CA1280707C - Catalytic two-stage co-processing of coal/oil feedstocks - Google Patents
Catalytic two-stage co-processing of coal/oil feedstocksInfo
- Publication number
- CA1280707C CA1280707C CA000506635A CA506635A CA1280707C CA 1280707 C CA1280707 C CA 1280707C CA 000506635 A CA000506635 A CA 000506635A CA 506635 A CA506635 A CA 506635A CA 1280707 C CA1280707 C CA 1280707C
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- Prior art keywords
- coal
- stage
- reaction zone
- hydrocarbon
- liquid
- Prior art date
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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
- C10G1/006—Combinations of processes provided in groups C10G1/02 - C10G1/08
Abstract
ABSTRACT OF THE DISCLOSURE
A process for two-stage catalytic co-processing of coal and heavy petroleum fractions to produce increased yields of low-boiling hydrocarbon liquid and gas products. In the process, the particulate coal is slurried with a petroleum residuum and optionally with a process-derived liquid solvent and fed into a first stage catalytic reaction zone operated at relatively mild conditions which promote controlled rate liquefaction of the coal while simultaneously hydrogenating the petroleum and hydrocarbon recycle oils at conditions favoring hydrogenation reactions. The first stage reactor is maintained at 650-800°F temperature, 1500-3500 psig hydrogen partial pressure and 10-100lb/hr/ft3 space velocity for the total coal and oil feed. From the first stage reaction zone the partially hydrogenated material is passed directly to the second stage catalytic reaction zone maintained at more severe conditions of 750-900°F temperature for further hydro-genation and catalytic hydroconversion reactions. By this process, the blended coal and petroleum feed materials are successively catalytically hydrogenated and hydroconverted at the selected conditions, which results in significantly increased yields of desirable low-boiling hydrocarbon liquid products and minimal production of undesirable residuum and unconverted coal and hydrogen gases, while catalyst life is substantially increased.
A process for two-stage catalytic co-processing of coal and heavy petroleum fractions to produce increased yields of low-boiling hydrocarbon liquid and gas products. In the process, the particulate coal is slurried with a petroleum residuum and optionally with a process-derived liquid solvent and fed into a first stage catalytic reaction zone operated at relatively mild conditions which promote controlled rate liquefaction of the coal while simultaneously hydrogenating the petroleum and hydrocarbon recycle oils at conditions favoring hydrogenation reactions. The first stage reactor is maintained at 650-800°F temperature, 1500-3500 psig hydrogen partial pressure and 10-100lb/hr/ft3 space velocity for the total coal and oil feed. From the first stage reaction zone the partially hydrogenated material is passed directly to the second stage catalytic reaction zone maintained at more severe conditions of 750-900°F temperature for further hydro-genation and catalytic hydroconversion reactions. By this process, the blended coal and petroleum feed materials are successively catalytically hydrogenated and hydroconverted at the selected conditions, which results in significantly increased yields of desirable low-boiling hydrocarbon liquid products and minimal production of undesirable residuum and unconverted coal and hydrogen gases, while catalyst life is substantially increased.
Description
)7~7 CATA~YTIC TWO-STAG~ CO-PROCESSING OF
COAL/OIL FE~DSTOCKS
BACKGRO~JD OF INVENTION
This invention pertains to co-processing coal/oil feed-stock3 in a two-stage catalytic hydroconversion process. It pertains more particulatly to such coal/oil co-processing to produce higher percentage conversion and increased yields of low-boiling hydrocarbon distillate liquid products, while mlnimizing hydrocarbon gases and heavy resid materials.
Coal/oil co-processing using a single stage catalytic ebullated bed reactor, has been shown to be an effective technique for simultaneous conversion o coal and residual oils to produce predominately hydrocarbon liquid products, as disclosed by U.S. Patent 4,0~5,504 to Chervenak, et al. At high percentage conversio. levels, the single stage hydrogenation procecs produces undesirably high yields of byproduct hydrocarbon gas (Cl-C3) and product quality decreases, i.e., the N2 and S contents of the distillate llquids increase. SeVeral other processes for simui-taneous processing of coal and petroleum feeds using two reactionstages have been proposed, such as disclosed by U.S. Patent Nos. 3,870,621 to Arnold; 4,306,960 to Gleim, and 4,330,390 to Rosenthal, et al. However, these processes all have shortcomings and do not achieve the flexibilityiand high yields o low-boiling hydrocarbon distillate liquids de~ired. Significantly ijmprove~
result~ have now ~een achieved by the present two-stage catalytic coal/oll co-processing proces~. ~
'' ';
. i';~
. 1.
7~7 ~uMM~ y ()I INVI:NI'I~)N
The present invention provides an improvecl hydrogcnntlon pro-cess in which particulate coal and liquid hydrocarbon feedstocks are co-peocessed in a catalytic two-stage ebullate-bed reactor sys-tem, to produce increased yields of low-boiling hydrocarbon distil-late liquids and minimal yield~ of hydrocarbon gas and high-boiling resid fractions. The first stage reactor is operated at mild hy-drogenation conditions of 650-800F temperature and 1000-4000 psig hydrogen partiaL pressure and at 10-100 lb coal and petroleum/hr ft' reactor volume to increase the hydrogen content of the dissolved .. _ _ _ .., , , _ ... .. . . ... ..
coal and oil feed, and recycle oil (if ~se~) molecules, while obtaining moderate conversion of the coal without producing re3ressive (coke forming) reactions.
The catalyst should be selected from the metals group con6isting of oxides or other metal compounds or components of cobalt, iron, molybdenum, nickel, tin, tung~ten and mixture~ thereof and other hydrocarbon hydrogenation cataly~t metal oxide~ known in the art, deposited on a base material selected from the group consis~-ing of alumina, magnesia, silica, titania, and similar materials.
Useful catalyst particle sizes can range from about 0.030 to 0.125 inch effective diameter The first stage reactor effluent material is passed to ~
direct-coupled second stage catalytic reactor, which is operated at somewhat more severe hydroconversion conditions of 750-900F
temperature and 1000-4000 psig hydrogen partial pressure to con~
vert the remaining unconverted coal and residual oil and to pro-duce high yields of high quality distillate liquid products, with minimal yields of hydrocarbon gases and high-boiling resid fract-ions. The catalyst used is similar or can be the same as that used in the first stage reactor. From the second stage reactor the I z~
effluent is phnse separule(l and distilled to provlde the com-bined hydrocarbon liquid distillate products.
This process improvement permits co-processing operations on blended coal and petroleum feedstocks at high conversion to pro-vide distillate liquid products, without encountering compatibility problems between the coal-derived and oil-derived products. The addition o a :first low severity hydrogenation reaction stage to increase the hydrogen content of thè fresh coal and oil feed materials (and recycle oil if present) reduces sulfur and nitrogen compounds in the liquid product and improves the solvent quality of the liquids needed to dissolve the coal, and also significantly improves the overall process performance and allows its successful applicat~on to a wider range o fcedstocks. Coal conversion in catalytic two-stage co-processing with solvent quality sensitive coals (such as Alberta sub-bituminous coal) are equivalent to that obtained with coal-only process derived solvent. High selectivity to hydrocar-bon liquids with minimum by-product gas yield have been achieved.
Also, it has been determined that the Watson characterization ~actors in relation to the mean average boiling point for the hydrocarbon liquid products produced by the present catalytic two-stage coal/oil co-processing process are intermediate those produced by a catalytictwo-stage coal liquefaction process and by catalytic petroleum hydroconversion processes.
