CN102909094B - Activation method for dehydrogenation catalyst at low temperature - Google Patents
Activation method for dehydrogenation catalyst at low temperature Download PDFInfo
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Abstract
The present invention discloses an activation method for a dehydrogenation catalyst at a low temperature, and the method comprises: the dehydrogenation catalyst, which is a platinum group metal-supported, is reduced at a low constant temperature before use, wherein hydrogen is used as a reducing gas, a reduction temperature is from 240 DEG C to350 DEG C, and the time of the constant temperature reduction is 1.0-8.0h, to prevent impact to the catalyst stability resulted from the active metal aggregation in the catalyst and exceedingly high initial activity which are caused by deep reduction of dehydrogenation-active metals, and simultaneously prevent impact to synergy resulted from the deep reduction of auxiliary components; and after the reduction, the temperature is raised to 550- 650 DEG C, a step of sulfurization is omitted, and hydrogen-containing feed gas is directly introduced for the dehydrogenation reaction. Compared with the prior art, the dehydrogenation catalyst active by the method of the present invention has a higher activity stability.
Description
Technical field
The invention relates to a kind of activation method of low-carbon alkanes catalytic dehydrogenation alkene catalyst, specifically, is about C
2~ C
5the activation method of Oxidative Dehydrogenation alkene catalyst.
Background technology
Along with the universal use of civil natural gas, effective utilization of refinery's liquefied gas becomes the focus of petrochemical industry, utilizes low-carbon alkanes resource valuable in liquefied gas significant with how becoming more meticulous.Preparing propylene by dehydrogenating propane and preparing isobutene through dehydrogenation of iso-butane just liquefied gas produce one of important channel of industrial chemicals, and it will become an emphasis of new century petrochemical technology research and development.
Low-carbon alkanes catalytic dehydrogenating reaction limits by thermodynamical equilibrium, must carry out under the harsh conditions of high temperature, low pressure.Too high reaction temperature, makes low-carbon alkanes cracking reaction and deep dehydrogenation aggravation, selective decline; Accelerate catalyst surface carbon deposit simultaneously, make rapid catalyst deactivation.Due to the shortening of catalyst life under lower alkane conversion and harsh reaction condition, dehydrogenating low-carbon alkane method is made to receive certain restriction when commercial Application.Therefore, exploitation has the key that the catalyst for preparing propylene with propane dehydrogenation of high selectivity and high stability and supporting technique become this technology.At present, dehydrogenating low-carbon alkane patented technology comprises in the world: the Oleflex technique of Uop Inc., the Catofin technique of ABB Lu Musi company, the Star technique of Kang Fei (Uhde) company, the FBD-4 technique of Snamprogetti/Yarsintz company, the PDH technique etc. of Lin De/BASF AG.In the device built, former Soviet Union's great majority adopt FBD-4 technique, and Catofin and Oleflex technique has become the leading technique adopted in new device.Oleflex technique is mainly catalyst based based on Pt, and Catafin technique is mainly with Cr
2o
3/ Al
2o
3be main.
Load type platinum is catalyst based is an important class in alkane dehydrogenating catalyst, and the production method of such catalyst is also open in the art.USP4914075, USP4353815, USP4420649, USP4506032, USP4595673, EP562906, EP98622 etc. report for propane catalyst based with other dehydrogenating low-carbon alkane Pt, have high alkane conversion and olefine selective.USP3897368 and CN87108352 discloses a kind of method of producing core-shell catalyst, and Pt optionally concentrates and is deposited on the outer surface of catalyst carrier, and the inner Pt content of catalyst carrier is lower, can improve the utilization rate of active metal.Above-mentioned this kind of Pt catalyst must use hydrogen reducing before use, and the catalyst after reduction is used for dehydrogenation reaction, in order to increase the stability of catalyst, generally carries out Passivation Treatment.In this kind of catalyst, reduction adopts the reduction of hydrogen constant temperature, and low-temperature reduction does not generally reach the reduction degree of depth, and therefore constant temperature reduction temperature is generally 400 ~ 650 DEG C, carries out Passivation Treatment again after reduction.As CN101138734A, CN101015802A in 400 ~ 600 DEG C of hydrogen streams constant temperature reductase 12 ~ 10h, CN1844324A at 400 DEG C hydrogen stream constant temperature reduction 7h, CN101108362A preferably at 450 ~ 550 DEG C in hydrogen stream constant temperature reduction 4 ~ 6h.Constant temperature reduction in hydrogen gas stream, although the active component of catalyst can be made to become elemental metals state, guarantee that metal component reaches drastic reduction, catalyst initial activity is higher, and the activity decrease of catalyst is very fast, less stable.Only have by passivation, the stability of catalyst could be improved.
