CN102020523B - Operating method for olefin conversion device - Google Patents
Operating method for olefin conversion device Download PDFInfo
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- CN102020523B CN102020523B CN2009101702744A CN200910170274A CN102020523B CN 102020523 B CN102020523 B CN 102020523B CN 2009101702744 A CN2009101702744 A CN 2009101702744A CN 200910170274 A CN200910170274 A CN 200910170274A CN 102020523 B CN102020523 B CN 102020523B
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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
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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 the 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 multiple important chemical and the raw material of polymkeric substance.Light olefin is produced by the petroleum cracking typically, limited supply due to competitive petroleum, and international price is increasingly surging, 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 day by day urgent, and the more and more important effect of performance.
Important alternative materials for the production of light olefin is 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 biomass derived raw material, Sweet natural gas, petroleum liquid also comprise by coal, recycled plastic, urban waste or the synthetic gas that contains the carbonaceous material of any organic materials etc. and producing.Due to wide material sources, the non-petroleums such as alcohol, alcohol derivate and other oxygenatedchemicals have wide economic outlook as olefin production.
Oxygenatedchemicals conversion of olefines technique is take oxygenatedchemicals as raw material, 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 occurs, with the processing method of preparing low-carbon olefins etc.Similar with the catalytic cracking process of maturation, conversion reaction and catalyzer coke burning regeneration carry out continuously, and the catalyzer after the continuous compensation regeneration of reactor is kept catalyst activity and product selectivity stable, and conversion reaction is steadily carried out.
Existing catalytic cracking unit start-up process is:
1) catalyzer in reactor, regenerator system all adds from revivifier, is adding the agent initial stage, relies on auxiliary chamber to add warm air and makes the catalyzer temperature-elevating that adds, and the top temperature that auxiliary chamber adds warm air generally is no more than 780 ℃; When in revivifier just the catalyzer material level of dress reach when flooding the combustion oil nozzle, and temperature sprays into combustion oil during 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 ℃, turn agent to reactor.
3) turn for the first time agent and complete after, close guiding valve, revivifier continues to add agent, heats up.
4) after revivifier catalyzer material level, temperature touch the mark, open guiding valve, turn for the second time agent.Because the revivifier space is more much larger than space reactor, only need first and second to turn agent, just can set up the catalyst recirculation between revivifier-reactor.The timed interval that turns agent for twice should be as far as possible short, relies on the steam fluidisation because change the thermocatalyst of reactor over to, and temperature can not cause catalyzer " and mud " slowly reducing.
5) start-up process of any device is all relative erratic process, can cause that the race of system catalyst is damaged, 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 complete in 4-8 hour to reaching feed conditions (be catalyzer material level and temperature touch the mark requirement) from adding agent.Different from the heavy oil product catalytic cracking unit, in the conversion of olefines device, oxygenatedchemicals conversion of olefines gas product is gone back a large amount of water of by-product and a small amount of C except the 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 large, and the gas products molecular-weight average is little, and the volumetric flow rate of gas product is large; Correspondingly, for regenerator system, 1) oxide compound conversion of olefines coking yield is low, only has 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 ton/years of methanol-to-olefins (MTO) device, reactor is under the reaction conditions of 0.20-0.40MPa (a), 450-550 ℃, and the gas product volume flow that goes out reactor is 64.297m
3/ s; Revivifier 0.15MPa (g), under the condition of 680 ℃, going out the regenerator flue gas volume flow is 23.11m
3/ s, reactor product tolerance is close to the regenerated flue gas amount of 3 times, and therefore, olefin reaction has determined large reaction, little regeneration, and reactor is large 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 large more than reactor.
In sum, because conversion of olefines device and heavy oil catalytically cracking equipment have following different process characteristic, thereby need to take different start-up methods:
1) two bodies are long-pending differs greatly, and reactor is much larger than revivifier, and is fully opposite 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 inclined tube and the guiding valve of setting are also less, and can not meet goes into operation as catalytic cracking unit when going into operation turns 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 to comprise molecular sieve, especially metalloaluminophosphate molecular sieve, especially easily those systems of the catalyzer of the metalloaluminophosphate molecular sieve of loss of catalytic activity owing to contacting with water molecules.The method provides heating and has loaded activated molecular sieve so that prevent can be due to the suitable means that contacts catalyst activity that occurs with water molecules and lose.
CN 101130466A disclose a kind of by methyl alcohol or/and the start-up method of the fluidization reaction unit of dme preparing low-carbon olefins, 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 ℃ backward reactor carries methyl alcohol or dme raw material, exothermic heat of reaction is rapidly heated to assigned temperature the reactive system device, thereby makes system reach rapidly normal operating condition.This method is applicable to the start-up process 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 due to the suitable means that contacts catalyst activity that occurs with water molecules and lose, catalyzer contacts with water molecules and makes catalyst deactivation is to occur under the high temperature more than 600 ℃, is difficult for making catalyst deactivation at 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 large, 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 separately agent, intensification, can't help revivifier to turn agent to reactor, and between two devices, catalyst-free is carried.
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, the revivifier 3, it is characterized in that:
When adding agent, can't help revivifier 3 and turn agent to reactor 2, between two devices, catalyst-free is carried.
In concrete enforcement,
The catalyzer temperature-elevating that described reactor 2, revivifier 3 add relies on the extraneous thermal source that arranges separately separately and adds thermal medium;
Described reactor 2 arranges the vapor superheater 1 that goes into operation, with the high-temperature steam heatable catalyst;
Described revivifier 3 arranges 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 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 reaches when flooding the combustion oil nozzle higher than 300-350 ℃ and revivifier 3 inner catalyst material levels, 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 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 on inclined tube, guiding valve is not opened, the 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 fluidization and conveying, introduce at a certain distance external gas on inclined tube, as steam, nitrogen, air etc., with loosening catalyzer, prevent from building bridge.) the non-steam of medium employing.
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, after 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 adopts 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 is because reactor 2, revivifier 3 add the dosage difference, and the catalyzer final temperature that adds is different, therefore, adds agent speed, heat-up rate difference, separately adds agent and intensification, is conducive to flexible control, reaches consistent on the time.
2 catalyzer temperature-elevatings of the present invention are because 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 turning agent; And avoided being reduced and " and mud " by its reactor that causes 2 catalyzer Yin Wendu, thereby stopped up inclined tube to be generated; Simultaneously, the race that also reduces reactor 2 in start-up process, revivifier 3 catalyzer is damaged.
In 4 start-up process when reactor, each self-chambering agent of revivifier, on inclined tube, guiding valve is not opened, two device catalyzer do not circulate, and inclined tube is loosening adopts non-steam medium, as air that can not condensation, nitrogen etc., has avoided the inclined tube obstruction.
Description of drawings
Below in conjunction with accompanying drawing, the present invention is described in further detail:
The schematic diagram of the start-up method of a kind of conversion of olefines device of Fig. 1
In 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 of normal temperature and superheated vapour 12 fully mix reactor 2 is interior, 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 relation according to a certain percentage, and the carrying out that adds agent and temperature rise along with reactor 2 need to be cooked correspondingly and adjust.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, the revivifier catalyzer 24 of normal temperature and high temperature air 22 fully mix revivifier 3 is interior, 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, only have question response device 2, revivifier 3 all to add enough catalyzer and reach separately final temperature reactor be not less than 350 ℃, when revivifier is not less than 550 ℃, just open guiding valve, come into operation and automatically control, make that between two devices, catalyzer circulates, carries, after circulation is normal, after two devices material level was separately automatically controlled and stablized, methyl alcohol or dme charging 13 came 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 (5)
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), the revivifier (3), it is characterized in that:
Reactor (2), revivifier (3) catalyzer introduce, divide a two-way to add agent from catalyst tank separately respectively;
When adding agent, can't help revivifier (3) and turn agent to reactor (2), between two devices, catalyst-free is carried;
Described reactor (2) arranges the vapor superheater (1) that goes into operation, and with the high-temperature steam heatable catalyst, the superheated vapour that described reactor (2) is introduced is as extraneous thermal source and add thermal medium;
Described revivifier (3) arranges auxiliary chamber (4), with the high temperature air heatable catalyst;
The temperature of described high-temperature steam is 400 ℃ to 500 ℃, and the temperature of described high temperature air is 700 ℃ to 750 ℃;
Go into operation when adding agent, before on inclined tube, guiding valve was not opened, in the inclined tube to be generated of reactive system, reaction outside heat removing lower oblique tube, catalyzer did not circulate, and the loosening medium of inclined tube adopts non-steam;
Described conversion of olefines device is comprising the methanol-to-olefins device.
2. the start-up method of conversion of olefines device as claimed in claim 1 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 ℃.
3. the start-up method of conversion of olefines device as claimed in claim 1 is characterized in that:
The catalyzer temperature-elevating that warm air makes revivifier (3) of adding of described auxiliary chamber (4) reaches when flooding the combustion oil nozzle higher than 300-350 ℃ and revivifier (3) inner catalyst material level, 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 ℃.
4. the start-up method of conversion of olefines device as claimed in claim 2 or claim 3 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, after 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.
5. the start-up method of conversion of olefines device as claimed in claim 1 is characterized in that:
Described conversion of olefines device comprises the preparing propylene from methanol device.
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| CN2009101702744A CN102020523B (en) | 2009-09-10 | 2009-09-10 | Operating method for olefin conversion device |
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| CN2009101702744A CN102020523B (en) | 2009-09-10 | 2009-09-10 | Operating method for olefin conversion device |
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| CN102020523B true CN102020523B (en) | 2013-06-05 |
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102863307A (en) * | 2012-07-23 | 2013-01-09 | 李小燕 | Methanol-to-olefin operating method and process |
| CN103588607B (en) * | 2012-08-15 | 2015-12-02 | 神华集团有限责任公司 | A kind of olefin conversion apparatus catalyzer that goes into operation adds agent method |
| CN103588606B (en) * | 2012-08-15 | 2015-10-28 | 神华集团有限责任公司 | A kind of start-up method of preparing light olefins from methanol device |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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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