CN114053755A - Extracting agent and extracting method for detecting harmful substances in interior wall coating - Google Patents
Extracting agent and extracting method for detecting harmful substances in interior wall coating Download PDFInfo
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Abstract
The invention belongs to the technical field of detection of harmful substances in coatings, and discloses an extracting agent and an extracting method for detecting harmful substances in interior wall coatings, wherein the extracting agent consists of hydrochloric acid buffer solution containing a derivative and a surfactant, acetonitrile and dichloromethane, and the volume ratio of the hydrochloric acid buffer solution to the acetonitrile to the dichloromethane is 70-50: 25-40: 5-10; the pH value of the hydrochloric acid buffer solution is 1.0-5.0. The extraction method comprises the following steps: the extracting agent is used for extracting harmful substances in the interior wall coating, and a rapid solvent extractor is used for extraction. The extracting agent and the extracting method have the advantages of strong applicability, multi-task treatment, high efficiency and the like.
Description
Technical Field
The invention belongs to the technical field of detection of harmful substances in coatings, and particularly relates to an extracting agent for detecting harmful substances in an interior wall coating and an extracting method for detecting harmful substances in the interior wall coating by using the extracting agent.
Background
The interior wall coating is prepared by taking synthetic resin emulsion as a base material, and mixing the base material with pigment, extender pigment and various auxiliary agents, can form a thin coating with a smooth surface after being coated, and is widely applied to the field of building home decoration.
Among the problems related to the quality safety of interior wall coatings, the excessive content of formaldehyde is one of the more serious problems. Although formaldehyde has a good antiseptic effect, when the formaldehyde exceeds a certain limit, skin mucosa irritation can be caused, adverse reactions such as skin allergy, nausea, headache and the like can be caused, and even the human liver and lung dysfunction and the genetic effects of carcinogenesis and mutagenesis can be caused. The existing formaldehyde detection methods mainly comprise spectrophotometry, gas chromatography and liquid chromatography. Spectrophotometry is a quantitative analysis of formaldehyde by adding a color-developing agent (acetylacetone) to colorless formaldehyde, followed by measuring its absorbance at a wavelength of 412 nm. However, in practice it has been found that for coloured samples, the absorbance values measured twice before and after addition of the colour developer must be subtracted. It is expected that any uncertainty in both assays (e.g., fine suspended particles in the test solution, etc.) will have a significant effect on the stability and sensitivity of the assay results. Since formaldehyde is unstable in air at a temperature below 150 ℃ and other gas-phase matrixes and can be rapidly polymerized to form dimers and trimers or be combined with moisture to generate the methyl glycol, the detection result is large in error by adopting direct gas chromatography or headspace gas chromatography. To overcome this disadvantage, formaldehyde is generally reacted with dinitrophenylhydrazine to form stable formaldehyde derivatives which are then analyzed by gas chromatography. When high performance liquid chromatography is adopted for analysis, formaldehyde does not have obvious absorption at the ultraviolet wavelength, and the formaldehyde can be subjected to chromatographic analysis only after being subjected to pretreatment reaction with a color-developing agent 2, 4-Dinitrophenylhydrazine (DNPH) before detection, but the treatment steps of the traditional derivatization or color-developing reaction are not only complicated and time-consuming, but also error operation is introduced.
Another serious problem in coatings is the excessive heavy metal content. The heavy metal meaning is that the density is more than 4.5g/cm3The heavy metals include gold, silver, copper, iron, mercury, lead, cadmium and the like, and the heavy metals are accumulated in a human body to a certain degree to cause chronic poisoning. But is said to be environmental pollutionThe heavy metal(s) mainly refers to heavy elements with significant biological toxicity, such as mercury (mercury), cadmium, lead, chromium, metalloid arsenic and the like. Heavy metals are very difficult to biodegrade, but instead can be concentrated hundreds of times under the action of biological amplification of the food chain and finally enter the human body. Heavy metals can interact strongly with proteins and enzymes in the human body, so that the heavy metals lose activity and can also accumulate in certain organs of the human body to cause chronic poisoning. The content of heavy metals is often determined by spectroscopy, including atomic absorption spectroscopy, X-ray atomic fluorescence spectroscopy, plasma atomic emission spectroscopy, and the like. According to different pretreatment methods of solid samples, the detected content can be divided into total metal content of whole total digestion, soluble heavy metal content of medium dissolution and the like.
