CN107202865B - Method for rapidly detecting stability and toxicity of heavy metals in household garbage incineration fly ash - Google Patents
Method for rapidly detecting stability and toxicity of heavy metals in household garbage incineration fly ash Download PDFInfo
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Abstract
The invention discloses a method for rapidly detecting the stability and toxicity of heavy metals in household garbage incineration fly ash, which comprises the steps of dividing a garbage fly ash sample to be detected into three parts, mixing the first part of fly ash with water, and then measuring the pH value, the lead ion, the chloride ion and the calcium ion concentration of a solution; mixing the second part of fly ash with water, dropwise adding an acetic acid solution to neutrality, and measuring the acid neutralization capacity; and mixing the third part of fly ash with strontium nitrate and glycerol absolute ethyl alcohol, titrating by benzoic acid absolute ethyl alcohol, and measuring the mass percentage of free calcium oxide in the fly ash. And finally, comprehensively judging whether the stability of the heavy metal of the fly ash is qualified or not by obtaining a plurality of indexes, namely whether the leaching toxicity reaches the standard or not. The method solves the problems of long time consumption, low efficiency and difficult on-site real-time supervision when the national standard leaching toxicity leaching method is used for judging the stability of the heavy metal in the in-situ fly ash of the landfill, shortens the national standard method which consumes more than 18 hours into a comprehensive judgment method which consumes less than 1 hour, and effectively improves the supervision efficiency of the stability of the heavy metal in the in-situ fly ash.
Description
Technical Field
The invention relates to a method for detecting pollution parameters of solid waste, in particular to a method for chemically detecting pollution parameters of incineration fly ash of household garbage, which is applied to the technical field of pollution control of a household garbage landfill.
Background
The municipal solid waste incineration fly ash is a substance collected in a heat recycling system and a flue gas purification system after the municipal solid waste incineration, and contains various harmful substances with high content, such as cadmium, lead, zinc, chromium and the like, which can be leached by water. If not properly treated, heavy metals will migrate and contaminate groundwater, soil and air. Therefore, the waste incineration fly ash is listed in national hazardous waste records, belongs to hazardous waste, and needs strict supervision and safe disposal. With the increasing urban population and the increasing urban domestic garbage, the garbage incineration is the inevitable choice for harmless and resource treatment of the garbage.
The fly ash contains a large amount of heavy metal pollutants, the leaching toxicity of the solidified fly ash treated by the mixing and solidifying process is obviously reduced after the solidified fly ash enters a landfill, and most of the fly ash meets the standard limit value but part of the fly ash exceeds the standard compared with the uncured fly ash. The existing methods for detecting the stability of heavy metals in fly ash are a sulfuric acid-nitric acid method and an acetic acid buffer solution method which are solid waste leaching toxicity leaching methods in the national environmental protection industry standard. However, the national standard method requires strict detection conditions, needs a plurality of professional instruments, takes a long time, and takes more than 18 hours for turning over. In the process of landfill disposal of the fly ash, the stability of heavy metals entering the fly ash of the landfill is difficult to monitor in real time on site according to the pollution control standard of the domestic refuse landfill by using a national standard leaching toxicity leaching method, so that part of fly ash with incomplete heavy metal stabilization directly enters the landfill for landfill, and the hidden danger of environmental pollution exists. Namely, the existing detection method for the stability of the heavy metals in the municipal solid waste incineration fly ash has the defects of long time and low efficiency, so that the pretreatment quality and the landfill process are difficult to implement coordinately, and the quality of the fly ash at the entrance is difficult to implement. Therefore, a detection method which is simpler, more convenient and more efficient than a national standard method is urgently needed to be found for rapidly evaluating the leaching toxicity of the heavy metals in the fly ash entering the field so as to realize effective control on pollution of the domestic garbage landfill.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art, and provides a method for rapidly detecting the stability and toxicity of heavy metals in household garbage incineration fly ash, which can simply, conveniently and rapidly detect the stability of the heavy metals in the household garbage incineration fly ash, provides a solution for quality control of landfill yard entrance fly ash, improves the supervision efficiency of the stability of the heavy metals in the entrance fly ash, and ensures the environmental safety.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for rapidly detecting the stability and toxicity of heavy metals in household garbage incineration fly ash comprises the following steps:
(1) providing a sample to be tested of the household garbage incineration fly ash, and dividing the provided sample to be tested of the household garbage incineration fly ash into three parts for later use respectively;
(2) mixing the first part of fly ash sample prepared in the step (1) with water, stirring for at least 14 minutes to obtain a first mixed solution, and measuring the pH value of the first mixed solution by adopting a pH meter; then adding 0.1ml of nitric acid with the mass percentage concentration of 65-68% into the first mixed solution to obtain a first mixed solution test solution, continuously stirring the first mixed solution test solution for at least 1 minute, and measuring the concentration of each water-soluble ion in the first mixed solution test solution by adopting an ion electrode method to obtain the concentration of each water-soluble ion in the first mixed solution as the concentration of each water-soluble ion in the first mixed solution; the water mixed with the first sample of fly ash is preferably distilled or deionized water; the stirring method preferably adopts magnetic stirring, electric mechanical stirring or manual stirring, and the rotating speed of stirring the first mixed solution is preferably controlled to be 150-200 r/min; in preparing the first mixed solution, the dosage ratio of the first fly ash sample to water is preferably 0.1 g: 100 ml; when preparing the first mixed solution test solution, the ratio of the amount of nitric acid to the amount of the first mixed solution is preferably 0.1 ml: 100 ml; when the concentration of each water-soluble ion in the first mixed solution is measured, the ion electrode preferably adopted by the assembled electrochemical detection device is any one of a lead ion electrode, a chloride ion electrode, a calcium ion electrode, a zinc ion electrode, a cadmium ion electrode, a chromium ion electrode and a copper ion electrode which is used independently or any combination of several electrodes;
(3) mixing the second part of fly ash sample prepared in the step (1) with water, stirring for at least 14 minutes to obtain a second mixed solution, dropwise adding 1mol/L of acetic acid into the second mixed solution, simultaneously monitoring the pH value of the second mixed solution, stopping dropwise adding the acetic acid into the second mixed solution when the second mixed solution becomes neutral, and recording the total amount of acetic acid consumed up to this point; the water mixed with the second sample of fly ash is preferably distilled or deionized water; the stirring method preferably adopts magnetic stirring, electric mechanical stirring or manual stirring, and the stirring speed of the second mixed solution is preferably controlled to be 150-200 r/min; when preparing the second mixed solution, the dosage ratio of the second fly ash sample to water is preferably 1 g: 100 ml; when monitoring the pH of the second mixed solution, preferably, the second mixed solution becomes neutral, namely the pH of the second mixed solution is 6.9-7.1;
(4) uniformly mixing the third fly ash sample prepared in the step (1), strontium nitrate and glycerol absolute ethyl alcohol, and stirring for at least 10 minutes under the conditions of constant-temperature water bath heating and stirring to obtain a third mixed solution; then monitoring the color change condition of the third mixed solution, when the third mixed solution is colored, dropwise adding a benzoic acid absolute ethyl alcohol solution with a set ratio into the third mixed solution until the color of the second mixed solution disappears, recording the total consumption of the benzoic acid absolute ethyl alcohol solution accumulated till now, and measuring the mass percentage of free calcium oxide in the third fly ash sample according to the titer of the benzoic acid absolute ethyl alcohol solution with the set ratio on calcium oxide to obtain the mass percentage of the free calcium oxide in the household garbage incineration fly ash sample to be detected, which is the mass percentage of the free calcium oxide in the household garbage incineration fly ash sample to be detected prepared in the step (1); the stirring method preferably adopts magnetic stirring, electric mechanical stirring or manual stirring, and the rotating speed for stirring the third mixed solution is preferably controlled to be 150-200 r/min; when preparing the third mixed solution, the dosage ratio of the third fly ash sample, the strontium nitrate and the glycerol absolute ethyl alcohol is preferably 0.5 g: 1 g: 30 ml; when the free calcium oxide content in the third fly ash sample is detected, the preferable constant-temperature water bath heating condition is that the water bath temperature is not higher than 90 ℃;
(5) in the steps (2) to (4), if the following conditions are met, the stability of the heavy metal in the sample to be tested of the municipal solid waste incineration fly ash prepared in the step (1) can be judged to be good, and the leaching toxicity basically cannot exceed the standard:
in the step (2), the pH value of the first mixed solution is measured to be 11.5-12.3, an ion electrode method is adopted, the concentration of water-soluble lead ions in the first mixed solution is measured to be not higher than 0.000058mol/L, the concentration of water-soluble chloride ions in the first mixed solution is measured to be not higher than 0.02mol/L, and the concentration of water-soluble calcium ions in the first mixed solution is measured to be 0.000008-0.003 mol/L;
in the step (3), 5ml to 9ml of acetic acid which is cumulatively consumed by acetic acid is dripped into the second mixed solution;
in the step (4), the mass percentage of free calcium oxide in the third fly ash sample is 10-18%.
As a preferred technical solution of the present invention, in the step (4), when the mass percentage of the free calcium oxide in the third sample of fly ash is measured, the following is specifically performed:
firstly, observing the color of the prepared third mixed solution, and if the third mixed solution is reddish, dropwise adding a benzoic acid absolute ethyl alcohol solution with a set ratio into the third mixed solution in a dropwise adding mode until the reddish color of the third mixed solution disappears;
repeatedly stirring the third mixed solution for at least 10 minutes, continuously monitoring the color change condition of the third mixed solution, if the third mixed solution does not turn reddish, recording the total consumption of the benzoic acid absolute ethyl alcohol solution which is consumed up to now, comparing the titer of the benzoic acid absolute ethyl alcohol solution on calcium oxide, and calculating the mass percentage of free calcium oxide in the third fly ash sample; and if the third mixed solution turns reddish again, continuously dropwise adding the benzoic acid absolute ethyl alcohol solution with the set proportion into the third mixed solution in a dropwise adding mode until the reddish color of the third mixed solution disappears, recording the total consumption of the benzoic acid absolute ethyl alcohol solution until the reddish color of the third mixed solution disappears, and calculating the mass percent of free calcium oxide in the third fly ash sample by comparing the titer of the benzoic acid absolute ethyl alcohol solution to calcium oxide.
As a preferable technical solution of the present invention, before the concentration of each water-soluble ion in the first mixed solution is measured in step (2), a chloride ion standard solution, a calcium ion standard solution, and a lead ion standard solution having a series of chloride ion concentrations are prepared, respectively, and a saturated potassium nitrate solution is prepared using potassium nitrate; then, placing the chloride ion electrode in one of the chloride ion standard solutions for activation, placing the calcium ion electrode in one of the calcium ion standard solutions for activation, placing the lead ion electrode in one of the lead ion standard solutions for activation, and placing the reference electrode in a saturated potassium nitrate solution for activation; then respectively assembling electrochemical detection devices, measuring the potential of each chloride ion standard solution by using a chloride ion electrode and a reference electrode, drawing a standard curve of the concentration and the potential of the chloride ions, measuring the potential of each calcium ion standard solution by using a calcium ion electrode and a reference electrode, drawing a standard curve of the concentration and the potential of the calcium ions, measuring the potential of each lead ion standard solution by using a lead ion electrode and a reference electrode, and drawing a standard curve of the concentration and the potential of the lead ions; when the concentration of each water-soluble ion in the first mixed solution is measured in the step (2), an electrochemical measuring device is assembled, a lead ion electrode, a chloride ion electrode and a calcium ion electrode are respectively placed into the first mixed solution test solution together with a reference electrode, displayed potentials are respectively recorded, and the potentials are converted into the concentration of each water-soluble lead ion, the concentration of each water-soluble chloride ion and the concentration of each water-soluble calcium ion in the first mixed solution test solution according to the standard curve of each ion concentration and the potential to be used as the concentration of each water-soluble ion in the first mixed solution.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the method solves the problems of long time consumption, low efficiency, difficulty in on-site real-time supervision and the like when the national standard leaching toxicity leaching method is used for judging the stability of the heavy metal in the in-situ fly ash of the landfill site at present, shortens the national standard method which consumes more than 18 hours into a comprehensive judgment method which consumes less than 1 hour, and can effectively improve the supervision efficiency of the stability of the heavy metal in the in-situ fly ash;
2. the method disclosed by the invention is simple, good in detection effect, simpler, more convenient and more efficient than a national standard method, capable of rapidly evaluating the heavy metal and leaching toxicity of the incoming fly ash, suitable for harmless resource treatment of various household garbage incineration fly ashes, capable of effectively realizing safety management of hazardous wastes and guaranteeing environmental safety.
Detailed Description
The preferred embodiments of the invention are detailed below:
the first embodiment is as follows:
in this embodiment, a method for rapidly detecting the stability and toxicity of heavy metals in fly ash from incineration of household garbage includes the following steps:
a. providing a to-be-detected sample of the household garbage incineration fly ash; dividing the provided sample to be detected of the household garbage incineration fly ash into three parts for later use respectively; respectively preparing the chloride ion concentration of 10 by using sodium chloride-1mol/L，10-2mol/L，10-3mol/L，10-4mol/L，10-5Respectively preparing calcium ion concentration of 10 with calcium chloride by using mol/L chloride ion standard solution-1mol/L，10-2mol/L，10- 3mol/L，10-4mol/L，10-5Respectively preparing 10 concentration of lead ions by using lead nitrate in mol/L calcium ion standard solution-1mol/L，10-2mol/L，10-3mol/L，10-4mol/L，10-5Preparing a saturated potassium nitrate solution by using potassium nitrate in a lead ion standard solution of mol/L;
b. placing a chloride ion electrode in step a 10 above-3Activating in a chloride ion standard solution of mol/L for 2 hours, and placing a calcium ion electrode in the step a 10-3Activating in a calcium ion standard solution of mol/L for 2 hours, and placing a lead ion electrode in the step a 10-3Activating for 2 hours in mol/L lead ion standard solution, and placing a 217 type reference electrode in the saturated potassium nitrate solution in the step a for activating for 2 hours;
c. measuring the potential of each chloride ion standard solution by using a chloride ion electrode and a reference electrode, drawing a standard curve of the concentration and the potential of chloride ions, measuring the potential of each calcium ion standard solution by using a calcium ion electrode and a reference electrode, drawing a standard curve of the concentration and the potential of calcium ions, measuring the potential of each lead ion standard solution by using a lead ion electrode and a reference electrode, and drawing a standard curve of the concentration and the potential of lead ions;
d. b, mixing the first part of fly ash sample prepared in the step a with water, namely placing 0.1g of fly ash and 100ml of distilled water in a beaker, placing the beaker on a magnetic stirrer, adding a particle of C40 type polytetrafluoroethylene stirrer into the beaker, adopting magnetic stirring, controlling the rotating speed of the stirrer to be 150-200 r/min, and stirring for 14min to obtain a first mixed solution;
e. d, a pH meter is adopted, a pH electrode is placed into the first mixed solution obtained in the step d, the pH electrode is slowly stirred until the reading on the pH meter is stable, and the pH value of the solution is recorded; the precision requirement of the adopted pH meter is that PTS is 97-100%;
f. adding 0.1ml of 65% nitric acid by mass into the solution obtained in the step d, stirring by magnetic force, controlling the rotating speed of a stirrer to be 150-200 r/min, and continuing stirring for 1min to obtain a first mixed solution test solution;
g. b, respectively placing the activated lead ion electrode, the activated chloride ion electrode and the activated calcium ion electrode in the step b into the first mixed solution test solution obtained in the step f by adopting an ion electrode method together with a reference electrode, respectively recording displayed potentials, and converting the potentials into the concentration of water-soluble lead ions, the concentration of chloride ions and the concentration of calcium ions in the first mixed solution test solution according to the standard curve in the step c to serve as the concentration of each water-soluble ion in the first mixed solution;
h. b, mixing the second part of fly ash sample prepared in the step a with water, namely placing 1g of fly ash and 100ml of distilled water in a beaker, placing the beaker on a magnetic stirrer by adopting magnetic stirring, adding one particle of C40 type polytetrafluoroethylene stirrer into the beaker, controlling the rotating speed of the stirrer to be 150-200 r/min, and stirring for 14min to obtain a second mixed solution;
i. putting a pH electrode into the second mixed solution obtained in the step h, slowly stirring the pH electrode, simultaneously dropwise adding 1mol/L acetic acid solution into the solution, simultaneously monitoring the pH value of the second mixed solution, stopping dropwise adding acetic acid into the second mixed solution until the pH meter shows that the second mixed solution is just neutral, and recording the total amount of acetic acid consumed up to this point; in the embodiment, the condition that the mixed solution is just neutral means that the reading of the pH meter is 6.90-7.10;
j. taking 0.5g of the third fly ash sample prepared in the step a, namely putting 0.5g of the fly ash sample, 30ml of glycerol absolute ethyl alcohol and 1g of strontium nitrate into a 250ml conical flask, uniformly mixing, connecting the conical flask with a condenser pipe, putting the conical flask on a water bath constant-temperature magnetic stirrer, adopting a C40 type polytetrafluoroethylene stirrer during stirring, controlling the rotating speed of the stirrer to be 150-200 r/min, and stirring for 10 minutes under the conditions of heating and stirring in a 90 ℃ constant-temperature water bath to obtain a third mixed solution;
k. monitoring the color change condition of the third mixed solution obtained in the step j, observing the color of the third mixed solution, titrating the third mixed solution until the reddish color disappears by using a benzoic acid absolute ethyl alcohol solution when the third mixed solution is found to be reddish, repeating the water bath constant-temperature stirring step in the step j, and continuing monitoring the color change condition of the third mixed solution after stirring the third mixed solution for at least 10 minutes; at the moment, the third mixed solution turns reddish again, the benzoic acid absolute ethyl alcohol solution with the set proportion is continuously dropwise added into the third mixed solution until the reddish color of the third mixed solution disappears, the total consumption of the benzoic acid absolute ethyl alcohol solution which is consumed up to now is recorded, the titer of the benzoic acid absolute ethyl alcohol solution to calcium oxide is compared, and the mass percentage of free calcium oxide in the third fly ash sample is calculated, namely the mass percentage of the free calcium oxide in the to-be-detected sample of the household garbage incineration fly ash prepared in the step a;
l, in the steps e, g, i and k, if the following conditions are met, the stability of the heavy metals in the household garbage incineration fly ash sample to be tested prepared in the step a is judged to be good, and the leaching toxicity basically cannot exceed the standard:
in the step e, measuring the pH value of the first mixed solution to be 11.5-12.3;
(ii) in the step g, an ion electrode method is adopted, the concentration of the water-soluble lead ions in the first mixed solution is measured to be not higher than 0.000058mol/L, the concentration of the water-soluble chloride ions in the first mixed solution is measured to be not higher than 0.02mol/L, and the concentration of the water-soluble calcium ions in the first mixed solution is measured to be 0.000008-0.003 mol/L;
(iii) in the step i, 5ml to 9ml of total acetic acid consumed in the second mixed solution dropwise adding acetic acid;
(iv) in the step k, the mass percentage of the free calcium oxide in the third fly ash sample is 10-18%.
