CN109722282B - Method for preparing alkylate - Google Patents
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Abstract
The invention discloses a method for preparing alkylate, which comprises the following steps: mixing isobutane with C4Performing alkylation reaction on olefin in the presence of water and an ionic liquid catalyst to obtain a reaction product containing alkylate oil; the ionic liquid catalyst comprises cations and anions, wherein the cations are at least one selected from isoquinoline cations, quinoline cations and benzimidazole cations, and the anions are at least one selected from hydrogen sulfate, trifluoromethanesulfonate, dihydrogen phosphate, p-toluenesulfonate, trifluoroacetate, tetrafluoroborate and hexafluoroborate. The method adopts the ionic liquid with cation of isoquinoline cation, quinoline cation or benzimidazole cation as the catalyst to prepare the alkylate oil, and has the advantages of mild reaction conditions, high reaction conversion rate and good selectivity.
Description
Technical Field
The invention relates to a method for preparing alkylate, in particular to a method for preparing alkylate by taking an ionic liquid as a catalyst.
Background
With the rapid development of the automobile industry and the enhancement of awareness of people about environmental protection, the demand of lead-free high-octane gasoline is increasing in countries around the world. In China, the national gasoline standard is continuously improved due to the increase of environmental pollution and the influence of haze. In the latest six-Beijing standard, the content of aromatic hydrocarbon and olefin in gasoline is strictly limited, the content of aromatic hydrocarbon is not more than 35 percent, and the content of olefin is not more than 15 percent. In this case, blending alkylate in gasoline is an effective way to maintain the high octane number and low vapor pressure of gasoline.
It is well known that the catalysts used in the current industry for the alkylation of alkanes and alkenes are mainly inorganic liquid superacids such as concentrated sulfuric acid and hydrofluoric acid. Although both of these techniques are well-established, these strong acids have the problems of high consumption, difficult regeneration, high corrosiveness and serious environmental pollution. Therefore, research and development of next-generation efficient novel alkylation catalysts is imminent. Compared with inorganic super acid, the solid acid catalyst overcomes the defects of corrosivity, toxicity and the like of concentrated sulfuric acid and hydrofluoric acid to a certain extent. However, solid acids as catalysts exist in different degrees, and it is difficult to economically and effectively solve the problems of low activity, easy deactivation, poor selectivity and the like caused by carbon deposition. These problems have resulted in the inability of solid acid catalysts to be used in large quantities in the alkylation industry.
The ionic liquid as the acid catalyst overcomes the defects of the conventional solvent to a certain extent, and has a certain application prospect.
Chinese patent CN101177371A discloses a method for alkylation of isoparaffin and olefin catalyzed by ionic liquid. The method uses isobutane and C4 olefin as reactants and adopts ionic liquid of imidazole or pyridine cation as an acidic liquid catalyst. Reacting at 70 deg.C and 1.6MPa for 0.5h, with 1-butene conversion of 100%, alkylate yield of 202.4%, and alkylate composition C8Total 74.3%, TMP: DMH is 4.0, and a good reaction effect is obtained.
Special for ChinaThe patent application CN105505450A discloses a preparation method of alkylated gasoline based on an ionic liquid catalyst. The method takes isobutane and butene as reactants and takes tetraazaadamantane and quaternary phosphorus ionic liquid composite solvent as an acid catalyst. Reacting at 10 deg.C and 0.2MPa for 20 min. Conversion of butene 99%, C8The content of trimethylpentane in the hydrocarbon was 80.2%.
Disclosure of Invention
The invention aims to provide a method for preparing alkylate, which adopts ionic liquid with cation of isoquinoline cation, quinoline cation or benzimidazole cation as catalyst to prepare alkylate, and has mild reaction condition, high reaction conversion rate and good selectivity.
