CA1107213A - Liquefaction of coal in a non-hydrogen donor solvent - Google Patents
Liquefaction of coal in a non-hydrogen donor solventInfo
- Publication number
- CA1107213A CA1107213A CA283,028A CA283028A CA1107213A CA 1107213 A CA1107213 A CA 1107213A CA 283028 A CA283028 A CA 283028A CA 1107213 A CA1107213 A CA 1107213A
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- CA
- Canada
- Prior art keywords
- hydrogen
- coal
- mixture
- metal compound
- soluble metal
- 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.)
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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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
-
- 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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
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- 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 catalytically liquefying coal to produce coal liquids is effected by forming a mixture of an oil soluble metal compound, a non-hydrogen donor solvent and coal, converting the compound to a catalyst within said mixture and reacting the mixture with hydrogen. The recovered solvent may be recycled to the liquefaction zone. Preferred compounds are molybdenum compounds.
A process for catalytically liquefying coal to produce coal liquids is effected by forming a mixture of an oil soluble metal compound, a non-hydrogen donor solvent and coal, converting the compound to a catalyst within said mixture and reacting the mixture with hydrogen. The recovered solvent may be recycled to the liquefaction zone. Preferred compounds are molybdenum compounds.
Description
2 1. Field o~ ~he I~vention -
3 This invention relates to a process for l-L~uefyillg
4 coal in a non-hy~rogen donor solvent to li~uid hy~roc~ on products ln the presence of a catalyst prepared in situ 6 rom a small amount of metals added to the mixture of coal 7 and solvent as oil soluble metal compounds.
8 20 Descript~on of th~ Prior Art .. . _ 9 Liquefaction of coal to coal liquids in a hydrogen donor solvent process is well known. In such a process, a 11 slurry of coal ln a h~drogen donor solvent is reacted in the 12 presence of molecular hydrogen at elevated temperature and 13 pressure. The hy~rogen donor solvent which becomes hydrogen 14 depleted during the coal liquefactîon reaction, in th~
prior art processes~ is generally subjected to a hydrogen~
16 ation stage prior to its being recycled to the liquefaction -17 zone.
18 It is also known to convert coal to liquid produc~s 19 by hydrogenation of coal which has been impregnated with an oil-soluble metal naphthenate or by hydrogenation of 21 coal in a liquid rnedium such as a hydrogen donor oil having 22 a boiling range of 250 to 325C. containing an oil-soluble 23 metal naphthenate. Concentrations as low as 0.01% metal 24 naphthenate catalysts, calculated as the metal, were folmd to be effective for the conversion of coal.
26 A process is known for the liquefaction of su~-27 bituminous coal in a hydrogen donor oil in the presence of 28 hydrogen, carbon monoxide, water, and an alkali metal or 29 ammonium molybdate in an amount ranging from 0.5 to lO
percent by weight of the coal.
, :llV7Z13 t It has now been found that when the coal lique-2 fac~ion reaction is conducted in the presence of a minor 3 amount of a catalyst produced from an added oil soluble metal compo~md, effective liquefactio~ of coal wlth molecu~
hydrogen will occur when a non~hydrogen donor solvent is 6 used. Furthermore, the non hydrogen donor solvent can be 7 recycled to the liquefaction zone without intervening 8 hydrogellation. Therefore, utiliza~ion of a nonQhydrogen 9 donor solven~ eliminates the need for an external solvent hydrogenation stage, such as is generally used in conven-11 tional coal hydrogen donor solvent liquefaction processes.
12 Additional advant~ges in the utilization of oil-13 soluble metal compounds in a non~hydrogen donor solvent 14 coal liquefaction process will become apparent in the following description.
16 The term "hydroconversion" with reference to coal 17 is used herein to designate conversion of coal to liquid hydrocarbons in the presence of hydrogen.
In accordance with the invention, there is 21 provided, a process for liquefying coal to produce an oil, 22 which comprises the steps of: (a) forming a mixture o~
23 coal, a non-hydrogen donor solvent and an added oil soluble 24 metal compound, said ~etal being selected from the group consisting of Groups VB, VIB, VIIB and VIII of the Periodic 26 Table of Elements and mixtures thereof, (b) converting said 27 oil-soluble compound to a catalyst within said mixture in 28 the presence of a hydrogen~containing gas;(c)n~ct~gthe re~ng 29 mixture with a gas comprising molecular hydrogen under coal ~ llquefaction conditions, in a liquefaction zone, and (d) . .. . ... . ,,, . ., ~
' ~ 1~ 7 ~ ~ 3 I recovering a coal liquefaction product mixture comprising 2 an oil product and solids o 3 In accol-dance with another embodimer,t of ~he 4 invention~ there is provicied a process for liquefying coal to produce an oil, which comprises: (a) forming a mixture 6 of wet coal, a non-hydrogen donor solvent and an ~dded oil-7 soluble metal ccmpound, said oil~soluble metal compound 8 being added in an amount ranging from about 10 to about 700 ~ wppm, calculated as the elemental metal, based on the weight of coal in said mixture, said metal being selected from the ll group consisting of Groups VB, VIB, VIIB and VIII of the 12 Periodic Table of Elements and mixtures thexeo~; (b) con l3 verting said oil~soluble metal compound to a catalyst within l4 said mixture in the presence of a hydrogen-containing gas;
(c) reacting the resulting mixture containing said catalyst 6 with a gas comprising hydrogen and from about 5 to about 50 17 mole percen~ carbon monoxide, under coal liquefaction 18 conditions, in a liquefaction zone; and (d) recovering a l9 coal liquefaction product mixture compri~ing an oil product and solids.
21 BRIEF DESCRIPTION OF T~E DRAWINGS
22 Figure 1 is a schematic flow plan of one em~odiment 23 of the invention~
24 Figure 2 is a schema~ic flow plan of another embodiment of the inventionO
26 ~ESCRIPTION OF THE PREFER~ED RMBODIMENTS
27 The process of the invention is generally applica-28 ble to hydroconvert coal to produce coal liquids (i.e.
normally liquid hydrocarbon products) in a non-hydrogen donor solvent process. The term "coal" is used herein to designate ,, 11~7Z13 a nor~ally solid ca~bonaceous material including all. ranks 2 of coal, SUCll as an~hracite coal, bituminous coal, semi-3 bituminous coal, subbituminous coal~ ~ignite, peat and 4 mixtures thereof.
In the process shown in Figure 1, the coal, in 6 particulate form, of a size ranging up to about 1/8 inch 7 particle size diameter, suitably 8 mesh (Tyler) is intro-8 duced by line 10 into a mixing zone 12 in which it is 9 mixed with a non hydrogen donor solvent introduced by line 14. The solvent and coal are admixed in a solvent-to-ll coal weight ratio ranging from about 0.8:1 to 4:1~ preferably 12 from about 1:1 to 2:1.
l3 The non-hydrogen donor solvents employed in the 1~ proress of ~he presen~ invention are solvents which contain less than 0.8 weight percent donatable hydrogen, based o~
l6 ~he weight of the total solvent. Preferably~ the solvent 17 will be a non-hydrogen donor compound or mixture of compounds 18 having an atmospheric boiling point ranging from about 350~.
