CN105502291A - Recovery method of sodium borohydride solution - Google Patents
Recovery method of sodium borohydride solution Download PDFInfo
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- CN105502291A CN105502291A CN201511022804.2A CN201511022804A CN105502291A CN 105502291 A CN105502291 A CN 105502291A CN 201511022804 A CN201511022804 A CN 201511022804A CN 105502291 A CN105502291 A CN 105502291A
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- CN
- China
- Prior art keywords
- sodium borohydride
- borohydride solution
- boiling
- recovery method
- reducing atmosphere
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Links
- 239000012279 sodium borohydride Substances 0.000 title claims abstract description 34
- 229910000033 sodium borohydride Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000011084 recovery Methods 0.000 title claims abstract description 23
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 28
- 238000009835 boiling Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000002829 reductive effect Effects 0.000 claims description 7
- 239000003637 basic solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract 5
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
- C01B6/15—Metal borohydrides; Addition complexes thereof
- C01B6/19—Preparation from other compounds of boron
- C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a recovery method of a sodium borohydride solution, which comprises the following steps: adding sodium metaborate and a reducer in a mole ratio of 1:(2.0-2.5) into a boiling chamber of a circulating fluid bed, wherein the temperature in the boiling chamber is controlled at 150 DEG C or above; introducing 1-5bar protective gas into a preheater of the circulating fluid bed at the flow rate of greater than 3m/s, and preheating to a certain temperature until the water content of the gas at the gas outlet on the top end of the circulating fluid bed is less than 100ppm; keeping the temperature in the boiling chamber at 250-300 DEG C, introducing a 3-10bar reducing atmosphere into the preheater of the circulating fluid bed at the flow rate of greater than 5m/s, and preheating to a certain temperature; and enabling the reducing atmosphere to flow into the boiling chamber to react with the sodium metaborate until the pressure of the reducing atmosphere in the boiling chamber becomes stable; and finally, discharging the reaction product from the bottom of the circulating fluid bed, and dissolving the reaction product in an alkaline solution, thereby obtaining the sodium borohydride solution. The method has the advantages of mature used equipment and simple technological conditions; and the recovery rate of the sodium borohydride solution can reach 95% or above.
Description
Technical field
The present invention relates to a kind of recovery method of sodium borohydride solution.
Background technology
Sodium borohydride (NaBH
4) at normal temperatures, pH value to be less than in the aqueous solution of 8 can fast and water react and generate sodium metaborate and discharge hydrogen, chemical equation is NaBH
4+ 2H
2o=NaBO
2+ 4H
2↑.So NaBH
4can be kept in strong base solution as hydrogen storage media, control hydrogen rate of release and burst size by the pH value of regulator solution.
In order to save production cost, also in order to reduce boron pollution, realize boron recycle, investigator attempts again reclaiming from sodium metaborate preparing sodium borohydride always.Sodium metaborate is the reacted product of sodium borohydride and water, and it passes through to dewater afterwards and metallic reducing agent, hydrogen reaction can regenerate sodium borohydride.Conventional operational path uses metallic reducing agent (such as MAGNESIUM METAL) to add that the hydrogen of certain pressure reacts under Elevated Temperature Conditions, and reaction formula is NaBO
2+ 2Mg+2H
2=NaBH
4+ 2MgO.In order to accelerate speed of reaction, this reaction usually need high temperature (100 ~ 400 DEG C) and high pressure hydrogen (10 ~ 30bar) or even have catalyzer condition under carry out, the reaction times is 1 ~ 3h, and transformation efficiency can reach more than 90%.But this recovery process generally adopts batch reactor, and the reaction times is longer, reaction needed high temperature, condition of high voltage, have impact on efficiency and the cost of this technique.
Summary of the invention
The present invention aims to provide the recovery method of sodium borohydride solution of a kind ofly to enhance productivity, reducing costs.The present invention is realized by following scheme:
A kind of recovery method of sodium borohydride solution, by sodium metaborate and reductive agent with mol ratio 1:(2.0 ~ 2.5) ratio add in the boiling-house of circulating fluidized bed, boiling room temp controls more than 150 DEG C, the shielding gas passing into 1 ~ 5bar afterwards with the flow velocity being greater than 3m/s is preheated to certain temperature to the primary heater unit of circulating fluidized bed, until the content of water in gas of the gas outlet on circulating fluidized bed top is less than 100ppm, in actual production, the shielding gas of quick flowing makes the fluidization of solid in boiling-house, crystal water rapid dehydration under fluidized state of sodium metaborate evaporates and protected gas takes away boiling-house, the dry raw-material time controling of boiling-house can reach the requirement of the content of water in gas of gas outlet at 5 ~ 10min, afterwards by temperature to 250 ~ 300 DEG C in boiling-house, the reducing atmosphere passing into 3 ~ 10bar with the flow velocity being greater than 5m/s is preheated to certain temperature to the primary heater unit of circulating fluidized bed, reducing atmosphere inflow boiling-house and sodium metaborate react afterwards, until the reducing atmosphere pressure level-off in boiling-house, in actual production, reducing atmosphere passes into boiling-house makes reaction solid particulate be turbulent state, boiling-house temperature remains on 250 ~ 300 DEG C, in reaction process, reducing atmosphere is consumed and causes pressure drop, and constantly supplementary reducing atmosphere can keep the hydrogen pressure in boiling-house progressively to tend towards stability, the time controling that general inflow boiling-house and sodium metaborate carry out reacting is at 20min ~ 2h, reducing atmosphere pressure level-off now in boiling-house, reaction in boiling-house terminates, finally reaction product discharged bottom circulating fluidized bed and be dissolved in basic solution, be i.e. obtained sodium borohydride solution.For obtaining purer sodium borohydride solution, insolubles can be filtered out.
Before passing into shielding gas, first the boiling-house of circulating fluidized bed vacuumized and be heated to more than 150 DEG C predrying 5 ~ 10min, predrainage is carried out to sodium metaborate, and then passing into preheated shielding gas sodium metaborate is dewatered completely.
Further, the preheating temperature of described shielding gas controls more than 100 DEG C, and the preheating temperature of described reducing atmosphere controls at 100 ~ 150 DEG C.Described shielding gas is one or more in nitrogen or rare gas element.Described reducing atmosphere is the atmosphere comprising hydrogen.
Further, described reductive agent is one or more in metallic lithium, sodium, magnesium, calcium, aluminum metal and alloy thereof.By product after reduction is metal oxide, and impurity passes through filtering separation.In actual production, consider Cost Problems, generally adopt the one in magnesium, magnesium alloy or its mixture.
Basic solution can select concentration to be one in the sodium hydroxide solution of 0.5 ~ 1mol/L or potassium hydroxide solution or its mixing.Sodium borohydride is dissolved in basic solution and by product---metal oxide is insoluble in basic solution, namely obtains the sodium borohydride solution that can be reused for release hydrogen after filtering out insolubles.
Further, the particle diameter of described sodium metaborate is 1/3 ~ 1/2 of reductive agent particle diameter.
The preparation method of sodium borohydride solution of the present invention, circulating fluidized bed technique is used to accelerate dehydration and the hydrogenation process of sodium metaborate, reducing atmosphere realizes Rapid Circulation flowing by external pressure, boiling-house entrance reducing atmosphere pressurizes, boiling-house outlet reducing atmosphere reduces pressure, control reducing atmosphere flow velocity, Gu the solid particulate fast fluidization participating in reaction is reached solid--gas three-phase medium (NaBO
2, reductive agent, reducing atmosphere) fully contact thus reduce the object that the mass transfer time reaches accelerated reaction speed, reduces catalyzer usage quantity, reduces the severe condition such as temperature of reaction and reducing atmosphere pressure.The inventive method, uses ripe circulating fluidised bed apparatus, and processing condition are comparatively simple, can improve more than the rate of recovery to 95% reclaiming sodium borohydride from sodium metaborate.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to the statement of embodiment.
