WO2019000381A1 - 一种合成气制芳烃的系统及方法 - Google Patents

一种合成气制芳烃的系统及方法 Download PDF

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WO2019000381A1
WO2019000381A1 PCT/CN2017/091068 CN2017091068W WO2019000381A1 WO 2019000381 A1 WO2019000381 A1 WO 2019000381A1 CN 2017091068 W CN2017091068 W CN 2017091068W WO 2019000381 A1 WO2019000381 A1 WO 2019000381A1
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gas
unit
separation unit
aromatic hydrocarbon
synthesis gas
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French (fr)
Inventor
崔宇
黄晓凡
汤效平
王彤
骞伟中
魏飞
高长平
王秀林
殷作如
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HUADIAN COAL INDUSTRY GROUP Co Ltd
Tsinghua University
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HUADIAN COAL INDUSTRY GROUP Co Ltd
Tsinghua University
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Priority to CN201780092655.8A priority Critical patent/CN110891925A/zh
Priority to US16/626,715 priority patent/US11332417B2/en
Priority to PCT/CN2017/091068 priority patent/WO2019000381A1/zh
Publication of WO2019000381A1 publication Critical patent/WO2019000381A1/zh
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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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0405—Apparatus
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/22—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
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    • C01—INORGANIC CHEMISTRY
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0485—Set-up of reactors or accessories; Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/09—Purification; Separation; Use of additives by fractional condensation
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
    • 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
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/04—Benzene
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    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/06—Toluene
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    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/08—Xylenes
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/44—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/46—Iron group metals or copper
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

Definitions

  • the invention relates to a system and a method for synthesizing gaseous aromatic hydrocarbons, and belongs to the technical field of petrochemical industry.
  • Triphenyl and “triene” are the basic chemical raw materials in the petrochemical industry.
  • triphenyl is the main aromatic hydrocarbon material, which is traditionally mainly derived from petroleum refining and coal retorting.
  • aromatic hydrocarbon raw materials mainly composed of benzene and para-xylene obtained by aromatic hydrocarbon reforming and aromatics combined process.
  • Basic chemical raw materials for fiber and new chemical materials are obtained by petroleum route, especially naphtha as raw material, and aromatic hydrocarbon raw materials mainly composed of benzene and para-xylene obtained by aromatic hydrocarbon reforming and aromatics combined process.
  • Basic chemical raw materials for fiber and new chemical materials are the supply of aromatic hydrocarbons continues to be tight and the price is high, which greatly affects the supply of raw materials for the subsequent chemical fiber and new materials industries.
  • Aromatic hydrocarbons In recent years, some researchers have developed a process route for the production of aromatic hydrocarbons from alcohol ethers using methanol and dimethyl ether as the main raw materials. The process is generally based on coal, gasification, change, methanol synthesis and purification, and then methanol. Aromatic hydrocarbons.
  • the method can alleviate the dependence of aromatic hydrocarbon raw materials on petroleum to a certain extent, but the process has the disadvantages of long production path, large investment, and large energy consumption; at the same time, a large amount of water is consumed in the process of producing methanol from coal, and methanol is produced. Water is also produced in the process of aromatics, resulting in a waste of large amounts of water.
  • Chinese patent application CN1880288A discloses a methanol/dimethyl ether aromatization technique which uses a modified ZSM-5 catalyst to separate the product into a gas phase and an oil phase product by cooling, and an oil phase product is subjected to extraction to obtain an aromatic hydrocarbon.
  • non-aromatic hydrocarbons taking into account the current process route of coal-to-methanol, the processing path of this process is long, and the shortcomings of large investment are undoubted.
  • the object of the present invention is to provide a system and a method for synthesizing aromatic hydrocarbons by using a synthesis gas, and synthesizing aromatic hydrocarbons by one-step synthesis of syngas, thereby overcoming the disadvantages of long production path, large investment, and high energy consumption of the aromatics process by methanol. .
  • the present invention first provides a system for synthesizing gaseous aromatic hydrocarbons, comprising: a synthesis gas purification unit, a synthesis gas conversion unit, a synthesis gas aromatic hydrocarbon unit, a gas-liquid separation unit, a liquefied gas separation unit, and a dry gas. Separation unit, dry gas conversion unit, oil-water separation unit;
  • the synthesis gas purification unit, the synthesis gas conversion unit, the synthesis gas aromatic hydrocarbon unit, and the gas-liquid separation unit are sequentially connected;
  • the gas-liquid separation unit is respectively connected to the liquefied gas separation unit and the oil-water separation unit;
  • the liquefied gas separation unit is connected to the dry gas separation unit;
  • the dry gas separation unit is respectively connected to the dry gas conversion unit and the synthesis gas aromatic hydrocarbon unit;
  • the dry gas conversion unit is connected to the synthesis gas aromatic hydrocarbon unit.
  • the syngas purification unit is used for purifying the synthesis gas as a raw material; the synthesis gas conversion unit is for adjusting the ratio of hydrogen to carbon monoxide in the synthesis gas; and the synthesis gas to produce an aromatic hydrocarbon unit for contacting the gas with the catalyst
  • the reaction produces an aromatic hydrocarbon;
  • the gas-liquid separation unit is used for separating the aromatic hydrocarbon product into a gas phase and a liquid phase; and the liquefied gas separation unit is for separating the gas phase separated by the gas-liquid separation unit into a liquefied gas and a dry gas, wherein the liquefied gas is used as Product output, dry gas enters the dry gas separation unit; dry gas separation unit is used to separate the dry gas separated by the liquefied gas separation unit into hydrogen, carbon monoxide and methane, ethane, ethylene, carbon dioxide, wherein methane and ethane can enter
  • the dry gas conversion unit is converted into synthesis gas (ie hydrogen and carbon monoxide), and a part of methane
  • oil moisture Liquid phase separation means for separating the gas-liquid separation unit is an oil phase (e.g., aromatics) and an aqueous phase, respectively, then the system enters the corresponding processing.
  • the liquefied gas separation unit is connected to the synthesis gas aromatic hydrocarbon unit for conveying liquefied gas and ethylene to the synthesis gas aromatic hydrocarbon unit, and the liquefied gas and ethylene produced by the synthesis gas to produce the aromatic hydrocarbon unit are separated. Return to the synthesis gas aromatics unit to further increase aromatics.
  • the present invention also provides a method for synthesizing gaseous aromatic hydrocarbons, which is carried out using the above system, the method comprising the steps of:
  • the raw syngas is introduced into the syngas purification unit for purification;
  • step d After cooling the reaction product obtained in step c, it is separated into a gas phase and a liquid phase by entering a gas-liquid three-phase separation unit, wherein the gas phase enters the liquefied gas separation unit and is separated into liquefied gas and dry gas, and the liquid phase enters the oil-water separation unit to be separated.
  • a gas-liquid three-phase separation unit wherein the gas phase enters the liquefied gas separation unit and is separated into liquefied gas and dry gas, and the liquid phase enters the oil-water separation unit to be separated.
  • step d the dry gas obtained in step d is separated into hydrogen, carbon monoxide and methane, ethane, ethylene, carbon dioxide into the dry gas separation unit;
  • step e The methane and ethane obtained in step e are converted into a synthesis gas, that is, hydrogen and carbon monoxide, into a dry gas conversion unit.
