CN101045884A - Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil - Google Patents

Abstract

Translated fromChinese

一种由渣油和重馏分油生产清洁柴油和低碳烯烃的方法，渣油与任选的催化裂解油浆进入溶剂脱沥青单元，所得的脱沥青油与任选的重馏分油进入加氢单元，在氢气的存在下进行加氢裂化反应，分离反应产物得到轻、重石脑油馏分、柴油馏分和加氢尾油；加氢尾油进入催化裂解单元，进行催化裂解反应，分离产物得到低碳烯烃、汽油馏分、柴油馏分和油浆，全部的催化裂解柴油馏分循环回催化裂解反应器，全部或部分的催化裂解油浆返回溶剂脱沥青单元。采用本发明提供的方法能由渣油和重馏分油最大量地生产丙烯、乙烯等低碳烯烃和低硫、低芳烃、高十六烷值的清洁柴油，其中丙烯收率大于27重％，而柴油能达到欧IV排放标准。

A method for producing clean diesel oil and light olefins from residual oil and heavy distillate oil, the residual oil and optional catalytic cracking oil slurry enters a solvent deasphalting unit, and the obtained deasphalted oil and optional heavy distillate oil enter hydrogenation Unit, in the presence of hydrogen, the hydrocracking reaction is carried out, and the reaction products are separated to obtain light and heavy naphtha fractions, diesel fractions and hydrogenated tail oil; the hydrogenated tail oil enters the catalytic cracking unit for catalytic cracking reaction, and the separated products are obtained low Carbon olefins, gasoline fraction, diesel fraction and oil slurry, all the catalytic cracking diesel fraction is recycled to the catalytic cracking reactor, and all or part of the catalytic cracking oil slurry is returned to the solvent deasphalting unit. Adopt the method provided by the present invention to produce low-carbon olefins such as propylene and ethylene and clean diesel oil with low sulfur, low aromatics and high cetane number from residual oil and heavy distillate oil in a large amount, wherein the propylene yield is greater than 27% by weight, Diesel can meet Euro IV emission standards.

Description

Translated fromChinese

一种由渣油和重馏分油生产清洁柴油和低碳烯烃的方法A method for producing clean diesel oil and low-carbon olefins from residual oil and heavy distillate oil

                         技术领域Technical field

本发明属于一个加氢处理工艺过程、一个不存在氢的情况下催化裂化步骤和一个在不存在氢的情况下精制过程处理烃油的多步工艺过程，更具体地说，是一种将渣油溶剂脱沥青、重馏分油加氢裂化以及加氢尾油催化裂解三种工艺过程有机结合生产清洁柴油和低碳烯烃的方法。The invention pertains to a multi-step process for treating hydrocarbon oils with a hydrotreating process, a catalytic cracking step in the absence of hydrogen and a refining process in the absence of hydrogen, and more particularly to a process for treating slag A method of organically combining three processes of oil solvent deasphalting, heavy distillate oil hydrocracking and hydrotreating tail oil catalytic cracking to produce clean diesel oil and low-carbon olefins.

                         背景技术 Background technique

我国国民经济有望保持二十年以上的快速增长，统计数据显示，若GDP增长1％，则油品需求增长0.5％，石化产品需求增长1％。可见，未来的油品和石化产品需求均将持续快速增长，其中石化产品需求增长的速度远高于油品。有限的原油资源与如何最大量地获得生产石化产品的基础原料(如乙烯和芳烃等)之间，将成为未来一段时间石化行业必须面对的一个突出矛盾。my country's national economy is expected to maintain rapid growth for more than 20 years. Statistics show that if GDP increases by 1%, the demand for oil products will increase by 0.5%, and the demand for petrochemical products will increase by 1%. It can be seen that the demand for oil products and petrochemical products will continue to grow rapidly in the future, and the growth rate of demand for petrochemical products is much higher than that of oil products. The limited crude oil resources and how to obtain the most basic raw materials for the production of petrochemical products (such as ethylene and aromatics) will become a prominent contradiction that the petrochemical industry must face in the future.

未来中国炼油工业发展将与乙烯、纤维原料工业发展紧密结合，着力实现炼油化工一体化，提高石化工业的整体竞争力。化工轻油是油化结合的关键之一，目前国内消费的化工轻油中，约78％用于生产乙烯，约17％用于生产对二甲苯。根据我国全面建设小康社会的经济指标，化工产品的人均占有量将会有很大的增长，这直接关系到化工原料的需求量。预计2007年中国乙烯能力将达到1100万吨左右，跃居世界第2位；2010年和2020年全国乙烯能力将分别达到1400万吨和2200-2400万吨。此外，预计2010对苯二甲酸(PTA)能力将达到766万吨。预计2010国内化工轻油需求量约为约5300万吨，2020年约8400-9000万吨。化工轻油需求量出现较大的增长后，依靠国内炼油厂增加原油加工量的方式难以满足其需求。In the future, the development of China's oil refining industry will be closely integrated with the development of ethylene and fiber raw material industries, and efforts will be made to realize the integration of oil refining and chemical industries and improve the overall competitiveness of the petrochemical industry. Chemical light oil is one of the keys to the combination of oil and gas. About 78% of the domestic consumption of chemical light oil is used for the production of ethylene, and about 17% is used for the production of p-xylene. According to the economic indicators of building a well-off society in an all-round way in my country, the per capita share of chemical products will increase greatly, which is directly related to the demand for chemical raw materials. It is estimated that China's ethylene capacity will reach about 11 million tons in 2007, ranking second in the world; in 2010 and 2020, the national ethylene capacity will reach 14 million tons and 22-24 million tons respectively. In addition, it is estimated that the capacity of terephthalic acid (PTA) in 2010 will reach 7.66 million tons. It is estimated that the domestic demand for chemical light oil will be about 53 million tons in 2010, and about 84-90 million tons in 2020. After a large increase in demand for chemical light oil, it is difficult to meet its demand by relying on domestic refineries to increase crude oil processing capacity.

与此同时，中东大规模以乙烷为原料的乙烯裂解装置投入运行，其乙烯产率高、生产成本很低，对于我国乙烯生产有很大的冲击；但该类装置基本不产丙烯，致使乙烯和丙烯供应出现不平衡的局面。因此，从重质原料通过炼油装置生产低碳烯烃、芳烃等化工原料，是解决化工轻油不足的必由之路。At the same time, a large-scale ethylene cracking unit using ethane as raw material in the Middle East has been put into operation. Its ethylene yield is high and the production cost is very low, which has a great impact on my country's ethylene production; The supply of ethylene and propylene is unbalanced. Therefore, the production of light olefins, aromatics and other chemical raw materials from heavy raw materials through refinery units is the only way to solve the shortage of chemical light oil.

