CN102380425B - Dehydrogenation catalyst reduction method - Google Patents
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Abstract
The invention discloses a dehydrogenation catalyst reduction method. Dehydrogenation catalyst is platinum family loading catalyst and is in programmed temperature rising reduction before being used, the programmed temperature rising reduction is performed within a temperature range between 350 DEG C and 600 DEG C, and temperature rising speed ranges from 0.5 DEG C/min to 10 DEG C/min. In an activating process of the dehydrogenation catalyst, after platinum-base catalyst is prepared by a conventional method, conventional constant-temperature reduction operation is omitted, a programmed temperature-rising reduction method is utilized to realizing activation reduction for the catalyst, so that metal particles of the catalyst after being in reduction are dispersed more uniformly, sizes of the particles are proper, and surface area of exposed elementary substance Pt is enlarged. Accumulation of activated metal of the catalyst due to deep reduction of dehydrogenation activated metal is avoided, deep reduction of addition agent components which do not need reduction can also be avoided, accordingly, service performances of the catalyst are improved, and particularly, selectivity of objective products and stability of long-term reaction are improved.
Description
Technical field
The invention relates to a kind of method of reducing of low-carbon alkanes catalytic dehydrogenation system alkene catalyst, the particularly method of reducing of C3～C4 dehydrating alkanes system alkene catalyst.
Background technology
Entered since the new century, world's petrochemical material and petroleum chemicals demand will sustainable growths, to continue to increase as the demand of petrochemical industry basic material propylene, and the propylene demand that conventional steam cracking and FCC technology production capacity can not satisfy quick growth, it is global in short supply that its market has been occurred.And deficient day by day along with petroleum resources, the production of propylene has been that raw material changes to the diversified technology path of raw material sources from simple dependence oil, particularly is the technology path that raw material is produced alkene with the low-carbon alkanes.In recent years, the technology that dehydrogenating propane is produced propylene had obtained large development, and it is very fast that particularly the technology of dehydrogenating propane (PDH) system propylene had the area development of resources advantage in recent years in the Middle East etc., becomes the third-largest propylene production.
The propane catalytic dehydrogenating reaction is subjected to thermodynamics equilibrium limit, must carry out under the harsh conditions of high temperature, low pressure.Too high reaction temperature makes propane cracking reaction and degree of depth dehydrogenation aggravation, and selectivity descends; Accelerate the catalyst surface carbon deposit simultaneously, make rapid catalyst deactivation.Because the shortening of catalyst life is restricted the PDH method under lower conversion of propane and the harsh reaction condition when commercial Application.Therefore, exploitation has the catalyst for preparing propylene with propane dehydrogenation of high selectivity and high stability and the key that supporting technology becomes this technology.The dehydrogenating propane technology is representative with the Oleflex technology of Uop Inc. and the Catafin technology of U.S. Air Product company.Oleflex technology is mainly catalyst based based on Pt, and Catafin technology is mainly with Cr
2O
3/ Al
2O
3Be main.
Load type platinum is catalyst based to be an important class in the alkane dehydrogenating catalyst, and the production method of such catalyst is also open in the art.USP4914075, USP4353815, USP4420649, USP4506032, USP4595673, EP562906, EP98622 etc. have reported that to be used for propane and other dehydrogenating low-carbon alkane Pt catalyst based, have high alkane conversion and olefine selective.USP3897368 and CN87108352 disclose a kind of method of producing hud typed 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 reactive metal.This above-mentioned class catalyst must be used hydrogen reducing before use, and the catalyst after the reduction is used for dehydrogenation reaction.In this class catalyst, the constant temperature reduction is adopted in reduction, and temperature is at 400～650 ℃.CN101138734A, CN101015802A be constant temperature reductase 12～10h in 400～600 ℃ of hydrogen streams, and CN1844324A is at 400 ℃ of following constant temperature reduction 7h, and CN101108362A is preferably at 450～550 ℃ of following constant temperature reduction 4～6h.Reduction can make the activity of such catalysts component become the elemental metals attitude, can also guarantee that the metal component particle disperses, but constant temperature reduction under higher temperature, cause the sintering of metallic particles easily, make the catalyst metal particles after the reduction bigger than normal, cause the surface area of the simple substance Pt that comes out less than normal, finally make activity of such catalysts and selectivity lower.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of method of reducing of alkane dehydrogenating catalyst, further improve the purpose product yield on the basis of existing technology, improve selection of catalysts simultaneously.
Dehydrogenation method of reducing of the present invention comprises following content: dehydrogenation is the platinum family loaded catalyst, dehydrogenation adopts temperature programmed reduction before use, temperature programmed reduction is operated in 350～600 ℃ of scopes, preferably in 400～550 ℃ of scopes, operate, 0.5～10 ℃/min of heating rate, preferred 0.5～5 ℃/min, the temperature programming time is 15～90min, is preferably 20～50min.
In the dehydrogenation method of reducing of the present invention, the control that in reduction process, heats up that temperature programmed reduction refers to.Dehydrogenation after the reduction uses the mist of hydrogen, hydrogen sulfide and nitrogen to vulcanize, and can carry out dehydrogenation reaction after the sulfuration, and vulcanization process can adopt this area routine techniques.
In the dehydrogenation method of reducing of the present invention, the temperature programmed reduction process feeds reducibility gas, generally uses hydrogen, also can be the mist of hydrogen and diluent gas, diluent gas can be the hydro carbons of nitrogen, C1～C4 etc., and hydrogen generally accounts for 10%～80% of mist volume.In the temperature programmed reduction process, the volume space velocity of reducibility gas is generally 500～5000h
-1
In the dehydrogenation method of reducing of the present invention, dehydrogenation is the platinum family loaded catalyst, catalyst generally is carrier with the aluminium oxide, is active component with in the platinum in the platinum family, palladium, iridium, rhodium or the osmium one or more, is 0.01%～2% of vehicle weight in the simple substance active component.Simultaneously can contain suitable auxiliary agent in the dehydrogenation, as Sn, K, rare earth metal etc., the content of Sn is counted 0.1%～10% of vehicle weight with simple substance, and the content of K is counted 0.1%～10% of vehicle weight with element.Dehydrogenation can adopt the method preparation of this area routine, and as adopting infusion process load dehydrogenation active component, auxiliary agent can and/or adopt infusion process to introduce in the preparing carriers process.
Existing dehydrogenation is taked constant temperature reduction under traditional higher temperature, though this activation method has the sufficient advantage of dehydrogenation activity metallic reducing when reduction, but the metallic particles selectivity that causes bigger than normal after the reduction is relatively poor relatively, and, along with the carrying out of reaction, active decline comparatively fast.In the activation method of dehydrogenation of the present invention, after adopting conventional method to prepare platinum based catalyst, do not carry out conventional restoring operation, adopt temperature-programmed reduction method that catalyst is carried out reduction activation, make the catalyst metal particles after the reduction disperse more even, granular size is more appropriate, and the surface area of the simple substance Pt that comes out increases.The catalyst activity accumulation of metal phenomenon of avoiding the reduction of dehydrogenation activity metal depth to cause, also can avoid some adjuvant component of not wishing to reduce by drastic reduction, influenced the synergy (the particularly synergy between active component Pt and the adjuvant component Sn) of auxiliary agent, and then improved the serviceability of catalyst, particularly improved the stability of purpose product selectivity and long-time reaction.When particularly adopting the mist that contains diluent gas to reduce, the reduction that can guarantee dehydrogenation active component and relevant auxiliary agent is in the good synergy scope with sulfuration, catalyst serviceability after the reduction is stable, and reduction process is easy to control.
Description of drawings
Fig. 1 is Pt particulate scan Electronic Speculum figure in the embodiment 1 temperature programmed reduction dehydrogenation.
