煤热解焦油化学破乳脱盐试验研究

为减少煤焦油乳状液水中大量无机盐对分馏塔冷凝器等设备的腐蚀,促进煤焦油与水分离,利用化学破乳方法对煤焦油进行了脱盐试验,探讨了煤焦油化学破乳的可行性,考察了破乳剂类型、破乳剂添加量、注水量、脱盐温度及停留时间等试验条件对煤焦油脱盐效果的影响。结果表明,自制聚醚破乳剂脱盐效果较佳,破乳剂添加量100×10~(-6),注水量15%,脱盐温度110℃,脱后煤焦油中盐含量均出现明显拐点,停留时间在一定范围内对脱盐效果影响甚微。因此,自制聚醚破乳剂较其他2种较广泛应用于煤焦油脱水的破乳剂具有更好的脱盐效果,这主要归因于其特殊结构与煤焦油中沥青质有很强的相互作用。     

中低温煤焦油电脱盐处理技术研究

采用电脱盐法,在破乳剂和脱金属剂共同作用下,对一种中低温煤焦油进行脱水、脱盐及脱金属预处理研究。确定电脱盐工艺最佳条件为:电场强度为1 000 V/cm,处理温度为140℃,注水比例为6%,破乳剂加入量为30~50 ppm,处理时间为20 min。在此工艺条件下处理后的煤焦油中盐含量由19.73 mg/L降低到12.96 mg/L,脱盐量达到34%以上,水含量由100%降低到13%,金属脱除量达到27%以上。经过预处理的煤焦油能够满足后续加工过程的需求。     

煤焦油脱盐脱水助剂筛选及评价

煤焦油加氢改质生产清洁燃料油工艺是目前煤焦油加工的重要手段。在煤焦油物料进入加氢阶段前,原料的脱盐、脱水、脱渣等净化预处理是保证煤焦油加氢工艺得以顺利进行的关键。由于煤焦油密度大且与水接近、黏度高、热稳定性差、含杂元素的极性类物质含量高的特点,导致煤焦油乳化液非常稳定,给煤焦油原料脱盐脱水的预处理带来更高难度。针对煤焦油的特点,设计了煤焦油脱盐脱水助剂评价筛选装置和方法,分别以中低温煤焦油和高温煤焦油为原料,开展煤焦油脱盐、脱水助剂筛选评价实验,并进一步考察了煤焦油在电场条件下脱盐脱水的效果。采用筛选出的助剂,中低温煤焦油经过二级脱盐脱水处理后,盐含量脱除率达到96%以上,脱水率达到91%以上,可以满足煤焦油后续加工基本进料要求。而高温煤焦油需经过四级电场处理后,原料盐含量脱除率才能达到90%以上,水含量脱除率在95%以上。     

响应面法优化煤焦油电脱盐工艺

在单因素实验基础上采用响应面分析法的中心组合设计原理优化了煤焦油电脱盐、脱水工艺。优化得到的工艺条件为:电脱温度110.97℃,电场强度983.06 V/cm,破乳剂注入量9.65μg/g,水注入量9.11%,脱金属剂注入量30μg/g,电脱总时间8 min。电脱后煤焦油中的金属含量为24~25μg/g,水份小于300μg/g,固体杂质小于400μg/g,符合加氢原料油的进料要求。     

煤焦油电脱盐脱水技术研究进展

煤焦油中含有的水、无机盐、金属和固体杂质会对后续加工装置产生不利影响,也会降低二次加工原料和后续产品的品质。因此,在煤焦油加工过程中,需先对煤焦油进行预处理。与其他预处理技术相比,煤焦油电脱盐脱水技术具有对原料适应性宽、处理过程中不易发生缩合生焦、脱盐脱水效果好等优点,具有广阔的发展空间。笔者简述了煤焦油电脱盐脱水技术原理,综述了煤焦油电脱盐脱水技术在破乳方面的研究热点,包括煤焦油破乳机理、破乳动力学以及破乳剂用量、破乳剂种类等因素对破乳效率的影响,探讨了针对煤焦油特性改进的电脱盐脱水技术和目前工业应用上存在的问题及解决对策。最后,提出开发新型破乳剂、进行破乳剂的复配和组合多种脱盐脱水技术是未来主要的研究和发展方向。     

低温煤焦油破乳脱水研究

以某种低温煤焦油为原料,研究了低温煤焦油的乳化现象,综合采用加热静置、添加破乳剂、搅拌、超声以及离心处理等破乳方法对低温煤焦油进行脱水,分析比较了各种方法的脱水效果,获得了优化的脱水实验条件.其结果为:在80℃恒温静置30min,破乳剂DH投加300×10-6,100r/min搅拌5min,0.4 W/cm2超声1 min,5 000r/min离心10 min条件下,可得到51.3%的脱水率.     

原油电脱盐装置操作条件优化

以鲁宁管输油为原料进行了破乳剂筛选、原油预处理研究,考察了鲁宁管输油电脱盐的影响因素,结果表明:破乳剂SXF 36对原油破乳效果较好;优化操作条件为:操作温度135~140℃,注水量为6%~7%,交直流复合电场强度为900~1 100 V/cm,注水量为6%~7%,破乳剂SXF 36注入量15~20μg/g,优化条件下原油经过脱盐三级预处理,脱后原油含盐由平均5.90 mg/L降低到2.52 mg/L,电脱盐切水含油平均122.1mg/L降到83.74 mg/L。     

百重七含泥沙原油破乳脱水研究

克拉玛依油田百重七稠油处理站原油乳状液中含有大量泥砂,泥沙体积含量0.6‰～1‰,给原油脱水造成困难。本文以百重七原油处理站所处理的综合原油为研究对象,研制出破乳脱水用的KXDS破乳剂;同时考察了影响原油破乳脱水的几个因素,确定出最佳破乳温度和破乳剂最佳加量。KXDS破乳剂应用于现场后,破乳剂用量由120 mg/kg降低到80 mg/kg,破乳脱水温度由85℃降低到65℃,脱后原油达到外输优质标准,污水水质达标。     

高效广谱微生物复合破乳剂的制备及其应用

为解决破乳剂的选择性强、破乳效率低的问题,采用化学破乳剂和微生物破乳剂复合的方法,研制出了广谱、高效、低成本的破乳剂,并用大庆三次采油采出液、塔河原油、南阳原油、蓬莱原油、俄罗斯混合原油进行了脱水、脱盐评价。结果表明:对于大庆油田采出液,微生物复合与化学破乳剂比较,脱水效率提高5%以上,脱出水含油可降低40%以上;对于易乳化的南阳原油、蓬莱原油,脱后含盐可达3 mg/L以下,脱出水含油可降低50%以上。工业应用表明:对于俄罗斯混合原油脱后含盐可达2 mg/L以下,脱出水含油可降低70%以上,脱后排水含油小于15 mg/L。所研制的微生物复合破乳剂适应性强,成本可降低20%~50%。     

油溶性原油破乳剂的实际应用

中国石油化工股份有限公司济南分公司原油脱盐装置设计能力为 500×10~4t/a,采用高速电脱盐和交直流电脱盐技术,主要加工胜利原油、临盘原油和进口原油,2018年开始使用江苏太湖新材料控股TH-BE01油溶性原油破乳剂,装置运行平稳,脱水、脱盐效果较为理想,总脱盐率基本稳定在92%以上,TH-BE01添加量为13mg/L,TH-BE01油溶性原油破乳剂具有加量小、提高装备脱盐率等特性。     

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.     

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.     

Highly moisture-proof polysilsesquioxane coating prepared via facile sol-gel process

A highly moisture-proof polysilsesquioxane coating was obtained from a new bis-silylated precursor, which was synthesized from 3-aminopropyltriethoxysilane (APTES) and m-xylylene diisocyanate (m-XDI) in tetrahydrofuran (THF) and verified by ¹H MAS NMR. For direct comparison purposes, an SiO₂ coating was also prepared by the Stöber method using tetraethoxysilane (TEOS) as the reactant. Interestingly, the coating obtained from the polysilsesquioxane sol exhibited a much higher moisture resistance capability than its counterpart, which was attributed to its more compact feature between nanoparticles as characterized by N₂ absorption experiment and transmission electron microscopy (TEM). Furthermore, its high transparency of about 92% showed potential for application in the protection of optical crystals.