EP2089370A1 - Procédé de production de 2-méthyltétrahydrofurane en une étape à partir de furfural sur un catalyseur - Google Patents

Procédé de production de 2-méthyltétrahydrofurane en une étape à partir de furfural sur un catalyseur

Info

Publication number
EP2089370A1
EP2089370A1 EP08774263A EP08774263A EP2089370A1 EP 2089370 A1 EP2089370 A1 EP 2089370A1 EP 08774263 A EP08774263 A EP 08774263A EP 08774263 A EP08774263 A EP 08774263A EP 2089370 A1 EP2089370 A1 EP 2089370A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
furfural
gas
thf
hydrogenation
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Withdrawn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
EP08774263A
Other languages
German (de)
English (en)
Inventor
Tobias Wabnitz
Daniel Breuninger
Jens Heimann
Rene Backes
Rolf Pinkos
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 EP08774263A priority Critical patent/EP2089370A1/fr
Publication of EP2089370A1 publication Critical patent/EP2089370A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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 a process for the one-stage preparation of 2-methyltetrahydrofuran from furfural on a catalyst.
  • 2-Methyltetrahydrofuran (hereinafter 2-Me-THF) is an organic solvent with high solubility.
  • 2-Me-THF is used as a replacement solvent for chemical syntheses of tetrahydrofuran (hereinafter THF), from which it advantageously differs by its lower, decreasing, with increasing temperature water solubility, as a fuel additive, since it is better miscible with common fuels based on hydrocarbons used as alcoholic additives, and as a comonomer for the preparation of polyethers having improved properties over the homopolymers.
  • THF tetrahydrofuran
  • 2-Me-THF is available from renewable raw materials. 2-Me-THF can be obtained from plant waste by digesting the hemicelluloses it contains into furfural and converting it into 2-Me-THF, thus contributing to sustainable development.
  • Kyosuke et al. J. Pharm. Soc. Jpn 66 (1946), 58 show that the direct conversion of furfural to 2-methyl-THF on Raney nickel catalysts at 260 0 C provides only small amounts of the desired product.
  • Kyosuke et al. instead, a two-step process via methylfuran as an isolated intermediate and the use of different catalysts for the two stages.
  • Cu-chromite is used after Adkins and in the second stage Raney-nickel.
  • a further disadvantage was the difficulty of isolating and purifying 2-Me-THF from the reaction mixture mixtures obtained, since the by-products THF, 2-pentanone and water as pure substances or in the form of their azeotropes have boiling points similar to those of 2-Me-THF.
  • the disclosed process has a number of disadvantages.
  • two catalysts and different reaction conditions are required for the individual stages of the reaction, which makes the technical implementation difficult and requires a spatial separation of the individual reactors.
  • the addition of hydrogen is required separately for each hydrogenation step, and the formation of carbon monoxide, which always occurs in small amounts from furfural under thermal stress, leads to deactivation of the nickel catalyst and to the formation of highly toxic, volatile Ni (CO). 4 .
  • CO highly toxic, volatile Ni
  • the present invention relates to a process for the one-stage hydrogenation of furfural with a hydrogen-containing gas in the presence of at least one noble metal of groups 8, 9 and / or 10 of the Periodic Table, in particular ruthenium, rhodium, iridium, gold, palladium and / or platinum, preferred Palladium and / or platinum, containing supported catalyst.
  • the catalyst used according to the invention has as active metal at least one noble metal of groups 8, 9 and / or 10 of the Periodic Table of the Elements, in particular ruthenium, rhodium, iridium, gold, preferably palladium and / or platinum, particularly preferably palladium, on a support.
  • the catalyst may additionally comprise metals of groups 4 and 7 to 12 of the Periodic Table of the Elements, as may optionally comprise elements of groups 1 and 2 of the Periodic Table of the Elements, especially sodium, potassium, calcium, magnesium. Preferably, it has no further active metals except palladium and platinum.
  • the application of the active metals may be carried out by soaking the carrier in aqueous metal salt solutions, such as e.g. aqueous palladium salt solutions, by spraying appropriate metal salt solutions onto the support or by other suitable methods such as impregnation.
  • the catalytically active metals can be applied to the carrier material by impregnation with solutions or suspensions of the salts or oxides of the relevant elements, drying and subsequent reduction of the metal compounds to the relevant metals or compounds of lower oxidation state by means of a reducing agent, preferably with hydrogen or complex hydrides become.
  • a reducing agent preferably with hydrogen or complex hydrides become.
  • Another possibility for applying the catalytically active metals to these supports is to impregnate the supports with solutions of easily decomposable salts, for example with nitrates, or thermally easily decomposable complex compounds, for example carbonyl or hydrido-complexes of the catalytically active metals and the soaked Carrier for the purpose of thermal decomposition of the adsorbed metal compounds to temperatures of 300 to 600 ° C to heat.
  • This thermal decomposition is preferably carried out under a protective gas atmosphere.
  • Suitable shielding gases are, for example, nitrogen, carbon dioxide, hydrogen or the noble gases.
  • the catalytically active metals can be deposited on the catalyst support by vapor deposition or by flame spraying. The content of these supported catalysts on the catalytically active metals is in principle not critical to the success of the process according to the invention. However, higher levels of catalytically active metals usually result in higher space-time conversions than lower levels.
  • Suitable metal salts of platinum and palladium are the nitrates, nitrosyl nitrates, halides, carbonates, carboxylates, acetylacetonates, chlorides, chloro complexes or amine complexes of the corresponding metals, the nitrates being preferred.
  • the metal salts or metal salt solutions can be applied simultaneously or in succession.
  • the metal salt solution coated or impregnated carriers are subsequently, preferably at temperatures between 100 0 C and 150 0 C, dried, and optionally at temperatures between 200 ° C and 600 0 C, preferably calcined between 350 ° C and 450 ° C , In the case of separate impregnation, the catalyst is dried after each impregnation step and optionally calcined as described above. The order in which the active components are soaked is freely selectable.
  • the coated and dried and optionally calcined supports are activated by treatment in a gas stream containing free hydrogen at temperatures between about 30 ° C and about 600 ° C, preferably between about 150 ° C and about 450 ° C.
  • the gas stream consists of 50 to 100 vol .-% H 2 and 0 to 50 vol .-% N 2 .
  • the metal salt solution or solutions are applied to the support (s) in an amount such that the total active metal content, based in each case on the total weight of the catalyst, is about 0.1 to about 30% by weight, preferably about 0.1 to about 10 wt%, more preferably about 0.25 to about 5 wt%, and especially about 0.5 to about 2.5 wt%.
  • Activated carbon for example in the form of the commercial product supersorbon coal from Donau Carbon GmbH, 60388 Frankfurt am Main, alumina, silica, silicon carbide, calcium oxide, titanium dioxide and / or zirconium dioxide or mixtures thereof, with activated carbon being preferably used.
  • the inventive method is characterized in that the reaction is effected in one stage and with only one catalyst.
  • the one-stage hydrogenation according to the invention can be carried out in one or more, in particular in two, three, four, five, six, seven, eight reactors.
