CN114349212A - Zirconium-hafnium separation alkaline washing residual water recycling and zirconium recycling method - Google Patents
Zirconium-hafnium separation alkaline washing residual water recycling and zirconium recycling method Download PDFInfo
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- 238000005406 washing Methods 0.000 title claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 56
- 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 45
- 238000000926 separation method Methods 0.000 title claims abstract description 33
- INIGCWGJTZDVRY-UHFFFAOYSA-N hafnium zirconium Chemical compound [Zr].[Hf] INIGCWGJTZDVRY-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000004064 recycling Methods 0.000 title claims abstract description 25
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 26
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 13
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims description 56
- 239000003513 alkali Substances 0.000 claims description 47
- 239000012452 mother liquor Substances 0.000 claims description 39
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 32
- 239000012074 organic phase Substances 0.000 claims description 30
- 239000011734 sodium Substances 0.000 claims description 22
- 238000000605 extraction Methods 0.000 claims description 21
- 230000008929 regeneration Effects 0.000 claims description 21
- 238000011069 regeneration method Methods 0.000 claims description 21
- 229910002651 NO3 Inorganic materials 0.000 claims description 18
- 235000010344 sodium nitrate Nutrition 0.000 claims description 16
- 239000004317 sodium nitrate Substances 0.000 claims description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 229910052735 hafnium Inorganic materials 0.000 claims description 12
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 239000003518 caustics Substances 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000003599 detergent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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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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- Extraction Or Liquid Replacement (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of wet-process zirconium hafnium metallurgy, and particularly relates to a method for recycling alkaline washing residual water from zirconium hafnium separation and zirconium recovery. The invention controls the reuse of the alkaline washing residual water, fully utilizes sodium carbonate and sodium bicarbonate which do not participate in the reaction in the alkaline washing residual water, improves the recovery rate of zirconium and greatly reduces the consumption of raw materials.
Description
Technical Field
The invention belongs to the technical field of wet-process zirconium-hafnium metallurgy, and particularly relates to a method for recycling alkaline washing residual water and zirconium in zirconium-hafnium separation.
Background
TBP-HNO3The + X extraction separation process technology is a new zirconium-hafnium wet separation technology at present, and is a key technology for producing nuclear grade zirconium (hafnium) sponge. The technology uses zirconium oxychloride as raw material to prepare extraction stock solution, uses HNO3+ X as medium, tributyl phosphate as extractant, sulfonated kerosene as diluent, sodium carbonate as organic phase regenerant and dilute nitric acid as regenerated organic phase water washing agent. By extracting and separating zirconium and hafnium, the nuclear grade zirconium dioxide and the nuclear grade hafnium dioxide products can be simultaneously prepared.
After alkali washing regeneration is carried out on the zirconium hafnium wet separation organic phase, the alkali washing residual water enters a wastewater treatment process for treatment. The residual alkaline washing water contains zirconium, sodium carbonate, sodium bicarbonate and other impurities, the residual alkaline washing water directly enters the wastewater for neutralization treatment, the wastewater discharge amount is large, wherein the zirconium in the residual alkaline washing water is not recycled, and the sodium carbonate and the sodium bicarbonate are not directly reused.
In view of the above disadvantages in the prior art, there is a need to design a method for recycling zirconium and hafnium separation alkaline washing residual water and zirconium.
Disclosure of Invention
The invention aims to design a method for recycling alkali washing residual water from zirconium-hafnium separation and zirconium recycling, which solves the problem that zirconium, sodium carbonate and sodium bicarbonate contained in alkali washing residual water cannot be reasonably utilized after alkali washing regeneration is carried out on an organic phase from zirconium-hafnium wet separation, realizes reduction of alkali washing agent consumption and improvement of zirconium recovery rate.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a zirconium hafnium separation alkali washing residual water recycling and zirconium recycling method comprises the following steps:
the method comprises the following steps: and (3) carrying out two-stage countercurrent washing regeneration on the organic phase subjected to the back extraction in the zirconium-hafnium separation process by using an alkali washing agent, carrying out water washing and acidification treatment on the generated regenerated organic phase, and carrying out treatment in the second step on the generated alkali washing residual water.
