WO2020155506A1 - Bottom-mounted gas-liquid enhanced emulsification fixed-bed reaction device and method - Google Patents

Bottom-mounted gas-liquid enhanced emulsification fixed-bed reaction device and method Download PDF

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WO2020155506A1
WO2020155506A1 PCT/CN2019/090262 CN2019090262W WO2020155506A1 WO 2020155506 A1 WO2020155506 A1 WO 2020155506A1 CN 2019090262 W CN2019090262 W CN 2019090262W WO 2020155506 A1 WO2020155506 A1 WO 2020155506A1
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gas
liquid
bubble breaker
bed reactor
reaction
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PCT/CN2019/090262
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French (fr)
Chinese (zh)
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张志炳
李大鹏
周政
门存贵
孟为民
黄传峰
罗华勋
高亚男
王宝荣
高伟
张锋
李磊
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南京延长反应技术研究有限公司
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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
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20—Mixing gases with liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • 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
    • 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
    • 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
    • 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
    • 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
    • B01J2208/00008—Controlling the process
    • B01J2208/00628—Controlling the composition of the reactive mixture
    • 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
    • B01J2208/00823—Mixing 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the invention relates to a bottom-mounted gas-liquid enhanced emulsification fixed bed reaction device and method.
  • trickle bed Fixed-bed gas-liquid-solid three-phase reactor, often called trickle bed or trickle bed, has the characteristics of mature technology, simple process and equipment structure, so it is the most widely used and has the most industrialized processes. It is mainly used for hydrogenation , Oxidation, chlorination, nitration and carbonylation reactions.
  • the bubble diameter (Sauter diameter) d 32 is the key parameter that determines the size of the phase boundary area and the core factor that determines the gas-liquid reaction rate.
  • Bubbles with a diameter between 1 ⁇ m and 1mm can be called microbubbles
  • the phase interface formed by microbubbles is called microinterface
  • the phase interface system formed by microbubble groups is called microinterface system.
  • the micro-interface system can enhance the gas-liquid mass transfer and reaction.
  • Microbubbles have the characteristics of rigidity, good independence, and are not easy to coalesce. Therefore, the gas-liquid of the microbubble system is fully mixed to obtain an emulsion containing a large number of microbubbles, and a relatively high phase boundary area ( ⁇ 1000m 2 ) is formed in the reactor /m 3 ).
  • the purpose of the present invention is to provide a bottom-mounted gas-liquid enhanced emulsification fixed-bed reaction device and method, which is suitable for fixed-bed gas-liquid-solid three-phase reaction. It can reduce the bubble size of the gas reactant in the fixed bed reactor from the traditional 3-10mm, shredded to 1 ⁇ m-1mm, which can double the gas-liquid mass transfer area, increase the mass transfer rate and hydrogenation reaction Efficiency to solve the problems of high temperature, high pressure, high material consumption, high investment, high safety risk and other issues in the traditional fixed-bed gas-liquid-solid three-phase reaction process.
  • the present invention adopts the following technical solutions:
  • a bottom-mounted gas-liquid enhanced emulsification fixed bed reaction device comprising:
  • the air inlet device including the gas raw material buffer tank, the compressor and the gas raw material preheater connected in sequence, is used for the raw material gas transportation;
  • the liquid feeding device including the liquid raw material tank, the feeding pump and the liquid raw material preheater connected in sequence, is used for the raw material liquid transportation;
  • At least one bubble breaker is arranged at the bottom of the fixed bed reactor, the bubble breaker is provided with a gas phase inlet, a liquid phase inlet, and a first outlet, the first outlet is connected to the fixed bed reactor;
  • the gas phase inlet Connect the gas feed preheater of the inlet device, and connect the liquid phase inlet to the liquid feed preheater of the liquid feed device;
  • the gas-liquid separator is provided with a second feed port, a gas phase outlet and a liquid phase outlet; the second feed port is connected to the second discharge port on the top of the fixed bed reactor.
  • the liquid raw material and the gas raw material enter the inside of the crusher from the liquid phase inlet of the crusher and the gas phase inlet of the crusher respectively, the liquid is shredded into the gas at a high speed, and the gas is shredded into a particle size compared with the traditional method With smaller micron-sized bubbles, the gas and liquid continue to collide with each other and break, and the bubbles are crushed to become finer and finer.
  • the gas and liquid are fully mixed to form a stable emulsion, and the emulsion is constantly renewing itself.
  • the micro-sized bubbles in the emulsion reaches 1 ⁇ m-1mm, which is similar to rigid beads, the micro-sized bubbles are not prone to coalescence when they collide with the catalyst particles, and can basically maintain the original shape. Therefore, the contact area between the gas phase and the liquid phase in the fixed bed reactor is increased geometrically, and the emulsification and mixing are more sufficient and stable, so as to achieve the effect of enhancing mass transfer and macro-reaction.
  • the use of the emulsified fixed bed reaction system for the gas-liquid-solid three-phase reaction can not only reduce the temperature and pressure of the reaction system, but also reduce the gas-liquid ratio, thereby effectively solving the disadvantages of the traditional fixed-bed gas-liquid-solid three-phase reactor.
  • the gas-liquid separation is slow due to relatively small bubbles, so a separator needs to be installed after the reactor to realize the separation of microbubbles and liquid.
  • the bubble breaker is a pneumatic bubble breaker, a hydraulic bubble breaker, or a gas-liquid linkage bubble breaker.
  • the bubble breaker can be pneumatic, hydraulic and gas-liquid linkage according to the energy input mode.
  • the pneumatic breaker is driven by gas, and the input gas volume is much larger than the liquid volume; the hydraulic breaker is driven by liquid, and the input gas volume is generally smaller than the liquid.
  • the gas-liquid linkage bubble breaker is driven by gas and liquid.
  • the bubble breaker can form micro-bubbles with an average diameter of 1 ⁇ m-1mm.
  • the scale of microbubbles is on the micron level, which is similar to rigid spheres. It is not easy to aggregate in the main body of the micro-interface strengthening reaction device.
  • the micro-interface strengthening reaction device can The gas-liquid phase boundary area is increased to more than 1000m 2 /m 3 , thereby significantly reducing the multi-phase reaction time and greatly reducing energy consumption and material consumption.
  • the bubble breakers are connected in series to form a bubble breaker group and then connected to a fixed bed reactor, or connected in parallel with the fixed bed reactor, or mixed in series and parallel. Fixed bed reactor connection.
  • the catalyst bed in the fixed bed reactor has one or more stages. Further, when the fixed bed reactor is provided with multiple catalyst beds, a heat exchanger is provided between the catalyst beds according to the process requirements.
  • the invention also provides a method for the gas-liquid intensified emulsification reaction of the above-mentioned device, which includes:
  • the gas and liquid raw materials enter the bubble breaker from the gas phase inlet and the liquid phase inlet respectively.
  • the gas is broken into micron-sized bubbles, mixed with the liquid to form a gas-liquid emulsion, and then enters the fixed bed reactor from bottom to top; Pass through the catalyst bed in the original form to form a gas-liquid enhanced emulsification fixed-bed reaction system; the product after the reaction enters the gas-liquid separator from the second discharge port for gas-liquid two-phase separation, and each is collected for subsequent processing .
  • the diameter of the micron-sized bubbles formed by the bubble breaker is 1 ⁇ m-1mm.
  • the input gas-liquid ratio of the bubble breaker is not higher than 1000:1.
  • reaction pressure in the bubble breaker is 1-10 MPa.
  • the reaction temperature in the bubble breaker is 220-400°C.
  • the reaction temperature and pressure are different.
  • the space velocity in the fixed bed reactor is 0.3-3.0 h -1 .
  • the operating temperature and pressure of the bubble breaker are slightly higher than the operating temperature and pressure in the reactor.
  • the size of the bubbles in the bubble breaker is small, it is more conducive to the progress of the reaction.
  • the operating temperature and pressure in the reactor can be further reduced.
  • the present invention Compared with the traditional fixed-bed gas-liquid-solid three-phase reaction, the present invention has the following advantages:
  • the traditional fixed-bed gas-liquid-solid three-phase reactor uses high pressure to improve the solubility of gaseous raw materials in liquid raw materials to enhance mass transfer.
  • the gas is broken to form an emulsion to increase the area of the gas-liquid phase boundary and achieve the effect of enhancing mass transfer.
  • the pressure can be greatly reduced by 20%-80%, thereby reducing energy consumption.
  • the gas-liquid ratio is generally controlled at 100-3000:1. This method greatly enhances the mass transfer, so the gas-liquid ratio can be greatly reduced, which not only reduces the material consumption of the gas, but also reduces the energy consumption of the subsequent gas cycle compression.
  • Figure 1 is a structural diagram of the bottom-mounted gas-liquid enhanced emulsification fixed bed reactor of the present invention, in which:
  • the bottom-mounted gas-liquid enhanced emulsification fixed bed reaction device as shown in Figure 1 includes:
  • the fixed-bed reactor 4 is equipped with a catalyst bed 8 inside and a second discharge port on the top; the catalyst bed 8 can be one or more layers. When multiple catalyst beds are used, heat exchange is set between the beds Device.
  • the air inlet device includes a gas raw material buffer tank 12, a compressor 13, and a gas raw material preheater 15 connected in sequence, for raw material gas delivery;
  • the liquid feed device includes a liquid raw material tank 9, a feed pump 10, and a liquid raw material preheater 11 connected in sequence, for raw material liquid transportation;
  • At least one bubble breaker is arranged at the bottom of the fixed bed reactor, the bubble breaker is provided with a gas phase inlet, a liquid phase inlet, and a first outlet, the first outlet is connected to the fixed bed reactor;
  • the gas phase inlet Connect the gas feed preheater of the inlet device, and connect the liquid phase inlet to the liquid feed preheater of the liquid feed device;
  • two bubble breakers are provided at the bottom of the fixed bed reactor, namely, a gas-liquid linkage bubble breaker 3 and a pneumatic bubble breaker 15.
  • the liquid phase inlet 1 of the gas-liquid bubble breaker and the liquid phase inlet 16 of the pneumatic bubble breaker are respectively connected to the liquid raw material preheater 11; the gas phase inlet 2 of the gas-liquid bubble breaker and the pneumatic bubble breaker
  • the gas phase inlets 17 are respectively connected to the gas raw material preheater 15; the first discharge ports of the gas-liquid separators 3 and 15 are respectively connected to the fixed bed reactor 4.
  • the gas-liquid separator 5 is provided with a second feed inlet, a gas phase outlet 6 and a liquid phase outlet 7; the second feed inlet is connected to the second outlet at the top of the fixed bed reactor.
  • This example specifically illustrates the method of using the apparatus of Example 1 to perform gas-liquid strengthening reaction.
  • the hydrogen is broken into micro-bubbles with an average diameter of 300-400 ⁇ m.
  • the gas and liquid are mixed vigorously to form a gas-liquid emulsion, which enters the bottom of the fixed bed reactor 4. At the end, it 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 separator 5 from the top of the fixed-bed reactor 4.
  • the unreacted H 2 and the H 2 S produced by the reaction in the fixed-bed reactor 4 are extracted from the gas-phase outlet 6 of the gas-liquid separator.
  • 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 bubble breaker is 3MPa, 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 be 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 reaction pressure in the bubble breaker is 10MPa, and the reaction temperature is 260°C.
  • a molybdenum nickel catalyst is used in the fixed bed reactor 4, and the space velocity is controlled to 0.8 h -1 .
  • the sulfur content in the raw gasoline is 160 ppm, which is reduced to 30 ppm after the process of this hydrodesulfurization reaction process.
  • Fresh hydrogen and kerosene pass through the gas phase inlet 2 of the gas-liquid linkage crusher and the liquid phase inlet 1 of the gas-liquid linkage crusher at a standard volume ratio of 0.3:1 all the way into the gas installed above the inside of the shell of the fixed bed reactor 4.
  • the other path enters the fixed bed reactor 4 through the gas phase inlet 17 of the pneumatic crusher and the liquid phase inlet 16 of the pneumatic crusher with a standard volume ratio of 600:1.
  • the pneumatic crusher 15 in. Under the action of the gas-liquid linkage crusher 3 and the pneumatic crusher 15, the hydrogen gas is crushed into micro-bubbles with an average diameter of 600 ⁇ m to 1 mm.
  • the reaction pressure in the bubble breaker is 1MPa, 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 3.0 h -1 .
  • the sulfur content in the raw material kerosene is 100 ppm, which is reduced to 30 ppm after the process of this hydrodesulfurization reaction process.
  • Example 2 The difference between this example and Example 2 is that the wax oil is hydrodesulfurized.
  • Fresh hydrogen and wax oil pass through the gas phase inlet 2 of the gas-liquid bubble breaker and the liquid phase inlet 1 of the gas-liquid bubble breaker with a standard volume ratio of 0.3:1 all the way into the inside of the shell installed in the fixed bed reactor 4.
  • the other path enters the fixed bed reaction through the gas phase inlet 17 of the pneumatic bubble breaker and the liquid phase inlet 16 of the pneumatic bubble breaker with a standard volume ratio of 600:1.
  • the arrangement of the gas-liquid linkage bubble breaker 3 and the pneumatic bubble breaker 15 is an offset arrangement.
  • the hydrogen is broken into micro-bubbles with an average diameter of 300-400 ⁇ m.
  • the gas and liquid are mixed vigorously to form a gas-liquid emulsion, which enters the side of the fixed bed reactor 4 , Flows from bottom to top, passes through a section of the catalyst bed 8, and undergoes hydrodesulfurization under the action of the catalyst.
  • the reaction product enters the gas-liquid separator 5 from the top of the fixed-bed reactor 4.
  • the unreacted H 2 and the H 2 S produced by the reaction in the fixed-bed reactor 4 are extracted from the gas-phase outlet 6 of the gas-liquid separator.
  • the liquid phase oil product after hydrodesulfurization is extracted from the liquid phase outlet 7 of the gas-liquid separator, and collected separately for subsequent processing.
  • the reaction pressure in the bubble breaker is 6.2MPa, and the reaction temperature is 400°C.
  • FZC-302 type catalyst is used in the fixed bed reactor 4, and the space velocity is controlled at 1.0 h -1 .
  • the sulfur content in the raw material wax oil is 130 ppm, which is reduced to 40 ppm after the process of this hydrodesulfurization reaction process.

Abstract

A bottom-mounted gas-liquid enhanced emulsification fixed-bed reaction device and a method thereof used for a gas-liquid enhanced emulsification reaction. A device comprising a fixed-bed reactor (4), at least one bubble breaker (3, 15), a gas-liquid separator (5), a gas intake device and a liquid intake device. A gas raw material and a liquid raw material being preheated and then respectively passing through gas-phase inlets (2, 17) and liquid-phase inlets (1, 16) into bubble breakers (3, 15); gas bubbles being broken-down into micron-scale gas bubbles and mixing with the liquid to form a gas-liquid emulsion before rising into the fixed-bed reactor (4), maintaining the original form thereof and passing through a catalyst bed layer (8), forming a gas-liquid enhanced emulsification fixed-bed reaction system; a product of the completed reaction passing from a second material outlet into the gas-liquid separator (5) so as to undergo gas-liquid two-phase separation, and each phase being collected and undergoing subsequent processing.

Description

下置式气液强化乳化固定床反应装置及方法Bottom-mounted gas-liquid enhanced emulsification fixed bed reaction device and method 技术领域Technical field
本发明涉及一种下置式气液强化乳化固定床反应装置及方法。The invention relates to a bottom-mounted gas-liquid enhanced emulsification fixed bed reaction device and method.
背景技术Background technique
固定床气液固三相反应器，常称滴流床或涓流床，其有技术成熟、工艺和设备结构简单等特点，因而应用最广泛，而且工业化的工艺也最多，主要用于加氢、氧化、氯化、硝化和羰基化等反应。Fixed-bed gas-liquid-solid three-phase reactor, often called trickle bed or trickle bed, has the characteristics of mature technology, simple process and equipment structure, so it is the most widely used and has the most industrialized processes. It is mainly used for hydrogenation , Oxidation, chlorination, nitration and carbonylation reactions.
随着国际社会环境保护力度的不断加大，全世界对高效节能的反应过程的需求与日剧增，人们对固定床气液固三相反应器系统投入了更大的关注。传统的固定床气液固三相反应器虽然对原料的适应性强、操作简单，但由于其受传质控制，因而反应效率较低。其根本原因是固定床反应器内的气泡尺度较大(一般为3-10mm)，故气液相界传质面积小(一般在100-200m 2/m 3)，因而限制了传质效率。因此，工程上不得不在操作中提高反应温度，或者通过高压将气体预溶解在液相反应物的方式，增加气体在液相中的溶解度以提高传质速率，从而强化反应过程。但高温高压操作会带来负面效应，即能耗和生产成本高、投资强度大、设备操作周期短、故障多、本质安全性差等。此外预溶解在液相反应物的小气泡在与固定床中催化剂颗粒的运动碰撞中，容易发生气泡的聚并，使得气泡直径变得更大，固定床内气液分布均匀性劣化。这些制约因素都会给工业化大规模生产带来挑战。 With the continuous increase in environmental protection in the international community, the world’s demand for highly efficient and energy-saving reaction processes has increased dramatically, and people have paid more attention to fixed-bed gas-liquid-solid three-phase reactor systems. Although the traditional fixed-bed gas-liquid-solid three-phase reactor has strong adaptability to raw materials and simple operation, its reaction efficiency is low because it is controlled by mass transfer. The fundamental reason is that the bubble size in the fixed bed reactor is relatively large (generally 3-10mm), so the mass transfer area of the gas-liquid phase boundary is small (generally 100-200m 2 /m 3 ), which limits the mass transfer efficiency. Therefore, engineering has to increase the reaction temperature during operation, or pre-dissolve the gas in the liquid phase reactant through high pressure to increase the solubility of the gas in the liquid phase to increase the mass transfer rate, thereby enhancing the reaction process. However, high temperature and high pressure operation will bring negative effects, namely high energy consumption and production cost, high investment intensity, short equipment operation cycle, many failures, and poor intrinsic safety. In addition, the small bubbles pre-dissolved in the liquid phase reactant collide with the movement of the catalyst particles in the fixed bed, and the bubbles are prone to coalescence, which makes the bubble diameter larger and deteriorates the uniformity of gas-liquid distribution in the fixed bed. These constraints will bring challenges to industrialized mass production.
气泡直径(Sauter直径)d 32是决定相界面积大小的关键参数，是决定气液反应速率的核心因素。直径在1μm～1mm之间的气泡可称为微气泡，由微气泡形成的相界面称为微界面，微气泡群形成的相界面体系，称为微界面体系。在气液反应过程中，微界面体系能够强化气液传质及反应。微气泡具有刚性特征，独立性好，不易聚并，因此微气泡体系的气液充分混合，可获得含有大量微气泡的乳化液，并在反应器内形成较高的相界面积(≥1000m 2/m 3)。 The bubble diameter (Sauter diameter) d 32 is the key parameter that determines the size of the phase boundary area and the core factor that determines the gas-liquid reaction rate. Bubbles with a diameter between 1μm and 1mm can be called microbubbles, the phase interface formed by microbubbles is called microinterface, and the phase interface system formed by microbubble groups is called microinterface system. In the gas-liquid reaction process, the micro-interface system can enhance the gas-liquid mass transfer and reaction. Microbubbles have the characteristics of rigidity, good independence, and are not easy to coalesce. Therefore, the gas-liquid of the microbubble system is fully mixed to obtain an emulsion containing a large number of microbubbles, and a relatively high phase boundary area (≥1000m 2 ) is formed in the reactor /m 3 ).
发明内容Summary of the invention
本发明的目的是提供一种下置式气液强化乳化固定床反应装置及方法，适用于固定床气液固三相反应。它可以将固定床反应器内的气体反应物的气泡尺度由传统的3-10mm，切碎缩小至1μm-1mm，从而可成倍地提高气液传质面积，提高传质速率和加氢反应效率，以解决传统固定床气液固三相反应过程中高温、高压、高物耗、高投资、高安全风险等问题。The purpose of the present invention is to provide a bottom-mounted gas-liquid enhanced emulsification fixed-bed reaction device and method, which is suitable for fixed-bed gas-liquid-solid three-phase reaction. It can reduce the bubble size of the gas reactant in the fixed bed reactor from the traditional 3-10mm, shredded to 1μm-1mm, which can double the gas-liquid mass transfer area, increase the mass transfer rate and hydrogenation reaction Efficiency to solve the problems of high temperature, high pressure, high material consumption, high investment, high safety risk and other issues in the traditional fixed-bed gas-liquid-solid three-phase reaction process.
为实现上述技术目的，本发明采用如下技术方案：To achieve the above technical objectives, the present invention adopts the following technical solutions:
一种下置式气液强化乳化固定床反应装置，包括：A bottom-mounted gas-liquid enhanced emulsification fixed bed reaction device, comprising:
固定床反应器，内设有催化剂床层，顶部设有第二出料口；Fixed-bed reactor with a catalyst bed inside and a second discharge port on the top;
进气装置，包括依次连接的气体原料缓冲罐、压缩机和气体原料预热器，用于原料气体输送；The air inlet device, including the gas raw material buffer tank, the compressor and the gas raw material preheater connected in sequence, is used for the raw material gas transportation;
进液装置，包括依次连接的液体原料罐、进料泵和液体原料预热器，用于原料液体输送；The liquid feeding device, including the liquid raw material tank, the feeding pump and the liquid raw material preheater connected in sequence, is used for the raw material liquid transportation;
至少一个气泡破碎器，设置于固定床反应器底部，所述气泡破碎器上设有气相入口、液相入口和第一出料口，所述第一出料口连接固定床反应器；气相入口连接进气装置的气体原料预热器，液相入口连接进液装置的液体原料预热器；At least one bubble breaker is arranged at the bottom of the fixed bed reactor, the bubble breaker is provided with a gas phase inlet, a liquid phase inlet, and a first outlet, the first outlet is connected to the fixed bed reactor; the gas phase inlet Connect the gas feed preheater of the inlet device, and connect the liquid phase inlet to the liquid feed preheater of the liquid feed device;
气液分离器，上设有第二进料口、气相出口和液相出口；所述第二进料口连接固定床反应器顶部的第二出料口。The gas-liquid separator is provided with a second feed port, a gas phase outlet and a liquid phase outlet; the second feed port is connected to the second discharge port on the top of the fixed bed reactor.
本发明的上述装置，在液体原料和气体原料分别从破碎器的液相入口和破碎器的气相入口进入破碎器内部时，液体高速切碎气体，气体被切碎成相比于传统方法粒径更小的微米级气泡，气液相互持续碰撞破碎，气泡被粉碎得愈来愈细，气液充分混合，形成稳定的乳化液，同时乳化液还在不断进行自身更新。此外由于乳化液中气泡尺度达到1μm-1mm，类似于刚性小球，微米级气泡在与催化剂颗粒的运动碰撞中，不容易发生气泡的聚并，基本可以保持原有形态。因此固定床反应器内气相与液相的接触面积成几何倍数的增加，并使得乳化混合更加充分和稳定，从而达到强化传质和宏观反应的效果。这样利用乳化固定床反应系统进行气液固三相反应，既可降低反应体系的温度和压力，又可减小气液比，从而能有效解决传统固定床气液固三相反应器的弊病。In the above-mentioned device of the present invention, when the liquid raw material and the gas raw material enter the inside of the crusher from the liquid phase inlet of the crusher and the gas phase inlet of the crusher respectively, the liquid is shredded into the gas at a high speed, and the gas is shredded into a particle size compared with the traditional method With smaller micron-sized bubbles, the gas and liquid continue to collide with each other and break, and the bubbles are crushed to become finer and finer. The gas and liquid are fully mixed to form a stable emulsion, and the emulsion is constantly renewing itself. In addition, because the size of the bubbles in the emulsion reaches 1μm-1mm, which is similar to rigid beads, the micro-sized bubbles are not prone to coalescence when they collide with the catalyst particles, and can basically maintain the original shape. Therefore, the contact area between the gas phase and the liquid phase in the fixed bed reactor is increased geometrically, and the emulsification and mixing are more sufficient and stable, so as to achieve the effect of enhancing mass transfer and macro-reaction. In this way, the use of the emulsified fixed bed reaction system for the gas-liquid-solid three-phase reaction can not only reduce the temperature and pressure of the reaction system, but also reduce the gas-liquid ratio, thereby effectively solving the disadvantages of the traditional fixed-bed gas-liquid-solid three-phase reactor.
本发明的反应体系由于气泡比较小，而导致的气液分离较慢，所以需要再反应器后设置分离器以实现微气泡与液体的分离。In the reaction system of the present invention, the gas-liquid separation is slow due to relatively small bubbles, so a separator needs to be installed after the reactor to realize the separation of microbubbles and liquid.
作为本发明的进一步改进，所述气泡破碎器为气动式气泡破碎器、液动式气泡破碎器或气液联动式气泡破碎器。气泡破碎器根据能量输入方式可为气动式、液动式和气液联动式，其中气动式破碎器采用气体驱动，输入气量远大于液体量；液动式破碎器采用液体驱动，输入气量一般小于液体量；气液联动式气泡破碎器采用气体和液体共同驱动。气泡破碎器内可形成平均直径在1μm-1mm之间的微气泡。微气泡尺度为微米级，类似于刚性小球，在微界面强化反应装置主体中不容易聚并，仅随反应过程中气泡内成分的消耗或外部压力变化而变化，因此微界面强化反应装置可使气液相界面积提高到1000m 2/m 3以上，从而显著减少多相反应时间，大幅降低能耗与物耗。 As a further improvement of the present invention, the bubble breaker is a pneumatic bubble breaker, a hydraulic bubble breaker, or a gas-liquid linkage bubble breaker. The bubble breaker can be pneumatic, hydraulic and gas-liquid linkage according to the energy input mode. The pneumatic breaker is driven by gas, and the input gas volume is much larger than the liquid volume; the hydraulic breaker is driven by liquid, and the input gas volume is generally smaller than the liquid. The gas-liquid linkage bubble breaker is driven by gas and liquid. The bubble breaker can form micro-bubbles with an average diameter of 1μm-1mm. The scale of microbubbles is on the micron level, which is similar to rigid spheres. It is not easy to aggregate in the main body of the micro-interface strengthening reaction device. It only changes with the consumption of the bubbles in the reaction process or the change of external pressure. Therefore, the micro-interface strengthening reaction device can The gas-liquid phase boundary area is increased to more than 1000m 2 /m 3 , thereby significantly reducing the multi-phase reaction time and greatly reducing energy consumption and material consumption.
作为本发明的进一步改进，所述气泡破碎器设有多个；气泡破碎器串联形成一个气泡破碎器组后连接固定床反应器，或与固定床反应器并联连接，或串并联混合的方式与固定床反应器连接。As a further improvement of the present invention, there are multiple bubble breakers; the bubble breakers are connected in series to form a bubble breaker group and then connected to a fixed bed reactor, or connected in parallel with the fixed bed reactor, or mixed in series and parallel. Fixed bed reactor connection.
作为本发明的进一步改进，所述固定床反应器中的催化剂床层为一段或多段。进一步的， 固定床反应器中设有多段催化剂床层时，催化剂床层间根据工艺需要设有换热器。As a further improvement of the present invention, the catalyst bed in the fixed bed reactor has one or more stages. Further, when the fixed bed reactor is provided with multiple catalyst beds, a heat exchanger is provided between the catalyst beds according to the process requirements.
本发明还提供了上述装置用于气液强化乳化反应的方法，包括：The invention also provides a method for the gas-liquid intensified emulsification reaction of the above-mentioned device, which includes:
气体原料和液体原料经预热后分别自气相入口和液相入口进入气泡破碎器，气体被破碎成微米级气泡，与液体混合形成气液乳化物后自下而上进入固定床反应器中；保持原有形态穿过催化剂床层，形成气液强化乳化固定床反应体系；反应完的产物自第二出料口进入气液分离器中，进行气液两相分离，各自收集，进行后续处理。After preheating, the gas and liquid raw materials enter the bubble breaker from the gas phase inlet and the liquid phase inlet respectively. The gas is broken into micron-sized bubbles, mixed with the liquid to form a gas-liquid emulsion, and then enters the fixed bed reactor from bottom to top; Pass through the catalyst bed in the original form to form a gas-liquid enhanced emulsification fixed-bed reaction system; the product after the reaction enters the gas-liquid separator from the second discharge port for gas-liquid two-phase separation, and each is collected for subsequent processing .
作为本发明的进一步改进，所述气泡破碎器形成的微米级气泡直径为1μm-1mm。As a further improvement of the present invention, the diameter of the micron-sized bubbles formed by the bubble breaker is 1 μm-1mm.
作为本发明的进一步改进，所述气泡破碎器输入气液比不高于1000：1。As a further improvement of the present invention, the input gas-liquid ratio of the bubble breaker is not higher than 1000:1.
作为本发明的进一步改进，所述气泡破碎器内反应压力为1～10MPa。As a further improvement of the present invention, the reaction pressure in the bubble breaker is 1-10 MPa.
作为本发明的进一步改进，所述气泡破碎器内反应温度为220～400℃。根据输入液体原料的不同，反应温度、压力存在区别。As a further improvement of the present invention, the reaction temperature in the bubble breaker is 220-400°C. Depending on the input liquid raw materials, the reaction temperature and pressure are different.
作为本发明的进一步改进，所述固定床反应器内空速为0.3～3.0h -1。 As a further improvement of the present invention, the space velocity in the fixed bed reactor is 0.3-3.0 h -1 .
本发明的反应体系，为保证气泡破碎器内体系进入反应器，气泡破碎器操作温度、压强略高于反应器内操作温度、压强，在气泡破碎器内气泡大小较小时，更利于反应进行，可进一步降低反应器内操作温度、压强。In the reaction system of the present invention, in order to ensure that the system in the bubble breaker enters the reactor, the operating temperature and pressure of the bubble breaker are slightly higher than the operating temperature and pressure in the reactor. When the size of the bubbles in the bubble breaker is small, it is more conducive to the progress of the reaction. The operating temperature and pressure in the reactor can be further reduced.
本发明相较于传统的固定床气液固三相反应的优点在于：Compared with the traditional fixed-bed gas-liquid-solid three-phase reaction, the present invention has the following advantages:
1.能耗低。传统的固定床气液固三相反应器通过高压来提高气体原料在液体原料中的溶解度，以加强传质。而本发明则是通过气体破碎形成乳化液，来增大气液两相的相界面积，达到强化传质的效果。与传统的固定床相比，压力可大幅下降20％-80％，从而降低了能耗。1. Low energy consumption. The traditional fixed-bed gas-liquid-solid three-phase reactor uses high pressure to improve the solubility of gaseous raw materials in liquid raw materials to enhance mass transfer. In the present invention, the gas is broken to form an emulsion to increase the area of the gas-liquid phase boundary and achieve the effect of enhancing mass transfer. Compared with the traditional fixed bed, the pressure can be greatly reduced by 20%-80%, thereby reducing energy consumption.
2.气液比低。传统固定床气液固三相反应器为了保证液体原料能充分反应，气液比一般控制在100-3000:1。本方法由于大幅度强化传质，因此可大幅减小气液比，这不但减少了气体的物耗，同时也降低了后续气体循环压缩的能耗。2. Low gas-liquid ratio. In order to ensure that the liquid raw materials can fully react in the traditional fixed-bed gas-liquid-solid three-phase reactor, the gas-liquid ratio is generally controlled at 100-3000:1. This method greatly enhances the mass transfer, so the gas-liquid ratio can be greatly reduced, which not only reduces the material consumption of the gas, but also reduces the energy consumption of the subsequent gas cycle compression.
3.工艺苛刻度低，生产安全性高，吨产品成本低，市场竞争力强。3. Low craftsmanship, high production safety, low product cost per ton, and strong market competitiveness.
附图说明Description of the drawings
图1为本发明的下置式气液强化乳化固定床反应装置结构图，其中：Figure 1 is a structural diagram of the bottom-mounted gas-liquid enhanced emulsification fixed bed reactor of the present invention, in which:
1-气液联动式气泡破碎器的液相入口；2-气液联动式气泡破碎器的气相入口；3-气液联动式气泡破碎器；4-固定床反应器；5-气液分离器；6-气液分离器的气相出口；7-气液分离器的液相出口；8-催化剂床层；9-液体原料罐；10-进料泵；11-液体原料预热器；12-气体原料缓冲罐；13-压缩机；14-气体原料预热器；15-气动式气泡破碎器；16-气动式气泡破碎器的液相入口；17-气动式气泡破碎器的气相入口。1- Liquid phase inlet of gas-liquid bubble breaker; 2- Gas phase inlet of gas-liquid bubble breaker; 3- Gas-liquid bubble breaker; 4- Fixed bed reactor; 5- Gas-liquid separator 6-gas phase outlet of gas-liquid separator; 7-liquid phase outlet of gas-liquid separator; 8-catalyst bed; 9-liquid raw material tank; 10-feed pump; 11-liquid raw material preheater; 12- Gas raw material buffer tank; 13-compressor; 14-gas raw material preheater; 15-pneumatic bubble breaker; 16-pneumatic bubble breaker's liquid phase inlet; 17-pneumatic bubble breaker's gas phase inlet.
具体实施方式detailed description
下面结合附图说明对本发明的技术方案做进一步阐述。The technical scheme of the present invention will be further described below in conjunction with the description of the accompanying drawings.
实施例1Example 1
如图1所示的下置式气液强化乳化固定床反应装置，包括：The bottom-mounted gas-liquid enhanced emulsification fixed bed reaction device as shown in Figure 1, includes:
固定床反应器4，内设有催化剂床层8，顶部设有第二出料口；催化剂床层8可为一层或多层，采用多层催化剂床层时，在床层间设置换热器。The fixed-bed reactor 4 is equipped with a catalyst bed 8 inside and a second discharge port on the top; the catalyst bed 8 can be one or more layers. When multiple catalyst beds are used, heat exchange is set between the beds Device.
进气装置，包括依次连接的气体原料缓冲罐12、压缩机13和气体原料预热器15，用于原料气体输送；The air inlet device includes a gas raw material buffer tank 12, a compressor 13, and a gas raw material preheater 15 connected in sequence, for raw material gas delivery;
进液装置，包括依次连接的液体原料罐9、进料泵10和液体原料预热器11，用于原料液体输送；The liquid feed device includes a liquid raw material tank 9, a feed pump 10, and a liquid raw material preheater 11 connected in sequence, for raw material liquid transportation;
至少一个气泡破碎器，设置于固定床反应器底部，所述气泡破碎器上设有气相入口、液相入口和第一出料口，所述第一出料口连接固定床反应器；气相入口连接进气装置的气体原料预热器，液相入口连接进液装置的液体原料预热器；At least one bubble breaker is arranged at the bottom of the fixed bed reactor, the bubble breaker is provided with a gas phase inlet, a liquid phase inlet, and a first outlet, the first outlet is connected to the fixed bed reactor; the gas phase inlet Connect the gas feed preheater of the inlet device, and connect the liquid phase inlet to the liquid feed preheater of the liquid feed device;
本实施例在固定床反应器底部设置两个气泡破碎器，分别为气液联动式气泡破碎器3和气动式气泡破碎器15。气液联动式气泡破碎器的液相入口1和气动式气泡破碎器的液相入口16分别连接液体原料预热器11；气液联动式气泡破碎器的气相入口2和气动式气泡破碎器的气相入口17分别连接气体原料预热器15；气液分离器3和15的第一出料口分别连接固定床反应器4。In this embodiment, two bubble breakers are provided at the bottom of the fixed bed reactor, namely, a gas-liquid linkage bubble breaker 3 and a pneumatic bubble breaker 15. The liquid phase inlet 1 of the gas-liquid bubble breaker and the liquid phase inlet 16 of the pneumatic bubble breaker are respectively connected to the liquid raw material preheater 11; the gas phase inlet 2 of the gas-liquid bubble breaker and the pneumatic bubble breaker The gas phase inlets 17 are respectively connected to the gas raw material preheater 15; the first discharge ports of the gas- liquid separators 3 and 15 are respectively connected to the fixed bed reactor 4.
气液分离器5，上设有第二进料口、气相出口6和液相出口7；所述第二进料口连接固定床反应器顶部的第二出料口。The gas-liquid separator 5 is provided with a second feed inlet, a gas phase outlet 6 and a liquid phase outlet 7; the second feed inlet is connected to the second outlet at the top of the fixed bed reactor.
实施例2Example 2
本实施例具体说明利用实施例1的装置进行气液强化反应的方法。This example specifically illustrates the method of using the apparatus of Example 1 to perform gas-liquid strengthening reaction.
新鲜氢气和汽油一路以0.25：1的标准体积比分别通过气液联动式气泡破碎器的气相入口2和气液联动式气泡破碎器的液相入口1进入安装在固定床反应器4的外壳内部下方的气液联动式气泡破碎器3中，另一路以800：1的标准体积比分别通过气动式气泡破碎器的气相入口17和气动式气泡破碎器的液相入口16进入安装在固定床反应器4的外壳内部下方的气动式气泡破碎器15中。在气液联动式气泡破碎器3和气动式气泡破碎器15的作用下，氢气被破碎成平均直径300～400μm的微气泡，气液剧烈混合形成气液乳化物，进入固定床反应器4底端，由下向上流动，穿过一段催化剂床层8，在催化剂的作用下进行加氢脱硫反应。反应产物由固定床反应器4顶端进入气液分离器5，固定床反应器4未反应完的H 2和反应生成的H 2S等气体从气液分离器的气相出口6采出，经加氢脱硫后的液相油品从气液分离罐的液相出口7采出，各自收集，进行后续处理。 Fresh hydrogen and gasoline pass through the gas phase inlet 2 of the gas-liquid bubble breaker and the liquid phase inlet 1 of the gas-liquid bubble breaker with a standard volume ratio of 0.25:1 all the way into the lower part of the shell installed in the fixed bed reactor 4. In the gas-liquid linkage bubble breaker 3, the other path enters the fixed bed reactor through the gas phase inlet 17 of the pneumatic bubble breaker and the liquid phase inlet 16 of the pneumatic bubble breaker with a standard volume ratio of 800:1 4 in the pneumatic bubble breaker 15 below the inside of the housing. Under the action of the gas-liquid bubble breaker 3 and the pneumatic bubble breaker 15, the hydrogen is broken into micro-bubbles with an average diameter of 300-400μm. The gas and liquid are mixed vigorously to form a gas-liquid emulsion, which enters the bottom of the fixed bed reactor 4. At the end, it 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 separator 5 from the top of the fixed-bed reactor 4. The unreacted H 2 and the H 2 S produced by the reaction in the fixed-bed reactor 4 are extracted from the gas-phase outlet 6 of the gas-liquid separator. 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.
气泡破碎器内反应压力为3MPa，反应温度为220℃。固定床反应器4内采用钼镍催化剂，空速控制为0.3h -1。原料汽油中硫含量为120ppm，经过本加氢脱硫的反应流程处理之后，降为20ppm。 The reaction pressure in the bubble breaker is 3MPa, 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 be 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.
实施例3Example 3
本实施例和实施例2的不同之处在于，采用一个气动式气泡破碎器进行气泡破碎。The difference between this embodiment and the second embodiment is that a pneumatic bubble breaker is used to break the bubbles.
新鲜氢气和汽油以1000：1的标准体积比分别通过气动式气泡破碎器的气相入口和气动式气泡破碎器的液相入口进入安装在固定床反应器4的外壳内部下方的气动式气泡破碎器中。在气动式气泡破碎器的作用下，氢气被破碎成平均直径1～300μm的微气泡。Fresh hydrogen and gasoline enter the pneumatic bubble breaker installed below the shell of the fixed bed reactor 4 through the gas phase inlet of the pneumatic bubble breaker and the liquid phase inlet of the pneumatic bubble breaker at a standard volume ratio of 1000:1. in. Under the action of the pneumatic bubble breaker, the hydrogen is broken into micro-bubbles with an average diameter of 1 to 300 μm.
气泡破碎器内反应压力为10MPa，反应温度为260℃。固定床反应器4内采用钼镍催化剂，空速控制为0.8h -1。原料汽油中硫含量为160ppm，经过本加氢脱硫的反应流程处理之后，降为30ppm。 The reaction pressure in the bubble breaker is 10MPa, and the reaction temperature is 260°C. A molybdenum nickel catalyst is used in the fixed bed reactor 4, and the space velocity is controlled to 0.8 h -1 . The sulfur content in the raw gasoline is 160 ppm, which is reduced to 30 ppm after the process of this hydrodesulfurization reaction process.
实施例4Example 4
本实施例和实施例2的不同之处在于，对煤油进行加氢脱硫。The difference between this example and example 2 is that kerosene is hydrodesulfurized.
新鲜氢气和煤油一路以0.3：1的标准体积比分别通过气液联动式破碎器的气相入口2和气液联动式破碎器的液相入口1进入安装在固定床反应器4的外壳内部上方的气液联动式破碎器3中，另一路以600：1的标准体积比分别通过气动式破碎器的气相入口17和气动式破碎器的液相入口16进入安装在固定床反应器4的外壳内部上方的气动式破碎器15中。在气液联动式破碎器3和气动式破碎器15的作用下，氢气被破碎成平均直径600μm～1mm的微气泡。Fresh hydrogen and kerosene pass through the gas phase inlet 2 of the gas-liquid linkage crusher and the liquid phase inlet 1 of the gas-liquid linkage crusher at a standard volume ratio of 0.3:1 all the way into the gas installed above the inside of the shell of the fixed bed reactor 4. In the liquid-linked crusher 3, the other path enters the fixed bed reactor 4 through the gas phase inlet 17 of the pneumatic crusher and the liquid phase inlet 16 of the pneumatic crusher with a standard volume ratio of 600:1. The pneumatic crusher 15 in. Under the action of the gas-liquid linkage crusher 3 and the pneumatic crusher 15, the hydrogen gas is crushed into micro-bubbles with an average diameter of 600 μm to 1 mm.
气泡破碎器内反应压力为1MPa，反应温度为250℃。固定床反应器4内采用钼镍催化剂，空速控制为3.0h -1。原料煤油中硫含量为100ppm，经过本加氢脱硫的反应流程处理之后，降为30ppm。 The reaction pressure in the bubble breaker is 1MPa, 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 3.0 h -1 . The sulfur content in the raw material kerosene is 100 ppm, which is reduced to 30 ppm after the process of this hydrodesulfurization reaction process.
实施例5Example 5
本实施例和实施例2的不同之处在于，对蜡油进行加氢脱硫。The difference between this example and Example 2 is that the wax oil is hydrodesulfurized.
新鲜氢气和蜡油一路以0.3：1的标准体积比分别通过气液联动式气泡破碎器的气相入口2和气液联动式气泡破碎器的液相入口1进入安装在固定床反应器4的外壳内部侧面的气液联动式气泡破碎器3中，另一路以600：1的标准体积比分别通过气动式气泡破碎器的气相入口17和气动式气泡破碎器的液相入口16进入安装在固定床反应器4的外壳内部侧面的气动式气泡破碎器15中。气液联动式气泡破碎器3和气动式气泡破碎器15的布置是对冲式布置。在气液联动式气泡破碎器3和气动式气泡破碎器15的作用下，氢气被破碎成平均直径300～400μm的微气泡，气液剧烈混合形成气液乳化物，进入固定床反应器4侧面，由下向上 流动，穿过一段催化剂床层8，在催化剂的作用下进行加氢脱硫反应。反应产物由固定床反应器4顶端进入气液分离器5，固定床反应器4未反应完的H 2和反应生成的H 2S等气体从气液分离器的气相出口6采出，经加氢脱硫后的液相油品从气液分离器的液相出口7采出，各自收集，进行后续处理。 Fresh hydrogen and wax oil pass through the gas phase inlet 2 of the gas-liquid bubble breaker and the liquid phase inlet 1 of the gas-liquid bubble breaker with a standard volume ratio of 0.3:1 all the way into the inside of the shell installed in the fixed bed reactor 4. In the gas-liquid linkage bubble breaker 3 on the side, the other path enters the fixed bed reaction through the gas phase inlet 17 of the pneumatic bubble breaker and the liquid phase inlet 16 of the pneumatic bubble breaker with a standard volume ratio of 600:1. In the pneumatic bubble breaker 15 on the inner side of the shell of the device 4. The arrangement of the gas-liquid linkage bubble breaker 3 and the pneumatic bubble breaker 15 is an offset arrangement. Under the action of the gas-liquid bubble breaker 3 and the pneumatic bubble breaker 15, the hydrogen is broken into micro-bubbles with an average diameter of 300-400μm. The gas and liquid are mixed vigorously to form a gas-liquid emulsion, which enters the side of the fixed bed reactor 4 , Flows from bottom to top, passes through a section of the catalyst bed 8, and undergoes hydrodesulfurization under the action of the catalyst. The reaction product enters the gas-liquid separator 5 from the top of the fixed-bed reactor 4. The unreacted H 2 and the H 2 S produced by the reaction in the fixed-bed reactor 4 are extracted from the gas-phase outlet 6 of the gas-liquid separator. The liquid phase oil product after hydrodesulfurization is extracted from the liquid phase outlet 7 of the gas-liquid separator, and collected separately for subsequent processing.
气泡破碎器内反应压力为6.2MPa，反应温度为400℃。固定床反应器4内采用FZC-302型催化剂，空速控制为1.0h -1。原料蜡油中硫含量为130ppm，经过本加氢脱硫的反应流程处理之后，降为40ppm。 The reaction pressure in the bubble breaker is 6.2MPa, and the reaction temperature is 400°C. FZC-302 type catalyst is used in the fixed bed reactor 4, and the space velocity is controlled at 1.0 h -1 . The sulfur content in the raw material wax oil is 130 ppm, which is reduced to 40 ppm after the process of this hydrodesulfurization reaction process.

Claims (10)

  1. 一种下置式气液强化乳化固定床反应装置，其特征在于，包括：A bottom-mounted gas-liquid enhanced emulsification fixed-bed reaction device is characterized in that it comprises:
    固定床反应器，内设有催化剂床层，顶部设有第二出料口；Fixed-bed reactor with a catalyst bed inside and a second discharge port on the top;
    进气装置，包括依次连接的气体原料缓冲罐、压缩机和气体原料预热器，用于原料气体输送；The air inlet device, including the gas raw material buffer tank, the compressor and the gas raw material preheater connected in sequence, is used for the raw material gas transportation;
    进液装置，包括依次连接的液体原料罐、进料泵和液体原料预热器，用于原料液体输送；The liquid feeding device, including the liquid raw material tank, the feeding pump and the liquid raw material preheater connected in sequence, is used for the raw material liquid transportation;
    至少一个气泡破碎器，设置于固定床反应器底部，所述气泡破碎器上设有气相入口、液相入口和第一出料口，所述第一出料口连接固定床反应器；气相入口连接进气装置的气体原料预热器，液相入口连接进液装置的液体原料预热器；At least one bubble breaker is arranged at the bottom of the fixed bed reactor, the bubble breaker is provided with a gas phase inlet, a liquid phase inlet, and a first outlet, the first outlet is connected to the fixed bed reactor; the gas phase inlet Connect the gas feed preheater of the inlet device, and connect the liquid phase inlet to the liquid feed preheater of the liquid feed device;
    气液分离器，上设有第二进料口、气相出口和液相出口；所述第二进料口连接固定床反应器顶部的第二出料口。The gas-liquid separator is provided with a second feed port, a gas phase outlet and a liquid phase outlet; the second feed port is connected to the second discharge port on the top of the fixed bed reactor.
  2. 根据权利要求1所述的装置，其特征在于，所述气泡破碎器为气动式气泡破碎器、液动式气泡破碎器或气液联动式气泡破碎器。The device of claim 1, wherein the bubble breaker is a pneumatic bubble breaker, a hydraulic bubble breaker, or a gas-liquid linkage bubble breaker.
  3. 根据权利要求1所述的装置，其特征在于，所述气泡破碎器设有多个；气泡破碎器串联形成一个气泡破碎器组后连接固定床反应器，或与固定床反应器并联连接，或串并联混合的方式与固定床反应器连接。The device according to claim 1, characterized in that there are multiple bubble breakers; the bubble breakers are connected in series to form a bubble breaker group and then connected to a fixed bed reactor, or connected in parallel with the fixed bed reactor, or It is connected to a fixed bed reactor in a series-parallel mixing manner.
  4. 根据权利要求1所述的装置，其特征在于，所述固定床反应器中的催化剂床层为一段或多段。The device according to claim 1, wherein the catalyst bed in the fixed bed reactor is one or more stages.
  5. 根据权利要求4所述的装置，其特征在于，所述固定床反应器中设有多段催化剂床层，催化剂床层间设有换热器。The device according to claim 4, wherein the fixed bed reactor is provided with multi-stage catalyst beds, and a heat exchanger is provided between the catalyst beds.
  6. 权利要求1～5任一项所述装置用于气液强化乳化反应的方法，其特征在于，包括：The method for gas-liquid intensified emulsification reaction with the device according to any one of claims 1 to 5, characterized in that it comprises:
    气体原料和液体原料经预热后分别自气相入口和液相入口进入气泡破碎器，气体被破碎成微米级气泡，与液体混合形成气液乳化物后自下而上进入固定床反应器中；保持原有形态穿过催化剂床层，形成气液强化乳化固定床反应体系；反应完的产物自第二出料口进入气液分离器中，进行气液两相分离，各自收集，进行后续处理。After preheating, the gas and liquid raw materials enter the bubble breaker from the gas phase inlet and the liquid phase inlet respectively. The gas is broken into micron-sized bubbles, mixed with the liquid to form a gas-liquid emulsion, and then enters the fixed bed reactor from bottom to top; Pass through the catalyst bed in the original form to form a gas-liquid enhanced emulsification fixed-bed reaction system; the product after the reaction enters the gas-liquid separator from the second discharge port for gas-liquid two-phase separation, and each is collected for subsequent processing .
  7. 根据权利要求6所述的方法，其特征在于，所述气泡破碎器形成的微米级气泡直径为1μm-1mm。The method according to claim 6, wherein the diameter of the micron-sized bubbles formed by the bubble breaker is 1 μm-1 mm.
  8. 根据权利要求6所述的方法，其特征在于，所述气泡破碎器输入气液比不高于1000：1。The method according to claim 6, wherein the input gas-liquid ratio of the bubble breaker is not higher than 1000:1.
  9. 根据权利要求6所述的方法，其特征在于，所述气泡破碎器内反应压力为1～10MPa。The method according to claim 6, wherein the reaction pressure in the bubble breaker is 1-10 MPa.
  10. 根据权利要求6所述的方法，其特征在于，所述气泡破碎器内反应温度为220～400℃。The method of claim 6, wherein the reaction temperature in the bubble breaker is 220-400°C.
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CN112142568A (en) * 2020-09-17 2020-12-29 南京延长反应技术研究院有限公司 Reinforced micro-interface preparation system and method for p-methylphenol
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1321715A (en) * 1970-05-14 1973-06-27 Nat Res Dev Gas bubble redistribution in fluidised beds
CN1214077A (en) * 1996-03-18 1999-04-14 切夫里昂美国公司 Gas-pocket distributor and method for hydroprocessing hydrocarbon feed stream
CN101632911A (en) * 2008-07-24 2010-01-27 中国石油化工股份有限公司 Up-flow reactor and application thereof
CN101668725A (en) * 2007-06-27 2010-03-10 Hrd有限公司 System and process for fischer-tropsch conversion
CN103666544A (en) * 2012-09-21 2014-03-26 中国石油化工股份有限公司 Hydro-treating method of reformate
CN107497372A (en) * 2016-06-14 2017-12-22 中国石油天然气集团公司 Hydrogenation reactor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010090811A1 (en) * 2009-01-20 2010-08-12 H R D Corporation Process for hydrodesulfurization, hydrodenitrogenation, hydrofinishing, or amine production
CN105038845B (en) * 2015-07-10 2017-08-29 中石化炼化工程（集团）股份有限公司 Device for strengthening bubbling bed hydrogenation reactor gas-liquid mass transfer
CN210229906U (en) * 2019-01-29 2020-04-03 南京延长反应技术研究院有限公司 Underneath type gas-liquid reinforced emulsification fixed bed reaction device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1321715A (en) * 1970-05-14 1973-06-27 Nat Res Dev Gas bubble redistribution in fluidised beds
CN1214077A (en) * 1996-03-18 1999-04-14 切夫里昂美国公司 Gas-pocket distributor and method for hydroprocessing hydrocarbon feed stream
CN101668725A (en) * 2007-06-27 2010-03-10 Hrd有限公司 System and process for fischer-tropsch conversion
CN101632911A (en) * 2008-07-24 2010-01-27 中国石油化工股份有限公司 Up-flow reactor and application thereof
CN103666544A (en) * 2012-09-21 2014-03-26 中国石油化工股份有限公司 Hydro-treating method of reformate
CN107497372A (en) * 2016-06-14 2017-12-22 中国石油天然气集团公司 Hydrogenation reactor

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