CN115259206B - Preparation method of high-purity thulium carbonate and high-purity thulium trifluoride - Google Patents
Preparation method of high-purity thulium carbonate and high-purity thulium trifluoride Download PDFInfo
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- AATUHDXSJTXIHB-UHFFFAOYSA-K trifluorothulium Chemical compound F[Tm](F)F AATUHDXSJTXIHB-UHFFFAOYSA-K 0.000 title claims abstract description 93
- ZXOGQNPNWAUSGY-UHFFFAOYSA-H thulium(3+);tricarbonate Chemical compound [Tm+3].[Tm+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O ZXOGQNPNWAUSGY-UHFFFAOYSA-H 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 34
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims description 118
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 76
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 claims description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 52
- 239000001099 ammonium carbonate Substances 0.000 claims description 52
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 52
- 239000012535 impurity Substances 0.000 claims description 42
- 239000013078 crystal Substances 0.000 claims description 40
- 229910052742 iron Inorganic materials 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 37
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 34
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 33
- 229910052793 cadmium Inorganic materials 0.000 claims description 33
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 33
- 229910052804 chromium Inorganic materials 0.000 claims description 33
- 239000011651 chromium Substances 0.000 claims description 33
- 229910017052 cobalt Inorganic materials 0.000 claims description 33
- 239000010941 cobalt Substances 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 33
- 239000011133 lead Substances 0.000 claims description 33
- 229910052759 nickel Inorganic materials 0.000 claims description 33
- 239000010936 titanium Substances 0.000 claims description 33
- 229910052719 titanium Inorganic materials 0.000 claims description 33
- 229910052720 vanadium Inorganic materials 0.000 claims description 33
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 23
- 239000012065 filter cake Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 17
- 230000005484 gravity Effects 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 13
- 239000012498 ultrapure water Substances 0.000 claims description 12
- AUYOHNUMSAGWQZ-UHFFFAOYSA-L dihydroxy(oxo)tin Chemical compound O[Sn](O)=O AUYOHNUMSAGWQZ-UHFFFAOYSA-L 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000010413 mother solution Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000013067 intermediate product Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 description 24
- 239000002184 metal Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 22
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 19
- 239000004744 fabric Substances 0.000 description 12
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000003556 assay Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/247—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/253—Halides
- C01F17/265—Fluorides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
In order to solve the technical problem that the purity of thulium trifluoride prepared by a traditional dry method is low, the invention provides a preparation method of high-purity thulium carbonate and high-purity thulium trifluoride, and thulium trifluoride with the purity of more than 99.9% can be produced. The method adopts relatively easily obtained thulium trioxide as a raw material, adopts a multistage conversion mode, firstly refines the raw material to obtain high-activity and high-purity thulium carbonate, then converts the thulium carbonate into a high-activity and high-purity intermediate product thulium carbonate which is easy to react with hydrofluoric acid, and finally utilizes the reaction of the intermediate product thulium carbonate and the hydrofluoric acid to obtain the high-purity thulium trifluoride.
Description
Technical Field
The invention relates to a preparation method of thulium trifluoride.
Background
The demand of fluoride photoelectric materials is increased year by year at present, and the fluoride photoelectric materials are mainly applied to optical fiber communication, laser crystals and precise circuit components. Thulium trifluoride is used as a high-end photoelectric material additive, and along with the development of market application, the index requirements of the thulium trifluoride are more and more strict.
Most thulium fluoride products circulated in the market are basically prepared by adopting a dry method, and have lower purity and higher other metal impurities. However, some special photoelectric materials in the market have very strict requirements on the purity and excessive metal element content of thulium trifluoride, and the main metal impurity content of iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like is required to be less than 1ppm, but the conventional dry production cannot meet the index requirement.
Disclosure of Invention
In order to solve the technical problem that the purity of thulium trifluoride prepared by a traditional dry method is low, the invention provides a preparation method of high-purity thulium carbonate and high-purity thulium trifluoride, and thulium trifluoride with the purity of more than 99.9% can be produced.