  • a synthesis gas that is, hydrogen and carbon monoxide
  • the catalyst used for producing the aromatic hydrocarbon in the synthesis gas aromatic hydrocarbon unit is a composite catalyst.
  • the composite catalyst includes a support and a first metal component and a second metal component.
  • the carrier used comprises a combination of one or more of ZSM-5 molecular sieve, ZSM-11 molecular sieve and ZSM-22 molecular sieve;
  • the first metal component is one of zinc, silver, gallium, antimony and bismuth;
  • the first metal component is 0.1 to 10% by mass of the total mass of the catalyst
  • the second metal component is one or more of iron, cobalt, chromium, manganese, and copper.
  • the content of the second metal component is 10-60% of the total mass of the catalyst, based on the metal; the content of the molecular sieve as the carrier is 30-90% of the total mass of the catalyst; the carrier, the first metal component, the second metal The sum of the masses of the components is 100%.
  • the liquefied gas separated by the liquefied gas separation unit enters the synthesis gas to produce an aromatic hydrocarbon unit to produce an aromatic hydrocarbon.
  • the dry gas separation unit separates a part of the hydrogen gas and carbon dioxide into the aromatic hydrocarbon processing unit.
  • step f a portion of methane, a portion of ethane, and all of the ethylene are produced, and the remaining all of the methane and all of the ethane are converted into a synthesis gas, that is, hydrogen and carbon monoxide, into a dry gas conversion unit.
  • a synthesis gas that is, hydrogen and carbon monoxide
  • the reaction temperature in the synthesis gas aromatic hydrocarbon unit is from 300 to 550 ° C; preferably from 380 to 520 ° C.
  • the volume space velocity in the synthesis gas aromatic hydrocarbon unit is from 100 to 100,000 h -1 ; preferably from 1,000 to 10,000 h -1 .
  • the reaction pressure in the synthesis gas aromatic hydrocarbon unit is from 1.0 to 10.0 MPa.
  • the molar ratio of carbon monoxide to hydrogen in the shifted synthesis gas at the outlet of the synthesis gas shift unit is from 1.0 to 3.5:1; preferably from 1.5 to 3.0:1.
  • the conversion pressure is 1.5 to 4.0 MPa, and the conversion temperature is 800 to 1000 °C.
  • the separation of the gas phase and the liquid phase in the gas-liquid three-phase separation unit may be carried out by a conventional cooling separation method; the separation of the gas phase into the liquefied gas separation unit into a liquefied gas and a dry gas may be carried out by a conventional oil absorption separation method; The separation of the oil-water separation unit into the oil phase and the water phase may be carried out by a conventional oil-water separation method; in the step e, the separation of the dry gas in the dry gas separation unit is performed by a combination of cooling oil absorption and adsorbent adsorption.
  • the coal-to-methanol process requires a large amount of water, and a large amount of carbon monoxide is needed for water gas conversion to provide methanol synthesis.
  • the hydrogen gas, and the problem of regenerating water in the process of producing aromatic hydrocarbons from methanol, resulting in waste of a large amount of water resources, the system and method for synthesizing aromatic hydrocarbons provided by the present invention use synthetic gas to synthesize aromatic hydrocarbons in one step, thereby overcoming methanol production.
  • the aromatics process has the advantages of long production path, large investment and high energy consumption. The investment is reduced by more than 15% and the energy consumption is reduced by more than 20%.
  • the invention provides a method for utilizing dry gas by-product of a synthesis gas aromatization process, which comprises generating carbon monoxide and hydrogen by separating dry gas and steam reforming of dry gas, as a return synthesis gas aromatization reaction system, The problem of utilization of by-products is solved, and the unit gas consumption per ton of aromatic hydrocarbon products is also reduced.
  • the present invention also provides a method for increasing the production of aromatic hydrocarbons by returning the liquefied gas by-produced in the synthesis gas to aromatics to the aromatic gas reaction system, thereby solving the problem of utilization of the liquefied gas and improving the yield of the aromatic hydrocarbon.
  • the invention solves the problem of utilizing dry gas of by-products from the perspective of recycling economy, reduces the water consumption in the process, and conforms to the concept of green chemistry.
  • Example 1 is a process flow diagram of a system and method for producing aromatic hydrocarbons from syngas provided in Example 1.
  • Example 2 is a process flow diagram of a system and method for syngas to produce aromatics provided in Example 5.
  • Example 3 is a process flow diagram of a system and method for syngas to produce aromatics provided in Example 6.
  • the present invention provides a system and method for producing aromatic hydrocarbons from coal, and the present invention will be further described below in conjunction with the accompanying drawings.
  • This embodiment provides a system for synthesizing gaseous aromatic hydrocarbons, the structure of which is shown in FIG.
  • the system comprises: a synthesis gas purification unit 1, a synthesis gas conversion unit 2, a synthesis gas aromatic hydrocarbon unit 3, a gas-liquid separation unit 4, a liquefied gas separation unit 5, a dry gas separation unit 6, a dry gas conversion unit 7, and an oil-water separation unit. 8;
  • the synthesis gas purification unit 1, the synthesis gas conversion unit 2, the synthesis gas aromatic hydrocarbon unit 3, and the gas-liquid separation unit 4 are sequentially connected;
  • the outlet of the gas-liquid separation unit 4 is connected to the liquefied gas separation unit 5 and the oil-water separation unit 8, respectively;
  • the outlet of the liquefied gas separation unit 5 is connected to the dry gas separation unit 6;
  • the outlet of the dry gas separation unit 6 is connected to the dry gas conversion unit 7 and the synthesis gas aromatic hydrocarbon unit 4, respectively;
  • the outlet of the dry gas conversion unit 7 is connected to the synthesis gas aromatic hydrocarbon unit 4.
  • the raw syngas is introduced into the syngas purification unit 1 for purification;
  • the first metal is zinc, antimony
  • the second metal is iron, cobalt, manganese
  • the oil phase components such as benzene, toluene, C 8 aromatic hydrocarbon, C 9 aromatic hydrocarbon, C 10 aromatic hydrocarbon and heavy aromatic hydrocarbon have the composition shown in Table 1.
  • the reacted product material enters the gas-liquid separation unit 4 and is separated into a gas phase product and a liquid phase product, wherein the liquid phase product enters the oil-water separation unit 8 and is separated into an oil phase and an aqueous phase, and the oil phase and the water phase respectively enter a corresponding post-system treatment. ;
  • the gas phase product separated by the gas-liquid separation unit 4 enters the liquefied gas separation unit 5 and is separated into liquefied gas and a part of ethylene and dry gas, wherein the liquefied gas and ethylene are used as products, and the dry gas enters the dry gas separation unit 6 and is separated into hydrogen, carbon monoxide and methane. , ethane, ethylene and carbon dioxide, wherein hydrogen, carbon monoxide is returned to the synthesis gas to produce aromatic hydrocarbon unit 3 for reaction, methane and ethane are converted into synthesis gas by the dry gas conversion unit 7, ie hydrogen and carbon monoxide, the conversion temperature is 900 ° C, conversion The pressure was 3.0 MPa and then returned to the synthesis gas to produce the aromatic hydrocarbon unit 3.
  • the present embodiment provides a method for synthesizing gaseous aromatic hydrocarbons, which is carried out by the system of embodiment 1, the method comprising the steps of:
  • the raw syngas is introduced into the syngas purification unit 1 for purification;
  • the gas is introduced into the synthesis gas to produce the aromatic hydrocarbon unit 3 for reaction.
  • the carrier of the catalyst used is ZSM-11 molecular sieve, the first metal is zinc, ruthenium, the second metal is iron, cobalt, copper, ZSM-11 molecular sieve, metal zinc,
  • the volumetric space velocity is 10000h -1 , and the gas forms a phase component such as gas phase, water phase, non-aromatic hydrocarbon, benzene, toluene, C 8 aromatic hydrocarbon, C 9 aromatic hydrocarbon, C 10 aromatic hydrocarbon and heavy aromatic hydrocarbon under the action of catalyst.
  • Table 2 shows.
  • the reacted product material enters the gas-liquid separation unit 4 and is separated into a gas phase product and a liquid phase product, wherein the liquid phase product enters the oil-water separation unit 8 and is separated into an oil phase and an aqueous phase, and the oil phase and the water phase respectively enter a corresponding post-system treatment. ;
  • the gas phase product separated by the gas-liquid separation unit 4 enters the liquefied gas separation unit 5 and is separated into liquefied gas and a part of ethylene and dry gas, wherein the liquefied gas and ethylene are used as products, and the dry gas enters the dry gas separation unit 6 and is separated into hydrogen, carbon monoxide and methane. , ethane, ethylene and carbon dioxide, wherein hydrogen, carbon monoxide is returned to the synthesis gas to produce aromatic hydrocarbon unit 3 for reaction, methane and ethane are converted into synthesis gas by the dry gas conversion unit 7, ie hydrogen and carbon monoxide, the conversion temperature is 1000 ° C, conversion The pressure was 2.0 MPa and then returned to the synthesis gas to produce the aromatic hydrocarbon unit 3.
  • the present embodiment provides a method for synthesizing gaseous aromatic hydrocarbons, which is carried out by the system of embodiment 1, the method comprising the steps of:
  • the raw syngas is introduced into the syngas purification unit 1 for purification;
  • the gas is introduced into the synthesis gas to produce the aromatic hydrocarbon unit 3 for reaction.
  • the carrier of the catalyst used is ZSM-22 molecular sieve, the first metal is zinc, gallium, the second metal is iron, cobalt, ZSM-22 molecular sieve, metal zinc, metal gallium.
  • the gas forms an oil phase component such as a gas phase, an aqueous phase, a non-aromatic hydrocarbon, a benzene, a toluene, a C 8 aromatic hydrocarbon, a C 9 aromatic hydrocarbon, a C 10 aromatic hydrocarbon, and a heavy aromatic hydrocarbon under the action of a catalyst, and its composition is shown in Table 3.
  • the reacted product material enters the gas-liquid separation unit 4 and is separated into a gas phase product and a liquid phase product, wherein the liquid phase product enters the oil-water separation unit 8 and is separated into an oil phase and an aqueous phase, and the oil phase and the water phase respectively enter a corresponding post-system treatment. ;
  • the gas phase product separated by the gas-liquid separation unit 4 enters the liquefied gas separation unit 5 and is separated into liquefied gas and a part of ethylene and dry gas, wherein the liquefied gas and ethylene are used as products, and the dry gas enters the dry gas separation unit 6 and is separated into hydrogen, carbon monoxide and methane. , ethane, ethylene and carbon dioxide, wherein hydrogen, carbon monoxide is returned to the synthesis gas to produce aromatic hydrocarbon unit 3 for reaction, methane and ethane are converted into synthesis gas by the dry gas conversion unit 7, ie hydrogen and carbon monoxide, the conversion temperature is 800 ° C, conversion The pressure was 2.0 MPa and then returned to the synthesis gas to produce the aromatic hydrocarbon unit 3.
  • This embodiment provides a system for synthesizing gaseous aromatic hydrocarbons, the structure of which is shown in FIG.
  • the system comprises: a synthesis gas purification unit 1, a synthesis gas conversion unit 2, a synthesis gas aromatic hydrocarbon unit 3, a gas-liquid separation unit 4, a liquefied gas separation unit 5, a dry gas separation unit 6, a dry gas conversion unit 7, and an oil-water separation unit. 8;
  • the synthesis gas purification unit 1, the synthesis gas conversion unit 2, the synthesis gas aromatic hydrocarbon unit 3, and the gas-liquid separation unit 4 are sequentially connected;
  • the outlet of the gas-liquid separation unit 4 is connected to the liquefied gas separation unit 5 and the oil-water separation unit 8, respectively;
  • the outlet of the liquefied gas separation unit 5 is connected to the dry gas separation unit 6 and the synthesis gas aromatic hydrocarbon unit 3;
  • the outlet of the dry gas separation unit 6 is connected to the dry gas conversion unit 7 and the synthesis gas aromatic hydrocarbon unit 4, respectively;
  • the outlet of the dry gas conversion unit 7 is connected to the synthesis gas aromatic hydrocarbon unit 4.
  • the raw syngas is introduced into the syngas purification unit 1 for purification;
  • the gas is introduced into the synthesis gas to produce the aromatic hydrocarbon unit 3 for reaction.
  • the carrier of the catalyst used is ZSM-5 molecular sieve, the first metal is zinc, ruthenium, the second metal is iron, cobalt, ZSM-5 molecular sieve, metal zinc, metal ruthenium.
  • the gas forms an oil phase component such as a gas phase, an aqueous phase, a non-aromatic hydrocarbon, a benzene, a toluene, a C 8 aromatic hydrocarbon, a C 9 aromatic hydrocarbon, a C 10 aromatic hydrocarbon, and a heavy aromatic hydrocarbon under the action of a catalyst, and its composition is shown in Table 4.
  • the reacted product material enters the gas-liquid separation unit 4 and is separated into a gas phase product and a liquid phase product, wherein the liquid phase product enters the oil-water separation unit 8 and is separated into an oil phase and an aqueous phase, and the oil phase and the water phase respectively enter a corresponding post-system treatment. ;
  • the gas phase product separated by the gas-liquid separation unit 4 enters the liquefied gas separation unit 5 and is separated into liquefied gas and a part of ethylene and dry gas, wherein the liquefied gas and ethylene are returned as raw materials to the synthesis gas to produce the aromatic hydrocarbon unit 3, and the dry gas enters the dry gas separation unit 6 Separation into hydrogen, carbon monoxide and methane, ethane, ethylene and carbon dioxide, wherein hydrogen and carbon monoxide are returned to the synthesis gas to produce aromatic hydrocarbon unit 3 for reaction, and methane and ethane are converted into synthesis gas, that is, hydrogen and carbon monoxide, into dry gas conversion unit 7.
  • the conversion temperature was 800 ° C
  • the conversion pressure was 2.0 MPa
  • This embodiment provides a system for synthesizing gaseous aromatic hydrocarbons, the structure of which is shown in FIG.
  • the system comprises: a synthesis gas purification unit 1, a synthesis gas conversion unit 2, a synthesis gas aromatic hydrocarbon unit 3, a gas-liquid separation unit 4, a liquefied gas separation unit 5, a dry gas separation unit 6, a dry gas conversion unit 7, and an oil-water separation unit. 8;
  • the synthesis gas purification unit 1, the synthesis gas conversion unit 2, the synthesis gas aromatic hydrocarbon unit 3, and the gas-liquid separation unit 4 are sequentially connected;
  • the outlet of the gas-liquid separation unit 4 is connected to the liquefied gas separation unit 5 and the oil-water separation unit 8, respectively;
  • the outlet of the liquefied gas separation unit 5 is connected to the dry gas separation unit 6 and the synthesis gas aromatic hydrocarbon unit 3;
  • the outlet of the dry gas separation unit 6 is connected to the dry gas conversion unit 7 and the synthesis gas aromatic hydrocarbon unit 4, respectively;
  • the outlet of the dry gas conversion unit 7 is connected to the synthesis gas aromatic hydrocarbon unit 4.
  • the raw syngas is introduced into the syngas purification unit 1 for purification;
  • the gas is introduced into the synthesis gas to produce the aromatic hydrocarbon unit 3 for reaction.
  • the carrier of the catalyst used is ZSM-11 molecular sieve, the first metal is zinc, silver, the second metal is iron, copper, ZSM-11 molecular sieve, metallic zinc, metallic silver.
  • the gas forms an oil phase component such as a gas phase, an aqueous phase, a non-aromatic hydrocarbon, a benzene, a toluene, a C 8 aromatic hydrocarbon, a C 9 aromatic hydrocarbon, a C 10 aromatic hydrocarbon, and a heavy aromatic hydrocarbon under the action of a catalyst, and its composition is shown in Table 5.
  • the reacted product material enters the gas-liquid separation unit 4 and is separated into a gas phase product and a liquid phase product, wherein the liquid phase product enters the oil-water separation unit 8 and is separated into an oil phase and an aqueous phase, and the oil phase and the water phase respectively enter a corresponding post-system treatment. ;
  • the gas phase product separated by the gas-liquid separation unit 4 enters the liquefied gas separation unit 5 and is separated into liquefied gas and a part of ethylene and dry gas, wherein the liquefied gas and ethylene are returned as raw materials to the synthesis gas to produce the aromatic hydrocarbon unit 3, and the dry gas enters the dry gas separation unit 6 Separation into hydrogen, carbon monoxide and methane, ethane, ethylene and carbon dioxide, wherein hydrogen and carbon monoxide are returned to the synthesis gas to produce aromatic hydrocarbon unit 3 for reaction, and methane and ethane are converted into synthesis gas, that is, hydrogen and carbon monoxide, into dry gas conversion unit 7.
  • the conversion temperature was 900 ° C
  • the conversion pressure was 3.0 MPa
  • This embodiment provides a system for synthesizing gaseous aromatic hydrocarbons, the structure of which is shown in FIG.
  • the system comprises: a synthesis gas purification unit 1, a synthesis gas conversion unit 2, a synthesis gas aromatic hydrocarbon unit 3, a gas-liquid separation unit 4, a liquefied gas separation unit 5, a dry gas separation unit 6, a dry gas conversion unit 7, and an oil-water separation unit. 8;
  • the synthesis gas purification unit 1, the synthesis gas conversion unit 2, the synthesis gas aromatic hydrocarbon unit 3, and the gas-liquid separation unit 4 are sequentially connected;
  • the outlet of the gas-liquid separation unit 4 is connected to the liquefied gas separation unit 5 and the oil-water separation unit 8, respectively;
  • the outlet of the liquefied gas separation unit 5 is connected to the dry gas separation unit 6;
  • the outlet of the dry gas separation unit 6 is connected to the dry gas conversion unit 7 and the synthesis gas aromatic hydrocarbon unit 4, respectively;
  • the outlet of the dry gas conversion unit 7 is connected to the synthesis gas aromatic hydrocarbon unit 4.
  • the raw syngas is introduced into the syngas purification unit 1 for purification;
  • the gas is introduced into the synthesis gas to produce the aromatic hydrocarbon unit 3, and the carrier of the catalyst used is ZSM-5 molecular sieve, the first metal is zinc, ruthenium, the second metal is iron, copper, ZSM-5 molecular sieve, metal zinc, metal ruthenium
  • the gas forms an oil phase component such as a gas phase, an aqueous phase, a non-aromatic hydrocarbon, a benzene, a toluene, a C 8 aromatic hydrocarbon, a C 9 aromatic hydrocarbon, a C 10 aromatic hydrocarbon, and a heavy aromatic hydrocarbon under the action of a catalyst, and its composition is shown in Table 6.
  • the reacted product material enters the gas-liquid separation unit 4 and is separated into a gas phase product and a liquid phase product, wherein the liquid phase product enters the oil-water separation unit 8 and is separated into an oil phase and an aqueous phase, and the oil phase and the water phase respectively enter a corresponding post-system treatment. ;
  • the gas phase product separated by the gas-liquid separation unit 4 enters the liquefied gas separation unit 5 and is separated into liquefied gas and a part of ethylene and dry gas, wherein the liquefied gas and ethylene are used as products, and the dry gas enters the dry gas separation unit 6 and is separated into hydrogen, carbon monoxide and methane.
  • the synthesis gas i.e., hydrogen and carbon monoxide, has a conversion temperature of 900 ° C and a conversion pressure of 3.0 MPa, and then returns to the synthesis gas to produce an aromatic hydrocarbon unit 3.

