CN102689931A - Method for producing iron oxide black from desiliconized sludge cake by one-step process - Google Patents
Method for producing iron oxide black from desiliconized sludge cake by one-step process Download PDFInfo
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- CN102689931A CN102689931A CN201210191410XA CN201210191410A CN102689931A CN 102689931 A CN102689931 A CN 102689931A CN 201210191410X A CN201210191410X A CN 201210191410XA CN 201210191410 A CN201210191410 A CN 201210191410A CN 102689931 A CN102689931 A CN 102689931A
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- iron oxide
- desiliconization
- mud
- oxide black
- mud cake
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Abstract
The invention discloses a method for producing iron oxide black from desiliconized sludge cake by a one-step process. By improving the material flow process, the invention utilizes Fe(OH)2, which is generated from ferrous chloride and ammonia water generated in the desiliconized sludge cake, to directly participate in the preparation of the iron oxide black, and abandons the past two-step method of respectively preparing a ferrous sulfate solution and ferrite yellow. Compared with the traditional technique, the invention reduces the production steps, enhances the efficiency, saves the consumption of waste acid and alkali liquor, and prepares the good-performance low-cost iron oxide black on the basis of the desiliconized sludge cake in the mass treatment process of steel mill acid washing waste liquor.
Description
Technical field
The present invention relates to technical field of inorganic material, be specifically related to the method that a kind of single stage method desiliconization mud cake is produced iron oxide black.
Technical background
Iron oxide black is a kind of a kind of Chemicals that extensive use is arranged in industries such as building, coating, can be used for colored cement, colored cement floor tile, color cement tile, imitative terra-cotta, concrete floor tile, colored mortar, color asphalt, terrazzo, mosaic ornamental slab for paving the floor, artificial marble and wall plaster etc.; Can also be used to making various paint, coating, printing ink.In other industry, can also be used to doing tinting material and weighting agent.
The method of traditional mode of production iron oxide black adopts copperas solution and sodium hydroxide reaction to generate ferrous hydroxide more; Ferrous hydroxide synthesizes the solution deposit that is settled out iron oxide black with red oxide of iron again; Traditional solution deposit is had relatively high expectations to raw-material; The product seed ratio is more single, and material cost is higher.
The filter waste material that desilication device produced when the desiliconization mud cake was cold rolling mill production magnetic iron oxide red, staple Fe
2O
3(about 30%), Fe (OH)
2(about 20%), H
2O (about 50%) also contains a small amount of SiO
2Deng impurity, the Fe in the staple
2O
3, Fe (OH)
2Content along with the prolongation of storage period, Fe
2O
3To increase, and Fe (OH)
2To reduce, reason is Fe (OH)
2Character is unstable, in air, very easily is oxidized to Fe
2O
3In the traditional technology, need prepare Fe respectively
2O
3, Fe (OH)
2Fe in the desiliconization mud cake
2O
3Can in the preparation of iron oxide black, use, thereby reduce iron plane expense consumption, the Fe in the desiliconization mud cake (OH) as the iron oxide yellow additive
2Substitute the synthetics of ferrous sulfate and liquid caustic soda, directly come into operation, reduced the consumption of ferrous sulfate and liquid caustic soda.
Chinese patent CN 100564267C discloses a kind of method of producing iron oxide black with the desiliconization mud cake; With steel mill's spent pickle liquor desiliconization mud cake is the raw material production iron oxide black; Adopted oxidation to synthesize synthetic method; Through ferrous and remaining vitriolic spent pickle liquor of sulfur acid and iron sheet prepared in reaction copperas solution, generate Fe (OH) through copperas solution and alkaline reaction again
2, at last through Fe (OH)
2With Fe
2O
3Prepared in reaction is iron black.Can find out, this process synthesis oxidation and the synthesis technique in traditional solution deposit, can effectively handle the iron and steel waste resources such as spent acid and desiliconization mud cake of Baosteel, and its green is processed into a kind of the confession conventionally uses nontoxic iron oxide black product.With utilizing iron sheet, sulfuric acid reaction certain cost advantage is arranged at the beginning of this technology utilization, but with utilize iron oxide red, iron oxide yellow tankage and by-product of white titanium pigment production to compare now not possess cost advantage.
