CN1182060A - Preparation of stannic ceramic pigment - Google Patents
Preparation of stannic ceramic pigment Download PDFInfo
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- CN1182060A CN1182060A CN 97118393 CN97118393A CN1182060A CN 1182060 A CN1182060 A CN 1182060A CN 97118393 CN97118393 CN 97118393 CN 97118393 A CN97118393 A CN 97118393A CN 1182060 A CN1182060 A CN 1182060A
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Abstract
The present invention adopts direct acidolysis of metal tin and calcium carbonate, sealed calcination in electric kiln, oxygen source make-up during calcination and prevention of metal vapour volatilization so as to raise pigment quality and lower cost greatly. The present invention can design stannic pigment precicely based on proportioning principle, and it is suitable for ceramic pigment producers and tin smilting enterprises.
Description
The present invention relates to ceramic stain, particularly a kind of stannic ceramic pigment and preparation method thereof.
Existing tin series ceramic pigment preparation method, wide selection tindioxide, lime carbonate, quartz, heavy complex acid potassium, ferric oxide, weisspiessglanz, manganese oxide, cupric oxide, titanium oxide, Vanadium Pentoxide in FLAKES, cobalt oxide, borax are raw material, with kiln is main preparation means, as " pottery " 1994 the 4th phases report " research and the application of agate red pyroceramic toner ", because the technical pure tindioxide of selecting for use generally is to use nitrate method production, can produce the tindioxide coarse-grain of some amount.In addition, existing manufacturing technique is main preparation means with kiln, and fuel, kiln utilization ratio are low, and open calcining pattern can make the volatilization of pigment composition, thereby change the pigment composition, influence quality product, and the increase cost.
The object of the invention provides a kind of select for use metallic tin and the direct acidolysis of lime carbonate, makes the method for stannic ceramic pigment.Adopt sealing method burning ceramics toner, the volatilization of pigment composition is reduced, the toner quality improves, and reduces the cost.
The objective of the invention is to reach by following approach
1, adds acidifying dissolving in the reactor and make tin protochloride, calcium chloride with metallic tin, lime carbonate and hydrochloric acid.
2, with stannous chloride solution and calcium chloride solution or (with) sodium silicate aqueous solution mixing coprecipitation crystallization synthesizes the colour generation carrier.
3, calcium hydroxide is made emulsion dispersion in boric acid aqueous solution, produce the coprecipitation crystallization, make mineralizer.
4, the pigment photoghraphic coupler is synthetic with one or more neutralization reactions or reduction among sodium antimonate, ferrous sulfate, copper sulfate, titanyl sulfate, rose vitriol, Manganous chloride tetrahydrate, sodium metavanadate, the heavy complex acid potassium.
5, above-mentioned 2,3,4 three step reaction terminal point PH=7-9 mix them, get the pigment base-material.
6, the pigment base-material is adorned close through washing, dehydration, ageing mixture, extrusion moulding, flat sign indicating number.
7, calcining kiln seals fully, the highest calcining temperature is 1150 ℃-1350 ℃, calcination time 240-480 minute, temperature-controlled process is that full stroke uniform heats up, and is lower than 50 ° of high fever calcining temperatures and each constant temperature 30 public clock of the highest calcining temperature, and calcining terminal point oxygen source keeps malleation, calcinate is through being crushed to 600 orders, use water rinse, the dehydration dry by the fire in, promptly get product.
Furtherly, the object of the invention can also reach by following approach:
1, be the colour generation carrier with metallic tin 0.26-0.63, lime carbonate 0-0.6, water glass 0-0.6 mol ratio prescription.
2, be mineralizer with boron trioxide 0-0.02, calcium hydroxide 0-0.02 mol ratio prescription.
For preparing different stannic ceramic pigments, can realize by the following method again:
1, tin network red ceramic pigment: with metallic tin 0.25-0.32, lime carbonate 0.28-0.35, water glass 0.26-0.5, mineralizer 0-0.02, potassium bichromate 0.001-0.02 mol ratio is prescription, 1180 ℃-1280 ℃ of the highest calcining temperatures, calcination time 360-420 minute.
2, standard cubic feet per day white pottery porcelain pigment: with metallic tin 0.4-0.55, lime carbonate 0.4-0.55, water glass 0-0.4, mineralizer 0-0.02 mol ratio is prescription, 1250 ℃-1350 ℃ of the highest calcining temperatures, calcination time 360-420 minute.