embodiment 1
A recovery method for sodium borohydride solution, adds in the boiling-house of circulating fluidized bed by sodium metaborate and MAGNESIUM METAL powder with the ratio of mol ratio 1:2.5, and wherein sodium metaborate particle diameter is 40 ~ 50 μm, and the particle diameter of MAGNESIUM METAL powder is 80 ~ 150 μm.Then the boiling-house of circulating fluidized bed vacuumized and be heated to more than 150 DEG C predrying 5 ~ 10min, predrainage is carried out to sodium metaborate; The nitrogen constantly passing into 2.5bar afterwards with the flow velocity of 3m/s is preheated to 100 DEG C to the primary heater unit of circulating fluidized bed, then nitrogen gas stream is through the dry starting material 10min of boiling-house, boiling room temp controls at 150 DEG C, sodium metaborate is dewatered completely, until the content of water in gas of the gas outlet on circulating fluidized bed top is less than 100ppm.Then the hydrogen constantly passing into 10bar with the flow velocity of 5m/s is preheated to 150 DEG C to the primary heater unit of circulating fluidized bed, hydrogen inflow boiling-house and sodium metaborate carry out reaction 1h afterwards, boiling-house temperature remains on 250 DEG C, and the hydrogen pressure now in boiling-house tends towards stability; Finally reaction product taken out from the bottom of circulating fluidized bed and be dissolved in the sodium hydroxide solution of 1mol/L concentration, after filtering out insolubles magnesium oxide, namely obtaining sodium borohydride solution.
Through measuring and calculating, the rate of recovery that the present embodiment method reclaims sodium borohydride from sodium metaborate reaches more than 95%.
embodiment 2
A recovery method for sodium borohydride solution, the method in its step and embodiment 1 is similar, and its difference is:
1, the mol ratio of sodium metaborate and MAGNESIUM METAL powder is 1:2.2, and the particle diameter of sodium metaborate is 10 ~ 20 μm, and MAGNESIUM METAL powder also uses ultrafine powder, and particle diameter is 20 ~ 60 μm;
2, the pressure of nitrogen is 3bar, and nitrogen gas stream is 5min through the boiling-house dry raw-material time;
3, the pressure of hydrogen is 8bar, and the time that hydrogen inflow boiling-house and starting material carry out reacting is 50min, and the temperature of boiling-house controls at 280 DEG C;
Through measuring and calculating, the rate of recovery that the present embodiment method reclaims sodium borohydride from sodium metaborate reaches more than 95%.
embodiment 3
A recovery method for sodium borohydride solution, the method in its step and embodiment 1 is similar, and its difference is:
1, the mol ratio of sodium metaborate and MAGNESIUM METAL powder is 1:2.0, and the particle diameter of sodium metaborate is 10 ~ 20 μm, and MAGNESIUM METAL powder also uses ultrafine powder, and particle diameter is 20 ~ 60 μm;
2, the flow rate control of hydrogen is 6m/s, and pressure is 5bar, and the time that hydrogen inflow boiling-house and starting material carry out reacting is 30min, and the temperature of boiling-house controls at 300 DEG C;
Through measuring and calculating, the rate of recovery that the present embodiment method reclaims sodium borohydride from sodium metaborate reaches more than 95%.
Claims (8)
1. the recovery method of a sodium borohydride solution, it is characterized in that: by sodium metaborate and reductive agent with mol ratio 1:(2.0 ~ 2.5) ratio add in the boiling-house of circulating fluidized bed, boiling room temp controls more than 150 DEG C, the shielding gas passing into 1 ~ 5bar afterwards with the flow velocity being greater than 3m/s is preheated to certain temperature to the primary heater unit of circulating fluidized bed, until the content of water in gas of the gas outlet on circulating fluidized bed top is less than 100ppm; Afterwards by temperature to 250 ~ 300 DEG C in boiling-house, the reducing atmosphere passing into 3 ~ 10bar with the flow velocity being greater than 5m/s is preheated to certain temperature to the primary heater unit of circulating fluidized bed, reducing atmosphere inflow boiling-house and sodium metaborate react, until the reducing atmosphere pressure level-off in boiling-house afterwards; Finally reaction product discharged bottom circulating fluidized bed and be dissolved in basic solution, be i.e. obtained sodium borohydride solution.
2. the recovery method of a kind of sodium borohydride solution as claimed in claim 1, is characterized in that: before passing into shielding gas, is first vacuumized by the boiling-house of circulating fluidized bed and is heated to more than 150 DEG C predrying 5 ~ 10min.
3. the recovery method of a kind of sodium borohydride solution as claimed in claim 1, is characterized in that: the preheating temperature of described shielding gas controls more than 100 DEG C, and the preheating temperature of described reducing atmosphere controls at 100 ~ 150 DEG C.
4. the recovery method of a kind of sodium borohydride solution as claimed in claim 1, is characterized in that: described reductive agent is one or more in metallic lithium, sodium, magnesium, calcium, aluminum metal and alloy thereof.
5. the recovery method of a kind of sodium borohydride solution as described in one of Claims 1 to 4, is characterized in that: described shielding gas is one or more in nitrogen or rare gas element.
6. the recovery method of a kind of sodium borohydride solution as described in one of Claims 1 to 4, is characterized in that: described reducing atmosphere is the atmosphere comprising hydrogen.
7. the recovery method of a kind of sodium borohydride solution as claimed in claim 5, is characterized in that: described reducing atmosphere is the atmosphere comprising hydrogen.
8. the recovery method of a kind of sodium borohydride solution as described in one of Claims 1 to 4, is characterized in that: the particle diameter of described sodium metaborate is 1/3 ~ 1/2 of reductive agent particle diameter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511022804.2A CN105502291B (en) | 2015-12-30 | 2015-12-30 | A kind of recovery method of sodium borohydride solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511022804.2A CN105502291B (en) | 2015-12-30 | 2015-12-30 | A kind of recovery method of sodium borohydride solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105502291A true CN105502291A (en) | 2016-04-20 |
| CN105502291B CN105502291B (en) | 2018-05-25 |
Family
ID=55710678
Family Applications (1)
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|---|---|---|---|
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| Country | Link |
|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020169106A (en) * | 2019-04-04 | 2020-10-15 | 株式会社Ｋｓｆ | Method and apparatus for immobilizing hydrogen |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3379511A (en) * | 1962-09-25 | 1968-04-23 | Degussa | Production of sodium borohydride |
| JP2005097047A (en) * | 2003-09-25 | 2005-04-14 | Nippei Toyama Corp | Tetrahydroborate production apparatus and method |
| CN1778668A (en) * | 2004-10-08 | 2006-05-31 | 罗门哈斯公司 | Direct elemental synthesis of sodium borohydride |
| WO2015190403A1 (en) * | 2014-06-11 | 2015-12-17 | 吉崎 敦浩 | Method and device for producing sodium borohydride |
-
2015
- 2015-12-30 CN CN201511022804.2A patent/CN105502291B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3379511A (en) * | 1962-09-25 | 1968-04-23 | Degussa | Production of sodium borohydride |
| JP2005097047A (en) * | 2003-09-25 | 2005-04-14 | Nippei Toyama Corp | Tetrahydroborate production apparatus and method |
| CN1778668A (en) * | 2004-10-08 | 2006-05-31 | 罗门哈斯公司 | Direct elemental synthesis of sodium borohydride |
| WO2015190403A1 (en) * | 2014-06-11 | 2015-12-17 | 吉崎 敦浩 | Method and device for producing sodium borohydride |
Non-Patent Citations (2)
| Title |
|---|
| BIN HONG LIU ET AL.: "Sodium Borohydride Synthesis by Reaction of Na2O Contained Sodium Borate with Al and Hydrogen", 《ENERGY & FUELS》 * |
| TENGJIAO OU ET AL.: "Thermodynamic and kinetic studies of NaBH4 regeneration by NaBO2eMgeH2 ternary system at isothermal condition", 《I N T E RNA T I ONAL JOURNAL O F HYDROGEN ENERGY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020169106A (en) * | 2019-04-04 | 2020-10-15 | 株式会社Ｋｓｆ | Method and apparatus for immobilizing hydrogen |
| JP7412893B2 (en) | 2019-04-04 | 2024-01-15 | 訓範 津田 | Sodium borohydride manufacturing method and sodium borohydride manufacturing device |
| JP7559199B2 (en) | 2019-04-04 | 2024-10-01 | 訓範 津田 | Sodium borohydride manufacturing method and sodium borohydride manufacturing apparatus |
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| CN105502291B (en) | 2018-05-25 |
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