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FLUID PHASE EQUILIBRIA · 2024 · IF 2.8

Determination and correlation of liquid-liquid equilibrium data for the extraction of glycerol carbonate from glycerol using 2-pentanone, cyclohexanone, and 4-methyl-2-pentanone

Hui Shi,Jiazuo Wei,Tiantian Xu,Yulei Guan,Jingjun Liu

Glycerol carbonate, a high-value derivative of glycerol, finds extensive applications in the cosmetics, pharmaceuticals, and food industries, as well as in plasticizers and battery electrolytes. This study assessed the feasibility of extracting glycerol carbonate from glycerol using three solvents: 2-pentanone, cyclohexanone, and 4-methyl-2-pentanone. The extraction performance of these solvents was evaluated through liquid-liquid equilibrium (LLE) measurements at atmospheric pressure and temperatures of 303.2 K, 313.2 K, and 323.2 K. Although 4-methyl-2-pentanone exhibited high extraction selectivity, the distribution coefficient of glycerol carbonate in it was less than one. Conversely, while cyclohexanone provided a high distribution coefficient, its extraction selectivity was low. In contrast, 2-pentanone demonstrated a relatively balanced extraction selectivity and capacity. The Non-Random Two-Liquid (NRTL) model was used as an activity model in the equilibrium data correlation, and the corresponding binary interaction parameters were estimated. The regressed parameters of the NRTL model successfully reproduced the phase equilibrium trends observed for all systems investigated, facilitating process design and solvent screening for glycerol carbonate extraction from glycerol.

CAS / MDL: 56-81-5
研究领域: 化学工程 · 材料科学
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Journal of Oleo Science · 2021 · IF 1.601

Effects of Solvents on the Glycerolysis Performance of the SBA-15 Supported Lipases

Wenyi Chen,Maomao Kou,Shaoyan Lin,Nanjing Zhong

In this study, Candida antarctica lipase B (CALB), Rhizomucor miehei lipase (RML) and Lecitase® Ultra (LU) were immobilized onto the mesoporous silica SBA-15. The glycerolysis performance of the obtained supported lipases (lipase@SBA-15) in solvent systems was carefully investigated. LU@SBA-15 exhibited good glycerolysis performance in solvent-free system, with diacylglycerols (DAG) content and triacylglycerols (TAG) conversion at 52.4 and 98.6% respectively obtained after 12 h reaction at 60°C. CALB@SBA-15 showed good glycerolysis activity in tert-pentanol and tert-butanol systems, with TAG conversion over 90% obtained. In addition, the present CALB@SBA-15 exhibited selectivity for monoacylglycerols (MAG) production, with glycerol to TAG molar ratio increased to 3:1, MAG content over 80% and TAG conversion over 99% could be obtained from both tert-pentanol and tert-butanol systems. However, RML@SBA-15 showed low glycerolysis activity neither in solvent nor in solvent-free systems. The present results favor the practical enzymatic design for MAG and DAG production.

研究领域: 生物化学 · 酶工程
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AICHE JOURNAL · 2022 ·Vol. 68 ·期 12 ·e17852 · IF 4.167

A readily available and efficient Pt/P25 (TiO2) catalyst for glycerol selective oxidation

Yang Zhao,Xinyi Zhang,Jiarui Yang,Mingyu Gao,Pengfei Yang,Qian Wang,Dianqing Li,Junting Feng

In this work, a commercial P25 (TiO 2 ) with phase junctions between (101) and (110) faces supported Pt catalyst was prepared for glycerol selective oxidation, giving a decent 76.8% glyceric acid (GLYA) yield, and good stability. The kinetic experiments calculated apparent activation energy, turnover frequency (TOF), and reaction rates, demonstrating Pt/P25 could facilitate glyceraldehyde (GLYAD) formation and inhibit GLYA over-oxidation. Series of structural techniques confirmed the 101/110 junctions in P25 contributed electronic effect on Pt through metal-support interface, which improved the oxygen activation ability and optimized the GLYAD/GLYA adsorption modes. Furthermore, progressive scale-up reactions were tested and the mass transfer limitations under different conditions were thoroughly studied. The obtained mass transfer factors suggested the gas–liquid and liquid–solid mass transfer were severely limited. Finally, through optimizing the conditions, Pt/P25 catalyst achieved 75.8% GLYA yield at 300 ml-scale reaction, realizing equivalent magnification with the 5 ml-scale experiment.

