CN108017487A - Method containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction - Google Patents

Method containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction Download PDF

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Publication number
CN108017487A
CN108017487A CN201610973691.2A CN201610973691A CN108017487A CN 108017487 A CN108017487 A CN 108017487A CN 201610973691 A CN201610973691 A CN 201610973691A CN 108017487 A CN108017487 A CN 108017487A
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fluidized
aromatic hydrocarbons
bed
catalyst
bed reactor
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CN108017487B (en
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李晓红
齐国祯
徐俊
王菊
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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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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/26Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
    • B01J8/28Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations the one above the other
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • 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

Abstract

The present invention relates to a kind of method containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, mainly solves the problems, such as that arenes selectivity is low in the prior art.The present invention is one section of fluidized-bed reactor and two sections of fluidized-bed reactors according to this from top to bottom, is linked together between two reactors with low pressure drop distribution grid by using the different fluidized-bed reactor of two diameters of arranged superposed;Total hydrocarbon feed enters the one section of fluidized-bed reactor and regenerative agent haptoreaction that temperature range is 530~600 DEG C, raw material containing oxygenatedchemicals enters the two sections of fluidized-bed reactors and the catalytic technical solution of half reclaimable catalyst that temperature range is 450~530 DEG C, preferably solves the problems, such as this, available in arene industrial production.

Description

Method containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction
Technical field
The present invention relates to a kind of method containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction.
Background technology
Aromatic hydrocarbons (especially triphen, benzene Benzene, toluene Toluene, dimethylbenzene Xylene, i.e. BTX) is important basic Organic synthesis raw material.Driven by downstream derivative thing demand, the market demand sustainable growth of aromatic hydrocarbons.
It is the main life of aromatic hydrocarbons with the steam cracking process of liquid hydrocarbon (such as naphtha, diesel oil, secondary operation oil) for raw material Production. art.The technique belongs to petroleum path production technology, in recent years, due to the limited supply of petroleum resources and higher valency Lattice, cost of material are continuously increased.By factor, alternative materials prepare aromatic hydrocarbons technology and cause to be paid close attention to more and more widely.China's coal Carbon resource relative abundance.With in recent years efficiently, long period catalyst for methanol and methanol device maximize the succeeding in developing of technology, coal The production cost of base methanol and/or dimethyl ether is greatly lowered, this is methanol and/or dimethyl ether downstream product (alkene, aromatic hydrocarbons Deng) production provide cheap raw material sources.Accordingly, it is considered to aromatic hydrocarbons is prepared as raw material using methanol and/or dimethyl ether.
The technology initially see Chang of Mobil companies in 1977 et al. (Journal of Catalysis, 1977, 47,249) methanol and its oxygenate conversion on ZSM-5 molecular sieve catalyst are reported and prepares the hydrocarbons such as aromatic hydrocarbons Method.1985, Mobil companies disclosed methanol, dimethyl ether turns first in its United States Patent (USP) applied US1590321 Change the result of study of aromatic hydrocarbons processed, it is catalyst which, which uses the phosphorous ZSM-5 molecular sieve for 2.7 weight %, and reaction temperature is 400~450 DEG C, methanol, dimethyl ether air speed 1.3h-1.
Chinese patent 201010111821.4,200910090002.3,200810102684.0,200910135643.6, 200910089699.2 use a reactor, and reactor only has a reaction zone, using single reaction temperature.Chinese patent Liquefied gas and ethene in 201410447321.6 systems proposed in the lighter hydrocarbons of aromatization of methanol reaction generation return to methanol virtue Structure reactor further converts.Alcohol/ether aromatization device in the system that Chinese patent 201410106062.0 proposes Below the C7 oil phases hydro carbons that product is isolated to further is reacted into alcohol/ether aromatization device.It is generally believed that contain During oxygenatedchemicals prepares aromatic hydrocarbons, oxygenatedchemicals, such as methanol, ethanol, the dehydration generation low-carbon first under acid catalysis Hydrocarbon, lower carbon number hydrocarbons further occur aromatization and obtain aromatic hydrocarbons.The suitable reaction temperature of aromatization of low carbon hydrocarbon reaction is than oxygen-containing Compound dehydration is high, is difficult to take into account the reaction of two classes using single reaction temperature.Oxygenatedchemicals is in the temperature higher than 500 DEG C Under degree, heat scission reaction easily occurs and generates low value-added methane, carbon monoxide, while increases coke content.To reduce this Partial reaction, reaction temperature is generally below 500 DEG C, and aromatization of low carbon hydrocarbon reacts suitable reaction temperature and is higher than 500 DEG C, therefore The problem of causing such prior art arenes selectivity relatively low.
