CN105983455B - A kind of regeneration method of organic oxide catalytic cracking arenes catalytic agent - Google Patents
A kind of regeneration method of organic oxide catalytic cracking arenes catalytic agent Download PDFInfo
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- CN105983455B CN105983455B CN201510041973.4A CN201510041973A CN105983455B CN 105983455 B CN105983455 B CN 105983455B CN 201510041973 A CN201510041973 A CN 201510041973A CN 105983455 B CN105983455 B CN 105983455B
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Abstract
The invention discloses a kind of regeneration methods of organic oxide catalytic cracking arenes catalytic agent, this method comprises: will contact from the reclaimable catalyst of organic oxide catalyst conversion for preparing arene reaction system the first regenerator of feeding with the main wind of oxygen deprivation again and again and regenerated again and again, semi regeneration catalyst and the first regenerated flue gas are obtained；By the semi regeneration catalyst be sent into Second reactivator with two again the main wind of oxygen deprivation contact and carry out two and regenerate；Wherein, by volume, the oxygen content of the main wind of the oxygen deprivation again and again and described two main wind of oxygen deprivation again is below the oxygen content of air.The regeneration method of organic oxide catalytic cracking arenes catalytic agent of the invention is compared with existing regeneration method, this method can effectively increase regenerator volume, guarantee the char length of reclaimable catalyst and burn effect, may also adapt to the different treating capacity of reactor and green coke amount.
Description
Technical field
The present invention relates to a kind of regeneration methods of organic oxide catalytic cracking arenes catalytic agent.
Background technique
Aromatic hydrocarbons is a kind of important organic chemical industry's basic material, wherein benzene, toluene and dimethylbenzene (including ortho-xylene,
Dimethylbenzene and paraxylene) purposes is very extensive, the application of end product include synthetic resin, synthetic fibers, synthetic rubber,
Coating, dyestuff and medicine and other fields.With China's socio-economic development, the demand to aromatic hydrocarbons is also growing, and China is every at present
The consumption figure of year aromatic hydrocarbons is more than 20,000,000 tons, has half need to be from external import.
Benzene, toluene and dimethylbenzene are mainly derived from petrochemical industry, and domestic petroleum chemical industry route production aromatic hydrocarbons accounts for about virtue
85% or more hydrocarbon production, production technology specifically include that naphtha catalytic reforming, cracking of ethylene petroleum naphtha hydrogenation extracting and it is low
Carbon aromatization of hydrocarbons etc., wherein naphtha catalytic reforming aromatic production accounts for about petrochemical industry route aromatic production 80%, and ethylene is split
Solution petroleum naphtha hydrogenation extracting aromatic production accounts for about 16%.Increasingly depleted with petroleum resources, crude oil price is high, gives stone
Oiling work route preparing aromatic hydrocarbon brings biggish cost pressure.The Energy Situation in China is the few oily deficency of more coals, 20th century 90
With economic sustainable growth since age, China's external oil dependency degree is continuously increased, and 1993 to 1996, China was external
Petroleum dependency degree reached 50.5% more than 30%, 2007 year for the first time substantially within 10%, by 2000, reached within 2013
57.39%, far more than 30% generally acknowledged in the world warning line.On the other hand, rich coal resources in China, in recent years in state's housekeeping
Under plan is supported, ammonia from coal, dimethyl ether and ethylene glycol industry are rapidly developed, according to statistics China's methanol output nearly 29,000,000 in 2013
Ton.Therefore, develop organic oxide catalytic cracking aromatic hydrocarbons technology to substitute traditional petrochemical industry route, aromatic hydrocarbons can be reduced
To the dependency degree of petroleum, there is important role to Chinese energy safety and aromatics production industry.
Using the technology of organic oxide catalytic cracking aromatic hydrocarbons, proposed in early days by Mobil Oil Corporation, the U.S., 1979
The patent US4156698A of year application, which is disclosed, utilizes the composite catalyst containing molecular sieve by C1-C4 alcohols or ether compound
The method for being converted into low-carbon alkene and aromatic hydrocarbons；It is proposed in the patent US4590321A of application in 1985 and utilizes ZSM-5 or ZSM-
11 wait molecular sieve catalysts by C2-C12Alkane, C2-C12Alkene, C1-C5Alcohols and C2-C12The non-aromatic compound such as ethers is converted into virtue
The technique of hydrocarbon；United States Patent (USP) US4686312A, US4724270A, US4822939A, US4822939A, US4049573A etc. are also public
The method of methanol or dimethyl ether aromatic hydrocarbons under different catalysts effect is opened.But the emphasis of these United States Patent (USP)s, which essentially consists in, to be ground
Study carefully the influence of catalyst composition and operation condition to aromatics conversion rate and selectivity, individual patents propose methanol or diformazan
The reaction process of ether aromatic hydrocarbons, but without clearly proposing the reaction-regeneration system of organic oxide aromatic hydrocarbons technology, reacting again
Generation method and reactor and regenerator pattern.
Currently, Ye Youduojia institute, the country researches and develops organic oxide aromatic hydrocarbons technology, it mainly include Tsing-Hua University
University, Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences, Sinopec Shanghai Petroleum Chemical Engineering Institute, the big fluidization of the Chinese Academy of Sciences
Learn physics Institute etc..Chinese patent CN 1880288A, which is disclosed, to be made using methanol as raw material in ZSM-5 Type Zeolites agent
With the technique of lower aromatic hydrocarbons processed, which will isolate low-carbon hydro carbons and liquid after the cooling of first stage reactor aromatization of methanol gas-phase product
Phase product, liquid product obtain aromatic hydrocarbons and non-aromatics through extraction and separation, and low-carbon hydro carbons enters the further aromatisation of second stage reactor,
To improve the overall selectivity of aromatic hydrocarbons.101823929 B of Chinese patent CN proposes a kind of methanol or dimethyl ether preparing aromatic hydrocarbon
System and technique, methanol or dimethyl ether are first reacted in aromatization reactor, hydrogen, methane, mixing C in reaction product8Aromatic hydrocarbons and
Part C9+Hydro carbons is as product, C2+Non-aromatics and except mixing C8Aromatic hydrocarbons and part C9+Aromatic hydrocarbons except hydro carbons can be then recycled into separately
One further aromatisation of reactor, improves the yield and selectivity of aromatic hydrocarbons.Chinese patent CN 101607858 B, CN
102190546 B, CN 102371176 B, CN 102371177 B etc. also individually disclose organic oxide catalytic cracking virtue
Hydrocarbon technique, organic oxide catalytic cracking arenes catalytic agent and preparation method.Above-mentioned patent equally focuses on that investigating difference urges
Agent composition and rare metal, the rare-earth metal modified influence to aromatization process, CN 1880288A and CN 101823929
B mainly proposes influence of the reaction product circulation aromatisation to aromatics yield.
It is big to go back by-product other than the aromatic hydrocarbons such as benzene, toluene and dimethylbenzene for organic oxide catalytic cracking aromatic hydrocarbons reactor product
The low-carbon alkenes, C such as the water and ethylene of amount, propylene5+Gasoline and organic oxide, gas flow is big, and gas products average molecular weight is small,
The volume flow of reaction process gas is big；Correspondingly, organic oxide aromatization process coking yield is very low, only heavy oil catalytic cracking
1/10th or so, for the hydrothermal deactivation for reducing catalyst, organic oxide catalytic cracking aromatic hydrocarbons regenerative system is not using
It regenerates completely, CO is contained in regenerated flue gas, consumption wind index is low, and therefore, regenerated flue gas volume flow is small, and reactor process tolerance is about
It is 8 times of regenerator flue gas amount.Therefore, organic oxide aromatization reaction regeneration feature determines reactor much larger than regeneration
Device.
Since regenerated flue gas amount is low, for the fluidized state for keeping catalyst in regenerator, regenerator diameter only has reactor
The 1/4~1/3 of diameter；On the other hand, the coke feature of organic oxide catalytic cracking aromatics production determines catalysis to be generated
Agent must have enough residence times, and the coke of the completely burned off reclaimable catalyst entrainment of ability, this requires regenerator volume must again
Palpus is sufficiently large；So that regenerator may be not only thin but also long, dense-phase bed height is very high, causes to burn to be exported with main wind and press
Power increases, reactor and regenerator facade arrange the problems such as having difficulties.
Chinese patent CN 103657744A discloses catalyst regenerator and the regeneration side of a kind of aromatization of methanol process
Method is axially arranged one to multiple lateral perforated baffles in the regenerated fluidized bed of multistage, forms two or more accumulation catalyst
Emulsion zone.Heat exchanger is set in one or more catalyst emulsion zones, control each emulsion zone operation temperature along it is axial (from
It is low to high) operation of the alternating temperature that gradually decreases；Inert gas decanting point, injection are set in one or more catalyst emulsion zones simultaneously
One of nitrogen, argon gas and helium are a variety of, and inert gas volume burns 0.05~1 with oxygen-containing gas volume for regenerator
Times, main function is that removing enters the regenerated flue gas that carries in reaction system regenerated catalyst, reduce in reactor CO2, CO and
The generation of fatty acid by-product.The injection rate that inert gas is injected in the invention is less, influences on regenerator volume little.
Summary of the invention
The object of the present invention is to provide a kind of regeneration method of organic oxide catalytic cracking arenes catalytic agent, this method
Regenerator volume can be effectively increased, guarantee the char length of reclaimable catalyst and burns effect, may also adapt to reactor not
Same treating capacity and green coke amount.
To achieve the goals above, the present invention provides a kind of regeneration side of organic oxide catalytic cracking arenes catalytic agent
Method, this method comprises: by the first regeneration is sent into from the reclaimable catalyst of organic oxide catalyst conversion for preparing arene reaction system
Device is contacted with the main wind of oxygen deprivation again and again and is regenerated again and again, obtains semi regeneration catalyst and the first regenerated flue gas；By it is described partly again
Raw catalyst be sent into Second reactivator with two again the main wind of oxygen deprivation contact and carry out two and regenerate, obtain regenerated catalyst and second again
Raw flue gas；The regenerated catalyst is sent back in organic oxide catalytic cracking aromatic hydrocarbons reaction system；Wherein, with volume
The oxygen content of meter, the main wind of the oxygen deprivation again and again and described two main wind of oxygen deprivation again is below the oxygen content of air.
Preferably, wherein the organic oxide is selected from C1-C10Alcohols, C2-C12Ethers and C3-C12In ketone extremely
Few one kind；The catalyst is the microspherical catalyst containing molecular sieve and carrier.
Preferably, wherein controlling the temperature regenerated again and again is 500-700 DEG C；Control described two regenerated temperature again
It is 600-800 DEG C.
Preferably, wherein the protium weight for controlling coke contained by the semi regeneration catalyst is the reclaimable catalyst
The 0-40 weight % of the protium weight of contained coke, it is described for controlling the carbon weight of coke contained by the semi regeneration catalyst
The 10-50 weight % of the carbon weight of coke contained by reclaimable catalyst；The content for controlling coke in the regenerated catalyst is
0.01-0.1 weight %.
Preferably, wherein this method further include: air is mixed with inert gas, obtains the main wind of total oxygen deprivation, it will be described total
The main wind of oxygen deprivation is divided into the main wind of oxygen deprivation again and again and described two main wind of oxygen deprivation again；The main wind of oxygen deprivation again and again is sent into described first
It, will be in described two again the oxygen deprivation main wind feeding Second reactivator in regenerator；The inert gas be selected from nitrogen, argon gas,
At least one of helium, carbon dioxide and flue gas, the flue gas are selected from first regenerated flue gas, the second regeneration cigarette
The mixture of gas and the first regenerated flue gas and the second regenerated flue gas after further burning in resulting gas at least one
Kind.
Preferably, wherein in terms of the volume under uniform pressure, the flow of the control main wind of oxygen deprivation again and again accounts for described total poor
The flow of the 5-95 body % of oxygen main airstream amount, the described two main wind of oxygen deprivation again of control account for the 5-95 of total oxygen deprivation main airstream amount
Body %.
Preferably, wherein in terms of the volume under uniform pressure, the flow of the control main wind of oxygen deprivation again and again accounts for described total poor
The flow of the 35-45 body % of oxygen main airstream amount, the described two main wind of oxygen deprivation again of control account for the 55-65 of total oxygen deprivation main airstream amount
Body %.
Preferably, wherein by volume, in total main wind of oxygen deprivation, the content of the inert gas is greater than 0 to 99.9
Body %.
Preferably, wherein according to the temperature regenerated again and again and/or described two again the adjustment of regenerated temperature it is described total poor
The temperature of the main wind of oxygen is 100-1000 DEG C.
Preferably, wherein the main wind of oxygen deprivation again and again is passed through into one or more oxygen deprivation main air distributors and is sent into described the
For regenerating in one regenerator, and/or will described two again the main wind of oxygen deprivation pass through one or more oxygen deprivation main air distributors feedings the
For regenerating in two regenerators；The oxygen deprivation main air distributor is selected from dendroid distributor pipe, ring type distributor pipe, porous type distribution
At least one of plate and cone hat type distribution rings.
Preferably, wherein first regenerator and the Second reactivator is set side by side；It is revolved by least one set of two-stage
The semi regeneration catalyst is separated with first regenerated flue gas and will be described in first regenerated flue gas submitting by wind separator
First regenerator；The regenerated catalyst is separated simultaneously with second regenerated flue gas by least one set of two stage cyclone separator
Second regenerated flue gas is sent out into the Second reactivator.
Preferably, wherein regenerate first regenerated flue gas sent out from first regenerator with from described second
It burns after second regenerated flue gas mixing that device is sent out, obtains combustion product gases and carry out energy regenerating.
Preferably, first regenerator and the Second reactivator are overlapped up and down and the setting of the first regenerator is the
Above two regenerators, and the junction of the first regenerator and Second reactivator is configured to only allow a small amount of catalyst of entrainment
Gas passes through；Second regenerated flue gas for carrying a small amount of regenerated catalyst secretly is fed to the bottom of first regenerator, with
The main wind of oxygen deprivation again and again is used for the described of the first regenerator together and regenerates again and again.
Preferably, wherein first regenerated flue gas is passed through at least one set of two stage cyclone separator and the semi regeneration
The first regenerator is sent out after catalyst separation.
The regeneration method of organic oxide catalytic cracking arenes catalytic agent provided by the invention has the advantages that
1, to organic oxide catalytic cracking aromatic hydrocarbons regenerative system topping up, regeneration body can be effectively increased
Long-pending and catalyst residence times guarantee the char length of reclaimable catalyst and burn effect, it is different to may also adapt to reactor
Treating capacity and green coke amount；
2, organic oxide catalytic cracking aromatic hydrocarbons regenerative system topping up, regenerator diameter increase, can subtract
Few catalyst dense-phase bed height reduces the energy consumption of main air blower to reduce the outlet pressure of main air blower；
3, the inlet velocity and separative efficiency for maintaining cyclone separator reduce expensive aromatized catalyst and run damage, reduce
Operating cost；
4, the heater of total main wind of oxygen deprivation is set, can satisfy the demand of going into operation and treating capacity and green coke amount changes
When regenerator heat balance, maintain the first regenerator and Second reactivator operation temperature, it is ensured that catalyst regeneration effect.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is organic oxide catalytic cracking aromatic hydrocarbons used by a kind of specific embodiment of regeneration method of the present invention
The regenerative system (i.e. eclipsed form regenerative system) of catalyst；
Fig. 2 is organic oxide catalytic cracking virtue used by another specific embodiment of regeneration method of the present invention
The regenerative system (i.e. block form regenerative system) of hydrocarbon catalyst.
Description of symbols
1 first regenerator, 2 Second reactivator, 3 main air blower, 4 heater
5 semi regeneration inclined tube, 6 semi regeneration slide valve, 7 oxygen deprivation main air distributor
8 oxygen deprivation main air distributor, 9 primary cyclone, 10 secondary cyclone
The main 14 main wind of total oxygen deprivation of wind of 11 air, 12 inert gas 13
The 15 main wind 16 2 of oxygen deprivation main 17 flue gases of wind of oxygen deprivation again again and again
18 first regenerated flue gas, 19 second regenerated flue gas
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of regeneration method of organic oxide catalytic cracking arenes catalytic agent, this method comprises: will
Reclaimable catalyst from organic oxide catalytic cracking aromatic hydrocarbons reaction system is sent into the first regenerator and the main wind of oxygen deprivation again and again
It contacts and is regenerated again and again, obtain semi regeneration catalyst and the first regenerated flue gas；The semi regeneration catalyst is sent into second
Regenerator with two again the main wind of oxygen deprivation contact and carry out two and regenerate, obtain regenerated catalyst and the second regenerated flue gas；By described in again
Raw catalyst sends back in organic oxide catalytic cracking aromatic hydrocarbons reaction system；Wherein, by volume, the oxygen deprivation master again and again
The oxygen content of wind and described two main wind of oxygen deprivation again is below the oxygen content of air.
According to the present invention, the organic oxide and the catalyst for organic oxide catalytic cracking aromatic hydrocarbons are this
Known to the technical staff of field, for example, the organic oxide can be for selected from C1-C10Alcohols, C2-C12Ethers and C3-C12Ketone
At least one of class；The catalyst can be the microspherical catalyst containing molecular sieve and carrier, and the molecular sieve is preferably
ZSM-5 molecular sieve.
Since in high temperature and high steam partial pressure, hydrothermal deactivation is more for organic oxide catalytic cracking arenes catalytic agent
Obviously, therefore first regenerator is to be operated using the oxygen deprivation of the first oxygen-containing gas, can control the temperature regenerated again and again
Be 500-700 DEG C, and since the burning velocity of Hydrogen In The Coke is far longer than the burning velocity of carbon, reclaimable catalyst first again
It gives birth under the regeneration condition that device more mitigates, the carbon of 50 weight %-90 weight % and 60 weight %-100 in coke can be burnt up and weigh %'s
Protium, although most of protium is burnt up in the first regenerator becomes water vapour, due to lower, the Ke Yiyou that burns temperature
Effect reduces the hydrothermal deactivation of catalyst.Second reactivator is the oxygen-enriched operation using the second oxygen-containing gas, can control described two
Regenerated temperature is 600-800 DEG C again, and regeneration condition is than the first regenerator harshness, since Hydrogen In The Coke element is in the first regenerator
Completely, Second reactivator can be under conditions of high temperature low steam partial pressure by catalyst 10 heavy %-50 for interior basic burning
The protium completely burned of the carbon of weight % and 0 weight %-40 weight %, to reduce the hydrothermal deactivation of catalyst, it can control
The protium weight of coke contained by the semi regeneration catalyst is the 0- of the protium weight of coke contained by the reclaimable catalyst
40 heavy %, the carbon weight that can control coke contained by the semi regeneration catalyst is coke contained by the reclaimable catalyst
The 10-50 weight % of carbon weight；And the content for preferably controlling coke in the regenerated catalyst is 0.01-0.1 weight %.
Method of the invention can also include: to mix air with inert gas, obtain the main wind of total oxygen deprivation, will be described total poor
The main wind of oxygen is divided into the main wind of oxygen deprivation again and again and described two main wind of oxygen deprivation again；The main wind of oxygen deprivation again and again is sent into described first again
It, will be in described two again the oxygen deprivation main wind feeding Second reactivator in raw device；The inert gas can be for selected from nitrogen, argon
At least one of gas, helium, carbon dioxide and flue gas, the flue gas can be for selected from first regenerated flue gas, described the
The mixture of two regenerated flue gas and the first regenerated flue gas and the second regenerated flue gas is after further burning in resulting gas
It is at least one.
A kind of specific embodiment according to the present invention, as shown in Figure 1, air 11 becomes main wind after the compression of main air blower 3
13, then the main wind 14 of total oxygen deprivation is mixed into inert gas 12；Total main wind 14 of oxygen deprivation is divided into two-way after heating up into heater 4, again and again
The main wind of oxygen deprivation 15 and two the main wind 16 of oxygen deprivation respectively enters the first regenerator 1 again and Second reactivator 2 is burnt；First regenerator, 1 He
Second reactivator 2 burn after flue gas through cyclone separator recycling entrainment catalyst after, flow out the first regenerator 1.Wherein, lazy
The volume flow of property gas 12 can be 0-100 times of 13 volume flow of wind based on, by volume, in total main wind of oxygen deprivation, institute
The content for stating inert gas can be for greater than 0 to 99.9 body %, preferably 10-70 body %, and makes the first regenerator 1 and second
The dense-phase bed of regenerator 2 maintains certain reserve to guarantee that coke burning degree and the gas flow rate in it are the left side 0.2-1.5m/s
The right side, guarantee catalyst burn effect and fluidized state is good；Simultaneously as supplementing suitable inert gas, can control
Primary cyclone 9 and 10 inlet velocity of secondary cyclone within the appropriate range, maintain the separation of cyclone separator
Efficiency reduces catalyst stack less.In terms of the volume under uniform pressure, can control the main wind of oxygen deprivation again and again flow account for it is described
The 5-95 body % of total oxygen deprivation main airstream amount, the flow that can control described two main wind of oxygen deprivation again account for total oxygen deprivation main airstream amount
5-95 body %；Preferably, the flow that can control the main wind of oxygen deprivation again and again accounts for the 35-45 of total oxygen deprivation main airstream amount
Body %, the flow that can control described two main wind of oxygen deprivation again account for the 55-65 body % of total oxygen deprivation main airstream amount.
Since organic oxide catalytic cracking aromatic hydrocarbons coking yield is low, the heat that releasing is burnt in regeneration is few, and burning heat release can
The lesser device of regenerator surface radiating, especially scale can be lower than, regenerator surface radiating ratio is larger.To solve above-mentioned ask
Device heating problems when inscribing and going into operation, heater 4 is arranged in the present invention, for heating the main wind 14 of total oxygen deprivation, and can be according to institute
State again and again regenerated temperature and/or described two again regenerated temperature adjust the main wind of total oxygen deprivation temperature be 100-1000 DEG C,
To ensure the heat balance of the first regenerator 1 and Second reactivator 2.The heater 4 can be auxiliary combustion chamber, and burning is situated between
Matter can include but is not limited to selected from least one of diesel oil, fuel gas and natural gas, this outer heating device 4 or electricity add
Hot device.
According to the present invention, for guarantee for regenerated gas be evenly distributed in the first regenerator and Second reactivator and with
Catalyst comes into full contact with, and burns effect and fluidized state to reach good, the main wind of oxygen deprivation again and again can be passed through one
Or multiple oxygen deprivation main air distributors are sent into first regenerator for regenerating, and/or by described two again the main wind of oxygen deprivation pass through
One or more oxygen deprivation main air distributors are sent into Second reactivator for regenerating；The oxygen deprivation main air distributor is this field skill
It, can be in dendroid distributor pipe, ring type distributor pipe, porous type distribution grid and cone hat type distribution rings known to art personnel
It is at least one.
According to the present invention it is possible to overlap first regenerator and the Second reactivator and the first regenerator up and down
It is arranged above Second reactivator, and the junction of the first regenerator and Second reactivator can be set to only allow to carry secretly
The gas of a small amount of catalyst passes through；Second regenerated flue gas can be fed to the bottom of first regenerator, and described
The main wind of oxygen deprivation is used for the described of the first regenerator together and regenerates again and again again and again.Furthermore it is also possible to by the first regeneration cigarette
Gas sends out the first regenerator after separating by least one set of two stage cyclone separator with the semi regeneration catalyst.The whirlwind point
It is well known to those skilled in the art from device, the present invention repeats no more.General one group of two stage cyclone separator includes concatenated one
A primary cyclone and a secondary cyclone；When multiple groups two stage cyclone separator is arranged, one cyclonic separation
The quantity of device and secondary cyclone is generally identical, between can be by the one-to-one connection of riser, can also be by multiple one
After the riser of grade cyclone separator merges into a concetrated pipe, then connect with multiple secondary cyclones, second level whirlwind divides
Riser from device is connect with collection chamber, and the collection chamber can be located at the inside of regenerator, can also be located at regenerator
It is external.
A kind of specific embodiment according to the present invention, as shown in Figure 1, when eclipsed form arranges the first regenerator 1 and second
When regenerator 2, the first regenerator 1 is connected between lower part, two regenerators by low pressure drop distribution grid in top, Second reactivator 2
It connects；The reclaimable catalyst containing coke that reaction system comes enters the first regenerator 1, burns with main 15 counter current contacting of wind of oxygen deprivation again and again
Coke after the hydrogen and part carbon of burning up the overwhelming majority, enters 2 lower part of Second reactivator by semi regeneration inclined tube 5, with two oxygen deprivation masters again
16 co-current contact of wind is burnt, and burns up most of carbon and fraction hydrogen in residual coke；The flue gas of Second reactivator 2 passes through low pressure drop
Distribution grid enters the first regenerator 1, through primary cyclone 9 and secondary cyclone 10 after mixing with the first regenerated flue gas
The catalyst for isolating overwhelming majority entrainment, subsequently into subsequent power recovery system.
According to the invention, it is further possible to which first regenerator and the Second reactivator is set side by side；It can pass through simultaneously
At least one set of two stage cyclone separator the semi regeneration catalyst is separated with first regenerated flue gas and by described first again
Raw flue gas sends out first regenerator；It can also be by least one set of two stage cyclone separator by the regenerated catalyst and institute
The second regenerated flue gas is stated to separate and second regenerated flue gas is sent out the Second reactivator, it then can also will be from described the
After first regenerated flue gas that one regenerator is sent out is mixed with second regenerated flue gas sent out from the Second reactivator
It burns, obtain combustion product gases and carries out energy regenerating.
Another kind specific embodiment according to the present invention, as shown in Fig. 2, when block form arranges the first regenerator 1 and the
When two regenerators 2, the reclaimable catalyst containing coke that reaction system comes enters the first regenerator 1, with the main wind 15 of oxygen deprivation again and again
Counter current contacting is burnt, and after the hydrogen and part carbon of burning up the overwhelming majority, is delivered to 2 lower part of Second reactivator by semi regeneration inclined tube 5,
With two again main 16 co-current contact of wind of oxygen deprivation burn, burn up most of carbon and fraction hydrogen in residual coke；First regenerator 1 is rich in
Flue gas 19 of the flue gas 18 and Second reactivator 2 of CO containing excess oxygen passes through primary cyclone 9 and second level cyclonic separation respectively
After device 10 isolates the catalyst of overwhelming majority entrainment, into flue is mixed and burned, CO and excess oxygen solid/liquid/gas reactions burn, flue gas 17
Into subsequent power recovery system.
According to the present invention, the catalyst bed layer height of the first regenerator can be controlled by semi regeneration slide valve 6, Second reactivator
Catalyst bed layer height can be by sending to the regeneration catalyzing dosage control of reactor.
The following examples will further illustrate the present invention in conjunction with attached drawing, but the present invention is not therefore and by any
Limitation.
As shown in Figure 1, organic oxide catalytic cracking used by a kind of specific embodiment of the method for the present invention is fragrant
Hydrocarbon system is eclipsed form regenerative system, and regenerative system mainly includes the first regenerator 1, Second reactivator 2, main air blower 3, heater
4, semi regeneration inclined tube 5 and semi regeneration slide valve 6, wherein the first regenerator 1 and 2 eclipsed form of Second reactivator arrangement, the first regenerator 1
On top, Second reactivator 2 is connected between lower part, two regenerators by low pressure drop distribution grid.
When normal operating, air 11 becomes main wind 13 after the compression of main air blower 3, then is mixed into the main wind of total oxygen deprivation with nitrogen 12
14；Total main wind 14 of oxygen deprivation is divided into two-way after becoming into the heating of heater 4: the main wind of oxygen deprivation 15 and two main wind 16 of oxygen deprivation again again and again, point
Not Jin Ru the first regenerator 1 and Second reactivator 2 burn, the first regenerator 1 and Second reactivator 2 burn after flue gas through two-stage
After rotation divides the catalyst of separator recycling entrainment, into subsequent energy recycling system.
It for 110 ton/days of methanol aromatic devices, is distributed according to reactor product, coking yield is the 0.5 of methanol inlet amount
Weight %-1.5 weight %, is far below Conventional catalytic cracking device；For diameter, the volume for guaranteeing the first regenerator 1 and Second reactivator 2
And the inlet velocity of primary cyclone 9 and secondary cyclone 10, it needs to supplement suitable inertia into main wind 13
Gas (the present embodiment uses nitrogen) 12, according to different coking yields, the inert gas volume flow of supplement is about main wind volume
2-10 times of flow, to maintain regenerator dense-phase bed linear speed about 0.4-0.8m/s, two stage cyclone separator inlet linear speed 15-
20m/s, it is ensured that the good separative efficiency for burning effect and fluidized state and two stage cyclone separator of catalyst in regenerator.
To guarantee to burn effect and reducing catalyst hydrothermal deactivation, 550 DEG C -650 of 1 operation temperature of the first regenerator is controlled
DEG C, 600 DEG C -700 DEG C of 2 operation temperature of Second reactivator.Methanol aromatic hydrocarbons regenerator is designed using hot wall, and regenerator is externally provided with
200mm thick insulation layer needs the temperature maintained according to the heat and regenerator surface radiating and regenerator for burning releasing, if
It sets electric heater 4 to heat the main wind of oxygen deprivation, the main wind of oxygen deprivation is heated to 800 DEG C -1000 DEG C.
The main wind self-heating device 4 of oxygen deprivation is divided into two-way after heating up, wherein the main 15 main wind 14 of the total oxygen deprivation of flow Zhan of wind of oxygen deprivation again and again
The 35-45% of flow；The 55-65% of two main 14 flows of wind of the main 16 total oxygen deprivation of flow Zhan of wind of oxygen deprivation again.Again and again the main wind 15 of oxygen deprivation by
Dendroid distributor pipe 7 enters the first regenerator bottoms, and reaction system carrys out the reclaimable catalyst containing coke into the first regenerator 1
Middle and upper part, reclaimable catalyst are burnt with the main wind counter current contacting of oxygen deprivation, after the hydrogen and part carbon of burning up the overwhelming majority, semi regeneration catalysis
Agent enters 2 lower part of Second reactivator by semi regeneration inclined tube 5, burns with main 16 co-current contact of wind of the second oxygen deprivation, burns up remaining burnt
Most of carbon and fraction hydrogen, the catalyst after regeneration continue to participate in instead from 2 top Returning reacting system of Second reactivator in charcoal
It answers.The flue gas rich in oxygen of Second reactivator 2 enters the first regenerator 1 by low pressure drop distribution grid, with the main wind of oxygen deprivation again and again
Mixing participates in burning, and the first regenerated flue gas isolates most folders through primary cyclone 9 and secondary cyclone 10
The catalyst of band, subsequently into subsequent power recovery system.
As can be seen that using regeneration methods of the invention, other than the advantages of having been described above, reaction system from embodiment 1
The weight %-1.2 weight % of reclaimable catalyst carbon deposition quantity 0.5 that system comes, the weight %-0.1 weight % of regeneration catalyzing carbon deposition quantity 0.05 after burning,
Regenerated catalyst activity and selectivity meets aromatization of methanol reaction and requires.
Claims (10)
1. a kind of regeneration method of organic oxide catalytic cracking arenes catalytic agent, this method comprises: organic oxidation will be come from
The reclaimable catalyst of object catalytic cracking aromatic hydrocarbons reaction system is sent into the first regenerator and contacts with the main wind of oxygen deprivation again and again and carry out one
It regenerates, obtains semi regeneration catalyst and the first regenerated flue gas；
By the semi regeneration catalyst be sent into Second reactivator with two again the main wind of oxygen deprivation contact and carry out two and regenerate, regenerated
Catalyst and the second regenerated flue gas；
The regenerated catalyst is sent back in organic oxide catalytic cracking aromatic hydrocarbons reaction system；
Wherein, by volume, the oxygen content of the main wind of the oxygen deprivation again and again and described two main wind of oxygen deprivation again is below the oxygen of air
Gas content；
This method further include: at least one of air and nitrogen, argon gas, helium, carbon dioxide and flue gas are mixed, obtained total
Total main wind of oxygen deprivation is divided into the main wind of oxygen deprivation again and again and described two main wind of oxygen deprivation again by the main wind of oxygen deprivation；It will be described poor again and again
The main wind of oxygen is sent into first regenerator, will be in described two again the oxygen deprivation main wind feeding Second reactivator；The flue gas is
Mixture selected from first regenerated flue gas, second regenerated flue gas and the first regenerated flue gas and the second regenerated flue gas
At least one of resulting gas after further burning；In the main wind of total oxygen deprivation, nitrogen used, argon are mixed with air
Gas, helium, carbon dioxide and the flue gas total content be greater than 0 and to be no more than 99.9 body %；
Second regenerated flue gas is fed to the bottom of first regenerator, is used for institute together with the main wind of oxygen deprivation again and again
The described of the first regenerator is stated to regenerate again and again；
The protium weight for controlling coke contained by the semi regeneration catalyst is the protium of coke contained by the reclaimable catalyst
The 0-40 weight % of weight, the carbon weight for controlling coke contained by the semi regeneration catalyst is coke contained by the reclaimable catalyst
The 10-50 weight % of the carbon weight of charcoal；The content for controlling coke in the regenerated catalyst is 0.01-0.1 weight %；Described in control
Regenerated temperature is 500-700 DEG C again and again；Control described two again regenerated temperature be 600-800 DEG C；
The catalyst is the microspherical catalyst containing molecular sieve and carrier, and the molecular sieve is ZSM-5 molecular sieve.
2. regeneration method according to claim 1, wherein the organic oxide is selected from C1-C10Alcohols, C2-C12Ethers and
C3-C12At least one of ketone.
3. regeneration method according to claim 1, wherein in terms of the volume under uniform pressure, the control main wind of oxygen deprivation again and again
Flow account for the 5-95 body % of total oxygen deprivation main airstream amount, the flow of the main wind of oxygen deprivation again of control described two accounts for total oxygen deprivation master
The 5-95 body % of wind flow.
4. regeneration method according to claim 1, wherein in terms of the volume under uniform pressure, the control main wind of oxygen deprivation again and again
Flow account for the 35-45 body % of total oxygen deprivation main airstream amount, the flow of the main wind of oxygen deprivation again of control described two accounts for total oxygen deprivation master
The 55-65 body % of wind flow.
5. regeneration method according to claim 1, wherein regenerated again according to the temperature regenerated again and again and/or described two
The temperature that temperature adjusts the main wind of total oxygen deprivation is 100-1000 DEG C.
6. regeneration method according to claim 1, wherein the main wind of oxygen deprivation again and again is passed through one or more main wind of oxygen deprivation point
Cloth device is sent into first regenerator for regenerating, and/or will described two again the main wind of oxygen deprivation pass through one or more oxygen deprivation masters
Wind distributor is sent into Second reactivator for regenerating；The oxygen deprivation main air distributor is selected from dendroid distributor pipe, ring type point
At least one of stringing, porous type distribution grid and cone hat type distribution rings.
7. regeneration method according to claim 1, wherein first regenerator and the Second reactivator is set side by side；It is logical
At least one set of two stage cyclone separator is crossed to separate the semi regeneration catalyst with first regenerated flue gas and by described first
Regenerated flue gas sends out first regenerator；By at least one set of two stage cyclone separator by the regenerated catalyst and described the
Two regenerated flue gas separate and second regenerated flue gas are sent out the Second reactivator.
8. regeneration method according to claim 7, wherein by first regenerated flue gas sent out from first regenerator with
It burns after second regenerated flue gas mixing that the Second reactivator is sent out, obtains combustion product gases and carry out energy time
It receives.
9. regeneration method according to claim 1, wherein overlap first regenerator and the Second reactivator up and down
And first regenerator be arranged above Second reactivator, and the junction of the first regenerator and Second reactivator is arranged to only
The gas for allowing to carry secretly a small amount of catalyst passes through；Carry secretly a small amount of regenerated catalyst second regenerated flue gas be fed to it is described
The bottom of first regenerator is used to regenerate again and again described in first regenerator together with the main wind of oxygen deprivation again and again.
10. regeneration method according to claim 9, wherein first regenerated flue gas is passed through at least one set of two stage cyclone point
The first regenerator is sent out after separating from device with the semi regeneration catalyst.
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| CN107282142A (en) * | 2017-07-05 | 2017-10-24 | 洛阳融惠化工科技有限公司 | A kind of renovation process and equipment that catalyst can be controlled to determine charcoal |
| CN110237779A (en) * | 2018-05-29 | 2019-09-17 | 青岛京润石化设计研究院有限公司 | A kind of catalyst multi-stage fluidized regeneration method and catalyst regenerator |
| CN115305107A (en) * | 2022-08-29 | 2022-11-08 | 中国石油化工股份有限公司 | External regenerator concurrent heating equipment of fluidized bed light hydrocarbon processing device |
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| US4332674A (en) * | 1980-07-15 | 1982-06-01 | Dean Robert R | Method and apparatus for cracking residual oils |
| CN101554598A (en) * | 2007-12-21 | 2009-10-14 | Bp北美公司 | System and method of regenerating catalyst in a fluidized catalytic cracking unit |
| CN103998129A (en) * | 2011-12-15 | 2014-08-20 | 环球油品公司 | Multiple burn zones with independent circulation loops |
| CN104220170A (en) * | 2012-03-20 | 2014-12-17 | 环球油品公司 | Improved robustness of coke burning from catalyst for light paraffin dehydrogenation process |
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2015
- 2015-01-28 CN CN201510041973.4A patent/CN105983455B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4332674A (en) * | 1980-07-15 | 1982-06-01 | Dean Robert R | Method and apparatus for cracking residual oils |
| CN101554598A (en) * | 2007-12-21 | 2009-10-14 | Bp北美公司 | System and method of regenerating catalyst in a fluidized catalytic cracking unit |
| CN103998129A (en) * | 2011-12-15 | 2014-08-20 | 环球油品公司 | Multiple burn zones with independent circulation loops |
| CN104220170A (en) * | 2012-03-20 | 2014-12-17 | 环球油品公司 | Improved robustness of coke burning from catalyst for light paraffin dehydrogenation process |
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