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WO2005058492A1 - Catalyseur ameliore pour l'hydrogenation d'acide maleique anhydrique avec y-butyrolactone et tetrahydrofurane - Google Patents

Catalyseur ameliore pour l'hydrogenation d'acide maleique anhydrique avec y-butyrolactone et tetrahydrofurane Download PDF

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Publication number
WO2005058492A1
WO2005058492A1 PCT/EP2004/013810 EP2004013810W WO2005058492A1 WO 2005058492 A1 WO2005058492 A1 WO 2005058492A1 EP 2004013810 W EP2004013810 W EP 2004013810W WO 2005058492 A1 WO2005058492 A1 WO 2005058492A1
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Prior art keywords
catalyst
hydrogenation
oxide
hydrogen
msa
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German (de)
English (en)
Inventor
Markus Rösch
Rolf Pinkos
Michael Hesse
Stephan Schlitter
Olga Schubert
Gunther Windecker
Alexander Weck
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BASF SE
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BASF SE
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    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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

Definitions

  • the present invention relates to an improved chromium-free catalyst for the preparation of defined BSA-free mixtures of ⁇ -butyloctolactone (GBL) and tetrahydrofuran (THF) by catalytic hydrogenation of C4-dicarboxylic acids and / or their derivatives such as maleic anhydride (MSA) in the gas phase.
  • GBL ⁇ -butyloctolactone
  • THF tetrahydrofuran
  • MSA maleic anhydride
  • Derivatives in this application are esters and anhydrides which, like the acids, may have one or more alkyl substituents.
  • the process uses a catalyst having a uniform structure which comprises mixtures of copper oxide and optionally at least one further oxide from groups 1 to 14 of the Periodic Table of the Elements in the active composition, and an oxide having acidic centers, preferably aluminum oxide the active composition and the oxide with acidic centers (also referred to below as acidic oxide) are pressed or extruded into max.20 mm 3 large moldings.
  • a catalyst having a uniform structure which comprises mixtures of copper oxide and optionally at least one further oxide from groups 1 to 14 of the Periodic Table of the Elements in the active composition, and an oxide having acidic centers, preferably aluminum oxide the active composition and the oxide with acidic centers (also referred to below as acidic oxide) are pressed or extruded into max.20 mm 3 large moldings.
  • the catalysts used according to US 5,072,009 correspond to the general formula Cu ⁇ Zn Al c M d O x , in which M is at least one element which is selected from the group consisting of the groups IIA and IIIA, VA, VIII, Ag, Au, den Groups HIEB 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 is a number between 0.001 and 500 and d is a number from 0 to ⁇ 200 and x corresponds to the number of oxygen atoms that are necessary according to the valence criteria.
  • Chromium-containing catalysts of the type Cu / Mn / Ba / Cr and Cu / Zn / Mg / Cr for the MSA gas phase hydrogenation are known from WO 97/43234.
  • BDO is mainly obtained in addition to small amounts of GBL and THF.
  • the hydrogenation is carried out at about 150 ° C to 300 ° C and a pressure of 5 bar to 100 bar in the gas phase.
  • JP 2-233631 The use of chromium oxide-free catalysts based on mixed Cu-Al oxides is disclosed in JP 2-233631.
  • the hydrogenation of MSA is to be carried out in such a way that almost exclusively THF and BDO are produced as the main products along with at most small amounts of GBL. This is then achieved by the use of the catalysts based on mixed Cu-Al oxides and by observing certain reaction conditions.
  • the MSA hydrogenation is carried out so that MSA in a solvent such as GBL, THF or Dissolved dioxane and this strongly diluted MSA solution is passed over the catalyst after their evaporation.
  • Example 6 describes the evaporation of MSA melt without solvent. Here, only a yield of THF of 76.3 mol% is obtained. As a by-product, 1, 4-butanediol (BDO) is formed in 20.4% yield.
  • the hydrogenation is carried out at temperatures between about 210 to 230 ° C and GHSV values of about 3200 to 9600. The hydrogen / MSA ratios are comparatively unfavorably high for industrial processes, in the examples from 200 to 800.
