Selective Ethylene Oligomerization Catalyzed by the Chromium Complex Bearing N-Tetrahydrofurfuryl PNP Ligand

通过胺基锂盐分离的方法合成了一种未有报道过的N-四氢糠基PNP配体E.; E分别与CrCl_3(THF)_3和Cr(CO)_6反应生成化合物[{Ph_2PN(CH_2OC_4H_7)PPh_2}CrCl_2(mu-Cl; )]_2(1)和[Ph_2PN(CH_2OC_4H_7)PPh_2]Cr(CO)_4(2).这三个化合物通过谱学和元素分析表征,化合物2进一步经; 过X射线单晶结构确认.在甲基铝氧烷(MAO)或其它助剂作用下,考察了1、2以及E/CrCl_3(THF)_3、E/Cr(acac)_3、E/Cr; Cl_2(THF)_2催化体系催化乙烯齐聚的性能.这些体系高选择性地催化乙烯四聚,最高活性为15.9 kg(product)/g(Cr)·h,; 1-辛烯的选择性最高可达63.6%.The N-tetrahydrofurfuryl diphoshinoamine (PNP) ligand (E) was synthesized by means of two-step salt elimination reactions where separation of the two kinds of the aminyl lithium salts for the respective reactions is necessary for obtaining a high yield of E. The ligand reacted with CrCl3(THF)(3) and Cr(CO)(6) to give P,P-chelation complexes [{Ph2PN(CH2OC4H7)PPh2} CrCl2(mu-Cl)](2) (1) and [Ph2PN(CH2OC4H7)PPh2] Cr(CO)(4) (2), respectively. Complexes E, 1 and 2 were characterized by spectroscopy and elemental analysis, of which complex 2 was further confirmed by X-ray crystallography. Upon activation with methylaluminoxane (MAO) or AlEt3, the catalyst systems including 1, 2, E/CrCl3(THF)(3), E/Cr(acac)(3) and E/CrCl2(THF)(2) were investigated. The best catalytic activity was achieved by 15.9 kg (product)/g (Cr)circle h in which a selectivity of 63.6% for 1-C-8 was obtained.National Natural Science Foundation of China [21473142, 21673191];; Innovative Research Team Program [IRT_14R31

Improvement of n-butanol recycling technique in industrialized production of silicon dioxide as flatting agent

针对福建某工厂现有工艺生产二氧化硅消光剂过程,采用间歇蒸馏方式回收正丁醇存在时间长、效率低等问题,提出使用双塔精馏工艺进行改进以缩短正丁醇回收时间和提高回收效率。对改进后的工艺使用流程模拟软件进行模拟计算,获得了新的工艺条件参数。改进后,冷凝分层温度为85℃,精馏塔一塔釜液中正丁醇质量分数为99.62%,精馏塔二塔釜中正丁醇质量分数为0.31%。在此基础上搭建了实验室规模精馏装置并进行了验证试验,试验结果与模拟计算值接近,相对平均偏差为5.4%,表明模拟计算的结果可信。模拟计算结果为工业装置的优化提供了依据。改进后,正丁醇回收率将大幅提高,生产周期由原来的10 H缩短为5 H,能耗显著降低。采用此工艺生产二氧化硅消光剂可大幅降低过程成本。In order to reduce time cost and increase efficiency in n-butanol recycling,a double-column distillation process was suggested to replace the existing batch process due to its high time consumption and low efficiency.The improved process was simulated with flow simulation software.The calculated results show that in the improved process,condensing temperature is 85 ℃,the mass fraction of n-butanol at the bottom of Column 1 and Column 2 is 99.62% and 0.31% respectively.The verification tests on lab-scale distillation device were carried out.It shows that the calculated results are close to the tested results,and the average relative deviation is 5.4%,which indicates the calculated results are credible,and can provide a basis for optimization in industrialized plants.Now,n-butanol recycling efficiency increases largely and production cycle is reduced from 10 h to 5 h and energy consumption drops remarkably,so production cost can be largely reduced

Optimization of Hydrometallurgical Purification for SiO_2 in the Process of Preparing Solar-grade Silicon

考察了Hf质量分数、H2C2O4质量分数、HnO3质量分数、酸浸时间、粒径、液体质量与固体质量的比值(简称液固比,下同)等因素对混酸法提纯SIO2工艺过程的影响,利用电感耦合等离子体发射光谱仪(ICP-OES)、场发射扫描电子显微镜(SEM)进行表征。结果表明,最佳工艺条件为:W(Hf)=2%、W(H2C2O4)=3%、W(HnO3)=30%、酸浸时间4 H、粒径100~120目、液固比4∶1、酸浸温度30℃。fE、Al、CA、P杂质的去除率分别达到99.99%、14.02%、73.27%、60.00%,经混酸法处理后SIO2中杂质总量的质量分数降至1.465x10-4。As a pre-treatment unit for preparing solar-grade silicon,hydrometallurgical route could remove most metallic impurities in silicon dioxide(SiO2) and raise the yield of the final product.Acid leaching of SiO2 could reduce the cost and energy consumption of industrialized development.Combined with high purity of reducing agent,the successor process of pyrometallurgy can also achieve "continuous casting".Factors such as the mass fraction of leaching agent,time,the particle size of SiO2,and the liquid-solid ratio were investigated,and the samples were characterized by means of ICP-OES,SEM,etc.The optimal reaction conditions were as follows:w(HF)=2%,w(H2C2O4)=3%,w(HNO3)=30%,reaction time 4 h,the average size of SiO2 powder particle 100～120 mesh,the liquid-solid ratio 4∶1,and room temperature 30 ℃.It was found that the final removal rates of impurities of Fe,Al,Ca,P could reach 99.99%,14.02%,73.27%,and 60.00% respectively and the mass fraction of total amount of impurities could be reduced to 1.465×10-4

Preparation and evaluation of insulin thiolated hyaluronic acid nanoparticles in vitro

目的制备胰岛素巯基化透明质酸纳米粒(InSulIn THIOlATEd HyAlurOnIC ACId nAnOPArTIClES,InS-HA-CyS-nPS),考察纳米粒的理化性质。方法以合成的具有生物黏附性质的巯基化透明质酸作为载体,采用超声乳化法制备纳米粒,考察其外观、粒径、zETA电位、包封率、载药量,并进行其冻干制剂的冻干保护剂筛选。结果制备的InS-HA-CyS-nPS粒径均一,外观圆整;平均粒径为(178.5±0.8)nM,PdI为(0.214±0.013),zETA电位为-(38.47±0.46)MV,超滤离心法测定载药纳米粒的包封率为(48.85±0.66)%,载药量为(4.79±0.13)%;选择10%的甘露醇为冻干保护剂,复溶后得到具有蓝色乳光的粒径均一的纳米粒混悬液。结论巯基化透明质酸纳米粒是蛋白多肽类药物口服给药的潜在载体,为下一步研究胰岛素纳米粒在大鼠体内药效、药动学研究提供前提和基础。Objective To prepare insulin thiolated hyaluronic acid nanoparticles( Ins-HA-Cys-NPs) and study its physicochemical properties.Methods The Ins-HA-Cys-NPs was prepared by ultrasonic emulsifying method,and the properties of nanoparticles including morphology,mean diameter,Zeta potential,entrapment efficiency and drug loading efficiency were studied,as well as the cryoprotectant selection.Results The prepared nanoparticles was round in appearance and the mean diameter was( 178.5 ± 0.8) nm,the polydispersity index was( 0.214 ± 0.013) and the Zeta potential was-( 38.47 ± 0.46) mV,while the entrapment efficiency was( 48.85 ± 0.66) %,drug loading efficiency was( 4.79 ± 0.13) %; 10%mannitol as cryoprotectant provided uniform and well dispersed suspension of nanoparticles with blue opalescence after redispersion.Conclusion The thiolated hyaluronic acid nanoparticles may be used as the carrier for oral drug delivery system of insulin,and it provides a basis for studies on rats in vivo.福建省自然科学基金(2012J05159

Study on removal boron from solargrade silicon with hydrometallurgy

湿法提纯作为冶金法制备太阳能级硅的前处理工序,可以去除大部分金属和硼杂质。研究了以氢氟酸-硫酸混合酸为浸出剂,有机溶剂甲醇作为后处理剂,去除硅粉中硼杂质的方法。采用电感耦合等离子体发射光谱仪(ICP)等对产品进行表征。酸浸过程优化工艺条件:硫酸质量分数为55%,氢氟酸质量分数为7%,酸浸温度为70℃、酸浸时间为4 H、液固质量比为8∶1。酸浸后可使硅粉中的硼杂质质量分数由6.893x10-6降至3.867x10-6,去除率为41.9%。在酸浸基础上采用有机溶剂甲醇作为后处理剂,杂质硼质量分数降至3.84x10-6,去除率为44.29%。从硼酸浸后形成的产物入手探索提高硼去除率的方法,实验验证了该方法的可行性,为研究湿法冶金预处理太阳能级硅提供了新的参考。As a pretreatment unit for preparing solargrade silicon(SG-Si) by metallurgic method,wet purification could remove most metallic impurities and nonmetallic impurities,such as boron.Experiment researched a new method to remove boron from SG-Si with mixed hydrofluoric acid-sulfuric acid as leaching agent and with organic solvent methanol as posttreatment agent.Samples were characterized by ICP and other analysis methods.When SG-Si powder had been leached at optimized conditions as follows:mass fraction of sulfuric acid was 55%,mass fraction of hydrofluoric acid was 7%,reaction temperature was 70 ℃,reaction time was 4 h,and liquid-solid mass ratio 8∶1,it was found that mass fraction of impurity boron in SG-Si was reduced to 3.867×10-6 from 6.893×10-6 and the removal rate was 41.9% after acid leaching;on the basis of the former procedure,mass fraction of impurity boron was reduced to 3.84×10-6 and the removal rate was 44.29% when treated with organic solvent.Experiment proved the feasibility of the method and provided a new reference for researching on the pretreatment of SG-Si by hydrometallurgy

Development and fluidized simulation of semi-continuous pilot reactor for carbon nanotubes preparation

第一作者：朱丽（1980—），女，硕士研究生，从事化工过程开发与设计研究。E-mail:[email protected]。联系人：汤培平，教授。E-mail:[email protected]。[中文文摘]在间歇过程的碳纳米管制备实验基础上结合经验公式,开发设计了制备碳纳米管的半连续中试流化床反应器,结果表明:催化剂100 g、反应温度650℃时,甲烷平均转化率23.2%,碳纳米管产率为177.5 g/h,操作周期为间歇反应器的1/3,反应器可较好地实现碳纳米管制备功能。用计算流体力学方法对此反应器内的气固两相流化行为进行数值模拟,得到在工况条件下,最佳的催化剂用量为100 g、操作气速为0.15 m/s等工艺参数。[英文文摘]Semi-continuous pilot test fluidized bed reactor for carbon nanotubes preparation was designed and fabricated,base on experiments of batch fluidized bed reactor and repeated calculations.When reaction temperature is 650 ℃,reaction time is 4 h,velocity of CH4,H2,N2 are 0.1m/s,0.008 m/s,0.016 m/s,the yield of carbon nanotubes is 177.5 g/h,conversion of CH4 is 23.2%,production cycle is shortened by 2/3.The fluidization behavior of gas-solid fluidization process was calculated by using the computational fluid dynamics(CFD) package Fluent6.1.And the optimal condition for carbon nanotubes is that the velocity of CH4 is 0.1m/s,and catalyst is 100g

基于微震监测的大范围破裂矿柱稳定性评价

柿竹园矿大范围破裂矿柱回采进行大爆破施工前,对装药区域的稳定性的监测与评价是确保大爆破施工安全与顺利实施的重要工作。基于柿竹园矿大范围破裂矿柱微震监测实例,详细分析了大范围破裂矿柱产生的原因,根据出矿对破裂矿柱稳定性的影响及微震监测结果,对破裂矿柱稳定性状态进行了评价。说明了微震监测能较准确地对破裂矿柱的活动状态进行监测,根据监测结果可以对破裂矿柱的稳定性状态进行较准确的评价与预警,为大爆破的施工与顺利实施提供了保障

Tannin dynamics of Kandelia candel roots in different salinity culture

对不同盐度(0‰-40‰)栽培下秋茄根的总酚、可溶性缩合单宁、结合缩合单宁、总缩合单宁的含量进行测定,探讨盐度对单宁生产的效应.结果表明:(1)不同盐度下栽培60-135d,总酚含量在相同盐度条件下随栽培时间的延长呈现出先波动而后升高的趋势,其中总酚最高含量出现在高盐度,说明一定的高盐度胁迫可以促进总酚的合成;总缩合单宁与可溶性缩合单宁含量变化趋势相似,其中可溶性缩合单宁含量显著高于结合缩合单宁.(2)在15‰盐度下栽培75-135d,秋茄根不同部位的总酚、可溶性缩合单宁、结合缩合单宁和总缩合单宁含量有相似的变化趋势,即由根尖往远离根尖的部位呈下降趋势.Total phenolics(TP),extractable condensed tannins(ECT),bound condensed tannins(BCT),and total condensed tannins(TCT) contents of Kandelia candel roots in different salinity culture were determined.In addition,the effect of salinity on tannin production was studied.The results showed as follows:(1) During the period of different salinity culture(from 60 d to 135 d),TP content fluctuated with increasing salinity,with the highest occurring in high salinity.ECT and TCT contents fluctuated under different salinity conditions with a consistent pattern.ECT contents were significantly higher than BCT contents.(2) At culture salinity of 15‰,the distribution of tannins in different parts of roots in the same period from 75 d to 135 d followed the identical pattern: the closer the root tip was,the higher the TP,ECT,BCT,and TCT contents were.福建省自然科学基金资助项目(B0410006);; 国家自然科学基金资助项目(40376026

Advances in Selective Ethylene Oligomerization Based on [PNP]-Ligand Chromium Catalysts

乙烯选择性三聚和四聚催化反应为制备1-己烯和1-辛烯提供了重要途径.在报道和披露的众多结构和组成的催化剂体系中,我们选择[PnP]配位骨架的铬催化剂体系,对其发展和应用进行了综述.论文以结构与催化性能的关联性为主线,阐述[PnP]骨架以及n和P上取代基的电子和立体空间效应对催化性能的影响.从目前的研究态势来看,[PnP]配位骨架的铬催化剂体系在乙烯选择性齐聚生产1-辛烯等线性α-烯烃方面具有发展潜力.The catalytic reaction for the selective ethylene trimerization and tetramerization provides a vital route to the production of 1-hexene and 1-octene.Among the numerous catalysts reported with diverse structures and compositions, we select the [PNP]-ligand based chromium catalysts and focus on illustration on their development and application.This contribution includes seven sections as ethylene(selective) oligomerization catalyst systems, [PNP]-ligand based Cr catalyst system, catalytic mechanism, ethylene oligomerization method, catalytic property, and conclusion and prospect, which will cover almost all of the [PNP]-ligand based Cr catalysts so far studied.In this article, we will mainly discuss the influence on the catalytic property owing to the electronic and/or steric characters of the skeleton as well as the substituents at both N and P atoms of the [PNP]-ligands.In view of the current advances in this field, this [PNP]-ligand based Cr catalyst system is of potencial in application for the production of LAO mainly as 1-octene.聚烯烃催化技术重点实验室基金(No.12DZ2260400); 国家自然科学基金(No.21473142); 教育部创新团队(No.IRT_14R31)资助项目~

催化裂解法制备碳纳米管中试反应器优化研究

对催化裂解法(CVD)间歇制备多壁碳纳米管(CNTs)的中试流化床反应器的结构进行优化研究,以期简化结构、改变出料方式、实现半连续化操作。实验结果表明:床层内置加热器开启,CNTs产量下降15%,床层阻力增加67%;预热层高度为零,反应4h,产率最高为9.2g/g;催化剂量为100g,最佳匣钵高度是35cm;将间歇操作调整为半连续操作,生产周期将从24.0h降为8.5h