Processing of Oil Refinery Gases: Oxidative Dehydrogenation of the Ethane–Ethylene Fraction

Oxidative transformations of the ethane–ethylene fraction of oil refinery gases, containing 20 vol % C₂H₄, on VMoTeNb oxide catalyst in the temperature interval 330–450°C were studied. Comparison with oxidative transformations of the individual components (oxidative dehydrogenation of C₂H₆ and oxidation of C₂H₄) shows that ethylene does not noticeably influence the ethane conversion, whereas ethane strongly suppresses the ethylene conversion. The maximal yield of ethylene from the ethane–ethylene fraction is close to that reached in oxidative dehydrogenation of ethane under similar conditions and amounts to 70–72%.     

Oxidative dehydrogenation of ethane with carbon dioxide over sulfated zirconia supported metal oxides catalysts

Several metal oxides supported on sulfated zirconia catalysts were tested for the oxidative dehydrogenation of ethane into ethylene by carbon dioxide. It is found that the catalytic behavior of supported oxide catalysts differ depending on the nature of metal oxides. Chromium oxide-sulfated zirconia exhibits the highest ethane conversion and medium level of ethylene selectivity, producing 38% ethylene yield at 50% ethane conversion at 650°C.     

羟基化氮化硼催化乙烷氧化脱氢制乙烯

乙烯是最为重要的化工原料之一,目前其工业来源主要来自于烃类的水蒸汽裂解过程.该过程本质上是一个高温均相裂解过程,温度(>800?℃)高,能耗大,碳排放严重.乙烷氧化脱氢制乙烯属于放热反应,反应温度低,速率快,无积碳等限制,是一条更富有竞争力的工艺路线.然而,常用的金属或金属氧化物催化剂容易导致乙烯深度氧化,从而降低了乙烯选择性.纳米碳材料在烃类氧化脱氢反应中展现出一定的催化活性,但容易被氧化,难以用于反应温度高的乙烷氧化脱氢反应.本文报道了羟基化的氮化硼(BNOH)可高效催化乙烷氧化脱氢制乙烯.氮化硼边沿羟基官能团脱氢生成了动态活性位,从而引发了乙烷的脱氢反应.BNOH对乙烷氧化脱氢制乙烯显示出高选择性.当乙烷转化率在11%,乙烯选择性可高达95%;当乙烷转化率增加到40%,乙烯选择性保持在90%.重要的是,当乙烷转化率超过60%时,BNOH仍然可保持80%的乙烯选择性以及50%的乙烯收率.这些性能指标与现有工业乙烷水蒸气裂解过程运行性能相当.进一步优化反应条件,BNOH催化剂能够实现高达9.1 gC2H4 gcat-1 h-1的时空收率.经过200 h的氧化脱氢反应测试,BNOH催化剂活性和选择性基本恒定,表明其具有非常好的稳定性.X射线粉末衍射结果显示,反应前后BNOH催化剂的物相没有发生变化.透射电子显微镜测试证实,反应后BNOH催化剂的形貌和微观结构也没有明显改变.X射线光电子能谱结果显示,反应200 h后BNOH催化剂表面的氧含量仅从反应前的6.9 atom%微增到8.3 atom%.1H固体核磁共振谱测试显示,反应200 h后,BNOH催化剂上羟基含量无明显改变.结合原位透射红外光谱和同位素示踪实验,初步确定了BNOH催化剂上引发乙烷氧化脱氢反应的活性中心.氮化硼边沿的氧官能团并不能引发乙烷的氧化脱氢反应,而羟基官能团才是氧化脱氢反应发生的活性位.在乙烷氧化脱氢条件下,分子氧脱除羟基官能团上的氢原子动态生成BNO·?和HO2·?活性位.密度泛函理论计算表明,乙烷首先在BNO·?或HO2·?位活化生成乙基自由基,这些中间物进一步与气相氧物种发生反应脱氢生成乙烯.动力学测试结果也验证了上述实验和理论结果.     

乙烷脱氢制乙烯技术研究进展及趋势

在碳中和及全球能源供需版图调整的背景下,乙烯生产原料轻质化成为主流趋势。乙烷脱氢制乙烯技术具有低能耗、低碳排、流程短、收率高、成本低等优势,但目前工业上主要通过乙烷蒸汽裂解法生产乙烯,其他方法工业化生产相对不成熟。本文简述了近年来乙烷脱氢制乙烯技术(包括直接催化脱氢、O₂辅助氧化脱氢、CO₂辅助氧化脱氢、化学链氧化脱氢、催化膜反应器脱氢等)工艺及催化剂的研究现状,同时介绍了其他新兴工艺及催化剂。乙烷脱氢制乙烯技术现阶段面临的挑战不仅在于开发更高效的催化剂及更低能耗的技术,更需要突破乙烷脱氢热力学平衡的限制设计合适的反应路径,其中催化膜反应器脱氢、化学链氧化脱氢工艺都具有非常广阔的市场和工业化发展前景。     

纳米Cr2O3系列催化剂上CO2氧化乙烷脱氢制乙烯反应

 采用溶胶－凝胶法和共沸蒸馏法耦合技术制备了纳米Cr2O3催化剂，并采用共沉淀法和共沸蒸馏法耦合技术制备了纳米Cr2O3／Al2O3，Cr2O3／ZrO2和Cr2O3／MgO复合催化剂．应用BET，XRD，XPS，TPR和TEM等物理化学方法对催化剂的结构和物化性质进行了表征，并考察了该系列催化剂上CO2氧化乙烷脱氢制乙烯的反应性能．结果表明，纳米Cr2O3催化剂上乙烷和CO2的转化率均明显高于常规Cr2O3催化剂，但乙烯的选择性低于常规Cr2O3催化剂；纳米复合催化剂中的复合成分显著影响催化剂的催化性能．其中，10％Cr2O3／MgO纳米复合催化剂在温度为973K时，乙烷转化率和乙烯选择性分别可达到61．54％和94．79％．纳米催化剂表面Cr的还原性以及Cr6＋／Cr3＋比值是影响乙烷转化率和乙烯选择性的重要因素．     

Effect of methane co-feeding on the selectivity of ethylene produced from oxidative dehydrogenation of ethane with CO2 over a Ni-La/SiO2 catalyst

A Ni-La/SiO₂ catalyst was prepared through the incipient wetness impregnation method and tested in the oxidative dehydrogenation of ethane (ODHE) with CO₂. The fresh and used catalysts were characterized by XRD and SEM techniques. The Ni-La/SiO₂ catalyst exhibited catalytic activity for the oxidative dehydrogenation of ethane, but with low ethylene selectivity in the absence of methane. The selectivity to ethylene increased with increasing molar ratio of methane in the feed. The carbon deposited on the catalyst surface in the sole ODHE with CO₂ was mainly inert carbon, while much more filamentous carbon was formed in the presence of methane. The filamentous carbon was easy to be removed by CO₂, which might play a role in improving the conversion of ethane to ethylene. The introduction of methane might affect the equilibrium of the CO₂ reforming of ethane and the ODHE with CO₂. As a consequence, the synthesis gas produced from CO₂ reforming of methane partly inhibited the reaction of ethane and promoted the ODHE with CO₂, thus increasing the selectivity of ethylene.     

Energochemical technologies: energy and bulk/basic chemicals in a single process

The exoergic reactions, which underlie the production of large-scale basic chemicals for organic industry, can be used for one-pot generation of energy and chemical products. Typical examples include methane oxidative conversion to produce synthesis gas and methane oxidative dimerization to give ethylene and ethane.     

纳米Cr2O3的制备、表征及催化性能

首次采用溶胶-凝胶法与共沸蒸馏法耦合技术制备了纳米Cr2O3粉体，并运用BET、TEM、XRD、FT-IR、XPS及H2-TPR对其进行表征，同时采用CO2氧化乙烷脱氢制乙烯反应作为探针反应，考察了纳米Cr2O3的催化性能。首次发现纳米ErgO3的FT-IR谱出现了蓝移现象，并且630cm^-1附近的伸缩振动峰强度增强。初步探讨了纳米氧化物的IR蓝移和红移的原因，指出晶型是影响纳米氧化物红外光谱特征的重要因素。实验结果表明纳米Cr2O3上乙烷和CO2转化率均明显高于常规Cr2O3催化剂；在700℃下，乙烷转化率高达77．1％，而乙烯产率达到了58．98％。     

Copper-containing catalysts for the oxidative dehydrogenation of organic compounds

A method of doping magnesium aluminum hydrotalcites, which are precursors for oxidative dehydrogenation oxide catalysts of various compositions, with copper(II) was developed, and copper(II)-containing oxide catalyst samples were synthesized. The catalytic properties of these catalysts were studied in the oxidative dehydrogenation of ethane, propane, and hexane. The conversion of ethane into ethylene on the copper-containing catalysts was established to proceed with high selectivities (90?C97%) and at low temperatures (400?C450°C).     

Effect of group VIII elements on the behavior of Li/CaO catalyst in the oxidative dehydrogenation of ethane

The effect of addition of group VIII elements to Li/CaO on the oxidative dehydrogenation of ethane has been investigated in the range of 550–650°c. Iron, cobalt and nickel promote the reaction. The experiments show that iron and cobalt additives in Li/CaO catalysts mainly increase the catalytic activity. Li/Ni/CaO catalyst gives a high ethane conversion and excellent ethylene selectivity. The results on the catalyst are probably due to coordinative interaction between lithium and nickel. The characteristics of the catalysts revealed by XRD also give evidence that the promotion for both catalytic activity and ethylene selectivity is directly related to the formation of favorable crystal phases.     

Surface Acidity／Basicity and Catalytic Reactivity of CeO2／γ—A12O3 Catalysts for the Oxidative Dehydrogenation of Ethane with Carbon Dioxide to Ethylene

Dehydrogenation of ethane to ethylene in CO2 was investigated over CeO2/γ-Al2O3 catalysts at 700℃ in a conventional flow reactor operating at atmospheric pressure. XRD, BET and microcalorimetric adsorption techniques were used to characterize the structure and surface acidity/basicity of the CeO2/γ-Al2O3 catalysts. The results show that the surface acidity decreased while the surface basicity increased after the addition of CeO2 to γ-Al2O3. Accordingly, the activity of the hydrogenation reaction of CO2 increased, which might be responsible for the enhanced conversion in the dehydrogenation of ethane to ethylene. The highest ethane conversion obtained was about 15% for the 25?O2/γ-Al2O3. The selectivity to ethylene was high for all the CeO2, γ-Al2O3 and CeO2/γ-Al2O3 catalysts.     

甲烷氧化偶联锂/氧化镁催化剂和纳米催化剂

The Li/MgO catalyst and nanocatalyst were prepared by the incipient wetness impregnation and sol-gel method, respectively. The catalytic performance of the Li/MgO catalyst and nanocatalyst on oxidative coupling of methane was compared. The catalysts prepared in two ways were characterized by X-ray powder diffraction, Brunauer-Emmett-Teller surface and transmission electron microscope. The catalyst was tested at temperature of 973-1073 K with constant total pressure of 101 kPa. Experimental results showed that Li/MgO nanocatalyst in the oxidative coupling of methane would result in higher conversion of methane, higher selectivity, and higher yield of main products (ethane and ethylene) compared to ordinary catalyst. The results show the improved influence of nanoscale Li/MgO catalyst performance on oxidative coupling of methane.     

Selective ethane conversion into aromatic hydrocarbons over Zn-ZSM-11 zeolite

The conversion of ethane into aromatic compounds at 550°C and atmospheric pressure over Zn-ZSM-11 zeolite (Si/Al=17; 2.5 wt.% of Zn as counter ion) has been studied in a flow reactor at different partial pressures of ethane. The observed products at different ethane conversion levels were formed through a variety of processes including ethane dehydrogenation, producing ethylene as the only primary unstable product. Ethylene underwent very rapid reactions through carbenium ion intermediates, producing aromatic hydrocarbons and C1-C4 hydrocarbons as secondary products.     

Pulse reactions of methane, ethane and ethylene over Li-, La- and Sm-promoted MgO catalysts in the presence and absence of free oxygen

Pulse reaction of methane in the presence and absence of free (or gaseous) oxygen and that of ethane and ethylene in the absence of free oxygen over Li−MgO, La−MgO and Sm−MgO (Li or La or Sm/Mg ratio=0.1) have been investigated for elucidating the role of lattice and free oxygen in oxidative coupling of methane (OCM) over these catalysts. No significant role is played by the lattice oxygen from these catalysts in the OCM process. The presence of free oxygen is essential for all these catalysts to be active and selective in OCM process. However, lattice oxygen plays some role in ethane conversion but a very significant role in ethylene conversion over these catalysts.     

Deactivation of a mixed oxide catalyst of Mo–V–Te–Nb–O composition in the reaction of oxidative ethane dehydrogenation

The operational stability of a mixed oxide catalyst of Mo–V–Te–Nb–O composition in the oxidative dehydrogenation of ethane (ratio of C₂H₆: O₂ = 3: 1) is studied in a flow reactor at temperatures of 340–400°C, a pressure of 1 atm, and a WHSV of the feed mixture of 800 h^?1. It is found that the selectivity toward ethylene is 98% at 340°C, but the conversion of ethane at this temperature is only 6%; when the temperature is raised to 400°C, the conversion of ethane is increased to 37%, while the selectivity toward ethylene is reduced to 85%. Using physical and chemical means (XPS, SEM), it is found that the lack of oxidant in the reaction mixture leads to irreversible changes in the catalyst, i.e., reduced selectivity and activity. Raising the reaction temperature to 400°C allows the reduction of tellurium by ethane, from the +6 oxidation state to the zerovalent state, with its subsequent sublimation and the destruction of the catalytically active and selective phase; in its characteristics, the catalyst becomes similar to the Mo–V–Nb–O system containing no tellurium.     

Oxidative Dehydrogenation of Ethane to Ethylene over LiCl/MnOx/PC Catalysts

The catalytic stability of LiCl/MnO_x/PC catalyst have been investigated, the deactivation mechanism was discussed. The experimental results show that ethane conversion decreases and ethylene selectivity keeps about 90% as reaction time increases. The main deactivation reasons of LiCl/MnO_x/PC catalyst for oxidative dehydrogenation of ethane (ODHE) to ethylene are the transition of active species Mn₂O₃ to MnO species and the loss of active component Cl in catalyst. Instead of ethane with FCC tailed‐gas, the stability of LiCl/MnO_x/PC catalyst has been largely improved.     

Magnesium iron aluminum hydroxosalts and oxide catalysts for oxidative dehydrogenation of alkanes and alcohols

Methods are developed for the synthesis of precursors for oxide catalysts containing iron hydroxocarbonate and magnesium aluminum hydroxocarbonate with hydrotalcite-type layered structure and decavanadate and paramolybdate ions in anionic interlayers. These precursors are used to synthesize oxide catalysts for oxidative dehydrogenation of alcohols and alkanes with high selectivity and good yields of the desired product in conversion of ethane to ethylene and alcohols to carbonyl compounds.     

Synthesis of complex hydroxo salts of magnesium, nickel, cobalt, aluminum, and bismuth and oxide catalysts on their base

Synthesis methods have been developed for the precursors of oxide catalysts that include the combination of magnesium nickel cobalt aluminum hydroxocarbonate, with a layered hydrotalcite-type structure and decavanadate and paramolybdate ions in the anion layers, and bismuth hydroxocarbonate. On the base of these precursors, multicomponent oxide catalysts have been manufactured for the oxidative dehydrogenation (OD) of light alkanes. Some of these catalysts showed high selectivities and high product yields in the conversion of ethane to ethylene.     

低碳烷烃与二氧化碳催化转化研究进展

页岩气革命为低碳经济发展提供了重要契机.在低碳烷烃(甲烷和乙烷)催化转化过程中,以二氧化碳作为氧化剂参与反应,通过C–H键的选择性活化可将页岩气转化为优质化工原料——合成气和乙烯,是一种低碳烷烃转化与二氧化碳资源化利用的工艺路线.本文总结了近年来甲烷干重整与乙烷和二氧化碳反应中与C–H键活化相关的研究进展,分析了甲烷干重整中镍基催化剂积碳及乙烷和二氧化碳反应中产物选择性的主要影响因素,并对该研究未来的发展方向进行了展望.     

Kinetics of the oxidative coupling of methane in the presence of model catalysts

The kinetics of the oxidative coupling of methane (OCM) in the presence of La/MgO and NaWMn/SiO₂ catalysts in a flow reactor at low reactant conversions was studied. It was found that, in spite of different compositions and properties of the test catalysts, the formation of ethane from methane and ethylene from ethane can be described within the framework of the Mars-van Krevelen redox model in both cases. The rate laws of side reactions, which lead to the formation of carbon oxides, are different from the rate laws of the target reactions of the conversion of methane into ethane and ethane into ethylene. The kinetic parameters required for the numerical simulation of the OCM process were determined for either of the catalysts.