CN114479917B

CN114479917B - Method for producing alkylate

Info

Publication number: CN114479917B
Application number: CN202011148794.8A
Authority: CN
Inventors: 喻惠利; 俞芳; 温朗友; 董明会; 夏玥穜; 郜亮
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-10-23
Filing date: 2020-10-23
Publication date: 2023-06-09
Anticipated expiration: 2040-10-23
Also published as: CN114479917A

Abstract

The present disclosure relates to a method of producing an alkylate, the method comprising:under alkylation reaction conditions, isobutane and C ₄ The olefin is contacted and reacted in the presence of sulfuric acid solution and a co-catalyst; wherein the co-catalyst comprises a phosphate ester and an acid-soluble oil. The alkylation reaction method adds the co-catalyst containing the phosphate and the acid-soluble oil into the sulfuric acid catalytic alkylation reaction, so that the catalytic activity of a sulfuric acid catalytic system is improved, and the C in the product alkylate is improved ₈ Selectivity of components and C ₈ Selectivity of high octane component of the components, C _5‑7 Component and C ₉ The content of the heavy components is greatly reduced, and the octane number of the product is obviously improved.

Description

Method for producing alkylate

Technical Field

The present disclosure relates to the field of alkylate production, and in particular, to a method for producing alkylate.

Background

With the rapid development of the automobile industry and the increasing strictness of automobile exhaust emission standards, the demand for clean gasoline production is increasing in all countries around the world. From isobutane and C ₄ Alkylation of olefins to form C ₈ Isooctane products, i.e. alkylates, which have the advantages of no olefins, no aromatics, low sulfur content, low vapor pressure, high octane number, and good antiknock properties, are the most desirable blending components for clean gasoline.

The current industrial methods for producing alkylate mainly include sulfuric acid method and hydrofluoric acid method. However, the waste acid emission of the sulfuric acid process is large, so that the environmental pollution is serious; hydrofluoric acid is a volatile highly toxic chemical, and has the problems of personal safety, environmental pollution and the like in the operation process. Therefore, developing an alkylation catalyst with low toxicity, low acid consumption, low production cost and high catalytic activity is an important research topic in the field of petrochemical catalytic reactions.

For many years, a great deal of manpower and material resources are invested at home and abroad to research and development of solid acid alkylation catalysts and processes, and the method is hoped to replace the current liquid acid alkylation technology and solve the problems of environmental pollution and equipment corrosion of liquid acid. The solid acid catalyst developed by research mainly comprises metal halides, molecular sieves, solid superacids, supported heteropolyacids and the like. Although the solid acid alkylation process has the advantages of low corrosiveness, safety, environmental protection and the like, the road for realizing industrialization by the solid acid alkylation process is still difficult and heavy. The solid acid catalyst has a common disadvantage that the initial activity of the solid acid catalyst is very good, but the deactivation is very fast, after a few hours or even tens of minutes, the active site is covered by macromolecular unsaturated hydrocarbon compounds generated by side reactions such as olefin self polymerization and the like in the reaction process, the catalyst regeneration cost is high, and the economy of the catalyst cannot compete with the sulfuric acid and hydrofluoric acid alkylation process.

Because ionic liquids are salts which exist in liquid form at room temperature and have many special properties, such as strong dissolution capacity, high thermal stability, very low vapor pressure, no corrosiveness, reusability, adjustable acid strength and the like, the research of using ionic liquids as catalysts for alkylation reactions has attracted great attention from scientific researchers. The alkylation reaction of isobutane and butene is catalyzed by modified chloroaluminate ionic liquid adopted by China university of Petroleum (Beijing), the alkylation level approaching or reaching the industrial sulfuric acid method can be obtained, but due to the adopted AlCl ₃ The ionic liquid is easy to hydrolyze when meeting water to release hydrogen chloride to cause the deactivation of the catalyst, and has the defects of severe requirement on water content, poor self stability and the like, so that the industrialization process is difficult and heavy.

RU2114808C1 proposes that sulfolane is used as an additive of sulfuric acid, when the addition amount of sulfolane is 5-10wt%, trimethylpentane in the product is increased by 1.2-1.3 times, the octane number of the product is increased by 4-5 units, and the acid consumption is reduced by 30-40%. However, C in the reaction product of this technique ₈ The content is low, the octane number of the product is low, and the quality and yield requirements of the alkylated oil product in the market are difficult to meet.

CN201110038062.8 is carriedThe method for preparing the alkylate by modifying the concentrated sulfuric acid by taking the trifluoroethanol or the ionic liquid as the auxiliary agent can improve the catalytic activity and the stability of the catalyst and improve C when the content of the trifluoroethanol and the ionic liquid is 1.0-10.0 wt% ₈ Selectivity and trimethylpentane mass. But there is a large gap with respect to the market demand for the quality and yield of alkylate product.

Disclosure of Invention

The present disclosure provides a method for producing an alkylate in order to increase the catalytic activity of a sulfuric acid catalyst system in an alkylation reaction and to increase product selectivity.

To achieve the above object, the present disclosure provides a method of producing an alkylate, the method comprising: under alkylation reaction conditions, isobutane and C ₄ The olefin is contacted and reacted in the presence of sulfuric acid solution and a co-catalyst; wherein the co-catalyst comprises a phosphate ester and an acid-soluble oil.

Alternatively, the phosphoric acid ester is used in an amount of 0.05 to 18 parts by weight, preferably 0.1 to 8 parts by weight, relative to 100 parts by weight of the sulfuric acid solution.

Alternatively, the acid-soluble oil is used in an amount of 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, relative to 100 parts by weight of the sulfuric acid solution.

Optionally, the weight ratio of the phosphate to the acid-soluble oil is 1: (1-20).

Optionally, the phosphate is one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, trioctyl phosphate and tricresyl phosphate.

Optionally, the mass concentration of sulfuric acid in the sulfuric acid solution is above 70%;

the sulfuric acid solution and the C ₄ The volume ratio of the olefin is (0.5-50): 1, a step of;

the isobutane and the C ₄ The volume ratio of the olefin is (1-160): 1, a step of;

the C is ₄ The olefin is one or more of 1-butene, n-2-butene, trans-2-butene and isobutene.

Optionally, the alkylation reaction conditions include: the reaction temperature is between-15 ℃ and 40 ℃ and the reaction pressure is between 0.1 and 1.5MPa.

Optionally, the alkylation reaction conditions include: the reaction time is 0.1-60 min; alternatively, the volume airspeed is 0.5 to 30 hours ^-1 。

Optionally, the method further comprises: carrying out alkylation reaction on the mixed carbon four raw materials in concentrated sulfuric acid, taking out a lower layer product after carrying out first phase separation on the obtained first mixture, mixing the lower layer product with water to obtain a second mixture, and taking out an upper layer product after carrying out second phase separation on the second mixture to obtain the acid-soluble oil;

the mixed carbon four raw materials comprise one or more of isobutane, n-butane, 1-butene, trans-2-butene, n-2-butene and isobutene, and the volume ratio of the alkane to the alkene of the mixed carbon four raw materials is 1: (0.5-2); the alkylation reaction conditions include: the reaction temperature is between-10 and 20 ℃, the reaction pressure is between 0.3 and 1.0MPa, and the reaction time is between 1 and 40 minutes.

Optionally, the co-catalyst further comprises a sulfonate.

Optionally, the weight ratio of the phosphate to the sulfonate is (0.02-1.0): 1, preferably (0.1 to 0.8): 1, a step of;

the sulfonate is one or more of 1, 3-propane sultone, 1, 4-butane sultone, ethyl methane sulfonate, 4-toluene sulfonate and 4-toluene sulfonate.

Optionally, the co-catalyst is a mixture of phosphate, sulfonate and the acid-soluble oil, wherein the weight ratio of the phosphate to the sulfonate to the acid-soluble oil is (0.06-0.4): (0.3-2): 1.

optionally, the sulfonate comprises 4-ethyl toluene sulfonate and 1, 4-butyl sultone, wherein the weight ratio of the 4-ethyl toluene sulfonate to the 1, 4-butyl sultone is 1: (0.9-1.1).

Optionally, the phosphoric acid ester comprises tributyl phosphate and triisobutyl phosphate, and the weight ratio of the tributyl phosphate to the triisobutyl phosphate is 1: (0.9-1.1).

Alternatively, the alkylation reaction is carried out in a batch reactor or a continuous reactor; the batch reactor comprises a kettle reactor; the continuous reactor is one or more of a horizontal reactor, a stepped reactor, a mixed packing tower reactor and a static mixing reactor.

The alkylation reaction method adds the co-catalyst containing the phosphate and the acid-soluble oil into the sulfuric acid catalytic alkylation reaction, so that the catalytic activity of a sulfuric acid catalytic system is improved, and the C in the product alkylate is improved ₈ Selectivity of components and C ₈ Selectivity of high octane component of the components, C _5-7 Component and C ₉ The content of the heavy components is greatly reduced, and the octane number of the product is obviously improved.

Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.

Detailed Description

The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.

The present disclosure provides a process for producing an alkylate comprising: under alkylation reaction conditions, isobutane and C ₄ The olefin is contacted and reacted in the presence of sulfuric acid solution and a co-catalyst; wherein the co-catalyst comprises a phosphate ester and an acid-soluble oil.

The disclosed process for producing an alkylate comprises reacting isobutane and C under alkylation reaction conditions ₄ The olefin is subjected to contact reaction in a sulfuric acid catalyst system and the obtained alkylated gasoline is recovered. The method for producing the alkylate adopts a sulfuric acid catalyst system containing phosphate and acid-soluble oil co-catalyst, has good catalytic activity and contains C in the alkylate ₈ High selectivity of component C ₈ The target product of the components has high selectivity of high-octane component Trimethylpentane (TMP), C _5-7 Component and C ₉ The content of the heavy components is greatly reduced, and the octane number of the product is obviously improved.

In order to make a sulfuric acid catalyst system containing a co-catalystHas higher catalytic activity and improves C in the final product of the alkylated gasoline ₈ Product selectivity, according to the present disclosure, the phosphate ester may be used in an amount of 0.05 to 18 parts by weight, preferably 0.1 to 8 parts by weight, and more preferably 0.2 to 6 parts by weight, relative to 100 parts by weight of the sulfuric acid solution; the amount of the acid-soluble oil may be 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight; the weight ratio of phosphate to acid-soluble oil may be 1: (1-20), preferably can be 1: (3-15); co-catalysts in this range are capable of exhibiting higher catalytic activity in the presence of sulfuric acid.

The present disclosure is not limited to the specific kind of phosphate, and may be a conventional choice in the art, for example, may be one or more of a phosphoric monoester, a phosphoric diester and a phosphoric triester, preferably a phosphoric triester, and the general formula of the phosphoric triester may be (RO) ₃ PO, wherein R can be alkyl, alkylaryl, polyoxyethylated alkyl or polyoxyethylated alkylaryl, for example, can be one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, trioctyl phosphate and tricresyl phosphate, and can be preferably one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate and tributyl phosphate.

The form and concentration of the sulfuric acid solution are not limited in the present disclosure, and may be any conventional choice in the art, and according to the present disclosure, the sulfuric acid solution may be an aqueous solution of sulfuric acid, preferably concentrated sulfuric acid, and the mass concentration of sulfuric acid in the aqueous solution of sulfuric acid may be 70% or more, preferably 85 to 99.8%, and further preferably 90 to 99%, and in a specific embodiment, the mass concentration of sulfuric acid in the sulfuric acid solution may be 98.3%, and the aqueous solution of sulfuric acid in the above range may form a sulfuric acid catalytic system having higher activity with the co-catalyst, thereby improving the selectivity of the product.

In order to convert the reactants in the alkylation reaction as much as possible to product alkylate gasoline, and to increase the final product yield, in one embodiment according to the present disclosure, isobutane is reacted with C ₄ The volume ratio of the olefin may be (1-160): 1, preferablyThe ground may be (6-120): 1, the amount of the reactant in the above range enables higher product yields. Wherein isobutane and C ₄ The volume ratio of olefin refers to liquid isobutane to liquid C ₄ The volume ratio of the olefins.

The mixed carbon four feedstock added in the process of the present disclosure may include C ₄ Olefins and isobutane, p C of the present disclosure ₄ The type of olefin is not limited, in one embodiment C ₄ The olefin may be one or more of 1-butene, n-2-butene, trans-2-butene and isobutene, and preferably may be a mixed olefin comprising 1-butene, n-2-butene, trans-2-butene and isobutene.

In a further embodiment, the mixed carbon four raw material may further include n-butane, the volume content of n-butane may be 1 to 6%, the volume content of 1-butene may be 1 to 6%, the volume content of n-2-butene may be 1 to 6%, the volume content of trans-2-butene may be 1 to 7%, and the volume content of isobutene may be 0 to 2% based on the total volume of the carbon four raw material.

In order to provide the reaction system with the proper amounts of reactants and catalyst to promote the forward progress of the reaction, maximize the catalytic activity of the co-catalyst system and increase the product yield, in one embodiment according to the present disclosure, the sulfuric acid solution is mixed with C ₄ The volume ratio of the olefin may be (0.5 to 50): 1, preferably (1 to 10): 1.

the specific conditions for the alkylation reaction are not limited by the present disclosure, and may be conventional choices in the art, and may specifically include: the reaction temperature is-15 ℃ to 40 ℃, preferably can be-5 ℃ to 20 ℃; the reaction pressure is 0.1 to 1.5MPa, preferably may be 0.2 to 0.8MPa. According to the present disclosure, the alkylation reaction may be a continuous reaction or a batch reaction, and in an embodiment of the batch reaction, the reaction time may be 0.1 to 60 minutes, preferably may be 1 to 20 minutes; in continuous reaction embodiments, the volume space velocity may be from 0.5 to 30 hours ^-1 Preferably 1 to 20 hours ^-1 。

The process of the present disclosure may be carried out in a variety of reactor forms, and in one embodiment, continuous reactors commonly used in the industry may be employed; the continuous reactor may be any one of a horizontal reactor, a step reactor, a mixed packed column reactor and a static mixing reactor, and preferably may be any one of a step reactor and a mixed packed column reactor.

In a further embodiment, the step reactor may be composed of a plurality of reaction sections, which may be separated by overflow plates, and each reaction section may be provided with a stirrer, respectively; in this embodiment, sulfuric acid solution, isobutane and C ₄ The olefin can be pumped into the reactor according to the feeding amount to react; after the reaction is finished, the mixed material containing the reaction product and the sulfuric acid solution can enter a sedimentation section for separation, the separated sulfuric acid solution is pumped into the reaction section for use, the separated reaction product can enter a product treatment and fractionation stage, finally an alkylation product is obtained, and the separated isobutane can be pumped into the reaction section for recycling.

In another embodiment, the alkylation reaction may be carried out using a batch reactor, which may be a kettle reactor. In further embodiments, the method of alkylation reaction may comprise: mixing concentrated sulfuric acid with a cocatalyst in a certain proportion, adding into a stirring reaction kettle, starting stirring, optionally starting refrigeration, and after the temperature reaches the reaction temperature, adding isobutane and C ₄ The olefin is prepared into mixed carbon four with a certain alkane-alkene ratio, the mixed carbon four is pumped into a reaction kettle for reaction by a pump, stirring is stopped after the reaction is finished, a reaction product and a catalyst are kept stand for layering, and the reaction product alkylate is obtained after separation, and the product analysis is carried out.

According to the present disclosure, acid-soluble oils can be produced by rearranging and polymerizing olefins and tertiary butyl carbanions, the initially produced polymer being highly unsaturated, ionized and capable of continuing to polymerize with olefins to produce a macromolecular polymer which, due to its high ionization, readily accepts hydride anions from isobutane to render isobutane (C) ₄ H ₉ ) ⁺ Thereby initiating the alkylation reaction.

In one embodiment according to the present disclosure, acid-soluble oil may be prepared by a process comprising pouring 600mL (1104 g) of concentrated sulfuric acid into a reaction vessel, replacing the air in the reaction vessel with nitrogen, and initiating agitation and refrigeration. Stirring and rotating speed is regulated to 1000r/min, temperature is controlled at 8 ℃, pressure is controlled at 0.45MPa, butane (which can comprise n-butane and isobutane) and olefin mixed raw material 600mL with the volume ratio of alkane to alkene of 1:1 are pumped to carry out alkylation reaction for 10min, wherein the olefin mixed raw material is mixed carbon tetraolefin, the composition and content of the mixed carbon tetraolefin and the mixed carbon tetraolefin can be the same or different, and in one embodiment, the mixed carbon tetraolefin used for preparing acid-soluble oil can comprise isobutane 40.3%, n-butane 9.7%, 1-butene 16.1%, trans-2-butene 18.5%, n-2-butene 14.8% and isobutene 0.6%. Stopping stirring after the reaction is finished, standing and layering the reaction product and sulfuric acid after the reaction, wherein the lower layer is a sulfuric acid layer, the upper layer is reaction product alkylate, and separating to obtain the sulfuric acid layer. The sulfuric acid layer was diluted with water and separated into a water phase (dilute sulfuric acid phase) and an acid-soluble oil phase to obtain an acid-soluble oil.

To further increase the reactivity of the sulfuric acid catalyst system, the C in the alkylate is increased ₈ Selectivity of components and C ₈ Selectivity of the target product high octane component of the component Trimethylpentane (TMP), according to one embodiment of the present disclosure, the co-catalyst may further contain a sulfonate, and further, the weight ratio of the phosphate to the sulfonate may be (0.02 to 1.0): 1, preferably (0.1 to 0.8): 1, the co-catalyst composition within the above range has a more excellent catalytic effect.

The kind of sulfonate is not particularly limited in the present disclosure, and may be specifically one or more of 1, 3-propane sultone, 1, 4-butane sultone, ethyl methane sulfonate, 4-toluene sulfonate and ethyl 4-toluene sulfonate, and preferably one or more of 1, 3-propane sultone, 4-toluene sulfonate and ethyl 4-toluene sulfonate.

In a preferred embodiment of the present disclosure, the co-catalyst may be a phosphate, sulfonate, and the acid-soluble oilThe weight ratio of the mixture, phosphate, sulfonate and the acid-soluble oil may be (0.02 to 1): (0.1-5): 1, preferably (0.06 to 0.4): (0.3-2): 1, a step of; further, the phosphate esters may include tributyl phosphate and triisobutyl phosphate, and the sulfonate esters may include ethyl 4-toluenesulfonate and 1, 4-butanesulfonic acid lactone; further, the mass ratio of tributyl phosphate to triisobutyl phosphate may be 1: (0.1 to 5), preferably 1: (0.9 to 1.1); the mass ratio of the 4-toluenesulfonic acid ethyl ester to the 1, 4-butanesultone can be 1: (0.1 to 5), preferably 1: (0.9-1.1). In this preferred embodiment, the above-described range and composition of the cocatalyst system provides superior reaction results, with the reaction product alkylate C ₈ Selectivity of components and C ₈ The selectivity of the high-octane component Trimethylpentane (TMP) of the target product in the components is further improved, and the research octane number and the motor octane number are also further improved.

The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby.

The acid-soluble oil in the examples is prepared by the following steps:

600mL (1104 g) of concentrated sulfuric acid was poured into the reaction vessel, the air in the reaction vessel was replaced with nitrogen, and stirring and refrigeration were started. Stirring and rotating speed to 1000r/min, controlling temperature at 8 ℃, controlling pressure at 0.45MPa, pumping 600mL of butane and olefin mixed raw material (mixed olefin or mixed C4) with the volume ratio of alkane to olefin of 1:1, wherein the specific composition is 40.3 percent of isobutane, 9.7 percent of n-butane, 16.1 percent of 1-butene, 18.5 percent of trans-2-butene, 14.8 percent of n-2-butene and 0.6 percent of isobutene, and carrying out alkylation reaction for 12min at 8 ℃ and 0.45MPa. Stopping stirring after the reaction is finished, standing and layering the reaction product and sulfuric acid after the reaction, wherein the lower layer is a sulfuric acid layer, the upper layer is reaction product alkylate, and separating to obtain the sulfuric acid layer. The sulfuric acid layer was diluted with water and separated into a water phase (dilute sulfuric acid phase) and an acid-soluble oil phase, yielding 65g of acid-soluble oil for use.

Comparative example

100mL (184 g) of concentrated sulfuric acid (98% by mass concentration, carbofuran technologies Co., ltd.) was poured into a batch stirring reactor, the air in the reactor was replaced with nitrogen, and stirring and refrigeration were started. Stirring and rotating speed is regulated to 1200r/min, temperature is controlled at 8 ℃, pressure is controlled at 0.4MPa, and 100mL of mixed carbon four raw material with the alkane-alkene volume ratio of about 8:1 is pumped into the reactor for alkylation reaction for 10min. After the reaction is completed, stopping stirring, standing and layering the reaction product and the catalyst, wherein the lower layer is the catalyst, and the upper layer is the reaction product alkylate, and separating to obtain the reaction product alkylate. Wherein the mixed carbon four raw materials comprise 87.4 wt% of isobutane, 1.7 wt% of normal butane, 3.3 wt% of 1-butene, 4.1 wt% of trans-2-butene, 3.1 wt% of normal 2-butene and 0.4 wt% of isobutene.

Comparative example 1

100mL (184 g) of concentrated sulfuric acid (the mass concentration is 98%) is poured into a batch stirring reaction kettle, 3mL (3.6 g) of ethyl methanesulfonate (the purity is > 99%) and 1.8g of acid-soluble oil (the carbofuran technology Co., ltd.) are added, air in the reaction kettle is replaced by nitrogen, and stirring and refrigeration are started. Stirring and rotating speed is regulated to 1200r/min, temperature is controlled at 8 ℃, pressure is controlled at 0.4MPa, and 100mL of mixed carbon four raw material with the alkane-alkene volume ratio of about 8:1 is pumped into the reactor for alkylation reaction for 10min. After the reaction is completed, stopping stirring, standing and layering the reaction product and the catalyst, wherein the lower layer is the catalyst, and the upper layer is the reaction product alkylate, and separating to obtain the reaction product alkylate. The specific composition of the mixed carbon four raw material comprises 87.4 wt% of isobutane, 1.7 wt% of normal butane, 3.3 wt% of 1-butene, 4.1 wt% of trans-2-butene, 3.1 wt% of normal 2-butene and 0.4 wt% of isobutene.

Example 1

100mL (184 g) of concentrated sulfuric acid (98% by mass concentration) is poured into a batch stirring reaction kettle, and ethyl methanesulfonate (purity of the product is obtained by the company of the technology Co., ltd.)>99%) 2.5mL (3.0 g), trimethyl phosphate (purity of the product of Baolinwei technology Co., ltd.)>99%) 0.5mL (0.6 g) and 1.8g of acid-soluble oil, the air in the reaction vessel was replaced with nitrogen, stirring and refrigeration were started. Stirring at a speed of 1200r/min, controlling the temperature at 8deg.C, and pressureAnd (3) controlling the pressure to be 0.4MPa, pumping 100mL of mixed carbon four raw material with the alkane-alkene volume ratio of about 8:1 into the mixture, and carrying out alkylation reaction for 8min. After the reaction is completed, stopping stirring, standing and layering the reaction product and the catalyst, wherein the lower layer is the catalyst, and the upper layer is the reaction product alkylate, and separating to obtain the reaction product alkylate. Wherein the specific composition of the mixed carbon four raw material comprises 87.4 weight percent of isobutane, 1.7 weight percent of normal butane, 3.3 weight percent of 1-butene, 4.1 weight percent of trans-2-butene, 3.1 weight percent of normal 2-butene and 0.4 weight percent of isobutene; sulfuric acid and C ₄ The olefin volume ratio is 9:1.

comparative example 2

Alkylated gasoline was prepared by the method of comparative example 1, except that: the co-catalyst was ethyl methanesulfonate (carbofuran technologies Co., ltd., purity > 99%) 3mL (3.6 g) and acid-soluble oil 3.7g.

Example 2

Alkylated gasoline was prepared by the method of example 1, except that: the co-catalyst was ethyl methanesulfonate (carbofuran technologies Co., ltd., purity > 99%) 2.5mL (3.0 g), triethyl phosphate (carbofuran technologies Co., ltd., purity > 99%) 0.5mL (0.6 g) and acid-soluble oil 3.7g.

Comparative example 3

Alkylated gasoline was prepared by the method of comparative example 1, except that: the co-catalyst was 3.7g of methyl 4-toluenesulfonate (carbofuran technologies Co., ltd., purity > 98%) and 3.7g of acid soluble oil.

Example 3

Alkylated gasoline was prepared by the method of example 1, except that: the co-catalyst was 3.1g of methyl 4-toluenesulfonate (carbofuran technologies Co., ltd., purity > 98%), 0.6mL (0.6 g) of tributyl phosphate (carbofuran technologies Co., ltd., purity > 99%), and 3.7g of acid-soluble oil.

Comparative example 4

Alkylated gasoline was prepared by the method of comparative example 1, except that: the co-catalyst was 3.7g of ethyl 4-toluenesulfonate (carbofuran technologies Co., ltd., purity > 98%) and 5.5g of acid-soluble oil, and the reaction temperature was controlled at 4℃and the pressure was controlled at 0.45MPa.

Example 4

Alkylated gasoline was prepared by the method of example 1, except that: the co-catalyst was 3.1g of ethyl 4-toluenesulfonate (carbofuran technologies Co., ltd., purity > 98%), 0.6mL (0.6 g) of tributyl phosphate (carbofuran technologies Co., ltd., purity > 99%) and 5.5g of acid-soluble oil, and the reaction temperature was controlled at 4℃and the pressure was controlled at 0.45MPa.

Comparative example 5

Alkylated gasoline was prepared by the method of comparative example 1, except that: the co-catalyst was 3.7g of 1, 3-propane sultone (Budweiser technologies Co., ltd., purity > 99%) and 5.5g of acid-soluble oil, and the reaction pressure was controlled at 0.45MPa.

Example 5

Alkylated gasoline was prepared by the method of example 1, except that: the co-catalyst was 3.1g of 1, 3-propane sultone (Budweiser technologies Co., ltd., purity > 99%), 0.5mL (0.6 g) of tricresyl phosphate (Budweiser technologies Co., purity > 98%) and 5.5g of acid-soluble oil, and the reaction pressure was controlled at 0.45MPa.

Comparative example 6

Alkylated gasoline was prepared by the method of comparative example 1, except that: the co-catalyst was 3.7g of 1, 3-propane sultone (purity >99% by carboline technologies Co., ltd.) and 9.2g of acid-soluble oil, and the reaction pressure was controlled at 0.45MPa.

Example 6

Alkylated gasoline was prepared by the method of example 1, except that: the co-catalyst was 3.1g (purity >99% by carbofuran technologies Co., ltd.) of 1, 3-propane sultone, 0.6mL (0.6 g) of trioctyl phosphate (purity >98% by carbofuran technologies Co., ltd.) and 9.2g of acid-soluble oil, and the reaction pressure was controlled at 0.45MPa.

Example 7

Alkylated gasoline was prepared by the method of example 1, except that: the co-catalyst was 3mL (4.0 g) of 1, 4-butanesultone (Budweiser technologies Co., ltd., purity > 99%), 1.2mL (1.3 g) of triisobutyl phosphate (Budweiser technologies Co., ltd., purity > 99%) and 3.7g of acid-soluble oil, and the reaction temperature was controlled at 6 ℃.

Example 8

Alkylated gasoline was prepared by the method of example 1, except that: the co-catalyst was 3mL (4.0 g) of 1, 4-butanesultone (Budweiser technologies Co., ltd., purity > 99%), 1.2mL (1.3 g) of triisobutyl phosphate (Budweiser technologies Co., ltd., purity > 99%) and 7.4g of acid-soluble oil, and the reaction temperature was controlled at 6℃and the reaction time was 15min.

Example 9

Alkylated gasoline was prepared by the method of example 1, except that: the co-catalyst was ethyl 4-tosylate (carbofuran technologies Co., ltd., purity > 98%) 2.3g,1, 4-Butanolide (carbofuran technologies Co., purity > 99%) 1.6mL (2.2 g), followed by tributyl phosphate (carbofuran technologies Co., purity > 99%) 0.5mL (0.5 g), triisobutyl phosphate (carbofuran technologies Co., purity > 99%) 0.5mL (0.5 g) and acid soluble oil 5.5g.

Example 10

Alkylated gasoline was prepared by the method of example 9, except that: the co-catalyst was tributyl phosphate (carbofuran technologies Co., ltd., purity > 99%) 2.5mL (2.75 g) and triisobutyl phosphate (carbofuran technologies Co., ltd., purity > 99%) 2.5mL (2.75 g) and acid-soluble oil 5.5g.

Example 11

Alkylated gasoline was prepared by the method of example 9, except that: the co-catalyst was tributyl phosphate (carbofuran technologies Co., ltd., purity > 99%) 5.0mL (5.5 g) and acid-soluble oil 5.5g.

The analysis results of the reaction product alkylate of examples and comparative examples are shown in Table 1. Wherein, the reaction product is quantitatively analyzed by a GC7890 gas chromatograph, the FID detector and the chromatographic column are capillary columns. The octane number of the reaction product was determined by near infrared spectroscopy (RON-NIR); TMP represents trimethylpentane, RON represents research octane number, and MON represents motor octane number.

TABLE 1

Analysis of results: from table 1, it can be seen from a comparison of the data of examples 1-11 and comparative examples 1-6 that the process of the present disclosure employs a catalyst comprising a phosphate ester and an acid-soluble oil as a co-catalyst, which significantly improves the selectivity of the reaction product, the product quality, and the alkylate octane number; as can be seen from a comparison of the data of example 10 and example 11, in the preferred embodiments of the present disclosure in which the phosphate esters include tributyl phosphate and triisobutyl phosphate, C can be further enhanced ₈ Selectivity to trimethylpentane, and product octane number; as can be seen from a comparison of the data of example 9 and example 10, in the preferred embodiment of the present disclosure in which tributyl phosphate and triisobutyl phosphate (the mass ratio of tributyl phosphate to triisobutyl phosphate is 1 (0.9 to 1.1) and 1, 3-propane sultone and 1, 4-butane sultone (the mass ratio of 1, 3-propane sultone to 1, 4-butane sultone) are 1 (0.9 to 1.1) together are sulfuric acid, the reaction product C ₈ Content of (C) and C ₈ The content of Trimethylpentane (TMP) which is a medium and high octane component is greatly increased, and C _5-7 Component and C ₉ The content of the heavy components is greatly reduced, and meanwhile, the octane number of the product is obviously improved.

The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.

In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.

Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.

Claims

1. A method of producing an alkylate, the method comprising: under alkylation reaction conditions, isobutane and C ₄ The olefin is contacted and reacted in the presence of sulfuric acid solution and a co-catalyst; wherein the co-catalyst comprises a phosphate ester and an acid-soluble oil;

carrying out alkylation reaction on the mixed carbon four raw materials in concentrated sulfuric acid, taking out a lower layer product after carrying out first phase separation on the obtained first mixture, mixing the lower layer product with water to obtain a second mixture, and taking out an upper layer product after carrying out second phase separation on the second mixture to obtain the acid-soluble oil;

wherein the phosphoric acid ester is used in an amount of 0.05 to 18 parts by weight relative to 100 parts by weight of the sulfuric acid solution;

the amount of the acid-soluble oil is 0.5 to 10 parts by weight relative to 100 parts by weight of the sulfuric acid solution;

the mass concentration of sulfuric acid in the sulfuric acid solution is more than 70%; the sulfuric acid solution and the C ₄ The volume ratio of the olefin is (0.5-50): 1, a step of; the isobutane and the C ₄ The volume ratio of the olefin is (1-160): 1, a step of;

the alkylation reaction conditions include: the reaction temperature is between-15 ℃ and 40 ℃ and the reaction pressure is between 0.1 and 1.5MPa.

2. The method according to claim 1, wherein the phosphoric acid ester is used in an amount of 0.1 to 8 parts by weight relative to 100 parts by weight of the sulfuric acid solution.

3. The method according to claim 1, wherein the acid-soluble oil is used in an amount of 1 to 8 parts by weight relative to 100 parts by weight of the sulfuric acid solution.

4. The method of claim 1, wherein the weight ratio of the phosphate ester to the acid-soluble oil is 1: (1-20).

5. The method of claim 1, wherein the phosphate is one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, trioctyl phosphate, and tricresyl phosphate.

6. The method of claim 1, wherein the C ₄ The olefin is one or more of 1-butene, n-2-butene, trans-2-butene and isobutene.

7. The process of any one of claims 1-6, wherein the alkylation reaction conditions comprise: the reaction time is 0.1-60 min; alternatively, the volume airspeed is 0.5 to 30 hours ^-1 。

8. The method of claim 1, wherein the mixed carbon four feedstock comprises one or more of isobutane, n-butane, 1-butene, trans-2-butene, n-2-butene, and isobutene, and the mixed carbon four feedstock has an alkane to alkene volume ratio of 1: (0.5-2); the alkylation reaction conditions include: the reaction temperature is between-10 and 20 ℃, the reaction pressure is between 0.3 and 1.0MPa, and the reaction time is between 1 and 40 minutes.

9. The method of claim 1, wherein the co-catalyst further comprises a sulfonate.

10. The method of claim 9, wherein the weight ratio of the phosphate to the sulfonate is (0.02-1.0): 1, a step of;

11. The method of claim 9 or 10, wherein the co-catalyst is a mixture of phosphate, sulfonate and acid-soluble oil, the weight ratio of phosphate, sulfonate and acid-soluble oil being (0.06-0.4): (0.3-2): 1.

12. the method of claim 11, wherein the sulfonate comprises ethyl 4-toluenesulfonate and 1, 4-butanesulfonic acid lactone, the weight ratio of ethyl 4-toluenesulfonate to 1, 4-butanesulfonic acid lactone being 1: (0.9-1.1).

13. The method of claim 1 or 9, wherein the phosphate ester comprises tributyl phosphate and triisobutyl phosphate, the weight ratio of tributyl phosphate to triisobutyl phosphate being 1: (0.9-1.1).

14. The process of claim 1, wherein the alkylation reaction is carried out in a batch reactor or a continuous reactor; the batch reactor comprises a kettle reactor; the continuous reactor is one or more of a horizontal reactor, a stepped reactor, a mixed packing tower reactor and a static mixing reactor.