甲烷液相部分氧化合成甲醇过程研究

以碘系列化合物为催化剂,在发烟硫酸溶剂中进行了甲烷液相选择性氧化制取甲醇。考察了催化剂种类、用量、反应温度、发烟硫酸浓度等工艺条件对反应收率的影响,探讨了甲烷液相选择性氧化的催化机理以及发烟硫酸中 SO3 含量的作用。实验结果表明,甲烷液相部分氧化的最佳催化剂为 I2,最佳的工艺条件为催化剂浓度为0.099 mol?L?1、反应温度 473K、发烟硫酸(SO350%(wt))、反应时间 3h。 在此条件下,甲烷转化的转化率可达 82.65%,选择性可达 70.43%。机理研究表明,甲烷在部分氧化反应中首先转化为硫酸单甲酯,然后进一步水解得到甲醇, 反应遵循亲电取代机理。发烟硫酸中的游离 SO3的作用就在于提供较好的亲电环境、反应的氧源以及亲核试剂。     

甲烷液相催化氧化制甲醇反应介质的研究进展

甲烷直接催化氧化制甲醇的研究,对于实现甲烷直接转化及边远地区天然气和油田伴生气的输配利用具有重要意义。从反应介质的角度对甲烷直接液相催化氧化制甲醇的研究进展进行了评述,分析了发烟硫酸、醋酸-杂多酸体系、离子液体、水介质的优缺点,并对该领域未来的研究和发展方向进行了展望。     

甲烷低温活化制甲醇研究进展

简要评述了当前国内外在甲烷直接部分氧化合成甲醇和甲烷经卤代后合成甲醇领域的研究进展。众多研究表明,甲烷多相催化氧化制甲醇是最具有工业化应用前景的技术,其中钼系催化剂的效果较好;以Pt、Pd配合物为催化剂的甲烷液相催化氧化法制甲醇方法具有较高的甲烷转化率和甲醇选择性,但是催化剂价格昂贵、反应条件苛刻、环境污染严重;甲烷气相均相氧化属于非催化反应,在高温高压下进行,且反应器须具备特殊的形式,结构复杂;虽然酶催化氧化法的选择性较高,但是生物酶的制备有一定难度,不适用于大范围应用,该路线目前仅限于实验室研究阶段;光催化氧化是一种环境友好的技术,反应条件温和、避免氧化剂应用,但是该类催化剂局限于半导体和盐类,还有待于进一步开发新型高效的催化剂。同时,甲烷经卤代后合成甲醇的方法对解决甲烷活化的难题具有独特优势,是一种比较有开发前景的路线,正在受到研究者们的密切关注。     

V2O5催化甲烷液相部分氧化工艺过程研究

以V2O5为催化剂,在发烟硫酸中进行了甲烷液相选择性氧化的研究工作,考察了V2O5催化剂用量、反应温度、反应时间、发烟硫酸浓度等工艺条件对反应收率的影响,进行了甲烷液相选择性氧化的催化机理探讨和宏观动力学推导.甲烷在部分氧化反应中首先转化为硫酸甲酯,后者进一步水解得到甲醇.甲烷转化率可达54.5%,选择性45.5%,相应的工艺条件为催化剂用量0.0175 mol、反应温度180C、发烟硫酸中SO3含量50%(wt)、反应时间2 h.V2O5催化甲烷液相部分氧化反应遵循亲代取代机理,甲烷液相部分氧化反应为一级反应.     

膜催化技术用于甲烷转化反应的研究进展

介绍了膜催化技术在甲烷转化反应中的应用,这些过程包括甲烷氧化偶联反应制乙烯,甲烷部分氧化制甲醇,甲烷水蒸气重整制合成气等,通过膜催化反应与传统催化反应的比较,揭示了膜催化技术的优点。     

甲烷直接转化的研究现状与展望

介绍了甲烷直接转化的国内外研究现状,系统阐述了近年来甲烷直接氧化制甲醇、甲醛,氧化偶联制乙烯,甲烷的芳构化,甲烷无氧同系化的研究进展。对新型纳米结构催化剂,微波辅助下的催化转化,以离子液体为介质的反应系统研究甲烷直接转化的新领域作了介绍。     

分子氧存在下镁铝水滑石负载高锰酸钾活化醇类液相氧化反应研究

用共沉淀和浸渍法分别制得镁铝水滑石固载MnO4-催化剂HT-MnO4-,并将该催化剂在温和条件下、以分子氧为氧化剂用于催化醇的液相氧化反应.以苯甲醇氧化反应为模型探讨了不同制备方法制得的催化剂以及温度、溶剂等条件对反应的影响,结果显示两种制备方法对催化性能影响的差别不大,非极性溶剂更有利于反应进行,苯甲醇转化率随着温度上升明显提高.XRD表征给出水滑石经过MnO4-阴离子交换以后,X射线衍射峰中最强峰对应晶面的平均粒径减小,但结构仍然完整;XPS表征表明HT-MnO4-中Mn的结合能较之KMnO4中的Mn有所降低.说明镁铝水滑石负载高锰酸钾远比高锰酸钾温和,在醇的液相氧化中同时起着催化剂和氧化剂的作用.     

醋酸混合溶剂中碘催化甲烷部分氧化过程研究

在醋酸和杂多酸混和溶剂中进行了甲烷液相部分氧化过程研究.进行了碘系列催化剂以及溶剂体系中杂多酸筛选,考察了催化剂用量、磷钨酸浓度、氧化剂类型、反应温度、压力等条件对甲烷转化的影响.结果表明,在磷钨酸浓度0.072 mol/L,碘含量0.04 mol/L,KMnO4为0.158 mol/L,温度210℃,压力4.0 Mpa条件下,甲烷转化率可达12.98%,目的产物醋酸甲酯选择性84.39%.初步探讨了醋酸和磷钨酸混合溶剂中碘催化甲烷液相选择性氧化的亲电反应机理.     

甲烷部分氧化反应的磷钨酸催化剂研究

以磷钨酸为催化剂和氧化剂,进行了无氧条件下的甲烷气固相部分氧化的实验研究,考察了磷钨酸催化剂的制备条件、载体影响以及反应温度对甲烷部分氧化反应的影响等.磷钨酸催化剂可有效催化甲烷部分氧化反应,甲烷首先转化生成醋酸甲酯,醋酸甲酯水解生成甲醇.制备的催化剂以SiO2为载体,采用载体质量15%(wt)的磷钨酸水溶液回流浸渍4 h、120℃干燥2 h、300℃焙烧4 h制得.甲烷部分氧化反应在0.10 MPa、267～280℃进行,甲烷转化率为26.61%,目的产物收率25.82%.     

天然气制甲醇合成气工艺及进展

论述了国内外天然气制甲醇合成气各工艺的研究现状,进展及发展方向。天然气制合成气的典型工艺是水蒸气催化转化法,其技术成熟,但投资大,能耗高,生产的合成气不适于直接用来合成甲醇。天然气与CO2催化转化工艺可制得富含CO的合成气,解决蒸气转化法氢过剩的问题,实现CO2的减排,目前对该法的研究主要集中在开发新型催化剂和优化反应条件等。两段转化法即一段炉采用蒸气转化,两段炉用富氧或纯氧转化,无需经转化炉前或炉后添加二氧化碳,就可达到合成甲醇原料气成分的要求。甲烷部分氧化法能耗低,反应易控制,可制得符合比例要求的甲醇合成气,但尚未见到该技术工业化的相关报道。甲烷自热转化工艺是在反应器中耦合了放热的甲烷部分氧化反应和强吸热的甲烷蒸气转化反应,反应体系本身可实现自供热,该工艺一般采用富氧空气或氧气,因此需氧气分离装置,增加了投资,这是制约其发展和应用的主要障碍。     

醋酸与磷钨钼酸混合溶剂中甲烷部分氧化研究

采用单因素考察法考察了以碘为催化剂,在醋酸和磷钨钼酸混合溶剂中各种工艺条件对甲烷液相部分催化氧化反应的影响。磷钨钼酸与醋酸的混合溶剂体系可用于甲烷部分氧化反应,以碘为催化剂有较好的催化效果。通过对液相产物的分析,提出了在醋酸与磷钨钼酸混合溶剂中甲烷液相部分氧化反应属于亲电取代反应机理。反应条件为碘催化剂浓度0.04 mol/L,混合溶剂中醋酸50 mL,磷钨钼酸0.14 mol/L,氧化剂K2S2O80.20 mol/L,温度210℃,压力4.0 MPa时,甲烷转化率可达32.79%,目的产物选择性可达96.64%。     

Characteristics of the Photocatalytic Oxidation of Methane into Methanol on V-Containing MCM-41 Catalysts

V-containing MCM-41 catalysts were prepared by a direct synthesis method under acidic and basic conditions and impregnation. Their photocatalytic reactivity was evaluated for the selective photocatalytic oxidation of methane with NO under UV irradiation at 295 K. Selective methanol formation was observed on V-MCM-41 prepared in acidic solution and imp-V/MCM-41, while only coupling reaction products were obtained on V-MCM-41 prepared in basic solution. The photocatalytic reactivity of the catalysts for the partial oxidation of methane was found to strongly depend on the local structure of the V-oxide species including the coordination and loading sites, i.e., the charge transfer excited states of the isolated tetrahedral V⁵⁺-oxide species supported on the catalyst surface act as the active sites for the selective photocatalytic oxidation of methane into methanol.     

Methanol formation from methane partial oxidation in CH4–O2–NO gaseous phase at atmospheric pressure

The reaction condition for high yield of methanol in a gaseous reaction between methane and oxygen in the presence of NO at atmospheric pressure was explored. Methane partial oxidation without NO (CH₄–O₂) gave only 1% conversion of methane at 966 K. The addition of NO led to a remarkable increase in methane conversion and to high selectivity to C₁-oxygenates. The conversion of methane attained 10% at 808 K in the presence of NO (0.5%) where the selectivities to methanol and formaldehyde were 22.1 and 24.1%, respectively. Nitromethane and carbon oxides were also observed in the product gas. The amount of nitromethane was almost equal and/or near to that of initial NO. The carbon monoxide produced was several times higher than carbon dioxide. Influences of NO concentration, ratio of methane to oxygen, water vapor, and dilution with helium gas on product distribution were measured. Low concentration of NO (0.35–0.55%) was favorable for methanol formation. High selectivity to methanol was obtained at low value of the ratio of methane to oxygen (2.0–3.0) or low concentration of dilution gas (<16%). The NO₂ added promoted methane partial oxidation and selectivity to methanol. Therefore, it was assured that NO_x promoted the formation of CH₃√ and CH₃O√ in the gas phase reaction for CH₄–O₂–NO.     

环己烷绿色氧化合成环己醇/环己酮(KA油)催化剂及机理研究进展

环己烷绿色氧化合成环己醇/酮(KA油)一直是饱和C—H氧化领域的研究热点。本文综述了近十年来过氧化氢环己烷氧化和分子氧液相环己烷氧化的催化研究情况,指出过氧化氢环己烷氧化反应虽然条件温和、环己烷转化率和KA油选择性高,但活性较高的反应体系一般为包含昂贵配合物、酸、溶剂和氧化剂的复杂均相体系,不利于产物和催化剂分离,同时过氧化氢利用率较低,氧化剂成本高。液相分子氧环己烷氧化采用多相催化剂,操作简单,其中金和纳米氧化物有望成为潜在的工业催化剂。对环己烷氧化机理成果进行分析,指出除了金属卟啉的氧异裂非自由基机理,环己烷氧化按自由基机理进行,为自催化反应,但催化剂可促进活性自由基产生,活化C—H键,提高反应速率。最后指出开发有潜力的环己烷氧化多相催化剂和探索反应机理是今后的研究方向。     

Partial oxidation of methane with air for methanol production in a post-plasma catalytic system

Partial oxidation of methane to methanol via post-plasma catalysis using a dielectric-barrier discharge was performed under mild reaction conditions. Air was used as the oxidizing co-reactant because of its economical practicality. Three catalysts impregnated with Pt, Fe₂O₃, CeO₂ on ceramic supports located downstream of the discharge zone were examined for increased selectivity towards methanol. It was found that all three catalysts had no significant effect on the conversion of methane, but enhanced methanol selectivity, which could be explained by a two-stage reaction mechanism. The Fe₂O₃-based catalyst showed the best catalytic activity, and high stability in the reaction. The methanol selectivity of the Fe₂O₃-assisted plasma process was 36% higher than that of the non-catalytic system at a rather low catalyst temperature (150 °C). In addition, the effects of input power, discharge frequency, discharge gap distance, total flow rate, and methane/air ratio on methane conversion and methanol yield were also studied.     

甲烷部分氧化制甲醇及甲醛

综述了甲烷部分氧化制甲醇及甲醛工艺在催化剂、载体、选择反应条件及氧化反应机理等方面的研究进展。建议研制开发新型的复合型催化剂。     

Biological conversion of methane to methanol

The conversion of methane to methanol is important to economic utilization of natural/shale gas. Methanol is a valuable liquid fuel and raw material for various synthetic hydrocarbon products. Its industrial production is currently based on a two-step process that is energy-intensive and environmentally unfriendly, requiring high pressure and temperature. The biological oxidation of methane to methanol, based on methane monooxygenase activity of methanotrophic bacteria, is desirable because the oxidation is highly selective under mild conditions, but conversion rate and yield and stability of catalytic activity should be improved up to an industrially viable level. Since methanotrophic bacteria produce methanol as only a precursor of formaldehyde that is then used to synthesize various essential metabolites, the direct use of bacteria seems unsuitable for selective production of a large amount of methanol. There are two types of methane monooxygenase: soluble (sMMO) and particulate (pMMO) enzyme. sMMO consisting of three components (reductase, hydroxylase, and regulatory protein) features an (αβγ)₂ dimer architecture with a di-iron active site in hydroxlase. pMMO, a trimer (pmoA, pmoB, and pmoC) in an α ₃ β ₃ γ ₃ polypeptide arrangement is a copper enzyme with a di-copper active site located in the soluble domain of pmoB subunit. Since the membrane transports electrons well and delivers effectively methane with increased solubility in the lipid bilayer, pMMO seems more rationally designed enzyme in nature than sMMO. The engineering/evolution/modification of MMO enzymes using various biological and chemical techniques could lead to an optimal way to reach the ultimate goal of technically and economically feasible and environmentally friendly oxidation of methane. For this, multidisciplinary efforts from chemical engineering, protein engineering, and bioprocess research sectors should be systematically combined.     

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。