CA2168458C - The preparation of 1,4-butanediol - Google Patents
The preparation of 1,4-butanediol Download PDFInfo
- Publication number
- CA2168458C CA2168458C CA002168458A CA2168458A CA2168458C CA 2168458 C CA2168458 C CA 2168458C CA 002168458 A CA002168458 A CA 002168458A CA 2168458 A CA2168458 A CA 2168458A CA 2168458 C CA2168458 C CA 2168458C
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- hydrogenation catalyst
- dihydrofuran
- butanediol
- rhenium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/28—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
- Pretreatment Of Seeds And Plants (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Photoreceptors In Electrophotography (AREA)
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 .degree.C and a pressure of 1 to 300 bar with the aid of a hydrogenating catalyst.
Description
~ 0050/44208 216 8 ~ ~ 8 The preparation of 1,4-butanediol The present invention relates to a process for preparing 1~4-butanediol~ _..
US A 4 209 651 mentions that 2,5-dihydrofuran can be used for the direct preparation of 1,4-butanediol. However, this patent does not indicate the measures needed to achieve this.
WO 92/20 667 by contrast discloses a process for preparing 1,4-butanediol from 2,5-dihydrofuran in which, in a first stage, 2,5-dihydrofuran is isomerized in the presence of rhodium/ or ru-thenium/phosphine complexes homogeneously dissolved in the reac-tion medium to 2,3-dihydrofuran and subsequently the latter is distilled out of the reaction mixture. The 2,3-dihydrofuran is then converted on an acidic catalyst with water into a mixture of 4-hydroxybutanal and 2-hydroxytetrahydrofuran, which is hydroge-nated in the presence of a hydrogenation catalyst to 1,4-butane-diol. Consequently this is a 3-stage process.
EP A 24 770 describes the one-stage preparation of 4-hydroxybuta-nal by reaction of 2,5-dihydrofuran in the presence of large amounts of water and using a catalyst which contains a metal of group VIIIb of the periodic table of the elements and has been treated with a base before use. The conversion in this case is only 55~, and the selectivity is likewise relatively low at 65~, so that the reaction mixture must first be worked up by distilla-tion before hydrogenation of the 4-hydroxybutyraldehyde to 1,4-butanediol.
US A 4 859 801 discloses the conversion of 2,3-dihydrofuran in the presence of water at a pH of 8 to 14 with an aldehyde and hy-drogen using a hydrogenation catalyst into mixtures of 1,4-butanediol and 2-alkyl-1,4-butanediol. The yield of 1,4-butanediol is modest in this case. In order to convert 2,5-dihydrofuran into 1,4-butanediol by this process it would initially have to be isomerized to 2,3-dihydrofuran in a reaction stage preceding the reaction described.
BE A 674 652 discloses the isomerization of 2,5-dihydrofuran to 2,3-dihydrofuran using catalysts from group VIIIb of the periodic table of the elements.
Since all the processes mentioned require multistage reactions in order to obtain 1,4-butanediol starting from 2,5-dihydrofuran, but such multistage procedures are associated with considerable costs which make the price of the 1,4-butanediol produced in the process uncompetitively high, it is an object of the present in-vention to find a process which makes it possible to prepare 1,4-butanediol in good yields and selectivities in one stage stating from 2, 5-dihydrofuran:
We have found that this object is achieved by a process for pre-paring 1,4-butanediol, which comprises reacting 2,5-dihydrofuran in one stage in the presence of water and hydrogen at from 20 to 300°C and under a pressure of from 1 to 300 bar on a hydrogenation catalyst.
Thus, the process according to the invention brings about the 3 reaction stages a) isomerization of the 2,5~iihydrofuran to 2,3-dihydrofuran according to equation (1) ---~ ( 1 ) O O
b) conversion of the 2,3-dihydrofuran with water into a mixture of 4-hydroxybutyraldehyde and its isomer 2-hydroxytetrahydrofuran according to equation (2) O
H
H2~ HO-CHy-CHz--CH2 \ + ~ ( 2 ) H O OH
O
and c) catalytic hydrogenation of the mixture of 4-hydroxybuty-raldehyde and 2-hydroxytetrahydrofuran (the two compounds are in equilibrium) obtained according to equation (2) to 1,4-butanediol according to equation (3) O
HO-CH -CH -CH -C + ~ H H~ HO-CH2-CH2-CH2-CH2--0H
Cat.
H O ~ OH
US A 4 209 651 mentions that 2,5-dihydrofuran can be used for the direct preparation of 1,4-butanediol. However, this patent does not indicate the measures needed to achieve this.
WO 92/20 667 by contrast discloses a process for preparing 1,4-butanediol from 2,5-dihydrofuran in which, in a first stage, 2,5-dihydrofuran is isomerized in the presence of rhodium/ or ru-thenium/phosphine complexes homogeneously dissolved in the reac-tion medium to 2,3-dihydrofuran and subsequently the latter is distilled out of the reaction mixture. The 2,3-dihydrofuran is then converted on an acidic catalyst with water into a mixture of 4-hydroxybutanal and 2-hydroxytetrahydrofuran, which is hydroge-nated in the presence of a hydrogenation catalyst to 1,4-butane-diol. Consequently this is a 3-stage process.
EP A 24 770 describes the one-stage preparation of 4-hydroxybuta-nal by reaction of 2,5-dihydrofuran in the presence of large amounts of water and using a catalyst which contains a metal of group VIIIb of the periodic table of the elements and has been treated with a base before use. The conversion in this case is only 55~, and the selectivity is likewise relatively low at 65~, so that the reaction mixture must first be worked up by distilla-tion before hydrogenation of the 4-hydroxybutyraldehyde to 1,4-butanediol.
US A 4 859 801 discloses the conversion of 2,3-dihydrofuran in the presence of water at a pH of 8 to 14 with an aldehyde and hy-drogen using a hydrogenation catalyst into mixtures of 1,4-butanediol and 2-alkyl-1,4-butanediol. The yield of 1,4-butanediol is modest in this case. In order to convert 2,5-dihydrofuran into 1,4-butanediol by this process it would initially have to be isomerized to 2,3-dihydrofuran in a reaction stage preceding the reaction described.
BE A 674 652 discloses the isomerization of 2,5-dihydrofuran to 2,3-dihydrofuran using catalysts from group VIIIb of the periodic table of the elements.
Since all the processes mentioned require multistage reactions in order to obtain 1,4-butanediol starting from 2,5-dihydrofuran, but such multistage procedures are associated with considerable costs which make the price of the 1,4-butanediol produced in the process uncompetitively high, it is an object of the present in-vention to find a process which makes it possible to prepare 1,4-butanediol in good yields and selectivities in one stage stating from 2, 5-dihydrofuran:
We have found that this object is achieved by a process for pre-paring 1,4-butanediol, which comprises reacting 2,5-dihydrofuran in one stage in the presence of water and hydrogen at from 20 to 300°C and under a pressure of from 1 to 300 bar on a hydrogenation catalyst.