The technical scheme of the invention is as follows:
the preparation method of the high-purity thulium carbonate is characterized by comprising the following steps of:
step 1, purifying thulium trioxide and ammonium carbonate
A. Purification of thulium trioxide
Step A1, firstly adding analytically pure nitric acid into a reactor, then adding high-purity water with the mass of 1:1-1.5 to dilute the mixture, and then slowly adding thulium trioxide into the mixture, wherein the molar ratio of the nitric acid to the thulium trioxide is 6-6.2:1, heating, stirring, wherein the pH at the end of the reaction is 1.5-2.5, adding high-purity water to dilute to a specific gravity of 1.1-1.15 after the reaction is completed, adding metastannic acid and 5-10% hydrochloric acid into the mixture, wherein the mass of the metastannic acid is 1/1000-1/500 of that of the diluted thulium nitrate solution, settling, filtering, and collecting supernatant to obtain the thulium nitrate solution; the reaction equation is: 6HNO 3 +Tm 2 O 3 ＝2Tm(NO 3 ) 3 +3H 2 O
Step A2, heating, concentrating and crystallizing the thulium nitrate solution, stirring and cooling, collecting crystals, and performing centrifugal drying, wherein iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese and lead are all less than 0.2ppm, so as to obtain high-purity hydrated thulium nitrate crystals;
B. purified ammonium carbonate
Adding reagent-grade ammonium carbonate into high-purity water for dissolution to obtain an ammonium carbonate solution with the mass fraction of 18-20%, filtering, removing impurities, and controlling iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese and lead in the ammonium carbonate solution to be less than 0.1ppm to obtain a pure ammonium carbonate solution; because the purity of the reagent grade ammonium carbonate is very high, wherein excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like are all less than 0.1ppm, the reagent grade ammonium carbonate can be used only by filtering the impurities;
step 2, preparing high-purity thulium carbonate
2.1, dissolving the hydrated thulium nitrate crystal obtained in the step 1 into a thulium nitrate solution with the specific gravity of 1.18-1.2 (at the moment, the thulium nitrate has poor water content and the specific gravity is the standard), adding the thulium nitrate solution into the ammonium carbonate solution obtained in the step 1, heating to more than 80 ℃, stirring and reacting for 1-2 hours, wherein the pH value at the end of the reaction is 8-9, and obtaining the high-purity thulium carbonate synthetic solution; the reaction equation is:
2Tm(NO 3 ) 3 +3(NH 4 ) 2 CO 3 ＝Tm 2 (CO 3 ) 3 +6NH 4 NO 3 ；
and 2.2, centrifuging the high-purity thulium carbonate synthetic solution while the high-purity thulium carbonate synthetic solution is hot, washing with water, wherein the mass fraction of nitrate in the medium-control mother solution is less than 0.02%, and the mass fractions of iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese and lead are all less than 0.3ppm, so as to obtain the high-purity thulium carbonate. The washing in this step is used to remove nitrate, and the high temperature during the subsequent preparation of thulium trifluoride can volatilize the vast majority of the residual trace nitrate.
Based on the above basic technical solution, the present invention further optimizes and defines the following:
further, in step A1, the pH is adjusted to 1.7; after the reaction is completed, water is added to dilute the mixture to a specific gravity of 1.12, and 5 to 7 mass percent of metastannic acid is added into the mixture.
In step A1, a filter element with an accuracy of 1 μm or more is used for filtering.
And (3) in the step (A2), heating the thulium nitrate solution to 100-105 ℃ for micro negative pressure concentration, stirring and cooling to 20-30 ℃ after a large amount of crystals are concentrated, taking out the crystals, and spin-drying the crystals by a centrifugal machine, wherein the content of iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese and lead is less than 0.2ppm, so as to obtain the high-purity hydrated thulium nitrate crystals.
Further, step 2.2 specifically includes: adding the high-purity thulium carbonate synthetic solution into a centrifugal machine while the high-purity thulium carbonate synthetic solution is hot, centrifuging by using 1500-mesh filter cloth at 1500 rpm, washing by using hot water, and controlling nitrate radical to be less than 0.02%, wherein iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese and lead are all less than 0.3ppm, thereby obtaining the high-purity thulium carbonate.
Further, the reaction endpoint pH in step 2.1 was 8.5.
The invention also provides high-purity thulium carbonate, which is characterized in that: the preparation method is adopted.
The invention also provides a preparation method of thulium trifluoride, which is characterized by comprising the following steps:
step one: the method is adopted to prepare high-purity thulium carbonate;
step two: preparation of high purity thulium trifluoride
Step 2.1), adding 50-55% of electronic grade hydrofluoric acid into a reaction kettle, preheating and heating, adding the high-purity thulium carbonate into the reaction kettle, heating to 80-90 ℃ according to the molar ratio of the hydrofluoric acid to the thulium carbonate of 6:1, carrying out heat preservation and stirring reaction for 3-4 hours, wherein the pH value of the reaction end point is 1.5-2, and removing carbonate radicals to obtain thulium trifluoride synthetic liquid; the reaction equation is: tm (Tm) 2 (CO 3 ) 3 +6HF＝2TmF 3 +3CO 2 +3H 2 O
Step 2.2) centrifuging the thulium trifluoride synthetic solution, washing free acid with water, and obtaining a thulium trifluoride filter cake;
step 2.3) carrying out gradient drying on the thulium trifluoride filter cake to obtain high-purity thulium trifluoride.
Based on the basic technical scheme, the invention also performs the following further optimization and limitation:
step 2.1) in step two the reaction endpoint pH was 1.5.
