DE2735609A1 - METHOD FOR LIQUIDIZING COAL - Google Patents

Description

The invention relates to a method for liquefying Coal in an NHD solvent (non-hydrogen donor solvent, i.e. no hydrogen donating solvent) to liquid hydrocarbon products in the presence a catalyst made in situ from a small amount of metals that is the mixture of coal and solvents are added as oil-soluble metal compounds.

The liquefaction of coal into liquid coal products in a hydrogen donor solvent is well known. In such processes, a slurry of coal in a hydrogen donor solvent in the presence of molecular hydrogen reacted at elevated temperature and pressure. In this known method, the Hydrogen donor solvent used during coal liquefaction depleted in hydrogen, generally prior to recycling to the coal liquefaction zone of a hydrogenation subject.

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It is also known to convert coal into liquid products by hydrogenating coal which is soluble in oil Metal naphthenate is impregnated, or carbon is hydrogenated in a liquid medium such as oil, which has a boiling range of 250 to 325 ° C and contains an oil-soluble metal naphthenate. It was found that, calculated as metal, concentrations on metal naphthenate catalysts are down to 0.01% effective for converting the carbon.

Furthermore, a method is known for liquefying subbituminous Coal in a hydrogen donor oil in the presence of hydrogen, carbon monoxide, water and an alkali or Ammonium molybdate, based on the coal, in an amount of 0.5 to 10% by weight.

It has now been found that an effective liquefaction of Coal with molecular hydrogen enters when a NHD solvent (non-hydrogen donor solvent) is used and carries out the coal liquefaction reaction in the presence of a small amount of a catalyst consisting of a added oil-soluble metal compound is produced. In addition, the NHD solvent can be used without having to use it must be subjected to hydrogenation, be returned to the liquefaction zone. Therefore, by using a NHD solvent eliminates the need for an external solvent

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medium hydrogenation stage as in conventional coal liquefaction processes using hydrogen donor solvents is generally required.

Other advantages of using oil-soluble metal compounds in an NHD solvent during coal liquefaction result from the following description and the claims. All ppm information in the description and in the claims are based on weight (i.e. weight ppm)

The term "hydroconversion" is used for a catalytic conversion of coal to liquid hydrocarbons in the presence of hydrogen.

The invention therefore relates to a method for liquefying coal to produce an oil, which is characterized in that is that one

(a) a mixture of coal, an NHD solvent and an oil-soluble metal compound with a metal from the Manufactures groups VB, VIB, VIIB or VIII of the periodic table or mixtures thereof,

(b) the oil-soluble metal compound in the mixture by heating to an elevated temperature in the presence of a Converting gas containing hydrogen into a catalyst,

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(c) the resulting mixture containing the catalyst in a liquefaction zone under coal liquefaction conditions reacts with a gas containing molecular hydrogen and

(d) a coal liquefaction product mixture containing an oil product and solids wins.

According to another embodiment of the invention, further proposed a method for liquefying coal to produce an oil, which is characterized in that man

(a) a mixture of wet charcoal, an NHD solvent and an added oil-soluble metal compound, the oil-soluble metal compound calculated as metal and based on the weight of the coal in the mixture, is added in an amount of about 10 to 700 ppm and one Metal compound is as defined above,

(b) the oil-soluble metal compound in the mixture in the presence of a hydrogen-containing gas in a catalyst converts,

(c) the resulting mixture containing the catalyst in a liquefaction zone under coal liquefaction conditions with a hydrogen and about 5 to 50 mole percent carbon monoxide containing gas and

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(d) a coal liquefaction product mixture containing an oil product and solids wins.

In the following the invention will be explained in more detail with reference to the drawings; show it:

Fig. 1 is a flow diagram of an embodiment of the invention Procedure;

Fig. 2 is a flow diagram of a further embodiment of the
method according to the invention.

