活性炭担载的铂催化剂在碱性条件下选择性氧化甘油制备乳酸

生物柴油是一种环境友好的燃料,随着其生产及应用的快速增长,其生产过程中重要的副产物甘油将会大量过剩.因此,将甘油转化为高附加值的化学品对于提高生物柴油整体竞争力具有重大意义.乳酸是重要的化工原料,可用于制备生物兼容和可降解的聚乳酸塑料,广泛应用于食品和医药等领域.近年来,由甘油制乳酸的研究受到格外关注,相对于水热反应和氢解反应等,催化选择氧化反应因温和的反应条件而更具竞争力.
　　目前,甘油催化选择氧化制乳酸一般需加入较高比例的NaOH,而碱的类型对反应性能的影响鲜有报道.另外,催化剂常采用TiO2和CeO2等氧化物载体,而炭载体具有比表面积较大、在酸碱溶液中稳定及贵金属易于回收等优点,在催化领域有着广泛应用.因此,本文研究了活性炭(AC)担载的Pt催化剂在甘油催化选择氧化制乳酸反应中的催化性能.
　　首先研究了Pt/AC催化剂和碱在甘油催化选择氧化制乳酸过程中的催化作用.实验发现, Pt/AC和碱协同作用才能得到乳酸. Pt/AC催化剂在甘油脱氢生成中间产物(甘油醛和二羟基丙酮)的过程中起主导作用,碱的存在能够促进甘油羟基脱氢;中间产物实验证实,中间产物生成乳酸过程中碱起主导作用,它促进甘油醛和二羟基丙酮脱水反应和坎尼扎罗重排反应获得乳酸.进一步研究发现,中间产物二羟基丙酮比甘油醛更有利于乳酸生成,而Pt/AC催化剂有利于中间产物氧化为甘油酸.
　　进一步研究了不同类型的碱对反应性能的影响.结果表明,碱金属氢氧化物(LiOH, NaOH, KOH)比碱土金属氢氧化物(Ba(OH)2)更有利于提高甘油转化率和乳酸选择性.在加入碱金属氢氧化物条件下,甘油转化率与其离子半径呈正相关,而乳酸选择性则呈相反趋势.在LiOH存在下,乳酸选择性明显高于NaOH和KOH条件.当LiOH：甘油摩尔比为1.5时,甘油转化率和乳酸选择性均最高.在较低的LiOH与甘油摩尔比时,随着反应的消耗,溶液中的OH–减少,其促进甘油脱氢的作用变弱,并且不利于中间产物进行坎尼扎罗反应,故反应活性和乳酸选择性较差;而当LiOH比例过高时,会导致溶解氧浓度迅速降低,从而使甘油转化率和乳酸选择性下降,同时副产物甘油酸的选择性有所提高.这可能是因为较高比例的碱会促进中间产物甘油醛生成,该中间产物在Pt/AC催化作用下发生进一步氧化反应生成甘油酸.
　　研究了反应时间对催化性能的影响.结果表明,反应6 h后,甘油已经完全转化,乳酸选择性最高,达到69.3%;进一步延长反应时间,乳酸选择性有所下降,而副产物乙酸选择性略有增加,这可能是部分乳酸分解所致. Pt/AC催化剂经5次循环使用后仍保持了较高的甘油转化率和乳酸选择性.     

聚苯胺-改性木质素磺酸钠复合材料基活性炭负载Pd催化剂对甲酸氧化的催化性能

将聚苯胺/改性木质素磺酸钠复合材料在不同炭化温度下进行处理得到活性炭材料,利用红外光谱、拉曼光谱、比表面积分析和扫描电镜等手段对其结构和表面性质进行了表征。通过液相还原方法将Pd纳米颗粒负载在所制备的活性炭材料上,获得Pd/C催化剂用于甲酸氧化,并采用X射线衍射、透射电镜和电化学测试等方法对该Pd/C催化剂进行表征。结果表明,以800℃下炭化得到的活性炭材料为载体所制备的Pd-AC800催化剂其催化性能最优;Pd粒径为5.4 nm,电化学活性面积为53.78 m²/g。由于在该催化剂上甲酸氧化通过直接途径进行,Pd-AC800可用作直接甲酸燃料电池的催化剂。     