研究领域: 催化化学 · 材料科学 · 反应动力学
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JOURNAL OF THE AMERICAN OIL CHEMISTS SOCIETY · 2020 ·Vol. 97 ·期 6 ·603-614 · IF 1.659

Na2SiO3-Catalyzed Glycerolysis of Sacha Inchi (Plukenetia volubilis L.) Oil into Di- and Monoacylglycerols

Jia Luo,Zeping Wang,Shangzhi Deng,Fan Zhang,Guirong Bao,Junni Mao,Wenjing Yang

Direct glycerolysis of novel edible Sacha Inchi ( Plukenetia volubilis L.) seed oil (PvLO) into diacylglycerols (DAG) and monoacylglycerols (MAG) was studied over solid Na 2 SiO 3 with or without microwave assistance. The glycerolysis yield was calculated by qualitative and semiquantitative analyses of 1 H NMR, 13 C NMR, and FT-IR spectra. The yields of ~33% 1, 3-DAG, ~16% 1, 2-DAG, ~40% 1-MAG, and ~2.3% 2-MAG were achieved after 16 hours at 120 °C in three consecutive cycles using acetone, with an interesterification rate of 92%. The modified oil showed enhanced gelation ability at low temperatures. The yield of 1, 2-DAG can be increased by adding acetone as solvent. The fatty acid compositions and unsaturated structure of lipids were less destroyed after alkaline glycerolysis. However, more α-linolenic and linoleic acids were transferred to the sn -2 position of glyceryl skeleton. The oxidative stability of the modified oil was still controllable. In summary, this work provides a feasible method to convert polyunsaturated plant oils into oils rich in DAG and MAG with less destructive impact on the olefinic structure of oil. Also, it provides a useful example of how to quickly evaluate the influence of chemical modification on the chemical structure of plant oils by using various spectral technologies.

CAS / MDL: 1344-09-8
研究领域: 食品科学 · 化学工程 · 植物油脂加工
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Science Bulletin · 2025 · IF 21.1

Adsorption configuration control on Pt-Bi2O3 for the oriented conversion of glycerol to glyceric acid via terminal hydroxyl oxidation

Han-Yue Yang,Bin Sun,Xue Xiao,Xuan Ai,Rui-Bin Jiang,Pei Chen,Yu Chen

Glycerol, a byproduct of biodiesel production, can be efficiently converted into valuable chemicals through electrocatalytic reaction. In this study, platinum (Pt) nanocrystals decorated on bismuth oxide (Bi 2 O 3 ) nanosheets (PtBi DONS) with an optimal Pt:Bi ratio of 1:1 were successfully synthesized using a galvanic replacement method. Pt 1 Bi 1 DONS exhibit remarkable electrocatalytic performance for glycerol electrooxidation, achieving an excellent catalytic activity (current of 0.82 A mg Pt –1 at 0.67 V vs. reversible hydrogen electrode (RHE)) and an exceptional selectivity of 96.6% for C 3 products, particularly glyceric acid. The superior performance stems from two key factors: (1) electron transfer from Bi 2 O 3 to Pt creates electron-rich Pt sites that suppress C–C bond cleavage and (2) Bi 2 O 3 facilitates favorable glycerol adsorption configurations through multiple hydroxyl group interactions. Mechanistic studies using operando spectroscopy and electrochemical impedance spectroscopy revealed that the synergistic effect between Pt and Bi 2 O 3 promotes rapid charge transfer and stable intermediate formation. Moreover, PtBi DONS showed excellent versatility in oxidizing other polyols compared with monoalcohols.

研究领域: 化学工程 · 材料科学
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MOLECULES · 2023 ·Vol. 28 ·期 5 ·2272 · IF 4.6

Transformation of CO2 with Glycerol to Glycerol Carbonate over ETS-10 Zeolite-Based Catalyst

Zhangxi Gao,Mei Xiang,Mingyang He,Weiyou Zhou,Jiayao Chen,Jiamin Lu,Zeying Wu,Yaqiong Su

Catalytic conversion of CO2with the surplus glycerol (GL) produced from biodiesel manufacturing has attracted much academic and industrial attention, which proves the urgent requirement for developing high-performance catalysts to afford significant environmental benefits. Herein, titanosilicate ETS-10 zeolite-based catalysts with active metal species introduced by impregnation were employed for coupling CO2with GL to efficiently synthesize glycerol carbonate (GC). The catalytic GL conversion at 170 °C miraculously reached 35.0% and a 12.7% yield of GC was obtained on Co/ETS-10 with CH3CN as a dehydrating agent. For comparison, Zn/ETS- Cu/ETS-10, Ni/ETS-10, Zr/ETS-10, Ce/ETS-10, and Fe/ETS-10 were also prepared, which showed inferior coordination between GL conversion and GC selectivity. Comprehensive analysis revealed that the presence of moderate basic sites for CO2adsorption-activation played a crucial role in regulating catalytic activity. Moreover, the appropriate interaction between cobalt species and ETS-10 zeolite was also of great significance for improving the glycerol activation capacity. A plausible mechanism was proposed for the synthesis of GC from GL and CO2in the presence of CH3CN solvent over Co/ETS-10 catalyst. Moreover, the recyclability of Co/ETS-10 was also measured and it proved to be recycled at least eight times with less than 3% decline in GL conversion and GC yield after a simple regeneration process through calcination at 450 °C for 5 h in air.Keywords:CO2;glycerol;glycerol carbonate;ETS-10 zeolite;cobalt-based catalyst

研究领域: 化学工程 · 环境科学
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2019 · IF 2.298

Solubilities and Thermodynamic Properties of NH3 in Glycerin and its Derivatives

Xiuzhi Duan,Yanhong Cui,Chao Zhang,Bao Gao,Dongshun Deng

The solubilities of ammonia (NH3) in glycerin (G) as well as its derivatives were determined at 303.15, 313.15, 323.15, and 333.15 K and pressure scope of 0–570.0 kPa by isochoric saturation method. Three glycerin derivatives include dl-1,2-isopropyli-deneglycerol (GAK), glycerol formal (GF), and 3-methoxy-1,2-propanediol (MP). Henry’s law constants together with thermodynamic property changes of dissolution Gibbs free energy, enthalpy, and entropy during NH3 dissolving were derived by fitting the experimental data. The results showed that the gravimetric solubilities of NH3 in these solvents changes along with the sequence of G > GF > MP > GAK. The increasing pressure or the decreasing temperature led to improvement of the solubility of NH3 in each solvent. The dissolution of NH3 presented as a spontaneous process due to the dissolving enthalpy less than zero at each condition. By comprehensive comparison of dissolving ability, properties, price, and environmental impact between present solvents and other absorbents in the literatures, glycerin was believed as a potential NH3 captures in the industry.

