NPS-1负载磷钨酸催化合成4-叔丁基-2-(α-甲基苄基）苯酚

以介孔分子筛NPS-1负载12-磷钨酸杂多酸为催化剂,4-叔丁基苯酚和苯乙烯为原料,合成4-叔丁基-2-（α-甲基苄基）苯酚（t-BAMBP）。采用正交实验研究介孔材料NPS-1负载12-磷钨酸对t-BAMBP合成反应的催化活性,考察反应温度、反应时间、原料配比和催化剂用量对t-BAMBP收率的影响。优化的工艺条件为：反应温度70 ℃,反应时间30 min,n（苯乙烯）∶n(4-叔丁基苯酚)=1.3∶1,催化剂用量为4-叔丁基苯酚质量的0.2%,t-BAMBP收率70.3%。     

Al-SBA-15介孔分子筛催化合成叔丁基苯酚

采用水热直接合成法合成了n(Si)∶n(Al)为10、25和50的Al-SBA-15介孔分子筛。用X射线衍射对材料进行了表征,结果表明,Al-SBA-15保持了母体SBA-15高度有序的六方介孔结构。并研究其在苯酚与甲基叔丁基醚的烷基化反应中的催化性能,结果表明,Al-SBA-15(25)催化剂具有较高的苯酚转化率和2,4-二叔丁基苯酚选择性,最佳工艺条件为：反应温度160 ℃,n(甲基叔丁基醚)∶n(苯酚)=1.5∶1,空速1.5 h^－1。在此条件下,苯酚转化率为73.2％,2,4-二叔丁基苯酚选择性为57.9％,催化剂Al-SBA-15(25)可稳定运行约80 h。     

硅酸钠为硅源的介孔分子筛SBA-15-SO3H的研究

在强酸性和水热条件下以硅酸钠（Na₂SiO₃·9H₂O）为硅源合成表面含磺酸基的介孔分子筛催化剂SBA-15-SO₃H。XRD结果表明，该分子筛具有规则的六方立柱形介孔结构。SBA-15-SO3H用于叔丁醇和乙醇合成乙基叔丁基醚（ETBE）的醚化反应研究，分别考察了反应温度、原料配比和反应时间等因素对醚化反应的影响。最佳操作条件为：温度120 ℃，n(乙醇)∶n(叔丁醇)=2∶1，反应时间5 h，m(催化剂) ∶m(原料)=1∶10。在此条件下，叔丁醇的转化率为62.83%。     

HPWA/SBA-15催化合成对叔丁基苯酚

以SBA-15负载磷钨酸（HPWA）为催化剂、甲基叔丁基醚（MTBE）和苯酚为原料在钢密封间歇反应釜中进行催化合成对叔丁基苯酚的实验研究。考察了HPWA负载量、催化剂用量、反应温度、反应时间及原料配比对烷基化反应的影响。实验结果表明,反应温度为160 ℃、负载HPWA质量分数30%、反应时间3 h、催化剂用量为原料质量的5%和原料配比n(MTBE)∶n(苯酚)＝2∶1时,苯酚的转化率为85.1%, 对叔丁基苯酚的选择性66.87%。实验中HPWA/SBA-15分子筛表现出较高的活性及选择性。     

H_3O_(40)PW_(12)/ZrO_2催化合成2-叔丁基对甲酚

实验以H_3O_(40)PW_(12)/ZrO_2为催化剂,采用对甲酚与叔丁醇为原料,在三口烧瓶中合成了2-叔丁基对甲酚。考察了磷钨酸浓度、催化剂用量、温度、时间、投料比对反应的影响,采用15%H_3O_(40)PW_(12)/ZrO_2催化剂,加入5%该催化剂,反应温度80℃,n(对甲酚)/n(叔丁醇)=1∶1.2,反应时间4 h,2-叔丁基对甲酚收率最高,达到70%,催化剂易于与产物分离,重复性能较好。     

