CN108677024B - Method for recovering rare metals lanthanum cerium and zirconium from smelting slag - Google Patents
Method for recovering rare metals lanthanum cerium and zirconium from smelting slag Download PDFInfo
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 37
- 238000003723 Smelting Methods 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000002893 slag Substances 0.000 title claims description 26
- 150000002739 metals Chemical class 0.000 title claims description 15
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 title description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 47
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 46
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 17
- 238000002386 leaching Methods 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 238000011084 recovery Methods 0.000 abstract description 11
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- -1 platinum group metals Chemical class 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
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- 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
- C22B7/04—Working-up slag
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/14—Obtaining zirconium or hafnium
-
- 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
- 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
- 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
- C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
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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
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Abstract
The invention relates to a secondary smelting slagA process for recovering rare-earth metals lanthanum, cerium and zirconium includes such steps as 1) breaking, acid immersion to obtain the solution of zirconium, lanthanum and cerium containing Al, Fe, Ca and Mg impurities, 3) hydrolysis to remove impurities, adding sodium hydroxide to the solution, and reaction of lanthanum and cerium to L a (OH)3And Ce (OH)3Precipitating, and separating and recovering lanthanum and cerium; 5) and (3) replacement: and adding magnesium metal into the filtrate, and replacing to obtain zirconium metal. The process has the advantages of high metal recovery rate, high recovery rate of the lanthanum and cerium greater than 92%, high recovery rate of the zirconium greater than 95%, simple process, environmental friendliness and easy realization of industrial recovery.
Description
Technical Field
The invention belongs to the technical field of non-ferrous metal recovery, and particularly relates to a method for recovering rare metals of lanthanum, cerium and zirconium from smelting slag.
Background
The rare metal is mainly used for manufacturing special steel, super-hard alloy and high-temperature resistant alloy, and is applied to the aspects of electrical industry, chemical industry, ceramic industry, atomic energy industry, rocket technology and the like. The rare earth metals represented by lanthanum and cerium have extremely important application, are important components of modern high-tech new materials, and a series of compound semiconductors, electronic optical materials, special alloys, novel functional materials, organic metal compounds and the like which are composed of rare earth metals and nonferrous metals all need to use the rare earth metals with unique performance. The dosage is not large, but is vital and cannot be used. Therefore, the material is widely used in modern communication technology, electronic computers, space navigation development, medicine and health, photosensitive materials, photoelectric materials, energy materials, catalyst materials and the like. Zirconium is a kind of vitamin in metallurgical industry because of its corrosion resistance, it can be dissolved in hydrofluoric acid and aqua regia, and can react with non-metal elements and many metal elements at high temperature to produce solid solution compound, so it is widely used in metallurgical industry, and plays a powerful role in deoxidation, denitrogenation and desulfurization. Zirconium has the characteristics of surprising corrosion resistance, extremely high melting point, ultrahigh hardness, strength and the like, is widely used in the fields of aerospace, war industry, nuclear reaction and atomic energy, and is a guarantee for the development of aerospace and nuclear industries in China.
The spent automobile catalyst contains platinum group metals of platinum, palladium and rhodium, and rare metals of lanthanum, cerium and zirconium. Platinum group metals platinum, palladium and rhodium are recovered from the spent automobile catalyst by adopting a plasma smelting method, the platinum group metals are enriched in smelting product molten matte, and rare metals lanthanum, cerium and zirconium are enriched in smelting slag in the smelting process. At present, an effective and rapid method for enriching and recovering rare metals of lanthanum, cerium and zirconium from smelting slag does not exist.
Patent No. CN201410407037.6 "method for efficiently and cleanly recovering platinum group metals from spent automotive catalysts" discloses a method for recovering platinum group metals from spent automotive catalysts, but it does not mention how to recover and treat rare metals of lanthanum, cerium and zirconium.
Disclosure of Invention
The invention provides a method for recovering rare metals of lanthanum, cerium and zirconium from smelting slag. Solves the technical problem of enriching and recovering rare metals of lanthanum, cerium and zirconium from smelting slag.
The specific technical scheme is as follows: a method for recovering rare metals of lanthanum, cerium and zirconium from smelting slag is characterized by comprising the following steps:
1) crushing: the spent automobile catalyst is subjected to 1600 ℃ high-temperature iron capture of smelting slag after plasma smelting, and ZrO in the smelting slag21.8-3.4% of CeO2L a with the content of 1.5-2.9%2O30.3-0.6% of MgO, 8.7-11% of Al2O331-34.6% of SiO229.5-35% of CaO, 15.1-19.8% of CaO, and Fe2O3The content is 0.5-2.0%. Crushing the smelting slag by using a ball mill, wherein the granularity is 75-150 mu m, so that valuable metals of zirconium, lanthanum and cerium in the smelting slag are fully exposed for subsequent leaching;
2) acid leaching: h with the mass percentage concentration of 15-25% is used for the crushed smelting slag2SO4Soaking with 40-60% of HCl, and H2SO4Soaking the mixture and HCl in a volume ratio of 1: 2-1: 6 at a temperature of 45-60 ℃ and a liquid-solid ratio of 4: 1-8: 1 for 3-8 h to obtain a solution of zirconium, lanthanum and cerium containing aluminum, iron, calcium and magnesium impurities;
3) hydrolysis and impurity removal: controlling the pH value of the solution to be 7-11, hydrolyzing aluminum, iron, calcium and magnesium impurities to generate precipitates, and filtering and removing the precipitates to obtain a solution containing zirconium, lanthanum and cerium;
4) adding sodium hydroxide into the solution, adding sodium hydroxide solution into the solution containing zirconium, lanthanum and cerium, and reacting lanthanum and cerium with the solution to generate L a (OH)3And Ce (OH)3Precipitating, and separating and recovering lanthanum and cerium;
5) and (3) replacement: adding magnesium metal into the filtrate, performing displacement to obtain zirconium metal, and filtering after displacement to obtain displacement slag, namely the zirconium metal.
The invention has the beneficial effects that: the method solves the technical problem of enriching and recovering rare metal lanthanum cerium and zirconium from smelting slag, realizes capture and utilization of the rare metal lanthanum cerium and zirconium by steps of acid leaching, hydrolysis impurity removal, sodium hydroxide adjustment and the like after crushing, is clean and pollution-free, has low reaction conditions and technical requirements, can finish the crushing process by adopting a ball mill which is a universal device, can finish the hydrolysis impurity removal and filtering processes by adopting traditional chemical equipment, and is easy to industrialize. The process has the advantages of high metal recovery rate, high recovery rate of metal lanthanum and cerium greater than 92 percent, high metal recovery rate of zirconium greater than 95 percent, simple process and environmental friendliness.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
In order to make the technical problems and technical solutions solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
First, embodiment 1:
1) 200g of smelting slag of the spent automobile catalyst after being subjected to 1600 ℃ high-temperature iron trapping plasma smelting is weighed, and the analytical component is ZrO2The content is 3.1 percent, CeO2The content is 2.9 percent, L a2O30.3% of MgO, 9.1% of Al2O3The content of SiO is 32.6 percent230.5 percent of CaO, 16.8 percent of CaO and Fe2O3The content was 0.6%, as shown in Table 1.
Crushing until the granularity is more than 95% and less than 85 μm, and placing into a round-bottom flask with a constant-temperature electric heating jacket.
2) 800ml of 15% H is added2SO4And 40% HCl leaching, H2SO4The volume ratio of HCl to HCl is 1:4, the leaching temperature is 50 ℃, the liquid-solid ratio is 4:1, and the leaching time is 3 h.
3) Filtering, wherein the filter residue is silicon oxide, and the filtrate contains aluminum, iron, calcium and magnesium impurities, zirconium, lanthanum and cerium. Slowly adding sodium hydroxide solution into the solution, continuously stirring, controlling the pH value of the solution to be 8.7, hydrolyzing aluminum, iron, calcium and magnesium impurities in the solution to generate corresponding hydroxide precipitates, and filtering the solution, wherein the mother solution is the solution containing zirconium, lanthanum and cerium.
4) Then, sodium hydroxide is added into the solution and stirred, lanthanum and cerium react with the solution to form L a (OH)3And Ce (OH)3Precipitating, filtering, drying the filter cake to obtain hydroxide precipitate of lanthanum and cerium, and separating to obtain 0.48 g of lanthanum and 4.36 g of cerium.
5) Then 3 g of magnesium metal was added to the mother liquor obtained after filtration, and 4.25 g of zirconium metal was obtained by substitution, and the recovery rates of lanthanum, cerium and zirconium reached 93.82%, 92.34% and 95.29%, respectively.
Second, example 2:
1) 200g of smelting slag of the spent automobile catalyst after being subjected to 1600 ℃ high-temperature iron trapping plasma smelting is weighed, and the analytical component is ZrO2Content of 2.8% CeO2The content is 2.4 percent, L a2O30.45% of MgO, 9.4% of Al2O3Content of 31.5% SiO228.5% of CaO, 17.8% of CaO, Fe2O3The content was 0.92%, as shown in Table 2.
Crushing until the granularity is more than 98% and less than 80 μm, and placing into a round-bottom flask with a constant-temperature electric heating jacket.
2) 1000ml of a composition of 25% H was added2SO4And 45% HCl leaching, H2SO4The volume ratio of HCl to HCl is 1:2, the leaching temperature is 45 ℃, the liquid-solid ratio is 5:1, and the leaching time is 5 h.
3) Filtering, wherein the filter residue is silicon oxide, and the filtrate contains aluminum, iron, calcium and magnesium impurities, zirconium, lanthanum and cerium. Slowly adding sodium hydroxide solution into the solution, continuously stirring, controlling the pH value of the solution to be 7.8, hydrolyzing aluminum, iron, calcium and magnesium impurities in the solution to generate corresponding hydroxide precipitates, and filtering the solution, wherein the mother solution is the solution containing zirconium, lanthanum and cerium.
4) Then, sodium hydroxide is added into the solution and stirred, lanthanum and cerium react with the solution to form L a (OH)3And Ce (OH)3Precipitating, filtering, drying a filter cake to obtain hydroxide precipitate of lanthanum and cerium, and separating to obtain 0.71 g of lanthanum and 3.65 g of cerium.
5) Then 3.5 g of magnesium metal was added to the mother liquor obtained after filtration, and 3.89 g of zirconium metal was obtained by substitution, and the recovery rates of lanthanum, cerium and zirconium reached 93.42%, 93.41% and 96.45%, respectively.
Third, example 3:
1) 200g of smelting slag of the spent automobile catalyst after being subjected to 1600 ℃ high-temperature iron trapping plasma smelting is weighed, and the analytical component is ZrO2The content is 2.79 percent, CeO2The content is 2.45 percent, L a2O30.5% of MgO, 10.5% of Al2O3Content 33.4% SiO232.5% of CaO, 17.4% of CaO, Fe2O3The content was 0.78%, as shown in Table 3.
Crushing to obtain powder with particle size over 90% smaller than 100 μm, and placing into round-bottom flask with constant-temperature electric heating jacket.
2) 1600ml of a composition of 25% H is added2SO4And 60% HCl leaching, H2SO4The volume ratio of HCl to HCl is 1:6, the leaching temperature is 60 ℃, the liquid-solid ratio is 8:1, and the leaching time is 8 h.
3) Filtering, wherein the filter residue is silicon oxide, and the filtrate contains aluminum, iron, calcium and magnesium impurities, zirconium, lanthanum and cerium. Slowly adding sodium hydroxide solution into the solution, continuously stirring, controlling the pH value of the solution to be 9.5, hydrolyzing aluminum, iron, calcium and magnesium impurities in the solution to generate corresponding hydroxide precipitates, and filtering the solution, wherein the mother solution is the solution containing zirconium, lanthanum and cerium.
4) Then, sodium hydroxide is added into the solution and stirred, lanthanum and cerium react with the solution to form L a (OH)3And Ce (OH)3Precipitating, filtering, drying the filter cake to obtain hydroxide precipitate of lanthanum and cerium, and separating to obtain 0.79 g of lanthanum and 3.71 g of cerium.
5) Then 4 g of magnesium metal was added to the mother liquor obtained after filtration, and 3.83 g of zirconium metal was obtained by substitution, and the recovery rates of lanthanum, cerium and zirconium reached 92.65%, 93.01% and 95.30%, respectively.
The present invention has been described in detail with reference to the specific and preferred embodiments, but it should be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and any modifications, equivalents and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (1)
1. A method for recovering rare metals of lanthanum, cerium and zirconium from smelting slag is characterized in that: the method comprises the following steps:
1) crushing: the spent automobile catalyst is subjected to 1600 ℃ high-temperature iron capture of smelting slag after plasma smelting, and ZrO in the smelting slag21.8-3.4% of CeO2L a with the content of 1.5-2.9%2O30.3-0.6% of MgO, 8.7-11% of Al2O331-34.6% of SiO229.5-35% of CaO, 15.1-19.8% of CaO, and Fe2O3The content of the zirconium, lanthanum and cerium in the smelting slag is 0.5-2.0%, the smelting slag is crushed by a ball mill, the granularity is 75-150 mu m, and the valuable metals zirconium, lanthanum and cerium in the smelting slag are fully exposed for subsequent leaching;
2) acid leaching: h with the mass percentage concentration of 15-25% is used for the crushed smelting slag2SO4Soaking with 40-60% of HCl, and H2SO4Soaking the mixture and HCl in a volume ratio of 1: 2-1: 6 at a temperature of 45-60 ℃ and a liquid-solid ratio of 4: 1-8: 1 for 3-8 h to obtain a solution of zirconium, lanthanum and cerium containing aluminum, iron, calcium and magnesium impurities;
3) hydrolysis and impurity removal: controlling the pH value of the solution to be 7-11, hydrolyzing aluminum, iron, calcium and magnesium impurities to generate precipitates, and filtering and removing the precipitates to obtain a solution containing zirconium, lanthanum and cerium;
4) adding sodium hydroxide into the solution: to a solution containing zirconium, lanthanum and ceriumAdding sodium hydroxide solution, lanthanum and cerium reacting with each other to form L a (OH)3And Ce (OH)3Precipitating, and separating and recovering lanthanum and cerium;
5) and (3) replacement: adding magnesium metal into the filtrate, performing displacement to obtain zirconium metal, and filtering after displacement to obtain displacement slag, namely the zirconium metal with the purity of 93%.
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| CN102453805A (en) * | 2010-10-27 | 2012-05-16 | 中国石油化工股份有限公司 | Method for recovering rare earth element from waste catalytic cracking catalyst containing rare earth element |
| CN105671304A (en) * | 2016-02-25 | 2016-06-15 | 昆明贵金属研究所 | Method for recycling rare earth and platinum group metal from spent automobile emission purification catalyst |
| CN107385214B (en) * | 2017-07-11 | 2019-09-20 | 连云港师范高等专科学校 | A method of segmentation acid hydrolyzation recycles valuable metal from spent FCC catalyst |
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