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WO2002038269A1 - Catalyseur d'alcoxylenation et procede de fabrication du catalyseur d'alcoxylenation - Google Patents

Catalyseur d'alcoxylenation et procede de fabrication du catalyseur d'alcoxylenation Download PDF

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Publication number
WO2002038269A1
WO2002038269A1 PCT/PL2001/000020 PL0100020W WO0238269A1 WO 2002038269 A1 WO2002038269 A1 WO 2002038269A1 PL 0100020 W PL0100020 W PL 0100020W WO 0238269 A1 WO0238269 A1 WO 0238269A1
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Prior art keywords
catalyst
calcium
alcohol
ethoxylenation
alkoxylenation
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PCT/PL2001/000020
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English (en)
Inventor
Wieslaw Hreczuh
Kazimierz Pyzalski
Zbigniew Tomik
Janusz Wackowski
Krystyna Rolnik
Marek Lukosek
Jan Szymanowski
Wladyslaw Domarecki
Andrzej Andrysiak
Grazyna Kaczor
Barbara Naraniecka
Renata Fiszer
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Instytut Ciezkiej Syntezy Organicznej Blachownia
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Priority to AU2001241297A priority Critical patent/AU2001241297A1/en
Publication of WO2002038269A1 publication Critical patent/WO2002038269A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding

Definitions

  • This invention relates to a method to obtain a catalyst for alkoxylenation, specifically, a catalyst for ethoxylenation and propoxylenation of organic compounds having a labile hydrogen atom or an ester bond.
  • the alkoxylenation process has been well known and used commercially.
  • the catalysts commonly used are alkaline metal compounds, such as sodium or potassium hydroxides and alcoholates. The reaction will always produce a polydisperse mixture of homologs and usually a portion of an unreacted reactant.
  • Sodium and potassium compounds are widely used as catalysts in alkoxylenation reactions.
  • sodium and potassium hydroxides are most commonly used and are known to provide products with low concentrations of polyethylene glycols and dioxane.
  • products obtained in the presence of such conventional catalysts, specifically where alcohol type reactants are used have the disadvantage of the reactant leaving in the reaction product too high a content of residue that has failed to react with alkylene oxide, and a high quantity of homologs with polyaddition degrees being much different from the average degree of ethoxylenation.
  • alkaline metal catalysts will be effective in alkoxylenation of reactants containing a group with a so-called labile hydrogen group but they will not be effective in alkoxylenation of an ester group.
  • Disclosed in the EP Pat. 0092256 is a method for the synthesis of ethoxylenated alcohols, catalyzed by calcium ethanolate and sulfuric acid. The components of the catalyst were added in catalytically effective quantities, directly either to the reactant subjected to ethoxylenation or to an intermediate low molecular alcohol system; the said catalytically effective quantities were used as the catalyst without being substantially diluted, that is, without lowering their concentration in the reaction medium relative to the intermediate solution. The use of the catalyst at concentrations in the range from 0.1% to 1% relative to the ethoxylated alcohol was claimed.
  • the preparation of the said group of alcoholate catalysts usually involves addition of certain intermediate steps by separately introducing a more stable metal salt or, for instance, metallic calcium or magnesium into the reactive low molecular alcohol to obtain a low molecular alcoholate, followed by a replacement reaction effected by admixing a fatty alcohol and evaporating the low molecular alcohol at an elevated temperature to obtain a higher alcohol alcoholate.
  • a more stable metal salt or, for instance, metallic calcium or magnesium into the reactive low molecular alcohol to obtain a low molecular alcoholate
  • a replacement reaction effected by admixing a fatty alcohol and evaporating the low molecular alcohol at an elevated temperature to obtain a higher alcohol alcoholate.
  • the method disclosed in the EP Pat. 0085167 relates to the manufacture of an ethoxylenated alcohol having a narrow homolog distribution, with the use of calcium acetate or magnesium acetate as catalysts, introduced directly to the ethoxylenated alcohol at concentrations in the range 0.05% to 5% by weight of the alcohol.
  • the reaction with ethylene oxide runs rather slowly in this case, making the synthesis a lengthy process.
  • the homolog distribution remains unaffected in this case; although narrower than in a process where alkaline catalysts such as KOH are used, the homolog distribution is still rather broad.
