CN115504695B - Phosphogypsum recycling method - Google Patents
Phosphogypsum recycling method Download PDFInfo
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- CN115504695B CN115504695B CN202211084896.7A CN202211084896A CN115504695B CN 115504695 B CN115504695 B CN 115504695B CN 202211084896 A CN202211084896 A CN 202211084896A CN 115504695 B CN115504695 B CN 115504695B
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- phosphogypsum
- slurry
- acidolysis
- washing
- countercurrent washing
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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 202
- 238000000034 method Methods 0.000 title claims abstract description 116
- 238000004064 recycling Methods 0.000 title description 21
- 238000005406 washing Methods 0.000 claims abstract description 143
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 101
- 238000003825 pressing Methods 0.000 claims abstract description 68
- 238000002156 mixing Methods 0.000 claims abstract description 64
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 35
- 238000011084 recovery Methods 0.000 claims abstract description 34
- 239000006260 foam Substances 0.000 claims abstract description 33
- 238000007667 floating Methods 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims description 151
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 120
- 239000007788 liquid Substances 0.000 claims description 79
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 76
- 238000001914 filtration Methods 0.000 claims description 39
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 239000004566 building material Substances 0.000 claims description 5
- 238000011085 pressure filtration Methods 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 abstract description 57
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 57
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 49
- 239000010440 gypsum Substances 0.000 abstract description 37
- 229910052602 gypsum Inorganic materials 0.000 abstract description 37
- 239000000843 powder Substances 0.000 abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 238000002386 leaching Methods 0.000 abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 abstract description 8
- 229910052700 potassium Inorganic materials 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 239000000706 filtrate Substances 0.000 description 49
- 239000012065 filter cake Substances 0.000 description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 18
- 239000012535 impurity Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 238000007790 scraping Methods 0.000 description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 description 12
- 235000017550 sodium carbonate Nutrition 0.000 description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 11
- 235000011941 Tilia x europaea Nutrition 0.000 description 11
- 239000004571 lime Substances 0.000 description 11
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002893 slag Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 239000003337 fertilizer Substances 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- -1 phosphorus compound Chemical class 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 238000004042 decolorization Methods 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 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 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B11/266—Chemical gypsum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- 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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/0445—Synthetic gypsum, e.g. phosphogypsum
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/143—Calcium-sulfate
- C04B22/144—Phosphogypsum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/65—Chroma (C*)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Removal Of Specific Substances (AREA)
- Extraction Or Liquid Replacement (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a phosphogypsum recovery method, which comprises the following steps: mixing phosphogypsum and carbonate, performing primary acidolysis to remove floating foam, performing secondary acidolysis, and then performing filter pressing and washing to obtain purified phosphogypsum. According to the phosphogypsum recovery method, after phosphogypsum is recovered, various performance indexes of phosphogypsum are obviously improved compared with those before treatment, wherein the soluble phosphorus of phosphogypsum is reduced to below 0.016%, the total phosphorus is reduced to about 0.1%, the pH value of gypsum leaching solution is improved to 6-7 from 1-2, the gypsum leaching solution can be directly discharged without treatment, the contents of Mg, na, fe, K, al and organic carbon are greatly reduced, the whiteness of the gypsum is improved to about 78 from 22.71, the purification degree of the gypsum is far higher than that of the conventional water washing and acidolysis process, and the quality index of the treated phosphogypsum is superior to the relevant requirements of building gypsum powder standard, and the phosphogypsum can be directly used as building gypsum.
Description
Technical Field
The invention belongs to the field of recovery, and particularly relates to a phosphogypsum recovery method.
Background
Phosphogypsum is a main byproduct generated in the process of preparing phosphoric acid by adopting a wet method, and the main component of phosphogypsum is calcium sulfate dihydrate, and each time 1 ton of phosphoric acid is produced (P is used as a raw material 2 O 5 Calculated as a percentage) yields about 4.5 to 5.5 tons of phosphogypsum byproduct. Phosphogypsum has complex composition, and besides calcium sulfate, phosphorus ore which is not completely decomposed, phosphoric acid which remains in the gypsum, silicon dioxide, fluoride, metal cation precipitation, acid insoluble substances, organic substances and the like.
Along with the continuous accumulation of phosphogypsum, the storage capacity of a slag yard is gradually reduced, and the phosphogypsum is piled up to occupy a large amount of land resources, wherein soluble impurities can cause serious environmental pollution along with rainwater seepage. Therefore, the phosphogypsum is pretreated, so that the quality of the phosphogypsum is improved, and the economic value of the phosphogypsum is improved, which is a key for solving the phosphogypsum problem. The existing phosphogypsum treatment methods include a lime neutralization method, a water washing method, a flotation method, a flash firing method and the like. The flotation method has high reagent cost and is uneconomical; the flash firing method has less treatment capacity; the lime neutralization method can eliminate soluble phosphorus and fluorine elements, but the phosphorus elements remain in the gypsum, so that phosphorus resource waste is caused. The water washing method can effectively remove soluble impurities and recover part of water-soluble phosphorus elements, but still cannot treat the non-water-soluble phosphorus which is nearly doubled in proportion to the water-soluble phosphorus in the phosphogypsum, and the water-soluble substance in the phosphogypsum is low in proportion, so that the content of calcium sulfate dihydrate is not greatly improved by water washing purification.
Disclosure of Invention
In order to overcome the problems of the prior art, one of the purposes of the present invention is to provide a phosphogypsum recovery method.
The second purpose of the invention is to provide phosphogypsum.
It is a further object of the present invention to provide an application of phosphogypsum in building materials.
The fourth object of the invention is to provide a phosphogypsum recovery system.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a method for recovering phosphogypsum, comprising the following steps:
mixing phosphogypsum and carbonate, performing primary acidolysis to remove floating foam, performing secondary acidolysis, and then performing filter pressing and washing to obtain purified phosphogypsum.
Preferably, the carbonate is a soluble carbonate or is formed by mixing a soluble carbonate and an insoluble carbonate. The soluble carbonate in the invention can dissociate calcium sulfate crystals in phosphogypsum, thereby releasing impurities wrapped in the calcium phosphate crystals and realizing the purpose of purifying phosphogypsum.
Preferably, the soluble carbonate is at least one of sodium carbonate and potassium carbonate.
Preferably, the mass percent of soluble carbonate is greater than 40% based on the total mass of carbonate.
Preferably, the insoluble carbonate is calcium carbonate.
Preferably, the calcium carbonate has a particle size of no more than 60 mesh. When the particle size of the calcium carbonate is larger than 60 meshes, the calcium carbonate is easy to generate a calcium sulfate coating phenomenon in the slow decomposition process, so that the reaction is not thoroughly carried out, and the purity of the final product is influenced.
Preferably, the mass ratio of phosphogypsum to carbonate is (4-9): 1, a step of; further preferably, the mass ratio of phosphogypsum to carbonate is (7-9): 1.
preferably, the acid liquor used in the primary acidolysis step is at least one of nitric acid and sulfuric acid; further preferably, the acid solution used in the primary acidolysis step is sulfuric acid.
Preferably, in the primary acidolysis step, the addition amount of sulfuric acid (calculated as pure sulfuric acid) is 18-22% of the mass of phosphogypsum.
Preferably, in the secondary acidolysis step, the addition amount of sulfuric acid (calculated as pure sulfuric acid) is 6-8% of the mass of phosphogypsum.
Preferably, the acid liquor used in the secondary acidolysis step is at least one of nitric acid and sulfuric acid; further preferably, the acid solution used in the secondary acidolysis step is sulfuric acid.
The added sulfuric acid has two positions, one part of the sulfuric acid reacts with calcium salt to form calcium sulfate precipitate which is left in gypsum to promote the grade of the gypsum, and the rest of the sulfuric acid returns to the phosphoric acid device along with the washing liquid to reduce the sulfuric acid consumption of the phosphoric acid device.
Preferably, the sulfuric acid is sulfuric acid with the mass fraction of 30% -50%; further preferably, the sulfuric acid is 35% -45% sulfuric acid by mass.
Preferably, the temperature of the primary acidolysis is 25-90 ℃.
Preferably, the temperature of the secondary acidolysis is 65-85 ℃.
Preferably, the secondary acidolysis time is 1-2 h.
Preferably, the phosphogypsum and carbonate are mixed for one acidolysis step, which comprises the following steps: mixing phosphogypsum, carbonate and water to obtain slurry A, and then introducing acid liquor from the bottom of the slurry A and stirring to obtain foam-containing slurry; further preferably, the phosphogypsum and carbonate are mixed for one acidolysis step, specifically: mixing phosphogypsum, carbonate and water to prepare slurry A, and then introducing acid liquor from the bottom of the slurry A, stirring, and adding the acid liquor for 15-50 min to obtain the foam-containing slurry. And in addition, the generated carbon dioxide gas can be hydraulically cut into fine foam through the stirring step, so that the foam-containing slurry is obtained. Acidolysis of residual phosphorite and decomposition of carbonate are carried out simultaneously in the process of fully reacting the slurry A with dilute sulfuric acid, carbon dioxide gas is generated, the carbon dioxide gas is cut by hydraulic force (stirring force) to generate fine powder, and the generated fine powder fully contacts with the reaction slurry and collides or adheres to enable organic impurities to be separated from phosphogypsum.
Preferably, the stirring speed is 300-1000 r/min; further preferably, the stirring speed is 300-600 r/min; still further preferably, the stirring rate is 300 to 500r/min; more preferably, the stirring rate is 350 to 500r/min.
Preferably, the solid content of the slurry A is 30-50%.
Preferably, the temperature of the slurry A is 25 to 90 ℃.
Preferably, the recovery method further comprises a step of allowing the primary acidolysis product to stand. In the standing process, the acidolysis product is layered, the upper layer is a floating foam, and the floating foam contains organic matters.
Preferably, the step of removing the froth specifically comprises: scraping the floating foam layer by a scraper, then carrying out filter pressing on the floating foam layer, wherein the solid obtained by filter pressing is decolored slag, and the liquid obtained by filter pressing is recovered to be used for preparing the solvent used for preparing the slurry A from phosphogypsum and carbonate.
Preferably, the washing is performed by countercurrent washing.
Preferably, the countercurrent washing has a stage number of 3 to 5 stages; further preferably, the countercurrent washing is performed in a number of 4 stages.
Preferably, the effluent of the next stage countercurrent washing is used as the wash liquid of the previous stage countercurrent washing.
Preferably, the filter pressing step specifically comprises: and (3) conveying the liquid obtained in the pressure filtration step to a phosphoric acid production workshop as a phosphoric acid production raw material, and filtering after preparing the solid obtained in the pressure filtration step into slurry B.
Preferably, the solid content of the slurry B is 30-50%.
In a second aspect, the invention provides phosphogypsum, made by the method provided in the first aspect.
Preferably, the phosphogypsum contains no more than 0.02% of water-soluble phosphorus; further preferably, the phosphogypsum contains no more than 0.016% of water-soluble phosphorus.
Preferably, the total phosphorus content in the phosphogypsum is not higher than 0.2%; further preferably, the total phosphorus content in the phosphogypsum is not higher than 0.14%.
Preferably, the fluorine content in the phosphogypsum is not higher than 0.04%; further preferably, the fluorine content in the phosphogypsum is not higher than 0.018%.
Preferably, the magnesium content in the phosphogypsum is not higher than 0.02%; further preferably, the magnesium content in the phosphogypsum is not higher than 0.009%.
Preferably, the sodium content in the phosphogypsum is not higher than 0.04%; further preferably, the sodium content in the phosphogypsum is not higher than 0.019%.
Preferably, the iron content in the phosphogypsum is not higher than 0.06%; further preferably, the iron content in the phosphogypsum is not higher than 0.04%.
Preferably, the potassium content in the phosphogypsum is not higher than 0.04%; further preferably, the potassium content in the phosphogypsum is not higher than 0.025%.
Preferably, the aluminum content in the phosphogypsum is not higher than 0.03%; further preferably, the aluminum content in the phosphogypsum is not higher than 0.01%.
Preferably, the whiteness of the phosphogypsum is 70-90; further preferably, the whiteness of the phosphogypsum is 77-90; still more preferably, the phosphogypsum has a whiteness of 77 to 80.
Preferably, the organic carbon content in the phosphogypsum is not higher than 0.03%; further preferably, the organic carbon content in the phosphogypsum is not higher than 0.014%.
In a third aspect, the invention provides the use of phosphogypsum in building materials.
Preferably, the building material is building gypsum.
The fourth aspect of the invention provides a phosphogypsum recovery system, which is used for implementing the phosphogypsum recovery method provided by the first aspect of the invention, and comprises an acidolysis device, a square groove, a formation groove, a filtering system and a countercurrent washing device, wherein the bottom of the acidolysis device is provided with a first acid liquid inlet, the acidolysis device is connected with the square groove, a scraper is arranged on the square groove, the square groove is connected with the formation groove, a second acid liquid inlet is arranged on the formation groove, the formation groove is connected with the filtering system, and a solid outlet of the filtering system is connected with the countercurrent washing device. Mixing phosphogypsum and carbonate, performing primary acidolysis in an acidolysis device, conveying the mixed phosphogypsum and carbonate into a square groove, removing floating foam by a scraper on the square groove, performing secondary acidolysis in a forming groove, performing filter pressing by a filtering device, and washing by a countercurrent washing device to obtain purified phosphogypsum.
