CN115247078B - Alkylated gasoline and preparation method thereof - Google Patents

Abstract

The invention provides an alkylated gasoline and a preparation method thereof, wherein the preparation method comprises the following steps: carrying out alkylation reaction on isoparaffin and olefin under the action of a strong acid catalyst and a cocatalyst to obtain alkylated gasoline; wherein the cocatalyst is an acid ester compound. In the invention, the addition of the acid ester compound as the cocatalyst can obviously improve the reaction microenvironment of the acid hydrocarbon two-phase interface in the alkylation reaction, improve the selectivity of isooctane (especially trimethylpentane) and the yield of the alkylated gasoline, and obviously improve the RON value of the alkylated gasoline.

Description

Alkylated gasoline and preparation method thereof

Technical Field

The invention belongs to the field of gasoline production, and specifically relates to an alkylated gasoline and a preparation method thereof.

Background technique

Alkylation clean gasoline is a production technology that uses isoparaffin (mostly isobutane) and one or more olefins (C3-C5 olefins) as alkylation reaction raw materials, and undergoes chemical addition reaction under strong acid catalysis to produce clean gasoline containing a mixture of various isoparaffins. The alkylation gasoline is mainly 2,2,4-trimethylpentane (TMP) and its isomers (such as 2,3,4-trimethylpentane), has the advantages of high octane number, low sensitivity, good anti-knock performance, and almost no olefins, sulfur and aromatics, and is an ideal blending component for motor gasoline.

At present, the alkylation technologies used globally are mainly hydrofluoric acid alkylation and concentrated sulfuric acid alkylation. Hydrofluoric acid is an extremely dangerous chemical. Once it leaks during the production process, it will cause huge casualties and property losses, and seriously damage the surrounding environment. Compared with the hydrofluoric acid method, concentrated sulfuric acid is relatively safe, has low production energy consumption, and mature technology. It will be the mainstream of my country's alkylation process in the next decade. At the same time, since my country has more low-end gasoline products and fewer high-end products, improving the activity of concentrated sulfuric acid catalysts, increasing the solubility and mass transfer of acid-hydrocarbon interfaces, and significantly improving the quality of alkylated gasoline, especially improving the octane number of products, is the first choice for the development of alkylated gasoline.

Solid acid alkylation and ionic liquid alkylation are new process technologies that have been actively developed at home and abroad in recent years. Solid acid catalysts are much safer and more environmentally friendly than hydrofluoric acid alkylation and concentrated sulfuric acid alkylation, but they have poor raw material adaptability, complex process operation, high equipment investment and operating costs, and easy catalyst deactivation; ionic liquid catalysts have higher catalytic activity than sulfuric acid and hydrofluoric acid, but the cost of ionic liquid catalysts is high, and catalyst stability and raw material adaptability require time and more industrial application equipment to test. There is still a long way to go for solid acid alkylation and ionic liquid alkylation to completely replace traditional liquid acid alkylation technology.

Since the industrialization of sulfuric acid-based _C4 alkylation, research on additives for sulfuric acid-based _C4 alkylation has been ongoing. Additives can effectively reduce the corrosiveness of sulfuric acid, sulfuric acid consumption, and improve product quality. The ALKAT-X sulfuric acid additive developed by BetzDearborn Hydrocarbon Process Chemicals can increase the octane number and reduce acid consumption; the XL-2100 sulfuric acid additive developed by Davis Applied Technologies can reduce acid consumption and increase liquid recovery; C.M. Frederic et al. used trialkylphosphamide or sulfonamide with 10 to 20 carbon atoms in each branch chain as a sulfuric acid alkylation additive, which can effectively improve _C8 selectivity and thus improve the octane number of alkylated gasoline; G.Holzman et al. used trifluoroacetic acid as a sulfuric acid alkylation additive, which can improve the alkylation effect by adjusting the acid strength of sulfuric acid, thereby reducing the selectivity of dimethylhexane in the product and improving the selectivity of trimethylpentane; V.I.Zakoshanskij used cyclopentane sulfone as a sulfuric acid additive, which can greatly improve the selectivity of the alkylation reaction and reduce acid consumption; but the above-mentioned additives or their types and structural information have been kept confidential, or the effect on improving the alkylated gasoline product is weak.

