CN117987660A - Nickel isotope simple substance hydrothermal reduction preparation method and nickel isotope simple substance prepared by same - Google Patents
Nickel isotope simple substance hydrothermal reduction preparation method and nickel isotope simple substance prepared by same Download PDFInfo
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- CN117987660A CN117987660A CN202410108775.4A CN202410108775A CN117987660A CN 117987660 A CN117987660 A CN 117987660A CN 202410108775 A CN202410108775 A CN 202410108775A CN 117987660 A CN117987660 A CN 117987660A
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- nickel
- simple substance
- isotope
- hydrothermal reduction
- nickel isotope
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 58
- 239000000126 substance Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000006722 reduction reaction Methods 0.000 claims abstract description 31
- -1 tetra (trifluorophosphine) nickel Chemical compound 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010668 complexation reaction Methods 0.000 claims abstract 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000012827 research and development Methods 0.000 abstract description 2
- 239000002341 toxic gas Substances 0.000 abstract description 2
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 7
- 238000007664 blowing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PXHVJJICTQNCMI-RNFDNDRNSA-N nickel-63 Chemical compound [63Ni] PXHVJJICTQNCMI-RNFDNDRNSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a hydrothermal reduction preparation method of a nickel isotope simple substance and the nickel isotope simple substance prepared by the same. The preparation method comprises the following steps: step 1: slowly dripping tetra (trifluorophosphine) nickel into ammonia water to perform decomposition and complexation reaction to obtain a mixed suspension; step 2: adding a composite reducing agent into the obtained mixed suspension to carry out hydrothermal reduction reaction; step 3: filtering the reaction solution, and drying the filter cake to obtain the elemental nickel isotope. Compared with a direct heating decomposition method, the method solves the risks of high temperature and extremely toxic gas generation in the conversion process, reduces the safety risk and is convenient for subsequent production. The whole process has few links, high yield and high product purity, the reaction process is in liquid phase, the safety risk is reduced, the environmental pollution is avoided, and the subsequent research and development production is facilitated.
Description
Technical Field
The invention relates to the technical field of smelting chemical industry (isotope direction), in particular to a hydrothermal reduction preparation method of a nickel isotope simple substance and the nickel isotope simple substance prepared by the same.
Background
Nickel is an important metal element and is widely applied to the fields of aviation, military, special alloy, batteries and the like. Nickel has been used in the battery field in addition to conventional chemical power supplies in the emerging direction of nuclear batteries, also known as "radioisotope batteries," which have been successfully used as power supplies for spacecraft, cardiac pacemaker power supplies, and some special military applications. Taking nickel as an example, the energy of beta particles emitted during decay of nickel isotope nickel-63 is converted into electric energy, and the nickel isotope battery is small in size and weight, is only 0.26g, works similarly under extreme air temperature and vibration conditions, and can be used for more than 50 years.
The nickel isotope of the core material of the nickel isotope battery is obtained by taking tetra (trifluorophosphine) nickel as a raw material, separating and then chemically reducing the nickel isotope into a nickel isotope simple substance. It can be seen that the important process is the chemical reduction of tetra (trifluorophosphine) nickel to prepare the elemental nickel isotopes.
The existing method for chemically reducing the elemental nickel isotopes by using tetra (trifluorophosphine) nickel as a raw material is still in a research stage. The method adopted by the technical investigation abroad is a direct heating decomposition method, but the method stays in theoretical research, has the problems of high safety risk, uncontrollable process conditions, low yield and the like, such as extremely toxic phosphorus trifluoride gas generated by tetra (trifluorophosphine) nickel in the heating decomposition process, and causes safety risk; meanwhile, the produced nickel isotope simple substance coating film is difficult to take out on the inner wall of the reactor, so that the rear-end process is complex and the yield is low. Secondly, the high-purity nickel (bulletin number: CN 116497231B) is prepared by taking tetra (trifluorophosphine) nickel as a raw material in China through a neutralization method, and the method is still in a research stage at present, and the problems of complex process, low purity, low yield and the like of the whole process exist.
Disclosure of Invention
Aiming at the defects of poor safety, complex process and the like of the existing method for preparing high-purity nickel, the invention provides a method for preparing nickel isotope simple substance by hydrothermal reduction.
The invention also aims to provide the nickel isotope simple substance prepared by the hydrothermal reduction preparation method, and the purity of the product is more than or equal to 99 percent.
Another object of the present invention is to provide the use of the above-mentioned elemental nickel isotopes in a nickel isotope battery.
The technical scheme adopted for realizing the purpose of the invention is as follows:
The hydrothermal reduction preparation method of the nickel isotope simple substance comprises the following steps:
Step 1: slowly dripping tetra (trifluorophosphine) nickel into a polytetrafluoroethylene three-mouth bottle filled with ammonia water cooled to minus 20 ℃ to 0 ℃ in advance, stirring at the speed of 300 rpm to 500rpm at the temperature of minus 20 ℃ to 0 ℃ and reacting for 2 hours to obtain mixed suspension;
in step1, the chemical reaction formula involved is as follows:
Ni(PF3)4+24NH3·H2O＝Ni+4(NH4)3PO3+12NH4F+12H2O (1)
Ni(PF3)4+28NH3·H2O＝[Ni(NH3)4](OH)2+4(NH4)3PO3+12NH4F+14H2O+H2 (2)
Step 2: transferring the obtained mixed suspension to a hydro-thermal synthesis reactor, wherein the lining material of the hydro-thermal synthesis reactor is polytetrafluoroethylene; adding hydrazine hydrate and sodium hypophosphite monohydrate as a composite reducing agent; wherein the molar ratio of hydrazine hydrate, sodium hypophosphite monohydrate and tetra (trifluorophosphine) nickel is (2-8): (0.1-1): 1, a step of; stirring for 3-5 min at the speed of 300-500 rpm, assembling a hydrothermal synthesis reactor, and putting the reactor into an oven for hydrothermal reduction reaction, wherein the hydrothermal reduction temperature is 120-160 ℃, and the reaction time is 1-4 h;
in step2, the chemical reaction formula involved is as follows:
2Ni2++N2H4+4OH▁＝2Ni+N2+4H2O (3)
Ni2++2H2PO2▁+2H2O＝Ni+2H2PO3▁+2H++H2 (4)
step 3: filtering the reacted mixture, and drying the filter cake at 150-200 ℃ for 2-10 h to obtain the elemental nickel isotope.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with a direct heating decomposition method, the preparation method for the nickel isotope simple substance by hydrothermal reduction solves the risks of high temperature and highly toxic gas generation in the conversion process, reduces the safety risk and is convenient for subsequent production.
2. Compared with a neutralization method, the preparation method of the nickel isotope simple substance through hydrothermal reduction has the advantages of less links in the whole process, high yield, high product purity, safety risk reduction and environmental pollution prevention in the reaction process in a liquid phase, and is convenient for subsequent research and development production.
Drawings
Fig. 1 shows a process flow diagram of a preparation method of a nickel isotope simple substance by hydrothermal reduction.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The hydrothermal reduction preparation method of the nickel isotope simple substance comprises the following steps:
Step 1: weighing electronic grade ammonia water 270.5g with the content of 25-28%, placing the polytetrafluoroethylene reaction kettle in a low-temperature constant-temperature tank, starting a cooling circulation temperature to be set to minus 15 ℃, weighing 20g of tetra (trifluorophosphine) nickel, slowly adding the nickel into the polytetrafluoroethylene reaction kettle by using an injection pump, simultaneously starting stirring, and regulating the rotating speed to 450rpm; after the dripping of the tetra (trifluorophosphine) nickel is completed, the heat preservation reaction is carried out for 2 hours;
Step 2: removing the mixed suspension after the reaction into a polytetrafluoroethylene lining of a hydro-thermal synthesis reactor, wherein the lining has a volume of 500ml, adding 6.063g of 80% hydrazine hydrate (N 2H4·H2 O), 2.6g of sodium hypophosphite monohydrate (NaH 2PO2·H2 O), starting stirring at a speed of 450rpm, assembling the hydro-thermal synthesis reactor after stirring for 3min, and placing the reactor into a 150 ℃ electrothermal blowing drying oven for reacting for 2h;
Step 3: after the reaction is completed and the hydrothermal synthesis reactor is cooled to normal temperature, opening a kettle cover to filter the reaction liquid, putting the filtered solid into a polytetrafluoroethylene tray, drying in an electrothermal blowing drying oven at 200 ℃ for 2 hours, and drying the obtained nickel isotope simple substance to obtain 2.63g of nickel isotope simple substance with the yield of 92.1%.
Example 2
The hydrothermal reduction preparation method of the nickel isotope simple substance comprises the following steps:
Step 1: weighing 268.8g of electronic grade ammonia water with the content of 25-28%, placing the polytetrafluoroethylene reaction kettle in a low-temperature constant-temperature tank, starting a cooling circulation temperature to be set to minus 15 ℃, weighing 20g of tetra (trifluorophosphine) nickel, slowly adding the nickel into the polytetrafluoroethylene reaction kettle by using an injection pump, simultaneously starting stirring, and regulating the rotating speed to 450rpm; and (3) after the completion of the dropwise addition of the tetra (trifluorophosphine) nickel, carrying out heat preservation reaction for 2 hours.
Step 2: removing the reaction liquid into a polytetrafluoroethylene lining of a hydro-thermal synthesis reactor, wherein the lining has a volume of 500ml, adding 15.219g of 80% hydrazine hydrate (N 2H4·H2 O), 5.16g of sodium hypophosphite monohydrate (NaH 2PO2·H2 O), starting stirring at a speed of 450rpm, assembling the hydro-thermal synthesis reactor after stirring for 3min, and placing the reactor into an electrothermal blowing drying box at 150 ℃ for reacting for 2h;
Step 3: after the reaction is completed and the hydrothermal synthesis reactor is cooled to normal temperature, opening a kettle cover to filter the liquid after the reaction, putting the filtered solid into a polytetrafluoroethylene tray, drying in an electrothermal blowing drying oven at 200 ℃ for 2 hours, and drying the obtained nickel isotope simple substance to obtain 2.702g of nickel isotope simple substance with the yield of 94.5%.
Example 3
The elemental detection results of the nickel isotopes prepared in example 1 and example 2 are shown in the following table:
According to the preparation methods in the two embodiments, the yield of the elemental nickel isotope product is over 90 percent, the product shape is good, and the purity of the detected product is more than or equal to 99 percent.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (12)
1. A preparation method of nickel isotope simple substance by hydrothermal reduction is characterized in that: the method comprises the following steps:
Step 1: slowly dripping tetra (trifluorophosphine) nickel into ammonia water to perform decomposition and complexation reaction to obtain a mixed suspension;
step 2: adding a composite reducing agent into the obtained mixed suspension to carry out hydrothermal reduction reaction;
Step 3: filtering the reaction solution, and drying the filter cake to obtain the elemental nickel isotope.
2. The method for preparing the nickel isotope simple substance by hydrothermal reduction according to claim 1, which is characterized in that: in the step 1, tetra (trifluorophosphine) nickel is slowly dripped into ammonia water cooled to the temperature of-20 ℃ to 0 ℃ in advance, and reacts for 2 hours at the temperature of-20 ℃ to 0 ℃ to obtain a mixed suspension.
3. The method for preparing the nickel isotope simple substance by hydrothermal reduction according to claim 2, which is characterized in that: in the decomposition re-complexation reaction, the stirring speed is 300-500rpm.
4. The method for preparing the nickel isotope simple substance by hydrothermal reduction according to claim 1, which is characterized in that: in the step 2, the obtained mixed suspension is transferred to a hydrothermal synthesis reactor, a composite reducing agent is added, and after the mixed solution is uniformly mixed, the hydrothermal synthesis reactor is assembled and is put into an oven for hydrothermal reduction reaction.
5. The method for preparing the nickel isotope simple substance by hydrothermal reduction according to claim 4, which is characterized in that: the composite reducing agent is mixed by hydrazine hydrate and sodium hypophosphite monohydrate.
6. The method for preparing the nickel isotope simple substance by hydrothermal reduction according to claim 5, which is characterized in that: the molar ratio of hydrazine hydrate, sodium hypophosphite monohydrate and tetra (trifluorophosphine) nickel is (2-8): (0.1-1): 1.
7. The method for preparing the nickel isotope simple substance by hydrothermal reduction according to claim 6, which is characterized in that: the hydrothermal reduction temperature is 120-160 ℃ and the reaction time is 1-4h.
8. The method for preparing the nickel isotope simple substance by hydrothermal reduction according to claim 7, which is characterized in that: in the hydrothermal reduction reaction, the stirring speed is 300-500rpm.
9. The method for preparing the nickel isotope simple substance by hydrothermal reduction according to claim 4, which is characterized in that: the lining material of the hydro-thermal synthesis reactor is polytetrafluoroethylene.
10. The method for preparing the nickel isotope simple substance by hydrothermal reduction according to claim 1, which is characterized in that: and 3, putting the filter cake into a polytetrafluoroethylene tray, and putting the polytetrafluoroethylene tray into a blast drying oven at 150-200 ℃ for drying for 2-10h to obtain the elemental nickel isotope.
11. A nickel isotope simple substance prepared by the method for preparing nickel isotope simple substance by hydrothermal reduction according to any one of claims 1-10.
12. Use of the elemental nickel isotopes according to claim 11 in a nickel isotope battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410108775.4A CN117987660A (en) | 2024-01-25 | 2024-01-25 | Nickel isotope simple substance hydrothermal reduction preparation method and nickel isotope simple substance prepared by same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410108775.4A CN117987660A (en) | 2024-01-25 | 2024-01-25 | Nickel isotope simple substance hydrothermal reduction preparation method and nickel isotope simple substance prepared by same |
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| CN117987660A true CN117987660A (en) | 2024-05-07 |
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| CN202410108775.4A Pending CN117987660A (en) | 2024-01-25 | 2024-01-25 | Nickel isotope simple substance hydrothermal reduction preparation method and nickel isotope simple substance prepared by same |
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- 2024-01-25 CN CN202410108775.4A patent/CN117987660A/en active Pending
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