CN103755182A - Ardealite cementing material and preparation method thereof - Google Patents
Ardealite cementing material and preparation method thereof Download PDFInfo
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- CN103755182A CN103755182A CN201410024353.5A CN201410024353A CN103755182A CN 103755182 A CN103755182 A CN 103755182A CN 201410024353 A CN201410024353 A CN 201410024353A CN 103755182 A CN103755182 A CN 103755182A
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- phosphogypsum
- ardealite
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- flyash
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003245 coal Substances 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 89
- 239000010881 fly ash Substances 0.000 claims description 29
- 238000001879 gelation Methods 0.000 claims description 21
- 239000003610 charcoal Substances 0.000 claims description 13
- 239000011812 mixed powder Substances 0.000 claims description 12
- 239000008188 pellet Substances 0.000 claims description 12
- 238000005070 sampling Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004568 cement Substances 0.000 abstract description 31
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000002440 industrial waste Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000010883 coal ash Substances 0.000 abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 12
- 239000002893 slag Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011083 cement mortar Substances 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 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
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000011507 gypsum plaster Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002367 phosphate rock Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- UJXVAJQDLVNWPS-UHFFFAOYSA-N [Al].[Al].[Al].[Fe] Chemical compound [Al].[Al].[Al].[Fe] UJXVAJQDLVNWPS-UHFFFAOYSA-N 0.000 description 1
- JNVCSEDACVAATK-UHFFFAOYSA-L [Ca+2].[S-]SSS[S-] Chemical group [Ca+2].[S-]SSS[S-] JNVCSEDACVAATK-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910001569 aluminium mineral Inorganic materials 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- BDWFYHUDXIDTIU-UHFFFAOYSA-N ethanol;propane-1,2,3-triol Chemical compound CCO.OCC(O)CO BDWFYHUDXIDTIU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910021326 iron aluminide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 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
- 230000002285 radioactive effect Effects 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses an ardealite cementing material and a preparation method thereof, which belongs to the technical field of ardealite, coal ash treatment and utilization and building materials. The ardealite cementing material is prepared by uniformly mixing and grinding ardealite, coal ash, coal and carbon as main raw materials, roasting for 30-50 minutes at 1,200-1,250 DEG C, and quenching to the room temperature so as to obtain a product. Ardealite and coal ash are roasted to prepare the ardealite cementing material, not only is a way for utilization of industrial wastes provided, is waste turned into wealth, are the ardealite recycling and secondary pollution problems thoroughly solved, and is the burden to the environment alleviated, but also the demand amount of natural raw materials in the cement industry is reduced, the cost is lowered, the situation of energy consumption and resource shortage is alleviated, and the ardealite cementing material is a green environment-friendly type cementing material with low carbon emission, and has good economic and social benefits.
Description
Technical field
The present invention relates to a kind of Phosphogypsum based Gelation Material and preparation method thereof, belong to phosphogypsum, flyash processing and utilizing and building material technical field.
Background technology
Phosphogypsum is that sulphur dioxide of phosphor chemical industry sulfuric acid reacts with Rock Phosphate (72Min BPL), the acid solid waste producing in Wet-process phosphoric acid (WPPA) process, and main component is CaSO
42H
2o.Phosphogypsum is except containing CaSO
4outward, also contain multiple harm environment and the biological detrimental impurity such as a small amount of undecomposed ground phosphate rock, the not phosphoric acid, Calcium Fluoride (Fluorspan), iron aluminide, acid non-soluble substance of washes clean and potential radioactive element radium (Ra), uranium (U), thorium (Th), cause current utilization ratio very low, a large amount of phosphogypsums of failing to utilize conventionally adopt outdoor storing up or the direct processing mode of discharge into sea, terrestrial environment and ocean are all caused to larger pollution, had a strong impact on the mankind's living environment.In May, 2006, China State Environmental Protection Administration in " ring letter (2006) No. 176 literary compositions " by qualitative phosphogypsum be Hazardous wastes.
According to statistics, 1 ton of P of every production
2o
5phosphoric acid approximately produces 4.8～5.5t phosphogypsum.The phosphoric acid salt director of the Institute Borrow of U.S. Florida Clifford is revealed on " within 2010, Chinese international phosphogypsum is stacked and comprehensive utilization technique exploitation and popularization symposial ", whole world industrial by-product phosphogypsum is stacked total amount and has been reached 5,600,000,000 t at present, every annual meeting increases 1.1～1.5 hundred million t newly, and newly-increased quantity also can be double during 2025 to the year two thousand forty.The current phosphogypsum annual emissions of China accounts for 1/3 left and right of world's quantity discharged, and utilization ratio also not enough total amount 10%.The accumulation of a large amount of phosphogypsums is serious harm ecotope around not only, and brings huge pressure to the Sustainable development of phosphorous chemical industry enterprise.Therefore, the disposal of resources utilization of phosphogypsum has become the focus of whole world research, how phosphogypsum safety is effectively disposed and to be utilized, and becomes main purpose of the present invention.
In recent years, the exploitation of phosphogypsum mainly concentrate on manufacture producing sulfuric acid and jointly cement and lime, cement setting retarder, ammonium sulfate and potassium sulfate and in agricultural as soil improvement agent, sulfur fertilizer and calcareous fertilisers etc.Wherein utilizing application of ardealite as cement retardant and producing sulfuric acid and jointly cement processed is the main direction of current phosphogypsum recycling.
Discussion on technology for production of SA with joint product cement from phosphogypsum produces sulfuric acid and cement exists more problem from the case history building up at present both at home and abroad, as: technique hear rate is high, throughput is low, easily even obstruction of ring formation, bonding in calcining kiln of material, the ventilation of kiln is obviously worsened, fuel combustion is incomplete, and output declines to a great extent.The cement clinker performance of producing is bad, and unstable product quality, does not reach relevant criterion.On the other hand, the technology of utilizing phosphogypsum to manufacture producing sulfuric acid and jointly lime also exists obtained lime sulfur-bearing too high, causes lime to be utilized, and causes the waste of resource and produces secondary pollution problems.Therefore, actively seek phosphogypsum new utilize method, improve its content in product application, be the fundamental way that finally solves phosphogypsum problem.
The present invention is different with cement technology from Discussion on technology for production of SA with joint product cement from phosphogypsum production sulfuric acid, adopts at high temperature calcining and decomposing generation of phosphogypsum CaO, with the SiO in phosphogypsum and flyash
2, Al
2o
3there is chemical reaction generation and contain C
2s, C
3s and C
3the phosphogypsum based cementitious material of the aluminosilicate minerals such as A, this material and Portland clinker mix and can make 28 days ultimate compression strength gelling material far above skillful material strength of cement by 4:6.Impurity in the process of high-temperature calcination simultaneously in phosphogypsum can form insoluble salt, thereby reduces the disadvantageous effect of phosphogypsum to cement performance.Add suitable charcoal component to contribute to the calcining and decomposing of phosphogypsum.But the present invention is different with cement technology from Discussion on technology for production of SA with joint product cement from phosphogypsum production sulfuric acid, and decomposing ardealite rate is less demanding, its undecomposed bassanite (anhydrous CaSO
4) can be used as cement setting retarder and be used, saved the plaster of paris, further save resource, and contributed to the raising of strength of cement.The recyclable sulfuric acid of preparing of flue gas that the calcining of this technology produces.
Active cement mixture prepared by currently available technology mainly contains silicon ash, slag, slag and flyash etc., and the activity of silicon ash and slag is higher, but price is also more expensive.Slag and flyash activity are relatively low, and prior art generally adopts gypsum to do activity excitant, and price is not cheap yet.
Based on the high carrying capacity of environment of Cement industry, high energy gamma source, consume present situation, the present invention utilizes industrial solid wastes-phosphogypsum and flyash calcining preparation Phosphogypsum based Gelation Material, and this has very important theory significance and good economy, society and environmental benefit for energy-conservation, the reduction of discharging that realize the utilization of resources of phosphogypsum, the Sustainable development that promotes phosphate fertilizer industry green, health and building material industry.
Summary of the invention
The object of the invention is to propose a kind of gelling material that phosphogypsum fires and preparation method thereof of utilizing, utilize the SiO in CaO and phosphogypsum and the flyash that phosphogypsum produces in high-temperature calcination decomposition course
2, Al
2o
3react and generate various silicate and aluminium mineral material, utilize undecomposed CaSO in phosphogypsum simultaneously
4replace the plaster of paris as cement setting retarder, preparation Phosphogypsum based Gelation Material, this Phosphogypsum based Gelation Material is made by following raw material, and each raw material and weight percent are: phosphogypsum 70～90%, coal, charcoal 10～20%, flyash 0～10%.
The preparation method who another object of the present invention is to provide described Phosphogypsum based Gelation Material, specifically comprises the steps:
(1) by grinding to granularity after phosphogypsum, coal, charcoal and flyash dry mixed, be the mixed powder that 0.08mm sieve screen over-size is less than 10%;
(2) in the ratio of 0.15 ~ 0.25ml/g, in water, add mixed powder, then make the pellet that diameter is 1～2cm;
(3) by the pellet obtaining in step (2), in temperature, be to calcine 30～50min at 1200～1250 ℃, after taking-up, be chilled to room temperature, grinding to 400 in sampling machine ± 10m
2/ kg, obtains desired product.
The invention has the beneficial effects as follows: the present invention has become the phosphogypsum that is difficult at present to dispose in addition recycling of a kind of useful green structural material, reduced the demand of Cement industry to natural matter, reduce production costs, effectively alleviate energy consumption and alleviated the tense situation of resource, be a kind of novel environmental type building materials, have significant Social benefit and economic benefit.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details, but protection scope of the present invention is not limited to described content.
Embodiment 1
Phosphogypsum based Gelation Material described in the present embodiment, is prepared by weight by following raw material: phosphogypsum 85%, coal, charcoal 10%, flyash 5%, the main chemical compositions of phosphogypsum used, flyash is as shown in table 1.
The main chemical constitution of table 1 phosphogypsum, flyash
Note: "-" be not for detecting.
Described in the present embodiment, the preparation method of Phosphogypsum based Gelation Material, specifically comprises the steps:
(1) by phosphogypsum, coal, charcoal and flyash dry mixed grinding to granularity, be the mixed powder that 0.08mm sieve screen over-size is less than 10%;
(2) in the ratio of 0.15ml/g, add water to make the pellet that diameter is 1cm mixed powder;
(3) by the pellet obtaining in step (2), in temperature, be to calcine 30min at 1200 ℃, after taking-up, be chilled to room temperature, grinding to 400 in sampling machine ± 10m
2/ kg, obtains desired product.
The main chemical constitution of the Phosphogypsum based Gelation Material that the present embodiment prepares is (wt%):
CaO：47.19；SiO
2：29.66；MgO：0.6；Fe
2O
3：1.89；Al
2O
3：4.53；SO
3：11.6；
f-CaO：0.089。
In this example, the decomposing ardealite rate of prepared calcined phosphogypsum gelling material is: 70.41%.
Calcined phosphogypsum gelling material prepared in 40% example is mixed with 60% Portland clinker, moulding in the die trial of 30mm × 30mm × 30mm after stirring in cement mortar mixer, (temperature is controlled at 20 ± 1 ℃ to cement standard maintaining box, relative humidity is greater than 90%) in maintenance to 3d and 28d length of time, its ultimate compression strength is: 3d-46.35 MPa, 28d-92.70 MPa.
Embodiment 2
Phosphogypsum based Gelation Material described in the present embodiment, is prepared by weight by following raw material: phosphogypsum 85%, coal, charcoal 15%, flyash 0, the main chemical compositions of phosphogypsum used, flyash is as shown in table 2.
The main chemical constitution of table 2 phosphogypsum, % flyash
Note: "-" be not for detecting.
Described in the present embodiment, the preparation method of Phosphogypsum based Gelation Material, specifically comprises the steps:
(1) by phosphogypsum, coal, charcoal and flyash dry mixed grinding to granularity, be the mixed powder that 0.08mm sieve screen over-size is less than 10%;
(2) in the ratio of 0.25ml/g, mixed powder is added to the water and makes the pellet that diameter is 2cm;
(3) by the pellet obtaining in step (2), in temperature, be to calcine 40min at 1230 ℃, after taking-up, be chilled to room temperature, grinding to 400 in sampling machine ± 10m
2/ kg, obtains desired product.
The main chemical constitution of the Phosphogypsum based Gelation Material that the present embodiment prepares is (wt%):
CaO：52.61；SiO
2：28.23；MgO：0.72；Fe
2O
3：1.06；Al
2O
3：2.88；SO
3：7.91；
f-CaO：0.048。
In this example, the decomposing ardealite rate of prepared calcined phosphogypsum gelling material is: 79.82%.
Calcined phosphogypsum gelling material prepared in 40% example is mixed with 60% Portland clinker, moulding in the die trial of 30mm × 30mm × 30mm after stirring in cement mortar mixer, (temperature is controlled at 20 ± 1 ℃ to cement standard maintaining box, relative humidity is greater than 90%) in maintenance to 3d and 28d length of time, its ultimate compression strength is: 3d-49.11 MPa, 28d-67.86 MPa.
Embodiment 3
Phosphogypsum based Gelation Material described in the present embodiment, is prepared by weight by following raw material: phosphogypsum 90%, coal, charcoal 10%, flyash 0%, the main chemical compositions of phosphogypsum used, flyash is as shown in table 3.
The main chemical constitution of table 3 phosphogypsum, flyash
Note: "-" be not for detecting.
Described in the present embodiment, the preparation method of Phosphogypsum based Gelation Material, specifically comprises the steps:
(1) by phosphogypsum, coal, charcoal and flyash dry mixed grinding to granularity, be the mixed powder that 0.08mm sieve screen over-size is less than 10%;
(2) in the ratio of 0.2ml/g, mixed powder is added to the water and makes the pellet that diameter is 1.5cm;
(3) by the pellet obtaining in step (2), in temperature, be to calcine 50min at 1250 ℃, after taking-up, be chilled to room temperature, grinding to 400 in sampling machine ± 10m
2/ kg, obtains desired product.
The main chemical constitution of the Phosphogypsum based Gelation Material that the present embodiment prepares is (wt%):
CaO：52.38；SiO
2：27.14；MgO：0.84；Fe
2O
3：1.06；Al
2O
3：2.34；SO
3：10.56；
f-CaO：0.071。
In this example, the decomposing ardealite rate of prepared calcined phosphogypsum gelling material is: 73.06%.
Calcined phosphogypsum gelling material prepared in 40% example is mixed with 60% Portland clinker, moulding in the die trial of 30mm × 30mm × 30mm after stirring in cement mortar mixer, (temperature is controlled at 20 ± 1 ℃ to cement standard maintaining box, relative humidity is greater than 90%) in maintenance to 3d and 28d length of time, its ultimate compression strength is: 3d-38.88MPa, 28d-72.18MPa.
Embodiment 4
Phosphogypsum based Gelation Material described in the present embodiment, is prepared by weight by following raw material: phosphogypsum 70%, coal, charcoal 20%, flyash 10%, the main chemical compositions of phosphogypsum used, flyash is as shown in table 4.
The main chemical constitution of table 4 phosphogypsum, flyash
Described in the present embodiment, the preparation method of Phosphogypsum based Gelation Material, specifically comprises the steps:
(1) by phosphogypsum, coal, charcoal and flyash dry mixed grinding to granularity, be the mixed powder that 0.08mm sieve screen over-size is less than 10%;
(2) in the ratio of 0.2ml/g, mixed powder is added to the water and makes the pellet that diameter is 1cm;
(3) by the pellet obtaining in step (2), in temperature, be to calcine 35min at 1220 ℃, after taking-up, be chilled to room temperature, grinding to 400 in sampling machine ± 10m
2/ kg, obtains desired product.
The main chemical constitution of the Phosphogypsum based Gelation Material that the present embodiment prepares is (wt%):
CaO：47.27；SiO
2：16.60；MgO：0.44；Fe
2O
3：2.67；Al
2O
3：2.73；SO
3：3.01
f-CaO：0.0059。
In this example, the decomposing ardealite rate of prepared calcined phosphogypsum gelling material is: 92.43%.
Calcined phosphogypsum gelling material prepared in 40% example is mixed with 60% Portland clinker, moulding in the die trial of 30mm × 30mm × 30mm after stirring in cement mortar mixer, (temperature is controlled at 20 ± 1 ℃ to cement standard maintaining box, relative humidity is greater than 90%) in maintenance to 3d and 28d length of time, its ultimate compression strength is: 3d-42.96MPa, 28d-80.04MPa.
In practice, due to cost, the reasons such as technique make the decomposition completely of phosphogypsum very difficult, in the present invention, the decomposing ardealite rate of prepared calcined phosphogypsum base high-activity gelled material is between 70%-80%, in to the influence factor of decomposing ardealite, gac volume is maximum influence factor, next is followed successively by calcining temperature, soaking time, doping quantity of fly ash, the temperature that pure phosphogypsum starts to decompose is about 1000～1030 ℃ of left and right, the temperature of decomposing is completely more than 1300 ℃, gac and flyash be added in the decomposition efficiency that has improved to a certain extent phosphogypsum, in the present invention, with phosphogypsum, be not decomposed into target completely, only be controlled in a rational scope, undecomposed CaSO
4can be used as cement setting retarder and be used, to reduce or need not mix gypsum outward, when economizing on resources, prepare highly active gelling material.In embodiment 1 ~ 4, adopt glycerin-ethanol method to show the measurement result of prepared product free ca: content is all less than 1%, meets the products standards of gelling material.
Embodiment 5(contrast experiment)
Respectively neat portland cement grog, 40% slag are mixed with 60% Portland clinker (chemical composition is in Table 5), moulding in the die trial of 30mm × 30mm × 30mm after stirring in cement mortar mixer, (temperature is controlled at (20 ± 1) ℃ to cement standard maintaining box, relative humidity is greater than 90%) in maintenance to 3d and 28d length of time, measure its ultimate compression strength and be respectively:
Neat portland cement grog: 3d-65.78MPa, 28d-75.92MPa;
The silicate mine slag cement of fine slag contents 40%: 3d-39.74MPa, 28d-46.00MPa;
The main chemical constitution of table 5 Portland clinker and slag
Can find out, more than all having exceeded 38MPa by the 3d ultimate compression strength of calcined phosphogypsum gelling material (example 1 ~ 4) sample of preparing, approached the silicate mine slag cement of fine slag contents 40%, along with the prolongation in the length of time, ultimate compression strength further increases substantially, and 28d intensity all substantially exceeds the silicate mine slag cement of fine slag contents 40%, even approaches or exceed the intensity level of neat portland cement grog sample, thereby the gelling material of utilizing phosphogypsum to fire in the present invention has possessed high activity.
The present invention has become the phosphogypsum that is difficult at present to dispose in addition recycling of a kind of useful green structural material, and really having accomplished turns waste into wealth.This invention is organically molten being integrated of development with Materials science by industrial waste disposal, not only thoroughly solved the secondary pollution problem of phosphogypsum producing sulfuric acid and jointly cement processed and lime, but also reduced the demand of Cement industry to natural matter, that the industrial wastes such as phosphogypsum, flyash are disposed to the breakthrough utilizing, the great demand that meets civil engineering material and environmental science Sustainable development, has significant scientific meaning and application prospect.
Claims (2)
1. a Phosphogypsum based Gelation Material, is characterized in that: this Phosphogypsum based Gelation Material is made by following raw material, and each raw material and weight percent are: phosphogypsum 70～90%, coal, charcoal 10～20%, flyash 0～10%.
2. the preparation method of Phosphogypsum based Gelation Material claimed in claim 1, is characterized in that specifically comprising the steps:
(1) by grinding to granularity after phosphogypsum, coal, charcoal and flyash dry mixed, be the mixed powder that 0.08mm sieve screen over-size is less than 10%;
(2) in the ratio of 0.15 ~ 0.25ml/g, in water, add mixed powder, then make the pellet that diameter is 1～2cm;
(3) by the pellet obtaining in step (2), in temperature, be to calcine 30～50min at 1200～1250 ℃, after taking-up, be chilled to room temperature, grinding to 400 in sampling machine ± 10m
2/ kg, obtains desired product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106116411A (en) * | 2016-06-26 | 2016-11-16 | 仇颖莹 | A kind of preparation method of Binder Materials |
| CN108002724A (en) * | 2017-12-06 | 2018-05-08 | 马鞍山拓锐金属表面技术有限公司 | A kind of method that two steps calcining prepares ardealite based cementitious material |
| CN113061011A (en) * | 2021-04-19 | 2021-07-02 | 贵州理工学院 | Method for manufacturing red mud-modified phosphogypsum mine filling material |
| CN114907035A (en) * | 2022-05-09 | 2022-08-16 | 贵州大学 | Preparation method of phosphogypsum-based multipurpose gelling precursor |
-
2014
- 2014-01-16 CN CN201410024353.5A patent/CN103755182A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 朱丽苹 等: "磷石膏热分解技术研究", 《粉煤灰》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106116411A (en) * | 2016-06-26 | 2016-11-16 | 仇颖莹 | A kind of preparation method of Binder Materials |
| CN108002724A (en) * | 2017-12-06 | 2018-05-08 | 马鞍山拓锐金属表面技术有限公司 | A kind of method that two steps calcining prepares ardealite based cementitious material |
| CN113061011A (en) * | 2021-04-19 | 2021-07-02 | 贵州理工学院 | Method for manufacturing red mud-modified phosphogypsum mine filling material |
| CN114907035A (en) * | 2022-05-09 | 2022-08-16 | 贵州大学 | Preparation method of phosphogypsum-based multipurpose gelling precursor |
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