EP2158192A1 - Procédé de fabrication de -caprolactone - Google Patents

Procédé de fabrication de -caprolactone

Info

Publication number
EP2158192A1
EP2158192A1 EP08760684A EP08760684A EP2158192A1 EP 2158192 A1 EP2158192 A1 EP 2158192A1 EP 08760684 A EP08760684 A EP 08760684A EP 08760684 A EP08760684 A EP 08760684A EP 2158192 A1 EP2158192 A1 EP 2158192A1
Authority
EP
European Patent Office
Prior art keywords
caprolactone
acid
preparation
ester
adipic
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Withdrawn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
EP08760684A
Other languages
German (de)
English (en)
Inventor
Rolf Pinkos
Gerd Tebben
Christophe Bauduin
Daniel Breuninger
Maria Guixa Guardia
Tilman Sirch
Thomas Krug
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 EP08760684A priority Critical patent/EP2158192A1/fr
Publication of EP2158192A1 publication Critical patent/EP2158192A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
    • C07D313/02—Seven-membered rings
    • C07D313/04—Seven-membered rings not condensed with other rings

Definitions

  • the invention relates to a preparation of ⁇ -caprolactone in a purity greater than 99%, characterized in that 6-hydroxycaproic ester containing 0.5 to 40 wt .-% adipic ester cyclized in the gas phase at 150 to 45O 0 C in the presence of oxidic catalysts and from the cyclization product is obtained by distillation ⁇ -caprolactone.
  • ⁇ -caprolactone or the polycaprolactones prepared therefrom by polyaddition serve for the production of polyurethanes.
  • DCL dicarboxylic acid solution
  • DCL dicarboxylic acid solution
  • adipic acid between 10 and 40% 6-hydroxycaproic acid
  • glutaric acid between 1 and 10% 5-hydroxyvaleric acid, between see 1 and 5%
  • 2-cyclohexanediols between 1 and 5%
  • 4-cyclohexanediols between 2 and 10% formic acid and a variety of other mono- and dicarboxylic acids, esters, oxo and oxa compounds, their individual contents generally not exceed 5%.
  • Examples which may be mentioned are acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oxalic acid, malonic acid, succinic acid, 4-hydroxybutyric acid and ⁇ -butyrolactone.
  • caprolactone from DCL is e.g. DE 1 618 143 has already been described.
  • This dehydrated DCL is thermally reacted with phosphoric acid and fractionated a mixture of dicarboxylic acids, caprolactone and a variety of other components.
  • the swamp falls z.T. solid and sparingly soluble.
  • the caprolactone has only a 98% purity even after further work-up by distillation.
  • DE 38 23 213 describes reacting 6-hydroxycaproic acid ester in the gas phase in the presence of oxidic catalysts and an inert carrier gas to form caprolactone.
  • WO 97/31883 describes a process for the preparation of 1,6-hexanediol and ⁇ -caprolactone from an adipic acid, 6-hydroxycaproic acid and small amounts of carboxylic acid mixture containing 1,4-cyclohexanediols, which is a by-product of the oxidation of cyclohexane Cyclohexanone / cyclohexanol with oxygen or oxygen-containing gases and by water extraction of the reaction mixture is obtained, which is obtained with a low molecular weight alcohol to the esterified corresponding carboxylic acid ester, the resulting esterification mixture with a first distillation stage of excess alcohol and low boilers freed from the bottom product in a second distillation stage into a 1, 4-cyclohexanediols substantially free ester fraction and at least the larger part of the cyclohexanediols-containing fraction performs, by a third distillation stage, a substantially 6-hydroxycaproic acid-
  • WO 97/31883 recommends the preparation of caprolactone in the liquid phase. According to Comparative Example 1 contained in this application, however, a significant decrease in the yield of caprolactone is observed for the cyclization in the liquid phase in the presence of 5 wt .-% of adipic acid ester, based on the 6-hydroxycaproic.
  • adipic acid diesters and 6-hydroxycaproic acid esters can form dimers, oligomers or polymers.
  • adipic acid dimethyl ester and 6-hydroxycaproic acid methyl ester may, for.
