CN117447170A - Phosphogypsum slag-based functional material and method for solidifying/stabilizing heavy metal polluted water or soil by using phosphogypsum slag-based functional material - Google Patents
Phosphogypsum slag-based functional material and method for solidifying/stabilizing heavy metal polluted water or soil by using phosphogypsum slag-based functional material Download PDFInfo
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- CN117447170A CN117447170A CN202311391556.3A CN202311391556A CN117447170A CN 117447170 A CN117447170 A CN 117447170A CN 202311391556 A CN202311391556 A CN 202311391556A CN 117447170 A CN117447170 A CN 117447170A
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- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 84
- 239000002893 slag Substances 0.000 title claims abstract description 83
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000002689 soil Substances 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 23
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 27
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 27
- 239000004571 lime Substances 0.000 claims abstract description 27
- 238000007711 solidification Methods 0.000 claims description 14
- 230000008023 solidification Effects 0.000 claims description 14
- 230000006641 stabilisation Effects 0.000 claims description 13
- 238000011105 stabilization Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 abstract description 25
- 239000002910 solid waste Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 239000004566 building material Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000007596 consolidation process Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 31
- 229910052793 cadmium Inorganic materials 0.000 description 12
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 239000002920 hazardous waste Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910001653 ettringite Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 208000005882 cadmium poisoning Diseases 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000404 calcium aluminium silicate Substances 0.000 description 1
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 1
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 1
- 229940078583 calcium aluminosilicate Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 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
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/143—Calcium-sulfate
- C04B22/144—Phosphogypsum
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses phosphogypsum slag-based functional material and a method for solidifying/stabilizing heavy metal polluted water or soil by using the phosphogypsum slag-based functional material, and belongs to the technical field of heavy metal polluted water and soil treatment. The phosphogypsum slag-based functional material comprises main components such as phosphogypsum, blast furnace slag, lime and the like, has the characteristics of high curing rate, good curing effect and the like, can realize consolidation of heavy metal polluted water or soil in a short time, has good curing/stabilizing effect, has low heavy metal leaching concentration, high strength and high growth speed of the obtained consolidated body, can realize resource utilization particularly, can be used as roadbed materials or other building materials, has low carbon, low energy consumption and economic applicability, and provides an effective way for resource utilization of industrial solid wastes.
Description
Technical Field
The invention relates to an environment functional material, in particular to an phosphogypsum slag-based functional material for solidifying/stabilizing heavy metals, belonging to the technical field of heavy metal pollution solution and soil treatment.
Background
In recent years, with rapid progress in industrialization and city, heavy metal pollution has become one of the most serious environmental problems worldwide. Among the various heavy metals, cadmium negatively affects human health, particularly bones, and may even threaten human life. The well-known Itai-Itai disease is caused by cadmium poisoning caused by mining and smelting. It has been reported that over 150 sites worldwide have been found to be contaminated with cadmium, with about 500 tens of thousands of people being at risk of exposure to cadmium. It is estimated that the annual worldwide consumption of cadmium can reach 2 to 2.4 tens of thousands of tons. If the cadmium is not safely treated, the released cadmium can enter water and soil through the transportation of rainwater and wind, and accumulate in animals and plants in the whole ecological system. When the accumulation amount exceeds the safety limit, serious damage is caused.
At present, the repair method for the heavy metal cadmium mainly comprises a physical technology, a chemical technology, a biological repair technology and a thermal stabilization technology. The physical technology mainly isolates or separates heavy metals by physical means, so that the heavy metals are intensively fixed. The chemical technology uses the principles of complexation, neutralization, oxidation, precipitation, reduction and the like to finally fix the heavy metal in the solidified body. Bioremediation technology utilizes the action of plants or microorganisms to enrich or alter the properties of heavy metals, which are then treated. The heat stabilization technique mainly improves the performance of the solidified body by heating at high temperature, so that the solidified body has the capability of fixing heavy metals.