3, tin titan yellow ceramic stain: with metallic tin 0.4-0.55, lime carbonate 0.04-0.05, titanyl sulfate 0.015-0.02, mineralizer 0-0.02, mol ratio is prescription, 1200 ℃-1300 ℃ of the highest calcining temperatures, calcination time 330-380 minute.
4, tin antimony ash ceramic stain: with metallic tin 0.5-0.63, water glass 0-0.4, metaantimmonic acid receive 0.01-0.015 mineralizer 0-0.02, and mol ratio is prescription.1150 ℃-1250 ℃ of the highest calcining temperatures, calcination time 330-360 minute.
5, the green ceramic stain of tin ash: with metallic tin 0.5-0.63, the violent 0.05-0.06 of chlorination, ferrous sulfate 0.015-0.02, copper sulfate 0.015-0.02, rose vitriol 0.004-0.005, water glass 0-0.4, mineralizer 0-0.02 mol ratio is prescription, 1230 ℃-280 ℃ of the highest calcining temperatures, calcination time 330-360 minute.
6, tin cobalt blue ceramic stain: with metallic tin 0.25-0.32, water glass 0.26-0.5, rose vitriol 0.03-0.05, mineralizer 0-0.02 mol ratio is prescription, 1200 ℃-1250 ℃ of the highest calcining temperatures, calcination time 330-360 minute.
7, tin cobalt violet ceramic stain: with metallic tin 0.5-0.6, potassium bichromate 0.005-0.009, rose vitriol 0.01-0.015, mineralizer 0-0.02, water glass 0-0.4 mol ratio is prescription, 1250 ℃-1280 ℃ of the highest calcining temperatures, calcination time 330-380 minute
The present invention selects for use metallic tin and the direct acidolysis of lime carbonate to handle, realize the uniform mixing of molecular level, generation has the calcium stannate crystal that the high degree of dispersion ultra-fine grain is formed, 70% left and right sides ideal calcium stannate crystal is arranged in the toner prescription, add the tinting material of coprecipitation, mineralizer and about 25% very stable SiO
2So, can guarantee the quality and the quantity of colour generation carrier in the toner prescription.Existing pigment preparation method extensive technology on raw material is changed into fine chemistry industry.Can use the tone of formulation principle design stannic ceramic pigment exactly.The present invention adopts sealing method burning ceramics toner, replenishes oxygen source in calcination process, and the volatilization of metal vapors is controlled to bottom line, and making sign indicating number is that the ceramic stain quality significantly improves, and cost decreases.Under the equal in quality condition, the inventive method can reduce in the prescription tindioxide absolute content more than 10%.
Below in conjunction with embodiment to the inventive method example 1 that elaborates:
Pour into 368 kilograms of fusions of heating of No. three metal tin slabs and to swash into tin flower in the cold water, again will (472 kilogram 31% hydrochloric acid adds in the reactor and carries out acidolysis, and tin adds 350 kilograms of limestone powders after spending whole dissolvings, and limestone powder all dissolves the back clarification filtration.The saturated aqueous solution that adds 100 liter of 8 degree Beaume sodium chloride aqueous solution of 30 kilogram weight potassiumchromate saturated aqueous solutions adding and 1010 kilograms of SODIUM METASILICATE PENTAHYDRATE preparations again reacts.Reaction end PH=9.Add 60 kilograms of mineralizers at last, the mixing post precipitation with centrifuge dewatering, ageing mixture, extrusion molding, setting, send the Sealing furnace oxidizing roasting.20 ℃, 1: 55 ℃ 360 public clock of temperature-controlled process at the uniform velocity heats up, and 1215 ℃ are incubated 30 minutes, and 1265 ℃ are incubated 30 minutes.Cooling back is broken into less than 200 purpose powders with Universalpulverizer, reenter sand mill and be milled to 600 order dischargings, with centrifuge dewatering, washing, drying, at last with drier to moisture less than 1%.Test package promptly makes tin chrome red pottery toner example 2:
Heat for 368 kilograms to dissolve to pour into No. three metal tin slabs and swash into the tin flower in the cold water, hydrochloric acid that again will 1472 kilogram 31% adds in the reactor carry out acidolysis, and tin adds 330 kilograms of limestone powders after spending whole dissolvings, and limestone powder all dissolves the back clarification filtration.Add volatile salt saturated aqueous solution, reaction end PH=9.Add 60 kilograms of mineralizers again, the mixing post precipitation with centrifuge dewatering, ageing mixture, moulding, setting, send the Sealing furnace oxidizing roasting.Temperature-controlled process: 20 ℃-1350 ℃ at the uniform velocity intensifications in 480 minutes.1300 ℃ are incubated 30 minutes, and 1350 ℃ are incubated 30 minutes.Cooling back is broken into less than 200 purpose powders with Universalpulverizer, reenter sand mill and be milled to 600 order dischargings, with centrifuge dewatering, washing, drying, at last with drier to moisture content less than 1%.Test package promptly makes standard cubic feet per day white pottery porcelain toner.Example 3:
Heat for 368 kilograms to dissolve to pour into No. three metal tin slabs and swash into the tin flower in the cold water, hydrochloric acid that again will 700 kilogram 31% adds in the reactor carry out acidolysis, and tin is spent clarification filtration after whole dissolvings.Add 30 liter of 8 degree Beaume sodium chloride aqueous solution, the saturated aqueous solution of 380 kilograms of SODIUM METASILICATE PENTAHYDRATE preparations reacts.Reaction end PH=9.Do not reach the adjustment of available volatile salt saturated aqueous solution.Add the saturated aqueous solution of 30 kilograms of titanyl sulfates preparation, saturated aqueous solution, 60 kilograms of mineralizers of 40 kilograms of ammonium meta-vanadate preparations again, the mixing post precipitation with centrifuge dewatering, ageing mixture, extrusion molding, setting, send the Sealing furnace oxidizing roasting.Temperature-controlled process: 20 ℃ of-1265 ℃ of 360 public clocks at the uniform velocity heat up, and 1215 ℃ are incubated 30 minutes, and 1265 ℃ are incubated 30 minutes.The cooling back is broken into less than 200 purpose powders with Universalpulverizer, reenters sand mill and is milled to 600 order dischargings, with centrifuge dewatering, washing, drying.At last with drier to moisture content less than 1%.Test package promptly makes tin titan yellow pottery toner.Example 4:
Heat for 368 kilograms to dissolve to pour into No. three metal tin slabs and swash into the tin flower in the cold water, to carry out acidolysis in 700 kilogram 31% the hydrochloric acid adding reactor again, tin adds the saturated aqueous solution that 30 kilograms of sodium antimonates are prepared after spending whole dissolvings, adds volatile salt saturated aqueous solution precipitation behind the clarification filtration again.Reaction end PH=9.Add 60 kilograms of mineralizers at last, the mixing post precipitation with centrifuge dewatering, ageing mixture, moulding, setting, send the Sealing furnace oxidizing roasting.Temperature-controlled process: 20 ℃-1250 ℃ at the uniform velocity intensifications in 360 minutes, 1200 ℃ are incubated 30 minutes, and 1250 ℃ are incubated 30 minutes.Cooling back is broken into less than 200 purpose powders with Universalpulverizer, reenter sand mill and be milled to 600 order dischargings, with centrifuge dewatering, washing, drying, at last with drier to moisture content less than 1%.Test package promptly makes tin antimony ash pottery toner.Example 5:
Heat for 368 kilograms to dissolve to pour into No. three metal tin slabs and swash into the tin flower in the cold water, to carry out acidolysis in 700 kilogram 31% the hydrochloric acid adding reactor again, tin adds the saturated aqueous solution of the saturated aqueous solution of the saturated aqueous solution of 30 kilograms of sodium antimonate preparations, 30 kilograms of copper sulfate preparations, 10 kilograms of rose vitriol preparations, saturated aqueous solution, the clarification filtration of 50 kilograms of Manganous chloride tetrahydrate preparations after spending whole dissolvings, adds volatile salt saturated aqueous solution precipitation again.Reaction end PH=9.Add 60 kilograms of mineralizers at last, the mixing post precipitation with centrifuge dewatering, ageing mixture, extrusion molding, setting, send the Sealing furnace oxidizing roasting.20 ℃-1265 ℃ at the uniform velocity intensifications in 360 minutes of temperature-controlled process, 1215 ℃ are incubated 30 minutes, and 1265 ℃ are incubated 30 minutes.The cooling back is broken into less than 200 purpose powders with Universalpulverizer, reenters sand mill and is milled to 600 order dischargings, with centrifuge dewatering, washing, drying.At last with drier to moisture content less than 1%.Test package promptly makes the green ceramic toner of tin ash.Example 6:
Heat for 368 kilograms to dissolve to pour into No. three metal tin slabs and swash into the tin flower in the cold water, hydrochloric acid that again will 700 kilogram 31% adds in the reactor carry out acidolysis, and tin is spent clarification filtration after whole dissolvings.Add 150 liter of 8 degree Beaume sodium chloride aqueous solution, the saturated aqueous solution of 1500 kilograms of SODIUM METASILICATE PENTAHYDRATE preparations reacts.Reaction end PH=9.Do not reach the adjustment of usable acid solution.Saturated aqueous solution, 60 kilograms of mineralizers of adding the preparation of 60 kilograms of rose vitriols again, mixing post precipitation with centrifuge dewatering, ageing mixture, moulding, setting, send the Sealing furnace oxidizing roasting.Temperature-controlled process: 20 ℃ of-1250 ℃ of 360 public clocks at the uniform velocity heat up, and 1200 ℃ are incubated 30 minutes, and 1250 ℃ are incubated 30 minutes.The cooling back is broken into less than 200 purpose powders with Universalpulverizer, reenters sand mill and is milled to 600 order dischargings, with centrifuge dewatering, washing, drying.At last with drier to moisture content less than 1%.Test package promptly makes tin titanium cobalt blue pottery toner.Example 7:
Heat for 368 kilograms to dissolve to pour into No. three metal tin slabs and swash into the tin flower in the cold water, hydrochloric acid that again will 700 kilogram 31% adds in the reactor carry out acidolysis, and tin is spent the saturated aqueous solution clarification filtration that adds the preparation of 7 kilogram weight potassiumchromates after whole dissolvings.Add volatile salt saturated aqueous solution precipitation again.Reaction end PH=9.The saturated aqueous solution that adds the preparation of 20 kilograms of rose vitriols again, 60 kilograms of mineralizers, mixing post precipitation with centrifuge dewatering, ageing mixture, moulding, setting, send the Sealing furnace oxidizing roasting.Temperature-controlled process: 20 ℃-1265 ℃ at the uniform velocity intensifications in 360 minutes, 1215 ℃ are incubated 30 minutes, and 1265 ℃ are incubated 30 minutes.The cooling back is broken into less than 200 purpose powders with Universalpulverizer, reenters sand mill and is milled to 600 order dischargings, with centrifuge dewatering, washing, drying.At last with drier to moisture content less than 1%.Test package promptly makes tin cobalt violet pottery toner.
Claims (9)
1, a kind of method of making tin series ceramic pigment is characterized in that:
A, add in the reactor acidifying dissolving and make tin protochloride, calcium chloride with metallic tin, lime carbonate and hydrochloric acid.
B, with stannous chloride solution and calcium chloride solution or (with) sodium silicate aqueous solution mixing coprecipitation crystallization synthesizes the colour generation carrier.
C, calcium hydroxide is made emulsion dispersion in boric acid aqueous solution, produce the coprecipitation crystallization, make mineralizer.
D, pigment photoghraphic coupler are synthetic with one or more neutralizations or reduction reaction among sodium antimonate, ferrous sulfate, copper sulfate, titanyl sulfate, rose vitriol, Manganous chloride tetrahydrate sodium metavanadate, the heavy complex acid potassium.
E, above-mentioned a, b, c three step reaction terminal point PH=7-9 mix them, get the pigment base-material.
F, pigment base-material are through washing, dehydration, ageing mixture, moulding, the loading of kiln of flat sign indicating number.
G, calcining kiln seal fully, the calcining top temperature is 1150 ℃-1350 ℃, calcination time 240-480 minute, temperature-controlled process is that full stroke uniform heats up, and is lower than 50 ° of high fever calcining temperatures and each constant temperature 30 public clock of the highest calcining temperature, and calcining terminal point oxygen source keeps malleation, calcinate is through being crushed to 600 orders, use water rinse, dewatered drying promptly gets product.
2, according to the described method of claim 1, it is characterized in that
A, be the colour generation carrier with metallic tin 0.26-0.63, lime carbonate 0-0.6, water glass 0-0.6 mol ratio prescription.
B, with boron trioxide 0-0.02, calcium hydroxide 0-0.02 mol ratio prescription is a mineralizer.
3, according to claim 1 or 2 described methods, it is characterized in that
With metallic tin 0.25-0.32, lime carbonate 0.28-0.35, water glass 0.26-0.5, mineralizer 0-0.02, potassium bichromate 0.001-0.02 mol ratio is prescription, 1180 ℃-1280 ℃ of the highest calcining temperatures, calcination time 360-420 minute.
4, according to claim 1 or 2 described methods, it is characterized in that
With metallic tin 0.4-0.55, lime carbonate 0.5-0.55, water glass 0-0.4, mineralizer 0-0.02 mol ratio is prescription, 1250 ℃-1350 ℃ of the highest calcining temperatures, calcination time 360-420 minute.
5, according to claim 1 or 2 described methods, it is characterized in that
With metallic tin 0.4-0.55, lime carbonate 0.04-0.05, titanyl sulfate 0.015-0.02, mineralizer 0-0.02 mol ratio is prescription, 1200 ℃-1300 ℃ of the highest calcining temperatures, calcination time 330-380 minute.
6, according to claim 1 or 2 described methods, it is characterized in that:
With metallic tin 0.5-0.63, water glass 0.04, metaantimmonic acid are received 0.01-0.015 mineralizer 0-0.02 mol ratio for filling a prescription 1150 ℃-1850 ℃ of the highest calcining temperatures, calcination time 330-360 minute.
7, according to claim 1 or 2 described methods, it is characterized in that:
With metallic tin 0.5-0.63, Manganous chloride tetrahydrate 0.05-0.06, ferrous sulfate 0.015-0.02, copper sulfate 0.015-0.025, rose vitriol 0.004-0.005, water glass 0-0.4, mineralizer 0-0.02 mol ratio is prescription, 1230 ℃-1280 ℃ of the highest calcining temperatures, calcination time 330-360 minute.
8, according to claim 1 or 2 described methods, it is characterized in that:
With metallic tin 0.25-0.32, water glass 0.26-0.5, rose vitriol 0.03-0.05, mineralizer 0-0.02 mol ratio is prescription, 1200 ℃-1250 ℃ of the highest calcining temperatures, calcination time 330-360 minute.
9, according to claim 1 or 2 described methods.It is characterized in that:
With metallic tin 0.55-0.6, potassium bichromate 0.005-0.009, rose vitriol 0.01-0.015, water glass 0-0.4, mineralizer 0-0.02 mol ratio is 1250 ℃-1280 ℃ of prescription, the highest calcining temperatures, calcination time 330-380 minute.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97118393A CN1067964C (en) | 1997-10-28 | 1997-10-28 | Preparation of stannic ceramic pigment |
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| Application Number | Priority Date | Filing Date | Title |
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| CN97118393A CN1067964C (en) | 1997-10-28 | 1997-10-28 | Preparation of stannic ceramic pigment |
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| CN1182060A true CN1182060A (en) | 1998-05-20 |
| CN1067964C CN1067964C (en) | 2001-07-04 |
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| CN97118393A Expired - Fee Related CN1067964C (en) | 1997-10-28 | 1997-10-28 | Preparation of stannic ceramic pigment |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503221A (en) * | 2018-04-20 | 2018-09-07 | 攀枝花学院 | Frit for porcelain enamel, enamel layer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100442A (en) * | 1986-01-24 | 1987-08-12 | 国家建筑材料工业局山东工业陶瓷研究设计院 | Red ceramic paint of zirconium and silver |
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1997
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503221A (en) * | 2018-04-20 | 2018-09-07 | 攀枝花学院 | Frit for porcelain enamel, enamel layer and preparation method thereof |
| CN108503221B (en) * | 2018-04-20 | 2021-07-27 | 攀枝花学院 | Enamel glaze, enamel glaze layer and preparation method thereof |
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| Publication number | Publication date |
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| CN1067964C (en) | 2001-07-04 |
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