CN102909098A - Reductive activation method for dehydrogenation catalyst by using low concentration hydrogen - Google Patents
Reductive activation method for dehydrogenation catalyst by using low concentration hydrogen Download PDFInfo
- Publication number
- CN102909098A CN102909098A CN2011102173995A CN201110217399A CN102909098A CN 102909098 A CN102909098 A CN 102909098A CN 2011102173995 A CN2011102173995 A CN 2011102173995A CN 201110217399 A CN201110217399 A CN 201110217399A CN 102909098 A CN102909098 A CN 102909098A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- dehydrogenation
- reduction
- catalyst
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a reductive activation method for a dehydrogenation catalyst by using low concentration hydrogen. The method comprises: the dehydrogenation catalyst, which is a platinum group metal-supported catalyst, is reduced by using the low concentration hydrogen before use, wherein the low concentration hydrogen reduction is performed by using hydrogen with a content of is 1%-10% based on the volume of nitrogen as reducing gas, at a temperature of 300 - 600 DEG C for 1.0-8.0h; and then adjusting the temperature to be 500 to 650 DEG C, cancelling the process of sulfuration passivation and directly feeding a hydrogen-containing feed gas for the dehydrogenation reaction. Compared with the prior art, the dehydrogenation catalyst reduced and activated by the method of the invention has a higher activity stability.
Description
Technical field
The invention relates to the reduction activation method of a kind of low-carbon alkanes catalytic dehydrogenation alkene catalyst processed, specifically, is about C
2~ C
5The reduction 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 the liquefied gas significant with how becoming more meticulous.Preparing propylene by dehydrogenating propane and preparing isobutene through dehydrogenation of iso-butane just liquefied gas are produced one of important channel of industrial chemicals, and it will become an emphasis of new century petrochemical technology research and development.
The low-carbon alkanes catalytic dehydrogenating reaction is subjected to thermodynamics equilibrium limit, must carry out under the harsh conditions of high temperature, low pressure.Too high reaction temperature makes low-carbon alkanes cracking reaction and degree of depth dehydrogenation aggravation, selective decline; Accelerated simultaneously the catalyst surface carbon deposit, made rapid catalyst deactivation.Because the shortening of catalyst life makes the dehydrogenating low-carbon alkane method be subject to certain restriction when commercial Application under lower alkane conversion and the harsh reaction condition.Therefore, exploitation has the catalyst for preparing propylene with propane dehydrogenation of high selectivity and high stability and the key that supporting technique becomes this technology.At present, the 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 of Lin De/BASF AG etc.In the device of having built, former Soviet Union's great majority adopt FBD-4 technique, and Catofin and Oleflex technique have become the leading technique that adopts in the new device.Oleflex technique is mainly catalyst based as main take Pt, and Catafin technique is mainly with Cr
2O
3/ Al
2O
3Be main.
Load type platinum is catalyst based to be an important class in the alkane dehydrogenating catalyst, and the production method of such catalyst is also open in the art.USP4914075, USP4353815, USP4420649, USP4506032, USP4595673, EP562906, EP98622 etc. have reported for propane and other dehydrogenating low-carbon alkane Pt catalyst based, have high alkane conversion and olefine selective.USP3897368 and CN87108352 disclose a kind of method of producing hud typed 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 reactive metal.Above-mentioned this class Pt catalyst must be used hydrogen reducing before use, and the catalyst after the reduction is used for dehydrogenation reaction, in order to increase the stability of catalyst, generally carries out Passivation Treatment.In this class catalyst, reduction pure hydrogen (the density of hydrogen General Requirements reaches more than 90%, preferably reaches more than the 99%) constant temperature that adopt reduce more, and low-temperature reduction does not generally reach the reduction degree of depth, therefore the constant temperature reduction temperature is generally 400 ~ 650 ℃, carries out vulcanizing treatment after the reduction again.Such as CN101138734A, CN101015802A constant temperature reductase 12 ~ 10h in 400 ~ 600 ℃ of hydrogen streams, CN1844324A is at 400 ℃ of lower hydrogen stream constant temperature reduction 7h, and CN101108362A is constant temperature reduction 4 ~ 6h in 450 ~ 550 ℃ of lower hydrogen streams preferably.The constant temperature reduction although can make the active component of catalyst become the elemental metals attitude, guarantees that metal component reaches drastic reduction in the High Purity Hydrogen air-flow, and the catalyst initial activity is higher, and the activity of catalyst descends very fast, less stable.Only have by the sulfuration passivation, could improve the stability of catalyst.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of catalyst for dehydrogenation of low-carbon paraffin reduction activation, save on the basis of existing technology the sulfuration passivating process, and further improved the purpose product yield, improve simultaneously the stability of catalyst.
