CN1125640A - Isobutane and butene alkylated solid heteropoly acid salt catalyzer - Google Patents
Isobutane and butene alkylated solid heteropoly acid salt catalyzer Download PDFInfo
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- CN1125640A CN1125640A CN 94120022 CN94120022A CN1125640A CN 1125640 A CN1125640 A CN 1125640A CN 94120022 CN94120022 CN 94120022 CN 94120022 A CN94120022 A CN 94120022A CN 1125640 A CN1125640 A CN 1125640A
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- CN
- China
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- alkane
- alkene
- catalyzer
- acid salt
- isobutane
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The catalyst for alkanisation of isobutane and butylene is the alkali-metal (Cs, K) and ammonium (NH4+, NCC2H5)4+) salt of 4 heteropoly acids (PW12, PMo12, SiW12 and SiMo12). The alkanisated oil contains 95% or more alkane component and oil yield rate is more than 150% (in ofefin weight). It features not deactivating during reaction, and no strong corrosion and poison.
Description
The invention belongs to Trimethylmethane and butene alkylated solid heteropoly acid salt catalyzer.
Along with the development of Modern Traffic cause, require more and more higher to oil engine Fuel Demand amount and quality of fuel.The output of whole world gasoline and additive thereof is the highest in all chemical, and synthetic what obtain is the motor spirit with good shock resistance with Trimethylmethane and butene alkylated method.This gasoline octane rating height, susceptibility is low, no aromatic hydrocarbons component, olefin(e) centent is very low, and the burning back is little to the pollution of environment.1940's has successively invented sulfuric acid and hydrofluoric acid is the method for catalyst Trimethylmethane and butene alkylated synthetic gasoline.Wherein the sulfuric acid process device has more than 70 covers in the world, existing more than 100 covers of hydrofluoric acid method, and more than 2,000 ten thousand tons of sulfuric acid processs of total production gasoline alkylate are catalyzer with 98% the vitriol oil, the hydrofluoric acid method is a catalyzer with 90% HF.These two kinds of acid all are to have severe corrosive, easily cause the severe contamination to environment, the material of harm humans health, thereby in decades, the various countries scientist exploring new catalyzer to replace this two kinds of catalyzer, has used molecular sieve, super acids (SO
4/ ZrO
2), ion-exchange resin, the BF of appendix
3Deng material is catalyzer, but not success of the research of these explorations.The problem of catalyst deactivation does not solve, this is the total problem of solid acid catalyst, A.Corma, A, Martinez, Catal.Rev.-Sci.Eng.35 (4) 483-570 (1993) has made disclosed report, because the solid acid catalyst of being made up of oxide compound generally all need just have enough activity under higher temperature of reaction, at this moment will cause alkene oligomerization, produce macromolecule product and make catalyst junction charcoal and inactivation, the catalyzer of therefore seeking new synthesizing alkylated gasoline has been regarded as one of problem to be solved of several urgency in a global difficult problem and the catalytic field.
The catalytic performance of heteropolyacid excellence shows in many organic reactions, it is highly effective catalyzer in many industrialized organic acid catalysis industry, Science Bulletin 39 (15) 1392 (1994) Xu Zheng, people such as Wu Yue disclose a kind of alkylated reaction of testing isobutyl a heatable brick bed and butylene under solid phase appendix condition, yet it is the same with its ground solid acid catalyst, the result also has building-up reactions to take place, and has only alkylation activity seldom.
The objective of the invention is with the solid heteropoly acid salt is catalyst Trimethylmethane and the butene alkylated gasoline alkylate of producing.
The invention provides a kind of catalyzer of new synthesis of alkyl carburetion.Be by phosphorus tungsten, the phosphorus molybdenum, silicon tungsten, four kinds of heteropolyacid synthetic of silicon molybdenum basic metal (Cs, K) and ammonium (NH
4 +, N (C
2H
5)
4 +) salt is as catalyzer, the mobility scale of basic metal and ammonium ion content (mole ratio): phosphorus series is 0.5-3.0, silicon series is 30 ℃ for the alkylating temperature of reaction of 0.5-4.0. catalyzing iso-butane alkane and butylene, alkane alkene ratio is 15: 1, the alkane component accounts for more than 95% in the alkylate oil, in the optimum oil yield of alkene weight greater than 150%.
Its analysis of components of the gasoline alkylate that the present invention obtains is better than the gasoline alkylate composition that obtains with sulfuric acid process, the product of nothing＞C9～C12 generates, generation selectivity to the trimethylpentane of high-octane rating composition in the alkylate oil is higher, catalyzer is non-inactivation in reaction, can use repeatedly, be insoluble to hydrocarbon phase, be easy to separate with product, hydrocarbon phase can be without alkali cleaning, washing directly can obtain the gasoline alkylate that main component is a trimethylpentane through distillation, the unreacting material of separating can be recycled, because it does not have the severe corrosive of sulfuric acid and hydrofluoric acid and toxic that the catalytic performance that is higher than these two kinds of acid is arranged again, being expected to replace with sulfuric acid or hydrofluoric acid is the catalyzer of alkylated reaction.Embodiment provided by the invention is as follows: embodiment 1.
Accurately take by weighing 0.5 gram Cs
2.5H
0.5PW
12To reactor, add alkane alkene than the alkane and the alkene that are 15, wherein alkene weighs 0.4378 gram, and 30 ℃ were reacted 2 hours, gets alkylate oil 0.8118 gram, in the oily yield 185.4% of alkene (weight), 100 ℃ of oven dry reused after 2 hours after C8 alkane selectivity 100%. catalyst separating, and reaction conditions is the same, and obtaining oily yield is 138.4%, using oily yield for the third time is 136.6%, and C8 alkane selectivity is 100%.Embodiment 2.
Accurately take by weighing 0.5 gram K
0.5H
2.5PW
12To reactor, add alkane alkene than the alkane and the alkene that are 15, wherein alkene weighs 0.4378 gram, and 30 ℃ were reacted 2 hours, get alkylate oil 0.5856 gram, oil yield 133.7%, C8 alkane selectivity 100%, 100 ℃ of oven dry reused after 2 hours after the catalyst separating, reaction conditions is the same, obtaining oily yield is 129.1%, and using oily yield for the third time is 120.1%, and C8 alkane selectivity is 100%.Embodiment 3.
Accurately take by weighing 0.5 gram (NH
4)
1.0H
2.0PW
12To reactor, add alkane alkene than the alkane and the alkene that are 15, wherein alkene weighs 0.4378 gram, and 30 ℃ were reacted 2 hours, got alkylate oil 0.6556 gram, in the oily yield 149.7% of alkene (weight), C8 alkane selectivity 100%.100 ℃ of oven dry reused after 2 hours after the catalyst separating, and reaction conditions is the same, and obtaining oily yield is 114.0%, and using oily yield for the third time is 112.1%, and C8 alkane selectivity is 100%.Embodiment 4.
Accurately take by weighing 0.5 gram Cs
1.5H
1.5PW
12To reactor, add alkane alkene than the alkane and the alkene that are 15, wherein alkene weighs 0.4378 gram, and 25 ℃ were reacted 2 hours, got alkylate oil 0.3876 gram, in the oily yield 88.5 of alkene (weight), C8 alkane selectivity 100%.Embodiment 5.
Accurately take by weighing 0.5 gram Cs
1.5H
1.5PW
12To reactor, add alkane alkene than the alkane and the alkene that are 8, wherein alkene weighs 0.4378 gram, and 30 ℃ were reacted 2 hours, got alkylate oil 0.3062 gram, in the oily yield 69.9% of alkene (weight), C8 alkane selectivity 100%.
Claims (1)
1. Trimethylmethane and butene alkylated solid heteropoly acid salt catalyzer is characterized in that adopting by phosphorus tungsten, the phosphorus molybdenum, and silicon tungsten, four kinds of heteropolyacid synthetic of silicon molybdenum basic metal (Cs, K) and ammonium (NH
4 +, N (C
2H
5)
4 +) salt is as catalyzer, the mobility scale of basic metal and ammonium ion content (mole ratio): phosphorus series is 0.5-3.0, silicon series is 0.5-4.0, the alkylating temperature of reaction of catalyzing iso-butane alkane and butylene is 30 ℃, alkane alkene ratio is 15: 1, the alkane component accounts for more than 95% in the alkylate oil, in the optimum oil yield of alkene weight greater than 150%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94120022 CN1125640A (en) | 1994-12-28 | 1994-12-28 | Isobutane and butene alkylated solid heteropoly acid salt catalyzer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94120022 CN1125640A (en) | 1994-12-28 | 1994-12-28 | Isobutane and butene alkylated solid heteropoly acid salt catalyzer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1125640A true CN1125640A (en) | 1996-07-03 |
Family
ID=5039459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94120022 Pending CN1125640A (en) | 1994-12-28 | 1994-12-28 | Isobutane and butene alkylated solid heteropoly acid salt catalyzer |
Country Status (1)
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| CN (1) | CN1125640A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049418C (en) * | 1996-12-11 | 2000-02-16 | 中国石油化工总公司 | Method for alkylation of isomeric paraffine and olefine |
| CN1057989C (en) * | 1998-04-22 | 2000-11-01 | 中国石油化工总公司 | Alkylation process of isomerized alkane and alkene |
| US7674945B2 (en) | 2004-01-19 | 2010-03-09 | China Petroleum & Chemical Corporation | Process for alkylation of an aromatic hydrocarbon or isoalkane with an olefin over the catalysis of a solid acid |
-
1994
- 1994-12-28 CN CN 94120022 patent/CN1125640A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049418C (en) * | 1996-12-11 | 2000-02-16 | 中国石油化工总公司 | Method for alkylation of isomeric paraffine and olefine |
| CN1057989C (en) * | 1998-04-22 | 2000-11-01 | 中国石油化工总公司 | Alkylation process of isomerized alkane and alkene |
| US7674945B2 (en) | 2004-01-19 | 2010-03-09 | China Petroleum & Chemical Corporation | Process for alkylation of an aromatic hydrocarbon or isoalkane with an olefin over the catalysis of a solid acid |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |