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1.
《Journal of Energy Chemistry》2016,(6)
Catalytic conversion of CO_2 into chemicals and fuels is an alternative to alleviate climate change and ocean acidification.The catalytic reduction of CO_2 by H_2 can lead to the formation of various products:carbon monoxide,carboxylic acids,aldehydes,alcohols and hydrocarbons.In this paper,a comprehensive thermodynamics analysis of CO_2 hydrogenation is conducted using the Gibbs free energy minimization method.The results show that CO_2 reduction to CO needs a high temperature and H_2/CO_2 ratio to achieve a high CO_2 conversion.However,synthesis of methanol from CO_2 needs a relatively high pressure and low temperature to minimize the reverse water-gas shift reaction.Direct CO_2 hydrogenation to formic acid or formaldehyde is thermodynamically limited.On the contrary,production of CH_4 from CO_2 hydrogenation is the thermodynamically easiest reaction with nearly 100%CH4 yield at moderate conditions.In addition,complex reactions with more than one product are also calculated in this work.Among the considered carboxylic acids(HCOOH,CH_3COOH and C_2H_5COOH),propionic acid dominates in the product stream(selectivity above 90%).The same trend can also be found in the hydrogenation of CO_2 to aldehydes and alcohols with the major product of propionaldehyde and butanol,respectively.In the process of CO_2 hydrogenation to alkenes,low temperature,high pressure,and high H_2 partial pressure favor the CO_2 conversion.C_4H_6 is the most thermodynamically favorable among all considered alkynes under different temperatures and pressures.The thermodynamic calculations are validated with experimental results,suggesting that the Gibbs free energy minimization method is effective for thermodynamically understanding the reaction network involved in the CO_2 hydrogenation process,which is helpful for the development of high-performance catalysts. 相似文献
2.
采用共沉淀法制备了一系列CuO含量不同(质量分数:50%-80%)的CuO-TiO2-ZrO2复合氧化物,并利用X射线衍射(XRD)、氮吸附(BET)、程序升温还原(H2-TPR)、程序升温脱附(H2/CO2-TPD)和氧化亚氮(N2O)反应吸附等多种方法对其进行了表征.以所制备的CuO-TiO2-ZrO2为甲醇合成活性组分与HZSM-5分子筛进行机械混合制成双功能催化剂CuO-TiO2-ZrO2/HZSM-5,在微型固定床流动反应器中,于250℃、3.0 MPa、H2/CO2(体积比2.8)以及空速1500 mL·g-1·h-1的条件下,对其催化CO2加氢直接合成二甲醚(DME)的性能进行了评价.结果表明:随着CuO-TiO2-ZrO2中CuO含量的增加,CO2的转化率先逐渐增大,至70%时达到最大,之后反而降低.DME的选择性随着催化剂中CuO含量的增加而增加,至≥70%时基本不变,故当CuO含量为70%时,DME的收率达到最大值(13.2%).催化剂上合成含氧化合物(甲醇和DME)的活性与催化剂中金属铜的比表面积之间有较好的对应关系. 相似文献
3.
制备了Cu-Zn-Al (4/50/5)催化剂(Cat)和Cu-Zn-Al-Li(40/50/5/5)催化剂(Cat-Li).并将其分别用于由CO/H_2和CO_2/H_2合成甲醇。诸如TPD、TPR、TPSR、脉冲、CD3I-捕获、同位素标记、EPR及原位DRIFT等技术和方法被用来表征这两种催化剂及研究反应机理,对处于去氢、含氢及含氧态催化剂进行了对比研究以期阐明表面氧和表面氢对CO_2和CO活化所起的作用。提出了一个由甲酸根和甲醛氢化及甲醇氧化结果为证的CO/CO_2氢化机理。由于通过Li 取代CuO晶格上的Cu2+形成的氢空位,在Cat中添加Li+改善了甲醇合成活性。CO_2能被一捕获的电子(F-中心)活化,生成的CO2-能容易地被氢化成甲酸根和亚甲基双草酰,后者分解生成H2CO和表面氧。CO能被表面氧活化,生成的CO2-将遵循CO_2氢化的途径。在CD3I-捕获的实验中,我们捕获了表面氧。在无表面氧时,CO可能直接氢化成甲酸基,即CO_2氢化中的一途径。由亚甲基双草酰产生的H2CO表面模型可能与由甲醛吸附或CO氢化生成的H2CO表面模型不同。 相似文献
4.
以热力学分析和动力学分析为基础,设计了几种实现CH4-CO2低温转化直接合成含氧有机物的混氢进料方式,通过实验对这些进料方式进行了初步探讨,并考察了甲烷活化及二氧化碳反应过程中混氢比例的影响.结果表明,与CH4/CO2进料方式相比,几种混氢进料方式都能提高乙酸收率,但需要很好地控制二氧化碳加氢反应.在甲烷活化过程中混氢,13.8%的氢气比例对甲烷的转化最有利,乙酸收率可达最高;在二氧化碳反应过程中混氢,混氢比例为50%时乙酸收率最高.催化剂的催化特性与其反应前后表面特征的变化相吻合. 相似文献
5.
CO2氧化丙烷脱氢MoO3-V2O5/SiO2催化剂研究 总被引:4,自引:0,他引:4
采用表面改性和等体积浸渍法制备了MoO3-V2O5/SiO2复合氧化物,采用TPR、IR、TPD和微反技术表征了催化剂对CO2和C3H8的吸附性能和CO2部分氧化丙烷脱氢的反应性能.结果表明:随MoO3加入量的增加,V=O还原温度降低,晶格氧更易活化.CO2和丙烷的活化温度降低,丙烷转化率增高,丙烯选择性下降.V=O中晶格氧的活化是CO2氧化丙烷制丙烯反应的关键. 相似文献
6.
The effects of Mg, La and Ca promoters on primary and secondary CO_2 and H_2O formation pathways during Fischer-Tropsch synthesis on precipitated Fe/Cu/SiO_2 catalysts are investigated. The chemisorbed oxygen atoms in the primary pathway formed in the CO dissociation steps reacted with co-adsorbed hydrogen or carbon monoxide to produce H_2O and CO_2 , respectively. The secondary pathway was the water-gas shift reaction. The results indicated that the CO_2 production led to an increase in both primary and secondary pathways, and H_2 O production
decreased when surface basicity of the catalyst increased in the order Ca >Mg >La. 相似文献
7.
《Journal of Energy Chemistry》2017,26(6):1039-1049
CO_2 conversion via photocatalysis is a potential solution to address global warming and energy shortage.Photocatalysis can directly utilize the inexhaustible sunlight as an energy source to catalyze the reduction of CO_2 to useful solar fuels such as CO, CH_4, CH_3OH, and C_2H_5OH. Among studied formulations, Cubased photocatalysts are the most attractive for CO_2 conversion because the Cu-based photocatalysts are low-cost and abundance comparing noble metal-based catalysts. In this literature review, a comprehensive summary of recent progress on Cu-based photocatalysts for CO_2 conversion, which includes metallic copper, copper alloy nanoparticles(NPs), copper oxides, and copper sulfides photocatalysts, can be found. This review also included a detailed discussion on the correlations of morphology, structure, and performance for each type of Cu-based catalysts. The reaction mechanisms and possible pathways for productions of various solar fuels were analyzed, which provide insight into the nature of potential active sites for the catalysts. Finally, the current challenges and perspective future research directions were outlined, holding promise to advance Cu-based photocatalysts for CO_2 conversion with much-enhanced energy conversion efficiency and production rates. 相似文献
8.
GuoHuaLAI RenXianZHOU XiaoXiangHAN XiaoMingZHENG 《中国化学快报》2004,15(12):1494-1496
The effect of transition metals (Cr, Mn, Fe, Co and Ni) on the hydrogenation of cinnamaldehyde over Pt/ZrO2 catalysts was studied in ethanol at 343K under 2.0MPa H2 pressure. PtCo/ZrO2 and PtFe/ZrO2 catalysts exhibit high selectivity and activity of hydrogenation for C=O (93.8% at 87.3% conversion and 83.6% at 88.6% conversion, respectively), and PtNi/ZrO2 exhibits high selectivity of hydrogenation for C=C (64.3% at 70.6% conversion). In the presence of trace H2O and NaOH, over the PtNi/ZrO2 (0.4wt%Ni) catalyst the selectivity to hydrocinnamalde hydereaches 90.6% and the conversion of cinnamaldehyde is 90.5%. 相似文献
9.
Fe—Silicalite—2催化剂表面CO2加氢反应性能的研究 总被引:3,自引:0,他引:3
研究了Fe/Silicalite-2催化剂CO2加氢低碳烯烃反应性能,利用CO2-TPD,CO2/H2-TPSR和CO/H2-TPSR表征手段,考察了铁含量及MnO助剂对Fe/Silicalite-2催化剂CO2吸附脱附及加氢反应性能的影响,表明随铁含量增加可提高催化剂对CO2的吸附能力,有利于提高CO2加氢反应的转化率。 相似文献
10.
11.
常压、脉冲微波强化丝光等离子体作用下甲烷与二氧化碳的反应研究 总被引:7,自引:0,他引:7
采用脉冲微波强化丝光等离子体反应装置,研究了甲烷氧化偶联与二氧化碳重 整制合成气(CO+H_2)副产乙炔、乙烯的反应。常压下,当CH_4和CO_2流量分别为 120,80mL/min,微波峰值功率120W,脉冲通断比为100/100ms时,CH_4和CO_2转化 率分别为70.8%,68.8%;CO, C_2H_2,C_2H_4选择性分别为75%,17.8%和4.1%,产物 中没有积炭。H_2/CO摩尔比值随原料气中甲烷比例的增加而增大,当CH_4/CO_2摩 尔比为2:1时,H_2/CO摩尔比达到2,这种比例的合成气能方便地用于下一步的 Fischer-Tropsch反应和其他化学品的合成。与其他等离子体反应相比,采用脉冲 强化常规丝光等离子体进行CH_4脱氢偶联与CO_2重整反应,能量效率明显提高,这 对于促进微波等离子体技术在C1化学中的应用具有重要的意义。 相似文献
12.
Cu/MoO3-TiO2/SiO2上光催化CO2和C3H8合成异丁烯醛的研究 总被引:2,自引:0,他引:2
采用表面改性法和等体积浸渍法制备了金属修饰的负载型复合半导体材料Cu/MoO3-TiO2/SiO2, 用X射线衍射、 比表面积测定、 红外光谱、 拉曼光谱和紫外-可见漫反射等技术对固体材料的结构、 吸光性能和化学吸附性能进行了表征, 研究了该材料对CO2和丙烷合成异丁烯醛的光促表面催化规律. 结果表明, 半导体活性组分MoO3和TiO2在所制备的催化剂Cu/MoO3-TiO2/SiO2表面形成化学键, 并存在多种活性吸附位; 金属Cu的修饰拓展了固体材料对光源的响应范围, 提高了反应体系的吸光能力; 固体材料对CO2和丙烷的有效吸附使其在较低温度下就能促进异丁烯醛的紫外光化学合成, 反应选择性达到85%左右. 根据实验结果对光促CO2和丙烷表面催化合成异丁烯醛的机理进行了讨论. 相似文献
13.
C_2h_3自由基与O_2反应机理的量子化学研究 总被引:1,自引:0,他引:1
用量子化学从头计算中UMP2(full)方法优化了C_2H_3自由基与O_2反应通道上 驻点(反应物、中间体、过渡态和产物)的几何构型,在Gaussian-3(G3)水平上计 算了它们的能量。在此基础上计算了该反应通道上各基元反应的反应活化能。通过 我们的研究发现,C_2H_3自由基与氧气反应存在着三元环、四元环和五元环反应机 理,且分别生成不同的产物,从反应活化能的计算结果扯CH_2O和CHO是反应的主要 产物,其次还可能生成CH_3 + CO_2, CH_2CO_2 + H, C_2H_2 + O_2H和COHCOH + H等产物,且它们生成几率逐渐减少,我们对生成产物CH_2O + CHO, CH_3 + CO_2, C_2H_2 + O_2H和COHCOH + H四条反应通道化学反应热的计算结果与实验吻 合较好。 相似文献
14.
The hydrogenation of carbon dioxide(CO_2) is one of important processes to effectively convert and utilize CO_2, which is also regarded as the key step at the industrial methanol synthesis. Water is likely to play an important role in this process, but it still remains elusive. To systematically understand its influence, here we computationally compare the reaction mechanisms of CO_2 hydrogenation over the stepped Cu(211) surface between in the absence and presence of water based on microkinetic simulations upon density functional theory(DFT) calculations. The effects of water on each hydrogenation step and the whole activity and selectivity are checked and its physical origin is discussed. It is found that the water could kinetically accelerate the hydrogenation on CO_2 to COOH, promoting the reverse water gas shift reaction to produce carbon monoxide(CO). It hardly influences the CO_2 hydrogenation to methanol kinetically. In addition, the too high initial partial pressure of water will thermodynamically inhibit the CO_2 conversion. 相似文献
15.
LI Jun RONG Huazhen CHEN Cong LI Ziyi ZUO Jiayu WANG Wenjian LIU Xinjian GUAN Yixing YANG Xiong LIU Yingshu ZOU Xiaoqin ZHU Guangshan 《高等学校化学研究》2022,38(1):250-256
High-silica SSZ-13 zeolite membranes are promising in industrial separations of light gases and continuous membranes are highly demanded for better separation performances. Herein, pure-phase, continuous and thin SSZ-13 zeolite membranes were synthesized using dual templates of N,N,N-trimethtyl-1-adamantammonium hydroxide(TMAdaOH) and tetraethylammonium hydroxide(TEAOH). Systematical investigations of TMAdaOH/TEAOH ratios and their concentrations show that TMAdaOH acts as the main structure-directing agent in the formation of the SSZ-13 zeolite. TMAdaOH cooperatively plays with TEAOH in promoting the SSZ-13 crystal intergrowth to form a continuous polycrystalline membrane. Additionally, appropriate introduction of TEAOH is able to adjust the membrane thickness to the crystal-comparable size of ca. 2.0 μm. The SSZ-13 membranes are further applied for N2/NO2separation, which is firstly reported on zeolite membranes. The gas permeation results show that the SSZ-13 membrane synthesized by the dual-template approach exhibits selective separation of N2 over NO2 with N2/NO2 separation factor of 7.6 and N2 permeance of 1.66×10-8 mol·m-2·s-1·Pa-1. 相似文献
16.
Ni-Na-Y分子筛对CO_2加氢反应显示出高的CO选择性和低活性。本文用EXAFS、FTIR、EPR和XRD对Ni-Na-Y分子筛进行了表征,结果表明,在H_2还原下首先形成小的Ni原子簇,接着在催化反应过程中粒径变大,并从超笼移向外表面。结果还表明,CO选择性的高低取决于分子筛的酸性、Na~+的存在和Ni原子簇的粒径大小。在CO气氛下的预处理将提高其生成CO的活性和选择性。 相似文献
17.
The metastable phase equilibria of the quaternary system NaCl+Na2CO3+Na2SO4+H2O were studied at 273.15 K. The salts' solubilities, densities and pH values of the equilibrated solution in this system were determined. According to the experimental data, the metastable equilibrium phase diagram, the diagram of density vs. composition and pH vs. composition diagram were plotted. The phase diagram consists of five univariant curves, four crystallization fields and two invariant points. The four crystallization fields correspond to sodium carbonate decahydrate (Na2CO3·10H2O), sodium sulfate decahydrate(Na2SO4·10H2O), sodium chloride(NaCl) and burkeite(2Na2SO4· Na2CO3), respectively. The crystallization field of sodium sulfate decahydrate(Na2SO4·10H2O) is the largest, which indicates that sodium sulfate is easy to saturate and crystallize from solution at 273.15 K. 相似文献
18.
《Journal of Energy Chemistry》2017,26(5):881-890
The Earth's sustainable development is threatened by the increasing atmospheric CO_2 level which can be attributed to the imbalance of CO_2 due to the rapid consumption of fossil fuels caused by human activities and the slow absorption and conversion of CO_2 by nature. One of the efficient methods for reconstructing the balance of CO_2 should involve the rapid conversion of CO_2 into fuels and chemicals.The hydrogenation of CO_2 with gaseous hydrogen is currently considered to be the most commercially feasible synthetic route, however, the supply of safe and economical hydrogen sources poses a significant challenge to up-scaling application. Direct utilization of hydrogen from dissociation of water, the most abundant, cheap and clean hydrogen resource, for the reduction of CO_2 would be one of the most promising approaches for CO_2 utilization. This paper provides an overview of the current advances in research on highly efficient reduction of CO_2 or NaHCO_3, a representative compound of CO_2, into formic acid/formate by in situ hydrogen from water dissociation with a metal/metal oxide redox cycle under mild hydrothermal conditions. 相似文献
19.
低镍催化剂上CO和CO_2加氢反应的对比研究 总被引:2,自引:0,他引:2
采用CO和CO_2对比加氢活性测试,XRD及TPR方法研究了两个不同Na助剂含量的低镍Ni/Al_2O_3体系的性能。实验发现,在低镍催化剂上CO_2在较低温度下就可加氢生成甲烷,而CO则需要更高的温度,CO_2无需先经逆变换生成CO,然后再加氢,它可直接加氢生成CH_4。在同一催化剂上,CO_2加氢生成CH_4的表现活化能要低于CO加氢生成CH_4反应的表现活化能。晶相NiO还原后形成的活性相对CO_2加氢反应的活性明显高于它对CO的加氢活性,非晶相镍氧化物还原后形成的活性相对CO的加氢反应特别有利。Na助剂的含量不同会造成Ni氧化物物种的分配不同,从而导致CO、CO_2的加氢活性及其随温度的变化也不相同,催化剂对CO、CO_2加氢反应作用的本质是不相同的。 相似文献
20.
《Microporous Materials》1994,2(2):105-117
Isostructural molecular sieves based upon AlPO4 and SiO2 chemistry were made for comparison of catalytic selectivity. The AFI and CHA structures were compared with B and Al substitution of SiO2 and Mg and Si substitution in the AlPO4 case. The conversion of methanol to hydrocarbons was studied. Materials were characterized for acidity by NH3 TPD and NH3 microcalorimetry. Methanol conversion was carried out with products analyzed by GC-MS and spent catalysts by 13C MAS NMR. Borosilicate sieves have acidity too low to carry out this catalytic transformation. Other substituting components were successful but product selectivity seemed to be governed by geometric features of the sieves, rather than by variable acidity due to different types of lattice substitution. Products from small pore molecular sieves SAPO-34 and SSZ-13 were largely olefinic and comprised of C5 and smaller. The large pore sieves, SAPO-5, MAPO-5, and SSZ-24, all produced aromatic-rich products. A considerable quantity of the recovered hydrocarbon was incorporated into penta- and hexamethylbenzene. 相似文献