DE2519817A1 - PROCESS FOR THE PRODUCTION OF BUTANDIOL- (1.4) - Google Patents

Description

HOECHST AKTIENGESELLSCHAFT 2519817

File number: 'HOE 75 / F 112

Date: May 2, 1975 Dr.MA/cr

Process for the preparation of butanediol (1.4)

The invention relates to a single-stage, catalytic process for the production of butanediol (1.4) from maleic anhydride, maleic acid or mixtures of both compounds. Butanediol- (1.4) is used, for example, as a preliminary product for the production of polyester fibers; butanediol- (1.4) is used, for example Terephthalic acid converted to polybutylene terephthalate at elevated temperature in the presence of catalysts.

Processes for the preparation of butanediol (1.4) are already known. In addition to a number of older syntheses, e.g. based on acetylene formaldehyde or 1,4-dihalobutane, more recently also described vv-butyrolactone as a starting material for the preparation of butanediol- (1.4).

On the other hand, there are no known industrially viable processes for the direct production of butanediol (1.4) from maleic anhydride or maleic acid which have hitherto worked economically. Although it is possible to convert maleic anhydride into butanediol (1.4) with a maximum yield of 64% , the Raney cobalt used as a catalyst is not suitable for continuous industrial operation because it is dissolved and partially formed by maleic anhydride and the maleic acid as an intermediate is irreversibly deactivated. In addition, the reaction requires extremely high pressures of about 8oo bar and temperatures of about 275 ° C., at which the diol formed is already dehydrated again with strong tetrahydrofuran formation.

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Also with nickel molybdate or nickel chromate catalysts, which are used in older processes are described, one obtains butanediol- (1.4) from maleic anhydride also only with a yield of about 50% in addition to large amounts of tetrahydrofuran. This will also be very high, technically more difficult to achieve pressures of approx. 8oo bar are required. These catalysts are also unstable in continuous operation and become like the copper-chromium oxides known for ester hydrogenation dissolved and deactivated by acids. This also applies in the same way to pure nickel catalysts.

With other catalysts described as more acid-stable, which contain, for example, rhenium, rhenium-molybdenum-cobalt or nickel-molybdenum-rhenium or also nickel-rhenium, maleic anhydride or maleic acid, on the other hand, can only convert a maximum of 9-14 % into butanediol (1.4) being transformed. The main products formed are succinic acid, tetrahydrofuran and V'-butyrolactone with a yield of over 90% in some cases. But here, too, it is mainly the nickel and cobalt components of the catalysts that dissolve. In other cases described, with rhenium catalysts from maleic anhydride or maleic acid, no butanediol (1.4) at all is formed, only succinic acid. The same is stated for platinum and rhodium catalysts. Finally, with palladium, eg Pd / carbon, maleic anhydride can only be hydrogenated to γ-butyrolactone or the reaction even stops at the succinic acid stage.

A catalytic process for the preparation of butanediol (1.4) has now been found, with which it is possible in one step Maleic anhydride or maleic acid or their mixtures with excellent Conversions and yields to convert directly to butanediol- (1.4) with a very good lifetime of the catalysts.

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This is very surprising, since according to the prior art, as mentioned above, reasonably passable yields only with unstable, Catalysts that are absolutely unsuitable for continuous technical operation can be achieved.

In contrast, more stable catalysts give, if at all, only very poor yields of 1,4-butanediol or even just succinic acid.

The present invention therefore relates to a method for the preparation of butanediol (1.4) from maleic anhydride, maleic acid or mixtures thereof, characterized in that one Maleic anhydride, maleic acid or their mixtures are hydrogenated in one stage in the presence of catalysts that simultaneously contain elements of the VII. subgroup or their compounds and elements' of the VIII. subgroup or their compounds or mixtures contain these elements and compounds.

The new process is particularly notable for the fact that there are practically no by-products v / ie tetrahydrofuran, j ^ -butyrolactone and succinic acid supplies and that also provides that elsewhere in the hydrogenation of maleic anhydride and maleic acid to tetrahydrofuran and ju ^ -butyrolactone described formation of n-butanol is insignificant.