The method according to the invention is suitable in very general terms
for hydroconversion of coal to produce liquid coal products (i.e. normally liquid hydrocarbon products) in an NHD solvent process.
The term "coal" is used throughout this description
used to denote normally solid carbonaceous material including all types of coal such as anthracite coal, bituminous coal, semi-bituminous coal, subbituminous coal, brown coal, peat, and mixtures thereof.

In the method shown in Fig. 1, the coal is in
Form of particles with particle diameters up to about 0.32 cm (suitably with a particle size corresponding to 8 Tyler

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mesh) is introduced via line 10 into a mixing zone 12 in which it with an NHD solvent fed in via line 14 is mixed. The solvent and char are used in a solvent / char weight ratio of about 0.8: 1 up to 4: 1 and preferably 1: 1 to 2: 1 mixed with one another.

The NHD solvents used in the process according to the invention are solvents which, based on the weight of the total solvent, contain less than 0.8% by weight of donor hydrogen. Preferably the solvent is an NHD compound or a mixture of such compounds having an atmospheric boiling point of 177 to 454 ° C and preferably 177 to less than 343 ° C. Suitable NHD solvents include aromatic compounds such as alkylbenzenes, alkynaphthalenes, alkylated polycyclic aromatics, heteroaromatics and mixtures thereof, as well as non-hydrogenated creosote oil, intermediates from the catalytic cracking of petroleum feedstocks, liquids obtained from coal, shale oil and similar materials. An oil-soluble metal compound, in which the metal is a metal of groups VB, VIB, VIIB, VIII or mixtures thereof, is added to the NHD solvent via line 16, so that in the mixing zone 12 a mixture of oil-soluble metal compound, NHD solvent and Coal is formed. The oil-soluble metal compound is calculated as metal and based on the

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Weight of the coal in the mixture, in an amount from 10 to less than 2000 ppm, preferably 25 to 950 ppm, in particular 50 to 700 ppm and particularly preferably 50 to 400 ppm were added.

Suitable oil-soluble metal compounds under the process conditions Convertible into active catalysts include (1) inorganic metal compounds such as Halides, oxyhalides, hydrated oxides, heteropoly acids (e.g. phosphomolybdic acid, molybdenum silica); (2) Metal salts of organic acids such as acyclic and alicyclic aliphatic carboxylic acids with two or more Carbon atoms (e.g. naphthenic acids), aromatic carboxylic acids (e.g. toluic acid), sulfonic acids (e.g. toluene sulfonic acid), sulfinic acid, mercaptans, xanthogenic acid, phenols, aromatic Di- and polyhydroxy compounds; (3) organometallic compounds such as metal chelates, e.g. with 1,3-diketones, Ethylenediamine, ethylenediaminetetraacetic acid, phthalocyanines, etc .; (4) Metal salts of organic amines such as aliphatic Amines, aromatic amines and quaternary ammonium compounds.

The metal component of the oil-soluble metal compound is

a metal of groups VB, VIB, VIIB or VIII of the periodic

Systems or mixtures thereof (periodic system of

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E. H. Sargent and Company, copyright 1962, Dyna Slide Company), i.e. vanadium, niobium, tantalum, chromium, molybdenum, tungsten, Manganese, rhenium, iron, cobalt, nickel and the precious metals including platinum, iridium, palladium, osmium, ruthenium and rhodium. Molybdenum, vanadium and chromium are preferably used, with molybdenum and chromium and in particular molybdenum are particularly preferred. Preferred compounds of the metals include the salts of acyclic (straight-chain or branched) aliphatic carboxylic acids, salts of alicyclic aliphatic carboxylic acids, heteropoly acids, hydrated oxides, carbonyls, phenates and organic amine salts. Particularly preferred types of metal compounds are the heteropoly acids, for example phosphomolybdic acid. Another preferred metal compound is a salt of an alicyclic aliphatic carboxylic acid such as metal naphthenate. Most preferred compounds are molybdenum naphthenate, vanadium naphthenate and chromium naphthenate.

When the oil-soluble metal compound to the NHD solvent is given, it dissolves in the solvent. To cool the catalyst, the metal compound (catalyst precursor) converted into the slurry of coal and NHD solvent.

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Various methods can be used to convert the dissolved metal compound into an active catalyst. A preferred method (pretreatment method) for forming the catalyst from the oil-soluble compound according to FIG Invention consists in that the mixture of metal compound, carbon and solvent in the presence of a hydrogen containing gas heated at a pressure of 36.2 to 353 kg / cm to a temperature of about 325 to 438 ° C. The hydrogen Gas containing may be pure hydrogen, but is usually a stream of hydrogen, which is some others Contains gaseous impurities, for example a hydrogen-containing gas stream obtained in the reforming process.

Preferably, the hydrogen-containing gas also contains hydrogen sulfide. The hydrogen sulfide can be about 1 to 90 mol.%, Preferably about 1 to 50 mol.% And in particular make up about 1 to 30 mole percent of the hydrogen-containing gas mixture. The pretreatment is carried out over a period of about 5 minutes to 2 hours, preferably from about 10 minutes to 1 hour. It is believed that the thermal Treatment in the presence of hydrogen or in the presence of hydrogen and hydrogen sulfide results in the conversion the metal compound in the corresponding metal-containing active catalyst, which also acts as a coking inhibitor acts, relieved.

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The coal / solvent slurry containing the resulting catalyst is then introduced into a coal liquefaction zone, which is described below.

Another method of converting the oil-soluble metal compound is to mix the metal compound, carbon and NHD solvent with a hydrogen containing one React gas so that a catalyst in the feed is produced in situ in the liquefaction zone. That Hydrogen containing gas can contain about 1 to 30 mole percent hydrogen sulfide contain.

Whatever the exact structure of the resulting conversion products the oil-soluble metal compound, the resulting metal component is a catalytically active one Agent and a coking inhibitor.

In the process shown in Fig. 1, the mixture of oil-soluble metal compound, NHD solvent and coal is removed via line 18 from the mixing zone 12 and fed into the pretreatment zone 13, into which in turn a gas mixture is introduced via line 15, the hydrogen and about 1 to 90 mol.%, Preferably 1 to 50 mol.% And in particular 1 to 30 mol.% Of hydrogen sulfide. The pretreatment zone is at a temperature of about

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342 to 415 ° C and a total pressure of 36.2 to 353 kg / cm ² . The pretreatment is carried out over a period of about 10 minutes to 1 hour. The product emerging from the pretreatment zone is removed via line 19. If desired, some of the hydrogen sulfide can be removed from this product. The product from the pretreatment zone is introduced into the liquefaction reactor 22 via line 19, and a gas containing hydrogen is fed into the liquefaction reactor 22 via line 20. The hydrogen containing gas may be pure hydrogen, but is generally a hydrogen stream containing some other gaseous impurities, for example a hydrogen containing gas stream from reforming processes. Suitable hydrogen-containing gas mixtures for feeding into the liquefaction zone include crude synthesis gases, i.e. gases containing hydrogen and about 5 to 50 mol% and preferably about 10 to 30 mol% carbon monoxide.

When wet coal (i.e. coal particles in conjunction with water) is used as a feedstock, it is special it is desirable to use raw synthesis gas, that is, a gas containing hydrogen and carbon monoxide. With such a In the embodiment, the metal compound is preferably a metal-containing organic compound calculated as metal and based on the weight of the coal alone, added in an amount of 10 to 700 ppm, and preferably 50 to 500 ppm.

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The gas fed in via line 20 can also contain hydrogen sulfide Contained in an amount of about 1 to 30 mol%.

The coal liquefaction zone is at a temperature of about 343 to 538 ° C, preferably 416 to 468 ° C and especially 440 to 468 ° C and a hydrogen partial pressure of

2 held from 36.2 to 353 and preferably 71.3 to 212 kg / cm. The throughput, which is defined as the unit volume of the mixture of coal and solvent per hour and per unit volume of the reactor (V / h / V), can vary greatly depending on the desired degree of conversion. Suitable throughputs can be found in the Range from about 0.1 to 10 volume units of feed per hour per unit volume of the reactor, preferably im Range from about 0.25 to 6 V / h / V and in particular in the range from about 0.5 to 2 V / h / V. That from the coal liquefaction zone emerging product is removed via line 24.

This product taken from the coal liquefaction zone contains gases, an oil product, and a solid residue that is catalytic in nature. That from the coal liquefaction zone Exiting product is passed on to a separation zone 26, from which the gases via line 28 overhead removed. This gas can be used to remove undesirable amounts of hydrogen sulfide and carbon dioxide in conventionally cleaned and then returned to the coal liquefaction zone. The solids can also be made from the oil product in a conventional manner

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be separated. This can be done, for example, by allowing it to settle or by centrifuging or filtering. the The separated solids are removed from the separation zone 26 via line 30. If desired, at least a part can the separated solids or the solids concentrate directly via line 31 into the coal liquefaction zone or be returned to the coal / solvent feedstock.

The remainder of the solids removed via line 30 can be discarded as such, since it usually does not contain economically recoverable amounts of char. The oil product is removed from the separation zone 26 via line 32 and passed on to a fractionation zone 34 in which a light fraction is obtained via line 36 which boils below about 204.degree. A heavy fraction is removed via line 38, and a middle fraction via line 40, that is a fraction that includes the NHD-solvent and boiling under atmospheric pressure at 204-371 ⁰ C. In a preferred embodiment of the process according to the invention, at least part of the middle fraction with a content of less than 0.8 wt returned directly to the coal liquefaction zone.

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It should be noted that in non-catalytic hydrogen donor coal liquefaction processes the heavy bottoms of the fractional distillation of the coal liquefaction oil product Contain solids. These heavy bottoms containing solids typically become one Subjected to fluidized bed coking, as a significant part of the carbon of the feedstock is in the form of solids is contained in coal (char) and must be recovered. In contrast, the solid residue in the present invention Process, since it does not contain significant amounts of coal, of which exiting the liquefaction zone Product separated in a known manner and discarded or used as a catalyst. The inventive method thus enables the coking stage to be switched off.

Fig. 2 shows various possible method modifications the treatment of the exiting from the liquefaction zone Product that is removed from the liquefaction reactor 22 via line 24. The one emerging from the liquefaction zone Product is introduced into a gas / liquid separator 26 in which hydrogen and light hydrocarbons can be removed overhead via line 28. For the further treatment of what is removed from the separating vessel 26 via line 30 liquid product containing dispersed catalyst solids, there are three preferred options that are practicable Options.

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If possible, "A" is the liquid / solid flow fed via line 32 into the concentration zone 34, where this is, for example, by distillation, solids precipitation or centrifugation into a pure, liquid product, which is removed via line 36, and a concentrated one Slurry in oil (i.e. 20 to 40 wt.%) Is separated. At least a portion of the concentrated slurry can be removed as a purge stream via line 38 to facilitate formation control of solid materials in the coal liquefaction reactor, and the rest of the slurry will be over Line 40 and line 30 passed back into the liquefaction reactor 22. The flushing stream can then be used for recovery The catalyst and liquid product can be filtered or burned or gasified to generate heat or hydrogen to deliver for the procedure.

Process option "B" omits the purge stream from the concentration zone 34 and all of the pulping concentrate removed via line 40 and introduced into the separation zone 44 via lines 30 and 42. In this A major part of the remaining liquid phase is removed from the solids by centrifugation, filtration or a zone Combination of settling and peeling separated. Liquid product is over line 46 and solids are over Line 48 removed from the zone. At least part of the

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Solids and associated liquids are used to regulate the formation of solids in the process is washed away via line 50 and the remainder of the solids is removed via line 52 and return line 30 to the liquefaction reactor 22 returned. The solids can either be recovered or after appropriate purification (not shown) for removal from adhering heavy oil and coke deposits.

