- Esterification or Thioesterification of Carboxylic Acids with Alcohols or Thiols Using Amphipathic Monolith-SO3H Resin
-
We have developed a method for the esterification of carboxylic acids with alcohols using amphipathic, monolithic-resin bearing sulfonic acid moieties as cation exchange functions (monolith-SO3H). Monolith-SO3H efficiently catalyzed the esterification of aromatic and aliphatic carboxylic acids with various primary and secondary alcohols (1.55.0 equiv) in toluene at 6080 °C without the need to remove water generated during the reaction. The amphipathic property of monolith-SO3H facilitates dehydration due to its capacity for water absorption. This reaction was also applicable to thioesterification, wherein the corresponding thioesters were obtained in excellent yield using only 2.0 equiv of thiol in toluene, although heating at 120 °C was required. Moreover, monolith-SO3H was separable from the reaction mixtures by simple filtration and reused for at least five runs without decreasing the catalytic activity.
- Ichihara, Shuta,Ishida, Moeka,Ito, Ryo,Kato, Ayumu,Monguchi, Yasunari,Nakamura, Shinji,Park, Kwihwan,Sajiki, Hironao,Takada, Hitoshi,Wakayama, Fumika,Yamada, Tsuyoshi,Yamada, Yutaro
-
p. 2702 - 2710
(2022/01/19)
-
- Gold-based catalyst for oxidative esterification of aldehydes to carboxylic acid esters
-
The present invention relates to novel catalysts for oxidative esterification, by means of which, for example, (meth)acrolein can be converted to methyl (meth)acrylate. The catalysts of the invention are especially notable for high mechanical and chemical stability even over very long periods. This especially relates to an improvement in the catalyst service life, activity and selectivity over prior art catalysts which lose activity and/or selectivity relatively quickly in continuous operation in media having even a small water content.
- -
-
Page/Page column 15
(2021/02/03)
-
- The effect of the bimetallic Pd-Pb structures on direct oxidative esterification of methacrolein with methanol
-
Supported palladium and palladium alloy were proved to be active catalysts for the oxidative esterification reaction of methacrolein with methonal to methyl methacrylate. Here we synthesized two types of structurally supported palladium alloy catalysts with ordered or disordered Pd3Pb intermetallic crystals by impregnation-reduction method as well as high temperature heat treatment. Importantly, the catalyst with disordered Pd3Pb crystals had 89% conversion for methylacrolein and 79% selectivity for methyl methacrylate, showing obvious higher activity than the catalyst with ordered Pd3Pb crystals. The morphology, metal arrangement and electron effect of the catalyst were analyzed by XRD, TEM and XPS. It was confirmed that more active sites and strong electron transfer between metals were the reasons for the excellent performance of the disordered catalyst. This study provides theoretical guidance for the further study of Pd-based catalysts for the oxidative esterification of methacrolein to methyl methacrylate.
- Diao, Yanyan,Qi, Miao,Song, Yuting,Wang, Ling,Wu, Xiangying
-
-
- Multicatalytic Transformation of (Meth)acrylic Acids: a One-Pot Approach to Biobased Poly(meth)acrylates
-
Shifting from petrochemical feedstocks to renewable resources can address some of the environmental issues associated with petrochemical extraction and make plastics production sustainable. Therefore, there is a growing interest in selective methods for transforming abundant renewable feedstocks into monomers suitable for polymer production. Reported herein are one-pot catalytic systems, that are active, productive, and selective under mild conditions for the synthesis of copolymers from renewable materials. Each system allows for anhydride formation, alcohol acylation and/or acid esterification, as well as polymerization of the formed (meth)acrylates, providing direct access to a new library of unique poly(meth)acrylates.
- Fouilloux, Hugo,Placet, Vincent,Qiang, Wei,Robert, Carine,Thomas, Christophe M.
-
supporting information
p. 19374 - 19382
(2021/07/21)
-
- The effect of viscosity on the coupling and hydrogen-abstraction reaction between transient and persistent radicals
-
The effect of viscosity on the radical termination reaction between a transient radical and a persistent radical undergoing a coupling reaction (Coup) or hydrogen abstraction (Abst) was examined. In a non-viscous solvent, such as benzene (bulk viscosity bulk 99% Coup/Abst selectivity, but Coup/Abst decreased as the viscosity increased (89/11 in PEG400 at 25 °C [bulk = 84 mPa s]). While bulk viscosity is a good parameter to predict the Coup/Abst selectivity in each solvent, microviscosity is the more general parameter. Poly(methyl methacrylate) (PMMA)-end radicals had a more significant viscosity effect than polystyrene (PSt)-end radicals, and the Coup/Abst ratio of the former dropped to 50/50 in highly viscous media (bulk = 3980 mPa s), while the latter maintained high Coup/ Abst selectivity (84/16). These results, together with the low thermal stability of dormant PMMA-TEMPO species compared with that of PSt-TEMPO species, are attributed to the limitation of the nitroxide-mediated radical polymerization of MMA. While both organotellurium and bromine compounds were used as precursors of radicals, the former was superior to the latter for the clean generation of radical species.
- Li, Xiaopei,Kato, Tatsuhisa,Nakamura, Yasuyuki,Yamago, Shigeru
-
p. 966 - 972
(2021/04/29)
-
- A CATALYST AND A PROCESS FOR THE PRODUCTION OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACIDS OR ESTERS
-
The invention discloses a catalyst comprising a silica support, a modifier metal and a catalytic alkali metal. The silica support has a multimodal pore size distribution comprising a mesoporous pore size distribution having an average pore size in the range 2 to 50 nm and a pore volume of said mesopores of at least 0.1 cm3/g, and a macroporous pore size distribution having an average pore size of more than 50 nm and a pore volume of said macropores of at least 0.1 cm3/g. The level of catalytic alkali metal on the silica support is at least 2 mol%. The modifier metal is selected from Mg, B, Al, Ti, Zr and Hf. The invention also discloses a method of producing the catalyst, a method of producing an ethylenically unsaturated carboxylic acid or ester in the presence of the catalyst, and a process for preparing an ethylenically unsaturated acid or ester in the presence of the catalyst.
- -
-
Page/Page column 40
(2021/02/05)
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- Second-Generation meta-Phenolsulfonic Acid-Formaldehyde Resin as a Catalyst for Continuous-Flow Esterification
-
A second-generation m-phenolsulfonic acid-formaldehyde resin (PAFR II) catalyst was prepared by condensation polymerization of sodium m-phenolsulfonate and paraformaldehyde in an aqueous H2SO4 solution. This reusable, robust acid resin catalyst was improved in both catalytic activity and stability, maintaining the characteristics of the previous generation catalyst (p-phenolsulfonic acid-formaldehyde resin). PAFR II was applied in the batchwise and continuous-flow direct esterification without water removal and provided higher product yields in continuous-flow esterification than any other commercial ion-exchanged acid catalyst tested.
- Hu, Hao,Ota, Hajime,Baek, Heeyoel,Shinohara, Kenta,Mase, Toshiaki,Uozumi, Yasuhiro,Yamada, Yoichi M. A.
-
supporting information
p. 160 - 163
(2020/01/02)
-
- Synthesis method for acrylate with low polymerization inhibitor content
-
The invention discloses a synthesis method for acrylate with a low polymerization inhibitor content. The method comprises the following steps: in the presence of at least one polymerization inhibitor,directly esterifying acrylic acid or methacrylic acid and corresponding alcohol serving as raw materials under the action of an acidic catalyst to synthesize corresponding acrylate or methacrylate, and introducing air into a reactor in the reaction process to take water generated by the reaction out of the reactor; after reacting for a period of time, filtering an esterification reaction solutionto remove the catalyst, and carrying out alkali washing and water washing to obtain a product acrylate or methacrylate, wherein the polymerization inhibitor is a compound polymerization inhibitor, and the compound polymerization inhibitor comprises a cobaloxime boron fluoride complex and a phenolic compound. By adopting the compound polymerization inhibitor, the usage amount of the polymerizationinhibitor can be reduced to 5-20 ppm, the oxygen content in the reactor is not required, the method is suitable for industrial production and application, the requirements of customers on acrylate products with low polymerization inhibitor content can be met, and a subsequent step of removing the polymerization inhibitor is omitted.
- -
-
Paragraph 0014-0021
(2020/05/01)
-
- HETEROGENEOUS CATALYST
-
A heterogeneous catalyst comprising a support and gold, wherein: (i) said support comprises alumina, (ii) said catalyst comprises from 0.1 to 5 wt% of gold, (iii) at least 90 wt% of the gold is in the outer 60% of catalyst volume, and (iv) particles of the catalyst have an average diameter from 200 microns to 30 mm; wherein weight percentages are based on weight of the catalyst. The catalyst of this invention is used in a process for producing methyl methacrylate (MMA) which comprises treating methacrolein with methanol in an oxidative esterification reactor.
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-
Page/Page column 5-7
(2020/01/24)
-
- Method for carrying out a heterogeneously catalysed reaction
-
A process for performing a heterogeneously catalysed reaction in a three-phase reactor, where there is at least one liquid phase, at least one gaseous phase and at least one solid phase in the reactor and the reactor has at least two zones, with the reaction mixture being conveyed downward in zone 1, the reaction mixture being conveyed upward in zone 2, zones 1 and 2 being separated from one another by a dividing wall, and in that the ratio between the average catalyst concentrations in zone 2 and in zone 1 is greater than 2.
- -
-
Page/Page column 8-10
(2020/04/09)
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- A PROCESS FOR THE PRODUCTION OF A CATALYST, A CATALYST THEREFROM AND A PROCESS FOR PRODUCTION OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACIDS OR ESTERS
-
The present invention relates to a process for producing a catalyst. The process comprises the steps of: a) providing an uncalcined metal modified porous silica support wherein the modifier metal is selected from one or more of boron, magnesium, aluminium, zirconium, hafnium and titanium, wherein the modifier metal is present in mono- or dinuclear modifier metal moieties; b) optionally removing any solvent or liquid carrier from the modified silica support; c) optionally drying the modified silica support; d) treating the uncalcined metal modified silica support with a catalytic metal to effect adsorption of the catalytic metal onto the metal modified silica support; and e) calcining the impregnated silica support of step d). The invention extends to an uncalcined catalyst intermediate and a method of producing a catalyst by providing a porous silica support having isolated silanol groups.
- -
-
Page/Page column 31-32
(2020/09/30)
-
- Preparation method for methyl methacrylate
-
The invention relates to a preparation method for methyl methacrylate. The preparation method comprises the following steps: introducing oxygen into isobutyraldehyde at a temperature of 50 to 60 DEG Cand a pressure of 0.1 to 0.3 MPa in the presence of a solid oxidation catalyst for oxidization of the isobutyraldehyde, carrying out a reaction at an oxygen space velocity of 1000 to 1200 hours for 10 to 36 hours, and separating the solid oxidation catalyst so as to obtain an isobutyric acid solution; adding a halogen element and acetic anhydride into the isobutyric acid solution, and carrying out a reaction at a normal pressure and a temperature of 80 to 100 DEG C for 1 to 5 hours so as to obtain a halogenated isobutyric acid solution; adding sodium hydroxide and first methanol into thehalogenated isobutyric acid solution, carrying out a reaction at a normal pressure and a temperature of 50 to 80 DEG C for 5 to 15 hours, and carrying out filtering to remove impurities so as to obtain a methacrylic acid solution; and adding second methanol, an ionic liquid catalyst and cyclohexane into the methacrylic acid solution, carrying out a reaction at 70 to 90 DEG C for 2 to 12 hours, andcarrying out filtering and separation so as to obtain the methyl methacrylate. The preparation method provided by the invention has simple preparation process and high yield.
- -
-
Paragraph 0036-0049
(2019/11/12)
-
- A METHOD FOR PRODUCTION OF METHYL METHACRYLATE BY OXIDATIVE ESTERIFICATION USING A HETEROGENEOUS CATALYST
-
A method for preparing methyl methacrylate from methacrolein and methanol. The method comprises contacting a mixture comprising methacrolein, methanol and oxygen with a heterogeneous catalyst comprising a support and a noble metal, wherein said catalyst has an average diameter of at least 200 microns and at least 90 wt% of the noble metal is in the outer 70% of catalyst volume, and wherein oxygen concentration at a reactor outlet is from 0.5 to 7.5 mol%.
- -
-
Page/Page column 6
(2019/02/13)
-
- A METHOD FOR PRODUCTION OF METHYL METHACRYLATE BY OXIDATIVE ESTERIFICATION USING A HETEROGENEOUS CATALYST
-
A method for preparing methyl methacrylate from methacrolein and methanol. The method comprises contacting in a tubular reactor having at least four zones a mixture comprising methacrolein, methanol, oxygen and a base with a catalyst bed of heterogeneous catalyst comprising a support and a noble metal, wherein reaction zones comprising catalyst beds alternate with mixing zones not comprising catalyst beds.
- -
-
Page/Page column 8
(2019/02/13)
-
- A METHOD FOR PRODUCTION OF METHYL METHACRYLATE BY OXIDATIVE ESTERIFICATION USING A HETEROGENEOUS CATALYST
-
A method for preparing methyl methacrylate from methacrolein and methanol; said method comprising contacting in a reactor a mixture comprising methacrolein, methanol and oxygen with a catalyst bed of heterogeneous catalyst comprising a support and a noble metal, wherein mass transfer rate of oxygen in hour-1 divided by space-time yield in moles methyl methacrylate/kg.catalyst hour in the catalyst bed is at least 25 kg catalyst/mole methyl methacrylate.
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-
Page/Page column 7
(2019/02/13)
-
- A METHOD FOR PRODUCTION OF METHYL METHACRYLATE BY OXIDATIVE ESTERIFICATION USING A HETEROGENEOUS CATALYST
-
A method for preparing methyl methacrylate from methacrolein and methanol. The method comprises contacting a mixture comprising methacrolein, methanol and oxygen with a heterogeneous catalyst comprising a support and a noble metal; wherein said catalyst has an average diameter of at least 200 microns and average concentration of methacrolein is at least 15 wt%.
- -
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Page/Page column 6
(2019/02/13)
-
- Cyanide-Free One-Pot Synthesis of Methacrylic Esters from Acetone
-
Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n-C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d6 and MeOH-d4, with DBU in acetonitrile afforded deuterated MMA (MMA-d8) in 70 % yield.
- Koyama, Minoru,Kawakami, Takafumi,Okazoe, Takashi,Nozaki, Kyoko
-
p. 10913 - 10917
(2019/08/02)
-
- The Effect of Viscosity on the Diffusion and Termination Reaction of Organic Radical Pairs
-
The effect of viscosity on the diffusion efficiency (Fdif) of an organic radical pair in a solvent cage and the termination mechanism, that is, the selectivity of disproportionation (Disp) and combination (Comb) of the geminated caged radical pair and the diffused radicals encountered, were investigated quantitatively by following the photolysis of dimethyl 2,2′-azobis(2-methylpropionate) (V-601) in the absence and presence of PhSD. Fdif and Disp/Comb selectivity outside the cage [Disp(dif)/Comb(dif)] are highly sensitive to the viscosity. In contrast, the Disp/Comb selectivity inside the cage [Disp(cage)/Comb(cage)] is rather insensitive. The difference in viscosity dependence between Disp(cage)/Comb(cage) and Disp(dif)/Comb(dif) is explained by the spin state of the radical pair inside and outside the cage and the spin state dependent configurational changes of the radical pair upon their collision. Given that the configurational change of the radicals associates the displacement and reorganization of solvents around the radicals, the termination outside the cage, which requires larger change than that inside the cage, is highly viscosity dependent. Furthermore, while the bulk viscosity of each solvent shows good correlation with Fdif and Disp/Comb selectivity, microviscosity is the better parameter predicting Fdif and Disp(dif)/Comb(dif) selectivity regardless of the solvents.
- Li, Xiaopei,Ogihara, Tasuku,Abe, Manabu,Nakamura, Yasuyuki,Yamago, Shigeru
-
supporting information
p. 9846 - 9850
(2019/07/10)
-
- Efficient and catalyst free synthesis of acrylic plastic precursors: Methyl propionate and methyl methacrylate synthesis through reversible CO2 capture
-
Methyl propionate (MP) and methyl methacrylate (MMA) are considered as industrially important precursors for large-scale acrylic plastic production. The existing industrial synthetic protocols for these precursors utilize expensive catalysts accompanied by toxic and explosive gases such as carbon monoxide, ethylene and hydrogen. Herein, we for the first time report highly selective, catalyst-free and room temperature synthesis of MP and MMA precursors through a reversible CO2 capture approach involving an organic superbase. In short, initially an equimolar mixture of an organic superbase 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and methanol was reversibly reacted with molecular CO2 and the obtained switchable ionic liquid, [DBUH][MeCO3], further reacted with an equivalent amount of propionic anhydride or methacrylic anhydride to form MP or MMA, respectively. These reactions were accomplished in different solvents such as DMSO and methanol, and in the case of methanol, separation of reaction products occurs from in situ formed DBU derivatives such as [DBU][propionate] or [DBU][methacrylate]. In the case of both MP and MMA syntheses, after the use of methanol as a solvent, good recovery of the alcoholic solution of esters was achieved where 85% and 92% yields of MP and MMA were obtained, respectively. Molecular DBU was recovered from its propionate and methacrylate salts using NaCl saturated alkaline solution. Furthermore, the recovered MMA with methanol was polymerised to poly-MMA using a benzoyl peroxide induced free radical polymerisation process. The synthesis and separation of MP or MMA and the recovery of DBU were monitored by NMR analysis. Hence, unlike DMSO, methanol not only functioned as a reagent in CO2 capture and as a solvent medium in MP, MMA and poly-MMA syntheses but also assisted in the recovery of DBU from the reaction mixture. Most importantly, here we present a more efficient, safer and single solvent based alternative synthetic approach for the synthesis of acrylic plastic precursors MP or MMA compared to existing industrial methods. Also, no toxic or expensive catalysts were required.
- Khokarale, Santosh Govind,Mikkola, Jyri-Pekka
-
p. 2138 - 2147
(2019/04/26)
-
- METHOD FOR PREPARATION OF HETEROGENEOUS CATALYSTS
-
A method for preparing a heterogeneous catalyst. The method comprises steps of: (a) combining (i) a support, (ii) an aqueous solution of a noble metal compound and (iii) a C2-C18 thiol comprising at least one hydroxyl or carboxylic acid substituent; to form a wet particle and (b) removing water from the wet particle by drying followed by calcination to produce the catalyst.
- -
-
Page/Page column 4; 7; 13
(2019/02/13)
-
- A CATALYST AND A PROCESS FOR THE PRODUCTION OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACIDS OR ESTERS
-
A catalyst has a modified silica support and comprises a modifier metal, zirconium and/or hafnium, and a catalytic metal on the modified support. The catalyst has at least a proportion, typically, at least 25%, of modifier metal present in moieties having a total of up to 2 modifier metal atoms. The moieties may be derived from a monomeric and/or dimeric cation source. A method of production:- provides a silica support with isolated silanol groups with optional treatment to provide isolated silanol groups (-SiOH) at a level of 2; contacting the optionally treated silica support with a monomeric zirconium or hafnium modifier metal compound to effect adsorption onto the support; optionally calcining the modified support for a time and temperature sufficient to convert the monomeric zirconium or hafnium compound adsorbed on the surface to an oxide or hydroxide of zirconium or hafnium in preparation for catalyst impregnation. A method of producing an ethylenically unsaturated carboxylic acid or ester, typically, an a, β ethylenically unsaturated carboxylic acid or ester, comprising the steps of contacting formaldehyde or a suitable source thereof with a carboxylic acid or ester in the presence of catalyst and optionally in the presence of an alcohol, wherein said catalyst is used.
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-
Page/Page column 45-50
(2019/04/11)
-
- A PROCESS FOR THE PRODUCTION OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACID ESTERS AND A CATALYST THEREFOR
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A process for the production of an ethylenically unsaturated carboxylic acid ester, preferably an α,? ethylenically unsaturated carboxylic acid ester is described. The process takes place by the reaction of formaldehyde or a suitable source thereof with a carboxylic acid ester in the presence of a basic metal methyl carbonate co-reactant, wherein the process produces a second basic metal salt and wherein the process includes the step of contacting the second basic metal salt with: a)carbon dioxide (CO2) and optionally, methanol, and/or b)dimethyl carbonate, to regenerate the basic metal methyl carbonate co-reactant. The invention includes use of carbon dioxide and/or dimethyl carbonate to regenerate a basic metal methyl carbonate.
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-
Page/Page column 27
(2018/05/03)
-
- OZONE-ACTIVATED NANOPOROUS GOLD AND METHODS OF ITS USE
-
The invention relates to nanoporous gold nanoparticle catalysts formed by exposure of nanoporous gold to ozone at elevated temperatures, as well as methods for production of esters and other compounds.
- -
-
Page/Page column 8; 26
(2018/01/17)
-
- Oxidative Esterification of Methacrolein to Methyl Methacrylate over Supported Gold Catalysts Prepared by Colloid Deposition
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Esterification is one of the most pivotal organic transformations. Au catalysts were prepared by using a colloid deposition method with poly(vinyl alcohol) (PVA) as a protective agent. The catalyst was used for the oxidative esterification of methacrylate (MAL) to methyl methacrylate (MMA). Three pre-treatments were used to remove the PVA, which is unfavorable for catalytic activity. It is found that the catalyst pre-treated at 300 °C showed substantially improved activity owing to the lower PVA loading compared with catalysts treated with hot water washing and water reflux. Surprisingly, it is also found that the distribution and loading content of Au particles was closely related to the pH of the colloid solution. We demonstrate that the deposition process is controlled by the different charge of the support surface at different colloid solution pH. Further, the catalysts with similar size Au particles loaded on TiO2, SiO2, Al2O3, CeO2, ZrO2, and ZnO were successfully prepared by controlling the colloid solution pH. The Au/ZnO catalyst presented the best performance, which may be a result of the strong basic surface sites that improved the formation of the intermediate and the strong interaction between Au and ZnO. This interaction caused an anchoring effect and changed the geometries of Au particles, which could enhance the stability of catalysts and promote the mobility of oxygen, respectively.
- Li, Yuchao,Zheng, Yanxia,Wang, Lei,Fu, Zhongjun
-
p. 1960 - 1968
(2017/06/13)
-
- Oxidative Esterification of Methacrolein to Methyl Methacrylate over Gold Nanoparticles on Hydroxyapatite
-
The catalytic production of methyl methacrylate through the direct oxidative esterification of methacrolein is important in terms of green chemistry and sustainable development. In the present work, Au nanoparticles supported on three needle-like, lamella-like, and rodlike hydroxyapatites were synthesized. We demonstrated that needle-like hydroxyapatite could facilitate the higher dispersion of Au species because of its high specific surface area, and the strong interaction between the Au nanoparticles and the support resulted in the formation of more surface defects because of the existence of partially encapsulated Au particles by the needle-like hydroxyapatite. The surface defects were related closely to the generation of strong basic sites. Compared with the other two materials, the Au supported on the needle-like hydroxyapatite catalyst, which had a large amount of surface acid–base sites, exhibited a much higher catalytic activity and selectivity to methyl methacrylate in the direct oxidative esterification of methacrolein with methanol under mild reaction conditions (i.e., ambient pressure, low reaction temperature of 70 °C, and low methanol/aldehyde ratio of 8:1). The superior catalytic performance of the Au supported on needle-like hydroxyapatite catalyst was attributable to a cooperative effect between abundant acid–base sites for the preferential chemisorption of methacrolein and highly dispersed active Au species for the favorable formation of β-hydride and oxygen activation. The present findings open a new and promising route for the practical production of methyl methacrylate using high-performance hydroxyapatite-supported metal catalyst systems.
- Gao, Jun,Fan, Guoli,Yang, Lan,Cao, Xinzhong,Zhang, Peng,Li, Feng
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p. 1230 - 1241
(2017/04/14)
-
- Engineering cyclohexanone monooxygenase for the production of methyl propanoate
-
A previous study showed that cyclohexanone monooxygenase from Acinetobacter calcoaceticus (AcCHMO) catalyzes the Baeyer-Villiger oxidation of 2-butanone, yielding ethyl acetate and methyl propanoate as products. Methyl propanoate is of industrial interest as a precursor of acrylic plastic. Here, various residues near the substrate and NADP+ binding sites in AcCHMO were subjected to saturation mutagenesis to enhance both the activity on 2-butanone and the regioselectivity toward methyl propanoate. The resulting libraries were screened using whole cell biotransfor-mations, and headspace gas chromatography-mass spectrometry was used to identify improved AcCHMO variants. This revealed that the I491A AcCHMO mutant exhibits a significant improvement over the wild type enzyme in the desired regioselectivity using 2-butanone as a substrate (40% vs 26% methyl propanoate, respectively). Another interesting mutant is the T56S AcCHMO mutant, which exhibits a higher conversion yield (92%) and kcat (0.5 s-1) than wild type AcCHMO (52% and 0.3 s-1, respectively). Interestingly, the uncoupling rate for the T56S AcCHMO mutant is also significantly lower than that for the wild type enzyme. The T56S/I491A double mutant combined the beneficial effects of both mutations leading to higher conversion and improved regioselectivity. This study shows that even for a relatively small aliphatic substrate (2-butanone), catalytic efficiency and regioselectivity can be tuned by structure-inspired enzyme engineering.
- Van Beek, Hugo L.,Romero, Elvira,Fraaije, Marco W.
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p. 291 - 299
(2018/02/02)
-
- PROCESS FOR PRODUCTION OF A SILICA-SUPPORTED ALKALI METAL CATALYST
-
A process for regenerating a silica-supported depleted alkali metal catalyst is described. The level of alkali metal on the depleted catalyst is at least 0.5 mol % and the silica support is a zero-gel. The process comprises the steps of contacting the silica supported depleted alkali metal catalyst with a solution of a salt of the alkali metal in a solvent system that has a polar organic solvent as the majority component. A re-impregnated catalyst prepared by the process of the invention any comprising a silica zero-gel support and a catalytic metal selected from an alkali metal in the range 0.5-5 mol % on the catalyst, wherein the surface area of the silica support is 2/g is also described. The invention is applicable to a process for preparing an ethylenically unsaturated acid or ester comprising contacting an alkanoic acid or ester of the formula R1—CH2—COOR3, with formaldehyde or a suitable source of formaldehyde.
- -
-
Paragraph 0085-0087
(2017/06/12)
-
- Method for synthesizing acrylic acid low-carbon alcohol ester through carbonylation of acetylene
-
The invention relates to a method for synthesizing acrylic acid low-carbon alcohol ester through carbonylation of acetylene. A nickel-containing compound and a bidentate ligand containing nitrogen and a VIA-th group element serve as catalysts, and acetylene, carbon monoxide and low-carbon alcohol are subjected to carbonylation reaction in a solvent to synthesize the acrylic ester at one step. The method has the characteristics of low catalyst cost, high reaction speed, no carbon deposition in the reaction process and the like.
- -
-
Paragraph 0019-0022; 0023-0024; 0027-0034
(2017/08/29)
-
- PROCESS FOR PRODUCING METHACRYLIC ACID COMPOUND
-
PROBLEM TO BE SOLVED: To provide a process for producing a methacrylic acid compound with good yield. SOLUTION: Provided is a production process for producing a methacrylic acid compound represented by formula (II) by reacting a propionic acid compound represented by formula (I) and a formaldehyde compound selected from formaldehyde hemiacetal, formaldehyde acetal, 1,3,5-trioxane and paraformaldehyde, under the presence of a solid acid catalyst and a solid base catalyst, in which, for 1 mole of the formaldehyde compound, 0.005 to 2 moles of water is supplied to the reaction system. (R1 is a hydrogen atom, or an alkyl group.) SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
- -
-
Paragraph 0039; 0043
(2017/03/24)
-
- METHOD FOR PRODUCING METHYLMETHACRYLATE
-
The present invention relates to a process for producing methyl methacrylate, comprising the following steps: A) producing methacrolein andB) reacting the methacrolein obtained in step A) in an oxidative esterification reaction to give methyl methacrylate, characterized in that the two steps A) and B) take place in a liquid phase at a pressure of from 2 to 100 bar, and step B) is carried out in the presence of a heterogeneous noble-metal-containing catalyst comprising metals and/or comprising metal oxides.
- -
-
Paragraph 0213; 0214
(2016/04/20)
-
- PROCESS FOR PREPARING UNSATURATED ESTERS PROCEEDING FROM ALDEHYDES BY DIRECT OXIDATIVE ESTERIFICATION
-
The present invention relates to a process for preparing methyl methacrylate by a direct oxidative esterification of methacrolein with oxygen and methanol, which is conducted in the liquid phase at a pressure of 2 to 100 bar with a gold catalyst. According to the invention, the liquid phase is withdrawn continuously from the reactor and optionally enriched with oxygenous gas, the pH, after the withdrawal, is adjusted to a pH between 5 and 9 by means of addition of a basic solution and this liquid phase is conducted back into the reactor again to an extent of at least 50%.
- -
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Paragraph 0056-0057
(2016/09/26)
-
- CATALYST FOR USE IN PRODUCTION OF METHYL METHACRYLATE, AND METHOD FOR PRODUCING METHYL METHACRYLATE
-
According to the present invention, a molded catalyst for use in the production of methyl methacrylate can be provided. The molded catalyst comprises synthetic faujasite-type zeolite and a layered magnesium silicate compound, wherein the sulfur content in the layered magnesium silicate compound is 0.10% by weight or less. According to the present invention, a method for producing methyl methacrylate can also be provided. The method is characterized by comprising a step of carrying out a gas-phase catalytic reaction of methyl α-hydroxyisobutyrate using the above-mentioned molded catalyst for use in the production of methyl methacrylate.
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Paragraph 0046
(2017/04/04)
-
- METHOD OF PRODUCING CARBOXYLIC ACID ESTER
-
PROBLEM TO BE SOLVED: To provide a method of efficiently producing carboxylic acid ester by inhibiting polymer production. SOLUTION: A method of producing carboxylic acid ester is characterized in that, in the presence of a catalyst comprising a group 10 metal compound, a phosphine compound, a phosphine oxide compound and a proton acid, a hydrocarbon having a carbon-carbon triple bond in a molecule is made to react with a compound having a hydroxyl group and carbon monoxide. COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0056; 0057
(2016/10/07)
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- A PROCESS FOR THE PRODUCTION OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACIDS OR ESTERS
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The present invention relates to a process for the production of an ethylenically unsaturated carboxylic acid or ester, preferably α,? ethylenically unsaturated carboxylic acids or esters, by the liquid phase reaction of formaldehyde or a suitable source thereof with a non-cyclic carboxylic acid ester in the presence of a basic metal salt.
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Page/Page column 19
(2016/10/31)
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- Lanthanum and Cesium-Loaded SBA-15 Catalysts for MMA Synthesis by Aldol Condensation of Methyl Propionate and Formaldehyde
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Abstract: Aldol condensation of methyl propionate (MP) and formaldehyde (FA) is a green and sustainable route to synthesize methyl methacrylate (MMA). In this work, lanthanum and cesium-loaded SBA-15 acid–base bifunctional catalysts for aldol condensation have been prepared by wetness impregnation method to maximize the yield of MMA. With the investigation of the relationship between the properties of catalysts and the catalytic performance, the appropriate acid–base sites for this reaction were provided. The results showed that La existed as LaONO3 on the catalysts and could constitute additional Lewis acid sites on the catalysts. The Cs-0.1La/SBA-15 (with La content of 0.1?%) exhibited higher catalytic activity than the other La-containing catalysts because of the higher density of medium base sites and medium acid sites. The catalysts calcined at 450?°C performed well on this reaction due to the formation of medium base sites on the catalysts as well as the big surface area around 400?m2/g and uniform pore size at 6?nm. When the MP/FA molar ratio was 1/1, the conversion of MP was 29.2?% and the selectivity of MMA could reach 90.4?%. Graphical Abstract: [Figure not available: see fulltext.]
- Wang, Yanan,Yan, Ruiyi,Lv, Zhaopo,Wang, Hui,Wang, Lei,Li, Zengxi,Zhang, Suojiang
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p. 1808 - 1818
(2016/08/30)
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- Method for preparing from glycolic acid ester from carbohydrate
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The invention provides a method for preparing glycolic acid ester from carbohydrate including cellulose, starch, hemicelluloses, cane sugar, glucose, fructose, fructosan, xylose and soluble xylooligosaccharide and a natural wood fibre raw material containing the above carbohydrate component. According to the method, carbohydrate or the natural wood fibre raw material containing the carbohydrate component used as a reaction material undergoes one-step catalytic conversion in an alcohol solvent of 100-400 DEG C by using one or more than two of tungsten oxide, tungsten sulfide, tungsten chloride, tungsten carbide, tungsten hydroxide, tungsten bronze, tungstic acid, tungstate, metatungstic acid, metatungstate, para-tungstic acid, paratungstate, peroxotungstic acid, peroxotungstate, tungsten-containing heteropoly acid and heteropolytungstate as a catalyst, so as to realize carbohydrate high-selectivity and high-yield preparation of glycolic acid ester. The reaction provided by the invention has remarkably advantages as follows: the raw materials are renewable resources, and atom economy is high.
