CN109651846B - Post-treatment method of rare earth sulfide - Google Patents
Post-treatment method of rare earth sulfide Download PDFInfo
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- CN109651846B CN109651846B CN201811622624.1A CN201811622624A CN109651846B CN 109651846 B CN109651846 B CN 109651846B CN 201811622624 A CN201811622624 A CN 201811622624A CN 109651846 B CN109651846 B CN 109651846B
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- rare earth
- earth sulfide
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- -1 rare earth sulfide Chemical class 0.000 title claims abstract description 48
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000012065 filter cake Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- 239000003350 kerosene Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000012025 fluorinating agent Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000008396 flotation agent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- MMXSKTNPRXHINM-UHFFFAOYSA-N cerium(3+);trisulfide Chemical group [S-2].[S-2].[S-2].[Ce+3].[Ce+3] MMXSKTNPRXHINM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 5
- 238000003682 fluorination reaction Methods 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 2
- 239000000049 pigment Substances 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000004224 protection Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001054 red pigment Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- OLXOEPPPBAHCOC-UHFFFAOYSA-N cerium(3+) lanthanum(3+) trisulfide Chemical compound [S-2].[La+3].[Ce+3].[S-2].[S-2] OLXOEPPPBAHCOC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XDAHMMVFVQFOIY-UHFFFAOYSA-N methanedithione;sulfane Chemical compound S.S=C=S XDAHMMVFVQFOIY-UHFFFAOYSA-N 0.000 description 1
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- KKZKWPQFAZAUSB-UHFFFAOYSA-N samarium(iii) sulfide Chemical compound [S-2].[S-2].[S-2].[Sm+3].[Sm+3] KKZKWPQFAZAUSB-UHFFFAOYSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a post-treatment method of rare earth sulfide, which is characterized in that the prepared rare earth sulfide primary powder is treated by the steps of the invention, and the pigment has bright color, strong tinting strength and covering power, good chemical stability and good heat resistance.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a post-treatment method of rare earth sulfide.
Background
With the increasing environmental protection situation, in recent years, many countries have made strict regulations to limit or prohibit the use of toxic pigments that pollute the environment, and colored inorganic pigments containing toxic heavy metals such as cadmium, chromium, lead, etc. that are being used in large quantities in the market are being eliminated. In the last 90 th century, marking paints on roads are regulated by legislation in countries such as Europe and America to be lead-free, and in the European Union of the last year, all red and yellow pigments are regulated not to contain cadmium. Therefore, the development of green, non-toxic and pollution-free high-performance red and yellow pigments is imminent.
The rare earth sulfide pigment is an environment-friendly inorganic pigment without heavy metals, is insoluble in water and strong alkaline solution, is easily soluble in acid and releases hydrogen sulfide gas, and has the chemical stability of 1500 ℃ in inert gas and reducing atmosphere and 350 ℃ in oxidizing atmosphere. In recent years, rare earth sulfide pigment has bright color and good weather resistance, so that the rare earth sulfide pigment is used as an environment-friendly color pigment in the fields of plastics, coatings and the like to replace toxic heavy metal pigment.
The most widely used preparation methods of rare earth sulfide pigments are two: one is a solid-solid synthesis method, and the other is a gas-solid synthesis method. The rare earth sulfide pigment synthesized by any method has the defects of poor tinting strength and covering power, low thermal stability and poor acid resistance.
Disclosure of Invention
Therefore, the present invention aims to obtain a rare earth sulfide for pigments which is non-toxic, has good dispersibility, and has improved tinting strength, hiding power, thermal stability and acid resistance, without affecting the color of the rare earth sulfide pigment itself.
The above object of the present invention is achieved by the following technical solutions:
a method for post-treatment of rare earth sulfides, the method comprising the steps of:
(1) mixing the rare earth sulfide primary powder with water to obtain a mixed solution; adding a flotation agent into the mixed solution, grinding and mixing in a colloid mill, removing floating aggregates during grinding, and filtering to obtain a filter cake.
(2) Washing the filter cake obtained in the step (1) with an alcoholic solution, mixing and stirring the washed filter cake and the alcoholic solution, adding a dispersing agent in the stirring process, and then grinding the mixture under an oxygen-free condition until the particle size of the rare earth sulfide in the mixed solution is 100-3000 nm;
(3) after the step (2) is finished, adding a fluorinating agent into the mixed solution for fluorination treatment;
(4) after the fluorination treatment in the step (3) is finished, adding zinc oxide and a catalyst into the mixed solution;
(5) immediately adding a transparent oxide precursor into the mixed solution after the step (4) is finished, and stirring for 1-3h at the speed of 100-1000 g/min;
(6) after the step (5) is finished, filtering, washing with alcohol and drying to obtain dry rare earth sulfide;
(7) and (4) screening the dried rare earth sulfide obtained in the step (6) by using a centrifugal screen to obtain a product.
