CN109775666B - Device and method for preparing sulfur by coal gasification in cooperation with calcium sulfate calcination and carbon thermal reduction - Google Patents
Device and method for preparing sulfur by coal gasification in cooperation with calcium sulfate calcination and carbon thermal reduction Download PDFInfo
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Abstract
The invention relates to a process and a method for preparing sulfur by coal gasification in cooperation with calcium sulfate calcination and carbon thermal reduction. Aiming at calcium sulfate at high temperatureReacts with carbon material and sulfur to generate high-concentration SO2Flue gas and metal calcium oxide, a U-shaped coal gasification calcining furnace, a charcoal heat reduction tower, a sulfur recovery device, various heat exchangers and the like are utilized, sulfur is prepared by using solid waste calcium sulfate which is difficult to treat through accurately controlling various reaction conditions, calcium oxide is produced as a byproduct, and the calcium oxide as the byproduct can replace limestone to be used as a desulfurization and denitrification agent.
Description
Technical Field
The invention belongs to the field of solid waste resource utilization, and particularly relates to a process and a method for preparing sulfur by coal gasification in cooperation with calcium sulfate calcination and carbon thermal reduction.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the rapid development of high-concentration phosphate fertilizer and phosphoric acid industries in China, the yield of the byproduct phosphogypsum is increased rapidly, and the main component of the phosphogypsum is CaSO4·2H2O and also contains a small amount of sulfate of other metal ions. At present, the annual emission amount of phosphogypsum in China is nearly hundred million tons, and the accumulated accumulation amount is nearly 5 hundred million tons. Although the domestic phosphogypsum has a certain utilization approach, the domestic phosphogypsum has certain problems, and the treatment amount is small, so that the current pollution situation of the domestic phosphogypsum cannot be relieved. Phosphogypsum contains acidic and harmful substances, and must be specially stacked, thus occupying land and wasting resources, and long-term stacking of phosphogypsum can pollute underground water.
Along with the continuous improvement of the environmental protection requirement of China, the sulfur-containing flue gas discharged by coal-fired power plants, steel plants and the like needs to be provided with a flue gas desulfurization deviceThe wet desulfurization unit mainly based on the limestone-gypsum method accounts for about 85% of the total installed capacity, and although the technology has the advantages of high desulfurization efficiency, stable operation and the like, a large amount of limestone needs to be consumed, the limestone is excessively exploited, the ecological environment is damaged, and the desulfurization by-product is low-quality desulfurization gypsum which has low value and is difficult to utilize. At present, the annual output of the desulfurized gypsum in China is about one hundred million tons, the components of the desulfurized gypsum are similar to that of phosphogypsum, and the main component is CaSO4·2H2O。
The sulfur has the lowest molecular weight and high unit value in all sulfur-containing products; the storage and transportation cost is low; and the sulfur can be used as a production raw material of most sulfur-containing products, and the application is wide. China is a country with shortage of sulfur resources, the import quantity and the consumption quantity of sulfur are in the forefront of the world every year, the external dependence is high, the sulfur is used as one of important chemical raw materials, and the market value and the application value of the sulfur are far higher than those of sulfuric acid.
Patent CN108640090A discloses carbothermic reduction of SO2A device and a method for preparing sulfur belong to the technical field of sulfur recovery, and comprise a storage bin, a gas-solid mixing bin, a carbon thermal reduction tower, a high-temperature gas-solid separator, an ash bucket and a carbon-based reducing agent buffer tank, wherein the carbon thermal reduction tower comprises a reaction section and the gas-solid mixing bin from top to bottom, the storage bin is connected with a material inlet of the gas-solid mixing bin, the top of the reaction section is provided with a reducing gas outlet, the reducing gas outlet is sequentially connected with the high-temperature gas-solid separator, the ash bucket and the carbon-based reducing agent buffer tank, the carbon-based reducing agent buffer tank is connected with a material return port of the gas-solid mixing bin, a bracket, a distribution plate and a make-up gas inlet are sequentially arranged inside the gas-solid mixing bin from top to bottom, a reaction gas inlet pipe enters the gas-solid mixing bin from the bottom of the gas-solid mixing bin, the bracket is2The flue gas of (2) carries out preliminary desulfurization, retrieves sulphur, has prevented the jam that leads to the fact of piling up of material, make full use of the material.
Patent 201710017333.9 discloses a method for preparing calcium oxide and sulfur from gypsum, which comprises the following steps: (1) pretreatment of gypsum: drying dihydrate gypsum to form dehydrated gypsum with the total water content of 2-10%, and grinding the dehydrated gypsum into gypsum powder; (2) decomposing gypsum: contacting the gypsum powder obtained in the step (1) with a sulfur-containing process gas, and reacting at 700-1200 ℃ to finally generate calcium oxide and sulfur dioxide gas; (3) and (3) reducing sulfur dioxide: contacting the sulfur dioxide gas prepared in the step (2) with a carbonaceous reducing agent, and reacting at 600-1000 ℃ to generate a sulfur-containing process gas, wherein the sulfur-containing process gas is divided into two streams, one stream is used for the gypsum decomposition reaction in the step (2), and the other stream is taken out and subjected to condensation, catalytic reaction, granulation and other processes to produce sulfur; the method has high gypsum conversion rate, consumes gypsum to produce calcium oxide and sulfur with high added value. However, the inventor finds that: the method has low utilization rate of raw materials and needs to improve energy consumption.
