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Número de publicaciónCN102875283 B
Tipo de publicaciónConcesión
Número de solicitudCN 201110193465
Fecha de publicación18 Nov 2015
Fecha de presentación12 Jul 2011
Fecha de prioridad12 Jul 2011
También publicado comoCN102875283A
Número de publicación201110193465.X, CN 102875283 B, CN 102875283B, CN 201110193465, CN-B-102875283, CN102875283 B, CN102875283B, CN201110193465, CN201110193465.X
Inventores齐国祯, 钟思青, 李晓红, 王洪涛
Solicitante中国石油化工股份有限公司, 中国石油化工股份有限公司上海石油化工研究院
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Enlaces externos:  SIPO, Espacenet
由甲醇和石脑油制备低碳烯烃的方法 Prepared by the method of methanol and naphtha, light olefins traducido del chino
CN 102875283 B
Resumen  traducido del chino
本发明涉及一种由甲醇和石脑油制备低碳烯烃的方法,主要解决现有技术中低碳烯烃收率低的问题。 The present invention relates to a method for producing light olefins methanol and naphtha, mainly to solve the prior art problem of a low yield of light olefins. 本发明通过采用主要包括以下步骤:(1)包括石脑油的原料进入第一反应区,产品物流和催化剂进入沉降器;甲醇原料进入第二反应区,产品物流和催化剂进入第三反应区,生成的产品物流和催化剂进入沉降器;(2)沉降器中气相物流进入分离工段,分离出包括低碳烯烃、C4~C8混合烃的产品,其中C4~C8混合烃的物流进入第四反应区,产品物流和催化剂进入第三反应区;(3)沉降器中催化剂进入再生器,再生后的催化剂分为三部分,一部分进入第一反应区,一部分进入第二反应区,一部分进入第四反应区的技术方案较好地解决了上述问题,可用于低碳烯烃的工业生产中。 By using the present invention includes the following steps: (1) comprises a naphtha feedstock into the first reaction zone, the product stream and the catalyst into the settling vessel; methanol feed to the second reaction zone, the product stream and the catalyst into the third reaction zone, the resulting product stream and catalyst into the settler; (2) settler vapor stream enters the separation section separated include olefins, C4 ~ C8 mixed hydrocarbon products, including C4 ~ C8 mixed hydrocarbon stream into the fourth reaction zone , the product stream and the catalyst into the third reaction zone; (3) settling the catalyst enters the regenerator vessel, the regenerated catalyst is divided into three parts, one part into the first reaction zone, a portion into the second reaction zone, a portion into the fourth reaction technical program areas can solve the above problems, it can be used for industrial production of light olefins.
Reclamaciones(5)  traducido del chino
1.一种由甲醇和石脑油制备低碳烯烃的方法,主要包括以下步骤: (1)包括石脑油的原料从第一反应区底部或沿第一反应区轴向方向上隔开的至少一个进料口的至少一个位置进入第一反应区,生成的产品物流和催化剂进入沉降器;包括甲醇的原料进入第二反应区,生成的产品物流和催化剂进入第三反应区,第三反应区生成的产品物流和催化剂进入沉降器; (2)沉降器中气相物流与催化剂分离后进入分离工段,分离出包括低碳烯烃、C4〜CS混合烃的产品,其中包括C4〜CS混合烃的物流进入第四反应区,生成的产品物流和催化剂进入第三反应区; (3)沉降器中催化剂经汽提后进入再生器再生,再生后的催化剂分为三部分,一部分进入第一反应区,一部分进入第二反应区,一部分进入第四反应区; 所述再生后的催化剂积炭量质量分数为0.0l〜0.5% ; 所述第一反应区进料中还包括水蒸气,水蒸气与石脑油的重量比为0.05〜1.5:1 ;第三反应区进料中主要为甲醇; 所述包括C4〜CS混合烃的物流从第四反应区底部或从沿轴向方向上隔开的至少一个进料口进入第四反应区; 所述第一反应区为提升管;第二反应区为提升管;第三反应区为快速床;第四反应区为提升管; 所述第一反应区中反应条件为:反应温度为570〜670°C,反应压力以表压计为0.01〜0.3MPa,气相线速为4〜10米/秒;第二反应区中反应条件为:反应温度为480〜6000C,反应压力以表压计为0.01〜0.3MPa,气相线速为4〜10米/秒;第三反应区中反应条件为:反应温度为480〜600°C,反应压力以表压计为0.01〜0.3MPa,气相线速为I〜3米/秒;第四反应区中反应条件为:反应温度为530〜630°C,反应压力以表压计为0.01〜0.3MPa,气相线速为4〜10米/秒。 1. A process for the preparation of methanol and naphtha, light olefins, including the following steps: (1) including naphtha feedstock from the bottom of the first reaction zone or axial direction along the first reaction zone spaced at least one location of the at least one feed opening into the first reaction zone, the product stream and the catalyst into the settler generated; feedstock comprising methanol into the second reaction zone, the product stream and the catalyst into the third reaction zone generated, the third reaction product stream and catalyst into the area generated by a settler; (2) of the settler gaseous stream separated from the catalyst into the separation section separated include olefins, C4~CS mixed hydrocarbon products, including mixed hydrocarbons C4~CS stream entering the fourth reaction zone, the product stream and a catalyst generated into the third reaction zone; (3) the catalyst settler after stripping regenerated into the regenerator, regenerated catalyst is divided into three parts, one part into the first reaction zone , a portion of the reaction zone into the second part into the fourth reaction zone; the catalyst coke content of the regenerated amount is 0.0l~0.5%; the first reaction zone feed further comprises steam, water vapor and 0.05~1.5 naphtha weight ratio: 1; the third reaction zone feed mainly methanol; the mixed hydrocarbon stream comprises C4~CS from the fourth or bottom of the reaction zone spaced from the axial direction at least one feed inlet into the fourth reaction zone; said first reaction zone for the riser; the second reaction zone to the riser; third reaction zone for quick bed; fourth reaction zone of the riser; the first reactor Area reaction conditions: reaction temperature is 570~670 ° C, the reaction pressure gauge pressure is 0.01~0.3MPa, vapor line speed is 4~10 m / s; second reaction zone reaction conditions: reaction temperature 480~6000C, reaction pressure gauge pressure is 0.01~0.3MPa, vapor line speed is 4~10 m / s; the third reaction zone reaction conditions: reaction temperature is 480~600 ° C, the reaction pressure to gauge counted as 0.01~0.3MPa, vapor line speed of I~3 m / sec; fourth reaction zone reaction conditions: reaction temperature is 530~630 ° C, the reaction pressure gauge pressure is 0.01~0.3MPa, vapor line speed of 4~10 m / s.
2.根据权利要求1所述由甲醇和石脑油制备低碳烯烃的方法,其特征在于所述催化剂包括ZSM-5分子筛,S12Al2O3摩尔比为10〜100。 The methanol and naphtha by the method of preparation of lower olefins according to claim 1, characterized in that said catalyst comprises a ZSM-5 zeolite, S12Al2O3 molar ratio of 10~100.
3.根据权利要求1所述由甲醇和石脑油制备低碳烯烃的方法,其特征在于所述石脑油馏程在20°C〜220°C之间。 3. The methanol and naphtha by the method of preparation of lower olefins according to claim 1, wherein said naphtha boiling point range between 20 ° C~220 ° C.
4.根据权利要求1所述由甲醇和石脑油制备低碳烯烃的方法,其特征在于所述再生后的催化剂活性指数大于0.8。 4. prepared from methanol and naphtha to light olefins method according to claim 1, characterized in that the catalyst activity after regeneration index greater than 0.8.
5.根据权利要求1所述由甲醇和石脑油制备低碳烯烃的方法,其特征在于所述再生后的催化剂分为三部分,20〜40%重量进入第一反应区,20〜40%重量进入第二反应区,20〜60%重量进入第四反应区。 5. The prepared from methanol and naphtha to light olefins method according to claim 1, characterized in that the regenerated catalyst is divided into three parts, 20~40% by weight into the first reaction zone, 20~40% by weight into the second reaction zone, 20~60 wt% into the fourth reaction zone.
Descripción  traducido del chino
由甲醇和石脑油制备低碳烯烃的方法 Prepared by the method of methanol and naphtha, light olefins

