CN102909010B - Dehydrogenation catalyst activation method combining high-temperature reduction with temperature programmed reduction - Google Patents
Dehydrogenation catalyst activation method combining high-temperature reduction with temperature programmed reduction Download PDFInfo
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Abstract
The present invention discloses a dehydrogenation catalyst activation method combining high-temperature reduction with temperature programmed reduction. The dehydrogenation catalyst is a platinum group metal-supported catalyst. The activation process comprises: performing the high temperature reduction at first, wherein hydrogen gas is used in the high temperature reduction at a temperature of 450-550 DEG C for 5-55min; then performing the temperature programmed reduction, wherein hydrogen gas is used for the reduction, the initial temperature is of 240-400 DEG C, the finish temperature is of 450-550DEG C, and the heating rate is 0.5-10 DEG C/min; and then adjusting the temperature to 500-650 DEG C, the process of sulfurization passivation and directly feeding hydrogen-containing feed gas for the dehydrogenation reaction. Compared with the prior art, the dehydrogenation catalyst reduced and activated by the method of the invention has a higher activity stability.
Description
Technical field
The invention relates to the activation method of a kind of low-carbon alkanes catalytic dehydrogenation alkene catalyst processed, specifically, is about C
2~ C
5the activation method of Oxidative Dehydrogenation alkene catalyst.
Background technology
Along with the universal use of civil natural gas, effective utilization of refinery's liquefied gas becomes the focus of petrochemical industry, how to become more meticulous and utilizes low-carbon alkanes resource valuable in liquefied gas significant.Preparing propylene by dehydrogenating propane and preparing isobutene through dehydrogenation of iso-butane just liquefied gas are produced one of important channel of industrial chemicals, and it will become an emphasis of new century petrochemical technology research and development.
Low-carbon alkanes catalytic dehydrogenating reaction is subject to thermodynamics equilibrium limit, must under the harsh conditions of high temperature, low pressure, carry out.Too high reaction temperature, makes low-carbon alkanes cracking reaction and degree of depth dehydrogenation aggravation, selectively declines; Accelerate catalyst surface carbon deposit simultaneously, made rapid catalyst deactivation.Due to the shortening of catalyst life under lower alkane conversion and harsh reaction condition, make dehydrogenating low-carbon alkane method in the time of commercial Application, be subject to certain restriction.Therefore, exploitation has the catalyst for preparing propylene with propane dehydrogenation of high selectivity and high stability and supporting technique becomes the key of this technology.At present, dehydrogenating low-carbon alkane patented technology comprises in the world: the Oleflex technique of Uop Inc., the Catofin technique of ABB Lu Musi company, the Star technique of Kang Fei (Uhde) company, the FBD-4 technique of Snamprogetti/Yarsintz company, the PDH technique of Lin De/BASF AG etc.In the device of having built, former Soviet Union's great majority adopt FBD-4 technique, and Catofin and Oleflex technique have become the leading technique adopting in new device.Oleflex technique is mainly catalyst based as main taking 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. have reported 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 active metal.Above-mentioned this class Pt catalyst must be used hydrogen reducing before use, and the catalyst after reduction, for dehydrogenation reaction, in order to increase the stability of catalyst, generally carries out Passivation Treatment.In this class catalyst, reduction adopts pure hydrogen constant temperature to reduce for a long time, and low-temperature reduction does not generally reach the reduction degree of depth, and therefore the long-time reduction temperature of constant temperature is generally 400 ~ 650 DEG C, carries out Passivation Treatment after reduction again.As CN101138734A, CN101015802A constant temperature reductase 12 ~ 10h in 400 ~ 600 DEG C of hydrogen streams, CN1844324A is hydrogen stream constant temperature reduction 7h at 400 DEG C, and CN101108362A is constant temperature reduction 4 ~ 6h in hydrogen stream at 450 ~ 550 DEG C preferably.In High Purity Hydrogen air-flow, constant temperature reduces for a long time, although can make the active component of catalyst become elemental metals state, guarantees that metal component reaches drastic reduction, and catalyst initial activity is higher, and the activity of catalyst declines very fast, less stable.Only have by sulfuration passivation, could improve the stability of catalyst.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of catalyst for dehydrogenation of low-carbon paraffin activation, save on the basis of existing technology sulfuration passivating process, and further improved object product yield, improve the stability of catalyst simultaneously.
High temperature reduction of the present invention is in conjunction with the dehydrogenation activation method of temperature programmed reduction, comprise following content: dehydrogenation is platinum family loaded catalyst, dehydrogenation activation process is first carried out high temperature reduction, then adopt temperature programmed reduction, high temperature reduction adopts hydrogen in the time of 450 ~ 550 DEG C, to reduce 5 ~ 55min, preferably 10 ~ 40min; Temperature programmed reduction adopts hydrogen reducing, and temperature programmed reduction initial temperature is 240 ~ 400 DEG C, and temperature programmed reduction end temp is 450 ~ 550 DEG C, and programming rate is 0.5 ~ 10 DEG C/min, preferably 0.5 ~ 5 DEG C/min; Then temperature is adjusted to 500 ~ 650 DEG C, cancels sulfuration passivation, and the unstripped gas that directly passes into hydrogen carries out dehydrogenation reaction.
In dehydrogenation activation method of the present invention, the hydrogen of reduction use concentration is by volume at least 90%, is preferably more than 95%.Temperature programmed reduction carries out the reduction of dehydrogenation when referring to intensification.
The detailed process of a kind of activation of the inventive method is as follows: first, under nitrogen atmosphere, with 0.5 ~ 30 DEG C/min heating rate, preferably temperature is raised to 450 ~ 550 DEG C by the heating rate of 5 ~ 15 DEG C/min, then gas is replaced by reduction hydrogen, constant temperature reduction; In nitrogen protection borehole cooling to 240 ~ 300 DEG C, adopt reduction hydrogen to carry out temperature programmed reduction.
The inventive method dehydrogenation is changed into after the reduction of constant temperature short time by the long-time reduction of traditional High Purity Hydrogen air-flow constant temperature before use, then carries out temperature programmed reduction, makes the reduction degree of active component Pt in dehydrogenation reach 30% ~ 50%.The reduction degree that active component is suitable, avoid on the one hand dehydrogenation activity metal depth to reduce the catalyst activity accumulation of metal initial activity causing and cross the not high phenomenon of high stability, also can avoid some adjuvant component of not wishing reduction by drastic reduction, affect the synergy of auxiliary agent, control the dehydrogenation of certain reduction degree in use, can further reduce, active slowly release reached the object that improves catalyst stability.
In dehydrogenation activation method of the present invention, dehydrogenation is platinum family loaded catalyst, catalyst is generally taking aluminium oxide or faintly acid molecular sieve as carrier, taking one or more in the platinum in platinum family, palladium, iridium, rhodium or osmium as active component, active component contains platinum, taking element active component as vehicle weight 0.01% ~ 2%.In dehydrogenation, simultaneously can contain suitable auxiliary agent, as one or more in Sn, La, K, rare earth metal etc., the content of Sn or La is counted 0.1% ~ 10% of vehicle weight with element, 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 adopted infusion process load dehydrogenation active component, auxiliary agent can and/or adopt infusion process to introduce in carrier preparation process.
Existing dehydrogenation is in the time of activation, take under traditional higher temperature the long-time method of reducing of constant temperature in hydrogen stream more, although this activation method has advantages of dehydrogenation activity metallic reducing fully and initial reaction is active high, but stability is relatively poor, along with the carrying out of reaction, active decline comparatively fast.In order to increase its stability, must vulcanize passivation.In the activation method of dehydrogenation of the present invention, platinum based catalyst adopts conventional method preparation, does not carry out conventional restoring operation, adopts after the pure hydrogen constant temperature reduction of high temperature certain hour, reduce after temperature, control heating rate reduction certain hour to control the reduction degree of Pt in catalyst.Its object is that the initial stage cracking performance that suppresses catalyst is beneficial to long-term stability.Catalyst has after certain reduction degree, and the unstripped gas that intensification passes into hydrogen reacts, and Pt in catalyst is further reduced.Reach active component Pt and reacted while reduce, actively slowly discharged the object to increase catalyst stability.After activation processing, improve the serviceability of catalyst, particularly improve the stability of the selective and long-time reaction of object product, the catalyst serviceability after activation is stable, and activation process is easy to control, and has saved sulfuration passivating process.
Detailed description of the invention
Dehydrogenation activation method of the present invention is controlled the reduction degree of Pt and has been replaced constant temperature under traditional higher temperature and reduce by controlling the recovery time and changing temperature program(me) heating reduction.Dehydrogenation of the present invention does not need passivation just can improve the stability of catalyst long time running.Dehydrogenation is preferably taking Pt as active component, and taking Sn or La as auxiliary agent, auxiliary agent can also comprise K, Na and rare earth metal etc. simultaneously.
Dehydrogenation can adopt conventional preparation method, and as adopted infusion process load dehydrogenation activity metal, auxiliary agent can and/or adopt dipping method to introduce in alumina support preparation process.
Catalyst of the present invention is to contain Sn aluminium oxide or faintly acid molecular sieve as carrier, and dehydrogenation activity metal component is generally selected from one or more in platinum, palladium, iridium, rhodium or the osmium in platinum family, is preferably platinum, and consumption is counted 0.01% ~ 2% of vehicle weight with element.The content of Sn is counted 0.1% ~ 10% of vehicle weight with element.
The present invention is to contain Sn aluminium oxide or faintly acid in the dehydrogenation of carrier, and Sn introduces the material containing Sn in the time of aluminium oxide plastic, then makes carrier.
The present invention is to contain Sn aluminium oxide or faintly acid molecular sieve in the dehydrogenation of carrier, and dehydrogenation activity metal component can be evenly distributed in catalyst, and preferably dehydrogenation activity metal component is concentrated and is distributed in catalyst outer layer, forms hud typed catalyst.
The present invention taking containing Sn aluminium oxide or faintly acid molecular sieve in the dehydrogenation of carrier, can contain suitable auxiliary agent, as one or more in alkali metal, alkaline-earth metal, rare earth metal and sulphur etc. simultaneously.
Introduce detailed process and the condition of a kind of typical dehydrogenation method for preparing catalyst and activation method below:
(1) taking alumina globule or faintly acid molecular sieve as carrier impregnation SnCl
4solution, wherein content can need to determine by using, and preferably counts 0.1% ~ 5% of aluminium oxide or faintly acid molecular sieve weight with element;
(2), containing after 800 DEG C of roastings of carrier of Sn, adopt supersaturation infusion process to introduce dehydrogenation active component; Can, by controlling the condition such as pH value and dip time of dipping solution, dehydrogenation active component mainly be concentrated in the certain thickness skin of carrier surface;
(3) in step (2), the catalyst intermediate after heat treatment is carried out steam dechlorination;
(4) in the catalyst that step (3) obtains, add the required alkali metal promoter of catalyst, auxiliary agent use amount can be determined by this area general knowledge as required.
(5) catalyst that step (4) obtains adopted after the hydrogen control constant temperature recovery time, reduced temperature and carried out temperature programmed reduction.
(6) dehydrogenation reaction is carried out under as the atmosphere of diluent at hydrogen.
Alumina support containing Sn in step (1) is introduced Sn in the time of aluminium oxide plastic, and then preparation is containing the alumina support of Sn.The described Sn alumina support that contains is prepared in cogelled mode, in the time of aluminium oxide plastic, introduce the material containing Sn, material containing Sn is generally soluble-salt, as nitrate, chloride etc., then by the existing method moulding in this area, as dripped a ball forming, extrusion modling etc., aluminium oxide plastic is known by 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) is generally selected from one or more elements in platinum, palladium, iridium, rhodium or the osmium in platinum family, and content can need to determine by using, preferably count 0.1% ~ 2% of vehicle weight with element.
Steam dechlorination described in step (3) for to process 1 ~ 20 hour at 300 ~ 700 DEG C, and the atmosphere of dechlorination is the air containing 10v% ~ 30v% water vapour, and chlorinity is less than 0.15wt%.
Described high temperature constant temperature reduction and other condition of temperature programmed reduction of step (5) is: the volume space velocity of reducing gases is 500 ~ 5000h
-1, absolute pressure 0.1 ~ 0.5MPa.
The described dehydrogenation reaction conditions of step (6) is: 500 ~ 650 DEG C of reaction temperatures, volume space velocity (hydrogen and unstripped gas sum, unstripped gas is low-carbon alkanes) 500 ~ 5000h
-1, absolute pressure 0.1 ~ 0.5MPa, hydrogen: the molar ratio of low-carbon alkanes is between 1:1 ~ 6:1.Described low-carbon alkanes is C
2~ C
5alkane, as propane, normal butane, iso-butane, pentane, isopentane etc.
Enforcement below by dehydrogenation of isobutane is described further technology of the present invention.Wherein the percentage composition of clear and definite benchmark is not weight percentage.In dehydrogenation, the implication of the reduction degree of Pt is that the ratio of the amount of total Pt in amount and the catalyst of the Pt that is reduced in catalyst is multiplied by 100%, measures or analytical method is TPR, TPD hydroxide titration method, ICP method or inorganic analysis method.
Example 1
Preparation is containing the alumina support of Sn.By after the aluminum trichloride solution of a certain amount of 0.98M and the mixing of 0.01M butter of tin solution, add a certain amount of 8% ammoniacal liquor, at 60 ~ 80 DEG C, in neutralizing tank, mix, control pH value 7.0 ~ 9.0, after filtration, washing, acidifying, the balling-up of pressurizeing in oil ammonia column, through super-dry, aging, 650 ~ 750 DEG C of roastings 4 hours, obtain the alumina globule containing Sn 0.8wt%.
The alumina globule carrier that contains 0.8% Sn, at 800 DEG C of roasting 3h, is flooded to 6h by the carrier after roasting and the aqueous solution that contains chloroplatinic acid at 70 DEG C, dry 2h at 120 DEG C, roasting 4h at 500 DEG C.Then in the air that contains water vapour, activate 4h.Then at 70 DEG C with contain KNO
3aqueous solution dipping 2h, dry, roasting under same condition.In catalyst, the load capacity of each component is: Pt 0.3wt%, Sn 0.8wt%, K 0.7wt%.
activation condition:first under nitrogen atmosphere, be warming up to 500 DEG C, 500 DEG C of constant temperature reduction 15min of hydrogen, nitrogen protection borehole cooling to 350 DEG C, at 350 ~ 500 DEG C of scope internal program heating reductions, heating rate is 2 DEG C/min.In activation process, the volume space velocity of reducing gases hydrogen is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 32%.
appreciation condition: catalyst volume 2.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 580 DEG C, hydrogen: the molar ratio of iso-butane is at 2:1.
result shows: this catalyst is being evaluated 48h continuously, and iso-butane conversion ratio is 38.88%, and selective isobutene is 95.65%, conversion ratio and selectively substantially constant, and coke content is only 0.75%, demonstrates good catalytic activity and stability.
Comparative example
The preparation of catalyst is with example 1, and different is that long-time reduction obtains catalyst through constant temperature in 500 DEG C of flow of pure hydrogen.
activation condition:500 DEG C of Cheng Hengwen reductase 12 h in High Purity Hydrogen air-flow, the volume space velocity of reducing gases is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 90%.
conditions of vulcanization: the volume space velocity of the mixed gas of hydrogen sulfide and hydrogen is 900 h
-1, molar ratio is 1:9,500 DEG C of temperature, passivation time 1h.
appreciation condition: catalyst volume 2.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 580 DEG C, hydrogen: the ratio of iso-butane is at 2:1.
result shows: this catalyst is being evaluated 48h continuously, and iso-butane conversion ratio is 34.6%, and selective isobutene is 95.4%, and conversion ratio declines 3.8 percentage points, selectively rises 0.5 percentage point, and coke content is 1.62%.
Example 2
Preparation is containing the alumina support of Sn.By after the aluminum trichloride solution of a certain amount of 1.08M and the mixing of 0.01M butter of tin solution, add a certain amount of 10% ammoniacal liquor, at 60 ~ 80 DEG C, in neutralizing tank, mix, control pH value 7.0 ~ 9.0, after filtration, washing, acidifying, the balling-up of pressurizeing in oil ammonia column, through super-dry, aging, 650 ~ 750 DEG C of roastings 4 hours, obtain the alumina globule containing Sn 1.0wt%.
The alumina globule carrier that contains 1.0% Sn, at 800 DEG C of roasting 3h, is flooded to 4h by the carrier after roasting and the aqueous solution that contains chloroplatinic acid at 70 DEG C, dry 2h at 120 DEG C, roasting 4h at 500 DEG C activates 4h in the air that contains water vapour.Then at 70 DEG C with contain KNO
3aqueous solution dipping 2h, dry, roasting under same condition.In catalyst, the load capacity of each component is: Pt 0.7wt%, Sn 1.0wt%, K 1.0wt%.
activation condition:first under nitrogen atmosphere, be warming up to 500 DEG C, 500 DEG C of constant temperature reductase 12 5min of hydrogen, nitrogen protection borehole cooling to 300 DEG C, 300 ~ 500 DEG C of temperature programmed reductions, heating rate is 1 DEG C/min.In activation process, the volume space velocity of reducing gases hydrogen is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 37%
appreciation condition: catalyst volume 3.0ml, volume space velocity 3000 h
-1, reaction pressure 0.1MPa, reaction temperature is 580 DEG C, hydrogen: the ratio of iso-butane is at 1:1.
result shows: this catalyst is being evaluated 72h continuously, and iso-butane conversion ratio is 38.27%, and selective isobutene is 96.46%, and conversion ratio declines 1.7 percentage points, has selectively increased by 0.7 percentage point, and coke content is only 1.76%, demonstrates good catalytic activity and stability.
Example 3
Prepare dehydrogenation according to the method that embodiment 1 is identical.
activation condition:first under nitrogen atmosphere, be warming up to 500 DEG C, 500 DEG C of constant temperature reduction 35min of high-purity hydrogen, nitrogen protection borehole cooling to 280 DEG C, 280 ~ 500 DEG C of temperature programmed reductions, heating rate is 3 DEG C/min.In activation process, the volume space velocity of reducing gases hydrogen is 3000h
-1.In dehydrogenation, the reduction degree of Pt is 45%
appreciation condition: catalyst volume 3.0ml, volume space velocity 2000 h
-1, reaction pressure 0.1MPa, reaction temperature is 590 DEG C, hydrogen: the ratio of iso-butane is at 2:1.
evaluation result: this catalyst is being evaluated after 24h continuously, and iso-butane conversion ratio is 39.42%, and selective isobutene is 95.88%, conversion ratio and selectively substantially constant, and coke content is only 0.98%, demonstrates good catalytic activity and stability.
Claims (10)
1. a high temperature reduction is in conjunction with the dehydrogenation activation method of temperature programmed reduction, dehydrogenation is platinum family loaded catalyst, it is characterized in that: dehydrogenation activation process is first carried out high temperature reduction, then adopt temperature programmed reduction, high temperature reduction adopts hydrogen in the time of 450～550 DEG C, to reduce 5～55min; Temperature programmed reduction adopts hydrogen reducing, and temperature programmed reduction initial temperature is 240～400 DEG C, and temperature programmed reduction end temp is 450～550 DEG C, and programming rate is 0.5～10 DEG C/min; Then temperature is adjusted to 500～650 DEG C, cancels sulfuration passivation, and the unstripped gas that directly passes into hydrogen carries out dehydrogenation reaction.
2. it is characterized in that in accordance with the method for claim 1: after reduction, in dehydrogenation, the reduction degree of active component Pt reaches 30%～50%.
3. it is characterized in that in accordance with the method for claim 1: the hydrogen of reduction use concentration is by volume at least 90%.
4. it is characterized in that in accordance with the method for claim 1: the recovery time of high temperature reduction is 10～40min.
5. it is characterized in that in accordance with the method for claim 1: the programming rate of temperature programmed reduction is 0.5～5 DEG C/min.
6. according to the method described in claim 1 or 2, it is characterized in that: dehydrogenation is platinum family loaded catalyst, taking one or more in the platinum in platinum family, palladium, iridium, rhodium or osmium as active component, active component contains platinum, taking element active component as vehicle weight 0.01%～2%.
7. in accordance with the method for claim 6, it is characterized in that: in dehydrogenation, contain auxiliary agent, auxiliary agent is one or more in Sn, K, rare earth metal.
8. in accordance with the method for claim 7, it is characterized in that: in dehydrogenation, the content of auxiliary agent Sn or La is counted 0.1%～10% of vehicle weight with element, the content of K is counted 0.1%～10% of vehicle weight with element.
9. in accordance with the method for claim 1, it is characterized in that: dehydrogenation reaction temperature is 500～650 DEG C, volume space velocity is 500～5000h
-1, absolute pressure 0.1～0.5MPa, hydrogen: the molar ratio of low-carbon alkanes is between 1:1～6:1.
10. it is characterized in that in accordance with the method for claim 9: low-carbon alkanes is C
2～C
5alkane.
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| CN101683618A (en) * | 2008-09-24 | 2010-03-31 | 华东理工大学 | Catalyst used for preparing amino acid salt through low-temperature oxidative dehydrogenation by using amino alcohol |
| CN101698152A (en) * | 2009-10-20 | 2010-04-28 | 武汉凯迪科技发展研究院有限公司 | Cobalt-based compounded catalyst and preparing method and application thereof |
| CN101898131A (en) * | 2009-05-25 | 2010-12-01 | 中国石油化工股份有限公司 | Dehydrogenation catalyst taking Sn-containing alumina as carrier and preparation method thereof |
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| US4786625A (en) * | 1987-02-25 | 1988-11-22 | Uop Inc. | Dehydrogenation catalyst compositon |
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