Studies on Pretreatment of Catalytic Cracking Slurry Oil with Added Furfural

Abstract:

In the experiment, the furfural added compound agent was applied to treat catalytic cracking slurry oil in order to utilize the saturated hydrocarbon and condensed-nuclei aromatics reasonably and soundly. The added agent could improve the dissolubility and selectivity of furfural and enhance the recovery and quality of treated oil. The optimum condition was as follows: compound ratio was 0.5:1; the added quantities were 8% relative to furfural volume; the temperature was 50°C; the solvent/oil ratio was 0.5:1. Under the condition, compared with that of furfural extraction, the recovery of treated oil was increased 14.8 wt%, the quality of treated oil also had been improved to some extent, and thus, the treated oil could be used as good stockfeed of catalytic cracking. The extract oil contained abundant condensed-nuclei aromatics, which could be used as good stockfeed to produce a high value-added chemical engineering product.     

新型稠环芳烃萃取剂的研究开发

中国石油化工股份有限公司九江分公司催化裂化重油抽提工艺以糠醛为萃取剂分离催化油浆或回炼油中稠环芳烃,但因糠醛在酸性物质存在以及一定的温度下,易与稠环芳烃起缩合反应,造成设备结焦。现开发新型稠环芳烃萃取剂来替代糠醛,对于完善和改进催化裂化重油抽提工艺,具有重要意义。新型稠环萃取剂在抽提效果、溶剂损失、经济效益均优于糠醛。     

糠醛抽出油调合道路石油沥青研究

将糠醛抽出油按不同比例分别掺入到伊重减渣和阿曼丙脱沥青中进行道路石油沥青调合试验,考察糠醛抽出油对沥青性能的影响。试验结果表明：糠醛抽出油能有效改善伊重减渣和阿曼丙脱沥青的某些性能指标,调合出合格的道路石油沥青产品。     

催化裂化轻循环油生产高辛烷值汽油或轻质芳烃(LTAG)技术关键及实践

基于对催化裂化轻循环油(LCO)烃类组成分子水平表征、LCO中稠环芳烃加氢反应规律和加氢LCO中四氢萘类单环芳烃的催化裂化与氢转移反应规律的认识,开发了将LCO高效转化为高辛烷值汽油或轻质芳烃的LTAG技术。LTAG技术是LCO加氢与催化裂化的集成技术,其技术关键是将LCO中稠环芳烃通过选择性加氢饱和反应生成四氢萘类单环芳烃,再通过强化加氢LCO中四氢萘类单环芳烃的催化裂化反应和抑制氢转移反应,实现LCO的高值化利用。加氢单元可采用LCO单独加氢或LCO与蜡油或渣油混合加氢模式;催化裂化单元可采用以下两种模式:①加氢LCO单独催化裂化生产高辛烷值汽油馏分或轻质芳烃;②加氢LCO与重油原料分层顺序进料催化裂化生产高辛烷值汽油馏分。LTAG技术对于炼油企业降低柴汽比、调整产品结构和提升产品质量提供了有力的支撑。该技术既解决了劣质LCO的出路问题,又弥补了市场短缺的高辛烷值汽油馏分或轻质芳烃的不足,具有显著的经济效益,在炼油企业得到广泛的应用。     

Application of “Micro-demolition Atomization” Theory in Feedstock Atomization for RFCCU

Abstract

Based on the “Micro-demolition Atomization” theory of emulsified heavy oil combustion, the heavy oil catalytic cracking feedstock was emulsified by compound nonionic surfactant. The water was dispersed uniformly into oil with drops about 1–5 µm, and could be formed stable water-in-oil emulsion with oil. After being in contact with high temperature regenerated catalyst, the emulsified feedstock was atomized demolishedly, which changed atomization mode and reduced the diameters of liquid drops to about 5 µm, enhanced the effect of catalytic cracking reaction, improved the selectivity of coke and increased the recovery of light oil. The pilotscale test result of catalytic cracking showed that, compared with unemulsified feedstock under the same conditions, the recovery of light oil was increased by 2–3%, the yield of coke was reduced by 0.5–1.0%, and the yield of dry gas was reduced by 0.5–1.5%,respectively. The application of the “Micro-demolition Atomization” theory in the feedstock atomization of the heavy oil catalytic cracking would change traditional atomization mode, and affect the catalytic cracking of the heavy oil significantly.     

Application of “Micro-demolition Atomization” Theory in Feedstock Atomization for RFCCU

Based on the “Micro-demolition Atomization” theory of emulsified heavy oil combustion, the heavy oil catalytic cracking feedstock was emulsified by compound nonionic surfactant. The water was dispersed uniformly into oil with drops about 1-5 µm, and could be formed stable water-in-oil emulsion with oil. After being in contact with high temperature regenerated catalyst, the emulsified feedstock was atomized demolishedly, which changed atomization mode and reduced the diameters of liquid drops to about 5 µm, enhanced the effect of catalytic cracking reaction, improved the selectivity of coke and increased the recovery of light oil. The pilotscale test result of catalytic cracking showed that, compared with unemulsified feedstock under the same conditions, the recovery of light oil was increased by 2-3%, the yield of coke was reduced by 0.5-1.0%, and the yield of dry gas was reduced by 0.5-1.5%,respectively. The application of the “Micro-demolition Atomization” theory in the feedstock atomization of the heavy oil catalytic cracking would change traditional atomization mode, and affect the catalytic cracking of the heavy oil significantly.     

FCC油浆中饱和烃的抽提方法研究

以糠醛为抽提溶剂、正辛烷为第二溶剂,采用双溶剂抽提法对中国石化九江分公司和广州分公司FCC油浆进行抽提分离,得到饱和烃和芳烃,考察双溶剂抽提的操作条件及抽余油（富含饱和烃）的组成和裂化性能。结果表明,最佳的抽提条件为：温度50～70 ℃;第一阶段剂油比m（糠醛）:m（油浆）:m（正辛烷）＝2.0:1.0:1.5,第二阶段剂油比m（糠醛）:m（抽余相）＝0.67:1.00,第三阶段剂油比m（糠醛）: m（抽余相）＝1.20:1.00;抽提次数8次,第四次和第五次抽提之间进行一次抽余相溶剂提浓。在该条件下,九江分公司和广州分公司FCC油浆抽提分离得到的抽余油中饱和烃质量分数分别为77%和74%,饱和烃收率分别为95.23%和91.58%,分离效果良好,且得到的抽余油具有良好的裂化性能,是优质的催化裂化原料。     

催化裂化过程芳烃转化及生焦关系探索

在小型固定流化床试验装置上考察了催化剂微反活性和剂/油质量比对加氢蜡油催化裂化反应中芳烃转化以及生焦量的影响。根据焦炭产率变化,按转化率将加氢蜡油催化裂化反应分为3个阶段,分别考察了各阶段中芳烃转化以及生焦之间的关系。定义了催化剂表观活性概念,并以此考察了汽油芳烃摩尔产率和焦炭产率与催化剂表观活性的关系。通过分析各馏分段中芳烃含量及生焦量随催化剂表观活性的变化得出,芳烃特别是多环芳烃对生焦反应至关重要。在剂/油质量比相同条件下,随着催化剂微反活性增加,汽油芳烃含量和焦炭产率增大;原料转化率相同条件下,随着催化剂表观活性增加,焦炭产率增大。     

用催化裂化重质芳烃制备多环芳烃树脂

以催化裂化回炼油中抽提出的重质芳烃为原料，在酸性催化剂作用下，与交联剂多聚甲醛反应制备多环芳烃树脂，对多环芳烃树脂进行了初步评价，结果表明：两种后处理工艺路线（溶剂沉降过滤法和减压蒸馏拔头法）得到的多环芳烃树脂平均相对分子质量较低，具有较好的热稳定性。与催化裂化重质芳烃原料相比，未反应芳烃油显示了较好的安定性，将多环芳烃树脂掺入聚氨酯系涂料中，试制的改性双组分聚氨酯系防腐涂料性能良好，具有一定的开发应用价值。     

脱沥青油及其糠醛抽余油的催化裂化性能研究

采用提升管催化裂化装置,考察脱沥青油（DAO）以及抽提条件分别为剂油质量比2:1、抽提温度80℃;剂油质量比2:1、抽提温度85℃两种工况下对DAO进行糠醛抽提所得到的抽余油A与B等三种催化裂化原料的裂化性能。实验结果表明：DAO经过糠醛抽提后所得抽余油的催化裂化转化率较高,轻质油收率较高,重油和焦炭产率较低,其催化裂化性能和裂化产品的性质均优于DAO。     

渣油接触裂化产物特征分子组成分析

以正构烷烃、萜烷生物标志物、多环芳烃和芳香噻吩系列作为特征化合物,采用GC-MS方法对渣油原料KWTVR、QLVR和THAR分别在3种接触剂A、B和C作用下的裂化产物进行分析。结果表明,9种产物中特征化合物分布差异明显,其分布受渣油原料和接触剂类型影响。3种渣油原料中QLVR的接触裂化改质效果最好,B剂最适合用作渣油预处理改质的接触剂。萜烷生物标志物的特殊分子结构对热作用和催化作用类型比较敏感,可指示反应的类型以及裂化反应的深度。对于同种渣油原料,产物中多环芳烃和噻吩系列的分布情况与接触裂化所使用的接触剂的活性强弱顺序有对应关系。由渣油接触裂化重馏分油产物中特征化合物的分布情况可推测渣油接触裂化反应路径。     

Commercial Application of RMC Technology in the 1.5 Mt／a Hydrocracking Unit at Shanghai Petrochemical Company

The RMC technology developed by RIPP has been applied in a 1.5Mt/a medium pressure hydrocracking unit at Shanghai Petrochemical Company. The unit was successfully put on stream in September 2002. Calibration of the performance of the commercial unit has shown that the RMC technology has higher hydrogenation activity and selectivity, and high quality product can be obtained under lower reaction temperature. The heavy naphtha with less than 0.5 ppm of sulfur and 58.5 m% potential aromatic content is a good feedstock for catalytic reforming unit. The diesel with less than 0.5 ppm of sulfur, 6.6 m% aromatics and cetane rating of 56 is a high-grade diesel fuel. The hydrocracked tail oil containing more than 14 m% hydrogen and mere 1.7m% aromatics could be used as a good feedstock for steam cracking process to produce ethylene.     

植物油催化裂解生成低碳烯烃和轻芳烃的研究

使用含择形分子筛的催化剂在固定流化床（FFB）装置上开展了对以棕榈油为代表的植物油及三种烃类原料的催化裂解试验研究,结合氢转移反应探讨了植物油催化裂解制取低碳烯烃和轻芳烃的优势。结果表明,植物油中的烃基部分具有很好的可裂化性,可生成与烃类原料相当的低碳烯烃及远高于烃类原料的轻芳烃,汽油重芳烃、柴油、重油等低价值、难利用产物的产率较低;植物油中的烃基部分极易发生芳构化,且容易进入择形分子筛孔道,选择性生成C6~C8的轻芳烃;植物油及脂肪酸催化裂解时通过氢转移反应以水的形式脱除了一部分氧,同时避免了烯烃被饱和,有利于兼顾低碳烯烃和轻芳烃的产率。     

糠醛抽出油、催化裂化重油研制橡胶用油

采用溶剂精制工艺处理糠醛抽出油、催化裂化重油（回炼油和油浆）,用以生产橡胶用油。通过实验证明,糠醛精制和KT液溶剂精制两种工艺均能生产橡胶用油,其副产物抽余油可作为催化裂化原料。同时对这两种工艺进行比较,结果表明,KT液溶剂精制工艺优于糠醛精制工艺。     

溶剂萃取法分离沙特中质原油VGO及其硫分布规律

以不同水含量的糠醛和N-甲基吡咯烷酮作萃取溶剂,沙中原油减压馏分油经3段萃取被分离为重芳烃相、中芳烃相、轻芳烃相和饱和烃相4个亚组分,采用气相色谱-质谱联用、傅里叶变换离子回旋共振质谱等方法分析了亚组分中烃类组成和硫化物的分布,考察了萃取分离过程各烃类的分离效率和芳烃萃取选择性。结果表明,3段萃取分离出的重芳烃相、中芳烃相和轻芳烃相中芳烃质量分数分别在89.6%~95.6%、80.8%~91.0%和63.9%~77.7%,表明糠醛和NMP是适于分离减压馏分油中芳烃的溶剂;芳烃环数增加,分子极性提高,溶剂对其溶解能力增强,极性较强的三环及以上芳烃主要存在于重芳烃相和中芳烃相;不同水含量的糠醛和NMP对芳烃,尤其是对三环及以上芳烃的分离效率高于饱和烃;水含量增加,溶剂的萃取分离效率降低,但对芳烃的萃取选择性β值提高;NMP对芳烃的萃取选择性高于糠醛。三环及以上噻吩类硫化物主要存在于重芳烃相和中芳烃相中,单、双环噻吩类硫化物基本均匀分布于各亚组分中。     

页岩油中碱性氮化物对催化裂化反应的阻滞作用及其结构表征

通过以不同浓度盐酸对页岩油中的碱性氮化物进行分离及定量添加碱氮模型化合物的方法,辅以高分辨质谱对不同样品中碱性氮化物的结构进行表征,研究了页岩油中碱性氮化物对其裂化反应的阻滞作用。结果表明：页岩油中碱性氮化物主要为带烷基侧链的吡啶、环烷基吡啶,而且盐酸浓度越高,所富集出的碱性氮化物类型越多;碱性氮化物的去除有利于页岩油催化裂化反应的发生,且除含量外,碱性氮化物的结构对页岩油裂化过程也存在较大的影响,相对分子质量越大、缩合程度越高的碱性氮化物越不利于页岩油催化裂化反应的进行。     

加氢轻循环油裂化反应规律研究

以加氢轻循环油（LCO）为原料,采用含Y型分子筛、活性中孔材料以及含β或MFI结构分子筛的不同类型催化剂在小型固定流化床ACE Model Rt装置上进行裂化反应实验,考察不同类型催化剂对加氢LCO中各组分的转化能力,并考察反应条件对加氢LCO裂化反应的影响。结果表明：采用含高活性Y型分子筛的催化剂能够得到较高的汽油收率及C6～C9芳烃收率,有利于提高汽油辛烷值或者获得较多的苯、甲苯、二甲苯等化工产品,但反应过程同时会生成双环及多环芳烃,抵消了部分加氢前处理的效果;反应温度和剂油比对加氢LCO裂化转化率影响较小;汽油收率随反应温度的提高而降低,剂油比对汽油收率的影响较小;提高反应温度会促进重质产物的生成,而提高剂油比则会抑制重质产物的生成;反应温度和剂油比的提高均有利于增加汽油中芳烃含量。     

减压渣油及其四组分在接触剂上的裂化反应规律

以减压渣油为原料,采用热解色谱和热重-质谱,考察了减压渣油及其四组分(饱和分、芳香分、胶质和沥青质)在惰性接触剂LHBK和酸性接触剂C上的裂化反应。结果表明：四组分在有孔无酸剂LHBK上裂化程度由强到弱的顺序为胶质、沥青质、芳香分、饱和分,在有孔有酸剂C上裂化程度由强到弱的顺序为饱和分、芳香分、胶质≈沥青质。四组分在2种接触剂上缩合反应生成的积炭均比减压渣油在接触剂上缩合反应生成的积炭具有更低的H/C摩尔比;接触剂的酸性明显促进了四组分的裂化,C_20-馏分产率明显增加;且增加了减压渣油裂化反应的生焦率,增加部分主要来自芳香分和胶质的催化裂化生焦。说明接触剂的酸性能促进饱和分C—C键、芳香分侧链C—C键断裂以及胶质和沥青质中键能较低的键断裂。     

河南油田超稠油复合催化降粘体系效果评价

河南油田创新地进行了稠油热采地下复合催化降粘技术研究。本实验考察了无水体系、含水体系、水热催化裂解体系、乳化降粘体系、乳化水热催化裂解复合体系（即复合催化降粘体系）对特超稠油作用后物理化学性质的变化以及对特超稠油的降粘效果,探讨了乳化水热催化裂解降粘的作用机理。结果表明,在催化剂作用下,特超稠油中重质组分发生部分裂解,原油物化性能得到明显改善,乳化水热催化裂解复合体系对河南油田超稠油的降粘率达98.7%。     

废橡胶粉/SBS复合改性沥青制备研究

以SK AH-70为基质沥青,外掺废胶粉和SBS,采用高速剪切法制备复合改性沥青。通过正交实验考察了沥胶比、糠醛抽出油掺量和稳定剂掺量对沥青性能的影响,确定最优条件为:沥胶比为3,糠醛抽出油加入量4%,稳定剂加入量3‰。在最优条件下制备的复合改性沥青软化点为61.0℃,5℃延度为30.0 cm,弹性恢复为85%。废胶粉/SBS复合改性沥青的性能明显优于胶粉改性沥青,而稍低于SBS改性沥青,但是其成本低廉、易于施工,并且性能达到SBS改性沥青的相关要求,具有良好的应用前景。