高浓度CO原料气脱H2催化剂H-846D的开发及研究

煤制乙二醇是以煤气化制取合成气（CO+H₂）,CO催化偶联合成草酸酯,再加氢合成乙二醇,需将CO中所含H₂净化脱除至小于100×10^-6。选择性氧化法贵金属催化剂存在含量高、抗CO、CO₂和H₂O中毒能力较差导致活性不稳定等缺点。以γ-Al₂O₃为载体,采用浸渍工艺制备一种高浓度CO原料气脱H₂催化剂H-846D,该催化剂通过贵金属Pd和多种非贵金属氧化物助剂的协同催化作用,适于高浓度CO原料气高效抗毒脱H₂。考察Pd含量、空速、压力和载体对催化剂性能的影响,结果表明,在压力0.5 MPa、空速1 600 h^-1和温度182 ℃条件下,通入含体积分数0.5%H₂、0.5%O₂和0.5%CO₂的CO原料气,可将高浓度CO气氛中的H₂选择性氧化脱除至小于100×10^-6,该催化剂贵金属用量较少。1 070 h的寿命试验结果表明,该催化剂活性好,脱除精度高,性能稳定,应用前景广阔。     

催化氧化脱除烯烃中微量一氧化碳的催化剂进展及机理探讨

催化氧化深度脱除烯烃中微量CO,具有工艺设备简单、易操作、脱除效率高等特点。本文综述了国内外深度脱除烯烃中微量CO的催化剂研究状况,接着介绍了CO氧化脱除机理,然后详细讨论了铜系催化剂上存在的3种氧化态（Cu²⁺、Cu¹⁺、Cu⁰）在CO氧化反应的活性差异以及活性晶格氧的性质对CO氧化活性的影响,并对该技术发展做了展望。     

选择性氧化脱除富氢氢源中CO的研究进展

介绍了将富氢氢源中CO脱除到质子交换膜燃料电池PtRu电极可以承受的CO浓度范围(<1×10-4)最经济和最可行的方法,综述了选择性氧化脱除富氢氢源中CO在催化剂、动力学和反应器优化设计等方面的研究进展,评述了Pt催化剂、Au和Ag催化剂及Cu金属催化剂。     

PtCoK/Al2O3催化剂涂层选择性氧化脱除富氢气氛中的CO

富氢气体中选择性氧化脱除CO是去除重整气中少量CO的有效方法。该文考察了K/Pt摩尔比对PtCoK/Al2O3催化剂涂层的影响。研究发现,适量K的添加能显著提高催化剂涂层的CO去除能力,最优K/Pt摩尔比是1～1.5,超过这个配比,CO脱除能力降低。将进口气氛中O2的体积分数从1%提高到1.5%,可提高CO转化率,但是对应的CO2选择性有所下降。富氢气中同时含有H2O和CO2对催化剂涂层活性影响微弱。连续反应100 h后,PtCoK/Al2O3催化剂涂层上CO转化率几乎未降低,催化剂涂层非常稳定,表明该催化剂涂层具有较强的工业化应用前景。     

深度脱除富氢气体中CO的纳米Ni/ZrO2催化剂

针对富氢气体中甲烷化反应深度脱除CO过程中催化剂活性不足的问题,研究了一种新型的纳米Zr O₂负载的Ni基催化剂。通过尿素水解法制备不同活性金属含量的纳米Ni/ZrO₂催化剂,在体积分数为3%CO、2%CO₂、95%H₂的富氢气氛中,采用固定床反应器,研究了在不同反应温度、体积空速WHSV等对CO转化率以及最终出口气体中CO浓度的影响,同时进行了催化剂寿命评价。研究结果表明：Ni O的负载质量分数为30%的催化剂,在反应温度为200～400℃、反应空速为1 000 h^-1的条件下,可以将CO的体积分数降低至2×10^-6以下,且催化剂在连续评价100 h内,催化剂性能稳定。研究认为,由于纳米Zr O₂对CO的吸附能力增强,有利于提高催化剂上CO甲烷化反应的效率和稳定性。     

密闭电石炉气脱氧催化剂的制备和表征

为脱除密闭电石炉气中体积分数为2%的O₂,制备了以铜为主催化剂,锰和钴为助催化剂,以活性炭为载体的低温高活性脱氧催化剂。在120 ℃,该催化剂可将体积分数为98%的CO、2%的O₂且流量为1.5 L·min^-1的原料气中的O₂脱除至0.2%以下,满足将密闭电石炉气作为化工原料气的要求。正交实验结果表明,催化剂活性组分质量分数为铜6.5%、锰4%和钴0.5%时,能将O₂体积分数脱至0.054 1%。BET比表面积和XRD表征表明,制备的催化剂是一种组分负载量接近其在载体上的单层分散阈值的氧化态Cu-Co-Mn负载型催化剂,其中,Co对活性组分均匀分布于活性炭表面起重要作用。     

富氢气体中CO优先氧化催化剂研究进展

以高纯氢为燃料的质子交换膜燃料电池广泛应用于电动汽车,但其阳极容易被富氢气体中含有的少量CO毒化,造成电池性能严重降低。富氢气体在进入燃料电池前,必须进行CO净化处理。优先氧化法是除去富氢气体中少量CO最简单经济有效的方法,常用催化剂主要有Pt系、Au系和Cu系催化剂。着重阐述负载Au催化剂的制备方法、载体调变、助剂改性以及其他因素（如反应气氛中CO与O₂浓度比、水蒸汽和CO₂等）对Au催化剂CO优先氧化反应催化性能的影响。介绍以CuO/CeO₂催化剂为典型的非贵金属氧化物催化剂用于CO优先氧化反应的研究成果以及制备方法、载体和助剂改性等对催化性能的影响和反相结构CeO₂/CuO的催化性能。考虑利用催化剂活性组分,尤其是Au与Cu之间的协同作用,选用合适的载体,进行催化剂组分的设计仍然是今后研究的热点。突破常规无定形金属氧化物作载体,通过设计合成具有特定形貌的载体,研究不同晶面和不同价态等因素对催化剂CO优先氧化催化性能的影响,也是一项很有意义的研究。     

负载型Ru/γ-Al_2O_3催化剂上富氢气体中CO选择性氧化去除研究

实验研究了以浸渍法制备的负载型Ru/γ-Al2O3催化剂体系上富氢气体中CO选择性氧化性能,考察了各反应工艺条件包括催化剂中贵金属的担载量、反应原料气中O2/CO的比、CO2和H2O的存在等因素对Ru/γ-Al2O3催化剂上CO选择性氧化活性的影响,采用H2-TPR和XRD手段对催化剂进行检测。研究发现,钌担载量为1%Ru/Al2O3在170~190℃具有很好的CO选择性氧化活性。O2/CO比值升高,提高了CO转化率的同时存在着更多的氢气消耗,氢气的竞争氧化对CO的氧化反应起了一定的抑制作用,CO2的存在对催化剂的性能起着抑制作用,而水的存在对CO去除反应有促进作用。     

低温深度脱除液相丙烯中微量CO的CuO(y)/CuxCe1-xOδ催化剂表征分析及性能实验

采用柠檬酸络合-浸渍的方法制备了CuO(y)/Cu_xCe_1-xO_δ催化剂,重点研究了CuO的载体掺杂和表面负载对催化剂结构性质、氧化还原性能、吸附性能及CO净化性能等的影响,旨在指导催化剂进一步改性,实现低温下深度脱除液相丙烯中微量CO的工业化应用。采用X射线衍射（XRD）、透射电镜（TEM）、X射线光电子能谱分析仪（XPS）、拉曼光谱仪（Raman）和程序升温化学吸附仪（H₂-TPR、CO-TPD）等手段表征了催化剂的结构和性质,结果显示,CuO掺杂的载体,Cu进入CeO₂晶体形成固溶体,有利于催化剂氧化还原性能;浸渍法负载CuO制得的催化剂,表面具有更多的还原态、高分散的Cu物种,有利于表面对CO吸附性能;两者协同作用共同促进了CO催化氧化性能的提升。CuO(0.40)/Cu_0.1Ce_0.9O_δ催化剂具有优异的CO净化性能,在50℃、3.0MPa的工况条件下,可将液相丙烯中CO体积分数从1×10^-5脱除至2.65±0.27×10^-8,达到聚合级烯烃对CO脱除深度的要求,稳定性能良好。     

Ru-La2O3/γ-Al2O3催化CO选择性氧化反应

采用浸渍法制备了Ru-La2O3/γ-Al2O3复合氧化物催化剂,在固定床微反装置中考察了催化剂中稀土La的掺杂量、氧气量、原料气中水和CO2含量以及空速等工艺条件对Ru-La2O3/γ-Al2O3催化剂在CO选择性氧化反应中催化性能的影响.结果表明,Ru/γ-Al2O3催化剂添加质量分数10%的La2O3后的催化性能较好,且具有较好到抗湿性和抗CO2能力.在原料气组成为65%H2,25%CO2,1%CO,9%He,氧气的分压与CO分压相等,气体流速为100 mL/min和气体空速为10 000 h-1的条件下,在110～170℃进行CO选择性氧化,CO转化率大于99%,CO的出口浓度小于100 μL/L,满足了质子交换膜燃料电池对富氢气体中CO浓度的要求.     

Preferential oxidation of CO in rich H2 over CuO/CeO2: Details of selectivity and deactivation under the reactant stream

A CuO/CeO₂ catalyst is examined with respect to its performance for preferential oxidation of CO in H₂-rich streams. Catalytic activity results are explained on the basis of characterization by operando-DRIFTS and complemented with the analysis of redox properties by electron paramagnetic resonance (EPR) and X-ray photoelectron spectra (XPS). General catalytic activity features are accounted for by comparative analysis of the activities for individual CO and H₂ oxidation, for which similar CuO and CeO₂ interfacial active sites appear to be involved. An interesting particularity is related to observation of a low temperature hydrogen oxidation process in which CO apparently acts as gaseous promoter. A deactivation process taking place rapidly under the reactant stream is evidenced and attributed to accumulation of hydroxyls on the interfacial active sites and/or to copper sintering in the course of the run.     

草酸盐热解法制备CoCeZrO复合氧化物用于催化CO-PROX的研究

针对目前CO-PROX反应中钴基催化剂体系研究较少的问题,设计开发了草酸盐热解法制备Zr掺杂CoCe催化剂体系,研究了不同Zr掺杂量对CO-PROX反应活性的影响。结果表明：当Zr和Ce物质的量之比为3∶20时,CO-PROX反应的活性最好,在110℃可将CO完全转化,且在100℃以下O₂至CO₂的选择性维持在100%。BET测试表明,该样品具有最大的比表面积110 m²/g。TEM和XRD表征结果表明,该样品具有最好的Co₃O₄结晶度。H₂-TPR结果表明该样品具有最好的被还原能力。这些都有利于反应活性的提高。     

介孔CuCe/M/CuCe(M=Co,Mn,Zr)催化剂富H_2中优先氧化CO的催化性能

优先氧化是去除富H2中CO最有效的方法,铜铈催化剂是该领域的研究热点。以SBA-15为模板剂,采用纳米刻蚀法合成系列介孔Cu Ce/M/Cu Ce(M=Co,Mn,Zr)催化剂,采用XRD、N2吸附-脱附、TEM、H2-TPR和O2-TPD对催化剂结构及形貌进行表征,并对其在富H2中CO优先氧化性能进行研究。结果表明,Mn有利于催化剂表面吸附氧的增加,有助于大量氧空位的产生,进而促进CO优先氧化性能的提高;Zr的加入抑制了Cu O的还原,且其表面氧脱附温度范围过宽,不利于催化剂催化氧化性能的释放。掺杂Co与Mn可以形成Ce-Cu-M-O固溶体,促进了催化剂表面氧和晶格氧之间的相互转化,最终有利于铜铈催化剂CO优先氧化性能的提高。     

MnOx/Pt/Al2O3 catalysts for CO oxidation in H2-rich streams

The catalytic activity of Pt on alumina catalysts, with and without MnO_x incorporated to the catalyst formulation, for CO oxidation in H₂-free as well as in H₂-rich stream (PROX) has been studied in the temperature range of 25–250 °C. The effect of catalyst preparation (by successive impregnation or by co-impregnation of Mn and Pt) and Mn content in the catalyst performance has been studied. A low Mn content (2 wt.%) has been found not to improve the catalyst activity compared to the base catalyst. However, catalysts prepared by successive impregnation with 8 and 15 wt.% Mn have shown a lower operation temperature for maximum CO conversion than the base catalyst with an enhanced catalyst activity at low temperatures with respect to Pt/Al₂O₃. A maximum CO conversion of 89.8%, with selectivity of 44.9% and CO yield of 40.3% could be reached over a catalyst with 15 wt.% Mn operating at 139 °C and λ = 2. The effect of the presence of 5 vol.% CO₂ and 5 vol.% H₂O in the feedstream on catalysts performance has also been studied and discussed. The presence of CO₂ in the feedstream enhances the catalytic performance of all the studied catalysts at high temperature, whereas the presence of steam inhibits catalysts with higher MnO_x content.     

Development of sulfur tolerant catalysts for the synthesis of high quality transportation fuels

In this paper, results concerning the development of sulfur tolerant catalysts for Fischer–Tropsch synthesis (FTS), C₂₊ alcohol synthesis, methanol and/or DME synthesis are presented. In the FTS reaction on Fe using H₂-rich syngas such as the biomass-derived syngas, the composition of catalyst pretreatment gas and the addition of MnO on Fe had strong impacts on its sulfur resistance as well as activity. Especially the Fe/MnO catalyst pretreated with CO showed a much lower deactivation rate and a higher FTS activity than an Fe/Cu/K catalyst in the presence of H₂S. For C₂₊ alcohol synthesis a novel preparation method was developed for a highly active MoS₂-based catalyst that is well known as the sulfur tolerant catalyst. Besides some metal sulfides were found to show higher CO hydrogenation activities than MoS₂. In particular, both Rh and Pd sulfides were active and selective for the methanol synthesis. Modified Pd sulfide catalyst, i.e. sulfided Ca/Pd/SiO₂, showed an activity that was about 60% of that of a Cu/ZnO/Al₂O₃ catalyst in the absence of H₂S. This catalyst preserved 35% of the initial activity even in the presence of H₂S. The sulfided Ca/Pd/SiO₂ mixed with γ-Al₂O₃ was also available for in situ DME synthesis in the presence of H₂S.     

Methanol synthesis from CO2-rich syngas over a ZrO2 doped CuZnO catalyst

ZrO₂-doped CuZnO catalyst prepared by successive-precipitation method was investigated by ICP-AES, BET, TEM, XRD, EXAFS, H₂-TPR and CO/CO₂ hydrogenation. The active phase of copper in CuZnO catalyst prepared by co-precipitation method was well-crystallized. The presence of ZrO₂ led to a high copper dispersion, which was distinctive from CuZnO. Though the activity for carbon monoxide hydrogenation was little lower than that of CuZnO catalyst, ZrO₂-doped CuZnO catalyst showed much higher activity and selectivity towards methanol synthesis from carbon dioxide hydrogenation. Moreover, ZrO₂-doped CuZnO catalyst showed high performance for methanol synthesis from CO₂-rich syngas.     

Sustainable H2 production from ethanol steam reforming over a macro-mesoporous Ni/Mg-Al-O catalytic monolith

A macro-meso-porous monolithic Ni-based catalyst was prepared via an impregnation route using polystyrene foam as the template and then used in the steam reforming of ethanol to produce a H₂-rich gas. The Ni/Mg-Al catalyst has a hierarchically macro-meso-porous structure as indicated by photographs and scanning electron microscopy (SEM). The surface area of the catalyst was 230 m²?g^-1 and the Ni dispersion was 5.62%. Compared to the pelletized sample that was prepared without a template, the macro-meso-porous Ni/Mg-Al monolith exhibited superior reactivity in terms of H₂ production and also had lower CH₄ yields at 700oC and 800oC. Furthermore, the monolithic catalyst maintained excellent activity and H₂ selectivity after 100-h on-stream at 700^oC, as well as good resistance to coking and metal sintering.     

CuO对Co_3O_4-CeO_2催化剂富氢气条件下CO优先氧化性能的影响

CO优先氧化方法是去除富氢气CO中最为有效的方法,而且钴铈催化剂又受到重点研究和关注。通过共沉淀法制备不同CuO掺杂量的8Co_3O_4-1CeO_2-c CuO催化剂,使用透射电镜、高分辨透射电镜、X射线粉末衍射、N_2吸附-脱附和程序升温还原以及比表面积等测试手段对催化剂进行表征,并对其在富氢气条件下CO优先氧化性能进行研究。结果表明,掺杂适量CuO的钴铈催化剂,其催化活性较未添加CuO的催化剂明显提高,其中钴铈铜物质的量比为8∶1∶1的催化剂其CO完全转化温度降低至115℃,同时添加适量CuO的催化剂粒径明显减小,表面分散度改善,增强了Cu-Co-Ce间相互作用,具有较好的催化活性。     

Silver modified Cu/SiO2 catalyst for the hydrogenation of methyl acetate to ethanol

A series of silver modified Cu/SiO_2 catalysts were synthesized with ammonia-evaporation method and applied in vapor-phase hydrogenation of methyl acetate to ethanol. The influence of additive ‘Ag' on the structural evolution of catalyst was systematically studied by several characterization techniques, such as N_2 adsorption–desorption, N_2O titration, PXRD, FTIR, in-situ FTIR, H_2-TPR, H_2-TPD, XPS and TEM. Results showed that incorporation of a small amount of Ag could enhance the structural stability, and the strong interaction between Cu and Ag species was conducive to increase the dispersion of copper species and create a suitable Cu~(+)/(Cu~0+ Cu~(+)) ratio, which was proposed to be responsible for the improved catalytic activity. The maximum conversion of MA(94.1%)and selectivity of ethanol(91.3%) over optimized Cu-0.5 Ag/SiO_2 and 120 h on stream without deactivation under optimal conditions demonstrates its excellent stability.