Olefin production by cofeeding methanol and n‐butane: Kinetic modeling considering the deactivation of HZSM‐5 zeolite

The joint transformation of methanol and n‐butane fed into a fixed‐bed reactor on a HZSM‐5 zeolite catalyst has been studied under energy neutral conditions (methanol/n‐butane molar ratio of 3/1). The kinetic scheme of lumps proposed integrates the reaction steps corresponding to the individual reactions (cracking of n‐butane and MTO process at high‐temperature) and takes into account the synergies between the steps of both reactions. The deactivation by coke deposition has been quantified by an expression dependent on the concentration of the components in the reaction medium, which is evidence that oxygenates are the main coke precursors. The concentration of the components in the reaction medium (methanol, dimethyl ether, n‐butane, C₂? C₄ paraffins, C₂? C₄ olefins, C₅? C₁₀ lump, and methane) is satisfactorily calculated in a wide range of conditions (between 400 and 550°C, up to 9.5 (g of catalyst) h (mol CH₂)^?1 and with a time on stream of 5 h) by combining the equation of deactivation with the kinetic model of the main integrated process. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Study of operating variables in the transformation of aqueous ethanol into hydrocarbons on an HZSM‐5 zeolite

With the aim of determining the possibilities of directly upgrading the liquid obtained from carbohydrate fermentation, the effect of operating conditions (temperature, space time, water content in the feed) has been studied in the catalytic transformation of aqueous ethanol into hydrocarbons on an HZSM‐5 zeolite in an isothermal fixed bed reactor. Special attention has been paid to the effect of water content on the yield, product distribution and catalyst deactivation. Although deactivation by coke decreases as the water content is increased, this content must be limited at 450 °C and higher temperatures in order to avoid irreversible deactivation of the catalyst by dealumination. © 2002 Society of Chemical Industry     

Conversion of isopropanol and mixed alcohols to hydrocarbons using HZSM‐5 Catalyst in the MixAlco™ process

HZSM‐5 (SiO₂/Al₂O₃=280 mol/mol) is used to produce hydrocarbons from reagent‐grade isopropanol and mixed alcohols made from lignocellulosic biomass (waste office paper and chicken manure) using the MixAlco? process. All studies were performed at 101 kPa (abs). The experiments were conducted in two sets: (1) vary temperature (300–T_max°C) at weight hourly space velocity (WHSV)=1.31 h^–1, and (2) vary WHSV (0.5–11.5 h^–1) at T=370°C. For isopropanol, T_max=450°C and for mixed alcohols T_max=520°C. For isopropanol, higher temperatures produced more gaseous products and more aromatics. High WHSV gives high concentration of C6+ olefins, whereas low WHSV gives high concentrations of C9 aromatics. For mixed alcohols, changes in temperature affected the product distribution similar to isopropanol. In contrast, WHSV did not affect the concentration of reaction products; only dehydration products were observed. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2549–2557, 2013     

HZSM-5分子筛催化甲醇制低碳烯烃性能的研究进展

综述了改性HZSM-5用于甲醇制取低碳烯烃的研究进展。主要从硅铝比、化学改性、品粒尺寸、引入介孔和高温水热处理五个改性手段对HZSM-5用于MTP反应的影响进行了调研。适量的B酸量是改性HZSM-5用于甲醇制烯烃反应时烯烃选择性的最关键影响因素,适当的孔道修饰能够提高HZSM-5的烯烃选择性。     

Preparation and Performances of Hierarchical Structured HZSM‐5 Washcoating on Stainless‐Steel Substrates

The washcoats of the hierarchical HZSM‐5 zeolite (through desilication) were prepared on the inner surface of SS304 stainless‐steel tubes. The properties of slurries and coatings were characterized by analysis of particle size, measurements of rheological property, loading, adhesion, and finally the catalytic cracking test. It was found that introducing mesoporosity on the zeolite crystals was beneficial for reducing the particle size during ball milling for slurries preparation, which was helpful for improving loading due to a significant change in the rheological property. As the interaction between the particles with different sizes was enhanced after ball milling, the adhesion of the prepared coatings was improved. The catalytic activity and stability of the hierarchical HZSM‐5 coatings for the catalytic cracking of n‐dodecane were 56% and 75% higher than that of the conventional one, respectively. This probably resulted from the enhanced diffusion rate of reactant and products in the crystals and the coatings.     

