CN116425437A - Method for deeply curing soluble phosphorus and fluorine in phosphogypsum by mechanical force ball milling - Google Patents
Method for deeply curing soluble phosphorus and fluorine in phosphogypsum by mechanical force ball milling Download PDFInfo
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- CN116425437A CN116425437A CN202310384316.4A CN202310384316A CN116425437A CN 116425437 A CN116425437 A CN 116425437A CN 202310384316 A CN202310384316 A CN 202310384316A CN 116425437 A CN116425437 A CN 116425437A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 81
- 239000011574 phosphorus Substances 0.000 title claims abstract description 81
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 81
- 239000011737 fluorine Substances 0.000 title claims abstract description 80
- 238000000498 ball milling Methods 0.000 title claims abstract description 72
- 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 69
- 238000000034 method Methods 0.000 title claims abstract description 36
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims abstract 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000011575 calcium Substances 0.000 claims abstract description 30
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000002699 waste material Substances 0.000 claims abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 42
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 21
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 16
- 239000000920 calcium hydroxide Substances 0.000 claims description 16
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 16
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000010438 granite Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 96
- 239000012071 phase Substances 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000010440 gypsum Substances 0.000 abstract description 11
- 229910052602 gypsum Inorganic materials 0.000 abstract description 11
- 239000000378 calcium silicate Substances 0.000 abstract description 7
- 229910052918 calcium silicate Inorganic materials 0.000 abstract description 7
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 67
- 230000000694 effects Effects 0.000 description 27
- 239000000047 product Substances 0.000 description 25
- 238000002386 leaching Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 239000012535 impurity Substances 0.000 description 15
- 238000007711 solidification Methods 0.000 description 8
- 230000008023 solidification Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- -1 however Substances 0.000 description 6
- 239000010865 sewage Substances 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000004683 dihydrates Chemical group 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910018512 Al—OH Inorganic materials 0.000 description 1
- 229910014458 Ca-Si Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- ZHQXROVTUTVPGO-UHFFFAOYSA-N [F].[P] Chemical compound [F].[P] ZHQXROVTUTVPGO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910002056 binary alloy Inorganic materials 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
- 239000004568 cement Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VVRKSAMWBNJDTH-UHFFFAOYSA-N difluorophosphane Chemical compound FPF VVRKSAMWBNJDTH-UHFFFAOYSA-N 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/005—Preparing or treating the raw materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a method for deeply curing soluble phosphorus and fluorine in phosphogypsum by mechanical force ball milling, which comprises the following steps: phosphogypsum, a calcium curing agent and an aluminum curing agent are put into a planetary ball mill together for grinding. Compared with the prior curing method, the method does not involve macroscopic liquid phase reaction for preparing a large amount of water consumption such as slurry, does not need to process waste liquid generated by a reaction process, can realize deep curing of soluble phosphorus and fluorine in a short time, the curing rate of the soluble phosphorus can be close to 100%, the curing rate of the soluble fluorine can be more than 98%, the pH value of a product can be controlled to be neutral to weak alkaline, and the cured product has gel material phases such as semi-hydrated gypsum, calcium silicate and the like, has certain strength after curing, can be used as a material with low compressive strength requirement, and provides a basis for recycling phosphogypsum.
Description
Technical Field
The invention belongs to the technical field of slag treatment, and particularly relates to a method for deeply solidifying soluble phosphorus and fluorine in phosphogypsum by mechanical force ball milling.
Background
Phosphogypsum is solid waste residue generated when phosphoric acid is produced by adopting hydrometallurgy process in phosphorus chemical industry, and has complex composition, and the main component is dihydrate gypsum (CaSO) 4 ·2H 2 O), residual phosphoric acid, fluoride, heavy metal soluble impurities and the like have a great negative effect on the recycling of phosphogypsum. Phosphogypsum is piled up, so that a large amount of land is occupied, water eutrophication can be caused, and certain potential safety hazard is caused to the environment. The soluble phosphorus, fluorine and other impurities in phosphogypsum leaching solution are main pollutants with great influence on the environment, when rainfall is encountered, a large amount of pollutants in phosphogypsum are released by infiltration of rainwater, a waste water recovery system is not arranged in a common dry storage yard, and a large amount of waste water generated by perennial accumulation leads the total phosphorus and fluoride of surrounding groundwater and surface water to exceed the standard, so that the water quality is deteriorated. It is therefore necessary to treat soluble phosphorus and fluorine impurities that are most severely contaminated in phosphogypsum.
