CN104549074A - Coaxial type sectional fluidized bed reaction device for preparing ethylene, propylene and aromatic hydrocarbon by converting methyl alcohol and/or dimethyl ether, and reaction method of reaction device - Google Patents
Coaxial type sectional fluidized bed reaction device for preparing ethylene, propylene and aromatic hydrocarbon by converting methyl alcohol and/or dimethyl ether, and reaction method of reaction device Download PDFInfo
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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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
- C07C2529/44—Noble metals
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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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- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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Abstract
The invention relates to a coaxial type fluidized bed reaction device for preparing ethylene, propylene and aromatic hydrocarbon by converting methyl alcohol and/or dimethyl ether, and a reaction method of the reaction device and mainly aims at solving the problem that the yield of the ethylene, the propylene and the aromatic hydrocarbon is low. The coaxial type fluidized bed reaction device for preparing the ethylene, the propylene and the aromatic hydrocarbon by converting the methyl alcohol and/or dimethyl ether adopts a system comprising a reactor (1), a regenerator (2) and a stripper (3); raw materials (15) and circulating materials (24) enter the reactor (1) from the lower part of a first reaction section (25) of the reactor and the lower part of a second reaction section (27) of the reactor respectively to be contacted with a catalyst for carrying out reaction, a carbon deposited catalyst obtained after the reaction flows downward and enters a to-be-regenerated inclined tube (7) connected with the bottom of the reactor (1) and then is lifted to the stripper (3) by virtue of a steam stripping vertical pipe (8), a stripped catalyst enters the regenerator (2) to be regenerated, the regenerated catalyst is subjected to degassing by virtue of a degassing tank (4), and the degassed catalyst flows downward and enters the first reaction section (25) of the reactor. By adopting the technical scheme, the problem is relatively well solved, and the coaxial type fluidized bed reaction device and the reaction method provided by the invention can be applied to industrial production of the ethylene, the propylene and the aromatic hydrocarbon.
Description
Technical field
The present invention relates to coaxial-type segmental fluidized bed reaction unit and the reaction method thereof of a kind of methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons.
Background technology
Ethene, propylene and aromatic hydrocarbons (especially triphen, benzene Benzene, toluene Toluene, dimethylbenzene Xylene, i.e. BTX) are important basic organic synthesis raw materials.By the driving of downstream derivative thing demand, the market requirement sustainable growth of ethene, propylene and aromatic hydrocarbons.
The steam cracking process being raw material with liquid hydrocarbon (as petroleum naphtha, diesel oil, secondary processing oil) is the main production of ethene, propylene and aromatic hydrocarbons.This technique belongs to petroleum path production technology, and in recent years, the supply limited due to petroleum resources and higher price, raw materials cost constantly increases.The factor be subject to, alternative materials is prepared ethene, propylene and aromatic hydrocarbons technology and is caused and pay close attention to more and more widely.Wherein, for coal-based methanol, dme raw material, due to rich coal resources in China, become a kind of important Chemical Manufacture raw material just gradually, become the important supplement of petroleum.Therefore, consider with methyl alcohol and/or dme for raw material prepares ethene, propylene and aromatic hydrocarbons.
In various existing methyl alcohol, dimethyl ether catalysis transformation technology, the product of methanol/dimethyl ether conversion aromatic hydrocarbons comprises ethene, propylene and aromatic hydrocarbons simultaneously.This technology sees the people (Journal of Catalysis, 1977,47,249) such as the Chang of Mobil company in 1977 at first and reports on ZSM-5 molecular sieve catalyzer methyl alcohol and oxygenatedchemicals transforms the method preparing the hydrocarbon polymers such as aromatic hydrocarbons.1985, Mobil company is in its US Patent No. 1590321 of applying for, disclose the result of study of methyl alcohol, dimethyl ether conversion aromatic hydrocarbons first, this research adopt phosphorous be 2.7 % by weight ZSM-5 molecular sieve be catalyzer, temperature of reaction is 400 ~ 450 DEG C, methyl alcohol, dme air speed 1.3 (Grams Per Hour)/gram catalyzer.
Relevant report and the patent in this field are more, but the object product of most of technology is aromatic hydrocarbons, and ethene, propylene belong to by product, and yield is low.Such as, patent in the agent of Methanol arenes catalytic: Chinese patent CN102372535, CN102371176, CN102371177, CN102372550, CN102372536, CN102371178, CN102416342, CN101550051, US Patent No. 4615995, US2002/0099249A1 etc.Such as, patent in Methanol aromatics process: US Patent No. 4686312, Chinese patent ZL101244969, ZL1880288, CN101602646, CN101823929, CN101671226, CN102199069, CN102199446, CN1880288 etc.
In addition, other products such as co-producing light olefins, the gasoline while that technological line being Methanol aromatic hydrocarbons disclosed in some patent, as patent CN102775261, CN102146010, CN102531821, CN102190546, CN102372537 etc.
Wherein, disclosed in patent CN102775261, Multi-function methanol working method and device utilize preparing low carbon olefin hydrocarbon with methanol, gasoline, aromatic hydrocarbons.The method adopts two-step approach production technique, the first step methanol feedstock produces low-carbon alkene under special-purpose catalyst 1 acts on, reaction gas containing low-carbon alkene after heat exchange, chilling, carrying out washing treatment, is synthesized aromatic hydrocarbons and or gasoline by second step under the effect of special-purpose catalyst 2.The reactor of two reaction process can be fixed bed or fluidized-bed.The method adopts two-step approach, and technical process is complicated.
Take methyl alcohol as the technique of raw material production low-carbon alkene and arene parallel cogeneration gasoline disclosed in patent CN102146010.Be raw material with methyl alcohol and adopt molecular sieve catalyst to produce low-carbon alkene and arene parallel cogeneration gasoline through methyl alcohol alkylation reaction and aromatization.The reactor of methyl alcohol alkylation reaction and aromatization is various types of fixed-bed reactor, pressure 0.01 ~ 0.5 MPa, temperature 180 ~ 600 DEG C.Total liquid yield is greater than 70 % by weight, and triphen yield is greater than 90 % by weight.The method also adopts two reactors, and technical process is complicated.
