CN102909093B - Method for stepwise activating dehydrogenation catalyst by using CO-containing gas and hydrogen gas - Google Patents

Method for stepwise activating dehydrogenation catalyst by using CO-containing gas and hydrogen gas Download PDF

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CN102909093B
CN102909093B CN201110217507.9A CN201110217507A CN102909093B CN 102909093 B CN102909093 B CN 102909093B CN 201110217507 A CN201110217507 A CN 201110217507A CN 102909093 B CN102909093 B CN 102909093B
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hydrogen
temperature
dehydrogenation
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CN102909093A (en
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李江红
张海娟
孙潇磊
王振宇
张喜文
宋喜军
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention discloses a method for stepwise activating a dehydrogenation catalyst by using a CO-containing gas and hydrogen gas. The dehydrogenation catalyst is a platinum group metal-supported catalyst. The reductive activation of the dehydrogenation catalyst is performed before use. The reductive activation process includes a reductive activation procedure by using the CO-containing gas the reducing gas, and a reductive activation procedure by using hydrogen as the reducing gas. The reductive activation temperature is 300-600 DEG C, the total reductive activation time is 0.5-10.0 hours, the time that using the CO-containing gas as the reducing gas accounts for 20% to 80% of the total reductive activation time, 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 enhances the catalyst activity stability of the dehydrogenation catalyst for light alkanes.

Description

With the method containing CO gas and hydrogen segmentation activation of dehydrogenation catalyst
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 segmentation reduction activation method of catalyst for dehydrogenation of low-carbon paraffin, both ensure that the conversion ratio of object product turn improved the activity stability of the selective of object product and long-time reaction.
The present invention is to comprise following content containing the method for CO gas and hydrogen segmentation activation of dehydrogenation catalyst: dehydrogenation is platinum family loaded catalyst, dehydrogenation carries out reduction activation before use, reduction activation process comprises carrying out reduction activation process containing CO gas for reducing gases, and is that reducing gases carries out reduction activation process with hydrogen.Reduction activation temperature is 300 ~ 600 DEG C, be preferably 350 ~ 550 DEG C, total reduction activation time is 0.5 ~ 10.0 hour, be preferably 1 ~ 5 hour, the time of carrying out reduction activation for reducing gases to contain CO gas is 20% ~ 80% of total reduction activation time, be preferably 30% ~ 60%, 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, can be pure CO gas containing CO gas, also can be the mist of CO and carrier gas, carrier gas be nitrogen or inert gas, and inert gas is as helium, neon, argon gas etc.The mist of preferred use CO and carrier gas, wherein CO generally accounts for 5% ~ 60% of mist volume.
In the inventive method, reduction activation process can adopt constant temperature to reduce or the associated methods of constant temperature reduction after temperature programmed reduction or first temperature programmed reduction.The associated methods of constant temperature reduction after preferred first temperature programmed reduction.Temperature programmed reduction and constant temperature reduce in conjunction with time, both recovery time ratios can be any.Most preferably to contain CO gas for adopting temperature programmed reduction during reducing gases, when taking hydrogen as reducing gases, adopt constant temperature reduction.Temperature programmed reduction process is generally: arbitrary temp section operation 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.Temperature programmed reduction refers to that the programming rate by controlling heats up, and passes into the method that reducing gases carries out catalyst reduction activation while intensification.
In the inventive method, dehydrogenation can carry out pretreatment before reduction activation, pretreatment carries out pretreatment at 250 ~ 400 DEG C with hydrogen, pretreatment also can adopt temperature programming process for constant temperature process, the heating rate of temperature programming is 0.5 ~ 5 DEG C/min, pretreatment total time is 0.5 ~ 3 hour, and pretreatment hydrogen volume air speed is 500 ~ 5000h -1.
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 the inventive method, 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 is when reducing, conventional hydrogen is taked to reduce, and constant temperature reduction under higher temperature, although this activation method has the sufficient advantage of dehydrogenation activity metallic reducing, but reduction after metallic particles bigger than normal cause selective relatively poor, and, along with reaction carrying out, activity decrease is very fast, and activity stability is poor.In the activation method of dehydrogenation of the present invention, to select containing CO gas and hydrogen as reducing gases, segmentation reduction is carried out to dehydrogenation.Not only dehydrogenation activity metallic reducing is abundant, and the specific area of catalyst increases, and improves the anticoking capability of dehydrogenation, reduces the coking rate of dehydrogenation.Both ensure that the conversion ratio of object product turn improved the activity stability of the selective of object product and long-time reaction.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 of the present invention reduction adopts the method for segmentation reduction, respectively with containing CO gas and hydrogen for reducing gases, the reducing process combined by temperature programming and constant temperature instead of the constant temperature reduction under traditional higher temperature.
Dehydrogenation of the present invention 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:first at 380 DEG C ~ 480 DEG C scope internal program heating reductions, reducing gases CO accounts for 20% of gaseous mixture gas volume, using nitrogen as carrier gas.Heating rate is 2 DEG C/min, then under 480 DEG C of constant temperatures, take hydrogen as reducing gases, reduction 40min.In reduction process, the volume space velocity of reducing gases is 2000h -1.
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 560 DEG C, hydrogen in charging: the molar ratio of propane 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 2000h -1, at 480 DEG C of reduction 90min, using pure hydrogen as reducing gases.
conditions of vulcanization: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:feed volume air speed 2000 h -1, reaction pressure 0.1MPa, reaction temperature is 560 DEG C, feed hydrogen: the mol ratio of propane is 1:1.Evaluation result is in table 1.
Example 2
The preparation of catalyst is with example 1.
reducing condition:first at 400 DEG C ~ 480 DEG C scope internal program heating reductions, reducing gases CO accounts for 30% of gaseous mixture gas volume, using nitrogen as carrier gas.Heating rate is 1 DEG C/min, then under 480 DEG C of constant temperatures, take hydrogen as reducing gases, reduction 30min.In reduction process, the volume space velocity of reducing gases is 800h -1,
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 560 DEG C, hydrogen in charging: the molar ratio of propane is 1:1.Evaluation result is in table 1.
Example 3
The preparation of catalyst is with example 1.
reducing condition: firstat 380 DEG C ~ 500 DEG C scope internal program heating reductions, reducing gases CO accounts for 40% of gaseous mixture gas volume, using nitrogen as carrier gas.Heating rate is 5 DEG C/min, then lowers the temperature under 480 DEG C of constant temperatures, take hydrogen as reducing gases, reduction 60min.In reduction process, the volume space velocity of reducing gases is 2000h -1,
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 560 DEG C, feed hydrogen: the molar ratio of propane is 1:1.Evaluation result is in table 1.
Example 4
The preparation of catalyst is with example 1.
reducing condition: firstat 350 DEG C ~ 420 DEG C scope internal program heating reductions, heating rate is that 2 DEG C/min, reducing gases CO account for 10% of gaseous mixture gas volume, using nitrogen as carrier gas.Then at 420 ~ 480 DEG C of scope internal program heating reductions, heating rate is 2 DEG C/min, and reducing gases is hydrogen.Last take hydrogen as reducing gases under 480 DEG C of constant temperatures, reductase 12 0min.In reduction process, the volume space velocity of reducing gases is 2000h -1,
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 560 DEG C, hydrogen in charging: the molar ratio of propane is 1:1.Evaluation result is in table 1.
Example 5
The preparation of catalyst is with example 1.
reducing condition: firstat 300 DEG C ~ 480 DEG C scope internal program heating reductions, reducing gases is CO, and heating rate is 3 DEG C/min, then under 480 DEG C of constant temperatures, take hydrogen as reducing gases, reduction 40min.In reduction process, the volume space velocity of reducing gases is 2000h -1.
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 560 DEG C, hydrogen in charging: the molar ratio of propane is 1:1.Evaluation result is in table 1.
Example 6
The preparation of catalyst is with example 1.
reducing condition: firstat 380 DEG C ~ 480 DEG C scope internal program heating reductions, take hydrogen as reducing gases, heating rate is 2 DEG C/min.Then, under 480 DEG C of constant temperatures, reducing gases CO accounts for 20% of gaseous mixture gas volume, using nitrogen as carrier gas, and constant temperature reduction 40min.In reduction process, the volume space velocity of reducing gases is 2000h -1.
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 560 DEG C, hydrogen in charging: the molar ratio of propane is 1:1.Evaluation result is in table 1.
Example 7
The preparation of catalyst is with example 1.
reducing condition: firstat 400 DEG C ~ 520 DEG C scope internal program heating reductions, reducing gases CO accounts for 20% of gaseous mixture gas volume, and using nitrogen as carrier gas, heating rate is 4 DEG C/min.Then, under 520 DEG C of constant temperatures, take hydrogen as reducing gases, reduction 30min.In reduction process, the volume space velocity of reducing gases is 2000h -1.
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 560 DEG C, hydrogen in charging: the molar ratio of propane is 1:1.Evaluation result is in table 1.
Example 8
The preparation of catalyst is with example 1.
reducing condition:first be reducing gases with hydrogen under 380 DEG C of constant temperatures, reductase 12 0 min; Then at 380 ~ 480 DEG C of scope internal program heating reductions, heating rate is that 2 DEG C/min, reducing gases CO account for 20% of gaseous mixture gas volume, using nitrogen as carrier gas.Last take hydrogen as reducing gases under 480 DEG C of constant temperatures, reductase 12 0min.In reduction process, the volume space velocity of reducing gases is 2000h -1.
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 560 DEG C, hydrogen in charging: the molar ratio of propane is 1:1.Evaluation result is in table 1.
Table 1 dehydrogenation evaluation result.
Initial stage conversion of propane % Latter stage conversion of propane % Initial stage Propylene Selectivity % Latter stage Propylene Selectivity %
Embodiment 1 24.9 19.8 92.4 91.8
Embodiment 2 24.1 20.3 92.5 92.3
Embodiment 3 23.2 21.4 92.6 92.4
Embodiment 4 25.2 19.5 91.4 91.4
Embodiment 5 22.8 21.2 93.1 93.0
Embodiment 6 24.7 19.9 92.0 92.0
Embodiment 7 25.3 19.5 91.4 91.2
Embodiment 8 24.3 19.7 91.7 91.6
Comparative example 25.2 15.0 91.8 90.2
The initial reaction time: 2 hours, react after 3 hours, the conversion of propane of comparative example is lower than embodiment 1.
Reaction time in latter stage: 40 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 keeps active preferably, improves the stability of long-time reaction simultaneously.

Claims (12)

1. one kind with the method containing CO gas and hydrogen segmentation activation of dehydrogenation catalyst, dehydrogenation is platinum family loaded catalyst, dehydrogenation carries out reduction activation before use, it is characterized in that: 0.01% ~ 2% of vehicle weight is counted with simple substance in the catalyst in platinum group metal, simultaneously containing auxiliary agent Sn, auxiliary agent Sn content counts 0.1% ~ 10% of vehicle weight with element, reduction activation process comprises carrying out reduction activation process containing CO gas for reducing gases, and is that reducing gases carries out reduction activation process with hydrogen; Reduction activation temperature is 300 ~ 600 DEG C, and total reduction activation time is the time of carrying out reduction activation to contain CO gas for reducing gases in 0.5 ~ 10.0 hour is 20% ~ 80% of total reduction activation time, and during reduction activation, the volume space velocity of reducing gases is 500 ~ 5000h -1.
2. in accordance with the method for claim 1, it is characterized in that: described reduction activation temperature is 350 ~ 550 DEG C, total reduction activation time is 1 ~ 5 hour, is 30% ~ 60% of total reduction activation time with the time of carrying out reduction activation for reducing gases containing CO gas.
3. in accordance with the method for claim 1, it is characterized in that: be pure CO gas containing CO gas, or the mist of CO and carrier gas, carrier gas is nitrogen or inert gas.
4. in accordance with the method for claim 3, it is characterized in that: the mist containing CO gas being CO and carrier gas, wherein CO accounts for 5% ~ 60% of mist volume.
5. in accordance with the method for claim 1, it is characterized in that: reduction activation process adopts the associated methods of constant temperature reduction after constant temperature reduction or temperature programmed reduction or first temperature programmed reduction.
6. in accordance with the method for claim 5, it is characterized in that: the associated methods that after reduction activation process adopts first temperature programmed reduction, constant temperature reduces.
7. in accordance with the method for claim 5, it is characterized in that: reduction activation process adopts to contain CO gas for adopting temperature programmed reduction during reducing gases, adopts constant temperature reduction when taking hydrogen as reducing gases.
8. according to the method described in claim 5,6 or 7, it is characterized in that: temperature programmed reduction process is the operation of arbitrary temp section in 300 ~ 600 DEG C, heating rate 0.5 ~ 10 DEG C/min; Temperature programmed reduction refers to that the programming rate by controlling heats up, and passes into the method that reducing gases carries out catalyst reduction activation while intensification.
9. in accordance with the method for claim 8, it is characterized in that: temperature programmed reduction process is the operation of arbitrary temp section in 350 ~ 550 DEG C, heating rate 0.5 ~ 5 DEG C/min.
10. in accordance with the method for claim 1, it is characterized in that: dehydrogenation carried out pretreatment before reduction activation, pretreatment carries out pretreatment at 250 ~ 400 DEG C with hydrogen, pretreatment also can adopt temperature programming process for constant temperature process, the heating rate of temperature programming is 0.5 ~ 5 DEG C/min, pretreatment total time is 0.5 ~ 3 hour, and pretreatment hydrogen volume air speed is 500 ~ 5000h -1.
11. in accordance with the method for claim 1, it is characterized in that: the dehydrogenation after reduction activation, use the mist of hydrogen, hydrogen sulfide and nitrogen to carry out sulfuration, after sulfuration, can dehydrogenation reaction be carried out, dehydrogenation reaction raw material is propane or butane, obtains propylene or butylene through dehydrogenation.
12. in accordance with the method for claim 1, it is characterized in that: described platinum family loaded catalyst, with one or more in the platinum in platinum family, palladium, iridium, rhodium or osmium for active component.
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