The present invention adopts the method for low-concentration hydrogen reduction activation dehydrogenation to comprise following content: dehydrogenation is the platinum family loaded catalyst, dehydrogenation adopts the low-concentration hydrogen reduction before use, the catalyst activity accumulation of metal phenomenon of avoiding the reduction of dehydrogenation activity metal depth to cause, avoid simultaneously adjuvant component by drastic reduction, affected synergism of additives, low-concentration hydrogen is reduced in nitrogen and contains 1% ~ 10%(volume) hydrogen as reducing gas, reduction 1.0 ~ 8.0h during 300 ~ 600 ℃ of temperature; Then adjust temperature to 500 ~ 650 ℃, cancellation sulfuration passivation, the unstripped gas that directly passes into hydrogen carries out dehydrogenation reaction.
In the inventive method, the low-concentration hydrogen reduction can be controlled the reduction degree of Pt in the catalyst, changed into the reduction of density of hydrogen in the control reducing gases by traditional High Purity Hydrogen air-flow constant temperature reduction, make that the reduction degree of Pt reaches 20% ~ 40% in the catalyst, in further dehydrogenation reaction process, active component Pt reduces while reacting, the active purpose that slowly discharges with the raising catalyst stability.
A kind of detailed process of dehydrogenation activation of the present invention is as follows: at first under nitrogen atmosphere, with 0.5 ~ 30 ℃/min heating rate, the heating rate of preferred 5 ~ 15 ℃/min is raised to 300 ~ 600 ℃ with temperature and is preferably 450 ~ 550 ℃, then gas composition is changed into 1% ~ 5%(volume is arranged in nitrogen) hydrogen, preferably contain 2% ~ 4% hydrogen, 300 ~ 600 ℃ preferably 450 ~ 550 ℃ the reduction 0.5 ~ 1.5h; Again gas composition is changed into 5% ~ 10%(volume is arranged in nitrogen) hydrogen, 300 ~ 600 ℃ preferably 450 ~ 550 ℃ the reduction 0.5 ~ 5h, preferred 1 ~ 4h.
In the dehydrogenation activation method of the present invention, dehydrogenation is the platinum family loaded catalyst, catalyst is generally take aluminium oxide or faintly acid molecular sieve as carrier, in platinum, palladium, iridium, rhodium or the osmium in the platinum family one or more are as active component, active component comprises platinum, take the element active component as vehicle weight 0.01% ~ 2%.Simultaneously suitable auxiliary agent be can contain in the dehydrogenation, such as in Sn, La, K, the rare earth metal etc. one or more, auxiliary agent Sn or La and K preferably contained.The content of auxiliary agent Sn or La is counted 0.1% ~ 10% of vehicle weight with element, and the content of K is counted 0.1% ~ 10% of vehicle weight with element.Dehydrogenation can adopt the method preparation of this area routine, and as adopting infusion process load dehydrogenation active component, auxiliary agent can and/or adopt infusion process to introduce in the carrier preparation process.
Existing dehydrogenation is when activation, take under traditional higher temperature constant temperature method of reducing in the hydrogen stream, although this activation method has the dehydrogenation activity metallic reducing fully and the high advantage of initial reaction activity, stability is relatively relatively poor more, along with the carrying out of reaction, active decline comparatively fast.In order to increase its stability, must vulcanize passivation.In the activation method of dehydrogenation of the present invention, platinum based catalyst adopts the conventional method preparation, does not carry out conventional restoring operation, adopts the control density of hydrogen to reduce to control the reduction degree of Pt in the catalyst.Its purpose is that the initial stage cracking performance that suppresses catalyst is beneficial to long-term stability.After catalyst had certain reduction degree, the unstripped gas pass into hydrogen that heats up reacted, and made that Pt further obtains reduction in the catalyst.Reached active component Pt and reduced while reacting, the active purpose that slowly discharges with the increase catalyst stability.Through after the activation process, improved the serviceability of catalyst, particularly improved the stability of the selective and long-time reaction of purpose product, the catalyst serviceability after the activation is stable, and activation process is easy to control, and has saved passivating process.
The specific embodiment
Dehydrogenation activation method of the present invention has replaced constant temperature reduction under traditional higher temperature by the reduction degree of density of hydrogen control Pt in the control reducing gases.Dehydrogenation of the present invention does not need passivation just can improve the stability of catalyst long time running.Dehydrogenation is preferably take Pt as active component, and take Sn as auxiliary agent, auxiliary agent can also comprise K, Na and rare earth metal etc. simultaneously.
Dehydrogenation can adopt conventional preparation method, and as adopting infusion process load dehydrogenation activity metal, auxiliary agent can and/or adopt dipping method to introduce in the alumina support preparation process.
Catalyst of the present invention is to contain Sn aluminium oxide or faintly acid molecular sieve as carrier, the dehydrogenation activity metal component generally is selected from one or more in platinum, palladium, iridium, rhodium or the osmium in the platinum family, be preferably platinum, can contain simultaneously other platinum group, consumption is counted 0.01% ~ 2% of vehicle weight with element.The content of Sn is counted 0.1% ~ 10% of vehicle weight with element.
The present invention is to contain Sn aluminium oxide or faintly acid in the dehydrogenation of carrier, and Sn introduces the material that contains Sn when aluminium oxide becomes glue, then make carrier.
The present invention is to contain Sn aluminium oxide or faintly acid molecular sieve in the dehydrogenation of carrier, and the dehydrogenation activity metal component can be evenly distributed in the catalyst, and preferred dehydrogenation activity metal component is concentrated and is distributed in the catalyst outer layer, forms hud typed catalyst.
The present invention can contain suitable auxiliary agent, such as alkali metal, alkaline-earth metal, rare earth metal etc. simultaneously to contain Sn aluminium oxide or faintly acid molecular sieve in the dehydrogenation of carrier.
The below introduces detailed process and the condition of a kind of typical dehydrogenation method for preparing catalyst and activation method:
(1) take alumina globule or faintly acid molecular sieve as carrier impregnation SnCl
4Solution, wherein content can need to determine by using, and preferably counts 0.1% ~ 5% of aluminium oxide or faintly acid molecular sieve weight with element;
(2) contain 800 ℃ of roastings of carrier of Sn after, adopt the supersaturation infusion process to introduce dehydrogenation active component; Can by conditions such as the control pH value of dipping solution and dip times, dehydrogenation active component mainly be concentrated in the certain thickness skin of carrier surface;
(3) catalyst intermediate after the heat treatment is carried out the steam dechlorination in the step (2);
(4) add the required alkali metal promoter of catalyst in the catalyst that step (3) obtains, the auxiliary agent use amount can be determined by this area general knowledge as required;
(5) catalyst that obtains of step (4) adopts the concentration reduction of hydrogen in the control reducing gases, and the reduction temperature scope is at 300 ~ 600 ℃;
(6) dehydrogenation reaction is carried out under as the atmosphere of diluent at hydrogen.
The alumina support that contains Sn in the step (1) is introduced Sn when aluminium oxide becomes glue, then preparation contains the alumina support of Sn.The described Sn of containing alumina support prepares in cogelled mode, when becoming glue, introduces in aluminium oxide the material that contains Sn, the material that contains Sn is generally soluble-salt, such as nitrate, chloride etc., then by the existing method moulding in this area, as dripping ball forming, extrusion modling etc., aluminium oxide becomes glue to be known by the technical staff.The preparation method of above-mentioned carrier is the known method of technical staff.
Wherein the described dehydrogenation activity metal of step (2) generally is selected from one or more elements in platinum, palladium, iridium, rhodium or the osmium in the platinum family, and content can need to determine by using, preferably count 0.1% ~ 2% of vehicle weight with element.
The described steam dechlorination of step (3) is that the atmosphere of dechlorination is for containing the air of 10v% ~ 30v% water vapour 300 ~ 700 ℃ of lower processing 1 ~ 20 hour, and chlorinity is less than 0.15wt%.
The described reducing condition of step (5) is 300 ~ 600 ℃ of temperature, preferred 450 ~ 550 ℃.For easy and simple to handle, reduction is preferably the constant temperature reduction.Other condition of reduction is: the volume space velocity of reducing gases is 500 ~ 5000h
-1, absolute pressure 0.1 ~ 0.5MPa.
The described dehydrogenation reaction conditions of step (6) is: 500 ~ 650 ℃ of reaction temperatures, 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 low-carbon alkanes is C
2~ C
5Alkane, such 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 clear and definite benchmark is not weight percentage.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 that is reduced in the catalyst multiply by 100% in the dehydrogenation, measures or analytical method is TPR, TPD hydroxide titration method, ICP method or inorganic analysis method.
Example 1
Preparation contains the alumina support of Sn.Behind the aluminum trichloride solution and the mixing of 0.01M butter of tin solution with a certain amount of 0.98M, add a certain amount of 8% ammoniacal liquor, under 60 ~ 80 ℃, in neutralizing tank, mix, control pH value 7.0 ~ 9.0, after filtration, washing, the acidifying, the balling-up of pressurizeing in the oil ammonia column is through super-dry, aging, 650 ~ 750 ℃ of roastings 4 hours, namely get the alumina globule that contains Sn 0.8wt%.
To contain the alumina globule carrier of 0.8% Sn at 800 ℃ of roasting 3h, with the carrier after the roasting and the aqueous solution that contains chloroplatinic acid dipping 6h under 70 ℃, at 120 ℃ of oven dry 2h, 500 ℃ of lower roasting 4h.Then in containing the air of water vapour, activate 4h.Then descend and contain KNO at 70 ℃
3Aqueous solution dipping 2h, dry, roasting under the same condition.The load capacity of each component is in the catalyst: Pt 0.3wt%, Sn 0.8wt%, K 0.7wt%.
Activation condition:At first under nitrogen atmosphere, be warming up to 500 ℃, then the 2%(volume arranged in nitrogen) hydrogen, 500 ℃ of constant temperature 0.5h, again gas composition is changed into the 5%(volume is arranged in nitrogen) hydrogen, 500 ℃ of constant temperature 1h.The volume space velocity of reducing gases is 3000h in the activation process
-1The reduction degree of Pt is 36% in the dehydrogenation.
Appreciation condition: catalyst volume 2.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 580 ℃, hydrogen: the ratio of iso-butane is at 2:1.
The result shows: this catalyst is being estimated 48h continuously, and the iso-butane conversion ratio is 38.58%, and selective isobutene is 95.17%, and conversion ratio descends 0.7 percentage point, and selectively substantially constant, coke content is 0.75% only, demonstrates good catalytic activity and stability.
Comparative example
The preparation of catalyst is with example 1, and different is to obtain catalyst through constant temperature reduction in 500 ℃ of flow of pure hydrogen, then vulcanizes passivation.
Activation condition:500 ℃ of Cheng Hengwen reduction 1.5h, the volume space velocity of reducing gases is 3000h
-1The reduction degree of Pt is 88% in the dehydrogenation.
Conditions of vulcanization: the volume space velocity of the mixed gas of hydrogen sulfide and hydrogen is 900 h
-1, molar ratio is 1:9,500 ℃ of temperature, passivation time 1h.