The national mandatory standard GB 18582-. The VOC, benzene, toluene, ethylbenzene and xylene can be directly tested by a gas chromatograph without complex sample pretreatment. The contents of free formaldehyde and soluble heavy metal need to have a longer sample pretreatment process. The standard specifies that free formaldehyde is measured spectrophotometrically using acetylacetone as a color-developing agent at 412 nm. Diluting a sample and fixing the sample in a volumetric flask, transferring liquid to a distillation flask, heating and collecting fractions, diluting the fractions and fixing the volume in another volumetric flask, adding an acetylacetone solution, heating in a constant-temperature water bath at 60 ℃ for 30min, cooling, pouring into a cuvette, and testing by using an ultraviolet-visible spectrophotometer, wherein blank tests are required for each test. The method comprises the following main steps of drying the coating to prepare a dry film, crushing the dry film by using crushing equipment, sieving the dry film by using a stainless steel metal sieve, treating the prepared coating dry film by using 0.07mol/L hydrochloric acid solution, stirring the obtained product on a stirrer for 1min, measuring the pH value of the obtained product by using an acidity meter, adjusting the pH value to be between 1.0 and 1.5, continuously stirring the obtained product at room temperature for 1h, standing the obtained product for 1h, filtering the obtained product by using a microporous filter membrane, and completing the on-machine test on the same day.
The full-automatic rapid solvent extraction instrument is designed in a full-automatic mode, can continuously and automatically extract 24 samples, has large sample processing flux and high extraction efficiency, and is suitable for sample pretreatment of existing analysis instruments such as gas chromatography, liquid chromatography, chromatography-mass spectrometry and the like. The rapid solvent extraction technology is a sample pretreatment method for rapidly extracting a solid or semisolid sample under the conditions of high temperature (50-200 ℃) and high pressure (5-20 MPa) developed in recent years, and compared with the common Soxhlet extraction, ultrasonic extraction, microwave extraction and other methods, the method has the advantages that the dosage of an organic solvent is small, only 15mL of solvent is needed for 10g of sample, and the treatment of waste liquid is reduced; the method is rapid, and the time for completing the whole extraction process is only 15 minutes generally; the influence of the matrix is small, solid and semisolid extraction can be carried out (the water content of a sample is less than 75%), and the same extraction conditions can be used for different matrixes; because the extraction process is vertical static extraction, a filter layer or an adsorption medium can be added at the bottom in advance when a sample is filled; the method is convenient to develop, and the mature solvent extraction method can be realized by a rapid solvent extraction method; the automation degree is high, the same sample can be extracted for multiple times according to the requirement, or the solvent extraction is changed, and all the extraction can be programmed by the user and controlled automatically; the extraction efficiency is high, and the selectivity is good; convenient use and good safety, and is confirmed to be the American EPA standard method with the standard method number of 3545. Effect of increasing temperature and increasing pressure on solvent extraction: the dissolving capacity of the analyte is improved, the action of the sample matrix on the analyte is reduced or the acting force between the matrix and the analyte is weakened, the analysis of the analyte from the matrix is accelerated and the analyte rapidly enters the solvent, the viscosity of the solvent is reduced, solvent molecules are favorably diffused into the matrix, the pressure is increased, the boiling point of the solvent is increased, and the solvent is ensured to be kept in a liquid state all the time in the extraction process.
