CN104525555A - Stabilizing treatment method and equipment for arsenic slag - Google Patents
Stabilizing treatment method and equipment for arsenic slag Download PDFInfo
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- CN104525555A CN104525555A CN201410841400.5A CN201410841400A CN104525555A CN 104525555 A CN104525555 A CN 104525555A CN 201410841400 A CN201410841400 A CN 201410841400A CN 104525555 A CN104525555 A CN 104525555A
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Abstract
The invention discloses stabilizing treatment method and equipment for arsenic slag. The method disclosed by the invention is simple in process, low in cost, efficient and fast to repair, and free of secondary pollution; the equipment by using the process is simple in structure, low in manufacturing cost, high in mechanical degree and convenient to operate, and is especially good in stabilizing treatment effect on arsenic slag with ultra-high concentration; and engineering application is facilitated.
Description
Technical field
The invention belongs to heavy metal waste slag process field, be specifically related to a kind of stabilization treatment method and the equipment that are applicable to arsenic slag.
Background technology
Arsenic is the main accompanying elements in nonferrous metallic ores, and in mining or smelting process, often produce various arsenic-containing waste, and these arsenic-containing wastes have severe toxicity, storing up, transports, controls in the process such as process improperly will become arsenic pollution sources.In history, except minority large enterprise, most enterprise does not effectively dispose arsenic-containing waste residue, and leaving over a large amount of history arsenic slag need carry out stabilisation harmless treatment.Because arsenic-containing waste residue solubility in water is large, there is secondary pollution to water body and soil, and China's dangerous solid wastes disposing level is low, starting late, most industry discarded object is directly piled and be there is factories and miness vacant lot, non-handicapping every, therefore waste residue stockyard arsenic in soil pollute also very serious.
In recent years, China's arsenic contamination accident is situation occurred frequently, and mostly occurs in mining area or smeltery intensively.Therefore, before arsenic slag landfill, necessary advanced line stabilization process, avoids environment.The processing method of existing arsenic slag or As polluted soil mainly comprises restoration of the ecosystem, chemical leaching, wet-treating and stabilisation/solidify & bury.The method such as phytoremediation, chemical leaching is only applicable to the lower situation of arsenic concentration.Smelting enterprise is when processing poisonous arsenic slag and mud, arsenic leaches by the conventional solution such as hot water or soda acid, then does precipitating reagent with calcium, iron, magnesium, aluminium salt and sulfide etc., carries out stabilization processes to arsenic leaching solution, but will produce a large amount of arsenic-containing waste residue after precipitation process, secondary pollution has a big risk.Stabilisation/immobilization technology, compared with other technologies, more can meet the requirement of repairing, the left over by history arsenic slag handling project many employings the method started at present from time and cost.At present, contaminated soil stabilizing surface treatment is a kind of method conventional in engineering reality, the steps include: that soil adds mixer after the process such as fragmentation, screening, then adds stabilizing agent, then namely send landfill disposal after stir process.But the method poor effect, and the arsenic slag that effectively can not process ultrahigh concentration.In general rehablitation project, arsenic content, at about 20-50 times of standard of landfill, processes than being easier to.But, due to the scarcity of resource, the lean ore that arsenic content is higher is exploited, the a lot of high-arsenic materials produced in smelting process are also utilized again, cause the waste residue arsenic concentration of discharge more and more higher, even pH>14, the Leaching >4000mg/L of part ultrahigh concentration arsenic slag.In pollution control process in the past, in heavy metal waste slag, arsenic Leaching generally exceeds standard tens times, Ji Shibei, conventional stabilisation/immobilization technology can effectively use, but the arsenic alkaline slag of several thousand times that those Leachings are exceeded standard, follow conventional lines method, equipment corrosion is large, and after process, the concentration of slag is still very high, is difficult to reach hazard waste landfill standard, therefore, conventional treatment method is also inapplicable, is badly in need of new stabilizing treatment technique and equipment.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, provides a kind of stabilizing treatment apparatus for arsenic slag and method.