The main treatment method of soluble phosphorus and fluorine impurities in phosphogypsum is water washing, a large amount of impurities can be taken away by water washing, but the impurities in phosphogypsum are hidden and firmly combined, the water consumption of water washing is huge, and the economic cost is high due to the reprocessing of wastewater after water washing. Another common treatment method is to neutralize and solidify the soluble phosphorus and fluorine impurities by lime, and convert the soluble phosphorus and fluorine impurities into stable precipitates, however, lime treatment is easy to generate direct alkali pollution, and the lime neutralization has high solidification reversibility on the soluble phosphorus and fluorine impurities, and the phosphorus and fluorine returns to the soluble state when meeting acidic conditions.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for deeply curing soluble phosphorus and fluorine in phosphogypsum by mechanical ball milling, which is characterized in that a series of physicochemical reactions are carried out on a calcium curing agent, an aluminum curing agent and phosphogypsum by mechanical ball milling, so that a Ca-Al binary cation system is formed, and the Ca-Al binary cation system is combined with the soluble phosphorus and fluorine in phosphogypsum more firmly, thereby remarkably improving the curing efficiency and achieving the effect of deep curing.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the method for deeply curing soluble phosphorus and fluorine in phosphogypsum by mechanical force ball milling is provided: phosphogypsum, a calcium curing agent and an aluminum curing agent are put into a planetary ball mill together for grinding.
According to the scheme, the calcium curing agent is one or more of calcium carbonate, calcium hydroxide, artificial granite waste residue and papermaking white mud, wherein the mass percentage of the calcium-containing compound is more than 90%.
According to the scheme, the aluminum curing agent is one or a mixture of aluminum hydroxide and kaolinite, wherein the mass percentage of the aluminum-containing compound is more than 95%.
According to the scheme, the sum of the mass of the calcium curing agent and the aluminum curing agent accounts for 1-10% of the mass of phosphogypsum.
According to the scheme, the molar ratio of the calcium element in the calcium curing agent to the aluminum element in the aluminum curing agent is 3:
2. under the condition, the calcium curing agent, the aluminum curing agent and phosphogypsum are ball-milled to obtain the gabion phase.
According to the scheme, the ball milling process conditions are as follows: the ball milling rotating speed is 400-600 rpm, and the ball milling time is 1-3 h.
According to the scheme, the ball milling tank is made of zirconia, and the ball material ratio is 25-50: 1.
the invention selects specificThe method comprises the steps of deep curing soluble phosphorus and fluorine impurities in phosphogypsum by a mechanical force ball milling method through a calcium curing agent, an aluminum curing agent and phosphogypsum, continuously and completely reacting products (residual sulfuric acid and residual phosphorus components) which are not fully reacted in phosphogypsum under the action of mechanical force high-energy ball milling, forming stable precipitates of orthophosphate, calcium fluoride, fluorapatite and the like by phosphate radical and fluorine ions and the calcium curing agent, partially dehydrating calcium sulfate dihydrate serving as a main component in phosphogypsum to form a gypsum gel phase of semi-hydrated gypsum, forming a cement gel phase of calcium silicate and the like by silicate impurity components and calcium-containing components under the action of ball milling, forming a stable condensate when meeting water, preventing the overflow of soluble substances, further fixing soluble phosphorus and fluorine, reacting the aluminum curing agent and the calcium curing agent to form a Ca-Al-OH, ca-Al-Si-OH multi-element system, and F - Will be associated with OH therein - Exchange and co-location occur, soluble fluorine is further fixed, and the deep curing effect is achieved.
