MXPA97000123A - Preparation of 1,4-butand - Google Patents

Abstract

The present invention relates to: A process for the preparation of 1,4-butadiol, in which 2,3-dihydroofuran is reacted in a hydrogenation catalyst, in a single step, in the presence of water and hydrogen at a temperature comprised between 20øC and 300øC, and under a pressure of 1 to 300 bar in a neutral environment or well

Description

PREPARATION OF 1, 4-BUTANDIOL The present invention relates to a process for the preparation of 1, -butand ol. WO 92/206? 7 relates to a process for the preparation of mixtures of 4-hydroxybutyldehyde / 2-hydrax and etrahydrofuran, wherein, in a first step, 2,5-dihydrofuran isomeric isomeric. , 3-dihydrafurane in the presence of rod-o-phosphine or ruthenium-phosphine complexes homogeneously dissolved in the reaction medium and then removed by distillation from the reaction mixture. The 2,3-dihydrofuran is then reacted with water in an acid catalyst to form a mixture of 4-h idrox-butanol and 2-h idrox and tetrahydrofuran, and this mixture is isolated. The. The proposed proposal is to convert the mixture obtained in this way to 1, -butanediol by idrogena ion. Starting from 2.3-h idrofuran, two stages are therefore required to reach. 1,4-butan iol. US-A 4,859,801 teaches that it is possible to cause the reaction of 2,3-hydrsfuran with an aldehyde and hydrogen in the presence of water at a pH of 8 to 14 using a hydrogenation catalyst to form 1,4-butanediol mixtures and 2-alkylated 1-1, 4-butanediol. The yield of 1, 4-butandol is moderate in this procedure. If the 2,3-dihydric acid used in the reaction is hydrogenated directly, the hydrophilic acid is formed from it as the main product. The 1, 4-butadiene is formed only in small amounts. E3 EP-A 340,170 relates to the hydrogenation of previously prepared 4-hydroxybutyl-3-hydroxybenzene / 2-hydroquinone mixtures in a separate process in a basic medium. in section 3 of an aldehyde to form 2-3 Iq? 11-1, 4 ~ butand 1 oles, part of this mixture is hydrogenated in 1,4-butane. Accordingly, the object of the present invention is to provide a process for the preparation of 1,4-butanediol starting from 2,3-d? H-idrofuran which makes it possible to obtain 1,4-butanediol in a single step with good performance and selectivity. Accordingly, we have found a process for the preparation of 1,4-buta d 10I, where ** a *. * T * a > z i Qna r _ * -: -. 1 ': > -dihydrofuran in a single stage, in the presence of water and hydrogen at a temperature of 20 ° to 300 ° C and under a pressure of 1 to 30 bar in a neutral environment or in a hydrogenated catalyst. In the process of the invention, two reaction steps are carried out in this way in a single-stage process, ie a) the reaction of 2,3-d? H? Drofuran with water to form a me.'c ] 3 of 4-h? Dra; < ibut 1 ra] dehí do v its isomer 7- hydroxy tetrahydrofuran as shown in equation (1) b) the catalytic hydrogenation of the mixture obtained in accordance with equation (1) and consisting of 4-hydroxybutyl-hydrodehyde and 2-hydroxy-tetrahydrofuran-both compounds being in equilibrium with each other-to form 1, 4- butandiol as shown in equation (2) HO - CH2 -CH2 -CH2-C vH + 00 <OH - ^ ca7t.? HO-CH2-CH2-CH2-CH2-OH (2) When the process of the present invention is carried out, 2,3-dihydric acid reacts generally with water in a molar ratio between 2,3-dihydrofuran and water from 1: 1 to 1: 100, preferably 1: 1. : 50, and with a higher degree of preference from 1: 1 to 1: 10 and in the presence of hydrogen and a hydrogenation catalyst at a pressure, in general terms, from 1 to 300 bar, preferably from 5 to 250 bar, and with a greater degree of preference of generally 15 to 200 bar and at a temperature of 20 ° C to 300 ° C, preferably of 40 ° C to 230 ° C and with a greater degree of preference of 80 * C to 200 ° C to form 1, 4 -butand? ol. The reaction of the present invention is carried out in a neutral or acidic environment, that is to say at a pH of the aqueous phase which is within the range of acidic or neutral pH, of preference *, i * at a pH within a range of 2 to 7.5, especially 4 to 7.2, and more specifically in the range of 6. When heterogeneous water-insoluble catalysts are used, the operation of the procedure in a neutral or undated environment indicates that the catalysts employed act non-basic and contain preferably acid centers. Dej Letuis or Broens ^ ed that influence the course of the reaction in the desired form, that is to achieve the formation of 1, 4-butandol in an edomintent manner. Suitable hydrogenation catalysts for use in the process of the invention are generally all the catalysts suitable for the hydrogenation of the groups c b and n. It is possible to