CN114235523A - Method for detecting content of heavy metal elements in fly ash of household garbage power plant - Google Patents
Method for detecting content of heavy metal elements in fly ash of household garbage power plant Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000010881 fly ash Substances 0.000 title claims abstract description 25
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 17
- 239000010813 municipal solid waste Substances 0.000 title claims abstract description 13
- 238000010790 dilution Methods 0.000 claims abstract description 47
- 239000012895 dilution Substances 0.000 claims abstract description 47
- 238000002386 leaching Methods 0.000 claims abstract description 43
- 238000001514 detection method Methods 0.000 claims abstract description 35
- 238000012360 testing method Methods 0.000 claims abstract description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000011088 calibration curve Methods 0.000 claims abstract description 11
- 238000012790 confirmation Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229960000583 acetic acid Drugs 0.000 claims abstract description 7
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000000523 sample Substances 0.000 claims description 69
- 239000000243 solution Substances 0.000 claims description 41
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 27
- 229910017604 nitric acid Inorganic materials 0.000 claims description 27
- 238000009616 inductively coupled plasma Methods 0.000 claims description 19
- 239000012086 standard solution Substances 0.000 claims description 19
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000013522 chelant Substances 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000005259 measurement Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052790 beryllium Inorganic materials 0.000 claims description 7
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- 239000011133 lead Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 6
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- 239000003365 glass fiber Substances 0.000 claims description 3
- 238000007603 infrared drying Methods 0.000 claims description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 3
- 229940012189 methyl orange Drugs 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims description 3
- 239000012488 sample solution Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000007306 turnover Effects 0.000 claims description 3
- 238000012795 verification Methods 0.000 claims description 3
- 238000011156 evaluation Methods 0.000 claims description 2
- 239000003814 drug Substances 0.000 abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 229910052786 argon Inorganic materials 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 description 4
- 239000010791 domestic waste Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000004056 waste incineration Methods 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 241001494115 Stomoxys calcitrans Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012898 sample dilution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
A detection method for the heavy metal element content in fly ash of a household garbage incineration power plant is characterized in that only glacial acetic acid one medicament is needed to be prepared in the leaching stage in the detection process, complicated leaching agent confirmation operation is not needed, a calibration curve is drawn only once in the detection stage, the concentration gradient of the curve is reasonably set, the dilution multiple of a suspected high-concentration sample can be confirmed before on-line detection, the preparation work of the medicament in HJ/T300-plus 2007 can be effectively simplified, the leaching agent confirmation operation is not needed, and various defects that HJ 781-plus 2016 requires multiple standard samples in the aspects of detecting the heavy metal content of the fly ash of the garbage incineration power plant and chelates of the fly ash are large, the concentration gradient of the calibration curve is unreasonable, the testing time is long, high-purity argon is consumed, the detection difficulty is high, the environment is polluted by high-concentration waste liquid and the like can be effectively solved. Compared with the prior art, the invention has obvious advantages in the aspects of sample testing period, material consumption, labor intensity, pollution control among samples, detection difficulty and the like.
Description
Technical Field
The invention relates to the technical field of solid waste detection, in particular to a method for detecting the content of heavy metal elements in fly ash of a household garbage incineration power plant.
Background
The fly ash of the domestic waste incineration plant contains more heavy metals and dioxin substances, and is listed in the national hazardous waste record (2016 edition), and the fly ash needs to be treated safely and harmlessly to protect the environment. The current method is to mix chelating agent to react with fly ash to form stable fly ash chelate, and the concentration of hazardous components in the leachate prepared by the solid waste leaching toxicity leaching method acetic acid buffer solution method (HJ/T300-2007) is lower than the limit value specified in the table 1 of the pollution control Standard of municipal solid waste landfill (GB 16889-2008), and then the leachate can be disposed in the municipal solid waste landfill. Therefore, the heavy metals in the fly ash and the chelate generated in the waste incineration process need to be continuously detected to judge whether the requirements of entering the field and landfill are met.
At present, the detection method of the content of heavy metals in domestic household garbage fly ash and chelates thereof is mainly divided into two steps, wherein the first step is a leaching stage, a heavy metal leachate is prepared by using HJ/T300-plus 2007, the second step is a detection stage, the leachate is prepared into a machine sample by using 7.3.2 in an inductively coupled plasma emission spectrometry (HJ 781-plus 2016) method for determining 22 metal elements in solid waste, and then the detection of copper, zinc, lead, cadmium, nickel, beryllium, barium and total chromium is completed by adopting the subsequent steps of the method.
However, the test ranges of HJ/T300-2007 and HJ 781-2016 are solid waste categories and are not established specifically for the detection of heavy metals in fly ash and its chelates. For the method of HJ/T300-2007, the following problems exist in the process of testing the waste fly ash and the chelate thereof: firstly, more kinds of medicines need to be prepared, and medicines which are easy to prepare are involved, so that the requirement on medicine management is high; ② the process of the extractant confirmation is complicated, and each sample takes at least more than 20 minutes; and thirdly, the overturning oscillation process needs to be controlled at 23 +/-2 ℃, and the requirement on the laboratory environment is high. For the HJ 781-2016 process, the following problems exist: firstly, 4 calibration curves need to be drawn, all samples need to be tested for four times on a machine, the testing time is long, more high-purity argon is consumed, more types of required standard substances are needed, and manpower and material resources are wasted; the reference concentration gradient of the solution in the standard series given by the method is greatly different from the limit value regulation in GB 16889-: the method suggests that the maximum concentration point of the standard curve is 5ppm, the specified entrance limit value is 100ppm, and the actual sample is 0.01ppm-180ppm, so that the detection requirement of the actual sample can not be met basically. In addition, the existing detection method lacks a means for rapidly screening suspected high-concentration samples in the leaching solution of fly ash and chelates thereof, cannot dilute the suspected high-concentration samples in advance before sample introduction, and can only dilute and re-determine the samples after sample introduction, but because the concentrations of all to-be-detected machine-mounted samples are unknown, if the concentrations of the samples are higher, a sample introduction system is polluted, and a sample introduction needle and a sample introduction pipeline need to be frequently cleaned or replaced; secondly, the salt deposition rate of parts such as an atomizer, a torch tube, a cold cone and the like of the inductively coupled plasma emission spectrometer is accelerated, and the cleaning frequency needs to be increased or the parts need to be directly replaced; and the possibility of pollution among samples is high, so that the detection results of the low-concentration samples and the blank samples of the batch of machine samples are influenced, the detection time and the detection difficulty are increased, or the test fails directly.
SUMMERY OF THE UTILITY MODEL
In order to solve the problems, the invention provides a method for detecting the content of heavy metal elements in fly ash of a domestic waste incineration power plant by referring to a relevant standard method and combining a large number of experimental experiences according to the composition characteristics of the fly ash of the domestic waste power plant and a chelate thereof, wherein after a heavy metal leachate is prepared by directly adopting a leaching agent #2 in HJ/T300-plus 2007, a hydrogen ion activity meter is used for measuring the hydrogen ion concentration index value (pH value) of the leachate, the sample dilution multiple is determined, then the leachate is treated according to 7.3.2 in the HJ 781-plus 2016 method, a suspected high-concentration sample is diluted to obtain a final machine sample, after the test conditions are optimized according to the specification of an inductively coupled plasma emission spectrometer manufacturer, the standard solution is introduced into the inductively coupled plasma emission spectrometer from low concentration to high concentration for measuring the emission intensity, and the mass concentration of a target element series is taken as a horizontal coordinate, and (3) establishing a calibration curve of the target element by taking the emission intensity value as a vertical coordinate, sequentially introducing the final upper sample into the inductively coupled plasma emission spectrometer in sequence to measure the emission intensity, and calculating the content according to the calibration curve. The invention only needs to prepare 1 medicament of glacial acetic acid in the extraction stage, does not need to carry out complicated extraction agent confirmation operation, only draws a calibration curve once in the detection stage, has reasonable curve concentration gradient arrangement, can confirm the dilution multiple of a suspected high-concentration sample before the on-line detection, can effectively simplify the preparation work of the medicament in HJ/T300-plus 2007, does not need to carry out extraction agent confirmation operation, and can effectively solve the defects of multiple types of standard samples, unreasonable calibration curve concentration gradient, long test time, more high-purity argon consumption, high possibility of pollution among samples, high detection difficulty, environment pollution of high-concentration waste liquid and the like in the aspect of detecting the fly ash of a garbage power plant and the heavy metal content of chelate thereof by HJ 781-plus 2016. Compared with the prior art, the invention has obvious advantages in the aspects of sample testing period, material consumption, labor intensity, pollution control among samples, detection difficulty and the like.
