SO42－/ZrO2/SBA-15催化丙烯和乙酸合成乙酸异丙酯的研究

水热合成了介孔材料SBA-15，并以其为载体负载固体超强酸SO₄^2－/ZrO₂，得到催化剂 SO₄^2－/ZrO₂/SBA-15，通过XRD对其进行表征。在固定床反应器中，以丙烯和乙酸为原料，研究该催化剂催化合成乙酸异丙酯的活性。对反应条件进行系统地考察，得出最佳反应条件：反应温度140 ℃,反应压力1.2 MPa,空速1 h^－1,n(C₃H₆)∶n(CH₃COOH)=3∶1。在此条件下乙酸异丙酯的产率最高可达79.6％。     

固体超强酸SO2-4/TiO2催化合成乙酸苯酯

以沉淀法制备了SO^2-₄/TiO₂和SO^2-₄/ZrO₂固体超强酸,采用Hammett指示剂对催化剂进行了表征。比较了不同催化剂对乙酸酐与苯酚直接酯化合成乙酸苯酯的催化活性,并考察了固体超强酸催化剂的制备条件及酯化反应条件对催化活性的影响。实验结果表明,SO^2-₄/TiO₂₂固体超强酸具有较高的催化活性,最佳合成条件：SO^2-₄/TiO₂于600 ℃焙烧4 h,固体超强酸SO^2-₄/TiO₂用量为原料总质量的3%,原料乙酸酐与苯酚物质的量比为1.05∶1.00,反应温度（140~150） ℃,反应时间1.5 h,乙酸苯酯收率为98.0%。     

Pd/Al2O3催化剂上CH4选择性还原NO的研究

考察了Pd/Al₂O₃、In/Al₂O₃和Co/Al₂O₃对甲烷选择性还原NO的催化活性。结果表明，采用浸渍法制备的Pd/Al₂O₃、In/Al₂O₃和Co/Al₂O₃三种催化剂，在有氧气氛下，用CH₄作还原剂催化还原NO时，Pd/Al₂O₃催化剂的活性最佳，热稳定性好，在550 ℃，用CH₄选择还原NO，Pd/Al₂O₃催化剂表现出较强的催化能力，NO的转化率达到100%。在高空速实验中，该催化剂亦表现出较高的活性，其活性顺序为Pd/Al₂O₃>In/Al₂O₃>Co/Al₂O₃。实验研究了助催化剂、氧含量以及空速对Pd/Al₂O₃催化剂活性的影响。     

煤矿瓦斯气中低浓度CH4吸附富集研究

煤矿通风口处瓦斯气的CH₄浓度太低无法回收利用，只能排往大气中，既浪费能源，又污染环境。在活性炭吸附存储CH₄的基础上，对活性炭选择性吸附富集CH₄进行了初步研究。考察了多种吸附材料在常温和常压下对瓦斯气中低浓度CH₄的选择吸附能力，并关联了吸附材料结构参数和吸附性能之间的关系。实验结果表明，活性炭对低浓度CH₄有较强的吸附性能，孔径是决定活性炭能否选择性吸附CH₄的主导因素，而微孔比表面积及微孔孔容是次要因素。氧化改性不利于活性炭对CH₄的吸附，高温处理过程是获得高吸附性能活性炭的有效手段。     

固体超强酸SO2－4-MoO3-ZrO2的酸强度与酯化催化性能

固体超强酸催化剂SO^2－₄-MoO₃-ZrO₂用于乙酸丁酯的合成，其催化活性高于SO^2－₄-ZrO₂和MoO₃-ZrO₂。用TPD技术对催化剂的酸强度及其分布进行了研究，结果表明，MoO₃对催化剂的酸强度及其分布具有调变作用，调变后的酸强度分布更有利于乙酸/正丁醇酯化反应的进行。     

CH4与CO检测气敏元件中催化剂的制备与反应性能研究

实现CH₄和CO的多参数检测，催化剂及其催化反应性能是基础。研究了纳米载体Al₂O₃的制备方法，对其孔径分布和前驱体的颗粒度进行了BET和TEM的测定，对CH₄和CO在Pd/Al₂O₃催化剂上的催化反应性能进行了评价。结果表明,采用共沉淀-凝胶工艺和控制制备条件可以得到适宜孔径的催化剂载体。CH₄和CO在Pd/Al₂O₃催化剂上的催化反应性能有较大的差异。催化反应可以满足对CH₄和CO的多参数检测的需要。     

CH4CO2催化重整制合成气的研究进展

综述了CH₄CO₂催化重整制合成气的研究进展，分析讨论了催化剂的研究状况、反应机理、动力学、催化剂失活特性和非常规供能方式在催化重整反应中的应用等。结果表明，CO₂催化重整过程开发成功的关键是有效抑制催化剂积炭失活。     

γ-Al2O3在CeO2-La2O3催化还原SO2中的作用

考察了反应温度对γ-Al₂O₃、CeO₂-La₂O₃和CeO₂-La₂O₃/γ-Al₂O₃催化CO还原SO₂到单质硫活性的影响。采用XRD表征了催化剂反应前后的物相变化。结果表明，温度过低或过高均不利于γ-Al₂O₃催化CO还原SO₂的反应。γ-Al₂O₃的介入提高了CeO₂和La₂O₃的分散性，使Redox 和COS两种反应机理在同一催化剂上的协同作用增强，使CeO₂-La₂O₃/γ-Al₂O₃在催化还原SO₂的反应中具有更低的反应温度和更高的活性。     

固体超强酸SO2－4/TiO2/La3+催化合成二甲基丙烯酸丁二醇酯

以自制稀土改性固体超强酸SO^2－₄/TiO₂/La³⁺为催化剂，高效合成了二甲基丙烯酸丁二醇酯。比较了不同催化剂的催化活性，并考察了固体酸的制备条件及酯化反应条件对催化活性的影响，得到最佳合成条件为:SO^2－₄/TiO₂/La³⁺于500 ℃下活化3 h，n(酸)∶n(醇)=2.8∶1，阻聚剂、催化剂质量分数分别为1.0%和1.2%，反应温度维持在120 ℃左右反应2 h左右，酯化率可达92.0%。     

i(SO4)2/SiO2催化合成苯甲酸异戊酯的研究

以Ti(SO₄)₂/SiO₂为催化剂，苯甲酸和异戊醇为原料，合成了苯甲酸异戊酯。对影响酯化反应的因素进行了研究。优化的工艺条件：负载硫酸钛质量分数为10%，催化剂用量为2.5 g·(0.05 mol-苯甲酸)^-1，醇酸物质的量比为4∶1，反应时间为90 min，苯甲酸的酯化率可达96.6%。     

CH4、CO2、O2直接合成乙酸的可行性研究

在分析总结了甲烷的临氧活化以及近年来国内外CH4-CO2直接转化合成乙酸研究成果的基础上,提出了在CH4-CO2体系中引入O2直接合成乙酸的新方法,并从反应热力学及反应机理方面进行了可行性分析。     

甲烷低温催化直接合成乙酸的新途径

对甲烷经合成气路线间接制乙酸的现状及在温和条件下直接转化制乙酸的研究进展作了述评．通过对间接与直接路线的比较．以及在直接路线中,甲烷低温氧化羰化和直接羧化制乙酸均相与非均相催化体系的分析。指出了CH4-CO2低温直接合成乙酸在工艺过程上的显著优势,尤其是采用非均相催化体系．该工艺为乙酸合成和CH4与CO2的绿色化学利用开辟了新途径。其研究将会丰富C1化学化工的理论与实践．并为实现热力学不利反应提供实验方法和理论依据。     

C1化学产品合成醋酸的研究

近年来醋酸合成方面的研究取得了很大的进展,其中包括甲醇羰基化、合成气一步合成醋酸、CO2加氢生成醋酸,CO2与甲烷的在等离子体状态下合成醋酸等。本文对C1化学在醋酸合成开发研究中的进展进行了论述。     

Carbon deposition from irradiated methane

Carbon-14 tracer techniques have been used to measure directly the carbon deposition resulting from the radiolysis of methane by itself and in the presence of carbon dioxide, oxygen and graphite. It is shown that carbon deposition is increased in the presence of carbon dioxide and decreased in the presence of oxygen. at high carbon dioxide pressures (40 cm Hg) and high doses (>100 Mrad), the majority of the methane is decomposed to deposit. Irradiation of methane by itself produces less deposit than in the presence of graphite and there is an enhancement of the surface deposit compared with that within the bulk of the graphite. The results of the analyses for light hydrocarbons produced during methane radiolysis over a range of conditions are also briefly discussed.     

An investigation on the reaction mechanism for the partial oxidation of methane to synthesis gas over platinum

The partial oxidation of methane to synthesis gas has been investigated by admitting pulses of pure methane, pure oxygen and mixtures of methane and oxygen to platinum sponge at temperatures ranging from 973 to 1073 K. On reduced platinum the decomposition of methane results in the formation of surface carbon and hydrogen. No deposition of carbon occurs during the interaction of methane with a partly oxidised catalyst. Oxygen is present in three different forms under the conditions studied: platinum oxide, dissolved oxygen and chemisorbed oxygen species. Carbon monoxide and hydrogen are produced directly from methane via oxygen present as platinum oxide. Activation of methane involving dissolved oxygen provides a parallel route to carbon dioxide and water. Both platinum oxide and chemisorbed oxygen species are involved in the oxidation of carbon monoxide and hydrogen. In the presence of both methane and dioxygen at a stoichiometric feed ratio the dominant pathways are the direct formation of CO and H₂ followed by their consecutive oxidation. A Mars-van Krevelen redox cycle is postulated for the partial oxidation of methane: the oxidation of methane is accompanied by the reduction of platinum oxide, which is reoxidised by incorporation of dioxygen into the catalyst.     

Low-Temperature Coupling of Methane

Methane is the main component of natural gas and its utilization amounts to ca. 1.7 × 10⁹ tons of oil equivalent per year [1]. Since the present reserve of methane is located in remote places, its transportation is a major problem. Methane coupling to form C₂₊ hydrocarbons is, therefore, of a primary importance because before transportation methane should be converted into hydrocarbons with higher boiling points, such as ethane, propane, etc. The catalytic conversion of methane can be carried out in several ways which have excellently been reviewed in Refs. 1 and 2. Basically, three routes exist: (i) the indirect route in which methane is first converted into syngas in presence of water (steam reforming), CO₂ (carbon dioxide reforming), or oxygen (partial oxidation) and the resultant syngas can be utilized in the traditional way; (ii) direct coupling in the presence of oxygen (oxidative coupling of methane, OCM) or hydrogen (two-step polymerization); and (iii) direct conversion in the presence of oxygen to oxygenates (CH₃OH, HCOH), in the presence of Cl₂, HCI to methane chlorides, in the presence of ammonia to HCN, etc.     

L'effet du molybdène sur l'oxydation partielle du méthane par l'oxygène-pur

An investigation was carried out to establish the influence of molybdenum powder on the partial oxidation of methane with pure oxygen and to find the reaction conditions that lead to its complete conversion to synthesis gas without excess oxygen nor formation of carbon dioxide, water vapor and carbon deposits. Carbidization of molybdenum by methane and its decarbidization by oxygen lead one to suggest steps that explain the observed products. Thermodynamic feasibility of the steps suggested was established from equilibrium constants. Gas compositions at equilibrium were calculated for various reaction conditions. Sixty experiments were carried out to verify the calculated compositions. The temperature was varied from 1200 to 1900°K; the weight of molybdenum, from 0 to 5 grams; the methane to oxygen ratio, from 1.6 to 2.2 and the hourly space velocity, from 50 to 250. Above 1600°K, 2 to 1 ratio stoichiometric mixtures of methane and oxygen in the presence of molybdenum, generally yield pure synthesis gas (no carbon deposits, water vapor or carbon dioxide). X-ray diffraction analysis of the solids in the reactor confirmed the presence of large amounts of molybdenum carbide (but no oxide). This is strong evidence in support of the role assigned to molybdenum in eliminating carbon deposits.     

Coproduction of acetic acid and hydrogen/power from natural gas with zero carbon dioxide emissions

A process plant flow sheet that coproduces acetic acid and hydrogen/power from natural gas with zero carbon dioxide emissions is developed. Two cases are explored: the production of acetic acid and hydrogen (Case 1) and the production of acetic acid and power (Case 2). This is realized by the selection of an appropriate reaction cluster whose sum results in the overall reaction that coproduces acetic acid and hydrogen/power. The concept of energetic self‐sufficiency is introduced and it imposes constraints on the system defined in terms of the ratio of oxygen feed to acetic acid produced. Heat and power integration of the converged flow sheet reveals an operating range for each case that guarantees energetic self‐sufficiency. Operating points are chosen to conduct a preliminary economic analysis and a carbon dioxide cost and performance metric calculation to quantify profitability and carbon capture potential of the overall process. © 2017 American Institute of Chemical Engineers AIChE J, 64: 860–876, 2018     

等离子体技术及其在催化领域中的应用

本文介绍了等离子体的特性，发生技术及其在催化剂的制备、再生和改性中的应用。并以甲烷与二氧化碳反应制合成气，甲烷与二氧化碳反应制乙酸及甲烷部分氧化制甲醇，甲烷偶联反应制低碳烃等为例介绍了等离子体技术在催化反应中的应用，分析了等离子体状态下的催化反应机理，从而预测了等离子体技术在催化领域中的应用前景。     

Oxidative methane conversion to carbon monoxide and hydrogen at low reactor wall temperatures over ruthenium supported on silica

Oxidative methane conversion to carbon monoxide and hydrogen is catalyzed over ruthenium supported on silica at reactor wall temperatures as low as 400° C when the flow rate of reactants (methane and oxygen) is significantly high. The conversion of methane and the yields of carbon monoxide and hydrogen increase with increase in the flow rate of the reactants while oxygen is always completely consumed. Addition of carbon dioxide to the reactant flow can increase the yield of carbon monoxide in the reaction, suggesting that carbon dioxide functions as an oxidant and the actual surface temperature of the catalyst is sufficiently high that thermal conversion of methane via carbon dioxide and water can take place.