酸性离子液体催化脂肪酸甲酯聚合制备二聚酸甲酯

 以 Brönsted-Lewis 酸性离子液体为催化剂, 用于催化生物柴油中不饱和脂肪酸甲酯聚合制备二聚酸甲酯反应, 考察了催化剂种类、催化剂用量、反应温度和时间等因素对聚合反应性能的影响, 得到较佳的反应条件. 结果表明, 当以 1-(3-磺酸)-丙基-3-甲基咪唑氯锌酸盐[HO3S-(CH2)3-mim]Cl-ZnCl2 (ZnCl2 摩尔分数为 0.67) 为催化剂, 生物柴油 15 g, m(生物柴油):m(离子液体) = 15:1, 于 240 oC 下反应 6 h 时, 二聚酸甲酯收率为 63.2%, 其中三聚体含量小于 5%. 另外, 该催化剂重复使用 5 次后, 二聚酸甲酯收率仍超过 63%, 表明其具有较好的重复使用性能. 离子液体的 Brönsted 和 Lewis 酸位的协同效应显著提高了其催化活性.     

焙烧温度对Nb2O5/α-Al2O3催化剂结构及催化性能的影响

 制备了Nb2O5/α-Al2O3催化剂并用于环氧乙烷水合反应制乙二醇,采用X射线衍射,热重-差热分析,红外光谱,吸附氨的程序升温脱附,吸附环氧乙烷的程序升温脱附,扫描电镜和透射电镜研究了焙烧温度对催化剂物理化学性质及催化性能的影响. 结果表明,焙烧温度明显影响氧化铌催化剂的结构、酸量及酸强度. 催化剂的结构不同,环氧乙烷在催化剂表面的吸附强度存在明显差别,而催化剂的酸量和酸强度影响其催化性能.     

粘土孔结构及添加铈对于催化剂上苯吸附-脱附-催化氧化性能的影响

采用3种不同孔结构的粘土材料,即Na型-蒙脱土(Na-mmt)、Al柱撑粘土(Al-PILC)和AlCe复合柱撑粘土(AlCe-PILC),以上述材料为载体,负载Mn和MnCe作为易挥发有机物(VOC)苯的氧化催化剂。利用N2吸附、程序升温还原(TPR)和程序升温表面反应(TPSR)等手段对催化剂的织构-结构、氧化-还原和吸附-脱附等性能进行了表征和分析。结果表明对于具有高比表面积和大孔径的改性粘土材料,添加适量的Ce有利于催化剂对低浓度苯的吸附,吸附量显著增加、脱附温度提高,上述条件都有利于对低浓度苯的深度氧化。同时,这一研究结果对改善"吸附-催化"一体化的低温吸附、高温脱附及氧化性能有极其重要的意义。     

芳香族二腈的聚合

具有(?)结构的芳香族二腈能用Lewis酸催化剂在约300℃进行聚合反应。研究了不同结构的二腈的聚合反应速度,并对所得聚合物的热氧化稳定性及形变温度进行测定。用红外光谱分析法证实了由氰基三聚环化生成了1,3,5-三嗪环。     

扭辫法对糠酸聚合反应机理的研究

应用扭辫分析法(TBA)及IR谱的解析,研究了糠酸在浓硫酸催化下的开环聚合反应机理,探讨了催化剂用量及温度等对聚合反应的影响。结果表明,在浓硫酸存在下,随着温度的升高,糠酸的聚合反应历程为分段的逐步聚合过程;糠酸在210℃以后方可聚合完全;糠酸树脂在350℃以下耐热性良好。     

多钨酸盐修饰ZrO2气凝胶催化四氢呋喃开环聚合

采用过量浸渍结合溶剂蒸发将磷钨杂多酸(TPA)分散于ZrO₂气凝胶表面(TPA的质量分数为5%-45%), 再经750 °C空气气氛焙烧得到多钨酸盐修饰ZrO₂固体酸催化剂. 借助N₂吸附、X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱、氨程序升温脱附(NH₃-TPD)和吡啶吸附红外(Py-IR)光谱对催化剂的结构及酸性质进行表征, 针对四氢呋喃(THF)开环聚合反应考察其酸催化性能. 研究发现, TPA与ZrO₂之间较强的相互作用抑制了ZrO₂的晶化, 同时也在一定程度上稳定了TPA的Keggin(凯金)-阴离子结构. 高温焙烧的催化剂中, 活性组分以ZrO₂锚定的表面相(包括含有畸变或缺陷型Keggin单元的杂多酸盐及以Zr为杂原子的类杂多酸物种等)和TPA完全分解形成的氧化物体相存在, 各物种的相对量取决于TPA的负载量. 催化剂表面同时具有中等强度的布朗斯特德(Brönsted)酸与路易斯(Lewis)酸中心, 且初始TPA负载量为20%的催化剂实现了活性组分在载体表面的单层覆盖, 因而显示最大的总酸量, 对THF聚合反应也表现出最高的催化活性. 在反应温度为40 °C、时间为20 h条件下, 聚合物收率达30.9%±2%, 数均相对分子质量为2698±100; 在催化剂重复使用6次过程中, 活性未见明显降低.     

催化剂酸碱性对异丙醇脱水活性的影响

研究了具有不同酸碱中心的催化剂对异丙醇脱水反应活性及选择性的影响,结果表明:催化剂表面有合适的酸碱强度和H_0,max值,能引起高的脱水活性和选择性。红外吸附态证实:在接近反应状态下,催化剂表面出现了-CH₂结构吸附,这表明反应物的碱基(OH基)与催化剂表面酸中心作用的同时,酸基(反应物的β-H)与催化剂表面碱作用,催化剂上这种酸碱活性中心协同作用结果使异丙醇脱水生成丙烯的过程很可能以协同机理方式进行。     

层柱稀土盐催化合成乙二醇单烷基醚乙酸酯反应动力学

本文以Ce(SO4)2进行了酯化反应动力学进行研究,比其它类型催化剂具有较高的催化反应活性,通过Ce4 阳离子进行层间取代增大了层柱粘土催化剂的L酸及B酸位的数量和强度,酯化反应过程中生成的水受到Ce4 的诱导作用,进而造成L酸位向B酸位转换(B酸为主),导致催化剂表面产生较强的B酸酸强度.pH值测定提供了有力支持,结果表明:只有B酸位大于70%,并且在加人层柱粘土催化剂后乙二醇单烷基醚溶液pH值小于1时,在50～150℃的温度范围内才有良好的酯化反应活性和选择性.活性实验表明了层柱粘土催化剂可以重复使用,XRD也表明了新鲜的和重复使用的催化剂组成和晶相一样;同时对反应动力学作用用积分法进行研究,提出了这类反应本质的一般动力学方程.     

四氢呋喃聚合介孔催化剂Zr-PHTS合成、表征及反应性能

在水-有机溶剂复合体系中,以P123为结构导向剂水热直接合成了锆掺杂介孔固体酸催化剂(Zr-PHTS),运用XRD、TEM、N2吸附-脱附以及NH3-TPD、Py-FTIR等手段对催化剂进行了表征.结果表明,在硅锆摩尔比20-100考察范围内,所得Zr-PHTS样品均显示有序二维六方晶相结构,具有以L酸为主的中等强度的酸性中心;随着锆引入量的变化Zr-PHTS的比表面积仅显示少量的变化,孔径维持在9.8 nm;在四氢呋喃聚合反应中Zr-PHTS显示出较好的催化活性,硅锆摩尔比30的样品表现出最佳的催化性能,聚合物收率达到40.4%,数均分子量2 135,推测催化剂表面酸性和孔结构决定了催化剂对四氢呋喃的聚合性能.     

几种吡啶衍生物在Y型分子筛上置换吸附的红外光谱研究

沸石分子筛是一类固体酸催化剂,常用吡啶及其衍生物这类碱性物质来测定其酸中心的类型和酸度.近年来,有些作者利用空间位阻胺在酸中心上的选择吸附性质,来进行固体酸催化剂表面的Bronsted酸和Lewis酸的测定.实验发现,同一种吡啶衍生物在不同的沸石分子筛上的吸附稳定性不同,不同的吡啶衍生物在同一种固体酸催化剂上的吸附稳定性也不相同.利用这一性质,我们曾用脉冲色谱法和红外光谱法研究了吡啶对于2,6-二甲     

Adsorption studies of acetic acid dimers on activated charcoal from organic solvents

Acetic acid exists as dimers in organic solvents like benzene, toluene and xylene. Adsorption of dimeric acetic acid on activated charcoal (AC) at various temperatures from benzene, toluene and xylene solutions have been studied. The system obeys Langmuir isotherm, thus signifying a monolayer adsorption of dimers. Corrections on AC-solvent pore volume fillings, molecular cross sectional surface area of acetic acid dimers, the adsorption equilibrium constants, the free energy change and the enthalpy change values are computed at different temperatures for the three solvents. The adsorption process has been found to be physisorption type. The FTIR measurements show that the adsorbed acetic acid dimer seems to retain the cyclic structure against the open chain non-cyclic structure.     

Effects of exchanged surfactant cations on the pore structure and adsorption characteristics of montmorillonite

Ca-montmorillonite (Ca-Mont) was exchanged with two quaternary amines, tetramethylammonium (TMA) chloride and hexadecyltrimethylammonium (HDTMA) bromide, to study the surfactant ion exchange effect on the pore structure, surface characteristics, and adsorption properties of montmorillonite. The revolution of both the surface area and pore structure of montmorillonite was characterized based on classical and fractal analyses of the nitrogen isotherms as well as the XRD patterns. The change of surface characteristics was identified from FTIR patterns and zeta-potential plots. The adsorption isotherms of acid dye, Amido Naphthol Red G (AR1), were then measured to identify the effects of the ion-exchange process on the adsorption properties of montmorillonite. It was found that the exchange processes might induce an increase or decrease in the surface area, pore size, pore volume, and surface fractal dimension D of montmorillonite, depending on the size, the molecular arrangement, and the degree of hydration of the exchanged ion in the clay. On the other hand, it was also found that the hydrophobic bonding by conglomeration of large C(16) alkyl groups associated with HDTMA could cause positive charge development on the surface of montmorillonite, which was not observed for TMA-modified montmorillonite (TMM). The effects of the alteration of the surface characteristics of montmorillonites on their adsorption selectivity for acid dye were discussed.     

Chemical modification of natural clays

Natural clay samples and calcined clay varieties treated with hydrochloric acid of various strengths were characterized by X-ray diffraction, positron annihilation spectroscopy, and IR spectroscopy. The specific surfaces and pore sizes were determined by nitrogen adsorption. The constituent phases of the clay were found to be nontronite, muscovite, quartz, and hematite; after calcination, quartz, muscovite, hematite, and an amorphous phase remained in the samples. The Brilliant Green adsorption properties and tribotechnical properties of the modified clays were studied. The natural clay was surface-modified chemically by means of consecutive exposure to 36.5% hydrochloric acid and an alkaline hydrolyzate of rice hulls. Calcination at 700°С destroyed the amorphous phase to a greater extent; exposure to acid provided a greater recovery of aluminum and iron ions from the surface of calcined samples. Native clay composites with an alkaline hydrolyzate of rice hulls were shown to have enhanced tribotechnical characteristics.     

Effect of particle size of activated clay on the adsorption of paraquat from aqueous solution

This paper describes the effect of particle size on the process of paraquat adsorption from aqueous solution onto an activated clay surface at 25 degrees C and initial pH 11.0. Measurements of the pore properties of the clay adsorbents with three different particle sizes (0.053-0.074 mm, 0.037-0.053 mm, and <0.037 mm) were carried out. The rates and isotherms of adsorption have been also investigated by batch methods under the controlled conditions. From the experimental results obtained, the adsorption process can be well described with the pseudo-second order model and Freundlich model for adsorption kinetics and adsorption isotherm, respectively. In addition, the effect of the particle size of the clay adsorbent on the adsorption kinetics was found to be of considerable significance; namely, the rate constant (k) of paraquat adsorption by the clay adsorbent decreased with increasing particle size. It was concluded that the pore properties (i.e., surface area and total pore volume) and particle size of the clay adsorbent played a significant role in determining adsorption capacity and adsorption rate, respectively.     

酸处理和负载ZnCl2粘土结构的影响及应用研究

目前,Ｆｒｉｅｄｅｌ－Ｃｒａｆｔｓ反应的催化剂主要还是容易造成严重污染的ＡｌＣｌ３,ＺｎＣｌ２和ＦｅＣｌ３等酸性氯化物。随着环保呼声的日益高涨,有的地方已实行环保一票否决制,故寻找可以代替ＡｌＣｌ３类的环境友好固体酸催化剂,已成为化工生产中的当务之急...     

Nanoscale pore morphology and distribution of lacustrine shale reservoirs:Examples from the Upper Triassic Yanchang Formation,Ordos Basin

Pore structure plays an important role in the gas storage and flow capacity of shale gas reservoirs. Fieldemission environmental scanning electron microscopy(FE-SEM) in combination with low-pressure carbon dioxide gas adsorption(CO2GA),nitrogen gas adsorption(N2GA),and high-pressure mercury intrusion(HPMI) were used to study the nanostructure pore morphology and pore-size distributions(PSDs) of lacustrine shale from the Upper Triassic Yanchang Formation,Ordos Basin. Results show that the pores in the shale reservoirs are generally nanoscale and can be classified into four types: organic,interparticle,intraparticle,and microfracture. The interparticle pores between clay particles and organic-matter pores develop most often,l with pore sizes that vary from several to more than 100 nm. Mercury porosimetry analysis shows total porosities ranging between 1.93 and 7.68%,with a mean value of 5.27%. The BET surface areas as determined by N2 adsorption in the nine samples range from 10 to 20 m2/g and the CO2 equivalent surface areas(2 nm)vary from 18 to 71 m2/g. Together,the HPMI,N2 GA,and CO2 GA curves indicate that the pore volumes are mainly due to pores 100 nm in size. In contrast,however,most of the specific surface areas are provided by the micropores. The total organic carbon(TOC) and clay minerals are the primary controls of the structures of nanoscale pores(especially micropores and mesopores). Micropores are predominantly determined by the content of the TOC,and mesopores are possibly related to the content of clay minerals,particularly the illite-montmorillonite mixed-layer content.     

Quantitative information on pore size distribution from the tangents of comparison plots

The comparison plot obtained from the nitrogen adsorption data has a similar shape to that of the curve of accumulating pore volume of a solid. The intrinsic nature of this relation is discussed. It is known that the derivatives of the accumulating pore volume with respect to the pore size are the pore size distribution (PSD) of the solid. Thus, the tangent curve of the comparison plot can display, at least qualitatively, the PSD of a solid, over a wide range of pore sizes (from approximately 1 to 50 nm) because the comparison plot is applicable to both micropores and mesopores. Quantitative pore structure information can be derived from the comparison plots by establishing a relationship between the t value and the pore size from the samples with uniform pore structure and known pore sizes, such as MCM-41 and alumina pillared clay samples. A calculation procedure to derive quantitative PSD from the comparison plots is suggested, giving reasonable results. This study proposes concise and reliable methods based on the comparison plots to derive information on pore structure in porous solids.     

Aqueous and gaseous adsorption from montmorillonite-carbon composites and from derived carbons

Clay-carbon composites and the carbons derived from demineralization of the clay template were examined for their aqueous adsorption properties (2,4,6-trichlorophenol and methylene blue) and for their gas adsorption/separation abilities regarding CO(2), CH(4), and N(2) gases. The sorption results are discussed in relation with their structural properties (surface area, pore width and volume, and surface chemistry). It was found that the properties of the adsorbents depend highly on the synthetic route, for instance, on the use of clay or H(2)SO(4) as structure mediating and activating agents, respectively. Particularly, the simultaneous use of clay and H(2)SO(4) leads to a synergistic action, which imparts to the final solids the highest sorption capacity and the best potential for separation of CO(2) from gaseous mixtures of CH(4) and N(2).     

孔径渐变的有序介孔炭的合成及电化学应用

以SBA-15为模板,硼酸为孔道扩张剂,蔗糖为碳源制备了一系列孔径渐变的有序硼杂介孔炭材料,并研究了其电化学电容性能。氮气静态吸附测试表明,当硼酸物质的量分数从0%增大到75%时,介孔炭的孔径从3.3nm增大至8.1nm,并保持有序的介孔结构。电化学测试表明,在KOH电解液中,硼杂介孔炭比电容明显高于未掺杂硼有序介孔炭,孔道有序性和孔径大小共同影响了炭材料的电容性能。当硼酸物质的量分数为50%时,炭材料的比电容性能最优。     

Development of Composite Adsorbents of Carbon and Intercalated Clay for N2and O2Adsorption: A Preliminary Study

Composite adsorbents of carbon and alumina intercalated montmorillonite were prepared and characterized by adsorption of N₂and O₂at various temperatures. The effects of pyrolysis, temperature, heating rate, subsequent degassing, and doping of cations and anions were investigated. The adsorption capacities of the composite adsorbents developed at higher temperatures (0 and −79°C) are found to be larger than those of normal alumina pillared clays. The experimental results showed that the framework of these adsorbents is made of alumina particles and clay sheets while the pyrolyzed carbon distributes in the space of interlayers and interpillars. The pores between the carbon particles, clay sheets, and alumina pillars are very narrow with very strong adsorption forces, leading to enhanced adsorption capacities at 0 and −79°C. The composite adsorbents exhibit features similar to those of carbonaceous adsorbents. Their pore structures, adsorption capacities, and selectivities to oxygen can be tailored by a controlled degassing procedure. Meanwhile, ions can be doped into the adsorbents to modify their adsorption properties, as usually observed for oxide adsorbents like zeolite and pillared clays. Such flexibility in pore structure tailoring is a potential advantage of the composite adsorbents developed for their adsorption and separation applications.