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EP3080063A1 - Procédé de production de 1,6-hexanediol - Google Patents

Procédé de production de 1,6-hexanediol

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Publication number
EP3080063A1
EP3080063A1 EP14809905.4A EP14809905A EP3080063A1 EP 3080063 A1 EP3080063 A1 EP 3080063A1 EP 14809905 A EP14809905 A EP 14809905A EP 3080063 A1 EP3080063 A1 EP 3080063A1
Authority
EP
European Patent Office
Prior art keywords
hydrogenation
muconic acid
catalyst
hexanediol
acid
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.)
Withdrawn
Application number
EP14809905.4A
Other languages
German (de)
English (en)
Inventor
Christoph Müller
Martin Bock
Marion DA SILVA
Rolf-Hartmuth Fischer
Benoit BLANK
Alois Kindler
Johann-Peter Melder
Bernhard Otto
Andreas Henninger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP14809905.4A priority Critical patent/EP3080063A1/fr
Publication of EP3080063A1 publication Critical patent/EP3080063A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C07C29/136—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 of >C=O containing groups, e.g. —COOH
    • C07C29/147—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 of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—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 of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • 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
    • C07C29/177—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 simultaneous reduction of a carboxy 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • 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
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a process for producing 1,6-hexanediol by subjecting muconic acid and / or one of its esters and / or one of its lactones to hydrogenation of the double bonds and reduction of the carboxylic acid and / or carboxylic acid ester groups.
  • the present invention further relates to 1, 6-hexanediol, which can be prepared by this method.
  • 1, 6-hexanediol is a sought monomeric component, which is used mainly in the polyester and polyurethane sector.
  • 1,6-hexanediol can be prepared by hydrogenation of adipic or adipic diesters in the presence of Cu, Co or Mn catalysts become. The synthesis is carried out at a temperature of 170 to 240 ° C and a pressure of 5 to 30 MPa. 1, 6-hexanediol can also be obtained by catalytic hydrogenation of caprolactone.
  • WO 2010/1 15759 describes a process for the preparation of 1, 6-hexanediol by catalytic hydrogenation of ester mixtures containing as main components oligo- and polyesters of adipic acid and 6-hydroxycaproic acid and by
  • Adipic acid is conventionally synthesized by oxidation of cyclohexene or cyclohexanone starting from benzene. But it can also be obtained in an environmentally friendly manner from biogenic sources.
  • HMDA hexamethylenediamine
  • US 4,968,612 describes a fermentation process for the preparation of muconic acid and the hydrogenation of the resulting muconic acid to adipic acid. Concretely, the muconic acid is reacted as a 40% by weight slurry in acetic acid and in the presence of a palladium catalyst on carbon. The water content of the acetic acid used is not specified. A disadvantage of this reaction is the use of corrosive acetic acid, which requires the use of high-quality corrosion-resistant reactors.
  • WO 2010/141499 describes the oxidation of lignin to vanillic acid, their decarboxylation to 2-methoxyphenol and further conversion to catechol and finally oxidation to muconic acid and the hydrogenation of thus obtained
  • Muconic acid with various transition metal catalysts to adipic acid The solvent used for the hydrogenation is not specified.
  • the present invention has for its object to provide an economical process for the preparation of 1, 6-hexanediol.
  • this process should not start from petrochemical C6 building blocks but from C6 building blocks that can be produced from renewable raw materials.
  • 1, 6-hexanediol to be made available in high yield and purity.
  • a muconic acid starting material which is selected from muconic acid, esters of muconic acid, lactones of muconic acid and mixtures thereof, a one- or two-stage reaction with hydrogen with hydrogenation of the double bonds and reduction of the carboxylic acid - and / or carboxylic ester groups to 1, 6-hexanediol.
  • the muconic acid used originates from renewable (biogenic) sources.
  • a first aspect of the invention is a process for the preparation of 1,6-hexanediol in which a) a muconic acid starting material selected from muconic acid, esters of muconic acid, lactones of muconic acid and mixtures thereof, b ) subjecting the Muconklasgangsmaterial a reaction with hydrogen in the presence of at least one hydrogenation catalyst to 1, 6-hexanediol, and c) subjecting the hydrogenation in step b) to a distillative separation to obtain 1, 6-hexanediol.
  • Another object of the invention is the use of a poly (muconic acid ester) of the general formula (VI)
  • 6-hexanediol Another object of the invention is 1, a C 14 / C 12 -lsotopenver- ratio in the range of 0.5 x 10 "12 to 5 ⁇ 10" 12 has.
  • a further subject of the invention is 1,6-hexanediol which can be prepared starting from biocatalytically synthesized muconic acid from at least one renewable raw material.
  • the muconic acid starting material provided in step a) contains no salts of the muconic acid.
  • the hydrogenation in step b) takes place in the liquid phase in the presence of water as the sole solvent.
  • the hydrogenation is carried out in step b) in the liquid phase in the presence of water as the sole solvent, wherein a heterogeneous transition metal catalyst is used as the hydrogenation catalyst.
  • the hydrogenation in step b) comprises the following substeps: b1) hydrogenating muconic acid or one of its esters in water as sole solvent to adipic acid in the presence of a first heterogeneous hydrogenation catalyst, and b2) hydrogenating the adipic acid obtained in step b1) in water as the sole solvent to 1,6-hexanediol in the presence of a second heterogeneous hydrogenation catalyst, wherein preferably the hydrogenation takes place continuously, at least in step b2).
  • Muconic acid (2,4-hexadiene dicarboxylic acid) exists in three stereoisomeric forms, the ice, cis, cis, trans, and trans, trans forms, which may be present as a mixture.
  • WO 2010/148080 teaches that upon heating cis, cis-muconic acid in water under reflux and subsequent crystallization, cis-trans-muconic acid is obtained in only 69% yield. The remaining mother liquor no longer consists of muconic acid but contains lactones and other unknown reaction products. From these results, those skilled in the art would have expected substantially lower adipic acid yields in the hydrogenation of water-suspended muconic acid, according to the preferred embodiment of the present invention. EMBODIMENTS OF THE INVENTION
  • the invention includes the following preferred embodiments:
  • a process for the preparation of 1, 6-hexanediol which comprises: a) providing a muconic acid starting material selected from muconic acid, esters of muconic acid, lactones of muconic acid and mixtures thereof, b) the muconic acid starting material to a reaction with hydrogen in the presence of at least one hydrogenation catalyst 1, 6-hexanediol, and c) subjecting the discharge from the hydrogenation in step b) to a distillative separation to obtain 1, 6-hexanediol.
  • step a) a muconic acid starting material is provided in which the muconic acid is removed from a regeneration origin, wherein their preparation is preferably carried out by biocatalytic synthesis of at least one renewable raw material.
  • a muconic acid starting material which is selected from muconic acid, Muconklaremonoestern, Mucon Listerediestern, poly (muconic acid esters) and mixtures thereof.
  • a muconic acid starting material which is selected from lactones (III), (IV) and (V) and mixtures thereof:
  • Step b) takes place in the liquid phase in the presence of a solvent which is selected from water, aliphatic C 1 to C 8 alcohols, aliphatic C 2 to C 6 diols, ethers and mixtures it.
  • a solvent which is selected from water, aliphatic C 1 to C 8 alcohols, aliphatic C 2 to C 6 diols, ethers and mixtures it.
  • a homogeneous or heterogeneous transition metal catalyst is used, preferably a heterogeneous transition metal catalyst.
  • a Mu acid starting material which is selected from Mucon Text- re, Muconklad and mixtures thereof and the hydrogenation catalyst at least 50 wt .-% cobalt, ruthenium or rhenium based on the total weight of the reduced catalyst.
  • a mu acid starting material which is selected from Muzonklad- rediester, poly (muconic acid esters) and mixtures thereof and the hydrogenation catalyst at least 50 wt .-% copper based on the total weight of the reduced catalyst.
  • step b) takes place at a temperature which is in the range of 50 to 300 ° C.
  • step b) takes place at a hydrogen partial pressure which is in a range of 100 to 300 bar.
  • step b) comprises the following substeps:
  • step b1) takes place at a temperature which is in the range of 50 to 160 ° C and the hydrogenation in step b2) takes place at a temperature in the range of 160 up to 240 ° C.
  • 1, 6-hexanediol characterized in that it comprises a C 14 / C 12 -lsotopeneat in the range of 0.5 x 10 "12 to 5 ⁇ 10.” 12
  • 1, 6-hexanediol characterized in that it can be prepared starting from biocatalytically synthesized from at least one renewable raw material Muconsaure.
  • esters of the muconic acid are the esters with a separate (external) alcohol component.
  • Lactones of muconic acid are understood as meaning the compounds (III) and (IV) obtainable by intramolecular Michael addition and the product (V) of the hydrogenation of the compound (III):
  • the lactone (V) can also be formed by intramolecular Michael addition of dihydromuconic acid. Regardless of its preparation, the lactone (V) may be formally referred to as "hydrogenated monolactone of muconic acid". The lactone (V) is understood in the context of the invention as the lactone of muconic acid.
  • the muconic acid provided in step a) of the process according to the invention comes from renewable sources.
  • this includes natural (biogenic) sources and non-fossil sources, such as crude oil, natural gas or coal.
  • the muconic acid provided in step a) of the method according to the invention is derived from carbohydrates, eg. As starch, cellulose and sugars, or lignin.
  • Renewable compounds, such as muconic acid have a different 14 C to 12 C isotope ratio than compounds derived from fossil sources such as petroleum. Accordingly, the muconic acid used in step a) preferably has a 14 C to 12 C isotope ratio in the range of
  • the production of muconic acid from renewable sources can be carried out by all methods known to those skilled in the art, preferably biocatalytically.
