CN101717321B - Method for catalyzing iso-butane/n-butene alkylation by solid acid - Google Patents
Method for catalyzing iso-butane/n-butene alkylation by solid acid Download PDFInfo
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- CN101717321B CN101717321B CN 200910200242 CN200910200242A CN101717321B CN 101717321 B CN101717321 B CN 101717321B CN 200910200242 CN200910200242 CN 200910200242 CN 200910200242 A CN200910200242 A CN 200910200242A CN 101717321 B CN101717321 B CN 101717321B
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- nafion
- sba
- solid acid
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Abstract
The invention belongs to the technical field of solid acid alkylation, and particularly discloses a method for catalyzing iso-butane and n-butene alkylation by solid acid. In the method, Nafion functional hydrophobic SBA-15 is adopted as a catalyst, iso-butane and n-butene is used as reactants, and continuous operation of a fixed bed reactor is adopted to realize the alkylation of the solid acid under the pressure condition of ensuring the reactants to be liquid at the temperature of between 30 and 110 DEG C. By using the catalyst, higher butene conversion rate and trimethylpentane (TMP) selectivity can be obtained.
Description
Technical field
The invention belongs to the solid acid alkylating technical field, be specifically related to a kind of method of solid acid catalysis Trimethylmethane and n-butene alkylation.
Background technology
High-quality gasoline alkylate is the fuel of current environmental protection and energy source of car active demand.The alkylate oil that the reaction of Trimethylmethane/n-butene alkylation is produced has that octane value is high, steam forces down, combustion heat value is high, the characteristics of sulfur-bearing nitrogen non-hydrocarbon component not, is desirable gasoline blend component.
Traditional alkylation process starts from the forties in last century, and it makes catalyzer with sulfuric acid or hydrofluoric acid, and selectivity is good, price is low.But, sulfuric acid corrosion equipment; Hydrofluoric acid toxicity is large, the serious harm HUMAN HEALTH.Therefore, along with the enhancing of social environment consciousness, the acid catalyzed alkylation process of liquid is greatly limited.
Solid acid alkylation processes is the environment-friendly type technique process of the alternative liquid acid technique developed in recent years, both at home and abroad to the existing history more than 20 years of its research.The maximum characteristics of this technique are environmental friendliness, do not produce problem of environmental pollution.
Summary of the invention
The purpose of this invention is to provide a kind of alkylating activity and selectivity high, and the solid acid catalysis Trimethylmethane of non-environmental-pollution and the method for n-butene alkylation.
The method of solid acid catalysis Trimethylmethane provided by the invention and n-butene alkylation, its step is the same with existing solid acid alkylating step, under the loading type mesoporous molecular sieve catalyst exists, liquid phase alkylation reaction occurs by Trimethylmethane and n-butene namely, adopt the fixed-bed reactor operate continuously, realize solid acid alkylating, wherein used catalyst is the hydrophobic type SBA-15 of Nafion functionalization.
The hydrophobic type SBA-15 of the catalyst n afion functionalization that the present invention is used, take the mesoporous molecule of the SBA-15 of high-sequential as carrier, with silylating reagent, this carrier surface is carried out hydrophobic treatment, and then carry out the Nafion functionalization and obtain, remember that this catalyzer is Nafion/Me-SBA-15.
In the present invention, the liquid phase alkylation reaction of the hydrophobic type SBA-15 institute catalysis of Nafion functionalization, temperature of reaction is 30-110 ℃, alkane alkene mol ratio (I/O) 5: 1-100: 1, WHSV is at 0.1-10.0h for the alkene liquid hourly space velocity
-1
In the present invention, in the hydrophobic type SBA-15 catalyzer of Nafion functionalization, the charge capacity of Nafion is 5-50wt.%, preferred 15-35wt.%.
In the present invention, the silylating reagent that the surface hydrophobicity treating processes of SBA-15 adopts is trimethylethoxysilane, triethyl-ethoxy-silicane alkane or trimethylammonium methoxy silane.
In the present invention, the preparation process of used catalyst is as follows:
(1) preparation of SBA-15 carrier:
With P123 (EO
20PO
70EO
20, BASF) be template, take TEOS as the silicon source, synthetic SBA-15 under strong acidic condition.Mole consisting of of reactant: P123: SiO
2: HCl: H
2O=1: 60: 350: 9000.Building-up process is: the 40mL concentrated hydrochloric acid is dissolved in the 210mL deionized water, then add 8g P123,40 constant temperature water baths stir 1h, then drip TEOS16.0g, 40 ℃ of constant temperature stir 24h, then mixture are transferred in the water heating kettle of 200mL with the tetrafluoroethylene inner sleeve, filter to get white solid after 100 ℃ of hydrothermal crystallizing 24h, 80 ℃ of oven dry, 550 ℃ of processing 6h of retort furnace remove template P123 under air atmosphere, obtain the white powder of SBA-15.
(2) hydrophobic treatment of SBA-15 carrier surface:
2.5 after～3g SBA-15 drying pre-treatment (200 ℃ of vacuum-drying); take 3～4g silylating reagent; be dissolved in 25～30ml dry toluene under argon shield; 90～110 ℃ were refluxed 10～14 hours; use respectively toluene and ethanol drip washing after filtration; dry under 80 ℃～85 ℃ at last, obtain the SBA-15 of hydrophobic type, be designated as Me-SBA-15.
(3) preparation of the hydrophobic type SBA-15 of Nafion functionalization:
The hydrophobic type SBA-15 of Nafion functionalization is by Nafion (5%Nafion water-alcohol solution, Dupont) impregnated in above-mentioned Me-SBA-15,55 ℃～65 ℃ were refluxed 5～7 hours, the solid that obtains obtained in 60 ℃～70 ℃ lower vacuum-dryings after at room temperature dry 10～12 hours in 10～12 hours again, was designated as Nafion/Me-SBA-15.
The catalytic performance of Nafion/Me-SBA-15:
The present invention is with Nafion/Me-SBA-15 and SBA-15 without hydrophobic treatment the Nafion/SBA-15 that carrier makes and compares, support of the catalyst is in advance after hydrophobic treatment, alkylating activity and selectivity is improved, work as TOS=1min, temperature of reaction is at 100 ℃, Nafion carrying capacity (wt.%) is 5-50%, and its performance is compared as follows:
Listed catalyzer in table, the Nafion carrying capacity is 30%.
Embodiment
Embodiment 1:
Take SBA-15 as carrier; after drying pre-treatment (200 ℃ of vacuum-drying); take 2.6g SBA-15; 3.5g trimethylethoxysilane or triethyl-ethoxy-silicane alkane; or the trimethylammonium methoxy silane, be dissolved in the 30ml dry toluene under argon shield, 100 ℃ were refluxed 12 hours; use respectively toluene and ethanol drip washing after filtration, obtain the surface through the Me-SBA-15 of hydrophobic treatment 80 ℃ of lower dried overnight at last.
(the 5%Nafion water-alcohol solution Dupont) impregnated in above-mentioned Me-SBA-15, and 60 ℃ were refluxed 6 hours, and the solid that obtains obtained final Nafion/Me-SBA-15 in 12 hours in 60 ℃ of lower vacuum-dryings after at room temperature dry 12 hours again with Nafion.Nafion wt.%=30 in final sample, acid content is 0.258mmol H
+/ g
cat
Embodiment 2:
With above-mentioned Nafion/Me-SBA-15 (Nafion wt.%=30) sample that makes, levigate rear compressing tablet is made 40-60 order particle.Sample is put into the fixed-bed reactor constant temperature zone, and reaction pressure 3.2-3.4Mpa, Trimethylmethane/1-butylene mol ratio 40: 1,1-butylene mass space velocity WHSV=1.4h are reacted in the lower 110 ℃ of activation of nitrogen atmosphere 10 hours after being cooled to temperature of reaction
-1, 100 ℃ of temperature of reaction, alkylation activity is as follows:
Embodiment 3:
With above-mentioned Nafion/Me-SBA-15 (Nafion wt.%=30) sample that makes, levigate rear compressing tablet is made 40-60 order particle.Sample is put into the fixed-bed reactor constant temperature zone, and reaction pressure 3.2-3.4Mpa, Trimethylmethane 2-butylene mol ratio 40: 1,2-butylene mass space velocity WHSV=2.0h are reacted in the lower 110 ℃ of activation of nitrogen atmosphere 10 hours after being cooled to temperature of reaction
-1, 100 ℃ of temperature of reaction, alkylation activity is as follows:
Embodiment 4:
With above-mentioned Nafion/Me-SBA-15 (Nafion wt%=10) sample that makes, levigate rear compressing tablet is made 40-60 order particle.Sample is put into the fixed-bed reactor constant temperature zone, and reaction pressure 3.2-3.4Mpa, Trimethylmethane/1-butylene mol ratio 5: 1,1-butylene mass space velocity WHSV=0.5h are reacted in the lower 110 ℃ of activation of nitrogen atmosphere 10 hours after being cooled to temperature of reaction
-1, 30 ℃ of temperature of reaction, alkylation activity is as follows:
Embodiment 5:
With above-mentioned Nafion/Me-SBA-15 (Nafion wt%=45) sample that makes, levigate rear compressing tablet is made 40-60 order particle.Sample is put into the fixed-bed reactor constant temperature zone, and reaction pressure 3.2-3.4Mpa, Trimethylmethane/2-butylene mol ratio 100: 1,2-butylene mass space velocity WHSV=10.0h are reacted in the lower 110 ℃ of activation of nitrogen atmosphere 10 hours after being cooled to temperature of reaction
-1, 110 ℃ of temperature of reaction, alkylation activity is as follows:
Claims (3)
1. solid acid catalyst that is used for catalyzing iso-butane alkane/n-butene alkylation, it is characterized in that take the mesoporous molecule of SBA-15 as carrier, with silylating reagent, this carrier surface is carried out hydrophobic treatment, and then carry out the Nafion functionalization and obtain, remember that this catalyzer is Nafion/Me-SBA-15, wherein, to process the silylating reagent that adopts be trimethylethoxysilane, triethyl-ethoxy-silicane alkane or trimethylammonium methoxy silane for described surface hydrophobicity;
In catalyzer, the charge capacity of Nafion is 5-50wt.%.
2. the application of catalyzer as claimed in claim 1 in catalyzing iso-butane alkane/n-butene alkylation is characterized in that carrying out liquid phase alkylation reaction under described catalyzer exists, and adopts the fixed-bed reactor operate continuously, realizes solid acid alkylating.
3. application according to claim 2 is characterized in that described liquid phase alkylation reaction, and temperature of reaction is 30-110 ℃, alkane alkene mol ratio 5: 1-100: 1, and WHSV is at 0.1-10.0h for the alkene liquid hourly space velocity
-1
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| CN101717321B true CN101717321B (en) | 2013-06-12 |
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Families Citing this family (4)
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| CN104151119B (en) * | 2014-08-08 | 2016-01-13 | 山东利丰达生物科技有限公司 | The method of octane-iso is prepared in the deep processing of a kind of carbon four |
| CN105170163B (en) * | 2015-09-11 | 2017-11-07 | 宁波海越新材料有限公司 | A kind of preparation method for the solid super acid catalyst being alkylated for isobutane and butene |
| CN106179511A (en) * | 2016-07-08 | 2016-12-07 | 盐城工学院 | A kind of support type NaHSO of oleophylic4catalyst and its preparation method and application |
| CN110498725B (en) * | 2018-05-16 | 2022-03-11 | 中国石油化工股份有限公司 | Solid acid catalyzed alkylation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056578A (en) * | 1976-03-04 | 1977-11-01 | Shell Oil Company | Isoparaffin-olefin alkylation process using a supported perfluorinated polymer catalyst |
| CN1569335A (en) * | 2003-07-16 | 2005-01-26 | 中国石油化工股份有限公司 | Solid acid complex catalyst and its preparing process |
-
2009
- 2009-12-10 CN CN 200910200242 patent/CN101717321B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056578A (en) * | 1976-03-04 | 1977-11-01 | Shell Oil Company | Isoparaffin-olefin alkylation process using a supported perfluorinated polymer catalyst |
| CN1569335A (en) * | 2003-07-16 | 2005-01-26 | 中国石油化工股份有限公司 | Solid acid complex catalyst and its preparing process |
Non-Patent Citations (9)
| Title |
|---|
| Alkylation of Raffinate II and Isobutane on Nafion Silica Nanocomposite for the Production of Isooctane;Prashant Kumar等;《Energy & Fuels》;20060131;第20卷(第2期);第481-487页 * |
| Mark A. Harmer等.High Surface Area Nafion† |
| Mark A. Harmer等.High Surface Area Nafion†Resin/Silica Nanocomposites: A New Class of Solid Acid Catalyst.《Journal of American Chemical Society》.1996,第118卷(第33期),第7708-7715页. * |
| P. Botella等.The Influence of Textural and Compositional Characteristics of Nafion/Silica Composites on Isobutane/2-Butene Alkylation.《Journal of Catalysis》.1999,第185卷(第2期),第371-377页. |
| Prashant Kumar等.Alkylation of Raffinate II and Isobutane on Nafion Silica Nanocomposite for the Production of Isooctane.《Energy & Fuels》.2006,第20卷(第2期),第481-487页. |
| Resin/Silica Nanocomposites: A New Class of Solid Acid Catalyst.《Journal of American Chemical Society》.1996,第118卷(第33期),第7708-7715页. |
| The Influence of Textural and Compositional Characteristics of Nafion/Silica Composites on Isobutane/2-Butene Alkylation;P. Botella等;《Journal of Catalysis》;19990725;第185卷(第2期);第372页，第1栏第2段，第374页第2栏第10-18行,第375页第1栏第3段 * |
| 介孔分子筛SBA-15的乙基化修饰和表征;刘妍等;《化学工程师》;20050830(第8期);第2页第1栏第20-27行,第2栏倒数第3段 * |
| 刘妍等.介孔分子筛SBA-15的乙基化修饰和表征.《化学工程师》.2005,(第8期),第1-3页. |
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Inventor after: Shen Wei Inventor after: Gu Yi Inventor after: Kuang Weiwei Inventor after: Huang Zhen Inventor after: Xu Hualong Inventor after: Qiu Jianli Inventor before: Shen Wei Inventor before: Gu Yi Inventor before: Kuang Weiwei Inventor before: Huang Zhen Inventor before: Xu Hualong Inventor before: Qiu Jianli |
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