CN1024684C - Chromium slag leaching and smelting detoxication method - Google Patents
Chromium slag leaching and smelting detoxication method Download PDFInfo
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- CN1024684C CN1024684C CN91102325A CN91102325A CN1024684C CN 1024684 C CN1024684 C CN 1024684C CN 91102325 A CN91102325 A CN 91102325A CN 91102325 A CN91102325 A CN 91102325A CN 1024684 C CN1024684 C CN 1024684C
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- Prior art keywords
- slag
- chromium
- iron
- water
- chrome
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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 of processing and comprehensively utilizing chromium slag by detoxification. The method of the present invention comprises the steps: water-solubility hexavalent chrome and sodium salt are extracted by water immersion from toxic chromium slag produced in the process of chrome salt production; an extract liquid is neutralized by nitric acid, lead nitrate or a lead acetate solution are added to prepare middle chrome, or the recovered extract liquid returns to the original production process for chrome salt production; a material is added to extract slag of the insoluble hexavalent chrome containing water to burn the self-fluxing sintered iron into blocks in a sintering furnace, and the self-fluxing sintered iron is fused and reduced at a high temperature in an iron casting stove or a cyclone furnace to obtain low-chromium cast iron by detoxification. The method has the advantages of thorough detoxification, simple technology, low investment, large processing amount for slag, no secondary pollution, favorable environmental benefit and obvious economic benefit.
Description
The present invention relates to the method for a kind of chromium slag (wet extraction chromium residue) detoxifcation treatment and comprehensive utilization, particularly a kind of with flooding chromium slag melting method for detoxification.
Chinese patent application 88104766.X discloses a kind of method of high-temperature fusion chromium residue detoxifying system cement potash fertilizer chromium cast iron contained.Though this method detoxifcation thoroughly, owing to contain sodium salt more (7～10%) in the chromium slag, direct smelting contains sodium salt chromium slag can make blast furnace produce accretion, destroys furnace charge intensity, makes the furnace charge efflorescence, damages furnace lining, air port etc. simultaneously, shortens blast furnace campaign.In addition, this method makes the higher chromium of utility value enter chromium cast iron contained, has reduced the economic benefit that the chromium slag is handled." vanadium chromium tailings fully utilizes and remove chromic research (two) " (" iron alloy ", (4), 26～30(1987)) disclose the thorough toxicide treatment process of another kind of energy.This method takes to reduce basicity of slag and silicon content in pig iron, adjusts the blast furnace design structure, adjusts wind speed, and the control draught temperature is strengthened measures such as slag alkaline discharging capacity, can control the influence of sodium salt effectively, but belong to passive way.In addition, there is the defective of aforesaid method equally in this method, has reduced the use value of chromium.As for other disinfection disposal of aluminium slag, or detoxifcation is not thorough, or uneconomical economically and be difficult to industrialization.
The objective of the invention is to avoid the weak point of above-mentioned existing method and provide a kind of and the chromium slag thoroughly can be detoxified, can fully utilize chromium contained in the chromium slag again, improve the method for the use value of chromium.
Another object of the present invention provides a kind of blast furnace that prevents and damages, and smelts the method for low-chromium cast-iron.
In order to achieve the above object, technical process (seeing accompanying drawing) and working method that the present invention adopts are: with the chromium slag with Mechanical Crushing to granularity less than 8mm, move in the extraction unit, at normal temperatures and pressures, inject diffusion water or chromium salt production waste water, lixiviate goes out water-soluble sexavalent chrome (Sodium chromate), sodium salt and other water-soluble cpds in the chromium slag.Vat liquor separates with the chromium slag from the water outlet outflow of extraction unit.
With nitric acid vat liquor is neutralized to pH6.0～8.0, adds lead nitrate or plumbic acetate solution, make reaction generate lead chromate.
Lead chromate is cleaned, with pressure filter lead chromate is leached and press dry, put in the drying room, 70～100 ℃ of oven dry down, be ground to the granularity of requirement, just become medium chrome yellow medium yellow, the system waste water that lead chromate produced is lower than national industrial wastewater discharge standard after treatment.
With lixiviate slag and granularity powdered iron ore (iron content 38～55%(weight) less than 6mm) (annotate: below be weight percent), coke is pressed the lixiviate slag: powdered iron ore: mixed coke=1: 1.0～2.4: 0.10～0.28(weight ratio), put in bleed type or the exhausting formula sintering oven, igniting, the back is continuous dries or exhausting, make furnace temperature rise to 1300～1500 ℃, the blended furnace charge is burnt till lump shaped self-fusible iron, and hexavalent chrome reduction is stable trivalent chromium compound in the sintering process.
Because of a large amount of SiO are arranged in the chromium slag
2Exist, so following reaction is further arranged:
With granularity greater than 5mm, self fluxed sinter iron, granularity less than 80mm are pressed sintered iron less than scum (iron content 48～65%) and the coke of 6mm: scum: coke: mixed Wingdale=1: 0.5～2.6: 0.1～1.5: 0.15～0.22(weight ratio), place cast iron stove or cyclone furnaces, under 1350～1500 ℃, through high-temperature fusion, reduction and detoxication, layering separates, and obtains low-chromium cast-iron and nontoxic slag.Its principal reaction has:
Embodiment
With the chromium slag with crusher in crushing to granularity less than 8mm, put into extraction unit.Test is diameter 250mm with extraction unit, the container that high 2.5m makes with steel plate, and charging opening is arranged at top, and water outlet is arranged at the bottom.Each lixiviate adds chromium slag 100Kg(siccative), the about 2m of bed depth.From the tap water or the chromium salt production waste water of 5～50 ℃ of charging opening adding water temperatures, the about 0.5l/min of flow.Water-soluble sexavalent chrome, sodium salt and other water-soluble cpds are dissolved, and the vat liquor that contains leachable flows out from the bottom water outlet.Density loss to 1.8～2.0g/l when the about 85～87g/l of water-soluble hexavalent chromium concentration in the initial stage vat liquor, water-flowing amount to 130～150l, because of content is low, no longer lixiviate is about to the lixiviate slag and pours out, and is standby.Above process repeats 32 times, and shared chromium slag 3200kg gets lixiviate slag 2790kg(siccative after the water logging).The chromium slag contains water-soluble sexavalent chrome 2.94% and contains Na before the water logging
2CO
311.18%, the lixiviate slag contains water-soluble sexavalent chrome 0.74% after the water logging, contains Na
2CO
31.54%.Water-soluble chromic leaching yield is 74.83%, Na
2CO
3Leaching yield be 86.23%, 32 lixiviate altogether vat liquor 4.64m
3, the analytical results of vat liquor sees Table 1.Nitric acid with 5.62～7.91mol/L transfers to pH6.0～8.0 with vat liquor, under constantly stirring, add 10～
Table 1:
Each component concentration (kg/m of pH
3)
Cr
6+SiO
2Fe
3+Al
3+Ca
2+Mg
2+K
+Na
+
12.70????15.18????0.067????0.0048????0.0040????0.021????0.0063????0.309????28.6
12% lead nitrate solution or plumbic acetate solution.Mole ratio by lead nitrate or plumbic acetate and Sodium chromate is that calculating in 1: 0.99 adds solution amount.Reaction is left standstill after finishing, and filters, and with fining process sedimentary lead chromate is cleaned, and uses the pressure filter press filtration at last, 70～100 ℃ of oven dry down, obtains containing the medium chrome yellow medium yellow 456kg of lead chromate 94.76%.It is calculated that the sexavalent chrome rate of recovery in the vat liquor is 98.70%.
The filtrate and the washing water of above-mentioned system medium chrome yellow medium yellow are entered in the wastewater disposal basin, get waste water and clear liquid analysis: pH=8.0, Pb
2+About 0.06ppm, Cr
6+About 23.6ppm.Waste water is through leaving standstill, clarifying, and the medium chrome yellow medium yellow particulate deposits thing that leaches returns in the vat liquor with nitric acid dissolve to be used again.Clear liquid sulfuric acid acidation after the filter adds ferrous sulfate, with Cr
6+Be reduced to Cr
3+, be neutralized to pH=8.0 with lime white again, make Cr
3+And Fe
3+Be converted into oxyhydroxide and precipitate.Filter once more, after the oxyhydroxide waste residue oven dry that leaches is collected, mix the lixiviate slag and participate in sintered ironmaking.Wastewater pH after the processing is about 7.8, Cr
6+＜0.004ppm, pb
2+About 0.06ppm is lower than national specified discharge standard.
Contain Fe in the lixiviate slag
2+About 6.63%, water-soluble sexavalent chrome is about 0.74%, Na
2CO
3About 1.54%.The lixiviate slag is added suitable quantity of water with powdered iron ore (iron content 38～55%), coke in table 2 ratio mix back sintering in the bleed type sintering oven.Bleed type sintering oven furnace diameter 2m, the high 0.8m of upper furnace, stove week is built refractory brick, and lower furnace portion has fire bars, shaft height overall 1.2m, the maximum charge amount 2000kg of stove, about 1300～1500 ℃ of furnace temperature.Agglutinating test repeats eight times, shared lixiviate slag 2570kg, and powdered iron ore 5225kg, coke 535kg produces sintered iron 6383kg.The mean value of each component concentration of sintered iron is as shown in table 3.
Test-results and the standard YB421-64 of Ministry of Metallurgical Industry contrast, the TFe in the product belongs to third-class, and FeO belongs to one-level, and S content belongs to substandard products, but all meets the standard laid down by the ministries or commissions of the Central Government.
Perhaps with mixture sintering in exhausting formula sintering oven of above-mentioned lixiviate slag, powdered iron ore, coke.The furnace diameter 1.0mm of exhausting formula sintering oven, shaft height overall 0.7m, there is fire bars the centre, there is the vent of diameter 0.25m to link to each other under the fire bars with induced exhaust, the single vortex dust-precipitator is established in the vent exit, the maximum charge amount 250kg of stove, the promotion to 1300 of furnace temperature～1500 ℃.Agglutinating test repeats six times, the results are shown in Table 4.Test shared lixiviate slag 208.8Kg for six times, powdered iron ore 470Kg, Jiao
Table 2:
Lot number lixiviate slag (kg) powdered iron ore (kg) coke (kg)
901????300????650????60
902????350????600????40
903????350????600????70
904????250????600????60
905????450????975????100
906????250????600????70
907????350????600????70
908????270????600????65
Add up to 2,570 5,225 535
Table 3:
Component I Fe FeO CaO MgO SiO
2Al
2O
3
%(weight) * 50.94 16.46 6.61 7.89 9.35 5.55
The water-soluble Cr of the full Cr of component
6+K Na S
%(weight) 1.46 0.00153 0.105 0.160 0.113
* calculate by the standard YB421-64 of Ministry of Metallurgical Industry, TFe=Fe/100-(CaO+MgO) * 100
Table 4:
Lot number lixiviate slag (kg) powdered iron ore (kg) coke (kg)
910????35????60????7
911????25????60????7
912????25????60????7
913????37.5????90????10.5
914????45.8????110????12.8
915????40.5????90????11.0
Add up to 208.8 470 55.3
Charcoal 55.3kg gets sintered iron 591kg.The mean value of each component concentration of sintered iron is as shown in table 5.With the standard YB421-64 of Ministry of Metallurgical Industry contrast, product meets the standard laid down by the ministries or commissions of the Central Government, belongs to third-class first grade.
Table 5:
Component TFe FeO CaO MgO SiO
2Al
2O
3
%(weight) * 52.86 15.15 8.78 7.10 7.90 4.06
The water-soluble Cr of the full Cr of component
6+K Na S
%(weight) 1.20 0.012 0.117 0.230 0.072
* annotate with table 3
From above-mentioned analytical results as can be seen, no matter with bleed type or exhausting formula sintering oven sintering, the chromium of various forms all changes stable trivalent chromium compound in the lixiviate slag in sintering process.The content of water-soluble sexavalent chrome and sodium is very low, and sinters piece into, is suitable for blast-furnace smelting and transportation.
The sintered iron that makes is crushed to granularity greater than 5mm,, gets 1786kg, add scum 2984kg again, coke 1660kg, Wingdale 195kg, cylinder iron stove or cyclone furnaces smelting under 1350～1500 ℃ after the mixing less than 80mm.The chemical ingredients of each material sees Table 6.
Table 6:
Each component concentration of name of material (% weight)
Fe Cr CaO MgO SiO
2Al
2O
3
Sintered iron 54.46 1.20 9.00 11.59 9.00 5.38
Scum 65.25 0.014 13.78 4.26 6.71 5.94
Coke 1.66 0.41 7.75 4.30
Wingdale 37.00 5.83 16.75 4.13
Smelting test repeats twice, must contain low-chromium cast-iron 2407kg, smelted furnace cinder 2301kg, and the cast iron chemical ingredients sees Table 7.
Table 7:
Composition Fe C S Si P Mn Cr Ti Cu
%(weight) 94.78 3.42 0.22 0.80 0.11 0.22 0.22 0.39 0.15
Standard GB 718-65 contrast with the pig iron meets the requirements substantially.Contain water-soluble sexavalent chrome in the analysis slag and be lower than 0.04ppm.The present invention compared with prior art sees the following form 8.
Table 8:
High-temperature fusion chromium slag vanadium chromium tailings is comprehensive
Classification the present invention detoxifies and makes the utilization of cement potassium and remove sexavalence
The research (two) of fertile chromium cast iron contained method chromium
Slag contains Cr
6+＜0.04 0.533～1.966＜10
（mg/kg）
Remove Na+ technology and have or not nothing
Detoxifcation thoroughly
The sharp medium chrome yellow medium yellow of chromium slag for comprehensive, chromium cast iron contained contain the vanadium chrome cast iron
With production kind low-chromium cast-iron
Claims (3)
1, a kind of method of chromium residue detoxifying treatment and comprehensive utilization is characterized in that:
1.. under 5～50 ℃ temperature, water or chromium salt production waste water lixiviate chromium slag;
2.. with nitric acid the vat liquor of water logging chromium slag is adjusted into pH6.0～8.0, adds lead nitrate or plumbic acetate formulations prepared from solutions medium chrome yellow medium yellow;
3.. the lixiviate slag behind the water logging chromium slag is pressed the lixiviate slag: powdered iron ore: after the mixed of coke=1: 1.0～2.4: 0.10～0.28 (weight ratio), in sintering oven, burn till self fluxed sinter iron under 1300～1500 ℃ temperature;
4.. press self fluxed sinter iron: scum: coke: after the mixed of Wingdale=1: 0.5～2.6: 0.10～1.5: 0.15～0.22 (weight ratio), place in cast iron stove or the cyclone furnaces, under 1350～1500 ℃, through high-temperature fusion, reduction and detoxication, layering separates, and obtains low-chromium cast-iron and nontoxic slag.
2, method according to claim 1, the concentration that it is characterized in that nitric acid is 5.62～7.91mol/L.
3, method according to claim 1 is characterized in that lead nitrate or plumbic acetate solution are 10～12%(weight).
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91102325A CN1024684C (en) | 1991-04-09 | 1991-04-09 | Chromium slag leaching and smelting detoxication method |
| EP19920302999 EP0508697A1 (en) | 1991-04-09 | 1992-04-03 | A re-calcination and extraction process for the detoxification and comprehensive utilization of chromic residues |
| RO92-200485A RO108787B1 (en) | 1991-04-09 | 1992-04-08 | Integral using of chrome residues and noxious removing working process |
| 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 |
|---|---|---|---|
| CN91102325A CN1024684C (en) | 1991-04-09 | 1991-04-09 | Chromium slag leaching and smelting detoxication method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1065687A CN1065687A (en) | 1992-10-28 |
| CN1024684C true CN1024684C (en) | 1994-05-25 |
Family
ID=4905541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91102325A Expired - Fee Related CN1024684C (en) | 1991-04-09 | 1991-04-09 | Chromium slag leaching and smelting detoxication method |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1024684C (en) |
| RO (1) | RO108787B1 (en) |
Cited By (1)
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115170A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | Method for preparing chromium hydroxide and chloride by detoxified chromium residue |
-
1991
- 1991-04-09 CN CN91102325A patent/CN1024684C/en not_active Expired - Fee Related
-
1992
- 1992-04-08 RO RO92-200485A patent/RO108787B1/en unknown
Cited By (1)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| RO108787B1 (en) | 1994-08-30 |
| CN1065687A (en) | 1992-10-28 |
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