WO2020155505A1 - 低压气液强化乳化床反应装置及方法 - Google Patents

低压气液强化乳化床反应装置及方法 Download PDF

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WO2020155505A1
WO2020155505A1 PCT/CN2019/090260 CN2019090260W WO2020155505A1 WO 2020155505 A1 WO2020155505 A1 WO 2020155505A1 CN 2019090260 W CN2019090260 W CN 2019090260W WO 2020155505 A1 WO2020155505 A1 WO 2020155505A1
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liquid
gas
bubble
reactor
bubble breaker
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PCT/CN2019/090260
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English (en)
French (fr)
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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院有限公司
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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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • 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
    • C10G45/22—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
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00893—Feeding means for the reactants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1077—Vacuum residues
    • 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

Definitions

  • the invention relates to a low-pressure gas-liquid enhanced emulsified bed reaction device and method.
  • Gas-liquid, gas-liquid-solid and other gas-liquid reaction processes are widely present in the fields of energy, petrochemicals, and fine chemicals.
  • 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.
  • Bubbling reactors and stirred-bubbling reactors are currently commonly used gas-liquid reactors.
  • the bubble diameter is usually larger than 3mm, or even centimeter level, and its mass transfer interface area is limited.
  • the turbulence of the liquid must be promoted by increasing the amount of air blown, so that the burst of the bubbles is aggravated to increase the number of bubbles, and then the interface area is increased. This move will inevitably reduce the gas utilization rate, increase the compressor power and exhaust emissions, resulting in the transition of energy consumption, material loss and environmental pollution.
  • Stirring-bubbling gas-liquid reactors often form large vortices that affect the macroscopic movement of bubbles but have little effect on bubble breaking.
  • the bubbles cannot be effectively broken, so the diameter is too large and the mass transfer area is limited, resulting in low reaction efficiency.
  • tower bubbling reactors In order to strengthen gas-liquid mass transfer, tower bubbling reactors generally add trays, static mixers and other internal parts in the tower to enhance mixing, while stirring tanks need to install different structures of stirring blades or inner cylinders to increase The gas content of the liquid layer.
  • the bubble diameter is usually 3-20mm, and the phase boundary area and mass transfer coefficient (liquid side, gas side, solid-liquid) provided are limited, so it is difficult to achieve breakthrough improvement in reaction performance.
  • 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.
  • d 32 gradually decreases, the volumetric mass transfer coefficient gradually increases; especially when d 32 is less than 1 mm, the volumetric mass transfer coefficient increases exponentially with the decrease of d 32 . Therefore, reducing d 32 to the micron level can greatly enhance the gas-liquid reaction.
  • Bubbles with a diameter between 1 ⁇ m 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.
  • the internal pressure of the bubble is inversely proportional to its radius, so microbubbles are also beneficial to increase the internal pressure of the bubble and increase the solubility of the gas. Therefore, in the gas-liquid reaction process, the micro-interface system can enhance the gas-liquid mass transfer, thereby accelerating the gas-liquid reaction. Microbubbles have rigid characteristics, 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 an emulsification with high phase boundary area and high reaction efficiency is formed in the reactor bed. The formation, operation and utilization of the emulsified bed require a high-performance crusher to divide the gas into micron-sized bubbles.
  • the purpose of the present invention is to provide a gas-liquid enhanced emulsified bed reaction device and method, which is suitable for a gas-liquid reaction system. Utilize the bubble size of the gas-liquid system between 1 ⁇ m and 1mm to form an emulsified system, thereby greatly increasing the gas holdup and gas-liquid mass transfer area of the system, accelerating the multiphase reaction process, increasing the gas utilization rate, and improving the environmental problems caused by excessive emissions. And solve the problems of high temperature, high pressure, high material consumption, high investment, high safety risk and so on in the traditional gas-liquid reaction process, thereby reducing the investment cost and operating cost of the equipment.
  • a low-pressure gas-liquid enhanced emulsified bed reaction device comprising:
  • the main body of the reactor the top of which is provided with a gas-liquid discharge port;
  • At least one bubble breaker is provided with an air inlet, a liquid inlet, and a material outlet, and the material outlet is connected to the reactor body;
  • a gas-liquid separator ; a gas-liquid discharge port connected to the main body of the reactor; an exhaust port is provided at the top of the gas-liquid separator, and a liquid outlet is provided at the bottom;
  • Circulating pump connected to the liquid outlet of the gas-liquid separator
  • Heat exchanger connected to the outlet pipeline of the circulating pump; the heat exchanger is provided with a liquid discharge port, the liquid discharge port is respectively connected with the liquid discharge pipeline and the circulating liquid pipeline, and the circulating liquid pipeline is connected with air bubbles Liquid inlet of the breaker.
  • the bubble breaker of the present invention is divided into pneumatic, hydraulic and gas-liquid linkage types according to the energy input mode or the gas-liquid ratio.
  • the pneumatic bubble breaker is driven by gas, and the input gas volume is much larger than the liquid volume; the hydraulic bubble breaker
  • the device is driven by liquid, and the input gas volume is generally less than the amount of liquid.
  • the gas-liquid linkage bubble breaker is driven by gas and liquid.
  • pneumatic and hydraulic bubble breakers can be connected in series to form a set of bubble breakers.
  • a reaction system can combine multiple bubble breakers in series or in parallel.
  • the bubble breaker can be installed above the main body of the reactor (upper type, gas-liquid emulsion enters the main body from top to bottom), or below the main body (down-mounted type, gas-liquid emulsion enters the main body from bottom to top), or on the side of the main body (Side-mounted, gas-liquid emulsion enters the main body from the side).
  • the three layout forms of the bubble breaker (upper-mounted, lower-mounted and side-mounted) can be used alone, or combined in pairs or all according to needs.
  • the bubble breaker is divided into pneumatic, hydraulic and gas-liquid linkage.
  • the pneumatic bubble breaker is driven by gas, and the input gas volume is much larger than the liquid volume; the hydraulic bubble breaker is driven by liquid.
  • the input air volume is generally less than the liquid volume.
  • the gas-liquid linkage is driven by gas and liquid.
  • pneumatic and hydraulic bubble breakers can be connected in series to form a set of bubble breakers.
  • a reaction system can combine multiple bubble breakers in series or in parallel.
  • the bubble breaker can fully mix the gas and liquid entering it, and the gas and liquid continue to collide, so that the bubbles are crushed, and micro bubbles with an average diameter of 1 ⁇ m-1mm are obtained.
  • the size of the microbubbles in the emulsion is on the micron level, which is similar to rigid beads. It is not easy to aggregate in the main body of the emulsified bed reaction device, and only changes with the consumption of the components in the bubbles or the change of external pressure during the reaction. Therefore, the emulsified bed reaction device can increase the gas-liquid phase boundary area to more than 1000m 2 /m 3 , thereby significantly reducing the multi-phase reaction time and greatly reducing energy consumption and material consumption.
  • a deflector tube is provided in the reactor.
  • the deflector can promote the full mixing of gas and liquid.
  • the upper part of the reactor body is provided with a bubble breaker
  • the upper part is connected to the gas-liquid mixing pipeline with the bubble breaker discharge port of the reactor body, and the gas-liquid emulsion in the upper breaker passes through the gas
  • the liquid mixing pipeline enters the main body of the reactor.
  • the bubble breaker is arranged on the top or side wall of the reactor body; a slag cleaning port is arranged at the lower part of the reactor body.
  • the present invention also provides a low-pressure gas-liquid enhanced emulsified bed reaction method using the above device, which includes:
  • the bubble breaker breaks the material into a micron-sized bubble system, thereby forming a gas-liquid emulsification system, and then enters the reactor body to continue the reaction;
  • the material after the reaction enters the gas-liquid separator from the gas-liquid outlet for gas-liquid separation, the gas is discharged from the exhaust port, and the liquid enters the circulating pump from the liquid outlet, and part of it is extracted after passing through the heat exchanger, and part of the bubble breaks.
  • the device is used for bubble breaking.
  • the method further includes the gas-liquid emulsification system and the solid powder catalyst in the main body of the reactor to form a gas-liquid solid pseudo-emulsification system.
  • the catalyst is a carbon-supported iron-based catalyst, which accounts for 0.2-1% of the mass of the input liquid raw material.
  • the micron-sized bubble system formed in the bubble breaker has an average bubble diameter of 1 ⁇ m-1mm.
  • the device and method of the present invention are suitable for gas-liquid reaction systems. It can reduce the bubble size of the gas-liquid system from the traditional 3-10mm to 1 ⁇ m-1mm, thereby greatly increasing the gas holdup and mass transfer area of the gas-liquid phase boundary, accelerating the multiphase reaction process, and improving the gas utilization rate. , Improve the environmental problems caused by excessive emissions, and solve the problems of high temperature, high pressure, high material consumption and energy consumption, high investment, high risk in the traditional gas-liquid reaction process, thereby reducing equipment investment costs and operating costs.
  • the reaction system of the present invention has relatively small bubbles, resulting in slower gas-liquid separation, so a dedicated high-efficiency gas-liquid separator (such as a suspension separator) needs to be installed after the reactor to realize the separation of microbubbles and liquid.
  • a dedicated high-efficiency gas-liquid separator such as a suspension separator
  • 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 gas-liquid reactor, the present invention has the following advantages:
  • the gas-liquid ratio is generally controlled at 2000-3000:1. 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 schematic diagram of the structure of a low-pressure gas-liquid enhanced emulsified bed reactor (underlying type);
  • Figure 2 is a schematic structural diagram of a low-pressure gas-liquid enhanced emulsified bed reactor (side-mounted type);
  • Figure 3 is a schematic diagram of the structure of a low-pressure gas-liquid enhanced emulsified bed reaction device (top-mounted type);
  • Figure 4 is a schematic diagram of the structure of a low-pressure gas-liquid enhanced emulsified bed reaction device (up and down opposed);
  • the low-pressure gas-liquid enhanced emulsified bed reaction device shown in Figure 1 includes a reactor body 1; the top of which is provided with a gas-liquid discharge port, connected to gas-liquid discharge pipelines 1-8;
  • a set of bubble breakers consists of a hydraulic bubble breaker 1-1 and a pneumatic bubble breaker 1-2 in series.
  • the pneumatic bubble breaker 1-2 is equipped with an air inlet, which is connected to the gas raw material pipeline 1-3; the liquid inlet is connected to the liquid raw material pipeline 1-7; the hydraulic bubble breaker 1-1 is equipped with an inlet
  • the liquid port is connected to the circulating liquid pipeline 4-2; the air inlet is connected to the gas inlet pipeline 1-4 of the hydraulic bubble breaker; the bubble breaker of this embodiment is arranged in the lower part of the reactor body 1;
  • Gas-liquid separator 2 connected to gas-liquid discharge pipelines 1-8; gas-liquid separator 2 is provided with an exhaust port on the top, connected to the exhaust pipeline 2-2, and a liquid outlet at the bottom, connected to the liquid outlet pipeline 2-1;
  • Circulating pump 3 connect the liquid outlet line 2-1;
  • the heat exchanger 4 is connected to the outlet pipe 3-1 of the circulating pump 3; the heat exchanger 4 is provided with a liquid discharge port, which is connected to the liquid discharge pipe 4-1 and the circulating liquid pipe 4-2.
  • the residual oil is sent to the pneumatic bubble breaker 1-2 from the liquid raw material pipeline 1-7; the hydrogen entering from the gas raw material pipeline 1-3 is divided into two ways, one way is through the pneumatic bubble breaker intake pipeline 1-6 It is sent into the pneumatic bubble breaker 1-2 as the breaking driving force, and the other way enters the hydraulic bubble breaker 1-1 through the air bubble breaker air inlet pipe 1-4, and is in the bubble breaker 1-1.
  • the circulating liquid sent from the circulating liquid pipeline 4-2 is broken into primary emulsion, and the obtained primary emulsion enters the pneumatic bubble breaker 1-2 through the primary emulsification pipeline 1-5.
  • the bubble breaker 1-2 hydrogen After fully mixing with residual oil to form microbubbles and gas-liquid emulsification system, it enters the reactor body 1 to form a flat plug flow to continue the reaction.
  • the emulsification system stops in the reactor body for 2.5 hours, and then passes through the top gas-liquid discharge pipeline 1-8 Enter the gas-liquid separator 2, the separated gas is sent to the subsequent treatment through the exhaust pipe 2-2, and the obtained liquid enters the circulating pump 3 through the liquid outlet pipe 2-1.
  • the liquid sent by the circulating pump 3 After the liquid sent by the circulating pump 3 enters the heat exchanger 4 through the outlet pipe 3-1, part of it is sent to the subsequent processing by the liquid discharge pipe 4-1, and the rest is sent to the circulating liquid pipe 4-2 as the bubble breaking power To the hydraulic bubble breaker 1-1.
  • the placement of the bubble breaker can form a flat plug flow emulsified bed reaction system, which is conducive to the improvement of product selectivity.
  • the ratio of gas and liquid raw materials entering the bubble breaker 1-2 in the above device is about 1-2000:1, the operating pressure of the bubble breaker 1-2 is 0.001-100MPa, and the operating temperature is 10-800°C;
  • the ratio of gas and liquid raw materials of the bubble breaker 1-1 is about 0.05-100:1.
  • the operating pressure of the crusher 1-2 is 0.001-100MPa, and the operating temperature is 10-800°C.
  • the bubble breaker 1-1 and 1-2 can be used in combination, or separately as needed.
  • the bubble breaker 1-1 and 1-2 should be used in combination; if the reaction gas-liquid is relatively large (>200), The bubble breaker 1-2 can be used alone; if the gas demand is small or the gas utilization rate is high, the bubble breaker 1-1 can be used alone.
  • the volume ratio of hydrogen to residual oil is 800:1, and it is sent to the pneumatic bubble breaker 1-2 via pipeline 1-6 as the driving force for crushing.
  • the other way uses the volume ratio of hydrogen to residual oil.
  • it enters the hydraulic bubble breaker 1-1 below the side of the emulsion bed reactor 1 through the pipeline 1-4, and is sent by the pipeline 4-2 in the bubble breaker 1-1.
  • the liquid is broken into primary emulsion, and the obtained primary emulsion enters the pneumatic bubble breaker 1-2 through the pipeline 1-5.
  • the gas and liquid are fully mixed to form microbubbles with an average diameter of 300 ⁇ 400 ⁇ m and the gas and liquid
  • the main body of the reaction system that enters the reactor 1 forms a flat plug flow to continue the reaction.
  • the emulsification system stops in the main body of the reactor for a period of time it enters the gas-liquid separator 2 through the top gas-liquid discharge pipeline 1-8 ,
  • the unreacted H 2 obtained from the separation and the H 2 S generated by the reaction are sent to the subsequent treatment via the pipeline 2-2, and the liquid phase oil obtained after hydrodesulfurization enters the circulating pump 3 via the pipeline 2-1.
  • the oil sent by the circulating pump enters the heat exchanger 4 through the pipeline 3-1, part of it is sent to the hydraulic bubble breaker from the pipeline 4-2 as the bubble breaking power, and the rest is sent to the follow-up by the pipeline 4-1 deal with.
  • the reaction pressure in the main body 1 of the emulsion bed reactor is 14 MPa, and the reaction temperature is 440°C.
  • the fixed bed in the reactor body 1 adopts a carbon-supported iron-based catalyst, and the space velocity is controlled to 0.8h -1 .
  • the sulfur content in the raw material residue is 0.2wt.%, which is reduced to 0.05wt.% after the process of the hydrodesulfurization reaction process.
  • the device of this embodiment is shown in Figure 2.
  • the difference from embodiment 1 is that the bubble breaker is arranged on the side of the reactor body 1; the lower part of the reactor body 1 is provided with a slag discharge port, which is connected to the slag cleaning pipeline 1. -9.
  • the liquid raw material is sent from the liquid raw material pipeline 1-7 to the pneumatic bubble breaker 1-2; the gas raw material entering from the gas raw material pipeline 1-3 is divided into two paths, one way is through the pneumatic bubble breaker intake pipeline 1- 6 Feed into the pneumatic bubble breaker 1-2 as the breaking driving force, and the other way enters the hydraulic bubble breaker 1-1 through the hydraulic bubble breaker air inlet pipe 1-4, in the bubble breaker 1-1
  • the circulating liquid sent through line 4-2 is broken into primary emulsion, and the obtained primary emulsion enters the pneumatic bubble breaker 1-2 through the primary emulsion pipeline 1-5, in the pneumatic bubble breaker 1-2
  • the gas-liquid is fully mixed to form microbubbles and gas-liquid emulsification system, it stays in the reactor body for a period of time, and then is sent to the gas-liquid separator 2 through the gas-liquid discharge line 1-8, and the separated gas is passed through the exhaust pipe Route 2-2 is sent to subsequent processing, and the obtained liquid enters the circulating
  • the materials in the reactor can be discharged from the slag cleaning pipeline 1-9 of the reactor body 1.
  • the feature of the side-mounted type is that the gas-liquid emulsion enters the reactor from the side, which can form a vortex in the reactor, which is conducive to macroscopic mass and heat transfer, and accelerates the reaction rate.
  • the ratio of gas and liquid raw materials entering the bubble breaker 1-2 is about 1-2000:1, the operating pressure of the bubble breaker 1-2 is 0.001-100MPa, and the operating temperature is 10-800°C;
  • the ratio of gas and liquid raw materials entering the bubble breaker 1-1 is about 0.05-100:1.
  • the operating pressure of the crusher 1-2 is 0.001-100MPa, and the operating temperature is 10-800°C.
  • the bubble breaker 1-1 and 1-2 can be used in combination, or separately as needed.
  • the bubble breaker 1-1 and 1-2 should be used in combination; if the reaction gas-liquid is relatively large (>200), The bubble breaker 1-2 can be used alone; if the gas demand is small or the gas utilization rate is high, the bubble breaker 1-1 can be used alone. If the reactor has a large volume (>10m 3 ), 2-4 sets of bubble breakers can be arranged on the side and fed into the reactor body from four inlets.
  • the coal tar is sent from pipeline 1-7 to the pneumatic bubble breaker 1-2 installed on the side of the emulsion bed reactor 1; the fresh hydrogen entering from 1-3 is divided into two routes One way is based on the standard of the volume ratio of hydrogen to coal tar of 800:1, and the pneumatic bubble breaker 1-2 is sent to the pneumatic bubble breaker 1-2 through the pipeline 1-6 as the crushing driving force, and the other way is based on the volume ratio of hydrogen to coal tar of 0.3:1 Standard, enter the hydraulic bubble breaker 1-1 on the side of the emulsion bed reactor 1 through the pipeline 1-4, and the circulating liquid sent from the pipeline 4-2 is broken into the primary emulsification in the bubble breaker 1-1 The obtained primary emulsion enters the pneumatic bubble breaker 1-2 through the pipeline 1-5.
  • the gas and liquid are fully mixed to form micro-bubbles with an average diameter of 300-400 ⁇ m and the gas-liquid emulsification system is then entered
  • the main body of the reaction system of the reactor 1 forms a vortex to continue the reaction.
  • the emulsification system stops in the main body of the reactor for a period of time, it enters the gas-liquid separator 2 through the top gas-liquid discharge pipes 1-8.
  • the H 2 generated by the reaction and the H 2 S generated by the reaction are sent to the subsequent treatment through the pipeline 2-2, and the liquid phase oil obtained after hydrodesulfurization enters the circulating pump 3 through the pipeline 2-1.
  • the oil sent by the circulating pump enters the heat exchanger 4 through the pipeline 3-1, part of it is sent to the hydraulic bubble breaker from the pipeline 4-2 as the bubble breaking power, and the rest is sent to the follow-up by the pipeline 4-1 deal with.
  • the reaction pressure in the main body 1 of the emulsion bed reactor is 12 MPa, and the reaction temperature is 440°C.
  • the fixed bed in the reactor body 1 adopts a carbon-supported iron-based catalyst, and the space velocity is controlled to be 1.0 h -1 .
  • the sulfur content in the raw coal tar is 0.4 wt.%, which is reduced to 0.05 wt.% after the process of the hydrodesulfurization reaction process.
  • the device of Example 3 is different from Example 1 in that the bubble breaker is a gas-liquid linkage type bubble breaker 1-12, which is arranged on the upper part of the reactor body 1.
  • the discharge port of the bubble breaker enters the reactor main body 1 through the gas-liquid mixing pipeline 1-10.
  • the reactor main body 1 is vertically provided with a draft tube 1-11; the lower part of the reactor body 1 is provided with a slag discharge port, which is connected with a slag cleaning pipe Road 1-9.
  • the liquid raw material and gas raw material enter the bubble breaker 1-12 through the liquid raw material pipeline 1-7 and the gas raw material pipeline 1-3 respectively, and are sent from the bubble breaker 1-12 through the circulating liquid pipeline 4-2.
  • the circulating liquid is broken into a microbubble gas-liquid system, and the obtained gas-liquid emulsion enters the reactor body 1 through the gas-liquid mixing pipeline 1-10, and then rushes into the guide tube 1-11.
  • the gas-liquid mixture reaches the bottom of the reactor body 1 along the guide tube 1-11, and then moves upward along the wall of the reactor body.
  • a part is drawn into the guide tube at the upper end of the guide tube 1-11 to form a circulating flow, and the rest is self-gassing
  • the liquid discharge pipeline 1-8 is sent to the gas-liquid separator 2, the separated gas is sent to the subsequent treatment via the exhaust pipeline 2-2, and the obtained liquid enters the circulation pump 3 via the liquid discharge pipeline 2-1.
  • the liquid sent by the circulating pump 3 enters the heat exchanger 4 through the outlet pipe 3-1, a part is sent to the subsequent processing by the liquid discharge pipe 4-1, and the rest is sent to the circulating liquid pipe 4-2 as the crushing power Gas-liquid linkage bubble breaker 1-12.
  • the materials in the reactor can be discharged from the slag cleaning pipeline 1-9 at the lower part of the reactor body.
  • the feature of the top-mounted type is that the main body of the reactor is a fully mixed flow type, which is conducive to macroscopic mass and heat transfer, and can accelerate the reaction rate.
  • the ratio of gas and liquid raw materials entering the bubble breaker 1-12 is about 0.05-100:1.
  • the operating pressure of the crusher 1-2 is 0.001-100MPa, and the operating temperature is 10-800°C.
  • the overhead device preferentially uses a gas-liquid linkage bubble breaker.
  • the mixed oil containing 30% residual oil and 70% coal tar and fresh hydrogen enter the bubble breaker through pipelines 1-7 and pipelines 1-3 at a standard volume ratio of 0.3:1.
  • the circulating fluid sent through the pipeline 4-2 is broken into a microbubble gas-liquid system, the average diameter of the microbubbles is 300-400 ⁇ m, and the obtained gas-liquid emulsion is passed through the mixing pipeline
  • 1-10 enters the main body of the reactor, it rushes into the guide tube 1-11.
  • the gas-liquid mixture reaches the bottom of the reactor body along the guide tube 1-11, and then moves upward along the wall of the reactor body.
  • Part of the gas-liquid mixture is drawn into the guide tube at the upper end of the reactor to form a circulating flow, and the rest is flowed from the top pipe 1-8 It is sent to the gas-liquid separator 2, and the unreacted H 2 obtained from the separation and the H 2 S generated by the reaction are sent to the subsequent treatment via the pipeline 2-2, and the liquid phase oil product obtained after the hydrodesulfurization is sent via the pipeline 2- 1 Enter the circulating pump 3. After the oil sent by the circulating pump enters the heat exchanger 4 through the pipeline 3-1, a part is sent to the gas-liquid linkage bubble breaker 1-12 from the pipeline 4-2 as the crushing power, and the rest is sent from the pipeline 4-1. Send it for follow-up processing.
  • the reaction pressure in the main body 1 of the emulsion bed reactor is 13 MPa, and the reaction temperature is 440°C.
  • the fixed bed in the reactor body 1 adopts a carbon-supported iron-based catalyst, and the space velocity is controlled to 0.6h -1 .
  • the sulfur content in the raw material mixed oil is 0.2wt.%, which is reduced to 0.05wt.% after the hydrodesulfurization reaction process is processed.
  • Example 4 The device of Example 4 is shown in Figure 4, and the difference from Example 1 is that the hydraulic bubble breaker 1-1 and the pneumatic bubble breaker 1-2 are respectively arranged on the upper and lower parts of the reactor body 1. , Forming an up and down hedge.
  • the discharge port of the hydraulic bubble breaker 1-1 enters the reactor main body 1 through the gas-liquid mixing pipeline 1-10, and the deflector pipe 1-11 is vertically arranged in the reactor main body 1.
  • the gas raw material entering from the gas raw material pipeline 1-3 is divided into two paths, a part of which enters the pneumatic bubble breaker 1-2 installed at the bottom of the reactor body 1 through the pneumatic bubble breaker inlet pipeline 1-6, and is broken into After the microbubbles, they rise into the main body 1 of the reactor.
  • the liquid raw material and the rest of the gaseous raw materials enter the hydraulic bubble breaker 1-1 through the hydraulic bubble breaker inlet pipe 1-4 and the liquid raw material pipeline 1-7 respectively, and then enter the hydraulic bubble breaker 1-1.
  • the circulating fluid sent through the circulating fluid pipeline 4-2 is broken into a microbubble gas-liquid system, and the obtained gas-liquid emulsion enters the main body of the reactor through the gas-liquid mixing pipeline 1-10, and then rushes into the guide tube 1- 11.
  • the gas-liquid mixture reaches the bottom of the reactor main body 1 along the guide tube 1-11, and is mixed with the microbubble flow generated by the bubble breaker 1-2 installed from the bottom of the reactor main body 1, and then moves upward along the wall surface of the reactor main body 1.
  • part of the rising micro-bubble flow is drawn into the guide tube at the upper end of the guide tube 1-11 to form a circulating flow, and the rest is sent from the gas-liquid discharge pipe 1-8 to the gas-liquid separator 2 to separate the resulting gas It is sent to the subsequent processing via the pipeline 2-2, and the obtained liquid enters the circulation pump 3 via the liquid outlet pipeline 2-1.
  • the liquid sent by the circulating pump enters the heat exchanger 4 through the outlet pipe 3-1, a part is sent to the subsequent treatment by the liquid discharge pipe 4-1, and the rest is sent to the circulating liquid pipe 4-2 as the crushing power Hydraulic bubble breaker 1-1.
  • the characteristic of the upper and lower opposing arrangement of the bubble breaker is that it is suitable for the reactant system with high atmospheric volume and high gas-liquid conversion rate.
  • the deflector cylinders 1-11 in the reactor main body 1 are conducive to macroscopic mass and heat transfer, and can accelerate the reaction rate.
  • the operating pressure of the gas raw material entering the bubble breaker 1-2 is 0.001-100MPa, and the operating temperature is 10-800°C; the ratio of the gas raw material and the liquid raw material entering the bubble breaker 1-1 is about 0.05-100 :1.
  • the operating pressure of the crusher 1-2 is 0.001-100MPa, and the operating temperature is 10-800°C.
  • the fresh hydrogen entering from the gas raw material pipeline 1-3 is divided into two paths, and one part enters the pneumatic crusher at the bottom of the reactor body 1 through the pneumatic bubble breaker inlet pipeline 1-6
  • the vessel 1-2 is broken into micro-bubbles with an average diameter of 300-400 ⁇ m, and then rises into the main body 1 of the reactor.
  • the mixed oil containing 40% residual oil and 60% coal tar and the remaining hydrogen enter the air bubbles through the hydraulic bubble breaker inlet pipe 1-4 and liquid raw material pipe 1-7 at a standard volume ratio of 0.3:1.
  • the circulating liquid sent through the pipeline 4-2 is broken into a micro bubble gas-liquid system, and the obtained gas-liquid emulsion enters the main body of the reactor through the mixing pipeline 1-10 Then, rush into the guide tube 1-11.
  • the gas-liquid mixture reaches the bottom of the reactor body along the guide tube 1-11, and after it collides with the flow of microbubbles generated by the bubble breaker 1-2 installed from the bottom of the reactor body, and then moves upward along the wall of the reactor body.
  • a part of the rising microbubble flow is drawn into the flow guide tube at the upper end of the guide tube 1-1 to form a circulating flow, and the rest is sent to the gas-liquid separator 2 from the top pipeline 1-8 to separate the unreacted H 2 and The H 2 S produced by the reaction is sent to the subsequent treatment via the pipeline 2-2, and the obtained oil product enters the circulation pump 3 via the pipeline 2-1.
  • the liquid sent by the circulating pump enters the heat exchanger 4 through the pipeline 3-1, a part is sent to the hydraulic bubble breaker 1-1 from the pipeline 4-2 as the crushing power, and the rest is sent by the pipeline 4-1
  • the pipeline 4-1 Follow-up processing.
  • the reaction pressure in the main body 1 of the emulsion bed reactor was 13 MPa, and the reaction temperature was 435°C.
  • the fixed bed in the reactor body 1 adopts a carbon-supported iron-based catalyst, and the space velocity is controlled to 0.8h -1 .
  • the sulfur content in the raw material mixed oil is 0.3 wt.%, which is reduced to 0.05 wt.% after the hydrodesulfurization reaction process is processed.

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Abstract

一种低压气液强化乳化床反应装置及方法，该装置包括反应器主体（1）、与反应器主体（1）连接的至少一个气泡破碎器、连接反应器主体（1）气液出料口的气液分离器（2）、循环泵（3）和换热器（4）。气体物料和液体物料首先送入破碎器，气体被破碎为微米级气泡，与液体剧烈混合形成气液乳化物后，进入反应器主体（1）中，由于微气泡低速和难聚并特性，在反应器主体（1）中形成气液乳化床反应体系，反应完成后反应物料进入气液分离器（2）中分离气体和液体，各自收集，进行后续处理。料液由料液泵输送，经过换热器（4）后一部分采出，一部分进入破碎器用于气泡破碎。

Description

低压气液强化乳化床反应装置及方法 技术领域
本发明涉及低压气液强化乳化床反应装置及方法。
背景技术
能源、石化、精细化工等领域广泛存在气液、气液固等气液反应过程。如氧化、加氢、氯化等气液多相反应，其宏观反应速率一般受制于传质过程。气液反应的体积传质系数主要受到传质系数及气液相界面积的共同影响。已有研究表明，相界面积对体积传质系数的影响程度较大，且容易调控。因此，增大相界面积被视为提高气液宏观反应速率的有效途径。
鼓泡反应器和搅拌-鼓泡反应器是目前常用的气液反应器。如PX氧化制TA的塔式鼓泡反应器，气泡直径通常大于3mm，乃至厘米级，其传质界面面积有限。为提高宏观反应速率，必须通过增加鼓气量来促进液体湍流，使气泡破裂加剧以增加气泡数目，进而增大界面面积。而此举必然降低气体利用率，增大压缩机功率和尾气排放，导致能耗过渡和物料损失及环境污染。搅拌-鼓泡式气液反应器内多形成对气泡宏观运动有影响而对气泡破碎影响较小的大涡，气泡不能有效破碎，故直径偏大，传质面积受限，以致反应效率偏低。为强化气液传质，塔式鼓泡反应器一般在塔内增设塔板、静态混合器等内件以加强混合，而搅拌釜则需安装不同结构的搅拌桨或内筒等结构，以增加液层的含气量。这两种反应器，由于所得气泡直径通常为3～20mm，所提供的相界面积和传质系数(液侧、气侧、固液)有限，故反应性能较难获得突破性的提高。
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。d 32逐渐减小时，体积传质系数逐渐增大；特别是当d 32小于1mm时，体积传质系数随d 32的减小以类似于指数形式快速增大。因此，将d 32减小到微米级，能够大幅度强化气液反应。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。根据Yang-Laplace方程，气泡的内压与其半径成反比，故微气泡也有利于提高气泡内压，提高气体的溶解度。因此气液反应过程中，微界面体系能够强化气液传质，进而加快气液反应。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，并在反应器内形成高相界面积，高反应效能的乳化床。乳化床的形成、运行和利用需要高效能的破碎器将气体分割为微米级气泡。
发明内容
本发明的目的是提供一种气液强化乳化床反应装置及方法，适用于含气液反应体系。利 用气液体系1μm～1mm之间的气泡尺度形成乳化体系，从而大幅度地提高体系气含率和气液传质面积，加速多相反应进程，提高气体利用率，改善过量排放造成的环境问题，并解决传统气液反应过程中高温、高压、高物耗、高投资、高安全风险等问题，由此降低设备的投资成本和运行费用。
本发明具体采用如下技术方案实现上述技术目的：
一种低压气液强化乳化床反应装置，包括：
反应器主体；其顶部设有气液出料口；
至少一个气泡破碎器；气泡破碎器上设有进气口、进液口和出料口，出料口连接反应器主体；
气液分离器；连接反应器主体的气液出料口；所述气液分离器顶部设有排气口，底部设有出液口；
循环泵；连接气液分离器的出液口；
换热器；连接循环泵的出口管路；所述换热器上设有液体出料口，液体出料口分别连接液体出料管路和循环液管路，所述循环液管路连接气泡破碎器进液口。
本发明所述的气泡破碎器根据能量输入方式或气液比分为气动式、液动式和气液联动式，其中气动式气泡破碎器采用气体驱动，输入气量远大于液体量；液动式气泡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则是气体和液体共同驱动。采用多个气泡破碎器时，可以将气动式、液动式气泡破碎器串联形成一组气泡破碎器。一个反应体系可以串联或并联的结合多个气泡破碎器。
气泡破碎器可以选择安装在反应器主体的上方(上置式，气液乳化物自上而下进入主体)、或者主体下方(下置式，气液乳化物自下而上进入主体)、或者主体侧面(侧置式，气液乳化物从侧方进入主体)。气泡破碎器的三种布置形式(上置式、下置式和侧置式)可单独使用，也可根据需要两两组合或全部使用。
气泡破碎器根据能量输入方式或气液比分为气动式、液动式和气液联动式，其中气动式气泡破碎器采用气体驱动，输入气量远大于液体量；液动式气泡破碎器采用液体驱动，输入气量一般小于液体量。气液联动式则是气体和液体共同驱动。采用多个气泡破碎器时，可以将气动式、液动式气泡破碎器串联形成一组气泡破碎器。一个反应体系可以串联或并联的结合多个气泡破碎器。气泡破碎器可将进入其中的气体和液体充分混合，气液持续碰撞作用，使气泡被粉碎，得到平均直径在1μm-1mm之间的微气泡。乳化物中微气泡尺度为微米级，类似于刚性小球，在乳化床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。因此乳化床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。需要注意的是，乳化床反应器中，由于气泡比较小，因为气液分离较慢，所以需要在反应器后设置专用的高效气液分离器(如悬液分离器)以实现微气泡与液体的分离。分离后的液体可作为驱动液体由循环泵送至液动式气泡破碎器。
作为本发明的进一步改进，所述反应器内设有导流筒。导流筒可促进气液充分混合。
作为本发明的进一步改进，所述反应器主体上部设有气泡破碎器时，上部与反应器主体的气泡破碎器出料口连接气液混合管路，上部破碎器内的气液乳化物经气液混合管路进入反应器主体。
作为本发明的进一步改进，所述气泡破碎器设置于反应器主体的顶部或侧壁；所述反应器主体下部设置清渣口。
本发明还提供了利用上述装置进行低压气液强化乳化床反应方法，包括：
向气泡破碎器的进气口、进液口分别通入气体物料和液体物料；
气泡破碎器将物料破碎形成微米级气泡体系，从而形成气液乳化体系，之后进入反应器主体继续反应；
反应结束的物料从气液出料口进入气液分离器中进行气液分离，气体从排气口排出，液体由出液口进入循环泵，经过换热器后一部分采出，一部分进入气泡破碎器用于气泡破碎。
作为本发明的进一步改进，所述方法还包括，气液乳化体系在反应器主体中和固体粉末催化剂形成气液固拟乳化体系。优选的，所述催化剂为碳载铁系催化剂，占输入液体原料质量的0.2～1％。
作为本发明的进一步改进，所述气泡破碎器中形成的微米级气泡体系，平均气泡直径为1μm-1mm。
本发明的装置和方法适用于含气液反应体系。它可以将气液体系的气泡尺度由传统的3-10mm，破碎缩小至1μm-1mm，从而大幅度地提高体系气含率和气液相界传质面积，加速多相反应进程，提高气体利用率，改善过量排放造成的环境问题，并解决传统气液反应过程中高温、高压、高物耗能耗、高投资、高风险等问题，由此降低设备的投资成本和运行费用。
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专用的高效气液分离器(如悬液分离器)以实现微气泡与液体的分离。
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。
本发明相较于传统的气液反应器的优点在于：
1.能耗低。传统的固定床气液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成微气泡体系，进而形成乳化床，可大幅增大气液两相的相界面积，达到强化传质的效果。因此可以适当调低压力，从而降低了能耗。
2.气液比低。传统气液反应器为了保证液体原料能充分反应，气液比一般控制在2000-3000:1。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。
3.工艺配置灵活，生产安全性高，吨产品成本低，市场竞争力强。
附图说明
图1为低压气液强化乳化床反应装置(下置式)结构示意图；
图2为低压气液强化乳化床反应装置(侧置式)结构示意图；
图3为低压气液强化乳化床反应装置(上置式)结构示意图；
图4为低压气液强化乳化床反应装置(上下对冲式)结构示意图；
图中：1反应器主体；2气液分离器；3循环泵；4换热器；1-1液动式破碎器；1-2气动式气泡破碎器；1-3气体原料管路；1-4液动式气泡破碎器进气管路；1-5初级乳化液管路；1-6气动式气泡破碎器进气管路；1-7液体原料管路；1-8气液出料管路；1-9清渣管路；1-10气液混合管路；1-11导流筒；1-12-气液联动式气泡破碎器；2-1出液管路；2-2排气管路；3-1出口管路；4-1液体出料管路；4-2循环液管路。
具体实施方式
下面结合附图，对本发明的具体实施方式进一步详细描述。以下实施例用于说明本发明，但不限制本发明的范围。
实施例1
如图1所示的低压气液强化乳化床反应装置，包括反应器主体1；其顶部设有气液出料口，连接气液出料管路1-8；
一组气泡破碎器；由液动式气泡破碎器1-1和气动式气泡破碎器1-2串联组成。气动式气泡破碎器1-2上设有进气口，连接气体原料管路1-3；进液口，连接液体原料管路1-7；液动式气泡破碎器1-1上设有进液口，连接循环液管路4-2；进气口，连接液动式气泡破碎器进气管路1-4；本实施例的气泡破碎器设置于反应器主体1的下部；
气液分离器2；连接气液出料管路1-8；气液分离器2顶部设有排气口，连接排气管路2-2，底部设有出液口，连接出液管路2-1；
循环泵3；连接出液管路2-1；
换热器4；连接循环泵3的出口管路3-1；换热器4上设有液体出料口，连接液体出料管 路4-1和循环液管路4-2。
氢气和常压渣油以一定体积配比分别通过气体原料管路1-3、液体原料管路1-7进入气泡破碎器中。渣油由液体原料管路1-7送到气动式气泡破碎器1-2；从气体原料管路1-3进入的氢气分为两路，一路经气动式气泡破碎器进气管路1-6送入气动式气泡破碎器1-2作为破碎驱动力，另一路经液动式气泡破碎器进气管路1-4进入液动式气泡破碎器1-1，在气泡破碎器1-1内被循环液管路4-2送来的循环液破碎成初级乳化液，所得初级乳化液经初级乳化管路1-5进入气动式气泡破碎器1-2，在气泡破碎器1-2中，氢气和渣油充分混合形成微气泡和气液乳化体系后，进入反应器主体1形成平推流继续反应，乳化体系停在反应器主体内停留2.5h后，经顶部气液出料管路1-8进入气液分离器2中，分离所得气体经排气管路2-2送至后续处理，所得液体经出液管路2-1进入循环泵3。循环泵3送出的液体经出口管路3-1进入换热器4后，一部分由液体出料管路4-1送去后续处理，其余则作为气泡破碎动力由循环液管路4-2送至液动式气泡破碎器1-1。气泡破碎器下置能够形成平推流乳化床反应体系，有利于产物选择性的提高。
上述装置中进入气泡破碎器1-2的气体原料和液体原料的配比约为1-2000:1，气泡破碎器1-2的操作压强为0.001-100MPa，操作温度为10-800℃；进入气泡破碎器1-1的气体原料和液体原料的配比约为0.05-100:1。破碎器1-2的操作压强为0.001-100MPa，操作温度为10-800℃。
气泡破碎器1-1和1-2可以组合使用，也可以根据需要单独使用。如气液反应迅速，放热量大的体系，需要将反应产物循环冷却以降低体系温度时，宜将气泡破碎器1-1和1-2组合使用；若反应气液比较大(>200)，则可单独使用气泡破碎器1-2；若气体需求量小或气体利用率要求高，则可单独使用气泡破碎器1-1。
以加氢脱硫反应为例，氢气与渣油体积比为800：1的标准，经管道1-6送入气动式气泡破碎器1-2作为破碎驱动力，另一路以氢气与渣油体积比为0.3：1的标准，经管路1-4进入乳化床反应器1的侧下方的液动式气泡破碎器1-1，在气泡破碎器1-1内被管路4-2送来的循环液破碎成初级乳化液，所得初级乳化液经管路1-5进入气动式气泡破碎器1-2，在气泡破碎器1-2中，气液充分混合形成平均直径300～400μm的微气泡和气液乳化体系后，进入反应器1的反应***主体形成平推流继续反应，乳化体系停在反应器主体内停留一段时间后，经顶部气液出料管路1-8进入气液分离器2中，分离所得未反应完的H 2和反应生成的H 2S等气体经管路2-2送至后续处理，所得加氢脱硫后的液相油品经管路2-1进入循环泵3。循环泵送出的油品经管路3-1进入换热器4后，一部分作为气泡破碎动力由管路4-2送至液动式气泡破碎器，其余则由管路4-1送去后续处理。
乳化床反应器主体1内反应压力为14MPa，反应温度为440℃。反应器主体1内固定床采用碳载铁系催化剂，空速控制为0.8h -1。原料渣油中硫含量为0.2wt.％，经过本加氢脱硫的反应流程处理之后，降为0.05wt.％。
实施例2
本实施例的装置如图2所示，与实施例1的不同之处在于，气泡破碎器设置于反应器主体1侧部；反应器主体1下部设有排渣口，连接清渣管路1-9。液体原料由液体原料管路1-7送到气动式气泡破碎器1-2；从气体原料管路1-3进入的气体原料分为两路，一路经气动式气泡破碎器进气管路1-6送入气动式气泡破碎器1-2作为破碎驱动力，另一路经液动式气泡破碎器进气管路1-4进入液动式气泡破碎器1-1，在气泡破碎器1-1内被经管路4-2送来的循环液破碎成初级乳化液，所得初级乳化液经初级乳化液管路1-5进入气动式气泡破碎器1-2，在气动式气泡破碎器1-2中，气液充分混合形成微气泡和气液乳化体系后，在反应器主体内停留一段时间，之后经气液出料管路1-8送入气液分离器2中，分离所得气体经排气管路2-2送至后续处理，所得液体经出液管路2-1进入循环泵3。循环泵3送出的液体经出口管路3-1进入换热器4后，一部分由液体出料管路4-1送去后续处理，其余则作为破碎动力由循环液管路4-2送至液动式气泡破碎器。清空时，反应器内的物料可由反应器主体1清渣管路1-9排出。侧置式的特点是气液乳化物从侧面进入反应器，可以在反应器内形成旋涡流，有利于宏观的传质和传热，加快反应速率。
上述装置中，进入气泡破碎器1-2的气体原料和液体原料的配比约为1-2000:1，气泡破碎器1-2的操作压强为0.001-100MPa，操作温度为10-800℃；进入气泡破碎器1-1的气体原料和液体原料的配比约为0.05-100:1。破碎器1-2的操作压强为0.001-100MPa，操作温度为10-800℃。
气泡破碎器1-1和1-2可以组合使用，也可以根据需要单独使用。如气液反应迅速，放热量大的体系，需要将反应产物循环冷却以降低体系温度时，宜将气泡破碎器1-1和1-2组合使用；若反应气液比较大(>200)，则可单独使用气泡破碎器1-2；若气体需求量小或气体利用率要求高，则可单独使用气泡破碎器1-1。如反应器体积较大(>10m 3)，可以在侧面布置2-4套气泡破碎器，从四个进口送入反应器主体内。
以加氢脱硫反应为例，煤焦油由管路1-7送到安装在乳化床反应器1的侧方的气动式气泡破碎器1-2；从1-3进入的新鲜氢气分为两路，一路以氢气与煤焦油体积比为800：1的标准，经管道1-6送入气动式气泡破碎器1-2作为破碎驱动力，另一路以氢气与煤焦油体积比为0.3：1的标准，经管路1-4进入乳化床反应器1的侧方的液动式气泡破碎器1-1，在气泡破碎器1-1内被管路4-2送来的循环液破碎成初级乳化液，所得初级乳化液经管路1-5进入气 动式气泡破碎器1-2，在气泡破碎器1-2中，气液充分混合形成平均直径300～400μm的微气泡和气液乳化体系后，进入反应器1的反应***主体形成旋涡流继续反应，乳化体系停在反应器主体内停留一段时间后，经顶部气液出料管路1-8进入气液分离器2中，分离所得未反应完的H 2和反应生成的H 2S等气体经管路2-2送至后续处理，所得加氢脱硫后的液相油品经管路2-1进入循环泵3。循环泵送出的油品经管路3-1进入换热器4后，一部分作为气泡破碎动力由管路4-2送至液动式气泡破碎器，其余则由管路4-1送去后续处理。
乳化床反应器主体1内反应压力为12MPa，反应温度为440℃。反应器主体1内固定床采用碳载铁系催化剂，空速控制为1.0h -1。原料煤焦油中硫含量为0.4wt.％，经过本加氢脱硫的反应流程处理之后，降为0.05wt.％。
实施例3
实施例3的装置与实施例1不同之处在于，气泡破碎器为气液联动式气泡破碎器1-12，设置于反应器主体1上部。气泡破碎器出料口经气液混合管路1-10进入反应器主体1，反应器主体1内垂直设置导流管1-11；反应器主体1下部设有排渣口，连接清渣管路1-9。
液体原料和气体原料分别经液体原料管路1-7和气体原料管路1-3进入气泡破碎器1-12内，在气泡破碎器1-12内被经循环液管路4-2送来的循环液破碎成微气泡气液体系，所得气液乳化物经气液混合管路1-10进入反应器主体1后，冲入导流筒1-11。气液混合物沿导流筒1-11到达反应器主体1底部，而后沿反应器主体壁面向上运动，一部分在导流筒1-11上端被卷吸入导流筒，形成循环流，其余则自气液出料管路1-8送入气液分离器2中，分离所得气体经排气管路2-2送至后续处理，所得液体经出液管路2-1进入循环泵3。循环泵3送出的液体经出口管路3-1进入换热器4后，一部分由液体出料管路4-1送去后续处理，其余则作为破碎动力由循环液管路4-2送至气液联动式气泡破碎器1-12。清空时，反应器内的物料可由反应器主体下部的清渣管路1-9排出。上置式的特点是反应器主体内为全混流型，有利于宏观的传质和传热，可加快反应速率。
上述装置中，进入气泡破碎器1-12的气体原料和液体原料的配比约为0.05-100:1。破碎器1-2的操作压强为0.001-100MPa，操作温度为10-800℃。
鉴于反应器主体内流体混合需要，上置式装置优先使用气液联动式气泡破碎器。
以加氢脱硫反应为例，含有30％渣油与含有70％煤焦油的混合油品和新鲜氢气以0.3：1的标准体积比分别经管路1-7和管路1-3进入气泡破碎器1-12内，在气泡破碎器1-12内被经管路4-2送来的循环液破碎成微气泡气液体系，微气泡平均直径为300～400μm，所得气液乳化物经混合管路1-10进入反应器主体后，冲入导流筒1-11。气液混合物沿导流筒1-11到达反应器主体底部，而后沿反应器主体壁面向上运动，一部分在反应器上端被卷吸入导流筒， 形成循环流，其余则由顶部管路1-8送入气液分离器2中，分离所得未反应完的H 2和反应生成的H 2S等气体经管路2-2送至后续处理，所得加氢脱硫后的液相油品经管路2-1进入循环泵3。循环泵送出的油品经管路3-1进入换热器4后，一部分作为破碎动力由管路4-2送至气液联动式气泡破碎器1-12，其余则由管路4-1送去后续处理。
乳化床反应器主体1内反应压力为13MPa，反应温度为440℃。反应器主体1内固定床采用碳载铁系催化剂，空速控制为0.6h -1。原料混合油品中硫含量为0.2wt.％，经过本加氢脱硫的反应流程处理之后，降为0.05wt.％。
实施例4
实施例4的装置如图4所示，和实施例1的不同之处在于，液动式气泡破碎器1-1和气动式气泡破碎器1-2分别设置于反应器主体1的上部和下部，形成上下对冲状。液动式气泡破碎器1-1出料口经气液混合管路1-10进入反应器主体1，反应器主体1内垂直设置导流管1-11。
从气体原料管路1-3进入的气体原料分为两路，一部分经气动式气泡破碎器进气管路1-6进入设置在反应器主体1底部的气动式气泡破碎器1-2，破碎成微气泡后，上升进去反应器主体1内。液体原料和其余气体原料分别经液动式气泡破碎器进气管路1-4和液体原料管路1-7进入液动式气泡破碎器1-1内，在液动式气泡破碎器1-1内被经循环液管路4-2送来的循环液破碎成微气泡气液体系，所得气液乳化物经气液混合管路1-10进入反应器主体后，冲入导流筒1-11。气液混合物沿导流筒1-11到达反应器主体1底部，与从反应器主体1底部设置的气泡破碎器1-2产生的微气泡流相向撞击混合后，沿反应器主体1壁面一起向上运动，上升微气泡流一部分在导流筒1-11上端被卷吸入导流筒，形成循环流，其余则自气液出料管路1-8送入气液分离器2中，分离所得气体经管路2-2送至后续处理，所得液体经出液管路2-1进入循环泵3。循环泵送出的液体经出口管路3-1进入换热器4后，一部分由液体出料管路4-1送去后续处理，其余则作为破碎动力由循环液管路4-2送至液动式气泡破碎器1-1。气泡破碎器上下对冲式布置的特点是适合于大气量且气液转化率要求高的反应物系。反应器主体1内的导流筒1-11，有利于宏观的传质和传热，可加快反应速率。
上述装置中，进入气泡破碎器1-2的气体原料操作压强为0.001-100MPa，操作温度为10-800℃；进入气泡破碎器1-1的气体原料和液体原料的配比约为0.05-100:1。破碎器1-2的操作压强为0.001-100MPa，操作温度为10-800℃。
以加氢脱硫反应为例，从气体原料管路1-3进入的新鲜氢气分为两路，一部分经气动式气泡破碎器进气管路1-6进入设置在反应器主体1底部的气动式破碎器1-2，破碎成平均直径300～400μm的微气泡后，上升进入反应器主体1内。含有40％渣油与含有60％煤焦油的混合 油品和其余氢气以0.3：1的标准体积比分别经液动式气泡破碎器进气管路1-4和液体原料管路1-7进入气泡破碎器1-1内，在气泡破碎器1-1内被经管路4-2送来的循环液破碎成微气泡气液体系，所得气液乳化物经混合管路1-10进入反应器主体后，冲入导流筒1-11。气液混合物沿导流筒1-11到达反应器主体底部，与从反应器主体底部设置的气泡破碎器1-2产生的微气泡流相向撞击混合后，后沿反应器主体壁面一起向上运动，上升微气泡流一部分在导流筒1-1上端被卷吸入导流筒，形成循环流，其余则顶部管路1-8送入气液分离器2中，分离所得未反应完的H 2和反应生成的H 2S等经管路2-2送至后续处理，所得油品经管路2-1进入循环泵3。循环泵送出的液体经管路3-1进入换热器4后，一部分作为破碎动力由管路4-2送至液动式气泡破碎器1-1，其余则由管路4-1送去后续处理。
乳化床反应器主体1内反应压力为13MPa，反应温度为435℃。反应器主体1内固定床采用碳载铁系催化剂，空速控制为0.8h -1。原料混合油品中硫含量为0.3wt.％，经过本加氢脱硫的反应流程处理之后，降为0.05wt.％。

Claims (10)

  1. 一种低压气液强化乳化床反应装置，其特征在于，包括：
    反应器主体；其顶部设有气液出料口；
    至少一个气泡破碎器；气泡破碎器上设有进气口、进液口和出料口，出料口连接反应器主体；
    气液分离器；连接反应器主体的气液出料口；所述气液分离器顶部设有排气口，底部设有出液口；
    循环泵；连接气液分离器的出液口；
    换热器；连接循环泵的出口管路；所述换热器上设有液体出料口，液体出料口分别连接液体出料管路和循环液管路，所述循环液管路连接气泡破碎器进液口。
  2. 根据权利要求1所述的装置，其特征在于，所述气泡破碎器设置于反应器主体的顶部、下部或侧壁。
  3. 根据权利要求1所述的装置，其特征在于，所述气泡破碎器为气液联动式气泡破碎器、气动式气泡破碎器、液动式气泡破碎器或其串联组合组成。
  4. 根据权利要求1所述的装置，其特征在于，所述反应器内设有导流筒。
  5. 根据权利要求1所述的装置，其特征在于，所述反应器主体上部设有气泡破碎器时，上部与反应器主体的气泡破碎器出料口连接气液混合管路，上部破碎器内的气液乳化物经气液混合管路进入反应器主体。
  6. 根据权利要求1所述的装置，其特征在于，所述气泡破碎器设置于反应器主体的顶部或侧壁；所述反应器主体下部设置清渣口。
  7. 一种利用权利要求1～6任一项所述装置进行低压气液强化乳化床反应方法，其特征在于，包括：
    向气泡破碎器的进气口、进液口分别通入气体物料和液体物料；
    气泡破碎器将物料破碎形成微米级气泡体系，从而形成气液乳化体系，之后进入反应器主体继续反应；
    反应结束的物料从气液出料口进入气液分离器中进行气液分离，气体从排气口排出，液体由出液口进入循环泵，经过换热器后一部分采出，一部分进入气泡破碎器用于气泡破碎。
  8. 根据权利要求7所述的方法，其特征在于，所述气泡破碎器中形成的微米级气泡体系，平均气泡直径为1μm-1mm。
  9. 根据权利要求7所述的方法，其特征在于，还包括，气液乳化体系在反应器主体中和固体粉末催化剂形成气液固拟乳化体系。
  10. 根据权利要求9所述的方法，其特征在于，所述催化剂为碳载铁系催化剂，所述催 化剂占输入液体原料质量的0.2～1％。
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