It can be seen that the existing standard test method, especially for both free formaldehyde content and soluble heavy metals, is tedious and time-consuming in sample processing, low in automation degree, labor-intensive and long in test period. Therefore, it is necessary to invent a new fast extracting agent with strong applicability and high efficiency and to resort to application schemes, so as to achieve the purpose of universally, fast and accurately determining the contents of harmful substances, namely free formaldehyde and soluble heavy metals in the interior wall.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an extracting agent and an extracting method for detecting harmful substances in an interior wall coating, and aims to solve the problems of low extracting efficiency, low applicability, complex operation process, long test period and the like in the prior art. The extractant is a liquid-liquid derivation-extractant universally applicable to interior wall coatings, and can be used for continuously finishing multi-task pretreatment of a coating sample on the same full-automatic rapid extraction instrument, wherein the multi-task pretreatment comprises synchronous extraction derivation of free formaldehyde and dissolution of four soluble heavy metals, and the liquid-liquid extraction is adopted, so that the coating is not required to be broken after being made into a dry film and heavy metals in the dry film are dissolved out, and the coating is not required to be distilled to extract formaldehyde and perform derivation determination step by step.
The invention provides an extracting agent for detecting harmful substances in interior wall coatings, which consists of hydrochloric acid buffer solution containing a derivative and a surfactant, acetonitrile and dichloromethane, wherein the volume ratio of the hydrochloric acid buffer solution to the acetonitrile to the dichloromethane is 70-50: 25-40: 5-10; the pH value of the hydrochloric acid buffer solution is 1.0-5.0.
A second aspect of the present invention provides an extraction method for harmful substance detection of interior wall paint, the extraction method comprising: the extracting agent is used for extracting harmful substances in the interior wall coating, and a rapid solvent extractor is used for extraction.
Compared with the prior art, the invention has the following beneficial effects:
1. the extracting agent formula is suitable for all interior wall coatings, including priming paint, finish paint, varnish, colored paint, emulsion paint, real stone paint, colorful paint, putty and the like;
2. the method comprises the following steps of multitasking, wherein the content detection of free formaldehyde and soluble heavy metals is a detection project specified by national standard GB 18582-;
3. the method has high efficiency, abandons the step processing procedures of extraction, derivatization, pH adjustment, membrane preparation and the like in a mode of simultaneously carrying out liquid-liquid derivatization and extraction, reduces the original sample processing period which needs at least 4 hours to 20min, and improves the efficiency by more than 10 times; the test steps and the use of various solvents and reagents are greatly reduced, the automatic continuous operation can be realized, and the whole quantitative detection work of harmful substances (specified according to national standards) of the interior wall coating can be completed within 1 h.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, the present invention provides an extraction agent for detecting harmful substances in interior wall coatings, the extraction agent is composed of hydrochloric acid buffer solution containing a derivatizing agent and a surfactant, acetonitrile and dichloromethane, wherein the volume ratio of the hydrochloric acid buffer solution to the acetonitrile to the dichloromethane is 70-50: 25-40: 5-10; the pH value of the hydrochloric acid buffer solution is 1.0-5.0.
In the invention, the derivatization agent is 2, 4-dinitrophenylhydrazine. The derivatization agent 2, 4-Dinitrophenylhydrazine (DNPH) and formaldehyde can react under the acidic condition to generate 2, 4-dinitrophenylhydrazone, and the substance is yellow or orange yellow in the system and has strong absorption to ultraviolet light of 355 nm. In this reaction, NH in DNPH2Removing two hydrogen atoms and connecting with carbon atoms in formaldehyde, and removing oxygen atoms from the carbon atoms in the formaldehyde to obtain hydrazone N ═ C.
According to the present invention, the content of the derivatizing agent may be 0.04-0.2 wt%, and within this content range, the peak area of the derivatizing agent tends to be stable and reaches a peak value, and preferably, the content of the derivatizing agent is 0.1 wt% in combination with the consideration of the balance between coating samples and the reduction of the contamination of the chromatography column by the excessive derivatizing agent.
According to the invention, the surfactant may be selected from polyoxyethylene alkylamines and/or sorbitan monostearate, preferably polyoxyethylene alkylamines. The surfactant may be present in an amount of 0.05 to 0.20 wt%.
In order to facilitate the detection of harmful substances in the extract, the pH value of the hydrochloric acid buffer solution is limited in the invention, when the pH value of the hydrochloric acid buffer solution is 1.0-5.0, the peak value of the hydrochloric acid buffer solution is better in derivative chromatography, and when the pH value is 2.0-4.0, the peak value is highest. That is, preferably, the pH of the hydrochloric acid buffer solution is 2.0 to 4.0.
The hydrochloric acid buffer solution can be selected from glutamic acid-hydrochloric acid buffer solution or potassium chloride-hydrochloric acid buffer solution according to the adjustment range of the pH value, and the glutamic acid-hydrochloric acid buffer solution is preferably selected.
In the invention, the peak shape of the UPLC main peak is improved by adding a small amount of dichloromethane, and the peak shape is symmetrical and the interference of aldehyde ketone impurities in the system is reduced due to the better extraction effect of the dichloromethane on the derivatives and the adjustment of the polarity and the emulsification effect of the system. Since the derivative is a non-polar compound, the addition of acetonitrile leads to better peak separation of the formaldehyde derivative.
According to a preferred embodiment of the invention, the extractant consists of glutamic acid-hydrochloric acid buffer solution containing 2, 4-dinitrophenylhydrazine and polyoxyethylene alkylamine, acetonitrile and dichloromethane, wherein the volume ratio of the glutamic acid-hydrochloric acid buffer solution to the acetonitrile to the dichloromethane is 70-50: 25-40: 5-10; the pH value of the glutamic acid-hydrochloric acid buffer solution is 2.0-4.0, the content of the 2, 4-dinitrophenylhydrazine is 0.1 wt%, and the content of the polyoxyethylene alkylamine is 0.05-0.20 wt%.
According to a second aspect of the present invention, there is provided an extraction method for harmful substance detection of interior wall paint, the extraction method comprising: the extracting agent is used for extracting harmful substances in the interior wall coating, and a rapid solvent extractor is used for extraction.
In the extraction of the rapid solvent extractor, the extraction time, the extraction temperature and the extraction pressure are main influence factors, the extraction time of the general rapid solvent extractor is 5-15min, the release of formaldehyde and heavy metals is most obvious in the first 10min of extraction, and the release amount is stable and does not increase remarkably along with the extension of the extraction time. The extraction temperature is usually 50-125 deg.C, the extraction pressure is usually 5-10MPa, and the influence on the release amount of harmful substances is similar to the extraction time. Namely, the extraction conditions include: the extraction temperature is 50-125 ℃, the extraction pressure is 5-10MPa, and the extraction time is 5-15 min.
For better extraction, preferably, the extraction conditions include: the extraction temperature is 70-100 ℃, the extraction pressure is 6-10MPa, and the extraction time is 10-15 min. Further preferably, the extraction conditions include: the extraction temperature is 100 ℃, the extraction pressure is 10MPa, and the extraction time is 10 min.
In the invention, the interior wall coating can be at least one of primer, finish paint, varnish, colored paint, emulsion paint, real stone paint, multicolor paint and putty. Aiming at different interior wall coatings, the invention can finely adjust the pH value of the hydrochloric acid buffer solution and the volume ratio of the hydrochloric acid buffer solution, the acetonitrile and the dichloromethane within a limited range to be suitable for different interior wall coatings.
The process parameters not defined in the present invention can be selected conventionally according to the prior art.
The present invention is further illustrated by the following examples. It is to be understood, however, that these examples are for the purpose of illustration and explanation only and are not intended to limit the present invention.
The primary equipment and primary reagents used in the following examples include:
the main equipment is as follows: dionex ASE350 Rapid solvent extractor, Thermo Fisher, USA; ultra-high performance liquid chromatograph (UPLC) with Waters Acquity UPLC C as chromatographic column18Reversed phase column, 50mm 2.1mm, 1.7 μm, column temperature 25 deg.C, flow rate 0.2mL/min, sample size 20 μ L, ultraviolet detector (UVD), Waters corporation, USA; inductively coupled plasma emission spectrometer (ICP-OES), Agilent Inc. USA.
The main reagents are as follows: formaldehyde-2, 4-dinitrophenylhydrazone (99%, o2 si); 2, 4-dinitrophenylhydrazine (98%, CNW); formaldehyde standard sample (1000mg/L, China measurement institute), standard substance solution of Cd, Cr, Hg and Pb (1000mg/L, China measurement institute); formaldehyde solution (37%, AR); dichloroethane and acetonitrile are both chromatographically pure (Fisher company, USA); other reagents were analytically pure.