19 to about 850F , more preferably ranging from about 350F.
to less than about 650F. Suitable non-hydrogen donor sol-21 vents include aromatic compounds such as aLkylbenzenes, alkyl 22 naphthalenesJ alkylated polycyclic aromatics, heteroaromatics 23 and mixtures thereof, etc., and streams such as unhydro-24 genated creosote oil, intermediate product streams from catalytic cracking of petroleum feedstocks, coal derived 26 liquids, shale oil and the like. An oil-soluble metal 27 compQund wherein the metal is selected from the group 2~ consisting of Groups VB, VIB, VIIB, VIII and mixtures 29 thereof of the Periodic Table of Elements is added to the ~ non-hydrogen donor solvent by line 16 so as to form a ; ~
~ mlxture of oil soluble metal compound3 ~on-hydrogen dorlor z solvent and coal in mixing zone 12. The oil-soluble metal 3 compound is added in an amount su~ficient to provide rom 4 about 10 to less than 2000 wppm) preferab~y from about 25 to 950 wpp~ more preferably, from about 50 to 7~0 wppm, 6 most preferably ~rom about 50 to 400 wppm, of the oil-7 soluble metal compound9 calculated as the elemental metal, ~ ~ based on the weight of coal in the mixture.
9 Suitable oil-soluble met~l compounds convertible to active catalysts under procPss conditions include (1) ll inorganic metal compounds such as halides, oxyhalides, 12 hydrated oxides, heteropoly acids (e~g. phosphomolybdic 13 acid, molybdosilisic acid), (2) metal salts of organic 14 ac~ds such as acyelic and alicyclic aliphatic carboxylic lS acids containing two or more carbon atoms (eOg. naphthenic 16 acids); aromatic carboxylic acids (eOg. toluic acid);
17 sul~onic acids (e.g. toluenesulfonic acid), sulfinic acids;
18 mercaptans9 xanthic acid9 phenols, di and polyhydroxy 19 aromatic compounds, (3) organometallic eompounds such .~s metal chelates, e.g~ with 1~3~diketone.~, ethylene diamine, 2l ethylene diamine tetraacetic acld, etc., 22 (4) metal salts of organic amines such as aliphAtic amines, 23 aromatic amines9 and quaternary ammonium compoundsO
24 `The metal constituent of the oil soluble metal compound is selected frcm the group consisting of Groups ?6 VB, VIB9 VIIB and VIII of the Periodic Table of Elements, 27 and mixtures thereof, in accordance with the table pub-28 lished by E. H. Sargent and Company, copyright 1962, Dyna Slide Company, that is, vanadium, niobium~ tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ' li~7213 1 cobalt, nickel and the noble metals including platinum, 2 iridium, pall~dium, osmium, ruthenium and rhodium. Tne 3 preferred metal consti~uent of the oil soluble metal 4 c~mpound is sel.ected from the gro~p consisting of molybdenum5 S vanadium an~ chromium. More preferably, the metal constit-6 uent of the oi~ soluble metal compound is selected from the 7 group consisting of molybdenum and chromium. Most prefer-8 ably, the metal constituent of the oil soluble metal compound 9 is molybdenum. Preferred compounds of the metals include lo the salts of acyclic (straight or branched chain) aliphatic 11 carboxylic acids, ~alts of alicyclic aliphatic carboxylic 12 acids, heteropslyacids; hydrated oxldes, carbonyls, phenolates 13 andorganic amine saltsO More preferred types of metal com~
14 pounds are the heteropoly acids, e.g. phosphomolybd~c aeid.
lS Another preferred metal compound is a salt of an alicyclic 16 aliphatic carboxylic acid guch a~ a metal naphthena~e~
17 The most preferred compounds are molybdenum naphthenate, 18 vanadium naphthenate and chromil~n naphthenate.
19 When the oil~soluble metal compound is added to the non-hydrogen doncr solventy lt dissolves in the solvent.
21 To fo~m the catalystD the metal compound ~catalyst precursor) 22 is converted within the slurry of coal and non~hydrogen 23 donor solvent.
24 Various methods can be used to convert the dis-solved metal compound in the coal~solvent slurry to an 26 active catalys~. A preferred method (pretreatment method) 27 of fonming the catalyst rom the oil~solubLe compound af 28 the present invention is to heat the mixture of metal compound, coal and solvent to a temperature ranging from about 325C. to about 438C. and at a pressure ranging .
-l i~ 7 ~ 1 3 l from about 500 to about 5000 psig, in the presence of a 2 hydrogerl-c~n~aining gas. The hyd~ogen-containi.rlg gas .~ay 3 be pure hydrogen but will generally be a hydrogen stream 4 co;ltaining some other gaseous contaminants9 for example, the hydrogen~containing effluent produced in reforming 6 processes, e~c.
7 Preferably the hydrogen-containing gas also comprises hydrogen sulfide. The hydrogen sulfide may com-9 prise from about 1 to about 90 mole percent, preferably from about 1 to about 50 mole percent D more prefera~ly from ll about 1 to 30 mole percent of the hydrogen~containing gas 12 mixture. The pretreatment is conducted for a period ranging l3 from about ~ min~tes to about 2 hours9 preferably for a 14 period ranging from about 10 minut~ to about 1 hour. The thermal treatment in the presence of hydrogen or in the 16 presence of hydrogen and hydrogen sulfide iæ believed to 7 facilitate conversion of the metal compound to the corre-18 sponding metal~containing active cataiysts which act also 19 as coking inhibitors.
The coal-solvent slurry containing the resulting 21 catalyst is then introduced into a coal liquefaction zone 22 which will be subsequently described.
23 Another method of con~erting the oil~soluble me~al 24 compound of the present invention is to react the mixture of metal compound, coal and non~hydrogen donor solvent with a 26 ~ydrogen-containing gas at coal liquefaction conditions to 2~ produce a catalyst in the chargestock, in situ, in the 28 liquefaction zone. The hydrogen~containing gas may comprise 29 from about 1 to about 30 mole percent hydrogen sul~ide.
Whatever the exact nature o~ the resulting con- ~-~1072~3 I version products of the givell oil~soluble m~tal compound, 2 the resulting metal componen~ ls a catalytic agent and a 3 coking inhibitor.
4 In the process shown in Figure 1, the mixture of oil~soluble metal compound9 a non hydrogen donor solvPnt, such as alpha methylnaphthalene, and coal is removed from 7 mixing zone 12 by line 18 and introduced into pretreatment 8 zone 13 into wllich a gaseous mlxture comprising hydrogen and 9 from about 1 to about 90 mole percent, preferably from about 1 to 50 mole percent, more preferably from about 1 to 30 ll mole percellt hydrogen sulfide is introduced by line 15. The 12 pretreatment zone is maintained at a temperature ranging 13 from about 342C. to about 415C. and at a total pressure 14 ranging from about 500 to abou~ 5000 psig. The pretreatment is conducted for a period of time ran~ing from about lO
16 minutes to about 1 hourO The pretreatment zone effluent 17 i8 removed by line l9o If desired, a-portion of the hydrogen 18 sulfide may be removed from the effluent. The pretreatment 19 zcne effluent is introdu~ed ~y line 19 into li~uefaction reactor 22. A hydrogen~containing gas is introduced into 21 liquefaction reactor 22 by Line 200 The hydrogen-containing 22 gas may be pure hydrogen but will generally be a hydrogen 23 stream containing some other gaseous contaminants 9 for 24 example, the hydrogen~contailling effluent produced in reorming. Suitable hydrogen~¢ontaining gas mixtures for 26 introduction into the liquefaction zone include raw synthesis 27 gas 9 that isS a gas containing hydrogen and from about 5 to 2g about 50, preerably rom about 10 to 30 mole pereent carbon 29 monoxide.
