CN106588527B - Produce the regenerative response system and reaction method of aromatic hydrocarbons and low-carbon alkene - Google Patents

Produce the regenerative response system and reaction method of aromatic hydrocarbons and low-carbon alkene Download PDF

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CN106588527B
CN106588527B CN201510670988.7A CN201510670988A CN106588527B CN 106588527 B CN106588527 B CN 106588527B CN 201510670988 A CN201510670988 A CN 201510670988A CN 106588527 B CN106588527 B CN 106588527B
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catalyst
reactor
gas
regenerator
regeneration
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CN106588527A (en
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金永明
钟思青
齐国祯
李晓红
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/40Ethylene production

Abstract

The present invention relates to a kind of regenerative response system and reaction method for producing aromatic hydrocarbons and low-carbon alkene, mainly solve the problems, such as that catalyst hydrothermal deactivation is serious in the prior art, service life is short, installation area is big.The present invention passes through coaxially arranged including reactor, two-stage regeneration device, raw material enters reactor and catalyst haptoreaction from reactor lower part, carbon deposited catalyst after reaction is lifted into the first regenerator gas-solid cyclone separator after stripper strips and carries out gas solid separation, catalyst is isolated to regenerate into the first regenerator, the degassed tank of the catalyst of semi regeneration, which enters Second reactivator, to be continued to regenerate, regenerate technical solution of the complete catalyst through catalyst standpipe Returning reactor, it preferably solves the problems, such as this, can be used in the industrial production of aromatic hydrocarbons and low-carbon alkene.

Description

Produce the regenerative response system and reaction method of aromatic hydrocarbons and low-carbon alkene
Technical field
The present invention relates to a kind of regenerative response system and method for producing aromatic hydrocarbons and low-carbon alkene.
Background technique
Aromatic hydrocarbons (especially triphen, benzene Benzene, toluene Toluene, dimethylbenzene Xylene, i.e. BTX) and low-carbon alkene (i.e. ethylene and propylene) is important basic organic chemical raw material, and derivative is widely used in chemical fibre, plastics and rubber etc. The production of chemical products and fine chemicals.In recent years, by the driving of downstream derivative object demand, the city of aromatic hydrocarbons and ethylene, propylene Field demand constantly increases.
Currently, the production technology of aromatic hydrocarbons and low-carbon alkene mainly from petroleum path, and China's oil resource is relatively deficient, A large amount of imports are needed, 2013, the petroleum interdependency in China had reached 58%.In recent years, international crude oil price is high-order always transports Row, the production technology of aromatic hydrocarbons and low-carbon alkene to petroleum path bring very big cost pressure.Wherein, for coal-based methanol, Dimethyl ether raw material is increasingly becoming a kind of important Chemical Manufacture raw material, is become petroleum due to rich coal resources in China Important supplement, diversification of resources may be implemented, optimize the structure of production, mitigate excessive dependence to petroleum.Accordingly, it is considered to first Alcohol or dimethyl ether are that raw material prepares aromatic hydrocarbons and low-carbon alkene.
In various existing methanol, dimethyl ether catalysis transformation technology, the product of methanol/dimethyl ether conversion aromatic hydrocarbons is simultaneously Including ethylene, propylene and aromatic hydrocarbons.The technology initially sees Chang of Mobil company in 1977 et al. (Journal of Catalysis, 1977,47,249) report methanol and its oxygenate conversion preparation virtue on ZSM-5 molecular sieve catalyst The method of the hydrocarbons such as hydrocarbon.1985, Mobil company disclosed for the first time in the United States Patent (USP) US1590321 of its application The result of study of methanol, dimethyl ether conversion aromatic hydrocarbons, it is catalysis which, which uses the phosphorous ZSM-5 molecular sieve for 2.7 weight %, Agent, reaction temperature are 400~450 DEG C, methanol, dimethyl ether air speed 1.3 (Grams Per Hour)/gram catalyst.
The relevant report and patent in the field are more, but the aromatic hydrocarbons of most of technologies, and ethylene, propylene belong to by-product, Yield is low.For example, the patent in terms of methanol arenes catalytic agent: Chinese patent CN102372535, CN102371176, CN102371177, CN102372550, CN102372536, CN102371178, CN102416342, CN101550051, the U.S. Patent US4615995, US2002/0099249A1 etc..For example, the patent in terms of methanol aromatics process: United States Patent (USP) US4686312, Chinese patent ZL101244969, ZL1880288, CN101602646, CN101823929, CN101671226, CN102199069, CN102199446, CN1880288 etc..
Wherein patent CN101602646 discloses that a kind of methanol/dimethyl ether produces the method for aromatic hydrocarbons and its Special reverse is answered Device, the technique of use or common block form reaction-regeneration technology.
In addition, while the technology path of some patent disclosures is methanol aromatic hydrocarbons co-producing light olefins, gasoline etc. other Product, such as patent CN102775261, CN102146010, CN102531821, CN102190546, CN102372537.
Wherein, Multi-function methanol processing method and device disclosed in patent CN102775261 utilize methanol production low-carbon alkene Hydrocarbon, gasoline, aromatic hydrocarbons.This method uses two-step method production technology, and first step methanol feedstock produces low under the effect of special-purpose catalyst 1 Carbon olefin, second step by the reaction gas containing low-carbon alkene after heat exchange, chilling, carrying out washing treatment, under the action of special-purpose catalyst 2 Synthesize aromatic hydrocarbons and/or gasoline.The reactor of two reaction process can be fixed bed or fluidized bed.This method uses two-step method, technique Process is complicated.
Patent CN102146010 discloses the work that low-carbon alkene and arene parallel cogeneration gasoline are produced using methanol as raw material Skill.Low-carbon alkene and aromatic hydrocarbons are produced through methanol alkylation reaction and aromatization using methanol as raw material and using molecular sieve catalyst Co-production gasoline.The reactor of methanol alkylation reaction and aromatization is various types of fixed bed reactors, pressure 0.01 ~0.5 megapascal, 180~600 DEG C of temperature.Total liquid yield is greater than 70 weight %, and triphen yield is greater than 90 weight %.This method also uses Two reactors, process flow are complicated.
The method that patent CN102531821 discloses methanol and the co-feeding production low-carbon alkene of naphtha and/or aromatic hydrocarbons, Using the ZSM-5 catalyst of load 2.2~6.0 weight %La and 1.0~2.8 weight %P, fixed bed reactors or stream can be used Fluidized bed reactor.Reaction temperature is 550~670 DEG C, air speed 1.0~5 (Grams Per Hour)/gram catalyst.The triolefin yield of this method It is higher, but BTX yield is low, and how only 5~17 weight % solve the problems, such as that catalyst hydrothermal deactivation does not also refer to.
By being analyzed above it is found that up to now, existing patented technology is concentrated mainly on the modification to catalyst, do not have yet There is detailed catalyst recovery process, for how to solve the problems, such as that hydrothermal deactivation also has not been reported in catalyst regeneration process; In addition, counting apparatus all uses height block form to be laid out mostly, occupied area is larger.The present invention pointedly proposes technical side Case solves the above problem.
It is above-mentioned existing using methanol or dimethyl ether as the fluidization that raw material produces aromatic hydrocarbons all use single regenerator into Row catalyst circulation reaction regeneration.To guarantee high activity of catalyst, need the carbon content of regenerated catalyst low as far as possible, 0.05 Therefore~0.1 weight % is hereinafter, unavoidably need high temperature regeneration, generally at 650~730 DEG C or so.Catalyst reaction generates Coke contain protium, protium oxidation reaction can generate vapor, and reclaimable catalyst can also carry a part of water secretly and enter regeneration Device.For molecular sieve catalyst, activity can be lost because of framework of molecular sieve dealuminzation under this hydro-thermal atmosphere, this inactivation is forever Long property and irreversible.For single regenerator reaction-regenerative device, the overwhelming majority of catalyst total amount is present in regenerator Interior, catalyst inventory is excessive in regenerator, and residence time of the catalyst in regenerator is long, and catalyst hydrothermal deactivation is serious, makes With service life reduction, the production cost increases.The present invention pointedly proposes two-stage regeneration device, and reclaimable catalyst is directly promoted to rotation Wind separator, and the technical solution of semi regeneration catalyst degassing tank is set, solve the above problem.
Summary of the invention
The first technical problem to be solved by the present invention is that catalyst hydrothermal deactivation is serious, service life is short, plant area The big problem of area provides the coaxial-type two-stage regeneration reaction system of the new methanol of one kind or dimethyl ether production aromatic hydrocarbons and low-carbon alkene System.The system and device has many advantages, such as effectively to mitigate catalyst hydrothermal deactivation, and installation area is small.
The second technical problem to be solved by the present invention is to provide the corresponding method of one of one kind and solution technical problem.
One of in order to solve the above problem, The technical solution adopted by the invention is as follows: a kind of methanol or dimethyl ether produce aromatic hydrocarbons With the coaxial-type two-stage regeneration reaction system of low-carbon alkene, mainly include reactor 16, the first regenerator 2, Second reactivator 9, Stripper 17, degassing tank 6, gas-solid cyclone separator 3 is equipped with inside the first regenerator 2, and top is equipped with exhanst gas outlet 20;Second again Raw 9 top of device is connected with 2 bottom of the first regenerator, and lower part is connected with built-in down pipe 13, and down pipe 13 passes through reactor 16, instead It answers and is equipped with gas-solid cyclone separator 18 inside device 16, top is equipped with product gas outlet 19, and reactor 16 passes through inclined tube 24 and stripping 17 top of device is connected, and stripper 17 is connected by inclined tube 21 with riser 5, riser 5 and the direct phase of gas-solid cyclone separator 3 Even;Second reactivator 9 is arranged above reactor 16, and the first regenerator 2 is arranged above Second reactivator 9;Reactor 16, One regenerator 2, Second reactivator 9 are on the same axis.
In above-mentioned technical proposal, reactor 16 is turbulent fluid bed reactor;First regenerator 2 with Second reactivator 9 There is an exhanst gas outlet;First regenerator, 2 down pipe, 13 bottom is equipped with catalyst slide valve 23;Catalyst down pipe 13 and reactor Diameter ratio is 0.05~0.2;First regenerator 2 and Second reactivator 9 configure regeneration gas distributor, 2 He of the first regenerator Gas distribution grid 12 is set between Second reactivator 9.
In order to solve the above problem two, The technical solution adopted by the invention is as follows: a kind of methanol or dimethyl ether produce aromatic hydrocarbons With the coaxial-type two-stage regeneration reaction method of low-carbon alkene, using device described in claim 1, the method includes following Several steps:
A) raw material 1 enters reactor 16 and catalyst haptoreaction from 16 lower part of reactor through unstrpped gas distributor 4, raw At reaction product and carbon deposited catalyst, reaction product is after gas-solid cyclone separator 18 isolates catalyst by reactor outlet 19 Into later separation device;
B) stripper 17 being connected with 16 lower part of reactor is advanced under carbon deposited catalyst, catalyst is after stripping again through mentioning It rises standpipe 5 and enters the progress gas solid separation of gas-solid cyclone separator 3;
C) catalyst isolated is regenerated into the first regenerator 2, into the reclaimable catalyst and first of the first regenerator 2 Smoke contacts annealing in hydrogen atmosphere that regenerating medium 14 and Second reactivator 9 generate burns carbon, obtained semi regeneration catalyst, flue gas continue into Enter gas-solid cyclone separator 3 to be separated;
D) the degassed tank 6 of the good catalyst of semi regeneration enters Second reactivator 9 and the contact of the second regenerating medium 11 continues to burn Carbon, which regenerates to obtain, regenerates complete regenerated catalyst and flue gas, and flue gas, which enters the first regenerator 2 through gas distribution grid 12, to be continued again It is raw, complete catalyst is regenerated through 13 Returning reactor 16 of catalyst standpipe.
In above-mentioned technical proposal, the fluidizing gas of degassing tank 6 is nitrogen or air;The first at least burning-off of regenerator 2 is to be generated On catalyst 80% hydrogen and 50% carbon, regeneration temperature is no more than 600 DEG C, the volume basis of oxygen in the first regenerating medium 14 Content is 2~21%;The regeneration temperature of Second reactivator 9 is no more than 700 DEG C, and the second regenerating medium 11 is air, obtains again Charcoal on raw catalyst, in terms of the mass percent of catalyst, weight percentage is lower than 0.1%.
In above-mentioned technical proposal, vapor volumn concentration is not higher than 0.8%, the in 2 exiting flue gas of the first regenerator Vapor volumn concentration is not higher than 0.2% in two regenerators, 9 flue gas.
In above-mentioned technical proposal, the reaction temperature of reactor 16 is 400~550 DEG C, and raw material 1 is methanol or dimethyl ether, weight Amount air speed is 0.1~5 (Grams Per Hour)/gram catalyst, and reaction pressure is 0~0.5 megapascal in terms of gauge pressure, what reactor 16 generated Charcoal on reclaimable catalyst, in terms of the mass percent of catalyst, weight percentage is 0.5~5%;Promotion medium 22 is nitrogen Gas or air.
In above-mentioned technical proposal, the catalyst is in ZSM-5, ZSM-23, ZSM-11, beta-molecular sieve, Y molecular sieve It is at least one;Catalyst load has one or more elements or oxide in Zn, Ag, P, Ga, Mn, Mg, with the quality of catalyst Percentages, content are 0.01~15 weight %.
Technical solution provided by the invention, due to using reactor 2, stripper 6, the first regenerator 9, Second reactivator 13 Coaxial-type arrangement, such arrangement general frame occupied area is small, compact-sized, initial stage put into it is smaller, compared to block form device, Two bases and two frames can be saved, occupied area is than 50% or more the reduction of block form, while cost can save 20- 30%.
Technical solution provided by the invention, using two sections of overlapping reconstituted forms.Reclaimable catalyst is stripped through nitrogen or air It is directly promoted to the progress gas solid separation gas-solid cyclone separator in the first regenerator Nei afterwards, can control to greatest extent to be generated Catalyst entrainment moisture content enters in regenerator.First regenerator bottoms are sent into one section of main wind, and under oxygen-lean atmosphere, at least burning-off is waited for 80% hydrogen and 50% carbon on raw catalyst, achieve the purpose that annealing in hydrogen atmosphere at a lower temperature.Semi regeneration catalyst is by degassing Tank enters back into Second reactivator after carrying out water vapor removing, high temperature can be avoided to greatest extent to be lauched the contact with catalyst. Two sections of main wind enter Second reactivator by the distributor of bottom, carry out the regeneration remaining coke of burning-off completely.Second reactivator Flue gas passes through top distribution grid and enters the first regenerator, and the excess oxygen in flue gas continues to burn utilization.It is burnt in Second reactivator When due to the water of generation it is seldom, catalyst hydrothermal dealumination phenomenon obviously weakens, and can effectively mitigate catalyst hydrothermal deactivation, prolong Long catalyst life.
Technical solution provided by the invention, due to using reactor 16, the first regenerator 2,9 coaxial-type cloth of Second reactivator It sets, such arrangement general frame occupied area is small, compact-sized, initial stage investment is smaller, compared to block form device, can save two A basis and two frames, reduction 50% or more of the occupied area than block form.
Using technical solution of the present invention, using the reaction system, the degassing tank 6 is fluidized using nitrogen, and first again 570 DEG C of device regeneration temperature is given birth to, the content of oxygen is 4 volume % in the first regenerating medium 1;The regeneration temperature of Second reactivator 9 is 650 DEG C, the second regenerating medium 14 be air, the obtained charcoal in regenerated catalyst, in terms of the mass percent of catalyst, content For 0.08 weight %.The reaction temperature of the reactor 16 be 490 DEG C, raw material 1 be methanol, weight space velocity be 1.2 (gram/it is small When)/gram catalyst, reaction pressure is 0.2 megapascal in terms of gauge pressure, the charcoal on reclaimable catalyst that reactor 16 generates, with catalysis The mass percent meter of agent, content are 1.5 weight %;Stripping fluid is nitrogen;Promotion medium is nitrogen.The catalyst uses Zn-ZSM-5;Aromatic hydrocarbons carbon base absorption rate only reduces by 1.5% after continuous service test after 500 hours, achieves preferable technology effect Fruit.
Detailed description of the invention
Fig. 1 is the schematic device of technical solution of the present invention.
1 is raw material in 1 in figure;2 be the first regenerator;3 be the first regenerator gas-solid cyclone separator;4 be unstrpped gas Distributor;5 be promotion standpipe;6 be degassing tank;7 be semi regeneration inclined tube;8 be catalyst down pipe;9 be Second reactivator;10 are Second reactivator gas distributor;11 be the second regenerating medium;12 be gas distribution grid;13 be built-in down pipe;14 be first Regenerating medium;15 be the first regenerator gases distributor;16 be reactor;17 be stripper;18 be reactor gas-solid cyclone point From device;19 be reaction product;20 be flue gas;21 be stripper inclined tube;22 be promotion medium;23 be catalyst slide valve;24 be anti- Answer device inclined tube;25 be degassing tank fluidized gas;26 be stripping gas.
Raw material enters reactor 16 and catalyst haptoreaction from 16 lower part of reactor through unstrpped gas distributor 4 in Fig. 1, Reaction product and carbon deposited catalyst are generated, reaction product is after gas-solid cyclone separator 18 isolates catalyst by reactor outlet 19 enter later separation device;The stripper 17 being connected with 16 lower part of reactor is advanced under carbon deposited catalyst, catalyst is through vapour Boosted standpipe 5 enters the progress gas solid separation of gas-solid cyclone separator 3 again after mentioning;The catalyst isolated enters the first regenerator 2 regeneration, the smoke contacts generated into the reclaimable catalyst of the first regenerator 2 and the first regenerating medium 14 and Second reactivator 9 Annealing in hydrogen atmosphere burns carbon, obtained semi regeneration catalyst, and flue gas goes successively to gas-solid cyclone separator 3 and separated;Semi regeneration is good to urge The degassed tank 6 of agent enters Second reactivator 9 and the contact of the second regenerating medium 11 continues charcoal regeneration and obtains regeneration completely again Raw catalyst and flue gas, flue gas continue to regenerate through gas distribution grid 12 into the first regenerator 2, regenerate complete catalyst through urging 13 Returning reactor 16 of agent standpipe.The present invention will be further described below by way of examples, but is not limited only to this implementation Example.
[embodiment 1]
Using device as shown in Figure 1.Using coaxial-type arrangement, catalyst down pipe and reactor diameter ratio are 0.1, First regenerator regeneration temperature is 500 DEG C, and gas phase linear speed is 0.4 meter per second.Regenerating medium is air, and oxygen content is 21 bodies Product %.Degassing tank fluidized gas is nitrogen.Second reactivator regeneration temperature is 600 DEG C, and gas phase linear speed is 0.55 meter per second.After regeneration Catalyst on charcoal, in terms of the mass percent of catalyst, content be 0.09 weight %.Water volume in first regenerator flue gas Percentage is 0.6%, and water volume percentage is 0.15% in Second reactivator flue gas.
The reaction condition of reactor are as follows: temperature is 400 DEG C, and reaction pressure is 0 megapascal, weight space velocity 0.15 in terms of gauge pressure (Grams Per Hour)/gram catalyst, gas phase linear speed are 0.03 meter per second.Using methanol as raw material, stripping fluid is nitrogen, promotes medium and is Nitrogen.Using Ag-Y-ZSM-23 catalyst, Ag constituent content is 0.23 weight %.
Through 500 hours continuous operations, aromatic hydrocarbons carbon base absorption rate reduced by 1%;Compare the block form reaction regeneration of same treating capacity Device, occupied area reduce 40%.
[embodiment 2]
Using device as shown in Figure 1.Using coaxial-type arrangement, catalyst down pipe and reactor diameter ratio are 0.05, the first regenerator regeneration temperature is 550 DEG C, and gas phase linear speed is 0.45 meter per second.Regenerating medium is that air and nitrogen mix Object, oxygen content are 16 volume %.Degassing tank fluidized gas is nitrogen.Second reactivator regeneration temperature is 650 DEG C, and gas phase linear speed is 0.6 meter per second.The charcoal on catalyst after regeneration, in terms of the mass percent of catalyst, content is 0.08 weight %.First again Water volume percentage is 0.7% in raw device flue gas, and water volume percentage is 0.08% in Second reactivator flue gas.
The reaction condition of reactor are as follows: temperature is 450 DEG C, and reaction pressure is 0.25 megapascal, weight space velocity 2 in terms of gauge pressure (Grams Per Hour)/gram catalyst, gas phase linear speed are 0.08 meter per second.Using methanol as raw material, stripping fluid is nitrogen, promotes medium and is Air.Using Mn-ZSM-11 catalyst, Mn constituent content is 12 weight %.
Through 500 hours continuous operations, aromatic hydrocarbons carbon base absorption rate reduced by 1.3%;Compare the block form reaction of same treating capacity again Generating apparatus, occupied area reduce 40%.
[embodiment 3]
Using device as shown in Figure 1.Using coaxial-type arrangement, catalyst down pipe and reactor diameter ratio are 0.2, First regenerator regeneration temperature is 600 DEG C, and gas phase linear speed is 0.5 meter per second.Regenerating medium is air and nitrogen mixture, oxygen Content is 5 volume %.Degassing tank fluidized gas is air.Second reactivator regeneration temperature be 690 DEG C, gas phase linear speed be 0.65 meter/ Second.The charcoal on catalyst after regeneration, in terms of the mass percent of catalyst, content is 0.05 weight %.First regenerator cigarette Water volume percentage is 0.75% in gas, and water volume percentage is 0.05% in Second reactivator flue gas.
The reaction condition of reactor are as follows: temperature is 480 DEG C, and reaction pressure is 0.1 megapascal in terms of gauge pressure, and weight space velocity is 0.6 (Grams Per Hour)/gram catalyst, gas phase linear speed are 0.067 meter per second.Using dimethyl ether as raw material, stripping fluid is nitrogen, is promoted Medium is air.Using Zn-P-ZSM-5 catalyst, Zn constituent content is 2.56 weight %, and P element content is 1.32 weight %.
Through 500 hours continuous operations, aromatic hydrocarbons carbon base absorption rate reduced by 2.2%;Compare the block form reaction of same treating capacity again Generating apparatus, occupied area reduce 40%.
[embodiment 4]
Using device as shown in Figure 1.Using coaxial-type arrangement, catalyst down pipe and reactor diameter ratio are 0.15, the first regenerator regeneration temperature is 500 DEG C, and gas phase linear speed is 0.4 meter per second.Regenerating medium be air and nitrogen mixture, Oxygen content is 8 volume %.Second reactivator regeneration temperature is 650 DEG C, and gas phase linear speed is 0.6 meter per second.Catalyst after regeneration On charcoal, in terms of the mass percent of catalyst, content be 0.1 weight %.Water volume percentage is in first regenerator flue gas 0.55%, water volume percentage is 0.18% in Second reactivator flue gas.
The reaction condition of reactor are as follows: temperature is 550 DEG C, and reaction pressure is 0.5 megapascal, weight space velocity 5 in terms of gauge pressure (Grams Per Hour)/gram catalyst, gas phase linear speed are 0.87 meter per second.Using methanol as raw material, stripping fluid is nitrogen, promotes medium and is Nitrogen.Using Ga- beta catalyst, Ga constituent content is 1.05 weight %.
Through 500 hours continuous operations, aromatic hydrocarbons carbon base absorption rate reduced by 1.8%;Compare the block form reaction of same treating capacity again Generating apparatus, occupied area reduce 40%.
[embodiment 5]
Using device as shown in Figure 1.Using coaxial-type arrangement, catalyst down pipe and reactor diameter ratio are 0.08, the first regenerator regeneration temperature is 600 DEG C, and gas phase linear speed is 0.5 meter per second.Regenerating medium be air and nitrogen mixture, Oxygen content is 2 volume %.Second reactivator regeneration temperature is 650 DEG C, and gas phase linear speed is 0.55 meter per second.Catalysis after regeneration Charcoal in agent, in terms of the mass percent of catalyst, content is 0.07 weight %.Water volume percentage in first regenerator flue gas It is 0.50%, water volume percentage is 0.2% in Second reactivator flue gas.
The reaction condition of reactor are as follows: temperature is 500 DEG C, and reaction pressure is 0.15 megapascal, weight space velocity 1 in terms of gauge pressure (Grams Per Hour)/gram catalyst, gas phase linear speed are 0.072 meter per second.Using methanol as raw material, stripping fluid is nitrogen, promotes medium For air.Using Zn-Mg-P-ZSM-5 catalyst, Zn constituent content is that 1.72 weight %, Mg constituent contents are 1.49 weight %, P element content is 2.12 weight %.
Through 500 hours continuous operations, aromatic hydrocarbons carbon base absorption rate reduced by 2%;Compare the block form reaction regeneration of same treating capacity Device, occupied area reduce 40%.
[comparative example 1]
According to condition described in embodiment 1 and step, two sections of regeneration are not provided with, and individually use a regenerator, stripping Reclaimable catalyst afterwards is directly mentioned to the first regenerator dilute phase section, and through 500 hours continuous operations, aromatic hydrocarbons carbon base absorption rate was reduced 8.5%;
[comparative example 2]
According to condition described in embodiment 1 and step, two sections of regeneration are set, are not provided with semi regeneration degassing tank, after stripping Reclaimable catalyst is directly mentioned to the first regenerator dilute phase section, and through 500 hours continuous operations, aromatic hydrocarbons carbon base absorption rate reduced by 4.5%;
Obviously, using two-stage regeneration reaction system of the invention and method, it can effectively mitigate catalyst hydrothermal deactivation, prolong Long catalyst life.

Claims (10)

1. a kind of regenerative response system for producing aromatic hydrocarbons and low-carbon alkene, mainly include reactor (16), the first regenerator (2), Second reactivator (9), stripper (17), degassing tank (6), the first regenerator (2) is internal to be equipped with the first regenerator gas-solid cyclone point From device (3), top is equipped with exhanst gas outlet (20);Second reactivator (9) top is connected with the first regenerator (2) bottom, lower part and Built-in down pipe (13) is connected, and down pipe (13) passes through reactor (16), and reactor gas-solid cyclone is equipped with inside reactor (16) Separator (18), top are equipped with product gas outlet (19), and reactor (16) is connected by inclined tube (24) with stripper (17) top, Stripper (17) is connected by inclined tube (21) with riser (5), riser (5) and the first regenerator gas-solid cyclone separator (3) It is connected directly;Above reactor (16), the first regenerator (2) is arranged on Second reactivator (9) for Second reactivator (9) setting Side;Reactor (16), the first regenerator (2), Second reactivator (9) are on the same axis.
2. the regenerative response system of production aromatic hydrocarbons and low-carbon alkene according to claim 1, feature is in reactor (16) For turbulent fluid bed reactor.
3. the regenerative response system of production aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that the first regeneration Device (2) and Second reactivator (9) only one exhanst gas outlet.
4. the regenerative response system of production aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that the first regeneration Device (2) down pipe (13) bottom is equipped with catalyst slide valve (23).
5. the regenerative response system of production aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that under catalyst Row pipe (13) and reactor diameter ratio are 0.05~0.2.
6. the regenerative response system of production aromatic hydrocarbons and low-carbon alkene according to claim 1, it is characterised in that the first regeneration Device (2) and Second reactivator (9) configure regeneration gas distributor, are arranged between the first regenerator (2) and Second reactivator (9) Gas distribution grid (12).
7. a kind of regenerative response method for producing aromatic hydrocarbons and low-carbon alkene, using any one reaction described in claim 1~6 System, the method including the following steps:
A) raw material (1) enters reactor (16) from reactor (16) lower part through unstrpped gas distributor (4) and catalyst contacts instead It answers, reaction product and carbon deposited catalyst is generated, after the reacted device gas-solid cyclone separator (18) of reaction product isolates catalyst Enter later separation device by reactor outlet (19);
B) stripper (17) being connected with reactor (16) lower part is advanced under carbon deposited catalyst, catalyst is after stripping again through mentioning It rises standpipe (5) and enters the first regenerator gas-solid cyclone separator (3) progress gas solid separation;
C) catalyst isolated is regenerated into the first regenerator (2), into the reclaimable catalyst and first of the first regenerator (2) Smoke contacts annealing in hydrogen atmosphere that regenerating medium (14) and Second reactivator (9) generate burns carbon, obtained semi regeneration catalyst, flue gas after The continuous first regenerator gas-solid cyclone separator (3) that enters is separated;
D) the degassed tank of the good catalyst of semi regeneration (6) enters Second reactivator (9) and the second regenerating medium (11) contact continues Charcoal regeneration obtains regenerating complete regenerated catalyst and flue gas, and flue gas enters the first regenerator (2) through gas distribution grid (12) Continue to regenerate, regenerates complete catalyst through catalyst standpipe (13) Returning reactor (16).
8. the regenerative response method of production aromatic hydrocarbons and low-carbon alkene according to claim 7, it is characterised in that the degassing The fluidizing gas of tank (6) is nitrogen or air.
9. the regenerative response method of production aromatic hydrocarbons and low-carbon alkene according to claim 7, which is characterized in that the first regeneration 80% hydrogen and 50% carbon on device (2) at least burning-off reclaimable catalyst, regeneration temperature are no more than 600 DEG C, the first regenerating medium (14) volumn concentration of oxygen is 2~21% in;The regeneration temperature of Second reactivator (9) is no more than 700 DEG C, the second regeneration Medium (11) is air, and the obtained charcoal in regenerated catalyst, in terms of the mass percent of catalyst, weight percentage is lower than 0.1%.
10. the regenerative response method of production aromatic hydrocarbons and low-carbon alkene according to claim 7, it is characterised in that the first regeneration Vapor volumn concentration is not higher than 0.8% in device (2) exiting flue gas, vapor volume hundred in Second reactivator (9) flue gas Content is divided to be not higher than 0.2%.
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