CN102909092A - Activating method for dehydrogenation catalyst of low concentration hydrogen high temperature reduction combined with low temperature reduction - Google Patents
Activating method for dehydrogenation catalyst of low concentration hydrogen high temperature reduction combined with low temperature reduction Download PDFInfo
- Publication number
- CN102909092A CN102909092A CN201110217583XA CN201110217583A CN102909092A CN 102909092 A CN102909092 A CN 102909092A CN 201110217583X A CN201110217583X A CN 201110217583XA CN 201110217583 A CN201110217583 A CN 201110217583A CN 102909092 A CN102909092 A CN 102909092A
- Authority
- CN
- China
- Prior art keywords
- temperature reduction
- reduction
- hydrogen
- dehydrogenation
- 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses an activating method for a dehydrogenation catalyst of low concentration hydrogen high temperature reduction combined with low temperature reduction. The dehydrogenation catalyst is a platinum group metal-supported catalyst. The dehydrogenation catalyst is treated by reduction activation before being used. The reduction activation treatment process comprises the steps of firstly performing the high temperature reduction and then the low temperature reduction, wherein the high temperature reduction employs a nitrogen-hydrogen mixed reducing gas with the volume content of hydrogen being 1%-8%, and reduces for 0.5-8.0 h at a temperature of 450-550 DEG C; and the low temperature reduction employs hydrogen as a reducing gas, and reduces for 1-8 h at a temperature of 240-400 DEG C; then adjusting the temperature to 500-650 DEG C; omitting sulfuration passivation; and directly passing through a raw material gas containing hydrogen to perform dehydrogenation reaction. Compared with a dehydrogenation catalyst reduced and activated by a conventional method, the dehydrogenation catalyst reduced and activated by the method has higher activity and stability.
Description
Technical field
The invention relates to the activation method of a kind of low-carbon alkanes catalytic dehydrogenation alkene catalyst processed, 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 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 adopts pure hydrogen constant temperature reduction, and low-temperature reduction does not generally reach the reduction degree of depth, so the constant temperature reduction temperature is generally 400 ~ 650 ℃, carries out Passivation 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 high temperature 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 activation, save on the basis of existing technology passivating process, and further improved the purpose product yield, improve simultaneously the stability of catalyst.
Low-concentration hydrogen high temperature reduction of the present invention is in conjunction with the dehydrogenation activation method of low-temperature reduction, comprise following content: dehydrogenation is the platinum family loaded catalyst, dehydrogenation carries out reduction activation before use to be processed, the reduction activation processing procedure is carried out first high temperature reduction, then carry out low-temperature reduction, the nitrogen of high temperature reduction employing hydrogen volume content 1% ~ 8% preferred 2% ~ 5%-hydrogen mixes reducing gases, at 450 ~ 550 ℃ of lower reduction 0.5 ~ 8.0h, preferred 0.5 ~ 1.5h; It is reducing gases that low-temperature reduction adopts hydrogen, at 240 ~ 400 ℃ of preferred 300 ~ 400 ℃ of lower reduction 1 ~ 8h, preferred 2 ~ 5h; 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, change two sections reduction activations under the suitable condition into by traditional High Purity Hydrogen air-flow constant temperature reduction, the reduction degree that makes Pt in the dehydrogenation is 30% ~ 50%.Catalyst activity accumulation of metal and the too high phenomenon that causes poor stability of initial activity of having avoided the reduction of dehydrogenation activity metal depth to cause also can avoid some adjuvant component of not wishing to reduce by drastic reduction, have affected synergism of additives.The certain reduction degree of control active component Pt makes catalyst further reduction in course of reaction, has reached active slow release to increase the purpose of catalyst stability.
In the inventive method, the purity of the reducing gases hydrogen that low-temperature reduction adopts is at least (volume) more than 90%, and is preferred more than 95%.High temperature reduction and low-temperature reduction process adopt the constant temperature restoring operation.