When wet coal (iOe. coal particles associated with _ g _ .
11'~7Z13 i !
1 water) is u~ilized as feed, it is particularly desirable to 2 utilize a raw syr.Ehes~s gas, ~hæt is~ a gas comprising 3 hydrogen and carbon monoxide. In such an embodiment9 the 4 metal compound, pre~erably a ~.etal~containing organic compound, is added in an amount ranging from 10 to 700 wppm, ~ preferably from 50 to 500 wppm, calculated as t~e element~l 7 metal9 based on the coal alone~ The gas introduced by line 8 20 may additionally contain hydrogen sulfide in an amount 9 ranging from about 1 to 30 mole percent.
o The coal liquefaction zone is maintained at a 11 temperature ranging from about 343 to 538C. (649.4 to 12 lOOO~F.)J preferably from about 416 to 468C. (780.~ to 13 89g.~F.), more preferably from about 440 to 468C. (824 to 14 875F.), and a hydrogen partial pressure ranging from about 500 psig to about 5000 p5ig~ preferably from about 1000 to 16 about 3000 psig. The space velocity, defined as volumes of 17 the mixture of coal and solvent feedstock per hour per ~olume 18 of reac~or (V/Hr./V), may vary widely depending on the 19 desired conversion level. Suitable 8pace velocities may range broadly from about 0.1 to 10 volumes feed per hour per 21 volume of reactor, preferably from about 0025 to 6 VlHr./~, 22 more preferably from about O.S to 2 VIHr./V. The coal lique-23 faction zone effluent is removed from t.he zone by line 24.
24 The effluent comprises gases, an oil product and a solid residue which is cataly~ic in nature. The ef1uent 26 is passed to a separation zone 26 from wh~ch gases are 27 removed overhead by line 28. This gas may be scrubbed by 28 conventional methods to remove any undesired amount of 29 hydrogen sulfide and carbon dioxide and thereafter it may ~ be recycled into the coal liquefaction zone. The solids may 1 be separated from ~he oil product by conventional means, 2 for example, by settling or centrifuging or filtration of 3 the oil-solids slurry. The separated solids are removed 4 from separ~tion zone 26 by lin~ 30~ If desired at least a portion of the separated solids or solids concentrate may 6 be recycled direc~ly to the coal liquefaction æone via line 7 31 or recycled to the coal-solvent chargestock.
8 The remaining portion of solids removed by line 9 30 may be`discarded as such since normally ~hey do not contain economically recoverable amounts of char. The oil 11 produc~ is removed rom separation zone 26 by line 32 and 12 passed to a fracti.onation zone 34 wherein a light fraction 13 boiling below about 400Fo (204~44Co) is recovered by line .~ 14 36. A heavy fraction is removed by line 38 and a.n inter- :
mediate range boiling fraction, that is, a raction boiling 16 from about 400 to about 700F~ (204044 to 371~11Co) at 17 atmospheric pressure, including the non~hydrogen donor 18 solvent, is recovered by line 40O In a preferred embodiment 19 of the present invention9 at ieast a portion of the inter-mediate fraction having less than 008 weight percent 21 donatable hydrogen, which includes the recovered non-hydrogen 22 donor solvent, is recycled via line 42, without any inter-23 vening rehydrogenation9 into mixing zone 12 or directly into 24 the coal liquefaction zone.
It should also be noted that in non-catalyzed 26 hydrogen donor coal liquefactio~. processes, ~the heavy 27 bottoms product resulting from fractional distillation of 28 the coal liquefaction oil product contains solids. The 29 solids-containing heavy bottom~ f~action is typically sub-3~ jected to a fluid coking operation since a substantial -1~07Z13 1 po~tion of the carbon of the chargestock emerges with the 2 solids in the form of char that must be recovered. In 3 contrast, in the process of the present invention, ~ince . 4 the solid residue of the liquefaction zone does not eontain any significa1lt amou.nt of char, the solids can be separated 6 from the coal liquefaction zone effluent by known means and 7 discarded or used as catalyst. The process of the present 8 invention would permit the elimination of the coking step~
9 Figure 2 shows various process options fox treating the coal liquefaction zone effluent which is removed from 11 the.coal liquefaction reactor 22 by line 24. The effluent 12 is introduced into a gas-liquid separator 26 where hydrogen 13 and light hydrocarbon~s are removed overhead by line 28.
14 Three preferred process options are available for the liquid stream containing dispersed catalyst solids which emerge 16 from separator vessel 26 via line 30.
17 In process optlon to be designated 'IA", the liqui~-18 solids stream is fed by line 32 to concentration zone 34 19 where by means, for example, of distilla~ion, solid precip-.20 itation or centrifugation, the ~tream i8 ~epara~ed into a 21 clean liquid product, which is withdrawn through li.ne 36, 22 and a concentrated slurry (e.g. 20 to 40 percent by weight) 23 in oil. At least a portion of the concentrated slurry can 24 be re ved as a purge stream through line 38 to control the buildup of solid materials in the coal liquefaction reactor, 26 and the balance of the slurry is returned by line 40 and . 27 line 30 to liquefaction reac~or 220 The purge stream may ~ be filtered subsequently to recover c~alyst and liquid product or it can be burned or gasified.to provide, respec-tively, heat and hydrogen for the pr3cess.
7~ 1 3 1 In the process option to be designated "B", the 2 purge stream from concen~ration zone 34 is omitted and the 3 entire slurry concentrate withdr~wn through line 40 i~ fed to separation zone 44 via lines 30 an.d 42. In thi.s æone, a major por~.ion of the remaining ll~uid phase is separated 6 from the solids by means of centrifugation, filtration or 7 a combination of settling and drawoff 9 etc.. Liquid is 8 removed from ~he ~one through line 46 and solids through line 48~. At least a portion of the solids and associated o remaining liquid are purged from the process vi.a line 50 to ll control the buildup of solids in the process and the balance 12 of the solids ~s recycled to liquefaction reactor 22 via line 52 which connects to recycle line 30. The solids can be recycled either as recovered or after suitable cleanup (not shown) to remove heavy adhering oil deposits and coke.
16 In option designated "C", the slurry of solids in 17 oi. exiting fro~ separator 26 via line 30 is fed direc~ly 18 to separation zone 44 by way of line 42 whereupon solids l9 and liquid product are separated by means of centrifugation or filtration. All or part of the solids exi~ing from 21 vessel 44 via line 48 may be purged fronn the process through 22 line 50 and the remainder recycled to ~he liquefac~ion 23 reactor. Liquid product is recovered through line 46. If 24 ~esired, at least a portion o the heavy fraction of the hydroconverted oil product may be recycled to ~he coal 26 liquefaction zone.
