CN101456542A - Method for reducing and decomposing phosphogypsum by carbon monoxide - Google Patents
Method for reducing and decomposing phosphogypsum by carbon monoxide Download PDFInfo
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- CN101456542A CN101456542A CNA2009100940266A CN200910094026A CN101456542A CN 101456542 A CN101456542 A CN 101456542A CN A2009100940266 A CNA2009100940266 A CN A2009100940266A CN 200910094026 A CN200910094026 A CN 200910094026A CN 101456542 A CN101456542 A CN 101456542A
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- phosphogypsum
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- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims abstract description 30
- 230000000996 additive effect Effects 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000004568 cement Substances 0.000 claims abstract description 17
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 14
- 230000023556 desulfurization Effects 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000002893 slag Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- 239000003517 fume Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 229910052602 gypsum Inorganic materials 0.000 abstract 1
- 239000010440 gypsum Substances 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 239000003245 coal Substances 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 239000005864 Sulphur Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000011507 gypsum plaster Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 241001347978 Major minor Species 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- -1 sodium-chlor, aluminium Chemical compound 0.000 description 1
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- Processing Of Solid Wastes (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a method for reducing and decomposing phosphogypsum through carbon monoxide, which comprises: pretreating the phosphogypsum, and preparing a composite additive; uniformly mixing the pretreated phosphogypsum and the composite additive according to certain proportion; and introducing CO into the mixture to reduce and decompose the phosphogypsum at a temperature of between 750 and 850 DEG C and in N2 atmosphere. The volume percentage of SO2 in tail gas is more than or equal to 10 percent, and the SO2 is directly used as qualified feed gas for producing sulfuric acid by double conversion double absorption acid production technology; a solid slag composition is CaO which is more than or equal to 70 weight percent, and can be used as cement clinker for cement production; and the dissolution rate of the gypsum is more than or equal to 98 weight percent, and the desulfurization efficiency is more than or equal to 94 weight percent.
Description
One, technical field
The present invention relates to the method that a kind of industrial residue phosphogypsum decomposes relieving haperacidity, belong to the innoxious of industrial residue phosphogypsum and resource utilization field.
Two, background technology
Phosphogypsum is the industrial residue that the Wet-process Phosphoric Acid Production process produces, and the phosphogypsum that produces with skies group Wet-process Phosphoric Acid Production process is an example, and its main component is counted with wt%: CaO 27～30, SO
3 is total37～42, SiO
28～12, Al
2O
30.1～0.3, Fe
2O
30.07～0.12, MgO 0.02～0.05, P
2O
5 is total0.8～1.4, F
Always0.2～0.6, crystal water 14～18, each composition sum is 100.The generation of phosphogypsum increases inevitably along with the increase of production of phosphate fertilizer amount, if do not have suitable treatment process then can only temporarily store up, forms the phosphogypsum heap.The phosphogypsum heap can take a large amount of soils, after rainwater soaks, and solubility P wherein
2O
5With objectionable constituent such as fluorochemical by water body environment scattering and permeating towards periphery, soil, water, atmosphere are caused severe contamination.On May 9th, 2006, Environmental Protection Administration is with the form of (2006) No. 176 literary compositions of ring letter, externally announced in 20 chemical industry comprising three ring companies, two phosphate fertilizer projects of Fu Rui company, the petrochemical industry construction project environmental risk investigation result report, first with the phosphogypsum slag qualitative be " Hazardous wastes ".Yet, contain a large amount of element sulphurs in the phosphogypsum, be a kind of abundant sulphur resource.In recent years, worldwide sulphur resource provisioning anxiety, the sulphur price is overall ascendant trend.The import volume of present China sulphur is 1,000 ten thousand t/a nearly, and the import interdependency is too high.Therefore from environmental angle and utilization of resources angle, a large amount of stackings of phosphogypsum have become the bottleneck of restriction phosphorous chemical industry Sustainable development, and