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Cas Database

107-21-1

107-21-1

Identification

  • Product Name:Ethylene glycol

  • CAS Number: 107-21-1

  • EINECS:203-473-3

  • Molecular Weight:62.0684

  • Molecular Formula: C2H6O2

  • HS Code:2905.31

  • Mol File:107-21-1.mol

Synonyms:Glycol;Norkool;Ethylene dihydrate;1,2-Dihydroxyethane;Monoethylene glycol;146AR;M.e.g.;Ethylenglykol;Monoethylenglykol tech.;Ethyleneglycol;Glycol alcohol;Ethylene alcohol;Tescol;ethanediol;Ethane-1,2-diol;Athylenglykol;2-hydroxyethanol;Lutrol 9;LUTROL-9;Ethylene glycol-D6;Zerex;Dowtherm SR 1;Fridex;Ucar 17;1,2-Ethanediol;

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Safety information and MSDS view more

  • Pictogram(s):HarmfulXn

  • Hazard Codes:Xn

  • Signal Word:Warning

  • Hazard Statement:H302 Harmful if swallowed

  • First-aid measures: General adviceConsult a physician. Show this safety data sheet to the doctor in attendance.If inhaled Fresh air, rest. Artificial respiration may be needed. Refer for medical attention. In case of skin contact Remove contaminated clothes. Rinse skin with plenty of water or shower. In case of eye contact First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention. If swallowed Rinse mouth. Induce vomiting (ONLY IN CONSCIOUS PERSONS!). Refer for medical attention . Inhalation of vapor is not hazardous. Ingestion causes stupor or coma, sometimes leading to fatal kidney injury. (USCG, 1999) /SRP:/ Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR as necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Ethylene glycol, glycols, and related compounds/

  • Fire-fighting measures: Suitable extinguishing media In case of fire in the surroundings: carbon dioxide, foam, powder, water spray. This chemical is combustible. Wear self-contained breathing apparatus for firefighting if necessary.

  • Accidental release measures: Use personal protective equipment. Avoid dust formation. Avoid breathing vapours, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust. For personal protection see section 8. Personal protection: filter respirator for organic gases and vapours adapted to the airborne concentration of the substance. Collect leaking and spilled liquid in sealable containers as far as possible. Wash away remainder with plenty of water. Collect leaking liquid in covered containers. Wash away spilled liquid with plenty of water.

  • Handling and storage: Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Avoid exposure - obtain special instructions before use.Provide appropriate exhaust ventilation at places where dust is formed. For precautions see section 2.2. Separated from strong oxidants and strong bases. Dry. Ventilation along the floor.Polyethylene glycols should be stored in well-closed containers in a cool, dry place. Stainless steel, aluminum, glass, or lined steel containers are preferred for the storage of liquid grades.

  • Exposure controls/personal protection:Occupational Exposure limit valuesBiological limit values Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday. Eye/face protection Safety glasses with side-shields conforming to EN166. Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU). Skin protection Wear impervious clothing. The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace. Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique(without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Respiratory protection Wear dust mask when handling large quantities. Thermal hazards

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  • Manufacture/Brand:TRC
  • Product Description:1,2-EthyleneGlycol(EthyleneGlycol)
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  • Product Description:Ethylene Glycol >99.5%(GC)
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Relevant articles and documentsAll total 724 Articles be found

Efficient conversion of microcrystalline cellulose to 1,2-alkanediols over supported Ni catalysts

Wang, Xicheng,Meng, Lingqian,Wu, Feng,Jiang, Yijun,Wang, Lei,Mu, Xindong

, p. 758 - 765 (2012)

Nickel supported on a variety of supports was evaluated in the batchwise hydrogenolysis of high-crystalline cellulose under hydrothermal conditions. The supports examined included Al2O3, kieselguhr, TiO 2, SiO2, activated carbon (AC), ZnO, ZrO2 and MgO. All tested catalysts can effectively convert cellulose while the choice of supports plays a critical role in the product distribution and selectivity. The Ni catalysts favour the formation of industrially attractive 1,2-alkanediols such as 1,2-propanediol, ethylene glycol, 1,2-butanediol and 1,2-hexanediol. It was found that the bifunctional ZnO-supported Ni catalysts displayed superior activities and the best result was obtained on 20% Ni/ZnO which exhibited complete conversion of cellulose with up to 70.4% total glycol yields. The mechanism of the reaction involved was tentatively proposed by identifying the products formed. The Royal Society of Chemistry 2012.

Cu-Mg-Zr/SiO2 catalyst for the selective hydrogenation of ethylene carbonate to methanol and ethylene glycol

Tian, Jingxia,Chen, Wei,Wu, Peng,Zhu, Zhirong,Li, Xiaohong

, p. 2624 - 2635 (2018)

A Cux-Mgy-Zrz/SiO2 catalyst with a total metal loading of 60 wt% prepared by a deposition-precipitation method was applied for the selective hydrogenation of ethylene carbonate to methanol and ethylene glycol in a fixed-bed reactor. As a result, the Cu8-Mg1-Zr0.47/SiO2 catalyst furnished 99% ethylene carbonate conversion with 85% selectivity to methanol and 99% selectivity to ethylene glycol under the optimized reaction conditions. Moreover, the Cu8-Mg1-Zr0.47/SiO2 catalyst also showed a good lifetime and neither the activity nor the selectivity decreased the during 208 h test. The reaction was found to depend sensitively on the Cu particle size, the surface acidity and the catalyst surface composition. The synergistic effect of balanced Cu0 and Cu+ sites was considered to play a critical role in attaining high yields of methanol and ethylene glycol. Boric oxide also had a positive effect on the hydrogenation of ethylene carbonate, affording higher selectivity to methanol under much milder conditions.

Hydrogenation of dimethyl oxalate to ethylene glycol over Cu/KIT-6 catalysts

Yu, Xinbin,Burkholder, Michael,Karakalos, Stavros G.,Tate, Gregory L.,Monnier, John R.,Gupton, B. Frank,Williams, Christopher T.

, p. 2403 - 2413 (2021)

Copper supported on KIT-6 mesoporous silica was preparedviaammonia evaporation (AE) method and applied for the catalytic hydrogenation of dimethyl oxalate (DMO) to ethylene glycol (EG). The high specific surface area and interconnected mesoporous channels of the support facilitated the dispersion of copper species. The effect of AE temperature and copper loading on the structure of catalysts and induced change in hydrogenation performance were studied in detail. The results showed that both parameters influenced the overall and/or intrinsic activity. The hydrogenation of DMO to EG was proposed to proceedviathe synergy between Cu0and Cu+sites and catalysts with high surface Cu0/Cu+ratio exhibited high intrinsic activity in the investigated range.

Catalytic Hydrogenation of Cyclic Carbonates using Manganese Complexes

Kaithal, Akash,H?lscher, Markus,Leitner, Walter

, p. 13449 - 13453 (2018)

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.

One-pot synthesized core/shell structured zeolite@copper catalysts for selective hydrogenation of ethylene carbonate to methanol and ethylene glycol

Ding, Yu,Tian, Jingxia,Chen, Wei,Guan, Yejun,Xu, Hao,Li, Xiaohong,Wu, Haihong,Wu, Peng

, p. 5414 - 5426 (2019)

Copper-based catalysts, with highly dispersed and stabilized Cu nanoparticles, intensified mass transfer and a well-balanced Cu0/Cu+ ratio at low Cu loadings, are highly desirable for the selective hydrogenation of ethylene carbonate to ethylene glycol and methanol, an efficient indirect route of CO2 utilization. A hierarchically core/shell-structured Silicalite-1@Cu composite was developed via a base-assisted chemoselective host-guest interaction between the silicon species of MFI-type Silicalite-1 and external Cu salt source. In situ generated mesoporosity and strong Cu-silicate interaction made the uniform Cu NPs firmly immobilized and highly dispersed outside the core S-1 crystals. The S-1@Cu hybrid possessed the co-existing Cu0/Cu+ active species with a suitable ratio, and served as a highly active, selective and robust catalyst for selective ethylene carbonate hydrogenation, providing a lifetime >350 h together with >99% ethylene carbonate conversion, >99% ethylene glycol yield, and more importantly 93% methanol yield at a relatively low Cu loading of 21.4 wt%.

