CN101554613B - Method for recycling industrial waste sulfate slag - Google Patents
Method for recycling industrial waste sulfate slag Download PDFInfo
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- CN101554613B CN101554613B CN2009100944765A CN200910094476A CN101554613B CN 101554613 B CN101554613 B CN 101554613B CN 2009100944765 A CN2009100944765 A CN 2009100944765A CN 200910094476 A CN200910094476 A CN 200910094476A CN 101554613 B CN101554613 B CN 101554613B
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- sulfate slag
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- iron
- acid
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Abstract
The invention provides a method for recycling industrial waste sulfate slag, which comprises the steps of sieving, stirring, magnetic separation, acid dipping, rinsing and drying to obtain iron-bearing materials. The method not only reallocates the available resource of the sulfate slag which is difficult to be processed and has high pollution, but also reduces the severe contamination of the sulfate slag to the environment and simultaneously lowers the production cost greatly; the metal recovery rate is 50 to 82 percent, high quality iron concentrate with the grade of iron being larger than 60 percent, the grade of sulfur being smaller than 0.3 percent and the grade of arsenic being smaller than 0.1 percent is obtained; simultaneously the recovery processing capacity is large, the equipment is simple, the investment is small, the operation is convenient, the sulfate slag material is not limited, both the sulfate slag with high iron content and the sulfate slag with low iron content can be recycled, and the method has good social benefit and remarkable economic effect.
Description
Technical field
The present invention relates to a kind of recovery and treatment method of sulfate slag, especially utilize the method for industrial waste acid recycling sulfate slag, belong to industrial waste residue disposal recovery technology field.
Background technology
China is utilizing troilite to produce in the technical process of sulfuric acid, and about 7,000 ten thousand tons of annual sulfate slag of discharging accounts for 1/3rd of the capable waste residue total amount of chemical industry.Because the quantity of slag is big, fine size, and fine day is existed everywhere, the phenomenon of red current of rainy day, and objectionable impurities such as problems such as sulphur, arsenic content height, causes the harm that is difficult to estimate to environment.Except the higher sulfate slag of iron content can recycle, the sulfate slag that remaining most of iron content is lower or on the low side all can not be handled at present, filled out but pile, and the time one is long, will the severe contamination groundwater resources.For accessible iron-holder for the sulfate slag more than 50%, because the sulfate slag granularity is thinner, viscosity is higher, and contain higher sulphur, arsenic, therefore it is little to exist iron grade increase rate in the industrial treatment process, and impurity falls such as sulphur, arsenic are low, and the rate of recovery is low, investment is big, problems such as operating cost height.Can not get effective solution for a long time always, seriously perplex and restricting the development of enterprise, make this valuable iron-containing resource can not get effective utilization again simultaneously.
Present processing method has: magnetic method, gravity separation method, chemical immersion method, flotation inverse flotation method, bacterial desulfurization method, magnetic separation post separating method, magnetization reduction roasting method and rotary kiln facture etc.Wherein comparatively practical technical process is: levigate → acidleach → flotation or magnetic separation → washing → dry iron-bearing material (powdery) that gets.But the deficiency that this technology exists is: (1) sulfate slag is through after the levigate processing, though help acidleach, but because levigate processing has changed the original thing phase of sulfate slag, the magnetic separation or the flotation that make it to be difficult to postorder sort, and are fundamentally restricting the raising of iron grade; Grinding attachment investment simultaneously is big, power consumption height (in the day output of 200 ton per days, the about 50KW of power consumption), processing cost height.(2) owing to directly enter the acidleach processing after levigate, make the entire process production line be in the acid environment fully, the one, heavy corrosion production equipment, place, strengthen equipment loss, cause the production cost height, the 2nd, abominable production environment is serious threat work on the spot person healthy also, the 3rd, a large amount of ore pulps need consume a large amount of acid, just can finish acidleach, not only increase production cost, also increase the weight of the pollution of acid.Therefore, must seek new technical solution in addition,, reduce simultaneously and pollute, reduce cost, improve the iron grade to realize the recycling of iron resource.
Summary of the invention
The object of the present invention is to provide a kind of method of recycling industrial waste sulfate slag, make it under low-cost, low acid consumption, free of contamination working condition, acquisition iron is of high grade, it is low to contain S, contain the low iron material of arsenic, simultaneously the iron-holder of the sulfate slag raw material handled is not limit, and equipment is simple, treating capacity is big, remarkable in economical benefits, the acid solution after the processing, waste water is capable of circulation uses again.
The present invention finishes by following technical proposal: a kind of method of recycling industrial waste sulfate slag is characterized in that through the following step:
A, the sulfate slag raw material is added water sieve, the mass concentration under must sieving is that 10～20% ore pulp and sieve are gone up particle, and particle reclaims;
B, add the amount of 30～80 gram inorganic agents, in A step gained ore pulp, add the inorganic agent of forming by following raw materials by weight percentage, stirred 5～10 minutes by sulfate slag raw material per ton:
Anion surfactant 50～80%
Ammonium sulfate 20～50%;
C, with the ore pulp of B step process through conventional magnetic separation, isolate ferrous material and mine tailing slurry;
D, add acid pickle to slip pH value 3～4 in the ferrous material that the C step is separated, stir acidleach 10～20 minutes, Separation of Solid and Liquid gets solid and pickle liquor, and the solid water cleans to neutral, and drying gets iron-bearing material, water lotion and pickle liquor recovery;
E, the mine tailing slurry that the C step is separated mix with water lotion and the pickle liquor that the D step reclaims, and leaching 5～10 minutes precipitates and isolates waste residue and contains the leachate of valency metal, the waste residue recovery;
F, with the isolated leachate that contains the valency metal of E step after routine is handled, reclaim valuable metal, waste liquid reclaims or returns the A step cycle and uses.
The screening of described A step is that conventional screening plant in prior art is finished on as vibratory sieve, rotary screen, adds water during screening, makes fines pass through screen cloth as far as possible.
Anion surfactant in the agent of described B step process is one or more in lauryl sodium sulfate, dodecyl sodium sulfate, sodium hexadecyl sulfate, sodium soap, the aliphatic acid, the selection of concrete kind and consumption is looked thing phase, the composition of sulfate slag raw material and is contained measuring and determines, to disperse each composition in the ore pulp, especially disperse to be blended in the impurity in the iron, reclaim iron resource to greatest extent.
The acid pickle of described D step is the waste sulfuric acid that produces in the titanium industrial production, perhaps the abraum salt acid solution that produces in the salt mine industrial production, the perhaps underproof waste sulfuric acid that produces in the sulfuric acid industry production, perhaps other industrial waste acid liquid.
The present invention has following advantage and effect:
(1), since the sulfate slag raw material without levigate processing, but directly add the water sieve branch, and neither change the rerum natura of raw material, help carrying out magnetic separation, improve iron grade and metal recovery rate, can save simultaneously the input and the Grinding procedure of grinding attachment again, reduce investment, reduce power consumption, day output meter with regard to 200 ton per days, screening machine power consumption is 1.5～3KW only, and the power consumption of levigate equipment is 50KW at least, cuts down the consumption of energy largely;
(2), because acidleach is after magnetic separation, promptly carry out in the ferrous material after having removed a large amount of impurity, not only reduced sour consumption largely, and the magnetic separation before the acidleach, stirring, screening plant do not produced any corrosion, the processing procedure of acidleach simultaneously and postorder all is to carry out in simple cement pit or groove, therefore, can reduce the input of equipment loss significantly, improve production environment, reduce and pollute, reduce staff's labour intensity;
(3), because whole technical process does not efflux any discarded liquid, recycle but reclaim or return, therefore, neither can pollute surrounding environment, can save the input amount of acid and inorganic agent again, reduce production costs largely;
(4) sulfate slag is after PROCESS FOR TREATMENT of the present invention, not only recyclable useful iron resource, can also reclaim valuable metal, waste residue after the recovery can be directly as cement producting material and brick-making raw material, not outside discourage any attempt to waste residue, therefore, 100% comprehensive utilization this trade waste of sulfate slag, making it turns waste into wealth.
In sum, after adopting such scheme, these difficult and heavy-polluted available resources of sulfate slag had both been integrated, reduced its severe contamination that environment is caused again, reduced simultaneously production cost by a relatively large margin, metal recovery rate reaches 50～80%, obtain the smart powder of high-quality iron of iron grade＞60%, sulphur＜0.3%, arsenic＜0.1%, recycling amount simultaneously is big, equipment simple, small investment, easy to operate, and the sulfate slag raw material is not limited, and the sulfate slag of high and low iron-holder all can recycle, have the good social benefit, and remarkable economic efficiency.
Description of drawings
Fig. 1 is the present invention's process chart.
The specific embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1
The main component of sulfate slag raw material is as follows:
Fe:43.87%, S:2.57%, As:0.41%, Zn:1.71%, SiO
2: 20%, all the other are clay and impurity.
A, above-mentioned sulfate slag raw material is added water and sieve with the conventional vibration of prior art, fines is fallen by the mesh of screen cloth as far as possible, the mass concentration must sieve under is 12% ore pulp and the particle that sieves, the particle recovery;
B, add the amount of 32 gram inorganic agents, in A step gained ore pulp, add the inorganic agent of forming by following raw materials by weight percentage, stirred 10 minutes by sulfate slag raw material per ton:
Lauryl sodium sulfate 50%
Ammonium sulfate 50%;
C, the ore pulp of B step process carried out magnetic separation with conventional magnetic separator of the prior art after, isolate ferrous material and mine tailing slurry;
D, in the ferrous material that the C step is separated, add the waste sulfuric acid that produces in the titanium industrial production to slip pH value 3, stir acidleach 20 minutes, Separation of Solid and Liquid gets solid and pickle liquor, and solid water again cleans to neutral, through the dry iron-bearing material that gets of routine, water lotion and pickle liquor are reclaimed, wherein the main component of iron-bearing material is as follows: Fe:60.61%, S:0.219%, As:0.083%, Zn:0.078%, SiO
2: 4.01%;
E, the mine tailing slurry that the C step is separated mix with water lotion and the pickle liquor that the D step reclaims, and leaching 5 minutes precipitates and isolates waste residue and contains the leachate of valency metal, the waste residue recovery;
F, with the isolated leachate that contains the valency metal of E step after the routine recycling of prior art, valuable metal arsenic and zinc, waste liquid returns the A step and recycles after adjusting.
Embodiment 2
The main component of sulfate slag raw material is as follows:
Fe:48.19%, S:1.18%, As:0.47%, SiO
2: 18%, all the other are clay and impurity.
A, above-mentioned sulfate slag raw material is added water and sieve with the conventional vibration of prior art, fines is fallen by the mesh of screen cloth as far as possible, the mass concentration must sieve under is 20% ore pulp and the particle that sieves, the particle recovery;
B, add the amount of 80 gram inorganic agents, in A step gained ore pulp, add the inorganic agent of forming by following raw materials by weight percentage, stirred 5 minutes by sulfate slag raw material per ton:
Dodecyl sodium sulfate 80%
Ammonium sulfate 20%;
C, the ore pulp of B step process carried out magnetic separation with conventional magnetic separator of the prior art after, isolate ferrous material and mine tailing slurry;
D, in the ferrous material that the C step is separated, add the abraum salt acid solution that produces in the salt mine industrial production to slip pH value 4, stir acidleach 10 minutes, Separation of Solid and Liquid gets solid and pickle liquor, solid water again cleans to neutral, and through the dry iron-bearing material that gets of routine, water lotion and pickle liquor are reclaimed, wherein the main component of iron-bearing material is as follows: Fe:62.39%, S:0.157%, As:0.071%, SiO
2: 5.0%;
E, the mine tailing slurry that the C step is separated mix with water lotion and the pickle liquor that the D step reclaims, and leaching 10 minutes precipitates and isolates waste residue and contains the leachate of valency metal, the waste residue recovery;
F, with the isolated leachate that contains the valency metal of E step after the routine recycling of prior art, valuable metal arsenic, waste liquid returns the A step and recycles after adjusting.
Embodiment 3
The main component of sulfate slag raw material is as follows:
Fe:46.77%, S:1.85%, As:0.45%, Zn:1.87%, SiO
2: 21%, all the other are clay and impurity.
A, above-mentioned sulfate slag raw material is added water and sieve with the conventional rotary screen of prior art, fines is fallen by the mesh of screen cloth as far as possible, the mass concentration must sieve under is 16% ore pulp and the particle that sieves, the particle recovery;
B, add the amount of 50 gram inorganic agents, in A step gained ore pulp, add the inorganic agent of forming by following raw materials by weight percentage, stirred 8 minutes by sulfate slag raw material per ton:
Sodium soap 62%
Ammonium sulfate 38%;
C, the ore pulp of B step process carried out magnetic separation with conventional magnetic separator of the prior art after, isolate ferrous material and mine tailing slurry;
D, in the ferrous material that the C step is separated, add waste sulfuric acid that sulfuric acid industry produces in producing to slip pH value 3, stir acidleach 15 minutes, Separation of Solid and Liquid gets solid and pickle liquor, and solid water again cleans to neutral, through the dry iron-bearing material that gets of routine, water lotion and pickle liquor are reclaimed, wherein the main component of iron-bearing material is as follows: Fe:61.16%, S:0.23%, As:0.07%, Zn:0.065%, SiO
2: 4.86%;
E, the mine tailing slurry that the C step is separated mix with water lotion and the pickle liquor that the D step reclaims, and leaching 8 minutes precipitates and isolates waste residue and contains the leachate of valency metal, the waste residue recovery;
F, with the isolated leachate that contains the valency metal of E step after the routine recycling of prior art, valuable metal arsenic and zinc, waste liquid returns the A step and recycles after adjusting.
Claims (4)
1. the method for a recycling industrial waste sulfate slag is characterized in that through the following step:
A, the sulfate slag raw material is added water sieve, the mass concentration under must sieving is that 10～20% ore pulp and sieve are gone up particle, and particle reclaims;
B, add the amount of 30～80 gram inorganic agents, in A step gained ore pulp, add the inorganic agent of forming by following raw materials by weight percentage, stirred 5～10 minutes by sulfate slag raw material per ton:
Anion surfactant 50～80%
Ammonium sulfate 20～50%;
C, with the ore pulp of B step process through conventional magnetic separation, isolate ferrous material and mine tailing slurry;
D, add acid pickle to slip pH value 3～4 in the ferrous material that the C step is separated, stir acidleach 10～20 minutes, Separation of Solid and Liquid gets solid and pickle liquor, and the solid water cleans to neutral, and drying gets iron-bearing material, water lotion and pickle liquor recovery;
E, the mine tailing slurry that the C step is separated mix with water lotion and the pickle liquor that the D step reclaims, and leaching 5～10 minutes precipitates and isolates waste residue and contains the leachate of valency metal, the waste residue recovery;
F, with the isolated leachate that contains the valency metal of E step after routine is handled, reclaim valuable metal, waste liquid reclaims or returns the A step cycle and uses.
2. the method for recycling industrial waste sulfate slag as claimed in claim 1 is characterized in that the screening of described A step is finished on vibratory sieve, rotary screen, adds water during screening.
3. the method for recycling industrial waste sulfate slag as claimed in claim 1, it is characterized in that anion surfactant in the agent of described B step process is one or more in lauryl sodium sulfate, dodecyl sodium sulfate, sodium hexadecyl sulfate, sodium soap, the aliphatic acid, the selection of concrete kind and consumption is looked thing phase, the composition of sulfate slag raw material and is contained measuring and determines.
4. the method for recycling industrial waste sulfate slag as claimed in claim 1, the acid pickle that it is characterized in that described D step is the waste sulfuric acid that produces in the titanium industrial production, the perhaps abraum salt acid solution that produces in the salt mine industrial production, the underproof waste sulfuric acid that produces during perhaps sulfuric acid industry is produced.
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| CN2009100944765A CN101554613B (en) | 2009-05-19 | 2009-05-19 | Method for recycling industrial waste sulfate slag |
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| CN2009100944765A CN101554613B (en) | 2009-05-19 | 2009-05-19 | Method for recycling industrial waste sulfate slag |
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| CN101554613B true CN101554613B (en) | 2011-06-29 |
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Families Citing this family (10)
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| CN102151690B (en) * | 2011-01-20 | 2013-04-03 | 杭州大地环保有限公司 | Method for treating arsenic sulfide residue |
| CN102251067A (en) * | 2011-07-04 | 2011-11-23 | 彭海洋 | Mehtod for extracting reduced iron by impurity removal of pyrite cinder |
| CN102304597B (en) * | 2011-08-26 | 2013-03-13 | 沈阳博联特熔融还原科技有限公司 | Method for smelting iron by utilizing sulfuric acid slag |
| CN103088203B (en) * | 2013-03-01 | 2015-08-12 | 罗涛 | The method of Iron concentrate is produced with sulfate slag |
| CN104789753A (en) * | 2015-02-11 | 2015-07-22 | 安徽盖娅环保科技有限公司 | New sulfur acid residue desulphurization method |
| CN106733140A (en) * | 2015-11-23 | 2017-05-31 | 湖南衡阳新澧化工有限公司 | A kind of method that utilization waste residue produces ferriferous oxide |
| CN108147658B (en) * | 2018-01-17 | 2018-12-11 | 成都绿锂环保科技有限公司 | A kind of high-valued method of comprehensive utilization of lithium slag |
| CN110002421B (en) * | 2019-05-17 | 2020-06-09 | 中南大学 | Method for preparing battery-grade iron phosphate by using sulfuric acid residues |
| CN111485101B (en) * | 2020-03-19 | 2021-03-09 | 广东华诺勤耕材料科技有限公司 | Method for recovering iron from iron-containing ore |
| CN112430729A (en) * | 2020-10-29 | 2021-03-02 | 张庆鲁 | Method for preparing iron ore powder by using sulfuric acid residues |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1057213A (en) * | 1990-06-09 | 1991-12-25 | 冶金部马鞍山钢铁设计研究院 | Process for dressing iron from low-rank iron pyrites roasted slag |
| CN1113479A (en) * | 1994-06-15 | 1995-12-20 | 江苏太平洋化学工业公司 | Manufacture of iron oxide red from waste sulfuric acid dregs |
| CN1425509A (en) * | 2002-11-27 | 2003-06-25 | 谢海泉 | Process for recovering and reutilizing sulfuric acid dregs waste material |
| CN1788851A (en) * | 2004-09-17 | 2006-06-21 | 武汉科技大学 | Sulfuric-acid residue sorting and refinement method |
| CN101049582A (en) * | 2007-03-27 | 2007-10-10 | 杨建华 | Technique for treating pyrile cinder |
-
2009
- 2009-05-19 CN CN2009100944765A patent/CN101554613B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057213A (en) * | 1990-06-09 | 1991-12-25 | 冶金部马鞍山钢铁设计研究院 | Process for dressing iron from low-rank iron pyrites roasted slag |
| CN1113479A (en) * | 1994-06-15 | 1995-12-20 | 江苏太平洋化学工业公司 | Manufacture of iron oxide red from waste sulfuric acid dregs |
| CN1425509A (en) * | 2002-11-27 | 2003-06-25 | 谢海泉 | Process for recovering and reutilizing sulfuric acid dregs waste material |
| CN1788851A (en) * | 2004-09-17 | 2006-06-21 | 武汉科技大学 | Sulfuric-acid residue sorting and refinement method |
| CN101049582A (en) * | 2007-03-27 | 2007-10-10 | 杨建华 | Technique for treating pyrile cinder |
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