研究领域: 化学工程 · 物理化学
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FOOD CONTROL · 2025 · IF 6.3

Investigating the synergistic effects of acylglycerols on the selective formation of 3-MCPD and glycidyl esters in model soybean oil systems

Yaoyao Zhang,Zhaohan Feng,Shangde Sun

The 3-monochloropropane-1, 2-diol esters (3-MCPDEs) and glycidyl esters (GEs), which are recognized as contaminants often produced during the deodorization process of refined edible oils, have garnered widespread attention and research interest in recent years due to their potential health risks to humans. Although there have been studies on the formation mechanisms of 3-MCPDEs and GEs, further clarification is still needed in the intrinsic synergistic effects of precursors. Herein, the synergistic effects of acylglycerols, including monoacylglycerols (MAGs), diacylglycerols (DAGs), and triacylglycerols (TAGs) on the formation of 3-MCPDEs and GEs were innovatively investigated through simulated deodorization experiments in model soybean oil systems. Additionally, the effects of simulated deodorization conditions, including temperatures, heating duration, chloride contents, and acylglycerol compositions on the production of 3-MCPDEs and GEs, were also investigated. The results indicated that under the simulated deodorization process and in the presence of chloride ions, the formation of 3-MCPDEs and GEs was facilitated by the synergistic interaction among MAGs, DAGs and TAGs. It is noteworthy that MAGs were more susceptible to forming 3-MCPDEs in the presence of chloride ions, whereas GEs predominantly resulted from the cyclization reaction of DAGs. Concurrently, when the MAGs content was less than 1%, or the presence of DAGs was less than 4% in the model system, the formation of both 3-MCPDEs and GEs was found to be below the EU regulatory limits, thus offering a solid theoretical basis for the control of 3-MCPDEs and GEs in refined oils.

CAS / MDL: 64-17-5 24589-78-4
研究领域: 食品科学 · 毒理学
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Journal of Cleaner Production · 2018 · IF 5.651

A cleaner approach for biodegradable lubricants production by enzymatic glycerolysis of castor oil and kinetic analysis

Shangde Sun,Gaoshang Wang,Ping Wang

Monoricinolein (MRO) and diricinolein (DRO) were renewable and biodegradable lubricants . In this paper, MRO and DRO were prepared by the novel cleaner enzymatic glycerolysis of castor oil (CO) in solvent-free system. Three commercial immobilized lipases (Novozym 435, Lipozyme RM IM and Lipozyme TL IM) were screened and compared, and Novozym 435 showed the best catalysis performance among the tested lipases. Effects of reaction variables (reaction pressure, reaction time, temperature, enzyme load, substrate ratio and water content) on the enzymatic glycerolysis of CO were investigated. High conversion of CO (92.48 ± 1.02%) and the maximum bio lubricants yields (54.47 ± 0.58% MRO and 38.01 ± 0.50% DRO) were achieved under the following conditions: enzyme load 5% (w/w, based on the total mass), CO/glycerol ratio at 1:6, 90 °C, and 3 h. The activation energies (Ea) for CO conversion and the formation of MRO and DRO were calculated as 33.75 kJ/mol, 22.26 kJ/mol and 24.37 kJ/mol, respectively, and the process showed high selectivity toward the formation of MRO. Reaction kinetic agreed with the ping-pong Bi-Bi mechanism with the inhibition of CO, and the kinetic values ( V max Vmax , K m ′ Km′ and K IA KIA ) were 0.0946 mol/(L·min), 1.6704 mol/L, and 0.89 mol/L, respectively.

CAS / MDL: 8001-79-4
研究领域: 生物化学 · 可再生资源工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

A simple two-step reaction for synthesizing demulsifiers for a high salt crude oil emulsion

Yajun Zhao,Min Huang,Xialing Wang,Yu Ding,Lingrui Chen,Qian Qu,Yuqi Tang,Yuanzhu Mi

In this paper, two demulsifiers (PDA-L and GDA-L) were synthesized by grafting lauric acid on polyethylene glycol diglycidyl ether or glycerol triglycidyl ether. The structure of PDA-L and GDA-L were analyzed by FTIR and 1 HNMR, and the demulsification performance in water-in-oil emulsion was detailly evaluated by the bottle test. The results showed that PDA-L exhibited higher demulsification efficiency (DE) compared to GDA-L, attributed to its more appropriate amphiphilic characteristics. Judging by the results, when the dosage of PDA-L was 500 mg/L, the DE could achieve 100 % within 4 h at a temperature of 50 °C, and it also had excellent demulsification performance in a wide pH range (4–10) and high salinity. The competitive adsorption behavior of asphaltenes and PDA-L at the oil–water interface was studied by interfacial tension and three-phase contact angle. Moreover, the effect of PDA-L on the interfacial film strength was studied by coalescence time of droplets and viscoelastic modulus. Based on previous tests, a possible demulsification mechanism was proposed. PDA-L features a hydrophilic core and two extended hydrophobic alkyl chains, allowing it to readily move to the oil–water interface. This process facilitates the replacement of asphaltene and the formation of an unstable composite film, thereby promoting demulsification.

CAS / MDL: 111-42-2
研究领域: 化学工程 · 石油工程
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2025 · IF 6.2

Glycerophospholipids Analysis Using Conventional 1H–31P HMBC and Its Application in Revealing the Characteristics of 18 Seaweeds

Shan-Peng Ma,Cong Wang,An-Zhen Chen,Xiu-Li Zhang,De-Peng Wang,Hong-Bing Liu

Glycerophospholipids (GPLs) are typical membrane lipids with important physiological and pharmacological functions, but little is known about their distribution characteristics in economic seaweeds. This study established a systematic evaluation method, including conventional 2D 1H–31P heteronuclear multiple bond correlation (HMBC) NMR for identifying GPLs and 1D 31P NMR for determining the contents, which were then applied to reveal subclasses characteristics of GPLs in 18 economic seaweeds in Asia. The results indicated that phosphatidylglycerol (PG) was the characteristic GPL subclass distributed in all of the 18 seaweeds (ranging from 0.08 to 1.75‰), generally with higher contents than that of known terrestrial plants. The characteristic chemical shifts of protons in the GPLs headgroup (H-1′) together with protons in the backbone (H-3) were summarized through 1H–31P HMBC spectrum, which were helpful in assigning GPL subclasses.

CAS / MDL: 60-00-4
研究领域: 生物化学 · 海洋生物学
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Science Bulletin · 2019 · IF 6.277

Glycerol aerobic oxidation to glyceric acid over Pt/hydrotalcite catalysts at room temperature

Junbo Zhang,Xiaolin Li,Ming Xu,Yusen Yang,Yinwen Li,Ning Liu,Xiaoyu Meng,Lifang Chen,Shuxian Shi,Min Wei

Glycerol (GLY) aerobic oxidation in an aqueous solution is one of the most prospective pathways in biomass transformation, where the supported catalysts based on noble metals (mainly Au, Pd, Pt) are most commonly employed. Herein, Pt nanoparticles supported on rehydrated Mg x Al 1 -hydrotalcite (denoted as re-Mg x Al 1 -LDH-Pt) were prepared via impregnation-reduction method followed by an in situ rehydration process, which showed high activity and selectivity towards GLY oxidation to produce glyceric acid (GLYA) at room temperature. The metal-support interfacial structure and catalyst basicity were modulated by changing the Mg/Al molar ratio of the hydrotalcite precursor, and the optimal performance was achieved on re-Mg 6 Al 1 -LDH-Pt with a GLY conversion of 87.6% and a GLYA yield of 58.6%, which exceeded the traditional activated carbon and oxide supports. A combinative study on structural characterizations (XANES, CO-FTIR spectra, and benzoic acid titration) proves that a higher Mg/Al molar ratio promotes the formation of positively charged Pt δ + species at metal-support interface, which accelerates bond cleavage of α-C–H and improves catalytic activity. Moreover, a higher Mg/Al molar ratio provides a stronger basicity of support that contributes to the oxidation of terminal-hydroxyl and thus enhances the selectivity of GLYA. This catalyst with tunable metal-support interaction shows prospective applications toward transformation of biomass-based polyols.

研究领域: 化学工程 · 催化科学 · 生物质转化
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