  • the dimeric ester CH3 ⁇ OC- (CH2) 4-COO- (CH2) 5-COOCH3 form, under the Incorporation of additional 6-hydroxycaproic can form oligomers or polymers.
  • dimers, oligomers or polymers still represent compounds which can be utilized by hydrogenation for 1,6-hexanediol, in the case of reactions in the gas phase, the risk of deposits of these high-boiling components on the cyclization catalyst is high, so that with a very shortened Catalyst life should be expected.
  • This object has been achieved with a process for the preparation of ⁇ -caprolactone in a purity of more than 99%, characterized in that 6-hydroxycaproic acid ester containing 0.5 to 40 wt .-%, preferably 0.6 to 25 wt .-%, especially preferably 0.7 to 15 wt .-%, adipic acid cyclized in the gas phase at 150 to 450 ° C in the presence of oxidic catalysts and recovered from the cyclization by distillation ⁇ -caprolactone.
  • Alcohols having 1 to 12 carbon atoms, cycloalkanols having 5 to 7 carbon atoms, aralkanols having 7 to 8 carbon atoms or phenols having 6 to 6 carbon atoms are generally used as esterifying alcohols of the 6-hydroxycaproic acid ester and the adipic acid ester consideration.
  • diols such as butanediol or pentanediol come into consideration in principle.
  • the ester groups in the 6-hydroxycaproic acid esters and the adipic diesters may be the same or different, but are preferably the same.
  • the particularly preferred educt is methyl 6-hydroxycaproate containing from 0.5 to 40% by weight of dimethyl adipate.
  • the preparation of the starting material of the process according to the invention, of the 6-hydroxycaproic acid ester containing from 0.5 to 40% by weight of adipic acid diester, can also be carried out according to DE-A 197 50 532, to which reference is expressly made and should be considered incorporated herein, take place.
  • 6-hydroxycaproic acid ester containing 0.5 to 40% by weight of adipic acid diesters is obtained by catalytic hydrogenation of adipic diesters or feed streams containing these esters as essential constituents, distillation of the hydrogenation effluent and separation of the hexanediol.
  • the hydrogenation is preferably carried out in the liquid phase.
  • hydrogenation catalysts heterogeneous but also homogeneous catalysts suitable for the hydrogenation of carbonyl groups are generally used in this process. They can be both fixed and mobile, e.g. in a fluidized bed reactor. Examples of this are e.g. in Houben-Weyl, Methods of Organic Chemistry, Volume IV / 1c, pp 16 to 26 described.
  • hydrogenation catalysts preference is given to those which contain one or more elements of group Ib, VIb, VIIb and VIIIb, and also IIIa, IVa and Va of the Periodic Table of the Elements, in particular copper, chromium, rhenium, cobalt, rhodium, nickel, palladium, Iron, platinum, indium, tin and / or antimony. Particular preference is given to catalysts which contain copper, cobalt and / or rhenium.
  • the production of the 6-hydroxycaproic acid ester containing 0.5 to 40 wt .-% adipic according to WO 97/31 883 such that a adipic acid, 6-hydroxycaproic acid and small amounts of 1, 4-cyclohexanediols containing carboxylic acid mixture, as by-product of the oxidation of Cyclohexane to cyclohexanone / cyclohexanol with oxygen or oxygen-containing gases by water extraction of the reaction mixture is obtainable, is esterified with a low molecular weight alcohol to the corresponding carboxylic acid esters, and the resulting esterification mixture is separated in at least one distillation stage.
  • methyl 6-hydroxycaproate containing from 0.5 to 40% by weight adipic acid dimethyl ester is obtained in which
  • the resulting esterification mixture is freed of excess methanol and low-boiling components in a first distillation stage
  • the 0.5 to 40% by weight of dimethyl adipate containing 6-Hydroxy- capronsäuremethylester stream is separated from the ester fraction in a third distillation stage.
  • FIG. 1 the process for the preparation of ⁇ -caprolactone according to WO 97/31883 is explained according to FIG. 1, in which the individual process steps are subdivided into further stages, wherein the stages 2, 3, 4 and 12, 13 and 14 for the Processes for the production of ⁇ -caprolactone are essential and stages 3 and 4 can also be summarized.
