CN114703385B - Technological method for extracting phosphorus and rare earth from rare earth-containing low-grade phosphorite - Google Patents
Technological method for extracting phosphorus and rare earth from rare earth-containing low-grade phosphorite Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 94
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 77
- 239000002367 phosphate rock Substances 0.000 title claims abstract description 39
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 34
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000011574 phosphorus Substances 0.000 title claims abstract description 33
- 238000002386 leaching Methods 0.000 claims abstract description 128
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 96
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 41
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 40
- 239000012141 concentrate Substances 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 20
- 239000010452 phosphate Substances 0.000 claims abstract description 20
- 238000005188 flotation Methods 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 17
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 15
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 15
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 15
- 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 claims abstract description 15
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 14
- -1 rare earth oxalate Chemical class 0.000 claims abstract description 14
- 239000002893 slag Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000001110 calcium chloride Substances 0.000 claims abstract description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 230000002000 scavenging effect Effects 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 6
- 239000011707 mineral Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000001914 filtration Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052585 phosphate mineral Inorganic materials 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- 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
- C01B25/324—Preparation from a reaction solution obtained by acidifying with an acid other than orthophosphoric acid
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of mineral separation, and provides a process method for extracting phosphorus and rare earth from rare earth-containing low-grade phosphorite, which comprises the following steps: s1, flotation: flotation is carried out on low-grade rare earth-containing phosphorite to obtain phosphate concentrate; s2, leaching with primary sulfuric acid: carrying out sulfuric acid leaching on the phosphate concentrate to obtain sulfuric acid leaching solution and primary leaching slag; s3, precipitating phosphorus: adding calcium chloride into the sulfuric acid leaching solution to precipitate phosphorus, thereby obtaining phosphorus-precipitating solid active calcium phosphate; s4, leaching by two-stage nitric acid: nitric acid leaching is carried out on the first-stage leaching slag to obtain nitric acid leaching liquid and second-stage leaching slag; s5, rare earth precipitation: adding oxalic acid into the nitric acid leaching solution to obtain rare earth oxalate. By the technical scheme, the problems that the recovery rate of rare earth is low and the separation of phosphorus and rare earth is difficult in the method for extracting rare earth elements from low-grade phosphorite in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of mineral separation, in particular to a process method for extracting phosphorus and rare earth from rare earth-containing low-grade phosphorite.
Background
Rare earth is an important strategic resource and is widely applied to the fields of military, metallurgy, petrochemical industry, agriculture, new energy sources and the like. Rare earth exists in nature mainly in the form of minerals, besides bastnaesite, cerini-niobium perovskite, monazite and other rare earth minerals, rare earth is also widely accompanied in other metal frames, wherein accompanying rare earth phosphate ore is one of the most representative mineral species, and in accompanying rare earth phosphate ore, rare earth is dispersed in phosphate minerals in a similar substitution form. At present, the phosphorite mainly takes medium and low grades as main materials, and has important significance in comprehensively recycling rare earth resources while developing the phosphorite.
At present, rare earth elements are extracted from low-grade phosphorite mainly by wet phosphoric acid method, hot phosphoric acid method, extraction method and other rare earth extraction methods. In the wet phosphoric acid method, the sulfuric acid method is most commonly applied, and in the process of decomposing phosphorite by sulfuric acid, on one hand, phosphorus and rare earth are difficult to separate, on the other hand, the separated rare earth is enriched in phosphogypsum, and the existing method for recovering rare earth from phosphogypsum has the problem of low recovery rate of rare earth and waste of rare earth resources.
Disclosure of Invention
The invention provides a process method for extracting phosphorus and rare earth from low-grade phosphorite containing rare earth, which solves the problems of low recovery rate of rare earth and difficult separation of phosphorus and rare earth in the prior art for extracting rare earth elements from low-grade phosphorite.