In process option "C", the slurry of solids in oil discharged from the separator 26 via conduit 30 exits, introduced directly via line 42 into the separation zone 44, where the solids and the liquid products through Centrifugation or filtration can be separated from each other. All or part of the from the boiler 44 via line 48 emerging solids can be removed from the process via line 50 and the remainder can be discharged into the Liquefaction reactor are returned. Liquid product is withdrawn via line 46. If desired, at least can a portion of the heavy fraction of the hydroconverted oil product can be returned to the coal liquefaction zone.

The inventive method can either batch or be carried out continuously.

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example

Comparative tests were carried out in which molybdenum naphthenate was used as a catalyst precursor in a NHD solvent, i.e. in Q £ -methylnaphthalene. These Experiments were compared with control experiments in which hydrogenated creosote oil with a donor hydrogen content of 1.54% by weight, i.e. a hydrogen donor solvent, is used became.

The feed used in these experiments was a 50/50 mixture of Wyodak coal and solvent. the The molybdenum concentration calculated as elemental metal and based on the carbon alone was 404 ppm by weight of molybdenum. In the tests in which a pretreatment was carried out, the pretreatment gas consisted of a mixture of 18% H-S and 82% hydrogen. The pretreatment conditions

2 was an initial pressure at room temperature of 106.5 kg / cm

and a pretreatment temperature of 385 ° C. The liquefaction conditions were 438 C and 142 kg / cm hydrogen pressure over a period of 1 hour. The results of this Experiments are summarized in the following table.

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Tabel

Coal liquefaction

404 ppm by weight Mo based on carbon as naphthenate
50/50 Wyodak coal / solvent

438 ° C, Attempt no. 1 hour, , 142 ⁺ kg / cm ² H 2 4th 5 I. solvent 1 2 3 A. B. IO Pretreatment A * A. B. vo Temperature, ₂ C - - - 385 385 I. Pressure, kg / cm (initial pressure - - - at room temperature) 106.5 106.5 α> Time, minutes - - - 30th 30th ο Pretreatment gas - - - H ₂ /18% H ₂ SH ₂ /18% H ₂ S CO Treatment gas - - - ^H 2 H ₂ Yields, mol% C to: H ₂ H ₂ H ₂ Δ cn CO + CO ₂
C ₁ -C ^ hydrocarbons Δ Δ Δ 6.00 5.10 ■ ^ oil ³ 6.1 5.84 6.21 4.24 5.60 ο coke 6.0 5.72 6.50 87.09 86.56 cn 68.5 83.03 69.61 2.67 2.74 19.4 5.51 17.68

Conradson carbon des

liquid product 13.21 11.0 16.3 5.81 6.87

Solvent A = hydrogenated creosote oil
Solvent B = 1-methylnaphthalene

* no catalyst

As can be seen from the table, the comparison of Experiment 3 with Experiment 1 shows that the NHD solvent with added Molybdenum gives slightly better results than the conventional hydrogen donor solvent (Run 1). Run 5 when compared to Run 1 shows that this process is much better than conventional hydrogen donor solvent liquefaction is. Experiment 5 compared with experiment 2 shows that the inventive method under preferred conditions for catalyzed hydrogen donor solvent liquefaction is superior. The comparison of Experiment 5 with Experiment 4 shows that under preferred conditions an NHD solvent is as powerful as a hydrogen donor solvent.

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Claims (40)

