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Número de publicaciónCN101165019 B
Tipo de publicaciónConcesión
Número de solicitudCN 200610117345
Fecha de publicación16 Jun 2010
Fecha de presentación20 Oct 2006
Fecha de prioridad20 Oct 2006
También publicado comoCN101165019A
Número de publicación200610117345.0, CN 101165019 B, CN 101165019B, CN 200610117345, CN-B-101165019, CN101165019 B, CN101165019B, CN200610117345, CN200610117345.0
Inventores谢在库, 刘俊涛, 钟思青, 张惠明
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
Method for producing ethylene and propylene
CN 101165019 B
Resumen
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.
Reclamaciones(6)  traducido del chino
  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 process for producing ethylene and propylene comprising the steps of: (a) to oxygen-containing compounds as raw materials, feedstock is first brought into contact with the catalyst from the reaction I bottom of the reactor to generate a first fluidized bed containing ethylene, propylene, C4 and above hydrocarbon effluent I, I effluent discharged from the first fluidized bed reactor into the upper portion of the subsequent section; (b) a first fluidized bed reactor II into the spent catalyst regenerator and the bottom of the regeneration from the regenerator gas contacting the regeneration flue gas discharged from the upper portion of the regenerator; (c) from the regenerator is regenerated catalyst III into the second fluidized bed reactor, and enables been regenerated catalyst III produces carbonaceous deposits passivating agent contact ; (d) a second IV fluid bed catalyst from the reactor after the return of the first passivation fluid bed reactor for reaction; wherein the oxygen-containing compound is selected from at least one of methanol or dimethyl ether; passivated agent is selected from C1 ~ C5 alcohol, at least one C2 ~ C10 ether or naphtha; catalyst I selected from a phosphorus or silicon aluminum composite zeolite molecular sieves or at least zeolite ZSM in.
  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。 1 according to the method of producing ethylene and propylene as claimed in claim wherein the first fluidized bed reactor the reaction temperature is 200~600 ° C, the reaction pressure was 0. 01~1. 5MPa, contact time 0 . 1~20 seconds, a weight ratio of catalyst to feed 0. 1~50; second fluidized bed reactor the reaction temperature is 100~55 (TC, a reaction pressure of 0. 01~ 1. OMPa, contact time 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。 2 according to the method of producing ethylene and propylene as claimed in claim wherein the first fluidized bed reactor the reaction temperature is 300~55 (TC, a reaction pressure of 0. 05~1. OMPa, contact time 0 . 2~10 seconds, a weight ratio of catalyst to feed 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。 1 4. The method for producing ethylene and propylene according to claim, 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。 1 according to the method of producing ethylene and propylene as claimed in claim wherein said catalyst is selected from SAP0-34 zeolite or ZSM-5 zeolite.
  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%。 1 6. The method for producing ethylene and propylene according to claim, characterized in that the second fluidized bed reactor of carbonaceous deposits on the catalyst in an amount of 2~12 wt%.
Descripción  traducido del chino

生产乙烯、丙烯的方法 Production of ethylene, propene

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 producing ethylene, propene, especially regarding the use of a regenerated catalyst 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 for regenerating the catalyst passivation, achieve an oxygen-containing compounds such as methanol or dimethyl ether catalytic efficient production of ethylene, propylene method.

背景技术 BACKGROUND

[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 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 driven by strong associations and industry sectors. 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 a modern petrochemical constitute two of the most important basic raw material.

[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 bulk of ethylene downstream products mainly include polyethylene, ethylene oxide, ethylene glycol, polyvinyl chloride, styrene, vinyl acetate, and so on. 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。 Ethylene production is a measure of the size of a country's level of development of the petrochemical industry and even the national flag. 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, carbonyl alcohols, acrylonitrile, propylene oxide, acrylic acid, isopropanol and the like, wherein the polypropylene accounts for more than half of the 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 percent of the world's production of propylene from ethylene steam cracker byproducts, 30% from refinery catalytic cracking (FCC) the production of gasoline and diesel oil by-products, a small amount (about 3%) by propane dehydrogenation and ethylene - butene translocation reaction. 预计未来乙烯及丙烯需求增长速度快于供应。 Ethylene and propylene expected future 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 higher ethylene and propylene demand growth, while the traditional mode of production show "shortage" of tension, and therefore need to supplement the needs of ethylene and propylene ethylene propylene yield by means of various other techniques.

[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 syngas, synthesis gas to methanol and olefin separation technology already has a mature experience of large-scale, but the process of olefins from methanol to olefin synthesis gas to break the chain of this industry and the difficulties, And the key technology can solve the grounds of non-oil resources to produce basic organic raw materials ethylene and propylene feedstock to provide 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, the demand for ethylene and propylene continued to rise, while the increasingly scarce oil resources in case. 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 of coal chemical production of propylene new route for China's oil supply greatly ease the tension, promote leapfrog development and structural adjustment of China's heavy chemical raw material route has important strategic significance and the 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 take from methanol or dimethyl ether ethylene, propylene and other olefins in the method of aluminum phosphate molecular sieve as catalyst upstream density phase circulating fluidized bed type process method, 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 cleavage 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 method 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 from methanol or dimethyl ether to 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 phosphoric silicoaluminophosphate molecular sieve (SAP0-34) as a catalyst, and the use of a gas-solid fluidized bed under a stream of short line contact reactors, the catalyst and the raw material in gas-solid fluidized bed under a stream of short line contact reactor contacting the reactant stream direction is downward; catalyst and the reaction product was provided out of the reactor into the lower part of the reactor Solid Separator rapid separation; separated catalyst enters the regenerator to burn the carbon regenerated, the catalyst system continuously regeneration, the reaction cycle. 该工艺二甲醚或甲醇的转化率大于98%。 The conversion of methanol or dimethyl ether process is more 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 ethylene propylene selectivity low technical 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] Technical Problem to be solved by the present invention is the presence of a conventional art document object product yield is low and the ethylene-propylene problem of low selectivity, to provide a new production of ethylene, propylene method. 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 high yield, good selectivity advantages.

[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] In order to solve the above problems, the present invention adopts the technical scheme is as follows, an ethylene, propylene production, comprising the steps of: (a) to oxygen-containing compounds as raw materials, raw material first from the first fluidized bed reactor bottom comes into contact with the catalyst I reaction containing ethylene, propylene, C4 and above hydrocarbons effluent I, I effluent from the first fluidized bed reactor is discharged into the upper portion of the subsequent section; (b) a first fluidized bed reactor The spent catalyst contacts the inner II into the regeneration gas from the regenerator and the bottom of the regenerator, and the regeneration flue gas discharged from the upper portion of the regenerator; (c) from the regenerator is regenerated catalyst III into the second fluidized bed reactor, and enables been regenerated catalyst III produces deactivator contact carbonaceous deposits; second fluidized bed catalyst reactor after passivation IV (d) from returning to the first fluidized bed reactor for reaction; wherein the oxygen-containing comprising at least one compound selected from 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, at least one of the above C4 hydrocarbons; the catalyst I selected from silicon aluminum phosphate molecular sieves or zeolite ZSM at least one or a composite molecular sieves.

[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 first aspect of the fluidized bed reactor the reaction temperature is 200~60 (TC, a reaction pressure of 0. 01~1. 5MPa, 0. 1~20 seconds contact time, the weight ratio of catalyst to feed 0. 1~50; second fluidized bed reactor the reaction temperature is 100~550 ° C, a reaction pressure of 0. 01~1 OMPa, a contact time of 0.5 seconds 1~10 first fluidized bed. The reaction temperature of the reactor is preferably in the range of 300~55 (TC, the reaction pressure is preferably in the range of 0. 05~1. OMPa, contact time is preferably in the range of 0. 2~10 seconds, and catalyst to feed weight ratio is preferably in the range of 0.2 ~ 10 passivation agent is preferably selected from methanol solutions, at least one DME Shang 4 or more hydrocarbons and the catalyst preferred embodiment, at least one selected from SAPO-34 zeolite or zeolite ZSM-5 zeolite in the compound or The second fluidized bed reactor of carbonaceous deposits on the catalyst 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 favorable for oxygen-containing compounds such as methanol or dimethyl ether in the catalytic conversion process, a catalyst such as SAPO-34 in the presence of an appropriate amount of coke improve the selectivity of ethylene propylene, and an appropriate amount of the catalyst coke control alone The burning rate and regeneration system charred degree of control and by fresh catalyst and deactivation of the catalyst is not only a mixed modulation is very difficult, while the effect is not very good; Based on the above analysis, the production of ethylene, propylene method of the invention , which reactor system prior to entering the reactor the regenerated catalyst, the first reactor was passivated by contacting the catalyst with a passivating agent activity maintained at a high level, and then re-enters through 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 present invention, technical solutions to SAPO-34 molecular sieve catalyst, methanol or dimethyl ether as raw materials, the first fluidized bed reactor, the reaction conditions as follows: reaction temperature 300~55 (TC, pressure 0.1 05~ 1. OMPa, 0. 2~10 seconds contact time, the weight ratio of catalyst to feed the second fluid bed reactor 0. 2~10 reaction conditions were: reaction temperature 100~55 (TC, pressure 0.01~l.OMPa under conditions of contact time 0. 1~15 seconds, and ethylene propylene diene may be greater than 75% yield, feed conversion rate reached 100%, and achieved good technical effect.

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] Figure 1 is a schematic view of invention, the oxygenate means ethylene, propylene production.

[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] Figure 1 l is a fluidized bed reactor I, 2 a regenerator, 3 a fluidized bed reactor II, 4 is the regeneration inclined pipe a, 5 is inclined to be raw tube, 6 is the regeneration inclined pipe b, 7 is a feedstock inlet, 8 is a passivating agent inlet, the inlet 9 is a regenerator, 10 is regenerated tobacco

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

[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 fluidized bed reactor II into the contact reaction, the reaction mixture after the cyclone separator, the reaction product gas mixture by the fluidized bed reactor I at the top of the outlet 11 introduced in subsequent processing section. 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。 The spent in the fluidized bed reactor I in the spent catalyst through the inclined tube 5 into the regenerator 2, the regenerator 2 good regeneration the regenerated catalyst into the inclined tube a fluidized bed reactor II, the passivating agent by blunt agent inlet 8 into the fluidized bed reactor II in contact with spent catalyst, the catalyst to produce carbonaceous deposits (coke), the catalyst deactivation after the fluidized bed reactor and then by regeneration inclined tube b I return fluidized I contacted the reaction bed reactor, the process is continuous. [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 is further illustrated by, but is not limited to this embodiment.

具体实施方式[0017]【实施例1】 DETAILED DESCRIPTION [0017] [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 the drawings, to SAP0-34 as catalyst and methanol as raw materials, butene _2 for passivating agent, the first fluid bed reactor the reaction conditions are as follows: reaction temperature 48 (TC, reaction pressure 0. 04MPa, the contact time of 6 seconds, a weight ratio of the catalyst with methanol the second fluidized-bed reactor 1. The reaction conditions were: reaction temperature 40 (TC, pressure 0. 06MPa, controls the second fluid bed reactor catalyst volume carbon content of 3%, the reaction results: yield of 48% of ethylene, propylene yield 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] The apparatus shown in the drawings l test uses to SAP0-34 as catalyst and methanol as raw material, methanol as the passivating agent, the first fluid bed reactor the reaction conditions are as follows: reaction temperature 45 (TC, the reaction pressure of 0. 02MPa, the contact time of 3 seconds, the weight ratio of the catalyst and the methanol is 0. 6. The second fluidized bed reactor the reaction conditions are as follows: reaction temperature 47 (TC, pressure 0. 02MPa, controls the second fluid bed reactor catalyst coke at 2%, the reaction results: yield of 45% of ethylene, propylene yield 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] The apparatus shown in the drawings l test uses to SAP0-34 as a catalyst, dimethyl ether as a raw material, naphtha for passivating agent, the first fluidized bed reactor reaction conditions as follows: reaction temperature 58 (TC, The reaction pressure is 0. 8MPa, the contact time of 10 seconds, the weight ratio of the catalyst with dimethyl ether to the second fluidized-bed reactor 1. 1. The reaction conditions were: reaction temperature 60 (TC, pressure 0.9MPa, control of the second fluidized bed reactor catalyst coke is 10%, the reaction results: yield of 42% of ethylene, propylene yield 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 drawings, to SAP0-34 as catalyst, dimethyl ether as raw material, an olefin and carbon four EPA-olefin, 50% of the mixed hydrocarbon as a passivating agent, the first fluid bed reactor control reaction conditions were: reaction temperature 52 (TC, reaction pressure 1. 2MPa, contact time 13 seconds, the weight ratio of the catalyst with dimethyl ether to the second fluidized bed reactor 6. The reaction conditions were: reaction temperature 50 (TC, pressure 1.5MPa, controls the second fluid bed reactor the amount of catalyst coke 4X, which reaction results: yield of 44% of ethylene, propylene yield 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 the drawings, to SAP0-34 as catalyst, methanol and dimethyl ether as raw material, methanol and dimethyl ether wherein the weight ratio of l: 2, tert-butyl alcohol as a passivating agent, the first a fluidized bed reactor the reaction conditions were: reaction temperature 540 ° C, the reaction pressure is 0. 2MPa, contact time of 4 seconds, the weight ratio of catalyst to feed is 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 are as follows: reaction temperature 53 (TC, pressure 0. 3MPa, controls the second fluid bed reactor the amount of catalyst 7% carbon, which reaction results: yield of 48% of ethylene, propylene 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 drawings, with ZSM-5 and SAP0-34 composite zeolite catalyst, the catalyst ZSM-5 accounts for 10%, SAP0-34 80%, methanol and dimethyl ether as raw material, wherein of methanol and dimethyl ether in a weight ratio of 2: l, methyl tert-butyl ether as the passivating agent, the first fluid bed reactor the reaction conditions are as follows: reaction temperature 50 (TC, reaction pressure 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, controls the second fluid bed reactor catalyst volume is 6% of carbon, the reaction Results as follows: 30% yield of ethylene, propylene yield 38% [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 drawings, with ZSM-5 and SAP0-34 composite zeolite catalyst, the catalyst ZSM-5 accounts for 5X, SAP0-34 80%, methanol and dimethyl ether as raw material, wherein the methanol the weight ratio of dimethyl ether 3: 1, diphenyl, a mixture of toluene and ethylbenzene as a passivating agent, the first fluid bed reactor the reaction conditions are as follows: reaction temperature 53 (TC, the reaction pressure of 0. 4MPa, 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, pressure 0. 5MPa, controls the second fluid bed reactor the amount of catalyst 7% carbon , which reaction results: yield of 35% ethylene, propylene yield 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, its reaction product, the ethylene yield of 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 drawings, in accordance with the conditions and the catalyst of Example 1, except that the second device without a fluidized bed reactor, the regenerated catalyst after the carbon deposition amount is 0.5%, the reaction product , ethylene yield is 43%, the propylene yield was 27%.

Citas de patentes
Patente citada Fecha de presentación Fecha de publicación Solicitante Título
CN1166478A24 May 19963 Dic 1997中国科学院大连化学物理研究所Preparation of ethylene, propylene and other low-carton olefine from methyl alcohol or dimethyl ether
CN1190270C30 Jun 199823 Feb 2005埃克森美孚化学专利公司Process for converting oxygenates to olefins using molecular sieve catalysts comprising desirable carbonaceous deposits
CN1356299A14 Dic 20013 Jul 2002清华大学Process and system for preparing low-carbon olefin from methanol or dimethylether
US43384753 Oct 19806 Jul 1982Mobil Oil CorporationConverting alcohols to hydrocarbons
US616628220 Ago 199926 Dic 2000Uop LlcFast-fluidized bed reactor for MTO process
Otras citas
Referencia
1高晋生等.甲醇制低碳烯烃的原理和技术进展.煤化工4.2006,4(5),全文.
2齐国祯等.甲醇制低碳烯烃(MTO)反应热力学研究.石油与天然气化工34 5.2005,4(5),全文.
Clasificaciones
Clasificación internacionalC07C1/20, C07C11/06, C07C11/04
Clasificación cooperativaY02P20/52, Y02P30/42, Y02P20/584
Eventos legales
FechaCódigoEventoDescripción
23 Abr 2008C06Publication
18 Jun 2008C10Entry into substantive examination
16 Jun 2010C14Grant of patent or utility model