Ag／ZSM—5／SiO2催化氧化乙醇制乙醛

进行了Ａｇ／ＺＳＭ／５／ＳｉＯ２催化氧化乙醇制乙醛的扩大实验。结果表明，该催化剂有较高的催化活性，在３４０℃，空速为１６４６ｈ＾－１时，乙醇转化率为９１．４％，乙醛选择性为９９．３％，而且其稳定性也较好。     

三氟乙醇催化氧化合成三氟乙醛

研究了三氟乙醇催化氧化合成三氟乙醛的钒系催化剂。以V₂O₅为活性组分,考察了以ZrO₂为载体,并在此基础上通过添加MoO₃、SnO₂和WO₃等助催化剂进行性能调变。结果表明,以ZrO₂为载体, n（V₂O₅）∶n（ZrO₂）=5,SnO₂作为助催化剂,在反应温度290 ℃、空速0.33 h^-1和原料配比n（O₂）∶n(三氟乙醇）=11.69最佳工艺条件下,三氟乙醇转化率达89.06%,三氟乙醛选择性达97.14%。     

浓硫酸催化合成乙醛缩二乙醇

以无水乙醇和无水乙醛为原料,浓硫酸为催化剂,制备了乙醛缩二乙醇。通过单因素实验确定较佳反应条件为:无水乙醇的用量为150 mL,无水乙醇与无水乙醛摩尔比为2.0∶1.0,温度为20℃,无水氯化钙用量为20 g,浓硫酸的用量为0.6 g,反应5 h,乙醛缩二乙醇的收率可达90.2%。     

氧气催化氧化乙苯制苯乙酮研究进展

高附加值的苯乙酮是一种非常重要的有机合成中间体.近年来以氧气为氧化剂催化乙苯制苯乙酮是催化有机合成领域的热门课题之一,但此方法尚未解决与氧气匹配的催化体系.较为系统地总结该反应的催化体系,包括金属纳米材料与金属氧化物催化、分子筛催化、碳材料催化、水滑石催化、金属有机框架材料催化、N-羟基邻苯二甲酰亚胺催化等.     

Ag／ZSM－5／SiO_2催化氧化乙醇制乙醛

进行了Ａｇ／ＺＳＭ－５／ＳｉＯ２催化氧化乙醇制乙醛的扩大实验。结果表明，该催化剂有较高的催化活性，在３４０℃，空速为１６４０ｈ－１时，乙醇转化率为９１．４％，乙醛选择性为９９．３％，而且其稳定性也较好。     

有机碱协同SnCl_2·2H_2O催化葡萄糖转化制备乳酸甲酯

以SnCl_2·2H_2O为催化剂,对比13种不同有机碱在催化葡萄糖醇解制备乳酸甲酯过程中的助催化作用,包括1-甲基咪唑、咪唑、1-乙烯基咪唑、三苯基膦、苯胺、邻菲罗啉、喹啉、2,6-二甲基吡啶、4,4-联吡啶、吡啶、4-甲基吡啶、2,6-二溴吡啶、2-溴吡啶等有机碱,考察反应时间、反应温度、有机碱与SnCl_2物质的量比的影响。结果表明,以2-溴吡啶为助催化剂,且与SnCl_2物质的量比为1∶1时,在220℃、2 MPa的氮气气氛反应6 h,乳酸甲酯收率最高,为44.6%。     

菲催化氧化制2,2′-联苯二甲酸

以质量分数30%的过氧化氢为氧化剂,Na₂WO₄·2H₂O 为催化剂,乙酸为溶剂,在酸性配体存在条件下,进行菲催化氧化制2,2′-联苯二甲酸。考察反应条件对产率的影响,确定较佳工艺为：菲25 mmol,30%过氧化氢用量20 mL,Na₂WO₄·2H₂O用量0.5 mmol,草酸2 mmol,在8 mL乙酸中回流反应3 h,得到高纯度2,2′-联苯二甲酸,收率达72%。产品结构经IR、¹H NMR、¹³C NMR 和元素分析进行了表征。     

钒铌氧化物催化剂催化氧化乙二醛制乙醛酸

对钒铌氧化物催化氧化乙二醛制乙醛酸进行研究,考察V₂O₅、Nb₂O₅及其混合物和工艺条件如乙二醛浓度、催化剂加入量、反应温度及反应时间对反应的影响。结果表明,HNO₃+NaNO₂+Nb₂O₅体系中,在乙二醛质量分数20%、催化剂用量1 g、反应温度318 K和反应时间2 h条件下,乙二醛转化率为82%,乙醛酸选择性为79%。以SiO₂为载体,采用共沉淀法制备Nb₂O₅/SiO₂催化剂,采用N₂等温吸附-脱附和XRD对催化剂进行表征,考察Nb₂O₅负载量和催化剂用量对催化氧化乙二醛合成乙醛酸的影响,并对催化剂稳定性进行研究。结果表明,Nb2O5能提高硝酸催化氧化乙二醛体系中乙二醛转化率和乙醛酸选择性,Nb₂O₅/SiO₂比纯Nb₂O₅的催化效果更好。HNO₃+NaNO₂+Nb₂O₅/SiO₂体系中,在催化剂用量5 g、活性组分Nb₂O₅负载质量分数18%和反应时间2 h条件下,乙二醛转化率为85%,乙醛酸选择性为87%,Nb₂O₅/SiO₂的稳定性和重复使用效果均良好。     

催化氧化三氟乙醇制备三氟乙醛和三氟乙酸

对三氟乙醇气相催化氧化制备三氟乙醛和三氟乙酸的工艺进行了研究,确定了以分子氧为氧化剂 、负载型V₂O₅为催化剂,采用固定床反应器进行反应,气相色谱法检测产品中的三氟乙醛和三氟乙酸的含量,并采用XRD和BET等分析方法对催化剂的性能进行了探讨。     

鸡蛋白四苯基锰卟啉催化乙醇氧化性能研究

使用鸡蛋蛋白(HEW)作为载体,制备鸡蛋白四苯基锰卟啉(Mn-TPP/HEW)催化剂并进行表征.考察该催化剂在不同时间、温度和压力等反应条件下的催化活性及其催化氧化乙醇生成乙醛和乙酸的能力.在最佳反应条件下,该催化剂得到的乙醇转化率和选择性(乙醛+乙酸)分别为18.3%、70.5%.并初步提出了可能的催化反应机理.     

纳米MOx/ZrO2催化剂上乙醇氧化合成乙醛性能研究

采用溶胶-凝胶法首先制备出Zr(OH)₄凝胶，再将凝胶用乙醇进行醇化处理，经烘干和焙烧制得ZrO₂纳米载体。载体颗粒粒径均匀，大小为20 nm左右。以ZrO₂为载体，采用浸渍法分别负载Fe₂O₃、CuO、NiO和Mo₂O₃等不同金属氧化物，制得负载型催化剂。通过XRD、TEM、SEM和IR等对催化剂进行表征。以乙醇氧化脱氢合成乙醛为探针反应，考察了催化剂的催化性能。实验结果表明，催化剂Fe₂O₃/ZrO₂在反应温度为573 K时，乙醇转化率为75.8%，乙醛选择性为97.3%。     

Catalytic wet oxidation of phenol over PtxAg1−xMnO2/CeO2 catalysts

Catalytic wet oxidation reactions of aqueous phenol over unpromoted, base- and noble-metal promoted MnO₂/CeO₂ catalysts were carried out under mild conditions (80–130°C, 0.5 MPa O₂) in a batch slurry reactor. Even though the catalyst-mediated oxidation was very effective in destroying phenol, only a moderate selectivity toward complete mineralization into CO₂ and H₂O was attained due to parallel formation of deactivating carbonaceous deposits. Promotion of the mixed-oxide catalysts with platinum and/or silver enhanced the mineralization selectivity and reduced appreciably the amount of deposits.     

Atom transfer radical polymerizations of methyl methacrylate catalyzed by EBiB/SnCl2·2H2O(FeCl2·4H2O)/FeCl3·6H2O/MA5-DETA systems

The ATRP of methyl methacrylate (MMA) with the system of FeCl₂·4H₂O, N,N,N′,N″,N″-penta(methyl acylate)diethylenetriamine (MA₅-DETA) and ethyl 2-bromoisobutyrate (EBiB) showed high activity and is not well-controlled. The addition of a certain amount of FeCl₃·6H₂O as the additive into the above system results in the decrease of the polymerization rate and the improvement of the controllability. When SnCl₂·2H₂O was added instead of FeCl₂·4H₂O, a novel catalyst system SnCl₂·2H₂O/FeCl₃·6H₂O/EBiB/MA₅-DETA formed shows better controllability, higher catalytic activity and higher initiating efficiencies (more than 90%) in comparison with the system FeCl₂·2H₂O/FeCl₃·6H₂O/EBiB/MA₅-DETA. The polydispersities of the polymers kept range from M_w/M_n=1.18-1.26. The real active species in the new system is Fe (II) formed from the reaction of FeCl₃·6H₂O with the active radical species produced from the reaction of SnCl₂·2H₂O with EBiB.     

