CN114956148A - Method for reducing content of rare earth elements in barium sulfate precipitate and application of hydrochloric acid solution - Google Patents
Method for reducing content of rare earth elements in barium sulfate precipitate and application of hydrochloric acid solution Download PDFInfo
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- CN114956148A CN114956148A CN202210769629.7A CN202210769629A CN114956148A CN 114956148 A CN114956148 A CN 114956148A CN 202210769629 A CN202210769629 A CN 202210769629A CN 114956148 A CN114956148 A CN 114956148A
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- barium
- barium sulfate
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 title claims abstract description 220
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 85
- 239000002244 precipitate Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000005406 washing Methods 0.000 claims abstract description 122
- 229910001422 barium ion Inorganic materials 0.000 claims abstract description 59
- 239000000047 product Substances 0.000 claims abstract description 32
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006227 byproduct Substances 0.000 claims abstract description 15
- 238000009854 hydrometallurgy Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 60
- 239000007787 solid Substances 0.000 claims description 28
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 27
- 229910001626 barium chloride Inorganic materials 0.000 claims description 27
- 239000012452 mother liquor Substances 0.000 claims description 23
- -1 rare earth carbonate Chemical class 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 3
- 239000013049 sediment Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/462—Sulfates of Sr or Ba
-
- 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
-
- 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
- C01F17/253—Halides
- C01F17/271—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for reducing the content of rare earth elements in barium sulfate precipitate and application of a hydrochloric acid solution, wherein the method comprises the following steps: (1) providing a rare earth hydrometallurgy byproduct barium sulfate precipitate, wherein the REO content in the barium sulfate precipitate is more than or equal to 10 wt%; (2) washing the barium sulfate precipitate by adopting a hydrochloric acid solution containing barium ions to remove rare earth elements; (3) washing with water to obtain a barium sulfate product; wherein, the REO content in the barium sulfate product is less than or equal to 0.06 wt%. The method can obviously reduce the content of the rare earth element in the barium sulfate sediment which is the byproduct of rare earth hydrometallurgy.
Description
Technical Field
The invention relates to a method for reducing the content of rare earth elements in barium sulfate precipitate and application of a hydrochloric acid solution.
Background
In the process of the rare earth hydrometallurgy, after the rare earth carbonate is dissolved by hydrochloric acid, sulfate radicals in the rare earth solution are removed by barium chloride, and the formed barium sulfate precipitate carries about 15 wt% of rare earth elements. For example, CN109266872A discloses a method for continuously removing sulfate from a rare earth solution, which adopts a specific device to react sulfate ions in the rare earth solution with barium ions to generate barium sulfate crystals; and the rare earth solution carrying the barium sulfate crystals sequentially flows through the n-stage continuous precipitation tanks and then enters a heat exchanger for cooling, the cooled rare earth solution carrying the barium sulfate crystals enters filtering equipment, the barium sulfate crystals are separated and concentrated and then discharged, and the low sulfate radical rare earth solution enters the next procedure. This patent document does not relate to the further treatment of barium sulphate crystals with a rare earth element incorporated therein.
The rare earth loss can be reduced by washing the barium sulfate precipitate with water. For example, CN113249597A discloses a method for purifying rare earth solution, in which a calcium-containing substance or barium compound is added to the rare earth solution, and then filtered to obtain barium sulfate and rare earth purified solution. The patent document performs acid washing and water washing on crude barium sulfate to remove impurities such as rare earth elements, but the content of the rare earth elements in the washing product is still high and is 1.5-2 wt%.
If the rare earth elements in the barium sulfate sediment which is the byproduct of rare earth hydrometallurgy are removed as much as possible, the yield of the rare earth elements can be improved, and the high-purity functional filler can be obtained. The high-purity barium sulfate can be used in the fields of coatings, printing ink, pigments, rubber, plastics and the like.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for reducing the content of rare earth elements in barium sulfate precipitate, which can reduce the content of rare earth elements in barium sulfate precipitate to 0.06 wt% or less. Furthermore, the whiteness of the barium sulfate solid obtained by the invention is more than or equal to 94. Another object of the present invention is to provide a use of a hydrochloric acid solution containing barium ions for reducing the content of rare earth elements in barium sulfate precipitates. The purpose of the invention is realized by the following technical scheme.
