- Synthesis of phthalate-free plasticizers by hydrogenation in water using RhNi bimetallic catalyst on aluminated SBA-15
-
In this study, rhodium-nickel bimetallic nanoparticles loaded on aluminated silica (RhNi/Al-SBA-15) were used as catalysts for the hydrogenation of phthalate in water to produce environmentally acceptable non-phthalate plasticizers. Chemical fluid deposition (CFD) was used to dope metals onto the aluminated silica support, which helped to create a uniform structure of RhNi on Al-SBA-15. The introduction of Ni helped to reduce the use of expensive Rh and increase the number of metal active sites by reducing the bimetallic nanoparticle size. Aluminated SBA-15 not only acted as the support for the RhNi bimetallic catalyst but also enhanced the reaction efficiency by introducing Br?nsted and Lewis acid sites and the absorption of phthalates on the catalyst in water. The physicochemical properties of prepared catalysts were characterized by N2 adsorption-desorption isotherm, X-ray diffraction (XRD), in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), Scanning electron microscopy (SEM), and Transmission electron microscopy (TEM). The catalytic performance of the synthesized catalysts was evaluated with the hydrogenation of dimethyl phthalate (DMP). Despite the low solubility of DMP in water, the hydrogenation using Rh0.5Ni1.5/Al-SBA-15 was carried out with an 84.4% reaction yield (cis-?:?trans- = 97.5?:?2.5) at 80 °C using 1000 psi of H2 after 2 h.
- Phan-Vu, Duc-Ha,Tan, Chung-Sung
-
-
Read Online
- PRODUCTION METHOD FOR 1,4-CYCLOHEXANEDICARBOXYLIC ACID DERIVATIVE, 1,4-DICYANOCYCLOHEXANE AND 1,4-BIS(AMINOMETHYL)CYCLOHEXANE
-
A production method for producing a 1,4-cyclohexanedicarboxylic acid derivative, involves subjecting an aqueous ammonia solution of 1,4-cyclohexanedicarboxylic acid to heat concentration, thereby precipitating a 1,4-cyclohexanedicarboxylic acid derivative as a crystal.
- -
-
Paragraph 0066; 0067; 0089
(2021/02/05)
-
- Catalyst for aqueous phase catalytic hydrogenation of phthalic acids and ester derivatives thereof and preparation method and application thereof
-
The invention discloses a catalyst for aqueous phase catalytic hydrogenation of phthalic acids and ester derivatives thereof, a preparation method and application thereof. The catalyst adopts an acidic composite carrier of aluminum-doped ordered mesoporous silica, and combines specific Si/Al, ordered mesoporous size and active component loading capacity to realize catalytic hydrogenation of phthalic acids and ester derivatives thereof in the water phase to prepare corresponding cyclohexanedicarboxylic acids and derivatives thereof. The catalyst is low in raw material cost, simple in preparation process and lower in noble metal loading capacity, wherein the catalytic reaction temperature is 40-100 DEG C, the hydrogen pressure is 3-6MPa, the reaction time is 0.2-3h, the conditions are mild,the solvent is pollution-free and the catalytic efficiency is high.
- -
-
Paragraph 0046-0051; 0055-0056
(2020/07/13)
-
- Catalytic hydrogenation products of aromatic and aliphatic dicarboxylic acids
-
Hydrogenation of aromatic dicarboxylic acids gave 100 % selectivity to respective cyclohexane dicarboxylic acid with 5 % Pd/C catalyst. 5 % Ru/C catalyst was observed to give over hydrogenation products at 493 K and at lower temperature (453 K) the selectivity for cyclohexane dicarboxylic acids was increased. Hydrogenation of phthalic acid with Ru-Sn/Al2O3 catalyst was observed to give phthalide instead of 1,2-benzene dimethanol or 2-hydroxy methyl benzoic acid. Ru-Sn/Al2O3 catalyst selectively hydrogenated the carboxylic group of cyclohexane dicarboxylic acids to give cyclohexane dimethanol. Use of proper catalysts and reaction conditions resulted in desired products.
- Shinde, Sunil B.,Deshpande, Raj M.
