Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
• • 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
  • C07D307/30—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 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
  • C07D307/32—Oxygen atoms
  • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/72—Copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
  • B01J23/8926—Copper and noble metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0215—Coating
  • B01J37/0221—Coating of particles
  • B01J37/0223—Coating of particles by rotation
• • 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
  • C07D307/06—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
  • C07D307/08—Preparation of tetrahydrofuran
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0215—Coating

Definitions

• the present invention relates to a process for the preparation of optionally alkyl-substituted ⁇ -butyrolactone and tetrahydrofuran by catalytic hydrogenation in the gas phase of substrates which are selected from the group consisting of maleic acid and succinic acid and derivatives of these acids.
• substrates which are selected from the group consisting of maleic acid and succinic acid and derivatives of these acids.
• this includes esters and anhydrides, which, like the acids, can have one or more alkyl substituents.
• a coated catalyst is used, which consists of an inert support material with a thin layer on it containing Cu and Al oxides.
• GBL and THF are maleic acid itself, succinic acid and its anhydride and the esters of these acids. If GBL and THF are to be produced which have alkyl substituents, it is advisable to use the corresponding alkyl-substituted species of the abovementioned acids, esters and anhydrides.
• the catalysts used according to this patent correspond to the general formula CuiZn b Al ⁇ M d O x , in which M is at least one element which is selected from the group consisting of the groups II A and IIIA, VA, VIII, Ag, Au, the groups IIIB to VIIB as well as lanthanides and actinides of the periodic table of the elements; b is a number between 0.001 and 500, c a number between 0.001 and 500 and d a number from 0 to ⁇ 200 and x corresponds to the number of oxygen atoms that are necessary according to the valence criteria.
• the catalysts according to this patent need not contain chromium, chromium-containing catalysts are described in all examples. According to these examples, a maximum THF yield of 96% is obtained, and the hydrogenation is carried out at pressures of 20 to 40 bar.
• a two-stage catalyst system for the hydrogenation of MA is described in US Pat. No. 5,149,836.
• the catalyst for the first stage is chrome-free, the catalyst for the second stage is based on Cu-Zn-Cr oxides.
• a catalyst composed exclusively of Cu and Al oxides for the MA gas phase hydrogenation to GBL is disclosed in WO 97/24346.
• the use of a catalyst with basically the same composition as described in WO 97/24346, namely based on Cu-Al oxides, is also disclosed in JP 2 233 631.
• the aim of this invention is to carry out the hydrogenation of MA so that the main products are THF and 1,4-butanediol in addition to little or no amounts of GBL.
• This is then achieved by using the catalysts based on mixed Cu-Al oxides and by observing certain reaction conditions.
• Typical mixtures obtained with this process contain approx. 15 to 20 mol% of 1,4-butanediol and 60 to 80 mol% of THF, the amount of THF even being able to be increased to over 99 mol% according to an example.
• This is achieved by using GBL as a solvent, in a multiple excess. If, on the other hand, work is carried out without a solvent, the yields decrease considerably, to values of around 75%.
• EP-A 0 404 408 discloses a catalyst for MA hydrogenation, the structure of which is fundamentally different from the catalysts in the references mentioned above.
• the catalytically active material essentially corresponds to the material that is disclosed in the above-cited US 5,072,009.
• the material is then applied to a substantially inert, at least partially porous support having an outer surface.
• the catalytically active material adheres to the outer and inner surface of the carrier.
• GBL is the preferred product.
• all the catalysts used in the examples contain Cr.
• the large amount of BSA formed is also disadvantageous here.
• the object of the present invention is to provide a catalyst for the gas phase hydrogenation of maleic acid and or succinic acid and or the above-mentioned derivatives, which can be used variably for the production of optionally substituted THF and / or GBL.
• the catalyst should be free of Cr.
• this catalyst should, under appropriate reaction conditions, enable high yields of THF with, at the same time, little formation of undesired by-product.
• a catalyst for the hydrogenation of C - dicarboxylic acids and / or their derivatives in the gas phase characterized in that this catalyst contains 5 to 100% by weight of Cu oxide and 0 to 95% by weight of one or more Metals or their compounds from the group consisting of Al, Si, Zn, La, Ce, the elements of Group III A to VIII A and Group IA and II A as the active mass and this mass on an inert carrier material in the form of a thin Layer is applied.
• C 4 -dicarboxylic acids and their derivatives are taken to mean, in relation to the present application, maleic acid and succinic acid, which may have one or more -C ⁇ -alkyl substituents, and the anhydrides and esters of these optionally alkyl-substituted acids.
• An example of such an acid is citraconic acid.
• MSA is preferably used.
• the active composition of a catalyst according to the invention consists of Cu oxide known per se, which may optionally have one or more other metals from the group mentioned above or their compounds.
• the active composition preferably contains no Cr.
• the proportion of Cu oxide is from 5 to 100% by weight, preferably 40 to 90% by weight.
• the other or the other metals or their compounds are present in proportions of 0 to 95% by weight, preferably 10 to 60% by weight. It has been observed that the activity of the catalyst increases in principle with increasing Cu oxide content.
• the catalyst preferably contains one or more other metals from the group consisting of Al, Si, Zn, La, Ce, the elements of groups IIIA to VIIIA and groups IA and ILA or a compound of these metals in the active composition, the Compound is preferably an oxide.
• the further metal from Pd, Zn, Zr and / or Al or their compounds.
• the amount of Cu oxide is 10 to 90% by weight, in particular 40 to 90% by weight
• the amount of Pd, Zn, Zr and / or Al Oxide is 90 to 10% by weight, in particular 60 to 10% by weight. If one of the metals mentioned or a compound thereof is present in addition to Cu oxide, it is preferred if this is Al or aluminum oxide. In this case, there is then either no further metal or only another metal or a compound thereof. If there is still another metal, this is preferably Pd or an oxide thereof.
• the catalyst according to the invention thus consists, in addition to the usual impurities, if appropriate, in particular of Cu and Al or the oxides thereof or Cu, Al and Pd or the oxides thereof, both embodiments having equal rights.
• the mixed catalyst used according to the invention can contain the respective metals in the form of a salt, preferably the oxide, or in elemental form. These arise in particular under a reducing hydrogen atmosphere. If the catalyst contains the above-mentioned metals or compounds thereof, preferably no further constituents are present apart from the usual impurities known to the person skilled in the art.
• the active composition is prepared in a manner known per se, for example by precipitation of the corresponding metal carbonates and / or hydroxides in aqueous solution, Wash, dry and calcine.
• the metal carbonates or hydroxides can be obtained, for example, by dissolving the corresponding metal salts in water and adding sodium carbonate solution.
• sodium carbonate solution For example, nitrates, sulfates, chlorides, acetates or oxalates are used as metal salts.
• the mass is then applied to the carrier in a customary manner, for example by mixing the powdery oxide mixture with the carrier in a stirring drum in the presence of a binder or adhesive.
• the carrier with precursor substances of the active composition, for example the carbonates, nitrates, oxalates or hydroxides of the respective metals mentioned.
• the respective metal compounds can be mixed and applied in one work step or in succession. This pretreated carrier is then subjected to a heat treatment to produce the active composition.
• the catalyst by suspending the powdery active composition and the carrier in water or an organic liquid and removing the water or the organic liquid to dryness, for example by heating.
• the proportion of the active mass in the total mass of the catalyst is from 5 to 60% by weight, preferably 15 to 30% by weight. If these values are exceeded, a behavior is achieved which approximates that of a full catalytic converter with the same active composition. If the active mass content is too low, on the other hand, the activity is too low in relation to the space filling of the catalyst.
• non-porous carrier materials Materials that are suitable for the production of the carrier are known, non-porous carrier materials.
• the supports should have a surface area of ⁇ 0.5 m / g and a porosity of ⁇ 0.05 cm 3 / g.
• porous supports which are used, for example, in accordance with EP-A 404 408, a higher mechanical stability and a higher bulk density of the catalyst are achieved in this way.
• the carrier can no longer absorb active mass due to the loading of the entire pore volume.
• suitable carrier materials include aluminum oxide, sintered corundum (highly annealed ⁇ -Al O 3 ), aluminum silicates such as, for example, mullite, magnesium silicates such as, for example, steatite, magnesium aluminum silicates such as, for example, cordierite, glass, silicon carbide, silicon dioxide, steel and other ceramic known to the person skilled in the art Materials.
• the carrier is inert. A rough surface of the carrier material may facilitate the adhesion of the active material.
• the carrier material is preferably selected from the group consisting of steatite, mullite, cordierite, silicon carbide and highly annealed aluminum oxide. In particular, the carrier material is steatite.
• the carrier material is brought into suitable shaped bodies serving as carriers.
• the geometry of this inert molded body and thus of the resulting coated catalyst according to the invention is not critical. For example, balls, saddle shapes, solid and hollow cylinders are suitable.
• the catalysts according to the invention have a specific structure due to the use of non-porous supports and the production process according to the invention.
• the active material is in the form of a thin, coherent layer on the outer surface of the carrier. Due to the lack of pores and due to the chosen coating process, there is no active material in the carrier itself.
• Reactors in which the catalyst is arranged as a fixed bed are suitable for the reaction. Tube-bundle reactors are particularly preferred in order to dissipate the heat released during the reaction cheaply.
• MSA is evaporated and passed through the reactor with a hydrogen-containing gas stream. A mixture with a high hydrogen content is preferred.
• the supply of other gaseous components such as water vapor, hydrocarbons such as methane, ethane or n-butane or carbon monoxide, has a favorable effect on the selectivity, activity or long-term stability.
• the concentration of the MSA is 0.1 to 5% by volume, preferably between 0.2 and 2% by volume. At much higher MSA concentrations, MSA condenses out in the reactor and covers the catalyst with a liquid film. In principle, concentrations which are substantially lower than those given above are possible, but these would reduce the space-time yield and make the process unnecessarily expensive.
• the temperature of the reaction is adjusted to values of 150 to 400 ° C, preferably 200 to 300 ° C. Higher temperatures favor the formation of by-products, lower temperatures lead to an unnecessary loss of activity of the catalyst.
• the pressure is set to values from 0.5 to 50 bar, preferably 1 to 10 bar.
• the GHSN is 10 to 50,000 h "1 , preferably between 100 and 10,000 h " 1 .
• the product distribution can be controlled by varying the GHSV.
• the product mixture can be separated by methods known to those skilled in the art. At least part of the unreacted hydrogen is preferably circulated and thus used again in the hydrogenation.
• the catalyst is subjected to activation, generally hydrogen pretreatment, before use in the reaction. This creates the active catalyst species. This is done by partially reducing the oxides present in the catalyst mixture to the elemental metal which is active in the catalytic reaction according to the invention.
• the catalyst according to the invention has a sufficient service life.
• the activity and / or selectivity of the catalyst should nevertheless decrease in the course of its operating time, it can be regenerated by measures known to the person skilled in the art.
• This includes reductive treatment of the catalyst in a hydrogen stream at elevated temperature. If necessary, the reductive treatment can be preceded by an oxidative treatment. In this case, a molecular mixture containing gas, for example air, flows through the catalyst bed at elevated temperature.
• a suitable solvent for example methanol, THF or GBL
• a metal salt solution consisting of 877 g of Cu (NO 3 ) 2 * 2.5H 2 O and 1472 g of Al (NO 3 ) 3 * 9H 2 O in 2000 ml of water and at the same time a 20% by weight Soda solution added while stirring.
• the soda dosing is chosen so that a pH of 6 is established in the precipitation vessel.
• sodium carbonate solution is metered in until a pH of 8 is reached in the precipitation vessel and stirring is continued at this pH for 15 min.
• the total consumption of soda solution is 5.5 kg.
• the suspension formed is filtered off and washed with water until the wash water running off no longer contains nitrate ( ⁇ 25 ppm).
• the filter cake is first dried at 120 ° C and then calcined at 600 ° C.
• Chemtech are placed in a watering drum and sprayed with 15 ml water / glycerol mixture (3: 1). Then 163 g of a grain size of ⁇ 100 microns ground active composition from Example 1 and a further 150 ml of the water-glycerol mixture are added continuously, so that the support is homogeneously coated with powder.
• the coated support is first dried at 120 ° C. for 2 h and then at 300 ° C. for 2 h with air circulation.
• a coated catalyst according to the invention 500 ml of surface roughened steatite balls with a diameter of 2-3 mm (from Chemtech) are placed in a watering drum and sprayed with 15 ml of water / glycerol mixture (3: 1). Then 433 g of the active material from Example 1 ground to a particle size of ⁇ 100 ⁇ m and a further 370 ml of the water-glycerol mixture are added continuously, so that the carrier is homogeneously coated with powder.
• the coated support is first dried at 120 ° C. for 2 h and then at 300 ° C. for 2 h with air circulation.
• Example la 220 g of the active composition from Example la are mixed with stirring with 273 ml of an aqueous palladium nitrate solution (noble metal content: 2.2 g Pd) and mixed thoroughly.
• the moist product is first dried at 100 ° C. and then calcined at 350 ° C.
• Chemtech are placed in a watering drum and sprayed with 12 ml water / glycerol mixture (3: 1). Then 170 g of the active material from Example 4a ground to a particle size of ⁇ 100 ⁇ m and a further 140 ml of the water / glycerol mixture are added continuously, so that the carrier is homogeneous is coated with powder.
• the coated support is dried at 120 ° C. for 2 h with air circulation.
• Example la 100 g of the active composition from Example la are mixed with stirring with 124 ml of an aqueous palladium nitrate solution (noble metal content: 11.1 g Pd) and mixed thoroughly.
• the moist product is first dried at 100 ° C and then calcined at 450 ° C.
• the coated carrier is dried at 120 ° C. for 2 h and then at 300 ° C. for 2 h with air circulation.
• Example 6a The preparation from Example 6a is repeated with the difference that the material is calcined at 800 ° C.
• the catalyst was subjected to a hydrogen pretreatment.
• the reactor was first flushed with 200 Nl / h of nitrogen at atmospheric pressure and at the same time heated to a temperature in the catalyst bed of 180 ° C. within one hour.
• the nitrogen volume flow was then increased to 950 Nl / h and an additional 50 Nl / h hydrogen fed.
• a slight increase in temperature in the catalyst bed to about 250 ° C. was observed.
• the nitrogen volume flow was gradually reduced to 500 Nl / h and the hydrogen flow to 500 Nl / h.
• the nitrogen volume flow was switched off and the hydrogen flow was raised to 600 Nl / h.
• Example 7 was repeated with the difference that 200 ml of the catalyst from Example 2 are used. The results are shown in Table 1.
• Example 7 was repeated with the difference that 200 ml of the catalyst from Example 3 are used. The results are shown in Table 1.
• Example 9 was repeated with the difference that 200 ml of the catalyst from Example 4 are used. The results are shown in Table 1.
• Example 9 was repeated with the difference that 200 ml of the catalyst from Example 5 are used. The results are shown in Table 1.
• Example 14
• Example 9 was repeated with the difference that 200 ml of the catalyst from Example 6 are used. The results are shown in Table 1.
• Example 9 Hydrogenation of maleic anhydride Example 9 was repeated with the difference that 200 ml of the catalyst from Example 7 are used. The results are shown in Table 1.
• Example 9 was repeated with the difference that 200 ml of the catalyst from Example 8 are used. The results are shown in Table 1.
• 400 g of the active composition from Example 1 are comminuted to a grain size of ⁇ 1 mm, mixed with 3% by weight of graphite powder, mixed thoroughly and pressed to tablets of 3 mm in diameter and 3 mm in height.
• Example 9 was repeated with the difference that 100 ml of the VoU catalyst from comparative example 1 were used.
• the results of the catalytic tests are given in Table 1. Table 1
• the shell catalyst delivers high GBL yields with only a slight increase in the GHSV without large amounts of BSA being formed at the same time (experiment 9.3).
• the THF selectivity for the full catalyst cannot be increased by more than 80% (experiment lx, 2x, 3x). It is therefore necessary to set a much more flexible product mix THF-GBL with the coated catalytic converter than with the full catalytic converter. This provides a significantly lower GBL yield with increased B SA formation (experiment 4x).

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• 2000
  • 2000-12-11 DE DE10061555A patent/DE10061555A1/de not_active Withdrawn
• 2001
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  • 2001-12-07 EP EP01989586A patent/EP1351763A1/de not_active Ceased
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