The curing/stabilization technique has the characteristics of rapidness, high efficiency, economy and stability. The basic principle is that harmful components of heavy metals are converted into an immovable or insoluble form through physical means (such as adsorption and physical encapsulation) or chemical reaction, so that the absorption of the heavy metals by plants is reduced to the greatest extent, and the contact risk with human beings and animals is reduced. The key to the curing/stabilizing technology is the development of curing/stabilizing agents. The conventional curing agent, such as ordinary Portland cement, has the environmental problems of high energy consumption, greenhouse gas emission, long-term metal leaching risk, air pollution and the like, and has the economic and social problems of high cost, low public acceptance and the like. Thus, there is a need to develop green sustainable curing agents.
Currently, curing agents with green sustainable potential mainly include: (1) Industrial solid waste base materials such as fly ash, red mud and slag; (2) biochar; (3) natural minerals such as clay, lime, zeolite; (4) Metal oxides such as iron oxide, manganese oxide, aluminum oxide, etc.; (5) nanomaterial produced by green synthesis method.
Industrial solid waste-based materials have great potential to become green sustainable curing agents. The method can not only stabilize heavy metals by utilizing the coupling effect between the solid waste base material and the heavy metals, but also realize the purpose of treating waste by recycling the solid waste. Phosphogypsum and blast furnace slag are two common industrial solid wastes, and at present, related reports on the phosphogypsum and blast furnace slag for repairing heavy metal contaminated soil exist, for example, chinese patent (publication number: CN 112480932A) discloses a composite heavy metal contaminated soil repairing medicament which comprises the following components in percentage by mass: 55-70% of white mud, 15-20% of metakaolin, 10-15% of blast furnace slag and 5-10% of phosphogypsum, which are mainly added into soil as a heavy metal contaminated soil remediation agent, and passivation and fixation of heavy metal contaminants are realized by generating calcium aluminosilicate gel so as to change the occurrence form of the heavy metal contaminants and reduce the leaching concentration of the heavy metal and the environmental risk. However, the heavy metal-polluted soil can not be consolidated into a consolidated body which has high strength and good stability and can be used as building materials and the like, and the consumption of the heavy metal-polluted soil is low.
Disclosure of Invention
Aiming at the defects of the prior art, the first aim of the invention is to provide an phosphogypsum slag-based functional material for solidifying/stabilizing heavy metals, which can not only solidify heavy metal polluted water or soil to form a solidified body with higher mechanical strength, be used as roadbed materials or other building materials and realize the recycling utilization of solid wastes such as phosphogypsum and the like, but also effectively fix the heavy metals, has low leaching concentration of the heavy metals, avoids secondary pollution to the environment, and takes phosphogypsum and blast furnace slag as main components, so that the solid wastes can be consumed in a large amount and the recycling utilization of the solid wastes can be realized.
The second purpose of the invention is to provide a method for solidifying/stabilizing heavy metal polluted soil or water body by using phosphogypsum slag-based functional material, which has the characteristics of high solidification rate, good solidification effect and the like, can solidify heavy metal polluted water or soil in a short time, has good solidification/stabilization effect, has low leaching concentration of heavy metal, high strength and high growth speed, can be used as resource, can be applied as roadbed material or other building materials, has low carbon, low energy consumption and economic applicability, and provides an effective way for recycling industrial solid waste.
In order to achieve the technical purpose, the invention provides an phosphogypsum slag-based functional material for solidifying/stabilizing heavy metals, which comprises the following components in percentage by mass: 50% -80% of blast furnace slag; 10% -45% of phosphogypsum; lime 3-25%.
In the phosphogypsum slag-based functional material, the blast furnace slag provides an active silicon aluminum phase and a calcium phase (CaO is more than 40 percent, siO) 2 Greater than 25%, al 2 O 3 Greater than 14%), phosphogypsum provides sulfate and lime provides an alkaline environment; the active silicon-aluminum phase can generate huge amount of ettringite (3CaO.Al) under the excitation of sulfate and alkali 2 O 3 ·3CaSO 4 ·32H 2 O) and calcium silicate hydrate (Ca) 5 Si 6 O 16 (OH)·4H 2 O) and the like, which are hydrated reaction productsHydration products are important factors for maintaining the matrix-solidified heavy metals, mechanical properties and long-term stability.
As a preferable scheme, the phosphogypsum slag-based functional material consists of the following components in percentage by mass: 50% -60% of blast furnace slag; 35% -45% of phosphogypsum; lime 4-6%. A large number of experiments show that when the addition amount of lime is about 5%, the mechanical strength of the formed consolidated body is improved along with the increase of the addition amount of phosphogypsum, so that the mass content of the preferable blast furnace slag is 50-60%, and the mass content of the phosphogypsum added in a matching way is 35-45%. Under the combination, the active silicon aluminum phase in the slag can be stimulated by an alkaline environment created by a sufficient amount of phosphate and a small amount of lime to generate enough ettringite, and the hydrated calcium silicate phase has few points, so that the mechanical strength and the solidification Cd can be ensured.
As a preferable scheme, the phosphogypsum slag-based functional material consists of the following components in percentage by mass: 60% -75% of blast furnace slag; 12-17% of phosphogypsum; lime 10-25%. A large number of experiments show that when the addition amount of phosphogypsum is about 15%, the addition amount of lime is controlled within the range of 10-25%, and when the addition amount of slag is controlled within the range of 60-75%, the mechanical strength of the formed consolidated body is relatively high, so that the mass content of lime is controlled to be 10-25%, and the mass content of blast furnace slag added in a matched manner is controlled to be 60-75%. Under the combination, enough active silicon aluminum phases in slag can be stimulated by enough lime alkali and a small amount of sulfate to generate enough hydrated calcium silicate, and the ettringite phases can be less, so that the mechanical strength and the solidification Cd can be ensured.
As a preferable scheme, the granularity of the blast furnace slag is-100 meshes, and the blast furnace slag comprises the following main chemical components in percentage by mass: caO greater than 40%, siO 2 Greater than 25%, al 2 O 3 Greater than 14%. The blast furnace slag is taken from an iron-making plant, dried, ground and crushed, and screened by a 100-mesh (0.150 mm) screen.
As a preferable scheme, the granularity of the phosphogypsum is-100 meshes, and the phosphogypsum comprises the following main chemical components in percentage by mass: SO (SO) 3 More than 30%, caO more than 20%, al 2 O 3 Greater than 10%, siO 2 Greater than 5%. The phosphogypsum is taken from a phosphate fertilizer plant, is ground and crushed after being dried, and passes through a 100-mesh (0.150 mm) screen.
As a preferred embodiment, the lime has a CaO mass content of greater than 95%.
The invention also provides a method for solidifying/stabilizing the heavy metal polluted water body, which comprises the steps of mixing the heavy metal polluted water body with the phosphogypsum slag-based functional material to form slurry, and carrying out mold filling, solidification, demolding and maintenance on the slurry to obtain a solidified body.
As a preferable scheme, the heavy metal polluted water and the phosphogypsum slag-based functional material are metered according to a liquid-solid mass ratio of 0.3-0.45.
The invention also provides a method for solidifying/stabilizing the heavy metal contaminated soil, which comprises the steps of uniformly mixing the heavy metal contaminated soil with the phosphogypsum slag-based functional material, spraying water on the surface of the mixture, compacting, and standing to obtain a solidified body.
As a preferable scheme, the mass ratio of the heavy metal contaminated soil to the phosphogypsum slag-based functional material is 100:20-40. Adding phosphogypsum slag-based functional materials according to the soil pollution degree; the evaluation standard adopts the soil pollution risk management and control standard of soil environmental quality construction land (GB 36000-2018); when the soil is less than moderate contamination (between 3-fold and 5-fold (inclusive) of the pollutant content) the mass ratio of phosphogypsum slag-based functional material to fine-grained soil may be 20:100. When the soil is higher than (containing) severe pollution (the pollutant content is above 5 times of the evaluation standard), the mass ratio of phosphogypsum slag-based functional material to fine-grained soil is improved to 40:100.
The heavy metal polluted soil or water body of the invention especially refers to cadmium polluted soil or water body, especially high concentration cadmium polluted soil or water body.