This is a technically simple and also very economical one new process for the production of 1,4-butanediol, which is not associated with any waste problems as it was before occur especially in the older processes for the production of butanediol (1.4) from dihalobutanes.

The catalysts used in the new process contain both elements or compounds of elements of VII the VIII. subgroup of the periodic table including mixtures of elements of the one group with compounds of elements of the Manganese, rhenium, ruthenium, rhodium, palladium, osmium, iridium and platinum are particularly suitable. Rhenium, palladium and platinum are preferably used.

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What is particularly surprising here is the fact that by a simple combination of elements of subgroup VII or their compounds with elements of subgroup VIII or their compounds a selectivity of butanediol (1.4) can be achieved, as it is with the elements from a group alone or their compounds, in particular with rhenium or palladium individually, is not achieved.

In addition, this was not expected to be practical quantitative conversions of maleic anhydride and / or maleic acid can be achieved without the activity of the invention Catalysts wears off noticeably. The inventive combination of the elements from VII. With the Elements of subgroup VIII, in particular rhenium and palladium and / or their compounds, therefore also has one surprisingly large stabilizing effect and significantly increases the life of the catalysts compared to those in described in the older literature. This is of decisive importance and conditional for continuous technical operation also the superiority of the new process over the older ones.

The catalysts are in the process according to the invention in generally used in powder form. But they can also be tabletted or with-if necessary. carrier inert materials used mixed.

Examples of possible carriers are: silicon dioxide, titanium dioxide, silicon dioxide-aluminum oxide, carbon, thorium oxide, Zirconia, silicon carbide, spinels and alumina.

In the event that supported catalysts or catalysts mixed with inert materials are used, the amount is catalytically active substances in general between o, l and 50% by weight of the total mass of the catalyst. The amount of inert materials (carriers) is thus generally between 99.9 and 5o% of the total mass of the catalyst.

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The ratio of the elements of subgroup VIII to those Subgroup VII is between 99: 1 and 1:99, preferred between Io: 1 and 1: Io.

The catalysts can be used both as elements and also as their compounds or as mixtures of the two, if appropriate together with carriers. Accordingly, the catalysts can also be prepared in such a way that suitable compounds are used directly begins, if necessary on supports, or that these compounds are reduced to a greater or lesser extent, possibly down to the elements.

Examples of possible compounds are: the oxides, oxide hydrates, Carbonates, nitrates, borides, carboxylates, such as acetates, propionates, butyrates, chelates of 1,3-diketo compounds, E.g. enolates such as acetylacetonate, benzoylacetonate, acetoacetic ester compounds the carboxylates, acetylacetonates, oxides and oxide hydrates are suitable. For technical and economic The reasons are the use of e.g. rhenium as a potassium barrier or rhenium heptoxide and the use of e.g. palladium as a Palladium (II) acetate or acetylacetonate is particularly preferred, especially since these products are commercially available.

For the production of palladium-rhenium catalysts, for example is generally a solution of a palladium carboxylate or a solution with carboxylic acids in palladium carboxylate Compound such as palladium oxide hydrate, palladium nitrate, palladium oxycarbonate or a salt of a 1,3-diketo compound j such as acetoacetic ester or acetylacetone in an anhydrous or water-containing carboxylic acid together with perrhenic acid or their salts applied to the carrier, namely by Soaking, dipping or suspending the carrier or by spraying it on. Instead of a palladium carboxylate, one can also use one Choose a compound that changes with the carboxylic acid into a palladium carboxylate, e.g. the oxide hydrate, the nitrate or the Palladium oxycarbonate. The carboxylic acid is then through

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Drying at higher temperatures in a vacuum or at normal pressure removed. The catalyst can now be used directly, but it is preferably used in the gas or liquid phase Treated with reducing agents at temperatures from 15 to 2oob.

