KR102551320B1 - Method for improving production yield of 2-butanol using solubilizer in butene hydration reaction - Google Patents

Abstract

The present invention relates to a hydration reaction of n-butene, and more particularly, to a method for improving the yield of 2-butanol produced from the hydration reaction of n-butene by introducing a dissolution enhancer.

Description

Method for improving production yield of 2-butanol using solubilizer in butene hydration reaction}

The present invention relates to a method for improving the production yield of 2-butanol by applying a solubilizer to the hydration reaction of n-butene, and more particularly, to the hydration reaction of n-butene using a surfactant as a solubilizer ( It relates to a method for producing 2-butanol through hydration reaction).

2-Butanol is also used for solvent or essence synthesis, but is mostly used as a raw material for methyl-ethyl-ketone (MEK). Since MEK is an effective solvent for substances such as vinyl resin, cellulose acetate, and nitrocellulose, it is used as a raw material for paints, coatings, frill inks, or adhesives.

Until now, most of MEK has been produced through the dehydrogenation process of 2-butanol in the presence of a copper or zinc-based catalyst. Butene-to-MEK process is proposed to increase profit in this process. This is a method of producing 2-butanol by hydrating n-butene produced in various petrochemical processes under an acid catalyst and then dehydrogenating it to produce MEK. Sulfuric acid is mainly used for hydration of butene, which has the advantage of simple reaction conditions and easy control, but has disadvantages such as severe corrosion of reaction equipment, additional sulfuric acid treatment cost, and environmental problems. Therefore, in order to solve the above problems, research on acid catalysts that can replace sulfuric acid, such as zeolite (Non-Patent Document 1), ion exchange resin (Non-Patent Document 2), and heteropoly acid (Non-Patent Document 3), has been conducted.

In the hydration process using an ion exchange resin as a catalyst, the reaction proceeds with a direct hydration mechanism in which water and n-butene react directly in a liquid phase (Non-Patent Document 3).

Therefore, the degree of dissolution of n-butene in water is an important factor in the activity of the reaction. Accordingly, the inventors of the present invention have developed a catalytic reaction process capable of producing 2-butanol in high yield using a solubility enhancer in order to increase the solubility of butene in water through continuous research.

(Non-Patent Document 1) S. M. Mahajani, M. M. Sharma, T. Sridhar, Chem. Eng. Sci., Volume 56, pages 5625-5633. (Non-Patent Document 2) D. Kallo, R. M. Mihlyi, Appl. Catal. A: Gen., Volume 121, pp. 45-56. (Non-Patent Document 3) T. Yamada, T. Muto, Sekiyu Gakkaishi, 34(3) pp. 201-209.

An object of the present invention is to provide a method for stably improving the yield of 2-butanol produced from n-butene using a solubility enhancer.

In order to achieve the above technical problem, the present invention provides a flow containing any one n-butene selected from 1-butene, cis-2-butene and trans-2-butene or a mixture of n-butene mixtures thereof as a raw material (10), and in producing 2-butanol from n-butene or n-butene mixed gas as raw material 10, the solubility of butene in water is increased by using a solubility enhancer, thereby producing 2-butanol in high yield. It provides a way to manufacture it.

In the raw material 10, it is preferable for this reaction that the n-butene or n-butene mixture gas is included in 50 wt% or more of the raw material flow.

The surfactant is a nonionic surfactant, and alkyl polyglucosides are used. When the nonionic surfactant is used, the balance between the hydrophilic group and the lipophilic group can be easily changed compared to other surfactants, thereby controlling the polarity of the molecule. This has the advantage of being able to select and use the optimal emulsifier according to the reactant, and also has the advantage that nonionic surfactants are stable even in acidic or alkaline media, so they are stable even in this reaction using an acid catalyst.

In addition, the present invention provides 2-butanol by the hydration reaction of n-butene, which includes the step of hydrating n-butene at a temperature and pressure in the range of 60 to 150 ° C. and 30 to 100 bar in the presence of an ion exchange resin catalyst. Provides a manufacturing method of.

In the present invention, the dissolution enhancer is added to the hydration reaction of n-butene or n-butene mixed gas as raw material 10, the hydration reaction proceeds in the fixed bed reactor 108 of the continuous high-pressure reactor, and the ion exchange A resin catalyst is filled in the fixed bed reactor (108).

The dissolution enhancer uses a surfactant, and the surfactant improves the hydration reaction by making polar water and non-polar butene (raw material) well mixed, but is not limited as long as it is stable in the reaction. It is preferable to use an acid catalyst for this reaction, and it is more preferable to use an alkyl polyglucoside in particular.

The solubility enhancer is injected in the form of a mixture of the solubility enhancer and distilled water, and the content of the solubility enhancer in the mixture is 1 to 30%.

Raw material n-butene or n-butene mixed gas is hydrated in the presence of an ion exchange resin catalyst filled in the fixed bed reactor 108, and the raw material is hydrated at a flow rate of LHSV 1 to 5h ^-1 through a mass flow controller. It is injected into the fixed bed reactor (103).

The hydration reaction is carried out at a reaction temperature of 60 to 150 ° C and a reaction pressure of 30 to 100 bar.

According to the present invention, when direct hydration of n-butene is performed in a liquid phase using a solubility enhancer, 2-butanol can be produced in a higher yield than when a solubility enhancer is not used.

1 is a schematic diagram of a continuous high-pressure reactor used in the production of 2-butanol through direct hydration from n-butene.