The technical scheme adopted by the invention for solving the technical problem is as follows: a method for detecting the content of heavy metal elements in fly ash of a household garbage incineration power plant is characterized by comprising the following steps:
step 01, weighing 50-100 g of sample in a 100mL ceramic crucible, drying the sample to constant weight at 105 +/-2 ℃, and calculating the water content of the sample;
step 02, diluting 17.25mL of glacial acetic acid to 1L by using reagent water, and preparing an extractant, wherein the pH value of the prepared solution is 2.64 +/-0.05;
step 03, weighing 75-100 g of sample, placing the sample in a 2L extraction bottle, and according to the water content of the sample, according to the liquid-solid ratio of 20: 1 (L: kg), calculating the capacity of the required leaching agent, adding the leaching agent to prepare a leaching solution sample, observing whether bubbles emerge, and if no bubbles emerge, tightly covering a bottle cap and fixing the bottle cap on a turnover oscillation device; if bubbles exist, waiting for 10min and then performing subsequent operation; and placing the extraction bottles filled with the sample and the leaching agent on an overturning oscillator in sequence, wherein the rotating speed of the overturning oscillator is set to be 30 +/-2 rpm, and the time is set to be 18 +/-2 h.
Step 04, referring to general rules of chemical reagent pH determination (GB/T9724-2007), measuring and recording the hydrogen ion concentration index value (pH value) of the leachate by using a hydrogen ion activity meter;
step 05, calculating the dilution factor of the sample according to the hydrogen ion concentration index value (pH value) measured in the step 04; the pH value of the leaching solution is less than or equal to 6.00, and the dilution multiple is 20; the pH value of the leaching solution is more than 6.00 and less than 7.00, and the dilution multiple is 10; the pH value of the leaching solution is more than or equal to 7.00 and less than 7.50, and the dilution multiple is 5; the pH value of the leaching solution is more than or equal to 7.50, and the leaching solution is not diluted;
step 06, mounting a glass fiber filter membrane or a microporous filter membrane with the aperture of 0.6-0.8 mu m on the filter, leaching the filter and the filter membrane by using 5% dilute nitric acid, discarding leacheate, filtering and collecting leachate, acidifying the collected leachate to the pH value of less than 2 by using GR-grade concentrated nitric acid, and storing at 4 ℃;
step 07, weighing 25.00mL of the leachate sample obtained in the step 06 into a 100mL polytetrafluoroethylene crucible, adding 5mL of GR-grade concentrated nitric acid, heating and digesting for 1-2 h (h is hour) at 180 ℃ on an electric hot plate, adding 2mL of GR concentrated nitric acid for continuing heating and digesting until the solution is clear, leaching the crucible with a proper amount of 1% dilute nitric acid solution, completely transferring into a 25mL volumetric flask, fixing the volume to a volume marking line with the 1% dilute nitric acid solution, and uniformly mixing to prepare an upper computer sample solution;
step 08, diluting the upper computer sample liquid according to the dilution multiple required in the step 05 to prepare the upper computer sample liquid with the dilution multiple, and simultaneously, reserving at least 20mL of undiluted stock solution for standby or retesting;
step 09, optimizing test conditions according to the specification of an inductively coupled plasma emission spectrometer manufacturer, igniting the plasma after the detector is corrected, setting according to working parameters provided by the manufacturer, and starting to prepare measurement after the instrument is preheated until various indexes are stable;
step 10, preparing a series of standard solutions of elements to be detected by using standard solutions of copper, zinc, lead, cadmium, nickel, beryllium, barium and chromium in sequence, preparing a series of standard curves by using 1% dilute nitric acid solution, wherein the concentration gradients are 0.1ppm, 0.2ppm, 0.5ppm, 1.0ppm, 2.0ppm, 5ppm and 10 ppm; introducing the standard solution into an inductively coupled plasma emission spectrometer from low to high in sequence, determining emission intensity according to measurement conditions set by a manufacturer specification, and establishing a calibration curve of a target element by taking the mass concentration of the target element series as a horizontal coordinate and the emission intensity value as a vertical coordinate;
step 11, flushing a sample introduction system and an atomization system of the inductively coupled plasma emission spectrometer by using a 1% dilute nitric acid solution, reducing a blank value of an observation instrument to the minimum, starting to analyze a sample after an analysis signal is stable, and measuring the blank sample according to the same operation steps and conditions;
step 12, for a sample without dilution times, outputting a result, namely a final detection result, by the inductively coupled plasma emission spectrometer; the sample with the dilution factor is input with the dilution factor in the test sequence when the test method is edited, and the output result of the instrument is the final detection result; when the dilution factor is not input in editing the test method, the calculation is carried out according to the formula, wherein rho is the calculation result, mg/L, rhoMeasuringThe result is output by the instrument, mg/L, and n is the dilution multiple and is dimensionless.
According to the preferable scheme of the invention, when the total number of the fly ash and the chelate samples thereof in the step 01 is less than or equal to 5, the moisture content measurement mode preferably adopts a microwave drying method or an infrared drying method, and the temperature condition is 105 +/-5 ℃.
In the preferred embodiment of the present invention, the hydrogen ion activity meter in step 04 should meet the requirement of "0.02 level" in 4.7 of "laboratory pH meter verification procedure" JJJG 119-.
According to the preferable scheme of the invention, the hydrogen ion activity meter in the step 04 can be carried out by using wide pH test paper, precise pH test paper, litmus reagent, phenolphthalein reagent, methyl orange reagent or other methods capable of qualitatively or semi-quantitatively judging the pH value, and the determination of the dilution multiple is not influenced.
In the preferred embodiment of the present invention, step 04 and step 06 can be replaced with each other.
In the preferable scheme of the invention, after the dilution times are determined in the steps 04 and 05, the measured values of the dilution of the upper sample are all in the range of a concentration curve or on the right side of the highest concentration point of the curve (the measured values are higher than the highest concentration point); if the detected value is on the right side of the highest concentration point, the stock solution retained in the step 06 is further diluted, and the dilution times are further diluted by 2 times on the original basis; if the detection value is on the left side of the highest concentration point, the sample remained in the step 06 is adopted to be directly tested on the computer.
According to the preferable scheme of the invention, the leachate is subjected to on-machine detection on the day after the preparation in the step 06, and acidification is not required.
According to the preferable scheme of the invention, the digestion operation in the step 07 can be further simplified into acid dispelling operation, namely only heating operation is carried out to remove redundant acidic substances in the leachate, the influence on the result is not more than 1%, and the judgment of the chelate entry standard is not influenced; if the atomizer, the atomizing chamber and the torch of the inductively coupled plasma emission spectrometer are replaced by acid-resistant components, the acid removing operation is not performed, i.e., step 07 is not performed.
In a preferred embodiment of the present invention, the standard solution of copper, zinc, lead, cadmium, nickel, beryllium, barium, and chromium used in step 10 may be replaced by a multi-element mixed standard solution containing the 8 elements, but the multi-element mixed standard solution should not contain substances that interfere with the 8 elements.
In the preferred embodiment of the invention, the confirmation mode that the blank value of the instrument is reduced to the minimum in the step 11 adopts at least 3 samples of 1% nitric acid solution to carry out evaluation and confirmation.
The invention has the beneficial effects that: the invention provides a method for detecting the content of heavy metal elements in fly ash of a household garbage incineration power plant, which only needs to prepare glacial acetic acid as a medicament in the leaching stage in the detection process without complicated leaching agent confirmation operation, only draws a calibration curve once in the detection stage, has reasonable curve concentration gradient arrangement, can confirm the dilution multiple of a suspected high-concentration sample before on-line detection, can effectively simplify the preparation work of drugs in HJ/T300-. Compared with the prior art, the invention has obvious advantages in the aspects of sample testing period, material consumption, labor intensity, pollution control among samples, detection difficulty and the like.
Detailed Description
A method for detecting the content of heavy metal elements in fly ash of a household garbage incineration power plant comprises the following steps:
step 01, weighing 50-100 g of sample in a 100mL ceramic crucible, drying the sample to constant weight at 105 +/-2 ℃, and calculating the water content of the sample;
step 02, diluting 17.25mL of glacial acetic acid to 1L by using reagent water, and preparing an extractant, wherein the pH value of the prepared solution is 2.64 +/-0.05;
step 03, weighing 75-100 g of sample, placing the sample in a 2L extraction bottle, and according to the water content of the sample, according to the liquid-solid ratio of 20: 1 (L: kg), calculating the capacity of the required leaching agent, adding the leaching agent to prepare a leaching solution sample, observing whether bubbles emerge, and if no bubbles emerge, tightly covering a bottle cap and fixing the bottle cap on a turnover oscillation device; if bubbles exist, waiting for 10min and then performing subsequent operation; and placing the extraction bottles filled with the sample and the leaching agent on an overturning oscillator in sequence, wherein the rotating speed of the overturning oscillator is set to be 30 +/-2 rpm, and the time is set to be 18 +/-2 h.
Step 04, referring to general rules of chemical reagent pH determination (GB/T9724-2007), measuring and recording the hydrogen ion concentration index value (pH value) of the leachate by using a hydrogen ion activity meter;
step 05, calculating the dilution factor of the sample according to the hydrogen ion concentration index value (pH value) measured in the step 04; the pH value of the leaching solution is less than or equal to 6.00, and the dilution multiple is 20; the pH value of the leaching solution is more than 6.00 and less than 7.00, and the dilution multiple is 10; the pH value of the leaching solution is more than or equal to 7.00 and less than 7.50, and the dilution multiple is 5; the pH value of the leaching solution is more than or equal to 7.50, and the leaching solution is not diluted;
step 06, mounting a glass fiber filter membrane or a microporous filter membrane with the aperture of 0.6-0.8 mu m on the filter, leaching the filter and the filter membrane by using 5% dilute nitric acid, discarding leacheate, filtering and collecting leachate, acidifying the collected leachate to the pH value of less than 2 by using GR-grade concentrated nitric acid, and storing at 4 ℃;
step 07, weighing 25.00mL of the leachate sample obtained in the step 06 into a 100mL polytetrafluoroethylene crucible, adding 5mL of GR-grade concentrated nitric acid, heating and digesting for 1-2 h (h is hour) at 180 ℃ on an electric hot plate, adding 2mL of GR concentrated nitric acid for continuing heating and digesting until the solution is clear, leaching the crucible with a proper amount of 1% dilute nitric acid solution, completely transferring into a 25mL volumetric flask, fixing the volume to a volume marking line with the 1% dilute nitric acid solution, and uniformly mixing to prepare an upper computer sample solution;
step 08, diluting the upper computer sample liquid according to the dilution multiple required in the step 05 to prepare the upper computer sample liquid with the dilution multiple, and simultaneously, reserving at least 20mL of undiluted stock solution for standby or retesting;
step 09, optimizing test conditions according to the specification of an inductively coupled plasma emission spectrometer manufacturer, igniting the plasma after the detector is corrected, setting according to working parameters provided by the manufacturer, and starting to prepare measurement after the instrument is preheated until various indexes are stable;
step 10, preparing a series of standard solutions of elements to be detected by using standard solutions of copper, zinc, lead, cadmium, nickel, beryllium, barium and chromium in sequence, preparing a series of standard curves by using 1% dilute nitric acid solution, wherein the concentration gradients are 0.1ppm, 0.2ppm, 0.5ppm, 1.0ppm, 2.0ppm, 5ppm and 10 ppm; introducing the standard solution into an inductively coupled plasma emission spectrometer from low to high in sequence, determining emission intensity according to measurement conditions set by a manufacturer specification, and establishing a calibration curve of a target element by taking the mass concentration of the target element series as a horizontal coordinate and the emission intensity value as a vertical coordinate;
step 11, flushing a sample introduction system and an atomization system of the inductively coupled plasma emission spectrometer by using a 1% dilute nitric acid solution, reducing a blank value of an observation instrument to the minimum, starting to analyze a sample after an analysis signal is stable, and measuring the blank sample according to the same operation steps and conditions;
step 12, for samples without dilution factor, inductive coupling and the likeThe plasma emission spectrometer outputs a result, namely a final detection result; the sample with the dilution factor is input with the dilution factor in the test sequence when the test method is edited, and the output result of the instrument is the final detection result; when the dilution factor is not input in editing the test method, the calculation is carried out according to the formula, wherein rho is the calculation result, mg/L, rhoMeasuringThe result is output by the instrument, mg/L, and n is the dilution multiple and is dimensionless.
Preferably, when the total number of the fly ash and the chelate samples thereof in the step 01 is less than or equal to 5, the moisture content is preferably measured by adopting a microwave drying method or an infrared drying method, and the temperature is 105 +/-5 ℃.
Preferably, the hydrogen ion activity meter in step 04 should meet the requirement of "0.02 level" in 4.7 of "laboratory pH meter verification protocol" JJJG 119-.
Preferably, the hydrogen ion activity meter in step 04 can be performed by using a wide pH test paper, a precision pH test paper, a litmus reagent, a phenolphthalein reagent, a methyl orange reagent or other methods capable of performing qualitative or semi-quantitative determination on the pH value, without affecting the determination of the dilution factor.
Preferably, step 04 and step 06 may be interchanged with each other.
Preferably, after the dilution times are determined in step 04 and step 05, all the measured values of the dilution of the upper sample are within the range of the concentration curve or on the right side of the highest concentration point of the curve (the measured values are higher than the highest concentration point); if the detected value is on the right side of the highest concentration point, the stock solution retained in the step 06 is further diluted, and the dilution times are further diluted by 2 times on the original basis; if the detection value is on the left side of the highest concentration point, the sample remained in the step 06 is adopted to be directly tested on the computer.
Preferably, the leachate is subjected to on-machine detection on the day after the preparation in step 06, and acidification is not required.
Preferably, the digestion operation in the step 07 can be further simplified into an acid dispelling operation, namely only a heating operation is performed to remove redundant acidic substances in the leachate, the influence on the result is not more than 1%, and the judgment of the chelate entry standard is not influenced; if the atomizer, the atomizing chamber and the torch of the inductively coupled plasma emission spectrometer are replaced by acid-resistant components, the acid removing operation is not performed, i.e., step 07 is not performed.
Preferably, the standard solution of copper, zinc, lead, cadmium, nickel, beryllium, barium and chromium used in step 10 can be replaced by a multi-element mixed standard solution containing the 8 elements, but the multi-element mixed standard solution should not contain substances which can interfere with the 8 elements.
Preferably, the confirmation of the lowest instrument blank in step 11 is evaluated by testing at least 3 samples of 1% nitric acid solution.
Claims (10)
1. A method for detecting the content of heavy metal elements in fly ash of a household garbage incineration power plant is characterized by comprising the following steps:
step 01, weighing 50-100 g of sample in a 100mL ceramic crucible, drying the sample to constant weight at 105 +/-2 ℃, and calculating the water content of the sample;
step 02, diluting 17.25mL of glacial acetic acid to 1L by using reagent water, and preparing an extractant, wherein the pH value of the prepared solution is 2.64 +/-0.05;
step 03, weighing 75-100 g of sample, placing the sample in a 2L extraction bottle, and according to the water content of the sample, according to the liquid-solid ratio of 20: 1 (L: kg), calculating the capacity of the required leaching agent, adding the leaching agent to prepare a leaching solution sample, observing whether bubbles emerge, and if no bubbles emerge, tightly covering a bottle cap and fixing the bottle cap on a turnover oscillation device; if bubbles exist, waiting for 10min and then performing subsequent operation; placing the extraction bottles filled with the sample and the leaching agent on an overturning oscillator in sequence, wherein the rotating speed of the overturning oscillator is set to be 30 +/-2 rpm, and the time is set to be 18 +/-2 h;
step 04, referring to general rules of chemical reagent pH determination (GB/T9724-2007), measuring and recording the hydrogen ion concentration index value (pH value) of the leachate by using a hydrogen ion activity meter;
step 05, calculating the dilution factor of the sample according to the hydrogen ion concentration index value (pH value) measured in the step 04; the pH value of the leaching solution is less than or equal to 6.00, and the dilution multiple is 20; the pH value of the leaching solution is more than 6.00 and less than 7.00, and the dilution multiple is 10; the pH value of the leaching solution is more than or equal to 7.00 and less than 7.50, and the dilution multiple is 5; the pH value of the leaching solution is more than or equal to 7.50, and the leaching solution is not diluted;
step 06, mounting a glass fiber filter membrane or a microporous filter membrane with the aperture of 0.6-0.8 mu m on the filter, leaching the filter and the filter membrane by using 5% dilute nitric acid, discarding leacheate, filtering and collecting leachate, acidifying the collected leachate to the pH value of less than 2 by using GR-grade concentrated nitric acid, and storing at 4 ℃;
step 07, weighing 25.00mL of the leachate sample obtained in the step 06 into a 100mL polytetrafluoroethylene crucible, adding 5mL of GR-grade concentrated nitric acid, heating and digesting for 1-2 h (h is hour) at 180 ℃ on an electric hot plate, adding 2mL of GR concentrated nitric acid for continuing heating and digesting until the solution is clear, leaching the crucible with a proper amount of 1% dilute nitric acid solution, completely transferring into a 25mL volumetric flask, fixing the volume to a volume marking line with the 1% dilute nitric acid solution, and uniformly mixing to prepare an upper computer sample solution;
step 08, diluting the upper computer sample liquid according to the dilution multiple required in the step 05 to prepare the upper computer sample liquid with the dilution multiple, and simultaneously, reserving at least 20mL of undiluted stock solution for standby or retesting;
step 09, optimizing test conditions according to the specification of an inductively coupled plasma emission spectrometer manufacturer, igniting the plasma after the detector is corrected, setting according to working parameters provided by the manufacturer, and starting to prepare measurement after the instrument is preheated until various indexes are stable;
step 10, preparing a series of standard solutions of elements to be detected by using standard solutions of copper, zinc, lead, cadmium, nickel, beryllium, barium and chromium in sequence, preparing a series of standard curves by using 1% dilute nitric acid solution, wherein the concentration gradients are 0.1ppm, 0.2ppm, 0.5ppm, 1.0ppm, 2.0ppm, 5ppm and 10 ppm; introducing the standard solution into an inductively coupled plasma emission spectrometer from low to high in sequence, determining emission intensity according to measurement conditions set by a manufacturer specification, and establishing a calibration curve of a target element by taking the mass concentration of the target element series as a horizontal coordinate and the emission intensity value as a vertical coordinate;
step 11, flushing a sample introduction system and an atomization system of the inductively coupled plasma emission spectrometer by using a 1% dilute nitric acid solution, reducing a blank value of an observation instrument to the minimum, starting to analyze a sample after an analysis signal is stable, and measuring the blank sample according to the same operation steps and conditions;
step 12, for a sample without dilution times, outputting a result, namely a final detection result, by the inductively coupled plasma emission spectrometer; the sample with the dilution factor is input with the dilution factor in the test sequence when the test method is edited, and the output result of the instrument is the final detection result; when the dilution factor is not input in editing the test method, the calculation is carried out according to the formula, wherein rho is the calculation result, mg/L, rhoMeasuringThe result is output by the instrument, mg/L, and n is the dilution multiple and is dimensionless.
2. The method according to claim 1, wherein the method comprises the steps of,
when the total number of the fly ash and the chelate samples thereof is less than or equal to 5 in the step 01, the water content measurement mode preferably adopts a microwave drying method or an infrared drying method, and the temperature condition is 105 +/-5 ℃.
3. The method according to claim 1, wherein the method comprises the steps of,
the hydrogen ion activity meter in step 04 should meet the requirement of "0.02 level" in 4.7 of "laboratory pH meter verification procedure" JJJG 119-.
4. The method according to claim 1, wherein the method comprises the steps of,
the hydrogen ion activity meter in the step 04 can be carried out by using wide pH test paper, precise pH test paper, litmus reagent, phenolphthalein reagent, methyl orange reagent or other methods capable of qualitatively or semi-quantitatively judging the pH value, and the determination of the dilution multiple is not influenced.
5. The method according to claim 1, wherein the method comprises the steps of,
step 04 and step 06 may be interchanged.
6. The method according to claim 1, wherein the method comprises the steps of,
after the dilution times are determined in the steps 04 and 05, diluting the upper sample, wherein the measured value is in the range of the concentration curve or on the right side of the highest concentration point of the curve (the measured value is higher than the highest concentration point); if the detected value is on the right side of the highest concentration point, the stock solution retained in the step 06 is further diluted, and the dilution times are further diluted by 2 times on the original basis; if the detection value is on the left side of the highest concentration point, the sample remained in the step 06 is adopted to be directly tested on the computer.
7. The method according to claim 1, wherein the method comprises the steps of,
and (06) detecting the leachate on the machine on the day after the preparation is finished, and acidifying is not needed.
8. The method according to claim 1, wherein the method comprises the steps of,
the digestion operation in the step 07 can be further simplified into acid dispelling operation, namely only heating operation is carried out to remove redundant acidic substances in the leachate, the influence on the result is not more than 1%, and the judgment of the chelate entry standard is not influenced; if the atomizer, the atomizing chamber and the torch of the inductively coupled plasma emission spectrometer are replaced by acid-resistant components, the acid removing operation is not performed, i.e., step 07 is not performed.
9. The method according to claim 1, wherein the method comprises the steps of,
in the step 10, the standard solution of copper, zinc, lead, cadmium, nickel, beryllium, barium and chromium can be replaced by the multi-element mixed standard solution containing the 8 elements, but the multi-element mixed standard solution does not contain substances which can generate mutual interference with the 8 elements.
10. The method according to claim 1, wherein the method comprises the steps of,
and (3) adopting a mode of confirming that the instrument blank value is reduced to the minimum in the step 11, and testing at least 3 samples of 1% nitric acid solution for evaluation and confirmation.
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| CN114610086A (en) * | 2022-04-08 | 2022-06-10 | 深圳能源环保股份有限公司 | PH value-based waste incineration fly ash treatment method and device and storage medium |
| WO2023103718A1 (en) * | 2021-12-09 | 2023-06-15 | 深圳市深能环保东部有限公司 | Method for measuring content of heavy metal elements in household garbage power plant fly ash |
| CN116558918A (en) * | 2023-04-27 | 2023-08-08 | 上海海关机电产品检测技术中心 | Method for simultaneously measuring Pb, cd, cr, hg, br content in electronic and electric products based on ICP-MS |
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| CN116754349B (en) * | 2023-08-16 | 2023-11-21 | 四川赛科检测技术有限公司 | ICP-OES-based digestion method for lithium sulfide impurity elements and content determination method thereof |
| CN117470618A (en) * | 2023-12-28 | 2024-01-30 | 中国科学院烟台海岸带研究所 | Ultrafiltration separation detection method for colloidal iron in seawater |
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