TWI839866B - A method for detecting the content of polycyclic aromatic hydrocarbons in incense burning products - Google Patents

Abstract

The invention relates to the field of detection of incense burning product, and provides a method for detecting the content of polycyclic aromatic hydrocarbons in incense burning products, comprising the following steps: (1) collecting smoke after burning incense; (2) adding methylene chloride and adding polycyclic aromatic hydrocarbon extractant after ultrasonic treatment to fully enrich polycyclic aromatic hydrocarbons, and then eluting through eluent, evaporate the eluent by rotary decompression or blow it to near dryness with gentle nitrogen, add ethyl acetate to reconstitute and add the internal standard substance as the sample to be tested; (3) prepare a series of standard working solutions containing different concentrations of the target substance, measure by gas chromatography-tandem mass spectrometry, and draw a standard curve; (4) sample tested by gas chromatography-tandem mass spectrometry and the peak area ratio of the secondary selected ions of the target substance and the corresponding internal standard substance is measured, and then substituted into the standard curve to obtain the content of various polycyclic aromatic hydrocarbons. The detection method of the invention fills the blank of the prior art, and has the advantages of simple and quick operation, accurate detection results and good repeatability.

Description

A method for detecting the content of polycyclic aromatic hydrocarbons in incense products

The present invention relates to the field of incense product testing technology, and in particular to a method for detecting the content of polycyclic aromatic hydrocarbons in incense products.

Polycyclic aromatic hydrocarbons (PAHs) are volatile hydrocarbons produced by incomplete combustion of organic substances such as coal, petroleum, wood, tobacco, and organic polymer compounds. They are highly toxic and carcinogenic and can cause a variety of harms to the human body, such as damage to the respiratory system, circulatory system, and nervous system, and damage to the liver and kidneys. They are considered to be the main organic pollutants that affect human health.

Incense products are widely used in public places such as religion, rituals, and sacrifices. Currently, temples need to burn a large amount of incense and other smoke-generating items for daily worship and blessing activities. Incense will release a variety of air pollutants such as particulate matter, formaldehyde, benzene and polycyclic aromatic hydrocarbons (PAHs). Accurately detecting the concentration of toxic and harmful substances after burning incense can improve the quality of incense products, reduce the adverse effects of harmful substances in incense products on health, and reduce the harm of incense burning activities to the ecological environment. The current incense standards mainly include GB 26386-2011 "General Technical Requirements for Safety of Incense Products" and GB/T26393-2011 "Test Methods for Harmful Substances in Incense Products", but neither of these two standards involves the detection requirements for the content of polycyclic aromatic hydrocarbons in the smoke after burning incense. At present, China has no standards to guide the detection of the content of polycyclic aromatic hydrocarbons emitted after burning incense products, and it is impossible to quickly and accurately detect the content of polycyclic aromatic hydrocarbons.

Patent application number CN201811576886.9 discloses a method for determining the content of 16 polycyclic aromatic hydrocarbons in incense smoke by thermal desorption/gas chromatography-mass spectrometry. The incense sample is burned in a space of 1.8m×1.8m×1.8m, and the smoke is absorbed and enriched into a thermal desorption tube filled with Tenax-TA filler by a sampling pump. After thermal desorption, GC-MS is used for detection in the selected ion (SIM) mode, and the external standard method is used for quantification. The results showed that the concentrations of 16 PAHs showed a good linear relationship in the range of 0.05~1.0mg/L, the correlation coefficients r were all greater than 0.995, the detection limit of the method was 0.06~1.10ng/m ³ , the average spike recovery was 89.2~100.7%, and the relative standard deviation was 1.7~5.0%. This method can effectively conduct qualitative and quantitative analysis of 16 PAHs in incense smoke, and it is simple, fast, and highly reliable, which can meet the experimental requirements.

Therefore, in view of the above content, the present invention provides a method for detecting the content of polycyclic aromatic hydrocarbons in incense products, which fills the gap in the existing technology. The detection method adopted is simple and fast to operate, and the detection results are accurate and have good repeatability.

