工业蒽中蒽、菲、咔唑的分离精制技术

按物理分离法、化学分离法与复合分离法3种类型，综述了蒽、菲和咔唑分离与精制技术的发展现状，分析了各种方法所具有的优势，同时指出了不足之处，对分离与精制技术的发展提出了指导性意见。     

精蒽蒽含量测定方法的改进

ＨＧ２－１４００－８０精蒽蒽含量测定过程中滴定终点不明显，结果偏差大，经研究实验，在加指示剂滴定前加适量溶剂，可使滴定终点更明显，与原方法比较蒽含量结果相同，平行样结果更接近。     

用紫外吸收光谱法测定粗蒽中菲、蒽的含量

用紫外吸收光谱法同时测定粗蒽中菲、蒽的含量,结果表明,采用环已烷作溶剂,吸收波长分别为293nm和357nm,在0.004～0.04g/L范围内,菲、蒽符合线性关系。该方法操作简单、测定迅速、结果准确。     

新型复合工艺制取蒽系产品的研究

研究了用复合工艺制取蒽系产品的新方法,该法可同时得到纯度９９．１４％的蒽、９６ ２８％的菲和９６．８８％的咔唑,具有流程简单、投资低和无环境污染等特点。     

粗蒽加工工艺的研究现状和进展

依据精细化工的发展和炼焦工业的现状，精蒽、精咔唑的供应紧张状况仍将持续。借鉴国外焦油加工工艺，开发符合国情的粗蒽分离新工艺是当条之急。本文主要介绍了粗蒽加工的生产工艺和发展趋势，提出了利用分子工程的研究方法进行了焦油加工基础研究的问题，对减少粗蒽加工成本、合理利用煤焦油资源有一定的启示。     

蒽烷基化和烷基转移合成2-戊基蒽工艺研究

2-戊基蒽是氧化法合成2-戊基蒽醌工艺的关键原料。以蒽和叔戊醇为原料经Friedel-Crafts烷基化合成了2-戊基蒽,由核磁共振氢谱(1H NMR)表征其结构,并考察催化剂、溶剂、反应物的量比、温度和时间对反应的影响。以烷基化的主要副产物二戊基蒽为原料,经烷基转移反应合成了2-戊基蒽,考察了催化剂、溶剂、温度、时间和反应物的量比对反应的影响。结果表明,AlCl3在烷基化和烷基转移反应中均具有良好的低温催化活性。在最佳烷基化反应条件下,蒽的转化率为92.8%,2-戊基蒽的收率为76.3%;在最佳烷基转移反应条件下,二戊基蒽的转化率为85.0%,2-戊基蒽的收率为68.9%。     

9—蒽甲醛的合成

以蒽、三氯氧磷和DMF为原料合成9－蒽甲醛。最佳工艺条件为：n(蒽）；n(三氯氧磷）；n(DMF)=1:2:1.4、反应温度90－95℃，反应时间15h、DMF加入速率为0．1ml/m、DMF加料时间约240分钟，产率达97％。     

提高粗蒽质量的生产经验

我厂焦油蒸馏装置采用两塔式切取混合馏分工艺，从蒽塔切取Ｉ蒽油，经结晶和真空过滤后，滤饼在立式离心机中离心分离得产品粗蒽。由于我厂的过滤机和离心机设备陈旧，近几年来粗蒽的质量难以达到国家标准，含蒽量仅在３３％左右。为此，我们在分析影响粗蒽质量和收率各因素的基础上，对生产工艺进行了适当的调整，取得了很好的效果。１影响粗蒽质量和收率的因素（１）Ｉ蒽油对粗蒽质量的影响。控制Ｉ蒽油的主要质量指标是３００℃和３６０℃前馏出量。３６０℃前馏出量直接影响Ｉ蒽油的粘度，同时也代表了Ｉ蒽油的含蒽量。对于３６０℃前馏…     

煤焦油中蒽、菲、咔唑的精制技术

主要介绍了煤焦油中蒽、菲和咔唑的精制方法,系统地总结了溶剂洗涤法、精馏-溶剂法、结晶-精馏法、乳化液膜法、区域熔融法、溶剂萃取-恒沸蒸馏-升华法和化学分离法、新型分离法等精制蒽、菲及咔唑的工艺原理,对各种方法所具有的优势及不足之处进行了评述。     

粗蒽精制方法述评

综述了各种粗蒽精制方法，比较了其优缺点，特别介绍了乳化液膜法精制粗蒽新工艺及其应用前景。     

蒽在N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和1-N-2-甲基吡咯烷酮中溶解度的测定与关联

用平衡法测定了蒽在N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMA)和1-N-2-甲基吡咯烷酮(NMP)中20—95℃下的溶解度;应用UNIFAC法建立了蒽在DMF、DMA和NMP中的溶解度的模型方程,并采用MATLAB语言对模型方程进行了求解,计算得到了蒽在DMF、DMA和NMP中的溶解度。结果表明,实验测定值与模型计算值总体规律吻合较好,蒽在DMF、DMA和NMP中溶解度模型计算值和实验值的平均偏差分别为17.56%,15.24%和29.65%,UNIFAC可以预测蒽在DMF、DMA和NMP中的溶解特性,为蒽的溶剂法分离过程中溶剂的选择和工艺优化提供了一定的理论依据。     

