CN101723459A - Method for manufacturing ceramic pigment chrome green from waste materials of chromium salt factory - Google Patents
Method for manufacturing ceramic pigment chrome green from waste materials of chromium salt factory Download PDFInfo
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- CN101723459A CN101723459A CN200810230600A CN200810230600A CN101723459A CN 101723459 A CN101723459 A CN 101723459A CN 200810230600 A CN200810230600 A CN 200810230600A CN 200810230600 A CN200810230600 A CN 200810230600A CN 101723459 A CN101723459 A CN 101723459A
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Abstract
The invention discloses a method for manufacturing a ceramic pigment chrome green from waste materials of a chromium salt factory, which comprises the following steps: taking rejected materials, namely acid sludge and waste acid water, of the chromium salt factory as raw materials, adding sodium carbonate and water into a reactor with a stirrer, adding the waste material, namely the acid sludge, of the chromium salt factory into the reactor after the sodium carbonate is completely dissolved to perform reaction, adding the waste acid water of the chromium salt factory after the reaction is completed, adjusting the pH value of the reaction solution, adding an industrial glucose or a sodium sulphite to perform reaction, standing and depositing the reaction result to obtain a clear liquid after reaction, adding an ammonia into the clear liquid, controlling the pH value to between 8 and 10, stopping adding the ammonia, and performing filter pressing and washing on the obtained solution to obtain a filter cake; and sequentially baking and cooling the filter cake, crushing the filter cake into powder, and thus obtaining the product, namely the chrome green. The method for manufacturing the ceramic pigment chrome green of the invention has the advantages of simple operation and low cost; the obtained product has a relatively strong tinting strength and can meet industrial requirements; and the method solves the problem of pollution of waste materials of the chromium salt factory, really realizes changing waste materials into things of value and has obvious economic and social benefits.
Description
One, technical field:
The present invention relates to a kind of production method of beramic color, particularly relate to a kind of method of utilizing waste materials of chromium salt factory to produce the beramic color chrome green.
Two, background technology:
In the media such as beramic color is generally water insoluble, oily, solvent and resin, can be scattered in the various media, it has opacifying power, tinting strength, and is relatively stable to light, being to be used for the painted material of decorating ceramic products, generally is by purified nonmetal oxide (as: SiO
2, CaO) with some metal oxide (as: Fe
2O
3) material that forms through high-temperature calcination.Beramic color is generally powdery, during use it is added in the good corresponding parent glaze of configured in advance and grinds, adjusts, and makes glaze slip, glaze slip is sprayed to porcelain base surface again, makes ceramic become stable color after high-temperature calcination.Kind according to nonmetal oxide that uses and metal oxide is different, and beramic color has different types of series, for example: Yellow series, red series, brown series, green-series, purple series, grey color system, black series or the like.
At present, the traditional technology of the general employing of the preparation of beramic color is about to each coloring oxide and silicate oxide (as: aluminum oxide, quartz, zirconium white etc.) and mixes according to certain ratio ball milling, arrives certain fineness through high-temperature calcination and ball milling then.The main drawback that traditional technology exists: (1) each oxide compound at high temperature reacts not exclusively, is difficult for allowing painted metal ion mixing in the stable ceramic mineral of high temperature color development; (2) used muriate, fluorochemical, nitrate, borate and the carbonate etc. of alkali metal containing and alkaline-earth metal in the production, and these salt compounds at high temperature decompose the gas that the back produced and can have a strong impact on environment.Shortcoming such as adopt that traditional technology produces that beramic color exists that cost is higher, contaminate environment, tinting strength are more weak.
Patent documentation report about beramic color and preparation method thereof also has many at present, for example: 1, application number is 200610031874.9, name is called a kind of preparation method of pyroceramic pigment, the material that adopts in this preparation method has cadmium salt soln, zirconium oxychloride, sodium sulphite or ammonium sulfide solution, silicate solutions, nitric acid etc., and calcining temperature is 800～1200 ℃.2, application number is 200510048271.5, and name is called high temperature scarlet ceramic pigment and production method, has adopted materials such as yttrium oxide, aluminum oxide, chromic oxide in production method, and synthesis temperature is 1350 ℃.3, application number is 200710061841.3, and name is called the production technique of high-temp resistant bismuth vanadate yellow ceramic pigment, has adopted Bismuth trinitrate (Bi (NO in this production technique
3)
3), ammonium vanadate (NH
4VO
3), material such as water glass and silicon-dioxide, maturing temperature is 500～900 ℃.