Highly efficient conversion of carbon dioxide catalyzed by polyethylene glycol-functionalized basic ionic liquids

Yang, Zhen-Zhen,Zhao, Ya-Nan,He, Liang-Nian,Gao, Jian,Yin, Zhong-Shu

, p. 519 - 527 (2012)

A series of polyethylene glycol (PEG)-functionalized basic ionic liquids (ILs) were developed for efficient CO2 conversion into organic carbonates under mild conditions. In particular, BrTBDPEG150TBDBr was proven to be a highly efficient and recyclable catalyst for the synthesis of cyclic carbonates without utilization of any organic solvents or additives. This is presumably due to the activation of epoxide assisted by hydrogen bonding and activation of CO2 by the ether linkage in the PEG backbone or through the formation of carbamate species with the secondary amino group in the IL cation on the basis of in situ FT-IR study under CO2 pressure. In addition, the subsequent transesterification of cyclic carbonate e.g. ethylene carbonate (EC) with methanol to dimethyl carbonate (DMC) can also be effectively catalyzed by BrTBDPEG150TBDBr, thanks to the activation of methanol by the secondary and tertiary nitrogen in the IL to easily form CH 3O-, realizing a so-called "one-pot two-stage" access to DMC from CO2 without separation of cyclic carbonate by using one kind of single component catalyst. Therefore, this protocol represents a highly efficient and environmentally friendly example for catalytic conversion of CO2 into value-added chemicals such as DMC by employing PEG-functionalized basic ILs as catalysts.

Adams,Baxendale

, p. 4215 (1958)

Aqueous phase reforming of glycerol using doped graphenes as metal-free catalysts

Esteve-Adell, Iván,Crapart, Bertrand,Primo, Ana,Serp, Philippe,Garcia, Hermenegildo

, p. 3061 - 3068 (2017)

Boron-doped graphene obtained by pyrolysis at 900°C of the boric acid ester of alginate was found to be the most active graphene among a series of doped and co-doped graphenes to promote the aqueous phase reforming of glycerol at 250°C. This reaction is of interest in the context of valorization of the aqueous wastes of carbohydrate syrups. Control experiments adding to undoped graphene 1 wt% of triphenylborane, tris(pentafluorophenyl)borane or bis(pinacolyl)diborane as models of possible boron atom types present in B-doped graphene, and boric acid that could be present in a residual amount after pyrolysis, show in all cases an increase in the catalytic activity of graphene. B-doped graphene has also activity for glucose aqueous phase reforming. B-doped graphene undergoes deactivation upon reuse, probably due to B leaching. The results show that graphenes are promising metal-free catalysts for aqueous phase reforming and are alternatives to those containing platinum.

Mechanistic aspects of the oxidative functionalization of ethane and ethanol by platinum(II) salts in aqueous medium. Role of platinum(II)-olefin and platinum(IV) - alkyl intermediates

Hutson, Alan C.,Lin, Minren,Basickes, Naomi,Sen, Ayusman

, p. 69 - 74 (1995)

The relative rate of C-H bond activation by the Pt(II) ion decreased in the order H-CH2CH3 > H-CH2CH2OH > H-CH(OH)CH3.The platinum(II)-ethylene complex, -, 1, was the key intermediate in the oxidation of ethane, ethanol, and diethyl ether to 1,2-ethanediol by platinum(II) in aqueous medium.In particular, the intermediacy of 1 in the oxidation of ethanol to 1,2-ethanediol and 2-chloroethanol was verified through labeling studies.In D2O, 1, upon oxidation with one of a number of oxidants, converted to 2-, 2. 2 in turn decomposed to a mixture of 1,2-ethanediol and 2-chloroethanol on heating.The rate conversion of 1 was a function of pH, the anions present, and the oxidant used.While the conversion of 1 to 2 involved a nucleophilic attack by water (or hydroxide ion), such a step was not observed in the absence of an oxidant.In basic D2O, the sequential replacement of Cl- by OD- in 1 occurred to successively form -, - and -.The process was reversed upon acidification.The species 2-, 3, appeared to be the source for the small quantities of hydroxy- and/or chloroacetaldehyde formed during the oxidation of 1. 3 was synthesized independently by the reaction of acetaldehyde with a mixture of PtCl42-, and PtCl62- in aqueous medium.When 1 was oxidized by Cl2 in CD3OD solution, the principal product was 2- 4, when a small amount of water was present, and CD3OCH2CH2OCD3 in the absence of water. Keywords: Platinum complex; C-H activation; Oxidation; Ethane; Ethylene; Ethanol

Efficient one-pot production of 1,2-propanediol and ethylene glycol from microalgae (Chlorococcum sp.) in water

Miao,Zhu,Wang,Tan,Wang,Liu,Kong,Sun

, p. 2538 - 2544 (2015)

The catalytic valorization of microalgae, a sustainable feedstock to alleviate dependence on fossil fuel and offset greenhouse gases emissions, is of great significance for production of biofuels and value-added chemicals from aquatic plants. Here, an interesting catalytic process is reported to convert microalgae (Chlorococcum sp.) into 1,2-propanediol (1,2-PDO) and ethylene glycol (EG) in water over nickel-based catalysts. The influences of reaction temperature, initial H2 pressure and reaction time on the product distribution were systematically investigated by using a batch reactor. Under optimal reaction conditions (at 250 °C for 3 h with 6.0 MPa of H2 pressure), microalgae were directly and efficiently converted over a Ni-MgO-ZnO catalyst and the total yield of polyols was up to 41.5%. The excellent catalytic activity was attributed to the smaller size and better dispersion of Ni particles on the MgO-ZnO supporter based on the characterization results as well as its tolerance to nitrogen-containing compounds. Besides, the reaction pathway was proposed based on the formation of reaction intermediates and the results of model compound conversion.

Hydrogenolysis of glycerol over supported bimetallic Ni/Cu catalysts with and without external hydrogen addition in a fixed-bed flow reactor

Cai, Fufeng,Pan, Donghui,Ibrahim, Jessica Juweriah,Zhang, Jun,Xiao, Guomin

, p. 172 - 182 (2018)

The role of high hydrogen pressure in the hydrogenolysis of glycerol to 1,2-propanediol has been studied extensively. Given the peculiar properties of hydrogen such as its inflammability and explosibility, the hydrogenolysis of glycerol without external hydrogen addition seems a more advantageous option. This study focuses on the conversion of glycerol to 1,2-propanediol over different supported bimetallic Ni/Cu catalysts in a fixed-bed flow reactor, using in situ hydrogen production and external hydrogen. Among the catalysts prepared, Ni/Cu/TiO2 catalyst was observed to efficiently catalyze the hydrogenolysis of glycerol to 1,2-propanediol under N2 pressure using 2-propanol as hydrogen source. This was due to the high Cu dispersion and Ni/Cu atomic ratio on the catalyst surface. However, the experimental results indicated that the effect of catalyst acid sites on glycerol hydrogenolysis was more noticeable when the reaction was performed under H2 pressure. The metal active sites of the catalyst played a significant role in the hydrogen production and also affected the glycerol hydrogenolysis with hydrogen produced from 2-propanol catalytic transfer hydrogenation (CTH) and glycerol aqueous phase reforming (APR). The stability study revealed that the Ni/Cu/TiO2 catalyst underwent serious deactivation during the hydrogenolysis of glycerol. The characterization results showed that the metal leaching and metal particles sintering were responsible for the catalyst deactivation when the glycerol hydrogenolysis was conducted using water as a solvent. However, the activity loss for reactions performed using 2-propanol as a solvent was mainly related to the metal particles sintering and the presence of adsorbed species on the catalyst surface.

Catalytic conversion of glucose and cellobiose to ethylene glycol over Ni-WO3/SBA-15 catalysts

Cao, Yueling,Wang, Junwei,Kang, Maoqing,Zhu, Yulei

, p. 90904 - 90912 (2015)

Hydrogenolysis of glucose and cellobiose, used as the model feedstocks, over Ni-WO3/SBA-15 catalysts has been investigated to probe the influencing factors for the conversion of cellulose to ethylene glycol (EG). The conversion of glucose and cellobiose to EG showed different dependencies on reaction temperature; a lower reaction temperature was needed for the former. Additionally, the surface atomic ratio of W to Ni on the Ni-WO3/SBA-15 catalysts was the key factor for the product distribution. Both glucose and cellobiose had their own optimum W-Ni ratio for the production of EG, and the ratio of W to Ni for glucose was slightly lower than that of cellobiose. On the other hand, the Ni-WO3/SBA-15 catalysts were thoroughly characterized by N2 adsorption-desorption, X-ray diffraction (XRD), hydrogen-temperature programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The results indicated that the reducibility of Ni-WO3/SBA-15 catalysts with high Ni loading was more similar to that of pure NiO. More importantly, the change of surface atomic content of Ni and W of Ni-WO3 catalysts with various Ni loadings resulted from the surface W species of the catalysts being gradually covered by Ni species with the increase of Ni loading.

Glycerol hydrogenolysis promoted by supported palladium catalysts

Musolino, Maria Grazia,Scarpino, Luciano Antonio,Mauriello, Francesco,Pietropaolo, Rosario

, p. 1143 - 1150 (2011)

Catalytic hydrogenolysis, with high conversion and selectivity, promoted by supported palladium substrates in isopropanol and dioxane at a low H 2 pressure (0.5MPa), is reported for the first time. The catalysts, characterized by using BET isotherms, transmission electron microscopy (TEM), temperature-programmed reduction (TPR), powder X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), were obtained by coprecipitation and impregnation techniques. The coprecipitation method allows catalysts with a metal-metal or a metal-support interaction to be obtained, which enhances the catalytic performance for both the conversion of glycerol and the selectivity to 1,2-propanediol. Analogous reactions carried out with catalysts prepared by using impregnation are less efficient. A study of the solvent and temperature effect is also presented. The obtained results allow the hydrogenolysis mechanism to be inferred; this involves both the direct replacement of the carbon-bonded OH group by an incoming hydrogen or the formation of hydroxyacetone as an intermediate, which subsequently undergoes a hydrogenation process to give 1,2-propanediol. Finally, catalytic tests on a large-scale reaction at a higher H2 pressure and recycling of the samples were carried out with the better performing catalysts (Pd/CoO and Pd/Fe 2O3 prepared by using coprecipitation) to verify possible industrial achievements.

Influence of support on the performance of copper catalysts for the effective hydrogenation of ethylene carbonate to synthesize ethylene glycol and methanol

Li, Fengjiao,Wang, Liguo,Han, Xiao,He, Peng,Cao, Yan,Li, Huiquan

, p. 45894 - 45906 (2016)

Hydrogenation of ethylene carbonate (EC) is an attractive and promising approach for indirect hydrogenation of CO2 to co-produce ethylene glycol (EG) and methanol (MeOH). In this work, thermodynamics of EC hydrogenation was firstly calculated, and the results disclosed that EC hydrogenation is exothermic (ΔrHθm = -71.59 kJ mol-1) and thermodynamically favorable (ΔrGθm = -25.62 kJ mol-1). The mesoporous silica supported copper catalysts were successfully prepared by facile ammonia evaporation method using KIT-6, MCM-41 and SBA-15 as support materials. The as-prepared Cu/KIT-6, Cu/MCM-41 and Cu/SBA-15 were thoroughly characterized by N2 physisorption, ICP-AES, N2O titration, FT-IR, XRD, H2-TPR, TEM, XPS and XAES. It was found that copper nanoparticles were well dispersed on these supports. Interestingly, a larger metallic Cu surface area with higher dispersion was obtained on SBA-15 when compared with KIT-6 and MCM-41. Furthermore, Cu0 and Cu+ species in various ratios were verified to co-exist on the surfaces of the three catalysts, which originated from CuO and copper phyllosilicate, respectively. The catalytic performances showed that Cu/SBA-15 exhibited a superior catalytic activity with a TON of 22.0 and 11.4 (mol mol-1) towards EG and MeOH, respectively. Importantly, 100% of EC conversion, 94.7% of EG yield and 62.3% of MeOH yield were achieved within a short reaction time of 4 h over Cu/SBA-15 under optimized conditions. The synergetic effect between Cu0 and Cu+ species, in which it was proposed that Cu0 species dissociated H2, while Cu+ species absorbed the carbonyl group of EC, was responsible for the higher catalytic activity of Cu/SBA-15.

Effect of Calcination Temperature on the Textural Properties and Catalytic Behavior of the Al2O3 Doped Mesoporous Monometallic Cu Catalysts in Dimethyl Oxalate Hydrogenation

Kong, Xiangpeng,Wu, Yuehuan,Yuan, Peihong,Wang, Man,Wu, Peng,Ding, Lifeng,Wang, Ruihong,Chen, Jiangang

, p. 2107 - 2115 (2021)

Abstract: Al2O3 doped mesoporous monometallic Cu catalysts were successfully synthesized though the self-assembly Cu species derived from the oxalate precursor undergoing thermal decomposing. The evolutions of microstructures, physicochemical and surface properties of the CuAl catalysts have been systematically characterized focusing on the effect of the calcination temperature during catalyst preparation. It is found that the textural and surface properties of the CuAl catalysts were profoundly affected by the calcination temperature, further determining the resultant catalytic behavior in dimethyl oxalate (DMO) hydrogenation. Particularly, the CuAl-500 possessing the maximum surface Cu+ sites and proper surface acid features exhibits?100.0% DMO conversion and 98.0% ethylene glycol (EG) selectivity in presence of the adequate active Cu0 sites, which is superior to that of the other catalysts under the identical reaction conditions. And no activity loss occurred for more than 200?h demonstrated of the outstanding stability of the CuAl-500 catalyst. Moreover, the synergistic effect between surface Cu+ and Cu0 sites should be responsible for DMO selective hydrogenation. Additionally, the strengthened chemical interaction between Cu and Al species endows the catalysts outstanding stability by suppressing the dispersive Cu NPs agglomeration during DMO hydrogenation. Graphic Abstract: [Figure not available: see fulltext.]

Identifying the components of the solid–electrolyte interphase in Li-ion batteries

Wang, Luning,Menakath, Anjali,Han, Fudong,Wang, Yi,Zavalij, Peter Y.,Gaskell, Karen J.,Borodin, Oleg,Iuga, Dinu,Brown, Steven P.,Wang, Chunsheng,Xu, Kang,Eichhorn, Bryan W.

, p. 789 - 796 (2019)

The importance of the solid–electrolyte interphase (SEI) for reversible operation of Li-ion batteries has been well established, but the understanding of its chemistry remains incomplete. The current consensus on the identity of the major organic SEI component is that it consists of lithium ethylene di-carbonate (LEDC), which is thought to have high Li-ion conductivity, but low electronic conductivity (to protect the Li/C electrode). Here, we report on the synthesis and structural and spectroscopic characterizations of authentic LEDC and lithium ethylene mono-carbonate (LEMC). Direct comparisons of the SEI grown on graphite anodes suggest that LEMC, instead of LEDC, is likely to be the major SEI component. Single-crystal X-ray diffraction studies on LEMC and lithium methyl carbonate (LMC) reveal unusual layered structures and Li+ coordination environments. LEMC has Li+ conductivities of >1 × 10?6 S cm?1, while LEDC is almost an ionic insulator. The complex interconversions and equilibria of LMC, LEMC and LEDC in dimethyl sulfoxide solutions are also investigated.

Design and preparation of hydrated MgAl supported Cu catalysts with high alkalinity by MOCVD for the hydrogenolysis of cellulose

Xiao, Zihui

, p. 343 - 349 (2017)

The unhydrated and hydrated MgAl supported Cu catalysts were successfully prepared by metal-organic chemical vapor deposition (MOCVD) method. The structure properties of metal-organic precursor, supports and catalysts were determined by 1H NMR, FTIR, XRD, N2 physisorption, TEM, N2O titration, and CO2-TPD. The hydration of support had a significant effect on the structure of the final catalysts. The hydrated Mg3Al1 support was benefited to the adsorption and deposition of CuII(hfac)2, resulting in the decrease of the reduction decomposition temperature. Due to the restoration of the layered structure, the 5%Cu/H-Mg3Al1 catalyst had a low BET surface area and pore volume. However, it exhibited higher base sites density and got better performance for cellulose hydrogenolysis compared to the 5%Cu/Mg3Al1 catalyst, which suggested that the hydration before reaction was superior to that during reaction for the catalytic performance, due to the competition between water and products (alcohols with strong adsorption) during reaction, resulting in a decrease in the concentration of in-situ formed surface OH? and the amount of base sites. It was noteworthy that unobvious change in phases of the 5%Cu/H-Mg3Al1 catalyst was observed before and after reaction, which provided a promising way to establish the relationship between structure and catalytic performance.

Ruthenium-catalysed hydrogenation of esters using tripodal phosphine ligands

Hanton, Martin J.,Tin, Sergey,Boardman, Brian J.,Miller, Philip

, p. 70 - 78 (2011)

The synthesis of a new tripodal phosphine ligand, N(CH2PEt 2)3, N-TriPhosEt is reported, and the use of tripodal ligands of this type, N(CH2PR2)3 (R = Ph, Et), in conjunction with ruthenium for the catalysed hydrogenation of dimethyl oxalate (DMO) is reported and contrasted with catalysis using the MeC(CH2PPh2)3 (TriPhosPh) ligand. A different order of reaction with respect to the DMO substrate is found, and the rate is slower. A study of the kinetics and mechanism of the hydrogenation of DMO with Ru(acac)3/TriPhosPh is described, along with the effect of different additives to the system. The performance of Ru(acac) 3/TriPhosPh/Zn system with unactivated ester substrates is probed and found to proceed significantly slower. Finally, based upon experimental observations, a mechanism is proposed for ester hydrogenation using ruthenium catalysts with tripodal phosphine ligands.

1,3-Dimethylimidazolium-2-carboxylate: A zwitterionic salt for the efficient synthesis of vicinal diols from cyclic carbonates

Sun, Jian,Yao, Xiaoqian,Cheng, Weiguo,Zhang, Suojiang

, p. 3297 - 3304 (2014)

The development of efficient, cheap and recyclable catalysts for reactions under mild reaction conditions is a very attractive topic in green chemistry. Herein, a series of basic ionic liquids (ILs) were investigated as catalysts for the synthesis of vicinal diols via the hydrolysis of cyclic carbonates in order to improve this kind of synthetic process. The effects of the IL structure, the molar ratio of cyclic carbonate to water, and various reaction parameters on the catalytic performance were investigated in detail. It was found that 1,3-dimethylimidazolium-2-carboxylate, a simple halogen-free zwitterionic catalyst, showed high activity (a space-time yield of 1086 h-1) and excellent selectivity for the preparation of ethylene glycol via the hydrolysis of ethylene carbonate. The catalyst could be reused over six times without obvious loss of catalytic activity. Also, it was applicable to a variety of cyclic carbonates for the production of their corresponding vicinal diols with high yields and selectivities. A possible catalytic cycle for this kind of catalytic process was proposed based on the experimental results, NMR spectroscopy and theoretical calculations. This reaction protocol opens a new possibility for chemical synthesis as a substitution for traditional base or basic ILs. This journal is the Partner Organisations 2014.

Anion-specific binding to n-hexadecyl phosphorylcholine micelles

Priebe, Jacks P.,Souza, Bruno S.,Micke, Gustavo A.,Costa, Ana C.O.,Fiedler, Haidi D.,Bunton, Clifford A.,Nome, Faruk

, p. 1008 - 1012 (2010)

Hexadecyl phosphorylcholine (HPC) micelles incorporate anions rather than cations in the interfacial region, giving an anionoid micelle with a negative zeta potential. Hydronium ion incorporation in the micellar pseudophase parallels the increase in the n

Studies on mechanism for homogeneous catalytic hydration of ethylene oxide: Effects of pH window and esterification

Yang, Zhi-Jian,Ren, Nan,Zhang, Ya-Hong,Tang, Yi

, p. 447 - 450 (2010)

Selective hydration of ethylene oxide (EO) was investigated with several inorganic salt systems as homogeneous catalysts. By optimizing reaction conditions, the highest monoethylene glycol (MEG) selectivity of 98% was obtained with >99% EO conversion at a water/EO molar ratio = 10. The effects of pH value and anion addition-esterification on MEG selectivity were systematically studied, and a comprehensive mechanism was proposed based on the results. The conclusion should be useful in developing high performance catalysts for the manufacture of MEG by EO hydration at a low water/EO ratio. Crown Copyright

The synthesis of highly reactive, multi-functional α,β-epoxy- and α-acetoxy-nitrosamines

Park, Misun,Gu, Feng,Loeppky, Richard N.

, p. 1287 - 1290 (1998)

The synthesis of the reactive acetates, trans-3-acetoxy-2-hydroxy-N-nitrosomorpholine 3 and N-(1-acetoxy-2-hydroxyethyl)-N-nitrosoethanolamine 12, of two α-hydroxynitrosamines has been accomplished through the ring opening of the corresponding epoxides, NEMOR and 10 which were prepared by dimethyldioxirane oxidation of the vinyl nitrosamines.

Efficient Photoelectrochemical Conversion of Methane into Ethylene Glycol by WO3 Nanobar Arrays

Ma, Jun,Mao, Keke,Low, Jingxiang,Wang, Zihao,Xi, Dawei,Zhang, Wenqing,Ju, Huanxin,Qi, Zeming,Long, Ran,Wu, Xiaojun,Song, Li,Xiong, Yujie

, p. 9357 - 9361 (2021)

Photoelectrochemical (PEC) conversion of methane (CH4) has been extensively explored for the production of value-added chemicals, yet remains a great challenge in high selectivity toward C2+ products. Herein, we report the optimization of the reactivity of hydroxyl radicals (.OH) on WO3 via facet tuning to achieve efficient ethylene glycol production from PEC CH4 conversion. A combination of materials simulation and radicals trapping test provides insight into the reactivity of .OH on different facets of WO3, showing the highest reactivity of surface-bound .OH on {010} facets. As such, the WO3 with the highest {010} facet ratio exhibits a superior PEC CH4 conversion efficiency, reaching an ethylene glycol production rate of 0.47 μmol cm?2 h?1. Based on in situ characterization, the methanol, which could be attacked by reactive .OH to form hydroxymethyl radicals, is confirmed to be the main intermediate for the production of ethylene glycol. Our finding is expected to provide new insight for the design of active and selective catalysts toward PEC CH4 conversion.

Catalytic conversion of cellulose to ethylene glycol over tungsten phosphide catalysts

Zhao, Guanhong,Zheng, Mingyuan,Wang, Aiqin,Zhang, Tao

, p. 928 - 932 (2010)

Tungsten phosphide (WP) showed good activity in the selective conversion of cellulose to ethylene glycol (EG). At a H2 initial pressure of 6 MPa and temperature of 245 °C, EG yield reached 25.4 mol over 20WP/AC (activated carbon) and 46.0 mol over 2Ni-20WP/AC, which demonstrated a remarkable synergy between Ni and WP.

Physical and chemical studies of tungsten carbide catalysts: Effects of Ni promotion and sulphonated carbon

Rodella, Cristiane B.,Barrett, Dean H.,Moya, Silvia F.,Figueroa, Santiago J.A.,Pimenta, Maria T. B.,Curvelo, Antonio Aprígio S.,Teixeira Da Silva, Victor

, p. 23874 - 23885 (2015)

Ni promoted tungsten carbides have been shown to be an effective catalyst for cellulose conversion reaction. With the use of both in situ and ex situ techniques an investigation into the physical and chemical aspects of the Ni-promoted tungsten carbide catalyst supported on activated carbon either in pure form or functionalized with sulfuric acid was conducted. In situ XRD analysis performed during the carburization process showed that non-promoted samples formed a mixture of nanosized W2C, WC1-x and WC carbide phases. In the case of Ni promoted catalysts, in situ XRD, XANES, XPS and TEM analysis revealed that Ni aids in lowering the carburization temperature by 50 °C but also assisted in the deposition of polymeric carbon onto the catalyst surface which reduced cellulose conversion. However, the results indicate beneficial effects caused by the high carbon coverage by stopping the W2C to WC carbide phase transition. Thus, carburization of Ni promoted samples produced only W2C phase, which is stable up to 800°C. The functionalization of activated-carbon with -SO3H not only increases the hydrolysis of cellulose but also lead to a greater dispersion of Ni over the catalyst. The resulting improvement in the interaction between Ni/W/C increases the cellulose transformation in a one-pot synthesis towards the production of ethylene glycol.

