CN105457569A - Double regenerator reaction device for preparing low-carbon olefins and aromatic hydrocarbon by converting methanol or dimethyl ether and reaction method for double regenerator reaction device - Google Patents
Double regenerator reaction device for preparing low-carbon olefins and aromatic hydrocarbon by converting methanol or dimethyl ether and reaction method for double regenerator reaction device Download PDFInfo
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Abstract
The invention relates to a double regenerator reaction device for preparing low-carbon olefins and aromatic hydrocarbon by converting methanol or dimethyl ether and a reaction method for the double regenerator reaction device, and mainly solves the problem that in the prior art, olefins and aromatic hydrocarbon are low in yield, and hydrothermal deactivation of a catalyst is severe. The problem is better solved by adopting a technical scheme that through the device comprises a reactor, a quick bed regenerator, a turbulent bed regenerator, a stripper, a settler and a degassing tank, raw materials enter into the reactor from the lower part of the reactor to be contacted with the catalyst to react, a carbon deposit catalyst after reaction enters into the quick bed regenerator and/or the turbulent bed regenerator through the stripper, a part of catalyst regenerated by the quick bed regenerator moves upward to the settler to be settled and then enters into the turbulent bed regenerator to be continuously regenerated, and the fully regenerated catalyst which is degassed in the degassing tank returns to the reactor. The device can be used for industrial production of olefins and aromatic hydrocarbon.
Description
Technical field
The present invention relates to two regenerator fluidized bed reaction and the reaction method thereof of a kind of methyl alcohol and/or dimethyl ether conversion alkene and aromatic hydrocarbons.
Background technology
Alkene 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 demand sustainable growth of alkene and aromatic hydrocarbons.
The steam cracking process being raw material with liquid hydrocarbon (as naphtha, diesel oil, secondary operations oil) is the main production of alkene 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, cost of material constantly increases.The factor be subject to, alternative materials is prepared alkene and aromatic hydrocarbons technology and is caused and pay close attention to more and more widely.Wherein, for coal-based methanol, dimethyl ether 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 dimethyl ether for raw material prepares alkene and aromatic hydrocarbons.
In various existing methyl alcohol, dimethyl ether catalysis transformation technology, the product of methanol/dimethyl ether conversion aromatic hydrocarbons comprises alkene and aromatic hydrocarbons simultaneously.This technology sees the people (JournalofCatalysis, 1977,47,249) such as the Chang of Mobil company in 1977 at first and reports on ZSM-5 molecular sieve catalyst methyl alcohol and oxygenatedchemicals transforms the method preparing the hydrocarbons 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 catalyst, reaction temperature is 400 ~ 450 DEG C, methyl alcohol, dimethyl ether air speed 1.3 (Grams Per Hour)/gram catalyst.
Relevant report and the patent in this field are more, but the object product of most of technology is aromatic hydrocarbons, and alkene belongs to accessory substance, 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 technology path being Methanol aromatic hydrocarbons disclosed in some patent, as patent CN102775261, CN102146010, CN102531821, CN102190546, CN102372537 etc.
Wherein, disclosed in patent CN102775261, Multi-function methanol processing method and device utilize preparing low carbon olefin hydrocarbon with methanol, gasoline, aromatic hydrocarbons.The method adopts two-step method production technology, 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 courses of reaction can be fixed bed or fluid bed.The method adopts two-step method, and technological process is complicated.
Take methyl alcohol as the technique that raw material produces 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 reactors, 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 technological process is complicated.
Be the method for the co-fed production low-carbon alkene of methyl alcohol and naphtha and/or aromatic hydrocarbons disclosed in patent CN102531821, adopt the ZSM-5 catalyst of load 2.2 ~ 6.0 % by weight La and 1.0 ~ 2.8 % by weight P, fixed bed reactors or fluidized-bed reactor can be adopted.Reaction temperature is 550 ~ 670 DEG C, air speed 1.0 ~ 5 (Grams Per Hour)/gram catalyst.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.
Alkene and the low problem of 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.
Above-mentioned existing fluidization of producing aromatic hydrocarbons for raw material with methyl alcohol and/or dimethyl ether all adopts single regenerator to carry out catalyst circulation reaction regeneration.For ensureing high activity of catalyst, needing the carbon content of regenerated catalyst as far as possible low, below 0.05 ~ 0.1 % by weight, therefore unavoidably needing high temperature regeneration, generally at about 650 ~ 730 DEG C.The coke that catalyst reaction generates is containing protium, and protium oxidation reaction can produce steam.For molecular sieve catalyst, can lose activity because of framework of molecular sieve dealuminzation under this hydro-thermal atmosphere, this inactivation is permanent and irreversible.For single regenerator reaction unit, the overwhelming majority of catalyst total amount is present in regenerator, and regenerator inner catalyst reserve is excessive, and the time of staying of catalyst in regenerator is long, and catalyst hydrothermal deactivation is serious, and service life reduces, and production cost increases.Propose to the property of the present invention is directed to the technical scheme of two regenerator, solve the problems referred to above.
Summary of the invention
One of technical problem to be solved by this invention be in prior art alkene and aromatics yield low, the technical problem that catalyst hydrothermal deactivation is serious, provides two regenerator fluidized bed reactions of a kind of methyl alcohol and/or dimethyl ether conversion alkene and aromatic hydrocarbons.This device has alkene and aromatics yield is high, effectively alleviate the advantage of catalyst hydrothermal deactivation.
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: two regenerator fluidized bed reactions of a kind of methyl alcohol and/or dimethyl ether conversion alkene and aromatic hydrocarbons, comprises the device of reactor 1, fast bed regenerator 2, turbulent bed regenerator 3, stripper 4, settler 5; Raw material 14 enters reactor 1 and catalyst exposure reaction from reactor 1 bottom, stripping standpipe 8 of passing through under reacted carbon deposited catalyst is promoted to stripper 4 stripping; Stripping rear catalyst enters fast bed regenerator 2 and/or turbulent bed regenerator 3; Regenerate through fast bed regenerator 2 on the semi regeneration catalyst obtained and be advanced into settler 5, the semi regeneration catalyst after sedimentation enters turbulent bed regenerator 3 and continues regeneration; Through turbulent bed regenerator 3 regenerate the regenerated catalyst obtained enter degassing tank 6 degassed after Returning reactor 1; Fast bed regenerator 2 is the first regenerator section 25, changeover portion 26, second regenerator section 27 from bottom to top, and regeneration temperature is 500 ~ 600 DEG C, and in regenerating medium 17, the content of oxygen is 2 ~ 21 volume %; Fast bed regenerator 2 and settler 5 are coaxially arranged, and the second regenerator section 27 top of fast bed regenerator 2 is positioned at settler 5; Turbulent bed regenerator 3 is close phase section 28, changeover portion 29, dilute phase section 30 from bottom to top; Regeneration temperature is 580 ~ 750 DEG C, and in regenerating medium 19, the content of oxygen is 21 ~ 30 volume %.
In technique scheme, be advanced into and the stripping inclined tube 7 be connected bottom reactor 1 under the carbon deposited catalyst that reactor 1 generates, then be promoted to stripper 4 through stripping standpipe 8; Stripping rear catalyst part enters fast bed regenerator 2 first regenerator section 25 through fast bed inclined tube to be generated 13, and part enters the close phase section 28 of turbulent bed regenerator 3 through turbulent bed inclined tube to be generated 9, or only enters the close phase section 28 of turbulent bed regenerator 3 through turbulent bed inclined tube to be generated 9; Regenerate through fast bed regenerator 2 on the semi regeneration catalyst obtained and be advanced into settler 5, the semi regeneration catalyst after sedimentation enters the close phase section 28 of turbulent bed regenerator 3 through semi regeneration agent carrier pipe 10 and continues regeneration; Regenerate the regenerated catalyst obtained to enter degassing tank 6 through degassing tank inclined tube 11 degassed through turbulent bed regenerator 3; Degassed rear regenerated catalyst is through regenerator sloped tube 12 Returning reactor 1.
In technique scheme, the height of fast bed regenerator 2 first regenerator section 25 accounts for 70 ~ 90% of fast bed regenerator total height; Second regenerator section 27 diameter and the first regenerator section 25 diameter ratio are 0.3 ~ 1.2:1, preferably 0.4 ~ 0.9:1; Second regenerator section 27 highly accounts for 9 ~ 27% of fast bed regenerator total height; Changeover portion 26 highly accounts for 1 ~ 3% of fast bed regenerator total height.
In technique scheme, the height of the close phase section 28 of turbulent bed regenerator 3 accounts for 60 ~ 90% of turbulent bed regenerator total height; Dilute phase section 27 diameter and close phase section 25 diameter ratio are 1.1 ~ 3:1, preferably 1.1 ~ 2:1; Dilute phase section highly accounts for 9 ~ 37% of turbulent bed regenerator total height; Changeover portion 29 highly accounts for 1 ~ 3% of turbulent bed regenerator total height;
In technique scheme, turbulent bed regenerator 3 inside or outer setting heat collector, heat collector height accounts for 30% ~ 80% of turbulent bed regenerator height.
In technique scheme, turbulent bed regenerator 3 top is provided with one group of gas-solid cyclone separator 32, is 1 ~ 3 grade; Settler 5 top is provided with one group of gas-solid cyclone separator 31, is 1 ~ 3 grade
In technique scheme, reactor 1, for reacting raw material 14 and catalyst exposure to the product be converted into based on alkene and aromatic hydrocarbons; Fast bed regenerator 2, for removing the hydrogen on carbon deposited catalyst in coke, generates semi regeneration catalyst; Turbulent bed regenerator 3, the coke on semi regeneration catalyst, generates regenerated catalyst; Stripper 4, goes out the product that carbon deposited catalyst carries for stripping; Settler 5, for the semi regeneration catalyst that the fast bed regenerator of sedimentation obtains; Degassing tank 6, for the regenerated flue gas that the regenerated catalyst after removing the regeneration of turbulent bed regenerator is further carried secretly.
For solve the problem two, the technical solution used in the present invention is as follows: two regenerator fluidized bed reaction methods of a kind of methyl alcohol and/or dimethyl ether conversion alkene and aromatic hydrocarbons, and adopt above-mentioned device, described method comprises following step:
A) raw material 14 enters reactor 1 and catalyst exposure reaction from reactor 1 bottom, reaction of formation product 24 and carbon deposited catalyst, and product 24 enters later separation device;
B) be advanced under carbon deposited catalyst and the stripping inclined tube 7 be connected bottom reactor 1, enter stripping standpipe 8 again, stripper 4 is promoted to through promoting medium 23, stripping is contacted with stripping fluid 15, carbon deposited catalyst after the stripped product 16 obtained and stripping, stripped product 16 enters later separation device;
C) the carbon deposited catalyst part after stripping enters fast bed regenerator 2 first regenerator section 25 through fast bed inclined tube to be generated 13, part enters the close phase section 28 of turbulent bed regenerator 3 through turbulent bed inclined tube to be generated 9, or only enters the close phase section 28 of turbulent bed regenerator 3 through turbulent bed inclined tube to be generated 9;
D) carbon deposited catalyst after stripping contacts annealing in hydrogen atmosphere in fast bed regenerator 2 with regenerating medium 17, burning carbon obtains semi regeneration catalyst and flue gas 18, on be advanced into settler 5, semi regeneration catalyst sedimentation, flue gas 18 is separated after semi regeneration catalyst through gas-solid cyclone separator 31 and enters follow-up flue gas energy recovery device, and the semi regeneration catalyst of sedimentation enters the close phase section 28 of turbulent bed regenerator 3 through semi regeneration agent carrier pipe 10;
E) carbon deposited catalyst after semi regeneration catalyst and/or stripping contacts with regenerating medium 19 to make charcoal and obtains regenerated catalyst and flue gas 20 in turbulent bed regenerator 3, and flue gas 20 enters follow-up flue gas energy recovery device or the regenerating medium as fast bed regenerator 2 after gas-solid cyclone separator 32 separation regeneration catalyst;
F) regenerated catalyst enters degassing tank 6 through degassing tank inclined tube 11 and contacts with degassed medium 21, remove flue gas 22 further, flue gas 22 enters follow-up flue gas energy recovery device or the regenerating medium as fast bed regenerator 2, regenerator sloped tube 12 Returning reactor 1 of passing through under the regenerated catalyst after degassed.
In technique scheme, the regeneration temperature of fast bed regenerator 2 is 500 ~ 600 DEG C, preferably 530 ~ 570 DEG C; Average gas superficial velocity is 1 ~ 8 meter per second, preferably 1.5 ~ 5 meter per seconds,
In technique scheme, in the regenerating medium 17 of fast bed regenerator 2, the content of oxygen is 2 ~ 21 volume %, preferably 3 ~ 15 volume %; Can be the mixture of flue gas 20 that the mixture of flue gas 20 that air or turbulent bed regenerator 3 obtain and/or the flue gas 22 that degassing tank 6 obtains or air and turbulent bed regenerator 3 obtain and/or the flue gas 22 that degassing tank 6 obtains.
In technique scheme, the regeneration temperature of turbulent bed regenerator 3 is 580 ~ 750 DEG C, preferably 630 ~ 700 DEG C; Average gas superficial velocity is 0.5 ~ 2 meter per second, preferably 0.8 ~ 1.5 meter per second.
In technique scheme, in the regenerating medium 19 of turbulent bed regenerator 3, the content of oxygen is 21 ~ 30 volume %, preferably 21 ~ 25 volume %; Can be air or air and O
2mixture.
In technique scheme, the charcoal on the regenerated catalyst that turbulent bed regenerator 3 obtains, with the mass percent of catalyst, content is lower than 0.1 % by weight, preferred lower than 0.08 % by weight further.
In technique scheme, the reaction temperature of reactor 1 is 400 ~ 550 DEG C, the weight space velocity of raw material 14 is 0.1 ~ 10 (Grams Per Hour)/gram catalyst, be 0 ~ 0.5 MPa in gauge pressure reaction pressure, the mass ratio of catalyst circulation amount and raw material 14 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.
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, aluminium oxide, silica; The mass ratio of active component and carrier is (10 ~ 50): (50 ~ 90), preferably (20 ~ 40): (60 ~ 80).
In technique scheme, catalyst cupport has one or more elements or oxide in Zn, Ag, P, Ga, Cu, Mn, Mg, preferred Zn, P; With the mass percent of catalyst, 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 component of catalyst is selected from ZSM-5 molecular sieve, with the weight percent meter of catalyst, and the Zn element of load 0.01 ~ 5 % by weight on catalyst or oxide, the P element of 0.1 ~ 8 % by weight or oxide.
In technique scheme, raw material 14 is methyl alcohol or dimethyl ether or both mixtures, particular methanol.
In technique scheme, in raw material 14, the mass percentage of water is 0.01 ~ 30 % by weight, preferably lower than 10 % by weight.
In technique scheme, stripping fluid 15 is water vapour or N
2or water vapour and N
2mixture, promote medium 23 be water vapour or N
2or water vapour and N
2mixture, degassed medium 21 is water vapour or N
2or water vapour and N
2mixture.
Technical scheme provided by the invention, adopt two regenerator regeneration, reclaimable catalyst in fast bed regenerator at low temperature, oxygen deprivation, quick annealing in hydrogen atmosphere in the short period, semi regeneration catalyst after annealing in hydrogen atmosphere enters turbulent bed regenerator at high temperature, oxygen enrichment, thoroughly burn carbon in the long period, finally obtains the high activity regenerated catalyst that carbon content is lower.Owing to can not generate a large amount of water when the semi regeneration catalyst of burned hydrogen continues to burn carbon under the hot conditions of 580 ~ 750 DEG C, catalyst hydrothermal dealumination phenomenon obviously weakens.
Technical scheme provided by the invention, adopts the fluidized-bed reactor of catalyst and reaction mass countercurrent movement, and effectively can promote contacting of reaction mass and catalyst active center, minimizing extends influence, and improves mass-transfer efficiency; Air speed adjustable range can also be expanded simultaneously, realize the object that maximum produces alkene and aromatic hydrocarbons easily.
Adopting technical scheme of the present invention, take methyl alcohol as raw material, and water content is 5 % by weight; Fast bed regenerator regeneration temperature is 560 DEG C, and average gas superficial velocity is 2 meter per seconds, and regenerating medium is air; Turbulent bed regenerator regeneration temperature is 650 DEG C, and average gas superficial velocity is 0.8 meter per second, and regenerating medium is air; The reaction temperature of reactor is 480 DEG C, be 0.2 MPa in gauge pressure reaction pressure, weight space velocity is 2 (Grams Per Hours)/gram catalyst, and the mass ratio of catalyst circulation amount and feedstock amount is 12: 1, and in reactor, the density of catalyst of reaction zone is double centner/rice
3, average gas superficial velocity 0.2 meter per second; Adopt Cu-ZSM-5 catalyst; 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.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram of technical scheme of the present invention, and Fig. 2 is the schematic diagram of fast bed regenerator, and Fig. 3 is the schematic diagram of turbulent bed regenerator.
1 be reactor in 1 ~ 2 in figure; 2 is fast bed regenerator; 3 is turbulent bed regenerator; 4 is stripper; 5 is settler; 6 is degassing tank; 7 is stripping inclined tube; 8 is stripping standpipe; 9 is turbulent bed inclined tube to be generated; 10 is semi regeneration agent carrier pipe; 11 is degassing tank inclined tube; 12 is regenerator sloped tube; 13 is fast bed inclined tube to be generated; 14 is raw material; 15 is stripping fluid; 16 is stripped product; 17 is fast bed regenerator regenerating medium; 18 is fast bed regenerator flue gas; 19 is turbulent bed regenerator regenerating medium; 20 is turbulent bed regenerator flue gas; 21 is degassed medium; 22 is degassing tank flue gas; 23 for promoting medium; 24 is product; 25 is fast bed regenerator first regenerator section; 26 is fast bed regenerator changeover portion; 27 is fast bed regenerator second regenerator section; 28 is the close phase section of turbulent bed regenerator; 29 is turbulent bed regenerator changeover portion; 30 is turbulent bed regenerator dilute phase section.
Fig. 1 Raw 14 enters reactor 1 and catalyst exposure reaction from reactor 1 bottom, reaction of formation product 24 and carbon deposited catalyst, and product 24 is separated after carbon deposited catalyst through gas-solid cyclone separator and enters later separation device; Be advanced under carbon deposited catalyst and the stripping inclined tube 7 be connected bottom reactor 1, enter stripping standpipe 8 again, stripper 4 is promoted to through promoting medium 23, stripping is contacted with stripping fluid 15, carbon deposited catalyst after the stripped product 16 obtained and stripping, stripped product 16 is separated after carbon deposited catalyst through gas-solid cyclone separator and enters later separation device; Carbon deposited catalyst part after stripping enters fast bed regenerator 2 first regenerator section 25 through fast bed inclined tube to be generated 13, part enters the close phase section 28 of turbulent bed regenerator 3 through turbulent bed inclined tube to be generated 9, or only enters the close phase section 28 of turbulent bed regenerator 3 through turbulent bed inclined tube to be generated 9; Carbon deposited catalyst after stripping contacts annealing in hydrogen atmosphere in fast bed regenerator 2 with regenerating medium 17, burning carbon obtains semi regeneration catalyst and flue gas 18, on be advanced into settler 5, semi regeneration catalyst sedimentation, flue gas 18 is separated after semi regeneration catalyst through gas-solid cyclone separator and enters follow-up flue gas energy recovery device, and the semi regeneration catalyst of sedimentation enters the close phase section 28 of turbulent bed regenerator 3 through semi regeneration agent carrier pipe 10; Carbon deposited catalyst after semi regeneration catalyst and/or stripping contacts with regenerating medium 19 to make charcoal and obtains regenerated catalyst and flue gas 20 in turbulent bed regenerator 3, and flue gas 20 enters follow-up flue gas energy recovery device or the regenerating medium as fast bed regenerator 2 after gas-solid cyclone separator separation regeneration catalyst; Regenerated catalyst enters degassing tank 6 through degassing tank inclined tube 11 and contacts with degassed medium 21, remove flue gas 22 further, flue gas 22 enters follow-up flue gas energy recovery device or the regenerating medium as fast bed regenerator 2, regenerator sloped tube 12 Returning reactor 1 of passing through under the regenerated catalyst after degassed.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Detailed description of the invention
[embodiment 1]
Adopt device as shown in Figure 1.Fast bed regenerator first regenerator section diameter is 1.5 meters, and it highly accounts for the 80%, second regenerator section diameter of fast bed regenerator height and the diameter ratio of the first regenerator section is 0.8:1, and it highly accounts for 15% of fast bed regenerator height.Regeneration temperature is 560 DEG C, and average gas superficial velocity is 2 meter per seconds.Regenerating medium is air, and oxygen content is 21 volume %.
Turbulent bed regenerator close phase section diameter is 3 meters, and it highly accounts for 70% of turbulent bed regenerator height, and dilute phase section diameter and close phase section diameter ratio are 1.3:1, and it highly accounts for 27% of turbulent bed regenerator height.The height of external heat collector accounts for 70% of regenerator height.Regeneration temperature is 650 DEG C, and average gas superficial velocity is 0.8 meter per second.Regenerating medium is air, and oxygen content is 21 volume %.Charcoal on catalyst after regeneration, with the mass percent of catalyst, content is 0.04 % by weight.
The reaction condition 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 catalyst, and the mass ratio of catalyst circulation amount and feedstock amount is 12: 1, and in reactor, the density of catalyst of reaction zone is double centner/rice
3, average gas superficial velocity 0.2 meter per second.Take methyl alcohol as raw material, water content is 5 % by weight.
Stripping fluid is water vapour.Lifting medium is steam.Degassed medium is N
2.
Adopt Cu-ZSM-5 catalyst.
The preparation process of Cu-ZSM-5 catalyst: by ZSM-5 molecular sieve, carrier and binding agent mechanical mixture, 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 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 alundum (Al2O3), 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 catalyst for 1.74:1 floods, at 120 DEG C dry 5 hours, then put into Muffle furnace roasting at 550 DEG C and within 6 hours, be prepared into the Cu-ZSM-5 catalyst that Cu constituent content is 8 % by weight.
[embodiment 2]
Adopt device as shown in Figure 1.Fast bed regenerator first regenerator section diameter is 1.8 meters, and it highly accounts for the 90%, second regenerator section diameter of fast bed regenerator height and the diameter ratio of the first regenerator section is 0.3:1, and it highly accounts for 9% of fast bed regenerator height.Regeneration temperature is 500 DEG C, and average gas superficial velocity is 1 meter per second.Regenerating medium is air, and oxygen content is 21 volume %.
Turbulent bed regenerator close phase section diameter is 2.6 meters, and it highly accounts for 90% of turbulent bed regenerator height, and dilute phase section diameter and close phase section diameter ratio are 3:1, and it highly accounts for 9% of turbulent bed regenerator height.The height of external heat collector accounts for 80% of regenerator height.Regeneration temperature is 580 DEG C, and average gas superficial velocity is 0.5 meter per second.Regenerating medium is the mixture of air and oxygen, and oxygen content is 30 volume %.Charcoal on catalyst after regeneration, with the mass percent of catalyst, content is 0.1 % by weight.
The reaction condition 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 catalyst, and the mass ratio of catalyst circulation amount and feedstock amount is 3: 1, and in reactor, the density of catalyst of reaction zone is 90 kgs/m
3, average gas superficial velocity 0.17 meter per second.Take methyl alcohol as raw material, water content is 30 % by weight.
Stripping fluid is N
2.Lifting medium is N
2.Degassed medium is steam.
Adopt Ag-Y-ZSM-23 catalyst.
The preparation process of Ag-Y-ZSM-23 catalyst: by Y molecular sieve, ZSM-23 molecular screen, carrier and binding agent mechanical mixture, 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 alundum (Al2O3), 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 Muffle furnace roasting at 550 DEG C and within 6 hours, be prepared into the Ag-Y-ZSM-23 catalyst that Ag constituent content is 0.1 % by weight.
[embodiment 3]
Adopt the device of embodiment 1.
Fast bed regenerator regeneration temperature is 600 DEG C, and average gas superficial velocity is 8 meter per seconds.Regenerating medium is the mixture of the flue gas that the flue gas that obtains of turbulent bed regenerator and degassing tank obtain, and oxygen content is 2 ~ 4 volume %.
Turbulent bed regenerator regeneration temperature is 750 DEG C, and average gas superficial velocity is 2 meter per seconds.Regenerating medium is air, and oxygen content is 21 volume %.Charcoal on catalyst after regeneration, with the mass percent of catalyst, content is 0.01 % by weight.
The reaction condition 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 catalyst, and the mass ratio of catalyst circulation amount and feedstock amount is 30: 1, and in reactor, the density of catalyst of reaction zone is 50 kgs/m
3, average gas superficial velocity 1 meter per second.Take methyl alcohol as raw material, water content is 0.01 % by weight.The height of the external heat collector of reactor accounts for 30% of height for reactor.
Stripping fluid is water vapour.Lifting medium is N
2.Degassed medium is N
2with the mixture of steam, volume ratio is 5:5.
Adopt Ga-beta catalyst.
The preparation process of Ga-beta catalyst: by beta-molecular sieve, carrier and binding agent mechanical mixture, 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, silica and alundum (Al2O3), 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 Muffle 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.Fast bed regenerator first regenerator section diameter is 2.5 meters, and it highly accounts for the 70%, second regenerator section diameter of fast bed regenerator height and the diameter ratio of the first regenerator section is 1.2:1, and it highly accounts for 27% of fast bed regenerator height.Regeneration temperature is 540 DEG C, and average gas superficial velocity is 3 meter per seconds.Regenerating medium is the flue gas that turbulent bed regenerator obtains, and oxygen content is 3 ~ 6 volume %.
Turbulent bed regenerator close phase section diameter is 4 meters, and it highly accounts for 60% of turbulent bed regenerator height, and dilute phase section diameter and close phase section diameter ratio are 1.1:1, and it highly accounts for 37% of turbulent bed regenerator height.The height of external heat collector accounts for 30% of regenerator height.Regeneration temperature is 720 DEG C, and average gas superficial velocity is 1.5 meter per seconds.Regenerating medium is air, and oxygen content is 21 volume %.Charcoal on catalyst after regeneration, with the mass percent of catalyst, content is 0.08 % by weight.
The reaction condition 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 catalyst, and the mass ratio of catalyst circulation amount and feedstock amount is 25: 1, and in reactor, the density of catalyst of reaction zone is 200 kgs/m
3, average gas superficial velocity 0.01 meter per second.Take dimethyl ether as raw material.
Stripping fluid is water vapour and N
2mixture, volume ratio is 5: 5.Lifting medium is N
2.Degassed medium is N
2with the mixture of steam, volume ratio is 9:1.
Adopt Mn-ZSM-11 catalyst.
The preparation process of Mn-ZSM-11 catalyst: by ZSM-11 molecular sieve, carrier and binding agent mechanical mixture, 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 alundum (Al2O3), 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 catalyst for 1:1 floods, at 120 DEG C dry 5 hours, then put into Muffle furnace roasting at 550 DEG C and within 6 hours, be prepared into the Mn-ZSM-11 catalyst that Mn constituent content is 9.09 % by weight.
[embodiment 5]
Adopt the device of embodiment 4.
Fast bed regenerator regeneration temperature is 580 DEG C, and average gas superficial velocity is 5 meter per seconds.Regenerating medium is the mixture that air and turbulent bed regenerator obtain flue gas, and oxygen content is 10 ~ 15 volume %.
Turbulent bed regenerator regeneration temperature is 700 DEG C, and average gas superficial velocity is 1.2 meter per seconds.Regenerating medium is air and oxygen mixture, and oxygen content is 27 volume %.Charcoal on catalyst after regeneration, with the mass percent of catalyst, content is 0.07 % by weight.
The reaction condition 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 catalyst, and the mass ratio of catalyst circulation amount and feedstock amount is 10: 1, and in reactor, the density of catalyst of reaction zone is 180 kgs/m
3, average gas superficial velocity 0.05 meter per second.Take methyl alcohol as raw material, water content is 10 % by weight.
Stripping fluid is water vapour.Promoting medium is water vapour and N
2mixture, volume ratio is 1: 9.Degassed medium is N
2.
Adopt Zn-P-ZSM-5 catalyst.
The preparation process of Zn-P-ZSM-5 catalyst: by ZSM-5 molecular sieve, carrier and binding agent mechanical mixture, 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 alundum (Al2O3), 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 Muffle 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 catalyst of 1.48 % by weight.
[embodiment 6]
Adopt device as shown in Figure 1.Fast bed regenerator first regenerator section diameter is 2 meters, and it highly accounts for the 80%, second regenerator section diameter of fast bed regenerator height and the diameter ratio of the first regenerator section is 1.1:1, and it highly accounts for 18% of fast bed regenerator height.Regeneration temperature is 530 DEG C, and average gas superficial velocity is 3 meter per seconds.Regenerating medium is the mixture of the flue gas that the flue gas that obtains of air and turbulent bed regenerator and degassing tank obtain, and oxygen content is 16 ~ 18 volume %.
Turbulent bed regenerator close phase section diameter is 2 meters, and it highly accounts for 80% of turbulent bed regenerator height, and dilute phase section diameter and close phase section diameter ratio are 2:1, and it highly accounts for 17% of turbulent bed regenerator height.The height of built-in heat collector accounts for 30% of regenerator height.Regeneration temperature is 720 DEG C, and average gas superficial velocity is 1.8 meter per seconds.Regenerating medium is air, and oxygen content is 21 volume %.Charcoal on catalyst after regeneration, with the mass percent of catalyst, content is 0.07 % by weight.
The reaction condition 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 catalyst, and the mass ratio of catalyst circulation amount and feedstock amount is 20: 1, and in reactor, the density of catalyst of reaction zone is 80 kgs/m
3, average gas superficial velocity 0.5 meter per second.Take dimethyl ether as raw material.
Stripping fluid is water vapour and N
2mixture, volume ratio is 2: 8.Promoting medium is water vapour and N
2mixture, volume ratio is 2: 8.Degassed medium is N
2with the mixture of steam, volume ratio is 7:3.
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 mechanical mixture, 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, silica and alundum (Al2O3), and the mass ratio of three is 5:2:3.
[embodiment 7]
Adopt the device of embodiment 6.
Fast bed regenerator regeneration temperature is 550 DEG C, and average gas superficial velocity is 2 meter per seconds.Regenerating medium is air, and oxygen content is 21 volume %.
Turbulent bed regenerator regeneration temperature is 650 DEG C, and average gas superficial velocity is 0.8 meter per second.Regenerating medium is air, and oxygen content is 21 volume %.Charcoal on catalyst after regeneration, with the mass percent of catalyst, content is 0.07 % by weight.
The reaction condition 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 catalyst, and the mass ratio of catalyst circulation amount and feedstock amount is 15: 1, and in reactor, the density of catalyst of reaction zone is double centner/rice
3, average gas superficial velocity 0.3 meter per second.With the mixture of methyl alcohol, dimethyl ether for raw material, both mass ratioes are 8:2.
Stripping fluid is water vapour.Promoting medium is water vapour and N
2mixture, volume ratio is 8: 2.Degassed medium is N
2with the mixture of steam, volume ratio is 2:8.
Adopt Zn-Ag-P-ZSM-5 catalyst.
The preparation process of Zn-Ag-P-ZSM-5 catalyst: by ZSM-5 molecular sieve, carrier and binding agent mechanical mixture, 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 alundum (Al2O3), 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 Muffle 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 catalyst of 1.51 % by weight.
[embodiment 8]
Adopt device as shown in Figure 1.Fast bed regenerator first regenerator section diameter is 1.7 meters, and it highly accounts for the 85%, second regenerator section diameter of fast bed regenerator height and the diameter ratio of the first regenerator section is 0.7:1, and it highly accounts for 12% of fast bed regenerator height.Regeneration temperature is 590 DEG C, and average gas superficial velocity is 6 meter per seconds.Regenerating medium is air, and oxygen content is 21 volume %.
Turbulent bed regenerator close phase section diameter is 2 meters, and it highly accounts for 70% of turbulent bed regenerator height, and dilute phase section diameter and close phase section diameter ratio are 2.2:1, and it highly accounts for 28% of turbulent bed regenerator height.The height of built-in heat collector accounts for 80% of regenerator height.Regeneration temperature is 740 DEG C, and average gas superficial velocity is 1.5 meter per seconds.Regenerating medium is air, and oxygen content is 21 volume %.Charcoal on catalyst after regeneration, with the mass percent of catalyst, content is 0.08 % by weight.
The reaction condition 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 catalyst, and the mass ratio of catalyst circulation amount and feedstock amount is 30: 1, and in reactor, the density of catalyst of reaction zone is 150 kgs/m
3, average gas superficial velocity 0.1 meter per second.Take methyl alcohol as raw material, water content is 0.01 % by weight.
Stripping fluid is water vapour and N
2mixture, volume ratio is 8: 2.Promoting medium is water vapour and N
2mixture, volume ratio is 5: 5.Degassed medium is N
2.
Adopt Zn-Mg-P-ZSM-5 catalyst.
The preparation process of Zn-Mg-P-ZSM-5 catalyst: by ZSM-5 molecular sieve, carrier and binding agent mechanical mixture, 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 alundum (Al2O3), 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 Muffle 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 catalyst of 2.35 % by weight.
Table 1
Claims (10)
1. two regenerator fluidized bed reactions for methyl alcohol and/or dimethyl ether conversion alkene and aromatic hydrocarbons, comprise the device of reactor (1), fast bed regenerator (2), turbulent bed regenerator (3), stripper (4), settler (5); Raw material (14) enters reactor (1) and catalyst exposure reaction from reactor (1) bottom, stripping standpipe (8) of passing through under reacted carbon deposited catalyst is promoted to stripper (4) stripping; Stripping rear catalyst enters fast bed regenerator (2) and/or turbulent bed regenerator (3); On the semi regeneration catalyst that the regeneration of fast bed regenerator (2) obtains, be advanced into settler (5), the semi regeneration catalyst after sedimentation enters turbulent bed regenerator (3) and continues regeneration; Through turbulent bed regenerator (3) regenerate the regenerated catalyst obtained enter degassing tank (6) degassed after Returning reactor (1);
Fast bed regenerator (2) is the first regenerator section (25), changeover portion (26), the second regenerator section (27) from bottom to top; Regeneration temperature is 500 ~ 600 DEG C, and in regenerating medium (17), the content of oxygen is 2 ~ 21 volume %;
Fast bed regenerator (2) and settler (5) are coaxially arranged, and the second regenerator section (27) top of fast bed regenerator (2) is positioned at settler (5);
Turbulent bed regenerator (3) is close phase section (28), changeover portion (29), dilute phase section (30) from bottom to top; Regeneration temperature is 580 ~ 750 DEG C, and in regenerating medium (19), the content of oxygen is 21 ~ 30 volume %.
2. two regenerator fluidized bed reactions of methyl alcohol according to claim 1 and/or dimethyl ether conversion alkene and aromatic hydrocarbons, be advanced into the stripping inclined tube (7) be connected with reactor (1) bottom under it is characterized in that the carbon deposited catalyst that reactor (1) generates, then be promoted to stripper (4) through stripping standpipe (8); Stripping rear catalyst part enters fast bed regenerator (2) first regenerator section (25) through fast bed inclined tube to be generated (13), part enters the close phase section (28) of turbulent bed regenerator (3) through turbulent bed inclined tube to be generated (9), or only enters the close phase section (28) of turbulent bed regenerator (3) through turbulent bed inclined tube to be generated (9); On the semi regeneration catalyst that the regeneration of fast bed regenerator (2) obtains, be advanced into settler (5), the semi regeneration catalyst after sedimentation enters the close phase section (28) of turbulent bed regenerator (3) through semi regeneration agent carrier pipe (10) and continues regeneration; Regenerate the regenerated catalyst obtained to enter degassing tank (6) through degassing tank inclined tube (11) degassed through turbulent bed regenerator (3); Degassed rear regenerated catalyst is through regenerator sloped tube (12) Returning reactor (1).
3. two regenerator fluidized bed reactions of methyl alcohol according to claim 1 and/or dimethyl ether conversion alkene and aromatic hydrocarbons, is characterized in that the height of fast bed regenerator (2) first regenerator section (25) accounts for 70 ~ 90% of fast bed regenerator total height; Second regenerator section (27) diameter and the first regenerator section (25) diameter ratio are 0.3 ~ 1.2:1, and it highly accounts for 9 ~ 27% of fast bed regenerator total height; Changeover portion (26) highly accounts for 1 ~ 3% of fast bed regenerator total height.
4. two regenerator fluidized bed reactions of methyl alcohol according to claim 1 and/or dimethyl ether conversion alkene and aromatic hydrocarbons, is characterized in that the height of the close phase section (28) of turbulent bed regenerator (3) accounts for 60 ~ 90% of turbulent bed regenerator total height; Dilute phase section (27) diameter and close phase section (25) diameter ratio are 1.1 ~ 3:1, and it highly accounts for 9 ~ 37% of turbulent bed regenerator total height; Changeover portion (29) highly accounts for 1 ~ 3% of turbulent bed regenerator total height; Turbulent bed regenerator (3) inside or outer setting heat collector, heat collector height accounts for 30% ~ 80% of turbulent bed regenerator height.
5. two regenerator fluidized bed reactions of methyl alcohol according to claim 1 and/or dimethyl ether conversion alkene and aromatic hydrocarbons, it is characterized in that turbulent bed regenerator (3) top is provided with one group of gas-solid cyclone separator (32), is 1 ~ 3 grade; Settler (5) top is provided with one group of gas-solid cyclone separator (31), is 1 ~ 3 grade.
6. two regenerator fluidized bed reaction methods for methyl alcohol and/or dimethyl ether conversion alkene and aromatic hydrocarbons, adopt the device described in claim 1 or 2, described method comprises following step:
A) raw material (14) enters reactor (1) and catalyst exposure reaction from reactor (1) bottom, reaction of formation product (24) and carbon deposited catalyst, product (24) enters later separation device;
B) the stripping inclined tube (7) be connected with reactor (1) bottom is advanced under carbon deposited catalyst, enter stripping standpipe (8) again, stripper (4) is promoted to through promoting medium (23), stripping is contacted with stripping fluid (15), carbon deposited catalyst after the stripped product (16) obtained and stripping, stripped product (16) enters later separation device;
C) the carbon deposited catalyst part after stripping enters fast bed regenerator (2) first regenerator section (25) through fast bed inclined tube to be generated (13), part enters the close phase section (28) of turbulent bed regenerator (3) through turbulent bed inclined tube to be generated (9), or only enters the close phase section (28) of turbulent bed regenerator (3) through turbulent bed inclined tube to be generated (9);
D) carbon deposited catalyst after stripping contacts annealing in hydrogen atmosphere in fast bed regenerator (2) with regenerating medium (17), burning carbon obtains semi regeneration catalyst and flue gas (18), on be advanced into settler (5), semi regeneration catalyst sedimentation, flue gas (18) is separated after semi regeneration catalyst through gas-solid cyclone separator (31) and enters follow-up flue gas energy recovery device, and the semi regeneration catalyst of sedimentation enters the close phase section (28) of turbulent bed regenerator (3) through semi regeneration agent carrier pipe (10);
E) carbon deposited catalyst after semi regeneration catalyst and/or stripping contacts with regenerating medium (19) to make charcoal and obtains regenerated catalyst and flue gas (20) in turbulent bed regenerator (3), and flue gas (20) enters follow-up flue gas energy recovery device or the regenerating medium as fast bed regenerator (2) after gas-solid cyclone separator (32) separation regeneration catalyst;
F) regenerated catalyst enters degassing tank (6) through degassing tank inclined tube (11) and contacts with degassed medium (21), remove flue gas (22) further, flue gas (22) enters follow-up flue gas energy recovery device or the regenerating medium as fast bed regenerator (2), regenerator sloped tube (12) Returning reactor (1) of passing through under the regenerated catalyst after degassed.
7. two regenerator fluidized bed reaction methods of methyl alcohol according to claim 6 and/or dimethyl ether conversion alkene and aromatic hydrocarbons, it is characterized in that, the regeneration temperature of fast bed regenerator (2) is 500 ~ 600 DEG C, average gas superficial velocity is 1 ~ 8 meter per second, in regenerating medium (17), the content of oxygen is 2 ~ 21 volume %, can be the mixture of flue gas (20) that the mixture of flue gas (20) that air or turbulent bed regenerator (3) obtain and/or the flue gas (22) that degassing tank (6) obtains or air and turbulent bed regenerator (3) obtain and/or the flue gas (22) that degassing tank (6) obtains, the regeneration temperature of turbulent bed regenerator (3) is 580 ~ 750 DEG C, and average gas superficial velocity is 0.5 ~ 2 meter per second, and the content of oxygen is 21 ~ 30 volume % in regenerating medium (19), can be air or air and O
2mixture, turbulent bed regenerator (3) regenerates the charcoal on the regenerated catalyst that obtains, and with the mass percent of catalyst, content is lower than 0.1 % by weight.
8. two regenerator fluidized bed reaction methods of methyl alcohol according to claim 6 and/or dimethyl ether conversion alkene and aromatic hydrocarbons, it is characterized in that the reaction temperature of reactor (1) is 400 ~ 550 DEG C, the weight space velocity of raw material (14) is 0.1 ~ 10 (Grams Per Hour)/gram catalyst, be 0 ~ 0.5 MPa in gauge pressure reaction pressure, the mass ratio of catalyst circulation amount and raw material (14) 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.
9. two regenerator fluidized bed reaction methods of methyl alcohol according to claim 6 and/or dimethyl ether conversion alkene and aromatic hydrocarbons, is characterized in that the active component of catalyst is ZSM-5, ZSM-23, ZSM-11, beta-molecular sieve, Y molecular sieve or the mutual composite molecular screen formed; Carrier is kaolin, aluminium oxide, silica; The mass ratio of active component and carrier is (10 ~ 50): (50 ~ 90); Catalyst cupport has one or more elements or oxide in Zn, Ag, P, Ga, Cu, Mn, Mg, and with the mass percent of catalyst, its content is 0.01 ~ 15 % by weight.
10. two regenerator fluidized bed reaction methods of methyl alcohol according to claim 6 and/or dimethyl ether conversion alkene and aromatic hydrocarbons, it is characterized in that raw material (14) is for methyl alcohol or dimethyl ether or both mixtures, the mass percentage of water is 0.01 ~ 30 % by weight; Stripping fluid (15) is water vapour or N
2or water vapour and N
2mixture, promote medium (23) be water vapour or N
2or water vapour and N
2mixture; Degassed medium (21) is water vapour or N
2or water vapour and N
2mixture.
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| CN107540496A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Methanol or the method for dimethyl ether production aromatic hydrocarbons and low-carbon alkene |
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| CN107540501A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The method that methanol feedstock prepares aromatic hydrocarbons |
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