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WO2019141778A1 - Estérification d'acides carboxyliques avec des oléfines à l'aide d'un matériau zéolithique ayant une structure de charpente de type bea - Google Patents

Estérification d'acides carboxyliques avec des oléfines à l'aide d'un matériau zéolithique ayant une structure de charpente de type bea Download PDF

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Publication number
WO2019141778A1
WO2019141778A1 PCT/EP2019/051150 EP2019051150W WO2019141778A1 WO 2019141778 A1 WO2019141778 A1 WO 2019141778A1 EP 2019051150 W EP2019051150 W EP 2019051150W WO 2019141778 A1 WO2019141778 A1 WO 2019141778A1
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Prior art keywords
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acid
formula
mixture
bea
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English (en)
Inventor
Ivana JEVTOVIKJ
Harald Roessler
Andreas Kuschel
Lukasz KARWACKI
Veronika Wloka
Xiaofan Yang
Ulrich Mueller
Joerg Rother
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta

Definitions

  • the present invention relates to a catalytic process for the preparation of an ester starting from a carboxylic acid and an alkene using a zeolitic material having a BEA-type framework structure as the catalyst.
  • esters such as fatty esters in the prior art is commonly carried out via the con- densation of fatty acids with alcohols in a homogeneously catalyzed process.
  • a state of the art process for fatty esters involves direct esterification of fatty acids (C12 and C14) with alcohol/ trans-esterification of methyl esters with alcohol in a semi-batch process, the reac- tion being homogeneously catalyzed in the presence of acidic catalysts such as sulfuric acid.
  • acidic catalysts such as sulfuric acid
  • US 5,189,201 describes the preparation of a lower fatty acid ester such as ethyl acetate or ethyl acrylate by a process in which a lower fatty acid (i.e. having up to four carbon atoms) such as acetic acid or acrylic acid is reacted with a lower olefin such as ethylene by using as solid cata- lyst a heteropoly-acid or its salt (for instance Cesium phosphotungstate).
  • a lower fatty acid i.e. having up to four carbon atoms
  • a lower olefin such as ethylene
  • WO 2010/146156 A1 relates to an organotemplate-free synthetic process for the production of a zeolitic material (zeolite beta) having a BEA framework structure comprising Y0 2 and optionally comprising X 2 0 3 , wherein Y is a tetravalent element, and X is a trivalent element.
  • zeolitic material zeolite beta
  • BEA framework structure comprising Y0 2 and optionally comprising X 2 0 3
  • Y is a tetravalent element
  • X is a trivalent element.
  • 2010/146156 A1 further relates to the use of said zeolitic material in exhaust gas treatment, preferably in the treatment of industrial or automotive exhaust gas.
  • Olefins have lower prices than the corresponding alcohol, hence give access to a more cost effective process for the production of an ester.
  • a hetero- geneous catalyst in place of a homogeneous catalyst enables a simplified process avoiding the disadvantages of semi-batch processing.
  • there remains the need for the provision of an improved process in particular with regard to the selectivity towards and the yield of the ester product.
  • a process which may be run for prolonged periods, in particular in a continuous mode while sustaining a high selectivity towards and achieving a high yield of the ester product.
  • esterifi- cation of carboxylic acids with alkenes can advantageously be carried out with a zeolitic materi- al having a BEA-framework structure as obtained from organotemplate-free synthesis as the catalyst.
  • the present invention relates to a process for production of an ester comprising: (1) preparing a mixture (M1 ) comprising a carboxylic acid of formula (I) and an alkene of formula (II)
  • R is hydrogen or an alkyl group
  • the zeolitic material having a BEA-type framework structure displays an X-ray diffrac tion pattern comprising at least the following reflections:
  • the BEA-type framework structure comprises YO 2 and X 2 O 3 , wherein Y is a tetravalent element, and X is a trivalent element.
  • the zeolitic material having a BEA-type framework structure used in the inventive process no particular restrictions apply relative to the method according to which the X-ray dif fraction is obtained for determining the diffraction angles and intensities of the reflections, pro- vided that the Cu K(alpha 1) radiation is used to this effect.
  • the inventive process it is however preferred that the X-ray diffraction pattern is obtained as described in the experi- mental section for determining the diffraction angles and intensities of the reflections displayed by the zeolitic material having a BEA-type framework structure used in the inventive process
  • R is an optionally branched and/or optionally substituted and/or optionally unsatu- rated alkyl group selected from the group consisting of optionally branched and/or optionally substituted and/or optionally unsaturated C1-C24 alkyl groups, more preferably C2-C22 alkyl groups, more preferably C4-C20 alkyl groups, more preferably C6-C18 alkyl groups, more pref- erably C8-C18 alkyl groups, more preferably C10-C16 alkyl groups, more preferably C12-C16 alkyl groups, more preferably C12-C14 alkyl groups, more preferably C12 or C14 alkyl groups, and more preferably C14 alkyl groups, wherein more preferably R is selected from the group consisting of optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decy
  • C 1 -C 24 alkyl refers to an alkyl residue having from 1 to 24 carbon atoms in the chain.
  • the alkyl residue may have, for example, 1 , 2, 3, 4, 5, or 6 carbon atoms in the chain (C 1 -C 6 alkyl) or 1 , 2, 3, or 4 carbon atoms in the chain (C 1 -C 4 alkyl).
  • R’ is an optionally branched and/or optionally substituted and/or optionally unsatu- rated alkyl group selected from the group consisting of optionally branched and/or optionally substituted and/or optionally unsaturated C1-C6 alkyl groups, more preferably C1-C5 alkyl groups, more preferably C1-C4 alkyl groups, more preferably C1-C3 alkyl groups, more prefer- ably C1-C2 alkyl groups, and more preferably C1 alkyl groups, wherein more preferably R is selected from the group consisting of optionally substituted methyl, ethyl, propyl, butyl, pentyl, and hexyl, more preferably from the group consisting of optionally substituted methyl, ethyl, propyl, butyl, and pentyl, more preferably from the group consisting of optionally substituted methyl, ethyl, propyl, and butyl, more preferably from the group consist
  • R is hydrogen or an optionally branched and/or optionally substituted and/or op- tionally unsaturated alkyl group selected from the group consisting of optionally branched and/or optionally substituted and/or optionally unsaturated C1-C6 alkyl groups, more preferably C1-C5 alkyl groups, more preferably C1-C4 alkyl groups, more preferably C1-C3 alkyl groups, more preferably C1-C2 alkyl groups, and more preferably C1 alkyl groups, wherein more preferably R is hydrogen or an alkyl group selected from the group consisting of optionally substituted me- thyl, ethyl, propyl, butyl, pentyl, and hexyl, more preferably from the group consisting of option- ally substituted methyl, ethyl, propyl, butyl, and pentyl, more preferably from the group consist- ing of optionally substituted methyl, e
  • the carboxylic acid of formula (I) is selected from the group consisting of optionally substituted formic acid, acetic acid, propionic acid, valeric acid, acrylic acid, methacrylic acid, and crotonic acid, wherein preferably the car- boxylic acid of formula (I) is optionally substituted acetic acid or acrylic acid.
  • the alkene of formula (II) is selected from the group consisting of optionally substituted ethylene, propylene, 1-butene, 2-butene, and isobu- tene, wherein more preferably the alkene of formula (II) is optionally substituted ethylene or propylene, preferably ethylene or propylene, and more preferably propylene.
  • the carboxylic acid of formula (I) is myristic acid and the alkene of formula (II) is propylene. It is alternatively preferred that the carboxylic acid of formula (I) is lauric acid and the alkene of formula (II) is propylene.
  • the carboxylic acid of formula (I) is acetic acid and the alkene of formula (II) is ethylene.
  • the carboxylic acid of formula (I) is acrylic acid and the alkene of formula (II) is ethylene.
  • the alkene : carboxylic acid molar ratio of the alkene of formula (II) to the carboxylic acid of formula (I) in the mixture (M1 ) prepared in (1) and reacted in (3) is in the range of from 0.1 : 1 to 1 : 0.1 , preferably from 0.3 : 1 to 1 : 0.3, more preferably from 0.5 : 1 to 1 : 0.5, more preferably from 0.7 : 1 to 1 : 0.7, more preferably from 0.8 : 1 to 1 : 0.8, more preferably from 0.85 : 1 to 1 : 0.85, more preferably from 0.9 : 1 to 1 : 0.9, and more preferably from 0.95 : 1 to 1 : 0.95.
