CN1063232A - Countercurrent circulation sectional leaching separation method for comprehensive utilization of chromium slag - Google Patents
Countercurrent circulation sectional leaching separation method for comprehensive utilization of chromium slag Download PDFInfo
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- CN1063232A CN1063232A CN91108352A CN91108352A CN1063232A CN 1063232 A CN1063232 A CN 1063232A CN 91108352 A CN91108352 A CN 91108352A CN 91108352 A CN91108352 A CN 91108352A CN 1063232 A CN1063232 A CN 1063232A
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- leaching
- slag
- chromium
- chromium slag
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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
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Abstract
The invention achieves the purpose of thoroughly detoxifying and fully utilizing the chromium slag according to the solubility difference of hydroxides of main components in the chromium slag under different acidity conditions. In the process, a plurality of leaching ponds are combined in series, and the chromium slag is leached for a plurality of times in a mode of hydrochloric acid countercurrent circulation sectional leaching, and is reduced and detoxified for a plurality of times, and meanwhile, the automatic enrichment and separation of main components in the slag are realized. After the separated substances are purified, the light magnesium oxide, the calcium sulfate hemihydrate, the chromium oxide and the aluminum oxide can be respectively prepared, and the final detoxified slag can also be used as a soil conditioner, so that the method has obvious economic benefit and environmental benefit.
Description
The invention belongs to the waste residue processing method in the inorganic chemical industry.This method be with the chromium slag with progressively segmentation leaching of leaching liquid, that has not only realized the chromium slag in leaching process thoroughly removes poison, but also with the compound in the chromium slag one by one segmentation separate, reach the purpose of comprehensive utilization chromium slag.
Chromium slag pollution on the environment is a long-term difficult problem that perplexs chromium salt production enterprise.This has all been carried out extensive studies both at home and abroad, the patent of application is more, and its technological core is to remove Cr
6+Ion.A kind of method is with Cr with reducing agent
6+Be reduced to Cr
3+And reach the purpose of chromium slag detoxification, promptly be an example as " the nontoxic extraction Ca. and Mg method of chromium slag reduction " (Chinese patent, patent No. 85105628A); Another kind method is with Cr
6+Change the slightly solubility chromate into, not only realized the detoxification of chromium slag, but also a kind of industrial chemicals is provided, (Chinese patent, application number 89104693.3, publication number CN1038771A) is again an example as " eliminating poison of chromium cinder comprehensive use ".But preceding a kind of method causes the difficulty of Separation of Solid and Liquid owing to the generation of hydroxide colloid mixture, and it is not thorough to remove poison simultaneously, therefore is difficult to implement in industrial production; Though then a kind of method has carried out removing once more poison, and the residual hazard situation of removing in the malicious waste residue is not provided the detection data, thoroughly also can not cause secondary pollution if remove poison.Above-mentioned two methods are not all separated utilization to the iron in the chromium slag, aluminium, silicon simultaneously, they are entered in the waste residue that removes poison again, and residual low price chromium regenerates chromic possibility in the waste residue, in this sense, put method to the separation of chromium slag with to remove poison all be inadequate for these two kinds.
Purpose of the present invention utilizes the dissolving of compound in different sour environments in the slag to realize automatic enrichment and separate with sedimentation equilibrium, finally realize the separation of calcium, magnesium, iron, aluminium, chromium, silicon, thereby reached the purpose that the chromium slag thoroughly removes poison and comprehensive utilization.