The technical scheme of the invention is as follows:
a process method for extracting phosphorus and rare earth from rare earth-containing low-grade phosphorite comprises the following steps:
s1, flotation: flotation is carried out on low-grade rare earth-containing phosphorite to obtain phosphate concentrate;
s2, leaching with primary sulfuric acid: carrying out sulfuric acid leaching on the phosphate concentrate to obtain sulfuric acid leaching solution and primary leaching slag;
s3, precipitating phosphorus: adding calcium chloride into the sulfuric acid leaching solution to precipitate phosphorus, thereby obtaining phosphorus-precipitating solid active calcium phosphate;
s4, leaching by two-stage nitric acid: nitric acid leaching is carried out on the first-stage leaching slag to obtain nitric acid leaching liquid and second-stage leaching slag;
s5, rare earth precipitation: adding oxalic acid into the nitric acid leaching solution to obtain rare earth oxalate.
As a further technical scheme, the flotation in the step S1 is three times of fine selection of primary roughing, secondary scavenging.
As a further technical scheme, during the primary roughing, the low-grade rare earth-containing phosphorite is ground until the ore granularity is-0.074 mm and the partial content of the low-grade rare earth-containing phosphorite accounts for more than 95% of the total ore.
As a further technical scheme, the collecting agent is oxidized paraffin soap during one-time roughing.
As a further technical scheme, when one-stage sulfuric acid leaching is carried out in the step S2, the leaching temperature is 12-20 ℃, the leaching time is 1.5-2.5h, and the liquid-solid ratio of sulfuric acid to phosphate concentrate is 3-6:1.
as a further technical scheme, in the step S4, when the second stage nitric acid is leached, the leaching temperature is 12-20 ℃, the leaching time is 2 hours, the leaching time is 1.5-2.5 hours, and the liquid-solid ratio of nitric acid to the first stage leaching slag is 3-6:1.
as a further technical scheme, the dosage of the calcium chloride in each liter of sulfuric acid leaching solution in the step S3 is 20-40g.
As a further technical scheme, the oxalic acid in each liter of nitric acid leaching solution in the step S5 is used in an amount of 1-6g.
As a further technical scheme, in the step S3, alkali is added to adjust the pH value of the sulfuric acid leaching solution to 8-9 before calcium chloride is added to the sulfuric acid leaching solution for precipitating phosphorus.
As a further technical scheme, in the step S5, alkali is added to adjust the pH value of the nitric acid leaching solution to 1.8-2.0 before oxalic acid is added to the nitric acid leaching solution.
The working principle and the beneficial effects of the invention are as follows:
1. in the invention, low-grade phosphorite is taken as raw material to extract phosphorus and rare earth, thus solving the resource utilization problem of low-grade phosphorite, in the extraction method, flotation and two-stage acid leaching are both carried out at normal temperature, and the P in the product is caused by the separation of phosphorus and rare earth by utilizing different leaching rates of sulfuric acid and nitric acid to phosphorus and rare earth 2 O 5 Grade 38.45%, P 2 O 5 The recovery rate is 78.69%, the rare earth oxalate REO grade is 1.59%, and the REO recovery rate is 72.69%, so that the problems that the recovery rate of rare earth is low and the separation of phosphorus and rare earth is difficult in the method for extracting rare earth elements from low-grade phosphorite in the prior art are solved.
2. In the invention, low-grade phosphorite is used as a raw material, and chemical grade active calcium carbonate and oxalic acid rare earth are obtained through floatation and two-stage acid leaching, so that the mode that the traditional beneficiation product is phosphate concentrate is broken.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a flow chart of a flotation process in example 1 of the present invention;
FIG. 2 is a two-stage acid leaching process flow chart in example 1 of the present invention:
FIG. 3 shows the concentration of sulfuric acid versus P in a stage of sulfuric acid leaching in experimental example 1 of the present invention 2 O 5 A REO leaching rate influence result graph;
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, the rare earth-containing low-grade phosphate ore sample was derived from a phosphate rock of the Sichuan-laid type in Qingqiang county of Shaanxi, which was a low-grade phosphate deposit found in the sixty of the last century, and the ore minerals of the phosphate rock ore were mainly collophanite (fluorocarbon apatite), argillite, quartz, calcite, dolomite, pyrite, and char, and the phosphate rock contained abundant rare earth, and the grade of Rare Earth Oxide (REO) was 200X 10 -6 ～1726×10 -6 In the selected phosphate rock sample P 2 O 5 Grade 1.13% -21.03%, and phase analysis shows that P in the fluorocarbon apatite 2 O 5 The content is 5.08 percent and the distribution rate is 97.65 percent.
Example 1
S1, flotation: taking P 2 O 5 Flotation is carried out on phosphorite with grade of 5.49 percent and REO grade of 505.4g/t to obtain P 2 O 5 Phosphate concentrate with grade of 14.63 percent and REO grade of 1217.98g/t and P 2 O 5 Tailings with grade of 1.55 percent and REO grade of 181.10 g/t;
the specific process is as follows:
roughing: during roughing, firstly grinding phosphorite until the ore granularity-0.074 mm part content accounts for 95% of the total ore, and then roughing by taking oxidized paraffin soap as a collector to obtain P 2 O 5 Roughing concentrate with grade of 10.95 percent and REO grade of 946.91g/t and P 2 O 5 Roughing tailings with grade of 2.16% and REO grade of 232.04 g/t;
and (5) one-time scavenging: scavenging the roughing tailings for one time to obtain P 2 O 5 Primary scavenging concentrate with grade of 6.34%, REO grade of 580.11g/t and P 2 O 5 Primary scavenging tailings with grade of 1.74 percent and REO grade of 206.98 g/t; returning the primary scavenging concentrate to the roughing step to continue roughing;
and (3) secondary scavenging: the primary scavenging tailings are subjected to secondary scavenging to obtain P 2 O 5 Secondary scavenging concentrate of grade 3.21%, REO grade 412.45g/t and P 2 O 5 Secondary scavenging tailings with grade of 1.55 percent and REO grade of 181.10 g/t; returning the secondary scavenging concentrate to the primary scavenging step to continue the primary scavenging;
primary selection: the roughing concentrate is subjected to primary concentration to obtain P 2 O 5 Primary concentrate with grade of 13.31%, REO grade of 1135.20g/t and P 2 O 5 Primary tailings of grade 5.48% and REO grade 543.56 g/t; returning the primary tailings to the roughing step for roughing;
secondary selection: performing secondary concentration on the primary concentration tailings to obtain P 2 O 5 Secondary concentrate of grade 13.96%, REO grade 1167.08g/t and P 2 O 5 Secondary concentration tailings with grade of 6.87% and REO grade of 732.146g/tThe method comprises the steps of carrying out a first treatment on the surface of the Returning the secondary tailings to the primary concentrating step to continue primary concentrating;
selecting for three times; performing tertiary concentration on the secondary concentration tailings to obtain P 2 O 5 Phosphate concentrate with grade of 14.63 percent and REO grade of 1217.98g/t and P 2 O 5 Tertiary tailings of grade 10.39% and REO grade 895.76 g/t; returning the tertiary tailings to the secondary concentrating step to continue secondary concentrating;
s2, leaching with primary sulfuric acid: adding 1000mL of sulfuric acid with the concentration of 150g/L into 200g of phosphate concentrate to perform primary sulfuric acid leaching, wherein the leaching temperature is 12-20 ℃, the leaching time is 2 hours, and filtering to obtain sulfuric acid leaching solution and primary leaching slag; p (P) 2 O 5 Leaching rate 83.86%, P 2 O 5 The recovery rate is 96.43%; the REO leaching rate is only 7.31%;
s3, precipitating phosphorus: adding 15g of sodium hydroxide into 1000mL of sulfuric acid leaching solution to adjust the pH to 8-9, adding 32g of calcium chloride to precipitate for 2h, and filtering to obtain phosphorus-precipitating solid and phosphorus-precipitating tail liquid, wherein the phosphorus-precipitating solid is active calcium phosphate Ca 10 (PO 4 ) 6 (OH) 2 Wherein P is 2 O 5 Grade is 38.45 percent, the chemical grade product standard is achieved, and REO grade is 1167.08g/t;
s4, leaching by two-stage nitric acid: adding 300mL of 150g/L nitric acid into 100g of primary leaching residue to perform secondary nitric acid leaching, wherein the leaching temperature is 12-20 ℃, the leaching time is 2 hours, and filtering to obtain nitric acid leaching solution and secondary leaching residue; the REO leaching rate is up to 97.20%;
s5, rare earth precipitation: adding 8g of sodium hydroxide into 1000mL of nitric acid leaching solution to adjust the pH value to 1.8-2.0, then adding 5g of oxalic acid to precipitate for 2 hours, and filtering to obtain rare earth precipitate and rare earth tail liquid, wherein the rare earth precipitate is rare earth oxalate, the REO grade is 1.59%, and the REO precipitation rate is 99.29%;
the final product is active calcium phosphate Ca 10 (PO 4 ) 6 (OH) 2 And oxalic acid rare earth, wherein the active calcium phosphate reaches the chemical grade product standard HG/T3583-2009, and P in the active calcium phosphate 2 O 5 Grade 38.45%, REO grade 1.59%, P in rare earth oxalate 2 O 5 The grade is improved by 6 times,the REO grade is improved by 30.8 times.
P of each concentrate and tailing in flotation process 2 O 5 Grade, REO grade, P 2 O 5 Recovery, REO recovery and overall yield are shown in the following table:
TABLE 1P of concentrate and tailings during flotation 2 O 5 Grade, REO grade, P 2 O 5 Recovery, REO recovery and overall yield
Example 2
S1, flotation: taking P 2 O 5 Flotation is carried out on phosphorite with grade of 5.49 percent and REO grade of 505.4g/t to obtain P 2 O 5 Phosphate concentrate with grade of 13.50%, REO grade of 1243.03g/t and P 2 O 5 Tailings with grade of 1.40% and REO grade of 143.09 g/t;
s2, leaching with primary sulfuric acid: adding 300mL of sulfuric acid with the concentration of 400g/L into 100g of phosphate concentrate to perform primary sulfuric acid leaching, wherein the leaching temperature is 12-20 ℃, the leaching time is 2.5 hours, and filtering to obtain sulfuric acid leaching solution and primary leaching slag; p (P) 2 O 5 Leaching rate is 99.59%; the REO leaching rate is only 42.41%;
s3, precipitating phosphorus: adding 30g of sodium hydroxide into 300mL of sulfuric acid leaching solution to adjust the pH to 8-9, adding 6g of calcium chloride to precipitate for 2h, and filtering to obtain phosphorus-precipitating solid and phosphorus-precipitating tail liquid, wherein the phosphorus-precipitating solid is active calcium phosphate Ca 10 (PO 4 ) 6 (OH) 2 Wherein P is 2 O 5 Grade 38.49 percent, and achieves the standard of chemical grade products; REO grade 150.2g/t;
s4, leaching by two-stage nitric acid: adding 300mL of nitric acid with the concentration of 180g/L into 100g of primary leaching residue to carry out secondary nitric acid leaching, wherein the leaching temperature is 12-20 ℃, the leaching time is 2.5h, and filtering to obtain nitric acid leaching solution and secondary leaching residue; REO leaching rate is up to 97.27%;
s5, rare earth precipitation: adding 20g of sodium hydroxide into 300mL of nitric acid leaching solution to adjust the pH value to 1.8-2.0, then adding 1g of oxalic acid to precipitate for 2 hours, and filtering to obtain rare earth precipitate and rare earth tail liquid, wherein the rare earth precipitate is rare earth oxalate, and the REO grade is 14530.05g/t, and the REO precipitation rate is 95.59%;
the final product is active calcium phosphate Ca 10 (PO 4 ) 6 (OH) 2 And oxalic acid rare earth, wherein the active calcium phosphate reaches the chemical grade product standard HG/T3583-2009, and P in the active calcium phosphate 2 O 5 Grade 38.49%, REO grade 14530.05g/t, P in rare earth oxalate 2 O 5 Recovery was increased by 6-fold and REO was increased by 27.75-fold.
