CN1062848C - Method for preparing alkylate oil by alkylating isobutane and butene - Google Patents
Method for preparing alkylate oil by alkylating isobutane and butene Download PDFInfo
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- CN1062848C CN1062848C CN94120018A CN94120018A CN1062848C CN 1062848 C CN1062848 C CN 1062848C CN 94120018 A CN94120018 A CN 94120018A CN 94120018 A CN94120018 A CN 94120018A CN 1062848 C CN1062848 C CN 1062848C
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- butene
- alkylation
- isobutane
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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)
Abstract
本发明属于异丁烷与丁烯烷基化制取烷基化油的方法，本发明选择杂多酸，包括PW12、PMO12、SiW12、SiMo12、PWnMo12-n其中n＝1～11，溶解于低碳脂肪酸、酯、酮、醚、醇等溶剂中，制成催化剂，催化异丁烷与丁烯的烷基化反应，烷基化油其烷烃组份在95%以上，以烯烃重量计的油收率为170-200%，催化剂在反应中不失活，无硫酸和氢氟酸的强腐蚀性及毒害性，烃相可不经碱洗、水洗、直接经蒸馏循环使用，可望取代以硫酸或氢氟酸为烷基化反应的催化剂。The present invention belongs to the method for preparing alkylated oil by alkylation of isobutane and butene. The present invention selects heteropolyacids, including PW 12 , PMO 12 , SiW 12 , SiMo 12 , PW n Mo 12-n where n= 1 to 11, dissolved in low-carbon fatty acids, esters, ketones, ethers, alcohols and other solvents to make catalysts to catalyze the alkylation reaction of isobutane and butene, and the alkane component of the alkylated oil is more than 95% , the oil yield based on the weight of olefins is 170-200%, the catalyst will not be deactivated during the reaction, there is no strong corrosiveness and toxicity of sulfuric acid and hydrofluoric acid, and the hydrocarbon phase can be directly recycled by distillation without alkali washing or water washing It is expected to replace sulfuric acid or hydrofluoric acid as the catalyst for alkylation reaction.
Description
The invention belongs to Trimethylmethane and the butene alkylated method of producing alkylate oil.
Gasoline alkylate is because it has the low susceptibility of high octane value, and no aromatic hydrocarbons component has high shock resistance and pollution-free as motor spirit, thereby is high-quality motor spirit and can be used as the gasoline concoction composition that is obtained by refining of petroleum.
At present industrial main be that catalyzer synthesizes this class gasoline by Trimethylmethane and butylene with sulfuric acid and hydrofluoric acid, and these two kinds of acid all have very big corrodibility, the sour waste disposal problem in the sulfuric acid catalysis process is subjected to the environment aspect and more and more pays close attention to.The liquid hydrogen fluoric acid for healthy be the potential hazardous material, along with improving constantly and possible law action that environment and safety problem aspect are paid close attention to, present alkylation process is faced with harsh examination.
Recently for over ten years, the various countries scientist is exploring new catalyzer to replace this two kinds of catalyzer.Used various molecular sieves (A.Corma, A.Martinez, C.Martinez Catal.Lett.28,187-201,1994), and super acids (T.Hosoi, T.Okada, S.Nojima, T.Imai Jpn.Patent 01,245,853; 01,245, material such as 854 1989), but these researchs are not success so far, this is because these catalyzer generally all need higher temperature of reaction, the side reaction of alkene oligomerization will take place so simultaneously, produce macromolecule product, thereby make catalyst junction charcoal inactivation, just present, also do not exist satisfied can replace sulfuric acid, the alkylation catalyst of hydrofluoric acid (National ResearchCouncil of the unite states:Catalysis of Looks to the Future, the catalysis prospect, BJ University Press P144,1993).
The objective of the invention is with in low-carbon oxygen-containing organic compound such as acid, alcohol, ester, ketone and composition thereof is catalyzer for dissolved heteropolyacid in the solvent, catalyzing iso-butane alkane and the butene alkylated gasoline alkylate of producing.
