CO_(2) hydrogenation to methanol over the copper promoted In_(2)O_(3) catalyst

The metal promoted In_(2)O_(3) catalysts for CO_(2) hydrogenation to methanol have attracted wide attention because of their high activity with high methanol selectivity.However,there was still no experimental confirmation if copper could be a good promoter for In_(2)O_(3).Herein,the Cu promoted In_(2)O_(3) catalyst was prepared using a deposition-precipitation method.Such prepared Cu/In_(2)O_(3) catalyst shows significantly higher CO_(2) conversion and space time yield(STY)of methanol,compared to the un-promoted In_(2)O_(3) catalyst.The loading of Cu facilitates the activation of both H_(2) and CO_(2) with the interface between the Cu cluster and defective In_(2)O_(3) as the active site.The Cu/In_(2)O_(3) catalyst takes the CO hydrogenation pathway for methanol synthesis from CO_(2) hydrogenation.It exhibits a unique size effect on the CO adsorption.At temperatures below 250℃,CO adsorption on Cu/In_(2)O_(3) is stronger than that on In_(2)O_(3),causing higher methanol selectivity.With increasing temperatu res,the Cu catalyst aggregates,which leads to the formation of weak CO adsorption site and causes a decrease in the methanol selectivity.Compared with other metal promoted In_(2)O_(3) catalysts,it can be concluded that the catalyst with stronger CO adsorption possesses higher methanol selectivity.

Triple the steady-state reaction rate by decorating the In_(2)O_(3)surface with SiO_(x)for CO_(2)hydrogenation

Indium oxide(In_(2)O_(3)),as a promising candidate for CO_(2)hydrogenation to C_(1) products,often suffers from sintering and activity decline,closely related to the undesirable structural evolution under reaction conditions.Based on the comprehension of the dynamic evolution,this study presents an efficient strategy to alleviate the agglomeration of In_(2)O_(3)nanoparticles by the surface decoration with highly dispersed silica species(SiO_(x)).Various structural characterizations combined with density functional theory calculations demonstrated that the sintering resulted from the over-reduction,while the enhanced stability originated from the anchoring effect of highly stable In-OSi bonds,which hinders the substantial formation of metallic In(In^(0))and the subsequent agglomeration.0.6Si/In_(2)O_(3)exhibited CO_(2)conversion rate of10.0 mmol g^(-1)h^(-1)at steady state vs.3.5 mmol g^(-1)h^(-1)on In_(2)O_(3)in CO_(2)hydrogenation.Enhanced steady-state activity was also achieved on Pd-modified catalysts.Compared to the traditional Pd/In_(2)O_(3)catalyst,the methanol production rate of Pd catalyst supported on 0.6Si/In_(2)O_(3)was enhanced by 23%,showing the potential of In_(2)O_(3)modified by SiO_(x)in serving as a platform material.This work provides a promising method to design new In_(2)O_(3)-based catalysts with improved activity and stability in CO_(2)hydrogenation.

Comparison of Perovskite Systems Based on AFeO_(3)(A=Ce,La,Y)in CO_(2) Hydrogenation to CO

CO_(2) is the most cost-eff ective and abundant carbon resource,while the reverse water-gas reaction(rWGS)is one of the most eff ective methods of CO_(2) utilization.This work presents a comparative study of rWGS activity for perovskite systems based on AFeO_(3)(where A=Ce,La,Y).These systems were synthesized by solution combustion synthesis(SCS)with diff erent ratios of fuel(glycine)and oxidizer(φ),diff erent amounts of NH 4 NO_(3),and the addition of alumina or silica as supports.Various techniques,including X-ray diff raction analysis,thermogravimetric analysis,Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy,energy-dispersive X-ray spectroscopy,N 2-physisorption,H_(2) temper-ature-programmed reduction,temperature-programmed desorption of H_(2) and CO_(2),Raman spectroscopy,and in situ FTIR,were used to relate the physicochemical properties with the catalytic performance of the obtained composites.Each specifi c perovskite-containing system(either bulk or supported)has its own optimalφand NH_(4) NO_(3) amount to achieve the highest yield and dispersion of the perovskite phase.Among all synthesized systems,bulk SCS-derived La-Fe-O systems showed the highest resistance to reducing environments and the easiest hydrogen desorption,outperforming La-Fe-O produced by solgel combustion(SGC).CO_(2) conversion into CO at 600°C for bulk ferrite systems,depending on the A-cation type and preparation method,follows the order La(SGC)<Y<Ce<La(SCS).The diff erences in properties between La-Fe-O obtained by the SCS and SGC methods can be attributed to diff erent ratios of oxygen and lanthanum vacancy contributions,hydroxyl coverage,morphology,and free iron oxide presence.In situ FTIR data revealed that CO_(2) hydrogenation occurs through formates generated under reaction conditions on the bulk system based on La-Fe-O,obtained by the SCS method.γ-Al_(2)O_(3) improves the dispersion of CeFeO_(3) and LaFeO_(3) phases,the specifi c surface area,and the quantity of adsorbed H_(2) and CO_(2).This led to a signifi cant increase in CO_(2) conversion for supported CeFeO_(3) but not for the La-based system compared to bulk and SiO_(2)-supported perovskite catalysts.However,adding alumina increased the activity per mass for both Ce-and La-based perovskite systems,reducing the amount of rare-earth components in the catalyst and thereby lowering the cost without substantially compromising stability.

Increased Oxygen Vacancies in CuO-ZnO Snowflake-like Composites Drive the Hydrogenation of CO_(2) to Methanol

Cu/ZnO is widely used in the hydrogenation of carbon dioxide (CO_(2)) to methanol (CH_(3)OH) to improve the lowconversion rate and selectivity generally observed. In this work, a series of In, Zr, Co, and Ni-doped CuO-ZnO catalysts wassynthesized via a hydrothermal method. By introducing a second metal element, the activity and dispersion of the activesites can be adjusted and the synergy between the metal and the carrier can be enhanced, forming an abundance of oxygenvacancies. Oxygen vacancies not only adsorb CO_(2) but also activate the intermediates in methanol synthesis, playing a keyrole in the entire reaction. Co3O4-CuO-ZnO had the best catalytic performance (a CO_(2) conversion rate of 9.17%;a CH_(3)OHselectivity of 92.77%). This study describes a typical strategy for multi-component doping to construct a catalyst with anabundance of oxygen vacancies, allowing more effective catalysis to synthesize CH_(3)OH from CO_(2).

Preparation of palladium-based catalyst by plasma-assisted atomic layer deposition and its applications in CO_(2) hydrogenation reduction

Supported Pd catalyst is an important noble metal material in recent years due to its high catalytic performance in CO_(2)hydrogenation.A fluidized-bed plasma assisted atomic layer deposition(FP-ALD) process is reported to fabricate Pd nanoparticle catalyst over γ-Al_(2)O_(3)or Fe_(2)O_(3)/γ-Al_(2)O_(3)support,using palladium hexafluoroacetylacetonate as the Pd precursor and H_(2)plasma as counter-reactant.Scanning transmission electron microscopy exhibits that highdensity Pd nanoparticles are uniformly dispersed over Fe_(2)O_(3)/γ-Al_(2)O_(3)support with an average diameter of 4.4 nm.The deposited Pd-Fe_(2)O_(3)/γ-Al_(2)O_(3)shows excellent catalytic performance for CO_(2)hydrogenation in a dielectric barrier discharge reactor.Under a typical condition of H_(2)to CO_(2)ratio of 4 in the feed gas,the discharge power of 19.6 W,and gas hourly space velocity of10000 h^(-1),the conversion of CO_(2)is as high as 16.3% with CH_(3)OH and CH4selectivities of 26.5%and 3.9%,respectively.

CO_(2)-assisted oxidation dehydrogenation of light alkanes over metal-based heterogeneous catalysts

Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.

海洋CO_(2)地质封存研究进展与发展趋势

CO_(2)捕集、利用和封存是中国实现“双碳”目标的核心技术,也是全球研究的热点。CO_(2)地质封存是其中的关键环节,特别是海洋CO_(2)地质封存是今后的重点发展方向。以国内外海洋CO_(2)地质封存的发展历程为基础,结合典型CO_(2)海洋封存示范项目案例,系统梳理了国内外海洋CO_(2)地质封存理论研究进展,分析了CO_(2)在井筒流动、相变与传热、CO_(2)流体运移与储层物性参数展布规律、海洋地质封存机制及封存潜力、地质封存盖层完整性及安全性评估等方面的研究现状。认识到中国目前对海底地质结构中CO_(2)注入过程的多相态转化、溶解、捕获传质特征及动力学特性认识尚浅,对海洋封存机制及不同封存机制之间的相互作用机理尚不明确,未来应开展海洋CO_(2)动态地质封存空间重构机制研究,解决地质封存相态转化及流体动态迁移机理等关键科学问题,揭示海洋CO_(2)地质封存机制的相互作用机理,形成适用于中国海洋地质封存CO_(2)高效注入和增效封存方法。

黄铁矿在CO_(2)气氛下非等温氧化转化及动力学分析

针对煤中常见含铁矿物黄铁矿在富氧燃烧典型气氛下转化特性,通过同步热分析结合烟气分析研究了黄铁矿在CO_(2)气氛下的转化行为.结果发现,黄铁矿在CO_(2)气氛下主要经历5个失重阶段且均为吸热过程,首先是黄铁矿颗粒表面硫脱除的起始热解段(相界面反应,n=1/2),活化能低于其在N_(2)气氛下近30 kJ/mol,为220.27 kJ/mol,随后裂解成磁黄铁矿(三维扩散,n=1/2)活化能与其在N_(2)(177.27 kJ/mol)下接近为178.1 kJ/mol;温度高于690℃,随着升温磁黄铁矿缓慢失硫,CO_(2)逐渐参与磁黄铁矿转化且释放SO_(2)和CO;820~1150℃经历双峰失重峰阶段,820~1020℃,氧化气体产物SO_(2)大量生成且在约1000℃达到体积浓度峰值;最后1020~1150℃,坩埚中残留物大量与CO_(2)持续氧化反应失重形成SO_(2)和CO,坩埚中形成复杂物相体系,铁硫化物和铁氧化物共存(或共融).CO_(2)参与黄铁矿产物转化失重阶段活化能分别为180.94 kJ/mol、229.69 kJ/mol和243.46 kJ/mol,动力学机制均为成核与生长(n=1).

“双碳”目标下火电厂CO_(2)计量技术研究现状与展望

中国电力行业CO_(2)排放量是CO_(2)排放的主要来源,其中火电厂CO_(2)排放量在电力行业中占比最大。在“双碳”目标下,CO_(2)计量技术可以实现对火电厂中CO_(2)排放量的直观判断,为火电厂CO_(2)减排提供重要支撑,促进火电厂参与碳交易,带动区域经济发展。结合国内外政策,讨论了目前通用CO_(2)计量方法的实施进展,总结归纳了以碳核算为主、碳监测为辅的火电厂CO_(2)计量方法存在的问题,并对火电厂CO_(2)计量技术应用的重难点进行了分析。最后,对火电厂CO_(2)计量技术的发展及应用进行了展望。

纳米SiO_(2)强化CO_(2)地质封存页岩盖层封堵能力机制试验

页岩为CO_(2)盐水层地质封存常见盖层岩石类型,强化盖层封堵能力有利于提高CO_(2)地质埋存量和安全性。为探究随CO_(2)混注纳米SiO_(2)(SNPs)强化盖层封堵能力的有效性和可行性,对CO_(2)地质封存页岩盖层样品开展原地条件下的超临界CO_(2)酸蚀反应试验,基础组为页岩样品-地层水、对照组为页岩样品-地层水+超临界CO_(2)、优化组为页岩样品-地层水+SNPs+超临界CO_(2),并采用核磁共振测试、场发射扫描电镜可视化观测、X射线衍射测试和岩石力学试验,探究CO_(2)酸蚀反应前后的页岩孔隙结构、表面形貌、矿物成分及力学性质特征。结果表明:优化组的大孔孔隙分量及孔隙度和渗透率增大幅度低于对照组;与对照组相比,优化组黏土矿物与碳酸盐岩矿物相对含量损失少,表明随CO_(2)混注SNPs可使岩样内部酸蚀作用减弱;SNPs在岩石端面吸附聚集或进入岩心孔喉,可使优化组页岩样品力学性能损伤程度降低;随CO_(2)混注SNPs有利于强化CO_(2)盐水层地质封存盖层封堵能力。

