- Heterogeneous cyclization of sorbitol to isosorbide catalyzed by a novel basic porous polymer-supported ionic liquid
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In this study, heterogeneous cyclization of sorbitol to isosorbide under basic condition was realized for the first time with a novel porous polymer-supported ionic liquid as catalyst. These polymer-supported ILs were synthesized through the suspension polymerization of 4-vinylbenzyl chloride and divinylbenzene, followed by a quaternization reaction. As compared to those of non-porous, the porous polymers had high specific surface area and large number of active sites. Consequently, they exhibited excellent catalytic activity in the cyclization of sorbitol with dimethylcarbonate (DMC) to isosorbide. As a result, a high conversion of sorbitol (99%) was achieved with 83% yield of isosorbide under optimized conditions. Importantly, the catalysts could be easily separated by decantation and reused for five times without obvious loss of catalytic activity.
- Wang, Yao-Feng,Xu, Bao-Hua,Du, Yi-Ran,Zhang, Suo-Jiang
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Read Online
- Aqueous-phase hydrodeoxygenation of sorbitol with Pt/SiO2-Al2O3: Identification of reaction intermediates
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Aqueous-phase hydrodeoxygenation of sugar and sugar-derived molecules can be used to produce a range of alkanes and oxygenates. In this paper, we have identified the reaction intermediates and reaction chemistry for the aqueous-phase hydrodeoxygenation of sorbitol over a bifunctional catalyst (Pt/SiO2-Al2O3) that contains both metal (Pt) and acid (SiO2-Al2O3) sites. A wide variety of reactions occur in this process including C{single bond}C bond cleavage, C{single bond}O bond cleavage, and hydrogenation reactions. The key C{single bond}C bond cleavage reactions include: retro-aldol condensation and decarbonylation, which both occur on metal catalytic sites. Dehydration is the key C{single bond}O bond cleavage reaction and occurs on acid catalytic sites. Sorbitol initially undergoes dehydration and ring closure to produce cyclic C6 molecules or retro-aldol condensation reactions to produce primarily C3 polyols. Isosorbide is the major final product from sorbitol dehydration. Isosorbide then undergoes ring opening hydrogenation reactions and a dehydration/hydrogenation step to form 1,2,6-hexanetriol. The hexanetriol is then converted into hexanol and hexane by dehydration/hydrogenation. Smaller oxygenates are produced by C{single bond}C bond cleavage. These smaller oxygenates undergo dehydration/hydrogenation reactions to produce alkanes from C1-C5. The results from this paper suggest that hydrodeoxygenation chemistry can be tuned to make a wide variety of products from biomass-derived oxygenates.
- Li, Ning,Huber, George W.
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Read Online
- METHOD FOR PURIFICATION OF ISOSORBIDE
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The invention relates to a process for purifying a crude isosorbide, in which the crude isosorbide is melted and converted, by cooling, into a crude isosorbide melt suspension consisting of isosorbide crystals and residual melt, the amount by weight of impurities in the isosorbide crystals being less than the amount by weight of impurities in the residual melt, optionally a part of the residual melt is separated off mechanically from the crude isosorbide suspension, further the isosorbide crystals in the melt isosorbide suspension are purified from residual melt by washing with a washing isosorbide melt, the amount by weight of impurities in the washing isosorbide melt being less than the amount by weight of impurities in the residual melt.
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Page/Page column 14; 15
(2021/02/26)
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- Sequential dehydration of sorbitol to isosorbide over acidified niobium oxides
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Isosorbide is a bio-based functional diol, which is prepared by sequential dehydration of sorbitol and widely used in plasticizers, monomers, solvents or pharmaceuticals. In this study, a variety of acidified Nb2O5catalysts were prepared and used for the sequential dehydration of sorbitol to isosorbide. Acidification can effectively regulate the surface acidity of catalysts, which was measured by pyridine infrared spectroscopy and NH3-TPD analysis. The catalytic performance was related to the surface acidity, including the reaction temperature and the amount of catalysts. After optimization of reaction conditions, the yield of isosorbide reached 84.1% with complete sorbitol conversion during reaction at 150 °C for 3 h over 2 M sulfuric acid modified Nb2O5. Finally, the reaction mechanism regarding the role of Lewis acid sites was discussed. This study is of great significance for further development of an efficient catalytic system for the dehydration of carbohydrates to isosorbide.
- Guo, Jiaxing,Huang, Long,Li, Cuiqing,Liu, Shanshan,Song, Yongji,Wang, Xincheng
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p. 4226 - 4234
(2021/06/30)
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- Efficient and selective aqueous photocatalytic mono-dehydration of sugar alcohols using functionalized yttrium oxide nanocatalysts
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The mono-dehydration of sugar alcohols such as d-sorbitol and d-mannitol generates 1,4-sorbitan and 1,4-mannitan, respectively, which are relevant platform molecules for the synthesis of detergents and pharmaceuticals. Most reported catalytic systems provided access to di-dehydrated products, while mono-dehydration required special efforts, particularly regarding selectivity and reaction temperature. A series of functionalized yttrium oxides were prepared via sol-gel synthesis in this work, which not only showed an interesting micropipe-like morphology, but also contained functional components. These materials were investigated as photocatalysts in the dehydration of d-sorbitol and d-mannitol, exhibiting high selectivity to mono-dehydration. The effects of solvent, temperature and catalyst were fully discussed. A catalytic mechanism was proposed based on the experimental results and calculations.
- Cheng, Yu,Fan, Chao,Guo, Lina,Huang, Benhua,Li, Xiaoyong,Luque, Rafael,Ma, Xiaomo,Meng, Xu,Pan, Cheng,Sun, Yang,Yang, Juncheng,Zhang, Junjie,Zhang, Weining,Zheng, Aqun
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p. 5333 - 5344
(2020/09/17)
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- Direct Amination of Isohexides via Borrowing Hydrogen Methodology: Regio- and Stereoselective Issues
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The regio and diastereoselective direct mono or diamination of bio-based isohexides (isosorbide and isomannide) has been developed through borrowing hydrogen (BH) methodology using a cooperative catalysis between an iridium complex and a Br?nsted acid. The access to chiral amino-alcohol (NH2-OH) and diamine (NH2-NH2), interesting optically pure bio-based monomers, was also proposed using BH strategy as a sustainable route for their obtention.