Preferably, in the step (1), the rare earth sulfide primary powder is a primary powder of cerium sulfide, lanthanum cerium sulfide or samarium sulfide; more preferably, the rare earth sulfide primary powder is cerium sulfide primary powder;
preferably, in the step (1), the mass ratio of the rare earth sulfide primary powder to water is 1: 1-5;
preferably, in step (1), the flotation agent is kerosene, diesel oil, vegetable oil;
preferably, in the step (1), the mass of the flotation agent is 3% -9% of the mass of the rare earth sulfide primary powder, and more preferably 5%;
preferably, in the step (1), the floating aggregate is an aggregate of the carbon powder and the flotation agent in the primary powder;
preferably, in step (2), the alcohol solution is selected from methanol, ethanol or butanol, more preferably 99% ethanol;
preferably, in the step (2), the mass of the alcohol solution for mixing with the filter cake is 2-10 times, more preferably 3 times that of the rare earth sulfide primary powder;
preferably, in step (2), the dispersant is a nonionic water-soluble or organic solvent-soluble polymer; more preferably cellulose and its derivatives, polyvinylamides, polyethylene oxides, polyethylene glycols, polyoxyethylenated polyoxypropylene glycols, polyacrylates, polyoxyethylenated acid esters, polyoxyethylenated alkylphenols, polyvinyl alcohols, alkanolamides, polyvinylpyrrolidone or xanthan gum-based compounds, more preferably polyvinylpyrrolidone;
preferably, in the step (2), the mass of the dispersing agent is 0.5-5% of the mass of the rare earth sulfide primary powder, and more preferably is 2%;
preferably, in step (2), the particle size is 300-800nm, preferably 500 nm;
preferably, in step (3), the fluorinating agent is a solid, liquid or gaseous fluorinating agent, more preferably a liquid or gaseous fluorinating agent;
preferably, in step (3), the fluorinating agent is selected from fluorine gas, hydrofluoric acid, ammonium fluoride, alkali metal fluoride or nitrogen fluoride, more preferably ammonium fluoride;
preferably, in the step (3), the mass of the fluorinating agent is 1-20% of that of the rare earth sulfide primary powder, and more preferably 5%;
preferably, in step (4), the zinc oxide has a particle size of less than 40 μm, more preferably 500 nm;
preferably, in the step (4), the mass of the zinc oxide is 1-15% of the mass of the rare earth sulfide primary powder; more preferably 5%;
preferably, in the step (4), the catalyst is ammonia water, sodium hydroxide, potassium hydroxide or sodium carbonate, and more preferably, ammonia water;
preferably, in the step (4), the mass of the catalyst is 5-60% of the mass of the rare earth sulfide primary powder; more preferably 25%;
preferably, in step (5), the transparent oxide precursor is selected from one or more of ethyl silicate (corresponding to silica), aluminum sulfate (corresponding to alumina), zirconium sulfate (corresponding to zirconia), calcium sulfate (corresponding to calcium oxide) or rare earth sulfate (corresponding to rare earth metal oxide); more preferably, the transparent oxide precursor is selected from ethyl silicate;
preferably, in the step (5), the mass of the transparent oxide precursor is 5-50% of the mass of the rare earth sulfide primary powder; more preferably 15%;
preferably, during step (5) the temperature is maintained at 10-40 ℃, more preferably at 25 ℃; maintaining a pH of 8-10, more preferably 9;
preferably, in step (7), the screen size of the centrifugal screen is 10-100 μm, more preferably 45 μm.
In a particular embodiment, the fluorination treatment of step (3) is carried out using the following conditions:
Ce2S3slurry concentration (which refers to a mixture obtained after the treatment in the step (2), namely rare earth sulfide, alcoholic solution and dispersing agent): 300-500 g/L;
NH4F solution concentration: 120-180 g/L;
and (4) treating the pH: more than 8 to 10;
treatment temperature: more than 20-30 ℃;
treatment time: 100 and 120 min.
In another specific embodiment, step (6) is performed after step (5) is performed 2 or more times, and when step (6) is performed after step (5) is performed 2 or more times, the transparent oxide precursor used in each execution of step (5) may be the same or different.
In yet another specific embodiment, step (5) is performed 2 times before step (6), wherein the transparent oxide precursor used in the first step (5) is ethyl silicate (corresponding to silica) and the transparent oxide precursor used in the second step (5) is aluminum sulfate (corresponding to alumina).
The rare earth sulfide pigment obtained by the post-treatment method has bright color, less carbon particle impurities, no larger particles in materials, uniform particle size distribution, improved tinting strength and covering power, improved ultraviolet resistance and weather resistance, good chemical stability and heat resistance of the obtained product, incomparable with organic red pigments, no heavy metal and environmental protection.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
Unless otherwise stated, the rare earth sulfide primary powders described in the following examples were prepared by the following steps:
1) uniformly mixing a rare earth compound and an additive, and filling the mixture into a reaction container, wherein the rare earth compound is cerium carbonate, the additive is sodium carbonate, and the addition ratio of the additive is that the molar ratio of Na to Ce is 0.8;
2) introducing inert gas into the reaction vessel to displace air in the reactor, and introducing mixed sulfur source gas of hydrogen sulfide and carbon disulfide after 30min, wherein the addition ratio of the gas sulfur source is that the molar ratio of S/Ce is 3;
3) heating from room temperature to 500 deg.C at a speed of 10 deg.C/min, maintaining for 60 min, heating to 900 deg.C at a speed of 10 deg.C/min, and maintaining for 120 min.
Example 1
(1) Mixing and grinding 400g of cerium sulfide primary powder and 1200g of water in a colloid mill, then adding 20g of kerosene, fishing out the kerosene and carbon powder after 5 minutes until no kerosene and carbon powder float on the surface of the mixed solution, and then filtering to obtain a filter cake;
(2) washing the filter cake obtained in the step (1) with 95% ethanol, mixing the washed filter cake with 95% ethanol according to the mass ratio of 1:2, adding 8g of PVP (polyvinylpyrrolidone) dispersing agent, and reducing the particle size of the pigment to 500nm by using a sand mill under the protection of nitrogen;
(3) then adding 20g of ammonium fluoride into the mixed solution at the temperature of 20-30 ℃ and reacting for 2 h;
(4) then adding 20g of zinc oxide and 200g of ammonia water into the mixed solution;
(5) adding 60g of tetraethoxysilane into the mixed solution within 2 hours, and stirring for 2 hours;
(6) then filtering, washing and drying;
(7) and (4) sieving the dried material by a 45-micron centrifugal sieve to obtain the product.
Example 2
(1) Mixing and grinding 400g of cerium sulfide primary powder and 1200g of water in a colloid mill, then adding 20g of kerosene, fishing out the kerosene and carbon powder after 5 minutes until no kerosene and carbon powder float on the surface of the mixed solution, and then filtering to obtain a filter cake;
(2) washing the filter cake obtained in the step (1) with 95% ethanol, mixing the washed filter cake with 95% ethanol according to the mass ratio of 1:2, adding 8g of PVP dispersant, and reducing the particle size of the pigment to 4000nm by using a sand mill under the protection of nitrogen;
steps (3) to (7) were the same as in example 1.
Example 3
(1) Mixing and grinding 400g of cerium sulfide primary powder and 1200g of water in a colloid mill, then adding 20g of kerosene, fishing out the kerosene and carbon powder after 5 minutes until no kerosene and carbon powder float on the surface of the mixed solution, and then filtering to obtain a filter cake;
(2) washing the filter cake obtained in the step (1) with 95% ethanol, mixing the washed filter cake with 95% ethanol according to the mass ratio of 1:2, adding 8g of PVP dispersant, and reducing the particle size of the pigment to 2000nm by using a sand mill under the protection of nitrogen;
steps (3) to (7) were the same as in example 1.
The coloring power of the products prepared in examples 1 to 3 was measured, and the results are shown in the following table:
| examples | Coloring power |
| 1 | 100 |
| 2 | 50 |
| 3 | 80 |
Example 4
Steps (1) to (3) are the same as in example 1;
only adding 20g of zinc oxide into the mixed solution when the step (4) is carried out, and not adding ammonia water;
steps (5) to (7) were the same as in example 1.
Example 5
Steps (1) to (3) are the same as in example 1;
adding 20g of zinc oxide and 50g of ammonia water into the mixed solution;
steps (5) to (7) were the same as in example 1.
Example 6
Steps (1) to (4) are the same as in example 1;
stirring for 2 hours only in the step (5), and adding no tetraethoxysilane;
steps (6) to (7) were the same as in example 1.
Example 7
Steps (1) to (4) are the same as in example 1;
step (5) adding 28g of tetraethoxysilane into the mixed solution within 2 hours, and stirring for 2 hours;
steps (6) to (7) were the same as in example 1.
The temperature resistance and H of the products obtained in examples 1 and 4 to 7 were measured2S release, results are shown in the following table:
| examples | Temperature resistance (DEG C) | H2S burst size (ppm) |
| 1 | 320 | 95 |
| 4 | 240 | 505 |
| 5 | 280 | 280 |
| 6 | 240 | 610 |
| 7 | 280 | 290 |
Claims (10)
1. A method for post-treatment of rare earth sulfides, the method comprising the steps of:
(1) mixing the rare earth sulfide primary powder with water to obtain a mixed solution; adding a flotation agent into the mixed solution, grinding and mixing in a colloid mill, removing floating aggregates in the grinding process, and filtering to obtain a filter cake;
(2) washing the filter cake obtained in the step (1) with an alcoholic solution, mixing and stirring the washed filter cake and the alcoholic solution, adding a dispersing agent in the stirring process, and then grinding the mixture under an oxygen-free condition until the particle size of the rare earth sulfide in the mixed solution is 500 nm;
(3) after the step (2) is finished, adding a fluorinating agent into the mixed solution for fluorination treatment;
(4) after the fluorination treatment in the step (3) is finished, adding zinc oxide and a catalyst into the mixed solution;
(5) immediately adding a transparent oxide precursor into the mixed solution after the step (4) is finished, and stirring for 1-3h at the speed of 100-1000 g/min;
(6) after the step (5) is finished, filtering, washing and drying to obtain dry rare earth sulfide;
(7) screening the dried rare earth sulfide obtained in the step (6) by a centrifugal screen to obtain a product
In the step (1), the rare earth sulfide primary powder is cerium sulfide primary powder; the flotation agent is kerosene, and the mass of the flotation agent is 5% of that of the rare earth sulfide primary powder; the floating aggregate is an aggregate of carbon powder and a flotation agent in the primary powder;
in the step (2), the alcoholic solution is ethanol; the mass of the alcohol solution for mixing with the filter cake is 2 times of the mass of the primary powder of the rare earth sulfide; the dispersing agent is polyvinylpyrrolidone; the mass of the dispersing agent is 2% of that of the rare earth sulfide primary powder;
in step (3), the fluorinating agent is ammonium fluoride; the mass of the fluorinating agent is 5% of that of the rare earth sulfide primary powder;
in the step (4), the mass of the zinc oxide is 5% of that of the rare earth sulfide primary powder; the catalyst is ammonia water; the mass of the catalyst is 50% of that of the rare earth sulfide primary powder;
in the step (5), the transparent oxide precursor is selected from ethyl silicate.
2. The method according to claim 1, wherein in the step (1), the mass ratio of the rare earth sulfide primary powder to the water is 1: 1-5.
3. The method of claim 1, wherein in step (4), the zinc oxide has a particle size of less than 40 μm.
4. The method according to claim 3, wherein in step (4), the zinc oxide has a particle size of 500 nm.
5. The method of claim 1, wherein the temperature is maintained at 10-40 ℃ during step (5).
6. The method of claim 5, wherein the temperature is maintained at 25 ℃ during step (5).
7. The method of claim 1, wherein the pH is maintained at 8-10 during step (5).
8. The method of claim 7, wherein during step (5), the pH is maintained at 9.
9. The method according to claim 1, wherein in the step (7), the centrifugal screen has a pore size of 10 to 100 μm.
10. The method according to claim 9, wherein in step (7), the centrifugal screen has a pore size of 45 μm.
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| CN112625464B (en) * | 2020-12-01 | 2021-10-26 | 景德镇陶瓷大学 | Preparation method of PEG (polyethylene glycol) and carbon powder refined cristobalite coated gamma-Ce 2S3 red pigment and product prepared by preparation method |
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| CN1241987A (en) * | 1996-11-19 | 2000-01-19 | 罗狄亚化学公司 | Use of a beta rare earth sulphide as colouring pigment and method for preparing same |
| CN1426376A (en) * | 2000-03-30 | 2003-06-25 | 罗狄亚稀土公司 | Composition based on rare earth metal sulplide with improved chemical stability, its preparation method and use as pigment thereof |
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| CN103819934A (en) * | 2014-02-25 | 2014-05-28 | 内蒙古大学 | Method for preparing coated rare earth sulfide pigment |
| CN104289319A (en) * | 2008-07-25 | 2015-01-21 | 塞特克技术公司 | Flotation reagents and flotation processes utilizing same |
| 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 |
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| CN1241987A (en) * | 1996-11-19 | 2000-01-19 | 罗狄亚化学公司 | Use of a beta rare earth sulphide as colouring pigment and method for preparing same |
| CN1426376A (en) * | 2000-03-30 | 2003-06-25 | 罗狄亚稀土公司 | Composition based on rare earth metal sulplide with improved chemical stability, its preparation method and use as pigment thereof |
| CN104289319A (en) * | 2008-07-25 | 2015-01-21 | 塞特克技术公司 | Flotation reagents and flotation processes utilizing same |
| CN102770214A (en) * | 2009-12-04 | 2012-11-07 | 巴里克黄金公司 | Separation of cooper minerals from pyrite using air-metabisulfite treatment |
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