  • the dicarboxylic acid solution (DCL) is generally an aqueous solution with a water content of 20 to 80%. Since an esterification reaction is an equilibrium reaction in which water is formed, it is expedient to remove water present in particular during esterification with, for example, methanol before the reaction, especially if water can not be removed during the esterification reaction, for example not azeotropically.
  • the dehydration in stage 1 can be carried out, for example, with a membrane system, or preferably by a distillation apparatus in which at 10 to 250 ° C, preferably 20 to 200 0 C, especially 30 to 200 ° C and a pressure of 1 to 1500 mbar, preferred 5 to 1 100 mbar, particularly preferably 20 to 1000 mbar water overhead and higher monocarboxylic acids, dicarboxylic acids and 1, 4-cyclohexanediols are separated off via bottom.
  • the bottom temperature is preferably chosen so that the bottom product can be withdrawn liquid.
  • the water content in the bottom of the column can be from 0.01 to 10% by weight, preferably from 0.01 to 5% by weight, particularly preferably from 0.01 to 1% by weight.
  • the separation of the water can be carried out in such a way that the water is predominantly acid-free or the lower monocarboxylic acids contained in the DCL, essentially formic acid, can be distilled off for the most part with the water, so that they do not undergo esterification in the esterification Bind esterification alcohol.
  • the carboxylic acid stream from stage 1 is mixed with alcohol ROH having 1 to 10 carbon atoms.
  • alcohol ROH having 1 to 10 carbon atoms.
  • methanol, ethanol, propanol or isopropanol or mixtures of the alcohols but preferably methanol on the one hand or C 4 and higher alcohols, in particular having 4 to 8 carbon atoms and preferably n- or i-butanol or n-pentanol or i Pentanol, on the other hand.
  • the mixing ratio of alcohol to carboxylic acid stream may be from 0.1 to 30, preferably from 0.2 to 20, particularly preferably from 0.5 to 10. This mixture passes as a melt or solution in the reactor of stage 2, in which the carboxylic acids are esterified with the alcohol.
  • the esterification reaction can be at 50 to 400 0 C, preferably 70 to 300 ° C, particularly preferably 90 to 200 0 C.
  • An external pressure can be applied, but the esterification is preferably carried out under autogenous pressure of the reaction system.
  • As Verest fürsapparat can be a stirred tank or flow tube or it can be used in each case more.
  • the residence time necessary for the esterification is between 0.3 and 10 hours, preferably 0.5 to 5 hours.
  • the esterification reaction can proceed without the addition of a catalyst, but a catalyst is preferably added to increase the reaction rate. It may be a homogeneous dissolved or a solid catalyst.
  • homogeneous catalysts are sulfuric acid, phosphoric acid, hydrochloric acid, sulfonic acids such as p-toluenesulfonic acid, heteropolyacids such as tungstophosphoric acid or Lewis acids such as aluminum, vanadium, titanium, boron compounds. Preference is given to mineral acids, in particular sulfuric acid.
  • the weight ratio of homogeneous catalyst to carboxylic acid melt is usually 0.0001 to 0.5, preferably 0.001 to 0.3.
  • solid catalysts are acidic or super acidic materials, e.g. acidic and super acidic metal oxides such as SiO 2, Al 2 O 3, Sn 2 O, ZrO 2, phyllosilicates or zeolites, all of which may be doped with mineral acid residues such as sulfate or phosphate for acid amplification, or organic ion exchangers having sulfonic acid or carboxylic acid groups.
  • the solid catalysts can be arranged as a fixed bed or used as a suspension.
  • the water formed in the reaction is conveniently used continuously, e.g. through a membrane or removed by distillation.
  • the completeness of the conversion of the free carboxyl groups present in the carboxylic acid melt is determined by the acid number (mg KOH / g) measured after the reaction. It is less the optionally added acid as a catalyst from 0.01 to 50, preferably 0.1 to 10. Not all present in the system carboxyl groups must be present as esters of the alcohol used, but a part may be in the form of dimeric or oligomeric esters with the OH end of Hydroxycapron- acid present.
  • the esterification mixture is fed in stage 3, a membrane system or preferably a distillation column. If a dissolved acid was used as a catalyst for the esterification reaction, the esterification mixture is expediently neutralized with a base, wherein 1 to 1, 5 base equivalents are added per acid equivalent of the catalyst.
  • bases are usually alkali or alkaline earth metal oxides, carbonates, hydroxides or -Alkoholate, or amines in substance or in the Esterification alcohol used dissolved. However, it can also be neutralized with basic ion exchangers.
  • the feed to the column is preferably carried out between the top and the bottom stream.
  • This stream can either be burned or preferably further processed in stage 11.
  • the bottom product obtained is an ester mixture which consists predominantly of the esters of the alcohol ROH used with dicarboxylic acids such as adipic acid and glutaric acid, hydroxycarboxylic acids such as 6-hydroxycaproic acid and 5-hydroxyvaleric acid, and of ON monomers and free or esterified 1, 4-cyclohexanediols consists. It may be useful to allow a residual content of water and / or alcohol ROH up to 4% by weight in the ester mixture.
  • the bottom temperatures are 70 to 25O 0 C, preferably 80 to 220 0 C, particularly preferably 100 to 190 ° C.
  • stage 4 This is a distillation column in which the feed takes place between the low-boiling components and the high-boiling components.
  • the column is operated at temperatures of 10 to 300 ° C, preferably 20-270 0 C, particularly preferably 30 to 250 ° C and pressures from 1 to 1000 mbar, preferably from 5 to 500 mbar, particularly preferably operated from 10 to 200 mbar.
  • the top fraction consists predominantly of residual water and residual alcohol ROH, esters of the alcohol ROH with monocarboxylic acids, predominantly C3 to C6 monocarboxylic acid esters with hydroxycarboxylic acids, such as 6-hydroxycaproic acid, 5-hydroxyvaleric acid and above all the diesters with dicarboxylic acids, such as adipic acid, glutaric acid and succinic acid, cyclohexanediols, caprolactone and valerolacetone.
  • esters of the alcohol ROH with monocarboxylic acids predominantly C3 to C6 monocarboxylic acid esters with hydroxycarboxylic acids, such as 6-hydroxycaproic acid, 5-hydroxyvaleric acid and above all the diesters with dicarboxylic acids, such as adipic acid, glutaric acid and succinic acid, cyclohexanediols, caprolactone and valerolacetone.
  • the said components can be separated together overhead or in a further preferred embodiment in the column of the stage 4 in a top stream containing predominantly residual water and residual alcohol and the above-mentioned components having 3 to 5 C-atoms and a side stream, which predominantly the above mentioned constituents of the C ⁇ ester, are separated.
  • the current containing the esters of the C ⁇ acids can then be fed into the stage 12 only in part or as a total stream, depending on how much caprolactone is to be prepared, according to the process preferred according to WO 97/31883 .
  • the high-boiling components of the stream from stage 4, predominantly consisting of dimeric or oligomeric esters, cyclohexanediols and unspecified partly polymeric constituents of the DCL, are separated off via the stripping section of the column of stage 4, can either be incinerated or in a preferred embodiment for the so-called transesterification in the described in WO 97/31883 stage 8 arrive.
  • Levels 3 and 4 can be combined, especially if only smaller quantities are processed. For this purpose, for example, in a batchwise fractional distillation, the C ⁇ ester stream can be obtained.
  • the stream of stage 4 containing mainly esters of C ⁇ acids is used.
  • this stream is separated in stage 12, a distillation column, into a stream containing predominantly adipic diester overhead and a stream containing predominantly 6-hydroxycaproic ester over the bottom.