The phosphogypsum and carbonate mixture is transferred to an acidolysis device after pulp mixing, then acid liquor is introduced from a first acid liquor inlet at the bottom of the acidolysis device, primary acidolysis is carried out in the acidolysis device, products after primary acidolysis are transferred to a square groove, and are placed in the square groove for layering, a floating foam layer containing organic matters is arranged at the top of the square groove, phosphogypsum pulp after primary acidolysis is arranged at the bottom of the square groove, a scraping machine on the square groove is used for scraping the floating foam layer, the pulp after scraping is transferred to a forming groove from the bottom of the square groove, acid liquor is introduced into the forming groove through a second acid liquor inlet on the forming groove, secondary acidolysis is carried out in the forming groove, products after secondary acidolysis are introduced into a filtering system for filtering, and then the solids filtered by the filtering system are subjected to countercurrent washing by a countercurrent washing device.
Preferably, the first acid inlet is connected with an acid storage device.
Preferably, the second acid inlet is connected with an acid storage device.
Preferably, the filter system comprises a filter pressing device, a slurry mixing device and a filter device, wherein the filter pressing device is connected with the formation tank, a liquid outlet of the filter pressing device is connected with the phosphoric acid production system, a solid outlet of the filter pressing device is connected with the slurry mixing device, the slurry mixing device is connected with the filter device, and a solid outlet of the filter device is connected with the countercurrent washing device. And conveying the secondary acidolysis product in the formation tank to a filter pressing device for filter pressing, and conveying the liquid after filter pressing by the filter pressing device to a phosphoric acid production system through a liquid outlet for recovering the phosphorus component in phosphogypsum, wherein the phosphorus component can be used for producing phosphoric acid after being recovered. And conveying the solid subjected to filter pressing by the filter pressing device to a slurry mixing device for slurry mixing through a solid outlet on the filter pressing device, conveying the slurry to a filtering device for filtering after slurry mixing, and washing the solid filtered by the filtering device through a countercurrent washing device.
Preferably, the recycling system further comprises a pulp mixer, and the pulp mixer is connected with the acidolysis device. The size mixer is used for mixing phosphogypsum and carbonate.
Preferably, the pulp mixer is connected to the liquid outlet of the filtering device. And delivering the liquid filtered by the filtering device to a pulp mixer to be used as pulp mixing liquid.
Preferably, the pulp mixer is connected with a water source.
Preferably, the filter device is a belt filter device.
Preferably, the size mixing device is connected with a water source.
Preferably, the square groove is connected with a filter press, and a liquid outlet of the filter press is connected with a pulp mixer. The floating foam layer is scraped into the filter press by the scraper on the square groove for filter pressing, and liquid during filter pressing of the filter press is conveyed to the pulp mixer through the liquid outlet of the filter press to be used as pulp mixing liquid. The solid produced by filter pressing of the filter press is decolored slag.
Preferably, the washing stage number of the countercurrent washing device is 3-6; further preferably, the countercurrent washing apparatus has a washing stage number of 4.
Preferably, the countercurrent washing apparatus comprises a primary countercurrent washing zone, a secondary countercurrent washing zone, a tertiary countercurrent washing zone and a quaternary countercurrent washing zone.
Preferably, the washing liquid inlet of the first-stage countercurrent washing zone is respectively connected with the liquid outlet of the second-stage countercurrent washing zone and a water source.
Preferably, the liquid outlet of the first-stage countercurrent washing zone is connected with a pulp mixing device.
Preferably, the washing liquid inlet of the secondary countercurrent washing zone is respectively connected with the liquid outlet of the tertiary countercurrent washing zone and a water source.
Preferably, the washing liquid inlet of the three-stage countercurrent washing zone is respectively connected with the liquid outlet of the four-stage countercurrent washing zone and a water source.
Preferably, the wash liquor inlet of the four stage counter current wash zone is connected to a water source.
Preferably, the water source is a process water source.
The beneficial effects of the invention are as follows: according to the phosphogypsum recovery method, after phosphogypsum is recovered, various impurity contents in phosphogypsum are obviously reduced compared with those before untreated phosphogypsum, wherein the soluble phosphorus of phosphogypsum is reduced to below 0.016%, the total phosphorus is reduced to about 0.1%, the pH value of gypsum leaching solution is increased from 1-2 to 6-7, the gypsum leaching solution can be directly discharged without treatment, the contents of Mg, na, fe, K, al and organic carbon are greatly reduced, the whiteness of the gypsum is increased to about 78 from 22.71, the purification degree of the gypsum is far higher than that of the conventional water washing and acidolysis process, and the quality index of the treated phosphogypsum is superior to the relevant requirements of building gypsum powder standards, and the phosphogypsum can be directly used as building gypsum.
In addition, the recovery method can realize the recovery of the phosphorus in the phosphogypsum, and the recovered phosphorus component is directly conveyed to a phosphoric acid production workshop for producing phosphoric acid. The waste liquid generated by filtering, washing and pressure filtration can be recycled, so that the utilization rate of raw materials is improved, the treatment cost of the waste liquid is reduced, and the production cost is saved.
The recycling system has the advantages of high automation degree, low labor intensity, simple equipment, low equipment cost and convenient maintenance, can realize the automatic recycling of phosphogypsum, can directly recycle waste liquid in the recycling process, and has high raw material utilization rate.
Drawings
FIG. 1 is a schematic flow chart of the phosphogypsum recovery method in examples 1 to 4 of the present invention.
Fig. 2 is a schematic diagram of the recovery system in embodiment 6 of the present invention.
FIG. 3 is a schematic view showing the structure of a countercurrent washing apparatus in example 6 of the present invention.
Detailed Description
Specific embodiments of the present invention will be described in further detail below with reference to the drawings and examples, but the practice and protection of the present invention are not limited thereto. It should be noted that the following processes, unless otherwise specified, are all realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
The methods for measuring the component content of purified phosphogypsum used in examples 1 to 4 are the measurement methods described in the phosphomolybdic acid quinoline gravimetric method, ICP-MS and Q/520122K-002-2020.
Example 1
The phosphogypsum recycling method in the embodiment specifically comprises the following steps:
(1) Phosphogypsum of certain phosphorus compound fertilizer plant in Hubei province is selected, the phosphogypsum is gray black in color, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the phosphogypsum is 0.4986%, the total phosphorus is 1.524%, and the pH of the leaching solution is between 1 and 2.
