WO2017202040A1 - 一种甲醇制丙烯的反应再生系统和方法 - Google Patents

一种甲醇制丙烯的反应再生系统和方法 Download PDF

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WO2017202040A1
WO2017202040A1 PCT/CN2017/070686 CN2017070686W WO2017202040A1 WO 2017202040 A1 WO2017202040 A1 WO 2017202040A1 CN 2017070686 W CN2017070686 W CN 2017070686W WO 2017202040 A1 WO2017202040 A1 WO 2017202040A1
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reaction
methanol
regeneration
reactor
switching valve
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PCT/CN2017/070686
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English (en)
French (fr)
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黄寻
肖文德
李学刚
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上海交通大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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

  • the present invention relates to a propylene production system and method, and more particularly to a reaction regeneration system and method for producing propylene from methanol.
  • Propylene is an important chemical raw material. With the development of industrial economy in various countries, its demand is increasing. At present, the main production method of propylene is the naphtha cracking process. However, global oil reserves are limited, and the distribution is uneven, and the price fluctuates greatly. Therefore, the development of non-oil route propylene production process is of great strategic significance to China, which is rich in oil and rich in coal.
  • German Patent DE 4009459 (1990) discloses a two-step process for the production of propylene from methanol using a ZSM-5 molecular sieve catalyst, the first step using an adiabatic fixed bed reactor, the catalyst being activated alumina, and the second step using a column tube.
  • the formula (heat exchange type) fixed bed reactor, the heat exchange medium is a high temperature molten salt.
  • WO2004018089 issued by the German company Lurgi, disclose a methanol-to-propylene reactor having a multi-stage adiabatic fixed bed structure in which the reaction feedstock is divided into multiple feeds, ie the first stage reactant outlet of the reactor. After mixing with the fresh raw material of the second section, the second section is entered, and the second section of the outlet material is mixed with the third section of the raw material and then enters the third section, and so on.
  • the patent WO200704124 of the Lurgi company discloses a method for producing propylene from methanol, which separates the reaction product into carbon two, carbon three, carbon four + carbon five, carbon five or more, aromatic hydrocarbons and water products, and carbon four + carbon.
  • Lurgi's Chinese patent CN200780020432 discloses a method for operating a multi-stage adiabatic fixed bed reactor, which uses water-saturated dimethyl ether and methanol vapor, and a liquid spray of methanol, dimethyl ether and water to enter the material distribution between the segments.
  • a nozzle that adjusts the injection ratio of the vapor and liquid to adjust the inlet temperature of the downstream bed.
  • the process of converting methanol into olefins has a large heat release, in order to ensure that the methanol conversion rate is not too low and the reaction temperature rise is not too high, the methanol inlet concentration of each stage is only 5-8 wt%.
  • a low methanol concentration reduces the methanol conversion rate, and an excessive number of reaction stages increases the residence time of the olefin, thereby increasing the formation of by-products such as alkanes and aromatics. Therefore, increasing the inlet concentration of methanol and reducing the number of reaction stages can effectively reduce the formation of by-products and increase the yield of propylene.
  • the invention relates to a reaction regeneration system of methanol to propylene, and as a regeneration system of a reaction system and a catalyst for catalyzing the production of propylene by methanol, the system comprises a reactor, a heating furnace, a heat exchanger, an inlet logistics switching valve, an outlet logistics switching valve and a separation unit.
  • the reactor inlet is sequentially connected with a heating furnace, a heat exchange passage of the heat exchanger and an inlet flow switching valve to form a raw material passage
  • the outlet of the reactor is sequentially connected with another heat exchange passage and an outlet flow of the heat exchanger.
  • the switching valve and the separation unit are connected to form a product passage;
  • the reactor is an adiabatic fixed bed reactor, the reactor is built with HZSM-5 high silica molecular sieve catalyst, the high silicon molecular sieve silicon / aluminum atomic ratio of 30 ⁇ 300;
  • the inlet flow switching valve has two inlet flow channels, one of which takes the reaction feed and the other takes the regeneration gas; the inlet flow switching valve can be a three-way valve that switches between the two inlet streams, or There are two shut-off valves with separate control opening and closing.
  • the outlet stream switching valve has two outlet stream passages, one of which takes the reaction product and the other takes the regeneration tail gas.
  • the outlet stream switching valve may be a three-way valve that switches between two outlet streams, or two two-way valves that are separately controlled to open and close.
  • the separation unit is a pressurization method for separating a reaction product from a gas containing mainly C1 to C4 alkanes, ethylene, propylene, water, a gasoline fraction mainly containing C5 or more alkanes and aromatic hydrocarbons, and a C4 to C7 high carbon olefin fraction.
  • atmospheric distillation towers are used for separating a reaction product from a gas containing mainly C1 to C4 alkanes, ethylene, propylene, water, a gasoline fraction mainly containing C5 or more alkanes and aromatic hydrocarbons, and a C4 to C7 high carbon olefin fraction.
  • atmospheric distillation towers are examples of the separation unit.
  • the methanol feedstock is mixed with the C4-C7 high-carbon olefin fraction as a reaction feed, and the reaction feed enters an inlet of the inlet stream switching valve, and then enters a heat exchange passage of the heat exchanger, and is heated.
  • the other heat exchange passage of the furnace, the reactor and the heat exchanger is further discharged through an outlet of the outlet stream switching valve to form a reaction product, and the reaction product enters the product separation unit;
  • the regeneration gas enters another inlet of the inlet stream switching valve, and then enters one heat exchange passage of the heat exchanger, the heating furnace, the other heat exchange passage of the reactor and the heat exchanger, and the other of the outlet flow switching valve
  • An outlet effluent forms a regenerative tail gas that enters the chimney.
  • the inlet flow switching valve further comprises an automatic control mechanism for controlling two inlet flow channels and opening and closing, the control mechanism being a pneumatic, electric or hydraulic component;
  • the outlet flow switching valve also includes an automatic control mechanism that controls the two outlet flow passages and opens and closes, the control mechanism being also a pneumatic, electric or hydraulic component.
  • the reactor is a separate adiabatic fixed bed reactor or a section of a multi-stage parallel insulated fixed bed reactor.
  • a reaction regeneration method for methanol-based propylene based on the above system which realizes periodic conversion of methanol catalytic dehydration to propylene reaction and catalyst regeneration process by periodic switching of reaction gas and regeneration gas, and the reaction regeneration method is specifically Includes the following steps:
  • the methanol feedstock is mixed with the C4-C7 high-carbon olefin fraction to form a reaction feed, the reaction feed enters an inlet of the inlet stream switching valve, and then enters a heat exchange passage of the heat exchanger to heat up, and after passing through the heating furnace, the reaction
  • the inlet of the vessel enters the reactor, and the reaction of catalytic dehydration to olefin is carried out in the reactor while the temperature is raised;
  • the product flows from the outlet of the reactor through another heat exchange channel of the heat exchanger to recover the heat of reaction, and then flows out through an outlet of the outlet stream switching valve to form a reaction product, and the reaction product enters the product separation unit for separation, and the main product is obtained.
  • the C4 to C7 high carbon olefin fraction is recycled, and is combined with a methanol feedstock as a reaction feed of the reactor to increase the selectivity of propylene or ethylene;
  • the HZSM-5 molecular sieve catalyst in the reactor is deactivated, and the conversion efficiency is gradually reduced until the methanol outlet conversion rate is reduced from an initial greater than 99% to less than 90 to 95%.
  • the inlet stream switching valve closes the inlet of the reaction feed, and at the same time opens the inlet of the regeneration gas, the outlet stream switching valve closes the outlet of the reaction product, and simultaneously opens the outlet of the regeneration tail gas, the dehydration reaction process is suspended, and the catalyst regeneration process is enabled;
  • the regeneration gas enters from the regeneration gas inlet of the inlet logistics switching valve, and then enters a heat exchange channel of the heat exchanger to heat up and heat up, then enters the heating furnace to further heat up, and then enters the reactor to perform the deactivated HZSM-5 molecular sieve catalyst.
  • the other heat exchange channel entering the heat exchanger cools and recovers heat, and then the exhaust gas outlet of the outlet flow switching valve is discharged into the chimney for emptying;
  • the inlet stream switching valve closes the inlet of the regeneration gas, and simultaneously opens the inlet of the reaction feed.
  • the outlet stream switching valve closes the outlet of the regeneration tail gas, and simultaneously opens the outlet of the reaction product, the catalyst regeneration process is suspended, and the dehydration reaction process is activated;
  • the methanol catalytic dehydration to propylene reaction process time is 50 to 500 hours, preferably 100 to 400 hours, more preferably 200 to 300 hours;
  • the catalyst regeneration process has a time of from 5 to 50 hours, preferably from 10 to 40 hours, more preferably from 20 to 30 hours.
  • the methanol raw material comprises methanol, dimethyl ether and water, wherein the mass fraction of methanol or dimethyl ether is 10 to 50%, and the mass fraction of water is 10 to 50%; the methanol raw material and the The mass ratio of the high carbon olefin fraction of C4 to C7 is from 10:1 to 1:1, preferably from 6:1 to 2:1, more preferably from 4:1 to 3:1.
  • the regeneration gas includes 1 to 10% by mass of oxygen, preferably 2.0 to 5.0%, and the diluted component is nitrogen, carbon dioxide or water vapor.
  • the inlet temperature of the reactor under the reaction state of methanol to propylene is 350-450 ° C, and the inlet temperature of the reactor in the state of catalyst regeneration is 450-650 ° C;
  • the temperature of the raw material stream before entering the heat exchanger is 50-150 ° C, and the temperature of the raw material stream coming out of the heat exchanger is 250-400 ° C;
  • the reactor inlet has an absolute pressure of 0.15-1.0 MPa.
  • the catalyst is a HZSM-5 type molecular sieve particle
  • the molecular sieve particle is spherical, cylindrical or circular column type, and has a diameter of 3-5 mm.
  • the single-pass life of the catalyst is generally 1-25 days.
  • the system can switch the catalyst regeneration, and the regeneration frequency can be replaced after 5-50 times. catalyst.
  • the present invention utilizes a single-stage adiabatic fixed bed reactor to produce olefins from methanol.
  • the present invention has the following advantages: (1) The reactor has only one stage, which greatly reduces the olefin in the reactor (especially The contact time of the recycled olefin with the catalyst, thereby largely avoiding the occurrence of hydrogen transfer reaction and reducing the formation of by-products; (2) the premise of ensuring that the temperature rise of the reactor is not excessive (generally less than 100 ° C) By increasing the methanol inlet concentration, the reactor space velocity can be increased and the amount of catalyst can be reduced.
  • FIG. 1 is a schematic view showing the structure of a reaction regeneration system for producing propylene from methanol according to a first embodiment of the present invention
  • FIG. 2 is a schematic view showing the structure of a reaction regeneration system for producing propylene from methanol according to a second embodiment of the present invention.
  • a reaction regeneration system for methanol to propylene and a regeneration system for a reaction system and a catalyst for catalyzing the production of propylene, the system includes a reactor 100, a heating furnace 200, a heat exchanger 300, and an inlet stream switching.
  • the valve 410, the outlet stream switching valve 420 and the separation unit 500, the inlet of the reactor 100 is sequentially connected with the heating furnace 200, one of the heat exchanger channels 300 and the inlet stream switching valve 410 to form a raw material passage, and the outlet of the reactor 100 is sequentially
  • the other heat exchange channel of the heat exchanger 300, the outlet stream switching valve 420 and the separation unit 500 are connected to form a product channel;
  • the reactor 100 is an adiabatic fixed bed reactor, and the reactor 100 is equipped with a HZSM-5 high silicon molecular sieve catalyst;
  • the valve 410 has two inlet flow passages, one of which takes the reaction feed 11 and the other with the regeneration gas 20;
  • the inlet flow switching valve 410 is a three-way valve that switches between the two inlet streams.
  • the outlet stream switching valve 420 has two outlet stream passages, one of which takes the reaction product 17 and the other proceeds from the regeneration tail gas 30.
  • the outlet stream switching valve 420 is a three-way valve that switches between two
  • the separation unit 500 is a high carbon olefin fraction in which the reaction product is separated into a gas 40 containing mainly C1 to C4 alkanes, ethylene 50, propylene 60, water 70, gasoline fraction 80 and C4 to C7 mainly containing C5 or more alkanes and aromatics.
  • a pressurized and atmospheric distillation column set of 90 is a high carbon olefin fraction in which the reaction product is separated into a gas 40 containing mainly C1 to C4 alkanes, ethylene 50, propylene 60, water 70, gasoline fraction 80 and C4 to C7 mainly containing C5 or more alkanes and aromatics.
  • the methanol feedstock 10 is mixed with the C4 to C7 high carbon olefin fraction 90 as the reaction feed 11, the reaction feed 11 enters an inlet of the inlet stream switching valve 410, and then enters a heat exchange passage of the heat exchanger 300 in turn.
  • the regeneration gas 20 enters another inlet of the inlet stream switching valve 410, and then enters a heat exchange passage of the heat exchanger 300, the heating furnace 200, the reactor 100 and another heat exchange passage of the heat exchanger 300, and then passes through
  • the other outlet of the mouth stream switching valve 420 flows out to form a regenerative tail gas 30, and the regeneration tail gas 30 enters the chimney.
  • the inlet logistics switching valve 410 further includes an automatic control mechanism for controlling the opening and closing of the two inlet flow passages 11 and 20, the control mechanism being a pneumatic, electric or hydraulic component; the outlet logistics switching valve 420 also includes controlling two outlet logistics passages 17 And 30 automatic control mechanism for opening and closing, the control mechanism is also pneumatic, electric or hydraulic components.
  • reactor 100 is a separate adiabatic fixed bed reactor or a section of a multi-stage parallel insulated fixed bed reactor.
  • a reaction regeneration method for methanol-based propylene based on the above system which realizes periodic conversion of methanol catalytic dehydration to propylene reaction and catalyst regeneration process by periodic switching of reaction gas and regeneration gas.
  • the regeneration method specifically includes the following steps:
  • the methanol feedstock 10 is mixed with the C4 to C7 high carbon olefin fraction 90 to form a reaction feed 11, and the reaction feed 11 enters an inlet of the inlet stream switching valve 410, and then enters a heat exchange passage of the heat exchanger 300 to be heated and heated.
