糠酸负载型钯催化剂选择性杂环氢化过程

采用水作溶剂的固定床操作系统,用钌、铑、钯、铂等作为担载金属,氧化硅、活性炭(AC)、γ-三氧化二铝等作为载体,制备了多种负载型催化剂,评价了它们的糠酸选择性杂环加氢催化性能.研究表明,金属钯的性价比最好,γ-三氧化二铝为催化剂的合适载体.优化了该催化剂上的操作条件,结果表明,在1.0 MPa、150℃、氢气空速4 000 h-1、糠酸水溶液的空速8.0 h-1的条件下,糠酸的色谱转化率达98.2%,四氢糠酸选择性为100%.催化剂1.0 w%Pd/γ-Al2O3连续运转260 h后未见活性和选择性下降,稳定性良好.提出了一个经济、环保、连续操作的糠酸选择性杂环加氢过程.     

Pd／γ-Al2O3催化剂上糠酸杂环选择性氢化甲酯化工艺

采用连续流动固定床微反应器,以糠酸、甲醇、氢气为原料, Pd/γ-Al2O3为催化剂,使糠酸一步加氢甲酯化生成α-四氢糠酸甲酯.研究了反应的温度、压力、气﹑液体流速等工艺条件对糠酸杂环选择性催化加氢甲酯化过程的影响.结果表明:在0.5MPa, 150℃,氢气流速5000mL*h-1,液体流速5.0mL*h-1(氢油比为50)时,呋喃甲酸转化率为99.0%,四氢糠酸甲酯的选择性98.2%,产率97.2%.催化剂连续运转360h后未见活性下降,稳定性良好.该工艺具有绿色、低压、易操作、高活性、高选择性、催化剂稳定、易分离等特点     

丁烯醛生产废水湿式催化氧化处理技术研究

利用双金属活性组分催化剂,考察了进仓温度、反应压力、催化剂空速和氧气用量等条件对催化湿式氧化处理某厂丁烯醛生产废水效果的影响,从而确定最优的工艺参数.对于该厂的丁烯醛生产废水,在进仓温度为190℃、反应压力为4.5 MPa、催化剂空速为1.5 h~(-1)及氧气用量为理论需氧量的1.25倍的反应条件下,丁烯醛生产废水COD降解率为97.2%、氨氮降解率为98.1%,为后续工程实施提供了基础数据.     

可见光辅助钯纳米催化剂的制备及应用研究

利用湿化学法的可见光动力学控制策略,在未添加表面活性剂的乙二醇水溶液体系中,以多壁碳纳米管(MWCNTs)为载体,通过一步法合成了钯多晶纳米催化剂,其平均粒径为16.5 nm.并通过傅立叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)、X射线衍射仪(XRD)和透射电子显微镜(TEM)完成了催化剂的微结构、组成和形貌的表征研究.结果表明,在可见光辅助下,乙二醇可以作为还原剂和稳定剂来制备纳米催化剂.由于金属的界面电子效应的影响,钯前驱体倾向于形成粒径比较大的多晶状颗粒.在对硝基苯酚(p-NP)的还原反应中,该催化剂的活化能为29.29 kJ/mol,室温下速率常数为0.248 4 min~(-1),显示出了较高的催化活性.     

非均相催化合成氨基甲酸甲酯工艺研究

以氧化铅为催化剂,甲醇与尿素为原料合成氨基甲酸甲酯.对所合成产物进行了熔点测定、红外、氢核磁谱及气相-质谱联用表征.考察了原料配比、反应温度、催化剂用量、反应时间等条件对合成反应的影响.在优化反应条件下MC的收率可达61.80%,选择性为98%.     

Fe-Mn/TiO_2低温选择催化还原NO_x

采用溶胶凝胶法制备Fe-Mn/TiO_2催化剂,考察Fe含量、水含量、空速、氧气浓度等条件对催化剂脱硝性能的影响.结果表明:Fe-Mn/TiO_2催化剂在100℃时,NO_x转化率达到90%;Fe/Ti摩尔比为0.2、煅烧温度500℃条件下制备的催化剂具有最高的脱硝活性,催化剂的活性温度窗口较宽,在80~375℃温度范围内转化率保持在80%以上;催化剂制备中所加H_2O含量8%时,催化剂活性最好;氧气浓度对NO_x去除率并无显著影响,只在较低温度阶段有所差别,即氧含量4%时低温100℃NO_x转化率达到80%;空速对催化剂脱硝率的影响主要在较低温度段(100℃).     

二氧化氯催化氧化中催化剂和实验条件的优选

研究了二氧化氯催化氧化法在处理难降解有机化工废水中催化剂的选择和实验条件的优化.在催化剂选择实验中以γ-Al2O3为载体共制备了29种催化剂,优选出Cu Co La Ce-O γ-Al2O3为本实验最佳的催化剂.通过实验确定本实验的最佳实验条件为:氧化剂24 mL/100 mL废水、反应时间70 min、pH＜7、催化剂投加量为3 g/100 mL废水.     

固体超强酸SO_4~(2-)/ZrO_2-TiO_2-Fe_2O_3催化合成乙酸异戊酯

用沉淀浸渍法制备固体超强酸SO42-/ZrO2-TiO2-Fe2O3催化剂,利用TG和XRD进行表征.将该催化剂用于醇酸反应制备乙酸异戊酯,考察了反应条件对酯化率的影响.结果表明,当Zr、Ti和Fe的摩尔比为1∶3∶2时,催化剂活性最高.其催化合成乙酸异戊酯的适宜工艺条件为:醇酸摩尔比1.3∶1,催化剂用量(以0.25 mol乙酸计)1.0 g,带水剂用量10 mL,反应时间3 h.在此条件下,酯化率达98.5%.     

固体超强酸SO2-4/ZrO2-TiO2-Fe2 O3催化合成乙酸异戊酯

用沉淀浸渍法制备固体超强酸SO24-/ZrO2-TiO2-Fe2O3催化剂,利用TG和XRD进行表征.将该催化剂用于醇酸反应制备乙酸异戊酯,考察了反应条件对酯化率的影响.结果表明,当Zr、Ti和Fe的摩尔比为1:3:2时,催化剂活性最高.其催化合成乙酸异戊酯的适宜工艺条件为:醇酸摩尔比1.3:1,催化剂用量(以0.25 mol乙酸计)1.0 g,带水剂用量10 mL,反应时间3 h.在此条件下,酯化率达98.5%.     

介孔磷酸锆催化活性及异山梨醇提纯

采用溶胶-凝胶法制备了一种介孔磷酸锆固体酸催化剂,通过X射线衍射、X射线荧光光谱、傅里叶红外光谱、比表面积及孔分布测定、吡啶红外吸附等表征手段确定了催化剂的结构特性,该催化剂在山梨醇脱水制备异山梨醇反应中表现出比传统固体酸催化剂更好的催化活性,由于固体酸催化剂具有与产物易分离的优点,通过对反应产物组分模拟简化了异山梨醇提纯工艺路线,制备异山梨醇纯度达到99.5%.制备的磷酸锆催化剂具有较大的潜力,可以很好地替代液体酸催化剂应用于反应之中,有着广阔的应用前景.     

A study on synthesis and oxidation mechanism of mono-alkyl phosphate

Oxidation of white phosphor, us by peroxides to produce mono-alkyl phosphate in the alcoholic solution has been studied under non-and catalytic conditions. In this paper, the mechanism of the oxidation process was analyzed. The content of mono-alkyl phosphalte in the product is affected by different types of alcoholic solution and peroxide solvent. The result shows the availabulity of the following order for the activity of the peroxide solvent and alcoholic solutions-tert-butyl hydroperoxide>(di) benzoyl peroxide>hydroperoxide; methanol> n-butyl alcohol> phenol. Under optimized reaction conditions: n (a white phosphorus) : n( tert-butyl hydroperoxide) : n (methanol)= 1:10:12, reaction temperature 80 ℃, reaction time 2.5 h, products of 80.0% mono-alkyl phosphonates can be provided when white phosphorus undergoes oxidation by tert-butyl hydroperoxide in the methanol solutions. When Cu (I), and Cn(Ⅱ) complexes are used as catalysts, it is possible to significantly enhance the oxidation of white phosphorus with the increase in the reaction rate. Th'e order for activity of catalysts is Cu(acac)2>Cu (CH3COO)2>Cu (C3 H7COO)2:>CuI>CuCI2. Noticeably, with Cu(acac)2 as catalyst, the selectivity for mono-alkyl phusphonates can reach 95% under adequate reaction conditions.     

Improvement of oil/water selectivity by stearic acid modified expanded perlite for oil spill cleanup

Ecological disasters and economic losses resulting from oil spills have reminded us the necessity for finding an environmentally friendly, cost-effective, and available in large-scale materials to minimize the oil spill effects. The development of high oil/water selectivity mineral sorbent for the removal of oil from the water is of great interest for oil spill cleanup. In this work, highly oil/water selectivity sorbent of expanded perlite modified with stearic acid was prepared by solution-immersion processes, and the characterization of sorbent was analyzed by Fourier transformation infrared (FT-IR) spectroscopy technique. The optimized amount of loaded stearic acid (SA) on the expanded perlite surface was found to be 2.0%. Then the sorption characteristics of unmodified expanded perlite (UMEP) and stearic acid modified expanded perlite (SMEP) were tested. The effects of different particles size, oil/water volume ratio and sorption simulated condition were investigated. It was found that expanded perlite modified with stearic acid could adsorb selectively oil from water in oil/water system. The maximum oil/water sorption ratio of SMEP was 46, which was about 191 times that of UMEP (0.24) in studied experimental range. The FT-IR analysis demonstrated the presence of long-chain alkyl group in the SMEP samples, which played an important role in oil/water selectivity of SMEP samples. The equilibrium were tested with Langmuir and Freundlich isotherm models, and oil sorption process of SMEP showed good correlation with the Langmuir isotherm model.     

一种固态聚醚型聚羧酸减水剂的合成及其机理研究

采用自由基本体聚合方法合成了一种便于包装运输储存的固态高效高性能聚醚型聚羧酸减水剂,通过对比实验研究了不同合成因素对水泥净浆流动度的影响关系,并优化了合成工艺.最佳工艺确定为：引发剂用量0.15g,链转移剂用量0.15g,丙烯酸用量8.17g,反应时间2h时,合成的固态聚醚型聚羧酸减水剂的减水效果最佳.采用表面张力,Zeta电位和吸附量初步探究其作用机理,其优异的分散效果主要依靠空间位阻实现.     

硅钨酸光催化降解甲基橙溶液研究

以硅钨酸为光催化剂,研究了其对模拟染料废水甲基橙的光催化脱色降解影响.结果表明,酸度、催化剂投加量、溶液初始浓度是影响催化降解效果的重要因素.最佳催化条件为,10mg/L的甲基橙溶液在紫外灯辐照下,硅钨酸浓度0.4g/L,溶液酸度pH=1.其对甲基橙溶液光催化降解效果比磷钨酸差.     

活性炭-臭氧氧化法预处理制药废水

采用活性炭催化臭氧氧化降解制药废水,考察了pH值、活性炭投加量、臭氧流量等因素对降解效果的影响,同时考察了活性炭催化臭氧氧化对废水的可生化性的影响.结果表明:pH值对去除效果影响显著,随着pH值增大,废水CODCr的去除率先上升,后降低;活性炭和臭氧的复合使用对反应体系有显著的协同催化效应,可使废水CODCr去除率由单独臭氧氧化的33.1%提高到72.57%.此外,活性炭催化臭氧氧化法显著提高了废水的可生化性,有利于进一步的生化处理.     

硅钨酸光催化降解甲基橙溶液研究

以硅钨酸为光催化剂,研究了其对模拟染料废水甲基橙的光催化脱色卫生解影响,结果表明,酸度、催化剂投加量、溶液初始浓度是影响催化降解效果的重要因素,最佳催化条件为,10mg/L的甲基橙溶液在紫外灯辐照下,硅钨酸浓度0.4g/L,溶液酸度pH=1,其对甲橙溶液光催化降解效果比磷钨酸差。     

环己烷上氨基和羟基的选择性反应-PM3研究

运用半经验的PM3方法计算反应体系中各原子的电荷分布和热力学函数,得到反应的平衡常数与理论产率,并考察了环己烷上不同取代基（氨基或羟基）在有、无催化剂时的不同选择性。结果表明反应能在较宽的温度范围内进行,且产物的含量能达到50％。     

特殊形貌氧化钙的制备及其催化合成生物柴油

利用化学还原法制备了不同形貌钙的氧化物,并研究了其作为固体催化剂制备生物柴油的催化性能.扫描电镜观察结果表明,钙的氧化物为六边形状和椭球状.60℃反应2 h的条件下,以六边形钙的氧化物为固体催化剂,生物柴油的转化率可以达到97.5%,高于椭球形钙的氧化物作为固体催化剂的85.6%.六边形状钙的氧化物优先暴露某一催化活性表面参与化学反应,其催化性能明显优于常见的球形结构,从而对生物柴油的催化转化效果更佳.     

四乙基碘化铵相转移催化合成N，N-二乙基苯胺

用四乙基碘化铵作相转移催化剂,在常压下由苯胺和溴乙烷合成N,N-二乙基苯胺,研究了多种反应因素对目的产物产率的影响,提出了常压催化合成目的产物的最佳工艺条件是：苯胺和溴乙烷的摩尔比为1：2.5,催化剂用量0．6g,在40mL质量分数为30×10^-2的氢氧化钠溶液中,反应温度55℃,常压反应5h,产品收率95．6％。     

A rapid method for the determination of dopamine in porcine muscle by pre-column derivatization and HPLC with fluorescence detection

A rapid method has been developed based on the sample preparation procedure named as QuEChERS （Quick, Easy, Cheap, Effective, Rugged and Safe）, combined with reversed-phase high performance liquid chromatography with fluorescence detector and C18 column after precolumn derivatization using o-phthalaldehyde and 2-mercaptoethanol to determine dopamine in porcine muscle. Methanol and deionized water （0.1% acetic acid, v/v） with a ratio of 60：40 was used as mobile phase. The flow rate was 0.8 mL/min and dopamine was eluted within 15 min. The linearity range was 0.003-8 μg/mL with r=0.9992. The detection limit for dopamine was 4 μg/kg and the quantification limit was 9 μg/kg. Recovery studies were carried out at 0.1, 0.5 and 1.0 mg/kg fortification levels and the average recoveries obtained ranged from 90.4% to 98.2% with relative standard deviations between 3.5% and 8.1%. The method was found to be suitable for detection of dopamine in animal product tissues at the maximum residue level.