WO2020186644A1 - Système de réaction amélioré à lit fixe descendant doté de micro-interface d'hydrogénation d'huile - Google Patents

Système de réaction amélioré à lit fixe descendant doté de micro-interface d'hydrogénation d'huile Download PDF

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WO2020186644A1
WO2020186644A1 PCT/CN2019/090342 CN2019090342W WO2020186644A1 WO 2020186644 A1 WO2020186644 A1 WO 2020186644A1 CN 2019090342 W CN2019090342 W CN 2019090342W WO 2020186644 A1 WO2020186644 A1 WO 2020186644A1
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gas
micro
fixed
oil
bed
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PCT/CN2019/090342
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English (en)
Chinese (zh)
Inventor
张志炳
周政
王宝荣
杨高东
孟为民
张锋
李磊
罗华勋
杨国强
田洪舟
曹宇
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南京延长反应技术研究院有限公司
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Priority to JP2020600108U priority Critical patent/JP3231823U/ja
Priority to RU2020129865U priority patent/RU205181U1/ru
Priority to DE212019000197.1U priority patent/DE212019000197U1/de
Publication of WO2020186644A1 publication Critical patent/WO2020186644A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/001—Controlling catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0278—Feeding reactive fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0492—Feeding reactive fluids
    • 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
    • C10G45/04—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 characterised by the catalyst used
    • 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
    • C10G45/04—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 characterised by the catalyst used
    • C10G45/06—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 characterised by the catalyst used containing nickel or cobalt metal, 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
    • C10G45/04—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 characterised by the catalyst used
    • C10G45/06—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 characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—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 characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or 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
    • 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
    • C10G45/22—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 with hydrogen dissolved or suspended in the oil
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/002—Apparatus for fixed bed hydrotreatment processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • B01J2208/00902—Nozzle-type feeding elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00938—Flow distribution elements
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/70—Catalyst aspects

Definitions

  • the invention relates to the technical field of fixed bed reaction systems, and in particular to a downward fixed bed oil hydrogenation micro-interface strengthening reaction system.
  • gas-liquid reaction processes such as gas-liquid, gas-liquid-solid, etc. are widely present in the oil product field.
  • gas-liquid multiphase reactions such as oxidation, hydrogenation, and chlorination
  • the macroscopic reaction rate is generally restricted by the mass transfer process.
  • the volumetric mass transfer coefficient of the gas-liquid reaction is mainly affected by the mass transfer coefficient and the area of the gas-liquid phase boundary. Studies have shown that the phase boundary area has a greater influence on the volumetric mass transfer coefficient and is easy to control. Therefore, increasing the phase boundary area is regarded as an effective way to increase the gas-liquid macroscopic reaction rate.
  • the fixed bed reactor is a commonly used form of chemical reactor, which means that the granular solid catalyst or solid reactant is filled in the reactor to form a certain height of the stacked bed.
  • the gas or oil materials flow through the static fixed bed through the particle gap At the same time, the heterogeneous reaction process is realized.
  • the characteristic of this type of reactor is that the solid particles filled in the equipment are fixed, which is different from the moving bed and fluidized bed in which the solid materials move in the equipment. It is also called a packed bed reactor.
  • Fixed-bed reactors are widely used in gas-solid phase reactions and liquid-solid phase reactions.
  • the problems of hydrogenation to react the hydrogen with the reaction oil are: high operating pressure, small gas-liquid mass transfer phase boundary area, slow apparent reaction speed, low gas utilization, large investment, and high Problems such as low consumption and difficult operation.
  • the present invention proposes a downward fixed-bed oil hydrogenation micro-interface strengthening reaction system, which aims to solve the problem that the existing hydrogen and oil contact area is small and cannot fully react and consumes large energy.
  • the present invention proposes a downward fixed-bed oil hydrogenation micro-interface strengthening reaction system, including: a fixed-bed reactor, a micro-interface generator, and a gas-liquid separation tank; wherein,
  • the micro-interface generator is arranged on the upper part of the fixed-bed reactor, and converts the pressure energy of hydrogen and/or the kinetic energy of oil products into the surface energy of hydrogen bubbles during the hydrogenation reaction, so that the hydrogen bubbles are broken into micro bubbles , And mixing the microbubbles with the oil to form a gas-liquid emulsion, and the gas-liquid emulsion enters the fixed-bed reactor through the upper part of the fixed-bed reactor for subsequent reactions;
  • the fixed-bed reactor is used as a reaction site for the hydrogenation reaction of oil products to form a stable gas-liquid enhanced fixed-bed reaction system when the gas-liquid emulsion enters it;
  • the gas-liquid separation tank is connected to the fixed-bed reactor, and is used for performing gas-liquid separation of the reaction-completed mixture in the fixed-bed reactor.
  • the micro-interface generator is selected from one of a pneumatic micro-interface generator, a hydraulic micro-interface generator, and a gas-liquid linkage micro-interface generator Or several.
  • the fixed-bed reactor includes a reaction tank and a catalyst bed; wherein,
  • the reaction tank is a tank body for providing a reaction space for the gas-liquid emulsion, and the reaction tank is provided with a discharge port for outputting the reacted mixture;
  • the catalyst bed is fixed inside the reaction tank, and a catalyst for improving the reaction efficiency of the gas-liquid emulsion is arranged in the bed.
  • the gas-liquid separation tank is provided with a liquid phase outlet and a gas phase outlet for respectively discharging the oil mixture and gas.
  • the above-mentioned downward fixed-bed oil hydrogenation micro-interface strengthening reaction system further includes: a raw material tank, a power mechanism and a feed preheater; wherein,
  • the raw material tank is connected to the power mechanism for storing hydrogen and reaction oil
  • the other end of the power mechanism is connected with the feed preheater to provide power for the delivery of hydrogen and oil raw materials;
  • the other end of the feed preheater is connected to the micro-interface reactor to preheat the hydrogen and oil raw materials to reach a specified temperature.
  • the raw material tank includes: an oil raw material tank and a gas raw material buffer tank; wherein,
  • the oil product raw material tank is connected to the feed pump for storing oil product raw materials
  • the gas raw material buffer tank is connected to the compressor for storing hydrogen.
  • the power mechanism includes: a feed pump and a compressor; wherein,
  • the feed pump is connected to the oil feed preheater to provide power for conveying oil raw materials
  • the compressor is connected to the gas feed preheater to provide power for hydrogen delivery.
  • the feed preheater includes: an oil feed preheater and a gas feed preheater; wherein,
  • the oil feed preheater is connected to the micro-interface generator, and is used to preheat the oil raw material to reach a specified temperature, and send it into the micro-interface generator;
  • the gas feed preheater is connected to the micro-interface generator, and is used to preheat the hydrogen gas to reach a specified temperature and send it into the micro-interface generator.
  • the diameter of the microbubbles is 1 ⁇ m ⁇ d ⁇ 1mm.
  • the beneficial effect of the present invention is that the fixed-bed hydrogenation micro-interface reaction system provided by the present invention, by adding a micro-interface generator to the fixed-bed reaction system, hydrogen is broken into a diameter of 1 ⁇ m
  • the gas with ⁇ d ⁇ 1mm forms a microbubble system.
  • the microbubbles have the advantages of rigidity, good independence, and not easy to coalesce.
  • the gas-liquid reaction is strengthened and the mass transfer efficiency is improved.
  • a large number of micro-bubbles in the emulsion form a higher phase boundary area in the reactor.
  • the fixed-bed hydrogenation micro-interface reaction system of the present invention provides a micro-interface generator, and has the advantages of high gas utilization rate, high desulfurization rate, low investment, low energy consumption, flexible process and the like in engineering.
  • FIG. 1 is a schematic structural diagram of a downward fixed-bed oil hydrogenation micro-interface strengthening reaction system provided by an embodiment of the present invention
  • FIG. 2 is a schematic structural diagram of a downward multi-stage fixed-bed oil hydrogenation micro-interface strengthening reaction system provided by an embodiment of the present invention.
  • the terms “installed”, “connected”, and “connected” should be understood in a broad sense, for example, it may be a fixed connection or It is a detachable connection or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication between two components.
  • installed e.g., it may be a fixed connection or It is a detachable connection or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication between two components.
  • FIG. 1 it is a downward fixed-bed oil hydrogenation micro-interface strengthening reaction system provided by an embodiment of the present invention.
  • the system has a micro-interface generator (Micro Interfacial Generator, referred to as MIG) installed on the upper part of the fixed-bed reactor
  • MIG Micro Interfacial Generator
  • the hydrogen is broken into microbubbles by the micro-interface generator, and the gas-liquid emulsion formed by mixing the microbubbles and the oil enters the fixed bed reactor through the upper inlet of the fixed bed reactor for subsequent reactions.
  • the reacted mixture is discharged through the outlet at the lower part of the fixed bed reactor to form a downward fixed bed hydrogenation micro-interface reaction system.
  • the system includes: a fixed bed reactor 4, a micro-interface generator, a gas-liquid separation tank 5, a raw material tank, a power mechanism, and a feed preheater; among them, the raw material tank is connected to the power mechanism to store hydrogen and reactant liquid , The other end of the power mechanism is connected with the feed preheater to provide power for transporting hydrogen and reactant liquid, and the other end of the feed preheater is connected with the micro-interface reactor to preheat the hydrogen and reactant liquid.
  • the micro-interface generator is arranged on the upper part of the fixed-bed reactor 4 to break the hydrogen into micro-bubbles, and the gas-liquid separation tank 5 is connected with the micro-interface generator to separate and discharge the reaction products;
  • the micro interface generator is set in The upper part of the fixed bed reactor 4 converts the pressure energy of hydrogen and/or the kinetic energy of the oil during the reaction into the surface energy of hydrogen bubbles during the hydrogenation reaction, so that the hydrogen gas is broken into microbubbles and The microbubbles are mixed with the oil in the reaction process to form a gas-liquid emulsion, and then the gas-liquid emulsion enters the fixed-bed reactor 4 through the upper inlet of the fixed-bed reactor 4 for subsequent reactions.
  • the product after the reaction is completed The outlet at the lower part of
  • micro-interface generator is not limited in this embodiment, and it only needs to be set in the lower part of the fixed bed reactor 4.
  • the raw material tank includes: a liquid raw material tank 9 and a gas raw material buffer tank 12, wherein the liquid raw material tank 9 and the gas raw material buffer tank 12 are used to store liquid raw materials and gas raw materials respectively;
  • the power mechanism includes: feed The pump 10 and the compressor 13, wherein the feed pump 10 and the compressor 13 are used to respectively provide power for conveying liquid raw materials and gas raw materials;
  • the feed preheater includes: a liquid raw material preheater 11 and a gas raw material preheater 14 Among them, the liquid raw material preheater 11 and the gas raw material preheater 14 are used to respectively preheat the liquid raw material and the gas raw material;
  • the inside of the micro-interface generator is provided with a catalyst bed to promote the gas-liquid emulsion reaction, which includes:
  • the gas-liquid linkage micro-interface generator 3 and the pneumatic micro-interface generator 15 are equipped with a gas-liquid linkage micro-interface generator liquid phase inlet 1 and a gas-liquid linkage micro-interface generator
  • the hydrogen gas enters the gas-liquid micro-interface generator 3 through the gas-liquid micro-interface generator gas phase inlet 2.
  • the other way enters the dynamic micro-interface generator 15 through the gas-phase inlet 17 of the pneumatic micro-interface generator.
  • the hydrogen entering the micro-interface generator is broken into micro-bubbles and mixed with oil to form a gas-liquid emulsion. Enter the inside of the fixed bed reactor 4 through the upper inlet of the fixed bed reactor 4, and fully and completely react under the catalysis of the catalyst.
  • the product is transferred to the gas-liquid separation tank through the lower outlet of the fixed bed reactor 4 5
  • the unreacted gas raw materials and other gases produced by the reaction are extracted from the gas-phase outlet 6 of the gas-liquid separation tank 5, and the liquid-phase reaction product is extracted from the liquid phase of the gas-liquid separation tank 5. It is extracted from outlet 7 and collected separately for subsequent processing.
  • the number of fixed bed reactors 4 is not limited in this example, and it only needs to be configured according to the needs of the reaction system.
  • the highest point of the outlet connecting pipe should be higher than the top of the fixed bed reactor.
  • the specific positions of the gas-phase outlet 6 and the liquid-phase outlet 7 of the gas-liquid separation tank 5 are also not limited, as long as they can discharge gas and oil.
  • the present invention is applicable to the catalyst systems already mentioned, as well as other hydrogenation catalyst systems not mentioned.
  • the operating temperature will be appropriately adjusted according to the activation temperature of the catalyst, without affecting the fact that the reactor of the present invention can greatly (or double) reduce the operating pressure and increase the space velocity under different catalyst systems. (Processing capacity) outstanding advantages.
  • the hydrogen is broken into micro-bubbles with an average diameter of 1 ⁇ m ⁇ d ⁇ 1mm, and the gas-liquid is vigorously mixed to form a gas-liquid emulsion, which enters the fixed bed for reaction
  • the bottom end of the vessel 4 flows from bottom to top, passes through a section of the catalyst bed 8, and undergoes the hydrodesulfurization reaction under the action of the catalyst.
  • the reaction product enters the gas-liquid separation tank 5 from the top of the fixed-bed reactor 4.
  • the unreacted H2 and H2S produced by the reaction in the fixed-bed reactor 4 are extracted from the gas-phase outlet 6 of the gas-liquid separation tank, and after hydrodesulfurization
  • the liquid phase oil product of the gas is extracted from the liquid phase outlet 7 of the gas-liquid separation tank, and collected separately for subsequent processing.
  • the reaction pressure in the fixed bed reactor 4 is 3 MPa, and the reaction temperature is 220°C.
  • a molybdenum nickel catalyst is used in the fixed bed reactor 4, and the space velocity is controlled to 0.3h-1.
  • the sulfur content in the raw gasoline is 120 ppm, which is reduced to 20 ppm after the process of this hydrodesulfurization reaction process.
  • the hydrogen is broken into micro-bubbles with an average diameter of 1 ⁇ m ⁇ d ⁇ 1mm, and the gas-liquid is vigorously mixed to form a gas-liquid emulsion, which enters the fixed bed reactor
  • the top of 4 flows from top to bottom, passes through a section of the catalyst bed 8, and undergoes hydrodesulfurization reaction under the action of the catalyst.
  • the reaction product enters the gas-liquid separation tank 5 from the bottom end of the fixed bed reactor 4.
  • the unreacted H 2 and the H 2 S generated by the reaction in the fixed bed reactor 4 are extracted from the gas-phase outlet 6 of the gas-liquid separation tank.
  • the liquid phase oil product after hydrodesulfurization is extracted from the liquid phase outlet 7 of the gas-liquid separation tank, and collected separately for subsequent processing.
  • the reaction pressure in the fixed bed reactor 4 is 4 MPa, and the reaction temperature is 250°C.
  • a molybdenum nickel catalyst is used in the fixed bed reactor 4, and the space velocity is controlled to 1.2 h -1 .
  • the sulfur content in the raw material kerosene is 150 ppm, which is reduced to 50 ppm after the process of this hydrodesulfurization reaction process.
  • the hydrogen is broken into micro-bubbles with an average diameter of 1 ⁇ m ⁇ d ⁇ 1mm, and the gas-liquid is vigorously mixed to form a gas-liquid emulsion, which enters the fixed bed reactor
  • the top of 4 flows from bottom to top, passes through a section of the catalyst bed 8, and undergoes hydrodesulfurization reaction under the action of the catalyst.
  • the reaction product enters the gas-liquid separation tank 5 from the bottom end of the fixed bed reactor 4.
  • the unreacted H 2 and the H 2 S generated by the reaction in the fixed bed reactor 4 are extracted from the gas-phase outlet 6 of the gas-liquid separation tank.
  • the liquid phase oil product after hydrodesulfurization is extracted from the liquid phase outlet 7 of the gas-liquid separation tank, and collected separately for subsequent processing.
  • the reaction pressure in the fixed bed reactor 4 is 1.5 MPa, and the reaction temperature is 250°C.
  • a molybdenum nickel catalyst is used in the fixed bed reactor 4, and the space velocity is controlled at 2.5 h -1 .
  • the sulfur content in the raw aviation kerosene is 100 ppm, which is reduced to 30 ppm after the process of this hydrodesulfurization reaction process.
  • the present invention is applicable to the catalyst systems already mentioned, as well as other hydrogenation catalyst systems not mentioned. Only when different catalysts are used, the operating temperature will be appropriately adjusted according to the activation temperature of the catalyst, without affecting the fact that the reactor of the present invention can greatly (or double) reduce the operating pressure and increase the space velocity under different catalyst systems. (Processing capacity) outstanding advantages.
  • micro-interface generator can also be used in other multi-phase reaction technology fields to form such as gas-liquid-solid micro-mixed flow, gas-liquid-solid micro-nano flow, gas-liquid-solid emulsified flow, gas-liquid-solid microstructure flow, multi-phase micro-mixed flow , Multi-phase micro-nano flow, multi-phase emulsified flow, multi-phase micro-structured flow, micro-bubble, micro-gas liquid flow, gas-liquid micro-nano emulsion flow, ultra-micro flow, ultra-micro fluidization, micro-dispersion flow, micro-turbulent flow, micro Bubble flow, micro-nano bubble flow, etc.
  • Multiphase fluids formed by micron-scale particles, or multi-phase fluids formed by micro-nano-scale particles can also be applied to microbubble mass transfer, microbubbles Transfer, microbubble reaction, microbubble absorption, microbubble oxygenation, microbubble contact type, micromixing, microbubble, microbubble, microfluidization, microbubble fermentation, microbubble bubbling and other reactions, as well as microbubble biochemical In reactors, microbubble bioreactors and other reactors, the mass transfer area of the phase boundary between the gas and/or liquid phase and the liquid and/or solid phase during the reaction process is effectively increased.
  • the beneficial effect of the present invention is that the fixed-bed hydrogenation micro-interface reaction system provided by the present invention, by adding a micro-interface generator to the fixed-bed reaction system, hydrogen is broken into a diameter of 1 ⁇ m ⁇ d ⁇ 1mm
  • the gas forms a microbubble system.
  • the microbubbles have the advantages of rigidity, good independence, and not easy to coalesce, so that during the gas-liquid reaction process, the gas-liquid reaction is strengthened, and the mass transfer efficiency is improved, thus obtaining an emulsification containing a large number of microbubbles Liquid, thereby forming a higher phase boundary area in the reactor.
  • the fixed-bed hydrogenation micro-interface reaction system of the present invention provides a micro-interface generator, and in engineering, has the advantages of high gas utilization, high desulfurization rate, low investment, low energy consumption, flexible process and the like.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un système de réaction amélioré à lit fixe descendant doté d'une micro-interface d'hydrogénation d'huile, comprenant un réacteur (4) à lit fixe et un générateur de micro-interface, le générateur de micro-interface étant disposé sur la partie supérieure du réacteur (4) à lit fixe et convertit l'énergie de pression de l'hydrogène et/ou l'énergie cinétique de l'huile pendant la réaction en énergie de surface de bulles et la transmet aux bulles d'hydrogène, de telle sorte que l'hydrogène est décomposé en microbulles, et les microbulles sont mélangées avec l'huile dans le processus de réaction pour former une émulsion gaz-liquide; le réacteur (4) à lit fixe est utilisé comme site de réaction pour l'hydrogénation afin de former un système de réaction à lit fixe amélioré gaz-liquide stable lorsque l'émulsion gaz-liquide entre à l'intérieur de celui-ci; un réservoir (5) de séparation gaz-liquide est relié au réacteur (4) à lit fixe et est utilisé pour la séparation gaz-liquide du mélange qui complète la réaction dans le réacteur (4) à lit fixe.
PCT/CN2019/090342 2019-03-15 2019-06-06 Système de réaction amélioré à lit fixe descendant doté de micro-interface d'hydrogénation d'huile WO2020186644A1 (fr)

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JP2020600108U JP3231823U (ja) 2019-03-15 2019-06-06 下り式固定層石油製品水素化マイクロ界面強化反応システム
RU2020129865U RU205181U1 (ru) 2019-03-15 2019-06-06 Устройство усовершенствованной микроповерхностной реакции гидрирования с нисходящим потоком и фиксированным слоем для производства нефтепродуктов
DE212019000197.1U DE212019000197U1 (de) 2019-03-15 2019-06-06 Abwärts verlaufendes Festbett-Ölprodukt-Hydrierung-Mikrogrenzfläche-Reaktionsverstärkungsystem

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CN113387332A (zh) * 2021-07-16 2021-09-14 南京延长反应技术研究院有限公司 一种制备双氧水的微界面氧化系统以及氧化方法
CN113877488A (zh) * 2021-11-16 2022-01-04 中国石油大学(华东) 一种基于管式微孔介质发泡机理的上流式加氢反应装置
CN114019107A (zh) * 2021-11-08 2022-02-08 南京延长反应技术研究院有限公司 一种蒽醌法制双氧水体系中微气泡强化的评测方法

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CN116392986B (zh) * 2023-06-09 2023-08-04 北京思达流体科技有限公司 1-(4-异丁基苯基)乙醇羰基化的连续化生产系统及操作方法

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CN112263970A (zh) * 2020-10-16 2021-01-26 洛阳融惠化工科技有限公司 一种从液固并流下行床中消除气相组分影响的方法及装置
CN112263970B (zh) * 2020-10-16 2022-09-09 洛阳融惠化工科技有限公司 一种从液固并流下行床中消除气相组分影响的方法及装置
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CN113877488A (zh) * 2021-11-16 2022-01-04 中国石油大学(华东) 一种基于管式微孔介质发泡机理的上流式加氢反应装置
CN113877488B (zh) * 2021-11-16 2023-07-04 中国石油大学(华东) 一种基于管式微孔介质发泡机理的上流式加氢反应装置

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AU2019101748A4 (en) 2020-10-15

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