  • the biocatalytic production of muconic acid from at least one renewable raw material is described, for example, in the following documents: US Pat. No. 4,968,612, US Pat.
  • WO 2010/148063 A2 WO 2010/148080 A2 and K. M. Draths and J. W. Frost, J. Am. Chem. Soc. 1994, 16, 339-400 and W. Niu et al., Biotechnol. Prog. 2002, 18, 201 - 21 1.
  • muconic acid (2,4-hexadiene dicarboxylic acid) exists in three isomeric forms, the cis, cis, cis, trans and trans, trans forms, which may be present as a mixture.
  • the term "muconic acid” encompasses the different conformers of muconic acid in any desired composition.
  • all conformers of the muconic acid and / or its esters and any mixtures thereof are in principle suitable.
  • a starting material is used which is enriched in cis, trans-muconic acid and / or its esters or which consists of cis, trans-muconic acid and / or their esters.
  • cis, trans-muconic acid and their esters have a higher solubility in water and in organic media than cis, cis-muconic acid and trans, trans-muconic acid.
  • step b) of the process according to the invention If a feedstock containing at least one component selected from cis, cis-muconic acid, trans, trans-muconic acid and / or esters thereof is used in step b) of the process according to the invention, this is added to an isomerization before or during the hydrogenation cis, trans-muconic acid or its esters.
  • the isomerization of cis, cis-muconic acid to cis, trans-muconic acid is shown in the following scheme:
  • Hydrogenation catalysts iodine or UV radiation in question. Suitable hydrogenation catalysts are those described below.
  • the isomerization can be carried out, for example, by the process described in WO 201 1/08531 1 A1.
  • the starting material for the reaction with hydrogen in step b) is preferably at least 80% by weight, particularly preferably at least 90% by weight, of cis, trans-muconic acid and / or its esters, based on the total weight of all muconic acid contained in the starting material and muconic ester conformers.
  • muconic acid starting material selected from muconic acid, muconic acid monoesters, muconic acid diesters, poly (muconic acid esters), lactones of muconic acid and mixtures thereof.
  • muconic acid polyester also denotes oligomeric muconic acid esters which has at least one repeating unit derived from the muconic acid or the diol used for ester formation and at least two repeat units bonded thereto via carboxylic acid ester groups.
  • the muconic acid monoester used is preferably at least one compound of the general formula (I)
  • Preferred as poly (muconic acid ester) is at least one compound of the general formula (VI)
  • the degree of polymerization of the poly denotes the sum of the repeat units which formally derive from muconic acid and the repeat units which formally derive from diols HO- (CH 2) x -OH.
  • the hydrogenation in step b) is carried out using a muconic acid starting material selected from muconic acid, muconic acid monoesters, muconic diesters, poly (muconic acid esters) and mixtures thereof.
  • the hydrogenation in step b) is carried out using a muconic acid starting material selected from lactones (III), (IV) and (V) and mixtures thereof:
  • a muconic acid starting material is used, which is selected from muconic acid, Muconklaremonoestern, Mucondochrediestern, poly (muconic acid esters) and mixtures thereof, wherein the hydrogenation takes place in the liquid phase.
  • the hydrogenation in step b) takes place in the liquid phase in the presence of a solvent which is selected from water, aliphatic C 1 to C 8 alcohols, aliphatic C 2 to C 6 diols, ethers and mixtures thereof.
  • a solvent which is selected from water, aliphatic C 1 to C 8 alcohols, aliphatic C 2 to C 6 diols, ethers and mixtures thereof.
  • the solvent is selected from water, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol and tert-butanol, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether and mixtures thereof. Aliphatic C to C5 alcohols, water and mixtures of these solvents are preferred.
  • methanol n-butanol
  • isobutanol water and mixtures of these solvents.
  • 1, 6-hexanediol can be used alone or in admixture with alcohols and / or water.
  • a solution which contains 10 to 60% by weight of muconic acid or one of its esters, particularly preferably 20 to 50% by weight, very particularly preferably 30 to 50% by weight. %, contains.
  • at least one muconic acid diester of the general formula (II) is used for the hydrogenation in step b).
  • Suitable hydrogenation catalysts for the reaction in step b) are in principle the transition metal catalysts known to those skilled in the art for hydrogenating carbon-carbon double bonds.
  • the catalyst comprises at least one transition metal of groups 7, 8, 9, 10 and 11 of the periodic table according to IU-PAC.
  • the catalyst comprises at least one transition metal selected from the group consisting of Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu and Au.
  • the catalyst has at least one transition metal from the group Co, Ni, Cu, Re, Fe, Ru, Rh, Ir.
  • the hydrogenation catalysts consist of said transition metals as such or comprise said transition metals supported, as precipitation catalysts, as Raney catalysts or as mixtures thereof.