; In the present invention, if the petroleum oil feed exceeds needed for slurrying the particulate coal ~eed to provide a pumpable fluid mi~ture, the recycle of hydroconverted hydrocarbon liquids or such slurrying may not be required. Otherwise, such recycle o heavy distilled hydrocarbon ractions is usuaLly done to provide increased conversion and yields o' low-boiling hydro-~lcarbon liquid products.
il -3-i~
B
~ Z 8~)7 13~ --3a-The present invention, therefore, resides in a two-stage continuous process for catalytic hydroconversion of a fluid blend of a solid carbonaceous material and heavy hydrocarbon liquid, comprising;
(a) mlxing a solld carbonaceous particulate material with sufflcient heavy hydrocarbon liquid having at least about 90 V% normally boiling above 650-F to provide a flowable B lurry mixture, the total hydrocarbon liquid/coal feed weight ratio being between about 1.0/1 and 3/1, with the solid aarbonaaeous material being between about 25 and 50 W % o~ the total feed material;
(b) feeding the flowable slurry mixture with hydrogen into a first stage back-mixed catalytic reaction zone containing an ebullated catalyst bed of particulate hydrogenation oatalyst, said reaction zone having an internal liquid recycle;
said catalyst containing an active metal component wherein the metal in said component i5 selected from the metals group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten, and mixtures thereof on a support material, said catalyst bed being maintained at 650-800-F temperature, 1000-4000 psig hydrogen partial pressure and feed rate of 10-100 lb carbonaceous materi.al plus heavy hydrocarbon liquid feed per hour per ft3 reaotion zone volume for hydrogenation reaction to partially hydrogenate and hydrooonvert the feed materials to hydrocarbon material contalning less. than 6 W% C1--C3 hydrocarbon gases, 15-25 W% 650-F-light li~uld ~raction and 60-70 W% 650-F-~ hydrocarbon material fraction;
(c) passing the total effluent material from ~aid first stage reaction zone wlth addltional hydrogen directly to a close-coupled second stage back-mixed catalytic reaction zone containing an ~ 30~7~7 -3b-ebullated catalyst bed &O as to avoid forming retrograde materials in the effluent, said catalyst containing an active metal component wherein the metal ln said component la selected from the ~atalq group consisting of cobalt, lron, molybdenum, nickel, tin, tungsten and mixtures thereof on a support material, said second stage reaction zone being maintalned at a higher temperature than the ~irst s-tage reaction zone, and at 750-900'F
temperature and 1000-~000 psig hydrogen partial pres~ure to convert the remaining unconverted carbonaceous materlal to hydrocarbon gases, hydrocarbon liquld fraction normally boiling between 400-650-F and including a high boiling residuum fraction;
(d) passing the resulting effluent material from said second stage reaction zone to successive phase separation and distillation steps to separate the gas material fraction; and (e) removlng unconverted coal and ash solids material and a heavy hydrocarbon bottoms liquid material, and thereby producing low-boiling hydrocarbon liquid products normally boiling between 150 F and 975 F.
- BRIEF DESCRIPTION OF DRAWINGS
Fig. 1 is a schematic flow diagram of a two-stage catalytic process for hydroconversion of coal/oil feedstocks according to the present invention.
;' .. . .
, DESCRIPTION OF INVENTION
In the present invention, improved hydrogenation and hydro-conversion of blended coal and oil feedstocks is provided in a two-stage catalytic process using ebullated catalyst bed reactors.
As is ~hown in the Fig. 1 process flow diagram for catalytic two-stage coal/oil co-processing, a coal such as bituminous, sub-bitum-inous or lignite, is provided at 10 and is passed through a coal preparation unit 12, where the coal is ground to a desired particle ~size such as 50-375 mesh (U.S. Sieve Series) and dried to a desired moisture content such as containing 2-10 W % moisture. The par-ticulate coal is then blended with fresh hydrocarbon liquid feed such as petroleum resid, heavy crude oil, tar sand bitumen, or shale oil provided at 11, and are mixed together at slurry tank 14 ~, ; . .
'. I, . ' i ;l '' \
~`! ' ' I _4-I . ' ;~æ
to provide a pumpable coal-oil slurry feed material. A total oil/coal weight ratio between about 1.4/1 and 3/1 can be used. If desired, a recycled process-derived slurrying oil at 15 can be ad-ditionally mixed with the coal and oil feedstocks. The resulting cosl-oil slurry is pumped at 16 to reactor pressure, preheated at 18, mixed with hydrogen gas at 17 and is fed into the lower end of the first stage reactor 20.
The first stage reactor 20 is preferably a catalytic ebullated ;bed reactor containing catalyst bed 22 and operating at moderate jconditions of 650-800F temperature and hydrogen partial pressure ; of 1000-4000 psig for hydrogenation and hydrocon~ersion of the ! blended feed materials. In the reactor the blended upflowing coal-oil feed material is effectively contacted with hydrogen in the presence of a particulate hydrogenation catalyst, as generally described by U.S. Patent No. Re 25,770. Conventional hydrogenation catalysts, including nickel molybdate, cobalt molybdate or nickel-tungsten on an alumina or silica support such as employed in the H-Coal~ or H-Oil~ Processes are utilized in the well-mixed ebul-lated bed reactor. Useful total feed rates are in the range of lO to 100 lb/hr/ft' reactor volume for each stage, with feed rates of 15-75 lb/hr/ft' usually being preferred depending on the par-ticular proportions of coal and oil in the feed and the products desired.
1 From the first stagr-. reactor 20,the total effluent stream 26 i! iY mixed with additional preheated hydrogen at 28 as needed and !1 is fed directly into the lower end of second-stage reactor 30 The dded hydrogen is preheated to increase the ternperature of the !1 first-stage reactor effluent to the desired second stage reactor temperature conditions. The second stage reactor 30 is preferably ;la catalytic ebullated bed reactor contain~g catalyst bed 32 and 2 operating at essentially the same pressure conditions as the first 1,,~,,"'1,,,, , ~
~} ~ 7(:~7 st~ge res~to~ (slightly low~r to allow ~or pressur~ drop nnd for-ward flow of ms~erials) ~nd a~ hi~her temperatures of 750-900F
utili~ed for further hydroconversion reactions. The second stage reactor uses catalysts which are similar to those for the first stage reactor. The first and second stage reactors may hsve equal volumes or they may be substantially different in volume depending ' ,on the product yield and product quality objectives.
From the second stage reactor~effluent 38 vapor and liquid ractions are separated at the existillg high pressure in separator 40, and the vapor fraction ~1 passed to hydrogen purification unit ~2 to provide a hydrogen recycle stream 43. The liquid fraction ~4 is pressure-red~ced at 47 to recover distillate liquid products in an atmospheric pressure fractionator 50 to produce desired distillate liquid prod~cts 51 and 52. The bottoms liquid stream 55 is passed to a liquid-solids separation step 56, from which fine solids material of unconverted coal and ash are removed ~t 57.
If desired, a portion of the atmospheric bottoms liquid from the liquid-solids separation step 56 can be advantageously recyaled to the iirst stage reaotor as ~lurrying oil 15. If sufficient liquid hydrocarbon feedstock is used to slurry the coal eed, use o~
recycled process-derived slurrying oil can be eliminated, to provide a once-through type operation ~or the feedstocks. Process-derived hydrocarbon streams which may be used for the coal slurrylng oil include distillate liquid product, and product oils which are recovered from the liquid-solids separation step, which may utilize hydroclones, filters, centriEuges, or solvent deashing technigues. The remainder of the a-tmospheri.c bottoms material rom separation step 56 is vacuum distilled to recover a vacuum gas oil stream and a pumpable vacuum bottom~ slurry material.
This invention will be further described by reEerence to the Eollowing Examples of operations, which should not be construed as limiting the invention.
~ 7~7 I .
/ . ' '.
Feed materials consisting of Alberta sub-bituminous coal alone, and also the coal mixed with equal portions of Cold Lake atmospheric rcsiduum, wcrc processed in a bench scale two-stage catalytic co-processing unit in accordance with this invention.
Inspection analysis of the Alberta sub-bituminous coal is provided in Table 1, and analysis for the Cold Lake residuum material is provided in Table 2. The first and second stage catalytic reactors were operated at 750~F and 825F temperature, respect~ly, and 2400 psig hydrogen partial pressure and at feed ratios for oil/
coal/recycle liquids as indicated in Table 3. Comparative results of these operations are shown in Table 3.
TAaLE 1 ANALYSIS OF ABBERTA SUB~BITUMINOUS COAL
Moisture, W Z 8-9 Ultimate Analysis, W /. Dry Basis Carbon 67.7 Hydrogen . 4.3 Nitrogen 1,.5 Sulfur 0 7 Ash 8.0 Oxygen (by difference) 17 8 tlydrogen/Carbon Atomic Rrelo 0~76 _7_ . ~'~
t .
ANALYSIS Ol COID LAKE RrSlDUUM
Gravlty, ~API 5 2 Uydrogen, W % 10 2 Nitrogen, W % 0.50 Oxygen,W %
Ni~kel, ppm Vanadium, ppm 240 Weight percent 975F~ ~aterial7~.2 '~ydrogen/Carbon Atomic Ratio1.46 .
y ~
. , .,. --_ ~ ~ 8(:~707 I
I
SUMMARY OF OPERATING CONDITIO~S AND YIELDS
A B
, Condition Coal OnlyCo-Processing W % Coal Feed 100 50 W % Oil Feed 0 50 Recycle Oil, W % on c081 170 70 First Stage Reactor Feed W % Co~l 37 37 Oil/coal/recycle0/1/1.71/1/0.7 Feed Space Velocity - lbs coal/hr/ft' reactor 20 20 - lbs coal+oil/hr/ft' reactor 20 40 First Stage Temperature, F 750 750 Second Stag~ Temperature, F 825 825 Reactor Pressure, psig 2500 2500 Yields, A % Dry Feed ; C4-390F Liquid 260 3 15 7 390-650DF Liquid37.0 25.8 ¦ 650-975F Liquid 7.6 27.5 975F~ Resid 2.3 11.8 Unconverted Coal8.1 4.2 Ash 8.0 4.0 H20, CO~ C02 16.0 8.0 NH3 1.5 0.7 H2S 4 2.7 Total (lOO+H2 reacted) 107.3 104.2 C4-975F liquid 64.9 69.0 j Performance Parameters Coal Conversion, ~ % MAF Coal91.3 91.2 975F~ Conversion, W % MAF Feed88.7 80.4 C4-975F Liquid, ~ % MAF Feed70.5 71.9 Barrels of C~-975F/Metric lll Ton MAF Feed 5.1 5.2 j'l _9_ ~' P
____ ~, ,.
7~
From these results, it is seen that for essentially twice as much feed material being co-processed through the two-stage-catalytic reactors, the present co-processing proce~s provides improv2d yields of C4-975F
liqu.ids and reduced yields of C1-C3 gas. Furthermore, it is pointed out that the yield of C4-975F material is actually increased.
Example 2 Other similar catalytic hydroprocessing operations were carried out separately on the Cold Lake atmospheric residuum material and on Alberta sub-bituminous coal blended with different ratios of the residuum Eeed and recycled processed-derived oil. In an alternative process arrangement, the coal/oil co-processing of Cold Lake atmospheric residuum and Alberta sub-bituminous coal was carried out in a once-through operati.ng mode, i.e., without recycle of any process-derived liquid, with results being shown in Table 4.
CATALYTIC TWO STAGE CO-PROCESSING YIELDS
Alberta Sub-Bituminous Coal/Cold Lake Atmospheric Residuum Oil/Coal/Recycle Weight Ratio 1.7/1/0 1/1/0.7 YIELDS, W % M.A.F. Coal Plus Oil C1-C3 Gas 2.7 3.8 C4-975F Liquid 74.4 71.9 Coal Conversion 92 91 975F ~ Conversion 80 80 Hydrodesulfurization, % 77 87 Hydrodemetallization, %
Hydrogen Efficiency 21 16 C4-975F, Bbl/Metric Ton Fresh Feed 5.4 5.2 These results show that comparable coal conversion, 975F -~ conversion material and liquid product yields and hydrodesulEurization were i`-'~
.
.2~7 .
~1 / ¦ achieved by catalytic two-stage hydroprocessing in accordance with ~ the present inv~ntion, as compared to separate catalytic hydrocon-¦ version of these feed ma~erials. Also, as shown in Table 4, the 1 low tempernture ~irst stage renction zon~ hydrocJenat~s th~ Ee~d coaland oil suf~iclen~ly ~:ue~ h~ u~ oL l~ro~ r.lvc~l rocyc:l o liquids can be elimin~ted. R~sults Eor the once--throu~ll l . operatiny mod~ similar to 13xam~1e~ 1 ~oal/o.Ll co ~ro~ lny ¦ ¦ were obtained . EXAMPLE 3 l . '.
Other comparable two-stage catalytic operations were carried out which shows chc advantage of recycling unconverted coal and ash solids to the first stage catalytic reactor in this two-stage coal/
oil co-processing process, the results being shown in Table 5.
. .
TWO-STAGE CO-PROCESSIN~ WITH LIQUID RECYCLE
Coal in Fresh F~ed, W % 50 50 ~irst Staee Feed Ratio, Oil/Coal/Recycle 1/1/0.7 1/1/0.7 ~ Recycle Liquid ~sed 550FtFiltered 550F~Liquid I Liquid Product Containing Solids Cl-C3 Gas~W % dry coal 3.6 3.8 C4-975F Liquids, W % dry coal 70.5 69.0 Coal Conversion, W % MAF Coal 88.7 91.2 (~2.5) C4~Liquid, W % MAF Coal Feed 82.1 84.2 (~2.1) From the results, it is seen that for otherwise equivalent operating conditions the recycle of unconverted coal and ash solids ,results in approximately 2. 5% increase in the coal conversion iand 2.1% lncrease in the production of C4~ liquids, based on the ~M.A.F. coal feed.
¦ Although this invention has been described broadly and in Illterms of certain preferred embodiment thereof, it will be under-jistood that modification and variations of the process can be made within the spirit and scope of the invention, which is defined by I~the following claims. -11-l _~
. . .
COAL/OIL FE~DSTOCKS
BACKGRO~JD OF INVENTION
This invention pertains to co-processing coal/oil feed-stock3 in a two-stage catalytic hydroconversion process. It pertains more particulatly to such coal/oil co-processing to produce higher percentage conversion and increased yields of low-boiling hydrocarbon distillate liquid products, while mlnimizing hydrocarbon gases and heavy resid materials.
