Solvolysis and isomerization of phenyloxirane catalyzed with niobic acid

Solvolysis and isomerization of phenyloxirane were studied with niobic acid (Nb₂O₅.xH₂O) as catalyst. In aqueous solution, niobic acid showed much higher hydrolysis performances in activity and selectivity than other solid acid catalysts. Selectivity of alcoholysis with methanol was much higher than that with other alcohols because of simultaneous isomerization and dehydration of alcohol.     

Absence of expected side-reactions in the dehydration reaction of fructose to HMF in water over niobic acid catalyst

The catalytic dehydration of fructose (FRU) to 5-hydroxymethylfurfural (HMF) usually runs with the formation of several side products. Among these, levulinic acid (LA) is often reported as the product of a consecutive reaction of HMF re-hydration. In this work, side reactions of the dehydration of FRU performed in very green conditions (water as solvent and niobic acid as solid catalyst) are taken into account. Experimental evidences are given that, in the used conditions: i) HMF is a final stable product, ii) no formation of LA, either deriving from a consecutive reaction of HMF or directly from FRU transformation, was observed, and iii) LA does not react to give condensation products with any other chemical species present in the reaction mixture.     

Synthesis of bio-additives: Acetylation of glycerol over zirconia-based solid acid catalysts

Acetylation of glycerol with acetic acid was investigated over ZrO₂, TiO₂–ZrO₂, WO_x/TiO₂–ZrO₂ and MoO_x/TiO₂–ZrO₂ solid acid catalysts to synthesize monoacetin, diacetin and triacetin having interesting applications as bio-additives for petroleum fuels. The prepared catalysts were characterized by means of XRD, BET surface area, ammonia-TPD and FT-Raman techniques. The effect of various parameters such as reaction temperature, molar ratio of acetic acid to glycerol, catalyst wt.% and time-on-stream were studied to optimize the reaction conditions. Among various catalysts investigated, the MoO_x/TiO₂–ZrO₂ combination exhibited highest conversion (~ 100%) with best product selectivity, and a high time-on-stream stability.     

硅胶负载的磷钨酸催化剂上萘的异丙基化反应

以负载于硅胶(SiO2)上的磷钨酸为催化剂,在100 mL间歇式不锈钢高压反应釜中,研究了萘与异丙醇的烷基化反应。结果表明,中低负载量的磷钨酸均匀分散于SiO2孔道内,负载量超过30％则产生聚积。负载量为30％的磷钨酸由于酸性强、酸量大且均匀分散而呈现较高的活性。对该催化剂,适宜的反应温度为200℃,醇萘比为3,低浓度反应有利于选择性的提高,产物分布随时间的关系曲线表明该反应属连串反应类型,反应温度是影响2,6-二异丙基萘(2,6-DIPN)产率的主要因素。     

ETBE synthesis over silicotungstic acid and tungstophosphoric acid catalysts calcined at different temperatures

Vapor phase ethyl tertiary butyl ether synthesis was investigated using heat treated heteropoly acid catalysts, namely silicotungtsic acid (STA) and tungstophosphoric acid-Keggin (TPA-K) and these results were compared with the results obtained with untreated catalysts. ETBE synthesis experiments showed that heat treatment of TPA-K at temperatures over 473 K had caused significant decrease of its catalytic activity. Activity of STA was more stable and deactivation of this catalyst was observed by heat treatment at 673 K and above. Heat treatment at high temperatures caused loss of constitutional water of STA and TPA-K, causing loss of protons, consequently the loss of acidity of the catalysts, resulting deactivation. FT-IR, TGA-DTA and DRIFTS analyses on pyridine-adsorbed catalysts supported the conclusions related to structural changes of STA and TPA-K with heat treatment. Highest ETBE yields were obtained at around 368 K, while at temperatures over 423 K formation of DEE and ethylene were observed due to dehydration of ethanol.     

Hydrogen production by aqueous-phase reforming of glycerol over nickel catalysts supported on CeO2

Nickel catalysts supported on CeO₂ were prepared and evaluated in aqueous-phase reforming of glycerol. Three different methodologies of synthesis were used: wet impregnation, co-precipitation and combustion, and the catalysts were characterized by chemical composition, textural analysis, crystalline structure and reducibility. The reaction was carried out in a batch reactor with solution of 1 and 10 wt.% glycerol, at 523 and 543 K. A maximum glycerol conversion of 30% was achieved by the catalyst prepared by combustion at 543 K using solution 1% glycerol. In the gas phase, the molar fraction of H₂ was always higher than 70% and formation of CH₄ was very low (< 1%). The increase in glycerol concentration decreases the conversion and H₂ formation.     

SBA-15固载磷钨酸催化剂的制备及催化合成叔丁基苯酚

以不同硅烷偶联剂改性的介孔分子筛SBA-15为载体、PW_(12)为催化剂,通过对SBA-15表面共价及非共价修饰制备磷钨酸@介孔分子筛/硅烷偶联剂复合催化剂PW_(12)@SBA-15/YSiX_3(YSiX_3=Apts、Atapts、Papts);并利用FT-IR、XRD、TEM、N_2吸附-脱附对其组成、结构及形貌进行表征。以改性SBA-15分子筛固载磷钨酸催化剂催化合成叔丁基苯酚为研究对象,考察不同硅烷偶联剂、反应温度、苯酚与叔丁醇物质的量比对催化合成叔丁基苯酚的影响,并获得合成叔丁基苯酚的最佳工艺条件,即反应温度145℃、n(苯酚)∶n(叔丁醇)=1∶2.5、重时空速2.2 h~(-1),该最佳反应条件下,PW_(12)@SBA-15/Apts催化剂催化合成叔丁基苯酚的催化活性最高,苯酚转化率为98.3%,2,4-二叔丁基苯酚选择性为57.3%.     

Catalytic activity of Pt and tungstophosphoric acid supported on MCM-41 for the reduction of NOx in the presence of water vapor

The catalytic activity of tungstophosphoric acid and Pt loaded MCM-41 for the catalytic reduction of NO_x with propene in the presence of water vapor was studied. Pt/MCM-41 was found to be most active, the loading with H₃PW₁₂O₄₀ led to an improved selectivity to N₂ formation and to an enhanced activity in the presence of water vapor. Hydrated tungstophosphoric acid generated additional sorption sites for C₃H₆ and led to a higher local concentration of the reducing agent on the catalyst surface, which was found to increase the activity of the Pt and H₃PW₁₂O₄₀ loaded catalysts in the presence of water vapor.     

负载型离子液体催化酯化法合成三醋酸甘油酯

研究了以磺酸咪唑基离子液体催化甘油和醋酸通过直接酯化法合成三醋酸甘油酯反应,结果表明,[(n-Bu-SO_3H)MIm][HSO_4]离子液体催化性能最好。采用浸渍法将其固载在SiO_2的表面,利用FT-IR对催化剂结构进行了表征,考察反应工艺条件对甘油转化率和三醋酸甘油酯选择性的影响,结果表明,在催化剂用量8%,醋酸与甘油物质的量比6∶1,110℃条件下反应8.0 h,甘油转化率可达到97.2%,对应的三醋酸甘油酯选择性可达21.2%。回收的催化剂经重复使用4次,反应体系中甘油转化率和三醋酸甘油酯选择性无明显下降。     

铌酸催化水解葡萄糖的研究

研究了铌酸催化水解葡萄糖溶液的反应,考察了不同热处理温度对铌酸催化剂活性的影响。研究发现,当热处理温度为400 ℃时,此类催化剂对葡萄糖催化水解生成乙酰丙酸（LA）的活性和选择性较好。对不同制备方法得到的铌酸催化剂活性进行比较,结果表明,直接水洗法制备得到的铌酸较有利于LA的生成。对用磷酸处理的铌酸催化剂进行考察发现,对于本反应体系,催化剂酸性的增加反而使活性下降。用XRD对催化剂的结构表征结果表明,催化剂活性与其表面是否结晶无明显关系。     

苯甲醛与甘油在二氧化硅负载的磷钨酸催化剂上的缩合反应

针对磷钨酸比表面积小和不易回收利用等缺点,采用溶胶-凝胶法制备了不同磷钨酸负载量的H3PW12O40/SiO2固体酸催化剂,用XRD和N2-吸附对H3PW12O40/SiO2固体酸催化剂进行了表征,研究了在苯甲醛和甘油缩合反应中的催化性能,考察了催化剂的焙烧温度、磷钨酸的负载量、催化剂用量和反应时间的影响。结果表明,H3PW12O40/SiO2固体酸是平均颗粒在(20.9～26.4)nm的无定形催化剂,在苯甲醛甘油缩醛的合成中具有高活性和高稳定性。最佳条件:焙烧温度500℃,H3PW12O40负载质量分数10%,催化剂用量0.5 g,n(苯甲醛)∶n(甘油)=1∶1.1、甲苯15 mL,反应时间2.0 h。最佳条件下,苯甲醛转化率达99.2%。H3PW12O40/SiO2固体酸催化剂独特的Keggin阴离子结构和表面酸中心、高比表面积和准液相在苯甲醛和甘油的缩合中具有重要作用。     

Catalytic wet air oxidation of acetic acid over different ruthenium catalysts

Ruthenium catalysts were prepared by impregnation of different supports: ZrO₂, CeO₂, TiO₂, ZrO₂–CeO₂ and TiO₂–CeO₂. Their activities for acetic acid oxidation in aqueous solution were investigated in a stirred reactor at a reaction temperature of 200 °C and total pressure of 4 MPa. The order of the catalyst activity obtained was RuO₂/ZrO₂–CeO₂ > RuO₂/CeO₂ > RuO₂/TiO₂–CeO₂ > RuO₂/ZrO₂ > RuO₂/TiO₂, which corresponds to surface concentration of non-lattice oxygen (defect-oxide or hydroxyl-like group) of these catalysts. The non-lattice oxygen on the catalyst surface plays an important role in the catalytic activity.     

