Use of the glycerol by‐product of biodiesel to modify the surface of expanded vermiculite to produce an efficient oil absorbent

BACKGROUND: Glycerol (Gly) a by‐product from biodiesel production was impregnated onto the surface of expanded vermiculite (EV) and reacted to produce a highly efficient absorbent to remove oils spilt on water. RESULTS: Expanded vermiculite was impregnated with glycerol at EV/Gly ratios of 1/1, 1/2, 1/3 and 1/4, and treated at 380, 480, 580 or 700 °C. Electrospray ionization mass spectroscopy, thermogravimetry, BET surface area, Hg porosimetry and Raman analyses indicated that residual NaOH from the biodiesel process catalyzed the polymerization of glycerol. At higher temperatures the polymer decomposed to form a carbon layer covering the EV surface. These materials were investigated for the removal of three different oils, i.e. diesel, soybean and engine oil spilt on water. CONCLUSION: This work showed that glycerol from biodiesel production can be used directly to produce a highly efficient absorbent to remediate oil spill accidents. The results obtained showed a remarkable increase on oil removal efficiency with a strong decrease on water absorption. Copyright © 2009 Society of Chemical Industry     

Modification of vermiculite by polymerization and carbonization of glycerol to produce highly efficient materials for oil removal

Impregnation and reaction of glycerol (Gly) on the surface of expanded vermiculite (EV) was used to produce a highly efficient absorbent to remove water spilled oils. The vermiculite was impregnated by glycerol containing 1, 2 and 4 mol% of H₂SO₄ at EV/Gly ratios, i.e. 1/1, 1/2 and 1/3, and heated to 380, 580 and 750 °C. SEM, TG, BET specific surface area, and Raman analyses indicated that glycerol at 380 °C forms a polymer layer. At higher temperatures, the polymer decomposed to form porous carbon covering the EV surface. These materials were investigated for the removal of three different oils, i.e. diesel, soybean and engine oil spilled on water. The obtained results showed a remarkable increase on oil removal of 600% compared to the non-modified EV.     

甘油氢解用固体超强碱负载的铜催化剂

用浸渍-燃烧法制备了固体超强碱MgO-CaO和MgO-SrO负载的高分散铜基催化剂,并将其用于甘油氢解制备1,2-丙二醇的反应。N₂吸附、X射线衍射、透射电子显微镜、H₂程序升温还原和N₂O氧化吸附及CO₂程序升温脱附等表征实验结果显示:Cu粒子均分散于Cu/MgO-CaO(或者Cu/MgO-SrO)催化剂的表面;与Cu/MgO相比,Cu/MgO-CaO和Cu/MgO-SrO具有更强的碱性,可以加速甘油的转化。上述结果表明,甘油氢解反应中铜催化剂的活性随碱性的增强而增加。     

Surface hydrolysis of postconsumer polyethylene terephthalate to produce adsorbents for cationic contaminants

In this work, the surface hydrolysis of postconsumer polyethylene terephthalate (PET) was used to produce an ion exchange material to adsorb cationic contaminants from water. The PET surface hydrolyses were carried out in neutral, alkaline, and acid media (NaOH or HNO₃ at 7, 10, and 15 mol L^?1) under reflux producing surface carboxylic acid sites (? COOH) characterized by ATR‐IR, pyridine adsorption, titration, TG, and DSC analyses. Acid hydrolysis produced high concentrations of ? COOH (up to 0.5 mmol g^?1_PET), whereas no significant concentration of carboxylic acid sites was obtained by neutral and alkaline hydrolysis. SEM analyses suggest that the acid sites are likely located at the cracks and defects produced on the PET surface by acid hydrolysis. Neutral or alkaline hydrolysis produced a very regular and smooth PET surface with very low acid site concentrations. The adsorption isotherms of Cd⁺² as a model of heavy metal and the dye methylene blue as a model of large organic cationic molecules showed high adsorption capacities for the HNO₃‐hydrolyzed PET, whereas no adsorption takes place on the neutral‐ or alkaline‐hydrolyzed polymer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5284–5291, 2006     

Purification of glycerol/water solutions from biodiesel synthesis by ion exchange: sodium removal Part I

