CN102649559A - Method for CO gas raw material dehydrogenation through catalytic oxidation reaction - Google Patents
Method for CO gas raw material dehydrogenation through catalytic oxidation reaction Download PDFInfo
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Abstract
The invention relates to a method for CO gas raw material dehydrogenation through catalytic oxidation reaction. The method mainly solves the technical problems of low hydrogenation rate and high CO loss rate in the CO gas raw material oxydehydrogenation process in the prior art. According to the method, mixed gas containing CO and hydrogen gas is adopted as raw materials, water is selected as terminating agents, the raw materials are in contact with catalysts in a reactor to take reaction under the conditions that the reaction temperature is 80-260 DEGC, the volume space velocity is 100-10000 hour<-1>, the oxygen gas/hydrogen gas mol ratio is (0.5-10):1, the reaction pressure is -0.08MPa to 5.0MPa, and the weight ratio of the raw materials to the terminating agents is (5-100):1, and effluent containing water is generated, wherein the adopted reactor is a fluidized bed reactor. Through the technical scheme, the problem is perfectly solved, and the method can be used in oxydehydrogenation industrial production of raw materials containing CO gas.
Description
Technical field
The present invention relates to the method for a kind of CO gas raw material by the catalytic oxidation dehydrogenation; Particularly about adopting CO gas raw material oxydehydrogenation fluidized-bed reactor coupling riser reactor; The fast device that divides is useful for the CO gas raw material by in the catalytic oxidative dehydrogenation reaction process.
Background technology
Barkite is important Organic Chemicals, is used for fine chemistry industry in a large number and produces various dyestuffs, medicine, important solvent, extraction agent and various midbody.Get into 21 century, barkite receives international extensively attention as degradable environment-friendly engineering plastics monomer.In addition, the barkite ordinary-pressure hydrolysis can get oxalic acid, and normal pressure ammonia is separated and can be got high-quality slow chemical fertilizer oxamyl.Barkite can also be used as solvent, produces medicine and dyestuff intermediate etc., for example carries out various condensation reactions with fatty ester, hexamethylene phenyl methyl ketone, amido alcohol and many heterogeneous ring compounds.It can also synthesize at the chest acyl alkali that pharmaceutically is used as hormone.In addition, the barkite low-voltage hydrogenation can prepare crucial industrial chemicals terepthaloyl moietie, and terepthaloyl moietie mainly relies on petroleum path to prepare at present, and cost is higher, and China needs a large amount of import terepthaloyl moietie every year, and import volume was nearly 4,800,000 tons in 2007.
The production route of tradition barkite utilizes oxalic acid to prepare with alcohol generation esterification, and the production technique cost is high, and energy consumption is big, and is seriously polluted, and prepared using is unreasonable.And adopt the carbon monoxide coupling technology to produce the focus that barkite has become domestic and international research.
As everyone knows; Carbon monoxide can be from the various gas mixtures that contain carbon monoxide separation and Extraction, the virgin gas that can be used for separating carbon monoxide in the industry comprises: the tail gas of synthetic gas, water-gas, semi-water gas and Iron And Steel Plant, calcium carbide factory and yellow phosphorus factory that Sweet natural gas and oil transform etc.It is pressure swing adsorption process that existing CO separates the main method of purifying; China has many companies to develop transformation fractionation by adsorption carbon monoxide new technology; Especially the high-efficiency adsorbent of developing; Carbon monoxide there are high loading capacity and selectivity, can solve a difficult problem of from the high virgin gas of nitrogen or methane content, isolating high-purity carbon monooxide, can design and build up large-scale carbon monoxide tripping device.However, by this technology isolated carbon monoxide from synthetic gas, under the prerequisite of taking into account the carbon monoxide yield, generally the content of its hydrogen can reach more than 1%.And research shows that the existence of hydrogen can cause the active reduction of follow-up CO coupling reaction catalyst, can't carry out until reaction, and therefore, the exploitation carbon monoxide selects the dehydrogenation technical meaning great.
At present, the dehydrogenation catalyst of report mainly contains Pd/Al both at home and abroad
2O
3, CoMo/Al
2O
3Deng, the dehydrogenating agent based on the manganese series metal oxide is also arranged, purify but these catalyzer or dehydrogenating agent generally are used for the dehydrogenation of non-reducing gas such as high purity nitrogen, high purity oxygen and carbonic acid gas, and reaction process is generally fixed-bed process.And exist down for the CO reducing gas, existing catalyzer and technology are low to the decreasing ratio of hydrogen, and the rate of loss of CO is high.As adopt the method and the catalyzer of the disclosed catalytic oxidative dehydrogenation of document CN97191805.8, and be raw material at the CO mixed gas that is used for hydrogen content 10%, 220 ℃ of temperature of reaction, volume space velocity 3000 hours
-1, oxygen/hydrogen mol ratio is 0.6: 1, and reaction pressure is under the condition of 0.5MPa, and the rate of loss of CO is up to 1.5%, and the content of hydrogen is up to 1000ppm in the reaction effluent.
The subject matter that the related technology of above-mentioned document exists is the difficult control of temperature, and catalyst selectivity is poor, and causes the CO rate of loss high.
Summary of the invention
Technical problem to be solved by this invention is to be used for the method for CO gas raw material by the catalytic oxidation dehydrogenation in the technical literature in the past; Exist the hydrogen decreasing ratio low; The technical problem that the CO rate of loss is high provides the method for a kind of new CO gas raw material by the catalytic oxidation dehydrogenation.This method is used for the CO gas raw material by the catalytic oxidative dehydrogenation process, has hydrogen decreasing ratio height, the advantage that the CO rate of loss is low.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of CO gas raw material is raw material by the method for catalytic oxidation dehydrogenation with the gas mixture that contains CO and hydrogen, is terminator to be selected from water; In temperature of reaction is 80～260 ℃, and volume space velocity is 100～10000 hours
-1Oxygen/hydrogen mol ratio is 0.5～10: 1; Reaction pressure is-0.08～5.0MPa; The weight ratio of raw material and terminator is under 5～100: 1 the condition, raw material through with reactor drum in the catalyzer contact reacts, generate the elute that contains water; Wherein used reactor drum is a fluidized-bed reactor; Basically be made up of settling vessel (5), stripper (11) and interchanger (3), comprise emulsion zone (A), zone of transition (B), negative area (C), material inlet (1), sparger or grid distributor (2), interchanger (3), riser tube (4), divide device (6), gas tube (7), cyclonic separator (8), collection chamber (9), product gas outlet (10), stripper (11), regenerator sloped tube (12) and inclined tube to be generated (13) soon, wherein emulsion zone (A) is connected with riser tube (4) through zone of transition (B) back of undergauge structure; Riser tube (4) upper end or end are provided with fast minute device (6); The fast spiral arm of device (6) that divides is positioned at outside the riser tube (4), in the coaxial gas tube that communicates of riser tube (4) (7); Gas tube (7) is positioned at settling vessel (5), and the freeboard of fluidized bed on top, negative area (C) is stretched in its upper end, and its lower end is positioned at the outer zone of transition of riser tube (4) (B) outer upper ends; Cyclonic separator (8) is positioned at settling vessel (5), and outside the gas tube (7), its top outlet communicates with collection chamber (9); Collection chamber (9) is positioned at settling vessel (5) top and is connected with product gas outlet (10); Stripper (11) one ends are connected with the bottom of settling vessel (5), and the other end of stripper (11) links to each other with inclined tube to be generated (13); Between the bottom of settling vessel (5) and emulsion zone (A) hypomere, interchanger (3) is set, an end of interchanger (3) is connected with the bottom of settling vessel (5), and the other end of interchanger (3) is connected with emulsion zone (A); Sparger or grid distributor (2) are positioned at emulsion zone (A) bottom, and the bottom of sparger or grid distributor (2) is provided with material inlet (1), it is characterized in that near riser tube (4) lower region, terminator inlet (15) being set.
Terminator inlet 15 is 0～4/5 of riser tube 4 length apart from the vertical range of riser tube 4 bottoms in the technique scheme; Terminator inlet 15 distributes along riser tube 4 lower regions ringwise; The internal diameter of riser tube 4 is 1/15～1/2 of emulsion zone A external diameters, and the height of riser tube 4 is 1/5～5/1 of emulsion zone A height; Regenerator sloped tube 12 is 1/10～1/2 of emulsion zone A vertical height with emulsion zone A communication port apart from emulsion zone A bottom vertical distance; The vertical height of zone of transition B is 1/20～1/2 of an emulsion zone A vertical height; The gas inlet distance set air chamber 9 top vertical ranges of cyclonic separator 8 are 1/10～1/1 of settling vessel diameter.
Reaction conditions is preferably in the technique scheme: temperature of reaction is 100～240 ℃, and volume space velocity is 500～6000 hours
-1, oxygen/hydrogen mol ratio is 0.5～6: 1, and reaction pressure is 0～2.0MPa, and the weight ratio of raw material and terminator is 10～80: 1, and the terminator feeding temperature is 10～80 ℃.Catalyzer is preferably selected from least a for active ingredient in platinum or the palladium, and carrier is preferably selected from the ball-aluminium oxide of 20～300 microns of particle diameter average out to.
As everyone knows, carbon monoxide and hydrogen are the stronger gas of reductibility, and under the condition of the two and oxygen coexistence, normal conditions are when hydrogen is removed in selective oxidation, and CO equally also can react and lose bigger.Be strong exothermal reaction for the reaction of CO and oxygen and the reaction of hydrogen and oxygen, reaction temperature rising can be far up to more than 100 ℃ under to a certain degree.Research is also found; In the selective oxidation dehydrogenation process, the decreasing ratio of hydrogen and the rate of loss of CO and temperature of reaction were closely related under carbon monoxide existed, and the decreasing ratio of the high more hydrogen of temperature is high more; But the rate of loss of CO is also high more; And temperature is low more, and the rate of loss of CO can be low more, but the decreasing ratio of hydrogen possibly cannot say for sure to demonstrate,prove.Therefore, in selective oxidation dehydrogenation process under the carbon monoxide existence, temperature controlling is extremely important.The present invention by the characteristic that fluidized-bed temperature is evenly distributed, can realize higher hydrogen decreasing ratio and lower CO rate of loss through adopting fluid catalyst.In addition; Consider and adopt the CO gas raw material by in the catalytic oxidation dehydrogenation reaction process; Under raw material and the catalyzer Long contact time situation, still can continue to transform, especially at the settling zone of CO gas raw material oxydehydrogenation fluidized-bed reactor; A large amount of unsegregated catalyzer can continue to react with CO under the condition of high temperature, cause the CO rate of loss high.The present invention also injects terminator through the zone, outlet position of leaving catalytic bed in catalyzer and reaction product; On the one hand; The terminator that temperature is lower contacts with pyroreaction mixture and catalyzer, can significantly reduce the temperature of reaction mixture and catalyzer, and this can further quicken the rapid temperature-fall period of pyroreaction mixture and catalyzer; After reaction mixture that temperature sharply reduces and catalyzer leave reaction zone; Side reaction is few, and it is little to continue the reaction odds, has reduced the rate of loss of raw material.
Description of drawings
The CO gas raw material that Fig. 1 adopts for the present invention is by the fluidized-bed reactor synoptic diagram of catalytic oxidation dehydrogenation.
A is that emulsion zone, B are that zone of transition, C are negative areas, the 1st among Fig. 1, material inlet, the 2nd, sparger or grid distributor, the 3rd, interchanger, the 4th, riser tube; The 5th, settling vessel, the 6th, divide device soon, the 7th, gas tube, the 8th, cyclonic separator; The 9th, collection chamber, the outlet of 10 product gas, the 11st, stripper, the 12nd, regenerator sloped tube; The 13rd, inclined tube to be generated, the 14th, stripped vapor inlet, the 15th, terminator inlet.
Raw material is introduced by material inlet 1 among Fig. 1, and through gas distributor or grid distributor 2 laggard emulsion zone A and the catalyzer contact reacts of going into fluidized-bed that distribute, catalyzer and reaction mixture are through zone of transition B entering riser tube 4; Behind vortex quick separation device 6 sharp separation of riser tube 4 upper ends (end); Most of catalyzer gets into the lower region of settling vessel C; The part catalyzer that reaction mixture is carried secretly gets into settling vessel 5 top dilute phase spaces and carries out secondary separation through cyclonic separator 8; Product gas after the separation gets into collection chamber 9 through the outlet of cyclonic separator 8, is drawn by product gas outlet 10.Return the lower region of settling vessel 5 through the dipleg of cyclonic separator 8 from the catalyzer after cyclonic separator 8 separation.The reclaimable catalyst of the C bottom, negative area in the settling vessel 5 gets into stripper 11; Behind stripped vapor stripping from stripped vapor inlet 14; Get into revivifier (revivifier omits among the figure) through inclined tube 12 to be generated, regenerator gets into CO gas raw material oxydehydrogenation fluidized-bed reactor emulsion zone A through regenerator sloped tube 12.In addition, the part catalyzer in the settling vessel 5 gets into CO gas raw material oxydehydrogenation fluidized-bed reactor emulsion zone A bottom and continues reaction with catalyst mix after interchanger 3 heat exchange, and whole process circulation is carried out.