Coal/oil co-processing using a single stage catalytic ebullated bed reactor, has been shown to be an effective technique for simultaneous conversion o coal and residual oils to produce predominately hydrocarbon liquid products, as disclosed by U.S. Patent 4,0~5,504 to Chervenak, et al. At high percentage conversio. levels, the single stage hydrogenation procecs produces undesirably high yields of byproduct hydrocarbon gas (Cl-C3) and product quality decreases, i.e., the N2 and S contents of the distillate llquids increase. SeVeral other processes for simui-taneous processing of coal and petroleum feeds using two reactionstages have been proposed, such as disclosed by U.S. Patent Nos. 3,870,621 to Arnold; 4,306,960 to Gleim, and 4,330,390 to Rosenthal, et al. However, these processes all have shortcomings and do not achieve the flexibilityiand high yields o low-boiling hydrocarbon distillate liquids de~ired. Significantly ijmprove~
result~ have now ~een achieved by the present two-stage catalytic coal/oll co-processing proces~. ~
'' ';
. i';~
. 1.
7~7 ~uMM~ y ()I INVI:NI'I~)N
The present invention provides an improvecl hydrogcnntlon pro-cess in which particulate coal and liquid hydrocarbon feedstocks are co-peocessed in a catalytic two-stage ebullate-bed reactor sys-tem, to produce increased yields of low-boiling hydrocarbon distil-late liquids and minimal yield~ of hydrocarbon gas and high-boiling resid fractions. The first stage reactor is operated at mild hy-drogenation conditions of 650-800F temperature and 1000-4000 psig hydrogen partiaL pressure and at 10-100 lb coal and petroleum/hr ft' reactor volume to increase the hydrogen content of the dissolved .. _ _ _ .., , , _ ... .. . . ... ..
coal and oil feed, and recycle oil (if ~se~) molecules, while obtaining moderate conversion of the coal without producing re3ressive (coke forming) reactions.
The catalyst should be selected from the metals group con6isting of oxides or other metal compounds or components of cobalt, iron, molybdenum, nickel, tin, tung~ten and mixture~ thereof and other hydrocarbon hydrogenation cataly~t metal oxide~ known in the art, deposited on a base material selected from the group consis~-ing of alumina, magnesia, silica, titania, and similar materials.
Useful catalyst particle sizes can range from about 0.030 to 0.125 inch effective diameter The first stage reactor effluent material is passed to ~
direct-coupled second stage catalytic reactor, which is operated at somewhat more severe hydroconversion conditions of 750-900F
temperature and 1000-4000 psig hydrogen partial pressure to con~
vert the remaining unconverted coal and residual oil and to pro-duce high yields of high quality distillate liquid products, with minimal yields of hydrocarbon gases and high-boiling resid fract-ions. The catalyst used is similar or can be the same as that used in the first stage reactor. From the second stage reactor the I z~
effluent is phnse separule(l and distilled to provlde the com-bined hydrocarbon liquid distillate products.
This process improvement permits co-processing operations on blended coal and petroleum feedstocks at high conversion to pro-vide distillate liquid products, without encountering compatibility problems between the coal-derived and oil-derived products. The addition o a :first low severity hydrogenation reaction stage to increase the hydrogen content of thè fresh coal and oil feed materials (and recycle oil if present) reduces sulfur and nitrogen compounds in the liquid product and improves the solvent quality of the liquids needed to dissolve the coal, and also significantly improves the overall process performance and allows its successful applicat~on to a wider range o fcedstocks. Coal conversion in catalytic two-stage co-processing with solvent quality sensitive coals (such as Alberta sub-bituminous coal) are equivalent to that obtained with coal-only process derived solvent. High selectivity to hydrocar-bon liquids with minimum by-product gas yield have been achieved.
Also, it has been determined that the Watson characterization ~actors in relation to the mean average boiling point for the hydrocarbon liquid products produced by the present catalytic two-stage coal/oil co-processing process are intermediate those produced by a catalytictwo-stage coal liquefaction process and by catalytic petroleum hydroconversion processes.
; In the present invention, if the petroleum oil feed exceeds needed for slurrying the particulate coal ~eed to provide a pumpable fluid mi~ture, the recycle of hydroconverted hydrocarbon liquids or such slurrying may not be required. Otherwise, such recycle o heavy distilled hydrocarbon ractions is usuaLly done to provide increased conversion and yields o' low-boiling hydro-~lcarbon liquid products.
il -3-i~
B
~ Z 8~)7 13~ --3a-The present invention, therefore, resides in a two-stage continuous process for catalytic hydroconversion of a fluid blend of a solid carbonaceous material and heavy hydrocarbon liquid, comprising;
(a) mlxing a solld carbonaceous particulate material with sufflcient heavy hydrocarbon liquid having at least about 90 V% normally boiling above 650-F to provide a flowable B lurry mixture, the total hydrocarbon liquid/coal feed weight ratio being between about 1.0/1 and 3/1, with the solid aarbonaaeous material being between about 25 and 50 W % o~ the total feed material;
(b) feeding the flowable slurry mixture with hydrogen into a first stage back-mixed catalytic reaction zone containing an ebullated catalyst bed of particulate hydrogenation oatalyst, said reaction zone having an internal liquid recycle;
said catalyst containing an active metal component wherein the metal in said component i5 selected from the metals group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten, and mixtures thereof on a support material, said catalyst bed being maintained at 650-800-F temperature, 1000-4000 psig hydrogen partial pressure and feed rate of 10-100 lb carbonaceous materi.al plus heavy hydrocarbon liquid feed per hour per ft3 reaotion zone volume for hydrogenation reaction to partially hydrogenate and hydrooonvert the feed materials to hydrocarbon material contalning less. than 6 W% C1--C3 hydrocarbon gases, 15-25 W% 650-F-light li~uld ~raction and 60-70 W% 650-F-~ hydrocarbon material fraction;
(c) passing the total effluent material from ~aid first stage reaction zone wlth addltional hydrogen directly to a close-coupled second stage back-mixed catalytic reaction zone containing an ~ 30~7~7 -3b-ebullated catalyst bed &O as to avoid forming retrograde materials in the effluent, said catalyst containing an active metal component wherein the metal ln said component la selected from the ~atalq group consisting of cobalt, lron, molybdenum, nickel, tin, tungsten and mixtures thereof on a support material, said second stage reaction zone being maintalned at a higher temperature than the ~irst s-tage reaction zone, and at 750-900'F
temperature and 1000-~000 psig hydrogen partial pres~ure to convert the remaining unconverted carbonaceous materlal to hydrocarbon gases, hydrocarbon liquld fraction normally boiling between 400-650-F and including a high boiling residuum fraction;
(d) passing the resulting effluent material from said second stage reaction zone to successive phase separation and distillation steps to separate the gas material fraction; and (e) removlng unconverted coal and ash solids material and a heavy hydrocarbon bottoms liquid material, and thereby producing low-boiling hydrocarbon liquid products normally boiling between 150 F and 975 F.
- BRIEF DESCRIPTION OF DRAWINGS
Fig. 1 is a schematic flow diagram of a two-stage catalytic process for hydroconversion of coal/oil feedstocks according to the present invention.
;' .. . .
, DESCRIPTION OF INVENTION
In the present invention, improved hydrogenation and hydro-conversion of blended coal and oil feedstocks is provided in a two-stage catalytic process using ebullated catalyst bed reactors.
As is ~hown in the Fig. 1 process flow diagram for catalytic two-stage coal/oil co-processing, a coal such as bituminous, sub-bitum-inous or lignite, is provided at 10 and is passed through a coal preparation unit 12, where the coal is ground to a desired particle ~size such as 50-375 mesh (U.S. Sieve Series) and dried to a desired moisture content such as containing 2-10 W % moisture. The par-ticulate coal is then blended with fresh hydrocarbon liquid feed such as petroleum resid, heavy crude oil, tar sand bitumen, or shale oil provided at 11, and are mixed together at slurry tank 14 ~, ; . .
'. I, . ' i ;l '' \
~`! ' ' I _4-I . ' ;~æ
to provide a pumpable coal-oil slurry feed material. A total oil/coal weight ratio between about 1.4/1 and 3/1 can be used. If desired, a recycled process-derived slurrying oil at 15 can be ad-ditionally mixed with the coal and oil feedstocks. The resulting cosl-oil slurry is pumped at 16 to reactor pressure, preheated at 18, mixed with hydrogen gas at 17 and is fed into the lower end of the first stage reactor 20.
The first stage reactor 20 is preferably a catalytic ebullated ;bed reactor containing catalyst bed 22 and operating at moderate jconditions of 650-800F temperature and hydrogen partial pressure ; of 1000-4000 psig for hydrogenation and hydrocon~ersion of the ! blended feed materials. In the reactor the blended upflowing coal-oil feed material is effectively contacted with hydrogen in the presence of a particulate hydrogenation catalyst, as generally described by U.S. Patent No. Re 25,770. Conventional hydrogenation catalysts, including nickel molybdate, cobalt molybdate or nickel-tungsten on an alumina or silica support such as employed in the H-Coal~ or H-Oil~ Processes are utilized in the well-mixed ebul-lated bed reactor. Useful total feed rates are in the range of lO to 100 lb/hr/ft' reactor volume for each stage, with feed rates of 15-75 lb/hr/ft' usually being preferred depending on the par-ticular proportions of coal and oil in the feed and the products desired.
1 From the first stagr-. reactor 20,the total effluent stream 26 i! iY mixed with additional preheated hydrogen at 28 as needed and !1 is fed directly into the lower end of second-stage reactor 30 The dded hydrogen is preheated to increase the ternperature of the !1 first-stage reactor effluent to the desired second stage reactor temperature conditions. The second stage reactor 30 is preferably ;la catalytic ebullated bed reactor contain~g catalyst bed 32 and 2 operating at essentially the same pressure conditions as the first 1,,~,,"'1,,,, , ~
~} ~ 7(:~7 st~ge res~to~ (slightly low~r to allow ~or pressur~ drop nnd for-ward flow of ms~erials) ~nd a~ hi~her temperatures of 750-900F
utili~ed for further hydroconversion reactions. The second stage reactor uses catalysts which are similar to those for the first stage reactor. The first and second stage reactors may hsve equal volumes or they may be substantially different in volume depending ' ,on the product yield and product quality objectives.
From the second stage reactor~effluent 38 vapor and liquid ractions are separated at the existillg high pressure in separator 40, and the vapor fraction ~1 passed to hydrogen purification unit ~2 to provide a hydrogen recycle stream 43. The liquid fraction ~4 is pressure-red~ced at 47 to recover distillate liquid products in an atmospheric pressure fractionator 50 to produce desired distillate liquid prod~cts 51 and 52. The bottoms liquid stream 55 is passed to a liquid-solids separation step 56, from which fine solids material of unconverted coal and ash are removed ~t 57.
If desired, a portion of the atmospheric bottoms liquid from the liquid-solids separation step 56 can be advantageously recyaled to the iirst stage reaotor as ~lurrying oil 15. If sufficient liquid hydrocarbon feedstock is used to slurry the coal eed, use o~
recycled process-derived slurrying oil can be eliminated, to provide a once-through type operation ~or the feedstocks. Process-derived hydrocarbon streams which may be used for the coal slurrylng oil include distillate liquid product, and product oils which are recovered from the liquid-solids separation step, which may utilize hydroclones, filters, centriEuges, or solvent deashing technigues. The remainder of the a-tmospheri.c bottoms material rom separation step 56 is vacuum distilled to recover a vacuum gas oil stream and a pumpable vacuum bottom~ slurry material.
This invention will be further described by reEerence to the Eollowing Examples of operations, which should not be construed as limiting the invention.
~ 7~7 I .
/ . ' '.
Feed materials consisting of Alberta sub-bituminous coal alone, and also the coal mixed with equal portions of Cold Lake atmospheric rcsiduum, wcrc processed in a bench scale two-stage catalytic co-processing unit in accordance with this invention.
Inspection analysis of the Alberta sub-bituminous coal is provided in Table 1, and analysis for the Cold Lake residuum material is provided in Table 2. The first and second stage catalytic reactors were operated at 750~F and 825F temperature, respect~ly, and 2400 psig hydrogen partial pressure and at feed ratios for oil/
coal/recycle liquids as indicated in Table 3. Comparative results of these operations are shown in Table 3.
TAaLE 1 ANALYSIS OF ABBERTA SUB~BITUMINOUS COAL
Moisture, W Z 8-9 Ultimate Analysis, W /. Dry Basis Carbon 67.7 Hydrogen . 4.3 Nitrogen 1,.5 Sulfur 0 7 Ash 8.0 Oxygen (by difference) 17 8 tlydrogen/Carbon Atomic Rrelo 0~76 _7_ . ~'~
t .
ANALYSIS Ol COID LAKE RrSlDUUM
Gravlty, ~API 5 2 Uydrogen, W % 10 2 Nitrogen, W % 0.50 Oxygen,W %
Ni~kel, ppm Vanadium, ppm 240 Weight percent 975F~ ~aterial7~.2 '~ydrogen/Carbon Atomic Ratio1.46 .
y ~
. , .,. --_ ~ ~ 8(:~707 I
I
SUMMARY OF OPERATING CONDITIO~S AND YIELDS
A B
, Condition Coal OnlyCo-Processing W % Coal Feed 100 50 W % Oil Feed 0 50 Recycle Oil, W % on c081 170 70 First Stage Reactor Feed W % Co~l 37 37 Oil/coal/recycle0/1/1.71/1/0.7 Feed Space Velocity - lbs coal/hr/ft' reactor 20 20 - lbs coal+oil/hr/ft' reactor 20 40 First Stage Temperature, F 750 750 Second Stag~ Temperature, F 825 825 Reactor Pressure, psig 2500 2500 Yields, A % Dry Feed ; C4-390F Liquid 260 3 15 7 390-650DF Liquid37.0 25.8 ¦ 650-975F Liquid 7.6 27.5 975F~ Resid 2.3 11.8 Unconverted Coal8.1 4.2 Ash 8.0 4.0 H20, CO~ C02 16.0 8.0 NH3 1.5 0.7 H2S 4 2.7 Total (lOO+H2 reacted) 107.3 104.2 C4-975F liquid 64.9 69.0 j Performance Parameters Coal Conversion, ~ % MAF Coal91.3 91.2 975F~ Conversion, W % MAF Feed88.7 80.4 C4-975F Liquid, ~ % MAF Feed70.5 71.9 Barrels of C~-975F/Metric lll Ton MAF Feed 5.1 5.2 j'l _9_ ~' P
____ ~, ,.
7~
From these results, it is seen that for essentially twice as much feed material being co-processed through the two-stage-catalytic reactors, the present co-processing proce~s provides improv2d yields of C4-975F
liqu.ids and reduced yields of C1-C3 gas. Furthermore, it is pointed out that the yield of C4-975F material is actually increased.
