中孔硫酸化氧化锆-氧化硅催化甘油转化制丙烯醛

一种中孔硫酸化的、只含Br?nsted酸位的氧化锆-氧化硅催化剂可将甘油转化为丙烯醛,其产率和选择性分别为81%和82%.即使在低温(523 K)下,产物时空收率可高达9.0 mmol h–1 gcat–1.本催化剂的活性和选择性高于典型的硫酸化的ZrO2催化剂.氧化硅稀释了锆物种而使得催化剂酸性更温和,较大的孔径使得传质更快,因此催化剂性能提高.     

气-液半间歇反应器中甘油氯化:用于生产氯代醇的新型催化剂(英)

Glycerol from biodiesel production can be an important industrial feedstock for chemical commodities as it can be used in the food,cosmetic,pharmaceutical and tobacco industries.However,crude glycerol derived from biodiesel production has a low value because of impurities.The purification of this glycerol into a high grade involves high costs and is not economically feasible for small and medium size plants.The glycerol conversion into chlorohydrins was studied using new homogeneous catalysts and hydrochloric acid as chlorination agent.This is an interesting alternative route to epichlorohydrin and then to epoxy resins.The behavior of two series of homologous catalysts,glycolic acid series(glycolic acid,di-glycolic acid and thio-glycolic acid) and amminoacid series(glutamic acid,aspartic acid and cysteine),were investigated for their activity and selectivity.Glycolic acids were more active than amminoacids.The pK_a values had a strong influence on selectivity(mono-chlorohydrins/di-chlorohydrins) for the amminoacid series,which was not observed for the glycolic acids.A kinetic model and reaction mechanism developed in a previous work were used for interpreting the kinetic runs.     

气-液半间歇反应器中甘油氯化:用于生产氯代醇的新型催化剂(英)

Glycerol from biodiesel production can be an important industrial feedstock for chemical commodities as it can be used in the food,cosmetic,pharmaceutical and tobacco industries.However,crude glycerol derived from biodiesel production has a low value because of impurities.The purification of this glycerol into a high grade involves high costs and is not economically feasible for small and medium size plants.The glycerol conversion into chlorohydrins was studied using new homogeneous catalysts and hydrochloric acid as chlorination agent.This is an interesting alternative route to epichlorohydrin and then to epoxy resins.The behavior of two series of homologous catalysts,glycolic acid series(glycolic acid,di-glycolic acid and thio-glycolic acid) and amminoacid series(glutamic acid,aspartic acid and cysteine),were investigated for their activity and selectivity.Glycolic acids were more active than amminoacids.The pK_a values had a strong influence on selectivity(mono-chlorohydrins/di-chlorohydrins) for the amminoacid series,which was not observed for the glycolic acids.A kinetic model and reaction mechanism developed in a previous work were used for interpreting the kinetic runs.     

复合金属氧化物催化剂用于甘油氧化制丙烯酸的研究进展

随着化石燃料的短缺及其利用所产生的环境问题,可再生生物质资源逐渐成为生产燃料以及化学品的重要来源。近年来,甘油作为生物柴油生产的主要副产物受到了人们的广泛关注,利用其生产高附加值产品以及开发相关的转化技术也成为了国内外学者研究的热点。在诸多转化技术中,甘油选择性氧化制丙烯酸展现出了广阔的发展前景,对该反应尤其是催化剂开展研究具有重要的经济意义和社会意义。文中综述了用于甘油选择性氧化制丙烯酸复合金属氧化物催化剂的研究现状,介绍了当前用于该反应的催化体系类型以及对甘油氧化制丙烯酸催化反应机理的认识,分析并提出了存在的问题以及对未来的展望。     

Synthesis and characterization of acrylamide/acrylic acid hydrogels crosslinked using a novel diacrylate of glycerol to produce multistructured materials

