CN101892071B - Method for producing alkylation gasoline by using boron trifluoride-trifluoroethanol complex as catalyst - Google Patents
Method for producing alkylation gasoline by using boron trifluoride-trifluoroethanol complex as catalyst Download PDFInfo
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- CN101892071B CN101892071B CN 201010225790 CN201010225790A CN101892071B CN 101892071 B CN101892071 B CN 101892071B CN 201010225790 CN201010225790 CN 201010225790 CN 201010225790 A CN201010225790 A CN 201010225790A CN 101892071 B CN101892071 B CN 101892071B
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Abstract
The invention relates to a method for producing high-octane gasoline by performing catalytic conversion on isobutane-butylene by using boron trifluoride-trifluoroethanol complex as a catalyst in the field of petrochemical industry. By performing the catalytic conversion on the isobutane-butylene with the catalyst, the alkylation gasoline can be produced highly selectively under certain reaction conditions; and after the reaction is finished, the catalyst can be conveniently separated from an alkylation product, and the process is simple. Compared with the conventional sulfuric acid process and hydrogen fluoride process, the process has the advantages of mild reaction conditions, high selectivity of C8, low catalyst cost, the easy separation of the catalyst from the product and high application safety, and thus is a completely novel alkylation gasoline production process.
Description
Technical field:
The invention belongs to petrochemical industry, be specifically related to a kind of method of utilizing novel alkylation catalyst to produce stop bracket gasoline.
Background technology:
People are since eighties of last century has been found alkylated reaction the forties, and the alkylated reaction of Trimethylmethane and butylene becomes the important clean gasoline means of production of petroleum chemical industry.The total about 170 cover alkyl plants in the whole world move the motor spirit of annual supply more than 10% now.Gasoline alkylate has high-octane rating (RON:92-98, MON:90～96), the advantage of low Reid Vapour Pressure, low-sulfur, low aromatic hydrocarbons.Can relax greatly during this gasoline combustion because the urban air pollution that motor vehicle exhaust causes is a kind of desirable gasoline blend component.
Industrial, the alkylated reaction of Trimethylmethane and butylene still adopts traditional alkylation process, i.e. sulfuric acid process and hydrofluoric acid method.With regard to Technology itself, the vitriol oil, hydrofluoric acid alkylation technology are all very ripe, and the alkylate oil of producing is best in quality.In addition, these two kinds of technologies are very strong to catalytic cracking gas adaptability, can produce good alkylate oil to various butylene (1-butylene, 2-butylene, iso-butylene).And through the development of decades, the relative unit of the vitriol oil, hydrofluoric acid alkylation and equipment are also all very ripe.Yet because the character of these two kinds of catalyzer own, they also exist insoluble defective, as serious equipment corrosion and problem of environmental pollution.In addition, the sulfuric acid alkylation technology also exists shortcomings such as sour consumption big (100kg acid/t oil), the molten oily by-product of acid are many, acid regeneration cost height.And hydrofluoric acid volatility height easily forms the hydrofluoric acid aerosol, and toxicity is big, the security system that anti-hydrofluoric acid leaks, and investment and running cost height, corrodibility is strong.Therefore, development environment close friend's alkylation novel process is a petrochemical industry difficult problem for a long time.
In recent decades, never stop to the improvement of traditional alkylation catalyst with to the exploration of novel alkylation catalyst.The alkylation catalyst of studying has solid acid, chlorine aluminic acid ionic liquid, heteropolyacid and liquid superacid etc., but these new catalytic technologies also can't replace traditional sulfuric acid process and hydrofluoric acid method, fail in the industrial large-scale application that obtains.
Boron trifluoride is often used as catalyst for reaction such as condensation, polymerization, isomerization at chemical field, still prepare the raw material of a tetrafluoro borate.Boron trifluoride is the poisonous corrosive gases with pungent stench and strong and stimulating at normal temperatures and pressures.In malaria, produce white cigarette, generate a large amount of smog when leaking in a large number.Therefore, on technology and safety, all have difficulties as alkylation catalyst with boron trifluoride merely.Boron trifluoride and oxygen-containing organic compound can form the stable comple that mol ratio is 1: 1 or 1: 2.Can form boiling point with ether such as boron trifluoride is 126 ℃ stable comple.In addition, boron trifluoride can also form two kinds of complex compounds that mol ratio is 1: 1 and 1: 2 with alcohols, and mol ratio is 1: 1 complex compound instability, and step-down or heating will be decomposed, and the complex compound that 1: 2 ratio forms can not decompose when distillation.Fluorine is the strongest element of electronegativity.When with the hydrogen on the fluorine substituted alcohols, the acidity of fluorinated alcohols just can strengthen.The complex compound that forms with fluorinated alcohols and boron fluoride can form a kind of liquid superacid.Therefore, this super acids can be used as the catalyzer of alkylated reaction.
Summary of the invention:
One object of the present invention is to provide a kind of new alkylation catalyst; Another object of the present invention is to adopt this new catalyzer, and forming a kind of is the novel process of raw material production alkylate oil with Trimethylmethane and butylene.
It is catalyzer that the present invention proposes with boron trifluoride and trifluoroethanol complex compound, is raw material with Trimethylmethane and butylene, and temperature of reaction is carried out between-20-80 ℃, reaction pressure is at 0.1-1MPa, raw material alkane alkene ratio is 1: 1-200: 1, and the reaction times is under the condition of 0.1-60min, the preparation alkylate oil.
In the aforesaid method, described catalyzer is the complex compound that boron trifluoride and trifluoroethanol form.
In the aforesaid method, described butene feedstock is 1-butylene, 2-butylene, iso-butylene or their mixture.
The alkylation that the present invention proposes, generation alkylate oil that can highly selective, after reaction was finished, catalyzer can separate with alkylate very easily, and technology is simple.Traditional sulfuric acid process of comparing and hydrofluoric acid method, this technological reaction mild condition, C8 selectivity height, catalyzer cost are low, and environmental pollution is little, is a kind of new alkylation process.
Embodiment:
The present invention will be described with specific embodiment below, but application of the present invention not only is confined to the listed scope of embodiment.
Preparation of catalysts
Embodiment 1:
Boron triflouride gas is fed in the 100 gram trifluoroethanols, and continuously stirring and with the dry ice cooling is taken away the reaction liberated heat.When the weight of trifluoroethanol no longer increases, the expression trifluoroethanol can not with more boron trifluoride generation complex reaction, the ratio of the amount of substance between boron trifluoride and the trifluoroethanol is 0.1: 1 to 1: 1, preferred ratio is 1: 1.Prepared complex compound namely can be used as alkylation catalyst.
The preparation of alkylate oil
Embodiment 2:
Boron trifluoride-trifluoroethanol complex compound of preparation in above-described embodiment 1 is added in the reactor of being with stirring for 20 milliliters, remove air in the reactor with nitrogen, vigorous stirring, utilize high-pressure pump with Trimethylmethane and 1-butylene 50ml, reactor pressure is at 0.4MPa, alkane alkene ratio is 10: 1 in the raw material, reacts 60min down at 0 ℃.After reaction was finished, the Trimethylmethane of reaction was not participated in emptying, after catalyzer and resultant are left standstill, and the product layering, the upper strata is alkylate oil, lower floor is catalyzer, can obtain alkylate oil after the separation.
Embodiment 3:
Boron trifluoride-trifluoroethanol complex compound 20ml of preparation in above-described embodiment 1 is added in the reactor of band stirring, remove air in the reactor with nitrogen, vigorous stirring, utilize high-pressure pump with Trimethylmethane and 2-butylene 50ml, reactor pressure is at 1MPa, alkane alkene ratio is 10: 1 in the raw material, reacts 1min down at 80 ℃.After reaction was finished, the Trimethylmethane of reaction was not participated in emptying, after catalyzer and resultant are left standstill, and the product layering, the upper strata is alkylate oil, lower floor is catalyzer, can obtain alkylate oil after the separation.
Embodiment 4:
Boron trifluoride-trifluoroethanol complex compound 20ml of preparation in above-described embodiment 1 is added in the reactor of band stirring, remove air in the reactor with nitrogen, vigorous stirring, utilize high-pressure pump with Trimethylmethane and iso-butylene 50ml, reactor pressure is at 0.4MPa, alkane alkene ratio is 50: 1 in the raw material, reacts 5min down at 30 ℃.After reaction was finished, the Trimethylmethane of reaction was not participated in emptying, after catalyzer and resultant are left standstill, and the product layering, the upper strata is alkylate oil, lower floor is catalyzer, can obtain alkylate oil after the separation.
Embodiment 5:
Boron trifluoride-trifluoroethanol complex compound 20ml of preparation in above-described embodiment 1 is added in the reactor of band stirring, remove air in the reactor with nitrogen, vigorous stirring, utilize high-pressure pump that Trimethylmethane and butylene (are comprised 1-butylene, 2-butylene and iso-butylene or its mixture) mixing raw material 50ml, reactor pressure is at 0.4MPa, and alkane alkene ratio is 10: 1 in the raw material, reacts 30min down at 20 ℃.After reaction was finished, the Trimethylmethane of reaction was not participated in emptying, after catalyzer and resultant are left standstill, and the product layering, the upper strata is alkylate oil, lower floor is catalyzer, can obtain alkylate oil after the separation.
Embodiment 6:
Boron trifluoride-trifluoroethanol complex compound 20ml of preparation in above-described embodiment 1 is added in the reactor of band stirring, remove air in the reactor with nitrogen, vigorous stirring, utilize high-pressure pump that Trimethylmethane and butylene (are comprised 1-butylene, 2-butylene and iso-butylene or its mixture) mixing raw material 50ml, reactor pressure is at 0.4MPa, and alkane alkene ratio is 10: 1 in the raw material, reacts 5min down at 20 ℃.After reaction was finished, the Trimethylmethane of reaction was not participated in emptying, after catalyzer and resultant are left standstill, and the product layering, the upper strata is alkylate oil, lower floor is catalyzer, can obtain alkylate oil after the separation.
Embodiment 7:
Boron trifluoride-trifluoroethanol complex compound 20ml of preparation in above-described embodiment 1 is added in the reactor of band stirring, remove air in the reactor with nitrogen, and continue punching press to 0.8MPa, vigorous stirring, utilize high-pressure pump with the mixing raw material 50ml of Trimethylmethane and butylene (comprising 1-butylene, 2-butylene and iso-butylene or its mixture), reactor pressure is at 1MPa, alkane alkene ratio is 20: 1 in the raw material, reacts 5min down at 30 ℃.After reaction was finished, the Trimethylmethane of reaction was not participated in emptying, after catalyzer and resultant are left standstill, and the product layering, the upper strata is alkylate oil, lower floor is catalyzer, can obtain alkylate oil after the separation.
Embodiment 8:
Boron trifluoride-trifluoroethanol complex compound 20ml of preparation in above-described embodiment 1 is added in the reactor of band stirring, remove air in the reactor with nitrogen, vigorous stirring, utilize high-pressure pump that Trimethylmethane and butylene (are comprised 1-butylene, 2-butylene and iso-butylene or its mixture) mixing raw material 50ml, reactor pressure is at 0.4MPa, and alkane alkene ratio is 60: 1 in the raw material, reacts 5min down at 40 ℃.After reaction was finished, the Trimethylmethane of reaction was not participated in emptying, after catalyzer and resultant are left standstill, and the product layering, the upper strata is alkylate oil, lower floor is catalyzer, can obtain alkylate oil after the separation.
Adopt gas-chromatography to carry out quantitative analysis alkylate oil, determine the kind of every kind of material by mass spectrum, adopt normalization method to carry out quantitatively.Obtain the alkylation oil composition.
The quantitative analysis results of embodiment 2-8 alkylate oil
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment the present invention is had been described in detail, those skilled in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the claim scope of the present invention.
Claims (2)
1. be the method for Preparation of Catalyst gasoline alkylate with boron trifluoride-trifluoroethanol complex compound, it is characterized in that with boron trifluoride-trifluoroethanol complex compound be catalyzer, be 0.1～1MPa in reaction pressure, temperature of reaction is between-20～80 ℃, reaction times is 0.1～60min, and raw material alkane alkene ratio is under 1: 1～200: 1 the reaction conditions, to be raw material with Trimethylmethane and butylene, raw material is contacted with catalyzer, produce stop bracket gasoline.
2. method according to claim 1 is characterized in that butene feedstock is 1-butylene, 2-butylene, iso-butylene or their mixture.
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| CN 201010225790 CN101892071B (en) | 2010-07-05 | 2010-07-05 | Method for producing alkylation gasoline by using boron trifluoride-trifluoroethanol complex as catalyst |
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| CN 201010225790 CN101892071B (en) | 2010-07-05 | 2010-07-05 | Method for producing alkylation gasoline by using boron trifluoride-trifluoroethanol complex as catalyst |
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| CN101892071B true CN101892071B (en) | 2013-08-21 |
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| US10369556B2 (en) | 2014-12-11 | 2019-08-06 | Uop Llc | Integrated process for gasoline production |
| CN109181741B (en) * | 2018-09-04 | 2020-12-08 | 任才银 | Method for reducing emission of toxic substances in automobile exhaust |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862258A (en) * | 1973-11-29 | 1975-01-21 | Mobil Oil Corp | Isoparaffin-olefin alkylation with added water and with a complex of a macroreticular acid cation exchange resin and bf{11 |
| US5345027A (en) * | 1992-08-21 | 1994-09-06 | Mobile Oil Corp. | Alkylation process using co-current downflow reactor with a continuous hydrocarbon phase |
| CN1277893A (en) * | 2000-07-05 | 2000-12-27 | 复旦大学 | Method for preparing modified beta zeolite catalyst used for alkylation reaction of isobutane/butylene |
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- 2010-07-05 CN CN 201010225790 patent/CN101892071B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862258A (en) * | 1973-11-29 | 1975-01-21 | Mobil Oil Corp | Isoparaffin-olefin alkylation with added water and with a complex of a macroreticular acid cation exchange resin and bf{11 |
| US5345027A (en) * | 1992-08-21 | 1994-09-06 | Mobile Oil Corp. | Alkylation process using co-current downflow reactor with a continuous hydrocarbon phase |
| CN1277893A (en) * | 2000-07-05 | 2000-12-27 | 复旦大学 | Method for preparing modified beta zeolite catalyst used for alkylation reaction of isobutane/butylene |
Non-Patent Citations (1)
| Title |
|---|
| H3PO4-BF3/ZrO2及H3PO4-BF3-H2SO4/ZrO2催化剂上异丁烷/丁烯的烷基化反应;千载虎，廖世军;《高等学校化学学报》;19900430;第11卷(第4期);380-384 * |
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Inventor after: Zhang Suojiang Inventor after: Xin Jiayu Inventor after: Zhang Zhen Inventor after: Zhao Guoying Inventor after: Zhang Xiangping Inventor after: Yan Dongxia Inventor before: Zhang Suojiang Inventor before: Xin Jiayu Inventor before: Zhang Zhen Inventor before: Zhao Guoying Inventor before: Zhang Xiangping Inventor before: Yan Dongxia |
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