CN110902710A - Preparation method of high-purity ytterbium fluoride optical glass additive - Google Patents
Preparation method of high-purity ytterbium fluoride optical glass additive Download PDFInfo
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Abstract
In order to solve the technical problem that the purity and the content of metal ion elements of ytterbium fluoride prepared by the existing method can not meet the requirements of a high-performance fluoride optical glass additive, the invention provides a preparation method of ytterbium fluoride serving as a high-purity optical glass additive, which comprises the following steps: 1. synthesizing and purifying ytterbium nitrate; 2. concentrating to prepare ytterbium nitrate crystal; 3. preparing ytterbium carbonate; 4. synthesizing ytterbium fluoride; 5. removing carbon dioxide; 6. and (5) roasting ytterbium fluoride. The invention roasts the ytterbium fluoride filter cake through special gradient temperature, so that the ignition weight loss of the ytterbium fluoride is 0.07-0.2%, and the purity of the prepared ytterbium fluoride can reach 99.90-99.95%. According to the invention, ytterbium nitrate and sodium carbonate are purified, so that metal ion elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb contained in ytterbium nitrate are all less than 0.3ppm, and Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the finally prepared ytterbium fluoride are all less than 1 ppm.
Description
Technical Field
The invention relates to ytterbium fluoride (YbF)3) In particular to a method for preparing the product with purity higher than99.9 percent, and the metallic ion element impurities of Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb are all less than 1ppm, and the preparation method is applied to the fluoride special optical glass material and used as the optical glass additive.
Background
At present, the demand of fluoride optical glass materials is increasing year by year, and the fluoride optical glass materials are mainly applied to the fields of optical fiber communication, medicine and the like. Fluoride optical glasses are composed mainly of alkaline earth metal fluorides and rare earth fluorides. The addition of ytterbium fluoride to the fluoride glass enables the fluoride glass to have excellent near infrared and special optical properties.
In addition, in the technical index requirements of fluoride optical glass, the purity of ytterbium fluoride added into the optical glass and the contents of metal ion elements of Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the optical glass are very strict. However, the purity of ytterbium fluoride prepared by the existing method is generally 98.5-99%, and the content of metal ion elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the ytterbium fluoride is 50-100ppm, which can affect the parameters of optical glass such as dispersion and transmittance, and thus can not meet the requirements of high-performance optical fluoride glass additives.
Disclosure of Invention
In order to solve the technical problem that the purity and the content of metal ion elements of ytterbium fluoride prepared by the existing method cannot meet the requirements of a high-performance fluoride optical glass additive, the invention provides a preparation method of the ytterbium fluoride high-purity optical glass additive.
The technical scheme of the invention is as follows:
the preparation method of the high-purity ytterbium fluoride optical glass additive is characterized by comprising the following steps of:
step 1, synthesizing and purifying ytterbium nitrate:
1.1) uniformly mixing the rare earth ytterbium oxide and deionized water according to the weight ratio of 3-4:8-10, gradually adding nitric acid, keeping the whole reaction temperature at 70-80 ℃, and obtaining a ytterbium nitrate solution, wherein the pH value at the end of the reaction is 2.5-3;
1.2) adding deionized water into the ytterbium nitrate solution, flushing the diluted ytterbium nitrate solution until the specific gravity is 1.15-1.2, heating to 100-105 ℃, preserving the heat for 2-3 hours, removing the head, and filtering into another container;
1.3) adding ytterbium hydroxide into the ytterbium nitrate filtrate obtained in the step 1.2), adjusting the pH value of the solution to 3-3.5, then adding a metastannic acid solution with the concentration of 5-7%, uniformly stirring, heating to 100-105 ℃, keeping the temperature for 30-60 minutes, removing the head, filtering, and putting into another container to obtain ytterbium nitrate filtrate; the volume ratio of the metastannic acid solution to the ytterbium nitrate filtering liquid is 0.5-0.7: 1000, parts by weight;
1.4) sampling from the ytterbium nitrate filtrate, carrying out ICP detection on the contents of metal elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the solution, and if the contents are less than 0.3ppm, indicating that the ytterbium nitrate filtrate obtained in the step 1.3) meets the subsequent preparation requirements, and entering the step 2; if the content of any element in the metal elements is more than or equal to 0.3ppm, returning to the step 1.3);
and step 2, concentrating to prepare ytterbium nitrate crystals:
2.1) heating and concentrating ytterbium nitrate filtrate qualified in ICP detection until the specific gravity is 1.50-1.55, and cooling the ytterbium nitrate filtrate in a cooling container to room temperature to obtain ytterbium nitrate crystals;
2.2) fishing out the ytterbium nitrate crystal, putting the ytterbium nitrate crystal into a centrifugal machine for liquid-solid separation, and washing off nitrate ions on the surface of the ytterbium nitrate crystal by using deionized water to be below 30ppm in the liquid-solid separation process; centrifuging and throwing for 30 minutes or more, and taking out ytterbium nitrate crystals;
step 3, preparing ytterbium carbonate:
3.1) placing the ytterbium nitrate crystal obtained in the step 2.2) into a container, adding deionized water to dissolve the ytterbium nitrate crystal into a ytterbium nitrate solution with the specific gravity of 1.05-1.10 for later use;
3.2) purification of sodium carbonate:
3.2.1) putting industrial sodium carbonate into another container, adding deionized water at the temperature of 80-90 ℃, and fully dissolving until the specific gravity is 1.1-1.15 to obtain a sodium carbonate solution;
