JPH02233632A - Production of 1,4-butanediol - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as a raw material for polyurethane resin, etc., in high efficiency and yield at a low cost under low pressure in one step with simplified production process by carrying out catalytic hydrogenation of maleic anhydride, etc., in vapor phase using a specific solid catalyst. CONSTITUTION:The objective compound useful as a raw material for polybutylene terephthalate resin, etc., can be produced by the catalytic hydrogen ation of maleic anhydride and/or succinic anhydride with H2 gas in the presence of a solid catalyst containing Cu and Mn preferably in a solvent such as gamma- butyrolactone at 170-280 deg.C under a pressure of 10-100kg/cm<2>G at a G.H.S.V of 1,000-100,000hr<-1> in vapor phase. The solid catalyst used in the present process is usually produced by reducing a metal oxide catalyst consisting of copper oxide - manganese oxide before use. For example, CuO - MnO2 is reduced by refluxing with an H2-containing N2 gas at a G.H.S.V of 2,400hr<-1> at 170-200 deg.C under a pressure of several tens kg/cm<2>. The facility cost and operation cost can be reduced by this process.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a process for producing 1,4-butanediol, and more particularly, maleic anhydride and/or succinic anhydride are treated with catalytic hydrogen in the gas phase in the presence of a catalyst. The present invention relates to a method for producing 1,4-butanediol.

BACKGROUND OF THE INVENTION 1. 4-Butanediol is a compound useful as a raw material for polybutylene terephthalate resins, polyurethane resins, and the like. Therefore, the development of an inexpensive and efficient method for producing i4-butanediol is strongly desired.

Heretofore, the following methods have been disclosed as methods for producing T-butyrolactone or 1,4-butanediol by catalytic hydrogenation of maleic anhydride and/or succinic anhydride or derivatives thereof.

(a) Process for producing T-butyrolactone by catalytically hydrogenating maleic anhydride or succinic anhydride in the gas phase using a zinc-copper-chromium catalyst (Japanese Patent Publication No. 44-32567
Publication No.).

(mouth) maleic anhydride and/or succinic anhydride,
In the presence of copper oxide perylium monoxide zinc monoxide reduction catalyst,
A method for producing γ-butyrolactone by catalytic hydrogenation in the gas phase (Japanese Patent Publication No. 47-23294).

<<8>> Process for producing 1,4-butanediol by hydrogenating maleic anhydride and/or maleic acid in the liquid phase in the presence of a catalyst containing an element or compound of subgroup ■ and subgroup Publication No. 51-133212).

(2) A method for producing 1,4-butanediol by hydrogenolyzing maleic acid diester or fumaric acid diester in the presence of a copper chromite catalyst in the gas phase (JP-A-61-22035) , special publication 1986-501702
Publication No.) etc.

The present inventors also promoted a method for producing 1,4-butanediol by carrying out catalytic hydrogenation of maleic anhydride and/or succinic anhydride in the gas phase in the presence of a copper oxide zinc monoxide catalyst. I am worried (Special application 1986 3-1 7 5 0
6 No. 2).

Problems to be Solved by the Invention However, the manufacturing method disclosed above had the following problems. That is, in the methods of catalytically hydrogenating maleic anhydride and/or succinic anhydride in the gas phase in the presence of a catalyst, only r-butyrolactone is produced, which does not meet the objective. Do 1
．． There was a problem that 4-butanediol could not be obtained. In addition, in a method of hydrogenating maleic anhydride and/or maleic acid in the liquid phase in the presence of a catalyst, about 2
There was a problem in that a high pressure of 0.00 kg/cd was required, and therefore a huge amount of equipment and operating costs were required. Furthermore, the method of hydrogenolyzing maleic acid diester etc. in the gas phase in the presence of a catalyst does not require the high pressure mentioned above, but requires a step to diesterize maleic anhydride, making the process extremely complicated. There was a problem with becoming. In other words, since the reaction of converting a monoester to a diester is an equilibrium reaction, two reaction steps are required for the reaction to proceed sufficiently, and if the monoesterification step is included, three additional reaction steps are required. is necessary.

