CN115784293A - Method for preparing rare earth cerium sulfide by supercritical hydrothermal method - Google Patents
Method for preparing rare earth cerium sulfide by supercritical hydrothermal method Download PDFInfo
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- CN115784293A CN115784293A CN202211445992.XA CN202211445992A CN115784293A CN 115784293 A CN115784293 A CN 115784293A CN 202211445992 A CN202211445992 A CN 202211445992A CN 115784293 A CN115784293 A CN 115784293A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 57
- -1 rare earth cerium sulfide Chemical class 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 1
- 229960001759 cerium oxalate Drugs 0.000 claims 1
- 239000000049 pigment Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000001054 red pigment Substances 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 239000002341 toxic gas Substances 0.000 abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002360 explosive Substances 0.000 abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000002019 doping agent Substances 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 2
- 238000004040 coloring Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000003086 colorant Substances 0.000 description 10
- 229910052684 Cerium Inorganic materials 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 239000001023 inorganic pigment Substances 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 239000012860 organic pigment Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 101710178035 Chorismate synthase 2 Proteins 0.000 description 3
- 101710152694 Cysteine synthase 2 Proteins 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005274 electronic transitions Effects 0.000 description 2
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- 239000012530 fluid Substances 0.000 description 2
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- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
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- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- MMXSKTNPRXHINM-UHFFFAOYSA-N cerium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Ce+3].[Ce+3] MMXSKTNPRXHINM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
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- 229910001994 rare earth metal nitrate Inorganic materials 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to a method for preparing rare earth cerium sulfide by a supercritical hydrothermal method, which takes rare earth nitrate as a raw material, a compound containing alkali metal as a doping agent and thiourea as a vulcanizing agent. The preparation method comprises the following steps: uniformly mixing the prepared rare earth nitrate solution, thiourea solution and alkali metal solution, putting the mixture into a high-pressure reaction kettle of a supercritical device, heating to 375-410 ℃ after air is exhausted, preserving heat for 24h when the pressure reaches 22.5-36 MPa, and finally washing to obtain the rare earth cerium sulfide. The preparation method is simple to operate, does not use flammable, explosive and toxic gases, is safe and environment-friendly, and is a novel green and environment-friendly preparation method. And the prepared rare earth cerium sulfide product has bright color and strong tinting strength. The coloring capability of the pigment far exceeds that of other inorganic red pigments such as iron oxide red, molybdenum-chromium red, manganese red and the like. Meanwhile, the product has the advantages of uniform particle size, good dispersibility, good temperature resistance, corrosion resistance and no toxicity.
Description
Technical Field
The invention belongs to the field of synthesis of rare earth materials, and particularly relates to a method for preparing rare earth cerium sulfide by a supercritical hydrothermal method.
Background
Pigments are generally classified into two major classes, organic pigments and inorganic pigments. The organic pigment has bright color and strong tinting strength,
although the color rendering properties of inorganic pigments are slightly inferior to those of organic pigments, they are superior to those of organic pigments in chemical stability, light fastness, weather resistance, hiding power, and the like. Therefore, the inorganic pigment is widely used in the fields of paint, plastics, rubber, building materials, painting pigments, printing ink, ceramics and the like.
Most of the common inorganic pigments contain toxic components such as lead, chromium, mercury and the like, which cause great harm to human bodies, are not beneficial to human health, and also do not accord with the strategy of sustainable development in China, so that the search of substitutes thereof is always a hot point for researches of researchers. With the increasing enhancement of the concept of protecting the environment, and the establishment of corresponding legal regulations for protecting the environment in many countries, the use of inorganic pigments containing toxic and heavy metals which cause pollution and harm to the environment and human bodies is limited or prohibited. For example, in the last 90 s of the century, marking paints on roads prescribed by north american and northern european legislation must be lead-free, and the european union, in addition, implemented the RoHS directive on 1/7/2006, limits the use of heavy metal substances such as lead, cadmium, mercury, chromium, etc., which have a number of negative effects on the production and use of pigments. Therefore, pigment manufacturers must develop high-performance non-toxic environment-friendly pigments to meet the social requirements for environmental protection and product quality, and therefore, the development of novel inorganic alternative pigments is urgent. With the progress of research, people turn their attention to rare earth elements, and among pigments of all hues, red color occupies a very important position, because red color represents the significance of life, vitality and enthusiasm, and brings people a positive and enthusiasm feeling, so that it is indispensable to find a method for preparing rare earth red pigment.
