技术领域technical field
本发明属于石油烃的催化转化方法，更具体地说，是涉及到一种劣质蜡油催化裂化与加氢处理的集成工艺的催化转化方法。The invention belongs to a catalytic conversion method of petroleum hydrocarbons, more specifically, relates to a catalytic conversion method of an integrated process of catalytic cracking and hydrotreating of inferior wax oil.
背景技术Background technique
常规的催化裂化工艺加工高硫劣质蜡油原料不但使催化裂化再生烟气中的SOX排放不符合环保要求，而且汽油与柴油产品中的硫含量均不能符合产品规格要求。因此，通常这些高硫劣质蜡油原料先经加氢处理，除去硫、氮和金属等杂质，饱和原料中的多环芳烃，提高其催化裂化反应性能，然后再作为催化裂化的原料，生产低硫汽油和柴油。The processing of high-sulfur and low-quality wax oil raw materials by conventional catalytic cracking technology not only makes the SOX emission in the catalytic cracking regeneration flue gas not meet the environmental protection requirements, but also the sulfur content in gasoline and diesel products cannot meet the product specification requirements. Therefore, usually these high-sulfur low-quality wax oil raw materials are first hydrotreated to remove impurities such as sulfur, nitrogen and metals, saturate the polycyclic aromatic hydrocarbons in the raw materials, and improve their catalytic cracking reaction performance, and then use them as raw materials for catalytic cracking to produce low Sulfur gasoline and diesel.
US4780193公开了一种采用加氢精制技术提高催化裂化原料质量的方法，该加氢精制装置的反应温度低于390℃，反应压力至少在10.0MPa以上，最好在12.0MPa以上。在有利于芳烃饱和的工艺条件下，通过加氢精制提高催化裂化装置原料的裂化性能，从而提高催化裂化装置的转化率，生产出高辛烷值的汽油调和组分。CN101684417A公开了一种优化的加氢-催化裂化组合工艺方法，蜡油原料在加氢处理反应区进行反应，得到的加氢蜡油作为催化裂化原料油，不经分馏直接进入催化裂化单元，催化重循环油循环回加氢处理反应区，热高压分离器顶部气相物流和催化轻循环与任选的粗柴油进入加氢改质反应区，进行加氢改质反应，反应生成物经分馏后得到加氢石脑油和加氢柴油。加氢处理单元和加氢改质单元公用氢气系统，降低装置设备投资和操作费用。产品方案灵活，可同时生产优质低硫汽油、优质柴油以及重整原料。US4780193 discloses a method for improving the quality of catalytic cracking raw materials by using hydrorefining technology. The reaction temperature of the hydrorefining unit is lower than 390° C., and the reaction pressure is at least 10.0 MPa, preferably 12.0 MPa. Under the process conditions that are favorable for the saturation of aromatics, the cracking performance of the raw material of the catalytic cracking unit is improved by hydrofining, thereby increasing the conversion rate of the catalytic cracking unit and producing high-octane gasoline blending components. CN101684417A discloses an optimized hydrogenation-catalytic cracking combined process method. The wax oil raw material is reacted in the hydrotreating reaction zone, and the hydrogenated wax oil obtained is used as the catalytic cracking raw material oil, and directly enters the catalytic cracking unit without fractionation, and the catalyzed The heavy cycle oil is recycled back to the hydrotreating reaction zone, the gaseous phase flow at the top of the hot high-pressure separator and the catalytic light cycle and the optional gas oil enter the hydrotreating reaction zone for hydrogenation and upgrading reaction, and the reaction product is fractionated to obtain Hydrogenated Naphtha and Hydrogenated Diesel. The hydrogen treatment unit and the hydrogenation upgrading unit share the hydrogen system, which reduces equipment investment and operating costs. The product scheme is flexible, and it can produce high-quality low-sulfur gasoline, high-quality diesel oil and reforming raw materials at the same time.
通常，劣质蜡油原料经加氢处理后可以改善其催化裂化性能，但在加氢处理过程中会因为馏程变轻而产生部分柴油、石脑油和轻烃，不利于多产汽油和丙烯。此外，多产异构烷烃的催化裂化工艺(MIP)对处理优质的催化裂化原料油，尤其是加氢蜡油，造成汽油烯烃含量偏低，液化气中的异丁烯含量偏低，产物分布不够优化，石油资源未充分利用。Generally, the catalytic cracking performance of low-quality wax oil raw materials can be improved after hydrotreating, but in the process of hydrotreating, some diesel oil, naphtha and light hydrocarbons will be produced due to the lighter distillation range, which is not conducive to the production of gasoline and propylene . In addition, the catalytic cracking process (MIP) that produces more isoparaffins treats high-quality catalytic cracking feedstock oil, especially hydrogenated wax oil, resulting in low olefin content in gasoline, low isobutene content in liquefied gas, and insufficient product distribution. , oil resources are not fully utilized.
MIP工艺已得到广泛的应用，目前已应用到近50套催化裂化装置，取得巨大的经济效益和社会效益。关于富含异丁烷的液化气和富含异构烷烃汽油的MIP技术详细描述见ZL99105904.2、ZL99105905.0和ZL99105903.4。The MIP process has been widely used, and has been applied to nearly 50 sets of catalytic cracking units, and has achieved huge economic and social benefits. See ZL99105904.2, ZL99105905.0 and ZL99105903.4 for a detailed description of the MIP technology of liquefied gas rich in isobutane and gasoline rich in isoparaffins.
随着环保法规对催化裂化生产过程以及产品质量要求日益严格，催化裂化即使处理加氢蜡油，催化裂化再生烟气中的SOX排放也难以符合环保要求，仍然需要增加再生烟气处理装置。当再生烟气处理装置处理较低含量的SOX烟气时，其处理效率将有所降低。此外，即使加氢蜡油催化裂化生产汽油硫含量较低，但仍然难以将汽油中的硫含量降低到10微克/克以下，汽油仍然需要后处理。当采用S-Zorb技术处理硫含量较低的汽油时，S-Zorb因汽油中的硫含量过低，难以维持其平衡操作，需从外界补充其他的硫化物，造成S-Zorb装置使用效益降低。With the increasingly stringent environmental protection regulations on the production process and product quality of catalytic cracking, even if the catalytic cracking process treats hydrogenated wax oil, the SOX emissions in the catalytic cracking regeneration flue gas are difficult to meet the environmental protection requirements, and it is still necessary to increase the regeneration flue gas treatment device. When the regenerative flue gas treatment device treats flue gas with a lower content of SOX , its treatment efficiency will be reduced. In addition, even though hydrogenated wax oil catalytic cracking produces gasoline with low sulfur content, it is still difficult to reduce the sulfur content in gasoline to below 10 μg/g, and gasoline still needs after-treatment. When S-Zorb technology is used to treat gasoline with low sulfur content, it is difficult to maintain its balanced operation due to the low sulfur content of S-Zorb in gasoline, and it is necessary to supplement other sulfur compounds from the outside, resulting in a decrease in the use efficiency of the S-Zorb unit .
发明内容Contents of the invention
本发明的目的是提供一种劣质蜡油催化裂化与加氢处理的集成工艺的催化转化方法。本发明的第一种实施方案如下：The purpose of the present invention is to provide a catalytic conversion method of an integrated process of catalytic cracking and hydrotreating of inferior wax oil. First kind of embodiment of the present invention is as follows:
本发明提供的催化转化方法包括以下步骤：Catalytic conversion method provided by the invention comprises the following steps:
(1)高硫蜡油与平衡活性较低的且活性分布相对均匀的热再生催化剂在催化裂化单元反应器的下部接触并发生裂化反应，生成的油气和含炭的催化剂上行在一定的反应环境下发生选择性地氢转移反应和异构化反应，分离反应油气得到包含液化气、汽油、柴油和催化蜡油的反应产物，待生催化剂经汽提、再生后循环使用；(1) The high-sulfur wax oil contacts the thermally regenerated catalyst with low equilibrium activity and relatively uniform activity distribution in the lower part of the catalytic cracking unit reactor and undergoes cracking reaction, and the generated oil gas and carbon-containing catalyst travel upward in a certain reaction environment Selective hydrogen transfer reaction and isomerization reaction occur under the condition of the reaction, and the reaction oil and gas are separated to obtain the reaction product including liquefied petroleum gas, gasoline, diesel oil and catalytic wax oil, and the raw catalyst is recycled after being stripped and regenerated;
(2)来自步骤(1)的催化蜡油和任选的其它二次加工的蜡油作为加氢处理装置的原料油，进入加氢处理单元进行多环芳烃选择性加氢。(2) The catalytic wax oil from step (1) and optional other secondary processed wax oils are used as the raw material oil of the hydrotreating unit, and enter the hydrotreating unit for selective hydrogenation of polycyclic aromatic hydrocarbons.
