CN110016362B

CN110016362B - Method for preparing alkylate oil by taking metal compound as auxiliary agent

Info

Publication number: CN110016362B
Application number: CN201910328246.4A
Authority: CN
Inventors: 赵国英; 张振华; 贾利娜; 张锁江
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2019-04-23
Filing date: 2019-04-23
Publication date: 2020-08-04
Anticipated expiration: 2039-04-23
Also published as: CN110016362A

Abstract

The invention belongs to the field of petrochemical industry, and particularly relates to a method for preparing alkylate oil by using a metal compound as an auxiliary agent, wherein isobutane and carbon tetraene are used as raw materials for alkylation reaction, strong protonic acid such as concentrated sulfuric acid is used as a catalyst, a lanthanum or bismuth metal compound is used as the auxiliary agent, the addition amount of the auxiliary agent is 0.5-10 wt%, the reaction temperature is-20-80 ℃, the pressure is 0.1-2.0 MPa, and the time is 0.1-60 min. The metal compound of lanthanum or bismuth is used as an alkylation auxiliary agent, so that high-quality and high-yield alkylate oil can be generated, the acid strength of the catalyst can be regulated, the selectivity of carbon eight components in the prepared alkylate oil is improved, the content of byproducts is reduced, a catalytic system can be recycled, and the acid consumption of a protonic acid catalyst is reduced. When the reaction is complete, the catalyst system can separate from the alkylate.

Description

Method for preparing alkylate oil by taking metal compound as auxiliary agent

Technical Field

The invention belongs to the field of petrochemical industry, and particularly relates to a method for preparing alkylate oil by using a metal compound as an auxiliary agent.

Background

Under the double-wheel drive of increasing the environmental treatment intensity and accelerating the upgrading of the quality of the finished oil, the requirement of the gasoline additive component with high octane number is greatly increased. The alkylation reaction of isobutane and olefin under the action of strong acid is an important process for producing clean gasoline components in the field of petrochemical industry, and the prepared alkylate oil becomes an ideal clean gasoline blending component due to the characteristics of high octane number, low vapor pressure, low sulfur, no aromatic hydrocarbon and the like.

The traditional alkylation catalyst is hydrofluoric acid and concentrated sulfuric acid, the hydrofluoric acid has strong corrosivity, toxicity and volatility, has great threat to human bodies and the environment, and is forbidden and forbidden to build hydrofluoric acid devices in partial areas. The alkylation process of concentrated sulfuric acid occupies a large proportion in the Chinese market, and although the process is mature, the problems of large waste acid discharge amount, high regeneration cost, environmental pollution and the like exist. Over the last several decades, many researchers have improved and perfected the concentrated sulfuric acid process to reduce acid consumption and improve the quality of alkylated products, which is mainly divided into two methods of strengthening acid-hydrocarbon mixing and adding auxiliary agentThe following studies were carried out. In the aspect of enhancing acid-hydrocarbon mixing, a novel reactor is designed and improved, such as a hypergravity reactor, an impinging stream reactor and the like, so as to improve the liquid-liquid mixing degree, enhance the heat exchange efficiency and the like. In the aspect of adding the auxiliary agent, the following researches are mainly divided into: 1) the surfactant is used as an auxiliary agent, so that the mixing degree of an acid-hydrocarbon interface can be increased, the solubility of isobutane can be increased, side reactions can be reduced, and the quality of an alkylated product can be improved. Such as dodecylbenzene sulfonic acid and p-phenylenediamine (US3655807, US3689590), N-trialkylphosphoric triamide (US 3865896) and the like. 2) The Buffer assistant delays the acidity change, prolongs the service life of the catalyst and the like by improving the acid-hydrocarbon interface. Example Huang et al (Ind. Eng. chem. Res.2015,54,1464-1469) use 0.5 wt% of [ Bmim ]][SbF₆]The catalyst is compounded with 40ml of concentrated sulfuric acid, the acid-hydrocarbon ratio is 40/50, the reaction time is 10min, the content of the obtained C8 is 90.07%, the selectivity of TMPs is 82.03%, the octane number is 98, and the service life of the catalyst is improved by nearly one time. Wang et al (Ind. Eng. chem. Res.,2016,55(30):8271-8280) use [ N₂₂₂₄]NTf₂And the catalyst and the trifluoromethanesulfonic acid form an ion Buffer effect, and the catalytic performance and the service life of the trifluoromethanesulfonic acid are also improved. 3) The hydrogen transfer aid enhances the rate of hydrogen transfer in the reaction control step, resulting in greater transfer of the alkylate to C8 and TMPs (trimethylpentanes). Such as amantadine and ionic liquids thereof, and the like.

The invention content is as follows:

the invention mainly aims to provide an auxiliary agent for improving protonic acid catalytic alkylation, which is used for improving the quality of an alkylation product and reducing acid consumption, and adopts the following specific technical scheme:

the invention provides a method for preparing alkylate by using a metal compound as an auxiliary agent, which is characterized in that under the alkylation condition of isobutane and olefin, protonic acid is used as a catalyst, and metal compounds such as lanthanum and bismuth are used as auxiliary agents to carry out alkylation reaction to obtain alkylate.

In the method provided by the invention, the olefin is one or a mixture of more than two of 1-butene, 2-butene, isobutene, ether carbon four and the like, and the molar ratio of isobutane to olefin is 1: 1-180: 1.

In the method provided by the invention, the catalyst is concentrated sulfuric acid, trifluoromethanesulfonic acid, hexafluoroisopropoxysulfonic acid and other protonic acids, the assistant is a metal compound of lanthanum or bismuth, such as lanthanum trifluoromethanesulfonate, triphenylbismuth and the like, and the catalyst and the assistant are used for preparing the alkylate oil in a concerted catalysis mode.

In the method provided by the invention, the addition amount of the auxiliary agent is 0.5-10 wt%.

In the method provided by the invention, the volume ratio of the catalyst to the mixed raw material hydrocarbon can be adjusted within 0.01-2 so as to obtain high-quality alkylate oil.

In the method provided by the invention, the alkylation reaction is carried out at the temperature of-20-80 ℃, the reaction pressure is 0.1-2.0 MPa, and the reaction time is 0.1-60 min.

In the method provided by the invention, the alkylation reaction is carried out in a stirring reactor, a packed bed reactor, a microfluid reactor, a hypergravity reactor, an ultrasonic reactor, a liquid-liquid two-phase mixing reactor and the like, and can be carried out intermittently or continuously.

Compared with the existing concentrated sulfuric acid alkylation process, the method for preparing the alkylate oil by using the metal compound as the auxiliary agent has the following advantages: the metal compound of lanthanum or bismuth is used as an alkylation auxiliary agent, so that the acid strength of the catalyst can be regulated, the selectivity of carbon eight components in the prepared alkylate oil is improved, the content of byproducts is reduced, a catalytic system can be recycled, and the acid consumption of a protonic acid catalyst is reduced.

The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.

The specific implementation mode is as follows:

in order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are further described below by way of specific embodiments. To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows.

Comparative example 1:

adding 40ml of concentrated sulfuric acid into a stirring reaction kettle, firstly replacing air in the kettle with nitrogen to keep a certain pressure in the kettle so as to keep mixed hydrocarbon liquid to participate in reaction, opening a stirring and constant-temperature tank, pumping 50ml of hydrocarbon mixed raw material at a feeding speed of 500m L/h by using a double-plunger micro-pump when the temperature in the kettle reaches 3 ℃, stopping stirring after 10min of reaction, collecting unreacted isobutane by an air bag to detect, pouring out liquid in the reaction kettle, standing and layering, wherein the upper layer is alkylate oil, the lower layer is acid, the alkylate oil is respectively washed three times by using a saturated sodium bicarbonate solution and deionized water, and is sent to a gas chromatograph for oil analysis, the oil analysis adopts a gas chromatograph (SHIMADZU GC 2014), the FID detector is a DB-Petro100m × 0.25.25 mm × 0.50 mu m capillary chromatographic column, and the composition of the alkylate oil is quantified by adopting a one-in method, and is shown in Table 1.

Example 1:

the procedure is as in comparative example 1, 40ml of concentrated sulfuric acid as catalyst and 0.05g of lanthanum triflate as auxiliary agent, the results are shown in Table 1.

Comparative example 2:

preparation of hexafluoroisopropoxysulfonic acid: slowly adding equimolar hexafluoroisopropanol into chlorosulfonic acid at-20 deg.C, stirring, and slowly raising to 140 deg.C until HCl gas is no longer released. The reaction mixture was distilled under reduced pressure to obtain hexafluoroisopropoxysulfonic acid. The procedure was as in comparative example 1, the catalyst was hexafluoroisopropoxysulfonic acid 10ml, and the results are shown in Table 1, with the other conditions being unchanged.

Example 2:

the procedure is as in comparative example 1, the catalyst is hexafluoroisopropoxysulfonic acid 10ml, the auxiliary is lanthanum trifluoromethanesulfonate 0.02g, and the results are shown in Table 1, except that the conditions are unchanged.

Example 3:

the procedure is as in comparative example 1, the catalyst is hexafluoroisopropoxysulfonic acid 10ml, the auxiliary is lanthanum trifluoromethanesulfonate 0.04g, and the results are shown in Table 1.

Example 4:

the procedure is as in comparative example 1, the catalyst is hexafluoroisopropoxysulfonic acid 10ml, the auxiliary is triphenylbismuth 0.02g, and the results are shown in Table 1.

Example 5:

the procedure is as in comparative example 1, the catalyst is hexafluoroisopropoxysulfonic acid 10ml, the auxiliary is triphenylbismuth 0.04g, and the results are shown in Table 1, except that the conditions are unchanged.

TABLE 1 alkylation Effect of the different examples

The applicant states that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting, although the present invention is described in detail with reference to the preferred embodiments, those skilled in the art can understand that modifications or equivalent substitutions can be made on the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, which shall be covered by the claims of the present invention.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A method for preparing alkylate oil by using a metal compound as an auxiliary agent is characterized in that isobutane and carbon tetraene are used as raw materials for alkylation reaction, strong-acid protonic acid is used as a catalyst, a lanthanum or bismuth metal compound is used as an auxiliary agent, the three materials are contacted in a reactor, the catalyst and the auxiliary agent are used for catalyzing alkylation reaction in a coordinated mode to prepare alkylate oil, after the reaction is finished, the alkylate oil with a high octane value can be obtained through standing and separation, wherein the strong-acid protonic acid is concentrated sulfuric acid, trifluoromethanesulfonic acid and hexafluoroisopropoxysulfonic acid, the lanthanum or bismuth metal compound is trifluoromethanesulfonic acid lanthanum and triphenylbismuth, and the addition amount of the auxiliary agent is 0.5-10 wt%.

2. The method according to claim 1, wherein the tetraolefin is 1-butene, 2-butene, isobutene, a mixture of four or more of the four tetraolefins, and the suitable molar ratio of isobutane to olefin is 1:1 to 180: 1.

3. The method according to claim 1, wherein the volume ratio of the catalyst to the mixed raw material of isobutane and carbon tetraolefin is adjusted within 0.01-2 to obtain better alkylate.

4. The method according to claim 1, wherein the alkylation reaction is carried out at a temperature ranging from-20 ℃ to 80 ℃, a reaction pressure ranging from 0.1 MPa to 2.0MPa, and a reaction time ranging from 0.1 min to 60 min.

5. The method of claim 1, wherein the alkylation reaction is carried out in a stirred reactor, a packed bed reactor, a microfluidic reactor, a hypergravity reactor, an ultrasonic reactor, a liquid-liquid two-phase mixing reactor, a batch reaction, or a continuous production.

6. The method of claim 1, wherein after the alkylation reaction, the alkylate is obtained by standing and separating, and the alkylate at the upper layer is taken out; the lower-layer catalytic system is continuously put into reaction, and the catalytic system can be recycled, so that the acid consumption is reduced.