At present; in the domestic patent documentation about seldom to the concrete report of beramic color chrome green production method; the inventor is through great deal of experimental; developed a kind of method of utilizing waste materials of chromium salt factory to produce the beramic color chrome green; this method not only can be produced the beramic color chrome green product that satisfies industrial requirements; and the pollution problem that has solved the chromium salt factory refuse, help environment protection.
Three, content of the present invention:
The technical problem to be solved in the present invention provides a kind of method of utilizing waste materials of chromium salt factory to produce the beramic color chrome green.
Address the above problem, the technical solution used in the present invention is:
The invention provides a kind of method of utilizing waste materials of chromium salt factory to produce the beramic color chrome green, the detailed step of this method is as follows:
A, step of reaction: soda ash and water are put in the reactor of belt stirrer, the add-on of water is 3 times of soda ash add-on, begin after the adding to stir and heat up, after soda ash fully dissolves, add waste materials of chromium salt factory acid mud, the part by weight of soda ash and sour the two add-on of mud is 1: 2～2.6, when temperature reaches 80～100 ℃, stop to heat up and continue to stir, reacted 1～3 hour, reaction finishes the back and adds the chromium salt factory waste acid water, the pH value to 2 of conditioned reaction solution～4, react after 1～2 hour, add industrial sugar or S-WAT, its add-on is 10～20% of a reaction soln total amount, obtain clear liquid behind the quiescent setting, add concentration and be 15～20% ammoniacal liquor in clear liquid, the pH value of control solution is to stop step of reaction agitator continuously stirring at 8～10 o'clock;
B, press filtration stage: step a gained reaction soln is carried out press filtration, washing, obtain filter cake after the washing;
C, roasting stage: step b gained filter cake is imported kiln carry out roasting, maturing temperature is 750～950 ℃, and roasting time is 4～6 hours, after the end it is cooled to below 50 ℃, its lapping powder being broken into fineness then is 320 purpose powder, is the product chrome green.
For the above-mentioned method of utilizing waste materials of chromium salt factory to produce the beramic color chrome green, soda ash described in the step a is industrial one-level soda ash, its purity＞98%, and the stirring velocity of described agitator is 38～45 rev/mins.
For the above-mentioned method of utilizing waste materials of chromium salt factory to produce the beramic color chrome green, the content of chromium sodium sulphate is 40～50% in the acid of waste materials of chromium salt factory described in the step a mud, and the content of Sodium chromate and sodium sulfate is 10～15%, and all the other are water; Contain 25～35% sulfuric acid and 35～45% sodium pyrosulfate in the chromium salt factory waste acid water, surplus is water and impurity.
For the above-mentioned method of utilizing waste materials of chromium salt factory to produce the beramic color chrome green, flame filter press or horizontal centrifuge are adopted in press filtration described in the step b.
For the above-mentioned method of utilizing waste materials of chromium salt factory to produce the beramic color chrome green, kiln described in the step c is rotary kiln or tunnel furnace.
Cr in the gained beramic color chrome green product of the present invention
2O
3Content greater than 95%.
Positive beneficial effect of the present invention:
1, to adopt the waste material acid mud and the waste acid water of chromium salt factory be raw material in the present invention, makes it obtain again utilizing, and solved the severe contamination problem of chromium salt factory refuse, helps environment protection.From environmental angle, the present invention has remarkable social benefit.
2, adopt the inventive method to produce the beramic color chrome green, simple to operate, products obtained therefrom can satisfy industrial requirements, and yield is higher, Cr in the products obtained therefrom chrome green
2O
3Content greater than 95%.
3. maturing temperature is lower in the production method of beramic color chrome green of the present invention, and production cost is lower, therefore, adopts the inventive method to produce beramic color chrome green remarkable in economical benefits.
4. adopt the beramic color chrome green tinting strength of production method preparation of the present invention stronger.
5, the present invention adopts waste materials of chromium salt factory to produce the beramic color chrome green; not only solve the severe contamination problem of chromium salt factory waste, helped environment protection, and produced the beramic color chrome green product that can satisfy industrial requirements; therefore, the present invention has remarkable economic efficiency and social benefit.
Four, embodiment:
Following examples only in order to further specify the present invention, do not limit content of the present invention.
Embodiment one: a kind of method of utilizing waste materials of chromium salt factory to produce the beramic color chrome green
Raw materials used soda ash is industrial one-level soda ash, its purity＞98%; The content of chromium sodium sulphate is 40～50% in the waste materials of chromium salt factory acid mud, and the content of Sodium chromate and sodium sulfate is 10～15%, and all the other are water; Contain 25～35% sulfuric acid and 35～45% sodium pyrosulfate in the chromium salt factory waste acid water, surplus is water and impurity.This method may further comprise the steps:
A, step of reaction: 1 ton of soda ash and 3 tons of water are put in the reactor of belt stirrer, the add-on of water is 3 times of soda ash add-on, begin after the adding to stir and heat up, the stirring velocity of agitator is 38～45 rev/mins, after soda ash fully dissolves, add 2 tons in waste materials of chromium salt factory acid mud, the part by weight of soda ash and sour the two add-on of mud is 1: 2, when temperature reaches 90 ℃, stop to heat up, continue to stir, reacted 2 hours, reaction finishes the back and adds the chromium salt factory waste acid water, reacted 1～2 hour the pH value to 2 of conditioned reaction solution～4, adds S-WAT then, its add-on is 15% of a reaction soln total amount, obtain clear liquid behind the quiescent setting, add concentration and be 15% ammoniacal liquor in clear liquid, the pH value of control solution is to stop in 9 o'clock;
B, press filtration stage: adopt flame filter press to carry out press filtration, washing step a gained reaction soln, obtain filter cake after the washing;
C, roasting stage: step b gained filter cake is imported rotary kiln carry out roasting, maturing temperature is 800 ℃, roasting time is 5 hours, after the end it is cooled to below 50 ℃, then its lapping powder being broken into fineness is 320 purpose powder, be the product chrome green, it is weighed obtains 0.27 ton of product, Cr in the chrome green product
2O
3Content greater than 95%.
Embodiment two: basic identical with embodiment one, something in common is no longer narrated, and difference is:
Add 2.5 tons in 1 ton of soda ash and sour mud among the step a, the part by weight of soda ash and sour the two add-on of mud is 1: 2.5, temperature of reaction is 100 ℃, reacted 1 hour, the add-on of S-WAT is 20% of a reaction soln total amount, obtain clear liquid behind the quiescent setting, add concentration and be 18% ammoniacal liquor in clear liquid, the pH value of control solution is to stop in 8 o'clock;
Adopt horizontal centrifuge that reaction soln is carried out press filtration among the step b;
Adopt rotary kiln to carry out roasting among the step c, maturing temperature is 750 ℃, and roasting time is 6 hours.
Obtain 0.32 ton of product chrome green at last.
Embodiment three: basic identical with embodiment one, something in common is no longer narrated, and difference is:
Add 4.4 tons in 2 tons of soda ash and sour mud among the step a, the part by weight of soda ash and sour the two add-on of mud is 1: 2.2, temperature of reaction is 80 ℃, reacted 3 hours, the add-on of S-WAT is 10% of a reaction soln total amount, obtains clear liquid behind the quiescent setting, and adding concentration is 20% ammoniacal liquor in clear liquid, the pH value of control solution is 10, reacts to stop in 1.5 hours;
Adopt horizontal centrifuge that reaction soln is carried out press filtration among the step b;
Adopt rotary kiln to carry out roasting among the step c, maturing temperature is 850 ℃, and roasting time is 4 hours.
Obtain 0.58 ton of product chrome green at last.
Embodiment four: basic identical with embodiment one, something in common is no longer narrated, and difference is:
Add 5.2 tons in 2 tons of soda ash and sour mud among the step a, the part by weight of soda ash and sour the two add-on of mud is 1: 2.6, temperature of reaction is 85 ℃, reacted 3 hours, the add-on of industry sugar is 13% of a reaction soln total amount, obtains clear liquid behind the quiescent setting, and adding concentration is 20% ammoniacal liquor in clear liquid, the pH value of control solution is 9, reacts to stop in 1 hour;
Adopt flame filter press that reaction soln is carried out press filtration among the step b;
Adopt rotary kiln to carry out roasting among the step c, maturing temperature is 950 ℃, and roasting time is 4 hours.
Obtain 0.65 ton of product chrome green at last.
Embodiment five: basic identical with embodiment one, something in common is no longer narrated, and difference is:
Add 2.5 tons in 1 ton of soda ash and sour mud among the step a, the part by weight of soda ash and sour the two add-on of mud is 1: 2.5, temperature of reaction is 95 ℃, reacted 2 hours, the add-on of S-WAT is 18% of a reaction soln total amount, obtains clear liquid behind the quiescent setting, and adding concentration is 15% ammoniacal liquor in clear liquid, the pH value of control solution is 8, reacts to stop in 2 hours;
Adopt horizontal centrifuge that reaction soln is carried out press filtration among the step b;
Adopt rotary kiln to carry out roasting among the step c, maturing temperature is 850 ℃, and roasting time is 4 hours.
Obtain 0.30 ton of product at last.
Embodiment six: basic identical with embodiment one, something in common is no longer narrated, and difference is:
Add 2.3 tons in 1 ton of soda ash and sour mud among the step a, the part by weight of soda ash and sour the two add-on of mud is 1: 2.3, temperature of reaction is 95 ℃, reacted 1.5 hours, the add-on of industry sugar is 18% of a reaction soln total amount, obtain clear liquid behind the quiescent setting, add concentration and be 20% ammoniacal liquor in clear liquid, the pH value of control solution is to stop in 9 o'clock;
Adopt horizontal centrifuge that reaction soln is carried out press filtration among the step b;
Adopt tunnel furnace to carry out roasting among the step c, maturing temperature is 850 ℃, and roasting time is 5 hours.
Obtain 0.28 ton of product chrome green at last.
Embodiment seven: basic identical with embodiment one, something in common is no longer narrated, and difference is:
Add 2.05 tons in 1 ton of soda ash and sour mud among the step a, the part by weight of soda ash and sour the two add-on of mud is 1: 2.05, temperature of reaction is 90 ℃, anti-2 hours, the add-on of S-WAT is 16% of a reaction soln total amount, obtain clear liquid behind the quiescent setting, add concentration and be 15% ammoniacal liquor in clear liquid, the pH value of control solution is to stop in 10 o'clock;
Adopt flame filter press that reaction soln is carried out press filtration among the step b;
Adopt tunnel furnace to carry out roasting among the step c, maturing temperature is 800 ℃, and roasting time is 5 hours.
Obtain 0.26 ton of product chrome green at last.
Embodiment eight: basic identical with embodiment one, something in common is no longer narrated, and difference is:
Add 2.55 tons in 1 ton of soda ash and sour mud among the step a, the part by weight of soda ash and sour the two add-on of mud is 1: 2.55, temperature of reaction is 85 ℃, reacted 2.5 hours, the add-on of industry sugar is 14% of a reaction soln total amount, obtain clear liquid behind the quiescent setting, add concentration and be 20% ammoniacal liquor in clear liquid, the pH value of control solution is to stop in 8 o'clock;
Adopt horizontal centrifuge that reaction soln is carried out press filtration among the step b;
Adopt rotary kiln to carry out roasting among the step c, maturing temperature is 800 ℃, and roasting time is 5 hours.
Obtain 0.33 ton of product chrome green at last.
Claims (6)
1. method of utilizing waste materials of chromium salt factory to produce the beramic color chrome green is characterized in that this method may further comprise the steps:
A, step of reaction: soda ash and water are put in the reactor of belt stirrer, the add-on of water is 3 times of soda ash add-on, begin after the adding to stir and heat up, after soda ash fully dissolves, add waste materials of chromium salt factory acid mud, the part by weight of soda ash and sour the two add-on of mud is 1: 2～2.6, when temperature reaches 80～100 ℃, reacted 1～3 hour, reaction finishes the back and adds the chromium salt factory waste acid water, reacted 1～2 hour the pH value to 2 of conditioned reaction solution～4, adds industrial sugar or S-WAT then and continue reaction, its add-on is 10～20% of a reaction soln total amount, obtain clear liquid behind the quiescent setting, add concentration and be 15～20% ammoniacal liquor in clear liquid, the pH value of control solution is 8～10 to stop;
B, press filtration stage: step a gained reaction soln is carried out press filtration, washing, obtain filter cake after the washing;
C, roasting stage: step b gained filter cake is imported kiln carry out roasting, maturing temperature is 750～950 ℃, and roasting time is 4～6 hours, after the end it is cooled to below 50 ℃, its lapping powder being broken into fineness then is 320 purpose powder, is the product chrome green.
2. the method for utilizing waste materials of chromium salt factory to produce the beramic color chrome green according to claim 1, it is characterized in that: soda ash described in the step a is industrial one-level soda ash, its purity＞98%.
3. the method for utilizing waste materials of chromium salt factory to produce the beramic color chrome green according to claim 1, it is characterized in that: the stirring velocity of agitator described in the step a is 38～45 rev/mins; The content of chromium sodium sulphate is 40～50% in the described waste materials of chromium salt factory acid mud, and the content of Sodium chromate and sodium sulfate is 10～15%, and all the other are water; Contain 25～35% sulfuric acid and 35～45% sodium pyrosulfate in the described chromium salt factory waste acid water, surplus is water and impurity.
4. the method for utilizing waste materials of chromium salt factory to produce the beramic color chrome green according to claim 1 is characterized in that: flame filter press or horizontal centrifuge are adopted in press filtration described in the step b.
5. the method for utilizing waste materials of chromium salt factory to produce the beramic color chrome green according to claim 1, it is characterized in that: kiln described in the step c is rotary kiln or tunnel furnace.
6. the method for utilizing waste materials of chromium salt factory to produce the beramic color chrome green according to claim 1 is characterized in that: Cr in the gained chrome green product
2O
3Content greater than 95%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159505A (en) * | 2013-03-29 | 2013-06-19 | 佛山市南海万兴材料科技有限公司 | Process for preparing zirconium-cadmium-selenium series colorant from recycled cadmium-containing wastewater |
| CN106046858A (en) * | 2016-06-01 | 2016-10-26 | 佛山市高明区海帝陶瓷原料有限公司 | Method for preparing black ceramic pigment with chromium-based waste materials and black ceramic pigment |
| CN106315675A (en) * | 2016-08-23 | 2017-01-11 | 张晓东 | Method for producing basic chromic sulfate by utilizing tannery waste chromium mud |
| CN114212821A (en) * | 2022-01-07 | 2022-03-22 | 重庆民丰化工有限责任公司 | Method for producing chromium green by using chromic anhydride by-product |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070187A (en) * | 2007-03-15 | 2007-11-14 | 李兴 | Chromium-salt clean production process |
-
2008
- 2008-10-27 CN CN2008102306001A patent/CN101723459B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159505A (en) * | 2013-03-29 | 2013-06-19 | 佛山市南海万兴材料科技有限公司 | Process for preparing zirconium-cadmium-selenium series colorant from recycled cadmium-containing wastewater |
| CN106046858A (en) * | 2016-06-01 | 2016-10-26 | 佛山市高明区海帝陶瓷原料有限公司 | Method for preparing black ceramic pigment with chromium-based waste materials and black ceramic pigment |
| CN106315675A (en) * | 2016-08-23 | 2017-01-11 | 张晓东 | Method for producing basic chromic sulfate by utilizing tannery waste chromium mud |
| CN106315675B (en) * | 2016-08-23 | 2017-09-15 | 张晓东 | A kind of method that utilization tanned wastes chromium mud produces chromium sulfate basic |
| CN114212821A (en) * | 2022-01-07 | 2022-03-22 | 重庆民丰化工有限责任公司 | Method for producing chromium green by using chromic anhydride by-product |
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Effective date of registration: 20160923 Address after: Chang'an Town, Beiliu City, the Guangxi Zhuang Autonomous Region City, Yulin 537400 Cross shop Industrial Zone Patentee after: ZHONGLI CERAMICS CO., LTD. Address before: 450100, Henan, Xingyang Province Wang Town, River Temple Village Patentee before: Zhang Xiaodong |
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