CN118206349A - Full-solid waste phosphogypsum-based aggregate and preparation method and application thereof - Google Patents
Full-solid waste phosphogypsum-based aggregate and preparation method and application thereof Download PDFInfo
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- CN118206349A CN118206349A CN202410279717.8A CN202410279717A CN118206349A CN 118206349 A CN118206349 A CN 118206349A CN 202410279717 A CN202410279717 A CN 202410279717A CN 118206349 A CN118206349 A CN 118206349A
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- solid waste
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- based aggregate
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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 108
- 239000002910 solid waste Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000008188 pellet Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000002893 slag Substances 0.000 claims description 72
- 239000004567 concrete Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910000831 Steel Inorganic materials 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 17
- 239000010959 steel Substances 0.000 claims description 17
- 239000011258 core-shell material Substances 0.000 claims description 16
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 239000010881 fly ash Substances 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 238000012423 maintenance Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 238000005469 granulation Methods 0.000 abstract description 19
- 230000003179 granulation Effects 0.000 abstract description 19
- 238000002156 mixing Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 13
- 239000003469 silicate cement Substances 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 27
- 239000004568 cement Substances 0.000 description 26
- 239000002245 particle Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 8
- 230000036571 hydration Effects 0.000 description 7
- 238000006703 hydration reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 239000011398 Portland cement Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910001653 ettringite Inorganic materials 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000353097 Molva molva Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005453 pelletization 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
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a full-solid waste phosphogypsum-based aggregate, and a preparation method and application thereof, and belongs to the technical field of building material artificial aggregates. The method comprises the following steps: adding water into the granulating material, pre-stirring to obtain a premix, and granulating the premix to obtain water-drop green pellets; continuously adding a granulating material or a reconstruction material into the water-drop green pellets, reconstructing the water-drop green pellets, and then continuously granulating to obtain capillary green pellets; and curing the capillary green pellets to obtain the full-solid waste phosphogypsum-based aggregate. The invention can realize quantitative control of the water consumption of granulation by mixing the granulation material with water, thereby obviously improving the granulation quality and efficiency; in addition, the water drop green balls are reconstructed by adding the granulating material or the reconstruction material, so that the process is simplified, and the adaptability of aggregate and silicate cement can be obviously improved.
Description
Technical Field
The invention belongs to the technical field of artificial aggregates of building materials, and particularly relates to a full-solid waste phosphogypsum-based aggregate, and a preparation method and application thereof.
Background
The wet process of phosphoric acid is to decompose phosphorite (fluorapatite) with concentrated sulfuric acid at 75-80 deg.c to extract phosphoric acid, and in this process, an industrial by-product gypsum, phosphogypsum, is produced. The main component of phosphogypsum is CaSO 4·2H2 O, but unlike natural gypsum, the phosphogypsum also contains a large amount of impurities including phosphorus and fluorine compounds, residual organic mineral flotation agents, acid, heavy metal elements and the like. These impurities greatly affect phosphogypsum properties, making it difficult to recycle in large quantities. At present, the comprehensive effective utilization rate of phosphogypsum is lower than 40%, and the yield of phosphogypsum is 4-5 times of that of phosphoric acid, so how to effectively treat phosphogypsum becomes a difficult problem for limiting the healthy development of the phosphorus chemical industry.
There have been some practices that the preparation of phosphogypsum-based Leng Nianjie aggregate based on "persulfate phosphogypsum slag cement" (hereinafter referred to as phosphogypsum-based aggregate) by using phosphogypsum is an effective way to consume phosphogypsum on a large scale, for example, chinese patent document CN113354376A discloses a phosphogypsum-based aggregate for road engineering and a preparation method thereof, the aggregate is prepared by mixing 50-80% phosphogypsum, 15-45% waste slag powder and 3-6% alkaline activator into powder, spraying a solution of sodium hexametaphosphate, cellulose ether and water by a granulator to prepare green pellets, and spraying organic silicon after the green pellets are immersed and cured to obtain the required aggregate; the Chinese patent document CN110451864A discloses a phosphogypsum baking-free ceramsite lightweight aggregate and a preparation method thereof, wherein the aggregate is prepared by uniformly mixing 80-90% of phosphogypsum, 3.3-10% of mineral powder, 6.5-10% of cement and a small amount of water, granulating by using granulating equipment while adding water at a speed of 1.25-1.5L/min to prepare a green pellet, curing for 14-28d by soaking or sprinkling water after initial setting and final setting, and drying, crushing and screening to obtain the required aggregate.
The existing phosphogypsum-based aggregate manufacturing process has the problems that the water for granulation is not controlled uniformly, and green balls are easy to bond with each other, so that the prepared phosphogypsum-based aggregate has uneven particle size and low strength, and the components contain excessive sulfate, so that the phosphogypsum-based aggregate is incompatible with silicate cement, and the like.
Disclosure of Invention
The invention aims to provide a full-solid waste phosphogypsum-based aggregate, and a preparation method and application thereof, which are used for solving the problems that the existing phosphogypsum-based aggregate manufacturing process has uneven control of water for granulation, and raw balls are easy to bond with each other, so that the prepared phosphogypsum-based aggregate has uneven particle size and low strength, and the components contain excessive sulfate, so that the phosphogypsum-based aggregate is incompatible with silicate cement, and the like.
In a first aspect, the invention provides a method for preparing a full solid waste phosphogypsum-based aggregate, comprising the following steps: adding water into the granulating material, pre-stirring to obtain a premix, and granulating the premix to obtain water-drop green pellets; continuously adding a granulating material or a reconstruction material into the water-drop green pellets, reconstructing the water-drop green pellets, and then continuously granulating to obtain capillary green pellets; curing the capillary green pellets to obtain a full-solid waste phosphogypsum-based aggregate; wherein, the granulating material comprises 70-85% phosphogypsum, 10-25% solid waste silicon-aluminum material and 1-20% solid waste alkali excitant by mass percent; the reconstruction material comprises 0-20% phosphogypsum, 60-90% solid waste silicon-aluminum material and 1-20% solid waste alkali excitant.
In the preparation method of the full-solid waste phosphogypsum-based aggregate, the inventor researches and discovers that the traditional sprinkling granulation refers to that particles are wetted in a form of spraying water mist in the granulation process, a layer of water film is formed on the surface, and a liquid bridge is formed among the particles due to the surface tension of water (0.072N/m at 25 ℃), so that the particles are caused to agglomerate and grow, but sprinkling is uneven, and the performance of the prepared aggregate is reduced. Specifically, if the water sprinkling amount is insufficient, the balling efficiency is low, the green ball strength is low, the defects of aggregate are many, and the performance is poor; if water is excessively sprayed, mud balls are easy to form, deform, have poor granularity uniformity, are mutually bonded, and are unfavorable for storage and transportation; at present, aggregate is prepared by adopting a process of alternately spraying water and adding materials, but the requirement on the granulating proficiency of workers is high, the manual requirement is strict, and the problems of longer granulating time, low production efficiency and the like exist.
Based on the above, the inventors of the present invention have further studied and found that, before granulation, the granulated material and water are mixed and the dispersion uniformity of the water is remarkably improved by adopting a mechanical stirring dispersion form, thereby avoiding the problems of uneven hydration and the like and avoiding dust pollution in the granulation process to a certain extent. The wet material collides and rubs under the drive of mechanical rotation, and is compacted and filled with moisture along with gaps among material particles, namely, the distance among particles is shortened and the liquid phase saturation is improved. According to the particle strength theory, the binding force among the particles mainly consists of the negative pressure of the capillary and the tensile force generated by the surface tension of the liquid bridge, and compaction and liquid phase saturation promotion increase the volume of the liquid bridge among the particles, so that the particles are fully infiltrated, the contact angle is reduced, the action area of the negative pressure of the capillary and the action area of the surface tension are increased, and the binding force among the particles and the binding strength of green balls are further improved. In addition, the shrinkage of the voids will cause the particles to tightly embed together, gradually squeezing water out of the surface of the green pellets, and the pellets will undergo 4 states in turn, namely a "pendulum state", "a" rope-belt state "," a "capillary state" and a "drop state", depending on the degree to which the inter-particle voids are filled with water. Wherein the green pellets have the highest bond strength when they reach a capillary state. The water drop state promotes the high-efficiency agglomeration growth among materials due to the existence of a surface water film. The low water content material is difficult to directly enter the capillary state, and the traditional process is to increase the sprinkling amount, increase the granulating time and strengthen the mechanical action, but the material is easy to pass through the capillary state and directly enter the water drop state, and form mud balls. In the invention, the water for granulation is properly surplus, the water enters a water drop state and grows under the mechanical action, and then the granulation material or the reconstruction material is added in a form of water neutralization of the material so as to reconstruct a capillary state. The prepared capillary green pellets are in a dry state, have high bonding strength, and are favorable for stabilizing the morphology of particles and avoiding adhesion or extrusion deformation between the green pellets during storage and transportation.