UEXKÜLL ä. STCLBERG PATENTANWÄLTE 2 HAMBURG 52 BESELERSTRASSE 4 DR. J.-D. FRHR. by UEXKÜLL DR. ULRICH GRAF STOLBERO DIPL.-ING. JÜRGEN SUCHANTKE Exxon Research and (Prio: October 12, 1976 Engineering Company US 731 858 - 14071) P.O. Box 55 Linden, N.J./V.St.A. Hamburg, July 19, 1977 Process for liquefying coal Patent claims 1. Process for liquefying coal for manufacture an oil, characterized in that one (a) a mixture of coal, an NHD solvent and an oil-soluble metal compound with a metal from groups VB, VJB, VIIB or VIII of the periodic table or a mixture of these, (b) the oil soluble metal compound in the mixture by heating to an elevated temperature in the presence 609815/0541 ORIGINAL INSPECTED converting a hydrogen-containing gas into a catalyst, (c) the resulting mixture containing the catalyst in a liquefaction zone under coal liquefaction conditions reacts with a gas containing molecular hydrogen and (d) a coal liquefaction product mixture containing an oil product and solids wins. 2. The method according to claim 1, characterized in that the oil product obtained is separated into fractions, among other things, a solvent fraction with less than 0.8% by weight of donor hydrogen is obtained and at least part of this solvent fraction, without carrying out a hydrogenation, into the liquefaction zone returns. 3. The method according to claim 1, characterized in that the oil-soluble metal compound is calculated in step (a) as metal and in an amount of about 10 to less based on the weight of the coal in the mixture added than 2000 ppm. 809815/0541 4. The method according to claim 1, characterized in that there is an oil-soluble metal compound from the group
consisting of inorganic compounds, salts of
organic acids, organometallic compounds
and salts of organic amines are used. 5. The method according to claim 1, characterized in that an oil-soluble metal compound from the group consisting of salts of acyclic aliphatic carboxylic acids and salts of alicyclic aliphatic
Used carboxylic acids. 6. The method according to claim 1, characterized in that there is a salt of naphthenic acid as the oil-soluble metal compound used. 7. The method according to claim 1, characterized in that an oil-soluble metal compound is used as Metal contains molybdenum, chromium or vanadium. 8. The method according to claim 1, characterized in that molybdenum naphthenate is used as the oil-soluble metal compound. 809815/0541 9. The method according to claim 1, characterized in that the oil-soluble metal compound is phosphomolybdic acid used. 10. The method according to claim 1, characterized in that a hydrogen-containing gas with a content of 1 to 90 mol.% hydrogen sulfide is used in process step (b) used. 11. The method according to claim 1, characterized in that in process step (b) one containing hydrogen Gas with a content of about 1 to 50 mol.% Hydrogen sulfide is used. 12. The method according to claim 1, characterized in that the oil-soluble metal compound is obtained by heating the mixture in the presence of the hydrogen-containing gas to a temperature of about 325 ° C to 538 ° C into a catalyst. 13. The method according to claim 1, characterized in that the oil-soluble metal compound is converted into a catalyst by first opposing the mixture of oil-soluble metal compound, coal and NHD solvent 809815/0541 war the hydrogen-containing gas heated to a temperature of about 325 ° C to 438 ° C, and then the resulting mixture containing the catalyst with hydrogen under coal liquefaction conditions implements. 14. The method according to claim 12, characterized in that a hydrogen-containing gas is used which also contains hydrogen sulfide. 15. The method according to claim 1, characterized in that the oil-soluble metal compound in situ in the presence of a hydrogen containing gas in the coal liquefaction zone under coal liquefaction conditions in converts a catalyst. 16. The method according to claim 1, characterized in that the coal liquefaction at a temperature in the range from about 343 to 538 C and a hydrogen partial pressure 2 in the range of 36.2 to 353 kg / cm. 17. The method according to claim 1, characterized in that about 0.1 to 10 volume units of the feed mixture permeated per hour per volume unit liquefaction zone. 809815/054 1 - D - 18. The method according to claim 1, characterized in that at least some of the solids are also extracted separated from the liquefaction product mixture and at least some of these separated solids into the liquefaction zone returns. 19. The method according to claim 1, characterized in that the catalyst is used as the only catalyst in the liquefaction zone used. 20. The method according to claim 1, characterized in that the solvent and the charcoal in a solvent / charcoal weight ratio from about 0.8: 1 to 4: 1 mixed together. 