CN101898131B - Dehydrogenation catalyst taking Sn-containing alumina as carrier and preparation method thereof - Google Patents
Dehydrogenation catalyst taking Sn-containing alumina as carrier and preparation method thereof Download PDFInfo
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- CN101898131B CN101898131B CN2009100117724A CN200910011772A CN101898131B CN 101898131 B CN101898131 B CN 101898131B CN 2009100117724 A CN2009100117724 A CN 2009100117724A CN 200910011772 A CN200910011772 A CN 200910011772A CN 101898131 B CN101898131 B CN 101898131B
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Abstract
The invention discloses a dehydrogenation catalyst taking Sn-containing alumina as a carrier and a preparation method thereof. The dehydrogenation catalyst takes the Sn-containing alumina as the carrier, nano fibers are carried on the pore surface of the carrier, and dehydrogenation active metal ingredients are carried by an immersion method. The preparation method for the catalyst comprises the following steps of: introducing the carrier to Sn when the alumina is gelled, carrying the carbon nano fibers to the Sn-containing alumina carrier in situ by ethylene cracking, then immersing the dehydrogenation active ingredients, and performing thermal treatment and water vapor treatment to obtain the final dehydrogenation catalyst. When the catalyst is used for a hydrocarbon dehydrogenation reaction process, in particular a propane dehydrogenation process, the catalyst has the advantages of high activity, high selectivity and the like, and particularly greatly improves the stability.
Description
Technical field
The present invention relates to a kind of dehydrogenation and preparation method thereof, particularly to contain the Catalysts and its preparation method that the Sn aluminium oxide is the preparing propylene by dehydrogenating propane of carrier.
Background technology
Got into since the new century; World's petrochemical material and petroleum chemicals demand will sustainable growths; To continue to increase as the demand of petrochemical industry basic material propylene, and conventional steam cracking and the technological production capacity of FCC can not satisfy the propylene demand of quick growth, 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 receives thermodynamics equilibrium limit, must under the harsh conditions of high temperature, low pressure, carry out.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 dehydrogenating propane technology is representative with the Oleflex technology of Uop Inc. and the Catafin technology of U.S. Air Product company.
Load type platinum is catalyst based to be in the alkane dehydrogenating catalyst important one type, and the production method of such catalyst is also open in the art.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.The CN1201715 patent discloses and has been 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 macropore, 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, through the modulation of catalyst, can improve the reactivity worth of dehydrogenating low-carbon alkane.Although alkane conversion and the olefine selective of these catalyst under some reaction condition is high, because catalyst is prone to coking deactivation under hot conditions, cause catalytic reaction to get poor stability, the service life of catalyst is shorter.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.But still do not improve the anti-carbon deposition ability and the stability 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.It is the catalyst for dehydrogenation of low-carbon paraffin of carrier with ZSM-5 that CN200610086006 relates to a kind of; CN200610126812 has selected with nanoscale single wall or many walls carbon mitron to be carrier, to be a kind of catalyst for dehydrogenation of low-carbon paraffin of active component with the transition metal oxide.In order to improve the economy of dehydrating alkanes technology, above-mentioned activity of such catalysts stability still needs further to improve.
Summary of the invention
Deficiency to prior art; The present invention provides a kind of alkane dehydrogenating catalyst and preparation method thereof; Major advantage is to cover containing the Sn alumina support specific area and pore structure all being optimized of charcoal; And can improve the acid centre number and the acid strength of carrier, carbon nano-fiber has good anti-coking performance, has improved the stability of catalyst greatly.
The present invention is to contain in the dehydrogenation that the Sn aluminium oxide is a carrier; To contain the Sn aluminium oxide is carrier; Carrier duct area load carbon nano-fiber, infusion process load dehydrogenation activity metal component, the amount of carbon nano-fiber is 5%～20% of a vehicle weight; The dehydrogenation activity metal component generally is selected from one or more in platinum, palladium, iridium, rhodium or the osmium in the platinum family, and consumption is counted 0.01%～2% of vehicle weight with simple substance.The content of Sn is counted 0.1%～10% of vehicle weight with simple substance.
The present invention is to contain in the dehydrogenation that the Sn aluminium oxide is a carrier, and Sn introduces the material that contains Sn when aluminium oxide becomes glue, process carrier then.
The present invention is to contain in the dehydrogenation that the Sn aluminium oxide is a carrier, and carbon nano-fiber adopts cracking of ethylene original position carrying method to load on the alumina support that contains Sn.The amount of the carbon nano-fiber that obtains can be carried out modulation through cracking temperature, volume space velocity and reaction time.
The present invention is to contain in the dehydrogenation that the Sn aluminium oxide is a 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, like alkali metal, sulphur etc. simultaneously to contain in the dehydrogenation that the Sn aluminium oxide is a carrier.
