碱改性介-微孔HZSM-5分子筛催化乙醇脱水制乙烯性能

对两种不同硅铝比的HZSM-5分子筛进行碱处理,制备介-微孔复合HZSM-5分子筛,研究乙醇脱水制乙烯的催化性能,并考察碱溶液浓度和处理温度对HZSM-5分子筛孔结构和表面酸性的影响。结果表明,适宜的碱处理条件有利于分子筛发生骨架脱硅和脱铝,从而形成介孔。碱处理对硅铝比低的HZSM-5分子筛酸性质影响明显,而硅铝比高的HZSM-5分子筛在碱处理过程中酸性质变化不明显,更易发生脱硅和脱铝而形成更多介孔。碱改性介-微孔HZSM-5分子筛催化剂使乙醇脱水制乙烯催化性能得到改善,尤其低温催化活性提高,这主要归功于碱处理中介孔的形成和表面酸性的调变。     

碱处理HZSM-5分子筛对神东煤热解产物分布的影响

使用NaOH溶液对HZSM-5分子筛进行处理,利用粉-粒流化床快速热解实验装置,考察了经过不同时间碱处理的HZSM-5分子筛对神东煤热解产物分布的影响。结果表明：适当的碱处理能够在不破坏HZSM-5分子筛晶相结构的情况下在晶体内部引入介孔,且随着碱处理时间的延长,分子筛的介孔孔容、介孔比表面积增加,孔径分布变宽,总酸量先增大后减小。碱处理0.5h的HZSM-5分子筛催化时焦油中苯、甲苯含量最大,较原煤热解分别增加了268%、296%;碱处理2h的HZSM-5分子筛催化下热解气体总含量达到最大,较原煤热解增加了24.8%;碱处理4h的HZSM-5催化时焦油中萘及萘的同系物、多环芳烃（除萘类）含量最大,分别较原煤增加了92%、192%。     

超声波碱处理改性对丝光沸石结构、酸性质及其催化性能的影响

基于丝光沸石（MOR）催化合成乙酸甲酯稳定性较差及传统碱处理MOR较难引入多级孔的特性,提出了利用超声波对MOR进行碱处理脱硅改性以制备多级孔MOR的技术。采用XRD、SEM、TEM、吡啶红外和N₂吸-脱附等手段对催化剂进行了表征,分别考察了超声波在不同碱浓度处理改性条件下对分子筛催化剂骨架结构、酸性质、孔结构以及催化合成乙酸甲酯性能的影响。结果表明,通过超声波及合适浓度的NaOH碱溶液处理后,MOR分子筛的酸量、介孔孔容、比表面积都增加、孔径分布变宽,催化剂的活性和稳定性等催化性能得以改善。改性后的MOR催化剂二甲醚（DME）转化率由35.3%增加到44.8%,使用寿命大大延长,但碱液浓度过高会严重破坏MOR分子筛骨架结构,催化活性及稳定性快速下降。     

碱处理HZSM-5催化纤维素热裂解制备芳烃

使用不同浓度的NaOH溶液(0.2~1.0mol/L)对不同硅铝比的HZSM-5沸石进行碱处理制备多级孔HZSM-5,研究了NaOH浓度对碱处理制备多级孔HZSM-5的影响规律以及多级孔HZSM-5在纤维素催化热裂解中的催化性能。采用N2吸附-脱附、XRD、TEM和NH_3-TPD对催化剂进行表征:XRD结果显示HZSM-5碱处理后,多级孔HZSM-5依然有MFI结构特征峰;N_2吸附-脱附和TEM表征结果表明碱处理后的ZSM-5晶体内有明显的介孔孔道,形成多级孔结构;NH3-TPD结果表明随着NaOH浓度的增加,多级孔HZSM-5的强酸量呈现先增加后减少的趋势,在0.4mol/L处达到最高值。在微型裂解仪与气相色谱-质谱联用装置中研究多级孔HZSM-5对纤维素催化热裂解制备芳烃的催化性能,结果显示硅铝比为25、38、50的HZSM-5芳烃产率分别从碱处理前的33.5%、35.6%和32.2%,最高增加至37.1%、38.5%和34.0%(0.4mol/L NaOH碱处理);焦炭产率分别由碱处理前的33.1%、31.5%和33.8%降低至29.1%、25.8%和29.8%。结果表明,通过有效调控碱处理条件能够提高纤维素催化热裂解过程中的芳烃产率,同时降低焦炭产率。     