Decomposition reactions of (hydroxyalkyl) nitrosoureas and related compounds: Possible relationship to carcinogenicity

Singer

, p. 1088 - 1093 (1985)

(Hydroxyalkyl)nitrosoureas and the related cyclic carbamates N-nitrosooxazolidones are potent carcinogens. The decompositions of four such compounds, 1-nitroso-1-(2-hydroxyethyl)urea, 3-nitrosooxazolid-2-one, 1-nitroso-1-(2-hydroxypropyl)urea, and 5-methyl-3-nitrosooxazolid-2-one, in aqueous buffers at physiological pH were studied to determine if any obvious differences in decomposition pathways could account for the variety of tumors obtined from these four compounds. The products predicted by the literature mechanisms of nitrosourea and nitrosooxazolidone decompositions (which were derived from experiments at pH 10-12) were indeed the products formed, including glycols, active carbonyl compounds, epoxides, and, from the oxazolidones, cyclic carbonates. Furthermore, it was shown that in pH 6.4-7.4 buffer epoxides were stable reaction products. However, in the presence of hepatocytes, most of the epoxide was converted to glycol. The analytical methods developed were then applied to the analysis of the decomposition products of some related dialkylnitrosoureas, and similar results were obtained. The formation of chemically reactive secondary products and the possible relevance of these results to carcinogenesis studies are discussed.

Enhanced catalytic performance for SiO2-TiO2 binary oxide supported Cu-based catalyst in the hydrogenation of dimethyloxalate

Wen, Chao,Yin, Anyuan,Cui, Yuanyuan,Yang, Xinli,Dai, Wei-Lin,Fan, Kangnian

, p. 82 - 89 (2013)

Copper based catalyst with Si-Ti binary-oxide support is synthesized via a facile ammonia evaporation method for selective hydrogenation of dimethyloxalate (DMO) to ethylene glycol (EG). 100% conversion of DMO and 90% selectivity to EG could be obtained over the Cu/SiO2-TiO2 catalyst at high liquid hourly space velocity (LHSV). Catalytic stability is greatly enhanced when the Si-Ti binary oxide is used as support because of the intimate interaction between copper species and the support. The improved catalytic performance compared to the unitary oxide-supported catalysts SiO2 and TiO2 could be attributed to the highly dispersed copper species stabilized by the binary support. Also, the electron transfer from TiO 2 to Cu-species is found to play an important role in improving the surface charge density of the metallic copper, which is helpful to improve the catalytic activity.

Hydrogenation of carbon monoxide by homogeneous ruthenium-rhenium bimetallic catalysts: effects of rhenium carbonyl as a promoter for ethylene glycol formation

Tanaka, Masahide,Kiso, Yoshihisa,Saeki, Kenji

, p. 99 - 104 (1987)

The activity of the ruthenium-halide catalyst for ethylene glycol formation from CO/H2 is enhanced by a rhenium carbonyl compound.The activity of the Ru-Re bimetallic catalyst is dependent upon the ratio of Re/Ru atoms and the ratio of moles of halide to atoms of Re.The activities of Ru-Re-alkali metal iodide catalysts increased with increasing ionic radius of alkali metal.

A New Aspect of the Pressure Effect in Syngas Conversion to Ethylene Glycol

Masuda, Takashi,Murata, Kazuhisa,Matsuda, Akio

, p. 1287 - 1289 (1986)

Pressure effect in syngas conversion to ethylene glycol (EG) is understood in terms of respective partial pressures of hydrogen (PH2) and carbon monoxide (PCO).A new mechanism is proposed to explain an etraordinary effect of PH2 on the selectivity to EG.

An effective and stable Ni2P/TiO2 catalyst for the hydrogenation of dimethyl oxalate to methyl glycolate

Chen, Hongmei,Tan, Jingjing,Zhu, Yulei,Li, Yongwang

, p. 46 - 49 (2016)

An effective and stable bifunctional Ni2P/TiO2 catalyst was proposed for gas-phase hydrogenation of dimethyl oxalate to corresponding alcohols. A 93.0% conversion of DMO with a selectivity of 88.0% to methyl glycolate was observed under 210 °C. Moreover, the catalyst showed an excellent stability which can be performed for 3600 h under the reaction conditions of 230 °C, 3 MPa H2 and the weight space velocity of 0.1 h?1.

Chiral Polyol Synthesis Catalyzed by a Thermostable Transketolase Immobilized on Layered Double Hydroxides in Ionic liquids

Ali, Ghina,Moreau, Thomas,Forano, Claude,Mousty, Christine,Prevot, Vanessa,Charmantray, Franck,Hecquet, Laurence

, p. 3163 - 3170 (2015)

In this work we set out to study the activity of a thermostable Transketolase (TK) from Geobacillus stearothermophilus (TKgst) in an ionic liquid as cosolvent, which has never been investigated before with this enzyme. 1-Butyl-3-methylimidazolium chloride ([BMIm][Cl]) in the range 30-50% in water maintained the total activity of TKgst and increased the reaction rate in the presence of pentoses as acceptor substrates, particularly d-ribose. To improve the synthetic process, TKgst was immobilized on an inorganic support, layered double hydroxides (LDHs), with excellent immobilization yield and catalytic activity using a simple, eco-compatible, efficient coprecipitation procedure. The biohybrid MgAl@TKgst was tested in 30% [BMIm][Cl] for the synthesis of a rare, very costly commercially available sugar, d-sedoheptulose, which was obtained in one step from d-ribose with an isolated yield of 82%. This biohybrid was reusable over four cycles with no loss of enzymatic activity. The particular activity of free and immobilized TKgst in [BMIm][Cl] holds promise to extend the applications of TKgst in other ionic liquids and unusual media in biocatalysis.

HOMOGENEOUS CATALYTIC HYDROGENATION OF DICARBOXYLIC ACID ESTERS. II

Matteoli, Ugo,Menchi, Gloria,Bianchi, Mario,Piacenti, Franco

, p. 233 - 238 (1986)

Hydrogenation of dimethyl oxalate in the presence of Ru(CO)2(CH3COO)2(PBu3)2 gives methyl glycolate and subsequently ethylene glycol.The formation of the glycol is favoured by hydroxylated solvents.

Selective Hydrogenolysis of Glycerol to Propylene Glycol on Supported Pd Catalysts: Promoting Effects of ZnO and Mechanistic Assessment of Active PdZn Alloy Surfaces

Sun, Qianhui,Wang, Shuai,Liu, Haichao

, p. 4265 - 4275 (2017)

Pd catalysts have received increasing attention for selective hydrogenolysis of glycerol to propylene glycol because of their good hydrothermal stability and high selectivity for cleavage of C-O bonds over C-C bonds. Addition of Zn can facilitate glycerol hydrogenolysis to propylene glycol on Pd surface, but the promoting role of Zn, stability of the resulting active PdZn alloys and reaction mechanism remain largely unexplored. Here, we synthesized monoclinic zirconia-supported PdZn (PdZn/m-ZrO2) catalysts via an incipient wetness impregnation method. Glycerol hydrogenolysis turnover rates (normalized per surface Pd atom measured by H2 chemisorption) and propylene glycol selectivity on these PdZn/m-ZrO2 catalysts depended sensitively on their Zn/Pd molar ratios, and Zn leaching from the PdZn alloy phases led to deactivation of PdZn/m-ZrO2. Such deactivation was efficiently inhibited when physical mixtures of Pd/m-ZrO2 and ZnO were directly used in glycerol hydrogenolysis, leading to in situ formation of PdZn alloy layers on Pd surfaces with excellent stability and recyclability. Dependence of turnover rates on glycerol and H2 concentrations, combined with the primary kinetic isotope effects (kH/kD = 2.6 at 493 K), reveals the kinetically relevant step of glycerol hydrogenolysis involving the α-C-H cleavage in 2,3-dihydroxypropanoxide intermediate to glyceraldehyde on PdZn alloys and Pd. Measured rate constants show that the transition state of α-C-H cleavage is more stable because of the stronger oxophilicity of Zn on PdZn alloys than on Pd, which thus facilitates α-C-H cleavage of the Zn-bound intermediate by adjacent Pd on PdZn alloys. Such synergy between Zn and Pd sites accounts for the observed superiority of PdZn alloys to Pd in glycerol hydrogenolysis. (Chemical Equation Presented).

