超声条件下柴油氧化脱硫的研究

采用H2O2-甲酸作为氧化剂将催化裂化柴油中的硫化物（主要为苯并噻吩类）氧化成相应的砜,同时引入超声波为反应提供能量,考察（油/剂）比、氧化温度、反应时间、萃取静置时间、（萃取剂/油）比和萃取次数等因素对脱硫效果的影响。在适宜条件下,脱硫率可达94.2%,收率可达90%以上。     

纯糠醛萃取脱除催化裂化柴油中的碱性氮化物

研究了以纯糠醛为溶剂脱除催化裂化柴油中的碱性氮化物；考察了剂油比，抽提次数，抽提温度，抽提时间，静置时间对脱碱氮的影响；并且考察了相同操作条件下糠醛对含硫化合物的脱除作用。实验结果表明，碱氮脱除率可达到90％以上，脱硫率可以达到85％以上；抽提在室温下进行，lOmin之内抽提可以完成，溶剂可以回收。     

Fractionation of oligomeric triacylglycerides and the relation to rejection limits for used frying oils

Precipitates enriched in oligomeric triacylglycerides were separated from thermally oxidized olive residue oil, conventional and high-oleic sunflower oils, and soybean oil by solvent fractionation in methanol/acetone at 4–5°C for 16 h. Different fractionation conditions were evaluated in an effort to isolate the oligomeric triacylglycerides (OTG). OTG, formed in frying oils upon heating at low concentations, were not detectable with conventional methods to determine polymeric compounds. The best conditions found from the different assays were the following: (i) weight of oil sample-to-solvent volume ratio of 1∶20; and (ii) solvent system methanol/acetone 10∶90 (vol/vol) for monounsaturated oils and 15∶85 (vol/vol) for polyunsaturated oils. Precipitates, enriched in oligomers, were formed when heated oils and used frying oils contained more than 27% polar compounds, a value which is widely accepted as the upper limit for use of frying oils.     

FCC汽油萃取脱硫过程萃取剂筛选

分别考察了4种萃取剂在单一或复配条件下,对3种模拟汽油中单一含硫化合物及FCC汽油70～160 ℃切割馏分的萃取脱硫效果,效果皆佳的萃取剂为环丁砜。考察了操作温度、剂油比、环丁砜和四甘醇复配对脱硫率的影响。结果表明：温度对萃取脱硫率的影响较小。适宜的萃取条件为温度35 ℃,剂油比3∶1。环丁砜单一溶剂萃取脱硫效果较优。     

超重力技术应用于不同磺化剂合成石油磺酸盐表面活性剂

With the application of HIGEE process intensification technology, petroleum sulfonate surfactant used for enhanced oil recovery was synthesized from petroleum fraction of Shengli crude oil with three sulfonating agents, including diluted liquid sulfur trioxide, diluted gaseous sulfur trioxide and fuming sulfuric acid. For each sulfonating agent, different operation modes (liquid-liquid or gas-liquid reaction with semi-continuous or continuous operation) were applied. The effects of various experimental conditions, such as solvent/oil mass ratio, sulfonating agent/oil mass ratio, gas/liquid ratio, gas concentration, reaction temperature, rotating speed, circulation ratio, reaction time and aging time, on the content of active matter and unsulfonated oil were investigated. Under relatively optimal reaction conditions, the target product was prepared with high mass content of active matter (up to 45.3%) and extremely low oil/water interfacial tension (4.5×10–3 mN•m–1). The product quality and process efficiency are higher compared with traditional sulfonation technology.     

成品柴油氧化萃取法脱硫脱氮工艺研究

以双氧水-有机酸体系作氧化剂,采用氧化反应与溶剂萃取相结合的方法对焦化柴油进行了氧化脱氮研究。通过单因素实验确定了最适宜的氧化工艺参数为：双氧水-甲酸作氧化体系,氧化温度为70℃,氧化时间为1 min,剂油体积比为0.24,V（双氧水）/V（有机酸）为0.5。萃取实验条件为：在室温条件下,萃取剂油比为0.8,搅拌5 min。以低硫、低氮成品柴油为例,考察了氧化萃取法在最佳工艺条件下对硫、氮的深度脱除,以及对硫类型和氮类型的选择性研究。结果表明：柴油回收率为94.20%,总氮脱出率为76.39%,总硫脱出率为87.38%,这种工艺对柴油中较难脱出的咔唑、噻吩类化合物具有较好的脱出效果。     

连续式FCC柴油萃取-光催化氧化深度脱硫

尽快降低燃料油中的硫含量是整个炼油业都无法回避的重大问题，炼油工业发达的国家已提出生产超低硫清洁燃料 （硫含量低于10 μg•g^-1）的目标。本文通过连续式FCC柴油萃取-光催化深度脱硫工艺，对FCC柴油进行精制，精制油中硫含量采用硫氮荧光分析仪测定，硫含量为45 μg•g^-1。实验结果表明：萃取操作的适宜条件为常压，萃取温度40℃，剂油比1.5∶1;反应操作的适宜条件为反应温度40℃，反应时间1 h，氧化剂用量为4%。在以上操作条件下，精制油中的硫含量为达到欧Ⅳ标准，精制油总收率超过96%。     

功率超声辅助下柴油氧化脱硫的研究

催化氧化脱硫是降低柴油硫含量的非加氢脱硫工艺,在催化氧化溶剂抽提的基础上,同时增加超声波为反应提供能量,开辟了一条全新的柴油氧化脱硫技术。考察了萃取剂的选择、萃取剂油比、萃取静置时间、萃取次数等对脱硫效果的影响。实验结果表明：在功率超声作用下,以H2O2为氧化剂,甲酸和磷酸为催化剂,氧化剂油比（体积比）=1：10,H2O2：催化剂（体积比）=1：1,反应温度50℃,反应时间10min时,萃取剂为DMF,萃取剂油比（体积比）=1：1,一次萃取20min,萃取次数2次为最佳。     

络合法脱除桦甸页岩油柴油馏分中碱性氮的研究

采用酸碱洗涤-溶剂萃取的方法对兰州窑街的页岩油中的氮类化合物进行了提取。产物经GC—MS进行了测定,用色谱峰面积归一化法确定各碱性氮的相对含量。结果显示,含氮化合物共检出87个。其中碱性氮化合物共有64个,主要分为吡啶、喹啉、苯胺3类。非碱性含氮化合物23个,主要分为吡咯、吲哚、咔唑3类。根据碱性氮的组成性质,分别考察了剂油比、不同反应时间、反应温度对脱氮效果的影响。结果表明,当剂油比为3％、反应温度55℃、反应时间为10min,脱氮效果最好,页岩油中碱氮脱除率可达到82．1％。     

A new method for obtaining ultra-low sulfur diesel fuel via ultrasound assisted oxidative desulfurization☆

Due to the requirement of stringent rules for ultra-low sulfur content of diesel fuels, it is necessary to develop alternative methods for desulfurization of fossil fuel derived oil. Using appropriate oxidants and catalysts with the assistance of ultrasound irradiation, model compounds such as dibenzothiophene can be quantitatively oxidized in minutes. For diesel fuels containing various levels of sulfur content, and through the use of catalytic oxidation and ultrasonication followed by solvent extraction, removal efficiency of sulfur-bearing compounds can reach or exceed 99% in a short contact time at ambient temperature and atmospheric pressure. This simple approach can be the basis for obtaining ultra-low sulfur-containing diesel oil. GC-PFPD, GC-MS, and GC-SIMDIS were used to monitor the change of organic sulfur compounds and hydrocarbons in diesels during the process.     

Peroxide-Assisted Oxidative Desulfurization of Nonhydrotreated Vacuum Gas Oil

The possibility of using a catalyst system based on hydrogen peroxide and formic acid for the oxidative desulfurization of nonhydrotreated vacuum gas oil has been explored. Conditions for the effective extraction of oxidized sulfur compounds from nonhydrotreated vacuum gas oil have been selected. The effect of oxidation and thermolysis conditions on the oxidative desulfurization process has been studied, and a 44% decrease in the total sulfur content in nonhydrotreated vacuum gas oil has been achieved.

     

有机溶剂萃取加拿大油砂应用研究

介绍了溶剂作为萃取剂分离油砂的技术,溶剂萃取油砂过程包含两个阶段:沥青相向溶剂的溶解过程和沥青、溶剂与砂粒的分离过程。考察了单一溶剂甲苯、丙酮、乙酸乙酯和甲苯/正庚烷、丙酮/正庚烷、乙酸乙酯/正庚烷组成的复合溶剂体系在相同条件下对油砂沥青的萃取率,在此基础上进一步对比了不同溶剂体系对沥青四组分饱和分、芳香分、胶质和沥青质的萃取效果,同时考察了不同浓度的沥青-溶剂溶液的表面张力,结果表明在油砂萃取过程中沥青-溶剂体系的表面张力主要取决于所选溶剂的种类,而沥青的浓度对溶液表面张力的影响不大。混合溶剂体系甲苯/正庚烷、丙酮/正庚烷、乙酸乙酯/正庚烷相比纯溶剂萃取率较高,其沥青溶液表面张力较低,是良好的分离油砂溶剂体系。     

Sulfur removal from hydrotreated petroleum fractions using ultrasound-assisted oxidative desulfurization process

Ultrasound-assisted oxidative desulfurization (UAOD) process was applied to diesel oil and petroleum product feedstock containing model sulfur compounds (benzothiophene, dibenzothiophene and dimethyldibenzothiophene). The influence of oxidant amount, volume of solvent for the extraction step and time and temperature of ultrasound treatment (20 kHz, 750 W, operating at 40%) was investigated. Using the optimized conditions for UAOD, sulfur removal up to 99% was achieved for model compounds in petroleum product feedstock using a molar proportion for H₂O₂:acetic acid:sulfur of 64:300:1, after 9 min of ultrasound treatment at 90 °C, followed by extraction with methanol (optimized solvent and oil ratio of 0.36). Using the same reagent amount and 9 min of ultrasound the removal of sulfur was higher than 75% for diesel oil samples. Sulfur removal without ultrasound using the same conditions was lower than 82% for model compounds and 55% for diesel oil samples showing that ultrasound improved the efficiency of oxidative desulfurization. In comparison to conventional hydrodesulfurization, the proposed UAOD process can be performed under relatively mild conditions (atmospheric pressure and 90 °C, without using metallic catalysts).     

宽馏分油加氢制取溶剂油和白油的研究

以洛阳金达石化有限责任公司特种油品厂10×104 t/a宽馏分装置的宽馏分油为原料,采用催化剂a和催化剂b组合工艺,在金达研发中心200 m L加氢装置上进行高压加氢制取溶剂油和白油等特种油品的研究。考察了反应压力(16.5~18.5 MPa)、反应温度(315~355℃)、质量空速(WHSV)(0.3~0.6 h-1)和氢油体积比(1 000:1~1 800:1)对加氢精制产物油性质的影响,并确定最佳的工艺参数。结果表明,产物油硫含量随着反应温度、压力、氢油体积比的增大而减小,随着空速的增大而增大;产物油芳烃含量随着反应压力、氢油体积比的增大而减小,随着反应温度和空速的增大而增大。对加氢产物油进一步蒸馏切割得到25%溶剂油馏分、60%白油馏分和11%减底尾油馏分。对产物油馏分进行含量分析,生成的产品油分别满足溶剂油和白油标准。     

Solvent screening for non‐aqueous extraction of Alberta oil sands

Non‐aqueous extraction of bitumen from oil sands has the potential to reduce fresh water demand of the extraction process and eliminate tailings ponds. In this study, different light hydrocarbon solvents, including aromatics, cycloalkanes, biologically derived solvents and mixtures of solvents were compared for extraction of bitumen from Alberta oil sands at room temperature and ambient pressure. The solvents are compared based on bitumen recovery, the amount of residual solvent in the extracted oil sands tailings and the content of fine solids in the extracted bitumen. The extraction experiments were carried out in a multistage process with agitation in rotary mixers and vibration sieving. The oil sands tailings were dried under ambient conditions, and their residual solvent contents were measured by a purge and trap system followed by gas chromatography. The elemental compositions of the extraction tailings were measured to calculate bitumen recovery. Supernatants from the extraction tests were centrifuged to separate and measure the contents of fine solid particles. Except for limonene and isoprene, the tested solvents showed good bitumen recoveries of around 95%. The solvent drying rates and residual solvent contents in the extracted oil sands tailings correlated to solvent vapour pressure. The contents of fine solids in the extracted bitumen (supernatant) were below 2.9% for all solvents except n‐heptane‐rich ones. Based on these findings, cyclohexane is the best candidate solvent for bitumen extraction, with 94.4% bitumen recovery, 5 mg of residual solvent per kilogram of extraction tailings and 1.4 wt% fine solids in the recovered bitumen. © 2012 Canadian Society for Chemical Engineering     

Extraction of oil from ground corn using ethanol

Corn oil was extracted from whole ground corn using ethanol as the solvent. The yield of oil was measured as a function of temperature, time of extraction, solvent-to-solids ratio, and ethanol concentration. Optimal conditions were a solvent-to-solids ratio of 4 mL/g corn, an ethanol concentration of 100%, 30 min of extraction time, and a temperature of 50°C. Under these conditions, a single batch extraction yielded ≈3.3 g oil/100 g corn, equivalent to 70% extraction efficiency. A three-stage extraction, where the same corn was exposed to fresh ethanol, resulted in a yield of ≈4.5 g/100 g corn (2.5 lb/bu of corn), equivalent to 93% recovery of the oil in corn. When anhydrous ethanol was used to repeatedly extract fresh corn, moisture was absorbed linearly by ethanol from the corn in successive stages, which, in turn, decreased oil yield and increased nonoil components in the extract.     

糠醛抽出油制取橡胶填充油的研究

为了研制符合一定标准的橡胶填充油,以糠醛为溶剂对大庆石化减二线糠醛抽出油进行再抽提。本研究采用单级抽提方法进行了一系列条件实验,考察研制橡胶填充油的应用可行性。主要考察了抽提温度和剂油比对橡胶填充油的质量和收率的影响。研究结果表明：当剂油比一定时,随着温度的升高,产品收率上升,芳香烃含量下降;当温度一定时,随着剂油比增大,产品收率先上升后下降,芳香烃含量先上升后下降。综合考虑产品的质量和收率,本实验范围内较适宜的操作条件为：抽提温度60℃,质量剂油比2.0。在此条件下,产品收率为52.3%,芳香烃组分的含量为80.6%,符合某些企业橡胶填充油的使用标准。     

乙醇提取-丙酮沉淀法提取分离茶皂素的工艺研究

以油茶饼粕为原料,采用乙醇提取-丙酮沉淀法对茶皂素进行提取分离。以茶皂素纯度和得率为考察指标,对乙醇体积分数、液料比、提取温度、提取时间、提取次数、提取液浓缩程度和丙酮用量等工艺参数进行了单因素优化。结果表明：体积分数95%的乙醇为提取溶剂,乙醇与预处理过的油茶饼粕液料比为9：1（mL：g）,提取温度为70℃,提取时间为4 h,提取次数为2次,提取液浓缩至刚好有固体析出,丙酮用量为4倍浓缩液体积量时提取分离效果较佳,得到的茶皂素纯度为85.17%,得率为9.82%。不同溶剂打浆对产品纯化效果的比较发现：丙酮、乙酸乙酯、无水乙醇、体积分数95%的乙醇作为打浆纯化溶剂用于提高茶皂素纯度效果均不明显。     

溶剂抽提法分离印尼油砂的实验研究

利用溶剂抽提法对印尼油砂进行萃取分离实验,综合考察了剂砂比、抽提温度、抽提时间、抽提次数等操作条件对油砂沥青提取的影响,确定较佳的油砂分离条件。结果表明,印尼油砂更适合采用溶剂抽提法分离,从油砂沥青提取率、操作成本和环保多角度考虑,在超声波的作用下,剂砂比为2．5,抽提温度40℃,抽提时间30min,抽提3次的条件下,油砂沥青的提取率较高,达到20．31％。     

高粘度润滑油馏分油溶剂精制小试对比

针对某炼厂高粘度润滑油馏分油进行了糠醛溶剂的单级抽提试验,并借助数学手段,确定了糠醛精制的最优操作条件.在此基础之上,进行了糠醛精制假三段抽提试验,确定了其适宜的操作条件,并与NMP精制进行了对比.试验结果表明,糠醛单级抽提适宜操作条件为:抽提温度115℃,剂油比1.8(V/V);在该操作条件下,精制油60℃折光率为1.462 8,油收率为83％;糠醛假三段试验适宜操作条件为:上段温度115℃、中段温度100℃、下段温度85℃,剂油比1.8(V/V).在该操作条件下,精制油60℃的折光率为1.460 9,油收率为84％;馏分油糠醛抽提与NMP抽提相比,在精制效果相当的情况下,无论单级还是假三段抽提,NMP精制的温度下降25℃,剂油比下降30％,油收率提高至少3个百分点,说明NMP作为抽提溶剂要优于糠醛.