  • the furnace 200 is then introduced into the reactor 100 from the inlet of the reactor 100, and the reaction of catalytic dehydration to olefins is carried out in the reactor 100 while the temperature is raised;
  • the product flows from the outlet of the reactor 100 through the other heat exchange channel of the heat exchanger 300 to recover the heat of reaction, and then flows out through an outlet of the outlet stream switching valve 420 to form a reaction product 17, and the reaction product 17 enters the product separation unit 500 for separation.
  • a gas fraction 40 mainly containing a C1-C4 alkane, ethylene 50, propylene 60, water 70, a gasoline fraction 80 containing a C5 or higher alkane and an aromatic hydrocarbon, and a high carbon olefin fraction 90 of C4 to C7;
  • the high carbon olefin fraction 90 of C4 to C7 is recycled, and is combined with the methanol raw material 10 as a reaction feed of the reactor 100 to increase the selectivity of propylene 60 or ethylene 50;
  • the HZSM-5 molecular sieve catalyst in the reactor 100 is deactivated, and the conversion efficiency is gradually reduced until the methanol outlet conversion rate is reduced from the initial 99% to less than 90-95%, and the import logistics is switched.
  • the valve 410 closes the inlet of the reaction feed 11 while opening the inlet of the regeneration gas 20, the outlet stream switching valve 420 closes the outlet of the reaction product 17, and simultaneously opens the outlet of the regeneration tail gas 30, the dehydration reaction process is suspended, and the catalyst regeneration process is enabled;
  • the regeneration gas 20 enters from the regeneration gas inlet of the inlet stream switching valve 410, and sequentially enters a heat exchange channel of the heat exchanger 300 to heat up and heat up, and then enters the heating furnace 200 to further heat up, and then enters the reactor 100,
  • the deactivated HZSM-5 molecular sieve catalyst is subjected to charring regeneration, and after the regeneration tail gas leaves the reactor 100, after entering the other heat exchange passage of the heat exchanger 300 to recover heat, the regeneration tail gas outlet of the outlet stream switching valve 420 is discharged into the chimney. Emptying
  • the inlet stream switching valve 410 closes the inlet of the regeneration gas 20, and simultaneously opens the inlet of the reaction feed 11 and switches the outlet stream.
  • the valve 420 closes the outlet of the regeneration tail gas 30 while opening the outlet of the reaction product 17, the catalyst regeneration process is suspended, and the dehydration reaction process is enabled;
  • reaction time of the methanol-catalyzed dehydration to propylene is 50 to 500 hours, preferably 100 to 400 hours, more preferably 200 to 300 hours; and the catalyst regeneration time is 5 to 50 hours, preferably 10 to 40 hours. More preferably, it is 20-30 hours.
  • the methanol raw material 10 comprises methanol, dimethyl ether and water, wherein the mass fraction of methanol or dimethyl ether is 10 to 50%, the mass fraction of water is 10 to 50%; the high content of methanol raw material 10 and C4 to C7
  • the mass ratio of the olefin fraction 90 is from 10:1 to 1:1, preferably from 6:1 to 2:1, more preferably from 4:1 to 3:1.
  • the flow rate of methanol starting material 10 to methanol is 1.0 to 10.0 kg of methanol per kg of catalyst per hour, preferably 2.0 to 5.0.
  • the regeneration gas 20 includes oxygen in a mass fraction of 1 to 10%, preferably 2.0 to 5.0%, and the diluted component is nitrogen, carbon dioxide or water vapor.
  • the inlet temperature of the reactor in the reaction state of methanol to propylene is 350-450 ° C, and the inlet temperature of the reactor in the state of catalyst regeneration is 450-650 ° C;
  • the temperature of the raw material stream before entering the heat exchanger is 50-150 ° C, and the temperature of the raw material stream coming out of the heat exchanger is 250-400 ° C;
  • the absolute inlet pressure of the reactor is 0.15-1.0 MPa.
  • the catalyst is HZSM-5 type molecular sieve particles, and the molecular sieve particles are spherical, cylindrical or circular column type, and the diameter is 3-5 mm.
  • the single-pass life of the catalyst is generally 1-25 days.
  • the system can switch the catalyst regeneration. After the regeneration times reach 5-50 times, the fresh catalyst can be replaced.
  • FIG. 2 is another embodiment of the present invention. Different from FIG. 1, the inlet switching valve 410 and the outlet cut are The valve 420 is composed of two valves that can be opened and closed separately, and can be a butterfly valve, a shut-off valve, or other valve having a switching function.
  • a methanol-to-propylene reaction regeneration device includes an inlet stream switching valve 410, a column-tube heat exchanger 300, a heating furnace 200, and a single-stage fixed-bed reactor 100.
  • the reactor 100 was charged with 50 tons of catalyst, and the catalyst was HZSM-5 type molecular sieve particles having a Si/Al ratio of 200. 10 methanol feed flow rate of 200 tons / hour; the recycle stream a mixture of water and hydrocarbons, water flow 252 t / h, C 2 and C 4 -C 6 hydrocarbon 775 tons / hr. After heating by heat exchange and heating, the temperature of the reactant stream 14 was 400 °C.
  • the temperature of the reaction stream 15 was 480 ° C, and the methanol conversion was 99%.
  • the yield of propylene 60 was 76.6 tons/hour, which corresponds to a propylene selectivity of 87.54%, a fuel gas and a liquefied gas of 3 tons/hour, and a mixed aromatic hydrocarbon of 4.5 tons/hour.
  • the methanol conversion rate drops to 95%.
  • the inlet and outlet of the inlet stream switching valve 410 and the outlet stream switching valve 420 are switched, so that the inlet stream of the apparatus is the regeneration gas 20, and the outlet stream is the regeneration tail gas 30.
  • a methanol-to-propylene reaction regeneration device includes an inlet stream switching valve 410, a column-tube heat exchanger 300, a heating furnace 200, and a single-stage fixed-bed reactor 100.
  • the reactor 100 was charged with 50 tons of catalyst, and the catalyst was a ZSM-5 type high silicon molecular sieve particle, and the silicon to aluminum ratio was the same as in Example 1.
  • the temperature of the reactant stream 14 was 400 °C.
  • the temperature of the reactant stream 15 was 480 ° C, and the methanol conversion was 99.9%.
  • the propylene production was 35.6 tons/hour, which corresponds to a propylene selectivity of 81.37%, a fuel gas and a liquefied gas of 3.5 tons/hour, and a mixed aromatics of 5.3 tons/hour.
  • the methanol conversion rate was reduced to 95%.
  • the inlet and outlet of the inlet stream switching valve 410 and the outlet stream switching valve 420 were switched, so that the inlet stream of the apparatus was the regeneration gas 20, and the outlet stream was the regeneration tail gas 30.
  • the export counter was measured.
  • the concentration of carbon dioxide in stream 15 should be less than 80 ppm, and regeneration can be considered complete, and the reactor enters the next cycle.
  • a methanol-to-propylene reaction regeneration device includes an inlet stream switching valve 410, a column-tube heat exchanger 300, a heating furnace 200, and a single-stage fixed-bed reactor 100.
  • the reactor 100 was charged with 50 tons of catalyst, and the catalyst was a ZSM-5 type high silicon molecular sieve particle, and the silicon to aluminum ratio was the same as in Example 1.
  • the temperature of the reactant stream 14 was 400 °C.
  • the temperature of the reaction stream 15 was 480 ° C, and the methanol conversion was 97%.
  • the propylene yield was 161 tons/hour, which corresponds to a propylene selectivity of 92.0%, a fuel gas and a liquefied gas of 5.5 tons/hour, and a mixed aromatics of 8.5 tons/hour.
  • the methanol conversion rate is reduced to 90%.
  • the inlet and outlet of the inlet stream switching valve 410 and the outlet stream switching valve 420 are switched, so that the inlet stream of the apparatus is the regeneration gas 20, and the outlet stream is the regeneration tail gas 30.
  • the concentration of carbon dioxide in the outlet reactant stream 15 was measured to be less than 15 ppm, and regeneration was considered complete, and the reactor was advanced to the next cycle.
  • reactor 100 is a fixed bed reactor comprising five separate beds, the beds are completely isolated, a distributor is installed above the bed, and a gas outlet is provided below the bed.
  • Each bed was filled with 10 tons of catalyst, and the catalyst was HZSM-5 type high silicon molecular sieve particles, and the silicon to aluminum ratio was the same as in Example 1.
  • the temperature of the reactant stream 14 was 400 ° C, and the average split into 5 strands of streams respectively entered the 5-stage bed.
  • the temperature of the reaction stream 15 was 480 ° C, and the methanol conversion was 99%.
  • the propylene production was 80 tons/hour, which corresponds to a propylene selectivity of 91.43%, a fuel gas and a liquefied gas of 3 tons/hour, and a mixed aromatic hydrocarbon of 4.5 tons/hour.
  • the methanol conversion rate drops to 95%.
  • the inlet and outlet of the inlet stream switching valve 410 and the outlet stream switching valve 420 are switched, so that the inlet stream of the apparatus is the regeneration gas 20, and the outlet stream is the regeneration tail gas 30.
  • the average divided into 5 streams respectively enters the 5-stage bed for regeneration.
  • the concentration of carbon dioxide in the outlet reactant stream 15 was measured to be less than 80 ppm, and regeneration was considered complete, and the reactor was advanced to the next cycle.
  • a methanol-to-propylene reaction regeneration device includes an inlet stream switching valve 410, a column-tube heat exchanger 300, a heating furnace 200, and a single-stage fixed-bed reactor 100.
  • the reactor 100 was charged with 50 tons of catalyst, and the catalyst was HZSM-5 type high silica molecular sieve particles, and the silicon to aluminum ratio was the same as in Example 1.
  • the temperature of the reactant stream 14 was 350 °C.
  • the temperature of the reaction stream 15 was 480 ° C, and the methanol conversion was 99%.
  • the propylene production was 155 tons/hour, the fuel gas and liquefied gas were 7 tons/hour, and the mixed aromatics were 13 tons/hour.
  • the methanol conversion rate drops to 95%.
  • the inlet and outlet of the inlet stream switching valve 410 and the outlet stream switching valve 420 are switched, so that the device inlet stream is the regeneration gas 20 and the outlet stream is the regeneration tail gas 30.
  • the concentration of carbon dioxide in the outlet reactant stream 15 was measured to be less than 50 ppm, and regeneration was considered complete, and the reactor was advanced to the next cycle.
  • a methanol-to-propylene reaction regeneration device includes a set of inlet flow switching valve 410 composed of two shut-off valves, a tubular heat exchanger 300, a heating furnace 200, and a unit.
  • the reactor 100 was charged with 50 tons of catalyst, and the catalyst was HZSM-5 type high silica molecular sieve particles, and the silicon to aluminum ratio was the same as in Example 1.
  • the valves corresponding to the reaction feed 11 and the reaction product 17 are first opened, and the valves corresponding to the regeneration gas 20 and the regeneration tail gas 30 are closed.
  • the methanol conversion rate drops to 95%.
  • the valves corresponding to the reaction feed 11 and the reaction product 17 are closed, and the valves corresponding to the regeneration gas 20 and the regeneration tail gas 30 are opened, so that the inlet stream of the device is the regeneration gas.
  • the export logistics is regenerative exhaust gas 30.

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Abstract

本发明涉及一种甲醇制丙烯的反应再生系统与方法，该系统包括反应器、加热炉、换热器、进口物流切换阀、出口物流切换阀及分离单元，通过控制进出口物流切换阀来实现反应、再生状态间的周期性切换；反应器内装填催化剂，反应过程中，反应物料经原料通道进入反应器，在反应器内反应后，经产物通道以产物形式排出；再生过程中，再生气经原料通道进入反应器，在反应器内对催化剂再生，再生尾气经产物通道从出口物流切换阀排出。与现有技术相比，本发明利用单段绝热固定床反应器由甲醇制备丙烯，减少了副产物的生成，具有极高的丙烯选择性；同时可以提高反应器空速，减少催化剂的用量。

Description

一种甲醇制丙烯的反应再生系统和方法 技术领域
本发明涉及一种丙烯生产系统与方法，尤其是涉及一种甲醇制丙烯的反应再生系统和方法。
背景技术
丙烯是一种重要的化工基础原料，随着各国工业经济的发展，其需求量越来越大。目前，丙烯的主要生产方法是石脑油裂解工艺。然而全球石油储量有限，且分布不均，价格波动较大，因此发展非石油路线的丙烯生产工艺，对贫油富煤的中国来说，具有非常重要的战略意义。
甲醇催化脱水制丙烯技术是一种最有竞争力的以煤为原料的丙烯生产方法。德国专利DE4009459(1990)公开了一种两步法由甲醇制丙烯的方法，采用ZSM-5分子筛催化剂，第一步采用绝热式固定床反应器，催化剂为活性氧化铝，第二步采用列管式(换热式)固定床反应器，换热介质为高温熔盐。德国Lurgi公司发表的德国专利DE10233975和世界专利WO2004018089公开了一种甲醇制丙烯的反应器，具有多段绝热固定床的结构，反应原料分为多股进料，即反应器的第一段反应物出口与第二段的新鲜原料混合后进入第二段，第二段的出口物料与第三段的原料混合后进入第三段，依次类推。另外，Lurgi公司的专利WO200704124公开了一种甲醇制丙烯的方法，将反应产物分离为碳二，碳三，碳四+碳五，碳五以上，芳烃和水几股产物，并且碳四+碳五产物流循环返回到反应器进口，以增加丙烯收率。Lurgi公司的中国专利CN200780020432公开了一种操作调节其多段绝热固定床反应器的方法，采用水饱和的二甲醚和甲醇蒸汽，以及甲醇、二甲醚和水的液体喷雾进入段间的物料分布喷嘴，调节所述蒸汽和液体的喷射比例，以便调节下游床层的进口温度。
由于甲醇转化成烯烃的过程放热量较大，为保证甲醇转化率不至于太低和反应温升不至于太高，每一级的甲醇进口浓度只有5-8wt％。然而，如此低的甲醇浓度降低了甲醇转化速率，且过多的反应级数增加了烯烃的停留时间，从而增加了烷烃和芳烃等副产物的生成。因此，提高甲醇的进口浓度，减少反应级数，可以有效降低副产物的生成并提高丙烯的产率。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种高丙烯选择性的甲醇制丙烯的反应再生系统与方法。
本发明的目的可以通过以下技术方案来实现：
一种甲醇制丙烯的反应再生系统，同时作为甲醇催化制丙烯的反应系统与催化剂的再生系统，该系统包括反应器、加热炉、换热器、进口物流切换阀、出口物流切换阀及分离单元，所述的反应器入口依次与加热炉、换热器其中一个换热通道和进口物流切换阀连通构成原料通道，所述的反应器的出口依次与换热器另一个换热通道、出口物流切换阀及分离单元连通构成产物通道；
所述的反应器为绝热固定床反应器，所述反应器内置有HZSM-5高硅分子筛催化剂，所述高硅分子筛的硅/铝原子比30～300；
所述进口物流切换阀有两个进口物流通道，其中一个走反应进料，另一个走再生气；所述的进口物流切换阀可以是一个在两股进口物流间切换的三通阀，也可以是两个分别设有单独控制启闭的截止阀。
所述出口物流切换阀有两个出口物流通道，其中一个走反应产物另一个走再生尾气。所述的出口物流切换阀可以是一个在两股出口物流间切换的三通阀，也可以是两个分别设有单独控制启闭的截止阀。
进一步地，所述分离单元为将反应产物分离出主要含C1～C4烷烃的燃气、乙烯、丙烯、水、主要含C5以上烷烃和芳烃的汽油馏分和C4～C7的高碳烯烃馏分的加压和常压精馏塔组。
进一步地，甲醇原料与所述C4～C7的高碳烯烃馏分混合后作为反应进料，所述反应进料进入进口物流切换阀的一个进口，再依次进入换热器的一个换热通道，加热炉，反应器和换热器的另一个换热通道，再经出口物流切换阀的一个出口流出形成反应产物，所述反应产物进入产物分离单元；
所述再生气进入进口物流切换阀的另一个进口，再依次进入换热器的一个换热通道，加热炉，反应器和换热器的另一个换热通道，再经出口物流切换阀的另一个出口流出形成再生尾气，所述再生尾气进入烟囱。
进一步地，所述进口物流切换阀还包括控制两个进口物流通道和启闭的自动控制机构，所述控制机构是气动、电动或油压元件；
所述出口物流切换阀也包括控制两个出口物流通道和启闭的自动控制机构，所述控制机构也是气动、电动或油压元件。
进一步地，所述的反应器为一独立的绝热固定床反应器或多段平行绝热固定床反应器中的一段。
一种基于上述系统进行甲醇制丙烯的反应再生方法，该方法通过反应气和再生气的周期性切换，实现甲醇催化脱水制丙烯反应和催化剂再生过程的周期性转换，所述的反应再生方法具体包括以下步骤：
A、甲醇催化脱水制丙烯反应过程：
甲醇原料与C4～C7的高碳烯烃馏分混合后形成反应进料，所述反应进料进入进口物流切换阀的一个进口，再进入换热器的一个换热通道升温，经过加热炉后从反应器入口进入反应器内，在反应器内进行催化脱水制烯烃的反应，同时温度升高；
反应后产物从反应器出口流经换热器另一个换热通道降温回收反应热，然后经出口物流切换阀的一个出口流出形成反应产物，所述反应产物进入产物分离单元进行分离，得到主要含C1～C4烷烃的燃气、乙烯、丙烯、水、主要含C5以上烷烃和芳烃的汽油馏分和C4～C7的高碳烯烃馏分；
所述C4～C7的高碳烯烃馏分循环利用，与甲醇原料合流作为反应器的反应进料，提高丙烯或乙烯的选择性；
随着催化脱水反应的进行，所述反应器中的HZSM-5分子筛催化剂结焦失活，转化效率逐渐降低，直到甲醇的出口转化率由初期的大于99％降低到小于90～95％，所述进口物流切换阀关闭反应进料的进口，同时开启再生气的进口，所述出口物流切换阀关闭反应产物的出口，同时开启再生尾气的出口，脱水反应过程暂停，催化剂再生过程启用；
B、催化剂再生过程：
再生气从进口物流切换阀的再生气进口进入，依次进入换热器的一个换热通道换热升温后，再进入加热炉进一步升温，再进入反应器，对失活的HZSM-5分子筛催化剂进行烧焦再生，再生尾气离开反应器后，进入换热器的另一个换热通道降温回收热量后，从出口物流切换阀的再生尾气出口排入烟囱排空；
所述再生过程中，再生尾气中CO2或CO含量不断降低，直到含量稳定或低于10～100ppmv时，所述进口物流切换阀关闭再生气的进口，同时开启反应进料的进口，所述出口物流切换阀关闭再生尾气的出口，同时开启反应产物的出口，催化剂 再生过程暂停，脱水反应过程启用；
重复上述A、B两个过程，实现所述甲醇催化脱水制丙烯反应过程和所述催化剂再生过程的周期性循环转换，从而实现甲醇制丙烯的生产连续化。
进一步地，所述甲醇催化脱水制丙烯反应过程的时间为50～500小时，优选为100～400小时，更优选为200～300小时；
所述催化剂再生过程的时间为5～50小时，优选为10～40小时，更优选为20～30小时。
进一步地，所述的甲醇原料中包含甲醇、二甲醚和水，其中甲醇或二甲醚的质量分数为10～50％，水的质量分数为10～50％；所述甲醇原料和所述C4～C7的高碳烯烃馏分的质量比为10:1～1:1，优选为6:1～2:1，更优选为4:1～3:1。
进一步地，所述甲醇原料折合为甲醇(1公斤二甲醚相当于64/46＝1.3913公斤甲醇)的流量为1.0～10.0公斤甲醇/公斤催化剂/小时，优选为2.0～5.0。
进一步地，所述再生气中包括质量分数1～10％的氧气，优选为2.0～5.0％，其稀释组分为氮气、二氧化碳或水蒸气等。
进一步地，甲醇制丙烯反应状态下反应器的进口温度为350-450℃，催化剂再生状态下反应器的进口温度为450-650℃；
进一步地，进入换热器前原料物流的温度为50-150℃，从换热器出来的原料物流的温度为250-400℃；
进一步地，所述的反应器进口绝对压力为0.15-1.0MPa。
进一步地，所述的催化剂为HZSM-5型分子筛颗粒，所述分子筛颗粒为球形、圆柱型或圆环柱型，直径3-5mm。
进一步地，所述的催化剂的单程寿命一般为1-25天，当甲醇转化率低于90-95％时，系统即可切换进行催化剂再生，再生次数达到5-50次后，即可更换新鲜催化剂。
本发明利用单段绝热固定床反应器由甲醇制备烯烃，与多段固定床反应器相比，本发明具有以下优点：(1)反应器只有1段，极大地降低了反应器中烯烃(特别是循环烯烃)与催化剂的接触时间，从而很大程度上避免了氢转移反应的发生，减少了副产物的生成；(2)在保证反应器温升不至于过大(一般小于100℃)的前提下，通过增加甲醇进口浓度，可以提高反应器空速，减少催化剂的用量。
附图说明
图1为本发明第一种实施方式中甲醇制丙烯的反应再生系统结构示意图；
图2为本发明第二种实施方式中甲醇制丙烯的反应再生系统结构示意图。
图中标号：100.反应器；200.加热炉；300.换热器；410.进口物流切换阀；420.出口物流切换阀；500.分离单元；10.甲醇原料；11.反应进料；12-16.反应物流；17.反应产物；20.再生气；30.再生尾气；40.燃气；50.乙烯；60.丙烯；70.水；80.汽油馏分；90.高碳烯烃馏分。
具体实施方式
如图1所示，一种甲醇制丙烯的反应再生系统，同时作为甲醇催化制丙烯的反应系统与催化剂的再生系统，该系统包括反应器100、加热炉200、换热器300、进口物流切换阀410、出口物流切换阀420及分离单元500，反应器100入口依次与加热炉200、换热器300其中一个换热通道和进口物流切换阀410连通构成原料通道，反应器100的出口依次与换热器300另一个换热通道、出口物流切换阀420及分离单元500连通构成产物通道；反应器100为绝热固定床反应器，反应器100内置有HZSM-5高硅分子筛催化剂；进口物流切换阀410有两个进口物流通道，其中一个走反应进料11，另一个走再生气20；进口物流切换阀410是一个在两股进口物流间切换的三通阀。出口物流切换阀420有两个出口物流通道，其中一个走反应产物17另一个走再生尾气30。出口物流切换阀420是一个在两股出口物流间切换的三通阀。
其中，分离单元500为将反应产物分离出主要含C1～C4烷烃的燃气40、乙烯50、丙烯60、水70、主要含C5以上烷烃和芳烃的汽油馏分80和C4～C7的高碳烯烃馏分90的加压和常压精馏塔组。
其中，甲醇原料10与C4～C7的高碳烯烃馏分90混合后作为反应进料11，反应进料11进入进口物流切换阀410的一个进口，再依次进入换热器300的一个换热通道，加热炉200，反应器100和换热器300的另一个换热通道，再经出口物流切换阀420的一个出口流出形成反应产物17，反应产物17进入产物分离单元500；
再生气20进入进口物流切换阀410的另一个进口，再依次进入换热器300的一个换热通道，加热炉200，反应器100和换热器300的另一个换热通道，再经出 口物流切换阀420的另一个出口流出形成再生尾气30，再生尾气30进入烟囱。
其中，进口物流切换阀410还包括控制两个进口物流通道11和20启闭的自动控制机构，控制机构是气动、电动或油压元件；出口物流切换阀420也包括控制两个出口物流通道17和30启闭的自动控制机构，控制机构也是气动、电动或油压元件。
其中，反应器100为一独立的绝热固定床反应器或多段平行绝热固定床反应器中的一段。
如图1所示，一种基于上述系统进行甲醇制丙烯的反应再生方法，该方法通过反应气和再生气的周期性切换，实现甲醇催化脱水制丙烯反应和催化剂再生过程的周期性转换，反应再生方法具体包括以下步骤：
A、甲醇催化脱水制丙烯反应过程：
甲醇原料10与C4～C7的高碳烯烃馏分90混合后形成反应进料11，反应进料11进入进口物流切换阀410的一个进口，再进入换热器300的一个换热通道升温，经过加热炉200后从反应器100入口进入反应器100内，在反应器100内进行催化脱水制烯烃的反应，同时温度升高；
反应后产物从反应器100出口流经换热器300另一个换热通道降温回收反应热，然后经出口物流切换阀420的一个出口流出形成反应产物17，反应产物17进入产物分离单元500进行分离，得到主要含C1～C4烷烃的燃气40、乙烯50、丙烯60、水70、主要含C5以上烷烃和芳烃的汽油馏分80和C4～C7的高碳烯烃馏分90；
C4～C7的高碳烯烃馏分90循环利用，与甲醇原料10合流作为反应器100的反应进料，提高丙烯60或乙烯50的选择性；
随着催化脱水反应的进行，反应器100中的HZSM-5分子筛催化剂结焦失活，转化效率逐渐降低，直到甲醇的出口转化率由初期的大于99％降低到小于90～95％，进口物流切换阀410关闭反应进料11的进口，同时开启再生气20的进口，出口物流切换阀420关闭反应产物17的出口，同时开启再生尾气30的出口，脱水反应过程暂停，催化剂再生过程启用；
B、催化剂再生过程：
再生气20从进口物流切换阀410的再生气进口进入，依次进入换热器300的一个换热通道换热升温后，再进入加热炉200进一步升温，再进入反应器100，对 失活的HZSM-5分子筛催化剂进行烧焦再生，再生尾气离开反应器100后，进入换热器300的另一个换热通道降温回收热量后，从出口物流切换阀420的再生尾气出口排入烟囱排空；
再生过程中，再生尾气中CO2或CO含量不断降低，直到含量稳定或低于10～100ppmv时，进口物流切换阀410关闭再生气20的进口，同时开启反应进料11的进口，出口物流切换阀420关闭再生尾气30的出口，同时开启反应产物17的出口，催化剂再生过程暂停，脱水反应过程启用；
重复上述A、B两个过程，实现甲醇催化脱水制丙烯反应过程和催化剂再生过程的周期性循环转换，从而实现甲醇制丙烯的生产连续化。
图1中，12-16分别表示不同装置或设备进口或出口的反应物流。
其中，甲醇催化脱水制丙烯反应过程的时间为50～500小时，优选为100～400小时，更优选为200～300小时；催化剂再生过程的时间为5～50小时，优选为10～40小时，更优选为20～30小时。
其中，甲醇原料10中包含甲醇、二甲醚和水，其中甲醇或二甲醚的质量分数为10～50％，水的质量分数为10～50％；甲醇原料10和C4～C7的高碳烯烃馏分90的质量比为10:1～1:1，优选为6:1～2:1，更优选为4:1～3:1。
其中，甲醇原料10折合为甲醇(1公斤二甲醚相当于64/46＝1.3913公斤甲醇)的流量为1.0～10.0公斤甲醇/公斤催化剂/小时，优选为2.0～5.0。
其中，再生气20中包括质量分数1～10％的氧气，优选为2.0～5.0％，其稀释组分为氮气、二氧化碳或水蒸气等。
其中，甲醇制丙烯反应状态下反应器的进口温度为350-450℃，催化剂再生状态下反应器的进口温度为450-650℃；
其中，进入换热器前原料物流的温度为50-150℃，从换热器出来的原料物流的温度为250-400℃；
其中，反应器进口绝对压力为0.15-1.0MPa。
其中，催化剂为HZSM-5型分子筛颗粒，分子筛颗粒为球形、圆柱型或圆环柱型，直径3-5mm。
其中，催化剂的单程寿命一般为1-25天，当甲醇转化率低于90-95％时，系统即可切换进行催化剂再生，再生次数达到5-50次后，即可更换新鲜催化剂。
图2是本发明的另一种实施方式。与图1不同的是，进口切换阀410和出口切 换阀420分别由两个可以单独启闭的阀门组成，可以是蝶阀，截止阀，或其他具有开关作用的阀门。
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
如图1所示，一种甲醇制丙烯的反应再生装置，包括一个进口物流切换阀410、一台列管式换热器300、一台加热炉200、一台单段式固定床反应器100、一个出口物流切换阀420和分离单元500。反应器100中装填50吨催化剂，催化剂为HZSM-5型分子筛颗粒，Si/Al比为200。甲醇原料10流量为200吨/小时；循环物流为水和烃类的混合物，流量为水252吨/小时、C2和C4-C6烃775吨/小时。经换热和加热炉加热后，反应物流14的温度为400℃。经反应后，反应物流15的温度为480℃，甲醇转化率为99％。经分离后，丙烯60产量为76.6吨/小时，相当于丙烯选择性为87.54％，燃料气和液化气为3吨/小时，混合芳烃为4.5吨/小时。
装置运行120小时后，甲醇转化率下降到95％，此时切换进口物流切换阀410和出口物流切换阀420的进出口，使装置进口物流为再生气20，出口物流为再生尾气30。再生气20为摩尔比氧气：氮气＝5:95的混合物，流量为100吨/小时。经加热炉200加热至500℃后，进入反应器100进行再生。24小时后，测得出口反应物流15中二氧化碳浓度低于10ppm，可以认为再生完成，反应器进入下一周期。
实施例2
如图1所示，一种甲醇制丙烯的反应再生装置，包括一个进口物流切换阀410、一台列管式换热器300、一台加热炉200、一台单段式固定床反应器100、一个出口物流切换阀420和分离单元500。反应器100中装填50吨催化剂，催化剂为ZSM-5型高硅分子筛颗粒，硅铝比同实施例1。甲醇原料10流量为100吨/小时；循环物流为水和烃类的混合物，流量为水126吨/小时、C2和C4-C6烃387吨/小时。经换热和加热炉加热后，反应物流14的温度为400℃。经反应后，反应物流15的温度为480℃，甲醇转化率为99.9％。经分离后，丙烯产量为35.6吨/小时，相当于丙烯选择性为81.37％，燃料气和液化气为3.5吨/小时，混合芳烃为5.3吨/小时。
装置运行300小时后，甲醇转化率下降到95％，此时切换进口物流切换阀410和出口物流切换阀420的进出口，使装置进口物流为再生气20，出口物流为再生尾气30。再生气20为摩尔比氧气：二氧化碳＝5:95的混合物，流量为500吨/小时。经加热炉200加热至550℃后，进入反应器100进行再生。24小时后，测得出口反 应物流15中二氧化碳浓度低于80ppm，可以认为再生完成，反应器进入下一周期。
实施例3
如图1所示，一种甲醇制丙烯的反应再生装置，包括一个进口物流切换阀410、一台列管式换热器300、一台加热炉200、一台单段式固定床反应器100、一个出口物流切换阀420和分离单元500。反应器100中装填50吨催化剂，催化剂为ZSM-5型高硅分子筛颗粒，硅铝比同实施例1。甲醇原料10流量为400吨/小时；循环物流为水和烃类的混合物，流量为水504吨/小时、C2和C4-C6烃1548吨/小时。经换热和加热炉加热后，反应物流14的温度为400℃。经反应后，反应物流15的温度为480℃，甲醇转化率为97％。经分离后，丙烯产量为161吨/小时，相当于丙烯选择性为92.0％，燃料气和液化气为5.5吨/小时，混合芳烃为8.5吨/小时。
装置运行100小时后，甲醇转化率下降到90％，此时切换进口物流切换阀410和出口物流切换阀420的进出口，使装置进口物流为再生气20，出口物流为再生尾气30。再生气20为摩尔比氧气：二氧化碳＝5:95的混合物，流量为500吨/小时。经加热炉200加热至600℃后，进入反应器100进行再生。24小时后，测得出口反应物流15中二氧化碳浓度低于15ppm，可以认为再生完成，反应器进入下一周期。
实施例4
与实施例1所不同的是，反应器100为包含5段独立床层的固定床反应器，床层之间完全隔离，床层上方分别安装分布器，床层下方设有气体出口。每段床层中装填10吨催化剂，催化剂为HZSM-5型高硅分子筛颗粒，硅铝比同实施例1。甲醇原料10流量为200吨/小时；循环物流为水和烃类的混合物，流量为水252吨/小时、C2和C4-C6烃775吨/小时。经换热和加热炉加热后，反应物流14的温度为400℃，平均分成5股物流分别进入5段床层。经反应后，反应物流15的温度为480℃，甲醇转化率为99％。经分离后，丙烯产量为80吨/小时，相当于丙烯选择性为91.43％，燃料气和液化气为3吨/小时，混合芳烃为4.5吨/小时。
装置运行120小时后，甲醇转化率下降到95％，此时切换进口物流切换阀410和出口物流切换阀420的进出口，使装置进口物流为再生气20，出口物流为再生尾气30。再生气20为摩尔比氧气：氮气＝5:95的混合物，流量为100吨/小时。经加热炉200加热至500℃后，平均分成5股物流分别进入5段床层进行再生。24小时后，测得出口反应物流15中二氧化碳浓度低于80ppm，可以认为再生完成，反应器进入下一周期。
实施例5
如图2所示，一种甲醇制丙烯的反应再生装置，包括一个进口物流切换阀410、一台列管式换热器300、一台加热炉200、一台单段式固定床反应器100、一个出口物流切换阀420和分离单元500。反应器100中装填50吨催化剂，催化剂为HZSM-5型高硅分子筛颗粒，硅铝比同实施例1。甲醇原料10流量为400吨/小时；循环物流为水和烃类的混合物，流量为水510吨/小时、C2和C4-C6烃1500吨/小时。经换热和加热炉加热后，反应物流14的温度为350℃。经反应后，反应物流15的温度为480℃，甲醇转化率为99％。经分离后，丙烯产量为155吨/小时，燃料气和液化气为7吨/小时，混合芳烃为13吨/小时。
装置运行150小时后，甲醇转化率下降到95％，此时切换进口物流切换阀410和出口物流切换阀420的进出口，使装置进口物流为再生气20，出口物流为再生尾气30。再生气20为摩尔比氧气：氮气＝5:95的混合物，流量为100吨/小时。经加热炉200加热至500℃后，进入反应器100进行再生。24小时后，测得出口反应物流15中二氧化碳浓度低于50ppm，可以认为再生完成，反应器进入下一周期。
实施例6
如图2所示，一种甲醇制丙烯的反应再生装置，包括一套由两个截止阀组成的进口物流切换阀410、一台列管式换热器300、一台加热炉200、一台单段式固定床反应器100、一套由两个截止阀组成的出口物流切换阀420和分离单元500。反应器100中装填50吨催化剂，催化剂为HZSM-5型高硅分子筛颗粒，硅铝比同实施例1。反应过程中，首先打开反应进料11和反应产物17所对应的阀门，关闭再生气20和再生尾气30所对应的阀门。甲醇原料10流量为200吨/小时；循环物流为水和烃类的混合物，流量为水252吨/小时、C2和C4-C6烃775吨/小时。经换热和加热炉加热后，反应物流14的温度为400℃。经反应后，反应物流15的温度为480℃，甲醇转化率为99％。经分离后，丙烯产量为80吨/小时，燃料气和液化气为3吨/小时，混合芳烃为4.5吨/小时。
装置运行120小时后，甲醇转化率下降到95％，此时关闭反应进料11和反应产物17所对应的阀门，打开再生气20和再生尾气30所对应的阀门，使装置进口物流为再生气20，出口物流为再生尾气30。再生气20为摩尔比氧气：氮气＝5:95的混合物，流量为100吨/小时。经加热炉200加热至500℃后，进入反应器100进行再生。24小时后，测得出口反应物流15中二氧化碳浓度低于60ppm，可以认 为再生完成，反应器进入下一周期。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (10)

  1. 一种甲醇制丙烯的反应再生系统，其特征在于，所述的反应再生系统包括反应器(100)、加热炉(200)、换热器(300)、进口物流切换阀(410)、出口物流切换阀(420)及分离单元(500)，所述的反应器(100)入口依次与加热炉(200)、换热器(300)其中一个换热通道和进口物流切换阀(410)连通构成原料通道，所述的反应器(100)的出口依次与换热器(300)另一个换热通道、出口物流切换阀(420)及分离单元(500)连通构成产物通道；
    所述的反应器(100)为绝热固定床反应器，所述反应器(100)内置有高硅HZSM-5分子筛催化剂；
    所述进口物流切换阀(410)有两个进口物流通道，其中一个走反应进料(11)，另一个走再生气(20)；
    所述出口物流切换阀(420)有两个出口物流通道，其中一个走反应产物(17)另一个走再生尾气(30)。
  2. 根据权利要求1所述的一种甲醇制丙烯的反应再生系统，其特征在于，所述分离单元(500)为将反应产物分离出主要含C1～C4烷烃的燃气(40)、乙烯(50)、丙烯(60)、水(70)、主要含C5以上烷烃和芳烃的汽油馏分(80)和C4～C7的高碳烯烃馏分(90)的加压和常压精馏塔组。
  3. 根据权利要求2所述的一种甲醇制丙烯的反应再生系统，其特征在于，甲醇原料(10)与所述C4～C7的高碳烯烃馏分(90)混合后作为反应进料(11)，所述反应进料(11)进入进口物流切换阀(410)的一个进口，再依次进入换热器(300)的一个换热通道，加热炉(200)，反应器(100)和换热器(300)的另一个换热通道，再经出口物流切换阀(420)的一个出口流出形成反应产物(17)，所述反应产物(17)进入产物分离单元(500)；
    所述再生气(20)进入进口物流切换阀(410)的另一个进口，再依次进入换热器(300)的一个换热通道，加热炉(200)，反应器(100)和换热器(300)的另一个换热通道，再经出口物流切换阀(420)的另一个出口流出形成再生尾气(30)，所述再生尾气(30)进入烟囱。
  4. 根据权利要求1所述的一种甲醇制丙烯的反应再生系统，其特征在于，所述进口物流切换阀(410)还包括控制两个进口物流通道(11)和(20)启闭的自 动控制机构，所述控制机构是气动、电动或油压元件；
    所述出口物流切换阀(420)也包括控制两个出口物流通道(17)和(30)启闭的自动控制机构，所述控制机构也是气动、电动或油压元件。
  5. 根据权利要求1所述的一种甲醇制丙烯的反应再生系统，其特征在于，所述的反应器(100)为一独立的绝热固定床反应器或多段平行绝热固定床反应器中的一段。
  6. 一种基于权利要求1-5中任一项所述系统进行甲醇制丙烯的反应再生方法，其特征在于，该方法通过反应气和再生气的周期性切换，实现甲醇催化脱水制丙烯反应和催化剂再生过程的周期性转换，所述的反应再生方法具体包括以下步骤：
    A、甲醇催化脱水制丙烯反应过程：
    甲醇原料(10)与C4～C7的高碳烯烃馏分(90)混合后形成反应进料(11)，所述反应进料(11)进入进口物流切换阀(410)的一个进口，再进入换热器(300)的一个换热通道升温，经过加热炉(200)后从反应器(100)入口进入反应器(100)内，在反应器(100)内进行催化脱水制烯烃的反应，同时温度升高；
    反应后产物从反应器(100)出口流经换热器(300)另一个换热通道降温回收反应热，然后经出口物流切换阀(420)的一个出口流出形成反应产物(17)，所述反应产物(17)进入产物分离单元(500)进行分离，得到主要含C1～C4烷烃的燃气(40)、乙烯(50)、丙烯(60)、水(70)、主要含C5以上烷烃和芳烃的汽油馏分(80)和C4～C7的高碳烯烃馏分(90)；
    所述C4～C7的高碳烯烃馏分(90)循环利用，与甲醇原料(10)合流作为反应器(100)的反应进料，提高丙烯(60)或乙烯(50)的选择性；
    随着催化脱水反应的进行，所述反应器(100)中的HZSM-5分子筛催化剂结焦失活，转化效率逐渐降低，直到甲醇的出口转化率由初期的大于99％降低到小于90～95％，所述进口物流切换阀(410)关闭反应进料(11)的进口，同时开启再生气(20)的进口，所述出口物流切换阀(420)关闭反应产物(17)的出口，同时开启再生尾气(30)的出口，脱水反应过程暂停，催化剂再生过程启用；
    B、催化剂再生过程：
    再生气(20)从进口物流切换阀(410)的再生气进口进入，依次进入换热器(300)的一个换热通道换热升温后，再进入加热炉(200)进一步升温，再进入反应器(100)，对失活的HZSM-5分子筛催化剂进行烧焦再生，再生尾气离开反应 器(100)后，进入换热器(300)的另一个换热通道降温回收热量后，从出口物流切换阀(420)的再生尾气出口排入烟囱排空；
    所述再生过程中，再生尾气中CO2或CO含量不断降低，直到含量稳定或低于10～100ppmv时，所述进口物流切换阀(410)关闭再生气(20)的进口，同时开启反应进料(11)的进口，所述出口物流切换阀(420)关闭再生尾气(30)的出口，同时开启反应产物(17)的出口，催化剂再生过程暂停，脱水反应过程启用；
    重复上述A、B两个过程，实现所述甲醇催化脱水制丙烯反应过程和所述催化剂再生过程的周期性循环转换，从而实现甲醇制丙烯的生产连续化。
  7. 根据权利要求6所述的一种甲醇制丙烯的反应再生方法，其特征在于，所述甲醇催化脱水制丙烯反应过程的时间为50～500小时，优选为100～400小时，更优选为200～300小时；
    所述催化剂再生过程的时间为5～50小时，优选为10～40小时，更优选为20～30小时。
  8. 根据权利要求6所述的一种甲醇制丙烯的反应再生方法，其特征在于，所述的甲醇原料(10)中包含甲醇、二甲醚和水，其中甲醇或二甲醚的质量分数为10～50％，水的质量分数为10～50％；所述甲醇原料(10)和所述C4～C7的高碳烯烃馏分(90)的质量比为10:1～1:1，优选为6:1～2:1，更优选为4:1～3:1。
  9. 根据权利要求6所述的一种甲醇制丙烯的反应再生方法，其特征在于，所述甲醇原料(10)折合为甲醇的流量为1.0～10.0公斤甲醇/公斤催化剂/小时，优选为2.0～5.0。
  10. 根据权利要求6所述的一种甲醇制丙烯的反应再生方法，其特征在于，所述再生气(20)中包括质量分数1～10％的氧气，优选为2.0～5.0％，其稀释组分为氮气、二氧化碳或水蒸气。
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CN115463613A (zh) * 2022-10-20 2022-12-13 浙江大学 一种高温高压下快速可控反应的立式多功能固定床装置
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