Be the method for the co-fed production low-carbon alkene of methyl alcohol and petroleum naphtha and/or aromatic hydrocarbons disclosed in patent CN102531821, adopt the ZSM-5 catalyzer of load 2.2 ~ 6.0 % by weight La and 1.0 ~ 2.8 % by weight P, fixed-bed reactor or fluidized-bed reactor can be adopted.Temperature of reaction is 550 ~ 670 DEG C, air speed 1.0 ~ 5 (Grams Per Hour)/gram catalyzer.The triolefin yield of the method is higher, but BTX yield is low, only has 5 ~ 17 % by weight.
Patent CN102372537 and CN102190546 discloses the method for preparing propylene by methanol transformation and aromatic hydrocarbons.These two patents develop on the basis of preparing propylene by methanol transformation technology, and propylene is the product of argument, and aromatics yield is lower.
The low problem of ethene, propylene and aromatics yield is all there is in above-mentioned patented technology.Propose technical scheme to the property of the present invention is directed to, solve the problems referred to above.
Summary of the invention
One of technical problem to be solved by this invention is the technical problem that ethene in prior art, propylene and aromatics yield are low, provides the coaxial-type segmental fluidized bed reaction unit of a kind of methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons.This system has the high advantage of ethene, propylene and aromatics yield.
Two of technical problem to be solved by this invention is to provide a kind of method corresponding with one of technical solution problem.
For one of solving the problem, the technical solution used in the present invention is as follows: the coaxial-type segmental fluidized bed reaction unit of a kind of methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, comprises reactor 1, revivifier 2, stripper 3; Reactor 1 is the first conversion zone 25, First Transition section 26, second conversion zone 27, second transition section 28, dilute phase section 29 from bottom to top; Raw material 15 and recycle stock 24 enter reactor 1 and catalyst exposure reaction respectively from reactor first conversion zone 25 bottom and reactor second conversion zone 27 bottom, be advanced under reacted carbon deposited catalyst and the inclined tube to be generated 7 be connected bottom reactor 1, stripper 3 is promoted to again through stripping standpipe 8, catalyzer after stripping enters revivifier 2 and regenerates, and the catalyzer after regeneration comes downwards to reactor first conversion zone 25 through degassing vessel 4 is degassed.
In technique scheme, the height of reactor first conversion zone 25 accounts for 5 ~ 50% of total reactor height; The diameter ratio of the second conversion zone 27 diameter and the first conversion zone 25 is 0.7 ~ 1.8:1, and it highly accounts for 20 ~ 70% of total reactor height; The diameter ratio of dilute phase section 29 diameter and the second conversion zone 27 is 1 ~ 2.5:1, and it highly accounts for 10 ~ 30% of total reactor height; The total height of First Transition section 26 and the second transition section 28 accounts for 5% of total reactor height.
In technique scheme, bottom reactor first conversion zone 25, be less than 70% of reactor first conversion zone 25 overall length to the distance of inclined tube 10 to be generated and reactor first conversion zone 25 junction.
In technique scheme, the external heat collector 5 of reactor 1, the height of heat collector 5 accounts for 30% ~ 95% of reactor 1 height.
In technique scheme, the external heat collector 6 of revivifier 2, the height of heat collector 6 accounts for 30% ~ 70% of revivifier 2 height.
In technique scheme, reactor 1, revivifier 2 and stripper 3 inside are equipped with one group of gas-solid cyclone separator, are 1 ~ 3 grade.
In technique scheme, raw material 15 enters reactor 1 and catalyst exposure reaction; The carbon deposited catalyst reaction product that stripping goes out to carry in stripper 3; Carbon deposited catalyst removes coke at revivifier 2 by the mode of burning.Catalyzer after regeneration enters degassing vessel 4 and removes regenerated flue gas further.
In technique scheme, reactor 1, for being converted into based on the product of ethene, propylene and aromatic hydrocarbons by raw material 15 and catalyst exposure reaction; Revivifier 2, removes the coke on carbon deposited catalyst for the mode by burning; Stripper 3, goes out the product that carbon deposited catalyst carries for stripping; Degassing vessel 4, for removing the regenerated flue gas of the catalyst entrainment after regeneration further.
For solve the problem two, the technical solution used in the present invention is as follows: the coaxial-type segmental fluidized bed reaction method of a kind of methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, adopt above-mentioned reaction unit, described reaction method comprises following step:
A) raw material 15 and recycle stock 24 enter reactor 1 and catalyst exposure reaction respectively from reactor first conversion zone 25 bottom and reactor second conversion zone 27 bottom, formation reaction product 16 and carbon deposited catalyst, reaction product 16 is separated after carbon deposited catalyst through gas-solid cyclone separator and enters subsequent separation system;
B) be advanced under carbon deposited catalyst and the inclined tube to be generated 7 be connected bottom reactor 1, enter stripping standpipe 8 again, stripper 3 is promoted to through promoting medium 22, stripping is contacted with stripping fluid 21, carbon deposited catalyst after the stripped product 19 obtained and stripping, stripped product 19 is separated after carbon deposited catalyst through gas-solid cyclone separator and enters subsequent separation system;
C) carbon deposited catalyst after stripping enters revivifier 2, contacts burn with regenerating medium 17, obtains the catalyzer after regenerating and flue gas 18;
D) catalyzer after regeneration enters degassing vessel 4 through degassing vessel inclined tube 9 and contacts with degassed medium 23, and remove regenerated flue gas 20 further, regenerator sloped tube 10 of passing through under the catalyzer after degassed enters reactor first conversion zone 25;
E) the external heat collector 5 of reactor 1, catalyzer enters heat collector 5 through the external heat collector inlet tube 11 of reactor, and temperature enters reactor 1 through reactor external warmer outlet pipe 12 after reducing;
F) the external heat collector 6 of revivifier 2, catalyzer enters heat collector 6 through the external heat collector inlet tube 13 of revivifier, and temperature enters revivifier 2 through reactor external warmer outlet pipe 14 after reducing.
