CN101612583B - Saturated alkane dehydrogenation catalyst with nonuniformly distributed active component - Google Patents
Saturated alkane dehydrogenation catalyst with nonuniformly distributed active component Download PDFInfo
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- CN101612583B CN101612583B CN2009101815668A CN200910181566A CN101612583B CN 101612583 B CN101612583 B CN 101612583B CN 2009101815668 A CN2009101815668 A CN 2009101815668A CN 200910181566 A CN200910181566 A CN 200910181566A CN 101612583 B CN101612583 B CN 101612583B
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Abstract
The invention relates to a saturated alkane dehydrogenation catalyst with a nonuniformly distributed active component. The catalyst adopts alumina as a carrier, and various catalytic components are loaded on the carrier nonuniformly by an impregnation method, wherein platinum as the active component is mainly distributed on the surface of the carrier, and tin, alkali metals and VIII metals as auxiliary agents are integrally and uniformly distributed in the carrier. The saturated alkane dehydrogenation catalyst with the nonuniformly distributed active component has outstanding selectivity and activity and good stability, so the one-way conversion rate can be significantly improved, and the service life of the catalyst can be prolonged.
Description
Technical field
The present invention is a kind of saturated hydrocarbons such as C of being used for
3～C
20Alkane, the dehydrogenation of alkylaromatic hydrocarbon, particularly be applicable to C
10～C
15The long linear dehydrating alkanes is produced the saturated alkane dehydrogenation catalyst of the active component non-uniform Distribution of monoolefine.
Background technology
Long-chain normal paraffin in the petroleum distillate is produced synthetic detergent raw material alkylbenzene or the higher aliphatic technology is a process route that grows up sixties end through dehydrogenation.1966, American UOP company delivered first piece of dehydrogenation of long-chain alkane catalyst patent.So far, the patent major part about this respect all belongs to Uop Inc..These patents are active component mostly with platinum, with arsenic, selenium, germanium, tin, lead, rhenium, iridium, tungsten, nickel, cobalt, indium etc. as second and third component, and to be added with alkali metal be auxiliary agent, as U.S. Pat 4210769,4216346,4595673,4551574,4677237 etc., the carrier of catalyst is for adopting forming oil column in these patents, pore distribution concentration, and have the γ-Al of high-specific surface area
2O
3Bead, various catalytic elements are evenly distributed in the carrier.
Chinese patent CN1033949A discloses a kind of preparation of stratiform dehydrogenation catalyst particles, flood after adopting the platinum, tin compound complexing of divalence respectively, platinum and other are helped urging the mean concentration of element in outside 100 micron layers of catalyst granules is the twice of concentration in particle core 200 micron diameters at least.
U.S. Pat 4786625,4827072,4973779,5012027 grades have been reported and have been utilized organic acid with multidentate ligand etc. to make platinum or other metals form the method for surface impregnation, adopt the mixed liquor and the stanniferous carrier impregnation of lithium nitrate and sulfuration hydroxysuccinic acid as US5012027, and then respectively with chloroplatinic acid and Chloroiridic Acid solution dipping, thereby obtain the catalyst that platinum and iridium are distributed in the surface.
U.S. Pat 6177381,6280608,6486370, employing spraying processes such as 6756515 prepare a kind of layered catalyst, at first preparing layered vector is that inner core is an inert carrier, the outer activated alumina that applies, and then realize the surface distributed of catalytic elements with the mode that catalytic elements is immersed in layered vector.
Correlative study shows, for saturated alkane dehydrogenation C particularly
10～C
15Dehydrogenation of long-chain alkane is produced the monoolefine reaction, and catalyst activity component top layer distributes can shorten reaction diffusion path, improves the selectivity and the stability of reaction.In foregoing invention, platinum tin complex liquid is not easy to stablize, and spraying process prepares also more complicated of layered vector, and control tin platinum relative amount is not had special event.
Summary of the invention
The purpose of this invention is to provide a kind of dehydrogen of saturated hydrocarbon that is used for, especially for long-chain C
10～C
15N-alkane is produced the catalyst of monoolefine.
Catalyst of the present invention is to be carrier with the alumina globule, adopt infusion process to load on the carrier various catalyst components are non-homogeneous, wherein platinum mainly is distributed in carrier surface as active component, and tin, alkalinous metal and group VIII metal are evenly distributed in the carrier as auxiliary agent.
The percentage by weight of each component of the present invention is: platinum 0.2～0.8%; Tin 0.4～1.3%; Alkali metal 0.1～1.5%; Group VIII metal 0.1～1.5%, all the other are carrier γ-Al
2O
3
Above-mentioned alkali metal is selected from least a among Li, Na, K, Mg, the Ca, and its total amount gets final product in 0.1-1.5%; At least a in above-mentioned group VIII metal chosen from Fe, cobalt, nickel, the palladium, its total amount satisfies 0.1-1.5% and gets final product.
Among the present invention, tin platinum content atomic ratio is bigger to the performance impact of catalyst, and platinum content is crossed low or the tin too high levels can cause that all catalyst performance descends.General tin pt atom ratio is 1～5, and its optimum value is 2～3.
Catalyst of the present invention need reduce 2～8 hours time with hydrogen under 400～600 ℃ before being used for the dehydrogenation of long-chain alkane reaction.The condition of its catalytic reaction is:
Reaction temperature: 450～650 ℃, reaction pressure: normal pressure～1MPa,
Liquid hourly space velocity (LHSV): 1～20h
-1, H
2/ hydrocarbon mol ratio: 4～8.
In the multicomponent dipping, different acid preserved material, platinum precursor altogether all may be prepared the platinum catalyst of various distributions.The applicant has very big influence through the pH value of discovering maceration extract for the absorption system of catalytic metal and alumina support, when the adjusting pH value makes it to help flooding the absorption of species, can obtain concentrated eggshell type distribution catalyst, and platinum group metal precursor preferably adopts platinum acid chloride solution, and competitive adsorbate preferably adopts hydrochloric acid solution.The present invention passes through to adjust the consumption of hydrochloric acid in the maceration extract, thereby makes platinum mainly be distributed in carrier surface, and other metal components such as tin, alkali metal and group VIII metal etc. then are to be evenly distributed in the carrier; And, obtained best catalytic performance by adjusting the tin platinum content.
The present invention has outstanding selectivity and activity, have stability preferably simultaneously, and the preparation method is simple.The present invention is used as dehydrogen of saturated hydrocarbon, especially for long-chain C
10～C
15N-alkane is produced the catalyst of monoolefine, can significantly improve conversion per pass, prolongs catalyst service life.
The specific embodiment
The following examples are used for the present invention is specifically described, but scope of the present invention is not limited.If no special instructions, all percentage compositions are weight content among following Comparative Examples and the embodiment.
Evenly the distribute preparation of catalyst A of Comparative Examples
Adopt the conventional method preparation to contain the H of 0.50% platinum content
2PtCl
6Solution, wherein content of hydrochloric acid is 5%; Preparation contains the SnCl of 0.91% tin content
4Solution, wherein content of hydrochloric acid is 5%; Preparation contains the NaCl solution of 0.5% sodium content and the CoCl of 0.6% cobalt content
2Solution mixes above-mentioned solution, with particle diameter be γ-Al of 2.2mm
2O
3The carrier contact, constantly shake and make dipping evenly, flood and vacuumize dry 30 minutes after 20 minutes, dried 4 hours down at 150 ℃ then, 450 ℃ of roastings 4 hours, carrier after the roasting is handled through steam dechlorination, makes finished catalyst A in reduction under 500 ℃ after 8 hours with hydrogen at last, and each tenor of catalyst is Pt0.45%, Sn0.77%, Na0.5%, Co0.5%, the Sn/Pt atomic ratio is 2.8.The various active elements of analyzing this catalyst with EDX are equally distributed in carrier.
Embodiment 1
Preparation contains the H of 0.50% platinum content
2PtCl
6Solution, wherein content of hydrochloric acid is 0.5%; Preparation contains the SnCl of 0.91% tin content
4Solution, wherein content of hydrochloric acid is 1%; Preparation contains the NaCl solution of 0.5% sodium content and the CoCl of 0.6% cobalt content
2Solution is respectively γ-Al of 2.2mm with particle diameter with above-mentioned solution
2O
3The carrier contact, each flooded 10 minutes, and the same catalyst A of other preparation methods makes finished catalyst B, and each tenor of catalyst is Pt0.45%, Sn0.77%, Na0.5%, Co0.5%, Sn/Pt atomic ratio are 2.8.Analyze in this catalyst 90% platinum by EDX and be distributed in 160 microns of the carrier surfaces, other active components then are to be evenly distributed in the carrier basically.
Catalyst A and B are used for C
10～C
15The dehydrogenation reaction of long chain alkane, its reactivity worth is as follows:
The dehydrogenation reaction performance of table 1 catalyst A and B
Reaction condition: reaction temperature: 485 ℃, liquid hourly space velocity (LHSV): 20h
-1, H
2/ hydrocarbon mol ratio: 6
Reaction pressure 0.1MPa
Compare with catalyst A, the selectivity and the conversion ratio of catalyst B significantly improve.
Embodiment 2
Catalyst B among method for preparing catalyst such as the embodiment 1 wherein is adjusted into 1.5 with the Sn/Pt atomic ratio, makes catalyst C, and each tenor of catalyst is Pt0.45%, Sn0.41%, Mg0.4%, Co0.5%.Analyze in this catalyst 90% platinum by EDX and be distributed in 250 microns of the carrier surfaces, other catalytic elements are evenly distributed in the carrier.Prepare catalyst D according to the preparation method in the Comparative Examples in addition, the Sn/Pt atomic ratio is adjusted into 1.5, the same C of each tenor in the catalyst, each catalytic elements is evenly distributed in the carrier.Catalyst is used for C
10～C
15The dehydrogenation of long-chain alkane reactivity worth is as follows:
The dehydrogenation reaction performance of table 2 catalyst C and D
Reaction condition is with embodiment 1.
Compare with catalyst B, the activity of catalyst C, selectivity, stability all have more significantly decline, but still are better than the equally distributed catalyst D of Pt.
Embodiment 3
Catalyst B among method for preparing catalyst such as the embodiment 1 wherein is adjusted into 5 with the Sn/Pt atomic ratio, makes catalyst E, and each tenor of catalyst is Pt0.40%, Sn1.22%, Na0.8%, Co0.5%.Analyze in this catalyst 90% platinum by EDX and be distributed in 200 microns of the carrier surfaces, other active components then are to be evenly distributed in the carrier basically.Prepare catalyst F according to the preparation method in the Comparative Examples in addition, the Sn/Pt atomic ratio is adjusted into 5, each tenor of catalyst is Pt0.40%, Sn1.22%, and Na0.8%, Co0.5%, each catalytic elements is evenly distributed in the carrier.Catalyst is used for C
10～C
15The dehydrogenation of long-chain alkane reactivity worth is as follows:
The dehydrogenation reaction performance of table 3 catalyst E and F
Reaction condition is with embodiment 1.
As can be seen, the activity of catalyst E, selectivity, stability all are weaker than catalyst B, but still are better than the equally distributed catalyst F of Pt.
Claims (10)
1. the saturated alkane dehydrogenation catalyst of an active component non-uniform Distribution, it is characterized in that this catalyst is carrier with the alumina globule, adopt infusion process to load on the carrier various catalyst components are non-homogeneous, wherein platinum mainly is distributed in carrier surface as active component, and tin, alkali metal and group VIII metal are evenly distributed in the carrier as auxiliary agent integral body.
2. catalyst according to claim 1 is characterized in that the composition percentage by weight of this catalyst is: platinum 0.2～0.8%; Tin 0.4～1.3%; Alkali metal 0.1～1.5%; Group VIII metal 0.1～1.5%, all the other are γ-Al
2O
3
3. catalyst according to claim 1 and 2 is characterized in that described alkali metal is selected from least a among Li, Na, the K; At least a in group VIII metal chosen from Fe, cobalt, nickel, the palladium.
4. catalyst according to claim 1 and 2 is characterized in that with at least a alternate base metal among Mg or the Ca.
5. catalyst according to claim 1 and 2, the atomic ratio that it is characterized in that tin platinum content in this catalyst is 1～5.
6. according to the described catalyst of claim 1, it is characterized in that tin platinum content atomic ratio is 2～3 in this catalyst.
7. according to the catalyst of the described saturated alkane catalytic dehydrogenation of claim 1, it is characterized in that utilizing hydrogen under 400-600 ℃, to reduce before catalyst uses 2～8 hours recovery times.
8. catalyst according to claim 1 is characterized in that this catalyst is used for the dehydrogenation of saturated hydrocarbons.
9. catalyst according to claim 8 is characterized in that this catalyst is used for C
3～C
20Alkane, the dehydrogenation of alkylaromatic hydrocarbon.
10. catalyst according to claim 8 is characterized in that this catalyst is used for C
10～C
15The dehydrogenation reaction of long linear alkane.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909098B (en) * | 2011-08-01 | 2015-04-15 | 中国石油化工股份有限公司 | Reductive activation method for dehydrogenation catalyst by using low concentration hydrogen |
| CN102909102B (en) * | 2011-08-01 | 2015-04-15 | 中国石油化工股份有限公司 | Short time reduction activation method of dehydrogenation catalyst |
| CN102909094B (en) * | 2011-08-01 | 2014-12-31 | 中国石油化工股份有限公司 | Activation method for dehydrogenation catalyst at low temperature |
| US9364815B2 (en) | 2013-11-07 | 2016-06-14 | Saudi Basic Industries Corporation | Method of preparing an alumina catalyst support and catalyst for dehydrogenation reactions, and its use |
| CN106552645B (en) * | 2015-09-30 | 2020-08-18 | 中国石油化工股份有限公司 | Supported catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method |
| CN106552646B (en) * | 2015-09-30 | 2020-04-28 | 中国石油化工股份有限公司 | Supported catalyst, preparation method and application thereof, and method for catalyzing ring opening of naphthenic hydrocarbon by hydrogenolysis |
| CN112934230B (en) * | 2019-11-26 | 2023-10-27 | 中国石油天然气股份有限公司 | Low Pt type long-chain alkane dehydrogenation catalyst, and preparation method and application thereof |
| CN112892612B (en) * | 2019-12-03 | 2023-01-17 | 中国石化集团金陵石油化工有限责任公司 | Catalyst for hydrocarbon conversion reaction |
| CN113908880A (en) * | 2021-11-02 | 2022-01-11 | 中国科学院山西煤炭化学研究所 | Dehydrogenation catalyst and preparation method and application thereof |
| CN115445612B (en) * | 2022-10-13 | 2024-05-24 | 钱颖 | Dehydrogenation catalyst, preparation method and application thereof and method for preparing benzene ring by cyclohexane dehydrogenation |
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