3.2.2) cooling the sodium carbonate solution to below 30 ℃, adding a trace amount of hydrogen peroxide, uniformly stirring, and standing for 30 minutes or more;
3.2.3) adding a sodium sulfide solution with the concentration of 1.5-3% into the solution obtained in the step 3.2.2), fully stirring, heating to 90-95 ℃, preserving heat for 2 hours, removing the head, filtering and putting into another container to obtain a purified sodium carbonate filtrate; the volume ratio of the sodium sulfide solution to the sodium carbonate solution obtained in the step 3.2.2) is 0.8-1: 1000, parts by weight; the volume ratio of the sodium sulfide solution to the sodium carbonate solution obtained in the step 3.2.2) is 1: 1000, parts by weight;
3.2.4) sampling from the sodium carbonate filtrate, detecting the contents of metallic elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the solution by ICP (inductively coupled plasma), and if the contents are less than 0.3ppm, indicating that the sodium carbonate filtrate obtained in the step 3.2.3) is qualified in purification, meeting the subsequent preparation requirements, and entering the step 3.3); if the content of Fe in the metal element is less than 0.3ppm and the content of any other element is more than or equal to 0.3ppm, returning to the step 3.2.3); if the Fe content in the metal element is more than or equal to 0.3ppm, returning to the step 3.2.2);
3.3) synthesizing ytterbium carbonate by using the ytterbium nitrate solution obtained in the step 3.1) and the sodium carbonate filtrate obtained in the step 3.2.4) and purifying to obtain qualified sodium carbonate filtrate, and preparing a ytterbium carbonate filter cake;
step 4, ytterbium fluoride synthesis:
4.1) adding high-purity hydrofluoric acid with the concentration of 45-65% into a polytetrafluoroethylene reaction kettle, adding deionized water, and stirring uniformly to prepare high-purity hydrofluoric acid with the concentration of 30-35%;
4.2) adding water into the ytterbium carbonate filter cake, stirring the ytterbium carbonate filter cake into paste with the solid content of 25-35%, heating the paste to 45-50 ℃, slowly adding the ytterbium carbonate paste into the high-purity hydrofluoric acid obtained in the step 4.1), and obtaining ytterbium fluoride precipitate, wherein the pH value of the synthesis reaction end point is 1-2;
step 5, removing carbon dioxide:
adding deionized water into the ytterbium fluoride precipitate synthesized in the step 4.2), stirring into paste with the solid content of 35-40%, heating to 90-110 ℃, and keeping the temperature for 2-3 hours to completely remove carbon dioxide; testing the pH value of the reactant during the heat preservation period, and if the pH value is not 1-2, supplementing high-purity hydrofluoric acid with the concentration of 30-35% for adjustment to keep the pH value at 1-2;
step 6, roasting ytterbium fluoride:
6.1) sending the ytterbium fluoride after removing the carbon dioxide in the step 5 into a plate-and-frame filter press for filter pressing, washing until chloride ions and sulfate ions in the ytterbium fluoride are less than 20ppm, pressing and drying to form a ytterbium fluoride filter cake, and taking out;
6.2) putting the taken out ytterbium fluoride filter cake into a ceramic crucible, and roasting at a gradient temperature rise to obtain a final ytterbium fluoride product; the gradient temperature-rising roasting specifically comprises the following steps:
the first stage is as follows: heating to 110-120 deg.c, roasting for 1.5-3 hr to eliminate ytterbium fluoride surface water;
and a second stage: heating to 450 ℃ and 500 ℃, and roasting for 1.5-3 hours to remove the crystal water of the ytterbium fluoride;
and a third stage: heating to 600-700 ℃, roasting for 1.5-3 hours, and removing the ytterbium fluoride structural water;
a fourth stage: the temperature is raised to 750 ℃ and 800 ℃, and the temperature is reduced to room temperature after roasting for 2 to 3 hours, thus obtaining the roasted final ytterbium fluoride product.
Further, in step 4.2):
and adding a little ytterbium carbonate paste into the high-purity hydrofluoric acid, stopping adding the ytterbium carbonate paste, slowly adding the ytterbium carbonate paste after large-particle ytterbium fluoride fine seeds are formed, and controlling the pH value at the end point of the synthesis reaction to be 1-2.
Further, in step 4.2): the pH value at the end of the synthesis reaction is 1.
Further, the volume ratio of the sodium carbonate to the hydrogen peroxide in the step 3.2.2) is 1000-1500: 1-1.5.
Further, 3.3) the method for synthesizing the ytterbium carbonate and preparing the ytterbium carbonate filter cake comprises the following specific steps:
3.3.1) adding ytterbium nitrate solution with the specific gravity of 1.05-1.10 into the reaction container, and slowly adding sodium carbonate filtrate qualified in the step 3.2.4) under the stirring state to generate ytterbium carbonate precipitate;
3.3.2) washing the ytterbium carbonate precipitate by a plate-and-frame filter press until nitrate ions and sodium ions are both less than 30ppm, and pressing to dry to obtain a ytterbium carbonate filter cake.
Further, the concentration of metastannic acid in step 1.3) is 4% or 6%.
Further, the concentration of the sodium sulfide solution in step 3.2.3) is 2%.
Further, in step 5, the temperature was raised to 105 ℃ and maintained at 1.5 pH for 2.5 hours.
Further, the gradient temperature-rising roasting in the step 6.2) specifically comprises the following steps:
the first stage is as follows: heating to 115 ℃, and roasting for 3 hours to separate the surface water of the ytterbium fluoride;
and a second stage: heating to 480 ℃, and roasting for 2 hours to remove the crystal water of ytterbium fluoride;
and a third stage: heating to 660 ℃, and roasting for 2 hours to remove ytterbium fluoride structural water;
a fourth stage: and raising the temperature to 785 ℃, roasting for 3 hours, and then reducing the temperature to room temperature to obtain a roasted final ytterbium fluoride product.
The invention has the advantages that:
1. the invention roasts the ytterbium fluoride filter cake through special gradient temperature, so that the ignition weight loss of the ytterbium fluoride is 0.07-0.2%, and the purity of the prepared ytterbium fluoride can reach 99.90-99.95%.
2. According to the invention, ytterbium nitrate and sodium carbonate are purified, so that metal ion elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb contained in ytterbium nitrate are all less than 0.3ppm, and Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the finally prepared ytterbium fluoride are all less than 1 ppm.
3. According to the invention, before the ytterbium fluoride is roasted, carbon dioxide in the ytterbium fluoride precipitate is removed, so that a byproduct of ytterbium carbonate is prevented from being generated subsequently, and the purity of the final ytterbium fluoride product is ensured.
4. According to the invention, the specific roasting temperature and roasting time are selected when the ytterbium fluoride filter cake is roasted at the first stage, so that the surface water of ytterbium fluoride is completely removed, the condition that the surface water is not completely removed to generate ytterbium oxyfluoride byproducts is avoided, and the purity of ytterbium fluoride products is ensured.
Detailed Description
The principle of the invention is as follows: ytterbium oxide (Yb)2O3) With nitric acid (HNO)3) Ytterbium nitrate (Yb (NO) is generated by reaction3)3) And ytterbium nitrate (Yb (NO) is added3)3) With sodium carbonate (Na)2CO3) The reaction produces ytterbium carbonate (Yb)2(CO3)3) Finally ytterbium carbonate (Yb)2(CO3)3) YbF (YbF) synthesis with high purity hydrofluoric acid (HF)3)。
The chemical reaction formula is as follows:
Yb2O3+6HNO3→2Yb(NO3)3+3H2O
2Yb(NO3)3+3Na2CO3→Yb2(CO3)3+6NaNO3
Yb2(CO3)3+6HF→2YbF3+3CO2↑+3H2O
example 1:
the preparation method of the high-purity optical glass additive ytterbium fluoride comprises the following steps:
step 1, synthesizing and purifying ytterbium nitrate:
1.1) uniformly mixing the rare earth ytterbium oxide and deionized water according to the weight ratio of 3:10, adding nitric acid in batches, keeping the whole reaction temperature at 70 ℃, and obtaining ytterbium nitrate solution, wherein the pH value of the reaction end point is 2.5; in the whole reaction process, the reactant should be kept clear and transparent, namely certain acidity is kept in the reaction process, and if the reactant is not clear and transparent, the nitric acid is supplemented to ensure that the reactant is clear and transparent;
1.2) adding deionized water into the ytterbium nitrate solution, flushing diluted ytterbium nitrate solution until the specific gravity is 1.15, heating to 105 ℃, preserving heat for 3 hours, removing the head, filtering and putting into another container;
1.3) adding ytterbium hydroxide into the ytterbium nitrate filtrate obtained in the step 1.2), adjusting the pH value of the solution to 3.5, then adding a 6% metastannic acid solution, uniformly stirring, heating to 105 ℃, keeping the temperature for 30 minutes, removing the head, filtering and putting into another container to obtain ytterbium nitrate filtrate; the volume ratio of the metastannic acid solution to the ytterbium nitrate filtrate is 0.5: 1000, parts by weight;
1.4) sampling from the ytterbium nitrate filtrate, detecting the contents of metallic elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in a sample solution through ICP (inductively coupled plasma mass spectrometer), and if the contents are less than 0.3ppm, indicating that the ytterbium nitrate filtrate obtained in the step 1.3) is qualified in purification, meeting the subsequent preparation requirements, and entering the step 2; if the content of any one element in the metal elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb is more than or equal to 0.3ppm, returning to the step 1.3);
and step 2, concentrating to prepare ytterbium nitrate crystals:
2.1) heating and concentrating ytterbium nitrate filtrate qualified by ICP detection until the specific gravity is 1.50, and cooling the ytterbium nitrate filtrate in a cooling container to room temperature to obtain ytterbium nitrate crystals;
2.2) fishing out the ytterbium nitrate crystal, putting the ytterbium nitrate crystal into a centrifugal machine with the capacity of 60L for liquid-solid separation, washing 5L-10L of ionized water during throwing, and washing off nitrate ions on the surface of the ytterbium nitrate crystal to be below 30 ppm; centrifuging and throwing for 30 minutes, and taking out ytterbium nitrate crystals;
step 3, preparing ytterbium carbonate:
3.1) placing the ytterbium nitrate crystal obtained in the step 2.2) into a container, adding deionized water to dissolve until the specific gravity is 1.10 for later use;
3.2) purification of sodium carbonate:
3.2.1) putting industrial sodium carbonate into another container, adding deionized water with the temperature of 90 ℃, and fully dissolving until the specific gravity is 1.1 to obtain a sodium carbonate solution;
3.2.2) cooling the sodium carbonate solution to below 30 ℃, adding a trace amount of hydrogen peroxide (the volume ratio of hydrogen peroxide to sodium carbonate solution is 1: 1000-1200), and standing for 30 minutes; the purpose of adding hydrogen peroxide is to oxidize ferrous ions in the sodium carbonate solution into ferric ions;
3.2.3) adding a sodium sulfide solution with the concentration of 2% into the solution obtained in the step 3.2.2), fully stirring, heating to 90 ℃, preserving the temperature for 2 hours, converting metal elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the solution into sulfide precipitates, removing the head, filtering and putting into another container to obtain a purified sodium carbonate filtrate; the volume ratio of the sodium sulfide solution to the sodium carbonate solution obtained in the step 3.2.2) is 0.8: 1000, parts by weight;
3.2.4) sampling from the sodium carbonate filtrate, detecting the contents of metallic elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the solution by ICP (inductively coupled plasma), and if the contents are less than 0.3ppm, indicating that the sodium carbonate filtrate obtained in the step 3.2.3) is qualified in purification, meeting the subsequent preparation requirements, and entering the step 3.3); if the Fe content is less than 0.3ppm and the content of any element of Cu, Ni, Cr, Co, Mn, Ti, V and Pb is more than or equal to 0.3ppm, returning to the step 3.2.3); if the Fe content is more than or equal to 0.5ppm, returning to the step 3.2.2);
3.3) synthesizing ytterbium carbonate and preparing a ytterbium carbonate filter cake:
3.3.1) adding ytterbium nitrate solution with the specific gravity of 1.10 into the enamel reaction vessel, and slowly adding sodium carbonate filtrate which is qualified in the step 3.2.4) in a stirring state to generate ytterbium carbonate precipitate; the enamel reaction vessel is adopted, so as to prevent metallic element impurities in the vessel from being introduced into reactants;
3.3.2) washing the ytterbium carbonate precipitate by a plate-and-frame filter press until nitrate ions and sodium ions are both less than 30ppm, and pressing to dry to obtain a ytterbium carbonate filter cake;
step 4, ytterbium fluoride synthesis:
4.1) adding high-purity hydrofluoric acid with the concentration of 65% into a polytetrafluoroethylene reaction kettle, adding deionized water, stirring uniformly, and preparing high-purity hydrofluoric acid with the concentration of 35%; the high-purity hydrofluoric acid is hydrofluoric acid with the contents of metallic element impurities of Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb less than 0.3 ppm;
4.2) adding water into the ytterbium carbonate filter cake, stirring the mixture into paste with the solid content of 35%, heating the paste to 45 ℃, adding a small amount of ytterbium carbonate paste into the high-purity hydrofluoric acid obtained in the step 4.1), stopping adding the ytterbium carbonate paste, slowly adding the ytterbium carbonate paste after large-particle ytterbium fluoride fine seeds are formed, and obtaining ytterbium fluoride precipitate with the pH value of the synthesis reaction end point of 1-2; in practice, high-purity hydrofluoric acid can also be slowly added into the ytterbium carbonate paste, but the adding sequence is not beneficial to the carbon dioxide crown emission, so that the time for completely removing the carbon dioxide in the step 5 is prolonged, and the preparation efficiency is influenced; the volume ratio of the ytterbium carbonate paste to the high-purity hydrofluoric acid is 2: 8;
step 5, removing carbon dioxide:
adding deionized water into the ytterbium fluoride precipitate synthesized in the step 4.2), stirring into paste with the solid content of 40%, heating to 105 ℃, keeping the temperature for 2.5 hours, and completely removing carbon dioxide (if the carbon dioxide cannot be completely removed, the purity of the final ytterbium fluoride finished product is influenced); testing the pH value of the reactant during the heat preservation period, and if the pH value is not 1-1.5, supplementing high-purity hydrofluoric acid with the concentration of 35% for adjustment to keep the pH value at 1-1.5;
step 6, roasting ytterbium fluoride:
6.1) sending the ytterbium fluoride after removing the carbon dioxide in the step 5 into a plate-and-frame filter press for filter pressing, washing until chloride ions and sulfate ions in the ytterbium fluoride are less than 20ppm, pressing and drying to form a ytterbium fluoride filter cake, and taking out;
6.2) putting the taken out ytterbium fluoride filter cake into a ceramic crucible, and roasting at a gradient temperature rise to obtain a final ytterbium fluoride product; the gradient temperature-rising roasting specifically comprises the following steps:
the first stage is as follows: heating to 115 ℃, and roasting for 3 hours to separate the surface water of the ytterbium fluoride;
and a second stage: heating to 480 ℃, and roasting for 2 hours to remove the crystal water of ytterbium fluoride;
and a third stage: heating to 660 ℃, and roasting for 2 hours to remove ytterbium fluoride structural water;
a fourth stage: and raising the temperature to 785 ℃, roasting for 3 hours, and then reducing the temperature to room temperature to obtain a roasted final ytterbium fluoride product.
Example 2:
the preparation method of the high-purity optical glass additive ytterbium fluoride comprises the following steps:
step 1, synthesizing and purifying ytterbium nitrate:
1.1) uniformly mixing the rare earth ytterbium oxide and deionized water according to the weight ratio of 4:8, adding nitric acid in batches, keeping the whole reaction temperature at 80 ℃, and obtaining ytterbium nitrate solution, wherein the pH value at the end point of the reaction is 3; in the whole reaction process, the reactant should be kept clear and transparent, namely certain acidity is kept in the reaction process, and if the reactant is not clear and transparent, nitric acid is supplemented to ensure that the reactant is clear and transparent;
1.2) adding deionized water into the ytterbium nitrate solution, flushing diluted ytterbium nitrate solution until the specific gravity is 1.2, heating to 100 ℃, preserving heat for 3 hours, removing the head, filtering and putting into another container;
1.3) adding ytterbium hydroxide into the ytterbium nitrate filtrate obtained in the step 1.2), adjusting the pH value of the solution to 3, then adding a 4% metastannic acid solution, uniformly stirring, heating to 100 ℃, keeping the temperature for 45 minutes, removing the head, filtering and putting into another container to obtain ytterbium nitrate filtrate; the volume ratio of the metastannic acid solution to the ytterbium nitrate filtrate is 0.7: 1000, parts by weight;
1.4) sampling the ytterbium nitrate filtrate, detecting the contents of metallic elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the solution by ICP (inductively coupled plasma), and if the contents are less than 0.3ppm, indicating that the ytterbium nitrate filtrate obtained in the step 1.3) is qualified in purification, meeting the subsequent preparation requirement, and entering the step 2; if the content of any one element in the metal elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb is more than or equal to 0.3ppm, returning to the step 1.3);
and step 2, concentrating to prepare ytterbium nitrate crystals:
2.1) heating and concentrating ytterbium nitrate filtrate qualified by ICP detection until the specific gravity is 1.55, and cooling the ytterbium nitrate filtrate in a cooling container to room temperature to obtain ytterbium nitrate crystals;
2.2) fishing out the ytterbium nitrate crystal, putting the ytterbium nitrate crystal into a 120L centrifuge with the capacity of 100-; centrifuging and throwing for 45 minutes, and taking out ytterbium nitrate crystals;
step 3, preparing ytterbium carbonate:
3.1) placing the ytterbium nitrate crystal obtained in the step 2.2) into a container, adding deionized water to dissolve the ytterbium nitrate crystal into a ytterbium nitrate solution with the specific gravity of 1.05 for later use;
3.2) purification of sodium carbonate:
3.2.1) putting industrial sodium carbonate into another container, adding deionized water with the temperature of 80 ℃, and fully dissolving until the specific gravity is 1.15 to obtain a sodium carbonate solution;
3.2.2) cooling the sodium carbonate solution to below 30 ℃, adding a trace amount of hydrogen peroxide (the volume ratio of hydrogen peroxide to sodium carbonate solution is 1.5: 1000-1500) and standing for 45 minutes after uniformly stirring;
3.2.3) adding a sodium sulfide solution with the concentration of 3% into the solution obtained in the step 3.2.2), fully stirring, heating to 95 ℃, preserving the temperature for 2 hours, converting metal elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the solution into sulfide precipitates, removing the head, filtering and putting into another container to obtain a purified sodium carbonate filtrate; the volume ratio of the sodium sulfide solution to the sodium carbonate solution obtained in the step 3.2.2) is 1: 1000, parts by weight;
3.2.4) sampling from the sodium carbonate filtrate, detecting the contents of metallic elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the solution by ICP (inductively coupled plasma), and if the contents are less than 0.3ppm, indicating that the sodium carbonate filtrate obtained in the step 3.2.3) is qualified in purification, meeting the subsequent preparation requirements, and entering the step 3.3); if the Fe content is less than 0.3ppm and the content of any element of Cu, Ni, Cr, Co, Mn, Ti, V and Pb is more than or equal to 0.3ppm, returning to the step 3.2.3); if the Fe content is more than or equal to 0.3ppm, returning to the step 3.2.2);
3.3) synthesizing ytterbium carbonate and preparing a ytterbium carbonate filter cake:
3.3.1) adding ytterbium nitrate solution with the specific gravity of 1.05 into the enamel reaction vessel, and slowly adding sodium carbonate filtrate which is qualified in the step 3.2.4) in a stirring state to generate ytterbium carbonate precipitate;
3.3.2) washing the ytterbium carbonate precipitate by a plate-and-frame filter press until nitrate ions and sodium ions are both less than 30ppm, and pressing to dry to obtain a ytterbium carbonate filter cake;
step 4, ytterbium fluoride synthesis:
4.1) adding high-purity hydrofluoric acid with the concentration of 45% into a polytetrafluoroethylene reaction kettle, adding deionized water, stirring uniformly, and preparing high-purity hydrofluoric acid with the concentration of 35%; the high-purity hydrofluoric acid is hydrofluoric acid with the contents of metallic element impurities of Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb less than 0.3 ppm;
4.2) adding water into the ytterbium carbonate filter cake, stirring the mixture into paste with the solid content of 30%, heating the paste to 45 ℃, adding a little ytterbium carbonate paste into the high-purity hydrofluoric acid obtained in the step 4.1), stopping adding the ytterbium carbonate paste, slowly adding the ytterbium carbonate paste after large-particle ytterbium fluoride fine seeds are formed, and synthesizing the reaction end point with the PH value of 1 to obtain ytterbium fluoride precipitate; the volume ratio of the ytterbium carbonate paste to the high-purity hydrofluoric acid is 2: 8
Step 5, removing carbon dioxide:
adding deionized water into the ytterbium fluoride precipitate synthesized in the step 4.2), stirring into paste with the solid content of 35%, heating to 90 ℃, and keeping the temperature for 3 hours to completely remove carbon dioxide; during the heat preservation period, testing the pH value of the reactant, and if the pH value is not 2, supplementing high-purity hydrofluoric acid with the concentration of 35% for adjustment to keep the pH value at 2;
step 6, roasting ytterbium fluoride:
6.1) sending the ytterbium fluoride after removing the carbon dioxide in the step 5 into a plate-and-frame filter press for filter pressing, washing until chloride ions and sulfate ions in the ytterbium fluoride are less than 20ppm, pressing and drying to form a ytterbium fluoride filter cake, and taking out;
6.2) putting the taken out ytterbium fluoride filter cake into a ceramic crucible, and roasting at a gradient temperature rise to obtain a final ytterbium fluoride product; the gradient temperature-rising roasting specifically comprises the following steps:
the first stage is as follows: heating to 120 ℃, and roasting for 2 hours to separate the surface water of the ytterbium fluoride;
and a second stage: heating to 500 ℃, and roasting for 1.5 hours to remove the crystal water of ytterbium fluoride;
and a third stage: heating to 700 ℃, and roasting for 1.5 hours to remove ytterbium fluoride structural water;
a fourth stage: and raising the temperature to 800 ℃, roasting for 2 hours, and then reducing the temperature to room temperature to obtain a roasted final ytterbium fluoride product.
Example 3:
step 1, synthesizing and purifying ytterbium nitrate:
1.1) uniformly mixing the rare earth ytterbium oxide and deionized water according to the weight ratio of 3:9, adding nitric acid in batches, keeping the whole reaction temperature at 75 ℃, and obtaining ytterbium nitrate solution, wherein the pH value at the end point of the reaction is 3; in the whole reaction process, the reactant should be kept clear and transparent, namely certain acidity is kept in the reaction process, and if the reactant is not clear and transparent, the nitric acid is supplemented to ensure that the reactant is clear and transparent;
1.2) adding deionized water into the ytterbium nitrate solution, flushing diluted ytterbium nitrate solution until the specific gravity is 1.17, heating to 105 ℃, keeping the temperature for 2.5 hours, removing the head, filtering and putting into another container;
1.3) adding ytterbium hydroxide into the ytterbium nitrate filtrate obtained in the step 1.2), adjusting the pH value of the solution to 3, then adding a 5% metastannic acid solution, uniformly stirring, heating to 100 ℃, keeping the temperature for 60 minutes, removing the head, filtering and putting into another container to obtain ytterbium nitrate filtrate;
1.4) sampling the ytterbium nitrate filtrate, detecting the contents of metallic elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the solution by ICP (inductively coupled plasma), and if the contents are less than 0.3ppm, indicating that the ytterbium nitrate filtrate obtained in the step 1.3) meets the subsequent preparation requirement, and entering the step 2; if the content of any one element in the metal elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb is more than or equal to 0.3ppm, returning to the step 1.3);
and step 2, concentrating to prepare ytterbium nitrate crystals:
2.1) heating and concentrating ytterbium nitrate filtrate qualified by ICP detection until the specific gravity is 1.50, and cooling the ytterbium nitrate filtrate in a cooling container to room temperature to obtain ytterbium nitrate crystals;
2.2) fishing out the ytterbium nitrate crystal, putting the ytterbium nitrate crystal into a centrifugal machine for liquid-solid separation, and washing off nitrate ions on the surface of the ytterbium nitrate crystal by using deionized water to be below 30ppm in the liquid-solid separation process; centrifuging and throwing for 40 minutes, and taking out ytterbium nitrate crystals;
step 3, preparing ytterbium carbonate:
3.1) placing the ytterbium nitrate crystal obtained in the step 2.2) into a container, adding deionized water to dissolve the ytterbium nitrate crystal into a solution with the specific gravity of 1.10 for later use;
3.2) purification of sodium carbonate:
3.2.1) putting industrial sodium carbonate into another container, adding deionized water with the temperature of 85 ℃, and fully dissolving until the specific gravity is 1.15 to obtain a sodium carbonate solution;
3.2.2) cooling the sodium carbonate solution to below 30 ℃, adding a trace amount of hydrogen peroxide (the volume ratio of hydrogen peroxide to sodium carbonate solution is 1.5: 1000-1400) and standing for 30 minutes;
3.2.3) adding a sodium sulfide solution with the concentration of 1.5 percent into the solution obtained in the step 3.2.2), fully stirring, heating to 95 ℃, preserving the temperature for 2 hours, converting metal elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the solution into sulfide precipitates, removing the head, filtering and putting into another container to obtain a purified sodium carbonate filtrate; the volume ratio of the sodium sulfide solution to the sodium carbonate solution obtained in the step 3.2.2) is 0.9: 1000, parts by weight;
3.2.4) sampling from the sodium carbonate filtrate, detecting the contents of metallic elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the solution by ICP (inductively coupled plasma), and if the contents are less than 0.3ppm, indicating that the sodium carbonate filtrate obtained in the step 3.2.3) is qualified in purification, meeting the subsequent preparation requirements, and entering the step 3.3); if the Fe content is less than 0.3ppm and the content of any element of Cu, Ni, Cr, Co, Mn, Ti, V and Pb is more than or equal to 0.3ppm, returning to the step 3.2.3); if the Fe content is more than or equal to 0.3ppm, returning to the step 3.2.2);
3.3) synthesizing ytterbium carbonate and preparing a ytterbium carbonate filter cake:
3.3.1) adding ytterbium nitrate solution with the specific gravity of 1.10 into the enamel reaction vessel, and slowly adding sodium carbonate filtrate which is qualified in the step 3.2.4) in a stirring state to generate ytterbium carbonate precipitate;
3.3.2) washing the ytterbium carbonate precipitate by a plate-and-frame filter press until nitrate ions and sodium ions are both less than 30ppm, and pressing to dry to obtain a ytterbium carbonate filter cake;
step 4, ytterbium fluoride synthesis:
4.1) adding high-purity hydrofluoric acid with the concentration of 45% into a polytetrafluoroethylene reaction kettle, adding deionized water, stirring uniformly, and preparing high-purity hydrofluoric acid with the concentration of 35%; the high-purity hydrofluoric acid is hydrofluoric acid with the contents of metallic element impurities of Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb less than 0.3 ppm;
4.2) adding water into the ytterbium carbonate filter cake, stirring the mixture into paste with the solid content of 25%, heating the paste to 50 ℃, adding 2.5kg of ytterbium carbonate paste into the high-purity hydrofluoric acid obtained in the step 4.1), stopping adding the ytterbium carbonate paste, slowly adding the ytterbium carbonate paste after large-particle ytterbium fluoride fine seeds are formed, and obtaining ytterbium fluoride precipitate when the pH value at the synthesis reaction end is 2;
step 5, removing carbon dioxide:
adding deionized water into the ytterbium fluoride precipitate synthesized in the step 4.2), stirring into paste with the solid content of 40%, heating to 110 ℃, and keeping the temperature for 2 hours to completely remove carbon dioxide; during the heat preservation period, testing the pH value of the reactant, and if the pH value is not 1.5, supplementing high-purity hydrofluoric acid with the concentration of 35% for adjustment so as to keep the pH value at 1.5;
step 6, roasting ytterbium fluoride:
6.1) sending the ytterbium fluoride after removing the carbon dioxide in the step 5 into a plate-and-frame filter press for filter pressing, washing until chloride ions and sulfate ions in the ytterbium fluoride are less than 20ppm, pressing and drying to form a ytterbium fluoride filter cake, and taking out;
6.2) putting the taken ytterbium fluoride filter cake into a ceramic crucible, and heating and roasting according to the following four temperature gradients:
the first stage is as follows: heating to 110 ℃, and roasting for 3 hours to separate the surface water of the ytterbium fluoride;
and a second stage: heating to 450 ℃, and roasting for 3 hours to remove the crystal water of ytterbium fluoride;
and a third stage: heating to 600 ℃, and roasting for 3 hours to remove ytterbium fluoride structural water;
a fourth stage: and raising the temperature to 750 ℃, roasting for 3 hours, and then reducing the temperature to room temperature to obtain a roasted final ytterbium fluoride product.
The results of the detection of the ytterbium fluoride products prepared in examples 1 to 3 were as follows:
example 1:
the purity is 99.95 percent, and the contents of metallic element impurities such as Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb are all less than 1 ppm.
Example 2:
the purity is 99.90 percent, and the contents of metallic element impurities such as Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb are all less than 1 ppm.
Example 3:
the purity is 99.90 percent, and the contents of metallic element impurities such as Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb are all less than 1 ppm.
Claims (9)
1. A preparation method of ytterbium fluoride as a high-purity optical glass additive is characterized by comprising the following steps:
step 1, synthesizing and purifying ytterbium nitrate:
1.1) uniformly mixing the rare earth ytterbium oxide and deionized water according to the weight ratio of 3-4:8-10, gradually adding nitric acid, keeping the whole reaction temperature at 70-80 ℃, and obtaining a ytterbium nitrate solution, wherein the pH value at the end of the reaction is 2.5-3;
1.2) adding deionized water into the ytterbium nitrate solution, flushing the diluted ytterbium nitrate solution until the specific gravity is 1.15-1.2, heating to 100-105 ℃, preserving the heat for 2-3 hours, removing the head, and filtering into another container;
1.3) adding ytterbium hydroxide into the ytterbium nitrate filtrate obtained in the step 1.2), adjusting the pH value of the solution to 3-3.5, then adding a metastannic acid solution with the concentration of 5-7%, uniformly stirring, heating to 100-105 ℃, keeping the temperature for 30-60 minutes, removing the head, filtering, and putting into another container to obtain ytterbium nitrate filtrate; the volume ratio of the metastannic acid solution to the ytterbium nitrate filtering liquid is 0.5-0.7: 1000, parts by weight;
1.4) sampling from the ytterbium nitrate filtrate, carrying out ICP detection on the contents of metal elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the solution, and if the contents are less than 0.3ppm, indicating that the ytterbium nitrate filtrate obtained in the step 1.3) meets the subsequent preparation requirements, and entering the step 2; if the content of any element in the metal elements is more than or equal to 0.3ppm, returning to the step 1.3);
and step 2, concentrating to prepare ytterbium nitrate crystals:
2.1) heating and concentrating ytterbium nitrate filtrate qualified in ICP detection until the specific gravity is 1.50-1.55, and cooling the ytterbium nitrate filtrate in a cooling container to room temperature to obtain ytterbium nitrate crystals;
2.2) fishing out the ytterbium nitrate crystal, putting the ytterbium nitrate crystal into a centrifugal machine for liquid-solid separation, and washing off nitrate ions on the surface of the ytterbium nitrate crystal by using deionized water to be below 30ppm in the liquid-solid separation process; centrifuging and throwing for 30 minutes or more, and taking out ytterbium nitrate crystals;
step 3, preparing ytterbium carbonate:
3.1) placing the ytterbium nitrate crystal obtained in the step 2.2) into a container, adding deionized water to dissolve the ytterbium nitrate crystal into a ytterbium nitrate solution with the specific gravity of 1.05-1.10 for later use;
3.2) purification of sodium carbonate:
3.2.1) putting industrial sodium carbonate into another container, adding deionized water at the temperature of 80-90 ℃, and fully dissolving until the specific gravity is 1.1-1.15 to obtain a sodium carbonate solution;
3.2.2) cooling the sodium carbonate solution to below 30 ℃, adding a trace amount of hydrogen peroxide, uniformly stirring, and standing for 30 minutes or more;
3.2.3) adding a sodium sulfide solution with the concentration of 1.5-3% into the solution obtained in the step 3.2.2), fully stirring, heating to 90-95 ℃, preserving heat for 2 hours, removing the head, filtering and putting into another container to obtain a purified sodium carbonate filtrate; the volume ratio of the sodium sulfide solution to the sodium carbonate solution obtained in the step 3.2.2) is 0.8-1: 1000, parts by weight;
3.2.4) sampling from the sodium carbonate filtrate, detecting the contents of metallic elements Fe, Cu, Ni, Cr, Co, Mn, Ti, V and Pb in the solution by ICP (inductively coupled plasma), and if the contents are less than 0.3ppm, indicating that the sodium carbonate filtrate obtained in the step 3.2.3) is qualified in purification, meeting the subsequent preparation requirements, and entering the step 3.3); if the content of Fe in the metal element is less than 0.3ppm and the content of any other element is more than or equal to 0.3ppm, returning to the step 3.2.3); if the Fe content in the metal element is more than or equal to 0.3ppm, returning to the step 3.2.2);
3.3) synthesizing ytterbium carbonate by using the ytterbium nitrate solution obtained in the step 3.1) and the sodium carbonate filtrate obtained in the step 3.2.4) and purifying to obtain qualified sodium carbonate filtrate, and preparing a ytterbium carbonate filter cake;
step 4, ytterbium fluoride synthesis:
4.1) adding high-purity hydrofluoric acid with the concentration of 45-65% into a polytetrafluoroethylene reaction kettle, adding deionized water, and stirring uniformly to prepare high-purity hydrofluoric acid with the concentration of 30-35%;
4.2) adding water into the ytterbium carbonate filter cake, stirring the ytterbium carbonate filter cake into paste with the solid content of 25-35%, heating the paste to 45-50 ℃, slowly adding the ytterbium carbonate paste into the high-purity hydrofluoric acid obtained in the step 4.1), and obtaining ytterbium fluoride precipitate, wherein the pH value of the synthesis reaction end point is 1-2;
step 5, removing carbon dioxide:
adding deionized water into the ytterbium fluoride precipitate synthesized in the step 4.2), stirring into paste with the solid content of 35-40%, heating to 90-110 ℃, and keeping the temperature for 2-3 hours to completely remove carbon dioxide; testing the pH value of the reactant during the heat preservation period, and if the pH value is not 1-2, supplementing high-purity hydrofluoric acid with the concentration of 30-35% for adjustment to keep the pH value at 1-2;
step 6, roasting ytterbium fluoride:
6.1) sending the ytterbium fluoride after removing the carbon dioxide in the step 5 into a plate-and-frame filter press for filter pressing, washing until chloride ions and sulfate ions in the ytterbium fluoride are less than 20ppm, pressing and drying to form a ytterbium fluoride filter cake, and taking out;
6.2) putting the taken out ytterbium fluoride filter cake into a ceramic crucible, and roasting at a gradient temperature rise to obtain a final ytterbium fluoride product; the gradient temperature-rising roasting specifically comprises the following steps:
the first stage is as follows: heating to 110-120 deg.c, roasting for 1.5-3 hr to eliminate ytterbium fluoride surface water;
and a second stage: heating to 450 ℃ and 500 ℃, and roasting for 1.5-3 hours to remove the crystal water of the ytterbium fluoride;
and a third stage: heating to 600-700 ℃, roasting for 1.5-3 hours, and removing the ytterbium fluoride structural water;
a fourth stage: the temperature is raised to 750 ℃ and 800 ℃, and the temperature is reduced to room temperature after roasting for 2 to 3 hours, thus obtaining the roasted final ytterbium fluoride product.
2. The method for preparing ytterbium fluoride as a high-purity optical glass additive according to claim 1, wherein in the step 4.2):
and adding a little ytterbium carbonate paste into the high-purity hydrofluoric acid, stopping adding the ytterbium carbonate paste, slowly adding the ytterbium carbonate paste after large-particle ytterbium fluoride fine seeds are formed, and controlling the pH value at the end point of the synthesis reaction to be 1-2.
3. The method for preparing ytterbium fluoride as a high-purity optical glass additive according to claim 2, wherein in the step 4.2): the pH value at the end of the synthesis reaction is 1.
4. The method for producing ytterbium fluoride as a high-purity optical glass additive according to any one of claims 1 to 3, characterized by comprising: the volume ratio of the sodium carbonate to the hydrogen peroxide in the step 3.2.2) is 1000-: 1-1.5.
5. The method for preparing ytterbium fluoride as a high-purity optical glass additive according to claim 4, wherein 3.3) the method for synthesizing ytterbium carbonate and preparing a ytterbium carbonate filter cake comprises the following steps:
3.3.1) adding ytterbium nitrate solution with the specific gravity of 1.05-1.10 into the reaction container, and slowly adding sodium carbonate filtrate qualified in the step 3.2.4) under the stirring state to generate ytterbium carbonate precipitate;
3.3.2) washing the ytterbium carbonate precipitate by a plate-and-frame filter press until nitrate ions and sodium ions are both less than 30ppm, and pressing to dry to obtain a ytterbium carbonate filter cake.
6. The method for preparing ytterbium fluoride as a high-purity optical glass additive according to claim 5, wherein: the concentration of metastannic acid in step 1.3) is 4% or 6%.
7. The method for preparing ytterbium fluoride as a high-purity optical glass additive according to claim 6, wherein: the concentration of the sodium sulfide solution in step 3.2.3) is 2%.
8. The method for preparing ytterbium fluoride as a high-purity optical glass additive according to claim 7, wherein: in step 5, the temperature is raised to 105 ℃, the temperature is maintained for 2.5 hours, and the pH value is kept at 1.5.
9. The method for preparing ytterbium fluoride as a high-purity optical glass additive according to claim 8, wherein:
the gradient temperature rising roasting in the step 6.2) is specifically as follows:
the first stage is as follows: heating to 115 ℃, and roasting for 3 hours to separate the surface water of the ytterbium fluoride;
and a second stage: heating to 480 ℃, and roasting for 2 hours to remove the crystal water of ytterbium fluoride;
and a third stage: heating to 660 ℃, and roasting for 2 hours to remove ytterbium fluoride structural water;
a fourth stage: and raising the temperature to 785 ℃, roasting for 3 hours, and then reducing the temperature to room temperature to obtain a roasted final ytterbium fluoride product.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700902A (en) * | 2009-11-04 | 2010-05-05 | 包头瑞达稀土材料有限公司 | Method for manufacturing rare earth fluoride |
| CN102992381A (en) * | 2012-09-22 | 2013-03-27 | 包头市京瑞新材料有限公司 | Method for preparing macrogranular ytterbium oxide |
| CN107500527A (en) * | 2017-09-30 | 2017-12-22 | 徐传龙 | A kind of continuous induction melting furnace draws ytterbium fluorine laser quartz pushrod and preparation method thereof |
| CN111592231A (en) * | 2020-05-25 | 2020-08-28 | 南京耶拿光电技术有限公司 | Ytterbium fluoride mixed coating material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700902A (en) * | 2009-11-04 | 2010-05-05 | 包头瑞达稀土材料有限公司 | Method for manufacturing rare earth fluoride |
| CN102992381A (en) * | 2012-09-22 | 2013-03-27 | 包头市京瑞新材料有限公司 | Method for preparing macrogranular ytterbium oxide |
| CN107500527A (en) * | 2017-09-30 | 2017-12-22 | 徐传龙 | A kind of continuous induction melting furnace draws ytterbium fluorine laser quartz pushrod and preparation method thereof |
| CN111592231A (en) * | 2020-05-25 | 2020-08-28 | 南京耶拿光电技术有限公司 | Ytterbium fluoride mixed coating material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115259206A (en) * | 2022-07-22 | 2022-11-01 | 承德莹科精细化工股份有限公司 | Preparation method of high-purity thulium carbonate and high-purity thulium trifluoride |
| CN115259206B (en) * | 2022-07-22 | 2024-02-20 | 承德莹科精细化工股份有限公司 | Preparation method of high-purity thulium carbonate and high-purity thulium trifluoride |
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