水热法由富锰渣制备4A分子筛工艺初探

研究了由富锰渣制备锰的过程中产生的硅铝废渣(酸浸渣)制备4A分子筛的工艺.以浓硫酸为浸取介质,将富锰渣中锰、铁、钙、镁等可溶性物质溶出,过滤所得固相酸浸渣在反应釜器中150℃、0.4MPa下与碱反应将硅铝溶出,以分析纯Al(OH)3,为铝源,补铝调整比例到4A分子筛合适的硅/铝比,使溶液中各物质摩尔比为SiO2/Al2O3≈2,H2O/Na2O≈28,Na2O/SiO2≈0.9.浓缩溶液至过饱和状态,加入EDTA.将过饱和状态的溶液在90℃恒温5h左右,加入NaCl少许,放冷使之结晶.过滤并洗涤晶体至pH值至9～10,在烘箱中105℃干燥,于马弗炉中5000℃右煅烧1h脱水,即得4A分子筛产品.研究了EDTA对结晶母液中有色离子的络合效果,结果表明对Fe3 有一定去除效果.由XRD分析,产品主要成分为4A分子筛,但还有杂晶.     

以富锰渣制备4A分子筛

研究了以富锰渣为原料，经过硫酸浸出、酸浸渣与碱固相高温煅烧熔融制备分子筛的工艺。以10％（质量分数）的硫酸为浸取介质，在90～100℃下反应2h，将富锰渣中锰、铁、钙、镁等可溶性物质溶出，液相中的锰用来制备硫酸锰。酸浸渣与碱固相反应，将硅铝溶出，补氢氧化铝，调整比例到4A分子筛合适的硅铝比，使溶液中各物质的量比为n（二氧化硅）／n（三氧化二铝）=2，n（水）／n（氧化钠）=28，n（氧化钠）／n（二氧化硅）=0．9。浓缩溶液至过饱和状态，在空气中冷却到30℃，再升温至90℃，恒温5h。加入氯化钠少许，放冷使之结晶。过滤并洗涤晶体至pH=9-10，于马弗炉中500℃左右煅烧1h即得4A分子筛产品。     

亚熔盐法粉煤灰脱铝渣水热处理后碱含量的影响因素

以亚熔盐法处理粉煤灰的脱铝渣为原料,采用动态水热法分解脱碱,研究了不同A/S(Al2O3/SiO2质量比)、C/S(CaO/SiO2质量比)和不同脱铝溶出工艺对硅渣碱含量的影响. 结果表明,随脱铝渣A/S增加,碱含量先降低后升高,脱铝渣A/S为0.11,硅渣Na2O含量降至1.18%,适当的A/S有利于提高硅渣中含铝托贝莫来石的晶化程度;脱铝渣C/S为0.98,硅渣Na2O含量仅有1.31%,随脱铝渣C/S增加,硅渣碱含量增加,C/S过高会降低硅酸钠钙(NaCaHSiO4)的分解率,不利于生成含铝托贝莫来石相;溶出时间和停留时间较长的脱铝渣在脱碱过程中不易生成含铝托贝莫来石.     

碱法提高铝硅矿物的铝硅比

采用NaOH溶液时铝硅矿物进行预脱硅处理,测出溶渣中SiO2和Al1O3的含量,计算得出渣中的铝硅比.考察液固比、溶出温度、溶出时间、碱浓度等因素对铝硅矿物溶出后渣中铝硅比的影响.实验表明,在液固比为40∶1、温度95℃、溶出时间3 h、40%碱浓度条件下,矿物的脱硅率可达55%以上.预脱硅后渣中铝硅比由0.89提高到...     

稻壳一步煅烧法制备A型分子筛的研究

将稻壳洗净后粉碎,与NaOH和铝源混合后在高温下煅烧,水热晶化制备A型分子筛.实验探究了不同硅铝比、煅烧温度和不同铝源的影响.运用了XRD、SEM、XRF等手段对样品进行表征,并对合成产物进行了亚甲基蓝吸附实验.结果表明:在n(Na2 O):n(SiO2)=6,n(SiO2):n(Al2 O3)=0.8～2.4,n(H2 O):n(Na2 O)=35,煅烧温度850℃时,采用Al(OH)3和NaAlO2都能得到形貌规整、结晶度较好的A型分子筛,并且对25.0 mg/L的亚甲基蓝溶液吸附效果较好,吸附容量4.76 mg·g-1,去除率95％以上.此方法的优点是原料价格低,工艺简单,易于推广.     

硅铝胶气相法合成MCM-22分子筛工艺条件的影响

以硅酸和偏铝酸钠为硅源和铝源制备硅铝胶,采用气相法合成MCM-22分子筛.考察了硅铝比、钠离子含量、模板剂六亚甲基亚胺(HMI)和水用量等工艺条件对合成的影响.结果发现,与水热晶化法相比,气相法合成中硅铝比范围变窄,所需Na 含量大大降低,合成的MCM-22分子筛结晶更完整,晶粒直径较大.原料组成为SiO2:(0.02～0.033)Al2O3:(0.085～0.1)Na :1.2HMI:20H2O,晶化温度和时间分别为150 ℃和5～7 d的实验合成条件较为适宜.     

偏高岭石-碱-硅酸钠水热反应体系13X分子筛的合成

以煤系高岭石为主要原料,经破碎、粉磨、煅烧、水热处理等工艺,在偏高岭石-碱-硅酸钠水热反应体系中合成了13X分子筛.扫描电镜分析表明:产物晶形完整、粒度为1μm左右且分布均匀.用X射线衍射测试方法研究混合物的硅铝的摩尔比[n(SiO2)/n(Al2O3)]、钠硅的摩尔比[n(Na2O)/n(SiO2)]、水钠的摩尔比[n(H2O)/n(Na2O)]以及陈化时间对13X分子筛合成的影响.研究表明:该水热反应体系的最佳配比为n(SiO2)/n(Al2O3);高于13X分子筛中自身的n(SiO2)/n(Al2O3)=2.5.反应适宜的碱度条件为:n(Na2O)/n(SiO2)=1.9,n(H2O)/n(Na2O)=40,碱度过高或过低均会出现P型分子筛杂相.陈化过程在13X分子筛的合成过程中不可缺少,其适宜的陈化时间为24h.该水热反应过程遵循分子筛的液相转化机理.     

利用氧氯化锆副产物合成硅酸钠的实验研究

利用氧氯化锆生产中排放的锆硅渣和废碱液作原料,通过水热-碱化反应合成硅酸钠.先将酸性硅渣与废碱液中和,经离心水洗得到中性二氧化硅凝胶,再在反应釜中与计量的NaOH溶液进行化合反应,然后对产物进行固液分离,最后将所得溶液浓缩即得产物.通过正交试验,研究了影响SiO2溶出率及硅酸钠模数的主要因素.结果表明,起始物的n(SiO2)/n(Na2O)比影响最大,其次依次为反应温度和反应时间.最优方案按n(SiO2)/n(Na2O)=2.5配制起始物,180℃下反应3h,由此可使锆硅渣的SiO2溶出率达82％,合成的硅酸钠模数为2.21,其各项技术指标均达到国标优等品水平.     

NaOH亚熔盐法处理拜尔法赤泥的铝硅行为

针对拜尔法赤泥铝/硅比偏高的问题,对NaOH亚熔盐法处理拜耳法赤泥过程中的Al, Si行为进行了研究. 考察了溶出温度、碱/泥比、添加CaO等主要因素对终赤泥化学成分和物相结构的影响. 结果表明,溶出温度高、碱/泥比大有利于Al2O3的回收,相应的终赤泥的铝/硅比较低. 在碱/泥比6、溶出温度230℃、时间2 h的条件下,氧化铝回收率可达79.22%,终赤泥的铝/硅比可降到0.39,终赤泥中的硅主要以NaCaHSiO4和Ca3(Fe0.87Al0.13)2(SiO4)1.65(OH)5.4形式存在. 在处理CaO/SiO2>1.2的拜尔法赤泥时继续添加CaO并不能继续提高Al2O3的回收率.     

黄陵煤矸石制备4A分子筛的研究

黄陵煤矸石的灰成分以SiO2、Al2O3为主,这些组分正是合成分子筛的原料.将煤矸石经过煅烧活化、酸浸除铁、碱熔预处理后,采用水热合成的方法制备4A分子筛.通过正交试验考察了n(Na2O)∶n(SiO2)、n(H2O)∶n(Na2O)、老化时间、晶化温度、晶化时间5个因素对分子筛钙离子交换性能的影响,实验结果表明:n(Na2O)∶n(SiO2)是对4A沸石钙离子交换量影响最大的因素,其次是晶化温度,最小的为老化时间;且在n(Na2O)∶ n(SiO2)为1.3,n(H2O)∶ n(Na2O)为45,老化时间8h,晶化时间4h,晶化温度85℃下制备所得4A分子筛的钙离子交换量达到296.84 mg CaCO3/g干沸石.自制分子筛的XRD及SEM检测分析表明,最优条件下制备出的4A分子筛晶型完整,轮廓清晰,呈立方体,颗粒大小均匀,在1～2 μm左右.     

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。