The invention provides a kind of catalyzer of new synthesis of alkyl carburetion.The present invention system comprises PW with heteropolyacid
12, PMo
12, SiW
12, PW
nMO
12-nHeteropolyacids such as (n=1～11), be dissolved in low carbon fatty acid by 10-70%, ester, ketone, ether, in the mixed solution equal solvent of alcohol and lipid acid and aliphatic alcohol ester, make catalyzer, the alkylated reaction of catalyzing iso-butane alkane and butylene is reflected in 10-70 ℃ and carries out, alkane alkene compares 1.5-18, its alkane component of catalysis synthetic alkylate oil is more than 95%, is 170～200% (theoretical amount 204%) in the oily yield of alkene (weight), and its analysis of components of the gasoline alkylate that obtains is better than the gasoline alkylate composition that obtains with sulfuric acid process, the product of nothing＞C9～C12 generates, and is higher to the generation selectivity of the trimethylpentane of the high-octane rating composition of alkylate oil.
Heteropolyacid of the present invention in catalyzer in reaction non-inactivation, slightly soluble in hydrocarbon phase, hydrocarbon phase can be without alkali cleanings, washing directly through distillation, separates unreacted Trimethylmethane and solvent in the hydrocarbon phase, makes it to recycle.Separate and to obtain the gasoline alkylate that major ingredient is a trimethylpentane simultaneously.This is catalyzer with the heteropolyacid in liquid phase, and catalyzing iso-butane alkane and butene alkylated method are not seen any report.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:
In the 1ml volume ratio is 1: 1 acetate, in the n-butyl acetate mixed solvent, adds 0.5 gram PW
12Heteropolyacid, adding volume ratio are 5: 1 alkane olefin liquid 1.7 grams, 30 ℃ of reactions 2 hours, obtain alkylate oil 1.1 grams, in alkene (weight) yield 173.6%, alkylation selectivity 84.1%.Embodiment 2:
In 0.5ml acetate, add 0.25 gram PW
12Heteropolyacid makes it to form saturated solution, adds and contains Trimethylmethane 54.5%, butylene, iso-butylene amounts to 38.4% hydrocarbon mixture 0.95 gram, 50 ℃ of reactions 3 hours, gets alkylate oil 0.25 gram, in the oily yield 69.3% of alkene (weight), alkylation selectivity 30.4%.
Embodiment 3:
In the 0.5ml butylacetate, add 0.25 gram PW
12Heteropolyacid makes it to form saturated solution, adds and contains Trimethylmethane 54.5%, butylene, iso-butylene amounts to 38.4% hydrocarbon mixture 0.99 gram, 50 ℃ of reactions 3 hours, gets alkylate oil 0.29 gram, in the oily yield 77.1% of alkene (weight), alkylation selectivity 17.4%.
Embodiment 4:
In the 1ml volume ratio is 1: 3 acetate and butylacetate mixing solutions, add 0.5 gram PW
12Heteropolyacid makes it to form saturated solution, adds and contains Trimethylmethane 54.5%, butylene, iso-butylene amounts to 38.4% hydrocarbon mixture 1.31 grams, 50 ℃ of reactions 3 hours, gets alkylate oil 0.75 gram, in the oily yield 150.7% of alkene (weight), alkylation selectivity 32.1%.
Embodiment 5:
In the 1ml volume ratio is 1: 9 acetate and butylacetate mixing solutions, add 0.5 gram PW
12Heteropolyacid makes it to form saturated solution, adds and contains Trimethylmethane 54.5%, butylene, iso-butylene amounts to 38.4% hydrocarbon mixture 1.30 grams, 50 ℃ of reactions 3 hours, gets alkylate oil 0.78 gram, in the oily yield 157.9% of alkene (weight), alkylation selectivity 27.8%.Embodiment 6:
In the 1ml volume ratio is 1: 1 acetate and butylacetate mixing solutions, add 0.5 gram PW
12Heteropolyacid makes it to form saturated solution, adds and contains Trimethylmethane 54.5%, butylene, iso-butylene amounts to 38.4% hydrocarbon mixture 0.9 gram, 40 ℃ of reactions 3 hours, gets alkylate oil 0.50 gram, in the oily yield 146.2% of alkene (weight), alkylation selectivity 59.6%.
