共查询到19条相似文献,搜索用时 812 毫秒
1.
不同结构的芳烃对加氢裂化催化剂积炭的影响 总被引:6,自引:2,他引:6
在高压连续流动微型反应器上采用催速老化技术考察了不同结构的芳烃在加氢裂化催化剂上积炭行为,并用热分析、傅立叶变换红外和物理吸附仪等手段对积炭催化剂的积炭类型、酸强度分布和孔结构的变化进行了研究。结果发现:单环芳烃中,随着取代基的碳链长度、数目及不饱和度的增加,催化剂更容易积炭。稠环芳烃的环数越多,反应生成的总积炭和假石墨型积炭越多。积炭越多的催化剂,比表面积降低越多。积炭主要沉积在催化剂的小孔内或堵塞小孔孔口,有些积炭在催化剂表面形成机械孔。积炭后,催化剂上不同强度的酸数目均较新鲜催化剂降低,尤其是萘和菲,使强酸严重削弱。 相似文献
2.
研究了邻苯二酚与乙醇气固相单醚化反应用固体酸催化剂表面上的积炭行为,并用TG-DTA,BET,GC-MS,FT-IR和元素分析等手段对积炭物种进行了表征.结果表明,催化剂上有两种类型的积炭,一类属可溶性积炭,主要由二苯醚及其衍生物组成,可在低温燃烧除去;另一类属不可溶性积炭,主要为缺氢的芳烃类聚合物或类石墨碳,需在高温下才能烧除.积炭主要发生在4~8nm范围的中孔内,导致反应后的催化剂大孔范围的孔分布所占的分数增大.随着反应的进行,总积炭量逐渐增多. 相似文献
3.
HZSM-5分子筛催化剂在催化苯氧化合成苯酚反应中的积炭和失活行为 总被引:1,自引:0,他引:1
在固定床反应器中进行了HZSM-5分子筛催化剂催化苯氧化生成苯酚时的积炭和失活实验,催化剂经高温水蒸气处理,反应条件为: 9.7%N2O-90.3%N2混合气流速115 ml/min,苯流速6 g/h,反应温度400 ℃. 采用TG,吸附吡啶的IR谱,13C NMR和低温N2吸附法对催化剂进行了表征,并用连续流动吸附法测定催化剂上正己烷和环己烷的吸附量. 结果表明,苯氧化生成苯酚的反应过程中,催化剂表面积炭导致分子筛微孔孔口堵塞是造成催化剂失活的主要原因. 与其他有机物在ZSM-5上的积炭相似,B酸中心是积炭的活性中心. 积炭物种主要为带有烷基的芳烃和多环芳烃,同时含有少量带有羟基的多环芳烃,这可能是由在L酸中心上生成的苯酚进一步氧化、脱氢和聚合形成的. 相似文献
4.
Mo/HZSM-5催化剂上甲烷无氧芳构化反应中积炭的研究 总被引:2,自引:0,他引:2
对经过程序升温表面甲烷无氧芳构化反应后的Mo/HZSM-5催化剂上的积炭进行程序升温加氢反应和程序升温二氧化碳反应,并对相应的催化剂上的积炭进行程序升温氧化反应和热重实验,以研究催化剂上的不同积炭物种.结果表明,甲烷无氧芳构化反应后有两类烧炭峰,一类是低温烧炭峰,另一类是高温烧炭峰;H2主要对高温烧炭峰发生作用,对低温烧炭峰几乎没有影响;CO2可同时对两种烧炭峰产生影响.由此推论,甲烷在无氧条件下直接转化生成芳烃的反应过程中,沉积在Mo/HZSM-5催化剂上的积炭有三种形式,即:能够与H2反应的积炭,能够与CO2反应的积炭和可能以Mo2C形式存在的物种. 相似文献
5.
不同条件下苯与丙烯烷基化反应的催化剂失活研究 总被引:1,自引:0,他引:1
对不同条件下苯与丙烯烷基化反应Hβ催化剂的寿命、失活催化剂的积炭量和积炭性质进行了研究。在5.7MPa下,随反应温度变化,反应介质在反应过程中所经历的相态变化不同,导致催化剂的寿命、失活催化剂的积炭量和积炭的性质也存在着较大差异。300℃时,反应介质处于接近于体系临界点的超临界相或高压液相状态,催化剂寿命最长,积炭量大。失活催化剂积炭的元素分析及TPO-MS表征结果发现,积炭的碳氢比与反应温度有关,温度越高,碳氢比越高;而积炭的脱炭温度与反应时间(催化剂寿命)相关,催化剂寿命越长,相应的脱炭温度也越高。 相似文献
6.
编辑同志: K_2O是氨合成催化剂的重要助剂,它在催化剂中的形态一直是人们注意的问题.文献[1,2]指出,催化剂中的K分为可溶性和不可溶性的两种;文献[3]又明确指出了K_2O,,KAlO_2和KFeO_2等是可溶性钾盐.贵刊在1983年第4卷第3期刊登的“球形氨合成催化剂中钾的溶出规律”一文中用化学分析的方法证明铁酸钾是不可溶性钾盐,该文所引用的资料也明确地说铁酸钾是不可溶性的,但他们都没有提出不可溶性的直接证据.因此,我们认为铁酸钾究竟是可溶性的还是非可溶性的值得进一步说明. 根据一般化学分析的碱熔法的实践,我们认为铁酸钾应该是可溶性钾盐.但为了说明问题,我们用 相似文献
7.
应用C_2H_4-H_2滴定方法考察了Pt/Al_2O_3和PtSn/A1_2O_3催化剂经过n-C_4H_(10)积炭反应及氧烧炭循环后催化剂金属中心的变化。发现随循环次数增加,Sn对Pt表面的分割作用减弱,催化剂单铂中心减少而多铂中心增加。积炭催化剂的程序升温表面反应进一步揭示了多次循环后PtSn/Al_2O_3催化剂上烃分子脱氢深度增加,表面含炭物加氢活性减弱。表明经过循环积炭-烧炭处理的双金属PtSn催化剂一定程度地表现出Pt/Al_2O_3催化剂的性质。 相似文献
8.
9.
合成了ZSM-5、ZSM-22、EU-1、MCM-22和ITQ-13具有十元环孔道结构的5种分子筛,研究了分子筛结构、酸性分布等因素对其在甲醇芳构化反应中催化性能的影响。研究表明,不同结构分子筛的形貌、酸性及孔径均存在较大差异,进而影响了其在甲醇制芳烃反应中的催化活性和稳定性。研究的5种分子筛中,ZSM-5表现出最佳的芳构化活性,芳烃收率达34.8%,MCM-22芳烃收率约为21.9%,而其他3种结构的分子筛催化剂基本未表现出甲醇芳构化活性。通过添加具有芳构化性能的Ga物种对ZSM-5和MCM-22进行改性,可显著提升芳烃收率,Ga/ZSM-5上芳烃收率达到40.8%,Ga/MCM-22上芳烃收率可提高到27.1%。另外,采用TG/DTA、GC等方法研究了失活催化剂的积炭情况,发现分子筛结构对积炭量、积炭组成及积炭分布存在显著影响。 相似文献
10.
甲烷在Co-Mo/HZSM-5催化剂上进行无氧芳构化反应的评价结果表明,Co的添加大大提高了Mo/HZSM-5催化剂在反应过程中的稳定性.BET实验证明,反应后的积炭对Co-Mo/HZSM-5催化剂孔道堵塞的程度较小.对积炭催化剂进行的一系列程序升温表面反应(如TPH,TPCO2和TPO)结果表明,TPO谱上有两个峰温明显不同的烧炭峰,Co的添加明显抑制了高温积炭的生成.H2主要与高温积炭发生反应,这部分积炭是催化剂失活的主要原因;CO2对低温积炭的影响则尤为明显.TEM结果表明,积炭催化剂上存在丝状积炭物种.碳丝不能与H2反应,但能被CO2除去.Co的添加促进了丝状积炭物种的生成,碳丝并不是导致催化剂失活的因素. 相似文献
11.
12.
本文综述了甲烷无氧芳构化反应及Mo基分子筛催化剂的研究进展。在众多的催化剂中以Mo基分子筛催化性能最佳。概括了催化剂中关于MoO<em>x前躯体结构和其在分子筛中落位,Mo2C物种和诱导期等;讨论了反应中涉及的中间产物、双功能机理以及催化剂失活等问题;归纳了催化剂制备过程中制备方法、焙烧温度与时间、Mo载量和分子筛硅铝比以及催化剂预处理对反应活性的影响;综述了提高催化剂催化性能和反应性能的各种方法,并对其分析,同时介绍了两种催化剂再生方法。最后,依据本实验室研究进展,对甲烷芳构化从工艺角度进行一些可行性讨论,并提出相关问题和展望。 相似文献
13.
Coking, deactivation, and regeneration of 5A zeolite during 1-hexene adsorption were studied on a fixed-bed adsorber and a themogravimetric analyzer. Adsorption activity measurement, scanning electron microscope (SEM) analysis, X-ray diffraction (XRD) analysis, FT-IR analysis, 1H NMR analysis, and porosity measurement were used to reveal the mechanism of coking and deactivation of 5A zeolite, and evaluate the influences of binder on them. There are distinct increases in both coke content and deactivation degree with increasing the adsorption temperature. Deactivation degrees of zeolite increase as coke contents rise, however, they display smaller increasing rate at higher coke content. The rates of coke formation and deactivation of 5A zeolite are significantly enhanced by the binder mainly due to the fact that the activity sites offered by the amorphous compounds contained in the binder catalyze the formation of coke precursors. As compared to the coke formed in zeolite with binder, the coke in binderless zeolite is more aromatic. The coke which consists of inflammable part and nonflammable part can be oxidatively removed completely while the temperature approaches 787 K. No destruction in 5A zeolite crystal structure was observed in the regenerated binderless sample. The formation of coke during 1-hexene adsorption on zeolite can be explained using the carbonization-cyclization reaction mechanism. Furthermore, the kinetics models for formation and removal of coke were developed. 相似文献
14.
Bonan Liu Liam France Chen Wu Zheng Jiang Vladimir L. Kuznetsov Hamid A. Al-Megren Mohammed Al-Kinany Saud A. Aldrees Tiancun Xiao Peter P. Edwards 《Chemical science》2015,6(9):5152-5163
A series of MoO3/H-ZSM-5 (Si/Al = 25) catalysts were prepared via calcination at a lower-than-usual temperature (400 °C) and subsequently evaluated in the methanol-to-hydrocarbon reaction at that same temperature. The catalytic properties of those catalysts were compared with the sample prepared at the more conventional, higher temperature of 500 °C. For the lower temperature preparations, molybdenum oxide was preferentially dispersed over the zeolite external surface, while only the higher loading level of MoO3 (7.5 wt% or higher) led to observable inner migration of the Mo species into the zeolite channels, with concomitant partial loss of the zeolite Brønsted acidity. On the MoO3 modified samples, the early-period gas yield, especially for valuable propylene and C4 products, was noticeably accelerated, and is gradually converted into an enhanced liquid aromatic formation. The 7.5 wt% MoO3/H-ZSM-5 sample prepared at 400 °C thereby achieved a balance between the zeolite surface dispersion of Mo species, their inner channel migration and the corresponding effect on the intrinsic Brønsted acidity of the acidic zeolite. That loading level also possessed the highest product selectivity (after 5 h reaction) to benzene, toluene and xylenes, as well as higher early-time valuable gas product yields in time-on-stream experiments. However, MoO3 loading levels of 7.5 wt% and above also resulted in earlier catalyst deactivation by enhanced coke accumulation at, or near, the zeolite channel openings. Our research illustrates that the careful adoption of moderate/lower temperature dispersion processes for zeolite catalyst modification gives considerable potential for tailoring and optimizing the system''s catalytic performance. 相似文献
15.
16.
