CN101306925A - Process for preparing modified ardealite by water-free calcining - Google Patents
Process for preparing modified ardealite by water-free calcining Download PDFInfo
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- CN101306925A CN101306925A CNA2008100586351A CN200810058635A CN101306925A CN 101306925 A CN101306925 A CN 101306925A CN A2008100586351 A CNA2008100586351 A CN A2008100586351A CN 200810058635 A CN200810058635 A CN 200810058635A CN 101306925 A CN101306925 A CN 101306925A
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- phosphogypsum
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- 238000001354 calcination Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title description 10
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical class O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 32
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004568 cement Substances 0.000 claims abstract description 18
- 239000000292 calcium oxide Substances 0.000 claims abstract description 10
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 235000012255 calcium oxide Nutrition 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000012190 activator Substances 0.000 claims description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 abstract description 3
- 229940043256 calcium pyrophosphate Drugs 0.000 abstract description 3
- 235000019821 dicalcium diphosphate Nutrition 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 abstract 1
- 238000005201 scrubbing Methods 0.000 abstract 1
- 229910052602 gypsum Inorganic materials 0.000 description 13
- 239000010440 gypsum Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 239000004566 building material Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052925 anhydrite Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000011507 gypsum plaster Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011469 building brick Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium 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
- 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 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 229940045916 polymetaphosphate Drugs 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000001038 titanium pigment Substances 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
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- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for preparing modified phosphogypsum through calcination without water scrubbing. The method is as follows: firstly, composite excitant and modifier are added into phosphogypsum and uniformly mixed, wherein, the weight percent of the phosphogypsum is between 85 and 95 percent; the weight percent of the composite excitant is between 2 and 5 percent; the weight percent of the modifier is between 3 and 10 percent; the composite excitant is green vitriol and aluminum sulphate, and the modifier is calcium oxide and cement; secondly, after uniform mixing, the mixture is dried at a drying temperature of between 100 and 110 DEG C, and the moisture of the phosphogypsum is lower than 8 percent; thirdly, the mixture enters into a calciner, is calcined for 0.5 to 1 hour at a temperature of between 150 and 300 DEG C, and is naturally cooled to prepare the modified phosphogypsum. The method decomposes and volatilizes harmful substances such as phosphor, fluorine, organic substances and so on contained in the phosphogypsum or converts the harmful substances into inert substance calcium pyrophosphate which is harmless to products, thereby not only avoiding secondary pollution but also reducing or avoiding influence of harmful chemical microconstituents contained in the phosphogypsum on the quality and the performance of the products. Moreover, the method shortens the processing time by 15 to 20 percent, saves the investment by 3 to 8 percent and reduces the energy consumption by 10 to 20 percent.
Description
Technical field
The present invention relates to phosphorous chemical industry, building material technical field, specifically describing is a kind of method of preparing modified ardealite by water-free calcining.
Background technology
Phosphogypsum is that Rock Phosphate (72Min BPL) and sulfuric acid react and the industrial residue that produces in the Wet-process Phosphoric Acid Production process, to produce 4～5 tons of phosphogypsums by the phosphoric acid that calculates 1 ton of every production, at present the quantity discharged in whole world phosphogypsum every year reaches more than 200,000,000 ton, but the utilization ratio of phosphogypsum does not surpass 10%, and the processing of phosphogypsum, disposal and comprehensive utilization have become a global difficult problem.China's phosphate fertilizer production ranks first in the world, and the phosphate fertilizer of production high density (as phosphorus ammonium, coarse whiting etc.) needs a large amount of phosphoric acid by wet processes, also can produce a large amount of phosphogypsum slags thereupon.Great majority are stored up or are toppled over, and the stacking of phosphogypsum not only takies a large amount of soils, expends a huge sum of money, and sour water leakage pollution water source, form secondary pollution.But containing abundant calcium, sulphur in the phosphogypsum again, is again valuable resource, and the phosphogypsum after the modification can be used to substitute the plaster of paris resource of growing tension.Therefore, from the angle of the environment protection and the utilization of resources, the processing of phosphogypsum slag is extremely urgent with utilization.
For eliminating the pollution of phosphogypsum to environment, make full use of resource, a lot of countries have all carried out comprehensive utilization of phosphogypsum research, at present, the country that phosphogypsum is carried out comprehensive utilization is mainly economic more developed countries such as Germany, Japan, and the country that phosphogypsum output is little, land resources is few, as countries such as Britain, France, Finland.
At present, developed country is relating to a plurality of industries aspect the phosphogypsum comprehensive utilization, wherein makes material of construction (gypsum plaster) and accounts for 45%, produces cement setting retarder 43%, produces calcium sulfate 6%, produces producing sulfuric acid and jointly cement 2%, is used for soil improvement 4%.
China starts late to the research and development of phosphogypsum utilization.The present domestic method for preparing ardealite setting retarder for cement generally is two water-half wet technologies, and phosphogypsum is made granulated product through operations such as purification, neutralization, calcining, rehydration, balling-up, and its main component is a terra alba.All contain impurity such as phosphorus, fluorine, organism in the phosphogypsum, need through washing, ageing pretreatment technology to remove.
The treatment process of phosphogypsum is disclosed in publication number CN1424273A, this method is: " at first phosphogypsum is mixed by 1: 1～1.5 weight ratio with water; became 200 purpose uniform sizing materials with ball mill grinding; with slurry and water by 1: 2～4 weight proportion dilution; the slurry after will dilute then through the one-level settling tank (long * wide * dark=20m * 4m * 3.5m) natural sedimentation; the one-level throw out; with first grade subsides gained supernatant liquor by second-level settling pond (long * wide * deeply=24m * 4m * 4m) natural sedimentation, get the two-stage precipitation thing, again that secondary sedimentation gained supernatant liquor is (long * wide * dark=30m * 4m * 4m) natural sedimentation by three grades of settling tanks, get three grades of throw outs, after at last throw outs at different levels being shoveled out natural air drying respectively, Tumbleing Dry makes finished product again.Wherein the one-level throw out is used to produce calcium phosphate, and the two-stage precipitation thing is used for production composite fertilizer or cement or building brick or plasterboard, and three grades of throw outs are used to produce vitriolate of tartar or paint.
The treatment process of phosphogypsum is disclosed in publication number CN101003422, this method is: with phosphogypsum be rich in silicon-dioxide, alchlor, the raw material of ferric oxide and coal, proportioning is by lime saturation ratio KH=0.67～1.0 in the manufacture of cement, silicate ratio n=1.7～2.7, prepare burden in aluminium-oxygen modulus P=0.8～1.7, the carbon of calcium sulfate and coal 1: 2 in molar ratio～2.5 batchings in the phosphogypsum, behind batching back combined grinding to 100～200 orders, add a certain amount of hydraulic pressure and make block material piece, to expect that piece puts into the block sintering kiln, 800～1400 ℃ of sintering 1.5～3 hours, material block sintering was cement products after through the crushing and grinding packing with coal or coal gas.The tail gas that contains sulfurous gas that kiln produces is used for producing sulfuric acid.
The treatment process of phosphogypsum is disclosed in publication number CN101050080, this method is: phosphogypsum and lime, Wingdale are mixed work in-process even, compression moulding becomes intensifier for adjusting congelation of cement after 800～1000 ℃ of calcinings according to certain ratio, mix as intensifier for adjusting congelation of cement with a certain proportion of grinding aid then.
There are problems such as the pretreatment technology one-time investment is big, energy consumption is high, the secondary pollution of sewage discharge is serious in above-mentioned technology, and product is lacked competitiveness economically.Popularize a lot of work of still needing of using in an all-round way.If adopt anhydrous calcining process both can eliminate the secondary pollution of phosphogypsum, cut down the consumption of energy, help economizing on resources, protecting environment again.
Summary of the invention
The object of the present invention is to provide a kind of method that adopts the water-free calcining phosphogypsum to produce modified ardealite, this method can be broken away from the traditional technology the old road that utilizes after phosphogypsum washing or the ageing, avoid secondary pollution, realized cleaner production, reached the purpose of energy-saving and emission-reduction.
Technical scheme of the present invention is as follows:
The present invention finishes according to the following steps:
(1) material chemical component: the main chemical compositions of phosphogypsum sees Table 1.
The main chemical compositions of table 1 phosphogypsum
| Title | CaO | SO 2 | Fe 2O 3 | Al 2O 3 | P 2O 5 | F | SiO 2 |
| Massfraction/% | 26～37 | 39～51 | 0.08～3.31 | 0.08～2.65 | 0.47～1.28 | 0.05～0.26 | 8.20～15.38 |
(2) adding of compound activator and modifying agent
Phosphogypsum at high temperature changes into CaSO4 (II type) variant, makes it to become insoluble (or microsolubility) anhydrite, though and this type of anhydrite intensity is high, extremely slow with the speed of water reaction, need to add a certain amount of exciting agent and excited.So in phosphogypsum, add compound activator (green vitriol+Tai-Ace S 150, Tai-Ace S 150=1: 1～1.5) and modifying agent (unslaked lime+cement both mass ratioes are: green vitriol:, both mass ratioes: unslaked lime: cement=2: 3～7), add-on is: phosphogypsum 85%～95%, compound activator 2～5%, modifying agent 3～10%, mixing;
(3) drying
The high-temperature flue gas that utilizes the calcining back to produce carries out drying to the phosphogypsum that adds compound activator and modifying agent, and drying temperature is controlled at 100～110 ℃, and oven dry back phosphogypsum moisture content is lower than 8%;
(4) calcining
Phosphogypsum after the oven dry is sent in circulating fluidized bed (existing installation) calcining kiln and calcined, calcining temperature is controlled at 150～300 ℃, can make in calcination process that eutectic phosphorus is converted into the inert Calcium Pyrophosphate in the phosphogypsum, partly titanium pigment is condensed into polymetaphosphate salt vitreum, has eliminated the detrimentally affect of phosphorus to the phosphogypsum performance.Fluorine also part is converted into insoluble compound and gas, also can remove impurity such as organism simultaneously, and phosphogypsum is sintered into dehydrated gyp-or the semi-hydrated gypsum that is widely used in material of construction.
SO in the modified ardealite of producing
3On content 〉=40%, fluorinion concentration＜0.5mg/L in the leach liquor, standard consistency 60%, presetting period 〉=6min, final setting time≤30min, folding strength＞2.5Mpa, ultimate compression strength 〉=4.9Mpa meets that " building materials gypsum " GB9776-88 premium grads requires and the relevant regulations of " chemical gypsum goods " HJ/T211-2005.
The major advantage that the present invention has compared with the prior art is as follows:
1, the present invention does not do washing or pre-treatment such as ageing to phosphogypsum, is the water-free calcining novel process, is suitable for all kinds of phosphogypsums, has broken away from the traditional technology the old road that utilizes after phosphogypsum washing or the ageing, has avoided secondary pollution;
2, the present invention passes through to add compound activator and properties-correcting agent and employing circulating fluidized bed calcining process in treating processes, the objectionable impurities that phosphorus contained in the phosphogypsum, fluorine, organism etc. impact product performance is decomposed volatilization or is converted into the inert substance Calcium Pyrophosphate harmless to product, both avoided secondary pollution, and reduced again or avoid in the phosphogypsum contained micro-harmful chemical component quality product, Effect on Performance;
3, the circulating fluidized bed calcining process of the present invention's employing makes full use of fume afterheat, make shorten 15～20% than conventional rotary kiln technology technology process period, investment saves 3%～8%, and energy consumption reduces by 10%～20%, realize cleaner production, reach the purpose of energy-saving and emission-reduction;
4, the present invention utilizes phosphogypsum self CaSO
4.2H
2The characteristics that O content is higher are utilized it as gypsum resource again, produce building material products such as cement setting retarder, gypsum brick, and market capacity is huge, store up problems such as the land occupation that brought and contaminate environment and have practical meaning for solving phosphogypsum;
5, the present invention promotes the development of phosphorous chemical industry recycling economy industrial chain for realizing that industrialization provides foundation.And help the automatization control of production technique and process and the raising of mechanization degree.
Embodiment
Embodiment 1:
Press phosphogypsum 91%, green vitriol 1%, Tai-Ace S 150 1%, unslaked lime 2%, the weight proportion batching of cement 5% mixes, and enters in the dryer and dries, and bake out temperature is controlled at 105 ℃, and makes phosphogypsum moisture be lower than 8%, enters calcining furnace then 200 ℃ of calcinings.The high-temperature flue gas that produces in the calcination process is recycled to dries phosphogypsum in the dryer, calcine and stop the heating and calcining stove after 0.5 hour, naturally cooling makes modified ardealite.
Product performance are as follows after measured:
SO
3Content 45%;
Fluorinion concentration 0.4mg/L in the leach liquor;
Standard consistency 60%;
Presetting period 7min;
Final setting time 28min;
Folding strength 2.6Mpa;
Ultimate compression strength 5.1Mpa;
The relevant regulations that meets the requirement of " building materials gypsum " GB9776-88 premium grads and " chemical gypsum goods " HJ/T211-2005.
Embodiment 2:
Press phosphogypsum 91%, green vitriol 1.5%, Tai-Ace S 150 1.5%, unslaked lime 2%, the weight proportion batching of cement 4% mixes, and enters in the dryer and dries, and bake out temperature is controlled at 105 ℃, and makes phosphogypsum moisture be lower than 8%.Enter calcining furnace then 300 ℃ of calcinings.The high-temperature flue gas that produces in the calcination process is recycled to dries phosphogypsum in the dryer, calcine and stop the heating and calcining stove after 0.5 hour, naturally cooling makes modified ardealite.
Product performance are as follows after measured:
SO
3Content 46%,
Fluorinion concentration 0.35mg/L in the leach liquor,
Standard consistency 60%,
Presetting period 8min,
Final setting time 29min,
Folding strength 2.7Mpa,
Ultimate compression strength 5.4Mpa,
The relevant regulations that meets the requirement of " building materials gypsum " GB9776-88 premium grads and " chemical gypsum goods " HJ/T211-2005.
Embodiment 3:
Press phosphogypsum 85%, green vitriol 2%, Tai-Ace S 150 3%, unslaked lime 3%, the weight proportion batching of cement 7% mixes, and enters in the dryer and dries, and bake out temperature is controlled at 105 ℃, and makes phosphogypsum moisture be lower than 8%.Enter calcining furnace then 200 ℃ of calcinings.The high-temperature flue gas that produces in the calcination process is recycled to dries phosphogypsum in the dryer, calcine and stop the heating and calcining stove after 0.5 hour, naturally cooling makes modified ardealite.
Product performance are as follows after measured:
SO
3Content 46%,
Fluorinion concentration 0.42mg/L in the leach liquor,
Standard consistency 61%,
Presetting period 10min,
Final setting time 30min,
Folding strength 2.8Mpa,
Ultimate compression strength 5.5Mpa,
The relevant regulations that meets the requirement of " building materials gypsum " GB9776-88 premium grads and " chemical gypsum goods " HJ/T211-2005.
Embodiment 4:
Press phosphogypsum 93%, green vitriol 1%, Tai-Ace S 150 1%, unslaked lime 2%, the weight proportion batching of cement 3% mixes, and enters in the dryer and dries, and bake out temperature is controlled at 105 ℃, and makes phosphogypsum moisture be lower than 8%.Enter calcining furnace then 300 ℃ of calcinings.The high-temperature flue gas that produces in the calcination process is recycled to dries phosphogypsum in the dryer, calcine and stop the heating and calcining stove after 0.5 hour, naturally cooling makes modified ardealite.
Product performance are as follows after measured:
SO3 content 40%,
Fluorinion concentration 0.44mg/L in the leach liquor,
Standard consistency 61%,
Presetting period 7min,
Final setting time 25min,
Folding strength 2.3Mpa,
Ultimate compression strength 5.0Mpa,
The relevant regulations that meets the requirement of " building materials gypsum " GB9776-88 premium grads and " chemical gypsum goods " HJ/T211-2005.
Claims (1)
1, a kind of method of preparing modified ardealite by water-free calcining is characterized in that being undertaken by following:
1) in phosphogypsum, adds compound activator and modifying agent, wherein phosphogypsum 85%～95%, compound activator 2～5%, modifying agent 3～10%, mixing; Compound activator is green vitriol+Tai-Ace S 150, and both mass ratioes are green vitriol: Tai-Ace S 150=1: 1～1.5; Modifying agent is unslaked lime+cement, and both mass ratioes are unslaked lime: cement=2: 3～7;
2) enter in the dryer after mixing and dry, bake out temperature is controlled at 100～110 ℃, and makes phosphogypsum moisture be lower than 8%;
3) enter calcining furnace then 150～300 ℃ of calcinings, the high-temperature flue gas that produces in the calcination process is recycled to dries phosphogypsum in the dryer, calcine after 0.5～1 hour, naturally cooling makes modified ardealite.
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| Publication Number | Publication Date |
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| CN101306925A true CN101306925A (en) | 2008-11-19 |
| CN100567192C CN100567192C (en) | 2009-12-09 |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475329B (en) * | 2009-02-09 | 2012-07-04 | 安徽德嘉新型建材有限公司 | Modified phosphogypsum powder and product thereof |
| CN103073207A (en) * | 2012-05-29 | 2013-05-01 | 中科创投(北京)科技有限公司 | Method for phosphogypsum harmless treatment and conversion into regeneration gypsum resource |
| CN103232180A (en) * | 2013-04-27 | 2013-08-07 | 丁海军 | Composition and application thereof |
| CN104176963A (en) * | 2014-08-06 | 2014-12-03 | 宣城市水东泰狮缓凝剂制品有限公司 | Phosphorus gypsum cement retarder |
| CN104628276A (en) * | 2015-02-02 | 2015-05-20 | 河南聚能新型建材有限公司 | Phosphogypsum treatment method |
| CN105347711A (en) * | 2015-10-26 | 2016-02-24 | 贵州腾峰科技有限责任公司 | Modified phosphogypsum and preparation method thereof |
| CN106145726A (en) * | 2016-05-24 | 2016-11-23 | 成都市斯贝佳科技有限公司 | The process of high-strength building gypsum prepared by a kind of ardealite |
| CN108516713A (en) * | 2018-03-16 | 2018-09-11 | 中南大学 | A kind of pretreatment of ardealite and application process |
| CN109437640A (en) * | 2018-10-25 | 2019-03-08 | 昆明理工大学 | Composite modifier for ardealite building gypsum plaster |
| CN109734341A (en) * | 2019-03-13 | 2019-05-10 | 西南科技大学 | A kind of method that ardealite physical chemistry brightened and prepared cementitious material |
| CN111664493A (en) * | 2020-05-22 | 2020-09-15 | 贵州开磷磷石膏综合利用有限公司 | Quick-heating floor heating module |
| CN113493320A (en) * | 2020-04-01 | 2021-10-12 | 云南镟淦科技有限公司 | Phosphogypsum processing technology |
| CN113816712A (en) * | 2021-10-15 | 2021-12-21 | 钟祥绿景环保科技有限公司 | Calcination-free production process of phosphogypsum environment-friendly building material |
| CN114477815A (en) * | 2022-03-03 | 2022-05-13 | 云南云天化股份有限公司 | Method for quickly whitening phosphogypsum |
| CN115849746A (en) * | 2022-12-22 | 2023-03-28 | 贵州长泰源节能建材股份有限公司 | Production method of phosphogypsum |
Family Cites Families (3)
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| CN1215011C (en) * | 2003-01-10 | 2005-08-17 | 宋才富 | Treating method of phosphogypsum |
| CN101003422B (en) * | 2007-01-17 | 2010-08-11 | 贵州大学 | New method for producing sulfuric acid and cement by using phosphogypsum |
| CN100453490C (en) * | 2007-05-16 | 2009-01-21 | 济南大学 | Intensifier for adjusting congelation of cement prepared from ardealite |
-
2008
- 2008-07-04 CN CNB2008100586351A patent/CN100567192C/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475329B (en) * | 2009-02-09 | 2012-07-04 | 安徽德嘉新型建材有限公司 | Modified phosphogypsum powder and product thereof |
| CN103073207A (en) * | 2012-05-29 | 2013-05-01 | 中科创投(北京)科技有限公司 | Method for phosphogypsum harmless treatment and conversion into regeneration gypsum resource |
| CN103073207B (en) * | 2012-05-29 | 2014-06-25 | 中科创投(北京)科技有限公司 | Method for phosphogypsum harmless treatment and conversion into regeneration gypsum resource |
| CN103232180A (en) * | 2013-04-27 | 2013-08-07 | 丁海军 | Composition and application thereof |
| CN103232180B (en) * | 2013-04-27 | 2014-07-09 | 丁海军 | Composition and application thereof |
| CN104176963A (en) * | 2014-08-06 | 2014-12-03 | 宣城市水东泰狮缓凝剂制品有限公司 | Phosphorus gypsum cement retarder |
| CN104176963B (en) * | 2014-08-06 | 2015-12-09 | 宣城市水东泰狮缓凝剂制品有限公司 | A kind of ardealite setting retarder for cement |
| CN104628276A (en) * | 2015-02-02 | 2015-05-20 | 河南聚能新型建材有限公司 | Phosphogypsum treatment method |
| CN105347711A (en) * | 2015-10-26 | 2016-02-24 | 贵州腾峰科技有限责任公司 | Modified phosphogypsum and preparation method thereof |
| CN106145726A (en) * | 2016-05-24 | 2016-11-23 | 成都市斯贝佳科技有限公司 | The process of high-strength building gypsum prepared by a kind of ardealite |
| CN108516713A (en) * | 2018-03-16 | 2018-09-11 | 中南大学 | A kind of pretreatment of ardealite and application process |
| CN109437640A (en) * | 2018-10-25 | 2019-03-08 | 昆明理工大学 | Composite modifier for ardealite building gypsum plaster |
| CN109734341A (en) * | 2019-03-13 | 2019-05-10 | 西南科技大学 | A kind of method that ardealite physical chemistry brightened and prepared cementitious material |
| CN109734341B (en) * | 2019-03-13 | 2021-05-28 | 西南科技大学 | Method for physical and chemical whitening of phosphogypsum and preparation of cementing material |
| CN113493320A (en) * | 2020-04-01 | 2021-10-12 | 云南镟淦科技有限公司 | Phosphogypsum processing technology |
| CN111664493A (en) * | 2020-05-22 | 2020-09-15 | 贵州开磷磷石膏综合利用有限公司 | Quick-heating floor heating module |
| CN113816712A (en) * | 2021-10-15 | 2021-12-21 | 钟祥绿景环保科技有限公司 | Calcination-free production process of phosphogypsum environment-friendly building material |
| CN114477815A (en) * | 2022-03-03 | 2022-05-13 | 云南云天化股份有限公司 | Method for quickly whitening phosphogypsum |
| CN114477815B (en) * | 2022-03-03 | 2023-01-31 | 云南云天化股份有限公司 | Method for rapidly whitening phosphogypsum |
| CN115849746A (en) * | 2022-12-22 | 2023-03-28 | 贵州长泰源节能建材股份有限公司 | Production method of phosphogypsum |
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