优化操作降低催化汽油的烯烃含量

介绍降低催化汽油烯烃含量的机理和途径，结合蜡油催化裂化装置的实际情况，从优化操作参数着手，采取降低反应温度、增加催化剂活性和拓宽汽油馏程等方法，使催化汽油烯烃的平均含量降低了6个百分点，初步达到了目的，并提出进一步改进的建议。     

降低催化裂化汽油烯烃含量的研究

采用加氢异构芳构化催化剂及其配套工艺，以催化裂化未脱硫未脱双烯烃全馏分汽油为原料，在反应温度390℃，反应压力2．0—3．0MPa，进料重时空速1．0h^—1，氢油体积比300-400条件下进行加氢、异构、芳构化反应，所得产物与原料相比，烯烃含量降低35．8个百分点，芳烃含量增加16个百分点，RON增加了0．3个单位。由于基本脱除了汽油中的双烯烃，使汽油的诱导期明显延长，其余各项分析数据基本达到国家车用汽油标淮。     

优化工艺条件降低催化裂化汽油烯烃含量

为满足环保要求,降低催化裂化汽油中的烯烃含量,北京燕山石油化工股份有限公司2Mt/a重油催化裂化装置进行了工艺条件的调整和优化。通过合理利用MGD技术,提高平衡剂活性,优化稳定塔的操作,改变终止剂及预提升介质等,将催化裂化汽油φ（烯烃）由67％左右降低到55％左右,收到了良好的效果;随着汽油烯烃含量的下降,RON下降了约1个单位,MON变化不大,汽油诱导期也无明显上升。为使用降烯烃催化剂创造了良好条件并积累了经验。     

优化工艺条件降低汽油烯烃含量

针对广州石化蜡油催化裂化装置汽油烯烃含量高的问题,对工艺条件进行了优化调整,包括降低反应温度、增大剂油比、提高催化剂活性、拓宽汽油馏程和提高稳定塔的稳定深度等。结果表明：控制反应温度为485℃,剂油体积比为5．5～7．0,催化剂活性约～70％,汽油馏程干点为205℃,稳定塔塔顶温度为59℃、塔底温度为180℃时,可使该装置汽油烯烃体积分数由43．2％下降至35％左右。     

降低催化裂化汽油烯烃含量过程优化调节

本文以200×104t/a催化裂化装置为例,要求成品汽油中烯烃含量不大于15.0%,经过内部核算,要求中间产品（稳汽）厂内控制目标为不大于28.0%。通过对反应温度、催化剂活性、吸收分馏系统等影响汽油烯烃含量的工艺操作进行了调整,达到一定效果后,再对催化剂的配方进行优化调整,以达到所要求的内控指标。     

缓和重整降低催化裂化汽油的烯烃含量

提出了缓和重整降低催化裂化汽油烯烃含量的技术路线,将催化裂化汽油切割为轻、重两种馏分,并对其中的重馏分先加氢精制,再进行缓和重整处理,使汽油的辛烷值得到恢复.该技术得到的汽油产品在满足汽油指标要求的条件下,辛烷值没有损失,总液体收率高,氢气能够自给且略有富余.介绍了两种工艺流程方案,均取得比较满意的结果,说明缓和重整降烯烃技术具有操作上的灵活性,通过技术路线及操作条件的凋整,可使炼油企业生产出符合汽油指标要求的汽油产品.     

催化裂化增产丙烯并降低汽油烯烃

针对ＤＣＣ技术的特殊性 ,北京石科院开发了ＤＣＣ增产丙烯并降低汽油烯烃含量的专利技术。安庆石化分公司在今年ＤＣＣ装置检修时 ,采用石科院的技术进行了装置改造 ,并进行了工业试验 ,这是目前国内首套应用ＤＣＣ增产丙烯并降低汽油烯烃含量专利技术的催化裂化装置。试验结果如下 :应用汽油回炼技术后 ,丙烯收率增加了 2 69% ,液化气收率增加了 4 3 1 % ,汽油烯烃降低了 1 0 1 3 % ;应用Ｃ4 回炼技术后 ,丙烯收率增加了 2 1 6% ;应用汽油回炼以及Ｃ4 回炼技术后 ,丙烯收率增加了 3 92 % ,液化气收率增加了 4 48% ,汽油烯烃降低了 6 1…     

