FI111458B - Process for the preparation of 1,4-butanediol - Google Patents

Abstract

In the proposed process for producing 1,4 butane diol, 2,5 dihydrofurane is reacted in a single step in the presence of water and hydrogen at a temperature of 20 to 300 DEG C and a pressure of 1 to 300 bar with the aid of a hydrogenating catalyst.

Description

111458

The present invention relates to a process for the preparation of 1,4-butanediol.

US-A-4,209,651 mentions that 2,5-dihydrofuran may be used to make 1,4-butanediol directly therefrom. But this patent does not mention the means by which this can be accomplished.

WO 92/20667, for its part, teaches a process for the preparation of 1,4-butanediol from 2,5-dihydrofuran by first isomerizing 2,5-dihydrofuran to 2,3-dihydrofuran in the presence of homogeneously dissolved rhodium or ruthenium / phosphine complexes, The 2,3-dihydrofuran is removed from the reaction mixture by distillation. The 2,3-dihydrofuran is then reacted with water in the presence of an acidic catalyst to form a mixture of 4-hydroxybutanal and 2-hydroxytetrahydrofuran which is hydrogenated in the presence of a hydrogenation catalyst to 1,4-butanediol. It is therefore a three-step process.

EP-A 24770 discloses a one-step preparation of 4-hydroxybutanal by reacting 2,5-dihydrofuran in the presence of a large amount of water with a catalyst containing a Group VIIIb metal of the Periodic Table of the Elements, which has been treated with a base before use. The yield is then only 55% and the seismic activity 65%, i.e. also relatively low, so that the reaction mixture must first be worked up by distillation before hydrogenation of 4-hydroxy-30 sibutyraldehyde to 1,4-butanediol.

US-A 4,859,801 teaches the reaction of 2,3-dihydrofuran, aldehyde and hydrogen in the presence of water at a pH of 8 to 14 and in the presence of a hydrogenation catalyst of 1,4-butanediol and 2-alkyl-1,4-butanediol. mixtures.

The yield of 1,4-butanediol is then modest. In order to convert 2,5-dihydrofuran by this method to 111458 2 into 1,4-butanediol, it must first be isomerized to 2,3-dihydrofuran in the reaction step preceding the reaction step described.

BE-A 674 652 teaches isomerization of 2,5-dihydrofuran to 2,3-dihydrofuran by means of the catalysts in Group VIIIb of the Periodic Table of the Elements.

Since all of the above processes require the use of a multistep reaction to convert 2,5-dihydrofuran to 1,4-butanediol and such a multistep process 10 becomes significantly expensive at an uncompetitive price for the process product 1,4-butanediol, it has been the object of the present invention to One-step preparation of 1,4-butanediol from 2,5-dihydrofuran with good yield and selectivity.

Accordingly, a process for the preparation of 1,4-butanediol has been found, which process is characterized in that the 2,5-dihydrofuran is reacted in one step with a hydrogenation catalyst at a temperature of 20 to 300 ° C and a pressure of 1 to 300 bar.

Thus, in the process of the invention, three reaction steps are a) isomerization of 2,5-dihydrofuran to 2,3-dihydrofuran according to Equation (1) 25

O --► O

o o b) Reaction of 2,3-dihydrofuran with water to a mixture of 4-hydroxybutyraldehyde and its isomer 2-hydroxytetrahydrofuran according to equation (2) and [===] ... M ». HO-CHs-CH2-Clfe-C + I (2 'i

N H <> '0H

111458 3 c) catalytic hydrogenation of a mixture of 4-hydroxybutyraldehyde and 2-hydroxytetrahydrofuran obtained according to equation (2) to 1,4-butanediol according to equation (3).

HD-CH3-Cfc-Cfla-C + [* 2- ». HO-CH-CH 3; -CH; -Ca2-OH

^ k Cat.

h 0 OH

¢ 3} is implemented in a single method step.

In carrying out the process of the invention, 2,5-dihydrofuran is generally reacted with water in a molar ratio of 2.5-10 dihydrofuran to water, generally 1: 1 to 1: 100, preferably 1: 1 to 1:50, and particularly preferably 1: 1 to 1:10, and in the presence of hydrogen and a hydrogenation catalyst at a pressure generally of from 1 to 300 bar, preferably from 5 to 200 bar and particularly generally from 10 to 150 bar at 20 to 300 ° C, preferably 15 to 40 to 230 ° C and particularly preferably 80 to 200 ° C. butanediol.

In the process of the invention, any catalyst suitable for the hydrogenation of carbonyl groups can generally be used as hydrogenation catalysts. Both hydrogenation catalysts soluble in ho-20 mogenically reaction medium, such as those described, for example, in Hou-ben-Weyl, Methoden der Organischen Chemie, Vol. IV / le, p.

45-67, Thieme Verlag, Stuttgart 1980, or also heterogeneous hydrogenation catalysts as described in Houben-Weyl, Methoden der Organischen Chemie, Vol. IV / 1c, pp. 16-26. Particularly preferred homogeneous catalysts are complexes formed with rhodium, ruthenium and cobalt with phosphine or phosphite ligands, the preparation of which is described, for example, in CA-A 30727641, H. Brunner, Hartley, The Chemistry of the Metal-Carbon Bond, vol. 5, pp. 110-124, John Wiley & Sons, New York 1989 and Toth et al., Inorg. Chim. Acta, 42, 153 (1980) and the literature cited therein.

111458 4

However, the process of the invention preferably uses heterogeneous hydrogenation catalysts, i.e., hydrogenation catalysts which are substantially insoluble in the reaction medium. These hydrogenation catalysts are preferably those containing one or more elements of groups Ib, VIb, VIIb and VIIb of the Periodic Table of the Elements, in particular copper, chromium, molybdenum, tungsten, rhenium, ruthenium, cobalt, rhodium, iridium, iridium, iron and / or platinum.

In the process of the invention, heterogeneous hydrogenation catalysts consisting of metals in activated, finely divided and high surface area, for example, raney nickel, raneycobalt, palladium, platinum or rhenium, can be used.

Further, in the process of the invention, for example, so-called. saostuskatalyyttejä. Such catalysts may be prepared by precipitating their catalytically active components from their saline solutions, in particular from their solutions of nitrates and / or acetates, for example by adding alkali metal and / or alkaline earth metal hydroxide solutions and / or carbonate solutions, for example, as sparingly soluble carbonates, then drying the resulting precipitates and then converting them by calcining generally at a temperature of 300-700 ° C, particularly 400-600 ° C. oxides, mixed oxides and / or mixed oxides which, by treatment with hydrogen or hydrogen-containing gases, are generally reduced at a temperature of 100 to 700 ° C, in particular 150 to 400 ° C. into metals and / or oxide compounds on the lower oxidation stage and converted to the actual catalytically active form. In this case, it is usually necessary to reduce the amount of water to completion. In the preparation of the precipitation catalysts containing the carrier material, the precipitation of the catalytically active component pathways can occur. in the presence of a carrier material. However, the catalytically active components may, however, also be precipitated preferably with the support material of the present invention. salt solutions.

The process of the invention preferably uses hydrogenation catalysts containing hydrogenated lysing metals or metal compounds precipitated on a carrier material. In addition to the above-mentioned precipitation catalysts, which contain not only the catalytic active components but also the carrier material, carrier catalysts in which the catalytic hydrogenating components are added to the support material, for example by impregnation, are generally suitable in the process of the invention.

