用加氢工艺制取高质量润滑油基础油

叙述了用环烷基、中间基及石蜡基原油，在现有的润滑油基础油生产工艺中引入加氢精制技术，采用润滑油馏分加氢脱酸、临氢降凝工艺和润滑油加氢处理工艺、润滑油溶剂萃取－中压加氢处理组合工艺，以及由蜡膏异构等项技术，制取ＬＶＩ、ＬＶＩＷ、ＨＶＩ、ＶＨＶＩ、ＵＨＶＩ各种基础油的研究结果。     

用加氢工艺制取高质量润滑油基础油

叙述了由环烷基，中间基及石蜡基原油，在现有的润滑基础油生产工艺中引入加氢精制技术，采用润滑油馏分加氢脱酸，临氢降凝工艺和润滑油加氢处理工艺，润滑油溶剂萃取－中压加氢处理组合工艺，以及由蜡膏异构等项技术，制取ＬＶＩ，ＬＶＩＷ，ＨＶＩ，ＶＨＶＩ，ＵＨＶＩ各种基础油的研究结果。     

国内外润滑油生产工艺综述

目前国内外以常减压、溶剂脱沥青、溶剂精制、溶剂脱蜡、补充精制等工艺为主生产基础油。但是加氢工艺发展很快，尤其是加氢异构工艺生产高粘度指数（ＶＨＶＩ）、超高粘度指数（ＵＨＶＩ）的基础油很有吸引力。由于环保的要求，合成润滑油将有较快的发展，应引起科研和生产单位的高度重视。分析我国加氢法生产基础油、合成法生产润滑油与国外生产工艺间存在的差距。     

加氢法制取润滑油基础油的工艺技术

以辽河、新疆、胜利、大庆原油和含硫油的润滑油馏分为原料,采用加氢技术制取润滑油基础油。中型试验结果表明,采用高压加氢处理、溶剂精制－中压加氢处理技术,配以溶剂脱蜡可以制取氧化安定性好的ＨＶＩ润滑油基础油;采用加氢处理／加氢异构脱脱蜡／加氢补充精制工艺,制取氧化安定性和低温流生好的ＨＶＩ和ＶＨＶＩ润滑油基础油也是可行的。与传统润滑油生产工艺相比,加氢法具有目的的产品收率高、质量好等优点。     

进一步发展我国润滑油基础油生产技术的意见

就我国润滑油生产状况及润滑油产品质量水平不高的原因进行了分析，对如何进一步发展我国润滑油基础油生产技术提出广一些建议，认为应加大ＨＶＩ基础油的比例，发展ＵＨＶＩ及ＶＨＶＩ基础油的生产工艺。     

基础油烃类组成对1—H2试验的影响—MVI和HVI基础油添加剂配方互换的可能性

按ＡＰＩ基础油换用规则，新疆ＭＶＩ基础油粘度指数小于８０，应属于第三类基础油。它的添加剂配方或复合剂不能换用第一类基础油，如大庆ＨＶＩ基础油或第二类基础油，如加氢处理基础油。否则应重做全部发动机试验予以确认。然而ＡＰＩ基础油换用规则有局限性。试验结果表明，用于新疆ＭＶＩ基础油的ＣＣ级油配方或复合剂可以换用于大庆ＨＶＩ基础油；而用于ＨＶＩ基础油的ＣＣ级添加剂配方或复合剂却不能换用于新疆ＭＶＩ基础油。     

高硫原油生产润滑油基础油技术的研究

用常规润滑油加工技术难以用高硫伊朗轻质原油润滑油馏分生产ＨＶＩ基础油。石油化工科学研究院开发了常规工艺与加氢处理相结合的组合工艺（ＲＬＴ 技术）,用高硫伊朗轻质原油润滑油馏分生产ＨＶＩ基础油的研究结果表明,采用ＲＬＴ 技术,可用高硫伊朗轻质原油润滑油馏分生产ＨＶＩ基础油（ＶＩ≥９５）和ＶＨＶＩ基础油（ ＶＩ≥１２０）,反应条件缓和,在调节产品质量方面具有很好的灵活性。ＲＬＴ 技术是一种生产高质量润滑油基础油的经济且先进的技术。     

