CN106734062A - It is a kind of iron vitriol slag is solidified after for the method for filling mine - Google Patents
It is a kind of iron vitriol slag is solidified after for the method for filling mine Download PDFInfo
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- CN106734062A CN106734062A CN201611073089.XA CN201611073089A CN106734062A CN 106734062 A CN106734062 A CN 106734062A CN 201611073089 A CN201611073089 A CN 201611073089A CN 106734062 A CN106734062 A CN 106734062A
- Authority
- CN
- China
- Prior art keywords
- iron vitriol
- vitriol slag
- slag
- iron
- filling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002893 slag Substances 0.000 title claims abstract description 56
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 title claims abstract description 39
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000011049 filling Methods 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004568 cement Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 9
- 239000000292 calcium oxide Substances 0.000 claims abstract description 9
- 238000007711 solidification Methods 0.000 claims abstract description 9
- 230000008023 solidification Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 239000008235 industrial water Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 229920002401 polyacrylamide Polymers 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 235000019353 potassium silicate Nutrition 0.000 claims description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- 230000006835 compression Effects 0.000 claims description 9
- 238000007906 compression Methods 0.000 claims description 9
- 230000002308 calcification Effects 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- -1 washed-residue Substances 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 238000002386 leaching Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract 1
- 229910052785 arsenic Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 208000004434 Calcinosis Diseases 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/20—Agglomeration, binding or encapsulation of solid waste
- B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B1/00—Dumping solid waste
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses the process after a kind of solidification of iron vitriol slag for filling in mine.The method is, by two sections of washings of iron vitriol slag, to wash rear liquid and return to former nickel processing system industrial water, washes rear slag and is dispersed in water, add quick lime, PFS, hydrogen peroxide oxidation is used after being sufficiently stirred for, the solidification of the additives such as cement, PAM is finally allocated into, for replacing part filling in mine aggregate.This method greatly reduces filling in mine cost, solves the long-term of iron vitriol slag and stores up problem, cost-effectively realizes the secondary utilization of iron vitriol slag.By detection, the leaching characteristic of heavy metal complies fully with country in the firming body sample for obtaining《Hazard waste landfill Environmental capacity standard》.
Description
Technical field
The present invention relates to the innoxious process for treating field of solid kind discarded object, relate in particular to one kind and consolidate iron vitriol slag
The method for being used to fill mine after change.
Background technology
The main purification method of iron is yellow modumite method in nickel cobalt wet smelting process, and the method is although simple to operate, examination
Agent consumption is few, low production cost, but there is the shortcomings of quantity of slag is big, iron vitriol slag stability is poor, heap sustainability is bad.General smeltery is equal
Slag can be selected to build nearby to store up the iron vitriol slag that yellow modumite method is produced, the land resource of preciousness, Er Qietie is not only taken
Heavy metal in alum slag, such as Ni, Zn, Cu, Pb, As, under the conditions of storing up naturally can continuous dissolution so as to polluted underground water and
Soil, causes environmental pollution.The innoxious technique for fixing of current iron vitriol slag has high temperature sintering, reduction roasting-magnetic separation, extraction
Deng, but because operation cost is high, cannot popularize application in an all-round way.
The content of the invention
The technical problems to be solved by the invention are directed to shortcoming of the prior art and provide one kind and solidify iron vitriol slag
Afterwards be used for fill mine method, this method reduce the cost of filling in mine, and avoid the heavy metal in iron vitriol slag due to
The long-term pollution stored up to natural conditions, for the treatment of iron vitriol slag provides a kind of new direction.
Adopted the following technical scheme that to solve technical problem of the invention：
It is a kind of iron vitriol slag is solidified after for the method for filling mine, comprise the following steps that：
（1）Iron vitriol slag is washed, wherein liquid-solid ratio is 2-3:1, washed-residue is obtained after agitator treating 20-30min, wash rear liquid and return to original
Nickel processing system industrial water；
（2）Solidification：Step（1）The washed-residue of gained adds water, and polyaluminum sulfate is added after adding quick lime calcification 10-15min
Iron PFS is sufficiently stirred for adding hydrogen peroxide, cement, waterglass and the polyacrylamide PAM that mass fraction is 30 % after 5-10min
Mix 10-20min in trommel mixer, mixing makes iron vitriol slag condense integral Binder Materials, overall Binder Materials 21-28 days
Compression strength reaches 11Mp, and wherein washed-residue is with the mass ratio of each additive, washed-residue：Quick lime：Bodied ferric sulfate：Dioxygen
Water：Cement：Waterglass=3-2.5:1-2:0.25-0.3:0.15-0.2:3-3.5:0.23-0.3；Polyacrylamide PAM with wash
The mass ratio for washing slag is 0.00015:1；
（3）Filling：By step（2）The outdoor maintenance of firming body of gained, temperature is 25-30 DEG C, and 10- is crushed to after 21-28 days
12mm is used for filling in mine.
The iron vitriol slag is iron content to be removed produced by iron using yellow modumite method in nickel, the cobalt wet smelting process of 20-25%
Iron vitriol slag.
The step（1）The washing of middle iron vitriol slag uses two sections of countercurrent washings, and two sections of wash waters return to first wash.
Step 2 reclaimed water, washed-residue, cement, bodied ferric sulfate, hydrogen peroxide, waterglass, the various additions of polyacrylamide
Ratio of mud when agent is mixing cured in trommel mixer is 0.45-0.50.
The present invention will remove iron vitriol slag produced by iron in nickel, the cobalt wet smelting process of iron content 20-25% using yellow modumite method
After washing, the washed-residue of gained adds a small amount of quick lime and makees activator, and PFS absorption adds hydrogen peroxide oxidation after being sufficiently stirred for, then
With cement and other additives（Adding ingredient proportioning is shown in Table 1）Mixing makes iron vitriol slag be condensed into the entirety of compression strength intensity 11Mp
Binder Materials.By being crushed to 10-12mm after the outdoor maintenance in 28 days cycles, filling in mine, obturation 28 to be used for instead of aggregate
Its compression strength >=5Mpa, meets the requirement of mine filler.
Table 2 prepares overall Binder Materials iron vitriol slag and solidifies each dispensing proportioning
| Washed-residue | Lime | PFS | H2O2（30%） | Cement | Waterglass | PAM | The ratio of mud |
| 3-2.5 | 1-2 | 0.25-0.3 | 0.15-0.2 | 3-3.5 | 0.23-1 | 0.15g/（Kg washed-residues） | 0.45-5.0 |
After reaction terminates, toxicity characteristic leaching procedure is carried out to solidification Binder Materials, according to《Leaching toxicity from solid waste method:Sulfuric acid
Nitrate method》(HJ/T299-2007), are detected, each poisonous and harmful element content in leachate using atomic fluorescence spectrum
Meet country《Hazard waste landfill Environmental capacity standard》（GB18598-2001）, can reach hazardous waste security landfill people
The limit value that standard specifies.
From technical scheme disclosed above, the method for the present invention is simple to operate, can make the iron containing various heavy
Alum slag safe and convenient ground is used for filling in mine, has both solved the problems, such as that slag was stored up, also for melting waste slag treatment provides a kind of new
Technology path, with universal society generalization meaning.
Brief description of the drawings
Fig. 1 is present invention process flow chart.
Specific embodiment
Embodiment 1
It is a kind of iron vitriol slag is solidified after for the method for filling mine, comprise the following steps that：Take what certain nickel factory slag head stored up the phase
Iron vitriol slag 300g, containing Ni 3.430%, Co 0.030%, Cu 2.040%, Fe 20.820%, As 2.1%, at normal temperatures, liquid-solid ratio
2:Agitator treating 20min under the conditions of 1, washery slag contains Ni 0.41%, Co 0.007%, Cu 1.64%, Fe 26.50%, As 2.44%,
Rear liquid 13.07g/L containing Ni is washed, former nickel processing system industrial water is returned.Overall Binder Materials is prepared, the siderotil after washing is taken
Slag 60g, is dispersed in 76mL water（The ratio of mud 0.5）, after adding 20g quick lime calcifications 10min, add 5g PFS to be sufficiently stirred for
The hydrogen peroxide that 3g mass fractions are 30%, 60g cement, 0.009g PAM, 4.6g waterglass is added to stir laggard after 5min
Row discharging molding, outdoor maintenance 28 days, compression strength 11Mpa after the demoulding, overall Binder Materials is crushed to 12mm and carries out mine fills
Fill out, 28 days compression strength of obturation meets the strength criterion >=5Mpa required by filling in mine.
Solidification slag 50g is taken, below 5mm, liquid-solid ratio 10 is crushed to:1 carries out water logging, and the holding level on the oscillator that leaches is shaken
Swing 18h, vibration rotating speed 100r/min.1.45mg/L containing Ni in leachate, Co 0.02mg/L, Cu 0.92mg/L, Fe
16.12mg/L, Pb<0.1 mg/L, As<The various poisonous and harmful element contents of 0.5mg/L are far below national standard.
Embodiment 2
It is a kind of iron vitriol slag is solidified after for the method for filling mine, comprise the following steps that：Treatment contains Ni 2.320, Co
0.006th, certain nickel factory of Cu 1.400, Fe 23.780, As 1.65 normally produce the iron vitriol slag 300g of output, at normal temperatures, liquid
Admittedly than 2:Agitator treating 30min under the conditions of 1, washery slag contains Ni 0.25%, Co 0.003%, Cu 1.05%, Fe 25.98%, As
0.4%.Wash water 10.24g/L containing Ni.Overall Binder Materials is prepared, the iron vitriol slag 60g after washing is taken, is dispersed in 76mL water（Water
Gray scale 0.5）, after adding 20g quick lime calcifications 15min, addition 3g mass fractions are 30% after adding 5g PFS to be sufficiently stirred for 5min
Hydrogen peroxide, 25g cement 60g, 0.01g PAM, 4.6g waterglass carries out discharging molding after stirring, outdoor after the demoulding to support
Shield 28 days, compression strength 11.25Mpa, overall Binder Materials is crushed to 10mm and carries out filling in mine, 28 days compression strength of obturation
Meet the strength criterion >=5Mpa required by filling in mine.
Solidification slag is tested by water logging, 0.22mg/L containing Ni in leachate, Co 0.03mg/L, Cu 1.20mg/L, Fe
16.66mg/L, Pb<0.1 mg/L, As<0.5mg/L, meets national standard.
Embodiment 3
It is a kind of iron vitriol slag is solidified after for the method for filling mine, comprise the following steps that：Treatment contains Ni 2.320, Co
0.006th, certain nickel factory of Cu 1.400, Fe 23.780, As 1.65 normally produce the iron vitriol slag 50kg of output, at normal temperatures, liquid
Admittedly than 3:Agitator treating 30min under the conditions of 1, slag contains Ni 0.40%, Co 0.003%, Cu 1.09%, Fe 25.78%, As 0.4%.
Wash water 10.68g/L containing Ni.Overall Binder Materials is prepared, the iron vitriol slag 25.0kg after washing is taken, 38.1L is dispersed in（The ratio of mud
0.45）In water, after adding 20kg quick lime calcifications 12min, 3.0kg PFS are added to add 2.0kg mass after being sufficiently stirred for 10min
Fraction is 30% hydrogen peroxide, and 35kg cement, 4.2g PAM, 10kg waterglass carries out discharging molding, after the demoulding after stirring
Outdoor maintenance 28 days, compression strength 11.15Mpa, overall Binder Materials is crushed to 12mm and carries out filling in mine, and obturation resists for 28 days
Compressive Strength meets the strength criterion >=5Mpa required by filling in mine.Solidification slag is tested by water logging, and Ni is contained in leachate
0.053mg/L, Co are not detected, Cu 0.048mg/L, Fe 0.11mg/L, Pb<0.1 mg/L, As<0.5mg/L, meets country
Standard.
Claims (4)
1. it is a kind of iron vitriol slag is solidified after for the method for filling mine, it is characterised in that comprise the following steps that：
（1）Iron vitriol slag is washed, wherein liquid-solid ratio is 2-3:1, washed-residue is obtained after agitator treating 20-30min, wash rear liquid and return to original
Nickel processing system industrial water；
（2）Solidification：Step（1）The washed-residue of gained adds water, and polyaluminum sulfate is added after adding quick lime calcification 10-15min
Iron PFS is sufficiently stirred for adding hydrogen peroxide, cement, waterglass and the polyacrylamide PAM that mass fraction is 30 % after 5-10min
Mix 10-20min in trommel mixer, mixing makes iron vitriol slag condense integral Binder Materials, overall Binder Materials 21-28 days
Compression strength reaches 11Mp, and wherein washed-residue is with the mass ratio of each additive, washed-residue：Quick lime：Bodied ferric sulfate：Dioxygen
Water：Cement：Waterglass=3-2.5:1-2:0.25-0.3:0.15-0.2:3-3.5:0.23-0.3；Polyacrylamide PAM with wash
The mass ratio for washing slag is 0.00015:1；
（3）Filling：By step（2）The outdoor maintenance of firming body of gained, temperature is 25-30 DEG C, and 10- is crushed to after 21-28 days
12mm is used for filling in mine.
2. it is according to claim 1 it is a kind of by iron vitriol slag solidify process, it is characterised in that：The iron vitriol slag be containing
Iron removes iron vitriol slag produced by iron to use yellow modumite method in nickel, the cobalt wet smelting process of 20-25%.
3. it is according to claim 1 and 2 it is a kind of by iron vitriol slag solidify process, it is characterised in that：The step（1）
The washing of middle iron vitriol slag uses two sections of countercurrent washings, and two sections of wash waters return to first wash.
4. it is according to claim 1 and 2 it is a kind of by iron vitriol slag solidify process, it is characterised in that：In the step 2
Water, washed-residue, cement, bodied ferric sulfate, hydrogen peroxide, waterglass, polyacrylamide various additives are mixed in trommel mixer
Ratio of mud when closing solidification is 0.45-0.50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611073089.XA CN106734062A (en) | 2016-11-29 | 2016-11-29 | It is a kind of iron vitriol slag is solidified after for the method for filling mine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611073089.XA CN106734062A (en) | 2016-11-29 | 2016-11-29 | It is a kind of iron vitriol slag is solidified after for the method for filling mine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106734062A true CN106734062A (en) | 2017-05-31 |
Family
ID=58900601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611073089.XA Pending CN106734062A (en) | 2016-11-29 | 2016-11-29 | It is a kind of iron vitriol slag is solidified after for the method for filling mine |
Country Status (1)
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| CN (1) | CN106734062A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111069232A (en) * | 2019-12-10 | 2020-04-28 | 赤峰中色锌业有限公司 | Method for washing and recovering zinc from zinc hydrometallurgy jarosite slag and innocent treatment of recovered slag |
| CN112458290A (en) * | 2020-11-06 | 2021-03-09 | 金川集团股份有限公司 | Harmless treatment method for solid waste of nickel-containing iron slag |
| CN113185256A (en) * | 2021-03-30 | 2021-07-30 | 中国十七冶集团有限公司 | Performance-controllable cement composite slurry and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111069232A (en) * | 2019-12-10 | 2020-04-28 | 赤峰中色锌业有限公司 | Method for washing and recovering zinc from zinc hydrometallurgy jarosite slag and innocent treatment of recovered slag |
| CN112458290A (en) * | 2020-11-06 | 2021-03-09 | 金川集团股份有限公司 | Harmless treatment method for solid waste of nickel-containing iron slag |
| CN113185256A (en) * | 2021-03-30 | 2021-07-30 | 中国十七冶集团有限公司 | Performance-controllable cement composite slurry and preparation method thereof |
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