CN111874936A - Preparation method of raw material for preparing nano rare earth oxide - Google Patents
Preparation method of raw material for preparing nano rare earth oxide Download PDFInfo
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- 239000002994 raw material Substances 0.000 title claims abstract description 44
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 85
- 238000000605 extraction Methods 0.000 claims abstract description 79
- 238000005406 washing Methods 0.000 claims abstract description 75
- 239000000460 chlorine Substances 0.000 claims abstract description 70
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 70
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000005352 clarification Methods 0.000 claims abstract description 55
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 20
- 229910002651 NO3 Inorganic materials 0.000 claims description 18
- 239000005416 organic matter Substances 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000012267 brine Substances 0.000 claims description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 19
- 239000012071 phase Substances 0.000 description 19
- 229910052692 Dysprosium Inorganic materials 0.000 description 15
- 229910052727 yttrium Inorganic materials 0.000 description 15
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 14
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- -1 rare earth chloride Chemical class 0.000 description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 238000004064 recycling Methods 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000003916 acid precipitation Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910003440 dysprosium oxide Inorganic materials 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- 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
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
- C01F17/17—Preparation or treatment, e.g. separation or purification involving a liquid-liquid extraction
-
- 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
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/218—Yttrium oxides or hydroxides
-
- 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
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a preparation method of a raw material for preparing a nano rare earth oxide, which comprises the following steps: (1) washing stage 1-loading rare earth organic dechlorination: the method comprises the following steps that (1) high-chlorine loaded rare earth organic enters a 1 st stage of a washing 1-stage mixed extraction tank, meanwhile, salt-free water is added into the last 1 st stage of the washing 1-stage mixed extraction tank, and chlorine in the high-chlorine loaded rare earth organic enters the salt-free water; (2) clarification 1 stage-reduction of organic entrainment: the loaded rare earth organic washed by the brine-free washing in the step (1) enters a clarification 1 stage, and the loaded rare earth organic treated by the clarification 1 stage forms low-chlorine loaded rare earth organic; (3) stripping section-qualified raw material output: and (3) feeding the low-chlorine loaded rare earth organic clarified in the step (2) into the 1 st stage of a stripping section, simultaneously adding nitric acid into the last 1 st stage of the stripping section, and stripping the rare earth in the low-chlorine loaded rare earth organic into a water phase in a countercurrent stripping manner to finally produce the raw material for preparing the nano rare earth oxide.
Description
Technical Field
The invention belongs to the technical field of rare earth materials, relates to a preparation method of a raw material for preparing a nano rare earth oxide, and particularly relates to a preparation method of a rare earth oxide.
Background
In recent years, with the development of nanotechnology, nanoscale rare earth oxide materials have been widely used in the fields of ultraviolet absorption, precision polishing, high-efficiency catalysis, electronic ceramics, optical fiber materials, luminescent materials, wave-absorbing materials and the like. The nano-grade rare earth oxide material has strict requirements on impurity control, for example, the chlorine content is high, powder defects can be caused, and the service life and the performance of a product are finally influenced.
In order to control the chlorine content in the product, the industry generally adopts hydrochloric acid to strip high-chlorine loaded rare earth organic to obtain a rare earth chloride feed liquid, then converts the rare earth chloride feed liquid into a rare earth nitrate feed liquid by the modes of oxalic acid precipitation, high-temperature ignition and nitric acid dissolution, wherein the rare earth nitrate feed liquid is a raw material for preparing nano-scale rare earth oxide, and the chlorine in the feed liquid is removed in the process of converting the rare earth chloride feed liquid into the rare earth nitrate feed liquid, so that the chlorine content of the nano-scale rare earth oxide of the final product can be ensured to be qualified.
However, the preparation process of the raw materials for preparing the nano-scale rare earth oxide has the defects of long flow, high energy consumption and high auxiliary material cost.
Disclosure of Invention
The invention aims to provide a method for preparing a raw material for preparing a nano rare earth oxide, which has the characteristics of short flow, low energy consumption and low auxiliary material cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of raw materials for preparing nano rare earth oxide comprises the following steps:
(1) washing stage 1-loading rare earth organic dechlorination: leading high-chlorine loaded rare earth organic from a conventional extraction separation rare earth production line, and enabling the high-chlorine loaded rare earth organic to enter the 1 st stage of a washing 1-stage mixed extraction tank, wherein the washing 1-stage mixed extraction tank has multiple stages, and simultaneously adding non-saline water into the last 1 stage of the washing 1-stage mixed extraction tank, and enabling the high-chlorine loaded rare earth organic to enter the non-saline water in the process of flowing from the 1 st stage of the washing 1-stage mixed extraction tank to the last 1 stage of the washing 1-stage mixed extraction tank in a counter-current washing mode;
(2) clarification 1 stage-reduction of organic entrainment: the loaded rare earth organic washed without the brine in the step (1) enters a clarification 1 stage, and after multi-stage clarification, water phase carried in the loaded rare earth organic is separated from the loaded rare earth organic, so that the loaded rare earth organic treated by the clarification 1 stage forms low-chlorine loaded rare earth organic with the water phase carrying amount of less than 0.005%;
(3) stripping section-qualified raw material output: and (3) feeding the low-chlorine loaded rare earth organic clarified in the step (2) into a 1 st stage of a back-extraction section, wherein the back-extraction section has multiple stages, adding nitric acid into the last 1 st stage of the back-extraction section, back-extracting the rare earth in the low-chlorine loaded rare earth organic into a water phase in a counter-current back-extraction mode, and finally outputting the raw material for preparing the nano rare earth oxide.
A preparation method of raw materials for preparing nanometer rare earth oxide further comprises the following steps (4) washing 2 stages to reduce the content of blank organic nitrate radical: and (4) feeding the separated blank organic matters after the nitric acid back extraction in the step (3) into the 1 st stage of the washing 2-stage mixed extraction tank, wherein the washing 2-stage mixed extraction tank has multiple stages, simultaneously adding the non-saline water into the last 1 stage of the washing 2 stage, and feeding the nitric acid carried in the blank organic matters into the non-saline water in a countercurrent washing mode.
A preparation method of raw materials for preparing nano rare earth oxide further comprises the step (5) of clarifying 2 stages-further reducing the content of blank organic nitrate radical: and (4) allowing the blank organic washed in the step (4) to enter a clarification 2 stage, and after multi-stage clarification, separating a water phase carried in the blank organic from the blank organic to ensure that the water phase carrying amount in the blank organic treated in the clarification 2 stage is less than 0.005%.
Further, the conventional extraction separation rare earth production line reversely extracts the high-chlorine rare earth-loaded organic matter by using hydrochloric acid.
Further, the high-chlorine-containing washed salt-free water generated after the treatment in the step (1) is returned to a conventional rare earth extraction and separation production line.
The volume of the brine-free water in the step (1) and the step (4) is equal to 1-20% of the volume of the high-chlorine rare earth loaded organic.
The mixed extraction tank of the washing section 1 in the step (1) and the mixed extraction tank of the washing section 2 in the step (4) are 3-15 grades.
In the step (3), the volume of the nitric acid is equal to 2-15% of the volume of the high-chlorine rare earth loaded organic matter.
The clarification in the step (2) and the clarification in the step (5) are both 3-5 grades.
Further, the blank organic matter after the clarification 2-stage treatment of the step (5) is returned to a conventional extraction separation rare earth production line.
By adopting the technical scheme, the qualified raw material for preparing the nano rare earth oxide is obtained by carrying out washing 1 section, clarification 1 section and back extraction section treatment on the high-chlorine loaded rare earth organic, so that the chlorine content is reduced, and the chlorine content is measured by experiments: the chlorine content can be reduced from 0.5g/L to 5-50mg/L through the washing 1-stage treatment; the chlorine content can be reduced from 5-50mg/L to less than 5mg/L through clarification 1-stage treatment; compared with the existing preparation process of the raw material for preparing the nano-scale rare earth oxide, the preparation method has the advantages that the flow is shortened, oxalic acid precipitation and high-temperature firing in the existing preparation process of the raw material for preparing the nano-scale rare earth oxide are not needed, and the overall process is simple, the energy consumption is low, and the auxiliary material cost is low.
Detailed Description
The invention discloses a preparation method of a raw material for preparing a nano rare earth oxide, which comprises the following steps:
(1) washing stage 1-loading rare earth organic dechlorination: leading high-chlorine loaded rare earth organic from a conventional extraction separation rare earth production line, and enabling the high-chlorine loaded rare earth organic to enter the 1 st stage of a washing 1-stage mixed extraction tank, wherein the washing 1-stage mixed extraction tank has multiple stages, and simultaneously adding non-saline water into the last 1 stage of the washing 1-stage mixed extraction tank, and enabling the high-chlorine loaded rare earth organic to enter the non-saline water in the process of flowing from the 1 st stage of the washing 1-stage mixed extraction tank to the last 1 stage of the washing 1-stage mixed extraction tank in a counter-current washing mode;
(2) clarification 1 stage-reduction of organic entrainment: the loaded rare earth organic washed without the brine in the step (1) enters a clarification stage 1, and after multi-stage clarification, water phase carried in the loaded rare earth organic is separated from the loaded rare earth organic, so that the loaded rare earth organic treated by the clarification stage 1 forms low-chlorine loaded rare earth organic with the water phase carrying amount of less than 0.005%, and chlorine stability of the nano rare earth oxide of the final product is ensured; because of the clarification time problem of the washing stage 1, the loaded rare earth organic is carried with about 0.3 percent of water phase, and the water phase contains the high-chlorine loaded rare earth organic, namely the water phase contains chloride ions remained after washing, which leads to the over-standard chlorine of the product, so the invention is provided with a step (2);
(3) stripping section-qualified raw material output: and (3) the low-chlorine loaded rare earth organic clarified in the step (2) enters the 1 st stage of a back-extraction section, the back-extraction section has multiple stages, nitric acid is added into the last 1 stage of the back-extraction section, the rare earth in the low-chlorine loaded rare earth organic is back-extracted into a water phase in a counter-current back-extraction mode, and finally, a raw material for preparing the nano rare earth oxide, namely the low-chlorine rare earth nitrate feed liquid is produced.
Further, the preparation method of the raw material for preparing the nano rare earth oxide, disclosed by the invention, further comprises the following steps of (4) washing 2 stages, namely reducing the content of blank organic nitrate radicals: and (4) feeding the blank organic separated after the nitric acid back extraction in the step (3) into the 1 st stage of the washing 2-stage mixed extraction tank, wherein the washing 2-stage mixed extraction tank has multiple stages, and simultaneously adding the non-saline water into the last 1 stage of the washing 2 stage to feed the nitric acid carried in the blank organic into the non-saline water in a countercurrent washing mode, so that the content of the washed blank organic nitrate is reduced.
Further, the preparation method of the raw material for preparing the nano rare earth oxide, disclosed by the invention, also comprises the step (5) of clarifying 2 stages, namely, further reducing the content of blank organic nitrate radicals: and (3) allowing the blank organic washed in the step (4) to enter a clarification 2 stage, and after multi-stage clarification, separating water phase carried in the blank organic from the blank organic, so that the water phase carrying amount in the blank organic treated in the clarification 2 stage is less than 0.005%, thereby ensuring the purity of the circulating organic, wherein if the blank organic is not subjected to the clarification 2 stage, the blank organic returns to a conventional extraction separation rare earth production line, the ammonia nitrogen content of the conventional extraction production system exceeds the standard, and the national environmental protection wastewater discharge standard cannot be met, so the method is provided with a step (5).
Further, the conventional extraction separation rare earth production line reversely extracts the high-chlorine rare earth-loaded organic matter by using hydrochloric acid.
And (3) further, returning the high-chlorine-content washed brine without salt generated after the treatment in the step (1) to a conventional rare earth extraction and separation production line for recycling.
And (3) further, the washed salt-free water containing nitric acid treated in the step (4) enters a stripping section of the step (3) for recycling.
Further, the chlorine concentration in the conventional extraction separation rare earth production line is adjusted to an initial value.
And (3) further, the blank organic matter treated by the clarification 2 stages in the step (5) returns to a conventional rare earth extraction and separation production line, so that the aim of recycling is fulfilled.
Preferably, the volume of the brine-free water in the step (1) and the step (4) is equal to 1-20% of the volume of the high-chlorine rare earth-loaded organic.
Preferably, the volume of nitric acid in step (3) is equal to 2% -15% of the volume of the high-chlorine rare earth-loaded organic.
Preferably, the concentration of the nitric acid is 5.0 mol/L.
Preferably, the clarification in step (2) and the clarification in step (5) are both in 3-5 grades.
Preferably, the mixed extraction tank of the washing 1 section in the step (1) and the mixed extraction tank of the washing 2 section in the step (4) are 3-15 grades.
Preferably, the stripping section is 8-10 grades.
In conclusion, the qualified raw material for preparing the nano rare earth oxide is obtained by carrying out washing 1 section, clarification 1 section and back extraction section treatment on the high-chlorine loaded rare earth organic, so that the chlorine content is reduced, and the chlorine content is measured by experiments: the chlorine content can be reduced from 0.5g/L to 5-50mg/L through the washing 1-stage treatment; the chlorine content can be reduced from 5-50mg/L to less than 5mg/L through clarification 1-stage treatment; compared with the existing preparation process of the raw material for preparing the nano-scale rare earth oxide, the preparation method has the advantages that the flow is shortened, oxalic acid precipitation and high-temperature firing in the existing preparation process of the raw material for preparing the nano-scale rare earth oxide are not needed, and the overall process is simple, the energy consumption is low, and the auxiliary material cost is low.
Moreover, the method can also reduce the nitrate content in the circulating organic, and the blank organic is washed and clarified by the non-saline water, so that the recycling of the blank organic is ensured to be pure. The invention needs less equipment, and the rare earth nitrate prepared by the invention has excellent quality.
The present invention will be described in further detail with reference to the following examples, which illustrate rare earth elements dysprosium and yttrium, but are not limited thereto, and the present invention is applicable to all rare earths.
Example 1
The invention discloses a preparation method of a raw material for preparing a nano rare earth oxide, which comprises the following steps:
(1) washing stage 1-dysprosium-loaded organic dechlorination: leading out 20L/min of high-chlorine dysprosium loaded organic compounds from a conventional dysprosium extraction separation production line, enabling the high-chlorine dysprosium loaded organic compounds to enter the 1 st stage of a washing 1-stage mixed extraction tank, wherein the washing 1-stage mixed extraction tank has 10 stages, simultaneously adding 1L/min of salt-free water into the last 1 stage of the washing 1 stage, performing 10-stage countercurrent washing to enable chlorine in the high-chlorine dysprosium loaded organic compounds to enter salt-free water, and finally returning the salt-free water containing high chlorine after washing to the conventional dysprosium extraction separation production line;
(2) clarification 1 stage-reduction of organic entrainment: the dysprosium-loaded organic matter which is washed without the brine in the step (1) enters a clarification 1 stage, and after 3-level clarification, a water phase carried in the dysprosium-loaded organic matter is organically separated from the dysprosium-loaded organic matter, so that the dysprosium-loaded organic matter treated by the clarification 1 stage forms a low-chlorine dysprosium-loaded organic matter with the water phase carrying amount of less than 0.005%;
(3) stripping section-qualified raw material output: the low-chlorine dysprosium-loaded organic matter clarified in the step (2) enters a 1 st stage of a stripping section, the stripping section has 8 stages, meanwhile, 1.8L/min of AR-grade 5.0mol/L nitric acid is added into the last 1 stage of the stripping section, and dysprosium is stripped into a water phase through 8-stage countercurrent stripping, so that a qualified raw material for preparing nano dysprosium oxide, namely a low-chlorine-root dysprosium nitrate feed liquid, is finally produced;
(4) washing 2 stage-reduction of blank organic nitrate content: the separated blank organic after the nitric acid back extraction in the step (3) enters the 1 st stage of a washing 2-stage mixed extraction tank, the washing 2-stage mixed extraction tank has 3 stages, meanwhile, 0.45L/min of salt-free water is added into the last 1 stage of the washing 2 stage, the nitric acid carried in the blank organic enters the salt-free water after 3-stage countercurrent washing, and finally, the salt-free water after the washing containing the nitric acid enters the back extraction section in the step (3), so that the content of the blank organic nitrate is reduced;
(5) clarification 2 stage-further reduction of blank organic nitrate content: and (4) allowing the blank organic washed in the step (4) to enter a clarification 2 stage, and after 3-stage clarification, separating the blank organic intermediate aqueous phase from the blank organic phase to ensure that the intermediate aqueous phase entrainment amount in the blank organic treated in the clarification 2 stage is less than 0.005%, and finally returning the blank organic phase to a conventional dysprosium extraction and separation production line to achieve the purpose of recycling.
Example 2
The invention discloses a method for preparing a low-chloride raw material for nano rare earth at low cost, which comprises the following steps:
(1) washing stage 1-yttrium-loaded organic dechlorination: leading 150L/min of high-chlorine yttrium-loaded organic from a conventional yttrium extraction separation production line, enabling the high-chlorine yttrium-loaded organic to enter the 1 st stage of a washing 1-stage mixed extraction tank, wherein the washing 1-stage mixed extraction tank has 15 stages, simultaneously adding 3L/min of brine-free water into the last 1 stage of the washing 1 stage, performing 15-stage countercurrent washing to enable chlorine in the high-chlorine yttrium-loaded organic to enter into the brine-free water, and finally returning the high-chlorine-containing washed brine-free water to the conventional yttrium extraction separation production line;
(2) clarification 1 stage-reduction of organic entrainment: allowing the yttrium-loaded organic subjected to the brine-free washing in the step (1) to enter a clarification 1 stage, and after 5-stage clarification, organically separating a water phase carried in the yttrium-loaded organic from the yttrium load, so that the yttrium-loaded organic subjected to the clarification 1 stage treatment forms a low-chlorine yttrium-loaded organic with the water phase carrying amount of less than 0.005%;
(3) stripping section-qualified raw material output: and (3) allowing the low-chlorine yttrium-loaded organic material clarified in the step (2) to enter a 1 st stage of a stripping section, wherein the stripping section has 10 stages, adding 12L/min of AR-stage 5.0mol/L nitric acid into the last 1 stage of the stripping section, performing 10-stage counter-current stripping, and stripping yttrium into a water phase to finally produce a qualified raw material for preparing nano yttrium oxide, namely the low-chlorine yttrium nitrate feed liquid.
(4) Wash 2 stage-reduction of blank organic nitrate: the separated blank organic matter after the nitric acid back extraction in the step (3) enters the 1 st stage of a washing 2-stage mixed extraction tank, the washing 2-stage mixed extraction tank has 3 stages, meanwhile, 2L/min of salt-free water is added into the last 1 stage of the washing 2 stage, the nitric acid carried in the blank organic matter enters the salt-free water after the 3-stage countercurrent washing, and finally the washed salt-free water containing the nitric acid enters the back extraction stage in the step (3), so that the content of the blank organic nitrate radicals is reduced;
(5) clarification 2 stage-further reduction of blank organic nitrate content: and (4) allowing the blank organic washed in the step (4) to enter a clarification 2 stage, separating the blank organic intermediate aqueous phase from the blank organic after 5-stage clarification, so that the intermediate aqueous phase entrainment of the blank organic treated in the clarification 2 stage is less than 0.005%, and finally returning the blank organic to a conventional yttrium extraction separation production line to achieve the purpose of recycling.
Therefore, the qualified raw material for preparing the nano rare earth oxide, namely the low-chlorine-root rare earth nitrate feed liquid is obtained by organically washing, clarifying and nitric acid back-extracting the high-chlorine load.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope 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 (10)
1. A preparation method of raw materials for preparing nano rare earth oxide is characterized by comprising the following steps:
(1) washing stage 1-loading rare earth organic dechlorination: leading high-chlorine loaded rare earth organic from a conventional extraction separation rare earth production line, and enabling the high-chlorine loaded rare earth organic to enter the 1 st stage of a washing 1-stage mixed extraction tank, wherein the washing 1-stage mixed extraction tank has multiple stages, and simultaneously adding non-saline water into the last 1 stage of the washing 1-stage mixed extraction tank, and enabling the high-chlorine loaded rare earth organic to enter the non-saline water in the process of flowing from the 1 st stage of the washing 1-stage mixed extraction tank to the last 1 stage of the washing 1-stage mixed extraction tank in a counter-current washing mode;
(2) clarification 1 stage-reduction of organic entrainment: the loaded rare earth organic washed without the brine in the step (1) enters a clarification 1 stage, and after multi-stage clarification, water phase carried in the loaded rare earth organic is separated from the loaded rare earth organic, so that the loaded rare earth organic treated by the clarification 1 stage forms low-chlorine loaded rare earth organic with the water phase carrying amount of less than 0.005%;
(3) stripping section-qualified raw material output: and (3) feeding the low-chlorine loaded rare earth organic clarified in the step (2) into a 1 st stage of a back-extraction section, wherein the back-extraction section has multiple stages, adding nitric acid into the last 1 st stage of the back-extraction section, back-extracting the rare earth in the low-chlorine loaded rare earth organic into a water phase in a counter-current back-extraction mode, and finally outputting the raw material for preparing the nano rare earth oxide.
2. The method of preparing a raw material for preparing a nano rare earth oxide according to claim 1, wherein: also comprises a step (4) of washing 2 stages, namely, reducing the content of blank organic nitrate radicals: and (4) feeding the separated blank organic matters after the nitric acid back extraction in the step (3) into the 1 st stage of the washing 2-stage mixed extraction tank, wherein the washing 2-stage mixed extraction tank has multiple stages, simultaneously adding the non-saline water into the last 1 stage of the washing 2 stage, and feeding the nitric acid carried in the blank organic matters into the non-saline water in a countercurrent washing mode.
3. The method of preparing a raw material for preparing a nano rare earth oxide according to claim 2, wherein: also comprises a step (5) of clarifying 2 stages, further reducing the content of blank organic nitrate radicals: and (4) allowing the blank organic washed in the step (4) to enter a clarification 2 stage, and after multi-stage clarification, separating a water phase carried in the blank organic from the blank organic to ensure that the water phase carrying amount in the blank organic treated in the clarification 2 stage is less than 0.005%.
4. A method for preparing a raw material for preparing nano rare earth oxide according to any one of claims 1 to 3, wherein: the conventional extraction separation rare earth production line reversely extracts high-chlorine rare earth-loaded organic matters by utilizing hydrochloric acid.
5. A method for preparing a raw material for preparing nano rare earth oxide according to any one of claims 1 to 3, wherein: returning the washed high-chlorine-content brine without salt generated after the treatment in the step (1) to a conventional rare earth extraction and separation production line.
6. A method for preparing a raw material for preparing nano rare earth oxide according to any one of claims 1 to 3, wherein: in the step (3), the volume of the nitric acid is equal to 2-15% of the volume of the high-chlorine rare earth loaded organic matter.
7. A method for preparing a raw material for preparing nano rare earth oxide according to any one of claims 2 to 3, wherein: the volume of the brine-free water in the step (1) and the step (4) is equal to 1-20% of the volume of the high-chlorine rare earth loaded organic.
8. A method for preparing a raw material for preparing nano rare earth oxide according to any one of claims 2 to 3, wherein: the mixed extraction tank of the washing section 1 in the step (1) and the mixed extraction tank of the washing section 2 in the step (4) are 3-15 grades.
9. The method of preparing a raw material for preparing a nano rare earth oxide according to claim 3, wherein: the clarification in the step (2) and the clarification in the step (5) are both 3-5 grades.
10. The method of preparing a raw material for preparing a nano rare earth oxide according to claim 3, wherein: and (5) returning the blank organic subjected to the clarification 2-stage treatment in the step (5) to a conventional extraction separation rare earth production line.
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