  • the catalysts used in the examples have a composition of 20 wt .-% CuO, 43.6 wt .-% ZnO and 18.1 wt .-% Al 2 O 3 , 32.6 wt .-% CuO 38.1 wt % ZnO and 9.5% by weight Al 2 O 3 , 24.2% by weight CuO, 36.4% by weight ZnO and 17.2% by weight Al 2 O 3 , 26.4 Wt .-% CuO, 52.9 wt .-%, ZnO, 7.6 wt .-% Al 2 O 3 and 1, 4 wt .-% CaO and 22.9 wt .-% CuO, 44.8 wt % ZnO and 16.3% by weight Al 2 O 3 . It is generally worked in a solvent such as GBL or dioxane, with a maximum THF selectivity of 94% is achieved. When the reaction is carried out without a solvent, the THF selectivity reaches a maximum value of 83%.
  • EP 0404408 claims a catalyst for MSA hydrogenation to THF and GBL having a substantially inert, at least partially porous, outer surface-carrying carrier and a catalytically active, coated on the outer surface of the carrier, strong on the outer surface the oxide of the carrier comprises, wherein the catalytically active oxide material comprises a mixed oxide catalyst of the formula Cu ⁇ n b Al c M d O x , wherein M is at least one element selected from the group consisting of Groups IIA to VA, Group VIII, Ag, Au, groups IIIB to VIIB, the rare earth metals and the transuranic, b is a number between 0.001 and 500, c is a number between 0.001 and 500 and d is a number from 0 to 200 and x is a number of oxygen atoms necessary according to valence criteria becomes.
  • This shell catalyst favors the formation of GBL as the preferred product arises.
  • Another disadvantage is the large amount of BSA formed.
  • DE 10061555 also discloses a copper oxide and alumina-containing coated catalyst for gas-phase dehydrogenation of MSA. From DE 10061556 a method for the selective production of THF using a Cu-Al catalyst is known. A disadvantage of the method is that there are only limited possibilities of influencing the product composition. If the temperature is lowered, the content of GBL in the discharge increases, but at the same time the content of BSA in the discharge increases.
  • the object of the present invention is to provide a catalyst and a process by which defined mixtures of GBL and THF can be prepared by hydrogenating MSA. This process should be able to be operated continuously and with chromium-free catalysts and as large as possible
  • the catalyst should be able to be operated with MSA which has not been pre-cleaned in a complicated manner, for example by distillation, and nevertheless has high stability, ie does not require frequent regeneration.
  • the method is intended to allow the operator the variability without a catalyst change, i. only by changing the operating parameters to obtain a modified product mixture in order to adapt flexibly and economically to the market requirements can. All accessible product mixtures should be as free of BSA as possible, on the one hand to prevent procedural problems (laying in pipelines), on the other hand, but also to minimize yield losses.
  • the catalyst according to the invention has a uniform structure structure. Its components are intimately mixed with each other, whereby the catalyst has no larger, differently structured components, as do, for example, coated catalysts.
  • the catalyst in the form of the inventive small moldings in a process for the hydrogenation of C 4 dicarboxylic acids and / or their derivatives, preferably maleic anhydride in the gas phase, the quantitative ratio of optionally alkyl-substituted value products GBL and THF while retaining all other reaction parameters only can be adjusted by varying the temperature in the reactor in the ratio 0: 1 to 1: 9 and thus a product distribution according to market requirements can be obtained without catalyst change.
  • the term C 4 -dicarboxylic acids and their derivatives in relation to the present application maleic acid and succinic acid, optionally a or more CC 6 alkyl substituents and the anhydrides of these optionally alkyl-substituted acids understood.
  • An example of such an acid is citraconic acid.
  • the respective anhydrides of a given acid are used.
  • the educt used is MSA.
  • the catalyst according to the invention is characterized in that it is able to make variable mixtures of GBL and THF accessible by gas phase hydrogenation of MSA in terms of their product ratios, which are largely free of BSA. It has a long service life and a high load capacity, so that reactivations can be omitted and reactor volume can be saved. All these points make a method practiced with this catalyst particularly economical.