Examples 1 to 5 are provided to illustrate the extractant and the extraction method for detecting harmful substances in interior wall coatings according to the present invention.
Example 1
An extractant for detecting harmful substances in interior wall coatings consists of glutamic acid-hydrochloric acid buffer solution containing 2, 4-dinitrophenylhydrazine and polyoxyethylene alkylamine, acetonitrile and dichloromethane, wherein the volume ratio of the hydrochloric acid buffer solution to the acetonitrile to the dichloromethane is 60: 35: 5; the pH value of the glutamic acid-hydrochloric acid buffer solution is 3.0. The content of 2, 4-dinitrophenylhydrazine is 0.1 wt%, and the content of polyoxyethylene alkylamine is 0.10 wt%.
An extraction method for detecting harmful substances in interior wall paint, comprising: the extracting agent is used for extracting harmful substances in the varnish, and a rapid solvent extractor is used for extraction. The method can be specifically carried out by the following 2 steps:
1) filling an extraction tank: adding a PEEK filtering membrane at the bottom of a 34mL extraction pool, and adding 1g of varnish and 20mL of extracting agent;
2) and (3) quick extraction: setting the extraction time for 10min, the extraction pressure for 10MPa and the extraction temperature for 100 ℃, and completing the extraction of the sample on a rapid solvent extractor.
The extraction effect of the extractant was tested by Ultra Performance Liquid Chromatography (UPLC) and plasma atomic emission spectroscopy (ICP). And (3) testing an extracted sample: and (3) taking a target detection object standard curve, performing on-machine test on the extract, and detecting the content of free formaldehyde and the content of heavy metals Cd, Cr, Hg and Pb by using UPLC and ICP-OES respectively. Specific results are shown in table 1.
Example 2
An extractant for detecting harmful substances in interior wall coatings consists of glutamic acid-hydrochloric acid buffer solution containing 2, 4-dinitrophenylhydrazine and polyoxyethylene alkylamine, acetonitrile and dichloromethane, wherein the volume ratio of the hydrochloric acid buffer solution to the acetonitrile to the dichloromethane is 70: 25: 5; the pH value of the glutamic acid-hydrochloric acid buffer solution is 2.5. The content of 2, 4-dinitrophenylhydrazine is 0.1 wt%, and the content of polyoxyethylene alkylamine is 0.15 wt%.
An extraction method for detecting harmful substances in interior wall paint, comprising: the extracting agent is used for extracting harmful substances in the stone-like paint, and the extraction is carried out by using a rapid solvent extractor. The method can be specifically carried out by the following 2 steps:
1) filling an extraction tank: adding a PEEK filtering membrane at the bottom of a 34mL extraction tank, and adding 1g of real stone paint and 20mL of an extracting agent;
2) and (3) quick extraction: setting the extraction time for 10min, the extraction pressure of 6MPa and the extraction temperature of 70 ℃, and completing the extraction of the sample on a rapid solvent extractor.
The extraction effect of the extractant was tested by Ultra Performance Liquid Chromatography (UPLC) and plasma atomic emission spectroscopy (ICP). And (3) testing an extracted sample: and (3) taking a target detection object standard curve, performing on-machine test on the extract, and detecting the content of free formaldehyde and the content of heavy metals Cd, Cr, Hg and Pb by using UPLC and ICP-OES respectively. Specific results are shown in table 1.
Example 3
An extractant for detecting harmful substances in interior wall coatings consists of glutamic acid-hydrochloric acid buffer solution containing 2, 4-dinitrophenylhydrazine and polyoxyethylene alkylamine, acetonitrile and dichloromethane, wherein the volume ratio of the hydrochloric acid buffer solution to the acetonitrile to the dichloromethane is 50: 40: 10; the pH value of the glutamic acid-hydrochloric acid buffer solution is 4.0. The content of 2, 4-dinitrophenylhydrazine is 0.1 wt%, and the content of polyoxyethylene alkylamine is 0.20 wt%.
An extraction method for detecting harmful substances in interior wall paint, comprising: the extractant is used for extracting harmful substances in the high-solid emulsion paint, and a rapid solvent extractor is used for extraction. The method can be specifically carried out by the following 2 steps:
1) filling an extraction tank: adding a PEEK filtering membrane at the bottom of a 34mL extraction tank, and adding 1g of high-solid emulsion paint and 20mL of an extracting agent;
2) and (3) quick extraction: setting the extraction time for 15min, the extraction pressure of 10MPa and the extraction temperature of 70 ℃, and completing the extraction of the sample on a rapid solvent extractor.
The extraction effect of the extractant was tested by Ultra Performance Liquid Chromatography (UPLC) and plasma atomic emission spectroscopy (ICP). And (3) testing an extracted sample: and (3) taking a target detection object standard curve, performing on-machine test on the extract, and detecting the content of free formaldehyde and the content of heavy metals Cd, Cr, Hg and Pb by using UPLC and ICP-OES respectively. Specific results are shown in table 1.
Example 4
An extractant for detecting harmful substances in interior wall coatings consists of glutamic acid-hydrochloric acid buffer solution containing 2, 4-dinitrophenylhydrazine and polyoxyethylene alkylamine, acetonitrile and dichloromethane, wherein the volume ratio of the hydrochloric acid buffer solution to the acetonitrile to the dichloromethane is 55: 35: 10; the pH value of the glutamic acid-hydrochloric acid buffer solution is 3.5. The content of 2, 4-dinitrophenylhydrazine is 0.1 wt%, and the content of polyoxyethylene alkylamine is 0.15 wt%.
An extraction method for detecting harmful substances in interior wall paint, comprising: the extracting agent is used for extracting harmful substances in the multicolor paint, and the extraction is carried out by using a rapid solvent extraction instrument. The method can be specifically carried out by the following 2 steps:
1) filling an extraction tank: adding a PEEK filter membrane at the bottom of a 34mL extraction tank, and adding 1g of multicolor paint and 20mL of an extracting agent;
2) and (3) quick extraction: setting the extraction time for 15min, the extraction pressure of 6MPa and the extraction temperature of 100 ℃, and completing the extraction of the sample on a rapid solvent extractor.
The extraction effect of the extractant was tested by Ultra Performance Liquid Chromatography (UPLC) and plasma atomic emission spectroscopy (ICP). And (3) testing an extracted sample: and (3) taking a target detection object standard curve, performing on-machine test on the extract, and detecting the content of free formaldehyde and the content of heavy metals Cd, Cr, Hg and Pb by using UPLC and ICP-OES respectively. Specific results are shown in table 1.
Example 5
An extractant for detecting harmful substances in interior wall coatings consists of glutamic acid-hydrochloric acid buffer solution containing 2, 4-dinitrophenylhydrazine and polyoxyethylene alkylamine, acetonitrile and dichloromethane, wherein the volume ratio of the hydrochloric acid buffer solution to the acetonitrile to the dichloromethane is 65: 30: 5; the pH value of the glutamic acid-hydrochloric acid buffer solution is 2.0. The content of 2, 4-dinitrophenylhydrazine is 0.1 wt%, and the content of polyoxyethylene alkylamine is 0.05 wt%.
An extraction method for detecting harmful substances in interior wall paint, comprising: the extracting agent is used for extracting harmful substances in the putty, and a quick solvent extractor is used for extraction. The method can be specifically carried out by the following 2 steps:
1) filling an extraction tank: adding a PEEK filtering membrane at the bottom of the 34mL extraction tank, and adding 1g of putty and 20mL of extracting agent;
2) and (3) quick extraction: setting the extraction time for 10min, the extraction pressure for 10MPa and the extraction temperature for 100 ℃, and completing the extraction of the sample on a rapid solvent extractor.
The extraction effect of the extractant was tested by Ultra Performance Liquid Chromatography (UPLC) and plasma atomic emission spectroscopy (ICP). And (3) testing an extracted sample: and (3) taking a target detection object standard curve, performing on-machine test on the extract, and detecting the content of free formaldehyde and the content of heavy metals Cd, Cr, Hg and Pb by using UPLC and ICP-OES respectively. Specific results are shown in table 1.
Comparative example 1
The extraction method for detecting the harmful substances in the interior wall coating according to the national mandatory standard GB 18582-2008 is adopted to extract formaldehyde and soluble heavy metal elements in the varnish (the extraction method is the same as that in the example 1), the extraction of the formaldehyde and the soluble heavy metal elements needs to be respectively carried out, and the method comprises the following specific steps:
1) extraction and detection of formaldehyde: diluting and fixing the sample in a volumetric flask, transferring the sample to a distillation flask, heating and collecting fractions, diluting and fixing the fractions in another volumetric flask, adding an acetylacetone solution, heating in a constant-temperature water bath at 60 ℃ for 30min, cooling, pouring the cooled fractions into a cuvette, and testing by using an ultraviolet-visible spectrophotometer, wherein the specific results are shown in table 1.
2) Extraction and detection of soluble heavy metals: firstly drying the coating to prepare a dry film, crushing the dry film by using crushing equipment, sieving the dry film by using a stainless steel metal sieve, treating the prepared dry film of the coating by using 0.07mol/L hydrochloric acid solution, stirring the dry film of the coating on a stirrer for 1min, measuring the pH value of the dry film by using an acidity meter, adjusting the pH value to be between 1.0 and 1.5, continuously stirring the dry film of the coating at room temperature for 1h, standing the dry film for 1h, filtering the dry film by using a microporous filter membrane, and completing the ICP-OES on-machine test on the same day, wherein the specific results are shown in Table 1.
Comparative example 2
The method for extracting formaldehyde and soluble heavy metal elements in the stone-like paint (same as the example 2) by adopting the extraction method for detecting the harmful substances in the national mandatory standard GB 18582-2008 interior wall paint comprises the following specific steps:
1) extraction and detection of formaldehyde: diluting and fixing the sample in a volumetric flask, transferring the sample to a distillation flask, heating and collecting fractions, diluting and fixing the fractions in another volumetric flask, adding an acetylacetone solution, heating in a constant-temperature water bath at 60 ℃ for 30min, cooling, pouring the cooled fractions into a cuvette, and testing by using an ultraviolet-visible spectrophotometer, wherein the specific results are shown in table 1.
2) Extraction and detection of soluble heavy metals: firstly drying the coating to prepare a dry film, crushing the dry film by using crushing equipment, sieving the dry film by using a stainless steel metal sieve, treating the prepared dry film of the coating by using 0.07mol/L hydrochloric acid solution, stirring the dry film of the coating on a stirrer for 1min, measuring the pH value of the dry film by using an acidity meter, adjusting the pH value to be between 1.0 and 1.5, continuously stirring the dry film of the coating at room temperature for 1h, standing the dry film for 1h, filtering the dry film by using a microporous filter membrane, and completing the ICP-OES on-machine test on the same day, wherein the specific results are shown in Table 1.
TABLE 1
| Free formaldehyde mg/kg | Cd mg/kg | Cr mg/kg | Hg mg/kg | Pb mg/kg | |
| Example 1 | 25.0 | 8.07 | 9.47 | 3.10 | 5.93 |
| Example 2 | 19.0 | 9.06 | 4.55 | 4.81 | 6.46 |
| Example 3 | 26.6 | 4.58 | 5.10 | 25.54 | 23.96 |
| Example 4 | 22.6 | 5.18 | 5.98 | 24.18 | 26.37 |
| Example 5 | 8.1 | 7.23 | 6.04 | 29.80 | 28.54 |
| Comparative example 1 | 23.9 | 7.88 | 9.10 | 3.26 | 6.22 |
| Comparative example 2 | 19.8 | 8.64 | 4.51 | 5.13 | 6.57 |
The results of the embodiment and the comparative example show that the extractant combined rapid solvent extractor can achieve better composite extraction and application by extracting the inner wall coating once, greatly simplifies the sample pretreatment steps of two items in the detection of harmful substances of the inner wall coating, realizes the automatic detection of the national standard specified full detection items, is environment-friendly, accurate and efficient, and in addition, the detection result obtained by adopting the extraction method of the invention is similar to the detection result obtained by adopting the existing extraction method, thereby proving the reliability of the extraction method of the invention.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. An extraction agent for detecting harmful substances in interior wall coatings is characterized by comprising a derivative agent and a surfactant, namely hydrochloric acid buffer solution, acetonitrile and dichloromethane, wherein the volume ratio of the hydrochloric acid buffer solution to the acetonitrile to the dichloromethane is 70-50: 25-40: 5-10; the pH value of the hydrochloric acid buffer solution is 1.0-5.0.
2. The extractant of claim 1, wherein the derivatizing agent is 2, 4-dinitrophenylhydrazine and the derivatizing agent is present in an amount of 0.04 to 0.2 wt.%.
3. The extraction agent according to claim 1, wherein the surfactant is polyoxyethylene alkylamine and/or sorbitan monostearate, and the content of the surfactant is 0.05-0.20 wt%.
4. The extractant of claim 3, wherein the surfactant is a polyoxyethylalkylamine.
5. The extractant of claim 1, wherein the pH of the hydrochloric acid buffer solution is 2.0-4.0, and the hydrochloric acid buffer solution is selected from glutamic acid-hydrochloric acid buffer solution or potassium chloride-hydrochloric acid buffer solution.
6. The extractant of claim 5, wherein the hydrochloric acid buffer solution is a glutamic acid-hydrochloric acid buffer solution.
7. An extraction method for detecting harmful substances in interior wall paint is characterized by comprising the following steps: the extraction of harmful substances from interior wall coatings is carried out using the extractant according to any one of claims 1 to 6, the extraction being carried out using a rapid solvent extractor.
8. The extraction process of claim 7, wherein the extraction conditions comprise: the extraction temperature is 50-125 ℃, the extraction pressure is 5-I0MPa, and the extraction time is 5-15 min.
9. The extraction process of claim 8, wherein the extraction conditions comprise: the extraction temperature is 70-100 ℃, the extraction pressure is 6-10MPa, and the extraction time is 10-15 min.
10. The extraction method of claim 7, wherein the interior wall paint is at least one of a primer, a topcoat, a varnish, a pigmented paint, a latex paint, a stone paint, a multicolor paint, and a putty.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115128199A (en) * | 2022-07-22 | 2022-09-30 | 郑州大学第一附属医院 | Method for detecting furfural compounds in suction head type microextraction injection and oral liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008131891A1 (en) * | 2007-04-28 | 2008-11-06 | Forschungszentrum Karlsruhe Gmbh | Method for magnetically supported extraction |
| CN105588901A (en) * | 2014-10-27 | 2016-05-18 | 中国石油化工股份有限公司 | Extraction liquid for extracting sorbitol-type transparent agent from polypropylene raw material and application thereof |
| CN107941958A (en) * | 2017-12-14 | 2018-04-20 | 菏泽学院 | A kind of method of free formaldehyde in measure water paint |
| CN108469472A (en) * | 2017-12-19 | 2018-08-31 | 江苏康达检测技术股份有限公司 | The assay method of concentration of formaldehyde in solid waste |
-
2020
- 2020-08-07 CN CN202010793139.1A patent/CN114053755B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008131891A1 (en) * | 2007-04-28 | 2008-11-06 | Forschungszentrum Karlsruhe Gmbh | Method for magnetically supported extraction |
| CN105588901A (en) * | 2014-10-27 | 2016-05-18 | 中国石油化工股份有限公司 | Extraction liquid for extracting sorbitol-type transparent agent from polypropylene raw material and application thereof |
| CN107941958A (en) * | 2017-12-14 | 2018-04-20 | 菏泽学院 | A kind of method of free formaldehyde in measure water paint |
| CN108469472A (en) * | 2017-12-19 | 2018-08-31 | 江苏康达检测技术股份有限公司 | The assay method of concentration of formaldehyde in solid waste |
Non-Patent Citations (1)
| Title |
|---|
| 康彦芳: "《化工分离技术》", 31 January 2014 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115128199A (en) * | 2022-07-22 | 2022-09-30 | 郑州大学第一附属医院 | Method for detecting furfural compounds in suction head type microextraction injection and oral liquid |
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