粗异戊烯在炼油三套装置的加工总结

粗异戊烯产自浙石化50万t/a裂解C5分离装置,年产8.8万t/a,粗异戊烯经过加氢后可作为汽油、乙烯原料或与甲醇反应生成高纯度的异戊烯。浙石化粗异戊烯可通过石脑油加氢装置、汽油加氢装置、S-Zorb装置加工。在石脑油加氢装置加工时,粗异戊烯进入拔头油作为乙烯原料送乙烯,解决了粗异戊烯因烯烃含量高不能直接送乙烯加工的问题;在汽油加氢装置加工时,粗异戊烯作为轻汽油馏分送至汽油醚化装置与甲醇反应,增加了工艺附加值;在S-Zorb装置加工时,由于粗异戊烯中的二烯烃自聚,使原料/反应产物换热器管程堵塞,造成偏流及换热效果下降,不能长期加工。     

低碳烯烃生产技术新进展

综述我国乙烯工业的产能、产量及原料组成情况,介绍了生产低碳烯烃的各种最新技术,如甲醇石脑油耦合、CO_2催化加氢、催化裂解、甲烷氧化偶联、原油直接裂解等技术的研究进展及应用情况,并指出了这些新技术是我国生产低碳烯烃的有效途径,要密切关注非石油路线制烯烃技术,保证石化工业的可持续发展。     

焦化液化气混合焦化汽油加氢技术及工业应用

焦化液化气作为延迟焦化装置产品,长期以来作为民用烃出厂,经济效益未得到充分开发.镇海炼化公司采用中石化大连石油化工研究院的焦化液化气和汽油混合加氢制备乙烯裂解料技术,建设了一套60万t·a-1的焦化液化气与焦化汽油混合加氢装置.生产出烯烃质量分数不大于1.0％的精制液化气和溴价不大于2.5 g Br·(100 g)-1的精制石脑油,可作为优质的乙烯裂解原料.对该工艺路线的技术特点、工业运行状况、经济效益等进行探讨分析,数据表明,焦化液化气和焦化汽油经新工艺路线加工后作为乙烯裂解原料,工艺路线简洁,经济效益显著.     

合成气制烃的催化过程和催化剂发展动态

4 合成气直接制烃催化剂提高合成过程竞争力的总趋势是控制选择性,开发定向合成催化过程和催化剂。目的产品是液体燃料汽油、柴油,化工原料乙烯、丙烯、异丁烯等低碳烯烃以及裂解原料低碳烷烃。4.1 合成低碳烯烃     

粗石脑油中二烯烃的选择性加氢脱除

预加氢反应单元作为重要的重整原料预处理单元,粗石脑油中的二烯烃属于高度不饱和烃,易在预加氢系统结焦,导致系统压降上升,催化剂堵孔失活,制约装置长周期平稳运行。本文选用国外2种典型的二烯烃加氢催化剂,采用选择性加氢技术,实现了二烯烃的深度脱除,从而抑制结焦反应,延长装置的整体开工时间。     

专利信息

工业碳五馏分 催化加氢制造成烷发明单位 上海石油化工高等 专科学校发明人 何美琴等 本发明是关于以工业碳五馏分为原料,经催化加氢制造戊烷的方法。石油烃的催化裂化过程或是石油烃的裂解制乙烯过程中的副产物——工业碳五馏分,是不饱和组分和饱和组分的混合物,其中大部分是非直链的不饱和碳五组分。本发明的方法就是直接利用工业     

林德公司与广石化进行技术交流

日前,西德林德公司 Karl Stork 先生一行到广州与广州石化总厂就林德-西拉斯裂解技术进行了技术交流。林德公司自1951年与美国西拉斯公司合作建设了第一套乙烯装置之后,便买下了西拉斯的裂解技术专利,并不断拓新。采用的原料以轻石脑油至加氢减压柴油等各种液态烃为主。目前林德-西拉斯裂解炉的主要参数如下表所示。     

C_4馏分加氢催化剂的应用

为了提高C_4馏分的利用价值并实现扩大乙烯裂解料的来源,使用自制的镍系加氢催化剂和钴-钼-镍系加氢精制催化剂,在固定床200 m L绝热评价装置上对C_4馏分液化石油气物料进行全加氢实验,论证镍系加氢催化剂适用于含有低碳含硫化合物C_4馏分的可行性,对模拟的某化工厂C_4馏分原料进行加氢饱和性能考察,对含有高浓度双烯烃和炔烃的丁二烯抽提装置尾气进行原料模拟和全加氢评价。结果表明,自制催化剂适用于含有低碳硫化物的C_4馏分全加氢,可以处理高含双烯烃的C_4物料,并具有良好的低温活性。     

催化裂化干气乙烯低聚催化剂活性组分研究

乙烯低聚制低碳烃是利用催化干气乙烯资源的有效途径。本文以催化干气为原料,在固定床反应装置上,采用HZSM-5催化剂,对乙烯低聚催化剂活性组分进行了研究。结果表明,活性组分含量20%~30%对提高烯烃收率有利;调节离子交换温度可以改善烯烃收率,但采用较快再生的流化床反应器更为合适。     

低温等离子体诱导低碳烃选择性催化还原NOx研究进展

综述了近年来低温等离子体诱导低碳烃选择性催化还原NOx的研究进展,详细介绍了难活化的甲烷及较易活化的非甲烷低碳烃气体如乙烯、丙烯及丙烷等的研究现状,探讨了低温等离子体诱导低碳烃选择性催化还原NOx的反应机理,并展望了低温等离子体诱导低碳烃选择性催化还原NOx今后研究方向。     

Vapour phase hydrogenation of olefins by formic acid over a Pd/C catalyst

It has been found that ethylene and propylene could be effectively hydrogenated by formic acid vapour over a Pd/carbon catalyst at low temperatures (<440 K). Surface hydrogen formation from formic acid is the rate-determining step for this hydrogenation reaction. Interaction of this hydrogen with the olefins is then fast. The conversion of formic acid in the presence of either of the olefins at any temperature is higher than in their absence. This has been explained by a much lower surface hydrogen concentration in the presence of the olefins. Direct experiments have confirmed that hydrogen inhibits the formic acid decomposition. Water vapour addition has a small positive effect on the decomposition of formic acid as well as on the hydrogenation of the olefins with formic acid. Catalysts consisting of gold supported on carbon or titania are both active in the production of hydrogen from formic acid. However, in contrast to the Pd/C catalyst, neither gives hydrogenation of the olefins with this acid.     

1,3-丙二醇的生产技术

综述了环氧乙烷羰基化法、丙烯醛水合加氢法和微生物发酵法生产 1 ,3-丙二醇工艺路线的原料、催化体系、工艺过程及研发状况。比较了 3种工艺路线的工艺特征、装置投资和生产成本。指出环氧乙烷羰基化法原料易得、成本较低 ,但技术难度高、设备投资大 ;丙烯醛水合加氢法成本略高 ,但反应条件缓和、技术开发相对容易 ,且拥有丙烯醛生产技术和基础 ;微生物发酵法反应条件温和、原料价廉易得、成本低 ,但距离工业化还有一定差距。     

一氧化碳对乙烯工业的影响

文章论述乙烯联合装置中一氧化碳(CO)的产生过程和控制方法、Co对乙烯装置、汽油加氢装置、聚内烯装置和全密度聚乙烯的影响、Co在乙烯联合装置的脱除方法以及Co变化对碳二加氢系统、甲烷化系统的操作方法.     

The hydrogenation of CO over molybdenum/alumina in the presence of ethylene; coupling of olefin metathesis and CO hydrogenation

Three reactions, CO hydrogenation, metathesis of C₂H₄ and CO hydrogenation in the presence of C₂H₄, have been investigated on Mo(+2)/Al₂O₃ under identical experimental conditions. The products of hydrogenation reactions were methane, ethylene and propylene. The results show that the initial rate of propylene formation for CO hydrogenation in the presence of ethylene is much larger, by a factor of 7, than the sum of the rate of propylene formation for CO hydrogenation and metathesis alone. Furthermore, it was found that¹³C labelled propylene was formed in the hydrogenation of¹³CO in the presence of ethylene. These results, taken as a whole, suggest that the same intermediate is formed in both CO hydrogenation and metathesis of ethylene, and that these intermediates can be either incorporated into ethylene and higher hydrocarbons by polymerization or incorporated into ethylene to form propylene via olefin metathesis.     

Synthesis of nanosized ethylene–propylene rubber latex via polyisoprene hydrogenation

Nanosized ethylene–propylene rubber (EPM) latex with a particle size of 47 nm was synthesized via an alternative route consisting of isoprene (IP) polymerization followed by hydrogenation. First, the IP monomer was polymerized by differential microemulsion polymerization to obtain polyisoprene (PIP) rubber latex with a particle size of 42 nm. The structure of synthetic PIP was hydrogenated at the carbon–carbon double bonds to produce an ethylene–propylene copolymer by diimide reduction in the presence of hydrazine and hydrogen peroxide using boric acid as promotor. The degree of hydrogenation was determined by proton nuclear magnetic resonance (¹H‐NMR) spectroscopy and the structure of the ethylene–propylene copolymer was identified by ¹³C‐NMR spectroscopy. In nanosized PIP hydrogenation, the hydrogenation level was found to be increased by boric acid addition. An EPM yield of 94% was achieved using a hydrogen peroxide : hydrazine ratio of 1.5 : 1. The EPM produced from PIP has high thermal stability with the maximum decomposition temperature of 510°C and a glass transition temperature of ‐42.4°C close to commercial ethylene–propylene diene rubber. Dynamic mechanical analysis indicated that EPM had a maximum storage modulus due to the saturated carbons domains of the ethylene segments in the polymer chains. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Hydrogenation of cis‐1,4‐poly(isoprene) catalyzed by OsHCl(CO)(O2)(PCy3)2

The quantitative hydrogenation of cis‐1,4‐poly(isoprene) (CPIP) provides an easy entry to the alternating copolymer of ethylene–propylene, which is difficult to prepare by conventional polymerization. The homogeneous hydrogenation of CPIP, in the presence of OsHCl(CO)(O₂)(PCy₃)₂ as catalyst, has been studied by monitoring the amount of hydrogen consumed during the reaction. The final degree of olefin conversion measured by computer‐controlled gas uptake apparatus was confirmed by infrared spectroscopy and ¹H nuclear magnetic resonance analysis. Kinetic experiments for CPIP hydrogenation in toluene solvent indicate that the hydrogenation rate is first order with respect to catalyst and carbon–carbon double bond concentration. A second‐order dependence on hydrogen concentration for low values and a zero‐order dependence for higher values of the hydrogen concentration was observed. The apparent activation energy for the hydrogenation of CPIP over the temperature range of 115–140°C was 109.3 kJ/mole. Mechanistic aspects of this catalytic process are discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 142–152, 2003     

CO2合成醇酯类化学品和高分子材料研究进展

我国作为煤炭大国,燃烧化石燃料产生大量CO₂。通过化学作用将CO₂转化为能源燃料、基础化学品或高分子材料,有利于实现碳氧资源综合利用。从CO₂直接利用和间接利用的角度出发,分别综述了CO₂资源化利用研究进展。直接利用方面,重点阐述了CO₂直接加氢合成甲醇和乙醇;同时CO₂可作为羰化剂合成有机碳酸酯和高分子材料,包括碳酸二乙酯、聚碳酸酯和CO₂基可降解聚合物。在间接利用方面,重点综述了CO₂经碳酸乙烯酯的酯交换反应合成碳酸二甲酯,以及碳酸乙烯酯加氢制备甲醇联产乙二醇的研究进展。CO₂加氢直接合成甲醇催化剂主要包括铜基催化剂、贵金属催化剂,由于贵金属的成本高,廉价的Cu基催化剂研究较为广泛。CO₂加氢直接合成乙醇研究较广泛的催化剂为贵金属(Rh、Pd、Ru)基催化剂体系,还需进一步研究廉价、高活性和高稳定性的催化剂。CO₂与乙醇直接合成碳酸二乙酯(DEC)研究较多的催化剂为铈基多相催化剂,但由于生成物中水分的影响,限制了DEC的收率。环氧化物和CO₂耦合反应生成DEC过程中不产生水,可以有效克服热力学的限制,因此高能化合物与CO₂的耦合路线是高效制备DEC的有效途径。CO₂与环氧化物共聚制备聚碳酸酯材料多采用稀土三元催化剂体系,环氧化物的转化率和聚碳酸酯选择性较高,目前已经实现工业应用。CO₂通过碳酸乙烯酯与甲醇酯交换合成DMC,多使用碱性较强的催化剂和含碱性基团的离子交换树脂。CO₂经碳酸乙烯酯加氢制备甲醇和乙二醇的反应中,铜基催化剂展现出优异的催化性能。CO₂化学转化利用是CO₂碳氧资源综合利用的重要途径,将有效支撑我国未来碳中和目标实现。     

CO hydrogenation on rhodium catalysts as studied by temperature programmed desorption and reaction

The addition of promoters to rhodium catalysts has been studied for CO hydrogenation. Differences in temperature programmed desorption and reaction show that the support and promoter have an influence on the dissociation of carbon monoxide. A low temperature methane peak appears at 110°C in the CO temperature programmed hydrogenation on the unpromoted catalyst. The mechanistic implications of these results are discussed.     

茂名乙烯装置脱丁烷塔堵塞原因分析及对策

茂名2号乙烯装置脱丁烷塔长时间运行,进料中的不饱和烯烃组分发生聚合结垢堵塞塔盘,降低了脱丁烷塔的分离效果,导致脱丁烷塔塔釜中碳四损失升高.针对脱丁烷塔碳四损失严重的问题,利用闲置的2号裂解汽油加氢装置后脱戊烷塔对其进行了流程改造,将脱丁烷塔与后脱戊烷塔串联操作,脱丁烷塔塔釜的物料采出作为脱戊烷塔进料,进一步分离回收碳四...     

Mitteilungen/announcements

A series of telechelic additives with molecular weights of 500–1500 for polyolefins was prepared by reaction of telechelic polyolefins with amino-, carboxy-and aldehyde end groups were obtained by hydrogenation of the corresponding telechelic polybutadienes which were prepared by radical polymerization of butadiene with appropriate functional initiators as well as by anionic polymerization of butadiene and termination with carbon dioxide, ethylene oxide and chloroacetaldehyde dimethyl acetal. Oligomeric polyolefins with stabilizer end groups attached by non-hydrolyzable C C-bonds were obtained by end-capping of living polybutadiene with appropriate functional additive components and subsequent hydrogenation. Preliminary tests of some of the telechelic additives demonstrated excellent compatibility with polypropylene and efficiencies similar to low-molecular standard additives.