A boron-doped carbon aerogel-supported Cu catalyst for the selective hydrogenation of dimethyl oxalate

Lu, Xiaodong,Lu, Xiaodong,Wang, Guofu,Yang, Yu,Kong, Xiangpeng,Chen, Jiangang

, p. 3232 - 3240 (2020)

Carbon aerogels (CA) were applied in the synthesis of Cu/CA catalysts by the impregnation method and the catalysts with boron-doped CA supports were systematically characterized and evaluated in the hydrogenation of dimethyl oxalate (DMO). The Cu/xB-CA catalyst with 25 wt% copper showed 100% DMO conversion and the highest ethylene glycol (EG) or methyl glycolate (MG) selectivity of 70% at 230 °C as well as a lifetime of over 150 h. The characterization results disclosed the reason the performance of the catalysts could be tuned facilely by changing the amount of boron doping, which effectively influenced the interrelation between copper and CA, acidity and alkalinity of catalysts and Cu dispersion. Both the original carbon aerogels and that promoted with little B could provide larger surface areas and high dispersion of the metal. The species, size of copper particles and the ratio of Cu+/(Cu+ + Cu0) could be regulated by boron doping, thus adjusting the type of hydrogenation products.

Vapour phase hydrogenolysis of glycerol over nano Ru/SBA-15 catalysts on the effect of preparatory routes and metal precursors

Pavankumar, Vanama,Srikanth, Chakravartula S.,Rao, Anipindi Nageswara,Chary, Komandur V. R.

, p. 3137 - 3146 (2014)

The effect of preparation method and metal precursor of ruthenium employed during the preparation of Ru/SBA-15 catalysts were investigated. The catalytic functionalities are evaluated during the vapour phase hydrogenolysis of glycerol to 1,2-propyleneglyc

Synergistic effect between Pd and Re on Pd-Re/SBA-15 catalysts and their catalytic behavior in glycerol hydrogenolysis

Li, Yuming,Liu, Huimin,Ma, Lan,He, Dehua

, p. 38680 - 38689 (2016)

Pd-Re/SBA-15 catalysts were prepared by the impregnation method. The influence of the interaction between Pd and Re in the Pd-Re catalysts on glycerol hydrogenolysis was investigated. Pd and Re had interaction which was confirmed by H2-TPR, XPS and EXAFS. In the Pd-Re catalysts, Re showed a higher oxidation state compared with that of the mono-component Re catalyst. The mechanically mixed Pd + Re catalysts showed a lower glycerol conversion than that of the bi-component Pd-Re catalysts, which suggested that the interaction of Pd and Re was very important in glycerol hydrogenolysis.

-

Ciamician,Silber

, (1911)

-

The kinetics of glycerol hydrodeoxygenation to 1,2-propanediol over Cu/ZrO2 in the aqueous phase

Gabrysch, Thomas,Muhler, Martin,Peng, Baoxiang

, p. 47 - 53 (2019)

The kinetics of glycerol hydrodeoxygenation to 1,2-propanediol via the selective cleavage of the primary C-O bond was systematically studied in the aqueous phase over a co-precipitated Cu/ZrO2 catalyst. Unsupported pure metallic Cu was used as reference catalyst. Batch experiments were performed in an autoclave by varying the reaction temperature (175–225 °C), H2 partial pressure (25–35 bar) and initial glycerol concentration (2–8 wt%). The Cu/ZrO2 catalyst was found to be highly selective to 1,2propanediol (up to 95%), and ethylene glycol was obtained as major by-product from parallel C–]C bond hydrogenolysis. The apparent activation energies amounting to 106 and 105 kJ mol-1 for Cu/ZrO2 and pure metallic Cu, respectively, of the hydrodeoxygenation pathway provide further evidence for metallic Cu acting as the active site. Kinetic analysis of the rate of glycerol consumption yielded a zero-order dependence on the concentration of glycerol suggesting an essentially almost full coverage of adsorbed glycerol as most strongly bound organic adsorbate. In contrast, a first-order dependence on hydrogen concentration was observed. Hydrogen is assumed to be not only required for the fast hydrogenation of the intermediate acetol, but also for the removal of adsorbed atomic oxygen originating from water dissociation to create empty sites for dissociative glycerol adsorption. Thus, the active Cu sites are assumed to be fully adsorbate-covered under reaction conditions.

Platinum on carbonaceous supports for glycerol hydrogenolysis: Support effect

Oberhauser, Werner,Evangelisti, Claudio,Jumde, Ravindra P.,Psaro, Rinaldo,Vizza, Francesco,Bevilacqua, Manuela,Filippi, Jonathan,Machado, Bruno F.,Serp, Philippe

, p. 111 - 117 (2015)

Metal vapor synthesis (MVS) technique was applied to generate Pt-nanoparticles of different size (1.3 nm and 2.5 nm) deposited onto carbonaceous supports, mainly characterized by a different surface area. The supported catalysts were employed in the glycerol hydrogenolysis reaction carried out under basic reaction conditions at 433 and 453 K to obtain 1,2-propanediol as the main liquid product. Comparison of the composition of the liquid- and gas-phase products obtained by the different catalysts showed a clear dependence of aqueous-phase reforming, water-gas shift reaction activity as well as 1,2-propanediol chemoselectivity on the degree of Pt-sintering occurring on different carbon supports. High-resolution transmission electron microscopic and X-ray powder diffraction studies carried out on as-synthesized and recovered heterogeneous catalysts provided clear evidences that a high surface area carbon support, such as Ketjen Black EC-600JD, notably retards nanoparticle aggregation.

-

Barrett, J.,Baxendale, J. H.

, p. 37 - 43 (1960)

-

-

Carnahan et al.

, p. 3766 (1955)

-

Size effects of Pt-Re bimetallic catalysts for glycerol hydrogenolysis

Deng, Chenghao,Duan, Xuezhi,Zhou, Jinghong,Chen, De,Zhou, Xinggui,Yuan, Weikang

, p. 208 - 214 (2014)

A series of Pt-Re/CNTs catalysts with different particle sizes have been synthesized and applied in glycerol hydrogenolysis to elucidate the size effects. The trend of turnover frequency (TOF) for these different sized Pt-Re/CNTs catalysts follows a volcanic curve, in which the TOF for Pt-Re/CNTs catalyst with particle size of 1.9 nm is ca. 7.5 times higher than that of 4.9 nm. X-ray photoelectron spectroscopy analysis revealed that the surface Pt/Re ratio decreased with the decrease of particle size. The enrichment of surface rhenium species on smaller particles probably led to the increase in the surface acidity, which could be one reason for the enhanced activity over smaller sized Pt-Re/CNTs catalysts. However, too small sized Pt-Re/CNTs catalyst (e.g., 1.5 nm) suffered from severe coking, resulting in the lower activity. Moreover, the hydrogenolysis of different substrates (glycerol, 1,2-propanediol and 1,3-propanediol) over different sized Pt-Re/CNTs catalysts was also investigated. It was revealed that the reactivity declined in the following order: glycerol > 1,3-propanediol > 1,2-propanediol, and the cleavage of secondary C-O bond was favored over larger sized Pt-Re/CNTs catalyst. Based on these results, a possible reaction pathway depending on Pt-Re particle size was proposed.

Effect of surface hydroxyl group of ultra-small silica on the chemical states of copper catalyst for dimethyl oxalate hydrogenation

Wang, Yue,Yang, Wenlong,Yao, Dawei,Wang, Shengping,Xu, Yan,Zhao, Yujun,Ma, Xinbin

, p. 127 - 135 (2020)

Cu/SiO2 catalyst prepared by ammonia evaporation method was reported to perform a great catalytic activity and selectivity in dimethyl oxalate (DMO) hydrogenation, which is one of the key steps in ethylene glycol (EG) synthesis from syngas. In recent years, significant advances have achieved on the nature of active sites and catalytic mechanism. However, the fabrication of Cu/SiO2 catalyst with controllable copper species remains challenging. Here, we reported a facile and effective approach to manipulate the surface hydroxyls of silica, which was revealed to be important factor for the formation of active species. An excellent linear correlation between surface hydroxyl groups of silica and the amount of Cu+ species was demonstrated, indicating that the formation of copper phyllosilicate can be kinetically favoured with increasing surface hydroxyls during preparation. Furthermore, as the copper phyllosilicate formation is enhanced, the specific surface area is significantly increased and the polymerization of copper hydroxide may be slow down, resulting in a highly improved dispersion of metallic copper as well. The enlarged surface areas of Cu0 and Cu+ species greatly enhanced the catalytic performance of Cu/SiO2 in DMO hydrogenation to EG. These understandings on the relationship between surface hydroxyl groups and chemical states of copper catalyst may lead to new possibilities in rational design of catalysts.