In technique scheme, the temperature of reactor 1 is 400 ~ 550 DEG C, be 0 ~ 0.5 MPa in gauge pressure reaction pressure, weight space velocity is 0.1 ~ 10 (Grams Per Hour)/gram catalyzer, the mass ratio of catalyst recirculation amount and raw material 15 inlet amount is 3 ~ 40: 1, average gas superficial velocity 0.01 ~ 1 meter per second.
In technique scheme, under maximum ethene, propylene operator scheme, temperature is 480 ~ 550 DEG C, be 0 ~ 0.3 MPa in gauge pressure reaction pressure, weight space velocity is 2 ~ 10 (Grams Per Hours)/gram catalyzer, the mass ratio of catalyst recirculation amount and raw material 15 inlet amount is 10 ~ 40: 1, average gas superficial velocity 0.06 ~ 1 meter per second.
In technique scheme, under maximum aromatic hydrocarbons operator scheme, temperature is 400 ~ 500 DEG C, be 0.1 ~ 0.5 MPa in gauge pressure reaction pressure, weight space velocity is 0.1 ~ 2 (Grams Per Hour)/gram catalyzer, the mass ratio of catalyst recirculation amount and raw material 15 inlet amount is 3 ~ 30: 1, average gas superficial velocity 0.01 ~ 0.3 meter per second.
In technique scheme, under coproduction ethene, propylene and aromatic hydrocarbons pattern, temperature is 440 ~ 520 DEG C, be 0.1 ~ 0.4 MPa in gauge pressure reaction pressure, weight space velocity is 0.3 ~ 4 (Grams Per Hour)/gram catalyzer, the mass ratio of catalyst recirculation amount and raw material 8 inlet amount is 5 ~ 30: 1, average gas superficial velocity 0.01 ~ 0.5 meter per second.
In technique scheme, the temperature of revivifier 2 is 580 ~ 720 DEG C, preferably 600 ~ 700 DEG C, preferably 630 ~ 680 DEG C further.
In technique scheme, the charcoal on the catalyzer after regeneration, with the mass percent of catalyzer, content is lower than 0.1 % by weight, preferred lower than 0.07 % by weight further.。
In technique scheme, catalyst activity component is ZSM-5, ZSM-23, ZSM-11, beta-molecular sieve, Y molecular sieve or the mutual composite molecular screen formed, preferred ZSM-5; Carrier is kaolin, aluminum oxide, silicon-dioxide; The mass ratio of active ingredient and carrier is (10 ~ 50): (50 ~ 90), preferably (20 ~ 40): (60 ~ 80).
In technique scheme, catalyst cupport has one or more elements or oxide compound in Zn, Ag, P, Ga, Cu, Mn, Mg, preferred Zn, P; With the mass percent of catalyzer, the element content on a catalyst of load is 0.01 ~ 15 % by weight, preferably 0.02 ~ 8 % by weight.
In technique scheme, the active ingredient of catalyzer is selected from ZSM-5 molecular sieve, with the weight percent meter of catalyzer, and the Zn element of load 0.01 ~ 5 % by weight on catalyzer or oxide compound, the P element of 0.1 ~ 8 % by weight or oxide compound.
In technique scheme, raw material 15 is methyl alcohol or dme or both mixtures, particular methanol.
In technique scheme, in raw material 15, the mass percentage of water is 0.01 ~ 30 % by weight, preferably lower than 10 % by weight.
In technique scheme, stripping fluid 21 is water vapor or N
2or water vapor and N
2mixture, promote medium 22 be water vapor or N
2or water vapor and N
2mixture, regenerating medium 17 is air or air and O
2mixture or air and N
2mixture, degassed medium 23 is water vapor or N
2or water vapor and N
2mixture.
Technical scheme provided by the invention, adopts the fluidized-bed reactor of catalyzer and reaction mass countercurrent movement, and effectively promote contacting of reaction mass and catalyst active center on the one hand, minimizing extends influence, and improves mass-transfer efficiency; Air speed regulation range can be expanded on the other hand, thus realize maximum ethene, propylene easily, the operator scheme of maximum aromatic hydrocarbons production object different from three kinds, coproduction ethene, propylene and aromatic hydrocarbons.
The present invention passes through separation and the by product recycle of product in methyl alcohol and/or dimethyl ether catalysis conversion reaction process, realizes the object of the yield of maximum ethene, propylene and aromatic hydrocarbons.And reactor reducing, raw material of different nature and recycle stock can be made to react under reaction conditions suitable separately respectively, improve object product yield further.
Adopt technical scheme of the present invention, operate under maximum ethene, propylene pattern, raw material 8 is methyl alcohol, the temperature of reaction of reactor 1 is 480 DEG C, be 0.2 MPa in gauge pressure reaction pressure, the weight space velocity of methyl alcohol is 2 (Grams Per Hours)/gram catalyzer, and the mass ratio of catalyst recirculation amount and methanol feeding amount is 12:1, and density of catalyst is 100 kgs/m
3, average gas superficial velocity 0.2 meter per second; Adopt Cu-ZSM-5 catalyzer; Ethene carbon base absorption rate is 25.0 % by weight, propylene carbon base absorption rate is 22.3 % by weight, aromatic hydrocarbons carbon base absorption rate be 39.2 % by weight, BTX carbon base absorption rates is 27.5 % by weight.
Adopt technical scheme of the present invention, operate under maximum aromatic hydrocarbons pattern, raw material 8 is methyl alcohol, the temperature of reaction of reactor 1 is 465 DEG C, be 0.25 MPa in gauge pressure reaction pressure, the weight space velocity of methyl alcohol is 0.3 (Grams Per Hour)/gram catalyzer, and the mass ratio of catalyst recirculation amount and methanol feeding amount is 10:1, and density of catalyst is 180 kgs/m
3, average gas superficial velocity 0.05 meter per second; Adopt Zn-P-ZSM-5 catalyzer; Ethene carbon base absorption rate is 11.4 % by weight, propylene carbon base absorption rate is 7.6 % by weight, aromatic hydrocarbons carbon base absorption rate be 70.8 % by weight, BTX carbon base absorption rates is 54.9 % by weight.
Adopt technical scheme of the present invention, operate under coproduction ethene, propylene and aromatic hydrocarbons pattern, raw material 8 is methyl alcohol, the temperature of reaction of reactor 1 is 460 DEG C, be 0.2 MPa in gauge pressure reaction pressure, the weight space velocity of methyl alcohol is 0.5 (Grams Per Hour)/gram catalyzer, and the mass ratio of catalyst recirculation amount and methanol feeding amount is 30:1, and density of catalyst is 150 kgs/m
3, average gas superficial velocity 0.1 meter per second; Adopt Zn-Mg-P-ZSM-5 catalyzer; Methanol feeding; Ethene carbon base absorption rate is 16.1 % by weight, propylene carbon base absorption rate is 13.7 % by weight, aromatic hydrocarbons carbon base absorption rate be 59.0 % by weight, BTX carbon base absorption rates is 44.9 % by weight.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram of technical scheme of the present invention,
Fig. 2 is the schematic diagram of reactor.
In figure in 1 ~ 2,1 is reactor; 2 is revivifier; 3 is stripper; 4 is degassing vessel; 5 is the external heat collector of reactor; 6 is the external heat collector of revivifier; 7 is inclined tube to be generated; 8 is stripping standpipe; 9 is degassing vessel inclined tube; 10 is regenerator sloped tube; 11 is reactor external heat collector entrance inclined tube; 12 is the external heat collector outlet pipe of reactor; 13 is revivifier external heat collector entrance inclined tube; 14 is the external heat collector outlet pipe of revivifier; 15 is methyl alcohol and/or dme; 16 is the product of reactor; 17 is regenerating medium; 18 is flue gas; 19 is stripped product; 20 is degassing vessel flue gas; 21 is stripping fluid; 22 for promoting medium; 23 is degassed medium; 23 is the conversion zone of reactor; 24 is recycle stock; 25 is reactor first conversion zone; 26 is reactor First Transition section; 27 is reactor second conversion zone; 28 is reactor second transition section; 29 is reactor dilute phase section.
In Fig. 1, raw material 15 and recycle stock 24 enter reactor 1 and catalyst exposure reaction respectively from reactor first conversion zone 25 bottom and reactor second conversion zone 27 bottom, formation reaction product 16 and carbon deposited catalyst, reaction product 16 is separated after carbon deposited catalyst through gas-solid cyclone separator and enters subsequent separation system; Be advanced under carbon deposited catalyst and the inclined tube to be generated 7 be connected bottom reactor 1, enter stripping standpipe 8 again, stripper 3 is promoted to through promoting medium 22, stripping is contacted with stripping fluid 21, carbon deposited catalyst after the stripped product 19 obtained and stripping, stripped product 19 is separated after carbon deposited catalyst through gas-solid cyclone separator and enters subsequent separation system; Carbon deposited catalyst after stripping enters revivifier 2, contacts burn with regenerating medium 17, obtains the catalyzer after regenerating and flue gas 18; Catalyzer after regeneration enters degassing vessel 4 through degassing vessel inclined tube 9 and contacts with degassed medium 23, removes regenerated flue gas 20 further, and regenerator sloped tube 10 of passing through under the catalyzer after degassed enters reactor first conversion zone 25; The external heat collector 5 of reactor 1, catalyzer enters heat collector 5 through the external heat collector inlet tube 11 of reactor, and temperature enters reactor 1 through reactor external warmer outlet pipe 12 after reducing; The external heat collector 6 of revivifier 2, catalyzer enters heat collector 6 through the external heat collector inlet tube 13 of revivifier, and temperature enters revivifier 2 through reactor external warmer outlet pipe 14 after reducing.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Adopt device as shown in Figure 1.
The diameter of reactor first conversion zone is 2 meters, highly accounts for 30% of total reactor height; The diameter ratio of the second conversion zone diameter and the first conversion zone is 1.2:1, and it highly accounts for 55% of total reactor height; The diameter ratio of dilute phase section diameter and the second conversion zone is 1.8:1, and it highly accounts for 10% of total reactor height.The height that the height of First Transition section accounts for the 3% of total reactor height, second transition section accounts for 2% of total reactor height.Arrange heat collector outside reactor, heat collector height accounts for 30% of height for reactor.Arrange heat collector outside revivifier, heat collector height accounts for 80% of revivifier height.
Reaction conditions is: temperature is 480 DEG C, is 0.2 MPa in gauge pressure reaction pressure, and the weight space velocity of methyl alcohol is 2 (Grams Per Hours)/gram catalyzer, and the mass ratio of catalyst recirculation amount and methanol feeding amount is 12: 1, average gas superficial velocity 0.2 meter per second.The temperature of revivifier is 650 DEG C.Charcoal on catalyzer after regeneration, with the mass percent of catalyzer, content is 0.04 % by weight.
Stripping fluid is water vapor.Lifting medium is water vapour.Regenerating medium is air.
Take methyl alcohol as raw material, water-content is 5 % by weight.The mass ratio that in recycle stock, Yi Wan ﹕ Bing Wan ﹕ C4 and C5 and C6 is non-aromatic is 2:3:5.Methyl alcohol and recycle stock charge-mass ratio are 15:1.
Adopt Cu-ZSM-5 catalyzer.
The preparation process of Cu-ZSM-5 catalyzer: by ZSM-5 molecular sieve, carrier and binding agent mechanically mixing, add suitable quantity of water, HCl, controls pH value and is not less than 3, slurry agitation evenly after at 500 DEG C spray shaping, make 60 ~ 300 object ZSM-5 catalyst intermediate.The mass ratio of ZSM-5 molecular sieve and matrix is 4:6; The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 25; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 7:3.Be the solution of 5% by Cu mass of ion percentage composition, with the weight ratio of solution and catalyzer for 1.74:1 floods, at 120 DEG C dry 5 hours, then put into retort furnace roasting at 550 DEG C and within 6 hours, be prepared into the Cu-ZSM-5 catalyzer that Cu constituent content is 8 % by weight.
[embodiment 2]
Adopt device as shown in Figure 1.
The diameter of reactor first conversion zone is 1.5 meters, highly accounts for 5% of total reactor height; The diameter ratio of the second conversion zone diameter and the first conversion zone is 1.8:1, and it highly accounts for 70% of total reactor height; The diameter ratio of dilute phase section diameter and the second conversion zone is 2.5:1, and it highly accounts for 20% of total reactor height.The height that the height of First Transition section accounts for the 2% of total reactor height, second transition section accounts for 3% of total reactor height.Arrange heat collector outside reactor, heat collector height accounts for 95% of height for reactor.Arrange heat collector outside revivifier, heat collector height accounts for 30% of revivifier height.
The reaction conditions of reactor is: temperature is 400 DEG C, be 0.5 MPa in gauge pressure reaction pressure, the weight space velocity of methyl alcohol is 10 (Grams Per Hours)/gram catalyzer, and the mass ratio of catalyst recirculation amount and methanol feeding amount is 3: 1, average gas superficial velocity 0.17 meter per second.The temperature of revivifier is 680 DEG C.Charcoal on catalyzer after regeneration, with the mass percent of catalyzer, content is 0.03 % by weight.
Stripping fluid is N
2.Lifting medium is N
2.Regenerating medium is air.
Take methyl alcohol as raw material, water-content is 30 % by weight.The mass ratio that in recycle stock, Yi Wan ﹕ Bing Wan ﹕ C4 and C5 and C6 is non-aromatic is 1:1:8.Methyl alcohol and recycle stock charge-mass ratio are 12:1.
Adopt Ag-Y-ZSM-23 catalyzer.
The preparation process of Ag-Y-ZSM-23 catalyzer: by Y molecular sieve, ZSM-23 molecular screen, carrier and binding agent mechanically mixing, add suitable quantity of water, HCl, control pH value and be not less than 3, slurry agitation evenly after at 500 DEG C spray shaping, make 60 ~ 300 object Y-ZSM-23 catalyst intermediate.The mass ratio of molecular sieve and matrix is 1:9; Y molecular sieve and ZSM-23 molecular screen mass ratio are 3:7; The silicoaluminophosphate molecular ratio of Y molecular sieve is 10; The silicoaluminophosphate molecular ratio of ZSM-23 molecular screen is 60; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 8:2.Be the solution of 1% by Ag mass of ion percentage composition, flood than for 0.1:1 with solution and catalyst weight, at 120 DEG C dry 5 hours, then put into retort furnace roasting at 550 DEG C and within 6 hours, be prepared into the Ag-Y-ZSM-23 catalyzer that Ag constituent content is 0.1 % by weight.
[embodiment 3]
Adopt the device of embodiment 1.
The reaction conditions of reactor is: temperature is 550 DEG C, be 0 MPa in gauge pressure reaction pressure, the weight space velocity of methyl alcohol is 10 (Grams Per Hours)/gram catalyzer, and the mass ratio of catalyst recirculation amount and methanol feeding amount is 40: 1, average gas superficial velocity 1 meter per second.The temperature of revivifier is 580 DEG C.Charcoal on catalyzer after regeneration, with the mass percent of catalyzer, content is 0.09 % by weight.
Stripping fluid is water vapor.Lifting medium is N
2.Regenerating medium is air and O
2mixture, volume ratio is 8: 2.
Take methyl alcohol as raw material, water-content is 10 % by weight.The mass ratio that in recycle stock, Bing Wan ﹕ C4 and C5 and C6 is non-aromatic is 2:8.Methyl alcohol and recycle stock charge-mass ratio are 10:1.
Adopt Ga-beta catalyst.
The preparation process of Ga-beta catalyst: by beta-molecular sieve, carrier and binding agent mechanically mixing, add suitable quantity of water, HCl, controls pH value and is not less than 4, slurry agitation evenly after at 500 DEG C spray shaping, make 60 ~ 300 object beta catalyst intermediates.The mass ratio of beta-molecular sieve and matrix is 5:5; The silicoaluminophosphate molecular ratio of beta-molecular sieve is 20; Matrix is the mixture of kaolin, silicon-dioxide and aluminium sesquioxide, and the mass ratio of three is 7:1:2.Be the solution of 2% by Ga mass of ion percentage composition, flood than for 0.4:1 with solution and catalyst weight, at 120 DEG C dry 5 hours, then put into retort furnace roasting at 550 DEG C and within 6 hours, be prepared into the Ga-beta catalyst that Ga constituent content is 0.8 % by weight.
[embodiment 4]
Adopt device as shown in Figure 1.
The diameter of reactor first conversion zone is 4 meters, highly accounts for 50% of total reactor height; The diameter ratio of the second conversion zone diameter and the first conversion zone is 0.7:1, and it highly accounts for 15% of total reactor height; The diameter ratio of dilute phase section diameter and the second conversion zone is 1:1, and it highly accounts for 30% of total reactor height.The height that the height of First Transition section accounts for the 3% of total reactor height, second transition section accounts for 2% of total reactor height.Arrange heat collector in reactor, heat collector height accounts for 30% of height for reactor.Arrange heat collector in revivifier, heat collector height accounts for 30% of revivifier height.
The reaction conditions of reactor is: temperature is 470 DEG C, be 0.3 MPa in gauge pressure reaction pressure, the weight space velocity of raw material is 1 (Grams Per Hour)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 25: 1, average gas superficial velocity 0.01 meter per second.The temperature of revivifier is 700 DEG C.Charcoal on catalyzer after regeneration, with the mass percent of catalyzer, content is 0.02 % by weight.
Stripping fluid is water vapor and N
2mixture, volume ratio is 5: 5.Lifting medium is N
2.Regenerating medium is air and N
2mixture, volume ratio is 9: 1.
Take dme as raw material.The mass ratio that in recycle stock, Yi Wan ﹕ C4 and C5 and C6 is non-aromatic is 3:7.Dme raw material and recycle stock charge-mass ratio are 14:1.
Adopt Mn-ZSM-11 catalyzer.
The preparation process of Mn-ZSM-11 catalyzer: by ZSM-11 molecular sieve, carrier and binding agent mechanically mixing, add suitable quantity of water, HCl, control pH value and be not less than 3, slurry agitation evenly after at 500 DEG C spray shaping, make 60 ~ 300 object ZSM-11 catalyst intermediate.The mass ratio of ZSM-11 molecular sieve and matrix is 3:7; The silicoaluminophosphate molecular ratio of ZSM-11 molecular sieve is 50; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 7:3.Be the solution of 10% by Mn mass of ion percentage composition, with the weight ratio of solution and catalyzer for 1:1 floods, at 120 DEG C dry 5 hours, then put into retort furnace roasting at 550 DEG C and within 6 hours, be prepared into the Mn-ZSM-11 catalyzer that Mn constituent content is 9.09 % by weight.
[embodiment 5]
Adopt device as shown in Figure 1.
The diameter of reactor first conversion zone is 3 meters, highly accounts for 50% of total reactor height; The diameter ratio of the second conversion zone diameter and the first conversion zone is 1:1, and it highly accounts for 20% of total reactor height; The diameter ratio of dilute phase section diameter and the second conversion zone is 1.5:1, and it highly accounts for 25% of total reactor height.The height that the height of First Transition section accounts for the 2.5% of total reactor height, second transition section accounts for 2.5% of total reactor height.Arrange heat collector in reactor, heat collector height accounts for 95% of height for reactor.Arrange heat collector in revivifier, heat collector height accounts for 80% of revivifier height.
The reaction conditions of reactor is: temperature is 465 DEG C, be 0.25 MPa in gauge pressure reaction pressure, the weight space velocity of methyl alcohol is 0.3 (Grams Per Hour)/gram catalyzer, and the mass ratio of catalyst recirculation amount and methanol feeding amount is 10: 1, average gas superficial velocity 0.05 meter per second.The temperature of revivifier is 630 DEG C.Charcoal on catalyzer after regeneration, with the mass percent of catalyzer, content is 0.07 % by weight.
Stripping fluid is water vapor.Promoting medium is water vapor and N
2mixture, volume ratio is 1: 9.Regenerating medium is air and O
2mixture, volume ratio is 9: 1.
Take methyl alcohol as raw material, water-content is 15 % by weight.In recycle stock, the mass ratio of Yi Wan ﹕ propane is 5:5.Methyl alcohol and recycle stock charge-mass ratio are 16:1.
Adopt Zn-P-ZSM-5 catalyzer.
The preparation process of Zn-P-ZSM-5 catalyzer: by ZSM-5 molecular sieve, carrier and binding agent mechanically mixing, add suitable quantity of water, H
3pO
4, control pH value and be not less than 3, slurry agitation evenly after at 500 DEG C spray shaping, make 60 ~ 300 object P-ZSM-5 catalyst intermediate.H
3pO
4the concentration of solution is 1 % by weight, and the weight ratio of solution and molecular sieve is 1.53:1.The mass ratio of ZSM-5 molecular sieve and matrix is 3.5:6.5; The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 25; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 7:3.Be the solution of 5% by Zn mass of ion percentage composition, flood than for 0.6:1 with solution and P-ZSM-5 catalyst weight, drying 5 hours at 120 DEG C, put into retort furnace roasting 6 hours at 550 DEG C again, being prepared into Zn constituent content is 2.87 % by weight, and P element content is the Zn-P-ZSM-5 catalyzer of 1.48 % by weight.
[embodiment 6]
Adopt the device of embodiment 5.
The reaction conditions of reactor is: temperature is 480 DEG C, be 0.1 MPa in gauge pressure reaction pressure, the weight space velocity of methyl alcohol is 2 (Grams Per Hours)/gram catalyzer, and the mass ratio of catalyst recirculation amount and methanol feeding amount is 20: 1, average gas superficial velocity 0.5 meter per second.The temperature of revivifier is 600 DEG C.Charcoal on catalyzer after regeneration, with the mass percent of catalyzer, content is 0.08 % by weight.
Stripping fluid is water vapor and N
2mixture, volume ratio is 2: 8.Promoting medium is water vapor and N
2mixture, volume ratio is 2: 8.Regenerating medium is air and O
2mixture, volume ratio is 5: 5.
Take methyl alcohol as raw material, water-content is 3 % by weight.The mass ratio that in recycle stock, Yi Wan ﹕ Bing Wan ﹕ C4 and C5 and C6 is non-aromatic is 3:3:4.Methyl alcohol and recycle stock charge-mass ratio are 12.5:1.
Adopt ZSM-5-beta catalyst.
The preparation process of ZSM-5-beta catalyst: by ZSM-5 molecular sieve, beta-molecular sieve, carrier and binding agent mechanically mixing, add suitable quantity of water, HCl, control pH value and be not less than 3, slurry agitation evenly after at 500 DEG C spray shaping, make 60 ~ 300 object ZSM-5-beta catalysts.The mass ratio of ZSM-5 and beta-molecular sieve and matrix is 3.5: 6.5.The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 38; The silicoaluminophosphate molecular ratio of beta-molecular sieve is 20; The mass ratio of ZSM-5 and beta-molecular sieve is 9:1.Matrix is the mixture of kaolin, silicon-dioxide and aluminium sesquioxide, and the mass ratio of three is 5:2:3.
[embodiment 7]
Adopt device as shown in Figure 1.
The diameter of reactor first conversion zone is 5 meters, highly accounts for 45% of total reactor height; The diameter ratio of the second conversion zone diameter and the first conversion zone is 1:1, and it highly accounts for 20% of total reactor height; The diameter ratio of dilute phase section diameter and the second conversion zone is 1:1, and it highly accounts for 30% of total reactor height.The height that the height of First Transition section accounts for the 2.5% of total reactor height, second transition section accounts for 2.5% of total reactor height.Arrange heat collector in reactor, heat collector height accounts for 95% of height for reactor.Arrange heat collector in revivifier, heat collector height accounts for 80% of revivifier height.
The reaction conditions of reactor is: temperature is 450 DEG C, be 0.15 MPa in gauge pressure reaction pressure, the weight space velocity of raw material is 0.8 (Grams Per Hour)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 15: 1, average gas superficial velocity 0.3 meter per second.The temperature of revivifier is 720 DEG C.Charcoal on catalyzer after regeneration, with the mass percent of catalyzer, content is 0.01 % by weight.
Stripping fluid is water vapor.Promoting medium is water vapor and N
2mixture, volume ratio is 8: 2.Regenerating medium is air and N
2mixture, volume ratio is 7: 3.
With the mixture of methyl alcohol, dme for raw material, both mass ratioes are 8:2.The mass ratio that in recycle stock, Yi Wan ﹕ Bing Wan ﹕ C4 and C5 and C6 is non-aromatic is 0.5:0.5:9.Raw material and recycle stock charge-mass ratio are 20:1.
Adopt Zn-Ag-P-ZSM-5 catalyzer.
The preparation process of Zn-Ag-P-ZSM-5 catalyzer: by ZSM-5 molecular sieve, carrier and binding agent mechanically mixing, add suitable quantity of water, H
3pO
4, control pH value and be not less than 3, slurry agitation evenly after at 500 DEG C spray shaping, make 60 ~ 300 object P-ZSM-5 catalyst intermediate.H
3pO
4the concentration of solution is 2.5 % by weight, and the weight ratio of solution and molecular sieve is 2:1.The mass ratio of ZSM-5 molecular sieve and matrix is 3.5:6.5; The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 28; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 8:2.Be 1% by Ag mass of ion percentage composition, Zn mass of ion percentage composition is the solution of 3%, flood than for 0.8:1 with solution and P-ZSM-5 catalyst weight, drying 5 hours at 120 DEG C, put into retort furnace roasting 6 hours at 550 DEG C again, being prepared into Zn constituent content is 2.32 % by weight, Ag constituent content is 0.78 % by weight, and P element content is the Zn-Ag-P-ZSM-5 catalyzer of 1.51 % by weight.
[embodiment 8]
Adopt the device of embodiment 1.
The reaction conditions of reactor is: temperature is 460 DEG C, be 0.2 MPa in gauge pressure reaction pressure, the weight space velocity of methyl alcohol is 0.5 (Grams Per Hour)/gram catalyzer, and the mass ratio of catalyst recirculation amount and methanol feeding amount is 30: 1, average gas superficial velocity 0.1 meter per second.The temperature of revivifier is 630 DEG C.Charcoal on catalyzer after regeneration, with the mass percent of catalyzer, content is 0.04 % by weight.
Stripping fluid is water vapor and N
2mixture, volume ratio is 8: 2.Promoting medium is water vapor and N
2mixture, volume ratio is 5: 5.Regenerating medium is air and O
2mixture, volume ratio is 7: 3.
Take methyl alcohol as raw material, water-content is 0.01 % by weight.The mass ratio that in recycle stock, Yi Wan ﹕ Bing Wan ﹕ C4 and C5 and C6 is non-aromatic is 1:1:8.Methyl alcohol and recycle stock charge-mass ratio are 30:1.
Adopt Zn-Mg-P-ZSM-5 catalyzer.
The preparation process of Zn-Mg-P-ZSM-5 catalyzer: by ZSM-5 molecular sieve, carrier and binding agent mechanically mixing, add suitable quantity of water, H
3pO
4, control pH value and be not less than 3, slurry agitation evenly after at 500 DEG C spray shaping, make 60 ~ 300 object P-ZSM-5 catalyst intermediate.H
3pO
4the concentration of solution is 4 % by weight, and the weight ratio of solution and molecular sieve is 2:1.The mass ratio of ZSM-5 molecular sieve and matrix is 3:7; The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 32; Matrix is the mixture of kaolin and aluminium sesquioxide, and both mass ratioes are 7:3.Be 2% by Mg mass of ion percentage composition, Zn mass of ion percentage composition is the solution of 3%, flood than for 1:1 with solution and P-ZSM-5 catalyst weight, drying 5 hours at 120 DEG C, put into retort furnace roasting 6 hours at 550 DEG C again, being prepared into Zn constituent content is 2.86 % by weight, Mg constituent content is 1.9 % by weight, and P element content is the Zn-Mg-P-ZSM-5 catalyzer of 2.35 % by weight.
Table 1
| Yield of ethene, % by weight | Propene yield, % by weight | Aromatics yield, % by weight | |
| Embodiment 1 | 25.0 | 22.3 | 39.2 |
| Embodiment 2 | 13.3 | 10.2 | 62.2 |
| Embodiment 3 | 30.2 | 18.1 | 34.8 |
| Embodiment 4 | 12.8 | 10.2 | 68.3 |
| Embodiment 5 | 11.4 | 7.6 | 70.8 |
| Embodiment 6 | 16.9 | 14.2 | 57.4 |
| Embodiment 7 | 13.4 | 12.8 | 61.7 |
| Embodiment 8 | 16.1 | 13.7 | 59.0 |
Claims (10)
1. a coaxial-type segmental fluidized bed reaction unit for methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, comprises reactor (1), revivifier (2), stripper (3); Reactor (1) is the first conversion zone (25), First Transition section (26), the second conversion zone (27), the second transition section (28), dilute phase section (29) from bottom to top; Raw material (15) and recycle stock (24) enter reactor (1) and catalyst exposure reaction respectively from reactor first conversion zone (25) bottom and reactor second conversion zone (27) bottom, the inclined tube to be generated (7) be connected with reactor (1) bottom is advanced under reacted carbon deposited catalyst, stripper (3) is promoted to again through stripping standpipe (8), catalyzer after stripping enters revivifier (2) regeneration, and the catalyzer after regeneration comes downwards to reactor first conversion zone (25) through degassing vessel (4) is degassed.
2. the coaxial-type segmental fluidized bed reaction unit of methyl alcohol according to claim 1 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, is characterized in that the height of reactor first conversion zone (25) accounts for 5 ~ 50% of total reactor height; The diameter ratio of the second conversion zone (27) diameter and the first conversion zone (25) is 0.7 ~ 1.8:1, and it highly accounts for 20 ~ 70% of total reactor height; The diameter ratio of dilute phase section (29) diameter and the second conversion zone (27) is 1 ~ 2.5:1, and it highly accounts for 10 ~ 30% of total reactor height; The total height of First Transition section (26) and the second transition section (28) accounts for 5% of total reactor height.
3. the coaxial-type segmental fluidized bed reaction unit of methyl alcohol according to claim 1 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, is characterized in that reactor first conversion zone (25) bottom is less than 70% of reactor first conversion zone (25) overall length to the distance of inclined tube to be generated (10) and reactor first conversion zone (25) junction.
4. the coaxial-type segmental fluidized bed reaction unit of methyl alcohol according to claim 1 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, it is characterized in that reactor (1) external heat collector (5), the height of heat collector (5) accounts for 30% ~ 95% of reactor (1) height; Revivifier (2) external heat collector (6), the height of heat collector (6) accounts for 30% ~ 70% of revivifier (2) height.
5. the coaxial-type segmental fluidized bed reaction unit of methyl alcohol according to claim 1 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, it is characterized in that reactor (1), revivifier (2) and stripper (3) inside are equipped with one group of gas-solid cyclone separator, is 1 ~ 3 grade.
6. a coaxial-type segmental fluidized bed reaction method for methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, adopt the reaction unit of claim 1 ~ 5 described in any one, described reaction method comprises following step:
A) raw material (15) and recycle stock (24) enter reactor (1) and catalyst exposure reaction respectively from reactor first conversion zone (25) bottom and reactor second conversion zone (27) bottom, formation reaction product (16) and carbon deposited catalyst, reaction product (16) is separated after carbon deposited catalyst through gas-solid cyclone separator and enters subsequent separation system;
B) inclined tube to be generated (7) be connected with reactor (1) bottom is advanced under carbon deposited catalyst, enter stripping standpipe (8) again, stripper (3) is promoted to through promoting medium (22), stripping is contacted with stripping fluid (21), carbon deposited catalyst after the stripped product (19) obtained and stripping, stripped product (19) is separated after carbon deposited catalyst through gas-solid cyclone separator and enters subsequent separation system;
C) carbon deposited catalyst after stripping enters revivifier (2), contacts burn with regenerating medium (17), obtains the catalyzer after regenerating and flue gas (18);
D) catalyzer after regeneration enters degassing vessel (4) through degassing vessel inclined tube (9) and contacts with degassed medium (23), and remove regenerated flue gas (20) further, regenerator sloped tube (10) of passing through under the catalyzer after degassed enters reactor first conversion zone (25);
E) reactor (1) external heat collector (5), catalyzer enters heat collector (5) through the external heat collector inlet tube (11) of reactor, and temperature enters reactor (1) through reactor external warmer outlet pipe (12) after reducing;
F) revivifier (2) external heat collector (6), catalyzer enters heat collector (6) through the external heat collector inlet tube (13) of revivifier, and temperature enters revivifier (2) through reactor external warmer outlet pipe (14) after reducing.
7. the coaxial-type segmental fluidized bed reaction method of methyl alcohol according to claim 6 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, it is characterized in that the temperature of reaction of reactor (1) is 400 ~ 550 DEG C, the weight space velocity of raw material (15) is 0.1 ~ 10 (Grams Per Hour)/gram catalyzer, be 0 ~ 0.5 MPa in gauge pressure reaction pressure, the mass ratio of catalyst recirculation amount and raw material (15) inlet amount is 3 ~ 40: 1, average gas superficial velocity 0.01 ~ 1 meter per second; The temperature of revivifier (2) is 580 ~ 720 DEG C, the charcoal on the catalyzer after regeneration, and with the mass percent of catalyzer, content is lower than 0.1 % by weight.
8. the coaxial-type segmental fluidized bed reaction method of methyl alcohol according to claim 6 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, is characterized in that the active ingredient of catalyzer is ZSM-5, ZSM-23, ZSM-11, beta-molecular sieve, Y molecular sieve or the mutual composite molecular screen formed; Carrier is kaolin, aluminum oxide, silicon-dioxide; The mass ratio of active ingredient and carrier is (10 ~ 50): (50 ~ 90); Catalyst cupport has one or more elements or oxide compound in Zn, Ag, P, Ga, Cu, Mn, Mg, and with the mass percent of catalyzer, its content is 0.01 ~ 15 % by weight.
9. the coaxial-type segmental fluidized bed reaction method of methyl alcohol according to claim 6 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, it is characterized in that raw material (15) is for methyl alcohol or dme or both mixtures, in mixture, the mass percentage of water is 0.01 ~ 30 % by weight.
10. the coaxial-type segmental fluidized bed reaction method of methyl alcohol according to claim 6 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, is characterized in that stripping fluid (21) is for water vapor or N
2or water vapor and N
2mixture, promote medium (22) be water vapor or N
2or water vapor and N
2mixture, regenerating medium (17) is air or air and O
2mixture or air and N
2mixture, degassed medium (23) is water vapor or N
2or water vapor and N
2mixture.
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| CN108786670A (en) * | 2017-04-27 | 2018-11-13 | 中国科学院大连化学物理研究所 | The device and method of methanol and/or dimethyl ether and toluene paraxylene co-producing light olefins |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6965057B2 (en) * | 2004-03-24 | 2005-11-15 | Exxonmobil Chemical Patents Inc. | Oxygenate to olefin process |
| US20070078287A1 (en) * | 2001-12-31 | 2007-04-05 | Lattner James R | Method for adding heat to a reactor system used to convert oxygenates to olefins |
-
2013
- 2013-10-28 CN CN201310512608.8A patent/CN104549074B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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