- Bahé, Florian,Grand, Lucie,Cartier, Elise,Jacolot, Ma?wenn,Moebs-Sanchez, Sylvie,Portinha, Daniel,Fleury, Etienne,Popowycz, Florence
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supporting information
p. 599 - 608
(2020/02/04)
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- Direct conversion of cellulose into isosorbide over Ni doped NbOPO4catalysts in water
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Isosorbide is a versatile chemical intermediate for the production of a variety of drugs, chemicals, and polymers, and its efficient production from natural cellulose is of great significance. In this study, bifunctional catalysts based on niobium phosphates were prepared by a facile hydrothermal method and used for the direct conversion of cellulose to isosorbide under aqueous conditions. NH3-TPD analysis showed that a high acid content existed on the catalyst surface, and pyridine infrared spectroscopic analysis confirmed the presence of both Lewis acid and Br?nsted acid sites, both of which played an important role in the process of carbohydrate conversion. XRD and H2-TPR characterization determined the composition and the hydrogenation centers of the catalyst. An isosorbide yield of 47% could be obtained at 200 °C for 24 h under 3 MPa H2 pressure. The Ni/NbOPO4 bifunctional catalyst retains most of its activity after five consecutive runs with slightly decreased isosorbide yield of 44%. In addition, a possible reaction mechanism was proposed that the synergistic effect of surface acid sites and hydrogenation sites was favorable to enhancing the cascade dehydration and hydrogenation reactions during the conversion of cellulose to isosorbide. This study provides as an efficient strategy for the development of novel multifunctional heterogeneous catalysts for the one-pot valorisation of cellulose. This journal is
- Guo, Jiaxing,He, Minyao,Li, Cuiqing,Liu, ShanShan,Song, Yongji,Wang, Hong,Wang, Xincheng
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supporting information
p. 10292 - 10299
(2020/07/14)
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- Biological upgrading of 3,6-anhydro-l-galactose from agarose to a new platform chemical
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Recently, the utilization of renewable biomass instead of fossil fuels for producing fuels and chemicals has received much attention due to the global climate change. Among renewable biomass, marine algae are gaining importance as third generation biomass feedstocks owing to their advantages over lignocellulose. Particularly, red macroalgae have higher carbohydrate contents and simpler carbohydrate compositions than other marine algae. In red macroalgal carbohydrates, 3,6-anhydro-l-galactose (AHG) is the main sugar composing agarose along with d-galactose. However, AHG is not a common sugar and is chemically unstable. Thus, not only AHG but also red macroalgal biomass itself cannot be efficiently converted or utilized. Here, we biologically upgraded AHG to a new platform chemical, its sugar alcohol form, 3,6-anhydro-l-galactitol (AHGol), an anhydrohexitol. To accomplish this, we devised an integrated process encompassing a chemical hydrolysis process for producing agarobiose (AB) from agarose and a biological process for converting AB to AHGol using metabolically engineered Saccharomyces cerevisiae to efficiently produce AHGol from agarose with high titers and yields. AHGol was also converted to an intermediate chemical for plastics, isosorbide. To our knowledge, this is the first demonstration of upgrading a red macroalgal biomass component to a platform chemical via a new biological route, by using an engineered microorganism.
- Kim, Dong Hyun,Liu, Jing-Jing,Lee, Jae Won,Pelton, Jeffrey G.,Yun, Eun Ju,Yu, Sora,Jin, Yong-Su,Kim, Kyoung Heon
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p. 1776 - 1785
(2020/03/26)
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- Kinetic analyses of intramolecular dehydration of hexitols in high-temperature water
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Intramolecular dehydration of the biomass-derived hexitols D-sorbitol, D-mannitol, and galactitol was investigated. These reactions were performed in high-temperature water at 523–573 K without added acid catalyst. The rate constants for the dehydration steps in the reaction networks were determined at various reaction temperatures, and the activation energies and pre-exponential factors were calculated from Arrhenius plots. The yield of each product was estimated as a function of reaction time and temperature using the calculated rate constants and activation energies. The maximum yield of each product from the dehydration reactions was predicted over a range of reaction time and temperature, allowing the selective production of these important platform chemicals.
- Yamaguchi, Aritomo,Mimura, Naoki,Shirai, Masayuki,Sato, Osamu
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- METHOD FOR PRODUCING DIANHYDROHEXITOL WITH A STEP OF DISTILLATION ON A THIN-FILM EVAPORATOR
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A method for producing 1,4:3,6-dianhydrohexitols, including the steps of: a) supplying at least one hexitol, b) dehydrating the hexitol, and c) distillating the dehydration product produced in step b), wherein: the hexitol is supplied in the form of an aqueous solution in step a); and the distillation is carried out by means of a thin-film evaporator in step c).
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Paragraph 0041-0049
(2019/04/14)
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- Confinement of Br?nsted acidic ionic liquids into covalent organic frameworks as a catalyst for dehydrative formation of isosorbide from sorbitol
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The confinement of Br?nsted acidic 1-methyl-3-(3-sulfopropyl)-1H-imidazol-3-ium hydrosulfate ([PSMIm][HSO4]) into the channel walls of two-dimensional (2D) COFs using a one-pot self-assembly strategy was achieved by incorporating an imine-linked TPB-DMTP-COF (TPB, triphenylbenzene; DMTP, dimethoxyterephthaldehyde) as the host. An appropriate loading of [PSMIm][HSO4] is crucial for the BIL-COF hybrids to maintain proper geometry in the channel and sufficient acidic sites for the sorbitol substrate and sorbitan intermediate to enter and react. The best yield of isosorbide (97%) from sorbitol to date was obtained in the presence of BIL-COF-30 as the catalyst under optimized conditions. Besides, BIL-COF-30 can be recycled for at least five runs without activity loss.
