WO1994007835A1 - Procede d'isomerisation de lactones en acides pentenoiques par catalyse acide ou basique - Google Patents
Procede d'isomerisation de lactones en acides pentenoiques par catalyse acide ou basique Download PDFInfo
- Publication number
- WO1994007835A1 WO1994007835A1 PCT/FR1993/000928 FR9300928W WO9407835A1 WO 1994007835 A1 WO1994007835 A1 WO 1994007835A1 FR 9300928 W FR9300928 W FR 9300928W WO 9407835 A1 WO9407835 A1 WO 9407835A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zsm
- basic
- acid
- metal
- phosphates
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
Definitions
- the present invention relates to a process for the isomerization of lactones, more particularly of the various valerolactones and their isomers, into pentenoic acids.
- patent EP-A-0 395 038 describes this carbonylation, at a temperature greater than or equal to 190 ° C. and in the presence of rhodium / H I or rhodium / H Br.
- the present invention aims precisely to solve this problem by allowing the isomerization of ia gamma-valerolactone or its isomers into pentenoic acids, which can again be hydroxycarbonylated to adipic acid. It consists of a process for isomerizing pentenoic acid from at least one lactone having 5 carbon atoms, characterized in that said lactone is brought into contact in vapor phase with a solid acid or basic catalyst.
- solid acid catalysts means solid compounds, most often metal oxides or metal salts, which cause the dehydration of methylbutynol to methylbutenyne (“methylbutynol” test) according to the reaction:
- solid basic catalysts will mean solid compounds, most often metal oxides or metal salts, which cause the downgrading of methylbutynol to acetylene and acetone ("methylbutynol" test) according to the reaction:
- lactones which can be used in the process of the invention are more particularly gamma-valerolactone (or 4-methyl butyrolactone), delta-valerolactone, 2-methyl butyrolactone, 3-ethyl propiolactone, ethyl -2 propiolactone, 2,3-dimethyl propiolactone.
- gamma-valerolactone is the most interesting because of its formation in the hydroxycarbonylation processes of pentene-3 oic acid to adipic acid.
- acid solid catalysts there may be mentioned acid molecular sieves, acid clays, bridged clays (or pillar clays), mass oxides and acid phosphates.
- the acid molecular sieves are more particularly the zeolites of pentasil structure, such as for example ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-48, of ferrierite structure, of mordenite structure and zeolites with a faujasite structure, such as, for example, zeolite X or zeolite Y.
- the zeolites of pentasil or mordenite structure are more particularly the zeolites of type ZSM-5, ZSM-11, ZSM-22, ZSM-23 and ZS -48 and mordenite having the general formula (I) expressed in terms of oxide ratios :
- . M represents an element chosen from hydrogen, NH 4 and the metals mono-, di-, tri-, and tetravalents,.
- X represents a trivalent element chosen from Al, Ga, Fe and B,.
- n represents a number from 1 to 4,.
- m represents a number equal to or greater than 10,.
- p represents a number from 0 to 40.
- Zeolites of the faujasite type of structure are more particularly those having the general formula (II) expressed in terms of oxide ratios:
- M represents an element chosen from hydrogen
- Z represents a trivalent element chosen from Al, Ga, Fe and B,.
- n represents a number from 1 to 4,
- . d represents a number equal to or greater than 2,.
- x represents a number from 5 to 100.
- the acid zeolites used in the context of the invention are in particular those in the formula of which the oxide associated with the silica is that of a trivalent metal.
- Zeolites are generally preferred in formula (I) or (II) in which M is chosen from hydrogen, NH 4 , alkali metals such as, for example Na, K, Li, Rb or Cs, alkaline earth metals teis as for example Be, Mg, Ca, Sr or Ba, rare earth metals such as for example La or Ce, transition metals such as for example Fe.
- smectites such as for example montmorillonites, beidellites, nontronites, hectorites, stevensites and saponites.
- Bridged clays which can be used as catalysts in the present process, are clays between the sheets of which bridges or pillars have been introduced which maintain a basic spacing. The basal spacing is the sum of the thickness of a sheet of clay and the interfoiial spacing. The preparation of these bridged clays has been described in particular in patent FR-A-2,563,446 as well as in patent FR-A-2,618,143.