  • the reaction mixture flows through the reactor or the reactors preferably from top to bottom.
  • the hydrogenation can be carried out in the gas phase or in the liquid phase; preference is given to working in the gas phase.
  • the process in the gas phase at a temperature of about 150 to 300 0 C is preferably carried out about 190 to 250 0 C.
  • the pressures used are generally at 1 to 15 bar absolute, preferably about 5 to 15 bar abs.
  • the pressure in this application is given as total pressure or absolute (abs.) Pressure.
  • the inventive method is generally at 150 to 250 ° C at pressures of 20 to 200 bar abs. carried out.
  • the process according to the invention can be carried out either continuously or batchwise, the continuous process being preferred.
  • the amount of furfururization hydrogenation is about 0.05 to about 3 kg per liter of catalyst per hour, more preferably about 0.1 to about 1 kg per liter of catalyst per hour.
  • hydrogenation gases it is possible to use any gases which contain free hydrogen and have no harmful amounts of catalyst poisons, such as CO, for example.
  • reformer exhaust gases can be used.
  • pure hydrogen is used as the hydrogenation gas.
  • inert carrier gases such as water vapor or nitrogen.
  • the hydrogenation according to the invention can be carried out in the absence or presence of a solvent or diluent, i. it is not necessary to carry out the hydrogenation in solution.
  • a solvent or diluent can be used.
  • any suitable solvent or diluent may be used. The selection is not critical, as long as the tion or diluent is able to form a homogeneous solution with the furfural to be hydrogenated.
  • Suitable solvents or diluents include the following: straight chain or cyclic ethers, such as tetrahydrofuran or dioxane, and aliphatic alcohols in which the alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 6 carbon atoms.
  • the amount of solvent or diluent used is not particularly limited and can be freely selected as needed, but those amounts are preferred which lead to a 10 to 70 wt .-% solution of the furfural intended for hydrogenation.
  • the hydrogenation reactor in the implementation of the hydrogenation in the liquid phase in the straight pass that is, without product recirculation, or in circulation (circulation), that is, a portion of the reactor leaving the hydrogenation mixture is recycled, operated.
  • the reaction products are completely condensed and separated after leaving the reactor.
  • the gaseous components, hydrogen and any additional carrier gas used, will partly recirculate back into the reactor (cycle gas mode).
  • the ratio of circulating gas to fresh gas volumes is at least 1: 1, preferably at least 5: 1, more preferably at least 10: 1.
  • Suitable reactors are fixed-bed reactors, such as, for example, tube-bundle reactors. In liquid mode, fluidized bed reactors can be used.
  • the reaction effluents of the hydrogenation according to the invention are condensed in a conventional manner, but preferably by cooling in a heat exchanger to 0 to 80 0 C. After condensation, a phase separation occurs.
  • the lower phase consists of more than 90% of water, while the upper phase in addition to the desired product 2-Me-THF only small amounts of well separated by an optionally subsequent purifying by-products.
  • 2-methyltetrahydrofuran (2-Me-THF) is obtained by the process according to the invention in very good yield and purity.
  • the phase separation can be carried out at ambient temperature.
  • the reaction effluents are preferably condensed at 60 ° C., since at this temperature the miscibility of 2-methyl-THF and water is particularly low.
  • Coal carrier added. The material was then dried for 40 hours at 100 0 C in a warming cabinet.
  • the catalyst thus prepared contained 5% by weight of palladium, based on the weight of the catalyst.
  • reaction products 2-Me-THF, 2-pentanone, 3-pentanone, 1-pentanol, THF, furan and methylfuran and the starting material furfural were analyzed by gas chromatography.
  • the mixtures were diluted with methanol or acetone (dilution 1:10 to 1: 100) or undiluted in the GC chromatograph (company HP, carrier gas: hydrogen) on a 30 m DB1 column (J + W) sprayed and at Oven temperatures of 60 0 C to 300 ° C (heating rate 8 Kelvin per minute to 220 0 C, then 20 Kelvin per minute to 300 0 C) with a flame ionization detector (temperature: 290 0 C) analyzed.
  • the purity was determined by integration of the signals of the chromatogram.
  • Example 1 In a continuous hydrogenation plant consisting of an evaporator, an oil-heated 3.81 jacketed tubular reactor and a separator and a cycle gas compressor, furfural was continuously hydrogenated on fixed bed catalysts in the gas phase.
  • the tube reactor was filled with 31 (equivalent to 1350 g) of a Pd catalyst (5% Pd / Supersorbon, 4 mm strands).
  • the tube reactor was flowed through from top to bottom.
  • the catalyst was activated by a method known to the expert without pressure with nitrogen / hydrogen mixtures at 200 0 C, so that the content of hydrogen in the mixed gas was slowly increased from 0 to 100%.
  • the system was pressed with hydrogen to 10 bar, fresh gas hydrogen adjusted to 150 NL / h, the evaporator on 290 0 C, the reactor tempered to 260 0 C and the cycle gas put into operation. In the evaporator 100 g / h single-stage furfural were promoted.
  • the recycle gas was adjusted to 1200 g / h, 95 NL / h of exhaust gas was sent for combustion.
  • the upper phase of the two-phase discharge had the following composition: furan 2.4% by weight, 2-methylfuran 2% by weight, THF 20% by weight, 2-MeTHF 49% by weight, 2-pentanone 9.2% by weight, 2-pentanol 0.5% by weight, 1-pentanol 0.9% by weight, the remainder to 100% unidentified by-products.
  • the by-products could be removed by prior art distillation to give the desired product 2-MeTHF in> 99% purity.
  • furfural was continuously hydrogenated on fixed bed catalysts in the gas phase.
  • the tube reactor was charged with 350 ml (equivalent to 173.3 g) of a Pd catalyst (5% Pd / supersorbone, 4 mm strands).
  • the tube reactor was flowed through from bottom to top.
  • the catalyst was activated by a method known to those skilled in the art at atmospheric pressure with nitrogen / hydrogen mixtures at 260 0 C, so that the content of hydrogen in the mixed gas was slowly increased from 0 to 100%. Subsequently, the system was pressed with hydrogen to 10 bar, fresh gas hydrogen adjusted to 150 NL / h, the evaporator to 240 0 C, the temperature of the reactor to 245 ° C.
  • 20 g / h of furfural were run from bottom to top over the catalyst (sumping method). It used 35 Nl / h Frischagas and 550NUh cycle gas. Under these conditions, furfural was fully implemented.
  • Tetraethylene glycol dimethyl ether was added to the reaction effluents in a manner known per se by metering 25 ml / h of tetraethylene glycol dimethyl ether into the gas stream between the tubular reactor and the precipitator. After releasing the stream into the unpressurized part, the liquid phase containing the reaction products was removed and collected in the separator.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Furan Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production de 2-méthyltétrahydrofurane par hydrogénation de furfural en une étape avec un gaz contenant de l'hydrogène, en présence d'un catalyseur supporté contenant au moins un métal noble des groupes 8, 9 et/ou 10 de la classification périodique des éléments.
EP08774263A 2007-07-02 2008-06-24 Procédé de production de 2-méthyltétrahydrofurane en une étape à partir de furfural sur un catalyseur Withdrawn EP2089370A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08774263A EP2089370A1 (fr) 2007-07-02 2008-06-24 Procédé de production de 2-méthyltétrahydrofurane en une étape à partir de furfural sur un catalyseur

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07111507 2007-07-02
EP08774263A EP2089370A1 (fr) 2007-07-02 2008-06-24 Procédé de production de 2-méthyltétrahydrofurane en une étape à partir de furfural sur un catalyseur
PCT/EP2008/058039 WO2009003882A1 (fr) 2007-07-02 2008-06-24 Procédé de production de 2-méthyltétrahydrofurane en une étape à partir de furfural sur un catalyseur

Publications (1)

Publication Number Publication Date
EP2089370A1 true EP2089370A1 (fr) 2009-08-19

Family

ID=39789581

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08774263A Withdrawn EP2089370A1 (fr) 2007-07-02 2008-06-24 Procédé de production de 2-méthyltétrahydrofurane en une étape à partir de furfural sur un catalyseur

Country Status (6)

Country Link
US (1) US20100099895A1 (fr)
EP (1) EP2089370A1 (fr)
JP (1) JP2010531839A (fr)
CN (1) CN101589033A (fr)
TW (1) TW200922930A (fr)
WO (1) WO2009003882A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102558106B (zh) * 2011-12-15 2014-12-17 北京金骄生物质化工有限公司 一种利用废弃生物质制备2-甲基四氢呋喃的方法
JP6168044B2 (ja) * 2012-03-09 2017-07-26 宇部興産株式会社 テトラヒドロフラン化合物の製造方法
CN102875500B (zh) * 2012-10-25 2015-03-25 凯莱英医药集团（天津）股份有限公司 2-甲基四氢呋喃的连续化生产方法
EP2951165B1 (fr) * 2013-01-30 2017-10-04 Council of Scientific and Industrial Research Procédé en une étape pour la conversion de furfural en tétrahydrofurane
US9650354B2 (en) 2013-06-25 2017-05-16 Council Of Scientific & Industrial Research Process for producing furan and its derivatives
CN106256810B (zh) * 2015-06-19 2019-01-25 中国石油化工股份有限公司 生物质原料生产芳烃的方法及该方法得到的组合物
CN106316765B (zh) * 2015-06-19 2019-04-12 中国石油化工股份有限公司 四氢呋喃类化合物芳构化的方法
EP3632958B1 (fr) * 2017-05-30 2024-04-24 Hodogaya Chemical Co., Ltd. Procédé de production d`un polyol de biopolyéther, polyol de biopolyéther, et résine biopolyuréthane
CN112717937A (zh) * 2020-12-29 2021-04-30 沈阳化工大学 糠醛气相加氢一步制2-mthf反应的催化剂制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS254357B1 (fr) * 1949-05-11 1950-12-16
US6479677B1 (en) * 2000-10-26 2002-11-12 Pure Energy Corporation Processes for the preparation of 2-methylfuran and 2-methyltetrahydrofuran
US7425657B1 (en) * 2007-06-06 2008-09-16 Battelle Memorial Institute Palladium catalyzed hydrogenation of bio-oils and organic compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009003882A1 *

Also Published As

Publication number Publication date
TW200922930A (en) 2009-06-01
CN101589033A (zh) 2009-11-25
JP2010531839A (ja) 2010-09-30
US20100099895A1 (en) 2010-04-22
WO2009003882A1 (fr) 2009-01-08

Similar Documents

Publication Publication Date Title
EP2051972B1 (fr) Procédé de fabrication en une étape de 2-méthyltétrahydrofurane à partir de furfural sur deux catalyseurs dans un garnissage structuré
WO2009003882A1 (fr) Procédé de production de 2-méthyltétrahydrofurane en une étape à partir de furfural sur un catalyseur
EP2707351B1 (fr) Procédé de préparation de pentane-1,2-diol
DE60304169T3 (de) Verfahren zur epoxidierung von olefinen
DE2519817A1 (de) Verfahren zur herstellung von butandiol-(1.4)
EP0815097B1 (fr) Procédé de fabrication de 1,4-butanediol et de tétrahydrofuranne à partir de furanne
DE2553761A1 (de) Verfahren zur katalytischen herstellung von gamma-butyrolacton
DE2723611B2 (de) Verfahren zur Herstellung von Äthylalkohol
DE2715666A1 (de) Verfahren zur herstellung von aethylenglykol
EP0796839B1 (fr) Procédé pour la préparation d'un mélange d'amino-méthyl-cyclohexanes et de diamino-méthyl-cyclohexanes
EP2595743A1 (fr) Catalyseur d'isomérisation
EP0711267B1 (fr) Procede de fabrication de 1,4-butanediol
EP0767769B1 (fr) Procede de preparation de 1,4-butanediol
DE68901742T2 (de) Verfahren zur herstellung von gamma-butyrolacton.
EP1501816A1 (fr) Procede de production de gamma-butyrolactone
WO2007135072A1 (fr) Procédé pour éviter des dépôts d'acide fumarique lors de la fabrication d'anhydride d'acide maléique
DE19718116A1 (de) Verfahren zur Herstellung von d,l-Menthol
EP1999102B1 (fr) Procede de fabrication de n,n-dimethylaminoethoxyethanol
DD203316A5 (de) Verfahren zur selektiven spaltung von polyalkylenglykolen
EP1904430B1 (fr) Procede d'hydrogenation de flux de matieres contenant des aldehydes
EP2356098A1 (fr) Procédé de production de tétrahydrofurane
DE102011006685A1 (de) Verfahren zur Herstellung von 2-Methyltetrahydrofuran aus 2-Methylfuran in der Flüssigphase
DE19941569A1 (de) Verfahren zur Herstellung von gamma-Butyrolacton
EP1768760B1 (fr) Procede pour separer par stripage de l'anhydride d'acide maleique de melanges en contenant
DE4304756C1 (de) Verfahren zur Darstellung von Salzen, chiraler, alpha-sauerstoffunktionalisierter Carbonsäuren

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090617

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20130103