Example 2 Other similar catalytic hydroprocessing operations were carried out separately on the Cold Lake atmospheric residuum material and on Alberta sub-bituminous coal blended with different ratios of the residuum Eeed and recycled processed-derived oil. In an alternative process arrangement, the coal/oil co-processing of Cold Lake atmospheric residuum and Alberta sub-bituminous coal was carried out in a once-through operati.ng mode, i.e., without recycle of any process-derived liquid, with results being shown in Table 4.
CATALYTIC TWO STAGE CO-PROCESSING YIELDS
Alberta Sub-Bituminous Coal/Cold Lake Atmospheric Residuum Oil/Coal/Recycle Weight Ratio 1.7/1/0 1/1/0.7 YIELDS, W % M.A.F. Coal Plus Oil C1-C3 Gas 2.7 3.8 C4-975F Liquid 74.4 71.9 Coal Conversion 92 91 975F ~ Conversion 80 80 Hydrodesulfurization, % 77 87 Hydrodemetallization, %
Hydrogen Efficiency 21 16 C4-975F, Bbl/Metric Ton Fresh Feed 5.4 5.2 These results show that comparable coal conversion, 975F -~ conversion material and liquid product yields and hydrodesulEurization were i`-'~
.
.2~7 .
~1 / ¦ achieved by catalytic two-stage hydroprocessing in accordance with ~ the present inv~ntion, as compared to separate catalytic hydrocon-¦ version of these feed ma~erials. Also, as shown in Table 4, the 1 low tempernture ~irst stage renction zon~ hydrocJenat~s th~ Ee~d coaland oil suf~iclen~ly ~:ue~ h~ u~ oL l~ro~ r.lvc~l rocyc:l o liquids can be elimin~ted. R~sults Eor the once--throu~ll l . operatiny mod~ similar to 13xam~1e~ 1 ~oal/o.Ll co ~ro~ lny ¦ ¦ were obtained . EXAMPLE 3 l . '.
Other comparable two-stage catalytic operations were carried out which shows chc advantage of recycling unconverted coal and ash solids to the first stage catalytic reactor in this two-stage coal/
oil co-processing process, the results being shown in Table 5.
. .
TWO-STAGE CO-PROCESSIN~ WITH LIQUID RECYCLE
Coal in Fresh F~ed, W % 50 50 ~irst Staee Feed Ratio, Oil/Coal/Recycle 1/1/0.7 1/1/0.7 ~ Recycle Liquid ~sed 550FtFiltered 550F~Liquid I Liquid Product Containing Solids Cl-C3 Gas~W % dry coal 3.6 3.8 C4-975F Liquids, W % dry coal 70.5 69.0 Coal Conversion, W % MAF Coal 88.7 91.2 (~2.5) C4~Liquid, W % MAF Coal Feed 82.1 84.2 (~2.1) From the results, it is seen that for otherwise equivalent operating conditions the recycle of unconverted coal and ash solids ,results in approximately 2. 5% increase in the coal conversion iand 2.1% lncrease in the production of C4~ liquids, based on the ~M.A.F. coal feed.
¦ Although this invention has been described broadly and in Illterms of certain preferred embodiment thereof, it will be under-jistood that modification and variations of the process can be made within the spirit and scope of the invention, which is defined by I~the following claims. -11-l _~
. . .
Claims (11)
1. A two-stage continuous process for catalytic hydroconversion of a fluid blend of a solid carbonaceous material and heavy hydrocarbon liquid, comprising;
(a) mixing a solid carbonaceous particulate material with sufficient heavy hydrocarbon liquid having at least about 90 V% normally boiling above 650°F to provide a flowable slurry mixture, the total hydrocarbon liquid/coal feed weight ratio being between about 1.0/1 and 3/1, with the solid carbonaceous material being between about 25 and 50 W % of the total feed material;
(b) feeding the flowable slurry mixture with hydrogen into a first stage back-mixed catalytic reaction zone containing an ebullated catalyst bed of particulate hydrogenation catalyst, said reaction zone having an internal liquid recycle;
said catalyst containing an active metal component wherein the metal in said component is selected from the metals group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten, and mixtures thereof on a support material, said catalyst bed being maintained at 650-800°F temperature, 1000-4000 psig hydrogen partial pressure and feed rate of 10-100 lb carbonaceous material plus heavy hydrocarbon liquid feed per hour per ft3 reaction zone volume for hydrogenation reaction to partially hydrogenate and hydroconvert the feed materials to hydrocarbon material containing less than 6 W% C1-C3 hydrocarbon gases, 15-25 W% 650°F-light liquid fraction and 60-70 W% 650°F+ hydrocarbon material fraction;
(c) passing the total effluent material from said first stage reaction zone with additional hydrogen directly to a close-coupled second stage back-mixed catalytic reaction zone containing an ebullated catalyst bed so as to avoid forming retrograde materials in the effluent, said catalyst containing an active metal component wherein the metal in said component is selected from the metals group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten and mixtures thereof on a support material, said second stage reaction zone being maintained at a higher temperature than the first stage reaction zone, and at 750-900°F
temperature and 1000-4000 psig hydrogen partial pressure to convert the remaining unconverted carbonaceous material to hydrocarbon gases, hydrocarbon liquid fraction normally boiling between 400-650°F and including a high boiling residuum fraction;
(d) passing the resulting effluent material from said second stage reaction zone to successive phase separation and distillation steps to separate the gas material fraction; and (e) removing unconverted coal and ash solids material and a heavy hydrocarbon bottoms liquid material, and thereby producing low-boiling hydrocarbon liquid products normally boiling between 150°F and 975°F.
(a) mixing a solid carbonaceous particulate material with sufficient heavy hydrocarbon liquid having at least about 90 V% normally boiling above 650°F to provide a flowable slurry mixture, the total hydrocarbon liquid/coal feed weight ratio being between about 1.0/1 and 3/1, with the solid carbonaceous material being between about 25 and 50 W % of the total feed material;
(b) feeding the flowable slurry mixture with hydrogen into a first stage back-mixed catalytic reaction zone containing an ebullated catalyst bed of particulate hydrogenation catalyst, said reaction zone having an internal liquid recycle;
said catalyst containing an active metal component wherein the metal in said component is selected from the metals group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten, and mixtures thereof on a support material, said catalyst bed being maintained at 650-800°F temperature, 1000-4000 psig hydrogen partial pressure and feed rate of 10-100 lb carbonaceous material plus heavy hydrocarbon liquid feed per hour per ft3 reaction zone volume for hydrogenation reaction to partially hydrogenate and hydroconvert the feed materials to hydrocarbon material containing less than 6 W% C1-C3 hydrocarbon gases, 15-25 W% 650°F-light liquid fraction and 60-70 W% 650°F+ hydrocarbon material fraction;
(c) passing the total effluent material from said first stage reaction zone with additional hydrogen directly to a close-coupled second stage back-mixed catalytic reaction zone containing an ebullated catalyst bed so as to avoid forming retrograde materials in the effluent, said catalyst containing an active metal component wherein the metal in said component is selected from the metals group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten and mixtures thereof on a support material, said second stage reaction zone being maintained at a higher temperature than the first stage reaction zone, and at 750-900°F
temperature and 1000-4000 psig hydrogen partial pressure to convert the remaining unconverted carbonaceous material to hydrocarbon gases, hydrocarbon liquid fraction normally boiling between 400-650°F and including a high boiling residuum fraction;
(d) passing the resulting effluent material from said second stage reaction zone to successive phase separation and distillation steps to separate the gas material fraction; and (e) removing unconverted coal and ash solids material and a heavy hydrocarbon bottoms liquid material, and thereby producing low-boiling hydrocarbon liquid products normally boiling between 150°F and 975°F.