  • a catalyst for ethoxylenation with unusually high catalytic activity, based on calcium and providing a narrow homolog distribution is disclosed in the US Pat. 4835321 and US Pat. 4775653.
  • the said group of catalysts are mixtures of calcium oxide or hydroxide with aluminum alcoholates and sulfuric acid. Preparation of the said catalyst involves, among other things, preliminary activation at an elevated temperature, even as high as 513 K, making it a burdensome and costly process.
  • the present authors have carried out a series of syntheses where calcium sulfate was introduced directly to the reactant subjected to ethoxylenation, in amounts below 0.1% relative to the lauryl alcohol subjected to ethoxylenation, and found the catalyst to show a relatively low catalytic activity with respect to the rate of the reaction; 610 g of ethylene oxide was added within 1217 minutes at 438 K to obtain a product whose average degree of polyaddition was 10.
  • 0361618, is a system comprising calcium compounds, mainly calcium oxide, calcium hydroxide and, optionally, calcium salts of carboxylic acids activated by dissolution or partial dissolution in a bi-functional solvent (activator), described by the general formula Z-X-Q-Y-Z' where Q denotes an organic radical, X and Y denote oxygen, sulfur or nitrogen while X may be identical to Y; Z and Z' denote hydrogen or organic radical, while Z may be identical to Z'.
  • Ethylene glycol is an example of the said activator described by the formula Z-X-Q-Y-Z'.
  • An oxy-salt modifier is added to the catalyst and, following its thermal treatment, the catalyst is transferred to the reactant that is subjected to ethoxylenation, to remove the excess Z-X-Q-Y-Z' activator at an elevated temperature.
  • the resulting catalyst provides a narrow homolog distribution of the products of fatty alcohol ethoxylenation.
  • polish patent PL 166429 Disclosed in the Polish patent PL 166429 is the use, as a catalyst, of mixtures comprising calcium acetate and, optionally, magnesium acetate and sulfuric acid, added directly to the reactor in catalytically effective quantities.
  • low conversion rates of ethylene oxide, around 1 mole of ethylene oxide per mole of alcohol per hour were obtained even for rather high concentrations of the catalyst (totaling, as a sum of active ingredients, about 0.6 % relative to the fatty alcohol). This is probably due to the poor solubility of calcium and magnesium acetates in the reaction medium.
  • Disclosed as an effective catalyst in the Polish patent PL 171663 is a mixture comprising calcium sulfate, calcium acetate, a low molecular calcium alcoholate and a crystalline phase being in the form of organic calcium and sulfur compounds and characterized by the presence of the following strong and medium reflections of a crystalline surface, at the following distances in the X-ray diffraction diagram: 12.1 -very strong, ⁇ .1-average, 3.6-average, 3.49-strong, 3.43, 3.33-average, 3.00-strong, 2.80-average, as well as a mixture of other crystalline derivatives of sulfur and calcium and low molecular alcohols which compounds are neutral to the course of the synthesis process.
  • the said catalyst when used in ethoxylenation of alcohols, provides products having a very low content of homologs whose polyaddition degrees are much different from the average degree of ethoxylenation.
  • the catalyst when added in a catalytically effective quantity directly to the reactant subjected to ethoxylenation in a crystalline form, the catalyst will not readily dissolve. in the reaction medium, necessitating higher concentrations and extending the duration of the synthesis initiation step.
  • a calcium catalyst was used in a mixture with addition of an ethoxylenated alcohol, inorganic acid and aluminum or titanium alcoholate.
  • Preparation of the catalyst also disclosed in the US Pat. 4775653 and US Pat. 4820673, is a complex and lengthy process, affecting significantly the costs of large-scale preparation of the catalyst.
  • German patent DE 3914131 Disclosed in the German patent DE 3914131 is calcinated hydrotalcide as an effective catalyst in ethoxylenation of esters and its further modification, obtained by using co-catalysts in the form of zinc hydroxide, alkaline earth metal salts such as magnesium carbonate or tin compounds disclosed in the German patent DE 19611999. Claimed in the US Pat. 5374750 is application of magnesium oxide in a mixture comprising from 0.1% to 10% of a specially prepared metal ion from the group comprising Al 3+ , Ga 3+ , ln 3+ , Tl 3+ , Co 3+ , Sc 3+ , La 3+ , and Mn 2+ .