In order to achieve the above object, the present invention provides a method for preparing an alkylate, which comprises: mixing isobutane with C4Performing alkylation reaction on olefin in the presence of water and an ionic liquid catalyst to obtain a reaction product containing alkylate oil;
wherein the ionic liquid catalyst comprises cations and anions, the cations are at least one selected from isoquinoline cations, quinoline cations and benzimidazole cations, and the anions are at least one selected from hydrogen sulfate, trifluoromethanesulfonate, dihydrogen phosphate, p-toluenesulfonate, trifluoroacetate, tetrafluoroborate and hexafluoroborate,
the isoquinoline cation is shown as a formula (1),
the quinoline cation is shown as a formula (2),
the benzimidazole cation is shown as a formula (3),
in the formulae (1) to (3), A1、A3、A4Each independently being hydrogen or a sulphonic acid group, A2Is hydrogen, a sulfonic acid group or a carboxyl group, and m, o and p are each independently an integer of 1 to 14.
Preferably, in the formulae (1) to (3), m and p are each independently an integer of 1 to 5, and o is an integer of 4 to 10.
Preferably, in said formulae (1) and (2), A1When it is hydrogen, A2Hydrogen, sulfonic acid group or carboxyl group.
Preferably, in said formulae (1) and (2), A1When it is a sulfonic acid group, A1At position 5 of the isoquinoline or quinoline cation, A2Is sulfonic acid group.
Preferably, in said formula (3), A1When it is a sulfonic acid group, A1At position 5, A, of the benzimidazole cation3、A4Each independently hydrogen or a sulfonic acid group.
Preferably, in the ionic liquid of the present invention, when there is a sulfonic acid group in the cation, the anion may be hydrogen sulfate, or may be another anion of the present invention, and when there is no sulfonic acid group in the cation, the anion needs to be hydrogen sulfate.
Preferably, the cation of the ionic liquid is the cation of the ionic liquid described in the examples, and the anion is hydrogen sulfate or trifluoromethanesulfonate.
The invention selects ionic liquid containing condensed rings of benzimidazole, quinoline or isoquinoline and the like in cations as a catalyst, and uses isobutane and C4Preparation of alkylate from olefin as reaction raw material, C in obtained alkylate8The hydrocarbon and trimethylpentane content is high, the used ionic liquid catalyst is acidic ionic liquid, the performance is stable, the dosage is small, the corrosivity is small, the environment is friendly, the ionic liquid and the reaction product are separated simply, and the separated ionic liquid catalyst can be recycled for multiple times.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The cation of the ionic liquid contains fused rings such as benzimidazole, quinoline or isoquinoline, and a benzene ring and a pyridine ring, and the benzene ring and an imidazole ring are connected to form a fused ring, so that a larger delocalized pi-bond can be formed. The electronic cloud distribution is more uniform, and the stability is better. Meanwhile, groups with sulfonic groups or carboxyl groups are connected to the positions of the benzene ring and N atoms of imidazole or pyridine ring, so that the acid density of the ionic liquid is greatly improved, and the alkylation reaction performance is remarkably improved.
The invention uses isobutane and C4Olefin is used as a reaction raw material, water is used as a solvent of the ionic liquid, alkylation reaction is carried out, the reaction condition is mild, the conversion rate is high, the acidity of the ionic liquid catalyst is high, the selectivity is good, the using amount is small, the corrosivity is low, and the ionic liquid catalyst is environment-friendly.
In the reaction product of the invention, the properties of the components are greatly different and easy to separate, and the method can also comprise the following steps: separating the reaction product containing the alkylate oil to obtain a product containing unreacted gas components, the ionic liquid catalyst and the alkylate oil, wherein the ionic liquid catalyst is not dissolved in the alkylate oil, and the product is directly separated by a liquid separation method. In order to improve the utilization rate of the raw material and the catalyst, the separated gas component and/or the ionic liquid catalyst containing unreacted gas can be reused. The ionic liquid catalyst used in the invention has stable property and can be used for many times.
In the present invention, the isobutane and C4The mass ratio of the olefins may be (1-40): 1, preferably (8-20): 1, the dosage of the ionic liquid is less, and the ionic liquid catalyst can account for the isobutane and the C410 to 50% by mass, preferably 15 to 45% by mass, of the total amount of olefins, and the mass ratio of the ionic liquid catalyst to water may be (0.1 to 1.2):1, preferably (0.1 to 0.6): 1. Said C is4The olefin may be at least one of 1-butene, 2-butene, and isobutene.
The alkylation reaction conditions of the present invention may include: the reaction temperature is from-10 ℃ to 100 ℃, preferably from 40 ℃ to 80 ℃, the reaction time is from 0.1 to 4 hours, preferably from 0.1 to 2 hours, and the reaction pressure is from 0.1 to 5 MPa, preferably from 0.4 to 1.5 MPa (the pressure is absolute).
The invention is further illustrated by the following examples and comparative examples, but is not limited thereto.
Examples 1-7 were used to provide ionic liquid catalysts of the present invention.
Example 1
This example prepared ionic liquid a: n- (3-sulfonic group) propyl-5-sulfonic group isoquinoline trifluoromethanesulfonate, the structural formula is as follows:
the preparation method comprises the following steps:
(1) adding 50ml of toluene into a 100ml round-bottom flask, then adding 5-isoquinoline sulfonic acid and 1, 3-propane sultone in a molar ratio of 1:1.2, magnetically stirring and uniformly mixing in an ice bath, reacting for about 12 hours until the mixture is completely solidified, soaking and washing the obtained white solid for 3 times by using diethyl ether and ethyl acetate (in a volume ratio of 2:1), and drying at 100 ℃ under reduced pressure to obtain the white solid which is N- (3-sulfonic acid group) propyl-5-sulfonic acid group isoquinoline.
(2) Adding a certain amount of N- (3-sulfonic group) propyl-5-sulfonic group isoquinoline into a 50ml round-bottom flask, magnetically stirring, slowly dropwise adding equimolar trifluoromethanesulfonic acid into the flask at 25 ℃, heating to 80 ℃ after dropwise adding is finished, reacting for 24h, and drying the obtained product at 100 ℃ under reduced pressure in a rotary evaporator to obtain the N- (3-sulfonic group) propyl-5-sulfonic group isoquinoline trifluoromethanesulfonate product.
Example 2
This example prepared ionic liquid b: n-butylisoquinoline hydrogensulfate, structural formula:
the preparation method comprises the following steps:
(1) adding 50ml of toluene into a 100ml round-bottom flask, then adding isoquinoline and N-butyl chloride in a molar ratio of 1:1.2, uniformly mixing by magnetic stirring, heating to 90 ℃, reacting for about 24 hours until the mixture is completely solidified, soaking and washing the obtained white solid for 3 times by using diethyl ether and ethyl acetate (in a volume ratio of 2:1), and drying under reduced pressure at 100 ℃ to obtain the white solid which is N-butylisoquinoline chloride salt.
(2) Adding a certain amount of N-butylisoquinoline chloride salt into a 50ml round-bottom flask, magnetically stirring, slowly dropwise adding 98% concentrated sulfuric acid with the same mole into the flask at 25 ℃, heating to 80 ℃ after dropwise adding is finished, reacting for 24 hours, and drying the obtained product at 100 ℃ under reduced pressure to obtain the N-butylisoquinoline bisulfate.
Example 3
This example prepared ionic liquid c: 1-octyl-3-methyl-5-sulfonic benzimidazole hydrogen sulfate, the structural formula is as follows:
the preparation method comprises the following steps:
(1) adding 50ml of toluene into a 100ml round-bottom flask, then adding 3-methyl-5-sulfobenzimidazole and chloro-n-octane with the molar ratio of 1:1.2, uniformly mixing by magnetic stirring, heating to 90 ℃, reacting for about 24 hours until the mixture is completely solidified, soaking and washing the obtained white solid for 3 times by using diethyl ether and ethyl acetate (the volume ratio is 2:1), and drying under reduced pressure at 100 ℃ to obtain the white solid which is 1-octyl-3-methyl-5-sulfobenzimidazole chloride.
(2) Adding a certain amount of 1-octyl-3-methyl-5-sulfonic benzimidazole chloride into a 50ml round bottom flask, magnetically stirring, slowly dropwise adding 98% concentrated sulfuric acid with the same mole into the flask at 25 ℃, heating to 80 ℃ after dropwise adding is finished, reacting for 24 hours, and drying the obtained product at 100 ℃ under reduced pressure to obtain the 1-octyl-3-methyl-5-sulfonic benzimidazole hydrogen sulfate.
Example 4
This example prepared ionic liquid d: 1-hexyl-3- (4-sulfonic group) butyl-5-sulfonic group benzimidazole triflate, the structural formula is as follows:
the preparation method comprises the following steps:
(1) adding 50ml of toluene into a 100ml round-bottom flask, then adding 1-hexyl-5-sulfonic acid benzimidazole and 1, 4-butane sultone in a molar ratio of 1:1.2, magnetically stirring and uniformly mixing in an ice bath, reacting for about 12 hours until the mixture is completely solidified, soaking and washing the obtained white solid for 3 times by using diethyl ether and ethyl acetate (in a volume ratio of 2:1), and drying at 100 ℃ under reduced pressure to obtain the white solid which is 1-hexyl-3- (4-sulfonic acid) butyl-5-sulfonic acid benzimidazole.
(2) Adding a certain amount of 1-hexyl-3- (4-sulfonic group) butyl-5-sulfonic benzimidazole into a 50ml round-bottom flask, magnetically stirring, slowly dropwise adding equimolar trifluoromethanesulfonic acid into the flask at 25 ℃, heating to 80 ℃ after dropwise adding is finished, reacting for 24h, and drying the obtained product at 100 ℃ under reduced pressure to obtain 1-hexyl-3- (4-sulfonic group) butyl-5-sulfonic benzimidazole trifluoromethanesulfonate.
Example 5
This example prepared ionic liquid e: 1, 3-di (4-sulfonic group) butyl-5-sulfonic group benzimidazole triflate, the structural formula is as follows:
the preparation method comprises the following steps:
(1) adding 50ml of toluene into a 100ml round-bottom flask, then adding 5-sulfobenzimidazole and 1, 4-butane sultone in a molar ratio of 1:2, magnetically stirring and uniformly mixing in an ice bath, reacting for about 12 hours until the mixture is completely solidified, soaking and washing the obtained white solid for 3 times by using diethyl ether and ethyl acetate (in a volume ratio of 2:1), and drying at 100 ℃ under reduced pressure to obtain the white solid which is 1, 3-di (4-sulfogroup) butyl-5-sulfobenzimidazole.
(2) Adding a certain amount of 1, 3-di (4-sulfonic group) butyl-5-sulfonic benzimidazole into a 50ml round bottom flask, magnetically stirring, slowly dropwise adding equimolar trifluoromethanesulfonic acid into the flask at 25 ℃, heating to 80 ℃ after dropwise adding is finished, reacting for 24 hours, and drying the obtained product at 100 ℃ under reduced pressure to obtain the 1, 3-di (4-sulfonic group) butyl-5-sulfonic benzimidazole trifluoromethanesulfonate product.
Example 6
This example systemPreparing an ionic liquid f: n- (3-sulfonic group) propyl quinoline bisulfate, the structural formula is as follows:
the preparation method comprises the following steps:
(1) adding 50ml of toluene into a 100ml round-bottom flask, then adding quinoline and 1, 3-propane sultone in a molar ratio of 1:1.2, magnetically stirring and uniformly mixing in an ice bath, reacting for about 12 hours until the mixture is completely solidified, soaking and washing the obtained white solid for 3 times by using diethyl ether and ethyl acetate (in a volume ratio of 2:1), and drying in vacuum to obtain the white solid which is N- (3-sulfonic group) propyl quinoline.
(2) Adding a certain amount of N- (3-sulfonic group) propyl quinoline into a 50ml round-bottom flask, magnetically stirring, slowly dropwise adding 98% concentrated sulfuric acid with the same mole into the flask at 25 ℃, heating to 80 ℃ after dropwise adding is finished, reacting for 24 hours, and drying the obtained product at 100 ℃ under reduced pressure to obtain the N- (3-sulfonic group) propyl quinoline hydrogen sulfate.
Example 7
This example prepared ionic liquid g: n-carboxymethyl quinoline bisulfate, the structural formula is as follows:
the preparation method comprises the following steps:
adding a certain amount of N-carboxymethyl quinoline chloride into a 50ml round-bottom flask, magnetically stirring, slowly dropwise adding 98% concentrated sulfuric acid with the same mole into the flask at 25 ℃, heating to 80 ℃ after dropwise adding is finished, reacting for 24 hours, and drying the obtained product at 100 ℃ under reduced pressure to obtain the N-carboxymethyl quinoline hydrogen sulfate.
The following examples were used to carry out alkylation reactions using ionic liquids as catalysts provided by the present invention.
Examples 8 to 14
15g of the ionic liquid provided by the invention and 50g of water are added into a high-pressure reaction kettle. After removing most of the air under reduced pressure, N was introduced2Replacing air in the reaction kettle, pressurizing to 1.0MPa, heating and stirring. When the temperature in the kettle reaches 60 ℃, 50g of mixed liquid material of isobutane and butene with the mass ratio of alkane to alkene of 10 is introduced for alkylation reaction for 0.2 h. After the reaction is finishedCooling to 25 deg.C, and reducing pressure to normal pressure. Collecting unreacted gas components, wherein the upper layer of the liquid-phase product is alkylate oil, and the lower layer is ionic liquid. The kind and content of hydrocarbon contained in the alkylate oil were analyzed by GC-MS (gas chromatography-mass spectrometer), the number of ionic liquid, the amount of each material and the reaction conditions used in the examples are shown in Table 1, and the reaction results are shown in Table 2.
And adding the ionic liquid obtained by separation after the reaction into a reaction kettle, and repeating the alkylation reaction for 10 times without obvious change of the catalyst effect.
In table 2, trimethylpentane: the dimethyl hexane mass ratio (TMP/DMH) is used to illustrate the performance of the alkylate. In general, trimethylpentane has a higher octane number than dimethylhexane, and thus, a higher TMP/DMH ratio indicates better alkylate performance.
Comparative example 1
Concentrated sulfuric acid is used as a catalyst.
15g of concentrated sulfuric acid having a concentration of 98 mass% was charged into the autoclave. After removing most of the air under reduced pressure, N was introduced2Replacing air in the reaction kettle, pressurizing to 1.0MPa, heating and stirring. When the temperature in the kettle reaches 10 ℃, 50g of mixed liquid material of isobutane and butene with the alkane/alkene mass ratio of 10:1 is introduced, and the reaction lasts for 0.2 h. After the reaction is finished, cooling to 25 ℃, and reducing the pressure to normal pressure. Collecting unreacted gas components, wherein the upper layer of the liquid-phase product is alkylate oil, and the lower layer is concentrated sulfuric acid. The kind and content of hydrocarbon contained in the alkylate were analyzed by GC-MS, the amount of each material and the reaction conditions are shown in Table 1, and the reaction results are shown in Table 2.
As can be seen from Table 2, when the ionic liquid of the present invention was used as a catalyst, compared with comparative example 1, in which concentrated sulfuric acid was used as a catalyst, C was contained in the reaction product8The hydrocarbon content, butene conversion and TMP/DMH ratio are all increased. The catalytic effect of the ionic liquid catalyst provided by the invention is superior to that of the traditional concentrated sulfuric acid catalyst.
TABLE 1
TABLE 2
Claims (11)
1. A process for preparing an alkylate comprising: mixing isobutane with C4Performing alkylation reaction on olefin in the presence of water and an ionic liquid catalyst to obtain a reaction product containing alkylate oil;
wherein the ionic liquid catalyst comprises cations and anions, the cations are at least one selected from isoquinoline cations, quinoline cations and benzimidazole cations,
the isoquinoline cation is shown as a formula (1),
the quinoline cation is shown as a formula (2),
the benzimidazole cation is shown as a formula (3),
in the formulae (1) to (3), A1、A3、A4Each independently being hydrogen or a sulphonic acid group, A2Is hydrogen, a sulfonic acid group or a carboxyl group, m, o and p are each independently an integer of 1 to 14,
in the ionic liquid, when a sulfonic acid group exists in a cation, an anion is selected from at least one of hydrogen sulfate, trifluoromethanesulfonate, dihydrogen phosphate, p-toluenesulfonate and trifluoroacetate, and when the sulfonic acid group does not exist in the cation, the anion is the hydrogen sulfate.
2. The method according to claim 1, wherein, in formulae (1) to (3), m and p are each independently an integer of 1 to 5, and o is an integer of 4 to 10.
3. The process according to claim 1 or 2, wherein in the formulae (1) and (2), A1When it is hydrogen, A2Hydrogen, sulfonic acid group or carboxyl group.
4. The process according to claim 1 or 2, wherein in the formulae (1) and (2), A1When it is a sulfonic acid group, A1At position 5 of the isoquinoline or quinoline cation, A2Is sulfonic acid group.
5. The method according to claim 1 or 2, wherein, in the formula (3), A1When it is a sulfonic acid group, A1At position 5, A, of the benzimidazole cation3、A4Each independently hydrogen or a sulfonic acid group.
6. The method of claim 1, wherein the method further comprises: separating the reaction product containing alkylate oil to obtain the ionic liquid catalyst and the unreacted gas component for reuse.
7. The method of claim 1, wherein the isobutane and C4The mass ratio of the olefin is (1-40): 1, the ionic liquid catalyst accounts for the isobutane and C410 to 50 mass% of the total amount of olefins, and the mass ratio of the ionic liquid catalyst to water is (0.1 to 1.2): 1.
8. The method of claim 1, wherein the isobutane and C4The mass ratio of the olefin is (8-20): 1, the ionic liquid catalyst accounts for the isobutane and C415-45 mass% of the total amount of olefins, and the mass ratio of the ionic liquid catalyst to water is (0.1-0.6): 1.
9. The process of claim 1, wherein the alkylation reaction conditions comprise: the reaction temperature is-10 deg.C-100 deg.C, and the reaction pressure is 0.1-5 MPa.
10. The process of claim 9, wherein the alkylation reaction conditions comprise: the reaction temperature is 40-80 deg.C, and the reaction pressure is 0.4-1.5 MPa.
11. The method of claim 1, wherein C is4The olefin is at least one selected from the group consisting of 1-butene, 2-butene and isobutene.
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| CN1958576A (en) * | 2006-10-27 | 2007-05-09 | 西北大学 | Acid ion liquid of benzimidazole salts, synthetic method, and application in reaction of esterification |
| CN101018757A (en) * | 2005-09-07 | 2007-08-15 | Lg化学株式会社 | Preparation of organic acids from aldehyde compounds by means of liquid phase oxidation reaction |
| CN101177371A (en) * | 2006-11-11 | 2008-05-14 | 中国科学院兰州化学物理研究所 | Method for alkylation of isoparaffin and olefin catalyzed by ion liquid |
| CN101928250A (en) * | 2010-07-16 | 2010-12-29 | 华东师范大学 | Carbamido and imidazolium-containing ionic liquid and preparation method thereof |
| CN102229569A (en) * | 2011-04-11 | 2011-11-02 | 新疆大学 | Method for preparing Br[phi]nsted acidic ionic liquid based on benzimidazole cations |
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| US8535560B2 (en) * | 2009-07-14 | 2013-09-17 | Ut-Battelle, Llc | Ionic liquids for separation of olefin-paraffin mixtures |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101018757A (en) * | 2005-09-07 | 2007-08-15 | Lg化学株式会社 | Preparation of organic acids from aldehyde compounds by means of liquid phase oxidation reaction |
| CN1958576A (en) * | 2006-10-27 | 2007-05-09 | 西北大学 | Acid ion liquid of benzimidazole salts, synthetic method, and application in reaction of esterification |
| CN101177371A (en) * | 2006-11-11 | 2008-05-14 | 中国科学院兰州化学物理研究所 | Method for alkylation of isoparaffin and olefin catalyzed by ion liquid |
| CN101928250A (en) * | 2010-07-16 | 2010-12-29 | 华东师范大学 | Carbamido and imidazolium-containing ionic liquid and preparation method thereof |
| CN102229569A (en) * | 2011-04-11 | 2011-11-02 | 新疆大学 | Method for preparing Br[phi]nsted acidic ionic liquid based on benzimidazole cations |
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