超声波碱处理改性对丝光沸石结构、酸性质及其催化性能的影响

基于丝光沸石(MOR)催化合成乙酸甲酯稳定性较差及传统碱处理MOR较难引入多级孔的特性,提出了利用超声波对MOR进行碱处理脱硅改性以制备多级孔MOR的技术。采用XRD、SEM、TEM、吡啶红外和N2吸-脱附等手段对催化剂进行了表征,分别考察了超声波在不同碱浓度处理改性条件下对分子筛催化剂骨架结构、酸性质、孔结构以及催化合成乙酸甲酯性能的影响。结果表明,通过超声波及合适浓度的Na OH碱溶液处理后,MOR分子筛的酸量、介孔孔容、比表面积都增加、孔径分布变宽,催化剂的活性和稳定性等催化性能得以改善。改性后的MOR催化剂二甲醚(DME)转化率由35.3%增加到44.8%,使用寿命大大延长,但碱液浓度过高会严重破坏MOR分子筛骨架结构,催化活性及稳定性快速下降。     

氢氧化钠改性ZSM-5分子筛的碳四烯烃催化裂解性能

用不同浓度的氢氧化钠溶液对ZSM-5分子筛进行改性,以X射线衍射(XRD)、扫描电镜(SEM)、氪-程序升温脱附(NH_3-TPD)和N_2吸附方法对改性后的催化剂进行表征,并考察了改性后的ZSM-5分子筛催化剂在碳四烯烃裂解反应中的催化性能。结果表明,氢氧化钠改性没有破坏该分子筛骨架结构,改性后催化剂的酸量、介孔孔径、介孔孔容和比表面积BET都有所增加,从而改善了催化剂的反应性能。氢氧化钠溶液的浓度为0.4 mol/L比较合适,用该浓度的氢氧化钠改性后的ZSM-5分子筛催化剂0.4AT-HZ在550℃和常压下进行碳四烯烃催化裂解反应。具有较高的稳定性,丁烯转化率可达到78%以上,丙烯收率大于38%,丙烷收率为7%。     

碱改性ZSM-5分子筛制备与催化加氢脱硫芳构化性能

采用0.2 mol/L的NaOH溶液以及浓度均为0.2 mol/L的NaOH和TPAOH的混合溶液,分别对ZSM-5分子筛进行脱硅处理。利用XRD、N_2吸附-脱附、SEM及NH_3-TPD等方法对处理前后样品进行表征。以脱硅处理后的ZSM-5分子筛为载体,采用等体积浸渍法制备了Co-Mo-P/ZSM-5催化剂,以全馏分FCC汽油为原料,考察了该催化剂的加氢脱硫及芳构化性能。结果表明,单纯强碱NaOH溶液处理对ZSM-5分子筛的晶体结构影响较大,造成分子筛骨架结构坍塌,酸性降低;TPAOH的存在保护ZSM-5分子筛骨架结构,提高ZSM-5分子筛的结晶度,并且在生成介孔的同时,最大限度地保留了原微孔结构,并调变了酸性。碱处理后制得的Co-Mo-P/HZSM-5(C-T)催化剂表现出良好的加氢脱硫与芳构化性能。     

