CN100999332A - Low temperature preparation method of rare earth sesquifide - Google Patents
Low temperature preparation method of rare earth sesquifide Download PDFInfo
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- CN100999332A CN100999332A CN 200610156299 CN200610156299A CN100999332A CN 100999332 A CN100999332 A CN 100999332A CN 200610156299 CN200610156299 CN 200610156299 CN 200610156299 A CN200610156299 A CN 200610156299A CN 100999332 A CN100999332 A CN 100999332A
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- rare earth
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Abstract
This invention relates to low temperature preparation method of rare earth sesquisulfide, which belongs to material synthesis domain. These invention materials are rare earth salt solution, sulfurizing agent, and gas vulcanizer. Add sulfurizing agent in rare earth salt solution. Molar ratio of sulfurizing agent is 10-50%. Concentrate and dry at 100deg-300deg, get predecessor of rare earth sulfurizing salt. Sulfurize predecessor of rare earth sulfurizing salt by gas vulcanizer. Sulfurizing temperature is lower than 1000deg. Product is monophase are earth sesquisulfide. Grade size is less than 1mum. This invention can prepare rare earth sesquisulfide of high purity and small grain size.
Description
One, technical field
The present invention relates to the preparation technology of the single-phase high-purity rare-earth sesquisulphide of a kind of low temperature preparation method of rare earth sesquifide, particularly temperature production, belong to the synthetic field of material.
Two, background technology
Rare earth sesquifide is because its excellent physical chemistry, Chang Zuowei luminescent material, mineral dye and thermoelectric material and be widely studied and applied.Red pigment cerium trisulfide for example, with its lovely luster, stable performance, and nontoxicity, can be widely used in the painted of plastics, coating, glasswork and stupalith, the sulfuration dysprosium is owing to high high-quality coefficient is arranged, and is huge at the application potential in elevated temperature heat electric material field.The mineral dye that uses contains cadmium mostly at present; plumbous; mercury etc. are to the very deleterious heavy metal element of human body; its range of application is subjected to strict restriction; many in recent years countries make strict rules; limit or ban use of the poisonous pigment that environment is polluted; the avirulent high-performance inorganic pigment prepared technology of the urgent searching of pigment manufacturer; to adapt to the requirement of society to environment protection and product performance; because the f-d transition of electron of rare earth element has the charge migration band; some rare-earth sulfide produces effective photoabsorption; can be used as mineral dye and use, as red cerium sulphide (Ce
2S
3), its color is dark red, nontoxicity, and strong covering power Heat stability is good, and strong absorption ultraviolet ray are the preferred material that replaces poisonous cadmium red.
At present, though people are doing big quantity research aspect the preparation of rare earth sesquifide, what great majority all adopted is High Temperature Gas solid phase vulcanizing method, and synthesis temperature all is higher than 1000 ℃, mainly contains following shortcoming:
(1) chemical reaction is gas phase/solid state reaction, and speed of response is slow, and treatment capacity is little, and productivity is low.
(2) product purity is lower, contains oxysulfide in various degree in the product.
(3) synthesis temperature height, power consumption is big, and the caused corrosion of high temperature has further increased production cost.
Owing to above reason, make the large-scale practical application of rare-earth sulfide be subjected to considerable restraint.
Three, summary of the invention
The key technical problem that the present invention will solve is: the low temperature preparation method that a kind of Cheap highly effective, less energy-consumption, oligosaprobic rare earth sesquifide are provided
Technical solution:
Technology of the present invention comprises two portions: low temperature prepares sulphide salt presoma and two processes of high temperature vulcanized preparation rare earth sesquifide.
Preparation technology of the present invention:
The preparation of presoma is that the salts solution with rare earth is a raw material, adds the sulfuration reagent of excessive 10-50% (mol ratio) in concentration is the rare earths salt of (0.1-1mo1/L), carries out the liquid phase vulcanization reaction under 70-110 ℃ of vigorous stirring, generates sulphide salt solution.Sulphide salt solution concentrates under 110-140 ℃ of vigorous stirring, through the solvent evaporation drying, is converted into particle diameter less than 1 micron sulphide salt precursor powder in 170-300 ℃ of temperature range.
High temperature vulcanized is to place in the tube furnace gaseous state vulcanizing agent that feeds drying to vulcanize being lower than under 1000 ℃ of temperature presoma, 1-8 ℃/min of control material heat-up rate, be warmed up to 550-1000 ℃, insulation 10-100min so just makes the pure rare earth sesquisulphide.Tail gas absorbs with alkali lye.
The present invention:
(1) at first at liquid phase production sulphide salt precursor powder material, powder size is evenly distributed, particle diameter is less than 1 micron.Because presoma has high surface, and follow-up curing temperature is reduced greatly, curing time also shortens dramatically.
(2) preparation of presoma is that the salts solution with high-purity rare-earth is a raw material.Rare earths salt comprises nitrate, vitriol, acetate, the muriate of rare earth, and carbonate, oxalate, oxyhydroxide and the oxide compound solution after acid is molten.The used sulfuration reagent of preparation presoma is ammonium sulfide, many ammonium sulfides, ammonium thiocyanate, thioacetamide, sulfo-ethylbenzene acid amides, sulfo-butyramide, Thionicotinamide, thiocarbamide, amido thiocarbamide, 4-phenyl thiosemicarbazide, N-phenylthiourea, thiosemicarbazide, thiophenol, thiophene, thiazole, mercaptan and thiophenol etc.The outlet temperature of preparation sulphide salt presoma: between (180-300 ℃).The reaction of preparation sulphide salt presoma can be expressed as:
RE
s++xX
n-+yS-R→RES
y·X
x
(3) the sulphide salt precursor powder gets product because its high surfactivity under 300-1000 ℃, is vulcanized in a short period of time with the gaseous state vulcanizing agent.The gaseous state vulcanizing agent comprises hydrogen sulfide, dithiocarbonic anhydride steam, sulphur steam.Curing temperature: (550-1000 ℃), insulation 10-100min.Be that the end reaction that example prepares rare earth sesquifide is with hydrogen sulfide:
RES
y·X
x+H
2S→RE
2S
3+xHX
(4) absorb tail gas by alkaline solution, to reduce environmental pollution.Alkali lye comprises sodium hydroxide, potassium hydroxide, calcium hydroxide.Absorption liquid can be used as auxiliary material, allocates in the rare earth original solution.
The technical indicator that the invention product can reach is as follows:
Purity 〉=99.95%
Particle diameter≤1 micron
Product is the single-phase RE sesquisulphide.
Four, embodiment
Embodiment 1:
Take by weighing 10 gram cerous carbonates, put into crucible and add a spot of water-wet, crucible is placed on the thermostatically heating plate heats, 110 ℃ of controlled temperature, in crucible, dropwise drip concentrated hydrochloric acid, dissolve fully up to cerous carbonate, this moment, solution became light yellow, and heating is up to crystallization occurring, use the 100ml dissolved in distilled water, recrystallize, 3 times like this, the nearly neutral pH 6-7 of solution.The thermostatically heating plate temperature transfers to about 160 ℃, at this moment, weighing 15g thioacetamide is put into crucible, and the stirring that does not stop is along with the evaporation of solvent, constantly produce milky gel, finish until solvent evaporation, take off crucible, put into baking oven and handle from the thermostatically heating plate, temperature is 180 ℃, has so just prepared presoma.Presoma is put into tube furnace carry out high temperature vulcanizedly under dithiocarbonic anhydride atmosphere, control rate of heating 4 ℃/min is heated to 800 ℃, insulation 1h, and product is the atropurpureus powder.Tail gas absorbs with the 1mol/L sodium hydroxide solution.
10ml tail gas absorption liquid is added in the above-mentioned nearly neutral solution, and still according to above-mentioned art breading, product is the bright red powder.
Embodiment 2:
Take by weighing 10 gram crystallization Lanthanum trichlorides, put into crucible and use the 100ml dissolved in distilled water, 110 ℃ of heating recrystallize, 2 times like this, solution is closely neutral.Temperature transfers to about 170 ℃, and weighing 15g thioacetamide is put into crucible, and the stirring that does not stop finishes until solvent evaporation, takes off crucible from the thermostatically heating plate, puts into baking oven and handles, and temperature is 180 ℃, and the preparation presoma is yellow.Presoma is put into tube furnace carry out high temperature vulcanizedly under dithiocarbonic anhydride atmosphere, control rate of heating 4 ℃/min is heated to 850 ℃, insulation 1h, and product is a white powder.Tail gas absorbs with the 1mol/L sodium hydroxide solution.
Embodiment 3:
Take by weighing 10 gram dysprosium oxides, put into crucible and with concentrated nitric acid dissolving, 110 ℃ of heating recrystallize use the 100ml dissolved in distilled water, 3 times like this, solution is neutrality closely.Temperature transfers to about 150 ℃, and weighing 15g thiosemicarbazide is put into crucible, and the stirring that does not stop finishes until solvent evaporation, takes off crucible from the thermostatically heating plate, puts into baking oven and handles, and temperature is 200 ℃, and the preparation presoma is creamy white.Presoma is put into tube furnace carry out high temperature vulcanizedly under dithiocarbonic anhydride atmosphere, control rate of heating 4 ℃/min is heated to 700 ℃, insulation 1h, and product is a white powder.Tail gas absorbs with the 1mol/L sodium hydroxide solution.