Disclosure of Invention
In order to overcome the problems, the invention combines the calcium sulfate reduction roasting process and SO2A technology for preparing sulfur by carbon thermal reduction provides a process and a method for preparing sulfur by coal gasification in cooperation with calcium sulfate calcination and carbon thermal reduction, and a corresponding device is designed. Calcium sulfate in carbon material and reducing gas (CO, H)2、S2Etc.) additive to decompose high-concentration SO under synergistic effect2Flue gas and solid calcium oxide powder, high concentration SO2The flue gas can be directly reduced into elemental sulfur steam through reaction with a carbon material at high temperature, and then the sulfur is recovered by a sulfur recovery device after dust removal, temperature reduction and fine dust removal processes in sequence; the solid calcium oxide powder can replace limestone to be used as a desulfurization and denitrification agent for wet desulfurization and denitrification and semi-dry desulfurization and denitrification, and the process can realize the recycling multifunctional utilization of calcium sulfate.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a device for preparing sulfur by coal gasification cooperating with calcium sulfate calcination and carbon thermal reduction comprises: the device comprises a U-shaped furnace, a high-temperature separator I, a calcium sulfate storage bin, a carbon material storage bin I, a carbon thermal reduction tower, a high-temperature separator II, a reheater, a dust removal device, a sulfur recovery device and a sulfur storage tank; the U-shaped furnace is divided into a left side calcining section and a right side coal gasification section, the left side calcining section is connected with a calcium sulfate storage bin and a carbon material storage bin I, an outlet at the upper part of the right side coal gasification section of the U-shaped furnace is connected with an inlet of a high temperature separator I, a material outlet at the bottom of the high temperature separator I is respectively connected with the right side coal gasification section of the U-shaped furnace and a calcium oxide cooler through a flow dividing device, a gas outlet at the top of the high temperature separator I is connected with a material inlet at the top of a carbon thermal reduction tower, an outlet at the side wall of the carbon thermal reduction tower is connected with a high temperature separator II, a material outlet at the bottom of the high temperature separator II is connected with a gas inlet at the side wall of the right side section of the U-shaped furnace, and a gas outlet at the top of the high temperature separator;
and the material inlet at the top of the carbon thermal reduction tower is also connected with a carbon material storage bin II.
At present, the problems of low utilization rate of raw materials and overlarge energy consumption generally exist in a device for preparing calcium oxide and sulfur from calcium sulfate. Therefore, the coal gasification and the calcium sulfate decomposition are synchronously carried out by utilizing the U-shaped furnace, and the reducing gas generated by the coal gasification provides heat and reducing substances for the calcium sulfate decomposition; on the other hand, the invention is also provided with a carbon thermal reduction tower, the optimal temperature of the process for preparing the sulfur is 700-1000 ℃, and is matched with the decomposition temperature (800-1100 ℃) of the calcium sulfate in the presence of reducing gas generated by coal gasification, so the conversion rate of the sulfur product is greatly improved by combining the carbon thermal reduction tower and the calcium sulfate, the spent coke and the reducing gas after the carbon thermal reduction reaction can be used as raw materials for coal gasification reaction or calcium sulfate decomposition, and the spent gas is mainly used as inert gas for transporting materials such as the calcium sulfate and heat, so that the influence of moisture on each reaction is reduced. Therefore, the invention effectively improves the utilization rate of raw materials and the energy consumption of operation by organically combining coal gasification, calcium sulfate decomposition and carbon thermal reduction.
In order to fully utilize the heat energy of the reducing gas containing sulfur steam and simultaneously deposit sulfur step by step, in some embodiments, the cooling medium of the reheater is carbon thermal reduction exhaust gas, and the carbon thermal reduction exhaust gas is also used as a carrier gas of preheated calcium sulfate, so that the carbon thermal reduction exhaust gas after heat absorption is more beneficial to decomposition and temperature rise of the calcium sulfate.
In some embodiments, the bottom of the carbothermic reduction tower is connected with an air inlet of the side wall of the coal gasification section at the right side of the U-shaped furnace, the dead coke discharged from the bottom of the carbothermic reduction tower and the dead coke discharged from the lower part of the high-temperature separator II are introduced into the U-shaped furnace through partial reducing gas to serve as raw materials of coal gasification reaction, so that the cyclic utilization of the dead coke is realized, the solid waste (the solid waste is the dead coke) generated in the carbothermic reduction process is eliminated, and meanwhile, the heat energy and the activity of the dead coke promote the improvement of the coal gasification reaction efficiency.
In some embodiments, the material outlet at the bottom of the dust remover is connected with the coal gasification section at the right side of the U-shaped furnace, and after solid powder in the reducing gas is separated by the dust remover, the solid powder can be used as a raw material for coal gasification reaction due to the fact that the main component is C, and the efficiency of the coal gasification reaction is improved.
In some embodiments, the gas outlet of the sulfur recovery device is further connected to the flue gas purification system, the U-shaped furnace left side calcination section and the reheater, respectively, a part of the exhaust gas after sulfur recovery is used as a conveying gas to convey calcium sulfate and a solid carbon material catalyst to the U-shaped furnace left side calcination section, a part of the exhaust gas is heated by the reheater, the temperature is raised from 120 ℃ to 250 ℃ to 500 ℃ to 800 ℃, the exhaust gas is returned to the carbon thermal reduction tower to be used as a temperature adjustment gas, and finally, the exhaust gas is discharged after entering the flue gas purification system.
In some embodiments, a preheater is disposed between the calcium sulfate storage bin and the U-shaped furnace. Calcium sulfate is converted into anhydrous calcium sulfate by preheating, and water vapor is discharged, so that the subsequent decomposition reaction is prevented from being influenced, and the cascade utilization of the waste heat of the system is realized.
In some embodiments, the calcium oxide cooler is connected with a calcium oxide storage bin, and calcium oxide can be used as a desulfurization and denitrification agent instead of limestone, so that the cooled calcium oxide is collected by the calcium oxide storage bin and is ready for use.
In some embodiments, the outlet of the calcium sulfate storage bin, the outlet of the carbon material storage bin, the carbon thermal reduction spent coke discharge and the outlet pipeline at the lower part of the high-temperature separator II are provided with an air locking feeder so as to accurately control the material conveying amount and ensure the sealing property of the system.
The invention also provides a method for preparing sulfur by coal gasification in cooperation with calcium sulfate calcination and carbon thermal reduction, which comprises the following steps:
the preheated calcium sulfate powder is contacted with solid carbon material and reducing gas at 800-1100 ℃, and the roasting slag and high-concentration SO are collected2Gases and partial excess reducing gases;
calcining slag and high-concentration SO2Gas and part of excessive reducing gas are subjected to gas-solid separation to enable SO2Reacting the gas and part of the excessive reducing gas with a carbon material at 500-1000 ℃ to generate elemental sulfur steam;
wherein the reducing gas is generated by carrying out coal gasification reaction on the spent coke and the reducing gas after the carbothermic reduction reaction.
Research shows that the self-decomposition temperature of calcium sulfate is 1350-1400 ℃, but carbon material and reducing gas (CO, H) are added2、S2Etc.) and the decomposition temperature of calcium sulfate is greatly reduced, the decomposition temperature is about 800-1100 ℃, the reduction of the temperature not only reduces the energy consumption, but also reduces the reduced temperature and reduces SO by carbon heat2The optimal temperature of the process for preparing the sulfur is matched with 700-1000 ℃, so that the conversion rate of the sulfur product can be greatly improved; the main components of the calcium sulfate reduction roasting product are solid metal calcium oxide and high-concentration SO2Gas (SO in gas)25% -30%) of high-concentration SO2The gas can directly enter a carbon thermal reduction tower to carry out oxidation-reduction reaction to prepare sulfur, and calcium oxide can be recycled as a desulfurizer; reducing gas cooperating with carbon material to reduce SO2The carbothermic reduction temperature is reduced from 700 ℃ to 1000 ℃ to 500 ℃ to 800 ℃, the energy consumption is reduced, and the economical efficiency is improved.
In some embodiments, the calcium sulfate, having a particle size of 60 μm to 3mm, is at least one of wet desulfurized gypsum, semi-dry desulfurized gypsum, natural gypsum and phosphogypsum;
the carbon material has a particle size of 60-3 mm and is at least one of coal powder, activated coke, activated semicoke, activated carbon, carbonized materials and graphite.
The invention provides a coal gasification cooperated with calcium sulfate calcination and carbon thermal reductionA process and a method for preparing sulfur. Aiming at the reaction of calcium sulfate with carbon material and sulfur at high temperature to generate high-concentration SO2Flue gas and metal calcium oxide, a U-shaped coal gasification calcining furnace, a charcoal heat reduction tower, a sulfur recovery device, various heat exchangers and the like are utilized, sulfur is prepared by using solid waste calcium sulfate which is difficult to treat through accurately controlling various reaction conditions, calcium oxide is produced as a byproduct, and the calcium oxide as the byproduct can replace limestone to be used as a desulfurization and denitrification agent.
The process has the beneficial effects that:
1. synergistic decomposition of calcium sulfate and SO with carbon material and reducing gas2The carbon thermal reduction greatly reduces the decomposition temperature of calcium sulfate and the carbon thermal reduction temperature;
2. the system energy is utilized in a gradient manner, so that the process energy consumption is reduced, and the economical efficiency is improved;
3. the solid waste calcium sulfate is recycled to produce high-value sulfur and calcium oxide, the calcium oxide can replace limestone to be used as a desulfurization and denitrification agent, and the sulfur is used as an important industrial raw material, so that the method has extremely high utilization value;
4. the spent coke discharged by the carbothermic reduction process is used as a coal gasification raw material, so that the problem that solid waste generated by the carbothermic reduction process is difficult to treat is solved, the consumption of high-quality carbon materials is saved, resources are saved, and the economy is improved.
The process provides a brand-new sustainable pollution-free treatment mode for the calcium sulfate solid waste which is difficult to treat at present, realizes the resource utilization of the calcium sulfate, can relieve the current situation of shortage of sulfur resources in China, reduces the external dependence degree of the sulfur resources, can replace limestone as a desulfurization and denitrification agent by the byproduct calcium oxide, reduces the exploitation of the limestone and protects the ecological environment, and therefore, the process has wide market prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a system diagram of a process and a method for preparing sulfur by coal gasification in cooperation with calcium sulfate calcination and carbothermic reduction in example 1.
The system comprises a calcium sulfate storage bin 1, a calcium sulfate preheater 2, a carbon material storage bin I3, a U-shaped furnace 4, a high-temperature separator I5, a calcium oxide cooler 6, a calcium oxide storage bin 7, a carbon material storage bin II 8, a carbon heat reduction tower 9, a high-temperature separator II 10, a high-temperature separator 11, a reheater 12, a fine dust removal device 13, a sulfur recovery device 14, a sulfur storage tank 15 and a flue gas purification system 15.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced by the background technology, the method aims at the problems that the low-grade gypsum (mainly calcium sulfate) in China is difficult to treat and the sulfur resource is in short supply. Therefore, the invention provides a process and a method for preparing sulfur by coal gasification in cooperation with calcium sulfate calcination and carbon thermal reduction, and the process mainly comprises the following steps:
calcium sulfate powder is firstly conveyed to a calcium sulfate preheater for preheating by accurately controlling the feeding amount through a feeding machine, the calcium sulfate powder is heated to 400-600 ℃ from normal temperature, a heating medium is inert gas or air, and the heat comes from the cooling heat release of a reaction solid product calcium oxide; conveying the preheated calcium sulfate to a calcining section at the left side of the U-shaped furnace by using carbon thermal reduction exhaust gas; the solid carbon material for calcium sulfate calcination accurately controls the feeding amount through a feeding machine, and the carbon thermal reduction exhaust gas is conveyed to the calcination section on the left side of the U-shaped furnace to be used as a solid catalyst for calcium sulfate calcination; in a carbothermic reduction towerConveying the spent coke participating in the carbothermic reduction reaction to a gasification section at the right side of the U-shaped furnace from a reducing gas for coal gasification reaction, wherein the reaction temperature is 1100-1500 ℃, the reducing gas is generated, and meanwhile, heat required by calcium sulfate calcination is provided, and the heat required by coal gasification is provided by a combustor; reducing gas passes through a channel at the bottom of the U-shaped furnace, enters a left calcining section from a right gasifying section, contacts with a solid carbon material and calcium sulfate in the calcining section to react at the reaction temperature of 800-1100 ℃, and the calcined product is calcining slag and high-concentration SO by accurately controlling the reaction conditions and the reaction process2Gases and partial excess reducing gases; the calcined gas-solid product firstly enters a high-temperature separator I, and the calcined slag after gas-solid separation is divided according to whether the mass fraction of calcium oxide in the slag reaches the standard: if the mass fraction of the calcium oxide does not reach the standard, the majority of calcium sulfate is not completely calcined, and at the moment, the roasting slag is returned to the U-shaped furnace for cyclic calcination through an L-shaped return valve on the left side of the flow dividing device, so that the calcination rate of the calcium sulfate is ensured; if the mass fraction of the calcium oxide reaches the standard, the calcium sulfate is more completely calcined, the calcium oxide enters a calcium oxide cooler through an L-shaped material returning valve on the right side of the flow dividing device to be cooled, the temperature is cooled from 900-1100 ℃ to 20-80 ℃, the heat released by the calcium oxide cooling is used for preheating the calcium sulfate, and the cooled roasting slag is stored in a calcium oxide storage bin; the gas after gas-solid separation contains 3 to 30 percent of SO2And 3% -30% of reducing gas, the reducing gas enters the carbon thermal reduction tower from the upper part, and generates oxidation-reduction reaction with the carbon material in the carbon thermal reduction tower at the temperature of 500-1000 ℃, and high-concentration SO2The carbon material is reduced into elemental sulfur steam, and the carbon material participating in the carbothermic reduction is input from the upper part of the carbothermic reduction tower by accurately controlling the feeding amount through a feeding machine; part of the coke exhausted after the carbothermic reduction is directly discharged from the bottom of the carbothermic reduction tower, and the other part of the coke exhausted after the carbothermic reduction is carried by the reducing gas, enters a high-temperature separator II and is discharged from the lower part of the high-temperature separator II, and the coke exhausted from the carbothermic reduction tower is conveyed to a gasification section at the right side of the U-shaped furnace through part of the reducing gas to be used as a coal gasification raw material; reducing gas separated by the high-temperature separator II enters a reheater to be cooled, the temperature of the reducing gas is reduced from 500-1000 ℃ to 450-500 ℃, and a cooling medium is carbon heat reduction exhaust gas; reducing gas part after temperature reductionConveying the spent coke to the right side of the U-shaped furnace as conveying gas, feeding one part of the spent coke into a fine dust removal device to remove solid powder with smaller particle size in the reducing gas, and returning the separated solid powder to the right gasification section of the U-shaped furnace as a raw material; the dedusted reducing gas enters a sulfur recovery device to be recovered to obtain sulfur, the collected sulfur is stored in a sulfur storage tank, part of the exhaust gas after sulfur recovery is used as conveying gas to convey calcium sulfate and a solid carbon material catalyst to a left side calcining section of a U-shaped furnace, part of the exhaust gas is heated by a reheater, the temperature is raised from 120-250 ℃ to 500-800 ℃, the exhaust gas returns to a carbon heat reduction tower to be used as temperature regulating gas, and finally part of the exhaust gas enters a flue gas purification system and is discharged.
The particle size of the calcium sulfate is 60-3 mm, and the calcium sulfate can be various calcium sulfate products such as wet desulphurization gypsum, semi-dry desulphurization gypsum, natural gypsum, phosphogypsum and the like;
the carbon material has the particle size of 60-3 mm, and can be various types of carbon materials such as coal powder, activated coke, activated semicoke, activated carbon, carbonized materials, graphite and the like;
the inert gas comprises a plurality of inert gases such as nitrogen, argon, helium and the like and mixtures thereof;
the particle size of the roasting slag is 60 mu m-3mm, and the main components are solid calcium oxide powder, calcium sulfate powder which is not completely calcined and a small amount of impurities;
the U-shaped furnace can be an entrained flow bed, a fluidized bed, a bubbling bed, a spouted bed, a settling bed and other furnace types; more specifically, the U-shaped furnace is a USC-80U-shaped furnace.
The reducing gas has the temperature of 1200-1500 ℃, and the main component of the reducing gas is N2、CO、H2、CH4、CO2Etc.;
the reducing gas has the temperature of 800-1100 ℃ and the main component of N2S steam (concentration 5% -35%), CO2Etc.;
the main component of the exhaust gas is N2、CO、CO2Etc.;
the main component of the spent coke is C, a substance after the carbothermic reduction reaction;
the feeding machine can be a screw feeding machine, an air locking feeding machine and other feeding forms;
the fuel of the combustor can be a combustor with various fuel forms such as pulverized coal, natural gas, diesel oil and the like;
the high-temperature separator can be a high-temperature cyclone separator, a high-temperature axial flow separator and other separators in various forms;
the fine dust removal device can be a metal mesh filter, a ceramic filter and other fine dust removal filters in various forms;
the carbon thermal reduction tower can be in various forms such as an entrained flow bed, a bubbling bed, a micro fluidized bed, a spouted bed and a fluidized bed;
the gas conveying process is provided with conveying power by a draught fan or a blower;
an outlet of the calcium sulfate storage bin, an outlet of the carbon material storage bin and an outlet pipeline at the lower part of the carbon thermal reduction spent coke discharge high-temperature separator II are provided with an air locking feeder, so that the sealing performance of the system is ensured while the material conveying amount is accurately controlled;
the reducing gas is separated into powdery roasting slag through a high-temperature separator, then cooled through a reheater and enters a fine dust removal device for secondary dust removal, and sulfur is condensed and recovered by a sulfur condenser. The purity of the recovered sulfur reaches more than 99.7 percent and meets the first-class standard of industrial sulfur.
Compared with the existing method for producing calcium oxide and sulfur by using gypsum, the method has the following advantages:
1. the process realizes the cascade utilization of system energy, and is more energy-saving;
2. the solid waste generated by the carbon thermal reduction is recycled for coal gasification reaction, so that reducing atmosphere and energy are provided for calcination, and the recycling degree is higher;
3. the process combines a high-temperature separator and a material returning device, and can realize the circulating calcination of calcium sulfate;
4. the calcium sulfate is calcined by the cooperation of multiple reducing substances, SO that the calcination temperature is reduced, and SO in calcination flue gas is increased2The concentration improves the calcination rate;
5. the process flow combines relatively complete devices and equipment, and is more feasible;
6. the process has the advantages that sulfur recovery is subjected to two-stage dust removal and filtration, so that the sulfur quality is higher;
7. in the process, calcium sulfate calcination and carbon thermal reduction are both fluidized reactions, so that gas-solid contact is better and reaction efficiency is higher.
The invention is further illustrated by the following figures and examples, wherein the raw materials used in the practice are commercially available products.
Example 1:
a device for preparing sulfur by coal gasification cooperating with calcium sulfate calcination and carbon thermal reduction comprises: the device comprises a U-shaped furnace 4, a high-temperature separator I (5), a calcium sulfate storage bin 1, a carbon material storage bin I (3), a charcoal heat reduction tower 9, a high-temperature separator II (10), a reheater 11, a dust removal device 12, a sulfur recovery device 13 and a sulfur storage tank 14; u type stove 4 divides into left side calcination section, right side coal gasification section, the left side calcination section links to each other with calcium sulfate storage bin 1, carbon material storage bin I (3), the export on U type stove 4 right side coal gasification section upper portion links to each other with high temperature separator I (5) import, the bottom material export of high temperature separator I (5) passes through diverging device and links to each other with U type stove 4 right side coal gasification section, calcium oxide cooler 6 respectively, the gas outlet at high temperature separator I (5) top links to each other with the material entry at carbothermic reduction tower 9 top, the export of carbothermic reduction tower 9 lateral wall links to each other with high temperature separator II (10), the material export of high temperature separator II (10) bottom with the air inlet of U type stove 4 right side coal gasification section lateral wall links to each other, the gas outlet and reheater 11, refined dust collector 12 at high temperature separator II (10) top, The sulfur recovery device 13 and the sulfur storage tank 14 are connected in sequence;
and a material inlet at the top of the carbon thermal reduction tower 9 is also connected with a carbon material storage bin II.
The operation method of the device comprises the following steps:
calcium sulfate powder is firstly conveyed to a calcium sulfate preheater 2 for preheating by accurately controlling the feeding amount through a feeding machine, the calcium sulfate powder is heated to 400-600 ℃ from normal temperature, a heating medium is inert gas or air, and heat comes from the cooling heat release amount of a reaction solid product calcium oxide; the preheated calcium sulfate is reduced by carbon heatConveying the exhaust gas to a calcining section at the left side of the U-shaped furnace 4; the solid carbon material for calcium sulfate calcination accurately controls the feeding amount through a feeding machine, and the carbon thermal reduction exhaust gas is conveyed to the calcination section on the left side of the U-shaped furnace 4 to be used as a solid catalyst for calcium sulfate calcination; conveying the spent coke participating in the carbothermic reduction reaction in the carbothermic reduction tower 9 to the right gasification section of the U-shaped furnace 4 from reducing gas for coal gasification reaction at the reaction temperature of 1100-1500 ℃, generating the reducing gas and providing heat required by calcium sulfate calcination, wherein the heat required by coal gasification is provided by a combustor; reducing gas enters a left calcining section from a right gasifying section through a channel at the bottom of the U-shaped furnace 4, contacts with a solid carbon material and calcium sulfate in the calcining section to react at the reaction temperature of 800-1100 ℃, and the calcined products are calcining slag, high-concentration SO2 gas and partial excessive reducing gas by accurately controlling the reaction conditions and the reaction process; the calcined gas-solid product firstly enters a high-temperature separator I (5), and the calcined slag after gas-solid separation is divided according to whether the mass fraction of calcium oxide in the slag reaches the standard: if the mass fraction of the calcium oxide does not reach the standard, the majority of calcium sulfate is not completely calcined, and at the moment, the roasting slag is returned to the U-shaped furnace 4 through an L return valve on the left side of the flow dividing device for cyclic calcination so as to ensure the calcination rate of the calcium sulfate; if the mass fraction of the calcium oxide reaches the standard, the calcium sulfate is more completely calcined, the calcium oxide enters a calcium oxide cooler 6 through an L material returning valve on the right side of the flow dividing device to be cooled, the temperature is cooled from 900-1100 ℃ to 20-80 ℃, the heat released by the calcium oxide cooling is used for preheating the calcium sulfate, and the cooled roasting slag is stored in a calcium oxide storage bin 7; the gas after gas-solid separation contains 3 to 30 percent of SO2And 3% -30% of reducing gas, enters the carbothermic reduction tower 9 from the upper part, and generates oxidation-reduction reaction with the carbon material in the carbothermic reduction tower 9 at the temperature of 500-1000 ℃, SO that high-concentration SO2The carbon material is reduced into elemental sulfur steam, and the carbon material participating in the carbothermic reduction is input from the upper part of the carbothermic reduction tower 9 by accurately controlling the feeding amount through a feeding machine; part of the spent coke after the carbothermic reduction is directly discharged from the bottom of the carbothermic reduction tower 9, part of the spent coke is carried by reducing gas to enter a high-temperature separator II (10) and is discharged from the lower part of the high-temperature separator II (10), and the spent coke discharged from the carbothermic reduction tower 9 is partially reduced throughConveying the raw gas to a gasification section at the right side of the U-shaped furnace 4 as a coal gasification raw material; reducing gas separated by the high-temperature separator II (10) enters a reheater 11 to be cooled, the temperature of the reducing gas is reduced from 500-1000 ℃ to 450-500 ℃, and a cooling medium is carbon heat reduction exhaust gas; one part of the reduced reducing gas is used as conveying gas to carry spent coke to the right side of the U-shaped furnace 4, one part of the reduced reducing gas enters a fine dust removal device 12 to remove solid powder with smaller particle size in the reducing gas, and the separated solid powder returns to the right gasification section of the U-shaped furnace 4 to be used as raw material; the dedusted reducing gas enters a sulfur recovery device 13 to be recovered to obtain sulfur, the collected sulfur is stored in a sulfur storage tank 14, part of the exhaust gas after sulfur recovery is used as conveying gas to convey calcium sulfate and solid carbon material catalyst to a left side calcining section of a U-shaped furnace 4, part of the exhaust gas is heated by a reheater, the temperature is raised from 120-250 ℃ to 500-800 ℃, the exhaust gas returns to a carbon thermal reduction tower 9 to be used as temperature regulating gas, and finally part of the exhaust gas enters a flue gas purification system 15 and is discharged.
Example 2:
a device for preparing sulfur by coal gasification cooperating with calcium sulfate calcination and carbon thermal reduction comprises: the device comprises a U-shaped furnace 4, a high-temperature separator I (5), a calcium sulfate storage bin 1, a carbon material storage bin I (3), a charcoal heat reduction tower 9, a high-temperature separator II (10), a reheater 11, a dust removal device 12, a sulfur recovery device 13 and a sulfur storage tank 14; u type stove 4 divides into left side calcination section, right side coal gasification section, the left side calcination section links to each other with calcium sulfate storage bin 1, carbon material storage bin I (3), the export on U type stove 4 right side coal gasification section upper portion links to each other with high temperature separator I (5) import, the bottom material export of high temperature separator I (5) passes through diverging device and links to each other with U type stove 4 right side coal gasification section, calcium oxide cooler 6 respectively, the gas outlet at high temperature separator I (5) top links to each other with the material entry at carbothermic reduction tower 9 top, the export of carbothermic reduction tower 9 lateral wall links to each other with high temperature separator II (10), the material export of high temperature separator II (10) bottom with the air inlet of U type stove 4 right side coal gasification section lateral wall links to each other, the gas outlet and reheater 11, dust collector 12 at high temperature separator II (10) top, The sulfur recovery device 13 and the sulfur storage tank 14 are connected in sequence;
and a material inlet at the top of the carbon thermal reduction tower 9 is also connected with a carbon material storage bin II.
In order to fully utilize the heat energy of the sulfur vapor and simultaneously deposit the sulfur step by step, in the embodiment of the invention, the cooling medium of the reheater 11 is the carbon thermal reduction exhaust gas, and the carbon thermal reduction exhaust gas is also used as the carrier gas of the preheated calcium sulfate, so the carbon thermal reduction exhaust gas after heat absorption is more beneficial to the decomposition and temperature rise of the calcium sulfate.
Example 3:
a device for preparing sulfur by coal gasification cooperating with calcium sulfate calcination and carbon thermal reduction comprises: the device comprises a U-shaped furnace 4, a high-temperature separator I (5), a calcium sulfate storage bin 1, a carbon material storage bin I (3), a charcoal heat reduction tower 9, a high-temperature separator II (10), a reheater 11, a dust removal device 12, a sulfur recovery device 13 and a sulfur storage tank 14; u type stove 4 divides into left side calcination section, right side coal gasification section, the left side calcination section links to each other with calcium sulfate storage bin 1, carbon material storage bin I (3), the export on U type stove 4 right side coal gasification section upper portion links to each other with high temperature separator I (5) import, the bottom material export of high temperature separator I (5) passes through diverging device and links to each other with U type stove 4 right side coal gasification section, calcium oxide cooler 6 respectively, the gas outlet at high temperature separator I (5) top links to each other with the material entry at carbothermic reduction tower 9 top, the export of carbothermic reduction tower 9 lateral wall links to each other with high temperature separator II (10), the material export of high temperature separator II (10) bottom with the air inlet of U type stove 4 right side coal gasification section lateral wall links to each other, the gas outlet and reheater 11, dust collector 12 at high temperature separator II (10) top, The sulfur recovery device 13 and the sulfur storage tank 14 are connected in sequence;
and a material inlet at the top of the carbon thermal reduction tower 9 is also connected with a carbon material storage bin II.
In this embodiment, the bottom of the char-heat reduction tower 9 is connected to the gas inlet of the side wall of the right coal gasification stage of the U-shaped furnace 4, and the lean coke discharged from the bottom of the char-heat reduction tower 9 is introduced into the U-shaped furnace 4 as a raw material for coal gasification reaction together with the lean coke discharged from the lower part of the high-temperature separator ii (10), so that the recycle of the lean coke is realized, and the heat energy and activity of the lean coke promote the improvement of the coal gasification reaction efficiency.
Example 4:
a device for preparing sulfur by coal gasification cooperating with calcium sulfate calcination and carbon thermal reduction comprises: the device comprises a U-shaped furnace 4, a high-temperature separator I (5), a calcium sulfate storage bin 1, a carbon material storage bin I (3), a charcoal heat reduction tower 9, a high-temperature separator II (10), a reheater 11, a dust removal device 12, a sulfur recovery device 13 and a sulfur storage tank 14; u type stove 4 divides into left side calcination section, right side coal gasification section, the left side calcination section links to each other with calcium sulfate storage bin 1, carbon material storage bin I (3), the export on U type stove 4 right side coal gasification section upper portion links to each other with high temperature separator I (5) import, the bottom material export of high temperature separator I (5) passes through diverging device and links to each other with U type stove 4 right side coal gasification section, calcium oxide cooler 6 respectively, the gas outlet at high temperature separator I (5) top links to each other with the material entry at carbothermic reduction tower 9 top, the export of carbothermic reduction tower 9 lateral wall links to each other with high temperature separator II (10), the material export of high temperature separator II (10) bottom with the air inlet of U type stove 4 right side coal gasification section lateral wall links to each other, the gas outlet and reheater 11, dust collector 12 at high temperature separator II (10) top, The sulfur recovery device 13 and the sulfur storage tank 14 are connected in sequence;
and a material inlet at the top of the carbon thermal reduction tower 9 is also connected with a carbon material storage bin II.
In this embodiment, the material outlet at the bottom of the dust separator 12 is connected to the right coal gasification stage of the U-shaped furnace 4, and the main component of the solid powder in the reducing gas after separation by the dust separator 12 is C, so that the solid powder can be used as a raw material for coal gasification reaction, thereby improving the efficiency of coal gasification reaction.
Example 4:
a device for preparing sulfur by coal gasification cooperating with calcium sulfate calcination and carbon thermal reduction comprises: the device comprises a U-shaped furnace 4, a high-temperature separator I (5), a calcium sulfate storage bin 1, a carbon material storage bin I (3), a charcoal heat reduction tower 9, a high-temperature separator II (10), a reheater 11, a dust removal device 12, a sulfur recovery device 13 and a sulfur storage tank 14; u type stove 4 divides into left side calcination section, right side coal gasification section, the left side calcination section links to each other with calcium sulfate storage bin 1, carbon material storage bin I (3), the export on U type stove 4 right side coal gasification section upper portion links to each other with high temperature separator I (5) import, the bottom material export of high temperature separator I (5) passes through diverging device and links to each other with U type stove 4 right side coal gasification section, calcium oxide cooler 6 respectively, the gas outlet at high temperature separator I (5) top links to each other with the material entry at carbothermic reduction tower 9 top, the export of carbothermic reduction tower 9 lateral wall links to each other with high temperature separator II (10), the material export of high temperature separator II (10) bottom with the air inlet of U type stove 4 right side coal gasification section lateral wall links to each other, the gas outlet and reheater 11, dust collector 12 at high temperature separator II (10) top, The sulfur recovery device 13 and the sulfur storage tank 14 are connected in sequence;
and a material inlet at the top of the carbon thermal reduction tower 9 is also connected with a carbon material storage bin II.
In this embodiment, the flue gas outlet of the sulfur recovery device 13 is further connected to the flue gas purification system 15, the left side calcination section of the U-shaped furnace 4, and the reheater 11, a part of the exhaust gas after sulfur recovery is used as a conveying gas to convey calcium sulfate and a solid carbon material catalyst to the left side calcination section of the U-shaped furnace 4, a part of the exhaust gas is heated by the reheater 11, the temperature is raised from 120 ℃ to 250 ℃ to 500 ℃ to 800 ℃, the exhaust gas is returned to the char heat reduction tower 9 as a temperature adjustment gas, and the last part of the exhaust gas is discharged after entering the flue gas purification system 15.
Example 5:
a device for preparing sulfur by coal gasification cooperating with calcium sulfate calcination and carbon thermal reduction comprises: the device comprises a U-shaped furnace 4, a high-temperature separator I (5), a calcium sulfate storage bin 1, a carbon material storage bin I (3), a charcoal heat reduction tower 9, a high-temperature separator II (10), a reheater 11, a dust removal device 12, a sulfur recovery device 13 and a sulfur storage tank 14; u type stove 4 divides into left side calcination section, right side coal gasification section, the left side calcination section links to each other with calcium sulfate storage bin 1, carbon material storage bin I (3), the export on U type stove 4 right side coal gasification section upper portion links to each other with high temperature separator I (5) import, the bottom material export of high temperature separator I (5) passes through diverging device and links to each other with U type stove 4 right side coal gasification section, calcium oxide cooler 6 respectively, the gas outlet at high temperature separator I (5) top links to each other with the material entry at carbothermic reduction tower 9 top, the export of carbothermic reduction tower 9 lateral wall links to each other with high temperature separator II (10), the material export of high temperature separator II (10) bottom with the air inlet of U type stove 4 right side coal gasification section lateral wall links to each other, the gas outlet and reheater 11, dust collector 12 at high temperature separator II (10) top, The sulfur recovery device 13 and the sulfur storage tank 14 are connected in sequence;
and a material inlet at the top of the carbon thermal reduction tower 9 is also connected with a carbon material storage bin II.
In this embodiment, a calcium sulfate preheater 2 is disposed between the calcium sulfate storage bin 1 and the U-shaped furnace 4. Calcium sulfate is converted into anhydrous calcium sulfate by preheating, and water vapor is removed, so that subsequent decomposition reaction is prevented from being influenced.
Example 6:
a device for preparing sulfur by coal gasification cooperating with calcium sulfate calcination and carbon thermal reduction comprises: the device comprises a U-shaped furnace 4, a high-temperature separator I (5), a calcium sulfate storage bin 1, a carbon material storage bin I (3), a charcoal heat reduction tower 9, a high-temperature separator II (10), a reheater 11, a dust removal device 12, a sulfur recovery device 13 and a sulfur storage tank 14; u type stove 4 divides into left side calcination section, right side coal gasification section, the left side calcination section links to each other with calcium sulfate storage bin 1, carbon material storage bin I (3), the export on U type stove 4 right side coal gasification section upper portion links to each other with high temperature separator I (5) import, the bottom material export of high temperature separator I (5) passes through diverging device and links to each other with U type stove 4 right side coal gasification section, calcium oxide cooler 6 respectively, the gas outlet at high temperature separator I (5) top links to each other with the material entry at carbothermic reduction tower 9 top, the export of carbothermic reduction tower 9 lateral wall links to each other with high temperature separator II (10), the material export of high temperature separator II (10) bottom with the air inlet of U type stove 4 right side coal gasification section lateral wall links to each other, the gas outlet and reheater 11, dust collector 12 at high temperature separator II (10) top, The sulfur recovery device 13 and the sulfur storage tank 14 are connected in sequence;
and a material inlet at the top of the carbon thermal reduction tower 9 is also connected with a carbon material storage bin II.
In this embodiment, the calcium oxide cooler 6 is connected to the calcium oxide storage bin 7, and calcium oxide can be used as a desulfurization and denitrification agent instead of limestone, so that the cooled calcium oxide is collected by the calcium oxide storage bin 7 for standby.
1. Calcium sulfate storage bin, 2 calcium sulfate preheater, 3 carbon material storage bin I, 4U-shaped furnace, 5 high-temperature separator I, 6 calcium oxide cooler, 7 calcium oxide storage bin, 8 carbon material storage bin II, 9 carbon thermal reduction tower, 10 high-temperature separator II, 11 reheater, 12 fine dust removal device, 13 sulfur recovery device, 14 sulfur storage tank, 15 flue gas purification system
Example 7:
a device for preparing sulfur by coal gasification cooperating with calcium sulfate calcination and carbon thermal reduction comprises: the device comprises a U-shaped furnace 4, a high-temperature separator I (5), a calcium sulfate storage bin 1, a carbon material storage bin I (3), a charcoal heat reduction tower 9, a high-temperature separator II (10), a reheater 11, a dust removal device 12, a sulfur recovery device 13 and a sulfur storage tank 14; u type stove 4 divides into left side calcination section, right side coal gasification section, the left side calcination section links to each other with calcium sulfate storage bin 1, carbon material storage bin I (3), the export on U type stove 4 right side coal gasification section upper portion links to each other with high temperature separator I (5) import, the bottom material export of high temperature separator I (5) passes through diverging device and links to each other with U type stove 4 right side coal gasification section, calcium oxide cooler 6 respectively, the gas outlet at high temperature separator I (5) top links to each other with the material entry at carbothermic reduction tower 9 top, the export of carbothermic reduction tower 9 lateral wall links to each other with high temperature separator II (10), the material export of high temperature separator II (10) bottom with the air inlet of U type stove 4 right side coal gasification section lateral wall links to each other, the gas outlet and reheater 11, dust collector 12 at high temperature separator II (10) top, The sulfur recovery device 13 and the sulfur storage tank 14 are connected in sequence;
and a material inlet at the top of the carbon thermal reduction tower 9 is also connected with a carbon material storage bin II.
In the embodiment, the outlet of the calcium sulfate storage bin 1, the outlets of the carbon material storage bins I and II (3 and 8) and the outlet pipeline at the lower part of the carbon thermal reduction spent coke discharge high-temperature separator II (10) are provided with the air locking feeder so as to accurately control the material conveying amount and ensure the sealing property of the system.
Example 8:
a method for preparing sulfur by coal gasification in cooperation with calcium sulfate calcination and carbon thermal reduction comprises the following steps:
the preheated calcium sulfate powder is contacted with solid carbon material and reducing gas at 800-1100 ℃, and the roasting slag and high-concentration SO are collected2Gases and partial excess reducing gases;
calcining slag and high-concentration SO2Gas and part of excessive reducing gas are subjected to gas-solid separation to enable SO2Reacting the gas and part of the excessive reducing gas with a carbon material at 500-1000 ℃ to generate elemental sulfur steam;
wherein the reducing gas is generated by carrying out coal gasification reaction on the spent coke and the reducing gas after the carbothermic reduction reaction.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. The utility model provides a device of coal gasification cooperation calcium sulfate calcination and carbothermic reduction preparation sulphur which characterized in that includes: the device comprises a U-shaped furnace, a high-temperature separator I, a calcium sulfate storage bin, a carbon material storage bin I, a carbon thermal reduction tower, a high-temperature separator II, a reheater, a dust removal device, a sulfur recovery device and a sulfur storage tank; the U-shaped furnace is divided into a left side calcining section and a right side coal gasification section, the left side calcining section is connected with a calcium sulfate storage bin and a carbon material storage bin I, an outlet at the upper part of the right side coal gasification section of the U-shaped furnace is connected with an inlet of a high temperature separator I, a material outlet at the bottom of the high temperature separator I is respectively connected with the right side coal gasification section of the U-shaped furnace and a calcium oxide cooler through a flow dividing device, a gas outlet at the top of the high temperature separator I is connected with a material inlet at the top of a carbon thermal reduction tower, an outlet at the side wall of the carbon thermal reduction tower is connected with a high temperature separator II, a material outlet at the bottom of the high temperature separator II is connected with a gas inlet at the side wall of the right side section of the U-shaped furnace, and a gas outlet at the top of the high temperature separator;
and the material inlet at the top of the carbon thermal reduction tower is also connected with a carbon material storage bin II.
2. The apparatus of claim 1, wherein the cooling medium of the reheater is spent carbon heat reduction gas.
3. The apparatus according to claim 1, wherein the bottom of the carbothermic reduction tower is connected to the air inlet of the side wall of the right coal gasification stage of the U-shaped furnace.
4. The device of claim 1, wherein a material outlet at the bottom of the dust removal device is connected with a coal gasification section at the right side of the U-shaped furnace.
5. The apparatus of claim 1, wherein the gas outlet of the sulphur recovery unit is further connected to a flue gas cleaning system, a left side calcination section of the U-shaped furnace and a reheater, respectively.
6. The apparatus of claim 1, wherein the calcium sulfate storage bin is provided with a preheater directly with the U-shaped furnace.
7. The apparatus of claim 1, wherein the calcium oxide cooler is connected to a calcium oxide storage bin.
8. The device as claimed in claim 1, wherein the outlets of the calcium sulfate storage bin, the carbon material storage bins I and II, the carbon thermal reduction spent coke discharge and the outlet pipeline at the lower part of the high-temperature separator II are provided with air locking feeders.
9. A method for preparing sulfur by coal gasification in cooperation with calcium sulfate calcination and carbothermic reduction, which is characterized by using the device of claim 1, comprising the following steps:
the preheated calcium sulfate powder is contacted with solid carbon material and reducing gas at 800-1100 ℃, and the roasting slag and high-concentration SO are collected2Gases and partial excess reducing gases;
calcining slag and high-concentration SO2Gas and part of excessive reducing gas are subjected to gas-solid separation to enable SO2Reacting the gas and part of the excessive reducing gas with a carbon material at 500-1000 ℃ to generate elemental sulfur steam;
wherein the reducing gas is generated by carrying out coal gasification reaction on the spent coke and the reducing gas after the carbothermic reduction reaction.
10. The method according to claim 9, wherein the calcium sulfate, having a particle size of 60 μm-3mm, is at least one of wet desulfurization gypsum, semi-dry desulfurization gypsum, natural gypsum and phosphogypsum;
the carbon material with the particle size of 60 mu m-3mm is at least one of coal powder, activated coke, activated semicoke, activated carbon, carbonized materials and graphite.
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| CN111498811B (en) * | 2020-03-18 | 2021-12-17 | 山东大学 | Process and device for gypsum calcination and CO coupling carbon thermal reduction |
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| CN101708825A (en) * | 2009-11-25 | 2010-05-19 | 四川大学 | Method for preparing calcium sulfide by reducing and decomposting gypsum through sulfur |
| JP2011020881A (en) * | 2009-07-15 | 2011-02-03 | Akita Univ | Method for converting calcium sulfate-containing material into calcium oxide and elemental sulfur, and method and system for recycling calcium sulfate-containing material |
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| JP2011020881A (en) * | 2009-07-15 | 2011-02-03 | Akita Univ | Method for converting calcium sulfate-containing material into calcium oxide and elemental sulfur, and method and system for recycling calcium sulfate-containing material |
| CN101708825A (en) * | 2009-11-25 | 2010-05-19 | 四川大学 | Method for preparing calcium sulfide by reducing and decomposting gypsum through sulfur |
| CN102491659A (en) * | 2011-12-02 | 2012-06-13 | 宋乐柱 | Fluidized bed type gypsum calcining device |
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