SiW_(12)/SBA-15介孔分子筛催化合成月桂酸乙酯

用传统的水热合成法制备纯硅介孔分子筛SBA-15,将SiW12负载在SBA-15上.采用X射线衍射(XRD)、红外光谱(IR)对不同负载量的催化剂进行了表征.表征结果表明,催化剂SiW12/SBA-15仍具有纯硅SBA-15的介孔结构,SiW12的Keggin结构保持完整.该催化剂用于月桂酸与乙醇的酯化反应,重点考察了硅钨酸的负载量、反应温度、酸醇比、催化剂用量等因素对酯化反应性能的影响.得到最佳反应条件为:硅钨酸的负载量为25%,反应温度90 ℃,酸醇比1:2.5,催化剂用量为月桂酸质量的1%,反应时间4 h.催化剂再生实验结果认为,SiW12/SBA-15介孔分子筛具有良好的再生性能和稳定性.     

SO42-/Al2O3-ZrO2/SBA-15固体酸催化合成棕榈酸甲酯

将Al(NO3)3.9H2O,Zr(NO3)4.5H2O与活化后的主体材料SBA-15分子筛通过尿素水解的方法,制备了改性SBA-15分子筛,进一步用硫酸浸渍处理改性分子筛以增强分子筛表面的酸活性中心。并采用红外光谱、扫描电镜、透射电镜等分析方法对试样进行了表征,结果表明,制得的催化剂SO24-/Al2O3-ZrO2/SBA-15仍然保持高度有序的介孔一维六角结构。并将其催化剂用于棕榈酸与甲醇的酯化反应中,采用正交实验确定较佳的工艺条件为:催化剂用量为1.2 g,n(棕榈酸)∶n(甲醇)=1∶12,反应时间为9 h,此条件下棕榈酸甲酯的反应收率可以达到82.3%,实验表明所合成的固体酸催化剂具有良好的催化性能。     

SiW12／SBA-15介孔分子筛催化合成月桂酸乙酯

用传统的水热合成法制备纯硅介孔分子筛SBA-15,将SiW12负载在SBA—15上。采用x射线衍射（XRD）、红外光谱（IR）对不同负载量的催化剂进行了表征。表征结果表明,催化剂SiW12／SBA-15仍具有纯硅SBA-15的介孔结构,SiW12的Keggin结构保持完整。该催化剂用于月桂酸与乙醇的酯化反应,重点考察了硅钨酸的负载量、反应温度、酸醇比、催化剂用量等因素对酯化反应性能的影响。得到最佳反应条件为：硅钨酸的负载量为25％,反应温度90℃,酸醇比1：2．5,催化剂用量为月桂酸质量的1％,反应时间4h。催化剂再生实验结果认为,SiW12／SBA-15介孔分子筛具有良好的再生性能和稳定性。     

介孔分子筛SiW_(12)/SBA-15催化合成柠檬酸三丁酯

:将硅钨酸负载在纯硅介孔分子筛SBA-15的表面上,XRD结果表明负载型催化剂SiW12/SBA-15具有纯硅SBA-15的介孔结构.将该催化剂用于合成柠檬酸三丁酯的酯化反应.采用正交实验考察了反应温度、催化剂用量、酸醇摩尔比对柠檬酸转化率的影响,得出最佳反应条件为:反应温度120℃、催化剂用量为总物料质量的1.5%、酸醇摩尔比1:4.在此条件下反应4 h,柠檬酸转化率可达到91.5%,产物的纯度为99.3%.     

Preparation of SO2-4/Al2O3-ZrO2/SBA-15 and catalytic activity in esterification of methyl palmitate

将Al(NO3)3·9H2O,Zr( NO3)4·5H2O与活化后的主体材料SBA-15分子筛通过尿素水解的方法,制备了改性SBA -15分子筛,进一步用硫酸浸渍处理改性分子筛以增强分子筛表面的酸活性中心.并采用红外光谱、扫描电镜、透射电镜等分析方法对试样进行了表征,结果表明,制得的催化剂S2-4-/Al2O3-ZrO2/SBA-15仍然保持高度有序的介孔一维六角结构.并将其催化剂用于棕榈酸与甲醇的酯化反应中,采用正交实验确定较佳的工艺条件为:催化剂用量为1.2g,n(棕榈酸)∶n(甲醇)=1∶12,反应时间为9h,此条件下棕榈酸甲酯的反应收率可以达到82.3％,实验表明所合成的固体酸催化剂具有良好的催化性能.     

