CN220514131U - Membrane reactor for preparing olefin by carbon dioxide hydrogenation - Google Patents
Membrane reactor for preparing olefin by carbon dioxide hydrogenation Download PDFInfo
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- CN220514131U CN220514131U CN202322004730.6U CN202322004730U CN220514131U CN 220514131 U CN220514131 U CN 220514131U CN 202322004730 U CN202322004730 U CN 202322004730U CN 220514131 U CN220514131 U CN 220514131U
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- separation membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 114
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000011148 porous material Substances 0.000 claims abstract description 19
- 238000010926 purge Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 239000002808 molecular sieve Substances 0.000 claims description 27
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 27
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000011865 Pt-based catalyst Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 50
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000007789 gas Substances 0.000 description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 239000011259 mixed solution Substances 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000000151 deposition Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001132 ultrasonic dispersion Methods 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 8
- 238000001027 hydrothermal synthesis Methods 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A membrane reactor for preparing olefin by carbon dioxide hydrogenation belongs to carbon dioxideThe technical field of olefin production, overcomes the defects of CO in the prior art 2 Low conversion. A membrane reactor for preparing olefin by carbon dioxide hydrogenation comprises a shell, a separation membrane and a support tube; the two ends of the shell are respectively provided with a raw material gas inlet and a raw material gas outlet; the support tube is arranged in the shell, and two ends of the support tube are respectively provided with a purge gas inlet and a purge gas outlet; the separation membrane is arranged on the outer surface of the supporting tube, and the average pore diameter of the separation membrane isA catalyst is arranged between the shell and the separation membrane. The membrane reactor for preparing olefin by carbon dioxide hydrogenation can push the reaction balance to move rightwards, thereby breaking through the bottleneck limit of the balance conversion rate of the chemical reaction in the process and improving CO 2 Is a conversion rate of (a).
Description
Technical Field
The utility model belongs to the technical field of olefin production by carbon dioxide, and particularly relates to a membrane reactor for olefin production by carbon dioxide hydrogenation.
Background
CO at present 2 The hydrogenation for preparing olefin can be realized by two paths: 1. synthetic route (CO) with CO as intermediate product 2 -FT path): CO 2 And H is 2 Warp knittingCO is generated through reverse water gas shift Reaction (RWGS) (formula 1), and then low-carbon olefin is prepared through Fischer-Tropsch synthesis reaction (FTO) (formula 2). 2. Synthetic route with methanol as intermediate (MeOH intermediate route): CO 2 And H is 2 Methanol is produced by the reaction (formula 3), and then alkene is produced by the dehydration reaction of methanol (formula 4). The main reactions involved in both synthetic pathways are as follows:
CO 2 +H 2 →CO+H 2 o (RWGS) equation 1
nCO+2nH 2 →C n H 2n +nH 2 O (FTO) equation 2
CO 2 +3H 2 →CH 3 OH+H 2 O (CO 2 to meta 1) equation 3
nCH 3 OH→C n H 2n +nH 2 O (MTO) equation 4
Wherein, the second synthetic path using methanol as intermediate product does not involve FT (Fischer-Tropsch) reaction, so that ASF distribution (product distribution rule of Fischer-Tropsch synthesis) limitation can be broken, and C is greatly improved 2 ＝ -C 4 ＝ Selectivity, thus is at present CO 2 Research hot spot in the field of hydrogenation to prepare low-carbon olefin. However, in the existing synthetic route for producing olefins by using methanol as an intermediate product, CO 2 Is lower.
CN 114436773 discloses a method for CO 2 A reactor and a process for preparing methanol and/or dimethyl ether by hydrogenation. By CO in 2 Introducing dehydrating agent in hydrogenation reaction to realize CO 2 The coupling of hydrogenation reaction and dehydration reaction promotes the movement of reaction balance, thereby improving the conversion rate of carbon dioxide. However, there is a certain difficulty in preparing and coupling the hydrogenation-dehydration composite catalyst, and there is an upper limit on the water absorption capacity of the catalyst.
