WO2015077116A1 - Process for producing hydrogen-rich coal tar - Google Patents

Process for producing hydrogen-rich coal tar Download PDF

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Publication number
WO2015077116A1
WO2015077116A1 PCT/US2014/065415 US2014065415W WO2015077116A1 WO 2015077116 A1 WO2015077116 A1 WO 2015077116A1 US 2014065415 W US2014065415 W US 2014065415W WO 2015077116 A1 WO2015077116 A1 WO 2015077116A1
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WO
WIPO (PCT)
Prior art keywords
stream
hydrogen
coal tar
catalyst
ammonia
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PCT/US2014/065415
Other languages
French (fr)
Inventor
John Q. Chen
Peter K. Coughlin
Stanley J. Frey
James A. Johnson
Vasant P. Thakkar
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Uop Llc
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Publication of WO2015077116A1 publication Critical patent/WO2015077116A1/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002Production 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts

Definitions

  • Coke Pyrolysis of coal produces coke and coal tar.
  • the coke-making or "coking” process consists of heating the material in closed vessels in the absence of oxygen to very high temperatures.
  • Coke is a porous but hard residue that is mostly carbon and inorganic ash, which can be used in making steel.
  • Coal tar is the volatile material that is driven off during heating, and it comprises a mixture of a number of hydrocarbon compounds. It can be separated to yield a variety of organic compounds, such as benzene, toluene, xylene, naphthalene, anthracene, and phenanthrene. These organic compounds can be used to make numerous products, for example, dyes, drugs, explosives, flavorings, perfumes, preservatives, synthetic resins, and paints and stains. The residual pitch left from the separation is used for paving, roofing, waterproofing, and insulation.
  • a process for producing hydrogen-rich coal tar includes introducing a coal feed into a pyrolysis zone, and contacting the coal feed with a hydrogen donor stream and a multifunctional catalyst in the pyrolysis zone.
  • the multifunctional catalyst includes a hydrogenation function for increasing the hydrogen content of said coal tar stream.
  • the process further includes pyrolyzing the coal feed with the hydrogen donor stream and the multifunctional catalyst to produce a coke stream and a coal tar stream comprising hydrocarbon vapor.
  • a process for producing hydrogen-rich coal tar includes introducing a coal feed into a pyrolysis zone and contacting the coal feed with at least a hydrogen donor stream and a multifunctional catalyst in the pyrolysis zone.
  • the hydrogen donor stream includes one or more of water, ammonia, and an organic hydrogen donor solvent, and the multifunctional catalyst including a hydrogenation function for increasing a hydrogen content of said coal tar stream.
  • the process further includes pyrolyzing the coal feed with the hydrogen donor stream and the catalyst to produce a coke stream and a coal tar stream comprising hydrocarbon vapor.
  • a coal feed 10 can be sent to a pyrolysis zone 15, a gasification zone 20, or the coal feed 10 can be split into two parts and sent to both.
  • the coal is heated to a high temperature, e.g., up to 2,000°C (3,600°F), in the absence of oxygen to drive off the volatile components and in the presence of a multifunctional catalyst.
  • a high temperature e.g., up to 2,000°C (3,600°F)
  • the coal feed 10 is heated with the catalyst and one or more hydrogen donors.
  • Example hydrogen donors include, but are not limited to, hydrogen gas, water, ammonia, and hydrogenated hydrocarbon solvents. Those of skill in the art will recognize that additional hydrogen donors could be used without departing from the scope of this invention.
  • the multifunction catalyst includes at least a hydrogenation function for increasing a hydrogen content of said coal tar stream.
  • Hydrogen present in the pyrolysis zone reacts on the hydrogenation function of the catalyst to increase hydrogen content of the coal tar stream.
  • additional functions may also be present.
  • the catalyst may include one or more of a function for decomposing ammonia to nitrogen and hydrogen and a function that causes water to react with coke 30 produced during pyrolysis to form carbon monoxide, carbon dioxide, and hydrogen.
  • the pyrolysis produces coke 30 and coal tar stream 35.
  • the coke 30 can be used in other processes, such as the manufacture of steel.
  • the coal tar stream 35 which comprises the volatile components from the coking process can be sent to a contamination removal zone 40, if desired. Additionally, because the coal is pyrolyzed with a hydrogenating catalyst, at least a portion of the hydrocarbon compounds present in the coal tar stream 35 are at least partially hydrogenated.
  • the contaminant removal zone 40 for removing one or more contaminants from the coal tar stream 35 or another process stream may be located at various positions along the process depending on the impact of the particular contaminant on the product or process and the reason for the contaminant's removal, as described further below.
  • the contaminant removal zone 40 can be positioned upstream of a separation zone 50.
  • Some contaminants have been identified to interfere with a downstream processing step or hydrocarbon conversion process, in which case the contaminant removal zone 40 may be positioned upstream of the separation zone 50 or between the separation zone 50 and the particular downstream processing step at issue. Still other contaminants have been identified that should be removed to meet particular product specifications.
  • various contaminant removal zones 40 may be positioned at different locations along the process.
  • a contaminant removal zone 40 may overlap or be integrated with another process within the system, in which case the contaminant may be removed during another portion of the process, including, but not limited to the separation zone 50 or the downstream hydrocarbon conversion zone. This may be accomplished with or without modification to these particular zones, reactors or processes.
  • the contaminant removal zone 40 is often positioned downstream of the hydrocarbon conversion reactor, it should be understood that the contaminant removal zone 40 in accordance herewith may be positioned upstream of the separation zone, between the separation zone 50 and the hydrocarbon conversion zone, or downstream of the hydrocarbon conversion zone or along other streams within the process stream, such as, for example, a carrier fluid stream, a fuel stream, an oxygen source stream, or any streams used in the systems and the processes described herein.
  • the contaminant concentration is controlled by removing at least a portion of the contaminant from the.
  • the term removing may refer to actual removal, for example by adsorption, absorption, or membrane separation, or it may refer to conversion of the contaminant to a more tolerable compound, or both.
  • the decontaminated coal tar feed 45 is sent to a separation zone 50 where it is separated into two or more fractions 55, 60, 25, 70, 75.
  • Coal tar comprises a complex mixture of heterocyclic aromatic compounds and their derivatives with a wide range of boiling points.
  • the number of fractions and the components in the various fractions can be varied as is well known in the art.
  • a typical separation process involves separating the coal tar into four to six streams.
