CN1027597C - Method for comprehensive utilization of chrome slag by back-melting - Google Patents

Method for comprehensive utilization of chrome slag by back-melting Download PDF

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Publication number
CN1027597C
CN1027597C CN92100772A CN92100772A CN1027597C CN 1027597 C CN1027597 C CN 1027597C CN 92100772 A CN92100772 A CN 92100772A CN 92100772 A CN92100772 A CN 92100772A CN 1027597 C CN1027597 C CN 1027597C
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chromium
return
slag
sodium
burning
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CN1074888A (en
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司徒其奖
许克明
曾德汉
温志
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Priority to CN92100772A priority Critical patent/CN1027597C/en
Priority to EP19920302999 priority patent/EP0508697A1/en
Priority to US07/865,123 priority patent/US5395601A/en
Priority to JP11515592A priority patent/JP2683763B2/en
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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 present invention relates to a method for the comprehensive utilization of chromium slag by a back-burning process, which provides a supplement of a chromium slag leaching and smelting detoxification method with the Chinese patent application number of 91102325.9. In the method for the comprehensive utilization of chromium slag by a back-burning process, the toxic chromium slag eliminated in the production process of chromium salt is added with a small quantity of chromium mineral powder and sodium carbonate, the mixture of the chromium slag, the chromium mineral powder and the sodium carbonate is put into a back-burning device, the back-burning process is carried out, back-burning agglomerate materials are leached by water to obtain leaching liquid comprising sodium chromate, and the leaching liquid is used for manufacturing chromium hydroxide, chromium oxide or basic chromic sulfate. The method for the comprehensive utilization of chromium slag by a back-burning process can fully recover and utilize sexavalent chromium and trivalent chromium and can also carry out thorough detoxification.

Description

Method for comprehensive utilization of chrome slag by back-melting
The present invention relates to a kind of chromium slag is returned and burn the method for comprehensive utilization that detoxifcation is handled.Method of the present invention is Chinese patent application number 91102325.9 replenishes.
Traditional chrome ore roasting is chromite ore fine to be added inert materials such as soda ash and a large amount of rhombspar, Wingdale make weighting agent, and high-temperature roasting in rotary kiln makes the chromium sesquioxide (Cr in the ore 2O 3) be converted into Sodium chromate (Na 2CrO 4).The molten leaching of Sodium chromate in the grog of water after with roasting, a large amount of useless chromium slags are discharged in the molten back of soaking.At present, one ton of sodium dichromate 99 of every production is discharged 2.5～3 tons of (Sodium chromate per ton is arranged 2.3～2.8 tons approximately) poisonous chromium slags approximately in the chromic salts industry, and remnants have 3～7%Cr in the chromium slag 2O 3, 8～11% Fe 2O 3, 0.5～1.5% water-solubility Cr + 6
The chromium slag returns that to burn principle roughly the same with chrome ore roasting principle, and difference is that the chrome ore roasting is based on chrome ore, allocates rhombspar, Wingdale, soda ash into, the small additions of chromium of arranging in pairs or groups slag; The chromium slag returns burning then based on the chromium slag, allocates small additions of chromium breeze, soda ash into, or adds an amount of coke powder again, does not add rhombspar and Wingdale.Purpose is to make the chromium slag return burning again once.
In the chrome ore roasting process, the Sodium chromate of leaching is used to make sodium dichromate 99, soaks the Cr in the residue chromium slag of back 2O 3And water-solubility Cr + 6All can't utilize, and discard, not only cause serious environmental to pollute, also waste useful resources with the chromium slag.China is poor chromium country, and chromium ore resource is limited, needs the import chrome ore.Will discharge 10.5 ten thousand tons of chromium slags every year in the chromium salt production of the whole nation, contains 5,200 tons of chromium sesquioxide (Cr approximately 2O 3) along with the chromium slag abandons, very unfortunate.The chromium slag returns firing method can make all kinds and the Cr that is difficult in the direct lixiviate toxicide chromium slag 2O 3Be converted into Na again 2CrO 4, Cr 2O 3Be used more effectively, chromium residue detoxifying is more thorough.After the chromium slag returns and burns processing, Cr 2O 3Can reclaim 50～60%, can remove 60～70% water-solubility Cr + 6
The object of the present invention is to provide and a kind ofly all kinds chromium cinder ladle can be drawn together new slag and accumulate for a long time the water-soluble Cr that contains + 6Lower old slag is detoxifcation and comprehensive utilization method thoroughly.
In order to reach above-mentioned purpose of the present invention, can adopt following technical process (seeing accompanying drawing) to realize that its working method is:
(1) with after the chromium slag oven dry, be crushed to granularity 80～100 orders, according to the chromium slag: chromite ore fine: soda ash: the weight batching of coke powder=1: 0.1～0.25: 0.1～0.25: 0～0.16 is than batching, and a little a little water mix the back and add in the stove.Make the stove temperature be elevated to 1000～1200 ℃ gradually, return about 30～60 minutes of burning time, obtain returning overburnt material.The chromium slag returns the also available rotary kiln of burning, returns and burns 1000～1200 ℃ of temperature, 2 hours time.
The chromium slag returns and burns that to learn reaction process as follows:
To return overburnt material and place in the high-rise extraction unit, the Na in the overburnt material is returned in the water filling lixiviate 2CrO 4Promptly gone out by lixiviate.Vat liquor is produced chromic oxide, basic chromium sulfate or medium chrome yellow medium yellow respectively as follows.Lixiviate slag after the lixiviate is handled (comprise lixiviate slag among the embodiment all Click here reason) by Chinese patent application numbers 91102325.9 described methods.
(2) vat liquor to precipitation tank in term, adds sulfur flour or sodium sulphite, with being steam heated to 100 ℃, the Na in the vat liquor with pump delivery 2CrO 4Be converted into chromium hydroxide [Cr(OH) 3].
Chromium hydroxide is sintered into chromic oxide (Cr through the washing of separating and filtering clear water under 1200 ℃ high temperature in calcining furnace 2O 3).
Or in chromium hydroxide, add sulfuric acid or sodium pyrosulfate, make basic chromium sulfate.
Mother liquor behind the separation of hydrogen chromic oxide can add sulfuric acid or sodium pyrosulfate reclaims Sulfothiorine.
(3) the sulfate of ammoniac sodium slag of generation was handled during the also available chromic anhydride of vat liquor was produced, and made basic chromium sulfate.Chromium salt factory is being produced chromic trioxide (CrO 3) time, discharging the deleterious sulfate of ammoniac sodium of a large amount of severe corrosives slag (mainly is NaHSO 4) fused salt, traditionally with Na 2SO 4H 2SO 4Represent, contain H 2SO 435～40%, Na 2SO 445～50%, Na 2Cr 2O 72H 2O2～3%).Water dissolving sulfate of ammoniac sodium slag after sedimentation removes disacidify mud impurity, gets clarifying NaHSO 4Solution.Add vat liquor in the neutralization reaction groove earlier, NaHSO reinjects 4Solution carries out neutralization reaction, and control pH6～7 get neutral chromium acid sodium solution through press filtration, and neutral chromium acid sodium solution is placed in the acidifier, add NaHSO once more 4Acidifying.
Acidizing fluid after the acidifying adds sucrose or formaldehyde, is heated to simultaneously more than 100 ℃, generates basic chromium sulfate and sodium sulfate.
After reacting completely, be cooled to 21～24 ℃, promptly separate out 10 aqueous sodium persulfate crystal, isolate 10 aqueous sodium persulfates, get qualified basic chromium sulfate with whizzer.
The aluminium slag of discharging in the aluminium slag that obtains with press filtration in aforementioned and settled sour mud of chromic anhydride slag and the chromium salt production process focuses in the lump.
(4) vat liquor also can be handled according to Chinese patent application number 91102325.9 described methods, adjusts the pH value with nitric acid, adds lead nitrate and makes medium chrome yellow medium yellow.
Embodiment one:
The chromium slag that test is used consists of: Cr 2O 35.43%, water-solubility Cr + 60.49%, Fe 2O 39.02%, CaO 29.67%, MgO25.90%, SiO 26.38%, Al 2O 36.79%; The chrome ore that uses contains Cr 2O 348.13%.
Go into chromite ore fine 16.6kg, soda ash 21kg, coke powder 10kg, a little a little water, behind the mixer mixing, insert in the disc type chromium slag stove,, return burning under the exhausting condition of negative pressure of 4900～6230Pa at 1000～1200 ℃, return 1 hour burning time, must return overburnt material 174kg, grog contains total chromium (with Cr 2O 3Meter) 11.26%, water-solubility Cr + 6(with Cr 2O 3Meter) 6.58%, Cr 2O 3Return and burn transformation efficiency 58.44%.
To return overburnt material and drop in the extraction unit and add lixiviate, Na 2CrO 4Vat liquor 0.161N 3, contain Na 2CrO 4151.4g/l.Insert in the precipitation reactor, add sulfur flour 7.32kg, directly with being steam heated to 100 ℃, Na 2CrO 4Play reduction reaction with Sulfur.After question response finished, filtering separation and washing obtained chromium hydroxide 23.5kg(weight in wet base), again with the chromium hydroxide oven dry, make chromic oxide 10.7kg(1200 ℃ of following calcinings and contain Cr 2O 392.4%).
Return the lixiviate slag that burns after the lixiviate and contain total chromium (with Cr 2O 3Meter) 1.96%, water-solubility Cr + 60.2%, Fe 2O 310.82%, CaO27.72%, MgO27.68%, SiO 27.31%, Al 2O 36.79%, the chromium slag burns after the lixiviate total chromium utilization ratio 64% in the slag, water-solubility Cr through returning + 6Decreasing ratio 59.18%.
Embodiment two:
Chromium slag, chromite ore fine that test is used are identical with embodiment one, get chromium slag 100kg(butt), adding chromite ore fine 20kg, soda ash 22.5kg, coke powder 9kg, add the water mixing after, in stove, return burning.Return burn temperature, the exhausting negative pressure is identical with embodiment one, returns 35 minutes burning time, must return overburnt material 114kg.Grog contains total chromium (with Cr 2O 3Meter) 12.31%, water-solubility Cr + 6(with Cr 2O 3Meter) 7.57%, Cr 2O 3Return and burn transformation efficiency 61.52%.
To return overburnt material and drop in the extraction unit and add flooding, concentration be the Na of 152.5g/l 2CrO 416.54kg(volume 0.108N 3).Na with alkalescence 2CrO 4Vat liquor is sent in the neutralization reaction groove, and (first in advance water removes sour mud impurity with the dissolving of chromic anhydride slag through sedimentation, makes the NaHSO of proportion 1.41～1.45 to add highly acid sodium bisulfate 4Solution), be neutralized to pH=6.5, remove aluminium hydroxide with the pressure filter press filtration subsequently, get neutral chromium acid sodium solution.
Neutral chromium acid sodium solution is sent into the acidification reaction groove, add above-mentioned sodium bisulfate once more, make the Sodium chromate acidifying transfer Na to pH=1.5～2 2Cr 2O 7, then add 2.18kg sucrose crystal grain slowly, and constantly stir, make it be converted into basic chromium sulfate.There is not Cr after testing + 6, show that reduction reaction is complete.Leave standstill and feed water coolant, make solution temperature reduce to 22 ℃, the Na in the solution to the reactive tank insulation jacket 2SO 4Become 10 aqueous sodium persulfate crystal and separate out, with whizzer it is separated at last, get liquid basic chromium sulfate 63.4kg, through check Cr(OH) SO 4Contain Cr 2O 311.83%, basicity 40.22% meets product requirement.The poisonous chromic anhydride waste residue of the shared 69kg strongly-acid of present embodiment makes NaHSO 4Aqueous solution 0.069N 3
Embodiment three:
Proportioning and test conditions by embodiment two repeat test, must return overburnt material 108kg, and grog contains total chromium (with Cr 2O 3Meter) 11.84%, water-solubility Cr + 6(with Cr 2O 3Meter) 7.29%, Cr 2O 3Return and burn transformation efficiency 61.56%.To return overburnt material and drop in the extraction unit and add lixiviate, the Na of concentration 154g/l 2CrO 4Solution 15kg(volume 0.098N 3), with Na 2CrO 4Solution is heated to 100 ℃, adds sulfur flour 4.5kg, carries out reduction reaction, also uses hot wash after filtration, gets chromium hydroxide 9kg.Under the condition of heated and stirred, add NaHSO 4Solution 0.018N 3, making basic chromium sulfate (liquid) 56.26kg, the liquid basic chromium sulfate contains Cr after testing 2O 311.2%, basicity 39.8%.
Embodiment four: (table 1 is seen the literary composition back)
With above-mentioned chromium slag oven dry, be crushed to granularity 80～100 orders, get 100 parts, allocate 25 parts of chrome ores into, 16 parts of soda ash after mixer mixes, are inserted in Φ 1800 * 28M rotary kiln and are returned burning, return and burn 1050 ℃ of temperature, return 2 hours burning time.Test is carried out 5 batches altogether, and the result is as follows: (table 2 is seen the literary composition back)
5 batches the test the grog that produces all get alkaline vat liquor 30.96N with flooding 3, Na 2CrO 4Concentration 300.37g/l, Na 2CrO 4Amount is scaled Na for 9299.7kg 2Cr 2O 72H 2O8555.4kg, leaching yield 85%.The alkaline vat liquor in test back all changes the sodium dichromate 99 Production Flow Chart over to.
Present embodiment co-processing chromium slag 65010kg gets grog 52983kg, returns and burns transformation efficiency 82.23%, leaching yield 85%.Chromium slag ingredient after the lixiviate: total chromium (Cr 2O 3) 3.56%, water-solubility Cr + 6(with Cr 2O 3Meter) 0.75%, Fe 2O 311.85%, CaO26.61%, MgO25.25%, SiO 26.16%, Al 2O 310.96% and handle before the chromium slag ratio, total chromium extracts 49.14%, water-solubility Cr + 6Remove 64.95%.Present method can fully be recycled sexavalent chrome and trivalent chromium, and thoroughly detoxifcation.
The chromium slag that uses and the composition of chrome ore are as follows:
% Cr 2O 3Water-solubility Cr + 6Fe 2O 3CaO MgO Sio 2Al 2O 3
(with Cr 2O 3Meter)
Chromium slag 7.0 2.14 10.16 31.68 23.8 5.4 9.96
Chrome ore 25.69/11.68 1.2 27.24 15.5 11.04
Batch total chromium grog of chromium slag chrome ore soda ash output grog grog water Cr + 6Transformation efficiency
（kg）????（kg）????（kg）????（kg）????（%）????（%）????（%）
1????7410????1800????1134????9485????9.26????8.7????93.95
2????16800????4200????2646????12820????13.53????10.6????78.34
3????12000????3000????1890????10738????13.30????9.23????69.40
4????14400????3600????2268????10110????10.47????9.81????93.70
5????14400????3600????2268????9830????11.69????9.59????81.99
Add up to 65,010 16,200 10,206 52,983 11.65 9.58 82.23

Claims (4)

1, a kind of method of chromium residue detoxifying treatment and comprehensive utilization, it is characterized in that: according to the chromium slag: chromite ore fine: soda ash: the weight batching of coke powder=1: 0.1～0.25: 0.1～0.25: 0～0.16 is than batching, a little a little water, mix back adding stove and return burning, return and burn 1000～1200 ℃ of temperature, return 30～60 minutes burning time, or adding rotary kiln internal return burns, return and burn 1000～1200 ℃ of temperature, return 2 hours burning time, water carries out lixiviate to returning overburnt material then.
2, method according to claim 1, it is characterized in that described return overburnt material with flooding after, add sulfur flour or sodium sulphite in the vat liquor, with being steam heated to 100 ℃, obtain chromium hydroxide, be sintered into chromic oxide then.
3, method according to claim 1, it is characterized in that described return overburnt material with flooding after, add the sodium bisulfate neutralization in the vat liquor, acidifying adds sucrose or formaldehyde again, is heated to 100 ℃, generates basic chromium sulfate and sodium sulfate.
4, method according to claim 3 is characterized in that described sodium bisulfate is the aqueous solution of sodium pyrosulfate slag.
CN92100772A 1991-04-09 1992-01-30 Method for comprehensive utilization of chrome slag by back-melting Expired - Fee Related CN1027597C (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN92100772A CN1027597C (en) 1992-01-30 1992-01-30 Method for comprehensive utilization of chrome slag by back-melting
EP19920302999 EP0508697A1 (en) 1991-04-09 1992-04-03 A re-calcination and extraction process for the detoxification and comprehensive utilization of chromic residues
US07/865,123 US5395601A (en) 1991-04-09 1992-04-08 Re-calcination and extraction process for the detoxification and comprehensive utilization of chromic residues
JP11515592A JP2683763B2 (en) 1991-04-09 1992-04-09 Recalcination and extraction methods for detoxification and integrated utilization of chromium residues

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN92100772A CN1027597C (en) 1992-01-30 1992-01-30 Method for comprehensive utilization of chrome slag by back-melting

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CN1074888A CN1074888A (en) 1993-08-04
CN1027597C true CN1027597C (en) 1995-02-08

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101504143B (en) * 2009-03-04 2013-02-13 潍坊华友亚麻纺织有限公司 Technique for using leather products industrial waste as fuel

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Publication number Priority date Publication date Assignee Title
CN101871046A (en) * 2010-06-29 2010-10-27 青川县天运金属开发有限公司 Method for recycling heavy metal pollution wastes
CN102718260B (en) * 2012-07-04 2014-04-30 甘肃锦世化工有限责任公司 Production method for coproduction of chromium chloride and chromic carbonate
CN106186067B (en) * 2016-07-06 2017-11-17 于佳湲 A kind of method using chromite as raw material clean manufacturing chrome green
CN111826533A (en) * 2020-07-22 2020-10-27 中信锦州金属股份有限公司 Method for producing low-silicon high-purity metal chromium by calcium-free roasting of sodium chromate alkaline solution through low-temperature impurity removal

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101504143B (en) * 2009-03-04 2013-02-13 潍坊华友亚麻纺织有限公司 Technique for using leather products industrial waste as fuel

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