Pb-Pt/AC催化甘油一步法制备丙酮酸

生物质能具有绿色环保、可再生、来源广泛和安全性高等优点,成为当前的研究热点.作为生物柴油的主要副产物,甘油是一种重要的生物质平台化合物.甘油的高效利用,不仅能够获得重要的精细化学品及聚合物,也可以延长生物柴油的产业链,降低其生产成本,增加其市场竞争力.丙酮酸是一种弱有机酸,为生物体内葡萄糖分解代谢的中间产物,在生物能量代谢和物质代谢过程中起着重要的枢纽作用.同时,由于它同时含有羧基和酮羰基,具有很强的反应性,可参与多种化学反应,在化学工业中有广泛应用.目前,工业上主要采用酒石酸脱水脱羧法生产丙酮酸,丙酮酸收率可达50–55%,但生产过程需要消耗大量的KHSO4粉末,生产成本高,且高耗能高污染,不符合可持续发展的要求.因此,利用可再生资源甘油在温和条件下生产丙酮酸显现出良好的应用前景.目前,由甘油一步法获得丙酮酸仅可通过发酵法实现,但是其规模化生产存在效率低、废弃物污染等问题.因此,研究化学方法由甘油一步制备丙酮酸可行也十分必要.本课题组以Pt/AC或Cu-Pt/AC为催化剂进行甘油氧化制备乳酸的研究,所得产物中几乎未检出丙酮酸;当以Pb-Pt/C为催化剂进行乳酸脱氢氧化制备丙酮酸,可获得较高选择性的丙酮酸.因此,本文通过向Pt/AC催化剂中引入Pb助剂,以期调变甘油氧化的产物分布,从而获得相对高的丙酮酸选择性.通过浸渍-沉积沉淀法(Im-DP)制备了一系列不同Pb载量(1–7.0 wt%)的xPb-5Pt/AC-Im-DP催化剂,并采用不同方法制备了一系列5Pb-5Pt/AC催化剂,用于在温和条件下甘油选择性氧化制备丙酮酸反应中.结果表明,Pb载量和催化剂制备方法都对其催化活性有显著影响.当xPb-5Pt/AC-Im-DP催化剂中Pb载量为1%时,甘油转化率和丙酮酸选择性均较单金属5Pt/AC催化剂高,但当Pb载量继续升高至3%及以上时,甘油转化率明显下降.我们推测这与Pb3(CO3)2(OH)2物种的形成有关.采用该方法制备催化剂时,Pb载量宜为5.0 wt%.保持Pt和Pb载量均为5.0 wt%,采用共沉积沉淀(Co-DP)、共浸渍(Co-Im)、以及对催化剂进行500oC氩气焙烧等,制备了具有Pb3(CO3)2(OH)2物种、铂铅合金物种(PtPb和PtxPb)和两物种均没有的5Pb-5Pt/AC催化剂.通过评价它们的催化性能,进一步探究了Pb3(CO3)2(OH)2物种、铂铅合金物种、表面金属价态与催化剂活性的关系.实验表明,Pb3(CO3)2(OH)2和表面Pb0物种不利于甘油的转化,铂铅合金对甘油转化有一定的促进作用,对丙酮酸生成显现出明显促进作用.通过对Co-DP、Im-DP催化剂进行500oC氩气焙烧,能够除去Pb3(CO3)2(OH)2物种,同时形成铂铅合金.综上,本文在温和条件下,采用Pb-Pt/AC催化剂进行甘油选择性氧化制备丙酮酸反应.采用优化的方法制备的5Pb-5Pt/AC催化剂在90oC条件下反应10 h,丙酮酸收率可达18.4%,这是目前甘油一步法氧化制备丙酮酸的最高值.进一步优化反应条件、催化剂组成与结构,探索反应机理仍十分必要.     

Catalytic pyrolysis of CHF3 over activated carbon and activated carbon supported potassium catalyst

The catalytic activity of activated carbon (AC) and activated carbon supported potassium for the decomposition of CHF₃ was investigated at temperatures between 873 and 1173 K and at a space velocity of 4300 h⁻¹. It is found that activated carbon supported potassium shows high and relatively stable activity during the pyrolysis of CHF₃ under the conditions studied. Compared with the gas phase reaction, the conversion of CHF₃ increases by up to 10 times between 873 and 1123 K, with the major products being C₂F₄ and C₃F₆. Selectivities as high as 55% to C₂F₄ and 35% to C₃F₆ are achieved under optimum conditions. The main byproduct HF readily reacts with K₂O in the catalyst, converting the catalyst from K₂O/AC into KF/AC. Selectivity to the major products remains relatively constant following this transformation.     

Oxidation of secondary amines to nitrones using magnetically separable tungstophosphoric acid supported on silica-encapsulated γ-Fe2O3 nanoparticles

Superparamagnetic tungstophosphoric acid supported on silica-encapsulated γ-Fe₂O₃ was used as an efficient catalyst for the direct oxidation of secondary amines to nitrones with hydrogen peroxide as the oxidant. The catalyst could be recycled up to four times without significant loss of activity.     

活性炭负载对甲苯磺酸催化合成己二酸二异辛酯

己二酸二异辛酯(Diisooctyl Adipate,DIOA)是聚氯乙烯、氯乙烯共聚物、聚苯乙烯、硝化纤维素、乙基纤维素等的优良耐寒增塑剂.     

Pre-formed activated carbon matting derived from the pyrolysis of biomass natural fibre textile waste

Low grade biomass fibre produced as a by-product from the flax and hemp industry was manufactured into a non-woven, pre-formed matting material via entanglement, layering and needling. The advantage of such a structure is that textile technology is used to form a self supporting fibre matrix, utilising the ease with which fibre can be worked. The non-woven matting was then pyrolysed and gasified with steam to produce activated carbon. The influence of pyrolysis process conditions on the production of chars and activated carbon from the pre-formed, non-woven textile matting were investigated.     

Efficient and green tetrahydropyranylation and deprotection of alcohols and phenols by using activated carbon supported sulfuric acid

A simple, green and efficient method for the DHP protection of various alcohols and phenols and the subsequent removal of the corresponding protective group in the presence of a catalytic amount of the activated carbon supported H2SO4 is described.     

活性炭固载磷钨酸催化合成丙酸丙酯

用活性碳固载磷钨酸催化剂合成了丙酸丙酯,考察了磷钨酸固载量、催化剂用量、醇酸摩尔比、反应温度、反应时间、带水剂用量对酯化反应的影响。在优化条件(催化固载量30．0％、催化剂用量2．5g/0．2mol丙酸、醇酸摩尔比1．2：1、反应温度110--116℃、反应时问2．51h、带水剂环己烷用量10mL下反应,丙酸丙酯收率为95．8％,催化剂可重复使用。     

对甲苯磺酸/活性炭/双氧水体系选择氧化苯乙烯生成苯甲醛(英文)

以双氧水为氧化剂,研究了对甲苯磺酸和活性炭体系选择氧化苯乙烯生成苯甲醛反应性能。考察了反应时间、温度、催化剂用量、苯乙烯和双氧水摩尔比等对苯乙烯选择氧化性能的影响.结果表明,对甲苯磺酸和活性炭的用量和用量比是一个重要因素,但对甲苯磺酸的酸性对氧化反应活性影响不大.对甲苯磺酸和双氧水相互作用,经非自由基过程氧化苯乙烯.通过分解双氧水产生氢氧自由基,活性炭显著提高对甲苯磺酸和双氧水体系氧化苯乙烯活性.在惰性或还原气氛中高温处理活性炭能降低其表面含氧基团数量,增加碱性,有效分解双氧水,产生相对较多的OH自由基.与未处理的活性炭相比,高温处理的活性炭进一步提高了对甲苯磺酸和双氧水体系氧化苯乙烯活性,但降低了苯甲醛选择性.经磺化,在活性炭表面引入的–SO_3H基团比含氧基团(–OH,–COOH)更有效与双氧水作用氧化苯乙烯.     

Analysis of graphene-like activated carbon derived from rice straw for application in supercapacitor

Activated carbons with large surface area, abundant microporosity and low cost are the most commonly used electrode materials for energy storage devices. A very slack activated carbon with ultra-thin two-dimensional (2D) layer structure was prepared by our proposed approach in this work, which includes a pre-treatment process and potassium hydroxide activation at high temperatures.     

Simultaneous adsorption of copper ions and humic acid onto an activated carbon

In this study, simultaneous adsorption of copper ions and humic acid (HA) from Aldrich onto an activated carbon is investigated. It is found that the HA adsorption in the absence of copper decreases as the pH is increased. It leads to a reduction of 34.7% in the specific surface area of carbon. There exists a critical concentration (CC) of HA for copper adsorption. At HA concentrations < CC, a decrease in copper adsorption is observed; however, the HA improves the adsorption at HA concentrations > CC. An increase in ionic strength can enhance the copper uptake; however, zinc and/or cobalt ions have an insignificant influence on copper adsorption. The adsorption is significantly increased by citric acid, whereas addition of EDTA slightly decreases the uptake. An intraparticle diffusion model is successfully used to describe the copper adsorption kinetics.     

Adsorption of some metal complexes derived from acetyl acetone on activated carbon and purolite S-930

A new Schiff base (HL) derived from condensation of p-anisidine and acetyl acetone has been prepared and used as a chelating ligand to prepare Cr(III), Mn(II), Co(II), Ni(II) and Cu(II) complexes. The study of the nature of these complexes formed in ethanol solution following the mole ratio method (2:1, L:M) gave results which were compared successfully with these obtained from isolated solid state studies. These studies revealed that the complexes having square planner geometry of the type (ML₂), M = Co(II), Ni(II) and Cu(II), and octahedral geometry of the type [Cr^IIIL₂(H₂O)₂]Cl and [MN^IIL₂(H₂O)₂]. The adsorption studies of three complexes Cr(III), Mn(II), and Co(II) on activated carbon, H and Na-forms of purolite S-930 resin show high adsorption percentage for Cr(III) on purolite S-930 due to ion exchange interaction compared with high adsorption of neutral Mn(II), Co(II) complexes on activated charcoal. Linear plot of log Q_e versus log C_e showed that the adsorption isotherm of these three complexes on activated carbon, H and Na-forms of purolite S-930 surface obeys Freundlich isotherm and was similar to S-curve type according to Giles classification which investigates heterogeneous adsorption. The regression values indicate that the adsorption data for these complexes fitted well within the Freundlich isothermal plots for the concentration studied. The accuracy and precision of the concentration measurements of these complexes were determined by preparing standard laboratory samples, the results show relative error ranging from ±1.08 to 5.31, ±1.04 to 4.82 and ±0.28 to 3.09 and the relative standard deviation did not exceed ±6.23, ±2.77 and ±4.38% for A1, A2 and A3 complexes, respectively.     

微波辐射活性炭固载钨硅酸催化合成丙酸异戊酯

丙酸异戊酯是一种用途广泛的香料,为无色透明液体,具有浓郁的菠萝和洋梨果实香气,广泛用于涂料和食品工业.目前,国内外主要用浓硫酸催化酯化来合成[1].这个工艺虽然成熟,浓硫酸的催化活性较高,价廉易得,但其酸性很强,易引起副反应,严重的腐蚀设备和污染环境[2],所以研究一种新型、高效、绿色的催化剂是十分必要的.     

活化玻碳电极直接测定全血中的尿酸

用阳极极化法在碱性溶液中活化玻碳电极, 研究了尿酸(UA)在活化玻碳电极(AGCE)上的电化学行为, 并提出一种利用微分脉冲伏安技术测定全血中尿酸的电化学分析方法. 在0.1 mol/L的乙酸缓冲溶液中(pH 5.0), 以0.1 mol/L KCl作为支持电解质, 尿酸在AGCE上于0.484 V 处产生一个灵敏的氧化峰. 微分脉冲伏安法测定其氧化峰电流与 UA 的浓度在5.0×10-6～2.0×10-4 mol/L范围内呈良好的线性关系, 相关系数为0.9989, 检出限为1.0×10-6 mol/L. 该方法操作简便, 重现性较好, 能在抗坏血酸存在下同时测定UA. 用于人血中UA的测定.     

锰负载量对活性炭载锰氧化物的结构及催化分解臭氧性能的影响简

将高锰酸钾与活性炭（AC）原位氧化还原制备的活性炭载锰氧化物（MnO_x/AC）用作臭氧分解的催化剂. 采用扫描电镜、X射线光电子能谱、X射线衍射、电子自旋共振波谱、拉曼光谱以及程序升温还原研究了设计Mn负载量对负载锰氧化物性质（形貌、氧化态和晶体结构）的影响. 结果表明,Mn负载量由0.44%增至11%,负载锰氧化物在活性炭表面由疏松的地衣状变为堆叠的纳米球状体,负载层的厚度由~180 nm增加至~710 nm,结构由氧化态+2.9到+3.1的低结晶β-MnOOH生长为由氧化态+3.7到+3.8的δ-MnO₂结晶. MnO_x/AC室温催化分解低浓度臭氧的活性与负载锰氧化物的形貌及含量密切相关. Mn负载量为1.1%的MnO_x/AC具有疏松的地衣状形貌,催化分解臭氧的性能最高,Mn负载量为11%的MnO_x/AC具有紧密的堆积结构,因而表现出最低的催化臭氧分解活性.     

Selective adsorption and removal ability of pine needle-based activated carbon towards Al(III) from La(III)

Rare earth elements are an important strategic resource. As one of the most valuable member, lanthanum plays a key role in lanthanide. However, trace Al(III) impurity in lanthanum materials can seriously damage the performance of lanthanum materials. In this paper, a nitrogen-containing activated carbon, AC-PN-700, was synthesized using pine needle as raw material and KOH as activator. The AC-PN-700 was characterized by surface area analyzer, elemental analysis and FT-IR. The adsorption and selective ability of AC-PN-700 towards Al(III) were investigated. The BET specific surface area of AC-PN-700 was 596.4 m².g^?1, and the average pore diameter was 2.7?nm. Depend on its large specific surface, well-developed internal pore structure and abundant nitrogen-containing functional groups, the AC-PN-700 possesses strong adsorption affinity and excellent recognition selectivity towards Al(III). The adsorption capacity of AC-PN-700 towards Al(III) could reach to 3.89?mg.g^?1, removal rate towards Al(III) was almost 100%, and relative selectivity coefficients with respect to La(III) is 9.5. The empirical Freundlich isotherm was found to describe well the equilibrium adsorption data. In addition, AC-PN-700 possesses better regeneration ability and reusability.     

Adsorption of cationic methylene blue dye using microwave-assisted activated carbon derived from acacia wood: Optimization and batch studies

This study assesses the performance of optimized acacia wood-based activated carbon (AWAC) as an adsorbent for methylene blue (MB) dye removal in aqueous solution. AWAC was prepared via a physicochemical activation process that consists of potassium hydroxide (KOH) treatment, followed by carbon dioxide (CO₂) gasification under microwave heating. By using response surface methodology (RSM), the optimum preparation conditions of radiation power, radiation time, and KOH-impregnation ratio (IR) were determined to be 360 W, 4.50 min, and 0.90 g/g respectively, which resulted in 81.20 mg/g of MB dye removal and 27.96% of AWAC’s yield. Radiation power and IR had a major effect on MB dye removal while radiation power and radiation time caused the greatest impact on AWAC’s yield. BET surface area, mesopore surface area, and pore volume of optimized AWAC were found to be 1045.56 m²/g, 689.77 m²/g, and 0.54 cm³/g, respectively. Adsorption of MB onto AWAC followed Langmuir and pseudo-second order for isotherm and kinetic studies respectively, with a Langmuir monolayer adsorption capacity of 338.29 mg/g. Mechanism studies revealed that the adsorption process was controlled by film diffusion mechanism and indicated to be thermodynamically exothermic in nature.     

Effects of the thermal decomposition of surface oxygen species on the chemical and catalytic properties of activated carbon supported Pt catalysts

Several carbon supported Pt catalysts were prepared by varying surface properties of support and tested for methylene chloride oxidation. They were investigated by BET, TPD, pH analysis and XPS. The Pt species would stabilize when the surface carbon was pregraphitized due to the π sites of basal plane. This revised version was published online in June 2006 with corrections to the Cover Date.     

载Mo和Ni-Mo酚醛树脂基活性炭加氢催化转化羰基硫的研究

将水溶性酚醛树脂与金属盐溶液混合形成均相体系,依次通过减压蒸馏、固化、炭化、活化和预硫化处理制备负载金属硫化物的活性炭脱硫剂;研究其对羰基硫（COS）的加氢转化催化活性,考察了担载金属的种类、担载量、反应温度、反应时间和COS入口浓度等因素对催化反应的影响。研究结果表明,水溶性酚醛树脂是制备催化剂炭载体的理想前驱体;Ni Mo双组分催化剂对COS的加氢催化转化活性明显高于Mo单组分催化剂;在金属硫化物/活性炭催化剂上,COS的催化加氢过程属于内扩散控制,加氢反应气氛中一定浓度含硫组分的存在是抑制催化剂失硫及维持其催化活性的必要条件。