Carboxylic acids are all liquid ones that can be evaporated without decomposition in a vacuum aliphatic carboxylic acids with 2 to 10 carbon atoms suitable. Acetic acid, propionic acid or butyric acid are preferred, but especially acetic acid.

The two solutions used to make the catalysts Compounds such as a palladium salt and a rhenium compound can be separately applied to the supports will. However, it is advantageous to use palladium and rhenium compounds to dissolve together in a carboxylic acid. But it is also possible to first use one of the palladium compounds mentioned above to apply to the carrier and then to pull up the solution of a rhenium compound in a carboxylic acid. the Inertia can be powdery or shaped, for example granules, pellets, tablets, extruded parts, saddle bodies, Rings or honeycomb tubes.

The reduction of the catalysts can be in the liquid phase, for example with hydrazine hydrate. However, it is advantageous at higher temperatures, e.g. from 100-2oo ° C in the gas phase with reducing vapors or gases such as hydrogen, methanol, formaldehyde, ethylene, propylene, butenes diluted or undiluted to reduce. An initially strong dilution with inert gases proved to be particularly favorable, such as nitrogen, carbon dioxide or noble gases and an increase in concentration that takes place with progressive reduction of the reducing agent, so that the reduction is terminated, for example, in pure hydrogen. The reduction can be done in a separate device as well as in the same apparatus, which is used for converting the Maleiimhydrdds and / or the maleic acid in. 1,4-butanediol is used.

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The catalysts can be pyrophoric. In these cases you have to they are treated accordingly. Particularly in these cases is a reduction of the catalyst and the subsequent conversion maleic acid and / or anhydride in one and the same apparatus is advantageous.

For technical operation, the one according to the invention is single-stage Direct process is also of great importance that practically no succinic acid is formed due to their extremely low solubility would easily turn out and thus lead to blockages of the apparatus or a further one Procedural stage would make necessary.

For the optimal design of the process according to the invention, the hydrogenolysis of the starting products maleic anhydride and / or maleic acid is generally carried out at elevated pressures and temperatures.

The reaction temperatures are generally between and 300.degree. C., preferably in the range from 150-25o.degree. The reaction pressure is generally between 50 and 500 bar. The range from 100 to 35o bar is preferred.

The hydrogen used for the hydrogenolysis of maleic anhydride or maleic acid is generally greater stoichiometric excess used. Unconverted hydrogen can be returned to the reaction as cycle gas. The reaction can be carried out either continuously or batchwise. The hydrogen generally comes from an industrial point of view purely for use. However, admixtures of inert gases, e.g. nitrogen, do not interfere with the course of the reaction. The reaction time in the process according to the invention is in generally between 5 minutes and 8 hours. E.g. it is about 3-6 hours when working discontinuously in the autoclave will.

Powdered contacts can be filtered off after the end of the experiment or centrifuged and used again without any noticeable loss of activity.

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When working continuously, e.g. in the trickle phase, generally tabletted or supported catalysts are used.

When the reaction is carried out in practice, the solvents known for hydrogenation, such as, for example, dioxane, tetrahydropyran or other cyclic or open-chain ethers, such as, for example, tetrahydrofuran or diethyl ether, can be used. Also suitable as solvents are polyalkylene glycol dialkyl ethers, for example tetramethylene glycol dibutyl ether, tetramethylene glycol dipentyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether and diethylene glycol dibutyl ether or mixtures of these or other solvents. Those whose boiling points are above 245 ° C. have proven particularly useful. The content of maleic acid and / or anhydride in the starting solution is then generally between 5 and 60%. For example, the use of maleic anhydride as a 2o-40% solution in 1,4-dioxane has proven itself. In the case of maleic acid, water is also suitable as a solvent. The amount of catalyst required for the hydrogenation is generally 0.5 to 25% of the amount of maleic anhydride or maleic acid.

Both maleic anhydride, such as maleic acid and any mixtures of the two can be used as starting products.

The reaction mixtures are generally worked up by fractional distillation.

Of the different procedures, e.g. in the batchwise production of butanediol- (1.4), the following has emerged Method particularly proven:

A solution of maleic anhydride in 1,4-dioxane is placed in a high pressure autoclave together with the catalyst, hydrogen pressed and the reaction mixture heated. After the reaction has ended, the mixture is cooled, the catalyst is separated off and the mixture is fractionally distilled.

The following examples serve to illustrate the process.

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example 1

There are 27 g of palladium acetate and 4 g of rhenium heptoxide Dissolved 80 ° C. in 1200 ml of acetic acid, added 100 g of kieselguhr, evaporated to dryness with stirring in vacuo and at 200 ° C. reduced in a hydrogen atmosphere.

0.5 moles of maleic anhydride (49 g) are dissolved in 100 ml of dioxane. The solution is poured into a 1-1 shaking autoclave together with 5 g of the powdered kieselguhr catalyst, which contains 0.6% palladium and 2.3% rhenium. Hydrogen is injected until the pressure has reached 215 bar and the temperature is quickly raised to 225-230 ° C. After about 6 hours, the reaction is interrupted and the reaction mixture is rapidly cooled. After the catalyst has been separated off, 151.5 g of a water-clear, colorless reaction solution containing 27.9 % 1,4-butanediol (42.2 g), corresponding to 93.8 % of theory, are obtained. contains. In addition to butanediol (1.4) and the solvent dioxane, water as well as smaller amounts of γ-butyrolactone, tetrahydrofuran, n-butanol and titrimetrically traces of succinic acid can be detected by gas chromatography.

Example 2

49 g of maleic anhydride are dissolved in 100 ml of dioxane. The solution will be together with 5.9 g of the already used in Example 1, filtered off, still slightly moist catalyst as described in Example 1 implemented. 149.8 g of another colorless, water-clear solution, the 28.2% 1,4-butanediol (42.3 g) contains. This corresponds to 93.9% of the total. In addition to the other substances mentioned in Example 1, the reaction mixture contains still small amounts of a polyester.

Example 3

The calculated amount Platinacetat and rhenium heptoxide are added at 6o C as the acetic acid solution with diatomaceous earth, dried and reduced as described in Example ^ 1,.

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- Io -

A solution of 58 g of maleic acid (0.5 mol) in 2oo ml of water is together with 6 g of the kieselguhr catalyst, the Io% platinum u.

Contains 2.8% rhenium, placed in a 1 liter steel autoclave.

Hydrogen is injected until the pressure has reached 195 bar u.

heats up quickly to 23o ° C.

After a reaction time of about 3 1/2 hours, a further 25 bar of hydrogen are added. After a total of 5 hours, the reaction will canceled because no further hydrogen uptake was observed can be. The catalyst is separated off with a centrifuge and 255 g of reaction solution are obtained.

The water-clear, colorless solution contains 16% or 40.8 g of butanediol (1.4), corresponding to 90.9 % of theory.

In addition to butanediol (1.4) and water, the reaction mixture also contains 0.53% tf-butyrolactone, 0.6 % n-butanol and smaller amounts of tetrahydrofuran, succinic acid and butyric acid.

Example 4

To produce the desired amount of the catalyst, palladium acetate, rhodium acetate and rhenium heptoxide are dissolved in acetic acid in the calculated amounts, aluminosilicate powder is added and, as in Example!, Dried and reduced. 0.5 moles of maleic anhydride (49 g) are dissolved in 100 g of tetrahydropyran (approx. 114 ml). Is added 5.2 g of the silica-alumina catalyst added, the 8.3% palladium, 4.2% of rhodium and 2.7% rhenium and returns the mixture into a o _r 5 liter stirred autoclave magnetic hub. After injecting 189 bar of hydrogen, the mixture is quickly heated to 220 ° C. and allowed to react for a total of 4 1/2 hours. After this time it is cooled rapidly, the catalyst is separated off and the reaction mixture is analyzed by gas chromatography.

147 g of a solution are obtained which contain 26.9% butanediol (1.4) (39.6 g). This corresponds to approx. 88% of the total.

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'- 11 -

Example 5

To produce the catalyst, 100 g of activated carbon are used

2
(81o m / g BET, ο.9 ml / g pore volume) _{soaked with a solution of 20 g Na 3} PdCl ₄ in 86 ml water, dried with stirring, soaked with a solution of 4 g NaOH in 88 ml H ₀ O and Left to stand for 2 h. It is then washed free of chloride, dried to a weight of 150 g, soaked with a solution of 6 g of Re ₂ O ₇ in 50 ml of water, dried with stirring and reduced in hydrogen at 200 ° C. 0.25 mol of ilealic anhydride (24 g) and 0.25 mol of maleic acid (29 g) are dissolved in 100 ml of slightly warmed dioxane. 5 g of the activated carbon powder catalyst, which contains 4.1% rhenium and 8.2% palladium oxide, are added to this mixture, and the mixture is placed in a 0.5-liter high-pressure shaking autoclave. After injecting 170 bar of hydrogen, the mixture is heated to 232 ° C. and allowed to react for 3 hours. A further 40 bar of hydrogen are then metered in and, after a further 1.5 hours, the reaction mixture is rapidly cooled. The catalyst is separated off.

149.3 g of reaction solution are obtained, which contains 39.8 g of butanediol (1.4) contain.

Example 6

The kieselguhr catalyst used in Example 1 is on a Tablet press pressed into tablets with a diameter of 6 mm and a thickness of 2 mm. 1 liter of this catalyst is poured into an approx. 2 in long stainless steel high pressure reactor of 5.5 cm inner diameter introduced. The apparatus is flushed with nitrogen and given then slowly add hydrogen until the pressure has reached 260 bar. At the same time bit of adding the hydrogen at the bottom At the end of the reactor, a 32% solution is added from the upper end of maleic anhydride in dioxane and allows it to trickle over the contact. Once at the bottom of the reactor liquid escapes, is slowly heated to an operating temperature of 225 ° C, while hydrogen continues at a metering rate of approx. 8 - 10 Nm / h and dioxane maleic anhydride at approx. 152o g / h were added two hours after the loading

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operating temperature of 225 ° C is every hour exiting reaction mixture analyzed. About 1560 g of reaction mixture are obtained per hour, which is on average Contains 25-26% butanediol (1.4). This corresponds to approx. 85-90% of the theoretically possible yield of 1,4-butanediol. After 3oo Operating hours, no drop in performance has yet been observed.

Example 7

There are 20 g of palladium acetate, 10 g of iridium acetate, 4 g of rhenium heptoxide dissolved in 600 ml of glacial acetic acid, then 100 g of kieselguhr are stirred in; the mixture is taken in a rotary evaporator Dried in a water jet vacuum at 60 ° C. The dried catalyst is in a 4o C warm, aqueous solution of Sodium borohydride reduced, then washed out and dried. It contains 8.2% palladium, 4% iridium and 2.3% rhenium as boride, the percentages being based on the elements.

5 g of this catalyst are placed in an autoclave together with 0.5 moles of maleic anhydride and 100 ml of dioxane and as indicated in Example 1, treated.

148.1 g of a water-clear, colorless reaction solution are obtained which contain 39.8 g of butanediol (1.4).

Example 8

19.5 g of palladium acetate, 7.7 g of ruthenium acetate and 3.3 g of rhenium heptoxide are dissolved in 900 ml of acetic acid and 100 g of zirconium oxide stirred in, dried in a rotary evaporator under vacuum and reduced in hydrogen at 2oo ° C.

0.5 mol of maleic acid (58 g) is dissolved in 100 ml of warm dioxane. To this are added 7.5 g of a zirconium oxide catalyst, which contains 8.1% Contains palladium, 2.5% ruthenium and 2.2% rhenium, and the mixture is placed in an 0.5 liter magnetic lifting stirrer autoclave. Man presses on 178 bar of hydrogen, heats quickly to 215 ° C and lets react for 3 1/2 hours. This is followed by cooling down, relaxing and analyzed the reaction solution. After filtering off the catalyst, 138 g of solution are obtained which contain 24.8% or 34.8 g of butanediol

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"- 13 (1.4) included, which corresponds to about 78% of theory.

Comparative example £

27 g of palladium acetate are dissolved in 1200 g of glacial acetic acid at 80 ° C., 100 g of kieselguhr are added and, as in Example!, Dried and reduced.

0.5 moles of maleic acid (149 φ are dissolved in 100 ml of dioxane. The solution is reacted together with 5 g of the kieselguhr catalyst, which contains 10% palladium, as indicated in Example 1. 148.3 g of a pale yellow reaction solution are obtained which contains only 3 _# 5 % (5.2 g) butanediol (1.4). The main product of the reaction is y-butyrolactone, which in the reaction solution contains 23.1%

is represented.

Comparative example 2

3.2 g of rhenium heptoxide are dissolved in 400 ml of glacial acetic acid, 100 g of kieselguhr are stirred in and, as in Example 1, dried and reduced.

The procedure is as in Comparative Example 1, but instead of the catalyst used there, 5 g of the SiC> 2 catalyst, the Contains 2.3% rhenium. This experiment gives 147.2 g of a reaction solution which contains only traces (<0.2%) of butanediol (1.4), Lo.2% tf-butyrolactone, but larger amounts of succinic acid, which partially fails, contains.

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Claims (12)

HOE 75 / F 112 gA / NSPRÜCHE !.! Process for the production of butanediol- (1.4) from maleic ^ w / anhydride, maleic acid or a mixture thereof », characterized by that one maleic anhydride, maleic acid or mixtures thereof in one stage in the presence of catalysts hydrogenated, the elements of the VII. Subgroup or their compounds and elements of the VIII. Subgroup or their compounds or mixtures of these elements and compounds. 2. The method according to claim 1, characterized in that the catalysts manganese or rhenium or their compounds as well as ruthenium, rhodium, palladium, osmium, iridium or platinum or their compounds. 3. The method according to claim 1 and 2, characterized in that the catalysts rhenium or its compounds and Contain palladium and platinum or their compounds. 4. The method according to claim 1-3, characterized in that as compounds of the elements of the VII. Or VI11.subgroup the oxides, oxide hydrates, carboxylates, chelates of 1.3 - diketo compounds, nitrates, carbonates or borides are used will. 5. The method according to claim 1-4, characterized in that the Catalysts are applied to a carrier. 6. The method according to claim 5, characterized in that the amount of catalytically active substances between o, l and 5o percent by weight of the total mass of the catalyst. 609846/0974 - 15 - HOE 75 / F 112 7. The method according to claim 5, characterized in that the carrier silicon dioxide, silicon dioxide-aluminum oxide, carbon, Titanium dioxide, thorium oxide, zirconium oxide, silicon carbide, spinels and aluminum oxides can be used. 8. The method according to claim 1-7, characterized in that the ratio of the active elements of the VII. Subgroup to those of the VIII. subgroup is between 99: 1 and 1:99. 9. The method according to claim 1 · *, characterized in that the The reaction temperature is between 5o and 3oo ° C. 10. The method according to claim 1-9, characterized in that the reaction pressure is between 5o and 5oo bar. 11. Process for the production of a palladium-rhenium catalyst, for the synthesis of butanediol- (1.4) from maleic anhydride, maleic acid or mixtures thereof, characterized in that a carboxylic acid solution of a palladium carboxylate is used or a palladium compound which converts into a carboxylate in the presence of a carboxylic acid together with perrhenic acid or applying their salts to a support, the carboxylic acid by drying at higher temperatures in a vacuum or at Normal pressure removed and the catalyst in the gas or liquid phase at temperatures from 15 to 2oo ° C with Reactants treated. 12. The method according to claim Ϊ1, characterized in that one a liquid aliphatic that can be evaporated without decomposition in a vacuum Carboxylic acid with 2 to 10 carbon atoms used. 609846/0974
INSPECTED