磺酸功能化MIL-101(Cr)固体酸催化降解纤维素为葡萄糖

以葡萄糖为原料,发烟硫酸为磺酸化试剂,MIL-101(Cr)为载体制备了碳基磺酸化固体酸催化剂C-SO_3H/MIL-101(Cr)。通过SEM、酸碱滴定、FT-IR和XRD等手段对催化剂进行表征;并考察了其催化降解纤维素为葡萄糖的水解反应性能。结果表明,磺酸化48 h的C-SO_3H(48)/MIL-101(Cr)固体酸催化剂能高效降解纤维素水解为葡萄糖,在反应温度140℃和反应时间12 h下,纤维素转化率达到91.7%,葡萄糖选择性为78.9%。同时催化剂稳定性较好,重复使用一次后,纤维素转化率降至85.3%。对催化剂活性下降原因进行探讨,结果表明,催化剂失活是由于在反应过程中催化剂表面磺酸基团脱落所造成的。     

炭质磺酸化固体酸催化剂的制备及催化合成生物柴油研究

以秸秆为原料,采用炭化和磺化方法制备炭质磺酸化固体酸催化剂,并通过XRD、SEM和FTIR对制备的催化剂结构进行表征。通过催化油酸和甲醇酯化反应制备生物柴油,考察相关因素对油酸转化率的影响。结果表明,在反应温度为68℃,催化剂质量为油酸质量的7%,反应时间为5 h,醇酸的物质的量比为12∶1,生物柴油转化率可达94.83%。     

炭质磺酸化固体酸催化剂的制备及催化合成生物柴油研究

以秸秆为原料,采用炭化和磺化方法制备炭质磺酸化固体酸催化剂,并通过XRD、SEM和FTIR对制备的催化剂结构进行表征。通过催化油酸和甲醇酯化反应制备生物柴油,考察相关因素对油酸转化率的影响。结果表明,在反应温度为68℃,催化剂质量为油酸质量的7%,反应时间为5 h,醇酸的物质的量比为12∶1,生物柴油转化率可达94.83%。     

一种微孔磺酸化固体酸的合成及其催化性能

通过对一种微孔有机芳香聚合物进行磺酸化制备了微孔固体酸催化剂。用傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、表面酸量测定、元素分析和比表面积测试对催化剂进行了表征,并以油酸与甲醇的酯化反应评价了催化剂的催化活性。结果表明,该催化剂具有较大的比表面积(540 m2/g)和孔容(0.40 cm3/g),表面酸量为2.9 mmol/g,其对酯化反应的催化活性要高于工业离子交换树脂(Amberlyst-15),在75℃反应6 h后,油酸转化率高达93%,并可再生使用。     

固体超强酸催化剂的研究进展

介绍了固体超强酸催化剂的特点和制备方法,讨论了固体超强酸催化剂对缩醛(酮)反应、酯化反应等反应催化作用,展望了固体超强酸催化剂的研发趋势.     

不同基质碳基固体酸催化剂制备及其催化酯化性能

分别以葡萄糖、蔗糖和淀粉为基质,对甲苯磺酸为磺酸基来源,采用一步碳化法制得3种碳基固体酸催化剂。用透射电子显微镜(TEM)、多点BET(Brunauer-Emmett-Teller)法(BET)、X射线衍射法(XRD)、红外光谱、元素分析和热重分析等对催化剂进行了表征,并以新型双子表面活性剂1,4-丁二醇双琥珀酸聚醚(3)正辛基混合双酯磺酸钠合成中的双酯化反应Ⅱ为探针,比较了三者的催化活性及重复性。结果表明:三种催化剂均为层状和片状的无定形碳架结构,葡萄糖基质碳基固体酸催化剂上磺酸基团含量最高,在制备工艺下均有较好的热稳定性;三者重复性均较好,其中葡萄糖基质碳基固体酸催化剂对于探针反应的催化酯化活性最好。     

生物质炭基磺酸化固体酸的制备及催化性能比较

以常见的碳水化合物葡萄糖、纤维素、蔗糖、医用棉为原料,采用碳化磺化法制备得到四种碳基磺酸化固体酸催化剂.采用傅里叶转换红外光谱(FT-IR )、表面酸量的测定等手段对这四种碳基磺酸化固体酸进行了表征.同时,将其用在乙酸乙酯的合成中,比较了其催化效率、稳定性.此外,还进行了再生实验.     

一种新型微孔磺酸化固体酸的合成与其催化性能

通过对一种新型的微孔芳香骨架的有机聚合物进行磺酸化制备了微孔固体酸催化剂。利用傅里叶变换红外光（FT-IR）、X射线衍射（XRD）、表面酸量测定、元素分析和比表面积测试等手段对催化剂进行了表征,并以油酸与甲醇的酯化反应评价了催化剂的催化活性。结果表明：该催化剂具有较大的比表面积和孔容,表面酸量为2.9mmol/g,其对酯化反应的催化活性要高于工业离子交换树脂（Amberlyst-15）,在75℃反应6 h后,油酸转化率可达93%,并可再生使用。     

磺化碳固体酸催化剂的制备及其催化性能的研究

以微晶纤维素(MCC)为原料制备了碳基磺酸化固体酸催化剂,用该磺化碳固体酸MCC进行糖化水解,考察其催化水解微晶纤维素的最优条件及碳化温度对催化剂催化活性的影响,并对其重复使用性及再生进行了研究。结果表明,反应温度180℃、反应时间6 h、催化剂用量0.15 g为最佳反应条件,最高糖产率为68.71%;400℃为最佳碳化温度。催化剂重复使用后,由于表面磺酸基团的脱落其活性有所下降,可以通过再磺化得到恢复。     

硫酸镓/凹凸棒石黏土固体酸催化剂的制备及其催化性能

采用凹凸棒石黏土负载硫酸镓(Ga2(SO4)3)制备了Ga2(SO4)3/凹凸棒石黏土固体酸催化剂,采用红外光谱及X衍射光谱等对催化剂结构进行了表征。通过乳酸丁酯的合成考察了催化剂的较优制备条件和催化性能,并对相应催化反应进行了动力学研究。结果表明催化剂的较优制备条件是:凹凸棒石黏土经1.2mol/L硫酸溶液酸化处理,Ga2(SO4)3负载量为5.7%,焙烧温度350℃,焙烧时间2.5h。在较优酯化反应条件下,平均酯化率为95.5%。动力学研究表明反应为准一级反应,表观活化能为45.072kJ/mol,378K时反应速率常数为2.35×10--2 min--1。     

二氧化硅-磺酸催化制备生物柴油的研究

通过溶胶-凝胶法制备二氧化硅,进而与氯磺酸反应制得二氧化硅-磺酸(SiO2-SO3H)固体酸催化剂,用于大豆油与乙醇的酯交换反应制备生物柴油,考察了催化剂的处理温度、乙醇与大豆油的摩尔比、催化剂用量、原料油油酸含量和反应时间的影响.结果表明,二氧化硅-磺酸(SiO2-SO3H)具有较高的酯交换反应催化活性.制备生物柴油的最佳条件如下:催化剂处理温度为120℃、醇油摩尔比为6∶1、催化剂质量分数为5.0%(以大豆油计)、正庚烷的质量分数(以大豆油计)为30.0%、反应时间为6.0 h,此时生物柴油产率可达97.84%.与固体碱催化剂相比,固体酸催化剂对原料的酸度有更强的适应性.     

松木粉制备高比表面积炭基固体酸催化剂

以一种廉价的农林废弃物——松木粉为原料,首先经过炭化和活化处理,制备活性炭,再通过苯磺酸重氮盐还原法处理活性炭引入磺酸基团(—SO₃H),从而制备出具有高比表面积的炭基固体酸催化剂(AC-SO₃H)。其比表面积达到 1364 m²/g,磺酸基密度为 1.36 mmol/g。以乙酸的酯化反应考察了炭基固体酸催化剂的催化活性,并与Amberlyst-15、Nafion NR50以及Nafion SAC-13等几种固体酸催化剂进行了比较。实验结果表明,炭基固体酸催化剂的催化活性仅略低于Amberlyst-15,高于Nafion NR50和Nafion SAC-13,炭基固体酸催化剂的成本也远远低于Nafion NR50和Nafion SAC-13。研究结果表明,以松木粉为原料,通过炭化、活化和磺化处理能够得到性能优异且成本低廉的炭基固体酸催化剂。     

松木粉制备高比表面积炭基固体酸催化剂

以一种廉价的农林废弃物——松木粉为原料,首先经过炭化和活化处理,制备活性炭,再通过苯磺酸重氮盐还原法处理活性炭引入磺酸基团（—SO3H）,从而制备出具有高比表面积的炭基固体酸催化剂（AC-SO3H）。其比表面积达到1364 m2/g,磺酸基密度为1.36 mmol/g。以乙酸的酯化反应考察了炭基固体酸催化剂的催化活性,并与Amberlyst-15、Nafion NR50以及Nafion SAC-13等几种固体酸催化剂进行了比较。实验结果表明,炭基固体酸催化剂的催化活性仅略低于Amberlyst-15,高于Nafion NR50和Nafion SAC-13,炭基固体酸催化剂的成本也远远低于Nafion NR50和NafionSAC-13。研究结果表明,以松木粉为原料,通过炭化、活化和磺化处理能够得到性能优异且成本低廉的炭基固体酸催化剂。     

Biodiesel Production Using a Carbon Solid Acid Catalyst Derived from β‐Cyclodextrin

A novel carbon solid acid catalyst was prepared by incomplete hydrothermal carbonization of β‐cyclodextrin into small polycyclic aromatic carbon sheets, followed by the introduction of –SO₃H groups via sulfonation with sulfuric acid. The physical and chemical properties of the catalyst were characterized in detail. The catalyst simultaneously catalyzed esterification and transesterification reactions to produce biodiesel from high free fatty acid (FFA) containing oils (55.2 %). For the as‐prepared catalyst, 90.82 % of the oleic acid was esterified after 8 h, while the total transesterification yield of high FFA containing oils reached 79.98 % after 12 h. By contrast, the obtained catalyst showed comparable activity to biomass (such as sugar, starch, etc.)‐based carbon solid acid catalyst while Amberlyst‐15 resulted in significantly lower levels of conversion, demonstrating its relatively high catalytic activity for simultaneous esterification and transesterification. Moreover, as the catalyst can be regenerated, it has the potential for use in biodiesel production from oils with a high FFA content.     

Synthesis and characterization of SBA-polyperoxyacid: An efficient heterogeneous solid peroxyacid catalyst for epoxidation of alkenes

SBA-propy-3-allyl-imidazolium chloride (SBA-Im-Allyl) was easily prepared by nucleophilic substitution of SBA-propylchloride (SBA-Cl) with imidazole and then quaternization with allyl chloride. Then, a novel solid polyperoxyacid was synthesized by anchoring and oxidation of polyacrylic acid onto the surface of SBA-Im-Allyl. FT-IR, SEM, TGA–DTG and BET have been used to characterize the solid polyperoxyacid. This new catalyst did not leach from the support and can be recycled by treatment with hydrogen peroxide solution, and also loading of the catalyst was measured by iodometric titration. The solid polyperoxyacid shows efficient catalytic activity toward epoxidation of alkenes.     

新型有序介孔炭基固体酸的制备及其催化双酚A合成

采用软模板法制得具有高度有序介孔孔道结构、高密度-SO₃H基团的新型有序介孔炭基固体酸催化剂。通过N₂吸附-脱附、X射线衍射、透射电镜、EDX能谱以及酸碱滴定等手段对催化剂进行了表征,考察了炭化温度对介孔炭基固体酸催化剂介孔孔道结构、表面酸性以及催化活性的影响。结果表明,500 ℃是最适宜的炭化温度,该炭化温度下制备的催化剂介观有序性较好且酸密度较高。所得的催化剂在丙酮与苯酚缩合生成双酚A的反应中表现出明显高于其它3种固体酸催化剂（001×7,D072,无定型炭基固体磺酸）的活性。可见,有序介孔炭基固体酸是一种高效的新型固体酸催化剂,在双酚A领域具有较好的应用潜力。     

负载型Cs2.5H0.5PW12O40醚化催化剂的制备与催化性能

制备了负载型磷钨酸铯 (Cs2 5H0 5PW1 2 O4 0 )催化剂 ,考察了载体种类、载体性质、制备方法和制备条件对催化剂性能的影响 ,对制备的催化剂进行了表征 ,并考察了负载型Cs2 5H0 5PW1 2 O4 0 作为醚化催化剂的催化活性 结果表明 ,大孔硅胶是Cs2 5H0 5PW1 2 O4 0 的适宜载体 ,硅胶的钠含量越低制备的Cs2 5H0 5PW1 2 O4 0 SiO2 催化剂的活性越高 .采用一步法和二步法制备的Cs2 5H0 5PW1 2 O4 0 SiO2 催化剂均具有较强的酸性、催化活性以及良好的稳定性 ,可以替代液体酸和阳离子交换树脂 ,成为一种环境友好的固体酸催化剂     

Sulfonated rice husk ash (RHA-SO3H): A highly powerful and efficient solid acid catalyst for the chemoselective preparation and deprotection of 1,1-diacetates

Rice husk ash (RHA), as a source of amorphous silica, was treated with chlorosulfonic acid and sulfonated rice husk ash (RHA-SO₃H) as a highly powerful solid acid catalyst was obtained and characterized with a variety of techniques including IR, TGA, SEM, XRD, pH analysis, Hammett acidity function and BET method. This solid acid showed excellent catalytic activity for the protection and deprotection of aldehydes with Ac₂O at room temperature under solvent free conditions. The procedure gave the products in excellent yields in very short reaction times and good to high yields. Also this catalyst can be reused for several times without loss of its catalytic activity.     

磺酸磁性石墨烯固体酸的制备、表征及初步应用研究

以氧化石墨烯,Co（NO3）2·6H2O和Fe（NO3）3·9H2O为离子源利用水热法一步制备磁性石墨烯（Co Fe2O4-h GO）,用磺酸重氮盐将其重氮化制得磺酸磁性石墨烯固体酸,采用FT-IR、XRD、VSM和酸碱反滴定法测对其进行了表征。结果表明,链接石墨烯的Co Fe2O4为单相立方尖晶石结构,平均粒径为27 nm,饱和比磁化强度MS为29.7 A·m2/kg,其表面酸量为2.7 mmol/g。用乙酸与正己醇的酯化反应初步评估其催化性能：在90℃,乙酸与正丁醇摩尔比为1∶1,催化剂用量为3wt%,反应时间为4 h的条件下,乙酸转化率为59.1%。     

Construction of a Brönsted-Lewis solid acid catalyst La-PW-SiO2/SWCNTs based on electron withdrawing effect of La(III) on π bond of SWCNTs for biodiesel synthesis from esterification of oleic acid and methanol

A novel solid Brönsted-Lewis acid catalyst La-PW-SiO₂/SWCNTs (single-wall carbon nanotubes) was synthesized from the synergistic modification of H₃PW₁₂O₄₀ (HPW) by single-walled carbon nanotubes functionalized with sidewall hydroxyl groups (SWCNTs–OH) and La³⁺ via sol–gel method. The freshly prepared catalyst was characterized by several methods, and the catalytic activity and stability of it were studied from the esterification of oleic acid and methanol. Results showed that the highest conversion of oleic acid was 93.1% (mass) and maintained as high as 88.7% (mass) after six cycles of La-PW-SiO₂/SWCNTs. The high catalytic activity and stability of La-PW-SiO₂/SWCNTs can be attributed to the strong electron withdrawing effect of La³⁺ on π bond of SWCNTs, because it can facilitate the formation of a large number of strong Lewis acid sites. Therefore, the reduction of catalytic activity of a solid acid catalyst due to the fact that hydration reaction of its Brönsted acid sites can be effectively reduced. La-PW-SiO₂/SWCNTs can be an efficient and economical catalyst, because it shows good catalytic activity and stability.