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Abstract

一种合成气制芳烃的系统及方法，该系统包括合成气净化单元(1)、合成气变换单元(2)、合成气制芳烃单元(3)、气液分离单元(4)、液化气分离单元(5)、干气分离单元(6)、干气转化单元(7)、油水分离单元(8)。该方法通过将液化气、干气的分离和干气的水蒸气重整生成一氧化碳和氢气，作为原料返回合成气芳构化反应系统，既解决了副产物的利用问题，也降低了吨芳烃产品的合成气单耗。该系统及方法从循环经济的角度出发，同时解决了副产品干气的利用问题，降低过程中水的消耗，符合绿色化学的概念。

Description

一种合成气制芳烃的系统及方法 技术领域
本发明涉及一种合成气制芳烃的系统及方法，属于石油化工技术领域。
背景技术
“三苯”、“三烯”是石油化工领域的基础化工原料。其中，“三苯”是主要的芳烃类物质，传统上主要来源于石油炼制和煤的干馏过程。目前，70％以上的芳烃是依靠石油路径得到，特别是以石脑油为原料，经过芳烃重整和芳烃联合工艺得到的以苯和对二甲苯为主的芳烃原料，是后续加工各种合成纤维和化学新材料的基础化学原料。但随着石油资源的日益短缺，芳烃的供应持续紧张，价格高居不下，极大地影响了后续化纤和新材料行业的原料供给。
近年来，一些研究者开发了一条以甲醇和二甲醚作为主要原料的醇醚制芳烃的工艺路线，该过程一般以煤为原料，经过气化、变化、甲醇合成和精制，再由甲醇制芳烃。该方法能够在一定程度上缓解芳烃原料对于石油的依赖性，但是该过程具有产品生产路径长、投资大、能耗大的缺点；同时煤制甲醇的过程中需要耗费大量的水，而甲醇制芳烃的过程中又会生成水，导致大量水资源的浪费。
中国专利申请CN1880288A公开了一种甲醇/二甲醚芳构化的技术，该技术采用改性的ZSM-5催化剂，经冷却将产品分离为气相和油相产品，油相产品经萃取分离得到芳烃和非芳烃，考虑到目前煤制甲醇的工艺路线，该过程的加工路径较长，投资大的缺点显现无疑。
发明内容
为解决上述技术问题，本发明的目的在于提供一种合成气制芳烃的系统及方法，采用合成气一步法合成芳烃，克服了经甲醇制芳烃过程生产路径长、投资大、能耗大的缺点。
为达到上述目的，本发明首先提供了一种合成气制芳烃的系统，其包括：合成气净化单元、合成气变换单元、合成气制芳烃单元、气液分离单元、液化气分离单元、干气分离单元、干气转化单元、油水分离单元；
其中，所述合成气净化单元、合成气变换单元、合成气制芳烃单元、气液分离单元依次连接；
所述气液分离单元分别与所述液化气分离单元、油水分离单元连接；
所述液化气分离单元与所述干气分离单元连接；
所述干气分离单元分别与所述干气转化单元、合成气制芳烃单元连接；
所述干气转化单元与所述合成气制芳烃单元连接。
在上述系统中，合成气净化单元用于对作为原料的合成气进行净化处理；合成气变换单元用于调整合成气中的氢气与一氧化碳的比例；合成气制芳烃单元用于使气体与催化剂接触反应制备芳烃；气液分离单元用于将制芳烃的产物分离为气相和液相；液化气分离单元用于将气液分离单元分离出的气相分离为液化气和干气，其中，液化气作为产品输出，干气进入干气分离单元；干气分离单元用于将液化气分离单元分离出的干气分离为氢气、一氧化碳以及甲烷、乙烷、乙烯、二氧化碳，其中，甲烷、乙烷可以进入干气转化单元转化成合成气(即氢气和一氧化碳)，也可以使一部分甲烷和一部分乙烷以及全部乙烯采出用作其他用途，其余全部甲烷、全部乙烷进入干气转化单元转化成合成气；干气转化单元用于将来自干气分离单元的气体转化成合成气；油水分离单元用于将气液分离单元分离出的液相分离为油相(例如芳烃)和水相，然后分别进入对应的后系统进行处理。
在上述系统中，优选地，液化气分离单元与合成气制芳烃单元连接，用于向合成气制芳烃单元输送液化气、乙烯，使合成气制芳烃单元产出的液化气、乙烯经分离后返回合成气制芳烃单元，进一步增产芳烃。
本发明还提供了一种合成气制芳烃的方法，其是采用上述系统进行的，该方法包括以下步骤：
a、使原料合成气进入合成气净化单元进行净化；
b、使经过净化的合成气进入合成气变换单元进行变换；
c、使经过变换的合成气、来自干气转化单元的一氧化碳和氢气、来自干气分离单元的一氧化碳和氢气进入合成气制芳烃单元生产芳烃；
d、将步骤c得到的反应产物冷却后，进入气液三相分离单元中分离为气相、液相，其中，气相进入液化气分离单元分离为液化气和干气，液相进入油水分离单元分离为油相和水相；
e、使步骤d得到的干气进入干气分离单元分离为氢气、一氧化碳以及甲烷、乙烷、乙烯、二氧化碳；
f、使步骤e得到的甲烷、乙烷进入干气转化单元转化为合成气，即氢气与一氧化碳。
在上述方法中，优选地，在步骤c中，在合成气制芳烃单元中生产芳烃采用的催化剂是复合型催化剂。该复合型催化剂包括载体和第一金属组分、第二金属组分。其中，所采用的载体包括ZSM-5分子筛、ZSM-11分子筛和ZSM-22分子筛中的一种或多种的组合；第一金属组分为锌、银、镓、镧、铈中的一种或多种的组合，第一金属组分的含量占催化剂总质量的0.1-10％，以金属计；第二金属组分为铁、钴、铬、锰、铜中的一种或多种的组合，第二金属组分的含量占催化剂总质量的10-60％，以金属计；作为载体的分子筛的含量占催化剂总质量的30-90％；载体、第一金属组分、第二金属组分的质量之和为100％。
在上述方法中，优选地，在步骤d中，液化气分离单元分离出的液化气进入合成气制芳烃单元生产芳烃。
在上述方法中，优选地，在步骤e中，干气分离单元分离得到的一部分氢气和二氧化碳进入芳烃加工单元。
在上述方法中，优选地，在步骤f中，使一部分甲烷、一部分乙烷和全部乙烯采出，其余全部甲烷和全部乙烷进入干气转化单元转化为合成气，即氢气与一氧化碳。
在上述方法中，优选地，在步骤c中，合成气制芳烃单元中的反应温度为300-550℃；优选380-520℃。
在上述方法中，优选地，在步骤c中，合成气制芳烃单元中的体积空速为100-100000h-1；优选1000-10000h-1。
在上述方法中，优选地，在步骤c中，合成气制芳烃单元中的反应压力为1.0-10.0MPa。
在上述方法中，优选地，在步骤c中，在合成气变换单元的出口处，经过变换的合成气中，一氧化碳与氢气的摩尔比为1.0-3.5：1；优选1.5-3.0:1。
在上述方法中，优选地，在步骤f中，在干气转化单元中转化生成合成气时，转化压力为1.5-4.0MPa，转化温度为800-1000℃。
在上述方法中，气液三相分离单元中分离气相和液相可以采用常规的冷却分离方式；气相进入液化气分离单元分离为液化气和干气可以采用常规的油吸收的分离方式；液相进入油水分离单元分离为油相和水相可以采用常规的油水分离方式；在步骤e中，干气在干气分离单元中的分离采用冷却油吸收和吸附剂吸附结合的分离方式。
针对煤经醇醚芳构化过程产品生产路径长、投资大、能耗大的缺点，以及煤制甲醇过程需要耗费大量的水，同时需要浪费大量一氧化碳进行水煤气转化提供甲醇合成所需 要的氢气，而在甲醇制芳烃过程中又重新生成水、导致大量水资源的浪费的问题，本发明提供的合成气制芳烃的系统及方法采用合成气一步法合成芳烃即克服了经甲醇制芳烃过程生产路径长、投资大、能耗大的缺点，投资降低15％以上，能耗降低20％以上。
本发明提供一种合成气芳构化过程副产干气的利用方法，通过将干气的分离和干气的水蒸气重整，生成一氧化碳和氢气，作为返回合成气芳构化反应系统，既解决了副产物的利用问题，也降低了吨芳烃产品的合成气单耗。
另一方面，由于合成气芳构化反应产品中水的生成量小，相比于现有的煤制芳烃系统，反应进料的氢碳比要求低，合成气变换的负荷大幅度下降，过程的水耗低。
同时，本发明也提供了一种将合成气制芳烃中副产的液化气返回合成气制芳烃反应系统来增产芳烃的方法，解决了液化气的利用问题，提高了芳烃的产率。
本发明从循环经济的角度出发，同时解决了副产品干气的利用问题，降低过程中水的消耗，符合绿色化学的概念。
附图说明
图1为实施例1提供的合成气制芳烃的系统及方法的工艺流程图。
图2为实施例5提供的合成气制芳烃的系统及方法的工艺流程图。
图3为实施例6提供的合成气制芳烃的系统及方法的工艺流程图。
主要组件符号说明：
1合成气净化单元、2合成气变换单元、3合成气制芳烃单元、4气液分离单元、5液化气分离单元、6干气分离单元、7干气转化单元、8油水分离单元
具体实施方式
本发明提供了一种煤制芳烃的系统及方法，下面结合附图对本发明做进一步说明。
实施例1
本实施例提供了一种合成气制芳烃的系统，其结构如图1所示。该系统包括：合成气净化单元1、合成气变换单元2、合成气制芳烃单元3、气液分离单元4、液化气分离单元5、干气分离单元6、干气转化单元7、油水分离单元8；
其中，合成气净化单元1、合成气变换单元2、合成气制芳烃单元3、气液分离单元4依次连接；
气液分离单元4的出口分别与液化气分离单元5、油水分离单元8连接；
液化气分离单元5的出口与干气分离单元6连接；
干气分离单元6的出口分别与干气转化单元7、合成气制芳烃单元4连接；
干气转化单元7的出口与合成气制芳烃单元4连接。
采用本实施例的系统利用合成气制芳烃时，可以按照以下步骤进行(工艺流程如图1所示)：
使原料合成气进入合成气净化单元1进行净化；
净化后的合成气进入合成气变换单元2，变换后的气体比例为H2:CO＝1.5：1；使气体进入合成气制芳烃单元3进行反应，所采用的催化剂的载体为ZSM-5分子筛，第一金属为锌、铈，第二金属为铁、钴、锰，ZSM-5分子筛、金属锌、金属铈、金属铁、金属钴、金属锰的质量比为ZSM-5：锌：铈：铁：钴：锰＝55:3:1:1:3:36，反应温度475℃，反应压力2.5MPa，体积空速为5000h-1，气体在催化剂的作用下生成气相、水相、非芳烃、苯、甲苯、C8芳烃、C9芳烃、C10芳烃和重芳烃等油相组分，其组成如表1所示。反应后的产品物料进入气液分离单元4分离为气相产品和液相产品，其中，液相产品进入油水分离单元8分离为油相和水相，油相和水相分别进入对应的后系统处理；
气液分离单元4分离的气相产品进入液化气分离单元5分离为液化气及部分乙烯和干气，其中，液化气和乙烯作为产品，干气进入干气分离单元6分离为氢气、一氧化碳和甲烷、乙烷、乙烯及二氧化碳，其中，氢气、一氧化碳返回合成气制芳烃单元3进行反应，甲烷、乙烷进入干气转化单元7转化为合成气，即氢气与一氧化碳，转化温度为900℃，转化压力为3.0MPa，然后返回合成气制芳烃单元3。
表1合成气制芳烃的反应产物
Figure PCTCN2017091068-appb-000001
实施例2
本实施例提供了一种合成气制芳烃的方法，其是实施例1的系统进行，该方法包括以下步骤：
使原料合成气进入合成气净化单元1进行净化；
净化后的合成气进入合成气变换单元2，变换后的气体比例为H2:CO＝2.0：1；
使气体进入合成气制芳烃单元3进行反应，所采用的催化剂的载体为ZSM-11分子筛，第一金属为锌、镧，第二金属为铁、钴、铜，ZSM-11分子筛、金属锌、金属镧、金属铁、金属钴、金属铜的质量比为ZSM-11：锌：镧：铁：钴：铜＝55:3:1:1:4:36，反应温度300℃，反应压力10MPa，体积空速为10000h-1，气体在催化剂的作用下生成气相、水相、非芳烃、苯、甲苯、C8芳烃、C9芳烃、C10芳烃和重芳烃等油相组分，其组成如表2所示。反应后的产品物料进入气液分离单元4分离为气相产品和液相产品，其中，液相产品进入油水分离单元8分离为油相和水相，油相和水相分别进入对应的后系统处理；
气液分离单元4分离的气相产品进入液化气分离单元5分离为液化气及部分乙烯和干气，其中，液化气和乙烯作为产品，干气进入干气分离单元6分离为氢气、一氧化碳和甲烷、乙烷、乙烯及二氧化碳，其中，氢气、一氧化碳返回合成气制芳烃单元3进行反应，甲烷、乙烷进入干气转化单元7转化为合成气，即氢气与一氧化碳，转化温度为1000℃，转化压力为2.0MPa，然后返回合成气制芳烃单元3。
表2合成气制芳烃的反应产物
Figure PCTCN2017091068-appb-000002
实施例3
本实施例提供了一种合成气制芳烃的方法，其是实施例1的系统进行，该方法包括以下步骤：
使原料合成气进入合成气净化单元1进行净化；
净化后的合成气进入合成气变换单元2，变换后的气体比例为H2:CO＝3.5：1；
使气体进入合成气制芳烃单元3进行反应，所采用的催化剂的载体为ZSM-22分子筛，第一金属为锌、镓，第二金属为铁、钴，ZSM-22分子筛、金属锌、金属镓、金属铁、金属钴的质量比为ZSM-22：锌：镓：铁：钴＝44:3:1:22:30，反应温度550℃，反应压力1.0MPa，体积空速为100000h-1，气体在催化剂的作用下生成气相、水相、非芳烃、苯、甲苯、C8芳烃、C9芳烃、C10芳烃和重芳烃等油相组分，其组成如表3所示。反应后的产品物料进入气液分离单元4分离为气相产品和液相产品，其中，液相产品进入油 水分离单元8分离为油相和水相，油相和水相分别进入对应的后系统处理；
气液分离单元4分离的气相产品进入液化气分离单元5分离为液化气及部分乙烯和干气，其中，液化气和乙烯作为产品，干气进入干气分离单元6分离为氢气、一氧化碳和甲烷、乙烷、乙烯及二氧化碳，其中，氢气、一氧化碳返回合成气制芳烃单元3进行反应，甲烷、乙烷进入干气转化单元7转化为合成气，即氢气与一氧化碳，转化温度为800℃，转化压力为2.0MPa，然后返回合成气制芳烃单元3。
表3合成气制芳烃的反应产物
Figure PCTCN2017091068-appb-000003
实施例4
本实施例提供了一种合成气制芳烃的系统，其结构如图2所示。该系统包括：合成气净化单元1、合成气变换单元2、合成气制芳烃单元3、气液分离单元4、液化气分离单元5、干气分离单元6、干气转化单元7、油水分离单元8；
其中，合成气净化单元1、合成气变换单元2、合成气制芳烃单元3、气液分离单元4依次连接；
气液分离单元4的出口分别与液化气分离单元5、油水分离单元8连接；
液化气分离单元5的出口与干气分离单元6和合成气制芳烃单元3连接；
干气分离单元6的出口分别与干气转化单元7、合成气制芳烃单元4连接；
干气转化单元7的出口与合成气制芳烃单元4连接。
采用本实施例的系统利用合成气制芳烃时，可以按照以下步骤进行(工艺流程如图2所示)：
使原料合成气进入合成气净化单元1进行净化；
净化后的合成气进入合成气变换单元2，变换后的气体比例为H2:CO＝2.5：1；
使气体进入合成气制芳烃单元3进行反应，所采用的催化剂的载体为ZSM-5分子筛，第一金属为锌、镧，第二金属为铁、钴，ZSM-5分子筛、金属锌、金属镧、金属铁、金属钴的质量比为ZSM-5：锌：镧：铁：钴＝54:3:1:15:27，反应温度450℃，反应压力4.0MPa，体积空速为10000h-1，气体在催化剂的作用下生成气相、水相、非芳烃、苯、 甲苯、C8芳烃、C9芳烃、C10芳烃和重芳烃等油相组分，其组成如表4所示。反应后的产品物料进入气液分离单元4分离为气相产品和液相产品，其中，液相产品进入油水分离单元8分离为油相和水相，油相和水相分别进入对应的后系统处理；
气液分离单元4分离的气相产品进入液化气分离单元5分离为液化气及部分乙烯和干气，其中，液化气和乙烯作为原料返回合成气制芳烃单元3，干气进入干气分离单元6分离为氢气、一氧化碳和甲烷、乙烷、乙烯及二氧化碳，其中，氢气、一氧化碳返回合成气制芳烃单元3进行反应，甲烷、乙烷进入干气转化单元7转化为合成气，即氢气与一氧化碳，转化温度为800℃，转化压力为2.0MPa，然后返回合成气制芳烃单元3。
表4扣除进料液化气的合成气制芳烃的反应产物
Figure PCTCN2017091068-appb-000004
实施例5
本实施例提供了一种合成气制芳烃的系统，其结构如图2所示。该系统包括：合成气净化单元1、合成气变换单元2、合成气制芳烃单元3、气液分离单元4、液化气分离单元5、干气分离单元6、干气转化单元7、油水分离单元8；
其中，合成气净化单元1、合成气变换单元2、合成气制芳烃单元3、气液分离单元4依次连接；
气液分离单元4的出口分别与液化气分离单元5、油水分离单元8连接；
液化气分离单元5的出口与干气分离单元6和合成气制芳烃单元3连接；
干气分离单元6的出口分别与干气转化单元7、合成气制芳烃单元4连接；
干气转化单元7的出口与合成气制芳烃单元4连接。
采用本实施例的系统利用合成气制芳烃时，可以按照以下步骤进行(工艺流程如图2所示)：
使原料合成气进入合成气净化单元1进行净化；
净化后的合成气进入合成气变换单元2，变换后的气体比例为H2:CO＝2：1；
使气体进入合成气制芳烃单元3进行反应，所采用的催化剂的载体为ZSM-11分子筛，第一金属为锌、银，第二金属为铁、铜，ZSM-11分子筛、金属锌、金属银、金属 铁、金属铜的质量比为ZSM-11：锌：银：铁：铜＝65:3:2:12:18，反应温度475℃，反应压力2.5MPa，体积空速为5000h-1，气体在催化剂的作用下生成气相、水相、非芳烃、苯、甲苯、C8芳烃、C9芳烃、C10芳烃和重芳烃等油相组分，其组成如表5所示。反应后的产品物料进入气液分离单元4分离为气相产品和液相产品，其中，液相产品进入油水分离单元8分离为油相和水相，油相和水相分别进入对应的后系统处理；
气液分离单元4分离的气相产品进入液化气分离单元5分离为液化气及部分乙烯和干气，其中，液化气和乙烯作为原料返回合成气制芳烃单元3，干气进入干气分离单元6分离为氢气、一氧化碳和甲烷、乙烷、乙烯及二氧化碳，其中，氢气、一氧化碳返回合成气制芳烃单元3进行反应，甲烷、乙烷进入干气转化单元7转化为合成气，即氢气与一氧化碳，转化温度为900℃，转化压力为3.0MPa，然后返回合成气制芳烃单元3。
表5扣除进料液化气的合成气制芳烃的反应结果
产品 选择性％
干气 10
液化气 11
油相非芳烃 4
芳烃 73
CO转化率 40
实施例6
本实施例提供了一种合成气制芳烃的系统，其结构如图3所示。该系统包括：合成气净化单元1、合成气变换单元2、合成气制芳烃单元3、气液分离单元4、液化气分离单元5、干气分离单元6、干气转化单元7、油水分离单元8；
其中，合成气净化单元1、合成气变换单元2、合成气制芳烃单元3、气液分离单元4依次连接；
气液分离单元4的出口分别与液化气分离单元5、油水分离单元8连接；
液化气分离单元5的出口与干气分离单元6连接；
干气分离单元6的出口分别与干气转化单元7、合成气制芳烃单元4连接；
干气转化单元7的出口与合成气制芳烃单元4连接。
采用本实施例的系统利用合成气制芳烃时，可以按照以下步骤进行(工艺流程如图3所示)：
使原料合成气进入合成气净化单元1进行净化；
净化后的合成气进入合成气变换单元2，变换后的气体比例为H2:CO＝1.5：1；
使气体进入合成气制芳烃单元3进行反应，所采用的催化剂的载体为ZSM-5分子筛，第一金属为锌、铈，第二金属为铁、铜，ZSM-5分子筛、金属锌、金属铈、金属铁、金属铜的质量比为ZSM-5：锌：铈：铁：铜＝70:3:2:12:13，反应温度475℃，反应压力2.5MPa，体积空速为5000h-1，气体在催化剂的作用下生成气相、水相、非芳烃、苯、甲苯、C8芳烃、C9芳烃、C10芳烃和重芳烃等油相组分，其组成如表6所示。反应后的产品物料进入气液分离单元4分离为气相产品和液相产品，其中，液相产品进入油水分离单元8分离为油相和水相，油相和水相分别进入对应的后系统处理；
气液分离单元4分离的气相产品进入液化气分离单元5分离为液化气及部分乙烯和干气，其中，液化气和乙烯作为产品，干气进入干气分离单元6分离为氢气、一氧化碳和甲烷、乙烷、乙烯及二氧化碳，其中，一部分氢气、一氧化碳被抽出作为后续芳烃加工的原料，剩余的氢气、一氧化碳返回合成气制芳烃单元3进行反应，甲烷、乙烷进入干气转化单元7转化为合成气，即氢气与一氧化碳，转化温度为900℃，转化压力为3.0MPa，然后返回合成气制芳烃单元3。
表6合成气制芳烃的反应产物
Figure PCTCN2017091068-appb-000005

Claims (16)

  1. 一种合成气制芳烃的系统，其包括：合成气净化单元(1)、合成气变换单元(2)、合成气制芳烃单元(3)、气液分离单元(4)、液化气分离单元(5)、干气分离单元(6)、干气转化单元(7)、油水分离单元(8)；
    其中，所述合成气净化单元(1)、合成气变换单元(2)、合成气制芳烃单元(3)、气液分离单元(4)依次连接；
    所述气液分离单元(4)分别与所述液化气分离单元(5)、油水分离单元(8)连接；
    所述液化气分离单元(5)与所述干气分离单元(6)连接；
    所述干气分离单元(6)分别与所述干气转化单元(7)、合成气制芳烃单元(3)连接；
    所述干气转化单元(7)与所述合成气制芳烃单元(3)连接。
  2. 根据权利要求1所述的系统，其中，所述合成气变换单元(2)用于调整合成气中的氢气与一氧化碳的比例。
  3. 根据权利要求1所述的系统，其中，所述液化气分离单元(5)与所述合成气制芳烃单元(3)连接。
  4. 一种合成气制芳烃的方法，其是采用权利要求1-3任一项所述的系统进行的，该方法包括以下步骤：
    a、使原料合成气进入合成气净化单元(1)进行净化；
    b、使经过净化的合成气进入合成气变换单元(2)进行变换；
    c、使经过变换的合成气、来自干气转化单元(7)的一氧化碳和氢气、来自干气分离单元(6)的一氧化碳和氢气进入合成气制芳烃单元(3)生产芳烃；
    d、将步骤c得到的反应产物冷却后，进入气液三相分离单元(4)中分离为气相、液相，其中，气相进入液化气分离单元(5)分离为液化气和干气，液相进入油水分离单元(8)分离为油相和水相；
    e、使步骤d得到的干气进入干气分离单元(6)分离为氢气、一氧化碳以及甲烷、乙烷、乙烯、二氧化碳；
    f、使步骤e得到的甲烷、乙烷进入干气转化单元(7)转化为合成气，即氢气与一氧化碳。
  5. 根据权利要求4所述的方法，其中，在步骤d中，所述液化气分离单元(5)分 离出的液化气、乙烯进入合成气制芳烃单元(3)生产芳烃。
  6. 根据权利要求4所述的方法，其中，所述干气分离单元(6)分离得到的一部分氢气和一氧化碳进入芳烃加工单元。
  7. 根据权利要求4所述的方法，其中，在步骤c中，合成气制芳烃单元(3)中生产芳烃采用的催化剂是复合型催化剂；该复合型催化剂包括载体和第一金属组分、第二金属组分；
    所述载体包括ZSM-5分子筛、ZSM-11分子筛和ZSM-22分子筛中的一种或多种的组合；所述载体的含量占所述复合型催化剂总质量的30-90％；
    所述第一金属组分为锌、银、镓、镧、铈中的一种或多种的组合，所述第一金属组分的含量占所述复合型催化剂总质量的0.1-10％；
    所述第二金属组分为铁、钴、铬、锰、铜中的一种或多种的组合，所述第二金属组分的含量占所述复合型催化剂总质量的10-60％；
    所述载体、第一金属组分、第二金属组分的质量之和为100％。
  8. 根据权利要求4所述的方法，其中，在步骤f中，使一部分甲烷、乙烷与乙烯采出，其余全部甲烷、乙烷进入干气转化单元(7)转化为合成气，即氢气与一氧化碳。
  9. 根据权利要求4所述的方法，其中，在步骤c中，合成气制芳烃单元(3)中的反应温度为300-550℃。
  10. 根据权利要求9所述的方法，其中，在步骤c中，合成气制芳烃单元(3)中的反应温度为380-520℃。
  11. 根据权利要求4所述的方法，其中，在步骤c中，合成气制芳烃单元(3)中的体积空速为100-100000h-1。
  12. 根据权利要求11所述的方法，其中，在步骤c中，合成气制芳烃单元(3)中的体积空速为1000-10000h-1。
  13. 根据权利要求4所述的方法，其中，在步骤c中，合成气制芳烃单元(3)中的反应压力为1.0-10.0MPa。
  14. 根据权利要求4所述的方法，其中，在步骤c中，在合成气变换单元(2)的出口处，经过变换的合成气中，一氧化碳与氢气的摩尔比为1.0-3.5：1。
  15. 根据权利要求14所述的方法，其中，所述一氧化碳与氢气的摩尔比为1.5-3.0:1。
  16. 根据权利要求4所述的方法，其中，在步骤f中，在干气转化单元(7)中转化生成合成气时，转化压力为1.5-4.0MPa，转化温度为800-1000℃。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101270297A (zh) * 2008-05-19 2008-09-24 中国科学院山西煤炭化学研究所 煤基合成气钴基费托合成液体燃料并附产芳烃的工艺
US20100144907A1 (en) * 2008-12-10 2010-06-10 Chevron U.S.A., Inc. Process for conversion of synthesis gas to hydrocarbons using a zeolite-methanol catalyst system
WO2014001354A1 (en) * 2012-06-27 2014-01-03 Saudi Basic Industries Corporation Catalyst and process for the selective production of lower hydrocarbons c1-c5 from syngass with low methane and co2 production
CN104326859A (zh) * 2014-09-03 2015-02-04 华电煤业集团有限公司 一种煤制芳烃的系统及方法
CN106268924A (zh) * 2016-07-13 2017-01-04 华电煤业集团有限公司 一种合成气直接制备芳烃的催化剂及其制备和应用
CN106588526A (zh) * 2015-10-20 2017-04-26 中国石油化工股份有限公司 一种以煤和炼厂干气为原料制烯烃的系统以及制烯烃的方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4180516A (en) * 1977-08-18 1979-12-25 Mobil Oil Corporation Conversion of synthesis gas to aromatic hydrocarbons
CN100548945C (zh) 2006-05-12 2009-10-14 中国科学院山西煤炭化学研究所 甲醇转化制芳烃工艺及催化剂和催化剂制备方法
CN104557415B (zh) * 2013-10-28 2016-08-17 中国石油化工股份有限公司 甲醇和/或二甲醚转化制芳烃联产液化气的系统及其方法
US9809758B2 (en) * 2014-07-24 2017-11-07 Exxonmobil Chemical Patents Inc. Production of xylenes from syngas
CN106607083B (zh) * 2015-10-21 2019-05-14 中国石油化工股份有限公司 合成气制芳烃的催化剂及其使用方法
CN105944751B (zh) * 2016-05-24 2019-06-21 江南大学 一种用于合成气直接制备芳香族化合物的催化剂及其制备与应用
CN107469857B (zh) * 2016-06-07 2020-12-01 中国科学院大连化学物理研究所 一种催化剂及合成气直接转化制芳烃的方法
CN106518591B (zh) * 2016-10-14 2019-10-01 中国科学院山西煤炭化学研究所 一种合成气制芳烃的联合工艺

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101270297A (zh) * 2008-05-19 2008-09-24 中国科学院山西煤炭化学研究所 煤基合成气钴基费托合成液体燃料并附产芳烃的工艺
US20100144907A1 (en) * 2008-12-10 2010-06-10 Chevron U.S.A., Inc. Process for conversion of synthesis gas to hydrocarbons using a zeolite-methanol catalyst system
WO2014001354A1 (en) * 2012-06-27 2014-01-03 Saudi Basic Industries Corporation Catalyst and process for the selective production of lower hydrocarbons c1-c5 from syngass with low methane and co2 production
CN104326859A (zh) * 2014-09-03 2015-02-04 华电煤业集团有限公司 一种煤制芳烃的系统及方法
CN106588526A (zh) * 2015-10-20 2017-04-26 中国石油化工股份有限公司 一种以煤和炼厂干气为原料制烯烃的系统以及制烯烃的方法
CN106268924A (zh) * 2016-07-13 2017-01-04 华电煤业集团有限公司 一种合成气直接制备芳烃的催化剂及其制备和应用

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