直馏柴油溶剂抽提精制

去除直馏柴油中的环烷酸，采用加氢精制法成本高，且氢源不足；采用碱洗法则损失大，污染严重。为此采用以助溶剂和溶剂组成的复合溶剂抽提方法脱除直馏柴油中的环烷酸，并对抽提的工艺条件进行了实验室研究。结果表明，采用单级抽提，剂油比为1～2：10，酸去除率达80％以上，柴油的回收率达99％以上，精制后柴油酸值合格，还可副产环烷酸。溶剂及助溶剂均可回收利用，不污染环境。     

胜利原油减一线油溶剂抽提分离石油酸

采用复合溶剂抽提分离胜利原油减一线油中的石油酸，经优选表明，复合溶剂的最佳配比为：活性组分A含量为1％—3％，60％乙醇含量为97％—99％；抽提的最佳剂油比为0.15。经复合溶剂抽提，可脱除减一线油中80％以上的石油酸，减一线精制油收率达99.3％，石油酸收率达0．62％，粗酸值为157mgKOH/g，复合溶剂可回收重复利用，回收率98.9％。采用该工艺每处理lt减一线油，可实现增值约10RMB￥。     

氨法精制直馏柴油的防乳化研究

为解决氨法精制直馏柴油使用乙醇作破乳剂时，存在乙醇用量与损耗大、溶剂和油比例高以及溶剂再生能耗高等问题，使用前期工作已开发出的SW－1破乳剂，考察氨法精掉的最佳的实验室操作条件。试验结果证明，SW-1破乳剂能满足氨法精制直馏柴油的防乳化要求，与使用乙醇破乳剂时相比，该工艺溶剂循环体积下降58．3％～75．0％；产品（氨精制柴油）酸度0．21mgKOH／100mL，无水分、氨、水溶性酸碱，钢片腐蚀合格，质量满足产品指标要求，优于碱洗电精制柴油。     

直馏柴油芳烃抽提工艺的优化

对模拟直馏柴油芳烃抽提萃取剂进行了筛选，优化了芳烃抽提条件；考察了不同反萃剂、水/溶剂比、反萃剂/溶剂比、精馏塔塔釜温度对溶剂回收过程的影响。结果表明：增大溶剂/原料比对提高萃取选择性和芳烃脱除率均有利；升温会导致选择性下降、芳烃脱除率提高；增大水/溶剂比、反萃剂/溶剂比及精馏塔塔釜温度均有利于提高回收溶剂纯度。在溶剂/原料质量比为3.0、萃取温度为60℃的最优萃取条件下，用3-甲基环丁砜(3-SUL)对实际直馏柴油进行7级逆流萃取，抽余油中芳烃质量分数降至6.6%,芳烃脱除率达到78.2%。在温度为20℃、反萃剂/溶剂质量比为0.5、水/溶剂质量比为0.15的最优反萃取条件下，用环戊烷对溶有萃取物的富溶剂进行3级反萃取，回收溶剂中3-SUL的质量分数为99.01%。     

采用新方法对直馏柴油进行脱酸的工艺研究

采用氨法对直馏柴油进行脱酸的中试研究结果表明，对于酸度大于30mgKOH／100ml柴油原料，该工艺的脱酸效果较好，且具有无高压电场、不使用强酸强碱、无“三废”排放及溶剂可循环使用等优点，是直馏柴油碱洗电精制的理想替代工艺。     

柴油选择性氧化-萃取脱硫工艺的研究

对柴油选择性氧化－萃取脱硫工艺在实验室进行了探索，初步试验结果表明：以过氧化酸为氧化剂，糖醛为萃取溶剂 ，采用该方法可有效脱险柴油中的硫化物，脱硫率一般在65％－80％。对长岭直馏塔柴油进行处理后硫含量可从1500μg/g降为472μg/g，符合国际燃料对柴油硫含量不大于500μg/g 的要求。同时可降低柴油的芳烃含量及密度，且十六烷值指数有所提高。该工艺有望为我国炼油企业生产清洁柴油提供一条新途径。     

醇氨法精制直馏柴油工艺的优化

醇氨法精制直馏柴油工艺存在破乳剂选择、精制柴油残余溶剂含量高、溶剂循环量大、需全部再生和再生能耗高等技术经济问题。为了解决这些问题，采用聚结过滤和溶剂部分循环再生法，对醇氨法精制直馏柴油工艺进行了优化。结果表明，与醇氨法原有工艺比较，优化工艺采用乙醇破乳剂，完全消除了精制油中的残余溶剂，取消了水洗操作，精制柴油中残余溶剂含量从19209μg／g下降至4．6μg／g，柴油与溶剂体积比由6提高到8，相分离时间由30min缩短至15min，溶剂循环量下降了25％，溶剂再生负荷和能耗下降了62．5％，精制柴油和环烷酸副产品质量完全满足产品指标要求。     

直馏柴油馏分加氢精制生产军用柴油中型试验

通过直馏柴油加氢精制生产－10号军用柴油的研究，在中型试验装置上考察了不同工艺条件对柴油质量的影响，获得了最佳工艺条件。结果表明，采用RN－1催化剂，在压力4．0MPa，温度250－260℃等工艺条件下，通过加氢精制可解决直馏柴油实际胶质超标问题，同时降低硫含量，满足－10号军用柴油质量要求。     

直馏柴油碱洗新工艺研究

介绍了利用膜分散技术进行克拉玛依石化公司直馏柴油碱洗脱酸工艺研究。讨论了溶剂组成、脱酸温度、剂油质量相比、连续相流量对脱酸效果的影响。研究表明,对连续相流通截面积为0．2cm。的膜分散萃取反应器,当脱酸溶剂中氨,乙醇,水的质量比例为4／40／50,试验温度65℃,连续相流量450g／min条件下,剂油作用比0．07时,能够将直馏柴油酸度降低到7mgKOH／100mL以下,并同时抽出粗酸值在170mgKOH／g以上的石油酸,石油酸纯度在70％以上。     

生产满足欧Ⅳ排放标准柴油的DDA-Ⅱ工艺

石油化工科学研究院通过中试研究开发了可由劣质柴油原料生产满足欧Ⅳ排放要求柴油的DDA-Ⅱ工艺技术。该技术采用非贵金属催化剂和两段高度集成的工艺流程，在适宜的工艺条件下，可将催化裂化柴油的芳烃含量降低至25％以下，硫含量降低至10μg／g以下，十六烷指数增加12．1～19．4个单位，产品柴油收率不低于95％；以直馏柴油或直馏柴油与催化裂化柴油的混合油为原料，可生产满足欧Ⅳ排放标准的柴油产品。     

减压渣油中钙赋存状态的研究

利用酸解的方法将低凝稠油减压渣油和超稠油减压渣油中的石油酸钙变为有机酸,采用醇碱溶液抽提的方法将石油酸抽提出来,通过红外光谱表征,证明是支化度较高、侧链较短的环烷酸。根据抽提物的模拟蒸馏数据对2种原油脱钙后柴油馏分和润滑油馏分酸值的增加情况进行了估算。     

Catalytic Oxidation of Petroleum Sulfide Concentrate with Hydrogen Peroxide

The catalytic properties of acetic and molybdic acids and acid sulfides were investigated in oxidation of petroleum sulfide concentrate with hydrogen peroxide. The efficiency of the catalysts was compared with respect to formation of sulfoxides and acid products. Acid sulfides extracted from the diesel fuel cut with sulfuric acid stripped during alkylation.     

石油酸腐蚀的动力学

 采用铁粉腐蚀法研究了石油酸的腐蚀特性,分析了柴油馏分石油酸腐蚀反应的动力学性质。结果表明,酸值相同时,柴油馏分中的石油酸腐蚀性比减四线馏分强,石油酸腐蚀高峰的温度与石油酸的平均沸点和分解温度有关。确定了石油酸动态腐蚀的表观总反应级数为2级,并求出反应活化能为55.6kJ/mol。     

石油酸的腐蚀动力学

采用铁粉腐蚀法研究了石油酸的腐蚀特性,分析了柴油馏分石油酸腐蚀反应的动力学性质.结果表明,酸值相同时,柴油馏分中的石油酸腐蚀性比减四线馏分强,石油酸腐蚀高峰的温度与石油酸的平均沸点和分解温度有关.确定了石油酸动态腐蚀的表观总反应级数为2级,并求出反应活化能为55.6 kJ/mol.     

石油产品酸含量测定标准的有效性研究

针对不同馏分石油酸的组成分布,利用基团贡献法对石油酸和酸含量测定标准中醇类、芳香类溶剂的溶解度参数等进行估算,混合溶剂与溶质具有相似的溶解度参数构成是改善测定有效性的基础。应用溶解度参数理论分析了溶质、溶剂、滴定剂间相互关系及对测定结果的影响,在满足国家标准使用基础上,明确了汽油、柴油、润滑油、原油的酸含量测定方法分别采用GB/T 258-2016、GB/T4945-2002、GB/T 7304-2000、GB/T 18609-2011,溶剂与溶质良好互溶,终点确定迅速、准确,酸含量测定更加科学、有效。     

高酸原油直接催化脱酸裂化成套技术开发和工业应用

利用分子模拟技术和量子化学理论研究了各种石油酸中原子的电荷分布、键级和在不同催化材料上的反应行为,发现羧基可从石油酸分子中脱除生成无腐蚀性的CO2和烃类化合物,尤其在酸性裂化催化剂作用下脱羧基速率更快、更彻底。开发了高酸原油经脱盐脱水后直接进入催化裂化提升管反应器与高温新型催化剂接触,瞬间汽化,同时实现脱酸和裂化反应,生成高价值石油产品的新工艺。工业应用结果：催化脱酸率大于99%,汽油、柴油可直接作为产品的调合组分,在平衡催化剂上金属污染总量达40 620 μg/g（其中镍为24 000 μg/g）时,总轻油收率比常规加工技术提高1.36百分点,能耗（相对于原油）降低271.7 MJ/t,对工业应用装置没有特殊防腐要求。为炼油企业扩大原油资源选择范围、降本增效提供了有效技术保障。     

Biodiesel production by direct esterification of fatty acids with propyl and butyl alcohols

The expected depletion of natural petroleum resources in the near future and pollution of the environment due to excessive carbon dioxide emissions by fossil fuel and its adverse effect on global warming constitute two major problems facing the whole world. In view of these problems, much research work is now directed worldwide to find fuels alternative to those derived from petroleum which should be renewable and more environmentally friendly fuels. Biodiesel fuel which is a blend of fatty acid esters with alcohols is considered the most suitable alternative fuel for diesel engines. In this scope of research work, a previous study (Soliman et al., 2013) has been made to explore the opportunity of utilizing the fatty acids that can be obtained from the waste of edible oil industry in Egypt to produce biodiesel fuel by direct esterification with methanol as well as ethanol in the presence of sulfuric acid as a catalyst. This paper is a continuation of that work where two other alcohols of a chain length longer than ethanol have been used being propanol and butanol. The performance of a diesel engine running using a 50% blend of regular diesel fuel and each of the two biodiesels prepared was compared to that using regular diesel fuel. The results have shown that the brake specific fuel consumption (BSFC) and the brake thermal efficiency at full engine loading were almost the same in all cases. This indicates that the produced fuel could be used as an efficient fuel substitute for diesel engines. By comparing the results of the present work to those reported in our previous work, it appeared that methanol which has the shortest carbon chain length is the most recommended in view of the brake thermal efficiency of a diesel engine at full loading.     

比较几种髙酸原油及其柴油、蜡油馏分的石油酸组成

Three high-acidity crudes,Dar,SZ36-1,and QHD326,were separated through distillation into several fractions,including diesel distillates,and VGOs.Samples were characterized by negative-ion ESI FT-ICR MS.The O 2 class species (petroleum carboxylic acids),which have a close relationship with corrosion of equipment caused by high-acidity crudes,were put in the focus of attention and were discussed in this paper.Monocyclic,bicyclic,and tricyclic naphthenic acids are the main types of petroleum carboxylic acids in naphthenic-base crudes (SZ36-1 and QHD326).But the main types of petroleum carboxylic acids in paraffinic-base crude (Dar) are aliphatic acids and monocyclic naphthenic acids.The O 2 class species in SZ36-1 and QHD326 are distributed in a wider range and have bigger DBE value (double-bond equivalence value) and carbon number than Dar.Bicyclic naphthenic acids have the highest proportion among petroleum carboxylic acids in diesel distillates,but monocyclic and tricyclic naphthenic acids also occupy a high proportion.Particularly,aliphatic acids in the diesel distillate of Dar still have high proportion among petroleum carboxylic acids.The distribution of petroleum carboxylic acids in VGO is basically identical.The bicyclic naphthenic acids assume the first place (about 25 m%),while the monocyclic and tricyclic naphthenic acids take the next place.The comparison of petroleum carboxylic acids in diesel distillates and VGOs has revealed that the molecules of carboxylic acids in VGOs are not only bigger but also more complicated.     

Deacidification of diesel using tetramethylammonium hydroxid/ammonia under demulsifier

Acids in diesel bring great harm to storage devices, transportation facilities and engines. Acids in diesel were removed by tetramethylammonium hydroxid (TMAH)/ammonia under nonylphenol ethoxylate as demulsifier. The effect of process parameters on removing acids was reviewed, such as volume ratio of TMAH to ammonia, volume ratio of deacidification agents to diesel, demulsifier dosage, deacidification temperature and deacidification time. The results showed that the optimum deacidification process was that volume ratio of TMAH to ammonia was 10:1, volume ratio of deacidification agents to diesel was 0.7:1, demulsifier dosage was 0.15?mL, deacidification temperature was 293 K and deacidification time was 5?min. Under the optimum process, deacidification rate of reached 88.36%. The deacidification process effectively removed acids in diesel, had a little effect on other physicochemical properties of diesel, moreover, the color of treated diesel also was greatly improved.