WO2012165909A2 - Procédé de valorisation d'hydrocarbures - Google Patents

Procédé de valorisation d'hydrocarbures Download PDF

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Publication number
WO2012165909A2
WO2012165909A2 PCT/KR2012/004359 KR2012004359W WO2012165909A2 WO 2012165909 A2 WO2012165909 A2 WO 2012165909A2 KR 2012004359 W KR2012004359 W KR 2012004359W WO 2012165909 A2 WO2012165909 A2 WO 2012165909A2
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WIPO (PCT)
Prior art keywords
raw material
hydrocarbon
hydrogen
proton
separation membrane
Prior art date
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Ceased
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PCT/KR2012/004359
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English (en)
Korean (ko)
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WO2012165909A4 (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, by removing a carbon double bond and oxygen by a hydrotreating reaction using a proton transfer medium having a proton (H + ) conductivity. It relates to a variety of raw materials and methods for upgrading fuel such as biodiesel.
  • Biodiesel (BD) is an environmentally friendly fuel that reduces CO 2 , which is the cause of global warming.It is a lower alkyl ester compound of long-chain fatty acids purified by transesterification of animal and vegetable oils and alcohols as shown in Scheme 1. Its characteristics are almost similar to those of ordinary diesel, making it a fuel that can be applied to the vehicle engines currently used.
  • first-generation biodiesel Fatty Acid Methyl Ester, FAME
  • FAME Food Acid Methyl Ester
  • First-generation biodiesel has a limited fuel properties depending on the properties of the raw materials, and only limited types of raw materials are applied.
  • biodiesel produced from palm oil which has the lowest production cost among vegetable oils, is difficult to apply to vehicles due to low temperature fluidity.
  • fuel conversion technology capable of actively coping with the diversification of raw materials is required.
  • Hydrogenation reaction is applied for biodiesel upgrading (BD upgrading) for high quality biodiesel production or for direct production of biodiesel from oil.
  • BD upgrading biodiesel upgrading
  • 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 property.
  • Second-generation biodiesel production research has shown excellent relevance to the current refinery process, leading major oil companies (Neste Oil (Finland, NExBTL), UOP (US, Ecofining), Petrobras (Brazil, H-Bio), NipponOil Corporation (Japan, BHD)) is a hydroprocessing process that is actively being performed mainly on BHD)), which supplies hydrogen gas to fuel as a raw material, and adds hydrogen to the fuel by means of a catalyst-stirring device to enhance the fuel.
  • US Pat. No. 7,244,351 in the prior art supplies hydrogen through a membrane to remove sulfur from hydrocarbons, where hydrogen is generated by electrolysis of water or aqueous solutions by the electrodes. Therefore, there is a problem to supply a separate electric energy, the treatment of by-products generated during electrolysis is also a significant problem. In particular, fouling may occur due to continuous electrolysis, which may cause the membrane to be blocked.
  • the present invention has been made to solve the problems of the prior art, a variety of raw materials having a hydrocarbon by removing the double bond and oxygen between the carbon by a hydrotreating reaction using a proton transfer medium having a proton (H + ) conductivity and It is a general purpose to provide a method of upgrading fuels such as biodiesel.
  • step 1 when the step of dissolving hydrogen in the milk fat (step 1) is a step of determining the reaction rate in the hydrotreating reaction, the operation pressure of the process can be kept low when excluding the hydrogen molecule dissolution step in the milk fat.
  • a proton transfer medium having proton conductivity between a portion supplied with hydrogen gas and a portion supplied with fuel so that the form of hydrogen supplied to the raw material becomes protons.
  • the protons which are dissociated directly from hydrogen by the proton delivery medium, are in direct contact with the fuel.
  • Hydrogen molecules are dissociative adsorption on the surface of the proton transfer medium as atoms and then migrated to hydrogen atoms or ionized with protons and electrons. That is, when the proton transfer medium is interposed between the hydrogen gas supply portion and the fuel supply portion, hydrogen atoms or protons may be directly delivered to and contact with the fuel. At this time, hydrogen atoms or protons are moved by surface movement or permeation of the proton transfer medium.
  • the present invention includes the steps of contacting hydrogen gas to a proton transfer medium having proton conductivity in a predetermined space; Dissociating protons (H +) by the proton delivery medium; Proton (H +) is moved along the proton delivery medium to supply protons (H +) to the raw material in contact with the proton delivery medium; And a process of removing the carbon double bond and oxygen in the raw material by contacting the raw material with the proton on a surface of the reaction catalyst disposed on or around the proton transfer medium.
  • the proton transfer medium may be the hydrogen separation membrane to which the reaction catalyst is applied.
  • the proton transfer medium may be a transfer rod coated with a proton conductive material on its surface. That is, protons may move along the surface of the proton transfer medium, or the protons may pass through the proton transfer medium.
  • the hydrocarbon upgrading apparatus for upgrading the hydrocarbon by the hydrocarbon upgrading method may be divided into a case where the proton moves on the surface of the proton transfer medium and a case where the proton penetrates the proton transfer medium.
  • the hydrocarbon upgrading apparatus includes a hydrogen separation membrane which is a proton delivery medium to which a reaction catalyst is applied on one side; A hydrogen supply unit supplying hydrogen gas to the other side of the hydrogen separation membrane at a predetermined pressure; And a raw material moving part separated from the hydrogen supply part by the hydrogen separation membrane and having a space in contact with the raw material on one side of the hydrogen separation membrane.
  • reaction catalyst is characterized in that it comprises at least one of Co, Ni, Mo, Pt, Pd, Ru.
  • one side of the hydrogen separation membrane is characterized in that the porous support for supporting the hydrogen separation membrane is formed.
  • the hydrogen separation membrane has the shape of a tube, the raw material moving portion is formed in the center thereof, the hydrogen supply portion is characterized in that the casing having a space inside the hydrogen separation membrane.
  • the hydrocarbon upgrading apparatus in the case where the proton moves the surface of the proton transfer medium, the housing having a space therein; A raw material supply pipe formed on one side of the housing and supplied with raw materials; A hydrogen supply pipe installed at an upper portion of the housing and supplied with hydrogen gas; A reactant discharge tube installed at a lower portion of the housing to discharge a reactant having completed the reaction; A transfer rod in which the surface is in contact with both the raw material and the hydrogen gas in the housing, and a proton transfer medium on which the proton conductive material is applied; And a reaction cage disposed around the delivery rod and accommodating a reaction catalyst therein.
  • the plurality of transfer rods are connected to each other, the plurality of transfer rods are characterized in that the rotating by the stirring means in the housing.
  • the housing is characterized in that the raw material circulation means for circulating the raw material by supplying the lower raw material to the upper supply again.
  • the housing is characterized in that the heating device for heating the raw material is installed.
  • Hydrocarbon advanced method using the proton conductive material disclosed in the present invention is a process that can produce low-cost high-end biofuel from a variety of hydrocarbon sources, and can increase the 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 pollutants generated by diesel vehicles.
  • 1 is a view schematically illustrating a case where protons penetrate the proton transfer medium in the hydrocarbon upgrading method of the present invention.
  • FIG. 2 is a perspective view showing an example of a hydrocarbon upgrading apparatus using the hydrocarbon upgrading method of the present invention.
  • FIG. 3 is a cross-sectional view of the hydrocarbon advanced device of FIG.
  • 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 of the hydrogen gas is delivered to the hydrogen proton (H +) through the transfer rod coated with the proton transfer material of FIG. 4.
  • FIG. 6 is an enlarged cross-sectional view of a reaction cage in which the hydrogenation catalyst of FIG. 4 is incorporated.
  • FIG. 7 is a perspective view showing another example of a hydrocarbon upgrading apparatus using a proton transfer medium.
  • the present invention uses a hydrogen separation membrane 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 moving unit 18 by the hydrogen separation membrane 12 that transmits hydrogen.
  • the porous support 10 is disposed on the surface of the hydrogen separation membrane 12 that is in contact with the hydrogen supply unit 16 to which hydrogen is supplied, and the reaction catalyst is formed on the surface that is in contact with the reactant moving unit 18 to which the reactant is supplied. 14) is located.
  • a Pd-based hydrogen separation membrane is used as the hydrogen separation membrane 12, but is not limited thereto.
  • the porous support 10 is provided, and the porous support 10 is subjected to a fine polishing process. More preferably, the fine polishing process has surface pores of about 10 mu m or less.
  • the porous support may be a metal support or ceramic support made of one metal selected from nickel (Ni), vanadium (V), niobium (Nb), stainless steel (SUS), tantalum (Ta), and titanium (Ti). have.
  • silicon carbide abrasive paper SiC is used to finely polish the porous support for a predetermined time at a predetermined polishing rate.
  • a metal powder slurry may be used to micropolize the porous support for a predetermined time at a predetermined polishing rate.
  • a mixture of alumina powder and distilled water may be used as the metal powder slurry.
  • a palladium layer is formed on the porous support 10 by a sputtering process, and a reaction catalyst 14 is coated on the upper side thereof.
  • a reaction catalyst 14 one or more catalysts of Ni, Co, Mo, Pd, Pt, and Ru may be used. Thereafter, a heat treatment process such as reflow can be added. Since the hydroprocessing reaction is carried out on the surface of the reaction catalyst 14, it is preferable that the surface of the reaction catalyst 14 is large so that the reaction catalyst 14 is in good contact with the liquid phase reactant.
  • the hydrogen separation membrane 12 is advanced oil through the following process.
  • the hydrogen gas supplied at a suitable pressure P1 through the hydrogen supply unit 16 from a hydrogen source such as a bomb (not shown) moves to the opposite reactant in the form of a proton through a hydrogen separation membrane.
  • the reactant (liquid oil) moves to the surface of the catalyst at a pressure (P2) that does not affect hydrogen permeation, and directly reacts with protons or protons that are diffused through the membrane to produce HBD.
  • the hydrogen gas is adsorbed on the surface of the hydrogen gas separation membrane 12 supplied through the bomb and dissociated into protons (H +), and the protons diffuse in the hydrogen separation membrane 12 to form the hydrogen separation membrane (
  • the reactant moving part 12 moves to the surface in contact with the moving part 18.
  • the pressure at which the hydrogen permeation moves may be provided by the bombe. Therefore, even without a separate pressurization device, since the hydrogen is supplied only by the pressure of the bomb itself, relatively low pressure operation is possible, and the hydrogen utilization efficiency can be improved.
  • the hydrocarbon upgrade apparatus 30 may be implemented using such a hydrogen separation membrane.
  • the hydrogen separation membrane 20 is formed in a tubular form, and a reactant moving part 28 is formed therein, and a casing 22 is formed outside of the hydrogen separation membrane 20 to form the surface of the hydrogen separation membrane 20 and the The space between the inner wall surface of the casing 22 forms the hydrogen supply part 26.
  • the casing 22 is arranged with a hydrogen supply pipe 24 connected to a hydrogen supply source (not shown).
  • the casing 22 is coupled to the reactant supply pipe 32 and the reactant discharge pipe 34 in communication with the reactant moving unit 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 reactant such as biodiesel may be used. Higher quality is possible.
  • tubular hydrogen separation membranes 20 may be provided in one casing 22 to which hydrogen is supplied.
  • a proton shear material is applied to exclude a step of dissolving hydrogen gas in a liquid raw material composed of biodiesel or hydrocarbon.
  • the transfer rod is used as the proton transfer medium.
  • the hydrocarbon advanced device 100 using the proton transfer material includes a housing 110 having a space therein, and a raw material supply pipe 114 formed on one side of the housing 110 to supply raw materials;
  • a hydrogen supply pipe 112 installed at an upper portion of the housing 110 to supply hydrogen gas, a reactant discharge tube 116 installed at a lower portion of the housing 110 to discharge a reactant having completed a reaction, and the housing ( 110, the surface of the raw material and the hydrogen gas in contact with both the inside and the transfer rod 124, the proton conductive material 126 is applied to the surface, disposed around the transfer rod 124 and the reaction catalyst 130 therein May comprise a reaction cage 128.
  • the housing 110 is preferably made of a metal material such as a rigid body that can receive electrons generated from hydrogen and ground to the outside.
  • the raw material supply pipe 114 is not limited in position, but is preferably disposed on the upper portion of the housing 110 is not pressured by the stored raw material, the 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).
  • Hydrogen is supplied through the hydrogen supply pipe 112 and may be supplied at a low pressure (10 bar or less).
  • the reactant discharge pipe 116 is to discharge the reactants having completed the advanced 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 capable of contacting both hydrogen gas and a raw material in a liquid state. Therefore, the transfer rod 124 is preferably in the form of a rod standing in the vertical direction.
  • the transfer rod 124 may use a SUS material.
  • Proton transfer material 126 is coated on 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 is a metal support or ceramic support made of a metal selected from nickel (Ni), vanadium (V), niobium (Nb), stainless steel (SUS), tantalum (Ta), and titanium (Ti). Can be.
  • the reaction cage 128 having a space therein is fixed to the lower side of the transfer rod 124, the reaction cage 128 has a network structure of the wall, the liquid raw material can freely enter and exit. .
  • reaction catalyst 130 including one or more of Co, Ni, Mo, Pt, Pd, and Ru is embedded in the reaction cage 128.
  • the reaction catalyst 130 may have a pellet or spherical shape to increase the contact area with protons and the raw material.
  • cross section of the reaction cage 128 may be selected from various shapes such as polygon, circle, cross.
  • a stirring means or a circulation means to facilitate the contact between the reaction catalyst 130 and the raw material and at the same time to facilitate the contact between the delivery rod 124 and the hydrogen gas.
  • the hydrocarbon advanced device 100 is provided with stirring means.
  • the transfer rod 124 is a stirring arm 122 for connecting a plurality of each other, a stirring shaft 120 is fixed integrally to the stirring arm 122, and the stirring shaft 120 It includes a stirring drive unit 118 for imparting 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 to the reaction temperature.
  • the raw material may be supplied to the housing 110 in a heated state.
  • the heating device 132 is preferably provided.
  • An electric heater may be used as the heating device 132, and other known heating devices may be used.
  • the hydrocarbon upgrading apparatus 100 of the present invention is basically configured as described above. Hereinafter, the operation of the hydrocarbon advanced device 100 will be described.
  • a liquid raw material is supplied to expose the upper portion of the transfer rod 124 into the housing 110 having a predetermined space.
  • hydrogen gas is supplied into the housing 110.
  • the stirring drive unit 118 to increase the contact of the hydrogen gas and the upper portion of the transfer rod 124, the raw material and proton at the lower portion of the transfer rod 124 and the surface of the reaction catalyst 130 Improves contact.
  • hydrogen gas is dissociated into protons on the upper side surface of the transfer rod 124 under an appropriate reaction temperature (200 to 400 ° C.), and then through the proton transfer material 126 to the lower side of the transfer rod 124. Will move.
  • electrons generated by dissociation of hydrogen gas may be removed by being grounded through the housing 110.
  • the dissociated protons reach the reaction catalyst 130 close to the surface of the transfer rod 124 at the lower portion of the transfer rod 124, and the raw material around the reaction catalyst 130 is combined with the protons. Carbon double bonds and oxygen in the raw material are removed.
  • the raw material is a carbon single bond and water is generated, and after a predetermined time when all of the raw material in the housing 110 is completed, discharged to the outside through the reactant discharge pipe 116, to remove the water from the reactant It goes through the process.
  • the hydrocarbon upgrading device 200 is basically the same as the hydrocarbon upgrading device 100, and there is a difference in means for circulating raw materials. Therefore, the same components as those of the hydrocarbon advanced device 100 in the hydrocarbon advanced device 200 will be omitted.
  • the hydrocarbon upgrading apparatus 200 is provided with a raw material circulation means for circulating the raw material up and down.
  • the raw material circulation means includes a circulation pipe 222 installed to the outside of the housing 210 and a circulation pump 224 installed on the circulation pipe 222.
  • the circulation pipe 222 communicates the lower and upper portions of the housing 210 with each other, and since the discharge direction of the circulation pump 224 has the upper direction of the housing 210, the lower portion of the housing 210.
  • the raw material on the side may continuously move to the upper side of the housing 210.
  • the continuous efficiency of the raw material increases the contact efficiency of the raw material to the reaction catalyst.
  • stirring means of the hydrocarbon upgrading device 100 and the circulation means of the hydrocarbon upgrading device 200 may be applied at the same time.
  • reaction catalyst 16 reaction catalyst 1626: hydrogen supply unit
  • stirring shaft 122 stirring arm
  • reaction cage 130 reaction catalyst

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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)

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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)

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

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WO (1) WO2012165909A2 (fr)

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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
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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
WO2012165909A4 (fr) 2013-05-30
WO2012165909A3 (fr) 2013-03-28
CN103797092A (zh) 2014-05-14
US20140100397A1 (en) 2014-04-10

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