CN115650280A - Preparation method of gallium salt - Google Patents
Preparation method of gallium salt Download PDFInfo
- Publication number
- CN115650280A CN115650280A CN202211103482.4A CN202211103482A CN115650280A CN 115650280 A CN115650280 A CN 115650280A CN 202211103482 A CN202211103482 A CN 202211103482A CN 115650280 A CN115650280 A CN 115650280A
- Authority
- CN
- China
- Prior art keywords
- gallium
- solid
- solution
- salt
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000002258 gallium Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 41
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims abstract description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims abstract description 28
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 150000001450 anions Chemical class 0.000 claims abstract description 12
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 52
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 26
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052733 gallium Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 14
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims description 14
- 229940044658 gallium nitrate Drugs 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- -1 sulfate radical Chemical class 0.000 claims description 4
- YEEGWNXDUZONAA-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-gallabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Ga+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YEEGWNXDUZONAA-UHFFFAOYSA-K 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- 229910000154 gallium phosphate Inorganic materials 0.000 claims description 2
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 claims description 2
- DWRNSCDYNYYYHT-UHFFFAOYSA-K gallium(iii) iodide Chemical compound I[Ga](I)I DWRNSCDYNYYYHT-UHFFFAOYSA-K 0.000 claims description 2
- LWFNJDOYCSNXDO-UHFFFAOYSA-K gallium;phosphate Chemical compound [Ga+3].[O-]P([O-])([O-])=O LWFNJDOYCSNXDO-UHFFFAOYSA-K 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 abstract description 3
- 238000012824 chemical production Methods 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 3
- 229910001195 gallium oxide Inorganic materials 0.000 description 3
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- GZGPRZYZKBQPBQ-UHFFFAOYSA-N 1,4-dioxaspiro[4.5]decane Chemical compound O1CCOC11CCCCC1 GZGPRZYZKBQPBQ-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910005269 GaF 3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000005292 diamagnetic effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a preparation method of gallium salt, belonging to the technical field of chemical production. The process of the invention comprises gallium chloride (GaCl) 3 ) Rapid preparation of solutions, anion (X) n‑ ) Target gallium salt (Ga) of n X 3 ) And (4) separating out, solid-liquid separating and the like. The method of the invention utilizes hydrochloric acid to rapidly dissolve the gallium sesquioxide solid, and then uses GaCl according to the solubility difference of the gallium salt 3 Conversion to Ga n X 3 Then saturated and separated out. The invention has the characteristic of high reaction speed, can produce various gallium salts, is beneficial to improving the production efficiency and simplifying the production flow.
Description
Technical Field
The invention relates to a preparation method of gallium salt, belonging to the technical field of chemical production.
Background
Digallium trioxide, the most stable gallium oxide, and is an amphoteric oxide. There are five isomers: α, β, γ, δ, ε, the most stable of which is the β -isomer. The burned gallium trioxide is insoluble in dilute nitric acid, dilute sulfuric acid, dilute hydrochloric acid, even concentrated nitric acid, and strong alkali aqueous solution, and can only pass through NaOH, KOH or KHSO 4 And K 2 S 2 O 7 Melting together to dissolve it, with a double excess of NH 4 The Cl melts together at 250 ℃ to form gallium chloride.
Gallium nitrate is a colorless transparent crystal, is easy to absorb moisture, is easy to decompose in air and has a boiling point of 200 ℃ (decomposing into Ga) 2 O 3 ). Is easily soluble in water (the mass fraction of gallium nitrate octahydrate dissolved in water is 45.84%), ethanol and the like, and is insolubleIn diethyl ether. It is widely applied in the fields of medicine, materials, catalysts and the like. Because gallium oxide is difficult to react with nitric acid, the preparation of gallium nitrate is difficult, and the application of gallium nitrate is limited. Gallium nitrate is currently produced primarily by placing gallium or gallium hydroxide in concentrated nitric acid.
In the prior art, the preparation method of gallium nitrate comprises the following steps: dissolving gallium sesquioxide into nitric acid solution, controlling the molar ratio of the gallium sesquioxide to the nitric acid to be 1.6-1.8, and repeatedly adding water, heating, evaporating, adding water and the like for 6-15 hours until a transparent and non-irritant solution is formed; at the water temperature of 40-80 ℃ and the system pressure of 0.05 multiplied by 10 5 ～0.5×10 5 Heating the solution in water bath for 8-16 hours under the condition of Pa, and removing most of water and nitric acid; and drying the concentrated solution at 40-80 ℃ under nitrogen or air at normal pressure for 18-36 hours to obtain the gallium nitrate.