Example 3
S1, flotation: taking P 2 O 5 Flotation is carried out on phosphorite with grade of 5.49 percent and REO grade of 505.4g/t to obtain P 2 O 5 Phosphate concentrate with grade of 14.63 percent and REO grade of 1217.98g/t and P 2 O 5 Tailings with grade of 1.55 percent and REO grade of 181.10 g/t;
s2, leaching with primary sulfuric acid: adding 300mL of sulfuric acid with the concentration of 600g/L into 100g of phosphate concentrate to perform primary sulfuric acid leaching, wherein the leaching temperature is 12-20 ℃, the leaching time is 1.5h, and filtering to obtain sulfuric acid leaching solution and primary leaching slag; p (P) 2 O 5 Leaching rate is 98.73%; the REO leaching rate is only 50.33%;
s3, precipitating phosphorus: adding 30g of sodium hydroxide into 300mL of sulfuric acid leaching solution to adjust the pH to 8-9, adding 6g of calcium chloride to precipitate for 2h, and filtering to obtain phosphorus-precipitating solid and phosphorus-precipitating tail liquid, wherein the phosphorus-precipitating solid is active calcium phosphate Ca 10 (PO 4 ) 6 (OH) 2 Wherein P is 2 O 5 Grade is 38.45%, and the standard of chemical grade products is achieved; REO grade is 286.4g/t;
s4, leaching by two-stage nitric acid: adding 300mL of nitric acid with the concentration of 120g/L into 100g of primary leaching residue to carry out secondary nitric acid leaching, wherein the leaching temperature is 12-20 ℃, the leaching time is 1.5h, and filtering to obtain nitric acid leaching solution and secondary leaching residue; the REO leaching rate is up to 97.20%;
s5, rare earth precipitation: adding 20g of sodium hydroxide into 300mL of nitric acid leaching solution to adjust the pH value to 1.8-2.0, then adding 1g of oxalic acid to precipitate for 2 hours, and filtering to obtain rare earth precipitate and rare earth tail liquid, wherein the rare earth precipitate is rare earth oxalate, and the REO grade is 1.53%, and the REO precipitation rate is 99%;
the final product is active calcium phosphate Ca 10 (PO 4 ) 6 (OH) 2 And oxalic acid rare earth, wherein the active calcium phosphate reaches the chemical grade product standard HG/T3583-2009, and P in the active calcium phosphate 2 O 5 Grade 38.45%, REO grade 1.53% in rare earth oxalate, P 2 O 5 Recovery was increased by 6-fold and REO was increased by 29.27-fold.
Experimental example 1
During the first stage of sulfuric acid leaching in the step S2, different sulfuric acid concentrations are studied for P 2 O 5 Influence of REO leaching rate, test conditions are shown in the following table:
TABLE 2 sulfuric acid concentration vs P 2 O 5 Influence of REO leaching Rate test conditions
The results are shown in FIG. 3, from which it can be seen that P 2 O 5 The REO leaching rate and the sulfuric acid concentration show a better linear relation, and under the same test condition, P 2 O 5 And the leaching rate of REO is greatly different. When the sulfuric acid concentration is 150g/L, the REO leaching rate is only 7.31%, and P 2 O 5 The leaching rate is 83.86 percent, which is the basis of the two-stage nitric acid leaching process, wherein the first stage sulfuric acid leaching is used for decomposing phosphorus, and the second stage nitric acid leaching is performed on the first stage leaching residue to decompose rare earth.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. A process method for extracting phosphorus and rare earth from low-grade phosphorite containing rare earth is characterized by comprising the following steps:
s1, flotation: flotation is carried out on low-grade rare earth-containing phosphorite to obtain phosphate concentrate;
s2, leaching with primary sulfuric acid: carrying out sulfuric acid leaching on the phosphate concentrate to obtain sulfuric acid leaching solution and primary leaching slag;
s3, precipitating phosphorus: adding calcium chloride into the sulfuric acid leaching solution to precipitate phosphorus, thereby obtaining phosphorus-precipitating solid active calcium phosphate;
s4, leaching by two-stage nitric acid: nitric acid leaching is carried out on the first-stage leaching slag to obtain nitric acid leaching liquid and second-stage leaching slag;
s5, rare earth precipitation: adding oxalic acid into the nitric acid leaching solution to obtain rare earth oxalate;
in the step S2, when the primary sulfuric acid is leached, the leaching temperature is 12-20 ℃, the leaching time is 1.5-2.5h, and the liquid-solid ratio of sulfuric acid to phosphate concentrate is 3-6:1, a step of;
in the step S4, when the second stage nitric acid is leached, the leaching temperature is 12-20 ℃, the leaching time is 1.5-2.5 hours, and the liquid-solid ratio of nitric acid to the first stage leaching slag is 3-6:1.
2. the process for extracting phosphorus and rare earth from low-grade phosphorite containing rare earth according to claim 1, wherein the flotation in the step S1 is three-time concentration of primary roughing and secondary scavenging.
3. The process for extracting phosphorus and rare earth from low-grade phosphorite containing rare earth according to claim 2, wherein the low-grade phosphorite containing rare earth is ground to a grain size of-0.074 mm and the partial content of the low-grade phosphorite containing rare earth is more than 95% of the total ore during the primary roughing.
4. The process for extracting phosphorus and rare earth from low-grade phosphorite containing rare earth according to claim 2, wherein the collector is oxidized paraffin soap during the primary roughing.
5. The process for extracting phosphorus and rare earth from low-grade phosphorite containing rare earth according to claim 1, wherein the dosage of calcium chloride in each liter of sulfuric acid leaching solution in the step S3 is 20-40g.
6. The process for extracting phosphorus and rare earth from low-grade phosphorite containing rare earth according to claim 1, wherein the oxalic acid content in each liter of nitric acid leaching solution in the step S5 is 1-6g.
7. The process for extracting phosphorus and rare earth from low-grade phosphorite containing rare earth according to claim 1, wherein in the step S3, alkali is added to adjust the pH value of the sulfuric acid leaching solution to 8-9 before calcium chloride is added to the sulfuric acid leaching solution for precipitating phosphorus.
8. The process for extracting phosphorus and rare earth from low-grade phosphorite containing rare earth according to claim 1, wherein in the step S5, alkali is added to adjust the pH value of the nitric acid leaching solution to 1.8-2.0 before oxalic acid is added to the nitric acid leaching solution.
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| CA2631190A1 (en) * | 2008-05-02 | 2009-11-02 | Arafura Resources Limited | Recovery of rare earth elements |
| CN102796888A (en) * | 2012-09-09 | 2012-11-28 | 贵州黔鸿瑞磷稀土***开发有限公司 | Process for extracting rare earth from phosphate concentrate |
| KR101422068B1 (en) * | 2013-11-14 | 2014-07-23 | 한국지질자원연구원 | Recovery method of rare earth elements and non rare earth elements from rare earth ore |
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| CN111979411A (en) * | 2020-09-25 | 2020-11-24 | 贵州省地质矿产中心实验室(贵州省矿产品黄金宝石制品质量检验站) | Method for separating phosphorus-enriched rare earth from rare earth-containing phosphorite |
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| CA2631190A1 (en) * | 2008-05-02 | 2009-11-02 | Arafura Resources Limited | Recovery of rare earth elements |
| CN102796888A (en) * | 2012-09-09 | 2012-11-28 | 贵州黔鸿瑞磷稀土***开发有限公司 | Process for extracting rare earth from phosphate concentrate |
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| CN111979411A (en) * | 2020-09-25 | 2020-11-24 | 贵州省地质矿产中心实验室(贵州省矿产品黄金宝石制品质量检验站) | Method for separating phosphorus-enriched rare earth from rare earth-containing phosphorite |
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