US3920536A - Coal dissolving process - Google Patents

Coal dissolving process Download PDF

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Publication number
US3920536A
US3920536A US323568A US32356873A US3920536A US 3920536 A US3920536 A US 3920536A US 323568 A US323568 A US 323568A US 32356873 A US32356873 A US 32356873A US 3920536 A US3920536 A US 3920536A
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United States
Prior art keywords
coal
oil
hydrogen
carbon monoxide
amount
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Expired - Lifetime
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US323568A
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English (en)
Inventor
Walter H Seitzer
Robert W Shinn
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Sun Research and Development Co
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Sun Research and Development Co
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Priority to US323568A priority Critical patent/US3920536A/en
Priority to DE2322316A priority patent/DE2322316A1/de
Priority to CA170,527A priority patent/CA996484A/en
Publication of USB323568I5 publication Critical patent/USB323568I5/en
Application granted granted Critical
Publication of US3920536A publication Critical patent/US3920536A/en
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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
    • C10G1/086—Characterised by the catalyst used
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S208/00—Mineral oils: processes and products
    • Y10S208/951—Solid feed treatment with a gas other than air, hydrogen or steam

Definitions

  • bituminous coal may be liquified by hydrogenating its slurry at 460C in a pasting oil using various catalysts such as nickel, molybdenum, iron, and tin.
  • various catalysts such as nickel, molybdenum, iron, and tin.
  • the process of that invention comprises dissolving sub-bituminous coal by heating a slurry of said coal in a solvent of anthracene oil especially bydrogenated to contain from about 7% to about 9% hydrogen, in the presence of carbon monoxide, hydrogen, and water, at about 400 to about 425C and at a total pressure of from about 2000 to about 5000- psig.
  • sub-bituminous coal may readily be essentially completely solubilized by an economical highly efficient process using a solvent which need not be especially hydrogenated. This is accomplished by hydrogenating sub-bituminous coal in the presence of a donor solvent oil, carbon monoxide, water, and an alkali metal or ammonium molybdate at an elevated temperature of about 400 to about 425C and at a total pressure of about 2000 to about 5000 psig. It appears that the molybdate present acts as a catalyst to effect liquefaction without use of the especially hydrogenated solvent. Furthermore, the pressure of hydrogen is relatively low since the total pressure in the system is the sum of the pressures of steam, carbon monoxide, and hydrogen, which will be about equal at operating temperature. In this way the coal is essentially completely solubilized at relatively low hydrogen pressure and the liquid which is obtained is readily handled and subjected to normal refinery operations to provide useful liquid fuels.
  • the coal used in the process of the invention will be a sub-bituminous coal and this will include lignite coals such as North Dakota lignite, Wyodak, Big Horn, Powder River Sub-Bituminous Coal, and the like.
  • the oil used in the process of the invention is a hydrogen donor solvent.
  • These donor solvent materials are well known and comprise aromatic hydrocarbons which are partially hydrogenated, generally having one or more of the nuclei at least partially saturated.
  • Several examples of such materials are tetralin, dihydronaphthalene, dihydroalkylnaphthalenes, dihydrophenanthrene, dihydroanthracene, dihydrochrysenes, tetrahydrochrysenes, tetrahydropyrenes, tetrahydrofluoranthenes and the like.
  • hydrogen donor solvents are the hydrophenanthrenes and hydroanthracenes such as dihydroanthracene. It will be understood that these materials may be obtained from any source, but are readily available from coal processing systems as anthracene oil, and the like. Of particular value are recycle oils from the coal dissolving process of the invention.
  • the molybdate salts which promote solution of the coal will preferably be an alkali metal (e.g., sodium, potassium, lithium, etc.) or an ammonium salt of molybdic acid; e.g., (NH )6Mo O .4I-I O.
  • the amount of molybdate salt used in the process may vary over a wide range, but the usual amount will be from about 0.5 to about 10% by weight of the coal used, preferably from about 1 to about 7%.
  • a slurry of powdered sub-bituminous coal in the solvent is introduced into a pressure reactor.
  • An amount of coal and solvent will generally be used such that the weight ratio of solvent to coal will be from about 1:1 to :1, preferably about 2:1. Although a higher ratio may be used, it may be uneconomical to do so.
  • water, carbon monoxide, and hydrogen are added as separate entities, water is placed in the reactor, and after closing it, it is pressured with carbon monoxide and with hydrogen.
  • the partial pressure of hydrogen should not be greater than, and preferably less than, the partial pressure of carbon monoxide.
  • both the hydrogen and the carbon monoxide make a contribution to the coal dissolution efficiency.
  • the partial pressure of hydrogen will be about the same as the carbon monoxide partial pressure.
  • the steam pressure generated from the water will preferably be equivalent to the hydrogen or carbon monoxide partial pressure.
  • the temperature is raised rapidly to the temperature range of about 400 to about 425C and the total pressure rises to between about 2000 to about 5000 psig.
  • the residence time for solution of the coal to occur is not critical and will usually be from about 0.5 to about 2 hours, preferably about 1 hour, during which time over 90% by weight of the coal will be brought into solution.
  • the particle size of the coal used is not a critical parameter of the process. While it is preferred to use coal which has been comminuted, coarse particles and very large pieces will also be affected by the process and brought into solution. In fact, the process may even be carried out in subterranean coal mines, the seams of coalbeing solubilized by feeding the solvent with suspended molybdate promoter, carbon monoxide and steam into a closed underground cavern to build up heat and pressure as required by the process. The solubilized coal is then pumped from the cavern for use as later described.
  • the source of carbon monoxide, water, and hydrogen will be producer gas which is readily available from various sources in refinery operations.
  • Producer gas is made by blowing a mixture of air or oxygen and steam through a bed of incandescent carbonaceous fuel and its compostion will vary depending upon the source of fuel and equipment used in making the gas (see Cost Engineering, July 1963, pages 4-l-l).
  • producer gas from coke made with oxygen contains on a percent by volume basis about 53% CO and about 31% hydrogen and such a gas is quite useful. It will be understood that the composition of the producer gas used may be adjusted so as to provide the desired partial pressures of hydrogen and carbon monoxide in the pressure reactor used in subject invention, but with a gas such as described above, no such adjustment is necessary.
  • producer gas may or may not contain water vapor, it may be adjusted to contain this component also, preferably in an amount such that the waterzCO molar ratio is from about 2:1 to 1:2, but, of course, water may be introduced into the reactor separately.
  • the major advantage in using producer gas is that it provides an economical source of reactant carbon monoxide and hydrogen, and, furthermore, does not need to be refined for use in the process as the other components (CO H 8, NH CH and N do not interfere. Since the process of the invention is uniquely suited to use of producer gas, it is particularly valuable in providing an economical coal dissolving process.
  • the dissolved coal formed by the process of the invention is a valuable product similar in many respects to a crude oil and is subjected to the usual refining operations to produce petroleum products.
  • the solution is merely filtered to remove the small amount of insoluble products present, and the filtrate treated in accord with conventional refinery techniques.
  • EXAMPLE 1 A l-liter stirred autoclave is charged with 33 g of powdered Wyodak coal 20 mesh) and 67 g of anthracene oil and then 15 g of water containing 2.0 g of ammonium molybdate. The reactor is sealed, pressure tested, and then pressured with 600 psig of hydrogen and 600 psig of carbon monoxide. The reactor is heated to 415C for 1 hour, the total pressure reaching 3300 psig. The reactor is then allowed to cool, and the product then filtered to remove the solids which are washed with a toluene-acetone mixture, dried, and weighed. The percent of coal dissolved is 89%. When the above experiment is repeated, but without the ammonium molybdate, the amount of coal dissolved is only 57%.
  • EXAMPLE 3 I TABLE II Dissolution of-Wyodak Coal 33 gms Wyodak Coal. 67 gms Anthracene Oil, l5 ml H 0, 2 gms Ammonium Molybdate, 415C, l hr, Stirred Autoclave psig, Start Final Percent Coal H, CO psig Dissolvcd EXAMPLE 4 As in Example 1, a stirred autoclave is charged with 33 g of Wyodak Coal, 67 g of anthracene oil, and g of water containing 2 g of ammonium molybdate.
  • water free producer gas adjusted to contain equal volumes of hydrogen and carbon monoxide is pressured in to 1200 psig. After heating for 1 hour at 415C, the total pressure is 3400 psig. After cooling and separation of solids, 92% of the coal is found to have been dissolved.
  • the process for dissolving sub-bituminous coal which comprises heating at about 400C. to about 425C. under a total pressure of from about 2000 to about 1% to about 7% hydrogen donor oil in a weight ratio to said coal of from about l :l to 5: 1, carbon monoxide, hydrogen in an amount such that its partial pressure is about the same as that of said carbon monoxide, water in an amount such that the molar ratio of water to carbon monoxide is from about 2:1 to 1:2, and as a promoter, an alkali metal or ammonium molybdate in an amount of from about 0.5 to about 10% by weight of said coal.
  • oil is a recycle oil amount such that the molar ratio of water to carbon monoxide is from about 2:1 to 1:2, and ammonium molybdate, the weight ratio of oil to coal being about 2: 1 the amount of hydrogen being such that its partial pressure is about the same as that of said carbon monoxide, and the amount of ammonium molybdate being from by weight of said coal.

