技术领域technical field
本发明涉及一种烃类的催化转化方法，更具体地说，本发明涉及一种使烃类原料油在复合式反应器中催化裂化获得高丙烯产率的方法。The invention relates to a method for catalytic conversion of hydrocarbons, more specifically, the invention relates to a method for catalytically cracking hydrocarbon feedstock oil in a composite reactor to obtain high propylene yield.
背景技术Background technique
以乙烯、丙烯为代表的低碳烯烃是最基本的化工原料，从石油烃制取低碳烯烃的传统方法是蒸汽热裂解法，适用的原料为乙烷、丙烷、丁烷、天然气、石脑油或轻柴油等轻质石油烃，其丙烯/乙烯比不能满足市场的需求。而重油催化裂化在生产汽油和柴油的同时也副产一定量的丙烯，但其产率仅占原料油的12％以下。Low-carbon olefins represented by ethylene and propylene are the most basic chemical raw materials. The traditional method of producing low-carbon olefins from petroleum hydrocarbons is steam thermal cracking. The suitable raw materials are ethane, propane, butane, natural gas, and naphtha. For light petroleum hydrocarbons such as oil or light diesel oil, the propylene/ethylene ratio cannot meet the market demand. While catalytic cracking of heavy oil produces gasoline and diesel oil, a certain amount of propylene is also by-produced, but its yield only accounts for less than 12% of the raw oil.
目前低碳烯烃生产主要以轻烃作为原料，但原料的短缺日益严重，所以开发以重油为原料而直接生产低碳烯烃的技术路线已成为潮流。At present, the production of light olefins mainly uses light hydrocarbons as raw materials, but the shortage of raw materials is becoming more and more serious. Therefore, it has become a trend to develop a technical route to directly produce light olefins using heavy oil as raw materials.
USP5670037公开了一种制取低碳烯烃的烃类催化转化方法，原料为不同沸程的石油馏分、渣油或原油，在流化床或移动床反应器内使用固体酸催化剂在温度480-680℃，压力0.12-0.4MPa，反应时间在0.1-6秒，剂油比4-12的条件下进行催化转化反应，反应后的催化剂经烧焦再生后返回反应器内循环使用。与常规的催化裂化及水蒸气热裂解方法比较，该方法可以得到更多的丙烯和丁烯。USP5670037 discloses a method for catalytic conversion of hydrocarbons to produce low-carbon olefins. The raw material is petroleum fractions, residues or crude oil with different boiling ranges. In a fluidized bed or moving bed reactor, a solid acid catalyst is used at a temperature of 480-680 ℃, pressure 0.12-0.4MPa, reaction time 0.1-6 seconds, and catalyst-to-oil ratio 4-12, the catalytic conversion reaction is carried out, and the catalyst after the reaction is burned and regenerated and then returned to the reactor for recycling. Compared with conventional catalytic cracking and steam thermal cracking methods, this method can obtain more propylene and butene.
USP5009769中公开的烃类裂化方法采用双提提升管反应器裂化不同性质的烃类原料。蜡油和渣油注入第一提升管，在剂油比5～10、停留时间1～4秒的条件下裂化；直馏汽油、直馏中间馏分油和催化重汽油注入第二提升管，在剂油比3～12、停留时间1～5秒的条件下裂化。两个提升管末端进入同一个沉降器中，且共用后续分馏系统。这种反应型式主要用于生产高芳烃高辛烷值汽油及低碳烃类。The method for cracking hydrocarbons disclosed in USP5009769 uses double-lift riser reactors to crack hydrocarbon feedstocks with different properties. Wax oil and residual oil are injected into the first riser and cracked under the conditions of solvent-to-oil ratio of 5-10 and residence time of 1-4 seconds; straight-run gasoline, straight-run middle distillate and catalytic heavy gasoline are injected into the second riser, Cracking under the conditions of agent-oil ratio of 3-12 and residence time of 1-5 seconds. Both riser ends enter the same settler and share the subsequent fractionation system. This type of reaction is mainly used to produce high-aromatic high-octane gasoline and low-carbon hydrocarbons.
USP7261807中公开了一种增加丙烯产率的催化裂化工艺。该工艺将至少部分汽油产物进入第二个提升管内重新进行裂化反应，并且所采用的催化剂组合物中除含有大孔USY沸石外，还含有ZSM-5等中孔沸石以及具有裂化性能的无机粘结剂组分。其中的无机粘结剂组分中含磷，其P/Al比为0.1～10。该工艺过程可大幅度增产低碳烯烃，特别是增加丙烯产率。A catalytic cracking process for increasing propylene yield is disclosed in USP7261807. In this process, at least part of the gasoline product enters the second riser for cracking reaction again, and the catalyst composition used not only contains large-pore USY zeolite, but also contains medium-pore zeolite such as ZSM-5 and inorganic viscose with cracking performance. Binder components. The inorganic binder component contains phosphorus, and its P/Al ratio is 0.1-10. The process can greatly increase the production of low-carbon olefins, especially increase the yield of propylene.
USP7323099公开了一种选择性生产低碳烯烃的两段催化裂化方法。在第一反应区，重质原料在含大孔和中孔分子筛催化剂的催化转化下，生产富含烯烃的汽油组分，第一反应区生成的富含烯烃汽油组分再在第二反应区在含中孔分子筛催化剂的催化转化下，生成低碳烯烃。USP7323099 discloses a two-stage catalytic cracking method for selectively producing light olefins. In the first reaction zone, the heavy raw materials are catalytically converted by catalysts containing large and medium pore molecular sieves to produce olefin-rich gasoline components, and the olefin-rich gasoline components produced in the first reaction zone are then processed in the second reaction zone Low-carbon olefins are produced under the catalytic conversion of a medium-pore molecular sieve catalyst.