21. The method according to claim 1, characterized in that. the solvent and the charcoal in a solvent / charcoal weight ratio from about 1: 1 to 2: 1 mixed together. 22. The method according to claim 1, characterized in that there is an NHD solvent based on the weight of the solvent used less than 0.8 wt.% donor hydrogen. 809815/0541 23. The method according to claim 22, characterized in that an NHD solvent is used which is a compound or a mixture of compounds having an atmospheric boiling point in the range of about 177 to 454 ° C. 24. The method according to claim 22, characterized in that an NHD solvent is used which is a compound or a mixture of compounds having an atmospheric boiling point in the range of about 177 to less than Contains 343 ° C. 25. The method according to claim 1, characterized in that in process step (a) a mixture of wet Coal, an NHD solvent and about 10 to 7OO ppm of the oil-soluble metal compound and in process stage (c) reacting the resulting mixture containing the catalyst with a gas containing hydrogen and contains about 5 to 50 mole percent carbon monoxide. 26. The method according to claim 25, characterized in that in process step (a) the oil-soluble metal compound, calculated as the metal and based on the weight of the Coal, in an amount of about 50 to 500 ppm. 809815/0541 27. The method according to claim 25, characterized in that there is a metal containing as the oil-soluble metal compound organic compound used. 28. The method according to claim 25, characterized in that there is a molybdenum-containing as the oil-soluble metal compound organic compound used. 29. The method according to claim 25, characterized in that the oil-soluble metal compound is phosphomolybdic acid used. 30. The method according to claim 1, characterized in that one in process step (a) a mixture of wet coal, an NHD solvent and an added oil-soluble, Molybdenum-containing, organic compound prepares, wherein the organic compound is calculated as Metal and, based on the weight of the coal in the mixture, in an amount of from about 10 to less than 2000 ppm is added, and in process step (c) the resulting mixture containing the catalyst with a Reacts gas containing hydrogen and about 5 to 50 mol.% Carbon monoxide. 809815/0541 31. The method according to claim 30, characterized in that there is a compound from the organic compound Group consisting of salts of organic acids, organometallic compounds and salts of organic amines used. 32. The method according to claim 30, characterized in that the organic compound is a compound selected from the group consisting of salts of acyclic aliphatic Carboxylic acids and salts of alicyclic aliphatic carboxylic acids are used. 33. The method according to claim 30, characterized in that the organic compound used is molybdenum naphthenate . 34. The method according to claim 30, characterized in that in process step (b) a hydrogen-containing Gas with a content of about 1 to 90 mole percent hydrogen sulfide is used. 35. The method according to claim 30, characterized in that in process step (c) a gas with an additional Content of about 1 to 30 mol.% Hydrogen sulfide used. 809815/0541 36. Coal liquefaction catalyst, characterized by following manufacturing method: (a) Preparation of a mixture of coal, an NHD solvent and an added oil-soluble metal compound, wherein the oil-soluble metal compound, calculated as metal and based on the weight of the coal in the mixture, in an amount from about 10 to less than 2000 ppm is added and the metal is a metal from groups VB, VIB, VIIB or VIII des periodic system or a mixture of these, (b) converting the oil-soluble compound in the mixture in the presence of a hydrogen-containing gas into a first catalyst, (c) Reaction of the resulting mixture containing the first catalyst with a mixture containing hydrogen Gas under coal liquefaction conditions in a liquefaction zone to obtain a product containing an oil product and a second catalyst, (d) separating the second catalyst from the product emerging from the liquefaction zone and (e) Obtaining the separated second catalyst. 809815/0541 37. Coal liquefaction catalyst according to claim 36, characterized in that the added in production step (a) Metal compound is molybdenum naphthenate. 38. Coal liquefaction catalyst according to claim 36, characterized in that the added in production step (a) Metal compound is phosphomolybdic acid. 39. Process for liquefying coal for manufacture of an oil, characterized in that a mixture of coal and an NHD solvent in the presence of the according to claim 36 in preparation step (e) obtained catalyst under coal liquefaction conditions a hydrogen-containing gas. 40. The method according to claim 1, characterized in that a gas is used in process step (c) which additionally contains about 1 to 30 mol% of hydrogen sulfide. 809815/0541