106989-11-1Relevant articles and documents
Degradation of tri(2-chloroisopropyl) phosphate by the UV/H2O2 system: Kinetics, mechanisms and toxicity evaluation
He, Huan,Ji, Qiuyi,Gao, Zhanqi,Yang, Shaogui,Sun, Cheng,Li, Shiyin,Zhang, Limin
, (2019)
A photodegradation technology based on the combination of ultraviolet radiation with H2O2 (UV/H2O2) for degrading tri(chloroisopropyl) phosphate (TCPP) was developed. In ultrapure water, a pseudo-first order reaction was observed, and the degradation rate constant reached 0.0035 min?1 (R2 = 0.9871) for 5 mg L?1 TCPP using 250 W UV light irradiation with 50 mg L?1 H2O2. In detail, the yield rates of Cl? and PO43? reached 0.19 mg L?1 and 0.58 mg L?1, respectively. The total organic carbon (TOC) removal rate was 43.02%. The pH value of the TCPP solution after the reaction was 3.46. The mass spectrometric detection data showed a partial transformation of TCPP into a series of hydroxylated and dechlorinated products. Based on the luminescent bacteria experimental data, the toxicity of TCPP products increased obviously as the reaction proceeded. In conclusion, degradation of high concentration TCPP in UV/H2O2 systems may result in more toxic substances, but its potential application for real wastewater is promising in the future after appropriate optimization, domestication and evaluation.
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Mossler
, p. 573 (1908)
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Slade et al.
, p. 135,139 (1942)
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Lactic acid production from aqueous-phase selective oxidation of hydroxyacetone
Albuquerque, Elise M.,Borges, Luiz E.P.,Fraga, Marco A.
, p. 64 - 70 (2015)
Lactic acid is an important chemical with a wide range of application in food, pharmaceutical and chemical industries. Its worldwide demand has increased due to the ever-growing market of poly(lactic acid) - PLA. This present contribution aims at studying the catalytic transformation of hydroxyacetone toward lactic acid over heterogeneous systems. Commercial Pt/Al2O3 powder catalysts were used and their main features were analyzed as concerning their chemical composition (XRF), crystalline structure (XRD), morphology (TEM) and porosity (N2 physisorption). Catalytic performance was evaluated in aqueous phase and the results showed that the catalytic activity and selectivity to lactic acid depends on the pH of the reaction medium, being mandatory to operate under strong alkaline conditions. Such reaction conditions promote both the initial oxidation of hydroxyacetone and the intramolecular disproportionation of the obtained aldehyde, which are fundamental steps to lactic acid formation. More importantly, this contribution reports the feasibility of alternatively using heterogeneous catalysts to produce lactic acid with high selectivity (>96%).q
SIMULTANEOUSLY OCCURRING HYDROXYLATION, HYDRATION, AND HYDROGENATION OF THE C=C BOND OF ALIPHATIC CARBOXYLIC ACIDS IN AQUEOUS SOLUTION BY GLOW DISCHARGE ELECTROLYSIS
Kokufuta, Etsuo,Shibasaki, Takami,Sodeyama, Touro,Harada, Kaoru
, p. 1569 - 1572 (1985)
Glow discharge electrolysis of maleic and acrylic acids in carbonate-free distilled water simultaneously afford the products into which OH and/or H groups are introduced, indicating the addition reactions of OH and H radicals to the C=C bond.
Preparation of Sn-Β-zeolite via immobilization of Sn/choline chloride complex for glucose-fructose isomerization reaction
Bayu, Asep,Karnjanakom, Surachai,Kusakabe, Katsuki,Abudula, Abuliti,Guan, Guoqing
, p. 426 - 433 (2017)
Well dispersion of tin species in an isolated form is a quite challenge since tin salts are easily hydrolyzed into (hydr)oxides during aqueous stannation of β-zeolite. In this study, immobilization of tin species on high silica commercial β-zeolite by using SnCl2/Choline chloride (ChCl) complex followed with calcination provided a convenient way to get well dispersed Sn in β-zeolite in the aqueous condition, which was observed based on electron microscopy images, UV visible spectra and X-ray diffraction pattern. The existence of ChCl facilitated tin species to incorporate into zeolite. (1?2) wt% of Sn loaded β-zeolites exhibited good catalytic activity and high selectivity for glucose-fructose isomerization reaction.
Highly active and recyclable Sn-MWW zeolite catalyst for sugar conversion to methyl lactate and lactic acid
Guo, Qiang,Fan, Fengtao,Pidko, Evgeny A.,Van Der Graaff, William N. P.,Feng, Zhaochi,Li, Can,Hensen, Emiel J. M.
, p. 1352 - 1356 (2013)
Not just sugar! Lewis-acidic Sn-MWW zeolites are obtained through postsynthesis functionalization of deboronated B-MWW with Sn. These materials are highly active, selective, and recyclable catalysts for the conversion of triose sugars to methyl lactate (in methanol) and lactic acid (in water). They also demonstrate good performance in the conversion of hexose sugars and sucrose to methyl lactate. Copyright
Production of carboxylic acids from glucose with metal oxides under hydrothermal conditions
Adam, Yousif S.,Fang, Yan,Huo, Zhibao,Zeng, Xu,Jing, Zhenzi,Jin, Fangming
, p. 3201 - 3211 (2015)
Abstract Production of low molecular weight carboxylic acids from glucose with the addition of metal oxides under hydrothermal conditions was investigated. The results showed that CuO, as an oxidant can significantly promote the production of lactic acid, and can also promote the production of acetic acid and formic acid. Fe3O4 can also enhance lactic acid production as a catalyst. The highest yields of 37.1, 9.4, and 4.9 % for lactic acid, acetic acid, and formic acid were achieved, respectively, which occurred at 300°C for 60 s with CuO 1.5 mmol, NaOH 2.5 M, and water filling 35 %.
Evaluation of a monolith-supported Pt/Al2O3 catalyst for wet oxidation of carbohydrate-containing waste streams
Patrick,Abraham
, p. 3480 - 3488 (2000)
Catalytic oxidation of glucose and cellulose has been demonstrated in a monolith reactor, a novel contacting device for the oxidation of carbohydrate feedstocks that allows the processing of nonsoluble components without reactor plugging. Catalytic enhancement is observed for glucose oxidation, and the catalyst promotes selectivity to two-carbon carboxylic acids. It is proposed that catalytic oxidation of glucose occurs through parallel pathways: thermal oxidation to a wide range of organic acids and selective catalytic oxidation to low molecular weight acids. On the other hand, cellulose oxidation was not always enhanced by the presence of the catalyst. Here, the effect of the catalyst was to enhance the conversion of the organic acids produced during thermal oxidation. However, these organic acids also catalyzed the primary conversion of cellulose, thus the conversion of cellulose decreased as the reaction temperature was increased. A kinetic model is provided that is consistent with the inverse temperature effect observed for the cellulose oxidation experiments. Catalytic oxidation of glucose and cellulose has been demonstrated in a monolith reactor, a novel contacting device for the oxidation of carbohydrate feedstocks that allows the processing of nonsoluble components without reactor plugging. Catalytic enhancement is observed for glucose oxidation, and the catalyst promotes selectivity to two-carbon carboxylic acids. It is proposed that catalytic oxidation of glucose occurs through parallel pathways: thermal oxidation to a wide range of organic acids and selective catalytic oxidation to low molecular weight acids. On the other hand, cellulose oxidation was not always enhanced by the presence of the catalyst. Here, the effect of the catalyst was to enhance the conversion of the organic acids produced during thermal oxidation. However, these organic acids also catalyzed the primary conversion of cellulose, thus the conversion of cellulose decreased as the reaction temperature was increased. A kinetic model is provided that is consistent with the inverse temperature effect observed for the cellulose oxidation experiments.
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Sevag,Swart
, p. 409 (1947)
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Silica-supported chromia-titania catalysts for selective formation of lactic acid from a triose in water
Takagaki, Atsushi,Goto, Hiroshi,Kikuchi, Ryuji,Oyama, S. Ted
, p. 200 - 208 (2019)
A variety of silica-supported metal oxide catalysts were prepared by the incipient wetness impregnation method and were used for the conversion of dihydroxyacetone to lactic acid. A titanium oxide catalyst with Br?nsted acid sites was selective to an intermediate, pyruvaldehyde and a chromium oxide catalyst with Lewis acid sites was selective to lactic acid. The co-impregnation of chromium- and titanium oxides with different ratios accelerated the reaction rate and improved the lactic acid yield up to 80% at 130 °C. Pyridine-adsorbed Fourier-transform infrared spectroscopy indicated that the silica-supported mixed oxides had both Br?nsted acid and Lewis acid sites and the trend of the Lewis/Br?nsted ratio was close to that of selectivity to lactic acid. Diffuse reflectance UV–vis spectroscopy showed that the silica-supported chromia-titania catalyst composed of isolated Cr and Ti species in tetrahedral coordination. Kinetic analysis revealed that the two critical rate constants, pyruvaldehyde formation and lactic acid formation, for the chromia-titania catalyst were much higher than those of the titania and chromia catalysts.
Transfer hydrogenation of carbon dioxide and bicarbonate from glycerol under aqueous conditions
Heltzel, Jacob M.,Finn, Matthew,Ainembabazi, Diana,Wang, Kai,Voutchkova-Kostal, Adelina M.
, p. 6184 - 6187 (2018)
The transfer hydrogenation of CO2 from glycerol to afford formic and lactic acid is a highly attractive path to valorizing two waste streams and is a significantly more thermodynamically favorable process than direct CO2 hydrogenatio
Selective hydrogenolysis of sorbitol to ethylene glycol and propylene glycol on ZrO2-supported bimetallic Pd-Cu catalysts
Jia, Yuqing,Liu, Haichao
, p. 1552 - 1559 (2015)
Sorbitol is one of the key building blocks in catalytic conversion of biomass, and its selective hydrogenolysis to ethylene glycol and propylene glycol provides a viable and sustainable route towards the synthesis of the two glycols. Herein, the hydrogenolysis of biomass-derived sorbitol was studied on Pd-modified Cu/monoclinic zirconia (Pd-Cu/ZrO2) catalysts with a wide range of Cu/Pd atomic ratios in the presence of La(OH)3. The bimetallic Pd-Cu/ZrO2 catalysts showed superior activities and selectivities to the two target glycols, compared with the monometallic Cu/ZrO2 and Pd/ZrO2 catalysts under identical conditions. At nearly 100% sorbitol conversion, a combined selectivity of 61.7% to ethylene glycol, propylene glycol, and glycerol was obtained on Pd-Cu/ZrO2 (Cu/Pd=5) at 493 K under 5.0 MPa H2. Pd-Cu/ZrO2 was also stable and recyclable, in contrast to Cu/ZrO2, which suffered severe deactivation because of agglomeration of Cu particles during sorbitol hydrogenolysis. Clearly, the presence of Pd improved not only the activity and selectivity of the Cu catalyst, but also the hydrothermal stability. Characterization of these catalysts by X-ray diffraction, diffuse-reflectance infrared Fourier transform spectroscopy of CO adsorption, and H2 temperature-programmed reduction suggests that the Cu particles deposited on the Pd surfaces with close contact and strong interaction between the two metals, most likely involving electron transfer from Pd to Cu. Such structural and electronic effects are proposed as the critical contributors to the significant promoting effect of Pd on the activity and stability of Pd-Cu catalysts in sorbitol hydrogenolysis. These findings provide useful information for design of new Cu-based catalysts with higher efficiency and stability for selective hydrogenolysis of polyols and other biomass-derived reactants under hydrothermal conditions.
Natural products chemistry and taxonomy of the marine cyanobacterium Blennothrix cantharidosmum
Clark, Benjamin R.,Engene, Niclas,Teasdale, Margaret E.,Rowley, David C.,Matainaho, Teatulohi,Valeriote, Frederick A.,Gerwick, William H.
, p. 1530 - 1537 (2008)
A Papua New Guinea field collection of the marine cyanobacterium Blennothrix cantharidosmum was investigated for its cytotoxic constituents. Bioassay-guided isolation defined the cytotoxic components as the known compounds lyngbyastatins 1 and 3. However, six new acyl proline derivatives, tumonoic acids D-I, plus the known tumonoic acid A were also isolated. Their planar structures were defined from NMR and MS data, while their stereostructures followed from a series of chiral chromatographies, degradation sequences, and synthetic approaches. The new compounds were tested in an array of assays, but showed only modest antimalarial and inhibition of quorum sensing activities. Nevertheless, these are the first natural products to be reported from this genus, and this inspired a detailed morphologic and 16S rDNA-based phylogenetic analysis of the producing organism.
A mechanism study on the efficient conversion of cellulose to acetol over Sn-Co catalysts with low Sn content
Liu, Xiaodong,Liu, Xiaohao,Ma, Longlong,Wang, Haiyong,Xiao, Tianci,Zhang, Ying
, p. 6579 - 6587 (2020)
Efficient conversion of renewable cellulose to high value-added C3 chemicals is a great challenge in the field of biomass valorization. In this work, we found that the combination of Co and Sn could significantly improve the efficiency of cellulose conversion to acetol. 54.4% yield of acetol and 66.6% total yield of C3 products were obtained when using 2%Sn-10%Co/SiO2 (2 wt% Sn content) as a catalyst. However, using the same Sn content of 2%Sn-10%Ni/SiO2, no acetol and only 7.1% yield of C3 products were produced. By studying the effects of different Sn and Co concentrations on cellulose conversion, it was found that the Sn species play an important role in catalyzing glucose conversion to C3 intermediates, while Co mainly played a role in hydrogenation, the same as Ni. The study demonstrated that Sn-Co/SiO2 with low Sn content can convert glucose to C3 intermediates more efficiently than the Sn-Ni/SiO2 catalyst. Moreover, Sn-Co/SiO2 could effectively convert C3 intermediates to acetol at a high temperature which is essential for acetol production from cellulose; but under the same conditions, the Sn-Ni/SiO2 catalyst tended to catalyze the polymerization of C3 intermediates. A series of characterization methods including AAS, TEM, HRTEM, EDS, XRD, ex situ XPS, in situ XPS, and CO2-TPD found that the combination of Sn and Co could significantly increase the noninteger valent SnOx species in the catalyst. These species increased the basicity of the catalyst and were beneficial in catalyzing the isomerization of glucose and the retro-aldol condensation of fructose. This journal is
AN INVESTIGATION OF THE TRANSFORMATIONS OF 2-AMINO-2-THIAZOLIN-4-ONE AND ITS DERIVATIVES IN AQUEOUS SOLUTIONS
Fedoseev, V. M.,Mandrugin, A. A.,Semenenko, M. N.
, p. 36 - 39 (1984)
It has been shown by thin-layer radiochromatography that the action of an aqueous solution of alkali on 2-amino-2-thiazolin-4-one and its 5-alkyl derivatives leads predominantly to the opening of the ring by a mechanism similar to the opening of lactams in an alkaline medium.
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Phelps,Johnson,Peterson
, p. 1606 (1939)
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Selective oxidation of 1,2-propanediol to lactic acid catalyzed by nanosized Mg(OH)2-supported bimetallic Au-Pd catalysts
Feng, Yonghai,Yin, Hengbo,Wang, Aili,Gao, Dezhi,Zhu, Xiaoyan,Shen, Lingqin,Meng, Minjia
, p. 49 - 60 (2014)
1,2-Propanediol co-produced in the dimethyl carbonate production is oversupplied in market. 1,2-Propanediol can also be facilely produced starting from glycerol, which is oversupplied in the biodiesel production. Catalytic conversion of low-valued 1,2-propanediol to high-valued and environmental benign lactic acid was investigated under mild reaction conditions over Au-Pd/Mg(OH)2 catalysts in our present work. The Au-Pd/Mg(OH) 2 catalysts were prepared by the sol-immobilization method and characterized by XRD, SEM, HRTEM, UV-vis DRS, and O2-TPD techniques. Small-sized Au and Pd nanoparticles were coalesced together to form secondary nanoparticles, which were well dispersed on the surfaces of Mg(OH)2 nanoslices. The Au and Pd nanoparticles synergistically catalyzed the oxidation of 1,2-propanediol with O2 to lactic acid in an alkaline solution. When the catalytic oxidation of 1,2-propanediol was carried out over Au 0.75Pd0.25/Mg(OH)2 catalyst at 60 °C for 240 min, the lactic acid selectivity of 88% was obtained at the 1,2-propanediol conversion of 97.5%. A power-function type reaction kinetic model well fitted the experimental data, r=-dCP/dt=kCP0.8PO21.4Wcat1.0. The reaction activation energy was 64 kJ mol-1.
