CN102976527A - Method for obtaining scandium-rich material from acidic wastewater of titanium dioxide environment-friendly workshop - Google Patents
Method for obtaining scandium-rich material from acidic wastewater of titanium dioxide environment-friendly workshop Download PDFInfo
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- CN102976527A CN102976527A CN2012105434760A CN201210543476A CN102976527A CN 102976527 A CN102976527 A CN 102976527A CN 2012105434760 A CN2012105434760 A CN 2012105434760A CN 201210543476 A CN201210543476 A CN 201210543476A CN 102976527 A CN102976527 A CN 102976527A
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- waste water
- scandium
- titanium dioxide
- acid waste
- calcium carbonate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a method for obtaining a scandium-rich material from acidic wastewater of a titanium dioxide environment-friendly workshop. The method comprises the following steps: reacting mineral powder containing calcium carbonate with the acidic wastewater produced from a production technological process of titanium dioxide till the pH value of the wastewater is 1.0-2.0, filtering to remove a gypsum precipitate; neutralizing collected filtrate with the calcium carbonate mineral powder, ending the reaction when the pH value is 4.2-4.3, filtering and collecting filtration residue to obtain the filtration residue containing 100-120g/t of scandium. The recovery rate of the scandium during the whole process is larger than 75%; and compared with a traditional acidic wastewater treatment method, the method provided by the invention has the advantages that not only the environmental pollution caused by direct discharge is reduced but also the scandium-rich raw material with higher economic value is obtained.
Description
Technical field
The present invention relates to the method that acid waste water is recycled between a kind of titanium dioxide environment-friendly vehicle, particularly a kind of method of between the titanium dioxide environment-friendly vehicle, obtaining rich scandium material the acid waste water.
Background technology
Titanium dioxide is considered at present the in the world best a kind of white pigment of performance, is widely used in the industry such as coating, plastics, papermaking, printing-ink, chemical fibre, rubber, makeup.Titanium white production has sulfuric acid process (with ilmenite and sulfuric acid reaction) and two kinds of techniques of chlorination process (take chlorine as medium) at present, because economical relatively backward, the titanium dioxide industry of China is started late, on production technology, abroad take chlorination process as main, China's major part is sulfuric acid process.The greatest problem of tradition sulfuric acid process is to produce a large amount of acid waste water, and acid waste water is except containing main component H
2SO
4, also contain certain FeSO
4, Al
2(SO
4)
3, Sc
2O
3Deng material, the not treated direct discharging of these waste water not only produces severe contamination to ecotope, also causes the serious waste of resource, therefore the processing of acid waste water is had important economy and social effect.
Summary of the invention
The present invention is different from the traditional treatment method of using Wingdale neutralizing acid wastewater to generate gypsum, compare with traditional method, the advantage of the inventive method is: not only reduced direct discharging to the pollution of environment, but also got access to the rich scandium raw material with higher economic worth.
Scandium, a kind of metallic element mainly is present in the extremely rare thortveitite, only contains the scandium of a few gram to tens grams in the thortveitite per ton.The scandium of simple substance generally is applied to alloy, and the oxide compound of scandium plays an important role on stupalith, Scium trioxide can be made the TV electron beam gun of solid statelaser, high definition of deposition material, the variable wavelength of semi-conductor coating and metal halide lamp etc., has important economic worth.Between the titanium dioxide environment-friendly vehicle in the acid waste water scandium concentration lower, wastewater flow rate is large, directly adopt extracting process can not obtain the Scium trioxide raw material with economic worth, and acid waste water must pass through neutralizing treatment in titanium white production, in N-process, divide two sections neutralizations, twice filtration to obtain rich scandium raw material, can obtain better economic benefit.
Present method comprises the steps:
Add the calcium carbonate mineral powder in A, the acid waste water and carry out the neutralization first time, neutralization is arrived pH between 1.0～2.0;
B, acid waste water remove by filter the gypsum deposition of for the first time neutralization reaction formation;
Filtrate after C, the filtration adds the calcium carbonate mineral powder and carries out the neutralization second time, and neutralization is arrived pH between 4.2～4.3;
The filter residue of for the second time neutralization reaction formation is collected in D, filtration;
Described acid waste water is the trade effluent summation of collecting in each operation of titanium white, contains H
2SO
4At 60～80g/l, TiOSO
4At 2～3g/l, and Sc
2O
3At 3～5mg/l;
Described calcium carbonate mineral powder fineness＜150 orders contains CaCO
3＞90%;
Described filter residue water content＜42% contains scandium concentration at 100～120g/t.
Preferably, the described method of obtaining rich scandium material between the titanium dioxide environment-friendly vehicle the acid waste water in above-mentioned A step, adds the calcium carbonate mineral powder and carries out the mechanical stirring mixing in the acid waste water.
Preferably, the described method of between the titanium dioxide environment-friendly vehicle, obtaining rich scandium material the acid waste water, in above-mentioned C step, filtrate adds the calcium carbonate mineral powder and carries out the mechanical stirring mixing.
Preferably, the described method of between the titanium dioxide environment-friendly vehicle, obtaining rich scandium material the acid waste water, in above-mentioned A step, neutralization is to pH=1.5 for the first time.
Preferably, the described method of between the titanium dioxide environment-friendly vehicle, obtaining rich scandium material the acid waste water, in above-mentioned A step, neutralization is to pH=4.2 for the second time.
Present invention focuses in the first time and the time by control pH value, with the main component H in the waste water
2SO
4Generating gypsum deposition by neutralization reaction removes by filter, and scandium is still stayed in the filtrate, and in the second time and the time by control endpoint pH, scandium is deposited in the slag, other impurity enters the content that improves scandium in the filter residue in the slag as little as possible, obtains after filtration richer scandium slag, in above-mentioned steps A and C, the rate of recovery of the scandium that employing mechanical stirring blending means obtains is better than using other stirring mixing method (for example wind stirring) greater than 75%.
Description of drawings
Fig. 1 is a kind of method flow diagram that obtains rich scandium material between the titanium dioxide environment-friendly vehicle the acid waste water of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing, can implement according to this with reference to the specification sheets literal to make those skilled in the art.
As shown in Figure 1, the invention provides a kind of method of between the titanium dioxide environment-friendly vehicle, obtaining rich scandium material the acid waste water, can produce a large amount of acid waste water in each operation of titanium dioxide, contain H in the described acid waste water
2SO
4At 60～80g/l, TiOSO
4At 2～3g/l, and Sc
2O
3At 3～5mg/l, add the calcium carbonate mineral powder in the acid waste water and carry out the neutralization first time, neutralization is arrived pH between 1.0～2.O, remove by filter the gypsum deposition of for the first time neutralization reaction formation, the filtrate after the filtration adds the calcium carbonate mineral powder and carries out the neutralization second time, neutralizes pH between 4.2～4.3, filter the rich scandium filter residue of collecting for the second time neutralization reaction formation, the method that adopts mechanical stirring to mix in twice N-process, described calcium carbonate mineral powder fineness＜150 orders contains CaCO
3＞90%.Described filter residue water content＜42%,, contain scandium concentration at 100～120g/t.The rate of recovery of the scandium that employing the inventive method obtains is greater than 75%.
Following embodiment illustrates a kind of method of obtaining rich scandium material between the titanium white environment-friendly vehicle the acid waste water of the present invention.
Embodiment one:
Under mechanical stirring, 4 liters of waste water between the titanium white environment-friendly vehicle with the calcium carbonate mineral powder pH value 1.0 that neutralizes, are filtered to get filter cake 809g, 3.6 liters of filtrates, with the calcium carbonate mineral powder pH value 4.2 that neutralizes, vacuum filtration is drained and is obtained filter cake 190g with filtrate, it is 109g/t that filter cake contains scandium, and the scandium rate of recovery is 85%.
Embodiment two:
Under mechanical stirring, 4 liters of waste water between the titanium white environment-friendly vehicle with the calcium carbonate mineral powder pH value 2.0 that neutralizes, are filtered to get filter cake 798g, 3.7 liters of filtrates, with the calcium carbonate mineral powder pH value 4.3 that neutralizes, vacuum filtration is drained and is obtained filter cake 205g with filtrate, it is 115g/t that filter cake contains scandium, and the scandium rate of recovery is 90%.
Embodiment three:
Under mechanical stirring, 4 liters of waste water between the titanium white environment-friendly vehicle with the calcium carbonate mineral powder pH value 1.5 that neutralizes, are filtered to get filter cake 836g, 3.3 liters of filtrates, with the calcium carbonate mineral powder pH value 4.3 that neutralizes, vacuum filtration is drained and is obtained filter cake 226g with filtrate, it is 117g/t that filter cake contains scandium, and the scandium rate of recovery is 92%.
Embodiment four:
Under mechanical stirring, with 5 liters of waste water between the titanium white environment-friendly vehicle with the calcium carbonate mineral powder pH value 2.0 that neutralizes, filter to get filter cake 1.02kg, 3.9 liters of filtrates, with filtrate with the calcium carbonate mineral powder pH value 4.3 that neutralizes, vacuum filtration is drained and is obtained filter cake 302g, and it is 112g/t that filter cake contains scandium, and the scandium rate of recovery is 87%.
Embodiment five:
Under mechanical stirring, with 5 liters of waste water between the titanium white environment-friendly vehicle with the calcium carbonate mineral powder pH value 1.0 that neutralizes, filter to get filter cake 1.05kg, 4.2 liters of filtrates, with filtrate with the calcium carbonate mineral powder pH value 4.2 that neutralizes, vacuum filtration is drained and is obtained filter cake 316g, and it is 105g/t that filter cake contains scandium, and the scandium rate of recovery is 89%.
Although embodiment of the present invention are open as above, but it is not restricted to listed utilization in specification sheets and the embodiment, it can be applied to various suitable the field of the invention fully, for those skilled in the art, can easily realize other modification, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend of describing.
Claims (5)
1. a method of obtaining rich scandium material between the titanium dioxide environment-friendly vehicle the acid waste water is characterized in that the method comprises the steps:
Add the calcium carbonate mineral powder in A, the acid waste water and carry out the neutralization first time, neutralization is arrived pH between 1.0～2.0;
B, acid waste water remove by filter the gypsum deposition of for the first time neutralization reaction formation;
Filtrate after C, the filtration adds the calcium carbonate mineral powder and carries out the neutralization second time, and neutralization is arrived pH between 4.2～4.3;
The filter residue of for the second time neutralization reaction formation is collected in D, filtration;
Described acid waste water is the trade effluent summation of collecting in each operation of titanium dioxide, contains H
2SO
4At 60～80g/l, TiOSO
4At 2～3g/l, and Sc
2O
3At 3～5mg/l;
Described calcium carbonate mineral powder fineness＜150 orders contains CaCO
3＞90%;
Described filter residue water content＜42% contains scandium concentration at 100～120g/t.
2. the method for obtaining rich scandium material between the titanium dioxide environment-friendly vehicle the acid waste water as claimed in claim 1 is characterized in that, in above-mentioned A step, adds the calcium carbonate mineral powder in the acid waste water and carries out the mechanical stirring mixing.
3. the method for obtaining rich scandium material between the titanium dioxide environment-friendly vehicle the acid waste water as claimed in claim 1 is characterized in that, in above-mentioned C step, filtrate adds the calcium carbonate mineral powder and carries out the mechanical stirring mixing.
4. the method for obtaining rich scandium material between the titanium dioxide environment-friendly vehicle the acid waste water as claimed in claim 1 is characterized in that, in above-mentioned A step, neutralization is to pH=1.5 for the first time.
5. the method for obtaining rich scandium material between the titanium dioxide environment-friendly vehicle the acid waste water as claimed in claim 1 is characterized in that, in above-mentioned A step, neutralization is to pH=4.2 for the second time.
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| CN201210543476.0A CN102976527B (en) | 2012-12-14 | 2012-12-14 | Method for obtaining scandium-rich material from acidic wastewater of titanium dioxide environment-friendly workshop |
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| CN102976527B CN102976527B (en) | 2014-06-25 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540752A (en) * | 2013-10-14 | 2014-01-29 | 广西冶金研究院 | Method for enriching scandium, titanium and vanadium from sulfuric acid method titanium dioxide waste acid, and for treating waste acid |
| CN104726724A (en) * | 2015-04-20 | 2015-06-24 | 中国恩菲工程技术有限公司 | Method for extracting scandium from nickel laterite ores |
| WO2023274838A1 (en) * | 2021-06-30 | 2023-01-05 | G S A (Environmental) Limited | PROCESS FOR THE RECOVERY OF RARE EARTH METALS FROM WASTE RESIDUES FROM TiO2 PRODUCTION |
| CN116177779A (en) * | 2022-12-09 | 2023-05-30 | 四川大学 | Recycling method of titanium white wastewater |
| JP7463181B2 (en) | 2020-04-22 | 2024-04-08 | Ｊｘ金属株式会社 | How to recover rare metals |
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| CN102275970A (en) * | 2011-05-20 | 2011-12-14 | 攀枝花市微创科技开发有限公司 | Comprehensive utilization method of titanium white waste acid and wastewater |
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Patent Citations (4)
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| JP2002192178A (en) * | 2000-12-22 | 2002-07-10 | Fuji Photo Film Co Ltd | Heavy metal trapping method and heavy metal recovering method |
| CN102011010A (en) * | 2009-09-07 | 2011-04-13 | 杨秋良 | Method for totally extracting vanadium, gallium and scandium by using titanium dioxide hydrolysis waste acid to leach steel slag containing vanadium |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540752A (en) * | 2013-10-14 | 2014-01-29 | 广西冶金研究院 | Method for enriching scandium, titanium and vanadium from sulfuric acid method titanium dioxide waste acid, and for treating waste acid |
| CN103540752B (en) * | 2013-10-14 | 2015-12-23 | 广西冶金研究院 | One is scandium-enriched, titanium and vanadium and useless acid-treated method thereof from titanium dioxide waste acid by sulfuric acid process |
| CN104726724A (en) * | 2015-04-20 | 2015-06-24 | 中国恩菲工程技术有限公司 | Method for extracting scandium from nickel laterite ores |
| JP7463181B2 (en) | 2020-04-22 | 2024-04-08 | Ｊｘ金属株式会社 | How to recover rare metals |
| WO2023274838A1 (en) * | 2021-06-30 | 2023-01-05 | G S A (Environmental) Limited | PROCESS FOR THE RECOVERY OF RARE EARTH METALS FROM WASTE RESIDUES FROM TiO2 PRODUCTION |
| GB2608597A (en) * | 2021-06-30 | 2023-01-11 | G S A Environmental Ltd | Process for the recovery of rare earth metals from waste residues from TiO2 production |
| CN116177779A (en) * | 2022-12-09 | 2023-05-30 | 四川大学 | Recycling method of titanium white wastewater |
| CN116177779B (en) * | 2022-12-09 | 2024-04-19 | 四川大学 | Recycling method of titanium white wastewater |
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| CN102976527B (en) | 2014-06-25 |
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