WO2012165909A4 - Procédé de valorisation d'hydrocarbures - Google Patents

Procédé de valorisation d'hydrocarbures Download PDF

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Publication number
WO2012165909A4
WO2012165909A4 PCT/KR2012/004359 KR2012004359W WO2012165909A4 WO 2012165909 A4 WO2012165909 A4 WO 2012165909A4 KR 2012004359 W KR2012004359 W KR 2012004359W WO 2012165909 A4 WO2012165909 A4 WO 2012165909A4
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WIPO (PCT)
Prior art keywords
proton
raw material
hydrogen
separation membrane
housing
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Ceased
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PCT/KR2012/004359
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English (en)
Korean (ko)
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WO2012165909A2 (fr
WO2012165909A3 (fr
Inventor
황경란
박종수
이진석
이신근
이춘부
이성욱
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Korea Institute of Energy Research KIER
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Korea Institute of Energy Research KIER
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Publication date
Priority claimed from KR1020110054066A external-priority patent/KR101298659B1/ko
Priority claimed from KR1020110073214A external-priority patent/KR101331785B1/ko
Application filed by Korea Institute of Energy Research KIER filed Critical Korea Institute of Energy Research KIER
Priority to CN201280030045.2A priority Critical patent/CN103797092B/zh
Priority to US14/123,734 priority patent/US20140100397A1/en
Publication of WO2012165909A2 publication Critical patent/WO2012165909A2/fr
Publication of WO2012165909A3 publication Critical patent/WO2012165909A3/fr
Publication of WO2012165909A4 publication Critical patent/WO2012165909A4/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C10G3/52—Hydrogen in a special composition or from a special source
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0221—Group 4 or 5 metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0223—Group 8, 9 or 10 metals
    • B01D71/02231—Palladium
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a hydrocarbon upgrading process using a proton conductive material, and more particularly, to a hydrocarbon upgrading process using a proton conductive medium having a proton (H + ) conductivity to remove carbon double bonds and oxygen, ≪ / RTI > and a method for upgrading fuels such as biodiesel.
  • Biodiesel (BD) is an environmentally friendly fuel that reduces CO 2 , which is the cause of global warming. It is a low alkyl ester compound of long chain fatty acid which is purified by transesterification reaction between copper / vegetable oil and alcohol, The characteristics are similar to those of general diesel fuel and are applicable to currently used vehicle engines.
  • the first-generation biodiesel (FAME) produced by reacting milk fat with alcohols in the presence of catalyst has problems such as clogging of fuel filter, corrosion of internal control device of distribution type high-pressure pump, corrosion of fuel injection nozzle Lt; / RTI > Due to these low fuel properties, they are actually being applied to vehicles at low mixing rates (5 to 20%).
  • glycerin, soap, salt, etc. are produced in the production of biodiesel, and high energy is consumed to separate and purify it.
  • First-generation biodiesel differs in fuel properties depending on the raw material properties, so only a limited number of raw materials are applied, and low-priced bulk feedstock supply is not smooth.
  • biodiesel produced from palm oil which has the lowest production cost among vegetable oils, is difficult to apply to cars because of low low temperature fluidity.
  • fuel conversion technology capable of actively coping with diversification of raw materials is needed.
  • the hydrogenation reaction is a reaction applied for biodiesel up-grading (BD upgrading) for production of high-quality biodiesel or biodiesel production directly from oil, and the second generation biodiesel (Hydrogenated Bio-Diesel, HBD ) Production process research is underway (Scheme 2).
  • the second-generation biodiesel has excellent fuel properties such as high cetane number (80-90), cloud point (-5 ⁇ -30) and storage stability, and there is no limit to the mixing ratio with conventional diesel.
  • the second generation biodiesel production research is very successful in the field of refinery process and its affiliation with major oil refining companies such as Neste Oil (Finland, NExBTL), UOP (USA, Ecofining), Petrobras (Brazil, H-Bio), NipponOil Corporation BHD) is a hydrotreating process in which hydrogen gas is supplied to fuel as raw material and hydrogen is added to the fuel by a catalyst-mediated agitator.
  • This hydrotreating process is a process used in the existing petrochemical industry and proved its stability and performance.
  • high pressure (50 ⁇ 60 bar) operation conditions are essential.
  • investment and operation costs are high. Therefore, it can only be commercialized if it is linked with existing plants.
  • the 2nd generation biodiesel production process requires a large amount of hydrogen, but its utilization efficiency is low.
  • U.S. Patent No. 7,244,351 prior art, provides hydrogen through a membrane to remove sulfur from hydrocarbons, where hydrogen is generated by electrolysis of water or aqueous solution by an electrode. Therefore, there is a problem of supplying separate electric energy, and the treatment of by-products generated in the electrolysis also becomes a serious problem. Particularly, there is a problem that fouling phenomenon occurs due to subsequent electrolysis and the film is occluded.
