CN1884048A - Process for reductive decomposition of phosphogypsum by sulfur coal - Google Patents
Process for reductive decomposition of phosphogypsum by sulfur coal Download PDFInfo
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- CN1884048A CN1884048A CN200610011002.6A CN200610011002A CN1884048A CN 1884048 A CN1884048 A CN 1884048A CN 200610011002 A CN200610011002 A CN 200610011002A CN 1884048 A CN1884048 A CN 1884048A
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- phosphogypsum
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- sulfur coal
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- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical group O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 60
- 239000003245 coal Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000011593 sulfur Substances 0.000 title claims description 42
- 229910052717 sulfur Inorganic materials 0.000 title claims description 42
- 238000000354 decomposition reaction Methods 0.000 title claims description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 19
- 230000002829 reductive effect Effects 0.000 title claims description 10
- 239000012265 solid product Substances 0.000 claims abstract description 15
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 38
- 239000000292 calcium oxide Substances 0.000 claims description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 11
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000005864 Sulphur Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000010440 gypsum Substances 0.000 description 4
- 229910052602 gypsum Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000011499 joint compound Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052934 alunite Inorganic materials 0.000 description 1
- 239000010424 alunite Substances 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000011469 building brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Abstract
The invention discloses a reducing method to resolve phosphogypsum through high-sulphur coal over 3 percent, which is characterized by the following: producing burner gas with not less than 15 percent SO2 as standard raw material gas in the two-transmitting two-adsorbing acid-preparing technology directly; making the disposed material with not less than 70 percent CaO solid product as standard cement raw material of over 425 number directly without waste. The invention improves dissolving rate of phosphogypsum not less than 95 percent and percentage of desulphurization not less than 90 percent, which forms a circulated economic industrial chain.
Description
The technical field is as follows: the invention relates to a method for producing high-concentration sulfur dioxide and qualified cement raw materials by using solid waste phosphogypsum, belonging to the technical field of phosphorus chemical industry.
Secondly, background art: the phosphogypsum is industrial waste residue generated by reaction of phosphorus ore and sulfuric acid in the wet-process phosphoric acid production process, 4-5 tons of phosphogypsum are generated by calculation for each 1 ton of phosphoric acid produced, the annual emission amount of the phosphogypsum all over the world currently reaches more than 2 hundred million tons, but the utilization rate of the phosphogypsum does not exceed 10%, and the treatment, disposal and comprehensive utilization of the phosphogypsum become a worldwide problem. The yield of phosphate fertilizers is the first world in China, and a large amount of wet-process phosphoric acid is needed for producing high-concentration phosphate fertilizers (such as ammonium phosphate, heavy calcium carbonate and the like), and a large amount of phosphogypsum waste residues are generated. Most of phosphogypsum is piled or dumped, the piling of the phosphogypsum not only occupies a large amount of land and consumes a large amount of capital, but also acidic water leaks to pollute a water source, and secondary pollution is formed. But the phosphogypsum contains rich calcium and sulfur and is a precious resource. At present, the worldwide supply of sulfur resources is short, the price of sulfur rises, China is a country relatively lack of sulfur resources, the import quantity of sulfur in China reaches 4Mt in 2000, and the import of imported phosphate fertilizer (according to the acid consumption) is equivalent to 5Mt of imported sulfur. The dependence of sulfur resources on the outside is over 50% in 2005. Therefore, the treatment and utilization of the phosphogypsum waste residue are urgent from the aspects of environmental protection and resource utilization.
At present, the method for utilizing the phosphogypsum at home and abroad mainly focuses on three aspects of industry, agriculture and building material industry. The preparation of sulfuric acid and the co-production of cement by phosphogypsum is a direction capable of recycling resources on a large scale, Germany Lurgi company carries out research, and China also carries out development and research work for a long time, but in the existing development and research, the phosphogypsum is mostly reduced by coke, the decomposition rate and the desulfurization rate are not high, and the generated SO is not high2Low concentration, large fluctuation, large equipment investment, high energy consumption, long production process, more production equipment, low conversion rate and the like, and is unreasonable in economy and environmental protection. And a lot of work is needed to be carried out for comprehensive popularization and application.
In publication No. CN1424273A, a method for treating phosphogypsum is disclosed, which is: firstly, mixing phosphogypsum and water according to a weight ratio of 1: 1-1.5, grinding the mixture into uniform slurry with 200 meshes by using a ball mill, diluting the slurry and the water according to a weight ratio of 1: 2-4, naturally precipitating the diluted slurry by using a primary precipitation tank (length multiplied by width multiplied by depth is 20m multiplied by 4m multiplied by 3.5m) to obtain primary precipitate, naturally precipitating the supernatant obtained by the primary precipitation in a secondary precipitation tank (length multiplied by width multiplied by depth is 24m multiplied by 4m) to obtain secondary precipitate, naturally precipitating the supernatant obtained by the secondary precipitation in a tertiary precipitation tank (length multiplied by width multiplied by depth is 30m multiplied by 4m) to obtain tertiary precipitate, shoveling out the precipitates respectively, naturally drying the precipitates, and drying the precipitates by using a drying machine to obtain a finished product. Wherein the first-level precipitate is used for producing calcium phosphate, the second-level precipitate is used for producing compound fertilizer or cement or building bricks or gypsum boards, and the third-level precipitate is used for producing potassium sulfate or paint.
The application of the modified phosphogypsum brick as a cement retarder is disclosed in the publication No. CN1389421A, and the method comprises the following steps: the modified phosphogypsum brick is prepared by uniformly stirring a mixture containing 80-95 wt% of phosphogypsum, 2-15 wt% of reinforcing agent and 3-10 wt% of modifier, wherein the sum of the components is 100 wt%, extruding and forming, and naturally drying, wherein the water content of the modified phosphogypsum brick is less than 10 wt%, and SO3>35 wt%, soluble P2O5Less than 0.1 wt% and pH value greater than 7, wherein the reinforcing agent is any one or more of blast furnace slag, fly ash, steel slag or other industrial waste residues. 3-10 wt% of modifier is 0-10 wt% of alkaline substance: one or two of carbide slag, caustic sludge, white mud, cement, lime and red mud, and 0-10 wt% of industrial aluminum slag or alunite or calcined bauxite. "
In publication No. CN1424273A, a method for preparing building gypsum powder by using phosphogypsum is disclosed, which comprises the following steps: the method comprises the steps of directly feeding the phosphogypsum as a byproduct of wet-process phosphoric acid and high-temperature flue gas at 400-700 ℃ into a dryer, scattering the phosphogypsum by a hammer head, fully mixing the phosphogypsum with the high-temperatureflue gas, carrying out heat exchange, calcining and dehydrating, and conveying the mixture to a bag-type dust collector along with air flow to separate to obtain a calcined product containing the semi-hydrated gypsum (the air flow temperature at the inlet of the bag-type dust collector is controlled at 150-170 ℃). Conveying the calcined product collected by the bag-type dust collector to a mill, adding an additive (when the additive is citric acid, the addition amount is 0.1-0.3% of the weight of the calcined product, when the additive is sodium citrate, the addition amount is 0.15-0.4% of the weight of the calcined product, when the additive is a mixture of citric acid and sodium citrate, the citric acid and the sodium citrate are prepared according to the proportion of 1: 0.2-5, and the addition amount is 0.2-0.4% of the weight of the calcined product), and grinding until the median diameter D50 value of the particles of the ground product is reduced to be less than 0.7 time of the median diameter D50 value of the particles of the calcined product before grinding to prepare the building gypsum powder.
China is a country which takes coal as main energy, the coal reserves are in the top of the world, the annual output is the first in the world, and the predicted total amount and the proven reserves of high-sulfur coal (the sulfur content is more than or equal to 3%) are 4260 hundred million t and 620 hundred million t respectively. Because coal produces a large amount of sulfur dioxide in the combustion process, the global environment is seriously threatened, and high-sulfur coal becomes a forbidden coal type in our country according to the fifteen-program of acid rain and sulfur dioxide pollution control in two-control-area. If the phosphogypsum is reduced and decomposed by high-sulfur coal, the sulfur in the high-sulfur coal can be fully utilized, the concentration of sulfur dioxide in the product is improved and stabilized, qualified raw material gas isprovided for an acid preparation process, meanwhile, the high-sulfur coal residue can also dilute harmful impurities in the phosphogypsum, and Si and Al in the high-sulfur coal residue are solidified in a solid product, so that favorable conditions are provided for the phosphogypsum to be used as a cement raw material. The whole process flow provides a new approach for reasonable utilization of the phosphogypsum and the high-sulfur coal, develops potential sulfur resources, reduces sulfur dioxide discharged into the atmosphere, generates good economic benefit, forms a circular economy industrial chain of a wet-process phosphoric acid enterprise, and realizes comprehensive utilization of the phosphogypsum.
Thirdly, the invention content:
the invention aims to provide a method for reductive decomposition of phosphogypsum by high-sulfur coal, which is used for reductive decomposition of phosphogypsum by high-sulfur coal with sulfur content more than or equal to 3 percent to produce SO2The furnace gas with the volume percentage content of more than or equal to 15 percent can be directly used as qualified raw material gas of a two-conversion two-absorption acid making process, the produced solid product with the CaO mass percentage content of more than or equal to 70 percent can be directly used as the raw material for producing qualified cement with No. 425 and above, no waste is generated in the process, the decomposition rate of phosphogypsum is more than or equal to 95 percent, and the desulfurization rate is more than or equal to 90 percent.
The invention is completed according to the following steps:
1. the raw material is phosphogypsum, the main chemical components of which by mass percentage can be 26-37 percent of calcium oxide, 39-51 percent of sulfur dioxide, 0.08-3.31 percent of ferric oxide, 0.08-2.65percent of aluminum oxide, 0.47-1.28 percent of phosphorus pentoxide, 0.05-0.26 percent of fluorine and 8.20-15.38 percent of silicon dioxide,
2. respectively drying phosphogypsum and high-sulfur coal with the sulfur content of more than or equal to 3% at 100-110 ℃ until the moisture content is less than 8 mass%, wherein the time is 1.5-2 hours;
3. uniformly mixing dried phosphogypsum and high-sulfur coal in a mass ratio of 20: 1-2, and then sending the mixture into a reduction decomposition furnace, controlling the furnace temperature to be 800-1350 ℃, and carrying out reduction decomposition reaction for 0.5-2 hours, wherein the main component CaSO in the phosphogypsum4① reacting with high-sulfur coal, continuously detecting the volume percentage of sulfur dioxide in the furnace gas on line by using a flue gas analyzer in the reaction process, when the volume percentage of sulfur dioxide is more than or equal to 15 percent, the reaction is complete,stopping heating the reduction decomposing furnace to produce SO2The furnace gas with the volume percentage content of more than or equal to 15 percent can be directly used as qualified raw material gas of a two-conversion two-absorption acid making process, the mass percentage content of CaO in a solid product is more than or equal to 70 percent, the solid product can be directly used as a qualified cement raw material for producing No. 425 cement, the decomposition rate of phosphogypsum is more than or equal to 95 percent, and the desulfurization rate is more than or equal to 90 percent. The main reaction equations that occur during reductive decomposition are:
the main advantages of the invention are:
(1) the phosphogypsum is decomposed by the process, the decomposition rate is more than or equal to 95 percent, the desulfurization rate is more than or equal to 93 percent, and the phosphogypsum is not required to be pretreated;
(2) the concentration of sulfur dioxide in the furnace gas is high and stable, and the sulfur dioxide can be directly used as a raw material gas for a sulfuric acid preparation process;
(3) si, Al and other elements in the high-sulfur coal are solidified in the solid product, and harmful impurities in the phosphogypsum are diluted at the same time, so that the generated solid product can be directly used for producing 425#The cement raw materials of the above labels;
(4) a new utilization approach is found for national banned high-sulfur coal due to serious environmental pollution caused by sulfur dioxide emission, and no environmental pollution is generated;
(5) the components of the phosphogypsum are furthest utilized and digested in the technical process, so that the problems of harmlessness and export of the phosphogypsum which is a hazardous waste are solved; the product is completely utilized, and no harmful substance enters the environment;
(6) the high-sulfur coal resource is reasonably utilized, the potential sulfur resource is developed, a circular economic industrial chain of wet-process phosphoric acid enterprises is formed, the comprehensive utilization of the phosphogypsum is realized, and the current situation of sulfur resource shortage in China is relieved.
