CN110487932A - The detection method of chlorine in a kind of solid waste - Google Patents
The detection method of chlorine in a kind of solid waste Download PDFInfo
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- CN110487932A CN110487932A CN201910783839.XA CN201910783839A CN110487932A CN 110487932 A CN110487932 A CN 110487932A CN 201910783839 A CN201910783839 A CN 201910783839A CN 110487932 A CN110487932 A CN 110487932A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N2030/645—Electrical detectors electrical conductivity detectors
Abstract
The invention discloses a kind of detection methods of chlorine in solid waste, are related to solid waste element determination technical field.The principle of this detection method includes: to prepare solid waste sample, then solid waste sample and KOH alkali fusion reagent mixing low temp are ashed, taken out, let cool, dissolved samples, constant volume, it mixes, it is spare after filtering, chlorine generates chloride in solid waste, and chloride is entered anion chromatographic column with alkali cleaning leacheate, is separated in the form of sulfate, it is detected with electric conductivity detector, according to the content of chlorine in the Mass Calculation solid waste of chloride ion.The detection method of chlorine in a kind of solid waste provided by the present invention, this method is easy to operate, reproducible, accuracy is high, can be applied to the measurement of chlorine in solid waste, and detection process is stablized, do not influenced by other factors.
Description
Technical field
The present invention relates to solid waste element determination technical field, the detection method of chlorine in specially a kind of solid waste.
Background technique
Chlorine is one of the harmful element in solid waste, and Cl is mainly with KCl, NaCl, hydrated magnesium chloride in solid waste
(MgCl2·6H2) etc. O the form of inorganic matters exists, and exists in the form of organic matter on a small quantity.Cl is main in burning and pyrolytic process
It is discharged in a manner of HCI gas, content (mass fraction, w) is more than 2% solid waste, in combustion can accelerated corrosion
Incinerator, in solid waste burning disposal process, corrosiveness is even more serious.High chlorine solid waste directly burn can generate with
Polychlorinated dibenzo-2 dislikes English (PCDDs) and polychlorinated dibenzo (PCDFs) is various organic chlorides (the carcinogenic, cause of representative
Abnormal, mutagenesis) and environment is polluted, and combustion product hydrogen chloride discharges into the atmosphere to form acid rain initiation environmental problem.Therefore
The content of chlorine has become one of the important Con trolling index of solid waste burning disposition in solid waste.
Inventor has found that current chloride ion method has Emhorn card intermixture to melt sample-sulphur hydracid potassium titration, high-temp combustion water
Solution-potentiometric titration, chromatography of ions etc., Emhorn card intermixture melts sample and handles sample, due to water-soluble in the commercially available drinox in China
Chlorinity is higher is difficult to meet chlorine measurement requirement in biomass for property.High-temperature combustion hydrolytic-potentiometric titration is that China's national standard is recommended
Method, measuring principle are by solid waste sample fuel and hydrolysis in oxygen and vapor mixed flow, and chlorine all turns in sample
Turn to chloride and quantitatively soluble in water.Using silver as indicator electrode, silver-silver chloride is reference electrode, with standard silver nitrate electricity
Chloride ion in the method direct titration condensate liquid of position calculates chlorinity in solid waste according to standard silver nitrate titration solution dosage.
High-temperature fuel hydrolysis-potentiometric titration is cumbersome, and titration end-point is indicated using potential jump, and influence factor is more, such as
The AgCl flocculent deposit generated in titration process is easy to be deposited on the measurement end of silver electrode and double salt bridge electrodes, makes measuring cell
Potential value cannot be provided correctly, thus influence the judgement to terminal.It simultaneously may also containing more other factors in solid waste
It will affect the measurement of chlorine, therefore the present invention provides a kind of measuring method of chlorine in improved solid waste.
Summary of the invention
The present invention is in order to solve the measurement of chlorine in solid waste and prevent other factors from measuring asking of having an impact to it
Topic provides a kind of detection method of chlorine in solid waste.
The present invention is achieved by the following technical solution: the detection method of chlorine in a kind of solid waste, including as follows
Step:
(1) sample preparation: solid waste is prepared to the sample that can be sieved by 0.5mm, 20g is taken to mix, it is dry to reach air
It is packed into sample bottle after dry state, is sealed, it is spare；
(2) sample treatment: weighing a certain amount of sample, be accurate to 0.0002g, be placed in crucible, adds 1.0g ± 0.1g hydrogen-oxygen
Change potassium, so that it is evenly distributed, be put into low temperature dry ashing in high-temperature electric resistance furnace, takes out, let cool；In crucible plus 20mL pure water, dissolution try
This solution is transferred in 100mL volumetric flask by sample, is washed crucible for several times with 20mL moisture, is incorporated in volumetric flask, is settled to water
Scale mixes, spare after 0.45 μm of filtering with microporous membrane；
Blank control group processing: in crucible, add 1.0g ± 0.1g potassium hydroxide, it is made to be evenly distributed, be put into high-temperature electric resistance furnace
Middle low temperature dry ashing is taken out, is let cool；In crucible plus this solution is transferred to by 20mL pure water, the potassium hydroxide after dissolution ashing
In 100mL volumetric flask, crucible is washed for several times with 20mL moisture, is incorporated in volumetric flask, be settled to scale with water, mix, through 0.45 μ
It is spare after m filtering with microporous membrane；
(3) chromatographiccondition: leacheate: 7.5mM Na2CO3/0.75mM NaOH；Flow velocity: 0.6mL ﹒ min-1；Sample introduction
Volume: 20 μ L；Column pressure: 0~20MPa；Column temperature: room temperature；Detection mode: Conductivity detection；
(4) ion chromatography test method: taking isometric sample solution, injects in ion chromatograph, records chromatogram, with
Chromatographic peak area integrated value is quantified, and the mass fraction (%) of chlorine in sample is calculated by formula (1):
W=(C-C0)*V/m*100 (1)
In formula: cl concn in C-test solution, unit are milligrams per liter mgL-1；C0Cl concn in-blank test, unit are
Milligrams per liter mgL-1；V-test solution volume, unit are milliliter mL；M-sample mass, unit are gram (g).
The principle of this detection method includes: the chlorine in solid waste by solid waste sample and KOH alkali fusion reagent mixing calcination
Chloride is generated, chloride is entered anion chromatographic column with alkali cleaning leacheate, is separated in the form of sulfate, electricity consumption
Detector detection is led, according to the content of chlorine in the Mass Calculation solid waste of chloride ion.
Compared with prior art the invention has the following advantages: chlorine in a kind of solid waste provided by the present invention
Detection method, this method is easy to operate, reproducible, accuracy is high, can be applied to the measurement of chlorine in solid waste, detection process
Stablize, is not influenced by other factors.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.
The detection method of chlorine, includes the following steps: in a kind of solid waste
(1) sample preparation: solid waste is prepared to the sample that can be sieved by 0.5mm, 20g is taken to mix, it is dry to reach air
It is packed into sample bottle after dry state, is sealed, it is spare；
(2) sample treatment: weighing a certain amount of sample, be accurate to 0.0002g, be placed in crucible, adds 1.0g ± 0.1g hydrogen-oxygen
Change potassium, so that it is evenly distributed, be put into low temperature dry ashing in high-temperature electric resistance furnace, takes out, let cool；In crucible plus 20mL pure water, dissolution try
This solution is transferred in 100mL volumetric flask by sample, is washed crucible for several times with 20mL moisture, is incorporated in volumetric flask, is settled to water
Scale mixes, spare after 0.45 μm of filtering with microporous membrane；
Blank control group processing: in crucible, add 1.0g ± 0.1g potassium hydroxide, it is made to be evenly distributed, be put into high-temperature electric resistance furnace
Middle low temperature dry ashing is taken out, is let cool；In crucible plus this solution is transferred to by 20mL pure water, the potassium hydroxide after dissolution ashing
In 100mL volumetric flask, crucible is washed for several times with 20mL moisture, is incorporated in volumetric flask, be settled to scale with water, mix, through 0.45 μ
It is spare after m filtering with microporous membrane；
(3) chromatographiccondition: leacheate: 7.5mM Na2CO3/0.75mM NaOH；Flow velocity: 0.6mL ﹒ min-1；Sample introduction
Volume: 20 μ L；Column pressure: 0~20MPa；Column temperature: room temperature；Detection mode: Conductivity detection；
Isometric sample solution is taken, is injected in ion chromatograph, chromatogram is recorded, with the progress of chromatographic peak area integrated value
It is quantitative.
1. it is as shown in table 1 to draw solid waste chloride ion standard curve.
1 standard curve icon of table
| Serial number | 1 | 2 | 3 | 4 | 5 | Parameter of curve |
| Concentration mg/L | 2 | 4 | 10 | 20 | 50 | Y=0.2143x-01251 |
| Peak area | 0.3660 | 0.7379 | 1.8859 | 3.9454 | 8.5844 | R2=0.998 |
2. blank sample measurement and detection limit calculate:
According to the Overall Steps of sample analysis, measurement result is scaled concentration by replication n (n >=7) secondary blank test
Or content, the standard deviation that n times are measured in parallel is calculated, (2) calculate its detection limit as follows, and the results are shown in Table 3:
MDL=t (n-1,0.99) × S (2)
In formula: MDL represents method detection limit；The parallel determination number of n representative sample；T represents freedom degree as n-1, confidence
T distribution when degree is 99%, as shown in table 2；S represents the standard deviation of n times parallel determination.
Table 2t value table
| It is measured in parallel number (n) | Freedom degree (n-1) | T (n-1,0.99) | Remarks |
| 7 | 6 | 3.143 | It is unilateral |
| 8 | 7 | 2.998 | It is unilateral |
| 7 | 6 | 3.707 | Bilateral |
| 8 | 7 | 3.499 | Bilateral |
3 blank value measurement result of table and method detection limit
When sample volume be 2g, be settled to 100mL, then limit of identification be 0.008mgkg-1.Increase sample weighting amount and
Reducing constant volume can be improved the detection limit of sample.
3. method precision:
It is measured in parallel same sample bottoms 7 times, by formula (3), (4) and (5) calculation method precision, as a result such as table
Shown in 4.
In formula: xkRepresent the k test result carried out in laboratory to a certain concentration level sample；Represent laboratory
The interior average value to a certain concentration level sample test；SiIt represents in laboratory to the standard deviation of a certain concentration level sample test
Difference；RSDiIt represents in laboratory to the relative standard deviation of a certain concentration level sample test.
4 precision test data of table
4. method accuracy:
It is measured in parallel certified reference material GBW07602 and GBW07603 each 7 times, by formula (6) calculation method accuracy,
The results are shown in Table 5.
In formula:Represent the average value tested a certain concentration or contents level standard substance；μ represents the dense of standard substance
Degree or content；REiRepresent the relative error tested a certain concentration or contents level standard substance.
5 accuracy test data of table
| Sample | GBW07602 | GBW07603 |
| Unit | % | % |
| 1 | 1.10 | 1.90 |
| 2 | 1.08 | 1.95 |
| 3 | 1.12 | 1.91 |
| 4 | 1.09 | 1.88 |
| 5 | 1.11 | 1.86 |
| 6 | 1.14 | 1.89 |
| 7 | 1.12 | 1.92 |
| Average value | 1.11 | 1.90 |
| Standard substance concentration | 1.13 | 1.93 |
| Relative standard deviation RE% | 1.8 | 1.5 |
It can thus be seen that the measuring method of chlorine is simple and quick in solid waste provided herein, detection limit shows
The concentration limit that noise can be distinguished over is smaller, can effectively detect the sample to be tested of low concentration, and this method precision
And accuracy is higher, illustrates that the result tested by measuring method provided by the present application is accurate and reliable.
In conclusion the measuring method of chlorine is simple and quick in solid waste provided by the present application, test result is accurate and reliable,
It can be applied to the measurement of chlorine in solid waste.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (1)
1. the detection method of chlorine in a kind of solid waste, characterized by the following steps:
(1) sample preparation: solid waste is prepared to the sample that can be sieved by 0.5mm, takes 20g to mix, reaches and be air-dried shape
It is packed into sample bottle after state, is sealed, it is spare；
(2) sample treatment: weighing a certain amount of sample, be accurate to 0.0002g, be placed in crucible, adds 1.0g ± 0.1g hydroxide
Potassium makes it be evenly distributed, and is put into low temperature dry ashing in high-temperature electric resistance furnace, takes out, lets cool；In crucible plus 20mL pure water, dissolution try
This solution is transferred in 100mL volumetric flask by sample, is washed crucible for several times with 20mL moisture, is incorporated in volumetric flask, is settled to water
Scale mixes, spare after 0.45 μm of filtering with microporous membrane；
Blank control group processing: in crucible, add 1.0g ± 0.1g potassium hydroxide, it is made to be evenly distributed, be put into low in high-temperature electric resistance furnace
Temperature ashing, takes out, lets cool；In crucible plus this solution is transferred to 100mL by 20mL pure water, the potassium hydroxide after dissolution ashing
In volumetric flask, crucible is washed for several times with 20mL moisture, is incorporated in volumetric flask, be settled to scale with water, mix, through 0.45 μm of micropore
It is spare after membrane filtration；
(3) chromatographiccondition: leacheate: 7.5mM Na2CO3/0.75mM NaOH；Flow velocity: 0.6mL ﹒ min-1；Sampling volume:
20μL；Column pressure: 0 ~ 20 MPa；Column temperature: room temperature；Detection mode: Conductivity detection；
(4) ion chromatography test method: taking isometric sample solution, injects in ion chromatograph, chromatogram is recorded, with chromatography
Integrating peak areas value is quantified, and the mass fraction (%) of chlorine in sample is calculated by formula (1):
w=(C-C0)*V/m*100 (1)
In formula: cl concn in C-test solution, unit are milligrams per liter mgL-1；C0Cl concn in-blank test, unit are milligram
Every liter of mgL-1；V-test solution volume, unit are milliliter mL；M-sample mass, unit are gram (g).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112229941A (en) * | 2020-09-29 | 2021-01-15 | 中国科学院地球化学研究所 | Halogen detection method in geological sample |
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| US4869794A (en) * | 1987-06-26 | 1989-09-26 | Commissariat A L'energie Atomique | Process for eliminating the chloride ions present in contaminated solid wastes, such as incineration ashes contaminated by actinides |
| CN101551367A (en) * | 2009-04-15 | 2009-10-07 | 四川大学 | Low pressure ion-exclusion chromatography for synchronously analyzing chloride and sulphide |
| CN105973666A (en) * | 2016-05-04 | 2016-09-28 | 新奥科技发展有限公司 | Chlorine and sulfur extraction and determination method and apparatus thereof |
| CN106053684A (en) * | 2016-06-21 | 2016-10-26 | 广东电网有限责任公司电力科学研究院 | Method for preprocessing sample in measurement of chlorine and fluorine content in biomass |
| CN109470813A (en) * | 2018-11-11 | 2019-03-15 | 华东理工大学 | The measuring method of chlorine and bromine content in plastics |
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2019
- 2019-08-23 CN CN201910783839.XA patent/CN110487932A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4869794A (en) * | 1987-06-26 | 1989-09-26 | Commissariat A L'energie Atomique | Process for eliminating the chloride ions present in contaminated solid wastes, such as incineration ashes contaminated by actinides |
| CN101551367A (en) * | 2009-04-15 | 2009-10-07 | 四川大学 | Low pressure ion-exclusion chromatography for synchronously analyzing chloride and sulphide |
| CN105973666A (en) * | 2016-05-04 | 2016-09-28 | 新奥科技发展有限公司 | Chlorine and sulfur extraction and determination method and apparatus thereof |
| CN106053684A (en) * | 2016-06-21 | 2016-10-26 | 广东电网有限责任公司电力科学研究院 | Method for preprocessing sample in measurement of chlorine and fluorine content in biomass |
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Non-Patent Citations (3)
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| H. BELEVI* ET AL.: "Simultaneous determination of fluorine, chlorine and sulfur in incinerator residues by oxidative high pressure digestion and ion chromatography", 《ANALUSIS》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112229941A (en) * | 2020-09-29 | 2021-01-15 | 中国科学院地球化学研究所 | Halogen detection method in geological sample |
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