The rare earth cerium sulfide (gamma-Ce 2S 3) is an environment-friendly red pigment which is bright red, strong in tinting strength, good in ultraviolet radiation resistance and free of heavy metal elements such as lead and cadmium, can effectively absorb a blue-green light part (490-500 nm) in a visible light region, has a dominant wavelength of about 608nm due to the electronic transition of 4f → 5d of Ce, and thus presents a bright red hue, and has strong absorption on ultraviolet rays due to the electronic transition of S3p → Ce5d, so that the red pigment also has the ultraviolet radiation resistance. Meanwhile, the cerium sulfide is insoluble in water and strong alkali solution, is easy to dissolve in acid and release hydrogen sulfide, has chemical stability of 1500 ℃ in inert gas and reducing atmosphere and 350 ℃ in oxidizing atmosphere, and has ideal thermal stability, so the rare earth cerium sulfide can be considered as a novel inorganic pigment for replacing cadmium red toxic pigment.
The most widely used methods for preparing rare earth cerium sulfide include two methods: solid phase reaction methods and H2S (CS 2) gas reduction methods. The sulfide synthesized by the solid phase method has large particles, more impurities and low chromatic value; the H2S (CS 2) gas reduction method uses toxic gases (H2S and CS 2) or generates toxic gases (SO 2 and SO 3), is not environment-friendly, and both methods are energy-consuming and difficult to react completely.
Disclosure of Invention
Compared with other methods for preparing the rare earth cerium sulfide, toxic, flammable and explosive vulcanizing agents such as H2S and CS2 are not used, the method is green and environment-friendly, the reaction energy consumption is low, the reaction is more sufficient, the content of impurities in the prepared rare earth cerium sulfide is low, the particle size is more uniform, and the chroma is more bright.
The supercritical fluid science technology is a green technology with low environmental load which is generally accepted, and completely accords with the concept of 'green science technology' of reducing or even realizing pollution-free sustainable development. On the other hand, from the viewpoint of energy saving, the supercritical technology has incomparable superiority compared with the industrial technology commonly used at present. At present, supercritical fluid research is mainly focused on supercritical carbon dioxide and supercritical water, wherein the supercritical water refers to a state when the temperature and pressure of a system exceed the critical point of water (critical temperature Tc =374.2 ℃ and critical pressure Pc =22.1 MPa). Because the performance parameters of water are greatly changed near the critical point, the multiphase reaction under the traditional solvent condition can be changed into homogeneous reaction, the diffusion coefficient is increased, and the mass transfer and heat transfer resistance is reduced, so that the diffusion is facilitated, the phase separation process is controlled, the reaction time can be shortened, the particle size, the morphology, the crystallinity and the like of a product are effectively controlled, and a plurality of chemical reactions are easier to occur in supercritical water.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing rare earth cerium sulfide by a supercritical hydrothermal method comprises the following experimental steps: uniformly mixing the rare earth compound solution, the sulfide solution and the alkali metal and/or alkaline earth metal solution to obtain a mixture A, putting the mixture A into a high-pressure reaction kettle of a supercritical device, heating to 375-410 ℃ after air in the high-pressure reaction kettle is removed, preserving heat for at least 24 hours when the pressure in the high-pressure reaction kettle reaches 22.5-36 MPa to obtain a solution with a precipitate B, and washing and drying the precipitate B to obtain the rare earth cerium sulfide.
Optionally, the alkali metal/alkaline earth metal is a mixed solution of one or more soluble salts containing Li, na, K or Ca.
Optionally, the rare earth compound is one or a mixture of more of rare earth metal sulfate of Ce, rare earth metal oxalate, rare earth metal chloride, rare earth metal borate and rare earth metal nitrate.
Optionally, the sulfide is one or more of thiourea, sodium sulfide, sodium thiosulfate and thioacetamide.
Optionally, the molar ratio of the sulfide to the rare earth compound is 1.5-2.
Optionally, the molar ratio of the cations in the dopant to the rare earth in the rare earth compound is 0.1-0.5.
Optionally, the PH of the mixture of the rare earth compound and the sulfide is 9 to 11.
Optionally, the supercritical reaction temperature is 375-410 ℃, the reaction pressure is 22.5-36 MPa, and the reaction time is 24h.
Optionally, the washing is to wash the precipitate B with deionized water and ethanol alternately, filter the washed precipitate B with a centrifuge, disperse the filtered product in deionized water or ethanol again, wash the precipitate B with ethanol for the last time, and centrifuge the centrifuge at a speed of 10000-12000 r/min.
Optionally, the drying temperature is 70-90 ℃, and the drying time is 12h.
The invention completely avoids using inflammable and explosive toxic gases such as hydrogen sulfide, carbon disulfide and the like in the implementation process, does not generate toxic gases, and is environment-friendly and safe. Meanwhile, the operation is simple, the energy consumption is low, and the reaction is more complete.
The rare earth cerium sulfide product prepared by the invention has bright color and strong tinting strength, and the tinting strength far exceeds that of iron oxide red, molybdenum chromium red, manganese red and other inorganic red pigments. Meanwhile, the product has uniform particle size, good dispersibility, good temperature resistance and corrosion resistance, no heavy metal element and no toxicity, and is a good substitute for toxic red pigment.
Drawings
FIG. 1 is an X-ray diffraction pattern of a rare earth cerium sulfide prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of rare earth cerium sulfide prepared according to example 1 of the present invention;
FIG. 3 is a UV-VIS diffuse reflectance spectrum of rare earth cerium sulfide prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. In which like parts are designated by like reference numerals. It should be noted that the terms "front," "back," "left," "right," "upper" and "lower" used in the following description refer to directions in the drawings, and the terms "bottom" and "top," "inner" and "outer" refer to directions toward and away from, respectively, the geometric center of a particular component.
Example 1
At room temperature, 4.34g of cerium source raw material (Ce (NO 3) 3.6H 2O) is weighed and dissolved in 150ml of deionized water, and the mixture is stirred for 30min by magnetic force to form uniform and stable cerium source solution for standby; 1.52g of sulfur source raw material (CH 4N 2S) is weighed and dissolved in 150ml of deionized water, and the solution is stirred for 30min by magnetic force to form uniform and stable sulfur source solution for later use. Dropwise adding the sulfur source solution into the cerium source solution, uniformly mixing, and adjusting the pH value of the mixed solution to 11 by using a 4mol/L NaOH solution. Transferring the prepared precursor liquid into a 500ml reaction kettle lining, then putting the reaction kettle into the lining, tightening the lining without air leakage, introducing N2, discharging air in the reaction kettle, then pressurizing to 3MPa, starting to heat up to 375 ℃, and keeping the temperature for 24 hours when the pressure reaches 22.5 MPa. And after the reaction is finished, closing the heating device, taking out the reaction kettle, and cooling to room temperature. And (3) washing the product obtained after the hydrothermal treatment with distilled water for 3 times and washing the product with ethanol for 3 times respectively, then placing the sample in an electric heating constant temperature air blast drying box, and drying the sample for 12 hours at 90 ℃ to obtain the final product.
The resulting product has chromaticity coordinates (L =45, a =52, b = 38).
Detected by an X-ray diffractometer, as shown in figure 1, the obtained red powder is gamma-Ce 2S3 with good crystallinity, and the product does not contain heavy metal elements and is non-toxic.
The observation of a scanning electron microscope shows that the prepared rare earth cerium sulfide has uniform grain diameter and good dispersity as shown in figure 3.
Through the observation of an ultraviolet visible spectrophotometer, as shown in fig. 2, the reflectivity of the sample in a 400-550 nm waveband is below 10%, the trend of the reflectivity steep increase in a 550-650 nm waveband is shown, and the reflectivity reaches the maximum in a 650-700 nm waveband, so that the appearance color of the sample is red.
The rare earth cerium sulfide powder prepared in this example was used as a colorant to be measured, and measured according to the measurement method of the relative tinting strength and the tint of a colored pigment by visual comparison.
The instrument adopted comprises:
automatic grinding machine: the diameter of the ground glass plate is 180-250 mm, the force is applied on a grinding machine by about 1kN, and the rotating speed is 70-120 r/min.
Adjusting a cutter: the steel conical cutter body is about 140-150 mm long, the widest part is about 20-25 mm, and the narrowest part is not less than 12.5mm.
Glass plate: colorless and transparent, and the size is about 150mm.
A wet film preparation device: the gap is 50-100 μm.
The white pigment paste is composed of 40 parts by mass of R-type titanium dioxide, 56 parts by mass of alkyd resin and 4 parts by mass of calcium stearate. The above components were mixed uniformly with a spatula, then ground on a triple roll mill until the fineness measured on a fineness plate was less than 15 μm, and stored in an airtight container.
The paint base adopts alkyd resin: a mixture based on 63% (m/m) linseed oil and 23% (m/m) phthalic anhydride meets the following requirements:
acid value: a maximum of 15mgKOH g;
viscosity (no solvent): 7-10 Pa.S;
hydroxyl value: about 40mgKOH/g.
The specific experimental steps are as follows:
grinding 1.5g of binder and 3g of the colorant to be tested on a grinder under the action of 1kN force, wherein the grinding is carried out for 50 revolutions each time, the grinding is carried out for 200 revolutions, slurry accounting for about one fourth of the total volume is taken out and stored in a suitable container, then the grinding is carried out for 300 revolutions and 400 revolutions, and a small part of the slurry which is the same as the grinding is respectively taken out and stored in a suitable container for standby.
1.5g of binder and 3g of selected cadmium red (CdSe 1-xSx) pigment are taken as standard samples, the most reasonable grinding revolution of the color paste is repeated, the color paste is arranged on a colorless glass plate for comparison, and the quality of the colorant to be detected is adjusted until the two colors are consistent when the comparison colors are inconsistent.
The relative tinting strength of the test samples was calculated by the following equation:
in the formula: a-mass (g) of the specimen which achieves the same tinctorial strength as the standard;
b-mass of standard sample (g).
The relative tinting strength of the colorant to be measured obtained by the measuring method is as follows: 93.3 percent
Example 2
Weighing 4.34g of cerium source raw material (Ce (NO 3) 3.6H 2O) at room temperature, dissolving in 150ml of deionized water, and magnetically stirring for 30min to form uniform and stable cerium source solution for later use; 1.5g of sulfur source raw material (CH 3CSNH 2) is weighed and dissolved in 150ml of deionized water, and the mixture is stirred for 30min by magnetic force to form uniform and stable sulfur source solution for standby. Dropwise adding the sulfur source solution into the cerium source solution, uniformly mixing, and adjusting the pH value of the mixed solution to 9 by using 4mol/L NaOH solution. Transferring the prepared precursor liquid into a 500ml reaction kettle lining, then putting the reaction kettle into the lining, tightening the lining without air leakage, introducing N2, discharging air in the reaction kettle, then pressurizing to 3MPa, starting to heat up to 395 ℃, keeping the pressure at 32MPa, and keeping the temperature for 24 hours. And after the reaction is finished, closing the heating device, taking out the reaction kettle, and cooling to room temperature. And (3) washing the product obtained after the hydrothermal treatment with distilled water for 3 times and washing the product with ethanol for 3 times respectively, then placing the sample in an electric heating constant temperature air blast drying box, and drying the sample for 12 hours at 70 ℃ to obtain the final product.
The resulting product has chromaticity coordinates (L × =44, a × =56, b × = 36).
The rare earth cerium sulfide powder prepared in this example was used as a colorant to be measured, and measured according to the measurement method of the relative tinting strength and the tint of a colored pigment by visual comparison.
The relative tinting strength of the colorant to be measured obtained by the measuring method is as follows: 92.9 percent
Example 3
Weighing 3.74g of cerium source raw material (CeCl3.7H2O) at room temperature, dissolving in 150ml of deionized water, and magnetically stirring for 30min to form uniform and stable cerium source solution for later use; 1.5g of sulfur source raw material (CH 3CSNH 2) is weighed and dissolved in 150ml of deionized water, and the solution is stirred for 30min by magnetic force to form uniform and stable sulfur source solution for standby. Dropwise adding the sulfur source solution into the cerium source solution, uniformly mixing, and adjusting the pH value of the mixed solution to 10 by using a 4mol/LNaOH solution. Transferring the prepared precursor liquid into a lining of a 500ml reaction kettle, then putting the lining into the reaction kettle, screwing the lining tightly without air leakage, introducing N2, discharging air in the reaction kettle, then pressurizing to 3MPa, starting to heat up until the temperature reaches 410 ℃, and keeping the temperature for 24 hours when the pressure reaches 36 MPa. After the reaction is finished, the heating device is closed, the reaction kettle is taken out, and then the reaction kettle is cooled to room temperature. And (3) washing the product obtained after the hydrothermal reaction with distilled water for 3 times and washing the product with ethanol for 3 times, then placing the sample in an electric heating constant-temperature air blast drying oven, and drying the sample for 12 hours at 70 ℃ to obtain the final product.
The resulting product has chromaticity coordinates (L × =42, a × =53, b × = 39).
The rare earth cerium sulfide powder prepared in this example was used as a colorant to be measured, and measured according to the measurement method of the relative tinting strength and the tint of a colored pigment by visual comparison.
The relative tinting strength of the colorant to be measured obtained by the measuring method is as follows: 92.5 percent
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (9)
1. A method for preparing rare earth cerium sulfide by a supercritical hydrothermal method is characterized by comprising the following steps: uniformly mixing the rare earth compound solution, the sulfide solution and the alkali metal and/or alkaline earth metal solution to obtain a mixture A, putting the mixture A into a high-pressure reaction kettle of a supercritical device, heating to 375-410 ℃ after air in the high-pressure reaction kettle is removed, preserving heat for at least 24 hours when the pressure in the high-pressure reaction kettle reaches 22.5-36 MPa to obtain a solution with a precipitate B, and washing and drying the precipitate B to obtain the rare earth cerium sulfide.
2. The supercritical hydrothermal method for preparing rare earth cerium sulfide as claimed in claim 1, wherein the rare earth compound is one or more of rare earth cerium sulfate, rare earth cerium oxalate, rare earth cerium chloride, rare earth cerium borate and rare earth cerium nitrate.
3. The supercritical hydrothermal method for preparing rare earth cerium sulfide as claimed in claim 1, wherein the sulfide is one or more of thiourea, sodium sulfide, thioacetamide and sodium thiosulfate.
4. The supercritical hydrothermal method for preparing rare earth cerium sulfide as claimed in claim 1, wherein the alkali metal and/or alkaline earth metal solution is a mixed solution containing one or more of soluble salts of Li, na, K or Ca.
5. The supercritical hydrothermal method for preparing rare earth cerium sulfide as claimed in claim 1, wherein the molar ratio of added sulfide to rare earth compound is 1.5-2.
6. The supercritical hydrothermal process for preparing rare earth cerium sulfide as claimed in claim 1, wherein the molar ratio of cations in the alkali metal and/or alkaline earth metal solution to rare earth in the rare earth compound is 0.1-0.5.
7. The supercritical hydrothermal process for preparing rare earth cerium sulfide as claimed in any one of claims 1 to 4, wherein the pH of the mixture of the rare earth compound and the sulfide is 9 to 11.
8. The supercritical hydrothermal method for preparing rare earth cerium sulfide according to any one of claims 1-4, wherein the washing is to wash the precipitate B with deionized water and ethanol alternately, the precipitate B is filtered by a centrifuge after washing, the filtered product is dispersed in deionized water or ethanol again, and the precipitate B is washed with ethanol for the last time, and the centrifuge speed of the centrifuge is 10000-12000 r/min.
9. The supercritical hydrothermal method for preparing rare earth cerium sulfide as claimed in any one of claims 1-4, wherein the drying temperature is 70-90 ℃ and the drying time is 12h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010058984A (en) * | 2008-09-01 | 2010-03-18 | Tohoku Univ | Synthetic process of organic modified metal sulfide nanoparticles by supercritical hydrothermal synthesis method |
| CN102515240A (en) * | 2011-11-28 | 2012-06-27 | 湖南师范大学 | Method for preparing red pigment cerium sulphide |
| WO2015149517A1 (en) * | 2014-04-02 | 2015-10-08 | 西安交通大学 | Supercritical hydrothermal synthesis method for metal or metal oxide nanoparticles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010058984A (en) * | 2008-09-01 | 2010-03-18 | Tohoku Univ | Synthetic process of organic modified metal sulfide nanoparticles by supercritical hydrothermal synthesis method |
| CN102515240A (en) * | 2011-11-28 | 2012-06-27 | 湖南师范大学 | Method for preparing red pigment cerium sulphide |
| WO2015149517A1 (en) * | 2014-04-02 | 2015-10-08 | 西安交通大学 | Supercritical hydrothermal synthesis method for metal or metal oxide nanoparticles |
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