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Method for producing ethylene and propylene

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Publication number
CN101165019B
CN101165019B CN 200610117345 CN200610117345A CN101165019B CN 101165019 B CN101165019 B CN 101165019B CN 200610117345 CN200610117345 CN 200610117345 CN 200610117345 A CN200610117345 A CN 200610117345A CN 101165019 B CN101165019 B CN 101165019B
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CN
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reactor
catalyst
regenerating
fluidized
bed
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CN 200610117345
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Chinese (zh)
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CN101165019A (en )
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谢在库
刘俊涛
钟思青
张惠明
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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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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/58Recycling
    • Y02P20/584Recycling of catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/40Ethylene production
    • Y02P30/42Ethylene production using bio-feedstock

Abstract

The present invention relates to one kind of ethylene and propylene producing process with high selectivity and high yield. The production process includes the following steps: 1. reaction of oxygen compound material in the first fluidized bed reactor through contacting with catalyst I to produce effluent I containing ethylene, propylene and C4 and C4+ hydrocarbons; and treating the effluent I ina post step; 2. regenerating the catalyst II to be regenerated from the first fluidized bed reactor through contacting with the regenerating gas in the regenerating reactor; 3. deactivating the regenerated catalyst III from the regenerating reactor through contact with deactivator capable of producing carbon deposit in the second fluidized bed reactor; and 4. returning the deactivated catalyst IVto the first fluidized bed reactor. The production process may be applied in industrial production.

Description

生产乙烯、丙烯的方法 Process for producing ethylene, propylene

技术领域 FIELD

[0001] 本发明涉及一种生产乙烯、丙烯的方法,特别是关于采用一个再生催化剂钝化处 [0001] The present invention relates to a process for the production of ethylene, propylene, in particular on the use of a catalyst regeneration Passivation

理系统对再生催化剂进行钝化处理,实现含氧化合物如甲醇或二甲醚催化高效生产乙烯、丙烯的方法。 Processing system of the regenerated catalyst passivation, oxygenate such as methanol or dimethylether catalytically efficient production of ethylene, propylene realized.

背景技术 Background technique

[0002] 石油化工是国民经济中重要的支柱产业,为工业、农业、交通和国防等部门提供大量化工原料,是国民经济中关联和带动性较强的产业部门之一。 [0002] petrochemical industry is an important pillar industry of the national economy, providing a large number of chemical raw materials for industry, agriculture, transportation and defense sectors, is one of the national economy and promote the relevance of a strong industrial sector. 而丙烯与乙烯则是构成现代石油化工最为重要的两大基础原料。 The propylene and ethylene is the most important modern constitute two basic petrochemical raw materials.

[0003] 乙烯的大宗下游产品主要有聚乙烯、环氧乙烷、乙二醇、聚氯乙烯、苯乙烯、醋酸乙烯等。 [0003] The main products of ethylene bulk downstream polyethylene, ethylene oxide, ethylene glycol, polyvinyl chloride, styrene, vinyl acetate and the like. 乙烯产量的大小是衡量一个国家石化工业乃至国民经济发达程度的标志。 The size of the ethylene production is a measure of a country's petrochemical industry and the level of development of the national economy logo. 丙烯主要用于生产聚丙烯、异丙苯、羰基醇、丙烯腈、环氧丙烷、丙烯酸、异丙醇等,其中聚丙烯占世界丙烯需求的一半以上。 Propylene mainly for the production of polypropylene, cumene, oxo alcohols, acrylonitrile, propylene oxide, acrylic acid, isopropanol and the like, in which more than half of the polypropylene world demand for propylene. 目前,世界上67%的丙烯来自蒸汽裂解生产乙烯的副产品,30%来自炼油厂催化裂化(FCC)生产汽、柴油的副产品,少量(约3% )由丙烷脱氢和乙烯-丁烯易位反应得到。 Currently, 67% of a propylene by-product from the steam cracking of the world production of ethylene, 30% from a refinery catalytic cracking (FCC) produced gasoline and diesel by-product, a small amount (about 3%) of propane dehydrogenation and ethylene - butene metathesis reaction. 预计未来乙烯及丙烯需求增长速度快于供应。 The next ethylene and propylene demand growing faster than supply.

[0004] 鉴于乙烯及丙烯的需求增长率较高,而传统的生产模式呈现"供不应求"的紧张状况,因此补充乙烯及丙烯需求需要借助于其他各种增产乙烯丙烯技术。 [0004] In view of the high demand growth ethylene and propylene, and the traditional mode of production presents "shortage" of tension, and therefore supplement ethylene and propylene demand need the help of various other ethylene propylene yield technology.

[0005] —直以来,煤或天然气制合成气、合成气制甲醇和烯烃分离技术已经具有规模化成熟经验,但是由甲醇到烯烃的过程是合成气到烯烃这个工业链条的断点和难点,而该关键技术的解决可以为由非石油资源生产基本有机原料乙烯、丙烯提供一条新的原料路线。 [0005] - straight since, coal or natural gas to synthesis gas, methanol synthesis gas and olefin separation technology has experienced a large-scale maturation, but the process of methanol synthesis gas to olefins are olefins and difficult to break this industrial chain, the key technology is solved by the non-petroleum resources can be the production of organic material, ethylene, propylene feed provides a new route. 尤其是近些年来,乙烯及丙烯的需求持续走高,而石油资源日趋匮乏的情况下。 Especially in recent years, demand for ethylene and propylene continued to rise, while the increasingly scarce oil resources. 如何开辟出一条非石油资源生产丙烯的煤化工新路线,对于极大地缓解我国石油供应紧张的局面,促进我国重化工的跨越式发展和原料路线的结构性调整,具有重要的战略意义和社会、经济效益。 How to open up a non-petroleum resources, coal chemical production of propylene new route for China's oil greatly ease the tight supply situation, promote leapfrog development and structural adjustment of raw material route of China's heavy chemical industry has important strategic significance and social, economic benefits.

[0006] 文献CN1166478A,公开一种由甲醇或二甲醚制取乙烯、丙烯等低碳烯烃的方法,该方法以磷酸铝分子筛为催化剂,采用上行式密相床循环流化式工艺方法,在优选的反应温度500〜570°C,空速2〜6小时—1及0. 01〜0. 05MPa条件下,使甲醇或二甲醚裂解制取乙烯、丙烯等低碳烯烃。 [0006] Document CN1166478A, discloses a method taken from the methanol or dimethyl ether of ethylene, propylene and other olefins, which method aluminum phosphate molecular sieve as catalyst upstroke dense bed type circulating fluidized process for, in the preferred reaction temperature is 500~570 ° C, at a space velocity of 2 ~ 6 h -1 and 0. 01~0. 05MPa conditions, methanol or dimethyl ether cracker to make ethylene, propylene and other olefins. 该方法目的产物的选择性低的技术缺点。 Low selectivity technical disadvantage of this process is the desired product.

[0007] 文献CN1356299A,公开了一种由甲醇或二甲醚生产低碳烯烃的工艺方法及其系统。 [0007] Document CN1356299A, discloses a process for producing a methanol or dimethyl ether, light olefins and the process for the system. 该工艺采用磷酸硅铝分子筛(SAP0-34)作为催化剂,利用气固并流下行式流化床超短接触反应器,催化剂与原料在气固并流下行式流化床超短接触反应器中接触、反应物流方向为下行;催化剂及反应产物出反应器后进入设置在该反应器下部的气固快速分离器进行快速分离;分离出的催化剂进入再生器中烧碳再生,催化剂在系统中连续再生,反应循环进行。 The process uses silicoaluminophosphate molecular sieves (SAP0-34) as a catalyst, and the use of gas-solid fluidized bed flow line short contact reactor, and catalyst to feed in gas-solid fluidized bed downflow reactor short contacts contacting the reactant stream is a downlink direction; and a catalyst reaction product from the reactor after entering Solid separator provided at a lower portion of the reactor for rapid separation; separated catalyst into the regeneration of carbon burning in the regenerator, catalyst is continuously in the system regeneration reaction cycle. 该工艺二甲醚或甲醇的转化率大于98%。 The process of conversion of methanol or dimethyl ether is greater than 98%. 但该方法同样存在乙烯丙烯选择性低的技术缺点。 However, this method also exists a low ethylene propylene selectivity art drawbacks. 发明内容 SUMMARY