Gallium sulfate is a white or colorless powder, has strong hygroscopicity, is slightly soluble in cold water, is easily soluble in hot water, alcohol, etc., and is insoluble in diethyl ether. The method is widely applied to the aspects of high-purity compound preparation reagents, organic reaction catalysts and the like, and can be used for synthesizing cyclohexanone ethylene ketal, edible spices isobutyl isobutyrate, butyl lactate, ethyl cinnamate and the like. The dissolved mass fraction of the octadecanoic acid gallium sulfate in the water is 36.80%, if the hydrate is heated, tetradecyl hydrate, heptahydrate and the like are dehydrated in sequence, and anhydrous substances of white powder can be obtained when the temperature is between 165 and 360 ℃. Currently, there are two common methods for preparing gallium sulfate: (1) putting gallium metal into sulfuric acid, and reacting at room temperature or under heating; (2) gallium hydroxide is dissolved in sulfuric acid. And concentrating and extracting the prepared gallium sulfate solution to obtain the gallium sulfate octadecahydrate crystal.
In the prior art, the preparation method of gallium sulfate is to take a certain amount of electrolytic waste liquid of gallium metal, to carry out vacuum filtration to remove black scum and passive film, to obtain relatively pure filtrate, to neutralize the filtrate to the end point with inorganic acid, and to neutralize the obtained Ga (OH) 3 Washing with hot water and filtering to obtain pure filter cake. Preparing a sulfuric acid solution with a certain concentration, placing a container containing sulfuric acid on a magnetic stirrer, setting the temperature at 70 ℃, and stirringThen adding a certain amount of gallium hydroxide filter cake, and reacting for 24-60 hours. After the reaction is finished, evaporating and concentrating the solution at the temperature of 60-70 ℃ to a saturated state, cooling the concentrated solution to room temperature, adding a quantitative organic mixture, then placing the mixture into the cooling solution for 2-4 hours to precipitate crystals of the gallium sulfate octadecahydrate, placing the precipitated crystals on filter paper for suction filtration, placing the crystals in a drying oven for drying at the temperature of 60-80 ℃, and grinding to obtain white powdery gallium sulfate octadecahydrate.
Gallium chloride is a white or colorless needle-like crystal, is easy to deliquesce, is very soluble in water and has a boiling point of 201.3 ℃. Is soluble in almost all solvents, even alkanes. It is the main precursor of most gallium derivatives, an important raw material for the synthesis of organogallium reagents. Can be used for spectral analysis and organic reaction catalyst. The coordination chemistry of Ga (III) and Fe (III) is similar, and gallium (III) compounds have been used as diamagnetic analogs of iron compounds. At present, there are two main routes for preparing gallium chloride: (1) reacting metal gallium with dry hydrogen chloride at 200 ℃, cooling and collecting; (2) reacting gallium sesquioxide with thionyl chloride at 200 ℃, and collecting by distillation.
In the prior art, the preparation method of gallium chloride comprises the following steps: firstly, adding liquid metal gallium into a reaction kettle, and then introducing chlorine into the liquid metal gallium; the temperature of the reaction kettle is regulated to be 200-400 ℃, and a main product gallium chloride and a byproduct gallium trichloride are obtained after a first preset time period; regulating the temperature of the reaction kettle to be 100-300 ℃, and obtaining liquid gallium trichloride and gaseous gallium trichloride after a second preset time period; evaporating the obtained gaseous gallium trichloride into a fractionating tube, and cooling to enable the gaseous gallium trichloride to become liquid gallium trichloride to flow into a storage device.
Therefore, at present, the reaction time is too long, the operation is complex, the production type is single, and the industrial production is difficult in the preparation process of the gallium salt.
Disclosure of Invention
The invention provides a preparation method of gallium salt aiming at the problems of overlong reaction time, complex operation, single production type and difficult industrial production in the preparation process of the gallium salt, the invention utilizes hydrochloric acid to quickly dissolve the solid gallium trioxide, and then converts gallium chloride into target gallium salt according to the solubility difference of the gallium salt and then saturatedly separates out the gallium salt; has the characteristic of high reaction speed, can produce various kinds of gallium salts, is beneficial to improving the production efficiency and simplifying the production flow.
A preparation method of gallium salt comprises the following specific steps:
(1) Preparing a gallium chloride solution: adding the gallium sesquioxide solid into a hydrochloric acid solution, and heating the solution under the condition of stirring until the gallium sesquioxide solid is completely dissolved to obtain a gallium chloride solution;
(2) Adding anions, and separating out target gallium salt: anion X n- Adding into gallium chloride solution, and converting the gallium chloride solution into GaCl 3 -Ga n X 3 Mixed solution, gaCl 3 -Ga n X 3 Ga in mixed solution n X 3 Mass greater than Ga n X 3 When the solubility is self-consistent, an anion X is added n- Reacting Ga n X 3 Supersaturation is separated out to obtain a solid-liquid mixture;
(3) Solid-liquid separation: and carrying out solid-liquid separation on the solid-liquid mixture, wherein the solid is the target gallium salt.
The mass fraction of the hydrochloric acid is 1-38%, and preferably, the mass fraction of the hydrochloric acid is 26-32%.
The heating temperature of the step (1) is 100-500 ℃, and the heating time is 0.5-5 h; preferably, the heating temperature is 100-300 ℃, and the heating time is 0.8-3 h;
the anion X in the step (2) n- Is sulfate radical, nitrate radical, bromide ion, iodide ion, phosphate radical, fluoride ion, iodate radical or citrate radical; anion X thereof n- The addition mode of (A) is sulfuric acid, nitric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, ammonium fluoride, iodic acid and potassium citrate.
Preferably, the anion X n- Is sulfate, nitrate, fluoride or iodate.
The target gallium salt Ga in the step (2) n X 3 Is selected from gallium sulfate, gallium nitrate, gallium bromide, gallium iodide, gallium phosphate,Gallium fluoride, gallium iodate, or gallium citrate. Preferably, the target gallium salt is gallium sulfate, gallium nitrate, gallium fluoride or gallium iodate.
The preparation principle of the gallium salt is as follows:
the gallium sesquioxide is an amphoteric oxide which, when dissolved in hydrochloric acid, reacts with H in the hydrochloric acid + Reaction to form Ga 3+ The related reaction formula is shown in (1). Ga 3+ And is easy to react with Cl in inorganic acid - Reaction to produce [ GaCl 4 ] - Coordinate ions to promote Ga 2 O 3 Thereby causing Ga to dissolve 2 O 3 The rapid dissolution is shown in a related reaction formula (2);
the chemical reaction equation is as follows:
Ga 2 O 3 +6H + ＝2Ga 3+ +3H 2 O (1)
Ga 3+ +4Cl - ＝[GaCl 4 ] - (2)
adding anion X to the solution n- Due to Ga n X 3 The mass soluble in solution is limited when Ga is in solution n X 3 When the mass of (A) is at a maximum, X is added n- ，Ga n X 3 And will precipitate.
The invention has the beneficial effects that:
(1) The invention utilizes the characteristic that hydrochloric acid can rapidly dissolve the gallium sesquioxide solid to rapidly prepare the gallium chloride solution, and can obviously shorten the dissolution time of the gallium sesquioxide.
(2) The invention utilizes the solubility difference of the gallium salt to convert the gallium chloride into the target gallium salt and then to carry out saturated precipitation, can be used for producing various gallium salts, and has simple process.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a preparation method of gallium salt (gallium sulfate) comprises the following specific steps:
(1) Adding the gallium sesquioxide solid into hydrochloric acid solution with the mass fraction of 26%, stirring to enable the gallium sesquioxide solid to be suspended in the solution, adjusting the heating temperature to be 100 ℃, keeping the temperature for 3 hours after the solution is boiled, and completely dissolving the gallium sesquioxide solid to obtain clear gallium chloride solution;
(2) Adding commercially available concentrated sulfuric acid dropwise into the gallium chloride solution, and converting the gallium chloride solution into GaCl 3 -Ga 2 (SO 4 ) 3 Mixing the solution as GaCl 3 -Ga 2 (SO 4 ) 3 Ga in mixed solution 2 (SO 4 ) 3 Has a mass fraction of more than 36.80% (Ga at room temperature) 2 (SO 4 ) 3 When the solubility of (2) was 36.80% (mass fraction, the same applies hereinafter), sulfuric acid and Ga were further added dropwise 2 (SO 4 ) 3 Separating out; when the solid is not increased any more, stopping adding the sulfuric acid to obtain a solid-liquid mixture;
(3) Carrying out solid-liquid separation on the solid-liquid mixture, wherein the solid is gallium sulfate; because the filtrate also contains a part of gallium sulfate, the Ga in the filtrate can be concentrated and distilled by virtue of the characteristic that gallium chloride and hydrochloric acid are easy to volatilize 2 (SO 4 ) 3 Separating out;
the solid obtained in this example was subjected to composition analysis, and the specific results are shown in Table 1.
TABLE 1 mass fraction of each ion in solid (%)
Ga in the solid of this example in mass percent 3+ 32.54% SO 4 2- 66.98% of the total Ga content, as calculated, is 2 (SO 4 ) 3 The purity of (2) was 99.0%.
Example 2: a preparation method of gallium salt (gallium nitrate) comprises the following specific steps:
(1) Adding the gallium sesquioxide solid into a hydrochloric acid solution with the mass fraction of 28%, stirring to enable the gallium sesquioxide solid to be suspended in the solution, adjusting the heating temperature to 150 ℃, keeping the temperature for 1.9 hours after the solution is boiled, and completely dissolving the gallium sesquioxide solid to obtain a clear gallium chloride solution;
(2) Adding commercial concentrated nitric acid dropwise into gallium chloride solution, and converting the gallium chloride solution into GaCl 3 -Ga(NO 3 ) 3 Mixed solution, when Ga (NO) in the mixed solution 3 ) 3 Is greater than 45.84% (at room temperature, ga (NO) 3 ) 3 When the solubility of (2) is 45.84%), nitric acid and Ga (NO) are further added dropwise 3 ) 3 Separating out; when the solid is not increased any more, stopping adding the nitric acid to obtain a solid-liquid mixture;
(3) Carrying out solid-liquid separation on the solid-liquid mixture, wherein the solid is gallium nitrate; because the filtrate also contains a part of gallium nitrate, the filtrate is concentrated and added with tributyl phosphate for extraction, and the extract liquid is subjected to back extraction, concentration and the like, so that the Ga (NO) in the filtrate can be obtained 3 ) 3 Separating out;
the solid obtained in this example was subjected to composition analysis, and the specific results are shown in table 2;
table 2 mass fraction of each ion in solid (%)
Ga in the solid of this example in mass percent 3+ 27.25% of NO 3 - 71.62% of Ga (NO) was found by calculation 3 ) 3 The purity of (2) was 98.0%.
Example 3: a preparation method of gallium salt (gallium fluoride) comprises the following specific steps:
(1) Adding the gallium sesquioxide solid into a hydrochloric acid solution with the mass fraction of 30%, stirring to enable the gallium sesquioxide solid to be suspended in the solution, adjusting the heating temperature to 200 ℃, keeping the temperature for 1.3 hours after the solution is boiled, and completely dissolving the gallium sesquioxide solid to obtain a clear gallium chloride solution;
(2) Commercially available ammonium fluoride powder was slowly added to the gallium chloride solution which was converted to GaCl 3 -GaF 3 Mixing the solution while mixing GaF in the solution 3 Is more than 0.0016 percent (GaF at room temperature) 3 When the solubility of (1) is 0.0016%), ammonium fluoride and GaF are further added 3 Separating out; when the solid is not increased any more, stopping adding the ammonium fluoride to obtain a solid-liquid mixture;
(3) Carrying out solid-liquid separation on the solid-liquid mixture, wherein the solid is gallium fluoride; gaF in the filtrate due to the low solubility of gallium fluoride 3 Treatment may not be performed;
the solid obtained in this example was subjected to composition analysis, and the specific results are shown in table 3;
TABLE 3 mass fraction of each ion in solid (%)
Ga in the solid of this example in mass percent 3+ 54.95% by weight, F - Accounting for 44.88 percent, the GaF can be found by calculation 3 The purity of (2) was 99.8%.
Example 4: a preparation method of gallium salt (gallium iodate) comprises the following specific steps:
(1) Adding the gallium sesquioxide solid into a hydrochloric acid solution with the mass fraction of 32%, stirring to enable the gallium sesquioxide solid to be suspended in the solution, adjusting the heating temperature to 300 ℃, keeping the temperature for 0.8h after the solution is boiled, and completely dissolving the gallium sesquioxide solid to obtain a clear gallium chloride solution;
(2) Commercially available iodic acid powder was slowly added to the gallium chloride solution, which was converted to GaCl 3 -Ga(IO 3 ) 3 Mixing solutions, when Ga (IO) in solution is mixed 3 ) 3 Is more than 0.85% (at room temperature, ga (IO) 3 ) 3 When the solubility of the acid is 0.85 percent), the iodic acid and the Ga (IO) are continuously added 3 ) 3 And (4) precipitating. When the solid is not increased any more, stopping adding the iodic acid to obtain a solid-liquid mixture;
(3) And (4) carrying out solid-liquid separation on the solid-liquid mixture, wherein the solid is the gallium iodate. Due to the fact thatThe solubility of gallium iodate is very low and Ga (IO) in the filtrate 3 ) 3 Treatment may not be performed;
the solid obtained in this example was subjected to composition analysis, and the specific results are shown in table 4;
TABLE 4 mass fraction of each ion in solid (%)
Ga in the solid of this example in mass percent 3+ 11.72% of IO 3 - 88.04%, ga (IO) is found by calculation 3 ) 3 The purity of (2) was 99.2%.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (5)
1. A preparation method of gallium salt is characterized in that: the method comprises the following specific steps:
(1) Preparing a gallium chloride solution: adding the gallium sesquioxide solid into a hydrochloric acid solution, and heating the solution under the condition of stirring until the gallium sesquioxide solid is completely dissolved to obtain a gallium chloride solution;
(2) Adding anions, and separating out target gallium salt: anion X n- Adding into gallium chloride solution, and converting the gallium chloride solution into GaCl 3 -Ga n X 3 Mixed solution, gaCl 3 -Ga n X 3 Ga in mixed solution n X 3 Mass greater than Ga n X 3 When the solubility is self-sufficient, an anion X is added n- Reacting Ga n X 3 Supersaturation is separated out to obtain a solid-liquid mixture;
(3) Solid-liquid separation: and carrying out solid-liquid separation on the solid-liquid mixture, wherein the solid is the target gallium salt.
2. The method of claim 1, wherein: the mass fraction of the hydrochloric acid in the step (1) is 1-38%.
3. The method of claim 1, wherein: the heating temperature in the step (1) is 100-500 ℃, and the heating time is 0.5-5h.
4. The method of claim 1, wherein: step (2) anion X n- Is sulfate radical, nitrate radical, bromide ion, iodide ion, phosphate radical, fluoride ion, iodate radical or citrate radical.
5. The method of claim 1, wherein: step (2) target gallium salt Ga n X 3 Is gallium sulfate, gallium nitrate, gallium bromide, gallium iodide, gallium phosphate, gallium fluoride, gallium iodate or gallium citrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211103482.4A CN115650280A (en) | 2022-09-09 | 2022-09-09 | Preparation method of gallium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211103482.4A CN115650280A (en) | 2022-09-09 | 2022-09-09 | Preparation method of gallium salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115650280A true CN115650280A (en) | 2023-01-31 |
Family
ID=84983884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211103482.4A Pending CN115650280A (en) | 2022-09-09 | 2022-09-09 | Preparation method of gallium salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115650280A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467157A (en) * | 2002-07-12 | 2004-01-14 | 清华大学 | Method for preparing gallium nitrate |
| CN1951823A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Process for preparing gallium nitrate |
| CN108439435A (en) * | 2018-03-24 | 2018-08-24 | 山东天化学股份有限公司 | A kind of method that direct method prepares potassium nitrate |
| CN108585051A (en) * | 2018-05-23 | 2018-09-28 | 中南大学 | A kind of method that copper chloride manganese liquid prepares LITHIUM BATTERY manganese sulfate |
| CN111908488A (en) * | 2020-07-30 | 2020-11-10 | 华融化学股份有限公司 | High-purity reagent-grade potassium chloride and production method thereof |
| CN112028025A (en) * | 2019-06-04 | 2020-12-04 | 泰安汉威集团有限公司 | Green production process of insoluble iodate |
| CN112408680A (en) * | 2019-11-29 | 2021-02-26 | 中冶长天国际工程有限责任公司 | Method for fine treatment of wastewater containing fluorine and chlorine |
| CN113998710A (en) * | 2020-07-28 | 2022-02-01 | 自然资源部天津海水淡化与综合利用研究所 | Method for separating potassium fluoride, potassium bromide, potassium carbonate and potassium bicarbonate mixed salt |
-
2022
- 2022-09-09 CN CN202211103482.4A patent/CN115650280A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467157A (en) * | 2002-07-12 | 2004-01-14 | 清华大学 | Method for preparing gallium nitrate |
| CN1951823A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Process for preparing gallium nitrate |
| CN108439435A (en) * | 2018-03-24 | 2018-08-24 | 山东天化学股份有限公司 | A kind of method that direct method prepares potassium nitrate |
| CN108585051A (en) * | 2018-05-23 | 2018-09-28 | 中南大学 | A kind of method that copper chloride manganese liquid prepares LITHIUM BATTERY manganese sulfate |
| CN112028025A (en) * | 2019-06-04 | 2020-12-04 | 泰安汉威集团有限公司 | Green production process of insoluble iodate |
| CN112408680A (en) * | 2019-11-29 | 2021-02-26 | 中冶长天国际工程有限责任公司 | Method for fine treatment of wastewater containing fluorine and chlorine |
| CN113998710A (en) * | 2020-07-28 | 2022-02-01 | 自然资源部天津海水淡化与综合利用研究所 | Method for separating potassium fluoride, potassium bromide, potassium carbonate and potassium bicarbonate mixed salt |
| CN111908488A (en) * | 2020-07-30 | 2020-11-10 | 华融化学股份有限公司 | High-purity reagent-grade potassium chloride and production method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109897070B (en) | Preparation method of tetraamminepalladium acetate (II) | |
| ZA200500319B (en) | Preparation of solid ammonium glyphosate using organinc solvent in extraction | |
| CN111004162B (en) | Method and device for preparing L-selenocysteine by using sodium triacetoxyborohydride as reducing agent | |
| US2654779A (en) | Method of preparation of guanidino fatty acids | |
| US4528175A (en) | Production of chromium (III) compounds | |
| CN109516487B (en) | Method for preparing calcium bicarbonate powder by solvent method | |
| CN115650280A (en) | Preparation method of gallium salt | |
| WO2019144475A1 (en) | Method for preparing high-valence iron salt | |
| US2277778A (en) | Process for producing salts | |
| CN107416864B (en) | Preparation method of ammonium ferrocyanide hydrate | |
| CN211998846U (en) | Device for separating potassium bisulfate and potassium sulfate mixture | |
| EP0448373A2 (en) | Chelate compositions and their production | |
| CN103664729B (en) | Method for preparing L-pyroglutamic acid | |
| US3848063A (en) | Process for the manufacture of high-purity lithium hexafluoroarsenate | |
| CN109183093B (en) | Preparation method of tetraammine palladium bicarbonate compound | |
| JPH024534B2 (en) | ||
| CN112409196A (en) | Preparation process of aminomethylbenzoic acid based on Delbin reaction | |
| CN110436520A (en) | The method for preparing vanadium product using sodium vanadate cleaning | |
| JP2828349B2 (en) | Method for producing tin trifluoromethanesulfonate | |
| US3670000A (en) | Process of producing difficulty soluble metal gluconates | |
| RU2747639C1 (en) | Method for synthesis of potassium monophosphate | |
| CN115535979B (en) | Potassium dihydrogen phosphate and method for preparing potassium dihydrogen phosphate by using calcium hydrogen phosphate | |
| CN110885288B (en) | Synthesis method of isooctyl p-methoxycinnamate | |
| CN112694075A (en) | Process for producing monopotassium phosphate by using potassium nitrate as raw material | |
| CN104030330A (en) | Method for preparing high-purity aluminum hydroxide through induced crystallization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |