CN114377557A - Clean production process for continuously preparing n-propanol - Google Patents
Clean production process for continuously preparing n-propanol Download PDFInfo
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- CN114377557A CN114377557A CN202210079349.3A CN202210079349A CN114377557A CN 114377557 A CN114377557 A CN 114377557A CN 202210079349 A CN202210079349 A CN 202210079349A CN 114377557 A CN114377557 A CN 114377557A
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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Abstract
The invention discloses a clean production process for continuously preparing n-propanol, belongs to the field of n-propanol preparation, and particularly relates to a preparation method of a permeable gas-liquid separation composite membrane, which comprises the following steps: adding KH560 and cyclamate into cyclodextrin solution for dispersion, and spray drying to obtain composite microcapsule; adding the modified porous silicon and the composite microcapsule into a PDMS solution, adding ethyl orthosilicate and dibutyltin dilaurate, reacting to obtain a membrane casting solution, coating the membrane casting solution on a basement membrane, and drying to obtain a permeable gas-liquid separation composite membrane; the modified porous silicon is modified by KH550 and KH 570. According to the invention, modified porous silicon, composite microcapsules, ethyl orthosilicate serving as a cross-linking agent and dibutyltin dilaurate serving as a catalyst are used for preparing a casting solution in a PDMS solution, and the casting solution is coated on a polytetrafluoroethylene basement membrane to prepare the permeable gas-liquid separation composite membrane.
Description
Technical Field
The invention belongs to the field of n-propanol preparation, and particularly relates to a clean production process for continuously preparing n-propanol.
Background
N-propanol is produced by the hydrogenation of propionaldehyde, which is obtained by the hydroformylation of ethylene by the reaction of carbon monoxide and hydrogen. The propionaldehyde hydrogenation catalyst can be selected from an activated nickel or cobalt catalyst, the hydrogenation reaction is carried out at a proper temperature and pressure, and the generated crude propanol product contains a small amount of impurities such as water, n-propyl propionate, di-n-propyl ether and the like, wherein the water and the n-propyl propionate are the most important impurities influencing the product quality, so the purification of the crude n-propanol from the hydrogenation reaction zone is completed by rectification, the small amount of water in the crude n-propanol can form two binary minimum azeotropes with the n-propanol and the n-propyl propionate, and after the azeotropes are extracted from the top of the tower, the qualified n-propanol product can be obtained.
CN101225018A, discloses a method for removing propyl propionate as a byproduct in a process for preparing n-propanol by hydrogenating propionaldehyde, and indicates that propyl propionate, water and n-propanol form a three-phase azeotrope, and the three-phase azeotrope contains about 5-45% of water, 40-70% of n-propanol and 5-25% of propyl propionate, and the three-phase azeotrope can cause great waste due to the unavailability; CN101774887A discloses a clean production process for preparing n-propanol by hydrogenating propionaldehyde, which adopts a pervaporation membrane to separate n-propanol and propyl propionate.
In the prior art, the invention aims to provide a clean production process for continuously preparing n-propanol, which can reduce various problems, such as the defect that a three-phase azeotrope containing propyl propionate, water and n-propanol cannot be recycled in a production method of the n-propanol, and a series of problems of catalyst loss, large heat loss, high solvent recovery energy consumption, poor tail gas treatment effect and the like in the production process.
Disclosure of Invention
The invention aims to provide a preparation method of a permeable gas-liquid separation composite membrane with good permeation flux and good separation effect.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a preparation method of a permeable gas-liquid separation composite membrane comprises the following steps:
adding KH560 and cyclamate into cyclodextrin solution for dispersion, and spray drying to obtain composite microcapsule;
adding the modified porous silicon and the composite microcapsule into a PDMS solution, adding ethyl orthosilicate and dibutyltin dilaurate, reacting to obtain a membrane casting solution, coating the membrane casting solution on a basement membrane, and drying to obtain a permeable gas-liquid separation composite membrane; the modified porous silicon is modified by KH550 and KH 570. Under the action of a catalyst, molecular chains of PDMS with bifunctional groups and TEOS with tetrafunctional groups form chemical bonds, and the PDMS and the TEOS can be connected to form a three-dimensional reticular structure. The crosslinked PDMS membrane has low mechanical strength and is compounded on a polytetrafluoroethylene microporous membrane formed by biaxial stretching, but when the composite membrane is prepared, PDMS can permeate into pores of the polytetrafluoroethylene microporous membrane to influence the permeability of the composite membrane. The invention introduces the modified porous silicon and the composite microcapsule into PDMS to prepare the permeable gas-liquid separation composite membrane, thereby improving the permeation flux of the permeable gas-liquid separation composite membrane and the separation factor of the permeable gas-liquid separation composite membrane.
Preferably, an anti-caking agent is added into the composite microcapsule, and the anti-caking agent is aluminum silicate.
Preferably, KH560 is added in an amount of 7-18wt% of the cyclodextrin solution.
Preferably, the addition amount of the cyclamate is 1-6wt% of the cyclodextrin solution.
Preferably, the amount of the composite microcapsule added is 1-5wt% of the PDMS solution.
The invention discloses a permeable gas-liquid separation composite membrane prepared by the method.
Preferably, the permeation flux of the permeation gas-liquid separation composite membrane is 380 g.m-2h-1The above.
Preferably, the preparation method of the permeable gas-liquid separation composite membrane comprises porous silicon preparation, modified porous silicon preparation and composite microcapsule preparation.
More preferably, in the preparation of the porous silicon, tetrapropylammonium hydroxide is added into deionized water and uniformly mixed to obtain tetrapropylammonium hydroxide solution, nano-silica is added, the mixture is stirred and mixed for 30-120min to form uniform colloid, then the uniform colloid is transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining and reacts for 18-48h at the temperature of 100-150 ℃, after the reaction is finished, the reacted mother liquor is taken out and centrifuged to obtain precipitate, the washing solution is washed by deionized water until the washing solution is neutral, the precipitate is dried, transferred to a muffle furnace and calcined for 4-9h at the temperature of 500-600 ℃, and the porous silicon is obtained after the calcination is finished and is cooled to room temperature.
Still more preferably, the tetrapropylammonium hydroxide solution has a tetrapropylammonium hydroxide content of 20 to 35 wt.%.
Still more preferably, the amount of nanosilica added is 12-26wt% of the tetrapropylammonium hydroxide solution.
Even more preferably, the room temperature is constant between 20-35 ℃.
More preferably, in the preparation of the modified porous silicon, the porous silicon is added into an alcohol-water solution, then a silane coupling agent is added, the pH value is adjusted to 8-9, the modification reaction is carried out for 6-18h at the temperature of 60-80 ℃, after the reaction is finished, the reaction product is cooled to room temperature, filtered, washed and precipitated by deionized water, and dried to obtain the modified porous silicon.
Still more preferably, the alcohol aqueous solution contains deionized water of ethanol, the alcohol aqueous solution contains 80-90wt% of ethanol, and the balance is deionized water.
Still more preferably, the silane coupling agent is KH550 and KH570, wherein the amount of KH550 is 3-5wt% and the amount of KH570 is 2-6wt% based on the aqueous alcohol solution.
More preferably, in the preparation of the composite microcapsule, cyclodextrin is added into deionized water, stirred, mixed and dissolved to obtain a cyclodextrin solution, then a silane coupling agent and cyclamate are added, a composite emulsion is obtained through high-speed dispersion, then the emulsion is dried by a spray dryer to obtain the composite microcapsule, and an anti-caking agent is added into the composite microcapsule to prevent caking.
Even more preferably, the cyclodextrin solution has a cyclodextrin content of 20-30 wt%.
Still more preferably, the silane coupling agent is KH560, and the amount of KH560 added is 7-18wt% of the cyclodextrin solution.
Still more preferably, the amount of added cyclamate is 1-6wt% of the cyclodextrin solution.
Still more preferably, the anti-caking agent is aluminum silicate, which is used in an amount of 3-5wt% of the composite microcapsule.
More preferably, in the preparation of the composite membrane for gas-liquid separation infiltration, PDMS (hydroxyl-terminated polydimethylsiloxane) is added into n-heptane, stirring, mixing and dissolving are carried out to obtain a PDMS solution, then modified porous silicon and composite microcapsules are added into the PDMS solution, a cross-linking agent ethyl orthosilicate is added, a catalyst dibutyltin dilaurate is added, stirring and reacting are carried out at the temperature of 50-70 ℃ for 2-6h, after the reaction is finished, cooling is carried out to the room temperature to obtain a casting membrane solution, a membrane scraping machine is adopted to coat the casting membrane solution onto a polytetrafluoroethylene basement membrane, drying is carried out at the temperature of 20-35 ℃ for 3-12h, then heating treatment is carried out at the temperature of 70-90 ℃ for 3-12h, and cooling is carried out to obtain the composite membrane for gas-liquid separation infiltration.
Even more preferably, the content of PDMS in the PDMS solution is 10-30 wt%.
Still more preferably, the modified porous silicon is added in an amount of 1-6wt% of the PDMS solution.
Still more preferably, the composite microcapsule is added in an amount of 1-5wt% of the PDMS solution.
Still more preferably, the amount of ethyl orthosilicate added is 2-6wt% of the PDMS solution.
Still more preferably, the amount of dibutyltin dilaurate added is from 0.01 to 0.08wt% of the PDMS solution.
More preferably, 3-quinuclidinone hydrochloride can be added in the preparation of the permeation gas-liquid separation composite membrane, and the addition amount of the 3-quinuclidinone hydrochloride is 0.6-3.6wt% of the PDMS solution. According to the method, modified porous silicon, composite microcapsules, a cross-linking agent ethyl orthosilicate and a catalyst dibutyltin dilaurate are adopted to be placed in a PDMS solution, and finally the permeable gas-liquid separation composite membrane is prepared.
The invention aims to provide a clean production method for continuously preparing n-propanol by using the permeable gas-liquid separation composite membrane.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a clean production method for continuously preparing n-propanol comprises the following steps:
reacting synthesis gas and ethylene in a hydroformylation reaction kettle to obtain crude propionaldehyde, and rectifying and separating to obtain propionaldehyde; the synthesis gas is hydrogen and carbon monoxide.
Mixing propionaldehyde and hydrogen, reacting in a hydrogenation reactor to obtain crude n-propanol, and rectifying and separating the crude n-propanol to obtain n-propanol and a byproduct residual liquid;
the by-product residual liquid passes through the liquid-phase material separated by the permeable gas-liquid separation composite membrane dehydration device, and the n-propanol is separated by the subsequent treatment of the liquid-phase material; the byproduct residual liquid is formed by three-phase azeotropy of propyl propionate, water and n-propanol.
Preferably, the synthesis gas and ethylene are present in a volume ratio of 1: 1-5.
Preferably, the propanal is mixed with hydrogen in a volume ratio of 1: mixing at a ratio of 20-100.
Preferably, in the preparation of propionaldehyde, the synthesis gas and ethylene are treated by an ethylene contract purification system and are pressurized, then are heated to 80-150 ℃, enter a hydroformylation reaction kettle to carry out a oxo-synthesis reaction, the temperature is controlled to be 80-150 ℃ while materials continuously enter, the pressure is 0.5-2.5MPa, the reacted gas is condensed to obtain crude propionaldehyde, and the uncondensed gas is used as a raw material to participate in the reaction again by a compressor circulation system.
More preferably, the crude propionaldehyde is rectified by a rectification system to obtain propionaldehyde, which is used in the next step.
More preferably, the synthesis gas is hydrogen and carbon monoxide, and the composition of the hydrogen and the carbon monoxide in the synthesis gas is that the volume ratio of 1: 0.5-2, the volume ratio of the synthesis gas to the ethylene is 1: 1-5.
Preferably, in the preparation of the n-propanol, propionaldehyde and hydrogen are mixed, the mixture enters a hydrogenation reactor, the reaction is carried out under the conditions that the temperature is 100-; and (3) rectifying the liquid-phase material separated by the permeation gas-liquid separation composite membrane dehydration device to separate the n-propanol and the propyl propionate in the liquid-phase material.
More preferably, the propanal is present in a volume ratio to hydrogen of 1: mixing at a ratio of 20-100.
The invention aims to provide a clean production method for continuously preparing n-propanol.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a clean production method for continuously preparing n-propanol comprises the following steps:
propionaldehyde preparation: the solid columnar catalyst is filled into a No. 1 fixed bed reactor, and the reactor is a radial phase reactor with a shell side filled with a catalyst tube and a moving heat medium. And (3) filling the synthesis gas into the reactor system to the pressure of 0.5-2.5MPa, starting a system circulating compressor to perform system circulation, and heating the synthesis gas by a heater to increase the temperature of the reactor to 80-150 ℃. And when the circulation of the reactor system is stable, starting a heating medium circulating pump, and supplying a heat transfer heating medium to the tube pass of the reactor to carry out heat transfer circulation. After the internal and external circulation is stable, mixing and heating the purified synthesis gas (H2, CO) and ethylene to 80-150 ℃, then feeding the mixture into a No. 1 fixed bed reactor, and controlling the mass ratio of the ethylene to the synthesis gas to be 1: 2.5, keeping the pressure of the reactor at 0.5-2.5MPa, feeding raw material gas from the bottom of the No. 1 reactor, and discharging reaction gas from the top. The reaction gas is cooled to a 1# crude aldehyde tank through a first-stage cooler, the uncondensed gas is subjected to multi-stage deep cooling to condense the propionaldehyde in the gas phase to a 2# crude aldehyde tank, the aldehyde content in the uncondensed gas is lower than 0.1%, and the gas enters a compressor circulation system. And partial purge gas controls the pressure and the non-condensed steam content of the system. The No. 1 fixed bed reaction is a strong exothermic reaction, and after the reaction starts, the reaction is circularly removed from the reactor by a heating medium system. Then the low-temperature water is prepared by heating the lithium bromide unit by a heating medium. The reaction heat is reasonably recovered. And (3) pressurizing the crude aldehyde in the No. 1 crude aldehyde tank and the No. 2 crude aldehyde tank through a pressurizing pump, sending the pressurized crude aldehyde into a gas tower, and carrying out gas stripping refining by utilizing raw material gas to obtain an aldehyde product for use in the No. 2 hydrogenation reaction.
Preparing n-propanol: and (3) performing hydrogen replacement on the 2# hydrogenation reaction system, and starting a circulation system of a hydrogen circulation compressor when the hydrogen content of the system is 5-50% and the system pressure is 0.8-2.5 MPa. Then the heater is started to heat the system, and the heating speed is controlled to be less than 20 ℃/h. When the temperature is raised to 100-150 ℃, the concentration in the hydrogen system is raised to 85-98%, and the start-up preparation work is completed under the condition of material-passing start-up. The reactor has several beds and several ply feeds, and each bed is equipped with cold hydrogen, hot hydrogen and propionaldehyde feeding system. Propionaldehyde is mixed with cold and hot hydrogen and then enters an ejector above a reactor bed layer, and is sprayed and atomized by the ejector and then reacts with a catalyst bed layer below the ejector in a contact manner. Controlling the hydrogen-oil ratio to be 100-20: 1, controlling the temperature of the reactor at 100-. And the reaction discharge gas enters a No. 3 crude alcohol tank after passing through a first-stage quenching heat exchanger, and the gas which is not condensed enters a No. 4 crude alcohol tank after passing through multi-stage deep cooling. After the alcohol content of the reaction gas after multistage condensation is lower than 0.1%, the reaction gas enters a compression circulation system and is subjected to a recycling reaction. The crude n-propanol is produced and is rectified and refined to obtain the product n-propanol.
Tail gas recovery: the purge gas of the 1# reactor system contains ethylene, synthesis gas and the like in a certain proportion, and the purge gas of the 2# reactor system contains hydrogen and the like in a certain proportion, so that the gas recycling value is high. After the two gases enter a tail gas system to be mixed, hydrogen is firstly separated out through a hydrogen recovery membrane, and then the hydrogen is pressurized through a compressor and enters a cryogenic ethylene recovery system to recover ethylene. And the carbon monoxide which cannot be recovered is used as final tail gas to enter the waste heat boiler system for combustion to produce preheated steam. All gases in the system are recycled, and finally tail gas is combusted, so that the energy is saved and the system is clean.
More preferably, the permeate gas-liquid separation composite membrane is used for purification of crude n-propanol.
According to the invention, the modified porous silicon, the composite microcapsule, the cross-linking agent ethyl orthosilicate and the catalyst dibutyltin dilaurate are used for preparing the casting solution in the PDMS solution, and the casting solution is coated on the polytetrafluoroethylene basement membrane to prepare the permeable gas-liquid separation composite membrane, so that the permeable gas-liquid separation composite membrane has the following beneficial effects: the permeation flux of the permeation gas-liquid separation composite membrane is high, and the permeation flux is 370--2h-1(ii) a The separation effect of the permeation gas-liquid separation composite membrane is good, and the separation factor is 13-9.5%. Therefore, the invention is a permeable gas-liquid separation composite membrane with good permeation flux and good separation effect and a preparation method thereof, and the permeable gas-liquid separation composite membrane can be used in a clean production method for continuously preparing n-propanol.
Drawings
FIG. 1 is a permeation flux diagram of a permeation gas-liquid separation composite membrane;
FIG. 2 is a separation factor graph of a permeate gas-liquid separation composite membrane;
FIG. 3 is a graph showing the swelling degree of a permeated gas-liquid separation composite membrane.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
a preparation method of a permeable gas-liquid separation composite membrane,
preparing porous silicon: adding tetrapropylammonium hydroxide into deionized water, uniformly mixing to obtain a tetrapropylammonium hydroxide solution, adding nano-silica, stirring and mixing for 60min to form uniform colloid, then transferring the colloid into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at the temperature of 120 ℃ for 36h, after the reaction is finished, taking out the reacted mother liquor, centrifuging to obtain a precipitate, washing the precipitate with deionized water until the washing liquid is neutral, drying the precipitate, transferring the precipitate into a muffle furnace, calcining at the temperature of 600 ℃ for 5h, and cooling to room temperature after the calcination is finished to obtain the porous silicon. The content of the tetrapropylammonium hydroxide in the tetrapropylammonium hydroxide solution is 30wt%, and the addition amount of the nano-silica is 24wt% of the tetrapropylammonium hydroxide solution. The room temperature was 25 ℃.
Preparing modified porous silicon: adding porous silicon into an alcohol-water solution, adding a silane coupling agent, adjusting the pH value to 8, carrying out modification reaction at the temperature of 80 ℃ for 12h, cooling to room temperature after the reaction is finished, filtering, washing the precipitate with deionized water, and drying to obtain the modified porous silicon. The alcohol-water solution contains deionized water of ethanol, the alcohol-water solution contains 90wt% of ethanol, and the balance is deionized water; the silane coupling agent is KH550 and KH570, wherein the addition amount of the KH550 is 4wt% of the alcohol-water solution, and the addition amount of the KH570 is 5wt% of the alcohol-water solution. The room temperature was 25 ℃.
Preparing a composite microcapsule: adding cyclodextrin into deionized water, stirring, mixing and dissolving to obtain a cyclodextrin solution, adding a silane coupling agent and cyclamate, dispersing at a high speed to obtain a composite emulsion, drying the emulsion by a spray dryer to obtain composite microcapsules, and adding an anti-caking agent into the composite microcapsules to prevent caking. The cyclodextrin content of the cyclodextrin solution was 26 wt%; the silane coupling agent is KH560, and the addition amount of the KH560 is 14wt% of the cyclodextrin solution; the addition amount of the cyclamate is 2.4wt% of the cyclodextrin solution; the anti-caking agent is aluminum silicate, and the usage amount of the aluminum silicate is 4wt% of the composite microcapsule.
Preparing a permeating gas-liquid separation composite membrane: adding PDMS (hydroxyl-terminated polydimethylsiloxane) into n-heptane, stirring, mixing and dissolving to obtain a PDMS solution, adding modified porous silicon and a composite microcapsule into the PDMS solution, adding a cross-linking agent ethyl orthosilicate, adding a catalyst dibutyltin dilaurate, stirring and reacting at 60 ℃ for 4 hours, cooling to room temperature after the reaction is finished to obtain a casting solution, coating the casting solution on a polytetrafluoroethylene base membrane by using a film scraping machine, drying at 30 ℃ for 6 hours, heating at 90 ℃ for 6 hours, and cooling to obtain a permeable gas-liquid separation composite membrane. The content of PDMS in the PDMS solution is 25wt%, the addition amount of the modified porous silicon is 5wt% of the PDMS solution, the addition amount of the composite microcapsule is 3wt% of the PDMS solution, the addition amount of ethyl orthosilicate is 5wt% of the PDMS solution, and the addition amount of dibutyltin dilaurate is 0.04wt% of the PDMS solution.
Example 2:
a preparation method of a permeable gas-liquid separation composite membrane,
this example is different from example 1 only in that the amount of the added cyclamate was 4.1wt% of the cyclodextrin solution in the preparation of the composite microcapsule.
Example 3:
a preparation method of a permeable gas-liquid separation composite membrane,
this example is different from example 1 only in that the amount of the added cyclamate was 5.6wt% of the cyclodextrin solution in the preparation of the composite microcapsule.
Example 4:
a preparation method of a permeable gas-liquid separation composite membrane,
this example is compared to example 3, except that the amount of aluminum silicate used in the preparation of the composite microcapsule was 3.3wt% of the composite microcapsule.
Example 5:
a preparation method of a permeable gas-liquid separation composite membrane,
this example is different from example 3 only in that the cyclodextrin content of the cyclodextrin solution in the composite microcapsule preparation was 21 wt%.
Example 6:
a preparation method of a permeable gas-liquid separation composite membrane,
preparing porous silicon: adding tetrapropylammonium hydroxide into deionized water, uniformly mixing to obtain a tetrapropylammonium hydroxide solution, adding nano-silica, stirring and mixing for 60min to form uniform colloid, then transferring the colloid into a stainless steel reaction kettle with a polytetrafluoroethylene lining, reacting at the temperature of 120 ℃ for 36h, after the reaction is finished, taking out the reacted mother liquor, centrifuging to obtain a precipitate, washing the precipitate with deionized water until the washing liquid is neutral, drying the precipitate, transferring the precipitate into a muffle furnace, calcining at the temperature of 600 ℃ for 5h, and cooling to room temperature after the calcination is finished to obtain the porous silicon. The content of the tetrapropylammonium hydroxide in the tetrapropylammonium hydroxide solution is 30wt%, and the addition amount of the nano-silica is 24wt% of the tetrapropylammonium hydroxide solution. The room temperature was 25 ℃.
Preparing modified porous silicon: adding porous silicon into an alcohol-water solution, adding a silane coupling agent, adjusting the pH value to 8, carrying out modification reaction at the temperature of 80 ℃ for 12h, cooling to room temperature after the reaction is finished, filtering, washing the precipitate with deionized water, and drying to obtain the modified porous silicon. The alcohol-water solution contains deionized water of ethanol, the alcohol-water solution contains 90wt% of ethanol, and the balance is deionized water; the silane coupling agent is KH550 and KH570, wherein the addition amount of the KH550 is 4wt% of the alcohol-water solution, and the addition amount of the KH570 is 5wt% of the alcohol-water solution. The room temperature was 25 ℃.
Preparing a composite microcapsule: adding cyclodextrin into deionized water, stirring, mixing and dissolving to obtain a cyclodextrin solution, adding a silane coupling agent and cyclamate, dispersing at a high speed to obtain a composite emulsion, drying the emulsion by a spray dryer to obtain composite microcapsules, and adding an anti-caking agent into the composite microcapsules to prevent caking. The cyclodextrin content of the cyclodextrin solution was 26 wt%; the silane coupling agent is KH560, and the addition amount of the KH560 is 14wt% of the cyclodextrin solution; the addition amount of the cyclamate is 5.6wt% of the cyclodextrin solution; the anti-caking agent is aluminum silicate, and the usage amount of the aluminum silicate is 4wt% of the composite microcapsule.
Preparing a permeating gas-liquid separation composite membrane: adding PDMS (hydroxyl-terminated polydimethylsiloxane) into n-heptane, stirring, mixing and dissolving to obtain a PDMS solution, then adding modified porous silicon, composite microcapsules and 3-quinuclidinone hydrochloride into the PDMS solution, adding a cross-linking agent ethyl orthosilicate, adding a catalyst dibutyltin dilaurate, stirring and reacting for 4 hours at the temperature of 60 ℃, cooling to room temperature after the reaction is finished to obtain a casting solution, coating the casting solution on a polytetrafluoroethylene basement membrane by using a membrane scraping machine, drying for 6 hours at the temperature of 30 ℃, heating for 6 hours at the temperature of 90 ℃, and cooling to obtain a permeable gas-liquid separation composite membrane. The content of PDMS in the PDMS solution is 25wt%, the addition amount of the modified porous silicon is 5wt% of the PDMS solution, the addition amount of the composite microcapsule is 3wt% of the PDMS solution, the addition amount of 3-quinuclidinone hydrochloride is 1.3wt% of the PDMS solution, the addition amount of ethyl orthosilicate is 5wt% of the PDMS solution, and the addition amount of dibutyltin dilaurate is 0.04wt% of the PDMS solution.
Example 7:
a preparation method of a permeable gas-liquid separation composite membrane,
this example is different from example 6 only in that 3-quinuclidinone hydrochloride was added in an amount of 2.4wt% based on the PDMS solution in the preparation of the permeate gas-liquid separation composite membrane.
Example 8:
a preparation method of a permeable gas-liquid separation composite membrane,
this example is different from example 6 only in that 3-quinuclidinone hydrochloride was added in an amount of 3.1wt% based on the PDMS solution in the preparation of the permeate gas-liquid separation composite membrane.
Example 9:
a preparation method of a permeable gas-liquid separation composite membrane,
this example is compared to example 8, except that the amount of aluminum silicate used in the preparation of the composite microcapsule was 4.9wt% of the composite microcapsule.
Example 10:
a preparation method of a permeable gas-liquid separation composite membrane,
this example is different from example 8 only in that the cyclodextrin content of the cyclodextrin solution in the composite microcapsule preparation was 28 wt%.
Example 11:
a clean process for continuously preparing n-propanol,
propionaldehyde preparation: the synthesis gas and ethylene are treated by an ethylene contract purification system and then are pressurized, the mixture is heated to 100 ℃, the mixture enters a hydroformylation reaction kettle to carry out a oxo reaction, the temperature of the mixture is controlled to be 100 ℃ while the material continuously enters, the pressure of the mixture is 1.5MPa, the reacted gas is condensed to obtain crude propionaldehyde, and the uncondensed gas is used as a raw material to participate in the reaction again by a compressor circulation system. And rectifying the crude propionaldehyde by a rectifying system to obtain propionaldehyde for the next step. The synthesis gas is hydrogen and carbon monoxide, and the components of the hydrogen and the carbon monoxide in the synthesis gas are in a volume ratio of 1: 1, synthesis gas and ethylene in a volume ratio of 1: 2.5.
Preparing n-propanol: mixing propionaldehyde and hydrogen, feeding the mixture into a hydrogenation reactor, reacting at the temperature of 130 ℃ and under the pressure of 2MPa to generate crude propanol, feeding the crude n-propanol into a rectification system, performing heat exchange and cooling to 40 ℃, performing gas-liquid separation to obtain n-propanol, wherein most of gas phase is hydrogen, feeding the hydrogen into an n-propanol preparation circulation system for recycling, rectifying the crude propanol, condensing and performing heat exchange on a three-phase azeotrope residual liquid formed by a byproduct propyl propionate generated by reaction, water and the n-propanol by a light-ends removal tower, and feeding the three-phase azeotrope residual liquid into a permeation gas-liquid separation dehydration device; and (3) rectifying the liquid-phase material separated by the permeation gas-liquid separation composite membrane dehydration device to separate the n-propanol and the propyl propionate in the liquid-phase material. Propionaldehyde and hydrogen in a volume ratio of 1: and mixing at a ratio of 50.
The permeate gas-liquid separation composite membrane of this example was from example 3.
Example 12:
this example differs from example 11 only in that the permeate gas-liquid separation composite membrane of this example was derived from example 5.
Example 13:
this example differs from example 11 only in that the permeate gas-liquid separation composite membrane of this example was derived from example 8.
Example 14:
a clean process for continuously preparing n-propanol,
propionaldehyde preparation: the synthesis gas and ethylene are treated by an ethylene contract purification system and then are pressurized, the mixture is heated to 100 ℃, the mixture enters a hydroformylation reaction kettle to carry out a oxo reaction, the temperature of the mixture is controlled to be 100 ℃ while the material continuously enters, the pressure of the mixture is 1.5MPa, the reacted gas is condensed to obtain crude propionaldehyde, and the uncondensed gas is used as a raw material to participate in the reaction again by a compressor circulation system. And rectifying the crude propionaldehyde by a rectifying system to obtain propionaldehyde for the next step. The synthesis gas is hydrogen and carbon monoxide, and the components of the hydrogen and the carbon monoxide in the synthesis gas are in a volume ratio of 1: 1, synthesis gas and ethylene in a volume ratio of 1: 2.5.
Preparing n-propanol: mixing propionaldehyde and hydrogen, feeding the mixture into a hydrogenation reactor, reacting at the temperature of 130 ℃ and under the pressure of 2MPa to generate crude propanol, feeding the crude n-propanol into a rectification system, performing heat exchange and cooling to 40 ℃, performing gas-liquid separation to obtain n-propanol, wherein most of gas phase is hydrogen, feeding the hydrogen into an n-propanol preparation circulation system for recycling, rectifying the crude propanol, condensing and performing heat exchange on a three-phase azeotrope residual liquid formed by a byproduct propyl propionate generated by reaction, water and the n-propanol by a light-ends removal tower, and feeding the three-phase azeotrope residual liquid into a permeation gas-liquid separation dehydration device; and (3) rectifying the liquid-phase material separated by the permeation gas-liquid separation composite membrane dehydration device to separate the n-propanol and the propyl propionate in the liquid-phase material. Propionaldehyde and hydrogen in a volume ratio of 1: and mixing at a ratio of 50.
The permeate gas-liquid separation composite membrane of this example was from example 10.
Example 15:
a clean process for continuously preparing n-propanol,
propionaldehyde preparation: the solid columnar catalyst is filled into a No. 1 fixed bed reactor, and the reactor is a radial phase reactor with a shell side filled with a catalyst tube and a moving heat medium. And (3) filling the synthesis gas into the reactor system to the pressure of 1.5MPa, starting a system circulating compressor to perform system circulation, and heating the synthesis gas by a heater to increase the temperature of the reactor to 120 ℃. And when the circulation of the reactor system is stable, starting a heating medium circulating pump, and supplying a heat transfer heating medium to the tube pass of the reactor to carry out heat transfer circulation. After the internal and external circulation is stable, the purified synthesis gas (H2, CO) and ethylene are mixed and heated to 120 ℃ and then enter a No. 1 fixed bed reactor, and the mass ratio of the ethylene to the synthesis gas is controlled to be 1: 2.5, keeping the pressure of the reactor at 1.5MPa, feeding raw material gas from the bottom of the No. 1 reactor, and discharging reaction gas from the top. The reaction gas is cooled to a 1# crude aldehyde tank through a first-stage cooler, the uncondensed gas is subjected to multi-stage deep cooling to condense the propionaldehyde in the gas phase to a 2# crude aldehyde tank, the aldehyde content in the uncondensed gas is lower than 0.1%, and the gas enters a compressor circulation system. And partial purge gas controls the pressure and the non-condensed steam content of the system. The No. 1 fixed bed reaction is a strong exothermic reaction, and after the reaction starts, the reaction is circularly removed from the reactor by a heating medium system. Then the low-temperature water is prepared by heating the lithium bromide unit by a heating medium. The reaction heat is reasonably recovered. And (3) pressurizing the crude aldehyde in the No. 1 crude aldehyde tank and the No. 2 crude aldehyde tank through a pressurizing pump, sending the pressurized crude aldehyde into a gas tower, and carrying out gas stripping refining by utilizing raw material gas to obtain an aldehyde product for use in the No. 2 hydrogenation reaction. The components of hydrogen and carbon monoxide in the synthesis gas are as follows according to the volume ratio of 1: 1.
preparing n-propanol: and (3) performing hydrogen replacement on the 2# hydrogenation reaction system, and starting a hydrogen circulating compressor circulating system when the hydrogen content of the system is 50% and the system pressure is 1.5 MPa. Then the heater is started to heat the system at a heating speed of 10 ℃/h. When the temperature is increased to 120 ℃, the concentration in the hydrogen system is increased to 95 percent, and the condition of material feeding and starting is met when the starting preparation work is completed. The reactor has several beds and several ply feeds, and each bed is equipped with cold hydrogen, hot hydrogen and propionaldehyde feeding system. Propionaldehyde is mixed with cold and hot hydrogen and then enters an ejector above a reactor bed layer, and is sprayed and atomized by the ejector and then reacts with a catalyst bed layer below the ejector in a contact manner. Controlling the hydrogen-oil ratio to be 80: 1, controlling the temperature of the reactor at 150 ℃ by adjusting the feeding amount of cold and hot hydrogen, controlling the pressure of the reactor at 1.5MPa by purge gas, and adjusting the load of the reactor according to the number of bed opening layers. And the reaction discharge gas enters a No. 3 crude alcohol tank after passing through a first-stage quenching heat exchanger, and the gas which is not condensed enters a No. 4 crude alcohol tank after passing through multi-stage deep cooling. After the alcohol content of the reaction gas after multistage condensation is lower than 0.1%, the reaction gas enters a compression circulation system and is subjected to a recycling reaction. The crude n-propanol is produced and is rectified and refined to obtain the product n-propanol.
After the crude propanol is rectified, a lightness-removing tower condenses and exchanges heat on a three-phase azeotrope residual liquid formed by a byproduct propyl propionate generated by the reaction, water and n-propanol, and then the three-phase azeotrope residual liquid is introduced into a permeable gas-liquid separation composite membrane dehydration device; and (3) rectifying the liquid-phase material separated by the permeation gas-liquid separation composite membrane dehydration device to separate the n-propanol and the propyl propionate in the liquid-phase material. Propionaldehyde and hydrogen in a volume ratio of 1: and mixing at a ratio of 50.
The permeate gas-liquid separation composite membrane of this example was from example 3.
Tail gas recovery: the purge gas of the 1# reactor system contains ethylene, synthesis gas and the like in a certain proportion, and the purge gas of the 2# reactor system contains hydrogen and the like in a certain proportion, so that the gas recycling value is high. After the two gases enter a tail gas system to be mixed, hydrogen is firstly separated out through a hydrogen recovery membrane, and then the hydrogen is pressurized through a compressor and enters a cryogenic ethylene recovery system to recover ethylene. And the carbon monoxide which cannot be recovered is used as final tail gas to enter the waste heat boiler system for combustion to produce preheated steam. All gases in the system are recycled, and finally tail gas is combusted, so that the energy is saved and the system is clean.
Example 16:
this example differs from example 15 only in that the permeate gas-liquid separation composite membrane of this example was derived from example 5.
Example 17:
this example differs from example 15 only in that the permeate gas-liquid separation composite membrane of this example was derived from example 8.
Example 18:
this example differs from example 15 only in that the permeate gas-liquid separation composite membrane of this example was derived from example 10.
Comparative example 1:
this comparative example is compared to example 3, except that no cyclamate was used in the composite microcapsule preparation.
Test example 1:
and (3) permeation flux test:
in the membrane device adopted for the permeation flux test, an inlet and an outlet of raw material steam are arranged on the upper layer of a permeation gas-liquid separation composite membrane, the raw material steam is in direct contact with the permeation gas-liquid separation composite membrane in the inlet and outlet process, only one outlet is arranged on the lower layer of the permeation gas-liquid separation composite membrane and used for permeating steam after passing through the membrane and condensing in a cold trap device, so that the permeating steam is condensed into penetrating fluid, and the penetrating fluid is analyzed by a gas chromatograph after being weighed. The effective area of the membrane in the membrane device is 63cm2。
Test samples: the permeate gas-liquid separation composite membranes prepared in the respective examples and comparative examples.
The test method comprises the following steps: the raw material liquid is a mixed liquid of water and normal propyl alcohol, the raw material liquid is heated to generate steam, the steam is conveyed into the membrane device through a pump, and the raw material steam passes through the membrane device, is discharged from a port 1 and a port 2 and then returns to the raw material liquid; the 3 ports are connected with a cold hydrazine device and then connected with a vacuum pump. After the test is started, the upper layer of the membrane device, namely the raw material steam layer, is kept at normal pressure, the lower layer of the membrane device, namely the permeation steam layer, is vacuumized to keep the negative pressure of 0.1MPa, and cold hydrazine is used for condensation to collect permeation liquid. The permeate was analyzed by gas chromatography.
The permeate flux was calculated as follows:
permeate flux = mass of permeate/(effective area of membrane x time).
The separation factor is calculated as follows:
separation factor = (content of n-propanol in penetrating fluid/content of water in penetrating fluid)/(content of n-propanol in raw material liquid/content of water in raw material liquid)
The permeation flux of the permeated gas-liquid separation composite membrane prepared in the present invention is shown in fig. 1, in which the permeation flux of the permeated gas-liquid separation composite membrane prepared in example 1 is 380.72g · m-2h-1The permeation flux of the permeated gas-liquid separation composite membrane prepared in example 2 was 384.86 g · m-2h-1Example 3 preparation of the resulting permeateThe permeation flux of the gas-liquid separation composite membrane is 402.49 g.m-2h-1The permeation flux of the permeated gas-liquid separation composite membrane prepared in comparative example 1 was 320.36 g · m-2h-1In example 3, compared with comparative example 1, the modified porous silicon is obtained by modifying the porous silicon with the silane coupling agent, the composite microcapsule is prepared from the cyclamate, the silane coupling agent and the cyclodextrin, the permeation flux of the permeation gas-liquid separation composite membrane is improved by using the modified porous silicon and the composite microcapsule for preparing the permeation gas-liquid separation composite membrane, and the use of the cyclamate in the composite microcapsule shows that the permeation flux of the permeation gas-liquid separation composite membrane can be effectively improved by using the composite microcapsule containing the cyclamate when the permeation gas-liquid separation composite membrane is prepared by using the method of the present invention, so that the method has an excellent effect; the permeation flux of the permeated gas-liquid separation composite membrane prepared in example 8 was 426.35 g m-2h-1In example 8, compared with example 3, it is shown that when the permeation gas-liquid separation composite membrane is prepared by the method of the present invention, the permeation flux of the permeation gas-liquid separation composite membrane is increased when 3-quinuclidinone hydrochloride is used, but the effect of increasing 3-quinuclidinone hydrochloride is not excellent as when the composite microcapsule containing cyclamate is used.
The separation factors of the composite membrane for gas-liquid permeation separation prepared by the present invention are shown in fig. 2, wherein the separation factor of the composite membrane for gas-liquid permeation separation prepared in example 1 is 13.2%, the separation factor of the composite membrane for gas-liquid permeation separation prepared in example 2 is 12.6%, the separation factor of the composite membrane for gas-liquid permeation separation prepared in example 3 is 12.1%, the separation factor of the composite membrane for gas-liquid permeation separation prepared in comparative example 1 is 14.6%, in example 3, compared with comparative example 1, the porous silicon is modified by the silane coupling agent to obtain modified porous silicon, the composite microcapsule is prepared by using cyclamate, silane coupling agent and cyclodextrin, the composite membrane for gas-liquid permeation separation is prepared by using the modified porous silicon and the composite microcapsule, the use of cyclamate in the composite microcapsule improves the separation effect of the composite membrane for gas-liquid permeation separation, the method has the advantages that when the permeable gas-liquid separation composite membrane is prepared according to the method, the separation effect of the permeable gas-liquid separation composite membrane can be effectively improved by using the composite microcapsule containing the cyclamate, and the permeable gas-liquid separation composite membrane has an excellent effect; the separation factor of the composite membrane for permeation gas-liquid separation prepared in example 8 is 9.4%, and the comparison between example 8 and example 3 shows that the separation effect of the composite membrane for permeation gas-liquid separation is improved when 3-quinuclidinone hydrochloride is used when the composite membrane for permeation gas-liquid separation is prepared according to the method of the present invention.
Swelling property test:
test samples: the permeate gas-liquid separation composite membranes prepared in the respective examples and comparative examples.
The test method comprises the following steps: drying the test sample at the temperature of 60 ℃ for 24h, weighing the weight of the test sample, then immersing the test sample into an n-propanol solution with the mass fraction of 5wt%, taking out after 12h, sucking the surface moisture, and weighing.
The swelling degree is calculated according to the following formula:
degree of swelling = (mass after swelling-mass before swelling)/mass before swelling × 100%.
The swelling degree of the composite membrane for gas-liquid separation prepared by the present invention is shown in fig. 3, wherein the swelling degree of the composite membrane for gas-liquid separation prepared in example 1 is 0.06%, the swelling degree of the composite membrane for gas-liquid separation prepared in example 2 is 0.06%, the swelling degree of the composite membrane for gas-liquid separation prepared in example 3 is 0.07%, the swelling degree of the composite membrane for gas-liquid separation prepared in comparative example 1 is 0.05%, and in example 3, compared with comparative example 1, the modified porous silicon is obtained by modifying the porous silicon with the silane coupling agent, the composite microcapsule is prepared with the cyclamate, the silane coupling agent and the cyclodextrin, the composite microcapsule is obtained by using the modified porous silicon and the composite microcapsule, the swelling performance of the composite membrane for gas-liquid separation is improved, but the swelling degree of the permeable gas-liquid separation composite membrane cannot be obviously improved, and the swelling degree of the permeable gas-liquid separation composite membrane is not high; the swelling degree of the permeated gas-liquid separation composite membrane prepared in example 8 was 0.08%, and it was found that the swelling degree of the permeated gas-liquid separation composite membrane was slightly increased and was also not high when 3-quinuclidinone hydrochloride was used in the preparation of the permeated gas-liquid separation composite membrane according to the present invention, as compared with example 3 in example 8.
In summary, when the composite microcapsule containing the cyclamate is used for improving the permeation membrane flux of the permeation gas-liquid separation composite membrane and improving the separation performance of the permeation gas-liquid separation composite membrane, the permeation gas-liquid separation composite membrane is not damaged, and the swelling performance is not changed. Similarly, when the 3-quinuclidinone hydrochloride is used in the permeation gas-liquid separation composite membrane, the swelling degree of the permeation gas-liquid separation composite membrane cannot be greatly increased.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. A preparation method of a permeable gas-liquid separation composite membrane comprises the following steps:
adding KH560 and cyclamate into cyclodextrin solution for dispersion, and spray drying to obtain composite microcapsule;
adding the modified porous silicon and the composite microcapsule into a PDMS solution, adding ethyl orthosilicate and dibutyltin dilaurate, reacting to obtain a membrane casting solution, coating the membrane casting solution on a basement membrane, and drying to obtain a permeable gas-liquid separation composite membrane; the modified porous silicon is modified by KH550 and KH 570.
2. The method for preparing a permeate gas-liquid separation composite membrane according to claim 1, wherein: an anti-caking agent is added into the composite microcapsule, and the anti-caking agent is aluminum silicate.
3. The method for preparing a permeate gas-liquid separation composite membrane according to claim 1, wherein: the addition amount of the cyclamate is 1-6wt% of the cyclodextrin solution.
4. A permeate gas-liquid separation composite membrane prepared by the process of any one of claims 1 to 3.
5. The permeated gas-liquid separation composite membrane according to claim 4, which has a permeation flux of 370 g-m "2 h" 1 or more.
6. A clean production method for continuously preparing n-propanol comprises the following steps:
reacting synthesis gas and ethylene in a hydroformylation reaction kettle to obtain crude propionaldehyde, and rectifying and separating to obtain propionaldehyde; the synthesis gas is hydrogen and carbon monoxide;
mixing propionaldehyde and hydrogen, reacting in a hydrogenation reactor to obtain crude n-propanol, and rectifying and separating the crude n-propanol to obtain n-propanol and a byproduct residual liquid;
the liquid phase material separated from the by-product residual liquid by the permeable gas-liquid separation composite membrane dehydration device of claim 4, and the n-propanol is separated by the subsequent treatment of the liquid phase material; the byproduct residual liquid is formed by three-phase azeotropy of propyl propionate, water and n-propanol.
7. The clean production method for continuously preparing n-propanol as claimed in claim 6, which is characterized in that: the volume ratio of the synthesis gas to the ethylene is 1: 1-5.
8. The clean production method for continuously preparing n-propanol as claimed in claim 6, which is characterized in that: the volume ratio of propionaldehyde to hydrogen is 1: mixing at a ratio of 20-100.
9. A clean production method for continuously preparing n-propanol comprises the following steps:
s1, reacting the synthesis gas containing H2 and CO with ethylene under the action of a catalyst to obtain propionaldehyde;
s2, generating and separating the n-propanol by the propionaldehyde hydrogenation reaction prepared in the previous step; the separation uses the permeate gas-liquid separation composite membrane of claim 4;
the purge gas in the S1 and S2 reaction systems is separated out hydrogen and ethylene and is recycled to S1 for recycling.
10. The clean production method for continuously preparing the n-propanol as claimed in claim 9, which is characterized in that: the pressure of the synthesis gas is 0.5-2.5 MPa.
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| CN116328544A (en) * | 2023-03-29 | 2023-06-27 | 山东中盛药化设备有限公司 | Mixed matrix membrane containing cyclodextrin material and preparation method and application thereof |
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Inventor after: Zhou Liyang Inventor after: Huang Jie Inventor after: Jia Tianxu Inventor after: Xu Feng Inventor after: Tu Qihui Inventor after: Zhou Qiang Inventor after: Zhong Junliang Inventor after: Wu Danping Inventor after: Li Zhongwei Inventor after: Wu Xihuan Inventor after: Zuo Zilong Inventor after: Huang Zunkang Inventor before: Tu Qihui Inventor before: Jia Tianxu Inventor before: Xu Feng Inventor before: Zhou Qiang Inventor before: Zhong Junliang Inventor before: Wu Danping Inventor before: Li Zhongwei Inventor before: Wu Xihuan Inventor before: Zuo Zilong Inventor before: Huang Zunkang Inventor before: Huang Jie |