BACKGROUND: In this study, equilibrium and kinetic data of the ion exchange of sodium from glycerol–water mixtures on the strong acid resin Amberlite‐252 were obtained. Basic parameters for the design of ion exchange units for the purification of the crude glycerol phase from biodiesel production have been determined. RESULTS: Equilibrium uptake of sodium ions with the strong acid ion exchanger Amberlite‐252 was studied at three temperatures. The Langmuir equation and the mass action law model were used to fit the experimental equilibrium data. Equilibrium constants and thermodynamic parameters were obtained at each temperature. Kinetic experiments were carried out to evaluate the effective diffusion coefficients of sodium on the resin Amberlite‐252 in glycerine–water media. CONCLUSIONS: Equilibrium results indicate that this process is favourable and also that its selectivity decreases with temperature increase from 303 to 333 K. Both models were able to fit the experimental equilibrium data. Kinetic experiments showed that the rate of mass transfer in this binary system is high. An Arrhenius type equation allowed the correlation of effective diffusion coefficients and temperature. The results indicate that the macroporous resin Amberlite‐252 could be useful for removal of sodium ions from glycerine/water solutions with a high salt concentration. Copyright © 2008 Society of Chemical Industry     

Purification of glycerol/water solutions from biodiesel synthesis by ion exchange: sodium and chloride removal. Part II

BACKGROUND: Equilibrium studies were carried out with the aim of finding the basic design parameters for ion exchange plants using a glycerol phase obtained from biodiesel production. The uptake of sodium and potassium ions on a strongly acidic ion exchanger, Amberlite IR‐120, in the proton form from glycerol/water mixtures has been studied. The effect on the selectivity towards sodium of the percentage of water in glycerine/water mixtures on the macroporous resin Amberlite 252 has been analyzed. Finally, chloride removal by a strongly basic anionic‐exchange resin Amberlite IRA‐420 at three different temperatures has been studied. RESULTS: The strongly acidic ion exchanger Amberlite IR‐120 exhibits higher selectivity for potassium versus sodium ions. The ideal mass action law model was able to fit the experimental equilibrium data. The equilibrium data obtained at different percentages of water in the glycerine/water mixture indicate that as the water content increased the resin selectivity for sodium uptake is reduced. The selectivity of the anion exchange resin Amberlite IRA‐420 for chloride ions decreases with temperature. The ideal mass action law was accurate enough to fit the equilibrium data of the three systems and allowed the equilibrium thermodynamic properties to be obtained. CONCLUSIONS: These results confirm that macroporous resin Amberlite 252 could be a good choice to remove sodium ions from glycerol/water solutions with a high salt concentration and also that a strongly basic anionic‐exchange resin could be used for chloride removal. Copyright © 2009 Society of Chemical Industry     

CeO_2/C有序介孔材料催化甘油转化制碳酸甘油酯

采用溶剂挥发自组装法制备有序介孔CeO_2/C复合材料,利用X射线衍射仪、N_2吸附-脱附仪和透射电子显微镜对样品进行表征,考察催化甘油酯交换制备碳酸甘油脂的催化性能。结果表明,在甘油用2 mmol、碳酸二甲酯10 mmol、有序介孔CeO_2/C复合材料0.1 g、N,N-二甲基乙酰胺5 m L、反应温度140℃和反应时间3 h条件下,CeO_2/C中CeO_2质量分数为16.3%时,甘油转化率和碳酸甘油脂选择性最高,分别为76%和81.8%。     

Utilization of biodiesel and glycerol for the synthesis of epoxidized acyl glycerides and its application as a plasticizer

In many regions, even if waste vegetable oil is used as raw material, the profits of biodiesel (fatty acid methyl ester, FAME) enterprises still remain restricted, and they are facing environmental problems caused by the by-product glycerol. Hence, value-added utilization of FAME and glycerol is a promising alternative to improve the competitiveness of biodiesel enterprises in the economy and environmental protection. In this paper, FAME and glycerol were utilized to prepare epoxidized acyl glycerides by transesterification and epoxidation. In the transesterification, acyl glycerides were prepared by reacting FAME and glycerol catalyzed by K₂CO₃. The contents of monoacyl glyceride, diacyl glyceride, and triacyl glyceride in the acyl glycerides were about 50%, 40%, and 10%, and the optimal conditions were a temperature of 200°C and the molar ratio of FAME to glycerol of 1:1. In the epoxidation, selectivity of epoxides was significantly affected by monoacyl glyceride content, and a treatment method was developed to control the monoacyl glyceride content <5%. In addition, the plasticity of epoxidized acyl glycerides to partially substitute dioctyl phthalate in polyvinyl chloride was studied, the overall mechanical properties, thermal stability, and extraction resistance were improved. In this work, FAME and glycerol were utilized to prepare epoxidized acyl glycerides with higher value-added, which provide a potential solution for improving the market competitiveness of biodiesel enterprises.     