技术领域 TECHNICAL FIELD

[0001] 本发明涉及一种由甲醇和石脑油制备低碳烯烃的方法。 [0001] The present invention relates to a methanol and naphtha produce light olefins.

技术背景 BACKGROUND

[0002] 低碳烯烃,即乙烯和丙烯,是两种重要的基础化工原料,其需求量在不断增加。 [0002] olefins, namely ethylene and propylene, are two important basic chemical raw materials, the demand is increasing. 一般地,乙烯、丙烯是通过石油路线来生产,但由于石油资源有限的供应量及较高的价格,由石油资源生产乙烯、丙烯的成本不断增加。 Generally, ethylene, propylene is produced by the oil route, but due to the limited supply of oil resources and higher prices, the cost of oil resources by the production of ethylene, propylene increasing. 近年来,人们开始大力发展替代原料转化制乙烯、丙烯的技术。 In recent years, people began to develop alternative feedstock into ethylene, propylene technology. 其中,一类重要的用于轻质烯烃生产的替代原料是含氧化合物,例如醇类(甲醇、乙醇)、醚类(二甲醚、甲乙醚)、酯类(碳酸二甲酯、甲酸甲酯)等,这些含氧化合物可以通过煤、天然气、生物质等能源转化而来。 Wherein, important class of alternative raw materials for the production of light olefins are oxygenates, such as alcohols (methanol, ethanol), ethers (dimethyl ether, methyl ethyl ether), esters (dimethyl carbonate, methyl formate ester), etc. These can be converted from oxygen-containing compounds by coal, natural gas, biomass and other energy sources. 某些含氧化合物已经可以达到较大规模的生产,如甲醇,可以由煤或天然气制得,工艺十分成熟,可以实现上百万吨级的生产规模。 Certain oxygenates can already achieve large-scale production, such as methanol, can be obtained from coal or natural gas, technology is very mature, can achieve megaton scale of production. 由于含氧化合物来源的广泛性,再加上转化生成轻质烯烃工艺的经济性,所以由含氧化合物转化制烯烃(OTO)的工艺,特别是由甲醇转化制烯烃(MTO)的工艺受到越来越多的重视。 Due to extensive source of oxygen-containing compounds, plus generate light olefins conversion process of the economy, so-to-olefin (OTO) from the oxygenate conversion process, in particular by the conversion of methanol to olefins (MTO) process more increasingly more attention.

[0003] 石脑油是一种轻质油品,由原油蒸馏或石油二次加工切取相应馏分而得。 [0003] Naphtha is a light oil from the distillation of crude oil or petroleum secondary processing corresponding cut fractions derived. 其沸点范围依需要而定,通常为较宽的馏程,如20-220°C。 Its boiling point range as necessary, and generally for the wider distillation range, such as 20-220 ° C. 石脑油是管式炉裂解制取乙烯,丙烯及催化重整制取苯、甲苯、二甲苯的重要原料。 Naphtha is a tube furnace cracking takes ethylene, propylene and catalytic reforming take an important raw material, benzene, toluene, xylene. 作为裂解原料,要求石脑油组成中烷烃和环烷烃的含量不低于70% (体积)。 As cracking feedstock, naphtha requirements consisting of alkanes and cycloalkanes content is not less than 70% (by volume). 石脑油催化裂解制低碳烯烃则是在催化剂存在的条件下,对石油烃类进行裂解来获得低碳烯烃的生产过程。 Catalytic cracking of naphtha to light olefins is in the presence of a catalyst, cracking of petroleum hydrocarbons to obtain light olefins production process. 同传统的管式炉蒸汽热裂解相比,该过程反应温度比蒸汽裂解反应约低50〜200°C,能耗显著降低;裂解炉管内壁结焦速率也会降低,从而可延长操作周期,增加炉管寿命;同时二氧化碳排放也会降低,减轻了污染,并可灵活调整产品结构。 Compared with conventional tube cracking furnace steam heat, the process reaction temperature than the steam cracking reactions about low 50~200 ° C, significantly reducing energy consumption; cracking furnace tube wall coking rate will be reduced, and thus extend the operation period, an increase of furnace tube life; at the same time will reduce carbon dioxide emissions, reduce pollution, and flexible adjustment of product structure.

