HZSM-5 zeolites undergoing the high-temperature process for boosting the bimolecular reaction in n-heptane catalytic cracking

High-temperature treatment is key to the preparation of zeolite catalysts.Herein,the effects of hightemperature treatment on the property and performance of HZSM-5 zeolites were studied in this work.X-Ray diffraction,N2physisorption,27Al magic angle spinning nuclear magnetic resonance(MAS NMR),and temperature-programmed desorption of ammonia results indicated that the hightemperature treatment at 650℃ hardly affected the inherent crystal and texture of HZSM-5zeolites but facilitated the conversion of framework Al to extra-framework Al,reducing the acid site and enhancing the acid strength.Moreover,the high-temperature treatment improved the performance of HZSM-5 zeolites in n-heptane catalytic cracking,promoting the conversion and light olefins yield while inhibiting coke formation.Based on the kinetic and mechanism analysis,the improvement of HZSM-5 performance caused by high-temperature treatment has been attributed to the formation of extra-framework Al,which enhanced the acid strength,facilitated the bimolecular reaction,and promoted the entropy change to overcome a higher energy barrier in n-heptane catalytic cracking.

Experiment and modeling of coke formation and catalyst deactivation in n-heptane catalytic cracking over HZSM-5 zeolites

Since paraffins catalytic cracking was of significant importance to light olefins and aromatics production,this work was intended to gain insights into the feature and model of coke formation and catalyst deactivation in n-heptane catalytic cracking over HZSM-5 zeolites. 18 tests of n-heptane catalytic cracking were designed and carried out over HZSM-5 zeolites in a wide range of operating conditions. A particular attention was paid to the measurement of the conversion, product distribution, coke content, and the porosity and acidity of the fresh and spent HZSM-5 zeolites. It was found that alkene and aromatic promoted coke formation, and it reduced the pore volume and acid site of HZSM-5 zeolites, tailoring its performance in n-heptane catalytic cracking. The specific relationship between HZSM-5 zeolites, n-heptane conversion, product distribution and coke formation was quantitively characterized by the exponential and linear function. Based on the reaction network, the coupled scheme of coke formation and catalyst deactivation were specified for n-heptane catalytic cracking. The dual-model was proposed for the process simulation of n-heptane catalytic cracking over HZSM-5 zeolites. It predicted not only the conversion and product distribution but also coke content with the acceptable errors.

果糖酸处理HZSM-5己烯芳构化催化剂的结构及性能

为提高HZSM-5己烯芳构化催化剂的BTX(苯、甲苯、二甲苯)选择性和寿命,利用果糖酸对HZSM-5进行处理(F-HZS),并与磷酸和硝酸处理的HZSM-5(P-HZS和N-HZS)进行对比,采用XRD、XRF、N_(2)吸附-脱附、NH_(3)-TPD、Py-FTIR等方法对催化剂结构进行表征,考察了催化剂己烯芳构化的催化性能。实验结果表明,酸处理后催化剂的MFI结构保留完整,且出现了介孔结构。催化剂的孔体积、硅铝比及B酸量和L酸量比值(B/L)增加,但酸量及酸强度下降,F-HZS的B/L最高,BTX选择性和寿命也明显高于P-HZS和N-HZS。在0.2 MPa、405℃,质量空速2 h-1条件下,F-HZS的BTX选择性为61.34%,寿命为60 h。

Ce改性HZSM-5分子筛催化甲醇与丁烯耦合转化制丙烯性能研究

为了进一步提高HZSM-5分子筛在甲醇与丁烯耦合转化制丙烯反应中的催化性能,采用浸渍法对HZSM-5分子筛进行Ce改性,得到了一系列具有不同Ce负载量的x Ce/HZSM-5催化剂。考察了Ce负载量和反应条件(甲醇与丁烯物质的量之比、反应温度和空时)对催化性能的影响,并结合催化剂表征结果,分析了Ce改性对催化性能和物化性质的影响,探讨了x Ce/HZSM-5催化剂的构效关系。结果表明,在温度550℃、压力0.1 MPa、甲醇与丁烯物质的量之比0.8、空时2.3(g cat·h)mol CH_(2)的最佳反应条件下,Ce负载量(w)为2.5%的2.5Ce HZSM-5催化剂具有最高的丙烯收率,为41.9%。Ce与HZSM-5分子筛上羟基官能团(OH)发生相互作用,降低了B酸酸量,同时生成新的L酸中心Ce(OH)^(2+),调变了催化剂表面酸中心密度和酸类型分布,提高了丙烯选择性和收率。

