Waterborne polyurethane wood coatings based on rapeseed fatty acid methyl esters

Trends in wood coatings are driven to waterborne systems and to renewable resources. Vegetable oils are well known for wood coatings, e.g. alkyds or polyurethane dispersions. In this context, fatty acid methyl esters turn out to be an alternative to technical fatty acids and vegetable oils. High contents of hydrophobic oil-based monomers require a sufficient understanding of the dispersion stability. This study shows the influence of hydrophobic monomers, ionic centers, degree of neutralization, and stirring procedure to the particle size distribution and dispersion stability. Furthermore, the impact of these parameters on the resulting coating film properties was investigated.     

新型转鼓反应器在脂肪酸甲酯连续磺化中的应用

设计了一种新型的转鼓反应器并用于脂肪酸甲酯的连续磺化反应。研究结果表明,新型转鼓反应器具有持液量小、液体中气含率高、气液停留时间分布均匀的特点。在转鼓转速为1 200 r/min、SO3体积分数为5%、SO3/FAME摩尔比为1.2∶1、85℃磺化、65℃老化、老化1 h的条件下,得到的产品中脂肪酸甲酯磺酸钠质量分数为84.9%,二钠盐质量分数为1.2%,二钠盐的质量分数明显小于文献报道值;得到的产品符合国家优级品要求。     

脂肪酸甲酯加氢脱氧和蒸汽裂解两步法制备生物烯烃

脂肪酸甲酯经生物烷烃制备轻质烯烃,有望缓解低原油价格导致的生物柴油产业发展困境。采用浸渍法制备了NiMo/Al₂O₃催化剂,首先考察其催化脂肪酸甲酯加氢脱氧制备生物烷烃的性能,然后进一步分析生物烷烃蒸汽裂解制烯烃的转化规律。结果表明,预硫化的NiMo/Al₂O₃能够高选择性地催化饱和脂肪酸甲酯加氢制备生物烷烃,并且催化剂的结构在反应1000 h后无明显改变。以上述烷烃为原料,在裂解炉出口温度为810℃,出口压力为0.10 MPa,物料停留时间为0.23 s和水油质量比为0.75的反应条件下进行蒸汽裂解,产物中乙烯、丙烯和丁二烯的收率分别达到36.30%、18.14%和7.46%,显著高于同等条件下石脑油原料得到的27.45%、14.74%和5.31%,表明源于脂肪酸甲酯的生物烷烃可以作为生产轻质烯烃的原料补充。     

氯代甲氧基脂肪酸甲酯增塑性能的研究

本文以不同比例的氯代甲氧基脂肪酸甲酯替代电缆料配方中的增塑剂DOP,考察了电缆料试片的最大力、抗张强度、断裂伸长率及邵氏硬度等指标。试验表明,当DOP为增塑剂总量40%,氯代甲氧基脂肪酸甲酯为增塑剂总量60%时,电缆料材料的各项性能指标均好于100%DOP的电缆料材料,其最大力为375N、抗拉强度为23.78MPa、断裂伸长率为324.42%、邵氏硬度75.86度。当DOP为增塑剂总量20%,氯代甲氧基脂肪酸甲酯为增塑剂总量80%时,电缆料材料的各项指标性能与100%DOP的电缆料材料性能相当。     

脂肪酸甲酯磺酸钠在衣用液体洗涤剂中的应用

对目前市售几种规格的脂肪酸甲酯磺酸钠（MES）产品进行了对比,提出了衣用液体洗涤剂配方和生产技术对MES产品的技术要求。研究了MES在衣用液体洗涤剂中与LAS、AES等其他类型表面活性剂复配对体系去污力、泡沫性能、稳定性以及储存过程中二钠盐含量变化的影响。结果表明,在衣用液体洗涤剂配方体系中,MES与LAS复配去污性能增效明显,与LAS＋AES复配有一定的去污增效作用,而与AES复配没有增效作用。随复配体系中MES加量的增加,洗衣液泡沫下降,随储存时间的延长和储存温度的升高,产品中二钠盐含量增加。     

脂肪酸甲酯磺酸盐的复合性能研究

用MES同AES-2、LAS或AOS进行复合,测定复合样品的表面张力、润湿力、泡沫性能及黏度,并对复合体系的性能进行讨论。结果表明：MES与AES-2复合体系的表面张力和润湿力具有负的协同效应,泡沫体积和黏度明显增加;MES与LAS复合体系的表面张力、润湿力和发泡性能具有负的协同效应,黏度明显增加;而MES与AOS体系的表面张力具有负的协同效应,润湿力有很好的协同效应,泡沫体积明显增加,但黏度无太大变化。在MES与AES-2、LAS或AOS复合体系中,当MES的质量分数为50%时,体系表现出特别的性能。     

不同碳链长度脂肪酸甲酯的催化裂化产物分布规律

以辛酸甲酯、癸酸甲酯、月桂酸甲酯3种碳链长度不同的脂肪酸甲酯为原料,LVR-60为催化剂,在固定床上考察不同温度（350～500℃）下碳链长度对脂肪酸甲酯催化裂化产物分布的影响规律。结果表明,随着脂肪酸甲酯碳链长度的增长,脂肪酸甲酯转化率不断提高,脱氧产生的CO、CO₂逐渐增加,液体产物中烃类的含量逐渐增加而含氧衍生物逐渐减少。提高反应温度有利于提高脂肪酸甲酯转化率,得到较多的烃类,降低液相产物中含氧衍生物的含量。在低温下,脂肪酸甲酯裂化生成的醛、酯、羧酸、酮等含氧衍生物的含量较高,其裂化过程中CO₂是主要的脱氧产物;而高温下有机液体产物中几乎不含含氧衍生物,CO为主要脱氧产物。     

磷钨酸铈催化合成棕榈酸和硬脂酸混合酸甲酯

采用磷钨酸铈作为催化剂,在反应温度67 ℃合成棕榈酸和硬脂酸混合酸甲酯反应,研究酸醇物质的量比、催化剂用量和反应时间对酯化反应的影响,并在最佳反应条件基础上研究催化剂的循环利用工艺。结果表明,在酸醇物质的量比1∶10、催化剂用量为棕榈酸和硬脂酸混合酸质量的8%、反应时间4 h和催化剂重结晶后循环利用10次条件下,棕榈酸和硬脂酸混合酸转化率均≥96.0%,催化剂反应前后的IR和XRD表征发现,催化剂均为Keggin型结构,未发生变化,表现出良好的催化活性。     

Estimation of heat of combustion of triglycerides and fatty acid methyl esters

Equations were developed for the estimation of gross heat of combustion (HG) of triglycerides (TGs) and fatty acid methyl esters (FAMEs) from their saponification number (SN) and iodine value (IV). HG of TG=1,896,000/SN − 0.6 IV — 1600 and HG of FAME=618,000/SN − 0.08 IV — 430. When these equations were tested on cottonseed oil, soybean oil, partially hydrogenated soybean oil, peanut oil, sunflower oil, sunflower oil methyl esters, soybean oil methyl esters and cottonseed oil methyl esters, predicted HG values agreed well with those reported in the literature.     

Simple, high-efficiency synthesis of fatty acid methyl esters from soapstock

We report a simple method that efficiently esterifies the fatty acids in soapstock, an inexpensive, lipid-rich by-product of edible oil production. The process involves (i) alkaline hydrolysis of all lipid-linked fatty acid ester bonds and (ii) acid-catalyzed esterification of the resulting fatty acid sodium salts. Step (i) completely saponified all glycerides and phosphoglycerides in the soapstock. Following water removal, the resulting free fatty acid sodium salts were rapidly and quantitatively converted to fatty acid methyl esters (FAME) by incubation with methanol and sulfuric acid at 35°C and ambient pressure. Minimum molar reactant ratios for full esterification were fatty acids/methanol/sulfuric acid of 1∶30∶5. The esterification reaction was substantially complete within 10 min and was not inhibited by residual water contents up to ca. 10% in the saponified soapstock. The product FAME contained >99% fatty acid esters, 0% triglycerides, <0.05% diglycerides, <0.1% monoglycerides, and <0.8% free fatty acids. Free fatty acid levels were further reduced by washing with dilute sodium hydroxide. Free and total glycerol were <0.01 and <0.015%, respectively. The water content was <0.04%. These values meet the current specifications for biodiesel, a renewable substitute for petroleum-derived diesel fuel. The identities and proportions of fatty acid esters in the FAME reflected the fatty acid content of soybean lipids. Solids formed during the reaction contained 69.1% ash and 0.8% protein. Their sodium content indicated that sodium sulfate was the prime inorganic component. Carbohydrate was the predominant organic constituent of the solid.     

脂肪酸甲酯磺酸盐的研究及应用进展

论述了脂肪酸甲酯磺酸盐的发展状况。介绍了脂肪酸甲酯磺酸盐优良的洗涤性能、可生物降解性和绿色环保等优异性能。对国内外脂肪酸甲酯磺酸盐的发展及生产技术进行了回顾。对我国脂肪酸甲酯磺酸盐的发展状况、未来趋势及发展前景进行了展望。面对石油资源日趋紧张,必然将人们引向油脂化工这一传统领域。脂肪酸甲酯磺酸盐丰富的原料来源、成本优势以及使用优势,使这些油脂基表面活性剂更具市场竞争力。     

The mechanism of ethane hydrogenolysis over ruthenium catalysts and the isokinetic effect

An analysis has been made of the compensation effect observed for literature data on ethane hydrogenolysis over ruthenium catalysts. Using a previously derived expression for the isokinetic temperature it is concluded that the rate determining step is the breaking of the Ru-C bond. This is in accordance with recent views of Sinfelt. In order to substantiate this conclusion a recently published kinetics investigation is reconsidered. The results show two mechanisms, one for ethane/hydrogen pressures < 2, the other one for ethane/hydrogen pressures > 3. In both cases the rate determining step seems to be the Ru-C bond breaking.     

脂肪酸甲酯磺酸盐的制备、性能及应用研究进展

脂肪酸甲酯磺酸盐是一种生物相容性好、去污力优良和抗硬水能力强的高效、低毒表面活性剂。简要介绍了脂肪酸甲酯磺酸盐的制备方法、物理化学性能及其在洗涤剂中的应用。     

Enzymatic synthesis of wax esters from rapeseed fatty acid methyl esters and a fatty alcohol

Wax esters were transesterified from fatty acid methyl esters of rapeseed and a fatty alcohol (1-hexadecanol, 16:0). The amounts of both the substrates were fixed to 0.1 mmol and an immobilized enzyme, Lipozyme, was used as catalyst. The experiment was performed following a statistic central composite design with five variables. The enzyme/lipid ratio was varied between 0.3–0.9 of the substrate weight and the enzyme was equilibrated to different water activities varying from 0.11 to 0.44. A temperature range of 50–80°C was investigated and the reaction time lasted up to 40 min. A solvent, isooctane, constituted 0–30% of the substrate weight. The first experimental series was performed in small closed test tubes. In the second series the caps of the test tubes were off to evaporate the methanol produced during the reaction. The highest initial reaction rate was 9.6 g_{wax esters}/g_enzyme · h. It appeared when: the enzyme/lipid ratio was low, 0.3, the temperature was high, 80°C; no isooctane was present; and the water activity was below 0.11. The initial reaction rate was independent of the caps on the test tubes. With the large amount of enzyme the yield of wax esters was above 70% after 10 min in both experimental series. In the reaction with caps, the reaction reached equilibrium at 83% after 20 min at 80°C. However, without caps the continuous evaporation of methanol increased the equilibrium constantly, and after 40 min at 80°C a yield of 90% was reached.     

An improved reversed-phase thin-layer chromatography method for separation of fatty acid methyl esters

Resolution of fatty acid methyl esters (FAME) by thin-layer chromatography often is complicated by co-migration of certain acyl-isomers in heterogeneous mixtures. However, a novel reversed-phase thin-layer chromatography method which employs 10% (wt/vol) silver nitrate in a mobile phase containing acetonitrile/1,4-dioxane/acetic acid (80:20:1, vol/vol/vol) allows one-dimensional resolution of a wide range of acyl-methyl esters. This innovation enables improved separation of saturated FAME ranging from C₁₂ to C₂₂, and geometric isomers of C₁₄ to C₂₂ unsaturated FAME by thin-layer chromatography.     

脂肪酸甲酯磺酸钠在洗涤剂中的应用性能研究

将脂肪酸甲酯磺酸钠(MES)分别配成液体和粉状洗涤剂,测定不同时间内MES的水解率、表面活性剂的发泡力、表面活性剂和洗涤剂的去污力。结果表明,MES在碱性液体洗涤剂和洗衣粉料浆中容易水解,在10%的碳酸钠溶液中水解率达28.87%;MES在硬水中的发泡力明显好于烷基苯磺酸钠(LAS)。无论是表面活性剂还是在洗涤剂中,MES均显示出超强的去污力,去污力比值是LAS的1.6~1.7倍;MES与LAS复配时,去污力无协同增效作用。     

铜基催化剂的制备及其在催化溴甲烷制二甲醚中的应用

采用浸渍法制备了不同载体和金属组分的系列负载型催化剂,考察对溴甲烷制二甲醚的催化活性,并采用XRD、TPR和BET进行表征。结果表明,铜基催化剂催化性能较好,且以Al2O3-1#为载体制备的催化剂催化性能更优。Cu O负载量较低时,具有较高的分散度;高温焙烧使催化剂的活性中心由分散态Cu O转变为晶相Cu O,导致Cu O利用率下降;添加助剂K可显著提高Cu O利用率。优选的催化剂制备条件为:以Al2O3-1#为载体,活性组分Cu O负载质量分数为5%,助剂K负载质量分数为0.8%,焙烧温度为350℃,此条件下制备的催化剂,CH3Br转化率和二甲醚选择性均为100%,催化剂的Cu O利用率达到88.04%;再生10次后,催化剂性能保持稳定,没有明显下降。     

脂肪酸甲酯磺酸盐制备和分析方法的研究进展

介绍了SO3磺化法和磺氧化法两种制备脂肪酸甲酯磺酸盐(MES)的方法,重点介绍了MES产品中形成深色杂质的原因及MES主要成分的基本分析方法,如薄层色谱、毛细管电泳、色质联用、容量分析等;同时从原料、反应设备、反应过程、成色机理等方面阐述了几种不同的抑制MES产品中形成深色杂质的方法,并对MES的发展前景进行了展望.     

甲氧基含量对氯代甲氧基脂肪酸甲酯应用性能的影响

本文以主要成分为十八碳脂肪酸甲酯的生物柴油为主要原料,以甲醇为甲氧基化试剂,在过氧化苯甲酰催化剂存在下,一步氯化法合成了氯代甲氧基脂肪酸甲酯,在反应时间为7～8h,温度为70～85℃的条件下合成的氯代甲氧基脂肪酸甲酯,探讨氯代甲氧基脂肪酸甲酯的甲氧基含量对其在PVC中增塑性能的影响。