Iron black preparation: mainly pass through Fe
2O
3And Fe (OH)
2Synthetic according to a certain percentage preparing, reaction process prepares Fe (OH) through ferrous sulfate and liquid caustic soda
2, prepare Fe (OH) through iron protochloride and ammoniacal liquor and produce technology in the desiliconization mud cake
2, both compositions are consistent, utilize the Fe (OH) in the desiliconization mud cake why not
2Directly prepare iron black product?
Summary of the invention
The objective of the invention is to defective to above-mentioned prior art; Provide a kind of single stage method desiliconization mud cake to produce the method for iron oxide black; With steel mill's spent pickle liquor desiliconization mud cake is raw material, and the one-step synthesis iron oxide black substitutes the technology that existing two-step approach is produced iron oxide black, the handling problem that solves the desiliconization mud cake on the one hand; Improve the waste streams transfer efficient on the other hand, reduce production costs simultaneously.
Single stage method desiliconization mud cake of the present invention is produced the method for iron oxide black, may further comprise the steps:
(1) the desiliconization mud cake adds the water making beating, processes the desiliconization material-mud, gets the 50ml slurry, adds 50ml, and concentration is 30% sulphuric acid soln, and the ferrous hydroxide colloid is reduced to copperas solution.Filtering liq is measured the content and the iron oxide content of ferrous sulfate respectively, calculates the initial molar ratio (Fe of slurry
2+: Fe
3+Mol ratio); Iron oxide red adds the water making beating, and it is for use to process the iron oxide red slurry;
(2) desiliconization material-mud and iron oxide red slurry are squeezed in the reaction kettle, then added copperas solution less than 1:2, greater than 1:2, then mend the iron oxide red slurry, finally make Fe in the mixed solution like initial proportioning like initial mol ratio
2+: Fe
3+Mol ratio be 1:2;
(3) be warming up to 90-110 ℃, add alkali lye, adjustment pH of mixed value is to 8-9, reaction 5 ~ 7h, filter, wash, dry iron oxide black.
Its reaction formula is:
FeSO
4+2NaOH→Na
2SO
4+Fe（OH）
2
Fe
2O
3+Fe（OH）
2→Fe
3O
4+H
2O
For guaranteeing Fe (OH) in the desiliconization mud cake
2Content, need reduce it to greatest extent and be exposed to airborne oxidization time, in the shortest time, be used for producing, promptly said desiliconization mud cake is the desiliconization mud cake of generation time in 10-48h.
Total solid content of ferrous hydroxide and iron oxide red is advisable to be adjusted to 15-20wt% in the middle desiliconization material-mud of step (1); The content of iron oxide red is adjusted to 15-20wt% in the iron oxide red slurry.
Said alkali lye comprises sodium hydroxide solution, potassium hydroxide solution, and concentration is 25-35%, preferred sodium hydroxide solution.
The concrete grammar of measuring hydroxide concentration of iron in the desiliconization material-mud in the step (1) is:
Get V
1Volume desiliconization material-mud to be measured adds V
2The sulfuric acid of volume 30% dissolves ferrous hydroxide wherein fully, and reaction formula is: Fe (OH)
2+ H
2SO
4→ FeSO
4+ 2H
2O;
Pass through the concentration C of ferrous ion in the dichromate titration assaying reaction liquid then
2, according to C
1=C
2(V
1+ V
2)/V
1Calculate the concentration C of ferrous ion in the desiliconization material-mud
1
Fe is mainly passed through in the iron oxide black
2O
3And Fe (OH)
2Synthetic according to a certain percentage preparing, the present invention is through improving the logistics flow process, utilized the Fe (OH) that produces iron protochloride and ammoniacal liquor generation in the technology in the desiliconization mud cake
2It is iron black to participate in preparation directly; Two steps that prepare copperas solution and iron oxide yellow before having abandoned respectively prepare iron black method; Reduced production stage, improved efficient with respect to traditional technology; Practice thrift spent acid and alkali lye consumption, simultaneously on a large amount of bases of handling steel mill's spent pickle liquor desiliconization mud cake, prepared excellent property, iron oxide black with low cost.
Embodiment
Embodiment 1:
Batching:
Silica removal mud cake making beating: get the desiliconization mud cake 1000kg that contains moisture 50% in the 24h that cold rolling mill produces, be added to and add 2m
3In the making beating still of water, disperse while add to throw, making beating still mixing speed 45 commentaries on classics/min, it is 2.5 cubic metres that stirring 2h makes mud cake fully be dispersed into TV, the slurry of solid content 20%.With the content of ferrous hydroxide in the dichromate titration mensuration desiliconization material-mud, the content that records ferrous hydroxide is 7.2wt% (180kg/2.5 cubic meter); Content with iron oxide red in the suction filtration oven drying method mensuration desiliconization material-mud records content 12.8wt% (320kg/2.5 cubic meter);
Iron oxide red making beating: 500kg iron oxide red dry powder is dropped into 2.5m
3In the water, record content 16.7wt%, get its 2/5, (contain iron oxide red 200kg, purpose is to improve the iron-holder of product) squeezed into reaction container, remaining 300kg is subsequent use.
Calculate initial molar ratio Fe
2+: Fe
3+Be 1:3.25 (180/90:2*520/160), need to mend ferrous iron concentration and be 1 cubic metre in the ferrous sulfate of 35wt%, after mending, final mol ratio is: 1:2 [(180/90+350/278): 2*520/160].
Add the sodium hydroxide solution liquid adjustment pH of mixed value to 9 of 25wt%, be warming up to 100 ℃, reaction 5h after treating to dewater fully, crosses 325 mesh sieves, the press filtration rinsing, 100 ℃ dry iron oxide black 715kg.Through test, reach the iron black requirement of products of industry standard architectural grade.
Claims (5)
1. single stage method desiliconization mud cake is produced the method for iron oxide black, it is characterized in that, may further comprise the steps:
(1) the desiliconization mud cake adds the water making beating, processes the desiliconization material-mud, measures the content and the iron oxide content of ferrous sulfate respectively; Iron oxide red adds the water making beating, and it is for use to process the iron oxide red slurry; Calculate the initial proportioning of two kinds of slurries, i.e. Fe
2+: Fe
3+Mol ratio;
(2) desiliconization material-mud and iron oxide red slurry are squeezed in the reaction kettle, be lower than 1:2, then add copperas solution, be higher than 1:2, then add the iron oxide red slurry, finally make Fe in the mixed solution like initial proportioning like initial proportioning
2+: Fe
3+Mol ratio be 1:2;
(3) be warming up to 90-110 ℃, add alkali lye, adjustment pH of mixed value is to 8-9, reaction 5 ~ 7h, filter, wash, dry iron oxide black.
2. the described single stage method desiliconization of claim 1 mud cake is produced the method for iron oxide black, it is characterized in that said desiliconization mud cake is the desiliconization mud cake of generation time in 10-48h, wherein is rich in the hydroxide iron.
3. the described single stage method desiliconization of claim 1 mud cake is produced the method for iron oxide black, it is characterized in that, total solid content of ferrous hydroxide and red stone is adjusted to 15-20wt% in the middle desiliconization material-mud of step (1); The content of iron oxide red is adjusted to 15-20wt% in the iron oxide red slurry.
4. the described single stage method desiliconization of claim 1 mud cake is produced the method for iron oxide black, it is characterized in that said alkali lye comprises sodium hydroxide solution, potassium hydroxide solution, and concentration is 25-35%.
5. the described single stage method desiliconization of claim 1 mud cake is produced the method for iron oxide black, it is characterized in that, the concrete grammar of measuring hydroxide concentration of iron in the desiliconization material-mud in the step (1) is: get V
1Volume desiliconization material-mud to be measured adds V
2The sulfuric acid of volume 30% dissolves ferrous hydroxide wherein fully; Pass through the concentration C of ferrous ion in the dichromate titration assaying reaction liquid then
2, according to C
1=C
2(V
1+ V
2)/V
1Calculate the concentration C of ferrous ion in the desiliconization material-mud
1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210191410.XA CN102689931B (en) | 2012-06-11 | 2012-06-11 | Method for producing iron oxide black from desiliconized sludge cake by one-step process |
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|---|---|---|---|
| CN201210191410.XA CN102689931B (en) | 2012-06-11 | 2012-06-11 | Method for producing iron oxide black from desiliconized sludge cake by one-step process |
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| CN102689931A true CN102689931A (en) | 2012-09-26 |
| CN102689931B CN102689931B (en) | 2014-05-14 |
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| CN201210191410.XA Expired - Fee Related CN102689931B (en) | 2012-06-11 | 2012-06-11 | Method for producing iron oxide black from desiliconized sludge cake by one-step process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109987641A (en) * | 2017-12-30 | 2019-07-09 | 天津友发钢管集团股份有限公司 | A kind of method that red soil prepares iron oxide black |
| CN113060948A (en) * | 2021-04-01 | 2021-07-02 | 重庆康尼睿能商贸有限公司 | Cement raw meal and preparation method of cement |
| CN113772741A (en) * | 2021-09-06 | 2021-12-10 | 江苏宇星科技有限公司 | Method for producing iron oxide black by liquid phase synthesis |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57175734A (en) * | 1981-04-21 | 1982-10-28 | Res Inst For Prod Dev | Preparation of ultrafine particle of fe3o4 |
| CN1807263A (en) * | 2006-02-21 | 2006-07-26 | 上海宝齐氧化铁有限公司 | Method for producing iron oxide black using desilicified mud cake |
| CN101560336A (en) * | 2008-04-18 | 2009-10-21 | 上海宝齐氧化铁有限公司 | Spherical iron oxide black and preparation technology thereof |
| CN102424428A (en) * | 2011-09-13 | 2012-04-25 | 上海宝齐氧化铁有限公司 | Technology for preparing iron oxide black for developer use with metallurgical waste |
-
2012
- 2012-06-11 CN CN201210191410.XA patent/CN102689931B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57175734A (en) * | 1981-04-21 | 1982-10-28 | Res Inst For Prod Dev | Preparation of ultrafine particle of fe3o4 |
| CN1807263A (en) * | 2006-02-21 | 2006-07-26 | 上海宝齐氧化铁有限公司 | Method for producing iron oxide black using desilicified mud cake |
| CN101560336A (en) * | 2008-04-18 | 2009-10-21 | 上海宝齐氧化铁有限公司 | Spherical iron oxide black and preparation technology thereof |
| CN102424428A (en) * | 2011-09-13 | 2012-04-25 | 上海宝齐氧化铁有限公司 | Technology for preparing iron oxide black for developer use with metallurgical waste |
Non-Patent Citations (2)
| Title |
|---|
| 张宏锦等: "钢厂含铁尘泥生产氧化铁颜料的研究开发", 《冶金环境保护》 * |
| 黄华特: "利用冶金废弃物制备球形铁黑", 《上海涂料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109987641A (en) * | 2017-12-30 | 2019-07-09 | 天津友发钢管集团股份有限公司 | A kind of method that red soil prepares iron oxide black |
| CN113060948A (en) * | 2021-04-01 | 2021-07-02 | 重庆康尼睿能商贸有限公司 | Cement raw meal and preparation method of cement |
| CN113772741A (en) * | 2021-09-06 | 2021-12-10 | 江苏宇星科技有限公司 | Method for producing iron oxide black by liquid phase synthesis |
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|---|---|
| CN102689931B (en) | 2014-05-14 |
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