[0008] 本发明所要解决的技术问题是以往文献技术中存在目的产品乙烯丙烯收率低及选择性低的问题,提供一种新的生产乙烯、丙烯的方法。 [0008] The present invention solves the technical problem of the conventional method in the presence of art document object product yields are low and low ethylene propylene selectivity problems and provide a new production of ethylene, propylene. 该方法具有目的产品乙烯丙烯收率高,选择性好的优点。 This method has the purpose of product ethylene propylene yield, good selectivity advantage.

[0009] 为了解决上述技术问题,本发明采用的技术方案如下,一种生产乙烯、丙烯的方法,包括以下步骤:(a)以含氧化合物为原料,原料首先从第一流化床反应器底部进入与催化剂I接触反应生成含有乙烯、丙烯、C4及其以上烃的流出物I,流出物I从第一流化床反应器上部排出进入后续工段;(b)第一流化床反应器中的待生催化剂II进入再生器内与来自再生器底部的再生气体接触再生,再生烟气从再生器上部排出;(c)来自再生器的已再生催化剂III进入第二流化床反应器,与能使已再生催化剂III产生碳质沉积物的钝化剂接触;(d)来自第二流化床反应器钝化后的催化剂IV返回第一流化床反应器进行反应;其中,含氧化合物选自含甲醇或二甲醚中的至少一种;钝化剂选自Q〜Cs醇、C^〜Q。 [0009] To solve the above problems, the present invention employs the following technical solution, a method of ethylene, propylene production, comprising the steps of: (a) oxygen-containing compounds as raw materials, a first material from the first fluidized bed reactor comes into contact with the bottom of the reaction catalyst I containing ethylene, propylene, C4 and above hydrocarbons effluent I, I is discharged into the effluent from the upper portion of the subsequent section a first fluidized bed reactor; (b) a first fluidized-bed reactor the spent catalyst regenerator II into contact with the regeneration gas from the bottom of the regenerator, and the regeneration flue gas is discharged from the upper portion of the regenerator; (c) from the catalyst regenerator is regenerated into a second fluidized bed reactor III, and III can produce regenerated catalyst has contacted the passivating agent carbonaceous deposits; IV after the reaction the catalyst is passivated (D) from the second fluidized bed reactor is returned to the first reaction; wherein the oxygen-containing at least one compound selected from the group comprising methanol or dimethyl ether; Q~Cs passivating agent is selected from alcohols, C ^ ~Q. 醚、C4以上烃类中的至少一种;催化剂I选自硅磷铝分子筛或ZSM型分子筛中的至少一种或其复合分子筛。 Ether, C4 hydrocarbons than at least one; catalyst I is selected from at least one phosphorus or silicon aluminum composite zeolite ZSM-type molecular sieve or molecular sieve.

[0010] 上述技术方案中第一流化床反应器的反应温度为200〜60(TC,反应压力为0. 01〜1. 5MPa,接触时间为0. 1〜20秒,催化剂与原料重量比为0. 1〜50 ;第二流化床反应器的反应温度为100〜550°C ,反应压力为0. 01〜1. OMPa,接触时间为0. 1〜10秒。第一流化床反应器的反应温度优选范围为300〜55(TC,反应压力优选范围为0. 05〜1. OMPa,接触时间优选范围为0. 2〜10秒,催化剂与原料重量比优选范围为0. 2〜10。钝化剂优选方案选自甲醇、二甲醚丄4及以上烃类中的至少一种。催化剂优选方案选自SAPO-34分子筛或ZSM-5分子筛中的至少一种或其复合分子筛。第二流化床反应器中催化剂上碳质沉积物重量含量为2〜12%。 [0010] The reaction temperature of the first aspect of the fluidized bed reactor is 200~60 (TC, reaction pressure of 0. 01~1. 5MPa, 0. 1~20 seconds contact time, the weight ratio of catalyst to feed 0. 1~50; reaction temperature in the second fluidized bed reactor is 100~550 ° C, reaction pressure of 0. 01~1 OMPa, a contact time of 0.5 seconds 1~10 first fluidized bed. the reaction temperature is preferably in the range of the reactor is 300~55 (TC, reaction pressure is preferably in the range of 0. 05~1. OMPa, contact time is preferably in the range of 0. 2~10 seconds, catalyst to feed weight ratio is preferably in the range of 0.2 ~ 10. deactivators embodiment is preferably selected from methanol, dimethyl ether Shang at least one or more hydrocarbons and 4 the catalyst preferred embodiment at least one selected from molecular sieve SAPO-34 or ZSM-5 molecular sieve or a zeolite composite the second fluidized-bed reactor over a catalyst of carbonaceous deposits is the content of 2~12 wt%.

[0011] 大量研究表明,对于含氧化合物如甲醇或二甲醚催化转化过程中,催化剂如SAPO-34中适量焦炭的存在对提高乙烯丙烯的选择性有利,而催化剂中适量焦炭的控制单靠再生系统的烧焦速率及烧焦程度的控制以及通过新鲜催化剂与失活催化剂的混合调变不仅是十分困难的,同时效果并不十分理想;基于以上分析,本发明的生产乙烯、丙烯的方法,其反应器系统中在再生催化剂进入反应器之前,先经过钝化处理反应器,通过与钝化剂接触使催化剂的活性保持在较高的水平,然后经钝化的催化剂再进入第一流化床反应器进行反应。 [0011] Numerous studies have shown, for oxygenates, such as methanol or dimethyl ether in the catalytic conversion process, an appropriate amount of the catalyst as coke selectivity of SAPO-34 in the presence of ethylene propylene is advantageously increased, and an appropriate amount of the catalyst coke alone control regeneration system and charred burning rate and degree of control by the mixing of fresh catalyst modulation deactivation of the catalyst is not only very difficult, while the effect is not very good; based on the above analysis, a process for producing ethylene and propylene of the present invention. that the reactor system before regeneration of the catalyst into the reactor, the first reactor and passivated by contacting the catalyst with a passivating agent activity maintained at a high level, and then by re-entering the first stream of catalyst deactivation bed reactor for reaction.

[0012] 采用本发明的技术方案,以SAPO-34分子筛为催化剂,甲醇或二甲醚为原料,第一流化床反应器反应条件为:反应温度300〜55(TC,压力0. 05〜1. OMPa,接触时间0. 2〜10秒,催化剂与原料重量比为0. 2〜10。第二流化床反应器反应条件为:反应温度100〜55(TC,压力0.01〜l.OMPa,接触时间0. 1〜15秒条件下,乙烯及丙烯双烯收率可大于75% ,原料转化率可达到100% ,取得了较好的技术效果。 [0012] The technical solution of the present invention, in order of SAPO-34 catalyst, methanol or dimethyl ether as raw material, the first fluidized bed reactor the reaction conditions are: a reaction temperature of 300~55 (TC, pressure 0.5 05~ 1. OMPa, 0. 2~10 seconds contact time, catalyst to feed weight ratio is 0. 2~10 second fluidized bed reactor the reaction conditions are: a reaction temperature of 100~55 (TC, pressure 0.01~l.OMPa under conditions of a contact time of 0.5 seconds 1~15, and ethylene propylene diene may be greater than 75% yield, feed conversion rate reached 100%, and achieved good results in the art.

附图说明 BRIEF DESCRIPTION

[0013] 图1为本发明含氧化合物生产乙烯、丙烯的装置示意图。 [0013] Fig 1 a schematic view of an oxygenate ethylene, propylene production apparatus of the present invention.

[0014] 图1中l是流化床反应器I,2是再生器,3是流化床反应器II,4是再生斜管a,5是待生斜管,6是再生斜管b, 7是原料入口, 8是钝化剂入口, 9是再生器入口, 10是再生烟 [0014] FIG. 1 is a fluidized bed reactor l I, 2 a regenerator, 3 a fluidized bed reactor II, 4 is reproduced inclined tube a, 5 is inclined tube spent, the regeneration inclined pipe 6 B, 7 is a raw material inlet, a passivating agent inlet 8, 9 are the regenerator inlet 10 is regenerated tobacco

4气,ll是反应混合物出口。 4 gas, ll the reaction mixture outlet.

[0015] 图1中含氧化合物原料由入口装置7从下部进入流化床反应器II接触反应,反应混合物经旋风分离器分离后,气体产物经流化床反应器I顶部的反应混合物出口11引入后续处理工段。 [0015] FIG. 1 by the oxygenate feedstock inlet means 7 from the lower portion of a fluidized bed reactor II into the contact reaction, the reaction mixture was separated after the cyclone, the product gas mixture was reacted at the top of the fluidized bed reactor outlet 11 I introducing a subsequent processing step. 在流化床反应器I中的待生催化剂经待生斜管5进入再生器2,再生器2内的再生好的催化剂经再生斜管a进入流化床反应器II,钝化剂经钝化剂入口8进入流化床反应器II与待生催化剂接触,使催化剂产生碳质沉积物(焦炭),经钝化后的催化剂再经流化床反应器I的再生斜管b返回流化床反应器I接触反应,该过程连续进行。 Spent in the fluidized bed reactor I via the spent catalyst pipe 5 obliquely enters regenerator 2, the regenerator 2 in a good reproduction of the regenerated catalyst into the fluidized bed a helical tube reactor II, a passivation agent by blunt agent inlet 8 into the fluidized bed reactor II into contact with the spent catalyst, the catalyst mass produce carbon deposits (coke), dried and then the passivated catalyst was regenerated fluidized bed reactor I fluidizing return chute b I catalytic bed reactor, the process is carried out continuously. [0016] 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。 [0016] The following examples of the present invention will be further illustrated by, but is not limited to this embodiment.

具体实施方式[0017]【实施例1】 DETAILED DESCRIPTION [0017] [Embodiment Example 1]

[0018] 试验采用附图1所示装置,以SAP0-34为催化剂,甲醇为原料,丁烯_2为钝化剂,第一流化床反应器反应条件为:反应温度48(TC,反应压力0. 04MPa,接触时间6秒,催化剂与甲醇重量比为1。第二流化床反应器反应条件为:反应温度40(TC,压力0. 06MPa,控制第二流化床反应器催化剂积碳量为3 % ,其反应结果为:乙烯收率48 % ,丙烯收率31 % 。[0019]【实施例2】 [0018] Test using the apparatus shown in figures 1 to SAP0-34 as catalyst and methanol as raw materials, butene _2 passivation agent, the first fluid bed reactor reaction conditions were: reaction temperature 48 (TC, the reaction pressure of 0. 04MPa, the contact time of 6 seconds, the reaction of methanol with a catalyst weight ratio of the second fluidized-bed reactor 1 as follows: reaction temperature 40 (TC, pressure 0. 06MPa, controls the second fluidized-bed reactor catalyst volume carbon in an amount of 3%, which is a result of the reaction: 48% yield of ethylene, propylene yield of 31% [0019] [Example 2].

[0020] 试验采用附图l所示装置,以SAP0-34为催化剂,甲醇为原料,甲醇为钝化剂,第一流化床反应器反应条件为:反应温度45(TC,反应压力0. 02MPa,接触时间3秒,催化剂与甲醇重量比为0. 6。第二流化床反应器反应条件为:反应温度47(TC,压力0. 02MPa,控制第二流化床反应器催化剂积碳量为2%,其反应结果为:乙烯收率45%,丙烯收率29%。[0021]【实施例3】 [0020] L test using the apparatus shown in the drawing, to SAP0-34 as catalyst and methanol as raw material, methanol as the passivating agent, the first fluid bed reactor reaction conditions were: reaction temperature 45 (TC, a reaction pressure of 0. MPa gauge, the contact time of 3 seconds, the reaction of methanol with a catalyst weight ratio is 0. 6. the second fluidized bed reactor as follows: reaction temperature 47 (TC, pressure 0.5 MPa gauge, a second fluidized bed reactor to control carbon catalyst in an amount of 2%, which is a result of the reaction: 45% yield of ethylene, propylene yield of 29% [0021] [Example 3].

[0022] 试验采用附图l所示装置,以SAP0-34为催化剂,二甲醚为原料,石脑油为钝化剂,第一流化床反应器反应条件为:反应温度58(TC,反应压力0. 8MPa,接触时间10秒,催化剂与二甲醚重量比为1. 1。第二流化床反应器反应条件为:反应温度60(TC,压力0.9MPa,控制第二流化床反应器催化剂积碳量为10%,其反应结果为:乙烯收率42%,丙烯收率22%。[0023]【实施例4】 [0022] L test using the apparatus shown in the drawing, to SAP0-34 catalyst, dimethyl ether as raw material, the passivating agent is naphtha, a first fluidized-bed reactor reaction conditions were: reaction temperature 58 (TC, the reaction pressure of 0. 8MPa, a contact time of 10 seconds, a weight ratio of dimethyl ether with a catalyst as a second fluidized-bed reactor 1. 1. the reaction conditions were: reaction temperature 60 (TC, 0.9MPa pressure, controlling a second fluidized bed the amount of catalyst coking reactor was 10%, which is a result of the reaction: 42% yield of ethylene, propylene yield of 22% [0023] [Example 4].

[0024] 试验采用附图1所示装置,以SAP0-34为催化剂,二甲醚为原料,碳四烯烃及碳五烯烃各50%的混合烃类为钝化剂,第一流化床反应器反应条件为:反应温度52(TC,反应压力1. 2MPa,接触时间13秒,催化剂与二甲醚重量比为6。第二流化床反应器反应条件为:反应温度50(TC,压力1.5MPa,控制第二流化床反应器催化剂积碳量为4X,其反应结果为:乙烯收率44% ,丙烯收率28 % 。[0025]【实施例5】 [0024] Test using the apparatus shown in the accompanying drawings, in SAP0-34 catalyst, dimethyl ether as raw material, 50% carbon and EPA Olefin is an olefin-based hydrocarbon mixture deactivators, a first fluidized bed reactor the reaction conditions is as follows: reaction temperature 52 (TC, reaction pressure 1. 2MPa, a contact time of 13 seconds, a weight ratio of dimethyl ether with a catalyst as a second fluidized bed reactor 6. the reaction conditions were: reaction temperature 50 (TC, pressure 1.5MPa, the control amount of the second carbon bed catalyst reactor 4X, which is a result of the reaction: 44% yield of ethylene, propylene yield of 28% [0025] [Example 5].

[0026] 试验采用附图1所示装置,以SAP0-34为催化剂,甲醇与二甲醚为原料,其中甲醇与二甲醚的重量比为l : 2,叔丁醇为钝化剂,第一流化床反应器反应条件为:反应温度540°C ,反应压力0. 2MPa,接触时间4秒,催化剂与原料重量比为0. 5。 [0026] Test using the apparatus shown in figures 1 to SAP0-34 catalyst, methanol and dimethyl ether as raw material, with methanol and dimethyl ether wherein the weight ratio of l: 2, tert-butyl alcohol deactivators, first a fluidized bed reactor the reaction conditions are: a reaction temperature of 540 ° C, reaction pressure of 0. 2MPa, a contact time of 4 seconds, the weight ratio of catalyst to feedstock of 0.5. 第二流化床反应器反应条件为:反应温度53(TC,压力0. 3MPa,控制第二流化床反应器催化剂积碳量为7%,其反应结果为:乙烯收率48 % ,丙烯收率30 % 。[0027]【实施例6】 The second fluidized bed reactor the reaction conditions were: reaction temperature 53 (TC, pressure 0. 3MPa, the control amount of the second bed catalyst coking reactor was 7%, which is a result of the reaction: 48% yield of ethylene, propylene in 30% yield. [0027] [Example 6]

[0028] 试验采用附图1所示装置,以ZSM-5及SAP0-34复合分子筛为催化剂,催化剂中ZSM-5占10%, SAP0-34占80%,甲醇与二甲醚为原料,其中甲醇与二甲醚的重量比为2 : l,甲基叔丁基醚为钝化剂,第一流化床反应器反应条件为:反应温度50(TC,反应压力0. 2MPa,接触时间8秒,催化剂与原料重量比为1。第二流化床反应器反应条件为:反应温度500°C ,压力0. 3MPa,控制第二流化床反应器催化剂积碳量为6% ,其反应结果为:乙烯收率30%,丙烯收率38%。[0029]【实施例7】 [0028] Test using the apparatus shown in the accompanying drawings, and ZSM-5 zeolite catalyst composite SAP0-34, the catalyst ZSM-5 accounts for 10%, SAP0-34 80% methanol and dimethyl ether as raw material, wherein the weight ratio of methanol to dimethyl ether is 2: l, methyl tert-butyl ether as the passivating agent, the first fluid bed reactor reaction conditions were: reaction temperature 50 (TC, reaction pressure of 0. 2MPa, contact time 8 second, the weight ratio of catalyst to feed the second fluid bed reactor 1. the reaction conditions were: reaction temperature 500 ° C, pressure 0. 3MPa, the control amount of the second carbon bed catalyst reactor is 6%, the reaction results: 30% yield of ethylene, propylene 38% yield [0029] [Example 7].

[0030] 试验采用附图1所示装置,以ZSM-5及SAP0-34复合分子筛为催化剂,催化剂中ZSM-5占5X,SAP0-34占80%,甲醇与二甲醚为原料,其中甲醇与二甲醚的重量比为3 : 1,二苯、甲苯与乙苯混合物为钝化剂,第一流化床反应器反应条件为:反应温度53(TC,反应压力0. 4MPa,接触时间4秒,催化剂与原料重量比为0. 7。第二流化床反应器反应条件为:反应温度58(TC,压力0. 5MPa,控制第二流化床反应器催化剂积碳量为7%,其反应结果为:乙烯收率35 % ,丙烯收率31 % 。[0031]【实施例8】 [0030] Test using the apparatus shown in the accompanying drawings, and ZSM-5 zeolite catalyst composite SAP0-34, the catalyst ZSM-5 accounts for 5X, SAP0-34 80% methanol and dimethyl ether as raw material, with methanol dimethyl ether weight ratio of 3: 1, diphenyl, a mixture of toluene and ethylbenzene as the passivating agent, the first fluid bed reactor reaction conditions were: reaction temperature 53 (TC, reaction pressure of 0. 4MPa, the contact time 4 seconds, the weight ratio of catalyst to feed is 0. 7. the second fluidized bed reactor the reaction conditions were: reaction temperature 58 (TC, 0. 5 MPa pressure, controlling the amount of the second carbon bed catalyst reactor 7% , as a result of the reaction: 35% yield of ethylene, propylene yield of 31% [0031] [Example 8]

[0032] 试验采用附图1所示装置,依据实施例7的条件及催化剂,只是催化剂采用ZSM-5分子筛,其反应产物中,乙烯收率为12% ,丙烯收率为48% 。 [0032] Test using the apparatus shown in the drawings, according to the conditions and the catalyst of Example 7, except that the catalyst using ZSM-5 zeolite, which is the reaction product, the ethylene yield was 12%, the propylene yield was 48%. [0033]【比较例1】 [0033] [Comparative Example 1]

[0034] 试验采用附图l所示装置,依据实施例1的条件及催化剂,只是装置中不加第二流化床反应器,再生后催化剂积碳量为0. 5%,其反应产物中,乙烯收率为43%,丙烯收率为27%。 [0034] L test using the apparatus shown in the drawing, according to the conditions and the catalyst of Example 1, except that the second device without a fluidized bed reactor, the regenerated catalyst coke in an amount of 0.5%, which is the reaction product of , ethylene yield was 43% and the propylene yield was 27%.

Claims (6)

  1. 一种生产乙烯和丙烯的方法,包括以下步骤:(a)以含氧化合物为原料,原料首先从第一流化床反应器底部进入与催化剂I接触反应生成含有乙烯、丙烯、C4及其以上烃的流出物I,流出物I从第一流化床反应器上部排出进入后续工段;(b)第一流化床反应器中的待生催化剂II进入再生器内与来自再生器底部的再生气体接触再生,再生烟气从再生器上部排出;(c)来自再生器的已再生催化剂III进入第二流化床反应器,与能使已再生催化剂III产生碳质沉积物的钝化剂接触;(d)来自第二流化床反应器钝化后的催化剂IV返回第一流化床反应器进行反应;其中,含氧化合物选自含甲醇或二甲醚中的至少一种;钝化剂选自C1~C5醇、C2~C10醚或石脑油中的至少一种;催化剂I选自硅磷铝分子筛或ZSM型分子筛中的至少一种或其复合分子筛。 A method for producing ethylene and propylene, comprising the steps of: (a) oxygen-containing compounds as raw materials, feedstock is first contacted with the catalyst into the reactor I from the bottom of the first fluidized bed reactor generating containing ethylene, propylene, C4 and above hydrocarbon effluent I, I exudates discharged from the upper fluidized bed reactor into the first subsequent stage; spent catalyst (b) a first fluidized bed reactor II into the regenerator and from the regenerator to the bottom of the regenerator contacting the regeneration gas, the regeneration flue gas discharged from the upper regenerator; (c) from the catalyst regenerator is regenerated into a second fluidized bed reactor III, and III can produce regenerated catalyst deactivator contacting the carbonaceous deposits ; (d) the catalyst after IV from the second fluidized bed reactor is returned to the first passivation fluid bed reactor for reaction; wherein the oxygen-containing compound selected from those having at least one of methanol or dimethyl ether; passivating is selected from C1 ~ C5 alcohol, at least one C2 ~ C10 ether or naphtha; catalyst I is selected from aluminum, silicon-phosphorus zeolite or ZSM-type molecular sieve or a compound of at least one molecular sieve.
  2. 2. 根据权利要求1所述生产乙烯和丙烯的方法,其特征在于第一流化床反应器的反应温度为200〜600°C,反应压力为0. 01〜1. 5MPa,接触时间为0. 1〜20秒,催化剂与原料重量比为0. 1〜50 ;第二流化床反应器的反应温度为100〜55(TC,反应压力为0. 01〜 1. OMPa,接触时间为0. 1〜10秒。 The process for producing ethylene and propylene according to claim 1, characterized in that the first fluidized bed reactor the reaction temperature is 200~600 ° C, reaction pressure of 0. 01~1. 5MPa, the contact time is 0 . 1~20 seconds, a weight ratio of catalyst to feedstock 0. 1~50; reaction temperature in the second fluidized bed reactor is 100~55 (TC, reaction pressure of 0. 01~ 1. OMPa, the contact time is 0 . 1~10 seconds.
  3. 3. 根据权利要求2所述生产乙烯和丙烯的方法,其特征在于第一流化床反应器的反应温度为300〜55(TC,反应压力为0. 05〜1. OMPa,接触时间为0. 2〜10秒,催化剂与原料重量比为0. 2〜10。 The process for producing ethylene and propylene of claim 2, characterized in that the first fluidized bed reactor the reaction temperature is 300~55 (TC, reaction pressure of 0. 05~1. OMPa, the contact time is 0 . 2~10 seconds, a weight ratio of catalyst to feedstock 0. 2~10.
  4. 4. 根据权利要求1所述生产乙烯和丙烯的方法,其特征在于钝化剂选自甲醇、二甲醚或石脑油中的至少一种。 4. A process for producing ethylene and propylene according to claim 1, characterized in that the passivating agent is selected from at least one of methanol, dimethyl ether, or naphtha.
  5. 5. 根据权利要求1所述生产乙烯和丙烯的方法,其特征在于所述催化剂选自SAP0-34 分子筛或ZSM-5分子筛。 The process for producing ethylene and propylene according to claim 1, wherein said catalyst is selected from SAP0-34 molecular sieve or zeolite ZSM-5.
  6. 6. 根据权利要求1所述生产乙烯和丙烯的方法,其特征在于第二流化床反应器中催化剂上碳质沉积物重量含量为2〜12%。 6. A process for producing ethylene and propylene according to claim 1, characterized in that the second fluidized-bed reactor the catalyst of carbonaceous deposits on the weight content of 2~12%.
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