还原工艺对费托合成铁基催化剂反应性能的影响

为获得还原参数对铁基费托合成反应性能的影响规律,利用铁基催化剂,在固定床反应器中考察还原氢碳比、温度、空速和压力对催化剂物理性能以及费托合成反应性能的影响。结果表明,在不同的还原工艺下,还原后的铁基催化剂比表面积下降,平均孔径增大;还原氢碳比和还原压力的升高抑制了催化剂的活性,CH_4和CO_2的选择性及C_2~C_4含量升高,C_(5+)含量下降,烃分布向轻质烃分布;还原温度和还原空速的增加有利于提高催化剂活性,还原温度的提高促使烃分布向轻质烃分布,还原空速的提高对产品分布影响不大。     

高温对浆态床中Fe-Cu-K-Si催化剂费托合成反应性能的影响

为了研究高温对费托铁基催化剂性能的影响,在浆态床反应器中考察了高温对Fe-Cu-K-Si费托合成催化剂反应活性及选择性的影响。催化剂评价结果表明,与265℃相比,320℃下搅拌釜内浆液高度降低22%,但液面高度保持平稳;CO转化率提高了20%,CO_2选择性降低了2%左右。提高反应温度后,CH_4和C_2~C_4选择性分别提高了4.7%和11.72%,C_2~C_4的烯烷比提高了1.99;C_3的烯烷比从4.27提高到7.64,C_2的烯烷比从3.00提高到3.87,但是C3的烯烷比提高幅度明显高于C_2。升高温度可提高费托合成的CO转化率、C_1~C_4低碳烃选择性及烯烷比,但也降低了C_(5+)的选择性。因此,工业生产中要根据烃类产品分布的实际需要来控制反应温度。     

费托合成蛋壳型催化剂活性组分厚度的模拟计算

采用Comsol-Multiphysics软件对蛋壳型Co基催化剂费托合成反应体系进行了CFD模拟计算。通过建立合理的费托合成催化剂颗粒三维模型进行计算,重点研究了催化剂活性组分厚度对费托合成反应产物分布、温度分布以及转化率的影响。结果表明:费托合成反应内扩散阻力较大,CO在催化剂表面和内部存在明显的浓度差。且由于H_2的扩散速率远大于CO的扩散速率,导致催化剂颗粒内部氢碳比很高,不利于油类和蜡类物质的生成;随着催化剂活性组分厚度的增加,CO转化率逐渐提高,甲烷和低碳烃的选择性逐渐增大,而C_(10)H_(22)和C_(22)H_(46)的选择性逐渐减小;催化剂颗粒内部的温度峰值逐渐向催化剂内部移动,不利于反应热的转移。对于尺寸为?2.5 mm的蛋壳型球形催化剂,较佳的催化剂活性组分厚度为0.125 mm。     

Fe-M(M=V、Cr、Mn)熔铁催化剂的费-托合成反应性能研究

采用高温熔融法制备了一系列Fe_3O_4-FeO基Fe-M(M=V,Cr,Mn)熔铁催化剂,考察了其在n(H_2)/n(CO)=1.5、反应温度320℃、反应压力2.0 MPa和空速11400 h~(-1)条件下的费托合成反应(FTS)催化性能,研究了V、Cr、Mn助剂对Fe_3O_4-FeO基熔铁催化剂FTS催化性能的影响。并结合X射线衍射(XRD)、H_2程序升温还原(H_2-TPR)、H_2/CO/CO_2程序升温脱附(TPD)等手段对反应前后催化剂的物化性能进行表征。结果表明,Mn、V、Cr助剂的添加都增加了催化剂表面的碱性,提高了低碳烯烃选择性(C_2~=～C_4~=)。其中,添加V和Cr助剂后的催化剂,CO的转化率都有所降低,C_(5+)高碳烃选择性也大幅度降低。虽然V助剂的添加其产物中低碳烯烃选择性提高最多,但是其CO转化率大幅度下降。而Mn助剂添加后,其CO转化率最高,副产物CH_4选择性最低,且目标产物低碳烯烃选择性升高。因此,Mn是Fe_3O_4-FeO基熔铁催化剂费-托合成反应有利的助催化剂。     

生物质合成气合成二甲醚的研究

在加压固定床反应装置上进行了生物质合成气合成二甲醚(DME)的研究.采用机械混合法制备二甲醚合成双功能催化剂.考察了组成为V(H_2):V(CO):V(CO_2):V(CH_4)=52:24:23:1的生物质合成气在不同反应温度、空速、压力下对合成二甲醚反应的影响.同时进行了102 h的催化剂的稳定性实验.结果表明,在260-300℃范围内,随反应温度的升高,CO转化率和二甲醚的选择性均先增大后减小;随反应压力的升高,CO转化率和二甲醚选择性都随之升高;原料气中高浓度的CO_2可导致铜基催化剂较快的失活.     

铁基费托合成催化剂研究进展

综述了近十年来铁基催化剂在费托合成反应中的研究进展,探讨了铁基催化剂活性组分的确定及影响铁基催化剂活性组分的因素,对比了3种催化剂制备方法（熔融法、沉淀法、负载法）和5种催化剂载体（氧化物、分子筛、碳材料、双孔材料和核壳材料）对费托合成反应性能的影响,从反应活性、选择性和反应稳定性3个方面阐述了助催化剂在费托合成反应中的作用。分析认为：碳化铁是铁基费托合成催化剂的活性组分;在铁基催化剂的制备过程中,选择适宜的制备方法、载体、助催化剂,可以达到提高费托合成反应活性、目的产物选择性和反应稳定性的效果。提出合成特定结构碳化铁、进一步研究铁基催化剂反应机理仍是未来研究的重点。     

费托合成催化剂表面碳-氧键活化的研究

本研究针对费托合成反应中催化剂的活性相,即金属碳化物的生成进行了表面碳-氧键活化的研究。在催化剂的预处理阶段,采用CO对铁基催化剂和钴基催化剂进行渗碳处理,形成碳化铁和碳化钴。XRD图和TEM图的分析结果证实了产物的形成。进一步的实验结果表明,钴基催化剂的目标产物选择性高于铁基催化剂。通过密度泛函理论模拟计算,发现铁基催化剂表面碳-氧键的活化能力低于钴基催化剂,差异为1.26eV。因此,钴基催化剂在费托合成反应中具有更高的活性和选择性。     

费托合成蛋壳型催化剂活性组分厚度的模拟计算

采用Comsol-Multiphysics软件对蛋壳型Co基催化剂费托合成反应体系进行了CFD模拟计算。通过建立合理的费托合成催化剂颗粒三维模型进行计算,重点研究了催化剂活性组分厚度对费托合成反应产物分布、温度分布以及转化率的影响。结果表明：费托合成反应内扩散阻力较大,CO在催化剂表面和内部存在明显的浓度差。且由于H₂的扩散速率远大于CO的扩散速率,导致催化剂颗粒内部氢碳比很高,不利于油类和蜡类物质的生成;随着催化剂活性组分厚度的增加,CO转化率逐渐提高,甲烷和低碳烃的选择性逐渐增大,而C₁₀H₂₂和C₂₂H₄₆的选择性逐渐减小;催化剂颗粒内部的温度峰值逐渐向催化剂内部移动,不利于反应热的转移。对于尺寸为?2.5 mm的蛋壳型球形催化剂,较佳的催化剂活性组分厚度为0.125 mm。     

工业费托合成浆态床反应器的模拟

作为煤间接液化工业装置的核心设备,费托合成反应器的性能对装置的经济性有着举足轻重的影响。基于双气泡的轴向扩散模型耦合尾气循环开发了浆态床反应器模拟软件,对神华宁煤4×10~6 t/a的煤间接液化工业装置的费托合成反应器进行了计算分析,得到了合成气转化率、产物选择性等数据。计算结果和运转数据相一致,验证了反应器模型的合理性。在此基础上,利用模型对新鲜合成气氢碳比的影响进行研究,结果表明,随氢碳比的增加,CO的总转化率的变化不显著,H_2的总转化率明显下降,CO_2的选择性下降,CH_4选择性上升,单位合成气产油率下降,说明氢碳比的提高,在抑制水煤气变换反应发生的同时会造成产品的轻质化。     

压力对CH_4/CO_2重整制取合成气反应性能的影响

以 Ni/CeO_2-Al_2O_3为催化剂,考察了压力对 CH_4/CO_2重整反应的影响。实验结果表明,提高反应压力不仅使甲烷和二氧化碳的转化率降低,并由于积炭的加剧致使催化剂的失活速度加快。提高原料气中 CO_2与 CH_4摩尔比,气体空速,反应温度可以提高催化剂稳定性,减缓催化剂的失括速度。向反应体系中加入消碳能力强的 O_2同样可以提高催化剂稳定性。     

Sapindaceae,cyanolipids, and bugs

Scentless plant bugs (Heteroptera: Rhopalidae) are so named because adults of the Serinethinae have vestigial metathoracic scent glands. Serinethines are seed predators of Sapindales, especially Sapindaceae that produce toxic cyanolipids. In two serinethine species whose ranges extend into the southern United States,Jadera haematoloma andJ. sanguinolenta, sequestration of host cyanolipids as glucosides renders these gregarious, aposematic insects unpalatable to a variety of predators. The blood glucoside profile and cyanogenesis ofJadera varies depending on the cyanolipid chemistry of hosts, and adults and larvae fed golden rain tree seeds (Koelreuteria paniculata) excrete the volatile lactone, 4-methyl-2(5H)-furanone, to which they are attracted.Jadera fed balloon vine seeds (Cardiospermum spp.) do not excrete the attractive lactone. Loss of the usual heteropteran defensive glands in serinethines may have coevolved with host specificity on toxic plants, and the orientation ofJadera to a volatile excretory product could be an adaptive response to save time.Mention of a commercial product does not consititute an endorsement by the USDA.     

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.     

2008～2009年世界塑料工业进展

收集了2008年7月～2009年6月世界塑料工业的相关资料,介绍了2008～2009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、环氧树脂、不饱和聚酯树脂)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。     

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.