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1.
考察了复合催化剂AlCl_3/SbCl_3的不同配制方法和质子捕捉剂2,6-二异丁基-4-甲基吡啶(DTBMP)对α-蒎烯阳离子聚合反应的影响。结果表明,AlCl_3和SbCl_3加热熔融复合比简单复合的引发聚合活性更高;DTBMP对该复合催化剂的聚合反应速率及其产物分子量分布均无明显影响,证明该复合催化剂形成的活性种本质上与质子H活性种不同,是新型活性种。根据27AlNMR对该体系活性种分析结果,认为引发阳离子是[Sb(V)Cl_4],抗衡阴离子是[Al_2Cl_7]  相似文献   

2.
本文系统地考察了甲苯和1,3,5-三甲苯在以Hβ为基质的改性沸石分子筛上烷基转移反应。探讨了金属Al,Bi和非金属P改性Hβ沸石对甲苯和1,3,5-3甲苯的转化率和对产物二甲苯的选择性影响规律。用氨程序升温脱附(NH3-TPD)和吡啶吸附红外(IR)方法考察了Hβ沸石表面酸性和酸中心分布以及改性对β沸石表面酸性的影响。发现:1)用Al改性后,催化活性大大超过未改性的Hβ分子筛;2)L酸中心对改性Hβ分子筛的烷基转移反应活性起重要作用。  相似文献   

3.
铝镁柱联粘土的制备及表征   总被引:4,自引:0,他引:4  
以铝镁双金属离子低聚物为交联剂,制备了复合柱联膨润土催化剂(简称为Al-Mg-PILC)。详细考察了Mg/Al比、Al/土比等因素对合成产品性能的影响。借助于XRD、BET、DTA表征手段,结合轻柴油裂解,三甲基苯转化反应,探讨催化剂表面酸性。结果表明,铝镁复合柱直径小于的相应值,所得柱联粘土表面总酸量较少,强酸比例增大。经350℃脱附后,其吡啶吸附量可保持25℃下吸附值的7%左右,而Al-PILC只保留2.5%。进一步证实了交联剂的改进对柱联粘土催化剂性能的影响。  相似文献   

4.
采用IR和XRD技术研究了B2O3/ZrO2催化剂的结构性质,用ICP-MS测定了样品中B2O3的含量,通过Hammet指示剂正丁胺滴定法测定了B2O3/ZrO2系列催化剂的表面酸性;研究了载体预处理温度对样品表面酸性和结构的影响,以及B2O3含量对样品催化性能的影响;比较了B2O3负载于ZrO2,Al2O3,SiO2,TiO2,MgO和HZSM-5上催化活性和目的产物选择性的差异,讨论了B2O3/ZrO2催化剂在气固相Beckmann重排反应中的作用特点  相似文献   

5.
通过脉冲微型反应催化色谱装置,考察了正己烷在Pt/Al2O3和Pt-Dy/Al2O3催化剂上的转化反应;用TPD、TPR和HOT技术研究了Pt-Dy/Al2O3催化剂的表面性质.结果表明,Dy和Pt之间存在相互作用,并发生电子效应和几何效应,但Dy的掺入未改变Pt/Al2O3催化剂表面固有的吸附中心性质  相似文献   

6.
氟氯有机化合物对HZSM-5分子筛改性过程中氟和氯的作用   总被引:2,自引:0,他引:2  
利用XRD,MAS,NMR,IR和XPS等手段研究了CF4-nCln改性的HZSM-5分子筛的体相和表面结构的变化。结果表明,改性过程中F和Cl均能使HZSM-5脱铝和脱硅。Cl可以使沸石骨架SiO2/Al2O3升高,而F除使沸石骨架脱铝外,还会极化其晶格。F比Cl更容易在沸石表面富集。F和Cl是通过取代O或OH与沸石表面Si或Al作用的。改性后的沸石表面有数种含氟表面物种存在。  相似文献   

7.
SAPO-34分子筛表面酸性质的研究   总被引:6,自引:0,他引:6  
以水热合成法制备了三个具有不同硅磷铝组成的硅磷酸铝分子筛SAPO-34样品,采用红外光谱(IR)和氨法程序升温脱附(TPD)两种方法考察了它们的表面酸性质。红外谱图中的3600cm-1和3621cm-1谱峰归属于处于SAPO-34分子筛结构中不同位置的两种桥联羟基(Si-OH-Al)的振动。NH3-IR测定结果显示,这两种羟基具有较强的B酸特性,并且是分子筛酸性的主要来源;而分子筛具有的L酸中心的酸性较弱。比较三个样品的NH3-TPD、NH_3-IR和骨架组成后发现,SAPO-34的酸性受其骨架硅含量的强烈影响:当Si/Al摩尔比小于1时,酸性随硅含量增高而变弱;当Si/Al摩尔比大于1时,酸性将随硅含量增高而变强。  相似文献   

8.
NiMoNx/γ-Al2O3催化剂的制备及加氢脱氮性能   总被引:6,自引:0,他引:6  
采用程度升温氮化(TPN)的方法制备了NiMoNx/γ-Al2O3催化剂,考察了它对吡啶加氢脱氮(HDN)反应的催化活性。结果表明,NiMoNx/γ-Al2O3催化剂的活性远远高于NiMoSx/γ-Al2O3催化剂和工业硫化态催化剂。对于NiMoZx/γ-Al2O3催化剂,助剂Ni的作用与硫化物体系中的Ni不同,它不仅是活化氢中心,同时也是脱氮中之心一,NiMoNx/γ-Al2O3催化剂的HDN活  相似文献   

9.
程时标  李凤仪 《分子催化》1996,10(5):333-338
通过脉冲微型反应催化色谱装置,考察了正己烷在Pt/Al2O3和Pt-Dy/Al2O3催化剂上的转化反应:用TPD、TPR和HOT技术研究了Pt-Dy/Al2O3催化剂的表面性质。  相似文献   

10.
SiO2负载的氮化钼催化剂的合成和表征   总被引:5,自引:1,他引:5  
采用MoO3/SiO2和NH3程序升温反应的方法合成了一系列不同Mo含量的Mo2N/SiO2催化剂,并采用XRD、BET、XPS、TPR、H2-TPD和IR等手段,结合中压下吡啶加氢脱氮反应,研究了它们的表面性质和反应性能。发现Mo2N/SiO2催化剂在反应性能和吸氢性质等方面类似于非负载的氮化钼。氮化前后,低Mo担载量催化剂的比表面积降低不大,在高Mo担载量下,由于氮化态的Mo-SiO2催化剂上  相似文献   

11.
Shan  Shufeng  Tian  Yiting  Chen  Feifei  Wu  Shikui  Zhou  Rujin  Xie  Ying  Li  Ning  Zeng  Xingye  Lin  Cunhui  Yu  Wei 《Catalysis Surveys from Asia》2022,26(1):35-45

NiMoS supported on ZSM-5 with different Si/Al ratio, crystallite size and pore structure was prepared by incipient impregnation method and applied in 1, 3, 5-trimethylbenzene (1, 3, 5-TMB) hydrodealkylation (HDAK). The physicochemical properties of samples were characterized by XRD, FTIR, SEM, N2 adsorption–desorption, NH3-TPD, Py-FTIR, H2-TPR, HRTEM and TGA. It is demonstrated that for microporous NiMoS/ZSM-5, acid amount and crystallite size of HZSM-5 are key factors affecting HDAK performance. The larger acid amount and smaller crystallite size can promote the conversion of 1, 3, 5-TMB, especially the dealkylation reaction, resulting in higher BTX yield. Compared to NiMoZ-3, mesopores in micro-mesoporous NiMoAKZ-3 are beneficial to accessibility of 1, 3, 5-TMB to NiMoS and acid sites in close proximity, and the diffusion of reactant and product molecules inside pores, thus resulting in superior HDAK performance of NiMoAKZ-3. Moreover, the reaction network of 1, 3, 5-TMB HDAK was revealed according to product distribution.

Graphic Abstract

NiMoS supported on ZSM-5 was developed for heavy aromatic hydrodealkylation (HDAK). Acid amount and crystallite size of microporous ZSM-5 are key factors affecting 1,3,5-trimethylbenzene (1,3,5-TMB) HDAK. Mesopores inside ZSM-5 facilitate accessibility of 1,3,5-TMB to NiMoS and acid sites in close proximity and improve HDAK performance.

  相似文献   

12.
The reaction of trimethylbenzene (TMB) over alumina-pillared montmorillonite (Al-PM) had been investigated in a fixed-bed flow reactor at 300 °C and atmospheric pressure. Al-PM calcined in the range 300-500 °C exhibited decreased layer distance, surface area and acid amount. The strong acid sites of Al-PM calcined at 500 °C were greatly diminished according to measurements of ammonia temperature-programmed desorption. Under our conditions the reaction proceeded mainly via isomerization and disproportionation with little dealkylation. The conversion of reactant decreased in the order 1,2,3-TMB ≥ 1,2,4-TMB > 1,3,5-TMB and the selectivity of isomerization in the order 1,2,3-TMB > 1,3,5-TMB > 1,2,4-TMB, corresponding to the order of diminishing thermal instability. Both the catalytic activity and the selectivity ratio of disproportionation to isomerization decreased with increased calcined temperature and time-on-stream. o-Xylene content in the total xylene produced from 1,2,4-TMB or 1,2,3-TMB greatly exceeded the composition at thermodynamic equilibrium. These results arc consistent with the decrease of both the strong acid sites and the pore size of Al-PM which exhibits the restricted transition state selectivity.  相似文献   

13.
以AlPO_4-5分子筛为载体,采用浸渍法制备Cu-Fe-MgO/AlPO_4-5催化剂,用于催化甲醇和水蒸气重整反应制氢气。采用XRD、N2吸附-脱附、H2-TPR、CO2-TPD和NH3-TPD等对催化剂进行表征。结果表明,加入Fe可以明显提高甲醇的转化率,但副产物二甲醚的选择性也增加,添加MgO对降低二甲醚具有明显的作用,但不能提高甲醇的转化率。AlPO_4-5负载Cu、Fe和MgO的质量分数分别为15%、6%和1%时具有较高的催化活性,在反应温度300℃、水醇物质的量比为1.1∶1和质量空速2.51 h~(-1)的条件下,对甲醇的转化率为93.08%,二氧化碳和氢气的选择性分别为95.80%和96.93%,对副产物一氧化碳和二甲醚的选择性分别为1.70%和2.51%。表征结果表明,Cu-Fe-MgO/AlPO_4-5同时含有弱酸弱碱和强酸强碱中心,适量的MgO增加了强碱中心的量,降低弱酸中心的强度,但对强酸中心影响不大。  相似文献   

14.
氧化镧催化剂上甲烷氧化偶联—不同制备方法的比较   总被引:5,自引:2,他引:5  
本文研究了5种不同制法的La_2O_3对甲烷氧化偶联的催化性能,其C_2选择性和C_2收率的相对顺序为:La_2O_3(1)>La_2O_3(2)>La_2O_3(4)>La_2O_3(5)>La_2O_3(3)。并运用XRU、XPS、CO_2-TPD、NH_3-TPD和IPA转化反应等技术分别对催化剂的体相结构和表面性质,表面酸碱性进行了测定。结果表明,由于制备方法的不同,导致了La_2O_3晶体表面结构的差异,这是影响催化性能的主要原因。同时还发现,催化剂的活性和C_2选择性与表面酸碱性存在着相依性,La_2O_3表面的总碱位数与总酸位数的比值,与其催化性能有较好的直接对应关系。  相似文献   

15.
The reaction of 1,2,3-trimethylbenzene (1,2,3-TMB) over HY zeolite was investigated in a fixed-bed flow reactor at 200-300 °C under atmospheric pressure. The reaction products include toluene, pentamethylbenzene and isomers of xylene, 1,2,3-TMB and tetramethylbenzene. Based on the time-on-stream theory, the types and initial selectivities of these products were determined from plots of product selectivity. 1,2,4-TMB is initially produced from 1,2,3-TMB via isomerization whereas o-xylene, m-xylene, 1,2,3,4- and 1,2,3,5-tetramethylbenzene were primarily formed by disproportionation of 1,2,3-TMB. Isomerization and disproportionation obeyed first- and second-order kinetics, respectively; both reactions proceeded via a carbonium ion mechanism with the former occurring by methyl transfer on the benzene ring whereas the latter proceeded through the diphenylmethane transition state. The activation energies are 31.6 and 37.2 kJ mol?1 for isomerizaion and disproportionation, respectively.  相似文献   

16.
用TPSR-MS技术研究了Cu,Zn和Ga改性H-ZSM-5沸石的活性中心性质及C1~C4醇的反应历程。结果表明,Zn-和Ga-ZSM-5有两种芳构化活性中心,即B酸和Zn,Ga活性物种;甲醇在Cu-ZSM-5上只生成二甲醚、CO和CO2,而在Zn-ZSM-5上芳构化反应历程为:(1)醇经由醚脱水生成烯烃,C2~C4醇学可单分子脱水生成烯烃;(2)烯烃中间物齐聚,齐聚物通过氢转移和脱氢途径环化、芳  相似文献   

17.
The oligomerization of ethylene in FCC dry gas over HZSM-5 catalyst with different Si/Al2 ratios was studied. The effect of acid density of catalyst on the oligomerization of ethylene was discussed. By increasing the acid density of catalyst, ethylene conversion showed a linear increase, while the yields of olefins decreased when the acid density of catalyst exceeded 0.14 mmolNH3/g owing to a promotion of hydrogen transfer reaction. Through comparing the average distance between acid sites on catalyst with kinetic diameters of olefins, it was found that the dimerization of ethylene was not restrained by the sparse distribution of acid sites, while the hydrogen transfer reaction of C3 and C4 olefins was limited. On these bases, a conclusion is proposed that the dimerization of ethylene proceeded via Eley-Rideal mechanism, while the hydrogen transfer reaction of C3 and C4 olefins followed the Langmuir-Hinshelwood mechanism.  相似文献   

18.
ZnCl2/NaY催化邻苯二酚与甲醇醚化反应;固体酸催化剂;愈创木酚  相似文献   

19.
采用聚合羟基复合阳离子合成交联蒙脱土Al-Ce-PILC, 并分别用NH4NO3和(NH4)2SO4处理后, 将其作为载体, 采用浸渍法制备了应用于C3H6选择性催化还原NO反应的铜基交联黏土催化剂Cu/Al-Ce-PILC. 用Py-IR, IR和DSC等表征技术研究了不同处理方式对Al-Ce-PILC的结构、 酸性和催化剂活性的影响. 结果表明, 未经处理的Al-Ce-PILC中同时存在L酸和B酸, 以L酸为主, Cu/Al-Ce-PILC上NO的最大转化率仅为18。5%; 用NH4NO3处理提高了L酸量, NO转化率降低; 而用(NH4)2SO4处理改变了Al-Ce-PILC的酸性结构, 增大了B酸量, 并形成了超强酸中心, 催化剂上NO转化率显著提高, 在350 ℃时达最大值50.2%. B酸对于Cu/Al-Ce-PILC上NO的还原是必要的, 它有利于C3H6吸附并适度氧化为活性中间物种, 其酸量和酸强度的增加是催化剂活性改善的主要原因.  相似文献   

20.
The conversion of 1,2,4-trimethy]benzene (1,2,4-TMB) over HY zeolite was studied at atmosoheric pressure and 200–300 °C by using a fixed-bed, integral-flow reactor. The types and initial selectivities of various products were obtained from plots of product selectivity according to the time-on-stream theory. The primary reaction included the isomerization and the disproportionation; the former led to the simultaneous formation of 1,2.3- and 1,3,5-TMB whereas the latter produced all isomers of xylene and tetramethylbenzene. The relative initial rate of disproportionation to isomerization decreased from 12.6 at 200 °C to 5.47 at 300 °C. The activation energies for the primary reactions were estimated and compared with those in the reaction of 1,2,3-TMB.  相似文献   

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