Chinese patent 200610012703.1 (using different catalyst), 200910089698.8 (double-fixed bed, catalysis Agent is different), 201210254472.0 (using different catalysts), 20100108008.1 (fixed bed reactors), 201010146915.5 propose to use two reactors, and the gas-phase product that first reactor reaction obtains partly or entirely enters The reaction was continued for second reactor.Wherein 200610012703.1,200910089698.8, the two of 201210254472.0 patents Different types of catalyst is respectively adopted in a reactor;200910089698.8,20100108008.1 patents it is all solid using two Fixed bed reactor;201010146915.5 the C2+ low-carbons hydrocarbon mixture that the product of patent aromatization reactor is isolated enters The problem of low-carbon hydro carbons reactor aromatisation, technological process is complicated, high energy consumption.
Chinese patent 201310346922.3 proposes multiple stage fluidized-bed device and the side of a kind of alcohol/ether catalytic cracking aromatic hydrocarbons Method, multiple Catalyst packing sections are separated into by horizontal multihole distributor by fluid bed.Multiple stage fluidized-bed dress described in the patent It is identical to put diameter from top to bottom.When it is described it is multiple stage fluidized-bed be four sections of fluid beds when, first, second Catalyst packing section of control Temperature is 450~500 DEG C, and the temperature for controlling the three, the 4th Catalyst packing sections is 420~450 DEG C, and the temperature is than relatively low. The raw material that the patent enters multiple stage fluidized-bed device is only alcohol/ether raw material.These conditions limit, and the arenes selectivity of this method is not It is high.
In above-mentioned patented technology all there are arenes selectivity it is low the problem of.The present invention pointedly proposes technical solution, Solves the above problem.
The content of the invention
The technical problems to be solved by the invention are the technical problems that arenes selectivity is low in the prior art, there is provided Yi Zhonghan There is the method for oxygen-containing compound material aromatic hydrocarbons two-stage reaction.It is excellent that this method has that technical process is simple, arenes selectivity is high Point.
The technical solution adopted by the present invention is as follows:A kind of catalyst including aluminosilicate molecular sieves, and overlapping cloth are provided The different fluidized-bed reactor of two diameters putting, is that one section of fluidized-bed reactor 1 and two sections of fluid beds are anti-according to this from top to bottom Device 2 is answered, is linked together between two reactors with low pressure drop distribution grid 11;Total hydrocarbon feed 7 enter temperature range for 530~ 600 DEG C of one section of fluidized-bed reactor 1, and 9 haptoreaction of regenerative agent through regenerator sloped tube 4 into one section of fluidized-bed reactor 1, The obtained product 10 rich in aromatic hydrocarbons enters subsequent separation system, and half obtained reclaimable catalyst 12 enters through half inclined tube 3 to be generated Two sections of fluidized-bed reactors 2;It is anti-that raw material 6 containing oxygenatedchemicals enters two sections of fluid beds that temperature range is 450~530 DEG C Device 2, and half reclaimable catalyst, 12 haptoreaction are answered, obtained product enters one section of fluidized-bed reactor through low pressure drop distribution grid 11 1, obtained reclaimable catalyst 8 returns to regenerator through inclined tube 5 to be generated and regenerates;It is distributed in two sections of fluidized-bed reactors 2 through low pressure drop Plate 11 enters the mass flow of catalyst and the quality of half reclaimable catalyst 12 in half inclined tube 3 to be generated of one section of fluidized-bed reactor 1 The ratio between flow is (0.1~0.9):1.
In above-mentioned technical proposal, it is preferable that the diameter and two sections of fluidized-bed reactions of one section of 1 main reaction region of fluidized-bed reactor The diameter ratio of device 2 is 3~1.01:1.
In above-mentioned technical proposal, it is preferable that total hydrocarbon feed 7 enters one section of fluid bed that temperature range is 550~590 DEG C Reactor 1;Raw material 6 containing oxygenatedchemicals enters two sections of fluidized-bed reactors 2 that temperature range is 470~520 DEG C.
In above-mentioned technical proposal, it is preferable that 11 inlet conversion rate of oxygenated compound of low pressure drop distribution grid is more than 80%.
In above-mentioned technical proposal, it is preferable that alkene gross mass percentage composition is more than 20% in gaseous stream.
In above-mentioned technical proposal, it is preferable that the carbon on half reclaimable catalyst 12, in terms of the quality of catalyst, content is 0.05~1.2%.
In above-mentioned technical proposal, it is preferable that when the weight space velocity of the raw material 6 containing oxygenatedchemicals is 0.2~5 small-1, mix When the weight space velocity for closing hydrocarbon feed 7 is 0.5~4 small-1
In above-mentioned technical proposal, it is preferable that the reaction gauge pressure of fluidized-bed reactor is 0~0.6 megapascal.
In above-mentioned technical proposal, it is preferable that total hydrocarbon feed 7 is less than 350 DEG C of hydro carbons or hydro carbons for more than two boiling range of carbon Mixture.
In above-mentioned technical proposal, it is preferable that two sections of fluidized-bed reactors 2 are equipped with least one set of built-in and/or external take heat Device.
In above-mentioned technical proposal, it is preferable that one section of 1 internal catalyst bed layer density of fluidized-bed reactor is 200~480,000 Gram/cubic metre, two sections of 2 internal catalyst bed layer density of fluidized-bed reactor are 150~400 kilograms per cubic meter.
In above-mentioned technical proposal, it is preferable that the inlet amount and total hydrocarbon feed 7 of the raw material 6 containing oxygenatedchemicals are fed The mass ratio of amount is 19~1.2:1.
In above-mentioned technical proposal, it is preferable that the raw material 6 containing oxygenatedchemicals include at least one selection methanol, ethanol, Normal propyl alcohol, isopropanol, C4~C20Alcohol, ethyl methyl ether, dimethyl ether, diethyl ether, Di Iso Propyl Ether, formaldehyde, dimethyl carbonate, acetone, The compound of acetic acid;The weight percentage of oxygenatedchemicals is at least 10% in raw material (6) containing oxygenatedchemicals.
In above-mentioned technical proposal, it is preferable that catalyst is at least one in modified element modified ZSM-5, ZSM-11 Kind, the modifying element is at least one of Zn, La, P, In, Ga, and in terms of the percentage by weight of catalyst, modifying element contains Measure as 0.01~15%.
In above-mentioned technical proposal, it is preferable that modifying element preferably is selected from least one of Zn, Ga and In.
In above-mentioned technical proposal, it is preferable that modifying element preferably is selected from Zn, Ga and In;It is highly preferred that the weight ratio of Ga and In For 1:1~5:1.
Result of study shows, in the range of 450~530 DEG C of temperature, the reaction of oxygenatedchemicals dehydration generation lower carbon number hydrocarbons, Conversion ratio is more than 99 weight %, when temperature is more than 530 DEG C, can aggravate the pyrolysis of oxygenatedchemicals, CO and CO in product2 Content increase.Aromatization of low carbon hydrocarbon reaction influenced by reaction temperature it is obvious, temperature be less than 530 DEG C, arenes selectivity is relatively low.Cause This can make oxygenatedchemicals and lower carbon number hydrocarbons that dehydration and aromatization, oxygen-containing chemical combination occur respectively under different temperature conditionss Dehydration generation lower carbon number hydrocarbons occurs in the range of 450~530 DEG C for thing, and lower carbon number hydrocarbons is high within the temperature range of 530~600 DEG C The aromatization of selectivity turns to aromatic hydrocarbons.In addition, oxygenatedchemicals dehydration is easier to occur, and aromatization of low carbon hydrocarbon reaction difficulty It is big, it is necessary to catalyst activity it is high.Therefore, the regenerated catalyst of lower carbon number hydrocarbons contact high activity can be made, with high selectivity aromatization Aromatic hydrocarbons is turned to, while obtains half reclaimable catalyst of certain carbon deposition quantity, in terms of the mass percent of catalyst, carbon content is 0.1~1.5%.The activity of half reclaimable catalyst can still meet the requirement of oxygenatedchemicals dehydration.Ground according to above-mentioned Study carefully result and obtain technical scheme.Technical solution using the present invention, aromatic hydrocarbons carbon base absorption rate are 75.5 weight %, are obtained Preferable technique effect.
Brief description of the drawings
Fig. 1 is the reaction unit schematic diagram of the present invention.
In Fig. 1,1 is one section of fluidized-bed reactor;2 be two sections of fluidized-bed reactors;3 be half inclined tube to be generated;4 is oblique for regeneration Pipe;5 be inclined tube to be generated;6 be the raw material containing oxygenatedchemicals;7 be total hydrocarbon feed;8 be spent agent;9 be regenerative agent;10 are Product rich in aromatic hydrocarbons;11 be low pressure drop distribution grid;12 be half reclaimable catalyst.
Total hydrocarbon feed 7 enters one section of fluidized-bed reactor 1 in Fig. 1, and enters one section of fluidized-bed reaction through regenerator sloped tube 4 9 haptoreaction of regenerative agent of device 1, the obtained product 10 rich in aromatic hydrocarbons enters subsequent separation system, while half obtained is to be generated Catalyst 12 enters two sections of fluidized-bed reactors 2 through half inclined tube 3 to be generated;Raw material 6 containing oxygenatedchemicals enters two sections of fluidisations Bed reactor 2, and half reclaimable catalyst, 12 haptoreaction, obtained product are anti-into one section of fluid bed through low pressure drop distribution grid 11 Device 1 is answered, obtained reclaimable catalyst 8 returns to regenerator through inclined tube 5 to be generated and regenerates.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Embodiment
【Embodiment 1】
The different fluidized-bed reactor of two diameters of arranged superposed, is one section of fluidized-bed reactor 1 according to this from top to bottom With two sections of fluidized-bed reactors 2, linked together with low pressure drop distribution grid 11 between two reactors.Total hydrocarbon feed 7 enters one Section fluidized-bed reactor 1, and 9 haptoreaction of regenerative agent through regenerator sloped tube 4 into one section of fluidized-bed reactor 1, obtained richness Product 10 containing aromatic hydrocarbons enters subsequent separation system, and half obtained reclaimable catalyst 12 enters two sections of fluidisations through half inclined tube 3 to be generated Bed reactor 2.Raw material 6 containing oxygenatedchemicals enters two sections of fluidized-bed reactors 2, and half reclaimable catalyst 12 contacts instead Should, obtained product enters one section of fluidized-bed reactor 1 through low pressure drop distribution grid 11, and obtained reclaimable catalyst 8 is through to be generated oblique Pipe 5 returns to regenerator regeneration.
Total hydrocarbon feed 7 is C3~C7Chain hydrocarbon is mixed, propane mass percentage is 30%.Original containing oxygenatedchemicals Material 6 is dimethyl ether.The mass ratio of 7 inlet amount of inlet amount and total hydrocarbon feed of raw material 6 containing oxygenatedchemicals is 19:1.
The diameter of one section of 1 main reaction region of fluidized-bed reactor and the diameter ratio of two sections of fluidized-bed reactors 2 are 3:1;Two sections Mass flow of catalyst and half through the one section of fluidized-bed reactor 1 of entrance of low pressure drop distribution grid 11 in fluidized-bed reactor 2 is to be generated The ratio between mass flow of half reclaimable catalyst 12 is 0.1 in inclined tube 3:1;11 inlet oxygenate conversion of low pressure drop distribution grid Rate is 80.1%, and alkene gross mass percentage composition is 20.1% in gaseous stream.Two sections of fluidized-bed reactors 2 are equipped with built in one group Heat collector.
One section of 1 reaction bed temperature of fluidized-bed reactor is 530 DEG C, and catalyst bed density is 200 kilograms/cube Rice.Two sections of 2 reaction bed temperatures of fluidized-bed reactor are 450 DEG C, and catalyst bed density is 150 kilograms per cubic meter, is contained When the weight space velocity of the raw material 6 of oxygenatedchemicals is 5 small-1, when the weight space velocity of total hydrocarbon feed 7 is 4 small-1, reacting gauge pressure is 0.3 megapascal.
Carbon on half reclaimable catalyst 12, in terms of the quality of catalyst, content 1.2%.
Using Zn-La-P-ZSM-5 catalyst, in terms of the mass percent of catalyst, Zn constituent contents are 7%, La elements Content is 5%, and P element content is 3%.
The result shows that aromatic hydrocarbons carbon base absorption rate is 68.7 weight %.
【Embodiment 2】
According to the condition and step described in embodiment 1, total hydrocarbon feed 7 is C2~C7Chain hydrocarbon is mixed, propane quality percentage contains Measure as 70%.Raw material 6 containing oxygenatedchemicals is methanol and alcohol mixture, and methanol and ethanol mass ratio are 8:2.Containing containing The mass ratio of 7 inlet amount of inlet amount and total hydrocarbon feed of the raw material 6 of oxygen compound is 1.2:1.
The diameter of one section of 1 main reaction region of fluidized-bed reactor and the diameter ratio of two sections of fluidized-bed reactors 2 are 1.01:1;Two Enter the mass flow of catalyst of one section of fluidized-bed reactor 1 with partly treating through low pressure drop distribution grid 11 in section fluidized-bed reactor 2 The ratio between mass flow of half reclaimable catalyst 12 is 0.9 in raw inclined tube 3:1;11 inlet oxygenatedchemicals of low pressure drop distribution grid turns Rate is 90%, and alkene gross mass percentage composition is 40% in gaseous stream.Two sections of fluidized-bed reactors 2 are equipped with one group and external take Hot device.
One section of 1 reaction bed temperature of fluidized-bed reactor is 600 DEG C, and catalyst bed density is 480 kilograms/cube Rice.Two sections of 2 reaction bed temperatures of fluidized-bed reactor are 530 DEG C, and catalyst bed density is 400 kilograms per cubic meter, is contained When the weight space velocity of the raw material 6 of oxygenatedchemicals is 0.2 small-1, when the weight space velocity of total hydrocarbon feed 7 is 0.5 small-1, reaction pressure Power is normal pressure.
Carbon on half reclaimable catalyst 12, in terms of the quality of catalyst, content 0.05%.
Using Zn-ZSM-5 catalyst, in terms of the mass percent of catalyst, Zn constituent contents are 0.01%.
The result shows that aromatic hydrocarbons carbon base absorption rate is 68.4 weight %.
【Embodiment 3】
According to the condition and step described in embodiment 1, total hydrocarbon feed 7 is C3~C7Chain hydrocarbon is mixed, propane quality percentage contains Measure as 40%.Raw material 6 containing oxygenatedchemicals is methanol, and methanol quality percentage composition is 98%.Contain oxygenatedchemicals The mass ratio of 7 inlet amount of inlet amount and total hydrocarbon feed of raw material 6 is 8:1.
The diameter of one section of 1 main reaction region of fluidized-bed reactor and the diameter ratio of two sections of fluidized-bed reactors 2 are 1.5:1;Two Enter the mass flow of catalyst of one section of fluidized-bed reactor 1 with partly treating through low pressure drop distribution grid 11 in section fluidized-bed reactor 2 The ratio between mass flow of half reclaimable catalyst 12 is 0.7 in raw inclined tube 3:1;11 inlet oxygenatedchemicals of low pressure drop distribution grid turns Rate is 95%, and alkene gross mass percentage composition is 60% in gaseous stream.Two sections of fluidized-bed reactors 2 are equipped with one group and external take Hot device.
One section of 1 reaction bed temperature of fluidized-bed reactor is 570 DEG C, and catalyst bed density is 380 kilograms/cube Rice.Two sections of 2 reaction bed temperatures of fluidized-bed reactor are 500 DEG C, and catalyst bed density is 300 kilograms per cubic meter, is contained When the weight space velocity of the raw material 6 of oxygenatedchemicals is 1 small-1, when the weight space velocity of total hydrocarbon feed 7 is 0.8 small-1, react gauge pressure For 0.2 megapascal.
Carbon on half reclaimable catalyst 12, in terms of the quality of catalyst, content 0.1%.
Using Zn-P-ZSM-5 catalyst, in terms of the mass percent of catalyst, Zn constituent contents are 3.5%, and P element contains Measure as 2.1%.
The result shows that aromatic hydrocarbons carbon base absorption rate is 74.8 weight %.
【Embodiment 4】
According to the raw material described in embodiment 3, condition and step.Using Zn-Ga-In-ZSM-5 catalyst, with catalyst Mass percent meter, Zn constituent contents for 3.5%, Ga constituent contents be 1.2%, In constituent contents be 1.2%.
The result shows that aromatic hydrocarbons carbon base absorption rate is 75.5 weight %.
【Embodiment 5】
According to the raw material described in embodiment 3, condition and step.Using Zn-Ga-In-ZSM-5 catalyst, with catalyst Mass percent meter, Zn constituent contents for 3.5%, Ga constituent contents be 2%, In constituent contents be 0.4%.
The result shows that aromatic hydrocarbons carbon base absorption rate is 76.0 weight %.
【Embodiment 6】
According to the catalyst described in embodiment 3, raw material and step, one section of 1 reaction bed temperature of fluidized-bed reactor is 540℃.Two sections of 2 reaction bed temperatures of fluidized-bed reactor are 460 DEG C.
The result shows that aromatic hydrocarbons carbon base absorption rate is 70.1 weight %.
【Embodiment 7】
According to the catalyst described in embodiment 3, raw material and step, one section of 1 reaction bed temperature of fluidized-bed reactor is 598℃.Two sections of 2 reaction bed temperatures of fluidized-bed reactor are 525 DEG C.
The result shows that aromatic hydrocarbons carbon base absorption rate is 72.5 weight %.
【Comparative example 1】
Using the operating procedure of embodiment 3, catalyst and reaction condition.One section of 1 catalyst bed temperature of fluidized-bed reactor Spend for 520 DEG C.Two sections of 2 reaction bed temperatures of fluidized-bed reactor are 440 DEG C.Alkene gross mass percentage composition in gaseous stream For 10%.The result shows that aromatic hydrocarbons carbon base absorption rate is 58.3 weight %.
【Comparative example 2】
Using the operating procedure of embodiment 3, catalyst and reaction condition.One section of 1 main reaction region of fluidized-bed reactor it is straight The diameter ratio of footpath and two sections of fluidized-bed reactors 2 is 1:1.The result shows that aromatic hydrocarbons carbon base absorption rate is 67.8 weight %.
【Comparative example 3】
Using the operating procedure and reaction condition of embodiment 3.Using Zn-P-ZSM-5 catalyst, with the quality hundred of catalyst Divide than meter, Zn constituent contents are 8.5%, and P element content is 7.1%.The result shows that aromatic hydrocarbons carbon base absorption rate is 69.1 weight %.
【Comparative example 4】
Using the operating procedure and reaction condition of embodiment 3.Using ZSM-5 catalyst.The result shows that aromatic hydrocarbons carbon base absorption rate For 65.3 weight %.

Claims (13)

1. a kind of method containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, including:
A kind of catalyst including aluminosilicate molecular sieves is provided, the different fluidized-bed reaction with two diameters of arranged superposed Device, is one section of fluidized-bed reactor (1) and two sections of fluidized-bed reactors (2) according to this from top to bottom, low pressure is used between two reactors Drop distribution grid (11) links together;
Total hydrocarbon feed (7) enters one section of fluidized-bed reactor (1) that temperature range is 530~600 DEG C, and through regenerator sloped tube (4) regenerative agent (9) haptoreaction of one section of fluidized-bed reactor (1) is entered, after the obtained product (10) rich in aromatic hydrocarbons enters Continuous piece-rate system, obtained half reclaimable catalyst (12) enter two sections of fluidized-bed reactors (2) through half inclined tube (3) to be generated;
Raw material (6) containing oxygenatedchemicals enters two sections of fluidized-bed reactors (2) that temperature range is 450~530 DEG C, and half Reclaimable catalyst (12) haptoreaction, obtained product enter one section of fluidized-bed reactor (1) through low pressure drop distribution grid (11), obtain The reclaimable catalyst (8) arrived returns to regenerator regeneration through inclined tube to be generated (5);
Enter the catalyst matter of one section of fluidized-bed reactor (1) in two sections of fluidized-bed reactors (2) through low pressure drop distribution grid (11) It is (0.1~0.9) to measure the ratio between mass flow of half reclaimable catalyst (12) in flow and half inclined tube (3) to be generated:1.
2. the method according to claim 1 containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, it is characterised in that low Pressure drop distribution plate (11) inlet conversion rate of oxygenated compound is more than 80%.
3. the method according to claim 1 containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, it is characterised in that gas Alkene gross mass percentage composition is more than 20% in phase logistics.
4. the method according to claim 1 containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, it is characterised in that one The diameter of section fluidized-bed reactor (1) main reaction region and the diameter ratio of two sections of fluidized-bed reactors (2) are 3~1.01:1.
5. the method according to claim 1 containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, it is characterised in that half Carbon on reclaimable catalyst (12), in terms of the quality of catalyst, content is 0.05~1.2%.
6. the method according to claim 1 containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, it is characterised in that contain When the weight space velocity for having the raw material (6) of oxygenatedchemicals is 0.2~5 small-1, the weight space velocity of total hydrocarbon feed (7) is 0.5~4 Hour-1
7. the method according to claim 1 containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, it is characterised in that stream The reaction gauge pressure of fluidized bed reactor is 0~0.6 megapascal.
8. the method according to claim 1 containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, it is characterised in that one Section fluidized-bed reactor (1) internal catalyst bed layer density is 200~480 kilograms per cubic meter, in two sections of fluidized-bed reactors (2) Catalyst bed density is 150~400 kilograms per cubic meter.
9. the method according to claim 1 containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, it is characterised in that mixed Close hydro carbons or hydrocarbon mixture that hydrocarbon feed (7) is less than 350 DEG C for more than two boiling range of carbon.
10. the method according to claim 1 containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, it is characterised in that contain The raw material (6) for having oxygenatedchemicals includes at least one selection methanol, ethanol, normal propyl alcohol, isopropanol, C4~C20Alcohol, ethyl methyl ether, Dimethyl ether, diethyl ether, Di Iso Propyl Ether, formaldehyde, dimethyl carbonate, acetone, the compound of acetic acid;Original containing oxygenatedchemicals The weight percentage for expecting oxygenatedchemicals in (6) is at least 10%.
11. the method according to claim 1 containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, it is characterised in that contain It is 19~1.2 to have the inlet amount of the raw material (6) of oxygenatedchemicals and the mass ratio of total hydrocarbon feed (7) inlet amount:1.
12. the method according to claim 1 containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, it is characterised in that urge Agent is at least one of modified element modified ZSM-5, ZSM-11, and the modifying element is in Zn, La, P, In, Ga At least one, in terms of the percentage by weight of catalyst, modifying element content be 0.01~15%.
13. the method according to claim 1 containing oxygen-containing compound material aromatic hydrocarbons two-stage reaction, it is characterised in that two Section fluidized-bed reactor (2) is equipped with least one set of built-in and/or external heat collector.
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CN110819373A (en) * 2018-08-07 2020-02-21 中石化广州工程有限公司 Device and method for preparing gasoline by using oxygen-containing compound
CN110818522A (en) * 2018-08-07 2020-02-21 中石化广州工程有限公司 Device and method for preparing aromatic hydrocarbon and low-carbon olefin from oxygen-containing compound
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CN112569875A (en) * 2019-09-30 2021-03-30 中国石油化工股份有限公司 Reducing fluidized bed reactor
CN114130313A (en) * 2021-11-08 2022-03-04 清华大学 C is to be3-C9Fluidized bed continuous reaction regeneration system and method for converting alkane into aromatic hydrocarbon
CN114130314A (en) * 2021-11-08 2022-03-04 清华大学 C is to be3-C9Continuous reaction regeneration system and method for converting hydrocarbon and alcohol ether into aromatic hydrocarbon
CN110818522B (en) * 2018-08-07 2022-09-09 中石化广州工程有限公司 Device and method for preparing aromatic hydrocarbon and low-carbon olefin from oxygen-containing compound

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CN108017483B (en) * 2016-11-04 2020-12-29 中国石油化工股份有限公司 Method for preparing aromatic hydrocarbon by high-selectivity conversion of raw material containing methanol and/or dimethyl ether
CN108017483A (en) * 2016-11-04 2018-05-11 中国石油化工股份有限公司 The method of raw material high selectivity conversion for preparing arene containing methanol and/or dimethyl ether
CN110819373B (en) * 2018-08-07 2021-12-14 中石化广州工程有限公司 Device and method for preparing gasoline by using oxygen-containing compound
CN110819375A (en) * 2018-08-07 2020-02-21 中石化广州工程有限公司 Device and method for preparing gasoline from oxygen-containing compound
CN110818521A (en) * 2018-08-07 2020-02-21 中石化广州工程有限公司 Device and method for preparing aromatic hydrocarbon and low-carbon olefin by using oxygen-containing compound
CN110818522A (en) * 2018-08-07 2020-02-21 中石化广州工程有限公司 Device and method for preparing aromatic hydrocarbon and low-carbon olefin from oxygen-containing compound
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CN110818521B (en) * 2018-08-07 2022-06-07 中石化广州工程有限公司 Device and method for preparing aromatic hydrocarbon and low-carbon olefin by using oxygen-containing compound
CN110819375B (en) * 2018-08-07 2021-12-14 中石化广州工程有限公司 Device and method for preparing gasoline from oxygen-containing compound
CN110818522B (en) * 2018-08-07 2022-09-09 中石化广州工程有限公司 Device and method for preparing aromatic hydrocarbon and low-carbon olefin from oxygen-containing compound
CN111099947A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 Method for preparing aromatic hydrocarbon by efficiently converting methanol
CN111097337A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 Zoned fluidized bed reaction-regeneration device and process for preparing aromatic hydrocarbon through methanol conversion
CN111099947B (en) * 2018-10-25 2022-08-12 中国石油化工股份有限公司 Method for preparing aromatic hydrocarbon by efficiently converting methanol
CN111097337B (en) * 2018-10-25 2022-04-05 中国石油化工股份有限公司 Zoned fluidized bed reaction-regeneration device and process for preparing aromatic hydrocarbon through methanol conversion
CN112569875A (en) * 2019-09-30 2021-03-30 中国石油化工股份有限公司 Reducing fluidized bed reactor
CN114130314A (en) * 2021-11-08 2022-03-04 清华大学 C is to be3-C9Continuous reaction regeneration system and method for converting hydrocarbon and alcohol ether into aromatic hydrocarbon
CN114130313A (en) * 2021-11-08 2022-03-04 清华大学 C is to be3-C9Fluidized bed continuous reaction regeneration system and method for converting alkane into aromatic hydrocarbon

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