EP1789378A2 - Procede d'oxyethylation catalytique - Google Patents
Procede d'oxyethylation catalytiqueInfo
- Publication number
- EP1789378A2 EP1789378A2 EP05742643A EP05742643A EP1789378A2 EP 1789378 A2 EP1789378 A2 EP 1789378A2 EP 05742643 A EP05742643 A EP 05742643A EP 05742643 A EP05742643 A EP 05742643A EP 1789378 A2 EP1789378 A2 EP 1789378A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- reactant
- ethylene oxide
- predesigned
- catalyst
- oxyethylation
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
Definitions
- This invention relates to a method for catalytic oxyethylation of organic compounds having an ester bond, enabling the efficiency of the catalysts used to be multiplied and the synthesis process to be accelerated.
- the oxyalkylation process has long been known and used commercially.
- the catalysts commonly used in the oxyalkylation processes are alkaline metal compounds, specifically sodium or potassium compounds.
- the reaction will always produce a polydisperse mixture of homologs and usually a portion of an unreacted reactant.
- Catalysts based on alkaline metals are effective as catalysts in oxyalkylation of reactants comprising a group with a so-called labile hydrogen atom although alkaline compounds are not effective as catalysts in oxyalkylation of an ester group.
- alkaline catalysts are responsible for a relatively broad homolog distribution and they usually leave a considerable amount of the unreacted reactant in the product.
- This category comprises a number of homogeneous and heterogeneous catalysts some of which have been used commercially.
- some problems are also frequently caused by a weak catalytic activity of the new type of the catalysts, which is manifested in longer times required to induce a reaction and/or in low reaction rates, specifically in the initial phases of the reaction.
- this refers to oxyethylation of esters.
- the possibility of increasing the concentrations of the said catalysts in excess is also limited because of the costs of their use on the one hand and cither the presence of an undesirable residue in the product or the expensive necessity to remove the residue on the other.
- ethylene oxide is fed depending on the reaction progress and the reaction mixture continues to be circulated until the desired conversion degree is achieved and is then discharged from the reactor.
- a preliminary reaction proceeds in a tank reactor where a desired quantity of oxirane is fed to a mixture of alcohol and catalyst and the reaction is continued in a tubular reactor, thus enabling the tubular reactor capacity to be sooner made available for handling more portions of the feed.
- the last case relates to superficial oxyethylation of low molecular alcohols.
- tubular reactors provide an opportunity to develop the heat-exchange surface in the reaction medium and to control reaction conditions by properly selecting the length of the reactor and adjusting flow rates.
- One technological solution in which the most preferable conditions for reacting gaseous and liquid reactants are favored to an extreme degree is a thin-film technology.
- a synthesis process carried out in a film reactor with a turbulent flow of the reactants provides the best possible conditions for phase-boundary mixing and diffusion of heterogeneous components.
- Thin-film reactors are mainly employed in highly exothermal processes due to their high ability to carry away the heat (DE Pat. 4128827, PL Pat. 182369).
- the catalyst in question displayed a rather weak activity in the investigated process of direct oxyethylation of esters.
- the synthesis proceeded rather slowly even at relatively high concentrations of the catalyst. Temperatures of 180°C or higher were required to induce the reaction.
- the catalytic systems referred to above were often used at high concentrations to ensure catalytic activities in the required ranges.
- Oxyethylation as a process, specifically oxyethylation of esters, is characterized by a prolonged time required to induce a reaction and a relatively low rate of conversion of ethylene oxide in the initial phase of the reaction, i.e., until an average polyaddition degree of approx. 3 moles of ethylene oxide per mole of the ester is obtained.
- Another typical phenomenon is a considerable acceleration of the rate of conversion of ethylene oxide as the oxyethylation reaction proceeds; this, for instance, is observed where the catalyst referred to in the patent P 343853 is employed.
- the situation is typical of a majority of catalysts for oxyethylation of esters and it results from the complex mechanism of the reaction that proceeds in stages.
- the catalyst's concentration relative to the oxyethylation reactant might be multiplied in a controlled manner in the initial phase of the reaction followed by reducing the catalyst's concentration relative to the reactant in the phase of fast synthesis which takes place later, thus obtaining a relatively low concentration of the catalyst in the final product.
- a predesigned total quantity of the catalyst is fed to a relatively small (preferably as small as possible) portion of the predesigned quantity of the reactant, whereafter oxyethylation is commenced by introducing a portion of the predesigned quantity of ethylene oxide to achieve the phase of fast acceleration of the conversion of ethylene oxide, i.e., activation of the catalyst that is present in a relatively high concentration in contact with the reactant and with ethylene oxide in the reaction environment.
- the synthesis process is then continued by introducing the remaining portion of the reactant and the remaining portion of ethylene oxide either in one step or gradually. Otherwise, a stream of (the remaining portion of) the reactant and a stream of ethylene oxide may be fed in parallel from the very beginning of the synthesis process.
- the gist of the invention is that, owing to the fact that the oxyethylation reaction is commenced in the presence of the entire predesigned quantity of the catalyst and a portion of the predesigned quantity of the reactant, the catalyst's concentration is many times as high in the reaction induction phase, thus enabling the reaction induction time to be minimized or eliminated and the rate of conversion of ethylene oxide in the first phase of synthesis to be increased.
- introduction of a substantial portion of the supplementary stream of the reactant and ethylene oxide as late as in the phase of the following fast reaction will not affect the conversion of ethylene oxide or the efficiency of synthesis in time, even though the activated catalyst gets relatively diluted.
- Example I shows an effective manner of oxyethylation according to the method of the invention.
- Examples II and HI show results obtained in the oxyethylation process based on a different manner of oxyethylation, known in the art.
- a 3-L stainless steel reactor is filled with 300 g of methyl esters of [fatty] acids obtained from rape seed oil (containing more than 90% of C ⁇ 8 ) and 5 g of a calcium catalyst obtained according to a method referred to in the Pat. Appl. PL 343853.
- the reactor was closed and heated to 130°C, drying the feed by purging with nitrogen for 30 minutes. When the drying operation was completed, the contents of the reactor was heated to 185°C and feeding ethylene oxide was commenced. The reaction commenced at once without any induction time and proceeded with good efficiency and without any disturbances. After 130 g (approx.
- ethylene oxide was fed another portion, i.e., 700 g of rape seed oil [fatty] acid methyl ester was introduced during 50 minutes.
- Ethylene oxide was continued to be fed: 870 g of ethylene oxide was fed in during another 60 minutes and the reactor was kept at the reaction temperature for 60 more minutes. On completion of the reaction, the material in the reactor was cooled down to 50°C, purged with nitrogen and discharged.
- FIG. 1 A diagram showing the relationship of the introduced quantity of ethylene oxide in time is shown in Fig. 1.
- Example II A diagram showing the relationship of the introduced quantity of ethylene oxide in time is shown in Fig. 1.
- Example II A diagram showing the relationship of the introduced quantity of ethylene oxide in time is shown in Fig. 1.
- Example II A diagram showing the relationship of the introduced quantity of ethylene oxide in time is shown in Fig. 1.
- Example II A diagram showing the relationship of the introduced quantity of ethylene oxide in time is shown in Fig. 1.
- Example II The synthesis was carried out as in Example I except that the reactor was filled with the total quantity of rape seed [oil fatty acid] methyl ester (1000 g) together with the catalyst (5 g) in a single step and then, as soon as the reaction temperature was achieved, feeding ethylene oxide was commenced. During 250 minutes of the synthesis merely about 280 g of ethylene oxide was introduced.
- FIG. 1 A diagram showing the relationship of the introduced quantity of ethylene oxide in time is shown in Fig. 1.
- Example II The synthesis was carried out as in Example II except that 10 g of the catalyst was introduced to the reaction which means that the concentration used was twice as high as that in Examples I and II. During 200 minutes of the synthesis merely about 1000 g of ethylene oxide was fed in.
- FIG. 1 A diagram showing the relationship of the introduced quantity of ethylene oxide in time is shown in Fig. 1.
Abstract
Selon la présente invention, une synthèse d'oxyéthylation est réalisée de telle manière qu'une quantité totale du catalyseur est acheminée vers une partie relativement petite (de préférence, plus petite que possible) de la quantité pré-attribuée du réactif. L'oxyéthylation est amorcée par introduction d'une partie de la quantité pré-attribuée d'oxyde d'éthylène en vue de parvenir à la phase d'accélération rapide de la conversion d'oxyde d'éthylène, à savoir, l'activation du catalyseur qui est présent dans une concentration relativement élevée en contact avec le réactif et avec l'oxyde d'éthylène dans l'environnement de réaction. Ce processus de synthèse se poursuit, ensuite, par introduction de la partie restante du réactif et de la partie restante d'oxyde d'éthylène en une seule étape ou progressivement. Dans le procédé de cette invention, comme la réaction d'oxyéthylation est amorcée en présence de la quantité entière pré-attribuée du catalyseur et d'une partie de la quantité pré-attribuée du réactif, la concentration du catalyseur est plusieurs fois aussi élevée en phase d'induction de la réaction, ce qui permet au temps d'induction de la réaction d'être minimisé ou éliminé et au taux de conversion de l'oxyde d'éthylène dans la première phase de synthèse d'être accru. Par ailleurs, l'introduction d'une partie importante du flux supplémentaire du réactif et de l'oxyde d'éthylène à un moment aussi tardif que dans la phase suivante de réaction rapide ne modifie pas la conversion d'oxyde d'éthylène ou l'efficacité de la synthèse, même si le catalyseur activé devient relativement dilué.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL368216A PL206132B1 (pl) | 2004-05-26 | 2004-05-26 | Sposób katalitycznego oksyetylenowania |
PCT/PL2005/000033 WO2005115964A2 (fr) | 2004-05-26 | 2005-05-25 | Procede d'oxyethylation catalytique |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1789378A2 true EP1789378A2 (fr) | 2007-05-30 |
Family
ID=34970650
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP05742643A Withdrawn EP1789378A2 (fr) | 2004-05-26 | 2005-05-25 | Procede d'oxyethylation catalytique |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1789378A2 (fr) |
PL (1) | PL206132B1 (fr) |
WO (1) | WO2005115964A2 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4273185A1 (fr) | 2022-05-04 | 2023-11-08 | PCC Rokita SA | Procédé de fabrication d'un produit de polyéther diol |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MY153870A (en) | 2008-10-29 | 2015-03-31 | Shell Int Research | Process for the preparation of acylated secondary alcohol alkoxylates and secondary alcohol alkoxylates |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5386045A (en) * | 1991-08-22 | 1995-01-31 | Vista Chemical Company | Process for alkoxylation of esters and products produced therefrom |
DE19611999C1 (de) * | 1996-03-27 | 1997-07-17 | Henkel Kgaa | Verfahren zur Herstellung alkoxylierter Fettsäurealkylester |
JP3907532B2 (ja) * | 2002-06-11 | 2007-04-18 | 株式会社日本触媒 | ヒドロキシアルキル(メタ)アクリレートの製造方法 |
-
2004
- 2004-05-26 PL PL368216A patent/PL206132B1/pl not_active IP Right Cessation
-
2005
- 2005-05-25 WO PCT/PL2005/000033 patent/WO2005115964A2/fr active Application Filing
- 2005-05-25 EP EP05742643A patent/EP1789378A2/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO2005115964A3 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4273185A1 (fr) | 2022-05-04 | 2023-11-08 | PCC Rokita SA | Procédé de fabrication d'un produit de polyéther diol |
WO2023214891A1 (fr) | 2022-05-04 | 2023-11-09 | Pcc Rokita Sa | Procédé de fabrication d'un produit de polyéther diol |
Also Published As
Publication number | Publication date |
---|---|
WO2005115964A2 (fr) | 2005-12-08 |
WO2005115964A3 (fr) | 2006-05-18 |
PL368216A1 (en) | 2005-11-28 |
PL206132B1 (pl) | 2010-07-30 |
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Legal Events
Date | Code | Title | Description |
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RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: MEXEO Owner name: SOKOLOWSKI, ADAM |
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Effective date: 20100122 |
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18D | Application deemed to be withdrawn |
Effective date: 20091201 |