CN113651300A - Method for improving phosphorus yield by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification - Google Patents
Method for improving phosphorus yield by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification Download PDFInfo
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 264
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 124
- 239000002367 phosphate rock Substances 0.000 title claims abstract description 75
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 62
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000011574 phosphorus Substances 0.000 title claims abstract description 52
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 52
- 238000000746 purification Methods 0.000 title claims abstract description 27
- ZQBZAOZWBKABNC-UHFFFAOYSA-N [P].[Ca] Chemical compound [P].[Ca] ZQBZAOZWBKABNC-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012065 filter cake Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 26
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 25
- 239000011707 mineral Substances 0.000 claims abstract description 25
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011575 calcium Substances 0.000 claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 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 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000001238 wet grinding Methods 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims description 21
- 150000003016 phosphoric acids Chemical class 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- MWKXCSMICWVRGW-UHFFFAOYSA-N calcium;phosphane Chemical compound P.[Ca] MWKXCSMICWVRGW-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011737 fluorine Substances 0.000 abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 2
- 239000003337 fertilizer Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 229910052593 corundum Inorganic materials 0.000 description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 description 12
- 229910019142 PO4 Inorganic materials 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 6
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 6
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 6
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 6
- 238000006115 defluorination reaction Methods 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 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
- 239000003054 catalyst Substances 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 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
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 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
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/2372—Anionic impurities, e.g. silica or boron compounds
- C01B25/2375—Fluoride or fluosilicate anion
-
- 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
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/2372—Anionic impurities, e.g. silica or boron compounds
- C01B25/2377—Sulfate
-
- 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
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/322—Preparation by neutralisation of orthophosphoric acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a method for improving phosphorus yield by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification, which belongs to the field of wet-process phosphoric acid purification and aims to overcome the defects of high phosphorus loss and high production cost of the traditional wet-process phosphoric acid purification, and comprises the following steps: step 1, extracting phosphorite and sulfuric acid to obtain phosphogypsum and phosphoric acid; step 2, grinding the phosphorite into mineral powder or wet grinding the phosphorite, and filtering the wet ground ore pulp to obtain a filter cake; step 3, adding the phosphoric acid obtained in the step 1 into a reaction tank, and adding the mineral powder or the filter cake obtained in the step 2 to ensure that the phosphoric acid and the ground phosphate rock fully react in the reaction tank; and 4, performing solid-liquid separation on the slurry after the reaction, extracting the solid, and deeply removing impurities from the clear liquid in the next stage. The method fully utilizes the high calcium content of the mineral powder or the filter cake to pretreat the phosphoric acid, fully utilizes the concentration of the phosphoric acid and the calcium source in the phosphorite to pretreat the phosphoric acid, reduces the sulfur and the fluorine in the phosphoric acid, improves the concentration and the pH value of the phosphoric acid, and realizes the purposes of improving the yield of the phosphorus and reducing the consumption of the sulfuric acid.
Description
Technical Field
The invention discloses a method for improving phosphorus yield by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification, and belongs to the field of wet-process phosphoric acid purification.
Background
Phosphate ore with high calcium-phosphorus ratio exists in large area of the country (the ratio of calcium content to phosphorus content in the phosphate oreAbove 1.43), some can reduce the calcium content by ore dressing, and some can only be used directly. In the phosphoric acid extraction link, the content of calcium in phosphorite directly influences the increase of sulfuric acid consumption, and under the normal condition of wet-process phosphoric acid extraction, phosphorite with the calcium-phosphorus ratio of less than 1.43 is used for producing 1 ton of P2O5The consumption of sulfuric acid is about 2.45 tons, if the calcium-phosphorus ratio of phosphorite is more than 1.43, the consumption of sulfuric acid is more than 2.5 tons, because the extraction process combines sulfate radicals and calcium in the phosphorite into calcium sulfate, the existing method solves the problem of high consumption of sulfuric acid by reducing the calcium-phosphorus ratio through ore blending. Several kinds of ores need to be matched for ore blending, the required field is wide, and the ore blending accuracy is poor.
The reaction sequence of the phosphoric acid impurity removing process is as follows: sulfur, iron, aluminum, fluorine, heavy metals. The higher the content of sulfur and fluorine in the phosphoric acid is, the lower the yield is, the more white fertilizer is produced, and the lower the content of sulfur and fluorine in the phosphoric acid is, the higher the defluorination yield is.
The traditional wet-process phosphoric acid purification method adopts calcium sources in calcium carbonate and lime to carry out defluorination and impurity removal, removes impurities such as sulfur, fluorine, iron, aluminum, magnesium and the like in the phosphoric acid, and the yield of purified phosphorus is basically between 75 and 83 percent; if the phosphorus ore impurity is high, the yield is even less than 80%, the grade of the byproduct fertilizer grade calcium hydrophosphate (white fertilizer) is obviously higher and larger, and the grade of the byproduct fertilizer grade calcium hydrophosphate (white fertilizer) even reaches P2O516-18 percent of calcium hydrophosphate product, and the white fertilizer content of each ton of calcium hydrophosphate product is 0.6-0.7t (the normal control grade P is2O5About 14 percent, the white fertilizer content of each ton of calcium hydrophosphate product is between 0.5 and 0.55t based on 40 percent of water content), the phosphorus loss is large, and the production cost is high.
Disclosure of Invention
The invention aims to: a method for improving phosphorus yield by using phosphorite with high calcium phosphorus ratio for wet-process phosphoric acid purification aims at solving the defects of high phosphorus loss and high production cost of the traditional wet-process phosphoric acid purification phosphoric acid.
The technical scheme adopted by the invention is as follows:
a method for improving the yield of phosphorus by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification comprises the following steps:
step 1, carrying out extraction reaction on phosphorite and sulfuric acid to obtain phosphogypsum and phosphoric acid;
step 2, grinding the phosphorite into mineral powder or wet grinding the phosphorite, and filtering the wet ground ore pulp to obtain a filter cake;
and 3, adding the phosphoric acid obtained in the step 1 into a reaction tank, adding the mineral powder or the filter cake obtained in the step 2, and enabling the phosphoric acid and the powdered rock phosphate to fully react in the reaction tank, wherein the adding amount of the mineral powder or the filter cake is P2O5The phosphorus ore for extraction which is equivalent to the phosphorus ore for producing the phosphoric acid2O5The amount of (c);
and 4, performing solid-liquid separation on the slurry after the reaction, extracting the solid, and deeply removing impurities from the clear liquid in the next stage.
In the technical scheme of the application, the phosphoric acid obtained in the step 1 contains sulfur, fluorine, iron, aluminum and magnesium impurities, and the phosphoric acid obtained in the step 1 also contains SO with the concentration of 2-3 percent4 2-The principle is that the characteristics of extracted phosphoric acid are utilized, the phosphoric acid has certain extraction capacity under the condition of certain concentration and temperature and containing a small amount of sulfate radicals, mineral powder or filter cakes provide a calcium source, and the first defluorination and impurity removal (sulfur removal) of the phosphoric acid are realized, and phosphorus-free loss (the concentration of the phosphoric acid is also increased). The invention provides a process for using phosphate ore with high calcium-phosphorus ratio to purify and remove impurities in wet-process phosphoric acid by a dihydrate method, wherein the phosphoric acid is used as a production raw material of feed-grade calcium hydrophosphate, impurities such as fluorine, metal ions and the like need to be removed from the phosphoric acid, phosphorus loss exists in the removal process, and the product cost is determined by the phosphorus loss. The method has the advantages that the ore with high calcium-phosphorus ratio is used independently, the characteristics of the ore can be fully utilized to remove impurities in advance from phosphoric acid, and calcium is fully utilized to achieve two purposes.
Preferably, the ratio of the calcium content to the phosphorus content of the phosphate ore in steps 1 and 2 is higher than 1.43.
Preferably, in the step 1, the mass ratio of the phosphorite to the sulfuric acid is 3.5-3.9: 2.5-2.8.
More preferably, in the step 1, the mass ratio of the phosphorite to the sulfuric acid is 3.5: 2.5.
Preferably, the mass concentration of phosphoric acid in step 1 is 16% or more.
Preferably, the cake moisture in step 2 is less than 20%.
Preferably, the step 3 is to add the mineral powder or the filter cake separately from 2 or more reaction tanks, stir the zones of the reaction tanks for reaction, guide the materials in a mode of combining overflow and underflow, and arrange 4 to 8 zones, which can be 4, 5, 6, 7 or 8 zones, in the reaction tanks.
The pre-extraction capacity of phosphoric acid to phosphorite is utilized to enable calcium in the phosphorite to react with phosphoric acid to generate calcium phosphate, the phosphoric acid has temperature, reaction heat is generated after the phosphoric acid reacts with the phosphorite, solid-liquid separation is carried out on slurry after reaction, the acid temperature after filtration is ensured to be higher than 45 ℃, more preferably higher than 50 ℃, and the reaction effect is better.
More preferably, the temperature of the phosphoric acid in step 3 is greater than 45 ℃.
More preferably, the linear velocity of the agitation in step 3 is greater than 5 m/s.
More preferably, the reaction time in step 3 is 1.2 to 2 hours.
Preferably, the yield of defluorinated phosphoric acid is more than 87%.
Preferably, the filter cake has a moisture content of less than 18%. Phosphoric acid reacts with phosphate ore, the higher the concentration of phosphoric acid, the better, the lower the concentration of water polyphosphoric acid, and the lower the reaction rate.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the invention, the high calcium content of the mineral powder or the filter cake is fully utilized to pretreat the phosphoric acid, the phosphoric acid concentration and the calcium source in the phosphorite are fully utilized to pretreat the phosphoric acid, the sulfur and the fluorine in the phosphoric acid are reduced (the sulfur is removed in the form of calcium sulfate, and the fluorine is removed in the form of calcium fluoride), the phosphoric acid concentration and the pH value are improved, and the purposes of improving the phosphorus yield and reducing the consumption of sulfuric acid are realized;
2. the ore with high calcium-phosphorus ratio is used independently, the characteristics of the ore can be fully utilized to remove impurities in advance from phosphoric acid, calcium is fully utilized, the use amount of a calcium source is reduced in the impurity removing process, and the two purposes are achieved;
3. same P2O5The production capacity and the consumption of sulfuric acid can be reduced by 6 percent, and the cost is saved;
4. the phosphorus yield can be improved to 87 percent by the same impurity removing effect, which is much higher than the yield of the traditional impurity removing method at present;
5. in industrial production, SO3The removal rate of the catalyst is controlled by adopting P2O5/SO3Index of (i.e. phosphoric acid concentration and SO in phosphoric acid)3Concentration ratio) of not less than 15 times, but only not less than 12 times, some lower and even less than 10 times can be guaranteed due to the quality reduction of phosphorite in the industry at present, SO that the defluorination yield is seriously influenced, the method ensures the filtering and washing effects and can greatly improve the SO (sulfur oxide) yield by changing the desulfurization mode through longer-time verification3Removal rate of (2), P2O5/SO3The index of the method can reach 20 times, even more than 20 times, the defluorination yield is improved by 5 percent, and the production cost of the calcium hydrophosphate is reduced by 8 percent, thereby greatly improving the production competitiveness of the product.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A method for improving the yield of phosphorus by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification comprises the following steps:
step 1, carrying out extraction reaction on phosphorite and sulfuric acid to obtain phosphogypsum and phosphoric acid, and extracting P in the phosphorite2O5% 27.59, CaO% 40.8, Fe2O3% content of 1.94, Al2O3% content of 2.95, MgO% content of 2.44;
step 2, grinding the phosphorite into mineral powderP in the phosphate ore for pretreatment2O5% content of 30.2, CaO% content of 45.2, Fe2O3% content of 0.17, Al2O3% content of 0.34, MgO% content of 2.88; the proportion of the phosphorite for desulfurization is 30 percent or more;
and 3, adding the phosphoric acid obtained in the step 1 into a reaction tank, wherein the temperature of the phosphoric acid is higher than 45 ℃, the reaction tank is provided with 4-8 areas, mineral powder or filter cakes are respectively added from 1, 2 and 3 areas of the reaction tank, the areas of the reaction tank are stirred for reaction, the stirring linear velocity is higher than 5 m/s, the material is guided by adopting a mode of combining overflow and underflow, so that the phosphoric acid and the powdered rock phosphate are fully reacted in the reaction tank, the reaction time is 1.2-2 hours, and the adding amount of the mineral powder or the filter cakes is P2O5The phosphorus ore for extraction which is equivalent to the phosphorus ore for producing the phosphoric acid2O5The amount of (c);
and 4, performing solid-liquid separation on the slurry after the reaction, extracting the solid, and deeply removing impurities from the clear liquid in the next stage.
