原料中柴油组分对催化裂化装置产品分布的影响

为探索催化裂化柴油的深加工途径,中国石化洛阳分公司将催化裂化柴油回炼蜡油加氢装置,导致蜡油加氢装置的精制蜡油中柴油组分上升,进而提高了催化裂化装置原料中柴油组分含量。通过对比催柴进蜡油加氢装置回炼前后催化裂化装置产品分布的变化情况,说明原料中柴油组分上升不利于提高催化裂化装置的产品转化率。     

荆门催化装置加工未加氢焦化蜡油工业运行

中国石化荆门分公司在焦化蜡油加氢精制装置停工期间制定并实施了未加氢焦化蜡油催化裂化加工方案:1号催化装置集中加工焦化蜡油;在此期间催化裂化油浆不作为焦化原料;应用高活性抗碱氮重油催化裂化催化剂;催化裂化装置实施大剂油比、高反应温度操作。运行数据显示:加工未加氢焦化蜡油期间,1号催化裂化装置掺渣率及产品收率等情况较为理想,此工业运行为催化装置加工未加氢焦化蜡油开辟了可行的工艺途径,取得了具有工业应用价值的技术进展。     

掺炼催化循环油的沸腾床与催化裂化组合技术开发

选择劣质渣油和催化裂化循环油作为原料,分别进行掺炼不同比例催化裂化循环油的渣油沸腾床加氢和加氢常渣催化裂化试验,并对组合工艺进行总流程比较。结果表明,液化气、汽油和柴油等高价值产品收率至少提高1.04%,焦炭等低价值产品的产量降低,效益大幅度提升。研究结果证明了循环油掺炼到沸腾床渣油加氢与催化裂化组合工艺技术的可行性,优化了沸腾床加氢与催化裂化的操作。     

重芳烃加氢转化生产轻芳烃技术的研究进展

阐述了国内外催化裂化柴油中重芳烃加氢转化生产轻芳烃技术的研究进展。通过介绍国外UOP公司开发的LCO Unicracking TM技术,LCO-XTM工艺技术,以及国内中国石化抚顺石油化工研究院(FRIPP)开发的FD2G技术,结合多环芳烃加氢精制及加氢裂化的反应过程,系统地阐述了催化裂化柴油中重芳烃加氢转化生产轻芳烃技术的主要内容。同时,对于该技术所选用的原料、技术路线及产品也进行了介绍。     

加氢裂化装置掺炼催化重柴油可行性分析

A公司1.2万t/a加氢裂化装置自首次开车以来平稳安全运行至今。为提高经济效益、合理利用石油资源,在加氢裂化装置原料中掺炼催化重柴油。针对掺炼催化裂化重柴油对加氢裂化装置的影响深入分析,对反应系统的调整、产品质量及产品分布进行了分析,对系统压降影响和混入高干点原料的问题提出了解决措施及建议。     

蜡油加氢裂化装置掺炼柴油技术应用

利用蜡油加氢裂化装置富裕生产能力掺炼减一线柴油及加氢焦化柴油,在掺炼过程中蜡油加氢裂化装置运行平稳。通过试验,蜡油加氢裂化装置对裂化减一线柴油及加氢焦化柴油效果明显,特别是加氢焦化柴油的转化率达91.38%。通过裂化柴油,提高了液化气、石脑油和航煤产品的产量,降低了柴汽比。通过测算,掺炼加氢焦化柴油效益达303.9元/吨,有效增加了炼厂的经营效益,提高了市场竞争力。     

未加氢焦化蜡油直接催化加工的技术改造

2011年9～10月,中国石化荆门分公司焦化蜡油加氢装置停工大修,为了解决焦化蜡油出路问题,在1#催化装置进行了未加氢焦化蜡油催化裂化的工业运行,运行方案为:①将装置催化剂更换为高活性抗碱性氮重油催化剂;②高反应温度,零回炼比操作方案;③提升管底部注入重整拔头油提高剂油比和裂化深度。运行期间,1#催化掺渣率及产品分布和收率等操作工况较为理想,该工业运行为催化裂化装置直接加工焦化蜡油开辟了一种新的可行的工艺途径,取得了具有工业应用价值的技术进展。     

蜡油加氢和催化裂化组合工艺的应用

广州石化210×10^4t／a蜡油加氢装置是广石化加工中东含硫原油及生产清洁燃料配套改造工程之一,该装置采用劣质蜡油加氢处理部分转化技术,对VGO、CGO、DAO进行加氢处理,从而为催化裂化装置提供优质蜡油原料。蜡油加氢和催化裂化组合工艺,为广州分公司提高含硫原油的综合加工能力,改善产品分布,降低运行成本,提高经济效益起到了重要的作用。本文着重对加氢处理装置的投产和组合工艺的运行效果进行分析。     

FF-24催化剂在镇海炼化蜡油加氢装置的工业应用

中国石化镇海炼化分公司为了提高180万t/a蜡油加氢装置运行效果(尤其是提高加氢脱氮率),于2012年换用抚顺石油化工研究院最新开发的蜡油加氢处理专用催化剂(FF-24)。要介绍了FF-24催化剂在中国石化镇海分公司180万t/a蜡油加氢装置的工业应用情况。工业应用结果表明:FF-24催化剂生产方案灵活,活性稳定性好,能满足生产优质低硫催化裂化原料及精制柴油的需要。     

我国焦化蜡油的加工技术及其进展

我国焦化蜡油与直馏蜡油相比含有较多的氮、绸环芳烃、胶质等组分，然而作为催化裂化(或加氢裂化)的掺兑原料，高含量的氮、稠环芳烃、胶质会使催化裂化(或加氢裂化)的轻质油收率降低、生焦率增大、装置的处理能力下降，尤其碱性氮化物会导致裂化催化剂中毒失活，是装置总转化率下降、汽油产率降低的重要原因^[1,2]。针对焦化蜡油的特点，目前我国在加工中所采取的措施有以下几种：优化催化裂化操作条件并采用高效抗氮催化剂来提高焦化蜡油的掺炼比；采用分段进料的吸附转化工艺(简称DNCC工艺)；以及焦化蜡油的加氢处理和溶剂精制等。几种方法均能在一定程度上加大焦化蜡油的掺炼比，改善裂化后的产品分布和产品质量，但与实际需要仍存在差距，需进一步改善与发展。     

降低柴汽比的催化柴油LTAG技术应用实践

LTAG技术的应用一方面催化柴油可以通过加氢后去催化裂化装置回炼,将催化柴油转化为汽油及液化气组分,减少了企业低十六烷值柴油组分,同时降低柴汽比;另一方面可大幅提高催化汽油辛烷值,同时降低烯烃含量,满足汽油质量升级的要求。本文以C企业采用催化柴油LTAG技术的应用实践为例,分析了该技术对企业结构调整的影响。     

催化裂化装置回炼加氢石脑油对产品的影响

加氢石脑油作为催化裂化装置急冷油进入提升管进行回炼,对回炼加氢石脑油期间产品分布和产品性质有较为明显的影响。干气、液化气和柴油收率明显下降,汽油收率明显升高,汽油辛烷值和芳烃含量也呈下降趋势,稳定汽油有效烯烃含量明显降低,对醚化反应操作有较大的影响。通过分析催化裂化装置回炼加氢石脑油对产品分布和产品性质的影响,为未来生产调整提供数据参考。     

Preparation of bio-fuels by catalytic cracking reaction of vegetable oil sludge

Biofuel production from vegetable oil is potentially a good alternative to conventional fossil derived fuels. Moreover, liquid biofuel offers many environmental benefits since it is free from nitrogen and sulfur compounds. Biofuel can be obtained from biomass (e.g. pyrolysis, gasification) and agricultural sources such as vegetable oil, vegetable oil sludge, rubber seed oil, and soybean oil. One of the most promising sources of biofuel is vegetable oil sludge. This waste is a major byproduct of vegetable oil factories. It consists of triglycerides (61%), free fatty acid (37%) and impurities (2%). The hydrocarbon chains of triglycerides and free fatty acid are mainly made up of C₁₆ (30%) and C₁₈ (36%) hydrocarbons. The others consist of C₁₂-C₁₇ hydrocarbon chains. Transesterification can help in converting vegetable oil sludge into biofuel. The disadvantage of this method is that a large amount of methanol is required. The alternative method for this conversion is catalytic cracking. The objective of this research is to evaluate and compare the pyrolysis process with cracking catalytic reaction of vegetable oil sludge by Micro-activity test MAT 5000 of Zeton-Canada.A ZSM-5/MCM-41 multiporous composite (MC-ZSM-5/MCM-41), was successfully synthesized using silica source extracted from rice husk. The material has the MCM-41 mesoporous structure, and its wall is constructed by ZSM-5 nanozeolite crystals. The porous system of the material includes pores of the following sizes: 5 Å (ZSM-5 zeolite), 40 Å (MCM-41 mesoporous material), and another porous system whose diameter is in the range of 100-500 Å (mesoporous system) formed by the burning of organic compounds that remain in the material during the calcination process. This pore system contributes to an increase in the catalytic performance of synthesized material.The results of vegetable oil sludge cracking reaction show that the product consists of fractions such as dry gas, liquefied petroleum gas (LPG), gasoline, light cycle oil (LCO), and (heavy cycle oil) HCO, which are similar to those of petroleum cracking process.MC-ZSM-5/MCM-41 catalyst is efficient in the catalytic cracking reaction of vegetable oil sludge as it has higher conversion and selectivity for LPG and gasoline products in comparison to the pyrolysis process. Product distribution (% of oil feed) of cracking reaction over MC-ZSM-5/MCM-41 is coke (3.4), total dry gas (7.0), LPG (31.1), gasoline (42.4), LCO (8.9), HCO (7.2); and that of pyrolysis are coke (19.0), total dry gas (9.3), LPG (16.9), gasoline (28.8), LCO (13.7), and HCO (12.3).These results have indicated a new way to use agricultural waste such as rice husk for the production of promising catalysts and the processing of vegetable oil sludge to obtain biofuel.     

FD2G加氢转化技术研发及应用

目前我国炼油市场柴汽比下降、环保法规日趋严格,催化柴油(LCO)油品价值降低,炼油企业急需调整产品结构,为其寻找新的出路。而国内面临着高辛烷值汽油短缺的情况,因此将催化柴油转化为高辛烷值汽油是一条降低柴汽比、增产汽油的有效途径。结合催化柴油的性质从反应机理、试验数据及工业应用等方面介绍了FD2G加氢转化技术。结果表明:FD2G加氢转化技术可将催化柴油加氢转化为高辛烷值汽油和清洁柴油调和组分,同时可生产轻质芳烃原料等高附加值产品。     

重质原料油生产轻烯烃的Ⅱ型催化裂解工艺和催化剂

Ⅱ型催化裂解是以重质油为原料生产丙烯、异丁烯和异戊烯等轻烯烃, 并同时兼产高辛烷值优质汽油的新催化工艺。该工艺使用新研制的新型择形催化剂, 可以加工减压馏分油、减压馏分油掺渣油或二次加工油以及全常压渣油, 并成功地进行了工业化试验。以临胜减压馏分油掺左右脱沥青油为原料, 可以得到12.52wt%~14.43wt%的丙烯和11.23wt%~11.41wt%的丁烯,同时还得到40wt%左右93号优质汽油。型催化裂解工艺开创了一条以重质油为原料生产轻烯烃和高辛烷值优质汽油的新途径     

动植物油生产清洁燃料和低碳烯烃的替代加工工艺

Since the production cost of biodiesel is now the main hurdle limiting their applicability in some areas, catalytic cracking reactions represent an alternative route to utilization of vegetable oils and animal fats. Hence, catalytic transformation of oils and fats was carried out in a laboratory-scale two-stage riser fluid catalytic cracking （TSRFCC） unit in this work. The results show that oils and fats can be used as FCC feed singly or co-feeding with vacuum gas oil （VGO）, which can give high yield （by mass）of liquefied petroleum gas （LPG）, C2-C4 oletms, tor example 45% LPG, 47% C2-C4 olefins, and 77.6% total liquid yield produced with palm oil cracking. Co-feeding with VGO gives a high yield of LPG （39.1%） and propylene （18.1%）. And oxygen element content is very low （about 0.5%） in liquid products, hence, oxygen is removed in the form of H2O, CO and CO2. At the same time, high concentration of aromatics （C7-C9 aromatics predominantly） in the gasoline fraction is obtained after TSRFCC reaction of palm oil, as a result of large amount of hydrogen-transfer, cyclization and aromatization reactions, Additionally, most of properties of produced gasoline and diesel oil fuel meet the requirements of national standards, containing little sulfur. So TSRFCC technology is thought to be an alternative processing technology leading to production of clean fuels and light olefins.     

Biofuel potential production from cottonseed oil: A comparison of non-catalytic and catalytic pyrolysis on fixed-fluidized bed reactor

Conversion of vegetable oils predominantly composed of triglycerides using pyrolysis type reactions represents a promising option for the production of renewable fuels and chemicals. The purpose of this article was to compare catalytic cracking with thermal cracking on production of gaseous hydrocarbon and gasoline conversion by cottonseed oil, and to discuss the difference on composition of products from catalytic cracking and thermal cracking. Reaction products are heavily dependant on the catalyst type (catalyst activation) and reaction conditions. They can range from dry gas to light distillate, such as dry gas, liquefied petroleum gas and gasoline. When the temperature of catalytic cracking is over 460 °C, the effects of thermal cracking must be considerable.     

多产异构烷烃催化裂化工艺影响因素分析

介绍了多产异构烷烃（MIP）催化裂化工艺在中石化安庆分公司120万t·a-1催化裂化装置上的工业应用情况,从工艺条件方面分析了该技术的主要影响因素。结果表明：反应温度、催化剂类型、原料油性质、第二反应区催化剂藏量等是影响MIP催化裂化技术的主要因素;第一反应区反应温度控制在515～520℃为宜;第二反应区急冷油注入量不宜大于10t·h-1;第二反应区催化剂藏量控制在4～5t为宜;焦化蜡油及石蜡基直馏蜡油先经抽提后再用作原料,可降低汽油的烯烃含量;使用MIP专用剂能更好地发挥MIP技术的功效。     

催化裂化组合式工艺探索性研究

介绍了一种将重油催化裂化和轻质油改质相结合的组合催化反应工艺，采用两段反应，将重油裂化和轻质油的改质在不同的反应器中进行，使轻质油在低温、长反应时间下反应，在不降低汽油辛烷值的同时可降低轻质油中的烯烃和硫含量。而重质原料在高温、大剂油比等较苛刻的条件下进行反应，在加强重油裂化深度的同时改进轻质油的品质。     

降低油浆和焦炭的裂化催化剂RSC-2006的工业应用

催化裂化催化剂RSC-2006采用焦炭选择性较好的大孔富硅基质以降低焦炭收率;添加活性基质组分以增强催化剂的重油裂化能力,同时调节基质的表面酸性,在保证重油预裂化能力的同时改善焦炭选择性;对分子筛进行物化处理,清理和疏通分子筛的孔道,改善分子筛对劣质重油催化裂化的可接近性;引入抗金属污染组分,提高催化剂的抗金属污染能力。工业应用结果表明,催化剂具有优异的重油转化能力和优良的焦炭选择性。与对比催化剂相比,油浆和焦炭收率降低,大幅增加高价值产品收率,液化气+汽油+柴油收率提高。