  • the mixture (M1 ) prepared in (1 ) and reacted in (3) contains 50 wt.-% or less of wa- ter based on 100 wt.-% of the carboxylic acid of formula (I), preferably 20 wt.-% or less, more preferably 10 wt.-% or less, more preferably 5 wt.-% or less, more preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more prefera- bly 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt- % or less of water based on 100 wt.-% of the carboxylic acid of formula (I).
  • mol% of the carboxylic acid of formula (I) preferably 20 mol% or less, more pref- erably 10 mol% or less, more preferably 5 mol% or less, more preferably 1 mol% or less, more preferably 0.5 mol% or less, more preferably 0.1 mol% or less, more preferably 0.05 mol% or less, more preferably 0.01 mol% or less, more preferably 0.005 mol% or less, more preferably 0.001 mol% or less, more preferably 0.0005 mol% or less, and more preferably 0.0001 mol% or less of an alcohol of the formula (IV) based on 100 mol% of the carboxylic acid of formula (I).
  • the mixture (M1) prepared in (1 ) and reacted in (3) preferably contains 50 wt.% or less of ele- ments and/or compounds other than the carboxylic acid of formula (I) and the alkene of formula (II) based on 100 wt.-% of the carboxylic acid of formula (I), preferably 20 wt.-% or less, more preferably 10 wt.-% or less, more preferably 5 wt.-% or less, more preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more prefera- bly 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt- % or less of elements
  • the catalyst in the reactor preferably con- tains 200 wt.% or less of elements and/or compounds other than the zeolitic material having a BEA-type framework structure based on 100 wt.-% of the zeolitic material having a BEA-type framework structure, preferably 100 wt.-% or less, more preferably 50 wt.-% or less, more pref- erably 20 wt.-% or less, more preferably 10 wt.-% or less, more preferably 5 wt.-% or less, more preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably preferably
  • the zeolitic material having a BEA-type framework structure comprised in the catalyst contains 5 wt.-% or less of a metal AM calculated as the element and based on 100 wt.-% of YO 2 contained in the framework structure of the zeolitic material having a BEA- type framework structure, preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt.-% or less of a metal AM calculated as the element and based on 100 wt.-% of YO 2 contained in the framework structure of the zeolitic material having a BEA
  • metal AM stands for Na, preferably for Na and K, more preferably for alkali metals, and more preferably for alkali and alkaline earth metals.
  • the zeolitic material having a BEA-type framework structure comprised in the catalyst contains 5 wt.-% or less of a metal TM calculated as the element and based on 100 wt.-% of YO 2 contained in the framework structure of the zeolitic material having a BEA- type framework structure, preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt.-% or less of a metal TM calculated as the element and based on 100 wt.-% of YO 2 contained in the framework structure of the zeolitic material having a
  • metal TM stands for Pt, Pd, Rh, and Ir, and preferably stands for transition metal elements of groups 3-12.
  • the catalyst in the reactor preferably contains 5 wt.-% or less of a metal AM calcu- lated as the element and based on 100 wt.-% of the catalyst, preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt.-% or less of a metal AM calculated as the element and based on 100 wt.-% of the catalyst, wherein the metal AM stands for Na, preferably for Na and K, more preferably for alkali metals, and more preferably for alkali and alkaline earth metals.
  • the catalyst contained in the reactor contains 5 wt.-% or less of a metal TM calculated as the element and based on 100 wt.-% of the catalyst, preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt.-% or less of a metal TM calculated as the element and based on 100 wt.-% of the catalyst,
  • the metal TM stands for Pt, Pd, Rh, and Ir, and preferably stands for transition metal elements of groups 3-12.
  • the zeolitic material having a BEA-type framework structure comprised in the catalyst contains 5 wt.% or less of phosphorous calculat- ed as the element and based on 100 wt.-% of Y0 2 contained in the framework structure of the zeolitic material having a BEA-type framework structure, preferably 1 wt.-% or less, more pref- erably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt.-% or less of phospho
  • the catalyst preferably contains 5 wt.% or less of phosphorous calculated as the element and based on 100 wt.-% of the catalyst, preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt.-% or less of a metal AM calculated as the element and based on 100 wt.-% of the catalyst.
  • the contacting of the mixture (M1) with the catalyst in (3) is conducted at a temperature in the range of from 80 to 250°C, preferably from 85 to 220°C, more preferably from 90 to 200°C, more preferably from 95 to 180°C, more preferably from 100 to 170°C, more preferably from 105 to 160°C, more preferably from 1 10 to 150°C, more preferably from 115 to 145°C, more preferably from 120 to 140°C, and more pref- erably in the range of from 125 to 135°C.
  • the contacting of the mixture (M1 ) with the catalyst in (3) is conducted at a pressure in the range of from 2 to 50 bar, preferably from 3 to 30 bar, more preferably from 4 to 25 bar, more preferably from 5 to 20 bar, more preferably from 6 to 17 bar, more preferably from 7 to 15 bar, more preferably from 7.5 to 13 bar, more prefera- bly from 8 to 12 bar, more preferably from 8.5 to 1 1.5 bar, more preferably from 9 to 1 1 bar, and more preferably in the range of from 9.5 to 10.5 bar.
  • the duration of the contacting of the mixture (M1 ) with the catalyst in (3) is in the range of from 0.05 to 12 h, preferably from 0.1 to 9 h, more preferably from 0.25 to 8 h, more preferably from 0.5 to 7.5 h, more preferably from 1 to 7 h, more preferably from 1.5 to 6.5 h, more preferably from 2 to 6 h, more preferably from 2.5 to 5.5 h, more preferably from 3 to 5 h, more preferably from 3.5 to 4.5 h, and more prefera- bly in the range of from 3.75 to 4.25 h.
  • the contacting of the mixture (M1) with the catalyst in (3) and the collecting of the reacted mixture (M2) in (4) is conducted in a continu- ous mode and/or in a batch mode, preferably in a continuous mode.
  • the process is conducted in a continuous mode and/or in a batch mode, more pref- erably in a continuous mode.
  • the process is conducted in a continuous mode at a weight hourly space velocity (WHSV) in the range of from 0.08 to 20 lv 1 , preferably from 0.09 to 15 Ir 1 , more preferably from 0.1 to 10 lv 1 , more preferably from 0.12 to 8 lv 1 , more preferably from 0.14 to 5 lv 1 , more preferably from 0.16 to 3 lv 1 , more preferably from 0.18 to 1 lv 1 , more preferably from 0.2 to 0.5 Ir 1 , more preferably from 0.22 to 0.3 Ir 1 , and more preferably in the range of from 0.24 to 0.26 Ir 1 .
  • WHSV weight hourly space velocity
  • the process preferably further comprises:
  • the process preferably further comprises:
  • the present invention further relates to a process for produc- tion of an ester starting from a dicarboxylic acid comprising:
  • R’ is an alkyl group
  • R is hydrogen or an alkyl group
  • R’ is an alkylene group
  • the zeolitic material having a BEA-type framework structure displays an X-ray diffrac tion pattern comprising at least the following reflections:
  • the BEA-type framework structure comprises YO 2 and X 2 O 3 , wherein Y is a tetravalent element, and X is a trivalent element.
  • R’ is a single bond or is is an optionally branched and/or optionally substituted and/or optionally unsaturated alkylene group selected from the group consisting of optionally branched and/or optionally substituted and/or optionally unsaturated C1-C16 alkylene groups, preferably C1-C14 alkylene groups, more preferably C1-C12 alkylene groups, more preferably C1-C10 alkylene groups, more preferably C2-C9 alkylene groups, more preferably C2-C8 al- kylene groups, more preferably C2-C7 alkylene groups, more preferably C3-C6 alkylene groups, more preferably C3-C5 alkylene groups, more preferably C3 or C4 alkylene groups, and more preferably C4 alkylene groups, wherein more preferably R’” is selected from the group consisting of optionally substituted methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene,
  • R’ is an optionally branched and/or optionally substituted and/or optionally un- saturated C1-C18 alkyl groups, preferably C2-C16 alkyl groups, more preferably C3-C14 alkyl groups, more preferably C4-C12 alkyl groups, more preferably C5-C10 alkyl groups, more pref- erably C6-C9 alkyl groups, more preferably C7 or C8 alkyl groups, and more preferably C8 alkyl groups, wherein more preferably R’ is selected from the group consisting of optionally substitut- ed methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, and hexadecyl, more preferably from the group consisting of
  • the alkene of formula (II) is selected from the group consisting of optionally substi- tuted C2-C18 alkene, preferably C3-C16 alkene, more preferably C4-C14 alkene, more prefera- bly C5-C12 alkene, more preferably C6-C10 alkene, more preferably C7-C9 alkene, more pref- erably C7 or C8 alkene, and more preferably C10 alkene, wherein more preferably the alkene of formula (II) is selected from the group consisting of optionally substituted ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, and hexa
  • the carboxylic acid of formula (G) is selected from the group consisting of optionally substituted oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane- dioic acid, and dodecanedioic acid, preferably from the group consisting of optionally substituted succinic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid, wherein more preferably the carboxylic acid of formula (G) is optionally substituted glutaric or adipic acid, preferably glu taric or adipic acid, and more preferably adipic acid.
  • the alkene : carboxylic acid molar ratio of the alkene of formula (II) to the carboxylic acid of formula (G) in the mixture (M1 ) prepared in (1 ) and reacted in (3) is in the range of from 0.1 : 1 to 20 : 1 , preferably from 0.5 : 1 to 15 : 1 , more preferably from 1 : 1 to 10 : 1 , more pref- erably from 1.3 : 1 to 5 : 1 , more preferably from 1.5 : 1 to 3 : 1 , more preferably from 1.7 : 1 to 2.5 : 1 , more preferably from 1.9 : 1 to 2.3 : 1 , and more preferably from 1.95 : 1 to 2.1 : 1.
  • the mixture (M1 ) prepared in (1) and reacted in (3) contains 50 wt.-% or less of water based on 100 wt.-% of the carboxylic acid of formula (G), preferably 20 wt.-% or less, more preferably 10 wt.-% or less, more preferably 5 wt.-% or less, more preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt.-% or less of water based on 100 wt.-% of the carboxylic acid of formula (G), preferably 20 wt.-% or less, more preferably
  • the mixture (M1 ) prepared in (1) and reacted in (3) comprises 50 mol% or less of an alcohol of formula (IV)
  • mol% of the carboxylic acid of formula (I’) preferably 20 mol% or less, more pref- erably 10 mol% or less, more preferably 5 mol% or less, more preferably 1 mol% or less, more preferably 0.5 mol% or less, more preferably 0.1 mol% or less, more preferably 0.05 mol% or less, more preferably 0.01 mol% or less, more preferably 0.005 mol% or less, more preferably 0.001 mol% or less, more preferably 0.0005 mol% or less, and more preferably 0.0001 mol% or less of an alcohol of the formula (IV) based on 100 mol% of the carboxylic acid of formula (G).
  • the mixture (M1) prepared in (1 ) and reacted in (3) contains 50 wt.% or less of ele- ments and/or compounds other than the carboxylic acid of formula (G) and the alkene of formula (II) based on 100 wt.-% of the carboxylic acid of formula (G), preferably 20 wt.-% or less, more preferably 10 wt.-% or less, more preferably 5 wt.-% or less, more preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more prefera- bly 0.001 wt.-% or less, more preferably 0.0005
  • the mixture (M1) prepared in (1 ) and reacted in (3) consists of a mixture of the car- boxylic acid of formula (G) and the alkene of formula (II).
  • the contacting of the mixture (M1 ) with the catalyst in (3) is conducted at a tem- perature in the range of from 80 to 250°C, preferably from 100 to 230°C, more preferably from 1 10 to 210°C, more preferably from 120 to 200°C, more preferably from 130 to 190°C, more preferably from 140 to 180°C, more preferably from 145 to 175°C, more preferably from 150 to 170°C, and more preferably in the range of from 155 to 165°C.
  • the process further comprises:
  • the zeolitic material having a BEA- type framework structure comprised in the catalyst displays a YO 2 : X 2 O 3 molar ratio in the range of from 2 to 300, preferably from 4 to 200, more preferably from 6 to 150, more preferably from 8 to 100, more preferably from 12 to 70, more preferably from 14 to 50, more preferably from 16 to 40, more preferably from 18 to 35, more preferably from 20 to 30, and more prefera- bly from 22 to 26.
  • Y may be any tetravalent element.
  • the tetra- valent element Y of the zeolitic material having a BEA-type framework structure comprised in the catalyst is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and a mixture of two or more thereof, Y more preferably being Si.
  • X may be any trivalent element.
  • the trivalent element X of the zeolitic material having a BEA-type framework structure comprised in the cata- lyst is selected from the group consisting of Al, B, In, Ga, and a mixture of two or more thereof, X more preferably being Al.
  • the zeolitic material having a BEA-type framework structure comprised in the cata- lyst has a total amount of acid sites in the range of from 0.25 to 1.0 mmol/g, preferably from 0.15 to 0.8 mmol/g, more preferably from 0.2 to 0.7 mmol/g, more preferably from 0.25 to 0.6 mmol/g, more preferably from 0.3 to 0.55 mmol/g, more preferably from 0.35 to 0.5 mmol/g, more preferably from 0.38 to 0.45 mmol/g, and more preferably from 0.4 to 0.42 mmol/g, wherein the total amount of acid sites is defined as the total molar amount of desorbed ammo- nia per mass of the zeolitic material determined according to the temperature programmed de- sorption of ammonia (NH 3 -TPD).
  • NH 3 -TPD temperature programmed de- sorption of ammonia
  • the zeolitic material having a BEA-type framework structure comprised in the cata- lyst has an amount of medium acid sites, wherein the amount of medium acid sites is defined as the amount of desorbed ammonia per mass of the zeolitic material determined according to the temperature programmed desorption of ammonia (NH 3 -TPD) in the temperature range of from 250 to 500 °C, wherein the amount of medium acid sites is at least 40% of the total amount of acid sites, preferably from 42 to 90%, more preferably from 44 to 80%, more preferably from 46 to 75%, more preferably from 48 to 70%, more preferably from 50 to 65%, more preferably from 53 to 60%, and more preferably from 55 to 57% of the total amount of acid sites.
  • the amount of medium acid sites is defined as the amount of desorbed ammonia per mass of the zeolitic material determined according to the temperature programmed desorption of ammonia (NH 3 -TPD) in the temperature range of from 250 to 500 °C, wherein the amount of medium acid
  • the amount of medium acid sites is in the range of from 0.10 to 0.90 mmol/g, preferably from 0.12 to 0.7 mmol/g, more preferably from 0.14 to 0.5 mmol/g, more preferably from 0.16 to 0.4 mmol/g, more preferably from 0.18 to 0.3 mmol/g, more preferably from 0.2 to 0.26 mmol/g, and more preferably from 0.22 to 0.24 mmol/g.
  • the zeolitic material having a BEA-type framework structure comprised in the cata- lyst has an amount of strong acid sites, preferably the amount of strong acid sites of the zeolitic material having a BEA-type framework structure comprised in the catalyst, defined as the amount of desorbed ammonia per mass of the zeolitic material determined according to the temperature programmed desorption of ammonia (NH 3 -TPD) in the temperature range above 500 °C, preferably in the range of from 0 to 0.10 mmol/g, preferably from 0.00 to 0.07 mmol/g, more preferably from 0.00 to 0.05 mmol/g, more preferably from 0.00 to 0.04 mmol/g, more preferably from 0.00 to 0.03 mmol/g, more preferably from 0.00 to 0.02 mmol/g, more preferably from 0.00 to 0.015 mmol/g, more preferably from 0.00 to 0.01 mmol/g, and more preferably from 0.00 to 0.005
  • the total amount of acid sites as well as the amount of medium acid sites and the amount of strong acid sites as used herein may readily be measured by known methods, preferably by temperature-programmed desorption of ammonia (NH 3 -TPD), preferably with an automated chemisorption analysis unit having a thermal conductivity detector, preferably by continuous analysis of the desorbed species by an online mass spectrometer, preferably the temperature being measured by a Ni/Cr/Ni thermocouple immediately above the sample in a quartz tube, more preferably wherein the online mass spectrometer monitors the desorption of ammonia by utilizing the molecular weight of ammonia of 16, wherein more preferably the automated chemi- sorption analysis unit is a Micromeritics AutoChem II 2920, wherein more preferably the online mass spectrometer is a OmniStar QMG200 from Pfeiffer Vacuum.
  • NH 3 -TPD temperature-programmed desorption of ammonia
  • said measurement comprises 1. a preparation step, 2. a saturation with NH 3 step, 3. a step wherein excess ammo- nia is removed and 4. a NH 3 -TPD step, more preferably wherein the 4. NH 3 -TPD step for the total amount of acid sites comprises heating under a He flow to 600 °C, preferably at a heating rate of 10 K/min, preferably wherein the temperature of 600 °C is then held for 30 minutes. It is more preferred that for determining the amount of medium acid sites, said 4. NH 3 -TPD step is carried out at the temperature range of from 250 to 500 °C. It is more preferred that for deter- mining the amount of strong acid sites, said 4.
  • NH 3 -TPD step is carried out in the temperature range above 500 °C. According to the present invention it is more preferred that the total amount of acid sites as well as the amount of medium acid sites and the amount of strong acid sites as used herein are determined according to the method described herein in the examples under“determination of the acid sites”.
  • the ratio of the amount of medium acid sites relative to amount of strong acid sites is greater than 0, preferably 10 or greater, more preferably 50 or greater, more preferably 100, more preferably 10 3 or greater, more preferably 10 4 or greater, more preferably 10 5 or greater, more preferably 10 6 or greater, more preferably 10 7 or greater, more preferably 10 8 or greater, and more preferably 10 9 or greater.
  • the zeolitic material having a BEA-type framework structure is obtainable and/or obtained according to an organotemplate-free synthetic process.
  • organotemplate-free synthetic process comprises
  • mixture prepared in (A) and crystallized in (B) does not contain an organotemplate as structure-directing agent.
  • the mixture prepared in (A) and crystallized in (B) contains 5 wt.-% or less of carbon calculated as the element and based on 100 wt.-% of Y contained in the mixture, preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more prefer- ably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt.-% or less of carbon calculated as the element and based on 100 wt.-% of Y con- tained in the mixture.
  • the zeolitic material having a BEA-type framework structure obtained in (B) comprises one or more alkali metals M, wherein M is preferably selected from the group consisting of Li, Na, K, Cs, and combinations of two or more thereof, more preferably from the group consisting of Li, Na, K, and combinations of two or more thereof, wherein more preferably the alkali metal M is Na and/or K, more preferably Na.
  • M is preferably selected from the group consisting of Li, Na, K, Cs, and combinations of two or more thereof, more preferably from the group consisting of Li, Na, K, and combinations of two or more thereof, wherein more preferably the alkali metal M is Na and/or K, more preferably Na.
  • the molar ratio M : YO 2 in the mixture prepared in (A) and crystallized in (B) is in the range of from 0.05 to 5, preferably from 0.1 to 2, more preferably from 0.3 to 1 , more preferably from 0.4 to 0.8, more preferably from 0.45 to 0.7, more preferably from 0.5 to 0.65, and more preferably from 0.55 to 0.6.
  • Y may be any tetravalent element.
  • Y is se- lected from the group consisting of Si, Sn, Ti, Zr, Ge, and a mixture of two or more thereof, Y more preferably being Si.
  • any suitable one or more sources of YO 2 can be used.
  • the one or more sources for YO 2 contained in the mixture prepared in (A) and crystallized in (B) comprises one or more silicates, more preferably one or more alkali metal silicates, wherein the alkali metal is preferably selected from the group consisting of Li,
  • the alkali metal is Na and/or K, and wherein more preferably the alkali metal is Na
  • the one or more sources for YO 2 con- tained in the mixture prepared in (A) and crystallized in (B) comprises water glass, preferably sodium and/or potassium silicate, more preferably sodium silicate.
  • the one or more sources for YO 2 contained in the mixture prepared in (A) and crystallized in (B) further compris- es one or more silicas, more preferably one or more silica hydrosols and/or one or more colloi dal silicas, and more preferably one or more colloidal silicas.
  • X may be any trivalent element.
  • X is selected from the group consisting of Al, B, In, Ga, and a mixture of two or more thereof, X more prefera- bly being Al.
  • any suitable one or more sources of X 2 O 3 can be used.
  • the one or more sources for X 2 O 3 contained in the mixture prepared in (A) and crys- tallized in (B) comprises one or more aluminate salts, preferably an aluminate of an alkali metal, wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb, and Cs, wherein more preferably the alkali metal is Na and/or K, and wherein more preferably the alkali metal is Na.
  • the molar ratio YO 2 : X 2 O 3 of the mix- ture prepared in (A) and crystallized in (B) is in the range of from 1 to 200, preferably from 5 to 100, more preferably from 10 to 50, more preferably from 15 to 40, more preferably from 20 to 30, more preferably from 23 to 25, and more preferably from 23.5 to 24.
  • the amount of seed crystals comprised in the mixture prepared in (A) and crystallized in (B) is in the range of from 0.1 to 30 wt.-% based on 100 wt.-% of the one or more sources of YO 2 in the mixture, calculated as YO 2 , preferably from 0.5 to 20 wt.-%, more prefera- bly from 1 to 10 wt.-%, more preferably from 1.5 to 5 wt.-%, more preferably from 2 to 4 wt.-%, and more preferably from 2.5 to 3.5 wt.-%.
  • the mixture prepared in (A) and crystallized in (B) further comprises one or more solvents, wherein said one or more solvents preferably comprises water, more preferably deion- ized water, wherein more preferably water is employed as the solvent further comprised in the mixture prepared in (A) and crystallized in (B), preferably deionized water.
  • the molar ratio H 2 0 : YO 2 of the mixture prepared in (A) and crystallized in (B) is in the range of from 5 to 100, preferably from 10 to 50, more preferably from 13 to 30, more preferably from 15 to 20, and more preferably from 17 to 18.
  • the crystallization in (B) involves heating of the mixture, prefera- bly at a temperature in the range of from 80 to 200°C, more preferably from 90 to 180°C, more preferably from 100 to 160°C, more preferably from 1 10 to 140°C, and more preferably from 1 15 to 130°C.
  • the crystallization in (B) is conducted under autogenous pressure, preferably under solvothermal conditions, and more preferably under hydrothermal conditions.
  • the mixture is preferably heated for a period in the range of from 5 to 200 h, preferably from 20 to 160 h, more preferably from 60 to 140 h, and more preferably from 100 to 130 h.
  • the organotemplate-free synthetic process for the prepa- ration of the zeolitic material having a BEA-type framework structure preferably further compris- es
  • steps (C) and/or (D) and/or (E) can be conducted in any order, and
  • one or more of said steps is preferably repeated one or more times.
  • the organotemplate-free synthetic process for the prepa- ration of the zeolitic material having a BEA-type framework structure preferably further compris- es
  • the organotemplate-free synthetic process for the prepa- ration of the zeolitic material having a BEA-type framework structure preferably further compris- es
  • (K) optionally drying and/or calcining, preferably drying and calcining the zeolitic material hav- ing a BEA-type framework structure obtained in (H), (I), or (J), preferably in (J);
  • steps (I) and/or (J) and/or (K) can be conducted in any order, and
  • one or more of said steps is preferably repeated one or more times.
  • the pH of the aqueous solution used for treating the zeolitic material in (H) has a pH in the range of from -1 to 4.5, more preferably of from -0.5 to 4, more preferably of from -0.2 to 3.5, more preferably of from -0.15 to 3, more preferably of from -0.1 to 2.5, more preferably of from -0.05 to 2, more preferably of from 0 to 1.5, more preferably of from 0.05 to 1 , more preferably of from 0.1 to 0.5, and more preferably of from 0.15 to 0.25.
  • the zeolitic material is added to the aqueous solution, and the mixture is heated, preferably at a temperature in the range of from 30 to 100°C, more preferably from 35 to 90°C, more preferably from 40 to 80°C, more preferably from 45 to 75°C, more preferably from 50 to 70°C, and more preferably from 55 to 65°C.
  • the mixture is heated for a period in the range of from 0.1 to 10 h, preferably from 0.1 to 7 h, more preferably from 0.5 to 5 h, more preferably from 0.5 to 4.5 h, more preferably from 1 to 4 h, more preferably from 1 to 3.5 h, more prefera- bly from 1.5 to 3 h, and more preferably from 1.5 to 2.5 h.
  • the organotemplate-free synthetic process for the prepa- ration of the zeolitic material having a BEA-type framework structure preferably further compris- es
  • one or more of said steps is preferably repeated one or more times.
  • the pH of the liquid aqueous system used for treating the zeo- litic material in (L) has a pH in the range of from 5.5 to 12, more preferably from 5.5 to 10, more preferably from 6 to 9, more preferably from 6 to 8.5, more preferably from 6.5 to 8, and more preferably from 6.5 to 7.5.
  • the zeolitic material is added to the liquid aqueous system, and the mixture is heated, more preferably at a temperature in the range of from 40 to 100°C, preferably of from 50 to 100°C, more preferably of from 60 to 100°C, more preferably of from 65 to 95°C, more preferably of from 70 to 95°C, more preferably of from 75 to 95°C, more preferably of from 80 to 90°C, and more preferably of from 85 to 90°C.
  • the mixture is heated for a period in the range of from 1 to 40 h, preferably from 3 to 30 h, more preferably from 5 to 25 h, more preferably from 6 to 20 h, more preferably from 7 to 15 h, more preferably from 7.5 to 12 h, more preferably from 8 to 10 h, and more preferably from 8.5 to 9.5 h.
  • the liquid aqueous system comprises water, preferably deionized water, wherein more preferably the liquid aqueous system is water, preferably deionized water.
  • (H) and (L), more preferably (H), (I), and (L), more preferably (H), (I), (K), and (L), and more preferably (H), (I), (J), (K), (L), (M), and (N) are repeated one or more times, prefera- bly one to five times, more preferably two to four times, and more preferably three times.
  • the organotemplate-free synthetic process for the prepa- ration of the zeolitic material having a BEA-type framework structure preferably further compris- es
  • (R) optionally drying and/or calcining, preferably drying and calcining the zeolitic material hav- ing a BEA-type framework structure obtained in (O), (P), or (Q), preferably in (Q);
  • steps (P) and/or (Q) and/or (R) can be conducted in any order, and
  • step (O) it is preferred that the pH of the aqueous solution used for treating the zeolitic material in (O) has a pH in the range of from -2 to 2, more preferably from -1.5 to 1 , more pref- erably from -1 to 0, more preferably from -0.7 to -0.1 , more preferably from -0.5 to -0.3, and more preferably from -0.45 to -0.35.
  • the zeolitic material is added to the aque- ous solution, and the mixture is heated, preferably at a temperature in the range of from 30 to 100°C, more preferably from 35 to 90°C, more preferably from 40 to 80°C, more preferably from 45 to 75°C, more preferably from 50 to 70°C, and more preferably from 55 to 65°C.
  • the mixture is heated for a period in the range of from 0.1 to 10 h, preferably from 0.1 to 7 h, more preferably from 0.5 to 5 h, more preferably from 0.5 to 4.5 h, more preferably from 1 to 4 h, more preferably from 1 to 3.5 h, more preferably from 1.5 to 3 h, and more preferably from 1.5 to 2.5 h.
  • the aqueous solution comprises a min- eral acid, preferably a mineral acid selected from the list consisting of HF, HCI, HBr, HNO 3 , H3PO4, H2SO4, H3BO3, HCIO4, and mixtures of two or more thereof, more preferably from the list consisting of HCI, HBr, HNO 3 , H 2 SO 4 , HCIO 4 , and mixtures of two or more thereof, more prefer- ably from the list consisting of HCI, HNO 3 , H 2 SO 4 , and mixtures of two or more thereof, wherein more preferably the aqueous solution comprises HCI and/or HNO 3 , preferably HNO 3 .
  • a min- eral acid preferably a mineral acid selected from the list consisting of HF, HCI, HBr, HNO 3 , H3PO4, H2SO4, H3BO3, HCIO4, and mixtures of two or more thereof, more preferably from the list consisting of HCI, HBr, H
  • drying in (E) and/or (G) and/or (K) and/or (N) and/or (R), preferably in (E), (G), (K), (N), and (R) is conducted at a temperature in the range of from 80 to 200°C, more preferably from 90 to 180°C, more preferably from 100 to 160°C, more preferably from 1 10 to 140°C, and more preferably from 115 to 130°C.
  • drying in (E) and/or (G) and/or (K) and/or (N) and/or (R), preferably in (E), (G), (K), (N), and (R) is conducted for a period in the range of from 1 to 120 h, preferably from 5 to 96 h, more preferably from 8 to 72 h, more preferably from 10 to 60 h, more preferably from 12 to 48 h, more preferably from 14 to 42 h, more preferably from 16 to 36 h, more preferably from 18 to 30 h, more preferably from 20 to 24 h, and more preferably from 21 to 23 h.
  • preferably calcining in (G) and/or (K) and/or (R), prefera- bly in (G), (K) and (R) is conducted at a temperature in the range of from 250 to 1 ,000°C, pref- erably from 300 to 900°C, more preferably from 350 to 850°C, more preferably from 400 to 800°C, more preferably from 450 to 750°C, more preferably from 500 to 700°C, and more pref- erably from 550 to 650°C.
  • calcining in (G) and/or (K) and/or (R), preferably in (G), (K) and (R) is conducted for a period in the range of from 0.5 to 36 h, more preferably from 1 to 24 h, more preferably from 1.5 to 18 h, more preferably from 2 to 12 h, more preferably from 2.5 to 9 h, more preferably from 3 to 7 h, more preferably from 3.5 to 6.5 h, more preferably from 4 to 6 h, and more preferably from 4.5 to 5.5 h.
  • the zeolitic material having a BEA-type framework struc- ture formed in (B) preferably comprises zeolite beta.
  • the seed crystals contained in the mixture prepared in (A) and crystallized in (B) comprise a zeolitic material having a BEA- type framework structure, preferably zeolite beta, and more preferably a zeolitic material having a BEA-type framework structure as obtainable and/or obtained according to the organotem- plate-free synthetic process for the preparation of the zeolitic material having a BEA-type framework structure as defined in in the process defined herein above.
  • a process for the production of an ester comprising:
  • R and R’ are alkyl groups
  • R is hydrogen or an alkyl group
  • the zeolitic material having a BEA-type framework structure displays an X-ray dif fraction pattern comprising at least the following reflections: wherein 100% relates to the intensity of the maximum peak in the 20-45° 20 range of the X-ray powder diffraction pattern, and
  • the BEA-type framework structure comprises YO 2 and X 2 O 3 , wherein Y is a tetra- valent element, and X is a trivalent element.
  • R is an optionally branched and/or optionally sub- stituted and/or optionally unsaturated alkyl group selected from the group consisting of op- tionally branched and/or optionally substituted and/or optionally unsaturated C1-C24 alkyl groups, preferably C2-C22 alkyl groups, more preferably C4-C20 alkyl groups, more pref- erably C6-C18 alkyl groups, more preferably C8-C18 alkyl groups, more preferably C10- C16 alkyl groups, more preferably C12-C16 alkyl groups, more preferably C12-C14 alkyl groups, more preferably C12 or C14 alkyl groups, and more preferably C14 alkyl groups, wherein more preferably R is selected from the group consisting of optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, o
  • R’ is an optionally branched and/or optionally substituted and/or optionally unsaturated alkyl group selected from the group consisting of optionally branched and/or optionally substituted and/or optionally unsaturat- ed C1-C6 alkyl groups, preferably C1-C5 alkyl groups, more preferably C1-C4 alkyl groups, more preferably C1-C3 alkyl groups, more preferably C1-C2 alkyl groups, and more preferably C1 alkyl groups, wherein more preferably R’ is selected from the group consisting of optionally substituted methyl, ethyl, propyl, butyl, pentyl, and hexyl, more preferably from the group consisting of optionally substituted methyl, ethyl, propyl, butyl, and pentyl, more preferably from the group consisting of optionally substituted methyl, ethyl, propyl, and
  • alkene of formula (II) is selected from the group consisting of optionally substituted ethylene, propylene, 1 -butene, 2- butene, and isobutene, wherein preferably the alkene of formula (II) is optionally substitut- ed ethylene or propylene, preferably ethylene or propylene, and more preferably propyl- ene.
  • mol% of the carboxylic acid of formula (I) preferably 20 mol% or less, more preferably 10 mol% or less, more preferably 5 mol% or less, more preferably 1 mol% or less, more preferably 0.5 mol% or less, more preferably 0.1 mol% or less, more preferably 0.05 mol% or less, more preferably 0.01 mol% or less, more preferably 0.005 mol% or less, more preferably 0.001 mol% or less, more preferably 0.0005 mol% or less, and more preferably 0.0001 mol% or less of an alcohol of the formula (IV) based on 100 mol% of the carboxylic acid of formula (I).
  • a process for the production of an ester comprising:
  • R’ is an alkyl group
  • R is hydrogen or an alkyl group
  • R is an alkylene group
  • the zeolitic material having a BEA-type framework structure displays an X-ray dif fraction pattern comprising at least the following reflections: wherein 100% relates to the intensity of the maximum peak in the 20-45° 20 range of the X-ray powder diffraction pattern, and
  • the BEA-type framework structure comprises YO 2 and X 2 O 3 , wherein Y is a tetra- valent element, and X is a trivalent element.
  • R’ is a single bond or is an optionally branched and/or optionally substituted and/or optionally unsaturated alkylene group selected from the group consisting of optionally branched and/or optionally substituted and/or optionally unsaturated C1-C16 alkylene groups, preferably C1-C14 alkylene groups, more preferably C1-C12 alkylene groups, more preferably C1-C10 alkylene groups, more preferably C2-
  • C9 alkylene groups more preferably C2-C8 alkylene groups, more preferably C2-C7 al- kylene groups, more preferably C3-C6 alkylene groups, more preferably C3-C5 alkylene groups, more preferably C3 or C4 alkylene groups, and more preferably C4 alkylene groups, wherein more preferably R’” is selected from the group consisting of optionally substituted methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, oc- tylene, nonylene, decylene, dodecylene, tetradecylene, and hexadecylene, more prefera- bly from the group consisting of optionally substituted methylene, ethylene, propylene, bu- tylene, pentylene, hexylene, heptylene, and octylene, more preferably from the group consisting of optionally substituted propylene, but
  • R’ is an optionally branched and/or optionally substituted and/or optionally unsaturated C1-C18 alkyl groups, preferably C2- C16 alkyl groups, more preferably C3-C14 alkyl groups, more preferably C4-C12 alkyl groups, more preferably C5-C10 alkyl groups, more preferably C6-C9 alkyl groups, more preferably C7 or C8 alkyl groups, and more preferably C8 alkyl groups, wherein more preferably R’ is selected from the group consisting of optionally substituted methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, and hexadecyl, more preferably from the group consisting of optionally substituted butyl, pentyl, hexyl, hexyl,
  • alkene of formula (II) is select- ed from the group consisting of optionally substituted C2-C18 alkene, preferably C3-C16 alkene, more preferably C4-C14 alkene, more preferably C5-C12 alkene, more preferably C6-C10 alkene, more preferably C7-C9 alkene, more preferably C7 or C8 alkene, and more preferably C10 alkene, wherein more preferably the alkene of formula (II) is selected from the group consisting of optionally substituted ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, and hexadecene, more preferably from the group consisting of optionally substituted 1
  • mol% of the carboxylic acid of formula (I’) preferably 20 mol% or less, more preferably 10 mol% or less, more preferably 5 mol% or less, more preferably 1 mol% or less, more preferably 0.5 mol% or less, more preferably 0.1 mol% or less, more preferably 0.05 mol% or less, more preferably 0.01 mol% or less, more preferably 0.005 mol% or less, more preferably 0.001 mol% or less, more preferably 0.0005 mol% or less, and more preferably 0.0001 mol% or less of an alcohol of the formula (IV) based on 100 mol% of the carboxylic acid of formula (G).
  • the mixture (M1) prepared in (1) and reacted in (3) contains 50 wt.% or less of elements and/or compounds other than the carboxylic acid of formula (G) and the alkene of formula (II) based on 100 wt.-% of the car- boxylic acid of formula (G), preferably 20 wt.-% or less, more preferably 10 wt.-% or less, more preferably 5 wt.-% or less, more preferably 1 wt.-% or less, more preferably 0.5 wt- % or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt.-% or less of
  • R is hydrogen or an optionally branched and/or optionally substituted and/or optionally unsaturated alkyl group selected from the group consisting of optionally branched and/or optionally substituted and/or op- tionally unsaturated C1-C6 alkyl groups, preferably C1-C5 alkyl groups, more preferably C1-C4 alkyl groups, more preferably C1-C3 alkyl groups, more preferably C1-C2 alkyl groups, and more preferably C1 alkyl groups, wherein more preferably R” is hydrogen or an alkyl group selected from the group consisting of optionally substituted methyl, ethyl, propyl, butyl, pentyl, and hexyl, more preferably from the group consisting of optionally substituted
  • the catalyst in the reac- tor contains 200 wt.% or less of elements and/or compounds other than the zeolitic mate- rial having a BEA-type framework structure based on 100 wt.-% of the zeolitic material having a BEA-type framework structure, preferably 100 wt.-% or less, more preferably 50 wt.-% or less, more preferably 20 wt.-% or less, more preferably 10 wt.-% or less, more preferably 5 wt.-% or less, more preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more prefera- bly 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-%
  • the process of any of embodiments 1 to 32, wherein in (2) and (3) the zeolitic material having a BEA-type framework structure comprised in the catalyst is in the H-form.
  • the process of any of embodiments 1 to 33, wherein in (2) and (3) the zeolitic material having a BEA-type framework structure comprised in the catalyst contains 5 wt.-% or less of a metal AM calculated as the element and based on 100 wt.-% of YO 2 contained in the framework structure of the zeolitic material having a BEA-type framework structure, pref- erably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more prefer- ably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt-
  • metal AM stands for Na, preferably for Na and K, more preferably for alkali metals, and more preferably for alkali and alkaline earth metals.
  • the zeolitic material having a BEA-type framework structure comprised in the catalyst contains 5 wt.-% or less of a metal TM calculated as the element and based on 100 wt.-% of YO 2 contained in the framework structure of the zeolitic material having a BEA-type framework structure, pref- erably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more prefer- ably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt- % or less, and more preferably 0.0001 wt.-% or less of a metal TM calculated as the ele- ment and based on 100 wt.-
  • metal TM stands for Pt, Pd, Rh, and Ir, and preferably stands for transition metal elements of groups 3-12.
  • the catalyst in the reac- tor contains 5 wt.-% or less of a metal AM calculated as the element and based on 100 wt.-% of the catalyst, preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.- % or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt.-% or less of a metal AM calculated as the element and based on 100 wt.-% of the catalyst,
  • metal AM stands for Na, preferably for Na and K, more preferably for alkali metals, and more preferably for alkali and alkaline earth metals.
  • metal TM stands for Pt, Pd, Rh, and Ir, and preferably stands for transition metal elements of groups 3-12.
  • the zeolitic material having a BEA-type framework structure comprised in the catalyst contains 5 wt.% or less of phosphorous calculated as the element and based on 100 wt.-% of YO 2 contained in the framework structure of the zeolitic material having a BEA-type framework structure, preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more prefer- ably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt- % or less, and more preferably 0.0001 wt.-% or less of phosphorous calculated as the el- ement and based on 100 wt.-% of YO 2 contained in
  • the catalyst contains 5 wt.% or less of phosphorous calculated as the element and based on 100 wt.-% of the catalyst, preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, more preferably 0.005 wt.-% or less, more preferably 0.001 wt.-% or less, more preferably 0.0005 wt.-% or less, and more preferably 0.0001 wt.-% or less of a metal AM calculated as the element and based on 100 wt.-% of the catalyst.
  • duration of the contacting of the mixture (M1 ) with the catalyst in (3) is in the range of from 0.05 to 12 h, preferably from 0.1 to 9 h, more preferably from 0.25 to 8 h, more preferably from 0.5 to 7.5 h, more pref- erably from 1 to 7 h, more preferably from 1.5 to 6.5 h, more preferably from 2 to 6 h, more preferably from 2.5 to 5.5 h, more preferably from 3 to 5 h, more preferably from 3.5 to 4.5 h, and more preferably in the range of from 3.75 to 4.25 h.
  • WHSV weight hourly space velocity
  • any of embodiments 1 to 44 wherein the zeolitic material having a BEA- type framework structure comprised in the catalyst displays a YO 2 : X 2 O 3 molar ratio in the range of from 2 to 300, preferably from 4 to 200, more preferably from 6 to 150, more preferably from 8 to 100, more preferably from 12 to 70, more preferably from 14 to 50, more preferably from 16 to 40, more preferably from 18 to 35, more preferably from 20 to 30, and more preferably from 22 to 26.
  • any of embodiments 1 to 45 wherein the tetravalent element Y of the zeo- litic material having a BEA-type framework structure comprised in the catalyst is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and a mixture of two or more thereof, Y preferably being Si.