Further, step 2.2) in step two is specifically: and (3) pouring the thulium trifluoride synthetic liquid into a centrifugal machine, adopting 2000-mesh filter cloth, 1500 revolutions per minute, centrifuging for 30 minutes, slightly washing with heated water, and washing free acid to obtain a thulium trifluoride filter cake.
Further, step 2.3) in the second step is specifically:
a first gradient: drying for 3-4 hours at 150-200 ℃, removing surface water and most of free acid, reducing corrosion to a furnace and an alloy plate during high-temperature drying, and ensuring the purity of the alloy plate;
a second gradient: drying at 500-550 ℃ for 3-4 hours to obtain high-purity thulium trifluoride, and detecting data: the excessive metal impurities such as cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like are all less than 0.5ppm, iron is less than 1ppm, the weight loss on ignition is less than 0.3%, the purity reaches more than 99.9%, and the characterization is shown in figure 1.
The beneficial effects of the invention are as follows:
1. the method adopts relatively easily obtained thulium trioxide as a raw material, adopts a multistage conversion mode, firstly refines the raw material to obtain high-activity and high-purity thulium carbonate, then converts the thulium carbonate into a high-activity and high-purity intermediate product thulium carbonate which is easy to react with hydrofluoric acid, and finally utilizes the reaction of the intermediate product thulium carbonate and the hydrofluoric acid to obtain the high-purity thulium trifluoride.
2. In the refining process of the raw materials, the thulium nitrate solution obtained by dissolving the thulium trioxide by nitric acid is acidic due to excessive nitric acid, and the metal impurities in the thulium nitrate solution can be effectively adsorbed by adopting the dilute acid treatment in an acidic environment, so that the content of elements such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like in the thulium nitrate solution is less than 0.2ppm. And then the thulium nitrate with high activity is converted into thulium nitrate which can be effectively and fully reacted with hydrofluoric acid, and thulium trifluoride particles which can be effectively filtered are obtained.
3. The method adopts a pulping mode, so that the prepared thulium carbonate can fully react with hydrofluoric acid to obtain high-purity thulium trifluoride, and meanwhile, the preparation efficiency is improved.
4. The invention also realizes the preparation of high-activity and high-purity thulium carbonate in the process of researching how to prepare high-purity thulium trifluoride, and specifically comprises the steps of dissolving raw material bismuth trioxide by nitric acid, removing heavy metal impurities by adopting dilute acid adsorption, recrystallizing filtered thulium nitrate solution to obtain high-purity thulium nitrate, and synthesizing the high-activity and high-purity thulium carbonate with filtered reagent-grade ammonium carbonate solution.
Drawings
FIG. 1 is an XRD pattern of thulium trifluoride prepared in example 1 of the present invention.
Detailed Description
The invention is characterized in that:
at present, few factories for producing thulium trifluoride are in the industry, basically laboratory products, most thulium trifluoride in the market is produced by a dry method, and is mainly applied to the metallurgical industry, the requirements on heavy metal impurities and content are not particularly strict, and the use requirements of high-purity photoelectric material additives can not be basically met by thulium fluoride synthesized by the dry method and thulium trifluoride produced by other modes in the market. The method mainly aims at the standard requirement of special high-purity photoelectric material additives to produce thulium trifluoride, adopts a special impurity removal process to purify thulium trifluoride firstly, carbonizes the thulium trifluoride after the purity reaches the use standard to prepare thulium carbonate capable of reacting, then reacts with hydrofluoric acid to obtain pure thulium trifluoride, and finally prevents pollution by gradient drying to obtain the high-purity thulium trifluoride with the purity of more than 99.9 percent.
The main reaction equation is:
6HNO 3 +Tm 2 O 3 ＝2Tm(NO 3 ) 3 +3H 2 O
2Tm(NO 3 ) 3 +3(NH 4 ) 2 CO 3 ＝Tm 2 (CO 3 ) 3 +6NH 4 NO 3
Tm 2 (CO 3 ) 3 +6HF＝2TmF 3 +3CO 2 +3H 2 O
example 1
This example prepares high purity thulium trifluoride by the following steps:
step 1, purifying thulium trioxide and ammonium carbonate
A. Purification of thulium trioxide
Step A1, firstly adding analytically pure nitric acid into a reaction kettle, then adding 1:1 mass of water to dilute the solution by one time, and then slowly adding thulium trioxide into the reaction kettle, wherein the molar ratio of the nitric acid to the thulium trioxide is 6:1, heating to 60 ℃, stirring and reacting for 30-60 minutes, wherein the pH value at the end of the reaction is 1.5, adding water to dilute the solution to a specific gravity of 1.15, adding metastannic acid (for adsorbing metal impurities in the coprecipitated thulium nitrate solution) with a mass of 1/500 of the mass of the diluted thulium nitrate solution, adding hydrochloric acid (for removing iron impurities in the thulium nitrate solution) with a mass fraction of 5-10%, stirring, settling, and filtering by a1 mu m filter element to obtain the thulium nitrate solution;
and A2, heating the thulium nitrate solution to 105 ℃ and concentrating under micro negative pressure, stirring, cooling to 25 ℃ after concentrating a large amount of crystals, taking out the crystals, and spin-drying the crystals by a centrifugal machine, wherein the content of excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like is less than 0.2ppm, so as to obtain the high-purity hydrated thulium nitrate crystals.
B. Purified ammonium carbonate
And 2.1, adding reagent-grade ammonium carbonate into high-purity water to be dissolved into an ammonium carbonate solution with the mass fraction of 20%, filtering by adopting a1 mu m filter core to remove mechanical impurities and trace insoluble matters, and controlling excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like in the ammonium carbonate solution to be less than 0.1ppm to obtain a pure ammonium carbonate solution.
Step 2, preparing high-purity thulium carbonate
2.1, dissolving the hydrated thulium nitrate crystal obtained in the step 1 into a thulium nitrate solution with the specific gravity of 1.18, adding the thulium nitrate solution into the pure ammonium carbonate solution obtained in the step 1, heating to the temperature of more than 80 ℃, stirring and reacting for 1-2 hours, wherein the pH value of the reaction end point is 8, and obtaining high-purity thulium carbonate synthetic liquid;
and 2.2, adding the high-purity thulium carbonate synthetic solution into a centrifugal machine while the high-purity thulium carbonate synthetic solution is hot, centrifuging at 1500 rpm by using 1500-mesh filter cloth, washing with hot water, and controlling the mass fraction of nitrate in the mother solution to be less than 0.02%, wherein excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like are all less than 0.3ppm, thereby obtaining the high-purity thulium carbonate.
Step 3, preparing high-purity thulium trifluoride
Step 3.1, adding 50% of electronic grade hydrofluoric acid into a reaction kettle, heating to above 60 ℃, adding the high-purity thulium carbonate obtained in the step 2.2 into the reaction kettle, heating to 80 ℃, preserving heat, stirring, reacting for 3-4 hours, wherein the pH value at the end of the reaction is 2, and removing carbonate to obtain thulium trifluoride synthetic liquid;
step 3.2, pumping thulium trifluoride synthetic solution into a centrifuge, adopting 2000-mesh filter cloth, performing 1500-turn/min centrifugation for 30 min, slightly washing with heated water, and washing free acid to obtain thulium trifluoride filter cake;
step 3.3, carrying out gradient drying on the thulium trifluoride filter cake
A first gradient: drying the thulium trifluoride filter cake in a tetrafluoro plate at 180 ℃ for 4 hours;
and transferring thulium trifluoride into an alloy aluminum plate, and drying at 550 ℃ for 4 hours to obtain a target product, wherein the XRD spectrum of the target product is shown in the attached figure 1, and the product is qualitatively thulium trifluoride without other impurity peaks. The Agilent 5110-ICP-OES detection shows that cobalt, nickel, titanium, vanadium, chromium, cadmium, copper and lead in the product are all less than 0.5ppm, iron is 0.93ppm, and the indexes meet the requirements. The specific assay analysis results are shown in table 1 below:
TABLE 1
Example 2
This example prepares high purity thulium trifluoride by the following steps:
step 1, purifying thulium trioxide and ammonium carbonate
A. Purification of thulium trioxide
Step A1, firstly adding analytically pure nitric acid into a reaction kettle, then adding water with the mass of 1:3 to dilute the solution, and then slowly adding thulium trioxide into the solution, wherein the molar ratio of the nitric acid to the thulium trioxide is 6:1, heating to 70 ℃, stirring and reacting for 30-60 minutes, wherein the pH value at the end of the reaction is 1, adding water to dilute the solution to a specific gravity of 1.1, adding metastannic acid (for adsorbing metal impurities in the coprecipitated thulium nitrate solution) with a mass of 1/800 of the mass of the diluted thulium nitrate solution, adding hydrochloric acid (for removing iron impurities in the thulium nitrate solution) with a mass fraction of 5-10%, stirring, settling, and filtering by a1 mu m filter element to obtain the thulium nitrate solution;
and A2, heating the thulium nitrate solution to 100 ℃ and concentrating under micro negative pressure, stirring, cooling to 20 ℃ after concentrating a large amount of crystals, taking out the crystals, and spin-drying the crystals by a centrifugal machine, wherein the content of excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like is less than 0.2ppm, so as to obtain the high-purity hydrated thulium nitrate crystals.
B. Purified ammonium carbonate
And 2.1, adding reagent-grade ammonium carbonate into high-purity water to be dissolved into an ammonium carbonate solution with the mass fraction of 20%, filtering by adopting a1 mu m filter core to remove mechanical impurities and trace insoluble matters, and controlling excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like in the ammonium carbonate solution to be less than 0.1ppm to obtain a pure ammonium carbonate solution.
Step 2, preparing high-purity thulium carbonate
2.1, dissolving the hydrated thulium nitrate crystal obtained in the step 1 into a thulium nitrate solution with the specific gravity of 1.2, adding the thulium nitrate solution into the pure ammonium carbonate solution obtained in the step 1, heating to 85 ℃, stirring and reacting for 1-2 hours, wherein the pH value of the reaction end point is 9, and obtaining the high-purity thulium carbonate synthetic solution;
and 2.2, adding the high-purity thulium carbonate synthetic solution into a centrifugal machine while the high-purity thulium carbonate synthetic solution is hot, centrifuging at 1500 rpm by using 1500-mesh filter cloth, washing with hot water, and controlling nitrate radical to be less than 0.02%, wherein excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like are all less than 0.3ppm, thereby obtaining the high-purity thulium carbonate.
Step 3, preparing high-purity thulium trifluoride
Step 3.1, adding 50% of electronic grade hydrofluoric acid into a reaction kettle, heating to above 60 ℃, adding the high-purity thulium carbonate obtained in the step 2.2 into the reaction kettle, heating to 85 ℃, preserving heat, stirring and reacting for 3-4 hours, wherein the pH value at the end of the reaction is 1, and removing carbonate to obtain thulium trifluoride synthetic liquid;
step 3.2, pumping thulium trifluoride synthetic solution into a centrifuge, adopting 2000-mesh filter cloth, performing 1500-turn/min centrifugation for 30 min, slightly washing with heated water, and washing free acid to obtain thulium trifluoride filter cake;
step 3.3, carrying out gradient drying on the thulium trifluoride filter cake
A first gradient: drying the thulium trifluoride filter cake in a tetrafluoro tray at 150 ℃ for 3 hours;
and transferring thulium trifluoride into an alloy aluminum plate, and drying at 500 ℃ for 4 hours to obtain a target product, wherein the XRD spectrum of the target product is basically consistent with that shown in the attached drawing 1, and the target product is qualitatively thulium trifluoride without other miscellaneous peaks. The Agilent 5110-ICP-OES detection shows that cobalt, nickel, titanium, vanadium, chromium, cadmium, copper and lead in the product are all less than 0.5ppm, iron is 0.86ppm, and the indexes meet the requirements. The specific assay analysis results are shown in table 2 below:
TABLE 2
Example 3
This example prepares high purity thulium trifluoride by the following steps:
step 1, purifying thulium trioxide and ammonium carbonate
A. Purification of thulium trioxide
Step A1, firstly adding analytically pure nitric acid into a reaction kettle, then adding 1:1.5 mass of water to dilute the solution, and then slowly adding thulium trioxide into the solution, wherein the molar ratio of the nitric acid to the thulium trioxide is 6.2:1, heating to 65 ℃, stirring and reacting for 30-60 minutes, wherein the pH of the reaction end point is 1.7, adding water to dilute to a specific gravity of 1.12, adding metastannic acid with a mass of 1/1000 of the mass of the diluted thulium nitrate solution, adding hydrochloric acid with a mass fraction of 5-10% (the hydrochloric acid is used for removing iron impurities in the thulium nitrate solution), stirring, settling, and filtering by a1 mu m filter element to obtain the thulium nitrate solution;
and A2, heating the thulium nitrate solution to 103 ℃ and concentrating under micro negative pressure, stirring, cooling to 30 ℃ after concentrating a large amount of crystals, taking out the crystals, and spin-drying the crystals by a centrifugal machine, wherein the content of excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like is less than 0.2ppm, so as to obtain the high-purity hydrated thulium nitrate crystals.
B. Purified ammonium carbonate
And 2.1, adding reagent-grade ammonium carbonate into high-purity water to be dissolved into an ammonium carbonate solution with the mass fraction of 20%, filtering by adopting a1 mu m filter core to remove mechanical impurities and trace insoluble matters, and controlling excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like in the ammonium carbonate solution to be less than 0.1ppm to obtain a pure ammonium carbonate solution.
Step 2, preparing high-purity thulium carbonate
2.1, dissolving the hydrated thulium nitrate crystal obtained in the step 1 into a thulium nitrate solution with the specific gravity of 1.19, adding the thulium nitrate solution into the pure ammonium carbonate solution obtained in the step 1, heating to 80 ℃, stirring and reacting for 1-2 hours, wherein the pH value of the reaction end point is 8.5, and obtaining high-purity thulium carbonate synthetic liquid;
and 2.2, adding the high-purity thulium carbonate synthetic solution into a centrifugal machine while the high-purity thulium carbonate synthetic solution is hot, centrifuging at 1500 rpm by using 1500-mesh filter cloth, washing with hot water, and controlling nitrate radical to be less than 0.02%, wherein excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like are all less than 0.3ppm, thereby obtaining the high-purity thulium carbonate.
Step 3, preparing high-purity thulium trifluoride
Step 3.1, adding 50-55% of electronic grade hydrofluoric acid into a reaction kettle, heating to above 60 ℃, adding the high-purity thulium carbonate obtained in the step 2.2 into the reaction kettle, wherein the molar ratio of the hydrofluoric acid to the thulium carbonate is 6:1, heating to 80-90 ℃, carrying out heat preservation and stirring for 3-4 hours, and removing carbonate radical at a reaction end point pH of 1.5 to obtain thulium trifluoride synthetic liquid;
step 3.2, pumping thulium trifluoride synthetic solution into a centrifuge, adopting 2000-mesh filter cloth, performing 1500-turn/min centrifugation for 30 min, slightly washing with heated water, and washing free acid to obtain thulium trifluoride filter cake;
step 3.3, carrying out gradient drying on the thulium trifluoride filter cake
A first gradient: drying the thulium trifluoride filter cake in a tetrafluoro tray at 200 ℃ for 3 hours;
and transferring the thulium trifluoride into an alloy aluminum plate, and drying at 520 ℃ for 3.5 hours to obtain a target product, wherein the XRD spectrum of the target product is basically consistent with that shown in the attached drawing 1, and the target product is qualitatively thulium trifluoride without other impurity peaks. The Agilent 5110-ICP-OES detection shows that cobalt, nickel, titanium, vanadium, chromium, cadmium, copper and lead in the product are all less than 0.5ppm, iron is 0.82ppm, and the indexes meet the requirements. The specific assay analysis results are shown in table 3 below:
TABLE 3 Table 3
Example 4
This example prepares high purity thulium trifluoride by the following steps:
step 1, purifying thulium trioxide and ammonium carbonate
A. Purification of thulium trioxide
Step A1, firstly adding analytically pure nitric acid into a reaction kettle, then adding 1:1.5 mass of water to dilute the solution, and then slowly adding thulium trioxide into the solution, wherein the molar ratio of the nitric acid to the thulium trioxide is 6.1:1, heating to 65 ℃, stirring and reacting for 30-60 minutes, wherein the pH of the end point of the reaction is 1.8, adding water to dilute the solution to a specific gravity of 1.14, adding 5-7% of metastannic acid (for adsorbing metal impurities in the coprecipitated thulium nitrate solution) with a mass fraction of 1/750 of the mass of the diluted thulium nitrate solution, adding 5-10% of hydrochloric acid (for removing iron impurities in the thulium nitrate solution), and filtering the solution by adopting a 1-mu m filter element to obtain the thulium nitrate solution;
and A2, heating the thulium nitrate solution to 105 ℃ and concentrating under micro negative pressure, stirring, cooling to 20 ℃ after concentrating a large amount of crystals, taking out the crystals, and spin-drying the crystals by a centrifugal machine, wherein the content of excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like is less than 0.2ppm, so as to obtain the high-purity hydrated thulium nitrate crystals.
B. Purified ammonium carbonate
And 2.1, adding reagent-grade ammonium carbonate into high-purity water to be dissolved into an ammonium carbonate solution with the mass fraction of 18%, filtering by adopting a1 mu m filter core to remove mechanical impurities and trace insoluble matters, and controlling excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like in the ammonium carbonate solution to be less than 0.1ppm to obtain a pure ammonium carbonate solution.
Step 2, preparing high-purity thulium carbonate
2.1, dissolving the hydrated thulium nitrate crystal obtained in the step 1 into a thulium nitrate solution with the specific gravity of 1.2, adding the thulium nitrate solution into the pure ammonium carbonate solution obtained in the step 1, heating to 90 ℃, stirring and reacting for 1-2 hours, wherein the pH value of the reaction end point is 8.7, and obtaining high-purity thulium carbonate synthetic liquid;
and 2.2, adding the high-purity thulium carbonate synthetic solution into a centrifugal machine while the high-purity thulium carbonate synthetic solution is hot, centrifuging at 1500 rpm by using 1500-mesh filter cloth, washing with hot water, and controlling nitrate radical to be less than 0.02%, wherein excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like are all less than 0.3ppm, thereby obtaining the high-purity thulium carbonate.
Step 3, preparing high-purity thulium trifluoride
Step 3.1, adding 55% by mass of electronic grade hydrofluoric acid into a reaction kettle, heating to above 60 ℃, adding the high-purity thulium carbonate obtained in the step 2.2 into the reaction kettle, wherein the molar ratio of the hydrofluoric acid to the thulium carbonate is 6:1, heating to 80 ℃, carrying out heat preservation and stirring for 3-4 hours, and removing carbonate radical to obtain thulium trifluoride synthetic liquid, wherein the pH value at the end point of the reaction is 1.7;
step 3.2, pumping thulium trifluoride synthetic solution into a centrifuge, adopting 2000-mesh filter cloth, performing 1500-turn/min centrifugation for 30 min, slightly washing with heated water, and washing free acid to obtain thulium trifluoride filter cake;
step 3.3, carrying out gradient drying on the thulium trifluoride filter cake
A first gradient: drying the thulium trifluoride filter cake in a tetrafluoro tray at 165 ℃ for 3.5 hours;
and transferring thulium trifluoride into an alloy aluminum plate, and drying at 535 ℃ for 3.5 hours to obtain a target product, wherein the XRD spectrum of the target product is basically consistent with that shown in the attached drawing 1, and the target product is qualitatively thulium trifluoride without other impurity peaks. The Agilent 5110-ICP-OES detection shows that cobalt, nickel, titanium, vanadium, chromium, cadmium, copper and lead in the product are all less than 0.5ppm, iron is 0.83ppm, and the indexes meet the requirements. The specific assay analysis results are shown in table 4 below:
TABLE 4 Table 4
Example 5
This example prepares high purity thulium trifluoride by the following steps:
step 1, purifying thulium trioxide and ammonium carbonate
A. Purification of thulium trioxide
Step A1, firstly adding analytically pure nitric acid into a reaction kettle, then adding water with the mass of 1:2 to dilute the solution, and then slowly adding thulium trioxide into the solution, wherein the molar ratio of the nitric acid to the thulium trioxide is 6.15:1, heating to 65 ℃, stirring and reacting for 30-60 minutes, wherein the pH of the reaction end point is 1.6, adding water to dilute the solution to a specific gravity of 1.13, adding metastannic acid with a mass of 1/580 of the mass of the diluted thulium nitrate solution, adding hydrochloric acid with a mass fraction of 5-10% (the hydrochloric acid is used for removing iron impurities in the thulium nitrate solution), stirring, settling, and filtering by a1 mu m filter element to obtain the thulium nitrate solution;
and A2, heating the thulium nitrate solution to 105 ℃ and concentrating under micro negative pressure, stirring, cooling to 20 ℃ after concentrating a large amount of crystals, taking out the crystals, and spin-drying the crystals by a centrifugal machine, wherein the content of excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like is less than 0.2ppm, so as to obtain the high-purity hydrated thulium nitrate crystals.
B. Purified ammonium carbonate
And 2.1, adding reagent-grade ammonium carbonate into high-purity water to be dissolved into an ammonium carbonate solution with the mass fraction of 19%, filtering by adopting a1 mu m filter core to remove mechanical impurities and trace insoluble matters, and controlling excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like in the ammonium carbonate solution to be less than 0.1ppm to obtain a pure ammonium carbonate solution.
Step 2, preparing high-purity thulium carbonate
2.1, dissolving the hydrated thulium nitrate crystal obtained in the step 1 into a thulium nitrate solution with the specific gravity of 1.18, adding the thulium nitrate solution into the pure ammonium carbonate solution obtained in the step 1, heating to 80 ℃, stirring and reacting for 1-2 hours, wherein the pH value of the reaction end point is 8.2, and obtaining high-purity thulium carbonate synthetic liquid;
and 2.2, adding the high-purity thulium carbonate synthetic solution into a centrifugal machine while the high-purity thulium carbonate synthetic solution is hot, centrifuging at 1500 rpm by using 1500-mesh filter cloth, washing with hot water, and controlling nitrate radical to be less than 0.02%, wherein excessive metal impurities such as iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese, lead and the like are all less than 0.3ppm, thereby obtaining the high-purity thulium carbonate.
Step 3, preparing high-purity thulium trifluoride
Step 3.1, adding 52% of electronic grade hydrofluoric acid into a reaction kettle, heating to above 60 ℃, adding the high-purity thulium carbonate obtained in the step 2.2 into the reaction kettle, heating to 80 ℃, preserving heat, stirring and reacting for 3-4 hours, adjusting the pH to 1.2, and removing carbonate to obtain thulium trifluoride synthetic liquid;
step 3.2, pumping thulium trifluoride synthetic solution into a centrifuge, adopting 2000-mesh filter cloth, performing 1500-turn/min centrifugation for 30 min, slightly washing with heated water, and washing free acid to obtain thulium trifluoride filter cake;
step 3.3, carrying out gradient drying on the thulium trifluoride filter cake
A first gradient: drying the thulium trifluoride filter cake in a tetrafluoro plate at 170 ℃ for 4 hours;
and transferring thulium trifluoride into an alloy aluminum plate and drying at 540 ℃ for 4 hours to obtain a target product, wherein the XRD spectrum of the target product is basically consistent with that shown in the attached figure 1, and the target product is qualitatively thulium trifluoride without other miscellaneous peaks. The Agilent 5110-ICP-OES detection shows that cobalt, nickel, titanium, vanadium, chromium, cadmium, copper and lead in the product are all less than 0.5ppm, iron is 0.9ppm, and the indexes meet the requirements. The specific assay analysis results are shown in table 4 below:
TABLE 4 Table 4
Claims (9)
1. The preparation method of the high-purity thulium carbonate is characterized by comprising the following steps of:
step 1, purifying thulium trioxide and ammonium carbonate
A. Purification of thulium trioxide
Step A1, firstly adding analytically pure nitric acid into a reactor, then adding high-purity water with the mass of 1:1-1.5 to dilute the mixture, and then slowly adding thulium trioxide into the mixture, wherein the molar ratio of the nitric acid to the thulium trioxide is 6-6.2:1, heating, stirring, wherein the pH at the end of the reaction is 1.5-2.5, adding high-purity water to dilute to a specific gravity of 1.1-1.15 after the reaction is completed, adding metastannic acid and 5-10% hydrochloric acid into the mixture, wherein the mass of the metastannic acid is 1/1000-1/500 of that of the diluted thulium nitrate solution, settling, filtering, and collecting supernatant to obtain the thulium nitrate solution;
step A2, heating, concentrating and crystallizing the thulium nitrate solution, stirring and cooling, collecting crystals, and performing centrifugal drying, wherein iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese and lead are all less than 0.2ppm, so as to obtain high-purity hydrated thulium nitrate crystals;
B. purified ammonium carbonate
Adding reagent-grade ammonium carbonate into high-purity water to be dissolved into an ammonium carbonate solution with the mass fraction of 18-20%, filtering, removing impurities, and controlling iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese and lead in the ammonium carbonate solution to be less than 0.1ppm to obtain a pure ammonium carbonate solution;
step 2, preparing high-purity thulium carbonate
2.1, dissolving the hydrated thulium nitrate crystal obtained in the step 1 into a thulium nitrate solution with the specific gravity of 1.18-1.2, adding the thulium nitrate solution into the ammonium carbonate solution obtained in the step 1, heating to more than 80 ℃, stirring and reacting for 1-2 hours, wherein the pH value of the reaction end point is 8-9, and obtaining high-purity thulium carbonate synthetic liquid;
and 2.2, centrifuging the high-purity thulium carbonate synthetic solution while the high-purity thulium carbonate synthetic solution is hot, washing with water, wherein the mass fraction of nitrate in the medium-control mother solution is less than 0.02%, and the mass fractions of iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese and lead are all less than 0.3ppm, so as to obtain the high-purity thulium carbonate.
2. The method for preparing high-purity thulium carbonate according to claim 1, characterized in that: in the step A1, the pH of the reaction end point is 1.7; after the reaction is completed, adding high-purity water to dilute the mixture to a specific gravity of 1.12, and adding 5-7% of metastannic acid into the mixture.
3. The method for preparing high-purity thulium carbonate according to claim 2, characterized in that: in the step A1, a filter element with the precision of more than or equal to 1 mu m is adopted for filtering.
4. A process for the preparation of high purity thulium carbonate according to any one of claims 1 to 3, characterized in that: and (A2) heating the thulium nitrate solution to 100-105 ℃ for micro negative pressure concentration, stirring, cooling to 20-30 ℃ after a large amount of crystals are concentrated, taking out the crystals, and spin-drying the crystals by a centrifugal machine, wherein the iron, cobalt, nickel, copper, titanium, vanadium, cadmium, chromium, manganese and lead are all less than 0.2ppm, thus obtaining the high-purity hydrated thulium nitrate crystals.
5. The method for preparing high-purity thulium carbonate according to claim 4, characterized in that: the reaction endpoint pH in step 2.1 was 8.5.
6. The utility model provides a high purity thulium carbonate which characterized in that: prepared by the method of any one of claims 1-5.
7. A method for preparing thulium trifluoride, which is characterized by comprising the following steps:
step one: preparing high-purity thulium carbonate by the method of any one of claims 1-5;
step two: preparation of high purity thulium trifluoride
Step 2.1), adding electronic grade hydrofluoric acid with the mass fraction of 50-55% into a reaction kettle, preheating and heating, adding the high-purity thulium carbonate into the reaction kettle, heating to 80-90 ℃, preserving heat and stirring for reaction for 3-4 hours, wherein the pH value at the end point of the reaction is 1.5-2, and removing carbonate radicals to obtain thulium trifluoride synthetic liquid;
step 2.2) centrifuging the thulium trifluoride synthetic solution, washing free acid with water, and obtaining a thulium trifluoride filter cake;
step 2.3) carrying out gradient drying on the thulium trifluoride filter cake:
a first gradient: drying at 150-200 deg.c for 3-4 hr;
a second gradient: drying at 500-550 deg.c for 3-4 hr to obtain high purity thulium trifluoride.
8. The method for preparing thulium trifluoride according to claim 7, characterized in that: step 2.1) in step two the reaction endpoint pH was 1.5.
9. A high purity thulium trifluoride, characterized in that: a method according to any one of claims 7 to 8.
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