CN1299403A中公开了一种由重质烃原料选择性生产C2～C4烯烃的两段催化裂化方法。重质原料在常规大孔沸石催化裂化催化剂存在下，在由催化裂化装置组成的第一反应段中将转化成较低沸点产物；将所生成的较低沸点产物中的石脑油馏分进入第二反应段中，在500～600℃温度下与含约10～50％平均孔径小于约0.7纳米的沸石催化剂接触生成裂化产物，其中丙烯产率最高达16.8％。CN1299403A discloses a two-stage catalytic cracking method for selectively producing C2-C4 olefins from heavy hydrocarbon raw materials. In the presence of conventional large-pore zeolite catalytic cracking catalysts, heavy raw materials will be converted into lower boiling point products in the first reaction section composed of catalytic cracking units; the naphtha fraction in the generated lower boiling point products will enter the second reaction section In the second reaction section, at a temperature of 500-600° C., it is contacted with a zeolite catalyst containing about 10-50% of the average pore diameter of less than about 0.7 nanometers to generate cracked products, of which the maximum yield of propylene is 16.8%.
CN102051213A中公开了一种催化裂解方法。重质原料与含择型沸石的裂化催化剂于至少包括两个反应区的第一提升管反应器的反应区I中接触反应，然后将反应物流引入第一提升管反应器的反应区II中并与引入反应区II的裂化催化剂接触反应，引入反应区I与反应区II的裂化催化剂之比为1∶0.05～0.5；将汽油馏分和/或C4烃送入第二提升管加流化床反应器的底部与含择型沸石的裂化催化剂接触并反应，同时将裂解重油引入第二提升管反应器和/或流化床反应器底部。A catalytic cracking method is disclosed in CN102051213A. The heavy raw material and the cracking catalyst containing type-selective zeolite are contacted and reacted in the reaction zone I of the first riser reactor comprising at least two reaction zones, and then the reactant stream is introduced into the reaction zone II of the first riser reactor and Contact with the cracking catalyst introduced into the reaction zone II, the ratio of the cracking catalyst introduced into the reaction zone I and the reaction zone II is 1:0.05-0.5; the gasoline fraction and/or C4 hydrocarbons are sent to the second riser and added to the fluidized bed for reaction The bottom of the reactor contacts and reacts with the cracking catalyst containing the type-selective zeolite, and at the same time, the cracked heavy oil is introduced into the bottom of the second riser reactor and/or the fluidized bed reactor.
CN102071054A中公开了一种催化裂化方法。将重质原料送入第一提升管反应器内与含择型沸石的催化剂接触并反应；将汽油馏分和/或C4烃引入第二提升管反应器，与含择型沸石催化剂接触反应后引入与第二提升管反应器串联的流化床反应器反应，同时将裂解重油引入第二提升管反应器和/或流化床反应器。A catalytic cracking method is disclosed in CN102071054A. Send the heavy raw material into the first riser reactor to contact and react with the catalyst containing type-selective zeolite; introduce the gasoline fraction and/or C4 hydrocarbon into the second riser reactor, and introduce it after contacting with the catalyst containing type-selective zeolite The fluidized bed reactor connected in series with the second riser reactor reacts, and at the same time, the cracked heavy oil is introduced into the second riser reactor and/or the fluidized bed reactor.
CN102206509A中公开了一种生产丙烯和轻芳烃的烃类催化转化方法。将重质原料送入第一反应器与含有改性β沸石的裂化催化剂接触并进行催化裂化反应，将C4烃馏分和/或轻汽油馏分送入第二反应器与含有改性β沸石的裂化催化剂接触并进行催化裂化反应，第二反应器反应后的催化剂和油气产物引入第三反应器继续进行反应。CN102206509A discloses a hydrocarbon catalytic conversion method for producing propylene and light aromatics. The heavy raw material is sent to the first reactor to contact with the cracking catalyst containing modified zeolite β for catalytic cracking reaction, and the C4 hydrocarbon fraction and/or light gasoline fraction is sent to the second reactor to be contacted with the cracking catalyst containing modified zeolite β The catalyst is contacted and undergoes a catalytic cracking reaction, and the catalyst and oil and gas products reacted in the second reactor are introduced into the third reactor to continue the reaction.
虽然上述方法中增加催化裂化汽油在第二反应区的催化转化可以增加丙烯产率，但有些技术牺牲了催化裂化汽油转化的丙烯选择性，有些技术靠重油催化裂化装置和生成的催化裂化汽油再在另外一套独立的装置进行催化转化、两套装置的催化剂及再生装置都不相同来实现增产丙烯的目的，使得工艺过程复杂。Although increasing the catalytic conversion of FCC gasoline in the second reaction zone in the above method can increase the yield of propylene, some technologies sacrifice the propylene selectivity of FCC gasoline conversion, and some technologies rely on heavy oil catalytic cracking unit and generated FCC gasoline to regenerate Catalytic conversion is carried out in another independent device, and the catalysts and regeneration devices of the two devices are different to achieve the purpose of increasing propylene production, which makes the process complicated.
发明内容Contents of the invention
本发明的目的是提出一种以石油烃为原料，使用含大孔沸石和中孔沸石的催化裂解催化剂，在复合反应器内和一定的操作条件下发生催化裂解反应，制取低碳烯烃特别是丙烯的方法，其特征在于上述反应生成的富含烯烃的碳四馏分和/或汽油馏分与经过孔道修饰处理的催化裂解催化剂在复合反应器内接触，在一定的操作条件下进行齐聚和裂化反应，进一步转化为丙烯。The purpose of this invention is to propose a kind of with petroleum hydrocarbon as raw material, use the catalytic cracking catalyst that contains large pore zeolite and medium pore zeolite, take place catalytic cracking reaction in compound reactor and under certain operating conditions, produce light olefin especially It is a method for propylene, which is characterized in that the C4 fraction and/or gasoline fraction rich in olefins generated by the above reaction are contacted in a composite reactor with a catalytic cracking catalyst processed through pore modification, and oligomerization and Cracking reaction, further converted to propylene.
本发明的目的是通过下述方案达到的：The object of the present invention is achieved by the following scheme:
(1)将经过预热的烃类原料送入复合反应器的催化裂解反应区内，与热的含大孔沸石和中孔沸石的催化裂解催化剂接触发生催化裂解反应，催化裂解反应所产生的产物物流和积炭催化剂经气固快速分离；(1) Send the preheated hydrocarbon feedstock into the catalytic cracking reaction zone of the composite reactor, and contact with the hot catalytic cracking catalyst containing large-pore zeolite and medium-pore zeolite to generate catalytic cracking reaction, and the catalytic cracking reaction produces The product stream and carbon-deposited catalyst are quickly separated by gas and solid;
(2)步骤(1)所述积炭催化剂经汽提后进入再生器在含氧气体存在下进行烧焦再生；(2) The carbon-deposited catalyst described in step (1) enters the regenerator after being stripped and burnt and regenerated in the presence of oxygen-containing gas;
(3)步骤(1)所述产物物流经分离得到包括富含丙烯的碳三馏分、富含丁烯的碳四馏分和富含烯烃的汽油馏分；(3) The product stream described in step (1) is separated to obtain a C3 fraction rich in propylene, a C4 fraction rich in butene and a gasoline fraction rich in olefins;
(4)富含丁烯的碳四馏分和/或富含烯烃的汽油馏分送入复合反应器的齐聚/裂化反应区内，与热的经过孔道修饰处理的催化裂解催化剂接触进行齐聚和裂化反应，齐聚和裂化反应所产生的产物物流和积炭催化剂经气固快速分离；(4) The C4 cuts rich in butene and/or the gasoline cuts rich in olefins are sent into the oligomerization/cracking reaction zone of the compound reactor, and are contacted with the catalytic cracking catalyst through the channel modification treatment of heat to carry out oligomerization and Cracking reactions, product streams and coke catalysts produced by oligomerization and cracking reactions are quickly separated by gas and solid;
(5)步骤(4)所述积炭催化剂经汽提后进入再生器在含氧气体存在下进行烧焦再生；(5) The carbon-deposited catalyst described in step (4) enters the regenerator after being stripped and carries out burnt regeneration under the presence of oxygen-containing gas;
(6)步骤(4)所述产物物流与步骤(1)所述产物物流一起进入产品分离系统经分离得到包括富含丙烯的碳三馏分的产品；(6) The product stream described in step (4) enters the product separation system together with the product stream described in step (1) and is separated to obtain a product comprising a C3 fraction rich in propylene;
(7)步骤(2)、(5)再生后的催化剂分为两部分，其中一部分直接送去催化裂解反应区循环使用，另一部分先送至催化剂孔道修饰区，与富含二环和/或三环芳烃的修饰剂接触并反应，再送去齐聚/裂化反应区循环使用。(7) The catalyst regenerated in steps (2), (5) is divided into two parts, one of which is directly sent to the catalytic cracking reaction zone for recycling, and the other part is first sent to the catalyst channel modification zone, and is rich in bicyclic and/or The modifying agent of tricyclic aromatic hydrocarbons contacts and reacts, and then is sent to the oligomerization/cracking reaction zone for recycling.
本发明的具体操作步骤如下：Concrete operation steps of the present invention are as follows:
(1)烃类原料经过预热后送入复合反应器的催化裂解反应区内，与热的含大孔沸石和中孔沸石的催化裂解催化剂接触，在反应温度为480～650℃、反应压力为0.15～0.4MPa、进料重时空速为1～200h-1、催化剂与原料的重量比为5～25∶1、水蒸气与原料的重量比为0.05～1∶1的条件下发生催化裂解反应，催化裂解反应所产生的产物物流1和积炭催化剂1经气固快速分离设施分离；(1) After preheating, the hydrocarbon raw material is sent to the catalytic cracking reaction zone of the composite reactor, and is in contact with the hot catalytic cracking catalyst containing large-pore zeolite and medium-pore zeolite. Catalytic cracking occurs under the conditions of 0.15-0.4MPa, feed weight hourly space velocity of 1-200h-1 , catalyst-to-raw material weight ratio of 5-25:1, water vapor-to-raw material weight ratio of 0.05-1:1 reaction, the product stream 1 and the carbon deposit catalyst 1 produced by the catalytic cracking reaction are separated through a gas-solid rapid separation facility;
(2)积炭催化剂1去汽提器，用水蒸气汽提出催化剂上吸附的反应产物，汽提后的积炭催化剂1进入再生器，在空气等含氧气体存在下于650～800℃下进行烧焦再生；(2) The carbon deposition catalyst 1 goes to the stripper, and the reaction product adsorbed on the catalyst is stripped out with water vapor, and the stripped carbon deposition catalyst 1 enters the regenerator, and is carried out at 650-800 ° C in the presence of oxygen-containing gases such as air. charred regeneration;
(3)产物物流1经分离得到包括富含丙烯的碳三馏分、富含丁烯的碳四馏分和富含烯烃的汽油馏分；(3) The product stream 1 is separated to obtain a gasoline cut comprising a C3 cut rich in propylene, a C4 cut rich in butene and a gasoline cut rich in olefins;
(4)富含丁烯的碳四馏分和/或富含烯烃的汽油馏分送入复合反应器的齐聚/裂化反应区内，与热的经过孔道修饰处理的催化裂解催化剂接触，在反应温度为500～650℃、反应压力为0.15～0.4MPa、进料重时空速为0.1～50h-1、催化剂与原料(包括碳四馏分和/或富含烯烃的汽油馏分)的重量比为8～40∶1、水蒸气与原料的重量比为0.05～1∶1的条件下进行齐聚和裂化反应，齐聚和裂化反应所产生的产物物流2和积炭催化剂2经气固快速分离设施分离；(4) C4 cuts rich in butene and/or gasoline cuts rich in olefins are sent into the oligomerization/cracking reaction zone of the composite reactor, and contact with the hot catalytic cracking catalyst through the channel modification treatment, at the reaction temperature 500～650℃, reaction pressure 0.15～0.4MPa, feed weight hourly space velocity 0.1～50h-1, catalyst to raw material (including C4 fraction and/or olefin-rich gasoline fraction) weight ratio of 8～ The oligomerization and cracking reactions are carried out under the conditions of 40:1, the weight ratio of water vapor to raw materials is 0.05-1:1, and the product stream 2 and carbon deposit catalyst 2 produced by the oligomerization and cracking reactions are separated by gas-solid rapid separation facilities ;
(5)积炭催化剂2去汽提器，用水蒸气汽提出催化剂上吸附的反应产物，汽提后的积炭催化剂2和积炭催化剂1一起进入再生器，在空气等含氧气体存在下于650～800℃下进行烧焦再生；(5) The carbon deposit catalyst 2 goes to the stripper, and the reaction product adsorbed on the catalyst is stripped out with water vapor, and the carbon deposit catalyst 2 and the carbon deposit catalyst 1 after the stripping enter the regenerator together, in the presence of oxygen-containing gases such as air Carry out burnt regeneration at 650～800℃;
(6)产物物流2与产物物流1一起进入产品分离系统经分离得到包括富含丙烯的碳三馏分；(6) Product stream 2 enters product separation system together with product stream 1 and obtains the C3 fraction that comprises rich in propylene through separation;
(7)再生后的催化剂分为两部分，其中一部分直接送去催化裂解反应区循环使用，另一部分先送至催化剂孔道修饰区，在温度为650～780℃、接触时间为0.1～3秒的条件下与富含二环和/或三环芳烃的修饰剂接触并反应，使其在催化裂解催化剂的大孔沸石上产生一定量的焦炭从而选择性堵塞催化剂大孔沸石的孔道，再送去齐聚/裂化反应区循环使用，循环至齐聚/裂化反应区与催化裂解反应区的催化剂重量比为0.3～3∶1，催化剂孔道修饰处理的修饰剂与烃类原料的重量比为0.05～0.3∶1。(7) The regenerated catalyst is divided into two parts, one of which is directly sent to the catalytic cracking reaction zone for recycling, and the other part is first sent to the catalyst channel modification zone. Contact and react with modifiers rich in bicyclic and/or tricyclic aromatic hydrocarbons under conditions, so that a certain amount of coke is produced on the large-pore zeolite of the catalytic cracking catalyst to selectively block the pores of the large-pore zeolite of the catalyst, and then sent to the Qi The polymerization/cracking reaction zone is recycled, the weight ratio of the catalyst recycled to the oligomerization/cracking reaction zone and the catalytic cracking reaction zone is 0.3-3:1, and the weight ratio of the modifier to the hydrocarbon raw material for catalyst pore modification treatment is 0.05-0.3 : 1.
本发明所用烃类原料选自直馏蜡油、焦化蜡油、脱沥青油、加氢精制油、加氢裂化尾油、减压渣油、常压渣油中的一种或几种。The hydrocarbon raw materials used in the present invention are selected from one or more of straight-run wax oil, coker wax oil, deasphalted oil, hydrorefined oil, hydrocracking tail oil, vacuum residue and normal pressure residue.
本发明提出的催化转化装置包括复合反应器、汽提器、再生器和产品分离系统。所述的复合反应器包括烃类原料催化裂解反应区、富含烯烃馏分齐聚/裂化反应区和催化剂孔道修饰区的组合式反应器，是由一个或一个以上的提升管反应器与流化床反应器构成的复合反应器，或者是由一个或一个以上的提升管反应器与两个流化床反应器构成的复合反应器，或者是由两个或两个以上的流化床反应器构成的复合反应器。另外，上述每种反应器可以根据需要分成两个或两个以上的反应区。优选的反应器是一个以上的提升管反应器与流化床反应器构成的复合反应器，更优选的反应器是由两个提升管反应器与流化床反应器构成的复合反应器。The catalytic conversion device proposed by the invention includes a compound reactor, a stripper, a regenerator and a product separation system. The composite reactor includes a catalytic cracking reaction zone for hydrocarbon raw materials, a combined reactor for olefin-rich fraction oligomerization/cracking reaction zone and catalyst channel modification zone, and is composed of one or more riser reactors and fluidized A composite reactor composed of a bed reactor, or a composite reactor composed of one or more riser reactors and two fluidized bed reactors, or a composite reactor composed of two or more fluidized bed reactors composed of composite reactors. In addition, each of the above-mentioned reactors can be divided into two or more reaction zones as required. A preferred reactor is a composite reactor composed of more than one riser reactor and a fluidized bed reactor, and a more preferred reactor is a composite reactor composed of two riser reactors and a fluidized bed reactor.
其中，所述的提升管选自等直径提升管反应器、等线速提升管反应器和变直径提升管反应器中的一种或几种。所述流化床反应器选自固定流化床反应器、散式流化床反应器、鼓泡床反应器、湍动床反应器、快速床反应器、输送床反应器和密相流化床反应器中的一种或几种。Wherein, the riser is selected from one or more of riser reactors with equal diameters, riser reactors with constant linear velocity and riser reactors with variable diameters. The fluidized bed reactor is selected from a fixed fluidized bed reactor, a dispersed fluidized bed reactor, a bubbling bed reactor, a turbulent bed reactor, a fast bed reactor, a transport bed reactor and a dense phase fluidized One or more of the bed reactors.
所述汽提器位于所述流化床反应器的下方，并且所述汽提器与所述流化床反应器的底部直接连通，至少一个所述提升管反应器的出口和所述流化床反应器的下部任意位置连通，而且所述流化床反应器的出口与所述沉降器内的气固分离设备的入口连通。The stripper is located below the fluidized bed reactor, and the stripper is directly communicated with the bottom of the fluidized bed reactor, at least one outlet of the riser reactor and the fluidized bed reactor Any position in the lower part of the bed reactor is communicated, and the outlet of the fluidized bed reactor is communicated with the inlet of the gas-solid separation equipment in the settler.
本发明的催化转化装置的催化剂再生器至少有两条催化剂输送通路向复合反应器提供热的再生催化剂。The catalyst regenerator of the catalytic conversion device of the present invention has at least two catalyst delivery paths to provide hot regenerated catalyst to the composite reactor.
在本发明中，使汽提器位于流化床反应器的下方，并且使汽提器与流化床反应器的底部连通。由此，向汽提器中供应的水蒸气可以向上通过流化床反应器作为其中发生的催化转化反应的注水蒸气而得到二次利用，有利于降低反应的总体能耗。In the present invention, the stripper is located below the fluidized bed reactor, and the stripper is communicated with the bottom of the fluidized bed reactor. Thus, the water vapor supplied to the stripper can pass upward through the fluidized bed reactor and be used as water injection vapor for the catalytic conversion reaction therein, which is beneficial to reduce the overall energy consumption of the reaction.
在本发明优选的催化转化装置中，并用了两个提升管反应器和流化床反应器，其中第一提升管是一个单独的反应器、而第二提升管反应器的出口和该流化床反应器的下部连通。In the preferred catalytic converter of the present invention, two riser reactors and a fluidized bed reactor have been used, wherein the first riser is a separate reactor, and the outlet of the second riser reactor is connected to the fluidized bed reactor. The lower part of the bed reactor communicates.
原料油在第一提升管反应器中与来自再生器的催化裂解催化剂接触发生催化裂解反应，催化裂解所产生的产物物流1和积炭催化剂1经气固快速分离设施分离，积炭催化剂1去汽提器汽提出催化剂上吸附的反应产物，而产物物流1经分离得到包括富含丙烯的碳三馏分、富含丁烯的碳四馏分和富含烯烃的汽油馏分。汽提后的积炭催化剂1进入再生器在含氧气体存在下进行烧焦再生。再生后的催化剂送至第一提升管下部循环使用。The raw oil contacts the catalytic cracking catalyst from the regenerator in the first riser reactor to undergo a catalytic cracking reaction, and the product stream 1 and carbon deposit catalyst 1 produced by catalytic cracking are separated by a gas-solid rapid separation facility, and the carbon deposit catalyst 1 is removed. The stripper strips the reaction products adsorbed on the catalyst, and the product stream 1 is separated to obtain a C3 fraction rich in propylene, a C4 fraction rich in butenes and a gasoline fraction rich in olefins. The stripped carbon-deposited catalyst 1 enters the regenerator for coke regeneration in the presence of oxygen-containing gas. The regenerated catalyst is sent to the lower part of the first riser for recycling.
富含丁烯的碳四馏分和/或富含烯烃的汽油馏分在第二提升管上部与来自同一提升管下部的经催化剂孔道修饰处理的催化裂解催化剂一起进入流化床反应器进行齐聚和裂化反应，齐聚和裂化反应所产生的产物物流2和积炭催化剂2经气固快速分离设施分离，积炭催化剂2去汽提器汽提出催化剂上吸附的反应产物，而产物物流2与产物物流1一起进入产物分离系统分离出富含丙烯的产物。汽提后的积炭催化剂2和积炭催化剂1一起进入再生器在含氧气体存在下进行烧焦再生。Butene-rich C4 fraction and/or olefin-rich gasoline fraction enter the fluidized bed reactor together with the catalytic cracking catalyst from the lower part of the same riser at the upper part of the second riser for oligomerization and Cracking reaction, product stream 2 and coke catalyst 2 produced by oligomerization and cracking reaction are separated through gas-solid rapid separation facility, coke catalyst 2 goes to the stripper to strip out the reaction product adsorbed on the catalyst, and product stream 2 and product Stream 1 enters the product separation system together to separate the product rich in propylene. The stripped coke catalyst 2 and the coke catalyst 1 enter the regenerator together for coke regeneration in the presence of oxygen-containing gas.
再生后的催化剂一部分直接送去催化裂解反应区循环使用，另一部分先送至催化剂孔道修饰区与富含二环和/或三环芳烃的修饰剂接触并反应，使其在催化裂解催化剂的大孔沸石上产生一定量的焦炭从而选择性堵塞催化剂大孔沸石的孔道，再送去齐聚和裂化反应区循环使用。Part of the regenerated catalyst is directly sent to the catalytic cracking reaction zone for recycling, and the other part is first sent to the catalyst channel modification zone to contact and react with modifiers rich in bicyclic and/or tricyclic aromatic hydrocarbons, so that it can be used in the bulk of the catalytic cracking catalyst. A certain amount of coke is produced on the pore zeolite to selectively block the pores of the catalyst large-pore zeolite, and then sent to the oligomerization and cracking reaction zone for recycling.
所述富含二环和/或三环芳烃的催化剂孔道修饰剂是二环和/或三环芳烃含量不低于60％的化合物，选自萘、萘的衍生物、蒽、蒽的衍生物、菲、菲的衍生物、催化裂化重柴油、催化裂化回炼油、蒸汽裂解重柴油、蒸汽裂解焦油、焦化循环油、煤焦油中的一种或几种。The catalyst pore modifier rich in bicyclic and/or tricyclic aromatic hydrocarbons is a compound with a bicyclic and/or tricyclic aromatic hydrocarbon content of not less than 60%, selected from naphthalene, derivatives of naphthalene, anthracene, derivatives of anthracene One or more of phenanthrene, phenanthrene derivatives, catalytic cracking heavy diesel oil, catalytic cracking recycle oil, steam cracking heavy diesel oil, steam cracking tar, coking cycle oil, and coal tar.
所述含大孔沸石和中孔沸石的双活性组分催化裂解催化剂，以催化剂的总重量为基准，其含有1％～60％的沸石混合物、5％～99％的耐热无机氧化物和0～70％的粘土。以所述沸石混合物的总重量为基准，所述沸石混合物中含有5％～75％的Y沸石、25％～95％的具有MFI结构的中孔沸石。The dual-active component catalytic cracking catalyst containing large-pore zeolite and medium-pore zeolite, based on the total weight of the catalyst, contains 1% to 60% of zeolite mixture, 5% to 99% of heat-resistant inorganic oxide and 0-70% clay. Based on the total weight of the zeolite mixture, the zeolite mixture contains 5% to 75% of Y zeolite and 25% to 95% of medium pore zeolite with MFI structure.
所述由Y沸石可以是各种已知方法制得的稀土Y沸石、稀土氢Y沸石、超稳Y沸石、稀土超稳Y沸石、或它们中的两种或两种以上的混合物。The Y zeolite can be rare earth Y zeolite, rare earth hydrogen Y zeolite, ultra-stable Y zeolite, rare earth ultra-stable Y zeolite, or a mixture of two or more of them prepared by various known methods.
所述具有MFI结构的沸石为具有pentasil结构的高硅沸石，选自ZSM-5和ZRP系列沸石中的一种或几种，特别是选自含稀土的ZRP沸石(CN1052290A、CN1058382A、US5232675)、含磷的ZRP沸石(CN1194181A、US5951963)、含磷和稀土的ZRP沸石(CN1147420A)、含磷和碱土金属的ZRP沸石(CN1211469A、CN1211470A、US6080698)以及含磷和过渡金属的ZRP沸石(CN1465527A、CN1611299A)中的一种或几种。The zeolite with the MFI structure is a high-silica zeolite with a pentasil structure, selected from one or more of ZSM-5 and ZRP series zeolites, especially ZRP zeolites containing rare earths (CN1052290A, CN1058382A, US5232675), ZRP zeolite containing phosphorus (CN1194181A, US5951963), ZRP zeolite containing phosphorus and rare earth (CN1147420A), ZRP zeolite containing phosphorus and alkaline earth metal (CN1211469A, CN1211470A, US6080698) and ZRP zeolite containing phosphorus and transition metal (CN1465527A, CN1611299A ) in one or more.
另外，所述具有MFI结构的沸石可以采用市售品，也可以采用本领域公知的各种方法进行制备，在此不赘述。In addition, the zeolite with the MFI structure can be commercially available, or can be prepared by various methods known in the art, which will not be repeated here.
所述的耐热无机氧化物选自SiO2和/或Al2O3；粘土选自高岭土和/或多水高岭土。The heat-resistant inorganic oxide is selected from SiO2 and/or Al2 O3 ; the clay is selected from kaolin and/or halloysite.
在本发明烃类催化转化方法的一个优选实施方案中，以所述烃类催化裂解催化剂的总重量为基准，所述烃类转化催化剂含有10％～50％的所述沸石混合物、10％～70％的所述耐热无机氧化物和0～60％的所述粘土。In a preferred embodiment of the hydrocarbon catalytic conversion method of the present invention, based on the total weight of the hydrocarbon catalytic cracking catalyst, the hydrocarbon conversion catalyst contains 10% to 50% of the zeolite mixture, 10% to 70% of the heat-resistant inorganic oxide and 0-60% of the clay.
本发明可以同时使用多种原料油，特别适于加工蜡油和/或渣油原料。The invention can use multiple raw materials at the same time, and is especially suitable for processing wax oil and/or residue raw materials.
与现有技术相比，本发明采用对催化剂孔道进行修饰的方法，使含大孔沸石和中孔沸石的双活性组分催化裂解催化剂不但对重质烃类原料催化裂解具有高的重油转化能力和高的丙烯选择性，而且丁烯和高烯烃汽油催化转化也具有高的丙烯选择性，从而达到多产丙烯的目的。而且与工艺操作条件结合，还可以显著降低干气和焦炭的产率，改善柴油质量。Compared with the prior art, the present invention adopts the method of modifying the pores of the catalyst, so that the dual active component catalytic cracking catalyst containing large-pore zeolite and medium-pore zeolite not only has high heavy oil conversion capacity for catalytic cracking of heavy hydrocarbon raw materials And high propylene selectivity, and the catalytic conversion of butene and high olefin gasoline also has high propylene selectivity, so as to achieve the purpose of producing more propylene. And combined with the process operating conditions, it can also significantly reduce the yield of dry gas and coke, and improve the quality of diesel oil.
附图说明Description of drawings
附图为与本发明提供的多产丙烯的烃类催化转化方法的基本流程示意图。The accompanying drawing is a schematic flow diagram of the method for catalytic conversion of hydrocarbons with high propylene production provided by 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.
附图为与本发明提供的多产丙烯的烃类催化转化方法的基本流程示意图。其中The accompanying drawing is a schematic flow diagram of the method for catalytic conversion of hydrocarbons with high propylene production provided by the present invention. in
1-重油催化裂解提升管反应器，1-Heavy oil catalytic cracking riser reactor,
11-向提升管反应器1输送再生催化剂的输送管，11 - delivery pipe for delivery of regenerated catalyst to riser reactor 1,
12-输送管11上的再生催化剂流量控制阀，12 - Regenerated catalyst flow control valve on delivery pipe 11,
13-提升管反应器1的原料油进料喷嘴，13 - Raw oil feed nozzle for riser reactor 1,
14-提升管反应器1出口的气固快速分离装置，14-gas-solid rapid separation device at the outlet of riser reactor 1,
2-含催化剂修饰区的轻质烯烃提升管反应器，2 - light olefins riser reactor with catalyst modification zone,
21-向提升管反应器2输送再生催化剂的输送管，21 - delivery pipe for delivery of regenerated catalyst to riser reactor 2,
22-输送管21上再生催化剂流量控制阀，22-the regenerated catalyst flow control valve on the delivery pipe 21,
23-催化剂修饰区的修饰剂喷嘴，23 - Modifier nozzle for catalyst modification zone,
24-提升管反应器2的碳四和/或汽油馏分喷嘴，24 - C4 and/or gasoline fraction nozzle for riser reactor 2,
25-提升管反应器2出口分布器，25 - riser reactor 2 outlet distributor,
3-流化床反应器，3- Fluidized bed reactor,
31-流化床反应器3内的挡板。31 —Baffles inside the fluidized bed reactor 3 .
4-沉降器，4 - settler,
41-初级旋风分离器；41 - primary cyclone separator;
42-顶部旋风分离器，42 - top cyclone separator,
5-汽提器，5- stripper,
51-汽提器5内的挡板，51 - the baffle in the stripper 5,
52-与汽提器5相连的待生催化剂输送管，52-the spent catalyst conveying pipe that links to each other with stripper 5,
53-输送管52上的待生催化剂流量控制阀，53-the spent catalyst flow control valve on the delivery pipe 52,
6-再生器。6 - Regenerator.
本发明的反应器是由提升管1、提升管2、流化床3构成的复合反应器。本示意图为简化流程，但这并不影响本领域普通技术人员对本发明的理解。The reactor of the present invention is a composite reactor composed of a riser 1 , a riser 2 and a fluidized bed 3 . This schematic diagram is a simplified process, but this does not affect the understanding of the present invention by those of ordinary skill in the art.
烃类原料经过预热至180～360℃后，与水蒸气一起通过喷嘴13喷入提升管反应器1，在温度480～650℃、优选500～600℃，压力0.15～0.4MPa优选0.18～0.28MPa(绝压)，催化剂与烃类原料的重量比为5～25，反应时间为0.1～6秒优选1～5秒的条件下，与由来自输送管11的热再生催化剂接触、反应。反应物流和积炭催化剂通过初级旋风分离器41和顶部旋风分离器42分离，反应物流进入产品分离回收系统，积炭催化剂进入汽提器5。After the hydrocarbon raw material is preheated to 180-360°C, it is sprayed into the riser reactor 1 through the nozzle 13 together with water vapor. MPa (absolute pressure), the weight ratio of the catalyst to the hydrocarbon feedstock is 5-25, and the reaction time is 0.1-6 seconds, preferably 1-5 seconds, to contact and react with the heat regenerated catalyst from the delivery pipe 11. The reactant stream and the coke-deposited catalyst are separated through the primary cyclone separator 41 and the top cyclone separator 42 , the reactant stream enters the product separation and recovery system, and the coke-deposited catalyst enters the stripper 5 .
在本发明一个优选方案中，为了提高丙烯的产率，先将富含二环和/或三环芳烃的修饰剂通过喷嘴23喷入提升管反应器2的底部，与来自输送管21的热再生催化剂接触，通过选择性生焦进行催化剂孔道修饰以堵塞催化剂大孔沸石的孔道，然后将分离得到的富含烯烃的C4烃类和轻汽油组分，通过喷嘴24喷入提升管反应器2的上部，与经过孔道修饰的催化剂接触反应，反应物流和催化剂通过提升管出口分布器25进入流化床反应器3底部，在流化床反应器中，在温度500～650℃优选520～600℃，压力0.15～0.4MPa优选0.18～0.28MPa(绝压)，催化剂与原料的重量比为8～40，重时空速0.1～50h-1优选1～20h-1的条件下进一步发生齐聚和裂化反应，将反应物流高选择性地转化为丙烯。In a preferred version of the present invention, in order to improve the productive rate of propylene, the modification agent that is rich in bicyclic and/or tricyclic aromatic hydrocarbons is sprayed into the bottom of riser reactor 2 through nozzle 23 earlier, and with the heat from transfer pipe 21 The regenerated catalyst is contacted, and the pores of the catalyst are modified by selective coking to block the pores of the catalyst large-pore zeolite, and then the separated olefin-rich C4 hydrocarbons and light gasoline components are sprayed into the riser reactor 2 through the nozzle 24 The upper part of the fluidized bed reactor contacts and reacts with the catalyst modified through the channels, and the reactant stream and the catalyst enter the bottom of the fluidized bed reactor 3 through the riser outlet distributor 25. In the fluidized bed reactor, at a temperature of 500～650° C. ℃, pressure 0.15～0.4MPa preferably 0.18～0.28MPa (absolute pressure), the weight ratio of catalyst to raw material is 8～40, weight hourly space velocity 0.1～50h-1 , preferably under the conditions of 1～20h-1 further oligomerization and The cracking reaction converts the reactant stream to propylene with high selectivity.
生成富含低碳烯烃的反应物流以及积炭催化剂经顶部旋风分离器42分离，反应物流进入产品分离回收系统，积炭催化剂进入汽提器5。The reactant flow rich in low-carbon olefins and the carbon-deposited catalyst are separated through the top cyclone separator 42 , the reactant flow enters the product separation and recovery system, and the carbon-deposited catalyst enters the stripper 5 .
分离得到的反应产物在产品分离回收系统进行进一步分离，得到富含乙烯的干气、富含丙烯的C3馏分、富含丁烯的C4馏分、富含烯烃的轻汽油、富含轻芳烃的重汽油、少量柴油和重油。The separated reaction products are further separated in the product separation and recovery system to obtain dry gas rich in ethylene, C3 fraction rich in propylene, C4 fraction rich in butene, light gasoline rich in olefins, and heavy oil rich in light aromatics. Gasoline, a small amount of diesel and heavy oil.
分离得到的积炭催化剂在汽提器5中用水蒸气汽提出吸附的烃类产物，由输送管52送至再生器6进行再生，再生后热催化剂分为两部分，其中一部分经输送管11及流量控制阀12返回提升管1的底部，另一部分则经输送管21及流量控制阀22返回提升管2的底部重复使用。The separated carbon-deposited catalyst is stripped with water vapor in the stripper 5 to remove the adsorbed hydrocarbon products, and sent to the regenerator 6 for regeneration through the delivery pipe 52. After regeneration, the hot catalyst is divided into two parts, one of which passes through the delivery pipe 11 and The flow control valve 12 returns to the bottom of the riser 1, and the other part returns to the bottom of the riser 2 through the delivery pipe 21 and the flow control valve 22 for reuse.
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。实施例和对比例中所使用的烃类原料为直馏蜡油，其性质列于表1。修饰剂为萘、催化裂化重柴油或蒸汽裂解重柴油，其性质列于表2。催化剂由中国石油化工股份有限公司催化剂齐鲁分公司生产，商品名称为MMC-2。The following examples will further illustrate the present invention, but do not limit the present invention thereby. The hydrocarbon feedstock used in the examples and comparative examples is straight-run wax oil, and its properties are listed in Table 1. The modifiers are naphthalene, catalytic cracking heavy diesel oil or steam cracking heavy diesel oil, and their properties are listed in Table 2. The catalyst is produced by China Petroleum and Chemical Corporation Catalyst Qilu Branch, and the trade name is MMC-2.
实施例1～3Examples 1-3
实施例1～3说明采用本发明提供的烃类原料催化转化方法时的效果。Examples 1-3 illustrate the effects of using the method for catalytic conversion of hydrocarbon feedstock provided by the present invention.
将催化剂MMC-2在800℃，用100％水蒸气老化10小时，使用中型试验装置，复合反应器中催化剂的装量为60千克。The catalyst MMC-2 was aged at 800° C. with 100% steam for 10 hours, using a medium-sized test device, and the catalyst loading in the composite reactor was 60 kg.
实施例1中烃类原料进提升管反应器1，修饰剂萘由喷嘴23进提升管反应器2，C4和轻汽油由喷嘴24送入提升管反应器2。In Example 1, the hydrocarbon raw material enters the riser reactor 1, the modifier naphthalene enters the riser reactor 2 through the nozzle 23, and C4 and light gasoline enter the riser reactor 2 through the nozzle 24.
实施例2中烃类原料进提升管反应器1，修饰剂催化裂化重柴油由喷嘴23进提升管反应器2，C4和轻汽油由喷嘴24送入提升管反应器2。In Example 2, the hydrocarbon raw material enters the riser reactor 1, the modifier catalytic cracking heavy diesel oil enters the riser reactor 2 through the nozzle 23, and C4 and light gasoline are sent into the riser reactor 2 through the nozzle 24.
实施例3中烃类原料进提升管反应器1，修饰剂蒸汽裂解重柴油由喷嘴23进提升管反应器2，C4和轻汽油由喷嘴24送入提升管反应器2。In Example 3, the hydrocarbon raw material enters the riser reactor 1, the modifier steam cracking heavy diesel oil enters the riser reactor 2 through the nozzle 23, and C4 and light gasoline are sent into the riser reactor 2 through the nozzle 24.
实施例中剂油比是指催化剂与新鲜进料的重量比。The catalyst-to-oil ratio in the examples refers to the weight ratio of catalyst to fresh feed.
操作条件和试验结果见表3。The operating conditions and test results are shown in Table 3.
对比例1Comparative example 1
与实施例相比，对比例1说明在相同的反应器中没有加修饰剂进行烃类原料催化转化方法时的效果。结果见表3。Compared with Examples, Comparative Example 1 illustrates the effect of carrying out the catalytic conversion method of hydrocarbon feedstock in the same reactor without adding modifier. The results are shown in Table 3.
通过对比例和实施例的比较可以明显地看出，实施例的丙烯产率更高。By comparing the comparative examples and examples, it can be clearly seen that the propylene yield of the examples is higher.
虽然以上通过实施例对本发明进行了详细的说明，但要指出的是，各种变形对本领域技术人员来说是显而易见的。因此，这些变形应包含在本发明中，除非这些变形超出了本发明的范围。Although the present invention has been described in detail through the examples above, it should be pointed out that various modifications will be apparent to those skilled in the art. Therefore, such modifications should be included in the present invention unless these modifications go beyond the scope of the present invention.
表1Table 1
表2Table 2
表3table 3
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110375175.7ACN103131463B (en) | 2011-11-23 | 2011-11-23 | Hydrocarbon catalytic conversion method for increasing propylene yield |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110375175.7ACN103131463B (en) | 2011-11-23 | 2011-11-23 | Hydrocarbon catalytic conversion method for increasing propylene yield |
| Publication Number | Publication Date |
|---|---|
| CN103131463A CN103131463A (en) | 2013-06-05 |
| CN103131463Btrue CN103131463B (en) | 2015-07-01 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110375175.7AActiveCN103131463B (en) | 2011-11-23 | 2011-11-23 | Hydrocarbon catalytic conversion method for increasing propylene yield |
| Country | Link |
|---|---|
| CN (1) | CN103131463B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20020189973A1 (en)* | 1998-12-30 | 2002-12-19 | Henry B. Erik | Fluid cat cracking with high olefins production |
| US20060108260A1 (en)* | 2004-11-19 | 2006-05-25 | Henry Brian E | Two stage fluid catalytic cracking process for selectively producing C2 to C4 olefins |
| CN101747929A (en)* | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing lower olefins and aromatics |
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