Method of the present invention is, at first chromium sizing become 50～80 purpose fine powders, and Main Ingredients and Appearance is as follows in the slag by analysis:
Chromium (Cr
2O
3Meter) 3～7%
Wherein water-soluble Cr VI (Cr
2O
3Meter) 0.5～0.6%
Solubility in acid Cr VI (Cr
2O
3Meter) 0.85～1%
Iron (Fe
2O
3Meter) 10～13%
Aluminium (Al
2O
3Meter) 5～7%
Silicon (SiO
2Meter) 8～11%
Calcium (CaO meter) 28～33%
Magnesium (MgO meter) 21～30.5%
Leaching for the first time:
The chromium slag is poured in the first leaching pond (seeing accompanying drawing), leaching liquid in the second leaching pond is injected the first leaching pond, this leaching liquid mainly is the hydrochloric acid solution of trivalent aluminium, chromium, iron, PH=3～5.When leaching, blast air agitation, finish through 5 hours afterreactions, leaving standstill 3 hours, the pH value of supernatant liquor is greater than 5, and its chemical reaction is:
Fe in like manner
3+, Al
3+Also generate Fe(OH respectively)
3↓ and Al(OH)
3↓.Leaching liquid and slag generation chemical reaction in this chemical environment, the Cr in the leaching liquid
3+, Fe
3+, Al
3+Form precipitation of hydroxide and enter in the slag, and Cr VI in the slag and calcium, magnesium enter in the leaching liquid.At this moment mainly contain Ca in the supernatant liquor
2+, Mg
2+, Cr
6+, then the supernatant liquor suction filtration is come out, Cr
6+Be reduced to Cr
3+, extract the compound of calcium magnesium again.
Remove poison:
In the supernatant liquor that takes out, add akali sulphide, Cr
6+Reduction becomes Cr
3+Generate precipitation of hydroxide, the small amounts of iron ion also precipitates with the form of iron sulfide in the solution.The product of dolomite after roasting being digested and be mixed with concentration is 30% digestion breast (it consists of the hydroxide of magnesium, calcium).This digestion breast is added in the above-mentioned solution, pH value is adjusted to 6.5～7 filter then, filter residue stays to be done further to utilize.The chloride of the main calcic of gained filtrate, magnesium separates again.
The separation of magnesium:
In above-mentioned filtrate, under continuous stirring condition, slowly add 30% digestion breast, stirred one hour after reaction is finished, then filtration control PH=8～8.5 again.At this moment magnesium has nearly all generated Mg(OH in the filtrate)
2↓ precipitation.And calcium also is retained in the filtrate.With Mg(OH)
2Washing of precipitate, refining, dry, roasting get content at last greater than 93% light magnesium oxide product.
The separation of calcium:
In the solution behind separating magnesium, slowly add 98% sulfuric acid, at this moment Ca
2+With CaSO
4Form precipitate, the hydrochloric acid that reaction generates will be used by the leaching liquid as slag in subsequent handling.With sedimentation and filtration, washing, dehydration, drying, make content greater than 98% half-H 2 O calcium sulphate 170 ℃ of roastings.It can be used for building materials, and decoration industry also can be used as the raw material of the potash fertilizer potassium sulfate of no chlorine root.
Leaching for the second time:
With the slag after the leaching for the first time, put into the second leaching pond, leaching liquid in the 3rd leaching pond is injected the second leaching pond, this leaching liquid mainly is ferric hydrochloride solution, air agitation is used in PH=3～5, after reaction in 5 hours finishes, left standstill again 3 hours, this moment supernatant liquor pH value no change almost.Its chemical reaction is:
Leaching liquid and slag generation chemical reaction in this chemical environment, the Fe in the leaching liquid
3+Form precipitation of hydroxide and enter in the slag, and the hydroxide of aluminium in the slag and chromium enters in the leaching liquid with the form of soluble-salt hydrochlorate, also partly stripping of the solubility in acid Cr VI in the slag at this moment enters in the leaching liquid.
Remove poison:
Take out above-mentioned after enrichment leaching liquid and to wherein adding akali sulphide, regulate PH=3～3.2, at this moment Cr with reclaiming hydrochloric acid
6+Be reduced into and be Cr
3+, the form of small amounts of iron ion generation iron sulfide precipitates in the leaching liquid, and filtered filtration residue stays for subsequent handling and uses.
Separating of aluminium and chromium:
Above-mentioned filtrate is added 30% digestion breast, regulate PH=5～5.5, generate the precipitation of hydroxide of trivalent aluminium and chromium, filter, filtrate is returned the second leaching pond, filter cake washing, obtain aluminium, trivalent chromium compound after the drying, it can make abrasive material as required, catalyst or corresponding salt.