  • the trivalent element X of the zeolitic material having a BEA-type framework structure comprised in the catalyst is selected from the group consisting of Al, B, In, Ga, and a mixture of two or more thereof, X preferably being Al.
  • the zeolitic material having a BEA- type framework structure comprised in the catalyst has a total amount of acid sites in the range of from 0.25 to 1.0 mmol/g, preferably from 0.15 to 0.8 mmol/g, more preferably from 0.2 to 0.7 mmol/g, more preferably from 0.25 to 0.6 mmol/g, more preferably from 0.3 to 0.55 mmol/g, more preferably from 0.35 to 0.5 mmol/g, more preferably from 0.38 to 0.45 mmol/g, and more preferably from 0.4 to 0.42 mmol/g,
  • the total amount of acid sites is defined as the total molar amount of desorbed ammonia per mass of the zeolitic material determined according to the temperature pro- grammed desorption of ammonia (NH3-TPD).
  • the zeolitic material having a BEA-type frame- work structure comprised in the catalyst has an amount of medium acid sites wherein the amount of medium acid sites is defined as the amount of desorbed ammonia per mass of the zeolitic material determined according to the temperature programmed desorption of ammonia (NH3-TPD) in the temperature range of from 250 to 500 °C, wherein the amount of medium acid sites is at least 40% of the total amount of acid sites, preferably from 42 to 90%, more preferably from 44 to 80%, more preferably from 46 to 75%, more preferably from 48 to 70%, more preferably from 50 to 65%, more preferably from 53 to 60%, and more preferably from 55 to 57% of the total amount of acid sites.
  • any of embodiments 48 to 51 wherein the ratio of the amount of medium acid sites relative to amount of strong acid sites is greater than 0, preferably 10 or greater, more preferably 50 or greater, more preferably 100, more preferably 10 3 or greater, more preferably 10 4 or greater, more preferably 10 5 or greater, more preferably 10 6 or greater, more preferably 10 7 or greater, more preferably 10 8 or greater, and more preferably 10 9 or greater.
  • mixture prepared in (A) and crystallized in (B) does not contain an organo- template as structure-directing agent.
  • the zeolitic material having a BEA-type framework structure obtained in (B) comprises one or more alkali metals M, wherein M is preferably selected from the group consisting of Li, Na, K, Cs, and combinations of two or more thereof, more preferably from the group consisting of Li, Na, K, and combinations of two or more thereof, wherein more preferably the alkali metal M is Na and/or K, more preferably Na.
  • any of embodiments 54 to 58, wherein the one or more sources for YO 2 contained in the mixture prepared in (A) and crystallized in (B) comprises one or more sil icates, preferably one or more alkali metal silicates, wherein the alkali metal is prefer ably selected from the group consisting of Li, Na, K, Rb, and Cs, wherein more prefer ably the alkali metal is Na and/or K, and wherein more preferably the alkali metal is Na, wherein more preferably the one or more sources for Y0 2 contained in the mixture prepared in (A) and crystallized in (B) comprises water glass, preferably sodium and/or potassium silicate, more preferably sodium silicate.
  • the one or more sources for YO 2 con- tained in the mixture prepared in (A) and crystallized in (B) further comprises one or more silicas, preferably one or more silica hydrosols and/or one or more colloidal silicas, and more preferably one or more colloidal silicas.
  • the one or more sources for X 2 O 3 contained in the mixture prepared in (A) and crystallized in (B) comprises one or more aluminate salts, preferably an aluminate of an alkali metal, wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb, and Cs, wherein more preferably the alkali metal is Na and/or K, and wherein more preferably the alkali met al is Na.
  • steps (C) and/or (D) and/or (E) can be conducted in any order, and wherein one or more of said steps is preferably repeated one or more times.
  • organotemplate-free synthetic process for the preparation of the zeolitic material having a BEA-type framework structure further comprises
  • (K) optionally drying and/or calcining, preferably drying and calcining the zeolitic materi- al having a BEA-type framework structure obtained in (H), (I), or (J), preferably in (J); wherein the steps (I) and/or (J) and/or (K) can be conducted in any order, and
  • one or more of said steps is preferably repeated one or more times.
  • organotemplate-free synthetic process for the preparation of the zeolitic material having a BEA-type framework structure further comprises
  • one or more of said steps is preferably repeated one or more times.
  • liquid aqueous system comprises water, preferably deionized water, wherein more preferably the liquid aqueous system is water, preferably deionized water.
  • (N) are repeated one or more times, preferably one to five times, more preferably two to four times, and more preferably three times.
  • organotemplate-free synthetic process for the preparation of the zeolitic material having a BEA-type framework structure further comprises
  • (R) optionally drying and/or calcining, preferably drying and calcining the zeolitic materi- al having a BEA-type framework structure obtained in (O), (P), or (Q), preferably in (Q); wherein the steps (P) and/or (Q) and/or (R) can be conducted in any order, and
  • one or more of said steps is preferably repeated one or more times.
  • the aqueous solution comprises a mineral acid, preferably a mineral acid select- ed from the list consisting of HF, HCI, HBr, HNO3, H3PO4, H2SO4, H3BO3, HCIO4, and mix- tures of two or more thereof, more preferably from the list consisting of HCI, HBr, HNO 3 , H 2 SO 4 , HCIO 4 , and mixtures of two or more thereof, more preferably from the list consist- ing of HCI, HNO 3 , H 2 SO 4 , and mixtures of two or more thereof, wherein more preferably the aqueous solution comprises HCI and/or HNO 3 , preferably HNO 3 .
  • the aqueous solution comprises HCI and/or HNO 3 , preferably HNO 3 .
  • drying in (E) and/or (G) and/or (K) and/or (N) and/or (R), preferably in (E), (G), (K), (N), and (R) is conducted at a tempera- ture in the range of from 80 to 200°C, more preferably from 90 to 180°C, more preferably from 100 to 160°C, more preferably from 1 10 to 140°C, and more preferably from 1 15 to 130°C.
  • drying in (E) and/or (G) and/or (K) and/or (N) and/or (R), preferably in (E), (G), (K), (N), and (R) is conducted for a period in the range of from 1 to 120 h, preferably from 5 to 96 h, more preferably from 8 to 72 h, more preferably from 10 to 60 h, more preferably from 12 to 48 h, more preferably from 14 to 42 h, more preferably from 16 to 36 h, more preferably from 18 to 30 h, more preferably from 20 to 24 h, and more preferably from 21 to 23 h.
  • the seed crystals contained in the mixture prepared in (A) and crystallized in (B) comprise a zeolitic material having a BEA- type framework structure, preferably zeolite beta, and more preferably a zeolitic material having a BEA-type framework structure as obtainable and/or obtained according to the organotemplate-free synthetic process for the preparation of the zeolitic material having a BEA-type framework structure as defined in any of embodiments 48 to 65.
  • Figure 1 displays the X-ray diffraction pattern (measured using Cu K alpha-1 radiation) of the zeolitic material obtained according to Reference Example 1.
  • the angle 2 theta in ° is shown along the abscissa and the intensities are plotted along the or- dinate.
  • Figure 2 shows the results from catalytic testing with regard to the yield in isopropyl myristate
  • the present invention is further illustrated by the following reference examples, examples, and comparative examples.
  • X-ray diffraction experiments on the powdered materials were performed using D8 Advance X- ray Diffractometer (Bruker AXS) equipped with a Lynx Eye detector using the Cu K alpha-1 ra- diation.
  • the samples were lightly ground using a mortar and pestle and filled into flat sample holders with a 2mm x 20mm cavity. The surface was flattened using a glass plate.
  • Cu-Ka radiation was used in a Bragg-Brentano geometry. Data was collected from 2- 50°(20) using a 0.02° step size and a dwell time of 2.4 seconds per step.
  • the parameters used in the X-ray diffraction experiment were as follows:
  • the temperature-programmed desorption of ammonia was conducted in an auto- mated chemisorption analysis unit (Micromeritics AutoChem II 2920) having a thermal conduc- tivity detector. Continuous analysis of the desorbed species was accomplished using an online mass spectrometer (OmniStar QMG200 from Pfeiffer Vacuum). The sample (0.1 g) was intro- Jerusalem into a quartz tube and analysed using the program described below. The temperature was measured by means of a Ni/Cr/Ni thermocouple immediately above the sample in the quartz tube. For the analyses, He of purity 5.0 was used. Before any measurement, a blank sample was analysed for calibration. 1.
  • Preparation Commencement of recording; one measurement per second. Wait for 10 minutes at 25 °C and a He flow rate of 30 cm 3 /min (room temperature (about 25 °C) and 1 atm); heat up to 600 °C at a heating rate of 20 K/min; hold for 10 minutes. Cool down under a He flow (30 cm 3 /min) to 100 °C at a cooling rate of 20 K/min (furnace ramp temperature); Cool down under a He flow (30 cm 3 /min) to 100 °C at a cooling rate of 3 K/min (sample ramp temperature).
  • NH 3 -TPD Commencement of recording; one measurement per second. Heat up under a He flow (flow rate: 30 cm 3 /min) to 600 °C at a heating rate of 10 K/min; hold for 30 min.
  • the amount of ammonia adsorbed was ascertained by means of the Micromeritics software through integration of the TPD signal with a horizontal baseline.
  • Reference Example 1 Organotemplate-free synthesis of zeolite beta a) Preparation of a zeolite having BEA framework structure (H-beta zeolite) a1) 335.1 g of NaAI0 2 (4.09 moles) were dissolved in 7314 g of H 2 O (406 moles) while stir- ring, followed by addition of 74.5 g of zeolite Beta seeds (commercially available from Ze- olyst International, Valley Forge, PA 19482, USA, under the tradename CP814C, CAS Registry Number 1318-02-1 , which was converted to the H-form by calcination at 550°C for 5 h, wherein a heat ramp of 1 °C/min was used for attaining the calcination tempera- ture).
  • H-beta zeolite BEA framework structure
  • the mixture was placed in a 20 L autoclave and 7340 g sodium waterglass solution (26 wt.-% S1O 2 and 8 wt.-% Na 2 0) and 1436 g Ludox® AS40 (9.5 moles) were added af- fording an aluminosilicate gel with a molar ratio of 1.00 S1O 2 : 0.0421 Al 2 0 3 : 0.285 Na 2 0 : 17.48 H 2 O.
  • the reaction mixture was heated in 3 h to a temperature of 120 °C using a constant heat ramp, wherein said temperature was then maintained 117 h.
  • a vessel was charged with 34.506 kg of an aqueous solution of HNO 3 (15 weight-%).
  • Total amount of acid sites 0.41 mmol/g, as determined according to the NH 3 -TPD meth- od described above.
  • Total amount of medium acid sites 0.23 mmol/g, as determined according to the NH 3 - TPD method described above.
  • Total amount of strong acid sites none detected according to the NH 3 -TPD method de- scribed above.
  • the X-ray diffraction pattern of the dealuminated zeolite is shown in Figure 1 , and displays a pattern typical for the BEA framework type.
  • the zeolitic material according to this Reference Example 2 is the zeolitic material CP814E as obtained from Zeolyst International.
  • the characterization of the material via XRD confirmed the CHA-type framework structure of the product.
  • the solutions are prepared separately.
  • the solution of the HPW is placed in a 2 I beaker with magnetic stirrer.
  • Solution 1 is then added to solution 2 by means of a dropping funnel within of 40 minutes time, in which white precipitate forms.
  • the resulting suspension is stirred over- night, after which the suspension is evaporated to dryness (25-30 mbar at 50°C) on a rotary evaporator; the resulting powder is dried in the drying cabinet at 100°C for 16 h and then pressed through a 0.5 mm filter.
  • the product is then heated in a muffle furnace to 300 0 C. with 2 K / min and heat treated for 3 h.
  • the elemental analysis of the product showed 9.9 wt.-% Cs and 66.7 wt.-% W.
  • Example 1 Catalyst Testing - Reaction of a monocarboxylic acid with an alkene
  • the hastelloy autoclave reactor (inner volume 300 ml) was tightly sealed and then pressurized with 10 bar of the alkene propylene.
  • the mixture was heated to a temperature of 130°C while stirring at 2000 rpm. After the corresponding reaction temperature was reached, the reaction temperature was maintained for 4h, while continuing stirring the reaction mixture inside the heated and pressurized hastelloy autoclave reactor.
  • the temperature of the reaction was 130°C and the propylene pressure kept constant at 10 bar by adding propylene continuously during the reaction.
  • the steel autoclave reactor was allowed to cool down to approximately 70°C, to keep the myristic acid liquid the pressure was released and the hastelloy autoclave reactor was opened.
  • the suspension was filtered, to remove all rests from the catalyst and 1 ml of the reaction mixture was subjected to a GC analysis.
  • Cesium phosphotungstate and several types of zeolites were chosen as solid acid catalysts for the catalytic testing.
  • the starting catalyst concentration was 5 wt%.
  • the list of all catalysts and details about their performance with regard to their selectivities for isopropyl myristate (I PM) are shown in the Table 1.
  • Table 1 Results from catalytic testing with regard to the yield in isopropyl myristate.
  • Example 1 and Comparative Example 7 catalysts were each then evaluated for prolonged reaction time as shown in Table 2.
  • Table 2 Results from catalytic testing with regard to the yield in isopropyl myristate (Prolonged Reaction Time)
  • Example 1 outperforms comparative example 7 over time, since after 17 hours the Example 1 catalyst continues to pro- vide improved yields of I PM, whereas the comparative Example 7 catalyst selectivity is decreas- ing over time. Accordingly, the Example 1 catalyst would be particularly beneficial when pro- longed reaction times are employed in a batch process. In this light, when a continuous process is carried out the performance of Example 1 would be superior over time compared to the com- parative example 7 catalyst.
  • Example 2 Catalyst Testing - Reaction of a decarboxylic acid with an alkene
  • diisodecylester of the adipic acid as products.
  • polymerization of the olefin only the dimer eicosene can be observed in the reactions. Unreacted adipic acid could be found in the precipitate, so the representation of the results below includes only the filtrate mixture.
  • Comparative Example 11 shows that the increase by 10 leads to a higher selectivity of the diester product, whereas the higher selectivity towards the monoester product is quite unexpectedly maintained for zeolite beta from Refer- ence Example 1 in Example 5 despite the very high concentration of the alkene educt in the reaction mixture.

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Abstract

La présente invention concerne un procédé catalytique pour la préparation d'un ester à partir d'un acide carboxylique et d'un alcène à l'aide d'un matériau zéolithique ayant une structure de charpente de type BEA en tant que catalyseur.
PCT/EP2019/051150 2018-01-17 2019-01-17 Estérification d'acides carboxyliques avec des oléfines à l'aide d'un matériau zéolithique ayant une structure de charpente de type bea Ceased WO2019141778A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12358802B2 (en) * 2020-02-24 2025-07-15 Universitat Politecnica De Valencia Crystalline zeolite-type material

Citations (4)

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Publication number Priority date Publication date Assignee Title
US4365084A (en) * 1980-12-19 1982-12-21 Mobil Oil Corporation Preparation of alkyl carboxylates
US5189201A (en) 1992-03-25 1993-02-23 Showa Denko K.K. Process for preparation of lower fatty acid ester
WO1999054276A1 (fr) * 1998-04-16 1999-10-28 Arco Chemical Technology, L.P. Preparation d'alkylester tertiaire
WO2010146156A1 (fr) 2009-06-18 2010-12-23 Basf Se Procédé de synthèse sans matrice organique pour la production d'un matériau zéolithique

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US4365084A (en) * 1980-12-19 1982-12-21 Mobil Oil Corporation Preparation of alkyl carboxylates
US5189201A (en) 1992-03-25 1993-02-23 Showa Denko K.K. Process for preparation of lower fatty acid ester
WO1999054276A1 (fr) * 1998-04-16 1999-10-28 Arco Chemical Technology, L.P. Preparation d'alkylester tertiaire
WO2010146156A1 (fr) 2009-06-18 2010-12-23 Basf Se Procédé de synthèse sans matrice organique pour la production d'un matériau zéolithique

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KRESNAWAHJUESA, O. ET AL: "The acylation of propene by acetic acid over H-[Fe]ZSM-5 and H-[Al]ZSM-5", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 212, no. 1-2, 1 April 2004 (2004-04-01), pages 309 - 314, XP002781340, DOI: 10.1016/J.MOLCATA.2003.11.015 *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12358802B2 (en) * 2020-02-24 2025-07-15 Universitat Politecnica De Valencia Crystalline zeolite-type material

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