CN103512930A - Method for determining adding amount of organic chelate heavy metal fixing agent - Google Patents
Method for determining adding amount of organic chelate heavy metal fixing agent Download PDFInfo
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- CN103512930A CN103512930A CN201210206650.2A CN201210206650A CN103512930A CN 103512930 A CN103512930 A CN 103512930A CN 201210206650 A CN201210206650 A CN 201210206650A CN 103512930 A CN103512930 A CN 103512930A
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Abstract
The invention relates to a method for determining the adding amount of an organic chelate heavy metal fixing agent. The method includes: immobilizing the heavy metal contained in heavy metal-containing dust, adding heavy metal-containing dust into a water solution containing acetic acid and an organic chelate heavy metal fixing agent to make a slurry, calculating the variation of oxidation reduction potential before and after adding of the heavy metal-containing dust, and determining the adding amount of the organic chelate heavy metal fixing agent according to the variation. According to the method provided by the invention, the necessary adding amount of the organic chelate heavy metal fixing agent can be more accurately determined.
Description
Technical field
The determining method of the organic chelate class heavy metal fixing agent addition that the present invention relates to make that heavy metal in the dust that burns or burn till or produce when the general discarded object of melting or industrial waste is innoxious, uses during stabilization.
Background technology
The dust that burns or burn till or discharge when the general discarded object of melting or industrial waste is the dust-like of the low boiling heavy metal class that contains volume, obligated enforcement is according to the leaching test of the HJT300-2007 of People's Republic of China (PRC) solid waste Leaching leaching method hac buffer method, suitably process, make it meet the standard value that household refuse landfill sites pollutes control criterion GB16889-2008.Suitably one of disposal route can be enumerated agent treated method, can be the most simply and process at an easy rate, thereby popularized.As the reagent treatment of agent treated method, can use organic chelate class reagent, mineral-type reagent, cement solidification method etc.
In Japan, as the method that determines to make containing the addition of the organic chelate class heavy metal fixing agent of the immobilization of heavy metals in heavy metal dusts, following methods is proposed: in the organic chelate class heavy metal fixative solution dissolving at organic chelate class heavy metal fixing agent, add containing heavy metal dusts, according to the variable quantity of the oxidation-reduction potential of slurry, determine the addition of organic chelate class heavy metal fixing agent.
No. 4254396th, [patent documentation 1] Jap.P.
But, in the prior art, there is following problem:
1) in the agent treated method by organic chelate class reagent, mineral-type reagent, cement solidification method etc., from considering to stablize process angle, really prevent that leaching ability of heavy metal from becoming prerequisite, but, from considering cost angle, without excessive nothing, adding insufficiently reagent, to become suitable addition also very important.But, be actually according to prior experimental result and determine reagent adding rate, with certain adding rate, process, the method can not be followed dust characteristic and be changed, aspect cost and stable processing aspect all have problems
Stablizing aspect processing, because can not confirm the variation at actual field dust, sometimes need again to implement test especially, confirm necessary addition.Therefore, analyze very consuming timely, and also exist to produce situation about not implementing during suitable treatments.
2) technology that patent documentation 1 is recorded can determine the addition as the organic chelate class heavy metal fixing agent of No. 13 tests of Japanese Environmental Agency of dissolution test Fa Japan bulletin, but, in the HJT300-2007 of People's Republic of China (PRC) solid waste Leaching leaching method hac buffer method, because of different from the not equal leaching test method of Japanese test solvent, so, the problem that existence can not correctly be measured.
Summary of the invention
The present invention puts forward for solving the existing problem of above-mentioned prior art, the object of the invention is to, provide a kind of and can make the method containing the addition of the fixing organic chelate class heavy metal fixing agent of the heavy metal containing in heavy metal dusts according to the correct decision of the HJT300-2007 of People's Republic of China (PRC) solid waste Leaching leaching method hac buffer method.
The present invention be a kind of can be according to the HJT300-2007 of People's Republic of China (PRC) solid waste Leaching leaching method hac buffer method, the correct method that determines the fixing organic chelate class heavy metal fixing agent addition containing the heavy metal in heavy metal dusts.The present invention first prepares aqueous acetic acid, with calcium hydroxide (lime hydrate) etc., is adjusted to certain pH, to this, is adjusted in the solution after certain pH, adds organic chelate class heavy metal fixing agent, prepares pretreatment solution.Measure after the ORP (oxidation-reduction potential) of pretreatment solution, add a certain amount of heavy metal dusts that contains, stir certain hour.If add containing heavy metal dusts, ORP rises than before adding, if after this stir certain hour, ORP is stable.The variable quantity (difference value) adding containing the ORP value before and after heavy metal dusts shows with the leaching ability of heavy metal measurer containing heavy metal dusts have very high correlativity.So the variable quantity demonstration of ORP value has very high correlativity with the addition of the organic chelate class heavy metal fixing agent of the immobilization of heavy metals necessity for containing heavy metal dusts.The necessary addition of so-called organic chelate class heavy metal fixing agent refers to and can, according to the test findings of the HJT300-2007 of People's Republic of China (PRC) solid waste Leaching leaching method hac buffer method, process and make leaching ability of heavy metal become the addition below certain value.
As follows as concrete means:
1) in pure water, add a certain amount of acetic acid, mix.Containing heavy metal dusts addition 100 weight portions, acetic acid addition is 30-40 weight portion relatively.In acetum after adjustment, add a certain amount of lime hydrate etc., stir certain hour, it is evenly mixed, make pH value for certain.
2) above-mentioned 1) solution in, add a certain amount of organic chelate class heavy metal fixing agent, mix, prepare solution.This solution is " pretreatment solution ".According to the concentration of organic chelate class heavy metal fixing agent, ORP value shows certain value.
3) if add a certain amount of heavy metal dusts that contains in pretreatment solution, be adjusted into pulp-like, heavy metal stripping from contain heavy metal dusts.The rapid chelating combination of organic chelate class heavy metal fixing agent of the heavy metal of stripping and dissolving, forms difficulty/insoluble compound, makes the immobilization of heavy metals of stripping.Along with chelating is in conjunction with carrying out, the concentration of the organic chelate class heavy metal fixing agent of dissolving reduces, that is, reducing substances consumption, ORP value rises to positive side.
4) if finish from the chelating association reaction containing the heavy metal of stripping heavy metal dusts and the organic chelate class heavy metal fixing agent of dissolving, ORP becomes necessarily.
5) ask for the ORP value and above-mentioned 4 before adding containing heavy metal dusts) the variable quantity (difference value) of ORP value.
6) respectively containing in heavy metal dusts (N number=2～3), can be according to the lubber-line of the variable quantity of the ORP trying to achieve (difference value) and the organic chelate class of trying to achieve according to HJT300-3007 leaching test heavy metal fixing agent in advance, from above-mentioned 5) measurement result determine the necessary addition of organic chelate class heavy metal fixing agent.
As for solving the means of above-mentioned problem, provide following methods: first add acetic acid/alkaline adjusting agent/organic chelate class, obtain pretreatment solution, measure ORP, after mensuration, add containing heavy metal dusts, observe that ORP rises and stable after, calculate this ORP value and add the difference value containing the ORP value before heavy metal dusts, determine the necessary addition of organic chelate class heavy metal fixing agent.
[containing the definition of heavy metal dusts]
Tie up to the dust that burns or burn till or produce when the general discarded object of melting or industrial waste, the ash that tower is cleaned in the gas cooled ash of the dust of collecting by particle collector, boiler ash, exhaust cooling tower, exhaust etc.
The peculiar effect > of each technical scheme of <
The present invention relates to a kind of method, it can, according to the HJT300-2007 of People's Republic of China (PRC) solid waste Leaching leaching method hac buffer method, determine for preventing as the necessary addition of processing the organic chelate class heavy metal fixing agent containing heavy metal dusts leaching ability of heavy metal of object.
The peculiar effect of each technical scheme is described below.
< technical scheme 1 >
In HJT300-2007 solid waste Leaching leaching method hac buffer method, solvent is used acetic acid or sodium acetate buffer aqueous solution.Except special circumstances, general, containing the proterties of heavy metal dusts due to in and sour gas (HCl, Sox) object in Exhaust Gas, use lime hydrate etc., therefore, aobvious alkalescence mostly, the solvent that leaching test is used is nearly all used aqueous acetic acid.The pH of aqueous acetic acid is 2.64 ± 0.05, puts into as the heavy metal dusts that contains of subjects and implement leaching test in this solvent.Liquid-solid ratio (L/S=liquid mL: be test portion weight g) 20, leaching method is used the rotary-type device that soaks into, make its 18hr (hour) soak into.Because solvent is that acid and L/S are high, leaching method adopts rotary-type and soaks into for a long time for 18 hours, makes containing the stripping quantity of heavy metal in heavy metal dusts very highly, from security standpoint, sees it is strict leaching test method.The technical program is the method for the decision organic chelate class heavy metal fixing agent addition corresponding with this HJT300-2007 solid waste Leaching leaching method hac buffer method.By using acetic acid, improved the stripping quantity containing heavy metal in heavy metal dusts, and in the pretreatment solution of acetic acid, organic chelate class heavy metal fixing agent, by interpolation, contain heavy metal dusts, the variation quantitative change of ORP value is large, can measure more accurately the necessary addition of organic chelate class heavy metal fixing agent.Particularly solvent is without pure water, and use acetic acid, make the variation quantitative change of ORP value large, and high with the correlativity of the necessary addition of organic chelate class heavy metal fixing agent in HJT300-2007 solid waste Leaching leaching method hac buffer method, can be more really and correctly determine addition.
The basic consideration for measuring principle by ORP is below described:
< measuring principle >
Organic chelate class heavy metal fixing agent is containing dithiocarbamate-based sequestrant, is sulfur compound ion (S substantially
2-) reducing substances.Therefore, low containing the ORP value of the aqueous solution of organic chelate class heavy metal fixing agent, the concentration of demonstration organic chelate class heavy metal fixing agent is higher, and ORP value is lower.The present invention is conceived to organic chelate class heavy metal fixing agent strong reducing property, using ORP as measuring principle.
If containing adding containing heavy metal dusts and mix in the aqueous solution (reductibility) of organic chelate class heavy metal fixing agent, the reagent concentration of organic chelate class heavy metal fixing agent, because of heavy metal and reagent reacting, along with time process, reagent concentration minimizing.That is,, from the heavy metal containing stripping heavy metal dusts and the reaction of organic chelate class heavy metal fixing agent, reagent concentration minimizing=ORP value raises.The heavy metal dissolving is more, with the consumption of organic chelate class heavy metal fixing agent reagent concentration,
the necessary adding rate of the organic chelate class heavy metal fixing agent of the variable quantity of this ORP value and HJT3000-2007 solid waste Leaching leaching method hac buffer method has correlativity, therefore, according to assay method of the present invention, can predict the necessary amount of organic chelate class heavy metal fixing agent.
< technical scheme 2 >
By regulation acetic acid with containing the ratio of the addition of heavy metal dusts, before and after adding containing heavy metal dusts, the correlativity of the necessary adding rate of the variable quantity of ORP value and the organic chelate class heavy metal fixing agent of HJT300-2007 solid waste Leaching method hac buffer method further improves, and precision uprises.
By acetic acid with containing the proportional divider of the addition of heavy metal dusts, be decided to be 0.30-0.40 scope according to as follows:
< HJT300-2007 solid waste Leaching leaching method hac buffer method >
1)
2)
This leaching test law regulation acetate concentration and liquid-solid ratio, so containing heavy metal dusts 1kg, acetic acid amount is 34.5g relatively.By the acetate concentration that relatively contains heavy metal dusts is made as to certain value, suppress respectively to contain the deviation of heavy metal dusts heavy metal amount of stripping from acetum, and identical with leaching test method relatively containing the acetate concentration of heavy metal dusts by being made as, further improve relevant to the necessary addition of organic chelate class heavy metal fixing agent in leaching test method.
< technical scheme 3 >
The object of technical scheme 3 is, by the pH of pulp-like solution is made as necessarily, reduces the impact of pH on ORP value.If the pH before and after adding containing heavy metal dusts is different, ORP value changes greatly, therefore, ORP value is used for to measuring principle occasion, take that to improve mensuration precision be object, and pH value of solution is established within the specific limits.By the pH of pulp-like solution is made as to alkalescence, can prevents the pH value dependence containing the leaching ability of heavy metal amount in heavy metal dusts, and can increase leaching ability of heavy metal amount again.Also as described in technical scheme 2, by the pH of pulp-like solution is made as to certain value, further improve relevant to the necessary addition of organic chelate class heavy metal fixing agent in leaching test method.
Accompanying drawing explanation
Fig. 1 represents pretreatment procedure one example in organic chelate class heavy metal fixing agent addition determining method of the present invention.
Fig. 2 represents mensuration operation one example in organic chelate class heavy metal fixing agent addition determining method of the present invention.
Fig. 3 represents that ORP changes schematic diagram.
Fig. 4 represents that difference Zhi ⊿ P calculates schematic diagram.
Fig. 5 represents the relation of " difference Zhi ⊿ P " and " the necessary addition of HJIT300-2007 ".
Fig. 6 represents to make lubber-line.
Fig. 7 represents reinforced management devices skeleton diagram.
Fig. 8 represents application method schematic diagram of the present invention.
Fig. 9 represents the lubber-line of embodiment 1, comparative example 1.
Figure 10 represents the lubber-line of embodiment 2, comparative example 2.
Figure 11 represents the ORP value variation diagram of processing procedure.
Figure 12 system represents the ORP value variation diagram of processing procedure with curve.
Embodiment
Below describe the example of organic chelate class heavy metal fixing agent addition determining method of the present invention in detail.
The present invention is the method for organic chelate class heavy metal fixing agent addition that determines according to following operation, measuring principle.
[pretreatment procedure]
Below describe " pretreatment procedure " in organic chelate class heavy metal fixing agent addition determining method of the present invention in detail.
1) in pure water X (volume L), add acetic acid, relatively containing heavy metal dusts A weight portion, add acetic acid 0.3～0.4 * A weight portion.The acetum adding can be also glacial acetic acid, still, is preferably, and uses the reagent injection pump of acetic acid special use automatically to inject, and uses the acetum of number % (1～10%) can reduce concentration deviation.Using acetic acid is owing to being acetate solvate according to the solvent of the HJT300-2007 of People's Republic of China (PRC) solid waste Leaching leaching method hac buffer law regulation.
2) add after acetic acid, use transit mixer to stir the aqueous solution of pure water and acetic acid mixing, under this state, add quantitative pH adjusting agent.PH adjusting agent so long as aobvious alkaline material just, be not particularly limited, still, lime hydrate preferably.Lime hydrate occasion, the alkaline ability of lime hydrate itself is high, and saturated pH value is 12.5, as long as add to a certain amount of more than, just can keep stable pH value, again, alkaline principal ingredient in dust is lime hydrate, therefore be preferably, using " lime hydrate " as pH adjusting agent, uses.The addition of pH adjusting agent, because the alkaline ability of each pH adjusting agent is different, while using lime hydrate, is preferably, and relatively, containing heavy metal dusts A weight portion, adds 0.5～2.0 * A weight portion.
3) add after pH adjusting agent, use transit mixer to stir, under this state, drip quantitative titration reagent, stir.
The addition of titration reagent is, relatively from the heavy metal containing heavy metal dusts stripping of determination object, and excessive interpolation.Titration reagent is organic chelate class heavy metal fixing agent, is made as and uses containing dithiocarbamate-based organic chelate class.Be preferably the reagent of the organic chelate class heavy metal fixing agent identical type of using while using with actual treatment.Kind as titration reagent, is preferably, piperazidine aminodithioformic acid and salt thereof, diethyldithiocar bamic acid and salt thereof, dimethyl dithiocarbamic acid and salt thereof, TEPA and salt thereof, polyamines aminodithioformic acid and salt thereof etc.The concentration of titration reagent is 0.5～3.0 % by weight preferably.
4) a series of stirring above-mentioned 1)～3) implements until ORP value and pH value stabilization, and it is more than 5 minutes being preferably mixing time, is more preferably stirring more than 15 minutes.Using the ORP value after ORP value stabilization as initial ORP value, be made as E start.
The charging sequence of each reagent is,
or
the order of acetic acid and pH adjusting agent is random, but titration reagent finally adds.
5) operation above-mentioned 1)～4) is pretreatment procedure.
Fig. 1 represents pretreatment procedure one example in organic chelate class heavy metal fixing agent addition determining method of the present invention.
As shown in Figure 1, in pretreatment procedure, carry out following steps:
Step 1: in pure water 3L, add 100ml, 1.725% acetum, stir.
Step 2: add lime hydrate 3-6g, stir 5 minutes (making pH value for certain).
Step 3: drip the titration reagent (1% concentration benchmark) of 5-15ml, stir 10-15 minute (completing pretreatment solution).
Step 4: after step 3 finishes, will add containing the ORP value before heavy metal dusts as initial ORP value.
[mensuration operation]
Below describe " mensuration operation " in organic chelate class heavy metal fixing agent addition determining method in detail.
1), after pretreatment procedure finishes, using under transit mixer stirring, drop into become object containing heavy metal dusts Y weight portion.Containing the input amount Y (weight portion) of heavy metal dusts because of the proterties of dust, particularly content of beary metal different, still, as a standard roughly, Y (weight portion)=X (L) * 10
-2～10
-3(liquid-solid ratio L/S=100～1000).
2) input becomes containing after heavy metal dusts of object, stirs institute and fixes time, and the ORP value of pulp-like solution rises, and the ORP value after stirring is fixed time, as ORP, is made as E end.E end, using the ORP value stabilization duration of pulp-like solution as cardinal principle target, is preferably, and input becomes containing after heavy metal dusts of object, stirs more than 10 minutes.But, according to containing the proterties of heavy metal dusts, also have mixing time be 10 minutes with interior situation, mixing time is not particularly limited.
3) according to above-mentioned 2), read ORP value: E end, asks difference Zhi ⊿ P=E end-E start.
Calculate after difference Zhi ⊿ P, use the automatic calculating formula determining according to lubber-line, determine that necessary reagent injects adding rate.
Fig. 2 represents mensuration operation one example in organic chelate class heavy metal fixing agent addition determining method of the present invention.
As shown in Figure 2, in measuring operation, carry out following steps:
Step 5: in pretreatment solution, drop into containing heavy metal dusts 5g while stir.
Step 6: drop into containing after heavy metal dusts, stir certain hour (for example, stirring more than 10 minutes).
After when step 7:ORP stablizes, finish (dropping into containing the ORP value after heavy metal dusts).
Fig. 3 represents that ORP changes schematic diagram, and as shown in Figure 3, abscissa represents time T, and ordinate represents ORP (mv).Under water state, be E1.Add after acetic acid, under water+acetic acid state, become E2.Then, add lime hydrate, under water+acetic acid+lime hydrate state, become E3.Then, add titration reagent, under pretreatment solution+titration reagent state, become E start.It is more than pretreatment procedure.
Then, add containing heavy metal dusts, after stirring institute fixes time, read ORP value: E end, asks difference Zhi ⊿ P=E end-E start.More than for measuring operation.
Below describe the establishing method of the automatic calculating formula determining according to lubber-line in detail.
1) about become determination object containing heavy metal dusts (about N=3), confirm the necessary addition of applicable organic chelate class heavy metal fixing agent.Confirm the dissolution test method confirmation of method according to the HJT300-2007 of People's Republic of China (PRC) solid waste Leaching leaching method hac buffer method of necessary addition.Organic chelate class heavy metal fixing agent, for containing dithiocarbamate-based sequestrant, can be enumerated Hg as object heavy metal, Cu, and Pb, Cd, Zn, the heavy metal that generally becomes object is mainly Pb.
Table 1
* 1: expression can meet the necessary addition (% by weight) of organic chelate class heavy metal fixing agent that household refuse landfill sites pollutes the standard of landfill value of control criterion GB16889-2008.
Table 1 represents, for the heavy metal dusts that contains that becomes determination object, to confirm the example of the necessary addition of applicable organic chelate class heavy metal fixing agent.
2) about above-mentioned 1) determine the necessary addition of organic chelate class heavy metal fixing agent containing heavy metal dusts (known dust: three kinds), according to above-mentioned " pretreatment procedure ", the order of " mensuration operation ", asks difference value ⊿ P.The most applicable detailed condition of the amount of research titration reagent, dust while asking difference Zhi ⊿ P etc.
Fig. 4 represents that difference Zhi ⊿ P calculates schematic diagram, represents to add containing heavy metal dusts A bis-kinds of B.As shown in the drawing, containing the more dust of the necessary addition of reagent in heavy metal dusts, difference value ⊿ P is higher.Reason is that the necessary addition of reagent is more, and residual reagent concentration in pulp-like solution is lower=and the consumption of titration reagent is larger, and ORP value becomes the direction that approaches E3 (solution of water+acetic acid+lime hydrate).
Add containing after heavy metal dusts, when becoming as object again,
time, can adopt the amount that again increases titration reagent, or increase the concentration of titration reagent, or increase the correspondences such as titration number of times of titration reagent.By such correspondence, even if changing, dust proterties also can carry out significantly correspondence.
In table 2, represent according to the relation of the necessary addition of HJT300-2007 and difference Zhi ⊿ P.
Table 2
For respectively, containing heavy metal dusts, as shown in Figure 5, ask for the relation of " difference Zhi ⊿ P " and " the necessary addition of HJIT300-2007 ", make lubber-line, for example, Y (%)=a ⊿ P+b.In Fig. 5, represent to make proximal line Y=aX.
If make lubber-line with this example, make lubber-line as shown in Figure 6, make the calculating formula of the necessary addition of organic chelate class heavy metal fixing agent.In Fig. 6, R
2represent related coefficient.
Fig. 7 represents reinforced management devices skeleton diagram.
In Fig. 7, symbol 1 represents charge door, and symbol 2 represents level sensor, symbol 3 represents setting/guidance panel, symbol 4 represents stirring machine/motor, and symbol 5 represents scavenging pump, and symbol 6 represents to control matrix, symbol 7 represents titration reagent pump, symbol 8 represents tank diameter (3L), and symbol 9 represents sensor, and symbol 10 represents acetic acid pump, symbol 11 represents make-up water pump, and symbol 12 represents draining valve.In addition, reinforced management devices can also comprise other accessories, for example, and water supply tank, acetic acid tank, titration reagent pot, cleaning fluid tank etc.
Reinforced management devices operation summary flow process is as follows:
1) carry out dewatering in tank diameter (sour cleaning solution), water cleans tank diameter once (automatically).
2) with make-up pump to the tank diameter 1L (automatically) that supplies water.
3) use acetic acid pump that quantitative acetum is joined to tank diameter (automatically).
4) get quantitative pH adjusting agent (being mainly lime hydrate), from charge door, add (manually).
5) after reinforced, again to tank diameter, supply water to 3L (automatically).
6) after stirring institute fixes time, use titration reagent pump to add quantitative titration reagent (automatically).
7) after stirring institute fixes time, get quantitative dust, from charge door, add (manually).
8) add after dust, stir institute and fix time, read ORP:E start/E end, the necessary adding rate (automatically) of being injected by automatic calculating formula visualizingre agent.
9) after mensuration finishes, discharge the pulp-like solution (automatically) in tank diameter.
10) after discharging, by the repeated multiple times washing/draining of supplying water, finally fill it up with the water of 3L, add after pickle, finish a series of processing (automatically).
Fig. 8 represents application method schematic diagram,
The following describes the embodiment of the present invention/comparative example.
[embodiment 1]
1) in the 5L still with stirring machine, add pure water 3L and 1.725% acetate solvate 100ml, with rotating speed 400rpm, stir.(stirring rate maintains 400rpm)
2) then,, in order to keep certain pH, add lime hydrate (Ca (OH)
2) 6g, stir 10 minutes.
3) add 1% aqueous solution 15ml of Kurita Water Industries Ltd's heavy metal fixing agent processed " Ashnite S-803 ", stir 5 minutes.
4) use ORP meter (East Asia electric wave system, electrode: platinum, Ag-AgCl, 3.3M KCl) to measure above-mentioned 3) ORP after finishing.This ORP is made as to E start.
5) after this, add dust F5g shown in following table, use while stirring ORP instrumentation to determine ORP15 minute.
Again, for dust G shown in following table 3, dust H, and as the only interpolation " lime hydrate " of non-processor dust test, carry out and above-mentioned same adjustment, measure ORP.
The constituent analysis result of test specimen dust is as shown in table 3 below, and the dissolution test result of " Ashnite S-803 " is as shown in table 4 below:
Table 3
| Analysis project | Unit | Dust F | Dust G | Dust H |
| Water percentage | % by weight | 1.0＞ | 1.2 | 1.0＞ |
| Former dust P-basicity | ‘mg-CaCO 3/g | 320 | 420 | 378 |
| Pb | ' mg/kg-dust | 1250 | 2800 | 4200 |
Table 4
Remarks: according to the HJT300-2007 of People's Republic of China (PRC) solid waste Leaching leaching method hac buffer method (Pb standard value: 0.25mg/L is following).
[embodiment 2]
1) use " reinforced management devices " as shown in Figure 7 to test.
2) in 5L tank diameter, add 1L pure water, add thereafter 1.725% acetum 100ml, stir.
3) after stirring, add 2L pure water, in order to keep certain pH, add Ca (OH)
25g, stirs 10 minutes.
4) add 1% aqueous solution 10ml of Kurita Water Industries Ltd's heavy metal fixing agent processed " Ashnite S-812 ", stir 5 minutes.
5) use ORP meter (East Asia electric wave system, electrode: platinum, Ag-AgCl, 3.3M KCl) to measure above-mentioned 3) ORP after finishing.Using this ORP as E start.
6) after this, add the object dust 5g shown in following table, with ORP instrumentation, determine ORP 10 minutes while stirring.
Again, even for the test of the only use " lime hydrate " as non-processor dust, also do and above-mentioned same adjustment, measure ORP.
Again, [comparative example 2] for being used reinforced management devices to implement test under the test condition that does not add acetate solvate.
The constituent analysis result of test specimen dust is as shown in table 5 below, and the dissolution test result of " Ashnite S-812 " is as shown in table 6 below:
Table 5
| Analysis project | Unit | Dust KN-1 | Dust KN-2 | Dust KN-3 |
| Water percentage | % by weight | 1.0＞ | 1.0＞ | 1.0＞ |
| Pb | ' mg/kg-dust | 1030 | 1560 | 2150 |
Table 6
The detailed test findings of embodiment 1,2/ comparative example 1,2 is as follows.
" Ashnite S-803 ": the organic chelate class heavy metal fixing agent of piperazidine aminodithioformic acid potassium
" Ashnite S-812 ": the organic chelate class heavy metal fixing agent of diethyldithiocar bamic acid potassium
Table 7
| |
The desirable adding rate (%) of S-803 | ⊿P(mv) |
| |
2 | 20 |
| |
4 | 38 |
| |
6 | 57 |
Table 8
| Comparative example 1 | The desirable adding rate (%) of S-803 | ⊿P(mv) |
| |
2 | 1 |
| |
4 | 4 |
| |
6 | 13 |
Table 9
| |
The desirable adding rate (%) of S-803 | ⊿P(mv) |
| Non-processor dust | 0.0 | 1 |
| Dust KN-1 | 1.5 | 14 |
| Dust KN-2 | 2.5 | 22 |
| Dust KN-3 | 3.0 | 29 |
Table 10
| Comparative example 2 | The desirable adding rate (%) of S-803 | ⊿P(mv) |
| Non-processor dust | 0.0 | 1 |
| Dust KN-1 | 1.5 | 3 |
| Dust KN-2 | 2.5 | 7 |
| Dust KN-3 | 3.0 | 12 |
For the purpose of understanding, Fig. 9 represents the lubber-line of embodiment 1, comparative example 1, and Figure 10 represents the lubber-line of embodiment 2, comparative example 2.
[test condition]
Table 11 represents test condition:
Table 11
| Project | Quantity | Unit |
| Dust | 5 | g |
| 1.725%CH 3COOH | 100 | ml |
| Pure water | 3 | L |
| Ca(OH) 2 | 6 | g |
| Stirring rate | 400 | |
| Ashnite S | ||
| 1 |
15 | ml |
[embodiment 1]
No.1
Sample: dust F
Ashnite S adding rate (%): 2.0
Table 12
， ⊿ ORP=E end-E start Zhong table 12.
Above-mentioned " process 1 ": in pure water 3L, add 100ml, 1.725% acetate solvate, with 400rpm, stir, the ORP value of adding after lime hydrate is passed.
" process 2 ": in the solution of " process 1 " gained, the ORP value of adding after " Ashnite " is passed.
" process 3 ": in the solution of " process 2 " gained, add containing the ORP value after heavy metal dusts and pass.
No.2
Sample: dust G
Ashnite S adding rate (%): 4.0
Table 13
No.3
Sample: dust H
Ashnite S adding rate (%): 6.0
Table 14
[comparative example 1]
No.1
Sample: dust F
Ashnite S adding rate (%): 2.0
Table 15
No.2
Sample: dust G
Ashnite S adding rate (%): 4.0
Table 16
No.3
Sample: dust H
Ashnite S adding rate (%): 6.0
Table 17
Reinforced management device experiment result is as follows:
[test condition]
Table 18 represents test condition:
Table 18
| Project | Quantity | Unit |
| Dust | 5 | g |
| 1.725%CH 3COOH | 100 | ml |
| Pure water | 3 | L |
| Ca(OH) 2 | 6 | g |
| Stirring rate | 400 | |
| Ashnite S | ||
| 1 |
10 | ml |
[embodiment 2]
No.4
Sample: dust KN-1
Ashnite S adding rate (%): 1.5
Table 19
No.5
Sample: dust KN-2
Ashnite S adding rate (%): 2.5
Table 20
No.6
Sample: dust KN-3
S-803 adding rate (%): 3.0
Table 21
No.7
Sample: non-processor dust test (Ca (OH) 2)
S-803 adding rate (%): 0.0
Table 22
[comparative example 2]
No.4
Sample: dust KN-1
Ashnite S adding rate (%): 1.5
Table 23
No.5
Sample: dust KN-2
Ashnite S adding rate (%): 2.5
Table 24
No.6
Sample: dust KN-3
S-803 adding rate (%): 3.0
Table 25
No.7
Sample: non-processor dust test (Ca (OH) 2)
S-803 adding rate (%): 0.0
Table 26
In the present invention, by experiment, try to achieve the necessary reagent adding rate of each F～H dust (three kinds).
In the present embodiment, the necessary adding rate of reagent " Ashnite S-803 " is as follows:
F dust: more than 2.0%
G dust: more than 4.0%
H dust: more than 6.0%
In the present invention, so-called " more than 2.0% ", comprises 2.0%, and other are all so analogized.
As mentioned above, use each F～H dust of knowing necessary reagent adding rate, implement the test based on embodiment.
As mentioned above, main points are as follows for measuring principle:
(1) the present invention be a kind of decision for make containing the immobilization of heavy metals of heavy metal dusts, as the method for the reagent addition of the organic sequestering agent of heavy metal fixing agent.
(2) be conceived to organic sequestering agent and show very strong reductibility, ORP is made as to measuring principle.
(3) if drop into containing heavy metal dusts and mix in comprising organic sequestering agent+vinegar aqueous acid, organic sequestering agent reacts and is consumed with the heavy metal of dissolving, and reagent concentration reduces, that is, ORP value uprises.Again, the heavy metal of dissolving is more, and reagent concentration reduces more, and therefore, it is large that the difference of ORP value variable quantity becomes.
(4) Chinese test method occasion, solvent is used acetic acid, by use acetum in solvent, consistent with Chinese test method, is a kind of assay method of measuring precision that improves.
As mentioned above, the test routine of comparative example is in embodiment program, not add the method for acetic acid to the test routine of the present embodiment.
First, in the invention described above embodiment/comparative example, so-called " non-processor dust " is to replace dust with " lime hydrate ", confirms the variable quantity of ORP value." lime hydrate " occasion, owing to not containing heavy metal, organic sequestering agent is not consumed, and before and after " lime hydrate " adds, ORP value changes hardly.
Should " non-processor dust " be to implement as the confirmation before measuring.
Then, actual each F～H dust that drops into, the variable quantity of confirmation ORP value.
From the invention described above embodiment/comparative example, all become following result: necessary reagent adding rate higher (F dust < G dust < H dust), organic sequestering agent is consumed more, and the variation quantitative change of ORP value is large.
But, comparative example assay method occasion, with embodiment comparison, the variable quantity of ORP value is little, and meanwhile, the related coefficient of lubber-line (variable quantity of ORP value and necessary reagent adding rate) is low.
Related coefficient is higher, and it is higher that meaning is measured precision.
Again, embodiment occasion, more known with comparative example, the interval of necessary reagent adding rate is little, can set without excessive or not enough reagent addition.
Example of the present invention has been described, but the present invention is not limited to above-mentioned example above, in the technology of the present invention thought range, can does all changes, they all belong to protection scope of the present invention.
Claims (4)
1. an addition determining method for organic chelate class heavy metal fixing agent, described fixing agent makes, containing the immobilization of heavy metals comprising in heavy metal dusts, to it is characterized in that:
In the aqueous solution containing acetic acid and organic chelate class heavy metal fixing agent, add containing heavy metal dusts, modulation forms pulp-like, calculate the variable quantity of the oxidation-reduction potential before and after adding containing heavy metal dusts, according to this variable quantity, determine the addition of organic chelate class heavy metal fixing agent.
2. the addition determining method of organic chelate class heavy metal fixing agent according to claim 1, is characterized in that:
Acetic acid and be 0.3～0.4:1 containing the weight ratio of heavy metal dusts.
3. the addition determining method of organic chelate class heavy metal fixing agent according to claim 1 and 2, is characterized in that:
Processing object is according to the HJT300-2007 of People's Republic of China (PRC) solid waste Leaching leaching method hac buffer method test findings, and the pH of dissolution fluid is more than 7.0 heavy metal dusts that contains.
4. the addition determining method of organic chelate class heavy metal fixing agent according to claim 1 and 2, is characterized in that:
Use pH adjusting agent to adjust pH value, to make in scope that the pH of above-mentioned pulp-like aqueous solution is 11.0～13.0.
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| CN104001299A (en) * | 2013-02-22 | 2014-08-27 | 栗田工業株式会社 | Stabilizing treatment method preventing heavy metal from dissolving from powder |
| CN106018281A (en) * | 2015-03-25 | 2016-10-12 | 住重环境工程技术株式会社 | Quantitative method and quantitative system of chelating agent |
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