CN105457570A - Coaxial two-stage regenerative reaction device for preparing low-carbon olefins and aromatic hydrocarbon by converting methanol or dimethyl ether and reaction method for coaxial two-stage regenerative reaction device - Google Patents
Coaxial two-stage regenerative reaction device for preparing low-carbon olefins and aromatic hydrocarbon by converting methanol or dimethyl ether and reaction method for coaxial two-stage regenerative reaction device Download PDFInfo
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Abstract
The invention relates to a coaxial double regenerator fluidized bed reaction device for preparing ethylene, propylene and aromatic hydrocarbon by catalytically converting methanol or dimethyl ether and a reaction method for the reaction device, and mainly solves the problem in the prior art that ethylene, propylene and aromatic hydrocarbon are low in yield, and hydrothermal deactivation of a catalyst is severe. The problem is better solved by virtue of a technical scheme that through a system which comprises a reactor, a first regenerator, a second regenerator, a stripper and a degassing tank, raw materials enter into the reactor from the lower part of the reactor to be contacted with a catalyst to react, a carbon deposit catalyst after reaction is stripped by the stripper and enters into the first regenerator to be regenerated, a semi-regenerated catalyst obtained enters into the second regenerator to be continuously regenerated through a delivery pipe, and the fully regenerated catalyst which is degassed in the degassing tank returns to the reactor. The reaction device can be used for industrial production of ethylene, propylene and aromatic hydrocarbon.
Description
Technical field
The present invention relates to the two regenerator fluidized bed reaction of coaxial-type 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 demand sustainable growth of ethene, propylene 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 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, cost of material 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, 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 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 (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 ethene, propylene belong 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.
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.
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 is that ethene in prior art, propylene and aromatics yield are low, the technical problem that catalyst hydrothermal deactivation is serious, provides the coaxial-type of a kind of methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons two regenerator fluidized bed reaction.This system has the advantage that ethene, propylene and aromatics yield are high, effectively alleviate 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: the two regenerator fluidized bed reaction of coaxial-type of a kind of methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, comprises the system of reactor 1, first regenerator 2, Second reactivator 3, stripper 4; Raw material 11 enters reactor 1 and catalyst exposure reaction from reactor 1 bottom, reacted carbon deposited catalyst is promoted to stripper 4 stripping through stripping standpipe 7; Stripping rear catalyst enters the first regenerator 2 and regenerates, and the semi regeneration catalyst obtained enters Second reactivator 3 through carrier pipe 22 and continues regeneration; Through Second reactivator 3 regenerate the holomorphosis catalyst obtained enter degassing tank 5 degassed after Returning reactor 1; Second reactivator 2 regenerates the flue gas generated and enters the regenerating medium of the first regenerator 2 as the first regenerator through cyclone separator 19; First regenerator 2 is close phase section 23, changeover portion 24, dilute phase section 25 from bottom to top; Regeneration temperature is 500 ~ 600 DEG C; Second reactivator 3 is close phase section 26, changeover portion 27, dilute phase section 28 from bottom to top; Regeneration temperature is 580 ~ 750 DEG C, and in regenerating medium 20, the content of oxygen is 21 ~ 30 volume %; First regenerator 2 and Second reactivator 3 are coaxially arranged, and are connected bottom the close phase section 23 of the first regenerator 2 with carrier pipe 22, and it is inner that close phase section 23 bottom of the first regenerator 2 and carrier pipe 22 are positioned at Second reactivator 3.
In technique scheme, be advanced into and the stripping inclined tube 6 be connected bottom reactor 1 under the carbon deposited catalyst that reactor 1 generates, then be promoted to stripper 4 through stripping standpipe 7; Stripping rear catalyst enters the close phase section 23 of the first regenerator 2 through inclined tube 8 to be generated; Regenerate the semi regeneration catalyst obtained through the first regenerator 2 and be advanced into Second reactivator 3 close phase section 26 continuation regeneration for 22 times through carrier pipe; Regenerate the regenerated catalyst obtained to enter degassing tank 5 through degassing tank inclined tube 9 degassed through Second reactivator 3; Degassed rear regenerated catalyst is through regenerator sloped tube 10 Returning reactor 1.
In technique scheme, the height of the close phase section 23 of the first regenerator 2 accounts for 70 ~ 90% of the first regenerator total height; Dilute phase section 25 diameter and close phase section 23 diameter ratio are 1.1 ~ 2:1, and it highly accounts for 9 ~ 27% of the first regenerator total height; Changeover portion 24 highly accounts for 1 ~ 3% of the first regenerator total height.
In technique scheme, the height of the close phase section 26 of Second reactivator 3 accounts for 50 ~ 85% of Second reactivator total height; Dilute phase section 28 diameter and close phase section 26 diameter ratio are 1.1 ~ 2:1, and it highly accounts for 14 ~ 47% of Second reactivator total height; Changeover portion 27 highly accounts for 1 ~ 3% of Second reactivator total height.
In technique scheme, Second reactivator 3 inside or outer setting heat collector, heat collector height accounts for 30% ~ 80% of Second reactivator height.
In technique scheme, the first regenerator 2 top is provided with one group of gas-solid cyclone separator 18, is 1 ~ 3 grade; Second reactivator 3 inside is provided with one group of gas-solid cyclone separator 19, is 1 ~ 3 grade; Gas-solid cyclone separator 19 exhanst gas outlet is connected with the first regenerator 2 main air entrance.
In technique scheme, reactor 1, for being converted into based on the product of ethene, propylene and aromatic hydrocarbons by raw material 11 and catalyst exposure reaction; First regenerator 2, for removing the hydrogen on carbon deposited catalyst in coke, generates semi regeneration catalyst; Second reactivator 3, the coke on semi regeneration catalyst, generates regenerated catalyst; Stripper 4, goes out the product that carbon deposited catalyst carries for stripping; Degassing tank 5, for the regenerated flue gas that the regenerated catalyst after removing Second reactivator regeneration is further carried secretly.
For solve the problem two, the technical solution used in the present invention is as follows: the two regenerator fluidized bed reaction method of coaxial-type of a kind of methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, adopt above-mentioned system, described method comprises following step:
A) raw material 11 enters reactor 1 and catalyst exposure reaction from reactor 1 bottom, reaction of formation product 12 and carbon deposited catalyst, and product 12 enters subsequent separation system;
B) be advanced under carbon deposited catalyst and the stripping inclined tube 6 be connected bottom reactor 1, enter stripping standpipe 7 again, stripper 4 is promoted to through promoting medium 13, stripping is contacted with stripping fluid 14, carbon deposited catalyst after the stripped product 15 obtained and stripping, stripped product 15 enters subsequent separation system;
C) carbon deposited catalyst after stripping enters the close phase section 23 of the first regenerator 2 through inclined tube 8 to be generated, contact regeneration with regenerating medium and obtain semi regeneration catalyst and flue gas 17, flue gas 17 is separated after semi regeneration catalyst through gas-solid cyclone separator 18 and enters follow-up smoke energy recovering system, and semi regeneration catalyst enters the close phase section 26 of Second reactivator 3 through carrier pipe 22;
D) semi regeneration catalyst contacts regeneration with regenerating medium 16 and obtains regenerated catalyst and flue gas in Second reactivator 3, and flue gas enters the first regenerator 2 after gas-solid cyclone separator 19 separation regeneration catalyst, as the regenerating medium of the first regenerator 2;
E) regenerated catalyst enters degassing tank 5 through degassing tank inclined tube 9 and contacts with degassed medium 20, and remove flue gas 21 further, flue gas 21 enters follow-up smoke energy recovering system, regenerator sloped tube 10 Returning reactor 1 of passing through under the regenerated catalyst after degassed.
In technique scheme, the regeneration temperature of the first regenerator 2 is 500 ~ 600 DEG C, preferably 530 ~ 570 DEG C; Average gas superficial velocity is 0.1 ~ 0.8 meter per second, preferably 0.2 ~ 0.6 meter per second; Regenerating medium is the flue gas that Second reactivator 3 produces.
In technique scheme, the regeneration temperature of Second reactivator 3 is 580 ~ 750 DEG C, preferably 630 ~ 700 DEG C; Average gas superficial velocity is 0.5 ~ 1.2 meter per second, preferably 0.6 ~ 1 meter per second.
In technique scheme, in the regenerating medium 20 of Second reactivator 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 Second reactivator 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 11 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 11 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 11 is methyl alcohol or dimethyl ether or both mixtures, particular methanol.
In technique scheme, in raw material 11, the mass percentage of water is 0.01 ~ 30 % by weight, preferably lower than 10 % by weight.
In technique scheme, stripping fluid 14 is water vapour or N
2or water vapour and N
2mixture, promote medium 13 be water vapour or N
2or water vapour and N
2mixture, degassed medium 20 is water vapour or N
2or water vapour and N
2mixture.
Technical scheme provided by the invention, adopt two regenerator regeneration, reclaimable catalyst in the first 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 ethene, propylene and aromatic hydrocarbons easily.
Adopting technical scheme of the present invention, take methyl alcohol as raw material, and water content is 5 % by weight; First regenerator regeneration temperature is 560 DEG C, and average gas superficial velocity is 0.3 meter per second; Second reactivator regeneration temperature is 680 DEG C, and average gas superficial velocity is 0.7 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 0.7 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 the first regenerator, and Fig. 3 is the schematic diagram of Second reactivator.
1 be reactor in 1 ~ 2 in figure; 2 is the first regenerator; 3 is Second reactivator; 4 is stripper; 5 is degassing tank; 6 is stripping inclined tube; 7 is stripping standpipe; 8 is inclined tube to be generated; 9 is regenerator sloped tube; 10 is degassing tank inclined tube; 11 is raw material; 12 is product; 13 for promoting medium; 14 is stripping fluid; 15 is stripped product; 16 is Second reactivator regenerating medium; 17 is the first regenerator flue gas; 18 is the first regenerator cyclone separator; 19 is Second reactivator cyclone separator; 20 is degassing tank medium; 21 is degassing tank flue gas; 22 is carrier pipe; 23 is the close phase section of the first regenerator; 24 is the first regenerator changeover portion; 25 is the first regenerator dilute phase section; 26 is the close phase section of Second reactivator; 27 is Second reactivator changeover portion; 28 is Second reactivator dilute phase section.
Fig. 1 Raw 11 enters reactor 1 and catalyst exposure reaction from reactor 1 bottom, reaction of formation product 12 and carbon deposited catalyst, and product 12 enters subsequent separation system; Be advanced under carbon deposited catalyst and the stripping inclined tube 6 be connected bottom reactor 1, enter stripping standpipe 7 again, being promoted to stripper 4 through promoting medium 13, contacting stripping with stripping fluid 14, carbon deposited catalyst after the stripped product 15 obtained and stripping, stripped product 15 enters subsequent separation system; Carbon deposited catalyst after stripping enters the close phase section 23 of the first regenerator 2 through inclined tube 8 to be generated, contact regeneration with regenerating medium and obtain semi regeneration catalyst and flue gas 17, flue gas 17 is separated after semi regeneration catalyst through gas-solid cyclone separator 18 and enters follow-up smoke energy recovering system, and semi regeneration catalyst enters the close phase section 26 of Second reactivator 3 through carrier pipe 22; Semi regeneration catalyst contacts regeneration with regenerating medium 16 and obtains regenerated catalyst and flue gas in Second reactivator 3, and flue gas enters the first regenerator 2 after gas-solid cyclone separator 19 separation regeneration catalyst, as the regenerating medium of the first regenerator 2; Regenerated catalyst enters degassing tank 5 through degassing tank inclined tube 9 and contacts with degassed medium 20, and remove flue gas 21 further, flue gas 21 enters follow-up smoke energy recovering system, regenerator sloped tube 10 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.First regenerator close phase section diameter is 1 meter, and it highly accounts for 80% of the first regenerator height, and the diameter ratio of dilute phase section diameter and close phase section is 1.3:1, and it highly accounts for 18% of the first regenerator height.Regeneration temperature is 560 DEG C, and average gas superficial velocity is 0.3 meter per second.
Second reactivator close phase section diameter is 1.5 meters, and it highly accounts for 70% of Second reactivator height, and dilute phase section diameter and close phase section diameter ratio are 1.1:1, and it highly accounts for 27% of Second reactivator height.The height of external heat collector accounts for 70% of regenerator height.Regeneration temperature is 680 DEG C, and average gas superficial velocity is 0.7 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 0.7 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.First regenerator close phase section diameter is 1.8 meters, and it highly accounts for the 90%, second regenerator section diameter of the first regenerator height and the diameter ratio of the first regenerator section is 2:1, and it highly accounts for 9% of the first regenerator height.Regeneration temperature is 500 DEG C, and average gas superficial velocity is 0.1 meter per second.
Second reactivator close phase section diameter is 2.6 meters, and it highly accounts for 85% of Second reactivator height, and dilute phase section diameter and close phase section diameter ratio are 2:1, and it highly accounts for 14% of Second reactivator 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 0.01 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.
First regenerator regeneration temperature is 600 DEG C, and average gas superficial velocity is 0.8 meter per second.
Second reactivator regeneration temperature is 750 DEG C, and average gas superficial velocity is 1.2 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.First regenerator close phase section diameter is 2.2 meters, and it highly accounts for the 70%, second regenerator section diameter of the first regenerator height and the diameter ratio of the first regenerator section is 1.1:1, and it highly accounts for 27% of the first regenerator height.Regeneration temperature is 540 DEG C, and average gas superficial velocity is 0.7 meter per second.
Second reactivator close phase section diameter is 3 meters, and it highly accounts for 50% of Second reactivator height, and dilute phase section diameter and close phase section diameter ratio are 1.1:1, and it highly accounts for 47% of Second reactivator 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 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 0.08 % 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.
First regenerator regeneration temperature is 580 DEG C, and average gas superficial velocity is 0.4 meter per second.
Second reactivator 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.First regenerator close phase section diameter is 1.7 meters, and it highly accounts for the 80%, second regenerator section diameter of the first regenerator height and the diameter ratio of the first regenerator section is 1.1:1, and it highly accounts for 18% of the first regenerator height.Regeneration temperature is 530 DEG C, and average gas superficial velocity is 0.2 meter per second.
Second reactivator close phase section diameter is 2 meters, and it highly accounts for 60% of Second reactivator height, and dilute phase section diameter and close phase section diameter ratio are 1.8:1, and it highly accounts for 37% of Second reactivator 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.
First regenerator regeneration temperature is 550 DEG C, and average gas superficial velocity is 0.4 meter per second.
Second reactivator 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.First regenerator close phase section diameter is 1 meter, and it highly accounts for the 85%, second regenerator section diameter of the first regenerator height and the diameter ratio of the first regenerator section is 0.7:1, and it highly accounts for 12% of the first regenerator height.Regeneration temperature is 590 DEG C, and average gas superficial velocity is 0.75 meter per second.
Second reactivator close phase section diameter is 2 meters, and it highly accounts for 70% of Second reactivator height, and dilute phase section diameter and close phase section diameter ratio are 1.7:1, and it highly accounts for 28% of Second reactivator 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 0.9 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 0.08 % 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
| 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. the two regenerator fluidized bed reaction of the coaxial-type of methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, comprises the system of reactor (1), the first regenerator (2), Second reactivator (3), stripper (4); Raw material (11) enters reactor (1) and catalyst exposure reaction from reactor (1) bottom, reacted carbon deposited catalyst is promoted to stripper (4) stripping through stripping standpipe (7); Stripping rear catalyst enters the first regenerator (2) regeneration, and the semi regeneration catalyst obtained enters Second reactivator (3) through carrier pipe (22) and continues regeneration; Through Second reactivator (3) regenerate the holomorphosis catalyst obtained enter degassing tank (5) degassed after Returning reactor (1); The flue gas that Second reactivator (2) regeneration generates enters the regenerating medium of the first regenerator (2) as the first regenerator through cyclone separator (19);
First regenerator (2) is close phase section (23), changeover portion (24), dilute phase section (25) from bottom to top; Regeneration temperature is 500 ~ 600 DEG C;
Second reactivator (3) is close phase section (26), changeover portion (27), dilute phase section (28) from bottom to top; Regeneration temperature is 580 ~ 750 DEG C, and in regenerating medium (20), the content of oxygen is 21 ~ 30 volume %;
First regenerator (2) and Second reactivator (3) are coaxially arranged, close phase section (23) bottom of the first regenerator (2) is connected with carrier pipe (22), and it is inner that close phase section (23) bottom of the first regenerator (2) and carrier pipe (22) are positioned at Second reactivator (3).
2. the two regenerator fluidized bed reaction of the coaxial-type of methyl alcohol according to claim 1 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, be advanced into the stripping inclined tube (6) 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 (7); Stripping rear catalyst enters the close phase section (23) of the first regenerator (2) through inclined tube to be generated (8); Regenerate through the first regenerator (2) the semi regeneration catalyst obtained under carrier pipe (22), be advanced into Second reactivator (3) close phase section (26) continuation regeneration; Regenerate the regenerated catalyst obtained to enter degassing tank (5) through degassing tank inclined tube (9) degassed through Second reactivator (3); Degassed rear regenerated catalyst is through regenerator sloped tube (10) Returning reactor (1).
3. the two regenerator fluidized bed reaction of the coaxial-type of methyl alcohol according to claim 1 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, is characterized in that the height of the close phase section (23) of the first regenerator (2) accounts for 70 ~ 90% of the first regenerator total height; Dilute phase section (25) diameter and close phase section (23) diameter ratio are 1.1 ~ 2:1, and it highly accounts for 9 ~ 27% of the first regenerator total height; Changeover portion (24) highly accounts for 1 ~ 3% of the first regenerator total height.
4. the two regenerator fluidized bed reaction of the coaxial-type of methyl alcohol according to claim 1 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, is characterized in that the height of the close phase section (26) of Second reactivator (3) accounts for 50 ~ 85% of Second reactivator total height; Dilute phase section (28) diameter and close phase section (26) diameter ratio are 1.1 ~ 2:1, and it highly accounts for 14 ~ 47% of Second reactivator total height; Changeover portion (27) highly accounts for 1 ~ 3% of Second reactivator total height; Second reactivator (3) inside and/or outer setting heat collector, heat collector height accounts for 30% ~ 80% of Second reactivator height.
5. the two regenerator fluidized bed reaction of the coaxial-type of methyl alcohol according to claim 1 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, it is characterized in that the first regenerator (2) top is provided with one group of gas-solid cyclone separator (18), is 1 ~ 3 grade; Second reactivator (3) inside is provided with one group of gas-solid cyclone separator (19), is 1 ~ 3 grade; Gas-solid cyclone separator (19) exhanst gas outlet is connected with the first regenerator (2) main air entrance.
6. the two regenerator fluidized bed reaction method of the coaxial-type of methyl alcohol and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, adopt the system described in claim 1 or 2, described method comprises following step:
A) raw material (11) enters reactor (1) and catalyst exposure reaction from reactor (1) bottom, reaction of formation product (12) and carbon deposited catalyst, product (12) enters subsequent separation system;
B) the stripping inclined tube (6) be connected with reactor (1) bottom is advanced under carbon deposited catalyst, enter stripping standpipe (7) again, stripper (4) is promoted to through promoting medium (13), stripping is contacted with stripping fluid (14), carbon deposited catalyst after the stripped product (15) obtained and stripping, stripped product (15) enters subsequent separation system;
C) carbon deposited catalyst after stripping enters the close phase section (23) of the first regenerator (2) through inclined tube to be generated (8), contact regeneration with regenerating medium and obtain semi regeneration catalyst and flue gas (17), flue gas (17) is separated after semi regeneration catalyst through gas-solid cyclone separator (18) and enters follow-up smoke energy recovering system, and semi regeneration catalyst enters the close phase section (26) of Second reactivator (3) through carrier pipe (22);
D) semi regeneration catalyst contacts regeneration with regenerating medium (16) and obtains regenerated catalyst and flue gas in Second reactivator (3), flue gas enters the first regenerator (2) after gas-solid cyclone separator (19) separation regeneration catalyst, as the regenerating medium of the first regenerator (2);
E) regenerated catalyst enters degassing tank (5) through degassing tank inclined tube (9) and contacts with degassed medium (20), remove flue gas (21) further, flue gas (21) enters follow-up smoke energy recovering system, regenerator sloped tube (10) Returning reactor (1) of passing through under the regenerated catalyst after degassed.
7. the two regenerator fluidized bed reaction method of the coaxial-type of methyl alcohol according to claim 6 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, it is characterized in that, the regeneration temperature of the first regenerator (2) is 500 ~ 600 DEG C, average gas superficial velocity is 0.1 ~ 0.8 meter per second, and regenerating medium is the flue gas that Second reactivator (3) produces; The regeneration temperature of Second reactivator (3) is 580 ~ 750 DEG C, and average gas superficial velocity is 0.5 ~ 1.2 meter per second, and the content of oxygen is 21 ~ 30 volume % in regenerating medium (16), can be air or air and O
2mixture; Second reactivator (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. the two regenerator fluidized bed reaction method of the coaxial-type of methyl alcohol according to claim 6 and/or dimethyl ether conversion ethene, propylene 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 (11) 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 (11) 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. the two regenerator fluidized bed reaction method of the coaxial-type of methyl alcohol according to claim 6 and/or dimethyl ether conversion ethene, propylene 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. the two regenerator fluidized bed reaction method of the coaxial-type of methyl alcohol according to claim 6 and/or dimethyl ether conversion ethene, propylene and aromatic hydrocarbons, it is characterized in that raw material (11) is for methyl alcohol or dimethyl ether or both mixtures, the mass percentage of water is 0.01 ~ 30 % by weight; Stripping fluid (14) is water vapour or N
2or water vapour and N
2mixture, promote medium (13) be water vapour or N
2or water vapour and N
2mixture; Degassed medium (20) is water vapour or N
2or water vapour and N
2mixture.
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