CN102134507A discloses a method for preparing alkylated gasoline by modifying concentrated sulfuric acid with trifluoroethanol or ionic liquid as an auxiliary agent. The trifluoroethanol used in the method forms hydrofluoric acid in the reaction environment, corroding equipment and pipelines; at the same time, the alcohol hydroxyl group can react with concentrated sulfuric acid, thereby reducing the concentration and acidity of the concentrated sulfuric acid. CN106635141A discloses a method for producing alkylated gasoline with the assistance of adamantyl ionic liquid, which improves the selectivity and RON value of the alkylated product; at the same time, the acid consumption in the alkylation reaction is large, and the cost of waste acid treatment is high.

Therefore, those skilled in the art still need to conduct further research on the auxiliary agents for sulfuric acid alkylation.

Summary of the invention

The main purpose of the present invention is to provide an alkylation gasoline and a preparation method thereof. The alkylation gasoline prepared by the method of the present invention has a higher _C8 component selectivity and a higher octane number.

In order to achieve the above object, the present invention provides a method for preparing alkylated gasoline, which comprises: subjecting isoparaffin and olefin to an alkylation reaction under the action of a strong acid catalyst and a co-catalyst to obtain alkylated gasoline; wherein the co-catalyst is an acid ester compound.

In the method for preparing alkylate gasoline of the present invention, the promoter is at least one of n-butyl acetate, isobutyl acetate, tert-butyl acetate, di-n-butyl carbonate, diisobutyl carbonate and di-tert-butyl dicarbonate.

In the method for preparing alkylated gasoline of the present invention, the isoparaffin has 4 to 8 carbon atoms, and the olefin has 2 to 8 carbon atoms.

In the method for preparing alkylate gasoline of the present invention, the isoparaffin includes isobutane and/or isopentane; and the olefin includes at least one of propylene, isobutylene, normal butene, cis-2-butene, trans-2-butene and pentene.

In the method for preparing alkylate gasoline of the present invention, the strong acid catalyst comprises at least one of sulfuric acid, HF acid, trifluoromethanesulfonic acid, salicylic acid, solid molecular sieve and chloroaluminate ionic liquid.

In the method for preparing alkylate gasoline of the present invention, the mass ratio of the isoparaffin to the olefin is 1 to 100:1; the mass ratio of the co-catalyst to the strong acid catalyst is 0.0005 to 0.1:1; and the mass ratio of the strong acid catalyst to the total amount of the isoparaffin and the olefin is 1:10 to 10:1.

In the method for preparing alkylated gasoline of the present invention, the temperature of the alkylation reaction is -10 to 25° C., and the pressure is 0.1 to 3.0 MPa.

The method for preparing alkylated gasoline of the present invention comprises: mixing the strong acid catalyst and the co-catalyst, and then contacting the mixture with the isoparaffin and the olefin to carry out an alkylation reaction.

The method for preparing alkylate gasoline of the present invention further comprises, after the alkylation reaction, allowing the reaction product to stand for stratification, wherein the upper layer is the alkylate gasoline and the lower layer is the strong acid catalyst and the co-catalyst.

In order to achieve the above object, the present invention also provides the above preparation method to obtain alkylated gasoline.

Beneficial effects of the present invention:

The present invention uses acid ester compounds as co-catalysts to synergistically catalyze the preparation of alkylated gasoline. The acid ester compounds can improve the interface performance of the reaction system and maintain the acidity of the system, significantly improving the stability of the strong acid catalyst and the quality of the alkylated gasoline (selectivity of trimethylpentane). In addition, the acid ester compounds only contain C, H, and O elements, do not contain S and N, and do not pollute the environment; and the acid ester compounds are stable in a strong acid environment; at the same time, the distribution coefficients of the acid ester compounds in the oil phase and the acid phase are greatly different. After the alkylation reaction, the acid ester compounds do not exist in the oil phase, reducing the separation cost of the co-catalyst, and having broad industrial application prospects.

Detailed ways

The following is a detailed description of the embodiments of the present invention. The embodiments are implemented based on the technical solution of the present invention, and detailed implementation methods and processes are given. However, the protection scope of the present invention is not limited to the following embodiments. The experimental methods in the following embodiments where specific conditions are not specified are usually based on conventional conditions.

The present invention provides a method for preparing alkylated gasoline, which comprises: subjecting isoparaffin and olefin to an alkylation reaction under the action of a strong acid catalyst and a co-catalyst to obtain alkylated gasoline; wherein the co-catalyst is an acid ester compound.

