CO2／H2和（CO／CO2）＋H2低压合成甲醇催化过程的本质

通过在Ｃｕ／ＺｎＯ／Ａｌ２Ｏ３催化剂上ＣＯ２＋Ｈ２，ＣＯ＋Ｈ２和（ＣＯ／ＣＯ２）＋Ｈ２催化反应动力学研究对合成甲醇动力学和反应机理进行了细致分析，提出合成甲醇的反应机理，解释了在（ＣＯ／ＣＯ２）＋Ｈ２合成甲醇过程中少量ＣＯ２的作用及合成甲醇的直接碳源。     

非贵金属催化剂用于CO选择性氧化脱除的研究

以Co和Ni为催化剂活性组分、活性炭为载体,通过饱和浸渍法制得非贵金属催化剂,采用XRD、SEM和TPD对催化剂性能进行表征,考察了该催化剂用于富氢气中CO选择性氧化活性及H₂O或/和CO₂对催化性能的影响。研究结果表明,催化剂以NiO和高分散的Co₃O₄为主要物相,催化剂吸附O₂的能力随着金属氧化物负载量的增加而增加,且催化剂对O₂分子的吸附能力明显强于CO₂分子。金属氧化物负载量为35%的催化剂表现出较高的CO选择性氧化活性和选择性,在低于473K时O₂氧化选择性达50%以上,此时可将CO浓度降到40×10^-6以下,达到燃料电池对氢燃料气的要求。同时,催化剂表现出较强的抗水蒸气和CO₂的能力。     

CO/H_2在Cu/ZrO_2催化剂表面吸附行为原位红外表征

用原位FT IR法比较了Cu ZrO2 和ZrO2 催化剂表面对CO及CO H2 的吸附行为。结果表明 ,CO在 5 0℃便可以在Cu ZrO2 表面形成b HCOO Zr、Zr COO- 和b HOCOOZr物种 ,吸附温度升高 ,b HOCOOZr逐渐分解生成Zr OH和CO2 ,而b HCOO Zr吸附物种逐渐增强。b HCOO Zr物种在Cu ZrO2 催化剂表面生成速率远远大于ZrO2 催化剂。在Cu ZrO2 催化剂表面 ,所形成的合成甲醇中间物种 (HCOO Zr和CH3O Zr)均和ZrO2 有关 ,意味着CO加氢反应主要在ZrO2 表面进行 ,铜组分主要向ZrO2 提供吸附CO及H2 物种。     

Selective CO methanation over amorphous Ni-Ru-B/ZrO_2 catalyst for hydrogen-rich gas purification

Amorphous Ni-Ru-B/ZrO2 catalysts were prepared by chemical reduction method. The effects of Ni-Ru-B loading and Ru/Ni mole ratio on the catalytic performance for selective CO methanation from reformed fuel were studied, and the catalysts were characterized by BET, ICP, XRD and TPD. The results showed that Ru strongly affected the catalytic activity and selectivity by increasing the thermal stability of amorphous structure, promoting the dispersion of the catalyst particle, and intensifying the CO adsorption. For the catalysts with Ru/Ni mole ratio under 0.15, the CO methanation conversion and selectivity increased significantly with the increasing Ru/Ni mole ratio. Among all the catalysts investigated, the 30 wt% Ni-Ru-B loading amorphous Ni61Ru9B30/ZrO2 catalyst with 0.15 Ru/Ni mole ratio presented the best catalytic performance,over which higher than 99.9%of CO conversion was obtained in the temperature range of 230℃～250℃,and the CO2 conversion was kept under the level of 0.9%.     

Selective CO methanation over amorphous Ni-Ru-B/ZrO2 catalyst for hydrogen-rich gas purification

Amorphous Ni-Ru-B/ZrO₂ catalysts were prepared by chemical reduction method. The effects of Ni-Ru-B loading and Ru/Ni mole ratio on the catalytic performance for selective CO methanation from reformed fuel were studied, and the catalysts were characterized by BET, ICP, XRD and TPD. The results showed that Ru strongly affected the catalytic activity and selectivity by increasing the thermal stability of amorphous structure, promoting the dispersion of the catalyst particle, and intensifying the CO adsorption. For the catalysts with Ru/Ni mole ratio under 0.15, the CO methanation conversion and selectivity increased significantly with the increasing Ru/Ni mole ratio. Among all the catalysts investigated, the 30 wt% Ni-Ru-B loading amorphous Ni₆₁Ru₉B₃₀/ZrO₂ catalyst with 0.15 Ru/Ni mole ratio presented the best catalytic performance, over which higher than 99.9% of CO conversion was obtained in the temperature range of 230°C～250°C, and the CO₂ conversion was kept under the level of 0.9%.     