In this work we propose a new crosslinking agent and the method to use it for the synthesis of acrylate based hydrogels. The use of this diacrylate of glycerol, synthesized in our laboratory, allows the generation of materials with well defined micro‐structures in the dry state, unique meso‐ and macro‐structures during swelling, and enhanced mechanical properties and swelling capacity in water. These properties depend on the crosslinking agent concentration, as well as synthesis thermal history. Poly(acrylamide‐co‐acrylic acid) hydrogels are commonly crosslinked with N, N′‐methylenebisacrylamide or N‐isopropylacrylamide. Here we obtain and use a new crosslinking agent, obtained from the reaction between glycerol and acrylic acid to produce a Diacrylate of glycerol (DAG). Two synthesis methods at equivalent molar ratio of acrylamide/acrylic acid (AM/AA) were analyzed. The mechanical properties, the swelling capacity, and the morphology at microscale of these hydrogels showed a well defined transition at a critical concentration of crosslinking agent. DAG induces the generation of hydrogels with hierarchichal structure. The micro‐structure surface morphology was investigated by scanning electron microscopy, the meso‐structure by polarized light microscopy and the macro‐structure by CCD imaging. The hydrogels with hierarchical structures showed improved mechanical properties when compared with structureless hydrogels. Control of the microstructure allows the generation of materials for different applications, i.e. templates or smart materials that interact with electromagnetic radiation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2667–2679, 2008     

Characterization of Catalysts for Glycerol Ester Production with Various Acetylating Agents

The use of raw materials from renewable sources by industries is essential to the sustainable development of modern society. The biodiesel produced by the transesterification of vegetable oils is a less polluting diesel fuel, but large amounts of glycerol (10% of total weight of product) are generated during the production process. The scientific community and industries of the sector know that, in the future, the amount of glycerol generated can cause a serious ecologic problem. Thus, it is essential to find alternatives for the consumption of this co-product, in its crude form and/or as high value-added derivatives. This work studied obtaining triacetate from the glycerol esterification reaction that was determined by electrospray ionization–mass spectrometry and gas chromatography–mass spectrometry. The reactions were carried out with sulfuric acid, phosphotungstic acid and in the absence of catalyst, using different acetylating agents (acetic acid and acetic anhydride). The phosphotungstic acid showed satisfactory performance in the catalytic esterification of glycerol when acetic acid and acid anhydride were used. The use of acetic anhydride as the acetylating agent favors the esterification reaction, decreasing the reaction time required for obtaining glycerol triacetate.     

腐植酸负载Pd/Ni双金属催化剂对Heck反应催化性能的研究

制备了腐植酸负载Pd/Ni双金属催化剂, 该催化剂能够成功催化溴苯与丙烯酸、苯乙烯等乙烯基化合物的Heck反应, 产率均在85%以上; 催化剂能够不同程度地重复使用, 在催化溴苯与丙烯酸反应中, 催化剂重复使用3次后仍可得到42.9%的产率, 而在催化溴苯与苯乙烯反应中, 催化剂重复使用7次后也可得到26.7%的产率; 并且对不同取代基芳基卤与丙烯酸的反应也有很好的催化活性.     

Glycerol-Based Retrievable Heterogeneous Catalysts for Single-Pot Esterification of Palm Fatty Acid Distillate to Biodiesel

The by-product of the previous transesterification, glycerol was utilised as an acid catalyst precursor for biodiesel production. The crude glycerol was treated through the sulfonation method with sulfuric acid and chlorosulfonic acid in a reflux batch reactor giving solid glycerol-SO₃H and glycerol-ClSO₃H, respectively. The synthesised acidic glycerol catalysts were characterised by various analytical techniques such as thermalgravimetric analyser (TGA), infrared spectroscopy, surface properties adsorption-desorption by nitrogen gas, ammonia-temperature programmed desorption (NH₃-TPD), X-ray diffraction spectroscopy (XRD), elemental composition analysis by energy dispersive spectrometer (EDX) and surface micrographic morphologies by field emission electron microscope (FESEM). Both glycerol-SO₃H and glycerol-ClSO₃H samples exhibited mesoporous structures with a low surface area of 8.85 mm²/g and 4.71 mm²/g, respectively, supported by the microscopic image of blockage pores. However, the acidity strength for both catalysts was recorded at 3.43 mmol/g and 3.96 mmol/g, which is sufficient for catalysing PFAD biodiesel at the highest yield. The catalytic esterification was optimised at 96.7% and 98.2% with 3 wt.% of catalyst loading, 18:1 of methanol-PFAD molar ratio, 120 °C, and 4 h of reaction. Catalyst reusability was sustained up to 3 reaction cycles due to catalyst deactivation, and the insight investigation of spent catalysts was also performed.     