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Paragraph 0023; 0035-0038
(2017/03/25)
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- An Oxidative Route for the Production of Methyl Methacrylate: A Study Over Iron Phosphate Catalysts
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Abstract: An iron phosphate catalyst prepared using the ammonia gel method was supported on silica (CAT 1) and a commercial iron phosphate catalyst was supported on silica using the wet impregnation method (CAT 2). The XRD patterns of both the catalysts showed the presence of quartz-like iron phosphate and a tridymite like phase. In situ XRD under a reducing environment and TPR showed the formation of iron pyrophosphate for both the catalysts at 500?°C. The M?ssbauer spectra of the catalysts were similar and showed the presence of the ferric ion only. NH3-TPD revealed the presence of Lewis and Br?nsted acidic sites on both the catalysts. Oxidative dehydrogenation reactions of methyl iso-burate (MIB) were carried out using a continuous flow fixed bed reactor at contact times of 0.4 and 0.8?s. The conversion of MIB was marginally higher at a contact time of 0.8?s. CAT 2 gave an 11?% yield of methyl methacryalate (MMA) compared to 21?% over CAT 1 at a contact time of 0.8?s. The conversion of MIB increased with co-feeding water. A maximum conversion of MIB (82?%) was obtained at 400?°C, giving a yield of 20?% MMA at a contact time of 0.8?s over CAT 1. However, co-feeding water increased the hydrolysis reaction also, which increased the yield towards iso-butyric acid and methacrylic acid. Graphical Abstract: [Figure not available: see fulltext.]
- Harilal, Avinash,Dasireddy, Venkata D. B. C.,Friedrich, Holger B.
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p. 1169 - 1181
(2016/07/06)
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- METHOD FOR PRODUCING UNSATURATED ACID ESTER OR UNSATURATED ACID
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The present invention relates to a method for producing an unsaturated-acid ester or an unsaturated acid, containing a step of reacting a compound (1) represented by the following formula (1) with a compound represented by the following formula (2) (excluding the compound (1)) in the presence of a Lewis acid catalyst at a temperature of the boiling point of the compound (1) or higher and 350° C. or lower, thereby obtaining products including a compound represented by the following formula (3): (in formula (1) and formula (3), R1, R2 and R4 each independently may be hydrogen atom or an alkyl group, R3 and R5 each independently are hydrogen atom or a deuterium atom, and X is a halogen atom; in formula (2) and formula (3), R6 may be hydrogen atom, an alkyl group or an aryl group, and R7 is hydrogen atom or a deuterium atom).
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Paragraph 0164-0170
(2016/06/01)
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- Method for producing unsaturated acid ester or unsaturated acid
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The present invention relates to a method for producing an unsaturated acid ester or an unsaturated acid, said method comprising a step of reacting a compound (1) represented by formula (1) with a compound represented by formula (2) (excluding the compound (1)) in the presence of a Lewis acid catalyst at a temperature that is equal to or higher than the boiling point of the compound (1) and is equal to or lower than 350 DEG C to thereby produce a product containing a compound represented by formula (3). (2) R6-OR7 [In formula (1) and formula (3), R1, R2 and R4 may independently represent a hydrogen atom or an alkyl group; R3 and R5 independently represent a hydrogen atom or a deuterium atom; and X represents a halogen atom. In formula (2) and formula (3), R6 may represent a hydrogen atom, an alkyl group or an aryl group; and R7 represents a hydrogen atom or a deuterium atom.]
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Paragraph 0172-0181; 0192
(2017/02/09)
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- PROCESS FOR PRODUCTION OF METHACRYLIC ACID ESTERS
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A method for producing α-, β-unsaturated carboxylic acid esters in high yield from acetone cyanohydrin and sulfuric acid through the separation and concurrent catalytic conversion of reaction side products to additional α-, β-unsaturated carboxylic acid ester product. The catalyst comprises at least one Group IA element, and boron as a promoter, on a porous support.
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Paragraph 0078-0088
(2016/05/10)
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- α-Methylenation of Methyl Propanoate by the Catalytic Dehydrogenation of Methanol
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A one-pot system for the conversion of methyl propanoate (MeP) to methyl methacrylate (MMA) has been investigated. In particular, this study is focused on the possibility of performing catalytic dehydrogenation of methanol for the in situ production of anhydrous formaldehyde, which is then consumed in a one-pot base-catalysed condensation with MeP to afford methyl 3-hydroxy-2-methylpropanoate, which spontaneously dehydrogenates to MMA, some of which is subsequently hydrogenated to methyl 2-methypropanoate (MiBu).
- Lorusso, Patrizia,Coetzee, Jacorien,Eastham, Graham R.,Cole-Hamilton, David J.
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p. 222 - 227
(2016/01/26)
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- NITRIDED MIXED OXIDE CATALYST SYSTEM AND A PROCESS FOR THE PRODUCTION OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACIDS OR ESTERS
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The invention relates to a method of producing an ethylenically unsaturated carboxylic acid or ester, preferably an α, β ethylenically unsaturated carboxylic acid or ester. The method includes contacting formaldehyde or a suitable source thereof with a carboxylic acid or ester in the presence of a catalyst and optionally in the presence of an alcohol. The catalyst comprises a nitrided metal oxide having at least two types of metal cations, M1 and M2, wherein M1 is selected from the metals of group 2, 3, 4, 13 (called also IIIA) or 14 (called also IVA) of the periodic table and M2 is selected from the metals of groups 5 or 15 (called also VA) of the periodic table. The invention extends to a catalyst system.
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Paragraph 0102; 0103
(2016/10/31)
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- PROCESS FOR THE PRODUCTION OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACIDS OR ESTERS AND A CATALYST THEREFOR
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A method of producing an ethylenically unsaturated carboxylic acid or ester such as (meth) acrylic acid or alkyl esters thereof, for example, methyl methacrylate is described. The process comprises the steps of contacting formaldehyde or a suitable source thereof with a carboxylic acid or ester, for example, propionic acid or alkyl esters thereof in the presence of a catalyst and optionally an alcohol. The catalyst comprises group II metal phosphate crystals having rod or needle like morphology or a suitable source thereof. The phosphate may be a hydroxyapatite, pyrophosphate, hydroxyphosphate, PO42? phosphate or mixtures thereof. The group II metal may be selected from Ca, Sr, Ba or mixtures thereof, for example, strontium hydroxyapatite and calcium hydroxyapatite. A catalyst system comprising a crystalline metal phosphate catalyst and a catalyst support is also described. The metal phosphate has rod/needle like morphology.
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Paragraph 0159; 0160-0162
(2015/11/16)
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- PREPARATION OF METHYL ACRYLATE VIA AN OXIDATIVE ESTERIFICATION PROCESS
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A process for producing methyl methacrylate, the process comprising contacting reactants comprising methacrolein, methanol and an oxygen-containing gas, under reaction conditions in the presence of a solid catalyst comprising palladium, bismuth and at least one third element X, where X is selected from the group consisting of P, S, Sc, V, Ga, Se, Y, Nb, Mo, La, Ce, and Nd, wherein the solid catalyst further comprises a support selected from at least one member of the group consisting of silica, alumina, calcium carbonate, active carbon, zinc oxide, titanium oxide and magnesium oxide.
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Page/Page column 7
(2015/02/25)
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- PREPARATION OF METHYL METHACRYLATE VIA AN OXIDATIVE ESTERIFICATION PROCESS
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A process for producing methyl methacrylate, the process comprising contacting reactants comprising methacrolein, methanol and an oxygen-containing gas, under reaction conditions in the presence of a solid catalyst comprising palladium, bismuth and at least one third element X selected from the group consisting of Fe, Zn, Ge, and Pb, wherein the solid catalyst further comprises a support selected from at least one member of the group consisting of silica and alumina.
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Page/Page column 6; 7
(2015/02/25)
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- PREPARATION OF METHYL METHACRYLATE VIA AN OXIDATIVE ESTERIFICATION PROCESS
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A process for producing methyl methacrylate, the process comprising contacting reactants comprising methacrolein, methanol and an oxygen-containing gas, under reaction conditions in the presence of a solid catalyst comprising palladium, bismuth and tellurium, wherein the solid catalyst further comprises a support selected from at least one member of the group consisting of silica, and alumina, with the proviso that the process produces less than 1 mole methyl formate per mole of methyl methacrylate.
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Page/Page column 6
(2015/02/25)
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- PROCESS FOR PRODUCING METHYL METHACRYLATE
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The present invention relates to a catalytic continuous process for producing methyl methacrylate, said process comprising the step of reacting methacrolein with oxygen and methanol in the presence of a heterogeneous noble-metal-containing catalyst in an oxidative esterification reaction to give methyl methacrylate, characterized in that the stationary concentration of the starting material methacrolein is equal to or less than 12 % by weight based on the total weight of the reaction mixture in the reactor, and the ratio F between the total liquid volume within the reactor expressed in litres divided by the total weight of catalyst in the reactor expressed in kilograms is equal to or less than 4.
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Page/Page column 9
(2015/07/07)
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- Uncovering the mechanism of homogeneous methyl methacrylate formation with P,N chelating ligands and palladium: Favored reaction channels and selectivities
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The catalytic alkoxycarbonylation of alkynes via palladium and P,N ligands, studied through a prototypical reaction involving propyne methoxycarbonylation yielding methyl methacrylate, has been explored at the B3PW91-D3/PCM level of density functional theory. Four different reaction routes have been probed in detail, spanning those involving one or two hemilabile P,N ligands and either hydride or carbomethoxy mechanisms. The cycle that is both energetically most plausible and congruent with experimental data involves Pd(0) and two P,N ligands acting cocatalytically in turn to shuffle protons via both protonation and deprotonation reactions. Other mechanisms proposed in the literature can be discounted because they would lead to insurmountable barriers or incorrect selectivities. For the preferred mechanism, the P,N ligand is found to be crucial in determining the strong regioselectivity and intrinsically controls the overall turnover of the catalytic cycle with moderate barriers (ΔGa§§ of 20.1 to 22.9 kcal/mol) predicted. Furthermore, the necessary acidic conditions are rationalized via a potential dicationic channel.
- Crawford, L. Ellis,Cole-Hamilton, David J.,Bühl, Michael
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p. 438 - 449
(2015/02/05)
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- METHOD FOR PRODUCING METHACRYLIC ACID ESTER
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The method for producing a methacrylic acid ester of the present invention comprises a dehydration reaction step of having acetone undergo a dehydration reaction in the presence of a dehydration reaction catalyst to obtain a reaction mixture; a propyne/propadiene separation step of separating a mixture containing propyne and propadiene as main components from the obtained reaction mixture; a propyne purification step of separating the separated mixture containing propyne and propadiene as main components into a liquid, gas, or gas-liquid mixture containing propyne as a main component, and a liquid, gas, or gas-liquid mixture containing propadiene as a main component; and a carbonylation reaction step of bringing the obtained liquid, gas, or gas-liquid mixture containing propyne as a main component into contact with carbon monoxide and an alcohol having 1 to 3 carbon atoms in the presence of a catalyst containing at least one selected from the group consisting of Group 8 metal elements, Group 9 metal elements, and Group 10 metal elements to obtain a methacrylic acid ester. According to the method of the present invention, it is possible to provide a method for producing a methacrylic acid ester, which is less likely to receive location restrictions and is also economically and industrially advantageous.
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Paragraph 0104; 0106
(2016/01/25)
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- METHOD OF PRODUCING METHACRYLATE ESTER
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PROBLEM TO BE SOLVED: To provide an efficient method of producing methacrylate esters. SOLUTION: A method of producing a methacrylate ester comprises reacting a compound having a hydroxyl group and carbon monoxide with methylacetylene in the presence of a catalyst containing a group 10 metal compound, a protonic acid and a phosphine compound and is characterized by reducing the partial pressure of carbon monoxide in the course of the reaction. The partial pressure of carbon monoxide is preferably reduced by 0.1 MPa or more, and the partial pressure of carbon monoxide at the beginning of the reduction of carbon monoxide is preferably 1.0 MPa or higher. COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0039-0042
(2016/10/07)
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