2. The hydroconversion process of claim 1, wherein said solid carbonaceous material is sub-bituminous coal.
3. The hydroconversion process of claim 1, wherein said heavy hydrocarbon liquid is petroleum residuum.
4. The hydroconversion process of claim 1, wherein the first stage temperature is 700-780 F, the second stage temperature is 780-860°F, and the hydrogen partial pressure is 1500-3500 psig.
5. The hydroconversion process of claim 1, wherein the oil/coal ratio is between 1.4/1 and 3.0/1.
6. The hydroconversion process of claim 2, wherein the coal is Alberta sub-bituminous coal.
7. The hydroconversion process of claim 3, wherein the petroleum residuum is Cold Lake atmospheric residuum.
8. A two-stage continuous process for catalytic hydroconversion of a fluid blend of sub-bituminous coal and petroleum atmospheric residuum liquid, the process comprising;
(a) mixing the particulate sub-bituminous coal with sufficient petroleum atmospheric residuum having at least about 90 V% normally boiling above 650°F and containing at least about 20 W% aromatic compounds to provide a flowable slurry mixture, the total petroleum residuum/coal feed weight ratio being between 1Ø/1 and 3/1, with the coal feed being between about 25 and 50 W% of the total hydrocarbon feed material;
(b) feeding the slurry mixture with hydrogen into a first stage back-mixed catalytic reaction zone containing an ebullated catalyst bed of particulate hydrogenation catalyst, said reaction zone having an internal liquid recycle ratio at least about 1:1, said catalyst containing an active metal component wherein the metal in said component is selected from the group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten, and combinations thereof deposited on a support material selected from the group consisting of alumina, magnesia, silica, titania and similar materials, said catalyst bed being maintained at 700-780°F temperature, 1500-3500 psia hydrogen partial pressure and feed rate of 15-75 pounds coal plus petroleum residuum oil per hr per fr3 reactor volume for hydrogenation and hydroconversion reactions to provide lower boilig hydrocarbon materials containing less than 6 W% C1-C3 hydrocarbon gases, 15-25 W% 650-F-light liquid fraction and 60-70- W% 650°F+ hydrocarbonmaterial fraction;
(c) passing the total effluent material from said first stage reaction zone together with additional hydrogen directly to a close-coupled second stage back-mixed catalytic reaction zone so as to avoid forming retrograde materials in the effluent, said catalyst containing an active metal oxide or other metal compound selected from the metals group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten and combinations thereof deposited on a support material selected from the group consisting of alumina, magnesia, silica, titania and similar materials, said second stage zone containing an ebullated catalyst bed maintained at a higher temperature than the first stage reaction zone, and at 780-860°F temperature, and 1500-3500 psig hydrogen partial pressure to hydroconvert the remaining coal and residuum material to hydrocarbon gases, hydrocarbon liquid fraction normally boiling between 400-650°F and including a high boiling residuum fraction;
(d) passing the resulting effluent material from said second stage reaction zone to successive phase separation and distillation steps to remove the gas material fraction; and (e) removing unconverted coal and ash solids material and a heavy hydrocarbon bottoms liquid material, recycling a hydrocarbon fraction normally boiling above about 550°F to the coal slurrying step, and thereby producing low-boiling hydrocarbon liquid products normally boiling between 150 and 975°F.
(a) mixing the particulate sub-bituminous coal with sufficient petroleum atmospheric residuum having at least about 90 V% normally boiling above 650°F and containing at least about 20 W% aromatic compounds to provide a flowable slurry mixture, the total petroleum residuum/coal feed weight ratio being between 1Ø/1 and 3/1, with the coal feed being between about 25 and 50 W% of the total hydrocarbon feed material;
(b) feeding the slurry mixture with hydrogen into a first stage back-mixed catalytic reaction zone containing an ebullated catalyst bed of particulate hydrogenation catalyst, said reaction zone having an internal liquid recycle ratio at least about 1:1, said catalyst containing an active metal component wherein the metal in said component is selected from the group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten, and combinations thereof deposited on a support material selected from the group consisting of alumina, magnesia, silica, titania and similar materials, said catalyst bed being maintained at 700-780°F temperature, 1500-3500 psia hydrogen partial pressure and feed rate of 15-75 pounds coal plus petroleum residuum oil per hr per fr3 reactor volume for hydrogenation and hydroconversion reactions to provide lower boilig hydrocarbon materials containing less than 6 W% C1-C3 hydrocarbon gases, 15-25 W% 650-F-light liquid fraction and 60-70- W% 650°F+ hydrocarbonmaterial fraction;
(c) passing the total effluent material from said first stage reaction zone together with additional hydrogen directly to a close-coupled second stage back-mixed catalytic reaction zone so as to avoid forming retrograde materials in the effluent, said catalyst containing an active metal oxide or other metal compound selected from the metals group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten and combinations thereof deposited on a support material selected from the group consisting of alumina, magnesia, silica, titania and similar materials, said second stage zone containing an ebullated catalyst bed maintained at a higher temperature than the first stage reaction zone, and at 780-860°F temperature, and 1500-3500 psig hydrogen partial pressure to hydroconvert the remaining coal and residuum material to hydrocarbon gases, hydrocarbon liquid fraction normally boiling between 400-650°F and including a high boiling residuum fraction;
(d) passing the resulting effluent material from said second stage reaction zone to successive phase separation and distillation steps to remove the gas material fraction; and (e) removing unconverted coal and ash solids material and a heavy hydrocarbon bottoms liquid material, recycling a hydrocarbon fraction normally boiling above about 550°F to the coal slurrying step, and thereby producing low-boiling hydrocarbon liquid products normally boiling between 150 and 975°F.
9. The hydroconversion process of claim 1, wherein a portion of the heavy hydrocarbon bottoms liquid material is recycled to the mixing step.
10. The hydroconversion process of claim 1, wherein said catalyst has a particle size range of 0.030-0.125 inch effective diameter.
11. A two-stage continuous process for catalytic hydroconversion of a fluid blend of a bituminous coal and heavy hydrocarbon liquid, comprising:
(a) mixing a particulate bituminous coal with sufficient heavy hydrocarbon liquid having at least about 90 V% normally boiling above 650°F to provide a flowable slurry mixture; the total hydrocarbon liquid/coal feed weight ratio being between about 1.0/1 and 3/1 with the bituminous coal material being between about 25 and 50 W% of the total feed material;
(b) feeing the flowable slurry mixture with hydrogen into a first stage back-mixed catalytic reaction zone containing an ebullated catalyst bed of particulate hydrogenation catalyst, said reaction zone having an internal liquid recycle ratio of at least about 1:1, said catalyst containing an active metal component wherein the metal in said component is selected from the group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten and mixtures thereof deposited on a support material, said catalyst bed being maintained at 650-800°F temperature, 1000-4000 psig hydrogen partial pressure and feed rate of 10-100 lb carbonaceous material plus heavy hydrocarbon liquid feed per hour per ft3 reaction zone volume for hydrogenation reaction to partially hydrogenate and hydroconvert the feed materials to hydrocarbon gases, 15-25 W% 650°F- light liquid fraction and 60-70 W% 650-F+ hydrocarbon material fraction;
(c) passing the total effluent material from said first stage reaction zone together with additional hydrogen directly to a close-coupled second stage back-mixed catalytic reaction zone containing an ebullated catalyst bed so as to avoid forming retrograde materials in the effluent, said catalyst containing an active metal component wherein the metal in said component is selected from the group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten and mixtures thereof deposited on a support material, said second stage reaction zone being maintained at a higher temperature than the first stage reaction zone, and at 750-900°F temperature and 1000-4000 psig hydrogen partial pressure to convert the remaining unconverted coal to hydrocarbon gases, a hydrocarbon liquid fraction normally boiling between 400-650°F and including a high boiling residuum fraction;
(d) passing the resulting effluent material from said second stage reaction zone to successive phase separation and distillation steps to separate the gas material fraction; and (e) removing unconverted coal and ash solids material and a heavy hydrocarbon liquid bottoms material, recycling a hydrocarbon fraction normally boiling above 550°F to the coal slurrying step, and thereby producing low-boiling hydrocarbon liquid products normally boiling between 150°F and 975°F.
