EP4093841B1 - Vollständig wiederverwendbare katalysatoren für veresterungsreaktionen - Google Patents

Vollständig wiederverwendbare katalysatoren für veresterungsreaktionen Download PDF

Info

Publication number
EP4093841B1
EP4093841B1 EP21704942.8A EP21704942A EP4093841B1 EP 4093841 B1 EP4093841 B1 EP 4093841B1 EP 21704942 A EP21704942 A EP 21704942A EP 4093841 B1 EP4093841 B1 EP 4093841B1
Authority
EP
European Patent Office
Prior art keywords
acid
catalyst
reaction
zinc
mmhg
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.)
Active
Application number
EP21704942.8A
Other languages
English (en)
French (fr)
Other versions
EP4093841C0 (de
EP4093841A1 (de
Inventor
Vincenzo BENESSERE
Maria Elena CUCCIOLITO
Martino Di Serio
Roberto Esposito
Massimo MELCHIORRE
Francesco RUFFO
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.)
Isuschem Srl
Original Assignee
Isuschem Srl
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 Isuschem Srl filed Critical Isuschem Srl
Publication of EP4093841A1 publication Critical patent/EP4093841A1/de
Application granted granted Critical
Publication of EP4093841C0 publication Critical patent/EP4093841C0/de
Publication of EP4093841B1 publication Critical patent/EP4093841B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/02—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with glycerol
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates

Definitions

  • the present invention relates to the production process of fatty acid esters.
  • the developed method allows the production of esters through esterification reaction between saturated, mono-unsaturated and poly-unsaturated C 4 -C 22 fatty acids (for example butyric acid, valeric acid, capronic acid, enanthic acid, caprylic acid, nonanoic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, myristoleic acid, sapienic acid, palmitoleic acid, heptadecenoic acid, oleic acid, elaidinic acid, vaccenic acid, asclepic acid, petroselinic acid, petroselaidic acid, gadoleic acid, gondoic acid, cetoleic acid, erucic acid, linoleic acid, rumenic acid,
  • the present method uses zinc oxide or zinc salts with basic anions (for example carboxylates and carbonate) as esterification catalyst between carboxylic acids and alcohols or poly-alcohols.
  • the catalyst is introduced as a powder into the reactant system. Once the reaction is complete and the ester is obtained, after the reaction mixture has been cooled to room temperature, a precipitate is separated from the mixture by simple filtration. The precipitate, used as a catalyst in subsequent reactions, showed without further treatments a catalytic activity comparable to the original catalyst.
  • Organic esters are a family of chemical compounds of very wide industrial use (solvents, surfactants, lubricants, biofuels, monomers). They are typically produced by esterification reactions starting from a carboxylic acid and an alcohol. This reaction is generally acid catalyzed and in equilibrium. Sulfuric acid is an effective esterification catalyst and, coupled with systems for removing water from the reaction environment, allows for convenient conversions. However, its use is problematic due to its strong corrosive action, and due to the intolerance of many functional groups to Broensted's acidity. Furthermore, the purification of the product often requires complex operations, which involve washing with aqueous solutions and resulting wastewater to be disposed of.
  • a product purification strategy involves the use of aqueous solutions with complexing agents such as nitrilotriacetic acid, ion exchange resins, water washing and a phase separation and a dehydration procedure of the aqueous phase.
  • complexing agents such as nitrilotriacetic acid, ion exchange resins, water washing and a phase separation and a dehydration procedure of the aqueous phase.
  • FR2552242 discloses a process for the manufacture of a fatty acid ester and glycerin of high purity, which comprises the reaction of a vegetable or anima; oil with a 1 - 18C aliphatic mono-alcohol in the presence of ZnO or a mixture of Zn and Al oxides and zinc aluminate, of formula ZnAl2O4, xZnO, yAl2O3, where -x and y are 0 - 2.
  • the present invention relates to a catalytic esterification process between carboxylic acids (C 4 -C 22 ) and monoalcohols (C 6 -C 22 ) or polyalcohols (C 3 -C 12 ) using zinc(II)-based catalysts that are completely and immediately recyclable, avoiding reactivation operations.
  • the catalyst preferably zinc oxide or zinc(II) salts with basic anions (for example carboxylates and carbonate), is introduced as a powder into the reagent system. At the end of the reaction, through simple filtration a solid is recovered which has the same catalytic performance as the originally introduced zinc(II) species.
  • the carboxylic acid, alcohol or polyalcohol are introduced in the appropriate stoichiometric ratio, in which the ratio in moles between the RCOOH fatty acid and (i) the mono-alcohol R'OH is between 1:1.01 and 1:2, more preferably between 1:1.1 and 1:1.2 (ii) the polyalcohol R'(OH) n is between 1:1 and 5:1, with n between 1 and 5.
  • the zinc(II) catalyst is added to the system in a stoichiometric ratio between fatty acid and zinc(II) between 1:0.02 and 1:0.001, more preferably between 1:0.01 and 1:0.005.
  • the reactor and the Claisen head are heated to 150-180°C and 100°C-120°C respectively.
  • the reaction time is between 4 and 6h and the working pressure during the reaction time is 760 mmHg. The following reactions occur:
  • Test 2.1 For the synthesis of 2-ethylhexyl nonanoate, 125 mmol of nonanoic acid (19.8 g; 22.0 mL; supplied by Sigma Aldrich, purity 99%), 150 mmol of 2-ethylhexyl alcohol (19.5 g; 23.5 mL; supplied by Sigma Aldrich, purity 99%) and 1.25 mmol zinc oxide (0.102 g; supplied by Sigma Aldrich, purity 99%) are vigorously mixed in a 100 mL flask equipped with a Claisen head fitted with a thermo-electric heating band.
  • the reaction vessel is heated to a temperature of 170°C, using a thermostated diathermic oil bath, while the temperature of the heating band on the Claisen head is set at 110°C using a thermocouple.
  • a graduated 5 mL Schlenk tube is mounted to monitor the reaction conversion by collecting the water produced by the reaction.
  • the reaction time is considered from the moment in which the catalyst is added, and the mixture is left to react at the set temperatures for 4 h; the working pressure is 760 mmHg.
  • the complete conversion is verified by sampling from the reaction mixture and NMR analysis (400 MHz Bruker). At the end of the reaction, the volume of water collected in the tube is between 1.5 and 1.6 mL.
  • the recovery vessel is replaced with a new 5 mL graduated Schlenk tube and a pressure of 100 mmHg is applied.
  • a pressure of 100 mmHg is applied.
  • about 0.5 mL of water and 3.5 mL of alcohol are collected.
  • the system is brought back to atmospheric pressure and is allowed to cool until it reaches room temperature.
  • the reaction mixture appears as a suspension of the solid insoluble catalyst in the ester.
  • the catalyst is easily separated by filtration at a reduced pressure between 1.5 and 100 mmHg on a P2 sintered glass filter, and the 2-ethylhexylnonanoate product is obtained with a purity greater than 99% ( 1 H and 13 C NMR analysis).
  • the content of zinc(II) in the product is lower than 2 ppm.
  • Test 2.2 For the synthesis of 2-ethylhexyl oleate, 125 mmol of oleic acid (35.3 g; 39.7 mL; supplied by Carlo Erba, purity 99%), 150 mmol of 2-ethylhexyl alcohol (19.5 g; 23.5 mL; supplied by Sigma Aldrich, purity 99%) and 1.25 mmol zinc oxide (0.102 g; supplied by Sigma Aldrich, purity 99%) are vigorously mixed in a 100 mL flask equipped with a Claisen head fitted with a thermo-electric heating band.
  • the reaction vessel is heated to a temperature of 170°C, using a thermostated diathermic oil bath, while the temperature of the heating band on the Claisen head is set at 110°C using a thermocouple.
  • a graduated 5 mL Schlenk tube is mounted to monitor the reaction conversion by collecting the water produced by the reaction.
  • the reaction time is considered from the moment in which the catalyst is added, and the mixture is left to react at the set temperatures for 6 h; the working pressure is 760 mmHg.
  • the complete conversion is verified by sampling from the reaction mixture and NMR analysis (400 MHz Bruker). At the end of the reaction, the volume of water collected in the tube is between 1.5 and 1.6 mL.
  • the recovery vessel is replaced with a new 5 mL graduated Schlenk tube and a pressure of 100 mmHg is applied.
  • a pressure of 100 mmHg is applied.
  • about 0.5 mL of water and 5 mL of alcohol are collected.
  • the system is brought back to atmospheric pressure and is allowed to cool until it reaches room temperature.
  • the reaction mixture appears as a suspension of the solid insoluble catalyst in the ester.
  • the catalyst is easily separated by filtration at a reduced pressure between 1.5 and 100 mmHg on a P2 sintered glass filter, and the 2-ethylhexyl oleate product is obtained with a purity greater than 96% ( 1 H and 13 C NMR analysis).
  • the content of zinc(II) in the product is lower than 10 ppm.
  • the double bond of oleic acid does not undergo chemical transformations and is inert during the process.
  • Test 2.3 For the synthesis of 1-hexyl nonanoate, 125 mmol of nonanoic acid (19.8 g; 22.0 mL; supplied by Sigma Aldrich, purity 99%), 150 mmol of 1-hexyl alcohol (15.3 g; 18.8 mL; supplied by Sigma Aldrich, purity 99%) and 1.25 mmol zinc oxide (0.102 g; supplied by Sigma Aldrich, purity 99%) are vigorously mixed in a 100 mL flask equipped with a Claisen head fitted with a thermo-electric heating band.
  • the reaction vessel is heated to a temperature of 170°C, using a thermostated diathermic oil bath, while the temperature of the heating band on the Claisen head is set at 110°C using a thermocouple.
  • a graduated 5 mL Schlenk tube is mounted to monitor the reaction conversion by collecting the water produced by the reaction.
  • the reaction time is considered from the moment in which the catalyst is added, and the mixture is left to react at the set temperatures for 4 h; the working pressure is 760 mmHg.
  • the complete conversion is verified by sampling from the reaction mixture and NMR analysis (400 MHz Bruker). At the end of the reaction, the volume of water collected in the tube is between 1.5 and 1.6 mL.
  • Test 2.4 For the synthesis of triolein, 40.0 mmol of glycerol (3.68 g; 2.92 mL; supplied by Sigma Aldrich, 99% purity), 122 mmol of oleic acid (34.6 g; 38.4 mL; supplied by Sigma Aldrich, 99% purity) and 1.2 mmol of zinc oxide (0.098 g; supplied by Sigma Aldrich, purity 99%) are vigorously mixed in a 100 mL flask equipped with a Claisen head fitted with a thermo-electric heating band. The reaction parameters are the same as described in example 2.1.
  • triolein is produced with a selectivity greater than 98% ( 1 H and 13 C NMR analysis).
  • the content of zinc(II) in the product is 1.4 ppm.
  • the double bond of oleic acid does not undergo chemical transformations and is inert during the process.
  • Test 2.5 For the synthesis of 2-ethylhexyl nonanoate, 125 mmol of nonanoic acid (19.8 g; 22.0 mL; supplied by Sigma Aldrich, purity 99%), 150 mmol of 2-ethylhexyl alcohol (19.5 g; 23.5 mL; supplied by Sigma Aldrich, purity 99%) and 1.25 mmol zinc acetate dihydrate (0.275 g; supplied by Sigma Aldrich, purity 99%) are vigorously mixed in a 100 mL flask equipped with a Claisen head fitted with a thermo-electric heating band.
  • the reaction vessel is heated to a temperature of 170°C, using a thermostated diathermic oil bath, while the temperature of the heating band on the Claisen head is set at 110°C using a thermocouple.
  • a graduated 5 mL Schlenk tube is mounted to monitor the reaction conversion by collecting the water produced by the reaction.
  • the reaction time is considered from the moment in which the catalyst is added, and the mixture is left to react at the set temperatures for 4 h; the working pressure is 760 mmHg.
  • the complete conversion is verified by sampling from the reaction mixture and NMR analysis (400 MHz Bruker). At the end of the reaction, the volume of water collected in the tube is between 1.5 and 1.6 mL.
  • the recovery vessel is replaced with a new 5 mL graduated Schlenk tube and a pressure of 100 mmHg is applied.
  • a pressure of 100 mmHg is applied.
  • about 0.5 mL of water and 3.5 mL of alcohol are collected.
  • the system is brought back to atmospheric pressure and is allowed to cool until it reaches room temperature.
  • the reaction mixture appears as a suspension of the solid insoluble catalyst in the ester.
  • the catalyst is easily separated by filtration at a reduced pressure between 1.5 and 100 mmHg on a P2 sintered glass filter, and the 2-ethylhexylnonanoate product is obtained with a purity greater than 99% ( 1 H and 13 C NMR analysis).
  • the content of zinc(II) in the product is 2.5 ppm.
  • Test 2.6 For the synthesis of 2-ethylhexyl nonanoate, 125 mmol of nonanoic acid (19.8 g; 22.0 mL; supplied by Sigma Aldrich, purity 99%), 150 mmol of 2-ethylhexyl alcohol (19.5 g; 23.5 mL; supplied by Sigma Aldrich, purity 99%) and 1.25 mmol zinc carbonate (0.156 g; supplied by Sigma Aldrich, purity 99%) are vigorously mixed in a 100 mL flask equipped with a Claisen head fitted with a thermo-electric heating band.
  • the reaction vessel is heated to a temperature of 170°C, using a thermostated diathermic oil bath, while the temperature of the heating band on the Claisen head is set at 110°C using a thermocouple.
  • a graduated 5 mL Schlenk tube is mounted to monitor the reaction conversion by collecting the water produced by the reaction.
  • the reaction time is considered from the moment in which the catalyst is added, and the mixture is left to react at the set temperatures for 4 h; the working pressure is 760 mmHg.
  • the complete conversion is verified by sampling the reaction mixture and NMR analysis (400 MHz Bruker). At the end of the reaction, the volume of water collected in the tube is between 1.5 and 1.6 mL.
  • the recovery vessel is replaced with a new 5 mL graduated Schlenk tube and a pressure of 100 mmHg is applied.
  • a pressure of 100 mmHg is applied.
  • about 0.5 mL of water and 3.5 mL of alcohol are collected.
  • the system is brought back to atmospheric pressure and is allowed to cool until it reaches room temperature.
  • the reaction mixture appears as a suspension of the solid insoluble catalyst in the ester.
  • the catalyst is easily separated by filtration at a reduced pressure between 1.5 and 100 mmHg on a P2 sintered glass filter, and the 2-ethylhexylnonanoate product is obtained with a purity greater than 99% ( 1 H and 13 C NMR analysis).
  • the zinc(II) content in the product is 7.6 ppm.
  • Test 3.1 To demonstrate the feasibility of using the recovered catalyst after ester synthesis described in Test 2.1, for the synthesis of 2-ethylhexyl nonanoate, 125 mmol nonanoic acid (19.8 g; 22.0 mL; supplied by Sigma Aldrich, purity 99 %), 150 mmol of 2-ethylhexyl alcohol (19.5 g; 23.5 mL; supplied by Sigma Aldrich, purity 99%) and the solid recovered in Test 2.1 without further treatment are vigorously mixed in a 100 mL flask equipped with a Claisen head fitted with a thermo-electric heating band.
  • the reaction vessel is heated to a temperature of 170°C, using a thermostated diathermic oil bath, while the temperature of the heating band on the Claisen head is set at 110°C using a thermocouple.
  • a graduated 5 mL Schlenk tube is mounted to monitor the reaction conversion by collecting the water produced by the reaction.
  • the reaction time is considered from the moment in which the catalyst is added, and the mixture is left to react at the set temperatures for 4 h; the working pressure is 760 mmHg.
  • the complete conversion is verified by sampling the reaction mixture and NMR analysis (400 MHz Bruker). At the end of the reaction, the volume of water collected in the tube is between 1.5 and 1.6 mL.
  • Test 3.2 To demonstrate the feasibility of using the recovered catalyst after ester synthesis described in Test 3.1, for the synthesis of 2-ethylhexyl nonanoate, 125 mmol nonanoic acid (19.8 g; 22.0 mL; supplied by Sigma Aldrich, purity 99 %), 150 mmol 2-ethylhexyl alcohol (19.5 g; 23.5 mL; supplied by Sigma Aldrich, purity 99%) and the solid recovered in Test 3.1 without further treatment are vigorously mixed in a 100 mL flask equipped with a Claisen head fitted with a thermo-electric heating band.
  • the reaction vessel is heated to a temperature of 170°C, using a thermostated diathermic oil bath, while the temperature of the heating band on the Claisen head is set at 110°C using a thermocouple.
  • a graduated 5 mL Schlenk tube is mounted to monitor the reaction conversion by collecting the water produced by the reaction.
  • the reaction time is considered from the moment in which the catalyst is added, and the mixture is left to react at the set temperatures for 4 h; the working pressure is 760 mmHg.
  • the complete conversion is verified by sampling the reaction mixture and NMR analysis (400 MHz Bruker). At the end of the reaction, the volume of water collected in the tube is between 1.5 and 1.6 mL.
  • Test 3.3 To demonstrate the feasibility of using the recovered catalyst after ester synthesis described in Test 2.5, for the synthesis of 2-ethylhexyl nonanoate, 125 mmol nonanoic acid (19.8 g; 22.0 mL; supplied by Sigma Aldrich, purity 99 %), 150 mmol 2-ethylhexyl alcohol (19.5 g; 23.5 mL; supplied by Sigma Aldrich, purity 99%) and the solid recovered in Test 2.5 without further treatment are vigorously mixed in a 100 mL flask equipped with a Claisen head fitted with a thermo-electric heating band.
  • the reaction vessel is heated to a temperature of 170°C, using a thermostated diathermic oil bath, while the temperature of the heating band on the Claisen head is set at 110°C using a thermocouple.
  • a graduated 5 mL Schlenk tube is mounted to monitor the reaction conversion by collecting the water produced by the reaction.
  • the reaction time is considered from the moment in which the catalyst is added, and the mixture is left to react at the set temperatures for 4 h; the working pressure is 760 mmHg.
  • the complete conversion is verified by sampling the reaction mixture and NMR analysis (400 MHz Bruker). At the end of the reaction, the volume of water collected in the tube is between 1.5 and 1.6 mL.
  • a graduated 5 mL Schlenk tube is mounted downstream of the Claisen head to monitor the reaction conversion by collecting the water produced by the reaction.
  • the reaction time is considered from the moment in which the catalyst is added, and the mixture is left to react at the set temperatures for 4 h; the working pressure is 760 mmHg.
  • the complete conversion is verified by sampling the reaction mixture and NMR analysis (400 MHz Bruker).
  • the volume of water collected in the tube is between 1.5 and 1.6 mL.
  • the recovery vessel is replaced with a new 5 mL graduated Schlenk tube and a pressure of 100 mmHg is applied. In this phase, lasting 40 minutes, about 0.5 mL of water and 3.5 mL of alcohol are collected.
  • the system is brought back to atmospheric pressure and is allowed to cool until it reaches room temperature.
  • the residue is separated by filtration at a reduced pressure ranging from 1.5 to 100 mmHg on a P2 sintered glass filter, and the 2-ethylhexylnonanoate product is obtained with a purity of 91% ( 1 H and 13 C NMR analysis).
  • the content of zinc(II) in the product is equal to about 2000 ppm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Claims (10)

  1. Katalytisches Veresterungsverfahren zur Synthese eines Fettsäureesters der allgemeinen Formel RCOO-R' durch Reaktion zwischen einer Fettsäure der allgemeinen Formel RCOOH und einem Monoalkohol der allgemeinen Formel R'OH, wobei:
    - R stellt eine gesättigte oder ungesättigte, lineare oder verzweigte Alkylgruppe, mit 4 bis 22 Kohlenstoffatomen dar;
    - R' stellt eine Gruppe dar, die 6 bis 16 Kohlenstoffatome enthält;
    wobei der Katalysator ein Zink(II)-Salz mit basischen Anionen ist, vorzugsweise Zinkoxid (ZnO), Zinkcarbonat (ZnCO3), Zinkacetat (Zn(OAc)2), und das aus den folgenden fünf aufeinanderfolgenden Phasen besteht:
    (i) einem Schritt des Erhitzens der Reaktionsmischung auf eine Temperatur zwischen 150 und 180 °C und bei einem Betriebsdruck von 760 mmHg, bis der Katalysator aufgelöst ist;
    (ii) einem Reaktionsschritt zwischen den verwendeten Spezies bei einer Temperatur zwischen 150 und 180 °C, bei einem Betriebsdruck von 760 mmHg, für einen Zeitraum zwischen 4 und 6 Stunden für die Synthese des gewünschten Esters, während dessen die verwendeten Temperaturbedingungen die Beseitigung des erzeugten Wassers durch Destillation ermöglichen;
    (iii) einem Schritt der Destillation der überschüssigen alkoholischen Fraktion und der verbleibenden Wasserspuren bei einem Druck von 100 mmHg für einen Zeitraum zwischen 30 und 60 Minuten;
    (iv) einem Schritt des Abkühlens der Reaktionsmischung, die den erzeugten Ester enthält, auf mindestens 90 Masse-% bei Umgebungstemperatur und -druck, bis ein Feststoff, der Zn(II) enthält, ausfällt;
    (v) einer Estertrennphase, erhalten durch Filtration des Feststoffs unter vermindertem Druck;
    wobei das Verfahren ermöglicht es, den am obigen Punkt (v) ausgefällten Feststoff als Katalysator für nachfolgende Veresterungsreaktionen ohne Verlust der katalytischen Aktivität zu recyceln.
  2. Katalytisches Veresterungsverfahren zur Synthese eines Fettsäureesters der allgemeinen Formel RCOO-R' durch Reaktion zwischen einer Fettsäure der allgemeinen Formel RCOOH und einem Polyalkohol der allgemeinen Formel R'(OH)n, wobei:
    - n ist ein Wert zwischen 2 und 5,
    - R stellt eine gesättigte oder ungesättigte, lineare oder verzweigte Alkylgruppe mit 4 bis 22 Kohlenstoffatomen dar,
    - R' stellt eine Gruppe mit 3 bis 12 Kohlenstoffatomen dar,
    wobei der Katalysator ein Zink(II)-Salz mit basischen Anionen ist, vorzugsweise Zinkoxid (ZnO), Zinkcarbonat (ZnCO3), Zinkacetatzink (Zn(OAc)2), und die folgenden vier aufeinanderfolgenden Phasen umfasst:
    (i) einen Schritt des Erhitzens der Reaktionsmischung auf eine Temperatur zwischen 150 und 180 °C und bei einem Betriebsdruck von 760 mmHg, bis der Katalysator aufgelöst ist;
    (ii) einen Reaktionsschritt zwischen den verwendeten Spezies bei einer Temperatur zwischen 150 und 180 °C, unter einem Betriebsdruck von 760 mmHg, für einen Zeitraum zwischen 4 und 6 Stunden für die Synthese des erhaltenen Esters, während dessen die verwendeten Temperaturbedingungen die Beseitigung des erzeugten Wassers durch Destillation ermöglichen;
    (iii) einen Schritt des Abkühlens der Reaktionsmischung, die den erzeugten Ester zu mindestens 90 Massen-%, bei Umgebungstemperatur und -druck enthält, bis ein Feststoff, der Zn(II) enthält, ausfällt;
    (iv) einen Schritt der Abtrennung des erzeugten Esters durch Filtration des Feststoffs unter vermindertem Druck;
    wobei das Verfahren ermöglicht es, den am obigen Punkt (iv) ausgefällten Feststoffs als Katalysator für nachfolgende Veresterungsreaktionen ohne Verlust der katalytischen Aktivität, zu recyceln.
  3. Katalytisches Verfahren nach Anspruch 1, wobei das Molverhältnis zwischen der Fettsäure RCOOH und dem Monoalkohol R'OH zwischen 1 : 1,01 und 1 : 2, besonders bevorzugt zwischen 1 : 1,1 und 1 : 1,2 liegt und der auf Zink(II) basierende Katalysator zwischen 1 : 0,02 und 1 : 0,001, besonders bevorzugt zwischen 1 : 0,01 und 1 : 0,005, liegt.
  4. Katalytisches Verfahren nach Anspruch 2, wobei das Molverhältnis zwischen der Fettsäure RCOOH und dem Polyalkohol R'(OH)n zwischen 1 : 1 und 5 : 1 liegt, der auf Zink(II) basierende Katalysator zwischen 1 : 0,02 und 1 : 0,001, bevorzugterweise zwischen 1 : 0,01 und 1 : 0,005, liegt.
  5. Katalytisches Verfahren nach Anspruch 1, wobei der Verfahrensschritt (v), ein Isolationsschritt, durch Filtration bei reduziertem Druck zwischen 1,5 und 100 mmHg auf gesinterten Glasfiltern mit einer Nennporosität zwischen 40 und 100 µm (P2) bis zur vollständigen Filtration des synthetisierten Produkts durchgeführt werden kann.
  6. Katalytisches Verfahren nach Anspruch 2, wobei der Verfahrensschritt (iv), ein Isolationsschritt, durch Filtration bei vermindertem Druck zwischen 1,5 und 100 mmHg auf gesinterten Glasfiltern mit einer Nennporosität zwischen 40 und 100 µm (P2) bis zur vollständigen Filtration des synthetisierten Produkts durchgeführt werden kann.
  7. Verfahren nach Anspruch 1 oder Anspruch 2, wobei die RCOOH-Fettsäure zur C4-C22-Familie der gesättigten Fettsäuren, einfach ungesättigten Fettsäuren, mehrfach ungesättigten Fettsäuren gehört, zum Beispiel: Buttersäure, Valeriansäure, Capronsäure, Enanthsäure , Caprylsäure, Nonansäure, Caprinsäure, Undecansäure, Laurinsäure, Tridecansäure, Myristinsäure, Pentadecansäure, Palmitinsäure, Margarinsäure, Stearinsäure, Nonadecansäure, Arachinsäure, Behensäure, Myristoleinsäure, Sapiensäure, Palmitoleinsäure Säure, Heptadecensäure, Ölsäure, Elaidinsäure, Vaccensäure, Asklepinsäure, Petroselinsäure, Petroselaminsäure, Gadoleinsäure, Gondoinsäure, Ketoleinsäure, Erucasäure, Linolsäure, Pansensäure, Säure α-Linolensäure, Y-Linolensäure , Stearidonsäure, Arachidonsäure, Thymnodonsäure, Cervonsäure.
  8. Verfahren nach Anspruch 1, wobei der Monoalkohol R'OH zur C6-C16-Familie linearer, verzweigter oder cyclischer Alkohole gehört, beispielsweise: 1-Hexanol, 1-Heptanol, 1-Octanol, 2-Octanol, 1-Nonanol, 1-Decanol, 1-Undecanol, 1-Dodecanol, 1-Tridecanol, 1-Tetradecanol, 1-Pentadecanol, 1-Hexadecanol, 11-Undecen-1-ol, 3-Methyl-3-pentanol, 2-Methyl-1-pentanol, 2-Ethyl-1-hexanol, 2-Propyl-1-heptanol, 2-Butyl-1-octanol, 2-Pentyl-1-nonanol, 2-hexyl-1-decanol, Cyclohexanol, Menthol.
  9. Verfahren nach Anspruch 2, wobei der Polyalkohol zur C3-C12-Familie der Polyalkohole und Alditole gehört, beispielsweise: Propylenglykol, 1,3-Butylenglykol, Glycerin, Erythrit, Pentaerythrit, Arabit, Xylit.
  10. Verwendung einer Verbindung ausgewählt aus Zinkcarbonat (ZnCO3) und Zinkacetat (Zn(OAc)2) als Katalysator im katalytischen Verfahren nach einem der Ansprüche 1 bis 8.
EP21704942.8A 2020-01-24 2021-01-25 Vollständig wiederverwendbare katalysatoren für veresterungsreaktionen Active EP4093841B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102020000001378A IT202000001378A1 (it) 2020-01-24 2020-01-24 Catalizzatori totalmente riciclabili per reazioni di esterificazione
PCT/IB2021/050551 WO2021149025A1 (en) 2020-01-24 2021-01-25 Totally recyclable catalysts for esterification reactions

Publications (3)

Publication Number Publication Date
EP4093841A1 EP4093841A1 (de) 2022-11-30
EP4093841C0 EP4093841C0 (de) 2023-10-25
EP4093841B1 true EP4093841B1 (de) 2023-10-25

Family

ID=70738793

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21704942.8A Active EP4093841B1 (de) 2020-01-24 2021-01-25 Vollständig wiederverwendbare katalysatoren für veresterungsreaktionen

Country Status (3)

Country Link
EP (1) EP4093841B1 (de)
IT (1) IT202000001378A1 (de)
WO (1) WO2021149025A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202200015849A1 (it) * 2022-07-27 2024-01-27 Itelyum Regeneration S P A Processo per la produzione di solventi e/o lubrificanti da fonti rinnovabili
CN115873160B (zh) * 2023-01-03 2025-11-07 佛山市顺德区永利华运动用品有限公司 一种可降解的手套防护块及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2752242B1 (fr) * 1996-08-08 1998-10-16 Inst Francais Du Petrole Procede de fabrication d'esters a partir d'huiles vegetales ou animales et d'alcools
US5898077A (en) 1997-10-07 1999-04-27 Matsumoto Yushi-Seiyaku Co., Ltd. Process for preparation of an ester
ES2374074T3 (es) * 2006-07-10 2012-02-13 A.& A. F.Lli Parodi S.R.L. Proceso para la producción de biodiésel.
MY148943A (en) 2006-08-28 2013-06-14 Univ Putra Malaysia Production of acylglycerol esters
FR2951092B1 (fr) * 2009-10-14 2013-03-08 Inst Francais Du Petrole Catalyseur heterogene de type spinelle aluminate de zinc sur-stoechiometrique en zinc et son utilisation dans un procede de preparation d'esters alcooliques a partir de triglycerides et d'alcools
DE102013015289A1 (de) * 2013-09-14 2015-03-19 Oxea Gmbh Verfahren zur Nachbehandlung von Polyolestern

Also Published As

Publication number Publication date
EP4093841C0 (de) 2023-10-25
EP4093841A1 (de) 2022-11-30
WO2021149025A1 (en) 2021-07-29
IT202000001378A1 (it) 2021-07-24

Similar Documents

Publication Publication Date Title
CN108164417B (zh) 制备甲基丙烯酸甲酯的方法
EP4093841B1 (de) Vollständig wiederverwendbare katalysatoren für veresterungsreaktionen
AU2008271501A1 (en) Method for producing (Meth)acrylates
KR101810384B1 (ko) 메틸 락테이트의 제조 방법
KR20130111230A (ko) 글리세롤 또는 글리세린으로부터 아크롤레인을 제조하는 방법
CN116116402B (zh) 一种催化剂，其制备方法以及采用其催化甲醇和丙烯酸甲酯制备3-甲氧基丙酸甲酯的方法
KR102644402B1 (ko) 2,6-나프탈렌디카르복실산의 제조 방법
PL82745B1 (de)
WO2014123711A1 (en) Homogeneous catalysts for biodiesel production
CN105658613A (zh) 多元醇酯的后处理方法
US4350668A (en) Recovery of cobalt component from 3-pentenoic ester synthesis
CA2964273C (en) Heterogeneous catalyst for transesterification and method of preparing same
JP2008174483A (ja) カルボン酸多価アルコールエステルの製造方法
JP4780835B2 (ja) アルコキシル化非イオン界面活性剤の製造方法
JP4092406B2 (ja) カルボン酸エステルの製造方法及びエステル化触媒
JP2859957B2 (ja) ジヒドロキシエステルの製造方法
CN108863793B (zh) 一种乙酸异丙酯的制备方法
CA1288439C (en) Method of synthesizing esters
EP1713754A2 (de) Verfahren zur herstellung von 3-alkoxy-1-propanolen und durch das produktionsverfahren erhaltene 3-alkoxy-1-propanole
JP5762327B2 (ja) ２，５−ジヒドロキシテレフタル酸の製造方法
WO2008147596A1 (en) Isopropyl alcohol from propylene using zirconium based mixed metal oxides
CN112979463B (zh) 一种离子液体催化酯化合成酯的方法
CN108586193A (zh) 一种利用3-甲氧基丙酸甲酯制备1，3-丙二醇的方法
US9187395B2 (en) Method for preparing acrolein from glycerol
CN114436828A (zh) 一种同时制备甲氧基乙酸甲酯和乙醇酸甲酯的方法

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220813

AK Designated contracting states

Kind code of ref document: A1

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

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20230517

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602021006230

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

U01 Request for unitary effect filed

Effective date: 20231122

U07 Unitary effect registered

Designated state(s): AT BE BG DE DK EE FI FR IT LT LU LV MT NL PT SE SI

Effective date: 20231130

U20 Renewal fee for the european patent with unitary effect paid

Year of fee payment: 4

Effective date: 20240124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240225

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240225

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240126

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240125

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602021006230

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20240726

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240125

U20 Renewal fee for the european patent with unitary effect paid

Year of fee payment: 5

Effective date: 20250120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20210125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20210125

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20250125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231025

U20 Renewal fee for the european patent with unitary effect paid

Year of fee payment: 6

Effective date: 20260121