Catalyst pore volume of the present invention is generally 0.40～0.48cm
3/ g, specific area is generally 180～240m
2/ g.
The present invention is that the preparation method of the dehydrogenation of carrier comprises following process to contain the Sn aluminium oxide:
(1) the carbon nano-fiber original position is loaded on the alumina support that contains Sn through cracking of ethylene;
(2) adopt infusion process load dehydrogenation active component, conditions such as pH value that can be through the control dipping solution and dip time mainly concentrate in the certain thickness skin of carrier surface dehydrogenation active component;
(3) material that obtains in the step (2) is heat-treated;
(4) catalyst intermediate after the heat treatment is carried out the steam dechlorination in the step (3).
Wherein the amount of the carbon nano-fiber of original position load is 5%～20% of a vehicle weight in the step (1); The method and the condition of cracking of ethylene original position load carbon nano-fiber are: place in the tubular reactor containing Sn alumina globule particle; Feed ethylene gas; 600 ℃～800 ℃ of cracking temperatures, reaction time 2h～20h.
The alumina support that contains Sn in the step (1) is introduced Sn when aluminium oxide becomes glue, preparation contains the alumina support of Sn then.The described Sn of containing alumina support prepares with cogelled mode;, introduces in aluminium oxide the material that contains Sn when becoming glue; The material that contains Sn is generally soluble-salt, like 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 method that the technical staff knew.
The described dehydrogenation activity metal of step (2) generally is selected from one or more in platinum, palladium, iridium, rhodium or the osmium in the platinum family, and content can need to confirm, generally count 0.01%～2% of vehicle weight with simple substance by use.The dehydrogenation activity metal adopts existing infusion process load.
The described heat treatment process of step (3) is to handle 1～40 hour down at 100～600 ℃, and heat treated is at inert gas environment.
The described steam dechlorination of step (4) is to handle 1～20 hour down at 300～700 ℃, and the atmosphere of dechlorination is the nitrogen that contains 10v%～30v% steam, and the content of halogens is less than 0.15wt%.
In step (1) and/or (2) process, can add the required auxiliary agent of catalyst, also can introduce auxiliary agent afterwards in step (4).Auxiliary agent kind and use amount can be as required confirm by this area general knowledge, as can add alkali metal promoter, the alkali metal promoter consumption is 0.1%～5% of a catalyst carrier weight.
Find after deliberation, in the Preparation of catalysts process, the in-situ modified Sn alumina support that contains of carbon nano-fiber, specific surface area of catalyst increases, and acid centre number and acid strength reduce, and have reduced pyrolysis product, have improved selection of catalysts property.In addition, be incorporated into Sn in the alumina support with cogelled method earlier, can make Sn disperse more evenly on the one hand; Can strengthen the active force between 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.This patent mainly provides the method for preparing high selectivity, high stability catalyst, shortens the problem of catalyst the evolving path, solution poor stability.
Description of drawings
Transmission electron microscope (TEM) figure of Fig. 1 original position load carbon nano-fiber alumina support.
The specific embodiment
Enforcement through dehydrogenating propane further specifies technology of the present invention below.
Instance 1
Preparation contains the alumina support of Sn.Behind the aluminum trichloride solution and the mixing of 0.01M butter of tin solution with 1.13M, the adding weight concentration is 7% ammoniacal liquor, under 60～80 ℃, in neutralizing tank, mixes; Control pH value 7.0～9.0; After filtration, washing, the acidifying, the balling-up of pressurizeing in the oil ammonia column is through overaging; 650 ℃ of roastings 4 hours, promptly get the alumina globule that contains Sn 1.0wt%.
The alumina globule particle that will contain Sn1.0wt% places in the tubular reactor, feeds ethylene gas, at 600 ℃ of following Pintsch process, through promptly getting the carrier of carbon fiber-containing amount 8% behind the 6h.
With the alumina support and the platinum acid chloride solution dipping 12h of the modification of load carbon nano-fiber, at 70 ℃ of rotation evaporates to dryness down, at 120 ℃ of oven dry 5h, roasting 4h under 500 ℃ of inert atmospheres then, activation 4h in containing the nitrogen of steam.Descend and contain KNO at 70 ℃ then
3Aqueous solution dipping 2h, dry, roasting under the same condition, reduction 4h obtains catalyst in 500 ℃ the hydrogen.The load capacity of each component is in the catalyst: Pt0.5wt%, Sn 1.0wt%, 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 620 ℃, according to the response situation adjustment response parameter of reality.
The result shows: this catalyst is being estimated 40h continuously, and conversion of propane is 32.3% (conversion ratio and selectivity percentage are molar percentage), and the propylene selectivity is 96.5%, and active the reduction is merely 1.5%.Demonstrate good catalytic activity and stability.
Instance 2
Preparation contains the alumina support of Sn.Aluminum trichloride solution and the 0.02M butter of tin solution of 1.15M are mixed, and the adding weight concentration is 10% ammoniacal liquor, under 60～80 ℃, in neutralizing tank, mixes; Control pH value 7.0～9.0; After filtration, washing, the acidifying, the balling-up of pressurizeing in the oil ammonia column is through overaging; 750 ℃ of roastings 4 hours, promptly get the alumina globule that contains Sn 2.0wt%.
The alumina globule particle that will contain Sn 2.0wt% places in the tubular reactor, feeds ethylene gas, at 700 ℃ of following Pintsch process, promptly gets the carrier that contains charcoal fibre weight 12% through behind the 8h.
The modified aluminium oxide supports and the platinum acid chloride solution of load carbon nano-fiber are being soaked 12h altogether, at 70 ℃ of following rotation evaporates to dryness, at 120 ℃ of oven dry 5h, roasting 4h under 500 ℃ of inert atmospheres then, activation 4h in containing the nitrogen of steam.Descend and contain KNO at 70 ℃ then
3Aqueous solution dipping 2h, dry, roasting under the same condition, reduction 4h obtains catalyst in 500 ℃ the hydrogen.The load capacity of each component is in the catalyst: Pt0.5wt%, Sn 2.0wt%, K 0.5wt%.
Appreciation condition: catalyst quality 3.0g, the mass space velocity of propane are 3.0h
-1, reaction pressure 0.1MPa, reaction temperature is 620 ℃, according to the response situation adjustment response parameter of reality.
The result shows: this catalyst is being estimated 50h continuously, and conversion of propane is 32.8%, and the propylene selectivity is that 97.1% active the reduction is merely 1%.Demonstrate good catalytic activity and stability.
Instance 3
Preparation contains the alumina support of Sn.Behind the aluminum trichloride solution and the mixing of 0.01M butter of tin solution with 1.0M, the adding weight concentration is 11% ammoniacal liquor, under 60～80 ℃, in neutralizing tank, mixes; Control pH value 7.0～9.0; After filtration, washing, the acidifying, the balling-up of pressurizeing in the oil ammonia column is through overaging; 700 ℃ of roastings 4 hours, promptly get the alumina globule that contains Sn 0.5wt%.
The alumina globule particle that will contain Sn 0.5wt% places in the tubular reactor, feeds ethylene gas, at 700 ℃ of following Pintsch process, promptly gets the carrier that contains charcoal fibre weight 12% through behind the 8h.
The modified aluminium oxide supports of load carbon nano-fiber is 600 ℃ of roasting 3h under inert atmosphere; Carrier after the roasting and platinum acid chloride solution are being soaked 6h altogether, rotating evaporate to dryness down, at 120 ℃ of oven dry 5h at 70 ℃; Roasting 4h under 500 ℃ of inert atmospheres then, activation 4h in containing the nitrogen of steam.Descend and contain KNO at 70 ℃ then
3Aqueous solution dipping 2h, dry, roasting under the same condition, reduction 4h obtains catalyst in 500 ℃ the hydrogen.The load capacity of each component is in the catalyst: Pt 0.3wt%, Sn 0.5wt%, K 0.5wt%.
Appreciation condition: catalyst quality 3.0g, the mass space velocity of propane are 3.0h
-1, reaction pressure 0.1MPa, reaction temperature is 620 ℃, according to the response situation adjustment response parameter of reality.
The result shows: this catalyst is being estimated 30h continuously, and conversion of propane is 31.2%, and the propylene selectivity is 96.7%, and active the reduction is merely 0.6%.Demonstrate good catalytic activity and stability.
Comparative example
Be a contrast experiment, not load of alumina globule carrier carbon nano-fiber, Sn loads on the catalyst carrier with dipping method and Pt jointly, and other preparation process of catalyst is with instance 1, and reaction condition is with instance 1.
The result shows: the catalyst of comparative example is being estimated 40h continuously, and conversion of propane is 28.5%, and the propylene selectivity is 95.6%, active decline 4%.And after the catalyst of embodiment 1 estimated 40h continuously, conversion of propane was 32.3%, and the propylene selectivity is 96.5%, and activity only descends 1.5%.
Table 1 embodiment and comparative example specific area, pore structure and catalyst acid quantitative changeization
| Specific area/m 2/g | Average pore size/nm | Pore volume/cm 3/g | Catalyst acid amount/mmol/g | |
| Instance 1 | 188 | 10.2 | 0.48 | 0.16 |
| Instance 2 | 214 | 8.3 | 0.44 | 0.12 |
| Comparative example | 174 | 11.4 | 0.50 | 0.24 |
Claims (8)
1. one kind to contain the dehydrogenation that the Sn aluminium oxide is a carrier; It is characterized in that: to contain the Sn aluminium oxide is carrier, carrier duct area load carbon nano-fiber, infusion process load dehydrogenation activity metal component; The amount of carbon nano-fiber is 5%～20% of a vehicle weight; The dehydrogenation activity metal component is selected from one or more in platinum, palladium, iridium, rhodium or the osmium in the platinum family, and consumption is counted 0.01%～2% of vehicle weight with simple substance, and the content of Sn is counted 0.1%～10% of vehicle weight with simple substance;
The Sn that wherein contains in the Sn alumina support introduces the material that contains Sn when aluminium oxide becomes glue, process carrier then; Wherein carbon nano-fiber adopts cracking of ethylene original position carrying method to load on the alumina support that contains Sn.
2. according to the described catalyst of claim 1, it is characterized in that: contain alkali metal promoter in the dehydrogenation.
3. said Preparation of catalysts method of claim 1 comprises following process:
(1) the carbon nano-fiber original position is loaded on the alumina support that contains Sn through cracking of ethylene, the amount of carbon nano-fiber is 5%～20% of a vehicle weight;
(2) adopt infusion process load dehydrogenation active component;
(3) material that obtains in the step (2) is heat-treated;
(4) catalyst intermediate after the heat treatment is carried out the steam dechlorination in the step (3).
4. according to the described method of claim 3; It is characterized in that: the process of original position load carbon nano-fiber is in the step (1): place in the tubular reactor containing the Sn alumina carrier particle; Ethylene gas is fed in the reactor; Ethene is 600 ℃～800 ℃ following cracking, and the carbon fiber that cracking generates combines with aluminium oxide, can obtain the composite carbon carrier.
5. according to the described method of claim 3; It is characterized in that: the alumina support that contains Sn in the step (1) is introduced Sn when aluminium oxide becomes glue; Preparation contains the alumina support of Sn then; The described Sn of containing alumina support prepares with cogelled mode, when aluminium oxide becomes glue, introduces the material that contains Sn.
6. according to the described method of claim 3, it is characterized in that: the described heat treatment process of step (3) is for handling 1～40 hour down at 100～600 ℃, and heat treatment is at inert gas environment.
7. according to the described method of claim 3, it is characterized in that: the described steam dechlorination of step (4) is for handling 1～20 hour down at 300～700 ℃, and the atmosphere of dechlorination is the nitrogen that contains 10v%～30v% steam.
8. according to the described method of claim 3, it is characterized in that: in step (1) and/or (2) process, add catalyst promoter, perhaps introduce auxiliary agent afterwards in step (4); Auxiliary agent comprises alkali metal, and the alkali metal promoter consumption is 0.1%～5% of a catalyst carrier weight.
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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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| CN102909095B (en) * | 2011-08-01 | 2014-12-10 | 中国石油化工股份有限公司 | Hydrogen-concentration-controlling stepwise reductive activation method for dehydrogenation catalyst |
| CN102909010B (en) * | 2011-08-01 | 2014-06-25 | 中国石油化工股份有限公司 | Dehydrogenation catalyst activation method combining high-temperature reduction with temperature programmed reduction |
| CN102909012B (en) * | 2011-08-01 | 2015-04-01 | 中国石油化工股份有限公司 | Activation method for dehydrogenation catalyst |
| CN103785384B (en) * | 2012-11-01 | 2016-02-10 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation |
| CN104588032A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Alkane dehydrogenation catalyst and preparation method thereof |
| CN105396583B (en) * | 2014-09-11 | 2018-06-12 | 中国石油化工股份有限公司 | A kind of catalyst for preparing propylene with propane dehydrogenation and its preparation method and application |
| 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 |
| CN105727980B (en) * | 2014-12-06 | 2018-02-09 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for preparing propene by oxidative dehydrogenation of propane |
| CN106311201B (en) * | 2015-06-30 | 2018-10-02 | 中国石油化工股份有限公司 | It is a kind of using mesoporous carbon containing Sn as dehydrogenation of isobutane Pt bases catalyst, preparation method and its application of carrier |
| CN105642273B (en) * | 2015-12-24 | 2018-02-23 | 江苏扬子催化剂有限公司 | The impregnation drying technique of chromium series microspheroidal fluid bed dehydrogenation of isobutane catalyst |
| CN107961783B (en) * | 2017-11-22 | 2021-05-14 | 航天长征化学工程股份有限公司 | Catalyst for synthesizing low-carbon olefin |
| CN114602442B (en) * | 2022-03-28 | 2023-01-10 | 福州大学 | Preparation method of low-carbon alkane dehydrogenation catalyst for moving bed |
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Cited By (1)
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