WO0031215公开了一种生产烯烃的催化裂化方法，该方法以减压瓦斯油为原料，采用的催化剂由基质和ZSM系列分子筛组成，其中基质部分包括惰性基质和少量活性基质，分子筛则采用大孔分子筛，该方法的低碳烯烃收率能超过13重％，比常规催化裂化方法高。WO0031215 discloses a catalytic cracking method for producing olefins. The method uses vacuum gas oil as a raw material. The catalyst used is composed of a substrate and a ZSM series molecular sieve. The yield of light olefins in the method can exceed 13% by weight, which is higher than the conventional catalytic cracking method.

WO0040677公开了一种加氢处理和催化裂化的组合工艺方法。该方法包括至少两个加氢处理装置和两个催化裂化装置。原料油先经第一个加氢处理装置得到第一个加氢尾油；第一个加氢尾油进入第一个催化裂化装置，得到石脑油、柴油和重油，其中重油进入第二个加氢处理装置进行加氢，得到第二个加氢尾油，第二个加氢尾油到第二个催化裂化装置进行裂化，再得到相应产品。该方法流程复杂，投资和操作成本高，丙烯产率较低。WO0040677 discloses a combined process of hydrotreating and catalytic cracking. The process includes at least two hydrotreating units and two catalytic cracking units. The raw oil first passes through the first hydrotreating unit to obtain the first hydrogenated tail oil; the first hydrogenated tail oil enters the first catalytic cracking unit to obtain naphtha, diesel oil and heavy oil, and the heavy oil enters the second The hydrotreating unit performs hydrogenation to obtain the second hydrogenated tail oil, and the second hydrogenated tail oil is sent to the second catalytic cracking unit for cracking to obtain corresponding products. The process of the method is complicated, the investment and operation costs are high, and the yield of propylene is low.

CN1171978C公布了一种高硫高金属渣油转化方法。该方法通过采用部分物料循环的方法，是溶剂脱沥青、加氢处理及催化裂化进行了整体有机组合，可以较大幅度降低投资和操作费用，提高了轻质油的收率和质量。但是该方法以汽油、柴油等轻质燃料为主要目的产品，低碳烯烃产率很低。CN1171978C discloses a method for converting high-sulfur and high-metal residue oil. By adopting the method of partial material circulation, the method is an overall organic combination of solvent deasphalting, hydrogenation treatment and catalytic cracking, which can greatly reduce investment and operating costs, and improve the yield and quality of light oil. However, this method takes light fuels such as gasoline and diesel oil as the main target products, and the yield of low-carbon olefins is very low.

                         发明内容Contents of invention

本发明的目的是在现有技术的基础上提供一种由渣油和重馏分油生产清洁柴油和低碳烯烃的方法。The purpose of the present invention is to provide a method for producing clean diesel oil and low-carbon olefins from residual oil and heavy distillate oil on the basis of the prior art.

本发明提供的方法包括下列步骤：Method provided by the invention comprises the following steps:

(1)渣油与任选的来自催化裂解单元的油浆进入溶剂脱沥青单元，经低分子溶剂进行溶剂抽提后得到脱油沥青和脱沥青油；(1) The residual oil and the optional oil slurry from the catalytic cracking unit enter the solvent deasphalting unit, and after carrying out solvent extraction with a low-molecular solvent, deoiled asphalt and deasphalted oil are obtained;

(2)脱沥青油与任选的重馏分油进入加氢单元，在氢气的存在下依次与加氢精制催化剂和加氢裂化催化剂接触进行加氢精制反应和加氢裂化反应，分离反应产物得到轻石脑油馏分、重石脑油馏分、柴油馏分和加氢尾油；(2) The deasphalted oil and the optional heavy distillate oil enter the hydrogenation unit, and in the presence of hydrogen, they are successively contacted with the hydrofinishing catalyst and the hydrocracking catalyst to carry out the hydrofinishing reaction and the hydrocracking reaction, and the reaction product is separated to obtain Light naphtha fraction, heavy naphtha fraction, diesel fraction and hydrogenated tail oil;

(3)加氢尾油进入催化裂解单元，在催化裂解催化剂的作用下进行裂解反应，分离反应产物得到乙烯、丙烯等低碳烯烃、汽油馏分、柴油馏分和油浆，其中全部的催化裂解柴油馏分循环回催化裂解反应器，全部或部分的催化裂解油浆返回溶剂脱沥青单元。(3) The hydrogenation tail oil enters the catalytic cracking unit, and the cracking reaction is carried out under the action of the catalytic cracking catalyst, and the reaction products are separated to obtain low-carbon olefins such as ethylene and propylene, gasoline fractions, diesel fractions and oil slurry, and all catalytic cracking diesel oil The fraction is recycled back to the FCC reactor and all or part of the FCC slurry is returned to the solvent deasphalting unit.

采用本发明提供的方法可由渣油和重馏分油最大量地生产丙烯、乙烯等低碳烯烃和低硫、低芳烃、高十六烷值的清洁柴油，其中丙烯收率大于27重％，而柴油能达到欧IV排放标准。除此以外，还能副产其它高价值的馏分油，如富含芳烃的裂解汽油馏分，其可以生产得到苯、甲苯、二甲苯等芳烃。The method provided by the invention can be used to produce low-carbon olefins such as propylene and ethylene and clean diesel oil with low sulfur, low aromatics and high cetane number from residual oil and heavy distillate oil in a large amount, wherein the propylene yield is greater than 27% by weight, and Diesel can meet Euro IV emission standards. In addition, other high-value distillates can also be produced by-products, such as aromatics-rich pyrolysis gasoline fractions, which can produce aromatics such as benzene, toluene, and xylene.

附图是本发明所提供的由渣油和重馏分油生产清洁柴油和低碳烯烃的方法原则流程示意图。The accompanying drawing is a schematic flow chart of the principle of the method for producing clean diesel and low-carbon olefins from residual oil and heavy distillate oil provided by the present invention.

                       具体实施方式 Detailed ways

本发明提供的方法是这样具体实施的：Method provided by the invention is implemented like this:

(1)溶剂脱沥青单元(1) Solvent deasphalting unit

渣油与任选的来自催化裂解单元的油浆进入溶剂脱沥青单元，经低分子溶剂进行溶剂抽提后得到脱油沥青和脱沥青油。所述的渣油为常压渣油和/或减压渣油，优选减压渣油。所述的低分子溶剂是选自C3～C8烷烃或烯烃、凝析油、轻石脑油、轻汽油中的一种或其混合物。溶剂脱沥青的原理是利用低分子溶剂对环烷烃、烷烃及低分子芳香烃有相当大的溶解度，而对胶质、沥青质则难溶或几乎不溶的特性，将胶质、沥青质自减压渣油和循环油浆中脱除。由于减压渣油中所含的重金属绝大部分存在于其胶质、沥青质中，所以脱沥青过程中同时也就脱去了大部分镍、钒等金属。溶剂脱沥青所得到的脱油沥青的组成以沥青质和胶质为主，并含有多环芳烃，可用于生产道路沥青、造气或发电。The residual oil and the optional oil slurry from the catalytic cracking unit enter the solvent deasphalting unit, and are subjected to solvent extraction with a low-molecular solvent to obtain deoiled asphalt and deasphalted oil. The residue is atmospheric residue and/or vacuum residue, preferably vacuum residue. The low-molecular solvent is selected from C3-C8 alkanes or olefins, condensate oil, light naphtha, light gasoline or a mixture thereof. The principle of solvent deasphalting is to use low-molecular-weight solvents that have considerable solubility in cycloalkanes, alkanes and low-molecular aromatics, but are insoluble or almost insoluble in colloids and asphaltenes. Residue oil and circulating oil slurry are removed. Since most of the heavy metals contained in the vacuum residue exist in its colloids and asphaltenes, most of the nickel, vanadium and other metals are also removed during the deasphalting process. The deoiled asphalt obtained by solvent deasphalting is mainly composed of asphaltenes and colloids, and contains polycyclic aromatic hydrocarbons, which can be used to produce road asphalt, generate gas or generate electricity.

溶剂脱沥青单元主要包括抽提部分和溶剂回收部分：减压渣油和催化裂解循环油浆在溶剂的亚临界条件下进行抽提，即操作温度和压力分别低于溶剂的临界温度和临界压力；脱沥青油溶液中的溶剂依次通过临界回收、闪蒸和汽提的方法进行回收；脱油沥青溶液中的溶剂依次通过闪蒸和汽提的方法进行回收。抽提部分的主要操作条件为：抽提温度50～280℃，抽提塔压力1.0～6.0MPa，溶剂比为1～15v/v。The solvent deasphalting unit mainly includes the extraction part and the solvent recovery part: the vacuum residue and the catalytic cracking cycle oil slurry are extracted under the subcritical condition of the solvent, that is, the operating temperature and pressure are lower than the critical temperature and critical pressure of the solvent respectively The solvent in the deasphalted oil solution is recovered through critical recovery, flashing and stripping in sequence; the solvent in the deoiled asphalt solution is recovered through flashing and stripping in sequence. The main operating conditions of the extraction part are: the extraction temperature is 50-280°C, the pressure of the extraction tower is 1.0-6.0MPa, and the solvent ratio is 1-15v/v.

催化裂解单元的油浆含一定量烷烃和低缩合芳烃以及大量的高缩合芳烃，虽然高缩合芳烃是生焦前驱物，但它同时又是优质沥青的调和组分。因此，将催化裂解油浆与减压渣油混合后共同作为溶剂脱沥青单元的进料，不但能充分利用油浆中有价值的组分，而且能有效脱除油浆中的催化裂解催化剂粉末，避免其沉积在后续加氢单元的反应器中造成反应器压降上升。催化裂解循环油浆的相对分子量比减压渣油的相对分子量小，但它芳香性很强，尤其是稠环芳烃的含量很高，相对分子量小使溶解度增大，芳香性强使溶解度降低，其综合效果是掺入油浆后的减压渣油在溶剂中的溶解度降低。因此，催化裂解循环油浆进脱沥青装置既可降低减压渣油的粘度，又可提高脱沥青油收率，还能改善脱沥青油性质和沥青质量。The oil slurry of the catalytic cracking unit contains a certain amount of alkanes, low-condensation aromatics and a large amount of high-condensation aromatics. Although high-condensation aromatics are coke precursors, they are also blending components of high-quality asphalt. Therefore, mixing the catalytic cracking oil slurry and the vacuum residue together as the feed of the solvent deasphalting unit can not only make full use of the valuable components in the oil slurry, but also effectively remove the catalytic cracking catalyst powder in the oil slurry , to avoid its deposition in the reactor of the subsequent hydrogenation unit causing the pressure drop of the reactor to rise. The relative molecular weight of catalytic cracking circulating oil slurry is smaller than that of vacuum residue, but it has strong aromaticity, especially the high content of polycyclic aromatic hydrocarbons. The small relative molecular weight increases the solubility, and the strong aromaticity reduces the solubility. The combined effect is that the solubility of the vacuum residue in the solvent after being blended into the oil slurry is reduced. Therefore, the catalytic cracking circulating oil slurry into the deasphalting unit can not only reduce the viscosity of vacuum residue, but also increase the yield of deasphalted oil, and can also improve the properties of deasphalted oil and the quality of asphalt.

(2)加氢单元(2) Hydrogenation unit

来自溶剂脱沥青单元的脱沥青油与任选的重馏分油进入加氢单元，在氢气的存在下先与加氢精制催化剂接触，在反应温度280～450℃，氢分压3.0～15.0MPa，体积空速0.2～10.0h^-1，氢油体积比200～3000Nm³/m³的反应条件下，进行加氢脱硫、加氢脱氮、芳烃饱和以及少量的烯烃饱和反应。其反应生成物不经分离与加氢裂化催化剂接触，在反应温度300～450℃，氢分压3.0～15.0MPa，体积空速0.1～10.0h^-1，氢油体积比300～3000Nm³/m³的反应条件下，进行裂化、开环及异构等分子结构发生变化的反应，其反应流出物经冷却分离后得到富氢气体和液相产物。富氢气体作为循环氢循环使用，液相产物经分馏系统分离后得到轻石脑油馏分、重石脑油馏分、柴油馏分和加氢尾油。The deasphalted oil and optional heavy distillate oil from the solvent deasphalting unit enter the hydrogenation unit, and in the presence of hydrogen, they are first contacted with the hydrofinishing catalyst, at a reaction temperature of 280-450 ° C, and a hydrogen partial pressure of 3.0-15.0 MPa, Under the reaction conditions of volume space velocity of 0.2-10.0h^-1 and hydrogen-oil volume ratio of 200-3000Nm³ /m³ , hydrodesulfurization, hydrodenitrogenation, aromatic hydrocarbon saturation and a small amount of olefin saturation reactions are carried out. The reaction product is contacted with the hydrocracking catalyst without separation, at a reaction temperature of 300-450°C, a hydrogen partial pressure of 3.0-15.0MPa, a volume space velocity of 0.1-10.0h^-1 , and a hydrogen-oil volume ratio of 300-3000Nm³ /m Under the reaction conditions of³ , the reactions of molecular structure changes such as cracking, ring opening and isomerization are carried out, and the reaction effluent is cooled and separated to obtain hydrogen-rich gas and liquid phase products. The hydrogen-rich gas is recycled as circulating hydrogen, and the liquid phase product is separated by a fractionation system to obtain light naphtha fraction, heavy naphtha fraction, diesel fraction and hydrogenated tail oil.

所述的重馏分油为减压瓦斯油或焦化瓦斯油或它们的混合物。优选减压瓦斯油，其馏程通常为350℃～600℃。The heavy distillate oil is vacuum gas oil or coker gas oil or their mixtures. Vacuum gas oil is preferred, and its distillation range is usually 350°C to 600°C.

加氢精制催化剂和加氢裂化催化剂可装填在一个反应器不同床层中，也可分别装填在两个反应器中，每个反应器间的反应流出物不进行分离。反应器内有多个催化剂床层的，使用每个床层间注冷氢的方式来控制床层温度。在加氢精制催化剂床层顶部装填一定数量的加氢保护剂，以脱除进料中的金属和残炭，延缓催化剂床层压降上升的速度，并防止下游加氢精制催化剂因沉积重金属而失活。加氢保护剂与加氢精制催化剂的装填体积比为1∶20～1∶4，二者确切的装填比例视加氢单元进料油中残炭、金属及沥青质含量而定。The hydrorefining catalyst and the hydrocracking catalyst can be packed in different bed layers of one reactor, or can be packed in two reactors respectively, and the reaction effluent between each reactor is not separated. If there are multiple catalyst beds in the reactor, the bed temperature is controlled by injecting cold hydrogen between each bed. Fill a certain amount of hydrogenation protection agent on the top of the hydrofinishing catalyst bed to remove the metal and carbon residue in the feed, delay the pressure drop of the catalyst bed, and prevent the downstream hydrofinishing catalyst from being damaged due to the deposition of heavy metals Inactivate. The loading volume ratio of the hydrogenation protecting agent and the hydrofining catalyst is 1:20~1:4, and the exact loading ratio depends on the residual carbon, metal and asphaltene contents in the feed oil of the hydrogenation unit.

所述的加氢精制催化剂为负载型催化剂，其载体为无定型氧化铝和/或硅铝，负载的金属组分为VIB族金属和/或VIII族非贵金属，VIB族的金属优选钼和/或钨，VIII族的非贵金属优选钴和/或镍。The hydrorefining catalyst is a supported catalyst, the carrier of which is amorphous alumina and/or silica-alumina, and the supported metal component is a VIB group metal and/or a VIII group non-noble metal, and the VIB group metal is preferably molybdenum and/or Or tungsten, the non-noble metal of group VIII is preferably cobalt and/or nickel.

所述的加氢裂化催化剂是一种由沸石与氧化铝复合成型载体负载至少一种第VIII族和至少一种第VIB族的金属组分及有机添加物的催化剂。优选的加氢裂化催化剂的组成为：以催化剂为基准，沸石3～60重％，氧化铝10～80重％，氧化镍1～15重％，氧化钨5～40重％，有机添加物含量为0.1～40重％。所述的沸石选自，所述的有机添加物选自含氧或含氮的有机物中的一种或几种。所述的含氧化合物选自有机醇、有机酸中的一种或几种，含氮化合物为有机胺。所用的加氢裂化催化剂通过协调金属组分和载体的功能，增强了其选择性开环能力，能使重质原料的烃族组成发生明显变化，其中链烷烃、环烷烃等饱和烃的含量大大增加，芳烃尤其是多环芳烃的含量减少，使得加氢尾油的氢含量得到明显提高。The hydrocracking catalyst is a catalyst in which at least one metal component of group VIII and at least one metal component of group VIB and organic additives are supported by a composite carrier of zeolite and alumina. The composition of the preferred hydrocracking catalyst is: based on the catalyst, 3-60 wt% of zeolite, 10-80 wt% of alumina, 1-15 wt% of nickel oxide, 5-40 wt% of tungsten oxide, organic additive content It is 0.1 to 40% by weight. The zeolite is selected from, and the organic additive is selected from one or more of oxygen-containing or nitrogen-containing organic substances. The oxygen-containing compound is selected from one or more of organic alcohols and organic acids, and the nitrogen-containing compound is an organic amine. The hydrocracking catalyst used enhances its selective ring-opening ability by coordinating the functions of the metal component and the carrier, and can significantly change the hydrocarbon group composition of heavy feedstock, in which the content of saturated hydrocarbons such as paraffins and naphthenes is greatly increased. The content of aromatic hydrocarbons, especially polycyclic aromatic hydrocarbons, decreased, so that the hydrogen content of hydrogenated tail oil was significantly increased.

脱沥青油与减压瓦斯油相比，不但馏分较重，且残炭、金属及沥青质等含量均高于后者。高残炭含量易导致加氢催化剂的快速结焦，引起加氢催化剂的失活和加氢反应器床层压降的快速上涨；金属沉积也是引起床层压降上涨另一原因，金属堵塞催化剂孔道可导致催化剂的永久性失活；沥青质作为结焦前驱物，极易引起加氢催化剂中的微孔堵塞，导致迅速失活。因此本方法为了缓解加工脱沥青油所带来的床层压降快速上升及加氢催化剂的失活等问题，采用了合理的催化剂级配方式，并采用抗中毒能力强的加氢裂化催化剂。此外，由于选用了芳烃加氢活性高及开环裂化选择性高的加氢裂化催化剂，既能将脱沥青油和任选的劣质重馏分油最大限度地转化为杂质含量低、氢含量高的加氢尾油，还能副产其它高价值的馏分油，例如所得的轻石脑油馏分硫含量低，既是优质的制氢原料或蒸汽裂解制乙烯原料也是低硫汽油的调合组分；重石脑油馏分硫和氮含量低、芳潜高，是催化重整的优质原料；柴油馏分硫和芳烃含量低、十六烷值高，是优质的清洁柴油，能达到欧IV排放标准。Compared with vacuum gas oil, deasphalted oil not only has heavier distillates, but also has higher content of carbon residue, metals and asphaltenes than the latter. High carbon residue content can easily lead to rapid coking of hydrogenation catalyst, causing deactivation of hydrogenation catalyst and rapid increase of pressure drop in hydrogenation reactor bed; metal deposition is also another reason for the increase in bed pressure drop, metal blocking catalyst pores It can lead to permanent deactivation of the catalyst; as a coking precursor, asphaltenes can easily cause micropore blockage in the hydrogenation catalyst, resulting in rapid deactivation. Therefore, in order to alleviate the rapid increase of bed pressure drop and the deactivation of hydrogenation catalyst caused by processing deasphalted oil, this method adopts a reasonable catalyst gradation method and uses a hydrocracking catalyst with strong anti-poisoning ability. In addition, due to the selection of a hydrocracking catalyst with high hydrogenation activity for aromatics and high selectivity for ring-opening cracking, it is possible to convert deasphalted oil and optional low-quality heavy distillate to the maximum extent into low impurity content and high hydrogen content. Hydrogenated tail oil can also by-produce other high-value distillates, such as the obtained light naphtha fraction with low sulfur content, which is not only a high-quality raw material for hydrogen production or steam cracking raw material for ethylene production, but also a blending component of low-sulfur gasoline; The heavy naphtha fraction has low sulfur and nitrogen content and high aromatic potential, and is a high-quality raw material for catalytic reforming; the diesel fraction has low sulfur and aromatic content, and high cetane number, and is a high-quality clean diesel oil that can meet Euro IV emission standards.

(3)催化裂解单元(3) Catalytic cracking unit

来自加氢单元的加氢尾油进入催化裂解单元，在催化裂解催化剂的作用下进行裂解反应，分离反应产物得到乙烯、丙烯等低碳烯烃、汽油馏分、柴油馏分和油浆，其中全部的催化裂解柴油馏分循环回催化裂解反应器，全部或部分的催化裂解油浆返回溶剂脱沥青单元。裂解汽油馏分富含芳烃，可用于生产苯、甲苯、二甲苯等芳烃，柴油馏分作为回炼油，能维持催化裂解单元热平衡同时增产烯烃。The hydrogenated tail oil from the hydrogenation unit enters the catalytic cracking unit, where it undergoes a cracking reaction under the action of a catalytic cracking catalyst, and the reaction products are separated to obtain low-carbon olefins such as ethylene and propylene, gasoline fractions, diesel fractions, and oil slurry, all of which are catalytic The cracked diesel fraction is recycled back to the catalytic cracking reactor, and all or part of the catalytic cracking oil slurry is returned to the solvent deasphalting unit. The pyrolysis gasoline fraction is rich in aromatics and can be used to produce aromatics such as benzene, toluene, and xylene. The diesel fraction is used as refinish oil, which can maintain the heat balance of the catalytic cracking unit and increase the production of olefins.

采用的催化裂解反应器是提升管反应器、流化床反应器或移动床反应器中任一种反应器或任两种反应器组合的复合反应器，其中任两种反应器组合的复合反应器包括由提升管与流化床构成的复合反应器、由两个或两个以上的提升管构成的复合反应器、由两个或两个以上的流化床构成的复合反应器、由两个或两个以上的移动床构成的复合反应器。上述反应器可以使用现有的催化裂化反应器，也可以对现有的催化裂化反应器进行必要的改造，还可以使用与现有催化裂化反应器结构和功能类似的反应器。复合反应器中的每个反应器内的催化裂解催化剂可以相同，也可以不同。The catalytic cracking reactor used is any reactor in riser reactor, fluidized bed reactor or moving bed reactor or a composite reactor of any combination of two reactors, wherein the composite reaction of any combination of two reactors The reactor includes a composite reactor composed of a riser and a fluidized bed, a composite reactor composed of two or more risers, a composite reactor composed of two or more fluidized beds, a composite reactor composed of two A compound reactor composed of one or more moving beds. The above-mentioned reactor can use the existing catalytic cracking reactor, can also carry out necessary modification to the existing catalytic cracking reactor, and can also use a reactor similar in structure and function to the existing catalytic cracking reactor. The catalytic cracking catalysts in each reactor in the composite reactor can be the same or different.

提升管反应器的反应条件为：反应温度500～650℃、反应压力(绝对压力)0.10～0.50MPa、停留时间1～10秒、催化裂解催化剂与催化裂解原料油的重量比5～40、水蒸汽与催化裂解原料油的重量比0.1～0.6。流化床反应器、移动床反应器、复合反应器中的流化床和/或移动床的反应条件为：反应温度500～650℃、反应压力(绝对压力)0.10～0.50MPa、空速1.0～20.0h^-1、催化裂解催化剂与催化裂解原料油的重量比5～40、水蒸汽与催化裂解原料油的重量比0.1～0.6。The reaction conditions of the riser reactor are: reaction temperature 500-650°C, reaction pressure (absolute pressure) 0.10-0.50 MPa, residence time 1-10 seconds, weight ratio of catalytic cracking catalyst to catalytic cracking feedstock oil 5-40, water The weight ratio of steam to catalytic cracking raw material oil is 0.1-0.6. The reaction conditions of the fluidized bed reactor, the moving bed reactor, and the fluidized bed and/or moving bed in the composite reactor are: reaction temperature 500-650°C, reaction pressure (absolute pressure) 0.10-0.50MPa, space velocity 1.0 ~20.0h^-1 , the weight ratio of catalytic cracking catalyst to catalytic cracking raw material oil is 5-40, and the weight ratio of water vapor to catalytic cracking raw material oil is 0.1-0.6.

所述的催化裂解催化剂包括沸石、无机氧化物和任选的粘土，各组分的含量分别为：沸石15～60重％、无机氧化物5～85重％、粘土0～70重％，其中沸石为中孔沸石和任选的Y型沸石的混合物，中孔沸石选自ZSM系列沸石，即ZSM-5、ZSM-11、ZSM-12、ZSM-23、ZSM-35、ZSM-38、ZSM-48和其它类似结构的沸石之中的一种或一种以上的混合物。Y型沸石选自稀土Y(REY)、稀土氢Y(REHY)、超稳Y和高硅Y中的一种或一种以上的混合物。无机氧化物作为粘结剂，选自二氧化硅和/或三氧化二铝。粘土作为载体，选自高岭土和/或多水高岭土。The catalytic cracking catalyst includes zeolite, inorganic oxide and optional clay, and the contents of each component are respectively: 15-60% by weight of zeolite, 5-85% by weight of inorganic oxide, and 0-70% by weight of clay, wherein The zeolite is a mixture of medium pore zeolites and optionally Y-type zeolites selected from the ZSM series of zeolites, namely ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM One or more mixtures of -48 and other similarly structured zeolites. The Y-type zeolite is selected from one or more mixtures of rare earth Y (REY), rare earth hydrogen Y (REHY), ultrastable Y and high silicon Y. Inorganic oxides as binders are selected from silicon dioxide and/or aluminum oxide. Clay as carrier is selected from kaolin and/or halloysite.

下面结合附图对本发明提供的方法进行进一步的说明，但并不因此限制本发明。The method provided by the present invention will be further described below in conjunction with the accompanying drawings, but the present invention is not limited thereby.

附图是本发明提供的由渣油和重馏分油生产清洁柴油和低碳烯烃的方法原则流程示意图。The accompanying drawing is a schematic flow chart of the method for producing clean diesel and low-carbon olefins from residual oil and heavy distillate oil provided by the present invention.

本发明所提供的由渣油和重馏分油生产清洁柴油和低碳烯烃的方法流程为：来自管线1的减压渣油和任选的来自管线18的催化裂解油浆混合后进入溶剂脱沥青单元2，经来自管线19的低分子溶剂抽提后得到脱油沥青和脱沥青油，其中脱油沥青经管线3抽出装置，脱沥青油经管线4抽出与来自管线5的重馏分油混合后进入加氢单元7，在来自管线6的氢气存在下，依次接触加氢精制催化剂和加氢裂解催化剂进行反应，其反应流出物经分离后所得的轻石脑油馏分、重石脑油馏分、柴油馏分和加氢尾油分别经管线8、9、10、11抽出。加氢尾油经管线11进入催化裂解单元，在催化裂解催化剂的作用下进行催化裂解反应，分离反应产物得到低碳烯烃、汽油馏分、循环油和油浆，低碳烯烃和汽油馏分分别经管线13和14抽出，循环油经管线15循环回催化裂解单元，油浆经管线16抽出后分为两路，一路经管线18循环回到溶剂脱沥青单元，另一路由管线17抽出装置。The process flow of the method for producing clean diesel oil and light olefins from residual oil and heavy distillate oil provided by the present invention is: the vacuum residual oil frompipeline 1 and the optional catalytic cracking oil slurry frompipeline 18 are mixed and then entersolvent deasphalting Unit 2, deoiled asphalt and deasphalted oil are obtained after extraction with low molecular solvent frompipeline 19, wherein deoiled asphalt is extracted throughpipeline 3, and deasphalted oil is extracted throughpipeline 4 and mixed with heavy distillate oil frompipeline 5 Enter thehydrogenation unit 7, in the presence of hydrogen from thepipeline 6, successively contact the hydrofinishing catalyst and the hydrocracking catalyst for reaction, the light naphtha fraction, heavy naphtha fraction, diesel oil fraction obtained after the reaction effluent is separated Distillate and hydrogenated tail oil are extracted throughpipelines 8, 9, 10 and 11 respectively. The hydrogenated tail oil enters the catalytic cracking unit through thepipeline 11, and the catalytic cracking reaction is carried out under the action of the catalytic cracking catalyst, and the reaction products are separated to obtain light olefins, gasoline fractions, cycle oil and oil slurry, and the light olefins and gasoline fractions are respectively passed through thepipeline 13 and 14 are drawn out, and the circulating oil is circulated back to the catalytic cracking unit through thepipeline 15. After the oil slurry is drawn out through thepipeline 16, it is divided into two routes.

本发明将溶剂脱沥青单元、加氢单元和催化裂解单元有机地结合在一起，通过催化剂的合理配比、反应条件的合理选择以及流程的优化组合，将重质原料最大限度地转化为化工原料，为炼厂提供了一种由单一的炼油向生产化工原料及高附加值下游产品发展和延伸的有效方法。The invention organically combines the solvent deasphalting unit, the hydrogenation unit and the catalytic cracking unit, and converts heavy raw materials into chemical raw materials to the greatest extent through the rational proportioning of catalysts, the reasonable selection of reaction conditions and the optimized combination of processes , providing an effective method for the refinery to develop and extend from a single refinery to the production of chemical raw materials and high value-added downstream products.

采用本发明提供的方法，可由渣油和重馏分油最大量地生产丙烯、乙烯等低碳烯烃和低硫、低芳烃、高十六烷值的清洁柴油，其中丙烯收率大于27重％，而柴油能达到欧IV排放标准。除此以外，还能副产其它高价值的馏分油，如富含芳烃的裂解汽油馏分，其可以生产得到苯、甲苯、二甲苯等芳烃；轻石脑油馏分硫含量低，既是优质的制氢原料或蒸汽裂解制乙烯原料也是低硫汽油的调合组分；重石脑油馏分硫和氮含量低、芳潜高，是催化重整的优质原料。By adopting the method provided by the invention, low-carbon olefins such as propylene and ethylene and clean diesel oil with low sulfur, low aromatics and high cetane number can be produced in a large amount from residual oil and heavy distillate oil, wherein the propylene yield is greater than 27% by weight, Diesel can meet Euro IV emission standards. In addition, other high-value distillates can also be produced by-products, such as pyrolysis gasoline fractions rich in aromatics, which can produce aromatics such as benzene, toluene, and xylene; light naphtha fractions have low sulfur content, which is a high-quality production Hydrogen raw material or steam cracking ethylene raw material is also a blending component of low-sulfur gasoline; heavy naphtha fraction has low sulfur and nitrogen content and high aromatic potential, which is a high-quality raw material for catalytic reforming.

实施例中所用的加氢精制催化剂和加氢裂化催化剂的商品牌号分别为RN-2和RHC-1，均由中国石化催化剂分公司长岭催化剂厂生产。实施例中所用的催化裂解催化剂的商品牌号为MMC-2，由中国石化催化剂分公司齐鲁催化剂厂生产。The trade names of the hydrorefining catalyst and the hydrocracking catalyst used in the examples are RN-2 and RHC-1 respectively, both of which are produced by Changling Catalyst Factory of Sinopec Catalyst Company. The trade name of the catalytic cracking catalyst used in the examples is MMC-2, produced by Qilu Catalyst Factory of Sinopec Catalyst Company.

                         实施例1Example 1

本实施例所用的原料为减压渣油与来自催化裂解单元油浆的混合物，混合原料性质如表1所示。混合原料和异戊烷溶剂分别从抽提塔的上部和下部进入，在抽提塔内进行逆流接触，在抽提塔顶温度180℃，抽提塔压力4.0MPa，溶剂比6.0v/v，停留时间30分钟的条件下进行一段抽提。从抽提塔顶部出来的液体物流依次经临界溶剂回收、闪蒸、汽提后得到脱沥青油，抽提塔底部物流依次经闪蒸、汽提回收溶剂后得到脱油沥青。所得脱沥青油的主要性质如表1所示，从表1中可以看出，脱沥青油的硫含量为2.0重％，金属含量为15.3μg/g，沥青质含量为0.005重％，脱沥青油的收率为67.2重％。The raw material used in this example is a mixture of vacuum residue and oil slurry from a catalytic cracking unit, and the properties of the mixed raw material are shown in Table 1. The mixed raw material and isopentane solvent enter from the upper and lower parts of the extraction tower respectively, and conduct countercurrent contact in the extraction tower. The temperature at the top of the extraction tower is 180°C, the pressure of the extraction tower is 4.0MPa, and the solvent ratio is 6.0v/v. A stage of extraction was carried out under the condition of a residence time of 30 minutes. The liquid flow from the top of the extraction tower is recovered by critical solvent, flashed and stripped to obtain deasphalted oil, and the bottom flow of the extraction tower is flashed and stripped to recover the solvent to obtain deoiled asphalt. The main properties of the obtained deasphalted oil are shown in Table 1. It can be seen from Table 1 that the sulfur content of the deasphalted oil is 2.0% by weight, the metal content is 15.3 μg/g, and the asphaltene content is 0.005% by weight. The oil yield was 67.2% by weight.

                         实施例2Example 2

本实施例所用的原料为实施例1得到的脱沥青油和一种减压瓦斯油以重量比1∶1混合后的混合物，减压瓦斯油性质如表2所示。此混合原料在氢气的存在下进入第一加氢反应器与加氢精制催化剂接触进行反应，反应产物不进行分离进入第二加氢反应器与加氢裂化催化剂接触进行反应，其反应流出物经冷却、分离和分馏后得到轻石脑油馏分、重石脑油馏分、柴油馏分和加氢尾油，反应条件和产品主要性质如表3所示。The raw material used in this example is the mixture of the deasphalted oil obtained in Example 1 and a vacuum gas oil at a weight ratio of 1:1. The properties of the vacuum gas oil are shown in Table 2. In the presence of hydrogen, the mixed raw material enters the first hydrogenation reactor to contact with the hydrorefining catalyst for reaction, and the reaction product is not separated and enters the second hydrogenation reactor to contact with the hydrocracking catalyst for reaction, and the reaction effluent is passed through After cooling, separation and fractionation, light naphtha fraction, heavy naphtha fraction, diesel fraction and hydrogenated tail oil were obtained. The reaction conditions and main properties of the products are shown in Table 3.

由表3可以看出，所得的轻石脑油馏分硫含量＜1μg/g，既是优质的制氢原料或蒸汽裂解制乙烯原料也是低硫汽油的调合组分；所得的重石脑油馏分硫和氮含量均小于0.5μg/g、且芳潜含量高，是催化重整的优质原料；所得的柴油馏分硫含量小于10μg/g，十六烷值为55，多环芳烃含量小于5重％，是优质的清洁柴油，能达到欧IV排放标准。尾油馏分的氢含量高达13.9重％，是催化裂解单元的优质原料。It can be seen from Table 3 that the sulfur content of the obtained light naphtha fraction is less than 1 μg/g, which is not only a high-quality hydrogen production raw material or steam cracking ethylene production raw material, but also a blending component of low-sulfur gasoline; the obtained heavy naphtha fraction sulfur content and nitrogen content are both less than 0.5μg/g, and the aromatic latent content is high, which is a high-quality raw material for catalytic reforming; the obtained diesel fraction has a sulfur content of less than 10μg/g, a cetane number of 55, and a polycyclic aromatic hydrocarbon content of less than 5% by weight , is a high-quality clean diesel oil that can meet Euro IV emission standards. The hydrogen content of the tail oil fraction is as high as 13.9% by weight, which is a high-quality raw material for the catalytic cracking unit.

                         实施例3Example 3

本实施例以实施例2所得的加氢尾油作为原料，在流化床反应器中进行反应，然后对产品进行分离，分离反应产物得到乙烯、丙烯等低碳烯烃、汽油馏分、柴油馏分和油浆，其中全部的柴油馏分循环回催化裂解反应器，全部或部分的油浆返回溶剂脱沥青单元。催化裂解的操作条件和产品分布如表4所示。从表4中可以看出，丙烯和乙烯收率分别高达27.3重％和10.6重％。This embodiment uses the hydrogenated tail oil obtained in Example 2 as a raw material, reacts in a fluidized bed reactor, and then separates the product, and separates the reaction product to obtain low-carbon olefins such as ethylene and propylene, gasoline fractions, diesel fractions, and Slurry, where the entire diesel fraction is recycled back to the catalytic cracking reactor and all or part of the slurry is returned to the solvent deasphalting unit. The operating conditions and product distribution of catalytic cracking are shown in Table 4. It can be seen from Table 4 that the yields of propylene and ethylene were as high as 27.3% by weight and 10.6% by weight, respectively.

                           表1  减压渣油+裂解油浆   脱沥青油   密度(20℃)，g/cm³   1.0108   0.9398   硫含量，重％   4.3   2.0   氮含量，重％   0.36   0.27   金属含量，μg/g   120   15.3   沥青质，重％   6.1   0.005   残炭，重％   19.2   3.7   收率，重％   67.2   馏程(ASTM D-1160)，℃   5％   -   455   30％   -   550   50％   -   584   70％   -   612   90％   -   655   95％   -   659   终馏点   -   682Table 1 Vacuum residue + cracking oil slurry deasphalted oil Density (20℃), g/^cm3 1.0108 0.9398 Sulfur content, wt% 4.3 2.0 Nitrogen content, wt% 0.36 0.27 Metal content, μg/g 120 15.3 Asphaltenes, weight % 6.1 0.005 Carbon residue, wt% 19.2 3.7 Yield, wt% 67.2 Distillation range (ASTM D-1160),℃ 5% - 455 30% - 550 50% - 584 70% - 612 90% - 655 95% - 659 end point - 682

                               表2   减压瓦斯油   减压瓦斯油   密度(20℃)，g/cm³   0.9163   馏程(D-1160)，℃   硫含量，重％   1.8   5％   349   氮含量，重％   0.11   30％   419   金属含量，μg/g   1.1   50％   446   沥青质，重％   23   95％   511   残炭，重％   0.19   终馏点   562Table 2 Vacuum Gas Oil Vacuum Gas Oil Density (20℃), g/^cm3 0.9163 Distillation range (D-1160), ℃ Sulfur content, wt% 1.8 5% 349 Nitrogen content, wt% 0.11 30% 419 Metal content, μg/g 1.1 50% 446 Asphaltenes, weight % twenty three 95% 511 Carbon residue, wt% 0.19 end point 562

                            表3   反应条件   加氢精制   加氢裂化   氢分压，MPa   14.0   14.0   反应温度，℃   375   375   体积空速，h^-1   0.9   1.4   氢油体积比，Nm³/m³   900   900   液体产品收率   轻石脑油馏分，重％   0.5   重石脑油馏分，重％   8.1   柴油馏分，重％   27.1   加氢尾油，重％   64.3   产品主要性质   轻石脑油馏分   重石脑油馏分   密度，(20℃)，g/cm³   0.669   0.750   硫含量，μg/g   ＜1   ＜0.5   氮含量，μg/g   -   ＜0.5   芳潜，重％   59   柴油馏分   加氢尾油   密度，(20℃)，g/cm³   0.8331   0.8681   硫含量，μg/g   ＜30   -   十六烷值   55   -   多环芳烃含量，重％   ＜5   氢含量，重％   -   13.9table 3 Reaction conditions Hydrofining Hydrocracking Hydrogen partial pressure, MPa 14.0 14.0 Reaction temperature, °C 375 375 Volumetric space velocity, h^-1 0.9 1.4 Hydrogen oil volume ratio, Nm³ /m³ 900 900 Liquid Product Yield Light naphtha fraction, weight % 0.5 Heavy naphtha fraction, weight % 8.1 Diesel fraction, weight % 27.1 Hydrogenated tail oil, wt% 64.3 Main properties of the product light naphtha fraction heavy naphtha fraction Density, (20°C), g/^cm3 0.669 0.750 Sulfur content, μg/g <1 <0.5 Nitrogen content, μg/g - <0.5 Fragrant potential, wt% 59 diesel fraction Hydrogenated tail oil Density, (20°C), g/^cm3 0.8331 0.8681 Sulfur content, μg/g <30 - cetane number 55 - PAH content, weight % <5 Hydrogen content, weight % - 13.9

              表4  催化裂解反应条件  反应温度，℃   600  反应压力(绝对压力)，MPa   0.195  空速，h^-1   6.0  剂油比   15  水蒸汽与原料油重量比   0.47  催化裂解产品分布，重％  H₂-C₂(不计乙烯)   5.30  乙烯   10.60  C₃-C₄(不计丙烯)   9.90  丙烯   27.30  C₅⁺汽油   27.00  柴油   8.55  油浆   5.15  焦炭   6.20Table 4 Catalytic cracking reaction conditions Reaction temperature, °C 600 Reaction pressure (absolute pressure), MPa 0.195 Airspeed, h^-1 6.0 Agent tooil ratio 15 Water vapor to raw oil weight ratio 0.47 Catalytic cracking product distribution, weight % H₂ -C₂ (excluding ethylene) 5.30 Vinyl 10.60 C₃ -C₄ (excluding propylene) 9.90 Propylene 27.30 C₅⁺ petrol 27.00 diesel fuel 8.55 oil slurry 5.15 coke 6.20

Claims (11)

1, a kind of method of producing clean diesel and low-carbon alkene by residual oil and heavy distillate comprises the following steps:

(1) residual oil enters the solvent deasphalting unit with optional from the unitary slurry oil of catalytic pyrolysis, obtains de-oiled asphalt and deasphalted oil after low molecular solvent is carried out solvent extraction;

(2) deasphalted oil enters hydrogenation unit with the heavy distillate of choosing wantonly, contact with hydrocracking catalyst with Hydrobon catalyst successively in the presence of hydrogen and carry out hydrofining reaction and hydrocracking reaction, reaction product isolated obtains light naphtha fraction, heavy naphtha fraction, diesel oil distillate and hydrogenation tail oil;

(3) hydrogenation tail oil enters the catalytic pyrolysis unit, under the effect of catalytic cracking catalyst, carry out scission reaction, reaction product isolated obtains low-carbon alkene, gasoline fraction, diesel oil distillate and slurry oils such as ethene, propylene, wherein whole catalytic pyrolysis diesel oil distillates loop back the catalytic cracking reaction device, and all or part of catalytic cracking slurry oil returns the solvent deasphalting unit.

2,, it is characterized in that the unitary operational condition of described solvent deasphalting is: 50～280 ℃ of extraction temperatures, extraction tower pressure 1.0～6.0MPa, solvent ratio 1～15v/v according to the method for claim 1.

3,, it is characterized in that described low molecular solvent is a kind of or its mixture that is selected from C3～C8 alkane or alkene, condensate oil, light naphthar, the petroleum naphtha according to the method for claim 1.

4, according to the method for claim 1, it is characterized in that described residual oil is long residuum and/or vacuum residuum, described heavy distillate is vacuum gas oil and/or coker gas oil.

5,, it is characterized in that described hydrofining reaction condition is: 280～450 ℃ of temperature of reaction, hydrogen dividing potential drop 3.0～15.0MPa, volume space velocity 0.2～10.0h according to the method for claim 1^-1, hydrogen to oil volume ratio 200～3000Nm³/ m³The hydrocracking reaction condition is: 300～450 ℃ of temperature of reaction, hydrogen dividing potential drop 3.0～15.0MPa, volume space velocity 0.1～10.0h^-1, hydrogen to oil volume ratio 300～3000Nm³/ m³

6, according to the method for claim 1, it is characterized in that described hydrocracking catalyst is a kind of by zeolite and the carrier loaded at least a group VIII of aluminum oxide composite molding and the metal component of at least a group vib and the catalyzer of organic additive, described organic additive is selected from and contains in oxygen or the nitrogenous organism one or more.

7, according to the method for claim 1 or 6, it is characterized in that described hydrocracking catalyst, with the catalyzer benchmark, it consists of: zeolite molecular sieve 3～60 heavy %, aluminum oxide 10～80 heavy %, nickel oxide 1～15 heavy %, Tungsten oxide 99.999 5～40 heavy %, organic additive content are 0.1～40 heavy %.

8,, it is characterized in that the unitary catalytic cracking reaction device of described catalytic pyrolysis is the compound reactor of any reactor or any two combination of reactors in riser reactor, fluidized-bed reactor or the moving-burden bed reactor according to the method for claim 1.

9, according to the method for claim 8, it is characterized in that the reaction conditions of described riser reactor is: the weight ratio 0.1～0.6 of weight ratio 5～40, water vapor and the catalytic pyrolysis stock oil of 500～650 ℃ of temperature of reaction, reaction pressure 0.10～0.50MPa, 1～10 second residence time, catalytic cracking catalyst and catalytic pyrolysis stock oil.

10,, it is characterized in that the fluidized-bed in described fluidized-bed reactor, moving-burden bed reactor, the compound reactor and/or the reaction conditions of moving-bed are: 500～650 ℃ of temperature of reaction, reaction pressure 0.10～0.50MPa, air speed 1.0～20.0h according to the method for claim 8^-1, catalytic cracking catalyst and catalytic pyrolysis stock oil the weight ratio 0.1～0.6 of weight ratio 5～40, water vapor and catalytic pyrolysis stock oil.

11, according to the method for claim 1, it is characterized in that described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, each components contents is respectively: zeolite 15～60 heavy %, inorganic oxide 5～85 heavy %, clay 0～70 heavy %, its mesolite is the mixture of mesopore zeolite and the y-type zeolite of choosing wantonly.

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