Challenges in Catalytic Manufacture of Renewable Pyrrolidinones from Fermentation Derived Succinate

Fermentation derived succinic acid ammonium salt is an ideal precursor for manufacture of renewable N-methyl pyrrolidinone (NMP) or 2-pyrrolidinone (2P) via heterogeneous catalysis. However, there are many challenges to making this a practical reality. Chief among the challenges is avoiding catalyst poisoning by fermentation by- and co-products. Battelle/Pacific Northwest National Laboratory have developed an effective technology strategy for this purpose. The technology is a combination of purely thermal processing, followed by simple catalytic hydrogenation that together avoids catalyst poisoning from fermentation impurities and provides high selectivity and yields of NMP or 2P.

     

控制论模型在丁二酸发酵过程中的应用

使用控制论模型来代替国内现有的动力学模型,对丁二酸发酵过程进行建模,然后使用粒子群算法进行参数优化.结果表明控制论模型拟合结果具有较好的可靠性.     

络合萃取法提取发酵液中丁二酸铵

为提高微生物发酵法生产丁二酸的产品提取收率,用三辛胺/正辛醇体系对发酵液进行络合萃取。比较硫酸和阳离子交换树脂两种前处理发酵液方式对络合萃取丁二酸的影响以及用氨水反萃制备丁二酸铵。结果表明,通过阳离子交换树脂前处理发酵液,三辛胺/正辛醇体系对丁二酸的萃取率高于硫酸前处理,达到91.3%;氨水是一种优良反萃剂;萃取剂重复使用5次,平均萃取率为90.4%,平均反萃率为94.9%,且萃取率和反萃率未见明显下降。     

High-Performance Multifunctional Fuel Additives Derived from Renewable Fatty Acids and Phosphazene

The increasing need for high-quality diesel fuel can be fulfilled by using environmental friendly, high-performance additives. We have synthesized novel fatty acid-derived multifunctional additives coupled with phosphazene moiety having the backbone of alternative nitrogen and phosphorous atoms which provided stability, while the additives possessed affinity for the metal surface to form a surface-complex film leading to the hindered metal contact and providing friction-reducing and antiwear properties. In addition, the applicability of the synthesized additives was investigated by testing the anti-oxidant and anticorrosion properties in polyethylene glycol (PEG200) which was taken as the reference base fluid. A rotating bomb oxidation test was used to evaluate the anti-oxidant characteristics, and a four-ball test for the tribological properties. Among the synthesized additives, phosphazene ester of erucic acid exhibited the best antiwear and antifriction properties; however, phosphazene ester of oleic acid was found to be the best anti-oxidant additive.     

MgAlLi Mixed Oxides Derived from Hydrotalcite for Catalytic Transesterification

Abstract  

MgAl hydrotalcite was synthesized and used as support for Li impregnation. MgAlLi oxides were obtained from heat treatment of the Li/MgAl hydrotalcite. These materials were characterized and evaluated as catalysts for model transesterification reactions. MgAl showed negligible activity under mild reaction conditions (50 °C and 0.5 h) whereas Li incorporation greatly increased the activity. The activities were correlated to their basicity determined by TPD of CO₂. Reuse tests showed catalyst deactivation after the third cycle, probably due to lithium leaching. However, the contribution to a homogeneous reaction has been dismissed. MgAlLi revealed to be a promising catalysts for transesterification reaction and thus for biodiesel production.     

复合型固体超强酸催化合成丁二酸二乙酯的研究

研究了复合型固体超强酸为催化剂催化合成丁二酸二乙酯,探讨了酯化反应条件和催化剂的制作工艺对酯产率的影响。实验结果表明,复合型固体超强酸（SO4^2 /ZrO2-Al2O3）具有较高的催化活性和选择性,在最佳工艺条件下酯主率可达78．6％。该工艺操作简便,条件易控制,对环境无污染。     

基于市政污泥的高效非均相Fenton催化材料的制备及其性能研究

以市政脱水污泥和(NH4)2Fe(SO4)2·6H2O试剂为原料,通过超声-浸渍法将铁元素成功掺杂于污泥载体上,得到了一种高效稳定的非均相Fenton催化剂,探讨了泥铁质量比、焙烧温度和时间等因素对催化剂性能的影响,确定了最佳的制备条件,并运用SEM、FT-IR和XRD等方法对合成样品进行表征,探究了所制备催化剂降解亚甲基蓝(MB)模拟废水的性能.试验结果表明,最佳的制备条件为泥铁质量比1:0.8,焙烧温度为500℃,焙烧时间为120 min.污泥基非均相Fenton催化剂中的铁元素主要以Fe2 O3的形式存在,并能均匀、分散地负载于污泥载体上,负载铁元素与污泥载体之间形成了Si-O-Fe和Fe-O键,具有较好的稳定性.在考察不同体系下MB降解试验发现,制备时引入超声作用可有效提高催化剂性能,反应80 min后对MB的脱色率可达99％,是污泥载体和铁氧化物为表面活性点位协同作用的结果.本研究提出了便捷的、环境友好的污泥回用方法,可有效降解染料废水,达到以废治废.     

磷钨酸催化合成丁二酸二乙酯的研究

磷钨酸作为丁二酸和乙醇的酯化催化剂,性能优于硫酸。本文探讨并找到了其较好的反应条件,酯化率达92 8％。     

α-生育酚琥珀酸酯合成反应工艺及动力学研究

研究了以4-二甲氨基吡啶为催化剂,由α-生育酚和琥珀酸酐合成α-生育酚琥珀酸酯(α-TOS)的酯化反应工艺和反应动力学。该合成反应最佳条件为:α-生育酚与琥珀酸酐配比为1∶3;催化剂用量1.5%;反应温度50℃;反应时间4 h,产率达84.5%,样品的纯度大于96%。通过对反应规律的研究,结果表明,在本实验条件下该合成反应表现为二级不可逆反应,表观活化能Ea=83.4 k J。     

氯化铁催化合成丁二酸二乙酯的研究

氯化铁作为了二酸和乙醇的酯化催化剂,性能优于硫酸。本文探讨并找到其较好的反应条件,酯化率达９０．４６％。     

丁二酸二异丙酯的树脂催化合成研究

本文阐述了用离子交换树脂替代无机酸、有机酸催化剂,催化合成1,4-二酮吡咯并吡咯类高档有机颜料的关键中间体丁二酸二异丙酯的方法。主要考察了不同类型树脂催化剂、催化剂用量、催化剂重复使用次数、异丙醇用量以及脱水剂用量对酯化收率的影响。酯化收率可以达到97．5％。     

微生物好氧发酵法生产甘油

生物好氧工业化生产甘油的工艺过程包括酶法葡萄糖液制备、种子制备、发酵和提取精制4个工 段,采用的载体蒸馏技术克服了甘油真空蒸馏得率低、残渣清除困难两大难题。该专题建立了年产1000t的发酵 甘油装置,并生产出食品级和医药级高品质甘油。     

基于Mn-MOF的多孔碳/MnO复合材料的制备及催化性能研究

首先通过溶剂法制备甲酸锰(Mn-MOF)晶体,接着以Mn-MOF为前驱体,在惰性条件下制备了结构、形貌可控的多孔碳/MnO复合物。采用XRD、BET和SEM表征Mn-MOF前驱体和多孔碳/MnO复合物的结构、形貌等。结果表明,600℃下获得的多孔碳/MnO复合物含有立方相MnO和无定型多孔碳。将多孔碳/MnO复合物用于催化臭氧分解,催化效率可达92.3%,重复利用性好。     

流化床二段法催化裂解废塑料制取燃料

应用新型的流化床催化裂解废塑料 ,并利用混合塑料为原料进行了中试试验 ,研究了催化改质中催化剂种类和温度对所得液体油品产率、组分和催化剂积碳等的影响以及催化裂解中温度对液体油品产率的影响。油品经催化改质后 ,质量得到明显提高 ,所生产的汽油和柴油符合 GB484-93车用汽油产品的标准和 GB2 5 2 - 94轻柴油产品国家标准     

四氯化碳催化加氢制氯仿

报道了四氯化碳催化加氢制氯仿过程中，反应物浓度、溶剂等因素对加氢速度的影响，讨论了不同初始条件下的反应级数和速度常数。对四氯化碳的转化在工业上具有积极的作用。     

对甲苯磺酸催化合成丁二酸二甲酯的研究

对甲苯磺酸作为丁二酸和甲醇的酯化催化剂,性能优于硫酸。本文探讨并找到了其较好的反应条件,酯化率达95．0％。     

Sulfosuccination of Methyl Ricinoleate and Methyl 12-Hydroxy Stearate Derived from Renewable Castor Oil and Evaluation of Their Surface Properties

Sulfosuccination of castor oil-derived methyl ricinoleate and methyl 12-hydroxy stearate have been carried out in the present work. Synthesis involves malenization of secondary alcohol of methyl ricinoleate/methyl 12-hydroxy stearate followed by sulfonation of maleic monoester to generate double-headed dianionic surfactant with carboxylate and sulfosuccinate functionalities in the head group region. Various reaction conditions were optimized for maximum production of these two sulfosuccinates. Both compounds were evaluated for surface and detergency properties. The surface tension study indicated that the critical micelle concentration of sulfosuccinated methyl ricinoleate and methyl 12-hydroxy stearate is 0.26 and 0.11 mM, respectively. The detergency property of these two surfactants indicated that they were excellent in wetting time emulsification and Ca-tolerance. However, these two surfactants exhibited very poor foam height and foam stability.     

Catalytic Transformations for Production of Fine Chemicals and Pharmaceuticals from Wood‐Derived Raw Materials

Wood is a valuable raw material for the production of fine chemicals. However, since wood extractives cannot be used directly, their chemical transformation is required. Catalytic processes, in particular, possess the advantages of being environmentally friendly and industrially attractive. The use of sugars for the production of sugar alcohols and terpene transformations, are well known examples. In contrast, catalytic processes for the utilization of fatty acids, phytosterols and lignans as raw materials are very rarely reported. The products obtained from these materials exhibit health promoting properties. The present mini‐review is focused on recent activities devoted to catalytic transformations of fatty acids, phytosterols and lignans derived from wood.     

Polymers from Renewable Resources. XXVII. Studies on Synthesis,Characterization, and Thermal properties of Resins Derived from Cardanyl Acrylate-Furfural-Organic Compounds

Cardanol, the major constituent of cashew nut shell liquid (CNSL), is extracted from CNSL by vacuum distillation at 3–4 mm pressure of mercury and 230–240°C temperature. Cardanyl acrylate, a derivative of cardanol, is prepared by the Kaliyappan method. A number of resins have been synthesized by condensing cardanyl acrylate with furfural and selective organic compounds in the presence of acid as catalyst. The resins have been characterized by Fourier transform infrared spectra. Solvent absorptivity of the resins have been studied by taking toluene and dimethyl formamide as solvents. The thermal behavior of the resins have been studied. The overall activation energy and order of degradation of the resins have also been evaluated using the Freeman-Anderson method.     

Bifunctional Materials for the Catalytic Conversion of Cellulose into Soluble Renewable Biorefinery Feedstocks

The combination of Br?nsted acidity with metallic functionality in a mesoporous catalyst offers a potential pathway for the conversion of cellulose into sugar alcohols that may be used as a sustainable source of renewable biorefinery feedstock. Supported Ru catalysts were prepared by evaporative deposition on various ordered mesoporous silicas (SBA-15) with different functionalities and characterized using multiple experimental techniques. The catalytic performance of the supported Ru catalysts was compared to that of the corresponding supports and of Ru/C. We studied the effects of functional group loading, reaction time and temperature on the activity and products yield of the bifunctional catalysts by monitoring the cellulose conversion and the production of sugars and sugar alcohols in a high-pressure batch reactor. Sorbitol is the main product obtained by the hydrolysis of cellulose to glucose followed by the corresponding reduction. Secondary products include sugars, ethylene glycol and glycerol. The activity of mesoporous silica catalysts increases with an increase in acid loading and the addition of Ru allows control of the selectivity towards sugar alcohols. Ruthenium supported on arenesulfonic acid-functionalized mesoporous silica (Ru/SBA-15S) displays the best catalytic performance. Ru/SBA-15S is more hydrothermally stable than SBA-15, but loses a significant fraction of its surface area, crystallinity, acidity and activity after prolonged exposure to water at 483?K.