合成气甲烷化催化剂的研究与进展

介绍了目前国内外甲烷化催化剂种类;综述了助剂、载体及制备方法对催化剂性能的影响;并对甲烷化催化剂的研究进行了展望,旨在为我国未来甲烷化催化剂的研究与发展提供参考。今后催化剂研究方向应包括三个方面:(1)与工艺技术结合,对不同工艺的催化剂进行优化;(2)开发抗硫催化剂,在保持催化活性的基础上提高其抗硫性能;(3)煤一步法制天然气催化剂的研究。     

甲烷二氧化碳重整镍基催化剂的研究进展

甲烷二氧化碳重整制合成气是对甲烷、二氧化碳这2种温室气体资源化利用的有效途径。近年来,研究最多的领域是关于该反应催化剂的开发,其中镍基催化剂的研究最广泛。为了全面了解甲烷二氧化碳重整反应及镍基催化剂的应用,介绍了甲烷二氧化碳重整反应的热力学研究及机理;分析了镍基催化剂的积碳原因及消碳途径;论述了镍基催化剂的载体、助剂、制备方法对催化剂催化性能的影响;最后对镍基催化剂未来的研究方向进行了展望。热力学研究结果显示,高温低压有利于甲烷二氧化碳重整反应的进行;针对甲烷二氧化碳重整反应的机理尚没有统一的定论,不同催化剂应用于该反应,作用机理也不同;镍基催化剂积碳主要由甲烷裂解反应、一氧化碳歧化反应及一氧化碳氧化还原反应产生,为解决积碳问题,从催化剂方面着手,通过调控催化剂性质抑制积碳;载体性质、助剂类型、制备方法不同会对镍基催化剂产生不同作用;镍基催化剂距离工业化应用还有一段距离,在未来发展中可优化催化剂制备条件,深入探究催化剂的积碳机理,理论与实践相结合,进一步探究镍基催化剂的性能。     

助剂对煤基合成气甲烷化反应用镍基催化剂的促进作用

助剂促进的合成气甲烷化反应用镍基催化剂具有反应活性高、使用寿命长以及甲烷选择性高等优点,被广泛应用于煤基合成气甲烷化制替代天然气反应中。本文重点介绍了贵金属、碱土金属、稀土金属以及过渡金属助剂等对活性镍基催化剂的分散度、还原度、双金属合金协同效应、镍基催化剂结构稳定性及其对合成气甲烷化反应速率和产物选择性的影响。较系统地分析了这些助剂改性镍基催化剂的作用机制。提出了非贵金属助剂以及复合助剂将是合成气甲烷化用镍基催化剂助剂研发的发展方向,旨在为煤基合成气制替代天然气甲烷化催化剂的研发提供借鉴和参考。     

煤制天然气镍基催化剂的研究进展

介绍煤制天然气的现状及CO加氢甲烷化机理;比较不同甲烷化反应器的优缺点;阐述合成气甲烷化镍基催化剂的性能,分析了2种不同载体硅胶和氧化铝的作用机理,并进一步分析了载体和制备方法对催化剂性能的影响。     

宽温型镍基甲烷化催化剂制备及催化性能

利用挤条成型及等体积浸渍法制备了负载型镍基甲烷化催化剂。通过H₂-TPR等表征方法对催化剂进行表征,研究了MgO对镍基催化剂中NiO与载体Al₂O₃相互作用力的影响。催化剂活性评价表明,助剂MgO在甲烷化反应中对CH₄选择性具有明显的促进作用。考察了催化剂的高温稳定性,并对镍基催化剂的低温失活现象进行了研究。     

甲烷部分氧化制合成气镍基催化剂的研究进展

镍基催化剂是甲烷部分氧化制合成气研究最多、最有前途的催化剂.相对其他催化剂它具有较好的抗积碳性、稳定性且价格低廉.如何提高甲烷在部分氧化反应中的转化率是当前备受关注的重要研究课题.从镍基催化剂的载体、助剂、制备方法等方面的研究进行了综述.     

非晶态Ni-B/MCM-22催化剂上二氧化碳甲烷化的研究

本文采用固定床反应装置考察了非晶态镍基催化剂CO2甲烷化催化反应活性。研究结果表明:以化学还原法制备的非晶态镍基催化剂的二氧化碳甲烷化活性较高;由XRD及TEM结果可知,非晶态镍基催化剂中镍的分散度较高;以MCM-22分子筛为催化剂载体的非晶态镍基催化剂CO2的转化率高于以γ-Al2O3为载体的非晶态催化剂。     

铝铈助剂对镍基甲烷化催化剂性能的影响

用沉淀法制备了镍基甲烷化催化剂,采用X-射线衍射、氢气程序升温还原和扫描电镜等技术对合成催化剂进行了表征.结果表明,铝助剂对形成微球状催化剂有较大的促进作用,铝铈助剂对镍基催化剂的还原有明显的促进作用,铈助剂大幅提高了催化剂的抗积碳能力.复合催化剂的催化活性明显高于单一催化剂.     

CRG技术在煤制合成天然气中的应用

介绍了甲烷化催化剂的研究现状及其构造,并对甲烷化镍基催化剂失活的原因进行了分析,指出硫中毒和积碳是造成催化剂失活的主要因素。分析了催化剂中的主要活性组分,载体及助剂的添加对CO甲烷化反应的影响。对大唐克旗煤制天然气甲烷化催化剂提出了改良的方法。     

CO2甲烷化催化剂的研究进展

CO₂甲烷化反应因其可以将温室气体CO₂转化为清洁能源(CH₄)而受到广泛关注。本文介绍了CO₂甲烷化反应的机理与热力学研究进展,分析了CO₂甲烷化催化剂活性中心、粒子尺寸和载体效应对催化剂反应性能的影响规律。介绍了高熵合金、溶出型金属等新型催化剂在CO₂甲烷化反应中的应用,总结了影响Ni基CO₂甲烷化催化剂反应稳定性的2个主要因素(粒子烧结和硫中毒)以及提高Ni基催化剂抗烧结和抗硫中毒的举措(利用限域效应、添加CeO₂等),从而为新型CO₂甲烷化催化剂的研究和开发提供理论基础。最后,对CO₂甲烷化催化剂的研究开发进行了展望。     

Performance of Ni/Nano-ZrO2catalysts for CO preferential methanation简

Large surface areas nano-scale zirconia was prepared by the self-assembly route and was employed as support in nickel catalysts for the CO selective methanation. The effects of Ni loading and the catalyst calcination temperature on the performance of the catalyst for CO selective methanation reaction were investigated. The cata- lysts were characterized by Brunauer-Emmett-Teller （BET）, transmission electron microscope （TEM）, X-ray dif- fraction （XRD） and temperature-programmed reduction （TPR）. The results showed that the as-synthesized Ni/nano-ZrO2 catalysts presented high activity for CO methanation due to the interaction between Ni active particle and nano zir- conia support. The selectivity for the CO methanation influenced significantly by the particle size of the active Ni species. The exorbitant calcination resulted in the conglomeration of dispersive Ni particles and led to the decrease of CO methanation selectivity. Among the catalysts studied, the 7.5% （by mass） Ni/ZrO2 catalyst calcinated at 500℃ was the most effective for the CO selective methanation. It can preferentially catalyze the CO methanation with a higher 99% conversion in the CO/CO2 competitive methanation system over the temperature range of 260-280℃, while keeping the CO2 conversion relatively low.     

甲烷化催化剂及其失活研究进展

阐述甲烷化催化剂活性组分、载体和助剂种类对催化性能的影响。分析催化剂失活的主要原因为中毒失活、积炭失活和烧结失活。目前在国内外工业装置上得到应用的主要为Al2O3、镁铝尖晶石类负载的Ni基甲烷化催化剂。通过载体改性、助剂添加及调配提升催化剂性能是催化剂研发的主要方向。复合载体可以形成特定的稳定结构,提高催化剂的热稳定性;其较高的比表面积利于Ni的分散;碱金属、碱土金属和稀土金属的添加,可以调变载体表面酸性和电负性,减小Ni晶粒尺寸,降低积炭的可能性。     

尿素燃烧法制备镍基甲烷化催化剂及其催化反应性能

以拟薄水铝石、硝酸镍以及镁、钴、镧和铁的硝酸盐为原料,尿素为燃烧剂,采用尿素燃烧法制备系列镍基(以及含助剂)甲烷化催化剂。通过XRD和BET等对催化剂结构进行表征,采用固定床反应器评价催化剂的合成气甲烷化催化反应性能,考察Ni含量、尿素与原料质量比、焙烧温度和不同助剂等对催化剂结构和性能的影响,评价催化剂的稳定性。结果表明,Ni O质量分数为7.5%~44.8%时,采用尿素燃烧法均可制备γ-Al2O3为载体的镍基甲烷化催化剂,最佳制备条件为:尿素与原料质量比3∶1,焙烧温度450℃,燃烧时间40 min。26.1%Ni O/γ-Al2O3催化剂表现出较好的催化性能,在230℃和常压条件下,CO转化率和CH4选择性分别达99.5%和98.3%。26.1%Ni O-2.6%La2O3/γ-Al2O3催化剂在(230~700)℃经过多次升降反应温度和1 460 h的长周期稳定性测试,表现出较好的稳定性和耐热冲击性能。     

Industrial catalysts for the hydrogenation of carbon oxides

Conditions for the synthesis, reduction and passivation of methanation catalysts are summarized. Requirements are given for preparing catalysts for use. The basic characteristics of industrial methanation catalysts and the conditions for their use are discussed. It is noted that the NIAP-07 domestic catalysts of the NKM series have a life span of 15 years. It is shown that the new high-performance nickel methanation catalyst has a lower activation temperature and can be manufactured in the form of rings, extrudates, or pellets. The use of a ring-shaped catalyst allows us to reduce the gas-dynamic resistance of a methanator and thus to economize on natural gas in ammonia production units. NIAP-KATALIZATOR has organized industrial production of methanation catalysts. The NIAP-07 (NKM) catalysts can be used in various industrial processes for purifying gases of carbon oxides via their hydrogenation.     

煤制天然气高CO甲烷化的研究进展

煤制天然气是目前煤化工的热门领域,文章主要介绍国内外煤制天然气的研究、开发及应用进展,对比分析了国内外高CO甲烷化催化剂,尤其是Ni基催化剂的研究进展和技术特点、反应器的设计及原理,及高CO甲烷化技术的研究方向。     

煤制天然气甲烷化催化剂及机理的研究进展

煤制天然气技术是将高碳能源转化为富氢、低碳能源的有效途径,发展以煤为原料、将合成气通过甲烷化反应制备天然气是今后煤清洁利用的重要途径。介绍了国内外煤制天然气的研究现状和甲烷化反应在煤制天然气中的应用。阐述了近年来CO、CO₂甲烷化催化剂中几种常见的氧化物负载型Ni基催化剂载体(Al₂O₃、ZrO₂、SiO₂、TiO₂)和催化剂助剂的制备方法以及化学结构特点,分析了一些新型催化剂载体（MWCNT、SiC、LaFeO₃）、贵金属催化剂、非晶态合金催化剂、钙钛矿催化剂的研究现状和制备方法对催化剂催化性能的影响。分别对因高温烧结、催化剂中毒和催化剂积炭在工业上引起的甲烷化催化剂失活进行分析,并提出催化剂的改进方法。阐述CO甲烷化反应的次甲基机理、表面碳机理和变换-甲院化反应机理;近年来CO₂甲烷化反应机理尽管一直存在分歧,但在催化过程中生成含碳中间物种的理论已被认同。今后甲烷化催化剂的研究方向包括开发新型甲烷化催化剂（低温催化剂、催化剂掺杂改性）、新型复合载体、抗硫催化剂（钼、钨催化剂）以及开发甲烷化新工艺和进一步深入探索甲烷化反应机理。     

Hydrogenation of carbon monoxide over nickel zeolite catalysts — effect of reduction and calcination

NiNaY zeolite catalysts were prepared by successive ion exchange of NaY. The catalysts were characterized for BET surface area, nickel metal area, nickel crystallite size and crystallinity. The methanation of carbon monoxide was studied in a fixed bed reactor in the temperature range of 523–673 K. Specific activities for methanation were found to vary with nickel concentration and crystallite size. The values of nickel metal area and specific methanation activity for the uncalcined catalysts were found to be higher compared to those of calcined catalysts. The effect of reduction at 723 K on the zeolite base structure and the effects of calcining the catalyst on metal area, crystallite size and activity are discussed.     

MONOLITHIC-SUPPORTED NICKEL CATALYSTS: I. METHANATION ACTIVITY RELATIVE TO PELLET CATALYSTS

The catalytic activity and selectivity of pellet and monolithic supported Ni/A1₂O₃ for methanation of carbon monoxide were investigated to determine the role of support geometry in catalyst performance. Turnover numbers, CO conversion versus temperature data, and product distributions were measured at space velocities from 15,000 to 50,000 hr^-1 and pressures of 140 to 2500 kPa. The data show that monolithic supported nickel is significantly more active and selective for methane production at both low and high CO conversions compared to nickel catalysts beads and pellets. Monolithic supported methanation catalysts apparently operate with a higher effectiveness and rate of mass transfer than do catalyst beads or pellets. Because of its superior activity, selectivity and tow pressure drop at high space velocities, monolithic nickel may be the ideal catalyst for use in a high throughput recycle methanator     

Characterization and methanation activity of supported nickel catalysts

The methanation of carbon monoxide was studied over various supported nickel catalysts in a fixed bed reactor in the temperature range of 250 to 400°C. The hydrogen to carbon monoxide ratio was kept higher than stoichiometric in order to avoid carbon formation. The catalyst particles had an average diameter of 80 pm and nickel contents ranging from 5 to 42 wt %. The performance of laboratory prepared catalysts was compared with commercial ones. The catalysts were characterized by BET surface area, pore volume and carbon monoxide chemisorption. Specific activities for the methanation reaction were obtained and were found to vary with nickel concentration and with crystallite size. There exists a crystallite size range in which the maximum activity was observed. Metal support interactions may also contribute to the vdation in specific activity. The activation energy was found to vary from 58.2 MJ/kmol to 119.4 MJ/kmol. It appears that the methanation reaction over Ni/aIumina catalysts is a structure sensitive reaction. A compensation effect was observed for this reaction.     

煤基合成气制甲烷工艺与催化剂研究进展

煤制天然气是煤炭高效清洁利用的重要途径,甲烷化是煤制天然气的关键反应,具有强放热、可逆和体积缩小的特点。针对甲烷化反应特点,工艺上主要采用多段绝热循环稀释CO含量、合成气变换与净化等策略实现高甲烷收率。对现有的传统甲烷化工艺进行归纳总结,并分析各自甲烷化工艺的特点。在此基础上,对甲烷化工艺路线进行比较,提出开发煤制天然气耐硫甲烷化新工艺,并对该工艺进行探讨。常规钼基耐硫甲烷化催化剂由于原料空速和转化率低,水热稳定性也有待提高,因而开发粗煤气多段耐硫甲烷化制天然气节能工艺及高效耐硫甲烷化催化剂是今后的研究方向。