WO2022089530A1 - 一种液-液混合器、包括其的液-液反应装置、和使用其的液-液反应方法 - Google Patents

一种液-液混合器、包括其的液-液反应装置、和使用其的液-液反应方法 Download PDF

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WO2022089530A1
WO2022089530A1 PCT/CN2021/127019 CN2021127019W WO2022089530A1 WO 2022089530 A1 WO2022089530 A1 WO 2022089530A1 CN 2021127019 W CN2021127019 W CN 2021127019W WO 2022089530 A1 WO2022089530 A1 WO 2022089530A1
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liquid
microchannel
mixing device
reaction
reactor
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PCT/CN2021/127019
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English (en)
French (fr)
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周峰
马会霞
杨秀娜
乔凯
张淑梅
姜睿
李澜鹏
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中国石油化工股份有限公司
中国石油化工股份有限公司大连石油化工研究院
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Priority to KR1020237017239A priority Critical patent/KR20230112627A/ko
Priority to US18/250,817 priority patent/US20240024830A1/en
Priority to EP21885257.2A priority patent/EP4238641A1/en
Publication of WO2022089530A1 publication Critical patent/WO2022089530A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • 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
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/45—Mixing liquids with liquids; Emulsifying using flow mixing
    • 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
    • B01F25/40—Static mixers
    • B01F25/45—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads
    • B01F25/452—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces
    • B01F25/4524—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces the components being pressed through foam-like inserts or through a bed of loose bodies, e.g. balls
    • B01F25/45242—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces the components being pressed through foam-like inserts or through a bed of loose bodies, e.g. balls through a bed of fibres, steel wool or wood chips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/30—Micromixers
    • B01F33/301—Micromixers using specific means for arranging the streams to be mixed, e.g. channel geometries or dispositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/30—Micromixers
    • B01F33/3035—Micromixers using surface tension to mix, move or hold the fluids
    • B01F33/30351—Micromixers using surface tension to mix, move or hold the fluids using hydrophilic/hydrophobic surfaces
    • 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
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • 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
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/10—Monohydroxylic acyclic alcohols containing three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/12—Monohydroxylic acyclic alcohols containing four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00783—Laminate assemblies, i.e. the reactor comprising a stack of plates
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00788—Three-dimensional assemblies, i.e. the reactor comprising a form other than a stack of plates
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00822—Metal
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00824—Ceramic
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/00819—Materials of construction
    • B01J2219/00831—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention belongs to the technical field of organic chemical industry. Specifically, the present invention relates to a liquid-liquid mixer, a liquid-liquid reaction device comprising the same, and a liquid-liquid reaction method using the same, in particular to an olefin hydration reaction device and an olefin hydration method, a A device for producing biodiesel and a method for obtaining biodiesel by transesterification.
  • the olefin hydration process is a three-phase catalytic reaction of liquid (olefin)-liquid (water)-solid (catalyst), so the reaction rate and conversion rate are greatly affected by liquid-liquid mass transfer.
  • the mutual solubility of the two liquid phases of olefin and water is relatively small, which restricts the reaction efficiency and production capacity of the olefin hydration process.
  • the reactor form of the cyclohexene direct hydration production device currently used in industry is a two-stage series-connected fully mixed tank reactor, and the single-pass conversion rate is low (generally ⁇ 10%), Causes a large amount of unreacted cyclohexene and cyclohexanol to be separated by multiple cycles of rectification, and the energy consumption is high.
  • CN109651081A proposes a reactive distillation method and device for preparing cyclohexanol by hydration of cyclohexene.
  • a phase transfer catalyst is added to the reaction solution, so that cyclohexene, water, catalyst and phase transfer catalyst form a slurry state solution , cyclohexene hydration reaction occurs in the reactive distillation tower to generate cyclohexanol.
  • the reactive distillation method can theoretically greatly improve the conversion rate of cyclohexene and reduce the energy consumption of the system, the hydration reaction rate is slow.
  • US3257469 uses polar organic solvents to increase the mutual solubility of olefins and water, thereby increasing the conversion rate of carbon pentaolefins by increasing the diffusion rate of reactant molecules to the catalyst surface and the diffusion rate of products to the solvent.
  • US4182920 adopts a tertiary olefin hydration reactor, the reaction temperature is 30-80°C, the reaction pressure is 0.46-1.4MPa (absolute pressure), the weight ratio of water/pentene is in the range of 0.59-1.18, and the weight ratio of acetone/pentene is in the range of 0.59-1.18. For 4.18-7.85, the reaction rate is still very slow.
  • CN1304917A adopts the method of isobutene and water countercurrent feeding to enter the tower, and the operation mode that product tert-butanol continuously exits the tower, to improve the two-phase concentration difference, improve the reaction rate and the isobutene conversion rate, but the method has a large water ratio, a space velocity Small size, difficult catalyst formation and other problems.
  • CN02151547.6 provides a method for preparing tert-butanol by hydration reaction with mixed C4 containing isobutene as raw material, in the presence of nonionic surfactant and catalyst, isobutene in the mixed C4 fraction and The water reacts in a catalytic distillation column to form tert-butanol.
  • the preparation method of tert-butanol provided by the invention greatly improves the conversion rate of isobutene and the selectivity of tert-butanol, and reduces the cost of producing tert-butanol.
  • CN98812676.1 provides a method for producing tert-butanol, in order to increase the mutual solubility of mixed C4 and water, tert-butanol is added to the reaction raw materials, and the conversion rate of the reaction can reach 80-90%,
  • This method relies on the action of the centrifugal pump to force the three-phase mixing of tert-butanol, water and liquid carbon tetrahydrocarbons to promote dissolution.
  • the forced mixing by the centrifugal pump method is only macroscopic mixing between phases, and it is difficult to mix microscopically. evenly.
  • Biodiesel has the advantages of good engine starting performance at low temperature, low sulfur content, no aromatic hydrocarbons that pollute the environment, high flash point, good safety performance, high cetane number, and good lubrication performance.
  • the biodiesel production in industry mostly adopts the transesterification method, which uses low-carbon alcohols such as methanol to replace the glycerol in the triglyceride in the raw oil by transesterification under the action of a catalyst to obtain biodiesel; transesterification;
  • the reaction is the core of the whole process, the prior art is mainly based on the triglyceride raw material and methanol as an immiscible system, and the mixing and dissolving of the two phases is relatively difficult, so that the transesterification process has low liquid-liquid mass transfer reaction rate, easy phase separation, There are many problems such as long time for the reaction to reach a given conversion rate.
  • CN1919973A uses a loop turbulent flow reactor to form a set of continuous biodiesel preparation devices.
  • the raw materials enter from the bottom of the loop turbulent flow reactor and react in the loop turbulent flow reactor, and the reacted mixture is removed from the top of the reactor. After discharging, a part of the material returns to the circulating mixing pump and enters the reactor again.
  • the purpose is to realize the repeated forced mixing of the raw materials, which requires a large energy consumption and a special reactor structure to achieve.
  • CN101550349 A method for preparing biodiesel by using supercritical technology.
  • the method converts grease and methanol into a homogeneous phase with an appropriate molar ratio under supercriticality, and carries out transesterification reaction.
  • the control pressure is 8-40MPA and the temperature is 300-450°C. It shortens the time for converting bio-oil into bio-diesel, and improves the reaction efficiency.
  • the supercritical bio-diesel needs to be carried out under high temperature and high pressure conditions, energy consumption and equipment investment are high, and it is easy to cause coke blockage under high temperature conditions. question.
  • CN1952046A proposes a method for producing biodiesel by transesterification.
  • the raw material oil and low-carbon alcohol participating in the reaction are passed into a transesterification reactor equipped with an ultrasonic emission device according to the reaction metering ratio, and the reaction is carried out under suitable conditions.
  • the purpose of the method of the invention is to improve the mutual solubility of raw oil and alcohol through the introduction of ultrasonic waves, improve the mass transfer reaction rate of the immiscible two phases, and shorten the reaction time, but the ultrasonic generation device in this method is difficult to industrialize, and in industrial devices On the realization of the entire mixing system of the material to achieve the same degree of uniformity.
  • CN201625532U discloses a high-shear emulsification reaction device for preparing biodiesel from waste oil, including a reaction kettle, a motor, and an emulsifier.
  • the motor is fixed outside the reaction kettle, and the emulsifier includes a jacket, a rotor and a stator.
  • the outer casing, the rotor and the stator are all coaxial hollow cylinders, one end of the outer casing passes through the outer casing of the reactor and is fixed on the motor casing, and the other end is connected with the stator; one end of the main shaft of the motor is fixedly connected to the rotor;
  • the outer walls of the rotor and the stator are axially provided with a plurality of through-slots penetrating the outer walls, and the rotor is located in the hollow inner cavity of the stator.
  • the utility model mainly performs strong shear emulsification on the reaction material to improve the material mixing. On the one hand, the degree of improvement by mechanical shearing is limited. rate and production efficiency are low.
  • the present invention designs a liquid-liquid mixer.
  • the liquid-liquid mixer of the present invention can be generally applied to liquid-liquid reactions with poor mutual solubility between reaction materials.
  • the liquid-liquid reaction described in the present invention refers to a reaction in which at least two liquid phases are included. Such reactions include but are not limited to liquid-liquid reactions, liquid-liquid-solid reactions, and in particular, the liquid-liquid reactions of the present invention The reaction did not include a gas phase feed stream.
  • the present invention provides a microchannel liquid-liquid mixing device
  • the microchannel liquid-liquid mixing device includes a microchannel component and a housing, the microchannel component is fixed in the housing, and one end of the housing is provided with an inlet , used for feeding at least two reaction liquid phases, and the other end is provided with a mixed material outlet;
  • the microchannel assembly includes a plurality of stacked sheets and lipophilic filaments and hydrophilic filaments filled in the gaps between adjacent sheets, and the fibrous filaments Several micro-channels are formed between the fiber and the fiber, and the fiber is clamped and fixed by the sheet.
  • the microchannel liquid-liquid mixing device is used for at least two reaction liquid phases to form a mixed material, and the at least two reaction liquid phases are cut and mixed by fiber filaments in the microchannel mixing device to form a mixed material.
  • the present invention provides a liquid-liquid reaction device comprising a microchannel mixing device I, a microchannel mixing device II and a reactor;
  • the microchannel mixing device I is of a shell-and-tube structure, and an inorganic membrane tube bundle is arranged inside the shell; the inlet end of the inorganic membrane tube bundle is communicated with the first liquid phase feed line, and the shell cavity outside the inorganic membrane tube bundle is connected to the second liquid.
  • the phase feeding pipeline is connected, and the outlet end of the inorganic membrane tube bundle is the outlet of the mixed material I; the microchannel mixing device I is used for the first liquid phase feed and the second liquid phase feed to form the mixed material I, and the second liquid phase feed is formed by the shell.
  • the inner cavity diffuses into the first liquid phase in the inorganic membrane tube through the pores of the inorganic membrane tube wall, and the two form a uniform mixture I under the shear force of the first liquid phase at a high flow rate in the tube, which is used as the main reaction feed;
  • a control device is provided in the microchannel mixing device 1, so that the ratio of the first liquid phase/second liquid phase is greater than or less than (preferably greater than) the theoretical ratio of the first liquid phase/second liquid phase of the reaction ;
  • the microchannel mixing device II is the microchannel liquid-liquid mixing device of the present invention, which includes a microchannel assembly and a shell, the microchannel assembly is fixed in the shell, and an inlet is provided at one end of the shell for the first liquid phase and the shell. The feed of the second liquid phase, the other end is provided with the mixed material II outlet; the microchannel component includes a plurality of stacked sheets and lipophilic filaments and hydrophilic filaments filled between the adjacent lamellae. Several microchannels are formed, and the fiber filaments are clamped and fixed by thin sheets; the microchannel mixing device II is used for the first liquid phase and the second liquid phase to form a mixed material II, and the first liquid phase and the second liquid phase are in the microchannel mixing device II.
  • the top, bottom or side of the reactor is provided with a feed port, the bottom, top or side is provided with a discharge port, and an intensified mass transfer material inlet is provided on the reactor body.
  • the intensified mass transfer material inlet can be set in the reactor. anywhere within.
  • the outlet of the mixed material I of the microchannel mixing device I is connected to the feed port through a pipeline, and the outlet of the mixed material II of the microchannel mixing device II is connected to the inlet of the enhanced mass transfer material.
  • the present invention provides a method for performing a liquid-liquid reaction using the liquid-liquid reaction apparatus of the present invention.
  • the liquid-liquid reaction includes: emulsion polymerization and suspension polymerization in polymer chemical industry, such as olefin polymerization in organic solvent; olefin hydration reaction; transesterification to produce biodiesel; oil hydrolysis; chemical reactions.
  • the present invention provides an olefin hydration reaction device, comprising a microchannel mixing device I, a microchannel mixing device II and an olefin hydration reactor;
  • the microchannel mixing device I is of a shell-and-tube structure, and an inorganic membrane tube bundle is arranged inside the shell; the inlet end of the inorganic membrane tube bundle is communicated with the water phase pipeline, and the shell cavity outside the inorganic membrane tube bundle is communicated with the olefin phase pipeline.
  • the outlet end of the tube bundle is the outlet of the mixture material I;
  • the microchannel mixing device I is used for the olefin phase and the water phase to form the mixture material I, and the olefin phase diffuses from the cavity in the shell to the water phase in the inorganic membrane tube through the pores of the tube wall of the inorganic membrane tube. Under the shearing force of the high-flow water phase in the tube, the two form a uniform mixture I, as the main reaction feed; wherein water-to-ene ratio ⁇ 1;
  • the microchannel mixing device II includes a microchannel component and a housing, the microchannel component is fixed in the housing, one end of the housing is provided with an inlet for feeding olefin phase and water phase, and the other end is provided with an outlet for mixed material II; the microchannel
  • the component includes a plurality of stacked sheets and lipophilic fiber filaments and hydrophilic fiber filaments filled between the adjacent sheets.
  • Microchannel mixing device II It is used for the olefin phase and the water phase to form a mixed material II, and the olefin phase and the water phase are in the micro-channel mixing device II, and are cut and mixed by the fiber to form the mixed material II; wherein the water-ene ratio is less than 1;
  • the olefin hydration reactor is provided with a feed port at the bottom, a discharge port at the top, an enhanced mass transfer material inlet at the side, a number of catalyst beds are arranged in the reactor, and the enhanced mass transfer material inlet is arranged at any position in the reactor, It is preferably arranged between two adjacent catalyst beds in a more convenient manner; the catalyst beds are filled with olefin hydration catalyst.
  • the outlet of the mixed material I of the microchannel mixing device I is connected to the feed port through a pipeline, and the outlet of the mixed material II of the microchannel mixing device II is connected to the inlet of the enhanced mass transfer material.
  • the present invention strengthens the mass transfer of the entire reaction process by improving the mixed state of olefin and water and the mixed feeding mode, improves the olefin hydration reaction rate and the single-pass conversion rate of raw materials, and reduces the overall Water to olefin ratio, improve the production efficiency of olefin hydration unit.
  • the water-to-olefin ratio described in the present invention is the mass ratio of the water phase to the olefin phase.
  • the overall water-to-olefin ratio refers to the mass ratio of the total amount of water phase added to the total amount of olefin added in the olefin hydration reaction device.
  • the present invention also provides a reaction device for producing biodiesel by transesterification, including a microchannel mixing device I, a microchannel mixing device II and a transesterification reactor;
  • the microchannel mixing device I is of a shell-and-tube structure, and an inorganic membrane tube bundle is arranged inside the shell; the inlet end of the inorganic membrane tube bundle is communicated with a low-carbon alcohol and a liquid catalyst pipeline, and the shell cavity outside the inorganic membrane tube bundle is connected to triglyceride.
  • the ester pipeline is connected, and the outlet end of the inorganic membrane tube bundle is the outlet of the mixture material I; the microchannel mixing device I is used for triglyceride and low-carbon alcohol and the liquid catalyst to form the mixture material I, and the triglyceride passes through the inorganic membrane from the cavity in the shell.
  • the pores of the tube wall diffuse into the low-carbon alcohol and the liquid catalyst in the inorganic membrane tube, and under the shearing force of the high-flow low-carbon alcohol and the liquid catalyst in the tube, the two form a uniform mixture I as the main reaction feed; wherein
  • the molar ratio of low-carbon alcohol to triglyceride is ⁇ 3;
  • the micro-channel mixing device II includes a micro-channel component and a housing, the micro-channel component is fixed in the housing, one end of the housing is provided with an inlet for feeding low-carbon alcohols, liquid catalysts and triglycerides, and the other end is provided with a mixed material II outlet;
  • the microchannel component includes a plurality of stacked sheets and lipophilic fiber filaments and hydrophilic fiber filaments filled in the gaps between adjacent sheets, and several microchannels are formed between the fiber filaments, and the fiber filaments are clamped and fixed by the sheets;
  • the micro-channel mixing device II is used for low-carbon alcohol, liquid catalyst and triglyceride to form mixed material II, and the low-carbon alcohol, liquid catalyst and triglyceride are in the micro-channel mixing device II, and are cut and mixed by fiber filaments to form mixed material II;
  • the molar ratio of low-carbon alcohol to triglyceride is less than 3.
  • the top, bottom or side of the transesterification reactor is provided with a feed port, the bottom, top or side is provided with a discharge port, and the intensified mass transfer material inlet is provided on the reactor body.
  • the intensified mass transfer material inlet can be set at anywhere in the reactor.
  • the outlet of the mixed material I of the microchannel mixing device I is connected to the feed port through a pipeline, and the outlet of the mixed material II of the microchannel mixing device II is connected to the inlet of the enhanced mass transfer material.
  • the reaction device and method for producing biodiesel by the transesterification method of the present invention enhance the mass transfer rate of the entire reaction process and improve the transesterification reaction by improving the mixed state of the triglyceride and the low-carbon alcohol and the mixed feeding mode. rate and single-pass conversion rate of raw materials, shorten the reaction time, and improve the production efficiency of biodiesel production units.
  • the number of microchannel mixing device I and microchannel mixing device II can be set according to actual needs, generally set 1-3 can meet the needs of the reaction.
  • the inorganic membrane tube bundles of the microchannel mixing device I can be one or more of ceramic membranes, metal membranes, metal/ceramic composite membranes, alloy membranes, molecular sieve composite membranes, zeolite membranes or glass membranes, etc.
  • the pore size on the wall of the inorganic membrane tube is 10nm-1 ⁇ m; the particle size d1 of the second liquid phase (such as olefin phase, triglyceride phase) in the mixed material I is 100-900 ⁇ m, preferably 300-500 ⁇ m.
  • the micro-channel components in the shell are divided into a feed end and a discharge end along the direction of the gap, a feed distribution space is set between the material inlet and the feed end, and the space between the material outlet and the discharge end is A discharge distribution space is set between, except for the feed end and the discharge end, the other ends of the micro-channel assembly are sealed with the shell.
  • the microchannel assembly includes a plurality of stacked sheets and lipophilic fiber filaments and hydrophilic fiber filaments filled in the gaps between adjacent sheets, and several microchannels are formed between the fiber filaments and the fiber filaments, and the fiber filaments are clamped and fixed by the sheets. ;
  • the quantity ratio of the lipophilic filaments and the hydrophilic filaments filled between the adjacent slices is 1:50-1:1;
  • the filaments can be arranged in a single layer or multiple layers, preferably 1-50 layers , more preferably 1-5 layers, preferably the hydrophilic filaments in any one layer are evenly distributed between the lipophilic filaments;
  • the quantitative ratio of the lipophilic filaments and the hydrophilic filaments in any one layer is 1: 50-1:1.
  • the projection of the adjacent two layers of fiber filaments along the vertical direction of the sheet is a mesh structure;
  • the mesh shape in the mesh structure can be any shape, such as polygons, circles, ellipses, etc.
  • the spacing between adjacent fiber filaments is generally 0.5 ⁇ m-50 ⁇ m, preferably equidistantly arranged, and the fiber filaments are any one of transverse, longitudinal or oblique directions along the surface of the sheet;
  • the The fiber filaments can be any curved shape, preferably a periodically changing curved shape, such as wave shape, zigzag shape, etc., preferably the shape of the fiber filaments in the same layer is the same, more preferably the shape of the fiber filaments in all layers is the same.
  • the diameter of the filaments is generally 0.5-50 ⁇ m, preferably 0.5-5 ⁇ m, and more preferably 0.5-1 ⁇ m.
  • the lipophilic filaments are generally polyester filaments, nylon filaments, polyurethane filaments, polypropylene filaments, polyacrylonitrile filaments, polyvinyl chloride filaments, or the surface is lipophilic (physical or chemical method).
  • At least one of the treated filaments; the hydrophilic filaments are generally selected from main chain or side chain containing carboxyl group (-COOH), amide group (-CONH-), amino group (-NH 2 -), or hydroxyl group (-OH) and other hydrophilic groups, and the more hydrophilic groups it contains, the better the hydrophilicity.
  • Commonly used ones are polypropylene fibers, polyamide fibers, acrylic fibers, or selected from Material Filaments that have been hydrophilically treated (physically or chemically).
  • the thickness of the sheet is generally 0.05mm-5mm, preferably 0.1-1.5mm.
  • the material of the sheet is generally determined according to the properties of the overflowing material and operating conditions, and can be any one of metal, ceramic, plexiglass, polyester and other materials, preferably stainless steel (SS30403, SS30408, SS32168, SS31603) material among metals.
  • the shape of the sheet can be any one of rectangle, square, polygon, circle, ellipse, sector, etc., preferably rectangle or square. The size and number of flakes can be designed and adjusted according to the actual needs of the reaction.
  • the reactor can be any reactor type, such as a fixed bed reactor, a tank reactor, a tower reactor, a tubular reactor or an improved form of the above-mentioned reactor, and 1 can be set as required.
  • the reactors are connected in parallel or in series; at least one stream of the mixed material formed by the microchannel mixing device II is introduced as an enhanced mass transfer material.
  • the reactor is a fixed-bed reactor, and one or more can be set up as required, and the reactors are connected in parallel or in series; each reactor is set with at least one catalyst Beds, preferably 1-4; at least one stream of the mixed material formed by the micro-channel mixing device II is introduced as an enhanced mass transfer material.
  • the reactor can be any type of reactor, such as a tank reactor, a tower reactor, a tubular reactor or an improved form of the above-mentioned reactor, which can be used as required.
  • One or more are set up, and the reactors are connected in parallel or in series; at least one stream of the mixed material formed by the microchannel mixing device II is introduced as an enhanced mass transfer material.
  • the present invention also provides an olefin hydration method, comprising: mixing an olefin phase with a water-to-ene ratio ⁇ 1 and an aqueous phase through a microchannel mixing device I to form a mixed material I, which is entered from the bottom of the olefin hydration reactor as a main reaction material;
  • the olefin phase and the water phase with an olefin ratio ⁇ 1 are mixed by the microchannel mixing device II to form a mixed material II, which is introduced into the reactor as an enhanced mass transfer material, and the mixed material I and the mixed material II undergo olefin hydration reaction in the catalyst bed, and the reaction product It flows out from the outlet at the top of the reactor and enters the next separation unit.
  • the operating conditions of the microchannel mixing device I are generally as follows: the temperature is at room temperature -250°C, and the pressure is 1.0-10.0 MPaG; the operating conditions of the microchannel mixing device II are generally as follows: the temperature is Normal temperature -200°C, pressure 1.0-10.0MPaG.
  • the olefin phase is generally any one of ethylene, propylene, n-butene, isobutene, isopentene or cyclohexene.
  • the olefin hydration reactor in the method of the present invention, generally adopts the form of bottom-in and top-out, which is beneficial to the uniform contact mass transfer between the olefin and the water.
  • the total water-to-olefin ratio of the olefin hydration reaction is determined according to the type of olefin that occurs in the olefin hydration reaction and the degree of difficulty of the reaction; in the microchannel mixing device I,
  • the mass ratio of water to olefin is generally 2:1-20:1.
  • a properly high water to olefin ratio can ensure the mass transfer reaction rate of the hydration process, but the volume of the reactor is larger, so long as the water phase in the reactor is maintained larger than the olefin phase.
  • the mass ratio of water to alkene is generally 1:20-1:1, and the water to alkene in this material is relatively low, that is, the proportion of alkene is relatively high, and can quickly break through as an enhanced mass transfer material.
  • the phase interface is transferred to the catalyst surface to supplement the olefin consumed by the reaction, so that the catalyst surface always maintains a large amount of olefin/water homogeneous phase rich in olefin molecules, thereby improving the single-pass conversion rate of the olefin hydration reaction.
  • the particle size d1 of the olefin droplets is 100-900 ⁇ m, preferably the dispersion uniformity ⁇ 80%, at this time, When entering the catalyst bed of the reactor to react, it can keep the olefin/water two-phase without phase separation during the reaction residence time, improve the mass transfer reaction rate, and achieve better reaction effect and single-pass conversion rate of olefin raw materials; microchannel mixing In the mixed material II formed by the device II, the particle size d2 of the olefin droplets is less than 100 ⁇ m, preferably 0.1-50 ⁇ m.
  • olefin molecules When introduced between the catalyst beds as an enhanced mass transfer material, due to the small particle size of the olefin and the dense olefin molecules, after the In the case of catalyst particles, olefin molecules can quickly break through the phase interface and transfer to the catalyst surface, which further strengthens the mass transfer of the reaction.
  • the added amount of the mixed material II is 1wt%-30wt% of the total material of the reactor (the total amount of the olefin phase and the water phase); the mixed material II is divided into multiple strands
  • the addition amount of each strand is gradually increased along the flow direction of the material in the reactor (for example, the latter strand is increased by 5-20 wt% relative to the former strand).
  • the water-to-ene ratio can also be reduced or unchanged along the flow direction of the material in the reactor.
  • the olefin molecules, especially the olefin molecules on the catalyst surface are gradually consumed, and the mass transfer driving force of the reaction process gradually decreases. Therefore, by supplementing the enhanced mass transfer material with high olefin content between the catalyst beds, it can quickly break through the phase interface and transfer it to the catalyst surface to replenish the olefins consumed by the reaction in time, so as to maintain a high level. reaction speed.
  • a catalyst with acid catalytic function such as mineral acid, benzene sulfonic acid, ion exchange resin, molecular sieve, etc.
  • acid catalytic function such as mineral acid, benzene sulfonic acid, ion exchange resin, molecular sieve, etc.
  • the olefin hydration reaction conditions are generally: temperature 80-250° C., pressure 1.0-10.0MPaG, space velocity 0.1-3.0h -1 , the reaction conditions required by different olefin raw materials different.
  • the water phase in the reactor is kept larger than the olefin phase at the same time, so as to realize the continuous mass transfer between the olefin phase and the water phase in the reactor;
  • the micro-mixing is carried out in various proportions, so that the droplet size (d1) of the olefin phase in the formed mixed material I is smaller than the droplet size (d2) of the olefin phase in the mixed material II, and the droplet density of the olefin phase in the mixed material I ⁇ Mixture
  • the density of droplets of the olefin phase in the II material so when the mixed material II containing the higher density olefin phase is introduced into the catalyst bed, it can quickly break through the phase interface, quickly replenish the olefin phase consumed by the reaction, and strengthen the
  • the purpose of mass transfer is to improve the olefin hydration reaction rate and the single-pass conversion rate of raw materials, which is beneficial to reduce the water-ene ratio, reduce the number of reactors or the reaction residence time
  • the density of olefin phase droplets refers to the number of olefin microdroplets dispersed in the aqueous phase per unit volume.
  • a certain proportion of metal fiber filaments are filled in the gaps between adjacent sheets, which can adhere and spread the water in the mixed feed of olefin and water along the surface of the fiber filaments, repeating the process. It is forced to be cut into micron-sized particles by filaments.
  • the fully mixed material contains dense olefin droplets and smaller-sized olefin droplets are used as enhanced mass transfer materials, which can quickly break through the phase interface and quickly replenish the olefin phase consumed by the reaction. For the purpose of enhancing mass transfer, reduce the water-ene ratio.
  • the present invention also provides a transesterification reaction method, comprising: mixing two phases with a molar ratio of low-carbon alcohol and triglyceride ⁇ 3 through a microchannel mixing device I to form a mixed material I, which is used as a main reaction material to enter the transesterification reaction Mixing the two phases with the molar ratio of low carbon alcohol and triglyceride ⁇ 3 through the micro-channel mixing device II to form the mixed material II, which is introduced into the reactor as an enhanced mass transfer material, and the mixed material I and the mixed material II are in the reaction
  • the transesterification reaction occurs in the vessel, and the reaction product flows out from the outlet of the reactor and enters the separation unit.
  • the operating conditions of the microchannel mixing device I are generally as follows: the temperature is normal temperature-150 ° C, the pressure is 0.5-3.0MPaG; the operating conditions of the microchannel mixing device II are generally as follows: temperature For normal temperature -150 °C, pressure 0.5-3.0MPaG. Wherein, the amount of the liquid catalyst is 0.5%-10% of the amount of the raw oil and fat.
  • the raw oil is triglyceride, mainly derived from animal oil or vegetable oil; the acid value of the raw oil can be between 0-130mgKOH/g fatty acid and oil (containing waste) oil), preferably refined vegetable oils such as jatropha oil, rapeseed oil, soybean oil, linseed oil, peanut oil, palm oil, and tea seed oil.
  • the aliphatic alcohol whose carbon number of the low-carbon alcohol is 1-6 can be a single fatty alcohol, or a mixture of one or more fatty alcohols, Methanol is preferred.
  • the transesterification reaction adopts an alkaline catalyst
  • the alkaline catalyst can be sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide , one or more mixtures of barium oxide and diethylamine.
  • the transesterification reaction conditions are as follows: the reaction pressure is 0.5-2.0MPaG, the reaction temperature is 100-150°C; the molar ratio of low-carbon alcohol to triglyceride is 1 :3-1:15, the dosage of basic catalyst is 0.5%-10% of the amount of raw oil.
  • the enhanced mass transfer material II may or may not contain a liquid catalyst.
  • the total residence time of the transesterification reactor is 0.5-7 hours, preferably 0.5-3.5 hours; during this time, the conversion rate is ⁇ 98.5%.
  • the molar ratio of low-carbon alcohol and triglyceride is generally 3:1-15:1, and an appropriately high alcohol oil mole
  • the ratio can ensure the mass transfer reaction rate of the transesterification process, but the volume of the reactor is larger, as long as the molar ratio of alcohol to oil in the reactor is maintained ⁇ 3; in the microchannel mixing device II, the molar ratio of alcohol to oil is generally It is 1:10-1:0.33, and the molar ratio of alcohol to oil in this material is low, that is, the proportion of triglycerides is high.
  • Triglyceride As an enhanced mass transfer material, it can quickly break through the phase interface and transfer to the surface of the catalyst to supplement the amount consumed by the reaction. Triglyceride, so that the catalyst surface always maintains a large amount of low-carbon alcohol/triglyceride homogeneous phase rich in triglyceride molecules, thereby improving the transesterification reaction rate and conversion rate.
  • the particle size d1 of the triglyceride droplets is 100-900 ⁇ m, preferably the dispersion uniformity ⁇ 80% , at this time, when entering the reactor, the two phases of low-carbon alcohol/triglyceride can be kept without phase separation during the reaction residence time, the mass transfer reaction rate can be improved, and a better reaction effect and triglyceride can be achieved.
  • Conversion rate; in the mixed material II formed by the microchannel mixing device II, the particle size d2 of the triglyceride droplets is less than 100 ⁇ m, preferably 0.1-50 ⁇ m.
  • the ester particle size is small and the triglyceride molecules are dense. When the transesterification reaction occurs, the triglyceride molecules can quickly break through the phase interface and transfer to the catalyst surface, which can further strengthen the mass transfer of the reaction.
  • the added amount of the mixed material II is 1wt% to 30wt% of the total material of the reactor (the total amount of triglyceride, methanol and liquid catalyst phase);
  • the amount of each strand added gradually increases along the direction from the inlet to the outlet of the material in the reactor (for example, the latter strand is increased by 5-20 wt% relative to the former strand).
  • the lower alcohol/triglyceride molar ratio can also be reduced or unchanged along the direction from the inlet to the outlet in the reactor.
  • the triglyceride molecules are gradually consumed, and the mass transfer driving force of the reaction process gradually decreases, and since the molar amount of low-carbon alcohol in the reactor is much larger than that of the triglyceride phase, so The low concentration of triglyceride molecules leads to the gradual reduction of triglyceride molecules on the catalyst surface. Therefore, by supplementing the enhanced mass transfer material with high triglyceride content between the catalyst beds, the phase interface can be quickly broken through to replenish the energy consumed by the reaction in time. triglycerides, thereby maintaining a high rate of transesterification.
  • both the feedstock oil and methanol are incompatible with each other, the phases are easily separated during the reaction process, the reaction rate is low, the conversion rate is low, and the residence time is low.
  • a kind of efficient transesterification method of the present invention produces the reaction device and method of biodiesel, this method passes through microchannel mixing equipment 1, will most of The raw oil, methanol and liquid catalyst are micro-mixed in a certain proportion, so that the reaction feed can keep two phases uniform and phase-separated during the reaction process in the reactor.
  • the number of moles is greater than the number of moles of triglycerides, so as to realize the continuous mass transfer of triglycerides, methanol and liquid catalysts in the reactor; Micro-mixing is carried out in another ratio, so that the droplet size (d1) of the triglyceride in the resulting mixture I is smaller than the droplet size (d2) of the triglyceride phase in the mixture II, and the droplet size (d2) of the triglyceride phase in the mixture I is Triglyceride Phase Droplet Concentration ⁇ Triglyceride Phase Droplet Concentration in Mixed Feed II, so when Mixed Feed II containing a higher concentration of triglyceride phase is introduced into the reactor, it can be quickly Break through the phase interface and quickly replenish the triglycerides consumed by the reaction, which can enhance the mass transfer, improve the transesterification reaction rate and the conversion rate of raw materials, and is beneficial to reduce the molar ratio of low-carbon alcohol/triglyceride and reduce the number
  • triglyceride droplet density refers to the number of triglyceride microdroplets dispersed in the methanol and liquid catalyst mixture per unit volume.
  • a certain proportion of metal fiber filaments are filled between the gaps between adjacent sheets, which can mix the water in the feed with triglyceride, methanol and liquid catalyst along the surface of the fiber filaments. Adhesion, spreading, and repeated forced cutting into micron-sized particles by filaments.
  • the well-mixed material contains dense olefin droplets and smaller-sized triglyceride droplets as the enhanced mass transfer material, which can quickly break through the phase interface and quickly
  • the oil consumed by the reaction is supplemented to enhance mass transfer and reduce the molar ratio of total methanol to triglyceride.
  • Figure 1A is a schematic diagram of the olefin hydration reaction apparatus of the present invention.
  • FIG. 1B is a schematic diagram of the microchannel components in the microchannel mixing device II
  • FIG. 2A is a schematic diagram of a reaction device for producing biodiesel by the transesterification method of the present invention.
  • 2B is a schematic diagram of the microchannel components in the microchannel mixing device II
  • 1A is taken as an example to illustrate the olefin hydration reaction device and the olefin hydration method of the present invention:
  • the olefin phase 101 and the water phase 102 are introduced into the microchannel mixing device I 103 at a ratio of water-ene ratio ⁇ 1 to form a mixed material I 107, wherein the olefin phase 101 is introduced into the shell space 6 of the microchannel mixing device I 103, and the water phase is 102 is introduced into the inorganic membrane tube bundle 105 of the microchannel mixing device I 103, the olefin phase 101 penetrates into the tube from the outside of the tube through the tube wall of the inorganic membrane tube, and the two are forcedly mixed under the high-speed shearing action of water to form a mixed material I 107 , enter the olefin hydration reactor 121 as the main reaction material, and react in the catalyst bed; another part of the olefin phase II 108 and the water phase II 109 are introduced into the microchannel mixing device II 110 at a ratio of water to olefin ratio ⁇ 1, and after passing through the microchannel
  • the olefin hydration reactor of the present invention is respectively applied to the hydration reactions of propylene, n-butene, isobutene and cyclohexene.
  • For specific reaction conditions see Comparative Example 1-1, Comparative Example 1-2, Comparative Example 1-3, Comparative Example 1-4, Example 1-1, Example 1-2, Example 1-3, Example 1- 4. Examples 1-5 and 1-6.
  • the olefin raw materials are commercially available, and the specific properties are shown in Table 1-1, Table 1-2, and Table 1-3 respectively.
  • the catalyst used for the hydration of propylene is DIAP type catalyst produced by Dandong Mingzhu Special Resin Co., Ltd.
  • the catalyst used for n-butene hydration is DNW-II type catalyst produced by Dandong Mingzhu Special Resin Co., Ltd.
  • the catalyst used for isobutene hydration is Dandong Mingzhu DT-017 type catalyst produced by Special Resin Co., Ltd.
  • the catalyst used for hydration of cyclohexene is Amberlyst 36 type resin catalyst.
  • the n-butene hydration reaction occurs with water under the action of a catalyst to prepare isopropanol.
  • the propylene raw material and water pass through a conventional static mixer, the model is SL-1.6/25-10.0-200, and the mixed material of the two enters the propylene hydration reactor for hydration reaction.
  • the mixing conditions were as follows: the temperature was 155°C, and the pressure was 8.0 MPa.
  • the reactor adopts an ordinary up-flow reactor, and three stages of catalyst beds are arranged in the reactor, and a distribution sieve plate is arranged at the inlet of each stage of the catalyst bed, and the aperture of the sieve plate is 3 mm.
  • the olefin/water mixture material is introduced into the olefin hydration reactor from the bottom of the reactor, and is uniformly distributed along the cross section of the reactor through the distribution sieve plate, then enters the catalyst bed for olefin hydration reaction, and finally leaves the olefin hydration reactor through the outlet at the top of the reactor. .
  • the reaction product was obtained through the propylene hydration reactor.
  • the reaction conditions, residence time and conversion rate of the raw materials are shown in Table 1-4.
  • the n-butene hydration reaction occurs with water under the action of a catalyst to prepare sec-butanol.
  • the n-butene raw material and water pass through a conventional static mixer, the model is SL-1.6/25-10.0-250, and are continuously mixed for three times, and the mixed material enters the n-butene hydration reactor for hydration reaction.
  • the mixing conditions were as follows: the temperature was 175°C, and the pressure was 8.0 MPa.
  • the reactor adopts an ordinary up-flow reactor, and four stages of catalyst beds are arranged in the reactor, and the inlet of each stage of catalyst beds is provided with a distribution sieve plate, and the aperture of the sieve plate is 2 mm.
  • the n-butene/water mixture material is introduced into the olefin hydration reactor from the bottom of the reactor, and after the distribution sieve plate is evenly distributed along the cross section of the reactor, it enters the catalyst bed for olefin hydration reaction, and finally leaves the olefin hydration reaction from the outlet at the top of the reactor. reactor.
  • the reaction product was obtained through the n-butene hydration reactor, and the reaction conditions, residence time and raw material conversion rate were shown in Table 1-4.
  • the isobutene hydration reaction with water under the action of a catalyst was carried out to prepare tert-butanol.
  • the isobutene raw material and water pass through a conventional static mixer, the model is SL-1.6/25-5.-200, and the mixed material of the two enters the isobutene hydration reactor for hydration reaction.
  • the mixing conditions were as follows: the temperature was 105°C, and the pressure was 2.6 MPa.
  • the reactor adopts an ordinary up-flow reactor, and two stages of catalyst beds are arranged in the reactor, and a distribution sieve plate is arranged at the inlet of each stage of the catalyst bed, and the aperture of the sieve plate is 3 mm.
  • the isobutene/water mixture material is introduced into the olefin hydration reactor from the bottom of the reactor, and after the distribution sieve plate is evenly distributed along the reactor cross-section, it enters the catalyst bed for olefin hydration reaction, and finally leaves the olefin hydration reactor through the outlet at the top of the reactor. .
  • isopropanol is prepared by hydration reaction of propylene with water under the action of a catalyst.
  • the water-alkene mass ratio is introduced into the microchannel mixing device 1 at a ratio of 12:1 to form a mixture material I, which enters the alkene hydration reactor as the main reaction material and reacts in the catalyst bed; the water-alkene mass ratio is in a ratio of 1:7.5
  • the mixed material II is formed through the microchannel mixing device II, and is introduced into the catalyst bed as an enhanced mass transfer material to strengthen the olefin hydration reaction process, and the reaction effluent leaves the reactor and enters the next separation unit.
  • the reactor adopts the reactor of the present invention, the bottom is in and the top is out, three-stage catalyst beds are arranged in the reactor, and an enhanced mass transfer is introduced between the first/second catalyst bed and the second/third catalyst bed.
  • Mixed material II the addition amount of mixed material II is 3.6 wt% of the total material of the reactor (the total amount of olefin phase and water phase), and the amount introduced between the first/second catalyst bed and the second/third catalyst bed
  • the ratio of mixture II is 1:1.5.
  • the flakes in the microchannel mixing component are made of stainless steel, the thickness of the flakes is 1.2 mm, and the gaps between the flakes are filled with 5 layers of metal fiber filaments with a diameter of 5 ⁇ m and a layer of ceramic fiber filaments with a diameter of 5 ⁇ m. Equally spaced, with a pitch of 1 ⁇ m.
  • the filaments are in the shape of a wavy line that changes periodically.
  • the operating conditions of the microchannel mixing device I are as follows: the temperature is 150°C and the pressure is 7.5 MPaG; the operating conditions of the microchannel mixing device II are as follows: the temperature is 125°C and the pressure is 7.0 MPaG.
  • reaction raw materials, the reactor structure, the reaction process, the operating conditions of the microchannel mixing device I, and the operating conditions of the microchannel mixing device II are the same as those in Example 1-1. Different from Example 1-1, this example adopts more moderate reaction conditions. Reaction conditions, residence time and raw material conversion are shown in Table 1-4.
  • the n-butene hydration reaction occurs with water under the action of a catalyst to prepare sec-butanol.
  • the water-alkene mass ratio is introduced into the microchannel mixing device 1 at a ratio of 3:1 to form a mixture material I, which enters the alkene hydration reactor as the main reaction material and reacts in the catalyst bed; the water-alkene mass ratio is in a ratio of 1:2
  • the mixed material II is formed through the microchannel mixing device II, and is introduced into the catalyst bed as an enhanced mass transfer material to strengthen the olefin hydration reaction process, and the reaction effluent leaves the reactor and enters the next separation unit.
  • the reactor adopts the reactor of the present invention, the bottom is in and the top is out, and four catalyst beds are arranged in the reactor, between the first/second catalyst bed, the second/third catalyst bed, and the third/fourth catalyst.
  • the enhanced mass transfer mixture II was introduced between the beds respectively, and the addition amount of the mixture II was 4.0 wt% of the total material of the reactor (the total amount of the olefin phase and the water phase), the first/second catalyst bed, the second/second catalyst
  • the ratio of the mixture II introduced between the third catalyst bed and the third/fourth catalyst bed is 1:1.2:1.5.
  • the slices in the microchannel mixing component are made of stainless steel, the thickness of the slices is 1.0mm, and the gaps between the slices are filled with 3 layers of glass fiber filaments with a diameter of 1 ⁇ m and a layer of ceramic fiber filaments with a diameter of 5 ⁇ m. Equally spaced, with a pitch of 1 ⁇ m.
  • the filaments are in the shape of a wavy line that changes periodically.
  • the operating conditions of the microchannel mixing device I are as follows: the temperature is 175°C and the pressure is 7.8 MPaG; the operating conditions of the microchannel mixing device II are as follows: the temperature is 135°C and the pressure is 7.0 MPaG.
  • reaction raw materials, the reactor structure, the reaction process, the operating conditions of the microchannel mixing device I, and the operating conditions of the microchannel mixing device II are the same as those in Examples 1-3. Different from Examples 1-3, this example adopts more moderate reaction conditions. Reaction conditions, residence time and raw material conversion are shown in Table 1-4.
  • the isobutene hydration reaction with water under the action of a catalyst was carried out to prepare tert-butanol.
  • the water-alkene mass ratio is introduced into the microchannel mixing device 1 at a ratio of 4:1 to form a mixed material I, which enters the alkene hydration reactor as the main reaction material, and reacts in the catalyst bed; the water-alkene mass ratio is in a ratio of 1:1.62
  • the mixed material II is formed through the microchannel mixing device II, and is introduced into the catalyst bed as an enhanced mass transfer material to strengthen the olefin hydration reaction process, and the reaction effluent leaves the reactor and enters the next separation unit.
  • the reactor adopts the reactor of the present invention, the bottom is in and the top is out, two-stage catalyst beds are arranged in the reactor, and the enhanced mass transfer mixture II is introduced between the first/second catalyst beds, and the amount of the mixture II added is the reactor
  • the ratio of the mixed material II introduced between the first/second catalyst bed and the second/third catalyst bed is 1:1.5 based on 2.0 wt% of the total material (the total amount of the olefin phase and the water phase).
  • the flakes in the microchannel mixing component are made of stainless steel, the thickness of the flakes is 1.5 mm, and the gaps between the flakes are filled with 8 layers of stainless steel fiber filaments with a diameter of 5 ⁇ m and 2 layers of ceramic fiber filaments with a diameter of 5 ⁇ m. Equally spaced, with a pitch of 1 ⁇ m.
  • the filaments are in the shape of a wavy line that changes periodically.
  • the operating conditions of the microchannel mixing device I are as follows: the temperature is 105°C and the pressure is 2.8 MPaG; the operating conditions of the microchannel mixing device II are as follows: the temperature is 85°C and the pressure is 2.1 MPaG.
  • reaction raw materials, the reactor structure, the reaction process, the operating conditions of the microchannel mixing device I, and the operating conditions of the microchannel mixing device II are the same as those in Examples 1-5. Different from Examples 1-5, this example adopts more moderate reaction conditions. Reaction conditions, residence time and raw material conversion are shown in Table 1-4.
  • the dispersion size and dispersion effect of the olefin droplets in the water in the method of the present invention are obtained by a high-speed camera, and the uniformity of the dispersed phase particles is obtained by selecting several characteristic particles. The smaller the particle size, the higher the uniformity. It shows that the effect of mixing and dispersing is better.
  • the method for measuring the mixing and dispersing effect of the present embodiment and the comparative example is: under the same conditions, through different mixing and dispersing methods (such as using a conventional static mixer, the microchannel mixing system I and the microchannel mixing system II in the reactor of the present invention) )
  • Mix the dispersed phase olefin and the continuous phase aqueous phase at least 10 groups of mixed material samples are obtained in each group of methods, and the British IX i-SPEED 5 high-speed camera is used to photograph the particle size of the dispersed phase in the mixed material sample, and the particles in the photo are taken. Add up, calculate the percentage of particles of various sizes, and obtain the normal distribution diagram of particles of various sizes, thereby obtaining particle uniformity.
  • the olefin hydration reaction device and the reaction method of the present invention are adopted, and are introduced from the bottom of the reactor as the main reaction material, so that the reaction feed is kept two-phase uniform in the reactor, which is an olefin.
  • the high conversion rate of the hydration reaction provides the precondition, and then another part of the olefin and water is formed into the mixed feed II through the micro-channel mixing device II under the condition that the water-to-ene ratio is less than 1, and is introduced into the catalyst bed as an enhanced mass transfer material.
  • the mixed feed II due to the small size of the olefin droplets and the dense olefin molecules, it can quickly break through the phase interface and replenish the olefin phase consumed by the reaction, thereby greatly enhancing the mass transfer of the entire reaction process, improving the olefin hydration reaction rate and the single-pass conversion of raw materials. rate, reduce the water-ene ratio, reduce the number of reactors or the reaction residence time, and improve the production efficiency of the olefin hydration unit.
  • FIG. 2A Take Fig. 2A as an example to illustrate the reaction device and method for producing biodiesel by transesterification of the present invention:
  • the triglyceride 201, the low-carbon alcohol and the liquid catalyst 202 are introduced into the micro-channel mixing device I 203 at a ratio of a low-carbon alcohol/triglyceride molar ratio ⁇ 3 to form a mixed material I 207, wherein the triglyceride 201 Introduced into the shell space 206 of the microchannel mixing device I 203, the low-carbon alcohol and the liquid catalyst 202 were introduced into the inorganic membrane tube bundle 205 of the microchannel mixing device I 203, and the triglyceride 201 penetrated from the outside of the tube to the tube wall of the inorganic membrane tube.
  • the slits 214 between the channel sheets 213 are continuously cut by the hydrophilic fibers 215 and lipophilic fibers 216 filled between the slits 214 to form a mixture II 217, which are respectively used as the enhanced mass transfer material 218 and the enhanced mass transfer material 219 ,
  • the enhanced mass transfer material 220 is introduced into the transesterification reactor 221, so that the enhanced mass transfer material can quickly replenish the triglycerides consumed in the reaction process, thereby achieving the purpose of enhancing mass transfer, and the material that completes the transesterification reaction is used as the reaction Product 222 leaves.
  • the raw material triglyceride used in Comparative Examples and Examples of the present invention is tung oil, and its properties are shown in Table 1.
  • the raw materials for the transesterification reaction are raw oil, methanol and basic catalyst (see Table 1 for the properties of the raw oil).
  • the raw oil, methanol and basic catalyst are introduced into the stirred tank for After stirring and mixing for 15-20 minutes, the feed pump is used to drive into a two-stage reactor for transesterification, wherein the first-stage reactor is a tower reactor, and the size of the reactor is The secondary reactor is a tubular reactor, and the size of the reactor is
  • the reactor operating conditions are as follows:
  • Feeding amount of raw material oil 1.5kg/h;
  • the reaction temperature is 120°C-125°C
  • the reaction pressure is 2.0MPaG
  • the base catalyst accounts for the mass fraction of raw oil and fat: 2.5%.
  • the conversion rate of the raw materials at the outlet of the primary reactor was 75.2%, and the conversion rate of the raw materials at the outlet of the secondary reactor was 87.4%;
  • the exchange reaction residence time (based on total material) was 3.44 hours.
  • a conventional biodiesel product transesterification reaction device and reaction method are adopted.
  • the raw materials for the transesterification reaction are raw oil, methanol and basic catalyst (see Table 1 for the properties of the raw oil).
  • the raw oil, methanol and basic catalyst are introduced into the impingement flow for reaction.
  • the feed pump is used to drive the two-stage reactor into a two-stage reactor for transesterification, wherein the first-stage reactor is a tower reactor, and the size of the reactor is The secondary reactor is a tubular reactor, and the size of the reactor is
  • the reactor operating conditions are as follows:
  • the reaction temperature is 120°C-125°C
  • the reaction pressure is 2.0MPaG
  • the base catalyst accounts for the mass fraction of raw oil and fat: 2.5%.
  • the conversion rate of the raw materials at the outlet of the primary reactor was 87.2%, and the conversion rate of the raw materials at the outlet of the secondary reactor was 90.5%;
  • the exchange reaction residence time (based on total material) was 2.87 hours.
  • the raw materials for the transesterification are raw oil, methanol and an alkaline catalyst (see Table 1 for the properties of the raw oil), and the three of the raw oil, methanol and alkaline catalyst are introduced into the microchannel mixing device I, wherein The raw oil/methanol is 6:1 with a molar ratio, and the raw oil is introduced into the shell side of the microchannel mixing device 1, and methanol and the liquid alkali catalyst are introduced into the tube side of the microchannel mixing device 1.
  • the mixture formed by the microchannel mixing device 1 Material I enters the two-stage transesterification reactor as the main reaction material, and transesterification reaction occurs, wherein the first-stage reactor is a tower reactor, and the size of the reactor is The secondary reactor is a tubular reactor, and the size of the reactor is The raw oil and methanol are formed into a mixed material II through a micro-channel mixing device II in a molar ratio of 1:1, and are introduced into the tower reactor and the tubular reactor as an enhanced mass transfer material to strengthen the transesterification process. The reaction effluent leaves the reactor and enters a separation unit.
  • the flakes in the microchannel mixing component are made of stainless steel, the thickness of the flakes is 1.2 mm, and the gaps between the flakes are filled with 5 layers of metal fiber filaments with a diameter of 5 ⁇ m and a layer of ceramic fiber filaments with a diameter of 5 ⁇ m. Equally spaced, with a pitch of 1 ⁇ m.
  • the filaments are in the shape of a wavy line that changes periodically.
  • the operating conditions of the transesterification reaction process are as follows:
  • Reaction temperature 120°C-125°C
  • the mass fraction of the base catalyst in the raw oil 2.5%
  • the process-enhancing mass transfer material added to the tower reactor was 25.6 wt% of the total reaction feed, and the process-enhancing mass transfer material added to the tubular reactor was 5.2 wt% of the total reaction feed.
  • the operating conditions of the microchannel mixing device I are as follows: the temperature is 120-125°C, and the pressure is 2.0 MPaG; the operating conditions of the microchannel mixing device II are as follows: the temperature is 120°C, and the pressure is 2.0 MPaG.
  • the conversion rate of raw materials in the primary transesterification reaction was 96.30%, and that in the secondary transesterification reaction was 98.7%; the residence time of the primary transesterification reaction was 0.87 hours, and the residence time of the secondary transesterification reaction was 0.87 hours. is 1.11 hours.
  • reaction raw materials, the reactor structure, the reaction process, the operating conditions of the microchannel mixing device I, and the operating conditions of the microchannel mixing device II are the same as those in Example 2-1.
  • this example changes the transesterification reaction conditions on the one hand, and appropriately adjusts the introduction position and introduction amount of the enhanced mass transfer material on the other hand.
  • the operating conditions of the transesterification reaction process are as follows:
  • Reaction temperature 120°C-125°C
  • the mass fraction of the base catalyst in the raw oil 2.5%
  • the process-enhancing mass transfer material added to the tower reactor was 16.6 wt% of the total reaction feed, and the process-enhancing mass transfer material added to the tubular reactor was 8.0 wt% of the total reaction feed.
  • the conversion rate of raw materials in the primary transesterification reaction was 97.10%, and that in the secondary transesterification reaction was 98.8%; the residence time of the primary transesterification reaction was 0.87 hours, and the residence time of the secondary transesterification reaction was 0.87 hours. is 1.11 hours.
  • the raw materials for the transesterification are raw oil, methanol and an alkaline catalyst (see Table 1 for the properties of the raw oil), and the three of the raw oil, methanol and alkaline catalyst are introduced into the microchannel mixing device I, wherein The raw oil/methanol is 5:1 with a molar ratio, the raw oil is introduced into the shell side of the microchannel mixing device 1, methanol and the liquid alkali catalyst are introduced into the tube side of the microchannel mixing device 1, and the mixture formed by the microchannel mixing device 1
  • Material I enters the two-stage transesterification reactor as the main reaction material, and transesterification reaction occurs, wherein the first-stage reactor is a tower reactor, and the size of the reactor is The secondary reactor is a tubular reactor, and the size of the reactor is
  • the raw material oil and methanol are formed into a mixed material II through a micro-channel mixing device II in a molar ratio of 1:2, and are introduced into the tower reactor and the tubular reactor as
  • the slices in the microchannel mixing component are made of stainless steel, the thickness of the slices is 1.0mm, and the gaps between the slices are filled with 3 layers of glass fiber filaments with a diameter of 1 ⁇ m and a layer of ceramic fiber filaments with a diameter of 5 ⁇ m. Equally spaced, with a pitch of 1 ⁇ m.
  • the filaments are in the shape of a wavy line that changes periodically.
  • the operating conditions of the transesterification reaction process are as follows:
  • Reaction temperature 120°C-125°C
  • the mass fraction of the base catalyst in the raw oil 2.5%
  • the process-enhancing mass transfer material added to the tower reactor was 20.0 wt% of the total reaction feed, and the process-enhancing mass transfer material added to the tubular reactor was 3.6 wt% of the total reaction feed.
  • the operating conditions of the microchannel mixing device I are as follows: the temperature is 120-125°C, and the pressure is 2.0 MPaG; the operating conditions of the microchannel mixing device II are as follows: the temperature is 120°C, and the pressure is 2.0 MPaG.
  • the conversion rate of the raw materials in the primary transesterification reaction was 97.0%, and the conversion rate of the raw materials in the secondary transesterification reaction was 98.9%; the residence time of the primary transesterification reaction was 1.01 hours, and the residence time of the secondary transesterification reaction was 1.01 hours. 1.30 hours.
  • reaction raw materials, the reactor structure, the reaction process, the operating conditions of the microchannel mixing device I, and the operating conditions of the microchannel mixing device II are the same as those in Example 2-3. Different from Examples 2-3, this example changes the feed amount and transesterification reaction conditions on the one hand, and appropriately adjusts the introduction position and introduction amount of the enhanced mass transfer material on the other hand.
  • the operating conditions of the transesterification reaction process are as follows:
  • Reaction temperature 120°C-125°C
  • the mass fraction of base catalyst in raw oil 3.0%;
  • the process-enhancing mass transfer material added to the tower reactor was 22.4 wt% of the total reaction feed, and the process-enhancing mass transfer material added to the tubular reactor was 3.2 wt% of the total reaction feed.
  • the conversion rate of raw materials in the primary transesterification reaction was 96.8%, and that in the secondary transesterification reaction was 99.1%; the residence time of the primary transesterification reaction was 1.01 hours, and the residence time of the secondary transesterification reaction was 1.01 hours. 1.30 hours.
  • the raw materials for the transesterification are raw oil, methanol and an alkaline catalyst (see Table 1 for the properties of the raw oil), and the three of the raw oil, methanol and alkaline catalyst are introduced into the microchannel mixing device I, wherein The raw oil/methanol is 8:1 with a molar ratio, and the raw oil is introduced into the shell side of the microchannel mixing device 1, and methanol and the liquid alkali catalyst are introduced into the tube side of the microchannel mixing device 1.
  • the mixture formed by the microchannel mixing device 1 Material I enters the two-stage transesterification reactor as the main reaction material, and transesterification reaction occurs, wherein the first-stage reactor is a tower reactor, and the size of the reactor is The secondary reactor is a tubular reactor, and the size of the reactor is The raw oil and methanol are formed into a mixed material II through a micro-channel mixing device II in a molar ratio of 1:1, and are introduced into the tower reactor and the tubular reactor as an enhanced mass transfer material to strengthen the transesterification process. The reaction effluent leaves the reactor and enters a separation unit.
  • the flakes in the microchannel mixing component are made of stainless steel, the thickness of the flakes is 1.5 mm, and the gaps between the flakes are filled with 8 layers of stainless steel fiber filaments with a diameter of 5 ⁇ m and 2 layers of ceramic fiber filaments with a diameter of 5 ⁇ m. Equally spaced, with a pitch of 1 ⁇ m.
  • the filaments are in the shape of a wavy line that changes periodically.
  • the operating conditions of the transesterification reaction process are as follows:
  • Reaction temperature 120°C-125°C
  • the mass fraction of the base catalyst in the raw oil 2.5%
  • the process-enhancing mass transfer material added to the tower reactor was 21.6 wt% of the total reaction feed, and the process-enhancing mass transfer material added to the tubular reactor was 1.5 wt% of the total reaction feed.
  • the operating conditions of the microchannel mixing device I are as follows: the temperature is 120-125°C, and the pressure is 2.0 MPaG; the operating conditions of the microchannel mixing device II are as follows: the temperature is 120°C, and the pressure is 2.0 MPaG.
  • the conversion rate of raw materials in the primary transesterification reaction was 97.8%, and that in the secondary transesterification reaction was 98.9%; the residence time of the primary transesterification reaction was 0.611 hours, and the residence time of the secondary transesterification reaction was 0.611 hours. is 0.782 hours.
  • reaction raw materials, the reactor structure, the reaction process, the operating conditions of the microchannel mixing device I, and the operating conditions of the microchannel mixing device II are the same as those in Example 2-5. Different from Examples 2-3, this example changes the feed amount and transesterification reaction conditions on the one hand, and appropriately adjusts the introduction position and introduction amount of the enhanced mass transfer material on the other hand.
  • the operating conditions of the transesterification reaction process are as follows:
  • Reaction temperature 120°C-125°C
  • the mass fraction of base catalyst in raw oil 3.0%;
  • the process-enhancing mass transfer material added to the tower reactor was 17.5 wt% of the total reaction feed, and the process-enhancing mass transfer material added to the tubular reactor was 6.4 wt% of the total reaction feed.
  • the conversion rate of raw materials in the primary transesterification reaction was 97.3%, and that in the secondary transesterification reaction was 98.8%; the residence time of the primary transesterification reaction was 0.611 hours, and the residence time of the secondary transesterification reaction was 0.611 hours. is 0.782 hours.
  • the dispersion size and dispersion effect of the triglyceride droplets in the low-carbon alcohol in the method of the present invention are obtained by a high-speed camera, and the uniformity of the dispersed phase particles is obtained by selecting several characteristic particles, and the smaller the particle size is , The higher the uniformity, the better the effect of mixing and dispersion.
  • the method for measuring the mixing and dispersing effect of the present embodiment and the comparative example is: under the same conditions, through different mixing and dispersing methods (such as using a conventional static mixer, a microchannel mixing system I and a microchannel mixing system II in the reactor of the present invention) )
  • Mix the disperse phase triglyceride and the continuous phase low-carbon alcohol phase at least 10 groups of mixed material samples are obtained in each group of methods, and use the British IX i-SPEED 5 high-speed camera to photograph the particle size of the dispersed phase in the mixed material samples , add the particles in the photo, calculate the percentage of particles of various sizes, and obtain the normal distribution map of particles of various sizes, thereby obtaining the particle uniformity.
  • the mixture material I formed by the raw material grease, low-carbon alcohol and the catalyst is formed by the microchannel mixing device I. It is introduced from one end of the reactor as the main reaction material, and the molar ratio of the low-carbon alcohol to the raw oil in the mixed material I is ⁇ 3, so that the reaction feed is kept two-phase uniform in the reactor, which provides a high conversion rate for the transesterification reaction. Preconditions, and then make another part of the molar ratio of low-carbon alcohol to triglyceride ⁇ 3.
  • the raw oil, methanol and catalyst are mixed through the microchannel mixing device II under the condition that the molar ratio of low-carbon alcohol to raw oil is less than 3.
  • Feed II is introduced into the transesterification reactor as an enhanced mass transfer material.
  • the mixed feed II due to the small size of the droplets of the raw oil and the dense molecules, it can quickly break through the phase interface and replenish the raw oil consumed by the reaction, thereby greatly strengthening the Mass transfer throughout the reaction process, improve transesterification reaction rate and single pass conversion rate of raw materials, reduce the molar ratio of low-carbon alcohols to triglycerides, reduce the number of reactors or reaction residence time, and improve the production of biodiesel plants by transesterification efficiency.

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Abstract

本发明公开了一种微通道液-液混合设备，所述的微通道液-液混合设备包括微通道组件和壳体，微通道组件固定于壳体内，壳体一端设置入口，用于至少两种反应液相的进料，另一端设置混合物料出口；微通道组件包含多个堆叠的薄片以及相邻薄片夹缝间填充的亲油性纤维丝和亲水性纤维丝，纤维丝与纤维丝间构成若干微通道，纤维丝通过薄片夹紧固定。所述的微通道液-液混合设备用于至少两种反应液相形成混合物料，所述的至少两种反应液相在微通道混合设备内经纤维丝切割、混合而形成混合物料。本发明还公开了包括上述微通道液-液混合设备的液-液反应装置以及液-液反应方法，如烯烃水合反应装置及烯烃水合方法和酯交换法生产生物柴油的反应装置及方法。

Description

一种液-液混合器、包括其的液-液反应装置、和使用其的液-液反应方法 技术领域
本发明属于有机化工技术领域。具体地说，本发明涉及一种液-液混合器、包括其的液-液反应装置、和使用其的液-液反应方法，特别地涉及一种烯烃水合反应装置及烯烃水合方法、一种生物柴油的生产装置以及通过酯交换反应得到生物柴油的方法。
背景技术
烯烃水合工艺是液(烯烃)-液(水)-固(催化剂)三相催化反应，因此反应速率及转化率受液-液传质的影响很大。而烯烃和水两液相的相互溶解度较小，制约了烯烃水合工艺的反应效率及产能。烯烃水合反应中，以环己烯水合制环己醇、正丁烯水合仲丁醇、异丁烯水合制备叔丁醇、异戊烯水合制叔戊醇为典型的、重要的烯烃水合反应。
在环己烯水合制环己醇过程中，目前工业上使用的环己烯直接水合生产装置的反应器形式是二级串联全混釜反应器，单程转化率较低(一般<10％)，造成大量未反应的环己烯与环己醇多次循环精馏分离，能耗较高。
CN109651081A提出了一种环己烯水合制备环己醇的反应精馏方法及其装置，该方法在反应液中加入相转移催化剂，使环己烯、水、催化剂和相转移催化剂形成浆态状溶液，在反应精馏塔内发生环己烯水合反应生成环己醇，反应精馏法虽然从理论上可以大大的提高环己烯的转化率，降低系统能耗，但水合反应速率慢。
US3257469使用极性有机溶剂用来增加烯烃与水的互溶性，通过增大反应物分子向催化剂表面的扩散速度和产物向溶剂中的扩散速度，从而提高碳五烯烃的转化率。
US4182920采用三级烯烃水合反应器，反应温度为30-80℃，反应压力为0.46-1.4MPa(绝压)，水/戊烯的重量比范围为0.59-1.18，丙酮/戊烯的重量比范围为4.18-7.85，反应速率仍然很慢。
异丁烯水合制备叔丁醇过程中，异丁烯等烃类与水的相互溶解度小，在以液态混合时，容易形成两液相。异丁烯水合的关键技术在于使碳四混烃与水形成均匀分散体或者溶液，以提高反应的转化率。
CN1304917A采用异丁烯与水逆流进料的方法进塔、并且产物叔丁醇连续出塔的操作方式，以提高两相浓度差，提高反应速率和异丁烯转化率，但是该方法存在水比大、空速小、催化剂成型困难等问题。
CN02151547.6(CN1511815A)提供了一种以含异丁烯的混合碳四为原料，通过水合反应制备叔丁醇的方法，在非离子型表面活性剂和催化剂存在下，混合碳四馏分中的异丁烯与水在催化蒸馏塔中反应生成叔丁醇。本发明提供的叔丁醇制备方法大大提高了异丁烯的转化率及叔丁醇选择性，降低了生产叔丁醇的成本。
CN98812676.1(CN1283174A)提供了一种生产叔丁醇的方法中，为了增加混合碳四与水的互溶性，在反应原料中加入了叔丁醇，反应的转化率可以达到80-90％，该方法依靠离心泵的作用将叔丁醇、水和液相碳四烃三相强制混合，促进溶解，但实际采用离心泵的方法进行强制混合，也只是相间宏观混合，很难在微观上混合均匀。
生物柴油具有良好的发动机低温启动性能、硫含量低、不含有对环境造成污染的芳香烃、闪点高、安全性能好、十六烷值高、润滑性能好等优势。目前工业上生物柴油生产多采用酯交换方法，是利用甲醇等低碳醇类物质，将原料油中的三甘酯中的甘油在催化剂作用下发生酯交换而取代下来，得到生物柴油；酯交换反应为整个工艺的核心，现有技术主要基于三甘酯原料和甲醇为不相溶体系，二相的混合溶解比较困难，使酯交换过程存在液-液传质反应速率低、容易分相、反应达到既定的转化率时间长等诸多问题。
为了解决上述问题，CN1919973A利用环路湍流反应器组成一套连续式制备生物柴油的装置，原料从环路湍流反应器底部进入，在环路湍流反应器中反应，经过反应的混合物从反应器顶部出料，一部分物料回到循环混合泵再次进入反应器，目的是实现原料的循环多次强制混合，需要较大的能耗和特殊的反应器结构来实现。
CN101550349采用超临界技术制备生物柴油的方法，该方法将油脂与甲醇适当的摩尔比在超临界下成为均相，进行酯交换反应，控制压力为8-40MPA，温度300-450℃，该发明缩短了生物油脂转化为生物柴油的时间，提高了反应效率，但由于超临界生物柴油的生物需要在高温高压条件下进行，能耗和设备投资都较高，而且高温条件下容易导致生焦堵塞等问题。
CN1952046A提出了一种酯交换反应生产生物柴油的方法，是将参加反应的原料油和低碳醇按反应计量比通入设有超声波发射装置的酯交换反应器中，在适宜条件下进行反应。该发明方法的目的是通过超声波的引入改善原料油和醇的互溶性，提高不相溶两相的传质反应速率，缩短反应时间，但该方法中的超声波发生装置难以工业化，以及在工业装置上实现物料的整个混合体系达到相同的均匀程度。
CN201625532U公开了一种废弃油脂制备生物柴油的高剪切乳化反应装置，包括反应釜、电机、乳化机，所述的电机固定于反应釜外部，所述乳化机包括外套、转子和定子，所述外套、转子和定子都为同轴空心圆柱体，所述的外套一端穿过反应釜的外壳并固定在电机外壳上，另一端连接有所述定子；所述电机的主轴一端与转子固定连接；转子及定子外壁上沿轴向均设有多条贯穿外壁的通透槽，转子处于定子的空心内腔中。该实用新型主要是对反应物料进行强烈剪切乳化从而希望能够改善物料混合，一方面采用机械剪切的方式改善的程度有限，另一方面高剪切乳化反应器为全混反应器，单程转化率和生产效率较低。
对于烯烃水合反应(一般为环己烯水合制环己醇、正丁烯水合仲丁醇、异丁烯水合制备叔丁醇、异戊烯水合制叔戊醇)，烯烃与水的互溶性大大影响了传质反应速率。而在生物柴油反应过程中，甘油三酸酯与低碳醇之间的不互溶造成了酯交换传质反应速率低、易分相、反应停留时间长、原料转化率低等诸多问题，虽然当前的研究者提出了许多新工艺和新设备，但酯交换反应情况并没有得到显著改善。
对于液液反应来说，反应物料之间不良的相互溶解性会造成反应单程转化率低、反应速率慢。因此，针对这一类的液液反应来说，需要提供一种新的、有效的工艺和设备以进一步解决上述问题。
发明内容
针对现有技术的不足，本发明设计了一种液-液混合器。本发明的液-液混合器可以普遍应用于反应物料之间相互溶解性差的液-液反应。本发明中所述的液-液反应是指其中包括至少两个液相的反应，这样的反应包括但不限于液-液反应，液-液-固反应，特别地，本发明的液-液反应不包括气相进料物流。
在一个方面中，本发明提供了一种微通道液-液混合设备，所述的微通道液-液混合设备包括微通道组件和壳体，微通道组件固定于壳体内，壳体一端设置入口，用于至少两种反应液相的进料，另一端设置混合物料出口；微通道组件包含多个堆叠的薄片以及相邻薄片夹缝间填充的亲油性纤维丝和亲水性纤维丝，纤维丝与纤维丝间构成若干微通道，纤维丝通过薄片夹紧固定。所述的微通道液-液混合设备用于至少两种反应液相形成混合物料，所述的至少两种反应液相在微通道混合设备内经纤维丝切割、混合而形成混合物料。
在另一个方面中，本发明提供了一种液-液反应装置，其包括微通道混合设备I、微通道混合设备II和反应器；
所述的微通道混合设备I为管壳式结构，壳体内部设置无机膜管束；无机膜管束入口端与第一液相进料管线连通，无机膜管束外部的壳内空腔与第二液相进料管线连通，无机膜管束出口端为混合物料I出口；微通道混合设备I用于第一液相进料和第二液相进料形成混合物料I，第二液相进料由壳内空腔经无机膜管管壁孔道扩散至无机膜管内第一液相中，在管内高流速第一液相的剪切力作用下二者形成均一的混合物料I，作为主反应进料；其中，优选地，在微通道混合设备I中提供控制装置，使得第一液相/第二液相的比值大于或小于(优选大于)该反应的第一液相/第二液相的理论比值；
所述的微通道混合设备II为本发明的微通道液-液混合设备，其包括微通道组件和壳体，微通道组件固定于壳体内，壳体一端设置入口，用于第一液相和第二液相的进料，另一端设置混合物料II出口；微通道组件包含多个堆叠的薄片以及相邻薄片夹缝间填充的亲油性纤维丝和亲水性纤维丝，纤维丝与纤维丝间构成若干微通道，纤维丝通过薄片夹紧固定；微通道混合设备II用于第一液相和第二液相形成混合物料II，第一液相和第二液相在微通道混合设备II内，经纤维丝切割、混合形成混合物料II；其中，优选地，在微通道混合设备II中提供控制装置，使得第一液相/第二液相的比值不大于或不小于(优选不大于)该反应的第一液相/第二液相的理论比值；
所述的反应器顶部、底部或侧部设置进料口，底部、顶部或侧部设置出料口，反应器本体上设置强化传质物料入口，原则上强化传质物料入口可以设置在反应器内任意位置。微通道混合设备I的混合物料I出口经管线与进料口连接，微通道混合设备II的混合物料II出口与强化传质物料入口连接。
在又一个方面中，本发明提供了一种使用本发明的液-液反应装置进行液-液反应的方法。所述液-液反应包括：高分子化工中的乳液聚合、悬浮聚合，如烯烃在有机溶剂中聚合；烯烃水合反应；酯交换法生产生物柴油；油脂水解；其它如硝化、磺化、烷基化等反应。
具体来说，本发明提供了一种烯烃水合反应装置，包括微通道混合设备I、微通道混合设备II和烯烃水合反应器；
所述的微通道混合设备I为管壳式结构，壳体内部设置无机膜管束；无机膜管束入口端与水相管线连通，无机膜管束外部的壳内空腔与烯烃相管线连通，无机膜管束出口端为混合物料I出口；微通道混合设备I用于烯烃相和水相形成混合物料I，烯烃相由壳内空腔经无机膜管管壁孔道扩散至无机膜管内水相中，在管内高流速水相的剪切力作用下二者形成均一的混合物料I，作为主反应进料；其中水烯比≥1；
所述的微通道混合设备II包括微通道组件和壳体，微通道组件固定于壳体内，壳体一端设置入口，用于烯烃相和水相进料，另一端设置混合物料II出口；微通道组件包含多个堆叠的薄片以及相邻薄片夹缝间填充的亲油性纤维丝和亲水性纤维丝，纤维丝与纤维丝间构成若干微通道，纤维丝通过薄片夹紧固定；微通道混合设备II用于烯烃相和水相形成混合物料II，烯烃相和水相在微通道混合设备II内，经纤维丝切割混合形成混合物料II；其中水烯比＜1；
所述的烯烃水合反应器底部设置进料口，顶部设置出料口，侧部设置强化传质物料入口，反应器内设置若干催化剂床层，强化传质物料入口设置在反应器内任意位置，优选以更加方便实施的方式设置在相邻两层催化剂床层之间；催化剂床层填装烯烃水合催化剂。微通道混合设备I的混合物料I出口经管线与进料口连接，微通道混合设备II的混合物料II出口与强化传质物料入口连接。
通过本发明的烯烃水合反应装置及烯烃水合方法，本发明通过改善烯烃和水的混合状态以及混合进料方式，强化整个反应过程的传质，改善烯烃水合反应速率和原料单程转化率，降低整体水烯比，提高烯烃水合装置的生产效率。本发明中所述的水烯比均为水相与烯烃相的质量比。整体水烯比是指烯烃水合反应装置中水相总加入量与烯烃总加入量的质量比。
具体来说，本发明还提供了一种酯交换法生产生物柴油反应装置，包括微通道混合设备I、微通道混合设备II和酯交换反应器；
所述的微通道混合设备I为管壳式结构，壳体内部设置无机膜管束；无机膜管束入口端与低碳醇及液体催化剂管线连通，无机膜管束外部的壳内空腔与甘油三酸酯管线连通，无机膜管束出口端为混合物料I出口；微通道混合设备I用于甘油三酸酯和低碳醇与液体催化剂形成混合物料I，甘油三酸酯由壳内空腔经无机膜管管壁孔道扩散至无机膜管内的低碳醇与液体催化剂中，在管内高流速低碳醇与液体催化剂的剪切力作用下二者形成均一的混合物料I，作为主反应进料；其中低碳醇与甘油三酸酯的摩尔比≥3；
所述的微通道混合设备II包括微通道组件和壳体，微通道组件固定于壳体内，壳体一端设置入口，用于低碳醇和液体催化剂与甘油三酸酯进料，另一端设置混合物料II出口；微通道组件包含多个堆叠的薄片以及相邻薄片夹缝间填充的亲油性纤维丝和亲水性纤维丝，纤维丝与纤维丝间构成若干微通道，纤维丝通过薄片夹紧固定；微通道混合设备II用于低碳醇和液体催化剂与甘油三酸酯形成混合物料II，低碳醇和液体催化剂与甘油三酸酯在微通道 混合设备II内，经纤维丝切割混合形成混合物料II；其中低碳醇与甘油三酸酯的摩尔比<3。
所述的酯交换反应器顶部、底部或侧部设置进料口，底部、顶部或侧部设置出料口，反应器本体上设置强化传质物料入口，原则上强化传质物料入口可以设置在反应器内任意位置。微通道混合设备I的混合物料I出口经管线与进料口连接，微通道混合设备II的混合物料II出口与强化传质物料入口连接。
通过本发明的酯交换法生产生物柴油的反应装置及方法，本发明通过改善甘油三酸酯与低碳醇的混合状态以及混合进料方式，强化整个反应过程的传质速率，改善酯交换反应速率和原料单程转化率，缩短反应时间，提高生物柴油生产装置的生产效率。
在本发明的液-液反应装置(如烯烃水合反应装置、酯交换法生产生物柴油反应装置)中，微通道混合设备I和微通道混合设备II的个数可以根据实际需要进行设置，一般设置1-3个满足反应需要即可。本发明装置中，所述的微通道混合设备I的无机膜管束可以为陶瓷膜、金属膜、金属/陶瓷复合膜、合金膜、分子筛复合膜、沸石膜或玻璃膜等中的一种或多种；无机膜管管壁上的孔径为10nm-1μm；混合物料I中第二液相(如烯烃相、甘油三酯相)的粒径大小d1为100-900μm，优选300-500μm。
本发明装置的微通道混合设备II中，壳体内微通道组件沿夹缝方向分为进料端和出料端，物料入口与进料端之间设置进料分布空间，物料出口与出料端之间设置出料分布空间，除进料端和出料端外，微通道组件其余各端均与壳体密封连接。
所述的微通道组件，包含多个堆叠的薄片以及相邻薄片夹缝间填充的亲油性纤维丝和亲水性纤维丝，纤维丝与纤维丝间构成若干微通道，纤维丝通过薄片夹紧固定；所述相邻薄片夹缝间填充的亲油性纤维丝和亲水性纤维丝的数量比例为1:50-1:1；所述纤维丝可以单层或多层排布，优选1-50层，更优选为1-5层，优选任意一层中的亲水性纤维丝均匀分布于亲油性纤维丝间；优选任意一层中亲油性纤维丝和亲水性纤维丝的数量比例为1:50-1:1。当为多层排布时，优选相邻两层纤维丝沿薄片垂直方向的投影为网状结构；网状结构中的网格形状可以为任意形状，如多边形、圆形、椭圆形等中的一种或多种组合；每层纤维丝中，相邻纤维丝的间距一般为0.5μm-50μm，优选等间距排布，纤维丝沿薄片表面横向、纵向或斜向等任意一种；所述的纤维丝可以为任意曲线形状，优选周期性变化的曲线形状，如波浪形、锯齿形等，优选同一层的纤维丝的形状相同，更优选所有层的纤维丝的形状都相同。
所述的微通道组件中，纤维丝的直径一般为0.5-50μm，优选为0.5-5μm，更优选为0.5-1μm。所述的亲油性纤维丝一般为聚酯纤维丝、尼龙纤维丝、聚氨酯纤维丝、聚丙烯纤维丝、聚丙烯腈纤维丝、聚氯乙烯纤维丝、或表面经过(物理或化学方法)亲油处理的纤维丝中的至少一种；所述的亲水性纤维丝一般选自主链或侧链含有羧基(-COOH)、酰胺基(-CONH-)、氨基(-NH 2-)、或羟基(-OH)等亲水性基团的高分子聚合物，且含有的亲水性基团数目越多，亲水性越好，常用的如丙纶纤维、聚酰胺纤维、丙烯酸纤维，或选自材料经过(物理或化学方法)亲水处理的纤维丝。
所述的微通道组件中，薄片厚度一般为0.05mm-5mm，优选0.1-1.5mm。薄片的材质一般根据过流物料性质、操作条件而定，可以为金属、陶瓷、有机玻璃、聚酯等材料中的任意一种，优选金属中的不锈钢(SS30403、SS30408、SS32168、SS31603)材料。薄片的形状可以为长方形、正方形、多边形、圆形、椭圆形、扇形、等任意一种，优选长方形或正方形。薄片的尺寸和数量可以根据反应实际需要进行设计调整。
本发明装置中，所述的反应器可以为任意反应器类型，如固定床反应器、釜式反应器、塔式反应器、管式反应器或上述反应器的改进形式，可以根据需要设置1个或多个，反应器之间并联或串联；至少引入一股由微通道混合设备II形成的混合物料作为强化传质物料。
对于烯烃水合反应来说，本发明装置中，所述的反应器为固定床反应器，可以根据需要设置1个或多个，反应器之间并联或串联；每个反应器设置至少1个催化剂床层，优选1-4个；至少引入一股由微通道混合设备II形成的混合物料作为强化传质物料。
对于酯交换反应来说，本发明装置中，所述的反应器可以为任意反应器类型，如釜式反应器、塔式反应器、管式反应器或上述反应器的改进形式，可以根据需要设置1个或多个，反应器之间并联或串联；至少引入一股由微通道混合设备II形成的混合物料作为强化传质物料。
本发明还提供一种烯烃水合方法，包括：将水烯比≥1的烯烃相和水相经微通道混合设备I混合形成混合物料I，作为主反应物料由烯烃水合反应器底部进入；将水烯比<1的烯烃相和水相经微通道混合设备II混合形成混合物料II，作为强化传质物料引入反应器内，混合物料I和混合物料II在催化剂床层发生烯烃水合反应，反应产物由反应器顶部出口流出，进入下一分离单元。
对于烯烃水合方法来说，本发明方法中，微通道混合设备I的操作条件一般如下：温度为常温-250℃，压力为1.0-10.0MPaG；微通道混合设备II的操作条件一般如下：温度为常温-200℃，压力1.0-10.0MPaG。
对于烯烃水合方法来说，本发明方法中，所述的烯烃相一般为乙烯、丙烯、正丁烯、异丁烯、异戊烯或环己烯等中的任意一种。
对于烯烃水合方法来说，本发明方法中，所述的烯烃水合反应器一般采用下进上出形式，有利于烯烃和水两相的均匀接触传质。
对于烯烃水合方法来说，本发明方法中，所述的烯烃水合反应的总水烯比根据发生烯烃水合反应的烯烃类型和反应的难易程度而定；所述的微通道混合设备I中，水烯质量比一般为2:1-20:1，适当高的水烯比可以保证水合过程的传质反应速率，但反应器体积更大，这里只要维持反应器中的水相大于烯烃相即可；所述的微通道混合设备II中，水烯质量比一般为1:20-1:1，该物料中的水烯比较低，即烯烃的比例含量较高，作为强化传质物料可以迅速突破相界面而传递至催化剂表面来补充反应消耗掉的烯烃，使催化剂表面始终保持有大量的富含烯烃分子的烯烃/水均一相，从而提高烯烃水合反应的单程转化率。
对于烯烃水合方法来说，本发明方法中，所述的微通道混合设备I形成的混合物料I中，烯烃液滴的粒径d1为100-900μm，优选分散均匀度≥80％，此时，进入反应器催化剂床层发生反应时，能够保持烯烃/水两相在反应停留时间内不发生相的分离，改善传质反应速率，达到较好的反应效果和烯烃原料单程转化率；微通道混合设备II形成的混合物料II中，烯烃液滴的粒径d2为小于100μm，优选0.1-50μm，作为强化传质物料引入催化剂床层之间时，由于烯烃粒径小、烯烃分子密集，在经过催化剂颗粒时烯烃分子能够迅速突破相界面传递至催化剂表面，起到进一步强化反应传质的目的。
对于烯烃水合方法来说，本发明方法中，所述的混合物料II的加入量为反应器总物料(烯烃相和水相总量)的1wt％-30wt％；混合物料II的分为多股加入时，优选沿物料在反应器内流动方向上各股加入量逐渐增加(例如后一股相对于前一股增加5-20wt％)。当然，沿反应器内物料流动方向水烯比也可以降低或不变。这里，随着烯烃水合反应的进行，烯烃分子尤其是催化剂表面的烯烃分子逐渐被消耗，反应过程的传质推动力逐渐减小，而由于反应器内水量远远大于烯烃相，所以烯烃分子浓度低导致催化剂表面的烯烃分子逐渐减少，所以通过催化剂床层间补充烯烃含量高的强化传质物料，能够迅速突破相界面而传递至催化剂表面来及时补充反应消耗掉的烯烃，从而保持较高的反应速率。
对于烯烃水合方法来说，本发明方法中，烯烃水合反应器的催化剂床层内一般可以采用具有酸催化功能的催化剂，如矿物酸、苯磺酸、离子交换树脂、分子筛等类型的催化剂。
对于烯烃水合方法来说，本发明方法中，烯烃水合反应条件一般为：温度80-250℃，压力1.0-10.0MPaG，空速为0.1-3.0h -1，根据烯烃原料不同所需要的反应条件不同。
现有技术中采用常规的烯烃/水混合方法、混合设备或具有混合功能的组件进行混合时，存在混合不均匀、状态不稳定、容易分相的问题，从而使烯烃水合的传质速率较低，因此即使在较高的水烯比时的单程转化率也很低，尤其对于正丁烯水合来说，采用常规反应器的单程转化率只有6％-8％。本发明的烯烃水合装置及反应方法中，通过微通道混合设备I，将大部分烯烃与水以一定比例进行微观混合，使反应进料在反应器内反应过程中能够保持两相均一、不分相，在此情况下同时保持反应器内为水相大于烯烃相，从而实现反应器内烯烃相与水相的连续传质；然后再通过微通道混合设备II，将部分烯烃与水以另一种比例进行微观混合，使形成的混合物料I中烯烃相的液滴尺寸(d1)小于混合物料II中烯烃相的液滴尺寸(d2)，混合物料I中的烯烃相液滴密集度<混合物II料中的烯烃相液滴密集度，因此当将含有更高密集度的烯烃相的混合物料II引入催化剂床层时，可以快速突破相界面、迅速补充反应消耗掉的烯烃相，起到强化传质的目的，改善烯烃水合反应速率和原料单程转化率，有利于降低水烯比，减少反应器数量或反应停留时间，提高烯烃水合装置的生产效率。这里，烯烃相液滴密集度是指单位体积内分散在水相中的烯烃微液滴的数量。同时，微通道混合设备II中的微通道组件的特殊结构，相邻薄片夹缝间填充一定比例的金属纤维丝，能够将烯烃和水混合进料中的水沿纤维丝表面粘附、铺展，反复被纤维丝强制切割为微米级尺寸粒子，混合充分的物料含有密集烯烃液滴的、更小尺寸烯烃液滴作为强化传质物料，可以快速突破相界面、迅速补充反应消耗掉的烯烃相，起到强化传质的目的，降低水烯比。
本发明还提供一种酯交换反应方法，包括：将低碳醇与甘油三酸酯的摩尔比≥3的两相经微通道混合设备I混合形成混合物料I，作为主反应物料进入酯交换反应器；将低碳醇与甘油三酸酯的摩尔比<3的两相经微通道混合设备II混合形成混合物料II，作为强化传质物料引入反应器内，混合物料I和混合物料II在反应器内发生酯交换反应，反应产物由反应器出口流出，进入分离单元。
对于酯交换反应方法来说，本发明方法中，微通道混合设备I的操作条件一般如下：温度为常温-150℃，压力为0.5-3.0MPaG；微通道混合设备II的操作条件一般如下：温度为常温-150℃，压力0.5-3.0MPaG。其中，液体催化剂用量为原料油脂用量的0.5％-10％。
对于酯交换反应方法来说，本发明方法中，所述原料油脂为甘油三酸酯，主要来源于动物油或植物油；原料油脂的酸值可以介于0-130mgKOH/g的脂肪酸和油脂(含地沟油)，优选小桐子油、菜籽油、大豆油、亚麻油、花生油、棕榈油、茶籽油等的精制植物油。
对于酯交换反应方法来说，本发明方法中，所述的低碳醇的碳数为1-6的脂肪醇，可以为单一的脂肪醇，也可以是一种或多种脂肪醇的混合物，优选甲醇。
对于酯交换反应方法来说，本发明方法中，所述的酯交换反应采用碱性催化剂，碱性催化剂可以为氢氧化钠、氢氧化钾、氢氧化钡、氢氧化钙、氧化镁、氧化钙、氧化钡、二乙胺中的一种或多种混合物。
对于酯交换反应方法来说，本发明方法中，所述的酯交换反应条件如下：反应压力0.5-2.0MPaG，反应温度为100-150℃；低碳醇与甘油三酸酯的摩尔比为1:3-1:15，碱性催化剂用量为原料油脂用量的0.5％-10％。
对于酯交换反应方法来说，本发明方法中，强化传质物料II中，可以包含或不包含液体催化剂。
对于酯交换反应方法来说，本发明方法中，酯交换反应器的总停留时间为0.5-7小时，优选0.5-3.5小时；在此时间内，转化率为≥98.5％。
对于酯交换反应方法来说，本发明方法中，所述的微通道混合设备I中，低碳醇与甘油三酸酯的摩尔比一般为3:1-15:1，适当高的醇油摩尔比可以保证酯交换过程的传质反应速率，但反应器体积更大，这里只要维持反应器中的醇油摩尔比≥3即可；所述的微通道混合设备II中，醇油摩尔比一般为1:10-1:0.33，该物料中的醇油摩尔比较低，即甘油三酸酯比例含量较高，作为强化传质物料可以迅速突破相界面而传递至催化剂表面来补充反应消耗掉的甘油三酸酯，使催化剂表面始终保持有大量的富含甘油三酸酯分子的低碳醇/甘油三酸酯均一相，从而提高酯交换反应速率和转化率。
对于酯交换反应方法来说，本发明方法中，所述的微通道混合设备I形成的混合物料I中，甘油三酸酯液滴的粒径d1为100-900μm，优选分散均匀度≥80％，此时，进入反应器时，能够保持低碳醇/甘油三酸酯两相在反应停留时间内不发生相的分离，改善传质反应速率，达到较好的反应效果和甘油三酸酯的转化率；微通道混合设备II形成的混合物料II中，甘油三酸酯液 滴的粒径d2为小于100μm，优选0.1-50μm，作为强化传质物料引入反应器之间时，由于甘油三酸酯粒径小、甘油三酸酯分子密集，在发生酯交换反应时甘油三酸酯分子能够迅速突破相界面传递至催化剂表面，起到进一步强化反应传质的目的。
对于酯交换反应方法来说，本发明方法中，所述的混合物料II的加入量为反应器总物料(甘油三酸酯和甲醇及液体催化剂相总量)的1wt％-30wt％；当混合物料II分为多股加入时，优选沿物料在反应器内从入口到出口方向上各股加入量逐渐增加(例如后一股相对于前一股增加5-20wt％)。当然，沿反应器内从入口到出口方向低碳醇/甘油三酸酯摩尔比也可以降低或不变。这里，随着酯交换反应的进行，甘油三酸酯分子逐渐被消耗，反应过程的传质推动力逐渐减小，而由于反应器内低碳醇摩尔量远远大于甘油三酸酯相，所以甘油三酸酯分子浓度低导致催化剂表面的甘油三酸酯分子逐渐减少，所以通过催化剂床层间补充甘油三酸酯含量高的强化传质物料，能够迅速突破相界面来及时补充反应消耗掉的甘油三酸酯，从而保持较高的酯交换反应速率。
对于酯交换反应方法来说，本发明方法中，针对生物柴油生产酯交换反应过程中原料油和甲醇的两相互不相溶、反应过程中容易分相、反应速率低、转化率低、停留时间长的问题，而现有技术缺乏有效的两相混合工艺及设备，为此本发明一种高效的酯交换法生产生物柴油的反应装置及方法，该方法通过微通道混合设备I，将大部分原料油脂与甲醇及液体催化剂以一定比例进行微观混合，使反应进料在反应器内反应过程中能够保持两相均一、不分相，在此情况下同时保持反应器内为甲醇及液体催化剂的摩尔数大于甘油三酸酯的摩尔数，从而实现反应器内甘油三酸酯与甲醇及液体催化剂的连续传质；然后再通过微通道混合设备II，将部分甘油三酸酯与甲醇及液体催化剂以另一种比例进行微观混合，使形成的混合物料I中甘油三酸酯的液滴尺寸(d1)小于混合物料II中甘油三酸酯相的液滴尺寸(d2)，混合物料I中的甘油三酸酯相液滴密集度<混合物料II中的甘油三酸酯相液滴密集度，因此当将含有更高密集度的甘油三酸酯相的混合物料II引入反应器时，可以快速突破相界面、迅速补充反应消耗掉的甘油三酸酯，起到强化传质的目的，改善酯交换反应速率和原料转化率，有利于降低低碳醇/甘油三酸酯摩尔比比，减少反应器数量或反应停留时间，提高酯交换法生产生物柴油装置的生产效率。这里，甘油三酸酯液滴密集度是指单位体积内分散在甲醇及液体催化剂混合物中的甘油三酸酯微液滴的数量。同时，微通道混合设备II中的微通道组件的特殊结构，相邻薄片夹缝间填充一定比例的金属纤维丝，能够将甘油三酸酯和甲醇及液体催化剂混合进料中的水沿纤维丝表面粘附、铺展，反复被纤维丝 强制切割为微米级尺寸粒子，混合充分的物料含有密集烯烃液滴的、更小尺寸甘油三酸酯液滴作为强化传质物料，可以快速突破相界面、迅速补充反应消耗掉的油脂，起到强化传质的目的，降低总甲醇与甘油三酸酯的摩尔比。
附图说明【修改附图】
图1A是本发明的烯烃水合反应装置的的示意图。
图1B为微通道混合设备II内微通道组件的示意图，
在图1A和1B中：
101     烯烃相I
102     水相I
103     微通道混合设备I
104     管壳式无机膜混合器的壳体
105     无机膜管束
106     无机膜管束外的壳体空间
107     混合物料I
108     烯烃相II
109     水相II
110     微通道混合设备II
111     微通道组件
112     微通道壳体
113     微通道薄片
114     微通道薄片间的夹缝
115     亲水性纤维丝
116     亲油性纤维丝
117     混合物料II
118     引入第一、第二催化剂床层间的强化传质物料
119     引入第二、第三催化剂床层间的强化传质物料
120     引入第三、第四催化剂床层间的强化传质物料
121     烯烃水合反应器
122     第一催化剂床层
123     第二催化剂床层
124     第三催化剂床层
125     第四催化剂床层
126     第一催化剂床层进料分布器
127     第二催化剂床层进料分布器
128     第三催化剂床层进料分布器
129     第四催化剂床层进料分布器
130     烯烃水合反应产物
图2A是本发明的酯交换法生产生物柴油的反应装置的示意图。
图2B为微通道混合设备II内微通道组件的示意图，
在图2A和2B中：
201     甘油三酸酯I
202     低碳醇与液体催化剂I
203     微通道混合设备I
204     管壳式无机膜混合器的壳体
205     无机膜管束
206     无机膜管束外的壳体空间
207     混合物料I
208     甘油三酸酯II
209     低碳醇与液体催化剂II
210     微通道混合设备II
211     微通道组件
212     微通道壳体
213     微通道薄片
214     微通道薄片间的夹缝
215     亲水性纤维丝
216     亲油性纤维丝
217     混合物料II
218     引入酯交换反应器的强化传质物料
219     引入酯交换反应器的强化传质物料
220     引入酯交换反应器的强化传质物料
221     酯交换反应器
222     物料分布器
223     酯交换反应产物
具体实施方式
下面结合附图说明和实施例对本发明进行详细说明，但不因此限制本发明。
以图1A为例说明本发明的烯烃水合反应装置及烯烃水合方法：
首先将烯烃相101和水相102以水烯比≥1的比例引入微通道混合设备I 103，形成混合物料I 107，其中烯烃相101引入微通道混合设备I 103的壳体空间6，水相102引入微通道混合设备I 103的无机膜管束105内，烯烃相101经无机膜管管壁由管外渗透至管内，在水的高速剪切作用下二者发生强制混合，形成混合物料I 107，作为主反应物料进入烯烃水合反应器121，在催化剂床层发生反应；另一部分烯烃相II 108和水相II 109以水烯比<1的比例引入微通道混合设备II 110，在经过微通道混合设备II 110中设置的微通道组件111内微通道薄片113间的夹缝114，被夹缝114间填充的亲水性纤维丝115和亲油纤维丝116多次连续切割后，形成混合物料II 117，分别作为第一/第二催化剂床层间的强化传质物料118、第二/第三催化剂床层间的强化传质物料119、第三/第四催化剂床层间的强化传质物料120引入烯烃水合反应器121的催化剂床层间，使该强化传质物料能够迅速补充反应过程中消耗掉的烯烃分子，从而起到强化传质的目的，完成烯烃水合反应的物料作为反应产物130离开。
将本发明的烯烃水合反应器分别应用于丙烯、正丁烯水合、异丁烯水合、环己烯水合反应中。具体反应条件见对比例1-1、对比例1-2、对比例1-3、对比例1-4、实施例1-1、实施例1-2、实施例1-3、实施例1-4、实施例1-5、实施例1-6。烯烃原料为市售，具体性质分别见表1-1、表1-2、表1-3。其中，丙烯水合采用的催化剂为丹东明珠特种树脂有限公司生产的DIAP型催化剂，正丁烯水合采用的催化剂为丹东明珠特种树脂有限公司生产的DNW-II型催化剂，异丁烯水合采用的催化剂为丹东明珠特种树脂有限公司生产的DT-017型催化剂，环己烯水合采用的催化剂为Amberlyst 36型树脂催化剂。
表1-1 丙烯原料组成
项目 组份 含量，wt％
1 丙烯 95.32
2 丙烷 3.43
3 丁烷 0.57
4 异丁烷 0.26
5 2-丁烯 0.38
表1-2 正丁烯原料组成
项目 组份 含量，wt％
1 丙烷 0.02
2 异丁烷 9.69
3 反-2丁烯 14.22
4 顺-2丁烯 5.77
5 丙烯 0.01
6 正丁烷 11.68
7 1-丁烯 58.48
8 异丁烯 0.13
表1-3 异丁烯原料组成
项目 组份 含量，wt％
1 丙烷 0.22
2 丙烯 0.35
3 异丁烷 0.43
4 异丁烯 98.35
5 反-丁烯 0.14
6 异戊烷 0.15
7 顺-丁烯 0.25
8 其它 0.11
对比例1-1
以表1-1中的丙烯为原料，与水在催化剂作用下发生正丁烯水合反应制备异丙醇。丙烯原料与水通过常规的静态混合器，型号为SL-1.6/25-10.0-200，二者混合物料进入丙烯水合反应器发生水合反应。混合条件如下：温度为155℃，压力为8.0MPa。反应器采用普通的上流式反应器，反应器内设置三段催化剂床层，每段催化剂床层的入口都设置分布筛板，筛板孔径为3mm。将烯烃/水混合物料从反应器底部引入烯烃水合反应器，经分布筛板沿反应器截面均匀分布后，进入催化剂床层发生烯烃水合反应，最终由反应器顶部出料口离开烯烃水合反应器。
以表1-1的丙烯为原料，经丙烯水合反应器得到反应产物，反应条件、停留时间及原料转化率见表1-4。
对比例1-2
以表1-2中的正丁烯为原料，与水在催化剂作用下发生正丁烯水合反应制备仲丁醇。正丁烯原料与水通过常规的静态混合器，型号为SL-1.6/25-10.0-250，连续三次混合，混合物料进入正丁烯水合反应器发生水合反应。混合条件如下：温度为175℃，压力为8.0MPa。反应器采用普通的 上流式反应器，反应器内设置四段催化剂床层，每段催化剂床层的入口都设置分布筛板，筛板孔径为2mm。将正丁烯/水混合物料从反应器底部引入烯烃水合反应器，经分布筛板沿反应器截面均匀分布后，进入催化剂床层发生烯烃水合反应，最终由反应器顶部出料口离开烯烃水合反应器。
以表1-2的正丁烯为原料，经正丁烯水合反应器得到反应产物，反应条件、停留时间及原料转化率见表1-4。
对比例1-3
以表1-3中的异丁烯为原料，与水在催化剂作用下发生异丁烯水合反应制备叔丁醇。异丁烯原料与水通过常规的静态混合器，型号为SL-1.6/25-5.-200，二者混合物料进入异丁烯水合反应器发生水合反应。混合条件如下：温度为105℃，压力为2.6MPa。反应器采用普通的上流式反应器，反应器内设置两段催化剂床层，每段催化剂床层的入口都设置分布筛板，筛板孔径为3mm。将异丁烯/水混合物料从反应器底部引入烯烃水合反应器，经分布筛板沿反应器截面均匀分布后，进入催化剂床层发生烯烃水合反应，最终由反应器顶部出料口离开烯烃水合反应器。
以表1-3的异丁烯为原料，经异丁烯水合反应器得到反应产物，反应条件、停留时间及原料转化率见表1-4。
实施例1-1
以表1-1中的丙烯为原料，与水在催化剂作用下发生丙烯水合反应制备异丙醇。将水烯质量比以12:1的比例引入微通道混合设备I形成混合物料I，作为主反应物料进入烯烃水合反应器，在催化剂床层发生反应；将水烯质量比以1:7.5的比例经微通道混合设备II形成混合物料II，作为强化传质物料引入催化剂床层间，对烯烃水合反应过程进行强化，反应流出物离开反应器，进入下一分离单元。
反应器采用本发明的反应器，下进上出，反应器内设置三段催化剂床层，第一/第二催化剂床层间、第二/第三催化剂床层间分别引入一股强化传质混合物料II，混合物料II的加入量为反应器总物料(烯烃相和水相总量)的3.6wt％，第一/第二催化剂床层间、第二/第三催化剂床层间引入的混合物料II比例为1:1.5。微通道混合设备II中，微通道混合组件中的薄片采用不锈钢材质，薄片厚度为1.2mm，薄片夹缝间填充5层直径为5μm的金属纤维丝和1层直径为5μm的陶瓷纤维丝，纤维丝等间距排布，间距为1μm。纤维丝为波浪线周期性变化的曲线形状。微通道混合设备I的操作条件如下：温度为150℃，压力为7.5MPaG；微通道混合设备II的操作条件如下：温度为125℃，压力7.0MPaG。
以表1-1的丙烯为原料，丙烯水合反应条件、停留时间及原料转化率见表1-4。
实施例1-2
本实施例中，反应原料、反应器结构、反应过程、微通道混合设备I的操作条件、微通道混合设备II的操作条件同实施例1-1。与实施例1-1不同的是，本实施例采用更加缓和的反应条件。反应条件、停留时间及原料转化率见表1-4。
实施例1-3
以表1-2中的正丁烯为原料，与水在催化剂作用下发生正丁烯水合反应制备仲丁醇。将水烯质量比以3:1的比例引入微通道混合设备I形成混合物料I，作为主反应物料进入烯烃水合反应器，在催化剂床层发生反应；将水烯质量比以1:2的比例经微通道混合设备II形成混合物料II，作为强化传质物料引入催化剂床层间，对烯烃水合反应过程进行强化，反应流出物离开反应器，进入下一分离单元。
反应器采用本发明的反应器，下进上出，反应器内设置四段催化剂床层，第一/第二催化剂床层间、第二/第三催化剂床层间、第三/第四催化剂床层间分别引入强化传质混合物料II，混合物料II的加入量为反应器总物料(烯烃相和水相总量)的4.0wt％，第一/第二催化剂床层间、第二/第三催化剂床层间、第三/第四催化剂床层间引入的混合物料II比例为1:1.2:1.5。
微通道混合设备II中，微通道混合组件中的薄片采用不锈钢材质，薄片厚度为1.0mm，薄片夹缝间填充3层直径为1μm的玻璃纤维丝和1层直径为5μm的陶瓷纤维丝，纤维丝等间距排布，间距为1μm。纤维丝为波浪线周期性变化的曲线形状。微通道混合设备I的操作条件如下：温度为175℃，压力为7.8MPaG；微通道混合设备II的操作条件如下：温度为135℃，压力7.0MPaG。
以表1-2的正丁烯为原料，水合反应条件、停留时间及原料转化率见表1-4。
实施例1-4
本实施例中，反应原料、反应器结构、反应过程、微通道混合设备I的操作条件、微通道混合设备II的操作条件同实施例1-3。与实施例1-3不同的是，本实施例采用更加缓和的反应条件。反应条件、停留时间及原料转化率见表1-4。
实施例1-5
以表1-3中的异丁烯为原料，与水在催化剂作用下发生异丁烯水合反应制备叔丁醇。将水烯质量比以4:1的比例引入微通道混合设备I形成混合物料I，作为主反应物料进入烯烃水合反应器，在催化剂床层发生反应；将水烯质量比以1:1.62的比例经微通道混合设备II形成混合物料II，作为强化传质物料引入催化剂床层间，对烯烃水合反应过程进行强化，反应流出物离开反应器，进入下一分离单元。
反应器采用本发明的反应器，下进上出，反应器内设置两段催化剂床层，第一/第二催化剂床层间引入强化传质混合物料II，混合物料II的加入量为反应器总物料(烯烃相和水相总量)的2.0wt％，第一/第二催化剂床层间、第二/第三催化剂床层间引入的混合物料II比例为1:1.5。
微通道混合设备II中，微通道混合组件中的薄片采用不锈钢材质，薄片厚度为1.5mm，薄片夹缝间填充8层直径为5μm的不锈钢纤维丝和2层直径为5μm的陶瓷纤维丝，纤维丝等间距排布，间距为1μm。纤维丝为波浪线周期性变化的曲线形状。微通道混合设备I的操作条件如下：温度为105℃，压力为2.8MPaG；微通道混合设备II的操作条件如下：温度为85℃，压力2.1MPaG。
以表1-3的异丁烯为原料，水合反应条件、停留时间及原料转化率见表1-4。
实施例1-6
本实施例中，反应原料、反应器结构、反应过程、微通道混合设备I的操作条件、微通道混合设备II的操作条件同实施例1-5。与实施例1-5不同的是，本实施例采用更加缓和的反应条件。反应条件、停留时间及原料转化率见表1-4。
表1-4 反应条件和结果
Figure PCTCN2021127019-appb-000001
本发明方法中的烯烃液滴在水中的分散尺寸和分散效果是通过高速摄像仪来获得，并通过选择若干个特征粒子来得到分散相粒子的均匀度，粒子尺寸越小、均匀度越高，说明混合分散的效果越好。为此，本实施例及对比例的混合分散效果的测定方法为：同一条件下通过不同混合分散方法(如采用常规静态混合器、本发明反应器内微通道混合系统I和微通道混合系统II)对分散相烯烃和连续相水相进行混合，每组方法至少取得10组混合物料样品，利用英国IX i-SPEED 5高速摄像机来拍摄混合物料样品中分散相的粒子尺寸大小，将照片中粒子加和，计算出各种尺寸粒子的百分含量，得到各种尺寸粒子的正态分布图，从而得到粒子均匀度。
由本实施例及对比例的混合效果可以看出，采用本发明的烯烃水合反应装置及反应方法，作为主反应物料从反应器底部引入，使反应进料在反应器内保持两相均一，为烯烃水合反应的高转化率提供前提条件，然后再使另一部分烯烃和水在水烯比<1的条件下通过微通道混合设备II形成混合进料II，作为强化传质物料引入催化剂床层间，混合进料II中由于烯烃液滴尺寸小、烯烃分子密集，能够快速突破相界面而补充反应消耗掉的烯烃相，从而大幅度强化整个反应过程的传质，改善烯烃水合反应速率和原料单程转化率，降低水烯比，减少反应器数量或反应停留时间，提高烯烃水合装置的生产效率。
以图2A为例说明本发明的酯交换法生产生物柴油的反应装置及方法：
首先将甘油三酸酯201和低碳醇与液体催化剂202以低碳醇/甘油三酸酯摩尔比比≥3的比例引入微通道混合设备I 203，形成混合物料I 207，其中甘油三酸酯201引入微通道混合设备I 203的壳体空间206，低碳醇与液体催化剂202引入微通道混合设备I 203的无机膜管束205内，甘油三酸酯201经无机膜管管壁由管外渗透至管内，在低碳醇与液体催化剂的高速剪切作用下二者发生强制混合，形成混合物料I 207，作为主反应物料进入酯交换反应器221，在反应器内发生酯交换反应；另一部分甘油三酸酯II 208和水相II 209以低碳醇/甘油三酸酯摩尔比<3的比例引入微通道混合设备II 210，在经过微通道混合设备II 210中设置的微通道组件211内微通道薄片213间的夹缝214，被夹缝214间填充的亲水性纤维丝215和亲油纤维丝216多次连续切割后，形成混合物料II 217，分别作为强化传质物料218、强化传质物料219、强化传质物料220引入酯交换反应器221，使该强化传质物料能够迅速补充反应过程中消耗掉的甘油三酸酯，从而起到强化传质的目的，完成酯交换反应的物料作为反应产物222离开。
本发明对比例和实施例所采用的原料甘油三酸酯为桐油，其性质见表1。
表1 原料性质
序号 项目 指标
1 色泽(罗维比色计1英寸槽) 黄：35，红：≤3.0
2 气味 具有桐油固有的正常气味，无异味
3 透明度(静置24h，20℃) 透明
4 酸价/mg(KOH)·g-1 3.0
5 水分及挥发物，％ 0.10
6 机械杂质，％ 无
对比例2-1
采用常规的生物柴油产品酯交换反应装置和反应方法，酯交换反应原料为原料油脂、甲醇和碱性催化剂(原料油脂性质见表一)，首先将原料油脂与甲醇和碱性催化剂引入搅拌釜进行搅拌混合15-20分钟后，再用进料泵打入两级反应器发生酯交换反应，其中一级反应器为塔式反应器，反应器尺寸为
Figure PCTCN2021127019-appb-000002
二级反应器为管式反应器，反应器尺寸为
Figure PCTCN2021127019-appb-000003
反应器操作条件如下：
原料油脂进料量：1.5kg/h；
反应温度为120℃-125℃；
反应压力为2.0MPaG；
醇油摩尔比：8-10(油脂分子量按880计，后续同)
碱催化剂占原料油脂的质量分数：2.5％。
在该反应条件下，一级反应器出口原料转化率为75.2％，二级反应器出口原料转化率为87.4％；一级酯交换反应停留时间(以总物料计)为2.02小时，二级酯交换反应停留时间(以总物料计)为3.44小时。
对比例2-2
采用常规的生物柴油产品酯交换反应装置和反应方法，酯交换反应原料为原料油脂、甲醇和碱性催化剂(原料油脂性质见表一)，首先将原料油脂与甲醇和碱性催化剂引入撞击流反应器进行撞击混合5-10分钟后，再用进料泵打入两级反应器发生酯交换反应，其中一级反应器为塔式反应器，反应器尺寸为
Figure PCTCN2021127019-appb-000004
二级反应器为管式反应器，反应器尺寸为
Figure PCTCN2021127019-appb-000005
反应器操作条件如下：
原料油脂进料量：1.8kg/h；
反应温度为120℃-125℃；
反应压力为2.0MPaG；
醇油摩尔比：8-10(油脂分子量按880计)
碱催化剂占原料油脂的质量分数：2.5％。
在该反应条件下，一级反应器出口原料转化率为87.2％，二级反应器出口原料转化率为90.5％；一级酯交换反应停留时间(以总物料计)为1.68小时，二级酯交换反应停留时间(以总物料计)为2.87小时。
实施例2-1
采用本发明的酯交换反应工艺，酯交换反应原料为原料油脂、甲醇和碱性催化剂(原料油脂性质见表一)，将原料油脂、甲醇和碱性催化剂三者引入微通道混合设备I，其中原料油脂/甲醇以摩尔比为6:1，原料油脂引入微通道混合设备I的壳程侧，甲醇和液体碱催化剂引入微通道混合设备I的管程侧，经微通道混合设备I形成的混合物物料I作为主反应物料进入两级酯交换反应器，发生酯交换反应，其中一级反应器为塔式反应器，反应器尺寸为
Figure PCTCN2021127019-appb-000006
二级反应器为管式反应器，反应器尺寸为
Figure PCTCN2021127019-appb-000007
将原料油脂和甲醇以摩尔比为1:1的比例经微通道混合设备II形成混合物料II，作为强化传质物料分别引入塔式反应器和管式反应器，对酯交换反应过程进行强化，反应流出物离开反应器，进入分离单元。
微通道混合设备II中，微通道混合组件中的薄片采用不锈钢材质，薄片厚度为1.2mm，薄片夹缝间填充5层直径为5μm的金属纤维丝和1层直径为5μm的陶瓷纤维丝，纤维丝等间距排布，间距为1μm。纤维丝为波浪线周期性变化的曲线形状。
酯交换反应过程操作条件如下：
油脂进料量：3.6kg/h；
反应温度：120℃-125℃；
反应压力：2.0MPaG；
碱催化剂占原料油脂的质量分数：2.5％；
塔式反应器加入的过程强化传质物料为总反应进料量的25.6wt％，管式反应器加入的过程强化传质物料为总反应进料量的5.2wt％。
微通道混合设备I的操作条件如下：温度为120-125℃，压力为2.0MPaG；微通道混合设备II的操作条件如下：温度为120℃，压力2.0MPaG。
在该反应条件下，一级酯交换反应中原料转化率为96.30％，二级酯交换反应中原料转化率为98.7％；一级酯交换反应停留时间为0.87小时，二级酯交换反应停留时间为1.11小时。
实施例2-2
本实施例中，反应原料、反应器结构、反应过程、微通道混合设备I的操作条件、微通道混合设备II的操作条件同实施例2-1。与实施例2-1不同的是，本实施例一方面改变了酯交换反应条件，另一方面适当调整了强化传质物料的引入位置和引入量。
酯交换反应过程操作条件如下：
油脂进料量：3.6kg/h；
反应温度：120℃-125℃；
反应压力：1.8MPaG；
碱催化剂占原料油脂的质量分数：2.5％；
塔式反应器加入的过程强化传质物料为总反应进料量的16.6wt％，管式反应器加入的过程强化传质物料为总反应进料量的8.0wt％。
在该反应条件下，一级酯交换反应中原料转化率为97.10％，二级酯交换反应中原料转化率为98.8％；一级酯交换反应停留时间为0.87小时，二级酯交换反应停留时间为1.11小时。
实施例2-3
采用本发明的酯交换反应工艺，酯交换反应原料为原料油脂、甲醇和碱性催化剂(原料油脂性质见表一)，将原料油脂、甲醇和碱性催化剂三者引入微通道混合设备I，其中原料油脂/甲醇以摩尔比为5:1，原料油脂引入微通道混合设备I的壳程侧，甲醇和液体碱催化剂引入微通道混合设备I的管程侧，经微通道混合设备I形成的混合物物料I作为主反应物料进入两级酯交换反应器，发生酯交换反应，其中一级反应器为塔式反应器，反应器尺寸为
Figure PCTCN2021127019-appb-000008
二级反应器为管式反应器，反应器尺寸为
Figure PCTCN2021127019-appb-000009
将原料油脂和甲醇以摩尔比为1:2的比例经微通道混合设备II形成混合物料II，作为强化传质物料分别引入塔式反应器和管式反应器，对酯交换反应过程进行强化，反应流出物离开反应器，进入分离单元。
微通道混合设备II中，微通道混合组件中的薄片采用不锈钢材质，薄片厚度为1.0mm，薄片夹缝间填充3层直径为1μm的玻璃纤维丝和1层直径为5μm的陶瓷纤维丝，纤维丝等间距排布，间距为1μm。纤维丝为波浪线周期性变化的曲线形状。
酯交换反应过程操作条件如下：
油脂进料量：3.6kg/h；
反应温度：120℃-125℃；
反应压力：2.0MPaG；
碱催化剂占原料油脂的质量分数：2.5％；
塔式反应器加入的过程强化传质物料为总反应进料量的20.0wt％，管式反应器加入的过程强化传质物料为总反应进料量的3.6wt％。
微通道混合设备I的操作条件如下：温度为120-125℃，压力为2.0MPaG；微通道混合设备II的操作条件如下：温度为120℃，压力2.0MPaG。
在该反应条件下，一级酯交换反应中原料转化率为97.0％，二级酯交换反应中原料转化率为98.9％；一级酯交换反应停留时间为1.01小时，二级酯交换反应停留时间为1.30小时。
实施例2-4
本实施例中，反应原料、反应器结构、反应过程、微通道混合设备I的操作条件、微通道混合设备II的操作条件同实施例2-3。与实施例2-3不同的是，本实施例一方面改变了进料量和酯交换反应条件，另一方面适当调整了强化传质物料的引入位置和引入量。
酯交换反应过程操作条件如下：
油脂进料量：4.0kg/h；
反应温度：120℃-125℃；
反应压力：2.0MPaG；
碱催化剂占原料油脂的质量分数：3.0％；
塔式反应器加入的过程强化传质物料为总反应进料量的22.4wt％，管式反应器加入的过程强化传质物料为总反应进料量的3.2wt％。
在该反应条件下，一级酯交换反应中原料转化率为96.8％，二级酯交换反应中原料转化率为99.1％；一级酯交换反应停留时间为1.01小时，二级酯交换反应停留时间为1.30小时。
实施例2-5
采用本发明的酯交换反应工艺，酯交换反应原料为原料油脂、甲醇和碱性催化剂(原料油脂性质见表一)，将原料油脂、甲醇和碱性催化剂三者引入微通道混合设备I，其中原料油脂/甲醇以摩尔比为8:1，原料油脂引入微通道混合设备I的壳程侧，甲醇和液体碱催化剂引入微通道混合设备I的管程侧，经微通道混合设备I形成的混合物物料I作为主反应物料进入两级酯交换反应器，发生酯交换反应，其中一级反应器为塔式反应器，反应器尺寸为
Figure PCTCN2021127019-appb-000010
二级反应器为管式反应器，反应器尺寸为
Figure PCTCN2021127019-appb-000011
将原料油脂和甲醇以摩尔比为1:1的比例经微通道混合设备II形成混合物料II，作为强化传质物料分别引入塔式反应器和管式反应器，对酯交换反应过程进行强化，反应流出物离开反应器，进入分离单元。
微通道混合设备II中，微通道混合组件中的薄片采用不锈钢材质，薄片厚度为1.5mm，薄片夹缝间填充8层直径为5μm的不锈钢纤维丝和2层直径为5μm的陶瓷纤维丝，纤维丝等间距排布，间距为1μm。纤维丝为波浪线周期性变化的曲线形状。
酯交换反应过程操作条件如下：
油脂进料量：4.0kg/h；
反应温度：120℃-125℃；
反应压力：2.0MPaG；
碱催化剂占原料油脂的质量分数：2.5％；
塔式反应器加入的过程强化传质物料为总反应进料量的21.6wt％，管式反应器加入的过程强化传质物料为总反应进料量的1.5wt％。
微通道混合设备I的操作条件如下：温度为120-125℃，压力为2.0MPaG；微通道混合设备II的操作条件如下：温度为120℃，压力2.0MPaG。
在该反应条件下，一级酯交换反应中原料转化率为97.8％，二级酯交换反应中原料转化率为98.9％；一级酯交换反应停留时间为0.611小时，二级酯交换反应停留时间为0.782小时。
实施例2-6
本实施例中，反应原料、反应器结构、反应过程、微通道混合设备I的操作条件、微通道混合设备II的操作条件同实施例2-5。与实施例2-3不同的是，本实施例一方面改变了进料量和酯交换反应条件，另一方面适当调整了强化传质物料的引入位置和引入量。
酯交换反应过程操作条件如下：
油脂进料量：4.0kg/h；
反应温度：120℃-125℃；
反应压力：1.8MPaG；
碱催化剂占原料油脂的质量分数：3.0％；
塔式反应器加入的过程强化传质物料为总反应进料量的17.5wt％，管式反应器加入的过程强化传质物料为总反应进料量的6.4wt％。
在该反应条件下，一级酯交换反应中原料转化率为97.3％，二级酯交换反应中原料转化率为98.8％；一级酯交换反应停留时间为0.611小时，二级酯交换反应停留时间为0.782小时。
本发明方法中的甘油三酸酯液滴在低碳醇中的分散尺寸和分散效果是通过高速摄像仪来获得，并通过选择若干个特征粒子来得到分散相粒子的均匀度，粒子尺寸越小、均匀度越高，说明混合分散的效果越好。为此，本实 施例及对比例的混合分散效果的测定方法为：同一条件下通过不同混合分散方法(如采用常规静态混合器、本发明反应器内微通道混合系统I和微通道混合系统II)对分散相甘油三酸酯和连续相低碳醇相进行混合，每组方法至少取得10组混合物料样品，利用英国IX i-SPEED 5高速摄像机来拍摄混合物料样品中分散相的粒子尺寸大小，将照片中粒子加和，计算出各种尺寸粒子的百分含量，得到各种尺寸粒子的正态分布图，从而得到粒子均匀度。
由本实施例及对比例的混合效果可以看出，采用本发明的生物柴油生产的酯交换反应装置及反应方法中，采用微通道混合设备I将原料油脂、低碳醇及催化剂形成的混合物料I作为主反应物料从反应器一端引入，其中的混合物料I中低碳醇与原料油脂的摩尔比≥3，使反应进料在反应器内保持两相均一，为酯交换反应的高转化率提供前提条件，然后再使另一部分低碳醇与甘油三酸酯的摩尔比≥3原料油脂和甲醇及催化剂在低碳醇与原料油脂的摩尔比<3的条件下通过微通道混合设备II形成混合进料II，作为强化传质物料引入酯交换反应器，混合进料II中由于原料油脂的液滴尺寸小、分子密集，能够快速突破相界面而补充反应消耗掉的原料油脂，从而大幅度强化整个反应过程的传质，改善酯交换反应速率和原料单程转化率，降低低碳醇与甘油三酸酯的摩尔比，减少反应器数量或反应停留时间，提高酯交换法生产生物柴油装置的生产效率。

Claims (40)

  1. 一种微通道液-液混合设备，所述的微通道液-液混合设备包括微通道组件和壳体，微通道组件固定于壳体内，壳体一端设置入口，用于至少两种反应液相的进料，另一端设置混合物料出口；微通道组件包含多个堆叠的薄片以及相邻薄片夹缝间填充的亲油性纤维丝和亲水性纤维丝，纤维丝与纤维丝间构成若干微通道，纤维丝通过薄片夹紧固定。
  2. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：微通道混合器的壳体内微通道组件沿夹缝方向，分为进料端和出料端，物料入口与进料端之间设置进料分布空间，物料出口与出料端之间设置出料分布空间，除进料端和出料端外，微通道组件其余各端均与壳体密封连接。
  3. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：所述的纤维丝可以单层或多层排布，优选1-50层，更优选为1-5层。
  4. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：所述的纤维丝为多层排布时，相邻两层纤维丝沿薄片垂直方向的投影为网状结构。
  5. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：任意一层中，优选地，每层纤维丝中，相邻纤维丝的间距为0.5μm-50μm，优选等间距排布；和/或，纤维丝沿薄片表面横向、纵向或斜向任意一种。
  6. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：所述的纤维丝为任意曲线形状，优选周期性变化的曲线形状。
  7. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：同一层的纤维丝的形状相同，更优选所有层的纤维丝的形状都相同。
  8. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：所述的纤维丝的直径为0.5-50μm，优选为0.5-5μm，更优选为0.5-1μm。
  9. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：所述的亲油性纤维丝为聚酯纤维丝、尼龙纤维丝、不锈钢纤维丝、聚氨酯纤维丝、聚丙烯纤维丝、聚丙烯腈纤维丝、聚氯乙烯纤维丝、或表面经过亲油处理的纤维丝材料中至少一种。
  10. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：所述的亲水性纤维丝选自主链或侧链含有亲水性基团的高分子聚合物或经过物理或化学方法亲水处理的纤维丝中的一种或多种。
  11. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：所述的亲水性纤维丝选自玻璃纤维丝、陶瓷纤维丝、丙纶纤维、聚酰胺纤维或丙烯酸纤维中一种或多种。
  12. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：所述的薄片厚度为0.05mm-5mm，优选0.1-1.5mm。
  13. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：所述相邻薄片夹缝间填充的亲油性纤维丝和亲水性纤维丝的数量比例为1:50-1:1。
  14. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：任意一层中的亲水性纤维丝均匀分布于亲油性纤维丝间。
  15. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：任意一层中亲油性纤维丝和亲水性纤维丝的数量比例为1:50-1:1。
  16. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：薄片的材质为金属、陶瓷、有机玻璃或聚酯材料中的任意一种或多种。
  17. 根据前述权利要求任一项所述的微通道液-液混合设备，其特征在于：薄片的形状为长方形、正方形、多边形、圆形、椭圆形或扇形中任意一种。
  18. 一种液-液反应装置，其包括微通道混合设备I、微通道混合设备II和反应器；
    所述的微通道混合设备I为管壳式结构，壳体内部设置无机膜管束；无机膜管束入口端与第一液相进料管线连通，无机膜管束外部的壳内空腔与第二液相进料管线连通，无机膜管束出口端为混合物料I出口；微通道混合设备I用于第一液相进料和第二液相进料形成混合物料I，第一液相进料由壳内空腔经无机膜管管壁孔道扩散至无机膜管内第一液相中，在管内高流速第一液相的剪切力作用下二者形成均一的混合物料I，作为主反应进料；其中，优选地，在微通道混合设备I中提供控制装置，使得第一液相/第二液相的比值大于或小于(优选大于)该反应的第一液相/第二液相的理论比值；
    所述的微通道混合设备II为根据权利要求1的微通道液-液混合设备，其包括微通道组件和壳体，微通道组件固定于壳体内，壳体一端设置入口，用于第一液相和第二液相的进料，另一端设置混合物料II出口；微通道组件包含多个堆叠的薄片以及相邻薄片夹缝间填充的亲油性纤维丝和亲水性纤维丝，纤维丝与纤维丝间构成若干微通道，纤维丝通过薄片夹紧固定；微通道混合设备II用于第一液相和第二液相形成混合物料II，第一液相和第二液相在微通道混合设备II内，经纤维丝切割、混合形成混合物料II；其中，优 选地，在微通道混合设备II中提供控制装置，使得第一液相/第二液相的比值不大于或不小于(优选不大于)该反应的第一液相/第二液相的理论比值；
    所述的反应器顶部、底部或侧部设置进料口，底部、顶部或侧部设置出料口，反应器本体上设置强化传质物料入口，原则上强化传质物料入口可以设置在反应器内任意位置。微通道混合设备I的混合物料I出口经管线与进料口连接，微通道混合设备II的混合物料II出口与强化传质物料入口连接。
  19. 根据权利要求18所述的液-液反应装置，其特征在于：所述的微通道混合设备I的无机膜管束为陶瓷膜、金属膜、金属/陶瓷复合膜、合金膜、分子筛复合膜、沸石膜或玻璃膜等中的一种或多种；无机膜管管壁上的孔径为10nm-1μm。
  20. 一种使用根据权利要求18所述的液-液反应装置进行的烯烃水合反应，其特征在于，所述的烯烃水合反应器为固定床反应器，强化传质物料入口设置在相邻两层催化剂床层之间；催化剂床层填装烯烃水合催化剂；烯烃水合反应器根据需要设置1个或多个，当多个时，反应器之间并联或串联；反应器内设置若干催化剂床层。
  21. 根据权利要求20所述的烯烃水合反应，其特征在于，将水烯比≥1的烯烃相和水相经微通道混合设备I混合形成混合物料I，作为主反应物料由烯烃水合反应器底部进入；将水烯比<1的烯烃相和水相经微通道混合设备II混合形成混合物料II，作为强化传质物料引入反应器内，混合物料I和混合物料II在催化剂床层发生烯烃水合反应，反应产物由反应器顶部出口流出，进入下一分离单元。
  22. 根据权利要求20所述的烯烃水合反应，其特征在于，微通道混合设备I的操作条件一般如下：温度为常温-250℃，压力为1.0-10.0MPaG；微通道混合设备II的操作条件一般如下：温度为常温-200℃，压力1.0-10.0MPaG。
  23. 根据权利要求20所述的烯烃水合反应，其特征在于，所述的烯烃相一般为乙烯、丙烯、正丁烯、异丁烯、异戊烯或环己烯等中的任意一种。
  24. 根据权利要求20所述的烯烃水合反应，其特征在于，所述的烯烃水合反应器一般采用下进上出形式。
  25. 根据权利要求20所述的烯烃水合反应，其特征在于，所述的微通道混合设备I中，水烯质量比一般为2:1-20:1；所述的微通道混合设备II中，水烯质量比一般为1:20-1:1。
  26. 根据权利要求20所述的烯烃水合反应，其特征在于，所述的微通道混合设备I形成的混合物料I中，烯烃液滴的粒径d1为100-900μm，优选分散均匀度≥80％；
    微通道混合设备II形成的混合物料II中，烯烃液滴的粒径d2为小于100μm，优选0.1-50μm。
  27. 根据权利要求20所述的烯烃水合反应，其特征在于，所述的混合物料II的加入量为反应器总物料(烯烃相和水相总量)的1wt％-30wt％；混合物料II的分为多股加入时，优选地，沿物料在反应器内流动方向上各股加入量逐渐增加(例如后一股相对于前一股增加5-20wt％)；和/或，优选地，沿反应器内物料流动方向水烯比降低或不变。
  28. 根据权利要求20所述的烯烃水合反应，其特征在于，烯烃水合反应器的催化剂床层内采用具有酸催化功能的催化剂，如矿物酸、苯磺酸、离子交换树脂、分子筛等类型的催化剂。
  29. 根据权利要求20所述的烯烃水合反应，其特征在于，烯烃水合反应条件一般为：温度80-250℃，压力1.0-10.0MPaG，空速为0.1-3.0h -1。
  30. 一种使用根据权利要求18所述的液-液反应装置进行的酯交换反应，其特征在于所述的反应器为釜式反应器、塔式反应器、管式反应器或上述反应器的改进形式，可以根据需要设置1个或多个，反应器之间并联或串联；至少引入一股由微通道混合设备II形成的混合物料作为强化传质物料。
  31. 根据权利要求30所述的酯交换反应，其特征在于：将低碳醇与甘油三酸酯的摩尔比≥3的两相经微通道混合设备I混合形成混合物料I，作为主反应物料进入酯交换反应器；将低碳醇与甘油三酸酯的摩尔比<3的两相经微通道混合设备II混合形成混合物料II，作为强化传质物料引入反应器内，混合物料I和混合物料II在反应器内发生酯交换反应，反应产物由反应器出口流出，进入分离单元。
  32. 根据权利要求30所述的酯交换反应，其特征在于：微通道混合设备I的操作条件一般如下：温度为常温-150℃，压力为0.5-3.0MPaG；微通道混合设备II的操作条件一般如下：温度为常温-150℃，压力0.5-3.0MPaG。其中，液体催化剂用量为原料油脂用量的0.5％-10％。
  33. 根据权利要求30所述的酯交换反应，其特征在于：所述原料油脂为甘油三酸酯，主要来源于动物油或植物油；原料油脂的酸值可以介于0-130mgKOH/g的脂肪酸和油脂(含地沟油)，优选小桐子油、菜籽油、大豆油、亚麻油、花生油、棕榈油、茶籽油等的精制植物油。
  34. 根据权利要求30所述的酯交换反应，其特征在于：所述的低碳醇的碳数为1-6的脂肪醇，可以为单一的脂肪醇，也可以是一种或多种脂肪醇的混合物，优选甲醇。
  35. 根据权利要求30所述的酯交换反应，其特征在于：所述的酯交换反应采用碱性催化剂，碱性催化剂可以为氢氧化钠、氢氧化钾、氢氧化钡、氢氧化钙、氧化镁、氧化钙、氧化钡、二乙胺中的一种或多种混合物。
  36. 根据权利要求30所述的酯交换反应，其特征在于：所述的酯交换反应条件如下：反应压力0.5-2.0MPaG，反应温度为100-150℃；低碳醇与甘油三酸酯的摩尔比为1:3-1:15，碱性催化剂用量为原料油脂用量的0.5％-10％。
  37. 根据权利要求30所述的酯交换反应，其特征在于：强化传质物料II中，可以包含或不包含液体催化剂。
  38. 根据权利要求30所述的酯交换反应，其特征在于：酯交换反应器的总停留时间为0.5-7小时，优选0.5-3.5小时。
  39. 根据权利要求30所述的酯交换反应，其特征在于：所述的微通道混合设备I中，低碳醇与甘油三酸酯的摩尔比一般为3:1-15:1；所述的微通道混合设备II中，醇油摩尔比一般为1:10-1:0.33。
  40. 根据权利要求30所述的酯交换反应，其特征在于：所述的微通道混合设备I形成的混合物料I中，甘油三酸酯液滴的粒径d1为100-900μm，优选分散均匀度≥80％；微通道混合设备II形成的混合物料II中，甘油三酸酯液滴的粒径d2为小于100μm，优选0.1-50μm。
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