CN115247078A - Alkylated gasoline and preparation method thereof - Google Patents

Abstract

The invention provides an alkylated gasoline and a preparation method thereof. The preparation method comprises: performing an alkylation reaction on isoparaffins and olefins under the action of a strong acid catalyst and a co-catalyst to obtain alkylated gasoline; wherein, the The cocatalyst is an acid ester compound. In the present invention, adding an ester compound as a cocatalyst can significantly improve the reaction microenvironment of the acid-hydrocarbon two-phase interface in the alkylation reaction, and improve the selectivity and alkylation of isooctane (especially trimethylpentane). The yield of gasoline increases significantly the RON value of alkylated gasoline.

Description

A kind of alkylated gasoline and preparation method thereof

technical field

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

Background technique

Alkylated clean gasoline uses isoparaffins (mostly isobutane) and one or more olefins (C3-C5 olefins) as the raw materials for the alkylation reaction. Clean gasoline production technology for isoparaffinic mixtures. The alkylated gasoline is mainly composed of 2,2,4-trimethylpentane (TMP) and its isomers (such as 2,3,4-trimethylpentane), with high octane number, high sensitivity Low, good anti-knock and almost free of olefin, sulfur and aromatic content and other advantages, it is an ideal blending component for motor gasoline.

At present, the alkylation technologies used in the world 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 has a mature process. It will be the mainstream of my country's alkylation process in the next ten years. At the same time, since there are many low-end gasoline products and few high-end gasoline products in my country, the activity of the concentrated sulfuric acid catalyst is improved, the solubility and mass transfer of the acid-hydrocarbon interface are improved, and the quality of alkylated gasoline is greatly improved, especially the octane number of the product is improved. The first choice for alkylated gasoline development.

Solid acid alkylation and ionic liquid alkylation belong to new process technologies actively developed at home and abroad in recent years. The safety and environmental protection of solid acid catalysts is far better than that of hydrofluoric acid alkylation and concentrated sulfuric acid alkylation, but the raw material adaptability is poor, the process operation is complicated, the equipment investment and operating costs are high, and the catalyst is easy to deactivate; ionic liquid catalysts are more efficient than sulfuric acid and Hydrofluoric acid has higher catalytic activity, but the cost of ionic liquid catalysts is high, and catalyst stability and raw material adaptability require time and more industrial application device testing. Solid acid alkylation and ionic liquid alkylation still have a long way to go to completely replace the traditional liquid acid alkylation technology.

Since the industrialization of sulfuric acid C ₄ alkylation, research on auxiliary agents for sulfuric acid C ₄ alkylation has been carried out. ALKAT-X sulfuric acid additives developed by BetzDearborn Hydrocarbon Process Chemicals can increase octane number and reduce acid consumption; XL-2100 sulfuric acid additives developed by Davis Applied Technologies can reduce acid consumption and improve liquid yield; CMFrederic et al. Trialkyl phosphoramines or sulfonamides with branched chains with 10 to 20 carbon atoms are sulfuric acid alkylation additives, which can effectively improve the C8 selectivity, thereby improving the octane number of alkylated gasoline; _G.Holzman et al. Trifluoroacetic acid is used as a sulfuric acid alkylation assistant, 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; VIZakoshanskij uses sulfolane As a sulfuric acid adjuvant, it can greatly improve the selectivity of the alkylation reaction and reduce the acid consumption; however, the above adjuvant or its type and structure information have been kept confidential, or the improvement effect on alkylated gasoline products is weak.

CN102134507A discloses a method for preparing alkylated gasoline by using trifluoroethanol or ionic liquid as auxiliary modified concentrated sulfuric acid, the trifluoroethanol used in the method forms hydrofluoric acid in the reaction environment, corrodes equipment and pipelines; The 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 help of adamantyl ionic liquid. The method improves the selectivity of alkylation products and has a low RON value; meanwhile, the acid consumption in the alkylation reaction is large, and the waste acid treatment high cost.

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

SUMMARY OF THE INVENTION

The main purpose of the present invention is to provide an alkylated gasoline and a preparation method thereof. _The alkylated gasoline prepared by the method of the present invention has higher C8 component selectivity and higher octane number.

In order to achieve the above object, the present invention provides a method for preparing alkylated gasoline, the preparation method comprising: performing an alkylation reaction on isoparaffins and olefins under the action of a strong acid catalyst and a cocatalyst to obtain alkylated gasoline; Wherein, the cocatalyst is an acid ester compound.

The preparation method of alkylated gasoline according to the present invention, wherein, the cocatalyst is n-butyl acetate, isobutyl acetate, tert-butyl acetate, di-n-butyl carbonate, diisobutyl carbonate, dicarbonate dicarbonate At least one of tert-butyl esters.

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

In the method for preparing alkylated gasoline according to the present invention, the isoparaffins include isobutane and/or isopentane; the olefins include propylene, isobutene, n-butene, cis-2-butene, At least one of trans-2-butene and pentene.

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

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

The preparation method of alkylated gasoline according to the present invention, wherein, the preparation method comprises: mixing the strong acid catalyst and the cocatalyst, and then contacting with the isoparaffin and the olefin to carry out an alkylation reaction .

The method for preparing alkylated gasoline of the present invention further comprises, after the alkylation reaction, the reaction product is allowed to stand for stratification, the upper layer is alkylated gasoline, and the lower layer is strong acid catalyst and 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 ester compounds as cocatalysts 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, and significantly improve the stability of the strong acid catalyst and the quality of the alkylated gasoline (three). selectivity to methylpentane). In addition, the acid ester compounds only contain C, H, O elements, without S, N, and do not pollute the environment; and the acid ester compounds are stable in a strong acid environment; at the same time, the acid ester compounds are in the oil phase and the acid phase. There is a huge difference in the distribution coefficients of the catalysts. After the alkylation reaction, the ester compounds do not exist in the oil phase, which reduces the separation cost of the cocatalyst and has a broad industrial application prospect.

Detailed ways

The embodiments of the present invention are described in detail below. This embodiment is implemented on the premise of the technical solution of the present invention, and provides detailed implementation methods and processes. However, the protection scope of the present invention is not limited to the following embodiments. The following The experimental methods that do not specify specific conditions in the examples are usually in accordance with conventional conditions.

The present invention provides a method for preparing alkylated gasoline, which comprises the following steps: performing an alkylation reaction on isoparaffins and olefins under the action of a strong acid catalyst and a co-catalyst to obtain alkylated gasoline; The catalyst is an acid ester compound.

During the reaction of isoparaffins and olefins, adding an ester cocatalyst to the strong acid catalyst can improve the interface properties of the reaction system and maintain the acidity of the system, and significantly improve the stability of the strong acid catalyst and the quality of alkylated gasoline (trimethyl selectivity to pentane). In detail, the role of ester co-catalysts is to improve the quality of alkylated gasoline produced by the alkylation of isoparaffins and olefins, that is, to increase the C ₈ content in the alkylated gasoline, inhibit the superposition of olefins, and reduce C ₉ + Content of by-products. At the same time, the reduction of C ₉ + by-products effectively delays the deactivation rate of acid catalysts, reduces catalyst consumption, reduces enterprise costs, and improves economic benefits; and ester co-catalysts are only composed of C, H, and O elements, which do not produce any environmental impact. In addition, the acid ester cocatalyst is stable in a strong acid environment, easy to separate from the product (alkylated gasoline) after the reaction, and has a broad industrial application prospect.

In one embodiment, the isoparaffins of the present invention have 3 to 8 carbon atoms; in another embodiment, the isoparaffins have 4 to 6 carbon atoms; in yet another embodiment, the isoparaffins include isobutyl alkane and/or isopentane.

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

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 sieve and chloroaluminate ionic liquid, 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 may be an organic acid or an inorganic acid, or a monobasic acid, a dibasic acid Acid or tribasic acid, alcohol can be monohydric alcohol, dihydric alcohol or 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, for example, has 1 to 10 carbon atoms. In another embodiment, the acid ester compound includes one of n-butyl acetate, isobutyl acetate, tert-butyl acetate, di-n-butyl carbonate, diisobutyl carbonate, and di-tert-butyl dicarbonate or various combinations.

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

The present invention adds 0.05% to 5% of the strong acid catalyst by weight of the ester co-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, and reduce the reaction by-products It can improve the catalytic activity of the strong acid catalyst, promote the reaction to move to the forward reaction direction, and play a significant role in improving the selectivity of the alkylation reaction, the yield of alkylated gasoline and the RON value.

In one embodiment, the method for preparing the alkylated gasoline of the present invention comprises: mixing a strong acid catalyst and a cocatalyst, mixing isoparaffins and olefins, and then contacting the strong acid catalyst and the cocatalysts with isoparaffins and olefins to conduct alkanes. base reaction. After the alkylation reaction is completed, the reacted materials enter the alkylated gasoline separation tank to stand for stratification, and the unreacted alkanes enter the tail gas condensation tank for recovery; 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 3.0 Mpa.

The present invention does not specifically limit the device for the above-mentioned alkylation reaction, and it can be a continuous production device used in industrial alkylation of sulfuric acid or hydrofluoric acid, or an alkylation reaction device (such as a fixed bed reactor, a slurry bed reactor, etc.) It can also be a reactor with a stirring device. The alkylation reaction can be carried out either batchwise or continuously in the above-mentioned apparatus. The isoparaffins, olefins, and acid ester cocatalysts in the present invention all exist in a high-pressure liquid state in the reaction device.

The technical solution of the present invention can be applied to the carbon tetraalkylation technology. The carbon tetraalkylation technology uses carbon tetraalkane such as isobutane as the alkylation raw material, and carries out the alkylation reaction with _C4 olefin to generate high octane number The technology of gasoline blending component 2,2,4-trimethylpentane (TMP), but the present invention is not limited thereto. The technical solutions of the present invention will be further described in detail below through specific embodiments.

Example 1

510g of concentrated sulfuric acid was injected into the low-temperature, corrosion-resistant batch reaction kettle. After removing the air in the reaction kettle with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at a speed of 3000r/min, and passed through a refrigerator to ensure the reaction. The temperature is 5°C. Immediately afterwards, 120 g of isobutane and 9 g of isobutene were mixed in a mixing tank (the mass ratio of alkenes was 13.3), and the temperature was lowered to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reaction kettle through a metering pump to carry out the alkylation reaction. The reaction temperature was 5°C, the reaction pressure was 0.5MPa, the rotation speed was 3000r/min, and the reaction time was 5min. After the alkylation reaction is completed, the reacted material enters the alkylated gasoline separation tank to stand for stratification, and the unreacted alkane enters the tail gas condensation tank for recovery; in the alkylated gasoline separation tank, the lower layer is concentrated sulfuric acid catalyst, and the upper layer is alkane. base gasoline. Take the upper layer of alkylated gasoline for quantitative analysis by gas chromatography, determine the type of substances by mass spectrometry, and use the normalization method for quantitative calculation.

Example 2

510g of concentrated sulfuric acid and 7.65g of n-butyl acetate auxiliary were injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at a rotating speed of 3000 r/min, and passed through a refrigerator. To ensure that the reaction temperature is 5 °C. Immediately afterwards, 120 g of isobutane and 9 g of isobutene were mixed in a mixing tank (the mass ratio of alkenes was 13.3), and the temperature was lowered to 5°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 5°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 3

510g of concentrated sulfuric acid and 7.65g of isobutyl acetate were injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at a rotating speed of 3000 r/min, and passed through a refrigerator. To ensure that the reaction temperature is 5 °C. Then, 120 g of isobutane and 9 g of isobutene were mixed in a mixing tank (the mass ratio of alkenes was 13.3) and the temperature was lowered to 5°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 5°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 4

510g of concentrated sulfuric acid and 7.65g of isobutyl acetate were injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at a rotating speed of 3000 r/min, and passed through a refrigerator. To ensure that the reaction temperature is 2 °C. Then, 123 g of isobutane and 6 g of isobutene were introduced into the mixing tank to be mixed (the mass ratio of alkenes was 20.5) and the temperature was lowered to 2°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 2°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 5

510g of concentrated sulfuric acid and 7.65g of tert-butyl acetate auxiliary were injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at the rotating speed of 3000r/min, and passed the refrigerator. To ensure that the reaction temperature is 5 °C. Immediately afterwards, 120 g of isobutane and 9 g of isobutene were mixed in a mixing tank (the mass ratio of alkenes was 13.3), and the temperature was lowered to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reaction kettle through a metering pump to carry out the alkylation reaction. The reaction temperature was 5°C, the reaction pressure was 0.5MPa, the rotation speed was 3000r/min, and the reaction time was 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 6

510g of concentrated sulfuric acid and 7.65g of tert-butyl acetate auxiliary were injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at the rotating speed of 3000r/min, and passed the refrigerator. To ensure that the reaction temperature is 5 °C. Then, 123 g of isobutane and 6 g of isobutene were mixed in a mixing tank (the mass ratio of alkenes was 20.5) and the temperature was lowered to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reaction kettle through a metering pump to carry out the alkylation reaction. The reaction temperature was 5°C, the reaction pressure was 0.5MPa, the rotation speed was 3000r/min, and the reaction time was 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 7

510g of concentrated sulfuric acid and 2.55g of di-n-butyl carbonate auxiliary were injected into the reactor, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the reactor stirred at a rotating speed of 3000 r/min, and refrigerated machine to keep the reaction temperature at 5 °C. Immediately afterwards, 120 g of isobutane and 9 g of isobutene were mixed in a mixing tank (the mass ratio of alkenes was 13.3), and the temperature was lowered to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reaction kettle through a metering pump to carry out the alkylation reaction. The reaction temperature was 5°C, the reaction pressure was 0.5MPa, the rotation speed was 3000r/min, and the reaction time was 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 8

510g of concentrated sulfuric acid and 2.55g of diisobutyl carbonate auxiliary were injected into the reactor, and after the air in the reactor was removed with nitrogen, the ultra-high-speed magnetic stirrer in the reactor stirred at a rotating speed of 3000r/min, and refrigerated machine to keep the reaction temperature at 5 °C. Then, 120 g of isobutane and 9 g of isobutene were mixed in a mixing tank (the mass ratio of alkenes was 13.3) and the temperature was lowered to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reaction kettle through a metering pump to carry out the alkylation reaction. The reaction temperature was 5°C, the reaction pressure was 0.5MPa, the rotation speed was 3000r/min, and the reaction time was 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 9

510g of concentrated sulfuric acid and 5.10g of diisobutyl carbonate auxiliary were injected into the reactor, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the reactor stirred at a rotating speed of 3000r/min, and refrigerated machine to keep the reaction temperature at 2 °C. Then, 123 g of isobutane and 6 g of isobutene were introduced into the mixing tank to be mixed (the mass ratio of alkenes was 20.5) and the temperature was lowered to 2°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump to carry out the alkylation reaction. The reaction temperature is 2°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 10

510g of concentrated sulfuric acid and 2.55g of di-tert-butyl dicarbonate auxiliary were injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at a rotating speed of 3000 r/min, and passed Refrigerator to keep the reaction temperature at 5°C. Immediately afterwards, 120 g of isobutane and 9 g of isobutene were mixed in a mixing tank (the mass ratio of alkenes was 13.3), and the temperature was lowered to 5°C. After the hydrocarbon mixture was premixed and cooled, it was injected into the reaction kettle through a metering pump to carry out the alkylation reaction. The reaction temperature was 5°C, the reaction pressure was 0.5MPa, the rotation speed was 3000r/min, and the reaction time was 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 11

510g of concentrated sulfuric acid and 5.10g of di-tert-butyl dicarbonate auxiliary were injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at a rotating speed of 3000 r/min, and passed Refrigerator to keep the reaction temperature at 2°C. Then, 123 g of isobutane and 6 g of isobutene were introduced into the mixing tank to be mixed (the mass ratio of alkenes was 20.5) and the temperature was lowered to 2°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump to carry out the alkylation reaction. The reaction temperature is 2°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 12

510g of concentrated sulfuric acid was injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at a rotating speed of 3000 r/min, and passed through a refrigerator to ensure that the reaction temperature was 5 °C. Immediately afterwards, 120 g of isobutane and 9 g of n-butene were mixed in a mixing tank (the mass ratio of alkenes was 13.3), and the temperature was lowered to 5°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 5°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 13

510g of concentrated sulfuric acid and 7.65g of tert-butyl acetate auxiliary were injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at the rotating speed of 3000r/min, and passed the refrigerator. To ensure that the reaction temperature is 5 °C. Immediately afterwards, 120 g of isobutane and 9 g of n-butene were mixed in a mixing tank (the mass ratio of alkenes was 13.3), and the temperature was lowered to 5°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 5°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 14

510g of concentrated sulfuric acid and 2.55g of di-tert-butyl dicarbonate auxiliary were injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at a rotating speed of 3000 r/min, and passed Refrigerator to keep the reaction temperature at 5°C. Immediately afterwards, 120 g of isobutane and 9 g of n-butene were mixed in a mixing tank (the mass ratio of alkenes was 13.3), and the temperature was lowered to 5°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 5°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 15

510g of concentrated sulfuric acid was injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at a rotating speed of 3000 r/min, and passed through a refrigerator to ensure that the reaction temperature was 5 °C. Immediately afterwards, 120 g of isobutane and 9 g of C ₄ before ether were passed into the mixing tank to be mixed (the mass ratio of alkenes was 13.3) and the temperature was lowered to 5°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 5°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 16

510g of concentrated sulfuric acid and 7.65g of tert-butyl acetate auxiliary were injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at the rotating speed of 3000r/min, and passed the refrigerator. To ensure that the reaction temperature is 5 °C. Immediately afterwards, 120 g of isobutane and 9 g of C ₄ before ether were passed into the mixing tank to be mixed (the mass ratio of alkenes was 13.3) and the temperature was lowered to 5°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 5°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Example 17

510g of concentrated sulfuric acid and 2.55g of di-tert-butyl dicarbonate auxiliary were injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at a rotating speed of 3000 r/min, and passed Refrigerator to keep the reaction temperature at 5°C. Immediately afterwards, 120 g of isobutane and 9 g of C ₄ before ether were passed into the mixing tank to be mixed (the mass ratio of alkenes was 13.3) and the temperature was lowered to 5°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 5°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Comparative Example 1

510g of concentrated sulfuric acid and 5.10g of methanesulfonic acid auxiliary were injected into the reaction kettle, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the kettle stirred at a rotating speed of 3000 r/min, and passed through a refrigerator. To ensure that the reaction temperature is 5 °C. Immediately afterwards, 120 g of isobutane and 9 g of isobutene were mixed in a mixing tank (the mass ratio of alkenes was 13.3), and the temperature was lowered to 5°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 5°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Comparative Example 2

510g of concentrated sulfuric acid and 2.55g of 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIm][HSO ₄ ]) auxiliary were injected into the reactor, and after the air in the reactor was removed with nitrogen, the ultra A high-speed magnetic stirrer was used for stirring at a rotational speed of 3000 r/min, and the reaction temperature was guaranteed to be 5 °C through a refrigerator. Immediately afterwards, 120 g of isobutane and 9 g of isobutene were mixed in a mixing tank (the mass ratio of alkenes was 13.3), and the temperature was lowered to 5°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 5°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Comparative Example 3

510g of concentrated sulfuric acid and 2.55g of sodium fluoride auxiliary were injected into the reaction kettle, and after the air in the reactor was removed with nitrogen, the ultra-high-speed magnetic stirrer in the kettle was stirred at a rotating speed of 3000 r/min, and the refrigerating machine was used for stirring. The reaction temperature was guaranteed to be 5°C. Immediately afterwards, 120 g of isobutane and 9 g of isobutene were mixed in a mixing tank (the mass ratio of alkenes was 13.3), and the temperature was lowered to 5°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 5°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

Comparative Example 4

510g of concentrated sulfuric acid and 2.55g of cycloheptatriene auxiliary were injected into the reactor, and after removing the air in the reactor with nitrogen, the ultra-high-speed magnetic stirrer in the reactor stirred at a rotating speed of 3000r/min, and passed the refrigerator. To ensure that the reaction temperature is 5 °C. Immediately afterwards, 120 g of isobutane and 9 g of isobutene were mixed in a mixing tank (the mass ratio of alkenes was 13.3), and the temperature was lowered to 5°C. After the hydrocarbon mixture is premixed and cooled, it is injected into the reaction kettle through a metering pump for alkylation reaction, the reaction temperature is 5°C, the reaction pressure is 0.5MPa, the rotation speed is 3000r/min, and the reaction time is 5min. After the alkylation reaction is completed, the layers are left to stand, and the alkylated gasoline is taken for analysis and calculation.

The alkylate gasoline quality obtained by the embodiment and comparative example of table 1

As can be seen from Table 1, n-butyl acetate, isobutyl acetate, tert-butyl acetate, di-n-butyl carbonate, diisobutyl carbonate, and di-tert-butyl dicarbonate can all significantly affect the concentrated sulfuric acid C alkane as cocatalysts _. The effect of the alkylation reaction increases the content of C ₈ components in the alkylation product, reduces the content of C ₉ + heavy components, and increases the RON value of the alkylated gasoline. 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 components in the alkylated gasoline obtained in Example 5 increased from 68.25% to 73.88%, C ₉ + The content of 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, and Example 16 with Example 1, Example 12, and Example 15, it can be seen that the quality of the alkylated gasoline obtained from different reaction raw materials after adding the ester co-catalyst was all improve.

Of course, the present invention can also have other various embodiments, without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the present invention, but these corresponding changes and deformation should belong to the protection scope of the claims of the present invention.

Claims (10)

1. a preparation method of alkylated gasoline, it is characterized in that, this preparation method comprises: carry out alkylation reaction with isoparaffin and olefin under the effect of strong acid catalyst and cocatalyst, obtain alkylated gasoline; The cocatalyst is an acid ester compound. 2. the preparation method of alkylated gasoline according to claim 1, is characterized in that, described cocatalyst is n-butyl acetate, isobutyl acetate, tert-butyl acetate, di-n-butyl carbonate, diisobutyl carbonate At least one of butyl ester and di-tert-butyl dicarbonate. 3 . The method for preparing alkylated gasoline according to claim 1 , wherein the isoparaffin has 4-8 carbon atoms, and the olefin has 2-8 carbon atoms. 4 . 4. The method for preparing alkylated gasoline according to claim 3, wherein the isoparaffins include isobutane and/or isopentane; the olefins include propylene, isobutene, n-butene, cis At least one of -2-butene, trans-2-butene, and pentene. 5. The preparation method of alkylated gasoline according to claim 1, wherein the strong acid catalyst comprises in sulfuric acid, HF acid, trifluoromethanesulfonic acid, salicylic acid, solid molecular sieve and chloroaluminate ionic liquid at least one of. 6 . The method for preparing alkylated gasoline according to claim 1 , wherein the mass ratio of the isoparaffin to the olefin is 1-100:1; the ratio of the cocatalyst to the strong acid catalyst The mass ratio is 0.0005-0.1:1; the mass ratio of the strong acid catalyst to the total amount of the isoparaffin and the olefin is 1:10-10:1. 7 . The method for preparing alkylated gasoline according to claim 1 , wherein the temperature of the alkylation reaction is -10-25° C. and the pressure is 0.1-3.0 MPa. 8 . 8 . The method for preparing alkylated gasoline according to claim 1 , wherein the preparation method comprises: mixing the strong acid catalyst and the cocatalyst, and then contacting with the isoparaffin and the olefin. 9 . , for the alkylation reaction. 9 . The method for preparing alkylated gasoline according to claim 1 , further comprising, after the alkylation reaction, the reaction product is allowed to stand for stratification, the upper layer is alkylated gasoline, and the lower layer is 9 . Strong acid catalysts and cocatalysts. 10. The preparation method according to any one of claims 1 to 9 obtains alkylated gasoline.