  • the present invention which is devised to solve the problems of the prior art, relates to a method for removing carbon double bonds and oxygen by a hydrotreating reaction using a proton transfer medium having proton (H + ) conductivity to produce various raw materials having hydrocarbons It is a general object to provide a method for upgrading a fuel such as biodiesel.
  • the inevitable reason for the progress of high-pressure operation in the hydrotreating reaction process is that the reaction of the hydrogen atom and the raw material is necessary in order to remove the carbon-carbon double bond and oxygen (C ⁇ C, R-CH ⁇ O, ROH, etc.) Since the reaction proceeds on the surface of the catalyst applied to the hydrotreating unit, the hydrogen gas must be dissolved in the raw material (Step 1), and the dissolved hydrogen must be diffused to the catalyst surface and adsorbed on the catalyst surface (Step 2) (Step 3) in which the adsorbed hydrogen is dissociated in the first reaction step can be engaged in the reaction.
  • step 1 determines the reaction rate in the hydrotreating reaction
  • the operation pressure of the process can be kept low when the hydrogen molecule dissolving step is omitted from the milk fat.
  • a proton transfer medium having proton conductivity is interposed between a portion to which hydrogen gas is supplied and a portion to which the fuel is supplied so that the form of hydrogen supplied to the raw material becomes proton , And the protons, which are directly dissociated from hydrogen by the proton transfer medium, are brought into direct contact with the fuel.
  • Hydrogen molecules dissociatively adsorb to hydrogen atoms on the surface of the proton transfer medium and then move to a hydrogen atom form or ionize into protons and electrons. That is, when this proton transfer medium is interposed between the portion where the hydrogen gas is supplied and the portion where the fuel is supplied, the hydrogen source and the proton can be directly transferred to and contacted with the fuel. At this time, hydrogen atoms or protons move by surface movement or permeation of the proton transmission medium.
  • the present invention provides a method for producing a proton-conducting membrane, comprising the steps of: contacting hydrogen gas to a proton-conducting medium having proton conductivity in a predetermined space; Dissociating the proton (H +) by the proton transfer medium; (H +) is supplied to a raw material which is moved to the proton transfer medium by moving the proton (H +) along the proton transfer medium; And contacting the raw material with the proton on the surface of the reaction catalyst disposed on or around the surface of the proton transfer medium to remove carbon double bonds and oxygen in the raw material.
  • the proton transfer medium may be the hydrogen separation membrane coated with the reaction catalyst.
  • the proton transfer medium may be a transferring rod coated with a proton conductive material on the surface thereof. That is, the proton can move along the surface of the proton transfer medium, or the proton can move through the proton transfer medium.
  • a hydrocarbon upgrading apparatus for upgrading hydrocarbons using such a hydrocarbon upgrading method can be divided into a case where the proton moves on the surface of the proton transferring medium and a case where the proton passes through the proton transferring medium, respectively.
  • the hydrocarbon upgrading apparatus when the proton is permeated through the proton transfer medium, includes a hydrogen separation membrane as a proton transfer medium to which a reaction catalyst is applied on one side; A hydrogen supply unit for supplying hydrogen gas to the other side of the hydrogen separation membrane at a predetermined pressure; And a material moving unit which is isolated from the hydrogen supply unit by the hydrogen separation membrane and has a space in contact with the raw material on one side of the hydrogen separation membrane.
  • the reaction catalyst includes at least one of Co, Ni, Mo, Pt, Pd, and Ru.
  • a porous support for supporting the hydrogen separation membrane is formed on one side of the hydrogen separation membrane.
  • the hydrogen separation membrane has a pipe shape, and a raw material transfer part is formed at the center thereof.
  • the hydrogen supply part is a casing having a space inside the hydrogen separation membrane.
  • the hydrocarbon upgrading device when the proton moves on the surface of the proton transfer medium, includes: a housing having a space therein; A raw material supply pipe formed at one side of the housing to supply the raw material; A hydrogen supply pipe installed on the upper portion of the housing to supply hydrogen gas; A reactant discharge pipe installed at a lower portion of the housing to discharge the reacted reaction product; A transferring rod which is a proton transferring medium in which a surface of the raw material and the hydrogen gas are in contact with each other in the housing and a proton conductive material is applied to the surface; And a reaction cage disposed around the transfer rod and containing a reaction catalyst therein.
  • a plurality of the transfer rods are connected to each other, and the plurality of transfer rods are rotated by stirring means inside the housing.
  • the housing is provided with a material circulation means for circulating the raw material by sucking the raw material of the lower portion and supplying it again to the upper portion.
  • the housing is provided with a heating device for heating the raw material.
  • the hydrocarbon upgrading method using the proton conductive material disclosed in the present invention is capable of producing low-cost and high-quality biofuels from various hydrocarbon sources and enhancing energy efficiency and hydrogen utilization efficiency.
