CN102909096B - Dehydrogenation catalyst activation method combining high-temperature reduction of short duration with low-temperature reduction - Google Patents
Dehydrogenation catalyst activation method combining high-temperature reduction of short duration with low-temperature reduction Download PDFInfo
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Abstract
The present invention discloses a dehydrogenation catalyst activation method combining high-temperature reduction of short duration with low-temperature reduction. The dehydrogenation catalyst is a platinum group metal-supported catalyst. The activation method comprises: performing the high-temperature reduction at first; then performing the low temperature reduction; wherein hydrogen gas is used in the high temperature reduction at a temperature of 450-550 DEG C for 5-55min, nitrogen-hydrogen mixed gas is used in the low-temperature reduction, with a volume content of the hydrogen gas being 2% to 20%, the low-temperature reduction temperature being 240-400 DEG C, and low-temperature reduction time being 1-8h; adjusting the temperature to 500-650 DEG C after the reduction is finished; omitting the process of sulfuration passivation and directly feeding a hydrogen-containing feed gas for the dehydrogenation reaction. Compared with the prior art, the dehydrogenation catalyst reduced and activated by the method of the invention has a higher activity stability.
Description
Technical field
The invention relates to 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 pure hydrogen constant temperature to reduce for a long time, and low-temperature reduction does not generally reach the reduction degree of depth, and therefore the long-time reduction temperature of constant temperature is generally 400 ~ 650 DEG C, carries out Passivation 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.In High Purity Hydrogen air-flow, constant temperature reduces for a long time, 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 sulfuration 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.
Short time high temperature of the present invention reduction, in conjunction with the dehydrogenation catalyst activation method of low-temperature reduction, comprises following content: dehydrogenation is platinum family loaded catalyst, and activation method comprises and first carries out high temperature reduction, then carries out low-temperature reduction; High temperature reduction adopts hydrogen 450 ~ 550 DEG C time, reduce 5 ~ 55min, preferably 10 ~ 40min; Low-temperature reduction adopts nitrogen hydrogen-hydrogen gas mixture, and wherein hydrogen volume content is 2% ~ 20% preferably 5% ~ 15%, and low-temperature reduction temperature is 240 ~ 400 DEG C and is preferably 300 ~ 400 DEG C, and the low-temperature reduction time is 1 ~ 8h preferably 2 ~ 5h; After reduction terminates, temperature is adjusted to 500 ~ 650 DEG C, cancel sulfuration passivation, the unstripped gas directly passing into hydrogen carries out dehydrogenation reaction.
In the inventive method, dehydrogenation before use by traditional High Purity Hydrogen air-flow constant temperature reduce for a long time change into the constant temperature short time reduce after, reduce the temperature to 240 ~ 400 DEG C, control the concentration constant temperature reduction certain hour of hydrogen in reducing gases, the reduction degree of Pt in catalyst is made to reach 30% ~ 50%, avoid dehydrogenation activity metal depth to reduce the catalyst activity accumulation of metal initial activity caused and cross the not high phenomenon of high stability, also some can be avoided not wish, and the adjuvant component reduced is by drastic reduction, have impact on the synergy of auxiliary agent.Control the reduction degree that active component Pt is certain, catalyst is reduced further in course of reaction, reaches active slow releasing to increase the object of catalyst stability.
In the inventive method, the purity of hydrogen that high temperature reduction adopts is at least more than 90% (volume), and preferably more than 95%.High temperature reduction and low-temperature reduction process adopt constant temperature restoring operation.
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, activity is given to divide and is comprised platinum, be vehicle weight in element active component 0.01% ~ 2%.Simultaneously can contain suitable auxiliaries in dehydrogenation, as in Sn, La, K, rare earth metal etc. one or more, the content of Sn or La counts 0.1% ~ 10%, K of vehicle weight content with simple substance 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 the long-time method of reducing of constant temperature in hydrogen stream more, although this activation method has the advantage that dehydrogenation activity metallic reducing is abundant and initial reaction activity is high, but stability is relatively poor, 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, do not carry out conventional restoring operation, after adopting high temperature pure hydrogen constant temperature reduction certain hour, lower temperature control density of hydrogen constant temperature reduction certain hour is to control the reduction degree of 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 sulfuration 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 and change temperature section reduction 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 take preferably Pt as active component, and with Sn or La for 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 element.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 and sulphur 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 element;
(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) after the catalyst that step (4) obtains adopts hydrogen to control the constant temperature recovery time, reduce the temperature to 240 ~ 400 DEG C, control the concentration cryogenic thermostat reduction of hydrogen in reducing gases, the high temperature pure hydrogen constant temperature recovery time is at 10 ~ 60min.Concentration 2% ~ the 20%(vol of hydrogen in cryogenic thermostat reduction), all the other are nitrogen.
(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%.
High temperature constant temperature reducing condition described in step (5) is temperature is 450 ~ 550 DEG C.In low-temperature reduction gas, the concentration of hydrogen is 2 ~ 20vol%, preferably 5 ~ 15vol%.Other condition of reduction is: the volume space velocity of reducing gases is 500 ~ 5000h
-1, absolute pressure 0.1 ~ 0.5MPa.
Dehydrogenation reaction conditions described in step (6) is: reaction temperature 500 ~ 650 DEG C, volume space velocity (hydrogen and unstripped gas sum, unstripped gas is 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 lower carbon number hydrocarbons 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 500 DEG C, hydrogen 500 DEG C of constant temperature reductase 12 0min, nitrogen protection borehole cooling, to 350 DEG C, then has 10%(volume in nitrogen) hydrogen, 350 DEG C of constant temperature 2h, in activation process, the volume space velocity of reducing gases is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 36%.
appreciation condition: catalyst volume 2.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 580 DEG C, hydrogen: the molar ratio of iso-butane is at 2:1.
result shows: this catalyst is evaluating 48h continuously, and iso-butane conversion ratio is 38.58%, and selective isobutene is 95.45%, 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, is reduced for a long time unlike constant temperature in 500 DEG C of flow of pure hydrogen and is obtained catalyst.
activation condition:500 DEG C of Cheng Hengwen reduction 3h in High Purity Hydrogen air-flow, the volume space velocity of reducing gases is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 92%
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, temperature 500 DEG C, passivation time 1h.
appreciation condition: catalyst volume 2.0ml, 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 34.2%, and selective isobutene is 95.5%, and conversion ratio declines 4.2 percentage points, selective rising 0.6 percentage point, 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:first be warming up in a nitrogen atmosphere 500 DEG C, high-purity hydrogen 500 DEG C of constant temperature reduction 40min, nitrogen protection borehole cooling is to 300 DEG C; in nitrogen, have 5%(volume) hydrogen; 300 DEG C of constant temperature 0.5h, then gas composition is changed in nitrogen, have 12%(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 43%.
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 1:1.
result shows: this catalyst is evaluating 72h continuously, and iso-butane conversion ratio is 37.27%, and selective isobutene is 96.56%, and conversion ratio declines 1.5 percentage points, selectively adds 0.8 percentage point, and coke content is only 2.06%, demonstrates good catalytic activity and stability.
Example 3
The method identical according to embodiment 1 prepares dehydrogenation.
activation condition:first be warming up in a nitrogen atmosphere 500 DEG C, high-purity hydrogen 500 DEG C of constant temperature reduction 30min, nitrogen protection borehole cooling, to 400 DEG C, has 6%(volume in nitrogen) hydrogen, 400 DEG C of constant temperature 2h, in activation process, 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 24h, and iso-butane conversion ratio is 39.62%, and selective isobutene is 95.68%, conversion ratio and selective substantially constant, and coke content is only 0.88%, demonstrates good catalytic activity and stability.
Claims (10)
1. short time high temperature reduction is in conjunction with the dehydrogenation catalyst activation method of low-temperature reduction, it is characterized in that: dehydrogenation is platinum family loaded catalyst, activation method comprises and first carries out high temperature reduction, high temperature reduction adopts hydrogen 450 ~ 550 DEG C time, reduce 5 ~ 55min, and the purity of hydrogen is by volume of more than 90%; Then carry out low-temperature reduction, low-temperature reduction adopts nitrogen-hydrogen mist, and wherein hydrogen volume content is 2% ~ 20%, and low-temperature reduction temperature is 240 ~ 400 DEG C, and the low-temperature reduction time is 1 ~ 8h; After reduction terminates, temperature is adjusted to 500 ~ 650 DEG C, cancel sulfuration passivation, the unstripped gas directly passing into hydrogen carries out dehydrogenation reaction.
2. in accordance with the method for claim 1, it is characterized in that: dehydrogenation is platinum family loaded catalyst, with one or more in the platinum in platinum family, palladium, iridium, rhodium or osmium for active component.
3. in accordance with the method for claim 2, it is characterized in that: active component is platinum, be vehicle weight in element active component 0.01% ~ 2%.
4. in accordance with the method for claim 3, it is characterized in that: after reduction, in dehydrogenation, the reduction degree of platinum is 30% ~ 50%.
5. in accordance with the method for claim 1, it is characterized in that: high temperature reduction and low-temperature reduction process adopt constant temperature restoring operation.
6. in accordance with the method for claim 1, it is characterized in that: the high temperature reduction time is 10 ~ 40min.
7. in accordance with the method for claim 1, it is characterized in that: low-temperature reduction adopts nitrogen-hydrogen mist, and wherein hydrogen volume content is 5% ~ 15%.
8. according to the method described in claim 1 or 6, it is characterized in that: low-temperature reduction temperature is 300 ~ 400 DEG C, the low-temperature reduction time is 2 ~ 5h.
9. in accordance with the method for claim 2, it is characterized in that: dehydrogenation contains one or more in auxiliary agent Sn, La, K, rare earth metal, the content of Sn or La counts 0.1% ~ 10%, K of vehicle weight content with element counts 0.1% ~ 10% of vehicle weight with element.
10. in accordance with the method for claim 1, it is characterized in that: dehydrogenation reaction temperature 500 ~ 650 DEG C, in hydrogen and unstripped gas sum, volume space velocity 500 ~ 5000h
-1, absolute pressure 0.1 ~ 0.5MPa, hydrogen: the molar ratio of low-carbon alkanes is between 1:1 ~ 6:1.
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2011
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