Anion water in gypsum (CaSO4·2H2O) and hemihydrate (CaSO4·1/2H2O)

The bonding nature of water in gypsum, CaSO₄·2H₂O, and hemihydrate, CaSO₄·1/2H₂O, was suggested by characteristic absorption bands of water and sulphate ions. The infrared spectral data indicate the presence of anion water in gypsum and hemihydrate through hydrogen bonding. Negative shifting of bending vibration of SO₄ ion and lowering and broadening of the O-H stretching vibration at around 3600 cm⁻¹ indicate the presence of both anion water and hydrogen bonding in gypsum and hemihydrate     

乙醇催化氧化、缩合和酯化反应的研究进展

乙醇是一种重要的基础化工产品,随着生物乙醇和煤制乙醇的大规模发展,乙醇的过剩问题越来越严重,因此,将乙醇催化转化为高附加值化学品具有重要意义。乙醇经催化氧化制乙醛、乙酸,经催化脱氢-缩合制乙缩醛,经催化脱氢-酯化制乙酸乙酯等催化反应过程,不仅可以消化日益增多的乙醇产能,提高乙醇附加值,而且有效地延伸了乙醇产业链,并带来巨大的社会效益和经济效益。对近年来乙醇经催化氧化制乙醛、乙酸,经催化加氢-缩合制乙缩醛,经催化脱氢-酯化制乙酸乙酯等催化反应的催化剂体系、反应工艺和反应机理等方面的研究进展进行归纳、总结和评述,并对研究工作的发展趋势进行展望。     

Catalytic behavior of YBa2Cu3O7-x in the partial oxidation of ethanol to acetaldehyde

The partial oxidation of ethanol to acetaldehyde was performed over YBa₂Cu₃O_7-x in a flow reactor. The catalytic characteristics of YB₂Cu₃O_7-x were compared with those of an individual oxide comprising the YBa₂Cu₃O_7-x . The structural change of YBa₂Cu₃O_7-x and the other catalysts after the reaction was measured by means of XRD and XPS, and it was found that the high oxidation state of copper in YBa₂Cu₃O_7-x was responsible for the higher activity and the higher selectivity for acetaldehyde.     

氧化铝负载不同晶型MnO2用于低温等离子体催化耦合降解乙醛和苯

制备了α-MnO₂/γ-Al₂O₃和β-MnO₂/γ-Al₂O₃负载型锰系氧化物催化剂,通过XRD、TEM、TG和H₂-TPR等手段对催化剂进行表征,分别考察催化剂与低温等离子体耦合协同去除乙醛和苯的效果。结果表明,MnO₂/γ-Al₂O₃催化剂的加入明显提高低温等离子体去除挥发性有机物的效率及CO₂选择性,α-MnO₂/γ-Al₂O₃的耦合效果优于β-MnO₂/γ-Al₂O₃。低温等离子体输入电压为16.8 kV,α-MnO₂/γ-Al₂O₃与低温等离子体耦合乙醛去除率可达100%。降解苯的效率较低,这是由于苯的化学结构更稳定。     

负载型钴锰复合金属氧化物催化剂催化分解N_2O

以ZrO_2为载体,采用浸渍法制备负载型钴锰复合金属氧化物催化剂,研究催化剂活性组分负载量、Co与Mn物质的量比、焙烧条件及含H_2O气氛对N_2O转化率的影响。结果表明,催化剂最佳制备条件为:活性组分Co负载质量分数3%,Co与Mn物质的量比为1∶1,焙烧升温速率2℃·min-1,焙烧温度900℃。该条件制备的负载型钴锰复合金属氧化物催化剂在反应温度850℃时,N_2O转化率达98.7%。当反应气氛中H_2O体积分数小于20%条件下,850℃时N_2O转化率高于90%,表明催化剂具有较强的抗水性能。     

Kinetics of CO and H2 oxidation over CuO-CeO2 catalyst in H2 mixtures with CO2 and H2O

The kinetics of CO and H₂ oxidation over a CuO-CeO₂ catalyst were simultaneously investigated under reaction conditions of preferential CO oxidation (PROX) in hydrogen-rich mixtures with CO₂ and H₂O. An integral packed-bed tubular reactor was used to produce kinetic data for power-law kinetics for both CO and H₂ oxidations. The experimental results showed that the CO oxidation rate was essentially independent of H₂ and O₂ concentrations, while the H₂ oxidation rate was practically independent of CO and O₂ concentrations. In the CO oxidation, the reaction orders were 0.91, −0.37 and −0.62 with respect to the partial pressure of CO, CO₂ and H₂O, respectively. In the H₂ oxidation, the orders were 1.0, −0.48 and −0.69 with respect to the partial pressure of H₂, CO₂ and H₂O, respectively. The activation energies of the CO oxidation and the H₂ oxidation were 94.4 and 142 kJ/mol, respectively. The rate expressions of both oxidations were able to predict the performance of the PROX reactor with accuracy. The independence between the CO and the H₂ oxidation suggested different sites for CO and H₂ adsorption on the CuO-CeO₂ catalyst. Based on the results, we proposed a new reaction model for the preferential CO oxidation. The model assumes that CO adsorbs selectively on the Cu⁺ sites; H₂ dissociates and adsorbs on the Cu⁰ sites; the adsorbed species migrates to the interface between the copper components and the ceria support, and reacts there with the oxygen supplied by the ceria support; and the oxygen deficiency on the support is replenished by the oxygen in the reaction mixture.