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Número de publicaciónCN102344328 A
Tipo de publicaciónSolicitud
Número de solicitudCN 201110208634
Fecha de publicación8 Feb 2012
Fecha de presentación25 Jul 2011
Fecha de prioridad25 Jul 2011
También publicado comoCN102344328B
Número de publicación201110208634.2, CN 102344328 A, CN 102344328A, CN 201110208634, CN-A-102344328, CN102344328 A, CN102344328A, CN201110208634, CN201110208634.2
Inventores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
Solicitante浙江大学
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos:  SIPO, Espacenet
Semi-continuous method for converting methyl alcohol into propylene by using moving bed technology
CN 102344328 A
Resumen
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.
Reclamaciones(10)  traducido del chino
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、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)。 A use of moving bed technology for converting methanol to propylene semi-continuous process, comprising the steps of: a) continuously introduced into the zeolite catalyst with the catalyst after a first reaction zone diluent, the methanol feed introduced into the first reaction zone with a molecular sieve catalyst at ~300 ° C, 0 IMPa~IMPa under 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; wherein the first reaction zone comprises at least one moving bed reactor; 2) through the molecular sieve catalyst after a first reaction zone into the second reaction zone of step 1) obtained in the first unit passed into the first stream second reaction zone 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 streams;. The second streams include ethylene, propylene, butylene, C1~C4 alkane and C5 components above; said second reaction zone comprises at least one moving bed reactor; 3) and the second streams generated in Step 1 magic after) the methanol feedstock heat, after dehydration and de-oxide to give the second reaction zone to return material, the second reaction zone effluent stream and a third reaction zone feed, the second reaction zone to return materials incorporated first streams recycled to step 2); said second reaction zone to return materials include ethylene, butene and C2~C4 alkane, said second reaction zone effluent stream comprising alkanes and C1 propylene, said third reaction zone C5 feed comprising the above components; 4) through the molecular sieve catalyst after entering the second reaction zone to the third reaction zone, a third reaction zone in step 3) obtained in the third feed introduced into the reaction zone and contacting the molecular sieve catalyst, . In the 465 ° C~540 ° C, 0 IMPa~0 5MPa conditions, the molecular sieve catalyst in the third reaction zone residence 30h~100h, generating a third streams; said third streams include propylene, ethylene, Ding alkenyl, C1~C4 alkane and C5 + hydrocarbon; said third reaction zone comprises at least one moving bed reactor; molecular sieve catalyst and a diluent mixed catalyst continuously fed to the first reaction zone, the molecular sieve catalyst continuously moving slowly, sequentially flows After the first reaction zone, a second reaction zone, a third reaction zone, the molecular sieve catalyst after a third reaction zone were collected periodically regenerated after the catalyst is regenerated, intermittently regenerated catalyst is incorporated in the molecular sieve catalyst is recycled to step 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 use of moving bed technology for converting methanol to propylene semi-continuous process according to claim 1, characterized in that, comprising: 5) in step 4) obtained in the third and the second reaction zone streams feedstock After separation heat, isolated ethylene, butene, and C2~C4 alkane stream is recycled to the first unit incorporated in 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。 3. The use of moving bed technology to claim 1, wherein the methanol is converted to propylene semi-continuous process, characterized in that 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。 4. The use of moving bed technology to claim 1, wherein the methanol is converted to propylene semi-continuous process, characterized in that, in step 1), the catalyst of the diluent is quartz sand 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。 5. The use of moving bed technology for converting methanol to propylene semi-continuous process according to claim 1, characterized in that, in step 1), the mass ratio of molecular sieve catalysts and catalyst diluent 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。 6. The use of moving bed technology for converting methanol to propylene semi-continuous process according to claim 1, wherein, in step 2, in the first of the streams introduced into the second reactor after addition of diluent materials area in contact with the zeolite catalysts.
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。 7. The use of moving bed technology for converting methanol to propylene semi-continuous process according to claim 6, characterized in that the material of the diluent 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。 8. Use according to any one of the moving bed technology to convert methanol to propylene semi-continuous process as claimed in claim wherein the mass ratio of the regenerated catalyst with a molecular sieve catalyst before catalyst regeneration is not incorporated as 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 use of moving bed technology for converting methanol to propylene semi-continuous process according to claim 1, characterized in that said first reaction zone, the second reaction zone and a third reaction zone feed stream in a reaction with zeolite catalyst was 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 use of moving bed technology for converting methanol to propylene semi-continuous process according to claim 1, characterized in that, WHSV said first reaction zone, the second reaction zone and a third reaction zone are 0. 1~ZOhr-1.
Descripción  traducido del chino

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 Technical 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 use of moving bed technology for preparing propylene, in particular to a moving bed technique used to convert methanol to propylene semi-continuous process.

背景技术 Background

[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 the 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。 With the world industrial economy, 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 route 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, leading to oil as raw material to produce propylene costs continue to rise, which led to relatively low-cost methanol production 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 decline in the future is difficult, for oil, less gas, coal-rich China, methanol, propylene production technology highlights more highly competitive 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 methanol to olefins process (MTO) and the United States UOP's 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)。 Domestic there fluidized bed methanol to propylene process MTO process (DMTO) CAS Dalian Institute of Chemical Physics, Tsinghua University developed and research and development (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 is mainly used for the preparation of 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 process is mainly to complete the German company Lurgi and the formation of patented technology developed by European patent EP0448000B1, Chinese patent CN1431982A etc. have been disclosed in the process methods and catalysts 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 method is based on modified ZSM-5 zeolite catalysts South German chemical company, using a single-stage and multi-stage adiabatic fixed bed reactor has a high propylene yield, while production of small amounts 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。 Due to the need for a fixed bed catalyst regeneration in situ intermittently, therefore, usually a plurality of fixed bed reactors (e.g., two open a standby, i.e., the use of two fixed-bed reactors, a fixed bed reactor standby) to switch to solve these problems, but that there is a system design approach equipment requirements, complex operation problems.

[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] The fluidized bed technology was originally developed by the UOP Research, in addition, there are also a DICP, Tsinghua University developed in the 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。 Mainly SAP0-34 catalyst fluidized bed technology, it has a high selectivity of 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 in 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] The moving bed technology because of solid backmixing within the bed is small, the reaction closer to plug flow, and thus feed conversion rate, and keep moving catalyst bed (regeneration) which can 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 the Chinese patent application discloses a moving bed methanol to propylene technology, through the use of bifunctional zeolite catalysts, using reactive - way to achieve regeneration cycle of the catalyst, while the introduction of cycle conversion by-products, thereby increasing propylene choice 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 one having a mesoporous nature of coke having a moderate rate. 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。 Moving bed regeneration technique is a continuous reaction technology, especially for catalysts 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 the same as the circulating fluidized bed continuous reaction regeneration, while no catalyst with 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] Authorization Publication No. CN1152944C of Chinese patent discloses the reaction zone contains four continuous reaction - reproducing apparatus; Publication No. CN 101367701A the Chinese patent application discloses a two-stage reaction zone, the oxygenate feedstock the first stage reaction zone to form product, and the product of the above components C5 through into the second reaction zone catalysts for carbon deposition, and then the second reaction zone pre coke catalyst for the first reaction zone, and finally The catalyst through 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 use of continuous reaction - reaction process for the continuous regeneration of the reproducing apparatus and the catalyst is delivered from the second reaction zone to the first reaction zone are required between the reaction system and the reaction system and the regeneration means adding a special stripper means to flow out of the reactor catalyst regeneration means to regenerate delivery, which requires a lot of power delivery, there is a high energy consumption, poor economic technical defects.

发明内容 DISCLOSURE

[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 for converting methanol to propylene semi-continuous process using moving bed technology, i.e. only one molecular sieve catalyst to achieve a moving bed of methanol to the three-stage reaction of propylene, and ultimately improve the yield of propylene purposes.

[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 method of using moving bed technology to convert 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 the [0010] 1) the molecular sieve catalyst diluent and catalyst is continuously introduced into the first reaction zone, the methanol feed through into the first reaction zone with a molecular sieve catalyst at ~300 ° C, 0. IMPa~IMPa conditions zeolite 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 first streams [0011] comprising 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; The first reaction zone [0012] comprising 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 of step 1) obtained in the first streams introduced into the 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 to stay 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; Second stream [0014] comprising ethylene, propylene, butylene, C1~C4 alkane and C5 components above;

[0015] 所述的第二反应区至少包括一个移动床反应器; The second reaction zone [0015] comprising 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) Step 2, after second stream of step 1) in methanol feedstock heat generated by dehydration and de-oxide separation (ie after the gas-liquid separation and removal of water by distillation and unconverted methanol and dimethyl ether oxide after separation) to obtain a second reaction zone returns expected, the second reaction zone effluent stream and a third reaction zone feed, the second reaction zone to return materials incorporated first 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 to return materials 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 above 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 after entering the second reaction zone to the third reaction zone, the third reaction zone obtained in step phantom feed passed into a third reaction zone into contact with a molecular sieve catalyst at 465 ° C~M0 .. ° C, 0 at IMI ^ a~0 5ΜΙ ^ conditions, the molecular sieve catalyst residence 30h~100h in the third reaction zone to produce a 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 C5 + 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] The molecular sieve catalyst and a diluent mixed catalyst continuously fed to the first reaction zone, the molecular sieve catalyst continuously moving slowly, sequentially flows through the first reaction zone, a second reaction zone, a third reaction zone, after the third reaction zone collected periodically regenerated molecular sieve catalyst after the catalyst is regenerated, the regenerated catalyst is incorporated intermittently recycled to the molecular sieve catalyst in step 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] The invention in order to get better results, the following as the present invention, a further preferred:

[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。 Semi-continuous process using a moving bed technique [0023], wherein the methanol is converted to propylene, further comprising: ¾ step 4) obtained in the second and third streams feeding the reaction zone after separating heat exchange, separation obtain ethylene, butene and C2~C4 alkane stream is recycled to the first unit incorporated magic step. 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 magic, making the present invention uses a moving bed technology to convert methanol to propylene in energy efficiency and material efficiency is further improved, with better economic benefits.

[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 can be specific choice of conventional moving bed reactor, such as Application No. 201010175837.1 of Chinese patent application discloses a compound containing oxygen as a raw material for the production of propylene tubular moving bed reactor China's patent application for the production of oxygen-containing compounds as raw materials propylene radial moving bed reactor, Application No. 200810120838.9 Application No. 200810120839.3 of Chinese patent application, discloses a method for oxygen-containing compounds as raw materials to produce propylene horizontal moving bed reactor.

[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 of the three reaction zone with a molecular sieve catalyst, said molecular sieve catalyst is preferably ZSM-5 zeolite, ZSM-5 zeolite catalyst is a molecular sieve having a pore properties with medium coke rate, but also in the abrasion resistance of the moving bed is better. 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 reaction is highly exothermic, so you need to add an inert, solid particles diluted catalyst heat capacity of a majority, 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 catalyst diluent for the ceramic particles or silica particles, generally used has a large heat capacity, the same particle size and the size of the 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。 Quality molecular sieve catalyst and catalyst diluent the ratio of 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 a mixture of methanol and water or methanol using 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 streams of DME to propylene and other olefins than direct heat of reaction from methanol to propylene is much lower, the present invention will be divided into three steps methanol into propylene, wherein the first The main step is to convert methanol to dimethyl ether (first reaction zone), a second step mainly dimethyl ether into propylene (second reaction zone), the third step is converted to higher hydrocarbons cracking propylene (s 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。 Whereby the methanol-to-propylene reaction heat into two parts, two parts of the reaction heat are released in the first and second reaction zone. 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 temperatures accelerate the reaction, while, dealuminated zeolite catalyst to accelerate the reaction, therefore, the present invention is the heat of reaction to convert methanol to propylene is divided into two parts, so as to avoid the process of converting methanol to propylene excessive temperature rise not only possible to suppress the formation of coke, and can inhibit the catalyst dealumination, to maintain high catalyst 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。 Step [0027] 2 ,, first unit of the stream after the addition of water vapor introduced into contact with the second reaction zone with a molecular sieve catalyst. 水蒸气可具体选用公用工程水蒸气。 The specific choice of utilities can steam 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。 Increase of water vapor can significantly reduce the molecular sieve catalyst coke, over a longer period of molecular sieve catalyst activity is maintained at a certain range of values. 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 streams of water vapor control 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, this temperature range can be effectively oxygenate conversion to olefins, lower temperatures in this range favor propylene production, while the more High temperature is advantageous for ethylene production, in order to make the conversion rate 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, the second reaction zone and a third reaction zone in the reaction feed stream with a molecular sieve catalyst flow was countercurrent. 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 lower portion of the reactor feed stream into the reaction zone, and removed from the upper portion of the reaction zone, the molecular sieve catalyst under gravity, to move 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, the conversion occurs in the initial stage, the reaction feed stream is brought into contact with part of the molecular sieve catalyst deactivation, and when the low velocity of the reaction feed stream in the subsequent conversion of the advanced stage of the reaction feed stream with a molecular sieve catalyst with higher activity, therefore, the methanol feedstock with a molecular sieve catalyst in counter-current flow can effectively 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 with the catalyst composition) of methanol to propylene conversion and distribution of the reaction product has a significant influence. 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 in contact with the catalyst material is not sufficient, the reaction conversion rate, and residence time is too long, easily lead product byproduct methane, propane, butane and other hydrocarbons, aromatics and other 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 weight hourly space velocity (WHSV) shows, WHSV refers to mass ratio of the catalyst to the reactor feed mass feed per hour reaction, WHSV greater the value representative of the shorter residence time, the present invention first a reaction zone, a second reaction zone and WHSV third reaction zone 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 molecular sieve catalyst in the reaction zone residence time is preferably for 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。 Incorporated after molecular sieve or molecular sieve catalyst after the catalyst from regenerated catalyst feed inlet into the moving bed reactor of the first reaction zone, in the slow-moving mobile bed reactor and continuously moves through the moving bed reactor of the second reaction zone, moving bed reactor a third reaction zone, 90~300 hours after removal of the catalyst into the moving bed reactor 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), the third through the molecular sieve catalyst after the reaction zone (i.e., coke molecular sieve catalyst) using a catalyst collector, the molecular sieve catalyst collected regularly supplied to the reproducing apparatus reproducing regenerated catalyst, regenerated catalyst and into the zeolite catalyst is recycled to step 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O〜3 : 7。 The quality of the regenerated catalyst with a molecular sieve catalyst unincorporated regenerated catalyst before (i.e. fresh molecular sieve catalyst) ratio 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 with the catalyst system independently reproducing apparatus, reproducing apparatus for reproducing centralized sent, not only save transport costs, but also reduces the complexity of the apparatus after the accumulated to a certain amount of catalyst that is.

[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 of converting methanol to propylene, comprising successively a series of catalyst addition tank, catalyst feed controller, a first reaction zone, a second reaction zone, a third reaction zone, a buffer tank discharging the catalyst, the catalyst discharge The controller and the 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, the second reaction zone and a third reaction zone comprises at least one respective 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。 Placed in the respective moving bed reactor different height levels, between adjacent moving bed reactor, a moving bed reactor at the bottom and the top of the next communication moving bed reactor, for example, by moving the line or string bed overlay then, after moving bed reactors each respectively connected to both ends of the catalyst feed controller, the catalyst buffer tank connected to the 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 of gravity on their own to move from top to bottom, from top to bottom through the respective moving bed reactor, the methanol feed stream with the catalyst is formed wrong, and can reduce energy consumption.

[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 valve device according to the controller as a catalyst catalyst feed to the high pressure from the low pressure delivery. 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 valveless device by a low pressure section, the transition in the middle section, a high pressure section and unloading pipe, blocking valves and throttle device connectivity subsidiary controlled area adjacent to both ends of the particles from the flow of low pressure to the high pressure stage and off.

[0035] 所述的催化剂出料控制器为无阀锁压装置。 [0035] The catalyst discharge controller is a valveless lock pressure device. 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 higher than the 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 of the first reaction zone, to achieve this, in the catalyst disposed imports A valveless lock-pressure transmission system, no valve lock pressure means the catalyst particles can be achieved by the delivery of a high pressure to low pressure, without leakage pressure moving bed reactor, the pressure to achieve a lock function, and the lock pressure devices can be controlled catalyst feed rate and can greatly reduce the flow of catalyst material during the next signs of wear.

[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。 [0036] The conversion of methanol to propylene reproducing apparatus further comprises means for zeolite catalysts in the catalyst collector fed regularly to take measures to artificial reproduction apparatus reproduced, 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。 The first reaction zone [0037], wherein the 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 located between said 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 provided between the heat exchanger means, not only can remove reaction heat generated during the reaction, for better control of each step of the reaction the reaction temperature, and heat exchange can preheat the inlet of each reaction zone material save the utility of heat input to achieve the purpose of the comprehensive utilization of thermal energy systems. 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, quench this time between the addition of a moving bed reactor, quench specific optional heat exchanger, can effectively remove the excess heat of reaction, as in step 3), second stream After the methanol feedstock with heat, chill means the specific use chilled liquid methanol feedstock, methanol or methanol can be used raw concrete mixture of methanol and water, when using methanol feed, processing of raw materials can increase the amount of methanol.

[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) of the present invention is incorporated intermittently regenerated catalyst molecular sieve catalyst (i.e., fresh molecular sieve catalyst), by continuously moving bed reaction zone, the catalyst coke centralized collection, regularly sent reproduction method using a molecular sieve catalyst to complete the three-stage reaction of methanol to dimethyl ether, dimethyl ether to propylene and higher hydrocarbons cracking achieve a material with a molecular sieve catalyst reactor continuous reaction , the molecular sieve catalyst feed the reactor and collecting the outer semi-continuous moving bed process, the reaction system to increase the independence and reproducing apparatus, to reduce the complexity of the entire 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 and the reaction was divided into three sections by reacting, three sections with the same molecular sieve catalyst, not only can improve the conversion of methanol to dimethyl ether reaction zone reduce the content of the final waste water separated methanol and carbon hydrocarbon C2~C4 back refining and cracking of C5 or more higher olefins ultimate goal of improving the selectivity to propylene, while avoiding the need for different catalyst batch operation It leads to the complexity of the 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 to convert methanol to reaction heat during the reaction of propylene etherification reaction heat into two sections, with the first reaction zone is discharged into the preheated reactor feed in the second reaction zone, propylene synthesis reaction The average temperature of the area can be effectively controlled, thereby reducing the carbon and the catalyst dealumination, and keep the 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) of the present invention through the addition of a catalyst and catalyst feed controller discharge controller solves the catalyst feed to the reaction apparatus and the implications of the sealing material, the use of coke catalyst centralized collection, regularly sent reproduction method, simplifying 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) of the present invention in each reaction zone between the moving bed heat exchanger means of the addition of the excess heat of reaction system for the import logistics section of the reaction zone temperature heating, utilization of reaction feed and product discharge 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, the catalyst continuous flow, to achieve a 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 invention uses a second reaction zone back to the refining part of the product (ethylene, butene and C2~C4 alkanes), 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 uses high carbon number of the third reaction zone a hydrocarbon cracking, refining and back part of the product (C2~C4 alkane, ethylene and butene) after the separation is returned to the second reaction zone, reduces the content of by-products improves 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 of the present invention to convert methanol to structural diagram of the apparatus of propylene. 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] Figure 1 for the conversion of methanol to propylene, comprising successively a series of catalyst addition tank STlJI agent feed controller Fl (without a catalyst composed of a low pressure to the valve means of the high-voltage transmission), a first reaction zone D1 The second reaction zone D2, third reaction zone D3, catalyst discharge buffer tank B, catalyst and catalyst discharge controller F2 collector ST2 (valveless lock means). 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, D2, and the third reaction zone a second reaction zone comprising D3 respectively 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。 Placed in the respective moving bed reactor different height levels, between adjacent moving bed reactor, a moving bed reactor at the bottom and the top of the next communication moving bed reactor, for example, by moving the line or string bed overlay then, moving bed reactors connected to each another with the catalyst after feeding controller F1, catalyst B buffer tank discharge connection. 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 reproducing apparatus further comprises means R, the molecular sieve catalyst in the catalyst collector ST2 conveyed using artificial periodic approach to reproducing the reproduction apparatus 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 transfer 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 exchange means HI, H2, H3 located between the moving bed reactor and / or the respective moving bed reactor, more precisely for preheating the material inlet of each reaction zone. 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。 Heat exchange means for utilizing El and E2 reaction zone effluent stream heat preheat the 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。 The present invention is the conversion of methanol to propylene apparatus further comprises a 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 moving bed technology for converting methanol to propylene semi-continuous process of the present invention, comprises 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) the zeolite catalyst with a catalyst from the catalyst feed tank STl diluent over the catalyst feed controller Fl Dl from the top of the first reaction zone was continuously fed to the first reaction zone Dl, by adjusting the lower end of the feed throttle device controller Fl control of the feed rate; s after methanol feedstock from the heat exchanger means Hl Dl bottom of the first reaction zone pass into contact with the first reaction zone Dl molecular sieve catalyst at 240 ° C~300 ° C, 0 IMPa~IMPa reaction. Under the conditions, the molecular sieve catalyst in the first reaction zone residence Dl 30h~100h, Dl top of the first reaction zone to produce a first outlet streams a;

[0049] 所述的第一股物流a包括甲醇、二甲醚和水; [0049], wherein a first streams include 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; The 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 phantom Dl after the first reaction zone from the top of the second reaction zone into the second reaction zone D2 D2, step 1) was obtained after a first streams from the second heat exchanger means H2 through the bottom of the reaction zone into the second reaction zone D2 D2 into contact with a 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, generating the first Two streams c D2 from the top outlet of the second reaction zone effluent;

[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 said second streams include ethylene, propylene, butylene, C1~C4 alkane and C5 components above;

[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) in a second step the magic streams in step 1 c) in methanol feedstock s El device after the heat exchanger, after dehydration and removal sepl oxide into the separation zone to obtain the return of the second reaction zone material d, the second reaction zone effluent stream pi and the third reaction zone feed e, the second reaction zone d incorporated first return feed streams to form a second reaction zone a feed recycled to step b 2);

[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 to return material d include ethylene, butene and C2~C4 alkane, said second reaction zone effluent stream comprising C1 Pl alkanes and propylene, the third reaction zone feed e including more than 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 alkanes (fuel gas), 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) through a molecular sieve catalyst of the second reaction zone D2 from the top of the third after the reaction zone into the third reaction zone D3 D3, the third step of the reaction zone phantom feed e obtained after the heat exchanger means H3 from D3 through third reaction zone into contact with 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, generating a third streams flowing from exit D3 f top third reaction zone;

[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 C5 + 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 streams f and feed in the second reaction zone after the heat exchanger into the separation zone E2 means sep2 separated, isolated ethylene, butene and C2~C4 alkane and stream into a first stream is recycled to step 2), to give the final separation include C1 alkanes (fuel gas containing a small amount of ethylene), propene, C5 + 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] Zeolite catalysts and a diluent mixed catalyst continuously fed to the first reaction zone Dl, the molecular sieve catalyst continuously moving slowly, sequentially flows through the first reaction zone D1, the second reaction zone D2, the third reaction zone D3, through a third D3 molecular sieve catalyst after the reaction zone, and then through a molecular sieve catalyst B after discharge buffer tank and catalyst discharge controller F2, molecular sieve catalyst feed rate of the catalyst discharge controller F2 under 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。 Catalyst collector collects ST2, artificial reproduction apparatus R regularly conveyed to the regenerated catalyst obtained in reproduction. 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。 Incorporated intermittently regenerated catalyst is recycled to the molecular sieve catalyst in step a), the quality of the regenerated catalyst with a molecular sieve catalyst is not incorporated into the catalyst prior to regeneration (i.e., fresh molecular sieve catalyst) ratio of 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] separation zone 1 and s s India India separation method can be referenced patents and patent 01810472. χ 200,580,025,151.1

所介绍的分离工艺方法。 The method described in the separation process.

[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 for the 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。 Quality molecular sieve catalyst and catalyst diluent the ratio of 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, the first streams added to the material after a diluent D2 through the second reaction zone in contact with a molecular sieve catalyst. 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 utilities can steam 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, D2 and the second reaction zone in the third reaction zone D3 reaction feed stream with a molecular sieve catalyst in counter-current flow. 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, D2, and the third the second reaction zone the reaction zone WHSV 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 1 shown [0066] 1 ~ 3 of the present embodiment of the apparatus of the methanol is converted to propylene configuration may be employed as shown.

[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 diluent with the catalyst zeolite catalyst continuously into the first reaction zone, the methanol feedstock inlet temperature was 240 ° C, the methanol feed introduced into the first reaction zone with a molecular sieve catalyst at 240 ° C The next ~280 ° C, 0. 2MPa~0 3MPa conditions, the molecular sieve catalyst residence 30h ,, in the first reaction zone to produce a first streams, outlet temperature of the first streams of 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, passed into the second reaction zone with a molecular sieve catalyst after step 1) obtained in the first streams added utility steam, The molar ratio of the first streams of water vapor 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. second reaction zone residence 30h, second stream to produce 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 streams include ethylene, propylene, butylene, C1~C4 alkane and C5 components above;

[0072] 第二反应区为一个移动床反应器; [0072] The second reaction zone as 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 the step 2, the second stream of step 1) after methanol feedstock exchanger, after dehydration and de-oxide obtained trace oxygenates including water, and then to give the second reaction zone return materials, the second reaction zone effluent stream and a third reaction zone feed, the second reaction zone to return material incorporated first streams loops 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] The second reaction zone to return materials include ethylene, butene and C2~C4 alkanes, the second reaction zone effluent stream comprises C1 paraffin and propylene, the third reaction zone feed comprises more than C5 component;

[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 C1 alkanes isolated (fuel gas), 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 after entering the second reaction zone to the third reaction zone, the third reaction zone obtained in step phantom feed introduced into the third reaction zone and contacting the 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 + hydrocarbon;

[0078] 所述的第三反应区为一个移动床反应器; [0078] The third reaction zone as 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) Step 4) obtained in the third and the second reaction zone streams feed after separation heat, isolated ethylene, butene, and the first unit is incorporated C2~C4 alkane stream is recycled to step 2 ,, finally isolated include C1 paraffins and a small amount of a mixture of ethylene (fuel gas), propylene, a small amount of the (: 3 ~ (; hydrocarbons (due to the industrial production, the failure of all third streams C3~C4 alkane, propylene and butylene all separation, in the final compound, C3~C4 still include small amounts of hydrocarbons, as liquefied petroleum gas), C5 + hydrocarbon (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] selection of the molecular sieve catalyst particles having a diameter of ZSM-5 zeolite 1. 5~2mm of. 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 molecular sieve catalyst diluent is substantially the same size of ceramic particles, zeolite catalyst mass ratio of diluent to catalyst is 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] moving bed molecular sieve catalyst from the bottom of the third reactor of the bed out of the reaction zone (the carbon catalyst) in the bed of a residence time of 90 hours, less than 3% of the coke, which was collected in the catalyst collector regularly focus to regeneration in the regenerator, regenerated catalyst, the amount of coke regenerated catalyst is lower than 0.5% (volume = coke deposited on the unit weight of catalyst coke quality). 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。 Incorporated intermittently regenerated catalyst is recycled to the molecular sieve catalyst in step a), the quality of regenerated catalyst and 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, the 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 mass balance is based on the experimental data by computer simulation is enlarged to an annual handling capacity of one million tons of methanol to obtain. 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%。 From Table 1, the methanol feed rate is 207383kg / h, the generated amount of propylene 6627 ^ g / h, the methanol conversion was 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, is meant to include a small amount of ethylene #, * represents the loss circulation material comprising; wherein LPG is C3~C4 hydrocarbons, mainly alkanes, including a small amount of an olefin; C5 + hydrocarbon gasoline containing a small amount of C4 hydrocarbons, mainly heavy components above C7; aqueous methanol dehydration product comprising unreacted methanol out of the trace and the resulting dimethyl ether, aldehydes and other trace oxygenates; a small amount of fuel gas is mainly C1-C2 hydrocarbon components (mainly alkanes C1, 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 a dry basis percentage 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 diluent with the catalyst zeolite catalyst continuously into the first reaction zone, the methanol feedstock inlet temperature was 260 ° C, the methanol feed introduced into the first reaction zone with a molecular sieve catalyst at 260 ° C The next ~300 ° C, 0. 4MPa~0 6MPa conditions, the molecular sieve catalyst residence 50h ,, in the first reaction zone to produce a first streams, outlet temperature of the first streams of 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, passed into the second reaction zone with a molecular sieve catalyst after step 1) obtained in the first streams added utility steam, The molar ratio of the first streams of water vapor 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. second reaction zone residence 50h, second stream to produce 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 streams include ethylene, propylene, butylene, C1~C4 alkane and C5 components above;

[0095] 第二反应区为一个移动床反应器; [0095] The second reaction zone as 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 the step 2, the second stream of step 1) after methanol feedstock exchanger, after dehydration and de-oxide obtained trace oxygenates including water, and then to give the second reaction zone return materials, the second reaction zone effluent stream and a third reaction zone feed, the second reaction zone to return material incorporated first streams loops 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] The second reaction zone to return materials include ethylene, butene and C2~C4 alkanes, the second reaction zone effluent stream comprises C1 paraffin and propylene, the third reaction zone feed comprises more than C5 component;

[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 further separated paraffins and a small amount of ethylene (fuel gas), 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 after entering the second reaction zone to the third reaction zone, the third reaction zone obtained in step phantom feed introduced into the third reaction zone and contacting the 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 + hydrocarbon;

[0101] 所述的第三反应区为一个移动床反应器; [0101] The third reaction zone as 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 Step 4) obtained in the third streams and a second reaction zone after separating the feed exchanger, isolated ethylene, butene, and the first unit is incorporated C2~C4 alkane stream is recycled to step 2 ,, finally isolated include C1 paraffins and a small amount of a mixture of ethylene (fuel gas), propylene, a small amount of the (: 3 ~ (; hydrocarbons (due to the industrial production, the failure of all third streams C3~C4 alkane, propylene and butylene all separation, in the final compound, C3~C4 still include small amounts of hydrocarbons, as liquefied petroleum gas), C5 + hydrocarbon (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 the molecular sieve catalyst particles having a diameter of ZSM-5 zeolite 1. 5~2mm of. 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 size molecular sieve catalyst particles of quartz sand, zeolite mass ratio of catalyst to diluent, the catalyst is 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] moving bed molecular sieve catalyst from the bottom of the third reactor of the bed out of the reaction zone (the carbon catalyst) in the bed of a residence time of 150 hours, less than 3% of the coke, which was collected in the catalyst collector regularly focus to regeneration in the regenerator, regenerated catalyst, the amount of coke regenerated catalyst is lower than 0.5% (volume = coke deposited on the unit weight of catalyst coke quality). 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。 Incorporated intermittently regenerated catalyst is recycled to the molecular sieve catalyst in step a), the mass ratio of the catalyst and the fresh regenerated 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 second reaction zone and a third reaction zone was 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 lists the mass balance under the above conditions, the mass balance is based on the experimental data, the annual handling capacity of one million tons of methanol 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%。 As apparent from Table 3, the methanol feed rate is 207383kg / h, the amount of propylene produced 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, # meant to include small amounts of ethylene, and * including material loss 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 a dry basis percentage 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 diluent with the catalyst zeolite catalyst continuously into the first reaction zone, the methanol feedstock inlet temperature was 280 ° C, the methanol feed introduced into the first reaction zone with a molecular sieve catalyst at 280 ° C Under ~320 ° C, 0. SMI ^ a~IMPa conditions, the molecular sieve catalyst residence in the first reaction zone 100h, generating a first streams, 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, passed into the second reaction zone with a molecular sieve catalyst after step 1) obtained in the first streams added utility steam, The molar ratio of the first streams of water vapor is 1: 4, the inlet temperature of the first streams of 480 ° C, at 480 ° C~530 ° C, 0 3MPa~ 0. 5MPa conditions, the molecular sieve catalyst in the first. second reaction zone residence 100h, second stream to produce 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] The second streams include ethylene, propylene, butylene, C1~C4 alkane and C5 components above;

[0119] 第二反应区为一个移动床反应器; [0119] The second reaction zone as 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 the step 2, the second stream of step 1) after methanol feedstock exchanger, after dehydration and de-oxide obtained trace oxygenates including water, and then to give the second reaction zone return materials, the second reaction zone effluent stream and a third reaction zone feed, the second reaction zone to return material incorporated first streams loops 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] The second reaction zone to return materials include ethylene, butene and C2~C4 alkanes, the second reaction zone effluent stream comprises C1 paraffin and propylene, the third reaction zone feed comprises more than C5 component;

[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 further separated paraffins and a small amount of ethylene (fuel gas), 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 after entering the second reaction zone to the third reaction zone, the third reaction zone obtained in step phantom feed introduced into the third reaction zone and contacting the 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, third streams to produce an 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 + hydrocarbon;

[0125] 所述的第三反应区为一个移动床反应器; [0125] The third reaction zone as 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) Step 4) obtained in the third and the second reaction zone streams feed after separation heat, isolated ethylene, butene, and the first unit is incorporated C2~C4 alkane stream is recycled to step 2 ,, finally isolated include C1 paraffins and a small amount of a mixture of ethylene (fuel gas), propylene, a small amount of the (: 3 ~ (; hydrocarbons (due to the industrial production, the failure of all third streams C3~C4 alkane, propylene and butylene all separation, in the final compound, C3~C4 still include small amounts of hydrocarbons, as liquefied petroleum gas), C5 + hydrocarbon (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 the molecular sieve catalyst particles having a diameter of ZSM-5 zeolite 1. 5~2mm of. 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 molecular sieve catalyst diluent is substantially the same size of ceramic particles, zeolite mass ratio of catalyst to catalyst diluent is 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] moving bed molecular sieve catalyst from the bottom of the third reactor of the bed out of the reaction zone (the carbon catalyst) in the bed of a residence time of 300 hours, less than 3% of the coke, which was collected in the catalyst collector regularly focus to regeneration in the regenerator, regenerated catalyst, the amount of coke regenerated catalyst is lower than 0.5% (volume = coke deposited on the unit weight of catalyst coke quality). 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。 Incorporated intermittently regenerated catalyst is recycled to the molecular sieve catalyst in step a), the quality of regenerated catalyst and 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 zone was 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 shows the mass balance under the above conditions, the mass balance is based on the experimental data, the annual handling capacity of one million tons of methanol 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 methanol feed rate is 207383kg / h, the amount of propylene produced is 69380kg / h, the methanol conversion rate of 100%.

[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] In Table 5, # meant to include small amounts of ethylene, and * including material loss 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 a dry basis percentage other than water, with respect to the product list methanol feed 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] be seen from the above three examples, the process according to the invention disclosed herein, can achieve better temperature control and catalyst-line response times and higher 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。 Furthermore, within the scope of the present disclosure operates selectively change the product to a lesser extent.

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Citada por
Patente citante Fecha de presentación Fecha de publicación Solicitante Título
CN102924214A *30 Oct 201213 Feb 2013浙江大学Production technique of propylene
CN102924214B *30 Oct 201225 Feb 2015浙江大学Production technique of propylene
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CN103333040A *21 Jun 20132 Oct 2013浙江大学Low energy consumption propylene production technology
Clasificaciones
Clasificación internacionalC07C11/06, C07C1/20
Clasificación cooperativaY02P20/52, Y02P30/42, Y02P20/584
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