  • a fraction comprising NH 3 , CO, and light hydrocarbons, a light oil fraction with boiling points between 0°C and 180°C, a middle oil fraction with boiling points between 180°C to 230°C, a heavy oil fraction with boiling points between 230 to 270°C, an anthracene oil fraction with boiling points between 270°C to 350°C, and pitch.
  • the light oil fraction contains compounds such as benzenes, toluenes, xylenes, naphtha, coumarone-indene, dicyclopentadiene, pyridine, and picolines.
  • the middle oil fraction contains compounds such as phenols, cresols and cresylic acids, xylenols, naphthalene, high boiling tar acids, and high boiling tar bases.
  • the heavy oil fraction contains benzene absorbing oil and creosotes.
  • the anthracene oil fraction contains anthracene.
  • Pitch is the residue of the coal tar distillation containing primarily aromatic hydrocarbons and heterocyclic compounds.
  • the decontaminated coal tar feed 45 is separated into gas fraction 55 containing gases such as NH 3 and CO as well as light hydrocarbons, such as ethane, hydrocarbon fractions 60, 65, and 70 having different boiling point ranges, and pitch fraction 75.
  • Suitable separation processes include, but are not limited to fractionation, solvent extraction, and distillation.
  • fraction 70 comprises partially hydrogenated hydrocarbons.
  • the fraction 70 may include hydrogenated naphthalenes, tetralin, and decalin and derivatives thereof.
  • the fraction 70 containing the at least partially hydrogenated hydrocarbons can be recycled to the pyrolysis zone as a hydrogen donor source.
  • the hydrocarbon fraction 65 is routed to an optional hydrotreating zone 80. Hydrotreating is a process in which hydrogen gas is contacted with a hydrocarbon stream in the presence of suitable catalysts which are primarily active for the removal of heteroatoms, such as sulfur, nitrogen, oxygen, and metals from the hydrocarbon feedstock.
  • hydrocarbons with double and triple bonds may be saturated. Aromatics may also be saturated.
  • Typical hydrotreating reaction conditions include a temperature of 290°C (550°F) to 455°C (850°F), a pressure of 3.4 MPa (500 psig) to 27.6 MPa (4,000 psig), a liquid hourly space velocity of 0.1 hr -1 to 4 hr -1 , and a hydrogen rate of 168 to 1,685 Nm 3 /m 3 oil (1,000- 10,000 scf/bbl).
  • Typical hydrotreating catalysts include at least one Group VIII metal, preferably iron, cobalt and nickel, and at least one Group VI metal, preferably molybdenum and tungsten, on a high surface area support material, preferably alumina.
  • Other typical hydrotreating catalysts include zeolitic catalysts, as well as noble metal catalysts where the noble metal is selected from palladium and platinum.
  • the hydrotreating process produces, as a byproduct, water 85.
  • the water 85 can be recycled to the pyro lysis zone 15 as a hydrogen donor source.
  • ammonia 90 is produced during the hydrotreating process. Ammonia 90 is optionally recycled to the pyro lysis zone 15 as a hydrogen donor source.
  • the hydrotreated hydrocarbon stream 95 is routed to a hydrocracking zone 100.
  • Hydrocracking is a process in which hydrocarbons crack in the presence of hydrogen to lower molecular weight hydrocarbons.
  • Typical hydrocracking conditions may include a temperature of 290°C (550°F) to 468°C (875°F), a pressure of 3.5 MPa (500 psig) to 27.6 MPa (4,000 psig), a liquid hourly space velocity (LHSV) of 0.5 to less than 5 hr "1 , and a hydrogen rate of 421 to 2,527 Nm 3 /m 3 oil (2,500-15,000 scf/bbl).
  • Typical hydrocracking catalysts include amorphous silica-alumina bases or low-level zeolite bases combined with one or more Group VIII or Group VIB metal hydrogenating components, or a crystalline zeolite cracking base upon which is deposited a Group VIII metal hydrogenating component. Additional hydrogenating components may be selected from Group VIB for incorporation with the zeolite base.
  • the hydrocracking produces ammonia 105 as a byproduct. As illustrated in the Figure, the ammonia 105 is preferably combined with the ammonia 90 output from the hydrotreating zone 80 and recycled to the pyrolysis zone 15 as a single ammonia stream 110. Alternatively, the ammonia stream 110 may include only one of the hydrotreating byproduct ammonia 90 and the hydrocracking byproduct ammonia 105.
  • one or more of the fractions 55, 60, 65, 70, 75, and the hydrocracked product 115 may be routed to additional downstream processing zones including, but not limited to hydrotreating zones, hydrocracking zones, fluid catalytic cracking zones, alkylation zones, transalkylation zones, oxidation zones, and hydrogenation zones.
  • Fluid catalytic cracking is a catalytic hydrocarbon conversion process accomplished by contacting heavier hydrocarbons in a fluidized reaction zone with a catalytic particulate material.
  • the reaction in catalytic cracking is carried out in the absence of substantial added hydrogen or the consumption of hydrogen.
  • the process typically employs a powdered catalyst having the particles suspended in a rising flow of feed hydrocarbons to form a fluidized bed.
  • cracking takes place in a riser, which is a vertical or upward sloped pipe.
  • a pre-heated feed is sprayed into the base of the riser via feed nozzles where it contacts hot fluidized catalyst and is vaporized on contact with the catalyst, and the cracking occurs converting the high molecular weight oil into lighter components including liquefied petroleum gas (LPG), gasoline, and a distillate.
  • LPG liquefied petroleum gas
  • the catalyst-feed mixture flows upward through the riser for a short period (a few seconds), and then the mixture is separated in cyclones.
  • the hydrocarbons are directed to a fractionator for separation into LPG, gasoline, diesel, kerosene, jet fuel, and other possible fractions.
  • the cracking catalyst While going through the riser, the cracking catalyst is deactivated because the process is accompanied by formation of coke which deposits on the catalyst particles.
  • Contaminated catalyst is separated from the cracked hydrocarbon vapors and is further treated with steam to remove hydrocarbon remaining in the pores of the catalyst.
  • the catalyst is then directed into a regenerator where the coke is burned off the surface of the catalyst particles, thus restoring the catalyst's activity and providing the necessary heat for the next reaction cycle.
  • the process of cracking is endothermic.
  • the regenerated catalyst is then used in the new cycle.
  • Typical FCC conditions include a temperature of 400°C to 800°C, a pressure of 0 to 688 kPag ( 0 to 100 psig), and contact times of 0.1 seconds to 1 hour. The conditions are determined based on the hydrocarbon feedstock being cracked, and the cracked products desired.
  • Zeolite-based catalysts are commonly used in FCC reactors, as are composite catalysts which contain zeolites, silica-aluminas, alumina, and other binders.
  • Transalkylation is a chemical reaction resulting in transfer of an alkyl group from one organic compound to another. Catalysts, particularly zeolite catalysts, are often used to effect the reaction.
  • the transalkylation catalyst may be metal stabilized using a noble metal or base metal, and may contain suitable binder or matrix material such as inorganic oxides and other suitable materials.
  • an polyalkylaromatic hydrocarbon feed and an aromatic hydrocarbon feed are provided to a transalkylation reaction zone.
  • the feed is usually heated to reaction temperature and then passed through a reaction zone, which may comprise one or more individual reactors. Passage of the combined feed through the reaction zone produces an effluent stream comprising unconverted feed and product monoalkylated hydrocarbons.
  • This effluent is normally cooled and passed to a stripping column in which substantially all C 5 and lighter hydrocarbons present in the effluent are concentrated into an overhead stream and removed from the process.
  • An aromatics-rich stream is recovered as net stripper bottoms, which is referred to as the transalkylation effluent.
  • the transalkylation reaction can be effected in contact with a catalytic composite in any conventional or otherwise convenient manner and may comprise a batch or continuous type of operation, with a continuous operation being preferred.
  • the transalkylation catalyst is usefully disposed as a fixed bed in a reaction zone of a vertical tubular reactor, with the alkylaromatic feed stock charged through the bed in an upflow or downflow manner.
  • the transalkylation zone normally operates at conditions including a temperature in the range of 130°C to 540°C.
  • the transalkylation zone is typically operated at moderately elevated pressures broadly ranging from 100 kPa to 10 MPa absolute.
  • the transalkylation reaction can be effected over a wide range of space velocities. That is, volume of charge per volume of catalyst per hour; weight hourly space velocity (WHSV) generally is in the range of from 0.1 to 30hr _1 .
  • the catalyst is typically selected to have relatively high stability at a high activity level.
  • Alkylation is typically used to combine light olefins, for example mixtures of alkenes such as propylene and butylene, with isobutane to produce a relatively high-octane branched-chain paraffmic hydrocarbon fuel, including isoheptane and isooctane.
  • an alkylation reaction can be performed using an aromatic compound such as benzene in place of the isobutane.
  • the product resulting from the alkylation reaction is an alkylbenzene (e.g. toluene, xylenes, ethylbenzene, etc.).
  • the reactants are mixed in the presence of a strong acid catalyst, such as sulfuric acid or hydrofluoric acid.
  • a strong acid catalyst such as sulfuric acid or hydrofluoric acid.
  • the alkylation reaction is carried out at mild temperatures, and is typically a two-phase reaction. Because the reaction is exothermic, cooling is needed. Depending on the catalyst used, normal refinery cooling water provides sufficient cooling. Alternatively, a chilled cooling medium can be provided to cool the reaction.
  • the catalyst protonates the alkenes to produce reactive carbocations which alkylate the isobutane reactant, thus forming branched chain paraffins from isobutane.
  • Aromatic alkylation is generally now conducted with solid acid catalysts including zeolites or amorphous silica-aluminas.
  • the alkylation reaction zone is maintained at a pressure sufficient to maintain the reactants in liquid phase.
  • a general range of operating pressures is from 200 to 7,100 kPa absolute.
  • the temperature range covered by this set of conditions is from -20°C to 200°C.
  • the temperature range is from 100°C to 200°C at the pressure range of 200 to 7,100 kPa.
  • Oxidation involves the oxidation of hydrocarbons to oxygen-containing compounds, such as aldehydes.
  • the hydrocarbons include alkanes, alkenes, typically with carbon numbers from 2 to 15, and alkyl aromatics, linear, branched, and cyclic alkanes and alkenes can be used.
  • Oxygenates that are not fully oxidized to ketones or carboxylic acids can also be subjected to oxidation processes, as well as sulfur compounds that contain -S-H moieties, thiophene rings, and sulfone groups.
  • the process is carried out by placing an oxidation catalyst in a reaction zone and contacting the feed stream which contains the desired hydrocarbons with the catalyst in the presence of oxygen.
  • the type of reactor which can be used is any type well known in the art such as fixed-bed, moving-bed, multi-tube, CSTR, fluidized bed, etc.
  • the feed stream can be flowed over the catalyst bed either up-flow or down-flow in the liquid, vapor, or mixed phase.
  • the feed stream can be flowed co-current or counter-current.
  • the feed stream can be continuously added or added batch-wise.
  • the feed stream contains the desired oxidizable species along with oxygen.
  • Oxygen can be introduced either as pure oxygen or as air, or as liquid phase oxidants including hydrogen peroxide, organic peroxides, or peroxy-acids.
  • the molar ratio of oxygen (0 2 ) to alkane can range from 5: 1 to 1 : 10.
  • the feed stream can also contain a diluent gas selected form nitrogen, neon, argon, helium, carbon dioxide, steam or mixtures thereof.
  • the oxygen can be added as air which could also provide a diluent.
  • the molar ratio of diluent gas to oxygen ranges from greater than zero to 10: 1.
  • the catalyst and feed stream are reacted at oxidation conditions which include a temperature of 300°C to 600°C, a pressure of lOl kPa to 5,066 kPa and a space velocity of 100 to 100,000 hr "1 .
  • Hydrogenation involves the addition of hydrogen to hydrogenatable hydrocarbon compounds.
  • hydrogen can be provided in a hydrogen-containing compound with ready available hydrogen, such as tetralin, alcohols, hydrogenated naphthalenes, and others via a transfer hydrogenation process with or without a catalyst.
  • the hydrogenatable hydrocarbon compounds are introduced into a hydrogenation zone and contacted with a hydrogen-rich gaseous phase and a hydrogenation catalyst in order to hydrogenate at least a portion of the hydrogenatable hydrocarbon compounds.
  • the catalytic hydrogenation zone may contain a fixed, ebulated or fluidized catalyst bed.
  • This reaction zone is typically at a pressure from 689 kPag (100 psig) to 13,790 kPag (2,000 psig) with a maximum catalyst bed temperature in the range of 177°C (350°F) to 454°C (850°F).
  • the liquid hourly space velocity is typically in the range from 0.2 hr "1 to 10 hr "1 and hydrogen circulation rates from 200 standard cubic feet per barrel (SCFB) (35.6 m 3 /m 3 ) to 10,000 SCFB (1778 m 3 /m 3 ).
  • syngas 130 which is a mixture of carbon monoxide and hydrogen.
  • the syngas 130 can be further processed using the Fischer-Tropsch reaction to produce gasoline or using the water-gas shift reaction to produce more hydrogen.
  • a first embodiment of the invention is a process for producing hydrogen-rich coal tar, comprising introducing a coal feed into a pyrolysis zone; contacting the coal feed with a hydrogen donor stream and a multifunctional catalyst in the pyrolysis zone, the multifunctional catalyst comprising a hydrogenation function for increasing hydrogen content of the coal tar stream; pyrolyzing the coal feed with the hydrogen donor stream and the multifunctional catalyst to produce a coke stream and a coal tar stream comprising hydrocarbon vapor.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, further comprising hydrotreating at least a portion of the coal tar stream, wherein the hydrotreating produces water, and the water is recycled to the pyrolysis zone as the hydrogen donor stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, further comprising hydrotreating at least a portion of the coal tar stream, wherein the hydrotreating produces ammonia, and the ammonia is recycled to the pyrolysis zone as the hydrogen donor stream, wherein the multifunctional catalyst further comprises a function for decomposing ammonia to nitrogen and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase a hydrogen content of the coal tar stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the hydrogenation function increases the hydrogen content of the coal tar stream by at least partially hydrogenating at least a portion of the hydrocarbon vapor.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, further comprising separating the partially hydrogenated hydrocarbon vapor from the coal tar stream; recycling the partially hydrogenated hydrocarbon vapor to the pyrolysis zone as the hydrogen donor stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the hydrogen donor stream comprises one or more of water, ammonia, and an organic hydrogen donor solvent.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the organic hydrogen donor solvent includes one or more of tetralin and decalin and derivatives thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the multifunction catalyst further includes a steam reforming function that causes the water to react with the coke stream to form carbon monoxide, carbon dioxide, and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase the hydrogen content of the coal tar stream.
  • the multifunction catalyst further includes a steam reforming function that causes the water to react with the coke stream to form carbon monoxide, carbon dioxide, and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase the hydrogen content of the coal tar stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, further comprising hydrocracking at least a portion of the coal tar stream, wherein the hydrocracking produces ammonia, and the ammonia is recycled to the pyrolysis zone as the hydrogen donor stream, wherein the multifunctional catalyst further comprises a function for decomposing ammonia to nitrogen and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase the hydrogen content of the coal tar stream.
  • a second embodiment of the invention is a process for producing hydrogen- rich coal tar, comprising introducing a coal feed into a pyrolysis zone; contacting the coal feed with at least a hydrogen donor stream and a multifunctional catalyst in the pyrolysis zone, the hydrogen donor stream comprising one or more of water, ammonia, and an organic hydrogen donor solvent, the multifunctional catalyst including a hydrogenation function for increasing a hydrogen content of the coal tar stream; pyrolyzing the coal feed with the hydrogen donor stream and the catalyst to produce a coke stream and a coal tar stream comprising hydrocarbon vapor.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising hydrotreating at least a portion of the coal tar stream, wherein the hydrotreating produces water, and the water is recycled to the pyrolysis zone as the hydrogen donor stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising hydrotreating at least a portion of the coal tar stream, wherein the hydrotreating produces ammonia, and the ammonia is recycled to the pyrolysis zone as the hydrogen donor stream, wherein the multifunctional catalyst further comprises a function for decomposing ammonia to nitrogen and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase hydrogen content of the coal tar stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the hydrogenation function increases the hydrogen content of the coal tar stream by at least partially hydrogenating at least a portion of the hydrocarbon vapor.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising separating the partially hydrogenated hydrocarbon vapor from the coal tar stream; recycling the partially hydrogenated hydrocarbon vapor to the pyrolysis zone as the hydrogen donor stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the organic hydrogen donor solvent includes one or more of tetralin and decalin and derivatives thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the multifunction catalyst further includes a steam reforming function that causes the water to react with the coke stream to form carbon monoxide, carbon dioxide, and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase the hydrogen content of the coal tar stream.
  • the multifunction catalyst further includes a steam reforming function that causes the water to react with the coke stream to form carbon monoxide, carbon dioxide, and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase the hydrogen content of the coal tar stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising hydrocracking at least a portion of the coal tar stream, wherein the hydrocracking produces ammonia, and the ammonia is recycled to the pyrolysis zone as the hydrogen donor stream, wherein the multifunctional catalyst further comprises a function for decomposing ammonia to nitrogen and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase the hydrogen content of the coal tar stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising hydrotreating at least a portion of the coal tar stream, wherein the hydrotreating produces water, and the water is recycled to the pyrolysis zone as the hydrogen donor stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising hydrotreating at least a portion of the coal tar stream, wherein the hydrotreating produces ammonia, and the ammonia is recycled to the pyrolysis zone as the hydrogen donor stream.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising combining the ammonia from the hydrotreating and the ammonia from the hydrocracking.

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Abstract

A process for producing hydrogen-rich coal tar includes introducing a coal feed into a pyrolysis zone, and contacting the coal feed with a hydrogen donor stream and a multifunctional catalyst in the pyrolysis zone. The multifunctional catalyst includes a hydrogenation function for increasing a hydrogen content of said coal tar stream. The process further includes pyrolyzing the coal feed with the hydrogen donor stream and the multifunctional catalyst to produce a coke stream and a coal tar stream comprising hydrocarbon vapor.

Description

PROCESS FOR PRODUCING HYDROGEN-RICH COAL TAR
STATEMENT OF PRIORITY
This application claims priority to U.S. Provisional Application No. 61/905,928 filed on November 19, 2013, the entirety of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
Many different types of chemicals are produced from the processing of petroleum. However, petroleum is becoming more expensive because of increased demand in recent decades.
Therefore, attempts have been made to provide alternative sources for the starting materials for manufacturing chemicals. Attention is now being focused on producing liquid hydrocarbons from solid carbonaceous materials, such as coal, which is available in large quantities in countries such as the United States and China.
Pyrolysis of coal produces coke and coal tar. The coke-making or "coking" process consists of heating the material in closed vessels in the absence of oxygen to very high temperatures. Coke is a porous but hard residue that is mostly carbon and inorganic ash, which can be used in making steel.
Coal tar is the volatile material that is driven off during heating, and it comprises a mixture of a number of hydrocarbon compounds. It can be separated to yield a variety of organic compounds, such as benzene, toluene, xylene, naphthalene, anthracene, and phenanthrene. These organic compounds can be used to make numerous products, for example, dyes, drugs, explosives, flavorings, perfumes, preservatives, synthetic resins, and paints and stains. The residual pitch left from the separation is used for paving, roofing, waterproofing, and insulation.
Increasing the hydrogen content of the coal tar helps to produce more useful products from the coal tar. Thus, there is a need for a process for producing hydrogen-rich coal tar.
SUMMARY OF THE INVENTION
In a first aspect, a process for producing hydrogen-rich coal tar includes introducing a coal feed into a pyrolysis zone, and contacting the coal feed with a hydrogen donor stream and a multifunctional catalyst in the pyrolysis zone. The multifunctional catalyst includes a hydrogenation function for increasing the hydrogen content of said coal tar stream. The process further includes pyrolyzing the coal feed with the hydrogen donor stream and the multifunctional catalyst to produce a coke stream and a coal tar stream comprising hydrocarbon vapor.
In another aspect, a process for producing hydrogen-rich coal tar includes introducing a coal feed into a pyrolysis zone and contacting the coal feed with at least a hydrogen donor stream and a multifunctional catalyst in the pyrolysis zone. The hydrogen donor stream includes one or more of water, ammonia, and an organic hydrogen donor solvent, and the multifunctional catalyst including a hydrogenation function for increasing a hydrogen content of said coal tar stream. The process further includes pyrolyzing the coal feed with the hydrogen donor stream and the catalyst to produce a coke stream and a coal tar stream comprising hydrocarbon vapor.
BRIEF DESCRIPTION OF THE DRAWING
The Figure illustrates one embodiment of the process of the present invention. DETAILED DESCRIPTION OF THE INVENTION
The Figure shows one embodiment of a coal pyrolysis process 5. A coal feed 10 can be sent to a pyrolysis zone 15, a gasification zone 20, or the coal feed 10 can be split into two parts and sent to both.
In the pyrolysis zone 15, the coal is heated to a high temperature, e.g., up to 2,000°C (3,600°F), in the absence of oxygen to drive off the volatile components and in the presence of a multifunctional catalyst. In particular, the coal feed 10 is heated with the catalyst and one or more hydrogen donors. Example hydrogen donors include, but are not limited to, hydrogen gas, water, ammonia, and hydrogenated hydrocarbon solvents. Those of skill in the art will recognize that additional hydrogen donors could be used without departing from the scope of this invention.
The multifunction catalyst includes at least a hydrogenation function for increasing a hydrogen content of said coal tar stream. Hydrogen present in the pyrolysis zone reacts on the hydrogenation function of the catalyst to increase hydrogen content of the coal tar stream. Depending on the hydrogen donor source, additional functions may also be present. For example, the catalyst may include one or more of a function for decomposing ammonia to nitrogen and hydrogen and a function that causes water to react with coke 30 produced during pyrolysis to form carbon monoxide, carbon dioxide, and hydrogen.
The pyrolysis produces coke 30 and coal tar stream 35. The coke 30 can be used in other processes, such as the manufacture of steel.
The coal tar stream 35 which comprises the volatile components from the coking process can be sent to a contamination removal zone 40, if desired. Additionally, because the coal is pyrolyzed with a hydrogenating catalyst, at least a portion of the hydrocarbon compounds present in the coal tar stream 35 are at least partially hydrogenated.
The contaminant removal zone 40 for removing one or more contaminants from the coal tar stream 35 or another process stream may be located at various positions along the process depending on the impact of the particular contaminant on the product or process and the reason for the contaminant's removal, as described further below. For example, the contaminant removal zone 40 can be positioned upstream of a separation zone 50. Some contaminants have been identified to interfere with a downstream processing step or hydrocarbon conversion process, in which case the contaminant removal zone 40 may be positioned upstream of the separation zone 50 or between the separation zone 50 and the particular downstream processing step at issue. Still other contaminants have been identified that should be removed to meet particular product specifications. Where it is desired to remove multiple contaminants from the hydrocarbon or process stream, various contaminant removal zones 40 may be positioned at different locations along the process. In still other approaches, a contaminant removal zone 40 may overlap or be integrated with another process within the system, in which case the contaminant may be removed during another portion of the process, including, but not limited to the separation zone 50 or the downstream hydrocarbon conversion zone. This may be accomplished with or without modification to these particular zones, reactors or processes. While the contaminant removal zone 40 is often positioned downstream of the hydrocarbon conversion reactor, it should be understood that the contaminant removal zone 40 in accordance herewith may be positioned upstream of the separation zone, between the separation zone 50 and the hydrocarbon conversion zone, or downstream of the hydrocarbon conversion zone or along other streams within the process stream, such as, for example, a carrier fluid stream, a fuel stream, an oxygen source stream, or any streams used in the systems and the processes described herein. The contaminant concentration is controlled by removing at least a portion of the contaminant from the. As used herein, the term removing may refer to actual removal, for example by adsorption, absorption, or membrane separation, or it may refer to conversion of the contaminant to a more tolerable compound, or both.
The decontaminated coal tar feed 45 is sent to a separation zone 50 where it is separated into two or more fractions 55, 60, 25, 70, 75. Coal tar comprises a complex mixture of heterocyclic aromatic compounds and their derivatives with a wide range of boiling points. The number of fractions and the components in the various fractions can be varied as is well known in the art. A typical separation process involves separating the coal tar into four to six streams. For example, there can be a fraction comprising NH3, CO, and light hydrocarbons, a light oil fraction with boiling points between 0°C and 180°C, a middle oil fraction with boiling points between 180°C to 230°C, a heavy oil fraction with boiling points between 230 to 270°C, an anthracene oil fraction with boiling points between 270°C to 350°C, and pitch.
The light oil fraction contains compounds such as benzenes, toluenes, xylenes, naphtha, coumarone-indene, dicyclopentadiene, pyridine, and picolines. The middle oil fraction contains compounds such as phenols, cresols and cresylic acids, xylenols, naphthalene, high boiling tar acids, and high boiling tar bases. The heavy oil fraction contains benzene absorbing oil and creosotes. The anthracene oil fraction contains anthracene. Pitch is the residue of the coal tar distillation containing primarily aromatic hydrocarbons and heterocyclic compounds.
As illustrated, the decontaminated coal tar feed 45 is separated into gas fraction 55 containing gases such as NH3 and CO as well as light hydrocarbons, such as ethane, hydrocarbon fractions 60, 65, and 70 having different boiling point ranges, and pitch fraction 75.
Suitable separation processes include, but are not limited to fractionation, solvent extraction, and distillation.
