制备条件对Co-Mo/TiO_2-Al_2O_3汽油HDS催化剂性能的影响

以蔗糖为辅助剂,采用溶胶-凝胶法制备了介孔氧化铝及相应的Co-Mo/TiO2-Al2O3汽油脱硫催化剂,并对其进行了TEM、XRD和N2吸附表征。以FCC汽油重馏分为原料,重点考察了不同条件下制得的Al2O3对催化剂选择性加氢脱硫性能的影响。结果表明,蔗糖(sucrose)添加量和pH值对Al2O3织构产生影响,进而影响到对应催化剂的加氢脱硫性能;在Al/sucrose摩尔比1∶1、pH值5.4时Al2O3的比表面积最大、孔径分布最窄,对应催化剂的选择性加氢脱硫活性最好;Al2O3的最可几孔径随pH值的增加而增大;溶胶老化温度对Al2O3的比表面积和孔容影响较大,但对最可几孔径和孔径分布影响较小。与Co-Mo/TiO2-sAl2O3(以sAl2O3表示市售Al2O3)催化剂相比,Co-Mo/TiO2-Al2O3催化剂具有较好的选择性加氢脱硫活性,在考察的条件范围内,脱硫率相同时其对应的烯烃饱和度低5%～15%左右。     

分子筛负载型加氢脱硫催化剂的制备及其性能

采用溶胶-凝胶法低温一步合成了2种纳米介孔分子筛,对合成的样品进行了表征,并将其分别负载30% Ni2P(Co2P),将该催化剂用于噻吩加氢脱硫实验,考察了其加氢脱硫性能及稳定性. 结果表明,样品具有介孔特性,晶粒粒径约30 nm,孔径集中在20 nm左右,比表面积为400 m2/g,有一定弱酸性,有较好的热稳定性. 4种催化剂的第一次加氢脱硫率以CTAC为模板剂的载体比以CTAB为模板剂的载体高,以Co2P为活性组分比Ni2P高,低温比高温高. 4种催化剂第二次加氢脱硫率都有较大程度的降低,以Ni2P为活性组分的催化剂减少比Co2P高,360℃比300℃高,以CTAB为模板剂所制催化剂减少比CTAC高.     

焦化粗苯加氢脱硫脱氮催化剂工艺条件研究

对研制的焦化粗苯预加氢催化剂HDA016和主加氢脱硫催化剂HDB017进行工艺条件试验,在预加氢温度180 ℃、主加氢温度270 ℃、液体流速0.15 L·h-1、氢油体积比600∶1、预加氢段液体空速1.88 h^-1、主加氢段液体空速0.75 h^-1和反应压力2.5 MPa条件下,进行催化剂连续寿命考察。结果表明,产品中硫含量低于0.7 mg·L^-1,氮含量约维持在1 mg·L^-1。采用压汞法对催化剂的比表面积以及孔结构进行测试,结果表明,预加氢催化剂HDA016比表面积219.3 m2·g-1,平均孔径1.56 nm,最可几孔径1.71 nm,孔容0.19 mL·g^-1;主加氢催化剂HDB017比表面积196.6 m²·g^-1,平均孔径1.58 nm,最可几孔径1.88 nm,孔容0.15 mL·g^-1。XRD测试结果显示,活性金属组分负载在γ-Al2O3上,达到了非常高的分散度。     

水热处理对体相加氢催化剂活性的影响

体相催化剂经水热处理后,催化剂孔结构发生了改变,孔容、孔径和比表面积增加。采用小型加氢装置加工处理不同超深度脱硫难度的柴油原料,对水热处理后的催化剂进行超深度加氢脱硫活性评价。评价结果表明,体相催化剂经水热处理后,提高体相催化剂的超深度加氢脱硫活性和芳烃饱和性能,加工处理超深度脱硫难度大的劣质柴油时,加氢活性提高更加明显。以直馏柴油为原料,在相同工艺条件下,精制油中硫含量小于10μg/g时,对比没经水热处理的催化剂,水热处理后催化剂的反应温度降低了5℃。而以催化柴油为原料,在相同工艺条件下,精制油中硫含量小于10μg/g时,水热处理后催化剂的反应温度比水热处理前的反应温度降低了13℃。水热处理后的体相催化剂具有良好的活性稳定性。     

CeO2对CoMo-Ox/Al2O3催化剂轻苯加氢性能的影响

采用等体积浸渍法制备了CoMo-Ox/Al2O3和CeCoMo-Ox/Al2O3催化剂,研究了不同质量分数的CeO2对CoMo-Ox/Al2O3催化剂加氢脱硫活性的影响,考察了不同工况对催化剂轻苯加氢性能的影响,同时测试了催化剂的选择性和稳定性。用XRD、BET对催化剂进行了表征,并对其活性进行了评价。结果表明,CeO2的引入增大了CoMo-Ox/Al2O3催化剂的比表面积、孔径和孔体积,提高了催化剂的加氢脱硫活性。通过对CeCoMo-Ox/Al2O3的1 000 h测试,发现该催化剂具有良好的选择性和稳定性。     

催化裂化原料加氢预处理催化剂的研制

为满足FCC原料预处理的要求,开发了一种高脱硫、脱氮活性的FCC原料预加氢处理催化剂。该催化剂以氟改性氧化铝为载体,Ni Mo为活性组分,比表面积为169 m2·g-1,孔容为0.31 m L·g-1,平均孔径为6.5 nm,最可几孔径为3.35 nm和8.00 nm,孔径(4~10)nm占71%,具有大孔容、高比表面积和活性金属组分分散性好等特点。在100 m L固定床加氢试验装置上,以中国石化青岛炼化公司的高硫低氮混合蜡油和江苏新海石化有限公司的高硫高氮焦化蜡油为原料进行加氢活性评价。结果表明,在反应温度370℃、反应压力10.0 MPa、空速1.0 h-1和氢油体积比700∶1条件下,高硫低氮混合蜡油的脱硫、脱氮率分别为98.0%和96.5%,对高硫高氮焦化蜡油的脱硫、脱氮率分别为93.2%和90.0%。催化剂表现出原料适应性强,能有效脱除原料中的硫氮化合物,具有较高的加氢活性。     

载体不同改性方法对Ni-W催化剂加氢脱硫性能影响

以大庆石化催化柴油和焦化柴油的混合油为原料,研究了载体不同元素改性对Ni-W催化剂加氢脱硫性能的影响。结果表明,锆改性后氧化铝载体ZT-3具有适宜的孔容、比表面积和孔径分布。以ZT-3为载体制备的催化剂JZ-3的加氢脱硫活性最高,在反应温度345℃、反应压力6.4MPa、氢油体积比500:1、空速2.0h~1的条件下,加氢柴油硫含量小于10μg/g。     

Ni-Mo/Al_2O_3催化剂制备方法的研究

经过一系列的实验研究,找到了相对切实可行的催化剂制备方法,结果表明,HDA-002型预加氢催化剂比表面积171.8m~2/g,平均孔径15.19A,最大孔径18.67A,最可几孔径5-30A,强度接近30N/mm,活性组分MoO_3含量16.7wt%,NiO含量6.04 wt%,助剂P2O5含量3.08wt%,催化剂脱烯烃转化率90%左右,脱硫转化率70%以上,脱氮转化率超过90%。     

焦化粗苯加氢精制催化剂的研究

对研制的焦化粗苯加氢脱硫催化剂进行工艺条件试验;在预加氢温度180℃,主加氢温度270℃,液体流速0.15 L·h~(-1),氢油体积比600:1,预加氢段液体空速1.88 h~(-1),主加氢段0.75 h~(-1)和反应压力2.5 MPa条件下,对HDA016预加氢催化剂和HDB017主加氢催化剂进行连续寿命考察,结果表明,产品中硫含量低于0.7 mg·L~(-1),氮含量维持在1 mg·L~(-1)。采用压汞法对催化剂的比表面积以及孔结构进行测试,并由DX~(-1)000型X射线衍射仪对催化剂进行XRD表征,结果表明,预加氢催化剂HDA016比表面积219.3 m2·g~(-1),平均孔径1.56 nm,最可几孔径1.71 nm,孔容0.19 m L·g~(-1);主加氢催化剂HDB017比表面积196.6 m2·g~(-1),平均孔径1.58 nm,最可几孔径1.88 nm,孔容0.15 m L·g~(-1)。XRD测试结果显示,活性金属组分负载在γ-Al2O3上,达到了非常高的分散度。     

浆态体系中吲哚对NiMo/g-Al2O3加氢脱硫性能的影响

以二苯并噻吩为模型化合物,在浆态反应釜中考察了吲哚对NiMo/g-Al2O3催化剂加氢脱硫性能的影响. 用微库仑仪、气相色谱-质谱联用仪对反应中的样品进行含硫量和组分分析,并对反应前后的催化剂进行性能表征. 结果表明,加入吲哚在一定程度上提高了活化阶段的反应速率,但显著降低了活化后的反应速率,导致加氢脱硫总体活性显著下降,脱硫率由70%降到约58%. 反应前后催化剂表面形貌和活性相晶体结构均无明显变化,但比表面积有所增加. 加入吲哚导致催化剂孔径减小约12%,积碳量增加约50%. 组分分析表明,加入吲哚后反应中生成的环己基苯显著减少,加氢路径受到抑制.     

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.     

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。     

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.