EP0396832A1 - Enzymatische Entschwefelung von Steinkohlen - Google Patents

Enzymatische Entschwefelung von Steinkohlen Download PDF

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Publication number
EP0396832A1
EP0396832A1 EP19890304725 EP89304725A EP0396832A1 EP 0396832 A1 EP0396832 A1 EP 0396832A1 EP 19890304725 EP19890304725 EP 19890304725 EP 89304725 A EP89304725 A EP 89304725A EP 0396832 A1 EP0396832 A1 EP 0396832A1
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EP
European Patent Office
Prior art keywords
sulfur
substrate
sulfatase
coal
enzyme
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Granted
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EP19890304725
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English (en)
French (fr)
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EP0396832B1 (de
Inventor
William M. Menger
Ernest E. Kern
Debra J. Trantolo
Donald L. Wise
David A. Odelson
Anthony S. Sinskey
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Houston Industries Inc
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Houston Industries Inc
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Priority to DE8989304725T priority Critical patent/DE68905180T2/de
Priority to ES198989304725T priority patent/ES2039855T3/es
Priority to EP89304725A priority patent/EP0396832B1/de
Priority to AT89304725T priority patent/ATE86290T1/de
Publication of EP0396832A1 publication Critical patent/EP0396832A1/de
Application granted granted Critical
Publication of EP0396832B1 publication Critical patent/EP0396832B1/de
Priority to GR930400664T priority patent/GR3008006T3/el
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Expired - Lifetime 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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion

Definitions

  • This invention relates to fossil fuel desulfurization, and particularly to coal desulfurization with enzymes such as oxidases and hydrolases.
  • coal desulfurization processes include physical methods such as pyrite flotation or magnetic separation. While these physical methods are convenient and economical, they are capable of removing only inorganic sulfur and generally result in notable energy losses.
  • chemical coal desulfurization processes such as oxidation with ferric salts, chlorine or ozone, or reduction with solvent-hydrogen mixture, are somewhat more effective in removing organic sulfur, but generally have numerous disadvantages, such as, corrosion problems from reagents, high energy requirements, and costly reagent recovery.
  • the growth of the microorganisms can also produce toxic by-products or compounds which may result in mortality or render the microorganisms incapable of catabolizing sulfur.
  • such fermentation processes are usually plagued with problems such as culture stability, mutation or contamination, reactor upsets, substrate variation, and the like.
  • the present invention involves the biochemical treatment of coal and other fossil fuels to remove sulfur or to desulfurize the fossil fuel.
  • the biochemical treatment comprises contacting the sulfur-containing fossil fuel with an enzyme or enzymes in an amount generally effective to reduce the amount of sulfur in the fuel.
  • the enzymes are added directly to the fossil fuel and need not be produced by microorganisms growing on the fossil fuel as a substrate or growth medium.
  • the process need not be controlled to maintain the viability of any enzyme-producing microorganisms, but can be optimized to favor enzymatically mediated conversion of the sulfur into a form that can be separated from the fossil fuel.
  • the present invention provides a method for desulfurizing a fossil fuel.
  • the process comprises optionally at least selectively oxidizing organic sulfur in a fossil fuel, and thereafter contacting the oxidized fossil fuel with a sulfur-removing enzyme, and recovering the fossil fuel with a reduced sulfur content.
  • the present invention includes a process for treating fossil fuels, and especially fossil fuels containing organic sulfur.
  • Contemplated fossil fuels include petroleum and coal; products of fossil fuel conversion processes, e.g., coal-derived liquids, are also considered.
  • coal includes any coalified organic material such as peat, lignite, sub-bituminous coal, bituminous coal and anthracitic coal.
  • the fossil fuel should contain organic sulfur to obtain the most benefit from treatment according to the present invention, although inorganic sulfur could also be removed by this process.
  • organic sulfur is generally meant organic thiophenes, sulfides and thiols, whereas inorganic sulfur generally refers to sulfates and metallic sulfides such as pyrite.
  • a two-step reaction pathway is generally employed. Initially, the organic sulfur is converted into a sulfur oxide, e.g., sulfate, by oxidation. However, in some rare instances oxidation may not be necessary, because the organic sulfur may be predominantly in the sulfate form or substantially only the naturally occurring sulfate is to be removed. In this sense, the oxidation can be considered to be an optional reaction. However, for optimal sulfur removal, oxidation is preferred. The oxidation substantially converts the organic sulfur into sulfate. The sulfate is enzymatically removed, for example, by hydrolysis induced by a surfur hydrolase, e.g., a sulfatase.
  • a surfur hydrolase e.g., a sulfatase.
  • the fossil fuel may be prepared for treatment according to the present method by generally known methods; e.g., solid fossil fuels, such as coal, can be ground and slurried in water.
  • the slurry can be prepared by grinding the solid fossil fuel to an appropriate particle size, typically 10-50 ⁇ m, and mixing it with water.
  • the invention is described hereinbelow with reference to a ground coal slurry with the understanding that other fossil fuels and media may be analogously employed.
  • the oxidation of the coal slurry may be effected by treatment with an oxidation enzyme, such as, a peroxidase, a laccase, or a like oxidase.
  • an oxidation enzyme such as, a peroxidase, a laccase, or a like oxidase.
  • a peroxidase is any enzyme having the E.C. number 1.11.1.7, e.g., horseradish peroxidase
  • a laccase is any enzyme having E.C. number 1.10.3.2, e.g., Pyricularis oxyzae laccase.
  • partial oxidation may be effected by mild alkaline or acidic treatment of the coal particles.
  • the coal is contacted with 5-10 parts by weight of caustic per 100 parts by weight coal.
  • the contact is for a brief period at an elevated temperature of 125-200°C, preferably 150-180°C.
  • the exposure to the elevated temperature is preferably effected by rapid heating to the treatment temperature, e.g., in less than about three minutes, preferably in less than about one minute, and most preferably in about thirty seconds.
  • the duration of the coal alkali contact at the treatment temperature is preferred about 1-10 minutes and especially preferred about 3-5 minutes.
  • the coal/alkali mixture is rapidly cooled or quenched to below 100°C, preferably in less than about three minutes, and most preferably in less than about one minute, i.e., about 30 seconds.
  • the oxidation serves to convert the organic sulfur moieties into sulfur oxide or moieties, such as sulfate. It is desirable to convert the maximum possible amount of organic sulfur to sulfur oxides. On the other hand, full oxidation to sulfur dioxide is generally undesirable, as also is excessive oxidation of the carbon in the coal matrix.
  • the desired degree of oxidation can be achieved by varying the type of alkali, oxidase or other oxidant, the oxidant concentration, duration of contact between the coal and the oxidant, and other conditions of treatment, e.g., pH, temperature, oxygen availability.
  • sulfatase includes any enzyme capable of hydrolyzing the sulfur moieties to yield a water-soluble sulfur compound. Specific examples include enzymes having the E.C. number 3.1.6.1, such as limpet sulfatase, Aerobacter aerogenes sulfatase, abalone entrail sulfatase, Helix pomatia sulfatase, and the like.
  • the coal particles may be treated with the sulfatase and/or oxidation enzymes, with or without additional chemical oxidation.
  • One contemplated process scheme is a fluidized bed reactor as illustrated in Fig. 1. Generally, uniform concentration and temperature are maintained throughout the fluid bed reactor 100, and the enzyme is immobilized on support particles E which are relatively larger in size than the coal particles in the slurry typically fed into the lower portion of the reactor 100. This size difference permits retention of the enzyme support particles E by catalyst retention screen S and gravity separation in the upper portion of the reactor 100 near the effluent port C in the conventional manner of fluid bed operation. Air or other suitable gas is typically supplied to the bottom of the reactor 100 to promote back mixing and CSTR conditions.
  • FIG. 2 An alternative processing scheme for a moving bed reactor, which generally follows the format of the Examples set forth below, is illustrated in Fig. 2.
  • the coal slurry is introduced from hold-up/preparation tank 200 generally to the upper end of inclined moving bed 202 and discharged from the lower end thereof.
  • the enzyme/sulfate solution effluent from the reactor is recovered by adsorption on a sorbent in enzyme adsorption unit 204.
  • the sulfate solution is readily separated from the sorbent and collected in tank 206 in which, for example, lime or other basic material may be used to precipitate the sulfate prior to disposal.
  • the adsorbed enzyme from unit 204 is then desorbed in unit 208.
  • the desorbed enzyme is then recycled to the reactor 202 along with any makeup enzyme, while the sorbent may be recycled through the enzyme adsorption/desorption cycle.
  • a suspension was prepared of 100 mg dibenzothiophene ("DBT") in 3 ml of 0.1 M Tris buffer, pH 7.0. To this suspension at room temperature was added 0.5 ml of horseradish peroxidase (Sigma P 8000) at 2 mg/ml in buffer, and 0.5 ml of Aerobacter aerogenes sulfatase (Sigma S 1629) at 2 mg/ml in buffer. The mixture was maintained at room temperature in an air atmosphere, and reaction samples were periodically removed and filtered. Solids were analyzed for elemental composition and such analyses are presented in Table 1.
  • spectral data demonstrate a spectral shift in the direction of longer wavelengths indicative of increased polarity which would be expected from conversion of DBT by the peroxidase/sulfatase enzymes.
  • the elemental analysis demonstrates an increase in oxygen content and a decrease in sulfur content. Moreover, it was also observed that starting reaction mixtures were distinctly two-phase liquid-solid mixtures whereas later reaction mixtures were strongly wetted and appeared as milky suspensions.
  • Example 1 The procedure of Example 1 was repeated using 100 mg ball-milled Wyodak coal instead of DBT. The results are presented in Table 2 and Fig. 4. TABLE 2 Elemental Analysis (weight percent) Sample Hours C H N S Wyodak Coal -- 65.96 4.57 0.95 1.70 Wyodak Coal/Peroxidase/Sulfatase 1 59.47 4.99 0.98 0.90 Wyodak Coal/Peroxidase/Sulfatase 2 60.42 5.12 1.15 0.79 Wyodak Coal/Peroxidase/Sulfatase 4 58.84 5.04 1.08 0.95 Wyodak Coal/Peroxidase/Sulfatase 24 60.35 5.30 1.22 0.30
  • Example 2 The procedure of Example 2 was repeated using Illinois No. 6 coal instead of Wyodak coal. The results are presented in Table 3 and Fig. 5. TABLE 3 Elemental Analysis (weight percent) Sample Hours C H N S Illinois No. 6 Coal 0 70.39 4.48 1.44 3.60 Illinois No. 6 Coal/Peroxidase/Sulfatase 1 58.72 5.01 0.94 0.91 Illinois No. 6 Coal/Peroxidase/Sulfatase 2 58.56 5.00 1.14 0.98 Illinois No. 6 Coal/Peroxidase/Sulfatase 4 58.36 5.07 1.22 1.72 Illinois No. 6 Coal/Peroxidase/Sulfatase 24 58.27 5.14 1.21 0.84