石蜡基原料油加氢异构脱蜡制润滑油基础油催化剂的研制

以AEL分子筛为载体,制备出一种贵金属异构脱蜡催化剂;以n-C12为模型物,以大庆炼化加氢预精制后的650SN糠醛精制油为实际原料考察该催化剂的加氢异构化催化性能。试验结果表明,所制备的异构脱蜡催化剂对n-C12以及650SN糠醛精制油均具有良好的异构化活性和选择性,其性能优于国外同类参比剂,加工650SN糠醛精制油时,可高收率地生产出优质API Ⅲ类润滑油基础油,目标产品倾点为－21 ℃,比采用参比剂时低6 ℃,重质基础油收率为62.79%,比采用参比剂时高5.55百分点。     

催化脱蜡工艺生产润滑油基础油

介绍用择形催化脱蜡催化剂对中东原油减压馏分糠醛精制油催化脱蜡,结果表明,对于高蜡含量的油料,采用异构脱蜡技术不仅可以降低油品的倾点,而且还可以保持很高的液体收率,用异构催化剂对加氢裂化尾油异构脱蜡液收可达９５％,其中大于３５０℃馏分收率为８０％,粘度指数达１２０,可做ＶＨＶＩ基础油馏分,而且不需要溶剂脱蜡。     

含Mg加氢异构脱蜡催化剂临氢异构性能研究

以制备的H-ZSM-23分子筛为载体,采用等体积共浸渍的方法制备加氢异构催化剂Pt/ZSM-23,Pt-Mg/ZSM-23-1%,Pt-Mg/ZSM-23-2%,研究Mg的引入对催化剂酸性质的影响,并以惠州加氢裂化尾油为原料,对Pt/ZSM-23和Pt-Mg/ZSM-23-2%的临氢异构性能进行研究。研究结果表明：Mg的引入可极大降低催化剂的中强酸含量,催化剂选择性提高;将Pt/ZSM-23和Pt-Mg/ZSM-23-2%按体积比1∶1级配装填,在反应温度为325 ℃、反应压力为13 MPa、氢油体积比为500、液时体积空速为1.1 h－1的条件下,基础油收率由75.0%提高至79.0%;1 000 h长周期运行期间催化剂性能稳定,150N润滑油基础油的倾点为－18 ℃、收率为48.0%,高于常规工业装置的46.0%,基础油总收率为79.3%,催化剂加氢异构性能优异,具备良好的工业化应用前景。     

油相中有机氯的相转移催化脱除研究

以200号芳烃溶剂油分别与环氧氯丙烷、三氯甲烷和氯化苯混合制成含有机氯的模拟油样,研究反应温度、反应时间、相转移催化剂及NaOH加入量对油相中有机氯脱除率的影响。实验结果表明:有机氯脱除率随反应温度升高、反应时间延长、相转移催化剂及NaOH加入量的增加均提高;油相中环氧氯丙烷的适宜脱除条件为:季胺碱0.05%,NaOH 0.6%,温度90℃,时间1 h;油相中三氯甲烷的适宜脱除条件为:季胺碱0.1%,NaOH 0.6%,温度100℃,时间1 h;油相中氯化苯的适宜脱除条件为:季胺碱0.15%,NaOH 1.2%,温度120℃,时间2 h。     

采用在线磁分离技术回收催化裂化平衡催化剂再利用

采用强磁场磁选技术，可以有选择地、大量地从催化裂化平衡剂中剔除老化程度高、受重金属(Ni、V、Fe)污染程度深的催化剂颗粒，使催化剂平衡活性得到改善，在减少新鲜催化剂补充量的基础上，提高原料油的总体转化水平。着重考察了华北、燕山等6家炼油企业催化裂化平衡催化剂经强磁场磁选后，回收部分的产率与磁化率的关系，以及采用最佳磁化率下的低磁剂样品与其原始平衡剂和高磁剂的重金属含量、微反活性的对比关系，提出了强磁场磁选技术在催化裂化工艺中的应用模式。     

含IM-5分子筛的催化裂化催化剂的反应性能

IM-5分子筛是一种具有中等孔径的三维孔道分子筛。通过对其老化后的分子筛结构和酸性特征分析发现,IM-5分子筛具有一定量的中孔,较强的酸性和较高的B酸比例,具有应用于FCC催化剂的结构和酸性基础。将含有IM-5分子筛的催化剂进行混合模型化合物催化裂化实验,发现其具有提高转化率和提高低碳烯烃收率的作用。以某加氢蜡油(HVGO)为原料油的催化裂化ACE评价结果也表明,引入新催化材料IM-5分子筛后,裂化HVGO原料的转化率增加约4.5百分点,液化气收率提高5百分点以上,汽油收率略有下降,轻循环油、油浆、焦炭收率均下降1百分点左右。因此IM-5是一种具有工业应用前景的中孔分子筛。     

Spherilene聚乙烯气相聚合工艺

本文论述了Spherilene聚乙烯气相聚合工艺及其工艺技术特点。该工艺采用轻烃替代氮气作为反应传热介质,改善了反应体系传热能力,降低了反应体系物料中结块的几率,使聚合生产过程更稳定。采用其独特的AvantZ催化剂可获得球形树脂颗粒。     

渣油催化裂化装置消除剂油比瓶颈的方法

介绍了渣油裂化催化剂的性能要点 ,讨论了渣油裂化催化剂性能的发挥、产品分布、汽油辛烷值等与剂油比的关系。指出渣油裂化一般采用氢转移活性低的催化剂 ,这种催化剂需要在高剂油比下操作 ;对渣油的裂化和提高汽油辛烷值也需要高的剂油比。现有一些催化剂循环量受到限制剂油比较低的装置可采用分段进料的方法 ,着重提高对渣油的剂油比。提出了现有几种装置提高剂油比的方法。     

Development of a Method for the Extraction of Oil from Clay by Friendly Phase Transfer Catalyst

Abstract

The separation of waste oil from clay was studied using benzyl triethanol ammonium chloride as phase transfer catalyst. The study showed that the surface tension has an effect on oil recovery. An induced air flotation process was used and polymeric decyl phenol formaldehyde ethoxylate was used as the collector. The effects of various parameters including concentration of catalyst, collector, time of flotation, contact angle, and zeta potential on oil extraction were studied. The results show that oil recovery increases with time of flotation up to a maximum and then levels off. Oil recovery is marginal if the flotation time is extended beyond 12 min. For example, oil recovery increases by only 4% for 25 g oil and 20 g surfactant in the feed when flotation time increases from 12 to 15 min. Oil recovery also increases with surfactant dosage. Furthermore, oil recovery was enhanced by controlling the interfacial tension at the oil–water and water–air interfaces. The mechanism of oil separation was discussed according to micelle composition and the calculated oil recovery obtained was 87%. Furthermore, the kinetic study proved that the process is first order and depends on catalyst concentration. Oil recovery follows a Gibbs adsorption equation. The molecular interaction parameter at the aqueous solution–air interface was also calculated. The results proved that the extraction of oil from solid phase can be conducted by adding phase transfer catalyst. Moreover, the article suggests a model of oil separation from soil according to specifications of adsorbed oil, including isoparaffin and n-paraffin that were analyzed by gas chromatography technique.     

重油加氢催化剂用于中/低温煤焦油加氢改质的中试研究

在3×400 mL固定床加氢中试装置上评价了重油固定床加氢催化剂（包括重油加氢保护剂、重油加氢精制催化剂和芳烃饱和催化剂）用于中/低温煤焦油加氢改质的效果。中试条件为：原料体积空速0.8 h-1（按加氢精制催化剂计算）,反应压力12.0 MPa和13.5 MPa,氢油比1 200∶1,保护剂床层平均反应温度270℃,精制催化剂床层平均反应温度350℃,芳烃饱和催化剂床层平均反应温度360℃,在2个操作压力下各运转120 h。结果表明：提高煤焦油加氢改质反应压力,有利于杂原子的脱除。煤焦油经过加氢改质后,残炭、杂原子、芳烃含量大大降低,各馏分产品性质明显改善。产物中石脑油馏分含量增加,芳烃潜含量高,可作为优质的催化重整原料;柴油馏分含量基本不变,硫、氮含量低,凝点低,可作为优质的柴油调合组分;蜡油馏分含量明显降低,残炭和金属含量少,可作为优质的催化裂化原料。上述结果表明将重油固定床加氢催化剂用于煤焦油加氢改质在技术上是可行的。     

Temperature distribution of fluids in a two-section two-phase closed thermosyphon wellbore

Compared with a conventional single section two-phase closed thermosyphon （TPCT） wellbore, a two-section TPCT wellbore has better heat transfer performance, which may improve the temperature distribution of fluid in wellbores, increase the temperature of fluid in wellheads and even more effectively reduce the failure rate of conventional TPCT wellbores. Heat transfer performance of two-section TPCT wellbores is affected by working medium, combination mode and oil flow rate. Different working media are introduced into the upper and lower TPCTs, which may achieve a better match between the working medium and the temperature field in the wellbores. Interdependence exists between the combination mode and the flow rate of the oil, which affects the heat transfer performance of a two-section TPCT wellbore. The experimental results show that a two-section TPCT wellbore, with equal upper and lower TPCTs respectively filled with Freon and methanol, has the best heat transfer performance when the oil flow rate is 200 L/h.     

沸石基油砂沥青改质催化剂的性能研究

研究和开发高效减黏、抗硫氮和重金属的水热催化裂化改质催化剂是油砂沥青资源利用技术的关键,以天然斜发沸石为基质制备氢型沸石载体和微孔镍基沸石催化剂,考察其应用于模型化合物水热裂化的性能和对加拿大麦肯河SAGD油砂沥青减黏改质的效果。结果表明：在正十六烷为模型化合物的水热裂化过程中,微孔镍基沸石催化剂表现出良好的催化裂化性能和优良的水热稳定性;在油砂沥青改质试验中,微孔镍基沸石催化剂能够显著降低油砂的黏度,增产中间馏分油,并在一定程度上降低硫、氮含量,可用于中低温和非临氢条件下的油砂沥青减黏改质。     

CATALYST EFFECTIVENESS FACTORS UNDER GAS-TO-LIQUID MASS TRANSFER LIMITING REGIME IN LIQUID PHASE METHANOL SYNTHESIS PROCESS

The effectiveness factors of methanol synthesis catalyst were experimentally measured under condition of gas-to-liquid mass transfer limiting regime in the liquid phase methanol synthesis process, where the synthesis catalyst is slurried in an inert liquid phase. The experimental measurements of effectiveness factors were based on an intrinsic methanol synthesis rate per unit mass of catalyst (gmol/kg cat.h) which is not limited by external mass transfer. The experiments were carried out under well-defined conditions of temperature, pressure, syngas feed flow rate, and impeller speed. The experiments were carried out in a 1-L stirred autoclave. The catalyst slurry ratios were varied from 10 g in 550 mL of Witco-40 oil (corresponding to a slurry ratio of 2.2%) to 150 g in 550 mLof Witco-40 oil (corresponding to a slurry ratio of 25.1%). The experimental measurements have been summarized in one single plot as generalized catalyst effectiveness factor as a function of catalyst slurry ratio. The results of this study are extremely significant and practical in their applicability because the data were obtained using commercial methanol catalysts under actual commercial operating conditions of liquid phase methanol synthesis process.