  • the catalyst according to the invention comprises copper oxide and an acidic oxidic material as the main constituent and may optionally contain one or more further metals or their compounds, preferably oxides, from groups 1 to 14 (IA to VIIIA and IB to IVB of the ancient IUPAC nomenclature) of Periodic Table of Elements. If such a further oxide is used, preference is given to using TiO 2 , ZrO 2 , SiO 2 , CaO, Na 2 O, Mn 2 O 3 , BaO, and / or MgO.
  • the proportion of copper oxide in the total mass of the catalyst is 5 to
  • the catalyst of the invention contains an acidic oxide which must have a suitable number of acidic sites.
  • the required proportion of the oxide having acidic centers depends on the amount of acidic centers contained therein.
  • Suitable acid oxides having a sufficient number of acidic sites are titanium dioxide, zirconia, silica and alumina, the use of which is preferred and mixed oxides of these oxides.
  • Particularly preferred catalyst compositions comprise ⁇ 70% by weight of copper oxide, in particular 10 to 65% by weight of CuO, and> 20% by weight, preferably> 30% by weight, in particular 35 to 90% by weight, of acidic oxide, on. Low copper oxide levels are also preferred because of the cost advantage achieved thereby. Due to the acidic oxides, high yields can be achieved.
  • the metals from groups 1 to 14 of the Periodic Table of the Elements may be present in the catalyst in an amount of up to 30% by weight.
  • the catalysts used may also contain one or more auxiliaries in an amount of 0 to 10 wt .-%.
  • auxiliaries are meant organic and inorganic substances which contribute to improved processing during catalyst preparation and / or to an increase in the mechanical strength of the catalyst bodies.
  • Such aids are known in the art; Examples include graphite, stearic acid, silica gel, cellulose compounds, starch, polyolefins, carbohydrates (sugars), waxes, alginates, as well as alumina, alumina hydro- xid, eg in the form of boehmite; Zirconia, silica and their sols, substituted and unsubstituted siloxanes and copper powder.
  • the catalysts can be prepared by methods known to those skilled in the art. Preference is given to processes in which the copper oxide is finely distributed and intimately mixed with the other constituents of the active composition and the acidic oxide. Particularly preferably, the corresponding metal salts and / or hydroxides are precipitated from aqueous solution, washed, dried and calcined. Suitable metal salts are, for example, nitrates, sulfates, carbonates, chlorides, acetates or oxalates. Subsequently, this starting material will be processed by known methods to the moldings, for example extrusion, tableting or by agglomeration, optionally with the addition of auxiliaries.
  • catalysts according to the invention can be prepared by applying the active material or precursor compounds of the active composition to an acidic oxide, for example by impregnation or vapor deposition. Further, catalysts of the present invention can be obtained by molding a mixture of active components and acidic oxide or their precursor compound with an oxide having acidic centers or a precursor compound thereof.
  • the catalysts are used as shaped bodies. Examples include strands, rib strands, other extrudate shapes, tablets, rings, balls, and chippings.
  • extrudates are particularly suitable extrudates. These are obtained by extruding the dried starting compound with an adjuvant (binder), for example boehmite or p-boehmite (AIOOH), and then calcined.
  • the binder can be pretreated prior to extrusion. This is preferably done with acid, such as with formic acid, nitric acid or hydrochloric acid.
  • acid such as with formic acid, nitric acid or hydrochloric acid.
  • Other adjuvants such as pore formers such as carboxymethyl cellulose, potato starch or stearic acid may additionally be added prior to extrusion.
  • the determination of the volume of the shaped bodies according to the invention is effected by calculation from the dimensions of the shaped bodies.
  • the catalyst in which, in addition to MSA, other C dicarboxylic acids defined above or their derivatives can be used as starting material, the catalyst is used in reduced, activated form. Activation takes place with reducing gases, preferably hydrogen or hydrogen / inert gas mixtures, either before or after incorporation into the reactor in which the process according to the invention is carried out. If the catalyst has been incorporated into the reactor in oxidic form, the activation can take place both before the system is started up with the hydrogenation according to the invention and during the startup, ie in situ, be performed.
  • the separate activation before starting the system is generally carried out with reducing gases, preferably hydrogen or hydrogen / inert gas mixtures at elevated temperatures, preferably between 100 and 300 ° C. In so-called in-situ activation, the activation takes place when the system starts up by contact with hydrogen at elevated temperature.
  • the BET surface area of the copper catalysts in the oxidic state is 10 to 400 m 2 / g, preferably 15 to 200 m 2 / g, in particular 20 to 150 m 2 / g.
  • the copper surface (N 2 O decomposition) of the reduced catalyst in the installed state is> 0.2 m 2 / g, preferably> 1 m 2 / g, in particular> 2 m 2 / g.
  • catalysts are used which have a defined porosity.
  • these catalysts show a pore volume of ⁇ 0.01 ml / g for pore diameters> 50 nm, preferably ⁇ 0.025 ml / g for pore diameters> 100 nm and in particular ⁇ 0.05 ml / g for pore diameters
  • the ratio of macropores lies with a diameter
  • the catalysts used in the invention generally have a sufficient life. In the event that the activity and / or selectivity of the catalyst should nevertheless decrease in the course of its operating time, this can be regenerated by measures known to the person skilled in the art.
  • This preferably includes a reductive treatment of the catalyst in a hydrogen stream at elevated temperature.
  • the reductive treatment may be preceded by an oxidative one.
  • the catalyst bed is mixed with a molecular oxygen-containing gas mixture, for example air, at elevated temperature.
  • a suitable solvent for example ethanol, THF or GBL, and then to dry in a gas stream.
  • Reactors in which the catalyst is arranged in a fixed bed are suitable for the process according to the invention. Particularly preferred are tube bundle reactors or plate reactors to the low heat released during the reaction dissipate. MSA is vaporized and passed through the reactor with a hydrogen-containing gas stream.
  • the ratio of the optionally alkyl-substituted value products GBL and THF can be adjusted while maintaining all other reaction parameters only by varying the temperature in the reactor in a ratio of 0: 1 to 1: 9. This is achieved on the one hand by a sufficiently high inlet temperature of the starting materials in the reactor. This is at values of> 220 to 300 ° C, preferably 235 to 270 ° C. In order to obtain an acceptable or high desired product selectivity and yield, the reaction must be carried out so that there is a suitably high reaction temperature at the catalyst bed on which the actual reaction takes place.
  • hot-spot temperatures are at values of 240 to 310 ° C, preferably 240 to 280 ° C.
  • the process is carried out so that the inlet temperature of the reaction gases is below this hot spot temperature.
  • the first hot spot lies spatially in the first half of the reactor after the entry point of the reaction mixture, in particular in the presence of a tube bundle reactor.
  • the first hot-spot temperature is 5 to 15 ° C, in particular 10 to 15 ° C, above the inlet temperature.
  • a second hot spot may be located at any point in the reactor and will be displaced spatially towards the reactor outlet by lowering the inlet temperature.
  • the second hot-spot temperature is 1 to 15 ° C, in particular 2 to 10 ° C, above the inlet temperature. If mainly THF-containing mixtures are to be obtained, this second hot-spot is preferably in the first 2/3 of the reactor; preferably GBL-containing mixtures are to be obtained, the second hotspot is in the last third, in particular at the reactor outlet.
  • the catalyst loading of the hydrogenation according to the invention is in the range from 0.02 to 2.0 kg of starting material / catalyst / hour.
  • the catalyst loading is the sum of freshly fed educt and recycled intermediate. If the catalytic converter Tort burden increased beyond the range mentioned, is generally observed an increase in the proportion of the intermediate product in the hydrogenation.
  • the catalyst loading is in the range of 0.05 to 1 kg of starting material I catalyst • hour.
  • starting material also means initially formed hydrogenation product, which is then hydrogenated further to product after recycling, for example GBL in the case of the use of MSA in the hydrogenation reaction.
  • the hydrogen / reactant molar ratio is likewise a parameter which has an important influence on the product distribution and also the economic viability of the process according to the invention. From an economic point of view, a low hydrogen / reactant ratio is desirable.
  • the lower limit is a value of 5, but generally higher hydrogen / reactant mole ratios of 20 to 650 are used.
  • the use of the catalysts according to the invention described above and the observance of the temperature values described above permit the use of favorable, low hydrogen / starting material ratios, which are preferably from 20 to 200, preferably from 40 to 150. The cheapest range is between 50 and 100.
  • a part, advantageously the main amount, of the hydrogen is circulated.
  • the cycle gas compressor known to those skilled in the art.
  • the amount of hydrogen chemically consumed by the hydrogenation is supplemented.
  • a portion of the recycle gas is discharged to remove inert compounds, such as n-butane.
  • the recirculated hydrogen may also be used, optionally after preheating, to evaporate the educt stream.
  • the pressure at which the hydrogenation according to the invention is carried out is at values of 1 to 100 bar, preferably 2 to 60 bar, in particular 5 to 15 bar.
  • the cooling temperature is 0 to 60 ° C, preferably 20 to 45 ° C.
  • the THF content of the circulating gas is 0.1 to 5% by volume, in particular 1 to 3% by volume.
  • THF and GBL are hydrogenated with hydrogen in the presence of copper catalysts to n-butanol.
  • the process according to the invention is characterized in that GBL and THF yields of more than 90%, in some cases even more than 95%, are achieved in spite of the high proportions of THF in the recycle gas, which are generally hydrogenated further to n-butanol become.
  • reactor types come all, for heterogeneously catalyzed reactions with a gaseous Edukt- and product stream suitable apparatus into consideration. Preference is given to tubular reactors, shaft reactors, plate reactors or reactors with internal heat removal, for example tube-bundle reactors. Particular preference is given to using tube bundle reactors.
  • Several reactors can be used in parallel or in series. In principle, an intermediate feed can take place between the catalyst beds. Also possible is an intermediate cooling between or in the catalyst beds. When using fixed bed reactors, a dilution of the catalyst by inert material is possible.
  • the gas stream leaving the reactor is cooled to 10 to 60 ° C.
  • the reaction products are condensed out and passed into a separator.
  • the non-condensed gas stream is withdrawn from the separator and fed to the cycle gas compressor.
  • a small amount of circulating gas is discharged.
  • the condensed reaction products are continuously removed from the system and fed to the workup.
  • As by-products are found in the condensed liquid phase mainly n-butanol in addition to small amounts of propanol.
  • the azeotrope of water and optionally alkyl-substituted THF, GBL and optionally by-product, separated by fractional distillation is dehydrated in a manner known per se and worked up by distillation to specification-compliant THF.
  • the process according to the invention is characterized in that starting materials of different purity to be hydrogenated can be used in the hydrogenation reaction.
  • a starting material of high purity in particular MSA
  • the catalyst used according to the invention and the other reaction conditions selected according to the invention also allow the use of educts, in particular MSA, which is contaminated with the customary compounds obtained in the oxidation of benzene, butenes or n-butane and possibly other components.
  • the hydrogenation process according to the invention may comprise an upstream stage which comprises preparing the starting material to be hydrogenated by partial oxidation of a suitable hydrocarbon and separating the starting material to be hydrogenated from the product stream thus obtained.
  • this educt to be hydrogenated is MSA.
  • MSA is preferably used, which originates from the partial oxidation of hydrocarbons. Suitable hydrocarbon streams are benzene, C-olefins (eg, n-butenes, C 4 raffinate streams) or n-butane. Particular preference is given to the use of n-butane, since it represents a low-cost, economical starting material. Methods for the partial oxidation of n-butane are for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6 , h Edition, Electronic Release, Maleic and Furfural Acids - Maleic Anhydrides.
  • reaction effluent is then taken up in a suitable organic solvent or mixture which has a boiling point higher than MSA at atmospheric pressure by at least 30 ° C.
  • This solvent is brought to a temperature in the range between 20 and 160 ° C, preferably between 30 and 80 ° C.
  • the maleic anhydride-containing gas stream from the partial oxidation can be brought into contact in many ways with the solvent: (i) introducing the gas stream into the solvent (eg via gas inlet nozzles or gassing rings), (ii) spraying the solvent into the gas stream and (iii ) Countercurrent contact between the upwardly flowing gas stream and the downwardly flowing solvent in a bottom or packed column.