Embodiment 7:
In the 1ml volume ratio is 1: 1 acetate and butylacetate mixing solutions, add 0.5 gram PW
12Heteropolyacid makes it to form saturated solution, adds and contains Trimethylmethane 54.5%, butylene, iso-butylene amounts to 38.4% hydrocarbon mixture 1.10 grams, 50 ℃ of reactions 3 hours, gets alkylate oil 0.61 gram, in the oily yield 143.5% of alkene (weight), alkylation selectivity 22.0%.
Embodiment 8:
In the 1ml volume ratio is 1: 1 acetate and butylacetate mixing solutions, add 0.5 gram PW
12Heteropolyacid makes it to form saturated solution, adds alkane alkene again than hydrocarbon mixture 1.3 grams that are 5,50 ℃ of reactions 1.5 hours, gets alkylate oil 0.376 gram, and in the oily yield 177.7% of alkene (weight), alkylation selects 42.7%.
Embodiment 9:
In the 1ml volume ratio is 1: 1 acetate and butylacetate mixing solutions, add 0.5 gram PW
12Heteropolyacid makes it to be formed into saturated solution, adds alkane alkene again than hydrocarbon mixture 1.2 grams that are 7,50 ℃ of reactions 3 hours, gets alkylate oil 0.279 gram, in the oily yield 162.8% of alkene (weight), alkylation selectivity 75.2%.
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94120018A CN1062848C (en) | 1994-12-28 | 1994-12-28 | Method for preparing alkylate oil by alkylating isobutane and butene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94120018A CN1062848C (en) | 1994-12-28 | 1994-12-28 | Method for preparing alkylate oil by alkylating isobutane and butene |
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| Publication Number | Publication Date |
|---|---|
| CN1125639A CN1125639A (en) | 1996-07-03 |
| CN1062848C true CN1062848C (en) | 2001-03-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94120018A Expired - Fee Related CN1062848C (en) | 1994-12-28 | 1994-12-28 | Method for preparing alkylate oil by alkylating isobutane and butene |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057989C (en) * | 1998-04-22 | 2000-11-01 | 中国石油化工总公司 | Alkylation process of isomerized alkane and alkene |
| CN1291954C (en) | 2004-01-19 | 2006-12-27 | 中国石油化工股份有限公司 | Akylation reaction method for solid acid catalyzed isomeric paraffine and olefins |
| CN106278785B (en) * | 2015-06-29 | 2019-01-08 | 中国石油化工股份有限公司 | A kind of solid acid alkylating reaction method of isoparaffin and alkene |
| CN109637816B (en) * | 2018-12-27 | 2020-08-04 | 东北师范大学 | Cu2S-SiW12/MoS2 composite counter electrode and preparation method thereof and quantum dot sensitized solar cell |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0440250A2 (en) * | 1990-02-02 | 1991-08-07 | Nippon Shokubai Co., Ltd. | Method of preparing alkylnaphthalene compounds |
| EP0481360A2 (en) * | 1990-10-16 | 1992-04-22 | Mitsui Petrochemical Industries, Ltd. | Process for producing alkyl-substituted aromatic hydrocarbon |
| CN1060833A (en) * | 1990-10-16 | 1992-05-06 | 三井石油化学工业株式会社 | The production method of alkyl-substituted aromatic hydrocarbon |
| EP0561284A1 (en) * | 1992-03-19 | 1993-09-22 | Idemitsu Kosan Company Limited | Process for alkylating isoparaffin |
-
1994
- 1994-12-28 CN CN94120018A patent/CN1062848C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0440250A2 (en) * | 1990-02-02 | 1991-08-07 | Nippon Shokubai Co., Ltd. | Method of preparing alkylnaphthalene compounds |
| EP0481360A2 (en) * | 1990-10-16 | 1992-04-22 | Mitsui Petrochemical Industries, Ltd. | Process for producing alkyl-substituted aromatic hydrocarbon |
| CN1060833A (en) * | 1990-10-16 | 1992-05-06 | 三井石油化学工业株式会社 | The production method of alkyl-substituted aromatic hydrocarbon |
| EP0561284A1 (en) * | 1992-03-19 | 1993-09-22 | Idemitsu Kosan Company Limited | Process for alkylating isoparaffin |
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|---|---|
| CN1125639A (en) | 1996-07-03 |
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