Fourthly, the specific implementation mode:
example 1: main chemical component mass/%, of phosphogypsum: CaO 35.73, SO248.31，Fe2O30.1，Al2O30.494，P2O50.5，F 0.06，SiO29.517, mixing dried phosphogypsum with high-sulfur coal with 3.6% of sulfur in a mass ratio of 20: 1.5, feeding into a reduction decomposing furnace, and controlling the furnaceThe temperature is 1200-1300 ℃, the reduction decomposition reaction is carried out for 1-1.5 hours, when the volume content of sulfur dioxide in furnace gas is continuously detected to be 15-18% on line by using a flue gas analyzer, the reaction is complete, the heating reduction decomposition furnace is stopped, after natural cooling, a solid product is taken out for analysis and calculation, the decomposition rate of phosphogypsum can be calculated to be 97%, the desulfurization rate is 95%, the content of calcium oxide in the generated solid product is 71%, and the phosphogypsum can be directly used as cement with the production strength grade of 32.5 (R).
Example 2: main chemical component mass/%, of phosphogypsum: CaO 36.03, SO2＝49.01，Fe2O3＝0.1，Al2O3＝0.59，P2O5＝1.01，F＝0.06，SiO2＝11.12，
Uniformly mixing dried phosphogypsum and high-sulfur coal with the sulfur content of 5.2% in a mass ratio of 20: 1.2, sending the mixture into a reduction decomposition furnace, controlling the furnace temperature to be 1000-1150 ℃, carrying out reduction decomposition reaction for 1.5-2 hours, continuously detecting the volume content of sulfur dioxide in the furnace gas to be 17-20% by using a flue gas analyzer on line, completely reacting, stopping heating the reduction decomposition furnace, naturally cooling, taking out a solid product, carrying out analysis and calculation, calculating the decomposition rate of the phosphogypsum to be 98%, the desulfurization rate to be 96%, and the content of calcium oxide in a generated solid product to be 73%, wherein the generated solid product can be directly used as cement with the production strength grade of 42.5 (R).
Example 3: mass of main chemical components/%: CaO 32.0, SO2＝45.31，Fe2O3＝0.1，Al2O3＝0.59，P2O5＝0.7，F＝0.08，SiO29.12, uniformly mixing dried phosphogypsum and high-sulfur coal with 4.3 percent of sulfur in a mass ratio of 20: 1.8, sending the mixture into a reduction decomposition furnace, controlling the furnace temperature to be 1100-1250 ℃, carrying out reduction decomposition reaction for 1-1.5 hours, continuously detecting the volume content of sulfur dioxide in furnace gas to be 17-19 percent on line by using a flue gas analyzer, completely reacting, stopping heating the reduction decomposition furnace, naturally cooling, taking out a solid product, carrying out analysis and calculation, calculating the decomposition rate of the phosphogypsum to be 98 percent, the desulfurization rate to be 96 percent, and directly using the generated solid product to produce cement with the strength grade of 42.5(R), wherein the calcium oxide content is 73 percent.
Claims (2)
1. A method for reductive decomposition of phosphogypsum by high-sulfur coal is characterized by comprising the following steps: the method is completed according to the following steps,
(1) respectively drying the phosphogypsum and high-sulfur coal with the sulfur content of more than or equal to 3% at the temperature of 100-110 ℃ until the moisture content is less than 8 wt%, and the time is 1.5-2 hours;
(2) uniformly mixing the dried phosphogypsum and the high-sulfur coal in a mass ratio of 20: 1-2, feeding the mixture into a reduction decomposition furnace, controlling the furnace temperature to be 800-1350 ℃, carrying out reduction decomposition reaction for 0.5-2 hours, and producing SO2Furnace gas with the volume percentage content of more than or equal to 15 percent and solid products with the mass percentage content of CaO of more than or equal to 70 percent.
2. The method for reductive decomposition of phosphogypsum with high-sulfur coal according to claim 1, characterized in that: the phosphogypsum comprises, by mass, 26-37% of calcium oxide, 39-51% of sulfur dioxide, 0.08-3.31% of ferric oxide, 0.08-2.65% of aluminum oxide, 0.47-1.28% of phosphorus pentoxide, 0.05-0.26% of fluorine and 8.20-15.38% of silicon dioxide.
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| CN100415639C CN100415639C (en) | 2008-09-03 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941806A (en) * | 2010-08-30 | 2011-01-12 | 瓮福（集团）有限责任公司 | Method for utilizing composite reducing agent to decompose phosphogypsum |
| CN101323436B (en) * | 2008-07-21 | 2012-05-30 | 昆明理工大学 | Method for reductively decomposion of ardealite by composite reducer |
| CN104831076A (en) * | 2015-06-04 | 2015-08-12 | 山东恒邦冶炼股份有限公司 | Resource recycling process of solid waste calcium sulfate |
| CN106044772A (en) * | 2016-05-25 | 2016-10-26 | 刘松 | Comprehensive utilization method for waste gypsum and high-sulfur coal |
| CN107324676A (en) * | 2017-07-24 | 2017-11-07 | 武汉理工大学 | The method that β semi-hydrated gypsums are prepared using low grade coal calcined phosphogypsum and carbide slurry |
| CN109467059A (en) * | 2018-12-18 | 2019-03-15 | 武汉科技大学 | A kind of Efficient utilization method of gypsum |
| CN111855604A (en) * | 2020-07-16 | 2020-10-30 | 济南裕兴化工有限责任公司 | Method for measuring conversion rate of limestone slurry in wet flue gas desulfurization |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955166B (en) * | 2009-07-20 | 2013-07-31 | 瓮福（集团）有限责任公司 | Method for decomposing semi-hydrated phosphogypsum |
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2006
- 2006-06-30 CN CNB2006100110026A patent/CN100415639C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323436B (en) * | 2008-07-21 | 2012-05-30 | 昆明理工大学 | Method for reductively decomposion of ardealite by composite reducer |
| CN101941806A (en) * | 2010-08-30 | 2011-01-12 | 瓮福（集团）有限责任公司 | Method for utilizing composite reducing agent to decompose phosphogypsum |
| CN104831076A (en) * | 2015-06-04 | 2015-08-12 | 山东恒邦冶炼股份有限公司 | Resource recycling process of solid waste calcium sulfate |
| CN106044772A (en) * | 2016-05-25 | 2016-10-26 | 刘松 | Comprehensive utilization method for waste gypsum and high-sulfur coal |
| CN107324676A (en) * | 2017-07-24 | 2017-11-07 | 武汉理工大学 | The method that β semi-hydrated gypsums are prepared using low grade coal calcined phosphogypsum and carbide slurry |
| CN107324676B (en) * | 2017-07-24 | 2019-11-26 | 武汉理工大学 | β-semi-hydrated gypsum method is prepared using low grade coal calcined phosphogypsum and carbide slurry |
| CN109467059A (en) * | 2018-12-18 | 2019-03-15 | 武汉科技大学 | A kind of Efficient utilization method of gypsum |
| CN109467059B (en) * | 2018-12-18 | 2022-05-24 | 武汉科技大学 | Efficient utilization method of gypsum |
| CN111855604A (en) * | 2020-07-16 | 2020-10-30 | 济南裕兴化工有限责任公司 | Method for measuring conversion rate of limestone slurry in wet flue gas desulfurization |
| CN111855604B (en) * | 2020-07-16 | 2023-03-14 | 济南裕兴化工有限责任公司 | Method for measuring conversion rate of limestone slurry in wet flue gas desulfurization |
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