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 can contain suitable auxiliary agent in the dehydrogenation, such as in Sn, La, K, the rare earth metal etc. one or more, the content of 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, along with the carrying out of reaction, active decline comparatively fast.In order to increase its stability, must carry out passivation.In the activation method of dehydrogenation of the present invention, platinum based catalyst adopts the conventional method preparation, do not carry out conventional restoring operation, behind the employing control density of hydrogen high temperature constant temperature reduction certain hour, the pure hydrogen constant temperature reduction of low temperature certain hour is with the reduction degree of Pt in the control catalyst again.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 the sulfuration 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 in the control reducing gases and change temperature section reduction control Pt.Dehydrogenation of the present invention does not need to vulcanize the stability that passivation just can improve the 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 to be containing Sn aluminium oxide or faintly acid molecular sieve as carrier, and the dehydrogenation activity metal component generally is selected from one or more in platinum, palladium, iridium, rhodium or the osmium in the platinum family, is preferably platinum, and consumption is counted 0.01% ~ 2% of vehicle weight with element.The content of Sn is counted 0.1% ~ 10% of vehicle weight with simple substance.
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 simultaneously to contain Sn aluminium oxide or faintly acid molecular sieve in the dehydrogenation of carrier, as alkali metal, alkaline-earth metal, rare earth metal and sulphur etc. one or more.
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 simple substance;
(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 constant temperature reduction of hydrogen in the control reducing gases, and constant temperature reduction temperature scope reduces the temperature to 240 ~ 400 ℃ at 450 ~ 550 ℃, constant temperature reduction under the pure hydrogen.
(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 first paragraph constant temperature of step (5) reducing condition is 450 ~ 550 ℃ of temperature, 240 ~ 400 ℃ of second segment reduction temperatures; The first paragraph reducing condition is the control density of hydrogen, and second segment is reduced to hydrogen reducing.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 (hydrogen and unstripped gas sum, unstripped gas are low-carbon alkanes) 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 alkane carbon hydrocarbon is C
3~ C
5Alkane, such as propane, normal butane, iso-butane, pentane, isopentane etc.
Enforcement below by dehydrogenating propane 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 1h, nitrogen protection borehole cooling to 350 ℃, constant temperature reductase 12 h under the hydrogen.The volume space velocity of reducing gases is 3000h in the activation process
-1The reduction degree of Pt is 34% in the dehydrogenation.
Appreciation condition: catalyst volume 2.0ml, volume space velocity 2000 h
-1, reaction pressure 0.1MPa, reaction temperature is 600 ℃, hydrogen: the molar ratio of propane is at 1:1.
The result shows: this catalyst is being estimated 24h continuously, and conversion of propane is 33.58%, and Propylene Selectivity is 96.17%, conversion ratio and selectively substantially constant, and coke content is 1.75% 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 reductase 12 h, the volume space velocity of reducing gases is 3000h
-1The reduction degree of Pt is 90% 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 600 ℃, hydrogen: the ratio of propane is at 1:1.
The result shows: this catalyst is being estimated 24h continuously, and the conversion ratio of propane is 30.2%, and Propylene Selectivity is 96.1%, and conversion ratio descends 2.7 percentage points, and selectively substantially constant, coke content is 2.12%.
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.Nitrogen protection borehole cooling to 300 ℃, constant temperature reduction 3h under the hydrogen.The volume space velocity of reducing gases is 3000h
-1The reduction degree of Pt is 39% in the dehydrogenation.
Appreciation condition: catalyst volume 3.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 590 ℃, hydrogen: the ratio of propane is at 2:1.
The result shows: this catalyst is being estimated 48h continuously, and conversion of propane is 22.77%, and Propylene Selectivity is 96.56%, and conversion ratio descends 1.6 percentage points, has selectively increased by 0.8 percentage point, and coke content is 2.46% 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, 500 ℃ of constant temperature 1.5h, nitrogen protection borehole cooling to 400 ℃, constant temperature reductase 12 h under the hydrogen.The volume space velocity of reducing gases is 3000h
-1The reduction degree of Pt is 46% in the dehydrogenation.
