CN1408676A - Process for producing tin base ceramic pigment - Google Patents
Process for producing tin base ceramic pigment Download PDFInfo
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- CN1408676A CN1408676A CN 01133266 CN01133266A CN1408676A CN 1408676 A CN1408676 A CN 1408676A CN 01133266 CN01133266 CN 01133266 CN 01133266 A CN01133266 A CN 01133266A CN 1408676 A CN1408676 A CN 1408676A
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Abstract
The present invention is production process of tin base ceramic pigment and features use of metal tin, instead of tin dioxide in producing tin base ceramic pigment. The technological process includes melting metal tin and slagging, calcination to synthesize, crushing calcinated matter, rinsing, drying and other steps. The product is chrome-tin red ceramic pigments. The production process has the features of short process, low cost, no environmental pollution, etc.
Description
The invention relates to a method for manufacturing a tin-based ceramic pigment, in particular to a method for manufacturing a chrome-tin red series ceramic pigment.
Ceramic pigment refers to a material used for decorating and coloring ceramic products, and is prepared from pure non-metal oxide (such as SiO)2CaO) and some metal oxides are calcined at high temperature to form stable compound, the finished product is powder, when it is used, it is added into the correspondent basic glaze (liquid state) prepared in advance, and is ground and regulated to obtain glaze slip, then the glaze slip is sprayed on the surface of porcelain blank, and after high-temperature calcination (glazing) the ceramic product can be made into stable colour. The ceramic pigments are classified into tin-based and zirconium-based series according to the types of metal oxides used, and each series is classified into a plurality of colors according to the color of the pigments.
The tin-based ceramic pigment is a series of dozens of materials, such as garden red, agate red, wine red, pepper red, rose red, chestnut red, date red, antimony gray, seawater blue, vanadium tin yellow and the like. The tin-based ceramic pigment can present various colors, the elegant color is popular with people, the color is easy to control in the glazing process, the color generation capability is strong, the color generation is uniform and stable, and the tin-based ceramic pigment is nontoxic, particularly since the eighties of the twentieth century, some calcining equipment which takes natural gas, liquefied petroleum gas and electric energy as fuel energy and can strictly control the atmosphere in a furnace can be widely applied, and the application of the tin-based ceramic pigment is rapidly developed, so that the tin-based ceramic pigment is widely applied to decoration and coloring of various ceramic products, particularly high-medium-grade ceramic products (such as sanitary wares, high-grade wall and floor tiles and the like) despite the high price, becomes one of the more beautiful ceramic pigments in the building and sanitary ceramic markets in recent years, and the research on the tin-based ceramic pigment is extremely active.
The production of tin-based ceramic pigment has been in the history of more than half a century, and many manufacturers exist, the production method is mainly a solid-phase synthesis method, and although wet methods such as chemical coprecipitation and sol-gel method are researched, no industrial production application is reported. At present, the domestic production adopts the traditional solid phase two-step synthesis methodThe process comprises preparing tin dioxide from metallic tin, mixing tin dioxide with quartz powder, light calcium carbonate and colorant, grinding, calcining, grinding, washing and drying. During the preparation process of the wet tin dioxide, NO and NO are inevitably generated2Although the gas and the acid-containing waste gas are treated by measures, the gas and the acid-containing waste gas still cause pollution to the environment, so that the traditional process formanufacturing the tin-based ceramic color has a series of problems of long flow, serious pollution, large tin loss, high cost and the like, and restricts the application and development of the tin-based ceramic color to a certain extent.
After the coloring mechanism of tin-base ceramic pigment is researched, the method for preparing the tin-base ceramic pigment in one step is provided according to the physicochemical properties of metallic tin and oxides thereof, namely, metallic tin is directly melted and oxidized with quartz powder and light calcium carbonate to prepare the ceramic pigment without preparing acid-method tin dioxide by a nitric acid method.
The invention aims to provide a manufacturing method for directly producing a tin-based ceramic pigment by using metal tin to replace tin dioxide, which has simple process and low cost.
The basis for producing the tin-based ceramic pigment by replacing tin dioxide with metallic tin provided by the invention is as follows: the metal is kept stable in the air at normal temperature, and the metal tin and the oxygen in the air generate oxidation reaction at the temperature of more than 150 ℃ to generate SnO and SnO2. The main chemical reactions are:
under certain conditions, metallic tin can be converted into tin dioxide to meet the requirement of firing tin-based ceramic pigments.
The process conditions of the manufacturing method provided by the invention are as follows:
1. melting and slagging of metallic tin: adding the metal tin, the fluxing agent and the mineralizer into a reaction pot according to a certain proportion, continuously stirring and grinding at the temperature of 400-800 ℃, starting to perform an oxidation reaction when the metal tin is heated to 150 ℃, accelerating the oxidation reaction of the metal tin along with the increase of the temperature, and increasing the conversion rate of the tin dioxide.
2. Mixing, moistening and grinding: and (3) screening the melted and slagging material, separating a small amount of unreacted metallic tin, returning the separated metallic tin to the ingredient, adding the material meeting the requirement into a mill, further mixing and carrying out wet milling on the material, the colorant and the additive to uniformly mix the components and achieve the granularity required by the firing condition.
3. Calcining and synthesizing: drying the wet-milled materials, then feeding the materials into a calcining synthesis process, carrying out high-temperature heat treatment on the pigment ingredients, carrying out a series of chemical reactions at high temperature, and finally preparing the colored artificial minerals meeting the requirements. Calcining synthesis conditions: the sintering temperature is 1200-1300 ℃, the temperature rise time is 5-7 hours, the constant temperature time is 2-3 hours, the discharging temperature is 550 ℃, and the oxidizing atmosphere is controlled by calcination synthesis.
4. Crushing, rinsing and drying the fired product: and crushing the fired material by wet-type wet grinding until the granularity reaches 0.5-30 mu m, washing away unreacted residues by water, and drying and screening the washed pigment to obtain the product.
Compared with the prior art, the invention has the following advantages:
1. the metallic tin is used asthe raw material to fire the tin-based ceramic pigment, the process is short, and a series of environmental pollution problems caused in the production process of tin dioxide are avoided.
2. And the process is short, so that the loss of tin is reduced, and the production cost is reduced.
The manufacturing method provided by the invention can be used for firing ceramic pigment by using by-products such as tin refining slag, oxidation slag generated in the processing process of tin materials and the like besides metal tin.
The invention is further illustrated by the following examples:
example 1
Mixing and heating metal tin, calcium carbonate and quartz sand according to the ratio of 29: 34: 27 to 800 ℃, continuously stirring and grinding for 1-2 hours, cooling and sieving, returning the metal tin reacted on the sieve to the ingredients, grinding the sieved substances, adding the oxide of colorant chromium and additive according to the proportion, adding a proper amount of water, mixing and grinding for 1-12 hours, discharging, drying and then putting into a calcining furnace, calcining for 1-3 hours at the temperature of 1200-1300 ℃, cooling the sintered substances, then grinding for 1-2 hours, washing the product for 2-5 times by water, drying and sieving to obtain the product of the garden red with the granularity of 74 mu m.
Example 2
Mixing and heating metal tin, calcium carbonate and quartz sand according to the ratio of 40: 30: 28 to 800 ℃, continuously stirring and grinding for 1-2 hours, cooling and sieving, returning the metal tin reacted on the oversize material to the ingredients, grinding the undersize material, adding a colorant chromium oxide or chromium salt and an additive according to the proportion, adding a proper amount of water, mixing and grinding for 1-12 hours, discharging, drying and then putting into a calcining furnace, calcining for 1-3 hours at the temperature of 1200-1300 ℃, cooling the calcined material and then grinding for 1-2 hours, washing the product for 2-5 times with water, drying and sieving to obtain the agate product with the particle size of 74 mu m.
Claims (3)
1. A process for preparing the pigment of Cr-Sn-red ceramic includes such steps as smelting tin, oxidizing for slagging, adding pigment, mixing, grinding, breaking, rinsing, drying and sieving.
2. The method for producing a tin-based ceramic colorant as claimed in claim 1, wherein the temperature for melting, oxidizing and slagging of metallic tin is 400-800 ℃.
3. The method for producing a tin-based ceramic coloring material as defined in claim 1, wherein the pigment material is subjected to a high-temperature heat treatment at a calcination synthesis temperature of 1200-1300 ℃ for a calcination time of 1-3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011332662A CN1164520C (en) | 2001-09-19 | 2001-09-19 | Process for producing tin base ceramic pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011332662A CN1164520C (en) | 2001-09-19 | 2001-09-19 | Process for producing tin base ceramic pigment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1408676A true CN1408676A (en) | 2003-04-09 |
| CN1164520C CN1164520C (en) | 2004-09-01 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011332662A Expired - Fee Related CN1164520C (en) | 2001-09-19 | 2001-09-19 | Process for producing tin base ceramic pigment |
Country Status (1)
| Country | Link |
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| CN (1) | CN1164520C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424040C (en) * | 2007-02-05 | 2008-10-08 | 桂林工学院 | Process of preparing chromium doping tin sphene type coloring material |
| CN102775191A (en) * | 2012-07-06 | 2012-11-14 | 佛山市南海万兴材料科技有限公司 | Seed crystal introduced chromium tin pink ceramic pigment and preparation method thereof |
| CN104529536A (en) * | 2014-12-20 | 2015-04-22 | 佛山铭乾科技有限公司 | Tin-based ceramic pigment and preparation method thereof |
-
2001
- 2001-09-19 CN CNB011332662A patent/CN1164520C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424040C (en) * | 2007-02-05 | 2008-10-08 | 桂林工学院 | Process of preparing chromium doping tin sphene type coloring material |
| CN102775191A (en) * | 2012-07-06 | 2012-11-14 | 佛山市南海万兴材料科技有限公司 | Seed crystal introduced chromium tin pink ceramic pigment and preparation method thereof |
| CN104529536A (en) * | 2014-12-20 | 2015-04-22 | 佛山铭乾科技有限公司 | Tin-based ceramic pigment and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1164520C (en) | 2004-09-01 |
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