CN115504442A - Preparation method of high-purity optical glass additive lithium phosphate - Google Patents
Preparation method of high-purity optical glass additive lithium phosphate Download PDFInfo
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- 229910001386 lithium phosphate Inorganic materials 0.000 title claims abstract description 111
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims abstract description 111
- 239000005304 optical glass Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000654 additive Substances 0.000 title abstract description 9
- 230000000996 additive effect Effects 0.000 title abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 98
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 36
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 34
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- AUYOHNUMSAGWQZ-UHFFFAOYSA-L dihydroxy(oxo)tin Chemical compound O[Sn](O)=O AUYOHNUMSAGWQZ-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 65
- 238000003756 stirring Methods 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 32
- 239000012498 ultrapure water Substances 0.000 claims description 23
- 239000012065 filter cake Substances 0.000 claims description 22
- 239000006228 supernatant Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000007865 diluting Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 50
- 229910052742 iron Inorganic materials 0.000 description 27
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 25
- 229910052793 cadmium Inorganic materials 0.000 description 25
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 25
- 229910052804 chromium Inorganic materials 0.000 description 25
- 239000011651 chromium Substances 0.000 description 25
- 229910017052 cobalt Inorganic materials 0.000 description 25
- 239000010941 cobalt Substances 0.000 description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 25
- 229910052802 copper Inorganic materials 0.000 description 25
- 239000010949 copper Substances 0.000 description 25
- 229910052759 nickel Inorganic materials 0.000 description 25
- 229910052720 vanadium Inorganic materials 0.000 description 25
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 25
- 239000007795 chemical reaction product Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000003556 assay Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
- C01B25/301—Preparation from liquid orthophosphoric acid or from an acid solution or suspension of orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a preparation method of high-purity lithium phosphate, which solves the technical problems that the purity and metal impurity indexes of the lithium phosphate prepared by the existing method cannot meet the requirements of the lithium phosphate as an optical glass additive, and the experimental high-purity product is difficult to produce in quantity. The invention adopts a multi-stage conversion mode, firstly adopts hydrochloric acid to dissolve lithium carbonate, and adopts a special material of metastannic acid as an adsorbent to adsorb and remove heavy metal impurities in the solution because the lithium chloride solution is acidic; filtering the solution, and adding diluted phosphoric acid solution; as phosphoric acid reacts with lithium chloride, hydrochloric acid is obtained as a byproduct, lithium phosphate is less separated out, and the hydrochloric acid can be directly used as seed crystal and added with reagent-grade ammonia water to neutralize the hydrochloric acid, so that lithium phosphate can be separated out.
Description
Technical Field
The invention belongs to the technical field of additives, and particularly relates to a preparation method of high-purity lithium phosphate.
Background
The lithium phosphate can be applied to battery materials, fluorescent materials and special optical glass, with the rapid development of the optical glass industry, the optical glass with various phosphate and villiaumite formulas grows in an explosive manner, and the required amount of various phosphate and villiaumite optical glass additives is larger and larger.
With the development of phosphate optical glass material technology, lithium phosphate is used as an optical glass additive and is increasingly widely applied, and the optical glass added with the lithium phosphate shows special optical property and refractive index and has good application prospect.
However, lithium phosphate produced in the current market is mainly used for fluorescent materials and special ceramics, the requirement on metal impurities in the lithium phosphate is not high, but if the lithium phosphate is used as a high-purity optical glass additive, the purity of the lithium phosphate and the contained metal impurities including iron, cobalt, nickel, copper, cadmium, chromium, vanadium and the like have high requirements, and the requirement index is quite strict, wherein the elements of the iron, the cobalt, the nickel, the copper, the cadmium, the chromium, the vanadium and the like are less than 0.5ppm; and few manufacturers for producing high-purity lithium phosphate in the market mostly are laboratory products, and the mass production is difficult.
Therefore, the present invention seeks a method for preparing high purity lithium phosphate.
Disclosure of Invention
The invention aims to solve the technical problems that the purity and the metal impurity index of lithium phosphate prepared by the existing method cannot meet the requirement of the lithium phosphate as an optical glass additive and the experimental high-purity product is difficult to produce in quantity, and provides a preparation method of the high-purity lithium phosphate, which can produce the lithium phosphate with the purity of more than 99.9 percent.
