煤基石脑油加氢研究

采用三段加氢工艺对煤基石脑油进行了加氢处理,重点研究了反应温度、压力、空速对一段加氢效果的影响,并对该段催化剂的使用寿命进行了考查,初步探讨了三段加氢反应温度对加氢性能的影响。研究结果表明经过三段加氢后的产品溴值小于1.0 g Br/100 g,总硫小于0.5μg/g,可用于汽油调和组分、芳烃抽提或环保溶剂油。     

加氢生产低芳溶剂油技术

介绍了国内外溶剂油生产技术的发展现状.为满足低芳溶剂油生产的不同需求,中国石化抚顺石油化工研究院先后开发出了高压加氢、中压两段加氢及低压加氢的系列化低芳溶剂油生产技术.溶剂油产品质量优良,达到了国外同类产品的水平.     

FH-FS柴油超深度加氢脱硫催化剂的芳烃加氢性能

中国石化抚顺石油化工研究院（FRIPP）开发了最新一代的柴油超深度加氢脱硫催化剂FH-FS，对其用于几种含硫、氮和芳烃差异较大柴油原料的加氢精制试验结果进行了分析，重点讨论了芳烃加氢性能。试验在200 mL小型加氢装置上进行，在氢油体积比500∶1、反应压力6.4 MPa和体积空速(1.0～2.5) h^－1等工艺条件下，使用FH-FS催化剂，精制油硫含量均可降至50 μg·g^－1以下，同时可脱除更多的芳烃，使多环芳烃脱除率达到71.0%～80.5%，密度下降(0.016 1～0.026 9) g·cm^－3，十六烷值提高1.5～15.8个单位，可较大幅度提升柴油质量。FH-FS催化剂在反应温度比参比剂低15 ℃时，脱硫和脱氮水平相当，但多环芳烃和总芳烃脱除率仍比参比剂高10个百分点以上。FH-FS催化剂对于炼油厂生产低芳烃、低密度和高十六烷值的优质超低硫(S＜50 μg·g^－1)，甚至是无硫（S＜10 μg·g^－1）柴油来说，是一非常有效的催化剂。     

新型乙炔加氢催化剂的工业应用

通过对原催化剂进行性能改进,制备新型C₂加氢催化剂,并对该催化剂的应用性能进行研究。结果表明,与国产1^#催化剂和进口2^#催化剂相比,新型C²加氢催化剂具有活性高、稳定性好、选择性高、乙烯增量高、聚合物生成量低和再生周期长等特点,具备工业应用条件。     

重整抽余油催化加氢制优质溶剂油

在低压条件下进行了重整抽余油加氢脱不饱和烃制优质溶剂油的试验。Pt/Al₂O₃催化剂在该反应中表现出优良的低压加氢反应活性和稳定性,经加氢处理后,重整抽余油中的烯烃转化率和芳烃转化率分别可达99%和95%以上。     

固定床加氢装置开工过程中要点和难点

加氢装置开工是每套装置最重要的环节,其中涉及的油联运、烘炉、氢气气密、硫化、钝化、循环氢量控制以及反应温度的控制都是要点、难点。供氢溶剂油加氢是将原料油适度加氢饱和转化为部分饱和的双环芳烃和部分饱和的多环芳烃,独立的芳烃饱和过程反应物的碳数不变(即不产生小分子),为加氢装置提供芳碳率适度的供氢溶剂油。此论文以溶剂油加氢与加氢精制、加氢裂化共用一套循环氢系统为例,首先对固定床加氢装置的开工要点和难点进行介绍,其次结合国内多套加氢装置实际开工过程以及开工中出现问题总结较好的开工经验,为以后新建装置开工提供借鉴^[1]。     

蒽的电化学加氢

在隔离式电解槽中,以制备的泡沫Pb为阴极,Pt丝为对电极,饱和甘汞电极（SCE）为参比电极,研究了不同电解体系的伏安曲线和蒽的阴极电化学加氢行为.实验发现：在已研究的体系中,蒽阴极电解加氢为二氢蒽,其中CH₃CN+EtOH+H₂O+Bu₄NBr是加氢效果较好的电解体系.进一步研究CH₃CN+EtOH+H₂O+Bu4NBr电解体系中H₂O浓度、溶剂组成和支持电解质Bu₄NBr的浓度以及温度等因素对蒽电解催化加氢效果的影响,结果表明较理想的电解体系组成为：［H₂O］＝5.5mol•L^-1,［CH₃CN］/［EtOH］＝2/1(v/v),［Bu₄NBr］＝0.50mol•L^-1,温度为35℃,在该条件下,电解反应6 h,二氢蒽的产率可达91.37％.     

渣油悬浮床加氢工艺研究

介绍了渣油悬浮床加氢技术领域的现状及抚顺石油化工研究院渣油悬浮床加氢技术特点。在不同反应器规模的连续式悬浮床加氢装置上的试验结果表明，研制的水溶性催化剂具有较强的原料适应性，在中等压力、空速约1.0 h^－1、催化剂加入量低于300 μg/g和一次通过的条件下处理常压渣油，小于500℃馏分油收率为70%～90%；处理减压渣油，小于500 ℃馏分油收率可达60%～80%，而过程甲苯不溶物质量分数低于10%。将悬浮床加氢技术与其他重油加工过程组合，可增加悬浮床加氢技术的灵活性，并有利于提高过程的总液体收率和经济性。     

FRIPP加氢生产超清洁溶剂油技术

介绍抚顺石油化工研究院开发的高压一段、中压两段及高压一段串联加氢法生产清洁溶剂油技术,利用此技术生产的清洁溶剂油产品质量达到国外同类产品的水平.在清洁溶剂油生产技术中,加氢法具有原料来源广泛,产品质量优良,生产过程无特殊环保问题等特点,将得到广泛的应用.     

神华煤液化残渣的加氢反应动力学

在微型反应管中,以神华煤液化残渣为原料,四氢萘为溶剂,在氢初压6 MPa、反应温度425～485℃、反应时间为0～30 min条件下,进行了煤液化残渣加氢实验,研究了煤液化残渣的加氢动力学特性。将氢化产物分为油气、沥青质和四氢呋喃不溶有机质,根据集总概念建立了煤液化残渣的加氢动力学模型,所建模型与实验值吻合程度高。在实验条件下,四氢呋喃不溶有机质向沥青质转化的活化能为147.41 kJ·mol^-1,沥青质向油气转化的活化能为34.81 kJ·mol^-1,沥青质缩合为四氢呋喃不溶有机质的活化能为173.48 kJ·mol^-1。     

重整装置原料预处理部分的优化设计

重整原料预处理是催化重整装置的一个重要组成部分。通过对先加氢后分馏和先分馏后加氢两种预处理工艺流程的对比，推荐采用先加氢后分馏的工艺流程，以60万t／a连续重整装置为例，对经过预加氢处理后的石脑油，采用先汽提后分馏和“二塔合一”工艺流程的主要设备、投资、能耗等进行了对比，推荐采用先汽提后分馏工艺流程设计方案。     

溶剂法对氨基苯磺酸的合成研究

将溶剂汽油进行惰性化处理后作为溶剂，在该溶剂中合成了对氨基苯磺酸，产品收率在９０％以上，溶剂回收率在９５％左右。     

Alternate use of heavy hydrotreatment and visbreaker naphthas by incorporation into diesel

In order to provide a solution for refineries having limited catalytic reforming capacity, a process scheme for incorporating most of the low octane heavy hydrotreatment and visbreaker naphthas into diesel is presented in this paper. This scheme involves blending the visbreaker naphtha with the feed to the diesel hydrotreatment units, processing this blend at the usual conditions for diesel hydrodesulfurization and changing the cut point in the diesel stabilizer.     

油砂沥青溶剂提取回收组合工艺

采用有机溶剂提取-超临界CO2回收溶剂这一组合方法对加拿大Athabasca油砂进行了提取分离及溶剂回收实验,通过实验筛选出最佳抽提溶剂为重整汽油。溶剂提取的最佳工艺条件:提取温度80℃,溶剂流量60mL/min,提取时间60min。在此条件下油砂沥青提取率达到92.74%。对超临界CO2-重整汽油体系的相行为进行研究,并通过实验综合考察了温度、压力、CO2流量以及回收时间等工艺操作条件对溶剂回收的影响。结果表明:在回收温度50℃,回收压力13MPa,溶剂与CO2分离温度70℃,压力5MPa,CO2流量7.5L/h,时间1h的条件下,重整汽油的回收率为98.71%。     

国内溶剂油精制技术现状

介绍了国内溶剂油精制技术的现状。催化加氢脱芳烃技术在工业生产中广泛应用，在适合的条件下，可以将原料中的芳烃脱除至较低水平；现有脱硫技术可以将溶剂油中的硫脱除至0.5 μg·g^-1以下。目前，我国溶剂油质量与国际溶剂油质量差距较大,生产符合国际质量标准的低芳烃和低硫含量的环保型溶剂油是今后发展的方向。     

Second row transition metal sulfides for the hydrotreatment of coal-derived naphtha II. Removal of individual sulfur compounds

The disappearance of individual sulfur compounds has been investigated during the hydrotreatment (simultaneous removal of sulfur, nitrogen and oxygen) of coal-derived naphtha over each of the bulk second row transition metal sulfides. The sulfur compounds in the naphtha mainly consist of thiols/sulfides, thiophene and substituted thiophenes. Thiols/sulfides are, in general, more easily converted than thiophenic compounds are. Lighter thiols/sulfides are intermediates in the conversion of higher boiling thiols/sulfides or thiophenes. Side chain alkyl C---C bond breaking is predominant during the disappearance of thiophenes over the Zr and Nb catalysts while C---S bond breaking is predominant over the other catalysts. Thiophenic compounds are hydrogenated prior to desulfurization over the Mo, Ru, Rh and Pd sulfides. Highly substituted thiophenes are the compounds most difficult to convert over the Mo, Ru, Rh and Pd sulfides. The substituted thiophenes exhibit different reactivity trends over molybdenum sulfide, on one hand, and the Group VIII sulfides, on the other, indicating different adsorption modes and surface mechanisms for their conversion over these catalysts. Individual sulfur compounds do not follow first order kinetics and the disappearance rate is limited by product inhibition. The overall removal of sulfur does not follow simple first or second order kinetics since the individual compounds do not react in parallel, independent or first order reactions.     

High efficient separation of olefin from fluid catalytic cracking naphtha: Separation mechanism and universal simulation method

The fluid catalytic cracking (FCC) naphtha critical component-oriented separation process is an efficient method to produce ultra-low-sulfur (<10 μg/g) gasoline with minimal loss of octane number (<1 RON). However, the product quality is highly dependent on the structure of the components of FCC naphtha. Aromatics and thiophene sulfides without a methyl side chain favor the separation of olefin. The major impulse of olefin separation is the solvent-induced dipole of aromatics or thiophene sulfides, leading to a “Plane-to-Plane” combination between the solvent and aromatics or thiophene sulfides, accompanied by a steric hindrance due to their side chains. This condition resulted in 2–3 times greater θ of benzene and thiophene compared with that of toluene and 3-methylthiophene. In addition, an improved non-random two-liquid model was proposed based on the above results, and a simulation method for FCC naphtha solvent extraction process was established. The calculation results accorded well with industry data.     

Effects of solvent composition on coprocessing coal with petroleum residua

The effect of solvent composition on coprocessing of coal and petroleum solvents is examined under a variety of reaction conditions. The effects of solvent modification procedures on enhancing methylene chloride/methanol (MeCl/MeOH) soluble coal conversion and pentane soluble oil production are studied. Solvent modification procedures performed prior to coprocessing reactions include pentane deasphalting, catalytic hydrotreatment, H-donor addition, and blending of coal-derived liquids with petroleum solvents. Oil production and coal conversion were variously affected by the different solvent modifications. Prior hydrotreatment of petroleum solvents generally enhanced coal conversion, as did H-donor addition. The presence of a hydrotreating catalyst exerted a leveling effect on the effects of solvent modification. Blending of coal liquids and petroleum solvents resulted in complex and not readily predictable interaction. Solvents yielding the highest MeCl/MeOH soluble coal conversion were not generally the optimal solvents for pentane soluble oil production.     

2-氨基-5-甲氧基苯磺酸的合成研究

以对氨基苯甲醚为原料，在溶剂汽油中经磺化合成了2-氨基-5-甲氧基苯磺酸，产品收率在86%以上，且不含致癌物，溶剂回收率在95%以上。     

Second row transition metal sulfides for the hydrotreatment of coal derived naphtha III. Removal of individual nitrogen compounds

The disappearance of individual nitrogen compounds is followed during the hydrotreatment of a coal-derived naphtha containing a mixture of nitrogen-, sulfur- and oxygen-containing heteroatom compounds over bulk second row transition metal sulfides. The naphtha contains mainly three types of nitrogen compounds: pyridines, anilines and quinolines. While quinoline is the least reactive of the three simplest compounds in these compound classes, substituted anilines are the compounds most difficult to remove from the naphtha. The presence or absence of an alkyl substituent exerts a strong influence on the reactivity of individual compounds and can over-shadow the differences between compound types. The reactivity patterns of the methyl-substituted pyridines indicate a steric hindrance about the nitrogen atom. The order of reactivity between alkyl-substituted anilines is different over the various sulfides with steric hindrance about the nitrogen atom indicated for only the higher activity catalysts. Except for molybdenum sulfide, the reactivity of quinoline is less than or equal to that of methyl-substituted quinolines. The individual nitrogen compounds do not disappear according to a first order rate expression but indicate strong product inhibition of the reaction rate. The overall removal of nitrogen does not follow simple first, zero or second order kinetics and shows similar kinetic behavior as for the disappearance of individual nitrogen compounds.