CN104437568A - Modified mesoporous carbon catalyst for preparing isobutene by isobutane dehydrogenation through oxidation by carbon dioxide and preparation method and application of modified mesoporous carbon catalyst - Google Patents
Modified mesoporous carbon catalyst for preparing isobutene by isobutane dehydrogenation through oxidation by carbon dioxide and preparation method and application of modified mesoporous carbon catalyst Download PDFInfo
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Abstract
The invention relates to a modified mesoporous carbon catalyst for preparing isobutene by isobutane dehydrogenation through oxidation by carbon dioxide and a preparation method and an application of the modified mesoporous carbon catalyst, and belongs to the technical fields of catalysts and preparation of basic organic chemical raw materials. Mesoporous carbon with a large surface area and a large aperture is taken as a catalyst carrier, and the catalyst is modified by a phosphorus-containing compound having 0.2%-4.0% by mass of phosphorus. The catalyst is free of any metal element loaded and has a low cost. At the reaction temperature ranging from 540 to 620 DEG C, the conversion rate of isobutane can reach 20-70% and the selectivity of isobutene can reach 55-99%, so the catalyst has bright industrialization application prospects.
Description
Technical field
Originally the present invention relates to Catalysts and its preparation method and the application of a kind of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane, be specifically related to gold/mesoporous carbon catalyst of a kind of highly active P Modification and its preparation method and application.
Background technology
Isobutene is current is mainly used in synthetic gasoline additive methyl tertiary butyl ether(MTBE) (MTBE), in addition also for the production of isoprene and the elastomer such as the fine chemicals such as methyl methacrylate, tert-butyl group alcohol and butyl rubber, isoprene rubber and Oppanol.The traditional source of isobutene mainly comes from steam cracking and catalytic cracking unit, but above technique isobutene is only as processed side product, and processing is separated with multistep affects its economy.Along with the development of isobutene downstream industry, the output of isobutene has been difficult to meet growing industrial requirement, estimates that the whole world in 2012 will more than 3,200,000 tons to the demand of isobutene.In recent years, although iso-butane cheap in refinery's liquefied gas or associated gas is converted into the isobutene arbitrary way that isobutene has become comparatively economic, however how to obtain high activity and optionally dehydrogenation of isobutane catalyst be still one of target of academia and industrial quarters pursuit.
Dehydrogenation of isobutane mainly contains anaerobic dehydrogenation, aerobic dehydrogenation and carbon dioxide oxidative dehydrogenation three kinds of approach.Anaerobic dehydrogenation adopts Cr usually
2o
3or precious metals pt series catalysts.With Cr
2o
3for the catalyst of representative has high toxicity, do not meet environmental requirement and the shortcoming such as inactivation is fast; With Pt be representative noble metal catalyst expensive, catalyst needs regenerate mostly for 7 ~ 10 days.The technique of anaerobic dehydrogenation maturation has the Linde technique of the Catofin technique of ABB Lummus company, the FBD-4 technique of Snamprogetti company, the Oleflex technique of Uop Inc., the STAR technique of Philips company and Linde company.
Compared with anaerobic dehydrogenation, although the dehydrogenation of iso-butane aerobic significantly can reduce reaction temperature, there is deep oxidation and the product distribution problem such as restive, this has been reported in many documents.Such as: Grabowski etc. by chromium oxide load at SiO
2, Al
2o
3, TiO
2, ZrO
2with on the different carriers such as MgO, research finds the CrOx/ TiO that K modifies
2with the CrOx/Al that K modifies
2o
3the highest isobutene yield can be obtained, but be only 9.6% and 9%(Applied Catalysis A:General, 144 volume 335th ~ 341 pages in 1996).The people such as the Wang CrO that utilized infusion process to prepare
x/ Ce
0.60zr
0.35y
0.05o
2nanocatalyst, at 30000 mLg
cat -1h
-1total air speed and reaction temperature be under the condition of 540 DEG C, can obtain 93% selective isobutene and close to 10% isobutene yield (Applied Catalysis A:General, 375 volume 272nd ~ 278 pages in 2010).Ni is incorporated into Al by the people such as Vislovskiy
2o
3in the V-Sb-O catalyst of load, iso-butane conversion ratio can be made to be increased to 42 ~ 44% by 36%, selective isobutene close to 70%(Applied Catalysis A:General, 250 volumes the 143rd – 150 pages in 2003).The people such as Schwartz, Xie of U.S.'s Oak Ridge National Laboratory adopt the graphitization mesoporous carbon of P Modification, oxygen-containing functional group mesoporous carbon for isobutene for oxo-dehydrogenation respectively, but the iso-butane low conversion rate obtained is in 10%, improves reaction temperature under Oxygen Condition and the burning of carbon carrier and reaction raw materials iso-butane can be caused to generate CO
x, therefore this process does not have industrial application value (Carbon, 49 volume 659th ~ 668 pages in 2011; Journal of Catalysis, 267 volume 158th ~ 166 pages in 2009).