-
p. 1137 - 1142
(2019/04/05)
-
- POWDERY 1,4-CYCLOHEXANEDICARBOXYLIC ACID
-
An object of the present invention is to provide a powder of high-purity 1,4-cyclohexanedicarboxylic acid with excellent powder flowability. The invention provides a powder of high-purity 1,4-cyclohexanedicarboxylic acid having particle size distributions (volume basis) such that D10 is within a range of 5 to 55 μm, D50 is within a range of 40 to 200 μm, and D90 is within a range of 170 to 800 μm; and having an aerated bulk density of 0.4 to 0.8 g/cm3, a packed bulk density of 0.5 to 1.0 g/cm3, and a compressibility of 10 to 23%.
- -
-
Paragraph 0133-0138
(2019/02/01)
-
- Method for synthesizing cyclohexanecarboxylic acid by catalyzing hydrogenation of benzene rings through rubidium-gallium-loaded catalytic material
-
The invention relates to the fine chemical engineering field and particularly relates to a method for synthesizing cyclohexanecarboxylic acid by catalyzing hydrogenation of benzene rings through a rubidium-gallium-loaded catalytic material. According to the method, aromatic ring carboxylic acid is catalyzed by virtue of the rubidium-gallium-loaded catalytic material in deionized water and generates selective addition reaction with hydrogen at a low temperature and a relatively low pressure so as to generate cyclohexanecarboxylic acid; the reaction temperature is low, the reaction pressure is lower than that in the prior art, no organic solvent is adopted, the side reactions are few, and the product is conveniently purified, and the method is suitable for industrial production; and the prepared rubidium-gallium-loaded catalytic material can be recycled, is high in catalytic activity and strong in selectivity and is a very promising novel catalytic material.
- -
-
Paragraph 0018; 0030
(2019/01/24)
-
- METHOD FOR PRODUCING 1,4-DICYANOCYCLOHEXANE, 1,4-BIS(AMINOMETHYL)CYCLOHEXANE AND 1,4-CYCLOHEXANEDICARBOXYLIC ACID
-
A method for producing 1,4-dicyanocyclohexane, having a step of obtaining 1,4-dicyanocyclohexane by subjecting a heated concentrate of an aqueous ammonia solution of 1,4-cyclohexanedicarboxylic acid to a cyanation reaction.
- -
-
-
- Preparation method for 1,4-cyclohexanedimethanol or 1,4-cyclohexanedicarboxylic acid
-
The invention relates to a preparation method for 1,4-cyclohexanedimethanol or 1,4-cyclohexanedicarboxylic acid. The preparation method for 1,4-cyclohexanedimethanol comprises the following steps: step 1, subjecting crotonaldehyde, formaldehyde and acrylate to a D-A cycloaddition reaction under base catalysis so as to produce ester group-substituted cyclohexene formaldehyde; and step 2, subjectinga resulting product to complete hydrogenation under the action of a transition metal catalyst to produce 1,4-cyclohexanedimethanol. The preparation method for 1,4-cyclohexanedicarboxylic acid comprises the following steps: step 1, subjecting crotonaldehyde, formaldehyde and acrylate to a D-A cycloaddition reaction under base catalysis so as to produce ester group-substituted cyclohexene formaldehyde; step 2, subjecting a double bond on the resulting product to hydrogenation so as to form an ester group-substituted cyclohexane formaldehyde or cyclohexane methanol; step 3, subjecting cyclohexane formaldehyde or cyclohexane methanol or a mixture thereof to a one-step oxidation reaction so as to form ester group-substituted cyclohexanecarboxylic acid; and step 4, carrying out hydrolysis on aresulting product of the previous step so as to produce 1,4-cyclohexanedicarboxylic acid. The invention provides novel processes for preparing the fine chemicals consisting of 1,4-cyclohexanedimethanol and 1,4-cyclohexanedicarboxylic acid from lignocellulose-based platform chemicals.
- -
-
Paragraph 0053; 0054; 0055
(2018/08/04)
-
- PREPARATION METHOD OF 1,4-CYCLOHEXANEDICARBOXYLIC ACID AND PREPARATION METHOD OF 1,4-CYCLOHEXANEDIMETHANOL
-
The present invention relates to a method for producing 1,4-cyclohexanedicarboxylic acid and a method for producing 1,4-cyclohexanedimethanol. According to the present invention, the method ensures high conversion rates by allowing most of the reactants to participate in a reaction, improves economic feasibility and efficiency in the reaction by simplifying a reaction process, achieves high selectivity by minimizing by-products within a short period of time, and stably controls flow rate of reactants and products. To this end, the method for producing 1,4-cyclohexanedicarboxylic acid includes a step of bringing terephthalic acid and hydrogen gas into contact via counter current in the presence of a metal catalyst which is immobilized on a silica carrier and contains a palladium (Pd) compound.COPYRIGHT KIPO 2018
- -
-
Paragraph 0117-0121; 0145; 0146
(2018/05/15)
-
- PREPARATION METHOD OF 1,4-CYCLOHEXANEDICARBOXYLIC ACID
-
The present invention relates to a method for producing 1,4-cyclohexanedicarboxylic acid. More specifically, the present invention relates to a production method which increases reaction efficiency and economic feasibility owing to more simplified reaction processes, minimizes production of byproducts, and enables the production of high purity 1,4-cyclohexanedicarboxylic acid. To this end, the production method includes a step of reducing terephthalic acid in the presence of a composite metal catalyst consisting of a palladium (Pd) compound and a nickel (Ni) compound.COPYRIGHT KIPO 2017
- -
-
Paragraph 0057; 0058; 0059
(2017/05/23)
-
- A process for preparing 1,4-diphenyl cyclohexane dicarboxylate
-
The present invention relates to a production method of 1,4-diphenyl cyclohexane dicarboxylate which is usable bio-based polycarbonate. More specifically, the present invention relates to a production method of 1,4-diphenyl cyclohexane dicarboxylate, which is a target material obtained by hydrolyzing 1,4-dimethyl cyclohexane dicarboxylate under acid or base conditions to prepare 1,4-cyclohexane dicarboxylic acid, and making the 1,4-cyclohexane dicarboxylic acid react with phenol through esterification.COPYRIGHT KIPO 2017
- -
-
Paragraph 0021; 0053-0055; 0057-0058
(2017/10/25)
-
- A preparation method for a catalyst and the catalyst and is trans -1,4-cyclohexane dicarboxylic acid synthetic method
-
The invention relates to a catalyst preparation method and a synthesis method of a catalyst and trans-1,4-cyclohexane dicarboxylic acid, mainly solves the problem of low selectivity of the catalyst on the trans-1,4-cyclohexane dicarboxylic acid when terephthalic acid is hydrogenated to prepare the 1,4-cyclohexane dicarboxylic acid. The preparation method of the catalyst adopts a method for producing the trans-1,4-cyclohexane dicarboxylic acid, the catalyst takes an activated carbon as a carrier, metals Pd and Pt are active ingredients, the content of Pd in the catalyst is 0.1-5wt%, and the molar ratio of Pd to Pt is 1:1; the method comprises the following steps: using of Pd-Pt hetero-dinuclear complex with required amount to soak the carrier (activated carbon), and then drying to obtain a catalyst precursor; b) using a reducing agent to reduce the compound of Pd and Pt in the precursor to metal to obtain a finished product of the catalyst. By the adoption of the technical scheme of the method, problems in the prior art is well solved, and the method can be used in the industrial production of preparing the trans-1,4-cyclohexane dicarboxylic acid.
- -
-
Paragraph 0029; 0030
(2016/11/09)
-
- Preparation method of 1,4-cyclohexanedimethanol
-
The invention discloses a preparation method of 1,4-cyclohexanedimethanol, which comprises the following steps: performing a primary hydrogenation reaction to terephthalic acid with a palladium-containing catalyst in a hydrogen atmosphere in a solvent of methanol to prepare 1,4-cyclohexane diformic acid; performing a secondary hydrogenation reaction to the 1,4-cyclohexane diformic acid with a copper- and zinc-containing catalyst in the hydrogen atmosphere in the solvent of methanol; and performing after-treatment after the reaction is finished to obtain the 1,4-cyclohexanedimethanol. The preparation method is simplified in operation steps and is increased in reaction yield.
- -
-
Paragraph 0014
(2016/10/31)
-
- Method for catalyzed synthesis of 1,4-cyclohexanedicarboxylic acid
-
The invention discloses a method for catalyzed synthesis of 1,4-cyclohexanedicarboxylic acid. A raw material 4-cyclohexanedicarboxylate is mixed with a catalyst and water, heating is performed to reach 80-100 DEG C for reaction, methanol separation is performed through distillation in the reaction process, the reaction liquid is cooled to reach room temperature after the reaction is completed, a large number of crystals precipitate and are filtered, and white powder, namely the 1,4-cyclohexanedicarboxylic acid, is obtained after a filter cake is dried. The catalyst is one of concentrated hydrochloric acid, concentrated sulfuric acid, phosphoric acid and 1,4-cyclohexanedicarboxylic acid. The catalyst used in the method is easy to obtain, the selected raw materials are cheap and easy to obtain, the reaction conditions are mild, the 1,4-cyclohexanedicarboxylic acid has very high selectivity and conversion rate, the product is also easy to separate, a catalyst containing mother liquor after separation can be continuously used, and waste gas, waste water and industrial residues are not produced in the whole reaction process.
- -
-
Paragraph 0032; 0033
(2017/04/03)
-
- Configurational effects on internal proton transfers and ion-neutral complex formation in stereoisomeric 1,4-di(alkoxymethyl)cyclohexanes on chemical ionization
-
Cis- and trans-1,4-dimethyl-1-d3-methoxymethyl-4-(2-methoxy-2-propyl)cyclohexane (3a-c and 3a-t), the isomeric 1,4-dimethyl-1-methoxymethyl-4-(2-d3-methoxy-2-propyl)cyclohexanes (3b-c and 3b-t) and 1,4-dimethyl-1-methoxymethyl-4-(2-d3-methoxy-2-propyl)cyclohexanes (3b-c and 3b-t) and 1,4-dimethyl-1-ethoxymethyl-4-(2-methoxy-2-propyl)cyclohexanes (3c-c and 3c-t) give rise to different isobutane chemical ionization (CI) mass spectra. The cis isomers exhibit abundant [MH-ROH]+ ions (100%, ROH originating from the tertiary alkoxy group), while no MH+ or [MH-R'OH]+ ions (R'OH originating from the primary alkoxyl) were detected in the mass spectra. This behaviour indicates an efficient proton transfer between the two ether functions in the transient MH+ ions of the cis isomers, resulting in the total and exclusive elimination of methanol from the tertiary position. In contrast to the cis diethers, the trans isomers 3a-t, 3b-t and 3c-t afford relatively abundant [MH-ROH]+ and [MH-R'OH]+ ions. This behaviour is consistent with protonation on each of the two distant non-interacting ether groups, resulting in two isomeric MH+ ions, each of which eliminates the corresponding alcohol. The highly stereospecific behaviour of the cis and trans diethers 3c and 3t is dependent on the presence of the methyl substituents at positions 1 and 4: identical mass spectra were obtained for cis- and trans-1-alkoxymethyl-4-(2-alkoxy-2-propyl)cyclohexanes (4c and 4-t) (four pairs with different 1- and 4-alkoxy groups), and both stereoisomers exhibit exclusive elimination of ROH originating from the tertiary methoxy group in each pair. The absence of [MH-R'OH]+ and MH+ ions in the isobutane CI mass spectra of 4-t requires proton transfer from the primary OR' to the tertiary OR group prior to the elimination of ROH, despite the large distance between them in the trans configuration. These results indicate isomerization of the fragmenting MH+ ions of 4-t to structures which allow a facile proton transfer from the primary the tertiary alkoxyl. The similarity of the mass spectra of 4-c and 4-t suggests trans → cis isomerization, which may occur via an ion-neutral complex.
- Denekamp,Mandelbaum
-
p. 1421 - 1428
(2007/10/03)
-
- Process for the preparation of cyclohexanedicarboxylic acids
-
Disclosed are processes for the preparation of cyclohexanedicarboxylic acids by the non-catalytic hydrolysis or acidolysis of dialkyl cyclohexanedicarboxylate esters. The processes provide a means for converting dialkyl cyclohexanedicarboxylate esters to cyclohexanedicarboxylic acids without the co-production of solid by-products which present disposal problems.
- -
-
-
