压力条件对龙口油页岩热解特性的影响

采用法国Setaram公司Themys HP型高压热重仪对我国龙口油页岩进行不同压力条件下的热解实验,利用产物释放特性指数,并通过分布活化能模型DAEM对不同压力条件下的热解反应进行动力学分析。研究表明龙口油页岩的热解主要包括页岩的脱水阶段、有机质热解阶段以及碳酸盐及黏土矿物的分解阶段;压力的升高对于龙口油页岩的热解过程有明显的影响,改变热解产物的析出速率,产物释放特性指数能很好地表征龙口油页岩在压力改变的条件下热解过程中产物的析出特性,热解压力小范围的升高(5bar)有利于挥发分的析出,过高的压力不利于挥发分的快速析出。动力学分析表明,热解低温阶段反应所需活化能在压力升高的条件下呈现出先增大后减小的趋势,但明显高于高温段热解活化能。适当提高压力有利于热解反应的进行。     

煤、油页岩和石油焦混烧特性及其动力学

为了充分利用劣质燃料油页岩和难以利用的高硫石油焦,以煤、劣质燃料油页岩及高硫燃料石油焦的混合燃料为研究对象,采用热重-差热的试验方法和差减微分法,对其混烧特性曲线和混烧特性机理进行分析,计算出试样各种燃烧特性参数及燃烧动力学参数。结果表明:煤、油页岩、石油焦的质量比为1∶6∶3的混烧试样S7的DTG曲线先后出现挥发分的析出着火燃烧峰和剩余固定碳的着火燃烧峰;煤、油页岩、石油焦的质量比为6∶3∶1的混烧试样S4的可燃特性指数及着火特性指数均大于油页岩及石油焦的值,而且混合试样的燃尽指数均大于煤及石油焦的值,同时,混合样品的综合燃烧特性指数均大于油页岩的值;试样S4的活化能最小,该混合试样的燃烧反应最容易进行。只要煤、油页岩及石油焦混合比例适当,其混合燃烧特性将优于油页岩及石油焦单独的燃烧特性。     

油页岩热解特性及其甲烷释放规律研究

为研究油页岩热解特性及热解过程中甲烷的释放规律,采用热重-傅里叶变换红外光谱（TG-FTIR）对龙口（LK）、内蒙（NM）、汪清（WQ）三个地区的典型油页岩进行热解实验,并结合固相红外（FTIR）对油页岩的官能团结构进行分析。研究结果表明,油页岩热解过程可分为四个阶段,热解反应及挥发分释放主要发生在第二阶段（400～600℃）。甲烷的析出与油页岩结构中的脂肪烃（光谱范围3000～2800 cm^-1）密切相关,脂肪烃含量越多,热解过程中释放的甲烷越多。通过对甲烷析出曲线分峰拟合及结合动力学分析,得出甲烷的生成是由一个脱吸附过程和四个化学反应共同作用的结果。     

油页岩热解特性及其甲烷释放规律研究

为研究油页岩热解特性及热解过程中甲烷的释放规律,采用热重-傅里叶变换红外光谱(TG-FTIR)对龙口(LK)、内蒙(NM)、汪清(WQ)三个地区的典型油页岩进行热解实验,并结合固相红外(FTIR)对油页岩的官能团结构进行分析。研究结果表明,油页岩热解过程可分为四个阶段,热解反应及挥发分释放主要发生在第二阶段(400~600℃)。甲烷的析出与油页岩结构中的脂肪烃(光谱范围3000~2800 cm-1)密切相关,脂肪烃含量越多,热解过程中释放的甲烷越多。通过对甲烷析出曲线分峰拟合及结合动力学分析,得出甲烷的生成是由一个脱吸附过程和四个化学反应共同作用的结果。     

低温灰化中不同有机质的内蒙古油页岩热解特性

运用低温灰化仪、热重-红外联用分析仪对3种内蒙古油页岩进行低温灰化和以20℃/min升温速率的热解实验,来探究低温灰化对油页岩热解特性的影响。通过热重(TG-DTG)曲线、红外分峰拟合曲线分析低温灰化前后官能团的变化,并考察了CO_2、CH_4、CnHm轻质气体随灰化时间的变化规律。结果表明:热解实验过程中,低温灰化后不同有机质含量的油页岩和原样的热重曲线有差别之处,灰样在第二阶段则趋于平缓,失重比例小,且随着灰化时间的增加,灰样的热重曲线逐渐向高温区移动。内蒙古油页岩原样的热解产物主要是CO_2和CH_4、CnHm,而灰样中轻质烷烃和芳香烃的含量均减少;内蒙古油页岩析出气体CH_4和CnHm曲线基本相似,呈高斯分布,CO_2的析出速率先缓慢增加后快速增加,达到最高值后又快速下降,直至析出结束。同时,对内蒙古油页岩和灰样进行热解动力学的研究,反应的活化能通过Coats-Redfem积分法进行分析,得出热解的化学反应动力学参数,其计算结果为油页岩的高效开发和经济利用提供了理论基础。     

油页岩颗粒的热解模型

以实验为依据,分析了油页岩的热解机理及特性,并充分考虑了油页岩中挥发分在整个热解过程的作用,在此基础上建立了与油页岩固有热解特性相适应的热解模型。在能量方程中考虑了油页岩挥发分的热解反应吸热量及其挥发分的释放对油页岩固体颗粒质量的影响,并根据油页岩的热解特性,采用分阶段模型来描述油页岩的热解过程,以减小一步本征动力学方程带来的较大误差,还对模型进行了实验验证。     

石油焦与煤混烧特性及动力学

以石油焦与煤的混合燃料为研究对象,采用TG—DTG—DSC联用实验技术对混合试样进行了燃烧热重实验。分析了混烧特性曲线,计算了各个燃烧特性指数,并采用差减微分法Freeman—Carroll计算了燃烧反应动力学参数。结果表明：各混合试样均只出现一个位于高温区段的DTG曲线峰和方向向下的DSC曲线的热量释放峰,混合试样的燃烧过程主要是高温阶段焦炭的着火燃烧过程;混合试样s2,S3及S5热量释放相对较少且不集中,燃烧时间长且不完全;混合试样S4及S6的热量释放集中且时间短,燃烧释放的热量相对较多;烟煤含量最多的混合试样s6的着火特性、燃尽特性指数及综合燃烧特性参数均高于其它混合试样以及石油焦的各个相应值,且试样s6的可燃特性指数也大于石油焦的可燃特性指数;混合试样活化能均小于石油焦燃烧的活化能,混合试样比石油焦更易着火燃烧;只要石油焦与煤的混合比例适当,石油焦掺烧烟煤后的燃烧特性优于石油焦单独燃烧特性,此为解决石油焦难以单独燃烧利用提供了方法。     

神木煤与生活污泥共热解特性及动力学分析

采用热重分析仪,对不同混合比例的煤泥混样进行热解特性及动力学研究。根据各试样的热重曲线(TG)和微熵热重曲线(DTG),计算热解特征参数和动力学参数,重点分析了生活污泥的添加量对神木煤热解过程的影响。结果表明:煤与生活污泥的热解过程有很大差异,主要表现在挥发分初析温度、总失重率及最大失重速率。随着污泥添加量的增加,煤泥混样热解各阶段的最大失重速率、热解总失重率逐渐增加,而热解初析温度及热解活化能逐渐减小,表明污泥的添加对煤的热解具有促进作用。污泥质量分数为90%时,煤泥混样的热解特性最优,挥发分综合释放特性指数D和热解活化能分别是煤单独热解时的2. 86倍和75%。     

褐煤与生物质共热解过程的协同效应

通过热重分析的方法对褐煤、生物质及褐煤生物质混合物的热解特性进行研究,以考察生物质与褐煤共热解过程中是否存在协同效应,结果表明:将褐煤与生物质按1∶1(质量比)的比例混合后,其初始热解温度及挥发分最大释放峰出现温度与生物质单独热解基本相同,热解终温与褐煤相比大幅度提前,混合物热解在各个阶段的失重率均大于其单独热解失重率的平均值.褐煤、生物质及其混合物的热解过程可以用一级和二级热解反应动力学模型描述,通过计算动力学参数,发现在整个主要热解过程中,混合物在各个温度段的E值均小于褐煤或生物质单独热解时的E值,热解反应更加容易进行.证明了生物质对褐煤的热解有促进作用,褐煤与生物质在共热解过程中存在协同效应.     

神木烟煤与桦甸油页岩的共热解特性

采用热重分析仪和固定床反应器研究了神木烟煤和桦甸油页岩的混合共热解特性及协同作用机制. 结果表明,神木煤与桦甸油页岩混合共热解的失重率高于计算值,表明二者在热解和挥发分逸出过程中存在相互作用,促进了挥发分释放,减少了半焦生成. 煤与油页岩的协同作用可增加热解油收率、降低半焦和水收率. 油页岩与煤质量比为1:1时,所得油收率最高,为9.84%,比计算值提高8.8%. 共热解有助于提高轻质油含量和收率,油页岩与煤质量比为1:4时,轻质油含量超过80%,收率约为7.5%,比计算值分别提高了8%和11.2%,表明添加少量油页岩可明显提高热解油品质. 共热解过程中油页岩产生的富氢组分及自由基能抑制煤热解产生的芳香族化合物的聚合反应,促进芳烃向产物油转化,提高热解油的收率和品质.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.