HZSM-5 的低温水热改性及其己烯芳构化性能

对HZSM-5在70,100和150℃下进行低温水热改性,分别制得催化剂T 70-HZ-5,T 100-HZ-5和T 150-HZ-5,利用X射线衍射仪、X射线荧光光谱仪、物理吸附仪、化学吸附分析仪和红外光谱仪等对上述催化剂进行表征,并对其己烯芳构化催化性能进行了评价。结果表明:低温水热改性保持了HZSM-5的完整晶相结构,提高了其硅铝比[n(Si)/n(Al)],B酸和L酸酸量比(B/L)及平均孔径;酸量的降低和孔径的增大有利于HZSM-5寿命的延长,B/L值的增大有利于选择性的提高;在反应温度405℃,反应压力0.2 MPa,质量空速2 h-1的条件下,T 100-HZ-5的催化寿命可达44 h,比改性前延长了36 h;当反应8 h时,HZSM-5的苯、甲苯和二甲苯混合物(BTX)选择性已迅速降到35%左右,而T 100-HZ-5的仍接近55%。

Ni-MgO复合改性对HZSM-5分子筛催化性能的影响

采用等体积浸渍法制备了Ni和MgO改性的HZSM-5催化剂,考察Ni和MgO含量对甲醇制备丙烯的影响,并利用XRD、SEM、BET、NH 3-TPD等方法考察了Ni和MgO对HZSM-5分子筛的酸强度和结构的影响,结果表明,少量的Ni-Mg复合改性的HZSM-5分子筛MFI结构没有改变,但有效改变了催化剂的酸强度和孔径结构,显著降低催化剂中强酸含量,微孔孔径由0.5105 nm降为0.5016 nm,0.5%Ni-0.5%Mg/HZSM-5分子筛表现出较佳的丙烯选择性,丙烯的选择性提高了11.5%。

花生秸秆热解挥发分在HZSM-5负载Ga催化剂上的裂解特性

生物质热解能够将木质纤维素类生物质转化为生物油,但粗油含氧量高、热值低。利用负载Ga的HZSM-5催化剂对生物质热解挥发分进行催化裂解,可以促进生物油的选择性脱氧和芳构化,实现生物油提质。分别采用离子交换法和水热法制备了两种负载Ga的HZSM-5催化剂(Ga-H5-E和Ga-H5-H),采用两段式固定床反应器进行了花生秸秆热解在线联合热解挥发分催化裂解实验。花生秸秆在反应器下段以10℃/min的加热速率从室温升温至700℃,其间逸出的挥发分通过保持在600℃的上段催化剂层进行催化裂解。结果表明,相比无负载的HZSM-5,Ga-H5-E和Ga-H5-H使BTX(苯、甲苯和二甲苯)产率分别提高了77%和93%,其中甲苯和二甲苯的增加尤为明显。采用热重分析仪、电感耦合等离子发射光谱仪、X射线衍射仪、扫描电子显微镜、能量色散X射线光谱仪、比表面积分析仪和化学吸附仪等对催化剂进行了表征分析。结果表明,两种Ga负载催化剂的积炭产率显著低于原催化剂(HZSM-5);Ga负载使催化剂强酸位显著增多,有利于增加脱氧反应的催化活性中心;相比于Ga-H5-E,Ga-H5-H含有容积较大的介孔和较小的平均孔径,而且更多Ga浸入了颗粒内部,这些差异可能促进乙烯和丙烯在介孔内发生芳香化反应,从而提高了单环芳香烃产量。

Study of the Conversion of Postconsumer Polystyrene on CeO2/HZSM-5 Type Materials

The catalytic conversion of polystyrene (PS) was studied in the presence of the materials type HZSM-5, CeO2, 10% CeO2/HZSM-5 and 20% CeO2/HZSM-5, which were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and nitrogen adsorption at 77K. The catalytic tests were performed via thermogravimetric analysis (TG) at heating rates of 5, 10 and 20˚C min−1 in a temperature range from 30˚C to 900˚C. For the tests, a ratio of 30% by mass of each catalytic material mixed with PS was used and the activation energy of the degradation process was determined by the Vyazovkin method. The obtained results showed that the addition of the catalyst to the PS in general reduced its degradation temperature. The 10% CeO2/HZSM-5 catalyst showed greater efficiency, as it resulted in lower activation energy for PS degradation. Thus, the combination of CeO2 with HZSM-5 resulted in materials with potential for application in the catalytic degradation of polystyrene and the results indicate that the production of a composite material can be a good strategy to generate an increase in catalytic activity and a decrease in energy process activation.

Removal of Organochlorine from Model Oil Using Mg-Modified ZSM-5 Zeolite:Dechlorination Performance,Regeneration,and Thermodynamics

Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were investigated by static adsorption experiments.The morphologies,structural features,and physicochemical properties of the adsorbents were characterized by X-ray diffraction,Brunauer-Emmett-Teller analysis,NH3 temperature-programmed desorption,scanning electron microscopy,transmission electron microscopy,and pyridine adsorption infrared spectroscopy.The Mg/ZSM-5 zeolite adsorbent possessed a relatively high specific surface area and good metal dispersion and exhibited the best dechlorination and regeneration performance.The characterization results revealed that introduction of the metal exerted a significant influence on the acidic properties of the catalyst surface.A decrease in the ratio of Brønsted acidic sites to Lewis acidic sites and an increase in the amount of moderately acidic sites were confirmed to be responsible for the excellent adsorption performance of the Mg-modified ZSM-5 zeolite.Furthermore,the Langmuir adsorption isotherm model was applied to study the adsorption equilibrium and thermodynamics of the Mg/ZSM-5 adsorbent under mild conditions.The results revealed that the removal of 1,2-dichloroethane by the Mg/ZSM-5 adsorbent was endothermic,spontaneous,disordered,and primarily involved physical adsorption.

HZSM-5分子筛一步法绿色合成

ZSM-5分子筛在吸附、催化中用途广泛,随着环保政策越来越严格,传统生产中面临的高耗能、高耗水及长流程给分子筛的应用带来阻碍。本文研究了以大孔硅胶、硝酸铝、正丙胺为原料一步法合成HZSM-5分子筛,考察了晶化时间的影响。结果表明,随着晶化时间延长,分子筛结构逐步生长,晶化36 h后成功制备出晶体呈棒状相互交错的高结晶度ZSM-5分子筛,其BET比表面积达到421 m^(2)/g,铝以四配位状态全部进入分子筛骨架。该合成方法流程简单,耗水量低,同时不添加高腐蚀性氟化氢,不需要铵交换,是一种有高效节能的分子筛绿色合成方法。

Effects of Light Rare Earth on Acidity and Catalytic Performance of HZSM-5 Zeolite for Catalytic Cracking of Butane to Light Olefins

The effects of rare earth（RE）on the structure,acidity,and catalytic performance of HZSM-5 zeolite were investigated.A series of RE/HZSM-5 catalysts,containing 7.54% RE（RE=La,Ce,Pr,Nd,Sm,Eu or Gd）,were prepared by the impregnation of the ZSM-5 type zeolites（Si/Al=64：1）with the corresponding RE nitrate aqueous solutions.The catalysts were characterized by means of FT-IR,UV-Vis,NH3-TPD,and IR spectroscopy of adsorbed pyridine.The catalytic performances of the RE/HZSM-5 for the catalytic cracking of mixed butane to light olefins were also measured with a fixed bed microreactor.The results revealed that the addition of light rare earth metal on the HZSM-5 catalyst greatly enhanced the selectivity to olefins,especially to propylene,thus increasing the total yield of olefins in the catalytic cracking of butane.Among the RE-modified HZSM-5 samples,Ce/HZSM-5 gave the highest yield of total olefins,and Nd/HZSM-5 gave the highest yield of propene at a reaction temperature of 600℃.The presence of rare earth metal on the HZSM-5 sample,not only modified the acidic properties of HZSM-5 including the amount of acid sites and acid type,that is,the ratio of L/B（Lewis acid/Brnsted acid）,but also altered the basic properties of it,which in turn promoted the catalytic performance of HZSM-5 for the catalytic cracking of butane.

Effects of Calcination Temperature on the Acidity and Catalytic Performances of HZSM-5 Zeolite Catalysts for the Catalytic Cracking of n-Butane

The acidic modulations of a series of HZSM-5 catalysts were successfully made by calcination at different treatment temperatures, i.e. 500, 600, 650, 700 and 800 ℃, respectively. The results indicated that the total acid amounts, their density and the amount of B-type acid of HZSM-5 catalysts rapidly decreased, while the amounts of L-type acid had almost no change and thus the ratio of L/B was obviously enhanced with the increase of calcination temperature （excluding 800 ℃）. The catalytic performances of modified HZSM-5 catalysts for the cracking of n-butane were also investigated. The main properties of these catalysts were characterized by means of XRD, N2 adsorption at low temperature, NH3-TPD, FTIR of pyridine adsorption and BET surface area measurements. The results showed that HZSM-5 zeolite pretreated at 800 ℃ had very low catalytic activity for n-butane cracking. In the calcination temperature range of 500-700 ℃, the total selectivity to olefins, propylene and butene were increased with the increase of calcination temperature, while, the selectivity for arene decreased with the calcination temperature. The HZSM-5 zeolite calcined at 700 ℃ produced light olefins with high yield, at the reaction temperature of 650 ℃ the yields of total olefins and ethylene were 52.8% and 29.4%, respectively. Besides, the more important role is that high calcination temperature treatment improved the duration stability of HZSM-5 zeolites. The effect of calcination temperature on the physico-chemical properties and catalytic performance of HZSM-5 for cracking of n-butane was explored. It was found that the calcination temperature had large effects on the surface area, crystallinity and acid properties of HZSM-5 catalyst, which further affected the catalytic performance for n-butane cracking.

Influence of the post-treatment of HZSM-5 zeolite on catalytic performance for alkylation of benzene with methanol

The porous material HZSM-5 zeolite with micro-mesopore hierarchical porosity was prepared by post-treatment(combined alkali treatment and acid leaching) of parent zeolite and its catalytic performance for benzene alkylation with methanol was investigated. The effect of post-treatment on the textural properties was characterized by various techniques(including ICP-AES, XRD, nitrogen sorption isotherms, SEM, NH3-TPD, Py-IR and TG). The results indicated that the post-treatment could modify the structural and acidic properties of HZSM-5 zeolite. In this procedure, not only additional mesopores were created by selective extraction of silicon but also the acidity was tuned. Consequently, the modified HZSM-5 zeolite showed larger external surface area with less acid sites as compared to the parent zeolite. It was found out that the modified zeolite exhibited a higher benzene conversion and xylene selectivity for alkylation of benzene with methanol as well as excellent life span of the catalyst than conventional ones. This can be explained by the facts that the presence of additional mesopores improved the diffusion property in the reactions. Furthermore, the modified zeolite showed an appropriate Br?nsted acidity for effective suppression of the side reaction of methanol to olefins, thus reduced the accumulation of coke on the HZSM-5 zeolite, which was favorable for the catalyst stability. In comparison with the parent HZSM-5 zeolite,the modified zeolite by alkali treatment and acid leaching showed better performance for the benzene alkylation with methanol.

Effects of Operating Conditions on the Catalytic Performance of HZSM-5 Zeolites in n-Pentane Cracking

In this work,n-pentane catalytic cracking over HZSM-5 zeolites was studied at 650°C under atmosphere pressure.A particular attention was paid to the measurement of n-pentane conversion,light olefins production,product distribution,coke deposit,etc.Several indexes were defined to evaluate the effects of operating conditions on the catalytic performance of HZSM-5 zeolites.It was found that decreasing the weight hourly space velocity,increasing the reactant partial pressure,and increasing the carrier gas flow rate could inhibit C-H bond breaking and enhance the C-C bond breaking and hydride transfer reactions,leading to reduced alkenes selectivity,which suppressed the formation of external coke and alleviated the deactivation of HZSM-5 zeolites.It was deduced that the catalytic stability of HZSM-5 zeolites was improved at the cost of alkenes selectivity.Compared with decreasing the weight hourly space velocity and increasing the reactant partial pressure,increasing the carrier gas flow rate could enhance the diffusion process and protect alkenes from being consumed in coke formation in order to improve the catalytic stability of HZSM-5 zeolites with less reduction of alkenes selectivity.

Influence of the Alkali Treatment of HZSM-5 Zeolite on Catalytic Performance of PtSn-Based Catalyst for Propane Dehydrogenation

The porous material ATZ with micro-mesopore hierarchical porosity was prepared by alkali treatment of parent HZSM-5 zeolite and applied for propane dehydrogenation. The zeolite samples were characterized by XRD, N2-physisorption, and NH 3-TPD analysis. The results showed that the alkali treatment can modify the physicochemical properties of HZSM-5 zeolite. In this case, the porous material ATZ showed larger external surface area with less acid sites as compared to the HZSM-5 zeolite. It was found out that the alkali treatment of HZSM-5 zeolite could promote the catalytic performance of PtSn/ATZ catalyst. The possible reason was ascribed to the low acidity of ATZ. Furthermore, the presence of mesopores could reduce the carbon deposits on the metallic surface, which was also favorable for the dehydrogenation reaction.

Low-temperature activation of methane over rare earth metals promoted Zn/HZSM-5 zeolite catalysts in the presence of ethylene

At low temperature of 723 K, methane can be easily activated in the presence of ethylene in the feed, and converted to higher hydrocarbons （C2-C4） and aromatics （C6-C10）, through its reaction over rare metals modified Zn/HZSM-5 zeolite catalysts without undesirable carbon oxides formation. Methane can get 37.3% conversion over the above catalysts under low temperature, and the catalysts show a longer lifetime than usual metal supported HZSM-5 zeolite catalysts without adding any rare earth metals. The effects of methane activation over various rare earth metal promoted Zn/HZSM-5 catalysts on the products and influences of several reaction conditions such as temperature, catalyst lifetime and molar ratio of CH4/C2H4 have been discussed.

Secondary Crystallization of Na_2CO_3-Modified HZSM-5 Zeolites with Tetrapropylammonium Hydroxide and Their Catalytic Performance in Thiophene Alkylation Reaction

The Na2CO3-modified HZSM-5 zeolites were further treated by tetrapropylammonium hydroxide(TPAOH) solution. The effect of TPAOH concentration on the secondary crystallization process was investigated. The resulting samples were characterized by a complementary combination of X-ray diffraction, N2 adsorption/desorption, scanning electron microscopy, X-ray fluorescence spectroscopy, XPS, 27 Al and 29 Si magic-angle spinning nuclear magnetic resonance spectroscopy, BET and temperature-programmed desorption techniques. The results showed that the secondary crystallization of the HZSM-5 zeolite could result in migration of non-framework species from the internal channels to the zeolite surface and their transformation into framework species. The catalytic activity of these modified samples for thiophene alkylation was evaluated. Both the activity and stability of the catalysts were improved after secondary crystallization.

Effect of external surface of HZSM-5 zeolite on product distribution in the conversion of methanol to hydrocarbons

The external surface of HZSM-5 zeolite was passivated by liquid siliceous deposition and by acidic sites poisoning with lepidine, respectively. Then methanol-to-hydrocarbons （MTH） reaction was investigated over the above as-prepared catalysts and the dissoluble coke on these used catalysts was analyzed by GC-MS, to study the role of the external surface of HZSM-5 in the catalytic reaction. Comparison with the experi- mental results based on parent ZSM-5 showed that the product distribution of MTH reaction was obviously influenced by the external surface. Evidences were listed as follows： （1） the final product on parent HZSM-5 showed higher aromatic selectivity, lower olefin selectivity, lower ra- tio of C2/C3＋ aliphatics and higher ratio of C3/C4＋ aliphatics than the reaction mixture produced by the sole catalysis of acidic sites in HZSM-5 channel; （2） a little of pentamethylbenzene and hexamethylbenzene in the product on parent HZSM-5, was produced via multi-methylation of methylbenzene on the external surface. The above conclusion may also be suitable for MTH reaction over other zeolites with 10-ring channel.

Thermal and hydrothermal stabilities of the alkali-treated HZSM-5 zeolites

有 micro-mesopore 的 HZSM-5 沸石层次孔被准备了由碱处理，和他们的热、热水的稳定性合成以后用 DTA， XRD，和 NH 3-TPD 描述技术被学习。比作未修改的沸石，因为 desilication 引起的中央毛孔的介绍，对待碱的 ZSM-5 沸石的热、热水的稳定性稍微被败坏。不过，对待碱的沸石框架能被维持直到温度增加了到 1175 ° C。