三河尖关闭煤矿煤层CO_(2)封存潜力研究

关闭煤矿煤层CO_(2)地质封存是CO_(2)封存的重要方式之一,也是短期内实现碳减排指标的有效手段之一。以江苏省徐州市三河尖关闭煤矿为例,分析了已采7号煤和9号煤的煤岩煤质特征,统计了剩余煤炭资源储量,运用模糊综合评价法,选取了稳定系数、上覆岩层性质、地质构造复杂程度、地下水指标、封存煤层压温比、封存煤层深厚比、封存煤层渗透率、采空塌陷程度和其他因素等9个主要影响因素指标对7号煤和9号煤封存CO_(2)稳定性进行评价,建立关闭煤矿煤层CO_(2)封存评价方法并评估CO_(2)封存潜力。结果表明,三河尖关闭煤矿7号煤和9号煤剩余储量较大,CO_(2)封存稳定性综合评价结果分别为86.209和87.698,评价等级均为较稳定,封存潜力较高。根据建立的关闭煤矿煤层CO_(2)封存评价方法,计算获得三河尖关闭煤矿7号和9号煤层CO_(2)理论封存量分别为207.6 Mt和80.9 Mt,并据此划分封存有利区为有利区、较有利区和不利区3个等级。研究可为关闭煤矿煤层CO_(2)封存研究提供基础依据。

一种基于“四区”的低渗透油藏CO_(2)埋存量计算方法及应用

CO_(2)驱油和埋存能有效减少温室气体排放量达到碳中和目标,已有的CO_(2)埋存量计算方法主要针对CO_(2)的静态埋存量进行粗略计算,未考虑实际生产过程中CO_(2)埋存量的变化。针对上述问题,运用CO_(2)溶解、CO_(2)波及体积和驱油机理,将CO_(2)驱油与埋存过程分为气相区、两相或近混相区、扩散区和油相区,并基于“四区法”计算CO_(2)埋存量,得到了不同烃类的注入孔隙体积倍数、注入压力、注气速度下的CO_(2)动态埋存量的变化规律。将研究成果应用于W油田低渗储层,结果表明:注入烃类孔隙体积倍数、压力、注气速度与总埋存量呈正相关性,当压力由12 MPa升至30 MPa,CO_(2)埋存总量增加15.53×10^(4)t;当注气速度由5 t/d增加至30 t/d,峰值CO_(2)埋存总量由3.51×10^(4)t提高至12.62×10^(4)t。研究成果可为同类油藏开展CO_(2)驱油与埋存项目提供新的思路。

CO_(2)分注井气嘴节流特性及矿场应用

为了解决CO_(2)分注井节流压差建立困难,气嘴易冲蚀的技术难题,通过构建CO_(2)物性变化的流动-传热耦合模型,揭示2级和3级节流气嘴的流场演化机制,优化设计气嘴结构、建立了绕流气嘴节流图版并开展现场应用。结果表明:流量为10 m3/d时,2级嘴径1.4 mm和3级嘴径1.6 mm的绕流气嘴分别能产生将近6 MPa和8 MPa的节流压差,证明绕流气嘴结构合理、性能可靠、能够达到调整层间压差的技术要求;参照气嘴图版优选的节流气嘴,现场应用20口井,节流压差可达4 MPa左右,调整后注入压力上升2.4 MPa,加强层相对吸气比例由9.7%上升至50.7%,有效调整了层间差异,解决了分注井小层吸气不均的问题。研究结果指导现场测调,为CO_(2)分注规模化应用提供技术支撑。

跨临界CO_(2)循环系统控制优化策略的研究进展

控制策略作为跨临界CO_(2)循环系统的重要组成部分,是保证系统高效节能运行的关键。介绍了系统最优排气压力经验计算和泊金汉π定理的反馈控制、基于梯度追踪和极值寻优的实时在线控制以及基于神经网络的预测控制等,详细分析了系统控制策略的发展历程和未来发展趋势,并总结如下:离线控制建立简单、成本低,但易受到环境因素和系统部件变化的影响而导致控制性能降低;实时在线控制策略可以实时追踪系统最大能源效率对应的排气压力,但由于寻优过程费时较长,导致控制系统的收敛时间过长;模型预测控制系统可以实现实时优化和快速收敛,有着良好的发展前景。结合新能源汽车、建筑供暖、轨道交通、商超冷藏、军工等实际场景对跨临界CO_(2)循环系统控制策略的应用特点和未来发展趋势进行分析,进一步说明了提高控制策略的适用性是未来研究的重要方向,并分析将广义预测控制、强化学习等具有自适应属性的方法应用于跨临界CO_(2)循环系统控制策略的可行性,同时探讨了开发适用于大规模循环系统和储能系统控制策略在我国“双碳”背景下的重要意义。

