CN101260015B - Method for preparing low-carbon olefins from oxygen-containing compound - Google Patents

Method for preparing low-carbon olefins from oxygen-containing compound Download PDF

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CN101260015B
CN101260015B CN 200810043301 CN200810043301A CN101260015B CN 101260015 B CN101260015 B CN 101260015B CN 200810043301 CN200810043301 CN 200810043301 CN 200810043301 A CN200810043301 A CN 200810043301A CN 101260015 B CN101260015 B CN 101260015B
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catalyst
sap0
weight
heat exchange
method
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CN 200810043301
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CN101260015A (en
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齐国祯
钟思青
张惠明
俞志楠
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中国石油化工股份有限公司
中国石油化工股份有限公司上海石油化工研究院
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/58Recycling
    • 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 relates to a method used to prepare low carbon alkene by means of oxygen compound, and mainly aims to solve the problem of the prior art that the yield of the low carbon alkene is low. The method adopts the following technical proposal: regenerated catalyst is fed into a heat exchanger through a catalyst conveying pipe, and then is fed into the bottom of a reaction zone after completing heat exchange with heat-exchange medium which is selected from oxygen compound or at least one product; and the heat-exchange medium is fed into the reaction zone after completing heat exchange with the regenerated catalyst. Therefore, the method solves the problem better through adopting the technical proposal and can be used in the industrial production of low carbon alkene.

Description

由含氧化合物制备低碳烯烃的方法 The method of preparing light olefins from oxygenates in

技术领域 FIELD

[0001] 本发明涉及一种由含氧化合物制备低碳烯烃的方法。 [0001] The present invention relates to a process for the preparation of light olefins from oxygenates is.

[0002] 技术背景 [0002] BACKGROUND OF THE INVENTION

[0003] 低碳烯烃,即乙烯和丙烯,是两种重要的基础化工原料,其需求量在不断增加。 [0003] olefins, namely ethylene and propylene, are two important basic chemical raw materials, the demand is increasing. 一般地,乙烯、丙烯是通过石油路线来生产,但由于石油资源有限的供应量及较高的价格,由石油资源生产乙烯、丙烯的成本不断增加。 Generally, ethylene, propylene are produced by the oil route, but due to limited supply of petroleum resources and the higher the price, the cost of production of ethylene from petroleum resources, increasing the propylene. 近年来,人们开始大力发展替代原料转化制乙烯、丙烯的技术。 In recent years, people began to develop alternative technologies feedstock into ethylene, propylene. 其中,一类重要的用于轻质烯烃生产的替代原料是含氧化合物,例如醇类(甲醇、乙醇)、醚类(二甲醚、甲乙醚)、酯类(碳酸二甲酯、甲酸甲酯)等,这些含氧化合物可以通过煤、天然气、生物质等能源转化而来。 Wherein, an important class of alternative raw materials for the production of light olefins are oxygenates, such as alcohols (methanol, ethanol), ethers (dimethyl ether, methyl ethyl ether), esters (dimethyl carbonate, methyl formate esters), these may be converted from an oxygenate by coal, natural gas, biomass and other energy. 某些含氧化合物已经可以达到较大规模的生产,如甲醇,可以由煤或天然气制得,工艺十分成熟,可以实现上百万吨级的生产规模。 Certain oxygenates have large-scale production can be achieved, such as methanol, may be obtained from coal or natural gas, very mature technology, can be implemented on a production scale megaton. 由于含氧化合物来源的广泛性,再加上转化生成轻质烯烃工艺的经济性,所以由含氧化合物转化制烯烃(OTO)的工艺,特别是由甲醇转化制烯烃(MTO)的工艺受到越来越多的重视。 Because of the extensive source oxygenate, together with conversion of light olefins to generate economic process, so the process to olefins (the OTO) conversion of the oxygenates, in particular by the conversion of methanol to olefins (MTO) process more to more attention.

[0004] US4499327专利中对磷酸硅铝分子筛催化剂应用于甲醇转化制烯烃工艺进行了详细研究,认为SAP0-34是MTO工艺的首选催化剂。 [0004] US4499327 patent applied for the conversion of methanol to olefins process silicoaluminophosphate zeolite catalysts were studied in detail, the preferred catalyst SAP0-34 that the MTO process. SAP0-34催化剂具有很高的轻质烯烃选择性,而且活性也较高,可使甲醇转化为轻质烯烃的反应时间达到小于10秒的程度,更甚至达到提升管的反应时间范围内。 SAP0-34 catalyst having a high light olefin selectivity, but the activity is higher, the conversion of methanol to light olefins allows the reaction time to the extent of less than 10 seconds, even more time to reach the reaction riser.

[0005] US6166282中公布了一种氧化物转化为低碳烯烃的技术和反应器,采用快速流化床反应器,气相在气速较低的密相反应区反应完成后,上升到内径急速变小的快分区后,采用特殊的气固分离设备初步分离出大部分的夹带催化剂。 [0005] US6166282 discloses a the conversion of oxygenates to light olefins and reactor technology, the use of a fast fluidized bed reactor, after completion of the reaction gas in the lower gas velocity dense phase reaction zone, rising to rapidly change the inner diameter fast after a small partition, gas-solid separation apparatus using special preliminary separation of the majority of entrained catalyst. 由于反应后产物气与催化剂快速分离,有效的防止了二次反应的发生。 Since the reaction product gas after the rapid separation of the catalyst, effectively prevents the occurrence of secondary reactions. 经模拟计算,与传统的鼓泡流化床反应器相比,该快速流化床反应器内径及催化剂所需藏量均大大减少。 Simulated calculation, compared with the conventional bubbling fluidized bed reactor, a fast fluidized bed of the desired inner diameter of the reactor volume and catalyst inventory is greatly reduced.

[0006] CN1723^52中公布了带有中央催化剂回路的多级提升管反应装置用于氧化物转化为低碳烯烃工艺,该套装置包括多个提升管反应器、气固分离区、多个偏移组件等,每个提升管反应器各自具有注入催化剂的埠,汇集到设置的分离区,将催化剂与产品气分开。 [0006] CN1723 ^ 52 published a multistage reaction apparatus for riser oxide catalyst with a central loop into light olefins process, the set of devices comprises a plurality of riser reactors, gas-solid separation zone, a plurality of offset components, etc., each of the riser reactors each having a catalyst injection port, aggregated to a separation zone provided to separate the catalyst and product gas.

[0007] 本领域所公知的,要保证高的低碳烯烃选择性,催化剂上需要一定数量的积碳,而且含氧化合物转化为低碳烯烃的过程中对反应温度等工艺参数十分敏感。 [0007] This known in the art, to ensure a high selectivity to light olefins, a certain amount of coke on the catalyst, and converting oxygenates to light olefins during the reaction process parameters such as temperature sensitive. 现有技术均存在反应区内催化剂积炭分布不均、反应温度波动大等问题。 The prior art catalysts are present in the reaction zone uneven distribution of carbon deposition, the reaction temperature fluctuation and so on. 本发明有针对性的解决了该问题。 The present invention has targeted to solve the problem.

[0008] 发明内容 [0008] SUMMARY OF THE INVENTION

[0009] 本发明所要解决的技术问题是现有技术中存在的低碳烯烃收率不高的问题,提供一种新的由含氧化合物制备低碳烯烃的方法。 [0009] The present invention solves the technical problem of the prior art lower olefin yields present not high, to provide a novel method for the preparation of light olefins from oxygenates is. 该方法用于低碳烯烃的生产中,具有低碳烯烃收率较高、低碳烯烃生产工艺经济性较高的优点。 The process for producing light olefins, the olefins having a high yield, the production of light olefins higher process economy advantages.

[0010] 为解决上述问题,本发明采用的技术方案如下:一种由含氧化合物制备低碳烯烃的方法,所述方法包括以下步骤:(a)提供一种流化床反应器,包括反应区、循环区、汽提区、分离区,使包括所述含氧化合物的原料与包括硅铝磷酸盐分子筛催化剂在所述反应区的有效条件下接触,形成包括低碳烯烃、催化剂的物流1 ;(b)所述物流1中的催化剂在分离区中被分离出来,形成待生催化剂,所述待生催化剂进入汽提区;(C)将经过汽提的所述待生催化剂分为两部分,其中第一部分通过催化剂输送管线进入再生器与再生介质接触,形成再生催化剂,第二部分通过催化剂输送管线返回到所述反应区的底部;(d)所述再生催化剂通过催化剂输送管线进入换热器,与换热介质换热后进入所述反应区底部;其中,所述换热介质选自甲醇、二甲醚、碳四以上烃、低碳烷烃 [0010] In order to solve the above problems, the present invention employs the following technical solution: A method for the preparation of light olefins from oxygenates, said method comprising the steps of: (a) provide a fluidized bed reactor comprising a reaction zone, recirculation zone, stripping zone, separation zone, the feedstock comprising said oxygenate with a catalyst comprising a silicoaluminophosphate molecular sieve in said reaction zone under conditions effective to form, the catalyst stream comprising olefins 1 ; (b) in the catalyst stream 1 is separated out in the separation zone, formed in the spent catalyst, the spent catalyst entering the stripping zone; (C) through the said stripped spent catalyst is divided into two portion, wherein the first portion through the catalyst transfer line to enter the regenerator and the regeneration medium contacting regenerated catalyst is formed, a second portion returned to the bottom of the reaction zone via catalyst transfer line; (d) the regenerated catalyst through the catalyst transfer line to enter the transducer heat, and the heat exchanger into the bottom of said reaction zone; wherein said heat exchange medium is selected from methanol, dimethyl ether, carbon four or more hydrocarbons, light alkane 、乙烯、丙烯或产品中的二烯烃中的至少一种,换热介质与原料的重量流率之比为0.01〜0.5 : 1 ;与再生催化剂换热后的换热介质进入反应区。 , Ethylene, propylene or products of at least one diene, the weight ratio of the flow rate of the heat exchange medium with the feedstock is 0.01~0.5: 1; and the heat exchange medium after the heat exchange the regenerated catalyst into the reaction zone.

[0011] 上述技术方案中,所述含氧化合物原料选自甲醇、二甲醚中的至少一种,优选方案选自甲醇;硅铝磷酸盐分子筛选自SAP0-5、SAP0-1 l、SAP0-17、SAP0-18、SAP0-34、SAP0-35、 SAP0-44或SAP0-56中的至少一种,优选方案选自SAP0-18或SAP0-34中的至少一种,更优选方案选自SAP0-34 ;所述反应器为快速流化床或提升管,优选方案选自快速流化床;所述换热介质优选方案选自甲醇、二甲醚、碳四以上烃或产品中的二烯烃中的至少一种,更优选方案选自未反应的甲醇、生成的二甲醚、碳四烯烃或二烯烃中的至少一种,最优选方案选自未反应的甲醇、生成的二甲醚或二烯烃中的至少一种;换热介质与原料的重量流率之比优选方案为0.05〜0.2 : 1,更优选方案为0.06〜0. 1 : 1 ;所述有效条件为:反应压力以表压计为0〜IMPa,反应温度为300〜600°C,原料重时空速为1〜50小时―1,反 [0011] In the above aspect, the oxygenate feedstock is selected from methanol, dimethyl ether, at least one, preferably selected from methanol embodiment; silicoaluminophosphate molecular sieve is selected SAP0-5, SAP0-1 l, SAP0 -17, SAP0-18, SAP0-34, SAP0-35, SAP0-44 SAP0-56 or at least one, preferably selected SAP0-18 embodiment SAP0-34 least one or more selected from the preferred embodiment SAP0-34; the reactor is a fast fluidized bed or riser, fast fluid bed is preferably selected embodiment; the preferred embodiment the heat exchange medium selected dimethanol, dimethyl ether, or hydrocarbons more than four carbon product methanol methanol olefins at least one, and more preferably selected from unreacted embodiment, to generate dimethyl ether, tetrakis olefins or diolefins at least one, most preferably selected from unreacted embodiment, to generate dimethyl ether at least one or two olefins; ratio of weight flow rate of the preferred embodiment of the heat exchange medium with the feedstock is 0.05~0.2: 1, more preferably 0.06~0 scheme 1: 1; the condition is valid: reaction pressure gauge pressure 0~IMPa, the reaction temperature is 300~600 ° C, a weight hourly space velocity of the raw material 1~50 hr -1, trans 区催化剂平均积炭量为0. 01〜7%重量,优选方案的所述有效条件为:反应压力以表压计为0. 01〜 0. 3MPa,反应温度为400〜500°C,原料重时空速为6〜25小时―1,反应区催化剂平均积炭量为1〜4%重量;所述第一部分通过催化剂输送管线进入再生器的待生催化剂占总待生催化剂的5〜90%重量,优选方案为15〜40%重量。 The average amount of coke catalyst zone 0. 01~7% by weight, the preferred embodiment is effective conditions: reaction pressure gauge pressure of 0. 01~ 0. 3MPa, the reaction temperature is 400~500 ° C, the raw material weight 6~25 hourly space velocity hr -1, the reaction zone average catalyst coke in an amount of 1 ~ 4% by weight; the first portion of spent catalyst entering the regenerator through the catalyst transfer line 5~90% by weight of the total spent catalyst , preferred embodiment of 15~40% by weight.

[0012] 本发明所述重时空速定义为包括单位时间内的原料进料量除以反应区内催化剂的活性组分(如分子筛)含量。 [0012] The present invention is defined by dividing the weight hourly space velocity of the active ingredient (e.g., molecular sieves) content of the reaction zone comprises a catalyst material feed amount per unit time.

