硅钨钼酸掺杂聚苯胺催化合成环己酮1，2-丙二醇缩酮

首次采用浸渍法制备了硅钨钼酸掺杂聚苯胺催化剂H4SiW6Mo6O40／PAn。以环己酮和1，2．丙二醇为原料合成环己酮1，2-丙二醇缩酮。探讨了硅钨钼酸掺杂聚苯胺催化剂对缩酮反应的催化活性，较系统地研究了原料量比，催化剂用量，反应时间诸因素对产品收率的影响。实验表明：硅钨钼酸掺杂聚苯胺是合成环己酮1,2-丙二醇缩酮的良好催化剂，在n（环己酮）：n（1，2-丙二醇）=1：1．7，催化剂用量为反应物料总质量的1．0％，环己烷为带水剂，反应时间1．0h的优化条件下，环己酮1．2-丙二醇缩酮的收率可达84．6％。     

乙醇选择性还原NOx的组合催化剂研究和应用

为了解决富氧条件下NOx排放问题，在发动机台架上对以乙醇作为还原剂时Ag／Al2O3的特性进行了实验研究，同时对Ag／Al2O3＋Cu／TiO2和Ag／Al2O3＋Cu／TiO2＋Pt／TiO2两种组合催化剂降低NOx的效果进行了对比分析。研究表明：Ag／Al2O3具有很好的NOx去除活性；与Ag／Al2O3＋Cu／TiO2相比，Ag／Al2O3＋Cu／TiO2＋Pt／TiO2催化剂组合具有更好的去除NOx并抑制THC和CO排放升高的综合性能。将Ag／Al2O3＋Cu／TiO2＋Pt／TiO2应用在实验发动机上，在EurolHESC工况下取得了64％的稳态Nq转化效率，并保持THC和CO排放基本不变。另外，本文也分析了组合催化剂对微粒（PM）各组分的影响。     

工艺参数对合成ZnO／Ag纳米复合抗菌剂产率的影响

通过正交实验，研究了反应温度、反应时间、反应物配比对ZnO／Ag纳米复合抗菌剂合成产率的影响规律。获得了高产率合成ZnO／Ag纳米复合抗菌剂的优选工艺条件：反应温度为10～25℃，ZnSO4与NH4HCO3的摩尔比为1：2-2．5，ZnSO4与NH4HCO3的反应时间为2．5～3h，AgNO3与NH4HCO3的摩尔比为1：1．5～2，反应时间为0．5h，ZnO／Ag的产率超过98％。XRD、TEM和SAED结果表明：ZnO／Ag纳米复合抗菌剂为具有纤锌矿结构的ZnO和立方结构的Ag组成。粒径为15～25nm，分散性较好。     

低游离酚壳法用热塑性酚醛树脂的合成

采用一种新型催化剂，用正交实验方法研究了催化剂用量、甲醛与苯酚配比、反应温度和反应时间对树脂产率的影响，优化了配方。最佳工艺为：反应温度85℃，催化剂用量2．0％，甲醛与苯酚的摩系比为1：1，反应时间6h，得到产率为112．1％，软化点为92．8℃的热塑性酚醛树脂。经高效液相色谱分析，树脂中游离酚为0．58％，并墨用^13C-NMR对其结构进行了表征。与一般合成酚醛树脂的方法相比，该工艺提高了产率，降低了树脂中游离酚含量。     

二氧化钛负载磷钨钼杂多酸催化合成缩醛(酮)

首次采用回流法制备了二氧化钛负载磷钨钼杂多酸催化剂H3PW6Mo6O40/TiO2,该催化剂的适宜制备条件为原料质量比m(TiO2)∶m(H3PW6Mo6O40)=1∶2.0,水的用量30 mL,回流反应时间2.0 h,活化温度150℃.以H3PW6Mo6O40/TiO2为催化剂,对以环己酮、丁酮、正丁醛、苯甲醛与二元醇(乙二醇、1,2-丙二醇)为原料合成的8种缩醛(酮)反应条件进行对比,较系统研究了醛(酮)与二元醇摩尔比、催化剂用量、反应时间对收率的影响.结果表明,在n(醛(酮∶n(乙二醇(1,2-丙二醇))=1.0∶1.4、催化剂用量占反应物料总质量的0.8%、反应时间1.0 h的条件下,8种缩醛(酮)的收率在53.0%～86.9%之间.     

赤泥酸浸的试验研究

以HCl和H2SO4为浸出剂,对赤泥中各有价金属的浸出条件进行了较系统的试验研究。结果表明,先采取低浓度HCl浸出,残渣再用高浓度H2SO4分解的两段浸出方式为佳。一段浸取盐酸浓度为6mol／L．液固比L／S=4：1．反应温度50℃,反应时间1h。Sc2O3的浸出率大于80％,TiO2的浸出率为1％左右。二段浸取硫酸浓度为92％．酸渣比为3：1．熟化温度为200℃,熟化时间为1．5h。TiO2的浸出率为96．57％。     

新型阻燃剂磷酸单（2—羟基丙基）酯及其锑合物的合成

以环氧丙烷、磷酸为原料合成了磷酸单（２－羟基丙基）酯，并以磷酸单（２－羟基丙基）酯和三氧化二锑为原料合成了磷酸单（２－羟基丙基）酯锑。实验结果表明，以丙酮为溶剂、反应温度为３０℃、反应时间为２ｈ，在催化作用下，磷酸单（２－羟基丙基）酯的收率为７２％；磷酸单（２－羟基丙基）酯锑的合成条件为以二甲基亚砜为溶剂、反应时间为４ｈ，产品的收率为８２％。将两种产品作为阻燃剂添加到环氧树脂中，添加量为１５％时，其氧化指数分别为２３．７和２６．８。     

HF-PCVD法TiO2纳米晶的粒径与晶型控制

以TiCl4和O2为反应体系，采用高频等离子化学气相沉积(HF-PCVD)法制备了晶化完整的锐钛和金红石混晶型TiO2纳米晶，球形体的晶粒分散性良好，分布较为均匀：研究了控制粒径大小和晶相组成的关键反应条件。XPS，TEM，XRD结果显示：增加TiCl4进料量、延长停留时间均利于锐钛相向金红石相转化，但粒径有所增大：添加A1C13使金红石相含量较未掺杂时有较大幅度提高，且粒径随掺铝量增加而减小。本实验条件下，TiO2纳米晶的粒径为25nm～60nm，金红石相含量在12．O％～53．6％间可控。     

高性能天然气汽车尾气净化钯催化剂的研制

考察了Pd、Pt、Pd-Rh和Pt-Rh对天然气汽车尾气净化催化剂的影响。制备了以La-A12O3、La-A12O3 Ce2O-ZrO2和La-A12O3 CeO2-ZrO2．MnOx为载体的天然气汽车尾气净化钯催化剂。结果表明,Pd／A12O3 CeO2．ZrO2．MnOx催化剂能极大地降低CH4的起燃温度并显著改善催化剂的反应性能。该催化剂经1000℃水热老化后,CH4的起燃温度仅上升了40℃,表现出优异的抗老化性能。     

自蔓延高温合成TiB2／Al2O3复合材料的力学性能

以普通商用TiO2为原料，与铝粉、碳化硼进行自蔓延（SHS）高温合成TiB2／Al2O3复合材料，通过差热和X射线衍射分析，确定了TiO2、Al及B4C的反应机制，得到了生成TiB2／Al2O3复合粉体的最佳工艺条件。测定了TiB2／Al2O3复合粉体相关的力学性能，得到材料的抗压强度为87．2MPa，抗弯曲强度为104．3MPa。SEM观察发现生成相中存在大量的气相或气孔，生成物微观区域不太均匀，材料的断裂形式主要为脆性断裂，生成物的颗粒尺寸为亚微米级。     

Short communication Catalytic synthesis of butyric esters with TiSiW_(12)O_(40)/TiO_2

The catalytic activities of TiSiW12O40/TiO2 in synthesizing ethyl ester, propyl ester, n-butyl ester, and amyl ester were reported. It was demonstrated that TiSiW12O40/TiO2 is an excellent catalyst. Various factors concerned with esterifica-tion were investigated. The optimum conditions were found: the mole ratio of alcohol to acid is 1.3:1, the mass ratio of catalyst to reactants is 1.5%, and the reaction time is 1.0 h. Under the optimum conditions, the yields are 88.0% for ethyl ester, 94.5% for propyl ester, 98.6% for n-butyl ester, 99.1 % for n-amyl ester, and 96.7% for iso-amyl ester, respectively.     

Catalytic synthesis of butyric esters with TiSiW12O40/TiO2

The catalytic activities of TiSiW12O40/TiO2 in synthesizing ethyl ester, propyl ester, n-butyl ester, and amyl esterwere reported. It was demonstrated that TiSiW12O40/TiO2is an excellent catalyst. Various factors concemed with esterifica-tion were investigated. The optimum conditions were found: the mole ratio of alcohol to acid is 1.3:1, the mass ratio ofcatalyst to reactants is 1.5%, and the reaction time is 1.0 h. Under the optimum conditions, the yields are 88.0% for ethylester, 94.5% for propyl ester, 98.6% for n-butyl ester, 99.1% for n-amyl ester, and 96.7% for iso-amyl ester, respectively.     

稀土固体超强酸SO_4~(2-)/TiO_2/La~(3+)的制备及其催化酯化作用

制备了稀土固体超强酸 SO2 - 4 / Ti O2 / L a3+ ,研究了以其为催化剂 ,癸二酸和无水乙醇为原料合成癸二酸二乙酯 ,并考察了影响反应的因素。结果表明 ,它是一种良好的酯化催化剂。     

Preparation of SO2-4/TiO2-WO3 solid superacid and its catalytic activity in acetalation and ketalation

SO2-4/TiO2-WO3 was prepared and its catalytic activity under different synthetic conditions was discussed with esterification of n-butanoic acid and n-butyl alcohol as probing reaction. The optimum conditions are found that the mass fraction of H2WO4 used in the compound is 12.5%, the calcination temperature is 580℃, the calcination time is 3 h, and the soaked consistency of H2SO4 is 1.0 mol.L-1. Then SO2-4 /TiO2-WO3 was applied as the catalyst in the catalytic synthesis of eight similar important ketals and acetals under the optimum conditions and revealed high catalytic activity. On condition that the molar ratio of aldehyde/ketone to glycol is 1:1.5, the mass fraction of the catalyst used in the reactants is 0.5%, and the reaction time is 1.0 h, the yields of ketals and acetals can reach 64.2%-95.1%. Moreover, it can be easily recovered and reused.     

Korrosionsinhibierung von Aluminiumpigmenten durch Ester der Gallussäure

Corrosion inhibition of aluminium pigments by esters of gallic acid Aluminium pigments corrode in mixtures of water and butyl glycol with the evolution of hydrogen, which can easily be measured gasvolumetrically. This corrosion reaction can be inhibited with addition of esters of gallic acid (gallates). The corrosion inhibiting effect of the gallates increases with increasing chain length of the ester alcohol; this connexion between the chemical structure of the inhibitors and the evolved volumes of hydrogen can be correlated mathematically with the help of an exponential function. The best inhibitor dodecyl gallate, which is an amphiphilic molecule with a chelating head group, showed protective values of about 99 %. To corroborate the assumption, that amphiphilic molecules with chelating head groups are in general effective inhibitors for the examined corrosion reaction, a second example, the amphiphilic agaric acid (α-hexadecyl citric acid) was tested in comparison to the head group (citric acid); again the amphiphilic molecule inhibited the corrosion reaction of aluminium pigment more effectively as the head group alone.     

Application conditions for ester cured alkaline phenolic resin sand

Five organic esters with different curing speeds: propylene carbonate(i.e. high-speed ester A); 1, 4-butyrolactone; glycerol triacetate(i.e. medium-speed ester B); glycerol diacetate; dibasic ester(DBE)(i.e. lowspeed ester C), were chosen to react with alkaline phenolic resin to analyze the application conditions of ester cured alkaline phenolic resin. The relationships between the curing performances of the resin(including pH value, gel pH value, gel time of resin solution, heat release rate of the curing reaction and tensile strength of the resin sand) and the amount of added organic ester and curing temperature were investigated. The results indicated the following:(1) The optimal added amount of organic ester should be 25 wt.%-30 wt.% of alkaline phenolic resin and it must be above 20 wt.%-50 wt.% of the organic ester hydrolysis amount.(2) High-speed ester A(propylene carbonate) has a higher curing speed than 1, 4-butyrolactone, and they were both used as high-speed esters. Glycerol diacetate is not a high-speed ester in alkaline phenolic resin although it was used as a high-speed ester in ester cured sodium silicate sand; glycerol diacetate and glycerol triacetate can be used as medium-speed esters in alkaline phenolic resin.(3) High-speed ester A, medium-speed ester B(glycerol triacetate) and low-speed ester C(dibasic ester, i.e., DBE) should be used below 15 °C, 35 °C and 50 °C, respectively. High-speed ester A or lowspeed ester C should not be used alone but mixed with medium-speed ester B to improve the strength of the resin sand.(4) There should be a suitable solid content(generally 45 wt.%-65 wt.% of resin), alkali content(generally 10 wt.%-15 wt.% of resin) and viscosity of alkaline phenolic resin(generally 50-300 mPa·s) in the preparation of alkaline phenolic resin. Finally, the technique conditions of alkaline phenolic resin preparation and the application principles of organic ester were discussed.     

马来海松酸聚乙二醇酯的制备及助焊性能

以马来海松酸酐及聚乙二醇200为原料,ZnO为催化剂,制备得到4种不同酸值的马来海松酸聚乙二醇酯,通过傅里叶红外光谱(FT-IR)对产物的结构进行表征,并考察其对Sn0.7Cu无铅钎料的助焊性能. 结果表明,当马来海松酸酐与聚乙二醇的摩尔量之比为1:0.5,1:1.0,1:1.5及1:2.0时,反应体系的酸值分别在3,4,7和10 h后达到稳定,得到的马来海松酸聚乙二醇酯的酸值分别为212.5,178,125.3,72.7 mg/g;酸值为178 mg/g的马来海松酸聚乙二醇酯对Sn0.7Cu钎料的助焊效果最佳,其在铜基板上形成的焊点饱满,表面光亮,扩展率达到75.8%,优于未经改性的天然松香.     

Acylation and oxidation of primary amines and alcohols catalyzed by nanoporous polyaniline emeraldine salt

We described the convenient and efficient catalytic acylation and oxidation of primary amines and alcohols compounds into amide/ester or aldehyde compounds using nanoporous polyaniline emeraldine salts catalysts. The reaction mechanism of acylation by polyaniline emeraldine salt catalyst is explained by acid catalyzed addition–elimination reaction, whereas oxidation process is proposed to occur through a radical pathway.     

石煤钒矿硫酸活化常压浸出提钒工艺

研究石煤钒矿的硫酸活化提钒方法。分别考察矿石粒度、硫酸浓度、活化剂用量、催化剂用量、反应温度、反应时间和浸出液固比等因素对钒浸出率的影响。结果表明:石煤提钒的优化条件为矿石粒度小于74μm的占80%、硫酸浓度150 g/L、活化剂CaF2用量(相对于矿石)60 kg/t、催化剂R用量20 g/L、反应温度90℃、反应时间6 h、液固比(体积/质量,mL/g)2:1,在此优化条件下,钒浸出率可达94%以上;在优化条件下,采用两段逆流浸出,可有效减少活化剂CaF2以及浸出剂硫酸的消耗量;经过两段逆流浸出萃取反萃氧化水解工艺,全流程钒资源总回收率可达86.9%;V2O5产品纯度高于99.5%。     

Protection of 2-(3-thienyl)ethanol with 3-thienylacetic acid and hard cross-linked conducting films by electropolymerization of the ester

The ester (compound 1) of 2-(3-thienyl)ethanol (T-etOH) with 3-thienylacetic acid was synthesized as a monomer whose two thiophene groups could be electropolymerized independently, becoming members of different polymer chains in a highly cross-linked highly insoluble polymer. Indeed, 1 was electropolymerized successfully alone and together with 3-methylthiophene (3MeT). Films of poly(1) are hard (3H, as opposed to <6B for poly(3MeT)), and the close proximity of the polymeric strands creates π-stacking interactions. The behavior of 1 suggests that by: (a) limiting the potential used for the oxidation of monomeric esters of T-etOH at the foot of their oxidation waves (<1.8 V versus Ag/AgCl) and (b) compensating for the decrease in the electrogenerated radical concentration by increasing the monomer concentration, practically all esters of T-etOH should be electropolymerizable. This was confirmed by durable film formation from the archetypical ester of T-etOH, the 2-(3-thienyl)ethyl acetate (T-etOAc), whose homoelectropolymerization is reported for the first time.