[0004] US6166282中公布了一种氧化物转化为低碳烯烃的技术和反应器,采用快速流化床反应器,气相在气速较低的密相反应区反应完成后,上升到内径急速变小的快分区后,采用特殊的气固分离设备初步分离出大部分的夹带催化剂。 [0004] US6166282 published an oxide is converted to light olefins and reactor technology, using fast fluidized bed reactor, the gas phase in the gas velocity lower dense phase reaction zone of the reactor is completed, up to the inner diameter of rapid change After small fast partition, using a special gas-solid separation equipment initially isolated from most of the entrained catalyst. 由于反应后产物气与催化剂快速分离,有效的防止了二次反应的发生。 Since the reaction product gas and catalyst rapid separation, effectively preventing the occurrence of secondary reactions. 经模拟计算,与传统的鼓泡流化床反应器相比,该快速流化床反应器内径及催化剂所需藏量均大大减少。 After the simulation, compared with the conventional bubbling fluidized bed reactor, the fast fluidized bed reactor volume required to hiding diameter and catalyst greatly reduced.

[0005] CN1723262中公布了带有中央催化剂回路的多级提升管反应装置用于氧化物转化为低碳烯烃工艺,该套装置包括多个提升管反应器、气固分离区、多个偏移元件等,每个提升管反应器各自具有注入催化剂的端口,汇集到设置的分离区,将催化剂与产品气分开。 [0005] CN1723262 announced a multi-stage riser reactor loop with a central catalyst for the conversion of oxygenates to light olefins process, the set of devices includes a plurality of riser reactor, gas-solid separation zone, a plurality of offset elements, etc., each riser reactor each having a catalyst injection port, bringing together to set up a separation zone, the catalyst is separated from the product gas. 但该方法存在低碳烯烃收率较低的缺点。 However, this method has the disadvantage of a low yield of light olefins.

[0006] EP0448000和EP0882692中公布了一种甲醇生产丙烯的方法,甲醇首先转化为DME和水,然后将混合物输送到第一台反应器,并向该反应器中加入蒸汽。 [0006] EP0448000 and EP0882692 published a methanol production method of propylene, methanol is converted to DME and water first, and then the mixture was fed to the first reactor, and adding steam to the reactor. 在第一反应器中甲醇和(或)二甲醚或其混合物与催化剂接触进行反应,催化剂采用含ZnO和CdO的专用ZSM-5催化剂,反应温度280〜570°C,压力0.01〜0.1MPa,制备得到以丙烯为主要烃类的产品。 Methanol and (or) dimethyl ether or a mixture thereof contact with the catalyst in the first reactor in the reactor, the catalyst ZSM-5 catalyst using special containing ZnO and CdO, the reaction temperature 280~570 ° C, pressure 0.01~0.1MPa, prepared propylene as the main hydrocarbon products. 较重产物如C5+烃继续在第二台反应器中进行反应转化为以丙烯为主的烃类,经冷却后送回分离器。 Heavy products such as C5 + hydrocarbon conversion reaction to proceed to a propylene-based hydrocarbons in the second reactor, cooled and sent back to the separator. 产品经压缩、进一步精制后可得到纯度为97%的化学级丙烯。 Products by compression, after further refined to a purity of 97% of chemical grade propylene. 但是该工艺中采用多个固定床反应器,由于催化剂的活性限制,因此需要频繁切换操作,而且取热问题也很复杂。 However, a plurality of fixed bed reactors used in this process, due to the limitation of the catalyst activity, requiring frequent switching operation, and the problem is very complex heat removal.

[0007] US 20070083071公布了一种烃催化裂解生产乙烯、丙烯的工艺方法,烃原料在催化裂解炉中转化为包括低碳烯烃的产品,然后将产品物流通过一系列工艺分离成C2〜C3烷烃、C2〜C3烯烃、C4+烃三种物流,将C2〜C3烷烃返回管式裂解炉进行热裂解,C4+烃返回催化裂解炉进行催化裂解,最终得到较高收率的乙烯、丙烯产品。 [0007] US 20070083071 discloses an catalytic cracking of hydrocarbons to produce ethylene, propylene process, the hydrocarbon feedstock is converted to products comprising light olefins in catalytic cracking furnace, and then separating the product stream through a series of processes into C2~C3 alkane , C2~C3 olefins, C4 + hydrocarbons three streams, will C2~C3 paraffin return tube cracking furnace pyrolysis, C4 + hydrocarbon catalytic cracking furnace return catalytic cracking and eventually get a higher yield of ethylene and propylene products. 该方法采用提升管反应器,反应物停留时间较短,低碳烯烃产品单程收率较低。 The method uses a riser reactor, the reactants residence time is shorter, one-pass yield lower olefins products.

[0008] 由于石脑油催化裂解和甲醇转化制烯烃反应的目的产物一一低碳烯烃相同,而且各自产品中的主要组分种类大致相同,采用的催化剂体系也大致相同,而从反应机理角度讲,都存在由大分子烃或中间体裂解为小分子烃类的过程,因此这两种工艺技术是有条件进行耦合的。 [0008] Since the purpose of the product of naphtha cracking and catalytic conversion of methanol to olefins reaction of one same light olefins, and the main component species in their product is substantially the same, the catalyst system used is almost the same, but from the perspective of the reaction mechanism speaking, both by the presence of hydrocarbon molecules into small molecules or intermediate hydrocarbon cracking process, so these two technology is conditional coupling of. 本发明有针对性的解决了该问题。 The present invention is targeted to solve this problem.

发明内容 SUMMARY OF THE INVENTION

[0009] 本发明所要解决的技术问题是现有技术中存在的低碳烯烃收率不高的问题,提供一种新的由甲醇和石脑油制备低碳烯烃的方法。 [0009] The technical problem to be solved by the present invention is the yield of light olefins present in the prior art is not high, to provide a new preparation from methanol and naphtha, low-carbon olefins. 该方法用于低碳烯烃的生产中,具有低碳烯烃收率较高的优点。 The process for the production of olefins, having the advantage of higher yields of light olefins.

[0010] 为解决上述问题,本发明采用的技术方案如下:一种由甲醇和石脑油制备低碳烯烃的方法,主要包括以下步骤:(I)包括石脑油的原料从第一反应区底部或沿第一反应区轴向方向上隔开的至少一个进料口的至少一个位置进入第一反应区,生成的产品物流和催化剂进入沉降器;包括甲醇的原料进入第二反应区,生成的产品物流和催化剂进入第三反应区,第三反应区生成的产品物流和催化剂进入沉降器;(2)沉降器中气相物流与催化剂分离后进入分离工段,分离出包括低碳烯烃、C4〜CS混合烃的产品,其中包括C4〜CS混合烃的物流进入第四反应区,生成的产品物流和催化剂进入第三反应区;(3)沉降器中催化剂经汽提后进入再生器再生,再生后的催化剂分为三部分,一部分进入第一反应区,一部分进入第二反应区,一部分进入第四反应区。 [0010] In order to solve the above problems, the technical aspect of the present invention is used as follows: A process for the production of methanol and naphtha, light olefins, including the following steps: (I) comprises a naphtha feedstock from the first reaction zone the bottom of the first reaction zone or along the axial direction of the at least one location spaced from the at least one feed opening into the first reaction zone, the product stream and the catalyst into the settler generated; feedstock comprising methanol into the second reaction zone to produce The product stream and catalyst into the third reaction zone, the product stream and the catalyst into the third reaction zone to generate a settler; (2) sedimentation vessel into the gaseous stream separated from the catalyst separation section to separate the light olefins including, C4~ CS mixed hydrocarbon products, including C4~CS mixed hydrocarbon stream into the fourth reaction zone, the product stream and a catalyst generated into the third reaction zone; (3) the catalyst settler after stripping into the regenerator the regeneration After the catalyst is divided into three parts, one part into the first reaction zone, part of the reaction zone into the second part of the reaction zone into the fourth.

[0011] 上述技术方案中,所述催化剂包括ZSM-5分子筛,S12Al2O3摩尔比为10〜100 ;所述再生后的催化剂积炭量质量分数为0.01〜0.5% ;所述第一反应区进料中还包括水蒸气,水蒸气与石脑油的重量比为0.05〜1.5: I;第三反应区进料中主要为甲醇;所述石脑油馏程在20°C〜220°C之间;所述第一反应区中反应条件为:反应温度为570〜670°C,反应压力以表压计为0.01〜0.3MPa,气相线速为4〜10米/秒;第二反应区中反应条件为:反应温度为480〜600°C,反应压力以表压计为0.01〜0.3MPa,气相线速为4〜10米/秒;第三反应区中反应条件为:反应温度为480〜600 °C,反应压力以表压计为0.01〜0.3MPa,气相线速为I〜3米/秒;第四反应区中反应条件为:反应温度为530〜630°C,反应压力以表压计为0.01〜0.3MPa,气相线速为4〜10米/秒;所述包括C4〜C8混合烃的物流从第四反应区底部或从沿轴向方向上隔开的至少一个进料口进入第四反应区;所述再生后的催化剂活性指数大于0.8 ;所述第一反应区为提升管;第二反应区为提升管;第三反应区为快速床;第四反应区为提升管;所述再生后的催化剂分为三部分,20〜40%重量进入第一反应区,20〜40%重量进入第二反应区,20〜60%重量进入第四反应区。 [0011] the above technical solution, the catalyst comprises a ZSM-5 zeolite, S12Al2O3 molar ratio of 10~100; the mass fraction of the amount of coke catalyst regeneration is 0.01~0.5%; the first reaction zone feed also includes water vapor, steam and naphtha weight ratio of 0.05~1.5: I; the third reaction zone feed is primarily methanol; between 20 ° C~220 ° C the naphtha distillation range ; said first reaction zone reaction conditions: reaction temperature is 570~670 ° C, the reaction pressure gauge pressure is 0.01~0.3MPa, vapor line speed is 4~10 m / s; second reaction zone reaction conditions: the reaction temperature is 480~600 ° C, the reaction pressure gauge pressure is 0.01~0.3MPa, vapor line speed is 4~10 m / s; the third reaction zone reaction conditions: reaction temperature is 480~600 ° C, the reaction pressure gauge pressure is 0.01~0.3MPa, vapor line speed of I~3 m / sec; fourth reaction zone reaction conditions: reaction temperature is 530~630 ° C, the reaction pressure gauge pressure as 0.01~0.3MPa, vapor line speed is 4~10 m / sec; the mixed hydrocarbon stream comprises C4~C8 from fourth into the first reaction zone or spaced from the bottom of the axial direction of at least one inlet Four reaction zone; the catalyst activity after regeneration index greater than 0.8; the first riser reaction zone is; the second reaction zone to the riser; third reaction zone for quick bed; fourth reaction zone of the riser; the said regenerated catalyst is divided into three parts, 20~40% by weight into the first reaction zone, 20~40% by weight into the second reaction zone, 20~60% by weight of the reaction zone into the fourth.

[0012] 再生催化剂活性指数用于体现失活催化剂的再生程度,以新鲜催化剂为基准,以固定条件下各催化剂转化轻石脑油的量进行相对比较,计算方法为:再生催化剂活性指数=(一定条件下再生催化剂转化的轻石脑油量/一定条件下新鲜催化剂转化的轻石脑油量)X 100%。 [0012] The regenerated catalyst activity index reflects the degree of regeneration for the deactivated catalyst to fresh catalyst as a benchmark to each catalyst under fixed conditions of light naphtha conversion amount relatively, calculated as: regenerated catalyst activity index = ( light naphtha amount of fresh catalyst converted under certain conditions, the regenerated catalyst under conversion amount of light naphtha / certain conditions) X 100%. 所述一定条件或固定条件是指采用流化床反应器,在反应温度为600°C、反应压力以表压计为0、气相停留时间为4秒的反应条件。 The certain condition or fixed condition refers to the use of a fluidized bed reactor, at a reaction temperature of 600 ° C, the reaction pressure is zero gauge pressure, vapor residence time of 4 seconds of reaction conditions.

[0013] 本发明所述的ZSM-5分子筛可以采用本领域所公知的方法,如水热合成法,进行制备,在所述分子筛催化剂上会选择性的负载具有脱氢功能的金属,脱氢功能的金属选自元素周期表中IB、IIB、VB、VIB、VIIB或VIII族中的至少一种,而将脱氢功能的金属负载于ZSM-5分子筛上的方法可采用本领域所公知的方法,如浸渍法或共沉淀法。 [0013] ZSM-5 zeolite of the present invention can be in the art known method is used, water hot synthesis, prepared on the molecular sieve catalyst can selectively load dehydrogenation functional metal, dehydrogenation function at least one metal selected from the Periodic Table IB, IIB, VB, VIB, VIIB or VIII of, and dehydrogenation function of the metal supported on ZSM-5 zeolite method known in the art may be used in this method such as impregnation or co-precipitation method. 负载脱氢功能金属的ZSM-5分子筛制备好后,加入粘结剂,做成混合浆料,采用喷雾干燥方法进行干燥成型,然后将成型后的催化剂粉末置于焙烧炉中进行焙烧,冷却后得到催化剂样品。 After loading dehydrogenation function metal ZSM-5 zeolite preparation is completed, adding a binder, made of mixed slurry, spray drying method for drying the molding, and then the catalyst powder after molding into roaster roasting, cooling to obtain a catalyst sample. 粘结剂可选择Si02、Al2O3等。 Binder choose Si02, Al2O3 and the like.

[0014] 采用本发明的方法,设置四个反应区,第一反应区主要用于石脑油催化裂解为低碳烯烃,第二反应区主要用于转化甲醇,第三反应区主要用于转化第二反应区和第四反应区中的气相物质,第四反应区主要用于转化C4〜CS混合烃副产物,而且在第一反应区、第四反应区采用轴向进料方式,降低原料分压,以期提高低碳烯烃转化率。 [0014] The method of the present invention, a four reaction zone, the first reaction zone is mainly used for catalytic cracking of naphtha to light olefins, mainly used in the second reaction zone the conversion of methanol, is mainly used for transformation of the third reaction zone the second reaction zone and a fourth vapor phase material in the reaction zone, a fourth reaction zone is mainly used for transformation C4~CS mixed hydrocarbon by-products, but also in the first reaction zone, a fourth reaction zone using the axial feed mode, to reduce raw materials partial pressure, in order to improve the conversion rate of light olefins. 本发明中沉降器和再生器可分开布置或可同轴设置,第一、第二、第三、第四反应区公用一个沉降器。 The present invention settlement and regenerator can be arranged separately or disposed coaxially, the first, second, third, fourth reaction zone a settler public. 第四反应区为第三反应区提供反应物和催化剂,同时起到为第三反应区降温的目的。 Fourth reaction zone to provide a third reaction zone the reactants and the catalyst, for the same time play the purpose of cooling the third reaction zone is. 因此,采用本发明的方法,不但实现能量优化,而且将甲醇和石脑油转化制备低碳烯烃耦合在一起,同时转化掉生成的高碳烃副产物,达到了提高低碳烯烃选择性的目的。 Accordingly, the present invention is a method, not only to achieve energy optimization, and the conversion of methanol to light olefins and naphtha coupled prepared together while the conversion of higher hydrocarbons generated off byproducts, the selectivity to achieve the purpose of improving light olefins .

[0015] 采用本发明的技术方案:所述催化剂包括ZSM-5分子筛,S12Al2O3摩尔比为10〜100 ;所述再生后的催化剂积炭量质量分数为0.01〜0.5% ;所述第一反应区进料中还包括水蒸气,水蒸气与石脑油的重量比为0.05〜1.5: I ;第三反应区进料中主要为甲醇;所述石脑油馏程在20°C〜220°C之间;所述第一反应区中反应条件为:反应温度为570〜6700C,反应压力以表压计为0.01〜0.3MPa,气相线速为4〜10米/秒;第二反应区中反应条件为:反应温度为480〜600°C,反应压力以表压计为0.01〜0.3MPa,气相线速为4〜10米/秒;第三反应区中反应条件为:反应温度为480〜600 °C,反应压力以表压计为0.0I〜0.3MPa,气相线速为I〜3米/秒;第四反应区中反应条件为:反应温度为530〜630°C,反应压力以表压计为0.01〜0.3MPa,气相线速为4〜10米/秒;所述包括C4〜C8混合烃的物流从第四反应区底部或从沿轴向方向上隔开的至少一个进料口进入第四反应区;所述再生后的催化剂活性指数大于0.8 ;所述第一反应区为提升管;第二反应区为提升管;第三反应区为快速床;第四反应区为提升管;所述再生后的催化剂分为三部分,20〜40%重量进入第一反应区,20〜40%重量进入第二反应区,20〜60%重量进入第四反应区,低碳烯烃碳基收率可达到65.06%重量,取得了较好的技术效果。 [0015] The technical solution of the present invention: the catalyst comprises a ZSM-5 zeolite, S12Al2O3 molar ratio of 10~100; the amount of the regenerated catalyst coke mass fraction 0.01~0.5%; the first reaction zone They feed also include water vapor, water vapor and the weight ratio of naphtha 0.05~1.5: I; the third reaction zone feed mainly methanol; the naphtha boiling point range between 20 ° C~220 ° C ; said first reaction zone in the reaction conditions: reaction temperature is 570~6700C, reaction pressure gauge pressure is 0.01~0.3MPa, vapor line speed is 4~10 m / s; second reaction zone reaction conditions: the reaction temperature is 480~600 ° C, the reaction pressure gauge pressure is 0.01~0.3MPa, vapor line speed is 4~10 m / s; the third reaction zone reaction conditions: reaction temperature is 480~600 ° C, the reaction pressure gauge pressure is 0.0I~0.3MPa, vapor line speed of I~3 m / sec; fourth reaction zone reaction conditions: reaction temperature is 530~630 ° C, the reaction pressure to gauge counted as 0.01~0.3MPa, vapor line speed is 4~10 m / sec; the mixed hydrocarbon stream comprises C4~C8 enter from the bottom of the fourth reaction zone or spaced from the axial direction of at least one inlet fourth reaction zone; the catalyst activity after regeneration index greater than 0.8; the first riser reaction zone is; the second reaction zone to the riser; third reaction zone for quick bed; fourth reaction zone to the riser; The regenerated catalyst is divided into three parts, 20~40% by weight into the first reaction zone, 20~40% by weight into the second reaction zone, 20~60% by weight into the fourth reaction zone, olefins carbon-based income rate could reach 65.06% by weight, and achieved good technical results.

附图说明 Brief Description

[0016] 图1为本发明所述方法的流程示意图。 [0016] FIG. 1 a schematic flow diagram of the method of the present invention.

[0017] 图1中,I为再生介质入口管线;2为待生塞阀;3为再生器;4为缓冲区;5为再生斜管输送蒸汽入口;6为第二反应区进料;7为第四反应区进料;8为缓冲区;9为第一反应区和第四反应区侧面进料口;10为第二反应区;11为待生立管;12为第三反应区;13为汽提介质入口管线;14为第一反应区出口粗旋;15为气固旋风分离器;16为烟气出口;17为沉降器;18为汽提器;19为第一反应区;20为第三反应区出口粗旋;21为第一反应区进料;22为产品出口管线;23为第四反应区;24为第三反应区进料;25为气固旋风分离器;26为再生斜管;27为再生斜管;28为再生斜管;29为缓冲区。 [0017] FIG. 1, I to regeneration medium inlet line; 2 is the spent plug valve; 3 regenerator; 4 buffer; for the regeneration inclined pipe 5 conveying the steam inlet; 6 for the second reaction zone feed; 7 for the fourth reaction zone feed; the buffer 8; 9 is the first reaction zone and a fourth side reaction zone inlet; 10 is a second reaction zone; 11 is the spent riser; 12 for the third reaction zone; 13 is a stripping medium inlet line; 14 is a first reaction zone outlet crude spin; 15 gas-solid cyclones; flue gas outlet 16; 17 settler; stripper 18; 19 is the first reaction zone; 20 for the third reaction zone export crude spin; 21 is the first reaction zone feed; 22 export pipeline; 23 for the fourth reaction zone; 24 for the third reaction zone feed; 25 is a gas-solid cyclones; 26 regenerative inclined tube; 27 is inclined tube regeneration; regeneration inclined pipe 28; 29 buffer.

[0018] 包括石脑油的原料从第一反应区19底部或沿第一反应区轴向方向上隔开的至少一个进料口9的至少一个位置进入第一反应区19,生成的产品物流和催化剂进入沉降器17 ;包括甲醇的原料进入第二反应区10,生成的产品物流和催化剂进入第三反应区12,第三反应区12生成的产品物流和催化剂进入沉降器17,沉降器17中气相物流与催化剂分离后进入分离工段,分离出包括低碳烯烃、C4〜CS混合烃的产品,其中包括C4〜CS混合烃的物流进入第四反应区23,生成的产品物流和催化剂进入第三反应区12,沉降器17中催化剂经汽提后进入再生器3再生,再生后的催化剂分为三部分,一部分进入第一反应区19,一部分进入第二反应区10,一部分进入第四反应区23。 [0018] 19 include a naphtha feedstock from a bottom of the first reaction zone or along the axial direction of the first reaction zone is separated from the at least one feed port 9 at least one position into the first reaction zone 19, the resulting product stream and catalyst into the settler 17; includes methanol feedstock into the second reaction zone 10, the product stream and a catalyst generated into the third reaction zone 12, a third reaction product stream and a catalyst into the settling zone 12 produced 17, settler 17 After separating the gaseous stream entering the catalyst separation section, separated include olefins, C4~CS mixed hydrocarbon products, including C4~CS mixed hydrocarbon stream into the fourth reaction zone 23, the product stream and catalyst into the first generation Third reaction zone 12, the catalyst settler vessel 17 after stripping regenerated into the regenerator 3, the regenerated catalyst is divided into three parts, one part into the first reaction zone 19, a portion into the second reaction zone 10, a portion into the fourth reaction District 23.

[0019] 下面通过实施例对本发明作进一步的阐述,但不仅限于本实施例。 [0019] The following Examples of the present invention will be further illustrated, but is not limited to this embodiment.

具体实施方式 detailed description

[0020]【实施例1】 [0020] [Example 1]

[0021] 在如图1所示的反应装置中,催化剂为ZSM-5,S12Al2O3摩尔比为100,负载Cu/Zn/Co,负载金属质量占催化剂质量的百分数为Cu:5.53 ;Zn:2.76 ;Co:1.68。 [0021] In the reaction apparatus shown in Figure 1, the catalyst is ZSM-5, S12Al2O3 molar ratio of 100, the load Cu / Zn / Co, the quality of the supported metal catalyst mass percentage of Cu: 5.53; Zn: 2.76; Co: 1.68. 包括石脑油的原料从第一反应区底部进入第一反应区,生成的产品物流和催化剂进入沉降器;甲醇的原料进入第二反应区,生成的产品物流和催化剂进入第三反应区,第三反应区生成的产品物流和催化剂进入沉降器,沉降器中气相物流与催化剂分离后进入分离工段,分离出包括低碳烯烃、C4〜CS混合烃的产品,其中C4〜CS混合烃的物流进入第四反应区,生成的产品物流和催化剂进入第三反应区,沉降器中催化剂经汽提后进入再生器再生,再生后的催化剂分为三部分,20 %重量进入第一反应区,20 %重量进入第二反应区,60 %重量进入第四反应区。 Including naphtha feedstock from the bottom of the first reaction zone into the first reaction zone, the product stream and a catalyst generated into the settler; methanol feedstock into the second reaction zone, the product stream and catalyst into the third generation of the reaction zone, the first Three product stream and a catalyst into the reaction zone is generated by a settler after settler vapor stream separated from the catalyst into the separation section separated include olefins, C4~CS mixed hydrocarbon products, including C4~CS mixed hydrocarbon stream into the The fourth reaction zone, the product stream and catalyst into the third generation of the reaction zone, settler catalyst into the regenerator after stripping regeneration, the regenerated catalyst is divided into three parts, 20% by weight into the first reaction zone, 20% by weight into the second reaction zone, 60% by weight into the fourth reaction zone. 第一反应区为提升管;第二反应区为提升管;第三反应区为快速床;第四反应区为提升管。 The first reaction zone is a riser; the second reaction zone to the riser; third reaction zone for quick bed; fourth reaction zone to the riser. 再生后的催化剂积炭量质量分数为0.01 %,第一反应区进料中还包括水蒸气,水蒸气与石脑油的重量比为1.5: 1,第三反应区进料中为甲醇,石脑油组成见表I。 The amount of the catalyst coke content after regeneration was 0.01%, the feed to the first reaction zone further comprises steam, steam and naphtha weight ratio of 1.5: 1, the third reaction zone feed is methanol, the stone Brain oil composition shown in Table I. 第一反应区中反应条件为:反应温度为570°C,反应压力以表压计为0.0lMPa,气相线速为4米/秒;第二反应区中反应条件为:反应温度为480°C,反应压力以表压计为0.0lMPa,气相线速为4米/秒;第三反应区中反应条件为:反应温度为482°C,反应压力以表压计为0.0lMPa,气相线速为I米/秒;第四反应区中反应条件为:反应温度为530°C,反应压力以表压计为0.01〜MPa,气相线速为4米/秒。 The first reaction zone reaction conditions: reaction temperature is 570 ° C, the reaction pressure gauge pressure is 0.0lMPa, vapor line speed of 4 m / sec; the second reaction zone reaction conditions: reaction temperature is 480 ° C The reaction pressure gauge pressure is 0.0lMPa, vapor line speed of 4 m / sec; third reaction zone reaction conditions: reaction temperature of 482 ° C, the reaction pressure gauge pressure is 0.0lMPa, Gas linear speed I m / s; fourth reaction zone reaction conditions: reaction temperature of 530 ° C, the reaction pressure gauge pressure is 0.01~MPa, vapor line speed of 4 m / sec. C4〜CS混合烃的物流从第四反应区底部进入第四反应区。 C4~CS mixed hydrocarbon stream into the fourth reaction zone from the bottom fourth reaction zone. 再生后的催化剂活性指数为0.93。 The regenerated catalyst activity index was 0.93. 甲醇与石脑油进料重量比为1:1。 Methanol and naphtha feedstock weight ratio of 1: 1. 保持催化剂流动控制的稳定性,产品气采用在线气相色谱分析,低碳烯烃碳基收率为59.28%重量。 Maintain the stability of the catalyst flow control, product gas using online gas chromatography analysis, a yield of lower olefins carbon 59.28% by weight of the base.

[0022]【实施例2】 [0022] [Example 2]

[0023] 按照实施例1所述的条件和步骤,催化剂为ZSM-5,S12Al2O3摩尔比为10,包括石脑油的原料从第一反应区底部和沿第一反应区轴向方向上的一个进料口进入第一反应区,该进料口距离第一反应区底部为1/2第一反应区高度。 [0023] As described conditions and procedures described in Example 1, the catalyst is a ZSM-5, S12Al2O3 molar ratio of 10, a naphtha feedstock comprising a first reaction zone and from the bottom along the axial direction of the first reaction zone a feed port into the first reaction zone, the distance between the first feed port at the bottom of the reaction zone is 1/2 the height of the first reaction zone. 再生后的催化剂分为三部分,40%重量进入第一反应区,40 %重量进入第二反应区,20 %重量进入第四反应区。 The regenerated catalyst is divided into three parts, 40% by weight into the first reaction zone, 40% by weight into the second reaction zone, 20% by weight into the fourth reaction zone. 再生后的催化剂积炭量质量分数为0.5%,第一反应区进料中还包括水蒸气,水蒸气与石脑油的重量比为0.05: 10第一反应区中反应条件为:反应温度为670°C,反应压力以表压计为0.0lMPa,气相线速为10米/秒;第二反应区中反应条件为:反应温度为600°C,反应压力以表压计为0.0lMPa,气相线速为10米/秒;第三反应区中反应条件为:反应温度为600°C,反应压力以表压计为0.0lMPa,气相线速为3米/秒;第四反应区中反应条件为:反应温度为630°C,反应压力以表压计为0.0lMPa,气相线速为10米/秒。 The amount of the catalyst coke content after regeneration was 0.5%, the feed to the first reaction zone further comprises steam, steam and naphtha weight ratio of 0.05: 10 first reaction zone reaction conditions: Reaction temperature 670 ° C, the reaction pressure gauge pressure is 0.0lMPa, vapor line speed of 10 m / sec; the second reaction zone reaction conditions: reaction temperature of 600 ° C, the reaction pressure gauge pressure is 0.0lMPa, Gas line speed of 10 m / sec; third reaction zone reaction conditions: reaction temperature of 600 ° C, the reaction pressure gauge pressure is 0.0lMPa, vapor line speed of 3 m / sec; fourth reaction zone the reaction conditions as follows: reaction temperature of 630 ° C, the reaction pressure gauge pressure is 0.0lMPa, vapor line speed of 10 m / sec. C4〜CS混合烃的物流从第四反应区底部和从沿轴向方向上的一个进料口进入第四反应区,该进料口距离第四反应区底部为1/2第四反应区高度。 C4~CS mixed hydrocarbon stream into the fourth reaction zone from the bottom fourth reaction zone and from the axial direction of a feed, the feed from the bottom opening fourth reaction zone is 1/2 the height of the fourth reaction zone . 再生后的催化剂活性指数为0.8。 The regenerated catalyst activity index is 0.8. 保持催化剂流动控制的稳定性,产品气采用在线气相色谱分析,低碳烯烃碳基收率为62.49%重量。 Maintain the stability of the catalyst flow control, product gas using online gas chromatography analysis, a yield of lower olefins carbon 62.49% by weight of the base.

[0024]【实施例3】 [0024] [Example 3]

[0025] 按照实施例1所述的条件和步骤,催化剂为ZSM-5,S12Al2O3摩尔比为70,包括石脑油的原料从第一反应区底部和沿第一反应区轴向方向上的两个进料口进入第一反应区,两个进料口距离第一反应区底部分别为1/3、1/2第一反应区高度。 [0025] As described conditions and procedures described in Example 1, the catalyst is a ZSM-5, S12Al2O3 molar ratio of 70, a naphtha feedstock comprising both from the bottom of the first reaction zone and a reaction zone along a first axial direction a feed port into the first reaction zone, from the bottom of the two feed ports were the first reaction zone 1 / 3,1 / 2 of the first reaction zone height. 再生后的催化剂分为三部分,30 %重量进入第一反应区,30 %重量进入第二反应区,40 %重量进入第四反应区。 The regenerated catalyst is divided into three parts, 30% by weight into the first reaction zone, 30% by weight into the second reaction zone, 40% by weight into the fourth reaction zone. 再生后的催化剂积炭量质量分数为0.05%,第一反应区进料中还包括水蒸气,水蒸气与石脑油的重量比为0.5: I。 The amount of the catalyst coke content after regeneration was 0.05%, the feed to the first reaction zone further comprises steam, steam and naphtha weight ratio of 0.5: I. 第一反应区中反应条件为:反应温度为650°C,反应压力以表压计为0.0lMPa,气相线速为7米/秒;第二反应区中反应条件为:反应温度为560°C,反应压力以表压计为0.0lMPa,气相线速为6米/秒;第三反应区中反应条件为:反应温度为550°C,反应压力以表压计为0.0lMPa,气相线速为6.3米/秒;第四反应区中反应条件为:反应温度为610°C,反应压力以表压计为0.0lMPa,气相线速为7米/秒。 The first reaction zone reaction conditions: reaction temperature is 650 ° C, the reaction pressure gauge pressure is 0.0lMPa, vapor line speed of 7 m / sec; the second reaction zone reaction conditions: reaction temperature is 560 ° C The reaction pressure gauge pressure is 0.0lMPa, vapor line speed of 6 m / s; the third reaction zone reaction conditions: reaction temperature of 550 ° C, the reaction pressure gauge pressure is 0.0lMPa, Gas linear speed 6.3 m / sec; fourth reaction zone reaction conditions: reaction temperature of 610 ° C, the reaction pressure gauge pressure is 0.0lMPa, vapor line speed of 7 m / sec. C4〜C8混合烃的物流从第四反应区底部和从沿轴向方向上的两个进料口进入第四反应区,两个进料口距离第四反应区底部分别为1/3、1/2第四反应区高度。 C4~C8 mixed hydrocarbon stream from the bottom of the fourth reaction zone and into the fourth reaction zone from the two feed in the axial direction of the mouth, the bottom two feed ports respectively from the fourth reaction zone 1 / 3,1 / 2 fourth reaction zone height. 再生后的催化剂活性指数为0.94。 The regenerated catalyst activity index was 0.94. 保持催化剂流动控制的稳定性,产品气采用在线气相色谱分析,低碳烯烃碳基收率为65.06%重量。 Maintain the stability of the catalyst flow control, product gas using online gas chromatography analysis, a yield of lower olefins carbon 65.06% by weight of the base.

[0026]【实施例4】 [0026] [Example 4]

[0027] 按照实施例1所述的条件和步骤,催化剂为ZSM-5,S12Al2O3摩尔比为30,包括石脑油的原料从第一反应区底部和沿第一反应区轴向方向上的三个进料口进入第一反应区,三个进料口距离第一反应区底部分别为1/4、1/3、1/2第一反应区高度。 [0027] The conditions and procedures as described in Example 1, the catalyst is a ZSM-5, S12Al2O3 molar ratio of 30, a naphtha feedstock comprising a first reaction zone and from the bottom of the first reaction zone along the axial direction of the three a feed inlet into the first reaction zone, three inlet from the bottom of the first reaction zone are 1 / 4,1 / 3,1 / 2, the first reaction zone height. 再生后的催化剂分为三部分,33 %重量进入第一反应区,40 %重量进入第二反应区,27 %重量进入第四反应区。 The regenerated catalyst is divided into three parts, 33% by weight into the first reaction zone, 40% by weight into the second reaction zone, 27% by weight into the fourth reaction zone. 再生后的催化剂积炭量质量分数为0.1%,第一反应区进料中还包括水蒸气,水蒸气与石脑油的重量比为0.25: I。 The amount of the catalyst coke content after regeneration was 0.1%, the feed to the first reaction zone further comprises steam, steam and naphtha weight ratio of 0.25: I. 第一反应区中反应条件为:反应温度为660°C,反应压力以表压计为0.3MPa,气相线速为5米/秒;第二反应区中反应条件为:反应温度为570°C,反应压力以表压计为0.3MPa,气相线速为5米/秒;第三反应区中反应条件为:反应温度为560°C,反应压力以表压计为0.3MPa,气相线速为4.8米/秒;第四反应区中反应条件为:反应温度为615°C,反应压力以表压计为0.3MPa,气相线速为4米/秒。 The first reaction zone reaction conditions: reaction temperature is 660 ° C, the reaction pressure gauge pressure of 0.3MPa, vapor line speed of 5 m / sec; the second reaction zone reaction conditions: reaction temperature is 570 ° C The reaction pressure gauge pressure of 0.3MPa, vapor line speed of 5 m / sec; third reaction zone reaction conditions: reaction temperature of 560 ° C, the reaction pressure gauge pressure of 0.3MPa, linear velocity of the gas phase 4.8 m / sec; fourth reaction zone reaction conditions: reaction temperature of 615 ° C, the reaction pressure gauge pressure of 0.3MPa, vapor line speed of 4 m / sec. C4〜C8混合烃的物流从第四反应区底部和从沿轴向方向上的两个进料口进入第四反应区,两个进料口距离第四反应区底部分别为1/3、1/2第四反应区高度。 C4~C8 mixed hydrocarbon stream from the bottom of the fourth reaction zone and into the fourth reaction zone from the two feed in the axial direction of the mouth, the bottom two feed ports respectively from the fourth reaction zone 1 / 3,1 / 2 fourth reaction zone height. 再生后的催化剂活性指数为0.94。 The regenerated catalyst activity index was 0.94. 保持催化剂流动控制的稳定性,产品气采用在线气相色谱分析,低碳烯烃碳基收率为60.67%重量。 Maintain the stability of the catalyst flow control, product gas using online gas chromatography analysis, a yield of lower olefins carbon 60.67% by weight of the base.

[0028]【比较例I】 [0028] [Comparative Example I]

[0029] 按照实施例1所述的条件和步骤,只是不设置第四反应区,低碳烯烃碳基收率为52.69%重量。 [0029] The conditions and procedures according to the embodiment, but without providing a fourth reaction zone, the carbon-based olefins yield 52.69% by weight.

[0030]【比较例2】 [0030] [Comparative Example 2]

[0031] 按照实施例1所述的条件和步骤,只是不设置第三反应区和第四反应区,低碳烯烃碳基收率为47.28%重量。 [0031] The conditions and procedures according to the embodiment, but is not provided the third and fourth reaction zone, the reaction zone, the carbon-based olefins yield 47.28% by weight.

[0032] 显然,采用本发明的方法,可以达到提高低碳烯烃收率的目的,具有较大的技术优势,可用于低碳烯烃的工业生产中。 [0032] Clearly, the method of the present invention can achieve the purpose of improving the yield of light olefins, with great technical advantages, it can be used for industrial production of light olefins.

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Clasificación internacionalC07C4/06, C10G11/00, C07C11/02, C07C1/20
Clasificación cooperativaY02P20/584
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