The embodiment firstly proposes that six methods, namely a rapid stirring solution pH measuring method, a water-soluble lead ion concentration measuring method, a water-soluble chloride ion concentration measuring method, a water-soluble calcium ion concentration measuring method, an acid neutralization capacity measuring method and a free calcium oxide content measuring method, are used for comprehensively judging whether the stability of the heavy metal of the incoming fly ash is qualified or not, namely whether the leaching toxicity reaches the standard or not. The method has important guiding significance for monitoring the fly ash landfill site, and can effectively improve the efficiency of monitoring the leaching toxicity of the fly ash in the site. The national standard leaching toxicity leaching method which takes more than 18 hours is shortened to a comprehensive judgment method which takes only 1 hour, so that the fly ash sample with excessive leaching toxicity can be conveniently and quickly detected, the working efficiency of a fly ash landfill for the quality control of fly ash is improved, the daily operation data can be timely fed back, and the pretreatment quality and the landfill process are coordinated. The method has convenient operability and good practical application benefit. Finally, whether the stability of the heavy metal in the fly ash generated by burning the household garbage is qualified or not is comprehensively judged through the 6 obtained indexes, namely whether the leaching toxicity reaches the standard or not is judged. The method solves the problems of long time consumption, low efficiency, difficulty in on-site real-time supervision and the like when the national standard leaching toxicity leaching method is used for judging the stability of the heavy metal in the in-situ fly ash of the landfill site at present, and can effectively improve the supervision efficiency of the stability of the heavy metal in the in-situ fly ash.
Example two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, experimental tests and verification analyses are performed on each part of samples prepared in the embodiment, and in order to further implement the technical effect of the technical scheme in the embodiment, the following detailed description is provided for the method for rapidly detecting the stability and toxicity of heavy metals in fly ash from incineration of household garbage, in combination with the embodiment, for the outstanding substantive features and remarkable progress:
the fly ash sample is selected as an example, the fly ash generated by the incineration plant of domestic garbage after stable chelation in 2016, 12 and 23 days is selected as an example, the Pb content of the fly ash sample selected here accounts for 3 per thousand of the total mass of the fly ash, then 1 per thousand, 2 per thousand and 3 per thousand of lead are respectively and manually added, and four ash samples are prepared in total, and the numbers of the ash samples are (i), (ii), (iii), (iv) and (iv), and the lead contents of the ash samples are respectively 3 per thousand, 4 per thousand, 5 per thousand and 6 per thousand.
Four samples were tested using each rapid test method and the results were as follows:
rapid stirring solution pH assay:
as can be seen from the pH data of the rapidly stirred solution, the data measured for the four ash samples are all 11.51, and according to the specification of the index standard in step l of the first example, the samples with good heavy metal stability and toxicity which do not exceed the standard can meet the following conditions:
after rapid stirring, the pH value of the mixed solution is 11.5-12.3. Therefore, the four ash samples are judged that the leaching toxicity of the heavy metals basically cannot exceed the standard.
Water-soluble calcium ion concentration determination method:
as can be seen from the data of the water-soluble calcium ion concentration measurement method, the data measured by the four ash samples are basically consistent and are close to 0.001mol/L, and according to the regulation of the index standard in the first embodiment, the samples with good heavy metal stability and up-to-standard toxicity meet the following conditions: the measured concentration of the water-soluble calcium ions is 0.000008mol/L to 0.003 mol/L. Therefore, the four ash samples are judged that the leaching toxicity of the heavy metals basically cannot exceed the standard.
Water-soluble chloride ion concentration determination method:
as can be seen from the data of the water-soluble chloride ion concentration determination method, the data measured by the four ash samples are basically consistent and are close to 0.005mol/L, and according to the specification of the index standard in the invention, the samples with good heavy metal stability should meet the following conditions: the measured concentration of the water-soluble chloride ions is 0 mol/L-0.02 mol/L. Therefore, the four ash samples are judged that the leaching toxicity of the heavy metals basically cannot exceed the standard.
Water-soluble lead ion concentration determination method:
as can be seen from the data of the water-soluble lead ion concentration measurement method, the data measured by the four ash samples are greatly different, and according to the provision of the index standard in the step l of the example I, the samples with good heavy metal stability and up-to-standard toxicity meet the following conditions: the water-soluble lead ion concentration is measured to be not more than 0.000058 mol/L. Samples No. I and No. II are determined that leaching toxicity basically does not exceed the standard. Samples Nos. three and four measured that the concentration of water-soluble lead ions was not within the specified safety range, so they were considered as being likely to be out of limits in leaching toxicity.
Acid neutralization capacity assay:
as can be seen from the data obtained from the acid neutralization capacity measurement method, the data obtained from the four ash samples are basically consistent and are close to 6.3ml, and the samples with good heavy metal stability and up-to-standard toxicity meet the following conditions according to the specification of the index standard in step l of example I: the total amount of acetic acid consumed is 5-9 ml. The four ash samples are considered to be substantially non-exceeding leaching toxicity.
Free calcium oxide assay:
as can be seen from the data of the free calcium oxide determination method, the data measured by the four ash samples are basically consistent and are close to 10.9%, and according to the specification of the index standard in the invention, the samples with good heavy metal stability should meet the following conditions: the mass percentage of free calcium oxide in the fly ash is 10-18%. The four ash samples are considered to be substantially non-exceeding leaching toxicity.
By comprehensively considering the results of the above six rapid detection methods, it can be concluded that: the leaching toxicity of the samples III and IV does not exceed the standard basically, and the heavy metal leaching toxicity of the samples III and IV is likely to exceed the standard due to the fact that the content of water-soluble lead ions in the samples III and IV is too high and exceeds the safety range.
The results of the validation using the national standard leaching toxicity leaching method were as follows:
as can be seen from the data of the national standard method, the Pb leaching amount of the samples I and II is less than the standard limit value of 5mg/L, so the leaching toxicity of the samples I and II reaches the standard; and Pb leaching amounts of samples No. III and No. IV are both larger than a standard limit value of 5mg/L, so that leaching toxicity of the samples No. III and No. IV exceeds the standard limit value.
The results obtained by combining the six rapid detection methods are compared with the results obtained by the national standard method, and the results obtained by combining the six rapid detection methods are that firstly, the leaching toxicity of the sample is basically not over standard, and thirdly, the leaching toxicity of the sample is over standard; the results of the national standard method are that firstly, the leaching toxicity of the sample reaches the standard, and thirdly, the leaching toxicity of the sample exceeds the standard. The two conclusions are consistent. Therefore, in practical applications, the embodiment and the method are effective.
Example three:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, a method for rapidly detecting the stability and toxicity of heavy metals in fly ash from incineration of household garbage includes the following steps:
a. the step is the same as the first embodiment;
b the step is the same as the first embodiment;
c. the step is the same as the first embodiment;
d. the step is the same as the first embodiment;
e. the step is the same as the first embodiment;
f. adding 0.1ml of nitric acid with the mass percentage concentration of 68% into the solution obtained in the step d, stirring by magnetic force, controlling the rotating speed of a stirrer to be 150-200 r/min, and continuing stirring for 1min to obtain a first mixed solution test solution;
g. the step is the same as the first embodiment;
h. the step is the same as the first embodiment;
i. the step is the same as the first embodiment;
j. the step is the same as the first embodiment;
k. monitoring the color change condition of the third mixed solution obtained in the step j, observing the color of the third mixed solution, titrating the third mixed solution until the reddish color disappears by using a benzoic acid absolute ethyl alcohol solution when the third mixed solution is found to be reddish, repeating the water bath constant-temperature stirring step in the step j, and continuing monitoring the color change condition of the third mixed solution after stirring the third mixed solution for at least 10 minutes; at the moment, the third mixed solution is not reddish, the total consumption of the benzoic acid absolute ethyl alcohol solution which is consumed up to now is recorded, the titer of the benzoic acid absolute ethyl alcohol solution to calcium oxide is compared, and the mass percentage of free calcium oxide in the third fly ash sample is calculated, namely the mass percentage of free calcium oxide in the to-be-detected sample of the household garbage incineration fly ash prepared in the step a;
the procedure is the same as in example one.
In this embodiment, the method for rapidly detecting the stability and toxicity of heavy metals in fly ash from incineration of household garbage includes the following steps: dividing the provided household garbage incineration fly ash sample to be tested into 3 parts, mixing and stirring the first part of fly ash and water, and then testing the pH value of the solution, the concentration of water-soluble lead ions, the concentration of water-soluble chloride ions and the concentration of water-soluble calcium ions in the solution; mixing the second part of fly ash with water, dropwise adding an acetic acid solution to neutrality, and measuring the acid neutralization capacity; and mixing the third part of fly ash with strontium nitrate and glycerol absolute ethyl alcohol, and measuring the mass percent of free calcium oxide in the fly ash by titration of benzoic acid absolute ethyl alcohol. Finally, whether the stability of the heavy metal in the fly ash generated by burning the household garbage is qualified or not is comprehensively judged through the 6 obtained indexes, namely whether the leaching toxicity reaches the standard or not is judged. The method also solves the problems of long time consumption, low efficiency, difficulty in on-site real-time supervision and the like when the national standard leaching toxicity leaching method is used for judging the stability of the heavy metal in the in-situ fly ash of the landfill site at present, shortens the national standard method which consumes more than 18 hours into a comprehensive judgment method which consumes less than 1 hour, and can effectively improve the supervision efficiency of the stability of the heavy metal in the in-situ fly ash.
The embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments, and various changes can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitution ways, so long as the invention is in accordance with the purpose of the present invention, and the technical principle and inventive concept of the method for rapidly detecting the stability and toxicity of heavy metals in fly ash from incineration of domestic waste of the present invention shall fall within the protection scope of the present invention.
Claims (7)
1. A method for rapidly detecting the stability and toxicity of heavy metals in household garbage incineration fly ash is characterized by comprising the following steps:
(1) providing a sample to be tested of the household garbage incineration fly ash, and dividing the provided sample to be tested of the household garbage incineration fly ash into three parts for later use respectively;
(2) mixing the first part of fly ash sample prepared in the step (1) with water, stirring for at least 14 minutes to obtain a first mixed solution, and measuring the pH value of the first mixed solution by using a pH meter; then adding 0.1ml of nitric acid with the mass percentage concentration of 65-68% into the first mixed solution to obtain a first mixed solution test solution, continuously stirring the first mixed solution test solution for at least 1 minute, and measuring the concentration of each water-soluble ion in the first mixed solution test solution by adopting an ion electrode method to obtain the concentration of each water-soluble ion in the first mixed solution as the concentration of each water-soluble ion in the first mixed solution;
(3) mixing the second part of fly ash sample prepared in the step (1) with water, stirring for at least 14 minutes to obtain a second mixed solution, dropwise adding 1mol/L of acetic acid into the second mixed solution while monitoring the pH of the second mixed solution, stopping dropwise adding the acetic acid into the second mixed solution when the second mixed solution becomes neutral, and recording the total amount of acetic acid consumed up to this point;
(4) uniformly mixing the third fly ash sample prepared in the step (1), strontium nitrate and glycerol absolute ethyl alcohol, and stirring for at least 10 minutes under the conditions of constant-temperature water bath heating and stirring to obtain a third mixed solution; then monitoring the color change condition of the third mixed solution, when the third mixed solution is colored, dropwise adding a benzoic acid absolute ethyl alcohol solution with a set ratio into the third mixed solution until the color of the second mixed solution disappears, recording the total consumption of the benzoic acid absolute ethyl alcohol solution accumulated till now, and measuring the mass percentage of free calcium oxide in the third fly ash sample according to the titer of the benzoic acid absolute ethyl alcohol solution with the set ratio on calcium oxide to obtain the mass percentage of the free calcium oxide in the household garbage incineration fly ash sample to be detected, which is the mass percentage of the free calcium oxide in the household garbage incineration fly ash sample to be detected prepared in the step (1);
(5) in the steps (2) to (4), if the following conditions are met, it can be determined that the stability of the heavy metals in the sample to be tested of the municipal solid waste incineration fly ash prepared in the step (1) is good, and the leaching toxicity basically does not exceed the standard:
in the step (2), the pH value of the first mixed solution is measured to be 11.5-12.3, an ion electrode method is adopted, the concentration of water-soluble lead ions in the first mixed solution is measured to be not higher than 0.000058mol/L, the concentration of water-soluble chloride ions in the first mixed solution is measured to be not higher than 0.02mol/L, and the concentration of water-soluble calcium ions in the first mixed solution is measured to be 0.000008-0.003 mol/L;
in the step (2), when preparing the first mixed solution, the ratio of the first part of fly ash sample to water is 0.1 g: 100 ml; when preparing the first mixed solution test solution, the ratio of the amount of the nitric acid to the amount of the first mixed solution is 0.1 ml: 100 ml;
in the step (3), 5ml to 9ml of acetic acid total amount consumed in the second mixed solution is dropwise added;
in the step (3), when preparing the second mixed solution, the usage ratio of the second fly ash sample to water is 1 g: 100 ml;
in the step (4), the mass percent of free calcium oxide in the third fly ash sample is 10-18%;
in the step (4), when a third mixed solution is prepared, the dosage ratio of the third fly ash sample, strontium nitrate and glycerol absolute ethyl alcohol is 0.5 g: 1 g: 30 ml.
2. The method for rapidly detecting the stability and toxicity of the heavy metals in the fly ash generated by incinerating the household garbage according to claim 1, which is characterized in that: in the step (2) and the step (3), distilled water or deionized water is adopted as water to be mixed with the first fly ash sample and the second fly ash sample respectively; in the steps (2) to (4), the stirring method adopts magnetic stirring, electromechanical stirring or manual stirring, and the stirring speed of the first mixed solution, the second mixed solution or the third mixed solution is controlled to be 150 to 200 r/min.
3. The method for rapidly detecting the stability and toxicity of the heavy metals in the fly ash generated by incinerating the household garbage according to claim 1, which is characterized in that: in the step (2), when the concentration of each water-soluble ion in the first mixed solution is measured, the ionic electrode used for assembling the electrochemical detection device is any one of a lead ion electrode, a chloride ion electrode, a calcium ion electrode, a zinc ion electrode, a cadmium ion electrode, a chromium ion electrode and a copper ion electrode, which is used alone or in combination.
4. The method for rapidly detecting the stability and toxicity of the heavy metals in the fly ash generated by incinerating the household garbage according to claim 1, which is characterized in that: in the step (3), when the pH of the second mixed solution is monitored, the second mixed solution becomes neutral, which means that the pH of the second mixed solution is 6.9 to 7.1.
5. The method for rapidly detecting the stability and toxicity of the heavy metals in the fly ash generated by incinerating the household garbage according to claim 1, which is characterized in that: in the step (4), when the amount of free calcium oxide in the third fly ash sample is detected, the constant-temperature water bath heating condition is that the water bath temperature is not higher than 90 ℃.
6. The method for rapidly detecting the stability and toxicity of the heavy metals in the fly ash generated by incinerating the household garbage according to claim 1, which is characterized in that:
in the step (4), when the mass percentage of free calcium oxide in the third fly ash sample is measured, firstly, observing the color of the prepared third mixed solution, and if the third mixed solution is reddish, dropwise adding a benzoic acid absolute ethyl alcohol solution with a set ratio into the third mixed solution in a dropwise adding mode until the reddish color of the third mixed solution disappears;
repeatedly stirring the third mixed solution for at least 10 minutes, continuously monitoring the color change condition of the third mixed solution, if the third mixed solution does not turn reddish, recording the total consumption of the benzoic acid absolute ethyl alcohol solution which is consumed up to now, comparing the titer of the benzoic acid absolute ethyl alcohol solution on calcium oxide, and calculating the mass percentage of free calcium oxide in the third fly ash sample; and if the third mixed solution turns reddish again, continuously dropwise adding the benzoic acid absolute ethyl alcohol solution with the set proportion into the third mixed solution in a dropwise adding mode until the reddish color of the third mixed solution disappears, recording the total consumption of the benzoic acid absolute ethyl alcohol solution until the reddish color of the third mixed solution disappears, and calculating the mass percent of free calcium oxide in the third fly ash sample by comparing the titer of the benzoic acid absolute ethyl alcohol solution to calcium oxide.
7. The method for rapidly detecting the stability and toxicity of the heavy metals in the fly ash generated by incinerating the household garbage according to claim 1, which is characterized in that: before measuring the concentration of each water-soluble ion in the first mixed solution in the step (2), preparing a chloride ion standard solution, a calcium ion standard solution and a lead ion standard solution with a series of chloride ion concentrations, and preparing a saturated potassium nitrate solution by using potassium nitrate; then, placing the chloride ion electrode in one of the chloride ion standard solutions for activation, placing the calcium ion electrode in one of the calcium ion standard solutions for activation, placing the lead ion electrode in one of the lead ion standard solutions for activation, and placing the reference electrode in a saturated potassium nitrate solution for activation; then respectively assembling electrochemical detection devices, measuring the potential of each chloride ion standard solution by using a chloride ion electrode and a reference electrode, drawing a standard curve of the concentration and the potential of the chloride ions, measuring the potential of each calcium ion standard solution by using a calcium ion electrode and a reference electrode, drawing a standard curve of the concentration and the potential of the calcium ions, measuring the potential of each lead ion standard solution by using a lead ion electrode and a reference electrode, and drawing a standard curve of the concentration and the potential of the lead ions; when the concentration of each water-soluble ion in the first mixed solution is measured in the step (2), an electrochemical measuring device is assembled, the lead ion electrode, the chloride ion electrode and the calcium ion electrode are respectively placed into the first mixed solution test solution together with the reference electrode, displayed potentials are respectively recorded, and the potentials are converted into the concentration of each water-soluble lead ion, the concentration of each water-soluble chloride ion and the concentration of each water-soluble calcium ion in the first mixed solution test solution according to the standard curve of each ion concentration and the potential to be used as the concentration of each water-soluble ion in the first mixed solution.
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| CN108680707B (en) * | 2018-05-18 | 2021-04-27 | 光大环保技术研究院（南京）有限公司 | Quantitative analysis method for all components of fly ash |
| 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 |
| 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 |
| 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 |
| CN115015224B (en) * | 2022-05-30 | 2023-04-25 | 南京理工大学 | Grading evaluation method for determining water body environment risk by using heavy metals contained in fly ash |
| CN115078648A (en) * | 2022-06-15 | 2022-09-20 | 深圳市航天新材科技有限公司 | Rapid detection method and post-treatment method for incineration fly ash quality |
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