EP0106364A2 - Katalysator zur Kohleverflüssigung und Kohleverflüssigungsverfahren mit Anwendung dieses Katalysators - Google Patents

Katalysator zur Kohleverflüssigung und Kohleverflüssigungsverfahren mit Anwendung dieses Katalysators Download PDF

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Publication number
EP0106364A2
EP0106364A2 EP83110422A EP83110422A EP0106364A2 EP 0106364 A2 EP0106364 A2 EP 0106364A2 EP 83110422 A EP83110422 A EP 83110422A EP 83110422 A EP83110422 A EP 83110422A EP 0106364 A2 EP0106364 A2 EP 0106364A2
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EP
European Patent Office
Prior art keywords
coal
catalyst
oxide
reaction
substance
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Application number
EP83110422A
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English (en)
French (fr)
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EP0106364A3 (de
Inventor
Mamoru Mizumoto
Hisao Yamashita
Shinpei Matsuda
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Hitachi Ltd
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Hitachi Ltd
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Publication date
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Publication of EP0106364A2 publication Critical patent/EP0106364A2/de
Publication of EP0106364A3 publication Critical patent/EP0106364A3/de
Withdrawn legal-status Critical Current

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    • 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

Definitions

  • This invention relates to a catalyst used in a process for liquefying coal by reacting coal with hydrogen and a process for liquefying coal using said catalyst.
  • Typical catalysts used in this coal liquefaction process are those carrying active components such as molybdenum, cobalt, nickel, etc., on a alumina carrier.
  • This invention provides a catalyst for coal liquefaction consisting essentially of at least one substance which is able to be molten metal at 350 to 500°C in an atmosphere of hydrogen.
  • This invention also provides a process for liquefying coal which comprises reacting coal in a solvent with hydrogen at a reaction temperature of 350 to 500°C under a reaction pressure of 50 to 700 kg/cm 2 in the presence of a catalyst consisting essentially of at least one substance which is able to be molten metal at 350 to 500°C in an atmosphere of hydrogen.
  • Fig. 1 is a graph showing a relationship between the conversion of coal and the reaction temperature
  • Fig. 2 is a graph showing a relationship between the conversion of coal and the reaction pressure.
  • the catalyst of this invention is quite different from the known catalysts and the coal liquefaction process using the special catalyst of this invention is fundamentally different from the known coal liquefaction . processes as will be explained below.
  • the catalysts are present in the state of solid during the coal liquefaction reaction. Even in the case of carrying a tin compound on the porous magnesium silicate carrier, the tin compound is not melted substantially and remains in the state of solid. In such a case, since the tin compound is carried on micropores of the carrier, it is difficult to reduce the tin compound with hydrogen, and thus it is difficult to melt the tin compound.
  • the catalyst of this invention when used, the catalyst is subjected to reduction and becomes molten metal during the coal liquefaction reaction.
  • the coal liquefaction reaction is proceeded in the presence of the molten metal thus produced as catalyst.
  • the catalysts show activity only in the third step.
  • the catalyst is present in the form of metal during the liquefaction raction. This is confirmed by X-ray diffraction. Further the presence of the catalyst in molten state is confirmed by differencial thermal analysis.
  • the substance which is able to be molten metal at 350 to 500°C in an atmosphere of hydrogen there can be used, for example, tin, zinc, bismuth, lead, gallium, cadmium, indium, selenium, tellurium, mercury and various compounds containing these metals, alone or as a mixture thereof.
  • any substances can be used as catalyst, so long as said substances can be molten metal at 350 to 500°C in an atmosphere of hydrogen.
  • metals there can be used metals as they are, metal oxides, metal chlorides, etc. Among them, the substances in the form of metal oxides are more preferable.
  • the metal oxides are stable chemically and easy to handle.
  • the substances used as catalyst in this invention those changing to molten metal during the coal liquefaction reaction and reacting with coal in such a state to produce organic compounds are preferable.
  • examples of such substances are tin, lead, zinc, cadmium, mercury and compounds containing these metals such as oxides, chlorides, etc.
  • the use of tin, zinc, lead and their oxides is preferable from the viewpoint of easiness on handling.
  • coal liquefaction reaction proceeds as follows:
  • the conversion of coal can be raised surprisingly highly.
  • stannic oxide used as catalyst, the coal conversion of as high as almost 100% can be obtained.
  • the shape of catalyst of this invention is not limitative, so long as the substance as catalyst is in the form of fine particles.
  • the particle size of catalyst is preferably 1 mm or less, more preferably 0.1 mm or less.
  • the particle size of catalyst is preferably 1 mm or less, more preferably 0.1 mm or less.
  • the catalyst of this invention does not use a carrier.
  • a carrier When a carrier is used, most portions of a catalyst do not change to molten metal at the time of coal liquefaction reaction and remains in the form of solid, which results in lowering the conversion of coal.
  • the conversion of coal also changes depending on the using amount of catalyst.
  • the catalyst of this invention in an amount of 0.01% by weight based on the weight of coal shows a sufficient effect.
  • the conversion of coal increases with an increase of the amount of catalyst used until 1% by weight of the catalyst based on the weight of coal and maintains its high value even if the catalyst amount is more than 1% by weight.
  • the effect of catalyst for coal conversion is the best when the using amount of catalyst becomes 1 % by weight based on the weight of coal. Therefore, the catalyst is used particularly preferably in an amount of 1 % by weight or more based on the weight of coal.
  • the catalyst is used in an amount of 0.2% by weight or more based on the weight of coal, remarkably high conversion of coal can be obtained.
  • the catalyst of this invention can be prepared by various processes.
  • tin oxides i.e., stannic oxide and stannous oxide
  • processes for preparing tin oxides there can be applied, for example, a process wherein metallic tin is reacted with an acid to synthesize stannic acid, followed by calcination and pulverization; a process wherein a salt of tin is hydrolyzed, followed by calcination and pulverization; a process wherein metallic tin is calcined in air and pulverized; a process wherein a salt of tin or an organotin compound is subjected to pyrolysis and pulverized; and the like.
  • processes for preparing zinc oxide there can be applied, for example, a process wherein an alkali is added to a water-sluble zinc salt to precipitate a hydroxide, followed by calcination and pulverization; a process wherein metallic zinc is calcined in air for oxidation, followed by pulverization; a process wherein an organozinc compound is subjected to pyrolysis, followed by pulverization; and the like.
  • the process wherein metallic tin is reacted with an acid to synthesize stannic acid, followed by calcination and pulverization is most preferable.
  • the processes for preparing zinc oxide the process wherein an alkali is added to a water-soluble zinc salt to precipitate a hydroxide, followed by calcination and pulverization i: most preferable.
  • the tin oxides or zinc oxide prepared by the most preferable processes as mentioned above is used as catalyst for coal liquefaction, the highest conversion of coal can be obtained compared with the cases of using tin oxides or zinc oxide prepared by other processes.
  • the resulting products are separated into gases, oils and solids (residue after liquefaction). Those which are retained as solids are ashes such as alumina, silica, etc., contained in coal, unreacted coal and the catalyst.
  • ashes such as alumina, silica, etc.
  • the recovery of the catalyst is very difficult and the residue after liquefaction is disposed.
  • In-contrast in the present invention, particularly when the substance which becomes molten metal at the time of liquefaction reaction and reacts with coal to produce organic compounds is used as catalyst, the conversion of coal becomes remarkably high and almost no unreacted coal is retained, so that the recovery of the catalyst is easy.
  • the solid can be used again as catalyst as it is.
  • the reaction temperature is usually 350 to 500°C, preferably 400 to 480°C. If the reaction temperature is higher than 500°C, the amount of gases increases too much and the amount of oils becomes too small. If the reaction temperature is lower than 350°C, there hardly takes place the reaction between coal and hydrogen and the liquefaction reaction does not proceed.
  • Fig. 1 is a graph showing a relationship between the reaction temperature and the conversion of coal when the coal liquefaction reaction is conducted by using stannic oxide having a particle size of 74 ⁇ m as catalyst in an amount of 5% by weight based on the weight of coal under a pressure of 150 kg/cm 2 for 30 minutes. It is clear that when the reaction temperature is 400°C or higher, the producing amount of oils (the area between the line of - o - o - and the line of - • - • -) increases.
  • the reaction pressure is usually 50 - 700 Kg/cm 2 , preferably 100 to 200 Kg/cm .
  • the reaction between coal and hydrogen does not proceed under an atmospheric pressure.
  • at least the pressure of 50 kg/cm 2 is necessary.
  • the maximum pressure should be determined considering the material of the reactor and resistance to pressure. The pressure of 700 kg/cm 2 or less is sufficient for the coal liquefaction reaction.
  • Fig. 2 is a graph showing a relationship between the reaction pressure and the conversion of coal when the coal liquefaction reaction is conducted by using stannic oxide having a particle size of 74 ⁇ m as catalyst in an amount of 5% by weight based on the weight of coal at a temperature of 450°C for 30 minutes.
  • the pressure is 100 kg/cm 2 or more, the yield of oils clearly increases.
  • the coal is preferably used in fine particles by pulverizing well.
  • the solvent there can be used anthracene oil, tetralin, creosote oil or liquiefied oils by the coal liquefaction reaction. It is most convenient to use the liquefied oils produced by the coal liquefaction reaction as a part of the solvent.
  • the amount of the solvent changes depending on the viscosity of the slurry. The more'the amount of solvent becomes, the smaller the treating amount of coal becomes. When the amount of the solvent used is small, the viscosity of the resulting slurry becomes lower and the feeding of coal to the reactor becomes difficult. It is preferable to use the solvent in an amount of 1 to 3 times as large as that of the weight of the coal.
  • the coal liquefaction was conducted by using stannic oxide (SnO 2 ) as catalyst.
  • the stannic oxide catalyst was prepared by reacting metallic tin with nitric acid, kneading the reaction product, drying, calcinating at 450°C for 3 hours, followed by pulverization.
  • the particle.size of the catalyst after the pulverization was 74 pm or less.
  • the thus produced stannic oxide in an amount of 1.0 g was mixed with 20 g of Taiheiyo coal (produced in Japan) and 40 g of creosote oil and placed in an autoclave with stirring.
  • the Taiheiyo coal had been crushed into a particle size of 0.1 to 0.4 mm.
  • the amount f the catalyst used was 5% by weight based on the weight of the coal.
  • reaction product was taken out of the autoclave and extracted with n-hexane to extract the oil component by a Soxhlet's extractor.. The residue was extracted with toluene to separate asphaltene.
  • the conversion of coal was obtained by a conventionally used dry ash free base (the calculation being conducted by withdrawing the amounts of ashes and water).
  • the conversion of coal, yields of oils, gases, asphaltene in the products were as follows:
  • the coal liquefaction was conducted by using zinc oxide (ZnO) as catalyst.
  • the zinc oxide catalyst was prepared by neutralizing zinc nitrate with ammonia water, filtering a precipitate produced, drying, calcinating at 450°C for 3 hours, followed by pulverization.
  • the particle size of catalyst after pulverization was 74 pm or less.
  • the coal liquefaction was conducted by using lead oxide (PbO) as catalyst.
  • the lead oxide catalyst was prepared by heating lead acetate in air at 450°C for 2 hours for pyrolysis to give lead oxide, followed by pulverization to give a particle size of 74 ⁇ m or less.
  • the coal liquefaction was conducted by using bismuth oxide (Bi 2 0 3 ) as catalyst.
  • the bismuth oxide catalyst was prepared by heating bismuth nitrate in air at 450°C for 2 hours to conduct pyrolysis, followed by pulverization to give a particle size of 74 um or less.
  • the coal liquefaction was conducted by using gallium oxide (Ga 2 0 3 ) as catalyst.
  • the gallium oxide catalyst was prepared by heating gallium nitrate in air at 450°C for 2 hours to conduct pyrolysis, followed by pulverization to give a particle size of 74 ⁇ m or less.
  • the coal liquefaction was conducted by using a catalyst carrying 5% by weight of stannic oxide on an alumina carrier.
  • the catalyst was prepared by kneading an aluminum hydroxide slurry obtained by hydrolysis of aluminum isopropoxide with stannic acid slurry, drying, calcining at 450°C for 3 hours, followed by pulverization.
  • the coal liquefaction was conducted by using a catalyst carrying molybdenum oxide (Mo03) and nickel oxide (NiO) on an alumina (Al 2 O 3 ) carrier.
  • the catalyst can be obtained commercially in Japan and has a particle size of 74 ⁇ m or less.
  • the conversion of coal can be raised to a remarkable height.
  • a catalyst consisting essentially of a substance such as stannic oxide or zinc oxide which is reduced to molten metal at the time of liquefaction reaction, followed by reaction with coal, the conversion of coal can be raised remarkably high.

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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)
  • Catalysts (AREA)
EP83110422A 1982-10-20 1983-10-19 Katalysator zur Kohleverflüssigung und Kohleverflüssigungsverfahren mit Anwendung dieses Katalysators Withdrawn EP0106364A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP57182918A JPS5973049A (ja) 1982-10-20 1982-10-20 石炭液化用触媒およびそれを使用した石炭液化方法
JP182918/82 1982-10-20

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EP0106364A2 true EP0106364A2 (de) 1984-04-25
EP0106364A3 EP0106364A3 (de) 1986-03-26

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EP83110422A Withdrawn EP0106364A3 (de) 1982-10-20 1983-10-19 Katalysator zur Kohleverflüssigung und Kohleverflüssigungsverfahren mit Anwendung dieses Katalysators

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EP (1) EP0106364A3 (de)
JP (1) JPS5973049A (de)
AU (1) AU551115B2 (de)
CA (1) CA1211400A (de)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE535723C (de) * 1921-11-18 1931-10-14 Progress Akt Ges Verfahren zur Verfluessigung von Kohle
DE547536C (de) * 1924-06-18 1932-03-23 Progress A G Verfahren zur Verfluessigung von Kohle
US1996009A (en) * 1925-02-14 1935-03-26 Standard Ig Co Conversion of solid fuels and products derived therefrom or other materials into valuable liquids

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE535723C (de) * 1921-11-18 1931-10-14 Progress Akt Ges Verfahren zur Verfluessigung von Kohle
DE547536C (de) * 1924-06-18 1932-03-23 Progress A G Verfahren zur Verfluessigung von Kohle
US1996009A (en) * 1925-02-14 1935-03-26 Standard Ig Co Conversion of solid fuels and products derived therefrom or other materials into valuable liquids

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Publication number Publication date
CA1211400A (en) 1986-09-16
AU2029683A (en) 1984-05-10
JPS5973049A (ja) 1984-04-25
AU551115B2 (en) 1986-04-17
EP0106364A3 (de) 1986-03-26

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