糠醇加氢制四氢糠醇催化剂的研究

制备了负载型镍催化剂 ,并加入碱性和过渡金属氧化物助剂 ,各种氧化物总负载量低于催化剂质量的 30 %。在 393～ 413K、0 .2 5～ 0 .4h-1、2 .0～ 4.0MPa条件下 ,用上述催化剂加氢还原糠醇制备四氢糠醇。对于含少量助剂的镍催化剂Ⅱ ,在 393K、4.0MPa和空速 0 .2 5h-1时 ,糠醇转化率可达 99%以上 ,四氢糠醇收率和选择性都达到或接近 97%。在相同反应条件和糠醇转化率条件下 ,四氢糠醇收率和选择性均比没有助剂的镍催化剂Ⅰ高 2 .0 % ,比骨架镍催化剂高3.0 %     

高活性、高选择性骨架镍在糠醇加氢中的应用研究

研究了以骨架镍为加氢催化剂,以糠醇为原料制备四氢糠醇。在中温和高温下制备了两种骨架镍催化剂A和B,研究了不同的反应条件对两种骨架镍催化剂的影响,确定了最佳反应条件。骨架镍催化剂A在60℃,7MPa,用量为4g/100mL糠醇时,四氢糠醇选择性99 56%,收率可达99 41%。骨架镍催化剂B在60℃,5MPa,用量为4g/100mL糠醇时,四氢糠醇的选择性、收率可接近100 00%。     

采用骨架钴和骨架镍催化剂加氢还原制备糠醇的研究

从钼、铬、铜和铁中筛选金属铬和铁作为助催化剂加入骨架钴或骨架镍催化剂，铬和铁的量分别为催化剂质量的３％和１％。在１００～１２０℃、１０～１２ＭＰａ条件下，用上述骨架钴或骨架镍催化剂在乙醇溶剂中，氢化还原糠醛制备糠醇。用骨架镍催化剂，反应产物含有７８５％的糠醇和１９６％的四氢糠醇；用骨架钴催化剂，反应产物含有９８８％的糠醇和０８％的四氢糠醇，收率９４％。在无乙醇溶剂条件下，反应产物含有９０５％的糠醇、０３％的四氢糠醇和９２％的糠醛。在１８０℃条件下，反应产物含有９０８％的糠醇和８９％的四氢糠醇。     

温和条件下糠醇加氢催化剂性能的研究

本文选用Ru/C、Ru/Al₂O₃、Pd/C、Pd/Al₂O₃、Pt/C、雷尼镍等催化剂用于糠醇加氢的釜式反应研究。研究发现,Ru/C催化剂在糠醇加氢制备四氢糠醇的反应中具有良好的反应性能。研究了在Ru/C催化剂作用下溶剂、反应温度、氢气压力、反应时间、催化剂的用量等因素对反应的影响,并对工艺条件进行了优化。得到最佳工艺条件：异丙醇作溶剂,反应温度为60℃、氢气压力为3 MPa、反应时间为6 h,原料与催化剂的质量比为20:1,糠醇的转化率达到100%,四氢糠醇的选择性大于95%。     

采用骨加钴和骨架镍催化剂加氢还原制备糠醇的研究

从钼、铬、铜和铁中筛选金属和铁作为助催化剂加入骨架钴或骨架镍催化剂,铬和铁的量分别为催化剂质量的３％和１％。在１００￣１２０℃、１．０￣１．２ＭＰａ条件下,用上述骨架钴或骨架醇和１９．６％的四氯糠醇;用骨架钴催化剂,反应产物含有７８．５％的糖醇和１９．６％的四氢糠醇;用骨架钴催化剂,反应产物含有９８．８％的糠醇和０．８％的四氢糖醇,收率９４％。在乙醇溶剂条件下,反应产物含有９０．５％的糠醇、０．３     

载体及镍源对镍催化剂催化苯酐选择性加氢反应的影响

分别以SiO2、TiO2、TiO2-SiO2、TiO2-Al2O3和TiO2-ZrO2为载体,以硝酸镍为镍源,采用浸溃法制备出一系列镍基催化剂,考察了不同载体对镍催化剂催化苯酐选择性加氢合成苯酞性能的影响;并考察了以TiO2-ZrO2为载体,分别以硝酸镍、乙酸镍和柠檬酸镍为镍源制备的镍催化剂的加氢性能.通过BET、XRD、SEM等方法对催化剂进行了表征.结果表明,载体对镍催化剂上苯酐加氢反应的影响较大,其中复合氧化物TiO2-SiO2和TiO2-ZrO2负载的镍催化剂上Niu活性组分晶粒度较小,分散度较高,催化剂表现出很好的催化活性和苯酞选择性.此外,以不同镍源制备的Ni/TiO2-ZrO2催化剂性能差异较明显,由乙酸镍制备的催化剂上Niu物种粒度较大,活性较低,由硝酸镍和柠檬酸镍制备的催化剂表现出很高的催化活性和选择性,其中由柠檬酸镍制备的催化剂性能略高于硝酸镍,在实验反应条件下,苯酐转化率为97.1%,苯酞收率为92.9%.     

Ni/ZnO-ZrO2催化低温乙醇水蒸气重整制氢

以草酸钠为共沉淀剂,采用共沉淀法制备了以ZnO-ZrO2为载体的镍基乙醇水蒸气重整制氢催化剂(Ni/ZnO-ZrO2)。考察了不同锌锆摩尔比的ZnO-ZrO2负载的镍基催化剂在300～450℃催化乙醇水蒸气重整制氢的反应性能。用TPR、TPO、XRD对催化剂试样进行了表征。结果表明,当n(Zn)∶n(Zr)=1∶1,Ni负载质量分数10%时,催化剂中有镍锌复合氧化物生成,350℃时乙醇转化率达100%,450℃氢气选择性接近90%;TPO结果表明,ZnO-ZrO2复合载体可以降低催化剂上的积炭量。     

Cu/TiO_2-SiO_2催化剂的制备及糠醛选择加氢活性研究

采用溶胶凝胶-水热法制备Cu/TiO2-SiO2催化剂,并运用XRD、BET对催化剂进行表征,以糠醛选择加氢制糠醇反应为探针,考察载体组成及Cu含量对催化剂活性的影响。结果表明,载体中引入适量的TiO2能够抑制Cu晶粒的增长,改善Cu粒子在催化剂中的分散性。载体中TiO2质量分数40%,Cu负载量(质量分数)20%时,制备的Cu/TiO2-SiO2催化剂具有较好的催化活性。     

Ni／TiO2催化剂催化邻硝基氯苯加氢制备2，2’-二氯氢化偶氮苯

采用浸渍法制备Ni/TiO2催化剂用于邻硝基氯苯加氢制备2,2'-二氯氢化偶氮苯,通过BET、XRD、SEM和活性评价等方法对催化剂的物化性质及催化性能进行了研究,考察了不同的镍负载量的Ni/TiO2催化剂以及反应温度、碱的用量等工艺条件对催化加氢法制备2,2'-二氯氢化偶氮苯的影响.结果表明,镍负载量为30%,反应温度控制在353K～363K,碱与邻硝基氯苯质量比为0.2时,邻硝基氯苯的转化率及2,2'-二氯氢化偶氮苯的选择性均高于99.0%.分析表明,影响Ni/TiO2催化剂活性及选择性的主要因素是催化剂的活性比表面积及载体TiO2与金属镍之间的强相互作用.     

新型负载型镍系催化剂的制备与应用研究

以羰基镍为源,制备了一系列高活性、低含量负载型镍催化剂。利用苯乙烯的加氢反应考察了催化剂载体类型、反应温度、反应压力、催化剂用量等因素对催化剂性能的影响以及催化剂的重复性能。结果如下:LY8062c载体的性能最为优异;反应活性随反应温度和压力的增大而增强;催化剂的用量少,镍的负载量低;本方法制备的催化剂重复使用性能较好。     

Ether alcohol sulfates from oleyl alcohol

Oleyl alcohol was caused to react with ethylene oxide, propylene oxide, and 1,2-butylene oxide in the presence of an alkaline catalyst. The first and second derivatives from each reaction were isolated by fractional distillation. Sulfation with dioxane-SO₃ gave high-purity oleyl ether sulfates, easily soluble, with good detergent and lime soap-dispersing properties. The use of chlorosulfonic acid or sulfuric acid as the sulfating agent for oleyl ether alcohols resulted in about 60% retention of the double bond, compared with oleyl alcohol, which under the same conditions retained only about 25% unsaturation. Oleyl ether alcohols sulfated with chlorosulfuric acid or sulfuric acid are easily sobuble and have good lime soap-dispersing properties. They are able to solubilize less soluble soaps and saturated ether alcohol sulfates. Presented at the AOCS Meeting, New Orleans, May 1967 E. Utiliz. Res. Dev. Div., ARS, USDA     

Polyvinyl alcohol and modified polyvinyl alcohol reverse osmosis membranes

A study was conducted on the insolubilization of polyvinyl alcohol. Polyvinyl alcohol was regarded as a stable material for the formation of gel layer base membranes, which could then be further modified to produce RO membranes with good salt retention. This paper reports the study of the in situ insolubilization of polyvinyl alcohol membranes. Laboratory and field trial experiments were conducted with some of these membranes, and the results are reported on. Some results of the first chemically modified polyvinyl alcohol membranes are also given.     

丁辛醇生产中重组分的利用途径

概述了以丙烯为原料的羰基合成反应系统中重组分的形成 ,较详细地阐述了国外先进的利用途径 ,并根据大庆石化公司化工二厂丁辛醇装置的具体情况提出了可采用的技术工艺路线。     

The determination of resudual alcohol in defatted alcohol washed soybean flakes

A method is deseribed for determination of residual alcohol in soybean flakes washed with aqueous alcohol and desolventized to prepare a high-protein food supplement. Theamount of alcohol removed from the flakes by extraction with acetone is determined quantitatively by esterification with phthalic anhydride. An excess of reagent is required since water, present in the sample causes a secondary reaction which consumes phthalic anhydride. This analysis has been applied to flakes containing from 0.2 to 10% of methanol, ethanol, or isopropanol. Accuracy of the method was established by adding known amounts of the three alcohols to soybean flakes. A relative error of less than 1% was obtained with a standard derivation of 0.05%.     

醇基液体燃料中醇含量检测方法探讨

建立了气相色谱法定量分析醇基液体燃料中甲醇、乙醇含量的分析方法。该方法以水为萃取溶剂,采用Porapark T玻璃填充柱分离,氢火焰离子化检测器检测,外标法定量。结果证明,该方法具有较好的精密度和准确度。     

The yeast alcohol dehydrogenase catalysed conversion of cinnamaldehyde to cinnamyl alcohol

The kinetics of the conversion of trans-cinnamaldehyde to trans-cinnamyl alcohol catalysed by yeast alcohol dehydrogenase (EC 1.1.1.1) have been characterised. Reaction with the free enzyme is curtailed after a short time as a result of inactivation by the substrate. It has been shown that immobilisation of the enzyme provides substantial protection against this inactivation. Use of the immobilised enzyme in a flow-through reactor further enhanced the enzyme lifetime, creating a viable synthetic process. The product cinnamyl alcohol may be recovered by continuous solvent extraction.     

Determination of chirality of alcohol or latent alcohol semiochemicals in individual insects

A method is described for determining the enantiomeric composition of chiral alcohols, lactones, and hydroxy acids in quantities ranging from 25 ng to 10 g. Derivatization of the substance with chirally pure acetyl lactate, followed by splitless capillary gas chromatography, enables enantiomeric determinations to be made within 1–3% of the actual value. This technique was applied in the determination of semiochemical inIps pini (Say),Apis mellifera (L.), andCryptolestes ferrugineus (Stephens). The results indicate that considerable variability exists within populations of some insects in the composition of their chiral semiochemicals, whereas others produce substances of constant composition.     

高碳醇的合成

首次选用石蜡、硼酸为原料,通过液相氧化反应合成硼酸酯,再与氢氧化钠发生水解反应制得高碳醇。应用红外定量分析原理对其含量进行分析。得到制备高碳醇的较优工艺条件：n（石蜡）∶n（硼酸）=1∶4,氧化时间为6 h,氧化温度为170℃,水解温度为80℃,水解时间为1 h。产物收率约为12.7%。