碱改性ZSM-5分子筛制备与催化加氢脱硫芳构化性能

采用0.2 mol/L的NaOH溶液以及浓度均为0.2 mol/L的NaOH和TPAOH的混合溶液,分别对ZSM-5分子筛进行脱硅处理。利用XRD、N_2吸附-脱附、SEM及NH_3-TPD等方法对处理前后样品进行表征。以脱硅处理后的ZSM-5分子筛为载体,采用等体积浸渍法制备了Co-Mo-P/ZSM-5催化剂,以全馏分FCC汽油为原料,考察了该催化剂的加氢脱硫及芳构化性能。结果表明,单纯强碱NaOH溶液处理对ZSM-5分子筛的晶体结构影响较大,造成分子筛骨架结构坍塌,酸性降低;TPAOH的存在保护ZSM-5分子筛骨架结构,提高ZSM-5分子筛的结晶度,并且在生成介孔的同时,最大限度地保留了原微孔结构,并调变了酸性。碱处理后制得的Co-Mo-P/HZSM-5(C-T)催化剂表现出良好的加氢脱硫与芳构化性能。     

多级孔ZSM-5分子筛的制备及其丙烷脱氢制丙烯的催化性能

采用不同浓度的四乙基氢氧化铵(TEAOH)溶液处理HZSM-5分子筛,并通过XRD、XRF、H2化学吸附、吡啶红外吸附(FT-IR)和N2低温物理吸附对样品进行表征分析,考察有机碱溶液对载体和催化剂物化性能的影响。表征结果显示,低浓度的TEAOH溶液处理HZSM-5后形成介孔-微孔多级孔道结构,介孔容积和外比表面积明显增加,进而提高催化剂表面Pt金属裸露度;高浓度有机碱处理则能够明显增加分子筛表面酸性,同时引起催化剂表面Pt分散度下降。采用有机碱处理后的载体上制备了Pt-Sn-Na/HZSM-5催化剂,并在固定床反应器上考察了丙烷脱氢制丙烯的催化活性。结果表明,随着有机碱溶液的增加,丙烷初始转化率逐渐增加,丙烯选择性则逐渐下降,稳定性呈现出先增加后减少的趋势。以20 mol·L-1有机碱溶液处理HZSM-5分子筛为载体制备的催化剂用于丙烷脱氢活性评价显示,反应120 h后丙烷化率为34.93%,丙烯选择为98.67%,该催化剂脱氢活性和稳定性较佳。     

碱改性对甲醇芳构化催化剂Zn/La-HZSM-5性能的影响

采用碱处理对Zn/La-HZSM-5分子筛进行改性,调变分子筛的酸性和择形性能,评价其在甲醇芳构化反应中的性能。采用N_2低温吸附-脱附、NH_3-TPD和XRD等方法表征催化剂。结果表明,碱处理的Zn/La-HZSM-5分子筛催化剂孔体积和比表面积增加,酸量碱处理后降低,Zn改性后增加,催化剂的催化性能显著改善。0.3 mol·L~(-1 )NaOH溶液处理的Zn/La-HZSM-5分子筛催化剂在0.1 Mpa、TOS=10 h、WHSV=0.8 h~(-1)、437℃的反应条件下轻质芳烃收率41.82%,具有较高的芳烃收率和反应稳定性。     

生物质/塑料共催化热解过程中HZSM-5失活分析

利用管式炉热解装置进行HZSM-5在线共催化热解玉米秸秆/高密度聚乙烯过程中的循环和再生利用实验,对玉米秸秆进行酸洗预处理,考察原料酸洗预处理对HZSM-5催化性能的影响。采用GC-MS（气相色谱-质谱联用仪）对生物油的化学组成进行分析,并对反应前、反应后以及再生催化剂进行TG（热重分析）、ICP-MS（电感耦合等离子体发射光谱仪）、SEM/EDS（场发射扫描电镜）、BET、NH₃-TPD（程序升温脱附技术）等表征分析。研究表明,HZSM-5催化玉米秸秆/高密度聚乙烯热解的主要产物为芳烃,随着催化剂重复利用次数的增加,芳烃含量逐渐降低,催化剂的比表面积、孔容、酸性等也随之降低,说明催化剂的活性逐渐降低;原料经酸洗预处理后有利于热解中间体的生成,加速了催化剂的结焦失活速率;催化热解酸洗玉米秸秆/高密度聚乙烯的催化剂经焙烧再生后其活性基本恢复至原有水平,而催化热解未处理玉米秸秆/高密度聚乙烯的催化剂再生后其活性有所降低,碱/碱土金属在HZSM-5催化剂上发生累积,从而引起酸性位点“中毒”失活,而原料经酸洗预处理后可有效降低催化剂上碱/碱土金属的累积量,有利于延长催化剂的使用寿命。     

ZSM-11分子筛的碱处理及其正十二烷催化裂解性能

研究了碱处理对ZSM-11分子筛的微观结构、酸性质和催化裂解性能的影响。采用不同浓度的氢氧化钠对ZSM-11分子筛进行碱处理,得到了级孔ZSM-11分子筛。用XRD,SEM,TEM, NH₃-TPD,N₂低温吸附-脱附等手段对碱处理后的分子筛进行了表征。以正十二烷为模型燃料,在550 ℃、4 MPa的条件下评价了分子筛的催化裂解性能。结果表明,碱处理导致HZSM-11分子筛晶粒内形成介孔、比表面积和酸量增加。碱处理的ZSM-11分子筛表现出较高的催化裂解活性。其中,用浓度为0.1 mol/L的氢氧化钠溶液处理的HZSM-11分子筛,催化活性最高。与未处理的HZSM-11分子筛相比,正十二烷的平均转化率提高了约58%。     

多级孔HZSM-5分子筛催化快速热解生物质制芳烃

采用酸和/或碱处理法制备了一系列多级孔HZSM-5分子筛,采用XRD、N₂吸附、XRF、TEM、²⁷Al MAS NMR和NH₃-TPD等表征手段对其孔道结构和酸性进行表征。表征结果表明,采用碱处理方法,可获得孔径集中于3~6 nm的介孔结构,通过改变酸、碱处理次序,可调变酸中心数量和强酸/总酸中心比例。在Py-GC/MS装置上,以纤维素和水稻秸秆为原料,研究多级孔分子筛结构对催化快速热解（CFP）制芳烃反应的影响。反应评价结果表明,同商品级HZSM-5相比,采用先碱后酸处理获得的多级孔HZSM-5分子筛（HZ-OH/H）,可将纤维素CFP芳烃碳产率由32.3%提高至43.6%,可将水稻秸秆CFP芳烃碳产率由23.0%提高至30.8%。多级孔HZ-OH/H分子筛的孔道结构和酸中心分布特征,对开发应用于生物质制芳烃的高效工业催化剂具有借鉴意义。     

微孔-双介孔核壳型HZSM-5@BMMs催化甲醇芳构化

采用外延法,以HZSM-5为核,双介孔分子筛BMMs为壳制备了多级孔核壳型HZSM-5@BMMs甲醇芳构化(MTA)催化剂。采用XRD、BET、NH3-TPD、SEM和TEM对催化剂进行了表征。结果表明:HZSM-5@BMMs具有明显的核壳结构和微孔-双介孔多级孔孔道,孔径集中分布于0.9、2.2和5.3 nm,其比表面积(510.8 m2/g)和孔容(0.399 cm3/g)均高于HZSM-5的比表面积(408.4 m2/g)和孔容(0.190 cm3/g),而酸量(0.573 mmol/g)和酸强度均低于HZSM-5的酸量(0.883 mmol/g)和酸强度。相同反应条件下HZSM-5@BMMs寿命比HZSM-5增加38 h,最高芳烃收率为25.7%,最高BTX(轻质芳烃:苯、甲苯、二甲苯)选择性为55.3%。     

硅烷化和有机弱碱改性Mo/HZSM-5对甲烷无氧芳构化催化性能的影响

催化剂的形态及晶粒的组装对其催化性能有重要影响,采用硅烷化处理对Mo基催化剂表面酸性进行毒化制备了核壳型（Mo基催化剂@Silicalite-1）复合材料;采用四丙基氢氧化铵或正丁胺有机弱碱对Mo/HZSM-5进行刻蚀,然后经过脱硅再结晶分别制备了表面富硅型中空结构Mo/HZSM-5微球和表面富硅、核内含有多级孔道的Mo/HZSM-5微球。采用XRD、TEM、N₂等温吸脱附和NH₃-TPD对催化剂结构进行表征,并考察了三种不同后处理方法对Mo基催化剂在甲烷无氧芳构化反应中催化性能的影响。硅烷化和有机碱处理均能够调变Mo/HZSM-5催化剂的表面酸性,而经有机碱处理以后,催化剂结晶度、介孔比表面积和孔容均具有不同程度的增加,三种不同后处理方法均能改善Mo/HZSM-5催化剂的反应稳定性,对产物的分布也产生了显著影响。     

Alkaline modification of ZSM-5 catalysts for methanol aromatization: The effect of the alkaline concentration

The effects of alkaline treatment on the physical properties of ZSM-5 catalysts and on their activities for methanol to aromatics conversion have been investigated. A mild alkaline treatment (0.2 and 0.3 mol/L NaOH) created mesopores in the parent zeolite with no obvious effect on acidity. The presence of mesopores gives the catalyst a longer lifetime and higher selectivity for aromatics. Treatment with 0.4 mol/L NaOH decreased the number of Brønsted acid sites due to dealumination and desilication, which resulted in a lower deactivation rate. In addition, more mesopores were produced than with the mild alkaline treatment. As a result, the lifetime of the sample treated with 0.4 mol/L NaOH was almost five times that of the parent ZSM-5. Treatment with a higher alkaline concentration (0.5 mol/L) greatly reduced the number of Brønsted acid sites and the number of micropores resulting in incomplete methanol conversion. When the alkaline-treated catalysts were washed with acid, some of the porosity was restored and a slight increase in selectivity for aromatics was obtained.     

Dealumination and desilication for Al-rich HZSM-5 zeolite via steam-alkaline treatment and its application in methanol aromatization

The hierarchical HZSM-5 was prepared via dealumination and desilication of commercial Al-rich HZSM-5, and characterized by X-ray diffraction, 27Al magic-angle spinning nuclear magnetic resonance, inductively coupled plasma mass spectrometry, scanning electron microscope, transmission electron microscope, N2 adsorption-desorption, NH3 temperature-programmed desorption, performed thermogravimetric and Raman spectrum. The results showed that partial framework of HZSM-5 was removed after steam treatment at 0.15 MPa, 500℃ for 3 h. HZSM-5 with high specific surface area and much mesoporosity was obtained by the subsequent alkaline treatment. The regulation of acid quantity was achieved by altering the concentration of alkaline. Dealumination and desilication of Al-rich HZSM-5 zeolites became more effective using a combination of steam and alkaline treatments than using alkaline treatment alone. Methanol aromatization reaction was employed to evaluate the catalytic performance of treated HZSM-5 at 0.15 MPa, 450℃ and MHSV of 1.5 h^-1. The results indicated that after steam treatment, HZSM-5 further treated with 0.2 mol/L NaOH exhibits the best catalytic performance: the selectivity of aromatics reached 42.1% and the lifetime of catalyst attained 212 h, which are much better than untreated HZSM-5.     

Realumination of dealuminated HZSM-5 zeolite by citric acid treatment and its application in preparing FCC gasoline hydro-upgrading catalyst

This article describes a novel citric acid treatment method for realuminating dealuminated HZSM-5 zeolite and its application in enhancing the performance of the zeolite derived FCC gasoline hydro-upgrading catalysts. A series of modified HZSM-5 zeolites were prepared by streaming and/or acid treatments and the influences of the different modification methods on the acidity, pore structure and catalytic performance of the modified HZSM-5 zeolite supported catalysts were compared in the present investigation. The results showed that compared with the single HCl or citric acid treatment, the steaming treatment, and the steaming/HCl treatments, the citric acid treatment after steaming exclusively increased the amount of framework Al species due to its realumination effect on the steamed HZSM-5 zeolite. This realumination effect of the citric acid treatment could optimize the ratio of framework Al to extra-framework Al in the steamed HZSM-5 zeolite and thus greatly improve the acidity distribution and pore structure of the corresponding catalyst. The catalytic performance assessments of the different zeolite supported catalysts for FCC gasoline hydro-upgrading revealed that the catalyst supported on the steaming/citric acid treated HZSM-5 zeolite had balanced initial and long-term activities in hydrodesulfurization, hydroisomerization and aromatization, high liquid yield and improved gasoline road octane number. The superior catalytic performance of the catalyst could be closely related to its suitable ratio of framework Al to extra-framework Al achieved by the combinational use of the steaming dealumination and the citric acid realumination, fully demonstrating the effectiveness of the steaming and citric acid treatments in optimizing the physicochemical properties and catalytic performance of HZSM-5 zeolite supported catalysts.     

Synergisms between matrices and ZSM-5 in FCC gasoline non-hydrogenating upgrading catalysts

This article describes a novel non-hydrogenating FCC gasoline upgrading catalyst system consisting of a kaolin/γ-Al₂O₃ binary-matrix and an active component zeolite HZSM-5. Different catalysts made from the different combinations of HZSM-5 with the three matrices (two kaolins and γ-Al₂O₃) or their binary mixtures were prepared and their catalytic performances were assessed in a continuously flowing fixed-bed reactor using FCC gasoline as feedstock. The results showed that compared with the single-matrix based HZSM-5 catalysts, the binary-matrix based HZSM-5 catalysts had much better catalytic performance. The characterization results of the acidity, specific area and pore structure properties of the catalysts revealed that the synergisms between the matrices and HZSM-5 in the acidity and pore distribution of the binary-matrix based catalysts accounted for their improved catalytic performance. Our results demonstrated that the non-hydrogenating catalyst system developed in the present investigation can convert olefins in FCC gasoline into aromatics that have higher research octane number (RON) and thus has potential application for FCC gasoline upgrading because of its excellent olefin reduction ability and RON preservability.     

Creating Mesopores in ZSM-5 Zeolite by Alkali Treatment: A New Way to Enhance the Catalytic Performance of Methane Dehydroaromatization on Mo/HZSM-5 Catalysts

Well-controlled treatment with alkali solution causes the etching of HZSM-5 framework, which results in the formation of the new porosity and channel structure with the coexistence of micropores and mesopores, as evidenced by nitrogen adsorption experiments. The dissolution of the zeolite framework, as revealed by the investigation of solid-state NMR, begins from the crystalline site with Si–O–Si linkages. The inertness of the alkali treatment toward Si–O–Al bond in the framework preserves the specific Brønsted acid site that is defined to be the bridging OH species over Si–O–Al units in zeolite. The Mo-modified catalysts derived from the alkali treatments showed a very high catalytic performance in the conversion of methane to aromatics (MDA) when compared with the conventional Mo/HZSM-5 catalyst. The unique selectivity to aromatics and stability of the catalysts derived from the alkali-treated ZSM-5 are attributed to the coexistence of mesopores and inherent micropores in the zeolites, which optimizes an environment for catalytic reaction and mass transfers. The channel with mainly 3–5?nm in diameters in the zeolites serves as the “aisle” to enhance the diffusion of molecules, especially the aromatics molecules, while the micropores have been identified to be the active cavities for the aromatics formation.