WO1994029406A1 - Procede d'hydroconversion catalytique - Google Patents

Procede d'hydroconversion catalytique Download PDF

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Publication number
WO1994029406A1
WO1994029406A1 PCT/US1994/006545 US9406545W WO9429406A1 WO 1994029406 A1 WO1994029406 A1 WO 1994029406A1 US 9406545 W US9406545 W US 9406545W WO 9429406 A1 WO9429406 A1 WO 9429406A1
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WO
WIPO (PCT)
Prior art keywords
hydroconversion
carbonaceous material
catalyst
metal
mixture
Prior art date
Application number
PCT/US1994/006545
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English (en)
Inventor
Lavanga R. Veluswamy
Claude C. Culross
Michel Daage
Ronald Liotta
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Exxon Research & Engineering Company
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Filing date
Publication date
Application filed by Exxon Research & Engineering Company filed Critical Exxon Research & Engineering Company
Priority to AU70592/94A priority Critical patent/AU7059294A/en
Publication of WO1994029406A1 publication Critical patent/WO1994029406A1/fr

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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

Definitions

  • This invention relates to a catalytic process for converting a carbonaceous material to a liquid product. More specifically, this invention relates to a process for hydroconverting coal in a hydroconverting zone to liquid hydrocarbon products in the presence of a catalyst prepared in situ, with the catalyst being added to a mixture of coal and solvent as an oil soluble metal compound. The process provides for a product which is low in gas content and has a low heteroatom concentration in the liquid fraction.
  • Catalytic hydroconversion of hydrocarbonaceous material to liquids employing a liquid transfer medium such as an organic solvent, is well known.
  • a liquid transfer medium such as an organic solvent
  • the hydrocarbonaceous material is slurried with a solvent and a catalyst, and is reacted in the presence of molecular hydrogen at elevated temperatures and pressures. See, for example, U.S. Patent No. 4,485,008.
  • Catalytic hydroconversion techniques generally produce relatively high gas yields and aromatic distillates with high heteroatom content. These types of distillate compounds generally have sulfur, nitrogen, or oxygen in the ring structure. Extensive downstream upgrading may be required in order to convert the aromatic distillates to gasoline or fuel oils and to remove heteroatoms from the products. Upgrading is expensive, however, Therefore, it is economically desirable to employ a catalytic hydroconversion procedure which reduces gas production as well as the heteroatom content of the raw liquid product.
  • the invention provides for a process for catalytically converting a heteroatom containing carbonaceous material to a hydroconversion product stream which comprises forming a mixture of carbonaceous material, hydrogen donor solvent, and a catalyst precursor, wherein said catalyst precursor is an oil soluble metal compound having a metal content of about 2-20 wt % on the basis of the carbonaceous material and said metal is selected from the group consisting of Groups II, III, IV, V, VIB, VIIB and VIII of the Periodic Table of Elements; converting the catalyst precursor to an active catalyst within the mixture by heating the mixture in the presence of hydrogen to form an activated catalyst mixture; reacting the activated catalyst mixture under hydrocarbon conversion conditions to form a hydroconversion product stream; separating the hydroconversion product stream into component streams comprising about 8-11 wt %, based on the carbonaceous material, of a C ⁇ -C 4 paraffins and olefins
  • Fig. 1 is a schematic flow plan of a preferred embodiment of this invention. DETAILED DESCRIPTION OF INVENTION
  • the process of the invention is generally applicable, but not limited to, the hydroconversion of heteroatom containing carbonaceous feeds such as heavy hydrocarbonaceous oils having constituents that generally have a boiling point above about 900°F, coal and mixtures thereof.
  • Suitable heavy hydrocarbonaceous oil feeds include heavy mineral oils; crude petroleum oils, including heavy mineral oils; residual oils such as atmospheric residuum and vacuum residuum; tar; bitumen; tar sand oils; shale oils; liquid products derived from coal liquefaction processes, including coal liquefaction bottoms, and mixtures thereof.
  • the process is also applicable for the simultaneous conversion of mixtures of coal and a hydrocarbonaceous oil.
  • coal refers to a normally solid carbonaceous material such as anthracite, bituminous coal, sub-bituminous coal, lignite and mixtures thereof. All boiling points referred to herein are atmospheric pressure boiling points unless otherwise specified.
  • the coal is preferably mixed with a hydrogen donor solvent.
  • the hydrogen donor solvent employed is preferably an intermediate stream which boils between about 350°F and 1000°F, preferably between about 400°F and about 900°F.
  • This stream comprises hydrogenated aromatics, naphthenic hydrocarbons, phenolic materials and similar compositions.
  • These compositions preferably include at least about 20 wt. %, preferably at least about 50 wt. %, compounds which function as hydrogen donors under typical hydroconversion conditions.
  • Such hydroconversion conditions are well known in the art.
  • Compounds which are acceptable as hydrogen donor solvents include hydrogenated creosote oil, hydrogenated intermediate product streams from catalytic cracking of petroleum feedstocks, and other coal-derived liquids which are rich in indane, C ⁇ 0 -C 12 tetralins, decalins, biphenyls, methylnaphthalene, dimethylnaphthalene, C 12 -C 1 3 acenaphthenes and tetrahydroacenaphthene and similar donor compounds.
  • the coal When the process is used to hydroconvert coal, the coal is preferably provided in particulate form.
  • the coal particles preferably are of a size which range up to about one eighth inch in diameter, suitably 8 mesh (Tyler) .
  • the coal particles and hydrogen donor solvent are preferably mixed at a solvent-to-coal weight ratio of about 1-5 to 1, more preferably about 1.5-2 to 1.
  • the catalyst of this invention is an oil-soluble metal compound or dispersible metal compound.
  • the metal compound may be a compound that is soluble in a hydrocarbonaceous oil or a compound that is soluble in a liquid organic medium that can be dispersed in the hydrocarbonaceous oil.
  • the metal compound may also be a compound that is water soluble, and an aqueous solution of the compound can be dispersed in the hydrocarbonaceous medium.
  • the catalyst of this invention is made by converting a metal containing, oil dispersible or oil soluble compound into an active metal catalyst under process conditions.
  • Suitable oil soluble compounds which are convertible to active metal-containing catalysts under process conditions include (1) metal-containing inorganic compounds such as metal-containing halides, oxyhalides, hydrated oxides, heteropoly acids (e.g., phosphomolybdic acid, molybdosilisic acid) ; (2) metal salts of organic acids such as acyclic and alicyclic aliphatic carboxylic acids containing two or more carbon atoms (e.g., naphthenic acids); aromatic carboxylic acids (e.g., toluic acid); sulfonic acids (e.g., toluenesulfonic acid); sulfinic aids; mercaptans, xanthic acid; phenols, di and polyhydroxy aromatic compounds; (3) metal-containing organometallic compounds including metal-containing chelates such as 1,3-
  • the metal constituent of the oil dispersible metal compound that is convertible to a solid, metal containing catalyst is selected from the group consisting of Groups II, III, IV, V, VIB, VIIB and VIII, and mixtures thereof of the Periodic Table of the Elements.
  • Non-limiting examples include zinc, antimony, bismuth, titanium, cerium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel and the noble metals including platinum, iridium, palladium, osmium, ruthenium, and rhodium.
  • the preferred metal constituent of the oil dispersible compound is selected from the group consisting of molybdenum, tungsten, vanadium, chromium, cobalt, titanium, iron, nickel and mixtures thereof.
  • Preferred compounds of the given metals include the salts of acyclic (straight or branch chained) aliphatic carboxylic acids, salts of cyclic aliphatic carboxylic acids, polyacids, carbonyls, phenolates and organoamine salts.
  • Oil dispersible metal compounds which can be used in this invention are further described in U.S. Patent No. 4,295,995, the teachings of which are incorporated herein by reference.
  • the preferred oil dispersible metal compounds of this invention are inorganic polyacids of metals selected from Groups VA, VIA, and mixtures thereof. Included in this group are vanadium, niobium, chromium, molybdenum, tungsten and mixtures thereof.
  • Suitable inorganic polyacids include phosphomolybdic acid, phosphotungstic acid, phosphovanadic acid, silicomolybdic acid, silicotungstic acid, silicovanadic acid and mixtures thereof.
  • the preferred polyacid is a phosphomolybdic acid.
  • heteropolyacids and “isopolyacids” are used in accordance with the definitions given in Advanced Inorganic Chemistry. 4th Edition, S.A. Cotton and Geoffrey Wilkinson, Interscience Publishers, N.Y., pages 852-861.
  • Another preferred metal compound is a salt of an alicyclic aliphatic carboxylic acid such as the metal naphthenate.
  • Other preferred types of metal compounds are the heteropoly acids, e.g., phosphomolybdic acid, as well as oil soluble and/or highly dispersible molybdenum complexes such as:
  • Ri and R 2 can be the same or different and each can be a Ci to C 18 alkyl group, a C 5 to C 8 cycloalkyl group, a C 6 to C 18 alkyl substituted cycloalkyl group, or a C 6 to Cis aromatic or alkyl substituted aromatic group, or
  • Ri and R 2 are as indicated above, and ⁇ -S denotes a sulfide (S " ) ligand bridging the two molybdenum atoms, or any related complex of molybdenum with dithiocarbamate, dithiophosphate, xanthates, or thioxanthate ligands.
  • S " sulfide
  • the molybdenum complex is dioxobis(n- dibutyldithiocarbamato)Mo0 2 , generally referred to as dioxoMoDTC.
  • the molybdenum complex is
  • Mo may be used alone as the metal component of the catalyst in the hydroconversion process, it is often promoted with certain metals in upgrading operations such as hydrotreating and hydrocracking.
  • metals include Ni, Co, Cu, Pt, Pd and Sn. These metals have been found to have a promoting effect on Mo, increasing liquid yields and cracking selectivity at high catalyst concentrations as well as reducing the presence of heteroatoms such as S and N.
  • NiEEX and PtEEX are generally referred to as NiEEX and PtEEX, respectively.
  • hydroconversion and slurry upgrading occur in one step, in the hydroconversion zone.
  • the catalyst entering the hydroconversion zone and subsequently recycled preferably comprises Mo or Mo promoted with Ni, Co, Cu, Pt, Pd or Sn.
  • the catalyst metal will comprise Mo and Ni at a molar ratio of between about 2:1 and 4:1, more preferably about 3:1.
  • the total concentration of metal on the basis of carbonaceous material will be about 2-20 wt %, preferably about 5-10 wt %.
  • the process of this invention will yield a product stream comprising about 8-11 wt %, based on the hydrocarbonaceous feed, of a C ⁇ -C 4 paraffins and olefins stream having a boiling point of less than about 80°F, and about 55-75 wt %, based on the hydrocarbonaceous feed, of a hydrocarbon distillate fraction having a boiling point of about 80-650°F.
  • About 40-60 wt % of the total distillate fraction will be a naphtha stream having a boiling point of about 80-350°F.
  • the reduced gas concentration in the conversion product is also reflected in the increased hydrogen to carbon ratio of the liquid product stream resulting from the process of this invention relative known processes.
  • the liquid product stream in this invention will have a hydrogen to carbon ratio of about 1.4 to 1.6.
  • the oil-soluble metal compound or dispersible metal compound is preferably dissolved in a hydrogen donor solvent and slurried with coal.
  • the metal compound is actually considered a catalyst precursor and should be activated to proceed with the hydroconversion process.
  • the catalyst precursor is preferably mixed with the solvent at a solvent to catalyst precursor ratio of about 1-2 to 1, more preferably about 1.6 to 1.
  • a preferred method of activating the catalyst precursor is to heat the mixture of catalyst precursor, carbonaceous material and solvent to a temperature ranging from about 600°F to 1000°F, at a pressure ranging from about 500 psig to 5000 psig, in the presence of a hydrogen-containing gas.
  • the hydrogen- containing gas can be molecular hydrogen or a hydrogen donating gas such as hydrogen sulfide.
  • the activation process can be performed prior to entering the hydroconversion zone, or the hydroconversion zone can be
  • particulate coal is added to mixing zone 1 through a line 2.
  • Catalyst precursor is to be dissolved in a hydrogen donor solvent is also added to mixing zone 1 through a line 3. After the coal, catalyst precursor and hydrogen donor solvent have been thoroughly mixed, the
  • a hydrogen gas is added to the mixture, for example, through a line 5 under hydroconversion conditions. It is not necessary, however, that the hydrogen gas be added at the hydroconversion zone 4. It can be added
  • the hydroconversion zone 4 is maintained at a temperature ranging from about 600-1000°F, preferably from about 700-
  • the hydrogen partial pressure within the hydroconversion zone 4 will preferably range from about 500 psig to 5000 psig, more preferably from about 1000 psig to 3000 psig.
  • the residence time in the hydroconversion zone 2 will be about 0.1 minute to 8 hours,
  • the hydroconversion product is removed from the hydroconversion zone 4, and sent to a separation zone 6 for separation into separate component product streams.
  • the 35 hydroconversion product comprises gas, liquid, and bottoms component streams at standard conditions.
  • the separation zone 6 is preferably operated at standard flash conditions.
  • the products of the hydroconversion zone 4 are flashed in the separation zone 6 at reduced pressure and at a temperature of about 400-800°F.
  • the gas component stream comprises components having a boiling point of less than about 80°F.
  • This stream includes compounds such as CO, C0 2 , H 2 S, NH 3 and hydrocarbons such as C ⁇ -C 4 paraffins and olefins.
  • a portion of the gas stream can be recycled to the hydroconversion zone 4, since the gas stream will typically contain a high concentration of a hydrogen gas.
  • the gas stream can also be scrubbed by conventional methods before or after recycle. Scrubbing can be used to reduce the content of hydrogen sulfide or carbon dioxide.
  • the liquid product component stream from the separation zone 6 is recovered as a distillate fraction having a boiling point of about 80-650°F.
  • the amount of distillate recovered is significant in comparison to known methods. Typically about 55-75 wt %, on the basis of carbonaceous feed, of the distillate is recovered. Of the total distillate recovered, about 40-60 wt % will be a naphtha product having a boiling point of about 80-350°F.
  • the non-naptha fraction can be used as a diesel or fuel oil.
  • the bottoms component stream will generally comprise a middle to heavy distillate fraction having a boiling point of at least about 650°F and solid carbonaceous material. Included with the solid carbonaceous material will be catalyst which typically passes through the hydroconversion zone 4, becoming part of the bottoms stream. As shown in Fig. 1, the bottoms stream is transferred to a separation zone 7, where it is to be further separated into its component parts.
  • the separation zone 7 can operate at either standard or vacuum conditions. Any of several, conventional means can be used as the separation zone 7. For example, a settling apparatus, distillation apparatus, centrifuge or filtration apparatus can be employed.
  • the bottoms stream is separated into its two major components, the middle to heavy distillate fraction and the solids carbonaceous material.
  • the middle to heavy distillate fraction preferably has a boiling point of about 650-1000°F and can be used in the hydroconversion reaction as the hydrogen donor solvent by recycling, for example, by a line 8 to the mixing zone 1.
  • the solids carbonaceous material separated from the bottoms stream is removed from separation zone 7 by way of line 9. Since, there is a significant amount of catalyst in the solids carbonaceous stream, a portion of the stream can be reused in the hydroconversion reaction by recycling, for example, by a line 10 to the mixing zone 1.
  • a recycle rate will be used to establish a solvent to coal to solids carbonaceous material ratio of about 0.5-3 to 1 to 0.1-2, more preferably about 1 to 1 to 1.
  • the catalyst recovery zone 11 Due to the high metals content of the catalytic reaction, it is also preferable, from an economic as well as an environmental basis, to send the remaining portion of the solids carbonaceous material by the line 9 to a catalyst recovery zone 11. Any of the known catalyst recovery methods can be incorporated into the process of this invention, and the catalyst can be recycled for use in the hydroconversion reaction. As one example, a substantial amount of the catalytic metal constituents can be recovered for recycle by burning the solids carbonaceous material at a temperature below the fusion temperature of the ash component to convert the metal catalyst into soluble metal- containing oxides.
  • This oxidized composition is then contacted with an aqueous solution of a basic alkali metal salt to extract the soluble metal-containing oxides in the form of soluble alkali salts of the metal-containing oxides. 5
  • soluble alkali metal salts are then used to make up the metals requirement for the hydroconversion catalyst by adding the salts to the mixing zone 1, for example, by way of a line 12 as shown in Fig. 1.
  • the remaining composition can be discarded. See, for example, U.S. Patent No. 104,417,972, the teachings of which are fully incorporated herein by reference.
  • Particulate Illinois-Monterrey coal, 40 gm, and preformed catalyst containing 10 wt % of a mixture of Ni and Mo, is slurried in 64 gm of a hydrogenated wide cut coal distillate fraction having a boiling point of about 400-
  • the slurry is heated to 775°F in a reaction vessel and reacted by contacting with molecular hydrogen at a hydrogen partial pressure of 2300 psig for 480 minutes.
  • a distillate fraction having a boiling point of 650-1000°F is recovered and recycled to the reaction vessel.
  • Particulate coal, hydrogenated wide cut coal distillate having a boiling point of about 650-1000°F and bottoms conversion product are continuously reacted in a hydroconversion reactor at a ratio of 1/1/1.
  • the hydrogenated wide cut coal distillate used in the reaction is recovered from a flash separation vessel which is used to separate the product from the hydroconversion reactor and from a vacuum distillation vessel which is used to separate a purge stream of the 650°+F products from the flash separation vessel.
  • the catalyst is a Mo catalyst which is maintained at a concentration of 500 PPM in the reactor.
  • the reaction is carried out at 840°F for 120 minutes under a hydrogen partial pressure of 2000 psig. The results are shown in Table 2.
  • composition wt % or PPM
  • Run 1 represents the process of this invention.
  • Run 2 represents a catalytic concentration typical in the prior art.

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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)

Abstract

Procédé permettant d'hydroconvertir du charbon dans une zone d'hydroconversion (4) en produits hydrocarbonés liquides. On ajoute du charbon particulaire dans une zone de mélange (1) par une ligne (2). On dissout un précurseur de catalyseur dans un solvant donneur d'hydrogène et on l'introduit dans la zone de mélange (1) par la ligne (3). Le mélange traverse une zone d'hydroconversion (4) dans des conditions d'hydroconversion pour former un produit d'hydroconversion qui est séparé dans des zones (6) et (7) sous forme d'écoulements de produits constituants séparés.
PCT/US1994/006545 1993-06-11 1994-06-10 Procede d'hydroconversion catalytique WO1994029406A1 (fr)

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AU70592/94A AU7059294A (en) 1993-06-11 1994-06-10 Catalytic hydroconversion process

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US7598593A 1993-06-11 1993-06-11
US08/075,985 1993-06-11

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2445343C1 (ru) * 2010-12-09 2012-03-20 Общество с ограниченной ответственностью "Олимпик Интегратор" (ООО "Олимпик Интегратор") Способ прямого ожижения углей
US8932451B2 (en) 2011-08-31 2015-01-13 Exxonmobil Research And Engineering Company Integrated crude refining with reduced coke formation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4424110A (en) * 1980-08-29 1984-01-03 Exxon Research And Engineering Co. Hydroconversion process
US5246570A (en) * 1992-04-09 1993-09-21 Amoco Corporation Coal liquefaction process using soluble molybdenum-containing organophosphorodithioate catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4424110A (en) * 1980-08-29 1984-01-03 Exxon Research And Engineering Co. Hydroconversion process
US5246570A (en) * 1992-04-09 1993-09-21 Amoco Corporation Coal liquefaction process using soluble molybdenum-containing organophosphorodithioate catalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2445343C1 (ru) * 2010-12-09 2012-03-20 Общество с ограниченной ответственностью "Олимпик Интегратор" (ООО "Олимпик Интегратор") Способ прямого ожижения углей
US8932451B2 (en) 2011-08-31 2015-01-13 Exxonmobil Research And Engineering Company Integrated crude refining with reduced coke formation

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Publication number Publication date
AU7059294A (en) 1995-01-03

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