Further, conventionally, there has been no known method for producing 1,4-butanediol by subjecting maleic anhydride and/or succinic anhydride to catalytic hydrogenation in the gas phase.

The present invention aims to solve the problems associated with conventional techniques such as high equipment and operating costs and complicated processes when producing 1,4-butanediol from maleic anhydride and/or succinic anhydride. and 1,4
- The purpose of the present invention is to provide an inexpensive and efficient method for producing butanediol.

Means for Solving the Problems Summary of the Invention The present inventors have disclosed that 1,4-butanediol is produced by directly hydrogenating maleic anhydride and/or succinic anhydride under low pressure without going through a diester. We considered that there would be great benefits if we could do this, and we investigated various gas phase hydrogenation methods.

Furthermore, the reason why only T-butyrolactone has conventionally been obtained through gas phase hydrogenation of maleic anhydride and/or succinic anhydride is that in both cases the reaction is carried out at a low hydrogen/raw material ratio and near normal pressure. When the hydrogenation reaction was carried out at a higher hydrogen/raw material ratio than before and under pressure within a range that could maintain the gas phase, it was discovered that 1,4-butanediol could be produced in high yield, and the present invention was completed. I ended up doing it.

That is, the present invention provides a method for producing 1,4-butanediol by catalytically hydrogenating maleic anhydride and/or succinic anhydride, in which the reaction is carried out in the gas phase in the presence of a catalyst containing copper and manganese. The present invention relates to a characteristic method for producing 1,4-butanediol.

Catalyst The catalyst used in the present invention is usually a previously reduced copper oxide manganese monoxide catalyst.

Such a catalyst can be made by dissolving a copper compound such as copper nitrate and a manganese compound such as manganese nitrate in water, and adding a sodium carbonate aqueous solution dropwise to the solution while stirring with heating until the solution becomes neutral. is collected by filtration, dried,
After passing through the firing process, it is prepared by molding into a predetermined shape using a molding machine. This preparation method yields a copper oxide manganese monoxide catalyst.

In the reduction of the catalyst of the present invention, for example, nitrogen gas containing 2% by volume of hydrogen is applied to the catalyst to reduce the gas hourly space velocity (G.H, S.V, hereinafter referred to as G, H) at room temperature and normal pressure. , S.
V. All values are expressed at room temperature and pressure. ) 170 under a pressure of several tens of kg/cd G at about 2400 hours-1
After circulating for one day and night at ℃, the hydrogen concentration was gradually increased to 10
The treatment is carried out by circulating the catalyst at a catalyst bed temperature of 200° C. for several hours at a concentration of 0% by volume.

Solvent The solvent used in the present invention is not particularly limited, but for example, T-butyrolactone, tetrahydrofuran, dimethyl ether, diethyl ether, 1,4-dioisane, etc. are used. Among these, T-butyrolactone is a good solvent for maleic anhydride and succinic anhydride, and is also a hydrogenation product. It is particularly preferred because it is considered to be an intermediate for Further, a solvent may not be used.

Contact Conditions The contact between the mixed gas of maleic anhydride and/or succinic anhydride and hydrogen gas and the catalyst can be appropriately selected from conventionally known methods. For example, a method of contacting the mixed gas with the contact using a fixed bed method, a method of bringing the mixed gas into contact with the contact using a moving bed method, a method of bringing the mixed gas into contact with the contact using a fluidized bed method, etc. can be adopted. Further, depending on the case, the mixed gas and the catalyst may be brought into contact in a batch manner.

The contact time between the mixed gas of maleic anhydride and/or succinic anhydride and hydrogen gas and the catalyst is determined by G, H, S. V.
t'1 0 0 0 ~ 1 0 0 0 0 0 h-1
, preferably about 1,500 to 20,000 hours.

The reaction temperature in the present invention is about 170 to 280°C, the reaction pressure is about 10 to 100 kg/catG, and the molar ratio of hydrogen gas to maleic anhydride and/or succinic anhydride is about 50 to 1500. It is. The reaction temperature, reaction pressure, and hydrogen gas/raw material molar ratio are appropriately selected from within a range that allows the system to be kept in the gas phase.

However, if the hydrogen gas/raw material molar ratio is less than 50, the reaction rate will drop and catalyst deterioration will occur due to the formation of carbonaceous substances, while if it exceeds 1500, a large amount of hydrogen will have to be recycled, making it uneconomical. Both are disadvantageous and undesirable.

Effects of the Invention According to the method of the present invention, 1,4-butanediol can be obtained in high yield from maleic anhydride and/or succinic anhydride in a one-step reaction.

Furthermore, since the diesterification step of maleic anhydride and/or co/% citric acid anhydride is not involved, the process can be significantly simplified. Furthermore, compared to liquid phase hydrogenation technology, 1,4-butanediol can be produced under much lower pressure, resulting in the effect of reducing equipment costs and operating costs.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Copper, manganese, potassium as metals each 15.3
A fixed bed reactor (15 mmφ
600mm) and 40kg/Cvl in a nitrogen stream.
It was heated to 170°C while pressurizing it to G. After that, nitrogen. Hydrogen was gradually added to the bare gas stream to produce nitrogen gas containing 2% by volume of hydrogen at 40 kg/cafG, 170
°C, G, }l. S. V, 2400 h-1 overnight circulation. Furthermore, while being careful not to let the catalyst bed temperature exceed 200°C, the hydrogen concentration was gradually increased to 100% by volume hydrogen, 40 kg/cnfG, 200°C,
G, I{. S, V. Reduction treatment was performed for 2 hours at 2400 hours-1.

After heating the above fixed bed reactor to 230°C, a T-butyrolactone solution of maleic anhydride (maleic anhydride/γ
-7tyrolactone = 1/1 molar ratio) and hydrogen per mol of the sum of maleic anhydride and T-butyrolactone.
00 moles under a pressure of 40 kg/cnfG. H.
S. V. It was distributed under the conditions of 7200 h-1. The product was analyzed by gas chromatography, and product identification was performed by GC-MS.

As a result, the conversion rate of maleic anhydride was 100 mol%, 1,4-butanediol was 67.2 mol%, and tetrahydrofuran was 5.4 mol%, based on the supplied maleic anhydride.
mol% and n-butanol were produced at 4.8 mol%.

In addition, a small amount of n-propanol was produced, but succinic anhydride was not detected in the product.

Example 2 Pressure during catalyst reduction treatment and reaction pressure were set to 15 kg/c
nG, reaction temperature 210°C, molar ratio of maleic anhydride and γ-butyrolactone 1/3, G, H. S. V. 3
The reduction treatment of the catalyst and the production of -,41-butanediol were carried out in the same manner as in Example 1, except that the reaction time was 200 hours-1.

As a result, the conversion rate of maleic anhydride was 100 mol%, 1,4-butanediol was 70.6 mol%, and tetrahydrofuran was 4.8 mol%, based on the supplied maleic anhydride.
mol % and n-butanol were produced at 6.4 mol %.

Incidentally, succinic anhydride was not detected in the product.

Example 3 Copper and manganese as metals are 22% by weight and 5% by weight, respectively.
Catalyst reduction treatment and production of 1,4-butanediyl oxide were carried out in the same manner as in Example 2, except that a commercially available copper manganese oxide catalyst containing 0% by weight (trade name N140, manufactured by Nissan Girdler) was used. I did it.

As a result, the conversion rate of maleic anhydride was 100 mol%, 1,4-butanediol was 22.4 mol%, and tetrahydrofuran was 1.8 mol%, based on the supplied maleic anhydride.
Mol% and n-butanol are 0. 8 mol% was produced. Incidentally, succinic anhydride was not detected in the product.

Example 4 Copper nitrate (Cu(NO.)2-3H*0) 4 8.
3 2 g and manganese nitrate (Mn(Nroa) 2”6
114.83g of Lb) was dissolved in 600mg of water.

While keeping this solution at 70-75°C, add 1 mol/g of the solution while stirring.
A sodium carbonate aqueous solution with a concentration of i is added, and the pH of the solution is 7.
The solution was added dropwise until the temperature reached 1, and then stirring was continued for 90 minutes while maintaining the temperature at about 80°C. After cooling, the obtained solid was filtered and heated to 60°C.
Washing was carried out using about 10 liters of hot water. Next, dry at 120℃ for 12 hours while blowing air, and then dry for 4 more hours.
After firing at 00°C for 3 hours, 50g of solid was obtained. After molding and pulverizing this solid, 6 to 10 mesh pieces were sieved to obtain a solid catalyst consisting of copper oxide and manganese oxide. The metal content of copper and manganese in the obtained catalyst was 21.2% by weight and 40.6% by weight, respectively.

Using 15 cc of the catalyst prepared above, the catalyst was reduced and 1,4-butanediol was produced in the same manner as in Example 2.

As a result, the conversion rate of maleic anhydride was 100 mol%, 1,4-butanediol was 56.0 mol%, and tetrahydrofuran was 4.2 mol%, based on the supplied maleic anhydride.
mol % and n-butanol were produced in an amount of 10.4 mol %. Incidentally, succinic anhydride was not detected in the product.

Example 5 The catalyst was reduced and 1,4-butanediyl was produced in the same manner as in Example 2, except that maleic anhydride was replaced with succinic anhydride. A reaction product was obtained.

Example 6 Using the reduction catalyst used in Example 4, a solution of maleic anhydride in 1,4-dioxane (maleic anhydride/1,4-dioxane = 173 molar ratio) and hydrogen were added at a ratio of 800 to 1 mole of maleic anhydride. In mole ratio, 210℃, 40kg
Under pressure of /enfG, G, H, S, V, 1 6 0
It was distributed under conditions of 0 h-1.

As a result, the conversion rate of maleic anhydride was 100 mol %, and 92.1 mol % of 1,4-butanediol and 6.3 mol % of tetrahydrofuran were produced based on the supplied maleic anhydride and acid.

Incidentally, succinic anhydride was not detected in the product.

Example 7 Using the reduction catalyst used in Example 4 and without using a solvent, a mixed gas of maleic anhydride and hydrogen (1:600 molar ratio) was heated at 220° C. under a pressure of 60 kg/cdG (7). ．． H
．． S. V. It was distributed under the condition of 4800 hours-1.

As a result, the conversion rate of maleic anhydride was 100 mol%, 1,4-butanediol was 95.4 mol%, and tetrahydrofuran was 2 mol%, based on the supplied maleic anhydride.
．． 6 mol% was produced. Note that succinic anhydride was not detected in the product.

Example 8 Instead of T-butyrolactone solution of maleic anhydride,
Using a solution of maleic anhydride and succinic anhydride dissolved in T-butyrolactone (maleic anhydride/succinic anhydride/T-butyrolactone = 3/1/4 molar ratio), hydrogen was dissolved in maleic anhydride, succinic anhydride, and T-butyrolactone. Catalyst reduction treatment and reaction were carried out in the same manner as in Example 1, except that 200 moles were distributed per 1 mole of butyrolactone.

As a result, the conversion rate of maleic anhydride was 100 mol %, 1,4-butanediol was 70.4 mol %, and tetrahydrofuran was 6.0 mol %, based on the sum of maleic anhydride and succinic anhydride supplied. 5 mol% and n-butanol 3
．． 9 mol% was produced.

Claims (1)

[Claims] (1) A method for producing 1,4-butanediol by catalytic hydrogenation of maleic anhydride and/or succinic anhydride, characterized by carrying out the reaction in a gas phase in the presence of a catalyst containing copper and manganese. A method for producing 1,4-butanediol.