In this example, non-desulfurized phosphoric acid P2O5/SO36.2, non-desulfurized phosphoric acid concentration 151.78g/l, desulfurized phosphoric acid P2O5/SO319.85, the concentration of the desulfurized phosphoric acid is 175.39g/l, and the grade of the white fertilizer (water content is 40 percent) P2O5% is 13.5, white fertilizer grade (water content is 40%) P of the prior art2O5The% is 16-18%, the white fertilizer yield (water content 40%) per ton of calcium bicarbonate product is 385kg, and the defluorinated phosphoric acid yield is 89.2%.
Example 2
A method for improving the yield of phosphorus by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification comprises the following steps:
step 1, carrying out extraction reaction on phosphorite and sulfuric acid to obtain phosphogypsum and phosphoric acid, and extracting P in the phosphorite2O5% content of 27.43, CaO% content of 40.53, Fe2O3% content of 1.94, Al2O3% content 2.71, MgO% content 2.2;
step 2, phosphoriteWet grinding, filtering the wet grinding ore pulp to obtain a filter cake, wherein the water content of the filter cake is less than 18%; p in the phosphate ore for pretreatment2O5% of 29.1, CaO% of 44.8, Fe2O3% content of 0.24, Al2O3% content of 0.58, MgO% content of 2.93; the proportion of the phosphorite for desulfurization is 30 percent or more;
and 3, adding the phosphoric acid obtained in the step 1 into a reaction tank, wherein the temperature of the phosphoric acid is more than 50 ℃, the reaction tank is provided with 4 areas, filter cakes are respectively added from 1, 2, 3 and 4 areas of the reaction tank, the areas of the reaction tank are stirred for reaction, the stirring linear velocity is more than 5 m/s, the material is guided by adopting a mode of combining overflow and underflow, so that the phosphoric acid and the powdered rock phosphate are fully reacted in the reaction tank, the reaction time is 1.2-2 hours, and the adding amount of the mineral powder or the filter cakes is P2O5The phosphorus ore for extraction which is equivalent to the phosphorus ore for producing the phosphoric acid2O5The amount of (c);
and 4, performing solid-liquid separation on the slurry after the reaction, extracting the solid, and deeply removing impurities from the clear liquid in the next stage.
In this example, non-desulfurized phosphoric acid P2O5/SO38.5, non-desulfurized phosphoric acid concentration 167.16g/l, desulfurized phosphoric acid P2O5/SO319.5, the concentration of desulfurized phosphoric acid is 194.14g/l, and the grade of white fertilizer (water content is 40 percent) P2O5% is 13.9, white fertilizer grade (water content is 40%) P of the prior art2O5% of the total amount of the defluorinated phosphoric acid is 16-18%, the yield of the white fertilizer per ton of calcium bicarbonate product is 400kg, and the yield of the defluorinated phosphoric acid is 88.4%.
Example 3
A method for improving the yield of phosphorus by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification comprises the following steps:
step 1, carrying out extraction reaction on phosphorite and sulfuric acid to obtain phosphogypsum and phosphoric acid, and extracting P in the phosphorite2O5% content of 27.02, CaO% content of 40.01, Fe2O3% content of 2.12, Al2O3% content 3.27, MgO% content 2.6;
step 2, phosphoriteGrinding into ore powder, P in the pretreated phosphorus ore2O5% 30.78, CaO% 48, Fe2O3% content of 0.27, Al2O3% content of 0.51, MgO% content of 2.6; the proportion of the phosphorite for desulfurization is 30 percent or more;
and 3, adding the phosphoric acid obtained in the step 1 into a reaction tank, wherein the temperature of the phosphoric acid is higher than 50 ℃, the reaction tank is provided with 6 areas, mineral powder is respectively added from 1, 2, 3 and 4 areas of the reaction tank, the areas of the reaction tank are stirred for reaction, the stirring linear velocity is higher than 5 m/s, the material is guided by adopting a mode of combining overflow and underflow, the phosphoric acid and the powdered rock phosphate are fully reacted in the reaction tank, the reaction time is 1.2-2 hours, and the adding amount of the mineral powder or the filter cake is P2O5The phosphorus ore for extraction which is equivalent to the phosphorus ore for producing the phosphoric acid2O5The amount of (c);
and 4, performing solid-liquid separation on the slurry after the reaction, extracting the solid, and deeply removing impurities from the clear liquid in the next stage.
In this example, non-desulfurized phosphoric acid P2O5/SO38.6, non-desulfurized phosphoric acid concentration 176.03g/l, desulfurized phosphoric acid P2O5/SO321, the concentration of desulfurized phosphoric acid is 212.4g/l, and the grade of white fertilizer (water content is 40 percent) P2O5% is 14.2, white fertilizer grade (water content is 40%) P of the prior art2O5% of the total amount of the defluorinated phosphoric acid is 16-18%, the white fertilizer yield per ton of calcium bicarbonate product is 358kg, and the defluorinated phosphoric acid yield is 90%.
Example 4
A method for improving the yield of phosphorus by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification comprises the following steps:
step 1, carrying out extraction reaction on phosphorite and sulfuric acid to obtain phosphogypsum and phosphoric acid, and extracting P in the phosphorite2O5% of 28.07, CaO% of 40.93, Fe2O3% content of 1.93, Al2O3% content of 2.44, MgO% content of 2.27;
step 2, carrying out wet grinding on the phosphorite, filtering the wet ground ore pulp to obtain a filter cake, and filtering the filter cake with waterThe content is less than 19 percent; p in the phosphate ore for pretreatment2O5% content of 29.87, CaO% content of 47.23, Fe2O3% content of 0.14, Al2O3% content of 0.46, MgO% content of 2.85; the proportion of the phosphorite for desulfurization is 20 percent or more;
and 3, adding the phosphoric acid obtained in the step 1 into a reaction tank, wherein the temperature of the phosphoric acid is higher than 50 ℃, the reaction tank is provided with 4 areas, mineral powder or filter cakes are respectively added from 1, 2, 3 and 4 areas of the reaction tank, the areas of the reaction tank are stirred for reaction, the stirring linear velocity is higher than 5 m/s, the material is guided by adopting a mode of combining overflow and underflow, so that the phosphoric acid and the powdered rock phosphate are fully reacted in the reaction tank, the reaction time is 1.2-2 hours, and the adding amount of the mineral powder or the filter cakes is P2O5The phosphorus ore for extraction which is equivalent to the phosphorus ore for producing the phosphoric acid2O5The amount of (c);
and 4, performing solid-liquid separation on the slurry after the reaction, extracting the solid, and deeply removing impurities from the clear liquid in the next stage.
In this example, non-desulfurized phosphoric acid P2O5/SO3A non-desulfurized phosphoric acid concentration of 184.29g/l, a desulfurized phosphoric acid P2O5/SO320.3, the concentration of the desulfurized phosphoric acid is 202g/l, and the grade of the white fertilizer (water content is 40 percent) P2O5% is 13.87, white fertilizer grade (water content is 40%) P of the prior art2O5% of the total amount of the defluorinated phosphoric acid is 16-18%, the white fertilizer yield per ton of calcium bicarbonate product is 380kg, and the defluorinated phosphoric acid yield is 89%.
Example 5
A method for improving the yield of phosphorus by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification comprises the following steps:
step 1, carrying out extraction reaction on phosphorite and sulfuric acid to obtain phosphogypsum and phosphoric acid, and extracting P in the phosphorite2O5% 28.59, CaO 42.41, Fe2O3% content of 1.54, Al2O3% content 1.94, MgO% content 2.19;
step 2, grinding the phosphorite into mineral powder, and performing P treatment on the phosphate ore for pretreatment2O5% 30.88, CaO% 44.5, Fe2O3% content of 2.1, Al2O3% content is 2.6, MgO% content is 1.9; the proportion of the phosphorite for desulfurization is 30 percent or more;
and 3, adding the phosphoric acid obtained in the step 1 into a reaction tank, wherein the temperature of the phosphoric acid is higher than 50 ℃, the reaction tank is provided with 5 areas, mineral powder or filter cakes are respectively added from 1, 2 and 3 areas of the reaction tank, the areas of the reaction tank are stirred for reaction, the stirring linear velocity is higher than 5 m/s, the material is guided by adopting a mode of combining overflow and underflow, so that the phosphoric acid and the powdered rock phosphate are fully reacted in the reaction tank, the reaction time is 1.2-2 hours, and the adding amount of the mineral powder or the filter cakes is P2O5The phosphorus ore for extraction which is equivalent to the phosphorus ore for producing the phosphoric acid2O5The amount of (c);
and 4, performing solid-liquid separation on the slurry after the reaction, extracting the solid, and deeply removing impurities from the clear liquid in the next stage.
In this example, non-desulfurized phosphoric acid P2O5/SO38.1, non-desulfurized phosphoric acid concentration 168.73g/l, desulfurized phosphoric acid P2O5/SO319.8, the concentration of the desulfurized phosphoric acid is 192.21g/l, and the grade of the white fertilizer (water content is 40 percent) P2O5% is 14.15, white fertilizer grade (water content is 40%) P of the prior art2O5% of the total amount of the defluorinated phosphoric acid is 16-18%, the yield of the white fertilizer per ton of calcium bicarbonate product is 410kg, and the yield of the defluorinated phosphoric acid is 87.6%.
Example 6
A method for improving the yield of phosphorus by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification comprises the following steps:
step 1, carrying out extraction reaction on phosphorite and sulfuric acid to obtain phosphogypsum and phosphoric acid, and extracting P in the phosphorite2O5% content of 27.71, CaO% content of 40.22, Fe2O3% content of 1.74, Al2O3% content is 2.5, MgO% content is 2.2;
step 2, carrying out wet grinding on the phosphate ore, and filtering the wet ground ore pulp to obtain a filter cake, wherein the water content of the filter cake is less than 18%; p in the phosphate ore for pretreatment2O5% content of 30.45, CaO% content of 47.81, Fe2O3% content of 0.46, Al2O3% content is 0.38, MgO% content is 3.02; the proportion of the phosphorite for desulfurization is 30 percent or more;
and 3, adding the phosphoric acid obtained in the step 1 into a reaction tank, wherein the temperature of the phosphoric acid is higher than 50 ℃, the reaction tank is provided with 8 areas, mineral powder or filter cakes are respectively added from 1, 2, 3 and 4 areas of the reaction tank, the areas of the reaction tank are stirred for reaction, the stirring linear velocity is higher than 5 m/s, the material is guided by adopting a mode of combining overflow and underflow, so that the phosphoric acid and the powdered rock phosphate are fully reacted in the reaction tank, the reaction time is 1.2-2 hours, and the adding amount of the mineral powder or the filter cakes is P2O5The phosphorus ore for extraction which is equivalent to the phosphorus ore for producing the phosphoric acid2O5The amount of (c);
and 4, performing solid-liquid separation on the slurry after the reaction, extracting the solid, and deeply removing impurities from the clear liquid in the next stage.
In this example, non-desulfurized phosphoric acid P2O5/SO38.5, non-desulfurized phosphoric acid concentration 180.3g/l, desulfurized phosphoric acid P2O5/SO320, the concentration of desulfurized phosphoric acid is 206.5g/l, and the grade of white fertilizer (water content is 40 percent) P2O5% is 13.76, white fertilizer grade (water content is 40%) P of the prior art2O5% of the total amount of the defluorinated phosphoric acid is 16-18%, the yield of the white fertilizer per ton of calcium bicarbonate product is 390kg, and the yield of the defluorinated phosphoric acid is 88.5%.
In each of the above examples, SO was in the extracted solution4 2-The concentration of (A) is 2-3%.
In the prior art, the white fertilizer yield (containing 40 percent of water) per ton of calcium hydrophosphate product is 500-600 kg.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for improving the yield of phosphorus by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification is characterized by comprising the following steps:
step 1, carrying out extraction reaction on phosphorite and sulfuric acid to obtain phosphogypsum and phosphoric acid;
step 2, grinding the phosphorite into mineral powder or wet grinding the phosphorite, and filtering the wet ground ore pulp to obtain a filter cake;
and 3, adding the phosphoric acid obtained in the step 1 into a reaction tank, adding the mineral powder or the filter cake obtained in the step 2, and enabling the phosphoric acid and the powdered rock phosphate to fully react in the reaction tank, wherein the adding amount of the mineral powder or the filter cake is P2O5The phosphorus ore for extraction which is equivalent to the phosphorus ore for producing the phosphoric acid2O5The amount of (c);
and 4, performing solid-liquid separation on the slurry after the reaction, extracting the solid, and deeply removing impurities from the clear liquid in the next stage.
2. The method for improving the yield of the phosphorus by using the phosphorite with the high calcium-phosphorus ratio for the wet-process phosphoric acid purification as claimed in claim 1, wherein the ratio of the calcium content to the phosphorus content in the phosphorite in the steps 1 and 2 is higher than 1.43.
3. The method for improving the phosphorus yield by using the phosphorite with the high calcium-phosphorus ratio for wet-process phosphoric acid purification according to claim 1, characterized in that in the step 1, the mass ratio of the phosphorite to the sulfuric acid is 3.5-3.9: 2.5-2.8.
4. The method for improving the yield of phosphorus by using phosphorite with high calcium-phosphorus ratio for wet phosphoric acid purification according to claim 1, characterized in that the mass concentration of phosphoric acid in step 1 is 16% or more.
5. The method for improving the phosphorus yield by using the phosphorite with high calcium phosphorus ratio for the wet-process phosphoric acid purification as claimed in claim 1, wherein the moisture content of the filter cake in the step 2 is less than 20%.
6. The method for improving the phosphorus yield by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification according to claim 1, characterized in that step 3 specifically comprises adding ore powder or filter cakes in 2 or more reaction tanks in different ways, stirring the reaction tank areas for reaction, guiding the materials by combining overflow and underflow, and arranging 4-8 reaction tanks.
7. The method for improving the phosphorus yield by using the phosphorite with high calcium phosphorus ratio for the wet-process phosphoric acid purification as claimed in claim 6, wherein the temperature of the phosphoric acid in the step 3 is more than 45 ℃.
8. The method for improving the yield of the phosphorus by using the phosphorite with the high calcium phosphorus ratio for the wet-process phosphoric acid purification, as recited in claim 6, characterized in that the linear velocity of the stirring in the step 3 is more than 5 m/s.
9. The method for improving the yield of the phosphorus by using the phosphorite with the high calcium phosphorus ratio for the wet-process phosphoric acid purification as claimed in claim 6, wherein the reaction time in the step 3 is 1.2-2 hours.
10. The method for improving the yield of phosphorus by using phosphorite with high calcium-phosphorus ratio for wet-process phosphoric acid purification according to claim 1, characterized in that the yield of defluorinated phosphoric acid is more than 87%.
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