基于简单碰撞理论的生物质焦炭气化反应的活化能

利用热重分析仪在800~1000℃及750~1000℃下分别对11种生物质原焦及6种生物质脱灰焦进行了CO2等温气化实验,用碳转化率x=0.2时的瞬时气化反应速率rc,0.2对反应速率rc进行无量纲化处理;根据简单碰撞理论,推导得出了生物质焦炭气化反应速率的表达式,求取了17种生物质焦炭气化反应的活化能;结合催化理论与简单碰撞理论建立了生物质焦炭气化反应活化能的经验预测模型. 结果表明,转化率达0.2后,各焦炭不同温度下无量纲气化反应速率曲线基本重合,表明不同温度下焦炭微观结构在转化过程中具有基本相同的演变规律. 各焦炭的活化能与催化剂所占据的活性位比例存在良好的对数关系. 忽略催化效应的影响,焦炭本征气化反应的活化能趋于某一定值,约为254.35 kJ/mol,而完全催化反应活化能约为66.02 kJ/mol.     

内蒙颗粒褐煤的气化特性研究

以粒度为5~10 mm的大颗粒内蒙褐煤为原料,分别以H2O(g)和CO2为气化剂,采用自制的煤炭地下气化模拟实验装置进行气化模拟实验,并测定煤气组分、气化残焦的微观结构,考察了气化剂种类、气化温度和气化时间对内蒙褐煤气化反应特性的影响。结果表明,CO2为气化剂时,随着反应温度升高,煤气中CO、H2、CH4含量越多,煤气热值也越高;以H2O(g)为气化剂时,H2含量随着反应温度升高而增大,CO含量则先增大后降低,CH4则降低,煤气热值最高可达12.19 MJ/m3;反应速率在气化约30 min时达到最大;H2O(g)气化的碳转化率、气化反应速率和煤气热值均高于CO2气化,表明H2O(g)作气化剂比CO2好。     

碱金属对焦炭与CO_2或水蒸汽气化反应的影响

采用自制的气-固相反应装置研究了K/Na对焦炭与CO_2和水蒸汽气化反应的影响.结果表明,K/Na对焦炭与CO_2气化反应的催化作用强于对焦炭与水蒸汽反应的催化作用,焦炭中Na含量由0.045wt%增加到0.727wt%,焦炭与CO_2和水蒸汽气化反应的反应性指数分别增加23.17%和14.35%,反应后焦炭强度分别降低27.55%和18.31%.焦炭中K/Na含量增加,焦炭与CO_2和水蒸汽气化反应明显开始温度、激烈反应温度和反应表观活化能均降低,焦炭中Na含量由0.045wt%增加到0.727wt%,焦炭与CO_2和水蒸汽气化反应明显开始温度分别降低170和20℃,激烈反应温度分别降低165和80℃,Na含量由0.045wt%增加到0.326wt%,表观活化能分别降低22.56和9.26 k J/mol.     

内蒙颗粒褐煤的气化特性研究

以粒度为5¹0 mm的大颗粒内蒙褐煤为原料,分别以H2O(g)和CO2为气化剂,采用自制的煤炭地下气化模拟实验装置进行气化模拟实验,并测定煤气组分、气化残焦的微观结构,考察了气化剂种类、气化温度和气化时间对内蒙褐煤气化反应特性的影响。结果表明,CO2为气化剂时,随着反应温度升高,煤气中CO、H2、CH4含量越多,煤气热值也越高;以H2O(g)为气化剂时,H2含量随着反应温度升高而增大,CO含量则先增大后降低,CH4则降低,煤气热值最高可达12.19 MJ/m3;反应速率在气化约30 min时达到最大;H2O(g)气化的碳转化率、气化反应速率和煤气热值均高于CO2气化,表明H2O(g)作气化剂比CO2好。     

一种褐煤热解煤焦的CO2气化反应特性

针对褐煤的热解-部分气化-残炭燃烧梯级利用工艺,以宁夏石沟驿褐煤为原料,采用水平管式炉在700℃～950℃温度范围内分别制备快速和慢速热解煤焦,考察了煤焦微晶结构和比表面积随制焦条件的变化.利用热重-质谱联用技术研究煤焦CO2气化反应特性,并采用不同评价指标对煤焦气化活性进行了表征.结果表明:气化温度每升高50℃,煤焦CO2气化反应速率增加50％以上;热解温度升高,虽然煤焦微晶结构的有序化程度加深,比表面积减小,但煤焦CO2气化反应活性主要受气化温度影响;快速热解煤焦的CO2气化反应活性高于慢速热解煤焦,二者的差异随着气化温度升高而增大;表征煤焦CO2气化活性的平均比气化速率和反应性指数存在线性关系.     

H2O和CO2对焦炭溶损反应动力学的研究

采用自制高温气固相反应连续测定装置,研究了900~1100℃下,CO2,H2O及其混合气体与焦炭的溶损反应. 结果表明,焦炭与H2O反应的溶损率远高于其与CO2反应后的溶损率,前者是后者的2~5倍. 相比与CO2的反应,焦炭与H2O的反应在颗粒外围更为剧烈,且不易在中心部位生成大的串孔及裂纹. 900℃时,与CO2、H2O反应开始的焦炭的主要气化方式分别为微孔生成、小孔扩张;1100℃时,分别为小孔扩张、微孔生成. 随着混合气体中H2O含量的增加,焦炭的溶损率不断增加. 当[H2O]/[CO2]=5/5和7/3时,焦炭与混合气体的共气化过程中均产生了明显的交互作用. 用缩核反应模型描述了焦炭与H2O和CO2气化反应的结果,得反应活化能分别为154.47和214.77 kJ/mol.     

焦炭在固定床反应器中的CO2气化实验研究

在固定床反应器上研究了焦炭在CO2气氛下的气化反应,分析了气化温度和颗粒大小,以及颗粒表面灰的聚集对气化反应的影响.采用两段阶梯式气化方法和扫描电镜(SEM),研究气化反应过程中灰的附着对气化效果的影响.结果表明,温度对气化反应有积极影响,在950 C～1265 C范围内温度越高气化效果越好,在1265 C时,焦炭转化率高达95%.颗粒粒径在小于20 mm时,其变化对气化效果的影响不明显,而大于20 mm时气化效果有明显的伴随下降趋势.这对于固定床气化焦炭时对焦炭的选取具有指导意义.     

煤种对煤与天然气共气化过程的影响

以移动床为反应器,进行煤与天然气共气化热态模拟实验,对无烟煤、瘦煤、肥煤与焦炭进行了对比研究,考察了煤种在不同喷吹参数H2O/CH4/O2时对高温火焰区温度、合成气有效成分H2+CO和H2/CO、以及CH4与水蒸汽转化率的影响. 结果表明,相对于焦炭,煤为原料时,高温火焰区温度略高,粗合成气有效成分H2+CO体积含量较高,且H2/CO更接近于热力学平衡值. 通过不同煤种的实验,可以直接制备H2/CO在1~2之间可调、有效成分H2+CO体积含量大于92%、残留CH4小于2%的粗合成气,CH4转化率超过90%,水蒸汽转化率高达75%. 煤种中高灰分含量有利于煤与天然气共气化过程.     

K_2CO_3对兰炭催化气化特性的影响

在固定床中考察了不同K_2CO_3植入浓度和不同温度条件下兰炭催化气化特性。结果表明,5%的催化剂植入浓度主要起到填充孔隙的作用,当植入浓度增加到10%以后,催化剂发生堆积会使颗粒表面及内部形成较多孔隙。提高气化温度可提高兰炭转化率,超过750℃之后碳转化率增幅减缓,催化剂饱和装载浓度为10%。在颗粒表面和开放孔隙中的高浓度C(O)才具有较高的脱附速率,并提高CO生成速率。在非催化条件下,随着气化的进行CO/CO_2下降,而H_2/(2CO_2+CO)先增后减。在催化条件下,H_2/(2CO_2+CO)稳定在1.5～1.7。催化剂兰炭样品中出现了K_2Ca(CO_3)_2双金属碳酸盐、K_2O、KO_2等活性组分,并随催化剂植入浓度的增加而增加。催化剂植入浓度的增加会导致失活现象加重,但兰炭在750℃条件下气化1 h催化剂没有完全失活。     

双流化床生物质气化动力学建模与分析

为进一步研究双流化床生物质气化器中合成气含量分布,将气化器鼓泡床层分为气泡相和乳化相,依据动力学反应分别进行各相质量和热量衡算,计算结果与实验值吻合较好. 随气化温度升高,CO含量增加,而H2和CO2含量降低;蒸汽与生物质质量比(S/B)增加促进水蒸汽变换和重整反应,消耗CO和CH4,生成H2和CO2,当S/B从0变化到1.2时,CO/H2变化44%,说明S/B增加主要促进了水蒸汽变换反应. 气化温度870℃及S/B=0.75条件下,当气化器高度为0~0.5 m时,H2O含量急剧下降,H2含量急剧上升,CO与CO2含量逐渐上升,当该高度大于0.5 m后,气化反应基本完成.     

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.     

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.     

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.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.     

2007～2008年世界塑料工业进展

收集了2007年7月～2008年6月世界塑料工业的相关资料,介绍了2007～2008年国外塑料工业的发展情况,提供了世界塑料产量、消费量及全球各类树脂的需求量及产能情况.按通用热塑性树脂(聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂)、工程塑料(尼龙、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚)、特种工程塑料(聚苯·硫醚、液晶聚合物、聚醚醚酮)、通用热固性树脂(酚醛、聚氨酯、不饱和聚酯树脂、环氧树脂)不同品种的顺序,对树脂的产量、消费量、供需状况及合成工艺、产品应用开发、树脂品种的延伸及应用的进一步扩展等技术作了详细介绍.     

2005～2006年国外塑料工业进展

收集了2005年7月～2006年6月国外塑料工业的相关资料,介绍了2005—2006年国外塑料工业的发展情况。提供了世界塑料产量、消费量及全球各类树脂生产量以及各国塑料制品的进出口情况。作为对比,介绍了中国塑料的生产情况。按通用热塑性树脂（聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂）、工程塑料（聚酰胺、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚）、通用热固性树脂（酚醛、聚氨酯、不饱和树脂、环氧树脂）、特种工程塑料（聚苯硫醚、液晶聚合物、聚醚醚酮）的品种顺序,对树脂的产量、消费量、供需状况及合成工艺、产品开发、树脂品种的延伸及应用的扩展作了详细的介绍。