CN104984982A - Innocent treatment method of electrolytic manganese and chromium residues - Google Patents
Innocent treatment method of electrolytic manganese and chromium residues Download PDFInfo
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- CN104984982A CN104984982A CN201510403752.7A CN201510403752A CN104984982A CN 104984982 A CN104984982 A CN 104984982A CN 201510403752 A CN201510403752 A CN 201510403752A CN 104984982 A CN104984982 A CN 104984982A
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- 238000000034 method Methods 0.000 title claims abstract description 43
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title abstract description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910052748 manganese Inorganic materials 0.000 title abstract description 8
- 239000011572 manganese Substances 0.000 title abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 97
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000003610 charcoal Substances 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims description 88
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 70
- QDLZHJXUBZCCAD-UHFFFAOYSA-N [Cr].[Mn] Chemical compound [Cr].[Mn] QDLZHJXUBZCCAD-UHFFFAOYSA-N 0.000 claims description 68
- 150000001875 compounds Chemical class 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000004744 fabric Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002203 pretreatment Methods 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 238000012216 screening Methods 0.000 abstract 2
- 239000002023 wood Substances 0.000 abstract 2
- 239000000047 product Substances 0.000 description 36
- 239000011651 chromium Substances 0.000 description 26
- 229910052804 chromium Inorganic materials 0.000 description 23
- 239000012071 phase Substances 0.000 description 18
- 230000008569 process Effects 0.000 description 7
- 238000002386 leaching Methods 0.000 description 6
- 239000002920 hazardous waste Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- BCFSVSISUGYRMF-UHFFFAOYSA-N calcium;dioxido(dioxo)chromium;dihydrate Chemical compound O.O.[Ca+2].[O-][Cr]([O-])(=O)=O BCFSVSISUGYRMF-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
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- 238000004088 simulation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/78—Recycling of wood or furniture waste
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses an innocent treatment method of electrolytic manganese and chromium residues. The innocent treatment method comprises the following steps of (1) pretreating; (2) igniting and arranging materials: firstly, putting igniting materials and wood at the bottom of a sintering furnace, then igniting the wood to burn into charcoal, so as to smash and lay with the height of 5 to 6 cm at the bottom of the sintering furnace, then laying a layer of sawdust with the thickness of 4 to 5 cm, subsequently, adding two shovelfuls of standby mixtures, and laying with the thickness of 3 to 4 cm; (3) sintering; (4) screening and returning to mines: screening finished products of sinters, returning the finished products of sinters of which the granularity is less than 5 mm to the mines as raw materials in the step of pretreatment, and storing the finished products of sinters of which the granularity is greater than or equal to 5 mm. The innocent treatment method has the advantages that innocent treatment can be performed on the electrolytic manganese and chromium residues, the problem of stacking of the electrolytic manganese and chromium residues is solved, the influence of the electrolytic manganese and chromium residues on the environment is eliminated, the obtained products have stronger stability and are easy to store, and certain economic benefits can be brought.
Description
Technical field
The invention belongs to field of metallurgy, particularly a kind of electrolytic manganese chromium slag innocent treatment method.
Background technology
Electrolytic Manganese Metal Plant Long-Time Service has chromium passivating, produces a large amount of hazardous waste chromium slag.Cr VI in chromium slag has very strong oxidisability, has strong basicity again, and therefore chromium slag belongs to hazardous waste, is put into China's " National Hazard refuse register ".The harm of chromium slag is huge, can only be stored in special chromium slag storehouse fixed point and pile up, but accumulation volume of cargo in storage over the years is considerable.If the outdoor placement of chromium slag of storing up, there is no rainproof, antiseepage, the anti-protective equipment such as to fly upward, can severe contamination surface water, underground water and soil, significant damage is caused to the mankind and environment.For solving risk hidden danger and the environmental problem in slag storehouse, being badly in need of a kind of technological operation simple, the method for effective harmless treatment can be carried out again simultaneously to chromium slag.
Chromium residue detoxifying method of comprehensive utilization has dry detoxified, cyclone furnace process waste residue, does glass colorant, chromium slag sintered ironmaking, the brickmaking of chromium slag, chromium slag cement, wet method detoxifcation etc.Existing document is issued and is replaced portion of flux and iron charge mixed sintering then to go ironmaking with chromium slag, but the chromium slag allocated into can not be too much, is less than 3% better, the chromium slag allocated into can affect the stability of raw material, the quality of finished product sintering deposit can be reduced to a certain extent, increase the rate of return mine, increase the use of fuel.Chromium slag does the flux sintering pig iron, do reducing agent reduction of hexavalent chromium with CO and C under the high temperature conditions, this approach technology maturation feasible process, thoroughly, cost is lower in removing toxic substances, economic benefit is obvious, environmental benefit is obvious, and chromium finally enters in the pig iron, and the chromium slag in document mostly is the chromium residue produced and discharge in the process of chromic salts and crome metal, its CaO, content of MgO are higher, can replace portion of flux.The chromium slag mentioned in the electrolytic manganese chromium slag that this patent is mentioned and most of document is different, and the electrolytic manganese chromium slag CaO in this patent, content of MgO are very low, can not play the effect replacing flux.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of electrolytic manganese chromium slag innocent treatment method, electrolytic manganese chromium slag is carried out harmless treatment, solve electrolytic manganese chromium slag slag storehouse and pile up problem, eliminate electrolytic manganese chromium slag to the impact of environment, the sintering deposit stability produced is stronger, be easy to store, certain economic benefit can be brought.
To achieve these goals, the present invention is achieved through the following technical solutions:
Electrolytic manganese chromium slag innocent treatment method, comprises the following steps:
(1) pretreatment: manganese oxide ore, electrolytic manganese chromium slag and anchracite duff are carried out being crushed to granularity≤5mm respectively, then by electrolytic manganese chromium slag: manganese oxide ore according to weight ratio be 1:6 ~ 20 with addition of, be also 0 ~ 40% return mine with addition of accounting for electrolytic manganese chromium slag, manganese oxide ore and the gross mass of returning mine, compound is obtained 4 ~ 5 times with the ore deposit mixing of heap cone method shovel again after accounting for electrolytic manganese chromium slag, manganese oxide ore and the anchracite duff of gross mass 14 ~ 15% of returning mine, then add water and make the water content of compound be 7%-9%, for subsequent use;
(2) igniting, cloth: first matches and timber are put into bottom sintering furnace, then light a fire timber to burn and smash to charcoal shape and be laid at the bottom of sintering furnace, high 5-6cm, the wooden chaff of the thick 4-5cm of the last layer that tiles, then compound for subsequent use is added, thick 3-4cm after tiling;
(3) sinter: open centrifugal AC air blower and carry out air blast, wind direction flows from the bottom up, then compound for subsequent use for step (1) is added sintering furnace by intermittence, run after 3-4h out of service until centrifugal AC air blower, change single-phase air blast carry out air blast 8-12h after compound sintered, after carrying out cooling 2-8h again, compound is down to normal temperature and is closed single-phase air blast, can obtain sintering deposit finished product;
(4) sieve, return mine: sintering deposit finished product is sieved, the sintering deposit finished product of granularity <5mm is carried out the raw material of returning mine as in pre-treatment step, the sintering deposit finished product of granularity >=5mm is stored.
In the present invention, the power of described single-phase air blast is 150W, and rotating speed is 2500-3000 r/min, and air quantity is 3.0-3.5m
3/ min, blast is 450-500Pa.
In the present invention, the power of described centrifugal AC air blower is 80W, and rotating speed is 25000-30000 r/min, and air quantity is 1.5-2.0m
3/ min, blast is 220-300Pa.
In the present invention, described electrolytic manganese chromium slag accounts for overall weight percent≤8.8% of raw material.
In the present invention, described matches be spoon oil paper, spoon oil polybag, spoon oil hay or spoon oil leaf.
In the present invention, content≤2% of CaO in electrolytic manganese chromium slag., MgO content≤3%.
The principle of the inventive method is:
Various granular material is mainly carried out high-temperature heating by oxide ore sintering mechanism, and under the condition of not exclusively fusing, the liquid phase by sintering generation bonds mineral grain, forms the porous of similar coke and has the sintering deposit of sufficient intensity.
