CN102909014B - Method for the reductive activation of dehydrogenation catalyst by using synthesis gas - Google Patents

Method for the reductive activation of dehydrogenation catalyst by using synthesis gas Download PDF

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CN102909014B
CN102909014B CN201110217422.0A CN201110217422A CN102909014B CN 102909014 B CN102909014 B CN 102909014B CN 201110217422 A CN201110217422 A CN 201110217422A CN 102909014 B CN102909014 B CN 102909014B
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reduction
temperature
accordance
catalyst
synthesis gas
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CN102909014A (en
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李江红
张海娟
王振宇
张喜文
孙潇磊
宋喜军
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention discloses a method for the reductive activation of a dehydrogenation catalyst by using a synthesis gas. The dehydrogenation catalyst is a platinum group metal-supported catalyst. The reductive activation of the dehydrogenation catalyst is performed before use. The synthesis gas is used as a reducing gas for the reductive activation, a reductive activation temperature is from 300 DEG C to 600 DEG C, the reductive activation time is from 0.5 hours to 10.0 hours, and the volume hourly space velocity of the reducing gas during the reductive activation is 500- 5000h<-1>. Compared with the prior art, the method of the present invention further improves the activity stability of the catalyst.

Description

With the method for synthesis gas reduction activation dehydrogenation
Technical field
The invention relates to a kind of reduction activation method of reduction activation method of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, particularly C3 ~ C5 dehydrating alkanes alkene catalyst.
Background technology
Since entering the new century, worldwide petrochemical raw material and petroleum chemicals demand will sustainable growths, continuation increases by the demand as petrochemical industry basic material propylene and butylene, and the steam cracking of routine and FCC technology production capacity can not meet the demand increased fast, what that its market is occurred is global is in short supply.And day by day deficient along with petroleum resources, the production of propylene has been that raw material changes to the diversified technology path of raw material sources from the simple oil that relies on, is particularly the technology path of waste alkene with low-carbon alkanes.In recent years, the technology that dehydrogenating propane produces propylene achieved large development, and particularly the technology of dehydrogenating propane (PDH) propylene processed had the regional development of resources advantage comparatively fast in recent years in the Middle East etc., became the third-largest propylene production.
Propane catalytic dehydrogenating reaction limits by thermodynamical equilibrium, must carry out under the harsh conditions of high temperature, low pressure.Too high reaction temperature, makes Deposition During Propane Pyrolysis react 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 conversion of propane and harsh reaction condition, PDH method is restricted 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.Current dehydrogenating propane technology with the Catafin technique of the Oleflex technique of Uop Inc. and Air Product company of the U.S. for representative.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 catalyst, must use hydrogen reducing before use, and the catalyst after reduction is used for dehydrogenation reaction.In this kind of catalyst, reduction adopts constant temperature reduction, and temperature is at 400 ~ 650 DEG C.CN101138734A, CN101015802A be constant temperature reductase 12 ~ 10h, CN1844324A constant temperature reduction 7h, CN101108362A preferably constant temperature reduction 4 ~ 6h at 450 ~ 550 DEG C at 400 DEG C in 400 ~ 600 DEG C of hydrogen streams.Reduction can make the active component of catalyst become elemental metals state, metal component Granular composite can also be guaranteed, but constant temperature fast restore at relatively high temperatures, easily cause the sintering of metallic particles, make the catalyst metal particles after reduction bigger than normal, cause the surface area of the simple substance Pt come out less than normal, finally make the activity and selectivity of catalyst lower.The water using pure hydrogen reduction to generate or OH -add the transfer ability of metallic atom or metallic compound, easily cause catalyst activity accumulation of metal.CN200410096308.7 is under temperature is 240 ~ 550 DEG C of conditions, molecular sieve, noble metal catalyst are contacted 5 ~ 30 hours with hydrogen with the gaseous mixture of ammonia, while reduction, strong acid center conductively-closed in molecular sieve, this method is not suitable for the reduction process of lower carbon number hydrocarbons dehydrogenation yet.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of reducing of catalyst for dehydrogenation of low-carbon paraffin, improve object product yield further on the basis of existing technology, improve the selective of catalyst simultaneously.
