CN102580478A - Integrated tubular ceramic oxygen permeating membrane separation reactor - Google Patents
Integrated tubular ceramic oxygen permeating membrane separation reactor Download PDFInfo
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- CN102580478A CN102580478A CN2012100745195A CN201210074519A CN102580478A CN 102580478 A CN102580478 A CN 102580478A CN 2012100745195 A CN2012100745195 A CN 2012100745195A CN 201210074519 A CN201210074519 A CN 201210074519A CN 102580478 A CN102580478 A CN 102580478A
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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 under the ceramic oxygen-permeable membrane high temperature oxygen in the separation of air to carry out oxygen to separate, more can utilize infiltration to carry out the ceramic oxygen-permeable membrane oxygen separate reactor of film reaction through the oxygen of film simultaneously.
Technical background
The 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 the pure oxygen preparation, fuel cell, sensor, a plurality of fields such as membrane reactor.Utilize its 100% characteristics optionally for oxonium ion, can be used for producing high-purity oxygen (＞99%), simultaneously, the mixed conductor membrane material has higher oxygen flux.Compare with oxygen generation method (like cryogenic separation and transformation absorption) used in the present industry, not only have very high selectivity with fine and close composite conductor oxygen-permeating film system oxygen, and can produce continuously, cut down the consumption of energy greatly and investment and running cost.At present; Composite conductor oxygen-permeating film not merely is used to separation of air system oxygen; Its application further expands to selective oxidation and the hydrogen production reaction that is used for the low-carbon (LC) hydro carbons as membrane reactor, like hydrocarbon oxidation preparing synthetic gas or hydrogen, methane oxidation coupling system ethane/ethylene, making ethylene from ethane oxidative dehydrogenation etc.For example, traditional methane reforming carries out through fixed bed reactors, and this reformation mode causes temperature runaway problem and reforming process use purity oxygen easily, must have special oxygen supply factory that oxygen is provided.Yet ripe at present air separation technology is cryogenic rectification and transformation absorption, and it consumes energy high, has increased the cost of partial oxidation of methane hydrogen greatly.And adopt with the oxygen permeable film material is that the membrane reactor of core component carries out partial oxidation of methane hydrogen; At high temperature the composite conductor oxygen-permeating film material can separate pure oxygen from air or other oxygen-containing gas; The separation and the methane partial reaction of oxygen can be carried out simultaneously; Can avoid the investment of the oxyen manutactory of costliness like this, simplify production process, reduce production costs.According to bibliographical information, this process is practiced thrift cost 25%～50% than present methane aqueous vapor preparing synthetic gas by reforming process.In addition, composite conductor oxygen-permeating film also can be used as high-temperature decomposition reaction (like H
2O and CO
2Decomposition reaction) oxygen separation membrane also can be used for the oxygen enrichment catalytic combustion to improve equilibrium conversion, improves flame holding, reduces NO
xAnd CO exhaust gas discharging amount.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 positive impetus.
Core component for this membrane reactor of composite conductor oxygen-permeating film; Through research to year; Developed the mixed conductor membrane material that multiple function admirable; Have 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 present research center of gravity progressively makes up transfer from material foundation research to applied membrane separation reactor.In the prior art; Chip and flat film also are not suitable for large-scale industrial application; On the one hand because this type of film configuration filling area is little, film thickness big, the oxygen flux of unit are is little, in membrane reactor, is difficult to large-area at its surperficial loading catalyst on the other hand; Sealing under the hot conditions and assembly connect also very difficult the solution simultaneously, are the fatal bottlenecks of its large-scale application of restriction.Therefore, the present more application of the film of this type of configuration fundamental research in the laboratory.The tubular membrane configuration then can improve the filling area, reduces thickness, improve permeation flux, and can adopt the cold junction sealing, reduces sealing difficulty greatly.Therefore, make up and a kind ofly have efficiently, stable, simple and easy, practical high-temperature tubular membrane separation reactor is to be the 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 and is applicable to that oxygen separates and the integral type high-temperature tubular membrane separation reactor of film reaction process for the deficiency of improving prior art.
Technical scheme of the present invention is: integral type high-temperature tubular membrane separation reactor, it is characterized in that this reactor by first gripper shoe (1A), mobile tube sheet (3), fixed tube sheet (4), and second gripper shoe (1B) is synthetic through guide rail (5) series successively; First gripper shoe (1A), second gripper shoe (1B) and fixed tube sheet (4) are fixing through fixture and guide rail (5); Move tube sheet (3) and the corresponding position of fixed tube sheet (4) and have the placement hole (12) of accepting the film pipe, film pipe (6) places placement hole (12); Move on the guide rail (5) between tube sheet (3) and first gripper shoe (1A) and be with spring (2); Move and be respectively equipped with air collecting chamber lid (7) on tube sheet (3) and the fixed tube sheet (4), the placement hole (12) that moves on tube sheet (3) and the fixed tube sheet (4) all places in the air collecting chamber lid (7), takes over (8) and links to each other with air collecting chamber lid (7); First gripper shoe (1A), 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), constitute the integral type film separate reactor.
Preferred described film pipe 6 is the ceramic pipe type film; Plasticity through routine is extruded, moulding by casting, the preparation of methods such as phase inversion method.Wherein membrane material is a 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 among La, Pr, Nd, Sm, Gd, Ba or the Sr; D, D ' are any one element of Cr, Mn, Fe, Co, Ni, Cu, Zn or Bi, and be synthetic through sol-gel process, solid reaction process, hydro-thermal method or coprecipitation.
Preferred described fixture is made up of fixed head 16, rubber o-ring 17 and screw 18: wherein rubber o-ring 17 places on the guide rail 5 between the first gripper shoe 1A, the second gripper shoe 1B and fixed tube sheet 4 and the fixed head 16, and screws through screw 18.
The central area radial that moves tube sheet 3 and fixed tube sheet 4 evenly has the placement hole 12 of accepting film pipe 6, and the placement hole periphery has the guide rail hole 13 of accepting guide rail 5; Tubular ceramic membrane places the placement hole 12 of fixed tube sheet 4 and mobile tube sheet 3, uses encapsulant 15 sealings.Hermetic unit is in outside the heating furnace heating region.
Move tube sheet for can prolong guide rail 5 moving-members.Move device spring 2 on the guide rail 5 between the tube sheet 3 and the first gripper shoe 1A, the stiffness factor k of preferred spring is 500～1500N/m.
Have only mid portion tubular membrane 6 and guide rail 5 to be in the heating furnace heating region in this reactor, 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, and opens pipe nipple and connect oilless vacuum pump.
According to the treating capacity in the actual use, the uniformity of Temperature Distribution and device physical dimension size, the number of film pipe generally is controlled at 10～25.
Perofskite type oxide in the material of the present invention can use 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 preparation of conventional methods such as phase inversion.
Beneficial effect:
The present invention is reasonable in design, has broken through traditional design concept, has improved the efficient and the practicality of reactor greatly.The film two ends all are fixed among the tube sheet, fix with respect to an end, and an end is the membrane reactor of fixing (unsettled) not, have improved the stability of reactor greatly.The tube sheet that links to each other with film Guan Yiduan simultaneously moves for prolonging guide rail, can dredge the axial expansion that film and membrane module cause in heating and cooling process effectively, has improved the mechanical stability of film.Moving significantly of spring restriction tube sheet offset the axially-movable at film and mobile tube sheet, further improves the stability of apparatus structure.Sealed end places outside the thermal treatment zone, and the cold junction sealing has solved conventional film reactor high temperature Sealing Technology difficult point, has reduced sealing difficulty effectively, and has improved airtight quality greatly.
Compact conformation of the present invention is reasonable, can be further to miniaturization, integrative development, and preparation small portable oxygen system.The present invention simultaneously is of many uses, is applicable to the tubular membrane of multiple configuration, like extra heavy pipe, tubule, hollow-fibre membrane etc.Broken through the restriction that traditional oxygen separation membrane reactor only can be applied to the preparation of pure oxygen separation especially; An end that the present invention is directed to conventional separators is shut; The structure of reactor of the single application that one end is bled; Brand-new design structure of reactor mentioned above, make this type of refractory ceramics membrane reactor can be applied to the film reaction process, have stronger creativeness and practicality.
Description of drawings:
Fig. 1 is the structural representation of invention integral type tubular type ceramic oxygen-permeable membrane separate reactor;
Fig. 2 moves tube sheet and Fixed Tubesheet Structure sketch map among Fig. 1;
Fig. 3 is for moving tube sheet, air collecting chamber lid, taking over the combination unit structure sketch map;
Fig. 4 is gripper shoe and a fixed head structural representation among Fig. 1;
Fig. 5 is gripper shoe unit and fixed tube sheet unit fixed form structural representation;
Wherein:
1A: first gripper shoe; 1B: second gripper shoe; 2: spring; 3: move tube sheet; 4: fixed tube sheet; 5: guide rail; 6: the film pipe; 7: the 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 among the embodiment 2;
Fig. 7 is the thermal expansion curve map of different guide material and film tube material among the embodiment 3, supposes that being in heating interval material raw footage is 20cm;
Fig. 8 is an oxygen flux change curve in time during 900 ℃ of 10 passage SCF tubule formula oxygen separators among the embodiment 5;
Fig. 9 is methane conversion and a selectivity temperature variation curve during 900 ℃ of 20 passage LSCF tubule formula membrane reactors among the embodiment 6;
Figure 10 is a methane conversion and selectivity change curve in time during 850 ℃ of 20 passage LSCF tubule formula membrane reactors among the embodiment 7.
The practical implementation method:
The material SrCo that relates 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 use 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 preparation of conventional methods 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 constitute integral type tubular type ceramic oxygen-permeable membrane separate reactor jointly.Membrane reactor module body part is formed through 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 places and moves between tube sheet 3 and the fixed tube sheet 4, concentrates through air collecting chamber lid 7 and takes over 8 and realize the air inlet and the operations of giving vent to anger.Whole membrane module places tube type resistance furnace 9, wherein removes the heating interval (by heat-preservation cotton 10, resistance wire 11 constitutes) that part film pipe and guide rod are in resistance furnace, and remainder all is in outside the thermal treatment zone.
Fig. 2 opens film pipe placement hole 12, guide rail hole 13, screwed hole 14 respectively, arranged distribution as shown in the figure for moving tube sheet and Fixed Tubesheet Structure sketch map on the dish; Tubular type ceramic oxygen-permeable membrane 6 inserts respectively and moves on tube sheet 3 and the fixed tube sheet 4 in the corresponding placement hole 12.As shown in Figure 3,12 of film pipe 6 and placement holes use high-temperature sealing material 15 to seal; Tube sheet 3,4 is threaded with air collecting chamber lid 7, adapter 8, realizes charging and discharging operation in the tubular membrane pipe.The unit of combining structure shown in Fig. 3 is not fixed with guide rail, cooperates with next-door neighbour's spring to be used to dredge the axial displacement that heating interval inner membrance pipe causes because of heating and cooling.
Except that mobile tube sheet 3, fixed tube sheet 4, two end supports plate 1A and 1B all are connected with guide rail 5 through 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, the fixed head through be positioned at rubber o-ring 17 and screw 18 on the guide rail carry out fastening, to reach the fixed support effect.
Constitute integral ceramics oxygen permeation membrane separate reactor according to above-mentioned installation connected mode combined films assembly and tubular heater: during making oxygen by air separation; Take over end sealing; One termination oilless vacuum pump; Logical compressed air in the stove, furnace temperature is heated to 500 ℃～1000 ℃, and the gas of extracting out through vavuum pump is pure oxygen.During film reaction, take over the logical feeding gas (like methane) of an end, logical compressed air in the termination gas collector, stove, furnace temperature is heated to 500 ℃～1000 ℃, and feeding gas then 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 done further elaboration:
Embodiment 2:
Reactor places tubular heater, and two ends fixed tube sheet and mobile tube sheet and hermetic unit all are in outside the heating furnace heating interval.Fluid sealant 704 silicon rubber sealants, this kind sealant heatproof is the highest 250 ℃, 200 ℃ of long-term maximum operation (service) temperatures, resistance to elevated temperatures is excellent.Confirm the distance of tube sheet (hermetic unit) as index, guarantee airtight quality and film pipe utilization rate apart from the heating furnace heating interval.Non-heating interval axial temperature distribution curve when Fig. 6 is tube furnace difference central temperature.Can be found out that by Fig. 6 along with the raising of temperature between tube furnace heating center, the fire door temperature also rises accordingly to some extent, the outer axially temperature of stove is along with reducing rapidly apart from the increase of fire door distance simultaneously.When apart from the about 5cm of fire door apart from the time, can guarantee that when different furnace temperature the temperature of tube sheet (hermetic unit) is less than 200 ℃, satisfy the requirement of sealing and peak use rate.Other is like inorganic sealant; Metal sealant heatproof temperature is far above organic encapsulant; Take all factors into consideration 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 apparatus, device is in (＞500 ℃) in the hot environment among the present invention, also has partial devices to be in the normal temperature environment simultaneously.Parts in the hot environment; In heating and cooling process, must bring bigger expansion or shrinkage phenomenon; And between the parts and and normal temperature environment in have bigger hot expansibility difference between parts, if can not solve the stress difference that material expands and brings effectively, will jeopardize membrane module structure stability greatly; Even causing the film tracheal rupture, imflammable gas is revealed and then the danger of blast.In the present embodiment, the hot expansibility of each parts in the hot environment is tested, Fig. 7 is the thermal expansion curve map of different guide material and film tube material, supposes that being in heating interval material raw footage is 20cm.Can find that by figure 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 are obviously greater than the thermal coefficient of expansion as quartz in the guide rail alternative materials and corundum; Because whole device and tube furnace are assembled into one; Two ends fixed tube sheet and tube furnace housing contacts can not be slided, therefore significantly relatively; Quartz material with minimum coefficient of thermal expansion is best guide material, is corundum material secondly.
The thermal coefficient of expansion of form 1 different guide rails and film tubing matter and relative length change
Embodiment 4:
Film pipe and guide rail all are in the hot environment, are heated to 900 ℃ from room temperature to be, the film pipe, can be found out shown in form 1 with respect to the length variations of guide rail, in the temperature-rise period, has bigger length variations, and and guide rail and normal temperature parts between exist than big difference.So between mobile tube sheet side and gripper shoe, add shock mount, and offset the film length of tube on the one hand and change the stress that brings, on the other hand whole device is provided support restriction, the mobile significantly unstability of bringing of tube sheet is moved in restriction.The selection basis of spring, the film length of tube changes, and the compression strength of film pipe through Hooke's law F=kx, calculates the stiffness factor of spring.Shown in form 2, be example with 20 channel membrane reactors, calculate the maximum stiffness factor of the employed spring of different film tube materials.Through this account form, can draw, different film pipes, different film pipes 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 end sealing, logical compressed air in the termination oilless vacuum pump, stove, furnace temperature is heated to 900 ℃.Structure of reactor is identical with structure described in the embodiment 1, uses 10 SCF tubular membrane, film pipe length overall 40cm, and tube sheet (hermetic unit) is 10cm apart from the distance of fire door, concrete film pipe and device parameter are shown in form 2.Oxygen flux change curve in time when Fig. 8 is 900 ℃ of 10 passage SCF tubule formula oxygen separators, reactor air side partial pressure of oxygen is 0.021MPa, and vacuum is 0.1MPa in the pipe, and the Stable Oxygen flux is 0.10L/min.The area of oxygen permeation membrane
L, D
oAnd D
iRepresent the effective length and the inner and outer diameter of film pipe respectively.Every square metre of membrane area of reactor per hour oxygen transmission rate is that 331.5L (is 331.5L/h/m
2).
Embodiment 6:
Structure of reactor is identical with structure described in the embodiment 1, uses 20 LSCF tubular membrane, film pipe length overall 40cm, and tube sheet (hermetic unit) is 10cm apart from the distance of fire door, concrete film pipe and device parameter are shown in form 2.Each probe temperature point stopped 1 hour, and each data repeats to guarantee more than 3 times result's accuracy.Fig. 9 has provided LSCF membrane reactor reactivity worth with the variation of temperature curve.Can know CH by figure
4Conversion ratio oxygen permeation flux and hydrogen productive rate increase with the rising of temperature.At 900 ℃, CH
4Conversion ratio is 93%; The rising with temperature before 800 ℃ of hydrogen selectivity increases, yet reduces to some extent later at 875 ℃, about 900 ℃, maintains 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 stability test result more than 240 hours under 850 ℃ of methane portion oxidation conditions.Structure of reactor is identical with structure described in the embodiment 1, uses 20 SCF tubular membrane, film pipe length overall 40cm, and tube sheet (hermetic unit) is 5cm apart from the distance of fire door, concrete film pipe and device parameter are shown in form 2.At test period, CH
4Conversion ratio, hydrogen selectivity, remain on 77%, 95% respectively, this explanation, membrane reactor of the present invention shows reactivity worth and very high long-time stability preferably.After reaction stops and reducing to room temperature; Tubular membrane still is kept perfectly; Find because the phenomenon of the film pipe fracture that material heat expansion and STRESS VARIATION cause in the heating and cooling process, explain 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 first gripper shoe (1A), moves tube sheet (3), fixed tube sheet (4), and second gripper shoe (1B) is synthetic through guide rail (5) series successively; First gripper shoe (1A), second gripper shoe (1B) and fixed tube sheet (4) are fixing through fixture and guide rail (5); Move tube sheet (3) and the corresponding position of fixed tube sheet (4) and have the placement hole (12) of accepting the film pipe, film pipe (6) places placement hole (12); Move on the guide rail (5) between tube sheet (3) and first gripper shoe (1A) and be with spring (2); Move and be respectively equipped with air collecting chamber lid (7) on tube sheet (3) and the fixed tube sheet (4), the placement hole (12) that moves on tube sheet (3) and the fixed tube sheet (4) all places in the air collecting chamber lid (7), takes over (8) and links to each other with air collecting chamber lid (7); First gripper shoe (1A), 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 the described integral type high-temperature tubular of claim 1 membrane separation reactor, it is characterized in that described film pipe (6) is the ceramic pipe type film; Wherein membrane material is a 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 among La, Pr, Nd, Sm, Gd, Ba or the Sr; D, D ' are any one element of Cr, Mn, Fe, Co, Ni, Cu, Zn or Bi.
3. according to the described integral type high-temperature tubular of claim 1 membrane separation reactor, it is characterized in that described guide rail (5) material is quartz or corundum material.
4. according to the described integral type high-temperature tubular of claim 1 membrane separation reactor; It is characterized in that described fixture is made up of fixed head (16), rubber o-ring (17) and screw (18): wherein rubber o-ring (17) places on the guide rail (5) between first gripper shoe (1A), second gripper shoe (1B) and fixed tube sheet (4) and the fixed head (16), and screws through screw (18).
5. according to the described integral type high-temperature tubular of claim 1 membrane separation reactor; It is characterized in that the central area radial that moves tube sheet (3) and fixed tube sheet (4) evenly has the placement hole (12) of accepting film pipe (6), the placement hole periphery has the guide rail hole (13) of accepting guide rail (5); Tubular ceramic membrane places the placement hole (12) of fixed tube sheet (4) and mobile tube sheet (3), uses encapsulant (15) sealing.
6. according to the described integral type high-temperature tubular of claim 1 membrane separation reactor, the stiffness factor k that it is characterized in that described spring is 500～1500N/m.
7. according to the described integral type high-temperature tubular of claim 1 membrane separation reactor, 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110791341A (en) * | 2019-11-14 | 2020-02-14 | 青岛九堡能源装备科技有限公司 | Small-size marsh gas purifies and purification device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101264860A (en) * | 2008-04-21 | 2008-09-17 | 上海大学 | Oxygen-permeating film reactor used for coke oven crude gas mixing reforming hydrogen preparation technique |
| 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 |
| CN101522291A (en) * | 2006-09-29 | 2009-09-02 | 辛维特有限公司 | Leak-proof membrane element and method of manufacturing such an element |
| WO2011158275A1 (en) * | 2010-06-16 | 2011-12-22 | ENEA - Agenzia nazionale per le nuove tecnologie, l'energia e lo sviluppo economico sostenibile | Membrane reactor for treating gases containing tritium |
-
2012
- 2012-03-20 CN CN201210074519.5A patent/CN102580478B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101522291A (en) * | 2006-09-29 | 2009-09-02 | 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 |
| CN101264860A (en) * | 2008-04-21 | 2008-09-17 | 上海大学 | Oxygen-permeating film reactor used for coke oven crude gas mixing reforming hydrogen preparation technique |
| WO2011158275A1 (en) * | 2010-06-16 | 2011-12-22 | ENEA - Agenzia nazionale per le nuove tecnologie, l'energia e lo sviluppo economico sostenibile | Membrane reactor for treating gases containing tritium |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791341A (en) * | 2019-11-14 | 2020-02-14 | 青岛九堡能源装备科技有限公司 | Small-size marsh gas purifies and purification device |
| CN110791341B (en) * | 2019-11-14 | 2020-11-17 | 江苏德瑞环保科技有限公司 | Small-size marsh gas purifies and purification device |
| 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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| CN102580478B (en) | 2014-02-26 |
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