the research focus in the innoxious and resource utilization field of phosphogypsum also is the problem that relevant enterprise presses for solution.At present, the effective rate of utilization of whole world phosphogypsum only is about 4.5%, and the utilization ratio of developed country's phosphogypsums such as Japan, Germany is higher relatively.With Japan is example, owing to lack plaster of paris resource in Japan, the phosphogypsum effective rate of utilization reaches more than 90%, the utilization ratio of other under-developed country's phosphogypsums is relatively very low, generally based on direct discharging (abandoning), China's phosphogypsum is still based on stacking, and effective rate of utilization is about 10%.The method of phosphogypsum utilization both at home and abroad mainly concentrates on industry, agricultural and three aspects of building materials.Phosphogypsum system producing sulfuric acid and jointly cement is a direction of can large-scale recovery utilizing phosphogypsum.As far back as 1916, the Muller of Germany and Kuhne have just developed the plaster of paris and have decomposed system producing sulfuric acid and jointly cement technology, and to have developed in succession with the plaster of paris, anhydrite and phosphogypsum be the device of raw material system producing sulfuric acid and jointly cement Britain, France, Poland, South Africa etc. thereafter.China has also carried out the development and research of long period in this regard, and coke reduction phosphogypsum is adopted in existing development research more, but since its rate of decomposition and desulfurization degree not high (rate of decomposition is meant CaSO in the phosphogypsum
4The part that has resolved into major-minor product C aO, CaS accounts for original CaSO
4The weight percent of amount; Desulfurization degree is meant CaSO in the phosphogypsum sample
4Middle S is converted into SO
2The part of being sloughed accounts for original CaSO
4The weight percent of amount), the key equipment problem is not resolved for a long time, be difficult to so far apply.In addition, also occur some in recent years and utilized coal gangue, high sulphur coal to wait the processing method of reducing and decomposing phosphogypsum, also all be in the laboratory study stage, and the suitability for industrialized production that is unrealized.The method that reduces ardealite decomposition temperature in a kind of phosphogypsum process of preparing sulfuric acid is disclosed in patent of invention CN101186281A.All be milled to particle diameter≤74 μ m with phosphogypsum, coal and by the composite by a certain percentage catalyzer of ferric oxide, silicon-dioxide, sodium-chlor, aluminium sesquioxide, ferric oxide, and temperature be 95～100 ℃ the oven dry 1.5～2.0 hours to water content less than 8wt%, above-mentioned phosphogypsum, coal, composite catalyst mix are sent into the reduction decomposition stove after evenly, temperature is 700～750 ℃ in the control stove, reacted 40～60 minutes, rate of decomposition can reach 99wt%, and desulfurization degree can reach 97.5wt%.A kind of method of utilizing the high sulphur coal reducing and decomposing phosphogypsum is disclosed in patent of invention CN1884048A.Earlier with the high sulphur coal of phosphogypsum and sulphur content 〉=3% respectively temperature be 100～110 ℃ down oven dry 1.5～2.0 hours to water content less than 8wt%, phosphogypsum that drying is crossed and high sulphur coal are in wt% then, send into the reduction decomposition stove after mixing by phosphogypsum: high sulphur coal=20:1～2, temperature is 800～1350 ℃ in the control stove, react 1.5～2.0 hours, but output SO
2The furnace gas of volumn concentration 〉=15%, can directly produce vitriolic acceptable material gas as the double conversion double absorption acid-making process, solid produces CaO 〉=70wt% in the product, can be directly as the qualified cement raw material of producing label more than No. 425.In patent of invention CN1935727A, disclose a kind of coal gangue and phosphogypsum of utilizing and produce sulfuric acid raw material-high density SO next life
2The method of flue gas and high strength cement raw material.Earlier with the high sulphur coal of phosphogypsum and sulphur content 〉=3% respectively temperature be 100～110 ℃ down oven dry 1.5～2.0 hours to water content less than 8wt%, and then phosphogypsum and coal gangue that drying is crossed sent into ball mill respectively, being milled to particle diameter≤76 μ m accounts for more than 90%, obtain phosphogypsum powder and coal gangue powder, then with phosphogypsum powder and coal gangue powder in wt%, by the phosphogypsum powder: coal gangue powder=1～10:1 batching also is mixed into compound, be 850～1350 ℃ of decomposing furnace internal heating reactions 0.5～2.0 hour with compound in temperature at last, SO
2Flue gas is used for acid-making process, and decompose slag is as cement raw material.
Three, summary of the invention
1, goal of the invention
In phosphogypsum system producing sulfuric acid and jointly cement industry, the decomposition of phosphogypsum is a key problem in technology, and the decomposition temperature that how to reduce phosphogypsum is whether phosphogypsum relieving haperacidity jointly producing cement technology can industrialized key problem.Therefore if calciner temperature is more than 1000 ℃, then the material of decomposing furnace is selected for use and is processed all and is very limited, and the decomposition temperature of phosphogypsum is dropped to have bigger practical significance below 1000 ℃.The decomposition reaction mechanism of phosphogypsum is very complicated, still is in the research exploratory stage so far, this decomposition course caloric receptivity greatly, generate CaS easily and cause desulfurization degree lower, adds suitable admixture and can reduce decomposition temperature, raising rate of decomposition and desulfurization degree greatly.The method that the purpose of this invention is to provide a kind of CO reducing and decomposing phosphogypsum; at can large-scale recovery utilizing problems such as the energy consumption height, rate of decomposition and the desulfurization degree that exist in the phosphogypsum system producing sulfuric acid and jointly cement technology of industrial residue phosphogypsum are low, with skies group high silicon content phosphogypsum (average SiO
28wt%) be object, add an amount of composite additive, with CO is that reductive agent makes phosphogypsum decompose down in relatively low temperature (750～850 ℃), reach higher rate of decomposition (more than the 98wt%) and desulfurization degree (more than the 94wt%), reclaim the sulphur resource in the phosphogypsum, finally reach energy saving purposes.
2, technical scheme
The used phosphogypsum of the present invention is the phosphogypsum that skies group Wet-process Phosphoric Acid Production process produces, and main component is counted with wt%: CaO 27～30, SO
3 is total37～42, SiO
28～12, Al
2O
30.1～0.3, Fe
2O
30.07～0.12, MgO 0.02～0.05, P
2O
5 is total0.8～1.4, F
Always0.2～0.6, crystal water 14～18, each composition sum is 100.(1) pretreated ardealite: behind the phosphogypsum natural air drying, drying is 10～30 minutes under temperature is 100～130 ℃, sloughs the above free-water of 97wt%, and the standard sieve of crossing 125 μ m obtains the phosphogypsum powder of particle diameter≤125 μ m.(2) make composite additive: composite additive is made in the following manner, and each component is all in wt%, and composite additive A composition is: SiO
22～10, Fe 10～25, Fe
2O
325～40, CaCl
220～35, Na
2CO
320～35, each component sum is 100; Composite additive B composition is: SiO
25～15, Fe 5～20, Fe
2O
310～25, CaCl
210～25, Na
2CO
310～25, NaCl 20～35, and each component sum is 100; Composite additive C composition is: SiO
210～20, Fe
2O
325～40, CaCl
230～50, ZnO 20～35, NaF
6Si 15～30, and each component sum is 100; Composite additive D composition is: SiO
22～10, Fe 5～20, Fe
2O
315～30, ZnO 10～20, CaCl
220～35, Na
2CO
315～30, NaF
6Si 5～20, and each component sum is 100.(3) batching: phosphogypsum powder and composite additive are mixed by proportioning, and each component is all in wt%, and its proportioning is phosphogypsum powder: composite additive=100:2～10, and wherein composite additive is optional a kind of among A, B, C, the D.(4) reduction decomposition: the compound of phosphogypsum powder and composite additive is sent into the reduction decomposition stove, at N
2Be rapidly heated under the atmosphere protection to temperature be 750～850 ℃, feed CO with the flow of 1～5mL/min then, and make the CO and the N of feeding
2Volume flow ratio be 1.5～3:9, and control stove in temperature be 750～850 ℃, the reaction times is 10～30 minutes, carries out SO in the tail gas with comprehensive fume component analysis instrument in the reaction process
2The online detection of concentration is with SO
2Volumn concentration 〉=10% is as reaction finishing control condition, tail gas can directly be produced vitriolic acceptable material gas as the double conversion double absorption acid-making process, the solid slag composition is CaO 〉=70wt%, can be used as cement clinker after the cooling and carry out manufacture of cement, phosphogypsum rate of decomposition 〉=98wt%, desulfurization degree 〉=94wt%.
3, Fa Ming positive effect
(1) higher phosphogypsum rate of decomposition (more than the 98wt%) and desulfurization degree (more than the 94wt%); What (2) produce contains SO
2Gas volume percentage composition 〉=10% can directly be produced vitriolic acceptable material gas as the double conversion double absorption acid-making process; (3) the solid slag composition is CaO 〉=70wt%, can be used as cement clinker after the cooling and carries out manufacture of cement; (4) technology is simple, and decomposition temperature reduces greatly.
Four, embodiment
Further specify the solution of the present invention and effect below by embodiment.
Embodiment 1: behind the phosphogypsum natural air drying, drying is 28 minutes under temperature is 105 ℃, slough the above free-water of 97wt%, the standard sieve of crossing 125 μ m obtains the phosphogypsum powder of particle diameter≤125 μ m, get above-mentioned phosphogypsum powder of 100g and composite additive A and be mixed by proportioning, each component is all in wt%, and its proportioning is phosphogypsum powder: composite additive=100:6, be placed on silica tube and send in the tube type resistance furnace, at N
2Be rapidly heated under the atmosphere protection to temperature be 780 ℃, feed CO with the flow of 3.0mL/min then, and make the CO and the N of feeding
2Volume flow ratio be 2:9, and control stove in temperature be 780 ℃, the reaction times is 13 minutes, carries out SO in the tail gas with comprehensive fume component analysis instrument in the reaction process
2SO is worked as in the online detection of concentration
2Volumn concentration reaches at 10% o'clock stops heating, and measuring the solid slag composition behind the naturally cooling is CaO=73.7wt%, and calculating the phosphogypsum rate of decomposition is 98.3wt%, desulfurization degree 94.2wt%.
Embodiment 2: behind the phosphogypsum natural air drying, drying is 15 minutes under temperature is 120 ℃, slough the above free-water of 97wt%, the standard sieve of crossing 125 μ m obtains the phosphogypsum powder of particle diameter≤125 μ m, get above-mentioned phosphogypsum powder of 100g and composite additive B and be mixed by proportioning, each component is all in wt%, and its proportioning is phosphogypsum powder: composite additive=100:5, be placed on silica tube and send in the tube type resistance furnace, at N
2Be rapidly heated under the atmosphere protection to temperature be 810 ℃, feed CO with the flow of 2.5mL/min then, and make the CO and the N of feeding
2Volume flow ratio be 1:3, and control stove in temperature be 810 ℃, the reaction times is 20 minutes, carries out SO in the tail gas with comprehensive fume component analysis instrument in the reaction process
2SO is worked as in the online detection of concentration
2Volumn concentration reaches at 10% o'clock stops heating, and measuring the solid slag composition behind the naturally cooling is CaO=74.0wt%, and calculating the phosphogypsum rate of decomposition is 98.5wt%, desulfurization degree 94.3wt%.
Embodiment 3: behind the phosphogypsum natural air drying, drying is 12 minutes under temperature is 125 ℃, slough the above free-water of 97wt%, the standard sieve of crossing 125 μ m obtains the phosphogypsum powder of particle diameter≤125 μ m, get above-mentioned phosphogypsum powder of 100g and composite additive C and be mixed by proportioning, each component is all in wt%, and its proportioning is phosphogypsum powder: composite additive=100:8, be placed on silica tube and send in the tube type resistance furnace, at N
2Be rapidly heated under the atmosphere protection to temperature be 825 ℃, feed CO with the flow of 3.5mL/min then, and make the CO and the N of feeding
2Volume flow ratio be 2:9, and control stove in temperature be 825 ℃, the reaction times is 17 minutes, carries out SO in the tail gas with comprehensive fume component analysis instrument in the reaction process
2SO is worked as in the online detection of concentration
2Volumn concentration reaches at 10% o'clock stops heating, and measuring the solid slag composition behind the naturally cooling is CaO=74.4wt%, and calculating the phosphogypsum rate of decomposition is 99.2wt%, desulfurization degree 94.5wt%.
Claims (1)
- The method of 1 one kinds of reducing and decomposing phosphogypsum by carbon monoxide comprises pretreated ardealite, makes composite additive, batching, and the reduction decomposition several steps is characterized in that:1.1 pretreated ardealite: the phosphogypsum main component is counted with wt%: CaO 27～30, SO 3 is total37～42, SiO 28～12, Al 2O 30.1～0.3, Fe 2O 30.07～0.12, MgO 0.02～0.05, P 2O 5 is total0.8～1.4, F Always0.2～0.6, crystal water 14～18, each composition sum is 100, and behind the natural air drying, drying is 10～30 minutes under temperature is 100～130 ℃, sloughs the above free-water of 97wt%, and the standard sieve of crossing 125 μ m obtains the phosphogypsum powder of particle diameter≤125 μ m;1.2 the making composite additive: composite additive is made in the following manner, each component is all in wt%, and composite additive A composition is: SiO 22～10, Fe 10～25, Fe 2O 325～40, CaCl 220～35, Na 2CO 320～35, each component sum is 100; Composite additive B composition is: SiO 25～15, Fe 5～20, Fe 2O 310～25, CaCl 210～25, Na 2CO 310～25, NaCl 20～35, and each component sum is 100; Composite additive C composition is: SiO 210～20, Fe 2O 325～40, CaCl 230～50, ZnO 20～35, NaF 6Si 15～30, and each component sum is 100; Composite additive D composition is: SiO 22～10, Fe 5～20, Fe 2O 315～30, ZnO 10～20, CaCl 220～35, Na 2CO 315～30, NaF 6Si5～20, each component sum is 100;1.3 batching: phosphogypsum powder and composite additive are mixed by proportioning, and each component is all in wt%, and its proportioning is phosphogypsum powder: composite additive=100:2～10, and wherein composite additive is optional a kind of among A, B, C, the D;1.4 reduction decomposition: the compound of phosphogypsum powder and composite additive is sent into the reduction decomposition stove, at N 2Be rapidly heated under the atmosphere protection to temperature be 750～850 ℃, feed CO with the flow of 1～5mL/min then, and make the CO and the N of feeding 2Volume flow ratio be 1.5～3:9, and control stove in temperature be 750～850 ℃, the reaction times is 10～30 minutes, carries out SO in the tail gas with comprehensive fume component analysis instrument in the reaction process 2The online detection of concentration is with SO 2Volumn concentration 〉=10% is as reaction finishing control condition, tail gas can directly be produced vitriolic acceptable material gas as the double conversion double absorption acid-making process, the solid slag composition is CaO 〉=70wt%, can be used as cement clinker after the cooling and carry out manufacture of cement, phosphogypsum rate of decomposition 〉=98wt%, desulfurization degree 〉=94wt%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103482586A (en) * | 2013-09-06 | 2014-01-01 | 北京科技大学 | Method for recycling calcium and sulfur in heavy metal chemical gypsum |
| CN109467059A (en) * | 2018-12-18 | 2019-03-15 | 武汉科技大学 | A kind of Efficient utilization method of gypsum |
| CN111498811A (en) * | 2020-03-18 | 2020-08-07 | 山东大学 | Process and device for gypsum calcination and CO coupling carbon thermal reduction |
| CN114229877A (en) * | 2022-01-04 | 2022-03-25 | 西南科技大学 | Method for decomposing phosphogypsum at low temperature |
-
2009
- 2009-01-09 CN CN2009100940266A patent/CN101456542B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103482586A (en) * | 2013-09-06 | 2014-01-01 | 北京科技大学 | Method for recycling calcium and sulfur in heavy metal chemical gypsum |
| CN103482586B (en) * | 2013-09-06 | 2015-01-28 | 北京科技大学 | Method for recycling calcium and sulfur in heavy metal chemical gypsum |
| 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 |
| CN111498811A (en) * | 2020-03-18 | 2020-08-07 | 山东大学 | Process and device for gypsum calcination and CO coupling carbon thermal reduction |
| CN114229877A (en) * | 2022-01-04 | 2022-03-25 | 西南科技大学 | Method for decomposing phosphogypsum at low temperature |
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