CN113816634A - Method for harmless resource recycling of wet-process phosphoric acid industrial by-products - Google Patents
Method for harmless resource recycling of wet-process phosphoric acid industrial by-products Download PDFInfo
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- CN113816634A CN113816634A CN202010565854.XA CN202010565854A CN113816634A CN 113816634 A CN113816634 A CN 113816634A CN 202010565854 A CN202010565854 A CN 202010565854A CN 113816634 A CN113816634 A CN 113816634A
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- phosphogypsum
- wet
- phosphoric acid
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- process phosphoric
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- 238000000034 method Methods 0.000 title claims abstract description 179
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 73
- 238000004064 recycling Methods 0.000 title claims abstract description 36
- 239000006227 byproduct Substances 0.000 title claims abstract description 23
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims abstract description 200
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 38
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011575 calcium Substances 0.000 claims abstract description 36
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 239000004567 concrete Substances 0.000 claims abstract description 17
- 239000004568 cement Substances 0.000 claims abstract description 16
- 239000004566 building material Substances 0.000 claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 239000011398 Portland cement Substances 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 239000002910 solid waste Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 107
- 239000002893 slag Substances 0.000 claims description 85
- 230000000149 penetrating effect Effects 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 33
- 238000007789 sealing Methods 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011863 silicon-based powder Substances 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkyl phosphate Chemical compound 0.000 claims description 16
- 230000018044 dehydration Effects 0.000 claims description 16
- 238000006297 dehydration reaction Methods 0.000 claims description 16
- 239000011268 mixed slurry Substances 0.000 claims description 16
- 239000002736 nonionic surfactant Substances 0.000 claims description 16
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 16
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 16
- KQFAFFYKLIBKDE-UHFFFAOYSA-M sodium;ethanesulfonate Chemical compound [Na+].CCS([O-])(=O)=O KQFAFFYKLIBKDE-UHFFFAOYSA-M 0.000 claims description 16
- 230000003750 conditioning effect Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 10
- KEZYHIPQRGTUDU-UHFFFAOYSA-N 2-[dithiocarboxy(methyl)amino]acetic acid Chemical compound SC(=S)N(C)CC(O)=O KEZYHIPQRGTUDU-UHFFFAOYSA-N 0.000 claims description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 239000000378 calcium silicate Substances 0.000 claims description 8
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 8
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003814 drug Substances 0.000 claims description 8
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 8
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 8
- 239000003049 inorganic solvent Substances 0.000 claims description 8
- 239000004571 lime Substances 0.000 claims description 8
- 239000008267 milk Substances 0.000 claims description 8
- 210000004080 milk Anatomy 0.000 claims description 8
- 235000013336 milk Nutrition 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 238000005728 strengthening Methods 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000009472 formulation Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/005—Preparing or treating the raw materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/024—Ingredients added before, or during, the calcining process, e.g. calcination modifiers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/028—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
- C04B11/036—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained for the dry process, e.g. dehydrating in a fluidised bed or in a rotary kiln, i.e. to obtain beta-hemihydrate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/36—Inorganic materials not provided for in groups C04B14/022 and C04B14/04 - C04B14/34
- C04B14/365—Gypsum
-
- 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
- C04B28/04—Portland 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a method for harmless resource recycling of byproducts in wet-process phosphoric acid industry, wherein a phosphogypsum harmless process measure is added at the tail end of a production line of the wet-process phosphoric acid process, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, after the extension of the production line of the wet-process phosphoric acid process is realized, phosphogypsum is directly subjected to harmless resource recycling, and the problem of environment-friendly disposal of a large amount of industrial solid wastes phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; meanwhile, the modified phosphogypsum is used as a building material raw material to react with ordinary portland cement to produce a cement-based phosphogypsum concrete building material product. The formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 70-90 parts of phosphogypsum, 5-10 parts of calcium powder, 1-5 parts of modified conditioner and 10-12 parts of water, wherein the invention realizes the harmless resource utilization on the phosphogypsum process line; the method lays a foundation for the sustainable development of the industry of the phosphorization industry, solves the problem of environmental pollution risk in the phosphogypsum which is the waste of the wet-process phosphoric acid industry, and can produce high-quality and hard cement-based phosphogypsum concrete building materials.
Description
Technical Field
The invention relates to a method for recycling phosphogypsum raw slag through baking-free, washing-free conditioning, harmless recycling and recycling, and belongs to the technical field of resource utilization of phosphogypsum industrial waste.
Background
The main process by-product of the wet-process phosphoric acid production line is phosphogypsum, and the phosphogypsum treated on the process production line has strong acidity and also has partial environmental pollutants such as phosphorus, fluorine and the like. The prior art can not carry out resource utilization after timely harmless disposal. Only the phosphogypsum slag can be discharged to a phosphogypsum slag yard for stacking, the acid strength is reduced and the impurity content is reduced through natural placement or a slow process in the stacking process of the slag yard, and the resource is recycled through calcination and water washing. In the process, the investment of environmental protection management of the slag field is extremely large, and meanwhile, certain environmental protection risks exist, and in fact, the by-products are naturally stockpiled in the slag field, so that the pollution elements are slowly released to the nature. With the strict environmental protection supervision, the discharge of the slag yard is strictly supervised, so that enterprises are forced to perform the seepage prevention of the slag yard and the treatment of wastewater, and the environmental protection cost of the enterprises is greatly increased.
The harmless recycling of the phosphogypsum becomes a necessary way of the industry, and the phosphogypsum raw slag on a wet-process phosphoric acid process line cannot be directly conditioned to realize the harmless recycling. The technology takes the phosphogypsum raw slag discharged from the tail end of the wet-process phosphoric acid process as a starting point, directly enters the phosphogypsum discharged from the tail end of the original process into a large-scale high-speed stirrer, gradually adds a conditioner into the stirrer, realizes extension of the original wet-process phosphoric acid process line, adjusts the pH value of the phosphogypsum through modification treatment, synchronously solidifies pollutants in the phosphogypsum, and realizes harmless resource utilization on the phosphogypsum process line. The method lays a foundation for the sustainable development of the industry of the phosphorization industry, solves the problem of environmental pollution risk in the phosphogypsum which is the waste of the wet-process phosphoric acid industry, and can produce high-quality and hard cement-based phosphogypsum concrete building materials. Thoroughly solves the defects of the prior phosphogypsum resource utilization technology.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry, so as to realize the harmless resource recycling on a phosphogypsum process line; the method lays a foundation for sustainable development of the phosphorus chemical industry, solves the problem of environmental pollution risk in the phosphogypsum which is a waste in the wet-process phosphoric acid industry, can produce high-quality and hard cement-based phosphogypsum concrete building materials, and can overcome the defects of the existing phosphogypsum resource utilization technology.
The technical scheme of the invention is as follows: the method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, after extension of the wet-process phosphoric acid process production line is realized, phosphogypsum is directly subjected to harmless resource recycling, and the problem of environment-friendly disposal of a large amount of industrial solid wastes phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; simultaneously, modified phosphogypsum is used as a building material raw material to react with ordinary portland cement to produce a cement-based phosphogypsum concrete building material product, and the formulation of the raw material for the harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 70-90 parts of phosphogypsum, 5-10 parts of calcium powder, 1-5 parts of modified conditioner and 10-12 parts of water, and the production steps are as follows:
s1, at the tail end of a wet-process phosphoric acid process production line, a belt scale is used as a weighing device, the raw phosphogypsum slag is added into a large-scale high-speed stirrer, and a modified conditioner of the phosphogypsum is added according to the weight proportion of the phosphogypsum to obtain mixed slurry with the pH value of 6-9; s2, adding calcium powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.
The raw material formula of the formula also comprises 3-10 parts of silicon powder by weight, and the silicon powder is gradually added in the process of continuously stirring after the calcium powder is added in the step S2.
The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent;
the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.
In the step s1, the water content of the phosphogypsum raw slag is 35-45 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 45-55 parts.
In step S2, the calcium powder is nano calcium carbonate, nano silica powder or a combination of the two.
In step S3, the aging time is 5-8 hours, and the drying temperature is 300 °.
The product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.
Compared with the prior art, the method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct has the beneficial effects that:
(1) realizing the harmless resource utilization on the phosphogypsum process line; lays a foundation for the sustainable development of the industry of the phosphorization industry, solves the problem of environmental pollution risk in the phosphogypsum which is the waste of the wet-process phosphoric acid industry, and lays a foundation for the harmless resource utilization of the by-products of the wet-process phosphoric acid process;
(2) the phosphogypsum harmless recycling process measures are added in the process links, the phosphogypsum process production line is extended and then is directly treated, so that the phosphogypsum is treated in time without entering a storage yard to generate the risk of environmental pollution;
(3) the calcium powder and the silicon powder are added according to the proportion through conditioning of a conditioner, and the mixture is dried to be used as a building material raw material to replace common sandstone materials to produce building material products;
(4) through conditioning of the conditioner, the problem of acid pollution caused by acid radical ions such as phosphorus, sulfur, fluorine and the like in the phosphogypsum raw material can be solved, and through a plurality of tests, the PH value of the produced hard concrete block is more than 7, so that the problem of acidity of the phosphogypsum raw material is thoroughly solved;
(5) the conditioning of the phosphogypsum, specifically, adding a certain proportion of penetrant for homogenization treatment according to the quality of the phosphogypsum raw slag, then adding a sealing agent to form a phosphogypsum sealing crystal, permanently sealing harmful substances in the phosphogypsum raw slag, thoroughly solving the problem of permeation and leakage of the harmful substances of the phosphogypsum, aging the phosphogypsum sealing crystal at a certain temperature and within a certain time to ensure the complete formation and stability of the sealing crystal, further adding a propping agent which can be selectively combined with the sealing crystal to ensure the integrity and the certain strength of the formed sealing crystal, realizing the stable sealing of the harmful substances fixed in crystal lattices, solving the condition that the phosphogypsum is damp and acid-returning, simultaneously solving the secondary pollution problem of the phosphogypsum product, finally adding a curing agent to improve the bonding and curing performance of the phosphogypsum sealing crystal, and realizing the finished product index of a novel product of the phosphogypsum, after the phosphogypsum raw slag is conditioned, harmful substances are sealed, and the conditioned phosphogypsum raw material has extremely low solubility of phosphorus, fluorine and heavy metals and no pollution risk to the environment;
(6) after the phosphogypsum is subjected to harmless treatment, the phosphogypsum is used as a sandstone substitute material and directly enters a production link, and the phosphogypsum is stockpiled without a special field, so that the field occupation and the environmental pollution are saved;
(7) after the phosphogypsum is modified, the physical and chemical properties are stable, the PH is maintained neutral, and repeated water absorption, moisture regain and caking can not be caused in the natural storage process; the stacking and the subsequent utilization are convenient;
(8) after the ardealite is modified, the ardealite can be directly blended with ordinary portland cement for use. The produced cement-based phosphogypsum concrete building material product has the advantages that harmful substances are completely sealed, the seepage is avoided, and the secondary pollution risk of the building material product is thoroughly solved.
Drawings
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Detailed Description
Example 1.
A method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, the phosphogypsum is directly subjected to harmless resource recycling after the extension of the wet-process phosphoric acid process production line is realized, and the problem of environment-friendly disposal of a large amount of industrial solid waste phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; the formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 70 parts of phosphogypsum, 5 parts of calcium powder, 1 part of modified conditioner and 10 parts of water, and the production steps are as follows:
s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry; s2, adding calcium powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.
The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent; the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.
In the step s1, the water content of the phosphogypsum raw slag is 35 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 45 parts; in step S1, pH value of PH 6-9; in step S2, the calcium powder is nano calcium carbonate, nano silicon dioxide powder or a combination of the two; in step S3, the aging time is 5-8 hours, and the drying temperature is 300 degrees; the product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.
Example 2.
A method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, the phosphogypsum is directly subjected to harmless resource recycling after the extension of the wet-process phosphoric acid process production line is realized, and the problem of environment-friendly disposal of a large amount of industrial solid waste phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; the formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 80 parts of phosphogypsum, 8 parts of calcium powder, 3 parts of modified conditioner and 11 parts of water, and the production steps are as follows:
s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry; s2, adding calcium powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.
The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent; the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.
In the step s1, the water content ratio of the phosphogypsum raw slag is 40 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 50 parts; in step S1, pH value of PH 6-9; in step S2, the calcium powder is nano calcium carbonate, nano silicon dioxide powder or a combination of the two; in step S3, the aging time is 5-8 hours, and the drying temperature is 300 degrees; the product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.
Example 3.
The method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, after extension of the wet-process phosphoric acid process production line is realized, phosphogypsum is directly subjected to harmless resource recycling, and the problem of environment-friendly disposal of a large amount of industrial solid wastes phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; the formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 90 parts of phosphogypsum, 10 parts of calcium powder, 5 parts of modified conditioner and 12 parts of water, and the production steps are as follows:
s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry; s2, adding calcium powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.
The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent; the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.
In the step s1, the water content ratio of the phosphogypsum raw slag is 45 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 55 parts; in step S1, pH value of PH 6-9; in step S2, the calcium powder is nano calcium carbonate, nano silicon dioxide powder or a combination of the two; in step S3, the aging time is 5-8 hours, and the drying temperature is 300 degrees; the product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.
The raw material formula of the formula also comprises 3-10 parts of silicon powder by weight,
example 4.
A method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, the phosphogypsum is directly subjected to harmless resource recycling after the extension of the wet-process phosphoric acid process production line is realized, and the problem of environment-friendly disposal of a large amount of industrial solid waste phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; the formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 70 parts of phosphogypsum, 5 parts of calcium powder, 1 part of modified conditioner, 10 parts of water and 3 parts of silicon powder, and the production steps are as follows:
s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry; s2, sequentially adding calcium powder, silicon powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.
The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent; the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.
In the step s1, the water content of the phosphogypsum raw slag is 35 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 45 parts; in step S1, pH value of PH 6-9; in step S2, the calcium powder is nano calcium carbonate, nano silicon dioxide powder or a combination of the two; in step S3, the aging time is 5-8 hours, and the drying temperature is 300 degrees; the product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.
Example 5.
A method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, the phosphogypsum is directly subjected to harmless resource recycling after the extension of the wet-process phosphoric acid process production line is realized, and the problem of environment-friendly disposal of a large amount of industrial solid waste phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; the formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 80 parts of phosphogypsum, 8 parts of calcium powder, 3 parts of modified conditioner, 11 parts of water and 7 parts of silicon powder, and the production steps are as follows:
s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry; s2 and S2, sequentially adding calcium powder, silicon powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.
The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent; the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.
In the step s1, the water content ratio of the phosphogypsum raw slag is 40 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 50 parts; in step S1, pH value of PH 6-9; in step S2, the calcium powder is nano calcium carbonate, nano silicon dioxide powder or a combination of the two; in step S3, the aging time is 5-8 hours, and the drying temperature is 300 degrees; the product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.
Example 6.
The method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, after extension of the wet-process phosphoric acid process production line is realized, phosphogypsum is directly subjected to harmless resource recycling, and the problem of environment-friendly disposal of a large amount of industrial solid wastes phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; the formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 90 parts of phosphogypsum, 10 parts of calcium powder, 5 parts of modified conditioner, 12 parts of water and 10 parts of silicon powder, and the production steps are as follows:
s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry; s2, sequentially adding calcium powder, silicon powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.
The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent; the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.
In the step s1, the water content ratio of the phosphogypsum raw slag is 45 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 55 parts; in step S1, pH value of PH 6-9; in step S2, the calcium powder is nano calcium carbonate, nano silicon dioxide powder or a combination of the two; in step S3, the aging time is 5-8 hours, and the drying temperature is 300 degrees; the product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.
Through multiple tests, in examples 1-6, the modified phosphogypsum does not have self-adhesiveness any more, the pH value of the phosphogypsum is maintained at about 7, the content of soluble P is not higher than 5ppm, the content of soluble F is not higher than 2ppm, the modified phosphogypsum is used as a building material raw material and can be directly blended with common silicate cement, and the blending ratio of the phosphogypsum reaches more than 70 parts, so that a phosphogypsum-based cement concrete product is obtained.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (8)
1. The method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, after extension of the wet-process phosphoric acid process production line is realized, phosphogypsum is directly subjected to harmless resource recycling, and the problem of environment-friendly disposal of a large amount of industrial solid wastes phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; simultaneously, modified phosphogypsum is used as a building material raw material to react with ordinary portland cement to produce a cement-based phosphogypsum concrete building material product, and the formulation of the raw material for the harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 70-90 parts of phosphogypsum, 5-10 parts of calcium powder, 1-5 parts of modified conditioner and 10-12 parts of water, and the production steps are as follows:
s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry;
s2, adding calcium powder and water into the mixed slurry, and stirring to obtain a mixed material;
and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.
2. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1, characterized in that: the raw material formula of the formula also comprises 3-10 parts of silicon powder by weight, and the silicon powder is gradually added in the process of continuously stirring after the calcium powder is added in the step S2.
3. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1 or 2, characterized in that: the conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent;
the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate;
the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.
4. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1 or 2, characterized in that: in the step s1, the water content of the phosphogypsum raw slag is 35-45 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 45-55 parts.
5. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1 or 2, characterized in that: in step S1, pH value is pH 6-9.
6. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1 or 2, characterized in that: in step S2, the calcium powder is nano calcium carbonate, nano silica powder or a combination of the two.
7. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1 or 2, characterized in that: in step S3, the aging time is 5-8 hours, and the drying temperature is 300 °.
8. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1 or 2, characterized in that: the product obtained in the step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete building material products.
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