27 The process of the invention may be conducted 28 either ~s a batch or as 8 continuous ~ype proceæs~
29 The following ex~mple i~ presen~ed to illustrate the invention.
. - 13 -llV7Z13 2 C.ompar~ti-~e e~perlmen~.s.were made ln which molyb-3 denum naphthenate was u~llized as ¢atal~3t precursor in a 4 non~hydrogen donor sol~vent9 tha~ is~ in alpha meth~l-
8 20 Descript~on of th~ Prior Art .. . _ 9 Liquefaction of coal to coal liquids in a hydrogen donor solvent process is well known. In such a process, a 11 slurry of coal ln a h~drogen donor solvent is reacted in the 12 presence of molecular hydrogen at elevated temperature and 13 pressure. The hy~rogen donor solvent which becomes hydrogen 14 depleted during the coal liquefactîon reaction, in th~
prior art processes~ is generally subjected to a hydrogen~
16 ation stage prior to its being recycled to the liquefaction -17 zone.
18 It is also known to convert coal to liquid produc~s 19 by hydrogenation of coal which has been impregnated with an oil-soluble metal naphthenate or by hydrogenation of 21 coal in a liquid rnedium such as a hydrogen donor oil having 22 a boiling range of 250 to 325C. containing an oil-soluble 23 metal naphthenate. Concentrations as low as 0.01% metal 24 naphthenate catalysts, calculated as the metal, were folmd to be effective for the conversion of coal.
26 A process is known for the liquefaction of su~-27 bituminous coal in a hydrogen donor oil in the presence of 28 hydrogen, carbon monoxide, water, and an alkali metal or 29 ammonium molybdate in an amount ranging from 0.5 to lO
percent by weight of the coal.
, :llV7Z13 t It has now been found that when the coal lique-2 fac~ion reaction is conducted in the presence of a minor 3 amount of a catalyst produced from an added oil soluble metal compo~md, effective liquefactio~ of coal wlth molecu~
hydrogen will occur when a non~hydrogen donor solvent is 6 used. Furthermore, the non hydrogen donor solvent can be 7 recycled to the liquefaction zone without intervening 8 hydrogellation. Therefore, utiliza~ion of a nonQhydrogen 9 donor solven~ eliminates the need for an external solvent hydrogenation stage, such as is generally used in conven-11 tional coal hydrogen donor solvent liquefaction processes.
12 Additional advant~ges in the utilization of oil-13 soluble metal compounds in a non~hydrogen donor solvent 14 coal liquefaction process will become apparent in the following description.
16 The term "hydroconversion" with reference to coal 17 is used herein to designate conversion of coal to liquid hydrocarbons in the presence of hydrogen.
In accordance with the invention, there is 21 provided, a process for liquefying coal to produce an oil, 22 which comprises the steps of: (a) forming a mixture o~
23 coal, a non-hydrogen donor solvent and an added oil soluble 24 metal compound, said ~etal being selected from the group consisting of Groups VB, VIB, VIIB and VIII of the Periodic 26 Table of Elements and mixtures thereof, (b) converting said 27 oil-soluble compound to a catalyst within said mixture in 28 the presence of a hydrogen~containing gas;(c)n~ct~gthe re~ng 29 mixture with a gas comprising molecular hydrogen under coal ~ llquefaction conditions, in a liquefaction zone, and (d) . .. . ... . ,,, . ., ~
' ~ 1~ 7 ~ ~ 3 I recovering a coal liquefaction product mixture comprising 2 an oil product and solids o 3 In accol-dance with another embodimer,t of ~he 4 invention~ there is provicied a process for liquefying coal to produce an oil, which comprises: (a) forming a mixture 6 of wet coal, a non-hydrogen donor solvent and an ~dded oil-7 soluble metal ccmpound, said oil~soluble metal compound 8 being added in an amount ranging from about 10 to about 700 ~ wppm, calculated as the elemental metal, based on the weight of coal in said mixture, said metal being selected from the ll group consisting of Groups VB, VIB, VIIB and VIII of the 12 Periodic Table of Elements and mixtures thexeo~; (b) con l3 verting said oil~soluble metal compound to a catalyst within l4 said mixture in the presence of a hydrogen-containing gas;
(c) reacting the resulting mixture containing said catalyst 6 with a gas comprising hydrogen and from about 5 to about 50 17 mole percen~ carbon monoxide, under coal liquefaction 18 conditions, in a liquefaction zone; and (d) recovering a l9 coal liquefaction product mixture compri~ing an oil product and solids.
21 BRIEF DESCRIPTION OF T~E DRAWINGS
22 Figure 1 is a schematic flow plan of one em~odiment 23 of the invention~
24 Figure 2 is a schema~ic flow plan of another embodiment of the inventionO
26 ~ESCRIPTION OF THE PREFER~ED RMBODIMENTS
27 The process of the invention is generally applica-28 ble to hydroconvert coal to produce coal liquids (i.e.
normally liquid hydrocarbon products) in a non-hydrogen donor solvent process. The term "coal" is used herein to designate ,, 11~7Z13 a nor~ally solid ca~bonaceous material including all. ranks 2 of coal, SUCll as an~hracite coal, bituminous coal, semi-3 bituminous coal, subbituminous coal~ ~ignite, peat and 4 mixtures thereof.
In the process shown in Figure 1, the coal, in 6 particulate form, of a size ranging up to about 1/8 inch 7 particle size diameter, suitably 8 mesh (Tyler) is intro-8 duced by line 10 into a mixing zone 12 in which it is 9 mixed with a non hydrogen donor solvent introduced by line 14. The solvent and coal are admixed in a solvent-to-ll coal weight ratio ranging from about 0.8:1 to 4:1~ preferably 12 from about 1:1 to 2:1.
l3 The non-hydrogen donor solvents employed in the 1~ proress of ~he presen~ invention are solvents which contain less than 0.8 weight percent donatable hydrogen, based o~
l6 ~he weight of the total solvent. Preferably~ the solvent 17 will be a non-hydrogen donor compound or mixture of compounds 18 having an atmospheric boiling point ranging from about 350~.
19 to about 850F , more preferably ranging from about 350F.
to less than about 650F. Suitable non-hydrogen donor sol-21 vents include aromatic compounds such as aLkylbenzenes, alkyl 22 naphthalenesJ alkylated polycyclic aromatics, heteroaromatics 23 and mixtures thereof, etc., and streams such as unhydro-24 genated creosote oil, intermediate product streams from catalytic cracking of petroleum feedstocks, coal derived 26 liquids, shale oil and the like. An oil-soluble metal 27 compQund wherein the metal is selected from the group 2~ consisting of Groups VB, VIB, VIIB, VIII and mixtures 29 thereof of the Periodic Table of Elements is added to the ~ non-hydrogen donor solvent by line 16 so as to form a ; ~
~ mlxture of oil soluble metal compound3 ~on-hydrogen dorlor z solvent and coal in mixing zone 12. The oil-soluble metal 3 compound is added in an amount su~ficient to provide rom 4 about 10 to less than 2000 wppm) preferab~y from about 25 to 950 wpp~ more preferably, from about 50 to 7~0 wppm, 6 most preferably ~rom about 50 to 400 wppm, of the oil-7 soluble metal compound9 calculated as the elemental metal, ~ ~ based on the weight of coal in the mixture.
9 Suitable oil-soluble met~l compounds convertible to active catalysts under procPss conditions include (1) ll inorganic metal compounds such as halides, oxyhalides, 12 hydrated oxides, heteropoly acids (e~g. phosphomolybdic 13 acid, molybdosilisic acid), (2) metal salts of organic 14 ac~ds such as acyelic and alicyclic aliphatic carboxylic lS acids containing two or more carbon atoms (eOg. naphthenic 16 acids); aromatic carboxylic acids (eOg. toluic acid);
17 sul~onic acids (e.g. toluenesulfonic acid), sulfinic acids;
18 mercaptans9 xanthic acid9 phenols, di and polyhydroxy 19 aromatic compounds, (3) organometallic eompounds such .~s metal chelates, e.g~ with 1~3~diketone.~, ethylene diamine, 2l ethylene diamine tetraacetic acld, etc., 22 (4) metal salts of organic amines such as aliphAtic amines, 23 aromatic amines9 and quaternary ammonium compoundsO
24 `The metal constituent of the oil soluble metal compound is selected frcm the group consisting of Groups ?6 VB, VIB9 VIIB and VIII of the Periodic Table of Elements, 27 and mixtures thereof, in accordance with the table pub-28 lished by E. H. Sargent and Company, copyright 1962, Dyna Slide Company, that is, vanadium, niobium~ tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ' li~7213 1 cobalt, nickel and the noble metals including platinum, 2 iridium, pall~dium, osmium, ruthenium and rhodium. Tne 3 preferred metal consti~uent of the oil soluble metal 4 c~mpound is sel.ected from the gro~p consisting of molybdenum5 S vanadium an~ chromium. More preferably, the metal constit-6 uent of the oi~ soluble metal compound is selected from the 7 group consisting of molybdenum and chromium. Most prefer-8 ably, the metal constituent of the oil soluble metal compound 9 is molybdenum. Preferred compounds of the metals include lo the salts of acyclic (straight or branched chain) aliphatic 11 carboxylic acids, ~alts of alicyclic aliphatic carboxylic 12 acids, heteropslyacids; hydrated oxldes, carbonyls, phenolates 13 andorganic amine saltsO More preferred types of metal com~
14 pounds are the heteropoly acids, e.g. phosphomolybd~c aeid.
lS Another preferred metal compound is a salt of an alicyclic 16 aliphatic carboxylic acid guch a~ a metal naphthena~e~
17 The most preferred compounds are molybdenum naphthenate, 18 vanadium naphthenate and chromil~n naphthenate.
19 When the oil~soluble metal compound is added to the non-hydrogen doncr solventy lt dissolves in the solvent.
21 To fo~m the catalystD the metal compound ~catalyst precursor) 22 is converted within the slurry of coal and non~hydrogen 23 donor solvent.
24 Various methods can be used to convert the dis-solved metal compound in the coal~solvent slurry to an 26 active catalys~. A preferred method (pretreatment method) 27 of fonming the catalyst rom the oil~solubLe compound af 28 the present invention is to heat the mixture of metal compound, coal and solvent to a temperature ranging from about 325C. to about 438C. and at a pressure ranging .
-l i~ 7 ~ 1 3 l from about 500 to about 5000 psig, in the presence of a 2 hydrogerl-c~n~aining gas. The hyd~ogen-containi.rlg gas .~ay 3 be pure hydrogen but will generally be a hydrogen stream 4 co;ltaining some other gaseous contaminants9 for example, the hydrogen~containing effluent produced in reforming 6 processes, e~c.
7 Preferably the hydrogen-containing gas also comprises hydrogen sulfide. The hydrogen sulfide may com-9 prise from about 1 to about 90 mole percent, preferably from about 1 to about 50 mole percent D more prefera~ly from ll about 1 to 30 mole percent of the hydrogen~containing gas 12 mixture. The pretreatment is conducted for a period ranging l3 from about ~ min~tes to about 2 hours9 preferably for a 14 period ranging from about 10 minut~ to about 1 hour. The thermal treatment in the presence of hydrogen or in the 16 presence of hydrogen and hydrogen sulfide iæ believed to 7 facilitate conversion of the metal compound to the corre-18 sponding metal~containing active cataiysts which act also 19 as coking inhibitors.
The coal-solvent slurry containing the resulting 21 catalyst is then introduced into a coal liquefaction zone 22 which will be subsequently described.
23 Another method of con~erting the oil~soluble me~al 24 compound of the present invention is to react the mixture of metal compound, coal and non~hydrogen donor solvent with a 26 ~ydrogen-containing gas at coal liquefaction conditions to 2~ produce a catalyst in the chargestock, in situ, in the 28 liquefaction zone. The hydrogen~containing gas may comprise 29 from about 1 to about 30 mole percent hydrogen sul~ide.
Whatever the exact nature o~ the resulting con- ~-~1072~3 I version products of the givell oil~soluble m~tal compound, 2 the resulting metal componen~ ls a catalytic agent and a 3 coking inhibitor.
4 In the process shown in Figure 1, the mixture of oil~soluble metal compound9 a non hydrogen donor solvPnt, such as alpha methylnaphthalene, and coal is removed from 7 mixing zone 12 by line 18 and introduced into pretreatment 8 zone 13 into wllich a gaseous mlxture comprising hydrogen and 9 from about 1 to about 90 mole percent, preferably from about 1 to 50 mole percent, more preferably from about 1 to 30 ll mole percellt hydrogen sulfide is introduced by line 15. The 12 pretreatment zone is maintained at a temperature ranging 13 from about 342C. to about 415C. and at a total pressure 14 ranging from about 500 to abou~ 5000 psig. The pretreatment is conducted for a period of time ran~ing from about lO
16 minutes to about 1 hourO The pretreatment zone effluent 17 i8 removed by line l9o If desired, a-portion of the hydrogen 18 sulfide may be removed from the effluent. The pretreatment 19 zcne effluent is introdu~ed ~y line 19 into li~uefaction reactor 22. A hydrogen~containing gas is introduced into 21 liquefaction reactor 22 by Line 200 The hydrogen-containing 22 gas may be pure hydrogen but will generally be a hydrogen 23 stream containing some other gaseous contaminants 9 for 24 example, the hydrogen~contailling effluent produced in reorming. Suitable hydrogen~¢ontaining gas mixtures for 26 introduction into the liquefaction zone include raw synthesis 27 gas 9 that isS a gas containing hydrogen and from about 5 to 2g about 50, preerably rom about 10 to 30 mole pereent carbon 29 monoxide.
When wet coal (iOe. coal particles associated with _ g _ .
11'~7Z13 i !