  • a bi-metallic catalyst comprising magnesium compounds and oxides of the elements of groups IV and VI of the Periodic Table, such as zinc or antimony, is described in the Japanese Pat. 08323200.
  • catalytic metal compounds are rendered in a more readily soluble form via alcohol exchange by indirect preparation of low molecular alcoholates or other derivatives of so-called activators, followed by mixing with a fatty alcohol or an ester subjected to ethoxylenation, and evaporating the lower boiling component.
  • catalysts in the crystalline form or, more generally, those less readily soluble in the alkoxylenation reaction medium have so far needed additional thermal treatment to be rendered into a more readily soluble form of alcoholates, or they have been used at elevated concentrations to provide the required catalytic activity.
  • an alkoxylenation catalyst with very high activity is obtained by preparing a catalyst concentrate by homogenization of calcium salts of low molecular carboxylic or hydroxycarboxylic acids or hydrates of the former (I) and a strong oxy-acid, preferably sulfuric acid (II), in a solution of alcohols or esters (III), where the components (I) and (II) make a total of 10% to 65% by weight of the concentrate added, to obtain a visually homogeneous suspension or paste.
  • Accurate homogenization of the concentrate provides a maximum size reduction and uniform dispersion of the components of the catalyst concentrate, despite their mutually limited solubilities.
  • the alkoxylenation catalyst obtained shows high activity which, at low concentrations, enables very good dispersion in the alkoxylenation reaction medium, to eventually minimize the duration of the reaction initiation and to obtain a high conversion rate of alkylene oxide.
  • the possibility to use the catalyst at very low concentrations has a favorable effect on the quality of the resulting products and helps reduce the possible costs of removal of the catalyst residue.
  • the preparation and storage of the catalyst of the present invention in the form of a concentrate without having to subject it to additional thermal treatment are inexpensive, safe and extremely convenient operations in practice.
  • the alkoxylenation catalyst resulting from the homogenization step is in the form of a visually homogeneous, liquid suspension or a homogeneous paste and it contains:
  • the calcium salt is preferably calcium acetate and/or calcium lactate and/or hydrates of the former.
  • the catalyst preferably contains the same alcohol or ester as the one that is subjected to ethoxylenation.
  • the gist of the method of the invention is that a calcium salt of a low molecular carboxylic and/or hydroxycarboxylic acid and/or a hydrate of the former (I) is mixed with a strong oxy-acid, preferably sulfuric acid (II), and with an alcohol and/or an ester (III) at a temperature in the range 283-368 K, wherein the components (I) and (II) at a concentration in the range 10% to 65%, as well as their proportions, temperatures, time and intensity of mixing are so selected as to obtain a product in the form of a visually homogeneous, liquid suspension or a visually homogeneous paste, for use as a catalyst in the process of alkoxylenation.
  • the calcium salt used is preferably calcium acetate and/or calcium lactate and/or hydrates of the former.
  • the alcohol and/or ester used are preferably the same alcohol or ester as the ones that are subjected to ethoxylenation.
  • the alkoxylation catalyst is obtained as a concentrate in the form of a visually homogeneous liquid or paste by homogenization of so-called active ingredients of the catalyst, which make a total of 10% to 65% by weight of the concentrate added and are introduced to alcohols or esters, the said active ingredients being partially or entirely insoluble in the alcohols or esters, used for making the catalyst concentrate as well as in the reactant subjected to ethoxylenation, and where the said reactant subjected to ethoxylenation may be identical to the alcohols or esters contained in the concentrate.
  • the ingredients of the catalyst concentrate are homogenized to obtain it in the form of a visually homogeneous, liquid suspension or paste, whereupon a concentrate in such form is added, in a catalytically active quantity, to the reactant subjected to ethoxylenation.
  • the active ingredients in the method of the invention are calcium acetate, calcium lactate and/or other calcium salts of low molecular carboxylic or hydroxycarboxylic acids and/or hydrates of the former, and sulfuric acid, as well as products of their reciprocal reactions, being formed during homogenization of the active ingredients referred to hereinabove.
  • the unusually high activity of the resulting alkoxylation catalyst obtained by the method of the invention in the form of a concentrate, is substantially due to maximum size reduction and dispersion of its insoluble or sparingly soluble components. Owing to the maximum development of an interfacial contact surface of the catalyst components and to their high concentration (from 10 % to 65 % by weight) during homogenization, the occurrence of favorable physical and chemical changes that determine the possibility of efficient utilization of the active ingredients of the catalyst in the reaction medium during alkoxylation is facilitated.
  • the said high content of components in the concentrated form of the catalyst provides favorable technical conditions or a fast and efficient homogenization of the insoluble components of the catalyst and facilitates favorable chemical changes, thus enabling formation of the catalyst in a macroscopically homogeneous form.
  • Examples I - VII are embodiments of the method to manufacture the ethoxylenation catalyst by the method of the invention; the effects of its application in the process of ethoxylenation are also shown.
  • Examples VIII - XII are the results of ethoxylenation processes effected with the use of catalysts having similar compositions, though prepared by state-of-the-art methods.
  • Examples XIII- XVIII provide the compositions of catalysts obtained by the method of the invention.
  • the charging container of a colloid mill with operating capacity of 6 dm 3 is filled with 3.6 kg of isopropanol, 1.1 kg of calcium acetate monohydrate and 0.275 kg of sulfuric acid.
  • the material is mixed vigorously at ambient temperature to fully homogenize the material contained in the colloid mill.
  • the catalyst is obtained as a concentrate in the form of a visually homogeneous, milky suspension. The usefulness of the resulting catalyst is verified in the ethoxylenation reaction, which is carried out in the following manner:
  • a 2-dm 3 stainless steel reactor is filled with 300 g (1 mole) of a methyl ester of rape seed oil acids and 3.7 g of the resulting catalyst concentrate.
  • the concentration of calcium, introduced with the catalyst concentrate, is 0.06 % relative to the methyl ester of rape seed oil acids added (which contains more than 90% of C-i ⁇ fraction).
  • the reactor is then tightly closed and the material contained therein is heated to 403 K, while drying the feed by purging with nitrogen for 30 minutes. On completion of the drying step, the material contained in the reactor is heated to 438 K and ethylene oxide is added. After a short initiation step, the reaction proceeds undisturbed, with good yield.
  • the product Having added the planned amount, 440 g (10 moles) of ethylene oxide, the product is kept at the reaction temperature for 60 more minutes, whereupon the material contained in the reactor is cooled down to 323 K, blown with nitrogen and discharged.
  • the average conversion rate of ethylene oxide is 4.1 mole per mole of ester per hour.
  • the resulting ethoxylenation product with a narrow homolog distribution has a fractional composition as shown in Table 1.
  • the charging container of a colloid mill with operating capacity of 6 dm 3 is filled with 1.125 kg of isopropanol, 2.5 kg of coconut alcohol having C12 -C14 fractions, 1.1 kg of calcium lactate and 0.275 kg of sulfuric acid.
  • the material is mixed vigorously at ambient temperature to fully homogenize the material contained in the colloid mill.
  • the catalyst is obtained as a concentrate in the form of a visually homogeneous, thick suspension. The usefulness of the resulting catalyst is verified in the ethoxylenation reaction:
  • a 2-dm 3 stainless steel reactor is filled with 300 g of coconut alcohol having C12 -C14 fractions, and 4.8 g of the catalyst concentrate. Consequently, the concentration of calcium is 0.06 % relative to the C12 -C14 fractions of alcohol added.
  • the reactor is then tightly closed and the material contained therein is heated to 403 K, while drying the feed by purging with nitrogen for 30 minutes. On completion of the drying step, the material contained in the reactor is heated to 438 K and ethylene oxide is added. After a short initiation step, the reaction proceeds undisturbed, with good yield.
  • the product Having added the planned amount, 660 g of ethylene oxide, the product is kept at the reaction temperature for 60 more minutes, whereupon the material contained in the reactor is cooled down to 323 K, blown with nitrogen and discharged.
  • the average conversion rate of ethylene oxide is 5.46 mole per mole of alcohol per hour.
  • the resulting ethoxylation product with a narrow homolog distribution has a fractional composition as shown in Table 1.
  • the container of a laboratory homogenizer is filled with 50.0 g of the mixture of C12 -C14 fraction alcohols being ethoxylenated, 22.5 g of isopropanol, 22 g of calcium acetate monohydrate and 5.5 g of sulfuric acid.
  • the material is mixed vigorously at 303 K to fully homogenize the components.
  • the catalyst is obtained as a concentrate in the form of a visually homogeneous, thick suspension.
  • a synthesis is carried out with the use of the resulting catalyst, as described in Example II, except that 2.43 g of the resulting concentrate is added to 300 g of the mixture of C12 -C14 fraction alcohols. Consequently, the concentration of calcium is 0.01 % relative to the C12 -C14 fraction of alcohols added. 670 g of ethylene oxide at an average rate of 4.23 mole per mole of alcohol per hour is added during the synthesis reaction.
  • the container of a laboratory homogenizer is filled with 15.8 g of isopropanol, 65 g of methyl ester of rape seed oil acids subjected to ethoxylenation, 15.4 g of calcium acetate monohydrate and 3.8 g of sulfuric acid.
  • the material is mixed vigorously at ambient temperature to fully homogenize the components. After several minutes the catalyst is obtained as a concentrate in the form of a visually homogeneous, thick suspension.
  • the container of a laboratory homogenizer is filled with 90.0 g of isopropanol, 8.0 g of calcium acetate monohydrate and 2.0 g of sulfuric acid.
  • the material is mixed vigorously at 303 K to fully homogenize the components. After several minutes the catalyst is obtained as a concentrate in the form of a visually homogeneous, thick suspension.
  • the container of a laboratory homogenizer is filled with 35.0 g of the mixture of C12 -C14 fraction alcohols being ethoxylenated, 54 g of calcium acetate monohydrate and 13.0 g of sulfuric acid. After mixing the material in the homogenizer for several minutes at 308 K to fully homogenize the components, the catalyst is obtained as a concentrate in the form of a visually homogeneous paste.
  • An ethoxylate synthesis reaction is carried out in the presence of the resulting catalyst, as described in Example II, except that 0.81 g of the resulting catalyst concentrate is added to 300 g of the mixture of C12 — C14 fraction alcohols. Consequently, the concentration of calcium is 0.03 % relative to the C12 ⁇ Ci4 fraction of alcohols added. 440 g of ethylene oxide at an average rate of 4.54 mole per mole of alcohol per hour is added during the synthesis reaction.
  • the container of a laboratory homogenizer is filled with 80.0 g of butanol, 16.0 g of calcium acetate monohydrate and 4.0 g of sulfuric acid. After mixing the material in the homogenizer for severalminutes to fully homogenize the components, the catalyst is obtained as a concentrate in the form of a visually homogeneous, milky suspension.
  • Example II An ethoxylation reaction with the use of the resulting catalyst is conducted as in Example II, except that 15.0 g of the catalyst is added to 300 g of n-butanol.
  • the concentration of calcium is 0.17 % relative to the n-butanol added.
  • Step II 714 g of the mixture of ethylene oxide and propylene oxide in a ratio of 1:1 by weight is added to 300 g of the product of Step I of the synthesis process, yielding a product with an average polyaddition degree of 15.1 mole of a mixture of alkylene oxide per 1 mole of butanol, with an average rate of conversion of the mixture of ethylene oxide and propylene oxide of 3.01 mole per mole of alcohol per hour.
  • Example I For comparison, the ethoxylation reaction is carried out as in Example I except that the catalyst in similar concentrations is added in the form of separate active ingredients that may result from a reaction of sulfuric acid with calcium acetate in the making of the catalyst concentrate, directly to the material being subjected to ethoxylenation:
  • the ethoxylenation reaction is carried out as in Example II except that calcium sulfate is the catalyst, and is added directly to the alcohol being subjected to ethoxylenation: 0.27 g of calcium sulfate is added to 300 g of C12 -C14 fraction alcohols. Consequently, the concentration of calcium is 0.026 % relative to the C12 -CM fraction of alcohols added. 660 g of ethylene oxide at an average rate of 0.49 mole per mole of alcohol per hour is added during the synthesis reaction.
  • Example II For comparison, the ethoxylenation reaction is carried out as in Example II except that calcium acetate monohydrate is the catalyst, and is added directly to the alcohol being subjected to ethoxylenation:
  • Example II For comparison, the ethoxylenation reaction is carried out as in Example II except that calcium acetate monohydrate and calcium sulfate are used as the catalyst, and are added directly to the alcohol being subjected to ethoxylenation:
  • Example II For comparison, the ethoxylenation reaction is carried out as in Example II except that calcium acetate monohydrate and sulfuric acid are used as the catalyst, and are added directly to the alcohol being subjected to ethoxylenation:
  • the ethoxylenation catalyst in the form of a homogeneous, milky suspension contains 72.5 % by weight of isopropanol, 22.0 % by weight of calcium acetate monohydrate and 5,5 % by weight of sulfuric acid, or products of their reciprocal reactions, being formed on homogenization.
  • the ethoxylenation catalyst in the form of a thick, homogeneous suspension contains 22.5 % by weight of isopropanol, 50 % by weight of a mixture of fraction C12 -CM alcohols, 22 % by weight of calcium lactate and 5,5 % by weight of sulfuric acid, products of their reciprocal reactions, being formed on homogenization.
  • the ethoxylenation catalyst in the form of a thick, homogeneous suspension contains 15.4 % by weight of calcium acetate monohydrate, 3,8 % by weight of sulfuric acid, 15.8 % by weight of isopropanol and 65 % by weight of methyl ester of rape seed oil acids, or products of their reciprocal reactions, being formed on homogenization.
  • the ethoxylenation catalyst in the form of a thick, homogeneous suspension contains 8.0 % by weight of calcium acetate monohydrate, 2.0 % by weight of sulfuric acid and 90 % by weight of isopropanol, or products of their reciprocal reactions, being formed on homogenization.
  • the ethoxylenation catalyst in the form of a thick, homogeneous suspension contains 52.0 % by weight of calcium acetate monohydrate, 13.0 % by weight of sulfuric acid and 35 % by weight of a mixture of C12 -CM alcohols, or products of their reciprocal reactions, being formed on homogenization.
  • the number denotes the quantity of oxyethylene groups attached to an alcohol or ester molecule, for example R/3 denotes an ethoxylate having 3 oxyethylene groups.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

L'invention concerne un catalyseur d'éthoxylation sous forme d'une suspension liquide, visuellement homogène ou d'une pâte homogène, qui contient les éléments suivants : des sels de calcium d'acides carboxyliques ou hydrocarboxyliques de faible masse moléculaire ou des hydrates de ceux-ci, de l'acide sulfurique et un alcool et/ou un ester, ou des produits de leurs réactions réciproques, formés lors de l'homogénéisation, le sel de calcium et l'acide sulfurique présentant une concentration totale comprise dans la gamme de 10 à 65 % en poids. L'invention concerne également un procédé de fabrication du catalyseur d'alcoxylènation, selon lequel le sel de calcium d'un acide carboxylique ou hydrocarboxylique de faible masse moléculaire ou un hydrate (I) de celui-ci est mélangé à de l'acide sulfurique (II), à un alcool et/ou un ester (III), à une température comprise entre 283 et 368 K, les constituants (I) et (II) présentant des concentrations comprises dans la gamme de 10 % à 65 % en poids, leurs proportions, températures, périodes et intensité de mélange étant choisies de sorte à obtenir un produit sous la forme d'une suspension liquide, visuellement homogène ou d'une pâte visuellement homogène, destinée à être utilisée comme catalyseur dans le processus d'alcoxylènation.
PCT/PL2001/000020 2000-11-13 2001-03-13 Catalyseur d'alcoxylenation et procede de fabrication du catalyseur d'alcoxylenation WO2002038269A1 (fr)

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AU2001241297A AU2001241297A1 (en) 2000-11-13 2001-03-13 An alkoxylenation catalyst and a method to manufacture the alkoxylenation catalyst

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PL34385300A PL343853A1 (en) 2000-11-13 2000-11-13 Oxyalkylenation catalyst and method of obtaining same
PLP-343853 2000-11-13

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1778397A1 (fr) * 2004-08-26 2007-05-02 Huntsman Petrochemical Corporation Catalyseurs d'alkoxylation a base de terres alcalines
EP2181763A1 (fr) * 2008-10-29 2010-05-05 Shell Internationale Research Maatschappij B.V. Catalyseur et procédé d'alcoxylation
WO2010049465A1 (fr) * 2008-10-29 2010-05-06 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'alcoxylates d'alcools secondaires acylés et alcoxylates d'alcools secondaires
US8034979B2 (en) 2004-09-23 2011-10-11 Monsanto Technology Llc Alkoxylated alkylamines/alkyl ether amines with peaked distribution
WO2012028435A1 (fr) 2010-09-02 2012-03-08 Kolb Distribution Ltd. Procédé d'alcoxylation d'esters alkyliques d'acides gras
KR20150003152A (ko) 2012-04-13 2015-01-08 라이온 가부시키가이샤 알콕실화 촉매, 상기 촉매의 제조 방법, 및 상기 촉매를 사용한 지방산 알킬에스테르알콕실레이트의 제조 방법
CN111068773A (zh) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 脂肪酸甲酯乙氧基化催化剂及其应用
WO2020239750A1 (fr) * 2019-05-28 2020-12-03 Clariant International Ltd Esters de glycérol éthoxylés et procédé de production associé

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EP1778397A4 (fr) * 2004-08-26 2008-08-27 Huntsman Spec Chem Corp Catalyseurs d'alkoxylation a base de terres alcalines
US7629487B2 (en) 2004-08-26 2009-12-08 Huntsman Petrochemical Llc Alkaline earth-based alkoxylation catalysts
EP1778397A1 (fr) * 2004-08-26 2007-05-02 Huntsman Petrochemical Corporation Catalyseurs d'alkoxylation a base de terres alcalines
US8034979B2 (en) 2004-09-23 2011-10-11 Monsanto Technology Llc Alkoxylated alkylamines/alkyl ether amines with peaked distribution
US8357636B2 (en) 2004-09-23 2013-01-22 Akzo Nobel N.V. Alkoxylated alkylamines/alkyl ether amines with peaked distribution
WO2010049465A1 (fr) * 2008-10-29 2010-05-06 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'alcoxylates d'alcools secondaires acylés et alcoxylates d'alcools secondaires
CN102203049A (zh) * 2008-10-29 2011-09-28 国际壳牌研究有限公司 用于制备酰化仲醇烷氧化物和仲醇烷氧化物的方法
EP2181763A1 (fr) * 2008-10-29 2010-05-05 Shell Internationale Research Maatschappij B.V. Catalyseur et procédé d'alcoxylation
US8664423B2 (en) 2008-10-29 2014-03-04 Shell Oil Company Process for the preparation of acylated secondary alcohol alkoxylates and secondary alcohol alkoxylates
RU2510964C2 (ru) * 2008-10-29 2014-04-10 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Способ получения ацилированных алкоксилатов вторичных спиртов и алкоксилатов вторичных спиртов
WO2012028435A1 (fr) 2010-09-02 2012-03-08 Kolb Distribution Ltd. Procédé d'alcoxylation d'esters alkyliques d'acides gras
US9056828B2 (en) 2010-09-02 2015-06-16 Kolb Distribution Ltd. Alkoxylation method of fatty acid alkyl esters
KR20150003152A (ko) 2012-04-13 2015-01-08 라이온 가부시키가이샤 알콕실화 촉매, 상기 촉매의 제조 방법, 및 상기 촉매를 사용한 지방산 알킬에스테르알콕실레이트의 제조 방법
CN111068773A (zh) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 脂肪酸甲酯乙氧基化催化剂及其应用
CN111068773B (zh) * 2018-10-18 2022-10-11 中国石油化工股份有限公司 脂肪酸甲酯乙氧基化催化剂及其应用
WO2020239750A1 (fr) * 2019-05-28 2020-12-03 Clariant International Ltd Esters de glycérol éthoxylés et procédé de production associé
CN114026059A (zh) * 2019-05-28 2022-02-08 科莱恩国际有限公司 乙氧基化甘油酯及其制备方法

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