CN102107902A - Method for preparing cerium sesquisulphide for red pigment by sulfur melting method - Google Patents
Method for preparing cerium sesquisulphide for red pigment by sulfur melting method Download PDFInfo
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- CN102107902A CN102107902A CN 201010621447 CN201010621447A CN102107902A CN 102107902 A CN102107902 A CN 102107902A CN 201010621447 CN201010621447 CN 201010621447 CN 201010621447 A CN201010621447 A CN 201010621447A CN 102107902 A CN102107902 A CN 102107902A
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- 238000000034 method Methods 0.000 title claims abstract description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 27
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000001054 red pigment Substances 0.000 title claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 9
- 239000011593 sulfur Substances 0.000 title abstract description 6
- 238000002844 melting Methods 0.000 title abstract 2
- 230000008018 melting Effects 0.000 title abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims abstract description 4
- 239000005864 Sulphur Substances 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 22
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 19
- -1 subcarbonate Chemical compound 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 150000003818 basic metals Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 230000002045 lasting effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000004073 vulcanization Methods 0.000 abstract description 4
- 239000011343 solid material Substances 0.000 abstract description 2
- 239000002671 adjuvant Substances 0.000 abstract 1
- 150000001785 cerium compounds Chemical class 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- MMXSKTNPRXHINM-UHFFFAOYSA-N cerium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Ce+3].[Ce+3] MMXSKTNPRXHINM-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- 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 7
- 102220043159 rs587780996 Human genes 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000002223 garnet Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WFLRGOXPLOZUMC-UHFFFAOYSA-N [Li].O=C=O Chemical compound [Li].O=C=O WFLRGOXPLOZUMC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 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
- 239000003610 charcoal Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910014103 Na-S Inorganic materials 0.000 description 1
- 229910014147 Na—S Inorganic materials 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ZCRPALBDTNNSTL-UHFFFAOYSA-N [O-2].S.[Ce+3] Chemical compound [O-2].S.[Ce+3] ZCRPALBDTNNSTL-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a method for preparing cerium sesquisulphide for red pigment by a sulfur melting method. The cerium sesquisulphide for the red pigment is prepared by reacting at a high temperature, wherein a cerium compound serves as a raw material; an alkali metal compound serves as an additive; sulfur serves as a vulcanizing agent; and active carbon serves as an adjuvant. Compared with the common gas vulcanizing agent vulcanization method, the preparation method has the advantages that: all the process reaction materials are solid materials and have obvious advantages; the materials are safe to use and convenient to transport; reaction speed is high and synthetic efficiency is high; and reaction tail gas has small discharge quantity and small recovery burden and is easy to recover. The process is suitable for preparing the cerium sesquisulphide for the red pigment on a large scale.
Description
Technical field
The present invention relates to the method that the molten legal system of a kind of sulphur is equipped with cerium sesqui sulfide used for red pigment, belong to chemical technology field.
Background technology
Red pigment is divided into organic red and inorganic red two big classes usually.Organic red lovely luster, strong coloring force, but its opacifying power, thermostability, the ability of light stability and ultra-violet radiation resisting is difficult to replace fully inorganic red, and the inorganic red that uses at present contains cadmium mostly, lead, and mercury etc. are to the very deleterious heavy metal element of human body.Human in recent years more and more higher to requirement on environmental protection, many countries make strict regulation limitations or ban use of the poisonous pigment that environment is polluted.The urgent preparation technology who seeks avirulent high-performance inorganic red of pigment manufacturer is 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 uses, as red pigment cerium sulphide (γ-Ce
2S
3) its color is dark red, nontoxicity, strong covering power, Heat stability is good, and strong absorption ultraviolet ray are the preferred material that replaces cadmium red.
From nineteen nineties, rare-earth sulfide tinting material and application thereof become one of research focus, and after this, countries such as France, Russia, Japan and the U.S. have successively applied for the national separately patent and the patent in the Europe and the world.
The preparation method of rare earth cerium sulphide, basically be gas vulcanization agent sulfurized method, for example French Luo Diya is at Chinese patents CN1201441, CN1271332, CN1426376, and European patent EP 0680930A is that rare earth compound and alkali metal compound mixture are at H
2S/CS
2Or high temperature is synthetic under the mixed atmosphere of the two.
Japanese patent laid-open 8-259229, the patent CN1111509C of Beijing Non-Ferrous Metal Research General Academy, CN1233752C are though be that rare earth compound and alkali metal compound mixture are at H
2The S effect is preparation sulfide down, but H
2S generates in Reaktionsofen, and reaction process feeds H
2, and be in that sulfur reaction is created on H in the cold zone material boat
2S, material reaction prepares sulfide in hydrogen sulfide and the high-temperature zone material boat.
The molten method of sulphur is synthesizing rare-earth oxysulfide a kind of method commonly used, and raw material is rare earth compound, alkaline carbonate and sulphur, reacts the synthesizing rare-earth oxysulfide at a certain temperature, is characterized in that synthetic method is simple, is beneficial to commercial scale production.The molten legal system of sulphur is equipped with rare-earth sulfide, does not appear in the newspapers, and close with the molten method of sulphur is Japanese Patent 19819, but its principle is a synthesizing rare-earth oxysulfide under the low temperature, the following and H of rare-earth oxide sulfate high temperature
2S further acts on synthesizing rare-earth sulfide.The patented technology scheme is with the mixture of Sedemesis, sulphur, the yellow soda ash graphite material boat of packing into, places in the tube furnace, feeds 10%H
2-90%Ar (percent by volume) is raised to 325 ℃ with 5 ℃/minute speed, is incubated 1 hour, is raised to 1200 ℃ with 5 ℃/minute speed again, is incubated 1 hour, obtains wine-colored γ-Ce
2S
3This method has reduced H
2S tail gas amount.But the boiling point of sulphur low (444.6 ℃), before reaching 1200 ℃ of high temperature, most sulfur vapors volatilize, cause H
2S is under-supply, and reaction not exclusively.
Summary of the invention
The objective of the invention is to work out a kind of simple, safety, cost is low, and is at high temperature can rapid reaction complete, and helps the preparation method of the molten method cerium sesqui sulfide used for red pigment of sulphur of environment protection.
The objective of the invention is to realize in the following manner:
Compound with cerium is a raw material, alkali metal compound is an additive, and sulphur is vulcanizing agent, and activated carbon is an auxiliary, the additional proportion of additive is that the mol ratio of basic metal/Ce is 0.05～0.5, and best additional proportion is that the mol ratio of basic metal/Ce is 0.15～0.25; The additional proportion of vulcanizing agent is that the mol ratio of S/Ce is 1.5～6.0, and best additional proportion is that the mol ratio of S/Ce is 2.0～4.0; The additional proportion of auxiliary is that the mol ratio of C/Ce is 1～4, and best additional proportion is that the mol ratio of C/Ce is 1.5～2.5; After the various reaction masses of requirement were mixed with mixing tank, the high purity graphite crucible of packing into was put into the flat-temperature zone of airtight tube type high-temperature furnace, and logical argon gas is driven the air in the reactive system; Equipment begins to heat up; temperature-rise period feeds argon shield; be warming up to 1000～1500 ℃ with 1～15 ℃ of/minute intensification speed; be incubated 30～180 minutes, tube furnace cooling, temperature-fall period sealed furnace caudal end egress or lasting feeding argon shield; be cooled to below 50 ℃ and come out of the stove; with the product depolymerization, wash with water, filter, dry, grind, obtain red γ-Ce
2S
3Powder.
The compound of described cerium is one or more the mixture in the carbonate, subcarbonate, nitrate, oxalate, vitriol of cerium dioxide or cerium.
Described alkali metal compound is one or more the mixture in alkaline carbonate, vitriol, sulphite, sulfide, the polysulfide;
The compound purity of described raw material cerium greater than 99% (with CeO
2/ ∑ REO meter, mass percent), additive purity is chemical pure, and the vulcanizing agent sulfur purity is a technical pure, and auxiliary activated carbon purity-fixed carbon mass percent is greater than greater than 80%.
The tube furnace argon gas is driven the time of air, and equipment heat-up rate and soaking time are decided on furnace capacity and charge amount.
γ-Ce
2S
3Building-up process can be divided into three phases: the fs is about 500 ℃, and this moment, Na-S formed melt, and sulphur begins to generate sulphur cerium oxide Ce near boiling point (444.6 ℃)
2O
2S; Subordinate phase is at 700-900 ℃, comprises Ce
2O
2The generation of S and Ce
2O
2S is at S
2, CS
2Effect Deng vulcanizing agent generates Ce down
2S
3, wherein gac plays absorption and suppresses S
2Volatilization and S
2Effect generates CS
2Deng effect; Phase III is more than 900 ℃, is Ce
2S
3Crystal formation transforms, grows and improves the stage, finally forms red gamma-Ce
2S
3It is good below 1400 ℃ that the synthetic top temperature is controlled at, and synthesis temperature is higher than 1400 ℃, and sintering phenomenon is arranged, and is unfavorable for follow-up washing and grinding technics.
According to the feature of reaction process staged reaction, the reasonable heat-up rate of control process:, control slower heat-up rate at 300～500 ℃ and 700～900 ℃, with 1～5 ℃/be divided into good, all the other stages, then control heat-up rate faster, with 5～15 ℃/be divided into good.
γ-Ce
2S
3Be the Th that possesses defective
3P
4The type cubic structure has metallic voids, and its stoichiometry is Ce
2.67 0.33S
4(represents the room).Discover that a spot of alkali metal cation can be stablized the γ phase, under the temperature condition of synthetic α or β, obtain the γ phase.Doped element partly or entirely is filled into γ-Ce
2S
3On the room of structure, also can replace the part cerium atom.Wherein, basic metal can reach peak concentration, and metering-type is A
0.5Ce
2.5S
4(A=Li, Na, K).Suitable doped element kind and consumption can be adjusted the electronic structure and the color of cerium sulphide.Considering that from the angle of synthetic cost additive is good with yellow soda ash, S-WAT, is 0.10～0.25 better with Na/Ce, and the mol ratio of Na/Ce is high more, and ruddiness is strong more, and color is dark more.
Behind the cerium sulphide end of synthesis, begin cooling, temperature-fall period should prevent the oxidation of air to product, and sealed furnace caudal end egress or the lasting argon shield state that feeds are lowered the temperature down, lower the temperature as adopting the sealed furnace caudal end egress, then should guarantee system's good sealing property.Because the chemically reactive of cerium sulphide is higher, should be cooled to below 50 ℃ and come out of the stove.
Synthetic product adds deionized water or distilled water, and depolymerization under the agitation condition then washes with water 2-3 time in the aqueous solution, and the soluble salt that separated and dissolved is residual utilizes the part activated carbon (activated carbon floats on water surface) of the differential liberation remnants of proportion simultaneously.The washing after-filtration is dried being lower than under 100 ℃ the temperature.The cerium sulphide of oven dry adopts the thorough isolating active carbon of cyclonic separator wind-force, is ground to desired particle size then.
The cerium sulphide building-up reactions produces a small amount of tail gas, and its basal component is: S
2, CS
2, CO, SO
2, COS, H
2S, CO
2
According to the character of each component of tail gas, the method for recovering tail gas of formulation is: the method that condensation-absorption-alkali absorbs.
113 ℃ of sulphur fusing points, tail gas is by drainer condensation recovery sulphur.
CS
246 ℃ of boiling points can adopt charcoal absorption-method of analysis.Tail gas is by active carbon bed, CS
2Be adsorbed, when gac reaches capacity, make CS with the way that heats
2Parse, condensation is reclaimed again, and gac can continue to use.
The principal reaction principle that alkali absorbs:
2NaOH+SO
2＝Na
2SO
3+H
2O
NaOH+H
2S＝Na
2S+H
2O
2NaOH+COS＝Na
2CSO
2+H
2O
6NaOH+3CS
2＝2Na
2CS
3+Na
2CO
3+H
2O
Na
2S+CS
2＝Na
2CS
3
Absorb the tail gas of handling through condensation-absorption-alkali,, directly discharge atmosphere through burn processing.
Institute's synthetic sesquialter cerium sulphide product is tested diffract spectral line and standard card 89-2260-Ce through X-ray diffraction analysis
2S
3Match (Fig. 1), the crystal formation that the sesquialter cerium sulphide of gained is described is the γ-Ce of cubic structure
2S
3Sesquialter cerium sulphide product has carried out the analysis of scanning electron microscope particle diameter grain looks, and the grain looks are class sphere (Fig. 2).Use UV365 UV, visible light near infrared spectrometer to measure, its chromaticity coordinates is: L
*36-39/a
*27-58/b
*12-43.
The advantage that the molten legal system of sulphur of the present invention is equipped with the cerium sesqui sulfide used for red pigment method is:
1. method of the present invention avoids directly using toxic gas H
2S or CS
2, and all adopting solid materials, material is safe in utilization, is convenient to accumulating.
2. gas vulcanization agent sulfidation is the gas-solid phase reaction process, and speed of response is limited by the diffusion of gas vulcanization agent in material, and method of the present invention is the gas-liquid-solid phase reaction process that vulcanizing agent and material closely contact, and speed of response is fast under the high temperature.
3. the reaction end gas quantity discharged is few, and the tail gas recycle burden is little, reclaims easily.
4. technology is fit to the mass preparation cerium sesqui sulfide used for red pigment.
Description of drawings
The XRD figure spectrum of Fig. 1-cerium sulphide sample;
The electron-microscope scanning picture of Fig. 2-cerium sulphide sample.
Concrete embodiment
Below with embodiment the molten legal system of sulphur of the present invention is equipped with the cerium sesqui sulfide used for red pigment method and is further described; to help the present invention and advantage thereof are done further to understand; protection scope of the present invention is not subjected to the qualification of these embodiment, and protection scope of the present invention is decided by claims.
Embodiment 1
Reaction mass: 100.00g cerium dioxide; The pure anhydrous sodium carbonate 3.10g of additive chemistry, the mol ratio of Na/Ce is 0.10; Vulcanizing agent technical pure sulphur 83.55g, the mol ratio of S/Ce is 4.5; Auxiliary activated carbon 17.40g, the mol ratio of C/Ce is 2.0.
After the various reaction masses of requirement were mixed with mixing tank, the high purity graphite crucible of packing into was put into the flat-temperature zone of airtight tube type high-temperature furnace, and logical argon gas is driven the air in the reactive system.6 liters/hour of argon flow amounts, the logical 20 minutes argon gas time.Heat up, the insulation system: room temperature～300 ℃, 20 minutes heating-up times; 300 ℃～500 ℃, 40 minutes heating-up times; 500 ℃～700 ℃, 20 minutes heating-up times; 700 ℃～900 ℃, 90 minutes heating-up times; 900 ℃～1100 ℃, 20 minutes heating-up times, 1100 ℃ are incubated 60 fens, then cooling.Intensification, insulating process procedure auto-control, each section that heats up at the uniform velocity heats up.Whole process of synthetic and temperature-fall period all feed 6 liters of/hour argon flow amounts.
Reaction end gas at first enters drainer, after condensation sulphur, tail gas are discharged by drainer, the tourie of coke is housed, and mainly adsorbs CS
2, feed aqueous sodium carbonate then, absorb remaining tail gas.
Furnace temperature is reduced to room temperature, takes out product, uses the deionized water depolymerization, washs 3 times, depolymerization and washing process, the part gac floats on water surface, and the water method isolating active charcoal that inclines filters then, 80 ℃ of oven dry, the thorough isolating active carbon of cyclonic separator wind-force grinds then, obtains γ-Ce
2S
3Color sample: bright-coloured large red, median size D50=1.0 μ m.
Embodiment 2
Reaction mass: cerous carbonate (folding CeO
250.0%) 100.00g; The pure anhydrous sodium carbonate 2.33g of additive chemistry, the mol ratio of Na/Ce is 0.15; Vulcanizing agent technical pure sulphur 27.85g, the mol ratio of S/Ce is 3.0; Auxiliary activated carbon 8.70g, the mol ratio of C/Ce is 2.0.
Its working method and equipment are substantially with embodiment 1, and only different is 700 ℃～900 ℃, and 60 minutes heating-up times, 1100 ℃ are incubated 30 fens, color sample: inferior bright-coloured large red, median size D50=0.75 μ m.
Embodiment 3
Reaction mass: the basic carbonate cerium (is obtained folding CeO by 120 ℃ of oven dry of cerous carbonate
290.0%) 100.00g; The pure anhydrous sodium carbonate 5.58g of additive chemistry, the mol ratio of Na/Ce is 0.20; Vulcanizing agent technical pure sulphur 66.98g, the mol ratio of S/Ce is 4.0; Auxiliary activated carbon 19.62g, the mol ratio of C/Ce is 2.5.
Its working method and equipment is substantially with embodiment 1, color sample: garnet, more bright-coloured, median size D50=0.80 μ m.
Embodiment 4
Reaction mass: 100.00g cerium dioxide; The pure Carbon Dioxide lithium of additive chemistry 2.15g, the mol ratio of Li/Ce is 0.10; Vulcanizing agent technical pure sulphur 83.55g, the mol ratio of S/Ce is 4.5; Auxiliary activated carbon 17.40g, the mol ratio of C/Ce is 2.0.
Its working method and equipment is substantially with embodiment 1, color sample: bright-coloured large red, median size D50=0.86 μ m.
Embodiment 5
Reaction mass: 100.00g cerium dioxide; The pure Anhydrous potassium carbonate 6.02g of additive chemistry, the mol ratio of K/Ce is 0.15; Vulcanizing agent technical pure sulphur 83.55g, the mol ratio of S/Ce is 4.5; Auxiliary activated carbon 17.40g, the mol ratio of C/Ce is 2.0.
Its working method and equipment is substantially with embodiment 1, color sample: inferior bright-coloured large red, median size D50=0.82 μ m.
Embodiment 6
Reaction mass: the basic carbonate cerium (is obtained folding CeO by 120 ℃ of oven dry of cerous carbonate
290.0%) 100.00g cerium dioxide; The pure Carbon Dioxide lithium of additive chemistry 3.87g, the mol ratio of Li/Ce is 0.20; Vulcanizing agent technical pure sulphur 66.98g, the mol ratio of S/Ce is 4.0; Auxiliary activated carbon 19.62g, the mol ratio of C/Ce is 2.5.
Its working method and equipment is substantially with embodiment 2, color sample: garnet, more bright-coloured, median size D50=0.75 μ m.
Embodiment 7
Reaction mass: the basic carbonate cerium (is obtained folding CeO by 120 ℃ of oven dry of cerous carbonate
290.0%) 100.00g cerium dioxide; The pure Anhydrous potassium carbonate 7.22g of additive chemistry, the mol ratio of K/Ce is 0.20; Vulcanizing agent technical pure sulphur 66.98g, the mol ratio of S/Ce is 4.0; Auxiliary activated carbon 19.62g, the mol ratio of C/Ce is 2.5.
Its working method and equipment is substantially with embodiment 2, color sample: garnet, more bright-coloured, median size D50=0.76 μ m.
Claims (7)
1. a sulphur melts the method that legal system is equipped with cerium sesqui sulfide used for red pigment, it is characterized in that: the compound with cerium is a raw material, and alkali metal compound is an additive, and sulphur is vulcanizing agent, activated carbon is an auxiliary, and the additional proportion of additive is that the mol ratio of basic metal/Ce is 0.05～0.5; The additional proportion of vulcanizing agent is that the mol ratio of S/Ce is 1.5～6.0; The additional proportion of auxiliary is that the mol ratio of C/Ce is 1～4; After the various reaction masses of requirement were mixed with mixing tank, the high purity graphite crucible of packing into was put into the flat-temperature zone of airtight tube type high-temperature furnace, and logical argon gas is driven the air in the reactive system; Equipment begins to heat up; temperature-rise period feeds argon shield; be warming up to 1000～1500 ℃ with 1～15 ℃ of/minute intensification speed; be incubated 30～180 minutes, tube furnace cooling, temperature-fall period sealed furnace caudal end egress or lasting feeding argon shield; be cooled to below 50 ℃ and come out of the stove; with the product depolymerization, wash with water, filter, dry, grind, obtain red γ-Ce
2S
3Powder.
2. the molten legal system of sulphur according to claim 1 is equipped with the method for cerium sesqui sulfide used for red pigment, it is characterized in that: the compound of described cerium is one or more the mixture in the carbonate, subcarbonate, nitrate, oxalate, vitriol of cerium dioxide or cerium.
3. the molten legal system of sulphur according to claim 1 is equipped with the method for cerium sesqui sulfide used for red pigment, it is characterized in that: described alkali metal compound is one or more the mixture in alkaline carbonate, vitriol, sulphite, sulfide, the polysulfide.
4. the molten legal system of sulphur according to claim 1 is equipped with the method for cerium sesqui sulfide used for red pigment, and it is characterized in that: the additional proportion of described additive is that the mol ratio of basic metal/Ce is 0.15～0.25.
5. the molten legal system of sulphur according to claim 1 is equipped with the method for cerium sesqui sulfide used for red pigment, and it is characterized in that: the additional proportion of described vulcanizing agent is that the mol ratio of S/Ce is 2.0～4.0.
6. the molten legal system of sulphur according to claim 1 is equipped with the method for cerium sesqui sulfide used for red pigment, and it is characterized in that: the additional proportion of described auxiliary is that the mol ratio of C/Ce is 1.5～2.5.
7. the molten legal system of sulphur according to claim 1 is equipped with the method for cerium sesqui sulfide used for red pigment, it is characterized in that: for above-mentioned preparation method's reaction end gas, the method that adopts condensation-absorption-alkali to absorb, at first condensation method recovery sulphur, then active carbon adsorption recovery CS
2, the tail gas of the aqueous solution that utilizes alkali-metal oxyhydroxide at last after to condensation-absorption absorbs fully.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120602A (en) * | 2011-01-20 | 2011-07-13 | 中国科学院长春应用化学研究所 | Preparation method of rare-earth colorant |
| CN103571179A (en) * | 2012-08-01 | 2014-02-12 | 山东道恩高分子材料股份有限公司 | Environment-friendly red color masterbatch for nylon |
| CN103708526A (en) * | 2013-11-26 | 2014-04-09 | 内蒙古大学 | Preparation method for rare earth sulfide pearlescent pigment |
| CN108715549A (en) * | 2018-06-05 | 2018-10-30 | 西北工业大学 | It is a kind of to prepare rare-earth sulfide γ-Ln2S3The method of crystalline ceramics |
| CN109796036A (en) * | 2017-12-28 | 2019-05-24 | 包头市宏博特科技有限责任公司 | A kind of vapor phase method preparation process of rare-earth sulfide |
| CN109867984A (en) * | 2019-01-25 | 2019-06-11 | 中国科学院包头稀土研发中心 | A kind of rare-earth oxide sulfate colorant and preparation method thereof |
| CN110746792A (en) * | 2019-11-12 | 2020-02-04 | 吉林省汇生科技有限责任公司 | Preparation method of rare earth sulfide compound |
| CN112280330A (en) * | 2020-08-05 | 2021-01-29 | 兰州大学 | Attapulgite-doped cerium sulfide pigment and preparation method thereof |
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| CN102120602A (en) * | 2011-01-20 | 2011-07-13 | 中国科学院长春应用化学研究所 | Preparation method of rare-earth colorant |
| CN102120602B (en) * | 2011-01-20 | 2012-07-04 | 中国科学院长春应用化学研究所 | Preparation method of rare-earth colorant |
| CN103571179A (en) * | 2012-08-01 | 2014-02-12 | 山东道恩高分子材料股份有限公司 | Environment-friendly red color masterbatch for nylon |
| CN103708526A (en) * | 2013-11-26 | 2014-04-09 | 内蒙古大学 | Preparation method for rare earth sulfide pearlescent pigment |
| CN109796036A (en) * | 2017-12-28 | 2019-05-24 | 包头市宏博特科技有限责任公司 | A kind of vapor phase method preparation process of rare-earth sulfide |
| CN108715549A (en) * | 2018-06-05 | 2018-10-30 | 西北工业大学 | It is a kind of to prepare rare-earth sulfide γ-Ln2S3The method of crystalline ceramics |
| CN109867984A (en) * | 2019-01-25 | 2019-06-11 | 中国科学院包头稀土研发中心 | A kind of rare-earth oxide sulfate colorant and preparation method thereof |
| CN110746792A (en) * | 2019-11-12 | 2020-02-04 | 吉林省汇生科技有限责任公司 | Preparation method of rare earth sulfide compound |
| CN112280330A (en) * | 2020-08-05 | 2021-01-29 | 兰州大学 | Attapulgite-doped cerium sulfide pigment and preparation method thereof |
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