Optimization for Silica Flatting Agent Manufacturing Process

沉淀法和气相法二氧化硅通称为白炭黑，因其补强性、增稠性、触变性、消光性、防粘性等特性广泛使用在橡胶、塑料、涂料、油漆等行业中。 白炭黑应用在涂料、油漆等行业作消光剂时，其消光原理有两点：一是增加涂膜表面的粗糙度，二是降低底材的反光强度。作为消光剂用白炭黑，对孔容有特定要求，国内消光剂产品孔容一般在1.0~1.8ml/g，国外产品能到达到2.0ml/g。工业生产中采用水玻璃过离子交换柱工艺制得硅胶，硅胶经过陈化、扩孔、干燥等处理后制成消光剂白炭黑。正丁醇通常在生产消光剂白炭黑过程中作为保持孔容及防塌陷的扩孔剂，目前工业上生产一吨消光剂，通常消耗正丁醇约为0.2吨。本文从扩孔剂正丁醇的替代、正丁...Precipitated silica and fumed silica are generally called white carbon black. Owing to a variety of characteristics such as reinforcing, thickening, thixotropy, light extinction and anti-sticking it is widely used in rubber, plastic, dope, paint and other industries. Flatting agent can not only increase the surface roughness of the coating but also reduce the reflective intensity of the substrat...学位：工学硕士院系专业：化学化工学院化学工程与生物工程系_化学工艺学号：2062008115160

Theoretical Study on the Electronic Spectra of cis-HOOOH and trans-HOOOH

用密度泛函方法(DFT)和全活化空间自洽场方法(CASSCF)以及耦合簇理论(CCSD)优化了反式和顺式HOOOH的平衡几何构型,用DFT计算了HOOOH顺反异构化反应的势能曲线和谐振动频率.用含时密度泛函理论(TD-DFT)和二阶全活化空间微扰理论(CASPT2)计算了反式和顺式HOOOH垂直激发能.计算结果表明:(1)反式异构体比顺式异构体稳定;(2)两种稳定构型的异构化反应有两种路径;(3)对于垂直跃迁能最低的单态和叁态,反式的垂直跃迁能比顺式的低;(4)在单激发态中,CASPT2方法预测的顺式HOOOH寿命最长的激发态为21A″,其跃迁能是167.43nm,寿命为1.44×10-5s;反式HOOOH寿命最长的激发态为21A,其跃迁能是165.52nm,寿命为2.07×10-5s.Equilibrium geometries of cis-HOOOH and trans-HOOOH have been investigated using the density functional theory (DFT), complete active space self-consistent-field (CASSCF), and coupled cluster with single and double replacement (CCSD) approaches. The harmonic vibrational frequencies on the optimized geometries were calculated using the DFT theory. The potential energy curve of the isomerization between the trans-HOOOH and cis-HOOOH was obtained by DFT calculations. Time-dependent density functional theory (TD-DFT) and complete active space perturbation theory of second order (CASPT2) calculations have been performed to obtain the vertical excitation energies of selected low-lying singlet and triplet excited states. Computed results show that: (1) trans-isomer is more stable than cis-isomer; (2) there are two pathways of the conversion between the trans-HOOOH and cis-HOOOH; (3) the vertical excitation energies of the lowest singlet and triplet excited states in trans-HOOOH are lower than those in cis-isomer; (4) in the singlet excited states, 21A state in trans-HOOOH and 21A″ state in cis-HOOOH have the longest lifetimes of 2.07×10-5 s and 1.44×10-5 s with the excitation energies of 165.52 and 167.43 nm, respectively.国家自然科学基金(20473062,20233020,20021002,20173042);; 厦门大学固体表面物理化学国家重点实验室开放课题基金(200306);; 河南省自然科学基金(0311011200,200510475012)资助项

Theoretical Study on Structures and Electronic Spectra of Linear Chain Cluster BC_(2n)B (n=1～12)

应用密度泛函理论,在B3LYP/6-31G*水平上优化得到了线性簇合物BC2B(n=1～12,D∞h)的平衡几何构型,并n计算了它们的谐振动频率.在优化平衡几何构型下,通过TD-B3LYP/cc-pvDZ和TD-B3LYP/cc-pvTZ计算,分别得到了n=1～12和n=1～7的X1Σg→11Σ+u电子跃迁的垂直激发能和对应的振子强度.在B3LYP/6-311+G*水平上计算得到+了簇合物BC2B(n=1～12,D∞h)的电离能.基于计算结果,导出了BC2B体系X1Σg→11Σ+u电子跃迁能以及第一电离能+nn与体系大小n的解析表达式.Using density functional theory, the geometries and the vibrational frequencies of linear chain BC2 B (n=1～12, D∞h) have been investigated at the B3LYP/6-31G* level. Time-dependent density func- n tional theory (TD-DFT) has been used to calculate the vertical transition energies and oscillator strengths for X1Σg →11Σ+u transitions of BC2 B with the cc-pvTZ and cc-pvDZ basis sets. At the B3LYP/6-311+G* + n level, the single-point energies of the clusters have been calculated in order to determine the first ionization energies. On the basis of present calculations, the explicit expressions for the size dependence of the excita- tion energy, the first adiabatic ionization energies (AIE) and vertical ionization energies (VIE) in linear car- bon chains were suggested.厦门大学固体表面物理化学国家重点实验室开放课题基金;; 国家自然科学基金;; 河南省自然科学基金(Nos. 20173042; 20233020; 20021002;0311011200)资助项目

Structure and Electronic Spectrum of Linear Carbon Chains LiC_(2n)Li Studied with Density Functional Theory

应用密度泛函理论,在B3LYP/6 31G(d)水平上优化得到了线型簇合物LiC2nLi(n=1 ~10,D∞h)的基态平衡几何构型,并计算了它们的谐振动频率.利用含时密度泛函理论,计算了簇合物LiC2nLi的X1∑ +g→11∑ +u跃迁的垂直激发能,以及相应的振子强度.基于计算结果,建立了跃迁能和体系大小n的解析关系式. 同时也计算了体系的第一绝热电离能,讨论了体系的电离能与体系大小n的关系.The geometries and the vibrational frequencies of linear chains LiC_(2n)Li(n=1~10) were investigated by density functional theory at the B3LYP/631G(d) level. Time-dependent density functional theory was used to calculate the vertical transition energies and oscillator strengths of X~1∑~+_g→1~1∑~+_u transitions in LiC_(2n)Li. Based on the present calculations, the explicit analytic expression between the vertical transition energies and n was obtained. Meanwhile, the first adiabaticionization energies werecalculated, and the relationship between the adiabaticionization energiesand nhas also been discussed.固体表面物理化学国家重点实验室(厦门大学)开放课题基金 (200306);; 国家自然科学基金 (20173042);; 河南省自然科学基金 资助项目(0311011200)

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

Structure and Electronic Spectrum of Linear Carbon Chain PC_(2n)P Studied with DFT

应用密度泛函理论,在B3LYP/6-31G**和B3LYP/6-311G**水平上优化得到了线型簇合物PC2nP(n=1-10)的基态平衡几何构型,计算了它们的谐振动频率.在基态平衡构型下,利用含时密度泛函理论,计算得到了簇合物PC2nP(n=1-10)的垂直激发能和相应的振子强度,导出了激发能与体系大小n的解析关系式.The geometries and the vibrational frequencies of linear carbon chain PC_ 2nP (n=1-10) were investigated by density functional theory(DFT) at the B3LYP/6-31G ** and B3LYP/6-311G ** levels. Time-dependent density functional theory (TD-DFT) was employed to calculate the vertical transition energies and oscillator strengths. On the basis of present calculations, the explicit expressions for the size dependence of the excitation energy in linear carbon chain was suggested.ThisresearchwassupportedbyStateKeyLaboratoryforPhysicalChemistryofSolidSurfaces(XiamenUniversity)(200306),andNaturalScienceFoundationofChina(20173042,20233020)

RAPD Studies of Parents of Three-Line Hybrid Rice

选用9个随机引物对31份杂交水稻亲本材料进行了rAPd分析，共检测到60条多态性带。聚类分析结果表明，所有供试材料可以被明确地区分。在9个随机引物中，有8个具有较高的多态性检测能力。以这8个引物为基础，选用任两个引物即可在任一对材料中检测出多态性的频率在9613%以上，而选用任3个引物则该频率在9921%以上。这显示了运用rAPd鉴定稻种具有简便、灵敏、高效的优点，在鉴定杂交稻种的实践中有着良好的应用前景。Seven rice male sterile lines, 12 maintainer lines and 12 restorer lines were analyzed by RAPD with 9 primers Altogether, 118 fragments were generated, of which 60 detected polymorphisms among rice lines tested.Cluster analysis showed that all lines could be uniquely distinguished by at least one RAPD marker.Eight of nine primers can detect high polymorphism.The frequencies of polymorphism in any pairs of lines would be higher than 96.13% when any two of the 8 primers were used.If any three of the 8 primers were used, the frequencies would be higher than 99.21%.The eight primers were therefore recommended as candidates for the identification of hybrid rice seeds.国家水稻基因组计划;农业部重点项

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

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

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