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Enzymes And Modification Thereof (AREA)
EP89304725A 1989-05-10 1989-05-10 Enzymatische Entschwefelung von Steinkohlen Expired - Lifetime EP0396832B1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE8989304725T DE68905180T2 (de) 1989-05-10 1989-05-10 Enzymatische entschwefelung von steinkohlen.
ES198989304725T ES2039855T3 (es) 1989-05-10 1989-05-10 Desulfuracion enzimatica del carbon.
EP89304725A EP0396832B1 (de) 1989-05-10 1989-05-10 Enzymatische Entschwefelung von Steinkohlen
AT89304725T ATE86290T1 (de) 1989-05-10 1989-05-10 Enzymatische entschwefelung von steinkohlen.
GR930400664T GR3008006T3 (de) 1989-05-10 1993-05-31

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP89304725A EP0396832B1 (de) 1989-05-10 1989-05-10 Enzymatische Entschwefelung von Steinkohlen

Publications (2)

Publication Number Publication Date
EP0396832A1 true EP0396832A1 (de) 1990-11-14
EP0396832B1 EP0396832B1 (de) 1993-03-03

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Family Applications (1)

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EP89304725A Expired - Lifetime EP0396832B1 (de) 1989-05-10 1989-05-10 Enzymatische Entschwefelung von Steinkohlen

Country Status (5)

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EP (1) EP0396832B1 (de)
AT (1) ATE86290T1 (de)
DE (1) DE68905180T2 (de)
ES (1) ES2039855T3 (de)
GR (1) GR3008006T3 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993022403A1 (en) * 1992-04-30 1993-11-11 Energy Biosystems Corporation Process for the desulfurization and the desalting of fossil fuels
US5358870A (en) * 1990-02-28 1994-10-25 Institute Of Gas Technology Microemulsion process for direct biocatalytic desulfurization of organosulfur molecules

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2641564A (en) * 1948-03-31 1953-06-09 Texaco Development Corp Process of removing sulfur from petroleum hydrocarbons and apparatus
US4808535A (en) * 1986-08-05 1989-02-28 Atlantic Research Corporation Acinetobacter species and its use in removing organic sulfur compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2641564A (en) * 1948-03-31 1953-06-09 Texaco Development Corp Process of removing sulfur from petroleum hydrocarbons and apparatus
US4808535A (en) * 1986-08-05 1989-02-28 Atlantic Research Corporation Acinetobacter species and its use in removing organic sulfur compounds

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 109, 1988, pages 170-171, abstract no. 233905h, Columbus, Ohio, US; O.G. NGAIZA et al.: "Enzymic removal of organic sulfur from coal", & PREPR. PAP. - AM. CHEM. SOC., DIV. FUEL CHEM. 1988, 33(4), 623-30 *
CHEMICAL ABSTRACTS, vol. 95, 1981, pages 190-191, abstrct no. 172382d, Columbus, Ohio, US; & DD-A-147 365 (VEB PETROLCHEMISCHES KOMBINAT SCHWEDT) 01-04-1981 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5358870A (en) * 1990-02-28 1994-10-25 Institute Of Gas Technology Microemulsion process for direct biocatalytic desulfurization of organosulfur molecules
WO1993022403A1 (en) * 1992-04-30 1993-11-11 Energy Biosystems Corporation Process for the desulfurization and the desalting of fossil fuels
US5356813A (en) * 1992-04-30 1994-10-18 Energy Biosystems Corporation Process for the desulfurization and the desalting of a fossil fuel
US5496729A (en) * 1992-04-30 1996-03-05 Energy Biosystems Corporation Process for the desulfurization and the desalting of a fossil fuel

Also Published As

Publication number Publication date
DE68905180D1 (de) 1993-04-08
DE68905180T2 (de) 1993-08-05
ATE86290T1 (de) 1993-03-15
ES2039855T3 (es) 1993-10-01
GR3008006T3 (de) 1993-08-31
EP0396832B1 (de) 1993-03-03

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