EP0121343B1 - Integrated ionic liquefaction process - Google Patents

Integrated ionic liquefaction process Download PDF

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Publication number
EP0121343B1
EP0121343B1 EP19840301391 EP84301391A EP0121343B1 EP 0121343 B1 EP0121343 B1 EP 0121343B1 EP 19840301391 EP19840301391 EP 19840301391 EP 84301391 A EP84301391 A EP 84301391A EP 0121343 B1 EP0121343 B1 EP 0121343B1
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EP
European Patent Office
Prior art keywords
stream
solvent
alkaline
alkali
gas
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Expired
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EP19840301391
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German (de)
English (en)
French (fr)
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EP0121343A1 (en
Inventor
Richard L. Bain
Charles M. Rastle
Clifford R. Porter
Herbert D. Kaesz
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Pentanyl Technologies Inc
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Pentanyl Technologies Inc
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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
    • 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
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes

Definitions

  • This invention relates to the liquefaction of carbonaceous materials and in particular to a method of producing useful products, including fuel products which can be used directly in petroleum-like refining processes, or as a feed stock for further chemical synthesis, or as a low sulfur fuel oil or the like, and, pseudo-plastic products with melting points in the range of from about 100°C to 200°C which are solid products at ambienttemperature and are characterized by their reduced sulfur and ash content which make them useful as fuel and coke substitutes.
  • Ionic liquefaction as used herein is intended to mean the chemical process described herein, which is characterized by polar solvent solubilization of the polymeric structure of carbonaceous materials susceptible to the described treatment methods, in the presence of alkali and alkaline earth compounds in amounts which favor ionic reactions involving the solubilized carbonaceous material and ionic species such as phenoxide, hydroxide, and formate ions, and favor stabilization of the ionic species to produce distillable products, low-sulfur fuel oils, and low-ash reduced-sulfur pseudo-plastic, normally solid products useful as fuel, coke, or petrochemical feedstock.
  • Appell et al. in their paper entitled “On the Mechanism of Lignite Liquefaction with Carbon Monoxide and Water", Chem. and Ind., VoI. 47, (1967), p. 1703, describe how using freshly powdered low-rank coal and a selected solvent will produce a 72% yield of a benzene-soluble oil when using operating pressures near 5000 psig and temperatures in excess of 365°C. Appell et al., also describes the use of a solvent comprising alpha-naphthol (a phenol), phenanthrene (a polycyclic aromatic hydrocarbon) and water in the presence of naturally occurring amounts of alkali or alkaline-earth metal compounds at similar operating conditions.
  • alpha-naphthol a phenol
  • phenanthrene a polycyclic aromatic hydrocarbon
  • Suitable organic constituents include aromatic alcohols, polycyclic aromatic hydrocarbons, partially hydrogenated and/or fully hydrogenated polycyclic aromatic hydrocarbons, typically having from 1 to 4 carbon rings, and more preferably from 2 to 3 carbon rings e.g.
  • naphthalene anthracene, phenanthrene, acenaphthene, 1-methylnaphthalene, 2-methylnaphthalene, Tetralin (tetrahydronaphthalene), gamma-picoline, isoquinoline, dihydronaphthalene, Decalin (decahydronaphthalene), 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, and mixtures and derivatives thereof.
  • solubilizing agents and/or other organic constituents will be present: then in subsequent operation, the organic constituents will be carbonaceous material-derived phenols of the type, and polycyclic aromatic hydrocarbons of the type, or derivatives related to the type, described hereinbefore.
  • Particularly useful organic phase solubilizing agents and/or other organic fraction constituents have a boiling point above 50°C, more preferably of from 100°C to 460°C, and most preferably of from 150°C to 400°C. In the practice of this latter embodiment, the solubilizing agent is typically from about 50 to 100 weight percent of the organic fraction of the solvent/ solute system.
  • alkali and alkaline-earth metal compounds include hydroxides, carbonates, bicarbonates, nitrates, sulfates, sulfites, sulfides, formates and other salts, mixtures thereof, and the like, although other compounds may be employed for the purpose.
  • Specific examples include NaOH, Na 2 C0 3 , NaHC0 3 , Na 2 S0 4 , NaN0 3 , KOH, K Z C0 3 , KHC0 2 , CaC0 3 , mixtures thereof and the like.
  • Presently preferred species are NaOH, KOH and Na 2 CO 3 in from about 1 part to about 40 parts per 400 parts by weight of the solvent/solute system, more usually 1 to about 15 parts per 400 parts by weight of the solvent/solute system.
  • the amount of alkali or alkaline-earth metal compound present for purposes of the present invention is an added amount, i.e. an amount in excess of the amount which would be present from the various naturally occurring alkali or alkaline-earth metal compounds.
  • the alkali or alkaline-earth metal compound content will be maintained at the desired level in a recycle solvent stream.
  • Example VI et seq. the combination of organic and inorganic fractions and constituents provide a beneficially synergistic effect on solubilizing of carbonaceous material.
  • reaction times of at least about 1 minute, more preferably from 10 minutes to 120 minutes, and most preferably from 15 minutes to 60 minutes are sufficient to result in enhanced solubilizing and the production and/or conversion of hydrocarbon liquids.
  • the parallel formate ion mechanism V to VII is This mechanism is believed to be enhanced at the mild conditions employed because of the intimate contact made possible by the phenolic solvent solubilization where there is competition for available ionic species in the presence of the water gas shift reaction VIII to X.
  • the summation of VIII, IX and X is the net water gas shift reaction XI:
  • the feed preparation at (A) comminutes the carbonaceous material, stream (1), by conventional means such as hammermills or ball mills or comparable equipment; and adds a water-alkali mixture stream (4); and recycle polar solvent streams (2) and (3), containing greater than 50% by weight of phenolic species.
  • the comminution process may be accomplished either dry or wet. If performed wet, then the recycle polar solvent may be used as the wetting agent, if proper precautions are taken.
  • recycle streams (2) plus (3) is between 1500 and 3500 parts by weight depending on the prepared form of the carbonaceous material, with 2000 parts by weight of solvent the most preferred amount.
  • the polar recycle solvent contains preferably greater than about 50% by weight of phenolic compounds, and more preferably greater than 60% by weight phenolic compounds.
  • the preferred amount of alkaline material in water-alkali mixture stream (4) is selected to be enough to produce the desired results. It has been found under the conditions disclosed herein that between about 25 parts and 400 parts by weight per 1000 parts by weight of carbonaceous material is effective with the more preferred amount being between about 25 and 150 parts by weight, and depending on the kinds and amounts of phenolic compounds employed, the preparation of the carbonaceous material and the conditions selected, the most preferred amount is about 50 parts.
  • the preferred reactor design is a high length to diameter ratio reactor with internal baffles to provide sufficient mixing of the polar solvent, alkali, and carbonaceous materials for the reaction mechanisms to proceed efficiently.
  • other reactor designs can, of course, be selected for use. Temperature and pressure may be adjusted for the optimum conversion of individual carbonaceous feed materials.
  • the preferred temperature range is 200 to 300°C (392 to 572°F); the most preferred temperature range is 200 to 250°C (392 to 482°F).
  • the slurry phase residence time is preferably less than 30 minutes, more preferably less than 15 minutes, and most preferably less than 5 minutes.
  • Preferred catalyst loadings are about 0.01 to 1.0 kg cat/kg oil/hr, more preferred loadings are about 0.01 to 0.5 kg cat/kg oil/hr, the most preferred loadings are about 0.05 to 0.15 kg cat/kg oil/hr.
  • Preferred hydrogen treatment rates are about 178 to 1424 m 3 H 2 /m 3 oil (1000 to 8000 SCFH 2 /BBI oil); more preferred hydrogen treatment rates are about 178 to 712 m 3 H 2 /m 3 oil (1000 to 4000 SCFHJBBI oil.
  • the refined liquids from the hydrogenation train will preferably have been converted to greater than 80 wt percent oils, more preferably than 90 wt percent oils, and most preferably greater than 95 wt percent oils, as defined by pentane solubility and ASTM D1160-77 distillation results.
  • the preferred viscosity of the refined oil is between about 5 x 10- 6 and about 1 x 10- 4 m 2 /s at 38°C (5 to 100 centistokes at 100°F), and more preferably between about 5 x 10- 6 and 2 x 10- 5 m 2 /s (5 to 20 centistokes at 100°F).
  • the preferred density of the refined oil is between about 1000 and 1100 kg/m 3 (1.0 to 1.1 grams/ml).
  • the refined oils, stream (17) of Fig. 1 and stream (38) from catalyst regeneration alkali recovery unit (V) are then sent to a distillation unit, unit (F) for final processing as will be described in detail hereinafter.
  • the preferred acid for this embodiment is sulfuric acid.
  • a portion of the sulfuric acid could come from acid gas removal operations, unit (I) of Fig. 1. Additional required sulfuric acid would have to be added as make-up acid, stream (121).
  • the light aqueous-rich stream (116) leaving the liquid separator is divided into two streams (118 and 120).
  • Stream (120) is mixed with make-up acid (121) and recycled to the crude product stabilizer (FF).
  • make-up acid can come from the acid-gas removal unit in the gas processing unit, (I) of Fig. 1, and from purchased acid.
  • the remaining aqueous liquids in the stream (118) are sent to a distillation tower (II) where water is vaporized, and transferred in stream (119) for recycling to the crude product stabilizer (FF).
  • An organic distillate, stream (126) and a spent acid stream, stream (127) consisting of heavy organics and alkaline salts such as Na 2 SO 4 are also produced.
  • Fig. 8 presents a modified schematic of the integrated ionic liquefaction process using acidification in an acidification unit (FF) for the ionic liquid stabilization, and acid recovery in an acid recovery unit (AR).
  • FF acidification unit
  • AR acid recovery unit
  • the acid will replace alkali atoms present as alkali-organic salts with hydrogen with the alkali being soluble in the aqueous layer.
  • the liquid extraction stream will include a final water wash of the filtrate to remove any remaining inorganic constituents as well as acid components still present in the organic layer.
  • the preferred temperature for the separation step (C1) is preferably between about 150 and 100°C (302 and 212°F).
  • the pressure is maintained at a sufficient level to obtain efficient separation, preferably between about 0.34 and 1.03 MPa (50 to 150 psia).
  • the solids content of the liquid in the stream (609) is typically reduced to less than about 1.0 percent by weight, the mineral matter content to less than about 0.5 percent by weight, and the alkaline species content to less than about 0.25 percent by weight.
  • the values obtained are dependent upon factors such as the degree of comminution used in the feed preparation, ionic liquefaction conditions, and filter equipment design.
  • the separation train should preferably be operated to reduce the alkaline compound content of the stream (609), of Fig.
  • the solid and liquid components are removed from the reactor and mixed in a high speed blender. Samples are removed from the blender and placed in 250 ml. centrifuge tubes. The samples are subjected to an empirical selective solvent extraction procedure using tetrahydrofuran (THF), toluene, and pentane to determine total conversion, preasphaltenes, asphaltenes, and oil plus gas.
  • THF tetrahydrofuran
  • toluene toluene
  • pentane pentane to determine total conversion, preasphaltenes, asphaltenes, and oil plus gas.
  • Carbon monoxide conversion is calculated from analysis, over time, of the exit gas, and plotted with temperature and the results shown in Fig. 12, wherein:
  • Example VI The foregoing procedure of Example VI is repeated except 15 g. of sodium carbonate was used replacing the 15 g. of sodium hydroxide.
  • the semi-batch liquefaction unit is heated, charged, and the products analyzed as previously described.
  • the results of the selective solvent extraction procedure are shown in Table 13.
  • Tables 12 and 13 demonstrate the significantly improved results obtained by practice o" the present invention.
  • Table 13 shows that the presence of the organic phase solubilizing agent, m-cresol. in the absence of the inorganic phase constituent as Example VI, yields a MAF conversion of 40 wt%.
  • the MAF conversion is 39 wt%, which is virtually unchangec from Example VI.
  • Example VIII under operating conditions of Examples VI and VII, the synergistic effect of the alkali/alkaline-earth constituent is observed as the yield is increased to 82.52 MAF wt%.
  • the organic phase solubility agent is a synthetic solvent which is considered to represent a recycle stream in a continuous liquefaction facility.

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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)
EP19840301391 1983-03-03 1984-03-02 Integrated ionic liquefaction process Expired EP0121343B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US47173183A 1983-03-03 1983-03-03
US471731 1983-03-03
US56422383A 1983-12-27 1983-12-27
US564223 1983-12-27

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EP0121343A1 EP0121343A1 (en) 1984-10-10
EP0121343B1 true EP0121343B1 (en) 1988-05-18

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EP (1) EP0121343B1 (it)
AU (2) AU573573B2 (it)
CA (1) CA1262240A (it)
DE (1) DE3471319D1 (it)
GR (1) GR79531B (it)
TR (1) TR21864A (it)
ZW (1) ZW3684A1 (it)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4846963A (en) * 1986-04-18 1989-07-11 Knudson Curtis L Ionic liquefaction process
US8398848B2 (en) 2008-10-02 2013-03-19 Exxonmobil Research And Engineering Company Desulfurization of heavy hydrocarbons and conversion of resulting hydrosulfides utilizing copper metal
US8968555B2 (en) 2008-10-02 2015-03-03 Exxonmobil Research And Engineering Company Desulfurization of heavy hydrocarbons and conversion of resulting hydrosulfides utilizing copper sulfide
US8696889B2 (en) 2008-10-02 2014-04-15 Exxonmobil Research And Engineering Company Desulfurization of heavy hydrocarbons and conversion of resulting hydrosulfides utilizing a transition metal oxide
EP2199366A1 (en) * 2008-12-10 2010-06-23 KiOR, Inc. Conversion of biomass to bio-oil using inorganic carbonates and decomposition and regeneration of inorganic carbonates
CN112480957A (zh) * 2020-10-23 2021-03-12 西安长庆科技工程有限责任公司 一种油田微正压原油稳定装置及工艺方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4085029A (en) * 1976-01-12 1978-04-18 Malek John M Method for separating liquid and solid products of liquefaction of coal or like carbonaceous materials
GB2075046B (en) * 1979-09-11 1983-08-24 Shimizu K Process for liquefying coal
ZA817140B (en) * 1980-10-27 1982-11-24 Seth Manu Coal conversion by solvolysis

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Publication number Publication date
AU575872B2 (en) 1988-08-11
DE3471319D1 (en) 1988-06-23
AU573573B2 (en) 1988-06-16
ZW3684A1 (en) 1984-06-20
TR21864A (tr) 1985-10-01
GR79531B (it) 1984-10-30
EP0121343A1 (en) 1984-10-10
AU2517184A (en) 1984-09-13
CA1262240A (en) 1989-10-10
AU3491384A (en) 1985-05-09

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