EP0045178A2 - Verflüssigung eines kohlenstoffhaltigen Materials mit einem Wasserstoffdonorlösungsmittel in der Gasphase - Google Patents

Verflüssigung eines kohlenstoffhaltigen Materials mit einem Wasserstoffdonorlösungsmittel in der Gasphase Download PDF

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Publication number
EP0045178A2
EP0045178A2 EP81303353A EP81303353A EP0045178A2 EP 0045178 A2 EP0045178 A2 EP 0045178A2 EP 81303353 A EP81303353 A EP 81303353A EP 81303353 A EP81303353 A EP 81303353A EP 0045178 A2 EP0045178 A2 EP 0045178A2
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EP
European Patent Office
Prior art keywords
hydrogen
hydrogen donor
coal
carbonous
donor material
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Application number
EP81303353A
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English (en)
French (fr)
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EP0045178A3 (de
Inventor
Daniel Ray Neskora
Richard Henry Schlosberg
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Filing date
Publication date
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of EP0045178A2 publication Critical patent/EP0045178A2/de
Publication of EP0045178A3 publication Critical patent/EP0045178A3/de
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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
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C10G1/042—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction by the use of hydrogen-donor solvents

Definitions

  • the present invention relates to a method for enhancing the conversion of carbonous materials such as coal, oil shale, and peat, to liquids, by use of specific type hydrogen donor materials under critical processing conditions.
  • a method for enhancing the conversion to liquids of solid carbonous materials selected from coal, oil shale, peat and solid products thereof comprises converting the carbonous material in the presence of a vapor phase hydrogen donor material containing one or more effective hydrogen donor solvents wherein each effective donor solvent is characterized by: (a) a heterocyclic ring in which the heteroatom is nitrogen, (b) having at least one donatable hydrogen located on the heterocyclic ring, and (c) becoming more unsaturated and/or aromatic upon the loss of the donatable hydrogen(s).
  • the conversion is performed at substantially atmospheric pressure, at an effective vapor residence time and at a temperature from about the boiling point of the hydrogen donor material to about 550°C.
  • the carbonous material is subbituminous coal
  • the hydrogen donor material comprises 1,2,3,4-tetrahydroquinoline
  • the pressure is atmospheric pressure
  • the maximum conversion temperature is about 500°C
  • the donor vapor residence time is about 1 second.
  • the carbonous material is coal or oil shale and the hydrogen donor material is recycled from a product stream resulting from the practice of the present invention.
  • Effective hydrogen donor compounds suitable for use herein include those compounds which: (a) contain a heterocyclic ring in which the heteroatom is nitrogen, (b) have at least one donatable hydrogen located on the heterocyclic ring, and (c) have a tendency to become more unsaturated and/or aromatic upon the loss of the donatable hydrogen(s).
  • Nonlimiting examples of such compounds include, 1,2,3,4-tetrahydroquinoline; 1,2,3,4-tetrahydroisoquinoline; 1,2,3,4-tetrahydrocarbazole; 1,2,3,4,5,6-hexahydrocarbazole; acrilan, piperidine, pyrrolidine, indoline and their alkylated derivates and mixtures thereof.
  • Preferred are 1,2,3,4-tetrahydroquinoline; 1,2,3,4-tetrahydroisoquinoline and indoline.
  • Such donor materials include tetralin, phenanthrene, C 12 and C13: acenaphthenes, their hydrogenated analogs and indole.
  • the pressure at which the carbonous material is converted herein is preferably about atmospheric pressure (14.7 psia), although pressures slightly higher or lower may be employed to facilitate mass transfer in the processing scheme.
  • the temperature at which conversion occurs in the presence of the hydrogen donor vapor may range from the initial boiling point of the hydrogen donor material to about 550°C.
  • the conversion temperature be about 200°C to about 500°C, more preferably from about 250°C to about 500°C; most preferred is about 350°C to about 500°C.
  • the residence time at which the donor vapor is in contact with the solid carbonous material, at conversion temperatures must be an effective residence time.
  • an effective residence time we mean a time long enough so that reaction with the carbonous material takes place, but short enough so that undesirable secondary reactions are minimized.
  • Such undesirable reactions include donor solvent degradation (other than loss of hydrogen) and irreversible combinations of donor molecules with either the converted or unconverted carbonous material.
  • donor solvent degradation other than loss of hydrogen
  • irreversible combinations of donor molecules with either the converted or unconverted carbonous material are minimize undesirable secondary reactions of first formed carbonous material derived fragments. That is, the donor material is preferably removed from the reaction zone, and cooled, substantially immediately after donating its hydrogen. This is generally a time from about 0.1 to about 30 seconds, although less than 10 seconds is generally desired. It will be noted that less than 0.1 second may also be feasible when the invention is employed in specially designed, short residence time reaction vessels.
  • a donor vapor residence time is chosen, based on the particular hydrogen donor material and the temperature employed, such that a minimal amount, e.g., no more than about 5 wt.% of the donor material is lost through degradation, other than by aromatization.
  • Figure 1 herein illustrates that at a maximum temperature of 500°C, at atmospheric pressure, at a donor to coal weight ratio of 1 to 1, and with 1,2,3,4-tetrahydroquinoline as the donor material, substantially maximum conversion to liquids is achieved within a donor vapor residence time of about seven-tenths of a second. Also illustrated in Figure 1 is a relative plot showing THQ degradation other than by aromatization at 500°C.
  • substantially maximum conversion of carbonous material to liquids and recovery of the hydrogen donor material or its aromatic form in relatively high yields for hydrogenation and recycling is achieved.
  • Recovery and hydrogenation of this material can be achieved by appropriate conventional methods suitable for such purposes.
  • hydrogenation can be accomplished with hydrogen in the presence of a suitable hydrogenation catalyst.
  • hydrogenation temperatures can range from about 100°C to about 450°C at pressures up to about 2000 psig.
  • a variety of hydrogenation catalysts can be employed such as those containing components from Group VIB and Group VIII, of the Periodic Table of the Elements, e.g., cobalt, molybdate or nickel molybdate, on a suitable support, such as alumina, silica, titania, etc.
  • a suitable support such as alumina, silica, titania, etc.
  • the hy-' drogenated product can then be fractionated to the desired boiling range and recycled to the reaction zone.
  • liquids derived therefrom are generally rich in cyclic nitrogen-containing compounds which can be separated from the product stream and hydrogenated, by conventional techniques, to give a recycle stream rich in the type hydrogen donor material suitable for use herein.
  • the effectiveness of any particular recycle stream may be determined by measuring the total donatable hydrogen associated with the heterocyclic nitrogen ring of those type donor solvents claimed herein.
  • the recycle stream is analyzed by any appropriate analytical technique, such as gas chromatography, to determine its content of specific suitable donor solvents and their concentrations, on a weight percent dry carbonous material basis.
  • any appropriate analytical technique such as gas chromatography
  • the number of donatable hydrogens on the heterocyclic nitrogen ring of the donor solvent can be easily calculated.
  • the number of donatable hydrogens, as calculated, can then be compared to a model curve for determining the projected liquid yield for that particular concentration of donatable hydrogens.
  • the recycle stream can then be upgraded with respect to the donor material depending on the desired liquid yield.
  • Figure 2 herein shows a plot of liquid yield (weight percent on dry coal basis) versus weight percent of donatable hydrogen on heterocyclic nitrogen ring on a dry coal basis, at a maximum temperature of 500°C, 1 atmospheric pressure, and helium as a sweep gas.
  • the plot was obtained by use of model hydrogen donor solvents . such as 1,2,3,4-tetrahydroquinoline; 1,2,3,4-tetrahydroisoquinoline; 1,2,3,4-tetrahydrocarbazole, and indoline and mixtures thereof at various solvent to coal ratios. Similar correlation curves can easily be prepared for oil shale and peat by routine experimentation by those having ordinary skill in the art.
  • the donor solvent/carbonous material ratio can range from about 0.1/1 to about 10/1, preferably about 0.1/1 to about 4/1.
  • the optimum ratio of donor material to carbonous material will depend on such things as the particular carbonous material being converted, the processing conditions employed, and the type and the concentration of the particular donor materials comprising the recycle solvent. Of course, the optimum ratio can be determined by routine experimentation by one having ordinary skill in the art.
  • any type of coal, peat, oil shale or products thereof which are normally solid at room temperature may be utilized in the practice of the present invention.
  • liquid yields from bituminous, subbituminous and lignite will be particularly enhanced. While not wishing to be limited by theory, the data herein suggest that there is a correlation between liquid yield and reactive organic functionality in the feed stock. Therefore, when coal is employed in the practice of the invention, lower rank coals are preferred because of their higher content of reactive organic functionality.
  • the carbonous material have as high a surface area as possible; although, it is not economically justifiable to pulverize the material to a very fine powder. Consequently, it is desirable to expose as much of the carbonous material surface area as possible without losing carbonous material as dust or fines or as the economics of material grinding or process equipment may dictate.
  • the carbonous material will be ground to a finely divided state and will contain a majority of particles less than about 4 mesh, U.S. sieve size.
  • the carbonous material may be dried by conventional drying techniques, for example, heating to a temperature of about 100°C to 110°C.
  • the carbonous material is fed to a reaction vessel and heated to the required temperatures.
  • the hydrogen donor material is introduced into the reaction vessel when the temperature of the carbonous material is greater than the boiling point of the donor material.
  • reaction vessels suitable for use herein include, fixed or fluid bed, as well as free fall or entrained solid reactors.
  • the main constraint in any reactor configuration is to minimize solvent vapor residence times for any given operating temperature, and can be determined routinely by those having ordinary skill in the art.
  • Example 18 15 grams of Green River Oil Shale was charged at room temperature and atmospheric pressure into a continuous gas flow batch fixed-bed tubular reactor.
  • Example 19 45 grams of Kentucky Devonian Oil Shale was charged, also at room temperature and pressure, into a continuous gas flow batch fixed-bed tubular reactor.
  • the reactors were heated to a temperature of about 500°C at a rate of about 400°C per hour and 25 grams and 42.6 grams of THQ, respectively, were introduced.
  • Identical base runs without THQ were run for comparative purposes. That is, Comparative Example O is the base for Example 18 and Comparative Example P is the base for Example 19.
  • the vapor residence time of solvent in contact with shale was approximately 1 second and solid residence time at which the shale was in contact with solvent vapor was about 40 minutes.
  • Helium was used as a sweep gas for all examples.
  • Table V The results of liquid and gaseous yield are shown in Table V below.

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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)
EP81303353A 1980-07-25 1981-07-22 Verflüssigung eines kohlenstoffhaltigen Materials mit einem Wasserstoffdonorlösungsmittel in der Gasphase Withdrawn EP0045178A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US17236980A 1980-07-25 1980-07-25
US172369 1980-07-25

Publications (2)

Publication Number Publication Date
EP0045178A2 true EP0045178A2 (de) 1982-02-03
EP0045178A3 EP0045178A3 (de) 1982-06-02

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EP81303353A Withdrawn EP0045178A3 (de) 1980-07-25 1981-07-22 Verflüssigung eines kohlenstoffhaltigen Materials mit einem Wasserstoffdonorlösungsmittel in der Gasphase

Country Status (6)

Country Link
EP (1) EP0045178A3 (de)
JP (1) JPS5774388A (de)
AU (1) AU539055B2 (de)
BR (1) BR8104794A (de)
CA (1) CA1164379A (de)
ZA (1) ZA815116B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4871699A (en) * 1988-01-11 1989-10-03 Amoco Corporation Process for reducing coke on spent catalyst in a fluid catalytic cracking unit
CN120684173A (zh) * 2025-07-11 2025-09-23 太原理工大学 一种油页岩地下加氢液化的系统及方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1482690A (en) * 1974-12-19 1977-08-10 Coal Ind Hydrogenation of coal
GB1564829A (en) * 1976-12-17 1980-04-16 Exxon Research Engineering Co Hydrogen-donor solvent coal liquefaction process
US4250014A (en) * 1978-08-21 1981-02-10 Exxon Research & Engineering Co. Coal liquefaction process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4871699A (en) * 1988-01-11 1989-10-03 Amoco Corporation Process for reducing coke on spent catalyst in a fluid catalytic cracking unit
CN120684173A (zh) * 2025-07-11 2025-09-23 太原理工大学 一种油页岩地下加氢液化的系统及方法

Also Published As

Publication number Publication date
AU7340581A (en) 1982-01-28
ZA815116B (en) 1982-07-28
BR8104794A (pt) 1982-04-13
JPS5774388A (en) 1982-05-10
EP0045178A3 (de) 1982-06-02
CA1164379A (en) 1984-03-27
AU539055B2 (en) 1984-09-06

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Inventor name: SCHLOSBERG, RICHARD HENRY