- Selective Hydrogenolysis of Glycerol to 1,3-Propanediol over Rhenium-Oxide-Modified Iridium Nanoparticles Coating Rutile Titania Support
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The effect of support in Ir-ReOx catalysts for glycerol hydrogenolysis to 1,3-propanediol was investigated. Rutile TiO2 support showed high activity, even higher than previously reported SiO2 support. Anatase TiO2, C, ZrO2, CeO2, Al2O3, and MgO supports showed very low activity of supported Ir-ReOx pairs. Higher Ir-based 1,3-propanediol productivity of Ir-ReOx/rutile catalyst was obtained at the initial stage even with lower Re/Ir ratio (typical Ir loading amount, 4 wt %, nominal ratio of 0.25; actual ratio of 0.24) without addition of H2SO4 than that of Ir-ReOx/SiO2. The 1,3-propanediol productivity over Ir-ReOx catalysts showed dependency on catalyst compositions (metal loading amount), and the relationship between catalyst structure and activity was further established over Ir-ReOx/rutile. Relatively high Ir loading amount in comparison with small surface area (6 wt %, on 6 m2 g-1 rutile TiO2) showed the highest activity (Ir-based activity). From combined characterization results altogether (TPR, TEM, XPS, XAS, CO adsorption, CO FT-IR) with a kinetics study, the Ir metal particles interacted with the partially oxidized ReOx cluster (average valence of Re: +3) almost totally covering the surface of rutile TiO2 particles, and the active site was the Ir-ReOx interface. Small amounts of Ir species were incompletely reduced; however, such IrOx species as well as rutile TiO2 support were not directly involved in glycerol hydrogenolysis. The role of rutile support was regarded as providing a unique environment for stabilization of uniform and small Ir-ReOx particles with very high surface density on rutile TiO2, which increased the number of active sites per Re amount.
- Liu, Lujie,Asano, Takehiro,Nakagawa, Yoshinao,Tamura, Masazumi,Okumura, Kazu,Tomishige, Keiichi
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- Influence of Pd precursors and Cl addition on performance of Pd-Re catalysts in glycerol hydrogenolysis to propanediols
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Pd-Re/SBA-15 catalysts with different Pd precursors were prepared by the impregnation method. N2 adsorption-desorption, XRD, H2-TPR, TEM and NH3-TPD were used to characterize the physical and chemical properties of the cat
- Li, Yuming,Liu, Huimin,Ma, Lan,He, Dehua
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- Aqueous-phase deoxygenation of glycerol to 1,3-propanediol over Pt/WO 3/ZrO2 catalysts in a fixed-bed reactor
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Deoxygenation of glycerol in aqueous medium catalyzed by Pt/WO 3/ZrO2 at relatively low temperatures (110-140°C) under hydrogen pressure range from 2 to 5 MPa in a fixed-bed continuous-flow reactor gives 1,3-propanediol (1,3-PDO) and n-propanol (n-PrOH) as the predominant products, indicating high selectivity for deoxygenation of the secondary hydroxyl group over the primary hydroxyl groups of the glycerol. The optimum catalyst was prepared by calcination of WO3/ZrO2 at 700°C and loading of 3.0 wt% Pt with W content of 10 wt%. The effect of reaction temperature, hydrogen pressure and initial water content were evaluated to find the optimum reaction conditions. The glycerol conversion and the yield of 1,3-PDO greatly depended on these factors. At 130°C, 4 MPa and 70.2% conversion, the yield of 1,3-PDO was up to 32.0% (1,3-PDO/1,2-PDO = 17.7). The proposed mechanism for glycerol deoxygenation in aqueous medium over Pt/WO 3/ZrO2 is an ionic pathway involving proton and hydride ion transfer steps.
- Qin, Li-Zhen,Song, Min-Jie,Chen, Chang-Lin
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- Pt/Nb-WOx for the chemoselective hydrogenolysis of glycerol to 1,3-propanediol: Nb dopant pacifying the over-reduction of WOx supports
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Selective hydrogenolysis of glycerol to 1,3-propanediol (1,3-PD) is an important yet challenging method for the transformation of biomass into value-added chemicals due to steric hindrance and unfavorable thermodynamics. In previous studies, chemoselective performances were found demanding and sensitive to H2 pressure. In this regard, we manipulate the chemical/physical characteristics of the catalyst supports via doping Nb into WOx and prepared 1D needle-, 2D flake-, and 3D sphere-stack mesoporous structured Nb-WOx with increased surface acid sites. Moreover, Nb doping can successfully inhibit the over-reduction of active W species during glycerol hydrogenolysis and substantially broaden the optimal H2 pressure from 1 to 5 MPa. When Nb doping is 2%, supported Pt catalysts showed promising performance for the selective hydrogenolysis of glycerol to 1,3-PD over an unprecedentedly wide H2 pressure range, which will guarantee better catalyst stability in the long run, as well as expand their applications to other hydrogen-related reactions.
- Yang, Man,Zhao, Xiaochen,Ren, Yujing,Wang, Jia,Lei, Nian,Wang, Aiqin,Zhang, Tao
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- Discovering positively charged Pt for enhanced hydrogenolysis of glycerol to 1,3-propanediol
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Atomically-dispersed Pt supported on WOx-modified tantalum oxide was developed as a highly active catalyst for selective hydrogenolysis of glycerol, with the productivity of 30.80 g gPt-1 h-1 toward 1,3-propanediol. The WOx species pre-deposited on T-Ta2O5 were found to assist the atomic dispersion of platinum. The WOx-stabilized Ptδ+ species adsorb hydrogen easily and facilitate the hydrogen heterolytic dissociation, which significantly enhances the capability of in situ generated Br?nsted acid sites and the hydrogenation activity. This provides a new strategy for developing bi-functional catalysts for a broad range of hydrogen and acid-involved reaction.
- Zhao, Binbin,Liang, Yu,Liu, Lei,He, Qian,Dong, Jinxiang
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- Polymerization mechanism of trimethylene carbonate carried out with zinc(II) acetylacetonate monohydrate
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The proposed mechanism of initiation and course of ring-opening polymerization of cyclic trimethylene carbonate (TMC) involving zinc(II) acetylacetonate is in accordance with the mechanism of monomer activation. At the first stage of the process, coordination of carbonate to Zn(Acac) 2·H2O complex occurs with the release of weakly coordinated water molecules. This free water molecule reacts with active TMC-Zn(Acac)2 complex. The reaction results in the formation of propanediol and CO2 emission. During further stages of the investigated process, the formed propanediols, or later the oligomeric diols produced with polymerization, are cocatalysts of the chain propagation reaction. The chain propagation occurs because of repeating activation of the TMC monomer through the creation of an active structure resulting in the exchange/transfer reaction between the zinc complex and the monomer, with its following attachment to the hydroxyl groups, carbonate ring opening, and formation of the carbonic unit of polymer chain.
- Pastusiak, Malgorzata,Dobrzynski, Piotr,Kaczmarczyk, Bozena,Kasperczyk, Janusz
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- Hydrogenation of 3-hydroxypropanal into 1,3-propanediol over bimetallic Ru-Ni catalyst
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A series of Ni-based catalysts, including Ru/SiO2, Ni/SiO2 and Ru-Ni/SiO2, were prepared and employed in the hydrogenation of 3-hydroxypropanal (3-HPA) to 1,3-propanediol (1,3-PDO). The catalysts were systematically characterized by means of XRD, TEM, HRTEM, SEAD, XPS, H2-TPD, H2-TPR and N2-physisorption. It was indicated that the introduction of Ru onto the Ni/SiO2 not only increased the porosity of catalyst and the degree of dispersion of Ni species but also promoted the reduction of Ni2+ to Ni0 and the generation of active hydrogen species. The catalytic performance evaluation showed that the Ru-40Ni/SiO2 catalyst, among all others, could provide the largest yield of 1,3-PDO (above 99.0%) and highest TOF (4.70 × 103 S-1). The optimized reaction conditions over the Ru-40Ni/SiO2 catalyst had been established as follows: reaction temperature = 80 °C, H2 pressure = 2.0 MPa and LHSV = 0.4 h-1. In consideration of its extremely low H2 pressure and very high yield of 1,3-PDO for the hydrogenation of 3-HPA, to the best of our knowledge, the Ru-40Ni/SiO2 catalyst appeared to be the most efficient catalyst among all others reported in the literature. The good performance enabled the Ru-40Ni/SiO2 catalyst to be very promising in its industrial application.
- Li, Li-Jun,Yi, Wen-Jun,Liu, Tian-Wei,Huang, Chen,Chao, Zi-Sheng
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- Solid acid co-catalyst for the hydrogenolysis of glycerol to 1,3-propanediol over Ir-ReOx/SiO2
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Hydrogenolysis of aqueous glycerol was conducted with Ir-ReO x/SiO2 catalyst and solid acid co-catalyst. Considering the reusability and activity, H-ZSM-5 is the most suitable solid co-catalyst. The property of Ir-ReOx/SiO2 + H-ZSM-5 system including kinetics and selectivity trends in various reaction conditions is similar to the case of Ir-ReOx/SiO2 + H2SO4. The catalyst stability, activity, and the maximum yield of 1,3-PrD of Ir-ReO x/SiO2 + H-ZSM-5 were slightly lower than Ir-ReO x/SiO2 + H2SO4. The role of added acid may be to protonate the surface of ReOx cluster to increase the number of hydroxorhenium site, which activates glycerol by the formation of glyceride species.
- Nakagawa, Yoshinao,Ning, Xuanhe,Amada, Yasushi,Tomishige, Keiichi
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- Nanoparticulate Pt on mesoporous SBA-15 doped with extremely low amount of W as a highly selective catalyst for glycerol hydrogenolysis to 1,3-propanediol
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It has been documented that W-modified Pt catalysts with relatively high tungsten contents are effective for the catalytic transformation of biodiesel-derived glycerol to 1,3-propanediol (1,3-PDO). Herein, we report a new finding that Pt/W-SBA-15 catalysts with extremely low W/Si atomic ratios (≤1/80) exhibit excellent catalytic performance in the hydrogenolysis of glycerol to 1,3-PDO. In particular, a Pt/W-SBA-15 catalyst with the W/Si ratio of as low as 1/640 (Pt/W-SBA-15(1/640)) gave rise to the highest 1,3-PDO selectivity of 70.8% at a high glycerol conversion of 86.8% and thus afforded the highest yield of 1,3-PDO of 61.5%. A combination of characterization techniques evidenced that tungsten was homogeneously incorporated into SBA-15 in the form of isolated tetragonal WO4 and only displayed Lewis acidity. The particle size of Pt evolved in a reverse volcanic curve with the W/Si ratio, with the smallest size being observed for Pt/W-SBA-15(1/640). Control experiments indicated strong synergy between Pt nanoparticles (NPs) and WO4 in the hydrogenolysis of glycerol. A probe reaction suggested that Br?nsted acid sites were generated in situ on the Pt/W-SBA-15 catalysts in a H2 atmosphere by the reaction between WO4 and spillover H atoms from the Pt NPs. It is plausible that the hydrided WO4 functioned as a highly selective active centre in the hydrogenolysis of glycerol to 1,3-PDO, whereas the Pt NPs played the role of a reservoir of spillover H atoms. Thus, a good match between the isolated WO4 and the small Pt NPs was responsible for the superior catalytic performance of Pt/W-SBA-15(1/640).
- Fan, Yiqiu,Cheng, Shijie,Wang, Hao,Ye, Danhong,Xie, Songhai,Pei, Yan,Hu, Huarong,Hua, Weiming,Li, Zhen Hua,Qiao, Minghua,Zong, Baoning
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- 1-Butanol production from glycerol by engineered Klebsiella pneumoniae
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To utilize the by-product of biodiesel production, Klebsiella pneumoniae, a well-known glycerol-fermenting microorganism, was engineered to produce 1-butanol. The modified CoA-dependent and 2-keto acid pathways were established by expressing the genes ter-bdhB-bdhA and kivd, respectively. The 1-butanol titer and specific BuOH yield were 15.03 mg L-1 and 27.79 mg-BuOH per g cell in KpTBB (K. pneumoniae overexpressing the genes ter-bdhB-bdhA), and 28.7 mg L-1 and 51.58 mg-BuOH per g cell in Kp-kivd (K. pneumoniae overexpressing the gene kivd), respectively. Moreover, the native products in K. pneumoniae fermentation were down regulated using the antisense RNA strategy. The resulting yield of 1,3-propanediol and 2,3-butanediol was reduced by 81% and 15%, respectively. This work reports a new strain, K. pneumoniae, for 1-butanol production and the application of an antisense RNA strategy as an effective method for reducing the main by-products.
- Wang, Miaomiao,Fan, Lihai,Tan, Tianwei
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- Facilitating Pt?WOx Species Interaction for Efficient Glycerol Hydrogenolysis to 1,3-Propanediol
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Designing efficient catalysts for glycerol hydrogenolysis to 1,3-propanediol (1,3-PDO), which involves the selective cleavage of the secondary C?O bond, is a challenging task. Current Pt?WOx-based catalysts often provide low atom efficiency of W and Pt toward 1,3-PDO production due to undesired catalyst structures. Herein, we fabricate the highly-dispersed substantially uniform WOx species on inert α-Al2O3 support by simple high-temperature heat-treatment, and the amount of Pt?WOx interface active sites could be adjusted by Pt loading, showing an excellent catalytic performance in glycerol hydrogenolysis at high concentration of glycerol, especially the unprecedented W efficiency (76 g1,3-PDOgW?1 h?1) toward 1,3-PDO. The high catalytic efficiency is attributed to the strong interaction between the isolated WO4 species and platinum, which could in-situ generate the Br?nsted acid sites during the reaction as evidenced by IR analysis with NH3 adsorption.
- Zhao, Binbin,Liang, Yu,Liu, Lei,He, Qian,Dong, Jin-Xiang
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- An efficient, selective process for the conversion of glycerol to propylene glycol using fixed bed raney copper catalysts
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Propylene glycol is formed in yields of up to 95% at 100% conversion using a Raney Cu catalyst in a fixed bed reactor. The reaction uses an 80% aqueous glycerol solution and a hydrogen pressure of 600 psi. The primary byproduct is ethylene glycol formed in 1-3% yield. In a reaction run continuously for 24 d using a sample of a commercial preparation of Raney Cu, the selectivity to propylene glycol at 100% glycerol conversion was 94.6% with a space-time yield (STY) of 0.49 g of 1,2-propylene glycol/mL Raney Cu/h. Ethylene glycol was formed in 2.5% yield, while methanol, ethanol, n-propanol 1,3-propylene glycol, and acetol were present in less than 1% yield.
- Tanielyan, Setrak K.,Marin, Norman,Alvez, Gabriela,Bhagat, Ramesh,Miryala, Balaraju,Augustine, Robert L.,Schmidt, Stephen R.
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- Understanding the promotional effect of Au on Pt/WO3 in hydrogenolysis of glycerol to 1,3-propanediol
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Pt/Au/WO3 bimetallic catalysts were prepared by impregnation of Pt onto preformed Au/WO3, obtained by a hexadecyl trmethyl ammonium bromide (CTAB)-assisted one-pot synthesis method. The resulting Pt/Au/WO3 catalysts exhibited remarkable synergistic effects for selective hydrogenolysis of glycerol to 1,3-propanediol. The characterization results showed that doping of Au promoted the reduction of both Pt and W at low temperatures and uniform dispersion of Pt on the WO3 support. Furthermore, more low-valence Pt species were produced on the WO3 surface after introduction of Au. These changes in electronic properties resulted in enhancement of both glycerol conversion and selectivity for 1,3-propanediol.
- Yang, Chaojun,Zhang, Fan,Lei, Nian,Yang, Man,Liu, Fei,Miao, Zhili,Sun, Yongnan,Zhao, Xiaochen,Wang, Aiqin
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- Promoting effect of re addition to Rh/SiO2 on glycerol hydrogenolysis
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Modification of Rh/SiO2 with ReOx enhanced the activity of glycerol hydrogenolysis remarkably and suppressed degradation reactions simultaneously. At the same time, the formation of 1,3-propanediol became more favorable on the Rh-ReOx/SiO2. Copyright
- Shimao, Akira,Koso, Shuichi,Ueda, Naoyuki,Shinmi, Yasunori,Furikado, Ippei,Tomishige, Keiichi
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- Towards selective electrochemical conversion of glycerol to 1,3-propanediol
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1,3-propanediol (1,3-PD) is a bulk chemical with myriad applications in polymers, lubricants, cosmetics, foods industries and in the synthesis of heterocyclic compounds. Current commercial production of 1,3-PD involves a thermocatalytic process using acrolein (DuPont) and ethylene oxide (Shell) as starting feedstock. These feedstocks are petroleum-based and there are many efforts at using glycerol as low cost biomass-derived feedstock for 1,3-PD production. A number of catalyst designs and bacterial & fungal strains are being explored for respective catalytic and fermentation routes to glycerol-to-1,3-PD. However, the electrochemical method received little attention for the purpose. In this work, in order to explore the possibility of using partly refined glycerol byproduct of biodiesel production as feedstock, we investigated conversion and 1,3-PD selectivity of glycerol electrolysis in chloride media. We demonstrated selective glycerol-to-1,3-PD conversion using Pt or RuO2-based dsa as anode and Zn or Pb as cathode in NaCl and KCl at pH 1. This electrochemical glycerol-to-1,3-PD conversion is not only green, it is a potential process network loop between biodiesel production and chlor-alkali industry.
- James, Olusola O.,Sauter, Waldemar,Schr?der, Uwe
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- Hydrogenolysis of glycerol to 1,3-propanediol over H-ZSM-5-supported iridium and rhenium oxide catalysts
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The hydrogenolysis of glycerol to 1,3-propanediol (1,3-PrD) over Ir-ReOx catalysts supported on H-ZSM-5 (denoted as Ir-ReOx/H-ZSM-5) was investigated. The glycerol conversion and 1,3-PrD yield strongly depended on the catalyst composition (Re/Ir) and the amount of metal loading. The analyses of the catalysts using X-ray powder diffraction and transmission electron microscopy revealed that a higher metal dispersion of Ir and a smaller Ir particle were encouraged by the addition of Re to the catalyst. Furthermore, a strong electronic interaction between Ir and Re in the Ir-ReOx/H-ZSM-5 catalyst was observed from X-ray photoelectron spectroscopy measurements. In the study on the effects of operating conditions, increasing the temperature and reaction time resulted in a higher glycerol conversion at the expense of 1,3-PrD selectivity due to over-hydrogenolysis, whereas increasing the pressure had a positive effect on 1,3-PrD selectivity. The highest 1,3-PrD yield observed was achieved at 2.8% with 14.9% glycerol conversion and 19.0% 1,3-PrD selectivity.
- Chanklang, Sarun,Mondach, Wongsaphat,Somchuea, Pooripong,Witoon, Thongthai,Chareonpanich, Metta,Faungnawakij, Kajornsak,Seubsai, Anusorn
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- Cu boosting the collaborative effect of Ni and H+in alloyed NiCu/saponite catalysts for hydrogenolysis of glycidol
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The effect of copper on various acid saponite supported Ni-Cu bimetallic catalysts, prepared with different Ni?:?Cu ratios, was studied for the liquid phase hydrogenolysis of glycidol on a batch reactor at 393 and 453 K. Characterization of the catalysts showed that Ni and Cu are in close contact as the XRD measurements evidenced the formation of an alloy. H2chemisorption results revealed that the measured metallic area progressively decreased with an increase in the wt% of copper. In the presence of high metal activity (higher Ni wt%), the formation of 1,2-propanediol (1,2-PD) outweighed, while acid activity led to the formation of dimerization and oligomerization products. The addition of Cu and the increase of the reaction temperature decreased the diol formation but boosted the 1,3-PD/1,2-PD ratio. This could be explained by an improvement of the collaborative effect between the metal Ni and the H+of the saponite. Therefore, the presence of an appropriate amount of Cu allowed the control of the hydrogenation capacity of Ni and enhanced the collaborative effect of Ni and H+favouring the formation of 1,3-propanediol with respect to 1,2-propanediol.
- Cesteros, Yolanda,Gebretsadik, Fiseha Bogale,González, María Dolores,Ruiz-Martinez, Javier,Salagre, Pilar
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- Alcohol-treated SiO2 as the support of Ir-Re/SiO2 catalysts for glycerol hydrogenolysis
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The surface of SiO2 support was pretreated by C1–C4 normal alcohols before the impregnation of iridium and rhenium precursors. These catalysts were applied in high concentration glycerol aqueous solution hydrogenolysis. The catalysts prepared from the pretreated supports exhibited high catalytic activity because of the formation of more active sites from a high dispersion of iridium oxide and rhenium oxide. The catalysts with the support pretreated by 1-propanol showed the highest glycerol conversion of 59.5%. The supports and catalysts were characterized by FT-IR, nitrogen adsorption, TPR, XRD, TEM, H2-chemisorption and NH3-TPD.
- Luo, Wenting,Lyu, Yuan,Gong, Leifeng,Du, Hong,Jiang, Miao,Ding, Yunjie
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- Selective hydrogenolysis of glycerol to 1,3-propanediol over a Pt/WO 3/TiO2/SiO2 catalyst in aqueous media
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SiO2-supported Pt/WO3/TiO2 catalysts were prepared; they were found to be more active and selective than the Pt/WO 3/TiO2 catalyst for glycerol hydrogenolysis to 1,3-propanediol in a slurry batch reactor. The influences of catalyst component, reaction medium, reaction temperature, H2 pressure and reaction time on glycerol hydrogenolysis over the Pt/WO3/TiO2/SiO 2 catalyst were investigated. XRD, TEM, NH3-TPD and Py-IR characterization were employed to reveal the roles of WO3 and TiO2 in the performance of the Pt based-catalysts. XRD patterns and TEM images showed that the presence of TiO2 species in the catalyst favored the dispersion of platinum. The weak Br?nsted acid sites formed by addition of WO3 to the catalyst were concluded to play a key role in selective formation of 1,3-propanediol, based on the results of NH 3-TPD and Py-IR characterization.
- Gong, Leifeng,Lu, Yuan,Ding, Yunjie,Lin, Ronghe,Li, Jingwei,Dong, Wenda,Wang, Tao,Chen, Weimiao
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- Production and productivity of 1,3-propanediol from glycerol by Klebsiella pneumoniae GLC29
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Interest in the development of the bioproduction of 1,3-propanediol, an important chemical intermediate with various industrial applications, has increased in recent years. Klebsiella pneumoniae is one of the most studied and efficient bacteria for 1,3-propanediol production from glycerol. A new isolate of K. pneumoniae was investigated using response surface methodology by central composite design for the production of 1,3-propanediol using glycerol. The effects of pH, temperature, stirrer speed, and glycerol concentration on the production and productivity of 1,3-propanediol were examined. Considering both production and productivity, the best conditions for glycerol conversion in 1,3-propanediol are: a pH range of 6.9-7.1, a temperature between 33 and 38.5°C, a stirrer speed of 110-180 rpm, and a glycerol concentration of 39-49 g l-1. Batch fermentation carried out at a pH of 7.0, a temperature of 35°C, a stirrer speed of 150 rpm, and a glycerol concentration of 40 g l-1 produced 20.4 g 1,3-propanediol l-1, with a maximum volumetric productivity of 2.92 g l-1 h-1 and a yield of 0.51 g g-1. The main byproducts were acetic acid (approximately 7.0 g l-1) and formate (approximately 3.7 g l-1). The newly isolated K. pneumoniae GLC29 showed potential for the conversion of glycerol into 1,3-propanediol, with high production and productivity.
- Da Silva, Gervásio Paulo,De Lima, Cristian J. Bolner,Contiero, Jonas
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- Mesoporous Ti-W oxide: Synthesis, characterization, and performance in selective hydrogenolysis of glycerol
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Mesoporous Ti-W oxides, bearing high surface area, large pore volume, uniform pore size and tunable W/Ti ratios in a wide range (10-40 mol%), were successfully fabricated via an evaporation-induced self-assembly (EISA) strategy. In this approach, the incorporation of W species not only effectively resulted in well-ordered mesoporous structures when calcined below 400 °C but also modified the acidic properties of the obtained oxide composites. The optimal acid amounts (0.47-0.67 mmol g-1 for 400 °C calcinations, 0.25-0.27 mmol g-1 for 500 °C calcinations) were obtained when the W concentration was between 10 and 20 mol%. When calcined at 500 °C, Bronsted acids were generated in Ti90W10-500 and Ti80W20-500. The catalytic performance of these mesoporous solid acids in glycerol hydrogenolysis was studied with a loading of 2 wt% Pt. Pt/Ti100-nWn-500s exhibited high selectivity to 1,3-propanediol (33.5% and 40.3%) and promising catalytic activities (18.4% and 24.2% glycerol conversion) when n is 10 and 20, respectively. This work presents a step forward in the development of highly efficient glycerol hydrogenolysis catalysts and a new understanding of the reaction mechanism of glycerol hydrogenolysis to 1,3-propanediol.
- Zhang, Yanhua,Zhao, Xiao-Chen,Wang, Yao,Zhou, Likun,Zhang, Junying,Wang, Jia,Wang, Aiqin,Zhang, Tao
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- Influence of the Support of Bimetallic Platinum Tungstate Catalysts on 1,3-Propanediol Formation from Glycerol
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Three aluminium oxide materials and a HZSM-5 zeolite were used as supports of bimetallic Pt-WOx catalysts to establish structure–activity relationships in the glycerol hydrogenolysis reaction. The surface W density and the intimate contact between Pt and WOx were key parameters. Surface W density controls the formation of polytungstates, the only species able to produce the weak Br?nsted acidity that is required to produce 1,3-propanediol selectively. The comparison between the HZSM-5 and the Al2O3 supports demonstrated that an increment of the medium Br?nsted acidity is detrimental for the selective 1,3-propanediol formation as it promotes reactions that yield 1-propanol and propane. An increase of the dispersion of Pt on the Pt/WOx/Al2O3 catalysts led to higher glycerol conversions but also promoted the hydrogenolysis routes that lead to 1,2- and 1,3-propanediol similarly. On the contrary, an increase of the Pt metal content favoured the hydrogenolysis route that leads to 1,3-propanediol significantly. A more intimate contact between Pt and WOx promoted the hydrogenation of the intermediate carbocation, formed and stabilised on a polytungstate active site, into 1,3-propanediol.
- García-Fernández, Sara,Gandarias, Inaki,Tejido-Nú?ez, Yaiza,Requies, Jesús,Arias, Pedro Luis
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- New bulk nickel phosphide catalysts for glycerol hydrogenolysis to 1,2-propanediol
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Transitional metal phosphides were found to have outstanding activity and stability in catalytic hydrotreatments. The bulk trinickel phosphide catalyst with the smallest phosphorus content among the nickel phosphides were synthesized by a hydrothermal method followed by an annealing treatment, and the resulting bulk trinickel phosphide catalysts presented a high purity and morphology of hexagonal prisms. The optimized synthesis conditions include a P:Ni ratio of 3 to 1 and a pH value of 5 in the hydrothermal synthesis stage and a calcination temperature of 773 K in the annealing treatment. The synthesized trinickel phosphides exhibited a low-temperature activity to selective glycerol hydrogenolysis and the high selectivity to 1,2-propanediol.
- Shi, Guojun,Su, Lijun,Jin, Kai
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- Direct Hydrogenolysis of Glycerol to Biopropanols over Metal Phosphate Supported Platinum Catalysts
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Abstract: Several metal phosphate supported platinum catalysts (Pt/AlP, Pt/TiP, Pt/ZrP and Pt/NbP) have been synthesized for the direct hydrogenolysis of glycerol to produce bio-propanols performed under mild reaction conditions. The catalysts were screened for its activity towards production of propanols from glycerol hydrogenolysis and the reaction has been optimized by studying various reaction parameters such as effect of platinum loading, reaction temperature, hydrogen flow rate, glycerol concentration and reaction time. Among the catalysts investigated, 2Pt/TiP presented a remarkable catalytic performance for vapour phase hydrogenolysis of glycerol with 100% conversion of glycerol and 97% selectivity to total propanols (1-propanol + 2-propanol) at 220 °C and atmospheric pressure. The high efficiency of 2Pt/TiP catalyst is probably be due to the strong acidity of catalyst and the uniform dispersion of small Pt particles on surface of TiP that could enable the dehydration-hydrogenation route of glycerol hydrogenolysis. Further, the structural characteristics of used catalyst have been investigated in order to understand the stability of the catalyst. Therefore, a more economical and sustainable approach of producing value added propanols from bio-derived glycerol over highly efficient catalytic system is herein presented. Graphical Abstract: [Figure not available: see fulltext.]
- Bhanuchander, Ponnala,Priya, Samudrala Shanthi,Kumar, Vanama Pavan,Hussain, Sk.,Pethan Rajan,Bhargava, Suresh K.,Chary, Komandur V. R.
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- New approaches to the Pt/WOx/Al2O3 catalytic system behavior for the selective glycerol hydrogenolysis to 1,3-propanediol
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Although the hydrogenolysis of glycerol to 1,2-propanediol is already well developed, the production of the more valuable 1,3-propanediol is still a challenge. To achieve this aim, it is essential to design catalysts showing high selectivity toward the CO cleavage of the secondary hydroxyl group in glycerol. In this work, two different series of Pt/WOx/Al2O3 catalytic systems were studied for the selective hydrogenolysis of glycerol to 1,3-propanediol. The results reveal the necessity to control the tungsten surface density in order to obtain highly dispersed polytungstate species, which are able to produce Br?nsted acidity and are involved in the selective formation of 1,3-propanediol. After optimization of the tungsten surface density, the effect of platinum content was also studied. It was found that by improving the interactions between platinum and tungsten oxides, it is possible to increase the selectivity toward 1,3-propanediol. Under optimized conditions, a selectivity toward 1,3-PDO of 51.9% at 53.1% glycerol conversion was obtained. Based on the characterization and activity test results, a reaction mechanism for the Pt-WOx catalytic system in glycerol hydrogenolysis to 1,3-propanediol was also proposed.
- García-Fernández,Gandarias,Requies,Güemez,Bennici,Auroux,Arias
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- Effect of perimeter interface length between 2D WO3 monolayer domain and γ-Al2O3 on selective hydrogenolysis of glycerol to 1,3-propanediol
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The relationship between the structure of W species on Pt/WO3/Al2O3 catalysts and their activity for selective hydrogenolysis of glycerol to 1,3-propanediol was investigated. Structural analysis by spectroscopic techniques including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and X-ray adsorption fine structure (XAFS) revealed the formation of two-dimensional WO3 monolayer domains on the surface of γ-Al2O3 at a WO3 loading level of below 20 wt%. Evaluation of the reduction properties of W species by H2 temperature programed reduction (TPR) suggested the presence of two kinds of W species with different reduction properties loaded on γ-Al2O3, and W species at the edge of a WO3 domain was reduced more easily than that inside of a WO3 domain. Furthermore, the length of the perimeter interface between a two-dimensional WO3 monolayer domain and γ-Al2O3 (W-Al perimeter interface) could be estimated from the difference in their reducibility. The positive correlation between W-Al perimeter interface length and the yield of 1,3-propanediol in hydrogenolysis of glycerol indicated that a W-(OH)-Al site at the W-Al perimeter interface functioned as a main active site.
- Aihara, Takeshi,Miura, Hiroki,Shishido, Tetsuya
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- Effect of promoters on the selective hydrogenolysis of glycerol over Pt/W-containing catalysts
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Diverse promoters, including noble metals (such as Ru, Ir and Rh) and transition metal oxides (such as Re, La, Fe, Zr, Sn and Ce oxides) were introduced into Pt/WOx and Pt/WOx/Al2O3 catalysts to investigate the ability of these promoters to modify activity and selectivity during glycerol hydrogenolysis to 1,3-propanediol. Among these, La exhibited the greatest promotional effect; the introduction of 0.1% La to the Pt/WOx improved activity, selectivity and stability, although the significant increase in selectivity came at the cost of a slight activity loss in the case of the Pt/WOx/Al2O3 catalyst. Transmission electron microscopy, high angle annular dark field scanning tunneling electron microscopy and NH3-temperature programmed desorption all demonstrated that the introduction of La generates a greater quantity of acidic sites on the catalyst surface, and that the majority of the La species are associated with Pt particles. Most of the other additives resulted in only minimal improvements or even detrimental effects with regard to both activity and selectivity, although some appear to improve the stability of the catalyst.
- Wang, Jia,Lei, Nian,Yang, Chaojun,Su, Yang,Zhao, Xiaochen,Wang, Aiqin
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- Study on the catalytic performance of 3-hydroxypropionaldehyde to1,3-propanediol over Ni/hydrogen mordenite by different method
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The catalyst for conversion of 3-hydroxypropionaldehyde to 1,3-propanediol was prepared by dry mixing, wet mixing, ion exchange and impregnation, respectively. The catalysts were characterized by transmission electron microscope and temperature programmed
- Tang, Yong,Shen, Ben-Xian,Ning, Chun-Li,Zhang, Chun-Lei,Zhao, Ji-Gang
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- Selective synthesis of 1,3-propanediol from glycidol over a carbon film encapsulated Co catalyst
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1,3-Propanediol (1,3-PDO) is an important chemical and feedstock in the synthesis of polytrimethylene terephthalate (PTT) resin, but the catalytic production of 1,3-PDO is difficult. In this work, a carbon film encapsulated Co nanoparticle catalyst (Co?NC) was synthesized via pyrolysis of Co2(1,4-benzenedicarboxylic acid)2(triethylenediamine) and tested in the synthesis of 1,3-PDO from glycidol. It was found that this Co?NC catalyst was highly active, selective and stable for this reaction under mild conditions. Characterization results indicated that the formation of 1,3-PDO was sensitive to the adsorbed hydrogen. The selectivity to 1,3-PDO reached its maximum over the Co?NC catalyst as carbon film encapsulation can inhibit the excessive adsorption and activation of H2 molecules, while the adsorbed dissociated hydrogen on naked Co NPs and/or N atoms (in the carbon shell) promoted the formation of propanol.
- Sun, Yanyan,Cai, Zhongshun,Li, Xuewen,Chen, Ping,Hou, Zhaoyin
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- Hydrogenation of dimethyl malonate to 1,3-propanediol catalyzed by a Cu/SiO2 catalyst: The reaction network and the effect of Cu+/Cu0 on selectivity
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1,3-Propanediol, a vital monomer for the manufacture of commodity polytrimethylene-terephthalate, is commercially produced nowadays through either hydration of acrolein or hydroformylation of ethylene oxide. Herein, for the first time, we present the investigation of an alternative route for 1,3-propanediol production from vapor-phase catalytic hydrogenation of syngas-derived dimethyl malonate on a Cu/SiO2 catalyst. The catalytic reaction network has been disclosed for the Cu/SiO2 catalyst, and the reaction proceeds through sequential hydrogenation with methyl 3-hydroxypropionate as the primary product, which can be further converted into 1,3-propanediol or methyl propionate. Excessive hydrogenation of 1,3-propanediol or methyl propionate leads to the formation of n-propanol. Meanwhile, a small amount of dimethyl malonate cracks into methyl acetate. The structural and textural properties of Cu/SiO2 catalysts with varied copper loadings were extensively characterized by X-ray diffraction, Fourier transform infrared spectroscopy, H2-temperature programmed reduction, X-ray photoelectron spectroscopy, N2 physisorption, CO chemisorption, N2O titration, and transmission electron microscopy. A correlation of the areal activity to copper components suggests that metallic copper modified by the co-present Cu+ species may be the active site for the hydrogenation. The highest 1,3-propanediol selectivity was achieved on a catalyst with a maximum Cu+/(Cu0 + Cu+) ratio of 0.41. The revelation of catalytic networks and insights into the active species can provide guidance for future rational design of catalysts for regioselective hydrogenation of CO bonds in dimethyl malonate.
- Zheng, Sainan,Zhu, Kake,Li, Wei,Ji, Yang
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- Glycerol Hydrogenolysis to 1,3-Propanediol on Tungstate/Zirconia-Supported Platinum: Hydrogen Spillover Facilitated by Pt(1 1 1) Formation
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In glycerol hydrogenolysis, WOx and ReOx catalysts have been investigated widely because of their importance for the selectivity of 1,3-propanediol, but few studies have focused on hydrogen spillover. In this work, the hydrogen spillover effect on the catalytic performance was investigated for a series of Pt/WO3/ZrO2 nanocatalysts. The spillover capacities were tuned by changing the tetragonal/monoclinic ZrO2 composition and thermal treatment conditions of the Pt precursor. H2/O2 titration and X-ray photoelectron spectroscopy (XPS) confirm that all of the catalysts present a uniform Pt dispersion and a similar surface electron environment. Diffuse reflectance infrared Fourier transform spectra of adsorbed CO and H2 chemisorption reveal the strong correlation between the amount of Pt(1 1 1) terraces and the spillover capacities. We demonstrate that the reaction rate is influenced by hydrogen spillover, but not the acid amount or acid strength of the catalysts in this case. The important roles of Pt(1 1 1) and WO3 in the spillover process are discussed.
- Zhou, Wei,Zhao, Yujun,Wang, Yue,Wang, Shengping,Ma, Xinbin
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- Ir-Re alloy as a highly active catalyst for the hydrogenolysis of glycerol to 1,3-propanediol
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In this work, bimetallic Ir-Re catalysts supported on KIT-6 are prepared by tuning the thermal treatment procedures, i.e., conventional calcination and reduction (Ir-Re/KIT-6-CR) and modified direct reduction (Ir-Re/KIT-6-R) after impregnation of two metal precursors. The structure of both catalysts is intensively characterized by H2-TPR, STEM-HAADF-EDX, XPS and CO-DRIFTS. Results indicate that an Ir-Re alloy forms on the KIT-6 support when direct reduction is employed, which exhibits excellent catalytic performance in hydrogenolysis of glycerol. The formation rate of 1,3-propanediol over Ir-Re/KIT-6-R reaches 25.6 mol1,3-PD molIr-1 h-1 at 63% glycerol conversion with the addition of amberlyst-15 under 8 MPa H2, 393 K and 20 wt% glycerol aqueous solution, almost twice that over Ir-Re/KIT-6-CR. It is revealed that Re species without prior calcination treatment could be fully reduced and therefore couple with Ir to form an Ir-Re alloy structure with enhanced resistance against particle aggregation, while the calcination and subsequent reduction leads to the formation of an Ir-ReOx structure since the rhenium oxide species generated during the calcination is difficult to be reduced.
- Deng, Chenghao,Duan, Xuezhi,Zhou, Jinghong,Zhou, Xinggui,Yuan, Weikang,Scott, Susannah L.
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- Selective hydrogenolysis of glycerol to 1,3-propanediol over egg-shell type Ir-ReOx catalysts
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The selective liquid-phase hydrogenolysis of glycerol to 1,3-propanediol over egg-shell catalysts in which the loadings of Ir and Re were both 2 wt% is reported. The shell thickness could be tuned by impregnating a hydrophobic silanized support with an aqueous solution of precursors containing various concentrations of ethanol and using entrapped air to prevent the impregnation solution from entering into the support pellets. The conversion of glycerol for the target reaction over egg-shell catalysts was higher than that over a uniform catalyst and was accompanied by a high selectivity for 1,3-propanediol over 1,2-propanediol. Reacting over the catalyst for which the impregnation solution ethanol concentration was 20 vol% resulted in the highest glycerol conversion (60.9%) and the highest yield of secondary hydroxyl group removal (30.2%). The properties of the egg-shell and uniform catalysts were characterized by XRD, TEM, XPS, H2-TPR, H2-pulse chemisorption and NH3-TPD. An appropriate diffusion distance of the reactants for egg-shell catalysts might result in better catalytic performance because of the high viscosity of the glycerol aqueous solution.
- Luo, Wenting,Lyu, Yuan,Gong, Leifeng,Du, Hong,Wang, Tao,Ding, Yunjie
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- Selective hydrogenolysis of glycerol to 1,3-propanediol catalyzed by Pt nanoparticles-AlOx/WO3
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Tungsten oxide-supported platinum nanoparticles containing aluminum oxide species (Pt-AlOx/WO3) act as a highly efficient heterogeneous catalyst for the hydrogenolysis of glycerol to 1,3-propanediol without any additives. High 1,3-propanediol selectivity was observed due to the concerted effect of the Pt nanoparticles, aluminum oxide, and tungsten oxide support. The Pt-AlOx/WO3 catalyst is reusable with maintaining its high catalytic performance.
- Mizugaki, Tomoo,Yamakawa, Takayuki,Arundhathi, Racha,Mitsudome, Takato,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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- Influence of catalyst pretreatment on catalytic properties and performances of Ru-Re/SiO2 in glycerol hydrogenolysis to propanediols
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Bimetallic Ru-Re/SiO2 and monometallic Ru/SiO2 catalysts were prepared by impregnation method and their catalytic performances were evaluated in the hydrogenolysis of glycerol to propanediols (1,2-propanediol and 1,3-propanediol) with a batch type reactor (autoclave) under the reaction conditions of 160 °C, 8.0 MPa and 8 h. Ru-Re/SiO2 showed much higher activity in the hydrogenolysis of glycerol than Ru/SiO2, and the pretreatment conditions of the catalyst precursors had great influence on the catalytic performance of both Ru-Re/SiO2 and Ru/SiO2 catalysts. The physicochemical properties of Ru-Re/SiO2 and Ru/SiO2, such as specific surface areas, crystal phases, morphologies/microstructures, surface element states, reduction behaviors and dispersion of Ru metal, were characterized by N2 adsorption/desorption, XRD, Raman, TEM-EDX, XPS, H2-TPR and CO chemisorption. The results of XRD, TEM-EDX and CO chemisorption characterizations showed that Re component had an effect on promoting the dispersion of Ru species on the surface of SiO2, and the measurements of H2-TPR revealed that the co-existence of Re and Ru components on SiO2 changed the respective reduction behavior of Re or Ru alone. High pre-reduction temperatures would decrease the activities of Ru-Re/SiO2 and Ru/SiO2 catalysts, compared with the corresponding calcined catalysts (without pre-reduction), which actually went through an in-situ reduction during the reaction. XPS analysis indicated that Ru species was in Ru0 metal state, while Re species was mostly in Re oxide state in the spent Ru-Re/SiO2 sample. Re component was probably in rhenium oxide state rather than Re0 metal state to take part in the reaction via interaction with Ru0 metal.
- Ma, Lan,He, Dehua
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- Hydrogenolysis of glycerol in an aqueous medium over Pt/WO3/zirconium phosphate catalysts studied by1H NMR spectroscopy
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Bifunctional Pt/WO3/zirconium phosphate catalyzes the liquid-phase hydrogenolysis of glycerol in an aqueous medium.1H NMR spectroscopy (solvent suppression pulse program) is employed to monitor this reaction. Propanediols (1,3 + 1,2-PDO) formed as the major product along with propanols (1- and 2-POs) as the minor product. A synergistic enhancement in glycerol conversion and selectivity to 1,3-PDO was observed when both Pt and WO3were present in the catalyst. Avolcano-shapevariation of catalytic activity with W content was observed. A catalyst with 8 wt% W and 1 wt% Pt exhibited the highest selective hydrogenolysis performance (glycerol conversion = 92.3% and total PDOs selectivity = 45.9% and 1,3-PDO selectivity = 20.8% at 200 °C). Dispersed Pt in contact with polytungstate-type WO3species was found to be the active catalytic site.1H NMR spectroscopy is demonstrated as an attractive technique toquantifythe products of a glycerol hydrogenolysis reaction.
- Bhowmik, Susmita,Enjamuri, Nagasuresh,Darbha, Srinivas
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- Glycerol hydrogenolysis to n-propanol over Zr-Al composite oxide-supported Pt catalysts
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Zr-Al mixed oxide supported Pt catalysts with different Zr/Al mole ratios (2.5%Pt/ZrxAl1–xOy) were synthesized by an impregnation method and used for the selective hydrogenolysis of glycerol to n-propanol in an autoclave reactor. The catalysts were fully characterized by X-ray powder diffraction, Brunauer-Emmett-Teller surface area analysis, CO chemisorption, H2 temperature- programmed reduction, pyridine-infrared spectroscopy, and NH3-temperature-programmed desorption. The results revealed that the Zr/Al ratio on the support significantly affected the size of the platinum particles and the properties of the acid sites on the catalysts. The catalytic performance was well correlated with the acidic properties of the catalyst; specifically, more acid sites contributed to the conversion and strong acid sites with a specific intensity contributed to the deep dehydration of glycerol to form n-propanol. Among the tested catalysts, 2.5 wt% Pt/Zr0.7Al0.3Oy exhibited excellent selectivity for n-propanol with 81.2% glycerol conversion at 240 °C and 6.0 MPa H2 pressure when 10% aqueous glycerol solution was used as the substrate. In addition, the effect of various reaction parameters, such as H2 content, reaction temperature, reaction time, and number of experimental cycles were studied to determine the optimized reaction conditions and to evaluate the stability of the catalyst.
- Li, Chuang,He, Bo,Ling, Yu,Tsang, Chi-Wing,Liang, Changhai
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- Promoting effect of WOx on selective hydrogenolysis of glycerol to 1,3-propanediol over bifunctional Pt-WOx/Al2O3 catalysts
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Despite 1,3-propanediol possessing high economic value, its production from glycerol hydrogenolysis is a challenging task. Herein, a series of WOx promoted Pt/Al2O3 catalysts with various WOx contents were prepared and investigated for selective production 1,3-propanediol from glycerol hydrogenolysis. To explore the structure feature, these catalysts were fully characterized by BET, CO chemisorption, HRTEM, XRD (in situ XRD), Raman, NH3-TPD, Py-IR, H2-TPR, and XPS. Among them, Pt-10WOx/Al2O3 achieved the highest 1,3-propanediol yield up to 42.4%, which was ascribed to the large concentration of Br?nsted acid sites, strong electronic interaction between Pt with WOx and hydrogen spillover. The strong correlation between 1,3-propanediol yield and Br?nsted acid site indicated its essential role for the formation of 1,3-propanediol. Meanwhile the linear correlation between 1,2-propanediol yield and Lewis acid site gave direct evidence that Lewis acid site preferentially generated 1,2-propanediol.
- Zhu, Shanhui,Gao, Xiaoqing,Zhu, Yulei,Li, Yongwang
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- Small Current but Highly Productive Synthesis of 1,3-Propanediol from Glycerol by an Electrode-Driven Metabolic Shift in Klebsiella pneumoniae L17
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Electrofermentation actively regulates the bacterial redox state, which is essential for bioconversion and has been highlighted as an effective method for further improvements of the productivity of either reduced or oxidized platform chemicals. 1,3-Propanediol (1,3-PDO) is an industrial value-added chemical that can be produced from glycerol fermentation. The bioconversion of 1,3-PDO from glycerol requires additional reducing energy under anoxic conditions. The cathode-based conversion of glycerol to 1,3-PDO with various electron shuttles (2-hydroxy-1,4-naphthoquinone, neutral red, and hydroquinone) using Klebsiella pneumoniae L17 was investigated. The externally poised potential of ?0.9 V vs. Ag/AgCl to the cathode increased 1,3-PDO (35.5±3.1 mm) production if 100 μm neutral red was used compared with non-bioelectrochemical system fermentation (23.7±2.4 mm). Stoichiometric metabolic flux and transcriptional analysis indicated a shift in the carbon flux toward the glycerol reductive pathway. The homologous overexpression of glycerol dehydratase (DhaB) and 1,3-PDO oxidoreductase (DhaT) enzymes synergistically enhanced 1,3-PDO conversion (39.3±0.8 mm) under cathode-driven fermentation. Interestingly, a small current uptake (0.23 mmol of electrons) caused significant metabolic flux changes with a concomitant increase in 1,3-PDO production. This suggests that both an increase in 1,3-PDO production and regulation of the cellular metabolic pathway are feasible by electrode-driven control in cathodic electrofermentation.
- Kim, Changman,Lee, Jae Hyeon,Baek, Jiyun,Kong, Da Seul,Na, Jeong-Geol,Lee, Jinwon,Sundstrom, Eric,Park, Sunghoon,Kim, Jung Rae
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- Rhenium-promoted Pt/WO3/ZrO2: An efficient catalyst for aqueous glycerol hydrogenolysis under reduced H2 pressure
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Rhenium, the non-noble metal with an acceptable price, was found to be a good additive that largely improved Pt/WO3/ZrO2 catalysis for glycerol hydrogenolysis. Compared with conventionally employed Pt/WO3/ZrO2, the Re-promoted catalyst led to almost quantitative glycerol conversion (>99% vs. 57.7%), giving useful C3 alcohols in excellent total selectivity (>95%) under reduced reaction pressure (2.5 MPa). The addition of Re led to such an impressive enhancement of the catalyst activity that even the reaction performed under atmospheric H2 pressure (0.1 MPa) afforded 96.8% glycerol conversion and a good selectivity of C3 compounds at 95.2%. Further XRD, Raman, BET, CO chemisorption, TEM, H2-TPR, XPS, NH3-TPD, 1H MAS NMR and Py-IR studies indicated that introduction of Re greatly improved the dispersion of Pt and catalyst acidity, and resulted in this largely enhanced catalyst activity.
- Tong, Qing,Zong, Anyi,Gong, Wei,Yu, Lei,Fan, Yining
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- Hydrogenolysis of Glycerol to 1,3-propanediol under Low Hydrogen Pressure over WOx-Supported Single/Pseudo-Single Atom Pt Catalyst
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Single/pseudo-single atom Pt catalyst was prepared on mesoporous WOx. The large surface area and abundant oxygen vacancies of WOx improve the Pt dispersion and stabilize the Pt isolation. This newly prepared catalyst exhibited outstanding hydrogenolysis activity under 1 MPa H2 pressure with a very high space-time yield towards 1,3-propanediol (3.78 g gPt-1 h-1) in Pt-W catalysts. The highly isolated Pt structure is thought to contribute to the excellent H2 dissociation capacity over Pt/WOx. The high selectivity towards 1,3-propanediol is attributed to the heterolytic dissociation of H2 at the interface of Pt and WOx (providing specific Br?nsted acid sites and the concerted dehydration-hydrogenation reaction) and the bond formation between glycerol and WOx, which favors/stabilizes the formation of a secondary carbocation intermediate as well as triggers the redox cycle of the W species (W6+?W5+).
- Wang, Jia,Zhao, Xiaochen,Lei, Nian,Li, Lin,Zhang, Leilei,Xu, Shutao,Miao, Shu,Pan, Xiaoli,Wang, Aiqin,Zhang, Tao
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- Hydrogenation of 3-hydroxypropanal to 1,3-propanediol over a Cu-V/Ni/SiO2 catalyst
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A Ni-based catalyst modified with copper and vanadium (5Cu-20V/30Ni/SiO2) was synthesized and employed in the hydrogenation of 3-hydroxypropanal (3-HPA) to 1,3-propanediol (1,3-PDO). Catalysts were systematically characterized via XRD, TEM, HRTEM, SAED, H2-TPD, N2 physisorption, H2-TPR, and XPS. It was indicated that the addition of Cu and V not only promoted the reduction of Ni2+ species and the generation of active hydrogen species, but also increased the dispersion of Ni species and the interaction between Ni particles and SiO2. The catalytic performance evaluation showed that the (5Cu-20V/30Ni/SiO2) could provide the largest yield of 1,3-PDO (above 76.8%) and highest TOF (4.32 × 103 s-1). The structure-activity relationship was clarified according to the characterization results. The optimized reaction conditions over the 5Cu-20V/30Ni/SiO2 catalyst were obtained as the reaction temperature of 80 °C, a H2 pressure of 2.0 MPa (H2), and an LHSV of 0.4 h-1. The employment of non-noble metals, the relatively low pressure of H2, and the relatively high yield of 1,3-PDO make 5Cu-20V/30Ni/SiO2 an efficient and economic catalyst that may have potential applications in industry.
- Li, Li-Jun,Yi, Wen-Jun,Liu, Tian-Wei,Huang, Chen,Li, An,Luo, Cai-Wu,Chao, Zi-Sheng
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- Aqueous-phase hydrogenolysis of glycerol to 1,3-propanediol over Pt-H 4SiW12O40/SiO2
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Hydrogenolysis of glycerol to 1,3-propanediol in aqueous-phase was investigated over Pt-H4SiW12O40/SiO2 bi-functional catalysts with different H4SiW12O 40 (HSiW) loading. Among them, Pt-15HSiW/SiO2 showed superior performance due to the good dispersion of Pt and appropriate acidity. It is found that Bronsted acid sites facilitate to produce 1,3-PDO selectively confirmed by Py-IR. The effects of weight hourly space velocity, reaction temperature and hydrogen pressure were also examined. The optimized Pt-HSiW/SiO2 catalyst showed a 31.4% yield of 1,3-propanediol with glycerol conversion of 81.2% at 200 °C and 6 MPa. Graphical Abstract: [Figure not available: see fulltext.].
- Zhu, Shanhui,Zhu, Yulei,Hao, Shunli,Chen, Lungang,Zhang, Bin,Li, Yongwang
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- Hydrogenolysis of Glycidol as an Alternative Route to Obtain 1,3-Propanediol Selectively Using MOx-Modified Nickel-Copper Catalysts Supported on Acid Mesoporous Saponite
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Ni and Cu mono- and bimetallic catalysts modified with various types of acid oxides MOx (M=Mo, V, W, and Re) were tested for the hydrogenolysis of glycidol as an alternative route to the hydrogenolysis of glycerol to obtain 1,3-propanediol (1,3-PrD). Characterization results revealed that the presence of modifiers affected the dispersion and reducibility of the NiO particles and the strength and amount of acid sites. Among the modifiers tested, Re led to the highest activity, a high propanediols selectivity, and the highest 1,3-PrD/1,2-propanediol (1,2-PrD) ratio. The Ni-Cu/Re ratio was optimized to improve the catalytic activity. The best catalytic result, with a 46 % 1,3-PrD yield and a 1,3-PrD/1,2-PrD ratio of 1.24, was obtained if the monometallic Ni catalyst at 40 wt % loading and modified with 7 wt % Re was used at 393 K and 5 MPa H2 pressure after 4 h of reaction. The overall 1,3-PrD yield starting from glycerol and assuming a two-step synthesis (glycerol→glycidol→1,3-PrD) and a yield of 78 % for the first step would be 36 %. This 1,3-PD yield is the highest for a reaction catalyzed by a non-noble metal and is comparable to the direct hydrogenolysis of glycerol using noble metal catalysts at a longer time and a high H2 pressure.
- Gebrestadik, Fiseha B.,Llorca, Jordi,Salagre, Pilar,Cesteros, Yolanda
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- Effect of promoters on hydrogenation of diethyl malonate to 1,3-propanediol over nano copper-based catalysts
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Copper-based catalysts were prepared via ammonia evaporation co-precipitation method. Structure evolutions of the catalysts were systematically characterized by XRD, FTIR, TG, SEM, N2-physisorption, ICP-AES, N2O chemisorption and XPS focusing on the influence of promoters on the catalytic behavior in the hydrogenation of diethyl malonate to 1,3-propanediol. The results showed that diethyl malonate conversion and 1,3-propanediol selectivity could reach 96.71% and 29.76% respectively at 473 K with 2.0 MPa and 1.8 h- 1 with boron as promoter. The improved catalytic performance of Cu-B/SiO2 catalyst could be attributed to more Cu0 formed with the inhibition of copper phyllosilicate and better dispersion of copper species.
- Ding, Tongmei,Tian, Hengshui,Liu, Jichang,Wu, Wenbin,Zhao, Bingqin
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- Method and system for producing 1, 3-propylene glycol from 1, 3-dichloropropanol
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The invention discloses a method and a system for producing 1, 3-propylene glycol from 1, 3-dichloropropanol. The method comprises the following steps: continuously inputting 1, 3-dichloropropanol into a reaction device provided with a dehydration catalyst for dehydration reaction to prepare 1, 3-dichloropropene; continuously inputting the 1, 3-dichloropropene and hydrogen into a reaction device provided with a hydrogenation catalyst for hydrogenation reaction to prepare 1, 3-dichloropropane; and carrying out hydrolysis reaction on a mixed reaction system containing the 1, 3-dichloropropane, ahydrolysis agent and a solvent to prepare the 1, 3-propylene glycol. According to the method, an intermediate product 1, 3-dichloropropanol of epoxy chloropropane prepared by a cheap glycerol chlorination method is used as a raw material, an important chemical raw material 1, 3-propylene glycol is prepared by three steps of dehydration, hydrogenation and hydrolysis, a new way is provided for preparing 1, 3-propylene glycol from glycerol, and the route has the advantages of mild conditions, low cost, environmental friendliness, economy and the like.
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Paragraph 0083; 0088-0089; 0090; 0095; 0097; 0103; 0109-0110
(2021/03/13)
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- Method for preparing alcohol compound through hydrogenation of carbonyl-containing compound
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The invention provides a method for preparing an alcohol compound through hydrogenation of a carbonyl-containing compound, the method comprises the following steps: firstly, contacting the carbonyl-containing compound with a nickel catalyst precursor to obtain a nickel-containing solution, then carrying out a contact reaction on the nickel-containing solution and hydrogen, converting the contained nickel into a nickel catalyst, and carrying out in-situ catalysis on the hydrogenation reaction of the carbonyl-containing compound, and obtaining the alcohol compound. According to the preparation method provided by the invention, the preparation of the nickel catalyst and the hydrogenation reaction of the carbonyl-containing compound are carried out in the same technological process for the first time, the prepared nickel catalyst is good in catalytic activity and long in service life, and the alcohol compound prepared by in-situ catalysis is high in yield and good in selectivity, so that the production cost of the alcohol compound can be remarkably reduced, the production efficiency is improved, and the method is particularly suitable for large-scale industrial production.
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Paragraph 0045-0049; 0062-0067
(2021/07/10)
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- Method and system for producing 1, 3-propylene glycol by multi-step method
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The invention discloses a method and a system for producing 1, 3-propylene glycol by a multi-step method. The method comprises the following steps: carrying out dehydration reaction on 1, 3-dichloropropanol and a dehydration catalyst to prepare 1, 3-dichloropropene; carrying out a first hydrolysis reaction on a first mixed reaction system containing the 1, 3-dichloropropene, a first hydrolysis agent and a first solvent to prepare 3-chloro-2-propene-1-alcohol; carrying out hydrogenation reaction on the 3-chloro-2-propene-1-alcohol and a hydrogenation catalyst to prepare 3-chloropropanol; and carrying out a second hydrolysis reaction on a second mixed reaction system containing the 3-chloropropanol, a second hydrolysis agent and a second solvent to prepare the 1, 3-propylene glycol. According to the method, 1, 3-dichloropropanol is used as a raw material, the important chemical raw material 1, 3-propylene glycol is prepared through a dehydration, hydrolysis, hydrogenation and hydrolysisfour-step method, and the method has the advantages of mild reaction conditions, low cost, environmental protection, economy and the like.
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Paragraph 0101; 0108-0110; 0117-0119; 0126-0128; 0135-0141
(2021/01/28)
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- Hydrodeoxygenation of C4-C6 sugar alcohols to diols or mono-alcohols with the retention of the carbon chain over a silica-supported tungsten oxide-modified platinum catalyst
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The hydrodeoxygenation of erythritol, xylitol, and sorbitol was investigated over a Pt-WOx/SiO2 (4 wt% Pt, W/Pt = 0.25, molar ratio) catalyst. 1,4-Butanediol can be selectively produced with 51% yield (carbon based) by erythritol hydrodeoxygenation at 413 K, based on the selectivity over this catalyst toward the regioselective removal of the C-O bond in the -O-C-CH2OH structure. Because the catalyst is also active in the hydrodeoxygenation of other polyols to some extent but much less active in that of mono-alcohols, at higher temperature (453 K), mono-alcohols can be produced from sugar alcohols. A good total yield (59%) of pentanols can be obtained from xylitol, which is mainly converted to C2 + C3 products in the literature hydrogenolysis systems. It can be applied to the hydrodeoxygenation of other sugar alcohols to mono-alcohols with high yields as well, such as erythritol to butanols (74%) and sorbitol to hexanols (59%) with very small amounts of C-C bond cleavage products. The active site is suggested to be the Pt-WOx interfacial site, which is supported by the reaction and characterization results (TEM and XAFS). WOx/SiO2 selectively catalyzed the dehydration of xylitol to 1,4-anhydroxylitol, whereas Pt-WOx/SiO2 promoted the transformation of xylitol to pentanols with 1,3,5-pentanetriol as the main intermediate. Pre-calcination of the reused catalyst at 573 K is important to prevent coke formation and to improve the reusability.
- Betchaku, Mii,Cao, Ji,Liu, Lujie,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi,Yabushita, Mizuho
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p. 5665 - 5679
(2021/08/16)
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- Preparation method for 1,3-propylene glycol from glycerol
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The invention relates to a preparation method for 1,3-propylene glycol from glycerol, wherein the preparation method comprises the steps of chlorohydrination reaction, cyclization reaction, hydrogenation reaction and the like. The glycerin conversion rate of the preparation method reaches 99% or above, the yield of 1,3-propylene glycol reaches 65% or above, and the preparation method has the advantages of being simple in process, mild in reaction condition, small in investment, high in technical safety and easy to operate and control.
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Paragraph 0066-0076
(2021/04/10)
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- Hydroformylation reaction ligand, hydroformylation catalyst and diol preparation method
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The invention discloses a hydroformylation reaction ligand, a hydroformylation catalyst and a diol preparation method According to the invention, the structural formula of the hydroformylation reaction ligand is shown in the specification, wherein R1 and R2 are mutually independent one of H, aryl or substituted aryl, thienyl, pyrrolyl, thiazolyl, imidazolyl and pyridyl; the ligand disclosed by the invention is high in catalytic activity and good in metal active center stability, by-products of aldehyde in a conventional hydroformylation reaction can be reduced, and linear diol with a high normal/isomer ratio can be obtained by a one-step method; and the method has the advantages of simple and convenient process, low cost and energy consumption, good production safety, high product quality and the like, and is particularly suitable for large-scale industrial production.
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Paragraph 0051; 0059-0060
(2021/06/22)
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- Protodeboronation of (Hetero)Arylboronic Esters: Direct versus Prehydrolytic Pathways and Self-/Auto-Catalysis
-
The kinetics and mechanism of the base-catalyzed hydrolysis (ArB(OR)2→ ArB(OH)2) and protodeboronation (ArB(OR)2→ ArH) of a series of boronic esters, encompassing eight different polyols and 10 polyfluoroaryl and heteroaryl moieties, have been investigated by in situ and stopped-flow NMR spectroscopy (19F,1H, and11B), pH-rate dependence, isotope entrainment,2H KIEs, and KS-DFT computations. The study reveals the phenomenological stability of boronic esters under basic aqueous-organic conditions to be highly nuanced. In contrast to common assumption, esterification does not necessarily impart greater stability compared to the corresponding boronic acid. Moreover, hydrolysis of the ester to the boronic acid can be a dominant component of the overall protodeboronation process, augmented by self-, auto-, and oxidative (phenolic) catalysis when the pH is close to the pKaof the boronic acid/ester.
- Assante, Michele,Geogheghan, Katherine J.,Hayes, Hannah L. D.,Jin, Na,Leach, Andrew G.,Lloyd-Jones, Guy C.,Noonan, Gary,Tomasi, Simone,Wei, Ran
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supporting information
p. 14814 - 14826
(2021/09/13)
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- Understanding the deactivation behavior of Pt/WO3/Al2O3 catalyst in the glycerol hydrogenolysis reaction
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The selective hydrogenolysis of glycerol to 1,3-propanediol is a highly important reaction for both improving the profitability of biodiesel and valorization of biomass. While intensive research efforts have been devoted to enhancing the catalytic activity and selectivity, little is focused on the stability although the latter is of paramount importance to practical applications. In this work, we investigated the stability of Pt/WO3/Al2O3 and observed a continuous deactivation trend during a 700 h time-on-stream run. Neither the leaching of active W nor the coking was responsible for the deactivation. Instead, XRD, HAADF-STEM and CO chemisorption results clearly showed the occurrence of significant aggregation of Pt particles, which caused a remarkable decrease of Pt-WOx interfacial sites. As a consequence, strong Br?nsted acid sites which were in situ formed by H2 dissociation at the Pt-WOx interfacial sites were reduced, leading to the deactivation of the catalyst.
- Lei, Nian,Liu, Fei,Miao, Zhili,Pan, Xiaoli,Wang, Aiqin,Wang, Hua,Zhang, Tao
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p. 1261 - 1267
(2020/03/13)
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- One-pot synthesis of 1,3-butanediol by 1,4-anhydroerythritol hydrogenolysis over a tungsten-modified platinum on silica catalyst
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Chemical production of 1,3-butanediol from biomass-derived compounds was first reported by 1,4-anhydroerythritol hydrogenolysis over a Pt-WOx/SiO2 catalyst. The reaction proceeded by ring opening hydrogenolysis of 1,4-anhydroerythritol followed by selective removal of secondary OH groups in 1,2,3-butanetriol, and an overall 1,3-butanediol yield up to 54% was then obtained. The performance of the Pt-WOx/SiO2 catalyst for 1,4-anhydroerythritol hydrogenolysis was closely correlated with that for glycerol hydrogenolysis to 1,3-propanediol. The optimized Pt-WOx/SiO2 (Pt: 4 wt% and W: 0.94 wt%) catalyst showed 57% yield of 1,3-propanediol.
- Asano, Takehiro,Liu, Lujie,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi
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supporting information
p. 2375 - 2380
(2020/05/14)
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- Synthesis method of 1,3-propylene glycol
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The invention discloses a synthesis method of 1,3-propylene glycol. The synthesis method comprises: carrying out a reaction for 4-12 h at 0-50 DEG C under normal pressure by using propenol, a chlorideand NaBH4 as raw materials and using ethylene glycol dimethyl ether as a solvent. According to the invention, the method does not require the adding of a catalyst, is simple and easy to implement, low in cost and mild in reaction condition.
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Paragraph 0013-0029
(2020/02/19)
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- PNN tridentate ligand, ruthenium complex, and preparation method and application of ruthenium complex
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The invention discloses a PNN tridentate ligand, a ruthenium complex, and a preparation method and an application of the ruthenium complex. The structure of the ruthenium complex is represented by formula I, and the ruthenium complex has good catalytic activity in a reaction of converting cyclic carbonate into methanol and a reaction of hydrogenating and degrading polyester and polycarbonate. In addition, the PNN tridentate ligand and the ruthenium complex of the PNN tridentate ligand are good in stability, and the synthesis process is simple.
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Paragraph 0187-0192
(2020/06/04)
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- Tetradentate phosphine ligand and preparation method thereof, hydroformylation catalyst and reaction method, and preparation method of 1, 3-propylene glycol
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The invention provides a tetradentate phosphine ligand, a preparation method of the tetradentate phosphine ligand, a hydroformylation catalyst, a reaction method of the hydroformylation catalyst and apreparation method of 1, 3-propylene glycol, and belongs to the technical field of compound materials. The general formula of the tetradentate phosphine ligand is shown in the specification, whereinR1 is hydrogen or halogen, R2 is a nitrogen-containing heterocyclic ring or a complex of the tetradentate phosphine ligand and a rhodium complex, can be used for carrying out a hydroformylation catalytic reaction, and can be used for preparing 1, 3-propylene glycol.
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Paragraph 0074-0075
(2020/08/25)
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- Insight into the nature of Br?nsted acidity of Pt-(WOx)n-H model catalysts in glycerol hydrogenolysis
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In glycerol hydrogenolysis, the conventional preparation methods for Pt-WOx catalysts on active supports usually result in the coexistence of various active sites, causing complex reaction network and declining the atom efficiency of W toward 1
- Huang, Shouying,Li, Wei,Li, Ying,Ma, Xinbin,Wang, Shengping,Wang, Xiaofei,Wang, Yue,Yao, Dawei,Zhao, Yujun,Zhou, Wei
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p. 154 - 163
(2020/06/01)
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- Chemical-Switching Strategy for Synthesis and Controlled Release of Norcantharimides from a Biomass-Derived Chemical
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Catalytic strategies were developed to synthesize and release chemicals for applications in fine chemicals, such as drugs and polymers, from a biomass-derived chemical, 5-hydroxymethyl furfural (HMF). The combination of the diene and aldehyde functionalities in HMF enabled catalytic production of acetalized HMF derivatives with diol or epoxy reactants to allow reversible synthesis of norcantharimide derivatives upon Diels-Alder reaction with maleimides. Reverse-conversion of the acetal group to an aldehyde yielded mismatches of the molecular orbitals in norcantharimides to trigger retro Diels-Alder reaction at ambient temperatures and released reactants from the coupled molecules under acidic conditions. These strategies provide for the facile synthesis and controlled release of high-value chemicals.
- Chang, Hochan,Huber, George W.,Dumesic, James A.
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p. 5213 - 5219
(2020/08/27)
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- Erbium-Catalyzed Regioselective Isomerization-Cobalt-Catalyzed Transfer Hydrogenation Sequence for the Synthesis of Anti-Markovnikov Alcohols from Epoxides under Mild Conditions
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Herein, we report an efficient isomerization-transfer hydrogenation reaction sequence based on a cobalt pincer catalyst (1 mol %), which allows the synthesis of a series of anti-Markovnikov alcohols from terminal and internal epoxides under mild reaction conditions (≤55 °C, 8 h) at low catalyst loading. The reaction proceeds by Lewis acid (3 mol % Er(OTf)3)-catalyzed epoxide isomerization and subsequent cobalt-catalyzed transfer hydrogenation using ammonia borane as the hydrogen source. The general applicability of this methodology is highlighted by the synthesis of 43 alcohols from epoxides. A variety of terminal (23 examples) and 1,2-disubstituted internal epoxides (14 examples) bearing different functional groups are converted to the desired anti-Markovnikov alcohols in excellent selectivity and yields of up to 98%. For selected examples, it is shown that the reaction can be performed on a preparative scale up to 50 mmol. Notably, the isomerization step proceeds via the most stable carbocation. Thus, the regiochemistry is controlled by stereoelectronic effects. As a result, in some cases, rearrangement of the carbon framework is observed when tri-and tetra-substituted epoxides (6 examples) are converted. A variety of functional groups are tolerated under the reaction conditions even though aldehydes and ketones are also reduced to the respective alcohols under the reaction conditions. Mechanistic studies and control experiments were used to investigate the role of the Lewis acid in the reaction. Besides acting as the catalyst for the epoxide isomerization, the Lewis acid was found to facilitate the dehydrogenation of the hydrogen donor, which enhances the rate of the transfer hydrogenation step. These experiments additionally indicate the direct transfer of hydrogen from the amine borane in the reduction step.
- Liu, Xin,Longwitz, Lars,Spiegelberg, Brian,T?njes, Jan,Beweries, Torsten,Werner, Thomas
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p. 13659 - 13667
(2020/11/30)
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- A HPPO by-product recycling synthetic 1, 3 - propanediol (by machine translation)
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The invention belongs to the technical field of organic chemical industry, relates to a HPPO by-product recycling synthetic 1, 3 - propanediol, more specifically, relates to a propylene HPPO process with methanol the reaction product of propylene glycol monomethyl ether as the raw material, and sequentially passes through the dewatering, borohydrite oxidation, hydrolysis of the three-step reaction synthesizes the high value added 1, 3 - propylene glycol, 1, 3 - propylene glycol total yield of 80% or more, purity 99.5% or more, the invention has the simple process route, rationalization of resources use, 1, 3 - propylene glycol yield and purity and the like. (by machine translation)
- -
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Paragraph 0042-0047
(2019/07/04)
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- Effective Hydrogenolysis of Glycerol to 1,3-Propanediol over Metal-Acid Concerted Pt/WOx/Al2O3 Catalysts
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Selective cleavage of secondary C?O bond is an important yet challenging strategy in glycerol valorization, and the product 1,3-propanediol (1,3-PDO) is of great value in polyester industry. Herein, we report a series of Pt/WOx/Al2O3 catalysts for selective hydrogenolysis of glycerol in a fixed-bed reactor and obtain the highest space-time yield of 1,3-PDO (191.7*10?3 g1,3-PDO h?1 g?1 cat.) to date. Both Pt and W have substantial effects on the 1,3-PDO yield with the optimum Pt/W atomic ratio of 1/2～1/4. Spectroscopy characterizations as well as chemisorption experiments reveal that at the medium domain size of WOx, hydrogen spillover can take place to the greatest extent due to the improved dispersion of Pt and the suitable reducibility of WOx. Dehydration/dehydrogenation tests of 2-butanol suggest that strong Br?nsted acid sites are created via hydrogen dissociation at the Pt?WOx interface and spillover to the neighboring oxygen atom. Such in situ formed protons are critical to the selective cleavage of secondary C?O bonds of polyols.
- Lei, Nian,Zhao, Xiaochen,Hou, Baolin,Yang, Man,Zhou, Maoxiang,Liu, Fei,Wang, Aiqin,Zhang, Tao
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supporting information
p. 3903 - 3912
(2019/07/18)
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- Interface synergy between IrOx and H-ZSM-5 in selective C–O hydrogenolysis of glycerol toward 1,3-propanediol
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Site-selective deoxygenation of hydroxyl groups represents essential processes to access valuable functionalized bio-based compounds with industrial potential. One of the challenging tasks in this context is to convert biodiesel-derived glycerol in the presence of abundant water directly to 1,3-propanediol (1,3-PDO), a key component of the emerging polymer industry. Herein, a monometallic iridium supported on H-ZSM-5 in the absence of Re oxophilic metal oxides was prepared via grinding-assisted impregnation procedures and attempted as an effective and recyclable catalyst for the aqueous-phase selective hydrogenolysis of glycerol toward 1,3-PDO in the absence of acid additives. The results revealed the necessity to control the Ir domain dispersions, Ir0/Ir3+ ratio and the amounts of overall acid/Br?nsted acid sites. Activity depended linearly on the amount of overall and Br?nsted acid sites, and 1,3-PDO selectivity increased in the presence of Ir-induced Br?nsted acid sites, denoted as Ir-O(H)-H-ZSM-5. We speculate that Ir-O(H)-H-ZSM-5 are generated by the interfacial synergistic interaction between IrOx and H-ZSM-5 through hydrogen spillover and reverse hydrogen spillover according to the reported literatures. The reaction mechanism to elucidate the role of Ir-O(H)-H-ZSM-5 sites in glycerol hydrogenolysis was also postulated based on extensive characterization and catalytic reaction results.
- Wan, Xiaoyue,Zhang, Qi,Zhu, Mingming,Zhao, Yi,Liu, Yongmei,Zhou, Chunmei,Yang, Yanhui,Cao, Yong
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p. 339 - 350
(2019/07/03)
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- Transfer hydrogenation of cyclic carbonates and polycarbonate to methanol and diols by iron pincer catalysts
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Herein, we report the first example on the use of an earth-abundant metal complex as the catalyst for the transfer hydrogenation of cyclic carbonates to methanol and diols. The advantage of this method is the use of isopropanol as the hydrogen source, thus avoiding the handling of flammable hydrogen under high pressure. The reaction offers an indirect route for the reduction of CO2 to methanol. In addition, poly(propylene carbonate) was converted to methanol and propylene glycol. This methodology can be considered as an attractive opportunity for the chemical recycling of polycarbonates.
- Liu, Xin,De Vries, Johannes G.,Werner, Thomas
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p. 5248 - 5255
(2019/10/11)
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- Capping experiments reveal multiple surface active sites in CeO2 and their cooperative catalysis
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Understanding of surface active sites (SAS) of CeO2 is crucial to its catalytic applications. In the present study, we have employed capping experiments, DFT calculations, and spectroscopic characterization to study pristine CeO2 catalyst. We find that multiple SAS coexist on the CeO2 surface: oxygen vacancies as redox sites and the coordinately unsaturated Ce cations near the oxygen vacancies and the neighboring oxygen ions as Lewis acid-base sites. Dimethylsulfoxide (DMSO), pyridine, and benzoic acid are utilized to cap the redox sites, Lewis acid sites, and base sites, respectively. Selective capping on the redox site does not have much effect on the acid-base catalysis, and vice versa, indicating the distinct surface proximity and independent catalysis of these SAS. We draw attention to a relationship between the well-known redox sites and the surface Lewis acid and Lewis base pairs on CeO2 surface, which are responsible for driving various heterogeneous catalytic reactions.
- Ren, Xiaoning,Zhang, Zhixin,Wang, Yehong,Lu, Jianmin,An, Jinghua,Zhang, Jian,Wang, Min,Wang, Xinkui,Luo, Yi
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p. 15229 - 15237
(2019/05/27)
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- Amino-polystyrene supported hexaethylene glycol-bridged ionic liquid as an efficient heterogeneous catalyst for water-mediated nucleophilic hydroxylation
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We report a simple and eco-friendly method for producing an amino-polystyrene supported hexaethylene glycol-bridged ionic liquid (APS-HEGBIL) based on the copolymerization of amino-styrene with 1-vinyl imidazolium ionic liquid bearing hexaethylene glycol moieties, and its characterization by several analytical techniques. The resulting APS-HEGBIL catalyst was found to be remarkably efficient at catalyzing the selective nucleophilic hydroxylation of alkyl halides to produce the corresponding alcohols in water, which acted as a solvent and a nucleophilic hydroxide source. The catalyst was easily recycled and maintained its catalytic activity and stability after ten cycles with excellent yields. The main attributes of the catalyst were that it significantly enhanced the nucleophilicity of water during reactions and promoted the rapid conversions of polar and base-sensitive alkyl halide reactants to alcohols in excellent yields. The combination of ionic liquids and polymeric materials afforded quasi-homogeneous catalysts that were recycled by simple filtration and provided environmentally benign means for conducted catalytic procedures.
- Reddy, Mudumala Veeranarayana,Kang, Seok Min,Yoo, Suah,Woo, Sang Sik,Kim, Dong Wook
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p. 9435 - 9442
(2019/04/01)
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- Method for preparing 1,3-propylene glycol with ethylene oxide coupling synthesis gas
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The invention provides a method for preparing 1,3-propylene glycol with ethylene oxide coupling synthesis gas and relates to the field of preparation of 1,3-propylene glycol. 3-hydroxy propionate is prepared by ethylene oxide, carbon monoxide and alcohol molecules through ring opening-carbonylation-esterification catalytic reaction, and the 1,3-propylene glycol is prepared by 3-hydroxy propionatethrough hydrogenated catalytic reaction. In the catalytic reaction of the ethylene oxide, carbon monoxide and alcohols, an N,O-ligand coordinated metal complex catalyst is used, preparation of the 3-hydroxy propionate is realized under the action of an organic solvent and an auxiliary agent, and the yield of the 3-hydroxy propionate can reach 97%. For the catalytic reaction of the 3-hydroxy propionate and hydrogen, a copper-containing mixed metal silica catalyst is used, and the yield of the 1,3-propylene glycol can reach 73%. The alcohol produced in hydrogenated catalytic reaction in the second step be recycled for the ring opening-carbonylation-esterification catalytic reaction in the first step.
- -
-
Paragraph 0010; 0061-0076
(2019/10/01)
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- Glycerin and the laevulinic acid one-step process for preparing 1, 3 - propylene glycol and γ - e lactone method
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The invention relates to a method for preparing 1,3-propylene glycol and gamma-valerolactone from glycerin and acetylpropionic acid by a one-step method. According to the method, a stainless steel high-pressure reactor with a volume of 50 ml is adopted; a catalyst used in the invention is Ru/C with its catalytic amount of 0.04g and with its composition by weight of Ru%=5%; and the rest is a carrier, namely activated carbon. A reaction material is a glycerin-acetylpropionic acid solution (concentration of acetylpropionic acid is 20 wt% and concentration ratio of acetylpropionic acid to glycerin is 1:1-10:1), and volume of the solution is 5 ml. A reaction solvent is water. Reaction temperature is 120-200 DEG C; reaction H2 pressure is 2-4 MPa; and reaction time is 0.5-12 h. In comparison with existing technologies for preparing 1,3-propylene glycol from glycerin, the invention is different in the following aspects: an acid reactant is added into the glycerin system; and by the utilization of a metal catalyst, the catalyst can cooperate with the acid reactant to selectively convert glycerin to 1,3-propylene glycol on one hand, and the acid reactant is simultaneously converted to a more valuable product on the other hand. The method provided by the invention has a wide application prospect.
- -
-
Paragraph 0019; 0020; 0055-0057
(2019/06/14)
-
- Preparation method of 1,3-propanediol
-
The invention discloses a preparation method of 1,3-propanediol, and relates to the technical field of chemical synthesis. According to the scheme, glycerol is used as a raw material to prepare 1,3 propylene glycol by using a functional group directional protection method, that is, a terminal hydroxyl group is selectively protected through an etherification reaction, secondary hydroxyl group is removed through a sulfonylation reaction and a reduction reaction, and a protective group is removed. The process of the preparation method provided by the invention has the characteristics of high yield, few byproducts, low cost, easy separation and the like, is an environment-friendly and economical route, overcomes the defects of complex operation and low yield in the prior art, and has a wide development prospect.
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Paragraph 0069; 0079-0081; 0082; 0092-0094; 0095; 0105-0107
(2019/09/17)
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- Pt/ZrO2 Prepared by Atomic Trapping: An Efficient Catalyst for the Conversion of Glycerol to Lactic Acid with Concomitant Transfer Hydrogenation of Cyclohexene
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A series of heterogeneous catalysts consisting of highly dispersed Pt nanoparticles supported on nanosized ZrO2 (20 to 60 nm) was synthesized and investigated for the one-pot transfer hydrogenation between glycerol and cyclohexene to produce lactic acid and cyclohexane, without any additional H2. Different preparation methods were screened, by varying the calcination and reduction procedures with the purpose of optimizing the dispersion of Pt species (i.e., as single-atom sites or extra-fine Pt nanoparticles) on the ZrO2 support. The Pt/ZrO2 catalysts were characterized by means of transmission electron microscopy techniques (HAADF-STEM, TEM), elemental analysis (ICP-OES, EDX mapping), N2-physisorption, H2 temperature-programmed-reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). Based on this combination of techniques it was possible to correlate the temperature of the calcination and reduction treatments with the nature of the Pt species. The best catalyst consisted of subnanometer Pt clusters (2+ and Pt4+) on the ZrO2 support, which were converted into extra-fine Pt nanoparticles (average size = 1.4 nm) upon reduction. These nanoparticles acted as catalytic species for the transfer hydrogenation of glycerol with cyclohexene, which gave an unsurpassed 95% yield of lactic acid salt at 96% glycerol conversion (aqueous glycerol solution, NaOH as promoter, 160 °C, 4.5 h, at 20 bar N2). This is the highest yield and selectivity of lactic acid (salt) reported in the literature so far. Reusability experiments showed a partial and gradual loss of activity of the Pt/ZrO2 catalyst, which was attributed to the experimentally observed aggregation of Pt nanoparticles.
- Tang, Zhenchen,Liu, Pei,Cao, Huatang,Bals, Sara,Heeres, Hero J.,Pescarmona, Paolo P.
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p. 9953 - 9963
(2019/10/17)
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- Method for preparing 1,3-propylene glycol by means of methyl 3-methoxypropionate
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The invention provides a method for preparing 1,3-propylene glycol by means of methyl 3-methoxypropionate, and relates to the field of chemical synthesis. Aiming at the problems that for an existing method, the technology condition is high, a reaction is harsh, and operation is complex, methyl 3-methoxypropionate serves as the main raw material, methyl 3-methoxypropionate is obtained through a hydrogenation reaction, demethylation is conducted, and reaction is conducted with hydroiodic acid, a target product 1,3-propylene glycol and methyl iodide are obtained, methyl iodide is subjected to catalytic cracking finally, and hydroiodic acid is obtained, wherein hydroiodic acid is reused in the demethylation process. For the whole scheme, the synthetic route is short, reaction selectivity is good, the cost is low, the yield is high, the quality is high, raw material resources are simple, the method does not refer to high temperature and high pressure, the technology is safe and reliable, operability is high, and the influence on the environment is low.
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Page/Page column 4-6
(2018/10/11)
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- Comparative study of WCX-based catalysts for aqueous phase hydrogenolysis of glycerol into bioadditives
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Hydrogenolysis of glycerol has been a subject of intensive research in recent decades. Great efforts have been made investigating the mechanism of bond cleavage using metal or metallic oxide catalysts. In this work, effects of a series of WCx-based catalysts, including WCx, Cu/WCx, Pt/WCx, Ru/WCx, CuRu/WCx and CuPt/WCx, were studied on hydrogenolysis of glycerol to investigate the role of each active phase. WO3-Based catalysts were employed as a comparison with the WCx-based catalysts. Hydrogenolysis of model compounds (1,2-PDO and EG) of glycerol was also studied using these catalysts, in attempts to determine the mechanism of the whole reaction. The presence of metal elements on WCx or WO3 can significantly improve the conversion of reactant. In addition, the ability of WCx to promote cleavage of C-C was verified. Ru is more beneficial for formation of EG than Pt, whereas Pt is favorable for formation of 1,2-PDO. It had been supposed that hydrogenolysis of glycerol by WCx-based catalysts occurred via two different but overlapping routes: WCx-related reactions caused by C-C cleavage and metal-related reactions caused by C-O cleavage, which happen simultaneously in the reaction. The current study not only demonstrates that the catalytic performance of WCx can be manipulated by varying metal loading, but also offers a possible mechanism for C-C and C-O cleavage in hydrogenolysis of glycerol, which could be beneficial when focusing on the target product.
- Wei, Lingfei,Bibi, Rehana,Tian, Wei,Chen, Lingyu,Zheng, Yu,Li, Naixu,Zhou, Jiancheng
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p. 3633 - 3641
(2018/03/06)
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- Catalytic Hydrogenation of Cyclic Carbonates using Manganese Complexes
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Catalytic hydrogenation of cyclic carbonates to diols and methanol was achieved using a molecular catalyst based on earth-abundant manganese. The complex [Mn(CO)2(Br)[HN(C2H4PiPr2)2] 1 comprising commercially available MACHO ligand is an effective pre-catalyst operating under relatively mild conditions (T=120 °C, p(H2)=30–60 bar). Upon activation with NaOtBu, the formation of coordinatively unsaturated complex [Mn(CO)2[N(C2H4PiPr2)2)] 5 was spectroscopically verified, which confirmed a kinetically competent intermediate. With the pre-activated complex, turnover numbers up to 620 and 400 were achieved for the formation of the diol and methanol, respectively. Stoichiometric reactions under catalytically relevant conditions provide insight into the stepwise reduction form the CO2 level in carbonates to methanol as final product.
- Kaithal, Akash,H?lscher, Markus,Leitner, Walter
-
supporting information
p. 13449 - 13453
(2018/09/25)
-
- Hydrogenation of CO2-Derived Carbonates and Polycarbonates to Methanol and Diols by Metal–Ligand Cooperative Manganese Catalysis
-
The first base-metal-catalysed hydrogenation of CO2-derived carbonates to alcohols is presented. The reaction proceeds under mild conditions in the presence of a well-defined manganese complex with a loading as low as 0.25 mol %. The non-precious-metal homogenous catalytic system provides an indirect route for the conversion of CO2 into methanol with the co-production of value-added (vicinal) diols in yields of up to 99 %. Experimental and computational studies indicate a metal–ligand cooperative catalysis mechanism.
- Zubar, Viktoriia,Lebedev, Yury,Azofra, Luis Miguel,Cavallo, Luigi,El-Sepelgy, Osama,Rueping, Magnus
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supporting information
p. 13439 - 13443
(2018/09/21)
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- The in situ transformation of the co-product formaldehyde in the reversible hydrolysis of 1,3-dixoane to obtain 1,3-propanediol efficiently
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Herein, a strategy is developed for efficient production of l,3-propanediol via the hydrolysis of 1,3-dioxane by the in situ transformation of the co-product formaldehyde (HCHO) in the presence of Eu(OH)3. The reversible hydrolysis reaction is promoted to yield 98% conversion and 99% 1,3-propanediol selectivity. Furthermore, HCHO is converted to formic acid (HCOOH) which could act as an acidic catalyst in the hydrolysis of 1,3-dioxane. The combination of FT-IR and control experiments demonstrates that HCOOH is generated via the hydrolysis of formate species which formed on the surface of Eu(OH)3.
- Wang, Yehong,Zhang, Jian,Zhang, Zhixin,Hou, Tingting,Zhang, Chaofeng,An, Jinghua,Wang, Feng
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supporting information
p. 1455 - 1458
(2018/04/12)
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- 1. 3 - Propanediol (by machine translation)
-
The present invention provides a 1, 3 - propanediol, comprising the following steps: providing the mass concentration is 8% -13% of 3 - hydroxypropanal aqueous solution of; the hydrogen and 3 - hydroxypropionaldehyde mixed solution, sequentially for a period of hydrogenation reaction and secondary hydrogenation reaction, to obtain the secondary hydrogenation reaction product; part of the two-stage hydrogenation reaction product circulation to a hydrogenation reaction. The 1, 3 - propanediol, through a portion of a two-stage hydrogenation reaction product circulation to a hydrogenation reaction, the absorption of the reaction heat, reducing the temperature of the hydrogenation reaction of the 1st hot spots, can effectively reduce the acetal impurity content in the product, improve the selectivity of the hydrogenation reaction. (by machine translation)
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-
Paragraph 0046; 0047; 0049; 0050; 0051
(2018/09/08)
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- Exploring the Reaction Pathways of Bioglycerol Hydrodeoxygenation to Propene over Molybdena-Based Catalysts
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The one-step reaction of glycerol with hydrogen to form propene selectively is a particularly challenging catalytic pathway that has not yet been explored thoroughly. Molybdena-based catalysts are active and selective to C?O bond scission; propene is the only product in the gas phase under the standard reaction conditions, and further hydrogenation to propane is impeded. Within this context, this work focuses on the exploration of the reaction pathways and the investigation of various parameters that affect the catalytic performance, such as the role of hydrogen on the product distribution and the effect of the catalyst pretreatment step. Under a hydrogen atmosphere, propene is produced primarily via 2-propenol, whereas under an inert atmosphere propanal and glycerol dissociation products are formed mainly. The reaction most likely proceeds through a reverse Mars–van Krevelen mechanism as partially reduced Mo species drive the reaction to the formation of the desired product.
- Zacharopoulou, Vasiliki,Vasiliadou, Efterpi S.,Lemonidou, Angeliki A.
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p. 264 - 275
(2017/12/15)
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- Aerobic Oxidation of 5-(Hydroxymethyl)furfural Cyclic Acetal Enables Selective Furan-2,5-dicarboxylic Acid Formation with CeO2-Supported Gold Catalyst
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The utilization of 5-(hydroxymethyl)furfural (HMF) for the large-scale production of essential chemicals has been largely limited by the formation of solid humin as a byproduct, which prevents the operation of stepwise batch-type and continuous flow-type processes. The reaction of HMF with 1,3-propanediol produces an HMF acetal derivative that exhibits excellent thermal stability. Aerobic oxidation of the HMF acetal with a CeO2-supported Au catalyst and Na2CO3 in water gives a 90–95 % yield of furan 2,5-dicarboxylic acid, an increasingly important commodity chemical for the biorenewables industry, from concentrated solutions (10–20 wt %) without humin formation. The six-membered acetal ring suppresses thermal decomposition and self-polymerization of HMF in concentrated solutions. Kinetic studies supported by DFT calculations identify two crucial steps in the reaction mechanism, that is, the partial hydrolysis of the acetal into 5-formyl-2-furan carboxylic acid involving OH? and Lewis acid sites on CeO2, and subsequent oxidative dehydrogenation of the in situ generated hemiacetal involving Au nanoparticles. These results represent a significant advance over the current state of the art, overcoming an inherent limitation of the oxidation of HMF to an important monomer for biopolymer production.
- Kim, Minjune,Su, Yaqiong,Fukuoka, Atsushi,Hensen, Emiel J. M.,Nakajima, Kiyotaka
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supporting information
p. 8235 - 8239
(2018/06/29)
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- CATALYTIC HYDROGENATION PROCESS FOR THE SYNTHESIS OF TERMINAL DIOLS FROM TERMINAL DIALKYL ALIPHATIC ESTERS
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A phosphorus ligand-free, mild, efficient and complete catalytic hydrogenation process is for the sustainable production of terminal diols from renewable terminal dialkyl esters with improved yield. Soluble, phosphorus ligand free Ru (II)-pincer type complexes can be used as catalysts in the hydrogenation process.
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Paragraph 0067; 0068; 0069
(2018/01/09)
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- Copper nanoparticles socketed in situ into copper phyllosilicate nanotubes with enhanced performance for chemoselective hydrogenation of esters
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Copper nanoparticles exsoluted in situ under a reducing atmosphere at elevated temperatures are socketed into the parent copper phyllosilicate nanotubes and exhibit excellent catalytic performance and superior stability for the selective hydrogenation of various esters to alcohols.
- Gong, Xiaoxiao,Wang, Meiling,Fang, Huihuang,Qian, Xiaoqi,Ye, Linmin,Duan, Xinping,Yuan, Youzhu
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supporting information
p. 6933 - 6936
(2017/07/10)
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- Selective Hydrogenolysis of Glycerol to 1,3-Propanediol: Manipulating the Frustrated Lewis Pairs by Introducing Gold to Pt/WOx
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A highly dispersed Au and Pt catalyst supported on WOx was developed for high performance in the selective hydrogenolysis of glycerol to 1,3-propanediol (1,3-PD) under very mild reaction conditions (81.4 % glycerol conversion, 51.6 % 1,3-PD selectivity at 413 K, 1 MPa H2). The highly dispersed Au decreased the original surface Lewis-acid sites on Pt/WOx but greatly increased its in situ generated Br?nsted-acid sites with the assistance of H2 through the formation of frustrated Lewis pairs. These in situ formed and spatially separated pairs of H+ and H? function as the active sites in glycerol conversion to 1,3-PD.
- Zhao, Xiaochen,Wang, Jia,Yang, Man,Lei, Nian,Li, Lin,Hou, Baolin,Miao, Shu,Pan, Xiaoli,Wang, Aiqin,Zhang, Tao
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p. 819 - 824
(2017/03/17)
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- Application of catalyst with multiple active components for preparing 1,3-propanediol by hydrogenolysis of glycerin
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The invention relates to a catalyst for preparing 1,3-propanediol by hydrogenolysis of glycerin as well as a preparation method thereof. The catalyst comprises a tungsten oxide-aluminum oxide (WO3-Al2O3) composite carrier and active components which comprise any one selected from ruthenium, rhodium, palladium, iridium and platinum (marked as A) and any one selected from gold, silver, copper, nickel, sodium oxide, lithium oxide, potassium oxide, magnesium oxide, gallium oxide, zinc oxide, iron oxide, molybdenum oxide, lanthanum oxide, zirconium oxide, cobalt oxide, rhenium oxide, tin oxide, and manganese oxide (marked as a component B). The prepared catalyst can be used for generating 1,3-propanediol by hydrogenolysis of glycerin at a certain hydrogen pressure and temperature with high conversion rate and high selectivity.
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Paragraph 0024; 0031; 0032
(2017/07/21)
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