(2) Sequentially weighing 900kg of phosphogypsum and 100kg of sodium carbonate, and mixing the phosphogypsum and the sodium carbonate to obtain a mixture; preparing a mixture of phosphogypsum and sodium carbonate and process water into mixed slurry according to the weight ratio of 1:2, wherein the temperature of the process water is 30 ℃, and fully stirring to uniformly distribute liquid phase and solid phase to obtain slurry A;
(3) Preparing dilute sulfuric acid with the mass fraction of 40%;
(4) Acidolysis decolorization: transferring the slurry A into a reaction container, wherein the stirring speed in the container is 350r/min, adding the sulfuric acid solution obtained in the step (3) into the slurry from the bottom of the reaction container, wherein the adding amount of the sulfuric acid solution is 450kg, and the adding time of the sulfuric acid is controlled to be 25min;
(5) Stirring for 20min after the sulfuric acid is added, then transferring the slurry with the foam into a square groove, standing for 30min, scraping off upper layer floating foam on the surface of the slurry after standing is finished, and separating organic impurities from the gypsum slurry;
(6) The upper layer floating foam scraped in the step (5) is sent to a filter press for filter pressing, the filter cake is decolorized slag, and the filtrate is sent to the step (2) for preparing slurry A after recovery treatment;
(7) Transferring the slurry with the upper layer of floating foam removed in the step (5) into a forming tank, and adding the dilute sulfuric acid prepared in the step (3) into the forming tank again, wherein the adding amount of the sulfuric acid solution is 180kg;
(8) Adding steam into the forming tank for heat preservation, controlling the temperature at 75 ℃, continuously stirring the slurry, and controlling the forming time at 1.5h;
(9) Carrying out filter pressing on the formed slurry, recycling the filtrate, and then sending the filtrate to a phosphoric acid workshop as a phosphoric acid production raw material, wherein the filter cake is subjected to slurry mixing by using process water, and the temperature and the dosage of the process water are the same as those of the process water in the step (2) in the example;
(10) Filtering the slurry obtained in the step (9), and recovering and conveying the filtered filtrate to the step (2) to prepare slurry A, and carrying out 4-level countercurrent washing on a filter cake to obtain purified phosphogypsum;
the filtrate of the subsequent stage washing in the 4-stage countercurrent washing in the step (10) is used as the washing liquid in the previous stage washing, the washing liquid in the final stage washing is process water, and the temperature and the consumption of the process water are the same as those of the process water in the step (2) in the example. And (3) in the step (10), the final filtrate after countercurrent washing can be recovered and conveyed to the step (9) for size mixing of the filter cake.
The content of the components of the purified phosphogypsum obtained in this example was tested to obtain: the purified gypsum contains 0.0136 percent of water-soluble phosphorus, 0.1142 percent of total phosphorus, 0.0167 percent of water-soluble fluorine, 23.14 percent of free water, white powder of gypsum after drying at 45 ℃ and 78.92 percent of whiteness.
Example 2
The phosphogypsum recycling method in the embodiment specifically comprises the following steps:
(1) Phosphogypsum of a certain phosphorus compound fertilizer plant in Hubei province is selected, the phosphogypsum is gray black in color, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the phosphogypsum is 0.4986%, the total phosphorus is 1.524%, and the pH of the leaching solution is between 1 and 2.
(2) According to mass ratio m Gypsum plaster ：m Soda ash ：m Lime powder 875kg of phosphogypsum, 62.5kg of sodium carbonate and 62.5kg of lime powder are weighed in sequence according to the ratio of 7:0.5:0.5, and then the three materials are mixed; preparing a mixture slurry from the mixture and process water according to the weight ratio of 1:2, wherein the process water is prepared from water and steam condensate, the temperature is controlled at 55 ℃, and the mixture is fully stirred to uniformly distribute liquid phase and solid phase, so as to obtain slurry A;
(3) Preparing 35% of dilute sulfuric acid;
(4) Acidolysis decolorization: transferring the slurry A into a reaction container, wherein the stirring speed in the container is 400r/min, adding the sulfuric acid solution obtained in the step (3) into the slurry from the bottom of the reaction container, wherein the adding amount of the sulfuric acid solution is 550kg, and the adding time of the sulfuric acid is controlled to be 35min;
(5) Stirring for 20min after the sulfuric acid is added, then transferring the slurry with the foam into a square groove, standing for 30min, scraping the foam on the surface of the slurry after standing is finished, and separating the organic impurities from the gypsum slurry;
(6) Conveying the froth scraped off from the surface of the slurry in the step (5) to a filter press for filter pressing, and conveying the filter liquor after filter pressing to the step (2) for preparing the slurry A after recovery treatment;
(7) The slurry after defoaming in the step (5) is moved into a forming tank, and dilute sulfuric acid prepared in the step (3) is added into the forming tank again, wherein the adding amount of the dilute sulfuric acid is 150kg;
(8) Adding steam into the forming tank for heat preservation, controlling the temperature at 70 ℃, continuously stirring the slurry, and controlling the forming time at 1h;
(9) Carrying out filter pressing on the formed slurry, recycling the filtrate, and then sending the filtrate to a phosphoric acid workshop as a phosphoric acid production raw material, wherein the filter cake is subjected to slurry mixing by using process water, and the temperature, the components and the dosage of the process water are the same as those of the process water used in the step (2) of the example;
(10) And (3) filtering the slurry obtained in the step (9), and recovering and conveying the filtered filtrate to the step (2) for preparing slurry A, and carrying out 4-level countercurrent washing on the filter cake to obtain purified phosphogypsum.
In the step (10), filtrate generated in the subsequent stage of washing during countercurrent washing is used as washing liquid in the previous stage of washing, washing liquid in the last stage of washing is process water, and the temperature, the components and the dosage of the process water are the same as those of the process water in the step (2) in the example. And (3) in the step (10), the final filtrate after countercurrent washing can be recovered and conveyed to the step (9) for size mixing of the filter cake.
The content of the components of the purified phosphogypsum obtained in this example was tested to obtain: the purified gypsum contains water-soluble phosphorus of 0.0124%, total phosphorus of 0.0912%, water-soluble fluorine content of 0.0142%, free water of 22.34%, white powder of gypsum after drying at 45deg.C, and whiteness of 78.31.
Example 3
The phosphogypsum recycling method in the embodiment specifically comprises the following steps:
(1) Phosphogypsum of a certain phosphorus compound fertilizer plant in Hubei province is selected, the phosphogypsum is gray black in color, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the phosphogypsum is 0.4986%, the total phosphorus is 1.524%, and the pH of the leaching solution is between 1 and 2.
(2) According to m Phosphogypsum ：m Soda ash ：m Lime powder The mass ratio of the phosphogypsum to the sodium carbonate is (8:0.4:0.6), and the phosphogypsum is (800 kg), the sodium carbonate is (40 kg) and the lime powder is (60 kg) sequentially weighed and mixed; preparing a mixture slurry from the mixture and process water according to a weight ratio of 1:2, wherein the process water is prepared from clear water and steam condensate, the temperature is controlled at 60 ℃, and the mixture is fully stirred to uniformly distribute liquid phases and solid phases, so as to obtain a slurry A;
(3) Preparing dilute sulfuric acid with the mass fraction of 45%;
(4) Acidolysis decolorization: transferring the slurry A into a reaction container, wherein the stirring speed in the container is 400r/min, adding the sulfuric acid solution obtained in the step (3) into the slurry from the bottom of the reaction container, wherein the adding amount of the sulfuric acid solution is 370kg, and the adding time of the sulfuric acid is controlled to be 25min;
(5) Stirring for 20min after the sulfuric acid is added, then transferring the slurry with the foam into a square groove, standing for 30min, scraping the foam on the surface of the slurry after standing is finished, and separating the organic impurities from the gypsum slurry;
(6) Conveying the froth scraped off from the surface of the slurry in the step (5) to a filter press for filter pressing, and conveying the filter liquor after filter pressing to the step (2) for adjusting to slurry A after recovery treatment;
(7) Transferring the slurry subjected to defoaming in the step (5) into a forming tank, and adding the dilute sulfuric acid prepared in the step (3) into the forming tank again, wherein the adding amount of the dilute sulfuric acid is 120kg;
(8) Adding steam into the forming tank for heat preservation, controlling the temperature at 70 ℃, continuously stirring the slurry, and controlling the forming time at 2h;
(9) Carrying out filter pressing on the formed slurry, recycling filtrate, and then conveying the filtrate to a phosphoric acid workshop as a phosphoric acid production raw material, wherein the filter cake is subjected to slurry mixing by using process water, and the temperature, the components and the dosage of the process water are the same as those of the process water used in the step (2) of the example;
(10) Filtering the slurry obtained in the step (9), and recovering and conveying the filtered filtrate to the step (2) to prepare slurry A, and carrying out 4-level countercurrent washing on a filter cake to obtain purified phosphogypsum;
in the step (10), filtrate generated in the subsequent stage of washing during countercurrent washing is used as washing liquid in the previous stage of washing, washing liquid in the last stage of washing is process water, and the temperature, the components and the dosage of the process water are the same as those in the step (2) in the example. And (3) in the step (10), the final filtrate after countercurrent washing can be recovered and conveyed to the step (9) for size mixing of the filter cake.