In one aspect, the invention provides a method for reducing the content of rare earth elements in barium sulfate precipitate, which comprises the following steps:
(1) providing a rare earth hydrometallurgy byproduct barium sulfate precipitate, wherein the REO content in the barium sulfate precipitate is more than or equal to 10 wt%;
(2) washing the barium sulfate precipitate by adopting a hydrochloric acid solution containing barium ions to remove rare earth elements;
(3) washing with water to obtain a barium sulfate product; wherein, the REO content in the barium sulfate product is less than or equal to 0.06 wt%.
According to the method of the invention, preferably, the HCl concentration in the hydrochloric acid solution containing barium ions is 0.4-2 mol/L, and the barium ion concentration calculated by barium chloride is 0.04-0.15 g/L.
According to the method provided by the invention, preferably, the barium sulfate precipitate is washed for N times by adopting a hydrochloric acid solution containing barium ions to remove rare earth elements, so as to obtain a barium sulfate product; wherein N is a natural number of 2-9.
According to the method, the washing temperature is preferably 50-95 ℃.
According to the method of the present invention, preferably, the step (2) includes:
washing the barium sulfate precipitate for one time by using a first washing liquid, and performing solid-liquid separation to obtain a first solid and a first mother liquor; wherein the first washing liquid is a hydrochloric acid solution containing barium ions, the HCl concentration is 0.4-2 mol/L, and the barium ion concentration calculated by barium chloride is 0.04-0.15 g/L;
washing the first solid for the second time by using a second washing liquid, and carrying out solid-liquid separation to obtain a second solid and a second mother liquor; wherein the second washing liquid is a hydrochloric acid solution containing barium ions, the HCl concentration is 0.4-2 mol/L, and the barium ion concentration calculated by barium chloride is 0.04-0.15 g/L;
washing the second solid for three times by using a third washing liquid, and carrying out solid-liquid separation to obtain a third solid and a third mother liquor; wherein the third washing liquid is a hydrochloric acid solution containing barium ions, the HCl concentration is 0.4-2 mol/L, and the barium ion concentration calculated by barium chloride is 0.04-0.15 g/L.
According to the method of the present invention, preferably, the second mother liquor is prepared and used as the first washing liquid; and the third mother liquor is used as a second washing liquid after being prepared.
According to the method of the present invention, preferably, the step (3) includes:
washing the third solid by using deionized water to obtain a barium sulfate product; wherein, the REO content in the barium sulfate product is less than 0.06 percent.
The method according to the present invention preferably further comprises the steps of:
and (3) blending the first mother liquor for dissolving the rare earth carbonate to form rare earth chloride.
On the other hand, the invention also provides the application of the hydrochloric acid solution containing barium ions in reducing the content of rare earth elements in barium sulfate precipitate, wherein the barium sulfate precipitate is a rare earth hydrometallurgy byproduct.
According to the use of the invention, preferably, the REO content in the barium sulfate precipitate is greater than or equal to 10 wt%; the REO content in the barium sulfate product washed by the hydrochloric acid solution containing barium ions is less than or equal to 0.06 wt%.
The invention adopts the hydrochloric acid solution containing barium ions to wash the barium sulfate sediment containing the rare earth elements, and can obviously reduce the content of the rare earth elements in the barium sulfate sediment. Compared with the traditional multiple water washing process, the invention can reduce the content of the rare earth element in the barium sulfate to less than or equal to 0.06 wt%. In addition, the washed filtrate can be used as washing liquid for recycling, so that the waste water is reduced, and the cost is reduced. Furthermore, the whiteness of the barium sulfate product obtained by the method is higher, and the barium sulfate product reaches the grade of a superior product.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
Research and experiments show that compared with the traditional method of adopting water washing and/or acid washing, the method for washing the barium sulfate precipitate as the rare earth hydrometallurgy by-product by adopting the hydrochloric acid solution containing barium ions can obviously reduce the content of the rare earth elements in the barium sulfate precipitate, thereby completing the invention.
The method of the invention comprises the following steps: (1) a step of providing a barium sulfate precipitate; (2) washing with a hydrochloric acid solution containing barium ions; (3) and (5) water washing. As described in detail below.
< step of providing barium sulfate precipitate >
First, a barium sulfate precipitate is provided. The barium sulfate precipitate may be a by-product of rare earth hydrometallurgy, for example, a by-product of barium sulfate precipitation formed by adding barium chloride to rare earth chloride, which is obtained by dissolving rare earth carbonate in a rare earth sulfate solution with ammonium bicarbonate and then in a rare earth chloride with hydrochloric acid.
In the present invention, the REO content in the rare earth hydrometallurgical by-product barium sulfate precipitate is 10 wt% or more, preferably 12 wt% or more, more preferably 14 wt% or more, and still more preferably 15 wt% or more. REO refers to the total amount of rare earth oxides, generally expressed in mass percent.
< step of washing with hydrochloric acid solution containing barium ion >
And washing the barium sulfate precipitate by adopting a hydrochloric acid solution containing barium ions to remove the rare earth elements. Preferably, washing the barium sulfate precipitate for N times by using a hydrochloric acid solution containing barium ions to remove rare earth elements to obtain a barium sulfate product; wherein N is a natural number of 2-9. N is preferably a natural number of 2 to 5, more preferably a natural number of 2 to 4. Thus being beneficial to reducing the content of the rare earth elements in the barium sulfate sediment and saving the processing time.
According to a specific embodiment of the invention, the barium sulfate precipitate is washed three times with a hydrochloric acid solution containing barium ions to remove rare earth elements, and a barium sulfate product is obtained.
In the present invention, the hydrochloric acid solution containing barium ions may be formed of a metal oxide or an inorganic salt containing barium element and hydrochloric acid. The barium-containing metal oxide includes barium oxide. The inorganic salt containing barium element includes barium chloride, barium carbonate, barium acetate, barium nitrate, etc.
In the hydrochloric acid solution containing barium ions, the concentration of HCl is 0.4-2 mol/L; preferably 0.5 to 1.7mol/L, and more preferably 0.7 to 1.5 mol/L. In the hydrochloric acid solution containing barium ions, the concentration of barium ions in terms of barium chloride is 0.04-0.15 g/L, preferably 0.05-0.15 g/L, more preferably 0.06-0.12 g/L, and still more preferably 0.07-0.1 g/L. This is advantageous for removing the rare earth elements from the barium sulfate precipitate.
The washing temperature may be 50 to 95 ℃, preferably 60 to 90 ℃, and more preferably 65 to 90 ℃. Such washing conditions are favorable for removing the rare earth elements in the barium sulfate precipitate.
In certain embodiments, the barium sulfate precipitate is subjected to a first washing with a first washing solution, and the first solid and the first mother liquor are obtained by solid-liquid separation; wherein the first washing liquid is a hydrochloric acid solution containing barium ions, the HCl concentration is 0.4-2 mol/L, and the barium ion concentration calculated by barium chloride is 0.04-0.15 g/L; washing the first solid for the second time by using a second washing liquid, and carrying out solid-liquid separation to obtain a second solid and a second mother liquor; wherein the second washing liquid is a hydrochloric acid solution containing barium ions, the HCl concentration is 0.4-2 mol/L, and the barium ion concentration calculated by barium chloride is 0.04-0.15 g/L; washing the second solid for three times by using a third washing liquid, and carrying out solid-liquid separation to obtain a third solid and a third mother liquor; wherein the third washing liquid is a hydrochloric acid solution containing barium ions, the HCl concentration is 0.4-2 mol/L, and the barium ion concentration calculated by barium chloride is 0.04-0.15 g/L.
The HCl concentration in the first washing liquid is preferably 0.7 to 1.6mol/L, more preferably 0.8 to 1.5mol/L, and still more preferably 0.9 to 1.3 mol/L. The concentration of barium ions in terms of barium chloride is preferably 0.06-0.14 g/L, more preferably 0.08-0.12 g/L. According to one embodiment of the present invention, the concentration of HCl in the first washing liquid is 0.6 to 1.0 mol/L; the concentration of barium ions is 0.06-0.1 g/L calculated by barium chloride.
The solid-liquid mass ratio of the barium sulfate precipitate to the first washing liquid is 1: 1.8-2.8, preferably 1: 1.9-2.5, and more preferably 1: 1.9-2.2.
The temperature of the first washing may be 50 to 95 ℃, preferably 60 to 90 ℃, and more preferably 65 to 90 ℃. According to one embodiment of the present invention, the primary washing temperature is 65 to 80 ℃. The primary washing time can be 0.5-3.5 h, preferably 1-3 h, and more preferably 1.5-2.5 h. This is advantageous for better reduction of the rare earth element content in the barium sulfate precipitate.
After the first washing step is finished, solid-liquid separation can be directly carried out. The manner of solid-liquid separation is not particularly limited, and those known in the art may be employed. For example, reduced pressure filtration may be employed.
The resulting first solid can be used directly in the second washing step.
The resulting first mother liquor may be formulated for dissolving rare earth carbonate to form rare earth chloride. Therefore, the production of waste water can be reduced, the cost is reduced, and the cyclic utilization of resources is facilitated.
The HCl concentration and the barium ion concentration of the second washing reagent may be the same as or different from those of the first washing reagent. In the second washing liquid, the HCl concentration may be 0.4 to 2mol/L, preferably 0.6 to 1.7mol/L, and more preferably 0.8 to 1.5 mol/L. The concentration of barium ion in terms of barium chloride may be 0.04 to 0.15g/L, preferably 0.05 to 0.14g/L, and more preferably 0.06 to 0.12 g/L.
The solid-liquid mass ratio of the barium sulfate precipitate to the second washing liquid is 1: 1.8-2.8, preferably 1: 1.9-2.5, and more preferably 1: 1.9-2.1.
The secondary washing temperature and time may be the same as in the primary washing step, or may be different. The secondary washing temperature may be 50 to 95 ℃, preferably 60 to 90 ℃, and more preferably 65 to 90 ℃. According to one embodiment of the present invention, the secondary washing temperature is 70 to 90 ℃. The secondary washing time may be 0.5 to 3.5 hours, preferably 1 to 3 hours, and more preferably 1.5 to 2.5 hours. This is advantageous for better reduction of the rare earth element content in the barium sulfate precipitate.
The second solid obtained can be used directly in the three washing steps.
The second mother liquor thus obtained can be used as the first washing liquid after blending. Specifically, the second mother liquor may be used as the first washing liquid after being mixed with hydrochloric acid and a small amount of barium chloride. Therefore, the production of waste water can be reduced, the cost is reduced, and the cyclic utilization of resources is facilitated.
The HCl concentration and the barium ion concentration in the third washing reagent may be the same as or different from those of the first washing reagent and the second washing reagent. In the third washing reagent, the HCl concentration may be 0.4 to 2mol/L, preferably 0.6 to 1.7mol/L, more preferably 0.8 to 1.5mol/L, and further preferably 0.9 to 1.3 mol/L. The concentration of barium ions in terms of barium chloride may be 0.04 to 0.15g/L, preferably 0.05 to 0.14g/L, and more preferably 0.05 to 0.1 g/L.
The solid-liquid mass ratio of the barium sulfate precipitate to the second washing liquid is 1: 1.8-2.8, preferably 1: 1.9-2.5, and more preferably 1: 1.9-2.1.
The temperature and time of the three-time washing may be the same as those in the one-time washing step or may be different. The temperature of the third washing can be 50-95 ℃, preferably 60-90 ℃, and more preferably 65-90 ℃. According to one embodiment of the present invention, the temperature of the third washing is 80 to 90 ℃. The time for the third washing can be 0.5-3.5 h, preferably 1-3 h, and more preferably 1.5-2.5 h. This is advantageous for better reduction of the rare earth element content in the barium sulfate precipitate.
The third solid obtained can be used directly in the water washing step.
The obtained third mother liquor may be used as the second washing liquid after being prepared. Specifically, the third mother liquor may be used as the second washing liquid after being mixed with hydrochloric acid and a small amount of barium chloride. Therefore, the method can reduce the generation of waste water, reduce the cost and is beneficial to the cyclic utilization of resources.
After the secondary washing step and the third washing step are finished, solid-liquid separation can be directly carried out. The manner of solid-liquid separation is not particularly limited, and those known in the art may be employed. For example, reduced pressure filtration may be employed.
< Water washing step >
Washing with water to obtain a barium sulfate product. And specifically, washing the third solid by using deionized water to obtain a barium sulfate product.
The solid-liquid mass ratio of the barium sulfate to the washing water is 1.5-2.2: 1, preferably 1.7-2.1: 1, such as 2:1, the washing temperature of the washing water is room temperature, and the washing time is 1 h.
The REO content in the barium sulfate product is less than or equal to 0.06 wt%, preferably less than 0.06 wt%, more preferably less than or equal to 0.04 wt%, and still more preferably less than or equal to 0.03 wt%.
The whiteness of the obtained barium sulfate product is more than 94, preferably more than or equal to 95.
< use of hydrochloric acid solution containing barium ion >
The invention also provides application of the hydrochloric acid solution containing barium ions in reducing the content of rare earth elements in barium sulfate precipitate, wherein the barium sulfate precipitate is a rare earth hydrometallurgy byproduct. The REO content in the barium sulfate sediment is more than or equal to 10 wt%; the REO content in the barium sulfate product washed by the hydrochloric acid solution containing barium ions is less than or equal to 0.06 wt%. The source of the barium sulfate precipitate and the specific operation content for reducing the content of the rare earth element in the barium sulfate precipitate are described in detail in the foregoing, and are not described in detail herein.
< analytical method >
Whiteness of barium sulfate: according to the whiteness measurement method in GB/T2899-.
REO content: the measurement is carried out by EDTA volumetric method.
In the following examples and comparative examples:
the rare earth hydrometallurgy by-product barium sulfate precipitation containing rare earth elements comes from: adding ammonium bicarbonate into the sulfuric acid rare earth solution to obtain rare earth carbonate, and dissolving the rare earth carbonate with hydrochloric acid to obtain a rare earth chloride solution; the rare earth chloride solution is treated with barium chloride to eliminate sulfate radical from the rare earth chloride solution to form barium sulfate precipitate and purify the rare earth chloride solution. In the barium sulfate precipitate, the REO content was 16.32 wt%.
Examples 1 to 3
Provides a rare earth hydrometallurgy byproduct barium sulfate precipitate which contains rare earth elements. And adding the barium sulfate precipitate into the first washing liquid, stirring, washing and filtering to obtain a first solid and a first mother liquid. The first washing liquid is a hydrochloric acid solution containing barium ions, wherein the HCl concentration is 0.5mol/L, and the barium chloride concentration is 0.05 g/L. Washing temperature T 1 Washing time t 1 . The first mother liquor can be used for dissolving rare earth carbonate after being prepared by hydrochloric acid.
And adding the first solid into the second washing liquid, stirring, washing and filtering to obtain a second solid and a second mother liquid. The second washing liquid is a hydrochloric acid solution containing barium ions, wherein the HCl concentration is 0.5mol/L, and the barium chloride concentration is 0.05 g/L. Washing temperature T 2 Washing time t 2 . The second mother liquor is used as a first washing liquid after being prepared by hydrochloric acid and barium chloride.
And adding the second solid into the third washing liquid, stirring, washing and filtering to obtain a third solid and a third mother liquid. The third washing liquid is a hydrochloric acid solution containing barium ions, wherein the HCl concentration is 0.5mol/L, and the barium chloride concentration is 0.05 g/L. Washing temperature T 3 Washing time t 3 . And the third mother liquor is used as a second washing liquid after being prepared.
Washing the third solid with deionized water (the solid-liquid mass ratio of the barium sulfate precipitate to the deionized water is 2, and washing at room temperature for 1h) to obtain a barium sulfate product. In the barium sulfate product, the content of REO is 0.03 wt%, and the whiteness of the barium sulfate product is 95.
Comparative example 1
This comparative example 1 is different from example 1 in that washing was performed using deionized water instead of the hydrochloric acid solution containing barium ions. The process parameters and the detection results of the obtained barium sulfate product are shown in table 1 below.
Comparative example 2
This comparative example 2 is different from example 1 in that washing was performed using deionized water instead of the hydrochloric acid solution containing barium ions, and the washing temperature was different. The process parameters and the detection results of the obtained barium sulfate product are shown in table 1 below.
Comparative example 3
This comparative example 3 differs from example 1 in that washing was performed using a hydrochloric acid solution containing no barium ion. The process parameters and the detection results of the obtained barium sulfate product are shown in table 1 below.
Comparative example 4
This comparative example 4 differs from example 1 in that washing was performed with a barium chloride solution containing no hydrochloric acid. The process parameters and the detection results of the obtained barium sulfate product are shown in table 1 below.
TABLE 1
As can be seen from the table, the method of the invention can reduce the content of rare earth elements in the barium sulfate sediment which is a byproduct of rare earth hydrometallurgy. Moreover, the obtained barium sulfate has better physical properties, can improve the added value and change waste into valuable.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. A method for reducing the content of rare earth elements in barium sulfate precipitate is characterized by comprising the following steps:
(1) providing a rare earth hydrometallurgy byproduct barium sulfate precipitate, wherein the REO content in the barium sulfate precipitate is more than or equal to 10 wt%;
(2) washing the barium sulfate precipitate by adopting a hydrochloric acid solution containing barium ions to remove rare earth elements;
(3) washing with water to obtain a barium sulfate product; wherein, the REO content in the barium sulfate product is less than or equal to 0.06 wt%.
2. The method according to claim 1, wherein the HCl concentration in the hydrochloric acid solution containing barium ions is 0.4 to 2mol/L, and the barium ion concentration in terms of barium chloride is 0.04 to 0.15 g/L.
3. The method according to claim 1, wherein the barium sulfate precipitate is washed with a hydrochloric acid solution containing barium ions for N times to remove rare earth elements, to obtain a barium sulfate product; wherein N is a natural number of 2-9.
4. The method according to claim 1, wherein the washing temperature is 50 to 95 ℃.
5. The method of claim 1, wherein step (2) comprises:
washing the barium sulfate precipitate for one time by using a first washing liquid, and performing solid-liquid separation to obtain a first solid and a first mother liquor; wherein the first washing liquid is a hydrochloric acid solution containing barium ions, the HCl concentration is 0.4-2 mol/L, and the barium ion concentration calculated by barium chloride is 0.04-0.15 g/L;
washing the first solid for the second time by using a second washing liquid, and carrying out solid-liquid separation to obtain a second solid and a second mother liquor; wherein the second washing liquid is a hydrochloric acid solution containing barium ions, the HCl concentration is 0.4-2 mol/L, and the barium ion concentration calculated by barium chloride is 0.04-0.15 g/L;
washing the second solid for three times by using a third washing liquid, and carrying out solid-liquid separation to obtain a third solid and a third mother liquor; wherein the third washing liquid is a hydrochloric acid solution containing barium ions, the HCl concentration is 0.4-2 mol/L, and the barium ion concentration calculated by barium chloride is 0.04-0.15 g/L.
6. The method of claim 5, wherein the second mother liquor is formulated for use as the first wash solution; and the third mother liquor is used as a second washing liquid after being prepared.
7. The method of claim 6, wherein step (3) comprises:
washing the third solid by using deionized water to obtain a barium sulfate product; wherein, the REO content in the barium sulfate product is less than 0.06 percent.
8. The method of claim 7, further comprising the steps of:
and (3) blending the first mother liquor for dissolving the rare earth carbonate to form rare earth chloride.
9. The application of the hydrochloric acid solution containing barium ions in reducing the content of rare earth elements in barium sulfate precipitate is characterized in that the barium sulfate precipitate is a rare earth hydrometallurgy byproduct.
10. Use according to claim 9, characterized in that the REO content in the barium sulphate precipitate is equal to or greater than 10 wt%; the REO content in the barium sulfate product washed by the hydrochloric acid solution containing barium ions is less than or equal to 0.06 wt%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585550A (en) * | 2009-04-13 | 2009-11-25 | 王嘉兴 | Method of precipitated barium sulfate coproduction hydrochloric acid with barium chloride |
| CN103130260A (en) * | 2013-03-19 | 2013-06-05 | 冉金友 | Production method of barium sulfate |
| CN108975375A (en) * | 2018-08-09 | 2018-12-11 | 株洲冶炼集团股份有限公司 | A kind of high whiteness native sulfate of barium production technology of high pure and ultra-fine |
| CN113249597A (en) * | 2020-09-14 | 2021-08-13 | 江西明达功能材料有限责任公司 | Method for purifying rare earth solution |
| CN114058882A (en) * | 2021-11-12 | 2022-02-18 | 四川江铜稀土有限责任公司 | Method for purifying barite and recovering rare earth from barite concentrate |
| CN114252313A (en) * | 2021-12-06 | 2022-03-29 | 贵州民族大学 | Method for rapidly analyzing content of barium sulfate in barite ore |
-
2022
- 2022-06-30 CN CN202210769629.7A patent/CN114956148A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585550A (en) * | 2009-04-13 | 2009-11-25 | 王嘉兴 | Method of precipitated barium sulfate coproduction hydrochloric acid with barium chloride |
| CN103130260A (en) * | 2013-03-19 | 2013-06-05 | 冉金友 | Production method of barium sulfate |
| CN108975375A (en) * | 2018-08-09 | 2018-12-11 | 株洲冶炼集团股份有限公司 | A kind of high whiteness native sulfate of barium production technology of high pure and ultra-fine |
| CN113249597A (en) * | 2020-09-14 | 2021-08-13 | 江西明达功能材料有限责任公司 | Method for purifying rare earth solution |
| CN114058882A (en) * | 2021-11-12 | 2022-02-18 | 四川江铜稀土有限责任公司 | Method for purifying barite and recovering rare earth from barite concentrate |
| CN114252313A (en) * | 2021-12-06 | 2022-03-29 | 贵州民族大学 | Method for rapidly analyzing content of barium sulfate in barite ore |
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