微波辅助ZrO2-SO42-/SBA-15催化合成棕榈酸甲酯

以三嵌段醚共聚物P123作为模板剂、正硅酸乙酯为硅源,合成介孔分子筛SBA-15.以SBA-15为载体,利用尿素水解法制备ZrO2-SO42-改性的固体酸催化剂,对其进行表征.实验结果表明,合成的固体酸催化剂具有典型的介孔结构特征.将催化剂应用于微波法催化合成棕榈酸甲酯,考察反应时间、反应温度、辐射功率、酸醇物质的量比和催化剂用量对酯化率的影响,结果表明,在n(十六酸)∶n(甲醇)=1∶15、SZ/SBA-15催化剂用量0.8g、反应时间20min、反应温度40℃和微波辐射功率400W条件下,酯化率可达87.70％,微波反应时间较传统合成方法大大缩短.     

SO42-/Al2O3-ZrO2/SBA-15固体酸催化合成棕榈酸甲酯

将Al(NO3)3.9H2O,Zr(NO3)4.5H2O与活化后的主体材料SBA-15分子筛通过尿素水解的方法,制备了改性SBA-15分子筛,进一步用硫酸浸渍处理改性分子筛以增强分子筛表面的酸活性中心。并采用红外光谱、扫描电镜、透射电镜等分析方法对试样进行了表征,结果表明,制得的催化剂SO24-/Al2O3-ZrO2/SBA-15仍然保持高度有序的介孔一维六角结构。并将其催化剂用于棕榈酸与甲醇的酯化反应中,采用正交实验确定较佳的工艺条件为:催化剂用量为1.2 g,n(棕榈酸)∶n(甲醇)=1∶12,反应时间为9 h,此条件下棕榈酸甲酯的反应收率可以达到82.3%,实验表明所合成的固体酸催化剂具有良好的催化性能。     

合成叔丁基苯酚的固体酸催化反应过程研究

在固定床反应器内进行了以固体酸催化合成叔丁基苯酚实验,结果表明,制备的催化剂活性稳定性优于HY分子筛。在反应压力6.0 MPa、反应温度260 ℃、n(苯酚)∶n(叔丁醇)=1∶3和质量空速4.4 h-1的较佳反应条件下进行苯酚与叔丁醇烷基化反应,苯酚转化率为78.3%,2-叔丁基苯酚选择性为10.3%,4-叔丁基苯酚选择性为63.5%,2,4-二叔丁基苯酚选择性为25.1%,催化剂活性稳定时间超过530 h。在反应压力6.0 MPa、反应温度240 ℃、n(苯酚)∶n(甲基叔丁基醚)=1∶3和质量空速1.3 h^-1条件下进行甲基叔丁基醚与苯酚烷基化反应,苯酚转化率为70.9%,2-叔丁基苯酚选择性为27.7%,4-叔丁基苯酚选择性为35.7%,2,4-二叔丁基苯酚选择性为29.7%。与叔丁醇相比,甲基叔丁基醚的苯酚烷基化活性和2,4-二叔丁基苯酚选择性均较高,但副产物较多。对于合成叔丁基苯酚,叔丁醇是较佳的烷基化试剂。     

PW_(12)-SBA-15催化剂的制备及其催化合成增塑剂TBC的研究

采用原位合成法将Keggin型结构的磷钨酸(PW_(12))负载于分子筛SBA-15上,制备出负载型催化剂,利用XRD、N2吸附-脱附、FTIR、NH3-TPD等技术对其进行表征。将负载型催化剂PW_(12)-SBA-15用于柠檬酸三丁酯(TBC)的催化合成,并对多种影响因素进行了分析。结果表明:SBA-15及PW_(12)的基本结构均能得到保持,催化剂具有良好的酸性中心;当PW_(12)负载量为27%、催化剂用量为1.4%、醇酸摩尔比为4:1、反应温度为150℃、反应时间为6 h时,酯化率达到95.59%;催化剂重复应用10次,催化性能稳定。     

改性MCM-41催化苯酚与叔丁醇烷基化反应性能研究

采用MCM-41分子筛催化剂进行液相催化苯酚与叔丁醇的烷基化反应,通过XRD、TEM、BET、NH₃-TPD等手段对催化剂进行表征,考察了反应条件对苯酚转化率、对叔丁基苯酚（PTBP）选择性以及改性处理对催化剂性能的影响。结果表明,酸改性后MCM-41分子筛并未改变其结构,酸性增强,微孔体积基本不变,比表面积、孔体积和孔径都增加。在反应温度为130℃、n（叔丁醇）∶n（苯酚）=7∶1的条件下,反应10 h内苯酚平均转化率为65%,PTBP选择性为60%。     

SBA-15分子筛负载磷钨酸催化合成己二酸

采用SBA-15分子筛等体积浸渍负载磷钨杂多酸制备了PW/SBA-15催化剂,应用XRD、DSG-TGA等对催化剂结构进行分析和表征。结果表明,SBA-15分子筛在负载磷钨酸后,磷钨杂多酸完全引入到SBA-15分子筛的骨架结构中,其稳定性大幅增加。同时采用"一锅煮"的方法用过氧化氢氧化环己烯制得己二酸,运用正交试验法和单因素实验法对催化剂性能进行评价。结果表明,催化剂用量1.75 g、反应时间9 h、反应温度80℃、n(H_2O_2)∶n(环己烯)=5.47∶1,反应开始加入13.75 mL的H_2O_2,4 h后再加入13.75 mL的H_2O_2条件下合成的己二酸收率和纯度最高。     

Characterization and catalytic properties of mesoporous CuO/SBA-16 prepared by different impregnation methods

CuO/SBA-16 catalysts were prepared by two different routes – the conventional impregnation method and the modified impregnation method with pH adjustment. These catalysts were characterized by X-ray diffraction (XRD), atomic absorption spectrometry (AAS), N₂ physisorption and hydrogen temperature programmed reduction (H₂-TPR) measurements which reveal that the cubic cage-like (Im3m) pore structure of the parent SBA-16 molecule sieves was well maintained throughout the synthesis. After introduction of Cu, a different CuO dispersion exists on these catalysts. The CuO/SBA-16 prepared by modified impregnation method has a single highly dispersed CuO which is considered as a highly efficient species for hydroxylation of phenol with H₂O₂. CuO/SBA-16 prepared by the conventional impregnation method shows the presence of bulk CuO species which is undesirable for this reaction.     

磷钨酸/SBA-15催化氧化-萃取柴油脱硫

以自制的SBA-15为载体,磷钨酸为活性组分,用过量浸渍法制备了HPW/SBA-15催化剂,并采用SEM、BET和TG-DTA对催化剂进行表征分析。H₂O₂为氧化剂,十六烷基三甲基溴化铵（CTAB）为相转移剂,以二苯并噻吩（DBT）的模型化合物（DBT为溶质、正辛烷为溶剂）进行氧化脱除为探针反应,考察了磷钨酸负载量和HPW/SBA-15的焙烧温度对催化剂活性的影响,同时考察了氧化-萃取工艺条件对真实柴油脱硫效果的影响。实验结果表明,磷钨酸最佳负载量为30%,HPW/SBA-15在250℃焙烧处理时活性最高;在n(H₂O₂)：n(S)=6、HPW/SBA-15用量为2.5%（基于柴油质量）、CTAB用量为0.4%（基于柴油质量）、萃取级数为4、温度60℃反应1.5h的条件下,柴油硫含量从1317mg/L降到39mg/L,脱硫率达到97.0%、收率不低于85.0%。气相色谱结果显示,该催化氧化脱硫体系容易脱除柴油中加氢难以脱除的二苯并噻吩及其衍生物。     

SBA-15的改性及催化文冠果油制备生物柴油

以介孔分子筛SBA-15为载体,采用直接合成法和后合成法镀饰Al后再负载碱金属盐KNO₃,制得负载型固体碱催化剂KNO₃-AlSBA-15和KNO₃-Al-SBA-15。用XRD、BET、SEM以及CO₂-TPD对催化剂进行表征。结果表明：在SBA-15上镀饰Al可以保护分子筛的介孔结构;进一步负载KNO₃,能够增强催化剂的碱性。将其应用于催化文冠果油酯交换制备生物柴油,结果显示催化剂KNO₃-Al-SBA-15的催化活性最好,优于传统均相催化剂,所得生物柴油产率可达92%,重复使用多次仍具有较好的催化效果。     

Promotion effect of cerium and lanthanum oxides on Ni/SBA-15 catalyst for ammonia decomposition

CeNi/SBA-15 and LaNi/SBA-15 catalysts were prepared by deposition–precipitation (DP) method and characterized by N₂ physical adsorption, XRD, H₂-TPR, H₂-chemisorption and TEM. Their catalytic performances in the ammonia decomposition reaction were tested and compared with Ni/SBA-15 catalyst. Addition of cerium and lanthanum oxides to the Ni/SBA-15 catalyst caused some decrease of BET surface area and pore volume of the catalysts, but led to a promotion effect to their catalytic activity which was closely related to the ratio of Ce (La)/Ni. The highest conversion of ammonia could be obtained when the Ce (La)/Ni ratio was around 0.3. The promotion effect is more evident on CeNi/SBA-15(0.3) than on LaNi/SBA-15(0.3) catalyst under identical reaction conditions. The CeNi/SBA-15 and LaNi/SBA-15 catalysts show smaller nickel particle size and easier reducibility in comparison with the Ni/SBA-15 catalysts.     

添加Sm对Pt /SBA-15催化苯完全氧化反应活性和热稳定性的影响

以Pt/SBA-15为催化剂,考察催化剂载体中添加Sm对于苯的完全氧化反应活性和热稳定性影响。采用了一种简便的记录起燃温度曲线和催化剂热稳定性评价方法,即向装载好催化剂的固定床反应器中持续通入恒定流量的反应气,逐步阶段性升高反应温度,同时在线检测出口尾气的浓度变化, 得到起燃温度曲线后,继续提高反应温度,然后恒定在某一设定的温度(如550℃)持续运行较长时间, 期间定时在线取样分析,如果有必要还可以连续考察降温情况下催化剂的反应活性情况。研究结果表明,几种催化剂低温活性次序为：Pt/SBA-15≈Pt/4%Sm₂O₃/SBA-15> Pt/Sm₂O₃> 4%Sm₂O₃/SBA-15,而对于高温稳定性则是Pt/4%Sm₂O₃/SBA-15> Pt/1.2%Sm₂O₃/SBA-15> Pt/SBA-15,Pt/Sm-SBA-15(SG)> Pt/SBA-15(SG)。总之,Sm的添加虽然未能提高Pt/SBA-15的低温催化活性,但是能明显提高催化剂在高温情况下活性的稳定性。1%Pt/4%Sm₂O₃/SBA-15同时具备较好的低温催化活性和高温稳定性,具有较好的应用前景。     

CoMo/Ti-SBA-15 catalysts for dibenzothiophene desulfurization

With a view to reducing the sulfur content in diesel fuels, novel desulfurization CoMo catalysts were supported on a Ti-loaded hexagonal mesoporous SBA-15 material. The Ti-SBA-15 substrates were synthesized using triblock copolymers as structure-directing agents. Catalytic activity was assessed in the model reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT), carried out in a batch reactor at T = 623 K and with a total hydrogen pressure of 3.1 MPa. The reaction proceeds via the direct desulfurization route (main route) and the hydrogenation (HYD) pathway. The incorporation of Ti into the SBA-15 afforded catalysts that were more active than the Ti-free counterpart, due to the enhancement of the DDS route in this reaction. This difference was explained in terms of a larger number of coordinately unsaturated sites (CUS) of the metal sulfide on Ti-loaded catalysts. Under steady-state conditions, the CoMoST20 catalyst with a Si/Ti ratio of 20 was the most active among the catalysts studied. Since this catalyst exhibited both Ti⁴⁺ ions incorporated into the SBA-15 framework and separate anatase TiO₂ clusters located on its surface, the activity enhancement on this sample was explained by the larger intrinsic activity of the “Co–Mo–S” phase located on these TiO₂ nanoparticles. The Ti-SBA-15 supports and the CoMo/Ti-SBA-15 catalysts were studied by N₂ adsorption–desorption isotherms, XRD, TEM, FTIR of adsorbed pyridine and NO, UV–vis DRS, TPR, micro-Raman and XPS spectroscopy.     

Preparation of High-Density Fuel Through Dimerization of β-Pinene

High-density fuel was prepared by catalytic dimerization and subsequent hydrogenation. Different amounts of phosphotungstic acid (H₃PW₁₂O₄₀, HPW) were loaded on mesoporous silica (SBA-15) by a simple impregnation method to prepare HPW/SBA-15 catalysts. The prepared catalysts were mesoporous. Characterizations indicated that the dispersion and the specific surface area depend on the HPW amount. The obtained dimers from catalytic dimerization of β-pinene underwent isomerization and then dimerized to form the heterogeneous products. At the optimum load of HPW, the HPW/SBA-15 catalyst displayed the highest catalytic activity and the increased yield of dimer for a 3-h reaction. After the subsequent hydrogenation reaction, the obtained hydrogenated dimer products displayed a density and a volume calorific value comparable to those of commercial JP-10.     

Hydrogenation of carbon dioxide over copper-pyrochlore/zeolite composite catalysts

The hydrogenation of CO₂ was studied over composite catalysts obtained by mixing Cu-based methanol synthesis catalyst and HY zeolite. A mechanism associating methanol synthesis and MTG (methanol to gasoline) reaction allowed the formation of C₁-C₄ hydrocarbons. It was found that the catalytic behaviors of the composite catalysts were favorably influenced by the characteristics of the methanol synthesis catalysts. The Cu-La₂Zr₂O₇ catalyst we recently developed associated with HY zeolite exhibited interesting performances in hydrocarbon synthesis. The addition of ZrO₂ to Cu---La₂Zr₂O₇/HY enhanced the ability to produce hydrocarbons. Comparing composite catalyst systems prepared with different Cu-based methanol synthesis catalysts, the effect of Na contamination on methanol and hydrocarbon formation over composite catalysts were also discussed.     

SBA-15固载酸性离子液体催化酯化反应性能

为了减少离子液体用量及解决催化剂分离问题,采用键合法制备了以SBA-15为载体的固载化离子液体催化剂[C₃SO₃HCP]HSO₄/SBA-15,通过FT-IR、TG、XRD、BET和TEM分析了催化剂的结构和稳定性。并将其应用于催化丁二酸酐和乙醇的酯化反应。结果表明:[C₃SO₃HCP]HSO₄被成功固定在SBA-15上,且具有较高的热稳定性和催化活性,克服了非均相催化剂活性不高与均相催化剂难以分离的不足。在催化剂用量为反应物总质量的5%、n(C₄H₄O₃):n(C₂H₅OH)=1:3,反应温度80℃;反应时间4 h、带水剂用量为反应物总质量的30%的条件下,酯收率达93.7%,且该催化剂循环使用8次后,仍具有较高的催化活性。此外,还考察了以[C₃SO₃HCP]HSO₄/SBA-15为催化剂催化合成系列酯也获得了较高的酯收率,且易于与产物酯分离。