Example 1: Preparation of 2-butanol from n-butene by hydration using a dissolution enhancer

While using a nonionic surfactant as a dissolution enhancer, a reaction for producing 2-butanol by a hydration reaction of n-butene was performed.

The reactor used in this example is shown in FIG. 1. The ion exchange resin catalyst is filled in a fixed bed reactor 108, and a 5% surfactant aqueous solution as a dissolution enhancer 11 and a raw material 10, which is n-butene or n-butene mixture gas, are supplied to the fixed bed reactor (108) by using a pump. 108) was injected at a constant flow rate.

The raw material 10, n-butene, is butene, and is any single normal butene selected from 1-butene, cis-2-butene, or trans-2-butene, or a mixture thereof, and the raw material 10 is the single normal butene. It is preferable that the content of butene (n-butene) or a mixture thereof includes at least 50 wt% or more of the raw material stream, and more preferably 70 wt% or more. When the content of butene is less than 50wt% in the flow of the raw material 10, there is a problem in that the yield of the product is lowered.

The raw material 10 is injected into the fixed bed reactor 108 through a mass flow controller 103 (MFC), and the mass flow controller 103 serves to control the flow rate of injected butenes.

The flow rate of butene controlled by the mass flow controller is preferably LHSV 1 to 5 h ^-1 , and more preferably LHSV 1 to 3 h ^-1 . When the flow rate is less than LHSV 1h ^-1 , production efficiency is lowered, and when LHSV is 5 h ^-1 or more, there is a problem in that butene conversion rate is lowered.

In FIG. 1, the injected solubility enhancer + distilled water 11 is in the form of a mixture of the solubility enhancer and distilled water. it is more preferable When the content of the solubility enhancer is less than 1%, the effect of enhancing the solubility is insignificant.

Among the dissolution enhancers used in Examples of the present invention, surfactant was TRITON™ BG-10 from Dow, which uses an alkyl polyglucoside among nonionic surfactants.

1, vapor 12 as a product means that unreacted butene is obtained in a gaseous state, and the flow from which the vapor 12 is removed flows from the first reservoir 110 to the second reservoir 111. , together with the unreacted water and the produced 2-butanol (14) discharged from the second reservoir (111), as part of which, secondary butyl alcohol generated through hydration and unreacted water are together A liquid sample 13 was obtained, and the results of the liquid sample 13 are shown in Table 1 below.

The temperature of the fixed bed reactor 108 was raised to 140° C., and the reactor pressure was increased to 60 bar, and then the reaction for producing 2-butanol was performed.

In the embodiment of the present invention, as the ion exchange resin catalyst used in the fixed bed reactor 108, an Amberlyst-15 solid acid catalyst, which is a cation exchange resin, was used.

After the start of the reaction, the product was sampled at intervals of 4 hours, and the conversion of 1-butene, the selectivity of 2-butanol, and the yield of 2-butanol were calculated as in Equations 1, 2, and 3 below.

[Equation 1]

[Equation 2]

[Equation 3]

Comparative Example 1: Preparation of 2-butanol from n-butene by hydration without using a solubility enhancer

The experiment was conducted in the same manner as in Example 1 except that the dissolution enhancer was not used.

Table 1 below shows the 2-butanol yield results of Example 1 and Comparative Example 1. In the case of using the solubility enhancer (Example 1), it can be confirmed that the yield of 2-butanol is greatly improved as the solubility of butene in water is stably increased.

The embodiments of the present invention described above should not be construed as limiting the technical spirit of the present invention. The protection scope of the present invention is limited only by the matters described in the claims, and those skilled in the art can improve and change the technical idea of the present invention in various forms. Therefore, these improvements and changes will fall within the protection scope of the present invention as long as they are obvious to those skilled in the art.

10 Raw material (n-butene or n-butene mixture gas)
11 solubility enhancer + distilled water
12 unreacted butenes
13 liquid sample
14 unreacted water and produced 2-butanol
101 on-off valve
102 pressure gauge
103 Mass flow controller
104 check valve
105 liquid pump
106 filter
107 Thermocouple
108 Fixed bed reactor
109 pressure regulator
110 1st reservoir
111 #2 reservoir

Claims (8)

Using a flow containing any n-butene selected from 1-butene, cis-2-butene, and trans-2-butene or a mixture of n-butene mixed gas as a raw material, and converting the raw material into 2-butanol A method for producing 2-butanol, characterized in that a surfactant is added as a dissolution enhancer to the hydration reaction, and the surfactant is an alkyl polyglucoside as a nonionic surfactant. delete The method for producing 2-butanol according to claim 1, wherein the raw material is hydrated in the presence of an ion exchange resin catalyst to produce 2-butanol. The method of claim 1, wherein the raw material contains 50 wt% or more of n-butene or n-butene mixed gas. The method for producing 2-butanol according to claim 1, wherein the hydration reaction is performed at a reaction temperature of 60 to 150 °C and a reaction pressure of 30 to 100 bar. The method of claim 3, wherein the ion exchange resin catalyst is charged in a fixed bed reactor of a continuous high-pressure reactor. The method of claim 6, wherein the raw material is injected into the fixed bed reactor at a flow rate of LHSV 1 to 5h ^-1 through a mass flow controller. The method of claim 1, wherein the solubility enhancer is a mixture of the solubility enhancer and distilled water, and the content of the solubility enhancer in the mixture is 1 to 30%.

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