CN112960799A - Rare earth soap wastewater purification and reuse method - Google Patents
Rare earth soap wastewater purification and reuse method Download PDFInfo
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- CN112960799A CN112960799A CN202110143902.0A CN202110143902A CN112960799A CN 112960799 A CN112960799 A CN 112960799A CN 202110143902 A CN202110143902 A CN 202110143902A CN 112960799 A CN112960799 A CN 112960799A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 75
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 38
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 38
- 239000000344 soap Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000000746 purification Methods 0.000 title abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 150000002500 ions Chemical class 0.000 claims abstract description 37
- 239000012535 impurity Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 26
- 238000004064 recycling Methods 0.000 claims abstract description 26
- 238000007127 saponification reaction Methods 0.000 claims abstract description 25
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 22
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 22
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 18
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 18
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 18
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002699 waste material Substances 0.000 claims abstract description 16
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 239000008213 purified water Substances 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 238000005507 spraying Methods 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 11
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 238000005188 flotation Methods 0.000 claims description 3
- 239000011575 calcium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910021655 trace metal ion Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
- C01F5/10—Magnesia by thermal decomposition of magnesium compounds by thermal decomposition of magnesium chloride with water vapour
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- 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)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Thermal Sciences (AREA)
- Geology (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses a rare earth soap wastewater purification and reuse method, which comprises the following steps: (1) firstly, performing primary oil removal on the rare earth soap wastewater to obtain oil-removed wastewater and waste oil; (2) adjusting the pH value of the deoiled wastewater, removing metal ions in the wastewater, and treating the wastewater by a filter press to obtain softened water and waste residues; (3) extracting softened water after ammonia saponification, and further removing metal ions to obtain ammonium-containing purified water and saponified organic water; (4) further removing waste oil from the ammonium-containing purified water to obtain wastewater with low metal impurity ions; (5) spraying HC l gas to the wastewater containing low-metal impurity ions through water to obtain ammonium chloride crystals and hydrochloric acid containing low-ammonium low-metal impurity ions; (6) and (3) reacting the crystal ammonium chloride with magnesium oxide to generate ammonia gas and magnesium chloride, absorbing the ammonia gas by the waste water containing low metal impurity ions to prepare ammonia water for recycling, dissociating the magnesium chloride and the water at high temperature to form magnesium oxide and HC l gas, continuously recycling the magnesium oxide, and recycling the HC l gas to the step (5).
Description
Technical Field
The invention belongs to the technical field of rare earth treatment, and relates to a method for purifying and recycling rare earth soap wastewater.
Background
In the rare earth production process, a saponifying agent is usually adopted for extraction, wherein the saponifying agent for rare earth extraction mainly adopts calcium hydroxide and the like, so that saponification wastewater generated in rare earth production is mainly calcium salt mixture with higher concentration, and the calcium salt mixture with higher concentration can cause larger pollution to water, so the saponification wastewater needs to be treated before being discharged, and the common treatment method of the saponification wastewater is difficult to recycle.
Disclosure of Invention
The invention aims to provide a rare earth saponification wastewater purification and recycling method capable of recycling wastewater.
In order to achieve the purpose, the invention adopts the following scheme: a rare earth soap wastewater purification and reuse method comprises the following steps: (1) firstly, carrying out primary oil removal on ammonium-containing organic rare earth soap wastewater to obtain oil-removed wastewater and waste oil; (2) adjusting the pH value of the deoiled wastewater by using an ammonium bicarbonate and ammonia water mixed solution, removing metal ions in the wastewater, and treating the wastewater by using a filter press to obtain softened water and waste residues; (3) extracting softened water after ammonia saponification in a saponification tank containing ammonia water and a P507 extracting agent, and further removing metal ions to obtain purified water containing ammonium and organic saponification; (4) further removing waste oil from the ammonium-containing purified water to obtain wastewater with low metal impurity ions; (5) spraying HCl gas through water in the wastewater with low metal impurity ions, and crystallizing ammonium chloride in high-concentration hydrochloric acid due to acidification and ion-sharing effect to obtain ammonium chloride crystals and hydrochloric acid containing low-ammonium low metal impurity ions; (6) and (3) reacting the crystal ammonium chloride with magnesium oxide to generate ammonia gas and magnesium chloride, absorbing the ammonia gas by the wastewater containing low-metal impurity ions to prepare ammonia water for recycling, dissociating the magnesium chloride and water at high temperature to form magnesium oxide and HCl gas, continuously recycling the magnesium oxide, and recycling the HCl gas to the step (5).
The method for purifying and recycling the rare earth soap wastewater also comprises the step (7) of preparing hydrochloric acid with low ammonium and low metal impurity ions and wastewater with the low metal impurity ions into low-concentration hydrochloric acid as back extraction acid for extracting rare earth.
Performing primary oil removal on the ammonium-containing organic rare earth soap wastewater in the step (1) through an air flotation oil remover; and (4) further removing waste oil after the ammonium-containing purified water is treated by an air floatation oil remover.
And (3) adjusting the pH value of the wastewater after oil removal in the step (2) to 7.5-11 by using a mixed solution of ammonium bicarbonate and ammonia water.
The concentration of the hydrochloric acid with low ammonium and low metal impurity ions is 7-9 mol/l.
By adopting the technical scheme, the PH value of the wastewater after oil removal is adjusted by the mixed solution of ammonium bicarbonate and ammonia water, softened water is extracted after ammonia saponification in a saponification tank containing ammonia water and a P507 extractant, metal ions such as Ca and the like are combined with carbonate to generate precipitation to form waste residues to be discharged out of a system, then the wastewater with low metal impurity ions is sprayed with HCl gas by water, and ammonium chloride is crystallized in high-concentration hydrochloric acid due to the same ion effect of acidification to obtain crystal ammonium chloride; then, enabling the crystal ammonium chloride to react with magnesium oxide to generate ammonia gas and magnesium chloride, enabling the ammonia gas to be absorbed by wastewater containing low-metal impurity ions to prepare ammonia water which can be used as a saponifying agent in a saponification tank containing the ammonia water and a P507 extracting agent for recycling, enabling the magnesium chloride and water to be dissociated at high temperature to form magnesium oxide and HCl gas, enabling the magnesium oxide to be recycled continuously, and recycling the HCl gas to the step (5); thereby reducing the discharge amount of the rare earth wastewater and achieving the recycling of the wastewater.
Detailed Description
In the process of producing rare earth, firstly, the rare earth back-extraction acid reacts with the loaded organic to be converted into rare earth feed liquid, and the rare earth feed liquid is converted into rare earth soap wastewater through saponification organic extraction.
The invention relates to a rare earth soap wastewater purification and reuse method, which comprises the following steps:
(1) firstly, preliminarily removing oil from ammonium-containing organic rare earth soap wastewater by an air flotation oil remover to obtain oil-removed wastewater and waste oil;
(2) adjusting the pH value of the deoiled wastewater by using an ammonium bicarbonate and ammonia water mixed solution, removing most metal ions in the wastewater, and treating by using a filter press to obtain softened water and waste residues;
(3) extracting softened water after ammonia saponification in a saponification tank containing ammonia water and a P507 extraction agent, further removing trace metal ions to obtain purified water containing ammonium and saponified organic components, wherein the saponified organic components are P507 and kerosene;
(4) the ammonium-containing purified water is further removed of waste oil after being treated by an air floatation oil remover, so that waste water with low metal impurity ions is obtained;
(5) spraying HCl gas through water in the wastewater containing low-metal impurity ions, and crystallizing ammonium chloride in high-concentration hydrochloric acid due to acidification and ion-homologous effect to obtain crystalline ammonium chloride and hydrochloric acid containing low-ammonium low-metal impurity ions at a concentration of 7-9mol/l (namely the concentration of the hydrochloric acid containing low-ammonium low-metal impurity ions is 7-9 mol/l); wherein, the content of metal impurity ions Me (Ca, Fe, Al and Zn) in the wastewater containing low metal impurity ions is less than or equal to 1mg/l, the content of ammonium in hydrochloric acid containing low-ammonium low metal impurity ions is 30-100g/l, and the content of metal ions Me (Ca, Fe, Al and Zn) in hydrochloric acid containing low-ammonium low metal impurity ions is less than or equal to 1 mg/l;
(6) reacting the crystal ammonium chloride with magnesium oxide to generate ammonia gas and magnesium chloride, wherein the ammonia gas is absorbed by wastewater containing low-metal impurity ions to prepare ammonia water serving as a saponifying agent in a saponification tank containing the ammonia water and a P507 extracting agent, the magnesium chloride and the water are dissociated at high temperature to form magnesium oxide and HCl gas, the magnesium oxide is continuously recycled, and the HCl gas is recycled to the step (5), wherein the temperature range of the high-temperature dissociation is 280-350 ℃;
(7) the hydrochloric acid with low ammonium and low metal impurity ions of 7-9mol/l and the wastewater with low metal impurity ions are prepared into low-concentration hydrochloric acid which is used as the back extraction acid of rare earth extraction, so as to achieve the technology of water recycling, wherein the concentration of the low-concentration hydrochloric acid is 2-6 mol/l.
Wherein, the back extraction acid of the rare earth extraction is converted into the rare earth soap wastewater through the extraction tank.
In the step (2), when the waste water after oil removal is added with the mixed solution of ammonium bicarbonate and ammonia water to reach the pH value of 7.5-11, 95% -99.9% of metal ions in the waste water after oil removal are removed; when the pH value of the wastewater after oil removal is adjusted to be more than 11 by adding the mixed solution of ammonium bicarbonate and ammonia water, P507 is saponified with softened water to easily form a third phase, phase separation is very difficult, so that the subsequent P507 extraction of rare earth is not normal in operation, and in order to control production, the mixed solution of ammonium bicarbonate and ammonia water is added into the wastewater after oil removal to adjust the pH value to be 7.5-11.
Therefore, the method adjusts the PH value of the wastewater after oil removal through the mixed solution of ammonium bicarbonate and ammonia water, extracts the softened water after ammonia saponification in a saponification tank containing ammonia water and a P507 extracting agent, ensures that metal ions such as Ca and the like are combined with carbonate to generate precipitation to form waste residues to be discharged out of a system, then sprays HCl gas through water on the wastewater with low metal impurity ions, and ammonium chloride is crystallized in high-concentration hydrochloric acid due to acidification and ion effect to obtain crystal ammonium chloride; then, enabling the crystal ammonium chloride to react with magnesium oxide to generate ammonia gas and magnesium chloride, enabling the ammonia gas to be absorbed by wastewater containing low-metal impurity ions to prepare ammonia water which can be used as a saponifying agent in a saponification tank containing the ammonia water and a P507 extracting agent for recycling, enabling the magnesium chloride and water to be dissociated at high temperature to form magnesium oxide and HCl gas, enabling the magnesium oxide to be recycled continuously, and recycling the HCl gas to the step (5); thereby reducing the discharge amount of the rare earth wastewater and achieving the recycling of the wastewater; moreover, the hydrochloric acid with low ammonium and low metal impurity ions and the wastewater with low metal impurity ions can be prepared into low-concentration hydrochloric acid as the back extraction acid of rare earth extraction, so as to achieve the purpose of full recycling of the wastewater.
The invention is illustrated by the following examples.
Precipitates were formed with metal ions at different pH conditions:
the metal ions (Ca, Fe, Al, Zn, etc.) in the waste water are removed by the mixed liquid of ammonium bicarbonate and ammonia water.
Me2++2OH-＝Me(OH)2↓
Me2++CO3 2-＝MeCO3↓
Example one: the pH of the mixed solution was adjusted to 7.5 to change the content of metal ions.
Example two: the pH of the mixed solution is adjusted to 8, and the content of metal ions is changed.
From the above table, it can be seen that: by adjusting the pH of the mixed solution, the pH of the mixed solution can be adjusted
The binding capacity to metal ions differs with P507:
using OH of the first step-And CO3 2-Performing P507 saponification
P507+NH4OH＝P507-NH4+H2O
P507+NH4HCO3＝P507-NH4+H2O+CO2↑
Further removing the high-valence metal ions (the high-valence metal ions are at least divalent) by utilizing a P507 extraction technology (Me is less than or equal to 1 mg/l); utilizing OH in demineralized water-And CO3 2-Saponification of P507 allows the organic energy to extract metal ions, and the ammonium chloride-containing aqueous ammonia solution used for the saponifier does not introduce metal ions.
Me2++P507-NH4＝P507-Me+NH4 +
Example one: the saponification rate of P507 is 5 percent, and the content of the high-valence metal ions is changed.
Example two: the saponification rate of P507 is 8 percent, and the content of the recovered high-valence metal ions is changed.
The technical contents and technical features of the present invention have been disclosed above, and the application of the present invention is not limited to the above, for convenience of description, dysprosium nitrate is taken as an example, and the present invention can be actually applied to products such as rare earth, cobalt nickel, aluminum, etc. Those skilled in the art may make various alterations and modifications based on the disclosure of the present invention without departing from the spirit of the invention. Therefore, the scope of the present invention should not be limited to the embodiments disclosed, but includes various alternatives and modifications without departing from the present invention, which are encompassed by the claims.
Claims (5)
1. The method for purifying and recycling the rare earth soap wastewater is characterized by comprising the following steps of:
(1) firstly, carrying out primary oil removal on ammonium-containing organic rare earth soap wastewater to obtain oil-removed wastewater and waste oil;
(2) adjusting the pH value of the deoiled wastewater by using an ammonium bicarbonate and ammonia water mixed solution, removing metal ions in the wastewater, and treating the wastewater by using a filter press to obtain softened water and waste residues;
(3) extracting softened water after ammonia saponification in a saponification tank containing ammonia water and a P507 extracting agent, and further removing metal ions to obtain purified water containing ammonium and organic saponification;
(4) further removing waste oil from the ammonium-containing purified water to obtain wastewater with low metal impurity ions;
(5) spraying HCl gas through water in the wastewater with low metal impurity ions, and crystallizing ammonium chloride in high-concentration hydrochloric acid due to acidification and ion-sharing effect to obtain ammonium chloride crystals and hydrochloric acid containing low-ammonium low metal impurity ions;
(6) and (3) reacting the crystal ammonium chloride with magnesium oxide to generate ammonia gas and magnesium chloride, absorbing the ammonia gas by the wastewater containing low-metal impurity ions to prepare ammonia water for recycling, dissociating the magnesium chloride and water at high temperature to form magnesium oxide and HCl gas, continuously recycling the magnesium oxide, and recycling the HCl gas to the step (5).
2. The method for purifying and recycling the rare earth soap wastewater as claimed in claim 1, which is characterized in that: and (7) preparing hydrochloric acid with low ammonium content and low metal impurity ions and wastewater with low metal impurity ions into low-concentration hydrochloric acid as stripping acid for rare earth extraction.
3. The method for purifying and recycling the rare earth soap wastewater as claimed in claim 1, which is characterized in that: performing primary oil removal on the ammonium-containing organic rare earth soap wastewater in the step (1) through an air flotation oil remover; and (4) further removing waste oil after the ammonium-containing purified water is treated by an air floatation oil remover.
4. The method for purifying and recycling the rare earth soap wastewater as claimed in claim 1, which is characterized in that: and (3) adjusting the pH value of the wastewater after oil removal in the step (2) to 7.5-11 by using a mixed solution of ammonium bicarbonate and ammonia water.
5. The method for purifying and recycling the rare earth soap wastewater as claimed in any one of claims 1 to 4, wherein: the concentration of the hydrochloric acid with low ammonium and low metal impurity ions is 7-9 mol/l.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606610A (en) * | 2019-08-30 | 2019-12-24 | 河南佰利联新材料有限公司 | Method for circularly treating metal chloride waste liquid by ammonia process |
| CN113754001A (en) * | 2021-09-07 | 2021-12-07 | 福建省长汀金龙稀土有限公司 | Resource recycling method for ammonium chloride wastewater generated by rare earth smelting |
| CN113816445A (en) * | 2021-10-19 | 2021-12-21 | 福建省长汀金龙稀土有限公司 | Method for treating calcium chloride-containing wastewater formed by extraction and separation of rare earth |
| CN113880292A (en) * | 2021-09-14 | 2022-01-04 | 天津市茂联科技有限公司 | Oil removing process for saponified water |
| CN115818868A (en) * | 2022-11-18 | 2023-03-21 | 科立鑫(珠海)新能源有限公司 | Method for deamination of cobalt carbonate production wastewater |
| CN117568631A (en) * | 2023-11-22 | 2024-02-20 | 湖北美辰环保股份有限公司 | Equipment and process for washing and extracting rare earth elements in phosphogypsum |
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| CN101549926A (en) * | 2009-04-29 | 2009-10-07 | 内蒙古包钢稀土高科技股份有限公司 | Rare earth extraction saponification waste-water cyclic utilization method |
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| CN110606610B (en) * | 2019-08-30 | 2022-05-17 | 河南佰利联新材料有限公司 | Method for circularly treating metal chloride waste liquid by ammonia process |
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| CN113816445A (en) * | 2021-10-19 | 2021-12-21 | 福建省长汀金龙稀土有限公司 | Method for treating calcium chloride-containing wastewater formed by extraction and separation of rare earth |
| CN115818868A (en) * | 2022-11-18 | 2023-03-21 | 科立鑫(珠海)新能源有限公司 | Method for deamination of cobalt carbonate production wastewater |
| CN117568631A (en) * | 2023-11-22 | 2024-02-20 | 湖北美辰环保股份有限公司 | Equipment and process for washing and extracting rare earth elements in phosphogypsum |
| CN117568631B (en) * | 2023-11-22 | 2024-04-09 | 湖北美辰环保股份有限公司 | Equipment and process for washing and extracting rare earth elements in phosphogypsum |
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