Thus, the process according to the invention brings about the 3 reaction stages a) isomerization of the 2,5~iihydrofuran to 2,3-dihydrofuran according to equation (1) ---~ ( 1 ) O O
b) conversion of the 2,3-dihydrofuran with water into a mixture of 4-hydroxybutyraldehyde and its isomer 2-hydroxytetrahydrofuran according to equation (2) O
H
H2~ HO-CHy-CHz--CH2 \ + ~ ( 2 ) H O OH
O
and c) catalytic hydrogenation of the mixture of 4-hydroxybuty-raldehyde and 2-hydroxytetrahydrofuran (the two compounds are in equilibrium) obtained according to equation (2) to 1,4-butanediol according to equation (3) O
HO-CH -CH -CH -C + ~ H H~ HO-CH2-CH2-CH2-CH2--0H
Cat.
H O ~ OH
(3) in a single stage.
AMENDED SHEET
In the process according to the invention, the 2,5-dihydrofuran is reacted with water in general with a 2,5-dihydrofuran/water molar ratio of from 1:1 to 1:100, preferably 1:1 to 1:50 and par-ticularly preferably l : Y to 1:10, and~wi:n--the presence--of---hydrogen and of a hydrogenation catalyst under a pressure of, in general, from 1 to 300 bar, preferably from 5 to 200 bar and, in particu lar, in general from 10 to 150 bar, at from 20 to 300°C, prefer ably 40 to 230°C and particularly preferably from 80 to 200°C to give 1,4-butanediol.
Hydrogenation catalysts which can be used in the process accord ing to the invention are, in general, all catalysts suitable for the hydrogenation of carbonyl groups. The catalysts used may ei they be soluble homogeneously in the reaction medium, as de scribed, for example, in Houben-Weyl, Methoden der Organischen Chemie, volume IV/lc, 45-67, Thieme Verlag, Stuttgart 1980, or else be heterogeneous as described in Houben-Weyl, Methoden der Organischen Chemie, volume IV/lc, 16-26. Particularly preferred homogeneous catalysts are the complexes of rhodium, ruthenium and cobalt with phosphine or phosphite ligands, whose preparation is described, for example, in CA-A 7 276 41, H. Brunner in Hartley:
The chemistry of the metal-carbon bond; Vol. 5, 110-124, John Wiley & Sons, New York 1989 and Toth et al., Inorg. Chim. Acta 42, (1980) 153 and the literature cited therein.
However, heterogeneous hydrogenation catalysts are preferably used in the process according to the invention, that is to say catalysts which are essentially insoluble in the reaction medium.
Preferred hydrogenation catalysts of this type contain one or more elements of group Ib, VIb, VIIb and VIIIb of the periodic table of the elements, in particular copper, chromium, molybde-num, tungsten, rhenium, ruthenium, cobalt, rhodium, iridium, nickel, palladium, iron and/or platinum.
Heterogeneous hydrogenation catalysts which can be used in the process according to the invention are those composed of metals in activated, finely divided form with a large surface area, for example Raney nickel, Raney cobalt, palladium, platinum or rhe-nium sponges.
It is furthermore possible to use, for example, precipitated cat-alysts in the process according to the invention. Catalysts of this type can be prepared by precipitating their catalytically active components from solutions of salts thereof, in particular from solutions of the nitrates and/or acetates thereof, for exam-ple by adding solutions of alkali metal and/or alkaline earth metal hydroxides and/or carbonates, as, for example, sparingly soluble hydroxides, oxide hydrates, basic salts or carbonates, subsequently drying the resulting precipitates and then convert-ing them by calcination at, in general, from 300 to 700°C, in par-ticular 400 to-600°C~ into the relevant oxides, mixed oxides andJ
or mixed valency oxides which are reduced by treatment with hy-drogen or with hydrogen-containing gases at, as a rule, from 100 to 700°C, in particular at 150 to 400°C, to the relevant metals and/or oxides of a lower oxidation state, and converted into the .
actual catalytically active form. In this connection, as a rule, reduction is continued until water is no longer formed.~To pre-pare precipitated catalysts which contain a carrier material, the precipitation of the catalytically active components can take place in the presence of the relevant carrier material. However, it is also possible and advantageous for the catalytically active components to be precipitated simultaneously with the carrier ma-terial from the relevant salt solutions.
The hydrogenation catalysts preferably employed in the process according to the invention contain the hydrogenation-catalyzing metals or compounds thereof deposited on a carrier material.
Apart from the abovementioned precipitated catalysts which also contain a carrier material in addition to the catalytically ac-tive components, supported catalysts which are generally suitable for the process according to the invention are those in which the hydrogenation-catalyzing components have been applied to a carrier material by, for example, impregnation.
The way the catalytically active metals are applied to the car-rier is, as a rule, not critical and can be brought about in a variety of ways. The catalytically active metals can be applied to these carrier materials for example by impregnation with solu-tions or suspensions of the salts or oxides of the relevant ele-ments, drying and subsequent reduction of the metal compounds to the relevant metals or compounds of a lower oxidation state using a reducing agent, preferably using hydrogen or complex hydrides.
Another possibility for the application of the catalytically ac-tive metals to these carriers comprises impregnating the carriers' with solutions of salts which can easily be thermally decomposed, eg. with nitrates, or with complex compounds which can easily be thermally decomposed, eg. with carbonyl or hydrido complexes of the catalytically active metals, and heating the impregnated car-riers at from 300 to 600°C for the thermal decomposition of the adsorbed metal compounds. This thermal decomposition is prefer-ably carried out under a protective gas atmosphere. Examples of suitable protective gases are nitrogen, carbon dioxide, hydrogen or the noble gases. It is furthermore possible to deposit the 0050/44208 21 fi 8 4 5 8 catalytically active metals on the carrier by vapor deposition or by flame spraying. The content of catalytically active metals in these supported catalysts is not in principle critical for the success of the process according to the invention. It is self-ev-5 ident to the skilled ~urorker that higher contents ofwcatalytically active metals in these supported catalysts lead to higher space-time conversions than do lower contents. However, the generally used supported catalysts have a content of catalytically active metals of from 0.1 to 80%, preferably 0.5 to 30%, of the total weight of the catalyst. Since these contents are based on the complete catalyst including carrier material but the vax'ious car-rier materials have very different specific gravities and specif-ic surface areas, however, contents higher or lower than these have no adverse effect on the result of the process according to the invention. It is, of course, also possible. to apply a plural-ity of the catalytically active metals to the particular carrier material. It is furthermore possible for the catalytically active metals to be applied to the carrier for example by the processes of DE A 25 19 817, EP-A1 477 219 and EP-A 285 420. The catalytic-ally active metals are present in the catalysts disclosed in the abovementioned publications in the form of an alloy produced by thermal treatment and/or reduction of the, for example, by im-pregnation on a deposited salts or complexes of the above-mentioned metals.
The activation of the precipitated catalysts and of the supported catalysts can also take place in situ in the reaction mixture by the hydrogen present therein, but these catalysts are preferably activated separately before use thereof.
Carrier materials which can generally be used are the oxides of aluminum and titanium, zirconium dioxide, silicon dioxide, kie-selguhr, silica gel, aluminas, eg. montmorillonite, silicates such as magnesium or aluminum silicates, zeolites such as ZSM-5 or ZSM-10 zeolites as well as active carbon. Preferred carrier materials are aluminum oxides, titanium dioxides, zirconium diox-ide and active carbon. It is, of course, also possible to use mixtures of various carrier materials as carriers for catalysts which can be used in the process according to the invention.