(a) mixing a particulate bituminous coal with sufficient heavy hydrocarbon liquid having at least about 90 V% normally boiling above 650°F to provide a flowable slurry mixture; the total hydrocarbon liquid/coal feed weight ratio being between about 1.0/1 and 3/1 with the bituminous coal material being between about 25 and 50 W% of the total feed material;
(b) feeing the flowable slurry mixture with hydrogen into a first stage back-mixed catalytic reaction zone containing an ebullated catalyst bed of particulate hydrogenation catalyst, said reaction zone having an internal liquid recycle ratio of at least about 1:1, said catalyst containing an active metal component wherein the metal in said component is selected from the group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten and mixtures thereof deposited on a support material, said catalyst bed being maintained at 650-800°F temperature, 1000-4000 psig hydrogen partial pressure and feed rate of 10-100 lb carbonaceous material plus heavy hydrocarbon liquid feed per hour per ft3 reaction zone volume for hydrogenation reaction to partially hydrogenate and hydroconvert the feed materials to hydrocarbon gases, 15-25 W% 650°F- light liquid fraction and 60-70 W% 650-F+ hydrocarbon material fraction;
(c) passing the total effluent material from said first stage reaction zone together with additional hydrogen directly to a close-coupled second stage back-mixed catalytic reaction zone containing an ebullated catalyst bed so as to avoid forming retrograde materials in the effluent, said catalyst containing an active metal component wherein the metal in said component is selected from the group consisting of cobalt, iron, molybdenum, nickel, tin, tungsten and mixtures thereof deposited on a support material, said second stage reaction zone being maintained at a higher temperature than the first stage reaction zone, and at 750-900°F temperature and 1000-4000 psig hydrogen partial pressure to convert the remaining unconverted coal to hydrocarbon gases, a hydrocarbon liquid fraction normally boiling between 400-650°F and including a high boiling residuum fraction;
(d) passing the resulting effluent material from said second stage reaction zone to successive phase separation and distillation steps to separate the gas material fraction; and (e) removing unconverted coal and ash solids material and a heavy hydrocarbon liquid bottoms material, recycling a hydrocarbon fraction normally boiling above 550°F to the coal slurrying step, and thereby producing low-boiling hydrocarbon liquid products normally boiling between 150°F and 975°F.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US72545785A | 1985-04-22 | 1985-04-22 | |
| US725,457 | 1985-04-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1280707C true CA1280707C (en) | 1991-02-26 |
Family
ID=24914644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000506635A Expired - Fee Related CA1280707C (en) | 1985-04-22 | 1986-04-15 | Catalytic two-stage co-processing of coal/oil feedstocks |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH0823019B2 (en) |
| AU (1) | AU581978B2 (en) |
| BE (1) | BE904635A (en) |
| CA (1) | CA1280707C (en) |
| DE (1) | DE3613367C2 (en) |
| ZA (1) | ZA862690B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA862692B (en) * | 1985-04-22 | 1987-03-25 | Hri Inc | Catalytic two-stage coal hydrogenation and hydroconversion process |
| US4874506A (en) * | 1986-06-18 | 1989-10-17 | Hri, Inc. | Catalytic two-stage coal hydrogenation process using extinction recycle of heavy liquid fraction |
| US4816141A (en) * | 1987-10-16 | 1989-03-28 | Hri, Inc. | Catalytic two-stage liquefaction of coal utilizing cascading of used ebullated-bed catalyst |
| CN111876189B (en) * | 2020-07-21 | 2022-09-02 | 中国神华煤制油化工有限公司 | Method for two-stage catalytic direct liquefaction of coal and application thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2444829A1 (en) * | 1974-09-19 | 1976-04-08 | Kabel Metallwerke Ghh | PROCESS FOR THE PRODUCTION OF THERMOPLASTICS OR ELASTOMERS THAT CAN BE CROSSED BY PLUGGING ON A SILANE COMPOUND IN THE PRESENCE OF MOISTURE |
| US4083769A (en) * | 1976-11-30 | 1978-04-11 | Gulf Research & Development Company | Catalytic process for liquefying coal |
| US4110192A (en) * | 1976-11-30 | 1978-08-29 | Gulf Research & Development Company | Process for liquefying coal employing a vented dissolver |
| GB1584583A (en) * | 1976-11-30 | 1981-02-11 | Gulf Research Development Co | Process for extending life of coal liquefaction catalyst |
| US4128471A (en) * | 1976-11-30 | 1978-12-05 | Gulf Research & Development Company | Coal liquefaction process employing carbon monoxide |
| JPS5761082A (en) * | 1980-09-30 | 1982-04-13 | Kobe Steel Ltd | Liquefaction of coal |
| US4495055A (en) * | 1982-04-05 | 1985-01-22 | Hri, Inc. | Coal catalytic hydrogenation process using direct coal slurry feed to reactor with controlled mixing conditions |
| JPS5968391A (en) * | 1982-10-12 | 1984-04-18 | Asahi Chem Ind Co Ltd | Coal liquefaction |
| DE3408095A1 (en) * | 1983-03-07 | 1984-09-20 | HRI, Inc., Gibbsboro, N.J. | Hydrogenation of undissolved coal and subsequent liquefaction of the hydrogenated coal |
| ZA862692B (en) * | 1985-04-22 | 1987-03-25 | Hri Inc | Catalytic two-stage coal hydrogenation and hydroconversion process |
-
1986
- 1986-04-10 ZA ZA862690A patent/ZA862690B/en unknown
- 1986-04-10 AU AU55951/86A patent/AU581978B2/en not_active Ceased
- 1986-04-15 CA CA000506635A patent/CA1280707C/en not_active Expired - Fee Related
- 1986-04-21 BE BE2/60964A patent/BE904635A/en not_active IP Right Cessation
- 1986-04-21 DE DE3613367A patent/DE3613367C2/en not_active Expired - Fee Related
- 1986-04-22 JP JP61091399A patent/JPH0823019B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| DE3613367A1 (en) | 1986-10-30 |
| ZA862690B (en) | 1988-11-30 |
| JPH0823019B2 (en) | 1996-03-06 |
| AU5595186A (en) | 1986-10-30 |
| BE904635A (en) | 1986-08-18 |
| DE3613367C2 (en) | 1994-03-17 |
| AU581978B2 (en) | 1989-03-09 |
| JPS61247790A (en) | 1986-11-05 |
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