  • the apparatus known to those skilled in the gas absorption can be used. When choosing the solvent to be used, care must be taken that this does not react with the educt, for example the preferably used MSA.
  • Suitable solvents are: tricresyl phosphate, dibutyl maleate, high molecular weight waxes, aromatic hydrocarbons having a molecular weight between 150 and 400 and a boiling point above 140 ° C, such as dibenzylbenzene; Dialkyl phthalates with -CC 8 alkyl groups, for example dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-n-propyl and di-iso-propyl phthalate; Di-dC-alkyl esters of other aromatic and aliphatic dicarboxylic acids, for example dimethyl-2,3-naphthalene-dicarboxylic acid, dimethyl-1,4-cyclohexane-dicarboxylic acid, methyl esters of long-chain fatty acids having, for example, 14 to 30 carbon atoms, high-boiling ethers, for example dimethyl ether of Polyethylene glycol, for example tetraethylene glycol dimethyl ether
  • the resulting after treatment with the absorbent solution generally has an MSA content of about 5 to 400 grams per liter.
  • the waste gas stream remaining after treatment with the absorbent mainly contains the by-products of the preceding partial oxidation, such as water, carbon monoxide, carbon dioxide, unreacted butanes, acetic and acrylic acids.
  • the exhaust stream is virtually free of MSA.
  • the dissolved MSA is expelled from the absorbent. This is done with hydrogen at or at most 10% above the pressure of the subsequent hydrogenation or alternatively in vacuo with subsequent condensation of remaining MSA.
  • a temperature profile is observed from the boiling points of MSA at the top and the almost MSA-free absorbent at the bottom of the column at the respective column pressure and the dilution with carrier gas (in the first case with hydrogen) results.
  • work is carried out at a head temperature of 130 ° C. and a pressure of 5 bar.
  • rectification installations may be located above the feed of the crude MSA stream.
  • the almost MSA-free absorbent withdrawn from the bottom is returned to the absorption zone.
  • a nearly saturated gas stream of MSA in hydrogen at a temperature of 180 ° C. and a pressure of 5 bar is withdrawn from the top of the column.
  • the H 2 / MSA ratio is about 20 to 650.
  • the condensed MSA is pumped into an evaporator and vaporized there in the recycle gas stream.
  • the MSA hydrogen stream still contains by-products which are formed in the partial oxidation of n-butane, butenes or benzene with oxygen-containing gases, as well as non-separated absorbent. These are, in particular, acetic acid and acrylic acid as by-products, water, maleic acid and the dialkyl phthalates which are preferably used as absorbents.
  • the MSA contains acetic acid in amounts of 0.01 to 1 wt .-%, preferably 0, 1 to 0.8 wt .-% and acrylic acid in amounts of 0.01 to 1 wt .-%, preferably 0.1 to 0 , 8 wt .-%, based on MSA.
  • acetic acid and acrylic acid are hydrogenated to give ethanol or propanol.
  • the maleic acid content is 0.01 to 1 wt .-%, in particular 0.05 to 0.3 wt .-%, based on MSA.
  • dialkyl phthalates are used as absorbents, their content in the MSA depends strongly on the correct operation of the stripping column, in particular on the reinforcing part. Phthalate contents of up to 1, 0 wt .-%, in particular up to 0.5 wt .-% should not be exceeded with appropriate operation, otherwise the consumption of absorbent is too high.
  • the thus obtained hydrogen / maleic anhydride stream is now fed to the hydrogenation zone and hydrogenated as described above.
  • the catalyst activity and -Standzeit is virtually unchanged compared to the use of strong, for example by distillation, prepurified MSA.
  • the process of the present invention allows GBL and THF yields to be at values of about 94%, preferably about 98%. It also achieves a high product selectivity. Examples
  • the resulting suspension is filtered off and washed with water until the effluent wash water no longer contains nitrate ( ⁇ 25 ppm).
  • the filter cake is slurried with water.
  • the resulting mash is sprayed at 120 to 135 ° C.
  • Example 2 a) Tablets (1, 5 ⁇ 2 mm) Shaped Volume: 3.5 mm 3
  • the spray powder from Example 1 is then calcined at 600 ° C.