N-Heterocyclic carbenes: Effective organic catalysts for living polymerization

An organocatalytic approach to living and condensation polymerization using N-heterocyclic carbenes as nucleophilic catalysts is detailed. The N-heterocyclic carbene catalyst platform is extremely versatile with the nature of the substituents having a pronounced effect upon catalyst stability and activity towards different substrates. Rapid screening of libraries of catalysts provided a basic understanding of catalyst structure (sterics, electronics, etc.) as it influences the polymerization rate, control, substrate and range of molecular weights. ROP from an immiscible ionic liquid (precatalyst reservoir) and a THF solution of monomer and initiator is presented as a simplified method of carbene formation. In situ activation of the ionic liquid generated a nucleophilic N-heterocyclic carbene, which migrates to the organic phase effecting ROP. Other simplified methods of generating carbene thermally from carbene adducts are also presented as polymerization catalysts.     

Au-Promoted Pt nanoparticles supported on MgO/SBA-15 as an efficient catalyst for selective oxidation of glycerol

A systematic study of Au-promoted and unpromoted Pt/MgO/SBA-15 catalyst is developed to separate the promoter effect from electron transfer effect between Au and Pt. Multi-characterizations revealed that Au and Pt metals in these bimetallic catalysts mainly exist in the form of alloy, and the main role of Au is to reduce the size of AuPt alloy nanoparticles, thus enhancing the adsorption and activation of intermediate products. Through the optimization of various factors (including MgO content, Au/Pt molar ratio, reaction temperature and time), the Au₁Pt₂/MgO/SBA-15 (0.05) catalyst exhibits excellent catalytic activity and glyceric acid selectivity for the selective oxidation of glycerol. Density functional theory calculation confirmed that the synergistic effect between Pt and Au active sites could facilitate the oxidation of primary hydroxyl group by promoting the activation of C H bond and the oxidation of aldehyde group. The results may give insights on designing effective Pt based bimetallic catalyst for selective oxidation of glycerol.     

An alternative spectrophotometric method for the determination of free glycerol in biodiesel

The presence of small amounts of free glycerol in fatty acid methyl esters used as diesel fuel or as heating fuel may represent the reason for some failures in engines and heating systems as well. Several methods are actually available for the determination of free‐glycerol traces in biodiesel, and most on them are based on gas‐chromatographic techniques. After a review of the existing methods, a new procedure based on periodate oxidation of glycerol, leading to the preparation of formaldehyde, on reaction with acetylacetone and on spectrophotometric measurement at 410 nm is illustrated. This method is simple, quick and economic and seems to be sufficiently reliable. Data related to recovery tests and analyses of real samples are shown, also in correlation with the existing reference method.     

Next-generation organometallic adsorbents for safe removal of excessive fluoride from aqueous systems

The presence of excessive fluoride contamination in aquatic environments causes large-scale health problems affecting about 260 million people across the globe. Here we have investigated a novel method to develop zirconium-based organometallic nanoadsorbents (ZrAN) for the removal of fluoride from aqueous systems. A series of ZrAN adsorbents composed of zirconyl methacrylate (ZrDMA) and acrylonitrile (AN) have been developed by varying the relative amounts of crosslinker, porogen, and comonomers. The spherical adsorbents have high porosity and excellent mechanical stability, properties that prevent material breakage and mass loss during practical use. Experimental factors such as effects of pH, initial fluoride concentration, adsorbent dose, coexisting anions, pH_pzc, isotherm models, and surface chemistry were investigated to clarify the adsorption properties of ZrAN. A high adsorption capacity of 46 mg/g was recorded with a high fluoride concentration of 60 mg/L, which outperformed many other reported adsorbents. Moreover, the ZrAN adsorbent performed well over a considerable pH range of 2–10 with significant removal at pH 6–8, which is the preferred range for groundwater applications. Additionally, the results of the toxicity characteristics leaching procedure suggested the ZrAN adsorbents were inert, do not leach out any contaminants (Zr, F⁻), and deliver safe and potable treated water. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46993.     

