CN1097653A - Producing isobutene from oxidative dehydrogenation of isobutane catalyzer and manufacture method thereof - Google Patents

Producing isobutene from oxidative dehydrogenation of isobutane catalyzer and manufacture method thereof Download PDF

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CN1097653A
CN1097653A CN93115308A CN93115308A CN1097653A CN 1097653 A CN1097653 A CN 1097653A CN 93115308 A CN93115308 A CN 93115308A CN 93115308 A CN93115308 A CN 93115308A CN 1097653 A CN1097653 A CN 1097653A
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fluorochemical
catalyzer
isobutane
oxidative dehydrogenation
oxide compound
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CN1044787C (en
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张伟德
汤丁亮
万惠霖
蔡启瑞
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Xiamen University
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Xiamen University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

A kind of based on the producing isobutene from oxidative dehydrogenation of isobutane catalyzer of rare earth with other metal oxide, fluorochemical.Contain particularly Ce of rare earth metal, La, Sm, Y, Nd, the oxide compound of Th or other metal such as Bi, Sn, Cr, Pb, Mg, Ca, the oxide compound of Ba also contains one or both fluorochemicals, and said fluorochemical is a rare earth metal, Ce particularly, La, Sm, Y, Nd, the fluorochemical of Th or Li, Na, K, Cs, Mg, Ca, Sr, Ba, Bi, Cr, Pb, the fluorochemical of Cd.The mol ratio of oxide compound and fluorochemical is (4: 1)～(1: 4).This catalyzer is made simple, and physical strength is good, and catalytic performance is stable, and temperature of reaction is low, iso-butylene yield height.

Description

Producing isobutene from oxidative dehydrogenation of isobutane catalyzer and manufacture method thereof
The present invention relates to the catalyzer that a kind of low-carbon alkanes oxydehydrogenation prepares corresponding alkene.
Trimethylmethane extensively is present in the petroleum gas, is one of major ingredient of liquefied petroleum gas (LPG).The product iso-butylene of isobutene for oxo-dehydrogenation is the important source material of synthetic gasoline additive methyl tertiary butyl ether (MTBE).Iso-butylene is mainly obtained by two kinds of approach at present: the one, obtain by steam cracking legal system ethylene by-product.The 2nd, obtain from the Trimethylmethane direct dehydrogenation.Steam splitting process will consume a large amount of heat energy, and requires the anti-high temperature more than 1200 ℃ of relevant metal pipe material.From Trimethylmethane direct dehydrogenation preparing isobutene is a kind of method preferably, but needs precious metals pt as catalyzer.
H.H.Kung etc. (see J.Catal., 1993,140: 226; Proceedings 9 th International Cengress on Catalysis P1554) have reported VMgO(vanadium magnesia, 40Wt% V 2O 560Wt% MgO) effect in the catalyzer isobutene for oxo-dehydrogenation, temperature of reaction is 500 ℃, and catalyst weight (g)/reaction gas flow velocity is: 380gmin/mol isobutane(air speed is about 1500ml/hg), the reaction gas proportioning is a Trimethylmethane: oxygen: helium=4: 8: 88.Its result is the Trimethylmethane transformation efficiency: 8.0%, and the iso-butylene yield: 5.12%, selective isobutene: 64%.
The purpose of this utility model is intended to develop a kind of based on the catalyzer of rare earth with the producing isobutene from oxidative dehydrogenation of isobutane of some other metal oxide, fluorochemical.
The present invention contains a kind of metal oxide, and said metal can be rare earth metal, particularly Ce, La, and Sm, Y, Nd, Th etc. can be other metals also, as Bi, Sn, Cr, Pb, Te, Cd, Mg, Ca, Sr, Ba etc.The said catalyzer of the present invention also contains one or both fluorochemicals, and said fluorochemical can be rare earth metal fluorochemical, particularly Ce, La, Sm, Y, Nd, the fluorochemical of Th etc. also can be Li, Na, K, Cs, Mg, Ca, Sr, Ba, Bi, Cr, Pb, the fluorochemical of Cd etc.The mol ratio of oxide compound and fluorochemical is (4: 1)～(1: 4), serves as better with (2: 1)～(1: 2), is preferably 1: 1.
Above-mentioned fluorochemical can be directly with commercially available fluorochemical, also can be with the soluble salt of rare earth or other metal with NH 4The aqueous solution of F directly is settled out corresponding fluorochemical.
Its manufacture method of said catalyzer is the salt that the fluorochemical of metering and the oxide compound of metering maybe can be decomposed into oxide compound to be mixed mill evenly, mix well into pasty state with distilled water, oven dry 2～6h is preferably 3h under 100 ℃, high-temperature roasting 3～8h is preferably 3～5h; The maturing temperature scope is 700～900 ℃, preferably at 800～900 ℃; Make needed granularity then, be generally 0.22～0.40mm.
Evaluating catalyst is to carry out in fixed-bed reactor, normal pressure, and temperature of reaction is generally 450～550 ℃, iso-butylene yield 7%～23%.
Catalyzer of the present invention is made simple, and physical strength is good, and catalytic performance is stable, can be used for producing isobutene from oxidative dehydrogenation of isobutane at a lower temperature, and the iso-butylene yield is higher.In addition, can not add diluent gas during dehydrogenation reaction, help the separation of product and improve the space-time yield of reaction.
The invention will be further described with embodiment below.
Embodiment 1: 4.34 gram Ce(NO 2) 26H 2O and 1.13 gram Y 2O 2Mix, add distilled water and grind well, under constantly stirring, splash into and contain NH 4The aqueous solution of F 1.11 grams was dried 3 hours down at 100 ℃, and 0.22 to 0.40mm granularity was made in 850 ℃ of following roastings in 3 hours.Prepared catalyzer is used for the reaction of producing isobutene from oxidative dehydrogenation of isobutane, and reaction conditions is: reaction gas proportioning: i-C 4H 10: 02=1: 1,500 ℃ of temperature of reaction, catalyst levels 0.5ml, air speed is 6000/h.Analytical reaction tail gas Trimethylmethane transformation efficiency as can be known is 15.4%, and generating selective isobutene is 71.3%, and the iso-butylene yield is 10.9%.Other condition is constant, and when temperature of reaction was 540 ℃, the Trimethylmethane transformation efficiency was 51.0%, and generating selective isobutene is 44.6%, and the iso-butylene yield is 22.8%.
Embodiment 2: take by weighing 0.64 gram TiO respectively 2, 2.96 the gram La(NO 3) 36H 2O, 0.31 gram NH 4With 0.086 gram CsNO 3, add distilled water, mix and grind well, 100 ℃ of oven dry 6 hours down,, make the 0.22-0.40mm granularity 750 ℃ of roastings 6 hours.Reaction conditions is with example 1, and the Trimethylmethane transformation efficiency is 25.0%, and selective isobutene is 64.2%, and the iso-butylene yield is 15.6%.When the alcoxyl ratio is 3: 5, when other condition was the same, the Trimethylmethane transformation efficiency was 30.7%, and selective isobutene is 56.3%, and the iso-butylene yield is 17.3%.
Embodiment 3:4.66 restrains Bi 2O 3Add and contain 4.34 gram Ce(NO 3) 36H 2In the aqueous solution of O, splash into the NH that contains 1.11 grams 4The aqueous solution of F grinds well, and 100 ℃ of down oven dry 2 hours, again 800 ℃ of following roastings 3 hours, makes 0.22 to 0.40mm granularity, the activity of evaluate catalysts under with the reaction conditions of example 1.The Trimethylmethane transformation efficiency is 11.4%, and selective isobutene is 64.3%, and the iso-butylene yield is 7.36%.
Embodiment 4: 3.94 gram CeF 3Add 1.68 gram Nd 2O 3In, mix, add distilled water and grind well, 100 ℃ of oven dry 3 hours down, the 0.22-0.40mm granularity is made in 880 ℃ of following roastings 3 hours.The Trimethylmethane transformation efficiency is 15.7% under with the reaction conditions of example 1, and selective isobutene is 71.8%, and the iso-butylene yield is 11.3%.In temperature of reaction is 520 ℃, and when other condition was same, the iso-butylene yield was 13.6%.
Embodiment 5: 0.01mol CaF 2Add 0.04mol Ca(NO 3) 2In, add distilled water and grind well, 100 ℃ of oven dry 3 hours down, the 0.22-0.40mm granularity is made in 700 ℃ of following roastings 8 hours.Under the reaction conditions with example 1, the iso-butylene yield is 12.3%.
Embodiment 6:0.04mol MgF 2Add and contain 0.01mol Ca(NO 3) 2The aqueous solution in, grind well, 100 ℃ of down oven dry 2 hours, again 700 ℃ of following roastings 3 hours, other condition is with example 1, the iso-butylene yield is 13.2 ℃.

Claims (7)

1, a kind of producing isobutene from oxidative dehydrogenation of isobutane catalyzer contains a kind of metal oxide, and said metal can be alkene earth metals, particularly Ce, La, Sm, Y, Nd, Th can be other metal also, as Bi, Sn, Cr, Pb, Te, Cd, Mg, Ca, Sr, Ba is characterized in that also containing one or both fluorochemicals, and said fluorochemical is alkene earth metals fluorochemical or Li, Na, K, Cs, Mg, Ca, Sr, Ba, Bi, Cr, Pb, the Cd fluorochemical, the mol ratio of oxide compound and fluorochemical is (4: 1)～(1: 4).
2, catalyzer as claimed in claim 1 is characterized in that said alkene earth metals fluorochemical is Ce, La, Sm, Y, Nd, the fluorochemical of Th.
3, catalyzer as claimed in claim 1 is characterized in that the mol ratio of oxide compound and fluorochemical is (2: 1)～(1: 2).
4, catalyzer as claimed in claim 1, the mol ratio that it is characterized in that oxide compound and fluorochemical is 1: 1.
5, a kind of manufacture method of producing isobutene from oxidative dehydrogenation of isobutane catalyzer, it is characterized in that said catalyzer is the fluorochemical of metering to be added to mix in the oxide compound that measures mill evenly, mix well into pasty state with distilled water, dry 2～6h down in 100 ℃, high-temperature roasting 3～8h, maturing temperature is 700～900 ℃, makes the particle of 0.22～0.40mm then.
6, the manufacture method of producing isobutene from oxidative dehydrogenation of isobutane catalyzer as claimed in claim 5 is characterized in that maturing temperature is 800～900 ℃, and roasting time is 3～5h.
7, the manufacture method of producing isobutene from oxidative dehydrogenation of isobutane catalyzer as claimed in claim 5 is characterized in that said drying time is 3h.
CN93115308A 1993-12-29 1993-12-29 Producing isobutene catalyst by oxidizing and dehydrogenating isobutane Expired - Fee Related CN1044787C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1086150C (en) * 1996-12-24 2002-06-12 中国科学院兰州化学物理研究所 Catalyst for producing isobutylene by catalytic dehydrogenation of isobutane and procedure thereof
CN103420768A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Method for preparing isobutene from isobutane

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5254781A (en) * 1991-12-31 1993-10-19 Amoco Corporation Olefins process which combines hydrocarbon cracking with coupling methane
EP0557790B1 (en) * 1992-02-28 1998-08-19 Sumitomo Chemical Company Limited Process for producing isobutylene by oxidative dehydrogenation of isobutane
CN1030136C (en) * 1992-06-25 1995-10-25 厦门大学 C2-n hydrocarbon catalyst produced from methane by oxidation coupling
CN1030377C (en) * 1992-08-21 1995-11-29 厦门大学 Catalyst for making ethylene from ethane oxidative dehydrogenation
CN1029915C (en) * 1992-10-19 1995-10-04 厦门大学 Catalyst for preparing propene by oxidative dehydrogenation of propane

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1086150C (en) * 1996-12-24 2002-06-12 中国科学院兰州化学物理研究所 Catalyst for producing isobutylene by catalytic dehydrogenation of isobutane and procedure thereof
CN103420768A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Method for preparing isobutene from isobutane
CN103420768B (en) * 2012-05-16 2016-01-13 中国石油化工股份有限公司 The method of Trimethylmethane preparing isobutene

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