CN102580478B - Integrated tubular ceramic oxygen permeating membrane separation reactor - Google Patents
Integrated tubular ceramic oxygen permeating membrane separation reactor Download PDFInfo
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- CN102580478B CN102580478B CN201210074519.5A CN201210074519A CN102580478B CN 102580478 B CN102580478 B CN 102580478B CN 201210074519 A CN201210074519 A CN 201210074519A CN 102580478 B CN102580478 B CN 102580478B
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Abstract
The invention relates to an integrated high-temperature tubular membrane separation reactor. The reactor is formed by sequentially serially combining supporting plates, a spring, a movable tube plate, a membrane tube and a fixed tube plate through four guide rails and a fixing device and arranged in a tubular electric furnace to form the integrated membrane separation reactor. A tubular ceramic membrane is arranged in placement holes in the fixed tube plate and the movable tube plate which are positioned at two ends and sealed by using a high-temperature sealant. The sealed part is positioned outside a heating area of a heating furnace. The movable tube plate is a component capable of moving along the guide rails, and is used for effectively dredging axial expansion of the membrane and a membrane assembly in the heating and cooling process. The reactor is reasonable in design, compact in structure and wide in application, and breaks through the conventional design concept; and the efficiency and the practicability of the reactor are greatly improved. The reactor is suitable for tubular membranes of multiple structures, breaks through the limitation that the conventional oxygen separation membrane reactor can only be applied to pure oxygen separation, can be applied to preparation of pure oxygen, and can also be applied to a membrane reaction process.
Description
Technical field
The present invention relates to a kind of integral type high-temperature tubular membrane separation reactor.Be specifically related to a kind ofly utilize separated airborne oxygen under ceramic oxygen-permeable membrane high temperature to carry out oxygen separation, more can utilize infiltration by the oxygen of film, to carry out the ceramic oxygen-permeable membrane oxygen separate reactor of film reaction simultaneously.
Technical background
Mixed conductor membrane material is the inorganic ceramic membrane material (Teraoka et al., Chem.Lett., 1985) of a kind of conduction electron simultaneously and oxonium ion, is widely used in pure oxygen preparation, fuel cell, sensor, a plurality of fields such as membrane reactor.Utilize it for 100% feature optionally of oxonium ion, can be used for producing high-purity oxygen (> 99%), meanwhile, mixed conductor membrane material has higher oxygen flux.Compare with current industrial oxygen generation method used (as cryogenic separation and pressure-variable adsorption), by fine and close composite conductor oxygen-permeating film oxygen, not only have and very high selectively and can produce continuously, greatly reduce energy consumption and investment and running cost.At present, composite conductor oxygen-permeating film is not merely used to separated air oxygen, its application further expands to selective oxidation and the hydrogen production reaction for low-carbon (LC) hydro carbons as membrane reactor, as hydrocarbon oxidation preparing synthetic gas or hydrogen, methane oxidation coupling ethane/ethylene processed, making ethylene from ethane oxidative dehydrogenation etc.For example, traditional methane reforming is undertaken by fixed bed reactors, and this reformation mode easily causes temperature runaway problem and reforming process use purity oxygen, must have special oxygen supply factory that oxygen is provided.Yet ripe air separation technology is cryogenic rectification and pressure-variable adsorption at present, and its power consumption is high, has greatly increased the cost of partial oxidation of methane hydrogen.And adopt, take the membrane reactor that oxygen permeable film material is core component and carry out partial oxidation of methane hydrogen, at high temperature composite conductor oxygen-permeating film material can be from air or other oxygen-containing gas separated pure oxygen, separation and the methane partial reaction of oxygen can be carried out simultaneously, can avoid like this investment of expensive oxyen manutactory, simplify production process, reduce production costs.According to the literature, this process is than present methane aqueous vapor preparing synthetic gas by reforming process cost-saving 25%～50%.In addition, composite conductor oxygen-permeating film also can be used as high-temperature decomposition reaction (as H
2o and CO
2decomposition reaction) oxygen separation membrane, to improve equilibrium conversion, also can be used for oxygen enrichment catalytic combustion, improves flame holding, reduces NO
xand the discharge capacity of CO waste gas.Corresponding research not only can produce significant impact to relevant chemical process, and the development of new high-tech material in the fields such as the energy, environmental protection is also produced to positive impetus.
Core component for this membrane reactor of composite conductor oxygen-permeating film, through the research to year, developed the mixed conductor membrane material of multiple function admirable, there is good permeability and stability, be specially adapted to high temperature, hypoxemia and reducing atmosphere environment, for exploitation high-performance oxygen separate reactor provides sturdy technical foundation and guarantee.And current research center of gravity progressively builds and shifts to applied membrane separation reactor from material foundation research.In prior art, chip and flat film are not also suitable for large-scale industrial application, on the one hand because this type of film configuration filling area is little, film thickness large, the oxygen flux of unit are is little, on the other hand in membrane reactor, be difficult to large-area at its surperficial loading catalyst, sealing under hot conditions and assembly connect also very difficult solution simultaneously, are the fatal bottlenecks of its large-scale application of restriction.Therefore, the current more application of the film of this type of configuration is in laboratory fundamental research.Tubular membrane configuration can improve filling area, reduces thickness, improve permeation flux, and can adopt cold junction sealing, reduces greatly sealing difficulty.Therefore, build and a kind ofly have efficiently, stable, simple and easy, practical high-temperature tubular membrane separation reactor is to be development trend and the research emphasis of high temperature mixed conductor membrane separation reactor at present.
Summary of the invention
Goal of the invention of the present invention provides a kind of integral type high-temperature tubular membrane separation reactor that is applicable to oxygen separation and film reaction process in order to improve the deficiencies in the prior art.
Technical scheme of the present invention is: integral type high-temperature tubular membrane separation reactor, it is characterized in that this reactor is by the first gripper shoe (1A), mobile tube sheet (3), fixed tube sheet (4), the second gripper shoe (1B) becomes by guide rail (5) successively tandem compound; The first gripper shoe (1A), the second gripper shoe (1B) and fixed tube sheet (4) are fixing by fixture and guide rail (5); Mobile tube sheet (3) and the corresponding position of fixed tube sheet (4) have the placement hole (12) of accepting film pipe, and film pipe (6) is placed in placement hole (12); The upper cover of guide rail (5) between mobile tube sheet (3) and the first gripper shoe (1A) has spring (2); On mobile tube sheet (3) and fixed tube sheet (4), be respectively equipped with air collecting chamber lid (7), placement hole (12) on mobile tube sheet (3) and fixed tube sheet (4) is all placed in air collecting chamber lid (7), takes over (8) and is connected with air collecting chamber lid (7); The first gripper shoe (1A), the second gripper shoe (1B), mobile tube sheet (3) and fixed tube sheet (4) are positioned at the non-thermal treatment zone of heating furnace (9), are integrally formed formula membrane separation reactor.
Preferably described film pipe 6 is ceramic pipe type film; By conventional plasticity, extrude moulding by casting, the method preparations such as phase inversion method.Wherein membrane material is perofskite type oxide, and this material is C by general formula
1-xc '
xd
yd '
1-yo
3-δperofskite type oxide and the composition of simple metal oxide, wherein, 0≤x <, 1,0≤y <, 1 ,-0.5 < δ < 0.5; C, C ' are any one element in La, Pr, Nd, Sm, Gd, Ba or Sr; D, D ' are any one element of Cr, Mn, Fe, Co, Ni, Cu, Zn or Bi, synthetic by sol-gel process, solid reaction process, hydro-thermal method or coprecipitation.
Preferably described fixture is comprised of fixed head 16, rubber o-ring 17 and screw 18: wherein rubber o-ring 17 is placed on the guide rail 5 between the first gripper shoe 1A, the second gripper shoe 1B and fixed tube sheet 4 and fixed head 16, and screws by screw 18.
The central area radial of mobile tube sheet 3 and fixed tube sheet 4 evenly has the placement hole 12 of accepting film pipe 6, and placement hole periphery has the guide rail hole 13 of accepting guide rail 5; Tubular ceramic membrane is placed in the placement hole 12 of fixed tube sheet 4 and mobile tube sheet 3, uses encapsulant 15 sealings.Hermetic unit is outside heating furnace heating region.
Mobile tube sheet is for can prolong guide rail 5 moving-members.On guide rail 5 between mobile tube sheet 3 and the first gripper shoe 1A, install spring 2, preferably the stiffness factor k of spring is 500～1500N/m.
In this reactor, only have mid portion tubular membrane 6 and guide rail 5 in heating furnace heating region, the distance of fixed tube sheet 4 and mobile tube sheet 3 partial distance heating furnace heating regions is 5～15 centimetres.
Two pipe nipples 8 can all be opened, and one of an air inlet is given vent to anger; Or one shut one and open, open pipe nipple and connect oilless vacuum pump.
According to the treating capacity in actual use procedure, the uniformity of Temperature Distribution and device physical dimension size, the number general control of film pipe is at 10～25.
Perofskite type oxide in material of the present invention can be used the conventional methods such as sol-gel process, solid reaction process, hydro-thermal method or coprecipitation synthetic, and the preparation method of film pipe can use plasticity to extrude, moulding by casting, the conventional method preparations such as phase inversion.
Beneficial effect:
The present invention is reasonable in design, has broken through traditional design concept, has greatly improved efficiency and the practicality of reactor.Film two ends are all fixed among tube sheet, with respect to one end, fix, and one end is the membrane reactor of fixing (unsettled) not, have greatly improved the stability of reactor.The tube sheet being connected with film pipe one end moves for prolonging guide rail simultaneously, can effectively dredge the axial expansion that film and membrane module cause in heating and cooling process, has improved the mechanical stability of film.Significantly moving of spring restriction tube sheet, offsets the axially-movable at film and mobile tube sheet, further improves the stability of apparatus structure.Sealed end is placed in outside the thermal treatment zone, and cold junction sealing, has solved conventional film reactor high temperature Sealing Technology difficult point, has effectively reduced sealing difficulty, and has greatly improved airtight quality.
Compact conformation of the present invention is reasonable, can, further to miniaturization, integrative development, prepare small portable oxygen system.The present invention is simultaneously of many uses, is applicable to the tubular membrane of multiple configuration, as extra heavy pipe, tubule, hollow-fibre membrane etc.Break through especially traditional oxygen separation membrane reactor and only can be applied to the restriction of the preparation of pure oxygen separation, shut the one end that the present invention is directed to conventional separators, the structure of reactor of the single application of bleeding in one end, brand-new design structure of reactor mentioned above, make this type of refractory ceramics membrane reactor can be applied to film reaction process, there is stronger creativeness and practicality.
Accompanying drawing explanation:
Fig. 1 is the structural representation of invention integrated tubular ceramic oxygen-permeable membrane separate reactor;
Fig. 2 is mobile tube sheet and Fixed Tubesheet Structure schematic diagram in Fig. 1;
Fig. 3 is mobile tube sheet, air collecting chamber lid, takes over combination unit structure schematic diagram;
Fig. 4 is gripper shoe and fixed plate structure schematic diagram in Fig. 1;
Fig. 5 is gripper shoe unit and fixed tube sheet unit fixed form structural representation;
Wherein:
1A: the first gripper shoe; 1B: the second gripper shoe; 2: spring; 3: mobile tube sheet; 4: fixed tube sheet; 5: guide rail; 6: film pipe; 7: air collecting chamber lid; 8: take over; 9: tube type resistance furnace; 10: heat-preservation cotton; 11: resistance wire; 12: placement hole; 13: guide rail hole; 14: screwed hole; 15: encapsulant; 16: fixed head; 17:O type circle; 18: screw.
Fig. 6 is non-heating interval axial temperature distribution curve during the different central temperature of tube furnace in embodiment 2;
Fig. 7 is the thermal expansion curve map of different guide material and film tube material in embodiment 3, supposes that in heating interval material raw footage be 20cm;
Fig. 8 is oxygen flux temporal evolution curve during 900 ℃ of 10 passage SCF thin-tube type oxygen separators in embodiment 5;
Fig. 9 is methane conversion and selective temperature variation curve during 900 ℃ of 20 passage LSCF thin-tube type membrane reactors in embodiment 6;
Figure 10 is methane conversion and selective temporal evolution curve during 850 ℃ of 20 passage LSCF thin-tube type membrane reactors in embodiment 7.
Specific implementation method:
The material SrCo relating in following examples
0.8fe
0.2o
3-δ(SCF), La
0.5sr
0.5co
0.8fe
0.2o
3-δ(LSCF), Ba
0.5sr
0.5co
0.8fe
0.2o
3-δ(BSCF) powder can be used the conventional methods such as sol-gel process, solid reaction process, hydro-thermal method or coprecipitation synthetic, and the preparation method of film pipe can use plasticity to extrude, moulding by casting, the conventional method preparations such as phase inversion.
Embodiment 1:
Fig. 1 is the structural representation of integral type tubular type ceramic oxygen-permeable membrane separate reactor.Membrane module and heating furnace are integrally formed formula tubular type ceramic oxygen-permeable membrane separate reactor jointly.Membrane reactor module body part is formed by four alundum tube guide rail 5 tandem compounds by the first gripper shoe 1A, spring 2, mobile tube sheet 3, fixed tube sheet 4, the second gripper shoe 1B successively.Tubular ceramic membrane 6 is placed between mobile tube sheet 3 and fixed tube sheet 4, concentrates by air collecting chamber and covers 7 and take over 8 and realize air inlet and give vent to anger operation.Whole membrane module is placed in tube type resistance furnace 9, wherein removes part film pipe and the guide rod heating interval (by heat-preservation cotton 10, resistance wire 11 forms) in resistance furnace, and remainder is all outside the thermal treatment zone.
Fig. 2 is mobile tube sheet and Fixed Tubesheet Structure schematic diagram, opens respectively film pipe placement hole 12, guide rail hole 13, screwed hole 14, as shown in the figure arranged distribution on dish; Tubular type ceramic oxygen-permeable membrane 6 inserts respectively in placement hole 12 corresponding on mobile tube sheet 3 and fixed tube sheet 4.As shown in Figure 3,12 of film pipe 6 and placement holes are used high-temperature sealing material 15 to seal; Tube sheet 3,4 and air collecting chamber lid 7, take over 8 and be threaded, realize charging and discharging operation in tubular membrane pipe.The unit of combining structure shown in Fig. 3 is not fixed with guide rail, coordinates for dredging the axial displacement that heating interval inner mold tube causes because of heating and cooling with next-door neighbour's spring.
Except mobile tube sheet 3, fixed tube sheet 4, two end supports plate 1A and 1B are all connected with guide rail 5 by fixed head 16, fixed head 16 structures and supporting plate structure similar (Fig. 4).Fig. 5 is gripper shoe unit and fixed tube sheet unit fixed form structural representation.Between gripper shoe/fixed tube sheet, fixed head by be positioned at rubber o-ring 17 on guide rail and screw 18 carry out fastening, to reach fixed support effect.
According to above-mentioned installation connected mode combined films assembly and tubular heater, be integrally formed formula ceramic oxygen-permeable membrane separate reactor: during making oxygen by air separation, the sealing of adapter one end, one termination oilless vacuum pump, logical compressed air in stove, furnace temperature is heated to 500 ℃～1000 ℃, and the gas of extracting out by vavuum pump is pure oxygen.During film reaction, take over the logical feeding gas (as methane) in one end, a termination gas collector, logical compressed air in stove, furnace temperature is heated to 500 ℃～1000 ℃, and feeding gas reacts with the pure oxygen that sees through film in pipe, the synthetic target product of reaction.
Below in conjunction with embodiment, the present invention is further elaborated:
Embodiment 2:
Reactor is placed in tubular heater, and two ends fixed tube sheet and mobile tube sheet and hermetic unit are all outside heating furnace heating interval.Fluid sealant 704 silicon rubber sealants, this kind of sealant heatproof is the highest 250 ℃, 200 ℃ of long-term maximum operation (service) temperatures, resistance to elevated temperatures is excellent.As index, determine that tube sheet (hermetic unit) is apart from the distance of heating furnace heating interval, guarantee airtight quality and film pipe utilization rate.Non-heating interval axial temperature distribution curve when Fig. 6 is the different central temperature of tube furnace.As seen from Figure 6, along with the raising of temperature between diamond heating center, fire door temperature also rises accordingly to some extent, and the outer axial temperature of stove reduces rapidly along with the increase apart from fire door distance simultaneously.When apart from the about 5cm of fire door apart from time, can guarantee when different furnace temperature, the temperature of tube sheet (hermetic unit) is less than 200 ℃, meets the requirement of sealing and peak use rate.Other is as inorganic sealant, metal sealing agent heatproof temperature is far above organic encapsulant, consider the factors such as temperature curve shown in the serviceability temperature requirement, installation difficulty, figure of sealant and film pipe utilization rate, tube sheet (hermetic unit) can be controlled at 5～15cm apart from the distance of fire door.
Embodiment 3:
Be different from normal temperature tubular membrane device device, in the present invention, device, in hot environment (500 ℃ of >), also has partial devices in normal temperature environment simultaneously.Parts in hot environment, in heating and cooling process, must bring larger expansion or shrinkage phenomenon, and between parts and and normal temperature environment in there is larger hot expansibility difference between parts, if can not effectively solve the stress difference that material expands and brings, to jeopardize greatly membrane module structure stability, even cause film tracheal rupture, the danger that imflammable gas is revealed and then exploded.In the present embodiment, the hot expansibility of all parts in hot environment is tested, Fig. 7 is the thermal expansion curve map of different guide material and film tube material, supposes that in heating interval material raw footage be 20cm.By figure, can be found, the length of material is linear the increasing along with the increase of temperature all.By 1 of form, perovskite ceramics material LSCF, the thermal coefficient of expansion of BSCF and SCF is obviously greater than the thermal coefficient of expansion as the quartz in guide rail candidate materials and corundum, because whole device and tube furnace are assembled into one, two ends fixed tube sheet and tube furnace housing contacts, relative sliding significantly, therefore, the quartz material with minimum coefficient of thermal expansion is best guide material, is secondly corundum material.
The thermal coefficient of expansion of the different guide rails of form 1 and film tubing matter and relative length change
Embodiment 4:
Film pipe and guide rail all in hot environment, are heated to 900 ℃ from room temperature and are, film pipe with respect to the length variations of guide rail as shown in Table 1, can be found out, in temperature-rise period, has larger length variations, and and guide rail and normal temperature parts between there is bigger difference.Therefore between mobile tube sheet side and gripper shoe, add shock mount, offset on the one hand film length of tube and change the stress bringing, on the other hand whole device is provided support to restriction, the significantly mobile unstability of bringing of moving-limiting tube sheet.The selective basis of spring, film length of tube changes, and the compression strength of film pipe, by Hooke's law F=kx, calculates the stiffness factor of spring.As shown in Table 2, the 20 channel membrane reactors of take are example, calculate the maximum stiffness factor of the spring that different film tube materials use.By this account form, can draw, different film pipes, different film pipe filling numbers, during different number of springs, the type selecting standard of spring.
The stiffness factor of different film tube material 20 channel membrane reactor springs during 2 900 ℃ of forms
Embodiment 5:
Reactor is taken over to one end sealing, a termination oilless vacuum pump, logical compressed air in stove, furnace temperature is heated to 900 ℃.Structure of reactor is identical with structure described in embodiment 1, uses 10 SCF tubular membrane, film pipe overall length 40cm, and tube sheet (hermetic unit) is 10cm apart from the distance of fire door, concrete film pipe and device parameter are as shown in Table 2.Oxygen flux temporal evolution curve when Fig. 8 is 900 ℃ of 10 passage SCF thin-tube type oxygen separators, in reactor, air side partial pressure of oxygen is 0.021MPa, and in pipe, vacuum is 0.1MPa, and stabilize oxygen flux is 0.10L/min.The area of oxygen permeation membrane
l, D
oand D
irepresent respectively effective length and the inner and outer diameter of film pipe.Every square metre of membrane area of reactor oxygen transmission rate per hour is that 331.5L (is 331.5L/h/m
2).
Embodiment 6:
Structure of reactor is identical with structure described in embodiment 1, uses 20 LSCF tubular membrane, film pipe overall length 40cm, and tube sheet (hermetic unit) is 10cm apart from the distance of fire door, concrete film pipe and device parameter are as shown in Table 2.Each probe temperature point stops 1 hour, and each Data duplication is guaranteed the accuracy of result for 3 times above.Fig. 9 has provided LSCF membrane reactor reactivity worth variation with temperature curve.As seen from the figure, CH
4conversion ratio oxygen permeation flux and hydrogen productive rate increase with the rising of temperature.At 900 ℃, CH
4conversion ratio is 93%; Hydrogen selectively before 800 ℃ the rising with temperature increase, yet at 875 ℃, reduce to some extent later, 900 ℃ of left and right, maintain more than 90%.
Embodiment 7:
For industrial applications, mixed conductor film reactor must possess the long-time stability under high temperature and reducing atmosphere.Figure 10 has provided LSCF membrane reactor more than 240 hours stability test result under 850 ℃ of methane portion oxidation conditions.Structure of reactor is identical with structure described in embodiment 1, uses 20 SCF tubular membrane, film pipe overall length 40cm, and tube sheet (hermetic unit) is 5cm apart from the distance of fire door, concrete film pipe and device parameter are as shown in Table 2.At test period, CH
4conversion ratio, hydrogen remain on 77%, 95% selectively, respectively, this explanation, and membrane reactor of the present invention shows good reactivity worth and very high long-time stability.Reaction stops and being down to after room temperature, it is complete that tubular membrane still keeps, do not find because the phenomenon of the film pipe fracture that in heating and cooling process, material heat expansion and STRESS VARIATION cause, illustrate that the present invention designs to can be good at solving the steady in a long-term operational issue of film in hot environment.
Claims (7)
1. integral type high-temperature tubular membrane separation reactor, is characterized in that by the first gripper shoe (1A), mobile tube sheet (3), fixed tube sheet (4), and the second gripper shoe (1B) becomes by guide rail (5) successively tandem compound; The first gripper shoe (1A), the second gripper shoe (1B) and fixed tube sheet (4) are fixing by fixture and guide rail (5); Mobile tube sheet (3) and the corresponding position of fixed tube sheet (4) have the placement hole (12) of accepting film pipe, and film pipe (6) is placed in placement hole (12); The upper cover of guide rail (5) between mobile tube sheet (3) and the first gripper shoe (1A) has spring (2); On mobile tube sheet (3) and fixed tube sheet (4), be respectively equipped with air collecting chamber lid (7), placement hole (12) on mobile tube sheet (3) and fixed tube sheet (4) is all placed in air collecting chamber lid (7), takes over (8) and is connected with air collecting chamber lid (7); The first gripper shoe (1A), the second gripper shoe (1B), mobile tube sheet (3) and fixed tube sheet (4) are positioned at the non-thermal treatment zone of heating furnace (9).
2. according to integral type high-temperature tubular membrane separation reactor claimed in claim 1, it is characterized in that described film pipe (6) is ceramic pipe type film; Wherein membrane material is perofskite type oxide, and this material is C by general formula
1-xc '
xd
yd '
1-yo
3-δperofskite type oxide and the composition of simple metal oxide, wherein, 0≤x<1,0≤y<1 ,-0.5< δ <0.5; C, C ' are any one element in La, Pr, Nd, Sm, Gd, Ba or Sr; D, D ' are any one element of Cr, Mn, Fe, Co, Ni, Cu, Zn or Bi.
3. according to integral type high-temperature tubular membrane separation reactor claimed in claim 1, it is characterized in that described guide rail (5) material is quartz or corundum material.
4. according to integral type high-temperature tubular membrane separation reactor claimed in claim 1, it is characterized in that described fixture is comprised of fixed head (16), rubber o-ring (17) and screw (18): the guide rail (5) that wherein rubber o-ring (17) is placed between the first gripper shoe (1A), the second gripper shoe (1B) and fixed tube sheet (4) and fixed head (16) is upper, and screws by screw (18).
5. according to integral type high-temperature tubular membrane separation reactor claimed in claim 1, the central area radial that it is characterized in that mobile tube sheet (3) and fixed tube sheet (4) evenly has the placement hole (12) of accepting film pipe (6), and placement hole periphery has the guide rail hole (13) of accepting guide rail (5); Tubular ceramic membrane is placed in the placement hole (12) of fixed tube sheet (4) and mobile tube sheet (3), uses encapsulant (15) to seal between film pipe (6) and placement hole (12).
6. according to integral type high-temperature tubular membrane separation reactor claimed in claim 1, it is characterized in that the stiffness factor k of described spring is 500～1500N/m.
7. according to integral type high-temperature tubular membrane separation reactor claimed in claim 1, it is characterized in that fixed tube sheet (4) and mobile tube sheet (3) are 5～15 centimetres from the distance of heating furnace heating region.
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| RU195987U1 (en) * | 2019-12-05 | 2020-02-12 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук | Pure oxygen plant |
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| CN1416946A (en) * | 2001-11-02 | 2003-05-14 | 中国科学院大连化学物理研究所 | Composite conductor oxygen-permeating film reactor and its application |
| CN2764471Y (en) * | 2005-01-14 | 2006-03-15 | 山东理工大学 | Ceramic electrolyte hollow fiber membrane tube bundle reactor |
| CN101522291B (en) * | 2006-09-29 | 2012-02-15 | 辛维特有限公司 | Leak-proof membrane element and method of manufacturing such an element |
| CN201175650Y (en) * | 2007-10-24 | 2009-01-07 | 山东理工大学 | Ceramic hollow fiber oxygen permeable membrane tube component for making oxygen by air separation |
| CN101264860B (en) * | 2008-04-21 | 2010-11-17 | 上海大学 | Oxygen-permeating film reactor used for coke oven crude gas mixing and reforming in hydrogen preparation technique |
| IT1401192B1 (en) * | 2010-06-16 | 2013-07-12 | Enea Agenzia Naz Per Le Nuove Tecnologie L En E Lo Sviluppo Economico Sostenibile | MEMBRANE REACTOR FOR THE TREATMENT OF GAS CONTAINING TRIZIO |
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