The following catalysts may be mentioned as examples of heteroge-neous catalysts which can be employed in the process according to the invention:
Platinum black, platinum on active carbon, platinum dioxide, pal-ladium on active carbon, palladium on aluminum oxide, palladium on silicon dioxide, palladium on barium sulfate, rhodium on ac-tive carbon, rhodium on aluminum oxide, ruthenium on silicon dioxide or active carbon, nickel on silicon dioxide, Raney nickel, cobalt on silicon dioxide, cobalt on aluminum oxide, Raney cobalt, carbonyl iron powder, rhenium black, Raney rhenium, rhenium on active carbon, rhenium/palladium on active carbon, rhenium/platinum on active carbon, copper on silicon dioxide, copper on aluminum oxide, copper on active carbon, Raney copper, platinum oxide/rhodium oxide mixtures, platinum/palladium on ac-tive carbon, copper chromite, barium chromite, nickel/chrornium oxide on aluminum oxide, dirhenium heptoxide (Re207), cobalt sul-fide, nickel sulfide, molybdenum(VI) sulfide, copper/molybde-num(VI) oxide/silicon dioxide/aluminum oxide catalysts and the catalysts disclosed in DE A 39 32 332, US A 3 449 445, EP-A
44 444, EP A 147 219, DE A 39 04 083, DE-A 23 21 101, EP-A
415 202, DE-A 2 366 264 and EP A 100 406.
Lewis and/or Bronsted acid components such as zeolites, aluminum oxides or silicon oxides, phosphoric acid or sulfuric acid can be added to the abovementioned catalysts. They are generally added in amounts of 0.01 to 5%, preferably of 0.05 to 0.5% and particu-larly preferably of 0.1 to 0.4% of the weight of the catalyst employed.
The process according to the invention is particularly preferably carried out using hydrogenation catalysts which contain Hronsted and/or Lewis acid centers. When catalysts of this type are used it is not generally necessary to add an additional Bronsted or Lewis acid to the reaction mixture.
Examples of homogeneous catalysts containing Bronsted acid cen-ters which can be used are transition metal complexes of metals of group VIIIb, in particular rhodium, ruthenium and cobalt com-plexes with phosphine or phosphite ligands which carry Bronsted acid functional groups such as carboxyl, sulfo and/or phospho groups as substituents, for example complexes of the said transi-tion metals with triphenylphosphine-p-sulfonic acid ligands. Li-gands of this type can be prepared, for example, by the process of Angew. Chem. 105, (1993) 1097.
Particularly advantageous results can be achieved in the process according to the invention with heterogeneous catalysts which contain Bronsted or Lewis acid centers. The catalytically active metals themselves, for example, can act as Bronsted or Lewis acid centers if they are not completely reduced to the relevant metals in the activation of the catalyst with hydrogen or hydrogen-con-taining gases. This applies, for example, to the rhenium and chromite-containing catalysts such as rhenium black and copper chromite. The rhenium is present in rhenium black as a mixture of metallic rhenium with rhenium compounds in higher oxidation states, and the latter may display effects like Lewis or Bronsted acids. It is furthermore possible for such Lewis or Bronsted acid centers to be introduced into the catalyst via the carrier mate-rial used: Examples of carrier materials containingTLewis-or Bronsted acid centers are the aluminum oxides, titanium dioxides, zirconium dioxide, silicon dioxide, the silicates, aluminas, zeo-lites and active carbon.
The hydrogenation catalysts particularly preferably used in the process according to the invention are therefore supported cata-lysts which contain elements of group Ib, VIb, VIIb and/or VIIIb of the periodic table of the elements, in particular elements of group Ib, VIIb and VIIIb of the periodic table of the elements, deposited on a carrier material acting as a Bronsted or Lewis acid. Examples of particularly advantageous catalysts are rhenium on active carbon, rhenium on zirconium dioxide, rhenium on tita-nium dioxide, rhenium on silicon dioxide, copper on active car-bon, copper on silicon dioxide and ruthenium on active carbon.
The process according to the invention can be carried out either continuously or batchwise. It is possible and advantageous to employ for continuous operation for example tubular reactors in which the catalyst is advantageously arranged in the form of a fixed bed through which the reaction mixture can be passed in a liquid-phase or trickle process. For batchwise operation it is possible to use either simple stirred reactors or, advanta-geously, loop reactors. When loop reactors are used, the catalyst is expediently arranged in the form of a fixed bed. If the starting material is not completely converted it can be returned to the reaction expediently either after removal of the required product by distillation or as part-stream together with the other reactants. This may prove advantageous in particular on continu-ous operation. In general, the yields of 1,4-butanediol are high-er from a continuous reaction than from a batchwise reaction on the same catalyst.
The process according to the invention can advantageously be car-ried out in the presence of a solvent which is inert under the reaction conditions, for example using water-soluble ethers such as tetrahydrofuran, dioxane or dimethoxymethane. It is also pos-sible and advantageous to employ alcohols, in particular the product 1,4-butanediol, as solvent'.
The discharge from the reaction in the process according to the invention is expediently worked up by distillation, when, apart from the main product 1,4-butanediol, the compounds which are formed in small amounts as by-products, tetrahydrofuran, y-butyro-lactone and butanol, can be obtained.
The 2,5-dihydrofuran starting material can be prepared by isomer-ization of vinyloxirane, for example by the-process-of US A 5 034 545 or US-A 5 082 956.
1,4-Butanediol is prepared on a large scale world-wide and is used as diol component for the preparation of, inter alia, poly-esters, polyurethanes and epoxy resins.
Examples Example 1 25 ml of a copper on silicon dioxide catalyst in the form of 4 mm pellets, with a copper content of 10% by weight, calculated as Cu and based on the complete catalyst, were packed into a tubular reactor with a capacity of 25 ml. The catalyst had been prepared by impregnating the silicon dioxide pellets with an ammoniacal copper carbonate/sodium nitrate solution and subsequently drying at 100°C. The catalyst was activated in a hydrogen atmosphere (100 1 H2/h) at 250°C for 2 hours. Subsequently 15 ml/h of a mix-ture of 2.8 parts by weight 2,5~iihydrofuran, 2.8 parts by weight of water and 1 part by weight of 1,4-dioxane were continuously passed over the catalyst under a hydrogen pressure of 120 bar and at a reactor temperature of 134°C.
The composition of the discharge from the reaction is indicated in the Table.
Example 2 The mixture of 2,5-dihydrofuran, water and 1,4-dioxane described in Example 1 was reacted as in Example 1 on a rhenium on active carbon catalyst which had a rhenium content of 6% by weight, calculated as Re and based on the total weight of the catalyst, under a hydrogen pressure of 120 bar and at 200°C. The rhenium on active carbon catalyst had been prepared by impregnating the active carbon pellets with an aqueous dirhenium heptoxide solu-tion and subsequently drying at 120°C. Before use it was activated with hydrogen at 300°C for 3 hours.
The composition of the discharge from the reaction is indicated in the Table.
0050/44208 21 s g 4 5 8 Example 3 A mixture of 2,5-dihydrofuran (3.1 parts by weight), 1,4-dioxane (3.1 parts by weight) and water (1 part by weight) was reacted as in Example 1 on a rhenium on-titanium dioxide catalyst--which--had -a rhenium content of 6% by weight, calculated as Re and based on the total weight of the catalyst, under a hydrogen pressure of 120 bar and at 154°C. The rhenium catalyst had previously been prepared by impregnating titanium dioxide pellets with aqueous rhenium heptoxide solution and drying at 120°C and was activated before use in a stream of hydrogen at 300°C for 3 hours:
The composition of the discharge from the reaction is indicated in the Table.
Example 4 A mixture of 2,5-dihydrofuran (1.5 parts by weight), tetrahydro-furan (1.1 parts by weight) and water (1 part by weight) was reacted as in Example 1 on a rhenium on titanium dioxide catalyst as in Example 3 under a hydrogen pressure of 120 bar and at 200°C.
In a second experiment, the flow rate of the reaction mixture was doubled to 50 ml/h.
The compositions of the discharges from the reaction are indi-cated in the Table.
Example Flow rateBD THF Conversion [ml/h] GBL [%]
HBA
BuOH
[mol%]
1 25 32 15 0.3 1 2 51 4 25 79 * 5 0 9 100 50 71 * - 9 2 9 95 BD: 1,4-butanediol, THF: tetrahydrofuran, GBL: y-butyrolactone;
HBA: 4-hydroxybutanal, BuOH: n-butanol *: The amount of THF formed in the experiments was not calcu-lated because the solvent was THF.
The mol% data are based on reacted 2,5-dihydrofuran.
0050/44208 216 8 ~ 5 8 i0 Example 6 2 g of a copper on active carbon catalyst (copper content: 10% by weight, calculated as Cu and based on the total weight of the - 5 catalyst), 5 g of 2,5-dihydrofuran and 2;6 g of water were introduced into a 50 ml metal autoclave with stirrer. The cata-lyst had previously been prepared by impregnating the active car-bon with an aqueous copper nitrate solution, drying at 100°C and activating in a stream of hydrogen at 250'C for 2 h. A pressure of 50 bar was produced in the autoclave by injecting hydrogen, and then the autoclave was heated at 150'C for one hour. The autoclave was subsequently cooled to room temperature and decompressed. The conversion was 85%, and 31 mol% 1,4-butanediol, 30 mol% tetra-hydrofuran, 2 mol% y-butyrolactone, 18 mol% 4-hydroxybutyraldehyde and 1 mol% butanol, in each case based on the amount of 2,5-dihy-drofuran reacted, were obtained.
Example 7 5 g of 2,5-dihydrofuran and 5.4 g of water were reacted as in Ex-ample 6 on 2 g of a ruthenium on active carbon catalyst whose ruthenium content was 3% by weight, calculated as Ru and based on the complete catalyst. The catalyst had been prepared by impreg-nating the active carbon with aqueous ruthenium nitrate solution, drying at 100'C and activating in a stream of hydrogen at 250'C
for 2 h. The 2,5~iihydrofuran conversion was 100%, and 51 mol%
1,4-butanediol, 35 mol% tetrahydrofuran, 1 mol% y-butyrolactone and 3 mol% butanol, in each case based on the amount of 2,5-dihy-drofuran reacted, were obtained.
Example 8 0.2 g of dirhenium heptoxide (Re20~) was dissolved in 5.1 g of wa-ter in a 50 ml metal autoclave with stirrer. A pressure of 40 bar was produced in the autoclave by injecting hydrogen, and then the autoclave was heated at 300°C for 1 hour. After the autoclave had been cooled and decompressed, 5 g of 2,5-dihydrofuran were put in the reactor. Hydrogen was again injected into the autoclave until' the pressure was 50 bar, and subsequently the autoclave was heated at 150'C for 1 hour and then cooled to room temperature and decompressed. The 2,5-dihydrofuran conversion was 99%, and mol% 1,4-butanediol, 36 mol% tetrahydrofuran, 1 mol% 4-hydrox-ybutyraldehyde, 3 mol% y-butyrolactone and 12 mol% butanol, in each case based on the amount of 2,5-dihydrofuran reacted, were 45 obtained.
0050/44208 216 8 4 5 ~
m Example 9 0.09 g of the homogeneous catalyst RuHCICo(PPh3)3 (Ph means phenyl), 5 g of 2,5-dihydrofuran and 5.1 g of water were introduced into a metal autoclave with stirrer, and~a--pressure of 50 bar was produced by injecting hydrogen. The autoclave was then heated at 150°C for 1 h and subsequently cooled to room tempera-ture and decompressed. The homogeneous discharge from the reac-tion showed a 2,5-dihydrofuran conversion of 90% and contained 40 mol% 1,4-butanediol, 10 mol% tetrahydrofuran and 5 mol% buta-nol, in each case based on the amount of 2,5-dihydrofuran reacted.
Example 10 25 ml of a copper- and rhenium-containing active carbon catalyst which had a copper content of 3% by weight, calculated as copper, and a rhenium content of 6% by weight, calculated as rhenium, in each case based on the total weight of the catalyst, were introduced into a tubular reactor with a capacity of 25 ml. The catalyst had been prepared by impregnating 4 mm active carbon pellets with an aqueous solution of copper nitrate and rhenium heptoxide, subsequently drying at 120°C and activating in a stream of hydrogen at 300°C for 3 hours. The reactor was operated contin-uously in a trickle process at 190°C under a pressure of 120 bar of hydrogen. 13 g of 2,5-dihydrofur.an per h and 7 g of water per h were pumped through two separate feedlines to the top of the reactor. 50 1/h of gas left the reactor. The conversion was 98%, and the 1,4-butanediol yield was 69%, the THF yield was 20%, the butyrolactone yield was 4% and the n-butanol yield was 6%. The remainder was predominantly 4-hydroxybutyraldehyde.
Example 11 400 ml of the catalyst from Example 2 were packed in a 400 ml tu-bular reactor. 200 g of 2,5-~ihydrofuran per h and 100 g of water per h were pumped through two separate feedlines into the head of the reactor at 190 - 200°C and under a pressure of 120 bar of hy-drogen. The reactor was operated with recirculation of product, and the circulation: feed ratio was 10:1. The off-gas stream amounted to 100 1/h. The reactor was operated continuously for 30 days, and samples were taken during this time, the conversion be-ing 100% and the following yields being obtained: 65 - 69%
1,4-butanediol, 25 - 30% THF, 1 - 3% butyrolactone, 5 - 6%
n-butanol. No inactivation of the catalyst had occurred even after 30 days.
AMENDED SHEET
In the process according to the invention, the 2,5-dihydrofuran is reacted with water in general with a 2,5-dihydrofuran/water molar ratio of from 1:1 to 1:100, preferably 1:1 to 1:50 and par-ticularly preferably l : Y to 1:10, and~wi:n--the presence--of---hydrogen and of a hydrogenation catalyst under a pressure of, in general, from 1 to 300 bar, preferably from 5 to 200 bar and, in particu lar, in general from 10 to 150 bar, at from 20 to 300°C, prefer ably 40 to 230°C and particularly preferably from 80 to 200°C to give 1,4-butanediol.
Hydrogenation catalysts which can be used in the process accord ing to the invention are, in general, all catalysts suitable for the hydrogenation of carbonyl groups. The catalysts used may ei they be soluble homogeneously in the reaction medium, as de scribed, for example, in Houben-Weyl, Methoden der Organischen Chemie, volume IV/lc, 45-67, Thieme Verlag, Stuttgart 1980, or else be heterogeneous as described in Houben-Weyl, Methoden der Organischen Chemie, volume IV/lc, 16-26. Particularly preferred homogeneous catalysts are the complexes of rhodium, ruthenium and cobalt with phosphine or phosphite ligands, whose preparation is described, for example, in CA-A 7 276 41, H. Brunner in Hartley:
The chemistry of the metal-carbon bond; Vol. 5, 110-124, John Wiley & Sons, New York 1989 and Toth et al., Inorg. Chim. Acta 42, (1980) 153 and the literature cited therein.
However, heterogeneous hydrogenation catalysts are preferably used in the process according to the invention, that is to say catalysts which are essentially insoluble in the reaction medium.
Preferred hydrogenation catalysts of this type contain one or more elements of group Ib, VIb, VIIb and VIIIb of the periodic table of the elements, in particular copper, chromium, molybde-num, tungsten, rhenium, ruthenium, cobalt, rhodium, iridium, nickel, palladium, iron and/or platinum.
Heterogeneous hydrogenation catalysts which can be used in the process according to the invention are those composed of metals in activated, finely divided form with a large surface area, for example Raney nickel, Raney cobalt, palladium, platinum or rhe-nium sponges.
It is furthermore possible to use, for example, precipitated cat-alysts in the process according to the invention. Catalysts of this type can be prepared by precipitating their catalytically active components from solutions of salts thereof, in particular from solutions of the nitrates and/or acetates thereof, for exam-ple by adding solutions of alkali metal and/or alkaline earth metal hydroxides and/or carbonates, as, for example, sparingly soluble hydroxides, oxide hydrates, basic salts or carbonates, subsequently drying the resulting precipitates and then convert-ing them by calcination at, in general, from 300 to 700°C, in par-ticular 400 to-600°C~ into the relevant oxides, mixed oxides andJ
or mixed valency oxides which are reduced by treatment with hy-drogen or with hydrogen-containing gases at, as a rule, from 100 to 700°C, in particular at 150 to 400°C, to the relevant metals and/or oxides of a lower oxidation state, and converted into the .
actual catalytically active form. In this connection, as a rule, reduction is continued until water is no longer formed.~To pre-pare precipitated catalysts which contain a carrier material, the precipitation of the catalytically active components can take place in the presence of the relevant carrier material. However, it is also possible and advantageous for the catalytically active components to be precipitated simultaneously with the carrier ma-terial from the relevant salt solutions.
The hydrogenation catalysts preferably employed in the process according to the invention contain the hydrogenation-catalyzing metals or compounds thereof deposited on a carrier material.
Apart from the abovementioned precipitated catalysts which also contain a carrier material in addition to the catalytically ac-tive components, supported catalysts which are generally suitable for the process according to the invention are those in which the hydrogenation-catalyzing components have been applied to a carrier material by, for example, impregnation.
The way the catalytically active metals are applied to the car-rier is, as a rule, not critical and can be brought about in a variety of ways. The catalytically active metals can be applied to these carrier materials for example by impregnation with solu-tions or suspensions of the salts or oxides of the relevant ele-ments, drying and subsequent reduction of the metal compounds to the relevant metals or compounds of a lower oxidation state using a reducing agent, preferably using hydrogen or complex hydrides.
Another possibility for the application of the catalytically ac-tive metals to these carriers comprises impregnating the carriers' with solutions of salts which can easily be thermally decomposed, eg. with nitrates, or with complex compounds which can easily be thermally decomposed, eg. with carbonyl or hydrido complexes of the catalytically active metals, and heating the impregnated car-riers at from 300 to 600°C for the thermal decomposition of the adsorbed metal compounds. This thermal decomposition is prefer-ably carried out under a protective gas atmosphere. Examples of suitable protective gases are nitrogen, carbon dioxide, hydrogen or the noble gases. It is furthermore possible to deposit the 0050/44208 21 fi 8 4 5 8 catalytically active metals on the carrier by vapor deposition or by flame spraying. The content of catalytically active metals in these supported catalysts is not in principle critical for the success of the process according to the invention. It is self-ev-5 ident to the skilled ~urorker that higher contents ofwcatalytically active metals in these supported catalysts lead to higher space-time conversions than do lower contents. However, the generally used supported catalysts have a content of catalytically active metals of from 0.1 to 80%, preferably 0.5 to 30%, of the total weight of the catalyst. Since these contents are based on the complete catalyst including carrier material but the vax'ious car-rier materials have very different specific gravities and specif-ic surface areas, however, contents higher or lower than these have no adverse effect on the result of the process according to the invention. It is, of course, also possible. to apply a plural-ity of the catalytically active metals to the particular carrier material. It is furthermore possible for the catalytically active metals to be applied to the carrier for example by the processes of DE A 25 19 817, EP-A1 477 219 and EP-A 285 420. The catalytic-ally active metals are present in the catalysts disclosed in the abovementioned publications in the form of an alloy produced by thermal treatment and/or reduction of the, for example, by im-pregnation on a deposited salts or complexes of the above-mentioned metals.
The activation of the precipitated catalysts and of the supported catalysts can also take place in situ in the reaction mixture by the hydrogen present therein, but these catalysts are preferably activated separately before use thereof.
Carrier materials which can generally be used are the oxides of aluminum and titanium, zirconium dioxide, silicon dioxide, kie-selguhr, silica gel, aluminas, eg. montmorillonite, silicates such as magnesium or aluminum silicates, zeolites such as ZSM-5 or ZSM-10 zeolites as well as active carbon. Preferred carrier materials are aluminum oxides, titanium dioxides, zirconium diox-ide and active carbon. It is, of course, also possible to use mixtures of various carrier materials as carriers for catalysts which can be used in the process according to the invention.
The following catalysts may be mentioned as examples of heteroge-neous catalysts which can be employed in the process according to the invention:
Platinum black, platinum on active carbon, platinum dioxide, pal-ladium on active carbon, palladium on aluminum oxide, palladium on silicon dioxide, palladium on barium sulfate, rhodium on ac-tive carbon, rhodium on aluminum oxide, ruthenium on silicon dioxide or active carbon, nickel on silicon dioxide, Raney nickel, cobalt on silicon dioxide, cobalt on aluminum oxide, Raney cobalt, carbonyl iron powder, rhenium black, Raney rhenium, rhenium on active carbon, rhenium/palladium on active carbon, rhenium/platinum on active carbon, copper on silicon dioxide, copper on aluminum oxide, copper on active carbon, Raney copper, platinum oxide/rhodium oxide mixtures, platinum/palladium on ac-tive carbon, copper chromite, barium chromite, nickel/chrornium oxide on aluminum oxide, dirhenium heptoxide (Re207), cobalt sul-fide, nickel sulfide, molybdenum(VI) sulfide, copper/molybde-num(VI) oxide/silicon dioxide/aluminum oxide catalysts and the catalysts disclosed in DE A 39 32 332, US A 3 449 445, EP-A
44 444, EP A 147 219, DE A 39 04 083, DE-A 23 21 101, EP-A
415 202, DE-A 2 366 264 and EP A 100 406.
Lewis and/or Bronsted acid components such as zeolites, aluminum oxides or silicon oxides, phosphoric acid or sulfuric acid can be added to the abovementioned catalysts. They are generally added in amounts of 0.01 to 5%, preferably of 0.05 to 0.5% and particu-larly preferably of 0.1 to 0.4% of the weight of the catalyst employed.
The process according to the invention is particularly preferably carried out using hydrogenation catalysts which contain Hronsted and/or Lewis acid centers. When catalysts of this type are used it is not generally necessary to add an additional Bronsted or Lewis acid to the reaction mixture.
Examples of homogeneous catalysts containing Bronsted acid cen-ters which can be used are transition metal complexes of metals of group VIIIb, in particular rhodium, ruthenium and cobalt com-plexes with phosphine or phosphite ligands which carry Bronsted acid functional groups such as carboxyl, sulfo and/or phospho groups as substituents, for example complexes of the said transi-tion metals with triphenylphosphine-p-sulfonic acid ligands. Li-gands of this type can be prepared, for example, by the process of Angew. Chem. 105, (1993) 1097.
Particularly advantageous results can be achieved in the process according to the invention with heterogeneous catalysts which contain Bronsted or Lewis acid centers. The catalytically active metals themselves, for example, can act as Bronsted or Lewis acid centers if they are not completely reduced to the relevant metals in the activation of the catalyst with hydrogen or hydrogen-con-taining gases. This applies, for example, to the rhenium and chromite-containing catalysts such as rhenium black and copper chromite. The rhenium is present in rhenium black as a mixture of metallic rhenium with rhenium compounds in higher oxidation states, and the latter may display effects like Lewis or Bronsted acids. It is furthermore possible for such Lewis or Bronsted acid centers to be introduced into the catalyst via the carrier mate-rial used: Examples of carrier materials containingTLewis-or Bronsted acid centers are the aluminum oxides, titanium dioxides, zirconium dioxide, silicon dioxide, the silicates, aluminas, zeo-lites and active carbon.
The hydrogenation catalysts particularly preferably used in the process according to the invention are therefore supported cata-lysts which contain elements of group Ib, VIb, VIIb and/or VIIIb of the periodic table of the elements, in particular elements of group Ib, VIIb and VIIIb of the periodic table of the elements, deposited on a carrier material acting as a Bronsted or Lewis acid. Examples of particularly advantageous catalysts are rhenium on active carbon, rhenium on zirconium dioxide, rhenium on tita-nium dioxide, rhenium on silicon dioxide, copper on active car-bon, copper on silicon dioxide and ruthenium on active carbon.
The process according to the invention can be carried out either continuously or batchwise. It is possible and advantageous to employ for continuous operation for example tubular reactors in which the catalyst is advantageously arranged in the form of a fixed bed through which the reaction mixture can be passed in a liquid-phase or trickle process. For batchwise operation it is possible to use either simple stirred reactors or, advanta-geously, loop reactors. When loop reactors are used, the catalyst is expediently arranged in the form of a fixed bed. If the starting material is not completely converted it can be returned to the reaction expediently either after removal of the required product by distillation or as part-stream together with the other reactants. This may prove advantageous in particular on continu-ous operation. In general, the yields of 1,4-butanediol are high-er from a continuous reaction than from a batchwise reaction on the same catalyst.
The process according to the invention can advantageously be car-ried out in the presence of a solvent which is inert under the reaction conditions, for example using water-soluble ethers such as tetrahydrofuran, dioxane or dimethoxymethane. It is also pos-sible and advantageous to employ alcohols, in particular the product 1,4-butanediol, as solvent'.
The discharge from the reaction in the process according to the invention is expediently worked up by distillation, when, apart from the main product 1,4-butanediol, the compounds which are formed in small amounts as by-products, tetrahydrofuran, y-butyro-lactone and butanol, can be obtained.
The 2,5-dihydrofuran starting material can be prepared by isomer-ization of vinyloxirane, for example by the-process-of US A 5 034 545 or US-A 5 082 956.
1,4-Butanediol is prepared on a large scale world-wide and is used as diol component for the preparation of, inter alia, poly-esters, polyurethanes and epoxy resins.
Examples Example 1 25 ml of a copper on silicon dioxide catalyst in the form of 4 mm pellets, with a copper content of 10% by weight, calculated as Cu and based on the complete catalyst, were packed into a tubular reactor with a capacity of 25 ml. The catalyst had been prepared by impregnating the silicon dioxide pellets with an ammoniacal copper carbonate/sodium nitrate solution and subsequently drying at 100°C. The catalyst was activated in a hydrogen atmosphere (100 1 H2/h) at 250°C for 2 hours. Subsequently 15 ml/h of a mix-ture of 2.8 parts by weight 2,5~iihydrofuran, 2.8 parts by weight of water and 1 part by weight of 1,4-dioxane were continuously passed over the catalyst under a hydrogen pressure of 120 bar and at a reactor temperature of 134°C.
The composition of the discharge from the reaction is indicated in the Table.
Example 2 The mixture of 2,5-dihydrofuran, water and 1,4-dioxane described in Example 1 was reacted as in Example 1 on a rhenium on active carbon catalyst which had a rhenium content of 6% by weight, calculated as Re and based on the total weight of the catalyst, under a hydrogen pressure of 120 bar and at 200°C. The rhenium on active carbon catalyst had been prepared by impregnating the active carbon pellets with an aqueous dirhenium heptoxide solu-tion and subsequently drying at 120°C. Before use it was activated with hydrogen at 300°C for 3 hours.
The composition of the discharge from the reaction is indicated in the Table.
0050/44208 21 s g 4 5 8 Example 3 A mixture of 2,5-dihydrofuran (3.1 parts by weight), 1,4-dioxane (3.1 parts by weight) and water (1 part by weight) was reacted as in Example 1 on a rhenium on-titanium dioxide catalyst--which--had -a rhenium content of 6% by weight, calculated as Re and based on the total weight of the catalyst, under a hydrogen pressure of 120 bar and at 154°C. The rhenium catalyst had previously been prepared by impregnating titanium dioxide pellets with aqueous rhenium heptoxide solution and drying at 120°C and was activated before use in a stream of hydrogen at 300°C for 3 hours:
The composition of the discharge from the reaction is indicated in the Table.
Example 4 A mixture of 2,5-dihydrofuran (1.5 parts by weight), tetrahydro-furan (1.1 parts by weight) and water (1 part by weight) was reacted as in Example 1 on a rhenium on titanium dioxide catalyst as in Example 3 under a hydrogen pressure of 120 bar and at 200°C.
In a second experiment, the flow rate of the reaction mixture was doubled to 50 ml/h.
The compositions of the discharges from the reaction are indi-cated in the Table.
Example Flow rateBD THF Conversion [ml/h] GBL [%]
HBA
BuOH
[mol%]
1 25 32 15 0.3 1 2 51 4 25 79 * 5 0 9 100 50 71 * - 9 2 9 95 BD: 1,4-butanediol, THF: tetrahydrofuran, GBL: y-butyrolactone;
HBA: 4-hydroxybutanal, BuOH: n-butanol *: The amount of THF formed in the experiments was not calcu-lated because the solvent was THF.
The mol% data are based on reacted 2,5-dihydrofuran.
0050/44208 216 8 ~ 5 8 i0 Example 6 2 g of a copper on active carbon catalyst (copper content: 10% by weight, calculated as Cu and based on the total weight of the - 5 catalyst), 5 g of 2,5-dihydrofuran and 2;6 g of water were introduced into a 50 ml metal autoclave with stirrer. The cata-lyst had previously been prepared by impregnating the active car-bon with an aqueous copper nitrate solution, drying at 100°C and activating in a stream of hydrogen at 250'C for 2 h. A pressure of 50 bar was produced in the autoclave by injecting hydrogen, and then the autoclave was heated at 150'C for one hour. The autoclave was subsequently cooled to room temperature and decompressed. The conversion was 85%, and 31 mol% 1,4-butanediol, 30 mol% tetra-hydrofuran, 2 mol% y-butyrolactone, 18 mol% 4-hydroxybutyraldehyde and 1 mol% butanol, in each case based on the amount of 2,5-dihy-drofuran reacted, were obtained.
Example 7 5 g of 2,5-dihydrofuran and 5.4 g of water were reacted as in Ex-ample 6 on 2 g of a ruthenium on active carbon catalyst whose ruthenium content was 3% by weight, calculated as Ru and based on the complete catalyst. The catalyst had been prepared by impreg-nating the active carbon with aqueous ruthenium nitrate solution, drying at 100'C and activating in a stream of hydrogen at 250'C
for 2 h. The 2,5~iihydrofuran conversion was 100%, and 51 mol%
1,4-butanediol, 35 mol% tetrahydrofuran, 1 mol% y-butyrolactone and 3 mol% butanol, in each case based on the amount of 2,5-dihy-drofuran reacted, were obtained.
Example 8 0.2 g of dirhenium heptoxide (Re20~) was dissolved in 5.1 g of wa-ter in a 50 ml metal autoclave with stirrer. A pressure of 40 bar was produced in the autoclave by injecting hydrogen, and then the autoclave was heated at 300°C for 1 hour. After the autoclave had been cooled and decompressed, 5 g of 2,5-dihydrofuran were put in the reactor. Hydrogen was again injected into the autoclave until' the pressure was 50 bar, and subsequently the autoclave was heated at 150'C for 1 hour and then cooled to room temperature and decompressed. The 2,5-dihydrofuran conversion was 99%, and mol% 1,4-butanediol, 36 mol% tetrahydrofuran, 1 mol% 4-hydrox-ybutyraldehyde, 3 mol% y-butyrolactone and 12 mol% butanol, in each case based on the amount of 2,5-dihydrofuran reacted, were 45 obtained.
0050/44208 216 8 4 5 ~
m Example 9 0.09 g of the homogeneous catalyst RuHCICo(PPh3)3 (Ph means phenyl), 5 g of 2,5-dihydrofuran and 5.1 g of water were introduced into a metal autoclave with stirrer, and~a--pressure of 50 bar was produced by injecting hydrogen. The autoclave was then heated at 150°C for 1 h and subsequently cooled to room tempera-ture and decompressed. The homogeneous discharge from the reac-tion showed a 2,5-dihydrofuran conversion of 90% and contained 40 mol% 1,4-butanediol, 10 mol% tetrahydrofuran and 5 mol% buta-nol, in each case based on the amount of 2,5-dihydrofuran reacted.
Example 10 25 ml of a copper- and rhenium-containing active carbon catalyst which had a copper content of 3% by weight, calculated as copper, and a rhenium content of 6% by weight, calculated as rhenium, in each case based on the total weight of the catalyst, were introduced into a tubular reactor with a capacity of 25 ml. The catalyst had been prepared by impregnating 4 mm active carbon pellets with an aqueous solution of copper nitrate and rhenium heptoxide, subsequently drying at 120°C and activating in a stream of hydrogen at 300°C for 3 hours. The reactor was operated contin-uously in a trickle process at 190°C under a pressure of 120 bar of hydrogen. 13 g of 2,5-dihydrofur.an per h and 7 g of water per h were pumped through two separate feedlines to the top of the reactor. 50 1/h of gas left the reactor. The conversion was 98%, and the 1,4-butanediol yield was 69%, the THF yield was 20%, the butyrolactone yield was 4% and the n-butanol yield was 6%. The remainder was predominantly 4-hydroxybutyraldehyde.
Example 11 400 ml of the catalyst from Example 2 were packed in a 400 ml tu-bular reactor. 200 g of 2,5-~ihydrofuran per h and 100 g of water per h were pumped through two separate feedlines into the head of the reactor at 190 - 200°C and under a pressure of 120 bar of hy-drogen. The reactor was operated with recirculation of product, and the circulation: feed ratio was 10:1. The off-gas stream amounted to 100 1/h. The reactor was operated continuously for 30 days, and samples were taken during this time, the conversion be-ing 100% and the following yields being obtained: 65 - 69%
1,4-butanediol, 25 - 30% THF, 1 - 3% butyrolactone, 5 - 6%
n-butanol. No inactivation of the catalyst had occurred even after 30 days.
Claims (11)
1. A process for preparing 1,4-butanediol, which comprises reacting 2,5-dihydrofuran in one stage in the presence of wa-ter and hydrogen at from 20 to 300°C and under a pressure of from 1 to 300 bar on a hydrogenation catalyst.
2. A process as claimed in claim 1, wherein a hydrogenation cat-alyst which contains at least one element from group Ib, VIb, VIIb or VIIIb of the periodic table of the elements is used.
3. A process as claimed in claim 1 or 2, wherein a heterogeneous hydrogenation catalyst is employed.
4. A process as claimed in any of claims 1 to 3, wherein a hydrogenation catalyst whose catalytically active component has been applied to a carrier is used.
5. A process as claimed in any of claims 1 to 4, wherein a hy-drogenation catalyst which contains one or more components with Brönsted or Lewis acid activity is used.
6. A process as claimed in any of claims 1 to 5, wherein a hydrogenation catalyst which contains rhenium is used.
7. A process as claimed in any of claims 1 to 5, wherein a hydrogenation catalyst which contains copper is used.
8. A process as claimed in any of claims 1 to 5, wherein a hydrogenation catalyst which contains nickel or cobalt is used.
9. A process as claimed in any of claims 1 to 5, wherein a hydrogenation catalyst which contains a platinum metal is used.
10. A process as claimed in any of claims 1 to 9, wherein a hydrogenation catalyst whose catalytically active component has been applied to a carrier material which contains alumi-num oxide, aluminas, silicon dioxide, zirconium dioxide, ti-tanium dioxide, a zeolite and/or active carbon is used.
11. A process as claimed in claim 1 or 2, wherein a homogeneous hydrogenation catalyst which contains an element of group VIIIb of the periodic table of the elements is used.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4325753.4 | 1993-07-31 | ||
| DE4325753A DE4325753A1 (en) | 1993-07-31 | 1993-07-31 | Process for the preparation of 1,4-butanediol |
| PCT/EP1994/002232 WO1995004023A1 (en) | 1993-07-31 | 1994-07-07 | Process for producing 1,4 butane diol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2168458A1 CA2168458A1 (en) | 1995-02-09 |
| CA2168458C true CA2168458C (en) | 2004-05-25 |
Family
ID=6494169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002168458A Expired - Fee Related CA2168458C (en) | 1993-07-31 | 1994-07-07 | The preparation of 1,4-butanediol |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0711267B1 (en) |
| JP (1) | JP3616642B2 (en) |
| KR (1) | KR100307255B1 (en) |
| CN (1) | CN1066702C (en) |
| AT (1) | ATE159237T1 (en) |
| AU (1) | AU7384794A (en) |
| CA (1) | CA2168458C (en) |
| DE (2) | DE4325753A1 (en) |
| ES (1) | ES2107852T3 (en) |
| FI (1) | FI111458B (en) |
| RU (1) | RU2119905C1 (en) |
| TW (1) | TW328947B (en) |
| WO (1) | WO1995004023A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4422051A1 (en) * | 1994-06-27 | 1996-01-04 | Basf Ag | Process for the preparation of 1,4-butanediol |
| DE4443529A1 (en) * | 1994-12-07 | 1996-06-13 | Basf Ag | Catalyst for carrying out reactions catalyzed by Lewis acid |
| DE19749201A1 (en) * | 1997-11-07 | 1999-08-12 | Degussa | Process for intermolecular etherification and ether cleavage |
| DE19929396B4 (en) * | 1999-06-26 | 2013-08-22 | Basf Se | Vacuum insulation units containing a sorbent |
| DE19935828A1 (en) * | 1999-07-29 | 2001-02-01 | Basf Ag | Production of pentanediols from alkoxydihydropyrans |
| CN103102246B (en) * | 2011-11-10 | 2014-10-22 | 中国科学院大连化学物理研究所 | Method for preparing 1,3-dihydric alcohol |
| EP2674552B1 (en) | 2012-06-12 | 2017-01-11 | iLOQ Oy | Electromechanical lock |
| CN104341269A (en) * | 2013-08-02 | 2015-02-11 | 胡小军 | Preparation method of 1,4-butanediol solution |
| CN105618051B (en) * | 2014-10-27 | 2018-01-26 | 中国科学院大连化学物理研究所 | A kind of catalyst for being used for CO hydrogenation synthesis higher alcohols coproduction naphtha and diesel oil and preparation method and application |
| BR112017012865B1 (en) * | 2014-12-18 | 2021-01-19 | Shell Internationale Research Maatschappij B.V. | process for the production of n-butanol and 1,4-butanediol from furan |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1248669B (en) * | 1965-01-07 | 1968-03-14 | Badische Anilin &. Soda-Fabrik Aktien gesellschaft, 6700 Ludwigshafen | Process for the preparation of 2 3-dihydrofurans |
| DE2519817A1 (en) * | 1975-05-03 | 1976-11-11 | Hoechst Ag | PROCESS FOR THE PRODUCTION OF BUTANDIOL- (1.4) |
| US4091041A (en) * | 1977-06-13 | 1978-05-23 | General Electric Company | Preparation of 1,4-diols by hydrolysis-hydrogenation of 2-alkoxytetrahydrofurans |
| US4476332A (en) * | 1983-12-21 | 1984-10-09 | Ethyl Corporation | Preparation of alkanediols |
| US4475004A (en) * | 1983-12-21 | 1984-10-02 | Ethyl Corporation | Preparation of alkanediols |
| US4879420A (en) * | 1988-05-06 | 1989-11-07 | E.I. Du Pont De Nemours And Company | Preparation of mixtures of butanediols |
| US4859801A (en) * | 1988-05-26 | 1989-08-22 | E. I. Du Pont De Nemours And Company | Synthesis of mixtures of butanediols |
| DE3909485A1 (en) * | 1989-03-22 | 1990-09-27 | Basf Ag | METHOD FOR PRODUCING BUTANDIOL-1,4 AND TETRAHYDROFURAN |
| US5254701A (en) * | 1991-05-20 | 1993-10-19 | Eastman Kodak Company | Process for the production of mixtures of 2-hydroxytetrahydrofuran and 4-hydroxybutanal |
-
1993
- 1993-07-31 DE DE4325753A patent/DE4325753A1/en not_active Withdrawn
-
1994
- 1994-07-07 AT AT94923711T patent/ATE159237T1/en not_active IP Right Cessation
- 1994-07-07 CN CN94192959A patent/CN1066702C/en not_active Expired - Fee Related
- 1994-07-07 JP JP50552095A patent/JP3616642B2/en not_active Expired - Fee Related
- 1994-07-07 AU AU73847/94A patent/AU7384794A/en not_active Abandoned
- 1994-07-07 EP EP94923711A patent/EP0711267B1/en not_active Expired - Lifetime
- 1994-07-07 DE DE59404358T patent/DE59404358D1/en not_active Expired - Lifetime
- 1994-07-07 ES ES94923711T patent/ES2107852T3/en not_active Expired - Lifetime
- 1994-07-07 CA CA002168458A patent/CA2168458C/en not_active Expired - Fee Related
- 1994-07-07 RU RU96108796/04A patent/RU2119905C1/en not_active IP Right Cessation
- 1994-07-07 WO PCT/EP1994/002232 patent/WO1995004023A1/en active IP Right Grant
- 1994-07-07 KR KR1019960700498A patent/KR100307255B1/en not_active IP Right Cessation
- 1994-07-29 TW TW083106943A patent/TW328947B/en not_active IP Right Cessation
-
1996
- 1996-01-30 FI FI960429A patent/FI111458B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| EP0711267B1 (en) | 1997-10-15 |
| JP3616642B2 (en) | 2005-02-02 |
| KR100307255B1 (en) | 2001-11-30 |
| TW328947B (en) | 1998-04-01 |
| FI960429A (en) | 1996-01-30 |
| DE59404358D1 (en) | 1997-11-20 |
| CN1128017A (en) | 1996-07-31 |
| WO1995004023A1 (en) | 1995-02-09 |
| ATE159237T1 (en) | 1997-11-15 |
| ES2107852T3 (en) | 1997-12-01 |
| EP0711267A1 (en) | 1996-05-15 |
| DE4325753A1 (en) | 1995-02-02 |
| CN1066702C (en) | 2001-06-06 |
| FI960429A0 (en) | 1996-01-30 |
| JPH09500877A (en) | 1997-01-28 |
| KR960703835A (en) | 1996-08-31 |
| RU2119905C1 (en) | 1998-10-10 |
| FI111458B (en) | 2003-07-31 |
| CA2168458A1 (en) | 1995-02-09 |
| AU7384794A (en) | 1995-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7038094B2 (en) | Hydrogenolysis of 5-carbon sugars, sugar alcohols, and methods of making propylene glycol | |
| US5905159A (en) | Method of producing 1,4-butanediol and tetrahydrofuran from furan | |
| US6841085B2 (en) | Hydrogenolysis of 6-carbon sugars and other organic compounds | |
| US4083809A (en) | Hydrogenation catalyst and method of producing same | |
| CA2168458C (en) | The preparation of 1,4-butanediol | |
| US5945571A (en) | Preparation of 1,4-butanediol | |
| JP2792986B2 (en) | Production method of alkanol | |
| JP3411285B2 (en) | Production method of γ-butyrolactone | |
| US5637735A (en) | Process for the preparation of gamma-butyrolactone | |
| US5977417A (en) | Preparation of 1,4-butanediol | |
| US5767326A (en) | Process for preparing hydroxymethylcyclopropane | |
| KR100538979B1 (en) | Method for the preparation of 1,4-butanediol from maleic ester | |
| KR100338131B1 (en) | Catalyst for the hydrogenation and method for preparing r-butyrolactone using the same catalyst | |
| KR960003794B1 (en) | Catalysts for hydrogenation of ester | |
| EP1431296A1 (en) | Process for preparing alpha- and beta-methyl-gamma-butyrolactone and 3-methyltetrahydrofuran | |
| MXPA97000123A (en) | Preparation of 1,4-butand |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |