CN101898138B - Method for preparing vulcanized dehydrogenation catalyst - Google Patents
Method for preparing vulcanized dehydrogenation catalyst Download PDFInfo
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- CN101898138B CN101898138B CN200910011771XA CN200910011771A CN101898138B CN 101898138 B CN101898138 B CN 101898138B CN 200910011771X A CN200910011771X A CN 200910011771XA CN 200910011771 A CN200910011771 A CN 200910011771A CN 101898138 B CN101898138 B CN 101898138B
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- 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
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- 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
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Abstract
The invention discloses a method for preparing a vulcanized dehydrogenation catalyst. The method comprises the following steps of: preparing an La and Sn-containing aluminum oxide carrier; dipping dehydrogenation active ingredients; performing vapor dechlorination process; and injecting a sulfur-containing compound and drying the carrier to obtain the dehydrogenation catalyst. The dehydrogenation catalyst prepared by the method has the advantages of high activity stability, long service life, high regeneration and the like when used for propane dehydrogenation and is particularly applicable to a technological process for preparing the propane by the propane dehydrogenation.
Description
Technical field
The present invention relates to a kind of preparation method of dehydrating alkanes system alkene catalyst, particularly the method for preparing catalyst of catalyst for preparing propylene with propane dehydrogenation reactivity and stability.
Background technology
Entered since the new century, world's petrochemical material and petroleum chemicals demand will sustainable growths, demand as petrochemical industry basic material propylene will continue to increase, and conventional steam cracking and FCC technology are produced the demand that the ability of propylene can not satisfy quick growth, and it is global in short supply that its market has been occurred.And deficient day by day along with petroleum resources, the production of propylene has been that raw material changes to the diversified technology path of raw material sources from simple dependence oil, particularly is the technology path that raw material is produced alkene with the low-carbon alkanes.In recent years, the technology that dehydrogenating propane is produced propylene had obtained large development, and it is very fast that particularly the technology of dehydrogenating propane (PDH) system propylene had the area development of resources advantage in recent years in the Middle East etc., becomes the third-largest propylene production.
The propane 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 propane cracking reaction and degree of depth dehydrogenation aggravation, and selectivity descends; Accelerate the catalyst surface carbon deposit simultaneously, make rapid catalyst deactivation.Because the shortening of catalyst life is restricted the PDH method under lower conversion of propane and the harsh reaction condition when commercial Application.Therefore, develop the key that the catalyst for preparing propylene with propane dehydrogenation with high activity, high selectivity and high stability becomes this technology.The CN1201715 patent disclosure be used for the low-carbon alkanes (Pt-Sn-K/Al of dehydrogenation of C1～C5)
2O
3The Preparation of catalysts method.The CN1579616 patent report with the macropore of research and development voluntarily, low heap than, have a γ-Al of double-pore structure
2O
3Bead is a carrier, is used for the catalyst of linear alkanes dehydrogenation, by the modulation of catalyst, can improve the reactivity worth of dehydrogenating low-carbon alkane.USP4914075, USP4353815, USP4420649, USP4506032, USP4595673, EP562906, EP98622 etc. have reported that to be used for propane and other dehydrogenating low-carbon alkane Pt catalyst based, have high alkane conversion and olefine selective.Although alkane conversion and the olefine selective height of these catalyst under some reaction condition owing to the easy coking deactivation of catalyst under hot conditions, causes catalytic reaction to get poor stability, the service life of catalyst is shorter.
In order to improve the anti-carbon deposition ability of catalyst, prolong the service life of catalyst, it is the stability that carrier improves dehydrogenating propane that CN200710025372 has adopted alumina modified mesoporous molecular sieve, and CN200710133324 adds inorganic oxide binder and does the stability that carrier improves catalyst in refractory oxides.Except the moulding of the selection of carrier and catalyst is very crucial, also be one of good measure to presulfiding of catalyst.The effect and the catalyst stability of presulfurization are closely related.Presulfurization in the main collector of dehydrogenation method for pre-sulphuration is loaded into reactor with catalyst in the prior art, introduces vulcanizing agent then and vulcanizes, and its weak point mainly is that the time is longer, influences the production efficiency of process units.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of preparation method of dehydrogenation, the dehydrogenation of the inventive method preparation has the strong advantage of anti-carbon deposition ability, the service life that can effectively improve catalyst when being used for dehydrogenating propane.
The preparation method of vulcanized dehydrogenation catalyst of the present invention may further comprise the steps:
(1) preparation contains the alumina support of La and Sn;
(2) the carrying alumina body and function infusion process load dehydrogenation active component of step (1) preparation is heat-treated then;
(3) catalyst intermediate after the heat treatment is carried out steam dechlorination processing in the step (2);
(4) catalyst intermediate that obtains in the step (3) is introduced sulfur-containing compound and dry, is finally contained the dehydrogenation of vulcanizing agent.
Wherein the described La of containing of step (1), Sn alumina support prepare in cogelled mode, when becoming glue, introduces in aluminium oxide the material that contains La and contain Sn, contain La and be generally soluble-salt with the material that contains Sn, 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 content of La and Sn can need definite by use, and generally account for vehicle weight in simple substance and be: La is 0.1%～10%, and Sn is 0.1%～10%.
Wherein the described dehydrogenation activity metal of step (2) is selected from one or more elements in platinum, palladium, iridium, rhodium or the osmium in the platinum family, is preferably platinum, and content can need to determine, generally count 0.1%～2% of vehicle weight with simple substance by using.The dehydrogenation activity metal can be dispersed on the carrier, also can be enriched in carrier surface and form shell-type catalyst, and the preparation method of shell-type catalyst is this area conventional method.Infusion process is this area conventional method, and the solution impregnation that contains the dehydrogenation activity slaine as employing contains the alumina support of La and Sn.
The described heat treatment process of step (2) is to handle 1～40 hour down at 100～600 ℃, and heat treated can be an inert gas environment, also can be that oxygen content is the oxygen atmosphere that has of 0.1v%～30v%.
The described steam dechlorination of step (3) is to handle 1～20 hour down at 300～700 ℃, and the atmosphere of dechlorination is the air that contains 10v%～30v% steam, and chlorinity requires less than 0.15wt% in the catalyst intermediate.
The described catalyst intermediate of step (4) is introduced the compound of sulphur.The compound concrete grammar of introducing sulphur is that the compound of sulphur is introduced with the form of solution, and dry then, the compound of sulfur-bearing can adopt K
2S, Na
2S or (NH
4)
2Among the S etc. one or more.The compound of sulfur-bearing is generally the total dehydrogenation activity theoretical metal of catalyst and needs 80%～105% of sulfur content.Catalyst is theoretical, and to need sulfur content be the amount that needs sulphur when contained dehydrogenation activity metal component is converted into sulfide (as platinic sulfide etc.) on the catalyst.
(1) and/or (2) process in can add the required auxiliary agent of catalyst, as alkali metal promoter etc., the auxiliary agent use amount can be determined by this area general knowledge as required.
The dehydrogenation of the inventive method preparation can be used for the corresponding olefin hydrocarbon of C3～C20 dehydrating alkanes system, and optimum is used for the preparing propylene by dehydrogenating propane process, and the dehydrogenating technology method is well known to those skilled in the art.
Find after deliberation, in the Preparation of catalysts process, earlier La and Sn are incorporated in the alumina support with cogelled method, can make La and Sn disperse more evenly on the one hand; Can strengthen the active force between La, Sn and the alumina support on the other hand, suppress Sn
4+Be reduced to zeroth order Sn
0, promoted the decentralization of dehydrogenation activity metal, stop the gathering of dehydrogenation activity metal in the pyroreaction environment, effectively improved activity of such catalysts stability.In the propane dehydrogenation catalyst of the present invention, behind the supported active metal component, introduce the compound of sulfur-bearing, make dehydrogenation activity metal and sulphur be combined into the material of certain form, effectively improved selection of catalysts, obviously reduce catalyst coke content in use, further improved activity of such catalysts stability.Method for preparing catalyst process of the present invention is simple, by optimizing the adding method of the various components of catalyst, makes the anti-carbon deposition ability of catalyst and life-span all be improved.When using the catalyst of the inventive method preparation, can also shorten device on-stream time, improve the production efficiency of device.
The specific embodiment
Enforcement below by dehydrogenating propane is described further technology contents of the present invention and effect.
Example 1
Preparation contains the alumina support of La and Sn.Aluminum trichloride solution, 0.01M butter of tin solution and 0.01M La (NO with 1.0M
3)
3Solution mixes, with weight concentration is that 10% ammoniacal liquor carries out precipitation reaction, precipitation reaction temperature is 60～80 ℃, 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 ℃ of roastings 4 hours, promptly get the alumina globule that contains La 0.5wt%, Sn 0.4wt%.During preparation La other alumina support different with Sn content, the consumption that can suitably adjust various raw materials gets final product.
The carrier after the roasting and the aqueous solution that contains chloroplatinic acid are flooded 6h down at 70 ℃, and at 120 ℃ of oven dry 5h, 500 ℃ of following roasting 4h activate 4h in containing the air of steam then.Descend and contain KNO at 70 ℃ then
3Aqueous solution dipping 2h, dry, roasting under the same condition, dipping (NH again
4)
2S solution, after the drying, reduction 4h obtains catalyst in 500 ℃ the hydrogen.The load capacity of each component (in carrier) is in the catalyst: Pt 0.5wt%, La 0.5wt%, Sn 0.4wt%, K 0.5wt%.
Appreciation condition: catalyst quality 3.0g, the mass space velocity of propane are 3h
-1, reaction pressure 0.1MPa, reaction temperature is 630 ℃, adjusts response parameter according to the response situation of reality.
The result shows: this catalyst is being estimated 52h continuously, and conversion of propane is 31.2% (conversion ratio and selectivity percentage are molar percentage), and the propylene selectivity is 96.3%.Coke content only is 4.52% (coke content is the percentage that accounts for catalyst weight).After catalyst behind the primary recycling was estimated 30h continuously, conversion of propane was 30.3%, and the propylene selectivity is 96.5%, demonstrates good catalytic activity and stability.
Example 2
Preparation contains the alumina support of La and Sn.Aluminum trichloride solution, 0.02M butter of tin solution and 0.03M La (NO with 1.03M
3)
3After solution mixes, the adding weight concentration is 11% 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, 750 ℃ of roastings 4 hours, promptly get the alumina globule that contains La 1.0wt%, Sn 2.0wt%.
The carrier after the roasting and the aqueous solution that contains chloroplatinic acid are flooded 6h down at 70 ℃, and at 120 ℃ of oven dry 5h, 500 ℃ of following roasting 4h activate 4h in containing the air of steam then.Descend and contain KNO at 70 ℃ then
3With aqueous solution dipping 2h, dry, roasting under the same condition, dipping (NH again
4)
2S solution, reduction 4h obtains catalyst in 500 ℃ the hydrogen.The load capacity of each component (in carrier) is in the catalyst: Pt0.8wt%, La 1.0wt%, Sn 2.0wt%, K 1.0wt%.
Appreciation condition: catalyst quality 3.0g, the mass space velocity of propane are 3h
-1, reaction pressure 0.1MPa, reaction temperature is 630 ℃, adjusts response parameter according to the response situation of reality.
The result shows: this catalyst is being estimated 52h continuously, and conversion of propane is 32.8%, and the propylene selectivity is 96.8%.Coke content only is 3.02%.After catalyst behind the primary recycling was estimated 30h continuously, conversion of propane was 32.1%, and the propylene selectivity is 96.4%.
Example 3
Preparation contains the alumina support of La and Sn.Aluminum trichloride solution, 0.01M butter of tin solution and 0.02M La (NO with 0.96M
3)
3After solution mixes, adding weight concentration is 11% 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, 700 ℃ of roastings 4 hours, promptly get the alumina globule that contains La 1.5wt%, Sn 1.0wt%.
The carrier after the roasting and the aqueous solution that contains chloroplatinic acid are flooded 6h down at 70 ℃, and at 120 ℃ of oven dry 5h, 500 ℃ of following roasting 4h activate 4h in containing the air of steam then.Descend and contain KNO at 70 ℃ then
3With aqueous solution dipping 2h, dry, roasting under the same condition, dipping (NH again
4)
2S solution, reduction 4h obtains catalyst in 500 ℃ the hydrogen.The load capacity of each component (in carrier) is in the catalyst: Pt0.3wt%, La 1.5wt%, Sn 1.0wt%, K 0.5wt%.
Appreciation condition: catalyst quality 3.0g, the mass space velocity of propane are 3h
-1, reaction pressure 0.1MPa, reaction temperature is 630 ℃, adjusts response parameter according to the response situation of reality.
The result shows: this catalyst is being estimated 60h continuously, and conversion of propane is 31.8%, and the propylene selectivity is 96.6%.Coke content only is 2.72%.After catalyst behind the primary recycling was estimated 40h continuously, conversion of propane was 31.1%, and the propylene selectivity is 96.4%.
Comparative example
Preparation of catalysts is with example 1, and La and Sn and the common dip loading of dehydrogenation activity metal do not add (NH among the comparative catalyst in catalyst
4)
2S introduces H behind the reactor of packing into
2The S sulfuration.Reaction condition is with example 1.
The result shows: catalyst is after estimating 52h continuously, and conversion of propane is 28.5%, and the propylene selectivity is 95.6%.Coke content is 8.02%.After catalyst behind the primary recycling was estimated 30h continuously, conversion of propane was 26.2%, and the propylene selectivity is 93.5%.Activity of such catalysts less stable, regenerability are also relatively poor.
Claims (9)
1. the preparation method of a vulcanized dehydrogenation catalyst may further comprise the steps:
(1) preparation contains the alumina support of La and Sn;
(2) the carrying alumina body and function infusion process load dehydrogenation active component of step (1) preparation is heat-treated then;
(3) catalyst intermediate after the heat treatment is carried out steam dechlorination processing in the step (2);
(4) catalyst intermediate that obtains in the step (3) is introduced sulfur-containing compound and dry, is finally contained the dehydrogenation of vulcanizing agent;
Wherein described La of containing of step (1) and Sn alumina support prepare in cogelled mode, introduce the material that contains La and contain Sn when aluminium oxide becomes glue.
2. in accordance with the method for claim 1, it is characterized in that: the content of La and Sn accounts for vehicle weight in simple substance and is: La is 0.1%～10%, and Sn is 0.1%～10%.
3. it is characterized in that in accordance with the method for claim 1: containing La is nitrate or chloride with the material that contains Sn.
4. it is characterized in that in accordance with the method for claim 1: the described dehydrogenation active component of step (2) is selected from one or more elements in platinum, palladium, iridium, rhodium or the osmium in the platinum family.
5. according to claim 1 or 4 described methods, it is characterized in that: dehydrogenation active component is counted 0.1%～2% of vehicle weight with simple substance.
6. it is characterized in that in accordance with the method for claim 1: the described heat treatment process of step (2) is for handling 1～40 hour down at 100～600 ℃.
7. in accordance with the method for claim 1, it is characterized in that: the described steam dechlorination of step (3) is for handling 1～20 hour down at 300～700 ℃, and the atmosphere of dechlorination is the air that contains 10v%～30v% steam.
8. in accordance with the method for claim 1, it is characterized in that: the method that the described catalyst intermediate of step (4) is introduced sulfur-containing compound is: sulfur-containing compound is introduced with the form of solution, and dry then, sulfur-containing compound adopts K
2S, Na
2S or (NH
4)
2Among the S one or more.
9. according to claim 1 or 8 described methods, it is characterized in that: sulfur-containing compound was theoretical 80%～105% of the sulfur content that needs of the total dehydrogenation active component of catalyst when the described catalyst intermediate of step (4) was introduced sulfur-containing compound.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9782754B2 (en) | 2012-07-26 | 2017-10-10 | Saudi Basic Industries Corporation | Alkane dehydrogenation catalyst and process for its preparation |
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|---|---|---|---|---|
| CN102908895B (en) * | 2011-08-01 | 2014-10-15 | 中国石油化工股份有限公司 | Method for removal of hydrogen sulfide in products in dehydrogenation device |
| CN102911000B (en) * | 2011-08-01 | 2014-12-31 | 中国石油化工股份有限公司 | Dehydrogenation method for light alkanes |
| CN102910997B (en) * | 2011-08-01 | 2014-08-20 | 中国石油化工股份有限公司 | Method for preparing olefins by using dehydrogenation of light alkanes with sulfur-containing substances added in raw materials |
| CN103785423B (en) * | 2012-11-01 | 2015-11-18 | 中国石油化工股份有限公司 | A kind of preparation method of vulcanized dehydrogenation catalyst |
| CN104591943B (en) * | 2013-11-03 | 2017-02-01 | 中国石油化工股份有限公司 | Saturated alkane dehydrogenation method |
| CN105642281B (en) * | 2014-12-04 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof |
| CN107262147B (en) * | 2017-06-14 | 2019-09-27 | 昆明理工大学 | A kind of Sulfur tolerance catalyst for catalytic combustion and preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5416052A (en) * | 1994-01-21 | 1995-05-16 | Intevep, S.A. | Catalyst for use in the dehydrogenation and isomerization of paraffins and method for preparing the catalyst |
| CN1155451A (en) * | 1996-01-24 | 1997-07-30 | 中国科学院大连化学物理研究所 | Preparation of low carbon alkane dehydrogenating catalyst |
| CN1223170A (en) * | 1998-01-15 | 1999-07-21 | 吉林化学工业公司研究院 | Catalyst composition for catalytic dehydrogenation of paraffin for preparing olefines and application thereof |
| CN1381440A (en) * | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Catalyst for preparing phenylamine or alkylphenylamine |
-
2009
- 2009-05-25 CN CN200910011771XA patent/CN101898138B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5416052A (en) * | 1994-01-21 | 1995-05-16 | Intevep, S.A. | Catalyst for use in the dehydrogenation and isomerization of paraffins and method for preparing the catalyst |
| CN1155451A (en) * | 1996-01-24 | 1997-07-30 | 中国科学院大连化学物理研究所 | Preparation of low carbon alkane dehydrogenating catalyst |
| CN1223170A (en) * | 1998-01-15 | 1999-07-21 | 吉林化学工业公司研究院 | Catalyst composition for catalytic dehydrogenation of paraffin for preparing olefines and application thereof |
| CN1381440A (en) * | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Catalyst for preparing phenylamine or alkylphenylamine |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9782754B2 (en) | 2012-07-26 | 2017-10-10 | Saudi Basic Industries Corporation | Alkane dehydrogenation catalyst and process for its preparation |
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