The manner in which catalytically active metals are added to the support is generally not critical and can be accomplished by a variety of means. Catalytically active metals may be added to these carrier materials, for example, by impregnation with the appropriate materials. solutions or suspensions of the salts or oxides of the elements, followed by drying and reduction of the metal compounds of the present invention. lower oxidation metals or compounds by the use of a baconizer, preferably hydrogen or hydride complexes. Another possibility for adding catalytically active metals to these carriers is to impregnate solutions of thermally degradable salts, for example, nitrates of catalytically active metals or complex solutions of thermally degradable complexes such as carbonyl or hydride complexes, to heat the adsorbed carriers to 300 ° . This thermal decomposition is preferably carried out in a shielding gas. Suitable shielding gases include, for example, nitrogen, carbon dioxide, hydrogen or noble gases. Further, the catalytically active metals may be precipitated on the catalyst support by evaporation or flame spraying. The concentration of catalytically active metals in these carrier catalysts is not, in principle, critical to the success of the process of the invention. It will be apparent to those skilled in the art that higher concentrations of catalytically active metals in these support catalysts result in higher thi / a / time yields than lower concentrations. However, carrier catalysts containing from 1 to 80% by weight, preferably from 0.5 to 30%, by weight of the total metal catalyst active catalysts are generally used. Since these concentration values are calculated from the total amount of catalyst and support material, but the density and specific surface area of the various support materials are very different, these values can be lowered or exceeded without adversely affecting the results obtained by the process of the invention. Of course, several catalytically active metals may also be added to the particular support material. The catalytically active metals may additionally be added to the carriers, for example, by the methods described in DE-A-2 519 817, EP-A 1 477 219 and EP-A 285 420. In the catalysts according to the above publications, catalytically active metals are alloys which has been prepared by heat treatment and / or reduction, for example, by absorption of precipitated salts or complexes of the above metals.

The precipitation catalysts and also the support catalysts can also be activated in situ in the reaction mixture by the presence of hydrogen, but these catalysts are preferably activated separately before use.

Suitable carrier materials are generally aluminum and titanium oxides, zirconium dioxide, silica, diatomaceous earth, silica gel, clay soils such as montmorillonite 30s, silicates such as magnesium or aluminum silicates, zeolites such as ZSM-5 or ZSM-10, activated carbon. Preferred carrier materials are alumina, titanium dioxide, zirconium dioxide and activated carbon. Of course, mixtures of different carrier materials can also serve as carriers for the catalysts useful in the process of the invention.

111458 7

Examples of heterogeneous catalysts useful in the process of the invention include the following catalysts:

Platinum Black, Platinum Activated Carbon, Platinum Dioxide, Palladium Activated Carbon, Palladium Silica, Palladium Barium Sulfate, Rhodium Activated Carbon, Rhodium Aluminum, Ruthenium Silica, Carboxylic Acid, Ruthenium Silica, , rhenium black, raneyrenium, rhenium on activated carbon, rhenium / palladium on activated carbon, rhenium / platinum on activated carbon, copper on silica, copper on alumina, copper on activated carbon, ranei copper on platinum oxide and rhodium oxide alloy, platinum / palladium on activated carbon, copper , di-rhenium heptoxide (Re 217), cobalt sulfide, nickel sulfide, molybdenum (VI) sulfide, copper / molybdenum (VI) oxide / silicon

dioxide / alumina catalysts, as well as DE-A 20 3 932 332, US-A 3 449 445, EP-A 44 444, EP-A 147 219, DE-A

3 904 083, DE-A 2 321 101, EP-A 415 202, DE-A 2 366 264 and EP-A 100 406.

Lewis and / or Brönsted acidic components such as zeolites, aluminum or silicon oxides, phosphoric acid or sulfuric acid may be added to the above catalysts. Their addition amounts are generally 0.01 to 5% by weight, preferably 0.05 to 0.5% by weight, and particularly preferably 0.1 to 0.4% by weight, based on the weight of the catalyst used.

The process of the invention is particularly preferably carried out using hydrogenation catalysts having Brönsted and / or Lewis acid centers. When using such catalysts, it is generally not necessary to add Brönsted or Lewis acid as an additive to the reaction mixture.

Bronsted acid centers containing homogeneous cat-lytic cells include, for example, transition metal complexes of metals of the VHIb group, in particular rhodium, ruthenium and cobalt containing complexes containing phosphine or 111458 8 phosphite ligands, substituted with Bronstedic acid, or phosphonic acid groups, for example complexes formed by said transition metals and triphenylphosphine-p-sulfonic acid ligands. Such ligands can be prepared, for example, by Angew. Chem. 105, 1097 (1993).

In the process of the invention, particularly advantageous results can be obtained with heterogeneous catalysts having Brönsted or Lewis acid centers. For example, the Brönsted and Lewis acid centers can serve as catalytic active metals themselves, provided they are not completely reduced. when activated into metals, the catalyst is hydrogen or hydrogen-containing gases. This applies, for example, to rhenium and chromite-containing catalysts such as rhenium black and copper chromite. In rhenium black, rhenium is a mixture of a rhenium metal and a higher degree of oxidation of rhenium compounds, whereby, for example, a Bröns-20 ted or Lewis acid effect can occur. In addition, such Lewis or Brönsted acid centers can be added to the support material used in the catalyst. Suitable carrier materials containing Lewis or Brönsted acidic centers include, for example, alumina, titanium dioxide, zir-25 conium dioxide, silica, silicates, clay soils, zeolites and activated carbon.

Thus, in the process of the invention, carrier catalysts containing the elements of the side groups I, VI, VII and / or VIII of the Periodic Table of the Elements, in particular the Bronnsted or Lewis Elements of the Periodic Table of the Elements of the Periodic Table of the Elements, are particularly preferred as hydrogenation catalysts. acid carrier material. Particularly preferred catalysts are, for example, rhenium on activated carbon, rhenium on zirconium dioxide, rhenium on titanium dioxide, re 111458 9 nium on silica, copper on activated carbon, copper on silica and ruthenium on activated carbon.

The method according to the invention can be implemented both continuously and batchwise. For continuous operation, for example, tubular reactors can be advantageously used, in which the catalyst is preferably in the form of a solid bed, over which the reaction mixture can be fed through a base or by draining. For batch operation, both simple mixing reactors and preferably loop reactors can be used. When using the loop reactors, the catalyst is suitably in the form of a solid bed. If the starting material reacts incompletely, this may conveniently be returned to the re-reaction either by distillation of the precious products or by fractional flow with other reaction products. This may be an advantage, especially for continuous operation. The yields of 1,4-butanediol are generally higher for continuous operation than for batch reaction with the same catalyst.

The process of the invention can be carried out preferably under reaction conditions in the presence of an inert solvent, examples of which are water soluble ethers such as tetrahydrofuran, dioxane or dimethoxymethane. Alcohols, in particular 1,4-butanediol, may also be advantageously used as a solvent.

The reaction product of the process of the invention is suitably subjected to distillation to yield, in addition to the 1,4-butanediol of the process product, small amounts of the by-products of tetrahydrofuran, γ-butyrolactone and butanol as valuable products.

The starting material 2,5-dihydrofuran can be prepared by isomerizing vinyloxirane, for example, according to the method described in US-A 5,034,545 or US-A 5,082,956.

Large quantities of 1,4-butanediol are manufactured worldwide and serve as a diol component in the manufacture of polyesters, polyurethanes and epoxy resins, among others.

eXAMPLES

Example 1 In a 25 ml tubular reactor was charged 25 ml of catholyte consisting of 4 mm copper plated silica filaments. The copper content of the catalyst was 10% by weight based on the total weight of the catalyst. The catalyst was prepared by impregnating the silica strands with 10 ammonium carbonate / sodium nitrate solution and then drying at 100 ° C. The catalyst was activated by heating for 2 hours at 250 ° C under a hydrogen atmosphere (100 L H2 / h). A mixture of 2.8 parts by weight of 2,5-dihydrofuran, 2.8 parts by weight of water and 1 part by weight of 1 was then passed continuously over the catalyst under a hydrogen pressure of 120 bar and a reactor temperature of 134 ° C. 4-dioxane.

The composition of the leaving reaction mixture is shown in the table.

Example 2 In a similar manner to Example 1, a mixture of 2,5-dihydrofuran, water and 1,4-dioxane as described in the Example was reacted under a hydrogen pressure of 120 bar and at 200 ° C in the presence of a rhenium activated carbon catalyst, with a rhenium content of 6% by weight based on the total weight of the catalyst. The Renium activated carbon catalyst was prepared by impregnating an aqueous solution of direnium heptoxide into the activated carbon filaments and then drying at 120 ° C. Prior to use, the catalyst was activated for 3 hours with hydrogen at 300 ° C.

The composition of the leaving reaction mixture appears from the table.

Example 3

In the same manner as in Example 1, a mixture of 2,5-dihydrofuran (3.1 parts by weight), 1,4-dioxane (3.1 parts by weight) and water (1 parts by weight) was reacted under hydrogen pressure. 120 bar and at a temperature of 154 ° C in the presence of a refluxing catalyst of 6% by weight based on the total weight of the catalyst. The rhenium catalyst was prepared by impregnating an aqueous solution of rhenium heptoxide 5 onto the titanium dioxide filaments and drying at 120 ° C. Prior to use, the catalyst was activated for 3 hours under a hydrogen flow at 300 ° C.

The composition of the leaving reaction mixture is shown in the table.

Example 4 10 As in Example 1, a mixture of 2,5-dihydrofuran (1.5 parts by weight), tetrahydrofuran (1.1 parts by weight) and water (1 parts by weight) was reacted under hydrogen pressure bar and at 200 ° C in the presence of the rhenium titanium dioxide catta 15 of Example 3. In the second experiment, the feed rate of the reaction mixture was doubled to 50 ml / h.

The composition of the leaving reaction mixture is shown in the table.

Ex. BD THP GBL GBL HBA BuOH Conversion (ml / h) feed (%) (mole%) 1 25 32 15 0.3 1 2 51 2 25 38 4 9 5 4 61 3 20 85 6 3 1 5 100 4 25 79 * 5 0 9 100 50 71 * 9 2 9 95 20 BD = 1,3-butanediol, THF = tetrahydrofuran, GBL = γ-butyrolactone, HBA = 4-hydroxybutanal, BuOH = n-butanol * In experiments reconstituted THF was not taken into account in the balance sheet because THF was used as a solvent. The molar percentage is calculated from the reacted 2,5-dihydrofuran.

111458 12

Example 6 In a 50 ml metal autoclave equipped with a stirrer was charged 2 g of copper-activated carbon catalyst (10% copper content by weight based on the total weight of copper catalyst), 5 g of 2,5-dihydrofuran and 2.6 g of water. The catalyst was prepared by pre-impregnation of activated carbon with an aqueous solution of copper nitrate, drying at 100 ° C and activating for 2 hours in a hydrogen stream at 250 ° C. The autoclave was pressurized from 50 bar to 10 bar with hydrogen and then heated to 150 ° C for one hour. The autoclave was then cooled to room temperature and depressurized. Conversion of 85% 31 mole% 1,4-butanediol, 30 mole% tetrahydrofuran, 2 mole% γ-butyrolactone, 18 15 mole% 4-hydroxybutyraldehyde and 1 mole% butanol based on the respective 2,5-dihydrofuran amount.

Example 7

In the same manner as in Example 6, 5 g of 2,5-tetrahydrofuran and 5.4 g of water were reacted in the presence of 2 g of a ruthenium activated carbon catalyst having a ruthenium content of 3% by weight based on the total weight of the catalyst. The catalyst was prepared by absorbing an activated carbon solution of ruthenium nitrate in water, drying at 100 ° C and activating for 2 hours in a hydrogen stream at 250 ° C. The conversion of 2,5-dihydrofuran was 100% to give 51 mole% 1,4-butanediol, 35 mole% tetrahydrofuran, 1 mole% γ-butyrolactone and 3 mole% butanol based on the respective 2,5-dihydrofuran reacted. .

Example 8 In a 50 ml metal autoclave equipped with a stirrer, 0.2 g of direnium heptoxide (Re2C7) was dissolved in 5.1 liters of water. The autoclave was pressurized to 40 bar with hydrogen pressure and then the autoclave was heated to 150 ° C for one hour. After the autoclave was cooled and depressurized, 5 g of 2,5-dihydrofuran was added to the reactor. The autoclave was repeatedly pressurized with hydrogen to 50 bar, then the autoclave was then heated to 150 ° C for one hour, after which it was cooled to room temperature and depressurized. The conversion of 2,5-dihydrofuran was 99% to give 45 mol% 1,4-butanediol, 36 mol% tetrahydrofuran, 1 mol% 4-hydroxybutyraldehyde, 3 mol% γ-butyrolactone and 12 mol% of butanol based on the amount of 2,5-dihydrofuran reacted in each case.

Example 9

A metal autoclave equipped with a stirrer was charged with 0.09 g of a homogeneous catalyst RuHClCo (PPhs) 3 (Ph is phenyl), 5 g of 2,5-dihydrofuran and 5.1 g of water, and pressurized with 50 bar of hydrogen. The autoclave was then heated to 150 ° C for one hour and then cooled to room temperature and depressurized. The conversion of 2,5-dihydrofuran was 90% and the removed homogeneous reaction mixture contained 40 mol% of 1,4-20 butanediol, 10 mol% of tetrahydrofuran and 5 mol% of butanol based on the amount of 2,5-dihydrofuran each reacted.

Example 10 A 25 ml tube reactor was charged with 25 ml of a copper 25 and rhenium activated carbon catalyst having a copper content of 3 wt% based on copper and a rhenium content of 6 wt% based on the total weight of the catalyst. The catalyst was prepared by absorbing into aqueous 4 mm activated carbon filaments an aqueous solution of ku-parinitrate and rhenium heptoxide, then drying at 12 ° C and activating for 3 hours under a hydrogen flow at 300 ° C. The reactor was operated continuously at a temperature of 190 ° C and a pressure of 120 bar of hydrogen by means of a drainage process. At the top of the reactor, 13 g of 2,5-dihydrofuran per hour and 7 g of water per hour were pumped through two 35 separate inlet lines. 111458 14 50 l / h of gas was discharged from the reactor. The conversion was 98% and the yield of 1,4-butanediol was 69%, the yield of THF was 20%, the yield of butyrolactone was 4% and the yield of n-butanol was 6%. The remainder consisted mainly of 4-hydroxybutyraldehyde.

Example 11 In a 400 mL tubular reactor was charged 400 mL of the catalyst of Example 2. 200 g of 2,5-dihydrofuran per hour and 100 g of water per hour were pumped to the top of the reactor via two separate inlet lines at a temperature of 190-200 ° C and 120 bar of hydrogen. The reactor was operated at product return with a 10: 1 ratio of cycle to inlet flow. 100 liters of gas were discharged per hour. The reactor was operated continuously for 30 days, during which time samples were taken. The following yields were obtained with 100% conversion: 1,4-butanediol, 65-69% yield, THF, 25-5% yield, butyrolactone, 1-3% yield, n-butanol, 5-5 yield. 6%. The catalyst had not been deactivated after 30 days.

Claims (11)

111458 Process for the preparation of 1,4-butanediol, characterized in that 2,5-dihydrofuran is reacted in one step in the presence of water and hydrogen at a temperature of 20 to 300 ° C and a pressure of 1 to 300 bar and in the presence of a hydrogenation catalyst. A process according to claim 1, characterized in that a hydrogenation catalyst is used which contains at least one element from group Ib, VIb, Vllb or VHIb of the Periodic Table of the Elements. Process according to claims 1 and 2, characterized in that a heterogeneous hydrogenation catalyst is used. Process according to Claims 1 to 3, characterized in that a hydrogenation catalyst is used, the catalytically active component of which is applied to a support. Process according to claims 1-4, characterized in that a hydrogenation catalyst is used which contains one or more components acting as Brönsted or Lewis acids. 6. A process according to claims 1-5, characterized in that a hydrogenation catalyst containing rhenium is used. A process according to claims 1-5, characterized in that a hydrogenation catalyst containing copper is used. Process according to claims 1-5, characterized in that a hydrogenation catalyst containing nickel or cobalt is used. Process according to claims 1-5, characterized in that a hydrogenation catalyst containing platinum metal is used. 111458 A process according to claims 1-9, characterized in that a hydrogenation catalyst is used, the catalytic active component of which is applied to a carrier material containing alumina, clay earth, silica, zirconium dioxide, titanium dioxide, zeolite and / or activated carbon. Process according to claims 1 and 2, characterized in that a homogeneous hydrogenation catalyst is used which contains an element from Group VIIIb of the Periodic Table of the Elements. 111458