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Semi-continuous method for converting methyl alcohol into propylene by using moving bed technology

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CN102344328A
CN102344328A CN 201110208634 CN201110208634A CN102344328A CN 102344328 A CN102344328 A CN 102344328A CN 201110208634 CN201110208634 CN 201110208634 CN 201110208634 A CN201110208634 A CN 201110208634A CN 102344328 A CN102344328 A CN 102344328A
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reaction
zone
catalyst
material
sieve
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CN 201110208634
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Chinese (zh)
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CN102344328B (en )
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严丽霞
唐玥琪
姜坤
廖祖维
张擎
汪燮卿
王靖岱
童国红
蒋斌波
阳永荣
黄正梁
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浙江大学
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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 invention discloses a semi-continuous method for converting methyl alcohol into propylene by using a moving bed technology, which comprises the following steps: mixing a molecular sieve based catalyst with a diluent, and then, introducing into a first reaction zone; introducing a methyl alcohol raw material into the first reaction zone to generate contact reaction with the molecular sieve based catalyst to generate a first material flow; introducing the first material flow into a second reaction zone to generate the contact reaction with the molecular sieve based catalyst to generate a second material flow; after the second material flow and the methyl alcohol raw material exchange heat and after dehydration and oxide removing are carried out, carrying out separation to obtain a second reaction zone return, a second reaction zone discharge and a third reaction zone feed, and merging the second reaction zone return into the first material flow; introducing the third reaction zone feed into a third reaction zone to be contacted with the molecular sieve based catalyst to generate a third material flow; and conveying the molecular sieve based catalyst into a regenerating unit at regular intervals by adopting a catalyst collector for regeneration, and intermittently merging into the molecular sieve based catalyst for circulation. Three stages of reaction of the methyl alcohol into the propylene are realized only by one molecular sieve based catalyst, thereby, the propylene yield is improved.

Description

一种使用移动床技术将甲醇转化为丙烯的半连续方法 A method of using moving bed technology for converting methanol to propylene semi-continuous process

技术领域 FIELD

[0001] 本发明涉及使用移动床技术制备丙烯的领域,具体涉及一种使用移动床技术将甲醇转化为丙烯的半连续方法。 [0001] The present invention relates to the field of preparation of propylene using moving bed technology, and particularly relates to a method of using a semi-continuous moving bed technology for converting methanol to propylene.

背景技术 Background technique

[0002] 丙烯是现代化学工业中一种重要的基础化工原料,是目前全球需求量第二大的化学品。 [0002] Propylene is a modern chemical industry is an important basic chemical raw materials, is currently the world's second largest demand for chemicals. 随着世界各国工业经济的发展,丙烯需求量将越来越大。 As the world's industrial economic development of countries, propylene demand will increase. 丙烯传统的生产路线是石油原料的催化裂解。 Propylene traditional production line is the catalytic cracking of petroleum feedstock. 由于世界石油总量有限,国际原油价格不断上涨,导致以石油为原料生产丙烯的成本不断升高,从而引发了以较为廉价的甲醇生产丙烯技术(MTP)的研究热潮。 Due to the limited amount of oil in the world, the international crude oil prices continue to rise, resulting in the cost of petroleum-producing propylene rising, which led to cheaper methanol production technology propylene (MTP) research boom. 在当前原油价格很高且今后也难以下降的情况下,对于缺油、少气、富煤的中国来说,甲醇生产丙烯工艺技术更加突显出较强的竞争力和深远的战略意义。 In the current high crude oil prices and the future is difficult to drop the case for lack of oil, less gas, coal-rich China, methanol and propylene production technology more competitive highlighted the strong and far-reaching strategic significance.

[0003] 目前,世界上比较成熟的甲醇制烯烃工艺主要有美国UOP公司的甲醇制烯烃工艺(MTO)和德国Lurgi公司的固定床甲醇制丙烯工艺(MTP)。 [0003] Currently, the world's more mature MTO process are the United States UOP's MTO process (MTO) and the German company Lurgi fixed bed methanol to propylene process (MTP). 国内则有中科院大连化学物理研究所开发的甲醇制低碳烯烃工艺(DMTO)和清华大学研究开发的流化床甲醇制丙烯工艺(FMTP)。 There are domestic fluidized bed methanol to propylene CAS Dalian Institute of Chemical Physics technology developed by MTO process (DMTO) and research and development of Tsinghua University (FMTP). MTO工艺主要用于制备乙烯和丙烯,MTP工艺则主要用于制备丙烯。 MTO process for the preparation of mainly ethylene and propylene, MTP process is mainly used for the preparation of propylene.

[0004] 固定床甲醇制丙烯工艺主要由德国Lurgi公司开发完成并形成专利技术,欧洲专利EP0448000B1、中国专利CN1431982A等均已公开了该工艺方法以及所使用的催化剂。 [0004] The fixed bed methanol to propylene and form a complete process is mainly developed by the German company Lurgi patents, European Patent No. EP0448000B1, have been disclosed in Chinese Patent No. CN1431982A, etc. and a process for the catalyst used. 该工艺方法基于德国南方化学公司提供的改性ZSM-5分子筛催化剂,采用单级与多级绝热固定床反应器,具有较高的丙烯收率,同时副产少量乙烯、汽油和液化石油气(LPG)。 The process is based on modified ZSM-5 zeolite catalyst South German Chemical Company, using single-stage and multi-stage adiabatic fixed bed reactor, having a higher propylene yield, while production of a small amount of ethylene, gasoline and liquefied petroleum gas ( LPG). 由于固定床中催化剂需进行原位间歇再生,因此,通常采用设置多个固定床反应器(如二开一备,即使用两个固定床反应器,备用一个固定床反应器)进行切换以解决上述问题,但该设计方式存在着系统设备要求高、操作复杂的问题。 Since the catalyst bed for an intermittent regeneration in situ, therefore, usually a plurality of fixed bed reactors (e.g., two open a preparation, i.e. the use of two fixed bed reactors, a spare fixed bed reactor) is switched to address the above problem, but there are high demands system device, the problem of complicated operation design.

[0005] 流化床技术最初由UOP公司研究开发成功,除此之外,目前国内也有大连化物所、 清华大学从事该工艺的开发。 [0005] fluidized bed technology originally developed by UOP's successful research and development, in addition, currently there are DICP, Tsinghua University in the development process. 流化床技术主要采用SAP0-34催化剂,它对低碳烯烃有很高的选择性,但对丙烯的单程选择性不高,而且SAP0-34催化剂在流化床中的磨损严重,这是今后其工业化应用需要攻克的难题。 Fluidized bed technology mainly SAP0-34 catalyst, it has a high selectivity to light olefins, but one way is not high selectivity towards propylene, and SAP0-34 catalyst in a fluidized bed of serious wear and tear, which is the future its industrial application needs to overcome the problem.

[0006] 移动床技术由于床内固体返混小、反应接近活塞流,因而原料转化率高,且床内催化剂不断移动(再生)因而能保持良好的催化性能,愈来愈受到研究人员的重视。 [0006] Since the moving bed technology within the bed solids backmixing small, approaching plug flow reactor, thus a high conversion of the feedstock and the catalyst continually moving bed (regenerated) and thus maintain good catalytic performance, more and more attention of researchers . 公开号为CN1803738A的中国专利申请公开了一种移动床甲醇制丙烯技术,通过采用双功能分子筛催化剂,利用反应-再生的方法实现催化剂的循环,同时引入副产物的循环转化,从而提高丙烯的选择性。 Publication No. CN1803738A Chinese patent application discloses a moving bed technique methanol to propylene, by using a bifunctional molecular sieve catalyst by the reaction - regeneration of the circulating catalyst to achieve, while introducing a cyclic conversion byproducts, thereby improving the selection of propylene sex. ZSM-5是一种具有中孔性质的分子筛催化剂,具有中等的积炭速率。 ZSM-5 zeolite catalyst is in pores having properties, having a moderate rate of coke. 移动床技术是一种连续反应再生的技术,尤其适用于具有中等积炭速率的催化剂。 Technique is a continuous moving bed regeneration reaction technique, especially for a catalyst having a moderate rate of coke formation. 它既可以像循环流化床一样连续反应再生,同时又不需要催化剂具有很高的耐磨性。 It can be as circulating fluidized bed reactor as a continuous regeneration, while no catalyst having a high wear resistance.

[0007] 授权公告号为CN1152944C的中国专利公开了含有四个反应区的连续反应-再生装置;公开号为CN 101367701A的中国专利申请公开了一种采用两段反应区,将含氧化合物原料在第一段反应区生成产物,再将产物中的C5以上组分通入第二反应区进行催化剂预积炭,再将第二反应区预积炭的催化剂用于第一反应区反应,最后将催化剂通入再生器。 [0007] authorized announcement No. CN1152944C Chinese patent discloses a continuous reaction in a reaction zone containing four - reproducing means; Publication No. of Chinese Patent Application No. CN 101367701A, discloses a two-stage reaction zone, the oxygenate feedstock generating a first reactor product and the product of the above component C5 into the second reaction zone catalyst pre-coke, coke and then a second pre-catalyst reaction zone for the first reaction zone of the reactor, and finally the catalyst into the regenerator. 这种利用连续反应-再生装置的反应连续再生的工艺方法和将催化剂从第二反应区输送到第一反应区,均需要在反应系统之间以及反应系统与再生装置之间增加特别的气提装置将反应器流出来的催化剂输送到再生装置再生,这需要很大的输送动力,存在着能耗过高、 经济效益欠佳的技术缺陷。 This reaction using a continuous - process for continuous regeneration of the reaction reproducing apparatus of the first reaction zone and the catalyst from the second reaction zone to transport, require an increase in the special stripping between the reaction system and the reaction system and the reproducing apparatus the catalytic reactor is conveyed to flow out reproduction apparatus for reproducing, which requires a large conveying power, there is a high energy consumption, poor economic technical drawbacks.

发明内容 SUMMARY

[0008] 本发明提供了一种使用移动床技术将甲醇转化为丙烯的半连续方法,仅用一种分子筛催化剂即实现了移动床内甲醇到丙烯的三段反应,最终实现提高丙烯收率的目的。 [0008] The present invention provides a method of using moving bed technology for converting methanol to propylene semi-continuous process, i.e. with only one molecular sieve catalyst to achieve a three-stage moving bed reactor of methanol to propylene, and ultimately increase the propylene yield purpose.

[0009] 一种使用移动床技术将甲醇转化为丙烯的半连续方法,包括以下步骤: [0009] A moving bed technology for converting methanol to propylene semi-continuous process, comprising the steps of:

[0010] 1)将分子筛催化剂与催化剂稀释剂混合后连续通入第一反应区,将甲醇原料通入第一反应区与分子筛催化剂接触,在〜300°C、0. IMPa〜IMPa条件下,分子筛催化剂在第一反应区内停留30h〜100h,产生第一股物流; After [0010] 1) mixing the catalyst with a molecular sieve catalyst diluent continuously into a first reaction zone, the methanol feed into a first reaction zone with a molecular sieve catalyst, at ~300 ° C, 0. IMPa~IMPa conditions, the molecular sieve catalyst in a first reaction zone residence 30h~100h, generating a first streams;

[0011] 所述的第一股物流包括甲醇、二甲醚和水; The [0011] first streams include methanol, dimethyl ether and water;

[0012] 所述的第一反应区至少包括一个移动床反应器; According to [0012] the first reaction zone comprises at least one moving bed reactor;

[0013] 2)经过第一反应区后的分子筛催化剂进入到第二反应区,将步骤1)中得到的第一股物流通入第二反应区与分子筛催化剂接触,在430°C〜530°C、0. IMPa〜0. SMPa条件下,分子筛催化剂在第二反应区内停留30h〜100h,产生第二股物流; [0013] 2) After the molecular sieve catalyst after a first reaction zone into the second reaction zone, the first streams in step 1) obtained into a second reaction zone with a molecular sieve catalyst at 430 ° C~530 ° .. C, 0 IMPa~0 under SMPa conditions, the molecular sieve catalyst in the second reaction zone residence 30h~100h, generating second stream;

[0014] 所述的第二股物流包括乙烯、丙烯、丁烯、C1〜C4烷烃和C5以上组分; The [0014] second stream comprising ethylene, propylene, butene, C1~C4 alkane and a C5 or more components;

[0015] 所述的第二反应区至少包括一个移动床反应器; The [0015] second reaction zone comprises at least one moving bed reactor;

[0016] 3)将步骤2、中产生的第二股物流与步骤1)中的甲醇原料换热后,经脱水和脱氧化物后进行分离(即经气液分离与精馏之后脱除水和未转化的甲醇及二甲醚等氧化物后进行分离),得到第二反应区返回料、第二反应区出料和第三反应区进料,第二反应区返回料并入第一股物流循环至步骤2); [0016] 3) The Step 2, the second stream feed exchanger of step 1) in methanol produced, after dehydration and removal oxide is separated (i.e., after removal of water by distillation and the gas-liquid separator for unconverted methanol and dimethyl ether oxide after separation), to give a second reaction zone recycle material, feeding the second reaction zone and the third reaction zone feed, the second reaction zone incorporated into the first return feed streams recycled to step 2);

[0017] 所述的第二反应区返回料包括乙烯、丁烯和C2〜C4烷烃,所述的第二反应区出料包括C1烷烃和丙烯,所述的第三反应区进料包括C5以上组分; [0017] The second reaction zone recycle material include ethylene, butene and C2~C4 alkane, said second reaction zone effluent stream comprising propylene alkanes and C1, the third reaction zone feed comprising C5 more component;

[0018] 4)经过第二反应区后的分子筛催化剂进入到第三反应区,将步骤幻中得到的第三反应区进料通入第三反应区与分子筛催化剂接触,在465°C〜M0°C、0. IMI^a〜0. 5ΜΙ^条件下,分子筛催化剂在第三反应区停留30h〜100h,产生第三股物流; [0018] 4) After the molecular sieve catalyst through the reaction zone into the second reaction zone to the third, the third step of the reaction zone feed phantom obtained into third reaction zone with a molecular sieve catalyst at 465 ° C~M0 .. ° C, 0 at IMI ^ a~0 5ΜΙ ^ conditions, the molecular sieve catalyst in the third reaction zone residence 30h~100h, generating third streams;

[0019] 所述的第三股物流包括丙烯、乙烯、丁烯、C1〜C4烷烃和C5以上烃; [0019] The third streams include propylene, ethylene, butene, C1~C4 alkane and a C5 or more hydrocarbon;

[0020] 所述的第三反应区至少包括一个移动床反应器; [0020] The third reaction zone comprises at least one moving bed reactor;

[0021] 分子筛催化剂与催化剂稀释剂混合后连续输送到第一反应区,分子筛催化剂缓慢连续移动,依次流经第一反应区、第二反应区、第三反应区,经过第三反应区后的分子筛催化剂收集后定期进行再生得到再生催化剂,再生催化剂间歇地并入分子筛催化剂中循环至步骤1)。 [0021] After the molecular sieve catalyst and a diluent mixed catalyst is continuously supplied to the first reaction zone, the molecular sieve catalyst is continuously moved slowly, sequentially through the first reaction zone, a second reaction zone, a third reaction zone, after the third reaction zone periodically regenerated molecular sieve catalyst to obtain regenerated catalyst was collected, the step of circulating a molecular sieve catalyst to regenerated catalyst incorporated intermittently 1).

[0022] 为了得到更好的发明效果,以下作为本发明的进一步的优选: [0022] In order to obtain better effects of the invention, the present invention further preferably:

[0023] 所述的使用移动床技术将甲醇转化为丙烯的半连续方法,还包括:¾将步骤4)中得到的第三股物流与第二反应区进料进行换热后进行分离,分离得到乙烯、丁烯和C2〜C4 烷烃并入第一股物流循环至步骤幻。 The moving bed technology [0023] The conversion of methanol to propylene semi-continuous process, further comprising: ¾ third streams in step 4) obtained in the second reaction zone feed is separated after heat exchange, separation to obtain ethylene, butene, and incorporated by C2~C4 alkane streams recycled to the first step phantom. 步骤幻的增加,使得本发明使用移动床技术将甲醇转化为丙烯中能量利用率和物料利用率进一步提高,具有更好的经济效益。 The step of increasing the magic, so that the present invention is the use of moving bed technology for converting methanol to propylene materials utilization and energy efficiency is further improved, with better economics.

[0024] 移动床反应器可具体选用现有的移动床反应器,如申请号为201010175837. 1的中国专利申请公开的一种用于以含氧化合物为原料生产丙烯的管式移动床反应器,申请号为200810120839. 3的中国专利申请公开的一种用于以含氧化合物为原料生产丙烯的径向移动床反应器,申请号为200810120838.9的中国专利申请公开的一种用于以含氧化合物为原料生产丙烯的卧式移动床反应器。 [0024] The moving bed reactor may be specific choice of conventional moving bed reactor, such as Application No. of China Patent Application No. 201010175837.1 disclosed a method for moving a tubular reactor bed oxygenate propylene as raw materials , application No. of China Patent application No. 200810120839.3 disclosed in Chinese patent application for radially moving bed reactor to produce oxygenate feedstock as propylene, application No. 200810120838.9 disclosed a method for the oxygen-containing Starting from the compounds of horizontal moving bed reactor to yield propylene.

[0025] 所述的三个反应区的催化剂为同一种分子筛催化剂,所述的分子筛催化剂优选为ZSM-5分子筛,ZSM-5分子筛是一种具有中孔性质的分子筛催化剂,具有中等的积炭速率, 而且在移动床内的耐磨损性较好。 [0025] The catalyst according to three same reaction zone molecular sieve catalyst, the molecular sieve catalyst is preferably a ZSM-5 zeolite, ZSM-5 molecular sieve is a molecular sieve catalyst has pore properties, with medium coke rate, and the wear resistance is better in the moving bed. 由于甲醇制丙烯反应为强放热反应,故需要添加惰性、大比热容的固体粒子稀释催化剂,防止出现局部热点。 Since methanol to propylene is highly exothermic reaction, it is necessary to add an inert, large specific heat capacity of the solid catalyst particles diluted, to prevent local hot spots. 所述的催化剂稀释剂为陶瓷颗粒或石英砂颗粒,一般选用具有较大的比热容、颗粒尺寸与分子筛尺寸相同的催化剂稀释剂。 The diluent for the catalyst of silica particles or ceramic particles, generally used has a large specific heat capacity, particle size and the same size molecular sieve catalyst diluent. 所述的分子筛催化剂与催化剂稀释剂的质量比为1 : 1〜20。 The molecular sieve catalyst mass ratio of diluent to catalyst is 1: 1~20. 甲醇原料可以是不同的工业原料,如采用甲醇或者甲醇与水的混合物,甲醇原料中可以包含少量的杂质。 Methanol feedstock may be various industrial raw materials, such as using a mixture of methanol and water or methanol, the methanol feedstock may contain small amounts of impurities.

[0026] 由于采用步骤1)中第一股物流的二甲醚生成丙烯和其他烯烃的反应热比直接从甲醇转化为丙烯要低很多,本发明将甲醇转化为丙烯分成三步,其中第一步主要是将甲醇转化为二甲醚(第一反应区),第二步主要是将二甲醚转化为丙烯(第二反应区),第三步是将高碳烃裂解转化为丙烯(第三反应区)。 [0026] As a result of step 1) in the first strand reaction heat DME to propylene and other olefins stream is much lower than the direct conversion of methanol to propylene, the present invention is a propylene conversion of methanol into three steps, wherein the first the main step is the conversion of methanol to dimethyl ether (first reaction zone), the second step is mainly the DME to propylene (second reaction zone), the third step is the cracking higher hydrocarbons to propylene (first three reaction zones). 从而将甲醇转化为丙烯的反应热分成两部分, 两部分反应热分别释放在第一和第二反应区。 Thereby converting methanol to propylene reaction heat into two parts, the two parts are heat of reaction released in the first and second reaction zones. 由于较高温度下焦炭形成反应加速,同时,分子筛催化剂脱铝反应加速,因此,本发明将甲醇转化为丙烯的反应热分成两部分,从而避免将甲醇转化为丙烯的过程中温度升高过快,不仅能够抑制焦炭的形成,而且可以抑制催化剂的脱铝,使催化剂保持高活性。 Because coke formation at higher temperature to accelerate the reaction, at the same time, the molecular sieve catalyst dealumination reaction accelerator, therefore, the present invention is the heat of reaction to convert methanol to propylene into two parts, thus avoiding to convert methanol to propylene rapid temperature increase during , not only inhibit coke formation, but can be suppressed dealuminated catalyst, the catalyst maintained a high activity.

[0027] 所述的步骤2、,第一股物流中加入水蒸气后通入第二反应区与分子筛催化剂接触。 The step of [0027] 2 ,, the first streams into the second reaction zone with a molecular sieve catalyst after addition of water vapor. 水蒸气可具体选用公用工程水蒸气。 The specific choice of public works water vapor water vapor. 水蒸气的增加可明显减少分子筛催化剂的积炭, 在较长时间之内使分子筛催化剂的活性保持在一定范围值。 Increasing the water vapor can significantly reduce coke molecular sieve catalyst, the molecular sieve catalyst is kept active within a certain range of values ​​over a longer time. 优选第一股物流与水蒸气的摩尔比控制在0.25〜4 : 1。 Preferably the molar ratio of the first stream and steam Control Unit in 0.25~4: 1.

[0028] 所述的第二反应区的反应温度选择430°C〜530°C,此温度范围下含氧化合物可以有效的转化为烯烃,此范围的较低温度有利于丙烯的生成,而较高温度有利于乙烯的生成,为了使得丙烯的转化率提高,反应温度优选为450°C〜500°C。 [0028] The reaction temperature of the second reaction zone selection 430 ° C~530 ° C, the oxygen-containing compound can be effectively converted to olefins at this temperature range, the lower temperature range is conducive to the formation of propylene It was high temperatures favor the formation of ethylene, such that in order to improve the conversion of propylene, the reaction temperature is preferably 450 ° C~500 ° C.

[0029] 所述的第一反应区、第二反应区和第三反应区中的反应原料流与分子筛催化剂流动呈逆流。 [0029] The first reaction zone, a second reaction zone and a third reaction zone in the reaction feed stream with a countercurrent flow of a molecular sieve catalyst. 其中,将反应原料流引入反应区的下部,并从反应区上部移出,分子筛催化剂在重力作用下,向下移动,从而呈现逆流。 Wherein the feed stream is introduced into the lower portion of the reaction the reaction zone, and removed from the upper portion of the reaction zone, the molecular sieve catalyst under gravity, moves downwardly, thereby presenting countercurrent. 当反应原料流的流速较高时,发生在转化的初始阶段,反应原料流是与部分失活的分子筛催化剂接触,而当反应原料流的流速较低时,发生在转化的随后深入阶段,反应原料流是与活性较高的分子筛催化剂接触,因此,甲醇原料与分子筛催化剂流动呈逆流能有效的保持了催化剂对低碳烯烃的选择性。 When the high velocity of the reaction feed stream occurs in the initial stage of the conversion, the reaction feedstream is contacted with a molecular sieve catalyst deactivation section, when the flow rate is low and the reaction feed stream in the subsequent stage of deep conversion of the reaction feed stream with a molecular sieve catalyst higher activity, and therefore, the methanol feed with a molecular sieve catalyst can effectively flow in countercurrent to maintain the selectivity of the catalyst to light olefins.

[0030] 催化剂在反应区的停留时间(即反应物与催化剂的接触时间)对甲醇转化为丙烯的转化率和反应产物分布有着显著的影响。 [0030] The residence time of the catalyst in the reaction zone (i.e., the contact time of the reaction product and the catalyst) for conversion of methanol to propylene conversion and product distribution of the reaction has a significant impact. 停留时间短,原料与催化剂接触不充分,反应转化率低,而停留时间太长,容易导致产物中甲烷、丙烷、丁烷等烷烃、芳烃等副产物增加。 Short residence time, contact with the catalyst material is not sufficient, the reaction conversion rate is low, and the residence time is too long, easily lead to product-product methane, propane, butane and other paraffins, aromatics increases. 反应物与催化剂的接触时间通常用重时空速(WHSV)表示,WHSV指每小时进料中反应原料的质量与反应器内催化剂质量的比值,WHSV数值越大代表停留时间越短,本发明第一反应区、第二反应区和第三反应区的WHSV都优选0. 1〜ZOhr-1。 The contact time of the reactants with the catalyst is usually a weight hourly space velocity (WHSV) represents, WHSV refers to the ratio of the mass of catalyst mass with the feedstock into the reactor feed per hour reaction, WHSV greater the value representative of the shorter residence time, the present invention a reaction zone, a second reaction zone and a third reaction zone WHSV are preferably 0. 1~ZOhr-1.

[0031] 所述的分子筛催化剂在反应区内的停留时间优选为90〜300h。 [0031] The residence time of the molecular sieve catalyst in the reaction zone is preferably 90~300h. 分子筛催化剂或者并入再生催化剂后的分子筛催化剂自进料入口进入第一反应区的移动床反应器后,在移动床反应器内缓慢移动,然后连续移动通过第二反应区的移动床反应器、第三反应区的移动床反应器,经过90〜300小时后移出移动床反应器进入催化剂收集器。 After the molecular sieve catalyst or a molecular sieve catalyst incorporated in a regenerated catalyst from the feed inlet into the moving bed reactor of the first reaction zone, moves slowly in a moving bed reactor, and then continuously moved through a moving bed reactor of the second reaction zone, moving bed reactor of the third reaction zone, 90~300 hours after removal of the moving bed reactor into the catalyst collector.

[0032] 步骤4)中,经过第三反应区后的分子筛催化剂(即积炭的分子筛催化剂)采用催化剂收集器,将收集到的分子筛催化剂定期输送到再生装置中再生得到再生催化剂,再生催化剂并入分子筛催化剂中循环至步骤1)。 [0032] Step 4), after the molecular sieve catalyst (i.e., molecular sieve catalyst coke) using the third reaction zone catalyst collector, the molecular sieve catalyst collected periodically supplied to reproducing means reproducing regenerated catalyst, regenerated catalyst and into the zeolite catalyst is recycled to step a). 所述的再生催化剂与未并入再生催化剂前的分子筛催化剂(即新鲜的分子筛催化剂)的质量比为O〜3 : 7。 The mass of the regenerated catalyst with a molecular sieve catalyst (i.e., fresh molecular sieve catalyst) before the regenerated catalyst ratio was not incorporated O~3: 7. 将反应系统与催化剂再生装置相独立,即催化剂积累到一定量之后集中送去再生装置再生,不但可以节省输送成本, 也减少了装置的复杂性。 The reaction system independent catalyst regeneration apparatus, reproduction apparatus for reproducing concentrated sent, not only save transport costs, but also reduces the complexity of the device after the catalyst is accumulated to a certain amount, ie.

[0033] 一种将甲醇转化为丙烯的装置,包括依次串联的催化剂加料罐、催化剂加料控制器、第一反应区、第二反应区、第三反应区、催化剂出料缓冲罐、催化剂出料控制器和催化剂收集器。 [0033] A method for converting methanol to propylene apparatus, comprising a catalyst addition tank in series, the catalyst feed controller, a first reaction zone, a second reaction zone, a third reaction zone, the catalyst buffer tank discharge, discharge catalyst and a controller catalyst collector. 其中,所述的第一反应区、第二反应区和第三反应区分别至少包括一个移动床反应器。 Wherein said first reaction zone, a second reaction zone and a third reaction zone includes at least one moving bed reactor. 各个移动床反应器置于不同的水平高度,相邻的移动床反应器之间,移动床反应器的底部与下一个移动床反应器的顶部连通,例如,可通过管线或者移动床重叠式串接,各个移动床反应器连接之后两端分别与催化剂加料控制器、催化剂出料缓冲罐连接。 Each of the moving bed reactor is placed in different height levels, between adjacent moving bed reactor, moving bed reactor at the bottom and the top of the next communication moving bed reactor, for example, it may be through line or moving bed overlay string then, after moving bed reactors each respectively connected to both ends of the catalyst feeder controller, buffer tank connected to the catalyst discharge. 通过这种方式连接的各个移动床反应器能够保证催化剂依靠自身重力自上而下移动,从上到下依次通过各个移动床反应器,原料甲醇与催化剂形成错流,并且可降低能耗。 Each moving bed reactors connected in this way to ensure that the catalyst moves from top to bottom on its own gravity, from top to bottom through the respective moving bed reactor, the methanol feed stream with the catalyst is formed wrong, and power consumption can be reduced.

[0034] 所述的催化剂加料控制器为催化剂由低压向高压输送的无阀装置。 [0034] No catalyst feed valve means according to the controller by a catalyst delivery of low pressure to the high pressure. 此无阀装置通过低压上段、过渡中间段、高压下段以及连通相邻两端区域的下料管、阻塞阀以及附属的节流装置来控制颗粒由低压向高压段的流动与截止。 This by no means the valve low-pressure section, an intermediate transition section and a lower section of the high-pressure pipe, the choke valve and the throttle device attached to both ends of the adjacent communication area controlled by the flow of particles to the high-pressure section and a low pressure off.

[0035] 所述的催化剂出料控制器为无阀锁压装置。 [0035] The catalyst discharge pressure controller valveless lock means. 当反应器内的压力高于外界大气压力时,为了将催化剂从料斗中输送到反应区,必须提高催化剂进料口的压力或者降低第一反应区的压力,为实现这个目的,在催化剂进口设置一个无阀锁压输送装置,无阀锁压装置可以实现催化剂颗粒由高压向低压的输送,而不泄露移动床反应器内的压力,实现一个锁压功能,并且该锁压装置可控制催化剂的下料速率并且能大大降低催化剂在下料流动过程中的磨损现象。 When the pressure in the reactor is greater than ambient atmospheric pressure, in order to transport the catalyst from the hopper to the reaction zone, the catalyst must be increased inlet pressure or reduced pressure in the first reaction zone, in order to achieve this object, a catalyst inlet provided a valveless lock pressure delivery device, pressure valveless lock means may be implemented by the transport of the catalyst particles to a high pressure and low pressure, without leakage of the pressure in the moving bed reactor, to achieve a press-lock feature, and the lock means may control the pressure of the catalyst and the feed rate of the catalyst can greatly reduce the fretting phenomenon during the next feed flow.

[0036] 该甲醇转化为丙烯的装置还包括再生装置,催化剂收集器中的分子筛催化剂采用人工输送的办法定期送到再生装置中进行再生,之后间歇地加入到催化剂加料罐中。 Means [0036] The conversion of methanol to propylene further comprises reproducing means, the molecular sieve catalyst employed in the catalyst collector approach to artificial conveyed periodically regenerated reproducing apparatus, then intermittently added to the catalyst feed tank.

[0037] 所述的第一反应区、第二反应区、第三反应区中均设有换热装置。 According to [0037] the first reaction zone, a second reaction zone, the reaction zone has a third heat exchange means. 所述的换热装置位于移动床反应器内和/或各移动床反应器之间。 Heat exchange means positioned between the moving bed reactor and / or the respective moving bed reactor. 在移动床反应器之间设置换热装置,不但可以移去反应过程中产生的反应热,便于更好的控制每步反应的反应温度,而且交换出的热量可以预热各反应区入口的物料,节省了公用工程热量的输入,达到了综合利用系统热能的目的。 In the moving bed reactor is provided between the heat exchange means, not only can remove reaction heat generated during the reaction, the reaction temperature to facilitate better control of the reaction of each step, and a heat exchanger in each reaction zone can be preheated material inlet , saving the utility heat input to achieve the purpose of energy utilization system. 当放热量过大时,此时在移动床反应器之间增设的激冷装置,激冷装置具体可选择换热器,可以有效移去多余的反应热,如步骤3)中第二股物流与甲醇原料换热后,激冷装置中的激冷液具体采用甲醇原料,甲醇原料具体可选用甲醇或者甲醇与水的混合物, 当采用甲醇原料时,可以提高甲醇原料的处理量。 When excessive heat, chilling means at this time between the addition of the moving bed reactor, quench heat exchanger particularly Alternatively, the reaction can effectively remove excess heat, such as in step 3) second stream after heat exchange with the feedstock methanol, chilled quench liquid employed in particular methanol feedstock, particularly methanol feed can be selected mixture of methanol and water or methanol, when using methanol feedstock can increase the processing amount of the methanol feedstock.