Claims (6)
1, the low temperature preparation method of rare earth sesquifide, it is characterized in that: the salts solution with rare earth is a raw material, in concentration is to add sulfuration reagent in the rare earths salt of 0.1-1mol/L, the excessive 10-50% of sulfuration reagent mol ratio, under 70-110 ℃ of vigorous stirring, carry out the liquid phase vulcanization reaction, generate sulphide salt solution or colloidal sol, sulphide salt solution or colloidal sol concentrate under 110-140 ℃ of vigorous stirring, through the solvent evaporation drying, in 170-300 ℃ of temperature range, transform particle diameter less than 1 micron sulphide salt precursor powder; The sulphide salt precursor powder is vulcanized with the gaseous state vulcanizing agent under 550-1000 ℃ of temperature, and the material heat-up rate is 1-8 ℃/min, and temperature: 550-1000 ℃, insulation 10-100min gets rare earth sesquifide; Tail gas absorbs with alkali lye.
2, the low temperature preparation method of rare earth sesquifide according to claim 1 is characterized in that: rare earth is Sc, Y or lanthanon a kind of.
3, the low temperature preparation method of rare earth sesquifide according to claim 1, it is characterized in that: rare earths salt is nitrate, vitriol, acetate, the muriate of rare earth, and a kind of in carbonate, oxalate, oxyhydroxide and the oxide compound solution after acid is molten.
4, the low temperature preparation method of rare earth sesquifide according to claim 1 is characterized in that: sulfuration reagent is one or more in ammonium sulfide, many ammonium sulfides, ammonium thiocyanate, thioacetamide, sulfo-ethylbenzene acid amides, sulfo-butyramide, Thionicotinamide, thiocarbamide, amido thiocarbamide, 4-phenyl thiosemicarbazide, N-phenylthiourea, thiosemicarbazide, thiophenol, thiophene, thiazole, mercaptan and the thiophenol.
5, the low temperature preparation method of rare earth sesquifide according to claim 1 is characterized in that: the gaseous state vulcanizing agent is a kind of in hydrogen sulfide, dithiocarbonic anhydride steam, the sulphur steam.
6, the low temperature preparation method of rare earth sesquifide according to claim 1 is characterized in that: alkali lye is a kind of in sodium hydroxide, potassium hydroxide, the calcium hydroxide.
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| CNB2006101562995A CN100491255C (en) | 2006-12-29 | 2006-12-29 | Low temperature preparation method of rare earth sesquifide |
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|---|---|---|---|
| CNB2006101562995A CN100491255C (en) | 2006-12-29 | 2006-12-29 | Low temperature preparation method of rare earth sesquifide |
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| CN100999332A true CN100999332A (en) | 2007-07-18 |
| CN100491255C CN100491255C (en) | 2009-05-27 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517295A (en) * | 2016-10-18 | 2017-03-22 | 西北工业大学 | Method for synthesizing high-stability gamma-Pr2S3 powder |
| CN108659573A (en) * | 2017-03-29 | 2018-10-16 | 中国科学院包头稀土研发中心 | Rare-earth pigment mixture and method |
| CN108659574A (en) * | 2017-03-29 | 2018-10-16 | 中国科学院包头稀土研发中心 | Coloring agent composition and method |
| CN109135336A (en) * | 2017-06-13 | 2019-01-04 | 中国科学院包头稀土研发中心 | A kind of coloring agent composition and preparation method thereof |
| CN113023761A (en) * | 2021-04-14 | 2021-06-25 | 中稀(常州)稀土新材料有限公司 | Industrial processing technology for effectively improving mixing and clarifying effects of dysprosium oxide |
-
2006
- 2006-12-29 CN CNB2006101562995A patent/CN100491255C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517295A (en) * | 2016-10-18 | 2017-03-22 | 西北工业大学 | Method for synthesizing high-stability gamma-Pr2S3 powder |
| CN108659573A (en) * | 2017-03-29 | 2018-10-16 | 中国科学院包头稀土研发中心 | Rare-earth pigment mixture and method |
| CN108659574A (en) * | 2017-03-29 | 2018-10-16 | 中国科学院包头稀土研发中心 | Coloring agent composition and method |
| CN109135336A (en) * | 2017-06-13 | 2019-01-04 | 中国科学院包头稀土研发中心 | A kind of coloring agent composition and preparation method thereof |
| CN113023761A (en) * | 2021-04-14 | 2021-06-25 | 中稀(常州)稀土新材料有限公司 | Industrial processing technology for effectively improving mixing and clarifying effects of dysprosium oxide |
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| CN100491255C (en) | 2009-05-27 |
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Assignee: Baotou Qingli environmental protection science and Technology Development Co., Ltd. Assignor: University of Science and Technology of Inner Mongolia Contract fulfillment period: 2009.6.1 to 2024.5.31 contract change Contract record no.: 2009150000025 Denomination of invention: Low temperature preparation method of rare earth sesquifide Granted publication date: 20090527 License type: Exclusive license Record date: 2009.9.17 |
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