The fluidized-bed reactor that the present invention adopts is used for the CO gas raw material by the catalytic oxidation certain embodiments; Use device shown in Figure 1, adopting precious metal palladium or platinum load aluminum oxide is catalyzer, and water is terminator; In temperature of reaction is 80～260 ℃, and volume space velocity is 100～10000 hours
-1, oxygen/hydrogen mol ratio is 0.5～10: 1, reaction pressure is-0.08～5.0MPa; The weight ratio of raw material and terminator is under 5～100: 1 the condition, raw material through with reactor drum in the catalyzer contact reacts, the hydrogen in the raw material is oxidized to water; In containing the gas raw material of CO, the volumn concentration of hydrogen is that the decreasing ratio of hydrogen can reach 100% greater than under 0～15% the condition; The rate of loss of CO can obtain better technical effect less than 0.2%.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
With the fluidized-bed reactor of Fig. 1, wherein, the terminator inlet is 1/5 of a riser tube length apart from the vertical range of riser tube bottom, and the internal diameter of riser tube is 1/10 of an emulsion zone external diameter, and the height of riser tube is 1/4 of an emulsion zone height.Fluidized-bed reactor regenerator sloped tube and emulsion zone communication port are 1/5 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance; The vertical height of fluidized-bed reactor zone of transition is 1/10 of an emulsion zone vertical height, and distance set air chamber top, the gas inlet vertical range of fluidized-bed reactor cyclonic separator is 1/5 of a settling vessel diameter.It with palladium content 0.5% palladium load aluminum oxide fluid catalyst; 80 microns of its particle diameter average out to, water is terminator, uses the CO mixed gas of hydrogen content 10% to be raw material; The weight ratio of raw material and terminator is 10: 1; The terminator feeding temperature is 40 ℃, 180 ℃ of temperature of reaction, and volume space velocity 2000 hours
-1, oxygen/hydrogen mol ratio is 0.55: 1, and reaction pressure is under the condition of 0.1MPa, and reaction result is: the rate of loss of CO is 0.32%, and the content of hydrogen is 0ppm in the reaction effluent.
[embodiment 2]
With the fluidized-bed reactor of Fig. 1, wherein, the terminator inlet is 1/8 of a riser tube length apart from the vertical range of riser tube bottom, and the internal diameter of riser tube is 1/12 of an emulsion zone external diameter, and the height of riser tube is 1/2 of an emulsion zone height.Fluidized-bed reactor regenerator sloped tube and emulsion zone communication port are 1/3 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance; The vertical height of fluidized-bed reactor zone of transition is 1/5 of an emulsion zone vertical height, and distance set air chamber top, the gas inlet vertical range of fluidized-bed reactor cyclonic separator is 1/3 of a settling vessel diameter.It with platinum content 0.2% palladium load aluminum oxide fluid catalyst; 120 microns of its particle diameter average out to, water is terminator, uses the CO mixed gas of hydrogen content 10% to be raw material; The weight ratio of raw material and terminator is 5: 1; The terminator feeding temperature is 40 ℃, 220 ℃ of temperature of reaction, and volume space velocity 4000 hours
-1, oxygen/hydrogen mol ratio is 0.6: 1, and reaction pressure is under the condition of 0.5MPa, and reaction result is: the rate of loss of CO is 0.21%, and the content of hydrogen is 1ppm in the reaction effluent.
[embodiment 3]
With the fluidized-bed reactor of Fig. 1, wherein, the terminator inlet is 1/15 of a riser tube length apart from the vertical range of riser tube bottom, and the internal diameter of riser tube is 1/6 of an emulsion zone external diameter, and the height of riser tube is 1/3 of an emulsion zone height.Fluidized-bed reactor regenerator sloped tube and emulsion zone communication port are 1/8 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance; The vertical height of fluidized-bed reactor zone of transition is 1/6 of an emulsion zone vertical height, and distance set air chamber top, the gas inlet vertical range of fluidized-bed reactor cyclonic separator is 1/4 of a settling vessel diameter.It with platinum content 0.3% palladium load aluminum oxide fluid catalyst; 180 microns of its particle diameter average out to, water is terminator, uses the CO mixed gas of hydrogen content 5% to be raw material; The weight ratio of raw material and terminator is 30: 1; The terminator feeding temperature is 60 ℃, 240 ℃ of temperature of reaction, and volume space velocity 6000 hours
-1, oxygen/hydrogen mol ratio is 0.8: 1, reaction pressure is-condition of 0.05MPa under, reaction result is: the rate of loss of CO is 0.43%, the content of hydrogen is 5ppm in the reaction effluent.
[embodiment 4]
With the fluidized-bed reactor of Fig. 1, wherein, the terminator inlet is 1/15 of a riser tube length apart from the vertical range of riser tube bottom, and the internal diameter of riser tube is 1/18 of an emulsion zone external diameter, and the height of riser tube is 1/6 of an emulsion zone height.Fluidized-bed reactor regenerator sloped tube and emulsion zone communication port are 1/5 of emulsion zone vertical heights apart from emulsion zone bottom vertical distance; The vertical height of fluidized-bed reactor zone of transition is 1/10 of an emulsion zone vertical height, and distance set air chamber top, the gas inlet vertical range of fluidized-bed reactor cyclonic separator is 1/8 of a settling vessel diameter.It with platinum content 0.5% palladium load aluminum oxide fluid catalyst; 60 microns of its particle diameter average out to, water is terminator, uses the CO mixed gas of hydrogen content 1% to be raw material; The weight ratio of raw material and terminator is 60: 1; The terminator feeding temperature is 80 ℃, 160 ℃ of temperature of reaction, and volume space velocity 800 hours
-1, oxygen/hydrogen mol ratio is 1: 1, and reaction pressure is under the condition of 0.8MPa, and reaction result is: the rate of loss of CO is 0.13%, and the content of hydrogen is 0ppm in the reaction effluent.
[comparative example 1]
With reference to each step and the reaction conditions of embodiment 1, just CO gas raw material oxidative dehydrogenation reactor adopts fixed-bed reactor, and does not add terminator, and reaction result is: the rate of loss of CO is 3.2%, and the content of hydrogen is 160ppm in the reaction effluent.
[comparative example 2]
With reference to each step and the reaction conditions of embodiment 2, just CO gas raw material oxidative dehydrogenation reactor adopts fixed-bed reactor, and does not add terminator, and reaction result is: the rate of loss of CO is 4.2%, and the content of hydrogen is 180ppm in the reaction effluent.
Claims (9)
1. a CO gas raw material is raw material by the method for catalytic oxidation dehydrogenation with the gas mixture that contains CO and hydrogen, is terminator to be selected from water, is 80～260 ℃ in temperature of reaction, and volume space velocity is 100～10000 hours
-1Oxygen/hydrogen mol ratio is 0.5～10: 1; Reaction pressure is-0.08～5.0MPa; The weight ratio of raw material and terminator is under 5～100: 1 the condition, raw material through with reactor drum in the catalyzer contact reacts, generate the elute that contains water; Wherein used reactor drum is a fluidized-bed reactor; Basically be made up of settling vessel (5), stripper (11) and interchanger (3), comprise emulsion zone (A), zone of transition (B), negative area (C), material inlet (1), sparger or grid distributor (2), interchanger (3), riser tube (4), divide device (6), gas tube (7), cyclonic separator (8), collection chamber (9), product gas outlet (10), stripper (11), regenerator sloped tube (12) and inclined tube to be generated (13) soon, wherein emulsion zone (A) is connected with riser tube (4) through zone of transition (B) back of undergauge structure; Riser tube (4) upper end or end are provided with fast minute device (6); The fast spiral arm of device (6) that divides is positioned at outside the riser tube (4), in the coaxial gas tube that communicates of riser tube (4) (7); Gas tube (7) is positioned at settling vessel (5), and the freeboard of fluidized bed on top, negative area (C) is stretched in its upper end, and its lower end is positioned at the outer zone of transition of riser tube (4) (B) outer upper ends; Cyclonic separator (8) is positioned at settling vessel (5), and outside the gas tube (7), its top outlet communicates with collection chamber (9); Collection chamber (9) is positioned at settling vessel (5) top and is connected with product gas outlet (10); Stripper (11) one ends are connected with the bottom of settling vessel (5), and the other end of stripper (11) links to each other with inclined tube to be generated (13); Between the bottom of settling vessel (5) and emulsion zone (A) hypomere, interchanger (3) is set, an end of interchanger (3) is connected with the bottom of settling vessel (5), and the other end of interchanger (3) is connected with emulsion zone (A); Sparger or grid distributor (2) are positioned at emulsion zone (A) bottom, and the bottom of sparger or grid distributor (2) is provided with material inlet (1), it is characterized in that near riser tube (4) lower region, terminator inlet (15) being set.
2. according to the method for the said CO gas raw material of claim 1, it is characterized in that reactor drum terminator inlet (15) is 0～4/5 of riser tube (a 4) length apart from the vertical range of riser tube (4) bottom by the catalytic oxidation dehydrogenation.
3. according to the method for the said CO gas raw material of claim 2, it is characterized in that reactor drum terminator inlet (15) distributes along riser tube (4) lower region ringwise by the catalytic oxidation dehydrogenation.
4. according to the method for the said CO gas raw material of claim 1 by the catalytic oxidation dehydrogenation, the internal diameter that it is characterized in that riser tube (4) is 1/15～1/2 of emulsion zone (A) external diameter, and the height of riser tube (4) is 1/5～5/1 of emulsion zone (A) height.
5. according to the method for the said CO gas raw material of claim 1, it is characterized in that regenerator sloped tube (12) and emulsion zone (A) communication port are 1/10～1/2 of emulsion zone (A) vertical heights apart from emulsion zone (A) bottom vertical distance by the catalytic oxidation dehydrogenation.
6. according to the method for the said CO gas raw material of claim 1 by the catalytic oxidation dehydrogenation, the vertical height that it is characterized in that zone of transition (B) is 1/20～1/2 of emulsion zone (A) vertical height.
7. according to the method for the said CO gas raw material of claim 1, it is characterized in that gas inlet distance set air chamber (9) the top vertical range of cyclonic separator (8) is 1/10～1/1 of a settling vessel diameter by the catalytic oxidation dehydrogenation.
8. according to the method for the said CO gas raw material of claim 1 by the catalytic oxidation dehydrogenation, it is characterized in that temperature of reaction is 100～240 ℃, volume space velocity is 500～6000 hours
-1, oxygen/hydrogen mol ratio is 0.5～6: 1, and reaction pressure is 0～2.0MPa, and the weight ratio of raw material and terminator is 10～80: 1, and the terminator feeding temperature is 10～80 ℃.
9. according to the method for the said CO gas raw material of claim 1 by the catalytic oxidation dehydrogenation, it is characterized in that catalyzer is selected from least a in platinum or the palladium and is active ingredient, carrier is selected from the ball-aluminium oxide of 20～300 microns of particle diameter average out to.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104667912A (en) * | 2014-07-10 | 2015-06-03 | 中国科学院福建物质结构研究所 | Catalyst for CO dehydrogenation fluidized bed reaction and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1243096A (en) * | 1998-07-29 | 2000-02-02 | 松下电器产业株式会社 | Hydrogen refining apparatus |
| JP2003144924A (en) * | 2001-11-09 | 2003-05-20 | Mitsubishi Chemicals Corp | Selective oxidation catalyst for hydrogen, selective oxidation method for hydrogen and dehydrogenation method for hydrocarbon |
| CN101164684A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Combined fluidized bed reactor |
| CN101543776A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Dehydrogenation catalyst for feed gas containing carbon monoxide, preparation method and application method thereof |
-
2011
- 2011-02-25 CN CN2011100455821A patent/CN102649559A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1243096A (en) * | 1998-07-29 | 2000-02-02 | 松下电器产业株式会社 | Hydrogen refining apparatus |
| JP2003144924A (en) * | 2001-11-09 | 2003-05-20 | Mitsubishi Chemicals Corp | Selective oxidation catalyst for hydrogen, selective oxidation method for hydrogen and dehydrogenation method for hydrocarbon |
| CN101164684A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Combined fluidized bed reactor |
| CN101543776A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Dehydrogenation catalyst for feed gas containing carbon monoxide, preparation method and application method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104667912A (en) * | 2014-07-10 | 2015-06-03 | 中国科学院福建物质结构研究所 | Catalyst for CO dehydrogenation fluidized bed reaction and preparation method and application thereof |
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Application publication date: 20120829 |