In order to achieve the purpose, the technical solution provided by the invention is as follows:
the preparation method of the high-purity lithium phosphate is characterized by comprising the following steps:
1.1, diluting analytically pure hydrochloric acid by adopting high-purity water until the mass fraction is 20-23%, adding lithium carbonate, heating and stirring for reaction to dissolve the lithium carbonate to be transparent, and diluting by adding high-purity water until the specific gravity is 1.08-1.1, so as to facilitate subsequent adsorption and coprecipitation of impurities;
the reaction equation is: li 2 CO 3 +2HCl→2LiCl+H 2 O+CO 2
Step 1.2, adding 2-3.5% by mass of hydrochloric acid into the solution obtained in the step 1.1 while adding metastannic acid, fully stirring and then settling, adsorbing and settling excessive metal impurities through metastannic acid, removing metal impurities (such as Fe) in the solution through hydrochloric acid reaction, and then collecting supernatant;
step 1.3, filtering the supernatant obtained in the step 1.2, wherein the central control metal impurity elements are less than 0.1ppm, so as to obtain a pure lithium chloride solution;
step 2, synthesizing lithium phosphate
Step 2.1, in order to ensure the purity of a target product, adding high-purity water to dilute the food-grade phosphoric acid superior product with the controlled metal impurity elements less than 0.3ppm until the mass fraction is 10-15%, adding the diluted product into the lithium chloride solution obtained in the step 1, stirring and heating the solution for reaction to obtain a synthetic solution;
2.2 in order to ensure the purity of a target product, controlling metal impurity elements in reagent-grade ammonia to be less than 0.1ppm, diluting the solution to the mass fraction of 10-12%, slowly adding the solution into the synthetic solution obtained in the step 2.1, keeping the temperature at 80-85 ℃, stirring and reacting for 30-40 minutes, adjusting the pH to 2-3 (the pH is adjusted to 2-3 to prevent lithium phosphate from hydrolysis because the solubility of lithium hydroxide is also very low; according to the feeding proportion, when 90% is fed according to the theoretical neutralization feeding amount in the ammonia neutralization process, beginning to slow down ammonia feeding, detecting the pH value of the solution by using precision test paper, adjusting the pH value to 2-3, stirring for 30 minutes, then measuring the pH value, and controlling to be proper if not changed), keeping the temperature at 80-85 ℃, stirring and reacting for 2-3 hours to fully form particles, thereby obtaining the lithium phosphate synthetic solution; because the lithium chloride reacts with the phosphoric acid to generate hydrochloric acid, most of lithium phosphate is dissolved in the hydrochloric acid, ammonia water is needed to be added for neutralization, the hydrochloric acid is converted into ammonium chloride, and the lithium phosphate is separated out from the hydrochloric acid;
the reaction equation is as follows: 3LiCl + H 3 PO 4 +3NH 4 OH→Li 3 PO 4 +3NH 4 Cl+3H 2 O
Step 3, dehydrating and drying lithium phosphate
3.1, performing filter pressing on the lithium phosphate synthetic solution obtained in the step 2, washing with water until the pH value is 5-6 (the content of chloride ions can be ensured to be less than 0.02 percent in the numerical range), and controlling the mass fraction of the chloride ions in the mother liquor to be less than 0.02 percent to obtain a lithium phosphate filter cake, wherein the collected mother liquor can be filtered, and ammonium chloride crystals can be obtained through evaporation and concentration, so that the reutilization of byproducts is realized;
step 3.2, performing gradient drying on the lithium phosphate filter cake obtained in the step 3.1, wherein the specific drying process is as follows:
drying for 2-3 hours at the first gradient of 200-300 ℃;
and drying the second gradient at 500-600 ℃ for 2-3 hours to obtain the high-purity lithium phosphate with the elements of iron, cobalt, nickel, copper, cadmium, chromium, vanadium and the like less than 0.5ppm, phosphorus pentoxide 30.3 +/-1 percent and purity more than 99.99 percent.
The metal impurity elements mainly refer to elements such as iron, cobalt, nickel, copper, cadmium, chromium, vanadium and the like.