The present invention comprises following content with the method for synthesis gas reduction activation dehydrogenation: dehydrogenation is platinum family loaded catalyst, dehydrogenation carries out reduction activation before use, reduction activation take synthesis gas as reducing gases, reduction activation temperature is 300 ~ 600 DEG C, be preferably 350 ~ 550 DEG C, the reduction activation time is 0.5 ~ 10.0 hour, and be preferably 1 ~ 5 hour, during reduction activation, the volume space velocity (the reducing gases volume computing with under standard state) of reducing gases is for 500 ~ 5000h -1.
In the inventive method, synthesis gas can be the synthesis gas in source arbitrarily, based on carbon monoxide and hydrogen in synthesis gas, simultaneously containing the component such as carbon dioxide, nitrogen, synthesis gas can be vaporized by the solid fuel such as coal or coke and be produced, also can be produced by the light hydrocarbons such as natural gas and naphtha, also can be produced through partial oxidation process by heavy oil.In the inventive method, require H in synthesis gas 2: the volume ratio of CO gas is 0.6:1.0 ~ 8.0:1.0, preferred H 2: the volume ratio of CO gas is 1.0:1.0 ~ 6.0:1.0, wherein H 2be 60% ~ 98% of synthesis gas with the volume content of CO gas.Synthesis gas can directly use, and uses after also can adjusting composition.
In the inventive method, reduction activation can adopt one of following two kinds of modes: (1) constant temperature reduction activation process, (2) first temperature programmed reduction then adopt constant temperature to reduce in conjunction with reduction activation process.In mode (1), be directly warmed up to the reduction of reduction temperature constant temperature, reduction temperature is 350 ~ 600 DEG C, preferably 400 ~ 550 DEG C, and the preferred recovery time is 0.5 ~ 10.0 hour.In mode (2), temperature programmed reduction is the operation of arbitrary temp section in 300 ~ 600 DEG C, preferably arbitrary temp section operation in 350 ~ 550 DEG C, heating rate 0.5 ~ 10 DEG C/min, preferably 0.5 ~ 5 DEG C/min, the temperature programming time is 15 ~ 90min, is preferably 20 ~ 40min; Then under temperature programming end temp, constant temperature reduces 0.5 ~ 5.0 hour.Temperature programmed reduction refers to that the programming rate by controlling heats up, and passes into the reduction activation method that reducing gases carries out catalyst while intensification.
Dehydrogenation after reduction activation, generally need to use the mist of hydrogen, hydrogen sulfide and nitrogen to carry out sulfuration, can carry out dehydrogenation reaction after sulfuration, vulcanization process can adopt this area routine techniques.Dehydrogenation reaction raw material is generally propane or butane, obtains propylene or butylene through dehydrogenation.
In dehydrogenation method of reducing of the present invention, dehydrogenation is platinum family loaded catalyst, and with one or more in the platinum in platinum family, palladium, iridium, rhodium or osmium for active component, 0.01% ~ 2% of vehicle weight is counted with simple substance in the catalyst in platinum group metal.Suitable auxiliaries can be contained, as IV A race element, alkali metal, thulium etc. in dehydrogenation simultaneously.IV A race element is preferably Sn, and its content counts 0.1% ~ 10% of vehicle weight with element, and alkali metal content counts 0.1% ~ 10% of vehicle weight with element.In finished catalyst, active metal and auxiliary agent preferably exist with the form of oxidation state, dehydrogenation can adopt the method for this area routine to prepare, as adopted infusion process load dehydrogenation active component, auxiliary agent and/or can adopt infusion process to introduce in carrier preparation process.
Catalyst carrier of the present invention is selected from high-temperature inorganic oxide, is generally the material that a kind of porous has adsorptivity.The composition of porous carrier should be uniform, and is infusibility under the conditions employed.Resistant to elevated temperatures inorganic oxide comprises: aluminium oxide, magnesia, chromium oxide, boron oxide, titanium oxide, zinc oxide, zirconia, or the mixture of following two oxides; And various pottery, various alumina, silica, synthesis or naturally occurring various silicate or clay.Preferred inorganic oxide carrier is Al 2o 3.Its crystal habit can be γ-Al 2o 3, θ-Al 2o 3, η-Al 2o 3, preferred crystal habit is γ-Al 2o 3.
Platinum group metal in catalyst can adopt co-precipitation, ion-exchange or impregnating mode to introduce carrier.Preferred method is the platinum group metal compounds impregnated carrier adopting water-soluble decomposable.Adoptable water soluble compound or complex are: chloroplatinic acid, chloro-iridic acid, the acid of chlorine palladium, ammonium chloroplatinate, bromoplatinic acid, tri-chlorination platinum, palladium nitrate, diaminourea palladium hydroxide, chlorine four ammonia palladium, chlorine six ammonia palladium, rhodium chloride hydrate, rhodium nitrate, tribromide iridium, iridochloride, iridic chloride, potassium hexachloroiridate or iridium sodium chloride etc.The chlorine-containing compound of preferred platinum, palladium, iridium, rhodium or osmium.
IV A race elemental constituent in catalyst can be adopted to introduce in any way in catalyst and reach component and is uniformly distributed.Suitable soluble compound is its oxide, chloride, nitrate or alkoxide, as stannous chloride, butter of tin, butter of tin pentahydrate, stannous bromide, germanium dioxide, germanium tetrachloride etc.Preferred butter of tin, germanium tetrachloride, most preferably butter of tin.In addition, introduce in the process that IV A race metal component also can be prepared at carrier.
Alkali and alkaline earth metal ions in catalyst can be introduced in catalyst in any known fashion, preferably by the method for the solution impregnating carrier of the water-soluble decomposable compound of alkali metal or alkaline-earth metal.Described alkali metal is preferably K, Na or Li.
Existing dehydrogenation, when reducing, takes traditional H 2reduction, and constant temperature reduction under higher temperature, although this activation method has the sufficient advantage of dehydrogenation activity metallic reducing, the metallic particles after reduction is bigger than normal to be caused selective relatively poor, and along with the carrying out of reaction, activity decrease is very fast, poor stability.In the activation method of dehydrogenation of the present invention, select synthesis gas to be reducing gases, improve reduction degree and the decentralization of catalyst, add the quantity of the active sites of catalyst surface.Adopt the reducing process that combines with constant temperature of temperature programming to carry out reduction activation to catalyst simultaneously, the catalyst metal particles after reduction is disperseed evenly, granular size is more appropriate, the surface area increase of the simple substance Pt come out.Avoid under violent reducing condition, Al 2o 3pt bunch of quick formation on surface also easily assembles the large Pt particle of formation, also some can be avoided not wish, and the adjuvant component reduced is by drastic reduction, have impact on the synergy (synergy particularly between active component Pt and adjuvant component Sn) of auxiliary agent, and then improve the serviceability of catalyst, in particular improve the stability of the selective of object product and long-time reaction.
Detailed description of the invention
Dehydrogenation method of reducing of the present invention adopts synthesis gas to be reducing gases, and the reducing process combined by temperature programming and constant temperature instead of the constant temperature reduction under traditional higher temperature.Dehydrogenation vulcanization process of the present invention preferably adopts the mixed gas of hydrogen sulfide, hydrogen and nitrogen as sulfuration gas.Dehydrogenation take preferably Pt as active component, counts 0.01% ~ 2% of vehicle weight with simple substance; Take Sn as auxiliary agent, the content of Sn counts 0.1% ~ 10% of vehicle weight with simple substance, and auxiliary agent can also comprise K, rare earth metal etc. simultaneously.
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 the ammoniacal liquor that appropriate mass concentration is 8%, 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 0.3wt%.
By the alumina globule carrier containing 0.3% 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 0.5wt%, Sn 0.3wt%, K 0.5wt%.
reducing condition:at 350 ~ 480 DEG C of scope internal program heating reductions, heating rate is 2 DEG C/min, then at 480 DEG C of constant temperature reduction 30min.In reduction process, the volume space velocity of reducing gases is 1500h -1, H in synthesis gas 2: the ratio of CO gas is 3.0:1.0, wherein H 2be 90% of synthesis gas with the volume content of CO gas.
conditions of vulcanization: the mass velocity 900h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen -1, molar ratio is 1:9:5, temperature 480 DEG C, cure time 40min.
appreciation condition: volume space velocity 2000 h of mist charging -1, reaction pressure 0.1MPa, reaction temperature is 520 DEG C, hydrogen in charging: the molar ratio of iso-butane is 1:1.Evaluation result is in table 1.
Comparative example
The preparation of catalyst is with example 1.
reducing condition: volume space velocity is 1500h -1, at 480 DEG C of reduction 80min, using high-purity hydrogen as reducing gases.
activation condition:the volume space velocity of the mixed gas of hydrogen sulfide, hydrogen and nitrogen is 900h -1, molar ratio is 1:9:5, temperature 480 DEG C, soak time 40min.
appreciation condition:volume space velocity 2000 h -1, reaction pressure 0.1MPa, reaction temperature is 520 DEG C, hydrogen: the mol ratio of iso-butane is 1:1.Evaluation result is in table 1.
Example 2
The preparation of catalyst is with example 1.
reducing condition:at 300 ~ 450 DEG C of scope internal program heating reductions, heating rate is 2.5 DEG C/min, then at 450 DEG C of constant temperature reduction 40min.In reduction process, the volume space velocity of reducing gases is 1500h -1, H in synthesis gas 2: the ratio of CO gas is 3.5:1.0, wherein H 2be 90% of synthesis gas with the volume content of CO gas.
conditions of vulcanization: the mass velocity 900h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen -1, molar ratio is 1:9:5, temperature 480 DEG C, cure time 40min.
appreciation condition: volume space velocity 2000 h of mist charging -1, reaction pressure 0.1MPa, reaction temperature is 520 DEG C, hydrogen: the molar ratio of iso-butane is 1:1.Evaluation result is in table 1.
Example 3
The preparation of catalyst is with example 1.
reducing condition:at 350 ~ 480 DEG C of scope internal program heating reductions, heating rate is 5.0 DEG C/min, then at 480 DEG C of constant temperature reduction 50min.In reduction process, the volume space velocity of reducing gases is 2500h -1, H in synthesis gas 2: the ratio of CO gas is 4.0:1.0, wherein H 2be 85% of synthesis gas with the volume content of CO gas.
conditions of vulcanization: the mass velocity 900h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen -1, molar ratio is 1:9:5, temperature 480 DEG C, cure time 40min.
appreciation condition: volume space velocity 2000 h of mist charging -1, reaction pressure 0.1MPa, reaction temperature is 520 DEG C, hydrogen: the molar ratio of iso-butane is 1:1.Evaluation result is in table 1.
Example 4
The preparation of catalyst is with example 1.
reducing condition:at 350 ~ 450 DEG C of scope internal program heating reductions, heating rate is 1.0 DEG C/min, then at 450 DEG C of constant temperature reduction 10min.In reduction process, the volume space velocity of reducing gases is 800h -1, synthesis gas H 2: the ratio of CO gas is 2.5:1.0, wherein H 2be 97% of synthesis gas with the volume content of CO gas.
conditions of vulcanization: the mass velocity 900h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen -1, molar ratio is 1:9:5, temperature 480 DEG C, cure time 40min.
appreciation condition: volume space velocity 2000 h of mist charging -1, reaction pressure 0.1MPa, reaction temperature is 520 DEG C, hydrogen in charging: the molar ratio of iso-butane is 1:1.Evaluation result is in table 1.
Example 5
The preparation of catalyst is with example 1.
reducing condition:at 480 DEG C of constant temperature reduction 90min.In reduction process, the volume space velocity of reducing gases is 1500h -1, H in synthesis gas 2: the ratio of CO gas is 6.0:1.0, wherein H 2be 75% of synthesis gas with the volume content of CO gas.
conditions of vulcanization: the mass velocity 900h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen -1, molar ratio is 1:9:5, temperature 480 DEG C, cure time 40min.
appreciation condition: volume space velocity 2000 h of mist charging -1, reaction pressure 0.1MPa, reaction temperature is 520 DEG C, hydrogen in charging: the molar ratio of iso-butane is 1:1.Evaluation result is in table 1.
Table 1 evaluation result.
Initial stage iso-butane conversion ratio % Initial stage selective isobutene % Latter stage iso-butane conversion ratio % Latter stage selective isobutene %
Embodiment 1 37.6 97.8 35.9 97.4
Embodiment 2 37.3 97.9 35.8 97.5
Embodiment 3 37.1 97.9 35.8 97.6
Embodiment 4 36.8 98.1 35.8 97.9
Embodiment 5 37.0 97.2 35.1 97.5
Comparative example 35.7 97.6 31.4 96.8
Initial stage: the reaction time is 4 hours
Latter stage: the reaction time is 50 hours
Conversion ratio and selective in mole.
As can be seen from the evaluation result of table 1, adopt method of reducing process dehydrogenation provided by the invention, dehydrogenation has good activity, particularly still maintains higher activity and selectivity through long stream catalyst, substantially increases the stability of catalyst.

Claims (12)

1. one kind with the method for synthesis gas reduction activation dehydrogenation, comprise following content: dehydrogenation is platinum family loaded catalyst, dehydrogenation carries out reduction activation before use, it is characterized in that: reduction activation take synthesis gas as reducing gases, reduction activation temperature is 300 ~ 600 DEG C, the reduction activation time is 0.5 ~ 10.0 hour, and during reduction activation, the volume space velocity of reducing gases is 500 ~ 5000h -1;
H in synthesis gas 2: the volume ratio of CO gas is 0.6:1.0 ~ 8.0:1.0, wherein H 2be 60% ~ 98% of synthesis gas with the volume content of CO gas.
2. in accordance with the method for claim 1, it is characterized in that: reduction activation temperature is 350 ~ 550 DEG C.
3. in accordance with the method for claim 1, it is characterized in that: the reduction activation time is 1 ~ 5 hour.
4. in accordance with the method for claim 1, it is characterized in that: H in synthesis gas 2: the volume ratio of CO gas is 1.0:1.0 ~ 6.0:1.0.
5. in accordance with the method for claim 1, it is characterized in that: reduction activation adopts constant temperature reduction activation process.
6. in accordance with the method for claim 5, it is characterized in that: constant temperature reduction activation process is for being directly warmed up to the reduction of reduction temperature constant temperature, and reduction temperature is 350 ~ 600 DEG C, and the recovery time is 0.5 ~ 10.0 hour.
7. in accordance with the method for claim 6, it is characterized in that: described reduction temperature is 400 ~ 550 DEG C.
8. in accordance with the method for claim 1, it is characterized in that: reduction activation adopt first temperature programmed reduction then to adopt constant temperature to reduce in conjunction with reduction activation process, temperature programmed reduction refers to that the programming rate by controlling heats up, and passes into the reduction activation method that reducing gases carries out catalyst while intensification.
9. in accordance with the method for claim 8, it is characterized in that: temperature programmed reduction is the operation of arbitrary temp section in 300 ~ 600 DEG C, heating rate 0.5 ~ 10 DEG C/min, and the temperature programming time is 15 ~ 90min; Then under temperature programming end temp, constant temperature reduces 0.5 ~ 5.0 hour.
10. in accordance with the method for claim 9, it is characterized in that: temperature programmed reduction is the operation of arbitrary temp section in 350 ~ 550 DEG C.
11. in accordance with the method for claim 9, it is characterized in that: temperature programmed reduction is the operation of arbitrary temp section in 350 ~ 550 DEG C, and heating rate is 0.5 ~ 5 DEG C/min, and the temperature programming time is 20 ~ 40min.
12. 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, 0.01% ~ 2% of vehicle weight is counted with simple substance in the catalyst in platinum group metal, count 0.1% ~ 10% of vehicle weight containing auxiliary agent Sn, auxiliary agent Sn content with element simultaneously.
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