Appreciation condition: catalyst volume 3.0ml, volume space velocity 2000 h
-1, reaction pressure 0.1MPa, reaction temperature is 610 ℃, hydrogen: the ratio of propane is at 1:1.
Evaluation result: this catalyst is after estimating 30h continuously, and conversion of propane is 33.20%, and Propylene Selectivity is 96.19%, and conversion ratio is substantially constant, selectively slightly raises, and coke content is 2.76% only, demonstrates good catalytic activity and stability.
Claims (10)
1. a low-concentration hydrogen high temperature reduction is in conjunction with the dehydrogenation activation method of low-temperature reduction, dehydrogenation is the platinum family loaded catalyst, dehydrogenation carries out reduction activation before use to be processed, it is characterized in that: the reduction activation processing procedure is carried out first high temperature reduction, then carry out low-temperature reduction, the nitrogen of high temperature reduction employing hydrogen volume content 1% ~ 8%-hydrogen mixes reducing gases, at 450 ~ 550 ℃ of lower reduction 0.5 ~ 8.0h; It is reducing gases that low-temperature reduction adopts hydrogen, at 240 ~ 400 ℃ of lower reduction 1 ~ 8h; Then adjust temperature to 500 ~ 650 ℃, cancellation sulfuration passivation, the unstripped gas that directly passes into hydrogen carries out dehydrogenation reaction.
2. it is characterized in that in accordance with the method for claim 1: the reduction degree of Pt is 30% ~ 50% in the rear dehydrogenation of reduction.
3. according to the not described method of claim, it is characterized in that: the reducing gases of high temperature reduction is that hydrogen volume content is nitrogen-hydrogen gas mixture of 2% ~ 5%.
4. according to claim 1 or 3 described methods, it is characterized in that: the high temperature reduction time is 0.5 ~ 1.5h.
5. it is characterized in that in accordance with the method for claim 1: the temperature of low-temperature reduction is 300 ~ 400 ℃.
6. according to claim 1 or 5 described methods, it is characterized in that: the low-temperature reduction time is 2 ~ 5h.
7. it is characterized in that in accordance with the method for claim 1: the purity of the reducing gases hydrogen that low-temperature reduction adopts is at least more than 90% in body.
8. it is characterized in that in accordance with the method for claim 1: high temperature reduction and low-temperature reduction process adopt the constant temperature restoring operation.
9. 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%.
10. in accordance with the method for claim 9, it is characterized in that: dehydrogenation contains one or more in auxiliary agent Sn, La, K, the rare earth metal, the content of 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110217583.XA CN102909092B (en) | 2011-08-01 | 2011-08-01 | Activating method for dehydrogenation catalyst of low concentration hydrogen high temperature reduction combined with low temperature reduction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110217583.XA CN102909092B (en) | 2011-08-01 | 2011-08-01 | Activating method for dehydrogenation catalyst of low concentration hydrogen high temperature reduction combined with low temperature reduction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102909092A true CN102909092A (en) | 2013-02-06 |
| CN102909092B CN102909092B (en) | 2015-04-01 |
Family
ID=47607807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110217583.XA Active CN102909092B (en) | 2011-08-01 | 2011-08-01 | Activating method for dehydrogenation catalyst of low concentration hydrogen high temperature reduction combined with low temperature reduction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102909092B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289218A (en) * | 2013-07-17 | 2015-01-21 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene from isobutane through dehydrogenation |
| CN107282078A (en) * | 2016-03-30 | 2017-10-24 | 南京克米斯璀化工科技有限公司 | Dehydrogenation of isobutane catalyst and preparation method thereof and dehydrogenating technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1130101A (en) * | 1994-11-29 | 1996-09-04 | 底古萨股份公司 | C6-15Catalyst for dehydrogenation of paraffin |
| JPH09313952A (en) * | 1996-05-22 | 1997-12-09 | Mitsubishi Chem Corp | Regenerating method for platinum-tin-based catalyst |
| 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 |
-
2011
- 2011-08-01 CN CN201110217583.XA patent/CN102909092B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1130101A (en) * | 1994-11-29 | 1996-09-04 | 底古萨股份公司 | C6-15Catalyst for dehydrogenation of paraffin |
| JPH09313952A (en) * | 1996-05-22 | 1997-12-09 | Mitsubishi Chem Corp | Regenerating method for platinum-tin-based catalyst |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| 《石油化工》 20061231 余长林等 助剂对Pt/gamma-Al2O3催化剂丙烷脱氢性能的影响 第35卷, 第3期 * |
| ODD A.BARIAS等: "Propane Dehydrogenation over Supported Pt and Pt-Sn Catalysts:Catalyst Preparation,Characterization,and Activity Measurements", 《JOURNAL OF CATALYSIS》, vol. 158, 31 December 1996 (1996-12-31) * |
| 余长林等: "助剂对Pt/γ-Al2O3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 |
|---|---|---|---|---|
| CN104289218A (en) * | 2013-07-17 | 2015-01-21 | 中国石油化工股份有限公司 | Catalyst for preparing isobutene from isobutane through dehydrogenation |
| CN107282078A (en) * | 2016-03-30 | 2017-10-24 | 南京克米斯璀化工科技有限公司 | Dehydrogenation of isobutane catalyst and preparation method thereof and dehydrogenating technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102909092B (en) | 2015-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102380425B (en) | Dehydrogenation catalyst reduction method | |
| CN109382122B (en) | Activation reduction method of low-carbon alkane dehydrogenation catalyst | |
| 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 | |
| CN102441444B (en) | A kind of preparation method of dehydrogenation | |
| CN102909013B (en) | Preparation method for dehydrogenation catalyst with steam dechlorination and reduction performed simultaneously | |
| CN102911000B (en) | Dehydrogenation method for light alkanes | |
| CN101898138B (en) | Method for preparing vulcanized dehydrogenation catalyst | |
| CN102909012B (en) | Activation method for dehydrogenation catalyst | |
| CN102380426B (en) | Activation method of dehydrogenation catalyst | |
| CN102909092B (en) | Activating method for dehydrogenation catalyst of low concentration hydrogen high temperature reduction combined with low temperature reduction | |
| CN102909098B (en) | Reductive activation method for dehydrogenation catalyst by using low concentration hydrogen | |
| CN102909103B (en) | Activating method for dehydrogenation catalyst of low concentration hydrogen reduction combined with temperature-programmed reduction | |
| CN102909101B (en) | Method for activating dehydrogenation catalyst by employing low concentration hydrogen via low temperature reduction | |
| 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 | |
| CN102909097B (en) | Reductive activation method for dehydrogenation catalyst at low constant temperature and programmed temperature | |
| CN102909094B (en) | Activation method for dehydrogenation catalyst at low temperature | |
| CN102909011A (en) | Activation and sulfurization method for dehydrogenation catalyst | |
| CN103041807B (en) | Preparation method of dehydrogenation catalyst for firstly reducing and further vulcanizing during dechloridation process of water vapor | |
| CN102463152B (en) | Method for processing dehydrogenation catalyst before application | |
| CN102909010B (en) | Dehydrogenation catalyst activation method combining high-temperature reduction with temperature programmed reduction | |
| CN102909096B (en) | Dehydrogenation catalyst activation method combining high-temperature reduction of short duration with low-temperature reduction | |
| CN102909102B (en) | Short time reduction activation method of dehydrogenation catalyst | |
| CN103041808B (en) | Preparation method of dehydrogenation catalyst for simultaneously performing water vapor dechloridation and activation of catalyst |
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 |