SCCO_(2)作用下不同含水性煤孔裂隙结构变化机制

深部煤层封存CO_(2)增产CH_(4)产出过程中,处于超临界状态的CO_(2)(SCCO_(2))与煤中矿物质发生反应,改变煤的孔隙性,进而影响煤层封存CO_(2)的效果和甲烷增产效果。为发现SCCO_(2)–H_(2)O–煤岩作用对煤中孔隙的影响特征,以焦煤为研究对象,开展了不同含水条件下的超临界CO_(2)改造煤实验,基于矿物组成和孔隙性测定结果,对比煤中主要矿物质和不同尺度的孔裂隙变化的差异,探讨了不同含水状态下SCCO_(2)流体对孔裂隙性的作用机制。研究表明:①SCCO_(2)作用后,煤体表面粗糙、疏松,且由于矿物溶蚀使得一些裂隙得到贯通,微裂隙连通性增强。②SCCO_(2)流体对煤具有“扩孔”作用,表现为微、小孔含量下降,中、大孔占比升高,也即微、小孔隙向大孔隙的转化,且孔隙连通性改善;进一步发现,萃余煤吸附孔的分形维数稍微增加,粗糙度增大,而渗流孔的分形维数显著降低,复杂性和非均质性降低。③SCCO_(2)对煤中碳酸盐类矿物的溶解性最好,其次是黏土矿物,且随着含水率增加,萃余煤中的碳酸盐矿物占比先增加后减小。SCCO_(2)使干燥基态、饱和水态煤样中碳酸盐矿物显著溶解,有效改善了孔隙结构,且对饱和水态煤样作用效果更好。空气干燥基态煤样经SCCO_(2)作用后,新生成的白云石矿物聚集在孔喉中造成堵孔效应,缩小原有大孔隙尺寸,是引起不同含水性煤孔隙差异性变化的主要原因。

适合致密油藏的超临界CO_(2)-气溶性表面活性剂复合吞吐技术

为了进一步提高致密油储层超临界CO_(2)吞吐的开发效果,探索适合致密油藏的超临界CO_(2)-气溶性表面活性剂复合吞吐技术,通过原油黏度实验、油气界面张力实验、最小混相压力实验、原油膨胀系数实验以及超临界CO_(2)-气溶性表面活性剂复合吞吐模拟实验,评价了不同类型气溶性表面活性剂的性能及其对吞吐采收率的影响。结果表明:气溶性表面活性剂GRS⁃1的综合性能更加突出,随着气溶性表面活性剂质量分数的不断增大,原油黏度、油气界面张力和最小混相压力均呈现出逐渐降低的趋势,而原油体积膨胀系数则逐渐增大,并且岩心的吞吐采收率和入口端压力也呈现出逐渐增大的趋势;随着混合流体注入量的增加以及闷井时间的延长,岩心吞吐采收率和入口端压力均逐渐增大,并且岩心的渗透率越大,吞吐采收率就越高;超临界CO_(2)-气溶性表面活性剂复合吞吐的最佳实验参数为气溶性表面活性剂GRS⁃1的质量分数0.6%、混合流体注入量0.5 PV、闷井时间3 h、吞吐轮次3次。该复合吞吐技术能够显著提高致密油藏的采收率,对高效开发致密油藏具有指导意义。

“双碳”愿景下CO_(2)驱强化采油封存技术工程选址指标评价

在国家能源安全和“双碳”战略愿景下,CO_(2)驱强化采油封存技术(CO_(2)-EOR)因能助力油气行业转型发展,成为“低碳化”乃至“负碳化”的首选技术和最现实的选择。无论是实验、数值模拟还是现场实践,目前国内外学者对CO_(2)-EOR研究侧重于CO_(2)作为高效的驱油“催化剂”本身及油藏CO_(2)-EOR适应性认识,对于工程选址评价缺乏统一标准和系统研究。在充分调研国内外文献的基础上,结合中国CO_(2)-EOR应用进展和工程实践,明确了CO_(2)-EOR工程选址可行性评价所需的通用依据,指出了CO_(2)-EOR工程选址遵循“CO_(2)封存与驱油双统一”、安全性、经济性的专属性原则,并从CO_(2)-EOR工程选址的地质、工程、安全、经济4个要素开展了较详尽系统的研究,定性-定量构建了“4+8+27”CO_(2)-EOR工程选址三级指标评价体系(GESE),以期为油藏开展CO_(2)-EOR工程选址提供借鉴,助力中国碳减排技术的应用与发展。

低渗砂岩油田CO_(2)驱化学机理及提高采收率研究

针对低渗砂岩油藏进行了CO_(2)驱开发技术研究,分析了CO_(2)驱油化学机理及主要影响因素。基于目标油藏流体特征进行了PVT拟合,确定其CO_(2)驱最小混相压力,明确了不同压力及注入时机对CO_(2)驱采收率、气油比、含水率及驱动压差等的影响规律,探究了CO_(2)泡沫驱在提高采收率方面的效用。结果表明:24.5 MPa为目标区域CO_(2)驱的最小混相压力,采收率会随着压力的升高而增加,28 MPa时CO_(2)驱提高采收率可达30.57%。气体突破时间、总采收率与CO_(2)注入时机密切相关,CO_(2)注入越早,越有利于采收率的提高,出口含水率为60%时注入可提高采收率39.13%。CO_(2)泡沫驱可以在一定程度上起到提高采收率的效用。

基于三维点云计算的CO_(2)-水-岩反应程度量化表征方法

CO_(2)地质封存是减少大气中CO_(2)排放,降低温室效应的重要途径,CO_(2)注入含水地层中时,CO_(2)-水-岩反应可能引起岩石矿物的侵蚀,对CO_(2)地质封存安全性产生显著影响。在室内实验中,通过表征岩石表面的形貌特征可以有效地评估CO_(2)-水-岩反应程度,为CO_(2)地质封存的安全性评估提供科学依据。通过三维点云计算可以精确量化地表征CO_(2)-水-岩反应程度,这种方法首先运用三维激光扫描技术,构建岩石表面的三维模型,确定CO_(2)-水处理前岩石表面三维模型的基准面,并基于处理前的均方根粗糙度确定处理后岩石表面三维模型的基准面。基于三维模型点云信息,提出了两种不同的体积计算新方法,并通过对规则模型体积的计算比较了两种计算方法的准确性与适用性,可根据实际情况选择两种计算方法量化表征CO_(2)-水处理前后岩石表面的侵蚀体积。最后,以陕西省咸阳市某煤矿煤样为例,开展了CO_(2)-水-岩反应模拟试验,验证了计算的可行性。试验结果表明:该文提出的侵蚀体积计算方法可有效地量化表征CO_(2)-水-岩反应程度,CO_(2)-水处理后岩石表面不同区域的侵蚀差异性明显,岩石表面的侵蚀体积与均方根粗糙度之间存在显著的正比关系,随着均方根粗糙度的增大,侵蚀体积也相应上升。

CuZn/CeO_(2)催化剂在CO_(2)加氢制甲醇中的应用研究

CO_(2)加氢制甲醇反应过程中产生的大量副产物水会加速催化剂中CuZn物种的聚集和烧结,导致催化剂严重失活。而CeO_(2)亲水性较弱,具有较高的水热稳定性,可以增强CuZn物种的分散。因此,通过水热合成法制备了一系列CeO_(2)载体晶面可调控的CuZn基催化剂,并在其中引入了适当浓度的氧空位。采用TEM、XRD和H_(2)-TPR等表征手段研究了合成的CeO_(2)载体及CuZn/CeO_(2)-y催化剂(y为rod、cube或otca)的形貌、结构和还原性能等物理化学性质,并考察了CuZn/CeO_(2)-y催化剂在CO_(2)加氢制甲醇反应中的催化性能。结果表明,暴露(110)晶面的纳米棒结构的CeO_(2)载体(CeO_(2)-rod)更有利于CuZn基物种的分散,并且CeO_(2)-rod与Cu物种形成了Cu—O—Ce界面,增强了催化剂同时吸附和活化CO_(2)和H_(2)的性能。因此,CuZn/CeO_(2)-rod表现出较高的CO_(2)转化率和甲醇选择性,在260℃、3MPa的条件下,甲醇时空收率为433.4g/(kg·h),甲醇选择性高达68.5%。同时,利用原位漫反射傅立叶变换红外光谱对CO_(2)加氢制甲醇的反应路径和重要中间物种的演变进行了详细研究,发现在CuZn/CeO_(2)催化剂的作用下,反应主要遵循甲酸盐路径,载体的晶面效应没有改变反应路径,但是提高了重要中间物种达到平衡的速率。