CN102389831B - Catalyst for preparing propylene through propane catalytic dehydrogenation and preparation method thereof - Google Patents
Catalyst for preparing propylene through propane catalytic dehydrogenation and preparation method thereof Download PDFInfo
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- CN102389831B CN102389831B CN2011102833586A CN201110283358A CN102389831B CN 102389831 B CN102389831 B CN 102389831B CN 2011102833586 A CN2011102833586 A CN 2011102833586A CN 201110283358 A CN201110283358 A CN 201110283358A CN 102389831 B CN102389831 B CN 102389831B
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Abstract
The invention relates to a catalyst for preparing propylene through propane catalytic dehydrogenation, which is a load type platinum-based catalyst and is characterized in that home-made mesoporous molecular sieves MCM-41 are used as carriers, metal Pt is used as an active ingredient, and metals Sn, Sn-Ce or Sn-Ce-Ca are used as auxiliary agents. In a preparation method, an isovolumetric continuous immersion method is adopted for preparation. The catalyst and the preparation method have the advantages that the isovolumetric continuous immersion method is adopted for preparing multi-component catalysts, wherein the content of any one component is easy to control, the prepared catalyst has higher specific surface area (700 to 900m<2>/g) and has high catalytic activity, the propane conversion rate is high, the propylene selectivity is good, the one-path stability is good, in addition, the service life is longer, the preparation method of the catalyst carriers is simple and feasible, the economic benefit is obvious, and good industrial development and application prospects are realized.
Description
Technical field
The present invention relates to the catalysis technique of preparing propylene by dehydrogenating propane, particularly a kind of Catalysts and its preparation method for preparing propylene for the propane catalytic dehydrogenation.
Background technology
Propylene is a kind of basic Organic Chemicals, and its economic worth is self-evident.Purposes relates to a lot of aspects, except for the manufacture of polypropylene, also in large quantities as the primary raw material of producing the products such as acrylonitrile, butanols, octanol, expoxy propane, isopropylbenzene and nonyl phenol, the oligomer of propylene is the Main Ingredients and Appearance that improves octane number in addition.At present, the propylene supply is mainly from the byproduct of naphtha pyrolysis ethene processed and petroleum catalytic cracking process.Along with the development of petro chemical industry, the demand of propylene is increasing, and supply falls short of demand further.How China's propane flammable gas aboundresources, but major part is used as domestic fuel will be measured rich inexpensive propane and react by catalysis dehydrogenation and make that market is in short supply, propylene that high added value is arranged, be difficult point and the focus of current research.At present, adopt the technology of preparing propylene by dehydrogenating propane to mainly contain: 1) oxidative dehydrogenation, 2) catalytic dehydrogenation, 3) membrane reactor dehydrogenation.Also carry out the dehydrogenation research of the low-carbon alkanes such as propane, butane aspect although China is domestic, not yet set up at present the dehydrogenating propane process units.Typical alkene industrialized producing technology has the Catofin technique of Lummus company and the Oleflex technique of Uop Inc., also has in addition the STAR technique of Phillips company and the PDH technique of Linde-BASF company.
The load type platinum series catalysts is the important alkane dehydrogenating catalyst of a class, can be used for reformation and the dehydrogenation of alkane.Such catalyst is to be prepared from by activity component metal platinum and the various metal promoters of interpolation.Platinum group catalyst possesses that conversion ratio is high, selectivity good, good stability and the characteristics such as environmentally friendly, thereby has extraordinary prospects for commercial application.
Summary of the invention
The object of the invention is to for above-mentioned technical Analysis, a kind of Catalysts and its preparation method for preparing propylene for the propane catalytic dehydrogenation is provided, this catalyst activity is high, selective good, long service life; This catalyst adopts equal-volume continuous impregnating legal system standby, and technique is simple, easy operating, is conducive to apply.
Technical scheme of the present invention:
A kind of catalyst for preparing propylene for the propane catalytic dehydrogenation, be the load type platinum series catalysts, it is characterized in that: be carrier by homemade mesopore molecular sieve MCM-41, take Pt metal as active component, consist of take metal Sn, Sn-Ce or Sn-Ce-Ca as auxiliary agent, in catalyst, the quality percentage composition of each component is: active component Pt 0.1-1.0%, auxiliary agent Sn 0.3-1.2%, Ce 0.5-3.0%, Ca 0.1-2.0%.
The preparation method of described mesopore molecular sieve MCM-41 is: after 4.0 g softex kws are added 104.0 mL deionized water for stirring dissolvings, slowly drip the 20.0mL ethyl orthosilicate, stir 10 min, more slowly drip 48.0mL ammoniacal liquor, stir 3-4 h under room temperature; Filter with sand core funnel after standing 48 h, wash to filtrate and be neutral, room temperature is dried in the shade and is namely got former powder; Former powder is put 120 ℃ of oven dry 12 h of people's baking oven, grind into powder, roasting in Muffle furnace first at 350 ℃ of constant temperature 2 h, then is warmed up to 550 ℃ of constant temperature 5 h, and is naturally cooling, namely obtains removing the mesopore molecular sieve MCM-41 of surfactant.
A kind of preparation method who prepares the catalyst of propylene for the propane catalytic dehydrogenation adopts equal-volume continuous impregnating legal system standby, and step is as follows:
1) preparation of powder MCM-41 carrier: the sample after roasting after fully grinding, is used powder with obtaining testing after 40 purpose sieve screenings;
2) first before dipping, first with carrier at 550 ℃ of lower roasting 4h, then with the first compounding agent solution dipping 12h, 60 ℃ ,-use the Rotary Evaporators desolventizing under the 0.08Mp pressure condition, dry 12h under 120 ℃, 550 ℃ of lower roasting 4h;
3) according to step 2) described in identical method flood again other compounding agent solution;
4) final impregnating active component platinum, method is the carrier that will flood after all compounding agent solutions, floods 12h with chloroplatinic acid aqueous solution, 60 ℃ ,-use the Rotary Evaporators desolventizing under the 0.08Mp pressure condition, dry 12h under 120 ℃, 550 ℃ of lower roasting 4h can make catalyst.
Described compounding agent solution take Sn as auxiliary agent is SnCl
2Ethanolic solution, SnCl
2The concentration of ethanolic solution is 0.0084-0.0337 mol/L.
Described compounding agent solution take Ce as auxiliary agent is Ce (NO
3)
3The aqueous solution, Ce (NO
3)
3The concentration of the aqueous solution is 0.0119-0.0714mol/L.
Described compounding agent solution take Ca as auxiliary agent is Ca (NO
3)
2The aqueous solution, Ca (NO
3)
2The concentration of the aqueous solution is 0.0083-0.167mol/L.
The concentration of described chloroplatinic acid aqueous solution is 0.0017-0.0170mol/L.
A kind of application for preparing the catalyst of propylene for the propane catalytic dehydrogenation is used for the propane catalytic dehydrogenation and prepares propylene, and the catalytic dehydrogenating reaction condition is: temperature 550-650 ℃, the space-time speed (GSHV) of pressure 0.1Mp, reaction gas are 2500-4000h
-1
Advantage of the present invention is: adopt continuous equi-volume impregnating to prepare multicomponent catalyst, wherein arbitrary constituent content all is easy to control; The catalyst of preparation has higher specific area (700-900m
2/ g); The catalyst of preparation has high catalytic activity, and conversion of propane is high, and is good to Propylene Selectivity, and one way good stability and life-span are longer; This catalyst carrier preparation method simple possible, remarkable in economical benefits has good commercial development application prospect.
Description of drawings
Fig. 1 is that A, B, three kinds of catalyst of C are to propane catalytic dehydrogenation conversion ratio.
Fig. 2 is that A, B, three kinds of catalyst of C are selective to the propane catalytic dehydrogenation.
The specific embodiment
The present invention is described further below by instantiation.
At first prepare mesopore molecular sieve MCM-41 powder, method is: after 4.0 g softex kws are added 104.0 mL deionized water for stirring dissolvings, slowly drip the 20.0mL ethyl orthosilicate, stir 10 min, slowly drip again 48.0mL ammoniacal liquor, stir 3-4 h under room temperature; Filter with sand core funnel after standing 48 h, wash to filtrate and be neutral, room temperature is dried in the shade and is namely got former powder; Former powder is put 120 ℃ of oven dry 12 h of people's baking oven, grind into powder, roasting in Muffle furnace first at 350 ℃ of constant temperature 2 h, then is warmed up to 550 ℃ of constant temperature 5 h, and is naturally cooling, namely obtains removing the mesopore molecular sieve MCM-41 of surfactant.
Embodiment 1:
A kind of preparation method who prepares the catalyst of propylene for the propane catalytic dehydrogenation adopts equal-volume continuous impregnating legal system standby, and step is as follows:
1) take homemade powder MCM-41 carrier 3.0g, in 550 ℃ of lower roasting 4h;
2) with concentration be the SnCl of 0.0168mol/L
2Ethanolic solution 9.0ml dipping 1) the MCM-41 carrier 12 h in the step after roasting, then 60 ℃ ,-use the Rotary Evaporators desolventizing under the 0.08Mp condition, dry 12h under 120 ℃, 550 ℃ of lower roasting 4h;
3) with concentration be again the H of 0.0068mol/L
2PtCl
6Aqueous solution 9.0ml dipping 2) the sample 12h of step after processing, 60 ℃ ,-use the Rotary Evaporators desolventizing under the 0.08Mp condition, dry 12h under 120 ℃, 550 ℃ of lower roasting 4h make catalyst A at last.
The catalyst A component is: Pt-Sn/MCM-41, and the catalytic reaction temperature is 550-620 ℃, and pressure is 0.1Mp, and reaction gas space-time speed (GSHV) is 2500-4000h
-1, after reaction gaseous product through the gas chromatograph on-line analysis, conversion of propane such as Fig. 1, propylene selective as Fig. 2.
Embodiment 2:
A kind of preparation method who prepares the catalyst of propylene for the propane catalytic dehydrogenation adopts equal-volume continuous impregnating legal system standby, and step is as follows:
1) take homemade powder MCM-41 carrier 3.0g, in 550 ℃ of lower roasting 4h;
2) with concentration be the Ce (NO of 0.0291mol/L
3)
3Aqueous solution 9.0ml floods 12h, then 60 ℃ ,-use the Rotary Evaporators desolventizing under the 0.08Mp condition, dry 12h under 120 ℃, 550 ℃ of lower roasting 4h;
3) to 2) sample after the step processes floods 0.0168mol/L SnCl again
2Ethanolic solution 9.0ml, its preparation process and the 2nd) step identical;
4) at last to 3) sample dipping concentration after the step processes is 0.0068mol/L H
2PtCl
6Aqueous solution 9.0ml, its preparation process and condition and step 2) identical, can make catalyst B.
The component of catalyst B is: Pt-Sn-Ce/MCM-41, the catalytic applications testing conditions is identical with embodiment 1, after reaction gaseous product through the gas chromatograph on-line analysis, conversion of propane such as Fig. 1, propylene selective as Fig. 2.
Embodiment 3:
A kind of preparation method who prepares the catalyst of propylene for the propane catalytic dehydrogenation adopts equal-volume continuous impregnating legal system standby, and step is as follows:
1) step 1) with embodiment 2 is identical;
2) with the step 2 of embodiment 2) identical;
3) step 3) with embodiment 2 is identical;
4) with the sample after the processing of step 3) step, then be the Ca (NO of 0.0167mol/L with concentration
3)
2Solution 9.0ml floods 12h, then 60 ℃ ,-use the Rotary Evaporators desolventizing under the 0.08Mp condition, dry 12h under 120 ℃, 550 ℃ of lower roasting 4h;
5) sample after above-mentioned processing be impregnated in the H that concentration is 0.0068mol/L
2PtCl
6In aqueous solution 9.0ml, then 60 ℃ ,-use the Rotary Evaporators desolventizing under the 0.08Mp condition, dry 12h under 120 ℃, 550 ℃ of lower roasting 4h can make catalyst C.
The component of catalyst C is: Pt-Sn-Ce-Ca/MCM-41, the catalytic applications testing conditions is identical with embodiment 1, after reaction gaseous product through the gas chromatograph on-line analysis, conversion of propane such as Fig. 1, propylene selective as Fig. 2.
Claims (5)
1. one kind is used for the preparation method that the propane catalytic dehydrogenation prepares the catalyst of propylene, the described catalyst for preparing propylene for the propane catalytic dehydrogenation is the load type platinum series catalysts, be carrier by homemade mesopore molecular sieve MCM-41, take Pt metal as active component, with metal Sn, Sn-Ce or Sn-Ce-Ca are that auxiliary agent consists of, in catalyst, the quality percentage composition of each component is: active component Pt 0.1-1.0%, auxiliary agent Sn 0.3-1.2%, Ce0.5-3.0%, Ca 0.1-2.0%, the preparation method of described homemade mesopore molecular sieve MCM-41 is after the 4.0g softex kw is added the dissolving of 104.0mL deionized water for stirring, slowly drip the 20.0mL ethyl orthosilicate, stir 10min, slowly drip again 48.0mL ammoniacal liquor, stir 3-4h under room temperature, filter with sand core funnel after standing 48h, wash to filtrate and be neutral, room temperature is dried in the shade and is namely got former powder, former powder is put into 120 ℃ of oven dry 12h of baking oven, grind into powder, roasting in Muffle furnace, first at 350 ℃ of constant temperature 2h, be warmed up to again 550 ℃ of constant temperature 5h, naturally cooling, namely obtain removing the mesopore molecular sieve MCM-41 of surfactant, it is characterized in that: adopt equal-volume continuous impregnating legal system standby, step is as follows:
1) preparation of powder MCM-41 carrier: the sample after roasting after fully grinding, is used powder with obtaining testing after 40 purpose sieve screenings;
2) first before dipping, first with carrier at 550 ℃ of lower roasting 4h, then with the first compounding agent solution dipping 12h, 60 ℃ ,-use the Rotary Evaporators desolventizing under the 0.08Mpa pressure condition, dry 12h under 120 ℃, 550 ℃ of lower roasting 4h;
3) according to step 2) described in identical method flood again other compounding agent solution;
4) final impregnating active component platinum, method is the carrier that will flood after all compounding agent solutions, floods 12h with chloroplatinic acid aqueous solution, 60 ℃ ,-use the Rotary Evaporators desolventizing under the 0.08Mpa pressure condition, dry 12h under 120 ℃, 550 ℃ of lower roasting 4h can make catalyst.
2. be used for according to claim 1 the preparation method that the propane catalytic dehydrogenation prepares the catalyst of propylene, it is characterized in that: described compounding agent solution take Sn as auxiliary agent is SnCl
2Ethanolic solution, SnCl
2The concentration of ethanolic solution is 0.0084-0.0337mol/L.
3. be used for according to claim 1 the preparation method that the propane catalytic dehydrogenation prepares the catalyst of propylene, it is characterized in that: described compounding agent solution take Ce as auxiliary agent is Ce (NO
3)
3The aqueous solution, Ce (NO
3)
3The concentration of the aqueous solution is 0.0119-0.0714mol/L.
4. be used for according to claim 1 the preparation method that the propane catalytic dehydrogenation prepares the catalyst of propylene, it is characterized in that: described compounding agent solution take Ca as auxiliary agent is Ca (NO
3)
2The aqueous solution, Ca (NO
3)
2The concentration of the aqueous solution is 0.0083-0.167mol/L.
5. be used for according to claim 1 the preparation method that the propane catalytic dehydrogenation prepares the catalyst of propylene, it is characterized in that: the concentration of described chloroplatinic acid aqueous solution is 0.0017-0.0170mol/L.
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| CN104248968B (en) * | 2013-06-28 | 2017-05-31 | 中国石油化工股份有限公司 | A kind of catalyst of propane direct dehydrogenation propylene and preparation method thereof |
| CN103977797B (en) * | 2014-05-20 | 2015-09-16 | 南开大学 | A kind of preparation method and application of the catalyst for preparing propylene by dehydrogenating propane |
| CN104941640A (en) * | 2015-05-29 | 2015-09-30 | 南开大学 | Catalyst for production of propylene through catalytic dehydrogenation of propane, and preparation method thereof |
| CN108855066B (en) * | 2017-05-10 | 2019-09-27 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
| CN110496635B (en) * | 2018-05-17 | 2022-01-04 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
| CN112221491A (en) * | 2019-06-30 | 2021-01-15 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with modified spherical mesoporous material as carrier and preparation method and application thereof |
| EP3858478A1 (en) * | 2020-01-31 | 2021-08-04 | SCG Chemicals Co., Ltd. | Stable, high selectivity catalysts and catalyst systems, and processes for their use |
| CN113828327B (en) * | 2020-06-24 | 2024-01-30 | 中国石油化工股份有限公司 | Catalyst, preparation method and application thereof, and method for preparing olefin by alkane dehydrogenation |
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| CN101411978A (en) * | 2008-11-28 | 2009-04-22 | 南开大学 | Catalyst for preparing propylene by propane dehydrogenation as well as preparation and application thereof |
| CN101875016A (en) * | 2009-11-19 | 2010-11-03 | 中国海洋石油总公司 | Catalyst for preparing methane by low-temperature oxidization of methane and preparation method and application thereof |
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