TW201331169A - Heterogeneous catalyst and co-production method of 1,4-butanediol, gamma-butyrolactone and tetrahydrofuran - Google Patents

Abstract

A co-production method of 1,4-butanediol, gamma-butyrolactone and tetrahydrofuran comprises using a heterogeneous catalyst containing a first active metal and a second active metal to catalyze the hydrogenation of aldehyde mixture containing 4-hydroxybutanal to obtain the 1,4-butanediol, the gamma-butyrolactone and the tetrahydrofuran. In particular, the heterogeneous catalyst comprises an inert carrier and a first active metal and a second active metal supported on the inert carrier.

Description

Heterogeneous catalyst and method for co-producing 1,4-butanediol, γ-butyrolactone and tetrahydrofuran

The present invention relates to the preparation of 1,4-butanediol and the co-production of derivatives thereof, in particular to the preparation of 1,4-butanediol and its derivatives in the presence of a heterogeneous catalyst having at least two active metals. Methods.

1,4 Butanediol (BDO) is an important organic and fine chemical raw material, which is widely used in medicine, chemical, textile, paper, automotive and household chemicals. Butanediol can also produce tetrahydrofuran (THF), polybutylene terephthalate (PBT), gamma butyrolactone (GBL), and methylpyrrolidone ( Important chemical materials such as 1-Methyl-2-pyrrolidone (NMP) and polyurethane resin (PU resin) and solvents. Tetrahydrofuran is an excellent solvent for many substances. It can dissolve polyethylene, vinylidene chloride, p-butylaniline, etc., and can be used as a solvent for polymerization and esterification. In addition to solvent applications, THF is mainly used to produce polytetramethyl ether glycol (PTMEG), and PTMEG can be used to prepare PU elastic fibers with diisocyanate. Γ-butyrolactone is an organic chemical raw material and pharmaceutical intermediate. In addition, GBL can also be used as an additive for lithium battery electrolytes.

In general, two aldehyde isomers, such as 4-hydroxybutanal and 2-methyl-3-hydroxypropanal, can be produced by hydroformylation of propylene alcohol, and the dialdehyde mixture is hydrogenated to produce 1 , 4-butanediol and 2-methyl-1,3-propanediol. In the hydrogenation reaction, it is preferred to carry a catalyst of nickel, ruthenium or osmium or Raney Nickel. The British patent No. 1493154 and the US patent No. 5426250 respectively carry out hydrogenation of a mixture of 4-hydroxybutyraldehyde-containing aldehydes using Raney nickel and nickel metal as catalysts, the reaction time is 6 to 8 hours, and the main product is 1,4- Butylene glycol, 2-methyl-1,3-propanediol and propanol. U.S. Patent No. 6,127,584 uses a metal ruthenium and rhodium as a catalyst, and a phosphorus compound is added to carry out a hydrogenation reaction of a mixture of 4-hydroxybutyraldehyde-containing aldehydes, and the product is 1,4-butanediol, 2-methyl-1. 3-propanediol and isobutanol.

U.S. Patent No. 4,665,205 proposes a process for the dehydration of 1,4-butanediol to THF using sulfuric acid as a catalyst. The conversion rate is close to 99.9%, but the sulfuric acid is highly corrosive and increases the cost of the process equipment. Japanese Patent No. 481075 proposes a method using alumina as a catalyst. The method requires vaporization of butanediol and subsequent gas-solid phase reaction at 250 ° C. The disadvantage of the reaction is that the catalyst treatment efficiency is low, resulting in an increase in production cost. U.S. Patent No. 2008/0161585 and Chinese Patent No. 101386610 respectively propose the use of solid heteropolyacids and zeolites as catalysts for the dehydration of butanediol in a liquid phase reaction, which also has the problems of low catalyst treatment capacity and short life.

Γ-butyrolactone is produced by dehydrogenation of 1,4-butanediol, and the catalyst for dehydrogenation reaction is a metal oxide containing active components such as copper, platinum, chromium, zinc, calcium, etc., and the usable carrier is active. Carbon, graphite, etc. Japanese Patent No. 3232874 produces γ-butyrolactone by dehydration of 1,4-butanediol with a Cu-Cr-Ba composite metal oxide, and the conversion rate is 96.1%, and the selectivity is 95.1%. European Patent No. 0584408 proposes a Cu-Cr-Ba or Cu-Cr-Mn-Ba composite metal oxide catalyst, and an alkali metal Na or K is added to the catalyst to carry out a gas phase reaction in a fixed bed reaction. And the selection rate can reach 91% and 94% respectively. Chinese Patent No. 1562473 proposes a Cu-Zn-Ce metal oxide containing no Cr as a catalyst, and the conversion rate is higher than 98%, and the selectivity is 95%.

