CN102020523A - Operating method for olefin conversion device - Google Patents
Operating method for olefin conversion device Download PDFInfo
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- CN102020523A CN102020523A CN2009101702744A CN200910170274A CN102020523A CN 102020523 A CN102020523 A CN 102020523A CN 2009101702744 A CN2009101702744 A CN 2009101702744A CN 200910170274 A CN200910170274 A CN 200910170274A CN 102020523 A CN102020523 A CN 102020523A
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Abstract
The invention belongs to an operating method for an olefin conversion device and relates to a device for preparing olefin such as methanol to olefin (MTO) and methanol to propylene (MTP) by using organic oxides such as methanol, dimethyl ether and the like. The method is characterized by comprising the following steps that: when the device is operated, catalysts of a reactor 2 and a regenerator 3 are respectively introduced from respective catalyst tank and are added in two paths; and the catalysts respectively added into the reactor and the regenerator are heated depending on an external heat source and a heating medium which are independently arranged, namely, the reactor 2 is provided with an operating steam superheater 1 to heat the catalyst by using high-temperature steam and the regenerator 3 is provided with an auxiliary combustor to heat the catalyst by using high-temperature air. When added, the catalysts are not transferred from the regenerator 3 to the reactor 2, namely the catalysts are not transferred between the reactor and the regenerator.
Description
Technical field
The invention belongs to a kind of start-up method of conversion of olefines device, relate to the device that organic oxygen compounds such as methyl alcohol, dme are produced alkene (as MTO, MTP).
Background technology
Light olefin is defined as ethene, propylene, butylene and composition thereof here, is to produce the multiple important chemical and the raw material of polymkeric substance.Light olefin is produced by the petroleum cracking typically, because the limited supply of competitive petroleum, and international price is surging day by day, produce light olefin from petroleum and seem more and more uneconomical, production cost also increases comparatively fast, for this reason, the exploitation of producing the light olefin technology based on alternative materials seems urgent day by day, and the more and more important effect of performance.
The important alternative materials that is used to produce light olefin is an oxygenatedchemicals, as alcohol, and especially methyl alcohol and ethanol, dme, methyl ethyl ether, diethyl ether, methylcarbonate and methyl-formiate etc.These oxygenatedchemicalss are a variety of can be produced by fermenting, perhaps derived from biomass material, Sweet natural gas, petroleum liquid, also comprise by coal, the synthetic gas that reclaims plastics, urban waste or contain the carbonaceous material of any organic materials etc. and producing.Because wide material sources, non-petroleums such as alcohol, alcohol derivate and other oxygenatedchemicals have wide economic outlook as olefin production.
Oxygenatedchemicals conversion of olefines technology is to be raw material with the oxygenatedchemicals, contact with special aluminosilicophosphate (SAPO) molecular sieve catalyst, use fluidization technique, under suitable reaction process condition, comprise temperature, pressure, bed air speed and apparent linear speed thereof, carbon deposition quantity of catalyst, reaction (stop) time and implement each factor control method each other etc., conversion reaction takes place, to produce the processing method of low-carbon alkene etc.Similar with sophisticated catalytic cracking process, conversion reaction and catalyzer coke burning regeneration carry out continuously, the catalyzer behind the continuous compensation regeneration of reactor, and it is stable to keep catalyst activity and product selectivity, and conversion reaction is steadily carried out.
The existing catalytic cracking unit process of going into operation is:
1) catalyzer in reactor, the regenerator system all adds from revivifier, is adding the agent initial stage, relies on auxiliary chamber to add the catalyzer temperature-elevating that warm air makes adding, and the top temperature that auxiliary chamber adds warm air generally is no more than 780 ℃; When in the revivifier just the catalyzer material level of dress reach when flooding the combustion oil nozzle, and temperature sprays into combustion oil when being higher than 300-350 ℃, relies on the combustion oil heatable catalyst, heat-up rate is accelerated.
2) be filled to certain material level when the revivifier inner catalyst, when temperature reaches more than 500 ℃, change agent to reactor.
3) for the first time change agent and finish after, close guiding valve, revivifier continues to add agent, heats up.
4) after revivifier catalyzer material level, temperature touch the mark, open guiding valve, carry out changeing the second time agent.Because the revivifier space is big more a lot of than space reactor, only need first and second to change agent, just can set up the catalyst recirculation between revivifier-reactor.Changeing the timed interval of agent for twice should lack as far as possible, relies on the steam fluidisation because change the thermocatalyst of reactor over to, and temperature can not cause catalyzer " and mud " slowly reducing.
5) process that goes into operation of any device all is relative erratic process, can cause that the race of system catalyst is decreased, and therefore, this process is carried out to such an extent that The faster the better.General, for catalytic cracking unit, device begins to need to finish in 4-8 hour to reaching feed conditions (be catalyzer material level and temperature touch the mark requirement) from adding agent.Different with the heavy oil product catalytic cracking unit, in the conversion of olefines device, oxygenatedchemicals conversion of olefines product gas is gone back a large amount of water of by-product and a spot of C except low-carbon alkenes such as ethene, propylene
4And organic oxygen compound, therein ethylene, propylene account for 23v%, and water accounts for 72v%, and gas volume is big, and the gas products molecular-weight average is little, and the volumetric flow rate of product gas is big; Correspondingly, for regenerator system, 1) oxide compound conversion of olefines coking yield is low, has only the 1/3-1/4 of heavy oil product catalytic cracking; 2) conversion reaction requires regenerated catalyst need contain the carbon of deciding of 1-2wt%, and regenerated flue gas contains CO, and consumption wind index is low, and therefore, total regenerated flue gas amount is little.For instance, 1,800,000 tons of/year methanol-to-olefins (MTO) device, reactor are under 0.20-0.40MPa (a), 450-550 ℃ reaction conditions, and the long-pending flow of product gas that goes out reactor is 64.297m
3/ s; Revivifier 0.15MPa (g), under 680 ℃ the condition, going out the regenerator flue gas volume flow is 23.11m
3/ s, reactor product tolerance approaches 3 times regenerated flue gas amount, and therefore, olefin reaction has determined big reaction, little regeneration, and reactor is big more than revivifier.And for catalytic cracking unit, the regenerated flue gas volumetric flow rate is 2.4 times of reaction oil gas volumetric flow rate, and revivifier is big more than reactor.
In sum, because the conversion of olefines device has following different process characteristic with heavy oil catalytically cracking equipment, thereby need take different start-up methods:
1) two bodies are long-pending differs greatly, and reactor is much larger than revivifier, and is opposite fully with catalytic cracking unit;
2) the green coke amount is few, has determined the regeneration system rapidly of conversion of olefines device, comprises that the equipment that revivifier, main air blower, auxiliary chamber etc. match is all less, and greatly reducing goes into operation adds agent and heat-up rate.
3) during normal running, the catalyst recirculation amount between conversion reaction two devices is little, and the inclined tube of setting and guiding valve are also less, and not satisfying when going into operation goes into operation as catalytic cracking unit changes the requirement of agent to reactor by revivifier.
CN 1836027A discloses a kind of method of starting reactive system, this reactive system is to use and comprises molecular sieve, especially metalloaluminophosphate molecular sieve, those systems of the catalyzer of the metalloaluminophosphate molecular sieve of loss of catalytic activity especially easily owing to contact with water molecules.This method provides heating and has loaded activated molecular sieve so that prevent can be owing to contact the suitable means that the catalyst activity that takes place loses with water molecules.
CN 101130466A disclose a kind of by methyl alcohol or/and dme is produced the start-up method of the fluidization reaction unit of low-carbon alkene, comprise that utilizing the auxiliary thermal source that goes into operation that the beds of circulating fluidization catalyst reaction device is heated to more than 200 ℃ or 300 ℃ the back carries methyl alcohol or dme raw material to reactor, exothermic heat of reaction is rapidly heated to assigned temperature the reactive system device, thereby makes system reach normal operating condition rapidly.This method is applicable to the process that goes into operation of heat release type fluidization catalytic reaction device, can simplified apparatus and operation, save cost.
CN 1836027A provide know clearly heating with load activated molecular sieve so that prevent can be owing to contact the suitable means that the catalyst activity that takes place loses with water molecules, catalyzer contacts with water molecules and makes catalyst deactivation is to take place under the high temperature more than 600 ℃, is difficult for making catalyst deactivation under lower temperature; CN 101130466A is after temperature rises to more than 200 ℃ or 300 ℃, carry methyl alcohol or dme raw material to reactor, the method that the reactive system device is rapidly heated by means of exothermic heat of reaction, because the reactive system catalyst inventory is big, with the auxiliary thermal source that goes into operation the beds of two device systems is heated to and also need expends the long time more than 200 ℃ or 300 ℃, and regeneration system rapidly is also kept this temperature at this moment, burns and can't carry out and make.
Summary of the invention
The object of the present invention is to provide a kind of start-up method of conversion of olefines device, reactor, revivifier divide two-way to add agent, intensification separately, and can't help revivifier changes agent to reactor, and catalyst-free is carried between two devices.
The start-up method of conversion of olefines device of the present invention is achieved in that
The start-up method of conversion of olefines device of the present invention comprises the preheating and the transfer of catalyzer between reactor 2 and revivifier 3 that add catalyzer, catalyzer in reactor 2, revivifier 3, it is characterized in that:
When adding agent, can't help revivifier 3 to reactor 2 commentaries on classics agent, catalyst-free is carried between two devices.
In concrete enforcement,
The catalyzer temperature-elevating that described reactor 2, revivifier 3 add relies on the extraneous thermal source that is provided with separately separately and adds thermal medium;
Described reactor 2 is provided with the vapor superheater 1 that goes into operation, with the high-temperature steam heatable catalyst;
Described revivifier 3 is provided with auxiliary chamber 4, with the high temperature air heatable catalyst;
After the described vapor superheater 1 that goes into operation was superheated to 400-500 ℃ with vapor temperature, injecting reactor 2 direct heating added the catalyzer of reactor 2, and its temperature is risen to more than 350 ℃;
Wherein, superheated vapour provides heat for catalyzer temperature-elevating on the one hand; As fluidizing medium, drive the air in the reactor 2 away on the other hand.
Adding the agent initial stage, the catalyzer temperature-elevating that warm air makes revivifier 3 of adding of described auxiliary chamber 4 is higher than 300-350 ℃ and revivifier 3 inner catalyst material levels and reaches when flooding the combustion oil nozzle, revivifier 3 sprays into combustion oil, relies on the combustion oil heatable catalyst, heats up and adds agent speed and all accelerate; Or whole process using auxiliary chamber 4 is heated to the catalyzer of revivifier more than 550 ℃; Auxiliary chamber only heats the catalyzer that adds in the revivifier 3, and makes its intensification.
The superheat steam temperature that described reactor 2 is introduced, flow etc. need satisfy fluidisation superficial linear vilocity and intensification, add the requirement of agent speed.
Go into operation when adding agent, before guiding valve is not opened on the inclined tube, catalyzer such as the inclined tube to be generated of reactive system, reaction outside heat removing lower oblique tube do not circulate, inclined tube is loosening (to be annotated: in order to keep stable catalyst fluidisation and conveying, on inclined tube, introduce external gas at a certain distance, as steam, nitrogen, air etc.,, prevent to build bridge with loosening catalyzer.) medium adopts non-steam.
When the dress agent finished, reactor 2 temperature were not less than 350 ℃, revivifier 3 temperature and are not less than 550 ℃, and two devices all reach needed material level 0-50kPa, behind the 50-65%, open regeneration, guiding valve to be generated, rely on the pressure equilibrium of self, reach the catalyst recirculation between two devices; At this moment, the loosening normal loosening medium that is adopted that moves of device that switches to of inclined tube.
Described conversion of olefines device is comprising methanol-to-olefins (MTO) device and preparing propylene from methanol (MTP) device.
Effect of the present invention is:
1 the present invention adds the dosage difference because of reactor 2, revivifier 3, and the catalyzer of adding temperature eventually is different, therefore, adds agent speed, heat-up rate difference, separately adds agent and intensification, helps flexible control, reaches consistent on the time.
2 catalyzer temperature-elevatings of the present invention are owing to two different heat sources of employing provide, so heat-up rate is fast.
3 by above-mentioned 1,2 reason, the curtailment of operation of the present invention, avoids repeatedly changeing agent; And avoided reducing and " and mud ", thereby stopped up inclined tube to be generated by its reactor that causes 2 catalyzer Yin Wendu; Simultaneously, the race that also reduces reactor 2, revivifier 3 catalyzer in the process that goes into operation is decreased.
4 when going into operation reactor in the process, each self-chambering agent of revivifier, and guiding valve is not opened on the inclined tube, two device catalyzer do not circulate, and inclined tube is loosening to adopt non-steam medium, as air that can not condensation, nitrogen etc., avoided the inclined tube obstruction.
Description of drawings
Below in conjunction with accompanying drawing the present invention is described in further detail:
The synoptic diagram of the start-up method of a kind of conversion of olefines device of Fig. 1
Among the figure: 1, the vapor superheater that goes into operation; 2, reactor; 3, revivifier; 4, auxiliary chamber; 5, reactor 2 catalyst tank 5; 6, revivifier 3 catalyst tank 6;
11, steam 11; 12, superheated vapour 12; 13, methyl alcohol or dme charging 13; 14, reactor product gas 14; 15, reactor 2 catalyzer add agent 15; 16, reactor 2 catalyst unloadings 16; 21, air 21; 22, high temperature air 22; 23, regenerated flue gas 23; 24, revivifier 3 catalyzer add agent 24; 25, revivifier 3 catalyst unloadings 25; 31, reclaimable catalyst 31; 32, regenerated catalyst 33
Embodiment
When going into operation, after steam 11 is heated to 400-500 ℃ through the vapor superheater 11 that goes into operation, become superheated vapour 12, be injected into reactor 2, simultaneously, autoreactor 2 catalyst tank 5 add reactor 2 catalyzer 15 of normal temperature, reactor 2 catalyzer 15 and superheated vapour 12 thorough mixing in reactor 2 of normal temperature, reactor heating 2 catalyzer, and make it to heat up, in order to control heat-up rate, the superheated vapour amount with add agent speed and concern according to a certain percentage, and, need do correspondingly and adjust along with reactor 2 adds the carrying out of agent and temperature rise.Simultaneously, for revivifier 3 systems, after air 21 is heated to 700-750 ℃ through auxiliary chamber 4, become high temperature air 22, be injected into revivifier 3, simultaneously, the revivifier catalyzer 24 that adds normal temperature from revivifier 3 catalyst tank 6, revivifier catalyzer 24 and high temperature air 22 thorough mixing in revivifier 3 of normal temperature, the reboiler catalyzer, and make it to heat up.When reactor 2 and revivifier add agent, intensification separately, reclaimable catalyst 31 and regenerated catalyst 32 between two devices do not circulate, its guiding valve is crack, have only question response device 2, revivifier 3 all to add enough catalyzer and reach separately temperature reactor at end be not less than 350 ℃, when revivifier is not less than 550 ℃, just open guiding valve, control automatically comes into operation, make that catalyzer circulates, carries between two devices, after circulation is normal, after the automatic control stabilization of two devices material level separately, methyl alcohol or dme charging 13 come into operation.When device is stopped work, open reactor 2 catalyst unloadings 16 and revivifier catalyst unloading 25 and unload agent to reactor 2 catalyst tank 5, revivifier catalyst tank 6 respectively.
Claims (8)
1. the start-up method of a conversion of olefines device comprises the preheating and the transfer of catalyzer between reactor (2) and revivifier (3) that add catalyzer, catalyzer in reactor (2), revivifier (3), it is characterized in that:
Reactor (2), revivifier (3) catalyzer introduce, divide two-way to add agent from catalyst tank separately respectively;
When adding agent, can't help revivifier (3) to reactor (2) commentaries on classics agent, catalyst-free is carried between two devices.
2. the start-up method of conversion of olefines device as claimed in claim 1 is characterized in that:
The catalyzer temperature-elevating that described reactor (2), revivifier (3) add relies on the extraneous thermal source that is provided with separately separately and adds thermal medium;
Described reactor (2) is provided with the vapor superheater (1) that goes into operation, with the high-temperature steam heatable catalyst;
Described revivifier (3) is provided with auxiliary chamber (4), with the high temperature air heatable catalyst.
3. the start-up method of conversion of olefines device as claimed in claim 2 is characterized in that:
After the described vapor superheater that goes into operation (1) was superheated to 400-500 ℃ with vapor temperature, injecting reactor (2) direct heating added the catalyzer of reactor (2), and its temperature is risen to more than 350 ℃.
4. the start-up method of conversion of olefines device as claimed in claim 2 is characterized in that:
The catalyzer temperature-elevating that warm air makes revivifier (3) of adding of described auxiliary chamber (4) is higher than 300-350 ℃ and revivifier (3) inner catalyst material level and reaches when flooding the combustion oil nozzle, revivifier (3) sprays into combustion oil, rely on the combustion oil heatable catalyst, heat up and add agent speed and all accelerate; Or whole process using auxiliary chamber (4) is heated to the catalyzer of revivifier more than 550 ℃.
5. the start-up method of conversion of olefines device as claimed in claim 2 is characterized in that:
The superheated vapour that described reactor (2) is introduced is as extraneous thermal source and add thermal medium.
6. the start-up method of conversion of olefines device as claimed in claim 1 is characterized in that:
Go into operation when adding agent, before guiding valve was not opened on the inclined tube, catalyzer did not circulate in the inclined tube to be generated of reactive system, the reaction outside heat removing lower oblique tube, and the loosening medium of inclined tube adopts non-steam.
7. as the start-up method of claim 3 or 4 described conversion of olefines devices, it is characterized in that:
When the dress agent finished, reactor (2) temperature was not less than 350 ℃, revivifier (3) temperature and is not less than 550 ℃, and two devices all reach 0-50kPa, behind the material level 50-65%, open regeneration, guiding valve to be generated, rely on the pressure equilibrium of self, reach the catalyst recirculation between two devices; At this moment, the loosening medium of inclined tube switches to the loosening medium of the normal operation of device.
8. the start-up method of conversion of olefines device as claimed in claim 1 is characterized in that:
Described conversion of olefines device is comprising methanol-to-olefins device and preparing propylene from methanol device.
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Cited By (15)
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| CN102863307A (en) * | 2012-07-23 | 2013-01-09 | 李小燕 | Methanol-to-olefin operating method and process |
| CN103193574A (en) * | 2012-01-10 | 2013-07-10 | 中国石油化工股份有限公司 | On-stream method of methanol to light olefin reaction-regeneration device |
| CN103588607A (en) * | 2012-08-15 | 2014-02-19 | 神华集团有限责任公司 | Alkene conversion apparatus start-working catalyst adding method |
| CN103588606A (en) * | 2012-08-15 | 2014-02-19 | 神华集团有限责任公司 | Work-starting method of apparatus for producing low carbon alkene from methanol |
| CN103666528A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Work starting method for catalytic cracking unit |
| CN103666530A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Work starting method for catalytic cracking unit |
| CN103666529A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Fresh catalyst adopted work starting method for catalytic cracking unit |
| CN103666525A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Fresh catalyst adopted work starting method for catalytic cracking unit |
| CN103666534A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Work starting method for catalytic cracking unit |
| CN103666532A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Fresh catalyst adopted work starting method for catalytic cracking unit |
| CN103666526A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Work starting method for catalytic cracking unit |
| CN103666533A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Fresh catalyst adopted work starting method for catalytic cracking unit |
| CN105983379A (en) * | 2015-01-28 | 2016-10-05 | 中国石化工程建设有限公司 | Starting method of apparatus for catalytically converting organic oxides to produce aromatic hydrocarbons |
| CN109456137A (en) * | 2018-11-01 | 2019-03-12 | 国家能源投资集团有限责任公司 | Methanol to olefins reaction-regeneration system stops start-up method |
| CN114456023A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Method for starting fluidized bed device for preparing aromatic hydrocarbon from oxygen-containing compound |
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| CN103193574A (en) * | 2012-01-10 | 2013-07-10 | 中国石油化工股份有限公司 | On-stream method of methanol to light olefin reaction-regeneration device |
| CN103193574B (en) * | 2012-01-10 | 2015-01-07 | 中国石油化工股份有限公司 | On-stream method of methanol to light olefin reaction-regeneration device |
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| CN103666525A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Fresh catalyst adopted work starting method for catalytic cracking unit |
| CN103666533B (en) * | 2012-09-20 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of method that catalytic cracking unit adopts live catalyst to go into operation |
| CN103666532A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Fresh catalyst adopted work starting method for catalytic cracking unit |
| CN103666526A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Work starting method for catalytic cracking unit |
| CN103666533A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Fresh catalyst adopted work starting method for catalytic cracking unit |
| CN103666529A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Fresh catalyst adopted work starting method for catalytic cracking unit |
| CN103666525B (en) * | 2012-09-20 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of method that catalytic cracking unit adopts live catalyst to go into operation |
| CN103666532B (en) * | 2012-09-20 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of method that catalytic cracking unit adopts live catalyst to go into operation |
| CN103666534B (en) * | 2012-09-20 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of catalytic cracking unit start-up method |
| CN103666528B (en) * | 2012-09-20 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of catalytic cracking unit start-up method |
| CN103666526B (en) * | 2012-09-20 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of catalytic cracking unit start-up method |
| CN103666534A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Work starting method for catalytic cracking unit |
| CN103666529B (en) * | 2012-09-20 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of method that catalytic cracking unit adopts live catalyst to go into operation |
| CN103666530B (en) * | 2012-09-20 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of catalytic cracking unit start-up method |
| CN103666530A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Work starting method for catalytic cracking unit |
| CN103666528A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Work starting method for catalytic cracking unit |
| CN105983379A (en) * | 2015-01-28 | 2016-10-05 | 中国石化工程建设有限公司 | Starting method of apparatus for catalytically converting organic oxides to produce aromatic hydrocarbons |
| CN105983379B (en) * | 2015-01-28 | 2019-01-25 | 中国石化工程建设有限公司 | A kind of start-up method of organic oxide catalytic cracking aromatic device |
| CN109456137A (en) * | 2018-11-01 | 2019-03-12 | 国家能源投资集团有限责任公司 | Methanol to olefins reaction-regeneration system stops start-up method |
| CN109456137B (en) * | 2018-11-01 | 2021-03-02 | 国家能源投资集团有限责任公司 | Work stopping and starting method of methanol-to-olefin reaction-regeneration system |
| CN114456023A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Method for starting fluidized bed device for preparing aromatic hydrocarbon from oxygen-containing compound |
| CN114456023B (en) * | 2020-10-21 | 2024-03-26 | 中国石油化工股份有限公司 | Method for starting fluidized bed device for preparing aromatic hydrocarbon from oxygen-containing compound |
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