1 water) is u~ilized as feed, it is particularly desirable to 2 utilize a raw syr.Ehes~s gas, ~hæt is~ a gas comprising 3 hydrogen and carbon monoxide. In such an embodiment9 the 4 metal compound, pre~erably a ~.etal~containing organic compound, is added in an amount ranging from 10 to 700 wppm, ~ preferably from 50 to 500 wppm, calculated as t~e element~l 7 metal9 based on the coal alone~ The gas introduced by line 8 20 may additionally contain hydrogen sulfide in an amount 9 ranging from about 1 to 30 mole percent.
o The coal liquefaction zone is maintained at a 11 temperature ranging from about 343 to 538C. (649.4 to 12 lOOO~F.)J preferably from about 416 to 468C. (780.~ to 13 89g.~F.), more preferably from about 440 to 468C. (824 to 14 875F.), and a hydrogen partial pressure ranging from about 500 psig to about 5000 p5ig~ preferably from about 1000 to 16 about 3000 psig. The space velocity, defined as volumes of 17 the mixture of coal and solvent feedstock per hour per ~olume 18 of reac~or (V/Hr./V), may vary widely depending on the 19 desired conversion level. Suitable 8pace velocities may range broadly from about 0.1 to 10 volumes feed per hour per 21 volume of reactor, preferably from about 0025 to 6 VlHr./~, 22 more preferably from about O.S to 2 VIHr./V. The coal lique-23 faction zone effluent is removed from t.he zone by line 24.
24 The effluent comprises gases, an oil product and a solid residue which is cataly~ic in nature. The ef1uent 26 is passed to a separation zone 26 from wh~ch gases are 27 removed overhead by line 28. This gas may be scrubbed by 28 conventional methods to remove any undesired amount of 29 hydrogen sulfide and carbon dioxide and thereafter it may ~ be recycled into the coal liquefaction zone. The solids may 1 be separated from ~he oil product by conventional means, 2 for example, by settling or centrifuging or filtration of 3 the oil-solids slurry. The separated solids are removed 4 from separ~tion zone 26 by lin~ 30~ If desired at least a portion of the separated solids or solids concentrate may 6 be recycled direc~ly to the coal liquefaction æone via line 7 31 or recycled to the coal-solvent chargestock.
8 The remaining portion of solids removed by line 9 30 may be`discarded as such since normally ~hey do not contain economically recoverable amounts of char. The oil 11 produc~ is removed rom separation zone 26 by line 32 and 12 passed to a fracti.onation zone 34 wherein a light fraction 13 boiling below about 400Fo (204~44Co) is recovered by line .~ 14 36. A heavy fraction is removed by line 38 and a.n inter- :
mediate range boiling fraction, that is, a raction boiling 16 from about 400 to about 700F~ (204044 to 371~11Co) at 17 atmospheric pressure, including the non~hydrogen donor 18 solvent, is recovered by line 40O In a preferred embodiment 19 of the present invention9 at ieast a portion of the inter-mediate fraction having less than 008 weight percent 21 donatable hydrogen, which includes the recovered non-hydrogen 22 donor solvent, is recycled via line 42, without any inter-23 vening rehydrogenation9 into mixing zone 12 or directly into 24 the coal liquefaction zone.
It should also be noted that in non-catalyzed 26 hydrogen donor coal liquefactio~. processes, ~the heavy 27 bottoms product resulting from fractional distillation of 28 the coal liquefaction oil product contains solids. The 29 solids-containing heavy bottom~ f~action is typically sub-3~ jected to a fluid coking operation since a substantial -1~07Z13 1 po~tion of the carbon of the chargestock emerges with the 2 solids in the form of char that must be recovered. In 3 contrast, in the process of the present invention, ~ince . 4 the solid residue of the liquefaction zone does not eontain any significa1lt amou.nt of char, the solids can be separated 6 from the coal liquefaction zone effluent by known means and 7 discarded or used as catalyst. The process of the present 8 invention would permit the elimination of the coking step~
9 Figure 2 shows various process options fox treating the coal liquefaction zone effluent which is removed from 11 the.coal liquefaction reactor 22 by line 24. The effluent 12 is introduced into a gas-liquid separator 26 where hydrogen 13 and light hydrocarbon~s are removed overhead by line 28.
14 Three preferred process options are available for the liquid stream containing dispersed catalyst solids which emerge 16 from separator vessel 26 via line 30.
17 In process optlon to be designated 'IA", the liqui~-18 solids stream is fed by line 32 to concentration zone 34 19 where by means, for example, of distilla~ion, solid precip-.20 itation or centrifugation, the ~tream i8 ~epara~ed into a 21 clean liquid product, which is withdrawn through li.ne 36, 22 and a concentrated slurry (e.g. 20 to 40 percent by weight) 23 in oil. At least a portion of the concentrated slurry can 24 be re ved as a purge stream through line 38 to control the buildup of solid materials in the coal liquefaction reactor, 26 and the balance of the slurry is returned by line 40 and . 27 line 30 to liquefaction reac~or 220 The purge stream may ~ be filtered subsequently to recover c~alyst and liquid product or it can be burned or gasified.to provide, respec-tively, heat and hydrogen for the pr3cess.
7~ 1 3 1 In the process option to be designated "B", the 2 purge stream from concen~ration zone 34 is omitted and the 3 entire slurry concentrate withdr~wn through line 40 i~ fed to separation zone 44 via lines 30 an.d 42. In thi.s æone, a major por~.ion of the remaining ll~uid phase is separated 6 from the solids by means of centrifugation, filtration or 7 a combination of settling and drawoff 9 etc.. Liquid is 8 removed from ~he ~one through line 46 and solids through line 48~. At least a portion of the solids and associated o remaining liquid are purged from the process vi.a line 50 to ll control the buildup of solids in the process and the balance 12 of the solids ~s recycled to liquefaction reactor 22 via line 52 which connects to recycle line 30. The solids can be recycled either as recovered or after suitable cleanup (not shown) to remove heavy adhering oil deposits and coke.
16 In option designated "C", the slurry of solids in 17 oi. exiting fro~ separator 26 via line 30 is fed direc~ly 18 to separation zone 44 by way of line 42 whereupon solids l9 and liquid product are separated by means of centrifugation or filtration. All or part of the solids exi~ing from 21 vessel 44 via line 48 may be purged fronn the process through 22 line 50 and the remainder recycled to ~he liquefac~ion 23 reactor. Liquid product is recovered through line 46. If 24 ~esired, at least a portion o the heavy fraction of the hydroconverted oil product may be recycled to ~he coal 26 liquefaction zone.
27 The process of the invention may be conducted 28 either ~s a batch or as 8 continuous ~ype proceæs~
29 The following ex~mple i~ presen~ed to illustrate the invention.
. - 13 -llV7Z13 2 C.ompar~ti-~e e~perlmen~.s.were made ln which molyb-3 denum naphthenate was u~llized as ¢atal~3t precursor in a 4 non~hydrogen donor sol~vent9 tha~ is~ in alpha meth~l-
5 naphthalene~ co~pared to c~ntrol ru.ns in which hydrogenated
6 c:reosote oil, having ~ don~table hydrogen content of 1. 54
7 weight percent, a hydrGgen donor solvent~ was utilized.
8 The chærg~s~ock used in these experiments was a
9 50/50 mixture of Wyodak coal and solvent. The molybdenum concentra.tion was 404 weight par~s per million molybdenum, 11 calculated as the elemental metalD based on coal alone. In 12 the runs9 in which pretrea~ment was performed, the pretreat-13 ments gas was a mixture of 18% H2S and 82% hydrogen. The 14 pretreatment conditi3ns were an initial pressure at room temperature of lS00 psig and a pretreatment ~emperature of : 16 725F. The liquefaction conditions were 820F. and 200 ~ 17 psig hydrogen for 1 hourO The results of these experiments 18 are summari7ed in the tableO
u~
o~ ~
o o ~/
I~
~ ~ 0 C`~ ~ ~
o o --l o ~ o ~
0 _ O C`J
~O~D~
;~
~e`l o~ o J~ 00 Q) 0 ~ u~o ~ ~ ~ ~
~--o ~ ~ o i~~ o ~ o oo o~
I_i O C~
P4~-1 0 J~
~ ~ ; U ' 'o ,V' ~ o ~
~ ~ o _1 ~0~ ~ ~ o O td ~ ~1 ooo~
~d ~rl ~ ~i ~ ~ o ~ ~ bO
a~ d O ~ i~
~ o ~
U ~-rl U ~ ~~d ~.
U h ~ ~ . _1 h C~ ¢ a~
o v ~ ~J i3.~ 1tn 4 O ~ tq + t.) aJ ~
O ~ l 0 ~ I O ~ P
V O c~ ~ g, o o ~Z;
P: ,~ ~ cn v~ ~c -~ 7 Z ~ 3 1 As can be seen from the table, run 3 compared with 2 n~n 1 shows ~hat non-hydrogen donor solvent with molyb~emlm 3 added perfcrms slightly ~etter than conventional hydrogen 4 donor solvent (run 1~. Rlm 5 compared with run 1 ~hows that this proces~ performs much better than conventional 6 hydrogen donor solvent liquefaction. Run 5 compared wlth 7 run ~ shows that preferred conditions for this process are 8 superi.or to catalyzed hydrogen donor solvent liquefaction.
9 ~un 5 versus run 4 shows that under preferr~ conditions, a non-hydrogen donor solvent has an equivalent performance to ll a hydrogen donor solvent.
u~
o~ ~
o o ~/
I~
~ ~ 0 C`~ ~ ~
o o --l o ~ o ~
0 _ O C`J
~O~D~
;~
~e`l o~ o J~ 00 Q) 0 ~ u~o ~ ~ ~ ~
~--o ~ ~ o i~~ o ~ o oo o~
I_i O C~
P4~-1 0 J~
~ ~ ; U ' 'o ,V' ~ o ~
~ ~ o _1 ~0~ ~ ~ o O td ~ ~1 ooo~
~d ~rl ~ ~i ~ ~ o ~ ~ bO
a~ d O ~ i~
~ o ~
U ~-rl U ~ ~~d ~.
U h ~ ~ . _1 h C~ ¢ a~
o v ~ ~J i3.~ 1tn 4 O ~ tq + t.) aJ ~
O ~ l 0 ~ I O ~ P
V O c~ ~ g, o o ~Z;
P: ,~ ~ cn v~ ~c -~ 7 Z ~ 3 1 As can be seen from the table, run 3 compared with 2 n~n 1 shows ~hat non-hydrogen donor solvent with molyb~emlm 3 added perfcrms slightly ~etter than conventional hydrogen 4 donor solvent (run 1~. Rlm 5 compared with run 1 ~hows that this proces~ performs much better than conventional 6 hydrogen donor solvent liquefaction. Run 5 compared wlth 7 run ~ shows that preferred conditions for this process are 8 superi.or to catalyzed hydrogen donor solvent liquefaction.
9 ~un 5 versus run 4 shows that under preferr~ conditions, a non-hydrogen donor solvent has an equivalent performance to ll a hydrogen donor solvent.
Claims (34)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for liquefying coal to produce an oil, which comprises the steps of:
(a) forming a mixture of coal, a non-hydrogen donor solvent and an added oil soluble metal compound, said metal being selected from the group consisting of Groups VB, VIB, VIIB
and VIII of the Periodic Table of Elements and mixtures thereof;
(b) converting said oil soluble compound to a catalyst within said mixture in the presence of a hydrogen-con-taining gas by heating said mixture to an elevated temperature ranging from about 325°C to about 538°C;
(c) reacting the resulting mixture with a gas comprising molecular hydrogen under coal liquefaction conditions including a temperature ranging from about 343°C to about 538°C, in a liquefaction zone, and (d) recovering a coal liquefaction product mixture comprising an oil product and solids.
(a) forming a mixture of coal, a non-hydrogen donor solvent and an added oil soluble metal compound, said metal being selected from the group consisting of Groups VB, VIB, VIIB
and VIII of the Periodic Table of Elements and mixtures thereof;
(b) converting said oil soluble compound to a catalyst within said mixture in the presence of a hydrogen-con-taining gas by heating said mixture to an elevated temperature ranging from about 325°C to about 538°C;
(c) reacting the resulting mixture with a gas comprising molecular hydrogen under coal liquefaction conditions including a temperature ranging from about 343°C to about 538°C, in a liquefaction zone, and (d) recovering a coal liquefaction product mixture comprising an oil product and solids.
2. The process of claim 1 wherein said oil product is separated into fractions, including a solvent fraction having less than 0.8 weight percent donatable hydrogen, and wherein at least a portion of said solvent, without intervening hydrogenation, is recycled to said liquefaction zone.
3. The process of claim 1 wherein said oil soluble metal compound in step (a) is added in an amount ranging from about 10 to less than 2000 weight parts per million, calculated as the elemental metal, based on the weight of the coal in said mixture.
4. The process of claim 1 wherein said oil soluble metal compound is selected from the group consisting of inorganic com-pounds, salts of organic acids, organometallic compounds and salts of organic amines.
5. The process of claim 1 wherein said oil soluble metal compound is selected from the group consisting of salts of acyclic aliphatic carboxylic acids and salts of alicyclic aliphatic carboxylic acids.
6. The process of claim 1 wherein said oil soluble metal compound is a salt of naphthenic acid.
7. The process of claim 1 wherein the metal constituent of said oil soluble metal compound is selected from the group consisting of molybdenum, chromium and vanadium.
8. The process of claim 1 wherein said oil soluble metal compound is molybdenum naphthenate.
9. The process of claim 1 wherein said oil soluble metal compound is phosphomolybdic acid.
10. The process of claim 1 wherein said hydrogen-containing gas of step (b) comprises from about 1 to 90 mole percent hydrogen sulfide.
11. The process of claim 1 wherein said hydrogen-containing gas of step (b) comprises from about 1 to 50 mole percent hydrogen sulfide.
12. The process of claim 1 wherein said oil soluble metal compound is converted by first heating the mixture of said soluble metal compound, coal and non-hydrogen donor solvent to the temperature ranging from about 325°C to about 438°C in the presence of said hydrogen-containing gas to form a catalyst within said mixture and subsequently reacting the resulting mixture containing the catalyst with hydrogen under coal liquefaction conditions.
13. The process of claim 1 wherein said hydrogen-containing gas also contains hydrogen sulfide.
14. The process of claim 1 wherein said oil soluble metal compound is converted in the presence of a hydrogen-con-taining gas in the coal liquefaction zone under coal liquefaction conditions thereby forming said catalyst in situ within said mixture in said liquefaction zone.
15. The process of claim 1 wherein said coal lique-faction conditions further include a hydrogen partial pressure ranging from 500 to 5000 psig.
16. The process of claim 1 wherein the space velocity of said mixture in said liquefaction zone ranges from about 0.1 to 10 volumes of mixture per hour per volume of liquefaction zone.
