to provide 0.5 to 200 kilograms solids per lO0 kilograms of oil in the first hydroprocessing zone 20. The contact particles are passed through the catalytic stage 30 and will exit with the liquid portion of the catalytic stage product through line 55. Solids can be separated before or after the recycle oil is separated from the net liquid product in line 55. If desired light liquids, e.g. 200C-I can be separated from the liquid of line 55 before recycle of the heavier fraction to zone 23. As shown in Figure 2, a portion of the liquid product from line 55 is passed to solid separation zone 70, e.g., a conventional settler, Eilter, hydroclone, or centrifuge, wherein it is separated into a solids-rich fraction 75 and a solids~lean fraction 80. The remainder of the liquid from line 55 is recycled throuyh line 90 to the first stage hydroprocessing zone 20. If desired, all or a portion of the separated solids from solids-rich stream 75 can be recycled to line 90, as shown by dotted line 77.
The contact particles function in the process as coke deposition sites and as a getter for metals, such as nickel, and vanadium, present in contaminated feedstocks.
As the contact particles are recycled t ~hey can accu~ulate sufficient metals to be economically recoverab]e by con-ventiollal technology~
~O
In addition to the porous contact particles, afinely-divided dispersed hydrogenation catalyst can be added to the first stage, e.~., through line 10. The dispersed catalyst can be added as a finely-divided transition metal compound such as a transition metal sulfide, nitrate and acetate, etc. Suitable transition metal compounds include Ni(NO3)2 6H2O, NiCO3, (NH4)6 MO7O24 2 ' ~ 2 4 CO(NO3)2-6H2O, ~oCO3 and various oxides and sulfides of iron, cobalt and nickel. The finely-divided catalytic material may alternately be added as an aqueous solution of one or more water soluble transition metal compounds such as molybdates, tungstates or vanadates of ammonium or alkali metals. Suitable emulsion catalysts and a method for their introduction is described in United States Patent 4,172,814 issued October 30, 1979 to Moll et al for "Emulsion Catalyst for Hydrogenation Catalyst". Alternately, the dispersed hydrogenation catalyst can be added as an oil suluble compound, e.g. organometallic compounds, such as molybdenurn naphthanates, cobalt naphthanates, molybdenum oleates, and others as are known in the art. If finely-divided iron compounds are employed, the feed can be contacted with H2S in sufficient quantity to convert the iron species to catalytic species. The finely-divided catalyst will pass through the first and second hydroprocessing zones and a portion will be recycled with the recycle oil stream in line 90.
The concentration of dispersed hydrogenation catalysts is preferably less than 20 weight percent of the feed calculated as catalytic metal and more preferably 0.001 to 5 weight percent of the feed to the first stage. When the finely .~
-8a-divided catalyst is added as an emulsion, the emulsion should contain about 0.00005-0.005 kilogram of catalytic metal per kilogram oE feed. The emulsion is preferably mixed by rapid agitation wi-th the feed prior to entry lnto the first hydro-processing zone wherein con-tact is made with any porous contact particles which may be used. In addition, the finely divided hydrogenation ~1 _9_ catalyst can be added with the recycled stream to the first hydroprocessing zone. The added hydrogenation cata-05 lyst is preferably added in an amount sufficient to sup-press coke formation ~lithin the first stage hydropro-cessing zone, and this amount can be readily determined for a particular system by routine experimentation.
When coal or coal containing particles are added to the feed to first hydroprocessing æone 20, the carbona-ceous matter in the coal will be at least partially con-verted to liquids and the coal minerals will be passed through the sy~tem. It is preferred that at least a por-tion of the minerals are removed before recycle of heavy liquid to prevent the build-up of minerals in the system.
An example of a suitable system is depicted in Figure 3.
Liquid product from high pressure separator 40 exits through line 55 to primary solid separation zone 100, which can be a settler, filterr centrifuge, hydrocloneJ
etc., to provide a solids-rich stream 103 and a solids lean stream 105. A portion of the solids-lean stream is recycled through line 90. As previously described, light liquids can be removed by fractionation or flashing prior to recycle of the remaining heavy components. Solids-lean stream 105 or a portion thereof is optionally treated in a secondary solid separation zone 110, and a solids-rich raction is rejected through line 112. The solids lean fraction 115 i5 fractionated in fractionation zone 85 into cuts 86, 87l 88 and 89. ~f desired, all or a portion of the heavy cuts can be recycled to zone 20 or elsewhere.
The coal or coal~containing solids can be added to the feed in an amount of 1 to 50 kilograms per 100 kilograms of oil feedO
Again referring to Figure 1, a heavy hydrocar-bonaceous oil feed, such as petroleum vacuum residuum, in line 5, i9 mixed with an emulsion prepared by the dis-persing aqueous ammonium heptamolybdate solution and ~uel oil, and aclded through line 10~ The amount of molybdenum ln the emulsion i9 sufficient to provide 0~00005 to 0,005 kilogram, preferably about .0002-0.0007 kilogram of molybdenum as m~tal per kilogram of residuum feed. The feed containing dispersed catalyst is passed through to the first stage hydrogenation zone 20 wherein it is contacted with hydrogen at a temperature of 400 to ~50C, a pressure of 170 to 200 atmospheres, a hydrogen pressure of 150 to 190 atmospheres, a hydrogen rate of 1500 to 1800 liters/liter of feed, and a residence time of 0.5 to 2 hours. Hydrogenation zone 20 is an upflow vessel which can contain a packed bed of attapulgite clay. The entire effluent from hydrogenation zone 20 is passed to second hydrogenation zone 30 through a conduit 25 The second hydrogenation zone 30 is an upflow vessel containing a fixed bed of hydrogenation catalyst comprising cobalt, molybdenum, and pho~phorus on ~ gamma alumina support.
The second hydrogenation zone 30 is preferably operated at a temperature below the first stage, and in the range of 360-400C, a pressure of 170 to 200 atmospheres, a residence time of 1 to 5 hours and a hydrogen pressure of 150 to 190 atmospheresr The effluent from the second hydrogenation zone 30 is passed through conduit 35 to high-pressure separator 40, where a recycle gas rich in hydrQgen gas is removed~ treated to remove acid gases, and recycled through line 50. A C4- hydrocarbon gas stream i~
removed through line 45 and the normally liquid product is recovered through line 55O A portion of the liquid product is passed through line 60 to fractionator 85.
Another portion of the liquid product i5 recycled through line 90. The recycled portion can be a whole boiling range liquid (C5~), or a higher boiling fraction, e~g.
200C~ or 350C+. The recycle por~ion typically contains at least about 10 and up to abou~ S0 weight percent components boiling about 500C. When a whole boiling range portion of the C5+ product of zone 30 is recycled, 5 to 100 kilograms is recycled per kilo~ram of feed oil.
~9~
Referring to Figure 3, heavy oil, such as a ~5 petroleum reslduum, is mixed with particulate bituminous coal (-30 mesh Tyler sieve) added through line 12 in a slurrying zone, not shown. The ratio of coal to residuum can vary from 0.01 kilogram of coal per lO0 kilograms of residuum to 50 or more kilograms of coal per 100 kilograms of residuum feed. The mixture passes ~o the first hydro-processing zone 20, which preferably contains no exter-nally supplied catalyst or contact particles~ In zone 20, the mixture is contacted with hydrogen at a temperature of 400 to 450C, a pressure of 170 to 200 atmospheres, a hydrogen pressure of 150 to 190 atmospheres, a hydrogen rate of 1500 to 1800 liters/liter of feed, and a residence time of 0~5 to 2 hours. The entire effluent from zone 20 is passed to the second hydrogenation zone 30 which is an upflow vessel containing a fixed bed of hydrogenation catalyst comprising cobaltl vanadium, and phosphorous on a gamma-aluminum support The second hydrogenation zone 30 is preferably opera~ed at a temperature of 360 to 400C, a pressure of 170 to 200 atmospheres, a residence time of l to S hours, and a hydrogen pressure of 150 to 190 atmospheres. The effluent from the second hydrogenation zone 30 is passed through conduit 35 to high pressure separator 40 wherein recycled gas rich in hydrogen is removed and recycled through line 50. A gaseous hydrocar-bon stream is rec~vered via line 459 The normally liquid product plus ash and undissolved coal are passed through line 55 to separator 100. A solids-rich fraction is rejected ~hrough line 103. A portion of the solids-lean stream lOS is recycled through line 90. If only a whole boiling C5~ stream is recycled through line 90, the ratio of recycled oil to heavy oil feed is preferably 5 to lO0 kilograms recycle oil per 100 kilograms of residuum feed.
~10 Regardless of whether contact particles or sus-C5 pended catalysts are employed, the conditions within the hydroprocessing zones, and the composi~ions of the recycle can vary approximately within the limits herein described.
It will be recognized by those familiar with the art of petroleum processing that the process of this invention can be carried out in a variety of embodiments other than those specifically described herein, without departing from the ~pirit and scope of this invention. Such embodiments are contemplated as equivalent to those described and claimed herein.
3a ~U
WITH RECYCLE OF RESIDUA
~5 BACKGROUND OF THE INVENTION
This invention relates to the hydroprocessing of heavy hydrocarbonaceous oils and more particularly to the hydroprocessing of oils containing signiEicant quantities of components boiling above 500C.
A number of heavy oil hydrogenation processes have been pr~posed which involve recycle of hydrogena~ed fractions. U.S. Patent 3,147,206 discloses a process wherein a heavy oil feed is reacted with a hydrogen-donor solvent in a first stage and a gas-oil fraction of the first stage product is hydrocracked in a second stage~ A
heavy portion of the first stage product is recycled to the first stage. U.S. Patent 3,238,118 discloses a pro-cess wherein a gas-oil fraction separated from a crude oil feed is hydrocracked and ~he hydrocrackate bottoms are used as a hydrogen~donor for thermal conversion o~ a resi~
dual fraction. U~Sr Patent 4,028,221 discloses a coal liqueaction process wherein low-rank coal is heat-soaked at low pressure in a pasting solvent prior to liquefac tion. A portion of residual produ_t is recycledO U~S.
Patent 4,083,769 discloses a two~stage coal liquefaction process wherein solids-containing oil is withdrawn from a high temperature dissolver and recycled. British Patent 1l551,177 discloses a two-stage coal liquefaction process 3~ wherein a product oil containing heavy components is recycled fro~ a second catalytic stage, U.S, Patent 3,839,187 discloses a heavy oil treatment process employing a recycled hydrogen-donor gas-oil fraction and particulate solids. U.5. Patent 4~090,947 discloses a hydroyen-donor diluent cracking process employing a premium coker gas-oil as the hydroyen-donor diluent. U.S. Patent 4~ 787 discloses conversion of coal/oil mixtures utilizing an oil-soluble catalyst~
~0 o ~1 .
