CN101757859A - Carbon membrane reactor and method for using the same - Google Patents
Carbon membrane reactor and method for using the same Download PDFInfo
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- CN101757859A CN101757859A CN 201010118376 CN201010118376A CN101757859A CN 101757859 A CN101757859 A CN 101757859A CN 201010118376 CN201010118376 CN 201010118376 CN 201010118376 A CN201010118376 A CN 201010118376A CN 101757859 A CN101757859 A CN 101757859A
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Abstract
The invention provides a carbon membrane reactor and a method for using the same. The carbon membrane reactor is characterized in that a non-defect carbon membrane is connected with the housing of the reactor; a hollow cavity is formed inside the housing of the reactor, wherein the hollow cavity communicated with a charging hole and a discharging hole for reactant constitutes a charging side, and the hollow cavity communicated with an inlet and an outlet for purge gas constitutes a permeating side; the non-defect carbon membrane is filled with catalysts, or alternatively, the catalysts are laid on the non-defect carbon membrane; The method for using the carbon membrane reactor comprises the following steps: adding the reactant on the charging side, and regulating the temperature and pressure to conduct chemical reaction; transferring the components in the products to the permeating side via the porous channels of the non-defect carbon membrane; and removing the components transferred to the permeating side by the purge gas, thereby leading the chemical reaction to be conducted in a forward direction. The invention has the following advantages that: the invention provides a device capable of synchronously conducting the chemical reaction and physical separation and increasing the conversion rate, yield and selectivity of the reaction; and the invention simplifies the production process and reduces the cost for devices and products.
Description
Technical field: the present invention relates to fields such as film separation and Chemical Engineering, specifically refer to a kind of membrane reactor and using method thereof.
Background technology: in recent years, that the film separation is very fast with the development that the course of reaction coupling is assembled into membrane reactor.Membrane reactor has been realized the integrated of course of reaction and separation process, can optionally remove certain product in chemical reaction process, breaks through the restriction of thermodynamics to chemical reaction equilibrium, thereby improves conversion ratio, selectivity and the yield of reaction.Membrane material is the core component of membrane reactor, and it has directly determined the performance and the application of membrane reactor.Because the pressure and temperature that a lot of chemical reactions all require to reach certain could carry out smoothly, conventional polymer film parting material obviously can't be competent at.Therefore people have turned to the inorganic material film with well high temperature resistant, high pressure resistant and separating property to sight, as pottery, zeolite, metal and charcoal etc.For pottery and stainless steel membrane material, pore size distribution range is bigger, and is difficult to obtain the material of average pore size less than 5nm, has limited its application at some separation field (Soria R.Catalysis Today, 1995,25 (3-4): 285-290.); And for zeolitic material, quality own is crisp frangible, be not easy to form the continuous film of large tracts of land, often need repeatedly film forming procedure, cause rete thicker and inhomogeneous, thereby increase diffusion and osmotic resistance (Ismail A F, the David L I B.J.Membr.Sci. of material to be separated, 2001,193 (1): 1-18; Sedigh M G, Onstot W J, Xu L, et al.J.PhysChem.A 1998,102 (44): 8580-8589.).Metal Palladium membrane material commonly used is relatively more expensive on the one hand, contains hydrogen or H on the other hand in reaction system
2During materials such as S, can have an effect and make separating effect not good, even produce dangerous (Damle A S, Gangwal S K, Venkataraman V K.Gasseparation and purification, 1994,8 (3): 137-147.).
Carbon membrane is a kind of inorganic porous membrane, except advantage such as efficient, energy-conservation, easy to operate with other membrane material, it also has many more tempting advantages, as heat-resisting, corrosion-resistant, chemical stability is good, long service life, separating property height, pore-size distribution are concentrated, adjustability is good, be easy to adopt several different methods to prepare the continuous film of large tracts of land.Current, day by day ripe both at home and abroad in the technology of carbon membrane aspect preparing.Researchers have successively developed the tubulose carbon membrane, tabular carbon membrane, hollow fiber carbon membrane (Saufi S M, etal., Carbon, 2004,42 (2): 241-259.) and spiral carbon membrane (a kind of spiral carbon membrane and preparation method thereof, Chinese patent, 200810012222).Carbon membrane is at drink water purifying (Bauer J M, et al., KeyEngineering Materials, 1991, (61-62): 207-212.), (Wang Tonghua is etc., novel charcoal material in beer aseptic filtration, 2000,15 (1): 6-11.), the processing of wastewater from chemical industry (Wang Xifeng, etc., membrane science and technology, 2001,21 (6): 59-62; Damle A S., Gas Sep.Pur., 1994,8 (3): 137-147.; Bauer J M, etal., Key Engineering Materials, 1991, (61-62): 207-212.), admixture of gas N
2/ O
2, CO
2/ N
2, CO
2/ CH
4, H
2/ N
2, alkane/olefin etc. separation and enrichment (Suda H, et al., J.Phys.Chem.B, 1997,101 (20): 3988-3994; Kita H, et al., J.Polym.Environ., 2002,10 (3): 69-75; Hayashi J, et al., Ind.Eng.Chem.Res., 1996,35 (11): 4176-4181.), and membrane catalytic reaction process (Rao M B, et al., J.Membr.Sci., 1996,110 (1): 109-118.) etc. the field all has application promise in clinical practice, has become when cephacoria to separate and the research and development focus in field such as Chemical Engineering.Therefore, carbon membrane is to promise to be one of industrialized membrane reactor material of large tracts of land most.
But, the research work of current porous carbon membrane much all concentrates on selection, the film build method of presoma and improves aspects such as separating property, report for application facet then also rests on theory analysis and tentatively inquires into, (the two-stage cure method prepares alkyd resin based carbon membrane to be difficult to instruct practical application in industry and production process, Chinese patent, 02144662; A kind of accent hole method of coal-based carbon film, Chinese patent, 03134196; MCMB parent tube formula carbon membrane and preparation method thereof, Chinese patent, 200710058369; Porouscarbon-carbon composite filtering membrane support with a carbon fibre matsubstrate, United States Patent (USP), 5238568; Manufacture of porous carbon membranes, United States Patent (USP), 4919860).Given this, the deep research work of inventor's process system proposes and has developed a kind of carbon membrane reactor and application thereof.
Summary of the invention:
Goal of the invention: the objective of the invention is with carbon membrane as core material with separating property, it is assembled into membrane reactor, be used for chemical reaction process, break the restriction of chemical balance by in course of reaction, optionally removing some component in the system, thereby improve conversion ratio, yield and the selectivity of reaction.
Technical scheme: the present invention implements by the following technical programs:
A kind of carbon membrane reactor comprises shell of reactor, and the zero defect carbon membrane is characterized in that: have reactant feeding mouth, reactant discharging opening, sweep gas inlet, sweep gas outlet on the shell of reactor; The zero defect carbon membrane is connected with shell of reactor, and at the relatively independent cavity of the inner formation of shell of reactor, wherein the cavity that communicates with reactant feeding mouth, reactant discharging opening is a feed side, and the cavity that communicates with sweep gas inlet, sweep gas outlet is a per-meate side; At the inner catalyst filling of zero defect carbon membrane or on the zero defect carbon membrane, lay catalyst.
Described zero defect carbon membrane is tabular, tubulose or hollow fiber.
Described zero defect carbon membrane is connected by carbon membrane tube connector or carbon membrane connecting plate with shell of reactor.
Described shell of reactor material is stainless steel, pottery, copper or metal alloy.
Described zero defect carbon membrane and shell of reactor are for being tightly connected, and connected mode is high-temperature seal adhesive, graphite gasket, graphite ferrule or welding.
When having a plurality of feed side, between a plurality of feed sides and reactant feeding mouth, reactant discharging opening, be connected by the material distributor.
The precursor of described zero defect carbon membrane is polyimides, poly furfuryl alcohol, phenolic resins, polyacrylonitrile, polyphenylene oxide or cellulose, charing atmosphere is inert gas or vacuum, carbonization temperature is 400～1000 ℃, zero defect carbon membrane supporter is carbonaceous, pottery, graphite, doughnut or stainless steel material, and film build method is coating or spraying or ultrasonic deposition or chemical vapour deposition (CVD).
A kind of using method of carbon membrane reactor is characterized in that: described application process is:
Zero defect carbon membrane and shell of reactor are tightly connected together, form relatively independent cavity, wherein with shell of reactor on reactant feeding mouth, the cavity that the reactant discharging opening communicates be feed side, with the sweep gas inlet on the shell of reactor), the cavity that communicates of sweep gas outlet is per-meate side; And these two kinds of cavitys can only carry out material Transfer by the loose structure of zero defect carbon membrane; Dose reaction mass at feed side, after the temperature and pressure of feed side reached required reaction condition, reaction mass carried out chemical reaction at feed side; Simultaneously, the component in the product is delivered to per-meate side by the porous channel of zero defect carbon membrane, and the sweep gas that is passed into per-meate side is taken away; Because the total amount of product reduces, and has therefore broken the restriction of the thermodynamics of closed system to chemical reaction equilibrium, make reaction continue to carry out, thereby improve conversion ratio, yield and the selectivity of chemical reaction to the positive reaction direction; And the material that has reacted flows out carbon membrane reactor from the reactant discharging opening.
The chemical reaction that can adopt the using method of described carbon membrane reactor to carry out has water-gas shift, cyclohexane dehydrogenation, dehydrogenation of isobutane and hydrogen production from methanol-steam reforming.
Advantage and effect: adopt such scheme, can in same reactor, realize the integrated of chemical reaction and separating substances, and improve conversion ratio, yield and the selectivity of reaction simultaneously; Shorten production technology, reduced equipment and product cost.
Description of drawings:
Fig. 1 is the structural representation of tubulose carbon membrane reactor of the present invention;
Fig. 2 is the vertical view of tubulose carbon membrane reactor of the present invention;
Fig. 3 is the structural representation of tabular carbon membrane reactor;
Fig. 4 is the vertical view of tabular carbon membrane reactor;
Fig. 5 is the structural representation of hollow fiber carbon membrane reactor;
Fig. 6 is the vertical view of hollow fiber carbon membrane reactor;
Description of reference numerals:
1, zero defect carbon membrane 2, shell of reactor 3, feed side 4, per-meate side 5, carbon membrane tube connector 6, reactant feeding mouth 7, reactant discharging opening 8, sweep gas inlet 9, sweep gas outlet 10, catalyst 11, material distributor 12, carbon membrane connecting plate.
The specific embodiment:
Below in conjunction with accompanying drawing the present invention is specifically described:
Fig. 1 is the structural representation of tubulose carbon membrane reactor of the present invention, and Fig. 2 is the vertical view of tubulose carbon membrane reactor of the present invention; As shown in the figure, at shell of reactor 2 upper axial end of the cylindrical shape thing feeding mouth 6 that responds, the corresponding other end thing discharging opening 7 that responds; Radially sweep gas inlet 8 is arranged the upper end at shell of reactor 2, there is sweep gas outlet 9 lower end; The zero defect carbon membrane 1 of tubulose is tightly connected by carbon membrane tube connector 5 and shell of reactor 2, connected mode is selected high-temperature seal adhesive, packing ring, cutting ferrule or welding as required, and the material of shell of reactor 2 is selected stainless steel, pottery, copper or metal alloy as required for use; At the zero defect carbon membrane 1 inner cavity that forms, be feed side 3, form two other cavitys at zero defect carbon membrane 1 and 2 of shell of reactor, be per-meate side 4; Feed side 3 communicates with reactant feeding mouth 6, reactant discharging opening 7; Per-meate side 4 communicates with sweep gas inlet 8, sweep gas outlet 9; At feed side 3 inner catalyst fillings 10, allow reaction mass enter in feed side 3 cavitys from reactant feeding mouth 6, control material and 10 times of contact of catalyst are carried out continuous chemical reaction under given reaction temperature and pressure; In course of reaction, the component that less molecule in the product or adsorptivity are stronger can be penetrated in the cavity of per-meate side 4 by the loose structure of zero defect carbon membrane 1, and along with the lasting sweep gas that feeds in the per-meate side 4 is taken carbon membrane reactor out of; And the material that has reacted flows out carbon membrane reactor from reactant discharging opening 7; The composition of material is by gas-chromatography or liquid chromatogram measuring in feed side 3 and per-meate side 4 cavitys; According to mass balance, the conversion ratio that obtains reacting, yield and selectivity.
The precursor of zero defect carbon membrane 1 of the present invention is polyimides, poly furfuryl alcohol, phenolic resins, polyacrylonitrile, polyphenylene oxide or cellulose, charing atmosphere is inert gas or vacuum, carbonization temperature is 400～1000 ℃, zero defect carbon membrane 1 supporter is carbonaceous, pottery, graphite, doughnut or stainless steel material, and film build method is coating or spraying or ultrasonic deposition or chemical vapour deposition (CVD).
The chemical reaction that can adopt the application process of carbon membrane reactor of the present invention to carry out has water-gas shift, cyclohexane dehydrogenation, dehydrogenation of isobutane and hydrogen production from methanol-steam reforming.
Fig. 3 is the structural representation of tabular carbon membrane reactor; Fig. 4 is the vertical view of tabular carbon membrane reactor; As shown in the figure, at the shell of reactor 2 tops one end thing feeding mouth 6 that responds, the other end thing discharging opening 7 that responds; At shell of reactor 2 bottoms one end sweep gas inlet 8 is arranged, the other end has sweep gas outlet 9; Flat zero defect carbon membrane 1 is tightly connected by carbon membrane connecting plate 12 and shell of reactor 2, connected mode is selected high-temperature seal adhesive, packing ring, cutting ferrule or welding as required, and the material of shell of reactor 2 is selected stainless steel, pottery, copper or metal alloy as required for use; Form two cavitys between zero defect carbon membrane 1 and shell of reactor 2, one of them cavity communicates with reactant feeding mouth 6, reactant discharging opening 7, is feed side 3; Another cavity communicates with sweep gas inlet 8, sweep gas outlet 9, is per-meate side 4; On flat zero defect carbon membrane 1, lay catalyst 10, allow reaction mass enter in feed side 3 cavitys, under given reaction temperature and pressure, control material and 10 times of contact of catalyst, carry out continuous chemical reaction from reactant feeding mouth 6; In course of reaction, the component that less molecule in the product or adsorptivity are stronger can be penetrated in the cavity of per-meate side 4 by the loose structure of zero defect carbon membrane 1, and along with the lasting sweep gas that feeds in the per-meate side 4 is taken carbon membrane reactor out of; And the material that has reacted flows out carbon membrane reactor from reactant discharging opening 7; The composition of material is by gas-chromatography or liquid chromatogram measuring in feed side 3 and per-meate side 4 cavitys; According to mass balance, the conversion ratio that obtains reacting, yield and selectivity.
The precursor of zero defect carbon membrane 1 of the present invention is polyimides, poly furfuryl alcohol, phenolic resins, polyacrylonitrile, polyphenylene oxide or cellulose, charing atmosphere is inert gas or vacuum, carbonization temperature is 400～1000 ℃, zero defect carbon membrane 1 supporter is carbonaceous, pottery, graphite, doughnut or stainless steel material, and film build method is coating or spraying or ultrasonic deposition or chemical vapour deposition (CVD).
The chemical reaction that can adopt the application process of carbon membrane reactor of the present invention to carry out has water-gas shift, cyclohexane dehydrogenation, dehydrogenation of isobutane and hydrogen production from methanol-steam reforming.
Fig. 5 is the structural representation of hollow fiber carbon membrane reactor; Fig. 6 is the vertical view of hollow fiber carbon membrane reactor; As shown in the figure, at shell of reactor 2 upper axial end of the cylindrical shape thing feeding mouth 6 that responds, the corresponding other end thing discharging opening 7 that responds; Radially sweep gas inlet 8 is arranged the upper end at shell of reactor 2, there is sweep gas outlet 9 lower end; The zero defect carbon membrane 1 of hollow fiber mode and the shell of reactor 2 by high-temperature seal adhesive, packing ring, cutting ferrule or welding is tightly connected, at the zero defect carbon membrane 1 inner cavity that forms, be feed side 3, between zero defect carbon membrane 1 and shell of reactor 2, form another kind of cavity, be per-meate side 4; Wherein be connected by material distributor 11 between feed side 3 and reactant feeding mouth 6, the reactant discharging opening 7, per-meate side 4 communicates with sweep gas inlet 8, sweep gas outlet 9; At feed side 3 inner catalyst fillings 10, allow reaction mass enter in feed side 3 cavitys from reactant feeding mouth 6, control material and 10 times of contact of catalyst are carried out continuous chemical reaction under given reaction temperature and pressure; In course of reaction, the component that less molecule in the product or adsorptivity are stronger can be penetrated in the cavity of per-meate side 4 by the loose structure of zero defect carbon membrane 1, and along with the lasting sweep gas that feeds in the per-meate side 4 is taken carbon membrane reactor out of; And the material that has reacted flows out carbon membrane reactor from reactant discharging opening 7; The composition of material is by gas-chromatography or liquid chromatogram measuring in feed side 3 and per-meate side 4 cavitys; According to mass balance, the conversion ratio that obtains reacting, yield and selectivity.
The precursor of zero defect carbon membrane 1 of the present invention is polyimides, poly furfuryl alcohol, phenolic resins, polyacrylonitrile, polyphenylene oxide or cellulose, charing atmosphere is inert gas or vacuum, carbonization temperature is 400～1000 ℃, zero defect carbon membrane 1 supporter is carbonaceous, pottery, graphite, doughnut or stainless steel material, and film build method is coating or spraying or ultrasonic deposition or chemical vapour deposition (CVD).
The chemical reaction that can adopt the application process of carbon membrane reactor of the present invention to carry out has water-gas shift, cyclohexane dehydrogenation, dehydrogenation of isobutane and hydrogen production from methanol-steam reforming.
Be specific embodiment below in conjunction with the present invention carried out:
Embodiment 1:
Be precursor with phenolic resins by soaking the method for stagnating be that 11mm, thickness are film forming on the porous sintered stainless steel supporter outside of 1.5mm at diameter, by solidify and 600 ℃ of argon gas in pyrolysis prepare the zero defect carbon membrane; Adopt Fig. 1, tubulose carbon membrane reactor shown in Figure 2, this zero defect carbon membrane is connected on the hollow tube on the stainless steel reactor shell by welding manner, carry out the preparing hydrogen by reforming methanol reaction.Fill Cu/ZnO/Al at zero defect carbon membrane pipe internal cavity
2O
3Catalyst; With the micro-measurement pump with the mixed liquor of first alcohol and water with the charging rate of 0.02mL/min with inert carrier gas (N
2) bring in the reactor and react.The per-meate side that forms between zero defect carbon membrane pipe and shell of reactor as sweep gas, is taken the gas molecule that generates in the course of reaction and preferential infiltration is come out of reaction system with Ar.After treating that system response is stable, by the composition of gas chromatographic detection from feed side outlet and per-meate side outlet effluent.And, obtain the yield of conversion of methanol, hydrogen and the selectivity of reaction by mass balance.Concrete reaction condition and data are as shown in the table:
| Sequence number | Sweep gas speed (mL/min -1) | Reaction temperature (℃) | Water alcohol ratio | Methanol conversion (%) |
| ??1 | ??30 | ??220 | ??1∶1 | ??30.3 |
| ??2 | ??80 | ??220 | ??1∶1 | ??42.8 |
| ??3 | ??350 | ??220 | ??1∶1 | ??78.2 |
| ??4 | ??250 | ??220 | ??0.8∶1 | ??62.3 |
| ??5 | ??250 | ??220 | ??2∶1 | ??81.3 |
| ??6 | ??250 | ??180 | ??1∶1 | ??65.9 |
| ??7 | ??250 | ??250 | ??1∶1 | ??88.0 |
| ??8 | ??112 | ??220 | ??1∶1 | ??35.3 |
| ??9 | ??250 | ??220 | ??1∶1 | ??66.6 |
| ??10 | ??250 | ??220 | ??1.5∶1 | ??71.9 |
| ??11 | ??250 | ??200 | ??1∶1 | ??73.4 |
Embodiment 2:
The length that with the polyimides is the precursor preparation is the doughnut of 150mm, prepares the zero defect carbon membrane of hollow fiber by pre-oxidation and 750 ℃ of vacuum pyrolysis.Adopt Fig. 5, hollow fiber carbon membrane reactor shown in Figure 6.This zero defect carbon membrane is sealedly and fixedly connected on the material distributor of ceramic of compact qualitative response device shell by viton gasket and high-temperature seal adhesive, carries out the reaction of cyclohexane dehydrogenation system benzene.In the cavity of zero defect carbon membrane, fill the Pt/Al of 0.5%wt
2O
3Catalyst; Cyclohexane after will vaporizing with the micro-measurement pump is with inert carrier gas (N
2) bring in the reactor after the dilution and react.Per-meate side between zero defect carbon membrane and shell of reactor as sweep gas, is taken the gas molecule that generates in the course of reaction and preferential infiltration is come out of reaction system with Ar.After treating that system response is stable, by the composition of gas chromatographic detection reactant discharging opening and per-meate side outlet material.Obtain the conversion ratio of benzene.Concrete reaction condition and data are as shown in the table:
| Sequence number | Charging flow velocity (mg/min -1) | Reaction temperature (℃) | Cyclohexane conversion (%) |
| ??1 | ??6.5 | ??170 | ??23 |
| ??2 | ??6.5 | ??180 | ??35 |
| ??3 | ??6.5 | ??200 | ??54 |
| ??4 | ??6.5 | ??220 | ??58 |
| ??5 | ??8.5 | ??200 | ??26 |
| ??6 | ??4.5 | ??200 | ??33 |
Embodiment 3:
With the polyacrylonitrile is that the length that precursor prepares is the doughnut of 200mm, by pre-oxidation and 650 ℃ of hollow fiber zero defect carbon membranes that vacuum pyrolysis prepares.Adopt Fig. 5, hollow fiber carbon membrane reactor shown in Figure 6.This zero defect carbon membrane is sealedly and fixedly connected on the material distributor of copper shell of reactor by graphite gasket and graphite ferrule, carries out the chemical reaction of preparing isobutene through dehydrogenation of iso-butane.In the cavity of hollow fiber zero defect carbon membrane, fill Cr
2O
3/ Al
2O
3Catalyst.With the micro-measurement pump with isobutane gas with inert carrier gas (N
2) bring in the reactor after the dilution and react.Per-meate side between hollow fiber zero defect carbon membrane and shell of reactor as sweep gas, is taken the gas molecule that generates in the course of reaction and preferential infiltration is come out of reaction system with Ar.After treating that system response is stable, by the composition of gas chromatographic detection from feed side outlet and per-meate side outlet effluent.Obtain the conversion ratio of iso-butane.Concrete reaction condition and data are as shown in the table:
| Sequence number | Charging flow velocity (mg/min -1) | Reaction temperature (℃) | Iso-butane conversion ratio (%) |
| ??1 | ??0.03 | ??450 | ??11.2 |
| Sequence number | Charging flow velocity (mg/min -1) | Reaction temperature (℃) | Iso-butane conversion ratio (%) |
| ??2 | ??0.06 | ??450 | ??9.1 |
| ??3 | ??0.09 | ??450 | ??8.5 |
| ??4 | ??0.03 | ??550 | ??35.7 |
| ??5 | ??0.06 | ??550 | ??28.6 |
| ??6 | ??0.09 | ??550 | ??22.4 |
Embodiment 4:
The porous graphite flat board be on the supporter with cellulose film forming, prepare the tabular zero defect carbon membrane of 100mm*150mm by 750 ℃ of nitrogen atmosphere pyrolysis.Adopt Fig. 3, tabular carbon membrane reactor shown in Figure 4, with this zero defect carbon membrane by graphite gasket and bolt mode sealing and fixing on the copper alloy shell of reactor, carry out the chemical reaction of Water gas shift/WGS.In the cavity of tabular zero defect charcoal one side and shell of reactor formation, fill ferrum-based catalyst.Enter the CO of reactor and the flow of Ar gas and water vapour with mass flow controller and micro pump control.Per-meate side N in tabular zero defect charcoal opposite side and shell of reactor formation
2As sweep gas, take the gas molecule that generates in the course of reaction and infiltration is come out of reaction system.After treating that system response is stable, by the composition of gas chromatographic detection from feed side outlet and per-meate side outlet effluent.Obtain the conversion ratio of CO.Concrete reaction condition and data are as shown in the table:
| Sequence number | ??H 2The O/CO mol ratio | Reaction temperature (℃) | CO conversion ratio (%) |
| ??1 | ??1∶2 | ??390 | ??45.2 |
| ??2 | ??1∶1 | ??390 | ??76.1 |
| ??3 | ??2∶1 | ??390 | ??89.3 |
| ??4 | ??1∶1 | ??320 | ??42.7 |
| ??5 | ??1∶1 | ??420 | ??78.5 |
Claims (9)
1. a carbon membrane reactor comprises shell of reactor (2), and zero defect carbon membrane (1) is characterized in that: have reactant feeding mouth (6), reactant discharging opening (7), sweep gas inlet (8), sweep gas outlet (9) on the shell of reactor (2); Zero defect carbon membrane (1) is arranged on shell of reactor (2) inside, at the relatively independent cavity of the inner formation of shell of reactor (2), wherein the cavity that communicates with reactant feeding mouth (6), reactant discharging opening (7) is feed side (3), and the cavity that communicates with sweep gas inlet (8), sweep gas outlet (9) is per-meate side (4); Lay catalyst (10) at the inner catalyst filling of zero defect carbon membrane (1) (10) or on zero defect carbon membrane (1).
2. according to the described a kind of carbon membrane reactor of claim 1, it is characterized in that: described zero defect carbon membrane (1) is tabular, tubulose or hollow fiber.
3. according to the described a kind of carbon membrane reactor of claim 1, it is characterized in that: described zero defect carbon membrane (1) is connected by carbon membrane tube connector (5) or carbon membrane connecting plate (12) with shell of reactor (2).
4. according to the described a kind of carbon membrane reactor of claim 1, it is characterized in that: described shell of reactor (2) material is fine and close stainless steel, pottery, copper or metal alloy.
5. according to the described a kind of carbon membrane reactor of claim 1, it is characterized in that: described zero defect carbon membrane (1) and shell of reactor (2) are for being tightly connected, and connected mode is high-temperature seal adhesive, graphite gasket, graphite ferrule or welding.
6. according to the described a kind of carbon membrane reactor of claim 3, it is characterized in that: when having a plurality of feed sides (3), between a plurality of feed sides (3) and reactant feeding mouth (6), reactant discharging opening (7), be connected by material distributor (11).
7. according to the described a kind of carbon membrane reactor of claim 1, it is characterized in that: the precursor of described zero defect carbon membrane (1) is polyimides, poly furfuryl alcohol, phenolic resins, polyacrylonitrile, polyphenylene oxide or cellulose, charing atmosphere is inert gas or vacuum, carbonization temperature is 400～1000 ℃, zero defect carbon membrane (1) supporter is carbonaceous, pottery, graphite, doughnut or stainless steel material, and film build method is coating or spraying or ultrasonic deposition or chemical vapour deposition (CVD).
8. using method of carbon membrane reactor according to claim 1, it is characterized in that: described using method is:
Zero defect carbon membrane (1) and shell of reactor (2) are tightly connected together, form relatively independent cavity, wherein with shell of reactor (2) on reactant feeding mouth (6), the cavity that reactant discharging opening (7) communicates be feed side (3), be per-meate side (4) with the sweep gas inlet (8) on the shell of reactor (2), the cavity that sweep gas outlet (9) communicates; And these two kinds of cavitys can only carry out material Transfer by the loose structure of zero defect carbon membrane (1); Add reaction mass at feed side (3), after the temperature and pressure of feed side (3) reached required reaction condition, reaction mass carried out chemical reaction at feed side (3); Simultaneously, the component in the product is delivered to per-meate side (4) by the porous channel of zero defect carbon membrane (1), and the sweep gas that is passed into per-meate side (4) is taken away; Because the total amount of product reduces, and has therefore broken the restriction of the thermodynamics of closed system to chemical reaction equilibrium, make reaction continue to carry out, thereby improve conversion ratio, yield and the selectivity of chemical reaction to the positive reaction direction; And the material that has reacted flows out carbon membrane reactor from reactant discharging opening (7).
9. the using method of described a kind of carbon membrane reactor according to Claim 8 is characterized in that: the chemical reaction that can adopt the using method of described carbon membrane reactor to carry out has water-gas shift, cyclohexane dehydrogenation, dehydrogenation of isobutane and hydrogen production from methanol-steam reforming.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016026799A1 (en) | 2014-08-20 | 2016-02-25 | Bayer Technology Services Gmbh | Method for phosgenating compounds containing hydroxyl, thiol, amino and/or formamide groups |
| CN113164904A (en) * | 2018-12-12 | 2021-07-23 | 沙特阿拉伯石油公司 | Membrane-based process for producing butanol from mixed butenes |
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| WO2009085252A1 (en) * | 2007-12-19 | 2009-07-09 | Saudi Arabian Oil Company | Suspended media granular activated carbon membrane biological reactor system and process |
| CN101597096A (en) * | 2009-06-30 | 2009-12-09 | 天津工业大学 | A kind of electro-catalytic membrane reactor device |
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| WO2016026799A1 (en) | 2014-08-20 | 2016-02-25 | Bayer Technology Services Gmbh | Method for phosgenating compounds containing hydroxyl, thiol, amino and/or formamide groups |
| CN107073434A (en) * | 2014-08-20 | 2017-08-18 | 拜耳股份公司 | Contain the method for the compound of hydroxyl, sulfydryl, amino and/or carbonylamino group for phosgenation |
| US10105675B2 (en) | 2014-08-20 | 2018-10-23 | Bayer Aktiengesellschaft | Method for phosgenating compounds containing hydroxyl, thiol, amino and/or formamide groups |
| CN107073434B (en) * | 2014-08-20 | 2018-10-26 | 拜耳股份公司 | Contain the method for the compound of hydroxyl, sulfydryl, amino and/or carbonylamino group for phosgenation |
| CN113164904A (en) * | 2018-12-12 | 2021-07-23 | 沙特阿拉伯石油公司 | Membrane-based process for producing butanol from mixed butenes |
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