N-doped carbon supported Pd catalysts for N-formylation of amines with CO_2/H_2

Using mesoporous N-doped carbons(NCs)derived from glucose and melamine as the supports,a series of Pd/NC catalysts were prepared,in which Pd nanoparticles with average size2.0 nm were uniformly distributed on the supports.It was indicated that the resultant Pd/NC catalysts were effective for N-formylation of amines with CO_2and H_2in ethanol without any additives.Especially,the catalyst Pd/NC-800-6.9%containing quaternary N showed the best performance,affording a series of formylamides in good or even excellent yields.Further investigation reveals that the interaction between the Pd nanoparticles and quaternary nitrogen in the NC support was responsible for the good performance of the catalyst.     

焙烧温度对Au/Fe2O3选择性氧化富氢气体中CO催化性能的影响

甲醇重整在线制氢作为质子交换膜燃料电池的燃料成为当前研究的热点。受重整反应动力学及热力学的限制，使得甲醇重整气(富氢气体)中除含有大量的氢气外还含有少量的CO，CO极易吸附在燃料电池阳极催化剂表面，使电池性能下降，因而必须去除重整气中的CO，选择性氧化脱除富氢气     

CO2＋H2制含氧化合物的研究

作为自然界中含有丰富碳源的CO_2,经过催化加氢制含氧化合物的研究,近年来为人们所关注,特别是CO_2加氢制甲醇.从CO_2出发制含氧化合物其前景是诱人的,则可利用碳和氧得到化学品,二则减少了自然界中的CO_2含量,有益于环境保护.本文对Cu-Zn系和Rh-V系催化剂进行初步考察.     

中空纤维Au-CeZr/FAU催化膜的制备及在富氢气氛CO选择性氧化反应中的应用

采用浸渍法制备了一系列不同Ce/Zr掺杂比例的FAU分子筛膜, 并进一步负载纳米金, 制备了Au-CeZr/FAU催化膜. 对催化膜的微观形貌及结构进行了表征, 并对其在富氢气氛中催化CO优先氧化性能进行了研究. H₂-TPR结果表明, Ce/Zr掺杂比为1∶1时制得的催化膜Au-Ce₁Zr₁/FAU具有最好的被还原能力, 更有利于Au的分散与还原; O₂-TPD结果表明, 该样品的氧物种比其它样品上的氧物种活性更高. 更好的被还原性能和更高的氧物种活性使得制备的Au-Ce₁Zr₁/FAU催化膜性能最佳, 在60 ℃时CO转化率与O₂选择性可以同时达到100%, 并且在经过10次热循环测试后仍然可以保持稳定的催化性能.     

Design of two-stage membrane reactor for the conversion of coke-oven gas to H_2 and CO

The catalyst function was achieved in two regions in an oxygen permeation membrane reactor: H2 dissociated and reacted with lattice oxygen or oxygen ions to form H2 O near the membrane surface. The H2 O formed could react with the residual CH4 away from the membrane surface area.     

制备方法对超细Cu／ZnO／Al2O3催化剂上CO2＋H2合成甲醇的影响

制备方法对超细Ｃｕ／ＺｎＯ／Ａｌ_２Ｏ_３催化剂上ＣＯ_２＋Ｈ_２合成甲醇的影响张玉龙，王欢，邓景发（复旦大学化学系，上海，２００４３３）关键词超细粒子，合成甲醇，Ｃｕ／ＺｎＯ／Ａｌ_２Ｏ_３催化剂，ＣＯ_２＋Ｈ_２ＣＯ２＋Ｈ２合成甲醇是目前的热门课题［１～...     

Enhancement of CO2 sorption uptake on hydrotalcite by impregnation with K2CO3

The awareness of symptoms of global warming and its seriousness urges the development of technologies to reduce greenhouse gas emissions. Carbon dioxide (CO(2)) is a representative greenhouse gas, and numerous methods to capture and storage CO(2) have been considered. Recently, the technology to remove high-temperature CO(2) by sorption has received lots of attention. In this study, hydrotalcite, which has been known to have CO(2) sorption capability at high temperature, was impregnated with K(2)CO(3) to enhance CO(2) sorption uptake, and the mechanism of CO(2) sorption enhancement on K(2)CO(3)-promoted hydrotalcite was investigated. Thermogravimetric analysis was used to measure equilibrium CO(2) sorption uptake and to estimate CO(2) sorption kinetics. The analyses based on N(2) gas physisorption, X-ray diffractometry, Fourier transform infrared spectrometry, Raman spectrometry, transmission electron microscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy were carried out to elucidate the characteristics of sorbents and the mechanism of enhanced CO(2) sorption. The equilibrium CO(2) sorption uptake on hydrotalcite could be increased up to 10 times by impregnation with K(2)CO(3), and there was an optimal amount of K(2)CO(3) for a maximum equilibrium CO(2) sorption uptake. In the K(2)CO(3)-promoted hydrotalcite, K(2)CO(3) was incorporated without changing the structure of hydrotalcite and it was thermally stabilized, resulting in the enhanced equilibrium CO(2) sorption uptake and fast CO(2) sorption kinetics.     

Synthesis of a red iron oxide/montmorillonite pigment in a CO2-rich brine solution

The homoionic calcium-montmorillonite was used to synthesize a red iron oxide/clay pigment in a CO2-rich brine solution (0.5 M of NaCl) by using an agitated batch-reactor (engineer autoclave). The operating conditions were 15 days of reaction, 200 bars of pressure and 150 degrees C of temperature. SEM/EDS, STEM/EDS, XRD and Infrared Spectrometry were performed to characterize before and after reaction the solid phase. The results showed the precipitation of spherical nanoparticles (50-500 nm) of iron oxide (Fe2O3) dispersed and/or coagulated in the clay-matrix. Evidently, this oxide produced red coloration in the final product. For this case, the Fe3+ cation was provided to the aqueous solution by the dissolution of Ca-montmorillonite, particularly, the dissolution of most fine particles contained in the starting clay material. The cation exchange process and precipitation of polymorph silica were also observed.     

K改性的Pt/Al2O3催化剂上CO氧化反应：反应动力学和红外光谱研究

CO氧化不仅具有重要的实用价值,而且在基础研究中被用于考察反应机理及催化剂结构敏感性等一些重要问题,因此,该反应在催化领域中具有重要意义. Pt基催化剂被广泛应用于CO氧化反应.其催化活性取决于催化剂的制备方法.其中,碱金属如Na、K等助剂的添加可有效促进催化活性,红外光谱证据表明,其促进作用在于碱金属的添加可降低CO与表面Pt原子的相互作用.尽管如此,催化剂上反应动力学证据却十分缺乏.反应动力学的研究可以提供一些本证反应信息如反应基元步骤、反应速率表达式以及反应机理等.通过对比不同催化剂之间的反应动力学行为,可以进一步解释碱金属对催化剂结构以及反应行为的影响.因此在本工作中,我们制备了一系列以K为助剂的Pt/Al2O3催化剂,并进行了CO氧化的反应动力学研究,考察了助剂对CO反应级数和反应活化能的影响.结合原位红外光谱表征,进一步揭示了助剂在反应中的作用.通过对比不同Pt和K含量的催化剂上CO氧化反应活性,我们发现, K的添加能促进反应活性,且随着催化剂中K含量的增加,促进程度越明显.例如,0.42K-2Pt/Al2O3上T50温度比对应的2Pt/Al2O3降低了30oC.不同催化剂上CO氧化的反应动力学实验表明,反应速率随着CO的分压的增加而降低;但随着O2分压的增加而增大.幂函数反应速率表达式推导得到的反应级数发现,对于含K的催化剂其CO的反应级数(约为–0.2)明显比不含K的催化剂(约为–0.5)中高,说明K的添加减弱了CO与表面Pt原子之间的吸附能力.但对O2的反应级数影响较小.例如：在0.42K-2.0Pt/Al2O3上反应速率表达式为r =6.55′10–7pco–0.22po20.63;而在2.0Pt/Al2O3上为r =2.56′10–7pco–0.53po20.70.表观反应活化能的计算表明,含K的催化剂上表观反应活化能较低,进一步说明K的添加有利于反应进行.根据反应速率表达式,我们进行了基元步骤的推导,并计算了反应动力学参数.结果发现,与不含K的催化剂相比,含K的催化剂中本征反应速率常数明显增加,而CO吸附平衡常数降低了一半,表明K的存在使CO在Pt表面上的覆盖度降低.我们还通过原位红外光谱对比了催化剂上CO吸附行为的差异.数据表明,与不含K的催化剂相比, K的添加一方面降低了CO在催化剂表面的吸附量(峰面积变小);另一方面显著降低了CO在Pt表面上的脱附温度,说明两者之间的相互作用力减弱.综上所述,通过反应动力学和红外光谱实验,我们认为K助剂与表面Pt原子相互作用后生成了较为稳定的Pt–O–K物种.尽管该物种的具体结构目前还不明确,但我们的实验证据表明,该物种的存在可以有效减弱CO与表面Pt原子之间的相互作用,降低CO的表面覆盖度并有利于O2在Pt表面的竞争吸附,从而降低了表面吸附的CO与O2之间反应的能垒,促进了反应性能.     

氧化铜/氧化锆甲醇合成催化剂的性能研究

以超临界干燥法制得的超细ＺｒＯ２为载体，浸渍铜后所得的ＣｕＯ／ＺｒＯ２催化剂对ＣＯ／Ｈ２合成甲醇呈现出较好的活性选择性，反应温度对催化剂的活性和选择性有较大的影响，ＸＰＳ结果表明，载体和活性组分间存在着相互作用，ＴＰＲ结果说明ＣｕＯ／ＺｒＯ２中的铜以两种形式存在，一种为体相铜，另一咱为高度分散的铜，后者的含量和甲醇产率存在着顺应关系，它应是关键的活性组分。     

A solid molecular basket sorbent for CO2 capture from gas streams with low CO2 concentration under ambient conditions

In this paper, a solid molecular basket sorbent, 50 wt% PEI/SBA-15, was studied for CO(2) capture from gas streams with low CO(2) concentration under ambient conditions. The sorbent was able to effectively and selectively capture CO(2) from a gas stream containing 1% CO(2) at 75 °C, with a breakthrough and saturation capacity of 63.1 and 66.7 mg g(-1), respectively, and a selectivity of 14 for CO(2)/CO and 185 for CO(2)/Ar. The sorption performance of the sorbent was influenced greatly by the operating temperature. The CO(2)-TPD study showed that the sorbent could be regenerated under mild conditions (50-110 °C) and was stable in the cyclic operations for at least 20 cycles. Furthermore, the possibility for CO(2) capture from air using the PEI/SBA-15 sorbent was studied by FTIR and proved by TPD. A capacity of 22.5 mg g(-1) was attained at 75 °C via a TPD method using a simulated air with 400 ppmv CO(2) in N(2).     

N-methylation of quinolines with CO_2 and H_2 catalyzed by Ru-triphos complexes

N-methyl-tetrahydroquinolines(MTHQs) are a kind of very useful chemicals, which can be obtained from N-methylation of amines.However, the methylation of quinolines which is a kind of highly unsaturated nitrogen-containing heterocyclic aromatic compounds has not been reported. In this work, we report the first work for the synthesis of MTHQs by methylation of quinolines using CO_2 and H_2. It was found that Ru(acac)_3-triphos [triphos: 1,1,1-tris(diphenylphosphinomethyl)ethanl] complex was very active and selective for the N-methylation reaction of quinolines, and the yield of the desired product could reach 99%.     

Characteristics of Au/MgxAlO hydrotalcite catalysts in CO selective oxidation

Gold catalysts, supported on a solid base of Mg_xAlO hydrotalcite, were prepared by a modified deposition precipitation method for CO selective oxidation. The preparation parameters and pretreatment of the catalysts were investigated. The pH and the HAuCl₄ concentration in the initial solution, and the Mg/Al molar ratio of Mg_xAlO affected the pH in the final solution and determined the actual gold loading of the catalyst. The calcination temperatures of the Mg_xAlO support and the Au/Mg_xAlO catalyst dominated the Au³⁺/Au⁰ ratio on the catalyst. The pretreatment of the catalyst as well as the gold loading and the Au³⁺/Au⁰ ratio, critically determined the activity of the catalyst for CO selective oxidation. Based on XPS and in situ DR-FTIR analyses, a mechanism for CO selective oxidation on 2%Au/Mg₂AlO was proposed. The hydroxyl group on Mg₂AlO also participated in the reaction.     

XPS study of potassium-promoted molybdenum carbides for mixed alcohols synthesis via CO hydrogenation

The X-ray photoelectron spectroscopy (XPS) was used to investigate the surface characteristic of potassium-promoted or un-promoted both β-Mo_2C and α-MoC_(1-x) pretreated by syngas at different temperatures, and the promotional effect of potassium on the catalytic performance was also studied. XPS results revealed that the content of surface Mo and its valence distribution between β-Mo_2C and α-MoC_(1-x) were quite different. Promoted by potassium, the remarkable changes were observed for surface composition and valence of Mo distribution over β-Mo_2C. Potassium had strong electronic effect on β-Mo_2C, which led to a higher Mo~(4+) content. On the contrary, potassium had little electronic effect on α-MoC_(1-x), and K-Mo interaction was weak. Therefore, Mo~0 and Mo~(2+) became the dominant species on the catalyst surface, and the Mo~(4+) content showed almost no increase as the pretreatment temperature enhanced. In terms of catalytic performance of molybdenum carbides, the increase in Mo~0 most likely explained the increase in hydrocarbon selectivity, yet Mo~(4+) might be responsible for the alcohols synthesis.