CN1233752C - Method for continuously preparing cerium sesquisulfide for red pigment - Google Patents
Method for continuously preparing cerium sesquisulfide for red pigment Download PDFInfo
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- CN1233752C CN1233752C CN 01139900 CN01139900A CN1233752C CN 1233752 C CN1233752 C CN 1233752C CN 01139900 CN01139900 CN 01139900 CN 01139900 A CN01139900 A CN 01139900A CN 1233752 C CN1233752 C CN 1233752C
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- Prior art keywords
- cerium
- compound
- red pigment
- sulphur
- alkali
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Links
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 69
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000001054 red pigment Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000005864 Sulphur Substances 0.000 claims abstract description 72
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 46
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 26
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910052786 argon Inorganic materials 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 39
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 39
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 238000011437 continuous method Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 14
- -1 Alkali metal sulfite Chemical class 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 12
- 230000001070 adhesive effect Effects 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 6
- 150000003818 basic metals Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 25
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 7
- 150000002431 hydrogen Chemical class 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000109 continuous material Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 20
- 229910001220 stainless steel Inorganic materials 0.000 description 20
- 239000010935 stainless steel Substances 0.000 description 20
- 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
- 229920003023 plastic Polymers 0.000 description 10
- 239000004033 plastic Substances 0.000 description 10
- 239000004568 cement Substances 0.000 description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 230000001627 detrimental effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 230000001172 regenerating effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 241000255964 Pieridae Species 0.000 description 2
- 238000010923 batch production 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
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- RMSNEUAKJNEDNS-UHFFFAOYSA-N carbon dioxide;cerium Chemical compound [Ce].O=C=O RMSNEUAKJNEDNS-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 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
- 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002932 luster Substances 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
- 239000011707 mineral Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000485 pigmenting effect Effects 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
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a method for preparing cerium sesquisulfide for red pigment. Cerium dioxide or a cerous compound is used as raw material, alkali carbonate or at least one of other compounds of an alkali metal is used as an additive, and the molar ratio to the alkali metal and cerium is from 0.05 to 0.5. The raw material is evenly mixed with the additive to prepared into furnace charge. An inner pipe of a sulphur furnace, an inner pipe of a rotary kiln and a gas pipeline in equipment form a closed system. Air in a reaction system is driven by nitrogen or argon. Sulfur is placed in the inner pipe of the sulphur furnace, and temperature is controlled to be from 300 to 450 DEG C. When the nitrogen or the argon is switched into hydrogen, the hydrogen reacts with sulphur steam to generate the mixed gas of hydrogen sulphide and the hydrogen. An included angle theta is formed between the inner pipe of the rotary kiln and a horizontal plane and is sloped toward a discharge hole, and temperature is controlled to be from 800 to 1400 DEG C. The inner pipe of the rotary kiln rotates, and the gas and the furnace charge reversely flow. The furnace charge reacts with the mixed gas generated from the sulphur furnace to generate a product, and a continuous material entering and discharging production mode is realized. The method has the advantages of energy consumption reduction and enhancement of equipment utilization rate.
Description
(1) technical field
The present invention relates to contain the preparation method of the cerium sesquisulfide for red pigment of alkali metal.
(2) background technology
Red can be divided into organic red pigment and inorganic red pigment two big classes.Organic red pigmenting power is strong, good dispersity, and lovely luster, it is widely used.Its shortcoming is that covering power, thermostability and light stability are relatively poor, not as inorganic red pigment, so organic red pigment can not replace inorganic red pigment fully, in fact, still uses inorganic red pigment both at home and abroad in a large number in coating and plastics etc. are produced.But employed inorganic red pigment contains the heavy metal element that cadmium, lead, mercury etc. directly jeopardize HUMAN HEALTH and environment mostly at present.Along with more and more higher, receive the concern of each country to requirement on environmental protection.Many countries have made strict regulation limitations or have banned use of this deleterious pigment.Current, the avirulent mineral dye of the urgent searching of pigment manufacturer is to satisfy the requirement of environment protection and product performance.
γ type sesquialter cerium sulphide pigment colour is dark red, nontoxic, strong covering power, Heat stability is good.It keeps stable under 350 ℃ the temperature in oxygen atmosphere, keep stable in inertia or reducing atmosphere under 1500 ℃ the temperature, is the preferred material that replaces poisonous cadmium red.
Chinese patent literature CN1248545A has proposed a kind of preparation method of new cerium sesquisulfide for red pigment.Its technology is to be that raw material or at least a alkali-metal other compound are additive with the cerium dioxide, and the add-on of additive is that the mol ratio of basic metal/cerium is 0.05～0.5; After the cerium dioxide of requirement and additive mixed, put into the reaction boat, place in the high-temperature zone of airtight tube furnace, sulphur places in the cold zone of airtight tube furnace, the feeding argon gas is driven the air in the reactive system continuously, is heated up in cold zone, high-temperature zone; Argon gas is switched to hydrogen; The high-temperature zone is warming up to 1000～1600 ℃ continuously, and constant temperature kept 75～150 minutes under 1000～1600 ℃ temperature, makes the tube furnace cooling, stops to feed hydrogen, closed tube stove caudal end egress, and reactive system is communicated with the gas-storing bag that is filled with argon gas.After the discharging, product is ground, wash with water, filter, oven dry.The advantage of this technology is to avoid directly using toxic gas hydrogen sulfide or dithiocarbonic anhydride, and has adopted hydrogen, and is easy to operate, free from environmental pollution, do not damage health of operators, and can prepare the dark red cubic r-Ce of color
2S
3But the weak point of this technology be step, can not continuous production, the energy consumption height, production efficiency is lower.
(3) summary of the invention
Purpose of the present invention just is to work out a kind of existing technological merit that both kept, and overcomes the method for the insufficient production cerium sesqui sulfide used for red pigment of prior art again.
A kind of continuous method for preparing cerium sesqui sulfide used for red pigment of the present invention, other compound with cerium dioxide or cerium is a raw material, alkaline carbonate or at least a alkali-metal other compound are additive, the mol ratio of basic metal/cerium is 0.05～0.5, other compound of said cerium comprises the carbonate of cerium, acetate, oxalate, tartrate, malonate, vitriol, said alkali-metal other compound comprises alkali-metal oxide compound, acetate, oxalate, sulfide, polysulfide, vitriol, sulphite is evenly made block furnace charge with other compound of raw material cerium dioxide or cerium and alkaline carbonate or at least a alkali-metal other compound; Interior pipe in the rotary kiln and horizontal plane have an angle theta, make the interior pipe opening for feed furnace charge plane of rotary kiln be higher than the discharge port furnace charge plane of pipe in it, place sulphur in the boiler tube of sulphur stove, interior pipe in the boiler tube of sulphur stove and the rotary kiln and gas piping constitute a closed system, drive air in the reactive system with nitrogen or argon gas, the gas flow direction is opposite with the direction of motion of furnace charge; Nitrogen or argon gas are switched to hydrogen, the interior pipe of rotary kiln rotates, the furnace tube temperature of sulphur stove is controlled at 300～450 ℃, the temperature of the interior pipe of rotary kiln is controlled at 800～1400 ℃, add furnace charge from the interior pipe opening for feed of rotary kiln, the traveling time of furnace charge in 800～1400 ℃ high-temperature area remained on more than 15 minutes, product is collected from the rotary kiln discharge port, broken or the pulverizing with product, and the process aftertreatment makes product.Aftertreatment can be adopted fluoridation, washes the technology of filtering drying with water.
Other compound of raw material cerium dioxide or cerium and alkaline carbonate or at least a alkali-metal other compound is even, make furnace charge, drying, drying temperature is 100～160 ℃.The mol ratio of basic metal/cerium is 0.05～0.5, is 0.2～0.3 for good with its mol ratio again.Said alkaline carbonate or alkali-metal other compound are good with anhydrous sodium carbonate or sodium sulphite anhydrous 99.3.The blended method can be the blending means of grinding, ball milling or comminution by gas stream.After mixing, make block furnace charge.In order to remove the moisture of furnace charge as far as possible, be preferably in drying under the temperature more than 110～160 ℃, be good with 0.5～2 hour.
In order to make furnace charge have good mobility, to avoid on the interior pipe of rotary kiln, producing furnace accretion, furnace charge also can adopt block furnace charge, and said block furnace charge can be wherein a kind of of cubes, rectangular parallelepiped, right cylinder, particulate state.If its length of cubes or rectangular parallelepiped can be respectively 6～40 millimeters, 6～10 millimeters, 6～10 millimeters, if its diameter of right cylinder can be 5～10 millimeters of Φ, high 3～6 millimeters.Their method for making is furnace charge to be put into mould be pressed into cubic rectangular-shaped or cylindrical shape.
The method for making of granular block furnace charge be with other compound of cerium dioxide or cerium and alkaline carbonate or at least a alkali-metal other compound evenly after, add the adhesive polyethylene alcohol solution, stir, drying is made the particulate state furnace charge (certainly by compacting, make cubic, rectangular-shaped, cylindric), and in 110～160 ℃ of dryings, and form the particulate state furnace charge, the particulate size with consistent for well, generally can be less than 0.9 millimeter, greater than 0.46 millimeter.The add-on of polyvinyl alcohol water solution is that the weight ratio of polyvinyl alcohol water solution/(other compound+alkaline carbonate of cerium dioxide or cerium or at least a alkali-metal other compound+SULPHUR POWDER) or polyvinyl alcohol water solution/(other compound+alkaline carbonate of cerium dioxide or cerium or at least a alkali-metal other compound) is 5～40: 100, and again with 10～15: 100 for well.The concentration of used polyvinyl alcohol water solution is weight percentage 1～10%, especially with its weight percentage 2～5% for well.
Adding sulphur in other compound of raw material cerium dioxide or cerium and alkaline carbonate or at least a alkali-metal other compound mixes, and under 120～160 ℃ temperature, heat, 0.5～2 hour heat-up time, make block furnace charge, the speed of response that generates the sesquialter cerium sulphide is accelerated.The mol ratio of sulphur/cerium is 0.1～3, is excellent with its mol ratio 1～1.5 again.Owing in block furnace charge, added sulphur, the sulphur of fusing strengthens the adhesive fastness of block furnace charge when heating, sulphur makes block furnace charge form vesicular when evaporating in rotary kiln, can strengthen the velocity of diffusion of hydrogen sulfide, has accelerated the speed of response of furnace charge and hydrogen sulfide.
Pack into the sulphur of interior pipe of sulphur stove, with the industrial sulphur of removing moisture content for well.Drive the air of the reactive system of sealing continuously with nitrogen of crossing through purification utensil or argon gas.The interior pipe of interior pipe in the sulphur stove and rotary kiln is heated up, when the temperature of sulphur stove reaches 250～300 ℃, nitrogen or argon gas are switched to hydrogen, in experiment of the present invention the flow control of hydrogen at 20～30 liters/hour, used hydrogen with by the hydrogen behind the purification utensil for well.The interior pipe of rotary kiln and horizontal plane have an angle theta, make the opening for feed of the interior pipe of rotary kiln be higher than in the discharge port of pipe.The diameter of pipe in rotary kiln after the length of its high-temperature zone (800～1400 ℃) and the material shape of piece and input speed are determined, utilizes the method for regulating the speed that material moves in the pipe in kiln to guarantee to expect that enough residence time are arranged in the high-temperature zone.And the speed that material moves is to be undertaken by the speed of pipe rotation in the control kiln and the size of angle theta.The time that block furnace charge is moved in 800～1400 ℃ high-temperature zone remained on more than 15 minutes, the time that block furnace charge is moved in 1100～1250 ℃ high-temperature area remains on 30～120 minutes for well, reaction is carried out fully like this, generates sesquialter cerium sulphide γ-Ce that red pigment is used
2S
3Input speed in the experiment of the present invention is 50～200 Grams Per Hours, and the interior pipe in the rotary kiln and the angle theta of horizontal plane are 0.2～10 °, more often adopt 0.2～1.0 °, and the speed control of its rotation is at 0.1～1.0r/min.The furnace tube temperature of sulphur stove is controlled at 300～450 ℃, again with 320～360 ℃ for well.The interior pipe temperature of rotary kiln is controlled at 800～1400 ℃, is good with 1100～1250 ℃ again.
Sesquialter cerium sulphide γ-Ce that the red pigment of producing in order to make is used
2S
3Performance better, preferably with the sesquialter cerium sulphide γ-Ce for preparing
2S
3With pH7～9, the Neutral ammonium fluoride (NH of concentration 11～150 grams per liters
4F) aqueous solution stirred after 0.5～2 hour, washed with water 2～5 times, after the filtration, dried and obtained the wine-colored sesquialter cerium sulphide output of excellent property at 105～120 ℃.Used bath water is a distilled water, and deionized water also can be the ortho-water of sediment-free.When washing with water, its solid-to-liquid ratio is 1: 3.
Used equipment has the sulphur stove, is made up of resistance furnace (7) and the inner stainless steel boiler tube (8) of embedding, is putting dewatered industrial sulphur (9) in the boiler tube.
Rotary kiln is made up of the interior pipe alundum tube (4) of kiln (3) and kiln, and alundum tube links to each other with transmission apparatus, and rotating speed can be controlled, and product collector (6) links to each other with alundum tube banded stainless steel sleeve pipe (5).Product collector (6) and sleeve pipe are made by stainless steel, and the bottom of product collector (6) receives bag (12) with plastic cement and is communicated with, automatic feeder (1) with link to each other with the D mouth of alundum tube, surge tank (13) communicates with the D mouth, also links to each other with absorption cell (14).Surge tank (13) and absorption cell (14) are exhaust gas processing device, and absorption cell fills sodium hydroxide solution in (14).
Nitrogen or argon gas are divided into two-way after removing wherein detrimental impurity such as moisture by nitrogen (or argon) gas purifier (10), one the tunnel enters stainless steel boiler tube (8) in the sulphur stove through linking pipeline, enters alundum tube (4) in the rotary kiln through linking pipeline and stainless steel sleeve pipe (5) again; Another road enters plastic cement by pipeline by the f valve and receives bag (12), through product collector (6), enters the stainless steel sleeve pipe, alundum tube, and they drive away the air in the tightness system jointly.Hydrogen is removed wherein detrimental impurity such as moisture by hydrogen gas cleaner (11), through linking pipeline, enter the stainless steel boiler tube (8) in the sulphur stove, at a certain temperature with the stainless steel boiler tube in sulfur vapor reaction, form the mixed gas of hydrogen sulfide and hydrogen, enter alundum tube (4) by pipe connecting B and stainless steel sleeve pipe (5) from C, and block furnace charge is entered the alundum tube (4) by automatic feeder continuously from the D mouth, and along with the mixed gas of the rotation of alundum tube and hydrogen sulfide and hydrogen is reverse and go.When temperature is suitable chemical reaction will take place, generate γ-Ce
2S
3, sulfurous gas (SO
2) and water (H
2O) gas, product γ-Ce
2S
3Move forward continuously, the plastic cement that falls into the product collector below receives bag (12), contains sulfurous gas (SO
2) and water (H
2O) and still unreacted hydrogen sulfide (H
2S) and hydrogen (H
2) tail gas, by absorption cell (14), absorb SO in the tail gas by the aqueous sodium hydroxide solution in the absorption cell
2, H
2Obnoxious flavoures such as S, the hydrogen of remainder is lighted discharging at outlet A place.γ-Ce
2S
3Handle through ammonium fluoride aqueous solution, washing, oven dry obtain red pigment sesquialter cerium sulphide product later.
Receiving bag (12) bottom at plastic cement has outlet, and sealing at ordinary times is hedged off from the outer world, and also has vent valve g and intake valve f in addition.F links to each other with argon gas cleaner (10), and g links to each other with tail gas treatment device by pipeline.During discharging, tighten the middle part that plastic cement receives bag, open intake valve f and vent valve g, feed nitrogen or argon gas, drive away a spot of H in the bag
2S and hydrogen.Close bleed valve g then, open the products export that plastic cement receives bag, draw off product, discharging finishes, the sealing outlet, while breakdown vent valve g is after the air in the nitrogen of feeding or the argon gas expeling plastic cement reception bag, close intake valve f and vent valve g, the middle part of unclamping polythene bag restores to the original state.
It should be noted the entire equipment system should with isolate from outer air, adopt sealing-duct to connect between the equipment, the junction between alundum tube and stainless steel tube and stainless steel sleeve pipe and the product collector all seals with the soft graphite pad.
The method advantage of the sesquialter cerium sulphide that preparation red pigment of the present invention is used just is:
1. because preparation method of the present invention is a successive, overcome the shortcoming of the batch production method of prior art.The batch production method must cooling before product is come out of the stove, after coming out of the stove, heats up again after producing the air must at first drive away in the tightness system again, and the energy consumption height, production efficiency is low.And method of the present invention saved the cooling product and come out of the stove, and step such as intensification has reduced energy consumption again, has saved the time, has improved plant factor, and production efficiency improves greatly.
2. owing to of the rotation of block furnace charge along with pipe in the rotary kiln, constantly expose its different position, contact with hydrogen sulfide, more owing to added sulphur when the block furnace charge of preparation, under higher furnace temperature, sulphur evaporates, make block furnace charge form vesicular, strengthen the velocity of diffusion of hydrogen sulfide in block furnace charge, accelerated the speed of gas-solid reaction, helped the carrying out of gas-solid phase reaction.
3. because block furnace charge has good mobility, on the alundum tube inwall, do not produce furnace accretion.
(4) description of drawings
Fig. 1 prepares cerium sesqui sulfide used for red pigment equipment synoptic diagram continuously
Among Fig. 1,1 is automatic feeder, and 2 is block furnace charge, 3 is rotary kiln, and 4 is pipe alundum tube in the rotary kiln, and 5 is the stainless steel sleeve pipe, 6 is product collector, and 7 is resistance furnace, and 8 is the boiler tube of the stainless steel of sulphur stove, 9 is sulphur, and 10 is argon gas or nitrogen purge device, and 11 is hydrogen gas cleaner, 12 are plastic cement reception bag, 13 is surge tank, and 14 is absorption cell, and 15 is absorption agent
(5) embodiment
Below with embodiment the method for preparing cerium sesqui sulfide used for red pigment of the present invention is further described; to help manufacture method of the present invention is 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
Cerium dioxide with purity 99% is a raw material, is additive with the chemical pure anhydrous sodium carbonate, and the mol ratio of alkali metallic sodium/cerium is 0.25, and the mol ratio of sulphur/cerium is 1; With cerium dioxide and anhydrous sodium carbonate and sulphur ground and mixed evenly after, under 160 ℃ temperature dry 0.5 hour, be pressed into rectangular parallelepiped, 29 millimeters * 7 millimeters * 6 millimeters, density 2.2g/cm
3, form block furnace charge, standby.
8 kilograms of the industrial sulphurs of in the boiler tube of the stainless steel of sulphur stove, packing into and removing moisture content, argon gas (GB/T4842-1995, purity 〉=99.9%) purifies through CL-2 type regenerative purification for argon device, remove the detrimental impurity in the argon gas, by the boiler tube 8 of sulphur stove, the interior pipe alundum tube 4 that plastic cement receives bag 12, product collector 6, stainless steel sleeve pipe 5, rotary kiln, drive air 2 hours wherein continuously, the flow of argon gas is 0.04 cubic metre/hour; Continue to feed argon gas, make sulphur stove and rotary kiln begin to heat up, the speed that heats up is 10 ℃/minute, when the furnace temperature (temperature of stainless steel tube) of sulphur stove when reaching 300 ℃, switch to the hydrogen that purifies with CL-1 type regenerative hydrogen gas cleaner, through hydrogen gas cleaner purify the detrimental impurity remove in the hydrogen (purity of former hydrogen 〉=99%GB/T3634-1995), the flow of hydrogen be 25 liters/hour, gas is lighted discharging at outlet A place.When the temperature of sulphur stove rises to 360 ℃, the temperature constant temperature that makes the sulphur stove is at 360 ℃, rotary kiln continues to be warming up to 1125 ℃ (temperature of alundum tube), make it remain on 1125 ℃, regulating the interior pipe of rotary kiln and the angle theta of horizontal plane is 0.3 °, make the interior pipe opening for feed D place of rotary kiln be higher than the discharge port of pipe in it, interior pipe alundum tube in the rotary kiln rotates, the speed of its rotation is that 0.16r/min begins to enter block furnace charge, block furnace charge automatic feeder adds from opening for feed D, its feed rate is 100 Grams Per Hours, the bloomer material is stirring in alundum tube to the C mouth and is moving, in moving, react, block furnace charge was moved 90 minutes in 1125 ℃ of humidity provinces, generate γ-Ce with hydrogen sulfide
2S
3Shift out rotary kiln, enter product collector, regularly collect, product is through levigate, mix with the ammonium fluoride aqueous solution of concentration 100 grams per liters of pH8 stir 1 hour after, with deionized water wash 3 times, solid-to-liquid ratio is 1: 3 during washing, filters back oven dry under 150 ℃ temperature and obtains wine-colored sesquialter cerium sulphide γ-Ce
2S
3Product.Product tristimulus coordinates UV365 spectrophotometric determination, measuring condition D
65Light source, 10 ° of visual fields, o/d, measurement result: L*=37.38, a*=53.33, b*=41.50; Product granularity MK3 particle size analyzer determination, median size D
50=2.5 μ m.
Embodiment 2
Its working method and equipment are substantially with embodiment 1, only different is to substitute argon gas with nitrogen, with the chemical pure sodium sulphite anhydrous 99.3 is additive, the mol ratio of alkali metallic sodium/cerium is 0.20, the mol ratio of sulphur/cerium is 1.5, with cerium dioxide and sodium sulphite anhydrous 99.3 and sulphur ground and mixed evenly after, under 110 ℃ temperature dry 2 hours, be pressed into right cylinder.6 millimeters of cylindrical diameter of phi, high 5 millimeters, density 2.2g/cm
3Form the bloomer material, standby, the flow of hydrogen is 30 liters/hour, and the temperature constant temperature of sulphur stove is at 300 ℃, and the temperature of rotary kiln is controlled at 1400 ℃, regulating the interior pipe of rotary kiln and the angle theta of horizontal plane is 1 °, the speed of the rotation of alundum tube is 1.0r/min, and its feed rate is 200 Grams Per Hours, and block furnace charge was moved 30 minutes in 1400 ℃ humidity province.Product tristimulus coordinates: L*=39.66, a*=51.67, b*=44.21; Median size D
50=4.9 μ m.
Embodiment 3
Its working method and equipment is substantially with embodiment 1, and the mol ratio of only different is alkali metallic sodium/cerium is 0.5, and the mol ratio of sulphur/cerium is 3, and cerium dioxide and anhydrous sodium carbonate and sulphur ground and mixed is even, and is under 140 ℃ temperature dry 1.5 hours, standby.The flow of hydrogen is 20 liters/hour, the temperature constant temperature of sulphur stove is at 400 ℃, the temperature of rotary kiln is controlled at 1000 ℃, the angle theta of regulating rotary kiln and horizontal plane is 0.2 °, the speed of rotating is 0.5r/min, its feed rate is 50 Grams Per Hours, and block furnace charge was moved 30 minutes in 1000 ℃ temperature province.Product tristimulus coordinates: L*=36.09, a*=52.21, b*=36.93; Median size D
50=1.3 μ m.
Embodiment 4
Its working method and equipment are substantially with embodiment 1, and only different is not add sulphur when the block furnace charge of preparation.Product tristimulus coordinates: L*=37.11, a*=47.44, b*=38.71; Median size D
50=2.7 μ m.
Embodiment 5
Its working method and equipment are substantially with embodiment 1, and only different is to substitute cerium oxide with the Carbon Dioxide cerium, substitutes anhydrous sodium carbonate with Anhydrous potassium carbonate, and the mol ratio of basic metal potassium/cerium is 0.15, and the mol ratio of sulphur/cerium is 1.5.Product tristimulus coordinates: L*=37.55, a*=50.42, b*=39.39; Median size D
50=2.3 μ m.
Embodiment 6
Its working method and equipment is substantially with embodiment 1, and the mol ratio of only different is alkali metallic sodium/cerium is 0.3, and the mol ratio of sulphur/cerium is 3.Product tristimulus coordinates: L*=40.12, a*=52.75, b*=40.72; Median size D
50=2.0 μ m.
Embodiment 7
Cerium dioxide with purity 99% is a raw material, with the anhydrous sodium carbonate is additive, the mol ratio of alkali metallic sodium/cerium is 0.2, with cerium dioxide and anhydrous sodium carbonate ground and mixed evenly after, add the adhesive polyethylene alcohol solution, the concentration of polyvinyl alcohol water solution is 2.5% weight percentage, the add-on of polyvinyl alcohol water solution is that the weight ratio of the polyethylene aqueous solution/(cerium dioxide+anhydrous sodium carbonate) is 20: 100, mix and make particle, drying is 1.8 hours under 140 ℃ temperature, and it is standby to form the granular furnace charge of 20～40 orders.
8 kilograms of the industrial sulphurs of in the boiler tube of the stainless steel of sulphur stove, packing into and removing moisture content, technical pure nitrogen purifies through CL-2 type regenerative nitrogen purge device, remove the detrimental impurity in the nitrogen, nitrogen is by the boiler tube polythene bag of the stainless steel of sulphur stove, the product collector, the stainless steel sleeve pipe, the interior pipe alundum tube of rotary kiln is driven the air 2 hours in the reactive system continuously, the flow of nitrogen is 0.04 cubic metre/hour, sulphur stove and rotary kiln are heated up, the speed that heats up is 10 ℃/minute, when the furnace temperature (temperature of stainless steel tube) of sulphur stove when reaching 250 ℃, switch to CL-1 type regenerative hydrogen gas cleaner purified hydrogen (remove the impurity of dehydrogenation in going through hydrogen gas cleaner, the purity of former hydrogen 〉=99% meets the GB/T3634-1995 standard), the flow of hydrogen is 25 liters/hour, and gas is lighted discharging at outlet A place.When the temperature of sulphur stove is 320 ℃, the temperature constant temperature that makes the sulphur stove is at 320 ℃, make rotary kiln continue to be warming up to 1200 ℃ (temperature of alundum tube), and remain on 1200 ℃, the interior pipe of regulating rotary kiln is 0.5 ° with the angle theta of horizontal plane, makes the interior pipe opening for feed D place of rotary kiln be higher than the discharge port of its interior pipe, the interior pipe rotation of rotary kiln, the speed of its rotation is 0.8r/min, begin to enter block furnace charge, block furnace charge is added from opening for feed D by automatic feeder, and its feed rate is 90 Grams Per Hours, block furnace charge is stirring in alundum tube to the C place and is moving, in moving, react, block furnace charge was moved 60 minutes in 1200 ℃ temperature province, generate product and shift out rotary kiln with hydrogen sulfide, enter product collector, regularly collect product, product is through levigate, with pH8.5, the ammonium fluoride aqueous solution of concentration 130 grams per liters mixed stirring after 1.5 hours, with deionized water wash 3 times, solid-to-liquid ratio is 1: 3 during washing, after the filtration, under 120 ℃ temperature, dry, obtain wine-colored sesquialter cerium sulphide γ-Ce
2S
3Product, product colourity colour code measurement result is: L*=37.20, a*=49.50, b*=37.22; Product median size D
50=2.9 μ m.
Embodiment 8
Its working method and equipment is substantially with embodiment 7, the cerium dioxide CeO that only different is with purity 99%
2For raw material and anhydrous sodium carbonate are additive, the mol ratio of alkali metallic sodium/cerium is 0.3, and the mol ratio of sulphur/cerium is 1.5.With cerium dioxide and anhydrous sodium carbonate and sulphur ground and mixed evenly after, add the adhesive polyethylene alcohol solution, the concentration of polyvinyl alcohol water solution is 5% weight percentage, the add-on of polyvinyl alcohol water solution is that the weight ratio of polyvinyl alcohol water solution/(cerium dioxide+anhydrous sodium carbonate+sulphur) is 15: 100, after mixing, is pressed into right cylinder, its diameter is 10 millimeters, high 3 millimeters, drying is 1.2 hours under 160 ℃ temperature, and is standby.The temperature of rotary kiln is controlled at 1250 ℃, products C e
2S
3Tristimulus coordinates measurement result: L*=38.36, a*=47.19, b*=39.69; The product median size is D
50=3.4 μ m.
Embodiment 9
Its working method and equipment are substantially with embodiment 7, only different is with cerium dioxide and anhydrous sodium carbonate and sulphur ground and mixed evenly after, add the adhesive polyethylene alcohol solution, the concentration of polyvinyl alcohol water solution is 1% weight percentage, the add-on of polyvinyl alcohol water solution is that the weight ratio of polyvinyl alcohol water solution/(cerium dioxide+anhydrous sodium carbonate+sulphur) is 50: 100, after mixing, be pressed into right cylinder, its diameter is 10 millimeters, high 3 millimeters, drying is 1.2 hours under 160 ℃ temperature, and is standby.The temperature of rotary kiln is controlled at 1250 ℃.Product tristimulus coordinates: L*=35.97, a*=44.79, b*=36.54; Median size D
50=3.0 μ m.
Embodiment 10
Its working method and equipment are substantially with embodiment 7, only different is with cerium dioxide and anhydrous sodium carbonate and sulphur ground and mixed evenly after, add the adhesive polyethylene alcohol solution, the concentration of polyvinyl alcohol water solution is 7%, and the add-on of polyvinyl alcohol water solution is that the weight ratio of polyvinyl alcohol water solution/(cerium dioxide+anhydrous sodium carbonate+sulphur) is 25: 100, after mixing, be pressed into right cylinder, its diameter is 10 millimeters, and is high 3 millimeters, drying is 1.2 hours under 160 ℃ temperature, and is standby.The temperature of rotary kiln is controlled at 1250 ℃.Product tristimulus coordinates: L*=36.23, a*=45.17, b*=37.79; Median size D
50=3.5 μ m.
Embodiment 11
Its working method and equipment are substantially with embodiment 7, only different is with cerium dioxide and anhydrous sodium carbonate and sulphur ground and mixed evenly after, add the adhesive polyethylene alcohol solution, the concentration of polyvinyl alcohol water solution is 4%, and the add-on of polyvinyl alcohol water solution is that the weight ratio of polyvinyl alcohol water solution/(cerium dioxide+anhydrous sodium carbonate+sulphur) is 30: 100, after mixing, be pressed into right cylinder, its diameter is 10 millimeters, and is high 3 millimeters, drying is 1.2 hours under 160 ℃ temperature, and is standby.The temperature of rotary kiln is controlled at 1250 ℃.Product tristimulus coordinates: L*=37.46, a*=46.61, b*=38.31; Median size D
50=3.3 μ m.
Embodiment 12
Its working method and equipment are substantially with embodiment 7, only different is to add the adhesive polyethylene alcohol solution, the concentration of polyvinyl alcohol water solution is 2% weight percentage, and the add-on of polyvinyl alcohol water solution is that the weight percent of polyvinyl alcohol water solution/(cerium dioxide+anhydrous sodium carbonate) is 10: 100.Product tristimulus coordinates: L*=36.20, a*=48.27, b*=35.13; Median size D
50=2.7 μ m.
Embodiment 13
Its working method and equipment are substantially with embodiment 7, only different is to add the adhesive polyethylene alcohol solution, the concentration of polyvinyl alcohol water solution is 3% weight percentage, and the add-on of polyvinyl alcohol water solution is that the weight percent of polyvinyl alcohol water solution/(cerium dioxide+anhydrous sodium carbonate) is 30: 100.Product tristimulus coordinates: L*=35.71, a*=47.17, b*=36.21; Median size D
50=3.0 μ m.
Embodiment 14
Its working method and equipment is substantially with embodiment 1, and only different is, with cerous carbonate (rare earth oxide total content TREO 45%, wherein main component CeO
2/ TREO 〉=95%) replaces cerium dioxide.Product tristimulus coordinates: L*=34.51, a*=55.31, b*=39.25; Median size D
50=1.5 μ m.
Embodiment 15
Its working method and equipment is substantially with embodiment 1, and only different is, with Sedemesis (rare earth oxide total content TREO 42%, wherein main component CeO
2/ TREO 〉=90%) replaces cerium dioxide.Product tristimulus coordinates: L*=37.20, a*=57.00, b*=41.30; Median size D
50=3.2 μ m.
Claims (16)
1. method for preparing continuously cerium sesqui sulfide used for red pigment is characterized in that:
1) other compound with cerium dioxide or cerium is a raw material, alkaline carbonate or at least a alkali-metal other compound are additive, the mol ratio of basic metal/cerium is 0.05～0.5, other compound of said cerium comprises carbonate, acetate, oxalate, tartrate, malonate, the vitriol of cerium, said alkali-metal other compound comprises alkali-metal oxide compound, acetate, oxalate, sulfide, polysulfide, vitriol, sulphite
2) evenly make block furnace charge with other compound of raw material cerium dioxide or cerium and alkaline carbonate or at least a alkali-metal other compound are mixed,
3) interior pipe in the rotary kiln and horizontal plane have an angle theta, make the interior pipe opening for feed furnace charge plane of rotary kiln be higher than the discharge port furnace charge plane of pipe in it, place sulphur in the boiler tube of sulphur stove, interior pipe in the boiler tube of sulphur stove and the rotary kiln and gas piping constitute a closed system
4) drive air in the reactive system with nitrogen or argon gas, the gas flow direction is opposite with the direction of motion of furnace charge,
5) nitrogen or argon gas are switched to hydrogen, the interior pipe of rotary kiln rotates, and the temperature of the boiler tube of sulphur stove is controlled at 300～450 ℃, and the interior pipe temperature of rotary kiln is controlled at 800～1400 ℃,
6) the interior pipe opening for feed from rotary kiln adds furnace charge, and the traveling time of furnace charge in 800～1400 ℃ high-temperature area remained on more than 15 minutes,
7) product is collected from the rotary kiln discharge port, and with the product crushing grinding, and the process aftertreatment makes product.
2. according to a kind of continuous method for preparing cerium sesqui sulfide used for red pigment of claim 1, it is characterized in that: with other compound and the alkaline carbonate or the mixed furnace charge of evenly making of at least a alkali-metal other compound of cerium dioxide or cerium, drying, drying temperature are 100～160 ℃.
3. according to a kind of continuous method for preparing cerium sesqui sulfide used for red pigment of claim 1, it is characterized in that: the mol ratio of basic metal/cerium is 0.2～0.3.
4. according to a kind of continuous method for preparing cerium sesqui sulfide used for red pigment of claim 1, it is characterized in that: alkaline carbonate comprises anhydrous sodium carbonate; Alkali metal sulfite comprises sodium sulphite anhydrous 99.3.
5. according to a kind of continuous method for preparing cerium sesqui sulfide used for red pigment of claim 1, it is characterized in that: with other compound of cerium dioxide or cerium and alkaline carbonate or at least a alkali-metal other compound evenly after, add the adhesive polyethylene alcohol solution, mix, drying is made block furnace charge; The add-on of polyvinyl alcohol water solution is that the weight ratio of polyvinyl alcohol water solution/(other compound+alkaline carbonate of cerium dioxide or cerium or at least a alkali-metal other compound) is 5～40: 100, and the concentration of used polyvinyl alcohol water solution is weight percentage 1～10%.
6. according to a kind of continuous method for preparing cerium sesqui sulfide used for red pigment of claim 1, it is characterized in that: in other compound of cerium dioxide or cerium and alkaline carbonate or at least a alkali-metal other compound, add SULPHUR POWDER and mix, block furnace charge is made in hot briquetting, and the mol ratio of sulphur/cerium is more than 0.1.
7. according to a kind of continuous method for preparing cerium sesqui sulfide used for red pigment of claim 6, it is characterized in that: the mol ratio of sulphur/cerium is 1～1.5, and the temperature of heating is 120～160 ℃.
8. according to a kind of continuous method for preparing cerium sesqui sulfide used for red pigment of claim 5 and 6, it is characterized in that: block furnace charge can be wherein a kind of of cubes, rectangular parallelepiped, right cylinder, particulate state.
9. a kind of continuous method for preparing cerium sesqui sulfide used for red pigment according to Claim 8, it is characterized in that: one of method for making of granular block furnace charge is, with other compound of cerium dioxide or cerium and alkaline carbonate or at least a alkali-metal other compound evenly after, add the adhesive polyethylene alcohol solution, mix in 110～160 ℃ of dryings, sieve and make particulate state; The add-on of polyvinyl alcohol water solution is that the weight ratio of polyvinyl alcohol water solution/(other compound+alkaline carbonate of cerium dioxide or cerium or at least a alkali-metal other compound) is 5～40: 100, and the concentration of used polyvinyl alcohol water solution is weight percentage 1～10%.
10. a kind of continuous method for preparing cerium sesqui sulfide used for red pigment according to Claim 8, it is characterized in that: one of method for making of granular block furnace charge is, after other compound of cerium dioxide or cerium and alkaline carbonate or at least a alkali-metal other compound and SULPHUR POWDER mixed, add the adhesive polyethylene alcohol solution, mix in 110～160 ℃ of dryings, sieve and make particulate state; The add-on of polyvinyl alcohol water solution is that the weight ratio of polyvinyl alcohol water solution/(other compound+alkaline carbonate of cerium dioxide or cerium or at least a alkali-metal other compound+SULPHUR POWDER) is 0～40: 100, and the concentration of used polyvinyl alcohol water solution is weight percentage 1～10%.
11. a kind of continuous method for preparing cerium sesqui sulfide used for red pigment according to claim 9, it is characterized in that: the add-on of polyvinyl alcohol water solution is that the weight ratio of polyvinyl alcohol water solution/(cerium dioxide+alkaline carbonate or at least a alkali-metal other compound) is 10～15: 100, and the concentration of used polyvinyl alcohol water solution is weight percentage 2～5%.
12. a kind of continuous method for preparing cerium sesqui sulfide used for red pigment according to claim 10, it is characterized in that: the add-on of polyvinyl alcohol water solution is that the weight ratio of polyvinyl alcohol water solution/(other compound+alkaline carbonate of cerium dioxide or cerium or at least a alkali-metal other compound+SULPHUR POWDER) is 10～15: 100, and the concentration of used polyvinyl alcohol water solution is weight percentage 2～5%.
13. a kind of continuous method for preparing cerium sesqui sulfide used for red pigment according to claim 1 is characterized in that: the interior pipe in the rotary kiln and the angle of horizontal plane are 0.2～10 °.
14. a kind of continuous method for preparing cerium sesqui sulfide used for red pigment according to claim 1 is characterized in that: the furnace tube temperature of sulphur stove is controlled at 320～360 ℃.
15. a kind of continuous method for preparing cerium sesqui sulfide used for red pigment according to claim 1 is characterized in that: the interior pipe temperature of rotary kiln is controlled at 1100～1250 ℃.
16. a kind of continuous method for preparing cerium sesqui sulfide used for red pigment according to claim 1, it is characterized in that: said aftertreatment is with said product and pH7～9, the ammonium fluoride aqueous solution that concentration is 11～150/ liters mixed stirring after 0.5～2 hour, wash with water, filter 105～120 ℃ temperature oven dry.
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| CN102107902A (en) * | 2010-12-22 | 2011-06-29 | 包头市宏博特科技有限责任公司 | Method for preparing cerium sesquisulphide for red pigment by sulfur melting method |
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| CN104176762A (en) * | 2014-07-02 | 2014-12-03 | 北京理工大学 | Method for preparing light rare earth deuteride by high-temperature direct process |
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| CN102107902B (en) * | 2010-12-22 | 2012-09-26 | 包头市宏博特科技有限责任公司 | Method for preparing cerium sesquisulphide for red pigment by sulfur melting method |
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