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Krebs
, p. 662 (1937)
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Relationship between Acid–Base Properties and the Activity of ZrO2-Based Catalysts for the Cannizzaro Reaction of Pyruvaldehyde to Lactic Acid
Albuquerque, Elise M.,Borges, Luiz E. P.,Fraga, Marco A.,Sievers, Carsten
, p. 2675 - 2683 (2017)
The Cannizzaro reaction of pyruvaldehyde to lactic acid is investigated in a flow reactor with ZrO2 catalysts with different structures and acid–base properties. The results show that a difference in the crystalline structures of two ZrO2 polymorphs strongly affects the conversion of pyruvaldehyde. The monoclinic phase of zirconia is the most active for this reaction. A good correlation is observed between the reaction rate and the concentration of Lewis acid sites of sufficient strength, which shows that these sites play a major role in the reaction. A reaction mechanism is proposed involving coordinatively unsaturated Zr4+ cations as sites for activating pyruvaldehyde molecules, whereas Zr4+?O2? pairs generate terminal OH groups through water dissociation.
Catalytic Oxidation of 1,2-Propanediol over Bimetallic Cu@Au Core/Shell Nanoparticles
Xue, Wuping,Yin, Hengbo,Lu, Zhipeng,Feng, Yonghai,Wang, Aili,Liu, Shuxin,Shen, Lingqin,Jia, Xingyuan
, p. 1139 - 1152 (2016)
Abstract: Bimetallic Cu@Au core/shell nanoparticles were prepared by the wet chemical reduction method using Tween as the organic modifier. The Cu@Au nanoparticles exhibited higher catalytic activity for the oxidation of 1,2-propanediol under mild reaction conditions than the sole Au nanoparticles. The Cu@Au nanoparticles with the mole ratios of Au to Cu of 0.015:0.985 and 0.035:0.965 exhibited high catalytic activities for the catalytic oxidation of 1,2-propanediol to lactic acid. A power function type reaction kinetic model well fitted the experimental data over the Cu0.985Au0.015 nanoparticle catalyst, r?=?–dn0/(dt·Wcat)?=?kC0 0.49P0 0.39, and the reaction activation energy was 34.1?kJ?mol?1. Graphical Abstract: [Figure not available: see fulltext.]
Unravelling the mechanism of glycerol hydrogenolysis over rhodium catalyst through combined experimental-theoretical investigations
Auneau, Florian,Michel, Carine,Delbecq, Francoise,Pinel, Catherine,Sautet, Philippe
, p. 14288 - 14299 (2011)
We report herein a detailed and accurate study of the mechanism of rhodium-catalysed conversion of glycerol into 1,2-propanediol and lactic acid. The first step of the reaction is particularly debated, as it can be either dehydration or dehydrogenation. It is expected that these elementary reactions can be influenced by pH variations and by the nature of the gas phase. These parameters were consequently investigated experimentally. On the other hand, there was a lack of knowledge about the behaviour of glycerol at the surface of the metallic catalyst. A theoretical approach on a model Rh(111) surface was thus implemented in the framework of density functional theory (DFT) to describe the above-mentioned elementary reactions and to calculate the corresponding transition states. The combination of experiment and theory shows that the dehydrogenation into glyceraldehyde is the first step for the glycerol transformation on the Rh/C catalyst in basic media under He or H2 atmosphere.
Adler,v.Euler,Hellstroem
, p. 968 (1936)
Electrosynthesis of amino acids from biomass-derivable acids on titanium dioxide
Fukushima, Takashi,Yamauchi, Miho
, p. 14721 - 14724 (2019)
Seven amino acids were electrochemically synthesized from biomass-derivable α-keto acids and NH2OH with faradaic efficiencies (FEs) of 77-99% using an earth-Abundant TiO2 catalyst. Furthermore, we newly constructed a flow-Type electrochemical reactor, named a "polymer electrolyte amino acid electrosynthesis cell", and achieved continuous production of alanine with an FE of 77%.
Microwave-assisted conversion of d-glucose into lactic acid under solvent-free conditions
Epane, Geraldine,Laguerre, Jean Claude,Wadouachi, Anne,Marek, Delphine
, p. 502 - 506 (2010)
The microwave-assisted alkaline degradation of d-glucose with alumina supported potassium hydroxide towards its conversion into lactic acid is reported. An experimental design approach was used to optimize the variables involved in this transformation. The reaction succeeded in yielding 75C-% of lactic acid starting from d-glucose using 1.5 equiv of KOH at 180 °C. The optimal conditions were applied to d-fructose, d-mannose and d-sucrose.
Photothermal strategy for the highly efficient conversion of glucose into lactic acid at low temperatures over a hybrid multifunctional multi-walled carbon nanotube/layered double hydroxide catalyst
Duo, Jia,Jin, Binbin,Jin, Fangming,Shi, Xiaoyu,Wang, Tianfu,Ye, Xin,Zhong, Heng
, p. 813 - 822 (2022/02/09)
The conversion of carbohydrates into lactic acid has attracted increasing attention owing to the broad applications of lactic acid. However, the current methods of thermochemical conversion commonly suffer from limited selectivity or the need for harsh conditions. Herein, a light-driven system of highly selective conversion of glucose into lactic acid at low temperatures was developed. By constructing a hybrid multifunctional multi-walled carbon nanotube/layered double hydroxide composite catalyst (CNT/LDHs), the highest lactic acid yield of 88.6% with 90.0% selectivity was achieved. The performance of CNT/LDHs for lactic acid production from glucose is attributed to the following factors: (i) CNTs generate a strong heating center under irradiation, providing heat for converting glucose into lactic acid; (ii) LDHs catalyze glucose isomerization, in which the photoinduced OVs (Lewis acid) in LDHs under irradiation further improve the catalytic activity; and (iii) in a heterogeneous-homogeneous synergistically catalytic system (LDHs-OH-), OH- ions are concentrated in LDHs, forming strong base sites to catalyze subsequent cascade reactions.
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.
Visible-light-driven prompt and quantitative production of lactic acid from biomass sugars over a N-TiO2photothermal catalyst
Cao, Yingying,Chen, Dandan,Li, Hu,Meng, Ye,Saravanamurugan, Shunmugavel
, p. 10039 - 10049 (2021/12/27)
Chemocatalytic production of lactic acid from biomass feedstock is an alternative route with high potential, but with the prerequisites of long reaction time, high temperature, and/or a tailored catalyst. In this work, an N-TiO2 photothermal catalyst prepared by a simple sol-gel method using urea as a nitrogen and carbon source could catalyse a variety of biomass sugars to quantitatively produce lactic acid (up to 98.9% yield) in water under visible light and at a low temperature of 60 °C in a time as short as 30 min. N-TiO2 provides a suitable valence band position (2.51 eV) for the photo-oxidation reaction, with more active species being formed on the catalyst surface (e.g., h+, e-, OH and O2) and a light-induced heating effect caused by the carbon photothermal layer, which can effectively activate carbohydrates to undergo a cascade reaction process. Theoretical calculations show that the charge of N-TiO2 is highly separated, in which the N element acts as an electron trap and is enriched with plenty of electrons, leading to effective isolation of holes and electrons. In addition, the N-TiO2 catalyst exhibits good reusability and can be recycled with little loss of activity. The developed N and C-enhanced photothermal synergistic protocol opens up an avenue for producing organic acids from renewable biomass resources under mild conditions. This journal is