employ homogeneously dissolved HL catalysts in the reaction medium, as described, for example, in Houben-We 1, Methoden aer Organischen Chemie, (Methods of Organic Chemistry), Vol. IV / c , page 45 to 67, Th eme Verlag, Stuttgart 1 80 or alternatively to heterogeneous heterogeneous ionization catalysts of? in accordance with that described in Hsuben-Weyl, Methoden der Organischen Chemie (Methods of Organic Chemistry) Vol. IV / lc, pages 16 to 26. The preferred homogeneous catalysts are, in particular, the complexes of rhodium, ruthenium and cobal or ligands of phosphite or phosphine, the preparation of which is described in, for example, CA-A 7,276 41, H. Brunner in Kart law: The chemistry of the meta 1-c bond bond (The chemistry of the metal-carbon bond); Vol. 5, pages 110 to 124, John Wiley Sons, New York 1989 and Tóth et al. Inorg. Chi. Acta 42, 153 (1980) and the bibliography cited here. Preferably, however, the process of the present invention is carried out using heterogeneous hydrogenation catalysts, i.e., the hydrogenation catalysts which are ultimately insoluble in the reaction medium. Among these hydrogenated ionizers are those containing t or several elements of group Ibm VI Tb, and VI Ib of the Periodic Table, especially copper, oar, or ruthenium or mixtures of these elements. Other tasting! Preferred binders are loa which contain at least one member of the group Ib, VI Ib, or VTIb and at least one additional element of the groups Tb, Vb, VIb, Vllb, VI I Ib, Illa, or bi n IVa of the Table Periodic, which forms a half alloy with said element or elements of group Tb, VI Ib, or VITTb. In addition to said copper, rowing and rutting elements, other elements, provided by way of example only, are chromia, molybdenum, tungsten, cobalt, radium, indium, nickel, palladium, iron and / or platinum. In the process of the present invention, use may be made of heterogeneous hydrolyzing catalysts consisting of metals in activated, finely divided form having a large surface area, for example, Paney copper or rowing sponge. The process of the present invention can also be employed, for example, which is known as pre-ipcation catalysts. Such catalysts can be prepared by precipitating their catalytically active components from their salt solutions, especially from the solutions of their nitrates and / or acetates, for example, by the addition of hydroxide solutions and / or alkali metal carbonate and / or metal of alkaline earths, said precipitates for example or hardly soluble hydroxides, hydrates of oxide, basic salts, or carbonate, followed by the drying of the obtained values and then au conversion by calcination in general at a temperature between 30 ° C and 700 ° C, espe- cially between 100 ° C and 60 ° C, in the respective oxides, mixed oxides / or oxides of mixed valence that are reduced by the treatment with hydrogen or with gases containing hydrogen, usually at a temperature between 100 * 0 and 700 ° C, especially at a temperature between 150 * C and 400 * 0, in the respective metals and / or omitted oxides of a lower oxidation stage and which are converted into the desired catalytically active form. The reduction usually continues until no more water forms. When preparing precipitation catalysts containing a support material, the precipitiation of the catalytically active components can be carried out in the presence of the respective support material. Alternatively, the catalytically active components can preferably be precipitated simultaneously with the support material from the respective salt solutions. It is preferred to operate the process of the present invention using hydrogenation catalysts containing, deposited in a support material, metals or metal compounds capable of catalyzing hydrogenation. Apart from the aforementioned precipitation catalysts which additionally contain a support material in addition to the catalytically active components in general terms, the supported catalysts in which the components having a catalytic hydrogenation action have been applied on a material of support, for example, by impregnation are suitable for the process of the present invention. The method used to apply the catalytically active metals on the support is not generally of critical importance and can be carried out in numerous ways. The catalytically active metals can be applied on these support materials, for example, by impregnation with solutions or suspensions of the salts or oxides of the respective elements, followed by the drying and reduction of the metal compounds in the respective metals or compounds of a low oxidation step by means of an oxidizing agent. reduction, preferably with the help of hydrogen or complex hydrides. Another possible method for applying the cytically active metals to these supports comprises the impregnation of the supports with salt solutions which can be easily decomposed thermally, for example with nitrates or complex compounds which can be easily decomposed thermally. example with complexes of carbo or hydride of the catalytically active metals, and the heating of the resulting impregnated supports to achieve the thermal decomposition of the metal compounds adsorbed, in temperatures of 300 * 0 to 600 * 0. This thermal decomposition is preferably carried out under a protective gas cover. Suitable protective shields are, for example, nitrogen, carbon dioxide, hydrogen, or noble gases. In addition, the tasting metals! 111 - merit assets can be deposited on the support d «? mediating catalyst deposition by vaporization or flame pulsing. Theoretically, the content of catalytically active metals in these supported catalysts of the present invention is not critical to the success of the process. It will be apparent to one skilled in the art that higher contents of catalytically active metals in these supported catchers lead to higher-than-average space yields. However, supported catalysts are generally used wherein a content of catalytically active metals is from 0.1 to 807 by weight, preferably from 0.5 to 30 V by weight, based on the total catalyst. Since these content data refer to the total catalyst, they include the support material, and since different support materials have very different specific gravities and very different specific surface areas, the actual values may be above or below the established ones. without this adversely affecting the result achieved by the method of the present invention. E niently, numerous catalytically active metals can be applied on the respective support material, if desired. In addition, the catalytically active metals can be applied to the support by the methods described in DE-A 2,519,817, EP-A 1,477,219, and EP-A 285,420, for example. In the catherers described in the aforementioned references, the catalytically active metals are present in the form of alloys produced by the heat treatment and / or the reduction of salts or complexes of the aforementioned metals after said salts or complexes have been deposited on a support, for example, by impregnation. The activation of the preci ation carriers and the supported catalysts can be achieved, if desired, in situ in the reaction mixture by the hydrogen present there. However, these caters are preferably activated separately before use. The support materials used are generally oxides of aluminum and titanium, zirconium dioxide, silicon dioxide, Kieaelguhr, silica gel, clayey earths, for example moptmoylum, silicates, such as, for example, magnesium or aluminum silicates, zeolites, such as ZSM-5 or ZSM-10 zeolites, as well as activated carbon. Preferred materials for support are aluminum oxides, titanium dioxides, zirconium dioxide, and activated carbon. Finally, if desired, mixtures of various support materials can serve as carriers for catchers that are to be used in the process of the present invention. The following catalysts can be mentioned as examples of heterologous catalysts which can be employed in the process of the present invention: manganese in activated carbon, rhenium in activated carbon, rhenium in silicon dioxide, rhenium / tin in activated carbon, rhenium / palladium in activated carbon, rhenium / copper in activated carbon, rhenium / nickel in activated carbon, copper in activated carbon, copper in dioxide of silicon, copper in aluminum oxide, copper chromite, and copper barium chromite. Components of Lewis acid and / or Broensted can be added to the catalysts, for example zeolites, aluminum or silicon oxides, phosphoric acid or sulfuric acid. They are usually added in amounts of 0.01 to 5V. by weight, preferably from 0.05 to 0.5 * by weight and especially from 0.1 to 0.4M by weight, based on the weight of the catalyst used. It is especially preferred to carry out the process of the present invention employing hydrogenation catalysts containing Broensted and / or Le? Is acid centers. When such catalysts are employed, it is generally unnecessary to perform additional addition of a Broensted or Lewis acid to the reaction mixture. Examples of homogeneous, useful catalysts containing Broensted acid centers are metal transition metal complexes of Figure VI Ib, especially complexes of rodiium, ruthenium and cobalt with phosphine and phosphine ligands, which carry Broepsted acid groups. functional groups, for example carboxylic groups, sulphunic acid groups, and / or phosphonic acid groups, co or substituents, for example complexes of the mentioned transition metals with tri-phenyl-1-phosphino-p-sulphonic acid ligands. Such ligands can be prepared as, for example, by the process described in Artgew. Chem. 105.1097 (1993). Particularly useful results can be achieved in the process of the present invention by the use of heterogeneous catalysts containing Broensted or Lewis acid centers. For example, the catalytically active metals themselves can act as co-centers of Broensted or Lewis acid if they are not totally reduced in the respective metals during activation of the catalyst with hydrogen or hydrogen peroxide. This applies, for example, to catherers containing rertium and chromite such as rhenium black and copper chromite. In rhenium black, rhenium is present in the form of a mixture of rhenium metal with rhenium compound in higher stages of oxidation in which case the latter can cause effects such as Lewis acid or Broepsted. In addition, such Lewis or Broensted acid centers can be introduced into the catalyst by means of the support material employed. As examples of used support materials containing Leis or Broensted acid centers, there may be mentioned aluminum oxides, titanium dioxide, zirconium dioxide, silicon dioxide, silicates, clay soils, zeolites and activated carbon. . Accordingly, it is particularly preferred to operate the process of the present invention employing, as carriers of hydragen in supported catalysts containing at least one element of groups Ib, VI Ib, or VITTb of the Periodic Table, especially copper, oar and / or route, or at least one element of the groups Ib, VI Tb, or VI I Ib and also at least one additional element of the groups Ib, Vb, VIb, VI Ib, VI I Ib, 11 Ja, or IVa of Periodic Table, said elements form a mixture or an alloy with said element (s) of groups Ib, Vllb, or VlIIb, deposited in a support material that is effective as Lewis or Broensted. Particularly advantageous catalysts are, for example, roasting in activated carbon, re or in dioxide of the conio, rowing in titanium dioxide, rowing in silicon dioxide, copper in activated carbon, copper in silicon dioxide, and ruthenium in carbon activated. The process of the present invention can be carried out either individually or in the form of a batch. In order to achieve continuous operation, tubular reactors can be used with advantage, for example, wherein the catalyst is preferably arranged in the form of a fixed bed, on which the reaction mixture can pass in the up flow mode or in the down flow mode. When the process is carried out in batch form, simple stirred reactors or, preferably, recycling reactors can be used. When recycling reactors are used, the catalyst is preferably in the form of a fixed bed. When there is an incomplete conversion of the initial material, can this be usefully recycled to the reaction already after the separation, by distillation, of the desired products, or in the form of a current? partial that includes the other products of the reaction. This can be particularly useful when the procedure is carried out continuously. Higher yields are generally obtained when the reaction is carried out continuously to produce 1, 4-butand that when the reaction is carried out in batch form using the same catalyst. The process of the present invention can be carried out advantageously in the presence of an inert solvent under the conditions of the reaction, for example, a water-soluble ether, for example tetrahydrofuran, dioxane, or ethoxyethane. Alternatively and with benefit, alcohols, especially the final product 1, 4-butand 10I, can be used as solvents.

The effluent obtained is generally an essentially composed mixture of excess water and 1,4-butane. Byproducts that may be present in the effluent in smaller amounts are, for example, ga-butyrolactone, tetrahydrofuran, and n-butanol. The effluent can be prepared by conventional methods, for example by distillation, by isolating 1, 4-butandol and any other by-product gamma-buvastatin, tetrahydrofuran, or n-butanol present in the effluent. In this process, any unconverted 2, 3-d-hydrofuran and any solvent used can be recovered and mixed with the reaction. In the case of the incomplete conversion of 2,3-dihydrofuran, the effluent can be treated later, before it is processed, in a follow-up reactor to achieve the quantitative conversion. The required 3-d? Hdrofuran as a starting material can be obtained, for example, using the procedure described in US-A 3,828,077 by partial hydrogenation of furan. Is 1, 4-butand prepared? It is used throughout the world in large quantities and serves as a diol component for the preparation of, inter alia, polyesters, polyurethanes and epoxy resins. EXAMPLES The yields given in the following examples are set in molar percentages and were determined by gas chromatography. EXAMPLE 1 In a mental autoclave having a capacity of 50 L and equipped with a stirrer were placed 2 g of a? Catalyst. rhenium in activated carbon that had been activated at 300 * 0 in hydrogen flow and had a rhenium content of 6% e? weight, calculated as Re and based on the weight of the catalyst, 5 g of 2,3-dihydrofuran, and 15 g of water. Hydrogen was not then introduced forcefully to establish a pressure of 50 bar and the autoclave was heated to 170 * 0. After a period of 1 hour, the autoclave was cooled and depressurized. The effluent had the following composition: 77% molar of 1, 4-butand isl, 20 mole% of gamma-butyrolactone, 1.3 mole% of tetrahydrofuran, 1.3 mole% of n-butanol and 0.3 mole% of n-prop ol . EXAMPLE 2 In a manner similar to that described in Example 1- 5 g of 2,3-d ih idrofuran and 5 g of water reacted for 2 hours in 2 g of a copper catalyst on activated carbon (copper content: 10% by weight, calculated co or Cu and based on the total weight of the catalyst, prepared by impregnation of activated carbon with the appropriate amount of a copper agar solution, followed by drying at a temperature of 120 * 0 and activation during 2 hours in a hydrogen flow at 300 * 0). The effluent had the following composition: 95 mol% of 1,4-butandol, 4 mol% of gamma-but rolacton, and 0.8 mol% of tetrahydrofuran. The remainder consisted essentially of the acetal of 2-hydroxy tetrahydrofuran and 1,4-butand 10I. EXAMPLE 3 25 mL of the catalyst described in Example 1 were placed in a tubular reactor having a capacity of 25 mL. 10 g / h of 2, 3-d? H? Drofuran and 5 g / h of water were then passed to the upper part of the reactor by means of two separate feed lines. The hydrogen pressure in the reactor was 120 bar, and the temperature was 166 * C. The exhaust gas regime was 50 L / h. In the effluent, 80% mole of 1,4-butanediol, 1.6% mole of tetrahydrofuran, 8.3% mole of gamma-but i rol actone, and 3.3% mole of n-butanol were found in a conversion of] 97%. The rest consisted of acetic acid of 2% and tetrahydrofuran and 1,4-butanedium. The effluent collected during a period of 8 hours was passed, upon completion of the test, again on the same catalyst under the same reaction conditions (a feed line 20 g / h). In a quantitative conversion of 2,3-d? H? drofuran, the following yields were obtained: 92 mol% of 1, -butandol, 1.9 mol% of tetrahydrofuran, 4.3 mol% of ga ma-bu < i tone and 2% mol r of n-bu anol.

Claims (11)

1. CLAIMS 1. A process for the preparation of 1,4-butanediol, where 2,3-dihydrofuran is reacted in a hydrogenation catalyst, in a single step, in the presence of water and hydrogen, at a temperature of 20 * 0 a 300 * 0 and under a pressure of 1 to 300 bar in a neutral or acidic environment.
2. 2. A process according to claim 1, wherein a heterogeneous hydrogenation catalyst is employed.
3. 3. A process according to claim 1 and claim 2, wherein a hydrogenation catalyst is used which contains at least one element of group Ib or VI Ib or VI I Ib of the Periodic Table or a mixture of said elements .
4. 4. A method according to the one defined in claims 1 to 3, wherein? HE? employs a hydrogenation catalyst from which the catalytically active component has been applied on a support.
5. 5. A process according to that defined in the rei indications 1 to 4, wherein a hydrogenation catalyst is used which contains one or more effective components with Broensted or Lewis acids.
6. 6. A process according to that defined in the rei indications 1 to 5, wherein a hydrogenation catalyst containing rhenium is used.
7. 7. A process according to the one defined in claims 1 to 5, wherein a hydrogenation catalyst containing copper is used.
8. 8. A process according to the one defined in claims 1 to 5, wherein a catalyst of 5 hydrogenation containing ruthenium.
9. 9. A process according to claim 1, wherein the catalyst contains at least one element from group Ib, VI Ib or VI Ib and also at least one additional element from group Ib, Vb, VIb, VI Ib, VI I Ib, Illa, and IVa of the Periodic Table forming a mixture or an alloy with said element or said elements of group Ib, or VI Ib or VI I Ib.
10. 10. A process according to that defined in claims 1 to 8, wherein a catalyst of After the hydrogenation, the catalytically active component of said catalyst has been applied onto a support material A- "containing aluminum oxide, clay soils, silicon dioxide, zirconium dioxide, titanium dioxide, a zealite, / or activated carbon.
11. 11. A process according to claim 1, wherein a homogeneous hydrogenation catalyst is used which contains an element of group VI I Ib of the Periodic Table. 25