酚醛树脂改性煤焦油沥青的热解特性

以酚醛树脂为改性剂,采用共混的方法对煤焦油沥青(煤沥青)进行改性.主要利用热重与傅立叶变换红外光谱联用仪(TG-FTIR)考察了不同共混比例改性煤沥青的热解特性.结果表明,随着酚醛树脂掺混量的增加,改性煤沥青中的n(H)∶n(C)逐渐减小;2 953cm~(-1)(—CH_3)和2 924cm~(-1)(—CH_2—)处透射峰强度逐渐减弱;1 512cm~(-1)(苯环C=C)处的透射峰强度逐渐增强;1 232cm~(-1)(芳香醚键=C—O—C)处和1 101cm~(-1)(脂链醚键C—O—C)处透射峰强度逐渐增强;随着酚醛树脂掺混量的增加,改性煤沥青的起始失重温度逐渐升高,最大失重速率逐渐降低;改性煤沥青热解挥发物在较宽的温度范围内析出;改性煤沥青的实际失重率大于理论失重率;酚醛树脂与煤沥青发生交联;酚醛树脂的添加使得芳香烃类、脂肪烃类和CH_4的释放量减少,并且挥发产物的析出发生在更宽的热解温度范围;芳香烃类和CH_4的释放量由低温向高温延伸.     

高温内压环境下聚乙烯燃气管道老化性能评价研究

将一批聚乙烯燃气管道试样置于80 ℃、1.1 MPa水浴环境下进行老化试验，老化时间分别为0、165、500、1 000 h，并通过差示扫描量热法（DSC）、热失重分析（TG）、傅里叶变换红外光谱分析（FTIR）和拉伸试验分别测试各老化试样对应的氧化诱导时间（等温OIT）、热分解温度（T_s）、官能团组成和断裂伸长率（ε），模拟分析高温内压环境下聚乙烯管道的老化性能变化规律。DSC、TG和拉伸试验结果显示，随着老化时间增加，聚乙烯管道的等温OIT、T_s和ε都逐渐降低，老化程度逐渐增加，并且管内壁的老化速率明显大于外壁；FTIR结果显示，随着老化时间增加，聚乙烯管材料的官能团谱图中1 720 cm^-1和3 400 cm^-1处分别出现了C=O和O—H的振荡峰，进一步证实了聚乙烯管材料分子链中引入了氧化反应产物。     

基于植物沥青的温拌再生沥青流变及疲劳性能研究

对生物质温拌再生沥青的流变性能和疲劳性能进行研究,选用70^#基质沥青以3.5%,5.5%,7.5%,9.5%,11.5%掺量的生物质温拌再生剂WL-3对室内模拟老化沥青进行再生,采用动态剪切流变仪(DSR)对生物质温拌再生沥青的相位角、复数模量、车辙因子等高温流变性能指标进行研究;通过线性振幅扫描(LAS)对生物质温拌再生沥青、70^#基质沥青和老化沥青的疲劳性能进行研究。结果表明,生物质温拌再生剂WL-3的加入降低了老化沥青的车辙因子、疲劳因子和应变恢复率(R),不可恢复蠕变柔量(Jnr)和疲劳寿命增加,提高了老化沥青的应力敏感性,流变特性得到较好恢复。     

3种沥青中正戊烷沥青质及其亚组分的分子特性研究

以3种沥青为研究对象,从中分离出正戊烷沥青质(As-5),又进一步从正戊烷沥青质(As-5)中分离出正庚烷沥青质(As-7)和重胶质两种亚组分,并分别对3种沥青的正戊烷沥青质、正庚烷沥青质和重胶进行了元素分析(EA)、凝胶色谱分析(GPC)、核磁共振氢谱分析(¹H NMR)的表征分析。结果表明：每种沥青的3种组分中均是正庚烷沥青质的C/H原子数比、重均分子量M_w和大小分子(LMS/SMS)含量比最大,同时具有最大的芳碳率f_A、芳环缩合程度和结构单元分子量usw。而重胶质的C/H原子数比、重均分子量M_w和大小分子(LMS/SMS)含量比均最小,同时具有最小的芳碳率f_A、芳环缩合程度和结构单元分子量usw。正戊烷沥青质的以上平均结构参数均处于其分离出的正庚烷沥青质和重胶质二者之间。在这些表征结果的基础上,对3种沥青中3种组分的溶解度参数δ进行计算,进一步分析了沥青组分的平均分子结构与溶解度参数之间的关系。     

抑烟环保型沥青性能试验分析

为了解决沥青路面摊铺会产生的大量有毒气体这一问题,本文在70^#基质沥青中添加抑烟剂制备抑烟沥青,并对其性能进行分析。首先通过自制沥青烟气收集装置分析了掺加不同比例的Sasobit和纳米CaCO₃在单掺和复配时对沥青抑烟效果的影响,然后采用动态剪切试验、弯曲流变试验以及储存稳定性试验分析了Sasobit和纳米CaCO₃对沥青性能的影响。试验结果表明,在最佳复配比例下的Sasobit和纳米CaCO₃,能使沥青烟气抑制效果达到12%,能明显改善70^#基质沥青的高温性能,对储存稳定性无影响。     

石油沥青和中温煤沥青共炭化改性的研究

研究了不同比例石油沥青和中温煤沥青在一定的温度和压力下共炭化对改性沥青性能的影响.利用元素分析仪、红外光谱仪、黏度仪和热失重仪进行分析表征,研究了共炭化工艺参数对改性沥青的理化性质和热性能的影响.结果表明,10％石油沥青添加量的改性沥青性能最优,结焦值达到51.93％.结合红外和热失重分析可得,改性沥青具有较好的热反应...     

神华煤直接液化残渣萃取组分改性石油沥青

以神华煤直接液化残渣索氏溶剂梯级萃取分别得到的重油(HS)、沥青烯(AS)和前沥青烯(PA)作为改性剂,对石油沥青进行改性,探究改性剂的掺混量对石油沥青性能的影响及其改性机制。研究表明:当HS作为改性剂时,最佳掺混量为1%;当AS作为改性剂时,最佳掺混量为4%;PA作为改性剂时得到的改性沥青,针入度和延度不能同时符合美国ASTM D5710—95标准40~55针入度的指标要求;HS和AS改性沥青与石油沥青相比在2924cm~(–1)及2847cm~(–1)处的—CH2—的伸缩振动吸收峰强度变弱,在改性过程中可能发生了烷基侧链脱氢反应;改性沥青与石油沥青的热失重相比,其最终失重温度都有所提高,当AS作为改性剂、加入量为4%时改性沥青最终失重温度提高最大为11℃;随着改性剂分子量的增大,其荧光显微镜图片中的荧光物质会越来越多,颗粒逐渐增大。     

铜基载氧体的焦炉煤气化学链燃烧特性

焦炉煤气(COG)是炼焦过程产生的主要副产品,含有复杂的气体成分(CO、H₂、CH₄、CO₂),化学链燃烧是一种可实现COG高效转化与高纯CO₂捕集的技术。通过溶胶凝胶法制备了一系列x(%)CuO/Ce-Zr-O(x=30、50、70、90)载氧体用于COG化学链燃烧反应特性研究。XRD表明,x(%)CuO/Ce-Zr-O载氧体物相由CuO和Ce_0.67Zr_0.33O₂固溶体组成。由于Zr⁴⁺进入CeO₂晶格中,在617 cm^-1处出现明显的氧空位Raman特征峰。H₂-TPR、CO-TPR、CH₄-TPR和COG-TPR结果表明加入Ce-Zr-O固溶体促使铜物种低温释氧能力增强。800℃下,CuO样品CO₂捕集率为34%,添加10%Ce_0.67Zr_0.33O<...     

玻璃镜片气泡结构及热变性三级中红外光谱研究

采用中红外(MIR)光谱技术研究玻璃镜片气泡结构,发现气泡结构的红外吸收模式主要为ν_{asO=C=O-一维}。采用变温中红外(MIR)光谱进一步研究了气泡结构的热稳定性,发现在303～393 K范围内的主要官能团(ν_H-O-H-一维、ν_{asO=C=O-一维}和δ_O=C=O-一维)的吸收频率及强度发生变化。采用二维MIR光谱深入研究了主要官能团(ν_H-O-H-二维、ν_{asO=C=O-二维}、δ_H-O-H-二维、ν_{sO=C=O-二维}、δ_O=C=O-二维)对热的敏感程度及变化快慢,发现玻璃镜片气泡结构红外吸收模式主要集中在3 420～3 380 cm^-1、2 365～2 335 cm^-1、1 660～1 630 cm^-1、1 350～1 330 cm^-1及680～660 cm^-15个频率区间,在这...     

生物质再生沥青高温流变特性研究

采用生物油研发沥青再生剂(SW-1),以2%,4%,6%,8%的掺量对不同老化状态下的沥青进行再生,对再生沥青的常规性能进行分析。并选用三种石油基再生剂(ZS-1、ZS-2、ZS-3)和生物质再生剂做对比研究,借助动态剪切流变仪,采用复数模量、相位角、车辙因子等指标对70^#基质沥青、轻度、重度老化沥青及再生沥青的高温流变性能进行研究。研究表明,掺加再生剂后,老化沥青的常规性能得到有效恢复,四种再生沥青的复数模量和车辙因子降低,相位角增大,沥青弹性性能呈减弱趋势,粘性性能呈增强趋势。其中生物质再生剂对老化沥青的性能指标提升明显。     

Synthesis,characterization and catalytic properties of mesoporous MCM-48 containing zeolite secondary building units

Mesoporous aluminosilicate MCM-48 containing zeolite secondary building units in the pore wall has been synthesized in alkaline media with a two-step procedure. The aluminosilicate precursors comprising zeolite secondary building units were first synthesized by carefully controlling reaction conditions and then were assembled using cotemplates of gemini surfactant [C₁₈H₃₇N(CH₃)₂(CH₂)₃N(CH₃)₂C₁₈H₃₇]²⁺ (18-3-18) and triethanolamine (TEA). X-ray Diffraction (XRD) patterns of the as-made samples indicated that highly ordered mesostructured MCM-48 was formed. Transmission Electron Microscopy (TEM) images further verified the formation of MCM-48 with uniform cubic pore channel system having the pore opening diameter of about 25 Å. Compared with the conventionally synthesized MCM-48, the as-synthesized MCM-48 sample showed an adsorption band at 520 600 cm^-1 in its FT-IR spectrum, which was assigned to five-membered ring vibration from zeolite structure. This suggested the presence of zeolite building units in the pore wall. N2 adsorption data showed that the material had a much higher specific surface area (1 200 m₂/g) than the conventional MCM-48(1 100 m₂/g). Finally, the catalytic performance of the as-made MCM-48 was evaluated by hydrogenation dealkylation reaction of heavy aromatic hydrocarbons. Catalytic results showed that the as-made MCM-48 catalyst exhibited higher conversion than the conventional MCM-48 catalyst. The as-made mesostructured MCM-48 may have a potential catalytic application in the conversion of bulky molecules.     

New high permeable polysulfone/ionic liquid membrane for gas separation

In this study, the effects of 1-Ethyl-3-methylimidazolium tetrafluoroborate ionic liquid on CO₂/CH₄ separation performance of symmetric polysulfone membranes are investigated. Pure polysulfone membrane and ionic liquid-containing membranes are characterized. Field emission scanning electron microscopy (FE-SEM) is used to analyze surface morphology and thickness of the fabricated membranes. Energy dispersive spectroscopy (EDS) and elemental mapping, Fourier transform infrared (FTIR), thermal gravimetric (TGA), X-ray diffraction (XRD) and Tensile strength analyses are also conducted to characterize the prepared membranes. CO₂/CH₄ separation performance of the membranes are measured twice at 0.3 MPa and room temperature (25 °C). Permeability measurements confirm that increasing ionic liquid content in polymer-ionic liquid membranes leads to a growth in CO₂ permeation and CO₂/CH₄ selectivity due to high affinity of the ionic liquid to carbon dioxide. CO₂ permeation significantly increases from 4.3 Barrer (1 Barrer=10^-10 cm³(STP)·cm·cm^-2·s^-1·cmHg^-1, 1cmHg=1.333kPa) for the pure polymer membrane to 601.9 Barrer for the 30 wt% ionic liquid membrane. Also, selectivity of this membrane is improved from 8.2 to 25.8. mixed gas tests are implemented to investigate gases interaction. The results showed, the disruptive effect of CH₄ molecules for CO₂ permeation lead to selectivity decrement compare to pure gas test. The fabricated membranes with high ionic liquid content in this study are promising materials for industrial CO₂/CH₄ separation membranes.     

孔活性炭储存CH4的分子模拟

吸附天然气被认为是未来最具有发展前景的CH₄储存方式之一,其中的关键是寻找合适的吸附剂,使其具有良好的CH₄吸脱附性能。以纳米多孔碳材料作为多孔活性炭的结构,采用巨正则蒙特卡洛（GCMC）和平衡分子动力学（EMD）的方法研究CH₄在纳米多孔碳材料中的吸附和扩散行为,通过考察不同因素的影响,期望获得高的CH₄吸附量和自扩散系数。其中,研究的主要因素有：构成多孔碳材料的石墨片微元的大小、多孔碳材料的不同密度、多孔碳材料的表面基团改性。结果表明：多孔碳材料对CH₄的吸附受石墨片微元种类和混合比例的影响不大;在所研究的多孔碳材料密度范围内,存在最优密度,能够获得最大的CH₄吸附量,此最优密度在0.50 g·cm^-3左右,但是多孔碳材料的表面经羟基修饰后,最佳材料密度发生了偏移,此时最优密度在0.72 g·cm^-3左右;此外,经表面改性后的多孔碳材料吸附量大小顺序为：CH₃ > OH > CO > COOH;对于CH₄在多孔碳材料中的扩散,总体规律是低的密度,并且经过COOH修饰,其CH₄自扩散系数最大。     

基于FTIR分析的稻草热解机理

The pyrolysis mechanism of rice straw (RS) was investigated using a tube reactor with Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analyzer. The results show that the maximum pyrolysis rate increases with increasing heating rate and the corresponding temperature also increases. The three-pseudocomponent model could describe the pyrolysis behavior of rice straw accurately. The main pyrolysis gas products are H2O, CO2, CO, CH4, HCHO (formaldehyde), HCOOH (formic acid), CH3OH (methanol), C6H5OH (phenol), etc. The releasing of H2O, CO2, CO and CH4 mainly focuses at 220-400°C. The H2O formation process is separated into two stages corresponding to the evaporation of free water and the formation of primary volatiles. The release of CO2 first increases with increasing temperature and gets the maximum at 309°C. The releasing behavior of CO is similar to H2O and CO2 between 200 and 400°C. The production of CH4 happens, compared to CO2 and CO, at higher temperatures of 275-400°C with the maximum at 309°C. When the temperature exceeds 200°C, hydroxyl and aliphatic C H groups decrease significantly, while C O, olefinic C C bonds and ether structures increase first in the chars and then the aromatic structure develops with rising temperature. Above 500°C, the material becomes increasingly more aromatic and the ether groups decreases with an increase of temperature. The aromatization process starts at ≈350°C and continues to higher temperatures.     

微藻油改性沥青耐老化性能研究

为缓解石油沥青短缺局势,探索微藻油用于沥青改性可行性及改性沥青长期性能,将微藻液经降解、离心、萃取得到微藻油并制备改性沥青。通过不同微藻油掺量下改性沥青延度、软化点和黏度确定微藻油最佳掺量,通过高低温流变试验、混合料路用性能试验分析微藻油改性沥青经旋转薄膜烘箱(RTFOT)短期老化、压力老化容器(PAV)长期老化和紫外老化后性能变化并与SBS改性沥青对比,借助红外光谱分析微藻油改性沥青分子结构组成。结果表明:微藻油掺量为30%(外掺质量分数)时,改性沥青延度达到最大值,软化点和黏度满足改性沥青要求;微藻油改性沥青和苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)改性沥青经RTFOT短期老化后性能差异不显著,微藻油改性沥青耐PAV长期老化和耐紫外老化性能优于SBS改性沥青,尤其是耐紫外老化性能更优。红外分析表明两种改性沥青均含有乙烯基双键、芳香族C—H、甲基和亚甲基等类似成分,但芳香族C—H、伸缩C—C成分含量存在差异。微藻油改性沥青比SBS改性沥青增加的酰胺不饱和基团和羧基利于改性沥青形成网络分子结构。     

Growth of faceted, ballas-like and nanocrystalline diamond films deposited in CH4/H2/Ar MPCVD

The influence of Ar addition to CH₄/H₂ plasma on the crystallinity, morphology and growth rate of the diamond films deposited in MPCVD was investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. X-Ray diffraction patterns indicate that diamond films of strong (111) and weak (400) texture are produced in these samples. Faceted diamond gradually turns into ballas-like diamond with graphitic inclusions when the Ar concentration increases to above 30 vol.%, as indicated by Raman spectra. As the Ar concentration goes above 90 vol.%, nanocrystalline diamond films are formed, characterized by a 1150-cm⁻¹ peak in the Raman spectra and morphology observation. Diamond growth by CH₃ or by C₂ mechanism is proposed to interpret the change in the growth rate of diamond films with the variation of Ar content in the plasma.     

PEO/聚吡咯中空纳米微球混合基质膜的制备及其CO2渗透分离性能

采用壳层具有介孔结构的聚吡咯中空纳米微球作为填料，和聚氧化乙烯单体共混自由基聚合制备了混合基质膜。结果表明，聚吡咯微球与基质相容性较好，未见明显团聚现象和缺陷。混合基质膜的渗透系数随填料含量的增加先增大后减少，在0.5%处达到最大值，CO₂渗透系数增长31%；CO₂/N₂分离系数有所降低，CO₂/CH₄分离系数则变化不大。研究表明，由于聚合物链段对微球壳层的介孔填充，气体在膜内的扩散系数不升反降，渗透系数的提高主要是由于溶解度系数的变化，而这也导致了溶解选择性的变化，进而影响了分离系数。     

反气相色谱法与汉森溶解度参数软件测定原煤的三维溶解度参数

采用反气相色谱法（IGC）研究原煤在温度433.15、443.15、453.15、463.15和473.15 K时的三维溶解度参数（HSP）,并使用外推法得到原煤室温（298.15 K）时HSP的色散力分量（δ_d）、极性力分量（δ_p）、氢键力分量（δ_h）以及校正溶解度参数（δ_t）分别为δ_d=20.83（J·cm^-3）^1/2,δ_p=11.95（J·cm^-3）^1/2,δ_h=11.08（J·cm^-3）^1/2,δ_t=26.44（J·cm^-3）^1/2。同时,采用汉森三维溶解度参数软件（HSPiP）模拟原煤在室温下的HSP,得到δ_d=19.92（J·cm^-3）^1/2,δ_p=11.18（J·cm^-3）^1/2,δ_h=11.47（J·cm^-3）^1/2,δ_t=25.56（J·cm^-3）^1/2。IGC与HSPiP得出的数据一致,研究结果为煤的热力学性质研究及其溶胀剂的选择等应用提供了参考。     

Hydrophobic modification of SAPO-34 membranes for improvement of stability under wet condition

SAPO-34 zeolite membranes show high efficiency for CO₂/CH₄ separation but suffer from the reduction of separation performance when exposed to humid atmosphere. In this work, n-dodecyltrimethoxysilane (DTMS) was used to modify the hollow fibers supported SAPO-34 membranes to increase the external surface hydrophobicity and thus sustain their performance under moisture environment. The modified membranes were fully characterized. Their separation performance was extensively investigated in both dry and wet gaseous systems and compared with the un-modified ones. The un-modified SAPO-34 membrane exhibited a high separation selectivity of 160 and CO₂ permeance of 1.18×10^-6 mol·m^-2·s^-1·Pa^-1 for separation of dry CO₂/CH₄ at 298 K. However, its separation selectivity declined to 0.9 and the CO₂ permeance was only about 1.7×10^-8 mol·m^-2·s^-1·Pa^-1 for wet CO₂/CH₄ at same temperature. High temperature (e.g. 353 K) could reduce the effect of moisture to improve SAPO-34 separation selectivity, but further increasing temperature (e.g. 373 K) led to decrease in CO₂/CH₄ separation selectivity. A significant decrease of selectivity was observed at higher pressure drop. The modified SAPO-34 membrane showed decreased CO₂ permeance but increased separation selectivity for dry CO₂/CH₄ gas mixture, and super performance for wet CO₂/CH₄ gas mixture due to the improved hydrophobicity of membrane surface. A separation selectivity of 65 and CO₂ permeance of 4.73×10^-8 mol·m^-2·s^-1·Pa^-1 for wet CO₂/CH₄ mixture can be observed at 353 K with a pressure drop of 0.4 MPa. Furthermore, the modified membrane exhibited stable separation performance during the 120-hour test for wet CO₂/CH₄ mixture at 353 K. The hydrophobic modification paves a way for SAPO-34 membranes in real applications.