CN109136539B - Integrated process of fluidized bed two-stage gasification and flash light burning magnesite - Google Patents
Integrated process of fluidized bed two-stage gasification and flash light burning magnesite Download PDFInfo
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- CN109136539B CN109136539B CN201810731247.9A CN201810731247A CN109136539B CN 109136539 B CN109136539 B CN 109136539B CN 201810731247 A CN201810731247 A CN 201810731247A CN 109136539 B CN109136539 B CN 109136539B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
- C04B2/102—Preheating, burning calcining or cooling of magnesia, e.g. dead burning
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
- C04B2/106—Preheating, burning calcining or cooling in fluidised bed furnaces
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
- C04B2/108—Treatment or selection of the fuel therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/10—Roasting processes in fluidised form
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
Abstract
The invention discloses a fluidized bed two-section gasification and flash light burning magnesite integrated process, and relates to a magnesite smelting process, wherein the process is used for drying/pyrolyzing or partially gasifying fuel under the heating of hot bed materials circularly entering a pyrolyzer or the oxidation of air fed into the pyrolyzer; gasifying the semicoke in a gasifier, and removing tar by utilizing high-temperature cracking, partial gasification and catalytic reforming action of the semicoke on the tar in the gasifier; then filtering and dedusting to generate clean fuel gas, performing gas-solid separation on the product of the clean fuel gas, and preheating magnesite powder by using the obtained high-temperature flue gas through a flue gas heat exchange system; the high-temperature light-burned magnesium generated by gas-solid separation is preheated by a product heat exchange system to clean air required by a gas burner, and the cooled light-burned magnesium product is conveyed to a storage tank. The invention directly integrates gas production and magnesite light burning, has the advantages of high integration level, high thermal efficiency, continuous and stable process and no coal gasification wastewater, and the flash light-burned magnesite powder product has high activity, uniform quality and wide popularization and application prospect.
Description
Technical Field
The invention relates to a magnesite smelting process, in particular to a process integrating fluidized bed two-stage gasification and flash light burning of magnesite.
Background
China is one of the most abundant countries of magnesite resources in the world, and the total reserved quantity of the ores is about 30 hundred million tons, which accounts for 25 percent of the total reserve in the world. The Liaoning magnesite is the most abundant, accounts for 85.6% of the total storage in China, is mainly concentrated in large stone bridges and sea cities, and has the annual extraction amount of about 1200 plus 1500 million tons. Magnesite is a main raw material for preparing magnesium compounds, light-burned magnesium is obtained by calcining magnesite, is widely used in the fields of building materials, chemical engineering, metallurgy, medicines and the like, is an ideal material for producing fire-proof plates, light partition plates, magnesium sulfate, papermaking, a desulphurization process, furnace protection slag splashing of steel mills and the like, and is also a raw material for preparing heavy-burned magnesium, high-purity magnesite sand and electric fused magnesium.
2771 calcining furnaces for producing refractory raw materials in Liaoning, wherein the number of the light-burning furnaces is 1367, and the yield of the light-burning magnesium oxide is over 400 million tons/year. For decades, the apparatus for preparing light-burned magnesia by calcining magnesite at high temperature has been used for calcining magnesite by the traditional process of combining a water gas generator with a reverberatory furnace or a shaft kiln, wherein the method for preparing light-burned magnesia by calcining magnesite by the shaft kiln is generally adopted, but the method generally adopts large magnesite which is put into the kiln for calcination. Because the process does not have a constant temperature maintaining process, the magnesite blocks fed into the furnace are large, and the phenomenon of over-burning on the surface and under-burning in the center is easy to occur, the obtained light-burned magnesia has the defects of uneven quality, low activity and the like. In addition, due to the limitation of the structure of the furnace body and the process conditions, the size of the charging material block of the shaft furnace has a little requirement, for example, the size of the charging material block of the shaft furnace is not less than 40 mm, so that the large batch of small-sized material blocks and fine ores can not be utilized. On the other hand, the ore with the grain size less than 25 mm is 40-45% produced in mining, and the part of ore is often discarded or used for paving, which causes huge resource waste, occupies land, pollutes the environment and causes serious environmental protection problems.
When the reverberatory furnace is used as a device for burning magnesite lightly, the heat consumption is as high as 7.40-8.54 GJ/t-MgO, the quality of the burnt MgO powder is unstable, and the dust concentration in the discharged waste gas is higher than 500mg/Nm3And even up to 1000mg/Nm3Above, the labor productivity is only 1100 t/man/year, the automation degree is low, and the method and the system are a very laggard light burning system and method.
The heat source generating equipment used in the light-burned magnesium kiln at the present stage is mainly a water gas producer, the tar content of the produced gas is high, in order to obtain clean gas, water is firstly used for spraying to condense the tar, and in the process, phenol water and other waste water are inevitably produced to cause environmental pollution.
In recent years, a great deal of research is carried out in China on the magnesite light burning process, but the center of the research lies in the realization of the magnesite light burning process, such as boiling furnace light burning magnesium oxide (Chinese patent CN85108710), suspension furnace light burning magnesium oxide (Chinese patent CN85106397, 201020131767.5), rotary kiln light burning magnesium oxide (Chinese patent 200710011301.4, 90107753.4, 201710676058.1), tunnel kiln light burning magnesium oxide (Chinese patent 200610047061.9, 200510046995.6, 200910148368.1), reflection kiln light burning magnesium oxide (Chinese patent 201320654961.5), vertical kiln light burning magnesium oxide (Chinese patent 201610545960.5), light burning magnesium oxide heat selection process (Chinese patent 200610134894.9, 201110049511.9) and the like, but the problems of the whole magnesium oxide light burning process are not specifically researched and discussed, and in addition, the problems are all improved on the basis of the traditional reactor, and the magnesite light burning technology is not fundamentally changed. Recently, patent application No. CN 106587666 a discloses an apparatus and method for producing light-burned magnesia by magnesite flotation concentrate powder. The device comprises a feeder, a flash evaporation dryer, a raw material dry product catcher, a multistage preheating system, a bag filter, a dynamic calciner, a gas combustion furnace, a finished product catcher, an induced draft fan and a pipeline system. The method comprises the following steps: (1) Magnesite flotation concentrate powder is sent into a flash evaporation dryer by a feeder to realize drying treatment; (2) The dried material is trapped by a raw material dry product trap and sent into a multi-stage preheating system to realize preheating treatment; (3) And (4) collecting the preheated materials through a multistage preheating system, and then sending the materials into a dynamic calcining furnace to realize calcination decomposition treatment so as to generate light-burned magnesia. The material drying, preheating and calcining process sections are dilute phase current-carrying heat exchange. The invention effectively utilizes the flotation dewatered concentrate powder of the low-grade magnesite to produce the light-burned magnesia, and realizes the light burning on an industrial scale, however, the invention does not effectively utilize the waste heat of the light-burned magnesia product, which causes a great loss of heat, and in addition, the light burning on the industrial scale still adopts the water gas generator, which does not solve the problems of phenol water waste water and the like.
In conclusion, the conventional technology for calcining magnesite at present falls behind, is high in energy consumption, only uses large-particle raw materials, is low in calcining reaction speed, is difficult to control product quality, adopts an intermittent operation mode, is high in labor cost, high in working strength, high in dust pollution and poor in working environment, and urgently needs to comprehensively upgrade the magnesite light burning technology.
Disclosure of Invention
The invention aims to provide a process integrating fluidized bed two-stage gasification and flash light-burning magnesite, wherein a totally-enclosed conveying bed is continuously calcined to replace 'reverberatory furnace' intermittent operation, so that the problems of high dust pollution and severe working environment in the light-burning process are solved, a two-stage gasification device is simple in structure, high in treatment capacity and low in manufacturing and maintenance cost, and the problems of low carbon conversion rate and energy waste caused by the production of pollutants such as tar, phenol water and the like in the traditional process are solved.
The purpose of the invention is realized by the following technical scheme:
the invention provides a process for integrating fluidized bed two-stage gasification and flash light burning magnesite, which directly integrates a (fuel) fluidized bed two-stage gasification gas production process and a magnesite powder conveying bed flash light burning process using the gas, and high-temperature gas which is not cooled at low temperature is directly burnt to provide heat for the magnesite powder conveying bed flash light burning.
The method specifically comprises the following steps:
the fuel is first fed into the pyrolyzer from a feeding device and dried/pyrolyzed or partially gasified under the heating of the hot bed material circulated into the pyrolyzer or the oxidation of air fed into the pyrolyzer.
The generated pyrolysis product enters a downstream gasification furnace through a pipeline, a gasification agent is introduced into the bottom of the gasification furnace, the semicoke is gasified in the gasification furnace, the tar is removed by utilizing the high-temperature cracking, partial gasification and catalytic reforming action of the semicoke on the tar in the gasification furnace, and the unreacted semicoke returns to the pyrolyzer after gas-solid separation.
The generated fuel gas exchanges heat with water and air through an air preheater and a waste heat boiler, and the water vapor and the air generated after the heat exchange are used as a gasifying agent and are introduced into the bottom of the gasification furnace together.
The gas after heat exchange is filtered and dedusted to generate clean gas, the clean gas is introduced into a combustor, hot flue gas generated by combustion rapidly calcines magnesite powder through gas-solid action, the gas velocity in a conveying bed reactor of the magnesite powder calciner is 3-20 m/s, and the particle size of the magnesite raw material is less than 200 mu m.
The product is subjected to gas-solid separation, the magnesite powder is preheated by high-temperature flue gas obtained through the gas-solid separation through a flue gas heat exchange system, the preheated mineral powder is conveyed into a calcining furnace, and the flue gas subjected to heat exchange is filtered and dedusted to reach the standard and then is discharged;
the high-temperature light-burned magnesium generated by gas-solid separation is preheated by a product heat exchange system to clean air required by a gas burner, and the cooled light-burned magnesium product is conveyed to a storage tank.
The fluidized bed two-stage gasification process mainly comprises the following steps: the fuel is sent into the pyrolyzer to be pyrolyzed or oxidized and pyrolyzed firstly, all generated pyrolysis products and semicoke are sent into the gasifier, and the temperature of the fuel gas after the waste heat boiler is higher than the temperature of the contained steam condensed and separated out of the wastewater, such as 100 ℃. The high-temperature gas after gas-solid separation and air indirectly exchange heat to preheat air, then steam is generated by a waste heat boiler of the gas, and the preheated air and the generated steam are sent to a gasification furnace and a pyrolyzer. The reactor of the gasification furnace is a rapid fluidized bed or a conveying bed, and the pyrolyzer is one or any combination of a bubbling/turbulent fluidized bed, a rapid fluidized bed, a conveying bed, a descending bed and a moving fluidized bed.
The flash light burning magnesite process mainly comprises the following steps: the magnesite powder calcining furnace adopts a conveying bed reactor, the gas burner uses preheated air, and the raw material entering the magnesite calcining furnace is the preheated magnesite powder. The high-temperature light-burned powder product after gas-solid separation and air required by gas combustion preheat air and cool the light-burned magnesium product through direct contact heat exchange, and the high-temperature flue gas after gas-solid separation and raw material magnesite powder directly contact heat exchange cooling flue gas to preheat magnesite powder.
The invention has the advantages and effects that:
1. the two-stage gasification device has the advantages of simple structure, large treatment capacity and low manufacturing and maintenance cost.
2. The invention has the advantages of high thermal efficiency and low tar content in the generated fuel gas, and solves the problems of low carbon conversion rate and energy waste caused by the output of pollutants such as tar, phenol water and the like in the traditional process.
3. The clean gas combustion flame produced by the invention can fully contact with magnesite, the reaction speed is high, and the product property is uniform.
4. The magnesite raw material used in the invention has small granularity, solves the problem that the reflection kiln can only use large-particle raw materials, and avoids the waste of resources.
5. The continuous calcination of the totally-enclosed conveying bed replaces the intermittent operation of a reverberatory furnace, and the problems of large dust pollution and severe working environment in the light-burning process are solved.
6. The invention has high heat recovery efficiency, fully utilizes the residual heat of the flue gas and the product, avoids a large amount of waste of heat and greatly reduces the energy consumption for producing light-burned magnesium.
The invention directly integrates gas production and magnesite light burning, has the advantages of high integration level, high thermal efficiency, continuous and stable process and no coal gasification wastewater, and flash light burning magnesite powder has high product activity, uniform quality and wide popularization and application prospect.
Drawings
FIG. 1 is a schematic representation of example 1 of the process flow of the present invention.
Detailed Description
In order that the objects, methods and advantages of the invention will become more apparent, the invention is further described in detail in the following description taken in conjunction with the accompanying drawings.
The process is characterized in that a fuel gas production process of fluidized bed two-stage gasification and a magnesite powder conveying bed flash light burning process using the fuel gas are directly integrated, and high-temperature fuel gas without low temperature cooling is directly burnt to provide heat for the magnesite powder conveying bed flash light burning.
The process for integrating fluidized bed two-stage gasification and flash light burning magnesite is characterized in that the fluidized bed two-stage gasification process mainly comprises the following steps: the fuel is sent into the pyrolyzer to be pyrolyzed or oxidized and pyrolyzed firstly, all generated pyrolysis products and semicoke are sent into the gasifier, and the temperature of the fuel gas after the waste heat boiler is higher than the temperature of the contained steam condensed and separated out of the wastewater, such as 100 ℃.
The process for integrating fluidized bed two-stage gasification and flash light-burning magnesite is characterized in that the process of flash light-burning magnesite mainly comprises the following steps: the magnesite powder calcining furnace adopts a conveying bed reactor, the gas burner uses preheated air, and the raw material entering the magnesite calcining furnace is the preheated magnesite powder.
The fluidized bed two-stage gasification process is characterized in that high-temperature gas after gas-solid separation and air are subjected to indirect heat exchange to preheat air, then steam is generated by a waste heat boiler of the gas, and the preheated air and the generated steam are sent to a gasification furnace and a pyrolyzer.
The process for flash light burning of magnesite is characterized in that the gas velocity in a conveying bed reactor of the magnesite powder calcining furnace is 3-20 m/s, and the particle size of the magnesite raw material is less than 200 mu m.
The flash light burning magnesite process features that the high temperature light burning powder product after gas-solid separation and the air for gas burning are contacted directly to exchange heat to preheat air and cool light burning magnesium product, and the high temperature fume after gas-solid separation and the magnesite powder as material are contacted directly to exchange heat to cool the fume to preheat magnesite powder.
Example one
As shown in fig. 1, the fuel is fed to a pyrolyzer and dried/pyrolyzed or partially gasified by heating of hot bed material circulated into the pyrolyzer or by oxidation of air fed into the pyrolyzer; the generated pyrolysis product is sent into a gasification furnace, and a gasification agent is introduced into the bottom of the gasification furnace to gasify the semicoke in the gasification furnace, and the tar is removed by utilizing the high-temperature cracking, partial gasification and catalytic reforming action of the semicoke on the tar in the gasification furnace; the generated fuel gas exchanges heat with water and air through an air preheater and a waste heat boiler, and the water vapor and the air after heat exchange are used as gasifying agents and are introduced into the bottom of the gasification furnace; then filtering and dedusting to generate clean fuel gas, introducing the clean fuel gas into a combustor, and quickly calcining magnesite powder by hot flue gas generated by combustion through gas-solid action; the product is subjected to gas-solid separation, the magnesite powder is preheated by high-temperature flue gas obtained through the gas-solid separation through a flue gas heat exchange system, the preheated mineral powder is conveyed into a calcining furnace, and the flue gas subjected to heat exchange is filtered and dedusted to reach the standard and then is discharged; the high-temperature light-burned magnesium generated by gas-solid separation is preheated by a product heat exchange system to clean air required by a gas burner, and the cooled light-burned magnesium product is conveyed to a storage tank.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. The integrated process for fluidized bed two-stage gasification and flash light burning of magnesite is characterized by comprising the following steps of:
firstly, fuel is added into a pyrolyzer from a feeding device, and the fuel is dried/pyrolyzed or partially gasified under the action of heating of hot bed material circularly entering the pyrolyzer or oxidation of air fed into the pyrolyzer;
the generated pyrolysis product enters a downstream gasification furnace through a pipeline, a gasification agent is introduced into the bottom of the gasification furnace, the semicoke is gasified in the gasification furnace, the tar is removed by utilizing the high-temperature cracking, partial gasification and catalytic reforming action of the semicoke on the tar in the gasification furnace, and the unreacted semicoke returns to a pyrolyzer after gas-solid separation;
the generated fuel gas exchanges heat with water and air through an air preheater and a waste heat boiler, and the water vapor and the air generated after the heat exchange are used as a gasifying agent and are introduced into the bottom of the gasification furnace;
filtering and dedusting the gas after heat exchange to generate clean gas, introducing the clean gas into a combustor, and rapidly calcining magnesite powder by hot flue gas generated by combustion through gas-solid action, wherein the gas speed in a conveying bed reactor of a magnesite calcining furnace is 3-20 m/s, and the particle size of a used magnesite raw material is less than 200 mu m;
the product is subjected to gas-solid separation, the magnesite powder is preheated by high-temperature flue gas obtained through the gas-solid separation through a flue gas heat exchange system, the preheated mineral powder is conveyed into a calcining furnace, and the flue gas subjected to heat exchange is filtered and dedusted to reach the standard and then is discharged;
preheating high-temperature light-burned magnesium generated by gas-solid separation by a product heat exchange system to clean air required by a gas burner, and conveying the cooled light-burned magnesium product to a storage tank;
the fluidized bed two-stage gasification process comprises the following steps: the device comprises a feeding device, a pyrolyzer, a gasification furnace, a gas-solid separation device, an air preheater, a waste heat boiler, a filter dust collector and the like, wherein fuel is fed into the pyrolyzer to be pyrolyzed or oxidized and pyrolyzed firstly, all generated pyrolysis products and semicoke are fed into the gasification furnace, and the temperature of gas after the waste heat boiler is higher than that of waste water separated by condensing contained steam; high-temperature gas after gas-solid separation and air indirectly exchange heat to preheat air, then steam is generated by a waste heat boiler of the gas, and the preheated air and the generated steam are sent to a gasification furnace and a pyrolyzer;
the reactor of the gasification furnace is a rapid fluidized bed or a conveying bed, and the pyrolyzer is one or any combination of a bubbling/turbulent fluidized bed, a rapid fluidized bed, a conveying bed, a descending bed and a moving fluidized bed;
the flash light-burning magnesite process comprises the following steps: the magnesite powder calcining furnace adopts a conveying bed reactor, the gas burner uses preheated air, and the raw material entering the magnesite calcining furnace is preheated magnesite powder; the high-temperature light-burned powder product after gas-solid separation and air required by gas combustion preheat air and cool the light-burned magnesium product through direct contact heat exchange, and the high-temperature flue gas after gas-solid separation and raw material magnesite powder directly contact heat exchange cooling flue gas to preheat magnesite powder.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810731247.9A CN109136539B (en) | 2018-07-05 | 2018-07-05 | Integrated process of fluidized bed two-stage gasification and flash light burning magnesite |
| PCT/CN2019/077423 WO2020007062A1 (en) | 2018-07-05 | 2019-03-08 | Fluidized bed two-stage gasification and flash light calcined magnesite integration process |
| ATA9240/2019A AT523311B1 (en) | 2018-07-05 | 2019-03-08 | Integrated process of two-stage fluidized bed gasification and flash weak burning of magnesite |
| RU2021102498A RU2770315C1 (en) | 2018-07-05 | 2019-03-08 | Combined method for two-stage gasification in a fluidised bed and soft flash firing of magnesite |
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| CN201810731247.9A CN109136539B (en) | 2018-07-05 | 2018-07-05 | Integrated process of fluidized bed two-stage gasification and flash light burning magnesite |
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| CN109136539A CN109136539A (en) | 2019-01-04 |
| CN109136539B true CN109136539B (en) | 2020-06-23 |
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| CN109136539B (en) * | 2018-07-05 | 2020-06-23 | 沈阳化工大学 | Integrated process of fluidized bed two-stage gasification and flash light burning magnesite |
| CN111747663B (en) * | 2020-08-20 | 2023-09-15 | 沈阳工业大学 | Device and process method for preparing light-burned magnesium oxide by suspension calcination |
| CN111777340B (en) * | 2020-08-20 | 2024-04-23 | 辽宁东大粉体工程技术有限公司 | Device for preparing light burned magnesia and enriching carbon dioxide by smoke self-circulation pyrolysis |
| CN112304092B (en) * | 2020-10-14 | 2022-10-04 | 沈阳化工大学 | Powder material fluidized bed sintering device |
| CN112779057A (en) * | 2020-12-31 | 2021-05-11 | 上海电气集团股份有限公司 | Comprehensive oil sludge treatment system and comprehensive oil sludge treatment method |
| CN117303757B (en) * | 2023-12-01 | 2024-02-20 | 岫岩满族自治县恒锐镁制品有限公司 | Light burning process and system for magnesite |
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| CH645083A5 (en) * | 1980-05-20 | 1984-09-14 | Escher Wyss Ag | METHOD AND DEVICE FOR RECALCINATING A SLAVE CONTAINING CALCIUM CARBONATE. |
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| Publication number | Publication date |
|---|---|
| RU2770315C1 (en) | 2022-04-15 |
| WO2020007062A1 (en) | 2020-01-09 |
| CN109136539A (en) | 2019-01-04 |
| AT523311A2 (en) | 2021-07-15 |
| AT523311A5 (en) | 2022-04-15 |
| AT523311B1 (en) | 2022-08-15 |
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