降低催化裂化汽油烯烃含量技术进展

介绍了降低催化裂化汽油烯烃含量的途径,包括选择合适的催化裂化工艺、应用降烯烃催化剂和助剂、选择中质中间基FCC原料、对原料进行预处理以及对催化裂化汽油进行后处理等。简述了各种催化裂化工艺和降烯烃催化剂及助剂在部分FCC装置的应用效果。指出要实现油品的清洁化,应开发FCC汽油醚化工艺,建造汽油加氢、重整、异构化和烷基化装置。     

优化操作降低重催汽油的烯烃含量

在多产柴油的生产方案下，通过调整操作参数，降低重催汽油烯烃的含量，取得了明显的效果，最低可降至39％，同时以装置的实际生产数据说明了反应温度、剂油比和催化剂活性等因素对重催化汽油烯烃含量的影响程度。     

降低催化裂化汽油烯烃含量的技术措施

为实现国Ⅵ汽油质量升级,分析了国ⅥA标准汽油生产中存在的问题,其主要原因为催化汽油烯烃含量高,影响国ⅥA标准汽油的调和。通过优化重催装置操作条件、应用新型降烯烃催化剂、优化汽油加氢装置操作条件、优化汽油醚化装置剩余碳五加工等技术措施,两套重催装置汽油烯烃体积分数由35%降至30%左右,汽油加氢装置汽油烯烃体积分数由24.7%降至18.9%,汽油的半成品罐汽油中烯烃体积分数由25.7%降低至21.5%,满足了国ⅥA标准汽油的调和需要,实现了国Ⅵ汽油的质量升级。     

Investigation of the Operating Conditions on Decreasing FCC Gasoline Olefin Content by GOR-Q Catalyst

Abstract

Based on a fixed-fluid-bed reactor and a GOR-Q catalyst, the influence of process parameters on decreasing gasoline olefin content was studied. The results show that the catalyst had an obvious effect on the decreasing gasoline olefins. A higher catalyst-to-oil ratio, lower weighted hourly space velocity, and lower reactor temperature give rise to lower gasoline olefin content. The reduction of fluid catalytic cracking (FCC) gasoline olefin content is achieved by decreasing olefins of low carbon number. Reaction temperature under 520°C and catalyst-to-oil ratio = 7.0 for a GOR-Q catalyst are advantageous for decreasing olefin content of FCC gasoline.     

Study on Olefin Decrement Reformulation and Increasing Light Olefins of FCC Gasoline by Catalytic Cracking

Abstract

Catalytic upgrading of fluid catalytic cracked (FCC) gasoline obtained from Huabei Petrochemical Company, PetroChina (Renqiu, Hebei, China), was investigated using a microreactor and gas chromatograph integrated unit in order to decrease the content of olefins in gasoline and increase the light olefins (ethylene, propylene, and butylene) content. The experimental results showed that the olefin content in upgraded gasoline can be decreased from 42.6% in raw material to nearly 10%, meeting the requirements of the new gasoline standard, whereas iso-alkane and aromatics contents were markedly increased, from 28.4 and 18.2% to 47 and 36.1%, respectively, so the octane number of gasoline should not be reduced. In addition, higher yields of light olefins were obtained after FCC gasoline was reformulated under laboratory conditions. Higher reaction temperature, longer reaction time, higher weight ratio of catalyst to oil, and higher catalyst activity were beneficial to decrease the olefin content of FCC gasoline and increase the yields of light olefins.     

催化裂解制烯烃的技术进展

与传统的蒸汽裂解技术相比 ,液体原料的催化裂解技术具有裂解温度低、烯烃收率高和产物分布灵活性高等优点 ,以催化裂解代替蒸汽裂解制乙烯一直是人们追求的目标。本文综述了催化裂解制烯烃技术的进展情况 ,介绍了目前主要研究的催化剂类型和有代表性的研究成果 ,并指出催化裂解制烯烃技术具有很好的开发前景。     

流化催化裂化汽油含硫化合物生成规律的考察

在小型固定流化床装置上采用流化催化裂化(FCC)催化剂、以FCC汽油轻馏分和H2S标准气为原料,考察了催化剂类型、原料组成和反应条件(反应温度、催化剂与原料油的质量比(剂油比)和重时空速)对硫化物生成的影响。实验结果表明,FCC汽油中的烯烃与H2S反应主要生成噻吩类硫化物和部分硫醇;在REUSY分子筛催化剂(催化剂A)上的硫化物收率比在ZRP型择形分子筛催化剂(催化剂B)上的高;且硫化物收率随H2S和烯烃含量的增加呈线性增长。受反应温度对烯烃转化程度的影响,较高的反应温度有利于抑制烯烃与H2S反应。因为反应机理及催化剂性质对噻吩类硫化物和硫醇的生成影响不同,两者收率随剂油比和重时空速的变化趋势不同,但变化幅度均不大,因而总硫化物收率随重时空速和剂油比的变化幅度也不大。     

操作条件对流化催化裂化汽油重馏分催化精馏加氢脱硫的影响

利用 CoMoP/Al_2O_3-TiO_2汽油加氢脱硫工业催化剂,在新型垂直筛板塔催化精馏装置上对流化催化裂化(FCC)汽油重馏分进行加氢脱硫,考察了进料口位置、压力、氢气与原料油的体积比、原料油的液态空速和回流比对催化精馏加氢脱硫效果的影响。实验结果表明,在进料口位置为第7塔节、压力2.0 MFa、反应段平均温度279℃、氢气与原料油的体积比300、液态空速2.0 h~(-1)、回流比2.0的条件下,FCC 汽油重馏分脱硫率达到95.73%,硫含量由850 42μg/g 降至36.32μg/g,辛烷值损失仅为0.6。将催化精馏加氢脱硫与固定床加氢脱硫进行了对比,结果表明,在相似的操作条件下,催化精馏加氢脱硫的脱硫率略低于固定床加氢脱硫,但油品的辛烷值损失较小。     

Analysis of Measures and Effect on Reducing Olefin Content in Gasoline

This article refers to major measures for reducing olefin content of automotive gasoline and the effect after adoption of these measures. The key for reducing olefin content in China＇s automotive gasoline pool is to reduce the olefin content of FCC naphtha. The domestic refiners apply the olefinreducing catalyst to decrease the olefin content of FCC gasoline as a convenient and cheap means to meet the national standard for automotive gasoline at the present phase. Furthermore, the novel domestic FCC reaction processes, such as the MIP, MGD, FDFCC and other processes can also apparently reduce olefin content in FCC gasoline. In order to further reduce the olefin content in gasoline to meet more stringent standard for automotive gasoline, Chinese refiners should optimize the processing scheme while aggressively disseminating hydrogenation process along with development of catalytic reforming, alkylation, etherification and other processes to completely change the simplistic composition of domestic gasoline pool.     

A New Downstream Process Design for a Fluid Catalytic Cracking Unit to Raise Propylene Yield and Decrease Gasoline Olefin Content

Abstract

Based on the paraffins, olefins, naphthenes, aromatics (PONA) composition of crude light gasoline, crude heavy gasoline, stabilized gasoline, and wet gas of a pilot plant fluid catalytic cracking (FCC) unit, it was found that the root cause of high gasoline olefin content and low propylene yield was low C₅ and C₆ olefin content of crude light gasoline. A new design for the main fractionater and absorber–stripper–stabilizer was presented to obtain stabilized light gasoline that contains more C₅ and C₆ olefins recracked in the secondary riser. Industrial studies on the revamped unit showed that gasoline olefin content was decreased markedly, though research octane number (RON) was preserved. In addition, propylene yield was raised to a higher level and unit energy consumption (or operating cost) was not increased.     

Energy Optimization Design of ARFCC Process for Reducing Gasoline Olefin

Abstract

In view of the high energy consumption inherent in the auxiliary riser fluid catalytic cracking (ARFCC) process, a new energy optimization design has been suggested in this paper to decrease its auxiliary system energy cost and improve its product quality. The heat distribution of an auxiliary fractional system has been optimized and its surplus heat was used to heat crude gasoline, making low-temperature liquid crude gasoline into gas, which was then fed into the auxiliary reactor. The application in an ARFCC unit with 75 t/h of crude gasoline to be reprocessed showed, after the energy optimization design, that when the crude gasoline feed was heated from 40°C to 219°C, the contact temperature difference between the feed and the regenerated catalyst reduced from 650°C to 322°C, process exergy loss decreased by 77.8%, and less dry gas and coke was formed in the auxiliary reactor. At the same time, the energy-use optimization of the auxiliary fractional system increased its exergy recovery efficiency by 25%, 9.73 GJ/hr more valid heat was recovered, and 23.5 t/h more medium pressure steam was produced by the heat of the regenerated catalyst replaced by gaseous crude gasoline. The total energy consumption of the ARFCC process was reduced by a 6.8 kgEO/t feed.     

操作参数对FCC汽油烯烃度的影响

在XTL-5小型提升管催化裂化试验装置上,考察了操作条件对汽油烯烃度的影响。在此基础上,分别构造了两个表示烯烃含量大小和氢转移反应强弱的参数——烯烃度和氢转移指数。还探讨了反应温度和剂油比等操作条件对FCC汽油烯烃度的影响规律及机理。