U.S. Patent No. 6,414, 347, the disclosure of which is incorporated herein by reference to U.S. Patent No. 4,642, 473, the entire disclosure of the present invention for the production of 1,4-butanediol and γ-butyrolactone. The aldehyde mixture of butyraldehyde continues to be homogeneously reacted under toluene solvent and hydrogen pressure to produce 1,4-butanediol, γ-butyrolactone and 2-methyl-1,3-propanediol, followed by extraction with water. And leave the catalyst in toluene. However, in the above method, since γ-butyrolactone is easily soluble in toluene, γ-butyrolactone in the toluene solution needs to be additionally recovered, resulting in an increase in energy consumption and catalyst loss.

In order to improve the efficiency of 1,4-butanediol co-production of its derivatives, simplify the manufacturing process, and improve the shortcomings of U.S. Patent No. 6426437, there is still a need to develop a co-production of 1,4-butanediol, γ-butyrolactone. And a method of tetrahydrofuran to simplify the production process, facilitate the separation of the catalyst, and increase the yield of γ-butyrolactone and/or tetrahydrofuran.

Accordingly, the present invention provides a method for co-production of 1,4-butanediol, γ-butyrolactone, and tetrahydrofuran, comprising: hydrogenating a mixture of 4-hydroxybutyraldehyde-containing aldehydes in the presence of a heterogeneous catalyst .

The present invention provides a heterogeneous catalyst comprising an inert support and a first active metal and a second active metal supported on the inert support.

In the present invention, 1,4-butanediol and its derivatives are produced from a mixture of aldehydes containing 4-hydroxybutanal under hydrogen conditions in the presence of a heterogeneous catalyst. In particular, the heterogeneous catalyst is a core-shell heterogeneous catalyst, and the first active metal and the second active metal constitute a core of the core-shell heterogeneous catalyst, and the inert support constitutes a shell of the core-shell heterogeneous catalyst.

In a specific embodiment, the first active metal is selected from the group consisting of ruthenium or osmium; and the second active metal is selected from the group consisting of iron, palladium, platinum, copper or chromium. Further, the material of the inert support is not particularly limited as long as it does not react with a mixture of aldehydes containing 4-hydroxybutanal, and usually the inert support system is selected from SiO ₂ , Al ₂ O ₃ or Zr _{2 .} O ₃ . Further, the weight ratio of the first active metal to the second active metal is from 4:1 to 1:1.

The aforementioned aldehyde mixture further includes 2-methyl-3-hydroxypropanal and propionaldehyde, and the hydrogenation reaction is carried out in the presence of water. Among them, 4-hydroxybutanal in the aldehyde mixture can produce 1,4-butanediol and derivatives γ-butyrolactone and tetrahydrofuran, which can be prepared from 2-methyl-3 hydroxypropanal in the aldehyde mixture. 2-Methyl-1,3-propanediol and its derivative isobutanol are obtained, and propanol can be obtained from propionaldehyde in the aldehyde mixture.

In the present invention, the heterogeneous catalyst is added in an amount of 0.1 to 5% by weight, preferably 0.4 to 2% by weight based on the total weight of the reaction liquid; the reaction temperature is between 150 and 250 ° C, preferably between 180 and 220 Between ° C; the reaction pressure is between 200 and 1500 psig, preferably between 250 and 500 psig.

The invention can be applied to batch process and continuous process, including Continuous Stirred Tank Reactor (CSTR), Packed Bed Reactor, Fluidized Bed Reactor and the like.

The method of the present invention can produce 1,4-butanediol by using the heterogeneous catalyst of the present invention, and increase the yield of γ-butyrolactone and/or tetrahydrofuran, especially when the reaction time is increased to 12 hours, and γ can be further raised. - Yield of butyrolactone and / or tetrahydrofuran. Furthermore, the yield of γ-butyrolactone can also be increased at a suitable weight ratio of the first active metal to the second active metal of from 4:1 to 1:1 and at a temperature. Further, the use of the heterogeneous catalyst of the present invention simplifies the production process and has the advantage that the catalyst is easily separated. In addition, since the method of the present invention can be carried out in water, it is only necessary to recover γ-butyrolactone in the aqueous phase, and it is not necessary to simultaneously recover γ-butyrolactone in the organic phase and the aqueous phase as in the prior art, so In addition to the simplification of the steps, the present invention does not require the treatment of the organic phase, and the loss of the catalyst which is soluble in the organic phase.