Effect of Zn doping on the hydrogenolysis of glycerol over ZnNiAl catalyst

Li, Xiaoru,Zhang, Chao,Cheng, Haiyang,He, Limin,Lin, Weiwei,Yu, Yancun,Zhao, Fengyu

, p. 1 - 6 (2014)

Nickel based catalyst is of interest in the industrial catalytic processes, and it is always modified by doping a second element to improve its catalytic properties. Understanding the role of dopant is extremely helpful in tailoring the active centers. In this work, Zn could induce a significant improvement of the catalytic performance of NiAl for the hydrogenolysis of glycerol. The Zn doped ZnNiAl catalysts exhibited high activity and the improved selectivity to 1,2-propanediol, it was about 2 times higher than the original ones. The ZnNi alloy formed in ZnNiAl was responsible for the noticeable catalytic performance. They preferred to coordinate with the end hydroxyl group of glycerol, promoted the cleavage of CO bond in glycerol, and resulted in the dominant formation of 1,2-propanediol. The findings described here will provide a useful knowledge for rational design of nickel-based catalysts, as well as reveal a new reaction model for the hydrogenolysis of glycerol.

-

Milas,Sussman

, (1937)

-

Structured Pd-Au/Cu-fiber catalyst for gas-phase hydrogenolysis of dimethyl oxalate to ethylene glycol

Zhang, Li,Han, Lupeng,Zhao, Guofeng,Chai, Ruijuan,Zhang, Qiaofei,Liu, Ye,Lu, Yong

, p. 10547 - 10550 (2015)

Galvanic co-deposition of 0.5 wt% Au and 0.1 wt% Pd on a microfibrous-structure using 8 μm Cu-fibers delivers a Pd-Au/Cu-fiber catalyst, which is highly active, selective and stable for the hydrogenolysis of dimethyl oxalate to ethylene glycol. Au and Pd synergistically promote the hydrogenolysis activity of Cu+ sites, while Au also critically stabilizes Cu+ sites to prevent deep reductive deactivation.

Efficient hydrogenation of dimethyl oxalate to ethylene glycol: Via nickel stabilized copper catalysts

Zhu, Junhua,Ye, Yingchun,Tang, Yi,Chen, Liangfeng,Tang, Kangjian

, p. 111415 - 111420 (2016)

CuNi/SiO2 nanocatalysts with Ni-stabilized Cu nanoparticles of around 10 nm were synthesized. After H2 reduction, the catalysts with grain size of around 25 nm showed very high performance in the catalytic hydrogenation of dimethyl oxalate to ethylene glycol under mild reaction conditions. The composition and structure of these nanocatalysts were characterized. This study showed that Ni played a key role in stabilizing Cu against deactivation. To meet the requirements of industrial application, the optimal CuNi/SiO2 nanocatalyst was tested under continuous reaction for over 2000 hours. The conversion and product selectivity were maintained at 99% and above 95%, respectively.

Promoting effect of Ru on Ir-ReOx/SiO2 catalyst in hydrogenolysis of glycerol

Tamura, Masazumi,Amada, Yasushi,Liu, Sibao,Yuan, Zhenle,Nakagawa, Yoshinao,Tomishige, Keiichi

, p. 177 - 187 (2014)

Ru-added Ir-ReOx/SiO2 catalysts worked as efficient catalysts for the selective hydrogenolysis of glycerol to 1,3-propanediol and 1-propanol. 0.9 wt% Ru-added Ir-ReOx/SiO2 catalyst demonstrated high activity for

Influence of Ni species on the structural evolution of Cu/SiO2 catalyst for the chemoselective hydrogenation of dimethyl oxalate

Yin, Anyuan,Wen, Chao,Guo, Xiaoyang,Dai, Wei-Lin,Fan, Kangnian

, p. 77 - 88 (2011)

A novel family of heterogeneous Cu-Ni/SiO2 catalysts with appropriate metal ratios displayed outstanding selectivity to methyl glycolate (96%) and to ethylene glycol (98%) in the chemoselective gas-phase hydrogenation of dimethyloxalate. The chemical states of nickel species were found to have a strong influence on the structural evolution of the catalysts and correspondent catalytic behaviors. The selectivity to the two products could be tuned by modulating the chemical states of nickel species. It is shown that oxidative nickel species are helpful in improving the dispersion of copper species because of the enrichment of copper on the surface of the nickel species, thus enhancing the catalytic activity and selectivity to ethylene glycol. The selectivity to methyl glycolate could be greatly improved by the Cu-Ni bimetallic catalyst. An 83% yield of methyl glycolate and a 98% yield of ethylene glycol could be obtained over the bimetallic Cu-Ni catalyst and the NiO-modified catalyst, respectively.

Investigation of Activated-Carbon-Supported Copper Catalysts with Unique Catalytic Performance in the Hydrogenation of Dimethyl Oxalate to Methyl Glycolate

Cui, Yuanyuan,Wang, Bin,Wen, Chao,Chen, Xi,Dai, Wei-Lin

, p. 527 - 531 (2016)

Copper-based activated-carbon (AC)-supported catalysts were synthesized by a facile ammonia evaporation-impregnation method. Unlike the conventional Cu/SiO2 catalyst, which showed highly catalytic selectivity towards ethylene glycol (EG) or EtOH, Cu/AC catalysts display unique selectivity to methyl glycolate (MG). The catalytic performance relies on the high content of surface Cu+ species and the relatively large copper particles with moderate hydrogenation activity.

Utilizing in situ spectroscopic tools to monitor ketal deprotection processes

Ralbovsky, Nicole M.,Lomont, Justin P.,Ruccolo, Serge,Konietzko, Janelle,McHugh, Patrick M.,Wang, Sheng-Ching,Mangion, Ian,Smith, Joseph P.

, (2021/12/08)

The use of protection groups to shield a functional group during a synthesis is employed throughout many reactions and organic syntheses. The role of a protection group can be vital to the success of a reaction, as well as increase reaction yield and selectivity. Although much work has been done to investigate the addition of a protection group, the removal of the protection group is just as important – however, there is a lack of methods employed within the literature for monitoring the removal of a protection group in real time. In this work, the process of removing, or deprotecting, a ketal protecting group is investigated. Process analytical technology tools are incorporated for in situ analysis of the deprotection reaction of a small molecule model compound. Specifically, Raman spectroscopy and Fourier transform infrared spectroscopy show that characteristic bands can be used to track the decrease of the reactant and the increase of the expected products over time. To the best of our knowledge, this is the first report of process analytical technology being used to monitor a ketal deprotection reaction in real time. This information can be capitalized on in the future for understanding and optimizing pharmaceutically-relevant deprotection processes and downstream reactions.

Stable ethanol synthesis via dimethyl oxalate hydrogenation over the bifunctional rhenium-copper nanostructures: Influence of support

Chen, Xingkun,Ding, Yunjie,Du, Zhongnan,Li, Zheng,Lin, Ronghe,Wang, Shiyi,Wang, Xuepeng,Zhu, Hejun

, p. 241 - 252 (2022/02/22)

Addition of oxophilc rhenium to decorate small copper nanoparticles has been validated to be an efficient method to prepare a low-copper catalyst for the direct synthesis of ethanol via dimethyl oxalate (DMO) hydrogenation process, and herein we investigated the impact of supports on the catalytic performance of ReCu catalysts. A series of materials including activated carbon (AC), Al2O3, SiO2, TiO2 and ZrO2 were utilized as the support and as prepared Re2Cu5 catalysts were evaluated. The results exhibited that the Re2Cu5/ZrO2 catalyst possesses the highest DMO hydrogenation activity and ethanol yield (~93%), which may be due to its lowest Cu0/Cu+ ratio (0.13), smallest Cu particle size (~0.84 nm) a relative high reduction degree (59%). The CO adsorption behavior characterized by in situ IR spectroscopy showed that a strong metal-support interaction creates an electron deficient environment of Cu nanoparticle, resulting in a lower Cu0/Cu+ ratio that enhances the activation of C[dbnd]O bond in the DMO molecular.