Summary of the invention
For the deficiencies in the prior art, the invention provides the method for a kind of catalyst for dehydrogenation of low-carbon paraffin activation, eliminate passivating process on the basis of existing technology, and further increase object product yield, improve the stability of catalyst simultaneously.
The Low-temperature activation method of dehydrogenation of the present invention comprises following content: dehydrogenation is platinum family loaded catalyst, dehydrogenation adopts low-temperature reduction before use, take hydrogen as reducing gas, reduction temperature is 240 ~ 350 DEG C, recovery time is 1.0 ~ 8.0h, the catalyst activity accumulation of metal phenomenon avoiding dehydrogenation activity metal depth to reduce causing and initial activity is too high affects catalyst stability, avoids adjuvant component by drastic reduction simultaneously, have impact on the synergy of auxiliary agent; After low-temperature reduction, when being warmed up to 550 ~ 650 DEG C, do not carry out sulfuration, the unstripped gas directly passing into hydrogen carries out dehydrogenation reaction.
In dehydrogenation catalyst activation method of the present invention, dehydrogenation catalyst activation method is: be reducing gas with hydrogen, and reduce at relatively low temperature, reduction temperature is preferably 280 ~ 350 DEG C, makes the reduction degree of Pt in catalyst reach 20% ~ 30%.In reducing gas, hydrogen volume content is at least more than 90%, is preferably more than 95%.
A kind of detailed process of activation is as follows: first in a nitrogen atmosphere, with 0.5 ~ 30 DEG C/min heating rate, preferably temperature is raised to 240 ~ 350 DEG C from room temperature by the heating rate of 5 ~ 15 DEG C/min, then changes gas composition into hydrogen, 240 ~ 350 DEG C of constant temperature 0.5 ~ 8h, preferably 2 ~ 5h; Again gas is changed into nitrogen temperature to 550 ~ 650 DEG C, pass into the reaction mass of hydrogen, reduce further again while carrying out reacting.
In dehydrogenation catalyst activation method of the present invention, dehydrogenation is platinum family loaded catalyst, catalyst generally with aluminium oxide or faintly acid molecular sieve for carrier, with one or more in the platinum in platinum family, palladium, iridium, rhodium or osmium for active component, wherein active component comprises platinum, and be vehicle weight in element active component 0.01% ~ 2%.Suitable auxiliaries can be contained in dehydrogenation simultaneously, as one or more in Sn, La, K, rare earth metal etc., the content preferably counting 0.1% ~ 10%, K of vehicle weight with element containing the content of auxiliary agent La, Sn or La counts 0.1% ~ 10% of vehicle weight with element.Dehydrogenation can adopt the method for this area routine to prepare, and as adopted infusion process load dehydrogenation active component, auxiliary agent and/or can adopt infusion process to introduce in carrier preparation process.
In the inventive method, in the unstripped gas of hydrogen, unstripped gas is lower carbon number hydrocarbons, hydrogen: the molar ratio of low-carbon alkanes is between 1:1 ~ 6:1, and described lower carbon number hydrocarbons is C
3~ C
5alkane, as propane, normal butane, iso-butane, pentane, isopentane etc.
In dehydrogenation catalyst activation method of the present invention, by the method for traditional high temperature constant temperature reduction (400 ~ 650 DEG C) then sulfuration passivation, change the method that then low-temperature reduction not sulfuration directly reacts into, in catalyst, the reduction degree of active component Pt is lower, but directly react in hydrogen reaction mass, reaching active component Pt reacts while reduce, and active slow releasing is to increase the effect of catalyst stability.
Existing dehydrogenation is when activating, to take under traditional higher temperature constant temperature method of reducing in hydrogen stream, although this activation method has dehydrogenation activity metallic reducing fully and the high advantage of initial reaction activity, stability is relatively poor more, along with the carrying out of reaction, activity decrease is very fast.In order to increase its stability, passivation must be carried out.In the activation method of dehydrogenation of the present invention, platinum based catalyst adopts conventional method preparation, does not carry out conventional restoring operation, adopts hydrogen low-temperature reduction to control the reduction degree of Pt in catalyst.Its object is to suppress the initial stage cracking performance of catalyst to be beneficial to long-term stability.After catalyst has certain reduction degree, the unstripped gas passing into hydrogen that heats up reacts, and Pt in catalyst is reduced further.Reaching active component Pt reacts while reduce, and active slow releasing is to increase the object of catalyst stability.After activation process, improve the serviceability of catalyst, in particular improve the stability of the selective of object product and long-time reaction, the catalyst serviceability after activation is stablized, and activation process is easy to control, and eliminates passivating process.
Detailed description of the invention
Under dehydrogenation catalyst activation method of the present invention instead of traditional higher temperature by the reduction degree of hydrogen low-temperature reduction control Pt, constant temperature reduces.Dehydrogenation of the present invention does not need passivation just can improve the stability of long-lasting catalytic running.Dehydrogenation is preferably active component with Pt, and take La as auxiliary agent, auxiliary agent can also comprise K, Na and thulium etc. simultaneously.
Dehydrogenation can adopt conventional preparation method, and as adopted infusion process load dehydrogenation activity metal, auxiliary agent and can adopt dipping method to introduce in carrying alumina production procedure.
Catalyst of the present invention with containing La aluminium oxide or faintly acid molecular sieve for carrier, dehydrogenation activity metal component is generally selected from one or more in platinum, palladium, iridium, rhodium or the osmium in platinum family, and be preferably platinum, consumption counts 0.01% ~ 2% of vehicle weight with element.The content of La counts 0.1% ~ 10% of vehicle weight with element.
The present invention is with in the dehydrogenation that is carrier containing La aluminium oxide or faintly acid, and La introduces the material containing La when aluminium oxide plastic, then make carrier.
The present invention is with in the dehydrogenation that is carrier containing La aluminium oxide or faintly acid molecular sieve, and dehydrogenation activity metal component can be uniformly distributed in the catalyst, and preferred dehydrogenation activity metal component integrated distribution, in catalyst outer layer, forms core-shell catalyst.
The present invention, can simultaneously containing suitable auxiliary agent with in the dehydrogenation that is carrier containing La aluminium oxide or faintly acid molecular sieve, as alkali metal, alkaline-earth metal, rare earth metal etc.
Introduce detailed process and the condition of a kind of typical dehydrogenation method for preparing catalyst and activation method below:
(1) with alumina globule or faintly acid molecular sieve for carrier impregnation LaCl
3solution, wherein content can need to determine by use, preferably counts 0.1% ~ 5% of aluminium oxide or faintly acid molecular sieve with element;
(2) containing after carrier 800 DEG C of roastings of La, supersaturation infusion process is adopted to introduce dehydrogenation active component; Can, by conditions such as the pH value of control dipping solution and dip times, dehydrogenation active component be made mainly to concentrate in the certain thickness skin of carrier surface;
(3) catalyst intermediate in step (2) after heat treatment carries out steam dechlorination;
(4) add the alkali metal promoter needed for catalyst in the catalyst that step (3) obtains, auxiliary agent use amount can be determined by this area general knowledge as required.
(5) catalyst that step (4) obtains adopts the reduction degree hydrogen low-temperature reduction of control Pt, and reduction temperature scope is at 240 ~ 350 DEG C.
(6) dehydrogenation reaction is carried out under the atmosphere of hydrogen as diluent.
Alumina support containing La in step (1) introduces La when aluminium oxide plastic, and then preparation is containing the alumina support of La.Described prepares in cogelled mode containing La alumina support, the material containing La is introduced when aluminium oxide plastic, material containing La is generally soluble-salt, as nitrate, chloride etc., then shaping by the existing method in this area, as dripped a ball forming, extruded etc., aluminium oxide plastic is known by technical staff.The method of preparation method known by technical staff of above-mentioned carrier.
Dehydrogenation activity metal wherein described in step (2) is generally selected from one or more elements in platinum, palladium, iridium, rhodium or the osmium in platinum family, and content can need to determine by use, preferably counts 0.1% ~ 2% of vehicle weight with element.
Steam dechlorination described in step (3) is process 1 ~ 20 hour at 300 ~ 700 DEG C, and the atmosphere of dechlorination is the air containing 10v% ~ 30v% water vapour, and chlorinity is less than 0.15wt%.
The reduction degree hydrogen low-temperature reduction condition of the control Pt described in step (5) is temperature 240 ~ 350 DEG C, preferably 280 ~ 350 DEG C.For easy and simple to handle, low-temperature reduction is preferably cryogenic thermostat reduction.Other condition of reduction is: the volume space velocity of reducing gases is 500 ~ 5000h
-1, absolute pressure 0.1 ~ 0.5MPa.
Dehydrogenation reaction conditions described in step (6) is: reaction temperature 500 ~ 650 DEG C, volume space velocity (comprising unstripped gas and hydrogen) 500 ~ 5000h
-1, absolute pressure 0.1 ~ 0.5MPa, hydrogen: the molar ratio of low-carbon alkanes is between 1:1 ~ 6:1.Described lower carbon number hydrocarbons is C
2~ C
5alkane, as propane, normal butane, iso-butane, pentane, isopentane etc.
Enforcement below by dehydrogenation of isobutane is described further technology of the present invention.Wherein the percentage composition of not clear and definite benchmark is weight percentage.In dehydrogenation, the implication of the reduction degree of Pt is that the ratio of the amount of total Pt in amount and the catalyst of the Pt be reduced in catalyst is multiplied by 100%, measures or analytical method is TPR, TPD hydroxide titration method, ICP method or inorganic analysis method.
Example 1
Preparation is containing the alumina support of La.After the aluminum trichloride solution of a certain amount of 0.98M and the mixing of 0.01M lanthanum trichloride solution, add a certain amount of 8% ammoniacal liquor, mix in neutralizing tank at 60 ~ 80 DEG C, control ph 7.0 ~ 9.0, filter, washing, after acidifying, balling-up of pressurizeing in oil ammonia column, through super-dry, aging, 650 ~ 750 DEG C of roastings 4 hours, obtain the alumina globule containing La 0.8wt%.
By the alumina globule carrier containing 0.8% La at 800 DEG C of roasting 3h, the carrier after roasting and the aqueous solution containing chloroplatinic acid are flooded 6h at 70 DEG C, dry 2h, roasting 4h at 500 DEG C at 120 DEG C.Then in containing the air of water vapour, 4h is activated.Then at 70 DEG C and containing KNO
3aqueous impregnation 2h, dry under same condition, roasting.In catalyst, the load capacity of each component is: Pt 0.3wt%, La 0.8wt%, K 0.7wt%.
activation condition:first 300 DEG C are warming up in a nitrogen atmosphere, then constant temperature reduction 3h under hydrogen.In activation process, the volume space velocity of reducing gases is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 28%.
appreciation condition: catalyst volume 2.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 580 DEG C, hydrogen: the molar ratio of iso-butane is at 2:1.
result shows: this catalyst is evaluating 48h continuously, and iso-butane conversion ratio is 40.58%, and selective isobutene is 95.47%, conversion ratio and selective coke content is only 0.45% with substantially constant during initial reaction, demonstrates good catalytic activity and stability.
Comparative example
The preparation of catalyst, with example 1, obtains catalyst, then sulfuration passivation unlike the reduction of constant temperature in 500 DEG C of hydrogen gas stream.In dehydrogenation, the reduction degree of Pt is 86%.
activation condition:500 DEG C of Cheng Hengwen reduction 1h, the volume space velocity of reducing gases is 3000h
-1.
conditions of vulcanization: the volume space velocity of the mixed gas of hydrogen sulfide and hydrogen is 900 h
-1, molar ratio is 1:9, temperature 500 DEG C, passivation time 1h.
appreciation condition: catalyst volume 2.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 580 DEG C, hydrogen: the ratio of iso-butane is at 2:1.
result shows: this catalyst is evaluating 48h continuously, and iso-butane conversion ratio is 34.2%, and selective isobutene is 95.1%, and conversion ratio declines 4.8 percentage points than initial activity, selective substantially constant, and coke content is 2.12%.
Example 2
Preparation is containing the alumina support of La.After the aluminum trichloride solution of a certain amount of 1.08M and the mixing of 0.01M lanthanum trichloride solution, add a certain amount of 10% ammoniacal liquor, mix in neutralizing tank at 60 ~ 80 DEG C, control ph 7.0 ~ 9.0, filter, washing, after acidifying, balling-up of pressurizeing in oil ammonia column, through super-dry, aging, 650 ~ 750 DEG C of roastings 4 hours, obtain the alumina globule containing La 1.0wt%.
By the alumina globule carrier containing 1.0% La at 800 DEG C of roasting 3h, the carrier after roasting and the aqueous solution containing chloroplatinic acid are flooded 4h at 70 DEG C, dry 2h at 120 DEG C, roasting 4h at 500 DEG C, activates 4h in containing the air of water vapour.Then at 70 DEG C and containing KNO
3aqueous impregnation 2h, dry under same condition, roasting.In catalyst, the load capacity of each component is: Pt 0.7wt%, Sn 1.0wt%, K 1.0wt%.
activation condition:first 260 DEG C are warming up in a nitrogen atmosphere, then constant temperature reduction 5h under hydrogen.In activation process, the volume space velocity of reducing gases is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 26%.
appreciation condition: catalyst volume 3.0ml, volume space velocity 2000 h
-1, reaction pressure 0.1MPa, reaction temperature is 600 DEG C, hydrogen: the ratio of propane is at 2:1.
result shows: this catalyst is evaluating 24h continuously, and conversion of propane is 32.17%, and Propylene Selectivity is 96.56%, and conversion ratio declines 1.6 percentage points, selectively adds 1.2 percentage points, and coke content is only 3.26%, demonstrates good catalytic activity and stability.
Example 3
The method identical according to embodiment 1 prepares dehydrogenation.
activation condition:first 350 DEG C are warming up in a nitrogen atmosphere, then constant temperature reductase 12 h under hydrogen.In activation process, the volume space velocity of reducing gases is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 30%.
appreciation condition: catalyst volume 3.0ml, volume space velocity 2000 h
-1, reaction pressure 0.1MPa, reaction temperature is 590 DEG C, hydrogen: the ratio of iso-butane is at 2:1.
evaluation result: this catalyst is after continuously evaluating 30h, and iso-butane conversion ratio is 39.12%, and selective isobutene is 95.24%, conversion ratio and selective substantially constant, and coke content is only 0.76%, demonstrates good catalytic activity and stability.
Claims (10)
1. the Low-temperature activation method of a dehydrogenation, it is characterized in that comprising following content: dehydrogenation is platinum family loaded catalyst, dehydrogenation adopts low-temperature reduction before use, take hydrogen as reducing gas, reduction temperature is 240 ~ 350 DEG C, not containing 300 DEG C, the recovery time is 1.0 ~ 8.0h; After low-temperature reduction, when being warmed up to 550 ~ 650 DEG C, do not carry out sulfuration, the unstripped gas directly passing into hydrogen carries out dehydrogenation reaction.
2. in accordance with the method for claim 1, it is characterized in that: reduction temperature is 280 ~ 350 DEG C, not containing 300 DEG C.
3. in accordance with the method for claim 1, it is characterized in that: in dehydrogenation, the reduction degree of Pt is 20% ~ 30%.
4. in accordance with the method for claim 1, it is characterized in that: during dehydrogenation reduction, be warming up to 240 ~ 350 DEG C first in a nitrogen atmosphere.
5. according to the method described in claim 1 or 2, it is characterized in that: the recovery time is 2 ~ 5h.
6. according to the method described in claim 1 or 3, it is characterized in that: dehydrogenation is platinum family loaded catalyst, and active component comprises the platinum in platinum family, be vehicle weight in element active component 0.01% ~ 2%.
7. in accordance with the method for claim 6, it is characterized in that: simultaneously containing auxiliary agent in dehydrogenation, auxiliary agent is one or more in Sn, La, K, rare earth metal.
8. in accordance with the method for claim 7, it is characterized in that: the content that in dehydrogenation, the content of auxiliary agent Sn or La counts 0.1% ~ 10%, K of vehicle weight with element counts 0.1% ~ 10% of vehicle weight with element.
9. in accordance with the method for claim 1, it is characterized in that: in the unstripped gas of hydrogen, unstripped gas is lower carbon number hydrocarbons, hydrogen: the molar ratio of low-carbon alkanes is between 1:1 ~ 6:1.
10. in accordance with the method for claim 9, it is characterized in that: low-carbon alkanes is C
2~ C
5alkane.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033756A (en) * | 1987-07-31 | 1989-07-12 | 埃尼里瑟奇公司 | Dehydrogenation catalyst and preparation method thereof and in the application for preparing with linear paraffinic hydrocarbons in the linear alpha-olefin |
| JP2005211845A (en) * | 2004-01-30 | 2005-08-11 | Chiyoda Corp | Dehydrogenation catalyst for hydrogenated aromatic compounds and manufacturing method therefor |
| CN101612583A (en) * | 2009-07-28 | 2009-12-30 | 中国石油化工集团公司 | A kind of saturated alkane dehydrogenation catalyst of active component non-uniform Distribution |
| CN101623633A (en) * | 2009-08-17 | 2010-01-13 | 清华大学 | Catalyst for preparing olefin by dehydrogenating low-carbon alkane, and preparation method and application thereof |
-
2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033756A (en) * | 1987-07-31 | 1989-07-12 | 埃尼里瑟奇公司 | Dehydrogenation catalyst and preparation method thereof and in the application for preparing with linear paraffinic hydrocarbons in the linear alpha-olefin |
| JP2005211845A (en) * | 2004-01-30 | 2005-08-11 | Chiyoda Corp | Dehydrogenation catalyst for hydrogenated aromatic compounds and manufacturing method therefor |
| CN101612583A (en) * | 2009-07-28 | 2009-12-30 | 中国石油化工集团公司 | A kind of saturated alkane dehydrogenation catalyst of active component non-uniform Distribution |
| CN101623633A (en) * | 2009-08-17 | 2010-01-13 | 清华大学 | Catalyst for preparing olefin by dehydrogenating low-carbon alkane, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Yiwei Zhang,et al.Effect of La addition on catalytic performance of PtSnNa/ZSM-5 catalyst for propane dehydrogenation.《Applied Catalysis A: General》.2007,第333卷 * |
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