蒽油馏分深加工工艺现状及研究进展

介绍了蒽油馏分深加工的2种工艺、蒽油精制分离提取精蒽、菲、咔唑工艺的现状及研究进展,阐述了蒽油馏分加氢生产轻质燃料油工艺研究进展、工艺原理、工艺流程等。对山西焦化集团有限公司未来建设蒽油深加工项目提出了建议。     

Optimization of solvent crystallization process in obtaining high purity anthracene and carbazole from crude anthracene

Solvent crystallization is the main method used for preparing anthracene and carbazole from the crude anthracene. The key to the optimization of this method is improving the solubility selectivity of the solvent by means of solvent modulating and process optimization. In this study, the solubility of anthracene, phenanthrene, and carbazole in xylene, dimethylformamide (DMF), DMF with amine/amide, isopropanolamine, and chlorobenzene is examined and the solid‐liquid ternary anthracene–carbazole–DMF/(DMF+19.96% isopropanolamine) system phase diagram is determined and applied in the solvent crystallization process. The results showed that the solubility selectivity of xylene increases with increased temperature. Also, selectivity increases with an increase of the amount of isopropanolamine in the mixture of DMF and isopropanolamine, while decreases with increased temperature. Through multiple washings of crude anthracene with xylene, DMF+19.96% isopropanolamine, and chlorobenzene, it was possible to obtain anthracene and carbazole of purity higher than 98 wt %. © 2013 American Institute of Chemical Engineers AIChE J, 60: 275–281, 2014     

Determination of crystalline thermodynamics and behavior of anthracene in different solvents

To screen suitable solvents for anthracene crystallization, the solubilities of anthracene and metastable zone width were determined in four different solvents, N,N‐dimethyl formamide (DMF), xylene, tetrachloroethylene, and diethylene glycol dimethyl ether from 30 to 80 °C at atmospheric pressure using a self‐made crystallizer. The cooling modes, solvents, and the effects of carbazole on the solvent crystallization process of anthracene were also investigated. The composition of mother liquors and solid products were measured by gas chromatography; the solids were analyzed by scanning electron microscope, X‐ray diffractometer, differential scanning calorimetry, granulometer, and fluorescence spectrometer. The results showed that a uniform anthracene crystal was obtained when using DMF under the forced circulation cooling mode. Solid solution of anthracene and carbazole was initially detected in solvent crystallization. The existence of carbazole in solution has an obvious effect on the crystal morphology of anthracene, to some extent, is beneficial to the crystal growth of anthracene. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2160–2167, 2018     

Comparison of anthracene and phenanthrene in coal liquefaction

A comparison of anthracene and phenanthrene as solvents was undertaken by liquefying either Wyodak or Kentucky 9/14 coal in the presence of hydrogen or nitrogen. Phenanthrene was found to be a better physical solvent than anthracene for liquefying both coals. Anthracene and its derivatives are better hydrogen-shuttling solvents than phenanthrene and its derivatives. Hydrogenation of anthracene to tetrahydro-anthracene was observed with both coals. Dihydroanthracene is a better hydrogen-shuttling solvent than dihydrophenanthrane in the liquefaction of Kentucky 9/14 coal. Anthracene is a better solvent than phenanthrene in the presence of 1-methylnaphthalene in liquefying both Wyodak coal under hydrogen and Kentucky 9/14 coal under nitrogen. The minerals in Kentucky 9/14 coal appear to be better hydrogenation catalysts than those in Wyodak coal. Labile hydrogen from coal appears to escape readily before reacting with hydrogen-shuttling solvents under the atmospheric environment.     

从煤焦油分离提纯蒽和咔唑工艺改进探讨

溶剂结晶-精馏法是目前从煤焦油中分离提纯蒽和咔唑的比较先进成熟的已工业化工艺,其杂质的脱除主要在溶剂结晶部分,操作步骤多,但杂质分离效果还不是很理想,最终影响产品纯度。通过实验研究,发现结晶物中高杂质母液的滞留是该工艺杂质分离效果难以提高的关键因素。提出了溶剂结晶结合抽滤-精馏法新工艺,给结晶箱组合气液分离器,实现结晶同步抽滤功能,降低结晶物的母液滞留量,可提高分离效果,减少溶剂循环量,提高产品纯度和回收率,降低装置能耗,增加产能,有较好的经济性。     

Oxidation kinetics of anthracene with nitrogen dioxide in acetic acid

Kinetics of liquid-phase oxidation of anthracene to anthraquinone with nitrogen dioxide in acetic acid as solvent has been studied. The reaction takes place through the anthrone as intermediate compound. The first and second reactions are first order with respect to anthracene and anthrone concentration, respectively. The values of the rate constants in the temperature range 60–95°C have been reported. According to the reaction system developed, an industrial process for the manufacture of anthraquinone of high purity has been proposed.     

由脱晶蒽油制备沥青树脂的研究

以脱晶蒽油为原料,苯甲醛为交联剂,在浓硫酸的催化作用下合成了沥青树脂.采用FT-IR和TCA分析手段研究了缩聚反应机理和热失重行为.试验过程中考察了合成条件对沥青树脂的结焦值、恩氏黏度和黏结强度等性能的影响.结果表明,脱晶蒽油与苯甲醛发生了阳离子聚合反应,与原料相比,沥青树脂的残炭值提高了24％,最大失重速率时的温度相对升高了143℃.改变合成工艺条件能调控沥青树脂的性能指标.