- Du, Yi-Ran,Xu, Bao-Hua,Pan, Jia-Sheng,Wu, Yi-Wei,Peng, Xiao-Ming,Wang, Yao-Feng,Zhang, Suo-Jiang
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supporting information
p. 4792 - 4799
(2019/09/09)
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- Catalytic dehydration of sorbitol to isosorbide in the presence of metal tosylate salts and metallized sulfonic resins
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Homogeneous catalytic dehydration of sorbitol to isosorbide has been performed with a series of metal tosylates as catalysts. Conversions up to 100 % and selectivities into isosorbide up to 67% were obtained with Bi(OTs)3. The metals were exchanged with acidic sites of sulfonic resins and the resulting materials were evaluated as heterogeneous catalysts. On the contrary to their homogeneous counter parts, the heterogenized metal sites are non-active. The catalytic activity of the modified resins was systematically diminished in comparison to the native resins. The inhibition is greatly dependent on the nature of the metal and, on a larger extent, of the used resin for the cation exchange.
- Dussenne, Corentin,Wyart, Hervé,Wiatz, Vincent,Suisse, Isabelle,Sauthier, Mathieu
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- PROCESS FOR MANUFACTURING DIANHYDROHEXITOL CRYSTALS WITH A STEP OF EVAPORATIVE CRYSTALLIZATION OF THE FIRST CRYSTALLIZATION MOTHER LIQUORS
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A process for manufacturing crystals of 1,4:3,6-dianhydrohexitols, by manufacturing a solution of an internal dehydration product of at least one hexitol, distilling the solution, crystallizing, and wherein the crystallization mother liquors undergo a step of evaporative crystallization. Unlike the prior art processes that seek to recycle the crystallization mother liquors, evaporative crystallization economically and efficiently replaces the succession of steps consisting of at least one concentration, then at least one step of purification by distillation, chromatography, or crystallization.
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Paragraph 0059-0070
(2019/05/18)
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- Method for preparing isosorbide
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The invention belongs to the technical field of supported acid catalysis, and concretely relates to a method for preparing isosorbide. The method is used for solving the problem of poor catalytic activity of existing SO/MxOy supported acids for dehydrating sorbitol to prepare isosorbide and the problem of high production cost due to a high temperature approaching 200 DEG C, needed by reaching a high isosorbide yield. The method in the invention is characterized in that sorbitol used as a reaction raw material is continuously dehydrated under heating and low-vacuum reaction conditions with a supported acid SO/ZrO2-Al2O3 as a catalyst to prepare isosorbide; and the SO/ZrO2-Al2O3 supported acid can be prepared by a coprecipitation process, a sol-gel process or a solventless grinding process. The method is suitable for dehydration of sorbitol to prepare isosorbide.
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Paragraph 0052-0055
(2019/10/01)
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- Effect of carbon chain length on catalytic C–O bond cleavage of polyols over Rh-ReOx/ZrO2 in aqueous phase
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Production of linear deoxygenated C4 (butanetriols, -diols, and butanols), C5 (pentanetetraols, -triols, -diols, and pentanols), and C6 products (hexanepentaols, -tetraols, -triols, -diols, and hexanols) is achievable by hydrogenolysis of erythritol, xylitol, and sorbitol over supported-bimetallic Rh-ReOx (Re/Rh molar ratio 0.5) catalyst, respectively. After validation of the analytical methodology, the effect of some reaction parameters was studied. In addition to C–O bond cleavage by hydrogenolysis, these polyols can undergo parallel reactions such as epimerization, cyclic dehydration, and C–C bond cleavage. The time courses of each family of linear deoxygenated C4, C5, and C6 products confirmed that the sequence of appearance of the different categories of deoxygenated products followed a multiple sequential deoxygenation pathway. The highest selectivity to a mixture of linear deoxygenated C4, C5, and C6 products at 80percent conversion was favoured under high pressure in the presence of 3.7wt.percentRh-3.5wt.percentReOx/ZrO2 catalysts (54–71percent under 80 bar) at 200 °C.
- Besson, Michèle,Da Silva Perez, Denilson,Perret, Noémie,Pinel, Catherine,Sadier, Achraf
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- Solvent-Free Production of Isosorbide from Sorbitol Catalyzed by a Polymeric Solid Acid
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A series of polymeric solid acid catalysts (PDSF-x) is prepared by grafting strong electron-withdrawing groups (?SO2CF3) on a sulfonic acid-modified polydivinylbenzene (PDS) precursor synthesized hydrothermally. The effect of acid strength on sorbitol dehydration is investigated. The textural properties, acidity, and hydrophobicity are characterized by using Brunauer–Emmett–Teller analysis, elemental analysis, and contact angle tests. The results of FTIR spectroscopy and X-ray photoelectron spectroscopy show that both ?SO3H and ?SO2CF3 are grafted onto the polymer network. We used solid-state 31P NMR spectroscopy to show that the acid strength of PDSF-x is enhanced significantly compared with that of PDS, especially for PDSF-0.05. As a result, PDSF-0.05 exhibits the highest isosorbide yield up to 80 %, a good turnover frequency of 231.5 h?1 (compared to other catalysts), and excellent cyclic stability, which is attributed to its large specific surface area, appropriate acid strength, hydrophobicity, and stable framework structure. In addition, a plausible reaction pathway and kinetic analysis are proposed.
- Yuan, Danping,Li, Lei,Li, Feng,Wang, Yanxia,Wang, Feng,Zhao, Ning,Xiao, Fukui
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p. 4986 - 4995
(2019/11/11)
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- Aluminum(III) triflate-catalyzed selective oxidation of glycerol to formic acid with hydrogen peroxide
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Glycerol is a by-product of biodiesel production and is an important readily available platform chemical. Valorization of glycerol into value-added chemicals has gained immense attention. Herein, we carried out the conversion of glycerol to formic acid and glycolic acid using H2O2 as an oxidant and metal (III) triflate-based catalytic systems. Aluminum(III) triflate was found to be the most efficient catalyst for the selective oxidation of glycerol to formic acid. A correlation between the catalytic activity of the metal cations and their hydrolysis constants (Kh) and water exchange rate constants was observed. At 70 °C, a formic acid yield of up to 72% could be attained within 12 h. The catalyst could be recycled at least five times with a high conversion rate, and hence can also be used for the selective oxidation of other biomass platform molecules. Reaction kinetics and 1H NMR studies showed that the oxidation of glycerol (to formic acid) involved glycerol hydrolysis pathways with glyceric acid and glycolic acid as the main intermediate products. Both the [Al(OH)x]n+ Lewis acid species and CF3SO3H Br?nsted acid, which were generated by the in-situ hydrolysis of Al(OTf)3, were responsible for glycerol conversion. The easy availability, high efficiency, and good recyclability of Al(OTf)3 render it suitable for the selective oxidation of glycerol to high value-added products.
- Kong, Kang,Li, Difan,Ma, Wenbao,Zhou, Qingqing,Tang, Guoping,Hou, Zhenshan
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p. 534 - 542
(2019/04/03)
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- A strategy of ketalization for the catalytic selective dehydration of biomass-based polyols over H-beta zeolite
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Biomass contains plentiful hydroxyl groups that lead to an oxygen-rich structure compared to petroleum-based chemicals. Dehydration is the most energy-efficient technique to remove oxygen; however, multiple similar vicinal hydroxyl groups in sugar alcohols impose significant challenges for their selective dehydration. Here, we present a novel strategy to control the etherification site in sugar alcohols by the ketalization of the vicinal-diol group for the highly selective formation of tetrahydrofuran derivatives. A ketone firstly reacts with terminal vicinal hydroxyl groups to form the 1,3-dioxolane structure. This structure of the constrained 1,3-dioxolane ring would improve the accessibility of reactive groups to facilitate intramolecular etherification. As a better leaving group than water, the ketone can also promote intramolecular etherification. Consequently, a range of tetrahydrofuran derivatives are produced in excellent yields with the H-beta zeolite catalyst under mild reaction conditions. This strategy opens up new opportunities for the efficient upgrading of biomass via the modification or protection of hydroxyl groups.
- Che, Penghua,Lu, Fang,Si, Xiaoqin,Ma, Hong,Nie, Xin,Xu, Jie
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supporting information
p. 634 - 640
(2018/02/14)
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- Transition metal triflate catalyzed conversion of alcohols, ethers and esters to olefins
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Herein, we report an efficient transition metal triflate catalyzed approach to convert biomass-based compounds, such as monoterpene alcohols, sugar alcohols, octyl acetate and tea tree oil, to their corresponding olefins in high yields. The reaction proceeds through C-O bond cleavage under solvent-free conditions, where the catalytic activity is determined by the oxophilicity and the Lewis acidity of the metal catalyst. In addition, we demonstrate how the oxygen containing functionality affects the formation of the olefins. Furthermore, the robustness of the used metal triflate catalysts, Fe(OTf)3 and Hf(OTf)4, is highlighted by their ability to convert an over 2400-fold excess of 2-octanol to octenes in high isolated yields.
- Keskiv?li,Parviainen,Lagerblom,Repo
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p. 15111 - 15118
(2018/05/04)
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- Mesoporous Al-promoted sulfated zirconia as an efficient heterogeneous catalyst to synthesize isosorbide from sorbitol
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Mesoporous aluminum-promoted sulfated zirconia (named as mAl-SZ) was directly prepared by grind method, and firstly used to catalyze the solvent-free dehydration of sorbitol to isosorbide. The physicochemical properties of as-prepared catalysts were characterized by FT-IR, TGA, XRD, N2 sorption, NH3-TPD and pyridine-infrared (IR) spectroscopy techniques in order to elucidate the relevance of the catalyst properties and the catalytic performance. It was found that the catalysts prepared by grind method possessed mesoporous structures with high surface area, pure tetragonal phase as well as high sulfur contents, which were advantage to eliminate diffusion limitation and generate abundant acidic sites, especially Br?nsted acidic sites. Furthermore, aluminum promoters could contribute to the considerable increase of the strong acidic sites and ratio of Br?nsted to Lewis acidic sites. Consequently, the mesoporous sulfated zirconia with 6 mol% Al-promoter (6Al-SZ) attained porous structure with improved acidic properties, thus showing the optimal catalytic behavior. The full sorbitol conversion with 73% isosorbide selectivity was achieved under milder conditions (175 °C, 2 h) than those of similar type of catalysts. In addition, the 6Al-SZ exhibited favorable reusability with insignificant drop in isosorbide yield during five reaction cycles.
- Zhang, Yi,Chen, Tong,Zhang, Gang,Wang, Gongying,Zhang, Hua
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p. 258 - 266
(2018/06/26)
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- Unravelling the Mechanism of the Ru/C-Catalysed Isohexide and Ether Isomerization by Hydrogen Isotope Exchange
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In this article we show that the catalytic isomerization of isohexide sugar alcohols as well as their respective ethers can occur by a hydride-based mechanism rather than a dehydrogenation/re-hydrogenation. C?H bonds in α-position to hydroxy and ether groups are activated using Ru/C as solid catalyst at temperatures as high as 160 °C and above. Hydrogen isotope exchange experiments proved that a full hydride exchange and isomerization is possible for isohexides but unexpectedly also for their methyl ethers. This is of great importance as it proves the co-existence of the both mechanisms for reactions that were so far assumed to occur solely by a dehydrogenation/re-hydrogenation. Hence, this co-existence should be taken into account for kinetic investigations of such reaction systems especially in the conversion of biomass-based chemicals under hydrogenation conditions. (Figure presented.).
- Engel, Rebecca V.,Niemeier, Johannes,Fink, Anja,Rose, Marcus
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supporting information
p. 2358 - 2363
(2018/05/08)
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- An Improved Process for Industrial Production of Isosorbide-5-mononitrate: Recycling of Wastes
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Different schemes were studied for the recovery of wastes generated during the industrial production of isosorbide-5-mononitrate (IS-5-MN). For the wastewater, disposal was achieved by hydrolysis of isosorbide-2-mononitrate (IS-2-MN) to the starting material isosorbide (IS) utilizing its alkaline environment, where NaOAc was also recovered effectively in the form of the trihydrate. For the solid waste, two different schemes were investigated: direct crystallization and catalytic hydrogenation. The former afforded useful isosorbide dinitrate (ISDN) efficiently, and the latter provided an efficient and scalable route to synthesize IS-5-MN from ISDN. The combinations of unit operations were evaluated on a 100 kg scale and proved to be feasible and robust. The waste recycling strategy provides an eco-friendly complement for the industrial-scale preparation of IS-5-MN, which minimizes waste emission during the process.
- Zhu, Shi-Guo,Yang, Jiang-Tao,Zhang, Gui-Min,Chen, Cheng-Fu,Zhang, Fu-Li
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p. 991 - 995
(2018/08/03)
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- Solvent free cyclodehydration of sorbitol to isosorbide over mesoporous sulfated titania with enhanced catalytic performance
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Mesoporous sulfated titania (MST), a solid acid catalyst has been prepared in one step by organic template free straightforward hydrolysis of titanium oxysulfate and subsequent calcination at different temperatures. The resultant nano-sized MST catalysts showed remarkable catalytic performances in solvent free cyclodehydration of sorbitol as compared to sulfated TiO2 prepared by conventional method. The catalyst activity of MST catalysts varied with calcination temperature and MST-450 (calcined at 450 °C) exhibited highest catalytic activity and isosorbide selectivity. The MST-450 catalyzed this dehydration reaction at comparatively lower reaction temperature and produced isosorbide with high selectivity in short reaction time. The complete conversion of sorbitol with 70% isosorbide selectivity was achieved in 2 h at 180 °C. The high catalytic activity of MST catalyst attributes to its high specific surface area, large pore size and hence facile diffusion of reactants into the pores and ease to access acid sites. Moreover, the effects of calcination temperature, sulfur content, catalyst amount, reaction temperature and reaction time on conversion and selectivity were studied and the catalyst was also reused.
- Dabbawala, Aasif A.,Alhassan, Saeed M.,Mishra, Dinesh K.,Jegal, Jonggeon,Hwang, Jin-Soo
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- A METHOD FOR PREPARATION OF ANHYDROSUGAR ALCOHOLS USINT A CATALYST THAT IS HETEROPOLY ACI SALT SUBSTITUTED WITH CESIUM
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The present invention relates to a method for preparing anhydrosugar alcohols which converts hydrogenated sugars to the anhydrosugar alcohols by dehydration using a heteropoly acid salt substituted with a cesium as a catalyst. The method for preparing the anhydrosugar alcohols can manufacture clear anhydrosugar alcohols of a high purity and also can process reactions under the low temperature due to a high reactivity of the catalyst. Furthermore, the method has an advantage of manufacturing the anhydrosugar alcohols with superior properties like the purity and a yield which are essential properties for polymerization.COPYRIGHT KIPO 2017
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Paragraph 0006; 0046; 0047
(2017/08/18)
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- Isosorbide synthesis from cellulose with an efficient and recyclable ruthenium catalyst
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Herein, we describe an efficient two-step pathway for isosorbide synthesis from cellulose with the use of new recyclable Ru-catalysts. We show that the oxidative and sulfonation treatments of the new Ru-catalysts increase the acidity and the hydrophilicity of the activated carbon support material, thus reducing the catalyst fouling caused by the build-up of insoluble products. Accordingly, the new Ru-catalysts are more resilient towards lignin containing cellulose than a commercial Ru/C catalyst, and the best Ru-catalyst maintains its high catalytic activity in four consecutive runs with dissolving pulp, microcrystalline cellulose and even with residual lignin containing bagasse pulp. Overall, our two-step approach provides isosorbide in high yields of 56-57 mol% (49-50 wt% of the substrate) from the cellulosic substrates.
- Keskiv?li, Juha,Rautiainen, Sari,Heikkil?, Mikko,Myllym?ki, Teemu T. T.,Karjalainen, Jaakko-Pekka,Lagerblom, Kalle,Kemell, Marianna,Vehkam?ki, Marko,Meinander, Kristoffer,Repo, Timo
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p. 4563 - 4570
(2017/10/13)
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- An efficient and selective conversion of sorbitol in ionic liquids: Use of ion exchange resin as a solid acid catalyst
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Sorbitol was readily converted by heating in hydrophobic ionic liquids by the presence of ion exchange resins. Chemoseletivity of the dehydration depended on the choice of ion exchange resin; Nafion selectively produced isosorbide while Amberlite gave 1,5-anhydrosorbitol along with unreacted sorbitol. Ionic liquids used in the reaction were readily recovered by simple extraction procedure. With these procedures, we succeeded to prepare isosorbide in pure form, not contaminated with either ionic liquids or acid catalyst, by simple experimental procedure.
- Kamimura, Akio,Murata, Kengo,Kawamoto, Takuji
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p. 3616 - 3618
(2017/08/23)
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- A METHOD FOR PREPARATION OF ANHYDROSUGAR ALCOHOLS USINT A CATALYST THAT IS HETEROPOLY ACI SALT SUBSTITUTED WITH AMMONIUM
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The present invention relates to a method of producing an anhydrosugar alcohol which dehydrates hydrogenated sugars to be thus converted into an anhydrosugar alcohol under the presence of a catalyst of an ammonium-substituted salt of heteropoly acid. The method of producing an anhydrosugar alcohol of the present invention can produce a clear high-purity anhydrosugar alcohol at the instant the reaction is completed, without additional purification processes such as neutralization processes and activated carbon treatment processes. Also, due to the high reactivity of the catalyst, the reaction can proceed at low temperatures without purification processes, and can produce the anhydrosugar alcohol having desirable values of pH and electrical conductivity, which are important properties in polymerization.COPYRIGHT KIPO 2017
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Paragraph 0047-0049
(2017/10/13)
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- Method of Preparing Anhydrosugar Alcohols
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The present invention relates to a method for producing anhydrous sugar alcohol in high yield, by simultaneously carrying out a decompression reaction and vacuum distillation in the presence of a catalyst with excellent reactivity under a decompressed condition. According to the present invention, it is possible to produce anhydrous sugar alcohol in higher yield, compared to existing reactions carried out by acid catalysts.COPYRIGHT KIPO 2017
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Paragraph 0047-0049
(2017/04/26)
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- Method using dehydrated sorbitol liquid to produce high-purity isosorbide solution
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The invention discloses a method using dehydrated sorbitol liquid to produce a high-purity isosorbide solution and belongs to the technical field of functional sugar purification. The method includes: preprocessing a raw material, to be more specific, performing decoloring and ion exchange treatment on the dehydrated sorbitol liquid; secondly, performing simulated moving bed separation, wherein DTF chromatographic separation resin is used as the absorbent of the simulated moving bed chromatography, deionized water is used as the eluent of the simulated moving bed chromatography, the particle size of the separation resin is 0.2-0.4mm, and the crosslinking degree of the separation resin is 2-8%. By the method which is simple to operate, high in product purity, low in cost, stable and efficient in equipment and applicable industrial production, the isosorbide solution with the purity being not smaller than 98% can be prepared.
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Paragraph 0029-0036
(2017/07/05)
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- Preparation method of dicarboxylic isosorbide
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The invention provides a preparation method of a dicarboxylic isosorbide. According to the preparation method, sorbitol is taken as a raw material, 0.5 to 48h of dehydration is carried out in the presence of a dehydration catalyst at N2 atmosphere at 100 to 180 DEG C, a monoprotic acid and an esterification catalyst are added, reaction temperature is increased to 185 to 250 DEG C for 0.5 to 48h of esterification, and reduced pressure distillation is carried out so as to obtain the dicarboxylic isosorbide product. The dicarboxylic isosorbide is a novel biomass-based plasticizer, can be used for replacing phthalic acid ester in production of polyvinyl chloride products such as agricultural plastic mulching film. Product yield of the preparation method is high; production separation is convenient; the preparation method is friendly to the environment; and application prospect is promising.
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Paragraph 0026
(2017/07/05)
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- Method for Producing Anhydrosugar Alcohol by High-Pressure Reaction
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The present invention relates to a method of producing anhydrosugar alcohol by dehydrating sugar alcohol at high pressure in the presence of a catalyst which is less acidic than a conventional sulfuric acid catalyst and which can suppress side reactions at high temperature. According to the present invention, anhydrosugar alcohol can be produced in a yield similar to that in a vacuum reaction.
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Paragraph 0044-0061
(2017/09/08)
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- A METHOD FOR PREPARATION OF ANHYDROSUGAR ALCOHOLS USING A SOLID ACID CATALYST LOADED WITH METAL
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The present invention relates to a method for preparing anhydrosugar alcohols comprising the step of dehydrating hydrogenated water and converting the same into anhydrosugar alcohols using a solid acid catalyst loaded with metal in the presence of hydrogen. The method for preparing anhydrosugar alcohols can manufacture transparent anhydrosugar alcohols of high purity without an additional decoloring process, and can manufacture anhydrosugar alcohols with high yield by improving low yield which is a problem of an existing solid acid catalyst.(AA) Yield (%)(BB) Hydrogen pressure (bar)COPYRIGHT KIPO 2017
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Paragraph 0045-0046
(2017/10/14)
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- Purification Method by Decoloring and Crystallization of Anhydrous Sugar Alcohols
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The present invention relates to a production method of anhydrous sugar alcohol, which dehydrates isosorbide and directly crystallizes the same without residence time after batch decolorization. According to the present invention, A decolorized reaction product is prevented from discoloring, thereby being able to produce a final product having excellent chromaticity.(AA) Continuous(BB) Storage tank(CC) Batch(DD) Bleaching(EE) No residence time(FF) Crystallization(GG) ProductCOPYRIGHT KIPO 2017
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Paragraph 0039-0044
(2017/11/14)
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- IMPROVED MANUFACTURING PROCESS OF ESTERS OF ANHYDROSUGAR ALCOHOL
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The present invention relates to a production process for anhydrous sugar alcohol ester. More specifically, the present invention relates to a production process for anhydrous sugar alcohol ester, which is free from reduction in physical properties of a target object anhydrous sugar alcohol ester, while using intermediate products of a sugar alcohol dehydration reaction. The production process of the present invention increases completion rate and speed of an ester reaction by using an excessive amount of fatty acid, and is also economically feasible since purity and yield are not degraded even when unreacted fatty acid is reused after retrieving the same by distillation, thereby enabling mass-production and commercialization.COPYRIGHT KIPO 2017
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Paragraph 0060-0061
(2017/11/22)
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- MANUFACTURING METHOD OF ANHYDROSUGAR ALCOHOL
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PROBLEM TO BE SOLVED: To provide a technology for enhancing yield of anhydrosugar alcohol, a conducting form of a continuous reactions and effective manufacturing method of anhydrosugar alcohol. SOLUTION: By using a specific organic solvent as a solvent and conducting a dehydration reaction of sugar alcohol in presence of the organic solvent and a catalyst, a separation of the catalyst and a product after completion of the reaction becomes easy and anhydrosugar alcohol can be manufactured at high yield and high selectivity. The anhydrosugar alcohol can be manufactured at high yield and high selectivity by extracting the anhydrosugar alcohol by using the organic solvent from the product obtained by a reaction for dehydrating sugar alcohol. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
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Page/Page column 11-16
(2017/12/01)
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- Br?nsted acidic ionic liquid-catalyzed dehydrative formation of isosorbide from sorbitol: Introduction of a continuous process
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A highly efficient synthesis of isosorbide from sorbitol was developed using Br?nsted acidic ionic liquids (BILs) as the catalyst for the first time. The structure-performance relationship was discussed extensively and a proper value of the Gutmann acceptor number (AN) rather than the inherent of acidity was found to be essential for an optimized yield of isosorbide. In addition, the excellent behavior of preferred BIL-4 in the consecutive recycling tests renders the construction of a continuous process probable. Systematic optimization demonstrated that a yield of 82% of isosorbide with a purity of 99.3% could be reached at balance.
- Deng, Jie,Xu, Bao-Hua,Wang, Yao-Feng,Mo, Xian-En,Zhang, Rui,Li, You,Zhang, Suo-Jiang
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p. 2065 - 2073
(2017/07/15)
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- ANTIBACTERIAL COMPOSITION CONTAINING AN ISOMER MIXTURE OF MONOSACCHARIDE ALKYL MONOACETALS OR MONOETHERS
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A bactericidal or bacteriostatic composition comprising an isomer mixture of monosaccharide alkyl monoethers or monoacetals, its use in the treatment or prevention of Gram-positive bacterial infections, its use as a hygiene or dermatological product for external use and a method for disinfecting surfaces.
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Paragraph 0150-0151
(2018/01/11)
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- Dehydration of sorbitol to isosorbide over sulfonic acid resins under solvent-free conditions
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Different commercial sulfonic acid resins (Purolite and Amberlyst type) have been evaluated as acid catalysts for the dehydration of sorbitol to isosorbide. These acidic resins differ in their acid properties, as well as in their thermal and mechanical stabilities. Dehydration of sorbitol has been carried out under solvent-free conditions, by melting sorbitol. At the beginning of reaction, different sorbitans (monodehydration products) were detected, whose dehydration and subsequent cyclization lead to the formation of isosorbide. A maximum yield of 75% is reached after 12?h at 413?K, by using a 5?wt% of Purolite CT269, at atmospheric pressure. This resin maintains its catalytic activity after four runs, and the stability is corroborated by the negligible presence of sulphur species (coming from sulfonic acid leaching) in the reaction medium. This suitable catalytic performance can be explained by its high acid capacity (5.2?meq?g?1) and mechanical and thermal stabilities associated to the macroreticular structure.
- Ginés-Molina, María José,Moreno-Tost, Ramón,Santamaría-González, José,Maireles-Torres, Pedro
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- A method for preparing for isosorbide (by machine translation)
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The invention discloses a isosorbide of the preparation method. In order to solid sorbitol as raw material, a solid acidic molecular sieve as the catalyst; the mass ratio of the solid sorbitol and molecular sieve 100: 1.0 - 5.0, in pressure is - 0.02 - - 0.06 mpa, temperature is 120 - 200 °C, under the molten state of the catalytic reaction of the 2 - 6 hours, to obtain the isosorbide. After the reaction is finished, the content of the product different sorbitol in 80% or more. The invention of the isosorbide preparation method, the use amount of the catalyst, the catalyst can be recovered for reuse, good reaction selectivity, high yield, after treatment is simple. (by machine translation)
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Paragraph 0025-0028
(2017/08/23)
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- Is water a suitable solvent for the catalytic amination of alcohols?
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The catalytic conversion of biomass and biogenic platform chemicals typically requires the use of solvents. Water is present already in the raw materials and in most cases a suitable solvent for the typically highly polar substrates. Hence, the development of novel catalytic routes for further processing would profit from the optimization of the reaction conditions in the aqueous phase mainly for energetic reasons by avoiding the initial water separation. Herein, we report the amination of biogenic alcohols in aqueous solutions using solid Ru-based catalysts and ammonia as a reactant. The influence of different support materials and bimetallic catalysts is investigated for the amination of isomannide as a biogenic diol. Most importantly, the transferability of the reaction conditions to various other primary and secondary alcohols is successfully proved. Hence, water appears to be a suitable solvent for the sustainable production of biogenic amines and offers great potential for further process development.
- Niemeier, Johannes,Engel, Rebecca V.,Rose, Marcus
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supporting information
p. 2839 - 2845
(2017/07/24)
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- One-Pot Preparation of Dimethyl Isosorbide from d-Sorbitol via Dimethyl Carbonate Chemistry
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Direct synthesis of dimethyl isosorbide (DMI) from d-sorbitol via dimethyl carbonate (DMC) chemistry is herein first reported. High yield of DMI was achieved using the nitrogen superbase 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst and performing the reaction in a stainless steel autoclave by increasing the temperature from 90 to 200 °C. In this procedure, DMC features its full capacity acting in the different steps of the process as carboxymethylating, leaving-group (cyclization), and methylating agent; DMC is also employed as the reaction media.
- Aricò,Aldoshin,Tundo
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- PROCESS FOR PRODUCING ISOHEXIDES
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A process is described for producing an isohexide by a base catalyzed conversion of a 1,2:5,6-diacetal of a hexitol to the isohexide.
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Paragraph 0040; 0041
(2017/12/15)
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- A 5 - isosorbide Mononitrate preparation method
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The invention provides a preparation method for isosorbide 5-mononitrate. The preparation method comprises the following steps: with isosorbide dinitrate as a raw materials and Pd/C as a catalyst in a special mixed solvent, carrying out selective hydrogenation reduction on 2-nitro, filtering after reaction, steaming to remove ethyl alcohol in filtrate, extracting residual concentrated liquid through ethyl acetate, washing extracting liquid through dilute acid, washing to be neutral through water, drying through anhydrous magnesium sulfate, filtering to remove a drying agent and steaming to remove ethyl acetate so as to obtain high-purity isosorbide 5-mononitrate. Compared with the prior art, the synthetic method provided by the invention is simple and easy to operate, impurities are easy to remove, the yield and purity are higher, the cost is reduced since the Pd/C and the solvent can be recycled and reused, isosorbide generated through over reduction can be recycled and the preparation method is suitable for industrial production.