In order to achieve the above object, technical scheme provided by the invention is:
The described stabilization treatment method for arsenic slag comprises the steps:
(1) arsenic slag is sieved, the granule arsenic slag after sieving is added in loading hopper together with ferrous salt, the remaining bulk waste residue after sieving is collected for subsequent use; The ratio of ferrous salt and arsenic slag is pressed Fe:As mol ratio 1:1.8-3.0 and is controlled;
(2) ferrous salt and arsenic slag mixture are sent into mixer and stir 3-7min;
(3) in mixer, the concentrated sulfuric acid is added, discharging after continuation stirring 3-7min; In every kg ferrous salt and arsenic slag mixture, the addition of the concentrated sulfuric acid is 30-50mL; Controlling liquid-solid ratio in mixer is 1.2-1.8:10;
Wherein, in the described arsenic slag of step (1), arsenic content is 60000-100000mg/kg, and arsenic leaching concentration is 3000-5000mg/L.
Treatment facility for said method comprises mixer, belt conveyer, vibratory sieve and charger; Described mixer is provided with lifting loading hopper, and described loading hopper is near belt conveyer front end; Be provided with vibratory sieve above the conveyer belt of described belt conveyer, described vibratory sieve rear end is provided with unloads slag chute; Described belt conveyer rear end is provided with stabilizing agent charger; Described mixer is also provided with mist acid exhaust device.Described mist acid exhaust device is pump drainage pump.
Preferably, described Vibration Screen screen distance 6-10cm, vibratory sieve, horizontal by 3-5 ° of angles, unloads slag chute horizontal by 10-15 ° of angles, and described slag dumping bottom land end is provided with feeder.
More preferably, treatment facility of the present invention also comprises hammer crusher.
The invention will be further described below:
The present invention, before actual motion, has carried out Chemicals work, compared for 3 kinds of reagent, and the phenanthroline finally determined in the application is best in effect and cost.Medicament adding proportion, dosing method etc., all carried out lab scale research, thus obtained optimum range before engineer applied, if variation, and stabilization processes weak effect.For pH>14, Leaching is the 500g High Concentration of Arsenic alkaline residue of 4053mg/L, arranges 4 groups of different ferrous sulfate heptahydrate addition experiments, after maintenance 1d, and total arsenic in sampling and measuring soil extract, acquired results is as shown in table 1:
Table 1
| Numbering | FeSO 4·7H 2O addition (g) | As:Fe mol ratio | Leach As concentration (mg/L) |
| 1 | 105 | 1:1.4 | 2.93 |
| 2 | 120 | 1:1.6 | 2.28 |
| 3 | 135 | 1:1.8 | 1.34 |
| 4 | 150 | 1:2.0 | 0.92 |
As seen from Table 1, along with the increase of ferrous sulfate heptahydrate consumption, leaching arsenic concentration reduces, and repairing effect is better.
The inventive method handling object concentration high alkalinity is large, therefore, relative to conventional method, should be noted that medicament ratio, avoids concentration can not fall.Meanwhile, according to pH situation, need acid adding, and conventional method does not need.
Arsenic slag and ferrous salt add by the present invention simultaneously, one is in order to abundant mixing, two is for the ease of mechanized operation, is convenient to the layout of engineering site, because will assemble medicine machine on mixer, cumbersome, devices such as mixer having done acid adding, added water, be antifog and corresponding metering device, more complicated, medicine machine also needs to be equipped with the device controlling dosage, therefore the present invention takes to add medicament on a moving belt, then enters mixer together.And directly dosing is in mixer, both solid states, stir energy consumption large, and mixing is difficult to evenly; In addition, avoid sulphuric acid inaccurate and affect last pH, causing stabilization effect poor.
What the present invention adopted is molysite arsenic removal, in order to make ferric arsenate precipitate energy stable existence, under needing the pH value of regulation system to maintain weakly acidic condition.According to document analysis, in acid range, effect of removing arsenic is best, is greater than the animal migration under acid condition due to arsenate ion animal migration in the basic conditions, therefore reduces pH and can effectively reduce leaching arsenic concentration, improve the stabilization effect of arsenic.Simultaneously, the analysis of experiments of being undertaken by engineering site is found, to the arsenic slag of pH<8, ferrous sulfate heptahydrate can be adopted separately as reparation medicament, but to high concentration height pH arsenic slag, need to add ferrous sulfate heptahydrate and sulfuric acid as reparation medicament, and the pH after stirring reaction should control to pH 4-5, maintenance is pH 5-6 after at least 1 day.Specific experiment is as follows:
(1) waste residue in certain non-ferrous metals industry garden, for the arsenic slag 1:pH=7.5 of sampling, Leaching is 3144mg/L.500g arsenic alkaline slag is added beaker, then adds a certain amount of medicament, stir 2min, medicament is mixed with arsenic slag, then adds running water in beaker by solid-to-liquid ratio requirement, hand operated mixing is even, leaves standstill maintenance 2d.Leaching after process is 1.7mg/L, reaches standard.And for pH=12, Leaching is the 500g arsenic alkaline slag of 3860mg/L, operating procedure is the same, and the Leaching after process is 6.8mg/L, not up to standard.
(2) in the process parameter optimizing test of ferrous sulfate heptahydrate stabilisation scheme, for pH>14, Leaching is the 500g High Concentration of Arsenic alkaline residue of 4053mg/L, and control the addition of the concentrated sulfuric acid, result is as table 2:
Table 2
As shown in Table 2, during process High Concentration of Arsenic alkaline residue, even add a small amount of acid, last Leaching is still not up to standard, and acid adding amount need reach certain value, guarantees that final pH is reduced to better acid.Therefore, during process High Concentration of Arsenic alkaline residue, sulphuric acid and the stabilisation of pH on arsenic have significant impact.
In addition, if the useless standard of landfill of danger specifies that the landfill waste residue leachate pH after processing is still higher, pH > 12 is not up to standard, could landfill after needing process.Therefore, acid adding reduces pH is necessary.
In exploration process of the present invention, originally be estimate to add dilute sulfuric acid, but in dilution, because a large amount of heat release causes operating difficulties, and diluted acid dosing apparatus easily corrodes and even bores a hole, therefore change into and directly adding inside the concentrated sulfuric acid to waste residue, and coordinate and add a certain amount of water to meet the requirement of solid-to-liquid ratio.If just a small amount of sulfuric acid, dilution does not have problems, but through engineering approaches application needs the relatively large concentrated sulfuric acid, is inconvenient to operate, and increase diluted acid dosing apparatus causes cost increase.
Another key reason adding the concentrated sulfuric acid instead of dilute sulfuric acid in the present invention is: dilute sulfuric acid, because moisture content is high, can cause the waste residue after processing to become sposh shape, or even mud soup, and this is unfavorable for landfill.The useless standard of landfill of danger specify moisture content higher than 85% refuse need pretreatment after can admission landfill.
In the present invention, arsenic slag starts to be solid-state, is sticky shape after adding the concentrated sulfuric acid.Suitable stirring, without liquid after stirring.
In addition, acid adding after first stirring in the present invention is on the one hand fully mixing further, avoids local arsenic slag not touch stabilizing agent and not up to standard.Meanwhile, stirring makes reaction easily.Stirring power increases air contact, promotes reaction.The corrosivity of the concentrated sulfuric acid is strong.If direct first acid adding, then add stabilizing agent and stir, one is that the reason of solid causes uneven, and two is the reactions such as the concentrated sulfuric acid may cause first neutralizing, oxidation.Experiment finds that in arsenic slag, add sulfuric acid can produce bubble, Mao Baiyan, proves to have carbonate to exist.These all may be unfavorable for the solid arsenic of heavy arsenic.
Equipment of the present invention mainly comprises mixer, belt conveyer, vibratory sieve, unloads slag chute, charger, hammer crusher.Described mixer, belt conveyer, hammer crusher are the product directly bought.Vibratory sieve, to unload slag chute, charger etc. then actual according to application, and designed, designed size is also processed, and material is steel common on market.For convenience of mechanized operation, all devices, according to elevation needs, weld the support of certain altitude.
In treatment facility of the present invention mixer be overhead system, its loading hopper can promote up and down.Loading hopper can guarantee that the arsenic slag that conveyer belt transports enters loading hopper after declining.Mixer connects concentrated sulfuric acid carrier pipe, running water carrier pipe, and electric cabinet, high-precision electronic acid-proof flowmeter, mist acid exhaust device are housed.Concentrated sulfuric acid conveyance conduit selects D50PPR hot-water line.Preservative treatment is done to mixer and sour contact surface, brushes more than three times epoxy resin.Stabilizing agent charger is installed in belt conveyer rear end.Charger sets capacity, controls the medicament stirring needs each time well.Loading hopper is equipped with motor, controls to feed in raw material to facilitate.Mesh size about the 8cm of described vibratory sieve, square structure off the net is V-type, and opening is determined according to the width of conveyer belt.Motor is equipped with vibratory sieve, in order to control the vibration of screen cloth.Vibratory sieve becomes 3-5 to spend angle with horizontal plane, low side is provided with and unloads slag chute.Unloading slag chute is horizontally set at above conveyer belt, and become 10-15 to spend angle with horizontal plane, low side is provided with the feeder of bulk waste residue, stone.Treatment facility of the present invention can also comprise hammer crusher, and this stone crusher, for collecting bulk waste residue, stone from the feeder unloading slag chute, is put into after these bulk waste residues and stone fragmentation on vibratory sieve, and so forth again.
Ultrahigh concentration arsenic slag excavator is transported to vibratory sieve by the present invention, and after sieving, granule arsenic slag enters loading hopper with conveyer belt.Bulk waste residue, glides along wire side, and is transported to hammer crusher process, the arsenic slag after fragmentation after unloading slag chute collection, is positioned over former arsenic slag place, waits for next round process.While arsenic slag sieves, by charger, stabilizing agent ferrous salt (as ferrous sulfate heptahydrate) is joined on conveyer belt, enter in the lump in loading hopper with arsenic slag.According to arsenic slag concentration, adding by Fe:As mol ratio 1.8-3.0 of ferrous salt.After filling the arsenic slag being mixed with ferrous salt, promote loading hopper.Mixed material puts into mixer, fully stirs 5min.After arsenic slag stirs, with sulfuric acid pump, the concentrated sulfuric acid is directly delivered to the stir storehouse of mixer by pipeline.In every kg ferrous salt and arsenic slag mixture, the addition of the concentrated sulfuric acid is 30-50mL.And according to sulphuric acid, supplement running water according to liquid-solid ratio 1.5:10.Continue stirring 5 ± 2 minutes, from mixer discharging.Arsenic slag pH value after on-site measurement process, if pH is within the scope of 5-6, then it is qualified to process, and the High Concentration of Arsenic alkaline residue of stabilization processes is transported to security landfill place.Otherwise, need acid adding stir process again.
The present invention selects the agitator with liftable loading hopper, makes conveyer belt elevation lower, does not need overhead, save space and cost.The mixer of overhead system, the transhipment of the arsenic slag after convenient process.
Screen cloth is directly placed in above conveyer belt by the present invention, saves space, and floor space is little, and the waste residue after simultaneously sieving directly falls within conveyer belt, does not need transhipment, saves human cost.
The present invention arranges mist acid exhaust device and does preservative treatment to mixer and sour contact surface on mixer, directly can add the concentrated sulfuric acid like this, and be unlikely to etching apparatus in process arsenic slag process.
In the inventive method, arsenic slag and medicament are added on conveyer belt simultaneously, can mix in advance, ensure that the abundant contact of two kinds of solids, be conducive to the effect of stabilization processes.
Compared with prior art, beneficial effect of the present invention is:
(1) the present invention can to ultrahigh concentration arsenic slag (concentration: 60000-100000mg/kg; Arsenic leaching concentration: 3000-5000mg/L) carry out stabilization processes, waste residue Leaching after process is low, reach " hazard waste landfill Environmental capacity standard " control limit 2.5mg/L that (GB18598-2001) specifies, achieve the stabilization treatment of ultrahigh concentration arsenic-containing waste residue or soil.
(2) constructing operation is easy, mechanization degree is high, is convenient to through engineering approaches application.And arsenic has severe toxicity, in processing procedure, avoid a large amount of manual operations, can ensure personal safety.For the poisonous arsenic slag of ultrahigh concentration, realize mechanization, automation is disposed, very necessary.
(3) device structure is simple, handling ease, low cost of manufacture.Stabilizing agent is common medicament, with low cost.
(4) present invention process is simple, and the processing time is short, repairs fast efficient, does not produce secondary pollution.
In a word, the invention provides a kind of stabilizing treatment apparatus and method of the ultrahigh concentration arsenic slag can applied as through engineering approaches.This method technique is simple, and cost is low, repairs fast efficient, does not produce secondary pollution.Use the equipment of this technique, structure is simple, cheap for manufacturing cost, and mechanization degree is high, easy to operate, is convenient to through engineering approaches application.Especially respond well to the stabilization processes of ultrahigh concentration arsenic slag.
Accompanying drawing explanation
Fig. 1 is treatment facility structural representation of the present invention.
In figure, 1-mixer, 2-belt conveyer, 3-vibratory sieve, 4-unloads slag chute, 5-charger, 6-loading hopper, 7-electric cabinet, 8-flowmeter, 9-high-precision electronic acid-proof flowmeter, 10-running water delivery pump, 11-sulfuric acid delivery pump, 12-mist acid exhaust device, 13-feeds in raw material motor, 14-vibratory sieve motor, 15-hammer crusher.
Detailed description of the invention
Embodiment 1
For a stabilization treatment method for arsenic slag, comprise the steps:
(1) arsenic slag is sieved, the granule arsenic slag after sieving is added in loading hopper together with ferrous salt, the remaining bulk waste residue after sieving is collected for subsequent use; The ratio of ferrous salt and arsenic slag is pressed Fe:As mol ratio 1:3.0 and is controlled;
(2) ferrous salt and arsenic slag mixture are sent into mixer and stir 3min;
(3) in mixer, the concentrated sulfuric acid is added, discharging after continuation stirring 3min; In every kg ferrous salt and arsenic slag mixture, the addition of the concentrated sulfuric acid is 50mL; Controlling liquid-solid ratio in mixer is 1.8:10;
Wherein, in the described arsenic slag of step (1), arsenic content is 60000-100000mg/kg, and arsenic leaching concentration is 3000-5000mg/L.
Embodiment 2
For a stabilization treatment method for arsenic slag, comprise the steps:
(1) arsenic slag is sieved, the granule arsenic slag after sieving is added in loading hopper together with ferrous salt, the remaining bulk waste residue after sieving is collected for subsequent use; The ratio of ferrous salt and arsenic slag is pressed Fe:As mol ratio 1:1.8 and is controlled;
(2) ferrous salt and arsenic slag mixture are sent into mixer and stir 7min;
(3) in mixer, the concentrated sulfuric acid is added, discharging after continuation stirring 7min; In every kg ferrous salt and arsenic slag mixture, the addition of the concentrated sulfuric acid is 30mL; Controlling liquid-solid ratio in mixer is 1.2:10;
Wherein, in the described arsenic slag of step (1), arsenic content is 60000-100000mg/kg, and arsenic leaching concentration is 3000-5000mg/L.
Embodiment 3
See Fig. 1, the described stabilizing treatment apparatus for arsenic slag comprises mixer 1, belt conveyer 2, vibratory sieve 3 and charger 5; It is characterized in that, described mixer 1 is provided with lifting loading hopper 6, and described loading hopper 6 is near belt conveyer 2 front end; Be provided with vibratory sieve 3 above the conveyer belt of described belt conveyer 2, described vibratory sieve 3 rear end is provided with unloads slag chute 4; Described belt conveyer 2 rear end is provided with stabilizing agent charger 5; Described mixer 1 is also provided with mist acid exhaust device 12.
Described vibratory sieve 3 mesh size 6-10cm, vibratory sieve 3, horizontal by 3-5 ° of angles, unloads slag chute 4 horizontal by 10-15 ° of angles, described in unload slag chute 4 bottom and be provided with feeder.
Described mixer 1 is also provided with electric cabinet 7, described mixer 1 is also connected with sulfuric acid delivery pump 11, running water delivery pump 10, the pipeline that sulfuric acid delivery pump 11 is connected with mixer 1 is provided with high-precision electronic acid-proof flowmeter 9, and the pipeline that running water delivery pump 10 is connected with mixer 1 is provided with flowmeter 8.
Described vibratory sieve 3 is also provided with vibratory sieve motor 14.Charger 5 is also provided with reinforced motor 13.
Described treatment facility also comprises hammer crusher 15.
Certain non-ferrous metals industry garden of embodiment 4 is left over heavy metal pollution place High Concentration of Arsenic and is polluted dregs recovery project example
(in arsenic slag, arsenic content is 60000-100000mg/kg to adopt excavator to take the brownish red arsenic slag of ultrahigh concentration, arsenic leaching concentration is 3000-5000mg/L), put into screen cloth and remove bulk matter, granule arsenic slag enters in loading hopper with conveyer belt.Add ferrous sulfate heptahydrate on conveyer belt by loading hopper, enter in the lump in loading hopper with arsenic slag.Rear lifting filled by loading hopper, proceeded in stir storehouse by material and fully stirs 5min.Then acid adding regulates arsenic slag pH, while acid adding, opens mixing plant, stirs and make mixture be sposh shape.The present embodiment adopts size to be 0.5m
3mixer, after often turning a full dish loading hopper, the amount of arsenic slag is about 800kg, and the amount of ferrous sulfate heptahydrate is about 250kg (5 bags), and the concentrated sulfuric acid consumes 40L, and running water consumes 40L.Waste residue after process, it is 5.4 that scene records pH.The pH of maintenance slag after 2 days is 5.5, and leachate As concentration is 0.3mg/L, meets " hazard waste landfill Environmental capacity standard ".
Claims (3)
1. for a stabilization treatment method for arsenic slag, it is characterized in that, described method comprises the steps:
(1) arsenic slag is sieved, the granule arsenic slag after sieving is added in loading hopper together with ferrous salt, the remaining bulk waste residue after sieving is collected for subsequent use; The ratio of ferrous salt and arsenic slag is pressed Fe:As mol ratio 1:1.8-3.0 and is controlled;
(2) ferrous salt and arsenic slag mixture are sent into mixer and stir 3-7min;
(3) in mixer, the concentrated sulfuric acid is added, discharging after continuation stirring 3-7min; In every kg ferrous salt and arsenic slag mixture, the addition of the concentrated sulfuric acid is 30-50mL; Controlling liquid-solid ratio in mixer is 1.2-1.8:10;
Wherein, in the described arsenic slag of step (1), arsenic content is 60000-100000mg/kg, and arsenic leaching concentration is 3000-5000mg/L.
2., for a treatment facility for method described in claim 1, comprise mixer (1), belt conveyer (2), vibratory sieve (3) and charger (5); It is characterized in that, described mixer (1) is provided with lifting loading hopper (6), and described loading hopper (6) is near belt conveyer (2) front end; Be provided with vibratory sieve (3) above the conveyer belt of described belt conveyer (2), described vibratory sieve (3) rear end is provided with unloads slag chute (4); Described belt conveyer (2) rear end is provided with stabilizing agent charger (5); Described mixer (1) is also provided with mist acid exhaust device (12).
3. treatment facility as claimed in claim 2, it is characterized in that, described vibratory sieve (3) mesh size 6-10cm, vibratory sieve (3) is horizontal by 3-5 ° of angles, unload slag chute (4) horizontal by 10-15 ° of angles, described in unload slag chute (4) bottom and be provided with feeder.
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