The content of the components of the purified phosphogypsum obtained in this example was tested to obtain: the purified gypsum contains water-soluble phosphorus of 0.01214%, total phosphorus of 0.1045%, water-soluble fluorine content of 0.0134%, free water of 22.58%, white powder of gypsum after drying at 45 ℃ and whiteness of 78.12.
Example 4
The phosphogypsum recycling method in the embodiment specifically comprises the following steps:
(1) Phosphogypsum of a certain phosphorus compound fertilizer plant in Hubei province is selected, the phosphogypsum is gray black in color, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the phosphogypsum is 0.4986%, the total phosphorus is 1.524%, and the pH of the leaching solution is between 1 and 2.
(2) 700kg of phosphogypsum, 80kg of calcined soda and 40kg of lime powder are weighed and mixed; preparing a mixture slurry from the mixture and process water according to the weight ratio of 1:1.7, wherein the process water is prepared from clear water and steam condensate, the temperature is controlled at 60 ℃, and the mixture is fully stirred to uniformly distribute liquid phase and solid phase, so as to obtain a slurry A;
(3) Preparing dilute sulfuric acid with the mass fraction of 40%;
(4) Acidolysis decolorization: transferring the slurry A into a reaction container, wherein the stirring speed in the container is 400r/min, adding the sulfuric acid solution obtained in the step (3) into the slurry from the bottom of the reaction container, wherein the adding amount of the sulfuric acid solution is 380kg, and the adding time of the sulfuric acid is controlled to be 30min;
(5) Stirring for 20min after the sulfuric acid is added, then transferring the slurry with the foam into a square groove, standing for 30min, scraping the foam on the surface of the slurry after standing is finished, and separating the organic impurities from the gypsum slurry;
(6) Conveying the froth scraped off from the surface of the slurry in the step (5) to a filter press for filter pressing, and conveying the filter liquor after filter pressing to the step (2) for adjusting to slurry A after recovery treatment;
(7) The slurry after defoaming in the step (5) is moved into a forming tank, and dilute sulfuric acid prepared in the step (3) is added into the forming tank again, wherein the adding amount of the dilute sulfuric acid is 120kg;
(8) Adding steam into the forming tank for heat preservation, controlling the temperature at 65 ℃, continuously stirring the slurry, and controlling the forming time at 1h;
(9) Carrying out filter pressing on the formed slurry, recycling filtrate, and then conveying the filtrate to a phosphoric acid workshop as a phosphoric acid production raw material, wherein the filter cake is subjected to slurry mixing by using process water, and the temperature, the components and the dosage of the process water are the same as those of the process water used in the step (2) of the example;
(10) Filtering the slurry obtained in the step (9), and recovering and conveying the filtered filtrate to the step (2) to prepare slurry A, and carrying out 4-level countercurrent washing on a filter cake to obtain purified phosphogypsum;
in the step (10), the filtrate obtained in the subsequent stage of washing in the 4-stage countercurrent washing is used as the washing liquid in the previous stage of washing, the washing liquid in the final stage of washing is process water, and the temperature, the components and the dosage of the process water are the same as those in the step (2) in the example. And (3) in the step (10), the final filtrate after countercurrent washing can be recovered and conveyed to the step (9) for size mixing of the filter cake.
The content of the components of the purified phosphogypsum obtained in this example was tested to obtain: the purified gypsum contains water-soluble phosphorus of 0.0114%, total phosphorus of 0.1113%, water-soluble fluorine content of 0.0127%, free water of 21.64%, white powder of gypsum after drying at 45deg.C, and whiteness of 79.24.
A schematic flow chart of the phosphogypsum recovery method in examples 1 to 4 of the present invention is shown in FIG. 1.
Example 5:
the phosphogypsum recycling method in the embodiment specifically comprises the following steps:
(1) Phosphogypsum of a certain phosphorus compound fertilizer plant in Hubei province is selected, the phosphogypsum is gray black in color, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the phosphogypsum is 0.4986%, the total phosphorus is 1.524%, and the pH of the leaching solution is between 1 and 2.
(2) According to m Phosphogypsum ：m Soda ash ：m Lime powder The mass ratio of =9:1:1 is measured out and the substances are mixed, 5 batches are weighed out and numbered a, b, c, d, e, and each batch is 2.2 tons;
(3) Placing the batch a in a container, adding 5.5 tons of process water, stirring and mixing to obtain uniform slurry, wherein the process water is prepared by mixing clear water and steam condensate, and the temperature is controlled at 70 ℃;
(4) Preparing dilute phosphoric acid with the mass fraction of 40%;
(5) Acidolysis decolorization: transferring the slurry prepared in the step (3) into a reaction container, continuously stirring at a rotating speed of 400r/min, and adding the dilute sulfuric acid prepared in the step (4) into the slurry from the bottom of the reaction container, wherein the adding amount of the dilute sulfuric acid is 950kg, and the adding time is controlled to be 35min;
(6) Stirring for 20min after the reaction is completed, discharging the reacted slurry into a square groove, standing for 30min, and fully layering the gypsum slurry and the organic foam;
(7) Scraping the upper layer of floating foam by a scraper, and conveying the square tank bottom to a forming tank;
(8) Delivering the foam-carrying liquid to a filter press for filter pressing treatment, wherein a filter cake is decolorized slag, and recovering filtrate to obtain filtrate A;
(9) The bottom flow is sent to a forming tank, 360kg of dilute sulfuric acid prepared in the step (4) is added, steam is added to the forming tank for heat preservation, the temperature is controlled at 65 ℃, the slurry is continuously stirred, and the forming time is controlled at 2h;
(10) Carrying out filter pressing on the slurry after complete formation, recovering and treating filtrate recovered by the filter pressing, and then sending the filtrate to a phosphoric acid workshop to serve as a phosphoric acid production raw material, adding process water into a filter cake after the filter pressing for size mixing, wherein the temperature, the components and the dosage of the process water are the same as those in the step (3) of the example, so as to obtain slurry A;
(11) The slurry A is fully stirred and then is sent to a filtering device for filtering, filtrate B is obtained by recycling filtrate after filtering by the filtering device, purified phosphogypsum is obtained by 4-level countercurrent washing of filter cakes, and filtrate C is obtained by recycling washing liquid generated by the filtering device;
(12) The filtrate of the back stage countercurrent washing in the 4 stage countercurrent washing in the step (11) is used as the washing liquid of the upper stage countercurrent washing, the washing liquid of the final stage countercurrent washing is process water, the dosage of the process water is 5.5 tons, and the temperature is controlled at 70 ℃;
(13) Mixing the recovered filtrate A and filtrate B, pulping the mixed material of the batch B, repeating the steps (5) to (11), and replacing the process water used in the repeated step (10) with filtrate C;
(14) Sequentially processing the rest 3 batches of gypsum according to the steps (5) to (10);
the gypsum recovered from 5 batches was analyzed, the analysis results are shown in Table 1 below, using the analytical methods of quinoline phosphomolybdate gravimetric method (for analysis of phosphorus component), ICP-MS (for analysis of metal component) and the test method described in Q/520122K-002-2020 (for analysis of organic carbon component), and the data in Table 1 are based on the dry basis mass of purified phosphogypsum after removal of free water.
TABLE 1 analysis results of phosphogypsum Components after 5 batches of recovered phosphogypsum in example 5
After 5 batches of phosphogypsum were treated according to the method of example 5 of the present invention, the 5 batches of phosphogypsum contained fluorine, water-soluble P 2 O 5 Total P 2 O 5 The contents of Mg, na, fe, K, al and organic carbon are greatly reduced, wherein the whiteness of phosphogypsum is reduced by22.71 is improved to about 78, the soluble phosphorus of phosphogypsum is reduced to below 0.016 percent, the total phosphorus is reduced to about 0.1 percent, the pH of the gypsum leaching solution is improved to 6-7 from 1-2, the phosphogypsum can be directly discharged, the purification degree of the phosphogypsum is far higher than that of the conventional water washing and acidolysis processes in the prior art, and the quality index of the treated phosphogypsum is superior to the related requirements of the standard of building gypsum powder, and the phosphogypsum can be directly used for building materials.
Example 6
As shown in fig. 2 and 3, this example provides a phosphogypsum recovery system, and the phosphogypsum recovery methods in embodiments 1 to 5 of the present invention can all be recovered by using the recovery system in this example.
The phosphogypsum recycling system in the embodiment comprises a slurry mixing machine, an acidolysis device, a square groove, a forming groove, a filter pressing device, a filter press, a slurry mixing device, a filtering device and a countercurrent washing device, wherein the slurry mixing machine is provided with a solid raw material inlet and a liquid inlet, phosphogypsum and carbonate are added through the solid raw material inlet of the slurry mixing machine, the liquid inlet of the slurry mixing machine is respectively connected with a water source, a liquid outlet of the filtering device and a liquid outlet of the filter press through pipelines, a slurry outlet of the slurry mixing machine is connected with the acidolysis device, a first acid liquid inlet is arranged at the bottom of the acidolysis device and is connected with a sulfuric acid storage device through pipelines, the acidolysis device is connected with the square groove, a scraper is arranged on the square groove, the square groove is connected with the filter press, the liquid outlet of the filter press is connected with the slurry mixing machine, the square groove is connected with the forming groove, the forming groove is connected with the filter pressing device, the liquid outlet of the filter pressing device is connected with a phosphoric acid production system, the solid outlet of the filter pressing device is connected with the slurry mixing device through pipelines, the slurry mixing device is respectively connected with the countercurrent washing device, and the belt type filtering device is connected with the liquid outlet of the filtering device. The countercurrent washing device in the embodiment has the washing stage number of 4, and comprises a first countercurrent washing zone, a second countercurrent washing zone, a third countercurrent washing zone and a fourth countercurrent washing zone, wherein the washing liquid inlet of the first countercurrent washing zone is respectively connected with a water source and the liquid outlet of the second countercurrent washing zone. The liquid outlet of the first-stage countercurrent washing zone is connected with a pulp mixing device. The washing liquid inlet of the second-stage countercurrent washing zone is respectively connected with a water source and a liquid outlet of the third-stage countercurrent washing zone; the washing liquid inlet of the third-stage countercurrent washing zone is respectively connected with a water source and a liquid outlet of the fourth-stage countercurrent washing zone. The washing liquid inlet of the four-stage countercurrent washing zone is connected with a water source, and the solid washed by the four-stage countercurrent washing zone is recovered phosphogypsum.
When the phosphogypsum and carbonate and the slurry mixing liquid are added into a slurry mixing machine to perform slurry mixing, the slurry is conveyed to an acidolysis device after slurry mixing, dilute sulfuric acid is introduced from the bottom of the acidolysis device and subjected to acidolysis reaction once, acidolysis products are conveyed into a square groove to stand and layer, a floating foam layer is scraped into a filter press by a scraper on the square groove to perform filter pressing, the solid after filter pressing is decolorized slag, and the liquid after filter pressing can be used for the slurry mixing machine to prepare the liquid of phosphogypsum and carbonate slurry. And conveying the residual slurry in the square groove to a forming groove, adding sulfuric acid into the forming groove for secondary acidolysis reaction, conveying the slurry to a filter pressing device for filter pressing after secondary acidolysis, conveying liquid generated by filter pressing to a phosphoric acid production system for producing phosphoric acid, regulating slurry of solid generated by filter pressing by a slurry regulating device, conveying the slurry to a belt type filtering device for filtering, and enabling liquid used in the slurry regulating device to be derived from process water or liquid discharged by a countercurrent washing device. And (3) conveying the liquid generated by filtering by the belt type filtering device to a pulp mixer for pulp mixing, conveying the solid generated by the belt type filtering device to a countercurrent washing device, and washing by the countercurrent washing device to obtain purified phosphogypsum.
Comparative example 1
The phosphogypsum recycling method in the embodiment specifically comprises the following steps:
(1) Phosphogypsum of a certain phosphorus compound fertilizer plant in Hubei province is selected, the phosphogypsum is gray black in color, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the phosphogypsum is 0.4986%, the total phosphorus is 1.524%, and the pH of the leaching solution is between 1 and 2.
(2) According to m Phosphogypsum ：m Soda ash ：m Lime powder The mass ratio of the components is weighed and mixed, and the total mass of phosphogypsum, calcined soda and lime powder is 2.2 tons;
(3) Placing the materials weighed in the step (2) into a container, adding 5.5 tons of process water, stirring and mixing to obtain uniform slurry, wherein the process water is prepared by mixing clear water and steam condensate, and the temperature is controlled at 70 ℃;
(4) Preparing dilute phosphoric acid with the mass fraction of 40%;
(5) Acidolysis decolorization: transferring the slurry prepared in the step (3) into a reaction container, continuously stirring at a rotating speed of 400r/min, and adding the dilute sulfuric acid prepared in the step (4) into the slurry from the bottom of the reaction container, wherein the adding amount of the dilute sulfuric acid is 1310kg, and the adding time is controlled to be 35min;
(6) Stirring for 20min after the reaction is completed, discharging the reacted slurry into a square groove, standing for 30min, and fully layering the gypsum slurry and the organic foam;
(7) Scraping the upper layer of floating foam by a scraper, and conveying the square tank bottom to a forming tank;
(8) Delivering the foam-carrying liquid scraped by the scraper in the step (7) to a filter press for filter pressing treatment, wherein a filter cake is decolorized slag, and delivering the filter liquor after filter pressing to the step (3) for slurry mixing after recovery treatment;
(9) The underflow liquid of the square groove in the step (7) is sent to a forming groove, steam is added into the forming groove for heat preservation, the temperature is controlled at 65 ℃, the slurry is stirred continuously, and the forming time is controlled at 2h;
(10) Carrying out filter pressing on the slurry after complete formation, recovering and treating filtrate recovered by the filter pressing, and then sending the filtrate to a phosphoric acid workshop to serve as a phosphoric acid production raw material, adding process water into a filter cake after the filter pressing for size mixing, wherein the temperature, the components and the dosage of the process water are the same as those in the step (3) of the example, so as to obtain slurry A;
(11) Filtering the slurry A obtained in the step (10), recovering the filtered filtrate, and conveying the filtrate to the step (3) for preparing slurry, and carrying out 4-level countercurrent washing on the filtered filter cake to obtain purified phosphogypsum;
in the step (11), the filtrate obtained in the subsequent stage of washing in the 4-stage countercurrent washing is used as the washing liquid in the previous stage of washing, the washing liquid in the final stage of washing is process water, and the temperature, the components and the dosage of the process water are the same as those in the step (3) in the example. And (3) in the step (11), the final filtrate after countercurrent washing can be recovered and conveyed to the step (10) for size mixing of the filter cake.
The components of the purified phosphogypsum obtained in this example were analyzed, and the analysis results are shown in Table 2 below, wherein the analysis methods used are a quinoline phosphomolybdate gravimetric method (for analyzing phosphorus components), an ICP-MS (for analyzing metal components), and a test method described in Q/520122K-002-2020 (for analyzing organic carbon components), and the data in Table 2 are based on the dry basis mass of the purified phosphogypsum after removal of free water.
TABLE 2 analysis results of phosphogypsum component recovered in comparative example 1
As is clear from Table 2, in comparative example 1, phosphogypsum was subjected to only one acid hydrolysis step as compared with example 5, and water-soluble F and water-soluble P in the recovered phosphogypsum were obtained 2 O 5 The contents of impurities such as Mg, na and the like are higher, so that the purity of the recovered phosphogypsum can be improved by adopting two acidolysis steps.
Comparative example 2
The phosphogypsum recycling method in the embodiment specifically comprises the following steps:
(1) Phosphogypsum of a certain phosphorus compound fertilizer plant in Hubei province is selected, the phosphogypsum is gray black in color, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the phosphogypsum is 0.4986%, the total phosphorus is 1.524%, and the pH of the leaching solution is between 1 and 2.
(2) Weighing 1.8 tons of phosphogypsum, placing the phosphogypsum in a container, adding 5.5 tons of process water, stirring and preparing into uniform slurry, wherein the process water is prepared by mixing clear water and steam condensate, and the temperature is controlled at 70 ℃;
(3) Preparing dilute phosphoric acid with the mass fraction of 40%;
(4) Primary acidolysis: transferring the slurry prepared in the step (2) into a reaction container, continuously stirring at a rotating speed of 400r/min, and adding the dilute sulfuric acid prepared in the step (3) into the slurry from the bottom of the reaction container, wherein the adding amount of the dilute sulfuric acid is 950kg, and the adding time is controlled to be 35min;
(5) Discharging the slurry after acidolysis into a square groove, standing for 30min to enable gypsum to fully settle, wherein black oily liquid is arranged above the square groove;
(6) Scraping the upper black oily liquid in the step (5) by using a scraper, separating out floating organic matters, recovering the oily liquid scraped by the scraper, adding activated carbon to adsorb the organic matters, and carrying out filter pressing on the liquid after the adsorption is finished, wherein an obtained filter cake is decolorized slag, and the filter cake after the filter pressing is conveyed to the step (2) for slurry adjustment after the recovery treatment;
(7) Delivering the underflow slurry in the square groove to a forming groove, adding 360kg of dilute sulfuric acid prepared in the step (3), adding steam into the forming groove for heat preservation, controlling the temperature at 65 ℃, continuously stirring the slurry, and controlling the forming time at 2h;
(8) Carrying out filter pressing on the slurry obtained after the formation in the step (7), recovering and treating the filtrate recovered by the filter pressing, and then sending the filtrate to a phosphoric acid workshop to serve as a raw material for producing phosphoric acid, adding process water into a filter cake obtained by the filter pressing, and mixing the slurry, wherein the temperature, the components and the dosage of the process water are the same as those in the step (2) in the example, so as to obtain slurry A;
(9) Filtering the slurry obtained in the step (8), and recovering and conveying the filtered filtrate to the step (2) to prepare slurry A, and carrying out 4-level countercurrent washing on a filter cake to obtain purified phosphogypsum;
in the step (9), the filtrate obtained in the subsequent stage of washing in the 4-stage countercurrent washing is used as the washing liquid in the previous stage of washing, the washing liquid in the final stage of washing is process water, and the temperature, the components and the dosage of the process water are the same as those in the step (2) in the example. And (3) in the step (9), the final filtrate after countercurrent washing can be recovered and conveyed to the step (8) for size mixing of the filter cake.
The components of the purified phosphogypsum obtained in this example were analyzed, and the analysis results are shown in Table 3 below, wherein the analysis methods used are a quinoline phosphomolybdate gravimetric method (for analyzing phosphorus components), an ICP-MS (for analyzing metal components), and a test method described in Q/520122K-002-2020 (for analyzing organic carbon components), and the data in Table 3 are based on the dry basis mass of the purified phosphogypsum after removal of free water.
TABLE 3 analysis results of the components of phosphogypsum recovered in comparative example 2
As is clear from Table 3, in comparative example 2, in comparison with example 5, no carbonate was added in the phosphogypsum, and water-soluble F and water-soluble P were contained in the phosphogypsum recovered 2 O 5 The contents of impurities such as Mg, na and the like are higher, wherein the content of the impurities of the organic carbon is obviously increased, and the whiteness is obviously reduced, so that the purity and whiteness of the recovered phosphogypsum can be obviously improved by adding carbonate in one acidolysis step when the phosphogypsum is recovered, and the content of the impurities of the organic carbon is reduced.
Comparative example 3:
the phosphogypsum recycling method in the embodiment specifically comprises the following steps:
(1) Phosphogypsum of a certain phosphorus compound fertilizer plant in Hubei province is selected, the phosphogypsum is gray black in color, the whiteness is 22.71, the free water content is 25.71%, the water-soluble phosphorus content of the phosphogypsum is 0.4986%, the total phosphorus is 1.524%, and the pH of the leaching solution is between 1 and 2.
(2) According to m Phosphogypsum ：m Soda ash ：m Lime powder The mass ratio of =9:0.4:1.6 is measured, the substances are mixed, and the total weight is 2.2 tons;
(3) Placing the material weighed in the step (2) into a container, adding 5.5 tons of process water, stirring and mixing to obtain uniform slurry, wherein the process water is prepared by mixing clear water and steam condensate, and the temperature is controlled at 70 ℃;
(4) Preparing dilute phosphoric acid with the mass fraction of 40%;
(5) Acidolysis decolorization: transferring the slurry prepared in the step (3) into a reaction container, continuously stirring at a rotating speed of 400r/min, and adding the dilute sulfuric acid prepared in the step (4) into the slurry from the bottom of the reaction container, wherein the adding amount of the dilute sulfuric acid is 950kg, and the adding time is controlled to be 35min;
(6) Stirring for 20min after the reaction is completed, discharging the reacted slurry into a square groove, standing for 30min, and fully layering the gypsum slurry and the organic foam;
(7) Scraping the upper layer of foam on the square groove in the step (6) by using a scraper, and conveying the bottom flow of the square groove to a forming groove;
(8) Conveying the foam-carrying liquid scraped by the scraper in the step (7) to a filter press for filter pressing treatment, wherein a filter cake is decolorized slag, and conveying the filter liquor after filter pressing to the step (3) for preparing slurry after recovery treatment;
(9) The underflow of the square groove in the step (7) is sent to a forming groove, 360kg of dilute sulfuric acid prepared in the step (4) is added, steam is added into the forming groove for heat preservation, the temperature is controlled at 65 ℃, the slurry is continuously stirred, and the forming time is controlled at 2h;
(10) Carrying out filter pressing on the slurry after complete formation, recovering and treating filtrate recovered by the filter pressing, and then sending the filtrate to a phosphoric acid workshop to serve as a phosphoric acid production raw material, adding process water into a filter cake after the filter pressing for size mixing, wherein the temperature, the components and the dosage of the process water are the same as those in the step (3) of the example, so as to obtain slurry A;
(11) Filtering the slurry obtained in the step (10), recovering the filtered filtrate, conveying the filtrate to the step (3) for preparing the slurry, and carrying out 4-level countercurrent washing on the filter cake to obtain purified phosphogypsum;
in the step (11), the filtrate obtained in the subsequent stage of washing in the 4-stage countercurrent washing is used as the washing liquid in the previous stage of washing, the washing liquid in the final stage of washing is process water, and the temperature, the components and the dosage of the process water are the same as those in the step (3) in the example. And (3) in the step (11), the final filtrate after countercurrent washing can be recovered and conveyed to the step (10) for size mixing of the filter cake.
The components of the purified phosphogypsum obtained in this example were analyzed, and the analysis results are shown in Table 4 below, using the analysis methods described in the weight method of quinoline phosphomolybdate (for analysis of phosphorus component), ICP-MS (for analysis of metal component) and Q/520122K-002-2020 (for analysis of organic carbon component), and the data in Table 4 are based on the dry mass of the purified phosphogypsum after removal of free water.
Table 4 analysis results of phosphogypsum component recovered in comparative example 3
As is clear from Table 4, in comparative example 3, the amount of soluble carbonate in the carbonate was reduced in the phosphogypsum recovered as compared with example 5, and the water-soluble F and water-soluble P in the phosphogypsum recovered 2 O 5 The contents of impurities such as Mg, na and the like are relatively increased, in particular to total P 2 O 5 The content of the organic carbon is obviously increased, so that when phosphogypsum is recovered, the purity of the recovered phosphogypsum can be obviously improved by adding carbonate in one acidolysis step, the content of the organic carbon impurities is reduced, and when the content of the soluble carbonate is more than 40%, various impurities wrapped by the phosphogypsum are released, so that the purity of the recovered phosphogypsum is higher.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A phosphogypsum recovery method is characterized in that: the recovery method comprises the following steps:
mixing phosphogypsum and carbonate, performing primary acidolysis to remove floating foam, performing secondary acidolysis, and then performing filter pressing and washing to obtain purified phosphogypsum; the phosphogypsum and carbonate are mixed for one acidolysis step, which comprises the following steps: mixing phosphogypsum, carbonate and water to obtain slurry A, and then introducing acid liquor from the bottom of the slurry A and stirring to obtain foam-containing slurry; the mass ratio of phosphogypsum to carbonate is (4-9): 1.
2. the phosphogypsum recovery method according to claim 1, characterized in that: the acid liquor used in the primary acidolysis step and/or the secondary acidolysis step is sulfuric acid.
3. The phosphogypsum recovery method according to claim 1, characterized in that: the washing adopts a countercurrent washing method.
4. A method for recovering phosphogypsum as claimed in claim 3, wherein: the number of stages of countercurrent washing is 2-6.
5. A method for recovering phosphogypsum as claimed in claim 3, wherein: the effluent of the next stage countercurrent washing is used as the wash liquid of the previous stage countercurrent washing.
6. The phosphogypsum recovery method according to claim 1, characterized in that: the filter pressing step specifically comprises the following steps: and (3) conveying the liquid obtained in the pressure filtration step to a phosphoric acid production workshop as a phosphoric acid production raw material, and filtering after preparing the solid obtained in the pressure filtration step into slurry B.
7. Phosphogypsum is characterized in that: the method according to any one of claims 1 to 6.
8. Use of phosphogypsum according to claim 7 in building materials.
9. A phosphogypsum recovery system, characterized in that: the recovery system is used for implementing the recovery method according to any one of claims 1-6, and comprises an acidolysis device, a square groove, a formation groove, a filtering system and a countercurrent washing device, wherein a first acid liquid inlet is formed in the bottom of the acidolysis device, the acidolysis device is connected with the square groove, a scraper is arranged on the square groove, the square groove is connected with the formation groove, a second acid liquid inlet is formed in the formation groove, the formation groove is connected with the filtering system, and a solid outlet of the filtering system is connected with the countercurrent washing device.
10. The phosphogypsum recovery system of claim 9, wherein: the filter system comprises a filter pressing device, a slurry mixing device and a filter device, wherein the filter pressing device is connected with the formation tank, a liquid outlet of the filter pressing device is connected with the phosphoric acid production system, a solid outlet of the filter pressing device is connected with the slurry mixing device, the slurry mixing device is connected with the filter device, and a solid outlet of the filter device is connected with the countercurrent washing device.
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