CN102515240A - Method for preparing red pigment cerium sulphide - Google Patents

Method for preparing red pigment cerium sulphide Download PDF

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Publication number
CN102515240A
CN102515240A CN2011103828176A CN201110382817A CN102515240A CN 102515240 A CN102515240 A CN 102515240A CN 2011103828176 A CN2011103828176 A CN 2011103828176A CN 201110382817 A CN201110382817 A CN 201110382817A CN 102515240 A CN102515240 A CN 102515240A
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ce2s3
mixed crystal
solution
gamma
red pigment
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CN102515240B (en
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邱忠贤
廉世勋
葛勇杰
余丽萍
荣春英
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Hunan Normal University
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Hunan Normal University
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Abstract

The invention relates to a technology for preparing red pigment Ce2S3, namely a liquid phase precipitation and high temperature crystal transformation two-step synthesis method. The technology comprises two steps: firstly, mixing Ce<3+> ionic liquid and S<2-> ionic liquid, and generating a precipitation reaction to synthesize an alpha-Ce2S3, beta-Ce2S3 and gamma-Ce2S3 mixed crystal precursor; and secondly, adding a proper amount of carbon powder, sodium carbonate, calcium carbonate and boracic acid into the mixed crystal precursor to modify the mixed crystal precursor, heating under the assistant of microwaves, turning alpha-Ce2S3 and beta-Ce2S3 into gamma-Ce2S3 at temperature of 1,200 DEG C, and improving the crystallinity of the gamma-Ce2S3. During the preparation, explosive and combustible gas H2 and toxic gas, such as H2S and CS2, are not used, so that toxic gas SO2 or SO3 is not produced, and the technology is safe and environment-friendly; by adopting the microwave assistant heating mode for high temperature crystal transformation, high efficiency and energy conservation are realized; and the obtained gamma-Ce2S3 particles are uniform, and are red.

Description

The preparation method of cerium sulphide red pigment
Technical field
The present invention relates to cerium sulphide red pigment (γ-Ce 2S 3) a kind of preparation method, belong to the synthetic technology of mineral dye.
Background technology
γ-Ce 2S 3, also be the sesquialter cerium sulphide.γ-Ce 2S 3Have good thermostability, weather resisteant and photostabilization, body colour is large red, and being expected to substitute deleterious cadmium sulfoselenide (CdSSe) becomes a kind of eco-friendly big red.France sieve Na Pulanke company reports γ-Ce at first 2S 3Synthetic and use.
Ce 2S 3α is arranged, three kinds of crystal formations of beta, gamma.α changes the β phase into about 900 ℃, β changes the γ phase into about 1200 ℃.γ-Ce 2S 3Belong to isometric system Th 3P 4N-type waferN is so its molecular formula also can be expressed as γ-Ce 2.67V 0.33S 4(V representes the room).At γ-Ce 2S 3The lattice vacancy place imports alkalimetal ion, alkaline earth metal ion or heavy rare earths ion, can regulate γ-Ce 2S 3Electronic structure, change its reflection spectrum and reflectivity, thereby regulate the cerium sulphide color.
European patent EP 0680930A, japanese patent laid-open 8-259229, Japanese Patent 2689819, Chinese patent CN98120016.8, CN01139900.7 and CN200810031536.4 etc. has put down in writing γ-Ce 2S 3The preparation method of pigment.First method is in tube type high-temperature furnace, to feed nitrogen hydrogen mixeding gas (H 2+ N 2), at high temperature with Ce 2(SO 4) 3Or Ce (SO 4) 2Be reduced into γ-Ce 2S 3Second method is in tube type high-temperature furnace, to feed H 2S or CS 2Gas, at high temperature the compound (comprising oxide compound, muriate, carbonate and oxalate etc.) with cerium is sulfided into γ-Ce 2S 3The third method is with H2 and sulfur vapor sulfuration CeO 2Generate γ-Ce 2S 3
The compound method of above-mentioned patent record has tangible weak point: (1) preparation process is used inflammable and explosive hydrogen (H 2), there is potential safety hazard; (2) use deleterious sulfide gas (H 2S, CS 2) or produce deleterious SO 2And SO 3Gas, harm environment and direct labor; (3) power consumption is high, long reaction time for traditional type of heating (globars or Si-Mo rod heating).So the synthetic technology of above-mentioned patent record is difficult to be fit to the suitability for industrialized production requirement.Though people such as Tsuzuki adopt mechanochemical reaction, the direct anhydrous CeCl of ball milling 3, CaS and CaCl 2Mixture has also obtained γ-Ce at normal temperatures 2S 3, but the foreign matter content in the product is very high, and size distribution is very inhomogeneous, also is impractical in suitability for industrialized production.
The objective of the invention is to invent a kind of about γ-Ce 2S 3The preparation method.At first, adopt the synthetic α-Ce of liquid phase sluggish precipitation 2S 3, β-Ce 2S 3And γ-Ce 2S 3Mixed crystal; Then, adopt the microwave-assisted heating, make mixed crystal be transformed into γ-Ce at 1200 ℃ 2S 3, obtain the uniform large red powder of body colour.Claim that this method is " it is brilliant that liquid-phase precipitation-high temperature changes " method.Present method has been avoided use flammable explosive gas and toxic gas fully, also can not produce toxic gas, safety and environmental protection; And adopt the microwave-assisted type of heating, energy-efficient.
Summary of the invention
Technical problem to be solved by this invention is to the deficiency of existing technology of preparing, and a kind of preparation γ-Ce is provided 2S 3New technology.This new technology is not used flammable explosive gas (H 2) and toxic gas (H 2S and CS 2), do not produce toxic gas (SO yet 2Or SO 3).Solving the technological technical scheme that is adopted of the present invention is " it is brilliant that liquid-phase precipitation-high temperature changes " two step synthesis methods:
(1) the first step, liquid-phase precipitation: with water-soluble cerous salt and water-soluble sulfide is that raw material is made into Ce 3+Solution and S 2-Solution is according to Ge 3+Ion and S 2-The ratio n of ionic amount of substance Ce: n s=1: 1.5-3.0 is with Ce 3+Solution slowly is added drop-wise to S 2-Stir in the solution and constantly, leave standstill to the deposition completion; Through filtration, washing, drying, obtain containing α-Ce 2S 3, β-Ce 2S 3And γ-Ce 2S 3The mixed crystal presoma.
In (2) second steps, it is brilliant that high temperature changes: in above-mentioned mixed crystal presoma, add an amount of alkali metal cpd, alkaline earth metal cpds, H 3BO 3And carbon dust, grind evenly, relay crucible and be placed in the program control microwave oven; Logical nitrogen or argon gas are caught up with the air in the most closed system, stop logical N 2, microwave oven is warming up to 1200 ℃, and constant temperature 1.0-4.0 hour, cool to room temperature again.Take out material, promptly get γ-Ce 2S 3Red pigment.
The present invention has following characteristics:
1, Ce 3+Ion and S 2-Precipitin reaction takes place and generates the cerium sulphide mixed crystal in ion in solution, do not use flammable explosive gas and toxic gas in the preparation process, does not also produce toxic gas, safety and environmental protection.
2, adopt microwave-assisted type of heating high temperature to change brilliant, energy-efficient.
The red pigment γ of indication of the present invention-Ce 2S 3Compound method be:
According to Ce 3+Ion and S 2-The ratio n of ionic amount of substance Ce: n S=1: 1.5-3.0 is measured Ce respectively 3+Solution and S 2-Solution.With Ce 3+Drips of solution is added to S 2-Also constantly stir in the solution and accomplish until deposition.Filter, wash, obtain containing α-Ce 2S 3, β-Ce 2S 3And γ-Ce 2S 3The mixed crystal presoma.The mixed crystal presoma is placed thermostatic drying chamber, and 80 ℃ dry down.In drying the mixed crystal presoma in add an amount of alkali metal cpd, alkaline earth metal cpds, carbon dust and H 3BO 3, mix, fully grind, obtain the modification presoma.Wherein, the add-on of alkalimetal ion, alkaline earth metal ion and carbon dust accounts for 0-30.0mol%, 0-60.0mol% and the 1.0-6.0mol% of cerium ion, H respectively 3BO 3Add-on account for the 5.0-10.0wt.% of whole material.The modification presoma is put into crucible, place in the program control microwave oven.Logical nitrogen or argon gas are caught up with the air in the most closed system, stop logical N 2Microwave oven is warming up to 1200 ℃, and constant temperature 1.0-4.0 hour, cool to room temperature again.Take out material, grind, wash, sieve, obtain red pigment γ-Ce 2S 3
Description of drawings
Fig. 1 Ce 2.31Na 0.23Ca 0.38S 4X-ray diffractogram
Embodiment
Instance 1Ce 2.31Na 0.23Ca 0.38S 4Red pigment
Take by weighing CeCl 32.46 gram, Na 2S9H 2O 5.4 grams are dissolved in the 100mL deionized water respectively, are made into CeCl 3Solution and Na 2S solution.With CeCl 3Drips of solution is added to Na 2In the S solution, it is complete that the limit edged is stirred to precipitin reaction.Filter, wash, obtain containing α-Ce 2S 3, β-Ce 2S 3And γ-Ce 2S 3The mixed crystal presoma.The mixed crystal presoma is placed thermostatic drying chamber, and 80 ℃ dry down.In drying the mixed crystal presoma in add Na 2CO 30.07 gram, CaCO 30.16 gram, H 3BO 30.3 gram, carbon dust 1.0 grams mix, and fully grind, and obtain the modification precursor.The modification precursor is placed the microwave oven of sealing, feed N earlier 2Catch up with the air in the most closed system, stop logical N 2, microwave oven is rapidly heated to 1200 ℃, is incubated 3.0 hours, naturally cools to room temperature.Take out product, ball milling, wash, sieve, dry, red powder.Detect through x-ray diffractometer, the gained red powder is the good γ-Ce of percent crystallinity 2S 3

Claims (2)

1. red pigment Ce 2S 3A kind of preparation method, it is characterized in that with water-soluble cerous salt and water-soluble sulfide be preparation of raw material Ce 3+Solution and S 2-Solution is according to Ge 3+Ion and S 2-The ratio n of ionic amount of substance Ce: n S=1: 1.5-3.0 is measured solution, with Ge 3+Solution slowly is added drop-wise to S 2-Stir in the solution and constantly, precipitin reaction takes place accomplish until deposition; Through filtration, washing, drying, obtain containing α-Ce 2S 3, β-Ce 2S 3And γ-Ce 2S 3The mixed crystal presoma.
2. crystal conversion method that is used for the said mixed crystal precursor of claim 1; It is characterized in that adding carbon dust high-temperature fixed sulfur, adding sodium ion and calcium ion occupy lattice vacancy in the mixed crystal presoma, adding boric acid is made fusing assistant; The microwave-assisted heating; At 1200 ℃ of constant temperature 1.0-4.0 hours, with α-Ce 2S 3And β-Ce 2S 3All change γ-Ce into 2S 3And raising γ-Ce 2S 3Percent crystallinity.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105129833A (en) * 2015-07-13 2015-12-09 盐城工学院 Method of preparing rare earth oxysulfide with carbon disulfide
CN106430274A (en) * 2016-08-29 2017-02-22 湖南科莱新材料有限公司 Method for preparing nano cerium sulfide by adopting liquid phase method
CN108046305A (en) * 2017-10-25 2018-05-18 景德镇陶瓷大学 A kind of composite mixed type γ~Ce of nanoscale low price ion2S3Red pigment and preparation method thereof
CN111484065A (en) * 2020-04-21 2020-08-04 甘肃翔达新颜料科技股份有限公司 Preparation method of novel rare earth red pigment gamma-Ce 2S3
CN112625464A (en) * 2020-12-01 2021-04-09 景德镇陶瓷大学 PEG (polyethylene glycol) and carbon powder refined cristobalite coated gamma-Ce2S3Preparation method of red pigment and product prepared by preparation method
US11505471B2 (en) 2017-12-18 2022-11-22 Rhodia Operations Mechanochemical synthesis of rare earth sulfides
CN115784293A (en) * 2022-11-18 2023-03-14 中国计量大学 Method for preparing rare earth cerium sulfide by supercritical hydrothermal method
CN115806305A (en) * 2022-11-18 2023-03-17 中国计量大学 Method for preparing rare earth cerium sulfide by supercritical carbon dioxide

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储茂友 等: "碱金属添加剂Na+对γ-Ce2S3红色颜料合成及颜色的影响", 《中国稀土学报》, vol. 20, no. 6, 31 December 2002 (2002-12-31), pages 680 - 683 *
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105129833A (en) * 2015-07-13 2015-12-09 盐城工学院 Method of preparing rare earth oxysulfide with carbon disulfide
CN106430274A (en) * 2016-08-29 2017-02-22 湖南科莱新材料有限公司 Method for preparing nano cerium sulfide by adopting liquid phase method
CN108046305A (en) * 2017-10-25 2018-05-18 景德镇陶瓷大学 A kind of composite mixed type γ~Ce of nanoscale low price ion2S3Red pigment and preparation method thereof
CN108046305B (en) * 2017-10-25 2019-10-15 景德镇陶瓷大学 A kind of composite mixed type γ~Ce of nanoscale low price ion2S3Red pigment and preparation method thereof
US11505471B2 (en) 2017-12-18 2022-11-22 Rhodia Operations Mechanochemical synthesis of rare earth sulfides
CN111484065A (en) * 2020-04-21 2020-08-04 甘肃翔达新颜料科技股份有限公司 Preparation method of novel rare earth red pigment gamma-Ce 2S3
CN111484065B (en) * 2020-04-21 2022-11-01 甘肃翔达新颜料科技股份有限公司 Red pigment gamma-Ce2S3Preparation method of (2)
CN112625464A (en) * 2020-12-01 2021-04-09 景德镇陶瓷大学 PEG (polyethylene glycol) and carbon powder refined cristobalite coated gamma-Ce2S3Preparation method of red pigment and product prepared by preparation method
CN115784293A (en) * 2022-11-18 2023-03-14 中国计量大学 Method for preparing rare earth cerium sulfide by supercritical hydrothermal method
CN115806305A (en) * 2022-11-18 2023-03-17 中国计量大学 Method for preparing rare earth cerium sulfide by supercritical carbon dioxide
CN115784293B (en) * 2022-11-18 2024-05-10 中国计量大学 Method for preparing rare earth cerium sulfide by supercritical hydrothermal method
CN115806305B (en) * 2022-11-18 2024-05-14 中国计量大学 Method for preparing rare earth cerium sulfide by supercritical carbon dioxide

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