CN102909101B - Method for activating dehydrogenation catalyst by employing low concentration hydrogen via low temperature reduction - Google Patents
Method for activating dehydrogenation catalyst by employing low concentration hydrogen via low temperature reduction Download PDFInfo
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Abstract
The invention discloses a method for activating a dehydrogenation catalyst by employing low concentration hydrogen via low temperature reduction. The dehydrogenation catalyst is a platinum group metal-supported catalyst. The method comprises the following steps of performing the low temperature reduction and activation by using low concentration hydrogen before the dehydrogenation catalyst is used, wherein the reducing gas is a mixture of nitrogen and hydrogen; the volume content of hydrogen is 1%-20%; the reduction temperature of the low temperature reduction us 240-400 DEG C; and the reduction time is 1.0-8.0 h; then heating to a temperature of 550-650 DEG C; omitting sulfuration passivation; and directly passing through a raw material gas containing hydrogen to perform dehydrogenation reaction. Compared with a dehydrogenation catalyst 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 a kind of activation method of low-carbon alkanes catalytic dehydrogenation alkene catalyst, specifically, is about C
2~ C
5the activation method of Oxidative Dehydrogenation alkene catalyst.
Background technology
Along with the universal use of civil natural gas, effective utilization of refinery's liquefied gas becomes the focus of petrochemical industry, utilizes low-carbon alkanes resource valuable in liquefied gas significant with how becoming more meticulous.Preparing propylene by dehydrogenating propane and preparing isobutene through dehydrogenation of iso-butane just liquefied gas produce one of important channel of industrial chemicals, and it will become an emphasis of new century petrochemical technology research and development.
Low-carbon alkanes catalytic dehydrogenating reaction limits by thermodynamical equilibrium, must carry out under the harsh conditions of high temperature, low pressure.Too high reaction temperature, makes low-carbon alkanes cracking reaction and deep dehydrogenation aggravation, selective decline; Accelerate catalyst surface carbon deposit simultaneously, make rapid catalyst deactivation.Due to the shortening of catalyst life under lower alkane conversion and harsh reaction condition, dehydrogenating low-carbon alkane method is made to receive certain restriction when commercial Application.Therefore, exploitation has the key that the catalyst for preparing propylene with propane dehydrogenation of high selectivity and high stability and supporting technique become this technology.At present, dehydrogenating low-carbon alkane patented technology comprises in the world: the Oleflex technique of Uop Inc., the Catofin technique of ABB Lu Musi company, the Star technique of Kang Fei (Uhde) company, the FBD-4 technique of Snamprogetti/Yarsintz company, the PDH technique etc. of Lin De/BASF AG.In the device built, former Soviet Union's great majority adopt FBD-4 technique, and Catofin and Oleflex technique has become the leading technique adopted in new device.Oleflex technique is mainly catalyst based based on Pt, and Catafin technique is mainly with Cr
2o
3/ Al
2o
3be main.
Load type platinum is catalyst based is an important class in alkane dehydrogenating catalyst, and the production method of such catalyst is also open in the art.USP4914075, USP4353815, USP4420649, USP4506032, USP4595673, EP562906, EP98622 etc. report for propane catalyst based with other dehydrogenating low-carbon alkane Pt, have high alkane conversion and olefine selective.USP3897368 and CN87108352 discloses a kind of method of producing core-shell catalyst, and Pt optionally concentrates and is deposited on the outer surface of catalyst carrier, and the inner Pt content of catalyst carrier is lower, can improve the utilization rate of active metal.Above-mentioned this kind of Pt catalyst must use hydrogen reducing before use, and the catalyst after reduction is used for dehydrogenation reaction, in order to increase the stability of catalyst, generally carries out Passivation Treatment.In this kind of catalyst, reduction adopts the reduction of pure hydrogen constant temperature, and low-temperature reduction does not generally reach the reduction degree of depth, and therefore constant temperature reduction temperature is generally 400 ~ 650 DEG C, carries out vulcanizing treatment again after reduction.As CN101138734A, CN101015802A in 400 ~ 600 DEG C of hydrogen streams constant temperature reductase 12 ~ 10h, CN1844324A at 400 DEG C hydrogen stream constant temperature reduction 7h, CN101108362A preferably at 450 ~ 550 DEG C in hydrogen stream constant temperature reduction 4 ~ 6h.Constant temperature reduction in High Purity Hydrogen air-flow, although the active component of catalyst can be made to become elemental metals state, guarantee that metal component reaches drastic reduction, catalyst initial activity is higher, and the activity decrease of catalyst is very fast, less stable.Only have by passivation, the stability of catalyst could be improved.
Summary of the invention
For the deficiencies in the prior art, the invention provides the method for a kind of catalyst for dehydrogenation of low-carbon paraffin activation, eliminate sulfuration passivating process on the basis of existing technology, and further increase object product yield, improve the stability of catalyst simultaneously.
The present invention adopts the method for low-concentration hydrogen low-temperature reduction activation of dehydrogenation catalyst, comprise following content: dehydrogenation is platinum family loaded catalyst, dehydrogenation adopts low-concentration hydrogen to carry out low-temperature reduction activation before use, reducing gas is the mixture of nitrogen and hydrogen, wherein the volume content of hydrogen is 1% ~ 20%, low-temperature reduction temperature is 240 ~ 400 DEG C, recovery time is 1.0 ~ 8.0h, then 550 ~ 650 DEG C are warmed up to, cancel sulfuration passivation, the unstripped gas directly passing into hydrogen carries out dehydrogenation reaction.
In the inventive method, dehydrogenation changes by the reduction of traditional High Purity Hydrogen air-flow high temperature constant temperature the concentration cryogenic thermostat controlling hydrogen in reducing gases into before use and reduces, the reduction degree of Pt in catalyst is made to reach 20% ~ 40%, dehydrogenation activity metal depth is avoided to reduce the catalyst activity accumulation of metal phenomenon caused, also some can be avoided not wish, and the adjuvant component reduced is by drastic reduction, have impact on the synergy of auxiliary agent.
The detailed process of a kind of activation of the present invention is as follows: first in a nitrogen atmosphere, with 0.5 ~ 30 DEG C/min heating rate, preferably temperature is raised to 240 ~ 400 DEG C by the heating rate of 5 ~ 15 DEG C/min, then gas composition is changed in nitrogen containing 1% ~ 10%(volume) reducing gases of hydrogen, hydrogen content preferably 4% ~ 8%, at 240 ~ 400 DEG C of constant temperature reduction 1 ~ 5h, preferably 2 ~ 4h; Again gas composition is changed in nitrogen containing 10% ~ 20%(volume) hydrogen, at 240 ~ 400 DEG C of constant temperature reduction 0.5 ~ 4h, preferably 1 ~ 3h.
In dehydrogenation catalyst activation method of the present invention, dehydrogenation is platinum family loaded catalyst, catalyst generally with aluminium oxide or faintly acid molecular sieve for carrier, with one or more in the platinum in platinum family, palladium, iridium, rhodium or osmium for active component, active component comprises platinum, and be vehicle weight in element active component 0.01% ~ 2%.Suitable auxiliaries can be contained in dehydrogenation simultaneously, auxiliary agent is as one or more in Sn, La, K, rare earth metal etc., the content of preferred promoter Sn or La counts 0.1% ~ 10% of vehicle weight with element, and the content of auxiliary agent K counts 0.1% ~ 10% of vehicle weight with element.Dehydrogenation can adopt the method for this area routine to prepare, and as adopted infusion process load dehydrogenation active component, auxiliary agent and/or can adopt infusion process to introduce in carrier preparation process.
Existing dehydrogenation is when activating, to take under traditional higher temperature constant temperature method of reducing in hydrogen stream, although this activation method has dehydrogenation activity metallic reducing fully and the high advantage of initial reaction activity, stability is relatively poor more, along with the carrying out of reaction, activity decrease is very fast.In order to increase its stability, passivation must be carried out.In the activation method of dehydrogenation of the present invention, platinum based catalyst adopts conventional method preparation, does not carry out conventional restoring operation, adopts and controls the reduction of density of hydrogen cryogenic thermostat with the reduction degree controlling Pt in catalyst.Its object is to suppress the initial stage cracking performance of catalyst to be beneficial to long-term stability.After catalyst has certain reduction degree, the unstripped gas passing into hydrogen that heats up reacts, and Pt in catalyst is reduced further.Reaching active component Pt reacts while reduce, and active slow releasing is to increase the object of catalyst stability.After activation process, improve the serviceability of catalyst, in particular improve the stability of the selective of object product and long-time reaction, the catalyst serviceability after activation is stablized, and activation process is easy to control, and eliminates passivating process.
Detailed description of the invention
Under dehydrogenation catalyst activation method of the present invention instead of traditional higher temperature by the reduction degree controlling density of hydrogen control Pt in reducing gases, constant temperature reduces.Dehydrogenation of the present invention does not need passivation just can improve the stability of long-lasting catalytic running.Dehydrogenation is preferably active component with Pt, and take 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 adopted infusion process load dehydrogenation activity metal, auxiliary agent and can adopt dipping method to introduce in carrying alumina production procedure.
Catalyst of the present invention with containing Sn aluminium oxide or faintly acid molecular sieve for carrier, dehydrogenation activity metal component is generally selected from one or more in platinum, palladium, iridium, rhodium or the osmium in platinum family, and be preferably platinum, consumption counts 0.01% ~ 2% of vehicle weight with simple substance.The content of Sn counts 0.1% ~ 10% of vehicle weight with simple substance.
The present invention is with in the dehydrogenation that is carrier containing Sn aluminium oxide or faintly acid, and Sn introduces the material containing Sn when aluminium oxide plastic, then make carrier.
The present invention is with in the dehydrogenation that is carrier containing Sn aluminium oxide or faintly acid molecular sieve, and dehydrogenation activity metal component can be uniformly distributed in the catalyst, and preferred dehydrogenation activity metal component integrated distribution, in catalyst outer layer, forms core-shell catalyst.
The present invention, can simultaneously containing suitable auxiliary agent with in the dehydrogenation that is carrier containing Sn aluminium oxide or faintly acid molecular sieve, as one or more in alkali metal, alkaline-earth metal, rare earth metal etc.
Introduce detailed process and the condition of a kind of typical dehydrogenation method for preparing catalyst and activation method below:
(1) with alumina globule or faintly acid molecular sieve for carrier impregnation SnCl
4solution, wherein content can need to determine by use, preferably counts 0.1% ~ 5% of aluminium oxide or faintly acid molecular sieve with simple substance;
(2) containing after carrier 800 DEG C of roastings of Sn, supersaturation infusion process is adopted to introduce dehydrogenation active component; Can, by conditions such as the pH value of control dipping solution and dip times, dehydrogenation active component be made mainly to concentrate in the certain thickness skin of carrier surface;
(3) catalyst intermediate in step (2) after heat treatment carries out steam dechlorination;
(4) add the alkali metal promoter needed for catalyst in the catalyst that step (3) obtains, auxiliary agent use amount can be determined by this area general knowledge as required.
(5) catalyst that step (4) obtains adopts the concentration cryogenic thermostat reduction controlling hydrogen in reducing gases, and constant temperature reduction temperature scope is at 240 ~ 400 DEG C.
(6) dehydrogenation reaction is carried out under the atmosphere of hydrogen as diluent.
Alumina support containing Sn in step (1) introduces Sn when aluminium oxide plastic, and then preparation is containing the alumina support of Sn.Described prepares in cogelled mode containing Sn alumina support, the material containing Sn is introduced when aluminium oxide plastic, material containing Sn is generally soluble-salt, as nitrate, chloride etc., then shaping by the existing method in this area, as dripped a ball forming, extruded etc., aluminium oxide plastic is known by technical staff.The method of preparation method known by technical staff of above-mentioned carrier.
Dehydrogenation activity metal wherein described in step (2) is generally selected from one or more elements in platinum, palladium, iridium, rhodium or the osmium in platinum family, and content can need to determine by use, preferably counts 0.1% ~ 2% of vehicle weight with element.
Steam dechlorination described in step (3) is process 1 ~ 20 hour at 300 ~ 700 DEG C, and the atmosphere of dechlorination is the air containing 10v% ~ 30v% water vapour, and chlorinity is less than 0.15wt%.
After prereduction described in step (5), constant temperature reducing condition is temperature 240 ~ 400 DEG C, preferably 280 ~ 360 DEG C.
Dehydrogenation reaction conditions described in step (6) is: reaction temperature 500 ~ 650 DEG C, volume space velocity 500 ~ 5000h
-1, absolute pressure 0.1 ~ 0.5MPa, unstripped gas is low-carbon alkanes, hydrogen: the molar ratio of low-carbon alkanes is between 1:1 ~ 6:1.Described low-carbon alkanes is C
3~ C
5alkane, as propane, normal butane, iso-butane, pentane, isopentane etc.
Enforcement below by dehydrogenation of isobutane is described further technology of the present invention.Wherein the percentage composition of not clear and definite benchmark is weight percentage.In dehydrogenation, the implication of the reduction degree of Pt is that the ratio of the amount of total Pt in amount and the catalyst of the Pt be reduced in catalyst is multiplied by 100%, measures or analytical method is TPR, TPD hydroxide titration method, ICP method or inorganic analysis method.
Example 1
Preparation is containing the alumina support of Sn.After the aluminum trichloride solution of a certain amount of 0.98M and the mixing of 0.01M butter of tin solution, add a certain amount of 8% ammoniacal liquor, mix in neutralizing tank at 60 ~ 80 DEG C, control ph 7.0 ~ 9.0, filter, washing, after acidifying, balling-up of pressurizeing in oil ammonia column, through super-dry, aging, 650 ~ 750 DEG C of roastings 4 hours, obtain the alumina globule containing Sn 0.8wt%.
By the alumina globule carrier containing 0.8% Sn at 800 DEG C of roasting 3h, the carrier after roasting and the aqueous solution containing chloroplatinic acid are flooded 6h at 70 DEG C, dry 2h, roasting 4h at 500 DEG C at 120 DEG C.Then in containing the air of water vapour, 4h is activated.Then at 70 DEG C and containing KNO
3aqueous impregnation 2h, dry under same condition, roasting.In catalyst, the load capacity of each component is: Pt 0.3wt%, Sn 0.8wt%, K 0.7wt%.
activation condition:first be warming up in a nitrogen atmosphere 300 DEG C, then in nitrogen, have 6%(volume/volume) hydrogen, 300 DEG C of constant temperature 3h, then gas composition is changed in nitrogen, have 15%(volume/volume) hydrogen, 300 DEG C of constant temperature 1h.In activation process, the volume space velocity of reducing gases is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 27%
appreciation condition: catalyst volume 3.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 580 DEG C, hydrogen: the ratio of iso-butane is at 2:1.
result shows: this catalyst is evaluating 48h continuously, and iso-butane conversion ratio is 39.06%, and selective isobutene is 95.32%, conversion ratio and selective substantially constant, and coke content is only 0.85%, demonstrates good catalytic activity and stability.
Comparative example
The preparation of catalyst, with example 1, obtains catalyst unlike the reduction of constant temperature in 500 DEG C of flow of pure hydrogen.
activation condition:500 DEG C of Cheng Hengwen reduction 3h, the volume space velocity of reducing gases is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 92%
appreciation condition: catalyst volume 3.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 580 DEG C, hydrogen: the ratio of iso-butane is at 2:1.
result shows: this catalyst is evaluating 48h continuously, and iso-butane conversion ratio is 36.5%, and selective isobutene is 95.2%, and conversion ratio declines 3.1 percentage points, selective substantially constant, and coke content is 1.52%.
Example 2
Preparation is containing the alumina support of Sn.After the aluminum trichloride solution of a certain amount of 1.08M and the mixing of 0.01M butter of tin solution, add a certain amount of 10% ammoniacal liquor, mix in neutralizing tank at 60 ~ 80 DEG C, control ph 7.0 ~ 9.0, filter, washing, after acidifying, balling-up of pressurizeing in oil ammonia column, through super-dry, aging, 650 ~ 750 DEG C of roastings 4 hours, obtain the alumina globule containing Sn 1.0wt%.
By the alumina globule carrier containing 1.0% Sn at 800 DEG C of roasting 3h, the carrier after roasting and the aqueous solution containing chloroplatinic acid are flooded 4h at 70 DEG C, dry 2h at 120 DEG C, roasting 4h at 500 DEG C, activates 4h in containing the air of water vapour.Then at 70 DEG C and containing KNO
3aqueous impregnation 2h, dry under same condition, roasting.In catalyst, the load capacity of each component is: Pt 0.7wt%, Sn 1.0wt%, K 1.0wt%.
activation condition:in nitrogen, have 8%(volume/volume) hydrogen, 320 DEG C of constant temperature 2h, then gas composition is changed in nitrogen, have 12%(volume/volume) hydrogen, 320 DEG C of constant temperature 2h.The volume space velocity of reducing gases is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 36%
appreciation condition: catalyst volume 3.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 580 DEG C, hydrogen: the ratio of iso-butane is at 3:1.
result shows: this catalyst is evaluating 120h continuously, and iso-butane conversion ratio is 31.67%, and selective isobutene is 96.76%, and conversion ratio declines 4.2 percentage points, selectively adds 1.3 percentage points, and coke content is only 2.56%, demonstrates good catalytic activity and stability.
Example 3
The method identical according to embodiment 1 prepares dehydrogenation.
activation condition:in nitrogen, have 5%(volume/volume) hydrogen, 350 DEG C of constant temperature 2h, then gas composition is changed in nitrogen, have 18%(volume/volume) hydrogen, 350 DEG C of constant temperature 1h.The volume space velocity of reducing gases is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 38%
appreciation condition: catalyst volume 3.0ml, volume space velocity 2000 h
-1, reaction pressure 0.1MPa, reaction temperature is 590 DEG C, hydrogen: the ratio of iso-butane is at 2:1.
evaluation result: this catalyst is after continuously evaluating 30h, and iso-butane conversion ratio is 40.12%, and selective isobutene is 96.24%, conversion ratio and selective substantially constant, and coke content is only 0.66%, demonstrates good catalytic activity and stability.
Claims (9)
1. one kind adopts the method for low-concentration hydrogen low-temperature reduction activation of dehydrogenation catalyst, it is characterized in that comprising following content: dehydrogenation is platinum family loaded catalyst, dehydrogenation adopts low-concentration hydrogen to carry out low-temperature reduction activation before use, reducing gas is the mixture of nitrogen and hydrogen, wherein the volume content of hydrogen is 1% ~ 20%, low-temperature reduction temperature is 240 ~ 400 DEG C, recovery time is 1.0 ~ 8.0h, then 550 ~ 650 DEG C are warmed up to, cancel sulfuration passivation, the unstripped gas directly passing into hydrogen carries out dehydrogenation reaction, wherein, described platinum group metal is platinum, the 0.01%-2% that its content is is vehicle weight in element active component.
2. in accordance with the method for claim 1, it is characterized in that: after dehydrogenation reduction, the reduction degree of Pt reaches 20% ~ 40%.
3. in accordance with the method for claim 1, it is characterized in that: dehydrogenation reduction activation process first in a nitrogen atmosphere, temperature is raised to 240 ~ 400 DEG C, then gas composition is changed into the reducing gases containing 1% ~ 10% hydrogen in nitrogen, at 240 ~ 400 DEG C of constant temperature reduction 1 ~ 5h; Again gas composition is changed into the hydrogen containing 10% ~ 20% in nitrogen, at 240 ~ 400 DEG C of constant temperature reduction 0.5 ~ 4h.
4. in accordance with the method for claim 1, it is characterized in that: dehydrogenation reduction activation process first in a nitrogen atmosphere, temperature is raised to 240 ~ 400 DEG C, then gas composition is changed into the reducing gases containing 4% ~ 8% hydrogen in nitrogen, at 240 ~ 400 DEG C of constant temperature reductase 12 ~ 4h; Again gas composition is changed into the hydrogen containing 10% ~ 20% in nitrogen, at 240 ~ 400 DEG C of constant temperature reduction 1 ~ 3h.
5. according to the method described in claim 1 or 2, it is characterized in that: containing auxiliary agent in dehydrogenation, auxiliary agent is one or more in Sn, K, rare earth metal.
6. in accordance with the method for claim 5, it is characterized in that: containing auxiliary agent in dehydrogenation, auxiliary agent is one or more in Sn, K, La.
7. in accordance with the method for claim 6, it is characterized in that: in dehydrogenation, the content of auxiliary agent Sn or La counts 0.1% ~ 10% of vehicle weight with element, and the content of auxiliary agent K counts 0.1% ~ 10% of vehicle weight with element.
8. in accordance with the method for claim 1, it is characterized in that: dehydrogenation reaction temperature is 500 ~ 650 DEG C, volume space velocity is 500 ~ 5000h
-1, absolute pressure 0.1 ~ 0.5MPa, unstripped gas is low-carbon alkanes, hydrogen: the molar ratio of low-carbon alkanes is between 1:1 ~ 6:1.
9. in accordance with the method for claim 8, it is characterized in that: low-carbon alkanes is C
2~ C
5alkane.
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| CN1130101A (en) * | 1994-11-29 | 1996-09-04 | 底古萨股份公司 | C6-15Catalyst for dehydrogenation of paraffin |
| EP1182180A1 (en) * | 2000-08-23 | 2002-02-27 | Institut Francais Du Petrole | Process for the dehydrogenation of organic compounds in the presence of a bimetallic 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 |
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| 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 |
| EP1182180A1 (en) * | 2000-08-23 | 2002-02-27 | Institut Francais Du Petrole | Process for the dehydrogenation of organic compounds in the presence of a bimetallic 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 |
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| Title |
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| 助剂对Pt/γ-A12O3催化剂丙烷脱氢性能的影响;余长林等;《石油化工》;20061231;第35卷(第3期);第217-220页 * |
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