  • the spread of eco-friendly biodiesel is expected to contribute to the reduction of national CO 2 emissions and the reduction of diesel vehicle pollutants.
  • FIG. 1 is a schematic view showing a case where a proton is permeated through a proton-transfer medium among the hydrocarbon upgrading methods of the present invention.
  • FIG. 2 is a perspective view illustrating an example of a hydrocarbon upgrading apparatus using the hydrocarbon upgrading method of the present invention.
  • Figure 3 is a cross-sectional view of the hydrocarbon upgrading device of Figure 2;
  • FIG. 4 is a schematic cross-sectional view showing another example of a hydrocarbon upgrading apparatus using the hydrocarbon upgrading method of the present invention.
  • FIG. 5 is a cross-sectional view illustrating the transfer of hydrogen gas to hydrogen proton (H +) through the transfer rod coated with the proton transfer material of FIG.
  • FIG. 6 is an enlarged cross-sectional view of the reaction cage with the hydrogenation reaction catalyst of FIG.
  • FIG. 7 is a perspective view showing still another example of a hydrocarbon upgrading apparatus using a proton transfer medium.
  • a hydrogen separation membrane is used as a proton transfer medium to exclude the step of dissolving hydrogen gas in a liquid raw material composed of biodiesel or hydrocarbon.
  • the reactor chamber is divided into a hydrogen supply unit 16 and a reactant transfer unit 18 with a hydrogen separation membrane 12 as a boundary.
  • the porous support 10 is disposed on a surface of the hydrogen separation membrane 12 which is in contact with the hydrogen supply part 16 to which hydrogen is supplied and the surface of the reactant, 14).
  • the Pd-based hydrogen separation membrane is used as the hydrogen separation membrane 12, but the present invention is not limited thereto.
  • the porous support 10 is provided and the porous support 10 is subjected to a fine polishing process. It is more preferable that the fine polishing process has surface pores of about 10 mu m or less.
  • the porous support may be a metal support or a ceramic support made of one metal selected from the group consisting of nickel (Ni), vanadium (V), niobium (Nb), stainless steel (SUS), tantalum (Ta), and titanium have.
  • the fine polishing process uses a silicon carbide abrasive paper (SiC) to finely polish the porous support at a predetermined polishing rate for a predetermined time.
  • SiC silicon carbide abrasive paper
  • the porous support can be finely polished for a predetermined time at a predetermined polishing rate using a metal powder slurry.
  • a metal powder slurry distilled water mixed with alumina powder may be used.
  • a surface modification process using a known dry plasma can be performed.
  • a palladium layer is formed on the porous support 10 by a sputtering process, and the reaction catalyst 14 is coated on the palladium layer.
  • the reaction catalyst 14 one or more of Ni, Co, Mo, Pd, Pt, and Ru may be used. Thereafter, a heat treatment process such as reflow can be added. Since the hydrotreating reaction is performed on the surface of the reaction catalyst 14, it is preferable that the reaction catalyst 14 has a large surface area as shown in FIG. 1 so as to be in contact with the liquid reaction product.
  • the hydrogen separation membrane 12 can be upgraded through the following process.
  • hydrogen gas supplied from a hydrogen supply source such as a bomb (not shown) through the hydrogen supply unit 16 to an appropriate pressure P1 is transferred to the opposite reactant in the form of a proton through the hydrogen separation membrane.
  • the reactant liquid oil migrates to the catalyst surface at a pressure (P2) that does not affect the permeation of hydrogen and reacts directly with the recombined hydrogen of protons or protons diffused through the separator to produce HBD.
  • the hydrocarbon upgrading device 30 can be implemented using the hydrogen separation membrane.
  • the hydrogen separation membrane 20 is formed in a tubular shape and a reaction part 28 is formed therein.
  • a casing 22 is formed outside the hydrogen separation membrane 20, and the surface of the hydrogen separation membrane 20, So that the space between the inner wall surfaces of the casing 22 constitutes the hydrogen supply portion 26.
  • the casing 22 is provided with a hydrogen supply pipe 24 connected to a hydrogen supply source (not shown).
  • the reactant supply pipe 32 and the reactant discharge pipe 34 are connected to the casing 22 to communicate with the reactant moving part 28.
  • the reactant supply pipe 32 and the reactant discharge pipe 34 are connected to the casing 22 by a known technique such as welding or screwing.
  • a plurality of pipe-shaped hydrogen separation membranes 20 may be installed in one casing 22 to which hydrogen is supplied.
  • the transferring rod is used as a proton transfer medium.
  • the hydrocarbon upgrading apparatus 100 using the proton transfer material includes a housing 110 having a space therein, a raw material supply pipe 114 formed at one side of the housing 110 and supplied with raw materials, A hydrogen supply pipe 112 installed at an upper portion of the housing 110 to supply hydrogen gas and a reactant discharge pipe 116 installed at a lower portion of the housing 110 to discharge a reacted reaction product, A transfer rod 124 which is in contact with the surface of the raw material and the hydrogen gas in the inside of the transfer rod 110 and on which the proton conductive material 126 is applied, (Not shown).
  • the housing 110 is preferably made of a metal material such as a rigid body that can receive electrons generated from hydrogen and ground the outside.
  • the position of the material supply pipe 114 is not limited, it is preferable that the material supply pipe 114 is disposed on the upper portion of the housing 110 because it is not subjected to the pressure by the raw material already stored.
  • a level sensor is installed in the housing 110, It is preferable to control the flow rate of the raw material supplied through the raw material supply pipe 114.
  • the reactant discharge pipe 116 discharges the reactant after completion of the upgrading process.
  • the reactant discharge pipe 116 is equipped with an open / close valve (not shown).
  • the transfer rod 124 is installed inside the housing 110, and has a shape and a length so that it can contact both the hydrogen gas and the liquid raw material. Therefore, it is preferable that the transfer rod 124 is in the form of a rod standing in the vertical direction.
  • the transfer rod 124 may be made of SUS material.
  • a proton transfer material 126 is applied to the outer circumferential surface of the transfer rod 124.
  • the proton transfer material may include one or more of Pd, Nb, Ti, and Tb, and the proton transfer material 126 may be fixed to the transfer rod 124.
  • the transfer rod 124 may be a metal support or a ceramic support made of one metal selected from the group consisting of Ni, V, Nb, SUS, Ta, Lt; / RTI >
  • a reaction cage 128 having a space therein is integrally fixed to the lower side of the transfer rod 124.
  • the reaction cage 128 has a wall structure so that liquid raw materials can freely go in and out .
  • the reaction cage 128 includes a reaction catalyst 130 containing at least one of Co, Ni, Mo, Pt, Pd and Ru.
  • the reaction catalyst 130 may have a pellet or a spherical shape to enlarge the contact area between the proton and the raw material.
  • the cross section of the reaction cage 128 may be selected from various shapes such as a polygonal shape, a circular shape, and a cross shape.
  • agitation means or circulation means for facilitating contact between the reaction catalyst 130 and the raw material, and for facilitating contact between the transfer rod 124 and the hydrogen gas.
  • the hydrocarbon upgrading apparatus 100 is provided with stirring means.
  • the transfer rod 124 may include a stirring arm 122 for connecting a plurality of the transfer rods 124 to each other, a stirring shaft 120 integrally fixed to the stirring arm 122, And a stirring driving unit 118 for applying a rotational force to forcibly rotate.
  • a heating device 132 is installed in the housing 110.
  • the heating device 132 serves to heat the raw material up to the reaction temperature. It is also possible to supply the raw material to the housing 110 in a heated state, but since heat loss occurs during the reaction time, it is preferable that the heating device 132 is provided.
  • an electric heater can be used, and other known heating devices can be used.
  • the hydrocarbon upgrading apparatus 100 of the present invention is basically configured as described above. Hereinafter, an operation of the hydrocarbon upgrading apparatus 100 will be described.
  • a liquid raw material is supplied to expose an upper portion of the transfer rod 124 into a housing 110 having a predetermined space.
  • hydrogen gas is supplied into the housing 110.
  • the stirring drive unit 118 is operated to increase the contact between the upper portion of the transfer rod 124 and the hydrogen gas so that the raw material and the proton are transferred to the surface of the reaction catalyst 130 Lt; / RTI >
  • hydrogen gas is dissociated into protons at the upper surface of the transfer rod 124 at an appropriate reaction temperature (200 to 400 ° C), and the hydrogen gas is released to the lower side of the transfer rod 124 through the proton transfer material 126 .
  • electrons generated when the hydrogen gas is dissociated can be removed by being grounded through the housing 110.
  • the dissociated protons reach the reaction catalyst 130 near the surface of the transfer rod 124 at the lower part of the transfer rod 124. At this time, the raw material around the reaction catalyst 130 is combined with the proton Thereby removing carbon double bonds and oxygen in the raw material.
  • the raw material is carbonized, the carbon single bond and water are generated. After completion of all the raw materials in the housing 110 after the lapse of a predetermined time, the raw material is discharged to the outside through the reactant discharge pipe 116, Process.
  • the hydrocarbon upgrading apparatus 200 is basically the same as the hydrocarbon upgrading apparatus 100 and differs in means for circulating the raw material. Therefore, the same components as those of the hydrocarbon refinement apparatus 100 in the hydrocarbon refinement apparatus 200 will not be described.
  • the hydrocarbon refining apparatus 200 is provided with a raw material circulating means for circulating raw materials up and down.
  • the raw material circulation means includes a circulation pipe 222 installed outside the housing 210 and a circulation pump 224 installed on the circulation pipe 222.
  • the circulation pipe 222 communicates the lower part and the upper part of the housing 210 and the discharge direction of the circulation pump 224 has the upper direction of the housing 210, Can be continuously moved to the upper side of the housing (210).
  • the continuous circulation of the raw material increases the contact efficiency of the raw material with respect to the reaction catalyst.
  • the agitation means of the hydrocarbon upgrading apparatus 100 and the circulation means of the hydrocarbon upgrading apparatus 200 may be applied at the same time.
  • stirring shaft 122 stirring arm
  • reaction cage 130 reaction catalyst
  • Heating device 222 Circulation tube

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de développement d'un combustible tel que diverses matières premières et divers biodiesels contenant des hydrocarbures, par lequel les doubles liaisons carbone-carbone et l'oxygène sont éliminés par une réaction d'hydrotraitement au moyen d'un milieu de protons ayant une conductivité. La présente invention permet ainsi de produire un biocarburant évolué à faibles coûts à partir de diverses sources d'hydrocarbures et d'améliorer l'efficacité énergétique et l'efficacité de l'utilisation d'hydrogène.
PCT/KR2012/004359 2011-06-03 2012-06-01 Procédé de valorisation d'hydrocarbures Ceased WO2012165909A2 (fr)

Priority Applications (2)

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CN201280030045.2A CN103797092B (zh) 2011-06-03 2012-06-01 烃改进方法
US14/123,734 US20140100397A1 (en) 2011-06-03 2012-06-01 Hydrocarbon Advancement Method

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020110054066A KR101298659B1 (ko) 2011-06-03 2011-06-03 수소분리막을 이용한 탄화수소 고급화방법
KR10-2011-0054066 2011-06-03
KR10-2011-0073214 2011-07-22
KR1020110073214A KR101331785B1 (ko) 2011-07-22 2011-07-22 프로톤 전도성물질을 이용한 탄화수소 고급화방법

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WO2012165909A2 WO2012165909A2 (fr) 2012-12-06
WO2012165909A3 WO2012165909A3 (fr) 2013-03-28
WO2012165909A4 true WO2012165909A4 (fr) 2013-05-30

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US (1) US20140100397A1 (fr)
CN (1) CN103797092B (fr)
WO (1) WO2012165909A2 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG11201502233XA (en) * 2012-09-21 2015-05-28 China Petroleum & Chemical Hydrocarbon oil hydrotreating method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR022239A1 (es) * 1999-01-11 2002-09-04 Texaco Development Corp Recuperacion de gas de purga de unidades de hidrotratamiento e hidrocraqueo
FR2806093B1 (fr) * 2000-03-08 2002-05-03 Inst Francais Du Petrole Procede d'hydrogenation selective comprenant une separation partielle d'hydrogene par membrane en amont d'une colonne reactive
FR2828187B1 (fr) * 2001-08-03 2003-12-05 Inst Francais Du Petrole Procede de recuperation d'hydrogene dans un effluent hydrocarbone gazeux, avec mise en oeuvre d'un reacteur membranaire
US7001446B2 (en) * 2002-03-05 2006-02-21 Eltron Research, Inc. Dense, layered membranes for hydrogen separation
US7501546B2 (en) * 2005-12-12 2009-03-10 Neste Oil Oj Process for producing a branched hydrocarbon component
CN101338217B (zh) * 2007-07-04 2012-03-07 中国石油天然气股份有限公司 一种汽油脱硫用复合膜的制造方法

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CN103797092B (zh) 2015-08-19
WO2012165909A2 (fr) 2012-12-06
WO2012165909A3 (fr) 2013-03-28
CN103797092A (zh) 2014-05-14
US20140100397A1 (en) 2014-04-10

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