  • the column is operated at pressures of 1 to 500 mbar, preferably 5 to 350 mbar, more preferably 10 to 200 mbar and bottom temperatures of 80 to 250 ° C, preferably 100 to 200 ° C, particularly preferably 1 10 to 180 ° C.
  • the head temperatures adjust accordingly.
  • adipic acid diester it may be advantageous to separate in step 12 together with the adipic acid diester also some hydroxycaproic acid ester. If the adipic acid diester is to be hydrogenated to 1,6-hexanediol, the contents of the adipic acid ester of hydroxycaproic acid ester are advantageously between 0.2 and 7% by weight. Depending on the alcohol component of the esters, this proportion of hydroxycaproic acid ester is separated together with the adipic acid diester via the top (for example methyl ester) or via bottom (for example butyl ester).
  • adipic acid diester containing 6-hydroxycaproic acid ester is converted in the gas phase to alcohol and caprolactone.
  • These mixtures of 6-hydroxycaproic acid esters and adipic diesters may also contain other components which may account for up to 20% by weight, but are preferably below 10%, more preferably below 5%. These components consist, for example, of 1,5-pentanediol, cyclohexanediols, unsaturated adipic diesters, pimelic diesters, caprolactone, 5-hydroxycaproic acid esters and also diesters based on, in particular, 6-hydroxycaproic esters.
  • the mixture of 6-hydroxycaproic acid ester and 0.5 to 40% by weight of adipic acid diester is passed in vapor form together with a carrier gas via oxide catalysts arranged in a fixed manner or moving in an upwards and downwards motion.
  • the evaporation takes place at 180 to 300 ° C. It may be advantageous additionally to coevaporate a solvent which is inert under the reaction conditions.
  • solvents are, for example, ethers such as tetrahydrofuran or dioxane but also alcohols in question. It is advantageous to use 10 to 95% strength by weight solutions of 6-hydroxycaproic acid esters and adipic diesters in such solvents as starting material for the process according to the invention.
  • Inert carrier gases are for example nitrogen, carbon dioxide, hydrogen or noble gases such as argon.
  • nitrogen or hydrogen is used as carrier gas.
  • 5 to 100 moles of carrier gas are used per mole of vaporous 6-hydroxycaproic acid ester, preferably 8 to 50 moles, more preferably 10 to 30 moles.
  • the carrier gas is preferably circulated by means of a blower or a compressor, a partial flow be discharged and can be supplemented accordingly by fresh gas.
  • Suitable catalysts are acidic or basic catalysts which may be homogeneously dissolved or heterogeneous. Examples are alkali metal and alkaline earth metal hydroxides, oxides, carbonates, alkoxylates or carboxylates, acids such as sulfuric or phosphoric acid, organic acids such as sulfonic acids or mono- or dicarboxylic acids, or salts of the abovementioned acids, Lewis acids, preferably from III , and IV. Main group or the I. to VIII. Subgroup of the Periodic Table of the Elements or oxides of rare earth metals or mixtures thereof.
  • Examples are magnesium oxide, zinc oxide, boron trioxide, titanium dioxide, silicon dioxide, tin dioxide, bismuth oxide, copper oxide, lanthanum oxide, zirconium dioxide, vanadium oxides, chromium oxides, tungsten oxides, iron oxides, cerium oxide, aluminum oxide, hafnium oxide, lead oxide, antimony oxide, barium oxide, calcium oxide, sodium hydroxide, potassium hydroxide, neodymium oxide , It is also possible to use mixtures of oxides, which may be mixtures of the individual components or else mixed oxides, as described, for example, in US Pat. in zeolites, clays or heteropoly acids.
  • the catalysts may have been pretreated, for example, with mineral acids to enhance acid strength, e.g. with sulfuric acid, phosphoric acid or hydrochloric acid.
  • silica-containing catalysts such as zeolites, clays, SiIi- ciumdioxid z.
  • Silica or catalysts containing silica components have proven particularly suitable.
  • the heterogeneous, preferably oxidic, catalysts can be fixedly arranged in the reaction zone and the vaporous mixture of esters and carrier gases passed over it. However, it is also possible for the catalyst to be in an up-and-down movement (fluidized bed).
  • a catalyst loading of from 0.01 to 40, preferably from 0.05 to 20, in particular from 0.07 to 10 g of starting material (mixture of 6-hydroxycaproic acid ester and from 0.5 to 40% by weight of adipic acid diester) per g of catalyst is advantageously maintained and hour.
  • the reaction to caprolactone is carried out at a temperature of 150 to 450 0 C, preferably at 200 to 400 0 C, in particular 230 to 300 0 C.
  • the reaction is carried out under atmospheric pressure.
  • slightly diminished pressure, z. B. up to 500 mbar or slightly elevated pressure, z. B. apply up to 5 bar. If a fixed catalyst is used, it has proven to be particularly favorable that a higher pressure is set before the catalyst than after the catalyst, so that possibly forming high-boiling components can not or less deposit on the catalyst NEN.
  • the reaction is condensed with suitable cooling devices. If a fixed catalyst is used, the reactor, for example a shaft or a tube bundle reactor, can be operated in an upward or downward flow manner. The reaction takes place in at least one reactor.
  • the reaction of the cyclization contains as the main component of the target product caprolactone, also released during the cyclization of lower alcohol, adipic diester and optionally unreacted 6-hydroxycaproic, optionally oligoester and optionally solvent.
  • This mixture is separated by single or multi-stage distillation in stage 14 under reduced pressure so that caprolactone is recovered in a purity of at least 99%.
  • the purity is preferably more than 99.5%, particularly preferably more than 99.8%.
  • the one-stage or multistage distillations for purifying the caprolactone are particularly preferred at bottom temperatures of 70 to 250 ° C., preferably 90 to 230 ° C., more preferably 100 to 210 ° C. and pressures of 1 to 500 mbar, preferably 5 to 200 mbar 10 to 150 mbar.
  • esterification alcohol which may still be present, as well as other C 1 to C 6 low boilers are separated off at the top, pure caprolactone is passed off via side stream and adipic acid diester and over the bottom. if not unreacted hydroxycaproic acid ester, which is recycled.
  • the adipic acid diester if appropriate together with dimeric or oligomeric esters, can be introduced into a hydrogenation reactor and converted into 1,6-hexanediol according to WO 97/31883 or DE-A-19750532.
  • oligomeric C ⁇ esters are formed, these can also be introduced into the hydrogenation to 1,6-hexanediol according to EP-B 1 030 827.
  • the reaction effluent was condensed out by means of a water cooler and analyzed.
  • the 6-hydroxycaproic acid methyl ester conversion was 98%
  • the caprolactone selectivity based on methyl 6-hydroxycaproate was 93%
  • the yield was 91%.
  • the adipic acid dimethyl ester conversion was only about 10%, which led predominantly to cyclopentanone.
  • the collected reaction effluents were batch distilled in a 1 m packed column. At 10 mbar, caprolactone was obtained in a purity of up to 99.8%.
  • Example 1 was repeated, with the difference that the catalyst used was silica (STR 5 mm, Davicat SMR # CCS-04-051, # 03GMD363 from Grace & Comp.) And the dimethyl adipate content was 10% by weight. It was achieved a 6-hydroxycaproic acid methyl ester conversion of 56%, the caprolactone selectivity was 98%, the yield 55%. Adipic acid dimethyl ester conversion was below 1%.
  • Example 2 from WO 97/31 883 was repeated with a hydroxycaproic acid-containing stream containing, based on the total amount not 0.1 but about 5% adipic acid dimethyl ester in the feed to remplissigphasencyclmaschine.
  • the amount of caprolactone-containing distillate was not 1225 g, corresponding to a caprolactone yield of> 90%, but only 900 g, corresponding to a caprolactone yield of ca. 75%.
  • the sump product quantity was correspondingly larger.
  • Comparative Example 1 was repeated, with the difference that 10% adipic acid dimethylester were in the feed.
  • the caprolactone yield was just under 10%, the remainder was oligomeric bottom product.

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

Abstract

L'invention concerne un procédé de fabrication de e-caprolactone ayant une pureté de plus de 99 %, consistant à cycliser un ester d'acide 6-hydroxycapronique contenant 0,5 à 40 % en poids de diester d'acide adipinique dans la phase gazeuse, à une température de 150 à 450 °C, en présence de catalyseurs oxydiques, et à produire du e-caprolactone à partir du produit de cyclisation par distillation.
EP08760684A 2007-06-14 2008-06-06 Procédé de fabrication de -caprolactone Withdrawn EP2158192A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08760684A EP2158192A1 (fr) 2007-06-14 2008-06-06 Procédé de fabrication de -caprolactone

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07110270 2007-06-14
PCT/EP2008/057114 WO2008152001A1 (fr) 2007-06-14 2008-06-06 PROCÉDÉ DE FABRICATION DE ε-CAPROLACTONE
EP08760684A EP2158192A1 (fr) 2007-06-14 2008-06-06 Procédé de fabrication de -caprolactone

Publications (1)

Publication Number Publication Date
EP2158192A1 true EP2158192A1 (fr) 2010-03-03

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US (1) US20100168445A1 (fr)
EP (1) EP2158192A1 (fr)
JP (1) JP2010529159A (fr)
KR (1) KR20100020036A (fr)
CN (1) CN101679342A (fr)
CA (1) CA2690867A1 (fr)
WO (1) WO2008152001A1 (fr)

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Publication number Priority date Publication date Assignee Title
US8466299B2 (en) * 2008-12-05 2013-06-18 Basf Se Process for preparing delta-valerolactone in the gas phase
BRPI0922311A2 (pt) 2008-12-09 2016-01-05 Basf Se processos para a purificação de polimetilol bruto, e para a produção de polímeros ou redes.
WO2010066674A2 (fr) 2008-12-09 2010-06-17 Basf Se Procédé de production de polyméthylols
SG172807A1 (en) 2009-01-12 2011-08-29 Basf Se Method for producing polymethylols
ES2421150T3 (es) * 2009-04-07 2013-08-29 Basf Se Método para la preparación de 1,6-hexanodiol y caprolactona
US8629306B2 (en) * 2009-04-07 2014-01-14 Basf Se Method for producing 1,6-hexanediol
CN103080098B (zh) * 2010-09-08 2014-11-05 巴斯夫欧洲公司 制备ε-己内酯和1,6-己二醇的方法
CN103570667B (zh) * 2012-08-09 2015-01-21 中国石油化工股份有限公司 一种连续制备ε一己内酯的方法
CN103588747B (zh) * 2012-08-17 2015-05-20 中国石油化工股份有限公司 一种ε-己内酯的生产方法及其设备
CN111995611A (zh) * 2020-08-18 2020-11-27 青岛科技大学 一种己内酯的合成工艺
CN111995613A (zh) * 2020-08-26 2020-11-27 青岛科技大学 一种制备己内酯的方法
CN112266372A (zh) * 2020-11-10 2021-01-26 安徽华业香料合肥有限公司 一种δ-己内酯合成香料的生产装置和方法

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DE3622012A1 (de) * 1986-07-01 1988-01-07 Basf Ag Verfahren zur herstellung zyklischer ketone
DE3823213A1 (de) * 1988-07-08 1990-01-11 Basf Ag Verfahren zur herstellung von caprolacton
MY118128A (en) * 1996-03-01 2004-09-30 Basf Ag The preparation of 1, 6-hexanediol and caprolactone
DE19750532A1 (de) * 1997-11-14 1999-05-20 Basf Ag Verfahren zur Herstellung von 1,6-Hexandiol und 6-Hydroxycapronsäure bzw. deren Estern

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US20100168445A1 (en) 2010-07-01
CA2690867A1 (fr) 2008-12-18
CN101679342A (zh) 2010-03-24
WO2008152001A1 (fr) 2008-12-18
JP2010529159A (ja) 2010-08-26
KR20100020036A (ko) 2010-02-19

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