Harmless treatment electrolytic manganese chromium slag is the high temperature reducing atmospheres condition based on sintering.In sintering process, the Cr VI in electrolytic manganese chromium slag and reducing agent C and CO etc. fully act on, and are reduced to trivalent chromium, make electrolytic manganese chromium slag reach harmless treatment; CaO, MgO, FeO etc. in sintering deposit, again with Cr
2o
3react, the chromium therefore in sintering deposit is mainly with picotite (MgOCr
2o
3), the form such as chromite and calcium chromate exists makes electrolytic manganese chromium slag reduction product more stable.
beneficial effect of the present invention is:
1. the present invention is by using updraught sintering method sintering, adopts the mode of intermittent cloth greatly can reduce requirement to blower pressure; Blower fan is air draught at normal temperatures, and require lower to blower fan capacitance, air blast can be arranged on ground, and workshop building is fairly simple.
2. the present invention first uses low power air blast to carry out air blast in the sintering stage, prevents starting stage raw material very few, and wind-force is crossed senior general's raw material and blown and fly, and the too fast meeting of air velocity causes heat energy in initial sintering stage sintering furnace to lose in a large number; After several hours, mixed anthracite is in the feed lighted, and forms one deck high temperature burning zone, and sintering starts, and extend in time and up pass gradually, change powerful air blast and carry out the time that air blast can shorten sintering, for sintering provides enough air quantity, ensure full combustion of fuel.
3. the electrolytic manganese chromium slag through process of the present invention can detoxify completely, stability improves greatly, greatly reduces the outdoor accumulation of electrolytic manganese chromium slag to the Harmfulness analyse of environment, eliminates slag storehouse and piles up hidden danger, electrolytic manganese chromium slag is fully utilized, change harmful to treasure, and present invention process is simple, cost is low, electrolytic manganese chromic wastes disposal amount is larger, sintering deposit finished product is easy to shipping storage, and to environment without substantial pollution, the harmless treatment for electrolytic manganese chromium slag more has the meaning of positive important.
Accompanying drawing explanation
Fig. 1 is flow chart of the present invention.
Detailed description of the invention
Below by way of specific embodiment, the invention will be further described.The present invention is not limited to following detailed description of the invention.
embodiment 1:
Electrolytic manganese chromium slag innocent treatment method, comprises the following steps:
(1) pretreatment: by manganese oxide ore, it is 5mm that electrolytic manganese chromium slag and anchracite duff carry out being crushed to granularity respectively, then by electrolytic manganese chromium slag: manganese oxide ore according to weight ratio be 1:6 with addition of, be also 30% return mine with addition of accounting for electrolytic manganese chromium slag, manganese oxide ore and the gross mass of returning mine, after the anchracite duff accounting for electrolytic manganese chromium slag and manganese oxide ore gross mass 14%, mix 4 times with heap cone method shovel ore deposit again and obtain compound, then add water and make the water content of compound be 7%, for subsequent use;
(2) igniting, cloth: first the paper and timber that spoon oil are put into bottom sintering furnace, then light a fire timber to burn and smash to charcoal shape and be laid at the bottom of sintering furnace, high 5cm, the wooden chaff of the thick 4cm of the last layer that tiles, then compound for subsequent use is added, thick 3cm after tiling;
(3) sinter: opening power is 80W, and rotating speed is 25000 r/min, and air quantity is 1.5m
3/ min, blast is that the centrifugal AC air blower of 220Pa carries out air blast, wind direction flows from the bottom up, then compound for subsequent use for step (1) is added sintering furnace by intermittence, run after 3h out of service until centrifugal AC air blower, replacing power is 150W, and rotating speed is 2500 r/min, and air quantity is 3.0m
3/ min, blast is that after the single-phase air blast of 450Pa carries out air blast 8h, compound has sintered, then after carrying out cooling 2h, compound is down to normal temperature and is closed single-phase air blast, can obtain sintering deposit finished product;
(4) sieve, return mine: sintering deposit finished product is sieved, the sintering deposit finished product of granularity <5mm is carried out the raw material of returning mine as in pre-treatment step, the sintering deposit finished product of granularity >=5mm is stored.
embodiment 2:
Electrolytic manganese chromium slag innocent treatment method, comprises the following steps:
(1) pretreatment: by manganese oxide ore, it is 4mm that electrolytic manganese chromium slag and anchracite duff carry out being crushed to granularity respectively, then by electrolytic manganese chromium slag: manganese oxide ore according to weight ratio be 1:9 with addition of, be also 25% return mine with addition of accounting for electrolytic manganese chromium slag, manganese oxide ore and the gross mass of returning mine, after the anchracite duff accounting for electrolytic manganese chromium slag, manganese oxide ore and gross mass 15% of returning mine, mix 5 times with heap cone method shovel ore deposit again and obtain compound, then add water and make the water content of compound be 9%, for subsequent use;
(2) igniting, cloth: first the polybag and timber that spoon oil are put into bottom sintering furnace, then light a fire timber to burn and smash to charcoal shape and be laid at the bottom of sintering furnace, high 5cm, the wooden chaff of the thick 5cm of the last layer that tiles, then compound for subsequent use is added, thick 3cm after tiling;
(3) sinter: opening power is 80W, and rotating speed is 28000 r/min, and air quantity is 1.6m
3/ min, blast is that the centrifugal AC air blower of 240Pa carries out air blast, wind direction flows from the bottom up, then compound for subsequent use for step (1) is added sintering furnace by intermittence, run after 4h out of service until centrifugal AC air blower, the power changing single-phase air blast is 150W, and rotating speed is 2800 r/min, and air quantity is 3.2 m
3/ min, blast is that after the single-phase air blast of 490Pa carries out air blast 12h, compound has sintered, then after carrying out cooling 8h, compound is down to normal temperature and is closed single-phase air blast, can obtain sintering deposit finished product;
(4) sieve, return mine: sintering deposit finished product is sieved, the sintering deposit finished product of granularity <5mm is carried out the raw material of returning mine as in pre-treatment step, the sintering deposit finished product of granularity >=5mm is stored.
embodiment 3:
Electrolytic manganese chromium slag innocent treatment method, comprises the following steps:
(1) pretreatment: by manganese oxide ore, it is 3mm that electrolytic manganese chromium slag and anchracite duff carry out being crushed to granularity respectively, then by electrolytic manganese chromium slag: manganese oxide ore according to weight ratio be 1:13 with addition of, do not add and return mine, after the anchracite duff accounting for electrolytic manganese chromium slag, manganese oxide ore and gross mass 14% of returning mine, mix 5 times with heap cone method shovel ore deposit again and obtain compound, then add water and make the water content of compound be 8%, for subsequent use;
(2) igniting, cloth: first the hay and timber that spoon oil are put into bottom sintering furnace, then light a fire timber to burn and smash to charcoal shape and be laid at the bottom of sintering furnace, high 5.5cm, the wooden chaff of the thick 4.5cm of the last layer that tiles, then compound for subsequent use is added, thick 3.5cm after tiling;
(3) sinter: opening power is 80W, and rotating speed is 30000 r/min, and air quantity is 2.0m
3/ min, blast is that the centrifugal AC air blower of 300Pa carries out air blast, wind direction flows from the bottom up, then compound for subsequent use for step (1) is added sintering furnace by intermittence, run after 3.5h out of service until centrifugal AC air blower, replacing power is 150W, and rotating speed is 3000 r/min, and air quantity is 3.5m
3/ min, blast is that after the single-phase air blast of 500Pa carries out air blast 9h, compound has sintered, then after carrying out cooling 3h, compound is down to normal temperature and is closed single-phase air blast, can obtain sintering deposit finished product;
(4) sieve, return mine: sintering deposit finished product is sieved, the sintering deposit finished product of granularity <5mm is carried out the raw material of returning mine as in pre-treatment step, the sintering deposit finished product of granularity >=5mm is stored.
embodiment 4:
Electrolytic manganese chromium slag innocent treatment method, comprises the following steps:
(1) pretreatment: by manganese oxide ore, it is 2mm that electrolytic manganese chromium slag and anchracite duff carry out being crushed to granularity respectively, then by electrolytic manganese chromium slag: manganese oxide ore according to weight ratio be 1:11 with addition of, be also 20% return mine with addition of accounting for electrolytic manganese chromium slag, manganese oxide ore and the gross mass of returning mine, after the anchracite duff accounting for electrolytic manganese chromium slag, manganese oxide ore and gross mass 15% of returning mine, mix 5 times with heap cone method shovel ore deposit again and obtain compound, then add water and make the water content of compound be 7%, for subsequent use;
(2) igniting, cloth: first the leaf and timber that spoon oil are put into bottom sintering furnace, then light a fire timber to burn and smash to charcoal shape and be laid at the bottom of sintering furnace, high 5cm, the wooden chaff of the thick 5cm of the last layer that tiles, then compound for subsequent use is added, thick 3.5cm after tiling;
(3) sinter: opening power is 80W, and rotating speed is 28000 r/min, and air quantity is 1.6m
3/ min, blast is that the centrifugal AC air blower of 240Pa carries out air blast, wind direction flows from the bottom up, then compound for subsequent use for step (1) is added sintering furnace by intermittence, run after 3h out of service until centrifugal AC air blower, the power changing single-phase air blast is 150W, and rotating speed is 2800 r/min, and air quantity is 3.2m
3/ min, blast is that after the single-phase air blast of 490Pa carries out air blast 10h, compound has sintered, then after carrying out cooling 4h, compound is down to normal temperature and is closed single-phase air blast, can obtain sintering deposit finished product;
(4) sieve, return mine: sintering deposit finished product is sieved, the sintering deposit finished product of granularity <5mm is carried out the raw material of returning mine as in pre-treatment step, the sintering deposit finished product of granularity >=5mm is stored.
embodiment 5:
Electrolytic manganese chromium slag innocent treatment method, comprises the following steps:
(1) pretreatment: by manganese oxide ore, it is 1mm that electrolytic manganese chromium slag and anchracite duff carry out being crushed to granularity respectively, then by electrolytic manganese chromium slag: manganese oxide ore according to weight ratio be 1:15 with addition of, be also 10% return mine with addition of accounting for electrolytic manganese chromium slag, manganese oxide ore and the gross mass of returning mine, after the anchracite duff accounting for electrolytic manganese chromium slag, manganese oxide ore and gross mass 15% of returning mine, mix 5 times with heap cone method shovel ore deposit again and obtain compound, then add water and make the water content of compound be 9%, for subsequent use;
(2) igniting, cloth: first the hay and timber that spoon oil are put into bottom sintering furnace, then light a fire timber to burn and smash to charcoal shape and be laid at the bottom of sintering furnace, high 5.5cm, the wooden chaff of the thick 4cm of the last layer that tiles, then compound for subsequent use is added, thick 3.5cm after tiling;
(3) sinter: opening power is 80W, and rotating speed is 26000 r/min, and air quantity is 1.8m
3/ min, blast is that the centrifugal AC air blower of 280Pa carries out air blast, wind direction flows from the bottom up, then compound for subsequent use for step (1) is added sintering furnace by intermittence, run after 3.5h out of service until centrifugal AC air blower, replacing power is 150W, and rotating speed is 2700 r/min, and air quantity is 3.3m
3/ min, blast is that after the single-phase air blast of 470Pa carries out air blast 11h, compound has sintered, then after carrying out cooling 6h, compound is down to normal temperature and is closed single-phase air blast, can obtain sintering deposit finished product;
(4) sieve, return mine: sintering deposit finished product is sieved, the sintering deposit finished product of granularity <5mm is carried out the raw material of returning mine as in pre-treatment step, the sintering deposit finished product of granularity >=5mm is stored.
embodiment 6:
Electrolytic manganese chromium slag innocent treatment method, comprises the following steps:
(1) pretreatment: by manganese oxide ore, it is 3mm that electrolytic manganese chromium slag and anchracite duff carry out being crushed to granularity respectively, then by electrolytic manganese chromium slag: manganese oxide ore according to weight ratio be 1:20 with addition of, be also 40% return mine with addition of accounting for electrolytic manganese chromium slag, manganese oxide ore and the gross mass of returning mine, after the anchracite duff accounting for electrolytic manganese chromium slag, manganese oxide ore and gross mass 15% of returning mine, mix 4 times with heap cone method shovel ore deposit again and obtain compound, then add water and make the water content of compound be 8%, for subsequent use;
(2) igniting, cloth: first the paper and timber that spoon oil are put into bottom sintering furnace, then light a fire timber to burn and smash to charcoal shape and be laid at the bottom of sintering furnace, high 6cm, the wooden chaff of the thick 4.5cm of the last layer that tiles, then compound for subsequent use is added, thick 4cm after tiling;
In the present invention, described single-phase air blast.
In the present invention, described centrifugal AC air blower.
(3) sinter: opening power is 80W, and rotating speed is 28500 r/min, and air quantity is 1.9m
3/ min, blast is that the centrifugal AC air blower of 285Pa carries out air blast, wind direction flows from the bottom up, then compound for subsequent use for step (1) is added sintering furnace by intermittence, run after 3.5h out of service until centrifugal AC air blower, replacing power is 150W, and rotating speed is 2950 r/min, and air quantity is 3.4m
3/ min, blast is that after the single-phase air blast of 495Pa carries out air blast 10h, compound has sintered, then after carrying out cooling 2-8h, compound is down to normal temperature and is closed single-phase air blast, can obtain sintering deposit finished product;
(4) sieve, return mine: sintering deposit finished product is sieved, the sintering deposit finished product of granularity <5mm is carried out the raw material of returning mine as in pre-treatment step, the sintering deposit finished product of granularity >=5mm is stored.
Under be classified as the experiment that Application Example 1-6 carries out, concrete data are in table 1:
Table 1 sinters proportioning
| Embodiment sequence number | Manganese oxide ore/kg | Electrolytic manganese chromium slag/kg | Return mine proportioning/% | Return mine weight/kg | Anchracite duff/% | Anthracite grain weight/kg | Mixture moisture/% |
| Embodiment 1 | 24 | 4 | 30 | 12 | 14 | 5.6 | 7 |
| Embodiment 2 | 27 | 3 | 25 | 10 | 15 | 6 | 9 |
| Embodiment 3 | 39 | 3 | / | / | 14 | 5.9 | 8 |
| Embodiment 4 | 22 | 2 | 20 | 6 | 15 | 4.5 | 7 |
| Embodiment 5 | 30 | 2 | 10 | 3.6 | 15 | 5.4 | 9 |
| Embodiment 6 | 20 | 1 | 40 | 14 | 15 | 5.3 | 8 |
Remarks: F represents the percentage of returning mine of gross mass accounting for electrolytic manganese chromium slag, manganese oxide ore and return mine;
The computational methods of weight of returning mine: (electrolytic manganese chromium slag+manganese oxide ore) × F/(1-F).
Table 2 electrolytic manganese chromium slag accounts for the overall weight percent list position of raw material: %
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Percentage | 8.8 | 6.5 | 6.3 | 5.8 | 4.9 | 2.5 |
Remarks: raw material comprises manganese oxide ore, electrolytic manganese chromium slag, returns mine and anchracite duff.
The physical property of the sintering deposit finished product that the concrete proportioning of each embodiment obtains in application table 1, in table 3; Wherein, finished product sintering deposit drop strength is tested: finished product sintering deposit is fallen 3 times continuously from 2m eminence, and the percentage that the finished product sintering deposit being greater than 5mm accounts for shatter test sample ore is drop strength index.
The physical property of table 3 sintering deposit finished product
| Embodiment sequence number | Material weight/kg before burning | Weight/kg after burning | Scaling loss/% | Yield rate % | The rate of return mine/% | Intensity/% |
| Embodiment 1 | 45.6 | 38.12 | 16.4 | 70.3 | 29.7 | 86.87 |
| Embodiment 2 | 46 | 37.35 | 18.80 | 71.4 | 28.6 | 87.8 |
| Embodiment 3 | 47.9 | 37.97 | 20.73 | 75.5 | 24.5 | 86.2 |
| Embodiment 4 | 34.5 | 27.2 | 21.16 | 74 | 26 | 87.0 |
| Embodiment 5 | 41 | 34.73 | 15.30 | 72.9 | 27.1 | 88.4 |
| Embodiment 6 | 40.3 | 34.39 | 14.67 | 72.4 | 27.6 | 86.3 |
Associative list 2 and table 3 data known: when the overall weight percent that electrolytic manganese chromium slag accounts for raw material is less than 8.8%, yield rate all can reach more than 70%; The intensity of sintering deposit, more than 85%, can meet the requirement of blast furnace to sintering deposit.
sintering deposit toxicity judges
Sintering deposit sample presentation is detected sintering deposit Leaching to chemical industry environmental protection monitoring station, and it the results are shown in Table 4.With reference to solid waste operative norm " hazardous waste judging standard leaching characteristic identification " (GB 5085.1-2007) and " discriminating of hazardous waste judging standard corrosivity " (GB 5085.1-2007), its partial excerpt is in table 5.
Solid waste Leaching leaching method-horizontal vibration method
As follows according to the horizontal vibration method that People's Republic of China's state environment protecting standard (HJ 557-2009) carries out operating in conjunction with this sintering experiment:
(1) Method And Principle
Take ultra-pure water as digestion agent, simulation solid waste is subject to leaching of surface water or underground water in specific occasion, and harmful constituent wherein leaches and the process of entered environment.
(2) instrument and equipment
Oscillator device: the reciprocating horizontal oscillation device of frequency-adjustable
Extraction flask: use for laboratory 250ml conical flask
Balance: precision is not less than ± 0.01g
Filter: funnel and filter paper
(3) sample
1. gather: sintering deposit sampling abrasive dust, after abrasive dust, granularity is less than 1mm
2. sample preparation: get 20g sintering deposit sample and be dissolved in 200ml ultra-pure water, liquid-solid ratio is 10:1(ml/g)
(4) experimental procedure
1. measurement of water-content coefficient: because sintering deposit moisture-free, so directly carry out the 2. walk operation
2. step is leached: take 20 g sintering deposit samples, be placed in 250 ml conical flasks, by liquid-solid ratio 10:1(ml/g) measure and add 200 ml ultra-pure waters, be vertically fixed on after covering tightly bottle cap on horizontal shaking device, regulate frequency of oscillation to be 110 ± 10 times/min, amplitude is 35 ~ 40 mm, takes off after 8 h that at room temperature vibrate, leave standstill 16 h, filter liquor charging sample after leaving standstill and detect Mn and Cr content (the results are shown in Table 4).
Table 4 sintering deposit toxicity leaches analysis result
Remarks: except pH value project, unit is mg/l; Project does not detect filling " L " after detection limit and represents.
Table 5 hazardous waste judging standard leaching characteristic identification (extracts) (unit: mg/l)
| Pollution factor | Numerical value |
| Copper | 100 |
| Zinc | 100 |
| Plumbous | 5 |
| Cadmium | 1 |
| Mercury | 0.1 |
| Arsenic | 5 |
| Total chromium | 5 |
| Nickel | 5 |
| Iron | / |
| Manganese | / |
| Selenium | 1 |
Comparison sheet 4 and table 5 known, every toxicity of sintering deposit leaches element all within standard limited value.Illustrating that chromium slag and oxide ore burn the sintering deposit is not poisonous solid, belongs to general solid product, can produce economic benefit.The pH value of horizontal vibration method is 6.17, does not belong to corrosive solid.
Claims (5)
1. electrolytic manganese chromium slag innocent treatment method, is characterized in that, comprises the following steps:
(1) pretreatment: manganese oxide ore, electrolytic manganese chromium slag and anchracite duff are carried out being crushed to granularity≤5mm respectively, then by electrolytic manganese chromium slag: manganese oxide ore according to weight ratio be 1:6 ~ 20 with addition of, be also 0 ~ 40% return mine with addition of accounting for electrolytic manganese chromium slag, manganese oxide ore and the gross mass of returning mine, compound is obtained 4 ~ 5 times with the ore deposit mixing of heap cone method shovel again after accounting for electrolytic manganese chromium slag, manganese oxide ore and the anchracite duff of gross mass 14 ~ 15% of returning mine, then add water and make the water content of compound be 7%-9%, for subsequent use;
(2) igniting, cloth: first matches and timber are put into bottom sintering furnace, then light a fire timber to burn and smash to charcoal shape and be laid at the bottom of sintering furnace, high 5-6cm, the wooden chaff of the thick 4-5cm of the last layer that tiles, then two shovels compound for subsequent use is added, thick 3-4cm after tiling;
(3) sinter: open centrifugal AC air blower and carry out air blast, wind direction moves from the bottom up, then compound for subsequent use for step (1) is added sintering furnace by intermittence, run after 3-4h out of service until centrifugal AC air blower, change single-phase air blast carry out air blast 8-12h after compound sintered, after carrying out cooling 2-8h again, compound is down to normal temperature and is closed single-phase air blast, can obtain sintering deposit finished product;
(4) sieve, return mine: sintering deposit finished product is sieved, the sintering deposit finished product of granularity <5mm is carried out the raw material of returning mine as in pre-treatment step, the sintering deposit finished product of granularity >=5mm is stored.
2. electrolytic manganese chromium slag innocent treatment method according to claim 1, is characterized in that, the power of described single-phase air blast is 150W, and rotating speed is 2500-3000 r/min, and air quantity is 3.0-3.5m
3/ min, blast is 450-500Pa.
3. electrolytic manganese chromium slag innocent treatment method according to claim 1, is characterized in that, the power of described centrifugal AC air blower is 80W, and rotating speed is 25000-30000 r/min, and air quantity is 1.5-2.0m
3/ min, blast is 220-300Pa.
4. electrolytic manganese chromium slag innocent treatment method according to claim 1, is characterized in that, described electrolytic manganese chromium slag accounts for overall weight percent≤8.8% of raw material.
5. electrolytic manganese chromium slag innocent treatment method according to claim 1, is characterized in that, described matches be spoon oil paper, spoon oil polybag, spoon oil hay or spoon oil leaf.
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| CN105524640A (en) * | 2016-01-19 | 2016-04-27 | 青岛理工大学 | Method for preparing energy gas by using chlorine-free plastic and simultaneously harmlessly treating chromium slag |
| CN105524639A (en) * | 2016-01-19 | 2016-04-27 | 青岛理工大学 | Method for preparing energy gas by using plastics and simultaneously harmlessly treating chromium slag |
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| CN105524640A (en) * | 2016-01-19 | 2016-04-27 | 青岛理工大学 | Method for preparing energy gas by using chlorine-free plastic and simultaneously harmlessly treating chromium slag |
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| CN105623690A (en) * | 2016-01-19 | 2016-06-01 | 青岛理工大学 | Method for preparing energy gas by using chlorine-containing plastics and simultaneously harmlessly treating chromium slag |
| CN105694938A (en) * | 2016-01-19 | 2016-06-22 | 青岛理工大学 | Method for preparing energy oil gas and simultaneously harmlessly treating chromium slag by using chlorine-containing plastics |
| CN105694987A (en) * | 2016-01-19 | 2016-06-22 | 青岛理工大学 | Method for preparing energy gas by using biomass and simultaneously harmlessly treating chromium slag |
| CN105524639B (en) * | 2016-01-19 | 2019-03-01 | 青岛理工大学 | Method for preparing energy gas by using plastics and simultaneously harmlessly treating chromium slag |
| CN105623690B (en) * | 2016-01-19 | 2019-05-03 | 青岛理工大学 | Method for preparing energy gas by using chlorine-containing plastics and simultaneously harmlessly treating chromium slag |
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| CN105694987B (en) * | 2016-01-19 | 2019-05-24 | 青岛理工大学 | Method for preparing energy gas by using biomass and simultaneously harmlessly treating chromium slag |
| CN108329049A (en) * | 2018-02-07 | 2018-07-27 | 贵州中科鸿塬环保科技有限公司 | A kind of puffing lightweight aggregate of electrolytic manganese residues and harmless regeneration processing utilize method |
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| CN111675549B (en) * | 2020-06-22 | 2023-03-10 | 山东洛尔环保科技有限公司 | Resource utilization method of hexavalent chromium contaminated soil |
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