CN1239679A - Catalyst for dehydrogenation of saturated hydrocarbon and its preparation - Google Patents
Catalyst for dehydrogenation of saturated hydrocarbon and its preparation Download PDFInfo
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- CN1239679A CN1239679A CN 98114083 CN98114083A CN1239679A CN 1239679 A CN1239679 A CN 1239679A CN 98114083 CN98114083 CN 98114083 CN 98114083 A CN98114083 A CN 98114083A CN 1239679 A CN1239679 A CN 1239679A
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Abstract
The catalyst contains platinum as active component and tin, potassium and magnesium as modifier. It features that the carrier is alumina with two-pore distributed large pore, low bulk weight and spinel structure; and that the catalyst consists of platinum 0.1-0.8 wt%, tin 0.5-2.0 wt%, potassium 0.2-1.3 wt% and magneisum 0.2-3.0 wt%. The catalyst of the present invention has high activity and selectivity as well as relatively high stability, and can be used for long period in the condition of raised conversion per pass.
Description
The present invention relates to the dehydrogenation of saturated hydrocarbon technology, a kind of novel dehydrogenation of saturated hydrocarbon platinum tin potassium/magnesium one aluminium oxide catalyst is provided especially, and technology of preparing.
Thereby making long-chain normal paraffin in oil gold-plating part be converted into monoolefine by method of dehydrogenating produces the technology of synthetic detergent raw material alkylbenzene and higher alcohols and has carried out commercial Application at the seventies, the used catalyst of these reactions mostly with VIII family precious metals pt as active constituent, germanium, tin, indium, thallium are as second component, and be auxiliary agent with alkali metal or alkaline-earth metal, technology related to the present invention comprises following three: US5,219, the 816 catalyst systems that propose are with the Pt-Ga/Mg-Al of Ga as second component
2O
3Catalyst, US4,595,673 Pt-Sn-Li-K/Al that propose
2O
3The method for making of catalyst is that Sn-Al soaks Pt behind the glue altogether, and Li soaks KCl after 540 ℃ of roastings again; The patent the most approaching with the present invention is GB2, and 284, the 769 a kind of catalyst that propose are by VIII family metal, alkali metal or alkaline-earth metal are formed, and also have the structure of part aluminate on the carrier, but its method for making are to soak Li salt successively, Sn salt, Pt salt, the Pt-Sn-Li/Al of method for making gained thus
2O
3Performance is best.Compare with these catalyst, adopt the prepared Pt-Sn-K/Mg-Al that forms of method provided by the invention
2O
3Catalyst shows better dehydrogenation stability.
The purpose of this invention is to provide a kind of dehydrogen of saturated hydrocarbon, especially for C
10～C
14Normal paraffin dehydrogenation is produced the catalyst of monoolefine, and this catalyst not only has activity and selectivity preferably, and advantages of higher stability is arranged, can be under the conversion per pass condition with higher long period of operation.
The catalyst that is used for dehydrogen of saturated hydrocarbon of the present invention, with platinum as active constituent, with tin potassium magnesium is the modulation agent, and the carrier of catalyst is to adopt high temperature to become the large aperture with diplopore distribution of glue method preparation to hang down bulk density, and the alumina globule with magnesia spinel structure.
Catalyst weight percentage is platinum 0.1～0.8%, tin 0.5～2.0%, and potassium 0.2～1.3%, magnesium 0.2～3.0%, all the other are aluminium oxide.For improving catalyst performance, the present invention has carried out modulation to the proportioning of active constituent and auxiliary agent, and tin pt atom ratio is 2～8: 1, its preferable ratio is 3～5: 1, and potassium pt atom ratio is 3～7: 1, and its preferable ratio is 4.4～5.8: 1, magnesium pt atom ratio is 4～26: 1, and its preferable ratio is 6～15: 1.
Preparation of catalysts process of the present invention is as follows:
One, the preparation of magnesium-modified carrier
A certain amount of alchlor and ammoniacal liquor neutralized under 60～80 ℃ of temperature generate aluminium hydroxide gel, filter then, washing, filter cake is through balling-up in oil ammonia column after the acidifying, and is dry then, 650～800 ℃, 2～10 hours, roasting, at last at 600～800 ℃, steam is to carry out the steam reaming under 0.1～2.0 condition to handle 4～30 hours with the catalyst support volume ratio.Above-mentioned bead was dipped in the magnesium salt solution more than 12 hours, 120 ℃ of dryings, the alumina globule that contains the magnesia spinel structure is prepared in 500～800 ℃ of roastings 4～30 hours, gained carrier physico-chemical property is: bulk density is 0.28～0.40 grams per milliliter, 80～160 meters of specific areas
2/ gram, total pore volume is greater than 1.0 milliliters/gram, and average pore size is greater than 200A, and particle diameter is 1.25～2.2 millimeters, and average crushing strength is 7.8～11.8N/ grain.
Two, the preparation of complexing location impregnated catalyst
(1) platinum salt and stannous chloride add sylvite after forming complex compound;
(2) above-mentioned mixed solution is dissolved in the alcohol hydrochloric acid aqueous solution makes maceration extract, concentration of ethanol is 10～70%wt, and the addition of hydrochloric acid is 2～10%wt of carrier amount;
(3) with the magnesium-modified carrier of (2) maceration extract dipping, add maceration extract liquid measure volume and be 0.7～1.2 times of carrier bulk, dry back is in 400～600 ℃, carries out roasting in 4～30 hours, after the steam treatment of the same terms, the water in air vapor content is 10～50%.
The ethanolic solution of maceration extract the most handy 40～60% in the above-mentioned Preparation of catalysts process.
Before catalyst uses in reactor or outward with moisture hydrogen less than 20ppm 400～600 ℃ of reduction, outlet is kept below the moisture 800ppm, the reduction rear catalyst promptly can be used for dehydrogen of saturated hydrocarbon, thereby prepares monoolefine.
The present invention is used for dehydrogen of saturated hydrocarbon, particularly dehydrogenation of long-chain alkane is produced the platinum tin potassium Mg catalyst of monoolefine, owing to adopt magnesium that alumina globule is carried out modification, formation has the carrier of magnesia spinel structure, and with complexing location dipping technology of preparing, catalyst is compared with the dehydrogenation of the same type of present industrial employing with the selection performance hydrocarbon dehydrogenation reaction is active, and catalyst has better stability; Under identical service cycle situation, can significantly improve the one way yield of product, reduce production costs, increase economic efficiency.
Give further instruction below by embodiment to technology of the present invention.
The preparation of embodiment 1 magnesium-modified carrier
With concentration is that the alchlor of/100 milliliters of 4 grams and the ammoniacal liquor of 6% weight connect the amount of calculation adding, under 60～80 ℃, in neutralizing tank, mix, control pH value 7.5～8.5, the generation aluminium hydroxide gel filters, the washing filter cake, with the nitric acid acidifying, the slurries that acidifying is good, add and depress balling-up, 650～750 ℃ of roastings 4 hours in activation furnace of aluminium hydroxide bead in becoming goalpost after aging, with with catalyst volume than being 0.2～1.0 steam uniform temp UR 12 hours, sieve out the alumina globule of φ 1.25～2.2mm after the cooling, take by weighing the above-mentioned bead of 100 grams, be dipped in the magnesium salts that 240 ml concns are 4.17gMg/l (magnesium nitrate or the magnesium chloride all can) solution and left standstill 10～20 hours, in 50～150 ℃ of baking ovens dry 8 hours then, 620 ℃ of roastings made the carrier with magnesia spinel structure more than 4 hours.
Embodiment 2 Preparation of catalysts (A)
Get carrier 100 grams that example 1 makes and place infuser, get 50 milliliters of the chloroplatinic acid aqueous solutions of platiniferous 0.01 grams per milliliter simultaneously, 11.25 milliliters of concentrated hydrochloric acids, 50.75 milliliters of the stannous chloride aqueous solution of stanniferous 0.03 grams per milliliter, 8.75 milliliters of the potassium oxide aqueous solution that contain potassium 0.05 grams per milliliter, adding the aqueous solution that contains 50% ethanol, to make the maceration extract volume be 0.8 times of carrier bulk, is deployed into maceration extract.Above-mentioned maceration extract is added in the infuser that carrier is housed, and dipping evenly back is dry, then in roaster during with air velocity 1500
-1, be warming up to 480～500 ℃, this roasting temperature 4 hours, again under uniform temp with the air-treatment of containing water vapor 30% 4 hours, stop into water steam then, continue the blowing air drying, cooling, with the hydrogen of moisture＜20ppm 500 ℃ of reduction 8 hours.The gained catalyst consists of platinum 0.5%, tin 1.52%, potassium 0.58%, magnesium 1%.
Embodiment 3 Preparation of catalysts (B)
Is carrier with above-mentioned example 1 without magnesium-modified alumina globule, presses embodiment 2 described method and conditions, makes catalyst (B), and its platinum tin potassium content is identical with (A).
Embodiment 4 Preparation of catalysts (C)
With reference to the method for embodiment 1, preparing the alumina globule with Li spinel structure is carrier, makes catalyst (C) by embodiment 2 described methods and condition, and it consists of platinum 0.5%, tin 1.52%, lithium 1%.
Embodiment 5 positive structure C
10～C
13Dehydrating alkanes is produced the monoolefine reaction
Be on 1.5 milliliters the fixed-bed flow reactor in the catalyst loading amount, adopt the initial activity of industrial dehydrating alkanes reaction condition evaluate catalysts, the stability of aging method evaluation catalyst is accelerated in employing, being raw material less than n-alkane gold-plating part of 1ppm through the hydrofinishing sulfur-bearing, at pressure is under the 0.10MPa, during liquid air speed 20
-1Hydrogen-hydrocarbon ratio 6: 1 (mol ratio), react under the condition that control catalyst reactor export center temperature is 450 ℃, selectivity by conversion ratio that generates oily product composition analysis n-alkane and generation monoolefine, improve temperature to 490 ℃ then, hydrogen hydrocarbon molal volume ratio is 1.6: 1, other condition is constant, life test was accelerated in running in 18 hours continuously, represent the stability of catalyst from generating oily bromine valency downward trend and whole mean value of accelerating process of the test, every running sample analysis after 2 hours the results are shown in table 1.
Comparative catalyst's initial activity of several dehydrogenation reactivity worth of table 1 is accelerated the average bromine valency of life test and is fallen selective (bromine valency) 123456789 bromine valency % %A 12.4 28.5 27.1 26.4 25.9 25.0 24.7 23.8 23.4 22.8 25.3 5.7 13.0 91B 12.1 26.8 25.7 24.9 23.6 22.6 22.1 21.7 20.2 20.2 23.1 6.6 12.7 90C 12.7 27.0 23.6 23.5 21.8 21.1 19.9 19.1 18.4 18.0 21.4 9.0 13.3 90 of conversion ratio
Claims (6)
1. a catalyst for dehydrogenation of saturated hydrocarbon as active constituent, is modulation agent with tin potassium magnesium with platinum, it is characterized in that:
(1) used carrier is for having diplopore distribution large aperture, low bulk density, the aluminium oxide of magnesia spinel structure;
(2) the composition percentage by weight of catalyst is:
Platinum 0.1～0.8%, tin 0.5～2.0%, potassium 0.2～1.3%, magnesium 0.2～3.0%.
2. according to the described catalyst for dehydrogenation of saturated hydrocarbon of claim 1, it is characterized in that: tin pt atom ratio is 2～8: 1, and potassium pt atom ratio is 3～7: 1, and magnesium pt atom ratio is 4～26: 1.
3. according to the described catalyst for dehydrogenation of saturated hydrocarbon of claim 1, it is characterized in that: tin pt atom ratio is 3～5: 1, and potassium pt atom ratio is 4.4～5.8: 1, and magnesium pt atom ratio is 6～15: 1.
4. the preparation method of the described catalyst for dehydrogenation of saturated hydrocarbon of claim 1 comprises carrier and Preparation of Catalyst, it is characterized in that:
(1) preparing carriers
The aluminium oxide that high temperature becomes the glue method to make, through 650～800 ℃, 2～10 hours, roasting, again at 600～800 ℃, steam is to carry out the steam reaming under 0.1～2.0 condition to handle 4～30 hours with the catalyst support volume ratio; Immerse in the magnesium salt solution at last and flood, drying, 500～800 ℃ of roastings made carrier in 4～30 hours;
(2) Preparation of Catalyst
(a) add sylvite after platinum salt and the stannous chloride aqueous solution;
(b) above-mentioned mixed solution is dissolved in the alcohol hydrochloric acid aqueous solution makes maceration extract, concentration of ethanol is 10～70%wt, and the addition of hydrochloric acid is 2～10%wt of carrier amount;
(c) with the magnesium-modified carrier of (b) maceration extract dipping, add maceration extract liquid measure volume and be 0.7～1.2 times of carrier bulk, dry back is in 400～600 ℃, carries out roasting in 4～30 hours, after the steam treatment of the same terms, the water in air vapor content is 10～50%.
5. according to the described catalyst for dehydrogenation of saturated hydrocarbon of claim 4, it is characterized in that: the concentration of ethanol water is 30～50%.
6. according to the described catalyst for dehydrogenation of saturated hydrocarbon of claim 4, it is characterized in that: moisture less than 20ppm before the catalyst action to enter the mouth, export moisture hydrogen and under 400～600 ℃, carry out reductase 12～12 hour less than 800ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114083A CN1099907C (en) | 1998-06-18 | 1998-06-18 | Catalyst for dehydrogenation of saturated hydrocarbon and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114083A CN1099907C (en) | 1998-06-18 | 1998-06-18 | Catalyst for dehydrogenation of saturated hydrocarbon and its preparation |
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| CN1239679A true CN1239679A (en) | 1999-12-29 |
| CN1099907C CN1099907C (en) | 2003-01-29 |
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| CN98114083A Expired - Fee Related CN1099907C (en) | 1998-06-18 | 1998-06-18 | Catalyst for dehydrogenation of saturated hydrocarbon and its preparation |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101642713B (en) * | 2008-08-07 | 2011-12-07 | 中国石油天然气股份有限公司 | C16-C19Long-chain normal alkane dehydrogenation catalyst and preparation method and application thereof |
| CN103990454A (en) * | 2014-05-20 | 2014-08-20 | 南京沃来德能源科技有限公司 | Low-carbon alkane dehydrogenation catalyst as well as preparation method and low-carbon alkane dehydrogenation process thereof |
| CN104084198A (en) * | 2014-07-15 | 2014-10-08 | 华陆工程科技有限责任公司 | Platinum aluminium oxide series catalyst for preparing propylene by propane dehydrogenation and preparation method of catalyst |
| WO2015025286A3 (en) * | 2013-08-21 | 2015-05-28 | Saudi Basic Industries Corporation | Selective zeolite supported catalysts for propane and butane dehydrogenation |
| CN105582921A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for light alkanes and use method for dehydrogenation catalyst |
| CN105582922A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of low-carbon alkane |
| CN108114717A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of C10~C13Long-chain normal paraffin dehydrogenation and its preparation and application |
| CN108325523A (en) * | 2018-02-02 | 2018-07-27 | 华东理工大学 | A kind of propane dehydrogenation catalyst and preparation method thereof |
| CN109745979A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | Dehydrogenation and its preparation method and application |
| CN115155613A (en) * | 2022-08-04 | 2022-10-11 | 西南化工研究设计院有限公司 | Preparation method and application of novel environment-friendly propane dehydrogenation catalyst |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4677237A (en) * | 1984-11-29 | 1987-06-30 | Uop Inc. | Dehydrogenation catalyst compositions |
| US4595673A (en) * | 1984-11-29 | 1986-06-17 | Uop Inc. | Dehydrogenation catalyst compositions and method of their preparation |
| US4788371A (en) * | 1987-12-30 | 1988-11-29 | Uop Inc. | Catalytic oxidative steam dehydrogenation process |
| CN1032678C (en) * | 1992-12-21 | 1996-09-04 | 中国石油化工总公司 | Catalyst for dehydrogen of saturated hydrocarbon |
| EP0714872B1 (en) * | 1994-11-29 | 2000-08-16 | Degussa-Hüls Aktiengesellschaft | Catalyst for the dehydrogenation of C6-C15 paraffins |
-
1998
- 1998-06-18 CN CN98114083A patent/CN1099907C/en not_active Expired - Fee Related
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| CN101642713B (en) * | 2008-08-07 | 2011-12-07 | 中国石油天然气股份有限公司 | C16-C19Long-chain normal alkane dehydrogenation catalyst and preparation method and application thereof |
| WO2015025286A3 (en) * | 2013-08-21 | 2015-05-28 | Saudi Basic Industries Corporation | Selective zeolite supported catalysts for propane and butane dehydrogenation |
| CN105473228A (en) * | 2013-08-21 | 2016-04-06 | 沙特基础工业公司 | Selective zeolite supported catalysts for propane and butane dehydrogenation |
| CN103990454A (en) * | 2014-05-20 | 2014-08-20 | 南京沃来德能源科技有限公司 | Low-carbon alkane dehydrogenation catalyst as well as preparation method and low-carbon alkane dehydrogenation process thereof |
| CN104084198A (en) * | 2014-07-15 | 2014-10-08 | 华陆工程科技有限责任公司 | Platinum aluminium oxide series catalyst for preparing propylene by propane dehydrogenation and preparation method of catalyst |
| CN105582921A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Dehydrogenation catalyst for light alkanes and use method for dehydrogenation catalyst |
| CN105582922A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of low-carbon alkane |
| CN105582921B (en) * | 2014-10-24 | 2019-04-12 | 中国石油化工股份有限公司 | Catalyst for dehydrogenation of low-carbon paraffin and its application method |
| CN105582922B (en) * | 2014-10-24 | 2019-07-05 | 中国石油化工股份有限公司 | Catalyst for dehydrogenating low-carbon alkane |
| CN108114717A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of C10~C13Long-chain normal paraffin dehydrogenation and its preparation and application |
| CN109745979B (en) * | 2017-11-03 | 2022-07-12 | 中国石油化工股份有限公司 | Dehydrogenation catalyst, preparation method and application thereof |
| CN109745979A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | Dehydrogenation and its preparation method and application |
| CN108325523A (en) * | 2018-02-02 | 2018-07-27 | 华东理工大学 | A kind of propane dehydrogenation catalyst and preparation method thereof |
| CN108325523B (en) * | 2018-02-02 | 2021-01-08 | 华东理工大学 | Propane dehydrogenation catalyst and preparation method thereof |
| CN115155613A (en) * | 2022-08-04 | 2022-10-11 | 西南化工研究设计院有限公司 | Preparation method and application of novel environment-friendly propane dehydrogenation catalyst |
| CN115155613B (en) * | 2022-08-04 | 2023-12-05 | 西南化工研究设计院有限公司 | Preparation method and application of novel environment-friendly propane dehydrogenation catalyst |
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