CN102909016B - Method for stepwise activating dehydrogenation catalyst by using gas mixture of hydrocarbon/hydrogen and hydrogen gas - Google Patents

Method for stepwise activating dehydrogenation catalyst by using gas mixture of hydrocarbon/hydrogen and hydrogen gas Download PDF

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CN102909016B
CN102909016B CN201110217509.8A CN201110217509A CN102909016B CN 102909016 B CN102909016 B CN 102909016B CN 201110217509 A CN201110217509 A CN 201110217509A CN 102909016 B CN102909016 B CN 102909016B
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CN102909016A (en
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李江红
张海娟
王振宇
孙潇磊
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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Abstract

The present invention discloses a method for stepwise activating a dehydrogenation catalyst by using a gas mixture of hydrocarbon/hydrogen 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 gas mixture of hydrocarbon/hydrogen as the reducing gas, and then a reductive activation procedure is performed by using the 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 gas mixture of hydrocarbon/hydrogen as the reducing gas accounts for 20%-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 improves the stability of the dehydrogenation catalyst for light alkanes.

Description

With the method for hydrocarbon/hydrogen mixed 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 reduction activation method of catalyst for dehydrogenation of low-carbon paraffin, improve the initial activity of catalyst on the basis of existing technology further, and improve the selective of object product.
The present invention comprises following content with the method for hydrocarbon/hydrogen mixed 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 with hydrocarbon/hydrogen gaseous mixture for reducing gases carries out reduction activation process, and is that reducing gases carries out reduction activation process with hydrogen.Reduction activation temperature is 300 ~ 600 DEG C, be preferably 350 ~ 500 DEG C, total reduction activation time is 0.5 ~ 10.0 hour, be preferably 1 ~ 5 hour, it is 20% ~ 80% of total reduction activation time with the time that hydrocarbon/hydrogen gaseous mixture carries out reduction activation for reducing gases, 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, hydrocarbon/hydrogen gaseous mixture is the gaseous mixture of hydrocarbon and hydrogen, and hydrocarbon is wherein CH 4, CH 4generally account for 5% ~ 70% of hydrocarbon/hydrogen gaseous mixture cumulative volume, preferably 10% ~ 50%.
In the inventive method, the associated methods that after reduction activation process can adopt constant temperature reduction, temperature programmed reduction or first temperature programmed reduction, constant temperature reduces.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 with hydrocarbon/hydrogen gaseous mixture for during reducing gases adopt temperature programmed reduction, 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, pretreatment carries out pretreatment at 200 ~ 350 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.
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, when reduction activation, takes traditional H 2reduction, and constant temperature reduction at relatively high temperatures, 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 required reaction temperature is higher.In the activation method of dehydrogenation of the present invention, select CH 4carry out step-by-step reduction with the mist of hydrogen and hydrogen, improve the reduction degree of catalyst, solve the shortcoming that active metal particles after reduction is bigger than normal simultaneously.Initial activity after catalyst reduction is higher than the catalyst of pure hydrogen reduction, and catalyst activity reduction is comparatively slow, improves the selective of object product simultaneously.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 reduction of the present invention adopts hydrogen and CH 4the mist of/hydrogen is that reducing gases carries out step-by-step reduction, and 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 300 ~ 460 DEG C of scope internal program heating reductions, heating rate is 4 DEG C/min, CH in reducing gases hydrocarbon/hydrogen gaseous mixture 4account for 10% of gaseous mixture gas volume; Then, under 460 DEG C of constant temperatures, take hydrogen as reducing gases, constant temperature reduction 50min.In reduction process, the volume space velocity of reducing gases is 1800h -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 460 DEG C, cure time 30min.
appreciation condition: volume space velocity 2000 h of mist charging -1, reaction pressure 0.1MPa, reaction temperature is 570 DEG C, expects into middle hydrogen: 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 1800h -1, at 460 DEG C of reduction 90min, using 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 460 DEG C, soak time 30min.
appreciation condition:feed volume air speed 2000 h -1, reaction pressure 0.1MPa, reaction temperature is 570 DEG C, hydrogen in charging: 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: firstat 300 ~ 460 DEG C of scope internal program heating reductions, heating rate is 2 DEG C/min, CH in reducing gases hydrocarbon/hydrogen gaseous mixture 4account for 35% of gaseous mixture gas volume; Then, under 460 DEG C of constant temperatures, take electrolysis hydrogen as reducing gases, constant temperature reduction 50min.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 460 DEG C, cure time 30min.
appreciation condition: volume space velocity 2000 h of mist charging -1, reaction pressure 0.1MPa, reaction temperature is 570 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:first at 350 ~ 450 DEG C of scope internal program heating reductions, heating rate is 2 DEG C/min, CH in reducing gases hydrocarbon/hydrogen gaseous mixture 4account for 20% of gaseous mixture gas volume; Then, under 450 DEG C of constant temperatures, take hydrogen as reducing gases, constant temperature reduction 60min.In reduction process, the volume space velocity of reducing gases is 1800h -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 460 DEG C, cure time 30min.
appreciation condition: the volume space velocity of mist charging is 2000 h -1, reaction pressure 0.1 is MPa, and reaction temperature is 570 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:first at 300 ~ 400 DEG C of scope internal program heating reductions, heating rate is 2 DEG C/min, CH in reducing gases hydrocarbon/hydrogen gaseous mixture 4account for 50% of gaseous mixture gas volume; Then rise reduction at 400 ~ 460 DEG C of scope internal programs, heating rate is 1 DEG C/min, and reducing gases is hydrogen.In reduction process, the volume space velocity of reducing gases is 1800h -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 460 DEG C, cure time 30min.
appreciation condition: volume space velocity 2000 h of mist charging -1, reaction pressure 0.1MPa, reaction temperature is 570 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 ~ 460 DEG C of scope internal program heating reductions, heating rate is 5 DEG C/min, CH in reducing gases hydrocarbon/hydrogen gaseous mixture 4account for 40% of gaseous mixture gas volume; Then, under 460 DEG C of constant temperatures, take electrolysis hydrogen as reducing gases, constant temperature reduction 60min.In reduction process, the volume space velocity of reducing gases is 1800h -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 460 DEG C, cure time 30min.
appreciation condition: volume space velocity 2000 h of mist charging -1, reaction pressure 0.1MPa, reaction temperature is 570 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 300 ~ 460 DEG C of scope internal program heating reductions, heating rate is 8 DEG C/min, CH in reducing gases hydrocarbon/hydrogen gaseous mixture 4account for 20% of gaseous mixture gas volume; Then, under 460 DEG C of constant temperatures, take hydrogen as reducing gases, constant temperature reduction 70min.In reduction process, the volume space velocity of reducing gases is 1800h -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 460 DEG C, cure time 30min.
appreciation condition: volume space velocity 2000 h of mist charging -1, reaction pressure 0.1MPa, reaction temperature is 570 DEG C, hydrogen: 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:first under 280 DEG C of constant temperatures, carry out pretreatment with hydrogen, constant temperature pretreatment 20 min; Then at 300 ~ 460 DEG C of scope internal program heating reductions, heating rate is 4 DEG C/min, CH in reducing gases hydrocarbon/hydrogen gaseous mixture 4account for 20% of gaseous mixture gas volume; Last take hydrogen as reducing gases under 460 DEG C of constant temperatures, constant temperature reductase 12 0min.In reduction process, the volume space velocity of reducing gases is 1800h -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 460 DEG C, cure time 30min.
appreciation condition: volume space velocity 2000 h of mist charging -1, reaction pressure 0.1MPa, reaction temperature is 570 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 % Latter stage Propylene Selectivity %
Embodiment 1 26.7 19.9 91.4
Embodiment 2 27.1 20.8 92.0
Embodiment 3 27.6 21.6 92.0
Embodiment 4 28.2 22.7 92.1
Embodiment 5 27.6 22.5 92.6
Embodiment 6 27.2 20.6 91.7
Embodiment 7 27.5 21.4 91.9
Comparative example 25.1 14.2 90.0
The initial reaction time: 1.5 hours
Reaction time in latter stage: 45 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, still maintain higher activity and selectivity through long stream catalyst.

Claims (11)

1. one kind with the method for hydrocarbon/hydrogen mixed 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: reduction activation process comprises with hydrocarbon/hydrogen gaseous mixture for reducing gases carries out reduction activation process, and be that reducing gases carries out reduction activation process with hydrogen; Reduction activation temperature is 300 ~ 600 DEG C, and total reduction activation time is 0.5 ~ 10.0 hour, and be 20% ~ 80% of total reduction activation time with the time that hydrocarbon/hydrogen gaseous mixture carries out reduction activation for reducing gases, 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: reduction activation temperature is 350 ~ 500 DEG C, total reduction activation time is 1 ~ 5 hour.
3. in accordance with the method for claim 1, it is characterized in that: be 30% ~ 60% of total reduction activation time with the time that hydrocarbon/hydrogen gaseous mixture carries out reduction activation for reducing gases.
4. in accordance with the method for claim 1, it is characterized in that: hydrocarbon/hydrogen gaseous mixture is the gaseous mixture of hydrocarbon and hydrogen, and hydrocarbon is wherein CH 4, CH 4account for 5% ~ 70% of hydrocarbon/hydrogen gaseous mixture cumulative volume.
5. in accordance with the method for claim 1, it is characterized in that: the associated methods that after reduction activation process adopts constant temperature reduction, temperature programmed reduction or first temperature programmed reduction, constant temperature reduces.
6. in accordance with the method for claim 1, it is characterized in that: the associated methods that after reduction activation process adopts first temperature programmed reduction, constant temperature reduces, with hydrocarbon/hydrogen gaseous mixture for adopting temperature programmed reduction during reducing gases, when taking hydrogen as reducing gases, adopting constant temperature reduction.
7. according to the method described in claim 5 or 6, 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.
8. in accordance with the method for claim 7, it is characterized in that: temperature programmed reduction process is the operation of arbitrary temp section in 350 ~ 550 DEG C, and heating rate is 0.5 ~ 5 DEG C/min.
9. in accordance with the method for claim 1, it is characterized in that: dehydrogenation carried out pretreatment before reduction, pretreatment carries out pretreatment at 200 ~ 350 DEG C with hydrogen, pretreatment is constant temperature process or adopts temperature programming 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.
10. 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.
11. in accordance with the method for claim 4, it is characterized in that: CH 4account for 10% ~ 50% of hydrocarbon/hydrogen gaseous mixture cumulative volume.
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CN1886193A (en) * 2003-11-27 2006-12-27 耐思特石油公司 Catalyst and method for the preparation thereof
CN101108362A (en) * 2006-07-19 2008-01-23 中国石化集团金陵石油化工有限责任公司 Catalyzer used for low carbon alkane catalytic dehydrogenation and method of manufacturing propylene by paraffin hydrocarbons catalytic dehydrogenation with the same as catalyzer

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1886193A (en) * 2003-11-27 2006-12-27 耐思特石油公司 Catalyst and method for the preparation thereof
CN101108362A (en) * 2006-07-19 2008-01-23 中国石化集团金陵石油化工有限责任公司 Catalyzer used for low carbon alkane catalytic dehydrogenation and method of manufacturing propylene by paraffin hydrocarbons catalytic dehydrogenation with the same as catalyzer

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