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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)
US323568A 1972-05-08 1973-01-15 Coal dissolving process Expired - Lifetime US3920536A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US323568A US3920536A (en) 1972-05-08 1973-01-15 Coal dissolving process
DE2322316A DE2322316A1 (de) 1972-05-08 1973-05-03 Verfahren zum aufloesen von subbituminoeser kohle
CA170,527A CA996484A (en) 1972-05-08 1973-05-07 Coal dissolving process

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US25099972A 1972-05-08 1972-05-08
US323568A US3920536A (en) 1972-05-08 1973-01-15 Coal dissolving process

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USB323568I5 USB323568I5 (2) 1975-01-28
US3920536A true US3920536A (en) 1975-11-18

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4011153A (en) * 1975-04-01 1977-03-08 The United States Of America As Represented By The United States Energy Research And Development Administration Liquefaction and desulfurization of coal using synthesis gas
US4019975A (en) * 1973-11-08 1977-04-26 Coal Industry (Patents) Limited Hydrogenation of coal
US4021329A (en) * 1976-01-15 1977-05-03 Suntech, Inc. Process for dissolving sub-bituminous coal
US4036731A (en) * 1974-12-19 1977-07-19 Coal Industry (Patents) Limited Hydrogenation of coal
US4038172A (en) * 1974-10-16 1977-07-26 Agency Of Industrial Science & Technology Method for removal of oxygen from oxygen-containing compounds
US4077867A (en) * 1976-07-02 1978-03-07 Exxon Research & Engineering Co. Hydroconversion of coal in a hydrogen donor solvent with an oil-soluble catalyst
US4101416A (en) * 1976-06-25 1978-07-18 Occidental Petroleum Corporation Process for hydrogenation of hydrocarbon tars
US4266083A (en) * 1979-06-08 1981-05-05 The Rust Engineering Company Biomass liquefaction process
US4345989A (en) * 1980-08-27 1982-08-24 Exxon Research & Engineering Co. Catalytic hydrogen-donor liquefaction process
JPS6140394A (ja) * 1984-08-01 1986-02-26 Mitsubishi Heavy Ind Ltd 石炭の改質方法
US5130013A (en) * 1983-05-06 1992-07-14 Mitsubishi Kasei Corporation Process for producing a liquefied coal oil and a catalyst for the process
US5151173A (en) * 1989-12-21 1992-09-29 Exxon Research And Engineering Company Conversion of coal with promoted carbon monoxide pretreatment
US5256278A (en) * 1992-02-27 1993-10-26 Energy And Environmental Research Center Foundation (Eerc Foundation) Direct coal liquefaction process
US5336395A (en) * 1989-12-21 1994-08-09 Exxon Research And Engineering Company Liquefaction of coal with aqueous carbon monoxide pretreatment
US5338441A (en) * 1992-10-13 1994-08-16 Exxon Research And Engineering Company Liquefaction process
US20080256852A1 (en) * 2007-04-20 2008-10-23 Schobert Harold H Integrated process and apparatus for producing coal-based jet fuel, diesel fuel, and distillate fuels
US20090200211A1 (en) * 2008-02-13 2009-08-13 Taylor David W Process for improved liquefaction of fuel solids
US9061953B2 (en) 2013-11-19 2015-06-23 Uop Llc Process for converting polycyclic aromatic compounds to monocyclic aromatic compounds

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59142848A (ja) * 1983-02-02 1984-08-16 Toshitaka Ueda 触媒
CA2963436C (en) 2017-04-06 2022-09-20 Iftikhar Huq Partial upgrading of bitumen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1919108A (en) * 1929-04-17 1933-07-18 Ici Ltd Destructive hydrogenation of solid carbonaceous material
GB406986A (en) * 1932-08-26 1934-02-26 Henry Dreyfus Improvements in the production of valuable organic compounds from carbonaceous materials by hydrogenation or reduction
GB407227A (en) * 1932-11-12 1934-03-15 Int Hydrogenation Patents Co Improvements in or relating to the production of hydrocarbons of low boiling point by the destructive hydrogenation of solid carbonaceous materials
US3687838A (en) * 1970-09-14 1972-08-29 Sun Oil Co Coal dissolution process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1919108A (en) * 1929-04-17 1933-07-18 Ici Ltd Destructive hydrogenation of solid carbonaceous material
GB406986A (en) * 1932-08-26 1934-02-26 Henry Dreyfus Improvements in the production of valuable organic compounds from carbonaceous materials by hydrogenation or reduction
GB407227A (en) * 1932-11-12 1934-03-15 Int Hydrogenation Patents Co Improvements in or relating to the production of hydrocarbons of low boiling point by the destructive hydrogenation of solid carbonaceous materials
US3687838A (en) * 1970-09-14 1972-08-29 Sun Oil Co Coal dissolution process

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4019975A (en) * 1973-11-08 1977-04-26 Coal Industry (Patents) Limited Hydrogenation of coal
US4038172A (en) * 1974-10-16 1977-07-26 Agency Of Industrial Science & Technology Method for removal of oxygen from oxygen-containing compounds
US4036731A (en) * 1974-12-19 1977-07-19 Coal Industry (Patents) Limited Hydrogenation of coal
US4011153A (en) * 1975-04-01 1977-03-08 The United States Of America As Represented By The United States Energy Research And Development Administration Liquefaction and desulfurization of coal using synthesis gas
US4021329A (en) * 1976-01-15 1977-05-03 Suntech, Inc. Process for dissolving sub-bituminous coal
US4101416A (en) * 1976-06-25 1978-07-18 Occidental Petroleum Corporation Process for hydrogenation of hydrocarbon tars
US4077867A (en) * 1976-07-02 1978-03-07 Exxon Research & Engineering Co. Hydroconversion of coal in a hydrogen donor solvent with an oil-soluble catalyst
US4266083A (en) * 1979-06-08 1981-05-05 The Rust Engineering Company Biomass liquefaction process
US4345989A (en) * 1980-08-27 1982-08-24 Exxon Research & Engineering Co. Catalytic hydrogen-donor liquefaction process
US5130013A (en) * 1983-05-06 1992-07-14 Mitsubishi Kasei Corporation Process for producing a liquefied coal oil and a catalyst for the process
JPS6140394A (ja) * 1984-08-01 1986-02-26 Mitsubishi Heavy Ind Ltd 石炭の改質方法
US5151173A (en) * 1989-12-21 1992-09-29 Exxon Research And Engineering Company Conversion of coal with promoted carbon monoxide pretreatment
US5336395A (en) * 1989-12-21 1994-08-09 Exxon Research And Engineering Company Liquefaction of coal with aqueous carbon monoxide pretreatment
US5256278A (en) * 1992-02-27 1993-10-26 Energy And Environmental Research Center Foundation (Eerc Foundation) Direct coal liquefaction process
US5338441A (en) * 1992-10-13 1994-08-16 Exxon Research And Engineering Company Liquefaction process
US20080256852A1 (en) * 2007-04-20 2008-10-23 Schobert Harold H Integrated process and apparatus for producing coal-based jet fuel, diesel fuel, and distillate fuels
US20090200211A1 (en) * 2008-02-13 2009-08-13 Taylor David W Process for improved liquefaction of fuel solids
US9074154B2 (en) * 2008-02-13 2015-07-07 Hydrocoal Technologies, Llc Process for improved liquefaction of fuel solids
US9061953B2 (en) 2013-11-19 2015-06-23 Uop Llc Process for converting polycyclic aromatic compounds to monocyclic aromatic compounds

Also Published As

Publication number Publication date
USB323568I5 (2) 1975-01-28
CA996484A (en) 1976-09-07
DE2322316A1 (de) 1973-11-29

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