17. The process of claim 1 comprising the additional steps of separating at least a portion of said solids from said liquefaction product mixture and recycling at least a portion of said separated solids to said liquefaction zone.
18. The process of claim 1 wherein said catalyst is the sole catalyst in said liquefaction zone.
19. The process of claim 1 wherein said solvent and coal are mixed in a solvent-to-coal weight ratio ranging from about 0.8:1 to about 4:1.
20. The process of claim 1 wherein said solvent and coal are mixed in a solvent-to-coal weight ratio ranging from about 1:1 to 2:1.
21. The process of claim 1 wherein said non-hydrogen donor solvent comprises less than 0.8 weight percent donatable hydrogen based on the weight of said solvent.
22. The process of claim 21 wherein said non-hydrogen donor solvent comprises a compound or a mixture of compounds having an atmospheric boiling point ranging from about 350°F to about 850°F.
23. The process of claim 21 wherein said non-hydrogen donor solvent comprises a compound or a mixture of compounds having an atmospheric boiling point ranging from about 350°F to less than about 650°F.
24. The process of claim 1 wherein in step (a) a mixture is formed of wet coal, a non-hydrogen donor solvent and from about 10 to about 700 wppm of said oil-soluble metal compound and wherein in step (c) said resulting mixture containing said catalyst is reacted with a gas comprising hydrogen and from about 5 to about 50 mole percent carbon monoxide.
25. The process of claim 24 wherein said oil soluble metal compound is added to step (a) in an amount ranging from about 50 to 500 wppm, calculated as the elemental metal, based on the coal.
26. The process of claim 24 wherein said oil soluble metal compound is a metal-containing organic compound.
27. The process of claim 24 wherein said oil soluble metal compound is a molybdenum-containing organic compound.
28. The process of claim 24 wherein said oil soluble metal compound is phosphomolybdic acid.
29. The process of claim 1 wherein in step (a) a mixture is formed of wet coal, a non-hydrogen donor solvent and an added oil-soluble molybdenum-containing organic compound, said organic compound being added in an amount ranging from about 10 to less than 2000 wppm, calculated as the elemental metal, based on the coal in said mixture, and wherein in step (c) said resulting mixture containing said catalyst is reacted with a gas comprising hydrogen and from about 5 to about 50 mole percent carbon monoxide.
30. The process of claim 29 wherein said organic compound is selected from the group consisting of salts of organic acids, organometallic compounds and salts of organic amines.
31. The process of claim 29 wherein said organic com-pound is selected from the group consisting of salts of acyclic aliphatic carboxylic acids and salts of alicyclic aliphatic carboxylic acids.
32. The process of claim 29 wherein said organic compound is molybdenum naphthenate.
33. The process of claim 29 wherein said hydrogen-containing gas of step (b) comprises from about 1 to 90 mole percent hydrogen sulfide.
34. The process of claim 29 wherein the gas of step (c) additionally comprises from about 1 to about 30 mole percent hydrogen sulfide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US73185876A | 1976-10-12 | 1976-10-12 | |
| US731-858 | 1976-10-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1107213A true CA1107213A (en) | 1981-08-18 |
Family
ID=24941233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA283,028A Expired CA1107213A (en) | 1976-10-12 | 1977-07-19 | Liquefaction of coal in a non-hydrogen donor solvent |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5347404A (en) |
| AU (1) | AU506863B2 (en) |
| BR (1) | BR7705747A (en) |
| CA (1) | CA1107213A (en) |
| DE (1) | DE2735609A1 (en) |
| FR (1) | FR2367813A1 (en) |
| GB (1) | GB1577464A (en) |
| ZA (1) | ZA773429B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4369106A (en) * | 1980-04-10 | 1983-01-18 | Exxon Research And Engineering Co. | Coal liquefaction process |
| ZA812418B (en) * | 1980-04-10 | 1982-04-28 | Exxon Research Engineering Co | Coal liquefaction process |
| US4485008A (en) * | 1980-12-05 | 1984-11-27 | Exxon Research And Engineering Co. | Liquefaction process |
| US4424109A (en) | 1981-04-07 | 1984-01-03 | Hydrocarbon Research, Inc. | Catalyst for coal liquefaction process |
| ZA822056B (en) * | 1981-08-05 | 1983-02-23 | Lummus Co | Coal liquefaction |
| EP0093809A1 (en) * | 1982-05-06 | 1983-11-16 | Exxon Research And Engineering Company | Process for the hydroconversion of carbonaceous and/or hydrocarbonaceous feeds |
| US4552642A (en) * | 1983-06-27 | 1985-11-12 | Ashland Oil, Inc. | Method for converting coal to upgraded liquid product |
| US4740295A (en) * | 1986-04-21 | 1988-04-26 | Exxon Research And Engineering Company | Hydroconversion process using a sulfided molybdenum catalyst concentrate |
| BR8701833A (en) * | 1986-04-21 | 1988-02-02 | Exxon Research Engineering Co | PERFECT PROCESS TO PREPARE A CATALYST AND PROCESS FOR HYDROCONVERSION OF A CARBONACEOUS LOAD STOCK |
| US4740489A (en) * | 1986-04-21 | 1988-04-26 | Exxon Research And Engineering Company | Method of preparing a hydroconversion sulfided molybdenum catalyst concentrate |
| JP4929233B2 (en) * | 2008-05-28 | 2012-05-09 | 本田技研工業株式会社 | Throttle body arrangement structure for general-purpose V-type engine |
| CN114768833A (en) * | 2022-03-31 | 2022-07-22 | 中国神华煤制油化工有限公司 | Catalyst oil coal slurry and preparation method thereof, and method for directly liquefying coal and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE707813C (en) * | 1935-12-22 | 1941-07-04 | I G Farbenindustrie Akt Ges | Process for the pressure extraction of coal, peat, bituminous slate and the like like |
| US3532617A (en) * | 1968-07-23 | 1970-10-06 | Shell Oil Co | Hydroconversion of coal with combination of catalysts |
| CA1079665A (en) * | 1976-07-02 | 1980-06-17 | Clyde L. Aldridge | Hydroconversion of an oil-coal mixture |
-
1977
- 1977-06-07 ZA ZA00773429A patent/ZA773429B/en unknown
- 1977-06-10 AU AU26021/77A patent/AU506863B2/en not_active Expired
- 1977-06-15 GB GB25020/77A patent/GB1577464A/en not_active Expired
- 1977-07-19 CA CA283,028A patent/CA1107213A/en not_active Expired
- 1977-08-06 DE DE19772735609 patent/DE2735609A1/en not_active Ceased
- 1977-08-29 BR BR7705747A patent/BR7705747A/en unknown
- 1977-09-07 FR FR7727149A patent/FR2367813A1/en active Granted
- 1977-10-11 JP JP12100477A patent/JPS5347404A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU2602177A (en) | 1978-12-14 |
| FR2367813A1 (en) | 1978-05-12 |
| JPS5347404A (en) | 1978-04-27 |
| GB1577464A (en) | 1980-10-22 |
| DE2735609A1 (en) | 1978-04-13 |
| FR2367813B1 (en) | 1981-04-30 |
| AU506863B2 (en) | 1980-01-24 |
| BR7705747A (en) | 1978-06-27 |
| ZA773429B (en) | 1978-04-26 |
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