GC-AED法研究催化裂化柴油中硫氮化合物

采用气相色谱-原子发射光谱（GC-AED）联用技术对FCC柴油中的含硫化合物、含氮化合物进行定性定量研究。结果表明：FCC柴油中硫化物的类型主要是噻吩类衍生物、苯并噻吩、苯并噻吩类衍生物、二苯并噻吩、二苯并噻吩类衍生物,其中苯并噻吩类衍生物、二苯并噻吩类衍生物的硫质量分数占总硫质量分数的93．6％以上。氮化物主要为碱性氮化物（Nb）和非碱性氮化物（Np）两大类型,其中碱性氮化物主要是苯胺及其衍生物,喹啉含量很低,约占总氮质量分数的0．1％,非碱性氮化物主要包括吲哚及其衍生物和咔唑及其衍生物,而咔唑类氮化物一般约占总氮质量分数的64％。不同来源的FCC柴油,其所含硫化物、氮化物的含量和分布不同。应根据其硫化物、氮化物的分布类型及规律,开发合适的柴油脱硫脱氮催化剂及相关工艺。     

乙酰胺基配位离子液体的合成及脱氮性能

以乙酰胺和无水氯化锌为原料合成配位离子液体CH_3CONH_2-x ZnCl_2(x=0.3、0.4、0.5),采用FTIR对其结构进行了表征,并分别采用含有喹啉、吲哚的模拟柴油考察配位离子液体对油品中碱性氮化物和非碱性氮化物的脱除性能。结果表明,CH_3CONH_2-0.3ZnCl_2具有较好的脱氮性能,在萃取时间20 min、沉降时间2 h、萃取温度50℃、剂油质量比1∶3的条件下,该离子液体对喹啉和吲哚的脱除率分别为96.8%和68.1%。在该条件下,经过4步萃取后,吲哚模拟油的累计脱氮率可达97.6%。配位离子液体CH_3CONH_2-0.3ZnCl_2在回收利用5次后,喹啉脱除率仍可达到91.5%,具有较好的重复使用性能。     

汽油中硫化物分析方法的研究

采用气相色谱-硫化学发光检测器联用技术,建立了催化裂化汽油和焦化汽油中各种硫化物类型分布的分析方法,并考察了色谱条件对不同汽油中各种硫化物分离的影响,对汽油中80余种硫化物进行了定性。该方法具有很好的重复性和准确度,同时对实际样品进行了分析,认为该方法切实可用。     

磷钨酸催化氧化吸附脱除模拟油中氮化物研究

将磷钨酸、质量分数30%双氧水负载于介孔硅胶吸附剂孔中制备成脱氮剂,脱氮剂中硅胶与磷钨酸、质量分数30%双氧水的质量比为50%∶26.7%∶23.3%。以喹啉、吲哚和咔唑为模型氮化物,二甲苯及二甲苯和十二烷的混合溶液作溶剂,配制成含氮模拟油。在间歇反应器中,对磷钨酸、氧化剂的作用进行了研究,考察了温度、氮化物质量浓度和性质对脱氮反应速率的影响。结果显示:磷钨酸可以深度脱除碱性氮化物和低浓度非碱性氮化物,氧化剂能强化脱氮速率和吸附剂对氮化物的选择性。脱氮剂在温度50℃,脱氮剂与喹啉、吲哚模拟油质量比在3∶30,脱氮剂与咔唑模拟油质量比在3∶25条件下,模拟油中的氮化物90 min内被深度脱除。脱氮剂具有良好的再生性能,再生后脱氮剂的脱氮能力下降很小。     

酸精制前后中低温煤焦油中氮的赋存形态及脱除规律

以酸精制预处理前后的中低温煤焦油馏分(360℃)为原料,采用酸中和-柱层析法分类、富集碱性组分和非碱性组分,并利用气相色谱/质谱联用(GC-MS)对其进行检测分析。研究结果表明,预处理前馏分中主要碱性氮化物为w(苯胺类)=0.16%、w(喹啉类)=0.63%与w(吡啶类)=0.13%,非碱氮化物为w(吲哚类)=0.16%、w(吡唑类)=0.23%、w(吡咯类)=0.03%和w(腈类)=0.01%;预处理后,可实现总氮74.54%的脱除率,苯胺、吡啶类化合物和分子量较小的喹啉化合物基本上被完全脱除,非碱氮化合物不易被脱除;碱氮中各种化合物被脱除的难易程度为喹啉类吡啶类苯胺类,非碱氮被脱除的难易程度为吲哚类吡咯类吡唑类腈类。     

Fe(Ⅵ)氧化含氮杂环化合物路径及机理

为了明确高铁酸钾[Fe(Ⅵ)]氧化降解含氮杂环化合物(NHCs)(吲哚、喹啉、吡啶)的机理，采用高效液相色谱、荧光光谱、气相色谱-质谱等方法，考察不同因素对NHCs降解效果的影响，捕捉自由基、识别氧化产物并推测反应路径。结果表明，当温度25℃、吲哚与Fe(Ⅵ)的物质的量比为1:15、pH为7时，15 min内吲哚的去除率为77.91%，过程中高价态铁起主导作用；当喹啉与Fe(Ⅵ)的物质的量比为1:5、pH为5时，10min内喹啉降解率为81.16%，羟基自由基(HO·)起重要作用；当吡啶与Fe(Ⅵ)的物质的量比为1:3、pH为7时，5 min内吡啶去除率为36.89%,HO·起一定作用。Fe(Ⅵ)对3种NHCs有一定矿化效果。Fe(Ⅵ)降解NHCs的第一步均为羟基化产物的生成，随后经加成、脱氮、脱羰等反应实现氮杂环开环。     

从喹啉釜残液中提取高品质吲哚的工艺研究

吲哚是重要的精细有机化工品,以喹啉釜残液为原料,通过质量分数12%的硫酸洗涤去除喹啉、异喹啉、2-甲基喹啉等组分;利用双溶剂萃取原理去除α-甲基萘、β-甲基萘等非极性物质,将吲哚质量分数提高至97.66%;对萃取液进行减压蒸馏,吲哚质量分数提高至99.73%;利用乙醇-环己烷混合溶剂对吲哚馏分进行溶剂结晶,吲哚质量分数提高至99.99%;吲哚提纯工艺的单程收率为47.68%。     

磷酸基咪唑离子液体脱除煤焦油柴油馏分中的氮化物

研究了不同磷酸基咪唑离子液体对煤焦油柴油馏分中氮化物的脱除效果.分别以磷酸酯和磷酸二氢根为阴离子合成了烷基碳链长度不同的咪唑磷酸酯和咪唑磷酸二氢盐离子液体,考察了不同条件下离子液体对煤焦油柴油馏分的脱氮效果.结果表明,酸性咪唑磷酸二氢盐离子液体脱氮效果优于咪唑磷酸酯离子液体,1-丁基-3-甲基咪唑磷酸二氢盐([BMim]H₂PO₄)离子液体的脱氮效果最佳.在剂油质量比为0.2、反应温度为40℃、反应时间和静置时间均为30min的条件下,[BMim]H₂PO₄对煤焦油柴油馏分的脱氮率为92.3%,循环使用5次后仍具有稳定的脱氮效果.     

酸性离子液体脱除柴油中碱性氮化物

合成离子液体N-甲基吡咯烷酮磷酸二氢盐([Hnmp]H_2PO_4),用吡啶红外探针法测定其酸性。采用500μg/g的喹啉模型油考察其对油品中碱性氮化物的脱除性能。结果表明,在剂油质量比1∶7,反应温度为30℃,反应时间为30 min,静置时间120 min的条件下,模型油中碱性氮化物的脱除率可达到98.64%。在离子液体[Hnmp]H_2PO_4回收利用4次后,碱氮脱除率仍在96%以上。同时该离子液体也能有效脱除碱氮含量高达0.52%(质量分数)的抚顺页岩油柴油馏分中的氮化物,当剂油质量比为1∶1时,柴油馏分的碱氮脱除率可达94.25%。     

酸性离子液体脱除柴油中碱性氮化物

合成离子液体N-甲基吡咯烷酮磷酸二氢盐([Hnmp]H_2PO_4),用吡啶红外探针法测定其酸性。采用500μg/g的喹啉模型油考察其对油品中碱性氮化物的脱除性能。结果表明,在剂油质量比1∶7,反应温度为30℃,反应时间为30 min,静置时间120 min的条件下,模型油中碱性氮化物的脱除率可达到98.64%。在离子液体[Hnmp]H_2PO_4回收利用4次后,碱氮脱除率仍在96%以上。同时该离子液体也能有效脱除碱氮含量高达0.52%(质量分数)的抚顺页岩油柴油馏分中的氮化物,当剂油质量比为1∶1时,柴油馏分的碱氮脱除率可达94.25%。     

加氢脱氮反应研究进展

介绍了油品加氢脱氮反应机理;详细综述了非杂环类化合物、碱性杂环化合物、非碱性杂环化合物等含氮化合物的加氢脱氮反应网络;还从活性组分、载体的改性、助剂的选择等加氢脱氮催化剂改性途径方面作了论述.     

一种简易脱除焦化柴油中碱性氮化合物的方法

用二氧化碳酸性水溶液洗涤焦化柴油，使油中的碱氮化合物溶于水，从而将碱氮从焦化柴油中分离出来。实验结果表明，大庆焦化柴油经此种方法洗涤后，可脱除碱氮约６０％。此方法工艺简单、投资少、成本低，目前可以作为加氢精制的预处理手段。     

催化柴油加氢改质的实验研究

对我国某小型炼厂（还没有新建加氢改质装置）的催化柴油进行加氢改质实验研究。通过实验对加氢改质前后产品质量对比,加氢改质后催化柴油硫氧氮和氧化不溶物含量与先前炼厂采取的通过添加柴油稳定剂以及酸碱精制方法处理的催化柴油性能进行对比。结果表明：要生产出符合GB252-2011的成品柴油,该炼厂新建加氢改质装置非常有必要。     

Comprehensive two-dimensional gas chromatography for basic and neutral nitrogen speciation in middle distillates

The molecular knowledge of nitrogen compounds in diesel feedstocks has become a key issue in the development of hydrotreatment processes, especially for ultra-low sulfur diesel production. Indeed, nitrogen species have a strong impact on the hydrodesulfurization (HDS) pathway, since basic nitrogen is known to poison acidic sites of HDS catalysts.Since conventional methods only allow a poor degree of information, the increased separation power of comprehensive two-dimensional gas chromatography (GC × GC-NCD) was used in this study to obtain a detailed overview of nitrogen compounds by type (basic/neutral), by family and by carbon breakdown in diesel and liquefied coal samples. Partially hydrogenated compounds such as tetrahydrocarbazole and tetrahydroquinoline derivatives could even be detected in liquefied coal samples as well as diesel from ebullated bed conversion units. Comparison of GC-NCD with GC × GC-NCD for quantitative determination of nitrogen compounds by family was achieved in a first step. These results demonstrate the superiority of GC × GC to allow for a comprehensive characterization of nitrogen compounds in diesel and related samples in one injection. Furthermore, nitrogen speciation by GC × GC-NCD technique allows identifying most nitrogen species in conventional diesel or liquefied coal samples, with no use of mass spectrometry.GC × GC-NCD was also applied to a wide range of diesel feedstocks obtained from distillation, cokefaction, FCC, ebullated bed hydroconversion units to correlate nitrogen species to the origin of the feedstocks or distillation end points, giving interesting indications on reaction mechanisms involved in the processes.     

Nitrogen compounds characterization in atmospheric gas oil and light cycle oil from a blend of Mexican crudes

The distribution of basic and non-basic nitrogen compounds along the distillation curves of the middle distillates atmospheric gas oil (AGO) and light cycle oil (LCO), used as feedstocks for diesel fuel production, is presented in this paper. For this purpose, the total and basic nitrogen content of true boiling point distillation fractions of AGO and LCO were obtained, followed by nitrogen compounds identification by a GC-MS technique. The ratio of quinoline, indole and carbazole derivatives was determined as 1/0.75/2.5 in AGO. In LCO, a 1/2.3/12.2 ratio of aniline, indole and carbazole derivatives was found. A complete physical and chemical characterization of both AGO and LCO is also presented.     

Hydrotreatment of Cracked Light Gas Oil

Since worldwide conversion processes are used to upgrade heavy oil to distillates, the hydrotreatment of light gas oil (LGO) as a downstream process has been used more extensively. This fraction (LGO) is produced from thermal or catalytic cracking or hydrocracking processes. It contains high amounts of unsaturates, nitrogen, and sulfur compounds which cause instability while in storage due to gum formation. The use of LGO as a fuel oil for diesel engines plugs the filter and produces sulfur and nitrogen emissions. These sulfur and nitrogen compounds arise from the cracking of heavy cuts and are aromatic-type molecules which are difficult to hydrogenate. This cut also possesses a low cetane index (CI) which must be increased (by aromatic hydrogenation) because of its poor motor performance. Color and color stability are associated with a high bromine number (BN, unsaturated content), nitrogen, and aromatic content. In order to improve these properties, a deep hydrogenation is sometimes required.     

Hydrotreatment of Cracked Light Gas Oil

Since worldwide conversion processes are used to upgrade heavy oil to distillates, the hydrotreatment of light gas oil (LGO) as a downstream process has been used more extensively. This fraction (LGO) is produced from thermal or catalytic cracking or hydrocracking processes. It contains high amounts of unsaturates, nitrogen, and sulfur compounds which cause instability while in storage due to gum formation. The use of LGO as a fuel oil for diesel engines plugs the filter and produces sulfur and nitrogen emissions. These sulfur and nitrogen compounds arise from the cracking of heavy cuts and are aromatic-type molecules which are difficult to hydrogenate. This cut also possesses a low cetane index (CI) which must be increased (by aromatic hydrogenation) because of its poor motor performance. Color and color stability are associated with a high bromine number (BN, unsaturated content), nitrogen, and aromatic content. In order to improve these properties, a deep hydrogenation is sometimes required.     

Oxidative desulfurization of synthetic diesel using supported catalysts: Part II. Effect of oxidant and nitrogen-compounds on extraction–oxidation process

Oxidative desulfurization (ODS) of a synthetic diesel was carried out at mild conditions (atmospheric pressure and 60 °C) in presence of V₂O₅/Al₂O₃ and V₂O₅/TiO₂ catalysts. Two main aspects were studied: the effect of the oxidant reagent and the presence of nitrogen compounds on ODS of benzothiophenic compounds prevailing in diesel, such as benzothiophene, dibenzothiophene and alkyl substituted in positions 4 and 6. Results show that activity is improved when using hydrogen peroxide, as oxidant reagent, and V₂O₅/Al₂O₃, as catalyst. This result was attributed to the high decomposition of peroxide due to the presence of catalyst. In presence of nitrogen compounds, the ODS activity decreases in the order: quinoline > indole > carbazole. In order to explain this effect, successive chemisorption of DBT and quinoline on V₂O₅/Al₂O₃ catalyst was evaluated by FT-IR, and the results show that DBT is displaced by quinoline, occupying the adsorption sites of catalyst. N-compound effect could be explained by strong adsorption of nitrogen compounds on catalytic sites.     

龙口页岩柴油络合萃取精制工艺研究

以龙口页岩油为原料,取其柴油馏分为研究对象,采用糠醛和FeCl3-甲醇溶液为络合萃取剂对龙口页岩柴油进行萃取络合研究。考察了糠醛及FeCl3-甲醇溶剂量对对页岩柴油色度和碱氮含量的影响。结果表明,络合萃取后龙口页岩柴油中碱性氮化物可得到有效的脱除。