CN102875305B - Method for preparing low carbon olefins from methanol - Google Patents

Method for preparing low carbon olefins from methanol Download PDF

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CN102875305B
CN102875305B CN201110195337.9A CN201110195337A CN102875305B CN 102875305 B CN102875305 B CN 102875305B CN 201110195337 A CN201110195337 A CN 201110195337A CN 102875305 B CN102875305 B CN 102875305B
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enter
reaction
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fluidized bed
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CN102875305A (en
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齐国祯
王洪涛
王华文
盛世春
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • 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
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

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Abstract

The invention relates to a method for preparing low carbon olefins from methanol to mainly solve a low yield problem of the low carbon olefins in the prior art. The method for preparing the low carbon olefins through adopting the methanol comprises the following steps: 1, allowing a methanol raw material to enter a rapid fluidized bed reaction zone to contact with a catalyst, allowing a generated gas phase material flow and the catalyst to enter a rough-cut cyclone, allowing the gas phase material flow to enter a settlement device and the catalyst to enter a gas-solid distribution zone, allowing parts of the catalyst in the gas-solid distribution zone to enter a downer reaction zone in order to contact with the methanol raw material, allowing the generated gas phase material flow and the catalyst to enter the rapid fluidized bed reaction zone, and allowing parts of the catalyst to enter a regenerator, and regenerating to form a regenerated catalyst; and 2, returning parts of the regenerated catalyst to the downer reaction zone, allowing parts of the regenerated catalyst in the downer reaction zone to enter a riser reaction zone in order to contact with above C4 hydrocarbons, allowing the generated gas phase material flow and the catalyst to enter the settlement device, carrying out steam stripping of the catalyst in the settlement device, and allowing the steam-stripped catalyst to enter the regenerator for regenerating. The above technical scheme well solves the problem, so the method can be applied to the industrial production of the low carbon olefins.

Description

The method of preparing light olefins from methanol
Technical field
The present invention relates to a kind of method of preparing light olefins from methanol.
Technical background
Low-carbon alkene, i.e. ethene and propylene, is two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are to produce by petroleum path, but due to the limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people start to greatly develop the technology of alternative materials conversion ethene processed, propylene.Wherein, the important alternative materials of producing for low-carbon alkene of one class is oxygenatedchemicals, such as alcohols (methyl alcohol, ethanol), ethers (dme, methyl ethyl ether), ester class (methylcarbonate, methyl-formiate) etc., these oxygenatedchemicalss can be transformed by coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, as methyl alcohol, can be made by coal or Sweet natural gas, and technique is very ripe, can realize the industrial scale of up to a million tonnes.Due to the popularity in oxygenatedchemicals source, add and transform the economy that generates low-carbon alkene technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), be particularly subject to increasing attention by the technique of preparing olefin by conversion of methanol (MTO).
In US4499327 patent, silicoaluminophosphamolecular molecular sieve catalyst is applied to preparing olefin by conversion of methanol technique and studies in detail, think that SAPO-34 is the first-selected catalyzer of MTO technique.SAPO-34 catalyzer has very high selectivity of light olefin, and activity is also higher, and can make methanol conversion is reaction times of low-carbon alkene to be less than the degree of 10 seconds, more even reaches in the reaction time range of riser tube.
Technology and reactor that a kind of methanol conversion is low-carbon alkene in US 6166282, are announced, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu of gas speed has reacted, rise to after the fast subregion that internal diameter diminishes rapidly, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Due to reaction after product gas and catalyzer sharp separation, effectively prevent the generation of secondary reaction.Through analog calculation, compared with traditional bubbling fluidization bed bioreactor, this fast fluidized bed reactor internal diameter and the required reserve of catalyzer all greatly reduce.But in the method, low-carbon alkene carbon base absorption rate is general all in 77% left and right, has the problem that yield of light olefins is lower.
In CN 1723262, having announced with the multiple riser reaction unit of central catalyst return is low-carbon alkene technique for oxygenate conversion, this covering device comprises multiple riser reactors, gas solid separation district, multiple offset components etc., each riser reactor has the port of injecting catalyst separately, be pooled to the disengaging zone of setting, catalyzer and gas product are separated.In the method, low-carbon alkene carbon base absorption rate is general all between 75～80%, has equally the problem that yield of light olefins is lower.
All there is the problem that yield of light olefins is lower in prior art, the present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the lower problem of yield of light olefins existing in prior art, and a kind of method of new preparing light olefins from methanol is provided.The method, for the production of low-carbon alkene, has advantages of that yield of light olefins is higher.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of method of preparing light olefins from methanol, comprise the following steps: the raw material that (a) is mainly methyl alcohol enters fast fluidized bed reaction zone, contact with the catalyzer that comprises sial phosphorus molecular sieve, the gaseous stream generating and catalyzer enter slightly and revolve, gaseous stream enters settling vessel through slightly revolving gaseous phase outlet, catalyzer enters gas-solid distribution zone through thick spin material leg, the catalyzer of gas-solid distribution zone is at least divided into two portions, a part enters down-flow fluidized bed using ECT reaction zone, contact with the raw material that comprises methyl alcohol, the gaseous stream and the catalyzer that generate enter fast bed reaction zone, a part enters revivifier regeneration, form regenerated catalyst, (b) described regenerated catalyst is at least divided into two portions, a part is returned to down-flow fluidized bed using ECT reaction zone, a part enters riser reaction zone, contact with the above hydrocarbon of C4, the gaseous stream and the catalyzer that generate enter described settling vessel, and the gaseous stream after gas solid separation enters centrifugal station, separate and obtain low-carbon alkene product and the above hydrocarbon by product of described C4, the above hydrocarbon by product of C4 enters riser reaction zone, and the catalyzer going out through gas solid separation in settling vessel enters revivifier regeneration after stripping.
In technique scheme, in the above hydrocarbon stream of described C4, C 4 olefin mass content is greater than 75%; Described sial phosphorus molecular sieve comprises SAPO-34; Described riser reaction zone reaction conditions is: temperature of reaction is 500～600 DEG C, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and gas phase linear speed is 4～12 meter per seconds; Down-flow fluidized bed using ECT reaction zone reaction conditions is: temperature of reaction is 380～460 DEG C, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and gas phase linear speed is 5～10 meter per seconds; Fast bed reaction zone reaction conditions is: temperature of reaction is 425～500 DEG C, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and gas phase linear speed is 1～3 meter per second; The average carbon deposition quantity massfraction of described regenerated catalyst is 0.01～0.5%; Describedly slightly revolve the gaseous stream that gaseous phase outlet goes out and enter the close phase section of settling vessel through described, contact and continue with the catalyzer in settling vessel and react; Described gas-solid distribution zone is positioned at top, described down-flow fluidized bed using ECT reaction zone, and gaseous stream and catalyzer enter down-flow fluidized bed using ECT reaction zone after gas-solid distribution zone is mixed with described methanol feedstock; The catalyzer of described gas-solid distribution zone is at least divided into two portions, and 20～75% enter down-flow fluidized bed using ECT reaction zone, and 25～80% enter revivifier regeneration, form regenerated catalyst; Described regenerated catalyst is at least divided into two portions, and 20～60% return to down-flow fluidized bed using ECT reaction zone, and 40～80% enter riser reaction zone.
The method of calculation of average coke content of the present invention are that carbon deposit quality on catalyzer is divided by described catalyst quality.Carbon deposit measuring method on catalyzer is as follows: will mix the catalyst mix with carbon deposit comparatively uniformly, then weigh the band C catalyst of 0.1～1 gram, be put in pyrocarbon analyser and burn, by infrared analysis burn generate carbonic acid gas quality, thereby obtain the carbonaceous amount on catalyzer.
The preparation method of sial phosphorus molecular sieve of the present invention is: first preparing molecular sieve presoma, is 0.03～0.6R by mole proportioning: (Si 0.01～0.98: Al 0.01～0.6: P 0.01～0.6): 2～500H 2o, wherein R represents template, and template is triethylamine, and constitutive material mixed solution obtains at the temperature of 100-250 DEG C after the crystallization of 1～10 hour; Again, molecular sieve presoma, phosphorus source, silicon source, aluminium source, template, water etc. are mixed according to certain ratio after at 110～260 DEG C hydrothermal crystallizing after at least 0.1 hour, finally obtain SAPO molecular sieve.The molecular sieve of preparation is mixed with the binding agent of required ratio, after the operation stepss such as, roasting dry through spraying, obtain final SAPO catalyzer, the weight percentage of binding agent in molecular sieve is between 10～90%.
In the present invention, " slightly revolve " and refer to the elementary cyclonic separator that is positioned at the outlet of riser tube or down-flow fluidized bed using ECT and can realizes gas-solid sharp separation, due to its separation efficiency lower (generally between 70～90%), therefore those skilled in the art is generally simply referred to as " slightly revolving ".And down-flow fluidized bed using ECT refers to that solid particulate presents the tubular reactor of flow pattern from top to bottom under solid particulate self gravitation or airflow acting force.
Adopt method of the present invention, three reaction zones are set, it is low-carbon alkene that fast bed reaction zone is mainly used in transforming methyl alcohol, and the main transform portion methyl alcohol in down-flow fluidized bed using ECT reaction zone is dme and low-carbon alkene, and in riser reaction zone, being mainly used in transforming the above hydrocarbon of C4 that methyl alcohol reaction generates is low-carbon alkene.In riser reaction zone, be high temperature, highly active regenerated catalyst, can ensure the above olefin conversion of higher C4, the high linear speed of riser tube can improve again selectivity of light olefin, and in riser tube, the reaction of C4 olefin cracking can be again the pre-carbon distribution of regenerated catalyst simultaneously.And fast bed reaction zone is after conversion methyl alcohol is low-carbon alkene, on catalyzer, form carbon distribution, but the catalyzer that this part contains carbon distribution still has catalytic activity, having the ability is completely dme by methanol conversion, generates low-carbon alkene simultaneously.Owing to being the catalyzer of pre-carbon distribution in down-flow fluidized bed using ECT reaction zone, there is the advantage that selectivity is higher, the raising that the advantage of the approximate plug flow of down-flow fluidized bed using ECT Gas-particle Flows is favourable selectivity of light olefin.Gaseous stream in down-flow fluidized bed using ECT continues to participate in reaction after entering fast fluidized bed reaction zone, dme and the above hydrocarbon of part C4 can react generation low-carbon alkene, and unreacted completely the above hydrocarbon of C4 continue reaction for low-carbon alkene entering behind settling vessel bottom, the final unreacted completely above hydrocarbon of C4 returns to riser reaction zone after separating and further generates low-carbon alkene.Therefore, adopt method of the present invention, can reach the object that improves yield of light olefins.
Adopt technical scheme of the present invention: in the above hydrocarbon stream of described C4, C 4 olefin mass content is greater than 75%; Described sial phosphorus molecular sieve comprises SAPO-34; Described riser reaction zone reaction conditions is: temperature of reaction is 500～600 DEG C, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and gas phase linear speed is 4～12 meter per seconds; Down-flow fluidized bed using ECT reaction zone reaction conditions is: temperature of reaction is 380～460 DEG C, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and gas phase linear speed is 5～10 meter per seconds; Fast bed reaction zone reaction conditions is: temperature of reaction is 425～500 DEG C, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and gas phase linear speed is 1～3 meter per second; The average carbon deposition quantity massfraction of described regenerated catalyst is 0.01～0.5%; Describedly slightly revolve the gaseous stream that gaseous phase outlet goes out and enter the close phase section of settling vessel through described, contact and continue with the catalyzer in settling vessel and react; Described gas-solid distribution zone is positioned at top, described down-flow fluidized bed using ECT reaction zone, and gaseous stream and catalyzer enter down-flow fluidized bed using ECT reaction zone after gas-solid distribution zone is mixed with described methanol feedstock; The catalyzer of described gas-solid distribution zone is at least divided into two portions, and 20～75% enter down-flow fluidized bed using ECT reaction zone, and 25～80% enter revivifier regeneration, form regenerated catalyst; Described regenerated catalyst is at least divided into two portions, 20～60% return to down-flow fluidized bed using ECT reaction zone, 40～80% enter riser reaction zone, low-carbon alkene carbon base absorption rate reaches 88.94% (weight), exceed and can reach more than 6 percentage points than the low-carbon alkene carbon base absorption rate of prior art, obtained good technique effect.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1 is methanol feed line; 2 is fast fluidized bed reaction zone; 3 is undergauge riser tube; 4 for slightly revolving; 5 for slightly revolving gaseous phase outlet pipeline; 6 is thick spin material leg; 7 is gas-solid distribution zone; 8 is methanol feed line; 9 is down-flow fluidized bed using ECT reaction zone; 10 is inclined tube to be generated; 11 is revivifier; 12 is regenerating medium feeding line; 13 is regenerator sloped tube; 14 is revivifier negative area; 15 is revivifier gas-solid cyclone separator; 16 is exhanst gas outlet; 17 is regenerator sloped tube; 18 is the above hydrocarbon feeding line of C4; 19 is raising section; 20 is riser reaction zone; 21 is the close phase section of settling vessel; 22 is settling vessel expanding reach; 23 slightly revolve for riser reaction zone exports; 24 is gas-solid cyclone separator in settling vessel; 25 is its outlet of product; 26 is regeneration standpipe; 27 stripping medium feeding lines.
The raw material that is mainly methyl alcohol enters fast fluidized bed reaction zone 2, contact with the catalyzer that comprises sial phosphorus molecular sieve, the gaseous stream generating and catalyzer enter and slightly revolve 4, gaseous stream enters the close phase section 21 of settling vessel through slightly revolving gaseous phase outlet 5, catalyzer enters gas-solid distribution zone 7 through thick spin material leg 6, the catalyzer of gas-solid distribution zone 7 is at least divided into two portions, a part enters down-flow fluidized bed using ECT reaction zone 9, contact with the raw material that comprises methyl alcohol, the gaseous stream and the catalyzer that generate enter fast bed reaction zone 2, a part enters revivifier 11 and regenerates, form regenerated catalyst, described regenerated catalyst is at least divided into two portions, a part is returned to down-flow fluidized bed using ECT reaction 9, a part enters riser reaction zone 20, contact with the above hydrocarbon of C4, the gaseous stream and the catalyzer that generate enter described settling vessel 22, gaseous stream after gas solid separation enters centrifugal station, separation obtains low-carbon alkene product and the above hydrocarbon by product of described C4, the above hydrocarbon by product of C4 enters riser reaction zone 20, the interior catalyzer going out through gas solid separation of settling vessel 22 enters revivifier 11 and regenerates after stripping.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
On reaction unit as shown in Figure 1, methanol feedstock enters fast fluidized bed reaction zone, contact with SAPO-34 catalyzer, the gaseous stream generating and catalyzer enter slightly and revolve, gaseous stream enters the close phase section of settling vessel through slightly revolving gaseous phase outlet, catalyzer enters gas-solid distribution zone through thick spin material leg, the catalyzer of gas-solid distribution zone is at least divided into two portions, 20% enters down-flow fluidized bed using ECT reaction zone, contact with methanol feedstock, the gaseous stream and the catalyzer that generate enter fast bed reaction zone, and 80% enters revivifier regeneration, forms regenerated catalyst.Described regenerated catalyst is at least divided into two portions, 20% returns to down-flow fluidized bed using ECT reaction zone, 80% enters riser reaction zone, contact with the above hydrocarbon of C4, the gaseous stream and the catalyzer that generate enter described settling vessel, and the gaseous stream after gas solid separation enters centrifugal station, separate and obtain low-carbon alkene product and the above hydrocarbon by product of described C4, the above hydrocarbon by product of C4 enters riser reaction zone, and the catalyzer going out through gas solid separation in settling vessel enters revivifier regeneration after stripping.In the above hydrocarbon stream of C4, C 4 olefin mass content is 88%, and riser reaction zone reaction conditions is: temperature of reaction is 500 DEG C, and reaction pressure is counted 0.01MPa with gauge pressure, and gas phase linear speed is 4 meter per seconds; Down-flow fluidized bed using ECT reaction zone reaction conditions is: temperature of reaction is 380 DEG C, and reaction pressure is counted 0.01MPa with gauge pressure, and gas phase linear speed is 5 meter per seconds; Fast bed reaction zone reaction conditions is: temperature of reaction is 425 DEG C, reaction pressure is counted 0.01MPa with gauge pressure, gas phase linear speed is 1 meter per second, the average carbon deposition quantity massfraction of regenerated catalyst is 0.01%, described gas-solid distribution zone is positioned at top, described down-flow fluidized bed using ECT reaction zone, and gaseous stream and catalyzer enter down-flow fluidized bed using ECT reaction zone after gas-solid distribution zone is mixed with methanol feedstock.Reactor product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 84.15% (weight).
[embodiment 2]
According to condition and step described in embodiment 1, the catalyzer of gas-solid distribution zone is at least divided into two portions, 75% enters down-flow fluidized bed using ECT reaction zone, 25% enters revivifier regeneration, form regenerated catalyst, described regenerated catalyst is at least divided into two portions, 60% returns to down-flow fluidized bed using ECT reaction zone, 40% enters riser reaction zone, in the above hydrocarbon stream of C4, C 4 olefin mass content is 75%, riser reaction zone reaction conditions is: temperature of reaction is 600 DEG C, and reaction pressure is counted 0.01MPa with gauge pressure, and gas phase linear speed is 12 meter per seconds; Down-flow fluidized bed using ECT reaction zone reaction conditions is: temperature of reaction is 460 DEG C, and reaction pressure is counted 0.01MPa with gauge pressure, and gas phase linear speed is 10 meter per seconds; Fast bed reaction zone reaction conditions is: temperature of reaction is 500 DEG C, and reaction pressure is counted 0.01MPa with gauge pressure, and gas phase linear speed is 3 meter per seconds, and the average carbon deposition quantity massfraction of regenerated catalyst is 0.5%.Reactor product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 85.39% (weight).
[embodiment 3]
According to condition and step described in embodiment 1, the catalyzer of gas-solid distribution zone is at least divided into two portions, 50% enters down-flow fluidized bed using ECT reaction zone, 50% enters revivifier regeneration, form regenerated catalyst, described regenerated catalyst is at least divided into two portions, 50% returns to down-flow fluidized bed using ECT reaction zone, 50% enters riser reaction zone, in the above hydrocarbon stream of C4, C 4 olefin mass content is 92%, riser reaction zone reaction conditions is: temperature of reaction is 560 DEG C, and reaction pressure is counted 0.01MPa with gauge pressure, and gas phase linear speed is 7 meter per seconds; Down-flow fluidized bed using ECT reaction zone reaction conditions is: temperature of reaction is 440 DEG C, and reaction pressure is counted 0.01MPa with gauge pressure, and gas phase linear speed is 6.6 meter per seconds; Fast bed reaction zone reaction conditions is: temperature of reaction is 450 DEG C, and reaction pressure is counted 0.01MPa with gauge pressure, and gas phase linear speed is 1.5 meter per seconds, and the average carbon deposition quantity massfraction of regenerated catalyst is 0.15%.Reactor product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 88.94% (weight).
[embodiment 4]
According to condition and step described in embodiment 3, the catalyzer of gas-solid distribution zone is at least divided into two portions, and riser reaction zone reaction conditions is: temperature of reaction is 550 DEG C, and reaction pressure is counted 0.3MPa with gauge pressure, and gas phase linear speed is 5 meter per seconds; Down-flow fluidized bed using ECT reaction zone reaction conditions is: temperature of reaction is 434 DEG C, and reaction pressure is counted 0.3MPa with gauge pressure, and gas phase linear speed is 4.5 meter per seconds; Fast bed reaction zone reaction conditions is: temperature of reaction is 438 DEG C, and reaction pressure is counted 0.3MPa with gauge pressure, and gas phase linear speed is 1.2 meter per seconds, and the average carbon deposition quantity massfraction of regenerated catalyst is 0.1%.Reactor product adopts online gas chromatographic analysis, and low-carbon alkene carbon base absorption rate is 87.01% (weight).
[comparative example 1]
According to condition and step described in embodiment 3, just riser reaction zone is not set, fast bed reaction zone, down-flow fluidized bed using ECT reaction zone, settling vessel are only set, yield of light olefins is 83.17% (weight).
[comparative example 2]
According to condition and step described in embodiment 3, down-flow fluidized bed using ECT reaction is not just set, the gaseous stream of fast bed reaction zone and catalyzer directly enter the close phase section of settling section, and yield of light olefins is 86.28% (weight).
[comparative example 3]
According to condition and step described in embodiment 3, down-flow fluidized bed using ECT reaction zone and riser reaction zone are not just set, the catalyzer of fast bed reaction zone and gaseous stream enter after settling vessel, gas gas-phase objects diffluence centrifugal station, catalyzer returns to revivifier, and yield of light olefins is 82.34% (weight).
Obviously, adopt method of the present invention, can reach the object that improves yield of light olefins, there is larger technical superiority, can be used in the industrial production of low-carbon alkene.

Claims (7)

1. a method for preparing light olefins from methanol, comprises the following steps:
(a) raw material that is mainly methyl alcohol enters fast fluidized bed reaction zone, contact with the catalyzer that comprises sial phosphorus molecular sieve, the gaseous stream generating and catalyzer enter slightly and revolve, gaseous stream enters settling vessel through slightly revolving gaseous phase outlet, catalyzer enters gas-solid distribution zone through thick spin material leg, the catalyzer of gas-solid distribution zone is at least divided into two portions, a part enters down-flow fluidized bed using ECT reaction zone, contact with the raw material that comprises methyl alcohol, the gaseous stream and the catalyzer that generate enter fast fluidized bed reaction zone, a part enters revivifier regeneration, forms regenerated catalyst;
(b) described regenerated catalyst is at least divided into two portions, a part is returned to down-flow fluidized bed using ECT reaction zone, a part enters riser reaction zone, contact with the above hydrocarbon of C4, the gaseous stream and the catalyzer that generate enter described settling vessel, and the gaseous stream after gas solid separation enters centrifugal station, separate and obtain low-carbon alkene product and the above hydrocarbon by product of described C4, the above hydrocarbon by product of C4 enters riser reaction zone, and the catalyzer going out through gas solid separation in settling vessel enters revivifier regeneration after stripping;
Wherein, described low-carbon alkene is ethene and propylene; The described elementary cyclonic separator that can realize gas-solid sharp separation for being positioned at leg outlet that slightly revolves, its separation efficiency is 70～90%; Described sial phosphorus molecular sieve comprises SAPO-34.
2. the method for preparing light olefins from methanol according to claim 1, is characterized in that in the above hydrocarbon stream of described C4, C 4 olefin mass content is greater than 75%.
3. the method for preparing light olefins from methanol according to claim 1, is characterized in that described riser reaction zone reaction conditions is: temperature of reaction is 500～600 DEG C, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and gas phase linear speed is 4～12 meter per seconds; Down-flow fluidized bed using ECT reaction zone reaction conditions is: temperature of reaction is 380～460 DEG C, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and gas phase linear speed is 5～10 meter per seconds; Fast bed reaction zone reaction conditions is: temperature of reaction is 425～500 DEG C, and reaction pressure is counted 0.01～0.3MPa with gauge pressure, and gas phase linear speed is 1～3 meter per second.
4. the method for preparing light olefins from methanol according to claim 1, is characterized in that the average carbon deposition quantity massfraction of described regenerated catalyst is 0.01～0.5%.
5. the method for preparing light olefins from methanol according to claim 1, is characterized in that describedly slightly revolving the gaseous stream that gaseous phase outlet goes out and entering the close phase section of settling vessel through described, contacts and continue to react with the catalyzer in settling vessel.
6. the method for preparing light olefins from methanol according to claim 1, is characterized in that being at least divided into two portions at the catalyzer of described gas-solid distribution zone, and 20～75% enter down-flow fluidized bed using ECT reaction zone, and 25～80% enter revivifier regeneration, form regenerated catalyst.
7. the method for preparing light olefins from methanol according to claim 1, is characterized in that being at least divided into two portions at described regenerated catalyst, and 20～60% return to down-flow fluidized bed using ECT reaction zone, and 40～80% enter riser reaction zone.
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Citations (4)

* Cited by examiner, † Cited by third party
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