  • the catalyst thus prepared contains 61% by weight of CuO and 39% by weight of Al 2 O 3 .
  • This is intensively mixed with 3% graphite and pressed into tablets of size 1, 5 x 2 mm. These tablets contained 59% by weight of CuO, 38% by weight of Al 2 O 3 and 3% by weight of carbon.
  • extrudate molding material volume 3.5-5.3 mm 3 boehmite is etched with formic acid, mixed with spray powder from Example 1 and extruded after addition of water in an extruder to strands of length 3 mm with a diameter of 1, 5 mm. The strands are then dried and calcined at 600 ° C. The extrudates contain 50% by weight of CuO and 50% by weight of Al 2 O 3 .
  • Example 3
  • the catalyst Before the start of the reaction, the catalyst is subjected to a hydrogen treatment in the pressureless hydrogenation apparatus.
  • the reactor is heated to 200 ° C and the catalyst activated the time indicated in Table 1 with the particular mixture of hydrogen and nitrogen at atmospheric pressure indicated.
  • the mixture is then bathed for 15 h at 250 ° C with 200 Nl / h of hydrogen.
  • the pressure apparatus used for the hydrogenation consists of an evaporator, a reactor, a cooler, a hydrogen supply, an exhaust gas line and a compressor. The pressure in the apparatus is kept constant.
  • the melted MSA is pumped from above through a plug-in tube onto the preheated (195 ° C.) evaporator and evaporated. From the bottom, a preheated mixture of fresh hydrogen and recycle gas enters the evaporator.
  • Example hydrogen and MSA get into the tempered reactor filled with catalyst (diameter 20 mm). After hydrogenation, the resulting mixture of GBL and THF leaves the reactor with water, other reaction products and hydrogen and is precipitated in the condenser. A portion of the recycle gas is discharged before the remainder, mixed with fresh hydrogen, re-enters the evaporator.
  • the reactor is filled with 1800 ml of the catalyst from Example 2a (total mass 1575 g) and activated according to 3a).
  • the mixture is then bathed for 15 h at 250 ° C with 200 Nl / h of hydrogen.
  • Pilot plant The pressure apparatus used for the hydrogenation consists of an evaporator, a reactor, a cooler, a hydrogen supply, an exhaust gas line and a compressor. The pressure in the apparatus is kept constant.
  • the melted MSA is pumped from above through a plug-in tube onto the preheated (195 ° C) evaporator and evaporated. From the bottom, a preheated mixture of fresh hydrogen and recycle gas enters the evaporator.
  • Example hydrogen and MSA get into the tempered reactor filled with catalyst (Diameter 34 mm). After hydrogenation, the resulting mixture of GBL and THF leaves the reactor with water, other reaction products and hydrogen and is precipitated in the condenser. A portion of the recycle gas is discharged before the remainder, mixed with fresh hydrogen, re-enters the evaporator.
  • the reactor is filled with 1200 ml of the catalyst from Example 2b and activated according to 4a).
  • the hydrogen to MSA ratio is 80: 1.
  • the condensed liquid reaction product, the exhaust gas and the recycle gas are quantitatively analyzed by gas chromatography.
  • the spray powder from Example 1 is then calcined at 600 ° C.
  • the catalyst thus prepared contains 61% by weight of CuO and 39% by weight of Al 2 O 3 . This is intensively mixed with 3% graphite and pressed into tablets of size 3 ⁇ 3 mm. These tablets contained 59% by weight of CuO, 38% by weight of Al 2 O 3 and 3% by weight of carbon. This catalyst has a volume of 21, 2 mm 3 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention se rapporte à un catalyseur exempt de chrome conçu pour l'hydrogénation d'acides dicarboxyliques C4 et/ou leurs dérivés, de préférence l'acide maléique anhydrique en phase gazeuse, sous la forme de corps façonné catalytique, qui présentent un mélange comprenant de 5 à 95 % en poids d'oxyde de cuivre et de 5 à 95 % en poids d'un oxyde comportant des noyaux acides. Ledit catalyseur est caractérisé par le fait que le volume du corps façonné est inférieur à 20 mm<3>. L'invention concerne également un procédé de production du mélange de gamma -butyrolactone (GBL) et de tétrahydrofurane (THF) éventuellement substitué par alkyle présentant un rapport 0 :1 à 9 :1, obtenu par hydrogénation d'acides dicarboxyliques C4 et/ou leurs dérivés, en présence dudit catalyseur. Selon ce procédé, le rapport des produits THF et GBL l'un par rapport à l'autre est mis en place uniquement par la variation des températures dans le réacteur.
PCT/EP2004/013810 2003-12-09 2004-12-04 Catalyseur ameliore pour l'hydrogenation d'acide maleique anhydrique avec y-butyrolactone et tetrahydrofurane Ceased WO2005058492A1 (fr)

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DE10357716A DE10357716A1 (de) 2003-12-09 2003-12-09 Verbesserter Katalysator für die Hydrierung von Maleinsäureanhydrid zu γ-Butyrolacton und Tetrahydrofuran
DE10357716.5 2003-12-09

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WO2005058492A1 true WO2005058492A1 (fr) 2005-06-30

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116060025A (zh) * 2021-10-31 2023-05-05 中国石油化工股份有限公司 一种加氢催化剂及其制备方法和应用
CN119897137A (zh) * 2023-10-26 2025-04-29 中国石油化工股份有限公司 一种顺酐加氢用镍基催化剂及制备方法和应用及顺酐液相加氢制丁二酸酐的方法
CN120754871A (zh) * 2025-09-08 2025-10-10 山西大学 一种以氧化铝陶瓷为支撑的顺酐加氢制γ-丁内酯催化剂、制备方法及应用

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EP0042471A1 (fr) * 1980-03-28 1981-12-30 Norsk Hydro A/S Catalyseur et procédé de préparation du catalyseur
EP0434061A1 (fr) * 1989-12-21 1991-06-26 Union Carbide Chemicals And Plastics Company, Inc. Hydrogénation par catalyseurs Cu-Al
WO1997034694A1 (fr) * 1996-03-21 1997-09-25 Engelhard Corporation PREPARATION ET UTILISATION DE CATALYSEURS SANS CHROME POUR DES APPLICATIONS DANS DES CATALYSEURS Cu/Cr
WO2002048128A2 (fr) * 2000-12-11 2002-06-20 Basf Aktiengesellschaft Procede de production de tetrahydrofurane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0042471A1 (fr) * 1980-03-28 1981-12-30 Norsk Hydro A/S Catalyseur et procédé de préparation du catalyseur
EP0434061A1 (fr) * 1989-12-21 1991-06-26 Union Carbide Chemicals And Plastics Company, Inc. Hydrogénation par catalyseurs Cu-Al
WO1997034694A1 (fr) * 1996-03-21 1997-09-25 Engelhard Corporation PREPARATION ET UTILISATION DE CATALYSEURS SANS CHROME POUR DES APPLICATIONS DANS DES CATALYSEURS Cu/Cr
WO2002048128A2 (fr) * 2000-12-11 2002-06-20 Basf Aktiengesellschaft Procede de production de tetrahydrofurane

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Title
CASTIGLIONI G.L., FERRARI M., GUERCIO A., VACCARI A., LANCIA R. AND FUMAGALLI C.: "Chromium-free catalysts for selective vapor phase hydrogenation of maleic anhydride to gamma-butyrolactone", CATALYSIS TODAY, vol. 27, 1996, pages 181 - 186, XP002315779 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116060025A (zh) * 2021-10-31 2023-05-05 中国石油化工股份有限公司 一种加氢催化剂及其制备方法和应用
CN116060025B (zh) * 2021-10-31 2024-05-31 中国石油化工股份有限公司 一种加氢催化剂及其制备方法和应用
CN119897137A (zh) * 2023-10-26 2025-04-29 中国石油化工股份有限公司 一种顺酐加氢用镍基催化剂及制备方法和应用及顺酐液相加氢制丁二酸酐的方法
CN120754871A (zh) * 2025-09-08 2025-10-10 山西大学 一种以氧化铝陶瓷为支撑的顺酐加氢制γ-丁内酯催化剂、制备方法及应用

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