  • inert carrier material for the hydrogenation catalysts used according to the invention in step b) virtually all support materials of the prior art, as they are advantageously used in the preparation of supported catalysts, for example carbon, S1O2 (quartz), porcelain, magnesium oxide, tin dioxide, Silici - Umcarbid, T1O2 (rutile, anatase), Al2O3 (alumina), aluminum silicate, steatite (magnesium silicate), zirconium silicate, cersilicate or mixtures of these support materials, are used.
  • Preferred support materials are carbon, alumina and silica.
  • a particularly preferred carrier material is carbon.
  • silica support material can silica materials of different origin and production, for. B.
  • pyrogenic silicas or wet-chemically prepared silicas such as silica gels, aerogels or precipitated silicas, are used for catalyst preparation (for the preparation of various SiO 2 starting materials see: W. Büchner, R. Sch Kunststoffs, G. Winter, KH Büchel: Industrial Inorganic Chemie, 2nd ed., P. 532-533, VCH Verlagsgesellschaft, Weinheim 1986).
  • the hydrogenation catalysts can be used as shaped bodies, for. B. in the form of spheres, rings, cylinders, cubes, cuboids or other geometric bodies.
  • Unsupported catalysts can be formed by conventional methods, e.g. By extruding, tableting, etc.
  • the shape of supported catalysts is determined by the shape of the support.
  • the support may be subjected to a molding process before or after application of the catalytically active component (s).
  • the hydrogenation catalysts may, for. B. in the form of pressed cylinders, tablets, pastilles, carriage wheels, rings, stars or extrudates, such as solid strands, polylobd strands, hollow strands and honeycomb bodies or other geometric bodies are used.
  • the catalyst particles generally have an average of the (largest) diameter of 0.5 to 20 mm, preferably 1 to 10 mm.
  • These include z. B. transition metal catalysts K in the form of tablets, for. B. with a diameter of 1 to 7 mm, preferably 2 to 6 mm, and a height of 3 to 5 mm, rings with z. B. 4 to 7 mm, preferably 5 to 7 mm, outer diameter, 2 to 5 mm in height and 2 to 3 mm hole diameter, or strands of different lengths of a diameter of z. B. 1, 0 to 5 mm.
  • Such forms can be obtained in a manner known per se by tableting, extrusion or extrusion.
  • the catalyst composition customary auxiliaries, for.
  • lubricants such as graphite, polyethylene oxide, celluloses or fatty acids (such as stearic acid) and / or molding aids and reinforcing agents, such as glass fibers, asbestos or silicon carbide, are added.
  • the catalyst can be present under the hydrogenation conditions both as a homogeneous and as a heterogeneous catalyst.
  • the catalyst is present under the hydrogenation conditions as a heterogeneous catalyst. If a heterogeneous catalyst is used, this can be applied, for example, to a reticulated carrier.
  • the heterogeneous catalyst can be applied to the inner wall of a tubular support, wherein the tubular support is flowed through by the reaction mixture.
  • the catalyst can be used as a particulate solid.
  • the hydrogenation in step b) takes place in the liquid phase and the catalyst is present in the form of a suspension.
  • the suspended catalyst can be kept in the reaction zone by retention methods known to those skilled in the art. These retention methods preferably comprise cross-flow filtration, gravity filtration and / or filtration by means of at least one filter candle.
  • a muconic acid starting material is used for the hydrogenation in step b) which is selected from muconic acid, muconic acid monoesters, lactones of muconic acid and mixtures thereof.
  • the hydrogenation in step b) is preferably carried out using a hydrogenation catalyst which contains at least 50% by weight of cobalt, ruthenium or rhenium, based on the total weight of the reduced catalyst.
  • a hydrogenation catalyst which contains at least 50% by weight of cobalt, ruthenium or rhenium, based on the total weight of the reduced catalyst.
  • catalysts which contain at least 50% by weight of cobalt are used for the hydrogenation, they may furthermore contain, in particular, phosphoric acid and / or further transition metals, preferably copper, manganese and / or molybdenum.
  • the preparation of a suitable catalyst precursor is known from DE 2321 101.
  • catalyst precursors can be reduced to the active, metallic cobalt-containing catalysts by treatment with hydrogen or mixtures of hydrogen and inert gases such as nitrogen. These catalysts are full contacts, which are predominantly made of metal and contain no catalyst support.
  • a muconic acid starting material is used for the hydrogenation in step b), which is selected from muconic diesters, poly (muconic acid esters) and mixtures thereof.
  • the hydrogenation in step b) preferably uses a hydrogenation catalyst which contains at least 50% by weight of copper, based on the total weight of the reduced catalyst.
  • Suitable catalysts are in principle all suitable for the hydrogenation of carbonyl homogeneous and heterogeneous catalysts such as metals, metal oxides, metal compounds or mixtures thereof into consideration.
  • homogeneous catalysts are, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume IV / 1 c, Georg Thieme Verlag Stuttgart, 1980, pp 45-67 and examples of heterogeneous catalysts are, for example in Houben-Weyl, methods of organic chemistry , Volume IV / 1 c, pp 16 to 26 described.
  • catalysts which contain one or more of the elements from subgroups I and VI. to VIII. of the Periodic Table of the Elements, preferably copper, chromium, molybdenum, manganese, rhenium, ruthenium, cobalt, nickel or palladium, particularly preferably copper, cobalt or rhenium.
  • the cobalt, ruthenium or rhenium-containing catalysts mentioned above can also be used in the hydrogenation of the muconic acid diesters, oligoesters and polyesters. However, it is preferred to use at least 50 wt .-% copper (based on the total weight of the reduced catalyst) containing catalysts instead of these catalysts.
  • the catalysts may consist solely of active components or their active components may be supported.
  • Suitable carrier materials are, in particular, O 2 O 3, Al 2 O 3, SiO 2, ZrO 2, ZnO, BaO and MgO or mixtures thereof.
  • catalysts as described in EP 0 552 463 A1.
  • These are catalysts which have in the oxidic form the composition Cu a AlbZr c MndOx, where a> 0, b> 0, c a 0, d> 0, a> b / 2, b> a / 4, a> c and a> d, and x denotes the number of oxygen ions required to maintain electroneutrality per formula unit.
  • the preparation of these catalysts can be carried out, for example, according to the specifications of EP 552 463 A1 by precipitation of sparingly soluble compounds from solutions containing the corresponding metal ions in the form of their salts.
  • Suitable salts are, for example, halides, sulfates and nitrates.
  • Suitable precipitants are all agents which lead to the formation of such insoluble intermediates, which can be converted by thermal treatment in the oxides.
  • Particularly suitable intermediates are the hydroxides and carbonates or bicarbonates, so that alkali metal carbonates or ammonium carbonate are used as particularly preferred precipitants.
  • the BET surface area of such catalysts is between 10 and 150 m 2 / g.
  • catalysts are suitable which have a BET surface area of 50 to 120 m 2 / g, wholly or partially contain crystals with spinel structure and copper in the form of copper oxide.
  • WO 2004/085 356 A1 also describes copper catalysts suitable for the process according to the invention, the copper oxide, aluminum oxide and at least one of the oxides of lanthanum, tungsten, molybdenum, titanium or zirconium and additionally pulverulent metallic copper, copper flakes, pulverulent cement, Graphite or containing a mixture thereof. These catalysts are particularly suitable for all mentioned ester hydrogenations.
  • step b) The hydrogenation in step b) can be carried out batchwise or continuously, with continuous hydrogenation being preferred.
  • the catalyst loading in continuous operation is preferably 0.1 to 2 kg, more preferably 0.5 to 1 kg of starting material to be hydrogenated per kg of hydrogenation catalyst and hour.
  • the molar ratio of hydrogen to muconic acid starting material is preferably 50: 1 to 10: 1, more preferably 30: 1 to 20: 1.
  • the muconic acid starting material is selected according to the invention from muconic acid, esters of muconic acid, lactones of muconic acid and mixtures thereof.
  • a muconic acid starting material which is selected from at least two of the abovementioned compounds, the amount of hydrogen used, depending on the proportion of the compounds to be hydrogenated, is chosen according to the abovementioned design rule.
  • the hydrogenation is carried out in n hydrogenation reactors connected in series (in series), n being an integer of at least 2. Suitable values for n are 2, 3, 4, 5, 6, 7, 8, 9 and 10. Preferably, n is 3 to 6 and in particular 2 or 3. In this embodiment, the hydrogenation is preferably carried out continuously.
  • the reactors used for the hydrogenation may independently have one or more reaction zones within the reactor.
  • the reactors may be the same or different reactors. These can be z. B. each have the same or different mixing characteristics and / or be subdivided by internals one or more times.
  • Suitable pressure-resistant reactors for the hydrogenation are known to the person skilled in the art. These include the commonly used reactors for gas-liquid reactions, such as. B. tube reactors, tube bundle reactors, gas circulation reactors, bubble columns, loop apparatus, stirred tank (which can also be designed as stirred tank cascades), air-lift reactors, etc.
  • the process according to the invention using heterogeneous hydrogenation catalysts can be carried out in fixed bed or suspension mode.
  • the fixed bed mode can be z. B. in sump or in trickle run.
  • the hydrogenation catalysts are preferably used as shaped bodies, as described above, for. In the form of pressed cylinders, tablets, pastilles, carriage wheels, rings, stars or extrudates, such as solid strands, poly-polar strands, hollow strands, honeycomb bodies, etc.
  • heterogeneous catalysts are also used.
  • the heterogeneous catalysts are usually used in a finely divided state and are finely suspended in the reaction medium before.
  • Suitable heterogeneous catalysts and processes for their preparation are those described above.
  • a reactor In the hydrogenation on a fixed bed, a reactor is used, in the interior of which the fixed bed is arranged, through which the reaction medium flows.
  • the fixed bed can be formed from a single or multiple beds.
  • Each bed may have one or more zones, wherein at least one of the zones contains a material active as a hydrogenation catalyst.
  • Each zone can have one or more different catalytically active materials and / or one or more different inert materials. Different zones may each have the same or different compositions. It is also possible to provide a plurality of catalytically active zones, which are separated from each other, for example, by inert shakes.
  • the individual zones may also have different catalytic activity. For this purpose, various catalytically active materials can be used and / or at least one of the zones an inert material can be added.
  • the reaction medium flowing through the fixed bed contains at least one liquid phase.
  • the reaction medium may additionally contain a gaseous phase.
  • loop apparatuses such as jet loops or propeller loops
  • stirred tank which can also be configured as ROWkesselkaskaden, bubble columns or air-lift reactors are used.
  • the continuous hydrogenation of the process according to the invention is preferably carried out in at least two fixed bed reactors connected in series (in series).
  • the Reactors are preferably operated in DC.
  • the feeding of the feed streams can be done both from above and from below.
  • At least two of the reactors may have a different temperature from each other.
  • each downstream reactor is operated at a higher temperature than the previous reactor.
  • each of the reactors may have two or more different temperature reaction zones.
  • a higher temperature than in the first reaction zone or in each subsequent reaction zone a higher temperature than in a preceding reaction zone can be set, for. B. to achieve the fullest possible conversion in the hydrogenation.
  • the hydrogenation in step b) is carried out using a hydrogenation device comprising at least two reactors or at least one reactor having at least two reaction zones.
  • the hydrogenation is carried out initially in a temperature range of 50 to 160 ° C and then in a temperature range of 160 to 240 ° C.
  • the carbon-carbon double bonds can be hydrogenated in the upstream part of the hydrogenation apparatus, and subsequently essentially the carboxylic acid and / or carboxylic acid ester groups can be reduced in the downstream part of the hydrogenation apparatus.
  • at least two of the reactors i.e., 2 to n of the reactors
  • each downstream reactor is operated at a higher pressure than the previous reactor.
  • the feeding of the hydrogen required for the hydrogenation can be carried out in the first and optionally additionally in at least one further reactor.
  • the feed of hydrogen takes place only in the first reactor.
  • the amount of hydrogen fed to the reactors results from the amount of hydrogen consumed in the hydrogenation reaction and the amount of hydrogen optionally discharged with the exhaust gas.
  • the setting of the reacted in the respective reactor portion of compound to be hydrogenated can, for. B. on the reactor volume and / or the residence time in the reactor.
  • the conversion in the first reactor, based on adipic acid or adipic acid ester formed, is preferably at least 70%, more preferably at least 80%.
  • the total conversion in the hydrogenation, based on hydrogenatable starting material, is preferably at least 97%, particularly preferably at least 98%, in particular at least 99%.
  • the selectivity in the hydrogenation, based on formed 1,6-hexanediol, is preferably at least 97%, particularly preferably at least 98%, in particular at least 99%.
  • one or more of the reactors may be provided with at least one cooling device.
  • at least the first reactor is provided with a cooling device.
  • the heat of reaction can be removed by cooling an external recycle stream or by internal cooling in at least one of the reactors.
  • the customary devices generally hollow body modules, such as field pipes, pipe coils, heat exchanger plates, etc. can be used.
  • the reaction can also be carried out in a cooled tube bundle reactor.
  • the hydrogenation is preferably carried out in n hydrogenation reactors connected in series, where n is an integer of at least two, and where at least one reactor has an external circulation stream from the reaction zone (external recycle stream, liquid recycle, loop mode).
  • n stands for two or three.
  • the hydrogenation is preferably carried out in n hydrogenation reactors connected in series, where n is preferably two or three, and the first to (n-1). Reactor has a guided in an external circuit current from the reaction zone.
  • the hydrogenation is preferably carried out in n hydrogenation reactors connected in series, n preferably being two or three, and the reaction being carried out adiabatically in the nth reactor (the last reactor through which the reaction mixture to be hydrogenated is passed).
  • the hydrogenation is carried out in n series-connected hydrogenation reactors, where n is preferably two or three, and wherein the n.
  • Reactor is operated in a straight pass. If a reactor is operated "in straight pass", it should be understood here and below that a reactor is operated without recycling the reaction product in the sense of the loop procedure.
  • the straight-through operation basically excludes backmixing internals and / or stirring devices in the reactor.
  • the heat of reaction occurring during the reaction is insufficient to maintain the desired temperature in the reactor. it may also be necessary to heat the reactor (or individual reaction zones of the second reactor). This can be done analogously to the previously described removal of the heat of reaction by heating an external circulation stream or by internal heating. In a suitable embodiment, the heat of reaction from at least one of the previous reactors can be used to control the temperature of a reactor.
  • the heat of reaction removed from the reaction mixture can be used to heat the feed streams of the reactors.
  • This can z. B. the feed stream of the compound to be hydrogenated in the first reactor at least partially mixed with an external recycle stream of this reactor and the combined streams are then fed into the first reactor.
  • the feed stream from the (m-1) th reactor in the mth reactor can be mixed with a recycle stream of the mth reactor and the combined streams then fed to the mth reactor
  • the feed stream of the compound to be hydrogenated and / or another feed stream can be heated by means of a heat exchanger which is operated with withdrawn hydrogenation heat.
  • a reactor cascade of n reactors connected in series is used, the reaction being carried out adiabatically in the nth (nth) reactor.
  • This term is understood in the context of the present invention in the technical and not in the physico-chemical sense.
  • Adiabatic reaction is understood to mean a procedure in which the amount of heat liberated in the hydrogenation is absorbed by the reaction mixture in the reactor. taken and no cooling is used by cooling devices.
  • the heat of reaction with the reaction mixture is discharged from the second reactor, except for a residual portion, which is discharged by natural heat conduction and heat radiation from the reactor to the environment.
  • the nth reactor is operated in a straight pass.
  • a two-stage reactor cascade is used for the hydrogenation, wherein the first hydrogenation reactor has a current conducted in an external circuit from the reaction zone.
  • a reactor cascade of two reactors connected in series is used, the reaction being carried out adiabatically in the second reactor.
  • a three-stage reactor cascade is used for the hydrogenation, wherein the first and the second hydrogenation reactor have a current conducted in an external circuit from the reaction zone.
  • a reactor cascade of three reactors connected in series is used, the reaction being carried out adiabatically in the third reactor.
  • additional mixing can take place in at least one of the reactors used. An additional mixing is particularly advantageous if the hydrogenation takes place at high residence times of the reaction mixture.
  • the currents introduced into the reactors are used by introducing them via suitable mixing devices, such as nozzles, in the respective reactors.
  • suitable mixing devices such as nozzles
  • a discharge is taken from each of the first to (n-1) th reactors, which still contains hydrogenatable components and is fed into the subsequently connected hydrogenation reactor.
  • the discharge is separated into a first and a second partial stream, wherein the first partial stream is recycled as a circular stream to the reactor to which it was taken and the second partial stream is fed to the subsequent reactor.
  • the discharge may contain dissolved or gaseous portions of hydrogen.
  • the discharge from the first to (n-1) th reactor is fed to a phase separation vessel, separated into a liquid and into a gaseous phase, the liquid phase separated into the first and the second partial stream and the gas phase at least partially the subsequent reactor supplied separately.
  • the discharge from the first to (n-1) th reactor is fed to a phase separation vessel and in a nen first hydrogen-depleted partial stream and a second hydrogen-enriched substream separates.
  • the first partial flow is then recycled as a circulating stream to the reactor, to which it has been removed and the second partial flow fed to the subsequent reactor.
  • the feed of the second to nth reactor with hydrogen is not carried out via a hydrogen-containing feed taken from the upstream reactor, but with fresh hydrogen via a separate feed line.
  • the process variant described above is particularly advantageous for controlling the reaction temperature and the heat transfer between the reaction medium, limiting apparatus walls and environment.
  • Another way to control the heat balance is to control the inlet temperature of the inlet of the compound to be hydrogenated.
  • a lower temperature of the incoming feed usually leads to an improved removal of the heat of hydrogenation.
  • the inlet temperature may be set higher to achieve a higher reaction rate and thus to compensate for the decreasing catalyst activity.
  • the service life of the hydrogenation catalyst used can thus be extended as a rule.
  • step b) of the process according to the invention comprises the following substeps: b1) hydrogenating muconic acid or one of its esters in aqueous solution to adipic acid or one of its esters in the presence of a first hydrogenation catalyst, and b2) hydrogenating the adipic acid or one of its esters in aqueous solution to 1,6-hexanediol in the presence of a second hydrogenation catalyst.
  • the first catalyst is Raney cobalt and / or Raney nickel and / or Raney copper.
  • the second catalyst comprises at least 50% by weight, based on the total weight of the reduced catalyst, of elements which are selected from the group consisting of rhenium, iron, ruthenium, cobalt, rhodium, iridium, nickel and copper ,
  • the second catalyst contain at least 50% by weight of elements which are selected from the group consisting of rhenium, ruthenium and cobalt.
  • the second catalyst contain at least 50% by weight of copper.
  • the hydrogenation in step b1) is preferably carried out at a temperature in the range of 50 to 160 ° C, more preferably 60 to 150 ° C, most preferably 70 to 140 ° C. In this temperature range, preferably more than 50%, particularly preferably more than 70%, very particularly preferably more than 90% of the carbon-carbon double bonds present in the muconic acid are hydrogenated.
  • the hydrogenation in step b) is preferably carried out at a temperature which is in the range from 160 to 240 ° C., particularly preferably from 170 to 230 ° C., very particularly preferably from 170 to 220 ° C.
  • a temperature which is in the range from 160 to 240 ° C., particularly preferably from 170 to 230 ° C., very particularly preferably from 170 to 220 ° C.
  • the not yet hydrogenated carbon-carbon double bonds and the carboxyl groups are hydrogenated.
  • Step b1) can be carried out, for example, in a first loop reactor and step b2) in a second loop reactor.
  • the reaction of step b2) can be completed in a subsequent tubular reactor.
  • a tubular reactor connects in a straight passage.
  • the hydrogenations can be carried out in bottom or trickle mode.
  • the reaction product obtained in the hydrogenation of muconic acid in water as solvent is an aqueous 1,6-hexanediol solution.
  • the water is removed by distillation in step c) and 1,6-hexanediol can be dissolved in high purity (> 97%) can be obtained.
  • the muconic acid hydrogenation is carried out, for example, in methanol as solvent, part of the muconic acid is converted in situ into the muconic acid monomethyl and muconic acid dimethylester.
  • the hydrogenation is a solution of 1,6-hexanediol in a mixture of methanol and water.
  • methanol and water are separated from 1, 6-hexanediol.
  • Methanol is preferably separated from water and recycled to the hydrogenation. Water is discharged.
  • n-butanol or isobutanol is used as the solvent in the hydrogenation of the hydrogen chloride, the mixture is obtained after cooling and venting of the hydrogenation effluent liquid two-phase mixture.
  • the aqueous phase is separated from the organic phase by phase separation.
  • the organic phase is distilled.
  • Butanol is separated off as the top product and is preferably recycled to the muconic acid hydrogenation.
  • 1, 6-hexanediol can, if necessary, be further purified by distillation.
  • muconic acid diesters are used for the hydrogenation, largely anhydrous solutions of 1,6-hexanediol are obtained, which can be worked up by distillation to give pure 1,6-hexanediol.
  • the resulting alcohols are preferably recycled to the esterification step.
  • a suspension of 24 g of cis, cis-muconic acid and 1 g of Raney Ni in 56 g of water was introduced into a 250 ml stirring autoclave, 3 MPa of hydrogen were pressed in and heated to 80.degree. After reaching the temperature of 80 ° C, the pressure was increased to 10 MPa and replenished so much hydrogen that the pressure remained constant. After 12 h reaction time was cooled to a temperature of 60 ° C, depressurized to atmospheric pressure and the solution was filtered from the catalyst. It was then slowly cooled to 20 ° C and thereby crystallized adipic acid as a white solid. In the Solution was in addition to adipic still lactone (V) can be detected. The yield of adipic acid was 95% and of lactone (V) 5%.
  • the outputs were analyzed by gas chromatography (% by weight, method with internal standard). The yield of 1, 6-hexanediol was 94%, the conversion of adipic acid was 98.5%. Other products that were found were 3% 6-hydroxycaproic acid, 1% 6-hydroxycaproic acid 1,6-hexanediol ester and 1% hexanol.

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Abstract

L'invention concerne un procédé de production de 1,6-hexandiol comprenant les étapes suivantes : a) disposer d'une matière première acide galactarique, sélectionnée entre acide galactatique, esters d'acide galactarique, lactones d'acide galactarique et des mélanges desdits composés, b) faire réagir la matière première acide galactarique avec de l'hydrogène en présence d'au moins un catalyseur d'hydrogénation pour obtenir du 1,6 hexanediol, et c) soumettre le produit issu de l'hydrogénation à l'étape b) à une séparation par distillation de manière à obtenir du 1,6-hexanediol.
EP14809905.4A 2013-12-13 2014-12-12 Procédé de production de 1,6-hexanediol Withdrawn EP3080063A1 (fr)

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EP14809905.4A EP3080063A1 (fr) 2013-12-13 2014-12-12 Procédé de production de 1,6-hexanediol
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US4968612A (en) 1984-07-27 1990-11-06 Celgene Corporation Continuous fermentation process for aromatic hydrocarbon bioconversion
DE4141199A1 (de) 1991-12-13 1993-06-17 Sued Chemie Ag Chromfreier katalysator fuer die hydrierung von organischen verbindungen, die die carbonylfunktionen enthalten
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CN1092174C (zh) 1996-03-01 2002-10-09 巴斯福股份公司 纯度超过99%的1,6－己二醇的制备方法
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ES2404534T3 (es) 2009-04-08 2013-05-28 Basf Se Proceso para la preparación de 1,6-hexandiol mediante hidrogenación de oligo- y poliésteres
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