CN102584526 discloses a membrane reactor for preparing methanol from synthesis gas, which membrane is permeable to methanol and water vapor. Specifically, the membrane reactor is provided with a catalyst outside the membrane tubes and an absorbent inside the membrane tubes. The reaction is carried out outside the membrane to generateMethanol and water vapor permeate through the membrane to the inside of the membrane reactor, dissolve in the absorbent and are transferred. Coupled with the absorbent through the membrane reactor, and effectively removes reaction products in time, thereby improving CO 2 Conversion rate. However, the separation of methanol products requires the desorption of the absorbent and is energy-efficient.
Disclosure of Invention
Therefore, the utility model aims to solve the technical problems of the prior art of CO 2 The conversion rate is low, thereby providing a membrane reactor for preparing olefin by hydrogenating carbon dioxide.
For this purpose, the utility model provides the following technical scheme.
In a first aspect, the present utility model provides a membrane reactor for producing olefins by hydrogenation of carbon dioxide, comprising a housing, a separation membrane and a support tube;
the two ends of the shell are respectively provided with a raw material gas inlet and a raw material gas outlet;
the support tube is arranged in the shell, and two ends of the support tube are respectively provided with a purge gas inlet and a purge gas outlet;
the separation membrane is arranged on the outer surface of the supporting tube, and the average pore diameter of the separation membrane is
A catalyst is arranged between the shell and the separation membrane.
Further, the material of the separation membrane is a catalyst A for preparing olefin from methanol, and the catalyst comprises CO 2 Catalyst B for preparing methanol.
Further, the catalyst comprises catalysts A and CO for preparing olefin from methanol 2 Catalyst B for preparing methanol.
Further, the support tube is Al 2 O 3 Or ZrO(s) 2 Preferably, the average pore diameter of the pipe wall of the support pipe is 100-200 nm;
further, the inner diameter of the supporting pipe is 6-10 mm;
further, the catalyst A for preparing olefin from methanol is an SAPO-34 molecular sieve, an SAPO-18 molecular sieve or a ZSM-5 molecular sieve;
further, the CO 2 The catalyst B for preparing the methanol comprises at least one of a Cu-based catalyst, a Pt-based catalyst, a Pd-based catalyst, inO and ZnO; more preferably, the catalyst B is CuO/ZnO/Al 2 O 3 (belonging to Cu-based catalyst, wherein CuO is active component, znO is auxiliary agent, al 2 O 3 Is a carrier), cuO/InO or ZnO/ZrO 2 (ZrO 2 Is a catalyst carrier);
further, the shell is made of stainless steel;
further, the separation membrane has an average pore diameter of
A preparation method of a membrane reactor comprises the steps of depositing and forming a separation membrane on a supporting tube by adopting a secondary synthesis method:
step 1, synthesizing seed crystals;
step 2, depositing seed crystals on the surface of the support tube;
and step 3, placing the support tube deposited with the seed crystal into the synthetic liquid for crystallization, and forming a separation membrane on the surface of the support tube.
Further, the separation membrane material is SAPO-34 molecular sieve;
the step of depositing the separation membrane on the support tube by a secondary synthesis method satisfies at least one of the following conditions:
(1) The step 1 comprises the following steps: preparing a mixed solution A from a silicon source, an aluminum source, a phosphorus source, a template agent and water, stirring, heating for crystallization, cooling to room temperature, washing the product to be neutral, drying and roasting to obtain seed crystals;
(2) The step 2 comprises the following steps: mixing seed crystal with absolute ethyl alcohol, and carrying out ultrasonic dispersion to prepare seed crystal liquid; sealing two ends of the support tube, immersing in seed crystal liquid, taking out, and drying;
(3) The step 3 comprises the following steps: preparing a mixed solution B from a silicon source, an aluminum source, a phosphorus source, a template agent and water, stirring, heating for crystallization, cooling to room temperature to obtain a synthetic solution, placing a support tube deposited with seed crystals in the synthetic solution for heating for crystallization, cooling to room temperature after the reaction is finished, washing the product to be neutral, and drying.