Step two: adding alkali into the alkali washing residual water for precipitation, controlling the precipitation temperature and PH, filtering the precipitation mother liquor, recovering zirconium from a filter cake through acid dissolution, and performing precipitation and pretreatment on the filtered precipitation mother liquor for the third treatment.
Step three: and (3) carrying out two-stage countercurrent washing regeneration on the precipitation mother liquor obtained after the organic phase is subjected to the back extraction in the zirconium-hafnium separation process and is treated in the second step, carrying out water washing and acidification treatment on the generated regenerated organic phase, and carrying out treatment in the second step on the generated alkaline washing residual water.
Step four: and D, analyzing and judging the precipitation mother liquor obtained in the step two until the nitrate radical in the precipitation mother liquor reaches 450g/L, and performing treatment in the step five.
Step five: adding acid into the mother liquid after the alkali residual water is precipitated for neutralization, and removing sodium nitrate and recovering the sodium nitrate in the sodium nitrate recovery process.
In the process method, in the organic phase after back extraction in the zirconium hafnium wet process in the step one, the volume ratio of sulfonated kerosene is 40%, the volume ratio of tributyl phosphate is 60%, the concentration of nitric acid in the organic phase after back extraction is 0.5-0.7 mol/L, p (Zr) is 0.4-0.7 g/L, and c (Na) in an alkaline detergent2CO3) 100-127 g/L, 1.2-2.1 g/L of p (Zr) in alkaline washing residual water, and c (Na)2CO3)＝10～18g/L,c(NaHCO3)＝50～75g/L。
In the process method of the invention, in the alkaline washing residual water and alkaline precipitation in the step two, the mass fraction of the liquid caustic soda is 32%, the precipitation temperature is 45-55 ℃, the precipitation end point PH is 12, and p (Zr) in the precipitation mother liquor is 0.0001-0.001 g/L, c (Na)2CO3)＝90～108g/L，c(NO3 -)＝120-485g/L。
In the process of the present invention, in the precipitation mother liquor in the third step, p (zr) ═ 0.0001 to 0.001g/L, c (naoh) ═ 0.1 to 10g/L, and c (Na) are present2CO3)＝90～108g/L，c(NO3 -) 120-450g/L, the number of stages of regeneration of countercurrent washing is 2, and the flow ratio is 3:1.
In the process method, the precipitation mother liquor in the step four is filtrate obtained by adding alkali into alkaline washing residual water, precipitating and filtering, the concentration of nitrate radicals is continuously increased accumulatively in the process of recycling the alkaline washing residual water, and when the washing regeneration temperature is controlled to be 25-35 ℃, the concentration of the nitrate radicals is controlled to be less than or equal to 450g/L, so that the effect of the precipitation of sodium nitrate on the alkaline washing regeneration effect of an organic phase is prevented from being influenced.
In the process method, the concentration of nitrate radical in the precipitation mother liquor in the fifth step is 475 g/L-570 g/L, and the pH value of the precipitation mother liquor is 6.8-7.2 after the precipitation mother liquor is neutralized by nitric acid.
The beneficial effects obtained by the invention are as follows:
the method takes alkaline washing residual water after organic phase alkaline washing regeneration in the wet separation process of zirconium and hafnium as a raw material, recovers zirconium in the form of precipitate by adding alkali for precipitation, recycles the precipitation mother liquor as an alkaline washing agent by controlling the amount of the added alkali, neutralizes sodium carbonate and sodium bicarbonate in the precipitation mother liquor by adding acid by controlling the concentration of nitrate radical in the precipitation mother liquor, and recovers sodium nitrate byproduct. The invention reduces the consumption of the alkaline detergent and improves the recovery rate of zirconium.
Drawings
FIG. 1 is a schematic flow chart of a method for recycling alkaline washing residual water and zirconium in zirconium-hafnium separation.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
As shown in figure 1, the invention provides a method for recycling zirconium and hafnium separation alkaline washing residual water and zirconium, which comprises the following steps:
the method comprises the following steps: and (3) carrying out two-stage countercurrent washing regeneration on the organic phase subjected to the back extraction in the zirconium-hafnium separation process by using an alkali washing agent, carrying out water washing and acidification treatment on the generated regenerated organic phase, and carrying out treatment in the second step on the generated alkali washing residual water.
Step two: adding alkali into the alkali washing residual water for precipitation, controlling the precipitation temperature and PH, filtering the precipitation mother liquor, recovering zirconium from a filter cake through acid dissolution, and performing precipitation and pretreatment on the filtered precipitation mother liquor for the third treatment.
Step three: and (3) carrying out two-stage countercurrent washing regeneration on the precipitation mother liquor obtained after the organic phase is subjected to the back extraction in the zirconium-hafnium separation process and is treated in the second step, carrying out water washing and acidification treatment on the generated regenerated organic phase, and carrying out treatment in the second step on the generated alkaline washing residual water.
Step four: and D, analyzing and judging the precipitation mother liquor obtained in the step two until the nitrate radical in the precipitation mother liquor reaches 450g/L, and performing treatment in the step five.
Step five: adding acid into the mother liquid after the alkali residual water is precipitated for neutralization, and removing sodium nitrate and recovering the sodium nitrate in the sodium nitrate recovery process.
In the process method, in the organic phase after back extraction in the zirconium hafnium wet process in the step one, the volume ratio of sulfonated kerosene is 40%, the volume ratio of tributyl phosphate is 60%, the concentration of nitric acid in the organic phase after back extraction is 0.5-0.7 mol/L, p (Zr) is 0.4-0.7 g/L, and c (Na) in an alkaline detergent2CO3) 100-127 g/L, 1.2-2.1 g/L of p (Zr) in alkaline washing residual water, and c (Na)2CO3)＝10～18g/L,c(NaHCO3)＝50～75g/L。
In the process method of the invention, in the alkaline washing residual water and alkaline precipitation in the step two, the mass fraction of the liquid caustic soda is 32%, the precipitation temperature is 45-55 ℃, the precipitation end point PH is 12, and p (Zr) in the precipitation mother liquor is 0.0001-0.001 g/L, c (Na)2CO3)＝90～108g/L，c(NO3 -)＝120-485g/L。
In the process of the present invention, in the precipitation mother liquor in the third step, p (zr) ═ 0.0001 to 0.001g/L, c (naoh) ═ 0.1 to 10g/L, and c (Na) are present2CO3)＝90～108g/L，c(NO3 -) 120-450g/L, the number of stages of regeneration of countercurrent washing is 2, and the flow ratio is 3:1.
In the process method, the precipitation mother liquor in the step four is filtrate obtained by adding alkali into alkaline washing residual water, precipitating and filtering, the concentration of nitrate radicals is continuously increased accumulatively in the process of recycling the alkaline washing residual water, and when the washing regeneration temperature is controlled to be 25-35 ℃, the concentration of the nitrate radicals is controlled to be less than or equal to 450g/L, so that the effect of the precipitation of sodium nitrate on the alkaline washing regeneration effect of an organic phase is prevented from being influenced.
In the process method, the concentration of nitrate radical in the precipitation mother liquor in the fifth step is 475 g/L-570 g/L, and the pH value of the precipitation mother liquor is 6.8-7.2 after the precipitation mother liquor is neutralized by nitric acid.
Example 1
Taking 20L of No. 1 alkaline washing residual water in a zirconium hafnium separation production site, removing oil and filtering, wherein p (Zr) in the alkaline washing residual water is 1.755g/L, and c (Na)2CO3)＝17.60g/L,c(NaHCO3)＝67.32g/L。
Adding the residual water after the 1# alkaline washing into a stirring tank, stirring and heating to 50 ℃, gradually adding 32% of liquid caustic soda until the pH value is 12, continuing heating and stirring, and aging for 30 min.
Filtering the precipitate, recovering zirconium from the residue, wherein the filtrate is 19.8L, and p (Zr) is 0.0004g/L, c (Na)2CO3)＝93.3/L，c(NO3 -)＝126.5g/L。
Taking 60L of organic phase after back extraction in the zirconium hafnium separation production field, and obtaining C (HNO) in the reverse extraction3) 0.71, p (zr) 0.59g/L, 2-stage counter-current caustic wash regeneration in a small mixer-settler, flow ratio: o/a is 3/1 (O/a),
collecting 2# alkali residual water, wherein p (Zr) in 2# alkali residual water is 1.556g/L, c (Na)2CO3)＝15.28g/L,c(NaHCO3)＝68.44g/L，c(NO3 -)＝258.4g/L。
Adding the residual water after the 2# alkali washing into a stirring tank, stirring and heating to 50 ℃, gradually adding 32% liquid alkali until the pH value is 12, continuing heating and stirring, and aging for 30 min.
Filtering the precipitate, recovering zirconium from the residue, wherein the filtrate is 19.7L, and p (Zr) is 0.0003g/L, c (Na)2CO3)＝90.5/L，c(NO3 -)＝264.47g/L。
Taking 59L of organic phase after back extraction in the zirconium hafnium separation production field, and obtaining C (HNO) in the reverse extraction3) 0.71, p (zr) 0.59g/L, 2-stage counter-current caustic wash regeneration in a small mixer-settler, flow ratio: o/a is 3/1 (O/a),
collecting 3# alkali residual water, wherein p (Zr) is 1.687g/L, c (Na) in 3# alkali residual water2CO3)＝13.88g/L,c(NaHCO3)＝76.84g/L，c(NO3 -)＝368.13g/L。
Adding the residual water after the 3# alkali washing into a stirring tank, stirring and heating to 50 ℃, gradually adding 32% liquid alkali until the pH value is 12, continuing heating and stirring, and aging for 30 min.
The precipitate was filtered, and the residue was subjected to zirconium recovery, to give 19.6L filtrate, in which p (zr) was 0.0005g/L, c (Na)2CO3)＝87.54/L，c(NO3 -)＝376.12g/L。
Taking 59L of organic phase after back extraction in the zirconium hafnium separation production field, and obtaining C (HNO) in the reverse extraction3) 0.71, p (zr) 0.59g/L, 2-stage counter-current caustic wash regeneration in a small mixer-settler, flow ratio: o/a is 3/1 (O/a),
collecting residual water of No. 4 alkali, wherein p (Zr) in residual water of No. 4 alkali washing is 1.667g/L, c (Na)2CO3)＝11.21g/L,c(NaHCO3)＝56.98g/L，c(NO3 -)＝459.15g/L。
Adding the residual water into a stirring tank, stirring and heating to 50 deg.C, gradually adding 32% liquid alkali until pH is 12, heating and stirring, and aging for 30 min.
The precipitate was filtered, and the residue was subjected to zirconium recovery, to give 19.5L filtrate, in which p (Zr) was 0.0005g/L, c (Na)2CO3)＝79.3/L，c(NO3 -)＝462.12g/L。
The filtrate is neutralized by the residual water after washing, and then the sodium nitrate is recovered in the sodium nitrate recovery process.
Example 2
The reverse thickness of the product is 9m when taking zirconium hafnium to separate the production field3And 0.58mol/L of the organic phase in the reaction, wherein p (Zr) is 0.66g/L, and the organic phase after the back extraction is subjected to two-stage alkali washing regeneration by using a zirconium-hafnium separating and mixing clarifier produced in a pilot plant, wherein the flow ratio is as follows: O/A3/1, alkali wash c (Na)2CO3) 112.1g/L, 1.98g/L of p (Zr) in the alkaline washing residual water, and c (Na)2CO3)＝16.5/L,c(NaHCO3)＝63.5g/L.
Adding the residual water into a stirring tank, stirring and heating to 50 deg.C, gradually adding 32% liquid alkali until pH is 12, heating and stirring, and aging for 30 min.
And filtering the precipitated material, recovering zirconium from filter residues, returning the precipitated mother liquor to be used as an alkaline detergent, and returning the precipitated mother liquor three times, wherein nitrate radical in alkaline washing residual water is 472 g/L.
Adding the precipitated mother liquor into nitric acid for neutralization, and recovering sodium nitrate in a sodium nitrate removing and recovering process.
Claims (9)
1. A zirconium hafnium separation alkali washing residual water recycling and zirconium recycling method is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: carrying out two-stage countercurrent washing regeneration on the organic phase subjected to the back extraction in the zirconium hafnium separation process by using an alkali washing agent, carrying out water washing and acidification treatment on the generated regenerated organic phase, and carrying out treatment in the second step on the generated alkali washing residual water;
step two: adding alkali into the alkali washing residual water for precipitation, controlling the precipitation temperature and PH, filtering the precipitation mother liquor, recovering zirconium from a filter cake through acid dissolution, and performing precipitation and pretreatment on the filtered precipitation mother liquor for the third treatment;
step three: carrying out two-stage countercurrent washing regeneration on the precipitation mother liquor obtained after the organic phase is subjected to the back extraction in the zirconium-hafnium separation process and is treated in the second step, carrying out water washing and acidification treatment on the generated regenerated organic phase, and carrying out the second step treatment on the generated alkaline washing residual water;
step four: analyzing and judging the precipitation mother liquor obtained in the second step until the nitrate radical in the precipitation mother liquor reaches 450g/L, and performing treatment in the fifth step;
step five: adding acid into the mother liquid after the alkali residual water is precipitated for neutralization, and removing sodium nitrate and recovering the sodium nitrate in the sodium nitrate recovery process.
2. The method for recycling zirconium and hafnium separation alkaline washing residual water and zirconium according to claim 1, wherein the method comprises the following steps: in the organic phase obtained after back extraction in the zirconium hafnium wet process in the first step, the volume percentage of the sulfonated kerosene is 40%, and the volume percentage of the tributyl phosphate is 60%.
3. The method for recycling zirconium and hafnium separation alkaline washing residual water and zirconium according to claim 2, characterized in that: the concentration of nitric acid in the organic phase after back extraction in the first step is 0.5-0.7 mol/L, p (Zr) is 0.4-0.7 g/L, and c (Na) is contained in alkali wash2CO3) 100-127 g/L, 1.2-2.1 g/L of p (Zr) in alkaline washing residual water, and c (Na)2CO3)＝10～18g/L,c(NaHCO3)＝50～75g/L。
4. The method for recycling zirconium and hafnium separation alkaline washing residual water and zirconium according to claim 3, wherein the method comprises the following steps: and in the alkali washing residual water and alkali precipitation in the second step, the mass fraction of the liquid alkali is 32%.
5. The method for recycling zirconium and hafnium separation alkaline washing residual water and zirconium according to claim 4, wherein the method comprises the following steps: in the second step, the precipitation temperature is 45-55 ℃, the pH of the precipitation end point is 12, and p (Zr) in the precipitation mother liquor is 0.0001-0.001 g/L, c (Na)2CO3)＝90～108g/L，c(NO3 -)＝120-485g/L。
6. The method for recycling zirconium and hafnium separation alkaline washing residual water and zirconium according to claim 5, wherein the method comprises the following steps: in the third step, p (Zr) 0.0001-0.001 g/L, c (NaOH) 0.1-10 g/L, and c (Na) are contained in the mother liquor2CO3)＝90～108g/L，c(NO3 -)＝120-450g/L。
7. The method for recycling zirconium and hafnium separation alkaline washing residual water and zirconium according to claim 6, wherein the method comprises the following steps: in the third step, the number of the countercurrent washing regeneration stages is 2, and the flow ratio is 3:1.
8. The method for recycling zirconium and hafnium separation caustic washing residual water and zirconium according to claim 7, wherein the method comprises the following steps: and the precipitation mother liquor in the fourth step is a filtrate obtained by adding alkali into alkali washing residual water, precipitating and filtering, the washing regeneration temperature is controlled to be 25-35 ℃, and the nitrate concentration is controlled to be less than or equal to 450 g/L.
9. The method for recycling zirconium and hafnium separation alkaline washing residual water and zirconium according to claim 1 or 8, characterized in that: and fifthly, the concentration of nitrate radical in the precipitation mother liquor is 475 g/L-570 g/L, and the PH of the precipitation mother liquor is 6.8-7.2 after the precipitation mother liquor is neutralized by nitric acid.
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| CN115504901A (en) * | 2022-09-22 | 2022-12-23 | 厦门稀土材料研究所 | [A336] Method for preparing nuclear-grade zirconium and nuclear-grade hafnium by extraction and separation of [DGA]-type ionic liquid in an acidic system |
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