CN116987893A - Method for recycling monazite slag - Google Patents
Method for recycling monazite slag Download PDFInfo
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- CN116987893A CN116987893A CN202311005258.6A CN202311005258A CN116987893A CN 116987893 A CN116987893 A CN 116987893A CN 202311005258 A CN202311005258 A CN 202311005258A CN 116987893 A CN116987893 A CN 116987893A
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- Prior art keywords
- uranium
- solid
- filtrate
- monazite
- rare earth
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- 239000002893 slag Substances 0.000 title claims abstract description 82
- 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 title claims abstract description 66
- 229910052590 monazite Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000004064 recycling Methods 0.000 title claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 67
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 65
- 239000000706 filtrate Substances 0.000 claims abstract description 60
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims abstract description 50
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 50
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 47
- 239000007787 solid Substances 0.000 claims abstract description 45
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 44
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 17
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 23
- 239000012074 organic phase Substances 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 239000001099 ammonium carbonate Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 12
- 235000010755 mineral Nutrition 0.000 claims description 12
- 239000011707 mineral Substances 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 235000017550 sodium carbonate Nutrition 0.000 claims description 11
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- 239000012716 precipitator Substances 0.000 claims description 7
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 229910052599 brucite Inorganic materials 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 30
- 238000011084 recovery Methods 0.000 abstract description 14
- 238000000605 extraction Methods 0.000 abstract description 13
- 230000001376 precipitating effect Effects 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- 230000032683 aging Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- -1 phosphate rare earth Chemical class 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 239000003350 kerosene Substances 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002918 waste heat Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- RUJLHPZAKCVICY-UHFFFAOYSA-J thorium(4+);disulfate Chemical compound [Th+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUJLHPZAKCVICY-UHFFFAOYSA-J 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910052845 zircon Inorganic materials 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GFRMDONOCHESDE-UHFFFAOYSA-N [Th].[U] Chemical compound [Th].[U] GFRMDONOCHESDE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000002419 base digestion Methods 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-N phosphoric acid;yttrium(3+) Chemical compound [Y+3].OP(O)(O)=O UXBZSSBXGPYSIL-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 150000003586 thorium compounds Chemical class 0.000 description 1
- VGBPIHVLVSGJGR-UHFFFAOYSA-N thorium(4+);tetranitrate Chemical compound [Th+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VGBPIHVLVSGJGR-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/402—Mixtures of acyclic or carbocyclic compounds of different types
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0221—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching
- C22B60/0226—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors
- C22B60/0234—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors sulfurated ion as active agent
-
- 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
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/026—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries liquid-liquid extraction with or without dissolution in organic solvents
-
- 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
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/0278—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries by chemical methods
-
- 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
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0291—Obtaining thorium, uranium, or other actinides obtaining thorium
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- 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)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
In the method for recycling the monazite slag, the sulfuric acid with the mass concentration of 60-75% and the monazite slag are utilized to carry out decomposition reaction at the temperature of 110-130 ℃, so that the decomposition rate of rare earth elements, thorium and uranium in a decomposition mixture can be effectively improved; meanwhile, in order to further improve the solubility of rare earth elements, thorium and uranium in the solution, water which is low in cost and easy to obtain is added into the application, so that after solid-liquid separation, the first filtrate containing the rare earth elements, thorium and uranium and the first solid containing zirconium can be obtained. Further, in the subsequent step of precipitating thorium, a metal compound precipitant is adopted, so that the recovery rate of rare earth can be effectively improved. Meanwhile, the recycling method of the monazite slag provided by the application does not need to use a large amount of reagents for extraction, and is environment-friendly in work.
Description
Technical Field
The application relates to the technical field of hydrometallurgy, in particular to a method for recycling monazite slag.
Background
Monazite is an important phosphate rare earth ore, often associated with zircon sand, ilmenite, rutile and other minerals, and associated with more radioactive elements such as thorium, uranium and the like. The sodium hydroxide alkali digestion decomposition method is generally adopted in industry to extract rare earth elements and phosphorus elements from monazite, and a large amount of precipitation slag is generated after extraction, and is industrially called monazite excellent slag. The rare earth chloride solution formed by the eugenolysis of hydrochloric acid after the monazite alkali is decomposed is further subjected to radioremoving operation, and the radionuclide can form slag to be deposited, so that the deslagging is formed. Fully dissolving the excellent slag with acid and hydrogen peroxide under a heating state, fully reacting uranium, thorium and rare earth in the monazite concentrate with hydrochloric acid, transferring the reaction product into a dissolving solution, and carrying out solid-liquid separation to obtain slag which is the full slag. Several types of slag are generally referred to as monazite slag and are treated together.