Co掺杂对Ce/MCM-41和Ce/SBA-15催化剂催化氧化甲苯性能的影响

以分子筛为载体,采用等体积浸渍法制备Ce/SBA-15、Ce/MCM-41、Ce Co/SBA-15和Ce Co/MCM-41催化剂。用N2吸附-脱附、X射线衍射、扫描电子显微镜、H2程序升温还原、X射线光电子能谱和傅立叶变换红外光谱等对载体和催化剂进行表征,并考察催化剂催化氧化甲苯的活性。结果表明,与载体相比,随着Ce和Co的浸渍,催化剂的比表面积和孔容下降,但仍然保持了载体的有序介孔结构。引入的Ce和Co没有进入分子筛骨架,而是以立方相固溶体形式存在于分子筛表面和孔道中。催化剂催化氧化甲苯活性顺序依次为:Ce Co/SBA-15>Ce Co/MCM-41>Ce/MCM-41>Ce/SBA-15。共浸渍Ce和Co的催化剂活性明显优于只浸渍Ce的催化剂,活性与其还原性能直接相关,Ce Co/SBA-15催化剂具有最低的还原温度和最好的供氧能力,从而表现出最优的催化性能。     

微波辅助ZrO2-SO42-/SBA-15催化合成棕榈酸甲酯

以三嵌段醚共聚物P123作为模板剂、正硅酸乙酯为硅源,合成介孔分子筛SBA-15.以SBA-15为载体,利用尿素水解法制备ZrO2-SO42-改性的固体酸催化剂,对其进行表征.实验结果表明,合成的固体酸催化剂具有典型的介孔结构特征.将催化剂应用于微波法催化合成棕榈酸甲酯,考察反应时间、反应温度、辐射功率、酸醇物质的量比和催化剂用量对酯化率的影响,结果表明,在n(十六酸)∶n(甲醇)=1∶15、SZ/SBA-15催化剂用量0.8g、反应时间20min、反应温度40℃和微波辐射功率400W条件下,酯化率可达87.70％,微波反应时间较传统合成方法大大缩短.     

介孔分子筛B-SBA-15催化合成柠檬酸三丁酯

采用直接和间接合成法,将硼原子嵌入介孔分子筛SBA-15骨架中,用柠檬酸与正丁醇的酯化反应评价催化剂的催化性能。间接和直接合成法合成的催化剂活性对比结果表明,间接合成法制备催化剂的活性高于直接合成催化剂。重点考察了催化剂中硅硼比、催化剂用量、反应温度和酸醇比等因素对间接合成催化剂酯化反应性能的影响。筛选出B-SBA-15催化剂最佳硅硼摩尔比为30∶1,最佳反应条件：催化剂用量为原料质量的1.5%,反应温度为130 ℃,酸醇摩尔比1∶6。试验结果表明,介孔分子筛催化剂 B-SBA-15具有较高的稳定性,是合成柠檬酸三丁酯较为理想的分子筛催化剂。     

基于固体酸HClO4/SBA-15催化的奥硝唑合成

将分子筛SBA-15上负载高氯酸,制备了一种固体酸催化剂(HCl O4/SBA-15),利用IR对其结构进行了表征。并以HCl O4/SBA-15为催化剂,2-甲基-5-硝基咪唑和环氧氯丙烷为原料合成了奥硝唑,考察了催化用量、反应时间、反应温度、不同溶剂对产物收率的影响。得到优化的反应条件为:催化剂质量分数为60%(以2-甲基-5-硝基咪唑的质量为基准,下同),异丙醇作溶剂,在0℃下反应8 h,奥硝唑收率达76.3%,纯度(HPLC)为99.8%。采用1HNMR、13CNMR和MS确认产物结构。该法合成的奥硝唑质量符合药典质量标准。催化剂重复使用3次后,产品收率仍能达到65.8%。     

介孔分子筛SBA-15-SO3H催化合成2-叔丁基对甲酚

以磺酸基介孔分子筛SBA-15-SO3H为催化剂,甲基叔丁基醚(MTBE)和对甲酚为原料合成了2-叔丁基对甲酚.考察了烷基化反应条件对反应转化率和选择性的影响以及催化剂的稳定性.结果表明,对甲酚转化率为87.4%,选择性为97.86%,SBA-15-SO3H分子筛是合成2-叔丁基对甲酚的理想催化剂.     

我国脂肪酸的生产和应用

简要介绍脂肪酸的分类、原料来源、生产工艺、品种以及用途。并对我国脂肪酸的生产现状进行了分析。重点介绍了脂肪酸在我国橡胶工业中、塑料助剂等领域的应用,脂肪酸甲酯作为表面活性剂在不同领域的广泛应用,最后还简述了癸二酸和改性醇酸树脂应用。     

酸液体系的研究现状分析和现场应用

酸化解堵与压裂改造相比,它具有施工相对简单和成本相对较低等特点,所以酸化解堵是一项各油田广泛使用的油气田增产技术。酸化解堵技术已有将近100历史,现已研制出具有不同特点的酸液体系,如乳化酸、泡沫酸、固体酸、多氢酸等,基本能满足复杂地质条件对酸液的要求。     

油酸的精制研究

油酸酰胺是一种很好的塑料添加剂 ,可用作塑料加工成型时的脱膜剂、润滑剂。油酸的原料来源很广 ,牛油、羊油、猪油等动物油油脂以及大豆油、花生油、棕榈油等植物油脂中都含有大量的油酸。由于油酸的来源和生产方法多种多样 ,因此其所含的脂肪酸种类及含量都不尽相同。除油酸外 ,还有亚油酸、亚麻酸等高不饱和脂肪酸。针对油酸中因含有大量的多不饱和组分如亚油酸、亚麻酸而容易产生氧化泛黄的问题 ,采取了尿素络合法对原料油酸进行精制 ,以减少原料中亚油酸、亚麻酸组分的含量。经气相色谱验证 ,产品达到了应用指标 ,提高了产品的抗氧性。     

The Growth‐Inhibiting Effects of Beef Fatty Acids on MCF‐7 Cells Are Influenced Mostly by the Depot Location and Inconsistently by the Biohydrogenation Intermediate Content

Biohydrogenation intermediates (BHI) including conjugated linoleic acid (CLA) isomers are formed during ruminal biohydrogenation of polyunsaturated fatty acids (PUFA) in ruminants. Although many studies have examined the anticarcinogenic effects of CLA, few studies have reported the anticarcinogenic properties of BHI in their natural form found in dairy and beef fats. The present study compared the growth‐inhibitory effects of fatty acids from beef perirenal fat (PRF) or subcutaneous fat (SCF) with low or high levels of BHI in MCF‐7 human breast cancer cells. Cells were exposed for 72 h to media containing increasing doses (50 to 400 μM) of different beef fat treatments. Fatty‐acid analysis showed that BHI were readily incorporated into cell phospholipids (PL) in a treatment‐dependent manner, but higher BHI in PL did not consistently inhibit growth. Culturing with low‐BHI PRF or high‐BHI PRF did not lead to growth inhibition, but low‐BHI SCF inhibited growth, and inhibition was further increased by high‐BHI SCF. Other classes of fatty acids may, therefore, be interacting with BHI resulting in differential effects on growth inhibition in human breast cancer cells.     

磷钼杂多酸的合成研究

介绍了磷钼杂多酸的合成。通过正交试验探讨了反应物料量比、三氧化钼浓度、反应温度和反应时间对产物产率的影响。结果表明,最适宜的反应条件为:反应物量比n(三氧化钼)∶n(磷酸)=12∶1.0、反应温度t=70℃、反应时间7 h、三氧化钼与水的质量比1∶8。经红外光谱分析及熔点测定确定所得产品为磷钼杂多酸化合物。并以磷钼杂多酸取代硫酸作催化剂制备乙酸乙醋来研究其催化活性,并与硫酸做催化剂进行对比实验收率为70.75%,超过硫酸催化剂水平。     

Fatty Acid Profiles in Sunflower Grains During Storage in Different Environments

This study aimed to evaluate the fatty acid profiles of sunflower oil extracted from hybrid grains produced and stored in different environments. The trials were conducted in Teresina (Piauí), Vilhena (Rondônia), and Jaguariúna (São Paulo) in randomized complete block design with 4 replicates. After harvesting, grains from 1 high oleic and 3 traditional hybrids were packed in kraft paper bags and stored in a covered shed and in a cold chamber up to 12 months. The fatty acid profiles were determined by gas chromatography after 0, 4, 8, and 12 months of storage. Analyses of variance were conducted in a split‐plot design, with hybrids being considered as whole plots and storage times as subplots. Tukey's test was performed to compare hybrids and regression analyses for storage times. The initial fatty acid profile of the grains of the same hybrid varied depending on the production location. The grain storage of high oleic and traditional sunflower hybrids during 12 months in covered shed and in cold chamber resulted in little changes in oil fatty acid profiles, regardless of the initial contents. These changes occurred only for linoleic and palmitic acids.     

Fatty Acid Profiles of Oil Obtained from Mid-Oleic Sunflowers Grown in Tropical Region

This study aimed to verify whether the fatty acid profiles of mid-oleic genotypes grown in the tropical region of Brazil fit the Codex Alimentarius and to examine the possibility of using traditional inbred lines to produce high-oleic hybrids. For this purpose, we assessed the fatty acid profile of six mid-oleic hybrids grown in environments with different minimum temperatures during oil formation in the achenes. The tests were conducted between 2015 and 2017 in an experimentally randomized complete block design with four replications. The oleic, linoleic, palmitic, and stearic acid contents were determined using gas chromatography. The mid-oleic hybrids presented varying levels of fatty acids, with oleic acid ranging between 43.6% and 84.6%, linoleic acid between 8.5% and 45.6%, palmitic acid between 3.9% and 5.7%, and stearic acid between 2.2% and 6.2%. Some of the fatty acid values were outside the ranges established by the CODEX STAN 210-1999 and were characteristic of high-oleic type sunflowers. This finding shows that we can take advantage of the potential of combining traditional inbred lines to produce high-oleic hybrids for faster and more economical breeding programs in these environments.     

Quality of Sunflower Oil Obtained in the Main Producing Region of Brazil: Adherence to the Codex Alimentarius

The objective of this work was to evaluate the quality of the oil extracted from sunflower achenes grown in Campo Novo de Parecis, the main producing region of Brazil, to optimize its use by the processing and food industries. In addition, the fatty acid profiles of the oil were checked for their adherence to the CODEX STAN 210–1999. Traditional and high-oleic genotypes were grown between 2014 and 2017 during trials with a randomized complete block experimental design with four replications. The contents of oleic, linoleic, palmitic, and stearic acids were determined using gas chromatography. The fatty acid profiles of traditional genotypes were observed to be outside the ranges established by the CODEX, with an oleic acid content above 39.4% and linoleic, palmitic, and stearic acid values lower than 48.3%, 2.7%, and 5.0%, respectively, as well as high-oleic sunflower oil with a stearic acid content of less than 2.6%. The availability of this information can, on the one hand, positively impact industries and encourage the use of better quality raw materials that are more technologically and nutritionally adequate. On the other hand, the commercialization of sunflower oil with a fatty acid profile outside the ranges established by CODEX can be difficult, because the contents are out of specification due to the climatic conditions in the cropping region.     

质子酸催化合成α-氯代十二酸工艺研究

采用廉价的浓硫酸为催化剂,氧气为自由基捕集剂,以十二酸为原料,经氯化合成α-氯代十二酸。系统考察了反应温度、催化剂用量、氯气流量、氧氯比、反应时间等因素的影响,得到最佳工艺条件:十二酸20 g,在反应温度135℃、催化剂10%、氯气流量50 mL·min-1、vO2/vCl2=1∶2、反应时间3 h,可实现十二酸基本完全转化,目标产物α-氯代十二酸选择性达到94.5%。     

草酸作助剂磷钨酸催化H2O2氧化环己醇合成己二酸

在无有机溶剂、无相转移催化剂条件下,以草酸作助剂,采用磷钨酸催化过氧化氢氧化环己醇的方法来制备己二酸。考察了磷钨酸用量、反应时间、反应温度、过氧化氢用量及草酸用量对己二酸的分离产率的影响,得到最佳工艺条件,即环己醇10.51 mL、磷钨酸0.6 mmol/L、草酸1.0 mmol/L,H2O2(30%)70 mL,温度85℃、时间8 h,己二酸的最大分离产率为77.83%,纯度为99.9%。