Fig. 2 is Pt particulate scan Electronic Speculum figure in the comparative example constant temperature reduction dehydrogenation.
The specific embodiment
Dehydrogenation method of reducing of the present invention is reduced by the constant temperature that temperature-programmed reduction method has replaced 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 is an active component with Pt preferably, is auxiliary agent with Sn, and auxiliary agent can also comprise K, rare earth metal etc. simultaneously.
Dehydrogenation can adopt conventional preparation method, and as adopting infusion process load dehydrogenation activity metal, auxiliary agent can and/or adopt dipping method to introduce in the alumina support preparation process.
In the dehydrogenation method of reducing of the present invention, a kind of concrete dehydrogenation is a carrier to contain the Sn aluminium oxide, the dehydrogenation activity metal component generally is selected from one or more in platinum, palladium, iridium, rhodium or the osmium in the platinum family, and consumption is counted 0.01%～2% of vehicle weight with simple substance.The content of Sn is counted 0.1%～10% of vehicle weight with simple substance.Contain in the dehydrogenation that the Sn aluminium oxide is a carrier, Sn introduces the material that contains Sn when aluminium oxide becomes glue, make carrier then.The dehydrogenation activity metal component can be evenly distributed in the catalyst, and preferred dehydrogenation activity metal component is concentrated and is distributed in the catalyst outer layer, forms hud typed catalyst.Can contain suitable auxiliary agent simultaneously in the dehydrogenation, as alkali metal, alkaline-earth metal, rare earth metal and sulphur etc.
Introduce the detailed process and the condition of a kind of typical dehydrogenation method for preparing catalyst and method of reducing and vulcanization process below:
(1) preparation contains the alumina globule of Sn, and wherein content can need to determine by using, and generally counts 0.1%～5% of vehicle weight with simple substance;
(2) contain 600～900 ℃ of roastings of alumina globule of Sn after, adopt the supersaturation infusion process to introduce dehydrogenation active component; Can be by conditions such as control pH value of dipping solution and dip times, make that dehydrogenation active component is mainly concentrated to be distributed in the certain thickness skin of carrier surface;
(3) catalyst intermediate behind the supported active metal component is carried out steam dechlorination in the step (2);
(4) add the required alkali metal promoter of catalyst in the catalyst that step (3) obtains, the auxiliary agent use amount can be determined by this area general knowledge as required;
(5) catalyst that obtains of step (4) adopts temperature programmed reduction, and heating rate is 1～5 ℃/min, and temperature range is at 400～600 ℃;
(6), heat up and carry out dehydrogenation reaction with after the mixed gas cure of hydrogen sulfide, hydrogen and nitrogen;
(7) dehydrogenation reaction is carried out under as the atmosphere of diluent at hydrogen.
The alumina support that contains Sn in the step (1) is introduced Sn when aluminium oxide becomes glue, preparation contains the alumina support of Sn then.The described Sn of containing alumina support prepares in cogelled mode, when becoming glue, introduces in aluminium oxide the material that contains Sn, the material that contains Sn is generally soluble-salt, as nitrate, chloride etc., then by the existing method moulding in this area, as dripping ball forming, extrusion modling etc., aluminium oxide becomes glue to be known by the technical staff.The preparation method of above-mentioned carrier is the known method of technical staff.
Wherein the described dehydrogenation activity metal of step (2) generally is selected from one or more elements in platinum, palladium, iridium, rhodium or the osmium in the platinum family, and content can need to determine, generally count 0.1%～2% of vehicle weight with simple substance by using.
The described steam dechlorination of step (3) is to handle 1～20 hour down at 300～700 ℃, and the atmosphere of dechlorination is the air that contains 10v%～30v% water vapour, and chlorinity is less than 0.15wt%.
The described temperature programmed reduction condition of step (4) in 350～600 ℃ of scopes, preferably in 400～550 ℃ of scopes, 0.5～10 ℃/min of heating rate, preferred 0.5～5 ℃/min.
The described conditions of vulcanization of step (5) is: the molar ratio of sulfiding gas hydrogen sulfide, hydrogen and nitrogen is 1: 9: (0～30), volume space velocity 900～1500h
-1, 400～550 ℃ of temperature, time 1～3h.
The described dehydrogenation reaction conditions of step (6) is: 550～650 ℃ of reaction temperatures, volume space velocity 1000～3000h
-1, absolute pressure 0.1～0.3MPa, hydrogen: the ratio of propane is between 1: 1～6: 1.
In the Preparation of catalysts process, Sn is incorporated in the alumina globule with cogelled method, flood active component then, more even, the active force that strengthens Sn and aluminium oxide that can make that Sn disperses cooperate the reduction process that suits, and can effectively suppress Sn
4+Be reduced to zeroth order Sn
0, stop the gathering of dehydrogenation activity metal in the pyroreaction environment.
Enforcement below by dehydrogenating propane is described further technology of the present invention.
Example 1
Preparation contains the alumina support of Sn.Behind the aluminum trichloride solution and the mixing of 0.01M butter of tin solution with a certain amount of 0.98M, add an amount of mass concentration and be 8% ammoniacal liquor, under 60～80 ℃, in neutralizing tank, mix, control pH value 7.0～9.0, after filtration, washing, the acidifying, the balling-up of pressurizeing in the oil ammonia column is through super-dry, aging, 650～750 ℃ of roastings 4 hours, promptly get the alumina globule that contains Sn 0.3wt%.
The alumina globule carrier that will contain 0.3%Sn floods 6h with the carrier after the roasting and the aqueous solution that contains chloroplatinic acid down at 70 ℃, at 120 ℃ of oven dry 2h, 500 ℃ of following roasting 4h at 800 ℃ of roasting 3h.In containing the air of water vapour, activate 4h then.Descend and contain KNO at 70 ℃ then
3Aqueous solution dipping 2h, dry, roasting under the same condition.The load capacity of each component is in the catalyst: Pt 0.5wt%, Sn 0.3wt%, K 0.5wt%.
Reducing condition: at 430～500 ℃ of scope internal program heating reductions, heating rate is 2 ℃/min, and the volume space velocity of hydrogen is 3000h in the reduction process
-1
Conditions of vulcanization: the mass velocity 900h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen
-1, molar ratio is 1: 9: 5,500 ℃ of temperature, cure time 1h.
Appreciation condition: catalyst volume 3.0ml, the volume space velocity 2000h of mist charging
-1, reaction pressure 0.1MPa, reaction temperature is 620 ℃, hydrogen: the molar ratio of propane is 1: 1.
The result shows: this catalyst is being estimated 22h continuously, and conversion of propane is 31.2%, and the propylene selectivity is 96.4%, and conversion ratio descends 1.2%, and selectivity is constant substantially, and coke content is 4.42% only, demonstrates good catalytic activity and stability.
Comparative example
Preparation of catalysts is with example 1, and different is to obtain catalyst through 500 ℃ of constant temperature hydrogen, vulcanizes then.Embodiment 1 temperature programmed reduction and comparative example constant temperature reduction Pt granular size are as depicted in figs. 1 and 2.
Reducing condition: 500 ℃ of constant temperature reduced 30 minutes, and volume space velocity is 3000h
-1
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: 5,500 ℃ of temperature, cure time 1h.
Appreciation condition: catalyst volume 3.0ml, volume space velocity 2000h
-1, reaction pressure 0.1MPa, reaction temperature is 620 ℃, hydrogen: the molar ratio of propane is 1: 1.
The result shows: this catalyst is being estimated 22h continuously, and conversion of propane is 29.2%, and the propylene selectivity is 96.1%, and conversion ratio descends 3.5%, and selectivity is constant substantially, and coke content is 6.02%.
Example 2
Preparation contains the alumina support of Sn.Behind the aluminum trichloride solution and the mixing of 0.01M butter of tin solution with a certain amount of 1.08M, add a certain amount of 10% ammoniacal liquor, under 60～80 ℃, in neutralizing tank, mix, control pH value 7.0～9.0, after filtration, washing, the acidifying, the balling-up of pressurizeing in the oil ammonia column is through super-dry, aging, 650～750 ℃ of roastings 4 hours, promptly get the alumina globule that contains Sn 1.0wt%.
The alumina globule carrier that will contain 1.0%Sn down floods 4h with the carrier after the roasting and the aqueous solution that contains chloroplatinic acid at 70 ℃ at 800 ℃ of roasting 3h, and at 120 ℃ of oven dry 2h, 500 ℃ of following roasting 4h activate 4h in containing the air of water vapour.Descend and contain KNO at 70 ℃ then
3Aqueous solution dipping 2h, dry, roasting under the same condition, 400～550 ℃ of temperature programmed reductions, heating rate are 2 ℃/min.The load capacity of each component is in the catalyst: Pt 0.7wt%, Sn 1.0wt%, K 1.0wt%.
Reducing condition: 400～500 ℃ of temperature programmed reductions, heating rate are 3 ℃/min, and the gas gas of hydrogen 40v% and nitrogen mixture volume space velocity are 4000h
-1
Conditions of vulcanization: the mass velocity 1000h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen
-1, molar ratio is 1: 9: 10,500 ℃ of temperature, cure time 1h.
Appreciation condition: catalyst volume 3.0ml, volume space velocity 3000h
-1, reaction pressure 0.1MPa, reaction temperature is 620 ℃, hydrogen: the molar ratio of propane was at 1: 1.
The result shows: this catalyst is being estimated 50h continuously, and conversion of propane is 28.1%, and the propylene selectivity is 96.2%, and conversion ratio descends 2.1%, and selectivity is constant substantially, and coke content is 7.16% only, demonstrates good catalytic activity and stability.
Example 3
Prepare dehydrogenation according to embodiment 1 identical method.
Reducing condition: 420～550 ℃ of temperature programmed reductions, heating rate are 4 ℃/min, and the hydrogen volume air speed is 1000h
-1
Conditions of vulcanization: the mass velocity 1200h of the mixed gas of hydrogen sulfide, hydrogen and nitrogen
-1, molar ratio is 1: 9: 10,500 ℃ of temperature, cure time 1h.
Appreciation condition: catalyst volume 3.0ml, volume space velocity 2000h
-1, reaction pressure 0.1MPa, reaction temperature is 620 ℃, hydrogen: the molar ratio of propane is 1: 1.
Evaluation result: this catalyst is after estimating 32h continuously, and conversion of propane is 30.12%, and the propylene selectivity is 96.4%, conversion ratio descends 2.2%, and selectivity is constant substantially, and coke content only is 4.46%, yield maintains more than 29%, demonstrates good catalytic activity and stability.
Claims (9)
1. the method for reducing of a dehydrogenation, dehydrogenation is the platinum family loaded catalyst, it is characterized in that: dehydrogenation adopts temperature programmed reduction before use, temperature programmed reduction is operated in 350～600 ℃ of scopes, 0.5～10 ℃/min of heating rate, the temperature programming time is 15～90min; Contain suitable auxiliary agent in the dehydrogenation, auxiliary agent is Sn, K or rare earth metal, and the content of Sn is counted 0.1%～10% of vehicle weight with simple substance, and the content of K is counted 0.1%～10% of vehicle weight with element.
2. in accordance with the method for claim 1, it is characterized in that: temperature programmed reduction is operated in 400～550 ℃ of scopes, 0.5～5 ℃/min of heating rate, and the temperature programming time is 20～50min.
3. in accordance with the method for claim 1, it is characterized in that: the dehydrogenation after the reduction uses the mist of hydrogen, hydrogen sulfide and nitrogen to vulcanize, and can carry out dehydrogenation reaction after the sulfuration.