Selectively chemo-catalytic hydrogenolysis of cellulose to EG and EtOH over porous SiO2 supported tungsten catalysts

Fan, Maohong,Mu, Shifang,Sun, Qi,Wang, Haiyong,Wang, Xiaolong,Wang, Yan,Weng, Yujing,Zhang, Mingwei,Zhang, Yulong

, (2022/03/15)

Cellulosic ethanol produced from lignocellulose biomass can alleviate the shortage of conventional fossil energy supply and reduce global CO2 emissions. Wherein, hydrogenolysis of cellulose to ethanol is a new method for the synthesis of fuel ethanol, which could theoretically utilizes all carbon atoms in glucose in the direct retro-aldol condensation (RAC) reaction to produce ethanol, and can potentially break through the technical bottleneck of biological methods. Herein, we show that the benefits of the mesoporous structure of tungsten-based catalysts can be leveraged to influence the selective hydrogenolysis of cellulose into C2 products. Comparing the performance of different pore size SiO2 supported tungsten catalysts and detailed characterizations revealed that the mesoporous structure of supports can affect the morphology, crystal sizes, and surface chemistry of the catalysts, which presented a combined effect on the hydrogenolysis reaction. Whereby, 51.5 wt% ethylene glycol (EG) was obtained from the direct hydrogenolysis of cellulose over Ru-WOx/SiO2 (500 ?) catalyst under 513 K, and 40.5 wt% ethanol (EtOH) was obtained from the direct hydrogenolysis of cellulose over Ir-WOx/SiO2 (500 ?) catalyst under 553 K, respectively.

Ce promoted Cu/γ-Al2O3 catalysts for the enhanced selectivity of 1,2-propanediol from catalytic hydrogenolysis of glucose

Balachandran Kirali, Arun Arunima,Marimuthu, Banu,Sreekantan, Sreejith

, (2022/03/31)

Ce promoted Cu/γ-Al2O3 catalysts were prepared with varying amounts of Cu (x = 0–10 wt%) and Ce (y = 0–15 wt%). The prepared catalysts were characterized and tested for the conversion of aqueous glucose (5 wt%) to 1,2-propanediol in a batch reactor. 10%Ce-8%Cu/γ-Al2O3 showed the complete conversion of glucose with 62.7% selectivity of 1,2-propanediol and total glycols (1,2-propanediol, ethylene glycol & 1,2-butanediol) of 81% at milder reaction conditions. Cu facilitated the hydrogenation activity and Ce loading optimize the acid/base sites of Cu/γ-Al2O3 which obtain high selectivity of 1, 2-propanediol. Catalyst reusability is reported.

Product Control and Insight into Conversion of C6 Aldose Toward C2, C4 and C6 Alditols in One-Pot Retro-Aldol Condensation and Hydrogenation Processes

Gao, Lou,Hou, Wenrong,Hui, Yingshuang,Tang, Yi,Zhan, Yulu,Zhang, Yahong

, p. 560 - 566 (2021/06/25)

Alcohols have a wide range of applicability, and their functions vary with the carbon numbers. C6 and C4 alditols are alternative of sweetener, as well as significant pharmaceutical and chemical intermediates, which are mainly obtained through the fermentation of microorganism currently. Similarly, as a bulk chemical, C2 alditol plays a decisive role in chemical synthesis. However, among them, few works have been focused on the chemical production of C4 alditol yet due to its difficult accumulation. In this paper, under a static and semi-flowing procedure, we have achieved the product control during the conversion of C6 aldose toward C6 alditol, C4 alditol and C2 alditol, respectively. About C4 alditol yield of 20 % and C4 plus C6 alditols yield of 60 % are acquired in the one-pot conversion via a cascade retro-aldol condensation and hydrogenation process. Furthermore, in the semi-flowing condition, the yield of ethylene glycol is up to 73 % thanks to its low instantaneous concentration.

Process route upstream and downstream products

Process route

water
7732-18-5

water

ethylene dibromide
106-93-4

ethylene dibromide

hydrogen bromide
10035-10-6,12258-64-9

hydrogen bromide

ethylene glycol
107-21-1

ethylene glycol

Conditions
Conditions Yield
water
7732-18-5

water

ethylene dibromide
106-93-4

ethylene dibromide

hydrogen bromide
10035-10-6,12258-64-9

hydrogen bromide

ethylene glycol
107-21-1

ethylene glycol

Conditions
Conditions Yield
water
7732-18-5

water

ethylene dibromide
106-93-4

ethylene dibromide

hydrogen bromide
10035-10-6,12258-64-9

hydrogen bromide

ethylene glycol
107-21-1

ethylene glycol

Conditions
Conditions Yield
sulfuric acid bis-(2-bromo-ethyl ester)

sulfuric acid bis-(2-bromo-ethyl ester)

water
7732-18-5

water

sulfuric acid
7664-93-9

sulfuric acid

hydrogen bromide
10035-10-6,12258-64-9

hydrogen bromide

ethylene glycol
107-21-1

ethylene glycol

Conditions
Conditions Yield
triglycol borate
35438-71-2

triglycol borate

water
7732-18-5

water

metaboric acid
13460-50-9

metaboric acid

ethylene glycol
107-21-1

ethylene glycol

Conditions
Conditions Yield
poly(ethylene terephthalate)

poly(ethylene terephthalate)

disodium terephthalate
10028-70-3

disodium terephthalate

ethylene glycol
107-21-1

ethylene glycol

Conditions
Conditions Yield
With sodium hydroxide; at 100 - 150 ℃; under 760.051 - 2250.23 Torr;
48%
polyethylene terephthalate

polyethylene terephthalate

terephthalic acid
100-21-0

terephthalic acid

ethylene glycol
107-21-1

ethylene glycol

Conditions
Conditions Yield
polyethylene terephthalate; With sodium hydroxide; In propan-1-ol; at 89 ℃; for 0.25h;
With hydrogenchloride; In propan-1-ol; water; Product distribution / selectivity;
96%
polyethylene terephthalate

polyethylene terephthalate

disodium terephthalate
10028-70-3

disodium terephthalate

ethylene glycol
107-21-1

ethylene glycol

Conditions
Conditions Yield
With sodium hydroxide; In octanol; at 183 ℃; for 0.0833333h; Product distribution / selectivity;
98%
With sodium hydroxide; In hexan-1-ol; at 147 ℃; for 0.25h; Product distribution / selectivity;
propylene glycol
57-55-6,63625-56-9

propylene glycol

ethanol
64-17-5

ethanol

carbon dioxide
124-38-9,18923-20-1

carbon dioxide

hydrogen
1333-74-0

hydrogen

ethylene glycol
107-21-1

ethylene glycol

hydroxy-2-propanone
116-09-6

hydroxy-2-propanone

Conditions
Conditions Yield
With prereduced 3 wtpercent Pt modified Ir supported on silica; In water; at 189.84 ℃; for 4h; under 15001.5 Torr; Inert atmosphere;
Conditions
Conditions Yield
With Pt-Mn/C; In water; at 225 ℃; under 22502.3 Torr; Catalytic behavior;

Global suppliers and manufacturers

Global( 584) Suppliers
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  • Hangzhou Keyingchem Co.,Ltd
  • Business Type:Lab/Research institutions
  • Contact Tel:+86-571-85378921
  • Emails:sales@keyingchem.com
  • Main Products:105
  • Country:China (Mainland)
  • Chemwill Asia Co., Ltd.
  • Business Type:Manufacturers
  • Contact Tel:021-51086038
  • Emails:sales@chemwill.com
  • Main Products:30
  • Country:China (Mainland)
  • Hangzhou Dingyan Chem Co., Ltd
  • Business Type:Manufacturers
  • Contact Tel:86-571-86465881,86-571-87157530,86-571-88025800
  • Emails:sales@dingyanchem.com
  • Main Products:95
  • Country:China (Mainland)
  • Amadis Chemical Co., Ltd.
  • Business Type:Lab/Research institutions
  • Contact Tel:86-571-89925085
  • Emails:sales@amadischem.com
  • Main Products:29
  • Country:China (Mainland)
  • COLORCOM LTD.
  • Business Type:Manufacturers
  • Contact Tel:+86-571-89007001
  • Emails:medkem@medkem.cn
  • Main Products:1
  • Country:China (Mainland)
  • Win-Win chemical Co.Ltd
  • Business Type:Lab/Research institutions
  • Contact Tel:0086-577-64498589
  • Emails:sales@win-winchemical.com
  • Main Products:55
  • Country:China (Mainland)
  • Shaanxi BLOOM TECH Co.,Ltd
  • Business Type:Lab/Research institutions
  • Contact Tel:+86-29-86470566
  • Emails:sales@bloomtechz.com
  • Main Products:80
  • Country:China (Mainland)
  • AmoyChem Co.,Ltd
  • Business Type:Other
  • Contact Tel:+86 592 605 1114
  • Emails:sales@amoychem.com
  • Main Products:45
  • Country:China (Mainland)
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