[0038] 与现有技术相比,本发明具有以下优点:[0039] 1)本发明再生催化剂间歇地并入分子筛催化剂(即新鲜的分子筛催化剂),连续的通过移动床反应区,积炭催化剂集中收集,定期送去再生的方法,使用一种分子筛催化剂即完成了甲醇制二甲醚、二甲醚制丙烯及高碳烃裂解的三段反应,实现了反应器内物料与分子筛催化剂反应连续,反应器外分子筛催化剂加料与收集半连续的移动床工艺,增加了反应系统与再生装置的独立性,减少了整套设备的复杂性。 [0038] Compared with the prior art, the present invention has the following advantages: [0039] 1) regeneration of the catalyst of the present invention incorporated into the molecular sieve catalyst is intermittently (i.e., fresh molecular sieve catalyst), by continuously moving bed reaction zone, the catalyst coke centralized collection, sent periodically regenerating method using a molecular sieve catalyst to complete the three-stage reaction of methanol to dimethyl ether, dimethyl ether of propylene and higher hydrocarbons cracking, the reactor contents achieved with the molecular sieve catalyst continuously , the molecular sieve outside of the reactor and catalyst feed collecting semi-continuous moving bed process, the reaction system to increase the independence of the reproducing device, reducing the complexity of the whole device.

[0040] 2)本发明使用移动床技术将甲醇转化为丙烯的半连续方法将反应分成了三段进行反应,三段用同一个分子筛催化剂,不但可以提高甲醇生成二甲醚反应段的转化率,减少最终分离出的废水中甲醇的含量,且C2〜C4低碳烃的回炼与C5以上高碳烯烃的裂解提高了最终目的产物丙烯的选择性,同时避免了操作上不同催化剂需要分批引出再生的复杂性。 [0040] 2) The present invention uses moving bed technology for converting methanol to propylene semi-continuous process the reaction the reaction into three segments, three segments with the same molecular sieve catalyst, not only can increase the conversion of methanol to dimethyl ether reaction zone , reduce the final content of the waste water in the separated methanol, and back to the refining and cracking of light hydrocarbons C2~C4 carbon C5 olefin selectivity is improved over the final desired product propylene while avoiding the need to operate different catalyst batches lead complex regeneration.

[0041] 3)本发明将甲醇转化为丙烯反应过程的反应热分为两段,利用第一反应区的醚化反应放出的反应热预热进入第二反应区的反应原料,使丙烯合成反应区内的平均温升能够有效控制,从而减少了催化剂的积碳和脱铝现象,保持了催化剂的高活性。 [0041] 3) of the present invention for converting methanol to propylene reaction heat during the reaction into two etherification reaction heat, released by the first reaction zone into the preheated reactor feed to the second reaction zone, the synthesis reaction of propylene the average temperature region can be effectively controlled, thereby reducing the phenomenon of carbon and dealuminated catalyst maintained high activity of the catalyst.

[0042] 4)本发明通过增设催化剂加料控制器和催化剂出料控制器解决了催化剂进料与出料对反应装置密封性的影响问题,采用积炭催化剂集中收集,定期送去再生的方法,简化了装置的设计复杂性。 [0042] 4) The present invention solves the catalyst feed and discharge means sealing the impact on the reaction by adding the catalyst feed and catalyst feed controller controller, using the catalyst coke centralized collection, sent periodically regenerating method, It simplifies the design complexity of the device.

[0043] 5)本发明在各反应区的移动床之间增设了换热装置,将系统多余的反应热用于加热高温段反应区的进口物流,综合利用了反应进料与产物出料流股的热能。 [0043] 5) In the present invention, each reaction zone between the moving bed heat exchange means of the addition, excess heat of reaction system for heating high-temperature stream inlet section of the reaction zone, the reaction feed utilization with the product stream energy stocks.

[0044] 6)本发明采用多反应区重叠布置,催化剂连续流动,实现了反应长期的连续进行。 [0044] 6) The present invention uses multiple reaction zone overlapping arrangement, a continuous flow of catalyst to achieve long-term continuous reaction. 本发明采用第二反应区回炼部分产物(乙烯、丁烯和C2〜C4的烷烃),提高了丙烯选择性。 The present invention employs a second reaction zone back to the refining part of the product (ethylene, butene and C2~C4 alkane), to improve the selectivity of propylene. 本发明采用第三反应区裂解高碳数的烃类,并将分离后的回炼部分产物(C2〜C4的烷烃、乙烯和丁烯)返回到第二反应区反应,降低了副产物的含量,提高了丙烯的收率。 The present invention employs a third reaction zone of cleaved carbon number hydrocarbons, and back to the refining part of the product after separation (C2~C4 alkane, ethylene and butene) returns to the second reaction zone, reduces the content of by-products , increasing the yield of propylene.

附图说明 BRIEF DESCRIPTION

[0045] 图1为本发明将甲醇转化为丙烯的装置的结构示意图。 [0045] Figure 1 is a schematic view of the invention for converting methanol to propylene apparatus configuration. 具体实施方式 detailed description

[0046] 如图1所示,为将甲醇转化为丙烯的装置,包括依次串联的催化剂加料罐STlJI 化剂加料控制器Fl (催化剂由低压向高压输送的无阀装置)、第一反应区D1、第二反应区D2、第三反应区D3、催化剂出料缓冲罐B、催化剂出料控制器F2和催化剂收集器ST2 (无阀锁压装置)。 [0046] 1, the conversion of methanol to propylene apparatus, comprising a catalyst addition tank STlJI agent feed controller Fl (without catalyst delivery valve means to a low pressure by the high pressure) in series, the first reaction zone D1 the second reaction zone D2, the third reaction zone D3, a buffer tank discharging the catalyst B, catalyst and catalyst discharge controller F2 collector ST2 (valveless lock pressure device). 第一反应区D1、第二反应区D2和第三反应区D3分别至少包括一个移动床反应器。 The first reaction zone D1, the second reaction zone and a third reaction zone D2 D3 includes at least one moving bed reactor. 各个移动床反应器置于不同的水平高度,相邻的移动床反应器之间,移动床反应器的底部与下一个移动床反应器的顶部连通,例如,可通过管线或者移动床重叠式串接,各个移动床反应器连接之后再与催化剂加料控制器F1、催化剂出料缓冲罐B连接。 Each of the moving bed reactor is placed in different height levels, between adjacent moving bed reactor, moving bed reactor at the bottom and the top of the next communication moving bed reactor, for example, it may be through line or moving bed overlay string then, each of the moving bed reactor is connected after the catalyst addition and then the controller F1, catalyst B buffer tank connected to the discharge. 该甲醇转化为丙烯的装置还包括再生装置R,催化剂收集器ST2中的分子筛催化剂采用人工输送的办法定期送到再生装置R中进行再生,之后间歇地加入到催化剂加料罐STl中。 The conversion of methanol to propylene apparatus further comprises means R regenerated molecular sieve catalyst in the catalyst collector ST2 approach using artificial periodically conveyed to the reproducing apparatus for reproducing the R, then intermittently added to the catalyst feed tank STl. 第一反应区D1、第二反应区D2、第三反应区D3中分别设有换热装置H1、H2、H3、E1和E2。 The first reaction zone D1, the second reaction zone D2, D3 in the third reaction zone are provided with heat exchange means H1, H2, H3, E1 and E2. 换热装置HI、 H2、H3位于移动床反应器内和/或各移动床反应器之间,用于较精确预热各反应区入口的物料。 Heat exchanger device HI, H2, H3 located between the moving bed reactor and / or the respective moving bed reactor for preheating the material more accurately each reaction zone inlet. 换热装置El和E2用于利用反应区出料的热量预热各反应区入口的物料。 El and E2 heat exchange means for utilizing the heat of reaction zone effluent stream preheated material inlet of each reaction zone. 本发明甲醇转化为丙烯的装置还包括分离区s印1、s印2。 Methanol conversion apparatus of the present invention further comprises a propylene separation zone printed s 1, s 2 and India.

[0047] 本发明使用移动床技术将甲醇转化为丙烯的半连续方法,包括以下步骤: [0047] The present invention is semi-continuous process using moving bed technology for converting methanol to propylene comprising the steps of:

[0048] 1)将分子筛催化剂与催化剂稀释剂由催化剂加料罐STl通过催化剂加料控制器Fl从第一反应区Dl顶部连续加入到第一反应区Dl,通过调节加料控制器Fl下端的节流装置控制进料的速度;甲醇原料s经过换热装置Hl后从第一反应区Dl底部通入到第一反应区Dl与分子筛催化剂接触,在240°C〜300°C、0. IMPa〜IMPa反应条件下,分子筛催化剂在第一反应区Dl停留30h〜100h,在第一反应区Dl顶部的出口产生第一股物流a ; [0048] 1) molecular sieve catalyst by a diluent to catalyst addition tank STl Dl from the top of the first reaction zone continuously added to the first reaction zone via catalyst feed controller Dl Fl, Fl the lower end of the addition by adjusting the throttle device controller controlling the speed of the feed; s after the methanol feed Hl from the bottom of the heat exchanger device Dl into the first reaction zone to the first reaction zone with a molecular sieve catalyst Dl, at 240 ° C~300 ° C, 0 IMPa~IMPa reaction. under the conditions, the molecular sieve catalyst in a first reaction zone residence Dl 30h~100h, Dl at the top of the first reaction zone a first outlet streams to produce a;

[0049] 所述的第一股物流a包括甲醇、二甲醚和水; [0049] The first strand of a stream comprising methanol, dimethyl ether and water;

[0050] 所述的第一反应区Dl至少包括一个移动床反应器; Said first reaction zone Dl [0050] comprising at least one moving bed reactor;

[0051] 幻经过第一反应区Dl后的分子筛催化剂从第二反应区D2顶部进入到第二反应区D2,将步骤1)中得到的第一股物流a经过换热装置H2后从第二反应区D2底部通入第二反应区D2与分子筛催化剂接触,在430°C〜530°C、0. IMPa〜0. 8MPa条件下,分子筛催化剂在第二反应区D2停留30h〜100h,产生第二股物流c从第二反应区D2顶部的出口流出; [0051] After the molecular sieve catalyst after the magic first reaction zone enters Dl D2 from the top of the second reaction zone to the second reaction zone D2, the first streams of step 1) obtained after a H2 from the second heat exchanger device D2 into the bottom of the reaction zone in contact with the second reaction zone D2 molecular sieve catalyst at 430 ° C~530 ° C, 0. IMPa~0. 8MPa conditions, the molecular sieve catalyst in the second reaction zone residence D2 30h~100h, generates a first c two streams flowing from the top of the outlet D2 of the second reaction zone;

[0052] 所述的第二股物流c包括乙烯、丙烯、丁烯、C1〜C4烷烃和C5以上组分; [0052] c of the second stream include ethylene, propylene, butylene, C1~C4 alkane and a C5 or more components;

[0053] 所述的第二反应区D2至少包括一个移动床反应器; [0053] D2 of the second reaction zone comprises at least one moving bed reactor;

[0054] 3)将步骤幻中的第二股物流c与步骤1)中甲醇原料s在换热装置El换热后,经脱水和脱氧化物后进入分离区sepl分离,得到第二反应区返回料d、第二反应区出料pi和第三反应区进料e,第二反应区返回料d并入第一股物流a形成第二反应区进料b循环至步骤2); [0054] 3) the second stream of step c phantom in step 1) in methanol feedstock s El exchanger after the heat exchanger means, after dehydration and removal sepl oxide separation zone separating the reaction zone to obtain a second return material d, the second reaction zone and a third reaction zone feed pi feed e, d the second reaction zone incorporated into the first return feed streams to the step of forming a second reaction zone feed cycle 2 b);

[0055] 所述的第二反应区返回料d包括乙烯、丁烯和C2〜C4烷烃,所述的第二反应区出料Pl包括C1烷烃和丙烯,所述的第三反应区进料e包括C5以上组分; [0055] The second reaction zone feed returns d include ethylene, butene and C2~C4 alkane, said second reaction zone effluent stream comprising C1 Pl alkanes and propylene, said third reaction zone feed e above include the C5 component;

[0056] 第二反应区出料pi进一步分离得到包括C1烷烃(燃料气)、丙烯; [0056] The second reaction zone effluent stream comprising C1 pi further isolated alkane (fuel gas), of propylene;

[0057] 4)经过第二反应区D2后的分子筛催化剂从第三反应区D3顶部进入到第三反应区D3,将步骤幻中得到的第三反应区进料e经过换热装置H3后从第三反应区D3底部通入第三反应区D3与分子筛催化剂接触,在465°C〜540°C、0. IMPa〜0. 5MPa条件下,分子筛催化剂在第三反应区D3停留30h〜100h,产生第三股物流f从第三反应区D3顶部的出口流出; [0057] 4) After the molecular sieve catalyst into the second reaction zone D2 D3 from the top of the third reaction zone to the third reaction zone D3, the third step of the reaction zone feed phantom obtained after the heat exchanger means e from H3 D3 third reaction zone into the bottom of the third reaction zone with a molecular sieve catalyst D3, at 465 ° C~540 ° C, 0. IMPa~0. 5MPa conditions, the molecular sieve catalyst in the third reaction zone residence D3 30h~100h, f streams to produce a third effluent from the outlet of the top of the third reaction zone D3;

[0058] 所述的第三股物流f包括丙烯、乙烯,丁烯、C1〜C4烷烃和C5以上烃; [0058] f said third streams include propylene, ethylene, butene, C1~C4 alkane and a C5 or more hydrocarbon;

[0059] 所述的第三反应区D3至少包括一个移动床反应器; [0059] D3 of the third reaction zone comprises at least one moving bed reactor;

[0060] 5)将步骤4)中得到的第三股物流f与第二反应区进料在换热装置E2换热后进入分离区sep2分离,分离得到乙烯、丁烯和C2〜C4烷烃并入第一股物流a循环至步骤2),最终分离得到包括C1烷烃(燃料气,包含少量乙烯)、丙烯、C5以上烃(汽油); [0060] 5) The Step 4) obtained in the third f streams fed into the second reaction zone the separation zone after separation sep2 heat exchanger E2 means isolated ethylene, butene and C2~C4 alkane and stream into a first stream is recycled to step 2), to give the final separation comprising C1 alkane (fuel gas, comprising a small amount of ethylene), propene, C5 or more hydrocarbon (gasoline);

[0061] 分子筛催化剂与催化剂稀释剂混合后连续输送到第一反应区Dl,分子筛催化剂缓慢连续移动,依次流经第一反应区D1、第二反应区D2、第三反应区D3,经过第三反应区D3后的分子筛催化剂,再经过分子筛催化剂出料缓冲罐B和催化剂出料控制器F2后,分子筛催化剂下料的速率由缓冲罐B下的催化剂出料控制器F2(无阀锁压装置)控制。 [0061] The molecular sieve catalyst and mixed catalyst diluent continuously fed to the first reaction zone Dl, the molecular sieve catalyst is continuously moved slowly and sequentially through the first reaction zone D1, the second reaction zone D2, the third reaction zone D3, through the third after the molecular sieve catalyst in the reaction zone D3, and then through the molecular sieve catalyst after the catalyst feed buffer tank B and a discharge controller F2, the feed rate of the molecular sieve catalyst from the catalyst feed controller F2 at the buffer tank B (valveless lock pressure device )control. 在催化剂收集器ST2收集,人工定期输送到再生装置R中再生得到再生催化剂。 ST2 in the catalyst collector to collect, transport to the reproduction apparatus for periodic manual regeneration R regenerated catalyst. 再生催化剂间歇地并入分子筛催化剂中循环至步骤1),所述的再生催化剂与未并入再生催化剂前的分子筛催化剂(即新鲜的分子筛催化剂)的质量比为0〜3 : 7。 The catalyst regeneration step is recycled to the molecular sieve catalyst incorporated intermittently 1), the mass of the regenerated catalyst with a molecular sieve catalyst (i.e., fresh molecular sieve catalyst) before the regenerated catalyst ratio was not incorporated 0~3: 7. [0062] 分离区s印1和s印2的分离方法可参考专利200580025151. 1和专利01810472. χ [0062] The separation zone s printing plate 1 and s 2 separation process may be referenced patents and patent 200580025151.1 01810472. χ

所介绍的分离工艺方法。 Process for the separation described.

[0063] 步骤1)中,所述的分子筛催化剂为ZSM-5分子筛。 [0063] Step 1), the molecular sieve catalyst is ZSM-5 zeolite. 所述的催化剂稀释剂为陶瓷或石英砂颗粒。 The catalyst diluent ceramic or quartz sand particles. 所述的分子筛催化剂与催化剂稀释剂的质量比为1 : 1〜20。 The molecular sieve catalyst mass ratio of diluent to catalyst is 1: 1~20.

[0064] 步骤2、中,所述的第一股物流a中加入物料稀释剂后通入第二反应区D2与分子筛催化剂接触。 [0064] Step 2, in the first streams in a diluent material is added after the second reaction zone into contact with a molecular sieve catalyst D2. 所述的物料稀释剂为水蒸气。 The diluent material is water vapor. 水蒸气可具体选用公用工程水蒸气。 The specific choice of public works water vapor water vapor.

[0065] 第一反应区D1、第二反应区D2和第三反应区D3中的反应原料流与分子筛催化剂流动呈逆流。 [0065] The first reaction zone D1, the second reaction zone and a third reaction zone D2 D3 the reaction feed stream with a countercurrent flow of a molecular sieve catalyst. 第一反应区D1、第二反应区D2和第三反应区D3的WHSV均为0. 1〜ZOhr^ The first reaction zone D1, WHSV of the second reaction zone and a third reaction zone D2 D3 are 0. 1~ZOhr ^

[0066] 本实施例1〜3的甲醇转化为丙烯的装置的结构可采用如图1所示的结构。 Structure as shown in methanol [0066] Example 1 ~ 3 of the present embodiment means conversion of propylene may be employed a configuration as shown in FIG.

[0067] 实施例1 [0067] Example 1

[0068] 1)将分子筛催化剂与催化剂稀释剂混合后连续通入第一反应区,甲醇原料的入口温度为240°C,将甲醇原料通入第一反应区与分子筛催化剂接触,在240°C〜280°C、 0. 2MPa〜0. 3MPa条件下,分子筛催化剂在第一反应区停留30h,,产生第一股物流,第一股物流的出口温度为280°C ; After [0068] 1) mixing the catalyst with a molecular sieve catalyst diluent continuously into a first reaction zone, the inlet temperature of the methanol feed to 240 ° C, the methanol feed into a first reaction zone with a molecular sieve catalyst at 240 ° C . at ~280 ° C, 0. 2MPa~0 3MPa conditions, the molecular sieve catalyst in a first reaction zone residence 30h ,, streams generate a first outlet streams of a first temperature 280 ° C;

[0069] 第一反应区为一个移动床反应器; [0069] The first reaction zone is a moving bed reactor;

[0070] 2)经过第一反应区后的分子筛催化剂进入到第二反应区,将步骤1)中得到的第一股物流中加入公用工程水蒸气后通入第二反应区与分子筛催化剂接触,第一股物流与水蒸气的摩尔比为1 : 1,第一股物流的进口温度为450°C,在450°C〜500°C、0. 15MPa〜 0. 2MPa条件下,分子筛催化剂在第二反应区停留30h,产生第二股物流,出口温度为500°C ; [0070] 2) After the molecular sieve catalyst after a first reaction zone into the second reaction zone into the second reaction zone with a molecular sieve catalyst after a first streams Step 1) was added a utility steam, the molar ratio of the first stream and steam stream is 1: 1, the inlet temperature of the first streams of 450 ° C, at 450 ° C~500 ° C, 0 15MPa~ 0. 2MPa conditions, the molecular sieve catalyst in the first. a second reaction zone residence 30h, generating second stream, an outlet temperature of 500 ° C;

[0071] 第二股物流包括乙烯、丙烯、丁烯、C1〜C4烷烃和C5以上组分; [0071] The second stream comprising ethylene, propylene, butene, C1~C4 alkane and a C5 or more components;

[0072] 第二反应区为一个移动床反应器; [0072] The second reaction zone is a moving bed reactor;

[0073] 3)将步骤2、中的第二股物流与步骤1)中甲醇原料换热后,经脱水和脱氧化物后得到包括微量含氧化合物的水,再进行分离,得到第二反应区返回料、第二反应区出料和第三反应区进料,第二反应区返回料并入第一股物流循环至步骤2); [0073] 3) in step 2, the second stream of step 1) in the methanol feed exchanger, after dehydration and removal of water traces include oxides obtained oxygen-containing compounds, and then separated to obtain a second reaction zone recycle material, feeding the second reaction zone and the third reaction zone feed, the second reaction zone incorporated into the first return feed streams are recycled to step 2);

[0074] 第二反应区返回料包括乙烯、丁烯和C2〜C4烷烃,第二反应区出料包括C1烷烃和丙烯,第三反应区进料包括C5以上组分; [0074] Back to the second reaction zone feed comprising ethylene, butene C2~C4 alkane and the second reaction zone effluent stream comprising propylene alkanes and C1, the third reaction zone feed comprising C5 components above;

[0075] 第二反应区出料进一步分离得到包括C1烷烃(燃料气)、丙烯; [0075] The second reaction zone effluent stream further comprises isolated C1 alkane (fuel gas), of propylene;

[0076] 4)经过第二反应区后的分子筛催化剂进入到第三反应区,将步骤幻中得到的第三反应区进料通入第三反应区与分子筛催化剂接触,第三反应区进料的进口温度为520°C, 在470°C〜520°C、0. IMI^a〜0. 15MPa条件下,分子筛催化剂在第三反应区停留30h,产生第三股物流,出口温度为470°C ; [0076] 4) After the molecular sieve catalyst through the reaction zone into the second reaction zone to the third, the third step of the reaction zone feed phantom obtained into third reaction zone with a molecular sieve catalyst, a third reaction zone feed the inlet temperature of 520 ° C, at 470 ° C~520 ° C, 0. IMI ^ a~0. 15MPa conditions, the molecular sieve catalyst in the third reaction zone residence 30h, third streams to produce an outlet temperature of 470 ° C;

[0077] 所述的第三股物流包括丙烯、乙烯、丁烯、C1〜C4烷烃,C5以上烃; [0077] The third streams include propylene, ethylene, butene, C1~C4 alkane, C5 or more hydrocarbon;

[0078] 所述的第三反应区为一个移动床反应器; [0078] The third reaction zone of a moving bed reactor;

[0079] 5)将步骤4)中得到的第三股物流与第二反应区进料进行换热后进行分离,分离得到乙烯、丁烯和C2〜C4烷烃并入第一股物流循环至步骤2、,最终分离得到包括C1烷烃和少量乙烯组成的混合物(燃料气)、丙烯、少量的(:3〜(;的烃类(由于在工业化生产中,未能将第三股物流中的全部C3〜C4烷烃、丙烯和丁烯全部分离,在最后的出料中,仍包括少量的C3〜C4的烃类,作为液化石油气),C5以上烃(汽油)。 [0079] 5) The third streams in step 4) obtained in the second reaction zone feed is separated after the heat exchanger, isolated ethylene, butene, and incorporated by C2~C4 alkane streams recycled to the first step the final mixture was separated to give 2 ,, (fuel gas), propylene, a small amount (including C1 paraffins and a minor amount of ethylene consisting of: 3 ~ (; hydrocarbons (due to the industrial production, the failure of all streams in the third C3~C4 alkane, propylene and butylene completely separated, the last batch, still includes small number C3~C4 hydrocarbons as liquefied petroleum gas), more C5 hydrocarbons (gasoline).

[0080] 分子筛催化剂选用颗粒直径为1. 5〜2mm的ZSM-5分子筛。 [0080] The selection of the molecular sieve catalyst particles having a diameter of ZSM-5 zeolite is 1. 5~2mm. 催化剂稀释剂为与分子筛催化剂尺寸大致相同的陶瓷颗粒,分子筛催化剂与催化剂稀释剂的质量比为1 : 3。 The catalyst and the diluent is substantially the same as the size of the molecular sieve catalyst ceramic particles, zeolite mass ratio of diluent to catalyst was 1: 3.

[0081] 从第三反应区的移动床反应器的床层底部移出的分子筛催化剂(积碳催化剂)在床内的停留时间为90小时,积炭量小于3%,将其收集在催化剂收集器中定期集中送到再生器中再生,得到再生催化剂,再生催化剂的积炭量低于0.5% (积炭量=单位重量催化剂上沉积的积炭质量)。 [0081] The molecular sieve catalyst is removed from the bottom of the moving bed reactor bed third reaction zone (catalyst coking) the residence time in the bed for 90 hours, less than 3% of the amount of coke, which is collected in the catalyst collector periodic regeneration concentrated to the regenerator, regenerated catalyst, regenerated catalyst coke deposition is less than 0.5% (= the amount of coke deposited on the catalyst weight soot mass). 再生催化剂间歇地并入分子筛催化剂中循环至步骤1),再生催化剂与新鲜的分子筛催化剂的质量比为1 : 7。 The catalyst regeneration step is recycled to the molecular sieve catalyst incorporated intermittently 1), the quality of regenerated catalyst with fresh molecular sieve catalyst ratio of 1: 7.

[0082] 所述的第一反应区、第二反应区和第三反应区的WHSV分别为lOhrilShr—1, 20hr_1o WHSV [0082] The first reaction zone, a second reaction zone and a third reaction zone, respectively lOhrilShr-1, 20hr_1o

[0083] 表1列出了上述条件下的物料平衡,该物料平衡是基于实验数据通过计算机模拟放大为百万吨甲醇每年处理量获得。 [0083] Table 1 lists the mass balance under the above conditions, the material balance is based on experimental data as one million tons per year of methanol processing amount obtained by computer simulation amplification. 从表1中可知,甲醇进料量为207383kg/h,所生成的丙烯量为6627^g/h,甲醇转化率大于98%。 As seen from Table 1, the methanol feed rate is 207383kg / h, the generated amount of propylene to 6627 ^ g / h, methanol conversion is greater than 98%.

[0084] 表1物料衡算 [0084] Table 1. Material Balance

Figure CN102344328AD00111

[0086] 表1中,#表示包括少量乙烯,*表示包括物料循环中的损失;其中LPG为C3〜C4 的烃类,主要为烷烃,包括少量烯烃;汽油为C5以上烃,包含少量的C4烃,主要是C7以上重组分;水为甲醇脱水的产物,包括未反应掉的微量甲醇及生成的二甲醚、醛类等微量含氧化合物;燃料气主要是少量C1-C2烃类组分(主要为C1烷烃,含有少量乙烯),焦炭为催化剂上的碳沉积,下同。 [0086] Table 1, include a minor amount of ethylene represents #, * represents material loss cycle comprising; wherein a hydrocarbon C3~C4 of LPG, predominantly alkanes, including small amounts of olefins; a C5 or more hydrocarbon gasoline containing a small amount of C4 hydrocarbons, mainly recombinant or more points C7; aqueous methanol dehydration product comprising unreacted methanol out of the trace and producing dimethyl ether, aldehydes and other trace oxygenates; a small amount of fuel gas mainly C1-C2 hydrocarbon components (mainly C1 paraffins, containing a small amount of ethylene), carbon coke deposited on the catalyst, the same below.

[0087] 将各产物换算成除水以外的干基百分含量,列出了相对于原料甲醇的产物分布, 如表2所示。 [0087] Each product was converted into dry percentages other than water, with respect to a list of starting material the methanol product distribution, as shown in Table 2.

[0088] 表2产物分布 [0088] Table 2 Product Distribution

Figure CN102344328AD00112
Figure CN102344328AD00121

[0090] 实施例2 [0090] Example 2

[0091] 1)将分子筛催化剂与催化剂稀释剂混合后连续通入第一反应区,甲醇原料的入口温度为260°C,将甲醇原料通入第一反应区与分子筛催化剂接触,在260°C〜300°C、 0. 4MPa〜0. 6MPa条件下,分子筛催化剂在第一反应区停留50h,,产生第一股物流,第一股物流的出口温度为300°C ; After [0091] 1) mixing the catalyst with a molecular sieve catalyst diluent continuously into a first reaction zone, the inlet temperature of the methanol feed to 260 ° C, the methanol feed into a first reaction zone with a molecular sieve catalyst at 260 ° C . at ~300 ° C, 0. 4MPa~0 6MPa conditions, the molecular sieve catalyst in a first reaction zone residence 50h ,, streams generate a first outlet streams of a first temperature 300 ° C;

[0092] 第一反应区为一个移动床反应器; [0092] The first reaction zone is a moving bed reactor;

[0093] 2)经过第一反应区后的分子筛催化剂进入到第二反应区,将步骤1)中得到的第一股物流中加入公用工程水蒸气后通入第二反应区与分子筛催化剂接触,第一股物流与水蒸气的摩尔比为4 : 1,第一股物流的进口温度为470°C,在470°C〜520°C、0. 2MPa〜 0. 4MPa条件下,分子筛催化剂在第二反应区停留50h,产生第二股物流,出口温度为520°C ; [0093] 2) After the molecular sieve catalyst after a first reaction zone into the second reaction zone into the second reaction zone with a molecular sieve catalyst after a first streams Step 1) was added a utility steam, and the molar ratio of the first vapor streams is 4: 1, the inlet temperature of the first streams of 470 ° C, at 470 ° C~520 ° C, 0 2MPa~ 0. 4MPa conditions, the molecular sieve catalyst in the first. a second reaction zone residence 5Oh, generating second stream, an outlet temperature of 520 ° C;

[0094] 第二股物流包括乙烯、丙烯、丁烯、C1〜C4烷烃和C5以上组分; [0094] The second stream comprising ethylene, propylene, butene, C1~C4 alkane and a C5 or more components;

[0095] 第二反应区为一个移动床反应器; [0095] The second reaction zone is a moving bed reactor;

[0096] 3)将步骤2、中的第二股物流与步骤1)中甲醇原料换热后,经脱水和脱氧化物后得到包括微量含氧化合物的水,再进行分离,得到第二反应区返回料、第二反应区出料和第三反应区进料,第二反应区返回料并入第一股物流循环至步骤2); [0096] 3) in step 2, the second stream of step 1) in the methanol feed exchanger, after dehydration and removal of water traces include oxides obtained oxygen-containing compounds, and then separated to obtain a second reaction zone recycle material, feeding the second reaction zone and the third reaction zone feed, the second reaction zone incorporated into the first return feed streams are recycled to step 2);

[0097] 第二反应区返回料包括乙烯、丁烯和C2〜C4烷烃,第二反应区出料包括C1烷烃和丙烯,第三反应区进料包括C5以上组分; [0097] Back to the second reaction zone feed comprising ethylene, butene C2~C4 alkane and the second reaction zone effluent stream comprising propylene alkanes and C1, the third reaction zone feed comprising C5 components above;

[0098] 第二反应区出料进一步分离得到包括C1烷烃和少量乙烯的混合物(燃料气)、丙烯; [0098] The second reaction zone effluent stream comprising a mixture of C1 to give further separation of alkanes and small amounts of ethylene (fuel gas), of propylene;

[0099] 4)经过第二反应区后的分子筛催化剂进入到第三反应区,将步骤幻中得到的第三反应区进料通入第三反应区与分子筛催化剂接触,第三反应区进料的进口温度为530°C, 在480°C〜530°C、0. IMPa〜0. 2MPa条件下,分子筛催化剂在第三反应区停留50h,产生第三股物流,出口温度为480°C ; [0099] 4) After the molecular sieve catalyst through the reaction zone into the second reaction zone to the third, the third step of the reaction zone feed phantom obtained into third reaction zone with a molecular sieve catalyst, a third reaction zone feed the inlet temperature of 530 ° C, at 480 ° C~530 ° C, 0 IMPa~0 2MPa conditions, the molecular sieve catalyst in the third reaction zone residence 50h, third streams to produce an outlet temperature of 480 ° C..;

[0100] 所述的第三股物流包括丙烯、乙烯、丁烯、C1〜C4烷烃,C5以上烃; [0100] The third streams include propylene, ethylene, butene, C1~C4 alkane, C5 or more hydrocarbon;

[0101] 所述的第三反应区为一个移动床反应器; [0101] The third reaction zone of a moving bed reactor;

[0102] 5)将步骤4)中得到的第三股物流与第二反应区进料进行换热后进行分离,分离得到乙烯、丁烯和C2〜C4烷烃并入第一股物流循环至步骤2、,最终分离得到包括C1烷烃和少量乙烯组成的混合物(燃料气)、丙烯、少量的(:3〜(;的烃类(由于在工业化生产中,未能将第三股物流中的全部C3〜C4烷烃、丙烯和丁烯全部分离,在最后的出料中,仍包括少量的C3〜C4的烃类,作为液化石油气)、C5以上烃(汽油)。 [0102] 5) The third streams in step 4) obtained in the second reaction zone feed is separated after the heat exchanger, isolated ethylene, butene, and incorporated by C2~C4 alkane streams recycled to the first step the final mixture was separated to give 2 ,, (fuel gas), propylene, a small amount (including C1 paraffins and a minor amount of ethylene consisting of: 3 ~ (; hydrocarbons (due to the industrial production, the failure of all streams in the third C3~C4 alkane, propylene and butylene completely separated, the last batch, still includes small number C3~C4 hydrocarbons as liquefied petroleum gas), more C5 hydrocarbons (gasoline).

[0103] 分子筛催化剂选用颗粒直径为1. 5〜2mm的ZSM-5分子筛。 [0103] selection of particle diameter of the molecular sieve catalyst of ZSM-5 in 1. 5~2mm. 催化剂稀释剂为与分子筛催化剂尺寸大致相同的石英砂颗粒,分子筛催化剂与催化剂稀释剂的质量比为1 : 5。 The catalyst and the diluent is substantially the same as the size of the molecular sieve catalyst of silica particles, zeolite mass ratio of diluent to catalyst is from 1: 5. [0104] 从第三反应区的移动床反应器的床层底部移出的分子筛催化剂(积碳催化剂)在床内的停留时间为150小时,积炭量小于3%,将其收集在催化剂收集器中定期集中送到再生器中再生,得到再生催化剂,再生催化剂的积炭量低于0.5% (积炭量=单位重量催化剂上沉积的积炭质量)。 [0104] molecular sieve catalyst is removed from the bottom of the moving bed reactor bed third reaction zone (catalyst coking) the residence time in the bed for 150 hours, less than 3% of the amount of coke, which is collected in the catalyst collector periodic regeneration concentrated to the regenerator, regenerated catalyst, regenerated catalyst coke deposition is less than 0.5% (= the amount of coke deposited on the catalyst weight soot mass). 再生催化剂间歇地并入分子筛催化剂中循环至步骤1),再生催化剂与新鲜的分子筛催化剂的质量比为3 : 7。 The catalyst regeneration step is recycled to the molecular sieve catalyst incorporated intermittently 1), the mass ratio of regenerated catalyst with fresh molecular sieve catalyst is 3: 7.

[0105] 所述的第一反应区、第二反应区和第三反应区的WHSV分别为1 Shi·—1,1 Shi·—1, 18hr_10 [0105] The first reaction zone, WHSV of the second reaction zone and a third reaction zone, respectively, 1 Shi · -1,1 Shi · -1, 18hr_10

[0106] 表3列出了上述条件下的物料平衡,该物料平衡是基于实验数据通过计算机模拟放大为百万吨甲醇每年处理量获得。 [0106] Table 3 shows the material balance under the above conditions, the material balance is based on experimental data as one million tons per year of methanol processing amount obtained by computer simulation amplification. 从表3中可知,甲醇进料量为207383kg/h,所生成的丙烯量为64451kg/h,甲醇转化率大于99%。 Seen from Table 3, the methanol feed rate is 207383kg / h, the generated amount of propylene is 64451kg / h, the methanol conversion was greater than 99%.

[0107] 表3物料衡算 [0107] Table 3 Material Balance

[0108] [0108]

Figure CN102344328AD00131

[0109] [0109]

[0110] 表3中,#表示包括少量乙烯,*表示包括物料循环中的损失; [0110] In Table 3, # represents a small amount of ethylene including, * represents a loss of material comprising a cycle;

[0111] 将各产物换算成除水以外的干基百分含量,列出了相对于原料甲醇的产物分布, 如表4所示。 [0111] Each product was converted into dry percentages other than water, with respect to a list of starting material the methanol product distribution, as shown in Table 4.

[0112] 表4产物分布 [0112] Table 4 Product Distribution

[0113] [0113]

Figure CN102344328AD00132
Figure CN102344328AD00141

[0114] 实施例3 [0114] Example 3

[0115] 1)将分子筛催化剂与催化剂稀释剂混合后连续通入第一反应区,甲醇原料的入口温度为280°C,将甲醇原料通入第一反应区与分子筛催化剂接触,在280°C〜320°C、 0. SMI^a〜IMPa条件下,分子筛催化剂在第一反应区停留100h,产生第一股物流,第一股物流的出口温度为320°C ; After [0115] 1) mixing the catalyst with a molecular sieve catalyst diluent continuously into a first reaction zone, the inlet temperature of the methanol feed to 280 ° C, the methanol feed into a first reaction zone with a molecular sieve catalyst at 280 ° C at ~320 ° C, 0. SMI ^ a~IMPa conditions, the molecular sieve catalyst in a first reaction zone residence lOOh, generating a first streams, the outlet temperature of the first streams of 320 ° C;

[0116] 第一反应区为一个移动床反应器; [0116] The first reaction zone is a moving bed reactor;

[0117] 2)经过第一反应区后的分子筛催化剂进入到第二反应区,将步骤1)中得到的第一股物流中加入公用工程水蒸气后通入第二反应区与分子筛催化剂接触,第一股物流与水蒸气的摩尔比为1 : 4,第一股物流的进口温度为480°C,在480°C〜530°C、0. 3MPa〜 0. 5MPa条件下,分子筛催化剂在第二反应区停留100h,产生第二股物流,出口温度为530 0C ; [0117] 2) After the molecular sieve catalyst after a first reaction zone into the second reaction zone into the second reaction zone with a molecular sieve catalyst after a first streams Step 1) was added a utility steam, the molar ratio of the first stream and steam stream is 1: 4, the first inlet temperature of streams 480 ° C, at 480 ° C~530 ° C, 0 3MPa~ 0. 5MPa conditions, the molecular sieve catalyst in the first. a second reaction zone residence lOOh, generating second stream, an outlet temperature of 530 0C;

[0118] 第二股物流包括乙烯、丙烯、丁烯、C1〜C4烷烃和C5以上组分; [0118] second stream comprising ethylene, propylene, butene, C1~C4 alkane and a C5 or more components;

[0119] 第二反应区为一个移动床反应器; [0119] The second reaction zone is a moving bed reactor;

[0120] 3)将步骤2、中的第二股物流与步骤1)中甲醇原料换热后,经脱水和脱氧化物后得到包括微量含氧化合物的水,再进行分离,得到第二反应区返回料、第二反应区出料和第三反应区进料,第二反应区返回料并入第一股物流循环至步骤2); [0120] 3) in step 2, the second stream of step 1) in the methanol feed exchanger, after dehydration and removal of water traces include oxides obtained oxygen-containing compounds, and then separated to obtain a second reaction zone recycle material, feeding the second reaction zone and the third reaction zone feed, the second reaction zone incorporated into the first return feed streams are recycled to step 2);

[0121] 第二反应区返回料包括乙烯、丁烯和C2〜C4烷烃,第二反应区出料包括C1烷烃和丙烯,第三反应区进料包括C5以上组分; [0121] Back to the second reaction zone feed comprising ethylene, butene C2~C4 alkane and the second reaction zone effluent stream comprising propylene alkanes and C1, the third reaction zone feed comprising C5 components above;

[0122] 第二反应区出料进一步分离得到包括C1烷烃和少量乙烯的混合物(燃料气)、丙烯; [0122] The second reaction zone effluent stream comprising a mixture of C1 to give further separation of alkanes and small amounts of ethylene (fuel gas), of propylene;

[0123] 4)经过第二反应区后的分子筛催化剂进入到第三反应区,将步骤幻中得到的第三反应区进料通入第三反应区与分子筛催化剂接触,第三反应区进料的进口温度为, 在490°C〜M0°C、0. IMPa〜0. 3MPa条件下,分子筛催化剂在第三反应区停留100h,产生第三股物流,出口温度为490°C ; [0123] 4) After the molecular sieve catalyst through the reaction zone into the second reaction zone to the third, the third step of the reaction zone feed phantom obtained into third reaction zone with a molecular sieve catalyst, a third reaction zone feed inlet temperature, at 490 ° C~M0 ° C, 0 IMPa~0 3MPa conditions, the molecular sieve catalyst in the third reaction zone residence 100h, streams to produce a third outlet temperature of 490 ° C..;

[0124] 所述的第三股物流包括丙烯、乙烯、丁烯、C1〜C4烷烃,C5以上烃; [0124] The third streams include propylene, ethylene, butene, C1~C4 alkane, C5 or more hydrocarbon;

[0125] 所述的第三反应区为一个移动床反应器; [0125] The third reaction zone of a moving bed reactor;

[0126] 5)将步骤4)中得到的第三股物流与第二反应区进料进行换热后进行分离,分离得到乙烯、丁烯和C2〜C4烷烃并入第一股物流循环至步骤2、,最终分离得到包括C1烷烃和少量乙烯组成的混合物(燃料气)、丙烯、少量的(:3〜(;的烃类(由于在工业化生产中,未能将第三股物流中的全部C3〜C4烷烃、丙烯和丁烯全部分离,在最后的出料中,仍包括少量的C3〜C4的烃类,作为液化石油气)、C5以上烃(汽油)。 [0126] 5) The third streams in step 4) obtained in the second reaction zone feed is separated after the heat exchanger, isolated ethylene, butene, and incorporated by C2~C4 alkane streams recycled to the first step the final mixture was separated to give 2 ,, (fuel gas), propylene, a small amount (including C1 paraffins and a minor amount of ethylene consisting of: 3 ~ (; hydrocarbons (due to the industrial production, the failure of all streams in the third C3~C4 alkane, propylene and butylene completely separated, the last batch, still includes small number C3~C4 hydrocarbons as liquefied petroleum gas), more C5 hydrocarbons (gasoline).

[0127] 分子筛催化剂选用颗粒直径为1. 5〜2mm的ZSM-5分子筛。 [0127] selection of particle diameter of the molecular sieve catalyst of ZSM-5 in 1. 5~2mm. 催化剂稀释剂为与分子筛催化剂尺寸大致相同的陶瓷颗粒,分子筛催化剂与催化剂稀释剂的质量比为1 : 8。 The catalyst and the diluent is substantially the same as the size of the molecular sieve catalyst ceramic particles, zeolite mass ratio of diluent to catalyst is from 1: 8.

[0128] 从第三反应区的移动床反应器的床层底部移出的分子筛催化剂(积碳催化剂)在床内的停留时间为300小时,积炭量小于3%,将其收集在催化剂收集器中定期集中送到再生器中再生,得到再生催化剂,再生催化剂的积炭量低于0.5% (积炭量=单位重量催化剂上沉积的积炭质量)。 [0128] molecular sieve catalyst is removed from the bottom of the moving bed reactor bed third reaction zone (catalyst coking) the residence time in the bed for 300 hours, less than 3% of the amount of coke, which is collected in the catalyst collector periodic regeneration concentrated to the regenerator, regenerated catalyst, regenerated catalyst coke deposition is less than 0.5% (= the amount of coke deposited on the catalyst weight soot mass). 再生催化剂间歇地并入分子筛催化剂中循环至步骤1),再生催化剂与新鲜的分子筛催化剂的质量比为2 : 7。 The catalyst regeneration step is recycled to the molecular sieve catalyst incorporated intermittently 1), the quality of regenerated catalyst with fresh molecular sieve catalyst ratio of 2: 7.

[0129] 所述的第一反应区、第二反应区和第三反应区的WHSV分别为air—1,12hr^, 16hr^0 [0129] The first reaction zone, WHSV of the second reaction zone and a third reaction zones were air-1,12hr ^, 16hr ^ 0

[0130] 表5列出了上述条件下的物料平衡,该物料平衡是基于实验数据通过计算机模拟放大为百万吨甲醇每年处理量获得。 [0130] Table 5 lists the material balance under the above conditions, the material balance is based on experimental data as one million tons per year of methanol processing amount obtained by computer simulation amplification. 从表5中可知,甲醇进料量为207383kg/h,所生成的丙烯量为69380kg/h,甲醇转化率100%。 From Table 5, the feed amount of methanol is 207383kg / h, the generated amount of propylene is 69380kg / h, the conversion rate of 100% methanol.

[0131] 表5物料衡算 [0131] TABLE 5 Material Balance

[0132] [0132]

Figure CN102344328AD00151

[0133] [0133]

[0134] 表5中,#表示包括少量乙烯,*表示包括物料循环中的损失; [0134] Table 5, comprising a small amount of ethylene represents #, * represents a loss of material comprising a cycle;

[0135] 将各产物换算成除水以外的干基百分含量,列出了相对于原料甲醇的产物分布, 如表6所示。 [0135] Each product was converted into dry percentages other than water, with respect to a list of starting material the methanol product distribution, as shown in Table 6.

[0136] 表6产物分布 [0136] TABLE 6 Product Distribution

[0137] [0137]

Figure CN102344328AD00152

[0138] 从上述三个实施例看出,按照本发明公开的工艺方法,能取得较好的温度控制与催化剂在线反应时间和较高的丙烯选择性。 [0138] From the above three embodiments, according to the process of the present invention disclosed herein, can achieve better temperature control of the catalyst and the reaction time line high propylene selectivity. 此外,在本发明公开的范围内进行操作,产物的选择性变化幅度较小。 In addition, operating within the scope of the present disclosure, changes in product selectivity lesser extent.

Claims (10)

1. 一种使用移动床技术将甲醇转化为丙烯的半连续方法,包括以下步骤:1)将分子筛催化剂与催化剂稀释剂混合后连续通入第一反应区,将甲醇原料通入第一反应区与分子筛催化剂接触,在〜300°C、0. IMPa〜IMPa条件下,分子筛催化剂在第一反应区停留30h〜100h,产生第一股物流;所述的第一股物流包括甲醇、二甲醚和水;所述的第一反应区至少包括一个移动床反应器;2)经过第一反应区后的分子筛催化剂进入到第二反应区,将步骤1)中得到的第一股物流通入第二反应区与分子筛催化剂接触,在430°C〜530°C、0. IMPa〜0. SMPa条件下,分子筛催化剂在第二反应区停留30h〜100h,产生第二股物流;所述的第二股物流包括乙烯、丙烯、丁烯、C1〜C4烷烃和C5以上组分;所述的第二反应区至少包括一个移动床反应器;3)将步骤幻中产生的第二股物流与步骤1)中的甲醇原料 A moving bed technology for converting methanol to propylene semi-continuous process, comprising the steps of: 1) the molecular sieve catalyst and the catalyst after the diluent continuously into a first reaction zone, the methanol feed into a first reaction zone contacted with a molecular sieve catalyst at ~300 ° C, 0 under IMPa~IMPa conditions, the molecular sieve catalyst in a first reaction zone residence 30h~100h, generating a first streams; the first streams include methanol, dimethyl ether and water; the first reaction zone comprises at least one moving bed reactor; 2) through a molecular sieve catalyst after a first reaction zone into the second reaction zone, the first streams in step 1) obtained in the first pass a second reaction zone into contact with a molecular sieve catalyst at 430 ° C~530 ° C, 0 IMPa~0 SMPa conditions, the molecular sieve catalyst in the second reaction zone residence 30h~100h, generating second stream;. the second streams include ethylene, propylene, butylene, C1~C4 alkane and a C5 or more component; the second reaction zone comprises at least one moving bed reactor; 3) and a second stream generated in step 1 magic ) in methanol feedstock 换热后,经脱水和脱氧化物后进行分离,得到第二反应区返回料、第二反应区出料和第三反应区进料,第二反应区返回料并入第一股物流循环至步骤2);所述的第二反应区返回料包括乙烯、丁烯和C2〜C4烷烃,所述的第二反应区出料包括C1烷烃和丙烯,所述的第三反应区进料包括C5以上组分;4)经过第二反应区后的分子筛催化剂进入到第三反应区,将步骤3)中得到的第三反应区进料通入第三反应区与分子筛催化剂接触,在465°C〜540°C、0. IMPa〜0. 5MPa条件下,分子筛催化剂在第三反应区停留30h〜100h,产生第三股物流;所述的第三股物流包括丙烯、乙烯、丁烯、C1〜C4烷烃和C5以上烃;所述的第三反应区至少包括一个移动床反应器;分子筛催化剂与催化剂稀释剂混合后连续输送到第一反应区,分子筛催化剂缓慢连续移动,依次流经第一反应区、第二反应区、 After the heat exchanger, after dehydration and removal oxides were separated recycle material to obtain a second reaction zone, a second reaction zone effluent stream and a third reaction zone feed, the second reaction zone incorporated into the first return feed streams recycled to step 2); the second reaction zone recycle material include ethylene, butene and C2~C4 alkane, said second reaction zone effluent stream comprising propylene alkanes and C1, the third reaction zone feed comprising C5 more component; 4) molecular sieve catalyst through the reaction zone into the second reaction zone to the third, the third reaction zone in step 3) to give the feed into third reaction zone with a molecular sieve catalyst, 465 ° C~ in .. 540 ° C, at 0 IMPa~0 5MPa conditions, the molecular sieve catalyst in the third reaction zone residence 30h~100h, generating third streams; said third streams include propylene, ethylene, butene, C1~C4 paraffins and C5 hydrocarbons above; said third reaction zone comprises at least one moving bed reactor; the molecular sieve catalyst and mixed catalyst diluent continuously fed to the first reaction zone, the molecular sieve catalyst is continuously moved slowly and sequentially through the first reaction zone the second reaction zone, 三反应区,经过第三反应区后的分子筛催化剂收集后定期进行再生得到再生催化剂,再生催化剂间歇地并入分子筛催化剂中循环至步骤1)。 Three reaction zones, the molecular sieve catalyst after the third reaction zone was collected periodically regenerated catalyst regeneration step is recycled to the molecular sieve catalyst in the regenerated catalyst is incorporated intermittently 1).
2.根据权利要求1所述的使用移动床技术将甲醇转化为丙烯的半连续方法,其特征在于,包括:5)将步骤4)中得到的第三股物流与第二反应区进料进行换热后进行分离,分离得到乙烯、丁烯和C2〜C4烷烃并入第一股物流循环至步骤2)。 The converting methanol to propylene semi-continuous process using moving bed technology according to claim 1, characterized in that, comprising: 5) The third streams in step 4) obtained in the second reaction zone feed is after separating the heat exchanger, isolated ethylene, butene, and incorporated by C2~C4 alkane streams recycled to the first step 2).
3.根据权利要求1所述的使用移动床技术将甲醇转化为丙烯的半连续方法,其特征在于,步骤1)中,所述的分子筛催化剂为ZSM-5分子筛。 The use of moving bed technology in claim 1 to convert methanol to propylene semi-continuous process as claimed in claim, wherein step 1), the molecular sieve catalyst is ZSM-5 zeolite.
4.根据权利要求1所述的使用移动床技术将甲醇转化为丙烯的半连续方法,其特征在于,步骤1)中,所述的催化剂稀释剂为陶瓷颗粒或石英砂颗粒。 The use of moving bed technology in claim 1 to convert methanol to propylene semi-continuous process as claimed in claim, wherein step 1), the diluent for the catalyst of silica particles or ceramic particles.
5.根据权利要求1所述的使用移动床技术将甲醇转化为丙烯的半连续方法,其特征在于,步骤1)中,所述的分子筛催化剂与催化剂稀释剂的质量比为1 : 1〜20。 The converting methanol to propylene semi-continuous process using moving bed technology according to claim 1, wherein in step 1), the mass ratio of diluent to catalyst zeolite is 1: 1~20 .
6.根据权利要求1所述的使用移动床技术将甲醇转化为丙烯的半连续方法,其特征在于,步骤2、中,所述的第一股物流中加入物料稀释剂后通入第二反应区与分子筛催化剂接触。 The converting methanol to propylene semi-continuous process using moving bed technology according to claim 1, wherein, in step 2, the first of the streams of material added in the diluent into the second reactor regions in contact with a molecular sieve catalyst.
7.根据权利要求6所述的使用移动床技术将甲醇转化为丙烯的半连续方法,其特征在于,所述的物料稀释剂为水蒸气。 The converting methanol to propylene semi-continuous process using moving bed technology according to claim 6, wherein said diluent material is water vapor.
8.根据权利要求1所述的使用移动床技术将甲醇转化为丙烯的半连续方法,其特征在于,所述的再生催化剂与未并入再生催化剂前的分子筛催化剂的质量比为0〜3 : 7。 Use according to claim 1 moving bed technology for converting methanol to propylene semi-continuous process as claimed in claim, wherein the mass ratio of the regenerated catalyst with molecular sieve catalyst prior to regeneration of the catalyst is not incorporated 0~3: 7.
9.根据权利要求1所述的使用移动床技术将甲醇转化为丙烯的半连续方法,其特征在于,所述的第一反应区、第二反应区和第三反应区中的反应原料流与分子筛催化剂流动呈逆流。 9. The converting methanol to propylene semi-continuous process using moving bed technology according to claim 1, wherein said first reaction zone, a second reaction zone and a third reaction zone feed stream with the reaction molecular sieve catalyst countercurrent flow.
10.根据权利要求1所述的使用移动床技术将甲醇转化为丙烯的半连续方法,其特征在于,所述的第一反应区、第二反应区和第三反应区的WHSV均为0. 1〜ZOhr-1。 10. The converting methanol to propylene semi-continuous process using moving bed technology according to claim 1, characterized in that, the WHSV of the first reaction zone, a second reaction zone and a third reaction zone are 0. 1~ZOhr-1.
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