4. in accordance with the method for claim 1, it is characterized in that: the temperature programmed reduction process feeds reducibility gas, and reducibility gas is a hydrogen, or the mist of hydrogen and diluent gas, and the volume space velocity of reducibility gas is 500～5000h
-1
5. in accordance with the method for claim 4, it is characterized in that: diluent gas is the hydro carbons of nitrogen, C1～C4, and hydrogen accounts for 10%～80% of mist volume.
6. in accordance with the method for claim 1, it is characterized in that: dehydrogenation is the platinum family loaded catalyst, catalyst is carrier with the aluminium oxide, with in the platinum in the platinum family, palladium, iridium, rhodium or the osmium one or more is active component, is 0.01%～2% of vehicle weight in the simple substance active component.
7. in accordance with the method for claim 1, it is characterized in that: auxiliary agent Sn introduces the material that contains Sn in the dehydrogenation when aluminium oxide becomes glue, makes carrier then.
8. in accordance with the method for claim 1, it is characterized in that: dehydrogenation carried out steam dechlorination before carrying out temperature programmed reduction handles, the steam dechlorination process is to handle 1～20 hour down at 300～700 ℃, the atmosphere of dechlorination is the air that contains 10v%～30v% water vapour, and chlorinity is less than 0.15wt%.
9. in accordance with the method for claim 3, it is characterized in that: the condition that the dehydrogenation after the reduction uses the mist of hydrogen, hydrogen sulfide and nitrogen to vulcanize is: the molar ratio of sulfiding gas hydrogen sulfide, hydrogen and nitrogen is 1: 9: (0～30), volume space velocity 900～1500h
-1, 400～550 ℃ of temperature, time 1～3h.
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| CN103420767B (en) * | 2012-05-16 | 2015-11-18 | 中国石油化工股份有限公司 | The preparation method of iso-butylene |
| CN103785383B (en) * | 2012-11-01 | 2016-08-03 | 中国石油化工股份有限公司 | A kind of dehydrogenation and preparation method thereof |
| CN103785384B (en) * | 2012-11-01 | 2016-02-10 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation |
| CN104549248B (en) * | 2013-10-22 | 2017-02-08 | 中国石油化工股份有限公司 | Preparation method for catalyst for dehydrogenation of low-carbon alkane |
| CN104588042B (en) * | 2013-11-01 | 2017-06-06 | 中国石油化工股份有限公司 | A kind of preparation method of vulcanization type propane dehydrogenation catalyst |
| CN107537590B (en) * | 2016-06-28 | 2020-07-10 | 中国石油化工股份有限公司 | Low-purity hydrogen reduction method for hydrocarbon steam conversion catalyst |
| CN110280239B (en) * | 2019-07-23 | 2022-05-03 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing 2, 3-dichloropyridine and preparation method and application thereof |
| CN113617372B (en) * | 2021-09-13 | 2023-10-27 | 中冶长天国际工程有限责任公司 | High-dispersion CO oxidation catalyst and preparation method and application thereof |
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| CN1033756A (en) * | 1987-07-31 | 1989-07-12 | 埃尼里瑟奇公司 | Dehydrogenation catalyst and preparation method thereof and in the application for preparing with linear paraffinic hydrocarbons in the linear alpha-olefin |
| CN1827218A (en) * | 2006-03-30 | 2006-09-06 | 上海工程技术大学 | Method for preparing supported nano copper nickel catalyst and application thereof in oxidative dehydrogenation reaction of alkylol amine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033756A (en) * | 1987-07-31 | 1989-07-12 | 埃尼里瑟奇公司 | Dehydrogenation catalyst and preparation method thereof and in the application for preparing with linear paraffinic hydrocarbons in the linear alpha-olefin |
| CN1827218A (en) * | 2006-03-30 | 2006-09-06 | 上海工程技术大学 | Method for preparing supported nano copper nickel catalyst and application thereof in oxidative dehydrogenation reaction of alkylol amine |
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