步骤(2)所得加氢蜡油返回到步骤(1)的催化裂化单元或其它催化裂化装置。The hydrogenated wax oil obtained in step (2) is returned to the catalytic cracking unit of step (1) or other catalytic cracking devices.
步骤(1)的汽油进入汽油脱硫装置，柴油进入柴油脱硫装置；The gasoline of step (1) enters the gasoline desulfurization device, and the diesel oil enters the diesel oil desulfurization device;
步骤(1)的再生烟气进入烟气处理装置进行处理，处理后的烟气排放。The regenerated flue gas in step (1) enters the flue gas treatment device for treatment, and the treated flue gas is discharged.
本发明提供的催化转化方法是这样具体实施的：Catalytic conversion method provided by the invention is implemented like this:
(1)、催化裂化单元(1), catalytic cracking unit
(a)、预热的高硫劣质原料油进入反应器与平衡活性较低的且活性分布相对均匀的热再生催化剂接触并发生裂化反应，反应温度为490℃～620℃，最好为500℃～600℃，反应时间为0.5秒～2.0秒，最好为0.8秒～1.5秒，催化剂与原料油的重量比(以下简称剂油比)为3～15∶1，最好为3～12∶1，催化剂平衡活性为35～60优选40～55；(a) The preheated high-sulfur low-quality raw material oil enters the reactor and contacts with the thermally regenerated catalyst with low equilibrium activity and relatively uniform activity distribution and undergoes cracking reaction. The reaction temperature is 490 ° C ~ 620 ° C, preferably 500 ° C ~600°C, the reaction time is 0.5 seconds to 2.0 seconds, preferably 0.8 seconds to 1.5 seconds, and the weight ratio of catalyst to raw oil (hereinafter referred to as the ratio of agent to oil) is 3 to 15:1, preferably 3 to 12: 1. The equilibrium activity of the catalyst is 35-60, preferably 40-55;
(b)、生成的油气和用过的催化剂上行，在一定的反应环境下发生选择性地氢转移反应和异构化反应，反应温度为420℃～550℃，最好为460℃～500℃，反应时间为2秒～30秒，最好为3秒～15秒，催化剂与原料油的重量比为3～18∶1，最好为3～15∶1，裂化反应和氢转移反应的水蒸汽与原料油的重量比(以下简称水油比)为0.03～0.3∶1，最好为0.05～0.3∶1，压力为130kPa～450kPa；(b) The generated oil and gas and the used catalyst go up, and selective hydrogen transfer reaction and isomerization reaction occur in a certain reaction environment, and the reaction temperature is 420°C-550°C, preferably 460°C-500°C , the reaction time is 2 seconds to 30 seconds, preferably 3 seconds to 15 seconds, the weight ratio of the catalyst to the raw oil is 3 to 18:1, preferably 3 to 15:1, the water in the cracking reaction and hydrogen transfer reaction The weight ratio of steam to raw oil (hereinafter referred to as water-oil ratio) is 0.03-0.3:1, preferably 0.05-0.3:1, and the pressure is 130kPa-450kPa;
(c)、分离反应产物得到富含丙烯的液化气、烯烃含量适中的汽油、柴油、催化蜡油及其它产品，待生催化剂经汽提进入再生器，经烧焦再生后循环使用。(c) Separating the reaction products to obtain propylene-rich liquefied gas, gasoline with moderate olefin content, diesel oil, catalytic wax oil and other products. The raw catalyst is stripped and sent to the regenerator, and recycled after burning.
(d)、催化蜡油经过滤装置或蒸馏装置除去少量的催化剂颗粒后进入加氢处理装置。(d), the catalytic wax oil enters the hydrotreating unit after removing a small amount of catalyst particles through a filter unit or a distillation unit.
该方法适用的反应器可以是选自等直径提升管、等线速提升管、流化床或变径提升管中之一，也可以是由等直径提升管和流化床构成的复合反应器。The reactor suitable for this method can be selected from one of equal-diameter riser, equal-linear-velocity riser, fluidized bed or variable-diameter riser, or a composite reactor composed of equal-diameter riser and fluidized bed. .
本发明提供的方法可以在等直径提升管、等线速提升管或流化床反应器中进行，其中等直径提升管与炼厂常规的催化裂化反应器相同，等线速提升管中流体的线速基本相同。等直径提升管、等线速提升管反应器从下至上依次为预提升段、第一反应区、第二反应区，流化床反应器从下至上依次为第一反应区、第二反应区，第一反应区、第二反应区的高度之比为10～40∶90～60。当使用等直径提升管、等线速提升管或流化床反应器时，在第二反应区底部设一个或多个冷激介质入口，和/或在第二反应区内设置取热器，取热器的高度占第二反应区高度的50％～90％。分别控制每个反应区的温度和反应时间。冷激介质是选自冷激剂、冷却的再生催化剂和冷却的半再生催化剂中的一种或一种以上的任意比例的混合物。其中冷激剂是选自液化气、粗汽油、稳定汽油、柴油、重柴油或水中的一种或一种以上的任意比例的混合物；冷却的再生催化剂和冷却的半再生催化剂是待生催化剂分别经两段再生和一段再生后冷却得到的，再生催化剂碳含量为0.1重％以下，最好为0.05重％以下，半再生催化剂碳含量为0.1重％～0.9重％，最好碳含量为0.15重％～0.7重％。The method provided by the invention can be carried out in equal-diameter risers, equal-linear-velocity risers or fluidized-bed reactors, wherein the medium-diameter risers are the same as the conventional catalytic cracking reactors in refineries, and the flow rate of fluid in the equal-linear-velocity risers Line speed is basically the same. Equal-diameter riser and constant-linear-velocity riser reactors are pre-lift section, first reaction zone, and second reaction zone from bottom to top; fluidized bed reactors are first reaction zone and second reaction zone from bottom to top , The height ratio of the first reaction zone and the second reaction zone is 10-40:90-60. When using a riser of equal diameter, a riser of constant linear velocity or a fluidized bed reactor, one or more cooling medium inlets are provided at the bottom of the second reaction zone, and/or a heat extractor is arranged in the second reaction zone, The height of the heat extractor accounts for 50%-90% of the height of the second reaction zone. The temperature and reaction time of each reaction zone are controlled separately. The chilling agent is one or a mixture of more than one selected from chilling agent, cooled regenerated catalyst and cooled semi-regenerated catalyst. Wherein the cold shock agent is selected from liquefied gas, crude gasoline, stable gasoline, diesel oil, heavy diesel oil or a mixture of more than one in any proportion in water; the cooled regenerated catalyst and the cooled semi-regenerated catalyst are the catalysts to be regenerated respectively After two-stage regeneration and one-stage regeneration and cooling, the carbon content of the regenerated catalyst is less than 0.1% by weight, preferably less than 0.05% by weight, and the carbon content of the semi-regenerated catalyst is 0.1% to 0.9% by weight, preferably 0.15% by weight. % by weight to 0.7% by weight.
本发明提供的方法也可以在由等直径提升管和流化床构成的复合反应器中进行，下部的等直径提升管为第一反应区，上部的流化床为第二反应区，分别控制每个反应区的温度和反应时间。在流化床的底部设一个或多个冷激介质入口，和/或在第二反应区内设置取热器，取热器的高度占第二反应区高度的50％～90％。分别控制每个反应区的温度和反应时间。冷激介质是选自冷激剂、冷却的再生催化剂和冷却的半再生催化剂中的一种或一种以上的任意比例的混合物。其中冷激剂是选自液化气、粗汽油、稳定汽油、柴油、重柴油或水中的一种或一种以上的任意比例的混合物；冷却的再生催化剂和冷却的半再生催化剂是待生催化剂分别经两段再生和一段再生后冷却得到的，再生催化剂碳含量为0.1重％以下，最好为0.05重％以下，半再生催化剂碳含量为0.1重％～0.9重％，最好碳含量为0.15重％～0.7重％。The method provided by the present invention can also be carried out in the compound reactor that is made of equal-diameter riser and fluidized bed, the equal-diameter riser of the bottom is the first reaction zone, and the fluidized bed of the top is the second reaction zone, respectively controlled The temperature and reaction time of each reaction zone. One or more cooling shock medium inlets are arranged at the bottom of the fluidized bed, and/or a heat collector is arranged in the second reaction zone, and the height of the heat collector accounts for 50% to 90% of the height of the second reaction zone. The temperature and reaction time of each reaction zone are controlled separately. The chilling agent is one or a mixture of more than one selected from chilling agent, cooled regenerated catalyst and cooled semi-regenerated catalyst. Wherein the cold shock agent is selected from liquefied gas, crude gasoline, stable gasoline, diesel oil, heavy diesel oil or a mixture of more than one in any proportion in water; the cooled regenerated catalyst and the cooled semi-regenerated catalyst are the catalysts to be regenerated respectively After two-stage regeneration and one-stage regeneration and cooling, the carbon content of the regenerated catalyst is less than 0.1% by weight, preferably less than 0.05% by weight, and the carbon content of the semi-regenerated catalyst is 0.1% to 0.9% by weight, preferably 0.15% by weight. % by weight to 0.7% by weight.
本发明提供的方法还可以在一种新型变径提升管反应器中进行的，详细描述见ZL99105903.4。预提升段的直径与常规的等直径提升管反应器相同，一般为0.02米～5米，其高度占反应器总高度的5％～10％。预提升段的作用是在预提升介质的存在下使再生催化剂向上运动并加速，所用的预提升介质与常规的等直径提升管反应器所用的相同，选自水蒸汽或干气。The method provided by the present invention can also be carried out in a novel variable-diameter riser reactor, see ZL99105903.4 for detailed description. The diameter of the pre-lift section is the same as that of a conventional equal-diameter riser reactor, generally 0.02 to 5 meters, and its height accounts for 5% to 10% of the total height of the reactor. The role of the pre-lift section is to move and accelerate the regenerated catalyst upwards in the presence of a pre-lift medium, the same as that used in conventional equal-diameter riser reactors, selected from steam or dry gas.
第一反应区的结构类似于常规的等直径提升管反应器，其直径可与预提升段相同，也可较预提升段稍大，第一反应区的直径与预提升段的直径之比为1.0～2.0∶1，其高度占反应器总高度的10％～30％。原料油和催化剂在该区混合后，在较高的反应温度和剂油比、较短的停留时间(一般为0.5秒～2.5秒)下，主要发生裂化反应。The structure of the first reaction zone is similar to a conventional equal-diameter riser reactor, and its diameter can be the same as that of the pre-lift section, or slightly larger than that of the pre-lift section. The ratio of the diameter of the first reaction zone to the diameter of the pre-lift section is 1.0～2.0:1, its height accounts for 10%～30% of the total height of the reactor. After the feedstock oil and catalyst are mixed in this zone, the cracking reaction mainly occurs at a relatively high reaction temperature, catalyst-to-oil ratio, and short residence time (generally 0.5 seconds to 2.5 seconds).
第二反应区比第一反应区要粗，其直径与第一反应区的直径之比为1.5～5.0∶1，其高度占反应器总高度的30％～60％。其作用是降低油气和催化剂的流速和反应温度。降低该区反应温度的方法，可以从该区与第一反应区的结合部位注入冷激介质，和/或通过在该区设置取热器，取走部分热量以降低该区反应温度，从而达到抑制二次裂化反应、增加异构化反应和氢转移反应的目的。冷激介质是选自冷激剂、冷却的再生催化剂和冷却的半再生催化剂中的一种或一种以上的任意比例的混合物。其中冷激剂是选自液化气、粗汽油、稳定汽油、柴油、重柴油或水中的一种或一种以上的任意比例的混合物；冷却的再生催化剂和冷却的半再生催化剂是待生催化剂分别经两段再生和一段再生后冷却得到的，再生催化剂碳含量为0.1重％以下，最好为0.05重％以下，半再生催化剂碳含量为0.1重％～0.9重％，最好碳含量为0.15重％～0.7重％。若设置取热器，则其高度占第二反应区高度的50％～90％。物流在该反应区停留时间可以较长，为2秒～30秒。The second reaction zone is thicker than the first reaction zone, the ratio of its diameter to the diameter of the first reaction zone is 1.5-5.0:1, and its height accounts for 30%-60% of the total height of the reactor. Its function is to reduce the flow rate and reaction temperature of oil gas and catalyst. The method for reducing the reaction temperature in this zone can be to inject a cooling shock medium from the junction of this zone and the first reaction zone, and/or by setting a heat collector in this zone to take away part of the heat to reduce the reaction temperature in this zone, so as to achieve The purpose of inhibiting secondary cracking reaction, increasing isomerization reaction and hydrogen transfer reaction. The chilling agent is one or a mixture of more than one selected from chilling agent, cooled regenerated catalyst and cooled semi-regenerated catalyst. Wherein the cold shock agent is selected from liquefied gas, crude gasoline, stable gasoline, diesel oil, heavy diesel oil or a mixture of more than one in any proportion in water; the cooled regenerated catalyst and the cooled semi-regenerated catalyst are the catalysts to be regenerated respectively After two-stage regeneration and one-stage regeneration and cooling, the carbon content of the regenerated catalyst is less than 0.1% by weight, preferably less than 0.05% by weight, and the carbon content of the semi-regenerated catalyst is 0.1% to 0.9% by weight, preferably 0.15% by weight. % by weight to 0.7% by weight. If a heat extractor is provided, its height accounts for 50% to 90% of the height of the second reaction zone. The residence time of the stream in the reaction zone can be longer, ranging from 2 seconds to 30 seconds.
出口区的结构类似于常规的等直径提升管反应器顶部出口部分，其直径与第一反应区的直径之比为0.8～1.5∶1，其高度占反应器总高度的0～20％。物流可在该区停留一定时间，以抑制过裂化反应和热裂化反应，提高流体流速。The structure of the outlet zone is similar to the top outlet part of a conventional equal-diameter riser reactor, the ratio of its diameter to the diameter of the first reaction zone is 0.8-1.5:1, and its height accounts for 0-20% of the total height of the reactor. The stream can stay in this zone for a certain period of time to suppress the overcracking reaction and thermal cracking reaction and increase the fluid flow rate.
该方法适用的高硫蜡油选自常压塔顶油、常压塔抽出的馏分油、直馏减压蜡油、浅度加氢蜡油、焦化蜡油(CGO)、脱沥青油(DAO)及其混合物，其特征为硫含量应大于0.5重％，最好大于1.0重％。The high-sulfur wax oil suitable for this method is selected from atmospheric tower top oil, distillate oil extracted from atmospheric tower, straight-run vacuum gas oil, lightly hydrogenated wax oil, coking gas oil (CGO), deasphalted oil (DAO ) and mixtures thereof, characterized in that the sulfur content should be greater than 0.5% by weight, preferably greater than 1.0% by weight.
步骤(2)所述其它二次加工蜡油选自CGO、DAO及其混合物。The other secondary processing wax oils in step (2) are selected from CGO, DAO and mixtures thereof.
该方法中的两个反应区可以适用所有同一类型的催化剂，既可以是无定型硅铝催化剂，也可以是沸石催化剂，沸石催化剂的活性组分选自Y型沸石、HY型沸石、超稳Y型沸石、ZSM-5系列沸石或具有五元环结构的高硅沸石、镁碱沸石中的一种或一种以上的任意比例的混合物，该沸石可以含稀土和/或磷，也可以不含稀土和磷。The two reaction zones in the method can be applied to all catalysts of the same type, which can be amorphous silica-alumina catalysts or zeolite catalysts. The active components of zeolite catalysts are selected from Y-type zeolite, HY-type zeolite, ultra-stable Y-type Type zeolite, ZSM-5 series zeolite or high silica zeolite with five-membered ring structure, ferrierite zeolite or a mixture of more than one in any proportion, the zeolite may contain rare earth and/or phosphorus, and may not contain rare earths and phosphorus.
该方法中的两个反应区也可以适用不同类型催化剂，不同类型催化剂可以是颗粒大小不同的催化剂和/或表观堆积密度不同的催化剂。颗粒大小不同的催化剂和/或表观堆积密度不同的催化剂上活性组分分别选用不同类型沸石，沸石选自Y型沸石、HY型沸石、超稳Y型沸石、ZSM-5系列沸石或具有五元环结构的高硅沸石、镁碱沸石中的一种或一种以上的任意比例的混合物，该沸石可以含稀土和/或磷，也可以不含稀土和磷。大小不同颗粒的催化剂和/或高低表观堆积密度的催化剂可以分别进入不同的反应区，例如，含有超稳Y型沸石的大颗粒的催化剂进入第一反应区，增加裂化反应，含有稀土Y型沸石的小颗粒的催化剂进入第二反应区，增加氢转移反应，颗粒大小不同的催化剂在同一汽提器汽提和同一再生器再生，然后分离出大颗粒和小颗粒催化剂，小颗粒催化剂经冷却进入第二反应区。颗粒大小不同的催化剂是以30～40微米之间分界，表观堆积密度不同的催化剂是以0.6～0.7g/cm3之间分界。The two reaction zones in the method may also be suitable for different types of catalysts, and the different types of catalysts may be catalysts with different particle sizes and/or catalysts with different apparent packing densities. Catalysts with different particle sizes and/or active components on catalysts with different apparent bulk densities are selected from different types of zeolites. A mixture of one or more than one of ferrierite and ferrierite with a membered ring structure in any proportion. The zeolite may contain rare earth and/or phosphorus, or may not contain rare earth and phosphorus. Catalysts with different particle sizes and/or high and low apparent bulk densities can enter different reaction zones, for example, catalysts with large particles containing ultrastable Y-type zeolite enter the first reaction zone to increase cracking reactions, and rare earth Y-type zeolite containing Small particles of zeolite catalysts enter the second reaction zone to increase the hydrogen transfer reaction. Catalysts with different particle sizes are stripped in the same stripper and regenerated in the same regenerator, and then the large and small particle catalysts are separated, and the small particle catalysts are cooled. into the second reaction zone. Catalysts with different particle sizes are separated by 30-40 microns, and catalysts with different apparent bulk densities are separated by 0.6-0.7 g/cm3 .
该方法适用的活性较低的催化剂是指催化剂活性在35～55，优选40～50。其可通过现有技术中的测量方法测量：企业标准RIPP 92-90--催化裂化的微反活性试验法《石油化工分析方法(RIPP试验方法)》，杨翠定等人，1990，下文简称为RIPP 92-90。所述催化剂活性是由轻油微反活性(MA)表示，其计算公式为MA＝(产物中低于204℃的汽油产量+气体产量+焦炭产量)/进料总量＊100％＝产物中低于204℃的汽油产率+气体产率+焦炭产率。轻油微反装置(参照RIPP 92-90)的评价条件是：将催化剂破碎成颗粒直径为420～841微米的颗粒，装量为5克，反应原料是馏程为235～337℃的直馏轻柴油，反应温度460℃，重量空速为16小时-1，剂油比3.2。The catalyst with lower activity applicable to the method refers to a catalyst with an activity of 35-55, preferably 40-50. It can be measured by measuring methods in the prior art: enterprise standard RIPP 92-90--micro-reactive test method of catalytic cracking "Petrochemical Analysis Method (RIPP Test Method)", Yang Cuiding et al., 1990, hereinafter referred to as RIPP 92-90. Described catalyst activity is represented by light oil slight reaction activity (MA), and its calculation formula is MA=(gasoline yield+gas yield+coke yield lower than 204 DEG C in the product)/feed total amount*100%=in the product Gasoline yield + gas yield + coke yield below 204°C. The evaluation conditions of the light oil micro-reaction device (refer to RIPP 92-90) are: the catalyst is crushed into particles with a particle diameter of 420-841 microns, the loading capacity is 5 grams, and the reaction raw material is a straight-distilled gas with a distillation range of 235-337°C. For light diesel oil, the reaction temperature is 460°C, the weight space velocity is 16 hours-1 , and the agent-to-oil ratio is 3.2.
该方法适用的活性分布相对均匀的催化剂是指加入到催化裂化装置内催化剂初始活性不超过80，优选不超过75，更优选不超过70；该催化剂的自平衡时间为0.1小时～50小时，优选0.1～30小时，更优选0.1～10小时。The catalyst with relatively uniform activity distribution applicable to this method means that the initial activity of the catalyst added to the catalytic cracking unit is no more than 80, preferably no more than 75, more preferably no more than 70; the self-balancing time of the catalyst is 0.1 hours to 50 hours, preferably 0.1 to 30 hours, more preferably 0.1 to 10 hours.
所述的催化剂自平衡时间是指催化剂在800℃和100％水蒸气条件(参照RIPP 92-90)下老化达到平衡活性所需的时间。The catalyst self-equilibrium time refers to the time required for the catalyst to reach the equilibrium activity after aging at 800°C and 100% water vapor (refer to RIPP 92-90).
所述活性分布相对均匀的催化剂例如可经下述3种处理方法而得到：The catalyst with relatively uniform activity distribution can be obtained, for example, through the following three treatment methods:
催化剂处理方法1：Catalyst treatment method 1:
(1)、将新鲜催化剂装入流化床，优选密相流化床，与水蒸汽接触，在一定的水热环境下进行老化后得到活性相对均匀的催化剂；(1), fresh catalyst is loaded into fluidized bed, preferably dense-phase fluidized bed, contacts with water vapor, after aging under certain hydrothermal environment, obtains the relatively uniform catalyst of activity;
(2)、将所述活性相对均匀的催化剂加入到相应的反应装置内。(2) Add the catalyst with relatively uniform activity into the corresponding reaction device.
处理方法1例如是这样具体实施的：Processing method 1, for example, is specifically implemented as follows:
将新鲜催化剂装入流化床优选密相流化床内，在流化床的底部注入水蒸汽，催化剂在水蒸汽的作用下实现流化，同时水蒸汽对催化剂进行老化，老化温度为400℃～850℃，优选500℃～750℃，最好为600℃～700℃，流化床的表观线速为0.1米/秒～0.6米/秒，最好为0.15秒～0.5米/秒，老化1小时～720小时优选5小时～360小时后，得到所述的活性相对均匀的催化剂，活性相对均匀的催化剂按工业装置的要求，加入到工业装置，优选加入到工业装置的再生器。Put the fresh catalyst into the fluidized bed, preferably a dense-phase fluidized bed, and inject water vapor at the bottom of the fluidized bed, the catalyst will be fluidized under the action of water vapor, and the water vapor will age the catalyst at the same time, the aging temperature is 400°C ~850°C, preferably 500°C~750°C, preferably 600°C~700°C, the apparent linear velocity of the fluidized bed is 0.1 m/s~0.6 m/s, preferably 0.15 s~0.5 m/s, After aging for 1 hour to 720 hours, preferably 5 hours to 360 hours, the catalyst with relatively uniform activity is obtained. The catalyst with relatively uniform activity is added to the industrial device according to the requirements of the industrial device, preferably to the regenerator of the industrial device.
催化剂处理方法2：Catalyst treatment method 2:
(1)、将新鲜催化剂装入流化床优选密相流化床，与含水蒸汽的老化介质接触，在一定的水热环境下进行老化后得到活性相对均匀的催化剂；(1), fresh catalyst is loaded into fluidized bed preferably dense-phase fluidized bed, contacts with the aging medium containing water vapor, obtains the relatively uniform activity catalyst after aging under certain hydrothermal environment;
(2)、将所述活性相对均匀的催化剂加入到相应的反应装置内。(2) Add the catalyst with relatively uniform activity into the corresponding reaction device.
催化剂处理方法2的技术方案例如是这样具体实施的：The technical scheme of catalyst treatment method 2 is such as such concrete implementation:
将催化剂装入流化床优选密相流化床内，在流化床的底部注入含水蒸汽的老化介质，催化剂在含水蒸汽的老化介质作用下实现流化，同时，含水蒸汽的老化介质对催化剂进行老化，老化温度为400℃～850℃，优选500℃～750℃，最好为600℃～700℃，流化床的表观线速为0.1米/秒～0.6米/秒，最好为0.15秒～0.5米/秒，水蒸汽与老化介质的重量比为0.20～0.9，最好为0.40～0.60，老化1小时～720小时优选5小时～360小时后，得到所述的活性相对均匀的催化剂，活性相对均匀的催化剂按工业装置的要求，加入到工业装置，优选加入到工业装置的再生器。所述老化介质包括空气、干气、再生烟气、空气与干气燃烧后的气体或空气与燃烧油燃烧后的气体、或其它气体如氮气。所述水蒸气与老化介质的重量比为0.2～0.9，最好为0.40～0.60。The catalyst is loaded into a fluidized bed, preferably a dense-phase fluidized bed, and an aging medium containing water vapor is injected at the bottom of the fluidized bed. The catalyst is fluidized under the action of the aging medium containing water vapor. Carry out aging, aging temperature is 400 ℃～850 ℃, preferably 500 ℃～750 ℃, preferably 600 ℃～700 ℃, the superficial linear velocity of fluidized bed is 0.1 m/s～0.6 m/s, preferably 0.15 seconds to 0.5 m/s, the weight ratio of water vapor to aging medium is 0.20 to 0.9, preferably 0.40 to 0.60, after aging for 1 hour to 720 hours, preferably 5 hours to 360 hours, the relatively uniform activity can be obtained Catalyst, the catalyst with relatively uniform activity is added to the industrial device according to the requirements of the industrial device, preferably to the regenerator of the industrial device. The aging medium includes air, dry gas, regeneration flue gas, gas after combustion of air and dry gas or gas after combustion of air and combustion oil, or other gases such as nitrogen. The weight ratio of the water vapor to the aging medium is 0.2-0.9, preferably 0.40-0.60.
催化剂处理方法3：Catalyst treatment method 3:
(1)、将新鲜催化剂输入到流化床优选密相流化床，同时将再生器的热再生催化剂输送到所述流化床，在所述流化床内进行换热；(1), fresh catalyst is input into fluidized bed preferably dense phase fluidized bed, and the heat regenerated catalyst of regenerator is delivered to described fluidized bed simultaneously, carries out heat exchange in described fluidized bed;
(2)、换热后的新鲜催化剂与水蒸汽或含水蒸气的老化介质接触，在一定的水热环境下进行老化后得到活性相对均匀的催化剂；(2) The fresh catalyst after heat exchange is in contact with water vapor or an aging medium containing water vapor, and after aging in a certain hydrothermal environment, a catalyst with relatively uniform activity is obtained;
(3)、将所述活性相对均匀的催化剂加入到相应的反应装置内。(3) Add the catalyst with relatively uniform activity into the corresponding reaction device.
本发明的技术方案例如是这样具体实施的：Technical scheme of the present invention is such as concrete implementation like this:
将新鲜催化剂输送到流化床优选密相流化床内，同时将再生器的热再生催化剂也输送到所述流化床，在所述流化床内进行换热。在流化床的底部注入水蒸汽或含水蒸汽的老化介质，新鲜催化剂在水蒸汽或含水蒸汽的老化介质作用下实现流化，同时，水蒸汽或含水蒸汽的老化介质对新鲜催化剂进行老化，老化温度为400℃～850℃，优选500℃～750℃，最好为600℃～700℃，流化床的表观线速为0.1米/秒～0.6米/秒，最好为0.15秒～0.5米/秒，老化1小时～720小时，优选5小时～360小时，在含水蒸汽的老化介质的情况下，所述水蒸气与老化介质的重量比为大于0～4，最好为0.5～1.5，得到在所述的活性相对均匀的催化剂，活性相对均匀的催化剂按工业装置的要求，加入到工业装置，优选加入到工业装置的再生器。此外，老化步骤后的水蒸汽进入反应系统(作为汽提蒸汽、防焦蒸汽、雾化蒸汽、提升蒸汽中的一种或几种分别进入催化裂化装置中的汽提器、沉降器、原料喷嘴、预提升段)或再生系统，而老化步骤后的含水蒸汽的老化介质进入再生系统，换热后的再生催化剂返回到该再生器内。所述老化介质包括空气、干气、再生烟气、空气与干气燃烧后的气体或空气与燃烧油燃烧后的气体、或其它气体如氮气。The fresh catalyst is conveyed into a fluidized bed, preferably a dense phase fluidized bed, while the hot regenerated catalyst from the regenerator is also conveyed into said fluidized bed where heat exchange takes place. Water vapor or aging medium containing water vapor is injected into the bottom of the fluidized bed, and the fresh catalyst is fluidized under the action of water vapor or aging medium containing water vapor. At the same time, water vapor or aging medium containing water vapor ages the fresh catalyst. The temperature is 400°C to 850°C, preferably 500°C to 750°C, preferably 600°C to 700°C, and the apparent linear velocity of the fluidized bed is 0.1 m/s to 0.6 m/s, preferably 0.15 sec to 0.5 m/s, aging for 1 hour to 720 hours, preferably 5 hours to 360 hours, in the case of an aging medium containing water vapor, the weight ratio of the water vapor to the aging medium is greater than 0 to 4, preferably 0.5 to 1.5 , to obtain the catalyst with relatively uniform activity, the catalyst with relatively uniform activity is added to the industrial device according to the requirements of the industrial device, preferably to the regenerator of the industrial device. In addition, the water vapor after the aging step enters the reaction system (as one or more of stripping steam, anti-coking steam, atomizing steam, and lifting steam, respectively entering the stripper, settler, and feed nozzle in the catalytic cracking unit , pre-lift section) or a regeneration system, and the aging medium containing water vapor after the aging step enters the regeneration system, and the regenerated catalyst after heat exchange returns to the regenerator. The aging medium includes air, dry gas, regeneration flue gas, gas after combustion of air and dry gas or gas after combustion of air and combustion oil, or other gases such as nitrogen.
通过上述处理方法，工业反应装置内的催化剂的活性和选择性分布更加均匀，催化剂的选择性得到明显改善，从而干气产率和焦炭产率明显的降低。Through the above treatment method, the activity and selectivity distribution of the catalyst in the industrial reaction device is more uniform, the selectivity of the catalyst is significantly improved, and thus the dry gas yield and coke yield are significantly reduced.
(2)加氢处理单元(2) Hydrotreating unit
催化蜡油先和/或其他二次加工的蜡油混合，然后加热并与氢气混合，进入装填加氢催化剂的加氢处理反应区，在8.0～16.0MPa压力下进行多环芳烃选择性加氢饱和，反应生成油进入带分离功能的热高分，热高压分离器顶部留出的气相物流是富氢气体和加氢处理反应生成的轻烃，而热高压分离器底部留出的液相物流是加氢蜡油。热高压分离器底部液相物流经热低压分离器进一步分离出溶解的气体后不经分馏直接作为催化裂化单元的原料或其他单元的原料。Catalytic wax oil is first mixed with/or other secondary processed wax oil, then heated and mixed with hydrogen, and then enters the hydrogenation reaction zone filled with hydrogenation catalyst, and performs selective hydrogenation of polycyclic aromatic hydrocarbons at a pressure of 8.0-16.0MPa Saturated, the oil produced by the reaction enters the hot high fraction with separation function, the gas phase stream left at the top of the hot high-pressure separator is hydrogen-rich gas and light hydrocarbons generated by hydrotreating reaction, and the liquid phase stream left at the bottom of the hot high-pressure separator It is hydrogenated wax oil. The liquid phase stream at the bottom of the hot high-pressure separator passes through the hot low-pressure separator to further separate the dissolved gas, and then it is directly used as the raw material of the catalytic cracking unit or other units without fractionation.
所述的催化蜡油(即FGO)为初馏点不小于260℃的馏分，氢含量不低于10.5重％。在更优选的实施方案中，所述催化蜡油为初馏点不小于330℃的馏分，氢含量不低于10.8重％。所述的二次加工的蜡油为焦化蜡油(CGO)、脱沥青油(DAO)及其混合原料油。The catalytic wax oil (ie FGO) is a fraction with an initial boiling point of not less than 260°C, and a hydrogen content of not less than 10.5% by weight. In a more preferred embodiment, the catalytic wax oil is a fraction with an initial boiling point of not less than 330° C., and a hydrogen content of not less than 10.8% by weight. The secondary processed wax oils are coker gas oil (CGO), deasphalted oil (DAO) and mixed raw oils thereof.
所述的加氢处理装置的反应系统通常为固定床反应器，加氢处理反应条件为：反应压力8.0～16.0MPa，优选11.0MPa～15.0MPa；反应温度300～430℃，优选310～380℃；体积空速0.2～5.0h-1，优选0.4～3.0h-1；氢油体积比300～1000Nm3/m3。The reaction system of the hydroprocessing unit is usually a fixed-bed reactor, and the reaction conditions for hydroprocessing are: reaction pressure 8.0-16.0MPa, preferably 11.0MPa-15.0MPa; reaction temperature 300-430°C, preferably 310-380°C ; Volumetric space velocity 0.2-5.0h-1 , preferably 0.4-3.0h-1 ; Hydrogen-oil volume ratio 300-1000Nm3 /m3 .
所述的加氢处理固定床反应器内的催化剂装填方式依次装填加氢保护剂、加氢脱金属脱硫剂和加氢处理催化剂。以整体催化剂体积为基准，加氢保护剂、加氢脱金属脱硫剂和加氢处理催化剂的装填体积百分数分别为2～20体积％，0～20体积％，60～98体积％。The catalyst loading method in the hydrotreating fixed-bed reactor is sequentially filled with a hydrogenation protecting agent, a hydrodemetallization desulfurizer and a hydrotreating catalyst. Based on the overall catalyst volume, the loading volume percentages of the hydrogenation protecting agent, the hydrodemetallization desulfurizer and the hydrotreating catalyst are 2-20 volume percent, 0-20 volume percent and 60-98 volume percent respectively.
所述的加氢保护剂的组成为0.5～5.0重％氧化镍、2.0～10.0重％氧化钼、余量为氧化铝载体。The composition of the hydrogenation protecting agent is 0.5-5.0% by weight of nickel oxide, 2.0-10.0% by weight of molybdenum oxide, and the balance is alumina carrier.
所述的加氢脱金属脱硫剂组成为2.0～7.0重％氧化钴、10.0～30.0重％氧化钼、余量为氧化铝载体。The composition of the hydrodemetallization desulfurizer is 2.0-7.0% by weight of cobalt oxide, 10.0-30.0% by weight of molybdenum oxide, and the balance is alumina carrier.
所述的加氢处理催化剂是负载在无定型氧化铝或/和硅铝载体上的VIB族或/和VIII族非贵金属催化剂，其中所述VIB族非贵金属为钼或/和钨，VIII族非贵金属为镍、钴、铁中的一种或多种。The hydrotreating catalyst is a VIB group or/and VIII group non-noble metal catalyst supported on an amorphous alumina or/and silica-alumina carrier, wherein the VIB group non-noble metal is molybdenum or/and tungsten, and the VIII group non-noble metal is The noble metal is one or more of nickel, cobalt and iron.
(3)其他辅助单元(3) Other auxiliary units
催化裂化单元的汽油送到汽油加氢脱硫或汽油吸附脱硫装置进行汽油脱硫，分别详见专利CN101314734A或CN1658965A，催化裂化单元的柴油进入柴油脱硫装置进行柴油脱硫；催化裂化单元的再生烟气进入烟气处理装置，进行烟气处理，处理后的烟气排放。The gasoline from the catalytic cracking unit is sent to the gasoline hydrodesulfurization or gasoline adsorption desulfurization unit for gasoline desulfurization, respectively see patent CN101314734A or CN1658965A for details, the diesel oil from the catalytic cracking unit enters the diesel desulfurization unit for diesel desulfurization; the regenerated flue gas from the catalytic cracking unit enters the flue gas The gas treatment device is used for flue gas treatment, and the treated flue gas is discharged.
本发明的优点在于：The advantages of the present invention are:
1、提高不同炼油技术使用效益，强化炼油技术更加合理的集成，为炼油生产过程清洁化和炼油产品清洁化提供了一条新的途径。1. Improve the use efficiency of different refining technologies, strengthen the more reasonable integration of refining technologies, and provide a new way for cleaning the refining production process and refining products.
2、提高了原料中氢的利用率，同时又提高加氢处理的氢的利用率，从而可以节约石油资源。2. The utilization rate of hydrogen in raw materials is improved, and the utilization rate of hydrogen in hydrotreating is improved at the same time, so that oil resources can be saved.
3、提高汽油产率、异丁烯产率和总液体产率。3. Improve gasoline yield, isobutene yield and total liquid yield.
附图说明Description of drawings
图1为本发明提供的催化裂化和加氢处理集成工艺方法原则流程示意图。Fig. 1 is a schematic flow chart of the principles of the catalytic cracking and hydrotreating integrated process method provided by the present invention.
图2是本发明的优选实施方式的流程示意图。Figure 2 is a schematic flow diagram of a preferred embodiment of the present invention.
具体实施方式Detailed ways
下面结合附图进一步说明本发明所提供的方法，但本发明并不因此而受到任何限制。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 thereto.
图1为本发明提供的催化裂化和加氢处理集成工艺方法原则流程示意图。Fig. 1 is a schematic flow chart of the principles of the catalytic cracking and hydrotreating integrated process method provided by the present invention.
高硫蜡油原料进入催化裂化反应单元进行催化裂化反应，将催化裂化反应单元分离得到的催化蜡油馏分输送到加氢处理单元进行选择性加氢，得到加氢蜡油，该加氢蜡油可以返回到原催化裂化单元，也可以输送到其它反应单元。The high-sulfur wax oil raw material enters the catalytic cracking reaction unit for catalytic cracking reaction, and the catalytic wax oil fraction separated by the catalytic cracking reaction unit is sent to the hydrogenation treatment unit for selective hydrogenation to obtain hydrogenated wax oil. It can be returned to the original catalytic cracking unit or sent to other reaction units.
图2是本发明的优选实施方式的流程示意图。图2是变径提升管反应器的催化裂化和固定床反应器的加氢处理集成工艺流程示意图，设备和管线的形状、尺寸不受附图的限制，而是根据具体情况确定。Figure 2 is a schematic flow diagram of a preferred embodiment of the present invention. Figure 2 is a schematic diagram of the integrated process flow of catalytic cracking in variable-diameter riser reactors and hydroprocessing in fixed-bed reactors. The shapes and sizes of equipment and pipelines are not limited by the drawings, but determined according to specific conditions.
图2中各编号说明如下：The numbers in Figure 2 are explained as follows:
1、3、4、6、11、13、17、18、21、22、23均代表管线；2为提升管的预提升段；5、7分别为提升管的第一反应区、第二反应区；8为提升管的出口区；9为沉降器，10为旋风分离器，12为汽提器，14为待生斜管，15为再生器，16为再生斜管，19为分离系统，20为加氢处理装置。1, 3, 4, 6, 11, 13, 17, 18, 21, 22, and 23 all represent pipelines; 2 is the pre-lift section of the riser; 5, 7 are the first reaction zone and the second reaction zone of the riser, respectively. 8 is the outlet area of the riser; 9 is the settler, 10 is the cyclone separator, 12 is the stripper, 14 is the inclined pipe to be produced, 15 is the regenerator, 16 is the regeneration inclined pipe, 19 is the separation system, 20 is a hydrotreating unit.
预提升蒸汽经管线1从提升管预提升段2进入，平衡活性较低且活性分布相对均匀的热再生催化剂经再生斜管16进入提升管预提升段由预提升蒸汽进行提升。预热后的原料油经管线4与来自管线3的雾化蒸汽按一定比例从提升管预提升段进入，与热催化剂混合后进入第一反应区5内，在一定的条件下进行裂化反应。反应物流与来自管线6的冷激剂和/或冷却的催化剂(图中未标出)混合进入第二反应区7，进行二次反应，反应后的物流进入出口区8，该反应区提高物流的线速，使反应物流快速进入气固分离系统中的沉降器9、旋风分离器10，反应产物经管线11去分离系统19。反应后带炭的待生催化剂进入汽提器12，经来自管线13的水蒸汽汽提后由待生斜管14进入再生器15，待生催化剂在来自管线17的空气中烧焦再生，烟气经管线18出再生器，热的再生催化剂经再生斜管16返回提升管底部循环使用。The pre-lift steam enters from the pre-lift section 2 of the riser through the pipeline 1, and the hot regenerated catalyst with low equilibrium activity and relatively uniform activity distribution enters the pre-lift section of the riser through the regenerated inclined tube 16 and is lifted by the pre-lift steam. The preheated raw oil enters from the pre-lifting section of the riser through the pipeline 4 and the atomized steam from the pipeline 3 in a certain proportion, mixes with the hot catalyst and enters the first reaction zone 5, and undergoes cracking reaction under certain conditions. The reactant stream is mixed with the chiller and/or cooled catalyzer (not shown among the figures) from the pipeline 6 and enters the second reaction zone 7 for secondary reaction. The reacted stream enters the outlet zone 8, and the reaction zone increases the flow rate. The linear velocity allows the reactant flow to quickly enter the settler 9 and the cyclone separator 10 in the gas-solid separation system, and the reaction product goes through the pipeline 11 to the separation system 19. After the reaction, the raw catalyst with charcoal enters the stripper 12, and after being stripped by the water vapor from the pipeline 13, it enters the regenerator 15 through the inclined pipe 14, and the raw catalyst is burnt and regenerated in the air from the pipeline 17. The gas exits the regenerator through the pipeline 18, and the hot regenerated catalyst returns to the bottom of the riser through the regenerating inclined pipe 16 for recycling.
在分离系统19，分离出干气、液化气，汽油、柴油(图中未标出)和催化蜡油，其中催化蜡油经管线21送到加氢处理装置20。In the separation system 19, dry gas, liquefied gas, gasoline, diesel oil (not shown in the figure) and catalytic wax oil are separated, wherein the catalytic wax oil is sent to the hydrotreating unit 20 through the pipeline 21 .
来自管线21的催化蜡油与新氢和/或循环氢(图中未标出)混合后，进入加氢处理装置20进行多环芳烃饱和反应，经分离得到轻馏分和加氢蜡油分别经管线22、23抽出，其中加氢蜡油经管线23与高硫蜡油混合进入提升管反应器或其它催化裂化装置。After the catalytic wax oil from the pipeline 21 is mixed with new hydrogen and/or recycled hydrogen (not shown in the figure), it enters the hydrotreating unit 20 to carry out the saturation reaction of polycyclic aromatic hydrocarbons. Pipelines 22 and 23 are drawn out, wherein the hydrogenated wax oil is mixed with high-sulfur wax oil through the pipeline 23 and enters the riser reactor or other catalytic cracking devices.
实施例Example
下面的实施例将对本发明予以进一步说明，但并不因此而限制本发明。实施例、对比例中所使用的原料油性质列于表1，催化裂化催化剂的牌号为CGP-1，CGP-1催化剂经800℃，100％水蒸汽分别老化12小时和30小时，得到两种不同活性水平的CGP-1，即平衡活性分别为50和62。加氢处理固定床反应区内装填的催化剂商业牌号分别为RG-10A/RG-10B/RMS-1/RN-32V，装填体积比例为4∶4∶15∶77，以上催化剂均由中国石化催化剂分公司生产。The following examples will further illustrate the present invention, but do not limit the present invention thereby. The raw material oil property used in the embodiment, the comparative example is listed in Table 1, and the trade mark of catalytic cracking catalyst is CGP-1, and CGP-1 catalyst is through 800 ℃, 100% steam aging respectively 12 hours and 30 hours, obtains two kinds CGP-1 at different activity levels, ie, the equilibrium activity was 50 and 62, respectively. The commercial grades of the catalysts loaded in the hydrotreating fixed-bed reaction zone are RG-10A/RG-10B/RMS-1/RN-32V, respectively, and the loading volume ratio is 4:4:15:77. The above catalysts are all made by Sinopec Catalyst branch production.
实施例1Example 1
本实施例说明采用本发明提供的方法，原料A经中型催化裂化装置和中型加氢处理装置处理后的产物分布和产品性质的情况。This example illustrates the product distribution and product properties of raw material A after being treated by a medium-sized catalytic cracking unit and a medium-sized hydrotreating unit using the method provided by the present invention.
预热的原料A先在中型催化裂化装置进行加工，中型催化裂化装置的反应器的预提升段、第一反应区、第二反应区、出口区总高度为15米，预提升段直径为0.025米，其高度为1.5米；第一反应区直径为0.025米，其高度为4米；第二反应区直径为0.1米，其高度为6.5米；出口区的直径为0.025米，其高度为3米；第一、二反应区结合部位的纵剖面等腰梯形的顶角为45°；第二反应区与出口区结合部位的纵剖面等腰梯形的底角为60°。表1所列的原料A进入该反应器内，在水蒸汽存在下，与热的催化剂CGP-1接触并发生反应，CGP-1催化剂平衡活性为50，分离反应产物得到酸性气、干气、液化气、催化汽油、催化柴油、催化蜡油和焦炭并可以计算其产物分布，待生催化剂经汽提进入再生器，再生催化剂经烧焦后循环使用。在一定的试验时间内，得到一定数量的催化蜡油，为中型加氢处理装置提供原料。加入到中型实验装置内的CGP-1催化剂是新鲜CGP-1经水热处理后的催化剂，其初始活性为72，然后与装置内的平衡催化剂混合，再经装置内的水热老化，该催化剂的自平衡时间为35小时，直到装置内的催化剂平衡活性为50。The preheated raw material A is first processed in a medium-sized catalytic cracking unit. The total height of the pre-lifting section, the first reaction zone, the second reaction zone, and the outlet zone of the reactor of the medium-sized catalytic cracking unit is 15 meters, and the diameter of the pre-lifting section is 0.025 meters, its height is 1.5 meters; the diameter of the first reaction zone is 0.025 meters, its height is 4 meters; the diameter of the second reaction zone is 0.1 meters, its height is 6.5 meters; the diameter of the outlet zone is 0.025 meters, its height is 3 meters m; the vertex angle of the isosceles trapezoid in the longitudinal section of the joint of the first and second reaction zones is 45°; the base angle of the isosceles trapezoid in the longitudinal section of the joint of the second reaction zone and the outlet zone is 60°. The raw material A listed in Table 1 enters the reactor, and in the presence of water vapor, contacts and reacts with hot catalyst CGP-1. The equilibrium activity of the CGP-1 catalyst is 50, and the reaction products are separated to obtain acid gas, dry gas, Liquefied petroleum gas, catalytic gasoline, catalytic diesel, catalytic wax oil and coke can be used to calculate the distribution of their products. The raw catalyst is stripped into the regenerator, and the regenerated catalyst is recycled after being burnt. Within a certain test time, a certain amount of catalytic wax oil is obtained to provide raw materials for medium-sized hydrotreating units. The CGP-1 catalyst added to the medium-scale experimental device is fresh CGP-1 after hydrothermal treatment, and its initial activity is 72, then mixed with the equilibrium catalyst in the device, and then subjected to hydrothermal aging in the device, the catalyst's The self-equilibrium time is 35 hours until the catalyst equilibrium activity in the device is 50.
催化蜡油在中型加氢处理装置上进行加氢处理，处理后分离反应产物得到酸性气、少量干气和液化气和加氢蜡油。在一定的试验时间内，得到一定数量的加氢蜡油，为中型催化裂化装置提供原料。加氢蜡油在中型催化裂化装置上加工的操作条件和催化剂完全与原料A相同。三次试验的总产物分布按规定的比例对三套产物分布进行加和处理，催化汽油性质和催化柴油性质按规定的比例对两次中型催化裂化所得到的汽油和柴油进行混兑，然后分析所得。试验的操作条件、产品分布和产品的性质列于表2和表3。The catalytic wax oil is hydrotreated in a medium-sized hydrotreating unit, and the reaction product is separated after treatment to obtain acid gas, a small amount of dry gas, liquefied gas and hydrogenated wax oil. Within a certain test period, a certain amount of hydrogenated wax oil is obtained to provide raw materials for medium-sized catalytic cracking units. The operating conditions and catalysts for processing hydrogenated wax oil on a medium-sized catalytic cracking unit are completely the same as those of raw material A. The total product distribution of the three tests is summed according to the specified ratio for the three sets of product distribution. The properties of catalytic gasoline and catalytic diesel are mixed according to the specified ratio. . The test operating conditions, product distribution and product properties are listed in Tables 2 and 3.
对比例1Comparative example 1
采用中型试验装置和催化剂与实施例1完全相同，所用的原料油也是表1所列的原料A。只是催化裂化CGP-1催化剂平衡活性为62，另外原料A先在中型加氢处理装置上进行加氢处理，处理后分离反应产物得到酸性气、少量干气、少量的液化气、石脑油、加氢柴油和加氢蜡油。在一定的试验时间内，得到一定数量的加氢蜡油，为中型催化裂化装置提供原料。加氢蜡油在中型催化裂化装置上加工的操作条件和催化剂完全与原料A相同。将两套中型试验装置的产物分布按规定的比例进行加和计算，得到两次试验总的产物分布，其产物分布列于表2。催化汽油、催化柴油和加氢柴油性质经分析所得。试验的操作条件、产品分布和产品的性质列于表2和表3。Adopt medium-scale test device and catalyzer to be exactly the same as embodiment 1, the raw material oil used is also the raw material A listed in table 1. Only the catalytic cracking CGP-1 catalyst has an equilibrium activity of 62. In addition, the raw material A is firstly hydrotreated in a medium-sized hydroprocessing unit, and the reaction product is separated after treatment to obtain acid gas, a small amount of dry gas, a small amount of liquefied gas, naphtha, Hydrogenated Diesel Oil and Hydrogenated Wax Oil. Within a certain test period, a certain amount of hydrogenated wax oil is obtained to provide raw materials for medium-sized catalytic cracking units. The operating conditions and catalysts for processing hydrogenated wax oil on a medium-sized catalytic cracking unit are completely the same as those of raw material A. The product distribution of the two sets of medium-sized test devices is summed according to the specified ratio, and the total product distribution of the two tests is obtained. The product distribution is listed in Table 2. The properties of catalytic gasoline, catalytic diesel and hydrogenated diesel are analyzed. The test operating conditions, product distribution and product properties are listed in Tables 2 and 3.
从表2和3可以看出，相对于对比例，本发明加工的氢耗为0.60重％，降低了45.45％，而液体产率(液化气产率+汽油产率+柴油产率)本发明增加了1.70个百分点，异丁烯产率由1.31重％上升到3.49重％，增加了166.41％。As can be seen from Tables 2 and 3, compared with the comparative example, the hydrogen consumption of the present invention is 0.60% by weight, which is 45.45% lower, while the liquid yield (liquefied gas yield+gasoline yield+diesel yield) of the present invention An increase of 1.70 percentage points, the yield of isobutene rose from 1.31% by weight to 3.49% by weight, an increase of 166.41%.
实施例2Example 2
本实施例说明采用本发明提供的方法，原料B经中型催化裂化装置和中型加氢处理装置处理后的产物分布和产品性质的情况。This example illustrates the product distribution and product properties of raw material B treated by a medium-sized catalytic cracking unit and a medium-sized hydrotreating unit using the method provided by the present invention.
预热的原料B先在中型催化裂化装置进行加工，中型催化裂化装置的反应器的预提升段、第一反应区、第二反应区、出口区总高度为15米，预提升段直径为0.025米，其高度为1.5米；第一反应区直径为0.025米，其高度为4米；第二反应区直径为0.1米，其高度为6.5米；出口区的直径为0.025米，其高度为3米；第一、二反应区结合部位的纵剖面等腰梯形的顶角为45°；第二反应区与出口区结合部位的纵剖面等腰梯形的底角为60°。表1所列的原料B进入该反应器内，在水蒸汽存在下，与热的催化剂CGP-1接触并发生反应，CGP-1催化剂平衡活性为50，分离反应产物得到酸性气、干气、液化气、催化汽油、催化柴油、催化蜡油和焦炭并可以计算其产物分布，待生催化剂经汽提进入再生器，再生催化剂经烧焦后循环使用。在一定的试验时间内，得到一定数量的催化蜡油，为中型加氢处理装置提供原料。加入到中型实验装置内的CGP-1催化剂是新鲜CGP-1经水热处理后的催化剂，其初始活性为70，然后与装置内的平衡催化剂混合，再经装置内的水热老化，该催化剂的自平衡时间为35小时，直到装置内的催化剂平衡活性为50。The preheated raw material B is first processed in a medium-sized catalytic cracking unit. The total height of the pre-lifting section, the first reaction zone, the second reaction zone, and the outlet zone of the reactor of the medium-sized catalytic cracking unit is 15 meters, and the diameter of the pre-lifting section is 0.025 meters, its height is 1.5 meters; the diameter of the first reaction zone is 0.025 meters, its height is 4 meters; the diameter of the second reaction zone is 0.1 meters, its height is 6.5 meters; the diameter of the outlet zone is 0.025 meters, its height is 3 meters m; the apex angle of the isosceles trapezoid in the longitudinal section of the joint of the first and second reaction zones is 45°; the base angle of the isosceles trapezoid in the longitudinal section of the joint of the second reaction zone and the outlet zone is 60°. The raw material B listed in Table 1 enters the reactor, and in the presence of water vapor, contacts and reacts with hot catalyst CGP-1. The equilibrium activity of the CGP-1 catalyst is 50, and the reaction products are separated to obtain acid gas, dry gas, Liquefied petroleum gas, catalytic gasoline, catalytic diesel, catalytic wax oil and coke can also be used to calculate the product distribution. The raw catalyst enters the regenerator after stripping, and the regenerated catalyst is recycled after being burnt. Within a certain test time, a certain amount of catalytic wax oil is obtained to provide raw materials for medium-sized hydrotreating units. The CGP-1 catalyst added to the medium-scale experimental device is fresh CGP-1 after hydrothermal treatment, and its initial activity is 70, and then mixed with the equilibrium catalyst in the device, and then undergoes hydrothermal aging in the device, the catalyst's The self-equilibrium time is 35 hours until the catalyst equilibrium activity in the device is 50.
催化蜡油在中型加氢处理装置上进行加氢处理，处理后分离反应产物得到酸性气、少量干气和液化气和加氢蜡油。在一定的试验时间内，得到一定数量的加氢蜡油，为中型催化裂化装置提供原料。加氢蜡油在中型催化裂化装置上加工的操作条件和催化剂完全与原料B相同。三次试验的总产物分布按规定的比例对三套产物分布进行加和处理，催化汽油性质和催化柴油性质按规定的比例对两次中型催化裂化所得到的汽油和柴油进行混兑，然后分析所得。试验的操作条件、产品分布和产品的性质列于表2和表3。The catalytic wax oil is hydrotreated in a medium-sized hydrotreating unit, and the reaction product is separated after treatment to obtain acid gas, a small amount of dry gas, liquefied gas and hydrogenated wax oil. Within a certain test period, a certain amount of hydrogenated wax oil is obtained to provide raw materials for medium-sized catalytic cracking units. The operating conditions and catalysts for the processing of hydrogenated wax oil in medium-sized catalytic cracking units are completely the same as those of raw material B. The total product distribution of the three tests is summed according to the specified ratio for the three sets of product distribution. The properties of catalytic gasoline and catalytic diesel are mixed according to the specified ratio. . The test operating conditions, product distribution and product properties are listed in Tables 2 and 3.
对比例2Comparative example 2
采用中型试验装置和催化剂与实施例1完全相同，所用的原料油也是表1所列的原料B。只是催化裂化CGP-1催化剂活性为62，另外原料B先在中型加氢处理装置上进行加氢处理，处理后分离反应产物得到酸性气、少量干气、少量的液化气、石脑油、加氢柴油和加氢蜡油。在一定的试验时间内，得到一定数量的加氢蜡油，为中型催化裂化装置提供原料。加氢蜡油在中型催化裂化装置上加工的操作条件和催化剂完全与原料B相同。将两套中型试验装置的产物分布按规定的比例进行加和计算，得到两次试验总的产物分布，其产物分布列于表4。催化汽油、催化柴油和加氢柴油性质是经分析所得到的。试验的操作条件、产品分布和产品的性质列于表4和表5。Adopt medium-scale test device and catalyzer to be exactly the same as embodiment 1, and the raw material oil used is also the raw material B listed in table 1. Only the catalyst activity of catalytic cracking CGP-1 is 62. In addition, the raw material B is firstly hydrotreated in a medium-sized hydroprocessing unit, and the reaction product is separated after treatment to obtain acid gas, a small amount of dry gas, a small amount of liquefied gas, naphtha, and Hydrogen Diesel and Hydrogenated Wax Oil. Within a certain test period, a certain amount of hydrogenated wax oil is obtained to provide raw materials for medium-sized catalytic cracking units. The operating conditions and catalysts for the processing of hydrogenated wax oil in medium-sized catalytic cracking units are completely the same as those of raw material B. The product distribution of the two sets of medium-sized test devices is summed and calculated according to the specified ratio, and the total product distribution of the two tests is obtained. The product distribution is listed in Table 4. The properties of catalytic gasoline, catalytic diesel and hydrogenated diesel are obtained by analysis. The operating conditions, product distribution and product properties tested are listed in Tables 4 and 5.
从表4和5可以看出，相对于对比例，本发明加工的氢耗为0.67重％，降低了39.09％，而液体产率(液化气产率+汽油产率+柴油产率)本发明增加了2.67个百分点，异丁烯产率由1.37重％上升到2.99重％，增加了118.25％。As can be seen from Tables 4 and 5, compared with the comparative example, the hydrogen consumption of the present invention is 0.67% by weight, which reduces 39.09%, while the liquid yield (liquefied gas yield+gasoline yield+diesel yield) of the present invention An increase of 2.67 percentage points, the yield of isobutene rose from 1.37% by weight to 2.99% by weight, an increase of 118.25%.
表1Table 1
表2Table 2
表3table 3
表4Table 4
表5table 5
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110079710.4ACN102719274B (en) | 2011-03-31 | 2011-03-31 | High efficiency catalytic conversion method of petroleum hydrocarbon |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110079710.4ACN102719274B (en) | 2011-03-31 | 2011-03-31 | High efficiency catalytic conversion method of petroleum hydrocarbon |
| Publication Number | Publication Date |
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| CN102719274A CN102719274A (en) | 2012-10-10 |
| CN102719274Btrue CN102719274B (en) | 2015-02-25 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110079710.4AActiveCN102719274B (en) | 2011-03-31 | 2011-03-31 | High efficiency catalytic conversion method of petroleum hydrocarbon |
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| CN106590742B (en)* | 2015-10-15 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of heavy charge oil treatment process |
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| CN1310223A (en)* | 2001-01-18 | 2001-08-29 | 中国石油化工股份有限公司 | Catalytic converting process for producing low-alkene gasoline and high-yield diesel oil |
| CN1313379A (en)* | 2000-03-10 | 2001-09-19 | 中国石油化工集团公司 | A method for hydrotreating inferior catalytic cracking raw materials |
| CN101942340A (en)* | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司 | Method for preparing light fuel oil and propylene from inferior raw material oil |
| CN101987972A (en)* | 2009-08-06 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for processing inferior crude oil through combined processes |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1237477A (en)* | 1999-04-23 | 1999-12-08 | 中国石油化工集团公司 | A riser reactor for fluidized catalytic conversion |
| CN1313379A (en)* | 2000-03-10 | 2001-09-19 | 中国石油化工集团公司 | A method for hydrotreating inferior catalytic cracking raw materials |
| CN1310223A (en)* | 2001-01-18 | 2001-08-29 | 中国石油化工股份有限公司 | Catalytic converting process for producing low-alkene gasoline and high-yield diesel oil |
| CN101942340A (en)* | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司 | Method for preparing light fuel oil and propylene from inferior raw material oil |
| CN101987972A (en)* | 2009-08-06 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for processing inferior crude oil through combined processes |
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| CN102719274A (en) | 2012-10-10 |
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