CN103785384B - A kind of preparation method of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation - Google Patents
A kind of preparation method of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, comprise the steps: that (1) preparation contains the alumina support of Sn and alkali metal promoter, wherein Sn and alkali metal promoter are introduced in plastic process, the alkali-metal amount introduced accounts for 10 ~ 70wt% of alkali metal total amount in final catalyst, is preferably 20 ~ 50wt%; (2) aluminium oxide containing Sn and alkali metal promoter prepared with step (1), for carrier, introduces alkali metal or alkali metal promoter component and dehydrogenation active component total immersion again on carrier after supported active metals Pt; (3) steam dechlorination is carried out to the catalyst of step (2) gained.Catalyst prepared by the method can reduce carbon distribution in long period dehydrogenation reaction process, minimizing alkali metal not easily runs off, and the stability of catalyst is largely increased.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, particularly a kind of preparation method of C2 ~ C5 dehydrating alkanes alkene catalyst, belongs to the catalyst preparation technology in Industrial Catalysis technical field.
Background technology
Along with transfering natural gas from the west to the east and eastern perfect further, the exploitation in gas field, the East Sea and the application of coal bed gas sending engineering of river gas, original civil liquefied gas is caused to steam again to refinery gradually.And the continuous expansion of China's ethene production capacity and oil refining scale, the total amount of liquefied gas is also among sustainable growth.Therefore, effective utilization of liquefied gas more and more receives the concern of people, now becomes the hot issue of petrochemical industry.
At present, preparing propylene by dehydrogenating propane is that liquefied gas produces one of important channel of industrial chemicals, and it will become an emphasis of new century petrochemical technology research and development.Preparing propylene by dehydrogenating propane not only can alleviate the propylene disparities between supply and demand of increasingly sharpening, and is also the key point of propane comprehensive utilization.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, the key that the catalyst for preparing propylene with propane dehydrogenation with high activity, high selectivity and high stability becomes this technology is developed.CN1201715 patent discloses the Pt-Sn-K/Al for dehydrogenating low-carbon alkane
2o
3the preparation method of catalyst.USP4,914,075, USP4,353,815, USP4,420,649, USP4,506,032, USP4,595,673, EP562,906, EP98,622 grades all report for propane catalyst based with other dehydrogenating low-carbon alkane Pt, have high alkane conversion and olefine selective.Although the alkane conversion of these catalyst under some reaction condition and olefine selective high, due to the easy carbon distribution inactivation of catalyst under the high temperature conditions, cause the poor stability of catalytic reaction, the service life of catalyst is shorter.Alkali-metal interpolation can the part acid site of catalyst neutralisation carrier surface, the precursor of carbon distribution is suppressed in the conversion on acidity of catalyst surface and the deposition on catalyst surface, thus strengthen the carbon accumulation resisting ability of catalyst, improve the stability of catalyst.In prior art, alkali-metal allotment is often flooded in the final step of catalyst preparing, active force between alkali metal and carrier is more weak, alkali-metal loss can be produced in actual commercial Application, and then along with the increase of the duration of runs and regeneration times, the carbon accumulation resisting ability of catalyst and stability all can be affected.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin.The method prepare catalyst can reduce carbon distribution in long period dehydrogenation reaction process, alkali metal not easily runs off, the stability of catalyst is largely increased.
A preparation method for catalyst for dehydrogenation of low-carbon paraffin, comprises the steps:
(1) preparation contains the alumina support of Sn and alkali metal promoter, and wherein Sn and alkali metal promoter are introduced in plastic process, and the alkali-metal amount of introducing accounts for 10 ~ 70wt% of alkali metal total amount in final catalyst, is preferably 20 ~ 50wt%;
(2) aluminium oxide containing Sn and alkali metal promoter prepared with step (1), for carrier, introduces alkali metal or alkali metal promoter component and dehydrogenation active component total immersion again on carrier after supported active metals Pt;
(3) steam dechlorination is carried out to the catalyst of step (2) gained.
In the inventive method step (1), by ammonia spirit and containing Sn, alkali metal promoter aluminum salt solution and stream is added in plastic cans, after cemented into bundles at ammonium concentration be to stir aging 0.2 ~ 4h, preferred ageing time 0.5 ~ 2h under the condition of 0.4 ~ 0.6M.Wherein, alkali metal promoter is generally selected from one or more elements in Li, Na, K.Aluminium salt comprises aluminum sulfate, aluminum nitrate, alchlor, preferred alchlor, and the chlorion of introducing removes, without the need to washing by follow-up steam dechlorination step.In aluminum salt solution containing Sn, alkali metal promoter, aluminum ions concentration is 0.5 ~ 1.6M, preferably 0.8 ~ 1.2M, flow velocity 0.1 ~ 20ml/min, preferably 0.1 ~ 5ml/min.Ammonia concn is 8 ~ 15wt%.Gelling temperature 60 ~ 80 DEG C, pH value is 7.0 ~ 12.0, is preferably 8.0 ~ 10.0.By slurries filtration, vacuum drying, shaping, roasting after aging, also can directly carry out vacuum drying, shaping, roasting without filtration.Baking temperature is 60 ~ 150 DEG C, and drying time is 8h ~ 48h, dry 16 ~ 32h at being preferably 80 ~ 120 DEG C.Sintering temperature is 400 DEG C ~ 800 DEG C, roasting time 2 ~ 24h, roasting 4 ~ 8h at being preferably 500 ~ 700 DEG C.Carrier forming method is the method that those skilled in the art is known, as dripped a ball forming, extruded etc.Above-mentioned alumina support can be spherical, bar shaped, microballoon or abnormity, and particle equivalent diameter is 0.1 ~ 5mm, is preferably 0.5 ~ 2mm.The carrying alumina surface area per unit volume of preparation is 200 ~ 240m
2/ g, 0.60 ~ 0.80cm
3/ g.
In the inventive method step (2), by Pt element wt content meter in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution or configure containing Pt and alkali-metal mixed aqueous solution.Flood 4 ~ 8h under 60 ~ 80 DEG C of conditions, baking temperature is 60 ~ 150 DEG C, and drying time is 1h ~ 24h, dry 4 ~ 8h at being preferably 80 ~ 120 DEG C.Sintering temperature is 400 DEG C ~ 800 DEG C, roasting time 2 ~ 24h, roasting 4 ~ 8h at being preferably 500 ~ 700 DEG C.
In the inventive method step (3), described steam dechlorination is process 1 ~ 20h at 300 ~ 800 DEG C, and process 4 ~ 8h at being preferably 500 ~ 700 DEG C, the atmosphere of dechlorination is the air containing 10v% ~ 30v% water vapour, makes chlorinity in catalyst be less than 0.15wt%.
A kind of catalyst for dehydrogenation of low-carbon paraffin, adopts above method to prepare, by weight percentage, containing 0.2 ~ 0.8wt%Pt, 0.5 ~ 3.0wt% alkali metal in catalyst, and 0.3 ~ 2.0wt%Sn.
Compared with prior art, preparation method's tool of a kind of catalyst for dehydrogenation of low-carbon paraffin of the present invention has the following advantages:
(1) catalyst for dehydrogenation of low-carbon paraffin that prepared by the inventive method has additive alkali metal and Sn is evenly distributed, and anti-carbon is strong, and alkali metal not easily runs off, and the activity stability of catalyst long-term operation significantly improves;
(2) the inventive method is particularly in the process that plastic is aging, the suitable concentration of ammonium ion is controlled by dropping ammoniacal liquor or distilled water, have adjusted the isoelectric point of plastic carrier, further enhancing the strong interaction between plastic carrier and alkali metal ion, effect particularly between meta-aluminic acid root and alkali metal ion, potassium ion is not easily run off in filtration, even washing, long period course of reaction, and improves the dispersion effect of alkali metal ion;
(3) method for preparing catalyst is simple, and mature technology, is conducive to the industrial production of catalyst.
Detailed description of the invention
Enforcement below by dehydrogenating propane is described further technology of the present invention.
Example 1
Configuration concentration is the aluminum trichloride solution of 0.98M, is added in aluminum trichloride solution by often liter of solution 0.0013mol butter of tin and 0.0026mol potassium nitrate.Under agitation, the slow also stream of ammoniacal liquor of above-mentioned solution and concentration 8wt% is added in plastic cans.Control temperature 70 C in plastic cans, above-mentioned aluminum trichloride solution coutroi velocity 2ml/min, control ammoniacal liquor and add speed, maintaining material pH value in plastic cans is 8.0 ~ 10.0.After cemented into bundles, slurries are made to stir aging 0.5h under ammonium concentration is the condition of 0.4M, then by slurries filtration, vacuum drying, shaping, roasting.Baking temperature is 80 DEG C, and drying time is 32h.Sintering temperature is 700 DEG C, roasting time 6h.Obtain the alumina support containing Sn0.3wt% and K0.2wt%.
By Pt content 0.4wt% in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution.Above-mentioned carrier floods 6h under 70 DEG C of conditions in containing the aqueous solution of chloroplatinic acid, then at 120 DEG C of dry 2h, and roasting 4h at 500 DEG C.By K content 0.8wt% in final catalyst, cut contained 0.2wt%K in carrier, take the appropriate potassium nitrate configuration aqueous solution, at 70 DEG C, flood 2h, roasting dry with similarity condition after leaching Pt.Gained material activates 4h in containing the air of 20v% water vapour.In final catalyst, the load capacity of each component is: Pt0.4wt%, Sn0.3wt%, K0.8wt%.Before reaction, gained catalyst is 500 DEG C of reduction 4h in a hydrogen atmosphere.
Appreciation condition: catalyst quality 3.53g, the mass space velocity of propane is 3h
-1, reaction pressure 0.1MPa, reaction temperature is 620 DEG C, according to the response situation adjustment response parameter of reality.
Result shows: the catalyst after 5 regeneration is evaluating 72h continuously, and conversion of propane is 31.7%, and Propylene Selectivity is 96.4%.Coke content is only 4.42%.After catalyst after 10 regeneration evaluates 72h continuously, conversion of propane is 29.8%, and Propylene Selectivity is 96.3%, and in catalyst, the weight content of potassium element is 0.8wt%.
Example 2
Configuration concentration is the aluminum trichloride solution of 1.18M, is added in aluminum trichloride solution by often liter of solution 0.0051mol butter of tin and 0.035mol lithium nitrate.Under agitation, the slow also stream of ammoniacal liquor of above-mentioned solution and concentration 10wt% is added in plastic cans.Control temperature 80 DEG C in plastic cans, above-mentioned aluminum trichloride solution coutroi velocity 5ml/min, control ammoniacal liquor and add speed, maintaining material pH value in plastic cans is 8.0 ~ 10.0.Slurries are made to stir aging 1h under ammonium concentration is the condition of 0.5M, then by slurries filtration, vacuum drying, shaping, roasting.Baking temperature is 100 DEG C, and drying time is 24h.Sintering temperature is 600 DEG C, roasting time 8h.Obtain the alumina support containing Sn1.0wt% and Li0.4wt%.
By Pt content 0.5wt% in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution.Above-mentioned carrier floods 8h under 60 DEG C of conditions in containing the aqueous solution of chloroplatinic acid, then at 100 DEG C of dry 4h, and roasting 4h at 600 DEG C.By Li content 0.7wt% in final catalyst, cut contained 0.4wt%Li in carrier, take the appropriate lithium nitrate configuration aqueous solution, at 60 DEG C, flood 8h, roasting dry with similarity condition after leaching Pt.Gained material activates 4h in containing the air of 30v% water vapour.In the agent of gained catalyst, the load capacity of each component is: Pt0.5wt%, Sn1.0wt%, Li0.7wt%.Before reaction, gained catalyst is 500 DEG C of reduction 4h in a hydrogen atmosphere.
Appreciation condition: catalyst quality 3.53g, the mass space velocity of propane is 3h
-1, reaction pressure 0.1MPa, reaction temperature is 620 DEG C, according to the response situation adjustment response parameter of reality.
Result shows: the catalyst after 5 regeneration is evaluating 72h continuously, and conversion of propane is 31.2%, and Propylene Selectivity is 95.2%.Coke content is only 5.46%.After catalyst after ten regeneration evaluates 72h continuously, conversion of propane is 30.6%, and Propylene Selectivity is 96.1%, and in catalyst, the weight content of elemental lithium is 0.7wt%.
Example 3
Configuration concentration is the aluminum trichloride solution of 1.08M, is added in aluminum trichloride solution by often liter of solution 0.007mol butter of tin and 0.0085mol potassium nitrate.Under agitation, the slow also stream of ammoniacal liquor of above-mentioned solution and concentration 15wt% is added in plastic cans.Control temperature 60 C in plastic cans, above-mentioned aluminum trichloride solution coutroi velocity 5ml/min, control ammoniacal liquor and add speed, maintaining material pH value in plastic cans is 8.0 ~ 10.0.Slurries are made to stir aging 2h under ammonium concentration is the condition of 0.5M, then by slurries vacuum drying, shaping, roasting.Baking temperature is 120 DEG C, and drying time is 16h.Sintering temperature is 500 DEG C, roasting time 8h.Obtain the alumina support containing Sn1.5wt% and K0.6wt%.
By Pt content 0.7wt% in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution.Above-mentioned carrier floods 6h under 70 DEG C of conditions in containing the aqueous solution of chloroplatinic acid, then at 120 DEG C of dry 4h, and roasting 4h at 700 DEG C.By K content 1.5wt% in final catalyst, cut contained 0.6wt%K in carrier, take the appropriate potassium nitrate configuration aqueous solution, at 70 DEG C, flood 6h, roasting dry with similarity condition after leaching Pt.Gained material activates 4h in containing the air of 20v% water vapour.In gained catalyst, the load capacity of each component is: Pt0.7wt%, Sn1.5wt%, K1.5wt%.Before reaction, gained catalyst is 500 DEG C of reduction 4h in a hydrogen atmosphere.
Appreciation condition: catalyst quality 3.0g, the mass space velocity of propane is 3h
-1, reaction pressure 0.1MPa, reaction temperature is 620 DEG C, according to the response situation adjustment response parameter of reality.
Result shows: the catalyst after 5 regeneration is evaluating 72h continuously, and conversion of propane is 31.8%, and Propylene Selectivity is 96.6%.Coke content is only 5.08%.After catalyst after ten regeneration evaluates 50h continuously, conversion of propane is 31.1%, and Propylene Selectivity is 96.1%, and in catalyst, the weight content of potassium element is 1.5wt%.
Example 4
Configuration concentration is the aluminum trichloride solution of 1.08M, is added in aluminum trichloride solution by often liter of solution 0.007mol butter of tin and 0.02mol sodium nitrate.Under agitation, the slow also stream of ammoniacal liquor of above-mentioned solution and concentration 8wt% is added in plastic cans.Control temperature 70 C in plastic cans, above-mentioned aluminum trichloride solution coutroi velocity 2ml/min, control ammoniacal liquor and add speed, maintaining material pH value in plastic cans is 8.0 ~ 10.0.After cemented into bundles, slurries are made to stir aging 2h under ammonium concentration is the condition of 0.6, then by slurries vacuum drying, shaping, roasting.Baking temperature is 100 DEG C, and drying time is 24h.Sintering temperature is 700 DEG C, roasting time 6h.Obtain the alumina support containing Sn1.5wt% and Na0.8wt%.
By Pt content 0.8wt% in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution.Above-mentioned carrier floods 6h under 70 DEG C of conditions in containing the aqueous solution of chloroplatinic acid, then at 120 DEG C of dry 4h, and roasting 4h at 700 DEG C.By Na content 1.8wt% in final catalyst, cut contained 0.8wt%Na in carrier, take the appropriate sodium nitrate configuration aqueous solution, at 70 DEG C, flood 6h, roasting dry with similarity condition after leaching Pt.Gained material activates 4h in containing the air of 20v% water vapour.In gained catalyst, the load capacity of each component is: Pt0.8wt%, Sn1.5wt%, Na1.8wt%.Before reaction, gained catalyst is 500 DEG C of reduction 4h in a hydrogen atmosphere.
Appreciation condition: catalyst quality 3.53g, the mass space velocity of propane is 3h
-1, reaction pressure 0.1MPa, reaction temperature is 620 DEG C, according to the response situation adjustment response parameter of reality.
Result shows: the catalyst after 5 regeneration is evaluating 72h continuously, and conversion of propane is 31.4%, and Propylene Selectivity is 96.3%.Coke content is only 5.12%.After catalyst after five regeneration evaluates 72h continuously, conversion of propane is 31.2%, and Propylene Selectivity is 96.0%, and in catalyst, the weight content of sodium element is 1.8wt%.
Comparative example
Dehydrogenation is prepared by patent 201010272305.X.
Configuration concentration is the aluminum trichloride solution of 0.98M, is added in aluminum trichloride solution by often liter of solution 0.0013mol butter of tin.Under agitation, the slow also stream of ammoniacal liquor of above-mentioned solution and concentration 8wt% is added in plastic cans.Control temperature 70 C in plastic cans, above-mentioned aluminum trichloride solution coutroi velocity 2ml/min, control ammoniacal liquor and add speed, maintaining material pH value in plastic cans is 8.0 ~ 10.0.After cemented into bundles, slurries are aging 0.5h under stirring, then by slurries filtration, dry, shaping, roasting.Baking temperature is 80 DEG C, and drying time is 4h.Sintering temperature is 700 DEG C, roasting time 6h.Obtain the alumina support containing Sn0.3wt%.
By Pt content 0.4wt% in final catalyst, take the appropriate chloroplatinic acid configuration aqueous solution.Above-mentioned carrier floods 6h under 70 DEG C of conditions in containing the aqueous solution of chloroplatinic acid, then at 120 DEG C of dry 2h, and roasting 4h at 500 DEG C.Gained material activates 4h in containing the air of 20v% water vapour.By K content 0.8wt% in final catalyst, take the appropriate potassium nitrate configuration aqueous solution, at 70 DEG C, flood 2h, roasting dry with similarity condition after leaching Pt.In gained catalyst, the load capacity of each component is: Pt0.4wt%, Sn0.3wt%, K0.8wt%.Before reaction, gained catalyst is 500 DEG C of reduction 4h in a hydrogen atmosphere.
Appreciation condition: catalyst quality 3.53g, the mass space velocity of propane is 3h
-1, reaction pressure 0.1MPa, reaction temperature is 620 DEG C, according to the response situation adjustment response parameter of reality.
Result shows: the catalyst after 5 regeneration is evaluating 72h continuously, and conversion of propane is 29.2%, and Propylene Selectivity is 95.8%.Coke content is 7.52%.After catalyst after 10 regeneration evaluates 72h continuously, conversion of propane is 27.18%, and Propylene Selectivity is 94.4%, and in catalyst, the weight content of potassium element is 0.7wt%.Compared with embodiment 1, all there is a certain distance in the stability of coke content, catalyst and the activity of circulation rear catalyst.
Claims (10)
1. a preparation method for catalyst for dehydrogenation of low-carbon paraffin, is characterized in that: comprise the steps:
(1) preparation contains the alumina support of Sn and alkali metal promoter, and wherein Sn and alkali metal promoter are introduced in plastic process, and the alkali-metal amount of introducing accounts for 10 ~ 70wt% of alkali metal total amount in final catalyst;
(2) aluminium oxide containing Sn and alkali metal promoter prepared with step (1), for carrier, introduces alkali metal or alkali metal promoter component and dehydrogenation active component total immersion again on carrier after supported active metals Pt;
(3) steam dechlorination is carried out to the catalyst of step (2) gained;
In step (1), by ammonia spirit and containing Sn, alkali metal promoter aluminum salt solution and stream is added in plastic cans, after cemented into bundles at ammonium concentration be to stir aging 0.2 ~ 4h under the condition of 0.4 ~ 0.6M.
2. method according to claim 1, is characterized in that: alkali metal promoter is selected from one or more in Li, Na, K, aluminium salt comprises aluminum sulfate, aluminum nitrate, alchlor.
3. method according to claim 1, is characterized in that: in the aluminum salt solution containing Sn, alkali metal promoter, aluminum ions concentration is 0.5 ~ 1.6M, flow velocity 0.1 ~ 20ml/min, and ammonia concn is 8 ~ 15wt%.
4. method according to claim 3, is characterized in that: in the aluminum salt solution containing Sn, alkali metal promoter, aluminum ions concentration is 0.8 ~ 1.2M, flow velocity 0.1 ~ 5ml/min.
5. method according to claim 1, is characterized in that: gelling temperature 60 ~ 80 DEG C, and pH value is 7.0 ~ 12.0.
6. method according to claim 1, is characterized in that: by slurries filtration, vacuum drying, shaping, roasting or directly carry out vacuum drying, shaping, roasting without filtration after aging.
7. method according to claim 6, is characterized in that: baking temperature is 60 ~ 150 DEG C, and drying time is 8h ~ 48h, and sintering temperature is 400 DEG C ~ 800 DEG C, roasting time 2 ~ 24h.
8. method according to claim 1, it is characterized in that: in step (2), by Pt element wt content meter in final catalyst, the mixed aqueous solution taking the appropriate chloroplatinic acid configuration aqueous solution or configure containing Pt, K, carrier 4 ~ 8h that under 60 ~ 80 DEG C of conditions, impregnation steps (1) is obtained, baking temperature is 60 ~ 150 DEG C, drying time is 1h ~ 24h,, sintering temperature is 400 DEG C ~ 800 DEG C, roasting time 2 ~ 24h.
9. method according to claim 1, is characterized in that: in step (3), and described steam dechlorination is process 1 ~ 20h at 300 ~ 800 DEG C, and the atmosphere of dechlorination is the air containing 10v% ~ 30v% water vapour.
10. a catalyst for dehydrogenation of low-carbon paraffin, is characterized in that: adopt arbitrary described method preparation in claim 1 to 9, by weight percentage, containing 0.2 ~ 0.8wt%Pt, 0.5 ~ 3.0wt% alkali metal in catalyst, and 0.3 ~ 2.0wt%Sn.
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| CN104190418A (en) * | 2014-08-19 | 2014-12-10 | 中国科学院山西煤炭化学研究所 | Catalyst for preparation of light olefins from light alkanes as well as preparation method and application of catalyst |
| CN105582917B (en) * | 2014-10-22 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of dechlorination method of noble metal dehydrogenation catalyst |
| CN107213919B (en) * | 2016-03-22 | 2020-05-12 | 北京安耐吉能源工程技术有限公司 | Alumina carrier, preparation method and application thereof |
| CN107213909B (en) * | 2016-03-22 | 2020-05-12 | 北京安耐吉能源工程技术有限公司 | Dehydrogenation catalyst and preparation method and application thereof |
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