- the bridging of clays can be carried out in particular using hydroxides of aluminum, vanadium, molybdenum, zirconium, iron, nobium, tantalum, chromium, lanthanum, cerium, titanium, gallium or mixed hydroxides of several of these metals.
- bridged clays can be modified, in particular by the action of a dihalogen, an ammonium halide or an acid such as sulfuric acid or hydrohalic acids.
- the halogen thus optionally introduced is preferably chlorine or fluorine.
- clays particularly beidellites, bridged with aluminum hydroxide are used in the process of the invention.
- the mass oxides are metal oxides, mixtures of metal oxides or modified metal oxides, in particular by the action of a dihalogen, an ammonium halide or an acid such as sulfuric acid or hydrohalic acids.
- the halogen thus optionally introduced is preferably chlorine or fluorine.
- SiO 2 / ALO 3 SiO 2 / Ga 2 O 3 , SiO 2 / Fe 2 O 3 , SiO 2 / B 2 O 3 , halogenated aluminas such as in particular the chlorinated aluminas and fluorinated aluminas, sulfated zirconia, niobium oxide or tungsten oxide.
- the acid phosphates which can be used in the process of the invention are in particular by way of examples the boron phosphates, alone or as a mixture with alumina or with silica, corresponding to different molar ratios H. j BO .JHgPO. introduced during synthesis, lanthanum phosphate, aluminum phosphates corresponding to different molar ratios introduced during the synthesis, phosphorus pentoxide / silica mixtures (usually called UOP catalysts), aluminophosphates with zeolitic structure (AIPO) and silico-aluminophosphates with zeolitic structure (SAPO).
- the basic solid catalysts which can be used in the process of the invention are in particular basic metal phosphates. Basic metal oxides, metal carbonates and basic molecular sieves.
- the basic metal phosphates are in particular the phosphates, the hydrogenophosphates and the dihydrogenophosphates of general formula (III):
- - A represents a metal atom, a group of metal atoms or in part a hydrogen atom
- - y represents a whole or fractional number from 3/4 to 3 depending on the valence of the elements A;
- Imp corresponds to a basic impregnation compound consisting of metal chosen from alkaline earth metals, alkali metals and their mixtures associated with a counter anion to ensure electrical neutrality;
- the coefficient z represents the weight ratio between the impregnating agent and the impregnating agent (PO. A) and it is between 0% and 20% and preferably between 2% and 10%.
- the basic phosphates used in the process of the invention are compounds of general formula (III) in which:
- - A more particularly represents calcium, zirconium, lanthanum, cerium, samarium, aluminum, boron, iron and partly hydrogen;
- - y represents a whole or fractional number from 3/4 to 3 depending on the valence of the elements A;
- Imp consists of an alkali metal or a mixture of alkali metals and a basic counter anion
- z is between 2% and 10%.
- basic phosphates mention may be made of lanthanum phosphate associated with a cesium, rubidium or potassium compound, cerium phosphate associated with a cesium, rubidium or potassium compound, phosphate samarium associated with a cesium, rubidium or potassium compound, calcium phosphate associated with a cesium, rubidium or potassium compound, calcium hydrogen phosphate associated with a cesium, rubidium or potassium compound, zirconium hydrogen phosphate associated with a compound of cesium, rubidium or potassium.
- the basic phosphates of formula (III) can be prepared by impregnation of a compound of formula (IV) PO 4 A ', in which A' has the same meaning as A, with a solution or a suspension of Imp in a solvent volatile, such as water preferably.
- an advantageous process for the preparation of phosphates of formula (III) consists in: a) carrying out the synthesis of the compound PO 4 A '; then preferably without separating PO 4 A 'from the reaction medium; b) introducing the impregnating agent Imp into the reaction medium; c) separating any residual liquid from the reaction solid; d) dry and possibly calcine.
- the basic metal oxides used in the process of the invention are the basic oxides or those which are made basic by treatment with a base such as an alkali metal or alkaline earth metal hydroxide.
- a base such as an alkali metal or alkaline earth metal hydroxide.
- basic metal oxides non-limiting mention may be made of the oxides of alkali metals, alkaline earth metals, metals of group IIIa of the periodic table of elements, transition elements or rare earths treated or not with a hydroxide of alkali metal.
- alumina treated with sodium hydroxide, zinc oxide, calcium oxide there may be mentioned more particularly alumina treated with sodium hydroxide, zinc oxide, calcium oxide.
- the basic molecular sieves used in the process of the invention are more particularly zeolites of pentasil structure such as for example ZSM-5, ZSM-11, ZSM-22, ZSM-23 or ZSM-48, of mordenite structure, ferrierite structure or faujasite structure such as zeolite X or zeolite Y, of general formula (V) expressed in terms of oxides:
- - E represents an alkali or alkaline earth metal, in whole or with a small proportion of hydrogen
- - T represents a trivalent metal chosen from Al, Ga, Fe and
- - a represents a number from 1 to 2
- - b represents a number equal to or greater than 2
- - r represents a number from 0 to 100.
- nonlimiting examples of basic molecular sieves mention may be made of the NaZSM-5 zeolite, the NaMOR zeolite, the 13XCs zeolite, the NaY zeolite, the KY zeolite and the CsY zeolite. The process is carried out continuously.
- the catalyst used can be placed in a fixed bed or be used in a fluidized bed. It can be used in mixture with inert solids, in order to increase the contact surface.
- the isomerization process is generally carried out at a temperature of 200 ° C to 500 ° C and preferably from 250 ° C to 400 ° C.
- the contact time defined as the ratio between the volume of the catalyst and the total gas flow (lactone + carrier gas if applicable) at the chosen temperature, usually varies from 0.1 seconds to 50 seconds and most often from 1 second at 10 seconds.
- the pressure is not critical. It generally ranges from atmospheric pressure to 10 MPa (100 bar) and preferably from atmospheric pressure to 1.5 MPa (15 bar).
- the lactone can be introduced alone into the reactor containing the catalyst.
- the inert gaseous vector can consist of a gas or a mixture of gases inert under the reaction conditions, such as, for example, nitrogen, argon, air, water vapor, gaseous carboxylic acids at the temperature at which the reaction takes place.
- gases inert under the reaction conditions such as, for example, nitrogen, argon, air, water vapor, gaseous carboxylic acids at the temperature at which the reaction takes place.
- the lactone represents from 10% to 100% by weight relative to the total weight of the gases introduced into the reaction and preferably from 40% to 100%.
- the process of the invention leads to the formation of a mixture of pentenoic acids, pentene-2-oic acid, pentene-3-oic acid and pentene-4-oic acid.
- Pentene-3-oic and pentene-4-oic acids can be hydroxycarbonylated by reaction with carbon monoxide and water to adipic acid.
- the pentene-2-oic acid can itself be isomerized into pentene-3-oic and pentene-4-oic acids which are directly valorized as indicated above.
- the isomerization reaction according to the invention being a thermodynamically difficult reaction, the rate of transformation of the lactone will be limited in practice generally to less than 80% and most often to less than 60%, the unprocessed lactone can then be easily recycled.
- the following examples illustrate the invention.
- the catalyst is conditioned to the temperature chosen for the reaction (300 ° C. unless otherwise indicated), by passing for two hours a stream of nitrogen (2 liters / hour under normal pressure and temperature conditions).
- the lactone is then injected via a syringe pump.
- lactone injection rates will be specified for each example: 3 they are expressed in cm (ml) of lactone in the liquid state.
- test After a warm-up of approximately 15 minutes, the test generally lasts 1 hour.
- the products leaving the reactor are trapped in a receiver containing 10 3 cm of acetonitrile.
- Si / Ai 120 75% of the elements M in formula (I) are H,
- M in formula (I) mainly represents NH 4 and minority H
- M in formula (I) mainly represents NH 4 and minority H
- M in formula (I) represents H in full.
- the operating conditions are those given in the general operating mode described above.
- the contact time (te) is approximately 1.4 seconds for each of the examples.
- P2 pentene-2-oic acid
- P3 pentene-3-oic acid
- P4 pentene-4-oic acid
- SiO 2 / AL0 3 (marketed by DEGUSSA) comprising 16% by weight of Si0 2 ,
- the operating conditions are those described above.
- the reaction time is 1 hour except -; __ 3
- Example 14 with chlorinated alumina where this time is 0.5 h, the temperature can be different from 300 ° C, the nitrogen flow can be different from 2 liters / hour and the rate of introduction of gamma-valerolactone can be different from 3.2 ml / h of liquid / hour.
- the operating conditions are those which have been described previously in the general operating mode, with the following differences:
- the operating conditions are those given in the general operating mode described above.
- the operating conditions are those given in the general operating mode described above.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019950701253A KR950703508A (ko) | 1992-10-02 | 1993-09-23 | 산성 또는 염기성 촉매에 의한 락톤의 펜텐산으로의 이성질화 방법(process for isomerization of lactones into pentenoic acids by acid or basic catalysis) |
BR9307159A BR9307159A (pt) | 1992-10-02 | 1993-09-23 | Processo de isomerização em ácido pentenóico de pelo menos uma lactona |
EP93920924A EP0662944A1 (fr) | 1992-10-02 | 1993-09-23 | Procede d'isomerisation de lactones en acides pentenoiques par catalyse acide ou basique |
JP6508767A JPH08500608A (ja) | 1992-10-02 | 1993-09-23 | 酸性又は塩基性触媒によってラクトンをペンテン酸に異性化する方法 |
SK418-95A SK41895A3 (en) | 1992-10-02 | 1993-09-23 | Process for isomerization of lactones into pentenoic acids by acid or basic catalysis |
PL93308208A PL308208A1 (en) | 1992-10-02 | 1993-09-23 | Isomerisation of lactones to pentenic acids in an acidic or basic catalysis process |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR92/12181 | 1992-10-02 | ||
FR9212181A FR2696448B1 (fr) | 1992-10-02 | 1992-10-02 | Procédé d'isomérisation de lactones en acides penténoïques par catalyse acide. |
FR9212182A FR2696449B1 (fr) | 1992-10-02 | 1992-10-02 | Procédé d'isomérisation de lactones en acides penténoïques par catalyse basique. |
FR92/12182 | 1992-10-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994007835A1 true WO1994007835A1 (fr) | 1994-04-14 |
Family
ID=26229794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1993/000928 WO1994007835A1 (fr) | 1992-10-02 | 1993-09-23 | Procede d'isomerisation de lactones en acides pentenoiques par catalyse acide ou basique |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0662944A1 (fr) |
JP (1) | JPH08500608A (fr) |
KR (1) | KR950703508A (fr) |
CN (1) | CN1089933A (fr) |
BR (1) | BR9307159A (fr) |
CA (1) | CA2146153A1 (fr) |
CZ (1) | CZ79795A3 (fr) |
MX (1) | MX9306070A (fr) |
PL (1) | PL308208A1 (fr) |
SG (1) | SG45321A1 (fr) |
SK (1) | SK41895A3 (fr) |
WO (1) | WO1994007835A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5948683A (en) * | 1997-10-18 | 1999-09-07 | Engelhard Corporation | Catalyst for selective oxidation of unsaturated hydrocarbons and methods of making and using the same |
WO2012134397A1 (fr) * | 2011-03-28 | 2012-10-04 | Agency For Science, Technology And Research | Synthèse de diacides |
US20180305286A1 (en) * | 2016-03-21 | 2018-10-25 | Novomer, Inc. | Systems and Processes for Producing Organic Acids Direct from Beta-Lactones |
US10662139B2 (en) | 2016-03-21 | 2020-05-26 | Novomer, Inc. | Acrylic acid production process |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018188402A (ja) * | 2017-05-10 | 2018-11-29 | 宇部興産株式会社 | ペンテン酸エステルの製造方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2382464A (en) * | 1942-01-30 | 1945-08-14 | Carbide & Carbon Chem Corp | Production of unsaturated carboxylic acids |
GB958225A (en) * | 1959-10-20 | 1964-05-21 | Celanese Corp | Improvements in the production of ª‡/ª‰-ethylenically unsaturated carboxylic acids |
US3944572A (en) * | 1973-04-11 | 1976-03-16 | Laporte Industries Limited | Lactones |
EP0142313A1 (fr) * | 1983-11-03 | 1985-05-22 | Mobil Oil Corporation | Méthode de préparation d'un catalyseur zéolitique |
FR2563446A1 (fr) * | 1984-04-25 | 1985-10-31 | Raffinage Cie Francaise | Nouvelle zeolite a structure bidimensionnelle et application de ladite zeolite |
US4701431A (en) * | 1984-12-24 | 1987-10-20 | Exxon Research And Engineering Company | Rare earth stabilized aluminum deficient zeolite |
-
1993
- 1993-09-23 SG SG1996003483A patent/SG45321A1/en unknown
- 1993-09-23 CZ CZ95797A patent/CZ79795A3/cs unknown
- 1993-09-23 CA CA002146153A patent/CA2146153A1/fr not_active Abandoned
- 1993-09-23 JP JP6508767A patent/JPH08500608A/ja active Pending
- 1993-09-23 WO PCT/FR1993/000928 patent/WO1994007835A1/fr not_active Application Discontinuation
- 1993-09-23 EP EP93920924A patent/EP0662944A1/fr not_active Ceased
- 1993-09-23 BR BR9307159A patent/BR9307159A/pt not_active Application Discontinuation
- 1993-09-23 KR KR1019950701253A patent/KR950703508A/ko not_active Application Discontinuation
- 1993-09-23 SK SK418-95A patent/SK41895A3/sk unknown
- 1993-09-23 PL PL93308208A patent/PL308208A1/xx unknown
- 1993-09-28 CN CN93118204A patent/CN1089933A/zh active Pending
- 1993-09-30 MX MX9306070A patent/MX9306070A/es unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2382464A (en) * | 1942-01-30 | 1945-08-14 | Carbide & Carbon Chem Corp | Production of unsaturated carboxylic acids |
GB958225A (en) * | 1959-10-20 | 1964-05-21 | Celanese Corp | Improvements in the production of ª‡/ª‰-ethylenically unsaturated carboxylic acids |
US3944572A (en) * | 1973-04-11 | 1976-03-16 | Laporte Industries Limited | Lactones |
EP0142313A1 (fr) * | 1983-11-03 | 1985-05-22 | Mobil Oil Corporation | Méthode de préparation d'un catalyseur zéolitique |
FR2563446A1 (fr) * | 1984-04-25 | 1985-10-31 | Raffinage Cie Francaise | Nouvelle zeolite a structure bidimensionnelle et application de ladite zeolite |
US4701431A (en) * | 1984-12-24 | 1987-10-20 | Exxon Research And Engineering Company | Rare earth stabilized aluminum deficient zeolite |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5948683A (en) * | 1997-10-18 | 1999-09-07 | Engelhard Corporation | Catalyst for selective oxidation of unsaturated hydrocarbons and methods of making and using the same |
WO2012134397A1 (fr) * | 2011-03-28 | 2012-10-04 | Agency For Science, Technology And Research | Synthèse de diacides |
EP2691361A1 (fr) * | 2011-03-28 | 2014-02-05 | Agency For Science, Technology And Research | Synthèse de diacides |
EP2691361A4 (fr) * | 2011-03-28 | 2014-09-17 | Agency Science Tech & Res | Synthèse de diacides |
US20150183703A1 (en) * | 2011-03-28 | 2015-07-02 | Agency For Science, Technology And Research | Synthesis of diacids |
US20180305286A1 (en) * | 2016-03-21 | 2018-10-25 | Novomer, Inc. | Systems and Processes for Producing Organic Acids Direct from Beta-Lactones |
US10662139B2 (en) | 2016-03-21 | 2020-05-26 | Novomer, Inc. | Acrylic acid production process |
US11827590B2 (en) | 2016-03-21 | 2023-11-28 | Novomer, Inc. | Acrylic acid, and methods of producing thereof |
Also Published As
Publication number | Publication date |
---|---|
CZ79795A3 (en) | 1995-09-13 |
SG45321A1 (en) | 1998-01-16 |
SK41895A3 (en) | 1995-09-13 |
MX9306070A (es) | 1994-05-31 |
EP0662944A1 (fr) | 1995-07-19 |
KR950703508A (ko) | 1995-09-20 |
PL308208A1 (en) | 1995-07-24 |
BR9307159A (pt) | 1999-03-30 |
CA2146153A1 (fr) | 1994-04-14 |
CN1089933A (zh) | 1994-07-27 |
JPH08500608A (ja) | 1996-01-23 |
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