Co改性Mo/MCM-22催化剂上甲烷无氧芳构化及积炭研究 总被引:2,自引:0,他引:2
研究了Co的添加对Mo/MCM-22催化剂甲烷无氧芳构化反应性能的影响.发现用共浸渍法制备的Co/Mo摩尔比为0.2的催化剂具有较高的活性,而先浸渍Mo后浸渍Co的催化剂具有较好的稳定性.XRD实验表明,Co及Mo的氧化物均高度分散在分子筛表面,其担载降低了分子筛的衍射强度.不同接触时间下催化剂的反应结果表明,接触时间长,积炭选择性随接触时间增加而迅速增加;接触时间短,积炭选择性随接触时间增加而减少.积炭催化剂的TG研究表明,催化剂上的积炭主要有两种形式.低温积炭随反应时间增加而迅速增多,高温积炭的变化则较为缓慢.低温积炭可能是导致催化剂活化和失活的主要原因.高温积炭可能是一种大分子量的碳氢物种,位于MCM-22分子筛的“超笼”中,表明MCM-22有较大的容积炭能力. 相似文献
17.
Nikolay Kosinov Evgeny A. Uslamin Lingqian Meng Alexander Parastaev Yujie Liu Emiel J. M. Hensen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(21):7142-7146
Non‐oxidative dehydroaromatization of methane over Mo/ZSM‐5 zeolite catalysts is a promising reaction for the direct conversion of abundant natural gas into liquid aromatics. Rapid coking deactivation hinders the practical implementation of this technology. Herein, we show that catalyst productivity can be improved by nearly an order of magnitude by raising the reaction pressure to 15 bar. The beneficial effect of pressure was found for different Mo/ZSM‐5 catalysts and a wide range of reaction temperatures and space velocities. High‐pressure operando X‐ray absorption spectroscopy demonstrated that the structure of the active Mo‐phase was not affected by operation at elevated pressure. Isotope labeling experiments, supported by mass‐spectrometry and 13C nuclear magnetic resonance spectroscopy, indicated the reversible nature of coke formation. The improved performance can be attributed to faster coke hydrogenation at increased pressure, overall resulting in a lower coke selectivity and better utilization of the zeolite micropore space. 相似文献
18.
Mohamed Mokhtar Mohamed 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):301-313
The transformation of ethanol on Fe ion-exchanged mordenite was compared in the temperature range of 200–400 °C for samples prepared in the solution and solid states. Ethane and methane were found as rather major products, compared to acetaldehyde and acetone. Diethyl ether was also detected as a dehydration product. The conversion was found to increase monotonically (to 96%) with increasing the Fe content (to 100%) and reaction temperature to 400 °C. The selectivity towards acetaldehyde and acetone was found maximum at the temperature 300 °C. Decrease in the catalyst Brönsted acidity due to ion-exchange in solution caused a marked increase in the selectivity toward acetaldehyde at 300 °C. At variance, Fe ion-exchanged in the solid state resulted in a higher Brönsted acidity catalyst of higher selectivity to acetone. The solid state exchanged catalyst formed more coke at 400 °C. The higher zeolite acidity catalyzes the ethane propagation into the coke precursors. The extraordinary formation of ethane as a dominant transformation product (in the absence of H2 gas supply) is explained mainly to the O-abstracting affinity of the Fe3+ ion. Methane may be formed as a result of decomposition reaction at high temperatures. Mössbauer and XRD were applied for characterizing different Fe species involved as active sites in the reaction. Coke deposited on the catalysts was measured by TGA. Other helpful information was obtained from BET of N2-adsorption and FT–IR of NH3-adsorption. Fair correlation between the active sites responsible for formation of the various products and the zeolite acidity is discussed along with a possible role for the surface area and pore structure in the reaction activity and selectivity. 相似文献
19.
Nora Comelli Liliana Grzona Omar Masini Esther N. Ponzi Marta I. Ponzi 《Reaction Kinetics and Catalysis Letters》2000,71(1):27-32
This works studies the deactivation of zirconium oxide, promoted by iron and manganese catalysts (SZFM), during the -pinene isomerization. Experiments were done in liquid phase by using a batch reactor, and the solid crystalline structure was studied by XRD while the acidity by FTIR. The deactivated catalyst exhibited coke deposits and lost its Brönsted acidity, though it still kept its crystalline structure. The nature of the coke deposit formed was analyzed by infrared spectroscopy (FTIR) as well as by Temperature Programmed Oxidation (TPO). Regeneration was done in air flow, where the temperature required to restore Brönsted acidity and to totally eliminate the coke deposits was of about 873 K. 相似文献