The main components of the monazite slag comprise elements such as thorium, rare earth, uranium, titanium, iron, zirconium, silicon and the like. The traditional method for extracting rare earth, thorium element and uranium element from monazite slag mainly comprises an acid process and an alkali process. The acid process mainly adopts concentrated acid roasting or curing and dissolving, and has high acid mist concentration and low leaching rate of thorium uranium, rare earth and the like in the recovery process, so that the recovery rate is affected, and the industrial application of the acid process is difficult. The alkaline process mainly adopts alkaline decomposition, but the method has high alkaline consumption and high cost, and the separation of thorium and rare earth is difficult, so that coprecipitation is easy to occur, and the recovery rate of rare earth elements and thorium is reduced.
Disclosure of Invention
Based on the above, the application provides a method for recycling monazite slag. The method for recycling the monazite slag is safe and environment-friendly, and can improve the recycling rate of uranium and zirconium; furthermore, the recycling method provided by the application is easy to be industrially applied.
The application provides a method for recycling monazite slag, which comprises the following steps:
mixing monazite slag and inorganic acid, and carrying out decomposition reaction at 110-130 ℃;
adding water for mixing, and preparing a zirconium-containing first solid and a first filtrate after solid-liquid separation; wherein the inorganic acid is a sulfuric acid aqueous solution with the mass concentration of 60-75%;
adding an extractant into the first filtrate to prepare uranium-containing organic phase and raffinate;
washing the uranium-containing organic phase by adopting a washing solution, and then carrying out a complexing reaction by utilizing an alkaline compound complexing agent to prepare a uranium-containing complex solution;
and heating the uranium-containing complex solution, acidifying to a pH value less than 6, and then carrying out solid-liquid separation to prepare a second filtrate and uranium-containing second solid.
In one embodiment, the ratio of the mass of the monazite slag to the volume of the mineral acid is 1kg: (0.8-1.5) L.
In one embodiment, the process parameters of the water addition mix include: the mixing temperature is 50-70 ℃.
In one embodiment, in the step of mixing with water, the ratio of the mass of the monazite slag to the volume of water is 1000kg: (3-5) m 3 。
In one embodiment, the alkaline compound complexing agent comprises one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, and ammonium bicarbonate.
In one embodiment, the extractant comprises, by volume, 4% to 8% trioctyl tertiary amine, 2% to 4% alcohol, and 88% to 94% solvent oil.
In one embodiment, the wash solution comprises an aqueous sulfuric acid solution having a molar concentration of 0.2mol/L to 0.5 mol/L.
In one embodiment, the method further comprises the step of treating the raffinate:
heating the raffinate to 50-75 ℃, adding a metal compound precipitator until the pH value is 4-5.5, and then carrying out solid-liquid separation to prepare a third filtrate and a third solid containing thorium.
In one embodiment, the metal compound precipitant has one or more of the following characteristics:
(1) The chemical components of the metal compound precipitant comprise MgO and MgCO 3 And Mg (OH) 2 One or more of the following;
(2) The metal compound precipitant includes one or more of magnesite and brucite.
In one embodiment, the method further comprises the step of treating the third filtrate:
mixing the third filtrate with seed crystals and an alkaline compound precipitator, and after the pH value is 6.8-7.2, carrying out solid-liquid separation to prepare a fourth filtrate and a fourth solid containing rare earth;
wherein the alkaline compound precipitant comprises one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate.
In the method for recycling the monazite slag, the sulfuric acid with the mass concentration of 60-75% and the monazite slag are utilized to carry out decomposition reaction at the temperature of 110-130 ℃, so that the decomposition rate of rare earth elements, thorium and uranium in a decomposition mixture can be effectively improved; meanwhile, in order to further improve the solubility of rare earth, thorium and uranium in the solution, water which is low in cost and easy to obtain is added into the application, so that after solid-liquid separation, the first filtrate containing the rare earth, thorium and uranium and the first solid containing zirconium can be obtained. Uranium, thorium and rare earth can be effectively separated by extracting the first filtrate, a uranium-containing organic phase and raffinate containing thorium and rare earth are obtained, and under the cooperation of low-acid washing of the uranium-containing organic phase and heating acidification treatment of a stripping complex, the recovery rate of uranium can be further improved. Further, in the subsequent step of precipitating thorium by utilizing raffinate, a metal compound precipitant is adopted, so that the co-precipitation of thorium and rare earth can be effectively reduced, and the recovery rate of thorium and rare earth can be further improved. Meanwhile, the recycling method of the monazite slag provided by the application does not need to use a large amount of reagents for extraction, and is environment-friendly in work.
Detailed Description
The method for recovering monazite slag is described more fully and clearly below with reference to specific examples. The present application may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
in the present application, the terms "plurality", "plural", "multiple", and the like are used in terms of the number of the terms "plurality", "multiple", and the like, and are not particularly limited, but are greater than 2 or equal to 2 in number. For example, "one or more" means one kind or two or more kinds.
In the present application, the terms "first", "second", "third", "fourth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying an importance or quantity of a technical feature indicated. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
In the application, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
In the present application, references to "preferred", "better", "preferred" are merely to describe embodiments or examples of better results, and it should be understood that they do not limit the scope of the present application.
In the present application, references to "further", "still further", "particularly" and the like are used for descriptive purposes and indicate that the application is not to be interpreted as limiting the scope of the application.
In the present application, reference to "optional", "optional" refers to the presence or absence of the "optional" or "optional" means either of the "with" or "without" side-by-side arrangements. If multiple "alternatives" occur in a technical solution, if no particular description exists and there is no contradiction or mutual constraint, then each "alternative" is independent.
In the present application, a numerical range (i.e., a numerical range) is referred to, and optional numerical distributions are considered to be continuous within the numerical range and include two numerical endpoints (i.e., a minimum value and a maximum value) of the numerical range and each numerical value between the two numerical endpoints unless otherwise specified. Where a numerical range merely refers to integers within the numerical range, including both end integers of the numerical range, and each integer between the two ends, unless otherwise indicated, each integer is recited herein as directly, such as where t is an integer selected from 1 to 10, and where t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Further, when a plurality of range description features or characteristics are provided, these ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The temperature parameter in the present application is not particularly limited, and may be a constant temperature treatment or may vary within a predetermined temperature range. It should be appreciated that the constant temperature process described allows the temperature to fluctuate within the accuracy of the instrument control. Allows for fluctuations within a range such as + -5 ℃, + -4 ℃, + -3 ℃, + -2 ℃, + -1 ℃.
In the present application, the term "percent concentration" refers to the final concentration unless otherwise specified. The final concentration refers to the ratio of the additive component in the system after the component is added.
The rare earth element and the phosphorus element are extracted from the monazite to generate a large amount of precipitation slag, which is industrially called monazite excellent slag. The rare earth chloride solution formed by the eugenolysis of hydrochloric acid after the monazite alkali is decomposed is further subjected to radioremoving operation, and the radionuclide can form slag to be deposited, so that the deslagging is formed. Fully dissolving the excellent slag in the heating state by using acid and hydrogen peroxide, fully reacting uranium, thorium and rare earth in the monazite concentrate with hydrochloric acid, transferring the reaction product into a dissolving solution, and carrying out solid-liquid separation to obtain slag which is the full slag. Typically, the monazite superior slag, the deslagging and the total slag are collectively referred to as monazite slag and are treated together.
The application provides a method for recycling monazite slag, which comprises the following steps:
s10, mixing monazite slag and inorganic acid, and carrying out decomposition reaction at the temperature of 110-130 ℃ to prepare a decomposition mixture; wherein the inorganic acid is a sulfuric acid aqueous solution with the mass concentration of 60-75%;
s20, adding water into the decomposition mixture, mixing, and preparing a zirconium-containing first solid and a first filtrate after solid-liquid separation;
s30, adding an extractant into the first filtrate to prepare a uranium-containing organic phase and raffinate; washing the uranium-containing organic phase by adopting a washing solution, and then carrying out a complexing reaction by utilizing an alkaline compound complexing agent to prepare a uranium-containing complex solution; and heating the uranium-containing complex solution, acidifying until the pH value is less than 6, and then carrying out solid-liquid separation to prepare a second filtrate and uranium-containing second solid.
In the method for recycling the monazite slag, the sulfuric acid with the mass concentration of 60-75% and the monazite slag are utilized to carry out decomposition reaction at the temperature of 110-130 ℃, so that the decomposition rate of rare earth elements, thorium and uranium in a decomposition mixture can be effectively improved; meanwhile, in order to further improve the solubility of rare earth, thorium and uranium in the solution, water which is low in cost and easy to obtain is added into the application, so that after solid-liquid separation, the first filtrate containing the rare earth, thorium and uranium and the first solid containing zirconium can be obtained. Uranium, thorium and rare earth can be effectively separated by extracting the first filtrate, a uranium-containing organic phase and raffinate containing thorium and rare earth are obtained, and under the cooperation of low-acid washing of the uranium-containing organic phase and heating acidification treatment of a stripping complex, the recovery rate of uranium can be further improved. Further, in the subsequent step of precipitating thorium, a metal compound precipitator is adopted, so that the co-precipitation of thorium and rare earth can be effectively reduced, and the recovery rate of thorium and rare earth can be further improved. Meanwhile, the recycling method of the monazite slag provided by the application does not need to use a large amount of reagents for extraction, and is environment-friendly in work.
In one example, in step S10, the volume ratio of the mass of the monazite slag to the mineral acid is 1kg: (0.8-1.5) L. It will be appreciated that the mass to mineral acid volume ratio of the monazite slag may be selected from 1kg: (0.8-1.5) L. Specifically, the volume ratio of the mass of monazite slag to the mineral acid includes, but is not limited to, 1kg:0.8L, 1kg:0.9L, 1kg:1L, 1kg:1.1L, 1kg:1.2L, 1kg:1.3L, 1kg:1.4L or 1kg:1.5L.
It is understood that in step S10, the temperature at which the decomposition reaction is performed may be selected from any value between 110 ℃ and 130 ℃. Specifically, the temperature at which the decomposition reaction is performed includes, but is not limited to, 110 ℃, 111 ℃, 115 ℃, 120 ℃, 125 ℃, or 130 ℃. The mass of the monazite slag and the volume ratio of the inorganic acid are limited, and the decomposition rate of rare earth elements, thorium and uranium in the monazite slag can be fully ensured at the decomposition temperature of 110-130 ℃, so that the concentration of the added inorganic acid can be reduced, and the acid mist phenomenon is avoided. In one example, the decomposition reaction is carried out for a period of 2 hours or more.
In one example, the specific procedure of step S10 is as follows:
mixing monazite slag and inorganic acid, carrying out decomposition reaction at 110-130 ℃, standing and aging for more than or equal to 2 hours, and extracting supernatant fluid to prepare a decomposition mixture;
sulfuric acid is added into the supernatant fluid, and after the mass concentration is regulated to be 60-75%, the mixture is reused for decomposing monazite slag.
The decomposition rate of rare earth elements, thorium and uranium in the decomposition mixture can be improved by controlling the parameters for carrying out the decomposition reaction, but the solubility of the rare earth elements and thorium sulfate is lower, so that most of the rare earth elements and thorium sulfate tend to remain in the decomposition mixture, and after the supernatant is extracted, the supernatant can be reused for decomposing monazite slag after the sulfuric acid is supplemented, so that the method is safe and environment-friendly.
In the process of the decomposition reaction in the step S10, a part of the reaction is as follows:
2RE(OH) 3 +3H 2 SO 4 →RE 2 (SO 4 ) 3 +6H 2 O
2Fe(OH) 3 +3H 2 SO 4 →Fe 2 (SO 4 ) 3 +6H 2 O
Th(OH) 4 +2H 2 SO 4 →Th(SO 4 ) 2 +4H 2 O
Na 2 U 2 O 7 +4H 2 SO 4 →2UO 2 SO 4 +2Na 2 SO 4 +4H 2 O。
in one example, during the mixing process of the water added in the step S20, the mass of the monazite slag and the volume ratio of water in the step S10 are 1000kg: (3-5) m 3 . It will be appreciated that the mass and water volume ratio of the monazite slag in step S10 includes, but is not limited to, 1000kg:3m 3 、1000kg：3.1m 3 、1000kg：3.2m 3 、1000kg：3.5m 3 、1000kg：4m 3 、1000kg：4.5m 3 、1000kg：4.8m 3 Or 1000kg:5m 3 。
In order to improve the solubility of rare earth sulfate and thorium sulfate, in one example, the process parameters of adding water and mixing in step S20 include: the mixing temperature is 50-70 ℃. Specifically, the temperature of the water addition mix includes, but is not limited to, 50 ℃, 55 ℃, 60 ℃, 65 ℃, or 70 ℃. In one example, step S20 mixes the decomposition mixture with water for a mixing time of 5 hours or longer.
In order to reduce the rare earth content in the zirconium-containing first solid, the complete decomposition of the zirconium-containing first solid is ensured. In one example, the process of step S10 is also included for re-performing the zirconium-containing first solid.
In one example, step S20 further includes a step of post-treating the zirconium-containing first solid, which is specifically as follows:
after adding water into the zirconium-containing first solid to wash until the pH value is more than 3, preparing slurry with the solid content of 20-40%, and stirring the slurry from a high-level tank to flow into a mongolian yurt and a shaking table for dressing.
The heavy sand or light mud is obtained by adopting a gravity separation mode such as a shaking table, a mongolian yurt and the like, and comprises the following components:
heavy sand: 25 to 60 percent of zircon, 15 to 30 percent of monazite and xenotime, 4 to 28 percent of mica kaolinite, 0.2 to 2.5 percent of rutile, 1 to 3 percent of quartz, 1 to 2 percent of rutile and 2 to 4 percent of spinel.
(II) light mud filter cake: 20 to 30 percent of regenerated compound (iron, zirconium, silicon, titanic acid and the like), 4.5 to 6.5 percent of regenerated rare earth (mainly tetravalent cerium) compound (cerium/rare earth > 85 percent) and 2 to 3 percent of thorium compound.
Wherein, the heavy sand contains zircon, and zirconium can be recovered.
In one example, in step S30, the basic compound complexing agent includes one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, and ammonium bicarbonate.
In one specific example, in step S30, the alkaline compound complexing agent used is an aqueous solution of sodium carbonate of 90g/L to 120 g/L.
Further, to reduce the content of other metals contained in the uranium containing organic phase. In one example, in step S30, the wash solution includes sulfuric acid at a molar concentration of 0.2mol/L to 0.5 mol/L.
In step S30, after heating the uranium-containing complex solution to a pH of < 6, the complex is thermally decomposed, and the specific reaction is as follows:
UO 2 (CO 3 ) 3 4- +4H + →UO 2 (CO 3 )↓+3H 2 O+2CO 2 ↑。
in one example, in step S30, the extractant includes, in volume percent, 4% to 8% trioctyl tertiary amine, 2% to 4% alcohol, and 88% to 94% solvent oil. According to the application, the extracting agent comprising trioctyl tertiary amine, alcohol and solvent oil is selected, so that uranium can be extracted efficiently, the uranium content in raffinate is less than 0.001g/L, and the recovery rate of uranium can be improved.
In the present application, the type of solvent oil may be exemplified by sulfonated kerosene or No. 260 solvent oil.
In one example, in step S30, the washing solution includes an aqueous sulfuric acid solution having a molar concentration of 0.2mol/L to 0.5 mol/L.
In one example, the method further comprises a step S40 of treating the raffinate:
heating the raffinate to 50-75 ℃, adding a metal compound precipitator until the pH value is 4-5.5, and then carrying out solid-liquid separation to prepare a third filtrate and a third solid containing thorium.
In one example, in step S40, the chemical composition of the metal compound precipitant used includes MgO, mgCO 3 And Mg (OH) 2 One or more of the following. It will be appreciated that in the present application, the type of adding the metal compound precipitant is not limited as long as it contains MgO, mgCO 3 And Mg (OH) 2 The chemical composition of (3) is just required. The substance containing the chemical component may be minerals, industrial magnesium oxide, industrial magnesium carbonate and industrial magnesium hydroxide. The minerals include magnesium carbonate, magnesium oxide and magnesium hydroxide-containing ore powder such as magnesite and brucite.
In one example, step S40 further comprises a step of washing the thorium-containing third solid, in particular as follows:
and washing the thorium-containing third solid by a dilute sulfuric acid solution until the pH value is 3.5-4.5, preparing thorium-containing solid and rare earth-containing filtrate, and combining the rare earth-containing filtrate into the third filtrate for subsequent treatment.
In the application, magnesium compound is adopted to neutralize and precipitate thorium, after solid-liquid separation, the third solid containing thorium is washed by dilute sulfuric acid solution until the pH value is 3.5-4.5, thus the thorium content in the third solid containing thorium can be improved, and the rare earth content of the third solid containing thorium is less than 1%.
In one example, the method further includes a step S50 of treating the third filtrate:
and mixing the third filtrate with seed crystals and an alkaline compound precipitator, and carrying out solid-liquid separation after the pH value is 6.8-7.2 to prepare fourth filtrate and fourth solid containing rare earth.
In one example, the alkaline compound precipitants used in step S50 include one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, and ammonium bicarbonate.
In step S50, the solid-liquid separation is performed by centrifugation, washing and drying.
In one example, in step S50, the seed crystal includes one or more of rare earth carbonate and rare earth oxalate.
The crystal seed and the alkaline compound precipitant are used for coprecipitation of rare earth, so that the precipitated rare earth has good crystal form, and the yield of rare earth can be further improved.
In one example, after step S50, a step of treating the fourth filtrate is further included, specifically as follows:
and (3) enriching the fourth filtrate and the wastewater generated in other processes by a membrane, evaporating, concentrating and recycling the wastewater, and supplying the evaporating waste heat to sulfuric acid slurrying reaction.
The waste water is concentrated and recycled after membrane enrichment, and the evaporating waste heat is supplied to sulfuric acid slurrying reaction, so that slag reduction, recycling and harm reduction can be realized. The process fundamentally solves the problems of 'three wastes' pollution, resource waste, large consumption of raw and auxiliary materials and the like generated in the rare earth smelting process, and realizes the green and efficient of rare earth and co-associated resources.
In the recycling method of monazite slag provided by the application, partial reactions are as follows:
2RE(OH) 3 +3H 2 SO 4 →RE 2 (SO 4 ) 3 +6H 2 O
2Fe(OH) 3 +3H 2 SO 4 →Fe 2 (SO 4 ) 3 +6H 2 O
Th(OH) 4 +2H 2 SO 4 →Th(SO 4 ) 2 +4H 2 O
Na 2 U 2 O 7 +4H 2 SO 4 →2UO 2 SO 4 +2Na 2 SO 4 +4H 2 O
UO 2 2+ +3HCO 3 - →UO 2 (CO 3 ) 3 4- +3H +
Th 4+ +HCO 3 - →Th(CO 3 ) 4 4- +H +
2RE 3+ +3HCO 3 - →RE 2 (CO 3 ) 3 ↓+H +
UO 2 (CO 3 ) 3 4- +4H + →UO 2 (CO 3 )↓+3H 2 O+2CO 2 ↑
Th(CO 3 ) 4 4- +4H + →Th(CO 3 ) 2 ↓+2H 2 O+2CO 2 ↑。
in one specific example, the method for recovering monazite slag comprises the following steps:
s110, mixing monazite slag with sulfuric acid with the mass concentration of 60% -75%, carrying out decomposition reaction at the temperature of 110 ℃ -130 ℃, standing and aging the decomposition solution after the decomposition reaction for more than or equal to 2 hours, and extracting supernatant fluid to prepare a decomposition mixture; adding sulfuric acid into the supernatant, adjusting the mass concentration to 60% -75%, and then reusing the mixture for decomposing monazite slag; wherein, the volume ratio of the mass of the monazite slag to the inorganic acid is 1kg: (0.8-1.5) L.
S120, mixing the decomposition mixture with 1000kg of water: (3-5) m 3 The mixture ratio of the mixture is stirred and mixed for more than or equal to 5 hours at the temperature of 50-70 ℃, after solid-liquid separation, a first solid and a first filtrate are prepared, the first solid is washed with water until the pH value is more than 3, a slurry is prepared, and the slurry flows into a mongolian yurt and a cradle for mineral separation through a high-level tank. And standing and aging the first filtrate for more than or equal to 24 hours, and taking supernatant to extract uranium.
S130, adding an extractant into the supernatant fluid in the step S120 to prepare a uranium-containing organic phase and raffinate; washing the uranium-containing organic phase by sulfuric acid with the concentration of 0.2-0.5 mol/L, and back-extracting by using sodium carbonate solution with the concentration of 90-120 g/L to prepare uranium-containing complex solution; and heating the uranium-containing complex solution, and after the pH is less than 6, carrying out solid-liquid separation to prepare a second filtrate and uranium-containing second solid. After 24 hours of aging of the second filtrate, the uranium concentration in the filtrate is less than 10 mg/l, the second filtrate may be mixed as reuse water with the decomposition mixture in step S120.
S140, heating the raffinate obtained in the step S130 to 50-75 ℃, adding magnesium oxide to pH 4-5.5, and then carrying out solid-liquid separation to prepare a third filtrate and a third solid containing thorium. And washing the thorium-containing third solid by a dilute sulfuric acid solution until the pH value is 3.5-4.5, preparing thorium-containing solid and rare earth-containing filtrate, and combining the rare earth-containing filtrate into the third filtrate for subsequent treatment.
S150, mixing the third filtrate, the seed crystal, sodium bicarbonate and/or ammonium bicarbonate, and carrying out solid-liquid separation after the pH value is 6.8-7.2 to prepare a fourth filtrate and a fourth solid containing rare earth.
S160, other filtrate of the fourth filtrate flows into a storage tank, the wastewater is concentrated and recycled after membrane enrichment, and the evaporation waste heat is supplied to sulfuric acid slurrying reaction.
It is to be understood that the present application is not limited to the apparatus for performing solid-liquid separation, and specifically, the apparatus for performing solid-liquid separation may be exemplified by a filter press, wherein a plate filter press, a chamber filter press, etc. known in the industry may be used. The mixing device in the application can be exemplified by a stirring tank, and the reaction device can be exemplified by a reaction kettle, wherein the stirring tank or the reaction kettle made of PP or PPH materials can be exemplified. In addition, the device for centrifugation is a three-foot high-speed centrifugal stainless steel or corrosion-resistant centrifuge which is familiar to the industry.
The following examples are provided to further illustrate the present application, but the present application is not limited to the following examples. Unless otherwise indicated, all the starting materials used in the examples were commercially available products.
The main chemical components of the monazite excellent slag are shown in table 1.
TABLE 1
| Element name | U 3 O 8 | ThO 2 | REO | Fe | P 2 O 5 |
| Mass ratio% | 0.61 | 15.03 | 7.02 | 2.81 | 0.51 |
| Element name | Cl - | SiO 2 | ZrO 2 | TiO 2 | Al 2 O 3 |
| Mass ratio% | 8.02 | 6.51 | 6.12 | 2.01 | 1.21 |
The main chemical components of the monazite total slag are shown in table 2.
TABLE 2
| Element name | U 3 O 8 | ThO 2 | REO | Fe |
| Mass ratio% | 0.05 | 2.02 | 3.51 | 3.60 |
| Element name | SiO 2 | ZrO 2 | TiO 2 | P 2 O 5 |
| Mass ratio% | 6.51 | 6.03 | 4.01 | 1.21 |
The main chemical components of the monazite slag removal and release are shown in table 3
TABLE 3 Table 3
| Element name | U | Th | RE | Fe | Ba |
| Mass ratio% | 2.43 | 4.73 | 14.11 | 12.61 | 4.47 |
| Element name | Si | Zr | Ti | Al | P |
| Mass ratio% | 5.98 | 3.48 | 6.63 | 1.71 | 1.61 |
Example 1
(1) Adding 4 tons of solitary excellent slag into 20m 3 Adding washing liquid and mineral separation water into a stirring tank, adding 1200L of sulfuric acid (adding sulfuric acid V: excellent slag W=1.2:1) in an amount of 60wt.% per ton of monazite slag, heating to 120 ℃, stirring and decomposing; after stirring for 4 hours, stopping stirring, and clarifying for 2 hours; opening an upper valve, pumping supernatant to prepare a decomposition mixture, supplementing sulfuric acid to the supernatant (reaching 60wt.% sulfuric acid), and returning acid-soluble new solitary Dan You slag;
(2) Adding the decomposition mixture into reuse water, 3.5 m/ton of decomposition mixture 3 Heating to 65deg.C, and stirring for 5 hr; the valve was opened and the slurry containing light mud was pumped into 12m 3 The PPH stirring transfer tank is used for preparing a first solid and a first filtrate through filter pressing by a filter press, the first solid is filled with water to wash a filter cake to pH 4 in the filter press, and discharged into 4m 3 The pulp mixing tank pumps pulp to the overhead tank and sends the pulp to the yurt for mineral separation. And standing and aging the first filtrate for 24 hours, and taking the supernatant to extract uranium.
(3) After the first solid was adjusted to a solids content of 30% by adding water, a slurry was prepared, the slurry was prepared from 6m 3 The PPH overhead tank flows into the yurt for mineral separation by stirring, and heavy sand is selected.
(4) Selecting an extract with an organic phase composition of N235% and 3% of mixed alcohol and 91% of sulfonated kerosene, adopting eight-stage countercurrent extraction to extract first filtrate to obtain a uranium-containing organic phase and raffinate, washing the uranium-containing organic phase with 0.2mol/L sulfuric acid 4-stage, adding 100g/L sodium carbonate to perform 5-stage back extraction to prepare a uranium-containing complex, and heating the uranium-containing complex to an end point pH of 5.5. And (3) carrying out solid-liquid separation to prepare uranium-containing second solid and second filtrate, wherein the uranium recovery rate is 73%. After 24 hours of ageing of the second filtrate, the uranium concentration in the filtrate is less than 10 mg/l, so the second filtrate can be used as reuse water.
(5) Pumping the raffinate from the step (4) into a pump of 20m 3 Glass fiber reinforced plastic stirring tank and heatingTo 65 ℃; slowly adding magnesium oxide to precipitate thorium, neutralizing the precipitate to pH 4 within 3.5 hr, and aging for 2 hr; and (3) filter pressing by a filter press to prepare a third solid containing thorium and a third filtrate, introducing a dilute sulfuric acid solution into the filter press to wash rare earth elements in the third solid containing thorium, and discharging the rare earth elements from the filter press to bagging after washing. The thorium-containing third solid (REO < 1%) is sent to process thorium nitrate or to packaging stock.
(6) Pumping the third filtrate into 12m 3 Adding seed crystal into PPH precipitation stirring tank, slowly adding ammonium bicarbonate to precipitate rare earth, precipitating for 3 hr until pH is 6.8, and aging for 2 hr; pumping into a horizontal centrifuge, washing, spin-drying, preparing a fourth solid containing rare earth and a fourth filtrate, and bagging the fourth solid containing rare earth.
(7) And (3) flowing the fourth filtrate and other filtrates into a storage tank, enriching the wastewater by a membrane, evaporating, concentrating and recycling the wastewater, and supplying the evaporating waste heat to sulfuric acid slurrying reaction.
Example 2
Example 2 is substantially the same as example 1, with the main difference that: in the step (1), sulfuric acid is added to a concentration of 75%, and sulfuric acid V: excellent slag w=0.8: 1, heating to 130 ℃ and stirring for decomposition; stirring is carried out for 4 hours.
Example 3
Example 3 is substantially the same as example 1, the main difference being that: in the step (1), sulfuric acid is added to a concentration of 68%, and sulfuric acid V: excellent slag w=1: 1, heating to 110 ℃ and stirring for decomposition; stirring is carried out for 4 hours.
Example 4
Example 4 is substantially the same as example 1, the main difference being that: in step (2), the decomposition mixture is added to reuse water, 5m per ton of decomposition mixture 3 Heated to 55℃and stirred for 5 hours.
Example 5
Example 5 is substantially the same as example 1, the main difference being that: in the step (4), an extraction liquid with the organic phase composition of N235 percent, mixed alcohol of 5 percent and sulfonated kerosene of 87 percent is selected, eight-stage countercurrent extraction is adopted to extract the first filtrate to obtain a uranium-containing organic phase, and after the uranium-containing organic phase is washed by 0.3mol/L sulfuric acid of 4 stages, 100g/L sodium carbonate of 5 stages is added for back extraction.
Example 6
Example 6 is substantially the same as example 1, the main difference being that: in the step (4), an extraction liquid with the organic phase composition of N235-4%, mixed alcohol of 2% and sulfonated kerosene of 94% is selected, 10-level countercurrent extraction is adopted to extract the first filtrate, a uranium-containing organic phase is obtained, after the uranium-containing organic phase is washed by 0.5mol/L sulfuric acid of 5 level, 120g/L sodium carbonate of 6 level is added for back extraction.
Example 7
Example 7 is substantially the same as example 1, the main difference being that: in step (5), heating the raffinate to 75 ℃; magnesium oxide is slowly added to precipitate thorium, and the precipitate is neutralized to pH 5 within 4 hours and aged for 3 hours.
Example 8
Example 8 is substantially the same as example 1, the main difference being that: in the step (6), seed crystal is added, and after ammonium bicarbonate is slowly added to precipitate rare earth, the rare earth is precipitated for 3.5 hours until the pH value is 7.2, and the rare earth is aged for 2 hours; pumping into a horizontal centrifuge, washing, and spin-drying to prepare a fourth solid containing rare earth and a fourth filtrate.
Example 9
Example 9 is substantially the same as example 1, the main difference being that: the treated monazite slag is full-dissolved slag.
Example 10
Example 10 is substantially the same as example 1, with the main difference that: the treated monazite slag is removed slag.
Example 11
Example 11 is substantially the same as example 1, the main difference being that: the volume percentage of the uranium extraction organic phase is N235 2%, the mixed alcohol is 3% and the sulfonated kerosene is 95%.
Comparative example 1
Comparative example 1 is substantially the same as example 1, with the main difference that: in the step (1), hydrochloric acid is added to a concentration of 60%, and hydrochloric acid V: excellent slag w=0.7: 1.
comparative example 2
Comparative example 2 is substantially the same as example 1, with the main difference that: in the step (1), hydrochloric acid is added to a concentration of 60%, and hydrochloric acid V: excellent slag w=1.5: 1.
comparative example 3
Comparative example 3 is substantially the same as example 1, with the main difference that: in the step (1), the mixture is heated to 90 ℃ and stirred for decomposition.
Comparative example 4
Comparative example 4 is substantially the same as example 1, with the main difference that: in the step (1), the mixture is heated to 140 ℃ and stirred for decomposition.
The process parameters used in the examples and comparative examples, as well as the recovery rates for zirconium, uranium, thorium and rare earth are shown in table 4.
TABLE 4 Table 4
As is clear from table 4, examples 1 to 11 in the present application can improve the recovery rate of rare earth elements and zirconium while ensuring the recovery rate of uranium and thorium, compared with comparative examples 1 to 4. In comparative examples 1 to 4, the recovery rate was affected by selecting different inorganic acids or by decreasing the decomposition reaction temperature, and further decreasing the degree of decomposition of each element.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. It should be understood that, based on the technical solutions provided by the present application, those skilled in the art may obtain technical solutions through logical analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent of the application should therefore be determined with reference to the appended claims, which are to be construed as in accordance with the doctrines of claim interpretation.
Claims (10)
1. The method for recycling the monazite slag is characterized by comprising the following steps of:
mixing monazite slag and inorganic acid, and carrying out decomposition reaction at 110-130 ℃;
adding water for mixing, and preparing a zirconium-containing first solid and a first filtrate after solid-liquid separation; wherein the inorganic acid is a sulfuric acid aqueous solution with the mass concentration of 60-75%;
adding an extractant into the first filtrate to prepare uranium-containing organic phase and raffinate;
washing the uranium-containing organic phase by adopting a washing solution, and then carrying out a complexing reaction by utilizing an alkaline compound complexing agent to prepare a uranium-containing complex solution;
and heating the uranium-containing complex solution, acidifying to a pH value less than 6, and then carrying out solid-liquid separation to prepare a second filtrate and uranium-containing second solid.
2. The method for recycling of solitary stone slag according to claim 1, characterized in that the ratio of mass of solitary stone slag to volume of mineral acid is 1kg: (0.8-1.5) L.
3. The method for recycling monazite slag according to claim 1, wherein the technological parameters of water addition and mixing include: the mixing temperature is 50-70 ℃.
4. The method for recycling monazite slag according to claim 1, wherein in the step of adding water and mixing, the ratio of the mass of the monazite slag to the volume of the water is 1000kg: (3-5) m 3 。
5. The method of claim 1, wherein the alkaline compound complexing agent comprises one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, and ammonium bicarbonate.
6. The method for recycling monazite slag according to claim 1, wherein the extractant comprises, by volume, 4% -8% of trioctyl tertiary amine, 2% -4% of alcohol and 88% -94% of solvent oil.
7. The method for recovering monazite slag according to claim 1, wherein the washing solution comprises an aqueous sulfuric acid solution having a molar concentration of 0.2mol/L to 0.5 mol/L.
8. The method for recycling monazite slag according to any one of claims 1 to 7, further comprising the step of treating the raffinate:
heating the raffinate to 50-75 ℃, adding a metal compound precipitator until the pH value is 4-5.5, and then carrying out solid-liquid separation to prepare a third filtrate and a third solid containing thorium.
9. The method of claim 8, wherein the metal compound precipitant has one or more of the following characteristics:
(1) The chemical components of the metal compound precipitant comprise MgO and MgCO 3 And Mg (OH) 2 One or more of the following;
(2) The metal compound precipitant includes one or more of magnesite and brucite.
10. The method of recycling monazite slag according to claim 8, further comprising the step of treating the third filtrate:
mixing the third filtrate with seed crystals and an alkaline compound precipitator, and after the pH value is 6.8-7.2, carrying out solid-liquid separation to prepare a fourth filtrate and a fourth solid containing rare earth;
wherein the alkaline compound precipitant comprises one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate.
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