Further, according to the principle of bonding agglomeration, when the material properties (such as water content and fineness) and the granulating mechanical parameters (such as diameter, inclination angle and rotating speed) are determined, the time point of the material entering a water drop state is determined, namely, the granulating process flow forms a cycle, so that the automatic control of the granulating process is realized, and the total time of one cycle is generally determined at 5-15min according to the material properties and target properties. The preparation process can obviously improve the granulating efficiency, optimize the moisture uniformity, the liquid phase saturation, the pore structure and the like of the green pellets, and further improve the early bonding strength of the green pellets.
In some embodiments, during the preparation of the green pellets in the form of water droplets, the water to pelletising material water ratio is (0.17-0.21): 1, which may be, for example, 0.17:1, 0.18:1, 0.19:1, 0.20:1, 0.21:1 or other values within this range; the pre-stirring is carried out in a stirrer, and the granulating comprises: placing a premix comprising 60-80 parts (e.g., 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, or other values within this range) of the granulation material into a centrifugal granulator to granulate for 3-10 minutes, e.g., 3 minutes, 5 minutes, 7 minutes, 10 minutes, or other values within this range; the rotation rate of the centrifugal granulator is 20-45r/min, and may be, for example, 20r/min, 25r/min, 30r/min, 35r/min, 40r/min, 45r/min or other values within this range.
In some embodiments, during the preparation of capillary green pellets, 20-40 parts (e.g., 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, or other values within this range) of granulating or reconstitution material is added to the water-drop green pellets, and granulating comprises: pelletization is carried out for 4 to 10 minutes, for example, 4 minutes, 5 minutes, 7 minutes, 10 minutes or other values within this range.
In some embodiments, when 20-40 parts of the granulation material is added continuously to the green pellets in the form of water droplets, capillary homogeneous green pellets are obtained; sealing and preserving capillary homogeneous green balls for 1-3d, such as 1d, 2d and 3d or other values in the range; then immersing in water for continuous curing for 13-27d, which may be 13d, 15d, 17d, 20d, 25d, 27d or other values within this range; obtaining the homogeneous full-solid phosphogypsum-based aggregate.
In some embodiments, when 20-40 parts of the reconstituted material is added to the water-drop green pellets, capillary core-shell green pellets are obtained; sealing and preserving the capillary core-shell green balls for 1-3d, and then soaking the core-shell green balls in water for continuous curing for 13-27d or soaking the core-shell green balls in sodium silicate curing liquid with the mass concentration of 3-15% (for example, 3%, 6%, 9%, 12%, 15% or other values in the range) for continuous curing for 6-27d, for example, 6d, 8d, 10d, 13d, 16d, 19d, 22d, 25d or other values in the range; obtaining the core-shell full-solid waste phosphogypsum-based aggregate.
In the invention, because the content of the active material in the reconstructed material is higher, the structure is more compact due to higher hydration degree after hydration hardening, and the dissolution of sulfate can be inhibited in a physical solid sealing mode by chemically combining the product ettringite with internal sulfate or by physically sealing, thereby realizing the aim of being compatible with a silicate cement system. In addition, the sodium silicate curing liquid can also obviously improve the early strength and carbonization resistance of aggregate and enhance the combination with matrix cement.
In some embodiments, phosphogypsum is in the form of powdered sand or wet agglomerate, the water content is 0-15%, the solid content is not less than 85%, and the content of soluble P impurity and F impurity is less than or equal to 3%.
In some embodiments, the solid waste aluminous material comprises granulated blast furnace slag of grade S95 or greater and at least one of high calcium fly ash of grade ii or greater or granulated yellow phosphorus slag of grade L95, wherein the CaO content in the high calcium fly ash is greater than 10%, and the granulated blast furnace slag of grade S95 or greater, the granulated blast furnace slag of grade ii or greater, the granulated yellow phosphorus slag of grade L95 are each treated with a 200 mesh or greater screen.
In the present invention, the solid waste silicon aluminum material includes granulated blast furnace slag of grade S95 or more and at least one of high calcium fly ash of grade ii or more or granulated yellow phosphorus slag of grade L95, for example, the solid waste silicon aluminum material may include granulated blast furnace slag of grade S95 or more, high calcium fly ash of grade ii or more; or may include only granulated blast furnace slag of grade S95 or more, L95 granulated yellow phosphorus slag; or the granulated blast furnace slag of S95 grade or above S95 grade, the high-calcium fly ash of II grade or above II grade and the L95 granulated yellow phosphorus slag can be simultaneously included.
And the proportion of each component in the solid waste silicon-aluminum material can be adjusted correspondingly according to the actual use condition.
In some embodiments, the solid waste alkali excitant comprises at least one of grade II or more steel slag powder, carbide slag and red mud, wherein the CaO content in the carbide slag is more than or equal to 65%, the pH value of the red mud is more than 10, the Na 2 O content is more than 5%, and the grade II or more steel slag powder, carbide slag and red mud are all processed by a screen with more than 100 meshes.
In the invention, the solid waste alkali excitant comprises at least one of steel slag powder of grade II or more, carbide slag and red mud, for example, the solid waste alkali excitant can only comprise steel slag powder of grade II or more; or only carbide slag; or only red mud; or only comprises the steel slag powder of grade II or above grade II and carbide slag; or only comprises the steel slag powder of grade II or more than grade II and red mud; or only comprises carbide slag and red mud; or comprises the steel slag powder of grade II or above, carbide slag and red mud.
And the proportion of each component in the solid waste alkali excitant can be adjusted correspondingly according to the actual use condition.
According to the invention, a synergistic effect is exerted among phosphogypsum, solid waste silicon aluminum materials and solid waste alkali excitant, wherein the solid waste alkali excitant provides OH - and breaks chemical bonds of the solid waste silicon aluminum materials, SO that the phosphogypsum is promoted to be dissolved and hydrated to generate hydrated calcium silicate gel, and the phosphogypsum provides a large amount of SO 4 2- and promotes partial hydration products to be converted into ettringite; the needle-shaped ettringite and the amorphous C-S-H gel are mutually staggered, and the excessive non-reacted phosphogypsum is wrapped and cured, so that the cementing system generates strength. Furthermore, the preparation process of the invention ensures that the moisture is uniformly dispersed among materials, creates conditions for full hydration of the material components, and optimizes the internal microcosmic and mesoscopic pore structure of the aggregate at the same time, thereby forming excellent service performance.
In a second aspect, the invention provides an all-solid waste phosphogypsum-based aggregate prepared by any one of the preparation methods.
In a third aspect, the invention provides the use of the above-described all-solid waste phosphogypsum-based aggregate in the preparation of concrete products.
The beneficial effects of the invention are as follows: compared with the prior art, the invention can realize quantitative control of water consumption of granulation and accurate control of granulation time by mixing the granulation materials and water, realize parameterization, automation and clean production of the granulation process, and obviously improve the granulation efficiency; meanwhile, the stirring dispersion mode is adopted to remarkably improve the dispersion uniformity of water, so that the particle size distribution of green pellets is more uniform, the liquid phase saturation, particle stacking and pore structure of the green pellets are optimized, and the early bonding strength of the green pellets is improved; meanwhile, the granulating material or the reconstruction material is added to reconstruct the water drop green balls, so that the process is simplified, and the adaptability of aggregate and silicate cement can be obviously improved; in addition, the recycling rate of solid waste is improved, the value-added application of low-quality solid waste is realized, artificial high-enthalpy materials such as cement, lime and the like are not needed, the material cost is reduced, the energy is saved, the environment is protected, and the environment-friendly value and the economic benefit are extremely high.
Drawings
FIG. 1 is a flow chart of a process for preparing an all-solid waste phosphogypsum-based aggregate in the invention;
FIG. 2 is a morphology diagram of the total solid waste phosphogypsum-based aggregate prepared in the embodiment 1 of the present invention, wherein (A) is a morphology diagram of capillary green pellets; and (B) is an aggregate CT diagram.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The experimental methods for which specific conditions are not specified in the examples are generally commercially available according to conventional conditions and those described in handbooks, or according to conditions recommended by the manufacturer, using general-purpose equipment, materials, reagents, etc., unless otherwise specified.
In the invention, phosphogypsum is undisturbed silt or wet agglomerate, the water content is 6.42%, the main component is CaSO 4·2H2 O, the solid content is 85%, and the content of soluble P (calculated by P 2O5) and F impurity is 3%; the S95 level granulated blast furnace slag is treated by a 600 mesh screen, the II level high calcium fly ash (the CaO content is 12.1%) is treated by a 400 mesh screen, the L95 level granulated yellow phosphorus slag is treated by a 600 mesh screen, the II level steel slag powder is treated by a 400 mesh screen, the carbide slag (the CaO content is 65.2%) is treated by a 100 mesh screen, the red mud (the pH value is more than 10, the Na 2 O content is 5.6%) is treated by a 100 mesh screen.
Referring to fig. 1, which is a process flow chart of the preparation process of the all-solid waste phosphogypsum-based aggregate, the preparation of the all-solid waste phosphogypsum-based aggregate comprises the following steps: adding water into the granulating material, pre-stirring to obtain a premix, and granulating the premix to obtain water-drop green pellets; continuously adding a granulating material or a reconstruction material into the water-drop green pellets, reconstructing the water-drop green pellets, and then continuously granulating to obtain capillary green pellets; curing the capillary green pellets to obtain a full-solid waste phosphogypsum-based aggregate; wherein, the granulating material comprises 70-85% phosphogypsum, 10-25% solid waste silicon-aluminum material and 1-20% solid waste alkali excitant by mass percent; the reconstruction material comprises 0-20% phosphogypsum, 60-90% solid waste silicon-aluminum material and 1-20% solid waste alkali excitant.
Example 1
The full solid waste phosphogypsum-based aggregate comprises a granulating material, wherein the granulating material comprises solid waste silicon-aluminum material formed by mixing 80% of phosphogypsum, 10% of blast furnace slag and 5% of yellow phosphorus slag, solid waste alkali excitant formed by mixing 2% of steel slag powder, 2% of carbide slag and 1% of red mud, and the raw materials are put into a mixer to be uniformly mixed, so that the granulating material is obtained.
The preparation method of the full solid waste phosphogypsum-based aggregate comprises the following steps:
1) Putting the granulating materials into a stirrer, adding water to control the water-to-material ratio to be 0.19:1, pre-stirring to obtain a premix, and putting the premix containing 70 parts of the granulating materials into a disc granulator rotating at a constant speed of 25r/min for granulating for 4min, wherein the disc inclination angle is 42 degrees, the diameter is 2m, and the depth is 0.2m, so as to obtain water-drop green balls;
2) Continuously adding 30 parts of granulating materials into a disk granulator containing water-drop green balls, and continuously granulating for 7min to obtain capillary green balls;
3) Sealing and preserving the capillary green pellets for 3d, and then soaking the green pellets in water for continuous maintenance for 25d to obtain the homogeneous full-solid phosphogypsum-based aggregate.
The capillary green pellets and the full solid waste phosphogypsum-based aggregate prepared in this example were subjected to performance test, and the results are shown in fig. 2.
Example 2
The full solid waste phosphogypsum-based aggregate comprises a granulating material, wherein the granulating material comprises solid waste silicon-aluminum material formed by mixing 80% of phosphogypsum, 4% of blast furnace slag, 10% of yellow phosphorus slag and 1% of high-calcium fly ash, and solid waste alkali-exciting agent formed by mixing 2% of steel slag powder, 2% of carbide slag and 1% of red mud, and the raw materials are put into a mixer to be uniformly mixed, so that the granulating material is obtained.
The preparation method of the full solid waste phosphogypsum-based aggregate comprises the following steps:
1) Putting the granulating materials into a stirrer, adding water to control the water-to-material ratio to be 0.19:1, pre-stirring to obtain a premix, and putting the premix containing 70 parts of the granulating materials into a disc granulator rotating at a constant speed of 25r/min for granulating for 4min, wherein the disc inclination angle is 42 degrees, the diameter is 2m, and the depth is 0.2m, so as to obtain water-drop green balls;
2) Continuously adding 30 parts of granulating materials into a disk granulator containing water-drop green balls, and continuously granulating for 7min to obtain capillary green balls;
3) Sealing and preserving the capillary green pellets for 3d, and then soaking the green pellets in water for continuous maintenance for 25d to obtain the homogeneous full-solid phosphogypsum-based aggregate.
Example 3
The full solid waste phosphogypsum-based aggregate comprises a granulating material, wherein the granulating material comprises solid waste silicon-aluminum material formed by mixing 80% of phosphogypsum, 10% of blast furnace slag and 5% of yellow phosphorus slag, solid waste alkali-exciting agent formed by mixing 1% of steel slag powder and 4% of carbide slag, and the raw materials are put into a mixer to be uniformly mixed, so that the granulating material is obtained.
The preparation method of the full solid waste phosphogypsum-based aggregate comprises the following steps:
1) Putting the granulating materials into a stirrer, adding water to control the water-to-material ratio to be 0.19:1, pre-stirring to obtain a premix, and putting the premix containing 70 parts of the granulating materials into a disc granulator rotating at a constant speed of 25r/min for granulating for 4min, wherein the disc inclination angle is 42 degrees, the diameter is 2m, and the depth is 0.2m, so as to obtain water-drop green balls;
2) Continuously adding 30 parts of granulating materials into a disk granulator containing water-drop green balls, and continuously granulating for 7min to obtain capillary green balls;
3) Sealing and preserving the capillary green pellets for 3d, and then soaking the green pellets in water for continuous maintenance for 25d to obtain the homogeneous full-solid phosphogypsum-based aggregate.
Example 4
The full solid waste phosphogypsum-based aggregate comprises a granulating material and a reconstructing material, wherein the granulating material comprises solid waste silicon-aluminum material formed by mixing 80% of phosphogypsum, 10% of blast furnace slag and 5% of yellow phosphorus slag, and solid waste alkali excitant formed by mixing 2% of steel slag powder, 2% of carbide slag and 1% of red mud; the reconstruction material comprises solid waste silicon aluminum material formed by mixing 10% of phosphogypsum, 15% of blast furnace slag, 45% of yellow phosphorus slag and 10% of high-calcium fly ash, and solid waste alkali excitant formed by mixing 12% of steel slag powder, 2% of carbide slag and 6% of red mud. And (3) putting the raw materials into a mixer for uniform mixing to obtain a granulating material and a reconstruction material respectively.
The preparation method of the full solid waste phosphogypsum-based aggregate comprises the following steps:
1) Putting the granulating materials into a stirrer, adding water to control the water-to-material ratio to be 0.19:1, pre-stirring to obtain a premix, and putting the premix containing 70 parts of the granulating materials into a disc granulator rotating at a constant speed of 25r/min for granulating for 4min, wherein the disc inclination angle is 42 degrees, the diameter is 2m, and the depth is 0.2m, so as to obtain water-drop green balls;
2) Continuously adding 30 parts of reconstruction materials into a disk granulator containing water-drop green balls, and continuously granulating for 7min to obtain capillary green balls;
3) Sealing and preserving the capillary green pellets for 3d, and then soaking the green pellets in sodium silicate curing liquid (the modulus is 1.2) with the mass concentration of 13% for continuous curing for 25d to obtain the core-shell full-solid waste phosphogypsum-based aggregate.
Example 5
The full solid waste phosphogypsum-based aggregate comprises a granulating material and a reconstructing material, wherein the granulating material comprises solid waste silicon-aluminum material formed by mixing 80% of phosphogypsum, 10% of blast furnace slag and 5% of yellow phosphorus slag, and solid waste alkali excitant formed by mixing 2% of steel slag powder, 2% of carbide slag and 1% of red mud; the reconstruction material comprises solid waste silicon aluminum material mixed by 15% of blast furnace slag, 55% of yellow phosphorus slag and 10% of high-calcium fly ash, and solid waste alkali excitant mixed by 12% of steel slag powder, 2% of carbide slag and 6% of red mud. And (3) putting the raw materials into a mixer for uniform mixing to obtain a granulating material and a reconstruction material respectively.
The preparation method of the full solid waste phosphogypsum-based aggregate comprises the following steps:
1) Putting the granulating materials into a stirrer, adding water to control the water-to-material ratio to be 0.19:1, pre-stirring to obtain a premix, and putting the premix containing 70 parts of the granulating materials into a disc granulator rotating at a constant speed of 25r/min for granulating for 4min, wherein the disc inclination angle is 42 degrees, the diameter is 2m, and the depth is 0.2m, so as to obtain water-drop green balls;
2) Continuously adding 30 parts of reconstruction materials into a disk granulator containing water-drop green balls, and continuously granulating for 7min to obtain capillary green balls;
3) Sealing and preserving the capillary green pellets for 3d, and then soaking the green pellets in water for continuous maintenance for 25d to obtain the core-shell full-solid waste phosphogypsum-based aggregate.
Comparative example 1
The preparation method of the all-solid waste phosphogypsum-based aggregate is basically the same as that of the embodiment 1, except that in the step 1), the water-material ratio is 0.16:1.
Comparative example 2
The preparation method of the all-solid waste phosphogypsum-based aggregate is basically the same as that of the embodiment 1, except that in the step 1), the rotating speed of the disk granulator is 15r/min.
Comparative example 3
The preparation method of the all solid waste phosphogypsum-based aggregate is basically the same as that of the example 1, except that in the step 1), the aggregate is granulated for 2min in a disc granulator.
Comparative example 4
The preparation method of the all-solid waste phosphogypsum-based aggregate is basically the same as that of the example 1, except that in the step 2), granulation is continued for 3min.
Performance testing
The all solid waste phosphogypsum-based aggregates prepared in examples 1 to 9 and comparative example were subjected to performance test, and the results are shown in the following table 1:
TABLE 1 full solid waste phosphogypsum-based aggregate Performance test results
As can be seen from the data in table 1, the fully solid waste phosphogypsum-based aggregate prepared in examples 1 to 5 has better performance, and the reconstituted materials with higher active ingredients are adopted in examples 4 and 5, so that after hydration hardening, the structure is more compact due to higher hydration degree, and the dissolution of sulfate can be inhibited by chemically combining the form of ettringite which is a product with internal sulfate or in a physical solid sealing form, so that the concentration of leachate S is extremely low, and sodium silicate curing liquid is adopted for curing, so that the early strength and carbonization resistance of the aggregate can be remarkably improved.
The results of the fact that the water content in the comparative example 1 is less, the granulating rotating speed in the comparative example 2 is lower, and the granulating time in the comparative examples 3 and 4 is shorter show that the fresh dropping strength is obviously reduced, the granulating (balling) efficiency is obviously reduced and the performance of the prepared full solid waste phosphogypsum-based aggregate is poor due to the fact that the water-material ratio and the granulating parameters are not in the optimal range of the invention, and the results show that the full solid waste phosphogypsum-based aggregate with better performance can be prepared by controlling the granulating rotating speed and the granulating time in the specific range by controlling the water-material ratio, and meanwhile, the granulating time can be accurately controlled by adopting the granulating technology, the parameterization, the automation and the clean production of the granulating process are realized, and the granulating efficiency is obviously improved.
Application testing
The raw materials used for the application test are as follows:
The common cement is Portland cement (P.O42.5) with the specific surface area of 300m 2/kg;
The persulfate cement is persulfate gypsum slag cement, and the concrete composition (mass ratio) is as follows: 45% phosphogypsum, 50% slag and 5% Portland cement;
the fine aggregate is natural river sand which is sand in 2 areas, and the fineness modulus is 2.8;
The coarse aggregate is the full solid waste phosphogypsum-based aggregate with the continuous gradation of 4.75-19mm prepared by the invention;
the water reducer is a polycarboxylate water reducer, and the water reducing rate is 15%.
The total solid waste phosphogypsum-based aggregate prepared in examples 1,2 and 4 was applied to the preparation of concrete comprising: 550 parts of ordinary cement or persulfate cement, 880 parts of fine aggregate, 770 parts of coarse aggregate, 180 parts of water and 3 parts of water reducer. The specific grouping is as follows:
application test example 1: the coarse aggregate adopts the full solid waste phosphogypsum-based aggregate in the embodiment 1, the cement adopts the common cement, and the rest is unchanged;
application test example 2: the coarse aggregate adopts the full solid waste phosphogypsum-based aggregate in the embodiment 2, the cement adopts the common cement, and the rest is unchanged;
Application test example 3: the coarse aggregate adopts the full solid waste phosphogypsum-based aggregate in the embodiment 4, the cement adopts the common cement, and the rest is unchanged;
application test example 4: the coarse aggregate adopts the full solid waste phosphogypsum-based aggregate in the embodiment 1, the cement adopts the over-sulfur cement, and the rest is unchanged;
Application test example 5: the coarse aggregate adopts the full solid waste phosphogypsum-based aggregate in the embodiment 2, the cement adopts the over-sulfur cement, and the rest is unchanged;
application test example 6: the coarse aggregate adopts the full solid waste phosphogypsum-based aggregate in the embodiment 4, the cement adopts the over-sulfur cement, and the rest is unchanged;
Concrete preparation steps in the application test examples are as follows:
Weighing the raw materials according to the formula proportion, and adding the water reducer into water and uniformly stirring; pouring the weighed fine aggregate and coarse aggregate into a concrete mixer, and mixing for 1-3min uniformly; pouring the cement into a concrete mixer for stirring for 1-3min, so that each component is uniformly mixed with the fine aggregate and the coarse aggregate; pouring water mixed with a water reducing agent into a concrete mixer, stirring for 1-2min, discharging, molding and standard curing for 7, 28, 90 and 180d to obtain full solid waste phosphogypsum-based aggregate concrete, and measuring the compressive strength at 7, 28, 90 and 180d respectively, wherein the test results are shown in Table 2:
TABLE 2 mechanical Property test results of fully solid waste phosphogypsum-based aggregate concrete
As can be seen from the data in table 2, the compressive strength of the concrete prepared using the portland cement in test examples 1 to 3 and using the aggregates in test examples 1 and 2 as homogeneous aggregates and using the aggregate in test example 3 as core-shell aggregate was found to be significantly higher than the compressive strength of the concrete prepared using test examples 1 and 2 using the core-shell aggregate in test example 3. The results show that the homogeneous aggregate in test examples 1 and 2 is not well compatible with Portland cement, the prepared concrete has low strength, the aim of being compatible with a Portland cement system can be fulfilled by using a reconstruction material, and the early strength and carbonization resistance of the aggregate can be remarkably improved and the combination with matrix cement is enhanced by curing with a sodium silicate curing liquid, so that the compressive strength of the concrete in test example 3 is remarkably improved.
The use of the cement for the tests 4-6 and the use of the aggregates for the tests 4 and 5 as homogeneous aggregates and the use of the aggregate for the test 6 as core-shell aggregates resulted in the finding that the concrete prepared in the tests 4 and 5 had a higher strength than the concrete prepared in the tests 1 and 2, and the results showed that both the core-shell aggregates and the homogeneous aggregates of the present invention were compatible with the cement for the sulfur, and the prepared concrete had a high strength. In addition, since the use of the cement was made of the persulfate, the strength of the prepared concrete was mainly determined by the strength of the aggregate, and thus the strength of the concrete in application test example 6 was slightly lower than that of the concrete in application test example 3, but higher than that of the concrete in application test examples 4 and 5.
It should be noted that, the foregoing embodiments all belong to the same inventive concept, and the descriptions of the embodiments have emphasis, and where the descriptions of the individual embodiments are not exhaustive, reference may be made to the descriptions of the other embodiments.
The foregoing examples merely illustrate embodiments of the invention and are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The preparation method of the full solid waste phosphogypsum-based aggregate is characterized by comprising the following steps:
Adding water into the granulating material, pre-stirring to obtain a premix, and granulating the premix to obtain water-drop green pellets;
Continuously adding a granulating material or a reconstruction material into the water-drop green pellets, reconstructing the water-drop green pellets, and then continuously granulating to obtain capillary green pellets;
Curing the capillary green pellets to obtain the full-solid waste phosphogypsum-based aggregate;
Wherein, the granulating material comprises 70-85% of phosphogypsum, 10-25% of solid waste silicon-aluminum material and 1-20% of solid waste alkali excitant by mass percent; the reconstruction material comprises 0-20% phosphogypsum, 60-90% solid waste silicon-aluminum material and 1-20% solid waste alkali excitant.
2. The method for preparing a total solid waste phosphogypsum-based aggregate according to claim 1, wherein in the preparation process of the water-drop green balls, the water-to-material ratio of the water to the granulating material is (0.17-0.21): 1, the pre-stirring is carried out in a stirrer, and the granulating comprises: and (3) placing the premix containing 60-80 parts of the granulating material into a centrifugal granulator for granulating for 3-10min, wherein the rotation speed of the centrifugal granulator is 20-45r/min.
3. The method for preparing a total solid waste phosphogypsum-based aggregate according to claim 1, wherein 20-40 parts of granulating material or reconstruction material is continuously added into the water drop green ball in the preparation process of the capillary green ball, and the granulating comprises: granulating for 4-10min.
4. The method for preparing a total solid waste phosphogypsum-based aggregate according to claim 3, wherein when 20-40 parts of granulating material is continuously added into the water drop green ball, capillary homogeneous green ball is obtained; and (3) sealing and preserving the capillary homogeneous green balls for 1-3d, and then soaking the capillary homogeneous green balls in water for continuous maintenance for 13-27d to obtain the homogeneous full-solid phosphogypsum-based aggregate.
5. The method for preparing a total solid waste phosphogypsum-based aggregate according to claim 3, wherein when 20-40 parts of the reconstruction material is continuously added into the water drop green ball, a capillary core-shell green ball is obtained; and (3) sealing and preserving the capillary core-shell green balls for 1-3 days, and then soaking the core-shell green balls in water for continuous curing for 13-27 days or soaking the core-shell green balls in sodium silicate curing liquid with the mass concentration of 3-15% for continuous curing for 6-27 days to obtain the core-shell full-solid waste phosphogypsum-based aggregate.
6. The method for preparing a total solid waste phosphogypsum-based aggregate according to any one of claims 1 to 5, wherein the phosphogypsum is an undisturbed silt or wet agglomerate, the water content is 0-15%, the solid content is not less than 85%, and the content of soluble P impurity and F impurity is not more than 3%.
7. The method for producing a total solid waste phosphogypsum-based aggregate according to any one of claims 1 to 5, wherein said solid waste silica alumina material comprises granulated blast furnace slag of grade S95 or more and at least one of high calcium fly ash of grade ii or more or granulated yellow phosphorus slag of grade L95, wherein the CaO content in said high calcium fly ash is more than 10%, and said granulated blast furnace slag of grade S95 or more, said high calcium fly ash of grade ii or more and granulated yellow phosphorus slag of grade L95 are each subjected to a screen of 200 mesh or more.
8. The method according to any one of claims 1 to 5, wherein the solid waste phosphogypsum-based aggregate comprises at least one of grade ii or more steel slag powder, carbide slag and red mud, wherein the CaO content in the carbide slag is not less than 65%, the pH value of the red mud is greater than 10, the na 2 O content is greater than 5%, and the grade ii or more steel slag powder, carbide slag and red mud are all subjected to a 100 mesh screen.
9. An all-solid waste phosphogypsum-based aggregate prepared by the preparation method of any one of claims 1 to 8.
10. Use of the all-solid waste phosphogypsum-based aggregate of claim 9 in the preparation of concrete products.
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