Further, the step 1 satisfies at least one of the conditions (1) to (5):
(1) In the mixed solution A, si: al: p: template agent: h 2 Molar ratio of o= (0.01 to 0.1): (0.2-2): (0.2-2): (1-10): (30-100);
(2) Stirring for 0.5-1.5h, heating and crystallizing for 12-48 h at 180-220 ℃;
(3) The washing is centrifugal washing, the centrifugal rotating speed is 3000-5000r/min, and the time is 5-10min;
(4) Drying at 60-100deg.C for 10-24 hr;
(5) Roasting temperature is 500-700 ℃ and roasting time is 3-8h. Regular proportioning and purifying time period
Further, the step 2 satisfies at least one of the conditions (1) to (5):
(1) The concentration of seed crystal in the seed crystal liquid is 0.5-2wt%;
(2) The ultrasonic dispersion power is 100-1000W, and the time is 30-60min;
(3) The time for immersing in the seed crystal liquid is 0.5-2 min;
(4) Drying at 60-100deg.C for 10-24 hr.
Further, the step 3 satisfies at least one of the conditions (1) to (5):
(1) In the mixed solution B, si: al: p: template agent: h 2 Molar ratio of o= (0.01 to 0.1): (0.1-1): (0.1-1): (1-10): (30-100);
(2) Stirring for 0.5-1.5h, heating and crystallizing for 12-48 h at 180-220 ℃;
(3) The washing is centrifugal washing, the centrifugal rotating speed is 3000-5000r/min, and the time is 5-10min;
(4) Placing the support tube deposited with the seed crystal into the synthetic liquid for heating and crystallizing to obtain the product: crystallizing at 180-220 deg.c for 24-48 hr;
(5) Drying at 60-100deg.C for 10-24 hr.
Further, the preparation of the mixed solution A and/or the mixed solution B comprises the following steps: mixing an aluminum source with water, adding a silicon source, then adding a phosphorus source, and then adding a template agent under stirring. The shell is made of stainless steel, and is exemplified by stainless steel ss316L or stainless steel ss32168.
The technical scheme of the utility model has the following advantages:
1. the utility model provides a membrane reactor for preparing olefin by carbon dioxide hydrogenation, which comprises a shell, a separation membrane and a support tube; the two ends of the shell are respectively provided with a raw material gas inlet and a raw material gas outlet; the support tube is arranged in the shell, and two ends of the support tube are respectively provided with a purge gas inlet and a purge gas outlet; the separation membrane is arranged on the outer surface of the supporting tube, and the average pore diameter of the separation membrane isA catalyst is arranged between the shell and the separation membrane.
The utility model relates to a reaction-separation coupled membrane reactor, the average pore diameter of a separation membrane is Within this range, when water is allowed to permeate the separation membrane, other gases are prevented from permeating the separation membrane as much as possible. CO 2 The byproduct water molecules generated in the methanol-to-olefin reaction and the methanol-to-olefin reaction permeate through the separation membrane and the support pipe wall, enter the support pipe, are removed through gas blowing, and push the reaction balance to move rightwards, so that the bottleneck limit of the balance conversion rate of the process chemical reaction is broken through, and the CO is promoted 2 Is a conversion rate of (a).
The membrane reactor has no upper limit on water absorption capacity and low energy consumption.
Drawings
In order to more clearly illustrate the embodiments of the present utility model or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present utility model, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is example 1 for CO 2 A schematic diagram of a membrane reactor structure for preparing olefin by hydrogenation.
Reference numerals:
1-raw material gas inlet, 2-raw material gas outlet, 3-purge gas inlet, 4-purge gas outlet, 5-shell, 6-separation membrane, 7-support tube and 8-CO 2 Preparing the methanol catalyst.
Detailed Description
The following examples are provided for a better understanding of the present utility model and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the utility model, any product which is the same or similar to the present utility model, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present utility model.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Commercial CuO/ZnO/Al in examples and comparative examples 2 O 3 Purchased from ICI company, uk; support tubes were purchased from Nanjing membrane materials industry institute of technology, inc.
Example 1
The embodiment provides a membrane reactor for preparing olefin by hydrogenation of carbon dioxide, which is shown in figure 1 and comprises a shell 5, a separation membrane 6 and a supporting tube 7; the separation membrane 6 is made of SAPO-34 molecular sieve. The separation membrane 6 is arranged on the support tube 7; the separation membrane 6 and the support tube 7 are arranged in the shell 5, and CO is arranged between the shell 5 and the separation membrane 6 2 Methanol preparation catalyst 8-commercial CuO/ZnO/Al 2 O 3 . The two ends of the supporting tube 7 are respectively provided with a purge gas inlet 3 and a purge gas outlet 4; the two ends of the shell 5 are respectively provided with a feed gas inlet 1 and a feed gas outlet 2. In this example, the separation membrane 6 has an average pore diameter ofThe support tube 7 is Al 2 O 3 The average pore diameter of the porous material is 100nm, and the inner diameter of the pipe diameter of the supporting pipe 7 is 8mm.
CO 2 And H 2 Enters the membrane reactor through a feed gas inlet 1, and is commercially used for CuO/ZnO/Al 2 O 3 Methanol and water are generated by the reaction under the catalysis of the separation membrane SAPO-34 molecular sieve, olefin and water are generated by the generated methanol under the catalysis of the separation membrane SAPO-34 molecular sieve, the water generated by the two reactions enters the supporting tube 7 through the separation membrane 6 and the supporting tube wall, and gas (such as air) entering through the purge gas inlet 3 is taken away through the purge gas outlet 4, so that the two reactions are promoted to move rightwards.
Example 2
The membrane reactor for producing olefins by hydrogenation of carbon dioxide provided in this example is basically the same as that of example 1, except that the separation membrane has an average pore diameter of
The embodiment provides a preparation method of a membrane reactor for preparing olefin by hydrogenation of carbon dioxide, which comprises the steps of depositing and forming a separation membrane on a supporting tube by adopting a secondary synthesis method:
(1) Synthesis of seed crystal: mixing pseudo-boehmite and deionized water, adding a certain amount of silica sol under stirring, slowly adding a certain amount of phosphoric acid at a rate of 20ml/min, and finally adding a triethylamine template agent (TEA) to prepare a mixed solution A, wherein Si in the mixed solution A: al: p: template agent: h 2 Molar ratio of O = 0.1:2:2:1.2:50, stirring for 1h, transferring into a polytetrafluoroethylene lining of a hydrothermal reaction kettle, crystallizing at 180 ℃ for 18h, cooling to room temperature after the reaction is finished, performing centrifugal washing at 3500r/min,centrifuging for 10min until the product is neutral, drying the product at 60 ℃ for 24h, and roasting at 600 ℃ for 6h to obtain the SAPO-34 molecular sieve seed crystal.
(2) Depositing a seed layer: mixing the SAPO-34 molecular sieve seed crystal prepared in the step (1) with absolute ethyl alcohol, performing ultrasonic dispersion, wherein the ultrasonic dispersion power is 800W, the time is 60min, and preparing seed crystal liquid with the concentration of 0.5wt%. The two ends of the support tube 7 were sealed, and then the support tube 7 was immersed in the seed crystal liquid, after 1min, the support tube 7 was slowly and smoothly taken out, transferred into a beaker, and dried in an oven at 60 ℃ for 24 hours.
(3) Preparation of SAPO-34 molecular sieve separation membrane: mixing pseudo-boehmite and deionized water, adding a certain amount of silica sol under the stirring condition, slowly adding a certain amount of phosphoric acid, and finally adding a triethylamine template agent to prepare a mixed solution B, wherein Si in the mixed solution B: al: p: template agent: h 2 Molar ratio of O = 0.1:2:2:1.2:60, stirring for 1h, transferring into a polytetrafluoroethylene lining of a hydrothermal reaction kettle, crystallizing at 180 ℃ for 12h, and cooling to room temperature after the reaction is finished to obtain a synthetic solution. Fixing the support tube 7 deposited with the seed crystal layer on a tetrafluoro bracket, placing the support tube 7 in a reaction kettle, placing 20mL of synthetic solution in the reaction kettle, crystallizing for 18 hours at 200 ℃, cooling to room temperature after the reaction is finished, washing to neutrality by deionized water, and drying for 24 hours at 60 ℃ to obtain the SAPO-34 molecular sieve separation membrane.
The average pore diameter of the separation membrane is
Assembling the support tube 7 with the separation membrane 6 with the casing 5, and disposing commercial CuO/ZnO/Al in the space formed by the separation membrane 6 and the casing 5 2 O 3 A membrane reactor for preparing olefin by carbon dioxide hydrogenation is obtained.
Example 3
The membrane reactor for producing olefins by hydrogenation of carbon dioxide provided in this example is basically the same as that of example 1, except that the separation membrane has an average pore diameter of
The embodiment provides a preparation method of a membrane reactor for preparing olefin by hydrogenation of carbon dioxide, which comprises the steps of depositing and forming a separation membrane on a supporting tube by adopting a secondary synthesis method:
(1) Synthesis of seed crystal: mixing pseudo-boehmite and deionized water, adding a certain amount of silica sol under stirring, slowly adding a certain amount of phosphoric acid at a rate of 20ml/min, and finally adding a triethylamine template agent (TEA) to prepare a mixed solution A, wherein Si in the mixed solution A: al: p: template agent: h 2 Molar ratio of O = 0.1:2:2:1.2:50, stirring for 1h, transferring into a polytetrafluoroethylene lining of a hydrothermal reaction kettle, crystallizing at 180 ℃ for 24h, cooling to room temperature after the reaction is finished, performing centrifugal washing at 3500r/min, centrifuging for 10min until the product is neutral, drying at 60 ℃ for 24h, and roasting at 600 ℃ for 6h to obtain the SAPO-34 molecular sieve seed crystal.
(2) Depositing a seed layer: mixing the SAPO-34 molecular sieve seed crystal prepared in the step (1) with absolute ethyl alcohol, performing ultrasonic dispersion, wherein the ultrasonic dispersion power is 800W, the time is 60min, and preparing seed crystal liquid with the concentration of 0.5wt%. The two ends of the support tube 7 were sealed, and then the support tube 7 was immersed in the seed crystal liquid, after 1min, the support tube 7 was slowly and smoothly taken out, transferred into a beaker, and dried in an oven at 60 ℃ for 24 hours.
(3) Preparation of SAPO-34 molecular sieve separation membrane: mixing pseudo-boehmite and deionized water, adding a certain amount of silica sol under the stirring condition, slowly adding a certain amount of phosphoric acid, and finally adding a triethylamine template agent to prepare a mixed solution B, wherein Si in the mixed solution B: al: p: template agent: h 2 Molar ratio of O = 0.1:2:2:1.2:60, stirring for 1h, transferring into a polytetrafluoroethylene lining of a hydrothermal reaction kettle, crystallizing at 180 ℃ for 24h, and cooling to room temperature after the reaction is finished to obtain a synthetic solution. Fixing the support tube 7 deposited with the seed crystal layer on a tetrafluoro bracket, placing the support tube 7 in a reaction kettle, placing 20mL of synthetic solution in the reaction kettle, crystallizing for 24 hours at 200 ℃, cooling to room temperature after the reaction is finished, washing to neutrality by deionized water, and drying for 24 hours at 60 ℃ to obtain the SAPO-34 molecular sieveAnd a separation membrane.
The average pore diameter of the separation membrane is
Assembling the support tube 7 with the separation membrane 6 with the casing 5, and disposing commercial CuO/ZnO/Al in the space formed by the separation membrane 6 and the casing 5 2 O 3 A membrane reactor for preparing olefin by carbon dioxide hydrogenation is obtained.
Example 4
The membrane reactor for producing olefins by hydrogenation of carbon dioxide provided in this example is basically the same as that of example 1, except that the separation membrane has an average pore diameter of
The embodiment provides a preparation method of a membrane reactor for preparing olefin by hydrogenation of carbon dioxide, which comprises the steps of depositing and forming a separation membrane on a supporting tube by adopting a secondary synthesis method:
(1) Synthesis of seed crystal: mixing pseudo-boehmite and deionized water, adding a certain amount of silica sol under stirring, slowly adding a certain amount of phosphoric acid at a rate of 20ml/min, and finally adding a triethylamine template agent (TEA) to prepare a mixed solution A, wherein Si in the mixed solution A: al: p: template agent: h 2 Molar ratio of O = 0.05:2:2:1.2:50, stirring for 1h, transferring into a polytetrafluoroethylene lining of a hydrothermal reaction kettle, crystallizing at 180 ℃ for 24h, cooling to room temperature after the reaction is finished, performing centrifugal washing at 3500r/min, centrifuging for 10min until the product is neutral, drying at 60 ℃ for 24h, and roasting at 600 ℃ for 6h to obtain the SAPO-34 molecular sieve seed crystal.
(2) Depositing a seed layer: mixing the SAPO-34 molecular sieve seed crystal prepared in the step (1) with absolute ethyl alcohol, performing ultrasonic dispersion, wherein the ultrasonic dispersion power is 800W, the time is 60min, and preparing seed crystal liquid with the concentration of 0.5wt%. The two ends of the support tube 7 were sealed, and then the support tube 7 was immersed in the seed crystal liquid, after 1min, the support tube 7 was slowly and smoothly taken out, transferred into a beaker, and dried in an oven at 60 ℃ for 24 hours.
(3) Preparation of SAPO-34 molecular sieve separation membrane: mixing pseudo-boehmite and deionized water, adding a certain amount of silica sol under the stirring condition, slowly adding a certain amount of phosphoric acid, and finally adding a triethylamine template agent to prepare a mixed solution B, wherein Si in the mixed solution B: al: p: template agent: h 2 Molar ratio of O = 0.1:2:2:1.2:60, stirring for 1h, transferring into a polytetrafluoroethylene lining of a hydrothermal reaction kettle, crystallizing at 180 ℃ for 24h, and cooling to room temperature after the reaction is finished to obtain a synthetic solution. Fixing the support tube 7 deposited with the seed crystal layer on a tetrafluoro bracket, placing the support tube 7 in a reaction kettle, placing 20mL of synthetic solution in the reaction kettle, crystallizing for 24 hours at 200 ℃, cooling to room temperature after the reaction is finished, washing to neutrality by deionized water, and drying for 24 hours at 60 ℃ to obtain the SAPO-34 molecular sieve separation membrane.
The average pore diameter of the separation membrane is
Assembling the support tube 7 with the separation membrane 6 with the casing 5, and disposing commercial CuO/ZnO/Al in the space formed by the separation membrane 6 and the casing 5 2 O 3 A membrane reactor for preparing olefin by carbon dioxide hydrogenation is obtained.
Example 5
This example provides the preparation method of the membrane reactor for producing olefins by hydrogenation of carbon dioxide of example 1, comprising the steps of depositing a separation membrane on a support tube by a secondary synthesis method:
(1) Synthesis of seed crystal: mixing pseudo-boehmite and deionized water, adding a certain amount of silica sol under stirring, slowly adding a certain amount of phosphoric acid at a rate of 20ml/min, and finally adding a triethylamine template agent (TEA) to prepare a mixed solution A, wherein Si in the mixed solution A: al: p: template agent: h 2 Molar ratio of O = 0.1:2:2:1.2:50, stirring for 1h, transferring into a polytetrafluoroethylene lining of a hydrothermal reaction kettle, crystallizing at 180 ℃ for 12h, cooling to room temperature after the reaction is finished, performing centrifugal washing at 3500r/min, and centrifuging for 10min until the product is neutralDrying the product at 60 ℃ for 24 hours, and roasting at 600 ℃ for 6 hours to obtain the SAPO-34 molecular sieve seed crystal.
(2) Depositing a seed layer: mixing the SAPO-34 molecular sieve seed crystal prepared in the step (1) with absolute ethyl alcohol, performing ultrasonic dispersion, wherein the ultrasonic dispersion power is 800W, the time is 60min, and preparing seed crystal liquid with the concentration of 0.5wt%. The two ends of the support tube 7 were sealed, and then the support tube 7 was immersed in the seed crystal liquid, after 1min, the support tube 7 was slowly and smoothly taken out, transferred into a beaker, and dried in an oven at 60 ℃ for 24 hours.
(3) Preparation of SAPO-34 molecular sieve separation membrane: mixing pseudo-boehmite and deionized water, adding a certain amount of silica sol under the stirring condition, slowly adding a certain amount of phosphoric acid, and finally adding a triethylamine template agent to prepare a mixed solution B, wherein Si in the mixed solution B: al: p: template agent: h 2 Molar ratio of O = 0.1:2:2:1.2:60, stirring for 1h, transferring into a polytetrafluoroethylene lining of a hydrothermal reaction kettle, crystallizing at 180 ℃ for 12h, and cooling to room temperature after the reaction is finished to obtain a synthetic solution. Fixing the support tube 7 deposited with the seed crystal layer on a tetrafluoro bracket, placing the support tube 7 in a reaction kettle, placing 20mL of synthetic solution in the reaction kettle, crystallizing for 12 hours at 200 ℃, cooling to room temperature after the reaction is finished, washing to neutrality by deionized water, and drying for 24 hours at 60 ℃ to obtain the SAPO-34 molecular sieve separation membrane.
The average pore diameter of the separation membrane is
Assembling the support tube 7 with the separation membrane 6 with the casing 5, and disposing commercial CuO/ZnO/Al in the space formed by the separation membrane 6 and the casing 5 2 O 3 A membrane reactor for preparing olefin by carbon dioxide hydrogenation is obtained.
Comparative example 1
This comparative example provides a membrane reactor for the hydrogenation of carbon dioxide to olefins, substantially identical to example 1, except that this comparative example does not contain a separation membrane 6, the sapo-34 molecular sieve is in particulate form with commercially available CuO/ZnO/Al 2 O 3 Is arranged in the shell 5 and divided after mixingAnd a release film 6.
Comparative example 2
This comparative example provides a membrane reactor for the hydrogenation of carbon dioxide to olefins, substantially identical to example 1, except that this comparative example does not contain a separation membrane 6, the sapo-34 molecular sieve is in particulate form with commercially available CuO/ZnO/Al 2 O 3 After mixing, the water absorbing agent is disposed between the casing 5 and the separation membrane 6, but on the outer surface of the support tube 7.
Test examples
Olefin, CO, was produced using the membrane reactors of examples 1-4 and comparative examples 1-2 2 The conversion of (2) is shown in the following table.
Table 1 CO 2 Conversion rate
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| CO 2 Conversion rate | 10.2％ | 13.4 | 18.1％ | 23.2％ | 6.8％ | 7.9％ |
As can be seen from Table 1, by adopting the membrane reactor for producing olefin by hydrogenation of carbon dioxide of the present utility model, the reaction equilibrium can be pushed to move rightward by removing water generated during the reaction and avoiding permeation of raw material gas through the separation membrane as much as possible, and CO can be greatly improved 2 Is a conversion rate of (a).
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present utility model.
Claims (5)
1. A membrane reactor for preparing olefin by hydrogenation of carbon dioxide is characterized by comprising a shell, a separation membrane and a supporting tube;
the two ends of the shell are respectively provided with a raw material gas inlet and a raw material gas outlet;
the support tube is arranged in the shell, and two ends of the support tube are respectively provided with a purge gas inlet and a purge gas outlet;
the separation membrane is arranged on the outer surface of the supporting tube, and the average pore diameter of the separation membrane is
A catalyst is arranged between the shell and the separation membrane.
2. The membrane reactor according to claim 1, wherein the material of the separation membrane is catalyst a for methanol to olefins, and the catalyst comprises CO 2 Catalyst B for preparing methanol.
3. The membrane reactor of claim 1, wherein the catalyst comprises methanol to olefins catalyst a and CO 2 Catalyst B for preparing methanol.
4. A membrane reactor according to claim 2 or 3, wherein at least one of the conditions (1) - (6) is satisfied:
(1) The supporting tube is Al 2 O 3 Or ZrO(s) 2 A porous support of (a);
(2) The inner diameter of the supporting pipe is 6-10 mm;
(3) The catalyst A for preparing olefin from methanol is an SAPO-34 molecular sieve, an SAPO-18 molecular sieve or a ZSM-5 molecular sieve;
(4) The CO 2 The catalyst B for preparing the methanol comprises at least one of a Cu-based catalyst, a Pt-based catalyst, a Pd-based catalyst, inO and ZnO;
(5) The shell is made of stainless steel;
(6) The average pore diameter of the separation membrane is
5. The membrane reactor according to claim 4, wherein the average pore diameter of the support tube wall is 100-200 nm.
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