重油生产丙烯的DCC工艺及催化剂进展

In the past several decades,SINOPEC has devoted continuously great efforts to the development of DCC technology,the only commercial process using heavy feeds aiming at propylene production.Recently,a series of research breakthroughs have been achieved in molecular refining.Based on the detailed analysis on the complex DCC reaction network,an innovative catalyst technology has been developed to Optimize Catalysis Kinetics (OCK in brief).The deep-cracking process can be improved with optimizing the availability of the active sites.The updated MFI and beta zeolites are used to boost the propylene selectivity.The latest generation catalyst DMMC-1 has been applied commercially.Compared with the best historical records in the past,the propylene yield upon application of the catalyst DMMC-1 increases by 2.4 m% coupled with an improved distribution of products.The DCC technology continues to assume a leading position for manufacturing propylene from heavy feedstocks.     

新型重油催化裂化催化剂HSC-1的研究开发

以高活性高稳定性的高稀土含量超稳改性分子筛为活性组元开发了新型重油催化裂化催化剂HSC-1,并利用XRF、BET、孔体积、磨损指数、粒度测定等对其化学组成及物化性能进行了分析,利用轻油微反及ACE对催化裂化性能进行了考察。结果表明,制备的催化剂HSC-1具有物化性能好、重油裂化能力及抗金属污染能力强、产物分布好、焦炭选择性及汽油选择性好,以及优异的降低汽油烯烃含量的特性。     

催化裂化烟机结垢成因分析及对策

Causes of scale deposition in flue gas turbine expander of FCCU were analyzed based on some aspects,including the types and operating conditions of flue gas turbines,properties and composition of feedstocks and catalysts,and operating conditions of the reactor and regenerator.Some countermeasures were proposed for preventing scale deposition in flue gas turbine of FCCU.     

系列新型重油催化裂化催化剂的工业开发与应用

采用特定方法对催化剂载体和活性分子筛进行改性，制得了一系列性能良好的载体和改性分子筛，并将其应用于重油催化剂上，针对不同炼油厂原料油的实际情况及市场的需求，研制开发出了系列重油催化裂化催化剂，改变了催化剂的活性，选择性，稳定性，并在工业装置上运转，取得了较好的效果。     

环烷烃混合烯烃催化裂化: 1. 单事件动力学模型 (SEMK)建立

Single-event microkinetic(SEMK) model of the catalytic cracking of methylcyclohexane admixed with 1-octene over REUSY zeolites at 693 K—753 K in the absence of coke formation is enhanced. To keep consistency with the wellknown carbenium ion chemistry, hydride transfer forming and consuming allylic carbenium ions in the aromatization of cycloparaffins are further investigated and differentiated. The reversibility of endocyclic β-scission and cyclization reactions is refined by accounting explicitly for the reacting olefins and resulting cycloparaffins in the corresponding thermodynamics. 24 activation energies for the reactions involved in the cracking of cycloparaffins are obtained by the regression of 15 sets of experimental data upon taking the resulting 37 main cracking products, i. e., responses into account. The enhanced SEMK model can adequately describe the catalytic behavior of 37 main products with conversion and temperature.     

金属氧化物对ZSM-5分子筛催化裂化性能的影响

Effects of metal oxide in ZSM-5 zeolite on its catalytic performance in fluid catalytic cracking reaction were studied via characterization by XRD and FT-IR spectroscopy using pyridine and collidine as molecular probes,and the modified ZSM-5 zeolite was evaluated in a micro reactor using standard light diesel fraction as the feedstock.Test results indicate that the metal species introduced into the ZSM-5 zeolite had led to the formation of Lewis acid centers.When the modified ZSM-5 zeolite with the metal species on its surface was used as the catalyst in FCC reaction,both the propylene yield and the propylene concentration in the liquefied petroleum gas increased,but in the meantime,more hydrogen and coke were formed at high conversion rate under the joint action of nonselective cracking of Lewis acid centers and dehydrogenation at metal centers on its outside surface.     

新型重油催化裂化催化剂HSC的工业应用

介绍了新型重油催化裂化催化剂HSC在A炼厂140万吨/年重油催化装置上的工业标定试验及工业应用情况。工业标定试验结果表明: 与基础剂相比,干气产率和油浆产率下降, 总液收增加了1.34个百分点,汽油产率增加了5.05个百分点,液化气产率增加了1.43个百分点。产品性质没有明显变化,催化剂抗磨损强度较高。通过中间标定、总结标定及后续的长期工业应用日常统计数据结果表明催化剂HSC具有较强的重油转化能力、较高的汽油产率、较好的产物分布和产品选择性。     

浸渍法制备Al-SBA-15分子筛的稳定性和催化性能研究

The mesoporous Al-SBA-15 zeolite was obtained via impregnation of pure silica-based SBA-15 zeolite with aluminum nitrate.The Al-SBA-15 sample was calcined in air at 800 ℃ for 6 h and hydrothermally treated at near 100 ℃ for 120 h,respectively,and then the thermal and hydrothermal stability of Al-SBA-15 sample was investigated by X-ray diffractometry (XRD),scanning electron microscopy (SEM),transmission electron microscopy (TEM) and nitrogen adsorption and desorption techniques.The Al-SBA-15 sample was also studied by 27 Al nuclear magnetic resonance (27 Al NMR) and ammonia temperature programmed desorption (NH 3-TPD) techniques.In addition,the catalytic activity of Al-SBA-15 zeolite was investigated by the Friedel-Crafts reactions of 2,4-di-tert-butylphenol with cinnamyl alcohol.The test results showed that the thermal and hydrothermal stability of Al-SBA-15 zeolite was better than that of SBA-15 zeo-lite.The Al-SBA-15 zeolite sample prepared by impregnation method exhibits more framework aluminum species and Al-O-Si units.Therefore,the number of the surface hydroxyl groups was reduced,resulting in the stabilization of framework structure ofAl-SBA-15 zeolite.The aluminum species can form weak and medium-strong acid sites with catalytic activity.     

重油催化裂化催化剂RCH的开发与工业应用

RCH催化剂是继我国第一代超稳Y型催化裂化催化剂之后，开发研制的新型渣油裂化催化剂。该剂沸石含量低，而在裂化性能、产品收率、焦炭选择性等方面均与国内外同类型催化剂相当，可替代进口催化剂在重油催化裂化（RFCC）装置上使用；该剂更具有平衡活性和轻质油收率高、稳定性好、裂化重质油能力和抗重金属污染能力强等特点，同时制备工艺先进，流程简单，属国际先进水平。     

重油催化裂化新型进料喷嘴的开发应用

催化裂化进料喷嘴对重油加工尤为重要。LPC—2型喷嘴是为重油加工,特别是为劣质渣油加工开发的新型进料喷嘴。其外型结构与LPC—1型相同,故可兼容。但预混合室、混合室和喷头的内部结构作了不少改进。与LPC—1型相比,在原料油性质、操作条件、催化剂性质大体相同的情况下,生焦率降低、轻油收率提高、产品分布改善、用汽量小,提高了经济效益。喷嘴属低压降喷嘴,有较大操作弹性。文中提出了喷嘴安装和操作的技术要求。     

乳化重油催化裂化反应的研究

用乳化重油和纯重油为原料进行催化裂化反应,在相同操作条件下,分别研究了它们对裂化产品分布、生焦量、产品质量、裂化催化剂性能等主要指标的影响。结果表明,乳化油比纯重油液体产率提高2．91％、液化气增加1．33％、生焦量下降2．32％、干气量稍低;乳化油汽油辛烷值为93．4,而纯重油汽油辛烷值93．0;两者对裂化催化剂性能的影响相当。     

FCC复活催化剂在重油催化裂化装置的工业应用

石油资源的重质化和劣质化,导致催化裂化(FCC)催化剂重金属污染问题日益突出。国内的FCC催化剂因失活多为一次性使用,需定期卸出废催化剂(即平衡催化剂)。大庆石化公司二套重油催化裂化装置试用某公司生产的FCC复活催化剂,应用结果表明,该复活催化剂可以部分替代新鲜催化剂进入装置使用,每年减少固体废弃物排放139.5 t,节约新鲜催化剂成本36.3万元,提高了行业整体经济效益。     

重油分级催化裂化反应性能

 利用小型固定流化床实验装置,对重油中不同馏程范围馏分裂化性能进行研究,发现重油中存在反应性能差异明显的两类馏分,且在减压渣油中仍含有部分优质馏分,依此采用分级方法将重油分为优质、劣质裂化原料。实验对比了各分级点分级后重油的催化裂化产物分布,也对比了重油分级前后催化裂化反应产物分布的变化。结果表明,适当提高分级点温度,将减压渣油中的一部分馏分切入优质原料,通过分别裂化可以改善重油整体的产物分布,并确定了长庆、济南重油适宜的分级点分别在500~540℃和500~520℃范围。分级后针对不同性质原料匹配各自的反应区间,重油整体的轻质油收率提高,焦炭和干气的收率降低;且随着催化裂化原料掺炼渣油比例的增加,采用重油分级催化裂化提高目的产物的优势越明显。     

乳化管输重油催化裂化试验研究

对利用乳化重油作为催化裂化原料进行了探讨 ,认为重油经乳化后减小了原料雾化后油滴直径 ,改善了催化剂与原料的接触环境和产品分布 ,在乳化剂用量 3 0 0 0 μg/g,掺水量 4%左右时 ,可以提高轻油收率 1 .80个百分点 ,干气和焦炭产率分别下降 0 .3 3和 0 .3 5个百分点 ,产品性质基本不变     

重油催化裂化装置进料系统改造

为了适应加工常渣的需要 ,胜利石油化工总厂 60× 1 0 4t/a重油催化裂化装置 (RFCCU) ,对进料系统进行改造 ,采用UPC鼓泡型喷嘴和分段进料 ,改善了原料油的雾化效果 ,降低蒸汽的用量 ,改善了产品分布 ,提高汽油产率 3 .2 3 %、轻油收率 0 .63 % ,提高经济效益 1 92 9.2万元 /a。     

气相高硅Y型分子筛催化剂在重油催化裂化装置上的工业应用试验

锦西石化分公司重油催化裂化装置采用了北京石科院研制、兰州石化分公司催化剂厂生产的气相高硅Y型分子筛催化剂LHA-28，工业应用结果表明，LHA-28催化剂提高了重油转化能力，液体收率高于对比剂，汽油的辛烷值、柴油的十六烷值与对比剂相比基本相当，是一种性能优良的催化剂。     

微波消解原子吸收法测定催化裂化催化剂中的重金属含量

用微波消解法，将样品在密闭容器内消解，测定催化剂中重金属的含量。经过样品测定与敞口消解法对照，结果一致。该方法具有样品损失少，结果可靠的优点。     

化学生热催化裂解体系对稠油降黏实验研究

为了更好地提高稠油油藏开发效果,采取化学生热与催化裂解方式来降低稠油黏度、提高地下稠油的流动能力非常必要。选择NaNO₂和NH₄Cl溶液作为化学生热剂,通过正交实验优选出生热剂最佳反应条件为:4 mol/L NaNO₂,4mol/L NH₄Cl,体系pH值为2。该条件下,反应温度和压力在短时间内迅速上升,分别达到峰值204℃和13.6 MPa,达到峰值的时间为6 min,反应基液温度升高149℃。油酸镍催化降黏体系最佳配方为:以反应原油的质量为基准,羧酸盐型油酸镍催化剂0.3%,供氢剂甲酸7%,助剂尿素7%,乳化剂十二烷基苯磺酸钠0.13%。该催化体系的最佳反应温度为280℃。油酸镍催化后,原油黏度由213.8 mPa·s降至74.2 mPa·s,降黏率为65.3%。当化学生热剂与催化裂解剂共同作用时,降黏率可达66.5%,饱和烃和芳烃含量增加,胶质和沥青质含量减小,催化降解效果较好。