ZSM-5(38)/Al-MCM-41复合分子筛对纤维素催化热解的影响

以纤维素为原料,以自制的不同硅铝比ZSM-5(38)/Al-MCM-41微-介孔复合分子筛为催化剂,在固定床反应器上进行了催化热解实验。采用XRD表征分子筛,采用GC-MS分析生物油成分,考查了催化剂的改变对生物质热解产物及生物油成分的影响。实验结果表明：添加催化剂后,生物油产率降低,且其含水率也有所增加。与未添加催化剂相比,生物油中D L-2,3-丁二醇有明显提高。其中,ZSM-5(38)/Al-MCM-41(20) 最有利于苯酚、愈创木酚 (2-甲氧基-苯酚) 的生成。此外,这几种催化剂均有利于小分子化合物的生成,其中,ZSM-5(38) 有利于C4~C5化合物的生成,微-介孔复合分子筛则有利于C6~C8化合物的生成。     

介孔分子筛对传统药物的原位载药及缓释研究

利用原位组装法将水难溶性的治疗冠心病药物槲皮素组装进入到介孔分子筛MCM-41孔道中,重点考察了介孔分子筛对药物的原位组装率和缓释率,验证此载药体系的优势。用X射线粉末衍射仪、扫描电镜、红外光谱对组装材料进行表征。原位组装法制得的产物载药率最高达到93%[m(药物)/m(药物总量)],与后组装制得产物的组装率70%相比,有明显提高;测定体外模拟肠液中的缓释率,可知原位组装的产品释放总量约为13 h后基本不再释放,总量大概为93%,高于后组装产品(87.25%)。实验结果表明MCM-41介孔分子筛原位组装槲皮素药物分子有明显优势。     

槲皮素在介孔分子筛孔道中的组装与缓释研究

采用后组装法将非水溶性的治疗冠心病药物槲皮素组装进入MCM-41介孔分子筛的孔道中,药物组装率达37%[m(药物)/m(药物总量)],用XRD,扫描电镜和IR对药物组装体进行了表征;通过测定组装体在体外模拟人工小肠液中的溶出速率,表明制得了槲皮素/MCM-41缓释体系。     

α-O-4型木质素二聚体模型物热解解聚机理

为了解木质素α-O-4连接部分的热解机理,以4-(3-羟基-1-苯氧基丙基)-苯酚为α-O-4型木质素二聚体模型化合物,采用密度泛函理论M06-2X/6-31+G(d,p)方法,对该二聚体热解过程中的反应物、中间产物、过渡态、产物进行几何结构的完全优化,通过计算各可能路径的反应能垒,确定了该模型化合物主要通过Cα-O键的均裂和协同断裂的方式发生裂解反应,主要生成苯酚、4-甲基苯酚、4-乙烯基苯酚和香豆醇等酚类产物以及乙醇、甲醇、甲醛等小分子物质,由此首次从理论上揭示了该模型化合物的详细热解解聚过程。     

山楂核干馏油GC-MS主要成分分析及含量测定

本研究目的在于建立气相色谱-质谱联用法(GC-MS)分析山楂核干馏油中挥发油、脂溶性成分以及气相色谱法(GC-FID)同时测定山楂核干馏油中活性成分的定量分析方法。采用GC-MS法对山楂核干馏油化学成分进行分析,共分析出62种化学成分,用峰面积归一化法测定各成分的相对百分含量,含量最高的化合物为醛类,占总量的55.96%。以GC-FID法同时测定山楂核干馏油中的主要成分的含量(糠醛、愈创木酚、2,6-二甲基苯酚、2-甲基苯酚、苯酚、2-甲氧基-4-甲基苯酚、2,6-二甲氧基苯酚、四氯愈创木酚、1,2,3-三甲氧基苯、3,4,5-三甲氧基甲苯),测得加样回收率范围为100.06%~102.44%,RSD范围为2.98%~4.57%。本方法准确、简便、重复性好,为山楂核干馏油制剂的内在质量控制及提升废弃物山楂核循环利用价值提供依据。     

巢湖蓝藻与农业废弃物共热解制取生物质油研究

采用蔗渣、玉米秸秆和棉花秸秆3种废弃物与蓝藻进行混合共热解试验,考察废弃物的加入对蓝藻热解液体产率及组分的影响。结果表明:添加3种废弃物均使共热解液体产率呈下降趋势。当蓝藻与废弃物以1∶1混合共热解时,以蓝藻和玉米秸秆共热解液体产率最高,为61.8%,且除苯酚类以外,液体产物组分与单一蓝藻热解产物组分相近,含氮化合物含量明显降低,相对含量由18.49%降至8.15%。与其它2种废弃物相比,蓝藻与玉米秸秆在适当比例下的共热解有利于改善热解油品质。     

熔盐热裂解生物质制生物油

为探讨热裂解条件对熔盐中生物质热裂解制生物油的影响,在自行设计的反应器中,以摩尔比为7∶6的ZnCl2-KCl混合熔盐作为热裂解的热载体、催化剂和分散剂,考察了500 ℃时添加的金属盐和生物质原料的影响,并采用气相色谱-质谱仪 (GC-MS) 对生物油的主要组成进行了分析。结果表明：添加的金属盐显著影响热裂解产物得率,稀土金属盐显著提高生物油得率,降低生物油的含水率,添加摩尔分数为5.0％ LaCl3时生物油得率为32.0％,含水率为61.5％;水稻秸秆热裂解的生物油和焦炭得率较高,稻壳热裂解的气体得率较高;金属添加盐对生物油组成有较强的选择性,LiCl和FeCl2对生物质向小分子裂解具有较强的催化作用,而CrCl3、CaCl2和LaCl3对生物油二次裂解具有抑制作用。研究结果为熔盐热裂解生物质制生物油提供了参考。     

固定化脂肪酶的创制及其在乙酸肉桂酯无溶剂制备中的应用

采用模板法结合辛基(C8)表面修饰制备疏水有序介孔SiO₂载体(OMS-C₈),在此基础上制得固定化脂肪酶(CSL@OMS-C8),成功应用于乙酸肉桂酯的无溶剂酶法制备。利用扫描电镜(SEM)、透射电镜(TEM)、N2-吸附脱附、傅里叶红外(FTIR)对载体材料和固定化酶进行表征。结果显示,OMS具有整齐有序的介孔结构,比表面积达149.9 m2/g,平均孔径为15 nm。经过疏水改性后,接触角从20°提高到120°。优化获得了乙酸肉桂酯的最佳反应条件为温度50℃,肉桂醇与乙酸乙烯酯的摩尔比1∶5,固定化酶添加量2 g/L,反应时间2 h,转化率达到96.6%。催化剂经过5次重复使用肉桂醇的转化率仍能达到80%。     

美丽海绵提取物防污损作用

从美丽海绵分离提取了2-去氧-1-氢-1,2,4,三唑、环(脯氨酸-甘氨酸)、尿嘧啶、环(脯氨酸-丙氨酸)、6-氨基嘌呤、4-(1-苯乙基)苯酚、1-氢-1,2,4,三唑和胆甾-5-烯-3β,7α-二醇等8种化合物,并研究了其对网纹藤壶金星幼虫的影响,其中6-氨基嘌呤(7.1 μg/cm2)和4-(1-苯乙基)苯酚(5.9μg/cm2)对金星幼虫具有明显的毒杀作用.美丽海绵可能通过这些活性化合物的协同作用来防止它种生物附着污损.     

花生茎叶酚性成分研究

运用大孔树脂对花生茎叶提取液进行富集,不同浓度乙醇洗脱,硅胶、RP-18、Sephadex LH-20等多种材料进一步分离纯化,研究花生茎叶化学成分,并通过理化方法和光谱分析对化合物进行结构鉴定。结果表明:从花生茎叶大孔树脂10%乙醇洗脱部位中分离并鉴定了10个化合物,分别为邻苯二甲酸二异丁酯(1)、水杨酸(2)、儿茶酚(3)、对羟基苯甲酸(4)、(反)-3,4-二羟基苯丙烯酸(5)、对羟基苯酚(6)、邻苯二甲酸二丁酯(7)、3,4-二羟基苯乙醇(8)、对羟基苯乙醇(9)、3,4-二羟基苯甲酸(10)。除化合物1、2和4外,其余均为首次从该植物中分离得到。     

The effects of different catalysts on the pyrolysis of industrial wastes (olive and hazelnut bagasse)

Pyrolysis of olive and hazelnut bagasse biomass samples with two selected catalysts, namely activated alumina and sodium feldspar, have been conducted in a fixed-bed reactor. Experiments were carried out under certain pyrolysis conditions in a fixed-bed Heinze reactor. The catalyst was mixed with feedstock in different percentages. The effects of catalysts and their ratio (10%, 20%, 30% and 40% w/w) on the pyrolysis product yields were investigated and the results were compared with the results of experiments performed without catalyst under the same conditions. The maximum bio-oil yields for the bio-oils obtained from pyrolysis of olive bagasse were found as 37.07% and 36.67% on using activated alumina and sodium feldspar as catalysts, respectively, while these values were 27.64% and 31.68%, respectively, for the bio-oils from hazelnut bagasse. The oxygen contents of the bio-oils were also markedly reduced while the yield of bio-oil was reduced by the use of catalysts. The pyrolysis oils were examined using some spectroscopic and chromatographic analysis techniques. The results were compared with the petroleum fractions and the possibility of being a potential source of bio-oils was investigated.     

Asymmetric epoxidation of olefins using novel chiral dinuclear Mn(III)-salen complexes with inherent phase-transfer capability in ionic liquids

Two new chiral dinuclear Mn(III)-Salen complexes with inherent phase-transfer capability have been synthesized, which serve as catalysts in the asymmetric epoxidation of nonfunctionalized alkenes. Experimental results show these complexes are effective catalysts for the asymmetric epoxidation of some cyclic alkenes and the catalysts have certain inherent phase-transfer capability during the epoxidation because of their weak water solubility. In general, good enantioselectivity and acceptable yields were achieved when NaClO was used as oxidant under three different reaction systems. Among these alkenes, the catalyst 6a gave the highest ee (94%) for 6-chloro-2,2-dimethylchromene in the presence of ionic liquid 2. Additionally, the recovery and recycling of one dimeric Mn(III)-Salen complex were tested to investigate atom efficiency of the catalyst in different reaction systems on the alkenes epoxidations. The catalyst 6a could be recovered and recycled for six times without losing activity and selectivity.     

Salen complexes with bulky substituents as useful tools for biomimetic phenol oxidation research.

The catalytic properties of bulky water-soluble Co-, Cu-, Fe- and Mn-salen complexes in the oxidation of phenolic lignin model compounds have been studied in aqueous water--dioxane solutions (pH 3--10). Mn catalysts were found to oxidize coniferyl alcohol in a same reaction time as horseradish peroxidase (HRP) enzyme and Mn and Co catalysts showed different regioselectivity suggesting a different substrate to catalyst interaction in the oxidative coupling. When the oxidation of material more relevant to plant polyphenolics was studied, the results indicated that the complexes catalyze one- and two-electron oxidations depending on the bulk of the substrate.     

A Curtin–Hammett mechanism for the copolymerization of ethylene and methyl acrylate monomer using a PymNox nickel catalyst as revealed by DFT computational studies

In this work, the copolymerization of ethylene and methyl acrylate (MA) as catalyzed by a new Ni-based PymNox organometallic compound was studied computationally. We recently tested the behavior of this type of catalyst in ethylene homopolymerization. Experimental results show that the unsubstituted catalyst Ni2 (aldimino PymNox catalyst) is unable to incorporate the MA monomer, whereas methyl-substituted Ni1 (acetaldimino PymNox catalyst) is able to achieve copolymerization. The reactivities of both catalysts were examined using density functional theory (DFT) models. Based on energy profiles calculated at the BP86 level, a Curtin–Hammett mechanism was proposed to explain the different reactivities of the catalysts in ethylene/MA copolymerization. Our results indicate that the methyl substituent Ni1 introduces additional steric hindrance that results in a catalyst conformation that is better suited to polar monomer incorporation. This model provides insights into the design of new catalysts to produce polar functionalized copolymers based on ethylene.     

Development of heterogeneous base catalysts for biodiesel production

Investigations were conducted on heterogeneous base catalysts for the transesterification of oil aimed at effective production of biodiesel. Thirteen different kinds of metal oxides containing calcium, barium, magnesium, or lanthanum were prepared as catalysts. Their catalytic activities were tested for transesterification at 60 degrees C with a 6:1 molar ratio of methanol to oil and a reaction time of 10h. The calcium-containing catalysts - CaTiO3, CaMnO3, Ca2Fe2O5, CaZrO3, and CaO-CeO2 - showed high activities and approximately 90% yields of methyl ester. Furthermore, catalytic durability tests were performed by repeating the transesterification reaction several times with the calcium-containing catalysts recovered from the previous reaction mixture. It was found that CaZrO3 and CaO-CeO2 show high durability and have the potential to be used in biodiesel production processes as heterogeneous base catalysts.     

Integrated biodiesel production: a comparison of different homogeneous catalysts systems

The most common catalysts for biodiesel production are homogeneous basic catalysts. In the present paper, a comparison is made of different basic catalysts (sodium methoxide, potassium methoxide, sodium hydroxide and potassium hydroxide) for methanolysis of sunflower oil. All the reactions were carried out under the same experimental conditions in a batch stirred reactor and the subsequent separation and purification stages in a decanter. The analytical methods included gas chromatography and the determination of fat and oil conventional parameters. The biodiesel purity was near 100 wt.% for all catalysts. However, near 100 wt.% biodiesel yields were only obtained with the methoxide catalysts. According to the material balance of the process, yield losses were due to triglyceride saponification and methyl ester dissolution in glycerol. Obtained biodiesel met the measured specifications, except for the iodine value, according to the German and EU draft standards. Although all the transesterification reactions were quite rapid and the biodiesel layers achieved nearly 100% methyl ester concentrations, the reactions using sodium hydroxide turned out the fastest.     

Methods for the immobilization of lipases and their use for ester synthesis

The lipase from Pseudomonas fluorescens was immobilized onto five different carriers: celite, octyl-silica, aminopropyl-silica, gluterdialdehyde-activated silica and Eupergit C250L. Activities and operational stabilities of the prepared catalysts were compared using the enantioselective acylation of (R,S)-1-phenylethanol by vinyl acetate as acyl donor and t-butylmethyl ether with variable water content (0.038-0.97% v/v) as reaction medium. The above carriers provide catalysts with widely different specific activities ranging from excellent 25 mmol/h mg protein (celite) to 0.07 mmol/h mg protein (glutardialdehyde-activated silica) on the lower end. The lipase immobilized onto Eupergit C250L exhibited the best operational stability among the catalysts studied. It retained 30% of its initial activity after 11 cycles of application, each with a duration between 2 and 6 h.     

Comparison of sulfuric and hydrochloric acids as catalysts in hydrolysis of Kappaphycus alvarezii (cottonii)

In this study, hydrolysis of marine algal biomass Kappaphhycus alvarezii using two different acid catalysts was examined with the goal of identifying optimal reaction conditions for the formation of sugars and by-products. K. alvarezii were hydrolyzed by autoclave using sulfuric acid or hydrochloric acid as catalyst with different acid concentrations (0.1-1.0 M), substrate concentrations (1.0-13.5%), hydrolysis time (10-90 min) and hydrolysis temperatures (100-130 (°)C). A difference in galactose, glucose, reducing sugar and total sugar content was observed under the different hydrolysis conditions. Different by-product compounds such as 5-hydroxymethylfurfural and levulinic acid were also observed under the different reaction conditions. The optimal conditions for hydrolysis were achieved at a sulfuric acid concentration, temperature and reaction time of 0.2 M, 130 °C and 15 min, respectively. These results may provide useful information for the development of more efficient systems for biofuel production from marine biomass.     

Catalytic pyrolysis of tobacco rob: kinetic study and fuel gas produced

The pyrolysis kinetics of tobacco rob (TR) was investigated using thermogravimetric analysis (TGA) under inert atmosphere, adding chemicals (dolomite and NiO) as catalysts by catalytic-mixing method. The TGA results showed that mass loss and mass loss rates were affected by catalysts. The conversion rates increased while the activation energy decreased. Moreover, the thermal decomposition behaviors of TR were studied in the fixed-bed reactor using dolomite and NiO/γ-Al₂O₃ as catalysts by catalyst-bed method. A series of experiments had been performed to explore the effects of catalysts, and reaction temperature on the composition and yield of fuel gas. The experiments demonstrated that the catalysts had a high activity of cracking tar and hydrocarbons, as well as yielding a high fuel gas production. For both methods, dolomite and NiO revealed better catalytic performance as a view of enhancing conversion rates and increasing product gas yield.