基于中压加氢改质方案的炼油流程协同优化

中国石化北京燕山分公司(简称燕山分公司）为增产高附加值产品、提升效益，对炼油系统进行了流程协同优化。中压加氢裂化装置掺炼催化裂化柴油，由加氢裂化方案改为加氢改质方案运行，将改质柴油送入三号催化裂化装置（简称三催化装置）的提升管进行回炼；同时，将焦化蜡油改入加氢裂化装置进行加工，而蜡油加氢装置不再加工焦化蜡油以改善催化裂化原料。协同优化后，中压加氢改质装置的柴油产品十六烷值提高7个单位；三催化装置的液化气收率提高1.96百分点，汽油收率增加0.88百分点，总液体收率增加2.28百分点；高压加氢裂化装置喷气燃料产品的密度（20 ℃）降低至806 kg/m3，烟点为23.8 mm，尾油BMCI由11.8降低至10.8；蜡油加氢装置精制蜡油的饱和分质量分数提高4.68百分点，芳香分质量分数降低5.96百分点，氮质量分数降低0.06百分点，使催化裂化原料性质得以改善。通过将中压加氢改质装置的喷气燃料馏分抽出送催化裂化装置回炼，与回炼改质柴油相比，催化裂化汽油的研究法辛烷值（RON）增加1.0个单位，改质柴油十六烷值提高4.8个单位。通过全炼油板块系统性优化，燕山分公司车用柴油产品的十六烷值由53.5降低至51.5，解决了质量过剩问题。     

Poly-functional Catalyst Development for Benzene Production from Alkyl-aromatic Mixture via Hydrodealkylation

Development of a poly-functional catalyst that has higher hydrodealkylation activity based on 15% Cr/γ- Al₂ O₃ was researched for benzene production from an alkyl-aromatic mixture via hydrodealkylation. For this goal, the effects of the promoters like Fe, Co, or Ni and their concentrations on the activity of a Cr/Al₂ O₃ catalyst were investigated. Toluene + n-heptane + tetrahydrotiophene (89:10:1 w%) model mixture, which has the same content as industrial aromatics, was used as feedstock. The activities of catalysis in reactions of hydrodealkylation, hydrocracking, and hydrogenolize with respect to conversions of toluene, heptane, and tetrahydrotiophene were tested, respectively. As to the obtained results, the catalyst including 5% Fe has a higher hydrodealkylation activity, compared to the catalyst including Co, and especially to the alumocrom catalyst not including a promoter, while it has a lower coke formation and reduced activity to the catalyst including Ni.     

悬浮床加氢裂化油溶性催化剂与沥青质的作用

在高压釜反应器中对添加了油溶性 Ni 催化剂(UPC-O)和水溶性 Ni 催化剂(UPC-W)的辽河稠油常压渣油(LHAR)进行了悬浮床加氢裂化实验。通过元素分析和傅里叶变换红外光谱(FTIR)分析对抑制反应生焦效果好的 UPC-O 与 LHAR 沥青质的作用进行了研究。元素分析结果显示,在 LHAR 中加入 UPC-O1000μg/g,沥青质和脱沥青质油中 Ni 含量分别出476μg/g和110μg/g 增加到7 559μg/g 和1 024μg/g,表明 UPC-O 在沥青质中有富集的趋势。FTIR 表征结果显示,UPC-O 和沥青质发生了相互作用。UPC-O 可在沥青质原位硫化为活性组分,对沥青质在悬浮床加氢裂化反应中的缩合起到好的抑制作用。     

The effect of aromatics on paraffin mild hydrocracking reactions (WNiPd/CeY–Al2O3)

The conversion of heavy paraffin and aromatics into a high-quality diesel fraction was performed in a microplant using a WNiPd/CeY-alumina catalyst. The effects of aromatics and naphtheno-aromatics on mild hydrocracking of hexadecane were studied at different concentrations. Two catalysts, with and without Pd and thermal treatment, were characterized by FTIR, XPS, and TPD of ammonia and ammonia plus naphthalene to complement previous study about the surface composition. The hydrocracking activity and selectivity were tested using different amounts and types of aromatics. This study demonstrated the presence of two acid strengths that contribute in different ways to paraffin and aromatics isomerization, ring opening, and cracking reactions. The product distribution obtained by mild hydrocracking of n-C₁₆ is between amorphous (SiO₂Al₂O₃) and Y-zeolite type of support. The aromatic adsorption on acid sites reduces the cracking rate and improves the survival of di- and tri-branched paraffin. A model for the path of reaction is discussed to explain the results.     

正庚烷-甲苯-三甘醇三元体系液-液相平衡数据的测定与关联

利用气相色谱法测定了常压下２５℃、４０℃和５０℃时正庚烷－甲苯－三甘醇体系的液－液相平衡数据，采用峰面积归一化法定量，所得数据准确、可靠。用ＮＲＴＬ模型对所测数据进行了热力学关联，求出了相应的模型参数。用该模型对本三元体系进行了预测，结果令人满意。     

Alternative hydrocarbon solvents for cottonseed extraction

Hexane has been used for decades to extract edible oil from cottonseed. However, due to increased regulations affecting hexane because of the 1990 Clean Air Act and potential health risks, the oil-extraction industry urgently needs alternative hydrocarbon solvents to replace hexane. Five solvents,n-heptane, isohexane, neohexane, cyclohexane, and cylopentane, were compared with commercial hexane using a benchscale extractor. The extractions were done with a solvent to cottonseed flake ratio of 5.5 to 1 (w/w) and a miscella recycle flow rate of 36 mL/min/sq cm (9 gal/min/sq ft) at a temperature of 10 to 45°C below the boiling point of the solvent. After a 10-min single-stage extraction, commercial hexane removed 100% of the oil from the flakes at 55°C; heptane extracted 100% at 75°C and 95.9% at 55°C; isohexane extracted 93.1% at 45°C; while cyclopentane, cyclohexane, and neohexane removed 93.3, 89.4, and 89.6% at 35, 55, and 35°C, respectively. Each solvent removed gossypol from cottonseed flakes at a different rate, with cyclopentane being most and neohexane least effective. Based on the bench-scale extraction results and the availability of these candidate solvents, heptane and isohexane are the alternative hydrocarbon solvents most likely to replace hexane. Presented in part at the AOCS Annual Meeting & Expo, Atlanta, Georgia, May 1994.     

Correlation of reactivity with chemical structure: Thermal hydrogenation of gas oils

The relationship between chemical structure and reactivity for thermal hydroprocessing was studied for five gas oils derived from Alberta bitumens. Chemical structure was characterized by combining data from ¹ H and ¹³ C nuclear magnetic resonance spectroscopy, class fractionation, and elemental analysis to calculate structural parameters. Thermal hydrotreating was performed in a continuous-flow stirred reactor at 420 and 440°C, 13.9 MPa hydrogen pressure, and 1.5 h¹ LHSV. Conversion of the 343–525°C boiling fraction of the gas oils was correlated with the concentration of naphthenic methylene groups in the feed. Formation of methane and ethane was dependent on the degree of condensation of the aromatic rings in the feed oils. Thermal desulfurization was highly correlated with the amount of saturates in the feed, and the aromaticity of the resin fraction. Hydrogen consumption increased with the aromaticity of the gas oil…     

膜分离过程中原料气流量的控制方法

介绍了气体膜分离原理;提出了理想膜过程的新概念;归纳了气体膜分离装置的运行特点;比较分析了气体膜分离过程中原料气流量控制的各种方法;提出通过在尾气侧安装调节阀来定量调节原料气流量的控制方法;该方法成功应用于金陵石化加氢裂化低分气中提取高浓氢的工艺中,验证了这种控制策略的正确性和有效性;整体的控制方案又进一步提高了膜分离装置的操作柔性及适应能力;该方法可同时保证渗透气快气浓度及回收率的性能指标,适用于所有气体膜分离过程中对处理气量的自动控制.     

The Viscosity of cottonseed oil,fractionation solvents and their solutions

Cold fractionation of cottonseed oil is made difficult by the high viscosity of the oil. This study was aimed at demonstrating the effect of solvents on the viscosity of mixtures between 0°C and 25°C with a view to facilitating the fractionation of refined cottonseed oil. The solvents used were acetone, methylethylketone, methylisobutylketone, hexane and heptane. Measurements of viscosity were carried out by means of a capillary viscometer. The ratio of the viscosity of cottonseed oil to that of pure solvents is of the order of 300. The viscosities of solutions of various ratios of solvent to oil (1/3, 1/1, 3/1) are between those of cottonseed oil and the pure solvents. The effect of the solvent/oil ratio overrides that of solvent nature. The effect of solvent in reducing the viscosity of cottonseed oil is by descending order: acetone, hexane, methylethylketone, heptane, methylisobutylketone.