Leaching for the third time:
After twice leaching, the Main Ingredients and Appearance of slag is the hydroxide and the oxide of iron, and silica and acid non-soluble substance wherein also have a spot of solubility in acid Cr VI not leach fully.Slag after twice leaching is put into the 3rd leaching pond, the leaching liquid in the 4th leaching pond is injected the 3rd leaching pond, this leaching liquid is the dilute hydrochloric acid solution that contains iron ion, and pH value is less than 3, and operation is with aforementioned.At this moment, the reaction of leaching liquid and slag is mainly:
Iron also has a little solubility in acid Cr VI to enter leaching liquid by entering leaching liquid in the slag.
Remove poison:
Taking-up is through the solution of enrichment, leaching is for the first time removed the filter residue (its Main Ingredients and Appearance is the sulfide and the trivalent chromium hydroxide of iron) that filter residue behind the poison and leaching for the second time remove behind the poison to add wherein, add recovered acid again and regulate PH=2, at this moment a small amount of Cr VI is reduced to Cr
3+, iron in the filter residue and chromium all enter solution, have not only realized further removing poison, have reclaimed chromium and iron again.
The separation of iron:
Digestion breast with 30% is adjusted to 3.2 with the PH of above-mentioned solution, and at this moment iron precipitates with the form of hydroxide, and filtration, filtrate are returned in the 3rd leaching pond.With after the washing of precipitate in 800～900 ℃ of roastings, obtain content and be higher than 92% Fe
2O
3, this product can be made pigment.
The 4th leaching:
Through the slag of continuous three leachings, Main Ingredients and Appearance is SiO
2Acid non-soluble substance, small amount of Fe
2O
3And the acid sexavalence sleever armpit part of very micro-end leaching.This slag is put into the 4th leaching pond, inject the leaching liquid of fetching from the 5th leaching pond, this leaching liquid is the watery hydrochloric acid that contains the small amounts of iron ion, PH less than 3 it be highly acid, the solubilized small amount of Fe
2O
3, and further leach the solubility in acid Cr VI and make it to enter solution.Operation such as preceding filters rear filtrate and injects three leaching ponds, ground, and filter residue enters the 5th leaching pond, and iron is not only further reclaimed in current leaching, and is the process of further removing poison.
The 5th leaching:
Add in the above-mentioned filter residue after the salt acid recovery that will when leaching for the first time, be produced in the calcium separation circuit process, it can make the chromium of mineral phase structure wherein dissolved, leaching liquid makes the drop hexavalent chromium reduction that is dissolved except that the filter residue (it mainly is FeS) behind the poison carries out removing completely poison adding for the second time then.Filter rear filtrate and directly inject the 4th leaching pond.Filter residue with in the ammoniacal liquor and after obtain SiO at last
2And acid non-soluble substance, it can be used as soil conditioner and inserts.
In sum, the present invention has realized the concentration and separation of thoroughly removing poison and Main Ingredients and Appearance of chromium slag by the adverse current segmentation leaching of chromium slag and leaching liquid, makes the chromium slag turn waste into wealth, turn harm into good.
Among the present invention, different components realize that the basic principle of enrichment is to utilize Ca
2+, Mg
2+, Cr
3+, Al
3+, Fe
3+Hydride deliquescent difference realizes under different acidity.Fe for example
3+Generate Fe(OH)
3The pH value of precipitation is 3, and pH value is all less than 3 in the 4th, the 5th leaching pond, and iron can only be with Fe in this chemical environment
3+Form be present in leaching liquid, and in the one the second leaching ponds, pH value is all more than or equal to 3, iron can only be with Fe(OH in this chemical environment)
3The form of ↓ precipitation is present in the slag.In countercurrent leaching process, first, second leaching pond resembles twice " fence " and has stoped iron to run off from leaching liquid, leaching liquid must have been surrendered iron and just can flow away, and the 4th, the 5th leaching pond has also prevented that as twice " fence " iron runs off from slag, and slag must " be emitted iron " to come and just can be gone out.Final iron can only " be caught up with " in the 3rd leaching pond, obtains enrichment, and then realizes separating.The enrichment principle of other component also is the same.
It is to be noted especially in counter-current extraction process of the present invention, as long as the initial concentration of hydrochloric acid in 10～20% scopes, replenishes 30% hydrochloric acid in case of necessity, calcium in the chromium slag, the magnesium integral molar quantity is 1: 2.01～1: 2.05 with the ratio of hydrochloric acid integral molar quantity.Because the precipitation between many components, dissolution equilibrium just can make the pH value in each pond keep basicly stable, reaches technological requirement, and need not carry out the adjusting of pH value on technology.This brings to production control and is convenient greatly.
In the method for the present invention, slag to be moved to the just convenience in order explaining of next leaching pond from a leaching pond, and in actual production, not need to do like this.For example after the 5th the leaching pond slagging-off, new slag is just poured this pond into, at this moment the 5th leaching pond has just become the first leaching pond, and the first original leaching pond has just become the second leaching pond, and the like, so each pond is slag bath during ordinary production, is again the slag input pond, they are cascaded and recycle, as long as this do proper arrangement with pipeline just can accomplish.About 60 hours of whole circulation leaching process, but can remove once finishing slag in per 12 hours, advance the chromium slag one time.The size in pond is according to handling how many calculating of the quantity of slag and deciding, and available polyvinyl chloride is made lining material.
In the method for the present invention, need in each circulation leaching, all to from the second leaching pond, not take out leaching liquid, be used for separating purifying making Al
2O
3, Cr
2O
3Batch mixing; Take out leaching liquid from the 3rd leaching pond, be used for separating the system Fe that purifies
2O
3Product, and, treat the Cr in the leaching liquid normally through after 4～5 circulation leachings
3+, Al
3+And Fe
3+Fully after the enrichment, just carry out the separation recovery of an above-mentioned substance.
In the method for the present invention, concentration of hydrochloric acid can be thinning after the circulation leaching, therefore when concentration of hydrochloric acid is lower than 10%, reach 10～20% technological requirement with control circulation leaching concentration of hydrochloric acid with the filtrate behind the separating magnesium by concentrating.When adopting part to take out to concentrate when being used to regulate concentration after making it reach full closing, contain sodium salt in the solution and separate out and to be recycled.
In of the present invention the method, the circulation leaching separates to be carried out at normal temperatures and pressures, and equipment is simple, and is easy to operate, and it is all very remarkable to remove malicious thoroughly economic benefit and environmental benefit.
The inventive method embodiment: (repeatedly mean value) as a result
Drop into material:
Chromium slag sulfuric acid (98%) replenishes hydrochloric acid (30%)
1 kilogram 1.8 kilograms 0.2 kilogram
Dolomite is through 1000 ℃ of roasting materials
0.8 kilogram
Isolated product:
MgO CaSO
41/2H
2O Fe
2O
3
0.38 2.1 kilograms 0.1 kilogram of kilogram
≥93%??≥98%??≥92%
Cr VI can't check
Cr
2O
3.Al
2O
3SiO
2And acid non-soluble substance
0.06 kilogram is decided on slag
Cr VI can't check
Accompanying drawing of the present invention is the main technique flow process that is used to discuss the circulated in countercurrent segmentation leaching partition method that chromium slag for comprehensive utilizes.
Claims (10)
1, a kind of eliminating poison of chromium cinder method of comprehensive utilization, it is characterized in that to fill a plurality of leachings pond tandem compound of chromium slag, adopt hydrochloric acid to carry out adverse current segmentation leaching mode, the chromium slag is repeatedly being leached, when reduction removes poison, realized the automatic concentration and separation of each component in the slag.
2, the method for claim 1 is characterized in that being divided into four leaching enrichment sections carrying out segmentation when leaching according to the acidity difference, i.e. PH＜3 section, the changeover portion between PH＜3 and PH=3～5, PH=3～5 section and PH＞5 section.
3,, it is characterized in that being silica and acid non-soluble substance in the chromium slag in PH＜3 section enrichment as claim 1,2 described methods.
4, as claim 1,2 described methods, it is characterized in that between PH＜3 and PH=3～5 the changeover portion enrichment be iron in the chromium slag.
5,, it is characterized in that being chromium and aluminium in the chromium slag in PH=3～5 section enrichment as claim 1,2 described methods.
6, as claim 1,2 described methods, it is characterized in that PH＞5 section enrichment be calcium, magnesium and Cr VI in the chromium slag, after will taking out the liquid hexavalent chrome reduction and removing poison and leach, first separating magnesium.Separating calcium again.
7,, it is characterized in that the mole total amount of calcium, magnesium in the chromium slag and the mole total amount ratio that leaches with hydrochloric acid are 1: 2.01～1: 2.05 as claim 1,2 described methods.
8,, it is characterized in that leaching the initial concentration of usefulness hydrochloric acid in 10～20% scope as claim 1,2 described methods.
9, as claim 1,2 described methods, it is characterized in that hydrochloric acid generates hydrochloride in leaching process, after deliming, generate hydrochloric acid again and carry out recycling.
10, as claim 1,2 described methods, with akali sulphide hexavalent chrome reduction is removed the filter residue that the poison back produces, turn back in the separation circuit of iron and go.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91108352A CN1033841C (en) | 1991-11-21 | 1991-11-21 | Countercurrent circulation sectional leaching separation method for comprehensive utilization of chromium slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91108352A CN1033841C (en) | 1991-11-21 | 1991-11-21 | Countercurrent circulation sectional leaching separation method for comprehensive utilization of chromium slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1063232A true CN1063232A (en) | 1992-08-05 |
| CN1033841C CN1033841C (en) | 1997-01-22 |
Family
ID=4909251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91108352A Expired - Fee Related CN1033841C (en) | 1991-11-21 | 1991-11-21 | Countercurrent circulation sectional leaching separation method for comprehensive utilization of chromium slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1033841C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102755985A (en) * | 2012-07-10 | 2012-10-31 | 辽宁沈宏集团股份有限公司 | Integral leaching detoxication and landfill treatment method of chromium slag |
| CN102825060A (en) * | 2012-09-10 | 2012-12-19 | 武汉钢铁(集团)公司 | Treatment method for chromium-containing waste residue in steel industry |
| CN103255294A (en) * | 2012-05-02 | 2013-08-21 | 唐翔 | Comprehensive reuse process of ferrochrome smelting slag |
| CN106929698A (en) * | 2015-12-30 | 2017-07-07 | 核工业北京化工冶金研究院 | A kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome |
| CN108642279A (en) * | 2018-04-13 | 2018-10-12 | 中南大学 | A kind of method that mixture of sulfuric phosphoric acid pressurization adverse current decomposes wolframite |
-
1991
- 1991-11-21 CN CN91108352A patent/CN1033841C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103255294A (en) * | 2012-05-02 | 2013-08-21 | 唐翔 | Comprehensive reuse process of ferrochrome smelting slag |
| CN102755985A (en) * | 2012-07-10 | 2012-10-31 | 辽宁沈宏集团股份有限公司 | Integral leaching detoxication and landfill treatment method of chromium slag |
| CN102755985B (en) * | 2012-07-10 | 2015-04-22 | 辽宁沈宏集团股份有限公司 | Integral leaching detoxication and landfill treatment method of chromium slag |
| CN102825060A (en) * | 2012-09-10 | 2012-12-19 | 武汉钢铁(集团)公司 | Treatment method for chromium-containing waste residue in steel industry |
| CN102825060B (en) * | 2012-09-10 | 2015-03-25 | 武汉钢铁(集团)公司 | Treatment method for chromium-containing waste residue in steel industry |
| CN106929698A (en) * | 2015-12-30 | 2017-07-07 | 核工业北京化工冶金研究院 | A kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome |
| CN106929698B (en) * | 2015-12-30 | 2019-02-26 | 核工业北京化工冶金研究院 | A kind of processing method of chromium slag nitration mixture enhanced leaching-extraction and recovery siderochrome |
| CN108642279A (en) * | 2018-04-13 | 2018-10-12 | 中南大学 | A kind of method that mixture of sulfuric phosphoric acid pressurization adverse current decomposes wolframite |
| CN108642279B (en) * | 2018-04-13 | 2020-05-26 | 中南大学 | Method for decomposing wolframite by pressurizing and countercurrent sulfur and phosphorus mixed acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1033841C (en) | 1997-01-22 |
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