铌酸光催化降解甲基橙溶液

以铌酸为光催化剂,在高压汞灯照射下,对模拟染料废水甲基橙溶液进行光催化降解,研究过氧化氢加入量、催化剂用量和甲基橙起始浓度对光催化降解的影响。结果表明,当甲基橙起始浓度为15 mg·L^-1、30%过氧化氢用量为5.0 mL·L^-1和催化剂用量为1.5 g·L^-1时,光照1 h,甲基橙溶液降解率达到97％,在较低浓度下,甲基橙溶液的光催化降解反应符合一级动力学方程。     

PtAu/ZrO_2催化甘油选择性制备乳酸

采用溶胶-沉积法制备了Pt Au/ZrO_2系列催化剂,在惰性气体气氛下用于催化甘油选择性制备乳酸。研究不同反应温度下,不同单金属负载和不同比例Pt Au双金属负载催化剂的催化活性以及不同气氛下催化剂重复使用性能,对催化剂进行BET、AAS和TEM等表征。结果表明,在浓度1.1 mol·L-1甘油水溶液10 m L、(1∶1)Pt Au/ZrO_2催化剂用量0.132 g、反应温度160℃、氮气压力1.4 MPa和反应时间6 h条件下,甘油转化率90%,乳酸选择性93.7%。催化剂重复使用性能实验验证了氧气气氛下催化剂活性保持良好。     

Cu基催化剂催化甘油氢解制备丙二醇

在间歇釜式反应器中考察Cu基催化剂在不同酸性条件下的甘油催化氢解反应性能,采用γ-Al₂O₃、SiO₂和SiC酸碱性不同的载体研究催化剂催化活性和选择性的影响,结果表明,3种载体的Cu基催化剂均对1,2-丙二醇的生成有较高的催化活性和选择性,但只有弱酸性SiO₂为载体时生成1,3-丙二醇。研究在底物中添加H₂SO₄（B酸）对甘油氢解反应性能的影响,发现质子酸的存在有利于1,3-丙二醇的生成,但易导致副反应发生,使1,2-丙二醇选择性大幅降低。研究用磷钨酸改性的Cu/SiO₂催化剂对甘油氢解反应的催化活性的影响,发现磷钨酸的加入有利于甘油氢解为1,3-丙二醇,且酸性越强,越容易发生副反应。随着Cu/HWP/SiO₂催化剂焙烧温度的升高,酸性减弱,丙二醇选择性提高,推测出质子酸作用下Cu基催化剂的甘油氢解反应机理。     

Catalytic dehydration of glycerol to acrolein over mesoporous MCM-41 supported heteropolyacid catalysts

Journal of Porous Materials - A series of vanadium substituted phosphomolybdic acid (VPMA) supported on mesoporous MCM-41 catalysts with varying VPMA content ranging from 10 to 50&nbsp;wt% were...     

磷钨酸/二氧化钛催化合成甲基丙烯酸丁酯的研究

采用浸渍法制备了磷钨酸／二氧化钛催化剂，用于催化合成甲基丙烯酸丁酯，其性能优于硫酸，在酸醇物质的量的比为1：1．15，催化剂用量为甲基丙烯酸质量的1．3％，酯化温度为120℃，反应时间75min的条件下，酯化率达91．7％，产品质量分数大于98％，并且催化剂可以使用多次。     

Gas-phase dehydration of glycerol over commercial Pt/γ-Al2O3 catalysts

Gas-phase dehydration of glycerol to produce acrolein was investigated over commercial catalysts based onγ-Al2O3, viz. A-64, A-56, I-62, AP-10, AP-56, AP-64 and KR-104. To understand the effect of Cl?anions, HCl-impregnated sup-ports have been investigated in the dehydration reaction of glycerol at 375 °C. For comparison, various H-zeolites were also examined. It was found that the glycerol conversion over the solid acid catalysts was strongly dependent on their acidity and surface area. And the relationship between the catalytic activity and the acidity of the catalysts was discussed. The outstanding properties of Pt/γ-Al2O3 catalyst systems for the dehydration of glycerol were revealed. Pt/γ-Al2O3 catalyst (AP-64) showed the highest catalytic activity after 50 h of reaction with an acrolein selectivity of 65%at a conversion of glycerol of 90%. Based on these results, catalysts based onγ-Al2O3 appear to be most promising for gas phase dehydration of glycerol.     

活性炭负载磷钨酸催化合成烷基多苷

用活性炭负载磷钨酸为催化剂,用二步法合成了十二烷基多苷(APG)。丁苷化反应的最优工艺条件是:磷钨酸负载量20%,用量为葡萄糖的5%,n(葡萄糖)∶n(丁醇)为5∶1,温度120℃,反应时间2 h。催化剂可以重复使用。在n(十二醇)∶n(葡萄糖)为2.5∶1时,可以用水萃取分离APG,得到的产品色浅且稳定。APG在水溶液中的临界胶束浓度为65.5 mg/L,表面张力为25.2 mN/m,泡沫力为160 mm,5 min后泡沫高度为158 mm。