Cu、Ni、Ru、Pt对费托合成Fe催化剂的助剂作用研究

考察了Cu、Ni、Ru、Pt对费托合成Fe催化剂的助剂作用。XRD结果表明,加入Cu、Ni助剂对催化剂有一定的分散作用,而Ru、Pt影响不大。XPS结果表明,所有添加的助剂在催化剂表面均有一定程度的富集,且4种过渡金属助剂与Fe存在不同程度的电荷相互作用。H₂-TPR表明,Cu、Pt、Ru在催化剂还原过程中首先还原为金属态,进而能够明显促进催化剂的还原。CO-TPD表明,加入Cu、Pt、Ni助剂对CO的吸附活化有明显的促进作用。用固定床反应器对催化剂的费托反应性能进行了评价,反应结果表明,加入Ru、Ni、Pt、Cu会依次提高催化剂的反应活性,Pt、Cu、Ru、Ni助剂会依次使催化剂的CH₄选择性增加,并降低C₅₊的选择性。     

Study on the Precursor Phase Composition of Fused Iron Catalyst for Fischer-Tropsch Synthesis

The effect of the precursor composition of fused iron catalyst on the performance of Fischer-Tropsch synthesis was investigated. XRD, BET and CO2 adsorption experiments were carried out to provide better insight into the relationship therein. The results showed that the selectivity of C5＋ hydrocarbon products was dependent on the mole ratio of Fe^2＋/Fe^3＋, which was represented by a hump-shaped curve. Catalysts with precursors containing Fe3O4 phase favored the magnetite spinal formation during F-T reaction, while Fe（1-x）O-based catalysts were more likely to favor the formation and growth of the iron carbide crystals.     

Zn助剂对铁基催化剂费托合成制低碳烯烃性能的影响

低碳烯烃(C2=–C4=)是十分重要的基础化工原料,目前主要采用热裂解或催化裂解石脑油、蜡油等工艺路线生产。近年来,针对全球范围的石油危机及我国富煤贫油这一基本的国情,以煤、天然气(页岩气)和生物质等丰厚的碳资源,经合成气制取低碳烯烃的工艺路线备受关注。其中,合成气经由甲醇或二甲醚间接制取烯烃技术(MTO/MTP)已经工业化;与之相比,费托合成直接生产低碳烯烃(FTO)工艺流程短、投资和操作费用低,具有良好的工业发展前景。目前,费托合成催化剂活性组分的研究主要集中于Fe, Co, Ni和Ru等元素,其中Fe基催化剂具有较高低碳烯烃选择性、较低甲烷选择性和制造廉价等优势,更适合于FTO反应。最近,人们大多聚焦于对负载型铁基催化剂的研究,但传统非负载型铁催化剂由于其制备简单、价格低廉,仍然具有巨大的开发前景。近来,我们组报道了采用微波水热法制备的Zr助剂改性Fe-Zr催化剂应用于CO加氢研究,提高了催化剂的活性,与传统Mn改性铁基催化剂相比, CO2选择性明显降低。目前,已有研究小组对Zn助剂提高铁基催化剂烯烃选择性进行报道,但反应过程中的严重积碳问题却少有研究。我们在Fe-Zr催化剂的基础上,进一步研究了Zn助剂在提高铁基催化剂低碳烯烃选择性、改善产物分布和降低反应过程积碳方面的作用。
　　我们分别采用微波水热法和浸渍法对铁基催化剂进行了Zn改性,并将其用于费托合成制取低碳烯烃反应。运用扫描电镜(SEM)、X射线衍射(XRD)、N2物理吸附(BET)、H2程序升温还原(H2-TPR)和X射线光电子能谱(XPS)技术手段对催化剂的物理和化学性质进行了表征。结果表明,两种方法改性后的铁基催化剂具有高低碳烯烃选择性和稳定性,重质烃(C5+)含量降低,且保持低CO2选择性。此外,采用两种方法Zn改性的铁基催化剂展现出了不同的特性。 XRD结果表明,反应前两种方法制备的样品α-Fe2O3物相晶粒大小均为15–18 nm,反应后浸渍法制备的样品对应物相(ZnFe2O4)晶粒大小约为25 nm、而微波水热法制备的样品约为20 nm,说明微波水热法改性的催化剂有效分散了Fe活性组分; H2-TPR结果显示,两种Zn助剂加入方法对催化剂Fe组分的还原行为有不同程度影响,体现了活性组分间不同的相互作用; XPS结果表明, Zn助剂改变了催化剂Fe活性位的化学性质,在微波水热法制得催化剂的表面Zn含量更低、分散度更高,而Zn助剂的加入对Zr组分没有明显影响。所有催化剂经200 h在线活性测试后,采用传统浸渍法制备的催化剂表面有大量积碳生成;而采用微波水热改性铁基催化剂积碳量明显减少,表现出更高的催化活性与稳定性。     