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Paragraph 0038; 0039; 0040
(2017/09/01)
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- METHOD FOR PRODUCING ISOPROPANOL BY CATALYTIC CONVERSION OF CELLULOSE
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This invention provides a method for producing isopropanol from cellulose, which is characterized by: cellulose is catalytically converted to isopropanol under existence of a Cu-Cr catalyst. In the method, the Cu-Cr catalyst contains an active phase of CuCr2O4 or further contains an active phase selected from a group consisting of CuO and Cr2O3; the mass ratio of cellulose and water is 15 wt% or below; and the temperature of catalytic reaction is 200-270℃.
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Page/Page column 14
(2017/07/13)
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- Application of glucose derived magnetic solid acid for etherification of 5-HMF to 5-EMF, dehydration of sorbitol to isosorbide, and esterification of fatty acids
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In this study, the catalytic activity of Glu-Fe3O4-SO3H was evaluated for three acid catalyzed reactions: etherification of 5-hydroxymethylfurfural (5-HMF) to 5-ethoxymethylfurfural (5-EMF) in ethanol, dehydration of sorbitol to isosorbide, and esterification of fatty acids with good yields and selectivity. Moreover, the catalyst can be easily separated from the reaction with an external magnetic force and reused at least five times without a significant decrease in catalytic activity.
- Thombal, Raju S.,Jadhav, Vrushali H.
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supporting information
p. 4398 - 4400
(2016/09/13)
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- METHOD FOR PREPARATION OF ANHYDROSUGAR ALCOHOLS USING LAYER CRYSTALLIZATION
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The present invention relates to a manufacturing method of anhydrosugar alcohol by using non-solvent layer crystallization and, more specifically, to a method for manufacturing high purity anhydrosugar alcohol in a short period of time by an eco-friendly method without using a solvent. The method is capable of simplifying facilities and improving yields, by using a layer crystallization technique without using a solvent, and crystallizing distillate obtained by distilling and treating after converting to anhydrosugar alcohol by dehydrating hydrogenated sugar under specific crystallization conditions.COPYRIGHT KIPO 2016
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Paragraph 0058-0063
(2016/10/07)
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- Continuous production of isosorbide method and the use of the device
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The invention relates to a method for continuously producing isosorbide, which comprises the following steps: (1) feeding: mixing sorbitol and a catalyst in a reactor; (2) reaction: under reduced pressure, controlling the temperature in the reactor to sequentially initiate first dehydration reaction and second dehydration reaction of the sorbitol so as to generate the isosorbide, and meanwhile, enabling the isosorbide and water to form a gaseous mixture; and (3) condensation separation: controlling the condensation temperature of the condenser to sequentially condense the isosorbide and water in the gaseous mixture from the reactor, thereby obtaining the isosorbide. The invention also relates to a device for the method.In the sorbitol dehydration reaction process, the isosorbide and water are separated in time by distillation, thereby promoting the selective dehydration reaction, simplifying the separation technique and implementing purification of the isosorbide.
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Paragraph 0043-0044
(2017/05/26)
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- ISOIDIDE MANUFACTURE AND PURIFICATION
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Methods are provided for the conversion of isosorbide to isoidide, wherein the isosorbide contains sorbitan impurities. The impurities in the isosorbide subjected to epimerization are converted to hydrodeoxygenation products. A method for synthesizing isoidide, comprising, providing an isosorbide containing one or more sorbitans; and, epimerizing the isosorbide to form an epimerization product comprising isoidide and hydrodeoxygenation products.
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Paragraph 00104
(2016/09/22)
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- METHOD FOR STABILIZING A COMPOSITION CONTAINING AT LEAST ONE PRODUCT OF INTERNAL DEHYDRATION OF A HYDROGENATED SUGAR, RESULTING COMPOSITION AND USES THEREOF
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A method for improving the stability of compositions of a product for internal dehydration of a hydrogenated sugar, in particular an isosorbide composition, the method involving the use of monoethanolamine, diethanolamine, triethanolamine and the mixtures thereof as a stabilization agent. The resulting compositions and their various uses thereof are also described.
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Paragraph 0080
(2016/04/19)
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- METHOD FOR PREPARATION OF ANHYDROSUGAR ALCOHOLS USING LAYER CRYSTALLIZATION WITH SOLVENT
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The present invention relates to a manufacturing method of anhydrosugar alcohol by using layer crystallization with a solvent and, more specifically, to a manufacturing method of high purity anhydrosugar alcohol, which has excellent energy efficiency in comparison with a non-solvent melt crystallization process. The method is capable of simplifying facilities and improving yields, by using a layer crystallization technique with a small amount of a solvent used, and crystallizing distillate obtained by distilling and treating after converting to anhydrosugar alcohol by dehydrating hydrogenated sugar under specific crystallization conditions.COPYRIGHT KIPO 2016
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Paragraph 0064-0069
(2016/10/07)
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- METHOD FOR PURIFYING ANHYDROUS SUGAR ALCOHOL, ANHYDROUS SUGAR ALCOHOL AND RESIN
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Provided are an anhydrosugar alcohol purification method, etc. with which an anhydrosugar alcohol can be efficiently purified and an anhydrosugar alcohol of excellent storage stability can be obtained, and which can limit discoloration and reduction of glass transition temperature of a resin obtained using said anhydrosugar alcohol. The anhydrosugar alcohol purification method is provided with a step for distilling an anhydrosugar alcohol from a substance to be distilled comprising active carbon and the anhydrosugar alcohol.
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Paragraph 0091; 0092
(2017/01/19)
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