[0013] 本发明所述的积炭量计算方法为一定质量的催化剂上的积炭质量除以所述的催化剂质量。 [0013] The amount of coke present invention is calculated as the mass of coke on the catalyst mass a mass of catalyst divided by the. 催化剂上的积炭质量测定方法如下:将混合较为均勻的带有积炭的催化剂混合, 然后精确称量一定质量的带碳催化剂,放到高温碳分析仪中燃烧,通过红外测定燃烧生成的二氧化碳质量,从而得到催化剂上的碳质量。 Coke on the catalyst mass measurement method is as follows: mixing the catalyst mixture with relatively uniform coke, and then precisely weighed with a mass of carbon catalyst, into the high temperature combustion carbon analyzer, by measuring the infrared carbon dioxide generated by the combustion mass, whereby the quality of the carbon on the catalyst.

[0014] 本领域所公知的,在甲醇或二甲醚向低碳烯烃的转化过程中会放出大量的热量, 而失活催化剂的烧炭再生过程也会放出大量的热,因此,甲醇或二甲醚制备低碳烯烃的过程属于反应和再生均强放热的过程。 [0014] well known in the art, in a methanol or dimethyl ether may emit a lot of heat during the conversion of light olefins, and the deactivated catalyst regeneration process of charcoal will emit a lot of heat, and therefore, methanol or dimethyl preparation of lower olefins process ether belong are strongly exothermic reaction and the regeneration process. 而由于催化剂再生需要较高的温度,因此反应器和再生器之间的温差一般在200°C以上,这就使得从再生器出来的再生催化剂在返回反应器的过程中带给反应器较多的热量,必然使得反应器内的热量过剩更为严重。 Since the catalyst regeneration require higher temperatures, so the temperature difference between the reactor and regenerator is generally above 200 ° C, which makes the regenerated catalyst from the regenerator to bring out more reactors in the process returns to the reactor heat, so that the inevitable excess heat in the reactor is more serious. 因此,本发明采用在再生催化剂输送管线上加换热器的方法,有效降低了再生催化剂的热量,从而减少了反应器内的过剩热。 Accordingly, the present invention is the method of adding a heat exchanger on the regenerated catalyst transfer line, effectively reducing the amount of heat of the regenerated catalyst, thereby reducing the excess heat in the reactor. 并且,本发明将从再生催化剂上取的这部分热量用于加热部分原料、加热循环利用的未反应的甲醇或二甲醚或者是加热部分生成的产品(如碳四烃),有效的利用了这部分热量,提高了工艺的经济性。 Further, the present invention is taken from that part of the heat for heating the catalyst regeneration portion of the feedstock, heating methanol or dimethyl ether or a heating portion of the resulting product (e.g., carbon Hydrocarbon) recycling unreacted, efficient use of this part of the heat and improve the economics of the process.

[0015] 采用本发明的技术方案:所述含氧化合物原料选自甲醇、二甲醚中的至少一种; 硅铝磷酸盐分子筛选自SAP0-5、SAP0-1U SAP0-17, SAP0-18、SAP0-34、SAP0-35、SAP0-44 或SAP0-56中的至少一种;所述反应器为快速流化床或提升管;换热介质与原料的重量流率之比为0.01〜0.5 : 1;所述有效条件为:反应压力以表压计为0〜IMPa,反应温度为300〜600°C,原料重时空速为1〜50小时―1,反应区催化剂平均积炭量为0. 01〜7%重量;所述第一部分通过催化剂输送管线进入再生器的待生催化剂占总待生催化剂的5〜90% 重量,低碳烯烃收率最高可达到81. 40%重量,取得了较好的技术效果。 [0015] The technical solution of the present invention: the oxygenate feedstock is selected from methanol, dimethyl ether is at least one; silicoaluminophosphate molecular sieve is selected SAP0-5, SAP0-1U SAP0-17, SAP0-18 , SAP0-34, SAP0-35, SAP0-44 SAP0-56 or at least one of; the reactor is a fast fluidized bed or riser; ratio of weight flow rate of the heat exchange medium with the feedstock is 0.01~0.5 : 1; the condition is valid: reaction pressure gauge pressure 0~IMPa, the reaction temperature is 300~600 ° C, a weight hourly space velocity of the raw material 1~50 hr -1, the reaction zone average catalyst coke in an amount of 0 . 01~7% by weight; the first portion of the catalyst entering the regenerator through a spent catalyst transfer line of the total spent catalyst 5~90% by weight, the yield of light olefins can reach 81.40% by weight, obtained better technical effect.

附图说明 BRIEF DESCRIPTION

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

[0017] 图1中,1为反应器原料进料;2为反应器反应区;3为气固快速分离设备;4为汽提区;5为待生催化剂循环斜管;6为待生催化剂去再生器输送管线;7为再生器再生区;8 为反应器气固旋风分离器;9为反应器分离区;10为产品集气室;11为产品气出口管线;12 为再生器稀相段;13为再生介质入口管线;14为再生催化剂输送管线;15为再生器外取热器;16为再生器气固旋风分离器;17为再生烟气出口管线;18为换热器入口管线;19为换热器;20为换热器出口管线;21为再生器;22为反应器。 In [0017] FIG. 1, a raw material feed is reactor; the reactor the reaction zone 2; 3 Solid Separator apparatus; 4 is a stripping zone; 5 cycles of spent catalyst chute; 6 spent catalyst transfer line to a regenerator; regenerative regeneration zone 7; 8 to the cyclone gas-solid reactor; the reactor separation zone 9; product plenum 10; outlet line 11 for the product gas; dilute phase 12 of regenerator section; inlet line 13 to regeneration medium; regenerated catalyst transfer line 14 to; 15 to take an outer heat regenerator; 16 is a gas-solid cyclone regenerator; regenerative flue gas outlet line 17; line 18 to heat exchanger inlet ; is a heat exchanger 19; outlet line 20 to a heat exchanger; regenerator 21; 22 of the reactor.

[0018] 包括含氧化合物原料的物流经进料管线1进入反应器22反应区2中,与分子筛催化剂接触,反应生成含有低碳烯烃的产品,携带待生催化剂经过气固快速分离设备3进入反应器分离区,其中,气固快速分离设备3分离出来的大部分催化剂进入汽提区4,而气相产品以及部分未被气固快速分离设备分离的催化剂经入旋风分离器8分离进行再次分离, 催化剂经过旋风分离器8的料腿返回到汽提区4,气相产品进入集气室10后经出口管线11 进入后续的分离工段。 [0018] comprising the feed stream via line 1 into the oxygenate feedstock reaction zone 22 in the reactor 2, in contact with a molecular sieve catalyst, reaction product containing light olefins, carrying spent catalyst through gas-solid separation device 3 quickly enter the reactor separation zone wherein most of the catalyst Solid separator 3 out of the separation device into the stripping section 4, and vapor phase products, and is not part of the catalyst was separated Solid separator apparatus into the cyclone separator 8 again separated the catalyst through a cyclone dipleg 8 is returned to the stripping zone 4, the product gas enters the plenum chamber 10 through outlet line 11 into the subsequent separation stage. 被气固快速分离设备3和旋风分离器8分离出的待生催化剂经过汽提后分为两部分,一部分通过催化剂循环斜管5返回到反应区2的底部;另外一部分经过催化剂输送管线6进入再生器21的再生区7中烧炭再生,焦炭燃烧生成的烟气经过旋风分离器16后通过烟气出口管线17进入后续的能量回收系统,再生完成的催化剂通过催化剂输送管线14进入换热器19中,与自管线18来的换热介质换热,换热后的再生催化剂通过催化剂输送管线返回到反应区2的底部继续反应,换热介质自管线20进入反应区。 Spent catalyst is quickly separated from the gas-solid cyclone apparatus 3 and 8 separated after stripping is divided into two parts, by circulating the catalyst chute 5 is returned to the bottom of the reaction zone 2; the other part through the catalyst transfer line to enter 6 the regenerator 21 of the regeneration zone 7 regenerated charcoal, coke combustion flue gases after the cyclone 16 into the subsequent flue gas energy recovery system through the outlet line 17, to complete the regenerated catalyst enters the heat exchanger 14 through the catalyst transfer line 19, the heat from the heat exchange medium line 18, the regenerated catalyst is returned through the catalyst transfer line heat exchanger to the bottom of the reaction zone 2 of the reaction was continued, the heat exchange medium from the line 20 into the reaction zone.

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

具体实施方式 Detailed ways

[0020]【实施例1〜4】 [0020] [Example 1 ~ 4]

[0021] 在快速流化床反应装置中,反应系统同图1。 [0021] In a fast fluidized bed reaction apparatus, the reaction system with FIG. 反应区平均温度为500°C,反应压力以表压计为0. IMPa,纯甲醇进料,甲醇重时空速为25小时―1,催化剂类型见表1,换热器19 中与再生催化剂的换热介质为甲醇,换热介质与原料的重量流率之比为0.05 : 1。 The average reaction zone temperature of 500 ° C, the reaction pressure gauge pressure of 0. IMPa, pure methanol feed, methanol weight hourly space velocity of 25 hr -1, the type of catalyst shown in Table 1, the heat exchanger 19 with regenerated catalyst heat transfer medium is methanol, the ratio of weight flow rate of the heat exchange medium with the feedstock of 0.05: 1. 第一部分通过催化剂输送管线6进入再生器21的待生催化剂占总待生催化剂的40 %重量,反应区2中的催化剂平均积炭量为2. 5%重量。 The first portion through the catalyst transfer line to enter the regenerator spent catalyst 6 21 40% by weight of the total spent catalyst, the average amount of coke in the catalyst reaction zone 2 was 2.5% by weight. 保持催化剂流动控制的稳定性,反应器出口产物采用在线气相色谱分析,实验结果见表1。 Maintaining stability of the control flow of the catalyst, the reactor outlet product using online gas chromatographic analysis of the experimental results shown in Table 1.

[0022] 表1 [0022] TABLE 1

[0023] [0023]

Figure CN101260015BD00051

[0024] [0023]【实施例5〜6】[0025] 按照实施例4所述的条件,只是改变反应器温度,实验结果见表2。 [0024] [0023] [Example 5 ~ 6] [0025] under the conditions described in Example 4, except changing the reaction temperature, the experimental results shown in Table 2.

[0026] 表2 [0026] TABLE 2

[0027] [0027]

Figure CN101260015BD00061

[0028]【实施例7〜8】 [0028] [Example 7~8]

[0029] 按照实施例4所述的条件,只是改变原料类型和原料重时空速,实验结果见表3。 [0029] under the conditions described in Example 4, except for changing the type of raw material and a weight hourly space velocity, the experimental results shown in Table 3.

[0030] 表3 [0030] TABLE 3

[0031] [0031]

参数 原料类型 原料重时空速,小时―1 低碳烯烃碳基收率,%重量实施例7 二甲醚 15 79.07实施例8 甲醇:二甲醚=5 : 1 6 79.68 Parameter Type raw material weight hourly space velocity, hr -1 based carbon olefins yield,% by weight of dimethyl ether 15 Example 7 79.07 Example 8 methanol: ether = 5: 16 79.68

[0032]【实施例9〜11】 [0032] [Embodiment] Example 9~11

[0033] 按照实施例4所述的条件,改变反应器型式、反应压力和原料重时空速,实验结果见表4。 [0033] under the conditions described in Example 4, changing the type of reactor, reaction pressure and feed weight hourly space velocity, the experimental results shown in Table 4.

[0034] 表4 [0034] TABLE 4

[0035][0036] 【实施例12〜14】 [0035] [0036] Example [12~14]

[0037] 按照实施例4所述的条件,改变第一部分通过催化剂输送管线6进入再生器21的 [0037] under the conditions described in Example 4, changing a first portion of the catalyst enters regenerator 21 through a transfer line 6,

Figure CN101260015BD00071

待生催化剂占总待生催化剂的比例和平均积炭量,实验结果见表5。 Spent catalyst and the average proportion of the total amount of coke in the spent catalyst, the experimental results shown in Table 5.

[0038] 表5 [0038] TABLE 5

[0039] [0039]

Figure CN101260015BD00081

[0040]【实施例I5】 [0040] I5 [Embodiment Example]

[0041] 按照实施例4所述的条件,换热器19中与再生催化剂的换热介质为二甲醚,换热介质与原料的重量流率之比为0.06 : 1,低碳烯烃收率为79. 72%重量。 [0041] under the conditions described in Example 4, the heat exchange medium in the heat exchanger 19 and the regenerated catalyst is dimethyl ether, the ratio of weight flow rate of the heat exchange medium and the raw material is 0.06: 1, the yield of light olefins to 79.72% by weight.

[0042]【实施例I6】 [0042] [Embodiment] Example I6

[0043] 按照实施例4所述的条件,换热器19中与再生催化剂的换热介质为1- 丁烯,换热介质与原料的重量流率之比为0. 1 : 1,低碳烯烃收率为80. 94%重量。 [0043] under the conditions described in Example 4, the heat exchange medium in the heat exchanger 19 and the regenerated catalyst is 1-butene, the weight ratio of the flow rate of the heat exchange medium and the raw material is 0.1: 1, lower olefins yield of 80.94% by weight.

[0044]【实施例17】 [0044] [Example 17]

[0045] 按照实施例4所述的条件,换热器19中与再生催化剂的换热介质为甲醇与二烯烃的混合物,甲醇与二烯烃的重量比为10 : 1,换热介质与原料的重量流率之比为0.2 : 1, 低碳烯烃收率为80. 15%重量。 [0045] under the conditions described in Example 4, the heat exchanger 19 and the catalyst regeneration medium is a mixture of methanol and diolefins, diolefins methanol weight ratio of 10: 1, the heat exchange medium to feed the ratio of weight flow rate of 0.2: 1, olefins yield 80.15% by weight.

[0046]【实施例I8】 [0046] [Embodiment] Example I8

[0047] 按照实施例4所述的条件,换热器19中与再生催化剂的换热介质为乙烯,换热介质与原料的重量流率之比为0. 01 : 1,低碳烯烃收率为79. 85%重量。 [0047] under the conditions described in Example 4, the heat exchanger 19 and the heat transfer medium of the regenerated catalyst is ethylene, the weight ratio of the flow rate of the heat exchange medium and the raw material is 0.01: 1, the yield of light olefins to 79.85% by weight.

[0048] 【实施例19】 [0048] [Example 19]

[0049] 按照实施例4所述的条件,换热器19中与再生催化剂的换热介质为甲醇和乙烯的混合物,甲醇与乙烯的重量比例为5 : 1,换热介质与原料的重量流率之比为0.5 : 1,低碳烯烃收率为81. 40%重量。 [0049] under the conditions described in Example 4, the heat exchange medium in the heat exchanger 19 and the regenerated catalyst is a mixture of methanol and ethylene, the weight ratio of methanol to ethylene was 5: 1, by weight of the feed stream and the heat exchange medium ratio of 0.5: 1, olefins yield 81.40% by weight.

[0050] 【比较例1】 [0050] [Comparative Example 1]

[0051] 按照实施例4所述的条件,只是将再生催化剂直接返回到反应区2下部,低碳烯烃碳基收率为78. 03%重量。 [0051] under the conditions described in Example 4, except that the regenerated catalyst is returned directly to the lower portion of the reaction zone 2, the carbon-based lower olefin yield 78.03% by weight.

[0052]【比较例2】 [0052] [Comparative Example 2]

[0053] 按照实施例13所述的条件,将再生催化剂直接返回到反应区2下部,低碳烯烃碳基收率为74.重量。 [0053] under the conditions described in Example 13, the regenerated catalyst is returned directly to the lower portion 2, light olefins yield of carbon-based reaction zone 74. wt.

[0054]【比较例3】 [0054] [Comparative Example 3]

[0055] 按照实施例4所述的条件,只是将换热介质换成水蒸气,换热后的水蒸气不进入反应区2中,低碳烯烃碳基收率为78. 86%重量。 [0055] under the conditions described in Example 4, except that the heat exchange medium into steam, the steam after heat exchange without entering the reaction zone 2, the carbon-based lower olefins yield of 78.86% by weight.

[0056] 显然,采用本发明的方法,可以达到提高低碳烯烃收率的目的,具有较大的技术优势,可用于低碳烯烃的工业生产中。 [0056] Obviously, the present invention method, the purpose of improving the yield of light olefins, with great technical advantages, can be used for industrial production of lower olefins.

Claims (9)

1. 一种由含氧化合物制备低碳烯烃的方法,所述方法包括以下步骤:(a)提供一种流化床反应器,包括反应区、循环区、汽提区、分离区,使包括所述含氧化合物的原料与包括硅铝磷酸盐分子筛催化剂在所述反应区的有效条件下接触,形成包括低碳烯烃、催化剂的物流1 ;(b)所述物流1中的催化剂在分离区中被分离出来,形成待生催化剂,所述待生催化剂进入汽提区;(c)将经过汽提的所述待生催化剂分为两部分,其中第一部分通过催化剂输送管线进入再生器与再生介质接触,形成再生催化剂,第二部分通过催化剂输送管线返回到所述反应区的底部;(d)所述再生催化剂通过催化剂输送管线进入换热器,与换热介质换热后进入所述反应区底部;其中,所述低碳烯烃为乙烯和丙烯;所述换热介质选自甲醇、二甲醚、碳四以上烃、 乙烯、丙烯或产品中的二烯烃 1. A method for the preparation of light olefins from oxygenates, said method comprising the steps of: (a) provide a fluidized bed reactor comprising a reaction zone, recirculation zone, stripping zone, separation zone, comprising a so the oxygenate feedstock comprises a compound with a silicoaluminophosphate molecular sieve catalyst under conditions effective to the reaction zone, comprising light olefins formed, the catalyst stream 1; (B) in the catalyst stream in a separation zone 1 is separated out, forming spent catalyst, said spent catalyst into the stripping zone; (c) undergone the stripped spent catalyst is divided into two parts, wherein a first portion enters the regenerator through the regenerated catalyst transfer line medium contact, form a regenerated catalyst and returned to the bottom of the second portion of the reaction zone via catalyst transfer line; (d) the regenerated catalyst entering the heat exchanger through the catalyst transfer line, and after the heat exchanger into the reaction medium a bottom region; wherein the lower olefin is ethylene and propylene; the heat exchange medium selected from methanol, dimethyl ether, carbon four or more hydrocarbons, ethylene, propylene or diene product 中的至少一种,换热介质与原料的重量流率之比为0.01〜 0.5 : 1 ;与再生催化剂换热后的换热介质进入反应区。 At least one, the ratio of weight flow rate of the heat exchange medium to feed 0.01~ 0.5: 1; and the heat exchange medium after the heat exchange the regenerated catalyst into the reaction zone.
2.根据权利要求1所述由含氧化合物制备低碳烯烃的方法,其特征在于所述含氧化合物原料选自甲醇、二甲醚中的至少一种;所述硅铝磷酸盐分子筛选自SAP0-5、SAP0-1U SAP0-17, SAP0-18、SAP0-34、SAP0-35、SAP0-44 或SAP0-56 中的至少一种;所述反应器为快速流化床或提升管。 2. The method of preparation of lower olefins from an oxygenate to claim 1, characterized in that the oxygenate feedstock is selected from methanol, dimethyl ether in at least one of; the silicoaluminophosphate molecular sieve is selected from SAP0-5, SAP0-1U SAP0-17, SAP0-18, SAP0-34, SAP0-35, SAP0-44 SAP0-56 or at least one of; the reactor is a fast fluidized bed or riser.
3.根据权利要求2所述由含氧化合物制备低碳烯烃的方法,其特征在于所述含氧化合物原料选自甲醇;所述硅铝磷酸盐分子筛选自SAP0-18或SAP0-34中的至少一种;所述反应器为快速流化床;所述换热介质选自甲醇、二甲醚、碳四以上烃或产品中的二烯烃中的至少一种,换热介质与原料的重量流率之比为0.05〜0.2 : 1。 3. The method of preparation of lower olefins from an oxygenate to claim 2, wherein said oxygenate feedstock is selected from methanol; said silicoaluminophosphate molecular sieve is selected SAP0-18 or SAP0-34 at least one of; the reactor is a fast fluidized bed; is selected from at least one of the heat exchange medium, the heat exchange medium to feed the weight of methanol, dimethyl ether, carbon four or more hydrocarbon products of dienes the ratio of flow rate of 0.05~0.2: 1.
4.根据权利要求3所述由含氧化合物制备低碳烯烃的方法,其特征在于所述硅铝磷酸盐分子筛为SAP0-34 ;所述换热介质选自未反应的甲醇、生成的二甲醚、碳四烯烃或二烯烃中的至少一种,换热介质与原料的重量流率之比为0.06〜0.1 : 1。 4. The method of preparing light olefins from oxygenates in the claim 3, characterized in that said silicoaluminophosphate molecular sieve is SAP0-34; the heat exchange medium is selected from methanol and unreacted dimethyl generated ether, at least one, the weight ratio of the heat exchange medium flow rate of the feedstock olefins or diolefins four carbon is from 0.06~0.1: 1.
5.根据权利要求4所述由含氧化合物制备低碳烯烃的方法,其特征在于所述换热介质选自未反应的甲醇、生成的二甲醚或二烯烃中的至少一种。 5. The method of preparing light olefins from oxygenates in the claim 4, wherein said heat exchange medium is selected from the unreacted methanol, dimethyl ether generating at least one or two olefins.
6.根据权利要求1所述由含氧化合物制备低碳烯烃的方法,其特征在于所述有效条件为:反应压力以表压计为0〜IMPa,反应温度为300〜600°C,原料重时空速为1〜50小时-1,反应区催化剂平均积炭量为0. 01〜7%重量。 6. The method of preparing light olefins from oxygenates in claim 1, wherein said effective conditions are: a reaction pressure gauge pressure 0~IMPa, the reaction temperature is 300~600 ° C, the raw material weight 1~50 hourly space velocity hr -1, the reaction zone average catalyst coke in an amount of 0.5% by weight 01~7.
7.根据权利要求6所述由含氧化合物制备低碳烯烃的方法,其特征在于所述有效条件为:反应压力以表压计为0. 01〜0. 3MPa,反应温度为400〜500°C,原料重时空速为6〜25 小时-1,反应区催化剂平均积炭量为1〜4%重量。 7. The method of preparing light olefins from oxygenates in claim 6, wherein said effective conditions: reaction pressure gauge pressure of 0. 01~0 3MPa, the reaction temperature is 400~500 ° C, a weight hourly space velocity of the raw material 6~25 hr -1, the reaction zone average catalyst coke in an amount of 1 ~ 4% by weight.
8.根据权利要求1所述由含氧化合物制备低碳烯烃的方法,其特征在于所述第一部分通过催化剂输送管线进入再生器的待生催化剂占总待生催化剂的5〜90%重量。 8. The method of preparing light olefins from oxygenates in the claim 1, wherein said first portion of spent catalyst entering the regenerator through the catalyst transfer line 5~90% by weight of the total spent catalyst.
9.根据权利要求8所述由含氧化合物制备低碳烯烃的方法,其特征在于所述第一部分通过催化剂输送管线进入再生器的待生催化剂占总待生催化剂的15〜40%重量。 9. The method of preparing light olefins from oxygenates in claim 8, wherein said first portion of spent catalyst entering the regenerator through the catalyst transfer line 15~40% by weight of the total spent catalyst.
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