低温高活性熔铁催化剂上的超临界相费托合成反应

在固定床反应器中超临界相条件下研究了熔铁催化剂上的费托合成反应,发现在超临界介质中反应物和产物更容易扩散,较好地抑制了催化剂表面非活性碳的沉积,从而提高了费托合成反应中的CO转化率和烯烃选择性,增加了链增长因子,降低了甲烷选择性.同时,考察了超临界介质、反应温度、压力、H2/CO比和空速等条件对费托合成反应的影响.结果表明,C5-8正构烷烃在催化剂活性温度下都是适宜的超临界介质.当温度和压力都在介质的临界点以上时,介质表现出较好的传质与传热性能,可改善费托合成反应性能.     

Characterization and catalytic performance of CeO2-Co/SiO2 catalyst for Fischer-Tropsch synthesis using nitrogen-diluted synthesis gas over a laboratory scale fixed-bed reactor

The surface species of CO hydrogenation on CeO2-Co/SiO2 catalyst were investigated using the techniques of temperature programmed reaction and transient response method. The results indicated that the formation of H2O and CO2 was the competitive reaction for the surface oxygen species, CH4 was produced via the hydrogenation of carbon species step by step, and C2 products were formed by the polymerization of surface-active carbon species （-CH2-）. Hydrogen assisted the dissociation of CO. The hydrogenation of surface carbon species was the rate-limiting step in the hydrogenation of CO over CeO2-Co/SiO2 catalyst. The investigation of total pressure, gas hourly space velocity （GHSV）, and product distribution using nitrogen-rich synthesis gas as feedstock over a laboratory scale fixed-bed reactor indicated that total pressure and GHSV had a significant effect on the catalytic performance of CeO2-Co/SiO2 catalyst. The removal of heat and control of the reaction temperature were extremely critical steps, which required lower GHSV and appropriate CO conversion to avoid the deactivation of the catalyst. The feedstock of nitrogen-rich synthesis gas was favorable to increase the conversion of CO, but there was a shift of product distribution toward the light hydrocarbon. The nitrogen-rich synthesis gas was feasible for F-T synthesis for the utilization of remote natural gas.     

单相Co_2C的制备及其费-托合成催化性能研究

采用CO与金属钴在温度280℃,压力2 MPa的条件下反应48 h后制备得到单相Co_2C催化剂。通过XRD、H2-TPR、TEM和XAS对催化剂的结构和组成进行表征并考察了单相Co_2C催化剂在费-托合成反应中的稳定性与催化性能。结果表明,随着费-托合成反应的进行,Co_2C催化剂的活性缓慢上升,同时伴随着产物中甲烷的选择性逐渐降低,C5+的选择性逐渐升高。对比反应前后催化剂发现,反应后的催化剂为Co_2C和少量金属Co的混合相,表明在费-托合成反应条件下,单相Co_2C会发生部分分解,生成的金属Co会导致CO的转化率和产物的选择性发生变化。     

炭化过程对铁基费托合成催化剂强度和结构的影响

以模型费托合成Fe基催化剂为研究对象,在纯CO气氛中对催化剂进行不同时间的预处理,采用多种手段对预处理后催化剂的物理化学性质和抗磨损能力进行了表征。结果表明,在预处理初期,随着预处理时间的延长,催化剂的炭化程度显著提高,伴随着催化剂比表面积的降低和颗粒粒径的减小,而催化剂的抗磨损能力逐渐提高。当预处理时间超过72 h后,继续延长预处理时间,催化剂的炭化程度不再增加,而积炭程度逐渐增加,伴随着催化剂比表面积和颗粒粒径的增加,催化剂的质量也同时增加,并导致催化剂的抗磨损能力逐渐降低。     

Influence of lanthanum on the performance of Zr-Co/activated carbon catalysts in Fischer-Tropsch synthesis

The influence of La loading on Zr-Co/activated carbon （AC） catalysts has been studied for Fischer-Tropsch synthesis. The catalyst samples were characterized by XRD, TPR, CO-TPD, and temperature programmed CO hydrogenation. The catalytic property was evaluated in a fixed bed reactor. The experimental results showed that CO conversion increased from 86.4% to 92.3% and the selectivity to methane decreased from 14.2% to 11.5% and C5＋ selectivity increased from 71.0% to 74.7% when low La loading （La = 0.2wt%） was added into the Zr-Co/AC catalyst. However, high loadings of La （La = 0.3-1.0 wt%） would decrease catalyst activity as well as the C5＋ selectivity and increase methane selectivity. XRD results displayed that La-modified Zr-Co/AC catalyst had little effect on the dispersion of Co catalyst. But, the results of TPR, CO-TPD, and temperature programmed CO hydrogenation techniques indicated that the extent of cobalt reduction was found to greatly influence the activity and selectivity of the catalyst. The addition of a small amount of La increased the reducibility of the Zr-Co/AC catalyst and restrained the formation of methane and improved the selectivity to long chain hydrocarbons. However, excess of La led to the decrease of the reducibility of Co catalyst thus resulted in higher methanation activity.     

Fischer-Tropsch, organometallics, and other friends

Recent researches on the mechanism of the Fischer-Tropsch hydrogenation of CO heterogeneously catalyzed by ruthenium, rhodium, cobalt or iron (on silica), both with and without added probe molecules, are reviewed. When the reactions are carried out under mild conditions of temperature, pressure and catalyst, we find that, although the absolute activities of the four catalysts differ, the relative product distributions are rather similar. Our data indicate that the primary products are largely n-1-alkenes (and methane); n-alkanes and some internal olefins are also produced, but these arise substantially from subsequent (secondary) reactions of the 1-alkenes. Mechanisms for the formation of 1-alkenes are suggested, both from our work and that of other groups, based upon data from (i) a variety of labeling and spectroscopic studies, (ii) model stoichiometric reactions of organometallic complexes, and (iii) some theoretical and computational data now available. The mechanism in best agreement with experimental data involves, (a) initiation via deoxygenation of coordinated CO and the production of a C₂ based surface species, probably a vinyl {CH₂CH_(ad)}, via formation of surface carbide, methylidyne and methylene; (b) propagation by reaction of surface methylene {CH_2(ad)} with surface vinyl or alkenyl {RCHCH_(ad)} to give a surface allyl {RCHCHCH_2(ad)}, followed by a 1,3-H shift to generate a new surface alkenyl {RCH₂CHCH_(ad)}; and (c) termination by hydride-mediated cleavage of the alkenyl chain from the catalyst giving the 1-alkene, RCH₂CHCH₂, directly. By contrast, the hydrogenation of CO homogeneously catalyzed by soluble complexes(chiefly of Ru) is reported to occur only under more stringent conditions and to lead mainly to methanol and ethylene glycol; clearly quite different mechanisms operate there.     

高分散费—托合成铁／活性炭催化剂的研究：Ⅴ.锰的助剂作用

使用原位穆斯堡尔谱和微型反应器考察了物相、锰含量和制备方法对Fe-Mn/AC催化剂F-T反应性的影响,并讨论了Fe-Mn/AC催化剂的表面结构及其与F-T反应性的关系。对于Fe-Mn/AC催化剂,将铁还原到金属态时具有很高的活性和对气态烯烃和高碳烃的选择性,锰含量对催化剂的活性和选择性影响不大;影响催化剂选择性的主要是受制备制约的铁-锰在活性炭载体表面的结构形态,对此我们提出了模型,只有当铁-锰处于高分散状态,作为助剂锰才能改善催化剂对气态烯烃和高碳烃的选择性,否则锰反而起不利的作用。