Appreciation condition: catalyst volume 2.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 580 ℃, hydrogen: the ratio of iso-butane is at 2:1.
The result shows: this catalyst is being estimated 48h continuously, and the iso-butane conversion ratio is 36.2%, and selective isobutene is 95.1%, and conversion ratio descends 2.8 percentage points, and selectively substantially constant, coke content is 1.12%.
Example 2
Preparation contains the alumina support of Sn.Behind the aluminum trichloride solution and the mixing of 0.01M butter of tin solution with a certain amount of 1.08M, add a certain amount of 10% ammoniacal liquor, under 60 ~ 80 ℃, in neutralizing tank, mix, control pH value 7.0 ~ 9.0, after filtration, washing, the acidifying, the balling-up of pressurizeing in the oil ammonia column is through super-dry, aging, 650 ~ 750 ℃ of roastings 4 hours, namely get the alumina globule that contains Sn 1.0wt%.
To contain the alumina globule carrier of 1.0% Sn at 800 ℃ of roasting 3h, with the carrier after the roasting and the aqueous solution that contains chloroplatinic acid dipping 4h under 70 ℃, at 120 ℃ of oven dry 2h, 500 ℃ of lower roasting 4h activate 4h in containing the air of water vapour.Then descend and contain KNO at 70 ℃
3Aqueous solution dipping 2h, dry, roasting under the same condition.The load capacity of each component is in the catalyst: Pt 0.7wt%, Sn 1.0wt%, K 1.0wt%.
Activation condition:The 3%(volume is arranged in nitrogen) hydrogen, 450 ℃ of constant temperature 0.5h, again gas composition is changed into the 6%(volume is arranged in nitrogen) hydrogen, 450 ℃ of constant temperature 1h.The volume space velocity of reducing gases is 3000h
-1The reduction degree of Pt is 26% in the dehydrogenation.
Appreciation condition: catalyst volume 3.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 580 ℃, hydrogen: the molar ratio of iso-butane is at 3:1.
The result shows: this catalyst is being estimated 120h continuously, and the iso-butane conversion ratio is 32.77%, and selective isobutene is 96.56%, and conversion ratio descends 3.6 percentage points, has selectively increased by 1.8 percentage points, and coke content is 2.76% only, demonstrates good catalytic activity and stability.
Example 3
Prepare dehydrogenation according to embodiment 1 identical method.
Activation condition:The 4%(volume is arranged in nitrogen) hydrogen, 400 ℃ of constant temperature 1.5h, again gas composition is changed into the 7%(volume is arranged in nitrogen) hydrogen, 400 ℃ of constant temperature 2h.The volume space velocity of reducing gases is 3000h
-1The reduction degree of Pt is 31% in the dehydrogenation.
Appreciation condition: catalyst volume 3.0ml, volume space velocity 2000 h
-1, reaction pressure 0.1MPa, reaction temperature is 590 ℃, hydrogen: the ratio of iso-butane is at 2:1.
Evaluation result: this catalyst is after estimating 30h continuously, and the iso-butane conversion ratio is 40.12%, and selective isobutene is 96.24%, conversion ratio and selectively substantially constant, and coke content is 0.66% only, demonstrates good catalytic activity and stability.
Claims (10)
1. method that adopts low-concentration hydrogen reduction activation dehydrogenation, it is characterized in that comprising following content: dehydrogenation is the platinum family loaded catalyst, dehydrogenation adopts the low-concentration hydrogen reduction before use, low-concentration hydrogen is reduced to and contains by volume 1% ~ 10% hydrogen in the nitrogen as reducing gas, reduction 1.0 ~ 8.0h during 300 ~ 600 ℃ of temperature; Then adjust temperature to 500 ~ 650 ℃, cancellation sulfuration passivation, the unstripped gas that directly passes into hydrogen carries out dehydrogenation reaction.
2. in accordance with the method for claim 1, it is characterized in that: the reduction degree of Pt in the low-concentration hydrogen reduction control catalyst makes that the reduction degree of Pt reaches 20% ~ 40% in the catalyst.
3. in accordance with the method for claim 1, it is characterized in that: adopt the low-concentration hydrogen reduction process to be: at first under nitrogen atmosphere, be warmed up to 300 ~ 600 ℃, then gas composition changed into 1% ~ 5% hydrogen is arranged in nitrogen, at 300 ~ 600 ℃ of reduction 0.5 ~ 1.5h; Again gas composition is changed into 5% ~ 10% hydrogen is arranged in nitrogen, at 300 ~ 600 ℃ of reduction 0.5 ~ 5h.
4. according to claim 1 or 3 described methods, it is characterized in that: reduction temperature is 450 ~ 550 ℃.
5. in accordance with the method for claim 3, it is characterized in that: at first under nitrogen atmosphere, be warmed up to 300 ~ 600 ℃, then gas composition changed into 2% ~ 4% hydrogen is arranged in nitrogen, at 300 ~ 600 ℃ of reduction 0.5 ~ 1.5h; Again gas composition is changed into 5% ~ 10% hydrogen is arranged in nitrogen, at 300 ~ 600 ℃ of reduction 1 ~ 4h.
6. according to claim 1 or 2 described methods, it is characterized in that: dehydrogenation is the platinum family loaded catalyst, in platinum, palladium, iridium, rhodium or the osmium in the platinum family one or more are as active component, and active component comprises platinum, take the element active component as vehicle weight 0.01% ~ 2%.
7. according to claim 1 or 6 described methods, it is characterized in that: contain simultaneously auxiliary agent in the dehydrogenation, auxiliary agent is one or more in Sn, La, K, the rare earth metal.
8. it is characterized in that in accordance with the method for claim 7: dehydrogenation contains auxiliary agent Sn or La and K.
9. in accordance with the method for claim 8, it is characterized in that: the content of auxiliary agent Sn or La is counted 0.1% ~ 10% of vehicle weight with element in the dehydrogenation, and the content of K is counted 0.1% ~ 10% of vehicle weight with element.
10. in accordance with the method for claim 1, it is characterized in that: 500 ~ 650 ℃ of dehydrogenation reaction temperature, volume space velocity 500 ~ 5000h
-1, absolute pressure 0.1 ~ 0.5MPa, hydrogen in the unstripped gas: the molar ratio of low-carbon alkanes is between 1:1 ~ 6:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110217399.5A CN102909098B (en) | 2011-08-01 | 2011-08-01 | Reductive activation method for dehydrogenation catalyst by using low concentration hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110217399.5A CN102909098B (en) | 2011-08-01 | 2011-08-01 | Reductive activation method for dehydrogenation catalyst by using low concentration hydrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102909098A true CN102909098A (en) | 2013-02-06 |
| CN102909098B CN102909098B (en) | 2015-04-15 |
Family
ID=47607813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110217399.5A Active CN102909098B (en) | 2011-08-01 | 2011-08-01 | Reductive activation method for dehydrogenation catalyst by using low concentration hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102909098B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588009A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Catalyst used for preparing olefin by dehydrating low carbon alkane, and preparation method thereof |
| JP2019137661A (en) * | 2018-02-15 | 2019-08-22 | Ｊｘｔｇエネルギー株式会社 | Method for producing alkene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4160745A (en) * | 1977-12-01 | 1979-07-10 | Exxon Research & Engineering Co. | Method of preparing highly active nickel catalysts and catalysts prepared by said method |
| CN101596465A (en) * | 2009-06-30 | 2009-12-09 | 北京大学 | Based on metallic catalyst of metal-organic framework and its production and application |
| 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
- 2011-08-01 CN CN201110217399.5A patent/CN102909098B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4160745A (en) * | 1977-12-01 | 1979-07-10 | Exxon Research & Engineering Co. | Method of preparing highly active nickel catalysts and catalysts prepared by said method |
| CN101596465A (en) * | 2009-06-30 | 2009-12-09 | 北京大学 | Based on metallic catalyst of metal-organic framework and its production and application |
| 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 (4)
| Title |
|---|
| 《React.Kinet.Catal.Lett.》 19881231 Yong-Xi Li,et al. STATE OF Sn IN Pt-Sn-ALUMINA CATALYST:XPS STUDY 第37卷, 第2期 * |
| 《石油化工》 20061231 余长林等 助剂对Pt／gamma-A12O3催化剂丙烷脱氢性能的影响 第35卷, 第3期 * |
| YONG-XI LI,ET AL.: "STATE OF Sn IN Pt-Sn-ALUMINA CATALYST:XPS STUDY", 《REACT.KINET.CATAL.LETT.》, vol. 37, no. 2, 31 December 1988 (1988-12-31) * |
| 余长林等: "助剂对Pt／γ—A12O3催化剂丙烷脱氢性能的影响", 《石油化工》, vol. 35, no. 3, 31 December 2006 (2006-12-31) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588009A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Catalyst used for preparing olefin by dehydrating low carbon alkane, and preparation method thereof |
| JP2019137661A (en) * | 2018-02-15 | 2019-08-22 | Ｊｘｔｇエネルギー株式会社 | Method for producing alkene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102909098B (en) | 2015-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102380425B (en) | Dehydrogenation catalyst reduction method | |
| CN102910997B (en) | Method for preparing olefins by using dehydrogenation of light alkanes with sulfur-containing substances added in raw materials | |
| CN101898130B (en) | Method for preparing dehydrogenation catalyst | |
| CN109382122B (en) | Activation reduction method of low-carbon alkane dehydrogenation catalyst | |
| CN101898138B (en) | Method for preparing vulcanized dehydrogenation catalyst | |
| CN102441444A (en) | Preparation method of dehydrogenation catalyst | |
| CN102911000B (en) | Dehydrogenation method for light alkanes | |
| CN102909012B (en) | Activation method for dehydrogenation catalyst | |
| CN102909013B (en) | Preparation method for dehydrogenation catalyst with steam dechlorination and reduction performed simultaneously | |
| CN102380426B (en) | Activation method of dehydrogenation catalyst | |
| CN102909098B (en) | Reductive activation method for dehydrogenation catalyst by using low concentration hydrogen | |
| CN102909095B (en) | Hydrogen-concentration-controlling stepwise reductive activation method for dehydrogenation catalyst | |
| CN102909099B (en) | Method for the reductive activation of dehydrogenation catalyst by using gas mixture of hydrocarbon/hydrogen | |
| CN102909101B (en) | Method for activating dehydrogenation catalyst by employing low concentration hydrogen via low temperature reduction | |
| CN102909092B (en) | Activating method for dehydrogenation catalyst of low concentration hydrogen high temperature reduction combined with low temperature reduction | |
| CN102909103B (en) | Activating method for dehydrogenation catalyst of low concentration hydrogen reduction combined with temperature-programmed reduction | |
| CN102909097B (en) | Reductive activation method for dehydrogenation catalyst at low constant temperature and programmed temperature | |
| CN102909011A (en) | Activation and sulfurization method for dehydrogenation catalyst | |
| CN102909094B (en) | Activation method for dehydrogenation catalyst at low temperature | |
| CN102463152B (en) | Method for processing dehydrogenation catalyst before application | |
| CN103041807B (en) | Preparation method of dehydrogenation catalyst for firstly reducing and further vulcanizing during dechloridation process of water vapor | |
| CN102909010B (en) | Dehydrogenation catalyst activation method combining high-temperature reduction with temperature programmed reduction | |
| CN103041808B (en) | Preparation method of dehydrogenation catalyst for simultaneously performing water vapor dechloridation and activation of catalyst | |
| CN102909102B (en) | Short time reduction activation method of dehydrogenation catalyst | |
| CN102909096B (en) | Dehydrogenation catalyst activation method combining high-temperature reduction of short duration with low-temperature reduction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |