CN104445342A - Rare-earth salt sulfate and preparation method thereof - Google Patents
Rare-earth salt sulfate and preparation method thereof Download PDFInfo
- Publication number
- CN104445342A CN104445342A CN201410678802.8A CN201410678802A CN104445342A CN 104445342 A CN104445342 A CN 104445342A CN 201410678802 A CN201410678802 A CN 201410678802A CN 104445342 A CN104445342 A CN 104445342A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- earth salt
- water
- sulfuric acid
- crystal
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 89
- 150000002910 rare earth metals Chemical class 0.000 title claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title 1
- 150000003839 salts Chemical class 0.000 title 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 81
- -1 salt sulfate Chemical class 0.000 claims abstract description 81
- 239000013078 crystal Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 230000009965 odorless effect Effects 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000001117 sulphuric acid Substances 0.000 claims description 44
- 235000011149 sulphuric acid Nutrition 0.000 claims description 44
- 230000000630 rising effect Effects 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 10
- 238000003828 vacuum filtration Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 3
- 210000003298 dental enamel Anatomy 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 2
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 8
- QLAFITOLRQQGTE-UHFFFAOYSA-H gadolinium(3+);trisulfate Chemical compound [Gd+3].[Gd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QLAFITOLRQQGTE-UHFFFAOYSA-H 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- 238000004886 process control Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 6
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 6
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 6
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 5
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 5
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 5
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 description 5
- RQXZRSYWGRRGCD-UHFFFAOYSA-H gadolinium(3+);tricarbonate Chemical compound [Gd+3].[Gd+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O RQXZRSYWGRRGCD-UHFFFAOYSA-H 0.000 description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- C01F17/282—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a rear-earth salt sulfate with good water solubility prepared through rear-earth salt sulfate. The rear-earth salt sulfate is characterized in that the rear-earth salt sulfate is powder-like odorless crystals in appearance, the chemical formula is RE2(SO4)3.nH2O, the rear-earth salt sulfate is dissolved in water and acid, the solution is clear, the solubility in water is decreased along with the increase of temperature, and the solubility in a sulfuric acid solution is decreased along with the increase of temperature. The preparation method comprises the following steps: adding rear-earth salt sulfate to the sulfuric acid solution for acid solubility, filtering and removing impurities, crystallization, rinsing and dehydration, and baking. The rear-earth salt sulfate is simple in technological process, low in acid soluble acidity, less in spent acid, less in equipment corrosion, free of environmental pollution, high in product yield and low in cost; the prepared rear-earth salt sulfate is good in water solubility.
Description
Technical field
The present invention relates to a kind of rare-earth products and preparation method, specifically a kind of sulfuric acid rare earth Salt And Preparation Method, particularly relate to a kind of sulfuric acid rare earth Salt And Preparation Method being prepared good water solubility by carbonated rare earth salt.
Background technology
Rare earth is one group of new function material simultaneously with multifrequency natures such as electricity, magnetic, light, superconduction, catalysis and biologies, it is the important foundation material of the high-tech sectors such as information technology, biotechnology, novel material, new energy technology and national defense construction, simultaneously also to some conventional industries of transformation, as agricultural, chemical industry, building materials etc. play an important role.Rare earth is of many uses, and the functional materials of rare earth can be used of a great variety, is forming a large-scale hi-tech industry group, is having very wide market outlook and very important strategic importance, have the laudatory title of " industrial VITAMIN ".Sulfuric acid rare earth is mainly used in sanitas, laboratory reagent, organic intermediate, fine chemicals, catalyst aid, bio-pharmaceuticals etc.
The preparation of current sulfuric acid rare earth salt, application number is the preparation method that application discloses a kind of anhydrous ceric sulfate of 200810150416.6, and it is with Ce (OH)
4for raw material, with the sulfuric acid dissolution cerous hydroxide of 9.1mol/L ~ 9.2mol/L, controlling solvent temperature is 70 DEG C ~ 80 DEG C, and rare earth concentration is 1.05 mol/L ~ 1.16mol/L, spent acid 4.4 mol/L ~ 4.6 mol/L, start stirring to make it to dissolve completely, filter, get filtrate limit heating in reactor, limit is stirred, make it to be concentrated into and separate out ceric sulfate crystal, centrifugally toast to obtain anhydrous powder shape ceric sulfate.The acid-soluble acidity of this preparation method is high, and spent acid is high, has certain corrodibility to equipment, and ceric sulfate prepared by this technique is water-soluble bad, and yield is low, and cost is higher.
Summary of the invention
The object of this invention is to provide a kind of sulfuric acid rare earth Salt And Preparation Method being prepared good water solubility by carbonated rare earth salt.
The present invention adopts following technical scheme to realize its goal of the invention, a kind of sulfuric acid rare earth salt, and outward appearance is Powdered odorless crystal, and chemical formula is RE
2(SO
4)
3.nH
20, under room temperature, n is 3 ~ 9, and water-soluble and sour, solution is limpid, the rising of the solubility with temperature in water and declining, and the solubleness in sulphuric acid soln reduces with the rising of acidity.
A kind of sulfuric acid rare earth salt, outward appearance is Powdered odorless crystal, and chemical formula is RE
2(SO
4)
3.nH
20, under room temperature, n is less than 0.5, and water-soluble and sour, solution is limpid, the rising of the solubility with temperature in water and declining, and the solubleness in sulphuric acid soln reduces with the rising of acidity.
A preparation method for sulfuric acid rare earth salt, it comprises the following steps:
(1) in enamel reactor, compound concentration is the sulphuric acid soln of 0.5mol/L ~ 2.0mol/L, is cooled to 30 DEG C ~ 35 DEG C; Slowly added by carbonated rare earth salt and carry out acid-soluble in the sulphuric acid soln prepared, solvent temperature 30 DEG C ~ 70 DEG C, obtains rare earth sulfate solution, to the pH value 3.5 ~ 4.0 of described solution;
(2) by step (1) gained rare earth sulfate solution filtering and impurity removing, obtain limpid rare earth sulfate solution, with dilute sulphuric acid adjust pH to 1.5 ~ 2;
(3) the step rare earth sulfate solution stirring heating that (2) gained is limpid is boiled, crystal is separated out, is less than 10g/L to the rare earth concentration in mother liquor;
By step (3) gained crystal mixing solutions be placed in strainer and filter, the gained crystal rinsed with deionized water of closely boiling, vacuum filtration obtains sulfuric acid rare earth salt;
(5) sulfuric acid rare earth salt centrifuge dewatering step (4) obtained, obtains the sulfuric acid rare earth salt containing 3 ~ 9 crystal water.
The present invention step (5) in, toast containing the sulfuric acid rare earth salt of 3 ~ 9 crystal water at 150 DEG C ~ 260 DEG C temperature, obtain anhydrous slufuric acid rare-earth salts.
The present invention step (1) in, the preferred concentration of described sulphuric acid soln is 1.0mol/L ~ 1.5mol/L.
Owing to adopting technique scheme, the present invention achieves goal of the invention preferably, and technical process is succinct, and acid-soluble acidity is low, and spent acid is low, and equipment corrosion is little, non-environmental-pollution and product yield is high, and cost is low; The sulfuric acid rare earth water-soluble of preparation is good.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
A kind of sulfuric acid rare earth salt, outward appearance is Powdered odorless crystal, and chemical formula is RE
2(SO
4)
3.nH
20, under room temperature, n is 3 ~ 9, and water-soluble and sour, solution is limpid, the rising of the solubility with temperature in water and declining, and the solubleness in sulphuric acid soln reduces with the rising of acidity.
A preparation method for sulfuric acid rare earth salt, it comprises the following steps:
(1) in enamel reactor, compound concentration is the sulphuric acid soln of 0.5mol/L ~ 2.0mol/L, is cooled to 30 DEG C ~ 35 DEG C; Slowly added by carbonated rare earth salt and carry out acid-soluble in the sulphuric acid soln prepared, solvent temperature 30 DEG C ~ 70 DEG C, obtains rare earth sulfate solution, to the pH value 3.5 ~ 4.0 of described solution;
(2) by step (1) gained rare earth sulfate solution filtering and impurity removing, obtain limpid rare earth sulfate solution, with dilute sulphuric acid adjust pH to 1.5 ~ 2;
(3) the step rare earth sulfate solution stirring heating that (2) gained is limpid is boiled, crystal is separated out, is less than 10g/L to the rare earth concentration in mother liquor;
By step (3) gained crystal mixing solutions be placed in strainer and filter, the gained crystal rinsed with deionized water of closely boiling, vacuum filtration obtains sulfuric acid rare earth salt;
(5) sulfuric acid rare earth salt centrifuge dewatering step (4) obtained, obtains the sulfuric acid rare earth salt containing 3 ~ 9 crystal water.
The sulphuric acid soln 2000L of the present embodiment preparation 0.6mol/L, be cooled to 30 DEG C, it is complete that the Phosbloc being 43.5 ﹪ by 298 ㎏ TREO while stirring adds dissolving in sulphuric acid soln, dissolution process controls solvent temperature 55 DEG C, to the pH value 3.5 of solution, now, the concentration of solution middle-weight rare earths is 0.37mol/L; By solution filtering and impurity removing, with dilute sulphuric acid adjust pH to 2, obtain limpid rare earth sulfate solution 2150L; Limpid rare earth sulfate solution stirring heating being boiled, crystal is separated out, is 5g/L to the rare earth concentration in mother liquor, obtains 1850L slip; For preventing dissolution of crystals, improve direct yield, by slip fast filtering, by the rinsed with deionized water of closely boiling, vacuum filtration obtains lanthanum sulfat, and filtrate obtains Phosbloc by sodium carbonate precipitation, makes the raw material of other rare-earth salts of preparation or lanthanum trioxide; By lanthanum sulfat centrifuge dewatering, obtain lanthanum sulfat 289.5 ㎏ containing crystal water, TREO=42.5 ﹪, direct yield is 94.91 ﹪.
The lanthanum sulfat outward appearance of preparation is Powdered odorless crystal, and water-soluble and sour, solution is limpid, the rising of the solubility with temperature in water and declining, and the solubleness in sulphuric acid soln reduces with the rising of acidity.
Embodiment 2:
A kind of sulfuric acid rare earth salt, outward appearance is Powdered odorless crystal, and chemical formula is RE
2(SO
4)
3.nH
20, under room temperature, n is less than 0.5, and water-soluble and sour, solution is limpid, the rising of the solubility with temperature in water and declining, and the solubleness in sulphuric acid soln reduces with the rising of acidity.
Step (5) in, toast containing the sulfuric acid rare earth salt of 3 ~ 9 crystal water at 150 DEG C ~ 260 DEG C temperature, obtain anhydrous slufuric acid rare-earth salts.
RE
2(SO
4)
3.nH
20→RE
2(SO
4)
3+ nH
20 (150℃～260℃)
Anhydrous slufuric acid rare-earth salts decomposes prepared by the present embodiment, controls decomposition temperature and time, can obtain the alkali formula sulfuric acid rare earth salt or the rare earth oxide that are insoluble in water.
RE
2(SO
4)
3→RE
2O
2SO
4+ 2SO
2↑+0
2↑ (855℃～946℃)
RE
2O
2SO
4→RE
2O
3+ SO
2↑+1/20
2↑ (1090℃～1250℃)
Wherein cerous sulfate is decomposed into the decomposition temperature of cerium oxide is 919 DEG C.
The present embodiment toasts de-crystal water to the lanthanum sulfat containing crystal water prepared by embodiment 1 at 200 DEG C of temperature, obtains anhydrous slufuric acid lanthanum 214.3 ㎏, TREO=57.4 ﹪.
Lanthanum sulfat outward appearance prepared by the present embodiment is Powdered odorless crystal, and water-soluble and sour, solution is limpid, the rising of the solubility with temperature in water and declining, and the solubleness in sulphuric acid soln reduces with the rising of acidity.The solubleness of described lanthanum sulfat in water (unit: g/100gH
2o), being 3.8g when 20 DEG C, is 1.5g when 40 DEG C.
Remaining with embodiment 1.
Embodiment 3:
The present invention step (1) in, the preferred concentration of described sulphuric acid soln is 1.0mol/L ~ 1.5mol/L.
The sulphuric acid soln 2000L of the present embodiment preparation 1.0mol/L, be cooled to 30 DEG C, it is complete that the Phosbloc being 43.5 ﹪ by 500 ㎏ TREO while stirring adds dissolving in sulphuric acid soln, dissolution process controls solvent temperature 65 DEG C, to the pH value 4.0 of solution, now, the concentration of solution middle-weight rare earths is 0.61mol/L; By solution filtering and impurity removing, with dilute sulphuric acid adjust pH to 2, obtain limpid rare earth sulfate solution 2200L; Limpid rare earth sulfate solution stirring heating being boiled, crystal is separated out, is 7g/L to the rare earth concentration in mother liquor, obtains 2000L slip; For preventing dissolution of crystals, improve direct yield, by slip fast filtering, by the rinsed with deionized water of closely boiling, vacuum filtration obtains lanthanum sulfat, and filtrate obtains Phosbloc by sodium carbonate precipitation, makes the raw material of other rare-earth salts of preparation or lanthanum trioxide; By lanthanum sulfat centrifuge dewatering, obtain lanthanum sulfat 460.4 ㎏ containing crystal water, TREO=44.5 ﹪; Then at the de-crystal water of baking at 200 DEG C of temperature, obtain anhydrous slufuric acid lanthanum 357.1 ㎏, TREO=57.37 ﹪, direct yield is 94.19 ﹪.
Remaining with embodiment 1,2.
Embodiment 4:
The sulphuric acid soln 1350L of the present embodiment preparation 1.48mol/L, be cooled to 30 DEG C, it is complete that the Phosbloc being 43.5 ﹪ by 500 ㎏ TREO while stirring adds dissolving in sulphuric acid soln, dissolution process controls solvent temperature 50 DEG C, to the pH value 3.5 of solution, now, the concentration of solution middle-weight rare earths is 0.83mol/L; By solution filtering and impurity removing, with dilute sulphuric acid adjust pH to 2, obtain limpid rare earth sulfate solution 1600L; Limpid rare earth sulfate solution stirring heating being boiled, crystal is separated out, is 8g/L to the rare earth concentration in mother liquor, obtains 1400L slip; For preventing dissolution of crystals, improve direct yield, by slip fast filtering, by the rinsed with deionized water of closely boiling, vacuum filtration obtains lanthanum sulfat, and filtrate obtains Phosbloc by sodium carbonate precipitation, makes the raw material of other rare-earth salts of preparation or lanthanum trioxide; By lanthanum sulfat centrifuge dewatering, obtain lanthanum sulfat 443.2 ㎏ containing crystal water, TREO=46.4 ﹪; Then at the de-crystal water of baking at 200 DEG C of temperature, obtain anhydrous slufuric acid lanthanum 357.6 ㎏, TREO=57.5 ﹪, direct yield is 94.54 ﹪.
Remaining with embodiment 1,2.
Embodiment 5:
The sulphuric acid soln 1000L of the present embodiment preparation 2.0mol/L, is cooled to 30 DEG C, and it is complete that the cerous carbonate being 49.9 ﹪ by 460 ㎏ TREO while stirring adds dissolving in sulphuric acid soln, dissolution process controls solvent temperature 38 DEG C, to the pH value 3.5 of solution, now, the concentration of solution middle-weight rare earths is 1.1mol/L; By solution filtering and impurity removing, with dilute sulphuric acid adjust pH to 2, obtain limpid rare earth sulfate solution 1200L; Limpid rare earth sulfate solution stirring heating being boiled, crystal is separated out, is 10g/L to the rare earth concentration in mother liquor, obtains 950L slip; For preventing dissolution of crystals, improve direct yield, by slip fast filtering, by the rinsed with deionized water of closely boiling, vacuum filtration obtains cerous sulfate, and filtrate obtains cerous carbonate by sodium carbonate precipitation, makes the raw material of other rare-earth salts of preparation or cerium oxide; By cerous sulfate centrifuge dewatering, obtain cerous sulfate 470.1 ㎏ containing crystal water, TREO=46.8 ﹪; Then at the de-crystal water of baking at 180 DEG C of temperature, obtain anhydrous ceric sulfate 382.62 ㎏, TREO=57.5 ﹪, direct yield is 95.85 ﹪.
Cerous sulfate outward appearance prepared by the present embodiment is Powdered odorless crystal, and water-soluble and sour, solution is limpid, the rising of the solubility with temperature in water and declining, and the solubleness in sulphuric acid soln reduces with the rising of acidity.The solubleness of described cerous sulfate in water (unit: g/100gH
2o), being 23.8g when 20 DEG C, is 10.3g when 40 DEG C.
Remaining with embodiment 1.
Embodiment 6:
The sulphuric acid soln 2000L of the present embodiment preparation 1.2mol/L, be cooled to 30 DEG C, it is complete that the gadolinium carbonate being 46.0 ﹪ by 630 ㎏ TREO while stirring adds dissolving in sulphuric acid soln, dissolution process controls solvent temperature 45 DEG C, to the pH value 3.5 of solution, now, the concentration of solution middle-weight rare earths is 0.72mol/L; By solution filtering and impurity removing, with dilute sulphuric acid adjust pH to 2, obtain limpid rare earth sulfate solution 2200L; Limpid rare earth sulfate solution stirring heating being boiled, crystal is separated out, is 6.1g/L to the rare earth concentration in mother liquor, obtains 2000L slip; For preventing dissolution of crystals, improve direct yield, by slip fast filtering, by the rinsed with deionized water of closely boiling, vacuum filtration obtains gadolinium sulphate, and filtrate obtains gadolinium carbonate by sodium carbonate precipitation, makes the raw material of other rare-earth salts of preparation or gadolinium sesquioxide; By gadolinium sulphate centrifuge dewatering, obtain gadolinium sulphate 620 ㎏ containing crystal water, TREO=44.5 ﹪; Then at the de-crystal water of baking at 200 DEG C of temperature, obtain anhydrous slufuric acid gadolinium 459.1 ㎏, TREO=60.1 ﹪, direct yield is 95.21 ﹪.
Gadolinium sulphate outward appearance prepared by the present embodiment is Powdered odorless crystal, and water-soluble and sour, solution is limpid, the rising of the solubility with temperature in water and declining, and the solubleness in sulphuric acid soln reduces with the rising of acidity.The solubleness of described gadolinium sulphate in water (unit: g/100gH
2o), being 2.87g when 20 DEG C, is 2.19g when 40 DEG C.
Remaining with embodiment 1.
Embodiment 7:
The sulphuric acid soln 1500L of the present embodiment preparation 2.0mol/L, be cooled to 30 DEG C, it is complete that the gadolinium carbonate being 46.0 ﹪ by 790 ㎏ TREO while stirring adds dissolving in sulphuric acid soln, dissolution process controls solvent temperature 45 DEG C, to the pH value 3.9 of solution, now, the concentration of solution middle-weight rare earths is 1.14mol/L; By solution filtering and impurity removing, with dilute sulphuric acid adjust pH to 2, obtain limpid rare earth sulfate solution 1750L; Limpid rare earth sulfate solution stirring heating being boiled, crystal is separated out, is 9.5g/L to the rare earth concentration in mother liquor, obtains 1550L slip; For preventing dissolution of crystals, improve direct yield, by slip fast filtering, by the rinsed with deionized water of closely boiling, vacuum filtration obtains gadolinium sulphate, and filtrate obtains gadolinium carbonate by sodium carbonate precipitation, makes the raw material of other rare-earth salts of preparation or gadolinium sesquioxide; By gadolinium sulphate centrifuge dewatering, obtain gadolinium sulphate 755.3 ㎏ containing crystal water, TREO=45.9 ﹪; Then at the de-crystal water of baking at 200 DEG C of temperature, obtain anhydrous slufuric acid gadolinium 576.9 ㎏, TREO=60.09 ﹪, direct yield is 95.39 ﹪.
Remaining with embodiment 1,6.
Embodiment 8:
The sulphuric acid soln 1770L of the present embodiment preparation 1.5mol/L, be cooled to 30 DEG C, it is complete that the yttrium carbonate being 40.0 ﹪ by 500 ㎏ TREO while stirring adds dissolving in sulphuric acid soln, dissolution process controls solvent temperature 40 DEG C, to the pH value 4.0 of solution, now, the concentration of solution middle-weight rare earths is 0.87mol/L; By solution filtering and impurity removing, with dilute sulphuric acid adjust pH to 2, obtain limpid rare earth sulfate solution 2020L; Limpid rare earth sulfate solution stirring heating being boiled, crystal is separated out, is 9.5g/L to the rare earth concentration in mother liquor, obtains 1700L slip; For preventing dissolution of crystals, improve direct yield, by slip fast filtering, by the rinsed with deionized water of closely boiling, vacuum filtration obtains yttrium sulfate, and filtrate obtains yttrium carbonate by sodium carbonate precipitation, makes the raw material of other rare-earth salts of preparation or yttrium oxide; By yttrium sulfate centrifuge dewatering, obtain yttrium sulfate 550.5 ㎏ containing crystal water, TREO=34.33 ﹪; Then at the de-crystal water of baking at 200 DEG C of temperature, anhydrous slufuric acid yttrium 396.98 ㎏ is obtained, TREO=47.51 ﹪.Direct yield is 94.30 ﹪.
Yttrium sulfate outward appearance prepared by the present embodiment is Powdered odorless crystal, and water-soluble and sour, solution is limpid, the rising of the solubility with temperature in water and declining, and the solubleness in sulphuric acid soln reduces with the rising of acidity.The solubleness of described yttrium sulfate in water (unit: g/100gH
2o), being 9.76g when 20 DEG C, is 4.90g when 40 DEG C.
Remaining with embodiment 1.
Claims (5)
1. a sulfuric acid rare earth salt, it is characterized in that outward appearance is Powdered odorless crystal, chemical formula is RE
2(SO
4)
3.nH
20, under room temperature, n is 3 ~ 9, and water-soluble and sour, solution is limpid, the rising of the solubility with temperature in water and declining, and the solubleness in sulphuric acid soln reduces with the rising of acidity.
2. a sulfuric acid rare earth salt, it is characterized in that outward appearance is Powdered odorless crystal, chemical formula is RE
2(SO
4)
3.nH
20, under room temperature, n is less than 0.5, and water-soluble and sour, solution is limpid, the rising of the solubility with temperature in water and declining, and the solubleness in sulphuric acid soln reduces with the rising of acidity.
3. a preparation method for sulfuric acid rare earth salt, is characterized in that it comprises the following steps:
(1) in enamel reactor, compound concentration is the sulphuric acid soln of 0.5mol/L ~ 2.0mol/L, is cooled to 30 DEG C ~ 35 DEG C; Slowly added by carbonated rare earth salt and carry out acid-soluble in the sulphuric acid soln prepared, solvent temperature 30 DEG C ~ 70 DEG C, obtains rare earth sulfate solution, to the pH value 3.5 ~ 4.0 of described solution;
(2) by step (1) gained rare earth sulfate solution filtering and impurity removing, obtain limpid rare earth sulfate solution, with dilute sulphuric acid adjust pH to 1.5 ~ 2;
(3) the step rare earth sulfate solution stirring heating that (2) gained is limpid is boiled, crystal is separated out, is less than 10g/L to the rare earth concentration in mother liquor;
By step (3) gained crystal mixing solutions be placed in strainer and filter, the gained crystal rinsed with deionized water of closely boiling, vacuum filtration obtains sulfuric acid rare earth salt;
(5) sulfuric acid rare earth salt centrifuge dewatering step (4) obtained, obtains the sulfuric acid rare earth salt containing 3 ~ 9 crystal water.
4. the preparation method of sulfuric acid rare earth salt according to claim 1, it is characterized in that step (5) in, the sulfuric acid rare earth salt containing 3 ~ 9 crystal water is toasted at 150 DEG C ~ 260 DEG C temperature, obtains anhydrous slufuric acid rare-earth salts.
5. the preparation method of sulfuric acid rare earth salt according to claim 3 or 4, it is characterized in that step (1) in, the preferred concentration of described sulphuric acid soln is 1.0mol/L ~ 1.5mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410678802.8A CN104445342B (en) | 2014-11-24 | 2014-11-24 | Sulfuric acid rare earth Salt And Preparation Method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410678802.8A CN104445342B (en) | 2014-11-24 | 2014-11-24 | Sulfuric acid rare earth Salt And Preparation Method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104445342A true CN104445342A (en) | 2015-03-25 |
| CN104445342B CN104445342B (en) | 2016-03-16 |
Family
ID=52892204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410678802.8A Active CN104445342B (en) | 2014-11-24 | 2014-11-24 | Sulfuric acid rare earth Salt And Preparation Method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104445342B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105460969A (en) * | 2016-01-05 | 2016-04-06 | 包头市新源抛光粉有限公司 | Preparation method for high-purity high-brightness needle-shaped cerium chloride |
| CN113044872A (en) * | 2021-04-14 | 2021-06-29 | 江苏温塑实业有限公司 | Preparation method of lanthanum sulfate |
| CN115321577A (en) * | 2022-08-29 | 2022-11-11 | 焦天棋 | Preparation method of yttrium oxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5973435A (en) * | 1982-07-26 | 1984-04-25 | ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク | Highly soluble ceric sulfate |
| CN1017419B (en) * | 1989-06-13 | 1992-07-15 | 甘肃稀土公司 | Preparation process of europium sulfate |
-
2014
- 2014-11-24 CN CN201410678802.8A patent/CN104445342B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5973435A (en) * | 1982-07-26 | 1984-04-25 | ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク | Highly soluble ceric sulfate |
| CN1017419B (en) * | 1989-06-13 | 1992-07-15 | 甘肃稀土公司 | Preparation process of europium sulfate |
Non-Patent Citations (2)
| Title |
|---|
| 刘新锦 等: "《无机元素化学》", 31 January 2010, article "硫酸盐", pages: 271 - 1 * |
| 孙晓白: "试剂硫酸铈的制备", 《湖南化工》, no. 3, 31 December 1988 (1988-12-31), pages 31 - 32 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105460969A (en) * | 2016-01-05 | 2016-04-06 | 包头市新源抛光粉有限公司 | Preparation method for high-purity high-brightness needle-shaped cerium chloride |
| CN105460969B (en) * | 2016-01-05 | 2017-08-01 | 内蒙古新雨稀土功能材料有限公司 | A kind of preparation method of high pure and high clear brightness needle-like cerous chlorate |
| CN113044872A (en) * | 2021-04-14 | 2021-06-29 | 江苏温塑实业有限公司 | Preparation method of lanthanum sulfate |
| CN115321577A (en) * | 2022-08-29 | 2022-11-11 | 焦天棋 | Preparation method of yttrium oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104445342B (en) | 2016-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111057848A (en) | A kind of solvent extraction method for extracting lithium from lithium-containing solution | |
| CN107557598B (en) | Method for preparing vanadium electrolyte | |
| CN109097565A (en) | A method of the high-efficiency cleaning Extraction of rare earth from ion adsorption type rare earth ore | |
| RU2736539C1 (en) | Method of producing vanadium oxide of a battery grade | |
| CN104445342B (en) | Sulfuric acid rare earth Salt And Preparation Method | |
| JP2003040622A (en) | process | |
| CN105803199B (en) | A kind of method that hydroxide precipitation method prepares low-sulfur rare earth oxide | |
| CN103224248B (en) | Method of preparing rare earth carbonate and recycling materials thereof | |
| WO2013073376A1 (en) | Method for recovering rare earth element | |
| JP5440569B2 (en) | Recovery method for heavy rare earth elements | |
| CN106348273A (en) | Extraction agent for preparing industrial phosphoric acid through hydrochloric acid method and extraction method thereof | |
| CN109593977A (en) | A method of removal is containing iron ion in neodymium, praseodymium, dysprosium and ferrous solution | |
| CN102977135B (en) | A kind of preparation method of the niobium complex aqueous solution | |
| CN103626230A (en) | Method for preparing vanadyl sulfate | |
| CN113430375A (en) | Method for separating low-valence ferrovanadium-chromium solution | |
| CN109022783A (en) | The method of the vanadium manganese of immersion liquid containing vanadic acid separation | |
| CN104276594A (en) | Process for preparing nano-zinc oxide by using zinc sulfide concentrate calcined zinc sand | |
| CN102744086B (en) | Preparation method of ZrO2-TiO2/SO42-solid acid catalyst | |
| CN102465203B (en) | Method for directly preparing cerium fluoride by extraction and separation | |
| CN104891577B (en) | The minimizing technology of fluorine ion in high-purity sulphuric acid manganese solution | |
| CN104326512B (en) | A kind of preparation method of nickelous fluoride | |
| CN103121716B (en) | A method for preparing vanadium pentoxide by vanadium solution | |
| JP3788185B2 (en) | Method for recovering cerium from a solution containing chromium and cerium | |
| CN112429774A (en) | Production method of nuclear-grade hafnium dioxide | |
| CN103449511A (en) | Strontium titanate submicron crystal and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |