介孔-大孔结构无定形硅-铝催化剂的核磁共振研究

合成了具有介孔-大孔双模型分级结构的无定形硅-铝催化剂,利用硅和铝核的固体魔角核磁共振谱,考察了合成样品中硅和铝结构上的原子特征.     

高硅ZSM-5在辛烷值助剂中的应用

研究了不同硅铝比ZSM-5分子筛的催化裂化反应性能,结果表明,高硅铝比ZSM-5分子筛能实现提高汽油辛烷值的同时控制液化气产率增幅较小。考察不同硅铝比的高硅ZSM-5分子筛的反应性能,高硅ZSM-5助剂在ACE装置上的评价结果表明,助剂能使液化气和汽油辛烷值小幅增加,同时也能增加汽油中的芳烃含量。随着ZSM-5分子筛硅铝比的增加,助剂控制液化气的性能逐渐增强,但同时提高汽油辛烷值的性能逐渐减弱。在实际应用中,适宜的ZSM-5分子筛硅铝比应根据目标用户的实际情况和要求灵活选择。     

硅铝凝胶制备与晶化研究

本文以铝胶和硅胶为原料,采用溶胶-凝胶方法进行了硅铝凝胶形成及晶化行为研究.结果表明,要形成稳定铝硅溶胶pH值必须控制在3以下,采用氨水和乙酰丙酮可调节胶凝时间.采用XRD和TEM研究了凝胶和不同温度热处理之后粉体组成和结构,从干凝胶至莫来石的整个形成过程首先是生成硅铝尖晶石,然后才是莫来石,所得到的粉体存在较为严重的二次团聚.在硅铝凝胶中引入氟化铝有助于莫来石晶须生成.     

气相化学法制备高硅铝比Y型沸石性能考宣传察

本研究以氮吸附、分析电镜（ＡＥＭ）、光电子能谱（ＥＳＣＡ）、固体核磁２９ＳｉＭＡＳＮＭＲ、２７ＡＩＭＡＳＮＭＲ及傅里叶红外（ＦＴ－ＩＲ）考察了用ＳｉＣｌ４气相化学法制备的高硅铝比Ｙ型沸石的吸附性能、孔结构、脱铝均匀性、硅铝分布及酸性，并对其催化剂进行了初步评价。结果表明，气相化学法可制备出晶胞参数变化范围宽、结晶保留度高的高硅铝比Ｙ型沸石，其骨架外铝以及二次孔均可调节。该沸石具有好的热稳定性和水热稳定性及良好的活性水平，适宜于作渣油催化裂化及提高汽油辛烷值的催化裂化催化剂的活性组元。     

Upgrading of a wood-derived oil over various catalysts

The upgrading of a bio-oil using a fixed bed micro-reactor operating at 1 atm, 3.6 WHSV and 330–410°C over various catalysts is reported. The catalysts used were HZSM-5, silicalite, H-mordenite, H-Y and silica-alumina. The yield of hydrocarbons as well as the extent of deoxygenation, coke formation and conversion of the non-volatile portion of the bio-oil were used as measures of catalyst performance. The maximum hydrocarbon yield when HZSM-5 was used occurred at 370°C and was 39.3 wt% of the bio-oil. For the other catalysts, the hydrocarbon yields increased with temperature and were up to 22.1 wt% for silicalite; 27.5 wt% for H-mordenite; 21.0 wt% for H-Y; and 26.2 wt% for silica-alumina at 410°C. The hydrocarbon selectivity with HZSM-5 and silicalite catalysts was mostly for gasoline range hydrocarbons (C₆ to C₁₂) and for H-mordenite and H-Y for kerosene range hydrocarbons (C₉ to C₁₅). The hydrocarbon fraction obtained with silica-alumina did not produce any defined distribution. The pore size, catalyst acidity and catalyst shape selectively affected the product distribution. The overall performance followed the order: HZSM-5 > H-mordenite > H/Y > silica-alumina, silicalite.     

富铝β沸石的制备和表征

采用微型晶化釜,在投料硅铝比(n(SiO_2):n(Al_2O_2),简称SAR)为3～14,含氟、低水含量以及无钠/低钠的SiO_2-Al_2O_3-四乙基氟化铵-H2O体系中、近中性和晶化温度170℃条件下,考察了富铝β沸石的晶相生长规律。采用XRD,SEM,~(27)Al MAS NMR,XRF,BET等方法,分析了铝源、晶化时间、系统水含量(n(H_2O):n(Si+Al))、投料SAR、原料焙烧温度等因素对晶化过程的影响。实验结果表明,以焙烧后的无钠/低钠硅铝胶为铝源有利于抑制杂相生成,适宜的n(H_2O):n(Si+Al)为3.5左右,晶化时间为7 d以上;投料SAR在10以下时,随焙烧温度的升高,晶化活性提高,经过1 000℃以上高温焙烧,投料SAR最低为7时能达到较高晶化活性;投料SAR在10以上时,随焙烧温度的升高,晶化活性降低,当投料SAR为10～14、焙烧温度为600℃时,可获得纯相、高结晶度和SAR为15以下的富铝β沸石;沸石产品形貌多为团聚体,多数试样可辨初级晶粒大小多为微米级(0.5～2.0μm),个别试样多为纳米级(30～100 nm)。     

MCM-56分子筛的合成和应用

分子筛MCM - 56是一种具有独特孔道结构的硅铝沸石 ,具有热稳定性好、比表面积大、吸附性强等特点。对MCM - 56分子筛的合成及在催化和吸附方面的应用做了介绍     

MOR@SAPO-11复合分子筛的合成及Pt/MOR@SAPO-11催化剂的加氢异构化性能

采用硅铝源法制备具有核壳结构的复合分子筛MOR@SAPO-11。利用XRD、SEM、N2物理吸附 脱附曲线、NH3-TPD和Py-FTIR等手段对MOR@SAPO-11复合分子筛的晶体结构、分子筛形貌和酸性质进行表征。结果表明,采用硅铝源法制备的复合分子筛MOR@SAPO-11呈现以丝光沸石为核,SAPO-11为壳的核壳结构。相比于单一分子筛MOR、SAPO-11和机械混合物MOR+ SAPO-11,MOR@SAPO-11复合分子筛具有更适宜的酸性和较高的B酸分布。这说明MOR@SAPO-11复合分子筛发生了协同作用,通过物理或者化学作用紧密相连,改善了自身的酸性。在相同的反应条件下,以硅铝源法制备的复合分子筛MOR@ SAPO-11为载体的Pt催化剂异构化活性和异构烃选择性比以单一分子筛和机械混合分子筛为载体的Pt催化剂有明显提高。     

异丙基萘的分子间烷基转移及其在制备2,6-二异丙基萘中的应用

Isopropylation of naphthalene with propene resulted in a variety of isomers having different alkylation levels. The most important isomer is 2,6-DIPN, which is the precursor of important monomer 2,6-naphthalene dicarboxylic acid used for making liquid crystal polymers. In order to increase the yield of 2,6-DIPN, the intermolecular transalkylation with naphthalene was applied to the mixture of other DIPNs and PIPN to obtain MIPN enriched product, which underwent isopropylation with propene to produce 2,6-DIPN in a higher yield. The experimental study showed that the preferable conditions for transalkylation were reaction temperature of 325℃, the molar ratio of isopropyl group to naphthyl group （IP/N） of 0.8 ： 1-0.9 ： 1, reaction time of 4h and 5% of amorphous silica-alumina by mass. The conversions of DIPN and PIPN in its mixture were 62%-69% and 87%-88% respectively and the yield of MIPN was greater than 40%. The mixture of MIPN enriched product and recovered MIPN from rectification was subject to isopropylation with propene at 275℃ over a shape-selective catalyst to produce 2,6-DIPN in a yield up to 38%. A recycled process of recovered components was established, through one cycle the yield of 2,6-DIPN based on naphthalene may be 2.8 times higher than before, and the utilization ratio of raw naphthalene was increased by 46%.     

NaY分子筛制备技术的综合改进

对NaY配方进行优化以降低外排母液中SiO2含量,将母液中SiO2回收形成硅铝胶重新用于合成分子筛。这2种工业生产方法,经过试验后在工业上得到成功应用。结果表明,在一定范围内调节硅铝胶加入量对NaY分子筛质量没有影响。通过上述应用,解决了催化裂化催化剂装置外排污水悬浮物高的难题。