Valorisation of glycerol as renewable feedstock: comparison of the exploration of chemical transformation methods aided by high throughput experimentation

Renewable feedstocks have been in the spotlight of intensive research activities over the past 10 years. Glycerol is one of the feedstock molecules which has been the target of numerous research efforts, for a number of reasons. First of all glycerol is currently readily available due to the fact that it is a couple product of the first generation biodiesel production. Secondly glycerol can be taken as a representative model substrate to explore the options of selective conversion of sugar alcohols to products of value. In our paper we discuss potential routes for the valorisation of glycerol which lead to intermediates already established within the petrochemical value chain and illustrate what impact high throughput experimentation may have as a success factor on research and development for this field. As illustrative examples we have chosen the oxidative transformation of glycerol to acrolein and acrylic acid and the carbonylation of glycerol to C4-acids.     

Cellulose hydrolysis catalyzed by highly acidic lignin-derived carbonaceous catalyst synthesized via hydrothermal carbonization

Acidic carbonaceous solids were synthesized from mass pine alkali lignin via hydrothermal carbonization followed by sulfonation. Hydrothermal carbonization of lignin in the presence of acrylic acid (LAHC-SO₃H) provided many more carboxylic groups than that in the absence of acrylic acid, allowing subsequent sulfonation to produce a highly active and stable catalyst for cellulose hydrolysis in the [BMIM]Cl-H₂O solvent system. The hydrochar and catalyst were characterized using field emission scanning electron microscopy, X-ray diffractometer, X-ray photoelectron spectroscopy, thermal gravimetric analysis, Fourier transform infrared spectrometer, Brunauer–Emmett–Teller and acid–base titration. Results showed that a high acid content of 5.48 mmol/g, including carboxylic group (2.85 mmol/g), phenolic hydroxyl group (1.05 mmol/g) and sulfonic acid group (1.58 mmol/g), contributed significantly to the highly efficient hydrolysis of cellulose. Further, it was found that addition of trace water in [BMIM]Cl was favorable to cellulose hydrolysis. The highest yield (75.4%) of total reducing sugar (TRS) obtained in [BMIM]Cl-H₂O at a mass ratio of 100:1 was more than twice that (36.1%) achieved in [BMIM]Cl without water; the corresponding reaction conditions were 50 mg of microcrystalline cellulose, 30 mg of catalyst, 1.0 g of [BMIM]Cl, 10 mg of H₂O, reaction temperature of 130 °C and reaction time of 2 h. Furthermore, the TRS yield with 5 cycles for LAHC-SO₃H was higher than 68.1%, and the catalytic activity of catalyst could be fully recovered (74.0% of TRS yield) easily by regeneration.     

Phase diagram and X-ray diffraction analysis of the acrylic acid–acrylamide system

The phase diagram of the acrylic acid–acrylamide system as determined by DTA and the supporting x-ray diffraction data are presented. This diagram shows that the system forms a 1 : 1 addition compound which decomposes above 0°C. There is also one eutectic point at a 67 mole-% acrylic acid composition.     

Pressure and concentration profiles in filter cake consisting of core/shell latex particle

Poly(styrene-co-acrylic acid) latex particles with different acrylic acid contents have been synthesized and used for filtration studies. Effective pressure and dry matter concentrations were measured at different positions in the filter cakes during the filtration processes, and dry matter concentration was not found to change significantly with effective pressure. Nevertheless, the local dry matter concentration did increase with time for latex particles containing 1 and 3%, w/w acrylic acid, which indicate that filter cake comprising latex particles with a high acrylic acid content will creep during the filtration stage. The filter cakes were examined using stepped-pressure filtration experiments as well, and an almost instantaneous deformation of the filter cake was observed after the pressure step. Furthermore, a minor deformation was observed over the following 2 h for latex particles both containing and not containing acrylic acid. This is thought to be due to the rearrangement of particles in the filter cake.     

Stabilization of Formate Dehydrogenase in a Metal–Organic Framework for Bioelectrocatalytic Reduction of CO2

The efficient fixation of excess CO₂ from the atmosphere to yield value‐added chemicals remains crucial in response to the increasing levels of carbon emission. Coupling enzymatic reactions with electrochemical regeneration of cofactors is a promising technique for fixing CO₂, while producing biomass which can be further transformed into biofuels. Herein, a bioelectrocatalytic system was established by depositing crystallites of a mesoporous metal–organic framework (MOF), termed NU‐1006, containing formate dehydrogenase, on a fluorine‐doped tin oxide glass electrode modified with Cp*Rh(2,2′‐bipyridyl‐5,5′‐dicarboxylic acid)Cl₂ complex. This system converts CO₂ into formic acid at a rate of 79±3.4 mm h^?1 with electrochemical regeneration of the nicotinamide adenine dinucleotide cofactor. The MOF–enzyme composite exhibited significantly higher catalyst stability when subjected to non‐native conditions compared to the free enzyme, doubling the formic acid yield.     

Exploring the potential of biodiesel derived crude glycerol into high value malic acid: Biosynthesis,process optimization and kinetic assessment

In this study, Zygosaccharomyces rouxii, a sugar tolerant yeast culture was explored for the production of high value malic acid using crude glycerol from biodiesel plant. In addition, the effect of addition of glutamic acid (precursor) (0.25 to 1%), temperature (15 to 30 ​°C) and time (0 to 24 days) of the fermentation process was also investigated by both conventional as well as Response Surface Methodology (RSM). The highest malic acid of 72.1 ​± ​0.05 ​g/L was obtained and RSM predicts the accurate optimized conditions such as 30% crude glycerol concentration in the fermentative media with 0.75% addition of precursor with initial pH 5 ​at 20 ​°C for 20 days. This study reveals that the crude glycerol can be efficiently used and the production of malic acid was raised with 3 folds correspond to no precursor under optimal conditions. The growth and product kinetics were studied by Monod, Logistic, Leudeking Piret as well as Logistic incorporated Leudeking-Piret models with and without precursor and Logistic incorporated Leudeking-Piret model allowed the best fit for the malic acid production.     

Synthesis and characterization of a multiarm poly(acrylic acid) star polymer for application in sustained delivery of cisplatin and a nitric oxide prodrug

Functionalized polymeric nanocarriers have been recognized as drug delivery platforms for delivering therapeutic concentrations of chemotherapies. Of this category, star‐shaped multiarm polymers are emerging candidates for targeted delivery of anticancer drugs, due to their compact structure, narrow size distribution, large surface area, and high water solubility. In this study, we synthesized a multiarm poly(acrylic acid) star polymer via macromolecular design via the interchange (MADIX)/reversible addition fragmentation chain transfer (MADIX/RAFT) polymerization and characterized it using nuclear magnetic resonance (NMR) and size exclusion chromatography. The poly(acrylic acid) star polymer demonstrated excellent water solubility and extremely low viscosity, making it highly suited for targeted drug delivery. Subsequently, we selected a hydrophilic drug, cisplatin, and a hydrophobic nitric oxide (NO)‐donating prodrug, O²‐(2,4‐dinitrophenyl) 1‐[4‐(2‐hydroxy)ethyl]‐3‐methylpiperazin‐1‐yl]diazen‐1‐ium‐1,2‐diolate, as two model compounds to evaluate the feasibility of using poly(acrylic acid) star polymers for the delivery of chemotherapeutics. After synthesizing and characterizing two poly(acrylic acid) star polymer‐based nanoconjugates, poly(acrylic acid)–cisplatin (acid–Pt) and poly(acrylic acid–NO (acid–NO) prodrug, the in vitro drug release kinetics of both the acid–Pt and the acid–NO were determined at physiological conditions. In summary, we have designed and evaluated a polymeric nanocarrier for sustained‐delivery of chemotherapies, either as a single treatment or a combination therapy regimen. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A kinetic investigation of radiation induced bulk polymerization of acrylic acid

The kinetics of the γ-ray induced polymerization of acrylic acid in bulk is investigated in a temperature interval of 20–50°C and a dose rate of 2.8–24.6 Gy/min. The reaction rate was observed to increase with increasing temperature and dose rate. The order of the reaction α, with respect to initiation i.e. dose rate, changed between 1.51 and 0.79 in the temperature interval studied. The kinetic analysis of the conversion curves was made according to equations developed by Magat for nonsteady state polymerizations taking place in precipitating media. k_p/k_t ratio thus determined for bulk polymerization of acrylic acid increased with increasing temperature and decreased with dose rate at a given temperature. This behavior as well as the change in the molecular weights of the poly(acrylic acid)s were explained to be as due to the termination of growing chain radicals occluded in the precipitated polymer by primary radicals.     

Microsphere resin chromatography combined with microbial biotransformation for the separation and purification of salvianolic acid B in aqueous extract of roots of Salvia multiorrihza Bunge

Salvianolic acid B was separated and purified from Salvia miltiorrhiza Bunge (danshen) by microbial transformation together with chromatography of microsphere resin. The aqueous extract of danshen was transformed by Fusarium graminearum in a bioreactor containing phosphate buffer (PBS), in which rosmarinic acid was transformed into danshensu and caffeic acid and the yield of salvianolic acid B was higher than 85%. After biotransformation, salvianolic acid B was purified by microsphere resin. A parallel test for making a comparison of microsphere resin chromatography between elution by methanol water solution and water was done. The purity of salvianolic acid B was up to 95% at the yield of 62% when impurities and salvianolic acid B were eluted by 45% and 55% methanol solution respectively. The purity of salvianolic acid B was up to 99% at the yield of 90% when distilled water was used to elute the impurities and salvianolic acid B. The total yield of salvianolic acid B was up to 75% at the purity over 99% while biotransformation combined with microsphere resin chromatography by water elution. Microbial biotransformation together with water elution of microsphere resin supplied an efficient method to eliminate the micromolecular impurities and a possible method to purify water-soluble compounds in traditional Chinese medicine.     

脂肪酶Novozym 435催化合成单月桂酸甘油酯

生物酶催化的有机化学反应具有选择性高、反应条件温和、环境友好等优点,本项目通过对酶催化合成单月桂酸甘油酯的反应条件和产物分离条件进行详细研究,将酶催化反应引入本科实验教学,使学生学习先进的知识技术。本项目的合成部分采用月桂酸:甘油=1:3.5 (摩尔比)的投料比、5%酶用量,在52℃反应80 min;回收脂肪酶后,洗涤除去甘油,蒸馏除去叔丁醇,最后用石油醚重结晶可得到纯度90%以上的高含量产品,分离产率47%–53%,实验的稳定性和重现性好,很适合作为一个大学本科有机实验项目。     

Analysis of the Production Process of Optically Pure <Emphasis Type="SmallCaps">d</Emphasis>-Lactic Acid from Raw Glycerol Using Engineered <Emphasis Type="Italic">Escherichia coli</Emphasis> Strains

Glycerol has become an ideal feedstock for producing fuels and chemicals. Here, five technological schemes for optically pure d-lactic acid production from raw glycerol were designed, simulated, and economically assessed based on five fermentative scenarios using engineered Escherichia coli strains. Fermentative scenarios considered different qualities of glycerol (pure, 98 wt.%, and crude, 85 wt.%) with concentrations ranging from 20 to 60 g/l in the fermentation media, and two fermentation stages were also analyzed. Raw glycerol (60 wt.%) was considered as the feedstock feeding the production process in all cases; then a purification process of raw glycerol up to the required quality was required. Simulation processes were carried out using Aspen Plus, while economic assessments were performed using Aspen Icarus Process Evaluator. D-Lactic acid recovery and purification processes were based on reactive extraction with tri-n-octylamine using dichloromethane as active extractant agent. The use of raw glycerol represents only between 2.4% and 7.8% of the total production costs. Also, the total production costs obtained of D-lactic acid in all cases were lower than its sale price indicating that these processes are potentially profitable. Thus, the best configuration process requires the use of crude glycerol diluted at 40 g/l with total glycerol consumption and with D-lactic acid recovering by reactive extraction. The lowest obtained total production cost was 1.015 US$/kg with a sale price/production cost ratio of 1.53.     

H2 enriched fuels from co-pyrolysis of crude glycerol with biomass

Pyrolysis of glycerol has been identified as a possible route for producing high added value fuels like renewable hydrogen (H₂). Crude glycerol (CG) is the main byproduct of biodiesel industry and without purification it is a low added value material due to the presence of impurities. Co-pyrolysis of CG with biomass may improve the efficiency of the process and as a primary step of gasification give important information concerning the maximization of H₂ concentration in the produced gas. Moreover, the thermochemical treatment of crude glycerol–biomass mixtures may offer several economic and environmental advantages in biodiesel industry and reduce the cost of biodiesel production. A mixture of CG with olive kernel (OK) was used as pyrolysis feed material. Pyrolysis of a 25 wt% mixture of CG with OK at high temperature (T = 720 °C) seemed to promote steam reforming reactions leading to an increase of H₂ concentration of 11.6 vv% in the pyrolysis gas in comparison to H₂ in gas obtained by low temperature pyrolysis (T = 520 °C).