Chemical kinetic modeling of i‐butane and n‐butane catalytic cracking reactions over HZSM‐5 zeolite

A chemical kinetic model for i‐butane and n‐butane catalytic cracking over synthesized HZSM‐5 zeolite, with SiO₂/Al₂O₃ = 484, and in a plug flow reactor under various operating conditions, has been developed. To estimate the kinetic parameters of catalytic cracking reactions of i‐butane and n‐butane, a lump kinetic model consisting of six reaction steps and five lumped components is proposed. This kinetic model is based on mechanistic aspects of catalytic cracking of paraffins into olefins. Furthermore, our model takes into account the effects of both protolytic and bimolecular mechanisms. The Levenberg–Marquardt algorithm was used to estimate kinetic parameters. Results from statistical F‐tests indicate that the kinetic models and the proposed model predictions are in satisfactory agreement with the experimental data obtained for both paraffin reactants. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2456–2465, 2012     

Undesired components in the transformation of biomass pyrolysis oil into hydrocarbons on an HZSM‐5 zeolite catalyst

The results of the catalytic transformation on HZSM‐5 zeolite of mixtures of components of biomass pyrolysis oil in the 673–723 K temperature range are evidence of the need for previously separating certain components (aldehydes, oxyphenols and furfural) that undergo severe thermal degradation by forming carbonaceous deposits at the reactor inlet ducts and on the catalyst itself. The deactivation of the catalyst is a consequence of the deposition of two different types of coke: one of catalytic origin (similar to that generated in the transformation of methanol and bioethanol) and the other of thermal origin, which is produced by the aforementioned degradation. The remaining oxygenate components react to each other with synergistic effect, which means that their reactivity is higher than that of the pure components. The results show that the aqueous fraction of biomass pyrolysis oil may be transformed into hydrocarbons on acid catalysts similarly to the more familiar transformation of methanol and bioethanol. Copyright © 2005 Society of Chemical Industry     

Conversion of isopropanol and mixed alcohols to hydrocarbons using HZSM‐5 catalyst in the MixAlco™ process. Part 2: Studies at 5000 kPa (abs)

This study employed HZSM‐5 (SiO₂/Al₂O₃ = 280 mol/mol) to produce hydrocarbons from reagent‐grade isopropanol and mixed alcohols made from lignocellulosic biomass (waste office paper and chicken manure) using the MixAlco? process. All studies were performed at P = 5000 kPa (abs). The experiments were conducted in two sets: (1) vary temperature (300–450°C) at weight hourly space velocity (WHSV) = 1.92 h^?1, and (2) vary WHSV (1.92–11.52 h^?1) at T = 370°C. For isopropanol at higher temperatures, the olefins undergo more cracking reactions to produce smaller molecules and more aromatics. At low temperatures, the molecules have less energy so they do not crack and therefore form larger molecules. At T = 300°C, the carbon distribution is bimodal at C9 and C12, which shows trimerization and tetramerization of propene. At 300°C, propene was the only gas produced, cracking did not occur and therefore preserved high‐molecular‐weight molecules. For mixed alcohols, higher temperatures show significant catalyst deactivation; however, isopropanol did not show any catalyst deactivation. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1707–1715, 2016     

Deactivation kinetics of a HZSM‐5 zeolite catalyst treated with alkali for the transformation of bio‐ethanol into hydrocarbons

The kinetics of deactivation by coke of a HZSM‐5 zeolite catalyst in the transformation of bioethanol into hydrocarbons has been studied. To attenuate deactivation, the following treatments have been carried out: (i) the zeolite has been subjected to a treatment with alkali to reduce the acid strength of the sites and (ii) it has subsequently been agglomerated into a macro and meso‐porous matrix of bentonite and alumina. The experimental study has been conducted in a fixed bed reactor under the following conditions: temperature, between 300 and 400°C; pressure, 1 atm; space‐time, up to 1.53 (g of catalyst) h (g of ethanol)^?1; particle size of the catalyst, between 0.3 and 0.6 mm; feed flowrate, 0.16 cm³ min^?1 of ethanol+water and 30 cm³ (NC) min^?1 of N₂; water content in the feed, up to 75 wt %; time on stream, up to 31 h. The expression for deactivation kinetics is dependent on the concentration of hydrocarbons and water in the reaction medium (which attenuates the deactivation) and, together with the kinetics at zero time on stream, allows the calculation of the evolution with time on stream of the yields and distribution of products (ethylene, propylene and butenes, C₁‐C₃ paraffins, and C₄‐C₁₂). By increasing the temperature in the 300–400°C range the role of ethylene on coke deposition is more significant than that of the other hydrocarbons (propylene, butenes and C₄‐C₁₂), which contribute to a greater extent to the formation of coke at 300°C. © 2011 American Institute of Chemical Engineers AIChE J, 58: 526–537, 2012.     

粘结助剂对ZSM-5甲醇制烯烃催化活性的影响

采用机械混合法在H-ZSM-5分子筛中添加不同氧化物粘结剂,考察其对甲醇制烯烃(MTO)催化反应性能的影响,并采用x射线衍射(XRD)、氨气-程序升温脱附(NH3-TPD)实验、傅立叶红外光谱(FT-IR)和热重(TG)分析表征催化剂结构.结果表明:在H-ZSM-5中分别添加不同的氧化物粘结剂SiO2,γ-Al2O3和Kaolin(H-ZSM-5和氧化物质量比2∶1),在催化剂1 g,CH3OH与N2物质的量之比1∶4,催化剂质量与原料流速之比(W/F)为10(g·h)/mol,反应压力0.1 MPa和反应温度723 K的条件下,反应3 h,甲醇转化率为100%;与H-ZSM-5相比,烯烃产物分布发生了变化,添加SiO2使C3=选择性下降,添加γ-Al2O3使C1选择性增加,添加Kaolin使C3=选择性增加,同时添加Kaolin与SiO2(Kaolin和siO2质量比2∶1)的H-ZsM-5具有最高的C2=～C4=选择性,其中C3=选择性为38%.添加氧化物降低了催化剂的总酸量,反应11 h前后催化剂的物相没有发生明显变化,积炭不明显.     

Mesoporous H‐ZSM‐5 for the Conversion of Dimethyl Ether to Hydrocarbons

The potential of hierarchical H‐ZSM‐5 zeolites was studied for the conversion of DME to fuel‐compatible hydrocarbons. For this purpose, hierarchical H‐ZSM‐5 zeolites have been prepared from commercial H‐ZSM‐5 by desilication and organosilane‐directed hydrothermal synthesis. The zeolites were characterized by X‐ray diffraction, NH₃‐TPD, DRIFTS, and N₂ physisorption measurements. The catalysts have been tested in a tube reactor (1 bar, 648 K). The results indicate important structural changes in framework and acidic sites, which are significant for the synthesis of gasoline‐range hydrocarbons.     

ZSM-5硅铝比对甲醇制丙烯反应产物的影响

采用红外光谱、X射线衍射、扫描电子显微镜、电感耦合等离子体焰炬(ICP)元素分析、氮低温吸附和吡啶红外等表征手段对合成的不同硅铝比ZSM-5催化剂进行了表征,并在微分反应器中考察了沸石硅铝比对甲醇制丙烯反应中丙烯收率和丙烯-乙烯质量比(P/E)的影响.结果表明,随着硅铝比增加,丙烯收率先升后降而乙烯收率则持续下降.机理分析表明,丙烯的稳定性低于乙烯是导致产物丙烯收率随催化剂酸性降低先升后降而乙烯收率连续下降的原因,是影响P/E比的关键因素.硅铝比为120的ZSM-5催化剂具有质量分率34.3%的丙烯收率,丙烯-乙烯质量比达到4.1,若要进一步提高丙烯收率和P/E比,需从其他方面(如扩散性能改善)对催化剂进行改性.     

Deoxygenation of Methanol over ZSM‐5 in a High‐Pressure Catalytic Pyroprobe

Deoxygenation is a critical step in making hydrocarbon‐rich biofuels from biomass constituents. Although the thermal effects of oxygenate aromatization have been widely reported, the effect of pressure on this critical reaction has not yet been closely investigated, one primary reason being the unavailability of a reactor that can pyrolyze oxygenates, especially those in solid form, under pressurized conditions. Here, the first of a series of studies on how oxygenates behave when catalytically pyrolyzed under elevated pressure and temperature conditions is reported. Methanol, the simplest alcohol, was selected as the candidate to study the chemical phenomena that occur under pressurized catalytic pyrolysis. The reactions were carried out over the shape‐selective catalyst ZSM‐5 (SiO₂/Al₂O₃ = 30) under varying pressure (0 to 2.0684 MPa (300 psi) in 0.3447 MPa (50 psi) increments) and temperature (500 to 800 °C in 50 °C increments) conditions. Benzene, toluene, ethyl benzene, and xylenes (BTEX) were analyzed as the deoxygenated products of the reaction. The results indicate that the reactor pressure significantly affects deoxygenated product composition.     

HZSM-5催化剂上甲醇制丙烯反应条件的研究

以HZSM-5分子筛为催化剂,在固定床反应器中考察了反应温度和原料空速对甲醇制丙烯性能的影响。结果表明,随着反应温度的升高,乙烯和丙烯选择性均增加,但温度过高容易引起催化剂的失活;而随原料空速的增大,甲醇转化率、乙烯和丙烯的选择性均呈下降趋势。最佳的反应条件为反应温度为460°C,原料液时空速为1.4 kg(Methanol)/kg(cat.).h。对添加粘结剂与未添加粘结剂成型后的催化剂性能比较,表明添加粘结剂成型后,甲醇转化率和丙烯选择性有所下降。     

液相合成甲醇催化剂活性的研究

The effects of reduction procedure, reaction temperature and composition of feed gas on the activity of a CuO-ZnO-Al2O3 catalyst for liquid phase methanol synthesis were studied. An optimized procedure different from conventional ones was developed to obtain higher activity and better stability of the catalyst. Both CO and CO2 in the feed gas were found to be necessary to maintain the activity of catalyst in the synthesis process. Reaction temperature was limited up to 523K, otherwise the catalyst will be deactivated rapidly. Experimental results show that the catalyst deactivation is caused by sintering and fouling, and the effects of CO and CO2 on the catalyst activity are also investigated. The experimental results indicate that the formation of water in the methanol synthesis is negligible when the feed gas contains both CO and CO2. The mechanism for liquid-phase methanol synthesis was discussed and it differed slightly from that for gas-phase synthesis.     

HZSM-5催化甲醇制丙烯工艺条件的考察

以工业应用的HZSM-5为催化剂,在连续固定床反应器中考察了反应温度和甲醇分压对甲醇制丙烯反应产物的影响,发现当温度大于450℃时,随着温度的升高,甲醇的转化率都能达到99%以上,乙烯和丙烯的总选择性增加,低碳烷烃选择性增加,高碳产物选择性下降;随着甲醇分压降低,甲醇转化率下降,产物丙烯/乙烯质量比(P/E比)增加,丙烯在甲醇分压为33 kPa时达到最高值,而当分压极低时,催化剂快速失活。从转化率、丙烯选择性、P/E比以及低碳烯烃产物选择性等多方面综合考虑,甲醇转化制丙烯的反应温度优选470℃,并建议甲醇分压为33 kPa。     

活性炭载体对甲醇氧化羰化合成碳酸二甲酯催化活性的影响

:采用气相直接法甲醇氧化羰化工艺路线合成碳酸二甲酯 ,以 Cu Cl2 为活性组分 ,用浸渍法制备催化剂。关联了两种煤质活性炭作为载体时孔结构与活性的关系 ,并考察了不同表面处理或表面改性方法对催化活性的影响。