The preparation method of the phosphogypsum slag-based functional material comprises the following steps: the method comprises the following steps:
(1) Drying blast furnace slag, grinding and crushing, and sieving with a 100-mesh (0.150 mm) sieve;
(2) Drying phosphogypsum, grinding and crushing, and sieving with a 100-mesh (0.150 mm) sieve;
(3) And fully stirring the ground and sieved phosphogypsum, blast furnace slag and lime powder according to the mixing ratio of 50% -80%, 15% -45% and 3% -25%, and uniformly mixing to obtain the phosphogypsum slag-based functional material.
The method for solidifying/stabilizing Cd pollution solution by phosphogypsum slag-based functional material comprises the following steps:
(1) Mixing the heavy metal pollution liquid to be repaired with phosphogypsum slag-based environment functional material according to a certain liquid-solid ratio (generally 0.4), and fully and uniformly stirring by using a stirrer to prepare the cementing material.
(2) And layering and placing the uniformly stirred cementing materials into a mold, and vibrating and compacting by using a vibrating table.
(3) The excess slurry on the mold was scraped off, the surface was covered with a plastic film to prevent evaporation of water, and the mold was released after 24 hours at room temperature.
(4) And (3) placing the demoulded test block into a standard curing room with the temperature of 20+/-2 ℃ and the relative humidity of more than 95% for curing for 27 days.
The method for solidifying/stabilizing Cd polluted soil by phosphogypsum slag-based functional material comprises the following steps:
(1) Excavating heavy metal contaminated soil to be repaired, removing massive impurities, crushing, and sieving with a 5mm or smaller sieve to obtain fine soil;
(2) Fully stirring phosphogypsum slag-based functional material and the treated fine soil according to a certain mass ratio, and mixing to form a uniform polluted soil solidified compound;
(3) Uniformly spreading the uniformly mixed polluted soil solidified compound according to a certain thickness, uniformly spraying water on the surface of the uniformly mixed polluted soil solidified compound to ensure that the polluted soil solidified compound reaches the optimal water content for compaction, wherein the optimal water content (by weight) of clay is about 15-25%, and the maximum compactness is 1.58-1.7 kN/m 3 Compacting using a machine; repeating the steps, and compacting the layers to obtain the design thickness.
(4) The composite matrix treated by the method is kept stand for 28 days, so that the soil polluted by the heavy metal ions can be solidified/stabilized, and the solidified matrix can be used as a roadbed material or can be directly buried.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
firstly, compared with other solidification/stabilization materials, the phosphogypsum slag-based functional material provided by the invention has good solidification/stabilization effects on heavy metal solution or heavy metal polluted soil in a short time, the leaching concentration of heavy metal of the consolidated body is low, the strength of the consolidated body is high, the growth speed is high, and the finally consolidated body can be used as a roadbed material or other building materials to realize resource utilization.
Secondly, the environment functional material provided by the invention has excellent solidifying/stabilizing effects on heavy metal polluted water or soil with high concentration (the heavy pollution is usually defined to be more than 5 times of an evaluation standard, the construction land control value of Cd is 172mg/kg, the heavy pollution is 860mg/kg or more), the metal leaching concentration of the stabilizer in each age is lower, and the limiting requirements of related standards such as hazardous waste landfill pollution control standard (GB 18598-2019) and hazardous waste identification standard leaching toxicity identification (GB 5085.3-2007) are met.
Thirdly, the phosphogypsum slag-based functional material provided by the invention mainly uses industrial solid waste slag and phosphogypsum as raw materials, has low cost, low carbon, low energy consumption and economic applicability, provides an effective way for recycling industrial solid waste, has better environmental friendliness and generates fewer secondary pollution problems compared with the traditional cement-based curing agent.
Fourth, the phosphogypsum slag-based functional material has strong adaptability, can be used for treating heavy metal polluted soil and heavy metal polluted water, has the characteristics of high curing rate, good curing effect, high strength growth speed and the like, and can be widely applied to treating various heavy metal polluted water or soil.
Drawings
FIG. 1 shows the effect of different proportions of components in phosphogypsum slag-based functional materials on the stabilization effect of heavy metal in a sample after 28d curing, (a) compressive strength; (b) leached metal concentration.
FIG. 2 is a diagram of the slag, phosphogypsum and lime materials used in the phosphogypsum slag-based functional material of the present invention.
FIG. 3 is a product diagram of the phosphogypsum slag based functional material of the present invention curing/stabilizing Cd contaminated liquid.
Fig. 4 is a product diagram of the phosphogypsum slag based functional material curing/stabilizing Cd soil of the present invention.
Detailed Description
The following is a further description in connection with the detailed description, but the detailed description should not be construed as limiting the invention. Various modifications and variations of the invention will be apparent to those skilled in the art in light of the teachings herein and are intended to be within the scope of the invention. In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments.
Example 1
The manufacturing process comprises the following steps:
firstly, slag, phosphogypsum and lime are respectively placed in an oven for drying, and then are ground and then screened by a 100-mesh (0.150 mm) screen, and the screened powder is reserved for standby.
And secondly, the value range of slag is 50% -80%, the value range of phosphogypsum is 15% -45%, the value range of lime is 5% -30%, the detailed raw material proportion design is shown in the table, and the total amount of each group of raw materials is 1.2kg. And then, fully and uniformly stirring the weighed slag, phosphogypsum and lime by using a planetary stirrer to prepare mixed powder.
TABLE 1 raw material proportion design, curing time and test Contents of phosphogypsum slag-based functional Material
And thirdly, adding a cadmium nitrate solution with the mass percent of 1 percent into the mixed powder according to the proportion of 0.4 of liquid-solid ratio. A planetary mixer was used, and the mixture was stirred at a slow speed for 120 seconds and then allowed to stand. The slurry at the bottom of the pan was shoveled with a small spatula within 15 seconds and finally the mixing process was terminated with rapid stirring for 120 seconds.
And fourthly, pouring the evenly stirred slurry into a cubic test mold (40 mm multiplied by 40 mm), and placing the slurry on a vibration table for vibrating for 10 seconds so as to remove bubbles in the slurry and ensure that the slurry is compact and even.
And fifthly, removing excessive slurry on the surface of the die by using a scraper, and covering the test die by using a plastic film. Subsequently, the mixture was allowed to stand at room temperature for 24 hours, and after it was sufficiently solidified, demolding was performed.
And seventh, transferring the sample to a standard curing room for curing after demolding. The temperature of the standard curing chamber needs to be adjusted to 20 ℃ and the relative humidity maintained at 95% to ensure that the sample can be cured and matured in the best environment.
Eighth step, testing process:
(1) Compressive strength: the Unconfined Compressive Strength (UCS) of the test pieces was measured according to the rules of the cement mortar strength test method (GB/T17671-2021). And (3) measuring the compressive strength of the sample during curing set time by adopting a computer-controlled bending pressure tester under the condition that the loading rate is 2400N/s+/-200N/s. After the compressive strength test is finished, residues of the crushed samples are collected and subjected to a heavy metal leaching test.
(2) Carbonization test: after the test piece is cured in a standard curing room for 28 days, a carbonization test is carried out on the test piece according to the standard of the test method for the long-term performance and durability of common concrete (GB/T50082-2009), and the long-term stability of a solidified body after carbonization is verified. CO 2 The concentration was maintained at (20.+ -. 3)%, the relative humidity was controlled at (70.+ -. 5)%, and the temperature was controlled within the range of (20.+ -. 2) ℃, and the bulk strength and the heavy metal of the carbonized part at 3, 7, 14 and 28 days of carbonization were testedBelongs to leaching amount. The carbonization test was mainly used to demonstrate the durability of the test block.
(3) Heavy metal leaching test: the test was performed according to the standard "method of leaching toxicity of solid waste sulfuric acid nitric acid method" (HJ/T299-2007). Lixiviant 1 # : the mass ratio is 2:1 to reagent water (1L water about 2 drops of the mixture) to a pH of 3.20.+ -. 0.05. The leaching process is carried out under the conditions that the turnover speed is kept at 30+/-2 rpm, the ambient temperature is controlled at 23+/-2 ℃ and the working time is controlled at 18+/-2 h by adopting the solid sample to the leaching agent ratio of 1:10 (kg/L). The heavy metal leachate was filtered through a 0.45 μm membrane and tested for heavy metal concentration using inductively coupled plasma mass spectrometry (ICP-MS).
Test results:
the test results of fig. 1 show the effect of the raw material proportion of phosphogypsum slag-based functional material on the curing effect, and as shown in fig. 1 (a), when the lime content is 5%, the compressive strength increases with the increase of Phosphogypsum (PG) content. However, when the lime content is 10%, 15%, 20%, 25% and 30%, respectively, the compressive strength decreases with increasing PG content. Compared with different raw material proportions, the PS with GGBS content of 50%, PG content of 45% and lime content of 5% has highest compressive strength, reaching 37.3MPa.
Furthermore, as shown in FIG. 1 (b), the metal leaching concentration is generally lower than the limit (1 mg/L) recommended in hazardous waste identification Standard leaching toxicity identification. The comparison of the samples shows that the metal leaching concentration of the P45C5 sample (PG content is 45%, caO content is 5%, slag content is 50%) is the lowest, 0.134 mug/L, and the highest compressive strength is 37.3MPa. In contrast, sample P45C30 (PG content: 45%, caO content: 30%, slag content: 25%) showed the highest metal leaching concentration (0.198. Mu.g/L) and the lowest compressive strength (8.13 MPa).
Therefore, based on the above results, it is recommended to use sample P45C5 as a curing agent for curing/stabilizing heavy metal cadmium because it has good mechanical properties and heavy metal stabilizing ability. For further application, the cadmium-doped cured product can meet the minimum strength requirements of 32.5 MPa and 15MPa standard for european building cements, respectively, when used as building materials or pavement base materials. If the cured cadmium cured product is used in a landfill, its strength value is much higher than 0.35MPa for the American default standard and 3.45MPa for the Canadian standard.
TABLE 2 compressive strength and heavy metal leaching concentration of uncarbonated samples
TABLE 3 compressive strength, heavy metal leaching concentration and depth of carbonization of carbonized samples
Example 2
The manufacturing process comprises the following steps:
firstly, respectively drying slag, phosphogypsum and lime, grinding, sieving with a 100-mesh (0.150 mm) sieve, and reserving for standby.
Second, according to slag: phosphogypsum: the proportion of lime is 50%:45%:5% of raw materials are weighed, and the weighed slag, phosphogypsum and lime are uniformly stirred by a planetary stirrer to prepare the curing agent.
Thirdly, excavating heavy metal cation Cd polluted soil (Cd content is 1000 mg/kg) to be repaired, removing massive impurities, crushing and sieving with a 5mm or smaller sieve to obtain fine-grained soil;
and fourthly, mixing the phosphogypsum slag-based functional material with Cd polluted soil according to the proportion of the curing agent/the polluted soil of 20% and 40%, uniformly stirring by using a planetary stirrer, adding water which enables the water content of the soil body to be about 20%, and continuously stirring to enable the mixture to be uniform.
Fifth, the mixture is put into a cylindrical die with the diameter of 39.1mm and the height of 80mm, and the mixture is pressed to the compactness of about 1.6KN/m by a press machine 3 。
Sixthly, scraping off redundant mixture on the surface of the die, transferring the sample into a standard curing room for curing after demolding, and controlling the temperature of the standard curing room to be (20+/-2) DEG C and the humidity to be more than or equal to 95%.
The testing process comprises the following steps:
(1) Compressive strength: an Unconfined Compressive Strength (UCS) test was performed on a stabilized cadmium contaminated soil sample according to Standard Test Method for Unconfined Compressive Strength Index of Chemical-organized Soils, ASTM (2008) standards with strain rate control of 1%/min. The compressive strength of the test pieces after curing for 7, 14 and 28 days was measured. After the compressive strength test is finished, residues of the crushed samples are collected and subjected to a heavy metal leaching test.
(2) Heavy metal leaching test: the same as in example 1.
Test results:
table 4 test block compressive Strength (MPa)
TABLE 5 Leaching concentration of heavy metals from test block (μg/L)
As shown by test result data in tables 4 and 5, the phosphogypsum slag-based functional material has good solidification and stabilization effects on Cd heavy metal solution and Cd polluted soil, and also has good carbonization resistance stability, and the heavy metal leaching concentration of the solidified body in each test age meets the regulations of hazardous waste landfill pollution control standard (GB 18598-2019) and hazardous waste identification standard leaching toxicity identification (GB 5085.3-2007), wherein the requirement is lower than 0.6mg/L, and the requirement is not higher than 1mg/L.
The mechanical properties of the cured/stabilized product required will also vary depending on the final handling of the cured/stabilized product. When contaminated stabilized soil is used for landfill treatment, the United states EPA recommends a strength of greater than 0.35MPa after 28 days of maintenance, and the stabilized soil strength of the Netherlands and French standards recommends greater than 1MPa. The material with the test block strength of more than 0.30MPa can be used as roadbed material, and the material with the test block strength of more than 0.68MPa can be used as base layer.
Claims (10)
1. Phosphogypsum slag-based functional material for solidifying/stabilizing heavy metals, which is characterized in that: comprises the following components in percentage by mass:
50% -80% of blast furnace slag;
10% -45% of phosphogypsum;
lime 3-25%.
2. Phosphogypsum slag based functional material for solidification/stabilization of heavy metals as claimed in claim 1, characterized in that:
the composite material consists of the following components in percentage by mass:
50% -60% of blast furnace slag;
35% -45% of phosphogypsum;
lime 4-6%.
3. Phosphogypsum slag based functional material for solidification/stabilization of heavy metals as claimed in claim 1, characterized in that:
the composite material consists of the following components in percentage by mass:
60% -75% of blast furnace slag;
12-17% of phosphogypsum;
lime 10-25%.
4. A phosphogypsum slag based functional material for solidification/stabilization of heavy metals according to any one of claims 1 to 3, characterized in that: the granularity of the blast furnace slag is less than 100 meshes, and the blast furnace slag comprises the following main chemical components in percentage by mass: caO greater than 40%, siO 2 Greater than 25%, al 2 O 3 Greater than 14%.
5. A phosphogypsum slag based functional material for solidification/stabilization of heavy metals according to any one of claims 1 to 3, characterized in that: the granularity of the phosphogypsum is less than 100 meshesThe main chemical components and mass fractions thereof are as follows: SO (SO) 3 More than 30%, caO more than 20%, al 2 O 3 Greater than 10%, siO 2 Greater than 5%.
6. A phosphogypsum slag based functional material for solidification/stabilization of heavy metals according to any one of claims 1 to 3, characterized in that: the CaO mass content of the lime is more than 95%.
7. A method for solidifying/stabilizing a heavy metal polluted water body is characterized by comprising the following steps: mixing heavy metal polluted water with the phosphogypsum slag-based functional material of any one of claims 1 to 6 to form slurry, and carrying out mold filling, curing, demolding and curing on the slurry to obtain a cured body.
8. The method for solidifying/stabilizing a heavy metal contaminated water body according to claim 7, wherein: the heavy metal polluted water and the phosphogypsum slag-based functional material are metered according to the liquid-solid mass ratio of 0.3-0.45.
9. A method for solidifying/stabilizing heavy metal contaminated soil, which is characterized by comprising the following steps: uniformly mixing heavy metal contaminated soil with the phosphogypsum slag-based functional material according to any one of claims 1 to 6, spraying water on the surface of the mixture, compacting the mixture, and standing the mixture to obtain a solidified body.
10. The method for solidifying/stabilizing heavy metal contaminated soil according to claim 9, wherein: the mass ratio of the heavy metal contaminated soil to the phosphogypsum slag-based functional material is 100:20-40.
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