In the process of isoparaffin and olefin reaction, adding acid ester co-catalyst to strong acid catalyst can improve the interface performance of reaction system and maintain the acidity of system, significantly improve the stability of strong acid catalyst and the quality of alkylated gasoline (selectivity of trimethylpentane). In detail, the role of acid ester co-catalyst is to improve the quality of alkylated gasoline produced by the alkylation reaction of isoparaffin and olefin, that is, to increase the _C8 content in alkylated gasoline, inhibit olefin superposition, and reduce the content of _C9 + by-products. At the same time, the reduction of _C9 + by-products effectively delays the deactivation rate of acid catalyst, reduces catalyst consumption, reduces enterprise cost, and improves economic benefits; moreover, acid ester co-catalyst is only composed of C, H, O elements, and does not harm the environment; moreover, acid ester co-catalyst is stable in strong acid environment, and is easy to separate from the product (alkylated gasoline) after reaction, and has broad prospects for industrial application.

In one embodiment, the isoalkane of the present invention has 3 to 8 carbon atoms; in another embodiment, the isoalkane has 4 to 6 carbon atoms; in yet another embodiment, the isoalkane includes isobutane and/or isopentane.

In one embodiment, the olefin of the present invention has 2 to 10 carbon atoms; in another embodiment, the olefin has 3 to 8 carbon atoms. The olefin may be a normal olefin or an isomeric olefin. In one embodiment, the olefin may include at least one of propylene, isobutylene, normal butene, cis-2-butene, trans-2-butene and pentene.

In one embodiment, the strong acid catalyst of the present invention comprises a combination of one or more of sulfuric acid, HF acid, trifluoromethanesulfonic acid, salicylic acid, solid molecular sieves and chloroaluminate ionic liquids, wherein the solid molecular sieve can be at least one of Y-type molecular sieve, USY molecular sieve, and ZSM-5. In another embodiment, the strong acid catalyst of the present invention is sulfuric acid.

The cocatalyst of the present invention is an acid ester compound. In one embodiment, the acid ester compound of the present invention is obtained by reacting an acid with an alcohol or a phenol, wherein the acid can be an organic acid or an inorganic acid, or a monobasic acid, a dibasic acid or a tribasic acid, and the alcohol can be a monohydric alcohol, a dihydric alcohol or a trihydric alcohol. The inorganic acid is, for example, carbonic acid, the organic acid is, for example, a carboxylic acid having 1 to 10 carbon atoms; the alcohol has, for example, 1 to 10 carbon atoms. In another embodiment, the acid ester compound includes a combination of one or more of n-butyl acetate, isobutyl acetate, tert-butyl acetate, di-n-butyl carbonate, diisobutyl carbonate, and di-tert-butyl dicarbonate.

In one embodiment, the mass ratio of isoparaffin to olefin of the present invention is 1 to 100:1; the mass ratio of the cocatalyst to the strong acid catalyst is 0.0005 to 0.1:1; the mass ratio of the strong acid catalyst to the total amount of isoparaffin and the olefin is 1:10 to 10:1. In another embodiment, the mass ratio of the cocatalyst to the strong acid catalyst of the present invention is 0.001 to 0.05:1.

The invention adds 0.05% to 5% of the acid ester promoter by weight of the strong acid catalyst, which can significantly improve the reaction environment of the acid-hydrocarbon interface in the alkylation reaction, reduce the alkylation reaction rate, reduce the olefin superposition rate, reduce the generation of reaction by-products, improve the catalytic activity of the strong acid catalyst, promote the reaction to move in the positive reaction direction, and play a significant role in improving the selectivity of the alkylation reaction, the yield of alkylation gasoline and the RON value.

In one embodiment, the preparation method of alkylated gasoline of the present invention comprises: mixing a strong acid catalyst and a co-catalyst, mixing isoparaffins and olefins, and then contacting the strong acid catalyst and the co-catalyst with the isoparaffins and olefins to carry out an alkylation reaction. After the alkylation reaction is completed, the reacted materials enter the alkylated gasoline separation tank for static stratification, and the unreacted alkanes enter the tail gas condensation tank for recovery; in the alkylated gasoline separation tank, the lower layer is the strong acid catalyst and the co-catalyst, and the upper layer is the alkylated gasoline. In another embodiment, the temperature of the alkylation reaction is -10°C to 50°C, and the reaction pressure is 0.1 to 3.0Mpa.

The present invention does not particularly limit the above-mentioned alkylation reaction device, which can be a continuous production device used for industrial sulfuric acid or hydrofluoric acid alkylation, or its alkylation reaction device (such as a fixed bed reactor, a slurry bed reactor, a packed bed reactor, a liquid-liquid two-phase mixing reactor, etc.), or a reactor with a stirring device. The alkylation reaction can be an intermittent reaction or a continuous reaction in the above-mentioned device. The isoparaffin, olefin, and acid ester cocatalyst in the present invention are all present in a high-pressure liquid state in the reaction device.

The technical solution of the present invention can be applied to C4 alkylation technology, which is a technology that uses C4 alkanes such as isobutane as alkylation raw materials and undergoes alkylation reactions with _C4 olefins to produce high-octane gasoline blending component 2,2,4-trimethylpentane (TMP), but the present invention is not limited thereto. The technical solution of the present invention will be further described in detail below through specific examples.

Example 1

510g of concentrated sulfuric acid was injected into a low-temperature, corrosion-resistant intermittent reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then, 120g of isobutane and 9g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to alkene was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the reacted materials entered the alkylation gasoline separation tank for static stratification, and the unreacted alkanes entered the tail gas condensation tank for recovery; in the alkylation gasoline separation tank, the lower layer was concentrated sulfuric acid catalyst and the upper layer was alkylation gasoline. The upper layer of alkylation gasoline was taken for gas chromatography quantitative analysis, the type of substance was determined by mass spectrometry, and the normalization method was used for quantitative calculation.

Example 2

510g of concentrated sulfuric acid and 7.65g of n-butyl acetate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Example 3

510g of concentrated sulfuric acid and 7.65g of isobutyl acetate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the alkylation gasoline was analyzed and calculated after standing for stratification.

Example 4

510g of concentrated sulfuric acid and 7.65g of isobutyl acetate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 2°C by a refrigerator. Then 123g of isobutane and 6g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 20.5) and cooled to 2°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 2°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Example 5

510g of concentrated sulfuric acid and 7.65g of tert-butyl acetate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Example 6

510g of concentrated sulfuric acid and 7.65g of tert-butyl acetate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 123g of isobutane and 6g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 20.5) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Example 7

510g of concentrated sulfuric acid and 2.55g of di-n-butyl carbonate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Example 8

510g of concentrated sulfuric acid and 2.55g of diisobutyl carbonate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Example 9

510g of concentrated sulfuric acid and 5.10g of diisobutyl carbonate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 2°C by a refrigerator. Then 123g of isobutane and 6g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 20.5) and cooled to 2°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 2°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Example 10

510g of concentrated sulfuric acid and 2.55g of di-tert-butyl dicarbonate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Embodiment 11

510g of concentrated sulfuric acid and 5.10g of di-tert-butyl dicarbonate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 2°C by a refrigerator. Then 123g of isobutane and 6g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 20.5) and cooled to 2°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 2°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Example 12

510g of concentrated sulfuric acid was injected into the reactor. After nitrogen was used to remove the air in the reactor, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and a refrigerator was used to ensure that the reaction temperature was 5°C. Then 120g of isobutane and 9g of n-butene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction. The reaction temperature was 5°C, the reaction pressure was 0.5MPa, the speed was 3000r/min, and the reaction time was 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Example 13

510g of concentrated sulfuric acid and 7.65g of tert-butyl acetate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of n-butene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Embodiment 14

510g of concentrated sulfuric acid and 2.55g of di-tert-butyl dicarbonate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of n-butene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Embodiment 15

510g of concentrated sulfuric acid was injected into the reactor, and after the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of pre-ether _C4 were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the mixture was allowed to stand for stratification, and the alkylated gasoline was taken for analysis and calculation.

Example 16

510g of concentrated sulfuric acid and 7.65g of tert-butyl acetate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of pre-ether _C4 were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Embodiment 17

510g of concentrated sulfuric acid and 2.55g of di-tert-butyl dicarbonate auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of pre-ether C ₄ were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Comparative Example 1

510g of concentrated sulfuric acid and 5.10g of methanesulfonic acid auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the alkylation gasoline was analyzed and calculated after standing for stratification.

Comparative Example 2

510g of concentrated sulfuric acid and 2.55g of 1-butyl-3-methylimidazole hydrogen sulfate ([BMIm][HSO ₄ ]) were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction. The reaction temperature was 5°C, the reaction pressure was 0.5MPa, the speed was 3000r/min, and the reaction time was 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Comparative Example 3

510g of concentrated sulfuric acid and 2.55g of sodium fluoride auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the stratification was allowed to stand, and the alkylated gasoline was taken for analysis and calculation.

Comparative Example 4

510g of concentrated sulfuric acid and 2.55g of cycloheptatriene auxiliary agent were injected into the reactor. After the air in the reactor was removed by nitrogen, the ultra-high-speed magnetic stirrer in the reactor was stirred at a speed of 3000r/min, and the reaction temperature was ensured to be 5°C by a refrigerator. Then 120g of isobutane and 9g of isobutylene were introduced into the mixing tank for mixing (the mass ratio of alkane to olefin was 13.3) and cooled to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reactor through a metering pump for alkylation reaction, with a reaction temperature of 5°C, a reaction pressure of 0.5MPa, a rotation speed of 3000r/min, and a reaction time of 5min. After the alkylation reaction was completed, the alkylation gasoline was analyzed and calculated after standing for stratification.

Table 1 Quality of alkylated gasoline obtained in Examples and Comparative Examples

As shown in Table 1, n-butyl acetate, isobutyl acetate, tert-butyl acetate, di-n-butyl carbonate, diisobutyl carbonate, and di-tert-butyl dicarbonate as co-catalysts can significantly affect the effect of concentrated sulfuric acid C ₄ alkylation reaction, increase the C ₈ component content of the alkylation product, reduce the C ₉ + heavy component content, and improve the RON value of the alkylation gasoline. By comparing Example 5 with Example 1, it can be seen that compared with the technical solution without co-catalyst in Example 1, the content of C ₈ component of the alkylation gasoline obtained in Example 5 increased from 68.25% to 73.88%, the content of C ₉ + heavy components decreased from 16.48% to 11.29%, and the RON value of the alkylation reaction product increased from 92.67 to 94.39, an increase of 1.72 units. By comparing Example 5, Example 13, Example 16 with Example 1, Example 12, and Example 15, it can be seen that the quality of the alkylation gasoline obtained after adding acid ester co-catalysts to different reaction raw materials is improved.

Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims (6)

1. A process for preparing an alkylated gasoline, comprising: carrying out alkylation reaction on isoparaffin and olefin under the action of a strong acid catalyst and a cocatalyst to obtain alkylated gasoline;

wherein the cocatalyst is at least one of n-butyl acetate, isobutyl acetate and tert-butyl acetate; the temperature of the alkylation reaction is-10-25 ℃, and the pressure is 0.1-3.0 MPa;

The mass ratio of the isoparaffin to the olefin is 1-100: 1, a step of; the mass ratio of the cocatalyst to the strong acid catalyst is 0.0005-0.1: 1, a step of; the mass ratio of the strong acid catalyst to the total amount of isoparaffin and olefin is 1:10-10:1.

2. The method for producing an alkylated gasoline according to claim 1, wherein the isoparaffin has 4 to 8 carbon atoms and the olefin has 2 to 8 carbon atoms.

3. The process for the preparation of alkylated gasoline according to claim 2, wherein the isoparaffins comprise isobutane and/or isopentane; the olefin includes at least one of propylene, isobutylene, n-butene, cis-2-butene, trans-2-butene and pentene.

4. The method for preparing alkylated gasoline of claim 1, wherein the strong acid catalyst comprises at least one of concentrated sulfuric acid, HF acid, trifluoromethanesulfonic acid, salicylic acid, solid molecular sieve, and chloroaluminate ionic liquid.

5. The method for producing an alkylated gasoline according to claim 1, comprising: the strong acid catalyst and the cocatalyst are mixed and then contacted with the isoparaffin and the olefin to carry out alkylation reaction.

6. The method for preparing alkylated gasoline of claim 1, further comprising, after the alkylation reaction, standing the reaction product for delamination, wherein the upper layer is the alkylated gasoline and the lower layer is a strong acid catalyst and a cocatalyst.