One or more of the fractions 55, 60, 65, 70, 75 can be further processed, as desired. As illustrated, fraction 70 comprises partially hydrogenated hydrocarbons. For example, the fraction 70 may include hydrogenated naphthalenes, tetralin, and decalin and derivatives thereof. The fraction 70 containing the at least partially hydrogenated hydrocarbons can be recycled to the pyrolysis zone as a hydrogen donor source. As illustrated in the Figure, the hydrocarbon fraction 65 is routed to an optional hydrotreating zone 80. Hydrotreating is a process in which hydrogen gas is contacted with a hydrocarbon stream in the presence of suitable catalysts which are primarily active for the removal of heteroatoms, such as sulfur, nitrogen, oxygen, and metals from the hydrocarbon feedstock. In hydrotreating, hydrocarbons with double and triple bonds may be saturated. Aromatics may also be saturated. Typical hydrotreating reaction conditions include a temperature of 290°C (550°F) to 455°C (850°F), a pressure of 3.4 MPa (500 psig) to 27.6 MPa (4,000 psig), a liquid hourly space velocity of 0.1 hr-1 to 4 hr-1, and a hydrogen rate of 168 to 1,685 Nm3/m3 oil (1,000- 10,000 scf/bbl). Typical hydrotreating catalysts include at least one Group VIII metal, preferably iron, cobalt and nickel, and at least one Group VI metal, preferably molybdenum and tungsten, on a high surface area support material, preferably alumina. Other typical hydrotreating catalysts include zeolitic catalysts, as well as noble metal catalysts where the noble metal is selected from palladium and platinum. In addition to producing a hydrotreated hydrocarbon stream 95, the hydrotreating process produces, as a byproduct, water 85. The water 85 can be recycled to the pyro lysis zone 15 as a hydrogen donor source. Similarly, ammonia 90 is produced during the hydrotreating process. Ammonia 90 is optionally recycled to the pyro lysis zone 15 as a hydrogen donor source.
The hydrotreated hydrocarbon stream 95 is routed to a hydrocracking zone 100. Hydrocracking is a process in which hydrocarbons crack in the presence of hydrogen to lower molecular weight hydrocarbons. Typical hydrocracking conditions may include a temperature of 290°C (550°F) to 468°C (875°F), a pressure of 3.5 MPa (500 psig) to 27.6 MPa (4,000 psig), a liquid hourly space velocity (LHSV) of 0.5 to less than 5 hr"1, and a hydrogen rate of 421 to 2,527 Nm3/m3 oil (2,500-15,000 scf/bbl). Typical hydrocracking catalysts include amorphous silica-alumina bases or low-level zeolite bases combined with one or more Group VIII or Group VIB metal hydrogenating components, or a crystalline zeolite cracking base upon which is deposited a Group VIII metal hydrogenating component. Additional hydrogenating components may be selected from Group VIB for incorporation with the zeolite base. In addition to the cracked hydrocarbon output stream 115, the hydrocracking produces ammonia 105 as a byproduct. As illustrated in the Figure, the ammonia 105 is preferably combined with the ammonia 90 output from the hydrotreating zone 80 and recycled to the pyrolysis zone 15 as a single ammonia stream 110. Alternatively, the ammonia stream 110 may include only one of the hydrotreating byproduct ammonia 90 and the hydrocracking byproduct ammonia 105.
Additionally, one or more of the fractions 55, 60, 65, 70, 75, and the hydrocracked product 115 may be routed to additional downstream processing zones including, but not limited to hydrotreating zones, hydrocracking zones, fluid catalytic cracking zones, alkylation zones, transalkylation zones, oxidation zones, and hydrogenation zones.
Fluid catalytic cracking (FCC) is a catalytic hydrocarbon conversion process accomplished by contacting heavier hydrocarbons in a fluidized reaction zone with a catalytic particulate material. The reaction in catalytic cracking is carried out in the absence of substantial added hydrogen or the consumption of hydrogen. The process typically employs a powdered catalyst having the particles suspended in a rising flow of feed hydrocarbons to form a fluidized bed. In representative processes, cracking takes place in a riser, which is a vertical or upward sloped pipe. Typically, a pre-heated feed is sprayed into the base of the riser via feed nozzles where it contacts hot fluidized catalyst and is vaporized on contact with the catalyst, and the cracking occurs converting the high molecular weight oil into lighter components including liquefied petroleum gas (LPG), gasoline, and a distillate. The catalyst-feed mixture flows upward through the riser for a short period (a few seconds), and then the mixture is separated in cyclones. The hydrocarbons are directed to a fractionator for separation into LPG, gasoline, diesel, kerosene, jet fuel, and other possible fractions. While going through the riser, the cracking catalyst is deactivated because the process is accompanied by formation of coke which deposits on the catalyst particles. Contaminated catalyst is separated from the cracked hydrocarbon vapors and is further treated with steam to remove hydrocarbon remaining in the pores of the catalyst. The catalyst is then directed into a regenerator where the coke is burned off the surface of the catalyst particles, thus restoring the catalyst's activity and providing the necessary heat for the next reaction cycle. The process of cracking is endothermic. The regenerated catalyst is then used in the new cycle. Typical FCC conditions include a temperature of 400°C to 800°C, a pressure of 0 to 688 kPag ( 0 to 100 psig), and contact times of 0.1 seconds to 1 hour. The conditions are determined based on the hydrocarbon feedstock being cracked, and the cracked products desired. Zeolite-based catalysts are commonly used in FCC reactors, as are composite catalysts which contain zeolites, silica-aluminas, alumina, and other binders. Transalkylation is a chemical reaction resulting in transfer of an alkyl group from one organic compound to another. Catalysts, particularly zeolite catalysts, are often used to effect the reaction. If desired, the transalkylation catalyst may be metal stabilized using a noble metal or base metal, and may contain suitable binder or matrix material such as inorganic oxides and other suitable materials. In a transalkylation process, an polyalkylaromatic hydrocarbon feed and an aromatic hydrocarbon feed are provided to a transalkylation reaction zone. The feed is usually heated to reaction temperature and then passed through a reaction zone, which may comprise one or more individual reactors. Passage of the combined feed through the reaction zone produces an effluent stream comprising unconverted feed and product monoalkylated hydrocarbons. This effluent is normally cooled and passed to a stripping column in which substantially all C5 and lighter hydrocarbons present in the effluent are concentrated into an overhead stream and removed from the process. An aromatics-rich stream is recovered as net stripper bottoms, which is referred to as the transalkylation effluent.
The transalkylation reaction can be effected in contact with a catalytic composite in any conventional or otherwise convenient manner and may comprise a batch or continuous type of operation, with a continuous operation being preferred. The transalkylation catalyst is usefully disposed as a fixed bed in a reaction zone of a vertical tubular reactor, with the alkylaromatic feed stock charged through the bed in an upflow or downflow manner. The transalkylation zone normally operates at conditions including a temperature in the range of 130°C to 540°C. The transalkylation zone is typically operated at moderately elevated pressures broadly ranging from 100 kPa to 10 MPa absolute. The transalkylation reaction can be effected over a wide range of space velocities. That is, volume of charge per volume of catalyst per hour; weight hourly space velocity (WHSV) generally is in the range of from 0.1 to 30hr_1. The catalyst is typically selected to have relatively high stability at a high activity level.
Alkylation is typically used to combine light olefins, for example mixtures of alkenes such as propylene and butylene, with isobutane to produce a relatively high-octane branched-chain paraffmic hydrocarbon fuel, including isoheptane and isooctane. Similarly, an alkylation reaction can be performed using an aromatic compound such as benzene in place of the isobutane. When using benzene, the product resulting from the alkylation reaction is an alkylbenzene (e.g. toluene, xylenes, ethylbenzene, etc.). For isobutane alkylation, typically, the reactants are mixed in the presence of a strong acid catalyst, such as sulfuric acid or hydrofluoric acid. The alkylation reaction is carried out at mild temperatures, and is typically a two-phase reaction. Because the reaction is exothermic, cooling is needed. Depending on the catalyst used, normal refinery cooling water provides sufficient cooling. Alternatively, a chilled cooling medium can be provided to cool the reaction. The catalyst protonates the alkenes to produce reactive carbocations which alkylate the isobutane reactant, thus forming branched chain paraffins from isobutane. Aromatic alkylation is generally now conducted with solid acid catalysts including zeolites or amorphous silica-aluminas.
The alkylation reaction zone is maintained at a pressure sufficient to maintain the reactants in liquid phase. For a hydrofluoric acid catalyst, a general range of operating pressures is from 200 to 7,100 kPa absolute. The temperature range covered by this set of conditions is from -20°C to 200°C. For at least alkylation of aromatic compounds, the temperature range is from 100°C to 200°C at the pressure range of 200 to 7,100 kPa.
Oxidation involves the oxidation of hydrocarbons to oxygen-containing compounds, such as aldehydes. The hydrocarbons include alkanes, alkenes, typically with carbon numbers from 2 to 15, and alkyl aromatics, linear, branched, and cyclic alkanes and alkenes can be used. Oxygenates that are not fully oxidized to ketones or carboxylic acids can also be subjected to oxidation processes, as well as sulfur compounds that contain -S-H moieties, thiophene rings, and sulfone groups. The process is carried out by placing an oxidation catalyst in a reaction zone and contacting the feed stream which contains the desired hydrocarbons with the catalyst in the presence of oxygen. The type of reactor which can be used is any type well known in the art such as fixed-bed, moving-bed, multi-tube, CSTR, fluidized bed, etc. The feed stream can be flowed over the catalyst bed either up-flow or down-flow in the liquid, vapor, or mixed phase. In the case of a fluidized-bed, the feed stream can be flowed co-current or counter-current. In a CSTR the feed stream can be continuously added or added batch-wise. The feed stream contains the desired oxidizable species along with oxygen. Oxygen can be introduced either as pure oxygen or as air, or as liquid phase oxidants including hydrogen peroxide, organic peroxides, or peroxy-acids. The molar ratio of oxygen (02) to alkane can range from 5: 1 to 1 : 10. In addition to oxygen and alkane or alkene, the feed stream can also contain a diluent gas selected form nitrogen, neon, argon, helium, carbon dioxide, steam or mixtures thereof. As stated, the oxygen can be added as air which could also provide a diluent. The molar ratio of diluent gas to oxygen ranges from greater than zero to 10: 1. The catalyst and feed stream are reacted at oxidation conditions which include a temperature of 300°C to 600°C, a pressure of lOl kPa to 5,066 kPa and a space velocity of 100 to 100,000 hr"1.
Hydrogenation involves the addition of hydrogen to hydrogenatable hydrocarbon compounds. Alternatively hydrogen can be provided in a hydrogen-containing compound with ready available hydrogen, such as tetralin, alcohols, hydrogenated naphthalenes, and others via a transfer hydrogenation process with or without a catalyst. The hydrogenatable hydrocarbon compounds are introduced into a hydrogenation zone and contacted with a hydrogen-rich gaseous phase and a hydrogenation catalyst in order to hydrogenate at least a portion of the hydrogenatable hydrocarbon compounds. The catalytic hydrogenation zone may contain a fixed, ebulated or fluidized catalyst bed. This reaction zone is typically at a pressure from 689 kPag (100 psig) to 13,790 kPag (2,000 psig) with a maximum catalyst bed temperature in the range of 177°C (350°F) to 454°C (850°F). The liquid hourly space velocity is typically in the range from 0.2 hr"1 to 10 hr"1 and hydrogen circulation rates from 200 standard cubic feet per barrel (SCFB) (35.6 m3 /m3) to 10,000 SCFB (1778 m3 /m3).
In some processes, all or a portion of the coal feed 10 and/or coke 30 is mixed with oxygen 120 and steam 125 and reacted under heat and pressure in the gasification zone 20 to form syngas 130, which is a mixture of carbon monoxide and hydrogen. The syngas 130 can be further processed using the Fischer-Tropsch reaction to produce gasoline or using the water-gas shift reaction to produce more hydrogen.
SPECIFIC EMBODIMENTS
While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.
A first embodiment of the invention is a process for producing hydrogen-rich coal tar, comprising introducing a coal feed into a pyrolysis zone; contacting the coal feed with a hydrogen donor stream and a multifunctional catalyst in the pyrolysis zone, the multifunctional catalyst comprising a hydrogenation function for increasing hydrogen content of the coal tar stream; pyrolyzing the coal feed with the hydrogen donor stream and the multifunctional catalyst to produce a coke stream and a coal tar stream comprising hydrocarbon vapor. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, further comprising hydrotreating at least a portion of the coal tar stream, wherein the hydrotreating produces water, and the water is recycled to the pyrolysis zone as the hydrogen donor stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, further comprising hydrotreating at least a portion of the coal tar stream, wherein the hydrotreating produces ammonia, and the ammonia is recycled to the pyrolysis zone as the hydrogen donor stream, wherein the multifunctional catalyst further comprises a function for decomposing ammonia to nitrogen and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase a hydrogen content of the coal tar stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the hydrogenation function increases the hydrogen content of the coal tar stream by at least partially hydrogenating at least a portion of the hydrocarbon vapor. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, further comprising separating the partially hydrogenated hydrocarbon vapor from the coal tar stream; recycling the partially hydrogenated hydrocarbon vapor to the pyrolysis zone as the hydrogen donor stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the hydrogen donor stream comprises one or more of water, ammonia, and an organic hydrogen donor solvent. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the organic hydrogen donor solvent includes one or more of tetralin and decalin and derivatives thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the multifunction catalyst further includes a steam reforming function that causes the water to react with the coke stream to form carbon monoxide, carbon dioxide, and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase the hydrogen content of the coal tar stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, further comprising hydrocracking at least a portion of the coal tar stream, wherein the hydrocracking produces ammonia, and the ammonia is recycled to the pyrolysis zone as the hydrogen donor stream, wherein the multifunctional catalyst further comprises a function for decomposing ammonia to nitrogen and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase the hydrogen content of the coal tar stream.
A second embodiment of the invention is a process for producing hydrogen- rich coal tar, comprising introducing a coal feed into a pyrolysis zone; contacting the coal feed with at least a hydrogen donor stream and a multifunctional catalyst in the pyrolysis zone, the hydrogen donor stream comprising one or more of water, ammonia, and an organic hydrogen donor solvent, the multifunctional catalyst including a hydrogenation function for increasing a hydrogen content of the coal tar stream; pyrolyzing the coal feed with the hydrogen donor stream and the catalyst to produce a coke stream and a coal tar stream comprising hydrocarbon vapor. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising hydrotreating at least a portion of the coal tar stream, wherein the hydrotreating produces water, and the water is recycled to the pyrolysis zone as the hydrogen donor stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising hydrotreating at least a portion of the coal tar stream, wherein the hydrotreating produces ammonia, and the ammonia is recycled to the pyrolysis zone as the hydrogen donor stream, wherein the multifunctional catalyst further comprises a function for decomposing ammonia to nitrogen and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase hydrogen content of the coal tar stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the hydrogenation function increases the hydrogen content of the coal tar stream by at least partially hydrogenating at least a portion of the hydrocarbon vapor. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising separating the partially hydrogenated hydrocarbon vapor from the coal tar stream; recycling the partially hydrogenated hydrocarbon vapor to the pyrolysis zone as the hydrogen donor stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the organic hydrogen donor solvent includes one or more of tetralin and decalin and derivatives thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the multifunction catalyst further includes a steam reforming function that causes the water to react with the coke stream to form carbon monoxide, carbon dioxide, and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase the hydrogen content of the coal tar stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising hydrocracking at least a portion of the coal tar stream, wherein the hydrocracking produces ammonia, and the ammonia is recycled to the pyrolysis zone as the hydrogen donor stream, wherein the multifunctional catalyst further comprises a function for decomposing ammonia to nitrogen and hydrogen, the hydrogen reacting on the hydrogenation function of the multifunction catalyst to increase the hydrogen content of the coal tar stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising hydrotreating at least a portion of the coal tar stream, wherein the hydrotreating produces water, and the water is recycled to the pyrolysis zone as the hydrogen donor stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising hydrotreating at least a portion of the coal tar stream, wherein the hydrotreating produces ammonia, and the ammonia is recycled to the pyrolysis zone as the hydrogen donor stream. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, further comprising combining the ammonia from the hydrotreating and the ammonia from the hydrocracking.
While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims.

Claims

1. A process for producing hydrogen-rich coal tar, comprising:
introducing a coal feed (10) into a pyro lysis zone (15);
contacting said coal feed (10) with a hydrogen donor stream (70, 85, 110) and a multifunctional catalyst in said pyrolysis zone (15); and,
pyrolyzing said coal feed (10) with the hydrogen donor stream (70, 85, 110) and said multifunctional catalyst to produce a coke stream (30) and a coal tar stream (35) comprising hydrocarbon vapor, wherein said multifunctional catalyst comprises a hydrogenation function for increasing hydrogen content of said coal tar stream (35).
2. The process of claim 1, further comprising:
hydrotreating at least a portion of said coal tar stream (35), wherein said hydrotreating produces water (85); and,
recycling the water (85) to said pyrolysis zone (15) as the hydrogen donor stream (85).
3. The process of claim 1, further comprising:
hydrotreating at least a portion of said coal tar stream (35), wherein said hydrotreating produces ammonia (90); and,
recycling the ammonia (90) to said pyrolysis zone (15) as said hydrogen donor stream (110), and,
wherein said multifunctional catalyst further comprises a function for decomposing ammonia to nitrogen and hydrogen, said hydrogen reacting on said hydrogenation function of said multifunction catalyst to increase a hydrogen content of said coal tar stream (35).
4. The process of any one of claims 1 to 3, wherein said hydrogenation function increases said hydrogen content of said coal tar stream (35) by at least partially hydrogenating at least a portion of said hydrocarbon vapor.
5. The process of claim 4, further comprising: separating said partially hydrogenated hydrocarbon vapor (70) from said coal tar stream (35);
recycling said partially hydrogenated hydrocarbon vapor (70) to said pyrolysis zone (15) as said hydrogen donor stream (70).
6. The process of any one of claims 1 to 3 wherein said hydrogen donor stream (70, 85, 110) comprises one or more of water, ammonia, and an organic hydrogen donor solvent.
7. The process of claim 6, wherein said organic hydrogen donor solvent
(70) includes one or more of tetralin and decalin and derivatives thereof.
8. The process of any one of claims 1 to 3, wherein said multifunction catalyst further includes a steam reforming function that causes said water (85) to react with said coke stream to form carbon monoxide, carbon dioxide, and hydrogen, said hydrogen reacting on said hydrogenation function of said multifunction catalyst to increase said hydrogen content of said coal tar stream (35).
9. The process of any one of claims 1 to 2, further comprising:
hydrocracking at least a portion of said coal tar stream (35), wherein said hydrocracking produces ammonia (105), and said ammonia is recycled to said pyrolysis zone
(15) as said hydrogen donor stream (110),
wherein said multifunctional catalyst further comprises a function for decomposing ammonia to nitrogen and hydrogen, said hydrogen reacting on said hydrogenation function of said multifunction catalyst to increase said hydrogen content of said coal tar stream (35).
10. The process of claim 3, further comprising:
hydrocracking at least a portion of said hydrotreated coal tar stream (95), wherein said hydrocracking produces ammonia (105), and said ammonia is recycled to said pyrolysis zone (15) as said hydrogen donor stream (110).
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