由直链不饱和脂肪酸异构制备支链脂肪酸的研究进展

介绍了直链不饱和脂肪酸制备支链脂肪酸的研究现状,综述了脂肪酸异构机理,异构催化剂如白土催化剂、沸石催化剂,催化剂的筛选原则,着重讨论了各种常用沸石对于脂肪酸异构反应不同的影响以及现有的合成工艺。分析了脂肪酸的分离技术,包括精馏分离法、溶剂结晶法、尿素包结法、超临界流体萃取法的优缺点,指出沸石催化生产支链饱和脂肪酸的关键问题是需要解决混合脂肪酸作为原料反应的选择性问题,其相关的基础性工作,如更明确的反应机理和催化剂结构参数对反应的影响,仍是将来的研究方向。     

Microbial conversion of linoleic and linolenic acids to unsaturated hydroxy fatty acids

The conversion of oleic acid to 10-hydroxystearic acid with resting cells ofNocardia cholesterolicum (NRRL 5767) has been previously reported. These same microorganisms also convert linoleic and linolenic acids to 10-hydroxy-12c-octadecenoic and 10-hydroxy-12c,15c-octadecadienoic acids, respectively. The reaction occurs best at 35°C and a pH of 6.5. Under optimum conditions, 75–80% of the unsaturated fatty acid substrate is converted to the corresponding hydroxy acid. The hydroxy products were characterized by gas chromatography, gas chromatographymass spectrometry, nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy. Other microorganisms that successfully converted these substrates include another strain ofNocardia cholesterolicum (NRRL 5768) andNocardia sp. (NRRL 5636). Presented at the 82nd Annual meeting of the American Oil Chemists’ Society, Chicago, IL, May 12–15, 1991.     

Metathesis of unsaturated fatty acids: Synthesis of long-chain unsaturated-α,ω-dicarboxylic acids

The self-metathesis of readily available monounsaturated FA has the potential of being an important pathway for the synthesis of symmetrical long-chain unsaturated-α,ω-dicarboxylic acids (C₁₈−C₂₆). Previous studies on the self-metathesis of monounsaturated FA esters using ruthenium catalysts in solution, however, suffered from low conversions as a result of the thermodynamic control of the reaction. We have found that the second-generation Grubbs catalyst can effectively catalyze the solvent-free self-metathesis of monounsaturated FA of varying purity (from 90 to 99%) to afford two important products—monounsaturated dicarboxylic acids and hydrocarbons—in very high molar conversions (>80%). This solvent-free self-metathesis reaction also works for monounsaturated FA containing additional functional groups. Reactions were conducted at catalyst loadings as low as 0.005 mol%, and turnover numbers as high as 10,800 could be obtained. This discovery represents an attractive approach to the large-scale production of useful monounsaturated-α,ω-dicarboxylic acids and long-chain unsaturated hydrocarbons by means of this solvent-free ruthenium-catalyzed self-metathesis of readily available monounsaturated FA.     

Biodegradation of estolides from monounsaturated fatty acids

Mono- and polyestolides, made from oleic acid, meadowfoam oil fatty acids and erucic acid, were subjected to biodegradation with mixed cultures of Penicillium verucosum, Mucor racemosus, and Enterobacter aerogenes. Fermentations were continued for 3, 5, 10, 15, 20, or 30 d. Meadowfoam oil and its fatty acids, oleic acid and soybean oil were also biodegraded under the same conditions. After 10 d, oleic acid and soybean oil were degraded 99.8 and 99.2%, respectively; meadowfoam oil and its fatty acids were degraded 89.0 and 97.7%, respectively. After 30 d, oleic acid-derived poly- and monoestolides were degraded 98.6 and 90.0%, respectively, meadowfoam estolides were degraded 75.7%, and erucic acid estolides were degraded 84.0%.     

复合氧化物催化剂催化氧化甲苯性能

以γ-Al2O3为催化剂载体,铜、锰为活性组分,稀土元素铈为助催化剂,采用浸渍法制备复合氧化物催化剂5%Cu/γ-Al2O3、5%Mn/γ-Al2O3、5%Cu-5%Mn/γ-Al2O3和5%Cu-5%Mn-1.6%Ce/γ-Al2O3,并考察其催化氧化甲苯性能。研究表明,复合氧化物催化剂催化氧化甲苯具有显著的效果,5%Cu-5%Mn/γ-Al2O3催化剂和5%Cu-5%Mn-1.6%Ce/γ-Al2O3催化剂表现出良好的低温活性和催化性能,对甲苯的完全燃烧温度分别为340℃和285℃。采用SEM和BET对催化剂进行表征,结果表明,催化剂的催化活性与活性组分在催化剂表面的分散度和催化剂的孔结构相关。     

The synthesis of silicon oleochemicals by hydrosilylation of unsaturated fatty acid derivatives

The hydrosilylation of fatty acid esters with terminal or internal double bonds catalysed by H₂ PtCl₆ is described. The reaction was carried out with good yields at ambient pressure under mild conditions. Methyl undec‐10‐enoate was reacted with chloro‐ or alkoxyhydrosilanes giving moderate to good yields (41—77%) and even its reaction with alkylhydrosilanes produced low yields (below 20%). Under optimised conditions the hydrosilylation of methyl linoleate gave only with reactive chlorohydrosilanes acceptable yields, between 25 to 83%, of regioisomers. The hydrosilylation of methyl α‐linolenate with dimethylchlorosilane gave a mixture of regioisomeric 1:1‐ and 2:1‐hydrosilylation adducts in a total yield of 40%. The hydrosilylation of ethyl oleate did not proceed at all under our conditions. In the case of methyl undec‐10‐enoate a biphasic solvent system permitted the simple separation and reuse of the homogeneous catalyst.     

Production of hydroxy fatty acids from unsaturated fatty acids byFlavobacterium sp. DS5 hydratase,a C-10 positional- andcis unsaturation-specific enzyme

A new microbial isolate,Flavobacterium sp. DS5, converted oleic and linoleic acids to their corresponding 10-keto-and 10-hydroxy fatty acids. The hydration enzyme seems to be specific to the C-10 position. Conversion products from α- and γ-linolenic acids were identified by gas chromatography/mass spectrometry, Fourier transform infrared, and nuclear magnetic resonance as 10-hydroxy-12(Z),15(Z)-octadecadienoic and 10-hydroxy-6(Z),12(Z)-octadecadienoic acids, respectively. Products from other 9(Z)-unsaturated fatty acids also were identified as their corresponding 10-hydroxy- and 10-keto-fatty acids.Trans unsaturated fatty acid was not converted. From these results, it is concluded that strain DS5 hydratase is indeed a C-10 positional-specific andcis-specific enzyme. DS5 hydratase prefers an 18-carbon monounsaturated fatty acid. Among the C₁₈ unsaturated fatty acids, an additional double bond at either side of the 9,10-position lowers the enzyme hydration activity. Because hydratases from other microbes also convert 9(Z)-unsaturated fatty acids to 10-hydroxy fatty acids, the C-10 positional specificity of microbial hydratases may be universal.     

Structure-activity relationship of unsaturated fatty acids as mosquito ovipositional repellents

Various straight-chain unsaturated fatty acids from C₁₄ to C₂₄ were evaluated for their ovipositional repellency against gravid females of the southern house mosquitoCulex quinquefasciatus Say, and the relationship between the structures of the fatty acids and their ovipositional repellency was determined. A double bond withZ configuration was prerequisite for an unsaturated fatty acid to be highly repellent;E isomers were less active or even inactive. No relationship was found between the repellency and the number of double bonds in the unsaturated fatty acids. In C₁₈ monounsaturated fatty acids, (Z)-9 acid was more active than (Z)-11 and (Z)-6 acids, indicating that a double bond at the 9 position rendered an acid highly repellent. Among (Z)-9-alkenoic acids of different chain lengths, the most repellent was C₁₈ acid which was also more active than (Z)-11-C₂₀, (Z)-13-C₂₂, and (Z)-15-C₂₄ acids. Oleic[(Z)-9-octadecenoic]acid, which met all these criteria, was the most ovipositionally repellent among the unsaturated fatty acids tested.Diptera: Culicidae.     

催化湿式氧化法治理H-酸母液废水的研究

H-酸母液是染料工业急需治理的高浓度有机废水,COD含量高,酸性强,一般的生化法尚不能有效治理。作者研制了具有高氧化活性的含贵金属-稀土金属双活性组分催化剂,对H-酸母液工业废水进行了催化湿式氧化(CWO)治理研究。CWO试验在固定床鼓泡式反应器连续反应装置上进行。试验考察了反应温度、反应压力、进水空速、废水pH值和气水比对催化湿式氧化法处理H-酸废水效果的影响。考虑反应工艺条件的影响和工厂实际情况以及对处理费用的要求,选定在248℃,4.0MPa,空速=2.0h-1,V(空气)∶V(水)=220∶1,废水pH=6.0的条件下,处理含CODCr46391mg/L,色度5600倍的H-酸母液废水,CODCr和色度的去除率分别达到95.4%和98.2%。处理后的废水可生化性有所提高,BOD/COD>0.3,可进一步用生化法降解排放,催化剂运转稳定性良好。根据小试结果初步估算治理H-酸废水费用约为(以COD计)0.6～0.7元/kg。     

Pelargonic acid in enhanced oil recovery

Oxidation of monounsaturated fatty acids, such as erucic and oleic acids, results in the formation of dibasic fatty acids, such as brassylic and azelaic acids. Dibasic acids find many industrial applications. Pelargonic acid is the co-product of the process. Expanded use of dibasic acids would require an expansion in the existing and possibly new uses for pelargonic acid and its derivatives. In this study, the potential for using pelargonic acid in enhanced oil recovery is investigated. Experimental results are presented for the enhanced oil recovery by waterflooding with the aid of a surfactant.In situ formation of surfactant at the oil-water interface vs. the formation of surfactant in the floodwater prior to injection is examined.     

Oxidative decarboxylation of unsaturated fatty acids

Long‐chain internal olefins were prepared by silver(II)‐catalyzed oxidative decarboxylation of unsaturated fatty acids by sodium peroxydisulfate. Similar to saturated carboxylic acids, 1‐alkenes were the major decarboxylation product in the additional presence of copper(II), whereas in the absence of copper(II) alkanes were predominantly formed. In both cases, the internal unsaturation of the fatty acids remained largely intact, although the moderate yields indicated that side reactions occurred to a significant extent. The simple procedure makes this multistep one‐pot reaction useful for the synthesis of a variety of internally unsaturated hydrocarbons. The purified products, almost all of which are prepared for the first time, may serve as reference compounds for studies on the heterogeneously catalyzed decarboxylation of triglycerides and fatty acids in the absence of hydrogen. Practical applications: The products of the chemistry described in this contribution, i.e., unsaturated long‐chain hydrocarbons, provide bio‐based building blocks for further chemical modification toward products which may be applied as (bio)fuels, lubricants, solvents, and polymeric materials.     

顺丁烯二酸酐催化氧化合成酒石酸

以纳米TiO₂为载体,通过浸渍法制备得到负载型催化剂W/TiO₂,通过催化氧化顺丁烯二酸酐合成酒石酸,研究了催化剂的催化性能。考察了反应温度、反应时间、反应物配比和催化剂用量等反应条件对氧化反应的影响。结果表明,反应温度70 ℃,反应时间6 h,掺杂钨质量分数为10％的W/TiO₂催化剂用量为顺丁烯二酸酐质量的4%和n（H₂O₂）∶n（顺丁烯二酸酐）＝3时,顺丁烯二酸酐转化率达90%。     

WHZSM-5的合成及其对环己酮的催化性能

采用无机法,以水玻璃为硅源,硫酸铝为铝源,钨酸为钨源,在酸性条件下合成了具有ZSM-5结构的微孔分子筛(WZSM-5),经过离子交换合成了WHZSM-5分子筛。通过X射线衍射、红外吸收光谱等手段对催化剂进行了表征。结果表明:所制得的分子筛具有ZSM-5的特征结构,钨原子进入了ZSM-5骨架;以质量分数30%双氧水为氧化剂,环己酮与双氧水体积比为1:5时,催化剂用量为5 g/L,反应温度100℃,反应时间为6 h,催化氧化效果最好,环己酮转化率达93%;催化剂连续使用5次,反应活性基本不变。     

催化氧化法合成环己酮技术研究进展

介绍了以环己烷为原料催化氧化合成环己酮的主要方法,分析了环己烷氧化采用的主要催化剂。环己烷硼酸催化氧化法和钴盐催化氧化法存在环己烷转化率低及结渣现象;分子筛催化氧化法、金属氧化物以及金属络合物仿生催化氧化法可提高环己烷转化率及醇酮选择性;金属络合物仿生催化氧化法具有良好的开发应用前景。     

油酸催化氧化制壬二酸

对利用油酸氧化制取壬二酸进行了较为系统的探索。在 50℃ ,pH =2 .5,适宜催化剂条件下 ,壬二酸的收率提高到 60 %,且反应条件温和 ,具备工业生产的价值。     

An integrated process of catalytic hydrolysis and membrane separation for fatty acids production from lard oil

An integrated process of catalytic hydrolysis and membrane separation was developed for fatty acids (FAs) production from lard oil. Both sulphonated cation exchange resin (SCER) and 0.98 g/g H₂SO₄ as catalysts were used to produce fatty acids (FAs) from lard oil by three‐step hydrolysis, respectively. Simultaneously, polyethersulphone (PES) ultrafiltration membrane was employed to separate glycerol and water from the products. The hydrophilicity and morphology of the pristine and used PES membranes were characterized by contact angle measurement and field‐emission scanning electronic microscopy, respectively. The final optimal yields of FAs obtained by SCER and H₂SO₄ catalysis at 100 °C and atmospheric pressure were 85.6 % at 16.0 h of operation and 94.5 % at 18.0 h of operation, respectively. Furthermore, the yield of FAs obtained from an integrated process of SCER‐catalyzed hydrolysis and membrane separation achieved up to 99.9 % at 10.0 h, 90 °C, and operating pressure of 100 kPa.

     

Autoxidation kinetics for fatty acids and their esters

The autoxidation kinetics for n-3 and n-6 polyunsaturated fatty acids and their esters, which are collectively referred to as polyunsaturated fatty acids (PUFA), were investigated. Changes in the amounts of unreacted n-6 PUFA during the entire period of autoxidation could be expressed by dY/dt−k ₁ Y(1 −Y), wereY was the fraction of unreacted PUFA,t was the time, andk ₁ was the rate constant. For n-3 PUFA, autoxidation had to be separated into two parts. The first half of autoxidation (Y ≥ 0.5) was expressed by the same equation as above, while the latter half (Y<0.5) relates to dY/dt=−k ₂ Y, wherek ₂ was the rate constant. The apparent activation energies and the frequency factors ofk ₁ andk ₂ were evaluated. The apparent activation energies were in a range of 50 to 60 kJ/mol for bothk ₁ andk ₂. The frequency factor became large as the number of double bonds of PUFA increased.     

TiSiW12O40/TiO2在酯化反应中的应用

介绍了固载杂多酸盐TiSiW₁₂O₄₀/TiO₂在催化合成酯（如一元羧酸酯、二元羧酸酯、羟基酸酯、氯乙酸酯、芳香酸酯、葡萄糖酯）中的研究进展。     

A rapid method for determining the oxidation of n-3 fatty acids

The stability of unsaturated fatty acids to oxidation was monitored by following gas chromatographic (GC) analyses of headspace volatiles in comparison to changes in polyunsaturated fatty acids (PUFA) and increases in malonaldehydevia the 2-thiobarbituric (TBA) assay. Pure standards of linoleic acid (Lo) and n-3 fatty acids [eicosapentaenoic (EPA) and docosahexaenoic acid (DHA)] were added to headspace vials, equilibrated in air for 10 min, followed by heating at 80°C in teflon-capped vials for different time intervals. Headspace analysis showed increases in acetaldehyde, propenal, and propanal, corresponding to the oxidation of n-3 fatty acids, whereas hexanal production corresponded to losses of linoleic acid. The analysis of propanal by GC-headspace after only five minutes of heating appeared to be the most effective method of monitoring the oxidation of n-3 fatty acids, as indicated by correlations between TBA values and loss of PUFA. The oxidation of Lo, EPA and DHA appeared to be a function of the number of double bonds. Correlations between PUFA depletion, TBA values and volatile formation indicate that under the prescribed conditions of this experiment, GC-headspace analysis of propanal and pentane/hexanal is an excellent method for following the oxidation of selected n-3 fatty acids and linoleic acid.     

催化超临界水氧化技术研究进展

催化超临界水氧化技术是在超临界水氧化技术基础上,借鉴催化湿式氧化技术发展起来的一种高效环保的有机废弃物处理技术,可以提高有机污染物的氧化速率,降低工艺条件,拥有十分广阔的应用前景。综述了近年来催化超临界水氧化技术在处理工业污水中催化剂、反应机理、反应动力学、反应器的研究进展。提出了催化超临界水氧化技术的研究方向,以期为催化超临界水氧化技术处理难降解有机污水的发展提供参考。