CN104549072A - Fluidized bed reaction system and method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether - Google Patents
Fluidized bed reaction system and method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether Download PDFInfo
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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Abstract
The invention relates to a fluidized bed reaction system and a fluidized bed reaction method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether. According to the fluidized bed reaction system and the fluidized bed reaction method, the problem that ethylene, propylene and aromatic hydrocarbon are low yield in the prior art are mainly solved. The fluidized bed reaction system comprises a reactor (1), a regenerator (2) and a stripper (3); raw materials (8) are fed to the bottom of a reactor reaction section (15) to be subjected to contact reaction with a catalyst, after the reaction, a carbon deposit catalyst is downwards conveyed into the stripper (3) through a to-be-generated inclined tube (4) which is connected with the bottom of the reactor (1), the stripped catalyst is upwards conveyed to the regenerator (2) through a stripping inclined tube (5) and a stripping vertical tube (6) and is regenerated, the regenerated catalyst is downwards conveyed to the reactor reaction section (15) through a catalyst regenerating inclined tube (7). According to the technical scheme, the problems are well solved. The fluidized bed reaction system and the fluidized bed reaction method can be well applied to the industrial production of ethylene, propylene and aromatic hydrocarbon.
Description
Technical field
The present invention relates to fluidized bed reaction system 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 fluidized bed reaction system 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 reaction 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 fluidized bed reaction system 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 conversion zone 15, transition section 16, dilute phase section 17 from bottom to top; Raw material 8 enters bottom reactor reaction section 15 and catalyst exposure reaction, reacted carbon deposited catalyst is descending, warp enters stripper 3 with the inclined tube to be generated 4 be connected bottom reactor 1, catalyzer after stripping goes upward to revivifier 2 regenerate through stripping inclined tube 5, stripping standpipe 6, and the catalyzer after regeneration comes downwards to reactor reaction section 15 through regenerator sloped tube 7.
In technique scheme, reactor 1 is conversion zone 15, transition section 16, dilute phase section 17 from bottom to top.
In technique scheme, the height of reactor 1 conversion zone 15 accounts for 60 ~ 85% of total reactor height; The diameter ratio of dilute phase section 17 diameter and conversion zone 15 is 1.1 ~ 2:1, and it highly accounts for 10 ~ 35% of total reactor height.
In technique scheme, transition section 16 highly accounts for 5% of total reactor height.
In technique scheme, bottom reactor reaction section 15, be less than 50% of reactor reaction section 15 overall length to the distance of inclined tube 4 to be generated and reactor reaction section 15 junction.
In technique scheme, reactor 1 inside or outer setting heat collector, heat collector height accounts for 30% ~ 95% of height for reactor; Revivifier 2 inside or outer setting heat collector, heat collector height accounts for 30% ~ 80% of revivifier 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, reactor 1, for being converted into based on the product of ethene, propylene and aromatic hydrocarbons by raw material 8 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.
For solve the problem two, the technical solution used in the present invention is as follows: the fluidized bed reaction method of a kind of methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, adopts above-mentioned reactive system, and described reaction method comprises following step:
A) raw material 8 enters reactor reaction section 15 and catalyst exposure reaction, formation reaction product 9 and carbon deposited catalyst, and reaction product 9 is separated after carbon deposited catalyst through gas-solid cyclone separator and enters subsequent separation system;
B) carbon deposited catalyst warp enters stripper 3 with the inclined tube to be generated 4 be connected bottom reactor 1 and contacts stripping with the stripping fluid 12 entered bottom stripper 3, carbon deposited catalyst after the stripped product 13 obtained and stripping, stripped product 13 is separated after carbon deposited catalyst through gas-solid cyclone separator and enters subsequent separation system;
C) carbon deposited catalyst after stripping enters stripping standpipe 6 through stripping inclined tube 5, is promoted to revivifier 2 through promoting medium 14;
D) carbon deposited catalyst after stripping contacts with the regenerating medium 10 entered bottom revivifier 2 and burns in revivifier 2, obtains the catalyzer after regenerating and flue gas 11;
E) catalyzer after regeneration is advanced into reactor reaction section 15 7 times through regenerator sloped tube.
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 8 inlet amount is 3 ~ 40: 1, and the density of catalyst of conversion zone 15 is 50 ~ 200 kgs/m
3, average gas superficial velocity 0.01 ~ 1 meter per second.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 8 inlet amount is 10 ~ 40: 1, and the density of catalyst of conversion zone 15 is 50 ~ 140 kgs/m
3, average gas superficial velocity 0.06 ~ 1 meter per second; 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 8 inlet amount is 3 ~ 30: 1, and the density of catalyst of conversion zone 15 is 100 ~ 200 kgs/m
3, average gas superficial velocity 0.01 ~ 0.3 meter per second; 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, and the density of catalyst of conversion zone 15 is 80 ~ 180 kgs/m
3, 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.
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 8 is methyl alcohol or dme or both mixtures, particular methanol.
In technique scheme, in raw material 8, the mass percentage of water is 0.01 ~ 30 % by weight, preferably lower than 10 % by weight.
In technique scheme, stripping fluid 12 is water vapor or N
2or water vapor and N
2mixture, promote medium 14 be water vapor or N
2or water vapor and N
2mixture, regenerating medium 10 is air or air and O
2mixture or air 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.
Adopt technical scheme of the present invention, operate under maximum ethene, propylene pattern, take methyl alcohol as raw material, the temperature of reaction of reactor is 480 DEG C, be 0.2 MPa in gauge pressure reaction pressure, weight space velocity is 2 (Grams Per Hours)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 12: 1, and in reactor, the density of catalyst of reaction zone is 80 kgs/m
3, average gas superficial velocity 0.08 meter per second; Adopt Cu-ZSM-5 catalyzer; Methanol feeding; Ethene carbon base absorption rate is 21.7 % by weight, propylene carbon base absorption rate is 18.3 % by weight, aromatic hydrocarbons carbon base absorption rate be 41.0 % by weight, BTX carbon base absorption rates is 32.8 % by weight.
Adopt technical scheme of the present invention, operate under maximum aromatic hydrocarbons pattern, take methyl alcohol as raw material, the temperature of reaction of reactor is 465 DEG C, be 0.25 MPa in gauge pressure reaction pressure, weight space velocity is 0.3 (Grams Per Hour)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 10: 1, and in reactor, the density of catalyst of reaction zone is 130 kgs/m
3, average gas superficial velocity 0.01 meter per second; Adopt Zn-P-ZSM-5 catalyzer; Methanol feeding; Ethene carbon base absorption rate is 11.1 % by weight, propylene carbon base absorption rate is 7.8 % by weight, aromatic hydrocarbons carbon base absorption rate be 62.2 % by weight, BTX carbon base absorption rates is 49.4 % by weight.
Adopt technical scheme of the present invention, operate under coproduction ethene, propylene and aromatic hydrocarbons pattern, take methyl alcohol as raw material, the temperature of reaction of reactor is 460 DEG C, be 0.2 MPa in gauge pressure reaction pressure, weight space velocity is 0.5 (Grams Per Hour)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 30: 1, and in reactor, the density of catalyst of reaction zone is 120 kgs/m
3, average gas superficial velocity 0.02 meter per second; Adopt Zn-Mg-P-ZSM-5 catalyzer; Methanol feeding; Ethene carbon base absorption rate is 16.5 % by weight, propylene carbon base absorption rate is 12.0 % by weight, aromatic hydrocarbons carbon base absorption rate be 53.5 % by weight, BTX carbon base absorption rates is 41.7 % by weight.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram of technical scheme of the present invention.
In Fig. 1,1 is reactor; 2 is revivifier; 3 is stripper; 4 is inclined tube to be generated; 5 is stripping inclined tube; 6 is stripping standpipe; 7 is regenerator sloped tube; 8 is methyl alcohol and/or dme; 9 is the product of reactor; 10 is regenerating medium; 11 is flue gas; 12 is stripping fluid; 13 is stripped product; 14 for promoting medium; 15 is the conversion zone of reactor; 16 is the transition section of reactor; 17 is the dilute phase section of reactor.
In Fig. 1, raw material 8 enters reactor reaction section 15 and catalyst exposure reaction, formation reaction product 9 and carbon deposited catalyst, and reaction product 9 is separated after carbon deposited catalyst through gas-solid cyclone separator and enters subsequent separation system; Carbon deposited catalyst warp enters stripper 3 with the inclined tube to be generated 4 be connected bottom reactor 1 and contacts stripping with the stripping fluid 12 entered bottom stripper 3, carbon deposited catalyst after the stripped product 13 obtained and stripping, stripped product 13 is separated after carbon deposited catalyst through gas-solid cyclone separator and enters subsequent separation system; Carbon deposited catalyst after stripping enters stripping standpipe 6 through stripping inclined tube 5, is promoted to revivifier 2 through promoting medium 14; Carbon deposited catalyst after stripping contacts with the regenerating medium 10 entered bottom revivifier 2 and burns in revivifier 2, obtains the catalyzer after regenerating and flue gas 11; Catalyzer after regeneration is advanced into reactor reaction section 15 7 times through regenerator sloped tube; Reaction product 9 and stripped product 13 enter subsequent separation system.
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 conversion zone diameter of reactor is 1.5 meters, and it highly accounts for 80% of total reactor height, and the diameter ratio of dilute phase section diameter and conversion zone is 2:1, and it highly accounts for 15% of total reactor height.Arrange heat collector outside reactor, heat collector height accounts for 85% of height for reactor.Arrange heat collector outside revivifier, heat collector height accounts for 80% of revivifier height.
The reaction conditions of reactor is: temperature is 480 DEG C, be 0.2 MPa in gauge pressure reaction pressure, weight space velocity is 2 (Grams Per Hours)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 12: 1, and in reactor, the density of catalyst of reaction zone is 80 kgs/m
3, average gas superficial velocity 0.08 meter per second.Regenerator temperature is 650 DEG C.Take methyl alcohol as raw material, water-content is 5 % by weight.
Stripping fluid is water vapor.Lifting medium is water vapour.Regenerating medium is air.
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.
Reaction result is in table 1.
[embodiment 2]
Adopt device as shown in Figure 1.The conversion zone diameter of reactor is 5 meters, and it highly accounts for 60% of total reactor height, and the diameter ratio of dilute phase section diameter and conversion zone is 1.1:1, and it highly accounts for 35% 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, weight space velocity is 10 (Grams Per Hours)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 3: 1, and in reactor, the density of catalyst of reaction zone is 50 kgs/m
3, average gas superficial velocity 0.17 meter per second.The temperature of revivifier is 680 DEG C.Take methyl alcohol as raw material, water-content is 30 % by weight.
Stripping fluid is N
2.Lifting medium is N
2.Regenerating medium is air.
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.
Reaction result is in table 1.
[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, weight space velocity is 10 (Grams Per Hours)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 30: 1, and in reactor, the density of catalyst of reaction zone is 200 kgs/m
3, average gas superficial velocity 1.2 meter per second.The temperature of revivifier is 580 DEG C.Take methyl alcohol as raw material, water-content is 0.01 % by weight.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.
Stripping fluid is water vapor.Lifting medium is N
2.Regenerating medium is air and O
2mixture, volume ratio is 8: 2.
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.
Reaction result is in table 1.
[embodiment 4]
Adopt device as shown in Figure 1.The conversion zone diameter of reactor is 3 meters, and it highly accounts for 70% of total reactor height, and the diameter ratio of dilute phase section diameter and conversion zone is 1.4:1, and it highly accounts for 25% of total reactor height.Arrange heat collector outside reactor, heat collector height accounts for 60% of height for reactor.Arrange heat collector outside revivifier, heat collector height accounts for 70% of revivifier height.
The reaction conditions of reactor is: temperature is 470 DEG C, be 0.3 MPa in gauge pressure reaction pressure, weight space velocity is 1 (Grams Per Hour)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 25: 1, and in reactor, the density of catalyst of reaction zone is 80 kgs/m
3, average gas superficial velocity 0.03 meter per second.The temperature of revivifier is 700 DEG C.Take dme as raw material.
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.
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.
Reaction result is in table 1.
[embodiment 5]
Adopt the device of embodiment 4.
The reaction conditions of reactor is: temperature is 465 DEG C, be 0.25 MPa in gauge pressure reaction pressure, weight space velocity is 0.3 (Grams Per Hour)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 10: 1, and in reactor, the density of catalyst of reaction zone is 130 kgs/m
3, average gas superficial velocity 0.01 meter per second.The temperature of revivifier is 630 DEG C.Take methyl alcohol as raw material, water-content is 10 % 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.
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.
Reaction result is in table 1.
[embodiment 6]
Adopt device as shown in Figure 1.The conversion zone diameter of reactor is 0.3 meter, and it highly accounts for 85% of total reactor height, and the diameter ratio of dilute phase section diameter and conversion zone is 2:1, and it highly accounts for 10% of total reactor height.Arrange heat collector in reactor, heat collector height accounts for 90% of height for reactor.Arrange heat collector outside revivifier, heat collector height accounts for 50% of revivifier height.
The reaction conditions of reactor is: temperature is 480 DEG C, be 0.1 MPa in gauge pressure reaction pressure, weight space velocity is 2 (Grams Per Hours)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 20: 1, and in reactor, the density of catalyst of reaction zone is double centner/rice
3, average gas superficial velocity 0.12 meter per second.The temperature of revivifier is 600 DEG C.Take dme as raw material.
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.
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.
Reaction result is in table 1.
[embodiment 7]
Adopt device as shown in Figure 1.The conversion zone diameter of reactor is 6 meters, and it highly accounts for 65% of total reactor height, and the diameter ratio of dilute phase section diameter and conversion zone is 1.1:1, and it highly accounts for 30% of total reactor height.Arrange heat collector outside reactor, heat collector height accounts for 80% of height for reactor.Arrange heat collector outside revivifier, heat collector height accounts for 40% of revivifier height.
The reaction conditions of reactor is: temperature is 450 DEG C, be 0.15 MPa in gauge pressure reaction pressure, weight space velocity is 0.8 (Grams Per Hour)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 6: 1, and in reactor, the density of catalyst of reaction zone is 70 kgs/m
3, average gas superficial velocity 0.04 meter per second.With the mixture of methyl alcohol, dme for raw material, both mass ratioes are 8:2.The temperature of revivifier is 720 DEG C.
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.
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.
Reaction result is in table 1.
[embodiment 8]
Adopt device as shown in Figure 1.The conversion zone diameter of reactor is 2 meters, and it highly accounts for 70% of total reactor height, and the diameter ratio of dilute phase section diameter and conversion zone is 1.3:1, and it highly accounts for 25% of total reactor height.Arrange heat collector outside reactor, heat collector height accounts for 90% 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 460 DEG C, be 0.2 MPa in gauge pressure reaction pressure, weight space velocity is 0.5 (Grams Per Hour)/gram catalyzer, and the mass ratio of catalyst recirculation amount and feedstock amount is 30: 1, and in reactor, the density of catalyst of reaction zone is 120 kgs/m
3, average gas superficial velocity 0.02 meter per second.The temperature of revivifier is 630 DEG C.Take methyl alcohol as raw material, water-content is 0.01 % 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.
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.
Reaction result is in table 1.
Table 1
Yield of ethene, % by weight | Propene yield, % by weight | Aromatics yield, % by weight | |
Embodiment 1 | 21.7 | 18.3 | 41.0 |
Embodiment 2 | 12.3 | 10.4 | 57.2 |
Embodiment 3 | 20.2 | 17.9 | 43.1 |
Embodiment 4 | 13.8 | 10.2 | 58.3 |
Embodiment 5 | 11.1 | 7.8 | 62.2 |
Embodiment 6 | 15.9 | 14.2 | 52.4 |
Embodiment 7 | 12.6 | 8.8 | 60.2 |
Embodiment 8 | 16.5 | 12.0 | 53.5 |
Claims (10)
1. a fluidized bed reaction system for methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, comprises reactor (1), revivifier (2), stripper (3); Reactor (1) is conversion zone (15), transition section (16), dilute phase section (17) from bottom to top; Raw material (8) enters reactor reaction section (15) bottom and catalyst exposure reaction, reacted carbon deposited catalyst is descending, the inclined tube to be generated (4) that warp is connected with reactor (1) bottom enters stripper (3), catalyzer after stripping goes upward to revivifier (2) regeneration through stripping inclined tube (5), stripping standpipe (6), and the catalyzer after regeneration comes downwards to reactor reaction section (15) through regenerator sloped tube (7).
2. the fluidized bed reaction system 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 reaction section (15) accounts for 60 ~ 85% of total reactor height; The diameter ratio of dilute phase section (17) diameter and conversion zone (15) is 1.1 ~ 2:1, and it highly accounts for 10 ~ 35% of total reactor height; Transition section (16) highly accounts for 5% of total reactor height.
3. the fluidized bed reaction system of methyl alcohol according to claim 1 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, is characterized in that reactor reaction section (15) bottom is less than 50% of reactor reaction section (15) overall length to the distance of inclined tube to be generated (4) and reactor reaction section (15) junction.
4. the fluidized bed reaction system of methyl alcohol according to claim 1 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, it is characterized in that reactor (1) inside or outer setting heat collector, heat collector height accounts for 30% ~ 95% of height for reactor; Revivifier (2) inside or outer setting heat collector, heat collector height accounts for 30% ~ 80% of revivifier height.
5. the fluidized bed reaction system of methyl alcohol according to claim 1 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, is characterized in that reactor (1), revivifier (2) and stripper (3) inside are equipped with 1 ~ 3 grade of gas-solid cyclone separator.
6. a fluidized bed reaction method for methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, adopt the reactive system described in claim 1 ~ 5, described reaction method comprises following step:
A) raw material (8) enters reactor reaction section (15) and catalyst exposure reaction, formation reaction product (9) and carbon deposited catalyst, and reaction product (9) is separated after carbon deposited catalyst through gas-solid cyclone separator and enters subsequent separation system;
B) inclined tube to be generated (4) that carbon deposited catalyst warp is connected with reactor (1) bottom enters stripper (3) and contacts stripping with the stripping fluid (12) entered from stripper (3) bottom, carbon deposited catalyst after the stripped product (13) obtained and stripping, stripped product (13) is separated after carbon deposited catalyst through gas-solid cyclone separator and enters subsequent separation system;
C) carbon deposited catalyst after stripping enters stripping standpipe (6) through stripping inclined tube (5), is promoted to revivifier (2) through promoting medium (14);
D) regenerating medium (10) contact that the carbon deposited catalyst after stripping enters from revivifier (2) bottom in revivifier (2) neutralization is burnt, and obtains the catalyzer after regenerating and flue gas (11);
E) catalyzer after regeneration is advanced into reactor reaction section (15) under regenerator sloped tube (7).
7. the 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 (8) 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 (8) inlet amount is 3 ~ 40: 1, and density of catalyst is 50 ~ 200 kgs/m
3, 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 fluidized bed reaction method of methyl alcohol according to claim 7 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 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 (8) is for methyl alcohol or dme or both mixtures, the mass percentage of water is 0.01 ~ 30 % by weight.
10. the 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 (12) is for water vapor or N
2or water vapor and N
2mixture, promote medium (14) be water vapor or N
2or water vapor and N
2mixture, regenerating medium (10) is air or air and O
2mixture or air and N
2mixture.
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