KF/MgO催化甘油和碳酸二甲酯酯交换合成甘油碳酸酯

采用浸渍法制备KF/MgCO₃前体,经高温焙烧后获得了一系列KF/MgO固体碱催化剂,用于催化碳酸二甲酯（DMC）和甘油（GL）酯交换反应合成甘油碳酸酯（GC）。系统考察了KF负载量和焙烧温度对催化剂活性的影响,并通过X射线衍射、N₂吸脱附等温线、扫描电子显微镜和哈米特酸碱滴定等一系列技术对催化剂的结构性能进行了表征。结果表明,当KF负载量为20%（质量分数）时,经550℃焙烧所获得的20%KF/MgO-550催化剂活性最高。经过反应工艺条件的优化,当催化剂与甘油的相对质量分数为2%,DMC与GL的摩尔比为3∶1,75℃条件下反应1.5h后,GC收率可以达到96.8%。当20%KF/MgO-550催化剂重复使用3次之后,GC的收率由96.8%降低到67.3%,经再生处理后20%KF/MgO-550的催化活性可以恢复并且表现出更优异的稳定性。     

Intercalative redox polymerization and characterization of poly(n‐vinyl‐2‐pyrrolidinone) in the gallery of vermiculite: A novel inorganic–organic hybrid material

In this article we present the synthesis of poly(N‐vinyl‐2‐pyrrolidinone) (PNVP)–vermiculite hybrid material and its characterization by various spectroscopic techniques, X‐ray diffraction (XRD), and thermal analysis. The polymer was synthesized by intercalative redox polymerization of the monomer at 110°C, using copper (II) ion‐exchanged vermiculite. XRD analysis following intercalative polymerization indicates the presence of two prominent peaks with corresponding d (002) spacing of 14.3 (intercalated) and 9.9 (not intercalated) Å, suggesting the formation of a partially intercalated hybrid material. Electron spin resonance studies of the intercalated material show values of “g” different from that of the Cu (II)‐ion‐exchanged vermiculite, indicating that polymer formed in the gallery of vermiculite complexes with the unreacted Cu (II). Thermogravimetric analysis indicates the amount of polymer in the gallery spacing to be ≈20 mass %, which is confirmed by I₂ labeling of the PNVP in the nanocomposite, followed by UV spectroscopy. The IR absorption peaks corresponding to PNVP, along with the XRD and thermal analysis data confirms that the gallery expansion is due to the formation of a partially intercalated inorganic‐organic hybrid material. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1825–1830, 2000     

An experimental and theoretical study of glycerol oxidation to 1,3‐dihydroxyacetone over bimetallic Pt‐Bi catalysts

It is important to utilize glycerol, the main by‐product of biodiesel, to manufacture value‐added chemicals such as 1,3‐dihydroxyacetone (DHA). In the present work, the performance of five different catalysts (Pt‐Bi/AC, Pt‐Bi/ZSM‐5, Pt/MCM‐41, Pt‐Bi/MCM‐41, and Pt/Bi‐doped‐MCM‐41) was investigated experimentally, where Pt‐Bi/MCM‐41 was found to exhibit the highest DHA yield. To better understand the experimental results and to obtain insight into the reaction mechanism, density functional theory (DFT) computations were conducted to provide energy barriers of elementary steps. Both experimental and calculated results show that for high DHA selectivity, Bi should be located in an adatom‐like configuration Pt, rather than inside Pt. A favorable pathway and catalytic cycle of DHA formation were proposed based on the DFT results. A cooperative effect, between Pt as the primary component and Bi as a promoter, was identified for DHA formation. Both experimental and theoretical considerations demonstrate that Pt‐Bi is efficient to convert glycerol to DHA selectively. © 2016 American Institute of Chemical Engineers AIChE J, 63: 705–715, 2017     

Synthesis of poly(glycerol methacrylate) and its application to dimensional stabilization of wood

The dimensional stabilization of wood is investigated using poly(glycerol methacrylate) (PGMA) prepared from polyglycerol and glycidyl methacrylate instead of the well‐known poly(ethylene glycol). PGMA allows waterborne treatment of wood, which after polymerization leads to the formation of a wood polymer composite with improved dimensional stability. Microscopic observations and a picture analysis permit the location of PGMA in the wood cell walls and explains the dimensional stabilization by its bulking effect. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 743–749, 2003     

甘油催化氢解制备丙二醇的研究现状

随着生物柴油产业的快速发展,作为生物柴油副产物的甘油逐渐过剩,合理有效地利用甘油能促进生物柴油产业的良性发展。丙二醇(1,2-丙二醇和1,3-丙二醇)是重要的化工中间体,具有较高的经济价值,利用可再生的甘油催化氢解制备丙二醇替代传统的石化路线符合绿色化学的要求,因而具有广阔的应用前景。简述了利用甘油催化氢解制备丙二醇的研究背景,详细分析了甘油催化氢解的机理(包括脱水-加氢机理、脱氢-加氢机理、直接氢解机理和螯合机理),从催化剂的角度综述了甘油催化氢解制备丙二醇的研究现状和取得的研究成果,并提出了未来甘油氢解的研究方向。     

Comparison of atmospheric aqueous glycerol and steam explosion pretreatments of wheat straw for enhanced enzymatic hydrolysis

BACKGROUND: The oversupply of cheap glycerol by the oleochemicals industry together with problems occurring in low‐boiling‐point organosolv pretreatments, has generated an interest in the use of glycerol in the organosolv pretreatment of lignocellulosic biomass. Atmospheric aqueous glycerol autocatalytic organosolv pretreatment (AAGAOP) is a promising strategy that can effectively enhance enzymatic hydrolysis of lignocellulosic biomass. As a cost‐effective technique, steam explosion pretreatment (SEP) is being adopted in industrial applications. Accordingly, work has been carried out to investigate how AAGAOP enhanced enzymatic hydrolysis of lignocellulosic biomass compares with the SEP method. RESULTS: Under controlled laboratory conditions, based on ≥ 90% cellulose recovery, AAGAOP removed ≥ 60% hemicellulose and ≥ 60% lignin from wheat straw while SEP led to ～80% hemicellulose and 10% lignin removal. Enzymatic hydrolysis yields of AAGAOP and SEP reached ～90% and ～70%, respectively. Physical‐chemical structural characterization by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT‐IR), helped explain the above results. The two methods gave priority to dissociating the guaiacyl lignin and had a relatively small effect on syringyl units. However, AAGAOP exhibited a superior performance. CONCLUSION: The two methods enhanced the enzymatic hydrolysis of lignocellulosic biomass by removing and/or altering physical‐chemical structural impediments. The AAGAOP technique, with some special advantages, was more effective than SEP in enhancing the recovery and enzymatic digestibility of cellulose. Copyright © 2008 Society of Chemical Industry     

Covalent organic frameworks-incorporated thin film composite membranes prepared by interfacial polymerization for efficient CO2 separation

Thin film composite (TFC) membranes with nanofillers additives for CO₂ separation show promising applications in energy and environment-related fields. However, the poor compatibility between nanofillers and polymers in TFC membranes is the main problem. In this work, covalent organic frameworks (COFs, TpPa-1) with rich —NH— groups were incorporated into polyamide (PA) segment via in situ interfacial polymerization to prepare defect-free TFC membranes for CO₂/N₂ separation. The formed covalent bonds between TpPa-1 and PA strengthen the interaction between nanofillers and polymers, thereby enhancing compatibility. Besides, the incorporated COFs disturb the rigid structure of the PA layer, and provide fast CO₂ transfer channels. The incorporated COFs also increase the content of effective carriers, which enhances the CO₂ facilitated transport. Consequently, in CO₂/N₂ mixed gas separation test, the optimal TFC (TpPa_0.025-PIP-TMC/mPSf) membrane exhibits high CO₂ permeance of 854 GPU and high CO₂/N₂ selectivity of 148 at 0.15 MPa, CO₂ permeance of 456 GPU (gas permeation unit) and CO₂/N₂ selectivity of 92 at 0.5 MPa. In addition, the TpPa_0.025-PIP-TMC/mPSf membrane also achieves high permselectivty in CO₂/CH₄ mixed gas separation test. Finally, the optimal TFC membrane showes good stability in the simulated flue gas test, revealing the application potential for CO₂ capture from flue gas.