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WO2013177723A1 - Process for producing olefin by dehydrogenation of alkane - Google Patents

Process for producing olefin by dehydrogenation of alkane Download PDF

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Publication number
WO2013177723A1
WO2013177723A1 PCT/CN2012/000836 CN2012000836W WO2013177723A1 WO 2013177723 A1 WO2013177723 A1 WO 2013177723A1 CN 2012000836 W CN2012000836 W CN 2012000836W WO 2013177723 A1 WO2013177723 A1 WO 2013177723A1
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WIPO (PCT)
Prior art keywords
catalyst
bed
enters
cyclone separator
dehydrogenating
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PCT/CN2012/000836
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French (fr)
Chinese (zh)
Inventor
庞春天
郝希仁
谢恪谦
丁洪春
Original Assignee
中国石油天然气集团公司
中国石油天然气华东勘察设计研究院
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Publication of WO2013177723A1 publication Critical patent/WO2013177723A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • This invention relates to an engineering process for the dehydrogenation of alkanes to olefins, and more particularly to a fluidized engineering process for the catalytic dehydrogenation of alkanes to olefins.
  • Olefins and di-olefins ethylene, propylene, butene, isobutylene, isoprene, butadiene, etc.
  • synthetic resins plastics
  • high octane gasoline blending components methyl tert-butyl ether, methyl uncle Widely used in amyl hydrazine and alkylated oils and other high value-added products.
  • hydrocarbons such as ethane steam cracking, naphtha steam cracking
  • catalytic cracking of olefins are steam cracked by hydrocarbons (such as ethane steam cracking, naphtha steam cracking), catalytic cracking of olefins.
  • catalytic dehydrogenation of terpene hydrocarbons is also an important technical route for the production of olefins and diolefins.
  • the alkane dehydrogenation catalyst is a fine powder type catalyst, so the successful development of a fluidized bed continuous regeneration alkane dehydrogenation olefin plant capable of simultaneously solving the problem of dehydrogenation of the terpene hydrocarbon and the fluidization of the fine powder catalyst will have a very strong technical cost.
  • the method for dehydrogenating a terpene hydrocarbon to an olefin according to the present invention: the raw material terpene hydrocarbon is preheated by a terpene hydrocarbon-reacting oil and gas heat exchanger and a raw material preheating furnace, and then enters the bottom of the dehydrogenation reactor, passes through the sputum distribution device and the catalyst bed The layer is uniformly contacted in countercurrent and dehydrogenation occurs, and the heat of reaction is provided by the bed catalyst. The reaction product leaves the dehydrogenation reactor after the catalyst is recovered in the dilute phase space by the cyclone separator.
  • the high temperature oil and gas enters the subsequent separation system after being cooled by the steam generator and the alkane reaction oil and gas heat exchanger; the catalyst to be produced enters the bottom of the dehydrogenation reactor.
  • a catalyst stripping section uniformly injecting fuel oil into the catalyst to be produced in the stripping section of the catalyst to be produced, or injecting fuel oil into the inclined tube before the riser to be produced, and the catalyst to be injected after the injection enters
  • the catalyst riser is to be sent to the bottom of the regenerator by the auxiliary main air heated by the auxiliary combustion chamber, and the scorch is continuously flowed in the regenerator, and the fuel oil is burned and exothermic to provide sufficient heat for the catalyst; the regenerated catalyst overflows to the regenerated catalyst In the stripping section, the stripped regenerated catalyst enters the upper part of the dehydrogenation reactor bed; the high temperature flue gas in the regenerator recovers the catalyst through the cyclone separator, and then leaves the regenerator to enter the tertiary cyclone to
  • the dehydrogenation reactor of the present invention is a single-stage countercurrent constant velocity bubble bed reactor; the dense phase bed of the reactor is in the shape of an inverted truncated cone, and the top diameter is large and the bottom diameter is small, which is realized by stepwise increase of the cross-sectional area of the bed.
  • the bed line has a line speed, a beryllium hydrocarbon distributor is arranged at the bottom of the bed, a catalyst distributor is arranged at the top, a multi-layer grid is arranged in the middle of the bed, and a two-stage cyclone separator is arranged in the dilute phase space.
  • the regenerator of the present invention is a single-stage co-current bubble bed regenerator; a catalyst distributor is arranged at the bottom of the regenerator bed, a multi-layer grid is arranged in the bed layer, and a two-stage cyclone separator is arranged in the dilute phase space.
  • the stripping section of the present invention is provided with a multi-layer grid baffle, and the grid is installed obliquely symmetrically, and the cross-sectional area of the single-layer grid is smaller than the cross-sectional area of the stripping section.
  • Fig. 1 is a schematic flow chart of a fluidized bed system for a fine powder catalyst of a dehydrogenation unit for a hydrocarbon. Among them: 1 alkane-reacting oil and gas heat exchanger, 2 raw material preheating furnace, 3 dehydrogenation reactor oil and gas steam generator, 5 spent catalyst stripping section, 6 auxiliary combustion chamber, 7 waiting catalyst riser, 8 regenerated catalyst Stripping section, 9 regenerator, 10 three-stage cyclone separator, 11 double action Spool valve, 12 flue gas pressure reducing orifice plate, 13 four-stage cyclone separator, 14 tricyclotron recovery catalyst storage tank, 15 critical flow rate nozzle
  • the raw material alkane is preheated through the alkane-reaction oil-gas heat exchanger 1 and the raw material preheating furnace 2, and then enters the bottom of the dehydrogenation reactor 3, and is uniformly contacted with the catalyst bed through the helium hydrocarbon distributor and dehydrogenation reaction occurs, and the reaction heat is generated.
  • the reaction product leaves the dehydrogenation reactor after the catalyst is recovered in the dilute phase space by the cyclone separator, and the high temperature oil and gas is cooled by the steam generator 4, the hydrocarbon-reacting oil and gas heat exchanger 1 and then enters the subsequent separation system;
  • the raw catalyst enters the catalyst stripping section 5 at the bottom of the dehydrogenation reactor, and uniformly injects the fuel oil into the catalyst to be produced in the stripping section of the catalyst to be produced, or in the inclined tube before the catalyst riser 7 to be produced
  • the fuel oil is injected, and the injected catalyst after entering the fuel enters the catalyst riser 7 to be produced, and the main wind heated by the auxiliary combustion chamber 6 is sent to the bottom of the regenerator 9 to complete the charring and fuel oil combustion in the regenerator.
  • the exotherm provides sufficient heat for the catalyst; the regenerated catalyst overflows to the regenerated catalyst stripping section 8, and is stripped to the upper part of the dehydrogenation reactor bed; the high temperature in the regenerator
  • the flue gas is recovered by the two-stage cyclone separator, and then leaves the regenerator to enter the third-stage cyclone separator 10 to further recover the catalyst fine powder, and the high-temperature flue gas leaving the third-stage cyclone separator passes through the double-acting slide valve 11 and the flue gas step-down hole.
  • the plate 12 After the plate 12 is depressurized, it enters the waste heat boiler to recover heat; the catalyst fine powder at the bottom of the third-stage cyclone separator enters the fourth-stage cyclone separator 13, and the catalyst fine powder at the bottom of the fourth-stage cyclone separator enters the tertiary cyclone to recover the catalyst storage tank 14
  • the flue gas at the top of the four-stage cyclone separator is depressurized by the critical flow nozzle 15 and then incorporated into the flue gas line after the flue gas depressurization orifice plate 12.
  • Part of the self-produced dry gas enters the auxiliary combustion chamber. 6
  • the combustion exotherm provides part of the heat to the catalyst, and a part of it enters the raw material preheating furnace to burn the heating material.
  • the isobutane feedstock is heated to 300-550 Torr and enters the bottom of the reactor bed.
  • the regenerated catalyst enters the top of the reactor bed.
  • the regenerant temperature is controlled at 650-750 ° C.
  • the reaction temperature is controlled at 500-620 °C
  • the top pressure of the reactor is controlled at 1- lObar (absolute pressure)
  • the mass space is controlled at 2-8ho.
  • the single-pass conversion rate of isobutane 40- 50% can be obtained by using the engineering method and equipment of the present invention. And has a selectivity to 80-90% by mole of isobutylene.
  • the invention provides an engineering scheme for fluidized bed continuous reaction regeneration of a fine powder catalyst for catalytic dehydrogenation of an alkane to olefin, which has the advantages of simple process and convenient operation, and solves the problem of fluidization of the fine powder catalyst and the supply of reaction heat, thereby This production process is continuous and stable.
  • the present invention is applicable to an industrial apparatus for catalytically dehydrogenating an alkane to a olefin using a fluidized bed.
  • the two-type industrial device can realize the continuous reaction regeneration process of catalytic hydrogenation of hydrocarbons to olefins, reduce energy consumption of industrial devices, improve production efficiency, save human resources, and adjust flexibility.
  • the single-pass conversion of the raw material alkane using the method is closer to the equilibrium conversion rate, and the selectivity of the target product (olefin) is higher, and the single-pass conversion of isobutane in the embodiment can reach 40-50%.
  • the selectivity can be 80-90% (molar), so it has good industrial applicability.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to a process for producing an olefin by the dehydrogenation of an alkane; a raw material alkane is preheated, sent to the bottom of a dehydrogenation reactor and comes into contact with a catalyst to carry out a dehydrogenation reaction; after recovering the catalyst by means of a cyclone separator in the space of a dilute phase, the reaction product leaves the dehydrogenation reactor, and the high-temperature oil gas is cooled and then sent to a separation system; the catalyst to be generated is sent to the stripping section for the catalyst to be generated at the bottom of the dehydrogenation reactor; after spraying with oil, the catalyst to be generated is sent to a raising tube for the catalyst to be generated, then to the bottom of a regenerator by using the main air after heating, and scorching and complementing of heat are completed in the regenerator; the regenerated catalyst flows to the stripping section for the regenerated catalyst; the stripped regenerated catalyst is sent to the bed layer of the dehydrogenation reactor; the high-temperature flue gas is passed through a cyclone separator for recovering the catalyst, sent to a three-stage cyclone separator for recovering the catalyst fine powder, and to a waste heat boiler for recovering heat; a part of the dry gas is sent to an auxiliary combustion chamber, and the other part is sent to a pre-heating boiler for the raw material; the present process solves the problems posed by the fluidization of a fine powder catalyst and the supply of the reaction heat.

Description

一种垸烃脱氢制烯烃的方法  Method for dehydrogenating hydrazine to olefin
技术领域 Technical field
本发明涉及一种烷烃脱氢制烯烃的工程方法， 更具体地说涉及烷烃 催化脱氢制烯烃装置的流化工程方法。  Field of the Invention This invention relates to an engineering process for the dehydrogenation of alkanes to olefins, and more particularly to a fluidized engineering process for the catalytic dehydrogenation of alkanes to olefins.
背景 Background
烯烃和二'烯烃（乙烯、 丙烯、 丁烯、 异丁烯、 异戊二烯和丁二烯等) 在合成树脂、 塑料、 高辛烷值汽油调和组分 （甲基叔丁基醚、 甲基叔戊 基醸和烷基化油） 及其它高附加值产品方面应用广泛。 这些炼烃除了通 过烃的蒸汽裂解（如乙烷蒸汽裂解， 石脑油蒸汽裂解)、 烯烃的催化裂解 Olefins and di-olefins (ethylene, propylene, butene, isobutylene, isoprene, butadiene, etc.) in synthetic resins, plastics, high octane gasoline blending components (methyl tert-butyl ether, methyl uncle Widely used in amyl hydrazine and alkylated oils and other high value-added products. These refineries are steam cracked by hydrocarbons (such as ethane steam cracking, naphtha steam cracking), catalytic cracking of olefins.
(如 Superflex技术）、 重油的催化裂解（如 TMP、 DCC技术）和重油催 化热解（如 CPP技术）等过程生产外， 垸烃催化脱氢也是烯烃和二烯烃 生产的重要技术路线。 In addition to processes such as superflex technology, heavy oil catalytic cracking (such as TMP, DCC technology) and heavy oil catalytic pyrolysis (such as CPP technology), catalytic dehydrogenation of terpene hydrocarbons is also an important technical route for the production of olefins and diolefins.
目前国外已经开发的烷烃脱氢工业化技术有 U0P公司的 Oleflex工 艺、 Luramus 公司的 Catofin 工艺、 Phillips 公司的 STAR 工艺、 Snamprogetti公司的 FBD- 4工艺、 Linde公司的 Linde工艺等， 但受供 热影响多采用固定床反应器。 烷烃脱氢催化剂是细粉型催化剂， 因此成 功开发能够同时解决浣烃脱氢给热问题和细粉催化剂流化问题的流化床 连续再生的烷烃脱氢制烯烃装置将具有非常强的技术成本优势， 市场前 景非常广阔。  At present, the alkane dehydrogenation industrialization technology developed abroad has U0P's Oleflex process, Luramus's Catofin process, Phillips' STAR process, Snamprogetti's FBD-4 process, Linde's Linde process, etc., but is affected by heat supply. A fixed bed reactor was employed. The alkane dehydrogenation catalyst is a fine powder type catalyst, so the successful development of a fluidized bed continuous regeneration alkane dehydrogenation olefin plant capable of simultaneously solving the problem of dehydrogenation of the terpene hydrocarbon and the fluidization of the fine powder catalyst will have a very strong technical cost. Advantages, the market prospects are very broad.
发明内容 Summary of the invention
本发明的目的是提供一种烷烃脱氢制烯烃的方法； 通过系统补燃技 术、 细粉催化剂的流化技术实现连续稳定的反应再生过程。  SUMMARY OF THE INVENTION It is an object of the present invention to provide a process for the dehydrogenation of alkanes to olefins; a continuous and stable reaction regeneration process by means of a system refueling technique, a fluidization technique of a fine powder catalyst.
本发明所述的垸烃脱氢制烯烃的方法： 原料垸烃经过垸烃-反应油气 换热器及原料预热炉预热后进入脱氢反应器底部， 通过焼经分布器后与 催化剂床层逆流均匀接触并发生脱氢反应， 反应热由床层催化剂提供， 反应产物在稀相空间经旋风分离器回收催化剂后离开脱氢反应器， 高温 油气经蒸汽发生器、 烷烃 反应油气换热器降温后进入后续分离系统； 待 生催化剂在脱氢反应器底部进入待生催化剂汽提段， 在待生催化剂汽提 段内向待生催化剂中均匀喷入燃料油， 或在待生提升管前的待生斜管中 喷入燃料油， 喷油后的待生催化剂进入待生催化剂提升管， 用辅助燃烧 室加热后的主风输送至再生器底部， 在再生器内顺流完成烧焦、 燃料油 燃烧放热为催化剂提供充足的热量； 再生催化剂溢流至再生催化剂汽提 段， 汽提后的再生催化剂进入脱氢反应器床层上部； 再生器内的高温烟 气经旋风分离器回收催化剂， 然后离开再生器进入三级旋风分离器进一 步回收催化剂细粉， 离开三级旋风分离器的高温烟气进入余热锅炉回收 热量； 装置自产干气一部分进入辅助燃烧室燃烧放热为催化剂提供部分 热量， 一部分进入原料预热炉燃烧加热原料。 The method for dehydrogenating a terpene hydrocarbon to an olefin according to the present invention: the raw material terpene hydrocarbon is preheated by a terpene hydrocarbon-reacting oil and gas heat exchanger and a raw material preheating furnace, and then enters the bottom of the dehydrogenation reactor, passes through the sputum distribution device and the catalyst bed The layer is uniformly contacted in countercurrent and dehydrogenation occurs, and the heat of reaction is provided by the bed catalyst. The reaction product leaves the dehydrogenation reactor after the catalyst is recovered in the dilute phase space by the cyclone separator. The high temperature oil and gas enters the subsequent separation system after being cooled by the steam generator and the alkane reaction oil and gas heat exchanger; the catalyst to be produced enters the bottom of the dehydrogenation reactor. a catalyst stripping section, uniformly injecting fuel oil into the catalyst to be produced in the stripping section of the catalyst to be produced, or injecting fuel oil into the inclined tube before the riser to be produced, and the catalyst to be injected after the injection enters The catalyst riser is to be sent to the bottom of the regenerator by the auxiliary main air heated by the auxiliary combustion chamber, and the scorch is continuously flowed in the regenerator, and the fuel oil is burned and exothermic to provide sufficient heat for the catalyst; the regenerated catalyst overflows to the regenerated catalyst In the stripping section, the stripped regenerated catalyst enters the upper part of the dehydrogenation reactor bed; the high temperature flue gas in the regenerator recovers the catalyst through the cyclone separator, and then leaves the regenerator to enter the tertiary cyclone to further recover the catalyst fine powder, leaving The high-temperature flue gas of the three-stage cyclone separator enters the waste heat boiler to recover heat; the self-produced dry gas of the device enters the auxiliary combustion The exothermic combustion catalyst to provide part of the heat, a portion of the feed to preheat combustion heating furnace feedstock.
本发明所述的脱氢反应器为单段逆流等速气泡床层反应器； 反应器 密相床层为倒置圆台形状， 顶部直径大、 底部直径小， 通过床层截面积 的步增来实现床层等线速， 床层底部设有垸烃分布器、 顶部设有催化剂 分布器， 床层中间设有多层格栅， 稀相空间设有两级旋风分离器。  The dehydrogenation reactor of the present invention is a single-stage countercurrent constant velocity bubble bed reactor; the dense phase bed of the reactor is in the shape of an inverted truncated cone, and the top diameter is large and the bottom diameter is small, which is realized by stepwise increase of the cross-sectional area of the bed. The bed line has a line speed, a beryllium hydrocarbon distributor is arranged at the bottom of the bed, a catalyst distributor is arranged at the top, a multi-layer grid is arranged in the middle of the bed, and a two-stage cyclone separator is arranged in the dilute phase space.
本发明所述的再生器为单段顺流气泡床再生器； 再生器床层底部设 有催化剂分布器， 床层内设有多层格栅， 稀相空间设有两级旋风分离器。  The regenerator of the present invention is a single-stage co-current bubble bed regenerator; a catalyst distributor is arranged at the bottom of the regenerator bed, a multi-layer grid is arranged in the bed layer, and a two-stage cyclone separator is arranged in the dilute phase space.
本发明所述的汽提段内设有多层格栅挡板， 格栅为倾斜对称安装， 单层格栅截面积小于汽提段横截面积。  The stripping section of the present invention is provided with a multi-layer grid baffle, and the grid is installed obliquely symmetrically, and the cross-sectional area of the single-layer grid is smaller than the cross-sectional area of the stripping section.
It图说明  It diagram description
图 1 是垸烃脱氢制烯烃装置细粉催化剂流化床系统流程示意图。 其中： 1烷烃 -反应油气换热器、 2原料预热炉、 3脱氢反应器 油气蒸汽发生器、 5待生催化剂汽提段、 6 辅助燃烧室、 7待生催化剂 提升管、 8再生催化剂汽提段、 9再生器、 10三级旋风分离器、 11双动 滑阀、 12烟气降压孔板、 13四级旋风分离器、 14三旋回收催化剂储罐、 15临界流速喷嘴 Fig. 1 is a schematic flow chart of a fluidized bed system for a fine powder catalyst of a dehydrogenation unit for a hydrocarbon. Among them: 1 alkane-reacting oil and gas heat exchanger, 2 raw material preheating furnace, 3 dehydrogenation reactor oil and gas steam generator, 5 spent catalyst stripping section, 6 auxiliary combustion chamber, 7 waiting catalyst riser, 8 regenerated catalyst Stripping section, 9 regenerator, 10 three-stage cyclone separator, 11 double action Spool valve, 12 flue gas pressure reducing orifice plate, 13 four-stage cyclone separator, 14 tricyclotron recovery catalyst storage tank, 15 critical flow rate nozzle
具体实肺式 Specific lung
下面结合图 1对垸烃催化脱氢制烯烃装置进行说明。  The apparatus for catalytically dehydrogenating a hydrazine to olefins will now be described with reference to FIG.
原料烷烃经过烷经-反应油气换热器 1及原料预热炉 2预热后进入脱 氢反应器 3底部， 通过垸烃分布器后与催化剂床层逆流均匀接触并发生 脱氢反应， 反应热由床层催化剂提供， 反应产物在稀相空间经旋风分离 器回收催化剂后离开脱氢反应器， 高温油气经蒸汽发生器 4、 垸烃-反应 油气换热器 1 降温后进入后续分离系统； 待生催化剂在脱氢反应器底部 进入待生催化剂汽提段 5，在待生催化剂汽提段内向待生催化剂中均匀喷 入燃料油， 或在待生催化剂提升管 7前的待生斜管中喷入燃料油， 喷油 后的待生催化剂进入待生催化剂提升管 7，用辅助燃烧室 6加热后的主风 输送至再生器 9底部， 在再生器内顺流完成烧焦、 燃料油燃烧放热为催 化剂提供充足的热量；再生催化剂溢流至再生催化剂汽提段 8，汽提后进 入脱氢反应器床层上部； 再生器内的高温烟气经两级旋风分离器回收催 化剂， 然后离开再生器进入三级旋风分离器 10进一步回收催化剂细粉， 离开三级旋风分离器的高温烟气经双动滑阀 11、烟气降压孔板 12降压后 进入余热锅炉回收热量； 三级旋风分离器底部的催化剂细粉进入四级旋 风分离器 13， 四级旋风分离器底部的催化剂细粉进入三级旋风分离器回 收催化剂储罐 14间断外运处理， 四级旋风分离器顶部的烟气经临界流速 喷嘴 15降压后并入烟气降压孔板 12后的烟气管线。 装置自产干气一部 分进入辅助燃烧室 6燃烧放热为催化剂提供部分热量， 一部分进入原料 预热炉燃烧加热原料。  The raw material alkane is preheated through the alkane-reaction oil-gas heat exchanger 1 and the raw material preheating furnace 2, and then enters the bottom of the dehydrogenation reactor 3, and is uniformly contacted with the catalyst bed through the helium hydrocarbon distributor and dehydrogenation reaction occurs, and the reaction heat is generated. Provided by the bed catalyst, the reaction product leaves the dehydrogenation reactor after the catalyst is recovered in the dilute phase space by the cyclone separator, and the high temperature oil and gas is cooled by the steam generator 4, the hydrocarbon-reacting oil and gas heat exchanger 1 and then enters the subsequent separation system; The raw catalyst enters the catalyst stripping section 5 at the bottom of the dehydrogenation reactor, and uniformly injects the fuel oil into the catalyst to be produced in the stripping section of the catalyst to be produced, or in the inclined tube before the catalyst riser 7 to be produced The fuel oil is injected, and the injected catalyst after entering the fuel enters the catalyst riser 7 to be produced, and the main wind heated by the auxiliary combustion chamber 6 is sent to the bottom of the regenerator 9 to complete the charring and fuel oil combustion in the regenerator. The exotherm provides sufficient heat for the catalyst; the regenerated catalyst overflows to the regenerated catalyst stripping section 8, and is stripped to the upper part of the dehydrogenation reactor bed; the high temperature in the regenerator The flue gas is recovered by the two-stage cyclone separator, and then leaves the regenerator to enter the third-stage cyclone separator 10 to further recover the catalyst fine powder, and the high-temperature flue gas leaving the third-stage cyclone separator passes through the double-acting slide valve 11 and the flue gas step-down hole. After the plate 12 is depressurized, it enters the waste heat boiler to recover heat; the catalyst fine powder at the bottom of the third-stage cyclone separator enters the fourth-stage cyclone separator 13, and the catalyst fine powder at the bottom of the fourth-stage cyclone separator enters the tertiary cyclone to recover the catalyst storage tank 14 Intermittent outbound processing, the flue gas at the top of the four-stage cyclone separator is depressurized by the critical flow nozzle 15 and then incorporated into the flue gas line after the flue gas depressurization orifice plate 12. Part of the self-produced dry gas enters the auxiliary combustion chamber. 6 The combustion exotherm provides part of the heat to the catalyst, and a part of it enters the raw material preheating furnace to burn the heating material.
异丁烷原料被加热到 300-550Ό ,进入反应器床层底部，再生催化剂 进入反应器床层顶部， 再生剂温度控制在 650-750°C， 反应温度控制在 500-620 °C , 反应器顶部压力控制在 1- lObar (绝压）， 质量空时控制在 2-8ho 使用本发明的工程化方法及设备可以获得异丁烷 40- 50%的单程转 化率， 并具有对异丁烯 80-90% (摩尔） 的选择性。The isobutane feedstock is heated to 300-550 Torr and enters the bottom of the reactor bed. The regenerated catalyst enters the top of the reactor bed. The regenerant temperature is controlled at 650-750 ° C. The reaction temperature is controlled at 500-620 °C, the top pressure of the reactor is controlled at 1- lObar (absolute pressure), and the mass space is controlled at 2-8ho. The single-pass conversion rate of isobutane 40- 50% can be obtained by using the engineering method and equipment of the present invention. And has a selectivity to 80-90% by mole of isobutylene.
ik实用性  Ik practicality
本发明提供了一种烷烃催化脱氢制烯烃的细粉催化剂流化床连续反 应再生的工程化方案， 流程简单、 操作方便， 解决了细粉催化剂的流化 问题和反应热的供给问题， 从而使该生产过程连续且稳定。 本发明适用 于采用流化床的烷烃催化脱氢制烯烃的工业装置。  The invention provides an engineering scheme for fluidized bed continuous reaction regeneration of a fine powder catalyst for catalytic dehydrogenation of an alkane to olefin, which has the advantages of simple process and convenient operation, and solves the problem of fluidization of the fine powder catalyst and the supply of reaction heat, thereby This production process is continuous and stable. The present invention is applicable to an industrial apparatus for catalytically dehydrogenating an alkane to a olefin using a fluidized bed.
使用该两器型式的工业装置可以实现烧烃催化脱氢制烯烃反应的连 续反应再生过程， 降低工业装置能耗、 提高生产效率、 节省人力资源并 且调节灵活。 使用该方法的工业装置原料烷烃的单程转化率与平衡转化 率较接近， 目的产物 （烯烃） 的选择性较高， 实施例中的异丁烷单程转 化率可以达到 40-50%， 异丁錄的选择性可以达到 80-90% (摩尔）， 因此 具有较好的工业实用性。  The two-type industrial device can realize the continuous reaction regeneration process of catalytic hydrogenation of hydrocarbons to olefins, reduce energy consumption of industrial devices, improve production efficiency, save human resources, and adjust flexibility. The single-pass conversion of the raw material alkane using the method is closer to the equilibrium conversion rate, and the selectivity of the target product (olefin) is higher, and the single-pass conversion of isobutane in the embodiment can reach 40-50%. The selectivity can be 80-90% (molar), so it has good industrial applicability.

Claims

权 利 要 求 书 claims
1. 一种烷烃脱氢制烯烃的方法， 其特征在于： 原料烷烃进入脱氢反 应器底部， 与催化剂床层逆流均匀接触并发生脱氢反应， 反应产物在稀 相空间经旋风分离器回收催化剂后离开脱氢反应器， 高温油气降温后进 入后续分离系统； 待生催化剂在脱氢反应器底部进入待生催化剂汽提段, 在待生催化剂汽提段内向待生催化剂中均匀喷入燃料油， 喷油后的待生 催化剂进入待生催化剂提升管， 用主风输送至再生器底部， 在再生器内 顺流完成烧焦、 燃枓油燃烧放热为催化剂提供充足的热量； 再生催化剂 溢流至再生催化剂汽提段， 汽提后的再生催化剂进入脱氢反应器床层上 部； 再生器内的高温烟气经旋风分离器回收催化剂， 然后离开再生器迸 入三级旋风分离器进一步回收催化剂细粉， 离开三级旋风分离器的高温 烟气进入余热锅炉回收热量； 装置自产干气一部分进入辅助燃烧室燃烧 放热为催化剂提供部分热量， 一部分进入原料预热炉燃烧加热原料。 1. A method of dehydrogenating alkanes to produce olefins, which is characterized in that: the raw material alkane enters the bottom of the dehydrogenation reactor, evenly contacts the catalyst bed in countercurrent and undergoes dehydrogenation reaction, and the reaction product is recycled through a cyclone separator in the dilute phase space. After that, it leaves the dehydrogenation reactor, and the high-temperature oil and gas enters the subsequent separation system after cooling down; the to-be-grown catalyst enters the to-be-grown catalyst stripping section at the bottom of the dehydrogenation reactor, and fuel oil is evenly sprayed into the to-be-grown catalyst in the to-be-grown catalyst stripping section. , the regenerated catalyst after fuel injection enters the regenerated catalyst riser, and is transported to the bottom of the regenerator by the main air. It completes coking in the regenerator downstream, and the heat released by the combustion of the fuel oil provides sufficient heat for the catalyst; the regenerated catalyst overflows Flows to the regenerated catalyst stripping section, and the stripped regenerated catalyst enters the upper part of the dehydrogenation reactor bed; the high-temperature flue gas in the regenerator recovers the catalyst through the cyclone separator, and then leaves the regenerator and flows into the three-stage cyclone separator for further recovery. Catalyst fine powder, high-temperature flue gas leaving the three-stage cyclone separator enters the waste heat boiler to recover heat; part of the dry gas produced by the device enters the auxiliary combustion chamber to burn and release heat to provide part of the heat for the catalyst, and part enters the raw material preheating furnace to burn and heat the raw materials.
2. 按照权利要求 1所述的垸烃脱氢制烯烃的方法，其特征在于： 原 料烷烃经过浣烃 -反应油气换热器及原料预热炉预热后进入脱氢反应器 底部。 2. The method for dehydrogenating alkane to produce olefins according to claim 1, characterized in that: the raw material alkane enters the bottom of the dehydrogenation reactor after being preheated by a hydrocarbon-reaction oil and gas heat exchanger and a raw material preheating furnace.
3. 按照权利要求 1所述的垸烃脱氢制烯烃的方法，其特征在于： 脱 氢反应热由床层催化剂提。 3. The method for dehydrogenating alkane to produce olefins according to claim 1, characterized in that: the heat of dehydrogenation reaction is extracted by the bed catalyst.
4. 按照权利要求 1所述的烷烃脱氢制烯烃的方法， 其特征在于： 原 料垸烃进入脱氢反应器底部， 通过垸烃分布器后与催化剂床层逆流均匀 接触。 4. The method of dehydrogenating alkanes to produce olefins according to claim 1, characterized in that: the raw material alkane enters the bottom of the dehydrogenation reactor, passes through the alkane distributor, and contacts the catalyst bed evenly in countercurrent flow.
5- 按照权利要求 1所述的垸烃脱氢制烯烃的方法， 其特征在于： 高 温油气经蒸汽发生器、 垸烃-反应油气换热器降温后进入后续分离系统。 5- The method of dehydrogenating alkenes to produce olefins according to claim 1, characterized in that: the high-temperature oil and gas enter the subsequent separation system after being cooled by the steam generator and the alkane-reaction oil and gas heat exchanger.
6. 按照权利要求 1所述的烧烃脱氢制烯烃的方法， 其特征在于： 在 待生提升管前的待生斜管中喷入燃料油。 6. The method of dehydrogenating paraffin to produce olefins according to claim 1, characterized in that: fuel oil is injected into the inclined tube to be burned in front of the rising tube to be burned.
7. 按照权利要求 1所述的烷烃脱氢制烯烃的方法， 其特征在于： 喷 油后的待生催化剂用辅助燃烧室加热后的主风输送至再生器底部。 7. The method of dehydrogenating alkanes to olefins according to claim 1, characterized in that: the to-be-generated catalyst after fuel injection is transported to the bottom of the regenerator using the main air heated by the auxiliary combustion chamber.
8. 按照权利要求 1所述的垸烃脱氢制烯烃的方法， 其特征在于： 脱 氢反应器为单段逆流等速气泡床层反应器； 反应器密相床层为倒置圆台 形状， 顶部直径大、 底部直径小， 通过床层截面积的步增来实现床层等 线速， 床层底部设有垸经分布器、 顶部设有催化剂分布器， 床层中间设 有多层格栅， 稀相空间设有两级旋风分离器。 8. The method for dehydrogenating paraffins to produce olefins according to claim 1, characterized in that: the dehydrogenation reactor is a single-stage countercurrent constant-velocity bubble bed reactor; the dense-phase bed of the reactor is in the shape of an inverted truncated cone, with the top The diameter is large and the bottom diameter is small. The linear velocity of the bed is achieved by increasing the cross-sectional area of the bed. There is a warp distributor at the bottom of the bed, a catalyst distributor at the top, and a multi-layer grid in the middle of the bed. The dilute phase space is equipped with two-stage cyclone separators.
9. 按照权利要求 1所述的烷经脱氢制烯烃的方法， 其特征在于： 再 生器为单段顺流气泡床再生器； 再生器床层底部设有催化剂分布器， 床 层内设有多层格栅， 稀相空间设有两级旋风分离器。 9. The method of producing olefins through dehydrogenation of alkanes according to claim 1, characterized in that: the regenerator is a single-stage downstream bubble bed regenerator; a catalyst distributor is provided at the bottom of the regenerator bed, and a catalyst distributor is provided in the bed. Multi-layer grid, dilute phase space is equipped with two-stage cyclone separator.
10. 按照权利要求 1所述的垸烃脱氢制烯烃的方法， 其特征在于： 汽提段内设有多层格栅挡扳， 格栅为倾斜对称安装， 单层格栅截面积小 于汽提段横截面积。 10. The method for dehydrogenating alkenes to olefins according to claim 1, characterized in that: the stripping section is provided with a multi-layer grille baffle, the grille is installed obliquely and symmetrically, and the cross-sectional area of the single-layer grille is smaller than that of the steam stripping section. Cross-sectional area of lift section.
11. 按照权利要求 1所述的嫁烃脱氢制烯烃的方法， 其特征在于- 原料被加热到 300- 550 'C , 进入反应器床层底部。 11. The method for producing olefins by dehydrogenating hydrocarbons according to claim 1, characterized in that - the raw material is heated to 300-550°C and enters the bottom of the reactor bed.
12. 按照权利要求 1所述的垸烃脱氢制嫖烃的方法， 其特征在于- 再生催化剂进入反应器床层顶部， 再生剂温度控制在 650-750Ό。 12. The method of dehydrogenating alkane to produce hydrocarbons according to claim 1, characterized in that - the regenerated catalyst enters the top of the reactor bed, and the regenerant temperature is controlled at 650-750°C.
13. 按照权利要求 1 所述的烷经脱氢制稀经的方法， 其特征在于： 反应温度控制在 500~620°C。 13. The method of dehydrogenating alkanes to produce dilute hydrocarbons according to claim 1, characterized in that: the reaction temperature is controlled at 500~620°C.
14. 按照权利要求 1所述的垸烃脱氢制烯烃的方法， 其特征在于： 反应器顶部压力控制在 l-10bar, 14. The method for dehydrogenating alkane to produce olefins according to claim 1, characterized in that: the pressure at the top of the reactor is controlled at 1-10bar,
15. 按照权利要求 1所述的烷烃脱氢制烯烃的方法， 其特征在于： 质量空时控制在 2 - 8h。 15. The method of dehydrogenating alkanes to produce olefins according to claim 1, characterized in that: the mass space time is controlled at 2-8h.
16. 按照权利要求 ί所述的烷经脱氢制烯经的方法， 其特征在于： 离开三级旋风分离器的高温烟气经双动滑阀、 烟气降压孔板降压后进入 余热锅炉回收热量。 16. The method for dehydrogenating alkanes to alkenes according to claim ί, characterized in that: the high-temperature flue gas leaving the three-stage cyclone separator enters after being depressurized by a double-action slide valve and a flue gas depressurization orifice plate. Waste heat boilers recover heat.
17. 按照权利要求 1所述的烷烃脱氢制烯烃的方法，其特征在于： 三 级旋风分离器底部的催化剂细粉进入四级旋风分离器， 四级旋风分离器 底部的催化剂细粉进入三级旋风分离器回收催化剂储罐间断外运处理。 17. The method for dehydrogenating alkanes to olefins according to claim 1, characterized in that: the fine catalyst powder at the bottom of the three-stage cyclone separator enters the fourth-stage cyclone separator, and the fine catalyst powder at the bottom of the four-stage cyclone separator enters the third-stage cyclone separator. The first-stage cyclone separator recovers the catalyst storage tank for intermittent outsourcing processing.
18. 按照权利要求 17所述的烷烃脱氢制烯经的方法， 其特征在于： 四级旋风分离器顶部的烟气经临界流速喷嘴降压后并入烟气降压孔板后 的烟气管线。 18. The method for dehydrogenating alkanes to alkenes according to claim 17, characterized in that: the flue gas at the top of the four-stage cyclone separator is depressurized by the critical flow rate nozzle and then merged into the flue gas after the depressurization orifice plate. pipeline.
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CN103449948B (en) 2015-02-25

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