Further, step 1.1 specifically comprises:
adding analytically pure hydrochloric acid into a reaction kettle, diluting the hydrochloric acid by adopting high-purity water until the mass fraction is 20%, adding lithium carbonate into the hydrochloric acid, heating to 80-90 ℃, stirring and reacting for 30-60 minutes to dissolve the lithium carbonate until the lithium carbonate is transparent, and diluting the lithium carbonate by adding high-purity water until the specific gravity is 1.08-1.1; wherein the molar ratio of the hydrochloric acid to the lithium carbonate is 2:1.
Further, step 1.2 specifically comprises:
adding 2-3.5% hydrochloric acid while adding metastannic acid into the obtained solution, fully stirring for at least 30 minutes, settling for at least 8 hours, and collecting supernatant;
wherein the addition amount of the metastannic acid is 1/500-1/1000 of the mass of the lithium carbonate.
Further, in step 1.3, the supernatant obtained in step 1.2 is filtered using a 1 micron filter cartridge.
Further, in step 2.1, heating to 70-80 ℃;
the molar ratio of the phosphoric acid to the lithium carbonate is 2: 3.
Further, step 3.1 specifically comprises:
and (3) pumping the lithium phosphate synthetic solution obtained in the step (2) into a plate-and-frame filter press, performing filter pressing by using filter cloth with the mesh size of more than 2000, washing with water until the pH value is 5-6, and obtaining a lithium phosphate filter cake, wherein the mass fraction of chloride ions in the medium control mother solution is less than 0.02%.
Further, in step 3.2, a ceramic plate is used for containing the lithium phosphate filter cake obtained in step 3.1 for drying.
Meanwhile, the invention also provides high-purity lithium phosphate, which is characterized in that: the preparation method is adopted to prepare the product.
An optical glass is characterized in that: the high-purity lithium phosphate prepared by the preparation method is added.
The conception of the invention is as follows:
the invention adopts a multi-stage conversion mode, firstly adopts hydrochloric acid to dissolve lithium carbonate, and adopts a special material of meta-stannic acid as an adsorbent to adsorb and remove heavy metal impurities in the solution because a lithium chloride solution is acidic, and also adds dilute hydrochloric acid when adding the meta-stannic acid for reacting to remove the metal impurity iron; filtering the solution, and adding diluted phosphoric acid solution; as phosphoric acid reacts with lithium chloride, hydrochloric acid is obtained as a byproduct, lithium phosphate is less separated out, and the hydrochloric acid can be directly used as seed crystal and added with reagent-grade ammonia water to neutralize the hydrochloric acid, so that lithium phosphate can be separated out. The specific reaction equation is as follows:
Li 2 CO 3 +2HCl→2LiCl+H 2 O+CO 2
3LiCl+H 3 PO 4 +3NH 4 OH→Li 3 PO 4 +3NH 4 Cl+3H 2 O
the invention has the advantages that:
1. the invention adopts the easily obtained lithium carbonate as the main raw material to prepare the high-purity lithium phosphate, and has simple preparation process and high product purity. Because lithium carbonate and phosphoric acid are directly synthesized, the obtained lithium phosphate has insufficient purity and higher metal impurity index. Therefore, the invention adopts a multi-stage conversion mode, firstly adopts hydrochloric acid to dissolve lithium carbonate, adopts a special material of metastannic acid as an adsorbent to adsorb and remove heavy metal impurities in the solution because the lithium chloride solution is acidic, and also adds dilute hydrochloric acid when adding metastannic acid for reacting to remove the metal impurity iron. Further, filtering the solution, and adding a diluted phosphoric acid solution; as phosphoric acid reacts with lithium chloride, hydrochloric acid is obtained as a byproduct, lithium phosphate is less separated out, and the hydrochloric acid can be directly used as seed crystal and added with reagent-grade ammonia water to neutralize the hydrochloric acid, so that lithium phosphate can be separated out.
2. The obtained lithium phosphate is dried by special gradient, so that the high-purity lithium phosphate with the content of 99.99 percent can be effectively prepared, wherein the content of iron, cobalt, nickel, copper, cadmium, chromium, vanadium and the like is less than 0.5ppm.
3. The method has the advantages of simple industrial operation equipment, mild production conditions, extremely low waste water and waste gas discharge, stable and reliable process, capability of mass production and capability of meeting market requirements.
4. The mother liquor of the invention can be filtered and evaporated and concentrated to obtain ammonium chloride crystals for further utilization, such as being used as fertilizer.
Drawings
Fig. 1 is an XRD pattern of the target product lithium phosphate.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
example 1
This example prepares high purity lithium phosphate by the following procedure
Step 1.1, adding 271kg of analytically pure hydrochloric acid into a reaction kettle, adding high-purity water to dilute the analytically pure hydrochloric acid to 20 mass percent, adding 100kg of lithium carbonate into the reaction kettle, wherein the molar ratio of the hydrochloric acid to the lithium carbonate is 2:1, heating the reaction kettle to 80 ℃, stirring the reaction kettle for 30 minutes, dissolving the reaction product to be transparent, adding high-purity water to dilute the reaction product to 1.09 specific gravity, adding 100g of metastannic acid into the reaction kettle, wherein the proportion of the metastannic acid is 1/1000 of the mass of the lithium carbonate, simultaneously adding 2-3.5 mass percent of hydrochloric acid, fully stirring the reaction product for 30 minutes, settling the reaction product for 8 hours, and collecting supernatant;
step 1.2, enabling the supernatant collected in the step 1.1 to pass through a 1-micron filter element, and controlling the content of iron, cobalt, nickel, copper, cadmium, chromium, vanadium and other elements to be less than 0.1ppm to obtain a pure lithium chloride solution;
step 2, lithium phosphate synthesis
Step 2.1, adding 105kg of food-grade phosphoric acid (with the mass fraction of 85%) and adding purified water to dilute the solution until the mass fraction is 10% (the mass fraction of elements such as iron, cobalt, nickel, copper, cadmium, chromium, vanadium and the like are all less than 0.3 ppm), adding the diluted solution into the lithium chloride solution obtained in the step 1.2, stirring the solution, and heating the solution to 80 ℃ for reaction to obtain a synthetic solution;
step 2.2, controlling the content of iron, cobalt, nickel, copper, cadmium, chromium, vanadium and other elements in the reagent-grade ammonia water to be less than 0.1ppm, diluting the reagent-grade ammonia water to the mass fraction of 10%, slowly adding the diluted reagent-grade ammonia water into the synthetic liquid obtained in the step 2.1, keeping the temperature at 80 ℃, stirring and reacting for 30 minutes, adjusting the pH value to 2-3, keeping the temperature at 80 ℃, stirring and reacting for 2 hours to fully form particles, and obtaining a lithium phosphate synthetic liquid;
step 3, dehydrating and drying lithium phosphate
3.1, pumping the lithium phosphate synthetic solution into a plate-and-frame filter press, performing filter pressing by adopting 2000-mesh filter cloth, washing with water until the pH value is 5-6, and obtaining a lithium phosphate filter cake, wherein the mass fraction of the central control chloride ions is less than 0.02%;
3.2, placing the lithium phosphate filter cake into a ceramic dish, paving the lithium phosphate filter cake and performing gradient drying;
drying for 3 hours at the first gradient of 200 ℃;
drying for 3 hours at 500 ℃ in a second gradient manner to obtain a target product, and determining the product as lithium phosphate by XRD (X-ray diffraction), as shown in figure 1; the product is measured by a quinmolybdic citraconic ketone mixed liquid method to obtain P 2 O 5 The content is 61.6%; and detecting by Agilent 5110-ICP-OES to obtain products with less than 0.5ppm of cobalt, nickel, titanium, vanadium, chromium, cadmium, copper and lead and 0.89ppm of iron, wherein the indexes meet the requirements. The specific assay analysis results are shown in table 1:
TABLE 1
Example 2
This example prepares high purity lithium phosphate by the following procedure
Step 1.1, adding 325kg of analytically pure hydrochloric acid into a reaction kettle, adding high-purity water to dilute the analytically pure hydrochloric acid to 20 mass percent, adding 120kg of lithium carbonate into the reaction kettle, wherein the molar ratio of the hydrochloric acid to the lithium carbonate is 2:1, heating the reaction kettle to 80 ℃, stirring the reaction kettle for 60 minutes, dissolving the reaction product to be transparent, adding high-purity water to dilute the reaction product to 1.1 specific gravity, adding 240g of metastannic acid into the reaction kettle according to the proportion of 1/500 of the mass of the lithium carbonate, simultaneously adding 2-3.5 mass percent of hydrochloric acid, fully stirring the reaction product for 30 minutes, settling the reaction product for 8 hours, and collecting supernatant;
step 1.2, enabling the settled supernatant to pass through a filter element with the diameter of 1 micron, and controlling the content of elements such as iron, cobalt, nickel, copper, cadmium, chromium, vanadium and the like to be less than 0.1ppm to obtain a pure lithium chloride solution;
step 2, lithium phosphate synthesis
Step 2.1, adding 125kg of food-grade phosphoric acid (with the mass fraction of 85%) and high-purity water to 10% by mass (the mass fraction of iron, cobalt, nickel, copper, cadmium, chromium, vanadium and other elements are all less than 0.3 ppm), adding the obtained solution into the lithium chloride solution obtained in the step 1.2, stirring and heating to 80 ℃ for reaction to obtain a synthetic solution;
step 2.2, diluting the reagent-grade ammonia water until the content of elements such as iron, cobalt, nickel, copper, cadmium, chromium, vanadium and the like is less than 0.1ppm, slowly adding the diluted reagent-grade ammonia water into the synthetic liquid obtained in the step 2.1, keeping the temperature at 80 ℃, stirring and reacting for 30 minutes, adjusting the pH value to 2-3, keeping the temperature at 80 ℃, stirring and reacting for 3 hours, fully forming particles, and obtaining a lithium phosphate synthetic liquid;
step 3, dehydrating and drying lithium phosphate
3.1, pumping the lithium phosphate synthetic solution into a plate-and-frame filter press, performing filter pressing by adopting 2000-mesh filter cloth, washing with water until the pH value is 5-6, and obtaining a lithium phosphate filter cake, wherein the mass fraction of the central control chloride ions is less than 0.02%;
3.2, placing the lithium phosphate filter cake into a ceramic dish, paving the lithium phosphate filter cake and performing gradient drying;
drying for 2 hours at the first gradient of 250 ℃;
drying the product for 2 hours at 580 ℃ in a second gradient manner to obtain a target product, wherein the product is characterized as lithium phosphate by XRD (X-ray diffraction), as shown in figure 1; the product is mixed with the quinmolybdic citraconic ketoneIn which P is determined by liquid method 2 O 5 The content is 61.3%; and detecting by Agilent 5110-ICP-OES to obtain products with less than 0.5ppm of cobalt, nickel, titanium, vanadium, chromium, cadmium, copper and lead and 0.76ppm of iron, wherein the indexes meet the requirements. The specific assay analysis results are shown in table 2:
table 2:
example 3
This example prepares high purity lithium phosphate by the following procedure
Step 1.1, adding 217kg of analytically pure hydrochloric acid into a reaction kettle, adding high-purity water to dilute the analytically pure hydrochloric acid to 20 mass percent, adding 80kg of lithium carbonate into the reaction kettle, wherein the molar ratio of the hydrochloric acid to the lithium carbonate is 2:1, heating the reaction kettle to 80 ℃, stirring the reaction kettle for 50 minutes, dissolving the reaction product to be transparent, adding high-purity water to dilute the reaction product to 1.08 specific gravity, adding 100g of metastannic acid into the reaction kettle, wherein the proportion of the metastannic acid is 1/800 of the mass of the lithium carbonate, simultaneously adding 2-3.5 mass percent of hydrochloric acid, fully stirring the reaction product for 30 minutes, settling the reaction product for 8 hours, and collecting supernatant;
step 1.2, enabling the supernatant collected in the step 1.1 to pass through a 1-micron filter element, and controlling the content of iron, cobalt, nickel, copper, cadmium, chromium, vanadium and other elements to be less than 0.1ppm to obtain a pure lithium chloride solution;
step 2, lithium phosphate synthesis
Step 2.1, adding 84kg of food-grade phosphoric acid (the mass fraction is 85%) and adding high-purity water to be diluted to 10% by mass (the mass fraction of elements such as iron, cobalt, nickel, copper, cadmium, chromium and vanadium are all less than 0.3 ppm), adding the diluted solution into the lithium chloride solution obtained in the step 1.2, stirring and heating to 80 ℃ for reaction to obtain a synthetic solution;
step 2.2, controlling the content of iron, cobalt, nickel, copper, cadmium, chromium, vanadium and other elements in the reagent-grade ammonia water to be less than 0.1ppm, diluting the reagent-grade ammonia water to the mass fraction of 10%, slowly adding the diluted reagent-grade ammonia water into the synthetic solution obtained in the step 2.1, keeping the temperature at 80 ℃, stirring and reacting for 30 minutes, adjusting the pH value to 2-3, keeping the temperature at 80 ℃, stirring and reacting for 2 hours to fully form particles, and obtaining a lithium phosphate synthetic solution;
step 3, dehydrating and drying lithium phosphate
3.1, pumping the lithium phosphate synthetic solution into a plate-and-frame filter press, performing filter pressing by adopting 2000-mesh filter cloth, washing with water until the pH value is 5-6, and obtaining a lithium phosphate filter cake, wherein the mass fraction of the central control chloride ions is less than 0.02%;
3.2, placing the lithium phosphate filter cake into a ceramic dish, paving the lithium phosphate filter cake and performing gradient drying;
drying for 2 hours at the first gradient of 300 ℃;
drying for 2 hours at 600 ℃ in a second gradient manner to obtain a target product, wherein the product is qualified as lithium phosphate by XRD (X-ray diffraction), as shown in figure 1; the product is measured by a quinmolybdic citraconic ketone mixed liquid method to obtain P 2 O 5 The content is 61.2%; through Agilent 5110-ICP-OES detection, the obtained product has less than 0.5ppm of cobalt, nickel, titanium, vanadium, chromium, cadmium, copper and lead and 0.85ppm of iron, and the indexes meet the requirements. Specific assay analysis results are shown in table 3:
table 3:
example 4
This example prepares high purity lithium phosphate by the following procedure
Step 1.1, adding analytically pure hydrochloric acid into a reaction kettle, adding high-purity water to dilute until the mass fraction is 23%, adding lithium carbonate into the reaction kettle, wherein the molar ratio of the hydrochloric acid to the lithium carbonate is 2:1, heating to 90 ℃, stirring and reacting for 50 minutes, dissolving to be transparent, adding high-purity water to dilute until the specific gravity is 1.08, adding metastannic acid into the reaction kettle in a proportion of 1/600 of the mass of the lithium carbonate, simultaneously adding hydrochloric acid with the mass fraction of 2-3.5%, fully stirring for 30 minutes, settling for 8 hours, and collecting supernatant;
step 1.2, enabling the supernatant collected in the step 1.1 to pass through a 1-micron filter element, and controlling the content of iron, cobalt, nickel, copper, cadmium, chromium, vanadium and other elements to be less than 0.1ppm to obtain a pure lithium chloride solution;
step 2, lithium phosphate synthesis
Step 2.1, adding food-grade phosphoric acid (the mass fraction is 85%) into high-purity water to be diluted to the mass fraction of 15% (the mass fractions of elements such as iron, cobalt, nickel, copper, cadmium, chromium, vanadium and the like are all less than 0.3 ppm), adding the diluted solution into the lithium chloride solution obtained in the step 1.2, stirring and heating up to 70 ℃ for reaction to obtain a synthetic solution;
step 2.2, controlling the content of iron, cobalt, nickel, copper, cadmium, chromium, vanadium and other elements in the reagent-grade ammonia water to be less than 0.1ppm, diluting the reagent-grade ammonia water to the mass fraction of 12%, slowly adding the diluted reagent-grade ammonia water into the synthetic solution obtained in the step 2.1, keeping the temperature at 85 ℃, stirring and reacting for 40 minutes, adjusting the pH value to 2-3, keeping the temperature at 85 ℃, stirring and reacting for 2 hours to fully form particles, and obtaining a lithium phosphate synthetic solution;
step 3, dehydrating and drying lithium phosphate
3.1, pumping the lithium phosphate synthetic solution into a plate-and-frame filter press, performing filter pressing by adopting 2000-mesh filter cloth, washing with water until the pH value is 5-6, and obtaining a lithium phosphate filter cake, wherein the mass fraction of the central control chloride ions is less than 0.02%;
step 3.2, placing the lithium phosphate filter cake into a ceramic dish, paving and carrying out gradient drying;
drying for 3 hours at the first gradient of 300 ℃;
drying at 600 ℃ for 3 hours in a second gradient manner to obtain a target product, wherein the product is characterized as lithium phosphate by XRD (X-ray diffraction), as shown in figure 1; the product is measured by a quinmolybdic citraconic ketone mixed liquid method to obtain P 2 O 5 The content is 61.4%; and detecting by Agilent 5110-ICP-OES to obtain products with less than 0.5ppm of cobalt, nickel, titanium, vanadium, chromium, cadmium, copper and lead and 0.83ppm of iron, wherein the indexes meet the requirements. Specific assay analysis results are shown in table 4:
table 4:
example 5
This example prepares high purity lithium phosphate by the following procedure
Step 1.1, adding analytically pure hydrochloric acid into a reaction kettle, adding high-purity water to dilute until the mass fraction is 22%, adding lithium carbonate into the reaction kettle, wherein the molar ratio of the hydrochloric acid to the lithium carbonate is 2:1, heating to 85 ℃, stirring and reacting for 40 minutes, dissolving to be transparent, adding high-purity water to dilute until the specific gravity is 1.1, adding metastannic acid into the reaction kettle in a proportion of 1/900 of the mass of the lithium carbonate, simultaneously adding hydrochloric acid with the mass fraction of 2-3.5%, fully stirring for 30 minutes, settling for 8 hours, and collecting supernatant;
step 1.2, enabling the supernatant collected in the step 1.1 to pass through a 1-micron filter element, and controlling the content of iron, cobalt, nickel, copper, cadmium, chromium, vanadium and other elements to be less than 0.1ppm to obtain a pure lithium chloride solution;
step 2, lithium phosphate synthesis
Step 2.1, adding pure water into food-grade phosphoric acid (the mass fraction is 85%) to be diluted to 13% (the mass fraction of elements such as iron, cobalt, nickel, copper, cadmium, chromium, vanadium and the like are all less than 0.3 ppm), adding the diluted solution into the lithium chloride solution obtained in the step 1.2, stirring and heating to 75 ℃ for reaction to obtain a synthetic solution;
step 2.2, controlling the content of iron, cobalt, nickel, copper, cadmium, chromium, vanadium and other elements in the reagent-grade ammonia water to be less than 0.1ppm, diluting the reagent-grade ammonia water to the mass fraction of 12%, slowly adding the reagent-grade ammonia water into the synthetic solution obtained in the step 2.1, keeping the temperature at 85 ℃, stirring and reacting for 40 minutes, adjusting the pH value to 2-3, keeping the temperature at 85 ℃, stirring and reacting for 3 hours to fully form particles, and obtaining a lithium phosphate synthetic solution;
step 3, dehydrating and drying lithium phosphate
3.1, pumping the lithium phosphate synthetic solution into a plate-and-frame filter press, performing filter pressing by adopting 2000-mesh filter cloth, washing with water until the pH value is 5-6, and obtaining a lithium phosphate filter cake, wherein the mass fraction of the central control chloride ions is less than 0.02%;
3.2, placing the lithium phosphate filter cake into a ceramic dish, paving the lithium phosphate filter cake and performing gradient drying;
drying for 2.5 hours at a first gradient of 280 ℃;
drying at 550 ℃ of the second gradient for 2.5 hours to obtain a target product, and determining the product as lithium phosphate by XRD (X-ray diffraction), as shown in figure 1; the product is measured by a quinmolybdic citraconic ketone mixed liquid method to obtain P 2 O 5 The content is 61.3%; obtained by detecting Agilent 5110-ICP-OESThe cobalt, nickel, titanium, vanadium, chromium, cadmium, copper and lead in the product are all less than 0.5ppm, and the iron content is 0.86ppm, so that the indexes meet the requirements. Specific assay analysis results are shown in table 5:
table 5:
through the five examples, the preparation method of the high-purity optical glass additive lithium phosphate provided by the invention is very stable, and the product index meets the requirement. The high-purity lithium phosphate prepared by the method can be used for preparing optical glass with special optical property and refractive index.
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications or substitutions can be easily made by those skilled in the art within the technical scope of the present disclosure.
Claims (9)
1. A preparation method of high-purity lithium phosphate is characterized by comprising the following steps:
step 1, lithium salt purification
Step 1.1, diluting analytically pure hydrochloric acid by adopting high-purity water until the mass fraction is 20-23%, adding lithium carbonate, heating and stirring for reaction to dissolve the lithium carbonate to be transparent, and diluting by adding high-purity water until the specific gravity is 1.08-1.1;
step 1.2, adding 2-3.5% by mass of hydrochloric acid into the solution obtained in the step 1.1 while adding metastannic acid, fully stirring, settling, and collecting supernatant;
step 1.3, filtering the supernatant obtained in the step 1.2, wherein the central control metal impurity elements are less than 0.1ppm, so as to obtain a pure lithium chloride solution;
step 2, synthesizing lithium phosphate
Step 2.1, adding high-purity water to dilute the food-grade superior phosphoric acid product until the mass fraction is 10-15% and adding the diluted product into the lithium chloride solution obtained in the step 1, stirring and heating the solution for reaction to obtain a synthetic solution, wherein the controlled metal impurity elements in the food-grade superior phosphoric acid product are less than 0.3 ppm;
step 2.2, controlling the content of metal impurity elements in the reagent-grade ammonia water to be less than 0.1ppm, diluting the reagent-grade ammonia water until the mass fraction is 10-12%, slowly adding the reagent-grade ammonia water into the synthetic liquid obtained in the step 2.1, keeping the temperature at 80-85 ℃, stirring and reacting for 30-40 minutes, adjusting the pH value to 2-3, keeping the temperature at 80-85 ℃, stirring and reacting for 2-3 hours, and obtaining a lithium phosphate synthetic liquid;
step 3, dehydrating and drying lithium phosphate
3.1, carrying out filter pressing on the lithium phosphate synthetic solution obtained in the step 2, washing with water until the pH value is 5-6, and obtaining a lithium phosphate filter cake, wherein the mass fraction of chloride ions in the medium control mother solution is less than 0.02%;
step 3.2, performing gradient drying on the lithium phosphate filter cake obtained in the step 3.1, wherein the specific drying process is as follows:
drying for 2-3 hours at the first gradient of 200-300 ℃;
and drying the second gradient at 500-600 ℃ for 2-3 hours to obtain the high-purity lithium phosphate.
2. The method for preparing high-purity lithium phosphate according to claim 1, wherein the step 1.1 comprises:
adding analytically pure hydrochloric acid into a reaction kettle, diluting the hydrochloric acid by adopting high-purity water until the mass fraction is 20-23%, adding lithium carbonate into the hydrochloric acid, heating to 80-90 ℃, stirring and reacting for 30-60 minutes to dissolve the lithium carbonate until the lithium carbonate is transparent, and diluting the lithium carbonate by adding high-purity water until the specific gravity is 1.08-1.1.
3. The method for preparing high-purity lithium phosphate according to claim 2, wherein the step 1.2 is specifically as follows:
adding 2-3.5% hydrochloric acid by mass while adding metastannic acid into the solution obtained in the step 1.1, fully stirring for at least 30 minutes, settling for at least 8 hours, and collecting supernatant;
wherein the addition amount of the metastannic acid is 1/500-1/1000 of the mass of the lithium carbonate.
4. The method for producing high-purity lithium phosphate according to claim 3, wherein:
in step 1.3, the supernatant obtained in step 1.2 is filtered using a 1 micron filter cartridge.
5. The method for producing high-purity lithium phosphate according to claim 4, wherein:
in step 2.1, the temperature is raised to 70-80 ℃.
6. The method for preparing high-purity lithium phosphate according to claim 5, wherein the step 3.1 comprises:
and (3) pumping the lithium phosphate synthetic solution obtained in the step (2) into a plate-and-frame filter press, performing filter pressing by using filter cloth with the mesh size of more than 2000, washing with water until the pH value is 5-6, and obtaining a lithium phosphate filter cake, wherein the mass fraction of chloride ions in the central control mother solution is less than 0.02%.
7. The method for producing high-purity lithium phosphate according to claim 6, wherein:
and 3.2, a ceramic plate is adopted to contain the lithium phosphate filter cake obtained in the step 3.1 for drying.
8. A high-purity lithium phosphate is characterized in that: prepared by the preparation method of any one of claims 1 to 7.
9. An optical glass characterized in that: adding high-purity lithium phosphate obtained by the preparation method of any one of claims 1 to 7.
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