Compared with oxygen, carbon dioxide is a kind of more weak oxidant, not only can be oxidized iso-butane and produce isobutene, and in course of reaction, self be converted into the relatively high CO of value, meet low-carbon economy demand for development.Relevant carbon dioxide oxidation iso-butane introduces (Catalysis Communications, 11 volume 132nd ~ 136 pages in 2009 to some extent in such as Publication about Document; Applied Catalysis A:General, 168 volume 243rd ~ 250 pages in 1998; Chinese Chemical Letters, 19 volume 1059th ~ 1062 pages in 2008; Journal of Molecular Catalysis A:Chemical, 315 volume 221st ~ 225 pages in 2010).ZL201010574040.9, ZL201110038365.x, ZL201110080513.4, ZL201110248721.0, ZL201110248722.5, ZL201110371388.2 utilize mesoporous carbon high-specific surface area, aperture feature that is large and that be beneficial to diffusion to construct Fe, Co, Ni, V, Cu, Cr catalyst of its load respectively, and these catalyst have the performance that good carbon dioxide selective oxidation iso-butane generates isobutene.
Summary of the invention
An object of the present invention is to provide the high activity P Modification gold/mesoporous carbon catalyst of a kind of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane.
Another object of the present invention is to provide the preparation method of a kind of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane high activity P Modification gold/mesoporous carbon catalyst.
Another object of the present invention is to provide the application of this catalyst for preparing isobutene through dehydrogenation of iso-butane under carbon dioxide atmosphere.
The technical solution adopted in the present invention is as follows:
A P Modification gold/mesoporous carbon catalyst for carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane, is characterized in that: this catalyst take mesoporous carbon as carrier, carries out modification with phosphorus, and in described catalyst, P elements counts 0.2% ~ 4.0% by mass percentage.
In described catalyst, the mass percentage of phosphorus is preferably 0.5% ~ 3.0%.
Described carrier mesoporous carbon, BET specific surface area 800 ~ 3100 m
2g
-1, average pore size is 2 ~ 8 nm, and pore volume is 0.4 ~ 2.1 mlg
-1, mesoporous is 20 ~ 100%.
A preparation method for carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane P Modification gold/mesoporous carbon catalyst, is characterized in that this preparation method comprises the steps:
(1) by appropriate dissolving oxalic acid in water, be made into 10 ~ 30gL
-1oxalic acid aqueous solution;
(2) in oxalic acid aqueous solution, the ratio being 3 ~ 10:1 in mesoporous carbon and oxalic acid mass ratio adds mesoporous carbon, adds hot reflux 3 ~ 5 hours under the condition of 100 ~ 130 DEG C;
(3) filter mesoporous carbon, under temperature is 160 ~ 200 DEG C of conditions, dries mesoporous carbon to constant weight;
(4) be dissolved in water by appropriate phosphorus-containing compound, being made into phosphorus mass concentration is 1 ~ 8gL
-1the aqueous solution;
(5) in the phosphorous aqueous solution, the ratio being 0.02 ~ 0.25:1 in the mesoporous carbon mass ratio after phosphorus and step (3) constant weight adds mesoporous carbon, and stirring, dry, roasting, obtain the P Modification gold/mesoporous carbon catalyst of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane.
In above-mentioned preparation method, described phosphorus-containing compound comprises phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, metaphosphoric acid and pyrophosphoric acid.
In above-mentioned preparation method, described phosphorus-containing compound preferably phosphoric acid and pyrophosphoric acid.
In above-mentioned preparation method, the baking temperature described in step (5) is 80 ~ 150 DEG C.
In above-mentioned preparation method, the roasting described in step (5) was in an inert atmosphere, through 560 ~ 750 DEG C of roastings 3 ~ 8 hours.
Above-mentioned preparation method, roasting inert atmosphere used refers to O
2volumetric concentration lower than 0.1% high-purity N
2, one in high-purity Ar or high-purity He gas.
Described carrier mesoporous carbon, BET specific surface area 800 ~ 3100 m
2g
-1, average pore size is 2 ~ 8 nm, and pore volume is 0.4 ~ 2.1 mlg
-1, mesoporous is 20 ~ 100%.
Described carrier mesoporous carbon, as having commodity CMK-1, CMK-3 of orderly pore structure, (unordered mesoporous carbon preparation can with reference to Journal of Materials Chemistry for the unordered mesoporous carbon prepared by organic carbon hydrate, metal halide carbonization, 19th volume 7759 ~ 7764 pages in 2009), CNT, nanometer rods and other commercial mesoporous carbons.
The object adding oxalic acid in preparation method of the present invention is not only to remove the trace impurity in mesoporous carbon, but also can promote dispersed on mesoporous carbon surface of phosphorus containg substances, improves the dehydrogenation of catalyst.
The invention still further relates to described P Modification gold/mesoporous carbon catalyst and prepare application in isobutene at carbon dioxide oxidation dehydrogenation of isobutane.
Being applied on dehydrogenation reactor of carbon dioxide oxidation iso-butane preparing isobutene catalyst provided by the invention is reacted, and dehydrogenation reactor is fixed bed, moving bed or fluid bed; Reaction temperature is 540 ~ 620 DEG C, and the amount ratio of iso-butane and carbon dioxide material is 1:1 ~ 1:11, and the overall flow rate of gas is every gram of catalyst 1 ~ 8L/ hour, and the reaction time is 1 ~ 30 hour.
Carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane P Modification gold/mesoporous carbon catalyst provided by the invention, preparation is simple, do not need any metallic element of load, there is lower cost, be under the condition of 540 ~ 620 DEG C in reaction temperature, catalytic oxidation dehydrogenation of isobutane under carbon dioxide atmosphere, can not cause carbon carrier and reaction raw materials iso-butane deep oxidation to generate CO and CO
2, the conversion ratio of iso-butane can reach 20 ~ 70%, and selective isobutene can reach 55 ~ 99%, has good industrial applications prospect.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with detailed description of the invention, but is limited by claim.
Detailed description of the invention
The invention will be further described for following examples, but be necessary to point out that following examples are only for the description to summary of the invention, and do not form limiting the scope of the invention, scope is as the criterion with claim.
Embodiment 1
A kind of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane P Modification gold/mesoporous carbon catalyst and preparation method thereof: compound concentration is 10gL
-1oxalic acid aqueous solution 1L, in above-mentioned solution, add surface area is 1320 m
2g
-1, average pore size is CMK-3 mesoporous carbon 30 g of 4.3 nm, 100 DEG C of backflows 5 hours, filter, dry CMK-3 to constant weight for 160 DEG C.Preparation 3.2gL
-1phosphate aqueous solution 0.5L, in this aqueous solution, add the oven dry sample 25g of CMK-3, through 150 DEG C dry 3 hours, under 750 DEG C of blanket of nitrogen, roasting 3 hours, obtains the gold/mesoporous carbon catalyst of P Modification, and measuring wherein phosphorus mass percentage is 0.2%.
Being loaded in fixed bed reactors by the gold/mesoporous carbon catalyst of prepared P Modification, is 5 Lg in air speed
cat -1h
-1, reaction temperature 620 DEG C and carbon dioxide and iso-butane amount of substance be than under the condition of 1:8, react after 1 hour, product and reactant are by online gas chromatographic analysis determination conversion ratio and selective, and the conversion ratio recording iso-butane is 21%, and in product, selective isobutene is 92.0%.
Embodiment 2
A kind of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane P Modification gold/mesoporous carbon catalyst and preparation method thereof: compound concentration is 30gL
-1oxalic acid aqueous solution 1L, in above-mentioned solution, add surface area is 1320 m
2g
-1, average pore size is CMK-3 mesoporous carbon 300 g of 4.3 nm, 130 DEG C of backflows 3 hours, filter, dry CMK-3 to constant weight for 200 DEG C.Prepare 25.3 gL
-1phosphate aqueous solution 0.5L, in this aqueous solution, add the oven dry sample 16g of CMK-3, through 100 DEG C dry 3 hours, under 630 DEG C of blanket of nitrogen, roasting 8 hours, obtains the gold/mesoporous carbon catalyst of P Modification, and measuring wherein phosphorus mass percentage is 3.6%.
Being loaded in fixed bed reactors by the gold/mesoporous carbon catalyst of prepared P Modification, is 3 Lg in air speed
cat -1h
-1, reaction temperature 610 DEG C and carbon dioxide and iso-butane amount of substance than under the condition of 1:8, reacting the conversion ratio recording iso-butane after 1 hour is 42%, and in product, selective isobutene is 91.3%.
Embodiment 3
A kind of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane P Modification gold/mesoporous carbon catalyst and preparation method thereof: compound concentration is 20gL
-1oxalic acid aqueous solution 1L, in above-mentioned solution, add surface area is 1320 m
2g
-1, average pore size is CMK-3 mesoporous carbon 160 g of 4.3 nm, 120 DEG C of backflows 3 hours, filter, dry CMK-3 to constant weight for 180 DEG C.Preparation 20.0gL
-1phosphate aqueous solution 0.5L, in this aqueous solution, add the oven dry sample 21g of CMK-3, through 150 DEG C dry 3 hours, under 620 DEG C of blanket of nitrogen, roasting 6 hours, obtains the gold/mesoporous carbon catalyst of P Modification, and measuring wherein phosphorus mass percentage is 3.0%.
Being loaded in fixed bed reactors by the gold/mesoporous carbon catalyst of prepared P Modification, is 3 Lg in air speed
cat -1h
-1, reaction temperature 590 DEG C and carbon dioxide and iso-butane amount of substance than under the condition of 1:5, reacting the conversion ratio recording iso-butane after 1 hour is 43%, and in product, selective isobutene is 92.1%.
Embodiment 4
A kind of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane P Modification gold/mesoporous carbon catalyst and preparation method thereof: compound concentration is 20gL
-1oxalic acid aqueous solution 1L, in above-mentioned solution, add surface area is 1320 m
2g
-1, average pore size is CMK-3 mesoporous carbon 160 g of 4.3 nm, 130 DEG C of backflows 3 hours, filter, dry CMK-3 to constant weight for 180 DEG C.Preparation 20.0gL
-1pyrophosphoric acid aqueous solution 0.5L, in this aqueous solution, add the oven dry sample 35g of CMK-3, through 150 DEG C dry 3 hours, under 610 DEG C of blanket of nitrogen, roasting 6 hours, obtains the gold/mesoporous carbon catalyst of P Modification, and measuring wherein phosphorus mass percentage is 1.0%.
Being loaded in moving-burden bed reactor by the gold/mesoporous carbon catalyst of prepared P Modification, is 1 Lg in air speed
cat -1h
-1, reaction temperature 590 DEG C and carbon dioxide and iso-butane amount of substance than under the condition of 1:1, reacting the conversion ratio recording iso-butane after 1 hour is 53%, and in product, selective isobutene is 91.5%.
Embodiment 5
A kind of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane P Modification gold/mesoporous carbon catalyst and preparation method thereof: compound concentration is 20gL
-1oxalic acid aqueous solution 1L, in above-mentioned solution, add surface area is 980 m
2g
-1, average pore size is commodity mesoporous carbon 160 g of 2.2 nm, 120 DEG C of backflows 3 hours, filter, dry mesoporous carbon to constant weight for 180 DEG C.Preparation 20.0gL
-1ammonium dihydrogen phosphate aqueous solution 0.5L, in this aqueous solution, add the oven dry sample 20g of commodity mesoporous carbon, through 160 DEG C dry 4 hours, under 560 DEG C of blanket of nitrogen, roasting 8 hours, obtains the gold/mesoporous carbon catalyst of P Modification, and measuring wherein phosphorus mass percentage is 4.0%.
Being loaded in fluidized-bed reactor by the gold/mesoporous carbon catalyst of prepared P Modification, is 4 Lg in air speed
cat -1h
-1, reaction temperature 620 DEG C and carbon dioxide and iso-butane amount of substance than under the condition of 1:8, reacting the conversion ratio recording iso-butane after 1 hour is 31%, and in product, selective isobutene is 87.2%.
Embodiment 6
A kind of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane P Modification gold/mesoporous carbon catalyst and preparation method thereof: compound concentration is 20gL
-1oxalic acid aqueous solution 1L, in above-mentioned solution, add surface area is 1230 m
2g
-1, average pore size be unordered mesoporous carbon 140 g(of 6.0 nm with reference to Journal of Materials Chemistry, the 19th volume in 2009 7759 ~ 7764 pages of preparations), 140 DEG C of backflows 3 hours, filter, 180 DEG C of unordered mesoporous carbon of oven dry are to constant weight.The ammonium dibasic phosphate aqueous solution of preparation 20g/L, adds this unordered mesoporous carbon 25g in this aqueous solution, and dry 3 hours through 150 DEG C, under 560 DEG C of blanket of nitrogen, roasting 8 hours, obtains the gold/mesoporous carbon catalyst of P Modification, and measuring wherein phosphorus mass percentage is 2.7%.
Being loaded in fixed bed reactors by the gold/mesoporous carbon catalyst of prepared P Modification, is 4 Lg in air speed
cat -1h
-1, reaction temperature 620 DEG C and carbon dioxide and iso-butane amount of substance than under the condition of 1:8, reacting the conversion ratio recording iso-butane after 1 hour is 29%, and in product, selective isobutene is 91.6%.
Claims (10)
1. a P Modification gold/mesoporous carbon catalyst for carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane, is characterized in that: described catalyst take mesoporous carbon as carrier, carries out modification with phosphorus, and in described catalyst, P elements counts 0.2% ~ 4.0% by mass percentage.
2. the P Modification gold/mesoporous carbon catalyst of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane according to claim 1, it is characterized in that: in described catalyst, the mass percentage of phosphorus is 0.5% ~ 3.0%.
3. the P Modification gold/mesoporous carbon catalyst of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane according to claim 1, is characterized in that: described carrier mesoporous carbon, BET specific surface area 800 ~ 3100 m
2g
-1, average pore size is 2 ~ 8 nm, and pore volume is 0.4 ~ 2.1 mlg
-1, mesoporous is 20 ~ 100%.
4. the preparation method of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane P Modification gold/mesoporous carbon catalyst according to claim 1, it is characterized in that, described preparation method comprises the steps:
(1) by appropriate dissolving oxalic acid in water, be made into 10 ~ 30gL
-1oxalic acid aqueous solution;
(2) in oxalic acid aqueous solution, the ratio being 3 ~ 10:1 in mesoporous carbon and oxalic acid mass ratio adds mesoporous carbon, adds hot reflux 3 ~ 5 hours under the condition of 100 ~ 130 DEG C;
(3) filter mesoporous carbon, under temperature is 160 ~ 200 DEG C of conditions, dries mesoporous carbon to constant weight;
(4) be dissolved in water by appropriate phosphorus-containing compound, being made into phosphorus mass concentration is 1 ~ 8gL
-1the aqueous solution;
(5) in the phosphorous aqueous solution, the ratio being 0.02 ~ 0.25:1 in the mesoporous carbon mass ratio after phosphorus and step (3) constant weight adds mesoporous carbon, and stirring, dry, roasting, obtain the P Modification gold/mesoporous carbon catalyst of carbon dioxide oxidation preparing isobutene through dehydrogenation of iso-butane.
5. preparation method according to claim 4, is characterized in that, described phosphorus-containing compound is phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, metaphosphoric acid or pyrophosphoric acid.
6. preparation method according to claim 4, is characterized in that, the baking temperature described in step (5) is 80 ~ 150 DEG C, and roasting is 560 ~ 750 DEG C of roastings in an inert atmosphere 3 ~ 8 hours.
7. preparation method according to claim 4, is characterized in that, described carrier mesoporous carbon BET specific surface area 800 ~ 3100 m
2g
-1, average pore size is 2 ~ 8 nm, and pore volume is 0.4 ~ 2.1 mlg
-1, mesoporous is 20 ~ 100%.
8. preparation method according to claim 7, is characterized in that, described carrier mesoporous carbon is selected from ordered mesopore carbon, unordered mesoporous carbon, CNT or nanometer rods.
9. P Modification gold/mesoporous carbon catalyst according to claim 1 prepares the application in isobutene at carbon dioxide oxidation dehydrogenation of isobutane.
10. P Modification gold/mesoporous carbon catalyst according to claim 9 prepares the application in isobutene at carbon dioxide oxidation dehydrogenation of isobutane, it is characterized in that, described dehydrogenation reaction is carried out on fixed bed, moving bed or fluid bed, reaction temperature is 540 ~ 620 DEG C, the amount ratio of iso-butane and carbon dioxide material is 1:1 ~ 1:11, air speed is every gram of catalyst 1 ~ 8L/ hour, and the reaction time is 1 ~ 30 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803820A (en) * | 2015-05-08 | 2015-07-29 | 中国科学院生态环境研究中心 | Method for producing isobutylene by catalyzing isobutane to dehydrogenate through carbon catalyst |
| CN106311201A (en) * | 2015-06-30 | 2017-01-11 | 中国石油化工股份有限公司 | Pt-based catalyst for dehydrogenation of isobutane by using carrier Sn-containing mesoporous carbon, preparation method and application thereof |
| CN109745978A (en) * | 2017-11-03 | 2019-05-14 | 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 |
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| EP0557790A2 (en) * | 1992-02-28 | 1993-09-01 | Sumitomo Chemical Company, Limited | Process for producing isobutylene by oxidative dehydrogenation of isobutane and catalyst therefor |
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2013
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| EP0557790A2 (en) * | 1992-02-28 | 1993-09-01 | Sumitomo Chemical Company, Limited | Process for producing isobutylene by oxidative dehydrogenation of isobutane and catalyst therefor |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803820A (en) * | 2015-05-08 | 2015-07-29 | 中国科学院生态环境研究中心 | Method for producing isobutylene by catalyzing isobutane to dehydrogenate through carbon catalyst |
| CN106311201A (en) * | 2015-06-30 | 2017-01-11 | 中国石油化工股份有限公司 | Pt-based catalyst for dehydrogenation of isobutane by using carrier Sn-containing mesoporous carbon, preparation method and application thereof |
| CN106311201B (en) * | 2015-06-30 | 2018-10-02 | 中国石油化工股份有限公司 | It is a kind of using mesoporous carbon containing Sn as dehydrogenation of isobutane Pt bases catalyst, preparation method and its application of carrier |
| CN109745978A (en) * | 2017-11-03 | 2019-05-14 | 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 |
| CN109745978B (en) * | 2017-11-03 | 2022-03-15 | 中国石油化工股份有限公司 | Propane dehydrogenation catalyst, preparation method thereof and method for preparing propylene by propane dehydrogenation |
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Application publication date: 20150325 |