The features and effects of the present invention are further illustrated by the following examples, which are not intended to limit the scope of the invention.

The conversion rates and yields described in this specification are calculated according to the following equation:

Conversion rate = [addition amount of aldehyde compound - residual amount of aldehyde compound after reaction] (mol) / amount of aldehyde compound added (mol)]

Yield = product formation amount (mol) / [aldehyde compound addition amount - residual amount of aldehyde compound after reaction] (mol)

Determination of catalyst metal content: The catalyst was boiled and nitrated by aqueous solution of nitric acid (1 wt%), and then formulated with 0.1 wt% Ru standard (Fluke), 0.1 wt% Fe standard (Aldrich), 0.1 wt% Pd standard (Fluke). A standard solution having a metal concentration of about 0.1% by weight is used to calibrate the metal calibration lines of the atomic absorption spectrometer to measure the metal content of the catalyst after nitrification.

Example 1

(1) Catalyst preparation

0.236 g of cerium chloride and 0.078 g of ferric nitrate were dissolved in 15 ml of deionized water, and 1.28 g of the polymer stabilizer polyvinylpyrrolidone was added, followed by the addition of reducing agent 0.52 ml of formaldehyde (please provide the amount of each compound added). Stir well in an alkaline environment, dissolve it, then wash with acetone, remove the black colloidal solution and dry. After the drying was completed, it was mixed with 5.735 ml of deionized water, 1.695 ml of ammonia water, and 33.215 ml of ethanol to be mutually miscible, and then 2.675 g of a template tetraethyl oxoxane (TEOS) was added, and the mixture was stirred for 24 hours to remove the black colloid. The solution was dried. Then, it is calcined in an air atmosphere at 400 ° C for 3 hours, and then calcined in a mixed atmosphere of argon and hydrogen for 3 to 5 hours, so that the desired inert support is cerium oxide and the weight ratio of Ru/Fe is 4:1. Catalyst. The catalyst was nitrated by nitric acid, and the metal content ratio of the catalyst was determined by atomic absorption spectroscopy to be 4:1.

(2) Hydrogenation reaction

The catalyst having a weight ratio of Ru/Fe of 4:1 was placed in a hydrogenation reactor, and the composition of the reaction liquid was 15.1% by weight of 4-hydroxybutyraldehyde and 3.6% by weight of 2-methyl-3-hydroxypropanal. 1.3 wt% of propionaldehyde (50 ml) having a water content of 80 wt% and a catalyst concentration of 0.4 wt%. The reaction temperature was controlled to 200 ° C and the pressure was set to 400 psig with hydrogen. Samples were taken at a reaction time of 3 hours, and the samples were analyzed by gas chromatography. The results are shown in Table 1.

Comparative example 1

50 ml of the reaction solution and Raney nickel catalyst were placed in a hydrogenation reactor, and the composition of the reaction liquid was 15.1 wt% of 4-hydroxybutyraldehyde, 3.6 wt% of 2-methyl-3-hydroxypropanal, and 1.3 wt% of C. The aldehyde was controlled to a reaction temperature of 200 ° C and pressurized to 400 psig with hydrogen. Samples were taken at a reaction time of 3 hours, and the samples were analyzed by gas chromatography. The results are shown in Table 1.

According to the results of the first experiment, the yield of γ-butyrolactone was improved as compared with Comparative Example 1. In addition, the present invention produces tetrahydrofuran as compared to U.S. Patent No. 6,426,473, and simplifies the process to avoid depletion of the catalyst.

Example 2

The catalyst preparation of Example 1 was repeated. The catalyst of Example 1 was subjected to a hydrogenation reaction test, and the reaction temperature was adjusted to 220 °C. From the experimental results in Table 2, as the reaction temperature increases, the yields of γ-butyrolactone and tetrahydrofuran increase significantly.

Example 3

The catalyst preparation of Example 1 was repeated. The hydrogenation reaction test was carried out using the catalyst of Example 1. The reaction pressure was adjusted to 300 psig. From the experimental results in Table 3, lowering the reaction pressure is beneficial to increase the yield of γ-butyrolactone.

Example 4

The catalyst preparation of Example 1 was repeated, and the amount of ruthenium chloride and iron nitrate was adjusted to obtain a catalyst having a Ru/Fe weight ratio of 2:1. The hydrogenation reaction test of Example 1 was carried out using this catalyst. The results are shown in Table 4.

Example 5

The catalyst preparation of Example 1 was repeated, and ferric nitrate was replaced with palladium nitrate to prepare a catalyst having a Ru/Pd weight ratio of 4:1. The hydrogenation reaction of Example 1 was carried out at 500 psig of the catalyst, and the results are shown in the table. Fives.

Example 6

The procedure of Example 5 was repeated to increase the reaction time to 12 hours, and the reaction results are shown in Table 5.

From the results of Table 5, the adjustment of the second active metal to Pd can increase the yield of tetrahydrofuran, and the yield can be further increased to 22.4% by prolonging the reaction time.

Claims (18)

A method for co-producing 1,4-butanediol, γ-butyrolactone and tetrahydrofuran, comprising: hydrogenating a mixture of 4-hydroxybutyraldehyde-containing aldehydes in the presence of a heterogeneous catalyst, wherein the heterogeneous catalyst comprises An inert support and a first active metal and a second active metal supported on the inert support. The method for co-producing 1,4-butanediol, γ-butyrolactone and tetrahydrofuran according to claim 1, wherein the heterogeneous catalyst is a core-shell heterogeneous catalyst, and the first active metal and the second active agent The metal constitutes the core of the core-shell heterogeneous catalyst, which constitutes the shell of the core-shell heterogeneous catalyst. A method of co-producing 1,4-butanediol, γ-butyrolactone, and tetrahydrofuran according to claim 1, wherein the first active metal is selected from the group consisting of ruthenium or osmium. A method of co-producing 1,4-butanediol, γ-butyrolactone and tetrahydrofuran according to claim 1, wherein the second active metal is selected from the group consisting of iron, palladium, platinum, copper or chromium. A method of co-producing 1,4-butanediol, γ-butyrolactone, and tetrahydrofuran according to claim 1, wherein the inert support system is selected from the group consisting of SiO ₂ , Al ₂ O ₃ or Zr ₂ O ₃ . The hydrogenation reaction is carried out at 150 to 250 ° C according to the method of co-production of 1,4-butanediol, γ-butyrolactone and tetrahydrofuran in the first paragraph of the patent application. The hydrogenation reaction is carried out at 180 to 220 ° C according to the method of co-production of 1,4-butanediol, γ-butyrolactone and tetrahydrofuran in the sixth paragraph of the patent application. The hydrogenation reaction is carried out at a pressure of from 200 to 1500 psig as in the method of co-production of 1,4-butanediol, γ-butyrolactone and tetrahydrofuran in the first paragraph of the patent application. The hydrogenation reaction is carried out at a pressure of from 250 to 500 psig as in the method of co-production of 1,4-butanediol, γ-butyrolactone and tetrahydrofuran of claim 8 of the patent application. The method for co-producing 1,4-butanediol, γ-butyrolactone and tetrahydrofuran according to claim 1, wherein the weight ratio of the first active metal to the second active metal is 4:1 to 1: 1. A method for co-producing 1,4-butanediol, γ-butyrolactone and tetrahydrofuran according to claim 1, wherein the aldehyde mixture further comprises 2-methyl-3hydroxypropanal and propionaldehyde. A method of co-producing 1,4-butanediol, γ-butyrolactone, and tetrahydrofuran according to claim 1, wherein the hydrogenation reaction is carried out in the presence of water. A heterogeneous catalyst comprising: an inert support; and a first active metal and a second active metal supported on the inert support. The heterogeneous catalyst according to claim 13, wherein the heterogeneous catalyst is a core-shell heterogeneous catalyst, and the first active metal and the second active metal constitute a core of the core-shell heterogeneous catalyst, and the inert carrier constitutes the catalyst The shell of a core-shell heterogeneous catalyst. The heterogeneous catalyst of claim 13, wherein the first active metal is selected from the group consisting of ruthenium or osmium. The heterogeneous catalyst of claim 13, wherein the second active metal is selected from the group consisting of iron, palladium, platinum, copper or chromium. The heterogeneous catalyst of claim 13, wherein the inert support system is selected from the group consisting of SiO ₂ , Al ₂ O ₃ or Zr ₂ O ₃ . The heterogeneous catalyst of claim 13, wherein the weight ratio of the first active metal to the second active metal is from 4:1 to 1:1.