UOS. Patents 3,183,180~ 3,412,010 and 4,116,819 disclose single stage processes employing bottoms recycle, and U.S. Patent 3,635,814 discloses a one-stage coal-liquefaction process employing recycle of a whole boiling product.
SUMMARY OF THE IN~ENTION
1 In the present invention, heavy oil is hydro-treated in a two-stage process, and residual components, i.e. components boiling above 500C, are recycled from the second stage product to the first stage~ It is believed that certain of the 500C~ components are hydrogenated in the second stage, and t~e presence of recycled residual components in the first stage enhances hydrogen transfer to the fresh feed components. In addition, recycle of residual components provides further opportunity for their conversion to lower boiling components.
~U More specifically, this invention comprises a process for hydroprocessing a heavy hydrocarbonaceous oil containing liquid components boiling above 500C compris-ingo (a) contacting said hydrocarbonaceous oil with hydrogen in a Eirst reaction zone under hydrogenation conditions to produce a first effluent comprising liquid components boiling above 500C~
(b) contacting at least a portion of said firs~
ef~luentl ~aid first effluent portion containing liquid components boiling above 500C, with hydrogen under hydro-processing conditions in the presence of a hydrogenation catalyst to produce a second effluent comprising liquid components boiling above 500C, and (c) recycling at least a portion of said second effluen~, said recycle portion containiny a substa-.,tial quantity o liquid components boiling above 500C. The phrase "liquid components boiling above 500C", includes hydrocarbonaceous components which are in a dissolved or liquid state at the temperature and pressure of the sys-tem, and which do not boil below 500~C at atmospherlc pressure, including non-dLsti]lable components which ~1 .
decompose before reaching their boiling points in vacuum distillation. The heavy oil can contain added solids such ~5 as porous metal getter particles, dispersed hydrogenation catalysts, and/or coal or coal-containing particles BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic flow diagram illustrat-ing the process of this invention when solids are not added~
Figure 2 is a schematic flow diagram illustrat-ing the process of this inven~ion when porous metal getter particles are addedO
Figure 3 is a schematic flow diagram illustrat~
ing the process of this invention when coal or coal-con-taining particles are added.
DETAILED DESCRIPTION
Suitable heavy oil feedstocks for the process of this invention include crude petroleu~, petroleum residua, such as atmospheric and vacuum residua, reduced crudes, deasphalted residua, heavy hydrocarbonaceous oils derived frc,m coal, including bituminous, sub-bituminous, brown coals and lignite, as we]l as hydrocarbonaceous liquids derived from oil shale, tar sands, gilsonite, etc.
Typically, the hydrocarbonaceous liquid feeds will contain more than about 10 or more than about 20 weight percent liquid components boiling above 500C~
Th~ process of this invention is particularly effective for hydroprocessing heavy oil feed which con-tains soluble metals compounds, at least 5 ppmw total Ni+
and V, or even 50 ppmw or more Ni ~ V, which is typical of crude petroleum, petroleum residua and shale oil or shale oil fractions.
3~ Figure 1 depicts the process when no solids or only small quantities of solids are added to the feed.
Referring to Figure 1, heavy oil feed is added in line 5 and mixed with hydrogen added throuyh line 15 and a recycle oil (to be hereinafter described) and hydrogenated in first hydroprocessing zone 20. If desired, entrained catalyst and/or contact particles can be adcled through line 10. Firs~ stage hydroprocessing conditions sui-table for use according -to this invention include a hydrogen partial pressure above 35 atmospheres; a temperature in the xange of 350 to 500C, prefe.rably 400 ~o 455C; a pressure of about 40 to 680 atmospheres, preferably 100 to 340 at.mospheres;
and a hydrogen ga.s rate of 355 to 3550 liters/liter of oil feed, preferably 380 to 1780 liters/liter of oil feed, and a residence time of more than 0.01 hours, preferably 0.1 to 10 hours, more preferably 0.1 to 1 hour. The first stage hydroprocessing zone is preferably operated in the absence of carbon monoxide; however~ small amounts of carbon monoxide may be present, e.g. in internally recycled gas to the hydro-proces.sing zone. If desired, the first stage hydroprocessing zone may be suf~iciently elongated to attain plugflow conditions; however, turbulent flow conditions in the first stage may also be employed. Preferably, the feed will flow upwardly through the first stage hydroprocessing zone. A
suitable feed distribution system is described and commonly assigned Canadian Patent application 377,087 entitled 20 "Gas Pocket Distributor for an Upflow Reactor".
If desired a finely-divided catalyst, to be herein-after described, can be added through line 10. Alternately, the first stage hydroprocessing zone can be operated in the absence of externally-provided catalyst or contact particles.
All or a portion of the product of the first stage reactor 2n is passed through line 25 to catalytic reactor 30.
The feed to catalytic reactor 30 contains at least a portion of the first stage product which boils above 500C, and preferably contains all or at least the major por~ion of the ..~.
-4a-200Cl- first stage product. If desired, light gases and low boiling hydrocarbon fractions, such as a C5-C~ naphtha cut, or a heavier cut, can be removed hefore passage of the remaining first stage product to catalytic stage 30.
The catalytic reaction zone 30 is a second hydro-processing zone and contains catalyst in -the form of a fluid-ized, packed or ~ixed bed. The entire liquid feed to the second stage preferably passes upwardly through a packed catalyst bed. A flow distributor, as described in the above Canadian Patent application 377,087, may be used if desired.
The packed bed can move perlodically, if desired, to permit catalyst replacement.
The preferred catalyst for the second stage comprises at least one hydrogenation component selected ~rom Groups VIB
and VIII, of the Periodic Table of the Elements, Handbook o~
Chemistry and Physics, 45th Ed. Chemical Rubber Co. (1964).
The hydrogenation components can be present as metals, oxides or sulfides. The hydrogenation component is supported on a refractory inorganic base, for example, alumina, silica and composites of alumina-silica, alumina~boria, silica-alumina-magnesia, or silica-alumina-titania. Phosphorous promoters Gan also be present in the catalyst. The suitable catalyst can contain, for example, 1 to 10% Co, 1 to 20% Mo, and 0.5 to 5% P on a gamma alumina support. Such a catalyst can be pre-pared according to the teachings of United ~tates Patent 4,113,661 to Tamm.
The second hydrogenatlon zone 30 is operated at a temperature lower than the first hydrogenation zone 20, generally at 315 to 455C, preferably 340 to 425C, more preferably 360 to 400C; a pressure generally 40 to 340 atmospheres, preferably 70 to 210 atmospheres, and more preferab~y 140 to 190 atmospheres; a space velocity of generally 0~1 to 2, preferably 0.2 to 1.5, and more preferably 0.25 to -5a-1 hr. l; a hydrogen feed rate of generally 170 to 3400 liters/
liter of Eeed, and preferably 340 to 2700 liters/liter, and more preferably 550 to 1700 ]iters/liter, The product from the seconcl stage 30 exits through line 35 and passes to high pressure separator 40, where a gaseous fraction is removed through line 50 for recycle ater removal of light hydrocarbon gases, sulfur oxides, carbon oxides, and water~ A light liquid product S can be recovered from the high pressure separator through line 45 and a heavier liquid product fraction is removed through line 55.
At least a portion of the heavy liquid product exiting catalytic reactor 30 is recycled through line 90 to the first hydrogenation 20ne 20. If desired, light liquids, e.g. 200C- can be separated from the liquid of line 55 before recycle of the heavier fraction to zone 20. The recycled portion contains a substantial quantity of liquid components boiling above 500C. By "substantial quantity" is meant more than the carry-over oi heavy fractions to distillate cuts in a distillation or fractionation process. The recycled fraction should con-tain at least 5 percent by weight materials boiling above 500C and generally will contain more than 10 weight per-cent or even more than 20 weight percent materials boiling above 500C. The net liquid product passes through line 60 to fractionator 8S where it is fractionated into prod-uct cuts 86, 87, 88 and 89. If desired, all or a portion of the heavier cuts can be recycled throuyh line 90.
The amount of recycle 500C+ mat.erial will generally range from about 5 to 1000 kilograms per 100 kilo~ram of heavy oil feed to the process, more preferably, 10 to 100 kilograms per 100 kilograms of feed.
Figure 2 depicts an embodiment of this invention wherein contact particles are added to the heavy oil feed to the fiirst stage. In Figures 2 and 3, the elements correspond ~o the like numbered elements in Figure 1, and the process can operate in the same manner as in Figure 1. The solids can be a wide variety of materials, such as coal, oil shale fines, coal treated with a catalyst, such as described in U.S. Patent 4,176,054, fly ash, separated coal ash, or bottom ash particles, coal liquefaction residues or other solid materials. The solid contact particles are preferably porous, i~e. non-glassy, such as coal, alumina, silica gel, clays, etc. and can be Ol -7-totally or substantially free of catalytic transition metals or transition metal compounds added to impart 05 catalytic activity to the solids. Waste catalyst fines which only incidently contain catalytic metals as a result of their prior service are suitable for use, when economically justified. The contact particles can contain added catalytic metal components.
The contact particles are preferably added through line 12 and are suspended in the heavy oil feed;
however, the particles can be present in a bed within the first stage hydroprocessing zone, i desired. When the particles are suspended in the feed to the first stage, they should be added in sufficient quantity to provide 0.5 to 200 kilograms solids per lO0 kilograms of oil in the first hydroprocessing zone 20. The contact particles are passed through the catalytic stage 30 and will exit with the liquid portion of the catalytic stage product through line 55. Solids can be separated before or after the recycle oil is separated from the net liquid product in line 55. If desired light liquids, e.g. 200C-I can be separated from the liquid of line 55 before recycle of the heavier fraction to zone 23. As shown in Figure 2, a portion of the liquid product from line 55 is passed to solid separation zone 70, e.g., a conventional settler, Eilter, hydroclone, or centrifuge, wherein it is separated into a solids-rich fraction 75 and a solids~lean fraction 80. The remainder of the liquid from line 55 is recycled throuyh line 90 to the first stage hydroprocessing zone 20. If desired, all or a portion of the separated solids from solids-rich stream 75 can be recycled to line 90, as shown by dotted line 77.
The contact particles function in the process as coke deposition sites and as a getter for metals, such as nickel, and vanadium, present in contaminated feedstocks.
As the contact particles are recycled t ~hey can accu~ulate sufficient metals to be economically recoverab]e by con-ventiollal technology~
~O
In addition to the porous contact particles, afinely-divided dispersed hydrogenation catalyst can be added to the first stage, e.~., through line 10. The dispersed catalyst can be added as a finely-divided transition metal compound such as a transition metal sulfide, nitrate and acetate, etc. Suitable transition metal compounds include Ni(NO3)2 6H2O, NiCO3, (NH4)6 MO7O24 2 ' ~ 2 4 CO(NO3)2-6H2O, ~oCO3 and various oxides and sulfides of iron, cobalt and nickel. The finely-divided catalytic material may alternately be added as an aqueous solution of one or more water soluble transition metal compounds such as molybdates, tungstates or vanadates of ammonium or alkali metals. Suitable emulsion catalysts and a method for their introduction is described in United States Patent 4,172,814 issued October 30, 1979 to Moll et al for "Emulsion Catalyst for Hydrogenation Catalyst". Alternately, the dispersed hydrogenation catalyst can be added as an oil suluble compound, e.g. organometallic compounds, such as molybdenurn naphthanates, cobalt naphthanates, molybdenum oleates, and others as are known in the art. If finely-divided iron compounds are employed, the feed can be contacted with H2S in sufficient quantity to convert the iron species to catalytic species. The finely-divided catalyst will pass through the first and second hydroprocessing zones and a portion will be recycled with the recycle oil stream in line 90.
The concentration of dispersed hydrogenation catalysts is preferably less than 20 weight percent of the feed calculated as catalytic metal and more preferably 0.001 to 5 weight percent of the feed to the first stage. When the finely .~
-8a-divided catalyst is added as an emulsion, the emulsion should contain about 0.00005-0.005 kilogram of catalytic metal per kilogram oE feed. The emulsion is preferably mixed by rapid agitation wi-th the feed prior to entry lnto the first hydro-processing zone wherein con-tact is made with any porous contact particles which may be used. In addition, the finely divided hydrogenation ~1 _9_ catalyst can be added with the recycled stream to the first hydroprocessing zone. The added hydrogenation cata-05 lyst is preferably added in an amount sufficient to sup-press coke formation ~lithin the first stage hydropro-cessing zone, and this amount can be readily determined for a particular system by routine experimentation.
When coal or coal containing particles are added to the feed to first hydroprocessing æone 20, the carbona-ceous matter in the coal will be at least partially con-verted to liquids and the coal minerals will be passed through the sy~tem. It is preferred that at least a por-tion of the minerals are removed before recycle of heavy liquid to prevent the build-up of minerals in the system.
An example of a suitable system is depicted in Figure 3.
Liquid product from high pressure separator 40 exits through line 55 to primary solid separation zone 100, which can be a settler, filterr centrifuge, hydrocloneJ
etc., to provide a solids-rich stream 103 and a solids lean stream 105. A portion of the solids-lean stream is recycled through line 90. As previously described, light liquids can be removed by fractionation or flashing prior to recycle of the remaining heavy components. Solids-lean stream 105 or a portion thereof is optionally treated in a secondary solid separation zone 110, and a solids-rich raction is rejected through line 112. The solids lean fraction 115 i5 fractionated in fractionation zone 85 into cuts 86, 87l 88 and 89. ~f desired, all or a portion of the heavy cuts can be recycled to zone 20 or elsewhere.
The coal or coal~containing solids can be added to the feed in an amount of 1 to 50 kilograms per 100 kilograms of oil feedO
Again referring to Figure 1, a heavy hydrocar-bonaceous oil feed, such as petroleum vacuum residuum, in line 5, i9 mixed with an emulsion prepared by the dis-persing aqueous ammonium heptamolybdate solution and ~uel oil, and aclded through line 10~ The amount of molybdenum ln the emulsion i9 sufficient to provide 0~00005 to 0,005 kilogram, preferably about .0002-0.0007 kilogram of molybdenum as m~tal per kilogram of residuum feed. The feed containing dispersed catalyst is passed through to the first stage hydrogenation zone 20 wherein it is contacted with hydrogen at a temperature of 400 to ~50C, a pressure of 170 to 200 atmospheres, a hydrogen pressure of 150 to 190 atmospheres, a hydrogen rate of 1500 to 1800 liters/liter of feed, and a residence time of 0.5 to 2 hours. Hydrogenation zone 20 is an upflow vessel which can contain a packed bed of attapulgite clay. The entire effluent from hydrogenation zone 20 is passed to second hydrogenation zone 30 through a conduit 25 The second hydrogenation zone 30 is an upflow vessel containing a fixed bed of hydrogenation catalyst comprising cobalt, molybdenum, and pho~phorus on ~ gamma alumina support.
The second hydrogenation zone 30 is preferably operated at a temperature below the first stage, and in the range of 360-400C, a pressure of 170 to 200 atmospheres, a residence time of 1 to 5 hours and a hydrogen pressure of 150 to 190 atmospheresr The effluent from the second hydrogenation zone 30 is passed through conduit 35 to high-pressure separator 40, where a recycle gas rich in hydrQgen gas is removed~ treated to remove acid gases, and recycled through line 50. A C4- hydrocarbon gas stream i~
removed through line 45 and the normally liquid product is recovered through line 55O A portion of the liquid product is passed through line 60 to fractionator 85.
Another portion of the liquid product i5 recycled through line 90. The recycled portion can be a whole boiling range liquid (C5~), or a higher boiling fraction, e~g.
200C~ or 350C+. The recycle por~ion typically contains at least about 10 and up to abou~ S0 weight percent components boiling about 500C. When a whole boiling range portion of the C5+ product of zone 30 is recycled, 5 to 100 kilograms is recycled per kilo~ram of feed oil.
~9~
Referring to Figure 3, heavy oil, such as a ~5 petroleum reslduum, is mixed with particulate bituminous coal (-30 mesh Tyler sieve) added through line 12 in a slurrying zone, not shown. The ratio of coal to residuum can vary from 0.01 kilogram of coal per lO0 kilograms of residuum to 50 or more kilograms of coal per 100 kilograms of residuum feed. The mixture passes ~o the first hydro-processing zone 20, which preferably contains no exter-nally supplied catalyst or contact particles~ In zone 20, the mixture is contacted with hydrogen at a temperature of 400 to 450C, a pressure of 170 to 200 atmospheres, a hydrogen pressure of 150 to 190 atmospheres, a hydrogen rate of 1500 to 1800 liters/liter of feed, and a residence time of 0~5 to 2 hours. The entire effluent from zone 20 is passed to the second hydrogenation zone 30 which is an upflow vessel containing a fixed bed of hydrogenation catalyst comprising cobaltl vanadium, and phosphorous on a gamma-aluminum support The second hydrogenation zone 30 is preferably opera~ed at a temperature of 360 to 400C, a pressure of 170 to 200 atmospheres, a residence time of l to S hours, and a hydrogen pressure of 150 to 190 atmospheres. The effluent from the second hydrogenation zone 30 is passed through conduit 35 to high pressure separator 40 wherein recycled gas rich in hydrogen is removed and recycled through line 50. A gaseous hydrocar-bon stream is rec~vered via line 459 The normally liquid product plus ash and undissolved coal are passed through line 55 to separator 100. A solids-rich fraction is rejected ~hrough line 103. A portion of the solids-lean stream lOS is recycled through line 90. If only a whole boiling C5~ stream is recycled through line 90, the ratio of recycled oil to heavy oil feed is preferably 5 to lO0 kilograms recycle oil per 100 kilograms of residuum feed.
~10 Regardless of whether contact particles or sus-C5 pended catalysts are employed, the conditions within the hydroprocessing zones, and the composi~ions of the recycle can vary approximately within the limits herein described.
It will be recognized by those familiar with the art of petroleum processing that the process of this invention can be carried out in a variety of embodiments other than those specifically described herein, without departing from the ~pirit and scope of this invention. Such embodiments are contemplated as equivalent to those described and claimed herein.
3a ~U
Claims (29)
1. A process for hydroprocessing a heavy hydrocar-bonaceous oil feed containing liquid components boiling above 500°C comprising:
(a) contacting said oil feed with hydrogen under hydrogenation conditions including a hydrogen pressure above 35 atmospheres in a first reaction zone to produce a first liquid effluent comprising liquid components boiling above 500°C;
(b) contacting at least a portion of said first effluent, said portion containing liquid components boil-ing above 500°C, with hydrogen in a second reaction zone under hydroprocessing conditions in the presence of a hydrogenation catalyst to produce a second effluent com-prising liquid components boiling above 500°C; and (c) recycling at least a portion of said second effluent to said first reaction zone, said recycled por-tion containing a substantial quantity of liquid compo-nents boiling above 500°C.
(a) contacting said oil feed with hydrogen under hydrogenation conditions including a hydrogen pressure above 35 atmospheres in a first reaction zone to produce a first liquid effluent comprising liquid components boiling above 500°C;
(b) contacting at least a portion of said first effluent, said portion containing liquid components boil-ing above 500°C, with hydrogen in a second reaction zone under hydroprocessing conditions in the presence of a hydrogenation catalyst to produce a second effluent com-prising liquid components boiling above 500°C; and (c) recycling at least a portion of said second effluent to said first reaction zone, said recycled por-tion containing a substantial quantity of liquid compo-nents boiling above 500°C.
2. A process according to Claim 1 wherein said hydrogenation conditions in said first reaction zone include a temperature in the range of 350 to 500°C, a pressure in the range of 40 to 680 atmospheres, a resi-dence time in the range of 0.1 to 10 hours and a hydrogen gas rate of 355 to 3550 liters/liter of feed; and said hydroprocessing conditions in said second reaction zone include a temperature lower than the temperature in the first reaction zone and in the range of 315 to 455°C, a pressure in the range of 40 to 340 atmospheres, a space velocity in the range of 0.1 to 2 hours-1, and a hydrogen feed rate of 170 to 3400 liters/liter of feed.
3. A process according to Claim 1 or 2 wherein said hydrocarbonaceous oil feed contains at least about 10 weight percent liquid components boiling above 500°C.
4. A process according to Claim 1 or 2 wherein said second stage catalyst is present in an ebullating bed.
5. A process according to Claim 1 or 2 wherein said second stage catalyst is present in a packed bed.
6. A process according to Claim 1 wherein said second stage catalyst comprises a hydrogenation component selected from Groups VIB and VIII of the Periodic Table on a support comprising Al2O3.
7. A process according to Claim 1 wherein said first hydrogenation zone contains porous contact parti-cles.
8. A process according to Claim 1, 2, or 7 wherein said recycled portion contains at least 5 weight percent components boiling above 500°C.
9. A process according to Claim 1, 2, or 7 wherein said recycled portion contains at least about 10 weight percent components boiling above 500°C.
10. A process for hydroprocessing a heavy hydrocar-bonaceous oil feed containing liquid components boiling above 500°C comprising:
(a) contacting said oil feed in a first reaction zone under hydrogenation conditions including a hydrogen presence of at least 35 atmospheres in the presence of externally-supplied porous contact particles to produce a first effluent comprising liquid components boiling above 500°C;
(b) contacting at least a portion of said first effluent, said first effluent portion containing liquid components boiling above 500°C and at least a portion of said contact particles, with hydrogen under hydropro-cessing conditions in a second reaction zone in the pre-sence of a hydrogenation catalyst to produce a second effluent comprising liquid components boiling above 500°C;
and (c) recycling at least a portion of said second effluent to said first reaction zone, said recycled portion containing a substantial quantity of liquid components boiling above 500°C.
(a) contacting said oil feed in a first reaction zone under hydrogenation conditions including a hydrogen presence of at least 35 atmospheres in the presence of externally-supplied porous contact particles to produce a first effluent comprising liquid components boiling above 500°C;
(b) contacting at least a portion of said first effluent, said first effluent portion containing liquid components boiling above 500°C and at least a portion of said contact particles, with hydrogen under hydropro-cessing conditions in a second reaction zone in the pre-sence of a hydrogenation catalyst to produce a second effluent comprising liquid components boiling above 500°C;
and (c) recycling at least a portion of said second effluent to said first reaction zone, said recycled portion containing a substantial quantity of liquid components boiling above 500°C.
11. A process according to Claim 10 wherein said recycled portion of said second effluent contains at least a portion of said contact particles.
12. A process according to Claim 10 or 11 wherein said hydrogenation conditions in said first reaction zone include a temperature in the range of 350 to 500°C, a pressure in the range of 40 to 680 atmospheres, a resi-dence time of 0.1 to 3 hours, and a hydrogen gas rate of 355 to 3550 liters/liter of feed, and said hydroprocessing conditions in said second reaction zone include a temperature lower than the temperatures of said first reaction zone in the range of 315 to 455°C, a pressure in the range of 40 to 340 atmospheres, a space velocity in the range of 0.1 to 2 hours-1 and a hydrogen feed rate of 170 to 3400 liters/liter of feed.
13. A process according to Claim 10 wherein said hydrocarbonaceous feed contains at least about 10 weight percent liquid components boiling above 500°C.
14. A process according to Claim 10 wherein said second stage catalyst is present as an ebullating bed.
15. A process according to Claim 10 wherein said second stage catalyst is present as a packed bed.
16. A process according to Claim 10 wherein said second stage catalyst comprises a hydrogenation component such as from Groups VIB and VIII and is supported on refractory oxide support comprising Al2O3.
17. A process according to Claim 10 wherein said hydrogenation in said first reaction zone is carried out in the presence of a dispersed hydrogenation catalyst.
18. A process according to Claim 10 wherein said dispersed hydrogenation catalyst is passed from said first stage to the second stage.
19. A process according to Claim 10 wherein said recycle portion contains at least 5 weight percent compo-nents boiling above 500°C.
20. A process according to Claim 10 wherein said recycled portion contains at least about 10 weight percent components boiling above 500°C.
21. A process for liquefying coal and hydroproces-sing a heavy hydrocarbonaceous oil containing liquid com-ponents boiling above 500°C comprising:
(a) forming a slurry comprising said hydrocarbona-ceous oil and said coal and contacting said slurry in a first reaction zone under hydrogenation conditions includ-ing a hydrogen pressure of at least 35 atmospheres to produce a first effluent comprising undissolved solids and liquid components boiling above 500°C;
(b) contacting at least a portion of said first effluent, said first effluent portion containing liquid components boiling above 500°C, with hydrogen under hydro-processing conditions in a second reaction zone in the presence of a hydrogenation catalyst to produce a second effluent comprising undissolved solids and liquid components boiling above 500°C and (c) recycling at least a portion of said second effluent to said first reaction zone, said recycled portion containing a substantial quantity of liquid components boiling above 500°C.
(a) forming a slurry comprising said hydrocarbona-ceous oil and said coal and contacting said slurry in a first reaction zone under hydrogenation conditions includ-ing a hydrogen pressure of at least 35 atmospheres to produce a first effluent comprising undissolved solids and liquid components boiling above 500°C;
(b) contacting at least a portion of said first effluent, said first effluent portion containing liquid components boiling above 500°C, with hydrogen under hydro-processing conditions in a second reaction zone in the presence of a hydrogenation catalyst to produce a second effluent comprising undissolved solids and liquid components boiling above 500°C and (c) recycling at least a portion of said second effluent to said first reaction zone, said recycled portion containing a substantial quantity of liquid components boiling above 500°C.
22. A process according to Claim 21 wherein said recycled portion of said second effluent contains at least a portion of said undissolved solids.
23. A process according to Claim 21 wherein said hydrocarbonaceous feed contains at least about 10 weight percent liquid components boiling above 500°C.
24. A process according to Claim 21 wherein said second stage catalyst is present as an ebullating bed.
25. A process according to Claim 21 wherein said second stage catalyst is present as a packed bed.
26. A process according to Claim 21 wherein said second stage catalyst comprises a hydrogenation component such as from Groups VIB and VIII and is supported on refractory oxide support comprising Al2O3.
27. A process according to Claim 21 wherein said hydrogenation in said first reaction zone is carried out in the presence of a dispersed catalyst.
28. A process according to Claim 21 wherein said recycle portion contains at least 5 percent by weight components boiling above 500°C.
29. A process according to Claim 21 wherein said recycle portion contains at least about 10 percent by weight components boiling above 500°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US38933882A | 1982-06-17 | 1982-06-17 | |
| US389,338 | 1982-06-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1199293A true CA1199293A (en) | 1986-01-14 |
Family
ID=23537846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000429277A Expired CA1199293A (en) | 1982-06-17 | 1983-05-31 | Two-stage hydroprocessing of heavy oils with recycle of residua |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS596283A (en) |
| CA (1) | CA1199293A (en) |
| DE (1) | DE3321690A1 (en) |
| GB (1) | GB2121817B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3572001D1 (en) * | 1984-01-19 | 1989-09-07 | Ruhrkohle Ag | Hydrogen gas distribution in coal liquefaction plants |
| US4564439A (en) * | 1984-06-29 | 1986-01-14 | Chevron Research Company | Two-stage, close-coupled thermal catalytic hydroconversion process |
| GB2182947B (en) * | 1985-11-19 | 1990-04-04 | Chevron Res | A multi-staged ,close coupled thermal catalytic hydroconversion process |
| DE3721545A1 (en) * | 1986-07-03 | 1988-01-07 | Takeda Chemical Industries Ltd | BATHROOM PREPARATION |
| EP0569092A1 (en) * | 1992-05-05 | 1993-11-10 | Shell Internationale Researchmaatschappij B.V. | Hydrotreating process |
| AU6295594A (en) * | 1993-04-07 | 1994-10-24 | Union Oil Company Of California | Integrated hydrocracking/hydrotreating process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1315559A (en) * | 1970-08-10 | 1973-05-02 | Exxon Research Engineering Co | Hydrocracking process for high end point feeds |
| US4330389A (en) * | 1976-12-27 | 1982-05-18 | Chevron Research Company | Coal liquefaction process |
-
1983
- 1983-05-31 CA CA000429277A patent/CA1199293A/en not_active Expired
- 1983-06-15 DE DE19833321690 patent/DE3321690A1/en not_active Withdrawn
- 1983-06-16 GB GB08316435A patent/GB2121817B/en not_active Expired
- 1983-06-16 JP JP10853883A patent/JPS596283A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS596283A (en) | 1984-01-13 |
| GB8316435D0 (en) | 1983-07-20 |
| GB2121817A (en) | 1984-01-04 |
| GB2121817B (en) | 1987-01-21 |
| DE3321690A1 (en) | 1983-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4695369A (en) | Catalytic hydroconversion of heavy oil using two metal catalyst | |
| US4376037A (en) | Hydroprocessing of heavy hydrocarbonaceous oils | |
| US4389301A (en) | Two-step hydroprocessing of heavy hydrocarbonaceous oils | |
| US4079004A (en) | Method for separating undissolved solids from a coal liquefaction product | |
| US4606809A (en) | Hydroconversion of heavy oils | |
| EP0048098B1 (en) | Upgrading of residual oil | |
| US11702603B2 (en) | Method for converting feedstocks comprising a hydrocracking step, a precipitation step and a sediment separation step, in order to produce fuel oils | |
| US3622498A (en) | Slurry processing for black oil conversion | |
| US4151070A (en) | Staged slurry hydroconversion process | |
| US4411767A (en) | Integrated process for the solvent refining of coal | |
| US4389303A (en) | Process of converting high-boiling crude oils to equivalent petroleum products | |
| EA011976B1 (en) | Process for recycling an active slurry catalyst composition in heavy oil upgrading | |
| US4300996A (en) | Three-stage coal liquefaction process | |
| US4379744A (en) | Coal liquefaction process | |
| US3453206A (en) | Multiple-stage hydrorefining of petroleum crude oil | |
| US4557822A (en) | Hydroconversion process | |
| US4081360A (en) | Method for suppressing asphaltene formation during coal liquefaction and separation of solids from the liquid product | |
| US3825488A (en) | Process for hydrorefining a hydrocarbon charge stock | |
| US4659452A (en) | Multi-stage hydrofining process | |
| CA1199293A (en) | Two-stage hydroprocessing of heavy oils with recycle of residua | |
| US4428820A (en) | Coal liquefaction process with controlled recycle of ethyl acetate-insolubles | |
| US4534847A (en) | Process for producing low-sulfur boiler fuel by hydrotreatment of solvent deashed SRC | |
| US4325800A (en) | Two-stage coal liquefaction process with interstage guard bed | |
| US4510038A (en) | Coal liquefaction using vacuum distillation and an external residuum feed | |
| US4331531A (en) | Three-stage coal liquefaction process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |