CN109694297A - The method for maintaining high arenes selectivity during methanol aromatic hydrocarbons - Google Patents
The method for maintaining high arenes selectivity during methanol aromatic hydrocarbons Download PDFInfo
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The present invention relates to a kind of methods for maintaining high arenes selectivity during methanol aromatic hydrocarbons, mainly solve the problems, such as that arenes selectivity is low in the prior art.The present invention cools down the partial regeneration catalyst of Returning reactor by using cooler, regenerated catalyst is through regenerating the low temperature conversion area of the close phase section of lower oblique tube Returning reactor after cooling, uncooled catalyst is through regenerating the aromatic hydrocarbons reaction zone of the upper close phase section of inclined tube Returning reactor, low temperature conversion area temperature is 450~480 DEG C, the temperature in aromatization area is the technical solution within the scope of 500~550 DEG C, it preferably solves the problems, such as this, can be used in the industrial production of aromatic hydrocarbons.
Description
Technical field
The present invention relates to a kind of methods for maintaining high arenes selectivity during methanol aromatic hydrocarbons.
Background technique
Aromatic hydrocarbons (especially triphen, benzene Benzene, toluene Toluene, dimethylbenzene Xylene, i.e. BTX) is important substantially
Organic synthesis raw material.By the driving of downstream derivative object 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 valence
Lattice, cost of material are continuously increased.By factor, alternative materials prepare aromatic hydrocarbons technology and cause to pay close attention to more and more widely.Wherein, right
A kind of important Chemical Manufacture raw material is increasingly becoming due to rich coal resources in China in coal-based methanol, dimethyl ether raw material,
Important supplement as petroleum.Accordingly, it is considered to prepare aromatic hydrocarbons as raw material containing oxygenatedchemicals.
The technology initially see Chang of Mobil company 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 company disclosed methanol, dimethyl ether turns in the United States Patent (USP) US1590321 of its application for the first time
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 1.3 (Grams Per Hour)/gram catalyst.
Patent in terms of methanol conversion for preparing arene catalyst is more, as Chinese patent CN102372535,
CN102371176、CN102371177、CN102372550、CN102372536、CN102371178、CN102416342、
CN101550051, United States Patent (USP) US4615995, US2002/0099249A1 etc..These patents are mainly around metal-modified
ZSM-5 molecular sieve catalyst, modified metal include Zn, Ga, Ag, Cu, Mn etc..
United States Patent (USP) US4686312, Chinese patent ZL101244969, ZL1880288, CN101602646,
CN101823929, CN101671226, CN102199069, CN102199446, CN1880288 etc. disclose a variety of methanol system virtues
The process route of hydrocarbon.Patent CN102775261, CN102146010, CN102531821, CN102190546, CN102372537
Other products such as co-producing light olefins, gasoline while methanol aromatic hydrocarbons.These patents mainly introduce various different routes
Methanol aromatic hydrocarbons method.
Chinese patent 200910162649.2 proposes that heavy oil catalytic cracking reaction-regenerative system thermal balance is adjusted flexibly in one kind
Method, by beside regenerator be arranged conventional regeneration catalyst heat collector while, set in regenerated catalyst
Set regenerated catalyst cooler, on the one hand the two coupling linkage controls regenerator temperature, on the other hand realize to entering riser
The heat and its temperature that reactor regenerated catalyst carries are adjusted, to realize heterogeneity feedstock oil in cracking reaction
The adjusting of required difference oil ratio.The method of the patent introduction is related to a kind of flexible regenerator heat taking method, makes regeneration catalyzing
The temperature of agent can be adjusted flexibly in 610~670 DEG C according to the difference of heavy oil feedstock property, and finish mixing temperature is 530~580
It is adjusted flexibly in DEG C.The method that the patent proposes maintains one reaction temperature of reactor.
Raw material aromatic hydrocarbons process containing oxygenatedchemicals uses the ZSM-5 molecular sieve catalyst of Metal Supported.With reaction
Time extends, and ZSM-5 molecular sieve can gradually framework dealumination, acidity decline in hydro-thermal atmosphere.The reduction of ZSM-5 molecular sieve acidity
It will lead to the decline of catalyst Aromatization Activity, arenes selectivity reduces.Due to the special skeleton structure of ZSM-5 molecular sieve, hydro-thermal
The phenomenon that inactivation, is inevitable.For the high arenes selectivity for maintaining the raw material aromatic hydrocarbons process containing oxygenatedchemicals stable, need
Reaction temperature is improved in time in the larger context in catalyst activity reduction, arenes selectivity decline.The present invention is directed to
Technical solution is proposed to property, solves the above problem.
Summary of the invention
The technical problem to be solved by the present invention is to the low technical problems of prior art arenes selectivity, provide a kind of methanol
The method for maintaining high arenes selectivity during aromatic hydrocarbons processed.This method has control method flexibly simple, and arenes selectivity is high
Advantage.
The technical solution adopted by the invention is as follows: a kind of method for maintaining high arenes selectivity during methanol aromatic hydrocarbons,
Raw material including methanol enters fluidized-bed reactor and the catalyst haptoreaction including ZSM-5 molecular sieve, the carbon deposit after reaction
Catalyst is regenerated through stripping laggard fluidized bed regenerator, and the regenerated catalyst of formation enters degassing tank, and degassing tank outlet is urged
Agent is at least divided into two-way, and all the way by regenerating upper inclined tube Returning reactor, another way is after cooler is cooling by under regeneration
Inclined tube Returning reactor；Wherein, the close phase section of reactor is divided into low temperature by the connector of inclined tube and reactor from bottom to top in regeneration
Zone of transformation and aromatization area, the temperature in low temperature conversion area are 450 DEG C~480 DEG C, and the temperature in aromatization area is 500 DEG C
~550 DEG C；The distance of the connector of inclined tube and reactor to reactor bottom accounts for the 10 of the close phase section total height of reactor in regeneration
~40%；Regeneration lower oblique tube and reactor connector to reactor bottom distance account for the close phase section total height of reactor 3~
15%；It is 20~60 that the difference of regenerated catalyst temperature in inclined tube is gone up in regenerated catalyst temperature and regeneration in the regeneration lower oblique tube
℃。
In above-mentioned technical proposal, it is preferable that degassing tank fluidizing agent is nitrogen or steam, and cooler fluidizing agent is nitrogen
Or steam, cooler is interior to be equipped at least one set of heat production coil pipe, and it is water or methanol that thermal medium is taken in heat production coil pipe.
In above-mentioned technical proposal, it is preferable that the temperature in low temperature conversion area is 450 DEG C~470 DEG C, the temperature in aromatization area
Degree is 505 DEG C~540 DEG C.
In above-mentioned technical proposal, it is preferable that fluidized-bed reactor is followed successively by close phase section, changeover portion and dilute phase from bottom to top
Section, dilute phase section is interior to be equipped at least one set of cyclone separator, wherein the ratio that close phase section accounts for total reactor height is 40~70%.
In above-mentioned technical proposal, it is preferable that in one embodiment of the invention, the connector of inclined tube and reactor is to instead in regeneration
The distance of device bottom is answered to account for the 35% of the close phase section total height of reactor；The connector of lower oblique tube and reactor is regenerated to reactor bottom
The distance in portion accounts for the 12% of the close phase section total height of reactor.
In above-mentioned technical proposal, it is preferable that the close phase section catalyst bed density of reactor is 150~450 kilograms/cube
Rice；The mass space velocity of methanol is 0.1~7 hour-1；Reaction gauge pressure is 0~0.5 megapascal.
In above-mentioned technical proposal, it is preferable that the carrier of catalyst is kaolin, aluminium oxide, silica；Active component and
The mass ratio of carrier is 10~50: 50~90.
In above-mentioned technical proposal, it is preferable that catalyst load has one or more elements in Zn, Ag, P, Ga, Cu, Mn, Mg
Or oxide, in terms of the weight percent of catalyst, content is 0.01~15%.
In above-mentioned technical proposal, it is preferable that degassing tank catalyst, by weight, 60~80% are returned by regenerating upper inclined tube
Reactor is returned, 20~40% pass through regeneration lower oblique tube Returning reactor after cooler is cooling.
In the present invention, when arenes selectivity reduces, the close phase section temperature of reactor is improved, it can be negative by adjusting heat production coil pipe
Lotus adjusts regulation of the temperature realization of one regenerated catalyst to close phase section reaction temperature；It can also be by adjusting the upper inclined tube of regeneration
The internal circulating load of catalyst realizes the regulation to close phase section reaction temperature in middle catalyst and regeneration lower oblique tube；It can also be taken by adjusting
The internal circulating load of catalyst and catalyst in regeneration lower oblique tube is realized anti-to close phase section in hot plate tube load and the upper inclined tube of adjustment regeneration
Answer the regulation of temperature.The mass ratio of catalyst activity component and carrier is 10~50: 50~90, preferably 20~40: 60~80.It urges
Agent load has one or more elements or oxide, preferably Zn, P in Zn, Ag, P, Ga, Cu, Mn, Mg；With the quality of catalyst
Percentages, the content of the element of load on a catalyst are 0.01~15%, preferably 0.02~8%.The active group of catalyst
It is selected from ZSM-5 molecular sieve, 0.01~5% Zn element or oxidation are loaded in terms of the weight percent of catalyst, on catalyst
Object, 0.1~8% P element or oxide.
The regenerated catalyst of Returning reactor is divided into two strand different with flow of temperature by the present invention, and by the close phase of reactor
Section is divided into two reaction zones domain, passes through the anti-of the accurate control two reaction zones domains of flow and temperature adjustment of two bursts of regenerated catalysts
Temperature is answered, while controlling the height in two reaction zones domain, so that in low temperature conversion area dehydration, which occurs, for methanol generates lower carbon number hydrocarbons,
The lower carbon number hydrocarbons aromatization highly selective in aromatization area turns to aromatic hydrocarbons, the aromatization of methanol reaction and lower carbon number hydrocarbons compared with
It is carried out under good operating condition.In addition, the present invention can neatly adjust two reaction zones according to catalyst activity situation of change
Reaction temperature, meet methanol reaction and lower carbon number hydrocarbons aromatization demand, the selectivity of aromatic hydrocarbons in product is tieed up always
It holds in higher level, achieves preferable technical effect.
Detailed description of the invention
Fig. 1 is the flow diagram of technical solution of the present invention.
Fig. 2 is reactor schematic diagram.
Fig. 3 is the close phase section schematic diagram of reactor
In FIG. 1 to FIG. 3,1 is reactor, and 2 be regenerator, and 3 be stripper, and 4 be degassing tank, and 5 be cooler, and 6 be stripping
Inclined tube, 7 be inclined tube to be generated, and 8 be degassing tank inclined tube, and 9 be to regenerate upper inclined tube, and 10 be cooler inclined tube, and 11 be to regenerate lower oblique tube, 12
To regenerate upper inclined tube slide valve, 13 be regeneration lower oblique tube slide valve, and 14 be slide valve to be generated, and 15 be reactor cyclone, and 16 is again
Raw device cyclone separator, 17 be raw material, and 18 be reaction product, and 19 be regenerating medium, and 20 be flue gas, and 21 be the close phase section of reactor,
22 be reactor changeover portion, and 23 be reactor dilute phase section, and 24 be low temperature conversion area, and 25 be aromatization area.
Raw material 17 enters reactor 1 and catalyst haptoreaction from close 21 lower part of phase section of reactor, generates reaction product 18
And carbon deposited catalyst, the reactor cyclone 15 that reaction product 18 is located at reactor dilute phase section 23 separate carbon deposited catalyst
Enter subsequent separation system afterwards；Carbon deposited catalyst enters stripper 3 through stripping inclined tube 6, and the carbon deposited catalyst after stripping is through to be generated
Inclined tube 7 enters regenerator 2 and regenerating medium 19 contacts coke burning regeneration and obtains regenerated catalyst and flue gas 20, and flue gas 20 is through regenerating
Device cyclone separator 16 enters subsequent smoke energy recovering system, the degassed tank of regenerated catalyst after isolating regenerated catalyst
Inclined tube 8 enters degassing tank 4, and partial regeneration rear catalyst is regenerated upper 9 Returning reactor 1 of inclined tube, partial regeneration rear catalyst warp
Cooler inclined tube 10 enters cooler 5, and cooling rear catalyst is through regenerating 11 Returning reactor 1 of lower oblique tube.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
[embodiment 1]
The raw material that methanol quality content is 70% enters fluidized-bed reactor and the contact of Ag-ZSM-5 molecular sieve catalyst is anti-
It answers, the carbon deposited catalyst after reaction is regenerated through stripping laggard fluidized bed regenerator, and the regenerated catalyst of formation enters degassing tank,
The catalyst of degassing tank outlet is divided into two-way, and by weight, 60% by regenerating upper inclined tube Returning reactor, and 40% through cooler
Pass through regeneration lower oblique tube Returning reactor after cooling；Wherein, in regeneration the connector of inclined tube and reactor by the close phase section of reactor
It is divided into low temperature conversion area and aromatization area from bottom to top, the temperature in low temperature conversion area is 450 DEG C, the temperature in aromatization area
Degree is 500 DEG C；The distance of the connector of inclined tube and reactor to reactor bottom accounts for the close phase section total height of reactor in regeneration
40%；The distance of connector to the reactor bottom of regeneration lower oblique tube and reactor accounts for the 3% of the close phase section total height of reactor.
Degassing tank fluidizing agent is nitrogen, and cooler fluidizing agent is nitrogen, is equipped with one group of heat production coil pipe in cooler, takes
It is water that thermal medium is taken in hot coil.Regenerate in lower oblique tube regenerated catalyst temperature and regenerate in upper inclined tube regenerated catalyst temperature it
Difference is 20 DEG C.The close phase section catalyst bed density of reactor is 150 kilograms per cubic meter；The mass space velocity of methanol is 7 hours-1；Instead
Answering gauge pressure is 0.5 megapascal.
The carrier of Ag-ZSM-5 catalyst is kaolin；Ag element mass content is 0.01%, active component and carrier
Mass ratio is 10: 90.Reaction result are as follows: methanol conversion 99.0%, the carbon-based selectivity of aromatic hydrocarbons one way are 62.8 weight %,
Selectivity of the BTX in total virtue is 80.1 weight %.
[embodiment 2]
According to condition described in embodiment 1 and step, methanol quality content is 80% in raw material, the temperature in low temperature conversion area
It is 480 DEG C, the temperature in aromatization area is 550 DEG C；In regeneration the connector of inclined tube and reactor to reactor bottom away from
From accounting for the 10% of the close phase section total height of reactor；The distance of connector to the reactor bottom of regeneration lower oblique tube and reactor accounts for instead
Answer the 15% of the close phase section total height of device.
Degassing tank fluidizing agent is steam, and cooler fluidizing agent is steam, is equipped with one group of heat production coil pipe in cooler, takes
It is methanol that thermal medium is taken in hot coil.It regenerates regenerated catalyst temperature in lower oblique tube and regenerates regenerated catalyst temperature in upper inclined tube
Difference be 60 DEG C.The regenerated catalyst of degassing tank outlet, by weight, 80% goes up inclined tube Returning reactor by regenerating, and 20%
Pass through regeneration lower oblique tube Returning reactor after cooler is cooling.The close phase section catalyst bed density of reactor is 450 kilograms/it is vertical
Square rice；The mass space velocity of methanol is 0.1 hour-1；Reaction gauge pressure is 0 megapascal.
Catalyst is Ga-ZSM-5, and carrier is aluminium oxide；Ga element mass content is 15%, the matter of active component and carrier
Amount is than being 10: 50.
Reaction result are as follows: methanol conversion 99.5%, the carbon-based selectivity of aromatic hydrocarbons one way are 61.7 weight %, and BTX is total
Selectivity in virtue is 82.3 weight %.
[embodiment 3]
According to condition described in embodiment 1 and step, methanol quality content is 98% in raw material, the temperature in low temperature conversion area
It is 470 DEG C, the temperature in aromatization area is 530 DEG C；In regeneration the connector of inclined tube and reactor to reactor bottom away from
From accounting for the 30% of the close phase section total height of reactor；The distance of connector to the reactor bottom of regeneration lower oblique tube and reactor accounts for instead
Answer the 10% of the close phase section total height of device.
Regenerating regenerated catalyst temperature in lower oblique tube and regenerating the difference of regenerated catalyst temperature in inclined tube is 40 DEG C.Degassing
The regenerated catalyst of tank outlet, by weight, 55% by regenerating upper inclined tube Returning reactor, and 45% leads to after cooler is cooling
Cross regeneration lower oblique tube Returning reactor.The close phase section catalyst bed density of reactor is 350 kilograms per cubic meter；The quality of methanol
Air speed is 4 hours-1；Reaction gauge pressure is 0.3 megapascal.
Catalyst is Mn-ZSM-5, and carrier is silica；Mn element mass content is 9%, active component and carrier
Mass ratio is 50: 50.
Reaction result are as follows: methanol conversion 99.6%, the carbon-based selectivity of aromatic hydrocarbons one way are 64.4 weight %, and BTX is total
Selectivity in virtue is 82.6 weight %.
[embodiment 4]
According to condition described in embodiment 1 and step, methanol quality content is 100% in raw material, the temperature in low temperature conversion area
Degree is 460 DEG C, and the temperature in aromatization area is 505 DEG C；The connector of inclined tube and reactor is to reactor bottom in regeneration
Distance accounts for the 35% of the close phase section total height of reactor；The distance of connector to the reactor bottom of regeneration lower oblique tube and reactor accounts for
The 12% of the close phase section total height of reactor.
Regenerating regenerated catalyst temperature in lower oblique tube and regenerating the difference of regenerated catalyst temperature in inclined tube is 50 DEG C.Degassing
The regenerated catalyst of tank outlet, by weight, 70% by regenerating upper inclined tube Returning reactor, and 30% leads to after cooler is cooling
Cross regeneration lower oblique tube Returning reactor.The close phase section catalyst bed density of reactor is 300 kilograms per cubic meter；The quality of methanol
Air speed is 1.5 hours-1；Reaction gauge pressure is 0.2 megapascal.
Catalyst is Zn-ZSM-5, and carrier is silica；Zn element mass content is 5%, active component and carrier
Mass ratio is 50: 90.
Reaction result are as follows: methanol conversion 99.8%, the carbon-based selectivity of aromatic hydrocarbons one way are 65.8 weight %, and BTX is total
Selectivity in virtue is 85.2 weight %.
[embodiment 5]
According to raw material as described in example 4, catalyst and step, only the temperature in low temperature conversion area is 475 DEG C, aromatisation
The temperature of reaction zone is 540 DEG C；The distance of the connector of inclined tube and reactor to reactor bottom accounts for the close phase of reactor in regeneration
The 20% of section total height；It is always high that the distance of connector to the reactor bottom of regeneration lower oblique tube and reactor accounts for the close phase section of reactor
The 5% of degree.
Regenerating regenerated catalyst temperature in lower oblique tube and regenerating the difference of regenerated catalyst temperature in inclined tube is 30 DEG C.Degassing
The regenerated catalyst of tank outlet, by weight, 50% by regenerating upper inclined tube Returning reactor, and 50% leads to after cooler is cooling
Cross regeneration lower oblique tube Returning reactor.The close phase section catalyst bed density of reactor is 200 kilograms per cubic meter；The quality of methanol
Air speed is 6 hours-1；Reaction gauge pressure is 0.4 megapascal.
Reaction result are as follows: methanol conversion 99.3%, the carbon-based selectivity of aromatic hydrocarbons one way are 63.1 weight %, and BTX is total
Selectivity in virtue is 83.3 weight %.
[embodiment 6]
According to fluidized-bed reactor as described in example 4, condition and step, only catalyst is Zn-Ga-ZSM-5, carrier
For silica；Zn element mass content is that 5%, Ga element mass content is 1.5%, and the mass ratio of active component and carrier is
50∶50。
Reaction result are as follows: methanol conversion 99.3%, the carbon-based selectivity of aromatic hydrocarbons one way are 63.7 weight %, and BTX is total
Selectivity in virtue is 83.4 weight %.
[embodiment 7]
According to fluidized-bed reactor as described in example 4, condition and step, only catalyst is Zn-P-ZSM-5, carrier
For silica；Zn element mass content is 10%, and P element mass content is 5%, and the mass ratio of active component and carrier is 50
∶50。
Reaction result are as follows: methanol conversion 99.6%, the carbon-based selectivity of aromatic hydrocarbons one way are 63.0 weight %, and BTX is total
Selectivity in virtue is 83.2 weight %.
[comparative example 1]
According to catalyst as described in example 4 and step, only the close phase section of fluidized-bed reactor is a reaction zone, reaction
500 DEG C of temperature, the close phase section catalyst bed density of reactor is 300 kilograms per cubic meter；The mass space velocity of methanol is 1.5 small
When-1；Reaction gauge pressure is 0.2 megapascal.
Reaction result are as follows: methanol conversion 98.2%, the carbon-based selectivity of aromatic hydrocarbons one way are 56.2 weight %, and BTX is total
Selectivity in virtue is 74.3 weight %.
[comparative example 2]
According to fluidized-bed reactor as described in example 4, catalyst and step, regenerated catalyst in lower oblique tube is only regenerated
Temperature and the difference for regenerating regenerated catalyst temperature in upper inclined tube are 10 DEG C.
Reaction result are as follows: methanol conversion 99.0%, the carbon-based selectivity of aromatic hydrocarbons one way are 58.5 weight %, and BTX is total
Selectivity in virtue is 79.4 weight %.
[comparative example 3]
According to fluidized-bed reactor as described in example 4, catalyst and step, the catalyst that only degassing tank exports, with
Poidometer, 40% by regenerating upper inclined tube Returning reactor, and 60% returns to reaction by regeneration lower oblique tube after cooler is cooling
Device.
Reaction result are as follows: methanol conversion 99.2%, the carbon-based selectivity of aromatic hydrocarbons one way are 59.4 weight %, and BTX is total
Selectivity in virtue is 78.0 weight %.
Claims (8)
1. a kind of method for maintaining high arenes selectivity during methanol aromatic hydrocarbons, the raw material including methanol enter fluidized-bed reaction
Device and catalyst haptoreaction including ZSM-5 molecular sieve, the carbon deposited catalyst after reaction are regenerated through stripping laggard fluidized bed
Device regeneration, the regenerated catalyst of formation enter degassing tank, and the catalyst of degassing tank outlet is at least divided into two-way, passes through regeneration all the way
Upper inclined tube Returning reactor, another way pass through regeneration lower oblique tube Returning reactor after cooler is cooling；Wherein, inclined tube in regeneration
The close phase section of reactor is divided into low temperature conversion area and aromatization area, low temperature conversion area from bottom to top with the connector of reactor
Temperature be 450 DEG C~480 DEG C, the temperature in aromatization area is 500 DEG C~550 DEG C；The company of inclined tube and reactor in regeneration
The distance of interface to reactor bottom accounts for the 10~40% of the close phase section total height of reactor；Regenerate the connection of lower oblique tube and reactor
The distance of mouth to reactor bottom accounts for the 3~15% of the close phase section total height of reactor；Regenerated catalyst in the regeneration lower oblique tube
Temperature and the difference for regenerating regenerated catalyst temperature in upper inclined tube are 20~60 DEG C.
2. the method for maintaining high arenes selectivity during methanol aromatic hydrocarbons according to claim 1, it is characterised in that de-
Gas tank fluidizing agent is nitrogen or steam, and cooler fluidizing agent is nitrogen or steam, is equipped at least one set in cooler and takes heat
Coil pipe, it is water or methanol that thermal medium is taken in heat production coil pipe.
3. the method for maintaining high arenes selectivity during methanol aromatic hydrocarbons according to claim 1, it is characterised in that low
The temperature of warm zone of transformation is 450 DEG C~470 DEG C, and the temperature in aromatization area is 505 DEG C~540 DEG C.
4. the method for maintaining high arenes selectivity during methanol aromatic hydrocarbons according to claim 1, it is characterised in that stream
Fluidized bed reactor is followed successively by close phase section, changeover portion and dilute phase section from bottom to top, and at least one set of cyclone separator is equipped in dilute phase section,
It is 40~70% that wherein close phase section, which accounts for the ratio of total reactor height,.
5. the method for maintaining high arenes selectivity during methanol aromatic hydrocarbons according to claim 1, it is characterised in that anti-
Answering the close phase section catalyst bed density of device is 150~450 kilograms per cubic meter；The mass space velocity of methanol is 0.1~7 hour-1；Instead
Answering gauge pressure is 0~0.5 megapascal.
6. the method for maintaining high arenes selectivity during methanol aromatic hydrocarbons according to claim 1, it is characterised in that urge
The carrier of agent is kaolin, aluminium oxide, silica；The mass ratio of active component and carrier is 10~50: 50~90.
7. the method for maintaining high arenes selectivity during methanol aromatic hydrocarbons according to claim 1, it is characterised in that urge
Agent load has one or more elements or oxide in Zn, Ag, P, Ga, Cu, Mn, Mg, in terms of the weight percent of catalyst,
Its content is 0.01~15%.
8. the method for maintaining high arenes selectivity during methanol aromatic hydrocarbons according to claim 1, it is characterised in that de-
Gas tank catalyst, by weight, 60~80% lead to after cooler is cooling by regenerating upper inclined tube Returning reactor, 20~40%
Cross regeneration lower oblique tube Returning reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710982608.2A CN109694297B (en) | 2017-10-20 | 2017-10-20 | Method for maintaining high aromatic selectivity in process of preparing aromatic hydrocarbon from methanol |
Applications Claiming Priority (1)
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0082701A1 (en) * | 1981-12-23 | 1983-06-29 | Mobil Oil Corporation | A process for producing a mixture of hydrocarbons rich in benzene, toluene, and xylene |
| EP0190816A1 (en) * | 1985-01-17 | 1986-08-13 | Mobil Oil Corporation | Process for converting oxygenates into liquid hydrocarbons |
| US4686312A (en) * | 1981-12-23 | 1987-08-11 | Mobil Oil Corporation | Aromatics production |
| US6187982B1 (en) * | 1999-10-15 | 2001-02-13 | Mobil Oil Corporation | Process for converting dienes and oxygenates to para-xylene and light olefins |
| CN102463072A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Reaction device for producing p-xylene |
| CN104557363A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Reaction device for preparing ethylene, propylene and arene by methyl alcohol and/or dimethyl ether transformation and reaction method of reaction device |
| CN104557366A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | System and method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether |
| CN204478524U (en) * | 2015-01-28 | 2015-07-15 | 中国石化工程建设有限公司 | A kind of organic oxygen compound catalytic cracking aromatic hydrocarbons reaction heat-obtaining system |
| CN105457570A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Coaxial two-stage regenerative reaction device for preparing low-carbon olefins and aromatic hydrocarbon by converting methanol or dimethyl ether and reaction method for coaxial two-stage regenerative reaction device |
| CN105985209A (en) * | 2015-01-28 | 2016-10-05 | 中国石化工程建设有限公司 | Method of producing aromatic hydrocarbon through catalytic conversion of organic oxides |
| CN105985210A (en) * | 2015-01-28 | 2016-10-05 | 中国石化工程建设有限公司 | Method of producing aromatic hydrocarbon through catalytic conversion of organic oxides |
-
2017
- 2017-10-20 CN CN201710982608.2A patent/CN109694297B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0082701A1 (en) * | 1981-12-23 | 1983-06-29 | Mobil Oil Corporation | A process for producing a mixture of hydrocarbons rich in benzene, toluene, and xylene |
| US4686312A (en) * | 1981-12-23 | 1987-08-11 | Mobil Oil Corporation | Aromatics production |
| EP0190816A1 (en) * | 1985-01-17 | 1986-08-13 | Mobil Oil Corporation | Process for converting oxygenates into liquid hydrocarbons |
| US6187982B1 (en) * | 1999-10-15 | 2001-02-13 | Mobil Oil Corporation | Process for converting dienes and oxygenates to para-xylene and light olefins |
| CN102463072A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Reaction device for producing p-xylene |
| CN104557363A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Reaction device for preparing ethylene, propylene and arene by methyl alcohol and/or dimethyl ether transformation and reaction method of reaction device |
| CN104557366A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | System and method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether |
| CN105457570A (en) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | Coaxial two-stage regenerative reaction device for preparing low-carbon olefins and aromatic hydrocarbon by converting methanol or dimethyl ether and reaction method for coaxial two-stage regenerative reaction device |
| CN204478524U (en) * | 2015-01-28 | 2015-07-15 | 中国石化工程建设有限公司 | A kind of organic oxygen compound catalytic cracking aromatic hydrocarbons reaction heat-obtaining system |
| CN105985209A (en) * | 2015-01-28 | 2016-10-05 | 中国石化工程建设有限公司 | Method of producing aromatic hydrocarbon through catalytic conversion of organic oxides |
| CN105985210A (en) * | 2015-01-28 | 2016-10-05 | 中国石化工程建设有限公司 | Method of producing aromatic hydrocarbon through catalytic conversion of organic oxides |
Non-Patent Citations (1)
| Title |
|---|
| TONG WANG: "Conversion of methanol to aromatics in fluidized bed reactor", 《CATALYSIS TODAY》 * |
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