CN107202865A - Heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash - Google Patents
Heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash Download PDFInfo
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Abstract
The invention discloses heavy metal stabilizing in a kind of domestic garbage incineration flyash and toxicity quick determination method, garbage flying ash testing sample is divided into three parts, first part of flying dust surveys pH value of solution, lead ion, chlorion and calcium ion concentration after being mixed with water；Second part of flying dust mixed with water after by the way that acetum is added dropwise to neutrality, survey acid-neutralizing capacity；3rd part of flying dust is mixed with strontium nitrate and glycerine absolute ethyl alcohol, is titrated by benzoic acid absolute ethyl alcohol, surveys free calcium oxide mass percent in flying dust.Finally by draw multiple indexs come comprehensive descision flying dust heavy metal stabilizing it is whether qualified, i.e., whether Leaching up to standard.The present invention is solved the problems, such as to exist when currently used national standard Leaching leaching method judges landfill yard admission fly-ash heavy metal stability with duration, efficiency is low and is difficult to live real-time monitoring, the time-consuming national standard method more than 18 hours is shorten to the time-consuming synthetic determination method less than 1 hour, admission fly-ash heavy metal stability supervisory efficiency is effectively improved.
Description
Technical field
The present invention relates to the dirt of the pollution parameters detection method, particularly domestic garbage incineration flyash of a kind of solid waste
Parameter chemical detection method is contaminated, applied to household refuse landfill sites pollution control technology field.
Background technology
Fly ash from burning city domestic garbage is collected using system, flue gas purification system in recuperation of heat after consumer waste incineration
Material, wherein there is the multiple harmful substances such as the content higher cadmium that can be flooded out, lead, zinc, chromium.If dealing with improperly, it will
Cause heavy metal transformation, polluted underground water, soil and air.Therefore, incineration of refuse flyash is put into《National Hazard waste name
Record》, belong to hazardous waste, it is necessary to strict supervision and safe disposal.With the continuous growth of urban population, domestic waste is not
Disconnected increase, waste incineration is the inevitable choice of garbage harmless recycling treatment.
Contain substantial amounts of heavy metal contaminants in flying dust, the solidification flying dust after mixing curing process processing enters landfill
Leaching is substantially reduced after, compares uncured flying dust, the overwhelming majority meets standard limited value, but also have the exceeded feelings in part
Condition.Method currently used for heavy metal stabilizing in detection flying dust is that solid waste in Environment Protect in China professional standard is leached
Toxicity leaching method sulfonitric method and hac buffer method.But the testing conditions of national standard method requirement it is strict, it is necessary to
Using a variety of special instruments, and it is longer to expend the time, and upset processing is time-consuming to be more than 18 hours.Each domestic large-scale flying dust landfill
Field is required for receiving the tens batch flying dusts produced from the multiple garbage burning factories in surrounding area daily, enters landfill in flying dust
During landfill stabilization, using national standard Leaching leaching method be difficult to according to《Household refuse landfill sites contamination control standard》
Live real-time monitoring is carried out to the heavy metal stabilizing for entering landfill yard flying dust, part heavy metal stabilization can be caused incomplete
Flying dust is directly entered landfill yard and filled, the hidden danger that there is environmental pollution.I.e. at present for fly ash from burning city domestic garbage
The detection method of middle heavy metal stabilizing, which exists, uses duration, the shortcoming of inefficiency, cause pretreatment quality and landfill process compared with
Difficult coordinated implementation, admission flying dust quality, which is checked on, to be difficult to implement.Therefore, it is a kind of more easy to be higher than national standard method in the urgent need to finding
The detection method of effect, carrys out the Leaching Heavy Metals of rapid evaluation admission flying dust, is realized with this dirty to household refuse landfill sites
Effective control of dye.
The content of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash, easy can rapidly detect house refuse
The stability of heavy metal in flying ash, is that the quality of landfill yard admission flying dust is checked on offer solution, improves admission flying dust
The supervisory efficiency of heavy metal stabilizing, guarantee environment safety.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
Heavy metal stabilizing and the quick determination method of toxicity, comprise the following steps in a kind of domestic garbage incineration flyash：
(1) domestic garbage incineration flyash testing sample is provided, and the domestic garbage incineration flyash testing sample of offer is divided
It is standby respectively for three parts；
(2) the first part of flying dust sample that will prepare in step (1) is mixed with water, and stirring obtains first after at least 14 minutes
Mixed liquor, using pH meter, measures the pH value of the first mixed liquor；Addition 0.1ml mass percentages in the first mixed liquor are stated then up
Specific concentration is 65~68% nitric acid, obtains the first mixed liquor test fluid, continues to stir the first mixed liquor test fluid at least 1 minute
Afterwards, then using ionic association constant, each water soluble ion concentration in the first mixed liquor test fluid is measured, as each in the first mixed liquor
Water soluble ion concentration；The water mixed with first part of flying dust sample is preferred to use distilled water or deionized water；Stirring means
Be preferred to use magnetic agitation, electric machinery stirring or stirring by hand, preferably control the rotating speed stirred to the first mixed liquor for 150~
200r/min；When preparing the first mixed liquor, the amount ratio of preferably first part flying dust sample and water is 0.1g：100ml；Preparing
During the first mixed liquor test fluid, preferably nitric acid dosage mixes liquid measure ratio with first for 0.1ml：100ml；Measuring the first mixed liquor
In each water soluble ion concentration when, the ion electrode that is preferred to use of assembling electrochemical detection device is lead ion electrode, chlorion
Any one electrode in electrode, calcium ion electrode, zinc ion electrode, Cadmium ion-selective electrode, chromium ion electrode and cupric ion electrode
It is used alone or any several electrodes is used in combination；
(3) the second part of flying dust sample that will prepare in step (1) is mixed with water, and stirring obtains second after at least 14 minutes
Mixed liquor, 1mol/L acetic acid is added dropwise into the second mixed liquor by the way of being added dropwise, while monitoring the second mixed liquor
PH, when the second mixed liquor is changed into neutrality, stops that acetic acid is added dropwise to the second mixed liquor, and record the vinegar of accumulative consumption so far
Sour total amount；The water mixed with second part of flying dust sample is preferred to use distilled water or deionized water；Stirring means are preferred to use
Magnetic agitation, electric machinery stirring or stirring by hand, preferably control to be 150~200r/ to the rotating speed that the second mixed liquor is stirred
min；When preparing the second mixed liquor, the amount ratio of preferably second part flying dust sample and water is 1g：100ml；Mixed in monitoring second
When closing the pH of liquid, it is 6.9~7.1 that preferably the second mixed liquor, which is changed into the neutral pH for referring to the second mixed liquor,；
(4) the 3rd part of flying dust sample, strontium nitrate and the glycerine absolute ethyl alcohol that will prepare in step (1) are uniformly mixed
Close, under water bath with thermostatic control heating and stirring condition, stirring obtains the 3rd mixed liquor after at least 10 minutes；Then monitoring the 3rd is mixed
The color change situation of liquid, when the 3rd mixed liquor is coloured, is then added dropwise into the 3rd mixed liquor by the way of being added dropwise
Benzoic acid ethanol solution with setting proportioning, the color to the second mixed liquor disappears, and records accumulative so far disappear
The total consumption of benzoic acid ethanol solution of consumption, according to drop of the benzoic acid ethanol solution with setting proportioning to calcium oxide
Fixed degree, measures the mass percent of free calcium oxide in the 3rd part of flying dust sample, is the house refuse prepared in step (1)
Free calcium oxide mass percent in flying ash testing sample；Stirring means are preferred to use magnetic agitation, electric machinery stirring
Or stirring by hand, preferably control to be 150~200r/min to the rotating speed that the 3rd mixed liquor is stirred；When preparing three mixed liquors,
It is preferred that the 3rd part of flying dust sample, strontium nitrate, the amount ratio of glycerine absolute ethyl alcohol are 0.5g：1g：30ml；Detecting the 3rd part of flying dust
In sample dissociate calcium oxide content when, it is preferred to use water bath with thermostatic control heating condition refer to that bath temperature is not higher than 90 DEG C；
(5) in step (2)~(4), the life rubbish prepared in step (1) is can determine that if following condition is met simultaneously
Heavy metal stabilizing is good in rubbish flying ash testing sample, and Leaching substantially will not be exceeded：
In step (2), the pH value for measuring the first mixed liquor is 11.5~12.3, using ionic association constant, measures first
Water-soluble plumbum ion concentration is not higher than 0.000058mol/L in mixed liquor, measures water-soluble chlorine ion concentration in the first mixed liquor
To be not higher than 0.02mol/L, it is 0.000008~0.003mol/L to measure water-soluble calcium ion concentration in the first mixed liquor；
In step (3), the acetic acid total amount that the accumulative consumption of acetic acid is added dropwise to the second mixed liquor is 5ml~9ml；
In step (4), the mass percent for measuring free calcium oxide in the 3rd part of flying dust sample is 10~18%.
As currently preferred technical scheme, in step (4), the free calcium oxide in the 3rd part of flying dust sample is measured
Mass percent when, it is specific as follows：
The color of the 3rd mixed liquor prepared is looked first at, if the 3rd mixed liquor is blush, to the 3rd mixed liquor
It is middle that the benzoic acid ethanol solution with setting proportioning is added dropwise by the way of being added dropwise, to the blush of the 3rd mixed liquor
Disappear；
Repeat and the 3rd mixed liquor is stirred after at least 10 minutes, continue to monitor the color change feelings of the 3rd mixed liquor
Condition, if the 3rd constant blush of mixed liquor, records the total consumption of benzoic acid ethanol solution of accumulative consumption so far,
And titer of the benzoic acid ethanol solution to calcium oxide is contrasted, calculate the matter of free calcium oxide in the 3rd part of flying dust sample
Measure percentage；If the 3rd mixed liquor is changed into blush again, continue to be added dropwise by the way of being added dropwise into the 3rd mixed liquor
Benzoic acid ethanol solution with setting proportioning, the blush to the 3rd mixed liquor disappears, and records so far tired
The total consumption of benzoic acid ethanol solution of consumption is counted, and contrasts titer of the benzoic acid ethanol solution to calcium oxide, is counted
Calculate the mass percent of free calcium oxide in the 3rd part of flying dust sample.
As currently preferred technical scheme, each water soluble ion concentration in the first mixed liquor of measurement in step (2)
Before, chlorion standard liquid, calcium ion standard liquid and lead ion standard with a series of chlorine ion concentrations are prepared respectively
Solution, and configure saturation potassium nitrate solution with potassium nitrate；Then, chlorine ion electrode is placed in one a chlorion standard liquid
It is middle to be activated, calcium ion electrode is placed in one in a calcium ion standard liquid and activated, lead ion electrode is placed in
Activated in one of lead ion standard liquid, also reference electrode is placed in saturation potassium nitrate solution and activated；So
Assemble electrochemical detection device respectively afterwards, the current potential of each chlorion standard liquid is determined with chlorine ion electrode and reference electrode, is painted
The standard curve of chlorine ion concentration and current potential processed, the electricity of each calcium ion standard liquid is determined with calcium ion electrode and reference electrode
Position, draws the standard curve of calcium ion concentration and current potential, and each lead ion standard liquid is determined with lead ion electrode and reference electrode
Current potential, draw the standard curve of plumbum ion concentration and current potential；Each water soluble ion in the first mixed liquor of measurement in step (2)
During concentration, electro-chemical measuring apparatus is assembled, lead ion electrode, chlorine ion electrode, calcium ion electrode are arranged in pairs or groups reference electrode respectively
It is put into the first mixed liquor test fluid, the current potential of display is recorded respectively, it is bent according to above-mentioned each ion concentration and the standard of current potential
Line, by current potential be converted into the first mixed liquor test fluid water-soluble plumbum ion concentration, Water soluble chloride ion concentration, water-soluble calcium from
Sub- concentration, is used as each water soluble ion concentration in the first mixed liquor.
The present invention compared with prior art, substantive distinguishing features and remarkable advantage is obviously protruded with following：
1. the present invention solves currently used national standard Leaching leaching method to judge landfill yard admission fly-ash heavy metal
Exist during stability and use duration, inefficiency, it is difficult to the problems such as live real-time monitoring, will the time-consuming national standard method more than 18 hours
The time-consuming synthetic determination method less than 1 hour is shorten to, the supervisory efficiency of admission fly-ash heavy metal stability can be effectively improved；
2. the inventive method is simple, Detection results are good, than national standard method more simple and effective, can rapid evaluation admission flying dust
Heavy metal and Leaching, be suitable for a variety of domestic garbage incineration flyash harmless resource utilization processing, can framework effectively
Realize the safety management of hazardous waste, guarantee environment safety.
Embodiment
Details are as follows for the preferred embodiments of the present invention：
Embodiment one：
In the present embodiment, heavy metal stabilizing and the quick determination method of toxicity in a kind of domestic garbage incineration flyash,
Comprise the following steps：
A., domestic garbage incineration flyash testing sample is provided；And the domestic garbage incineration flyash testing sample of offer is provided
It is three parts, standby respectively；It is 10 that chlorine ion concentration is respectively configured with sodium chloride-1Mol/L, 10-2Mol/L, 10-3Mol/L, 10-4mol/
L, 10-5Mol/L chlorion standard liquid, it is 10 that calcium ion concentration is respectively configured with calcium chloride-1Mol/L, 10-2Mol/L, 10- 3Mol/L, 10-4Mol/L, 10-5Mol/L calcium ion standard liquid, it is 10 that plumbum ion concentration is respectively configured with plumbi nitras-1mol/
L, 10-2Mol/L, 10-3Mol/L, 10-4Mol/L, 10-5Mol/L lead ion standard liquid, saturation potassium nitrate is configured with potassium nitrate
Solution；
B. chlorine ion electrode is placed in 10 in above-mentioned steps a-3Activated 2 hours in mol/L chlorion standard liquid, by calcium
Ion electrode is placed in 10 in above-mentioned steps a-3Activated 2 hours in mol/L calcium ion standard liquid, lead ion electrode is placed in
State 10 in step a-3Activated 2 hours in mol/L lead ion standard liquid, 217 type reference electrodes are placed in above-mentioned steps a and embezzled
Activated 2 hours with potassium nitrate solution；
C. the current potential of each chlorion standard liquid is determined with chlorine ion electrode and reference electrode, chlorine ion concentration and electricity is drawn
The standard curve of position, the current potential of each calcium ion standard liquid is determined with calcium ion electrode and reference electrode, calcium ion concentration is drawn
With the standard curve of current potential, the current potential of each lead ion standard liquid is determined with lead ion electrode and reference electrode, lead ion is drawn
The standard curve of concentration and current potential；
D. prepare in step a first part of flying dust sample is mixed with water, i.e., put 0.1g flying dusts with 100ml distilled water
In beaker, beaker is placed on magnetic stirring apparatus, a C40 type polytetrafluoro stirrer is added into beaker, is stirred using magnetic force
Mix, the rotating speed for controlling stirrer is 150~200r/min, stirs 14min, obtains the first mixed liquor；
E. pH meter is used, pH electrodes are put into the first mixed liquor obtained by above-mentioned steps d, slow agitation pH electrodes, until
Stable reading on pH meter, records the pH value of solution；The pH meter required precision used is PTS 97~100%；
F. the nitric acid that 0.1ml mass percent concentrations are 65% will be added in above-mentioned steps d resulting solutions, is stirred using magnetic force
Mix, the rotating speed for controlling stirrer is 150~200r/min, continue to stir 1min, obtain the first mixed liquor test fluid；
G. use ionic association constant, lead ion electrode, chlorine ion electrode, calcium by above-mentioned steps b Jing Guo activation process from
Sub-electrode reference electrode of arranging in pairs or groups respectively is put into the first mixed liquor test fluid obtained by above-mentioned steps f, and the electricity of display is recorded respectively
Current potential is converted into the first mixed liquor test fluid water-soluble plumbum ion concentration, chlorine by position, the standard curve in above-mentioned steps c
Ion concentration, calcium ion concentration, are used as each water soluble ion concentration in the first mixed liquor；
H. prepare in step a second part of flying dust sample is mixed with water, i.e., be placed in 1g flying dusts with 100ml distilled water
In beaker, using magnetic agitation, beaker is placed on magnetic stirring apparatus, a C40 type polytetrafluoro stirrer is added into beaker,
The rotating speed for controlling stirrer is 150~200r/min, stirs 14min, obtains the second mixed liquor；
I. pH electrodes are put into the second mixed liquor obtained by above-mentioned steps h, slow agitation pH electrodes, while toward drop in solution
Plus 1mol/L acetum, while the pH of the second mixed liquor is monitored, until pH meter shows that the second mixed liquor is just changed into neutral
Untill, stop that acetic acid is added dropwise to the second mixed liquor, and record the acetic acid total amount of accumulative consumption so far；In the present embodiment,
Mixed liquor is just changed into neutrality and refers to that pH meter reading is 6.90~7.10；
J. the 3rd part of flying dust sample 0.5g prepared in step a is taken, i.e., by 0.5g flying dusts sample, the anhydrous second of 30ml glycerine
Alcohol and 1g strontium nitrates are placed in 250ml conical flask, are uniformly mixed, and conical flask connected into upper condenser pipe, and by conical flask
It is placed on constant temperature water bath magnetic stirring apparatus, using C40 type polytetrafluoro stirrer during stirring, and controls the rotating speed of stirrer to be
150~200r/min, under 90 DEG C of water bath with thermostatic control heating and stirring condition, after stirring 10 minutes, obtains the 3rd mixed liquor；
K. the color change situation of the 3rd mixed liquor obtained by monitoring above-mentioned steps j, observes the color of the 3rd mixed liquor, this
The mixed liquors of Shi Faxian the 3rd are changed into blush, then blush disappearance is titrated to benzoic acid ethanol solution, is repeated above-mentioned
Constant temperature water bath whipping step in step j, is stirred after at least 10 minutes to the 3rd mixed liquor, continues to monitor the 3rd mixed liquor
Color change situation；Now, the 3rd mixed liquor is changed into blush again, then continues into the 3rd mixed liquor using the side being added dropwise
The benzoic acid ethanol solution with setting proportioning is added dropwise in formula, and the blush to the 3rd mixed liquor disappears, and records this
Untill add up the total consumption of benzoic acid ethanol solution of consumption, and contrast titration of the benzoic acid ethanol solution to calcium oxide
Degree, calculates the mass percent of free calcium oxide in the 3rd part of flying dust sample, is that the house refuse prepared in step a is burnt
Burn free calcium oxide mass percent in flying dust testing sample；
L. in step e, g, i and k, if can determine that the house refuse for preparing in step a if meeting following condition simultaneously
Heavy metal stabilizing is good in flying ash testing sample, and Leaching substantially will not be exceeded：
(I) in step e, the pH value for measuring the first mixed liquor is 11.5~12.3；
(II), using ionic association constant, measures water-soluble plumbum ion concentration in the first mixed liquor and is not higher than in step g
0.000058mol/L, it is not higher than 0.02mol/L to measure water-soluble chlorine ion concentration in the first mixed liquor, measures the first mixing
Water-soluble calcium ion concentration is 0.000008~0.003mol/L in liquid；
(III) in step i, the acetic acid total amount that the accumulative consumption of acetic acid is added dropwise to the second mixed liquor is 5ml~9ml；
(IV) in step k, the mass percent for measuring free calcium oxide in the 3rd part of flying dust sample is 10~18%.
The present embodiment is proposed with quick agitating solution pH determination methods, water-soluble plumbum ion concentration determination method, water first
Dissolubility chlorine ion concentration determination method, water-soluble calcium ion concentration determination method, acid-neutralizing capacity determination method, free calcium oxide are containing measurement
Determine whether the heavy metal stabilizing that method this six kinds of methods carry out comprehensive descision admission flying dust is qualified, i.e., whether Leaching is up to standard.This
Methodology has important directive significance for flying dust landfill admission supervision, can effectively improve the supervision of admission flying dust Leaching
Efficiency.The time-consuming national standard Leaching leaching method more than 18 hours is shorten to the synthetic determination method of time-consuming only 1 hour,
The exceeded flying dust sample of Leaching can be conveniently and efficiently detected, the work that flying dust landfill yard is checked on for flying dust quality is improved
Make efficiency, daily operation data can be fed back in time, coordinate pretreatment quality and landfill process.The present embodiment method has just
Prompt operability, good practical application benefit.Carry out comprehensive descision consumer waste incineration finally by this 6 indexs drawn to fly
Whether the heavy metal stabilizing of ash is qualified, i.e., whether Leaching is up to standard.The present embodiment solves currently used national standard and leaches poison
Property leaching method come judge during landfill yard admission fly-ash heavy metal stability exist use duration, inefficiency, it is difficult to scene in real time
The problems such as supervision, the supervisory efficiency of admission fly-ash heavy metal stability can be effectively improved.
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, it is that experiment test and checking analysis are carried out to each several part sample prepared by embodiment, in order to enter
The technique effect of the technical scheme of one step embodiment one, a kind of consumer waste incineration provided with reference to embodiment the present embodiment
Heavy metal stabilizing and the quick determination method of toxicity in flying dust are detailed to prominent substantive distinguishing features and significant progressive progress
Ground is described：
Choosing the domestic garbage incineration flyash after the chelating stabilization of Shanghai Lao Gang incineration plants generation on December 23rd, 2016 is
Pb contents account for the 3 ‰ of flying dust gross mass in example, the flying dust sample chosen herein, then artificial addition 1 ‰, 2 ‰ and 3 ‰ respectively again
Lead, altogether be made four ash samples, numbering is that 1., 2., 3., 4., their lead content is respectively 3 ‰, 4 ‰, 5 ‰ and 6 ‰.
Four samples are tested using each quick determination method, result are obtained as follows：
Quick agitating solution pH determination methods：
The data that four ash samples measure are can be seen that from quick agitating solution pH data the same, be all 11.51, according to
The regulation of criterion in the step l of embodiment one, the good sample of heavy metal stabilizing and toxicity is not exceeded should meet following
Condition：
Mixed liquor pH value is 11.5~12.3 after quick stirring.So four ash samples are all identified as Leaching Heavy Metals
Substantially will not be exceeded.
Water-soluble calcium ion concentration determination method：
The data that four ash samples measure are can be seen that from the data of water-soluble calcium ion concentration determination method basically identical, all
Close to 0.001mol/L, according to the regulation of criterion in embodiment one, heavy metal stabilizing is good and toxicity sample up to standard
Following condition should be met：The water-soluble calcium ion concentration measured is 0.000008mol/L~0.003mol/L.So four ash samples
All being identified as Leaching Heavy Metals substantially will not be exceeded.
Water soluble chloride ion concentration mensuration method：
The data that four ash samples measure are can be seen that from the data of Water soluble chloride ion concentration mensuration method basically identical, all
Close to 0.005mol/L, according to the regulation of criterion in the present invention, the good sample of heavy metal stabilizing should meet following bar
Part：The Water soluble chloride ion concentration measured is 0mol/L~0.02mol/L.So four ash samples are all identified as Leaching of Heavy Metals
Toxicity substantially will not be exceeded.
Water-soluble plumbum ion concentration determination method：
The data differences that four ash samples measure are can be seen that from the data of water-soluble plumbum ion concentration determination method larger, press
According to the regulation of criterion in the step l of embodiment one, heavy metal stabilizing is good and toxicity sample up to standard should meet following
Condition：The water-soluble plumbum ion concentration measured is no more than 0.000058mol/L.Number and 2. a number sample is identified as Leaching 1.
Substantially will not be exceeded.3. number and 4. a number sample measures water-soluble plumbum ion concentration not in defined safe range, thus they
It is identified as Leaching and is likely to exceeded.
Acid-neutralizing capacity determination method：
The data that four ash samples measure are can be seen that from the data of acid-neutralizing capacity determination method basically identical, all approach
6.3ml, according to the regulation of criterion in the step l of embodiment one, heavy metal stabilizing is good and toxicity sample up to standard should
Meet following condition：The acetic acid total amount of consumption is 5~9ml.It will not surpass substantially so four ash samples are all identified as Leaching
Mark.
Free calcium oxide content determination：
The data that four ash samples measure are can be seen that from the data of free calcium oxide determination method basically identical, all approach
10.9%, according to the regulation of criterion in the present invention, the good sample of heavy metal stabilizing should meet following condition：In flying dust
Free calcium oxide mass percent is 10%~18%.So four ash samples be all identified as Leaching substantially will not be exceeded.
Consider the result of six kinds of quick determination methods of the above, can be inferred that：1. number and 2. leaching poison of number sample
3. number and 4. number sample, due to the too high levels of water-soluble lead ion, has exceeded safe range property substantially will not be exceeded, so 3.
Number and 4. the Leaching Heavy Metals of number sample are likely to exceeded.
The result verified using national standard Leaching leaching method is as follows：
The 1. number and 2. Pb leaching contents both less than standard limited value of number sample is can be seen that from the data of above national standard method
5mg/L, so their Leaching is up to standard；3. number and 4. a number sample P b leaching contents are both greater than standard limited value 5mg/L and,
So their Leaching is exceeded.
The result and the result of national standard method that six kinds of quick determination methods synthesis are drawn, which compare, can see, with six
Plant quick determination method to integrate drawing a conclusion that 1., 2. a number sample Leaching substantially will not be exceeded, 3., 4. number sample leaches poison
Property is exceeded；The result that national standard method is measured is that 1., 2. number sample Leaching is up to standard, 3., and 4. number sample Leaching is exceeded.Two
The conclusion that person draws is consistent.So in actual applications, the method for embodiment one has effective.
Embodiment three：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, heavy metal stabilizing and the quick determination method of toxicity in a kind of domestic garbage incineration flyash,
Comprise the following steps：
A. this step is identical with embodiment one；
This step of b is identical with embodiment one；
C. this step is identical with embodiment one；
D. this step is identical with embodiment one；
E. this step is identical with embodiment one；
F. the nitric acid that 0.1ml mass percent concentrations are 68% will be added in above-mentioned steps d resulting solutions, is stirred using magnetic force
Mix, the rotating speed for controlling stirrer is 150~200r/min, continue to stir 1min, obtain the first mixed liquor test fluid；
G. this step is identical with embodiment one；
H. this step is identical with embodiment one；
I. this step is identical with embodiment one；
J. this step is identical with embodiment one；
K. the color change situation of the 3rd mixed liquor obtained by monitoring above-mentioned steps j, observes the color of the 3rd mixed liquor, this
The mixed liquors of Shi Faxian the 3rd are changed into blush, then blush disappearance is titrated to benzoic acid ethanol solution, is repeated above-mentioned
Constant temperature water bath whipping step in step j, is stirred after at least 10 minutes to the 3rd mixed liquor, continues to monitor the 3rd mixed liquor
Color change situation；Now, the 3rd constant blush of mixed liquor, then record the anhydrous second of benzoic acid of accumulative consumption so far
The total consumption of alcoholic solution, and titer of the benzoic acid ethanol solution to calcium oxide is contrasted, calculate in the 3rd part of flying dust sample
The mass percent of free calcium oxide, is free oxidation in the domestic garbage incineration flyash testing sample prepared in step a
Calcium mass percent；
L. this step is identical with embodiment one.
In the present embodiment, heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash, including
Following steps：The domestic garbage incineration flyash testing sample of offer is divided into 3 parts, first part of flying dust surveys molten after being mixed with water
Water-soluble plumbum ion concentration in the pH of liquid, solution, Water soluble chloride ion concentration, water-soluble calcium ion concentration；Second part of flying dust
By the way that acetum is added dropwise to neutrality after being mixed with water, acid-neutralizing capacity is surveyed；3rd part of flying dust and strontium nitrate and glycerine are anhydrous
Ethanol is mixed, by the titration of benzoic acid absolute ethyl alcohol, surveys free calcium oxide mass percent in flying dust.Finally by what is drawn
Whether the heavy metal stabilizing that this 6 indexs carry out comprehensive descision domestic garbage incineration flyash is qualified, i.e., whether Leaching is up to standard.
The present embodiment also solves currently used national standard Leaching leaching method to judge landfill yard admission fly-ash heavy metal stability
When exist and use duration, inefficiency, it is difficult to the problems such as live real-time monitoring, the time-consuming national standard method more than 18 hours is shorten to
The time-consuming synthetic determination method less than 1 hour, can effectively improve the supervisory efficiency of admission fly-ash heavy metal stability.
The embodiment of the present invention is illustrated above, but the invention is not restricted to above-described embodiment, can also be according to this hair
The purpose of bright innovation and creation makes a variety of changes, and that is done under all Spirit Essences and principle according to technical solution of the present invention changes
Become, modify, substitute, combine or simplify, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention, as long as not
The technical principle and invention of heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash of the present invention
Design, belongs to protection scope of the present invention.
Claims (10)
1. heavy metal stabilizing and the quick determination method of toxicity in a kind of domestic garbage incineration flyash, it is characterised in that including
Following steps：
(1) domestic garbage incineration flyash testing sample is provided, and the domestic garbage incineration flyash testing sample of offer is divided into three
Part, it is standby respectively；
(2) the first part of flying dust sample that will prepare in the step (1) is mixed with water, and stirring obtains first after at least 14 minutes
Mixed liquor, using pH meter, measures the pH value of the first mixed liquor；Addition 0.1ml mass percentages in the first mixed liquor are stated then up
Specific concentration is 65~68% nitric acid, obtains the first mixed liquor test fluid, continues to stir the first mixed liquor test fluid at least 1 minute
Afterwards, then using ionic association constant, each water soluble ion concentration in the first mixed liquor test fluid is measured, as each in the first mixed liquor
Water soluble ion concentration；
(3) the second part of flying dust sample that will prepare in the step (1) is mixed with water, and stirring obtains second after at least 14 minutes
Mixed liquor, 1mol/L acetic acid is added dropwise into the second mixed liquor by the way of being added dropwise, while monitoring the second mixed liquor
PH, when the second mixed liquor is changed into neutrality, stops that acetic acid is added dropwise to the second mixed liquor, and record the vinegar of accumulative consumption so far
Sour total amount；
(4) the 3rd part of flying dust sample, strontium nitrate and the glycerine absolute ethyl alcohol that will prepare in the step (1) are uniformly mixed
Close, under water bath with thermostatic control heating and stirring condition, stirring obtains the 3rd mixed liquor after at least 10 minutes；Then monitoring the 3rd is mixed
The color change situation of liquid, when the 3rd mixed liquor is coloured, is then added dropwise into the 3rd mixed liquor by the way of being added dropwise
Benzoic acid ethanol solution with setting proportioning, the color to the second mixed liquor disappears, and records accumulative so far disappear
The total consumption of benzoic acid ethanol solution of consumption, according to drop of the benzoic acid ethanol solution with setting proportioning to calcium oxide
Fixed degree, measures the mass percent of free calcium oxide in the 3rd part of flying dust sample, is the life prepared in the step (1)
Free calcium oxide mass percent in incineration of refuse flyash testing sample；
(5) in the step (2)~(4), the life prepared in the step (1) is can determine that if following condition is met simultaneously
Heavy metal stabilizing is good in incineration of refuse flyash testing sample living, and Leaching substantially will not be exceeded：
In the step (2), the pH value for measuring the first mixed liquor is 11.5~12.3, using ionic association constant, measures first
Water-soluble plumbum ion concentration is not higher than 0.000058mol/L in mixed liquor, measures water-soluble chlorine ion concentration in the first mixed liquor
To be not higher than 0.02mol/L, it is 0.000008~0.003mol/L to measure water-soluble calcium ion concentration in the first mixed liquor；
In the step (3), the acetic acid total amount that the accumulative consumption of acetic acid is added dropwise to the second mixed liquor is 5ml~9ml；
In the step (4), the mass percent for measuring free calcium oxide in the 3rd part of flying dust sample is 10~18%.
2. heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash according to claim 1, its
It is characterised by：In the step (2) and step (3), mixed respectively with first part of flying dust sample and second part of flying dust sample
The water of conjunction uses distilled water or deionized water；In the step (2)~(4), stirring means use magnetic agitation, electric machinery
Stirring or by hand stirring, control the stirring to the first mixed liquor, the second mixed liquor or the 3rd mixed liquor rotating speed be 150~
200r/min。
3. heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash according to claim 1, its
It is characterised by：In the step (2), when preparing the first mixed liquor, the amount ratio of first part of flying dust sample and water is
0.1g：100ml；When preparing the first mixed liquor test fluid, the nitric acid dosage mixes liquid measure ratio with first for 0.1ml：
100ml。
4. heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash according to claim 1, its
It is characterised by：In the step (2), in each water soluble ion concentration in measuring the first mixed liquor, Electrochemical Detection is assembled
The ion electrode that device is used is lead ion electrode, chlorine ion electrode, calcium ion electrode, zinc ion electrode, Cadmium ion-selective electrode, chromium
Any one electrode in ion electrode and cupric ion electrode is used alone or any several electrodes are used in combination.
5. heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash according to claim 1, its
It is characterised by：In the step (3), when preparing the second mixed liquor, the amount ratio of second part of flying dust sample and water is
1g：100ml.
6. heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash according to claim 1, its
It is characterised by：In the step (3), when monitoring the pH of the second mixed liquor, the second mixed liquor is changed into neutrality and refers to that second mixes
The pH for closing liquid is 6.9~7.1.
7. heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash according to claim 1, its
It is characterised by：In the step (4), prepare three mixed liquors when, the 3rd part of flying dust sample, strontium nitrate, glycerine without
The amount ratio of water-ethanol is 0.5g：1g：30ml.
8. heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash according to claim 1, its
It is characterised by：In the step (4), when dissociating calcium oxide content in detecting the 3rd part of flying dust sample, the water bath with thermostatic control of use
Heating condition refers to that bath temperature is not higher than 90 DEG C.
9. heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash according to claim 1, its
It is characterised by：
In the step (4), in the mass percent of free calcium oxide in measuring the 3rd part of flying dust sample, look first at and match somebody with somebody
The color of the 3rd mixed liquor made, if the 3rd mixed liquor is blush, into the 3rd mixed liquor using the side being added dropwise
The benzoic acid ethanol solution with setting proportioning is added dropwise in formula, and the blush to the 3rd mixed liquor disappears；
Repeat and the 3rd mixed liquor be stirred after at least 10 minutes, continue to monitor the color change situation of the 3rd mixed liquor,
If the 3rd constant blush of mixed liquor, the total consumption of benzoic acid ethanol solution of accumulative consumption so far is recorded, and
Benzoic acid ethanol solution is contrasted to the titer of calcium oxide, the quality of free calcium oxide in the 3rd part of flying dust sample is calculated
Percentage；If the 3rd mixed liquor is changed into blush again, continue that tool is added dropwise by the way of being added dropwise into the 3rd mixed liquor
There is the benzoic acid ethanol solution that setting is matched, the blush to the 3rd mixed liquor disappears, and record so far accumulative
The total consumption of benzoic acid ethanol solution of consumption, and titer of the benzoic acid ethanol solution to calcium oxide is contrasted, calculate
Go out the mass percent of free calcium oxide in the 3rd part of flying dust sample.
10. heavy metal stabilizing and the quick determination method of toxicity in domestic garbage incineration flyash according to claim 1, its
It is characterised by：In the step (2) in the first mixed liquor of measurement before each water soluble ion concentration, preparation respectively is with one
Chlorion standard liquid, calcium ion standard liquid and the lead ion standard liquid of row chlorine ion concentration, and configure full with potassium nitrate
And potassium nitrate solution；Then, chlorine ion electrode is placed in one in a chlorion standard liquid and activated, by calcium ion electricity
Pole is placed in one in a calcium ion standard liquid and activated, and lead ion electrode is placed in one a lead ion standard liquid
It is middle to be activated, also reference electrode is placed in saturation potassium nitrate solution and activated；Then assembling Electrochemical Detection is filled respectively
Put, the current potential of each chlorion standard liquid is determined with chlorine ion electrode and reference electrode, the mark of chlorine ion concentration and current potential is drawn
Directrix curve, the current potential of each calcium ion standard liquid is determined with calcium ion electrode and reference electrode, calcium ion concentration and current potential is drawn
Standard curve, the current potential of each lead ion standard liquid is determined with lead ion electrode and reference electrode, draw plumbum ion concentration with
The standard curve of current potential；In the step (2) in the first mixed liquor of measurement during each water soluble ion concentration, assembling electrochemistry is surveyed
Device is measured, lead ion electrode, chlorine ion electrode, calcium ion electrode reference electrode of arranging in pairs or groups respectively are put into the first mixed liquor test fluid
In, the current potential of display is recorded respectively, according to above-mentioned each ion concentration and the standard curve of current potential, current potential is converted into first and mixed
Water-soluble plumbum ion concentration, Water soluble chloride ion concentration, water-soluble calcium ion concentration in liquid test fluid are closed, the first mixed liquor is used as
In each water soluble ion concentration.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108535301A (en) * | 2018-01-21 | 2018-09-14 | 上海环境卫生工程设计院有限公司 | A method of various heavy content in flying dust is measured using XRF instrument quantitatives |
| CN108680707A (en) * | 2018-05-18 | 2018-10-19 | 光大环保技术研究院（南京）有限公司 | A kind of flying dust full constituent quantitative analysis method |
| CN110672538A (en) * | 2019-11-13 | 2020-01-10 | 辽宁石油化工大学 | Method for reducing content of heavy metal ion lead in incineration fly ash by using phosphate solution |
| CN114235523A (en) * | 2021-12-09 | 2022-03-25 | 深圳市深能环保东部有限公司 | Method for detecting content of heavy metal elements in fly ash of household garbage power plant |
| CN114544266A (en) * | 2020-11-20 | 2022-05-27 | 中国兵器工业第五九研究所 | A chloride ion real-time supervision device for among atmospheric environment |
| CN115015224A (en) * | 2022-05-30 | 2022-09-06 | 南京理工大学 | Grading evaluation method for determining water body environment risk by using heavy metal contained in fly ash |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004156970A (en) * | 2002-11-05 | 2004-06-03 | Shimadzu Techno Research:Kk | Simple method for measuring teq using indicator isomer |
| CN103091200A (en) * | 2012-12-30 | 2013-05-08 | 浙江工业大学 | Method and device for detecting metal aluminum content in burned ash |
| CN103411792A (en) * | 2013-07-29 | 2013-11-27 | 同济大学 | Method for detecting content of soluble salt in slag aggregate of waste incinerator |
-
2017
- 2017-05-12 CN CN201710333714.8A patent/CN107202865B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004156970A (en) * | 2002-11-05 | 2004-06-03 | Shimadzu Techno Research:Kk | Simple method for measuring teq using indicator isomer |
| CN103091200A (en) * | 2012-12-30 | 2013-05-08 | 浙江工业大学 | Method and device for detecting metal aluminum content in burned ash |
| CN103411792A (en) * | 2013-07-29 | 2013-11-27 | 同济大学 | Method for detecting content of soluble salt in slag aggregate of waste incinerator |
Non-Patent Citations (2)
| Title |
|---|
| 张晓樵: "生活垃圾焚烧飞灰毒性浸出规律及水洗预处理废水资源化处理探索", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 李萍: "生活垃圾焚烧飞灰重金属检测试验方法探讨", 《环境研究与监测》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108535301A (en) * | 2018-01-21 | 2018-09-14 | 上海环境卫生工程设计院有限公司 | A method of various heavy content in flying dust is measured using XRF instrument quantitatives |
| CN108680707A (en) * | 2018-05-18 | 2018-10-19 | 光大环保技术研究院（南京）有限公司 | A kind of flying dust full constituent quantitative analysis method |
| CN110672538A (en) * | 2019-11-13 | 2020-01-10 | 辽宁石油化工大学 | Method for reducing content of heavy metal ion lead in incineration fly ash by using phosphate solution |
| CN114544266A (en) * | 2020-11-20 | 2022-05-27 | 中国兵器工业第五九研究所 | A chloride ion real-time supervision device for among atmospheric environment |
| CN114544266B (en) * | 2020-11-20 | 2023-12-22 | 中国兵器工业第五九研究所 | Chloride ion real-time monitoring device used in atmosphere environment |
| CN114235523A (en) * | 2021-12-09 | 2022-03-25 | 深圳市深能环保东部有限公司 | Method for detecting content of heavy metal elements in fly ash of household garbage power plant |
| CN114235523B (en) * | 2021-12-09 | 2024-01-16 | 深圳市深能环保东部有限公司 | Method for detecting heavy metal element content of fly ash of household garbage power plant |
| CN115015224A (en) * | 2022-05-30 | 2022-09-06 | 南京理工大学 | Grading evaluation method for determining water body environment risk by using heavy metal contained in fly ash |
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