The invention has the beneficial effects that: compared with the prior curing method, the method does not involve macroscopic liquid phase reaction for preparing a large amount of water consumption such as slurry, does not need to process waste liquid generated by a reaction process, can realize deep curing of soluble phosphorus and fluorine in a short time, the curing rate of the soluble phosphorus can be close to 100%, the curing rate of the soluble fluorine can be more than 98%, the pH value of a product can be controlled to be neutral to weak alkaline, and the cured product has gel material phases such as semi-hydrated gypsum, calcium silicate and the like, has certain strength after curing, can be used as a material with low compressive strength requirement, and provides a basis for recycling phosphogypsum.
Drawings
FIG. 1 is a graph showing the curing effect and pH value of soluble phosphorus and fluorine in comparative example 1 under different ball milling time;
FIG. 2 is a graph showing the curing effect and pH of soluble phosphorus and fluorine at different calcium carbonate addition levels in comparative example 2;
FIG. 3 is a graph showing the curing effect and pH of soluble phosphorus and fluorine at different ball milling times in comparative example 2;
FIG. 4 is a graph showing the curing effect and pH test of soluble phosphorus and fluorine at various total addition amounts in example 1;
FIG. 5 is a graph showing the curing effect and pH of soluble phosphorus and fluorine at various calcium carbonate substitution levels in example 2;
FIG. 6 is a graph showing the curing effect and pH test of soluble phosphorus and fluorine at various artificial residues and kaolin total addition levels in example 3;
FIG. 7 shows the ball-milled products obtained in comparative example 3 and examples 1 to 3, and phosphogypsum raw materials 500r/min, wherein the ball-milled products, calcium hydroxide and aluminum hydroxide are subjected to independent ball milling for 3 hours according to Ca: al molar ratio 3: 2X-ray diffraction pattern of the product after ball milling for 3 hours at 500 r/min.
Detailed Description
The present invention will be described in further detail below with reference to the accompanying drawings, so that those skilled in the art can better understand the technical scheme of the present invention.
Phosphogypsum used in the comparative example and the embodiment of the invention is sourced from a certain phosphating plant in Hubei province, wherein the phosphogypsum comprises the following chemical components in percentage by mass: caO 27.91%, SO 3 38.86％，SiO 2 8.82％，Al 2 O 3 1.32％，P 2 O 5
1.21％，K 2 O 0.59％，F 0.56％，Fe 2 O 3 0.48％，MgO 0.29％，Na 2 O0.15%, loss on ignition 19.47%, others 0.34%. The main component is CaSO 4 ·2H 2 O、CaHPO 4 ·2H 2 O, etc.
The ball mills used in the comparative examples and examples of the present invention are: the German fly planetary ball mill is of the type Pulverisette7, the ball milling tank and the grinding balls are made of zirconia, the inner diameter of the ball milling tank is 45 cm, the diameter of the grinding balls is 1.5 cm, and the ball-to-material ratio is 25-50: 1.
comparative example 1
A method for deeply curing soluble phosphogypsum by mechanical force ball milling comprises the following steps: weighing 4g phosphogypsum in a zirconium tank, placing the zirconium tank in a planetary ball mill for ball milling without adding a curing agent, setting the ball milling rotating speed to be 600r/min, and ball milling for 3 hours.
Carrying out chemical analysis on soluble phosphorus and soluble fluorine in products obtained by ball milling for 1h and 2h, accurately weighing 2.5g of the products in a polyethylene bottle, adding 25mL of ultrapure water, oscillating for 8h at room temperature, standing for 16h, taking the leachate, filtering the leachate by a 45 mu m filter screen, and measuring the mass concentration of the soluble phosphorus and the soluble fluorine by adopting an ultraviolet spectrophotometry and an ion-selective electrode method. The curing effect of soluble phosphorus and fluorine under different ball milling time and the pH value test result of the leaching solution are shown in figure 1 (blue line shows concentration and red line shows curing rate), soluble phosphorus and fluorine impurities in phosphogypsum are cured in a large amount under the ball milling effect, the curing rates of the soluble phosphorus and fluorine are 96.64% and 80.54% respectively during ball milling for 2 hours, and the pH value of the leaching solution is increased along with the increase of ball milling time, which shows that most of the soluble phosphorus and fluorine can be cured by ball milling under the condition that no alkaline reagent is added, and possible reasons are that unreacted components exist in phosphogypsum raw materials, and the components react under the mechanical force ball milling effect.
During the ball milling process, the main component of phosphogypsum, dihydrate gypsum (CaSO 4 ·2H 2 O) is dehydrated and converted into semi-hydrated gypsum (CaSO) through physical and chemical changes 4 ·0.5H 2 O), and the semi-hydrated gypsum has self-cementing function, and is quickly solidified and hardened after meeting water, so that soluble phosphorus and fluorine are not beneficial to leaching. The method utilizes the components and the gelation property of PG (phosphogypsum) to achieve the aim of curing, does not need to add a modifying additive, has simple industry and can also keep the pH value in the weak acid range.
Comparative example 2
A method for deeply curing soluble phosphogypsum by mechanical force ball milling comprises the following steps: and (3) weighing phosphogypsum and calcium carbonate with total mass of 4g in a zirconium tank, controlling the calcium carbonate to respectively account for 1%, 3%, 5%, 7.5% and 10% of the weight of the phosphogypsum, setting the ball milling time to be 1h, and performing co-milling at the ball milling rotating speed of 600 r/min.
The soluble phosphorus and fluorine of the product were tested in the same manner as in comparative example 1. The curing effect of soluble phosphorus and fluorine under different calcium carbonate addition amounts and the result of the leachate pH value test chart are shown in figure 2 (blue line represents concentration and red line represents curing rate in the figure), the curing rates of soluble phosphorus and soluble fluorine in phosphogypsum are respectively 99.40% and 63.74% when 1% of calcium carbonate is added, and the curing rate of soluble phosphorus and soluble fluorine only fluctuates in a small range along with the continuous rise of the addition amount of calcium carbonate, and the pH value rises but does not change greatly.
Under the condition that the adding amount of calcium carbonate is 5%, the leaching concentration of soluble phosphorus is less than 0.5mg/L, the I-class water discharge standard of phosphorus in the sewage discharge standard of China is achieved, the curing effect is not greatly changed when the adding amount of calcium carbonate is continuously improved, and therefore condition optimization is carried out under the condition of 5% adding amount.
And under the condition of 5% of the added amount of calcium carbonate, weighing phosphogypsum and calcium carbonate with the total mass of 4g in a zirconium tank, setting the ball milling time to be 1h, 2h and 3h, and carrying out co-milling at the ball milling rotating speed of 600 r/min. The curing effect of soluble phosphorus and fluorine under different ball milling time and the pH value test result of the leaching solution are shown in figure 3 (blue line represents concentration and red line represents curing rate in the figure), the curing effect of the soluble phosphorus after the ball milling time is prolonged is obviously improved, the curing rate of the soluble phosphorus reaches 99.65% when the 5% calcium carbonate addition is ball-milled for 1h, the phosphorus content in the leaching solution accords with the common industrial wastewater emission standard, but the curing effect of the soluble fluorine does not change greatly with the extension of the ball milling time; the solidification rate of the soluble fluorine is 62.79 percent when ball milling is carried out for 1h, the solidification rate of the soluble fluorine is improved to 79.8 percent when the ball milling time is prolonged to 3h, and the leaching concentration is not reduced to the emission standard yet. The curing mechanism of the soluble phosphorus and fluorine in this comparative example is similar to that of comparative example 1, but calcium carbonate provides the phosphogypsum with alkalinity, effectively neutralizes the unreacted acid therein, so that the curing rate is further improved, particularly the curing of the soluble phosphorus, but the curing of fluorine is not favored in an alkaline environment.
Example 1
A method for deeply curing soluble phosphogypsum by mechanical force ball milling comprises the following steps: calcium hydroxide, aluminum hydroxide (purity 95 wt%) and phosphogypsum are put into a planetary ball mill for co-grinding, the total mass of the three is 4g, the sum of the mass of the calcium hydroxide and the mass of the aluminum hydroxide accounts for 1%, 3% and 5% of the phosphogypsum, and the calcium hydroxide and the aluminum hydroxide Ca are controlled: the Al molar ratio is 3:2, ball milling rotating speed 500r/min and ball milling time 3h.
The product was chemically analyzed for soluble phosphorus and fluorine, and the analytical procedure was the same as in comparative example 1. The curing effect and pH value test results of the soluble phosphorus and fluorine under different total addition amounts are shown in figure 4 (blue line shows concentration and red line shows curing rate in the figure), the curing rate of the soluble phosphorus and the soluble fluorine can reach 99.93% and 83.62% under the condition that the total addition amount of calcium hydroxide and aluminum hydroxide is 1%, leaching concentration steadily decreases along with the increase of the addition amount, the curing rate increases, the leaching concentration of the soluble phosphorus and the soluble fluorine is respectively 0.056mg/L and 0.99mg/L when the total addition amount is 5%, the curing rate is respectively 99.96% and 98.59%, the effects of deep phosphorus fixation and deep fluorine fixation are achieved, but the pH value also increases obviously, the pH value exceeds 9 when the total addition amount is 5%, and the leaching liquid needs to be neutralized to a certain extent at the later stage so as to reach the pH value limit requirement of sewage discharge.
Carrying out chemical analysis on soluble phosphorus and soluble fluorine of a ball-milled product under the condition that the total addition amount of calcium hydroxide and aluminum hydroxide is 5%, accurately weighing 2.5g of the product in a polyethylene bottle, adding 50mL of acetic acid-sodium acetate standard buffer (pH range is 4.93+/-0.05), oscillating for 18 hours at room temperature, taking a leaching solution, passing through a 45 mu m filter screen, measuring the mass concentration of the soluble phosphorus and the soluble fluorine in the leaching solution by adopting an ultraviolet spectrophotometry and an ion-selective electrode method, and measuring the concentration of the soluble phosphorus in the leaching solution to be 3.14mg/L and the solidification rate to be 97.62%; the concentration of the soluble fluorine is 4.08mg/L, the curing rate is 94.23%, and the curing rate of the soluble fluorine is kept at a level above 90% even under the acidic condition, so that the Ca-Al binary system plays a role in deep fixation, and is not easy to redissolve in acid.
The XRD pattern of the ball-milled product (labeled PG-CH-AH) under the condition that the sum of the mass of the calcium hydroxide and the mass of the aluminum hydroxide accounts for 5% of that of phosphogypsum is shown in figure 7, and the ball-milled product (labeled Single mill PG) is obtained by separately ball-milling the phosphogypsum raw material with 500r/min for 3 hours, wherein the mass of the calcium hydroxide and the mass of the aluminum hydroxide are calculated according to Ca: al molar ratio 3:2 after ball milling at 500r/min for 3h, the product (marked as CH-AH) was compared, and the ball milling curing mechanism was similar to phosphogypsum alone from the XRD pattern of the three co-milling: the eutectic phosphorus was completely converted, the dihydrate gypsum produced hemihydrate gypsum, calcium silicate produced, etc., except that the peak at 29.6 ° was higher than the 29.1 ° peak, whereas the phosphogypsum alone was ball milled at a lower 29.6 ° peak, at which point hydration was foundThe calcium silicate phase, which illustrates the possible occurrence of Ca-Si gel phase to further consolidate soluble phosphorus and fluorine impurities by cementation upon co-grinding of the three. At the same time, the peak of 31.7 DEG is higher than that of 31.0 DEG in the system, which is attributed to the fact that calcium hydroxide and aluminum hydroxide are ball-milled under the condition to form a product (CH-AH), the main phase of which is gabbrote (Katonite), and the chemical formula of which is Ca 3 Al 2 (OH) 12 Soluble phosphorus and fluorine impurity anions in phosphogypsum can enter Ca 3 Al 2 (OH) 12 Replacement of OH - And with OH - Co-location occurs to deeply cure the soluble phosphorus fluorine.
The cured product of this example has binder phases such as semi-hydrated gypsum and hydrated calcium silicate (as can be seen in XRD pattern of FIG. 7), and has a certain strength after curing, and can be used as binder with low compressive strength requirement.
Example 2
A method for deeply curing phosphogypsum soluble phosphorus fluoride by mechanical force ball milling is similar to that of example 1, in order to reduce the pH value of a ball milling product, calcium carbonate is adopted to replace calcium hydroxide partially or completely for ball milling, and Ca is adopted as follows: al molar ratio 3:2, 5% of the total addition amount is added and is co-ground with phosphogypsum, the ball milling parameters are set to be the same as that of the example 1, and the substitution amounts are respectively 50% and 100% (mole percent).
The curing effect and the pH value test results of the soluble phosphorus and fluorine under different calcium carbonate substitution amounts are shown as 5 (blue line represents concentration and red line represents curing rate in the figure), 50% (mol percent) of calcium carbonate is used for replacing calcium hydroxide, and the curing rates of the soluble phosphorus and the soluble fluorine are 99.95% and 82.22% respectively; the solidification rate of soluble phosphorus is 99.97% and 90.32% when completely replacing calcium hydroxide, and the pH value of ball milling products is obviously reduced to the discharge standard (respectively reduced to 8.72 and 8.49 and lower than the pH limit of sewage discharge) under the two replacement amounts. The reason for the reduced rate of soluble fluorine is that 50% calcium carbonate can not or only generate a small amount of calcium-aluminum complex after replacement, the binary cation system is less formed, and the curing of fluorine ions is mainly based on calcium combination to form calcium fluoride and neutralization under alkaline conditions. After complete replacement, the binary cation system is reformed, the fixing effect on fluorine is stronger, and the concentration of phosphorus and fluorine in the leaching solution reaches the emission standard.
In the embodiment, when calcium carbonate is adopted to replace calcium hydroxide to carry out ball milling, the XRD pattern of a product (marked as PG-CC-AH) obtained after ball milling for 3 hours at 500r/min is shown in figure 7, the system still generates gel phases such as semi-hydrated gypsum and concretion phases to concrete soluble phosphorus and fluorine impurities in phosphogypsum, and simultaneously generates a calcium-aluminum binary cation system to further solidify the soluble phosphorus and fluorine, so that the solidifying effect of the soluble phosphorus and fluorine is kept at a higher level.
Example 3
A method for deeply curing soluble phosphogypsum by mechanical force ball milling comprises the following steps: artificial granite residues (calcium carbonate content 90%) and kaolin (according to Al are used 2 O 3 39.5% by mass of aluminum) as a calcium-based curing agent and an aluminum-based curing agent, respectively, and phosphogypsum raw materials, and the calcium-based curing agent and the aluminum-based curing agent Ca: al molar ratio is 3:2, ball milling parameters are set to be the same as that of the example 1, and the total mass percentages of the calcium curing agent and the aluminum curing agent are respectively set to be 3%, 5%, 7.5% and 10%.
The results of the soluble phosphorus and fluorine curing effect and the pH value test under the total addition of different artificial sentry residues and kaolin are shown in FIG. 6 (the blue line shows the concentration and the red line shows the curing rate in the figure), and the soluble phosphorus and the soluble fluorine of the embodiment are limited by the activity and the components, and the curing rate is lower than that of a pure reagent, but the effect is still higher than that of a comparative example 2, and it is presumed that a binary Ca-Al cation system can be formed under the method of the embodiment, or more gel phases are formed, and the curing rate is also improved along with the increase of the addition of the two, the curing rate of the soluble phosphorus reaches 99.97% under the total addition of 10%, the effect of deep phosphorus fixation can be achieved, the curing rate of the soluble fluorine is 84.75%, the pH value is 8.40, the pH value is neutral to weak alkaline, and the fluorine ion concentration of the leaching solution does not reach the sewage discharge standard, but the soluble fluorine can be further fixed by increasing the addition amount or by strengthening the ball milling condition, and the discharge standard is reached.
When the total mass percentage of the calcium curing agent and the aluminum curing agent in the embodiment is set to be 5%, XRD patterns (shown in figure 7) of products (PG-CS-KL) obtained by ball milling for 3 hours at 500r/min can be seen that peaks of 29.6 degrees and 31.7 degrees are increased, because silicon-containing components in kaolin are compared with gel such as calcium silicate hydrate and the like in ball milling materials, and soluble phosphorus and fluorine are wrapped and solidified, so that the soluble phosphorus and fluorine are not easy to dissolve, the curing efficiency is improved, and meanwhile, a gelled product with certain strength can be prepared.
Comparative example 3
A method for deeply curing soluble phosphogypsum by mechanical force ball milling comprises the following steps: weighing calcium hydroxide and aluminum hydroxide with the total mass of 4g, wherein Ca: the Al molar ratio is 3:2, ball milling for 3 hours at 500r/min to obtain a Ca-Al synthetic product, then weighing phosphogypsum and Ca-Al synthetic product accounting for 5% of the mass of phosphogypsum, adding 2.5g of the total mass of the phosphogypsum and the Ca-Al synthetic product into a polyethylene bottle, then adding 25mL of ultrapure water, oscillating for 8 hours at room temperature, standing for 16 hours, taking the leaching solution, filtering the leaching solution by a 45 mu m filter screen, and analyzing the concentration of soluble phosphorus and the concentration of soluble fluorine of the leaching solution by adopting the method of comparative example 1, wherein the concentration of the soluble phosphorus in the leaching solution is 0.0082mg/L, and the solidification rate is 99.97%; the concentration of soluble fluorine is 0.98mg/L, the solidification rate is 98.61%, the deep solidification effect is achieved, but the pH value is 9.81, and the standard of sewage discharge is not met.
The precipitate (PG+ (CH-AH)) was dried at 60℃overnight and then ground for XRD analysis, the result being shown in FIG. 7, the main phase of which was CaHPO 4 ·2H 2 O is a eutectic phosphorus structure in phosphogypsum, is extremely easy to decompose and return to an ionic state when meeting acid, and has strong reversibility.
Claims (7)
1. A method for deeply curing soluble phosphorus and fluorine in phosphogypsum by mechanical force ball milling is characterized by comprising the following steps: phosphogypsum, a calcium curing agent and an aluminum curing agent are put into a planetary ball mill together for grinding.
2. The method for deep curing soluble phosphorus and fluorine in phosphogypsum by mechanical force ball milling of claim 1, which is characterized in that: the calcium curing agent is one or more of calcium carbonate, calcium hydroxide, artificial granite waste residue and papermaking white mud, wherein the mass percentage of the calcium-containing compound is more than 90%.
3. The method for deep curing soluble phosphorus and fluorine in phosphogypsum by mechanical force ball milling of claim 1, which is characterized in that: the aluminum curing agent is one or a mixture of aluminum hydroxide and kaolinite, wherein the mass percentage of the aluminum-containing compound is more than 95%.
4. The method for deep curing soluble phosphorus and fluorine in phosphogypsum by mechanical force ball milling of claim 1, which is characterized in that: the sum of the mass of the calcium curing agent and the aluminum curing agent accounts for 1-10% of the mass of phosphogypsum.
5. The method for deep curing soluble phosphorus and fluorine in phosphogypsum by mechanical force ball milling of claim 1, which is characterized in that: the molar ratio of the calcium element in the calcium-based curing agent to the aluminum element in the aluminum-based curing agent is 3:2.
6. the method for deep curing soluble phosphorus and fluorine in phosphogypsum by mechanical force ball milling of claim 1, which is characterized in that: the ball milling process conditions are as follows: the ball milling rotating speed is 400-600 rpm, and the ball milling time is 1-3 h.
7. The method for deep curing soluble phosphorus and fluorine in phosphogypsum by mechanical force ball milling of claim 1, which is characterized in that: the ball milling tank is made of zirconia, and the ball material ratio is 25-50: 1.
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| Title |
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| 新谷昌之等: "メカノケミカル法によるペルフルオロオクタンスルホン酸（PFOS）およびペルフルオロオクタン酸（PFOA）の分解", 《化学工学論文集》, vol. 34, no. 5, 31 December 2008 (2008-12-31), pages 540 * |
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