、苯並[b]苯并苊、苯並[k]苯并苊、苯並[a]芘、茚並[1,2,3-cd]芘、二苯並[a,h]蒽和苯並[g,h,i]芘；所述多環芳烴萃取劑是2,6-二氨基蒽醌、2,5-二羥基-1,4-對苯二甲醛在溶劑中進行縮合反應製得，所述多環芳烴萃取劑的製備過程中添加磁性沸石分子篩奈米顆粒；(3)配製一系列含有不同濃度目標物的標準工作溶液，濃度依次為：1ng/mL、2ng/mL、5ng/mL、10ng/mL、20ng/mL、50ng/mL、100ng/mL，通過氣相色譜-串聯質譜進行測定，並擬合得到標準曲線；(4)通過氣相色譜-串聯質譜對待測樣品進行測定，測得目標物和 對應內標物的二級選擇離子峰面積比，代入標準曲線，求得樣品中的各種多環芳烴的含量。 To achieve the above-mentioned object, the present invention is realized by the following technical scheme: A method for detecting the content of polycyclic aromatic hydrocarbons in incense products, comprising the following steps: (1) a test bench is set in the middle of a 1.0m×1.0m×1.0m sealed glass box, one side of which is provided with a sampling device, incense is ignited on the test bench, and sampling is performed for 40 minutes at a flow rate of 0.5L/min, and a total of 20L of smoke is collected in the sampling device. The top and both sides of the box are provided with fans; the sampling device comprises a shell, the top of the shell is provided with a plurality of sampling ports, the sampling ports are connected to one end of the sampling tube through an air duct, the other end of the sampling tube is connected to one end of a gas flow regulating element, the other end of the gas flow regulating element is connected to a negative pressure pump through a negative pressure tube; (2) dichloromethane is added to the sampling tube, ultrasonicated for 30-60 minutes, and then poured into a collection bottle, and polycyclic aromatic hydrocarbons are added at the same time. The polycyclic aromatic hydrocarbons are fully contacted with the polycyclic aromatic hydrocarbons by the polycyclic aromatic hydrocarbon extractant, and then the polycyclic aromatic hydrocarbons are fully enriched by the polycyclic aromatic hydrocarbons by the polycyclic aromatic hydrocarbon extractant. A permanent magnet is placed on the outer wall of one side of the collection bottle to attract and fix the polycyclic aromatic hydrocarbons extractant. The solution in the collection bottle is poured out, and the permanent magnet is removed. The eluent is added to the collection bottle, and the mixture is shaken in a vortex mixer to elute the polycyclic aromatic hydrocarbons. Then, the permanent magnet is used to remove the eluent. The magnet realizes the separation of the solid phase magnetic zeolite molecular sieve nanoparticles and the liquid phase, and the eluent is poured out, which is a solution containing polycyclic aromatic hydrocarbons; the eluent is evaporated by rotary decompression or blown to near dryness with gentle nitrogen, 1 ml of ethyl acetate is added to dissolve and an internal standard is added to serve as a sample to be tested; the internal standard is one or more of the deuterated compounds of 16 polycyclic aromatic hydrocarbons, and the 16 polycyclic aromatic hydrocarbons are naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, benzoacenaphthene, pyrene, benzo[a]anthracene,

, benzo[b]benzoacenaphthene, benzo[k]benzoacenaphthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[g,h,i]pyrene; the polycyclic aromatic hydrocarbon extractant is prepared by condensation reaction of 2,6-diaminoanthraquinone and 2,5-dihydroxy-1,4-terephthalaldehyde in a solvent, and magnetic zeolite molecular sieve nanoparticles are added during the preparation of the polycyclic aromatic hydrocarbon extractant; (3) preparing a series of standard samples containing different concentrations of the target substances The working solutions, with concentrations of 1 ng/mL, 2 ng/mL, 5 ng/mL, 10 ng/mL, 20 ng/mL, 50 ng/mL, and 100 ng/mL, were measured by gas chromatography-tandem mass spectrometry and fitted to obtain a standard curve; (4) The samples to be tested were measured by gas chromatography-tandem mass spectrometry to obtain the secondary selective ion peak area ratio of the target substance and the corresponding internal standard, which was substituted into the standard curve to obtain the content of various polycyclic aromatic hydrocarbons in the sample.

99.999%；恒流模式，流速為1.5mL/min；分流進樣，分流比10：1：進樣量為1μL；採用的質譜條件為：電離方式為電子轟擊源，離子源溫度為280℃，電離能為70ev；掃描方式：多反應監測MRM模式；碰撞氣：氮氣，流量1.5mL/min。 Further improvements are: in the gas chromatography-tandem mass spectrometry, the chromatographic conditions adopted are: use HP-5MS capillary chromatographic column, specification 30m×0.25mm×0.25μm; program heating: initial temperature 80℃, hold for 1min, then increase to 180℃ at 10℃/min, then increase to 280℃ at 5℃/min, hold for 15min; carrier gas is nitrogen, purity

99.999%; constant flow mode, flow rate is 1.5mL/min; split injection, split ratio is 10:1: injection volume is 1μL; the mass spectrometry conditions used are: ionization mode is electron bombardment source, ion source temperature is 280℃, ionization energy is 70ev; scanning mode: multiple reaction monitoring MRM mode; collision gas: nitrogen, flow rate is 1.5mL/min.

A further improvement is that the preparation of the polycyclic aromatic hydrocarbons includes the following steps: dissolving 2,6-diaminoanthraquinone and 2,5-dihydroxy-1,4-terephthalaldehyde in a solvent, adding 4-6 mol/L acetic acid solution as a catalyst, stirring and mixing evenly, adding magnetic zeolite molecular sieve nanoparticles, and then heating to 100-110°C in a nitrogen atmosphere for 75-85h. After the reaction, the solid separated is washed with acetone and n-hexane in turn to wash away the unreacted monomers remaining in the pores, and finally vacuum dried at 120-140°C for 4-8h to obtain a polycyclic aromatic hydrocarbon extractant.

A further improvement is that the amount of the solvent added is 15-25 times the mass of 2,6-diaminoanthraquinone, and the mass ratio of the acetic acid solution to the solvent is 1:12-16.

A further improvement is that the mass ratio of the 2,6-diaminoanthraquinone, 2,5-dihydroxy-1,4-terephthalaldehyde, and magnetic zeolite molecular sieve nanoparticles is 20-30:12-28:25-50.

烷、均三甲苯、N,N-二甲基乙醯胺中的任意一種或兩種以上混合而成。 A further improvement is that the solvent is 1,4-dihydro-

It is composed of any one of alkane, mesitylene and N,N-dimethylacetamide or a mixture of two or more thereof.

A further improvement is that the magnetic zeolite molecular sieve nanoparticles are prepared by the following method: polyethylene glycol and sodium polyacrylate are added to a sodium hydroxide aqueous solution, stirred to completely dissolve, and solution A is obtained; ferrous sulfate heptahydrate, ferric chloride hexahydrate, and zeolite molecular sieve are added to deionized water, stirred and mixed for 15-25 minutes, and then solution A is slowly added dropwise at 70-80°C in an inert gas atmosphere, and the reaction is continued for 40-60 minutes after the addition is completed to obtain a precursor of Fe ₃ O ₄ ; Fe ₃ O The precursor of ₄ is reacted at 135-155°C for 3.5-4.5h, cooled to room temperature, and then the reaction product is magnetically separated to obtain a black solid; the black solid is rinsed with deionized water 2-4 times and dried to obtain magnetic zeolite molecular sieve nanoparticles.

A further improvement is that the mass ratio of the ferrous sulfate heptahydrate, ferric chloride hexahydrate, zeolite molecular sieve, sodium hydroxide, polyethylene glycol and sodium polyacrylate is 1:1.5-1.7:0.4-0.6:1.1-1.3:0.6-0.8:0.9-1.2.

By adopting the above technical scheme, the beneficial effects of the present invention are as follows: the polycyclic aromatic hydrocarbon extractant is formed by the condensation reaction of the primary amino group in the molecular structure of 2,6-diaminoanthraquinone and the aldehyde group in the molecular structure of 2,5-dihydroxy-1,4-terephthalaldehyde, and belongs to a covalent organic skeleton material, and has the characteristics of large specific surface area, high porosity and containing a special nano-channel structure. These characteristics can be used to fully adsorb and load polycyclic aromatic hydrocarbons and improve the recovery of polycyclic aromatic hydrocarbons. There is a strong π-π interaction between the benzene ring structure on the covalent organic skeleton and the benzene ring of the polycyclic aromatic hydrocarbon, which can firmly adsorb the polycyclic aromatic hydrocarbons on the polycyclic aromatic hydrocarbon extractant to achieve full enrichment of the polycyclic aromatic hydrocarbons. The polycyclic aromatic hydrocarbon extractant contains magnetic zeolite molecular sieve nanoparticles. After selectively enriching the polycyclic aromatic hydrocarbons, they can be separated from the solution through an external magnetic field, greatly reducing the processing time and cost.

The reaction principle for preparing magnetic zeolite molecular sieve nanoparticles is: Fe ²⁺ +2Fe ³⁺ +8OH- ⁼ Fe ₃ O ₄ ↓+4H ₂ O. Soluble iron salt and soluble ferrous salt solution are mixed, then alkaline solution is added, reaction temperature and time are controlled, and finally nano-scale magnetic Fe ₃ O ₄ particles are obtained. Although the Fe ₃ O ₄ particles prepared according to the above method have a nearly spherical morphology, the proportion of particles with defects is large, which affects the adsorption performance and magnetic properties of the magnetic nanoparticles to a certain extent. The applicant unexpectedly found that by adding two high molecular polymers, polyethylene glycol and sodium polyacrylate, the above problems can be solved, and magnetic nanoparticles with regular shapes and only a small amount of spherical particles with defects can be obtained. Zeolite molecular sieve is a hydrate of crystalline aluminum silicate. When the Fe ₃ O ₄ precursor reacts at high temperature, the water molecules of the zeolite molecular sieve are removed and the remaining atoms form a cage-shaped structure. The cage-shaped structure of the zeolite molecular sieve can make the polycyclic aromatic hydrocarbon extractant fully contact with the polycyclic aromatic hydrocarbons to form a π-π conjugate system, further improving the adsorption capacity of polycyclic aromatic hydrocarbons.

The present invention collects smoke containing polycyclic aromatic hydrocarbons through a sampling device. The sampling device is not only simple and convenient to operate, but also can collect multiple smoke samples at the same time. After testing them separately, the average value is taken, and the result is more accurate. Installing a fan in the glass box can promote the rapid and uniform mixing of the incense smoke in the box, and the content of polycyclic aromatic hydrocarbons in the collected smoke is closer to the actual situation. The content of each different polycyclic aromatic hydrocarbon in the polycyclic aromatic hydrocarbon compounds released after burning incense is not the same. In order to make the content of polycyclic aromatic hydrocarbons in the incense smoke reach a measurable level, the actual content of 16 polycyclic aromatic hydrocarbons is detected. This application burns 10 incense sticks at one time.

Compared with GC-MS and HPLC, the method of the present invention has the advantages of accurate operation, high sensitivity and good repeatability, and is particularly suitable for the detection and analysis of polycyclic aromatic hydrocarbons in incense products. Before injection, the sample is pre-treated with a polycyclic aromatic hydrocarbon extractant, which is simple and quick, has a good enrichment effect on polycyclic aromatic hydrocarbons, and greatly reduces the processing time and cost.

1:Test bench

2: Fan

3: Shell

4: Sampling port

5: Airway

6: Sampling tube

7: Gas flow regulating element

8: Negative pressure tube

9: Negative pressure pump

Figure 1 is a schematic diagram of the structure of the glass square box of the present invention.

The following will be combined with specific examples to explain in detail the implementation of the present invention, so that the implementation process of how the present invention applies technical means to solve technical problems and achieve technical effects can be fully understood and implemented accordingly.

Unless otherwise specified, the technical means used in the embodiments are conventional means known to those with ordinary knowledge in the technical field to which the present invention belongs, and the reagents and products used are also commercially available. The source of the reagents used, the trade name, and the components of the reagents that need to be listed are all indicated when they first appear.

Implementation Example 1

The preparation of polycyclic aromatic hydrocarbon extractant includes the following steps:

S1. Preparation of magnetic zeolite molecular sieve nanoparticles

Polyethylene glycol 600 and sodium polyacrylate are added to a sodium hydroxide aqueous solution, stirred to completely dissolve, and solution A is obtained; ferrous sulfate heptahydrate, ferric chloride hexahydrate, and zeolite molecular sieve are added to deionized water, stirred and mixed for 15 minutes, and then solution A is slowly added dropwise at 70°C in an inert gas atmosphere, and the reaction is continued for 60 minutes after the addition is completed to obtain a precursor of Fe ₃ O ₄ , wherein the mass ratio of ferrous sulfate heptahydrate, ferric chloride hexahydrate, zeolite molecular sieve, sodium hydroxide, polyethylene glycol 600 and sodium polyacrylate is 10:15:4:11:6:9; Fe ₃ O The precursor of ₄ was reacted at 135°C for 4.5 hours, and after cooling to room temperature, the reaction product was magnetically separated to obtain a black solid; the black solid was rinsed twice with deionized water and dried to obtain magnetic zeolite molecular sieve nanoparticles;

S2, condensation reaction

烷/均 三甲苯混合溶劑(體積比1：2)中，加入4mol/L乙酸溶液作為催化劑，攪拌混合均勻後加入磁性沸石分子篩奈米顆粒，然後在氮氣氣氛下，升溫至100℃下反應85h，反應後分離得到的固體依次用丙酮、正己烷洗滌，洗去殘留在孔道中的未反應單體，最後120℃下真空乾燥8h，即得多環芳烴萃取劑。所述2,6-二氨基蒽醌、2,5-二羥基-1,4-對苯二甲醛、磁性沸石分子篩奈米顆粒的質量比為20：12：25，所述溶劑的加入量為2,6-二氨基蒽醌質量的25倍，所述乙酸溶液與溶劑的質量比為1：12。 Dissolve 2,6-diaminoanthraquinone and 2,5-dihydroxy-1,4-terephthalaldehyde in 1,4-dihydro-1,4-terephthalaldehyde.

4 mol/L acetic acid solution is added as a catalyst to a mixed solvent of 1:2 in volume ratio of 2,6-diaminoanthraquinone/mesitylene, and then magnetic zeolite molecular sieve nanoparticles are added after stirring and mixing evenly, and then the temperature is raised to 100°C for reaction for 85 hours under a nitrogen atmosphere. The solid separated after the reaction is washed with acetone and n-hexane in turn to wash away the unreacted monomers remaining in the pores, and finally vacuum dried at 120°C for 8 hours to obtain a polycyclic aromatic hydrocarbon extractant. The mass ratio of the 2,6-diaminoanthraquinone, 2,5-dihydroxy-1,4-terephthalaldehyde, and magnetic zeolite molecular sieve nanoparticles is 20:12:25, the amount of the solvent added is 25 times the mass of 2,6-diaminoanthraquinone, and the mass ratio of the acetic acid solution to the solvent is 1:12.

Example 2

The preparation of polycyclic aromatic hydrocarbon extractant includes the following steps:

S1. Preparation of magnetic zeolite molecular sieve nanoparticles

Polyethylene glycol 600 and sodium polyacrylate are added to a sodium hydroxide aqueous solution, stirred to completely dissolve, and solution A is obtained; ferrous sulfate heptahydrate, ferric chloride hexahydrate, and zeolite molecular sieve are added to deionized water, stirred and mixed for 20 minutes, and then solution A is slowly added dropwise at 75°C in an inert gas atmosphere, and the reaction is continued for 50 minutes after the addition is completed to obtain a precursor of Fe ₃ O ₄ , wherein the mass ratio of ferrous sulfate heptahydrate, ferric chloride hexahydrate, zeolite molecular sieve, sodium hydroxide, polyethylene glycol 600 and sodium polyacrylate is 10:16:5:12:7:10; Fe ₃ O The precursor of ₄ was reacted at 145°C for 4 hours, and the reaction product was magnetically separated after cooling to room temperature to obtain a black solid; the black solid was rinsed with deionized water for 3 times and dried to obtain magnetic zeolite molecular sieve nanoparticles;

S2, condensation reaction

烷/均三甲苯混合溶劑(體積比1：2)中，加入5mol/L乙酸溶液作為催化劑，攪拌 混合均勻後加入磁性沸石分子篩奈米顆粒，然後在氮氣氣氛下，升溫至105℃下反應80h，反應後分離得到的固體依次用丙酮、正己烷洗滌，洗去殘留在孔道中的未反應單體，最後130℃下真空乾燥6h，即得多環芳烴萃取劑。所述2,6-二氨基蒽醌、2,5-二羥基-1,4-對苯二甲醛、磁性沸石分子篩奈米顆粒的質量比為25：20：36，所述溶劑的加入量為2,6-二氨基蒽醌質量的20倍，所述乙酸溶液與溶劑的質量比為1：14。 Dissolve 2,6-diaminoanthraquinone and 2,5-dihydroxy-1,4-terephthalaldehyde in 1,4-dihydro-1,4-terephthalaldehyde.

5 mol/L acetic acid solution is added as a catalyst to a mixed solvent of 2,6-diaminoanthraquinone/mesitylene (volume ratio 1:2), and magnetic zeolite molecular sieve nanoparticles are added after stirring and mixing evenly, and then the temperature is raised to 105°C for reaction for 80 hours under a nitrogen atmosphere. The solid separated after the reaction is washed with acetone and n-hexane in turn to wash away the unreacted monomers remaining in the pores, and finally vacuum dried at 130°C for 6 hours to obtain a polycyclic aromatic hydrocarbon extractant. The mass ratio of the 2,6-diaminoanthraquinone, 2,5-dihydroxy-1,4-terephthalaldehyde, and magnetic zeolite molecular sieve nanoparticles is 25:20:36, the amount of the solvent added is 20 times the mass of 2,6-diaminoanthraquinone, and the mass ratio of the acetic acid solution to the solvent is 1:14.

Example 3

The preparation of polycyclic aromatic hydrocarbon extractant includes the following steps:

S1. Preparation of magnetic zeolite molecular sieve nanoparticles

Polyethylene glycol 600 and sodium polyacrylate are added to a sodium hydroxide aqueous solution, stirred to completely dissolve, and solution A is obtained; ferrous sulfate heptahydrate, ferric chloride hexahydrate, and zeolite molecular sieve are added to deionized water, stirred and mixed for 25 minutes, and then solution A is slowly added dropwise at 80° C. in an inert gas atmosphere, and the reaction is continued for 40 minutes after the addition is completed to obtain a precursor of Fe ₃ O ₄ , wherein the mass ratio of ferrous sulfate heptahydrate, ferric chloride hexahydrate, zeolite molecular sieve, sodium hydroxide, polyethylene glycol 600, and sodium polyacrylate is 10:17:6:13:8:12; Fe ₃ O The precursor of ₄ was reacted at 155°C for 3.5 hours, and after cooling to room temperature, the reaction product was magnetically separated to obtain a black solid; the black solid was rinsed with deionized water for 4 times and dried to obtain magnetic zeolite molecular sieve nanoparticles;

S2, condensation reaction

烷/均三甲苯混合溶劑(體積比1：2)中，加入6mol/L乙酸溶液作為催化劑，攪拌混合均勻後加入磁性沸石分子篩奈米顆粒，然後在氮氣氣氛下，升溫至 110℃下反應75h，反應後分離得到的固體依次用丙酮、正己烷洗滌，洗去殘留在孔道中的未反應單體，最後140℃下真空乾燥4h，即得多環芳烴萃取劑。所述2,6-二氨基蒽醌、2,5-二羥基-1,4-對苯二甲醛、磁性沸石分子篩奈米顆粒的質量比為30：28：50，所述溶劑的加入量為2,6-二氨基蒽醌質量的15倍，所述乙酸溶液與溶劑的質量比為1：16。 Dissolve 2,6-diaminoanthraquinone and 2,5-dihydroxy-1,4-terephthalaldehyde in 1,4-dihydro-1,4-terephthalaldehyde.

6 mol/L acetic acid solution is added as a catalyst to a mixed solvent of 1:2 in volume ratio of 2,6-diaminoanthraquinone/mesitylene, and then magnetic zeolite molecular sieve nanoparticles are added after stirring and mixing evenly, and then the temperature is raised to 110°C for reaction for 75 hours under a nitrogen atmosphere. The solid separated after the reaction is washed with acetone and n-hexane in turn to wash away the unreacted monomers remaining in the pores, and finally vacuum dried at 140°C for 4 hours to obtain a polycyclic aromatic hydrocarbon extractant. The mass ratio of the 2,6-diaminoanthraquinone, 2,5-dihydroxy-1,4-terephthalaldehyde, and magnetic zeolite molecular sieve nanoparticles is 30:28:50, the amount of the solvent added is 15 times the mass of 2,6-diaminoanthraquinone, and the mass ratio of the acetic acid solution to the solvent is 1:16.

Example 4

、苯並[b]苯并苊、苯並[k]苯并苊、苯並[a]芘、茚並[1,2,3-cd]芘、二苯並[a,h]蒽和苯並[g,h,i]芘；所述多環芳烴萃取劑是2,6-二氨基蒽醌、2,5-二羥基-1,4-對苯二甲醛在溶劑中進行縮合反應製得，所述多環芳烴萃取劑的製備過程中添加磁性沸石分子篩奈米顆粒；(3)配製一系列含有不同濃度目標物的標準工作溶液，濃度依次為：1ng/mL、2ng/mL、5ng/mL、10ng/mL、20ng/mL、50ng/mL、100ng/mL，通過氣相色譜-串聯質譜進行測定，並擬合得到標準曲線；(4)通過氣相色譜-串聯質譜對待測樣品進行測定，測得目標物和對應內標物的二級選擇離子峰面積比，代入標準曲線，求得樣品中的各種多環芳烴的含量。 A method for detecting the content of polycyclic aromatic hydrocarbons in incense products, wherein: the method comprises the following steps: (1) sampling in a 1.0m×1.0m×1.0m sealed glass box, the structure schematic diagram of the glass box is shown in FIG1, a test bench 1 is provided in the middle of the glass box, a sampling device is provided on one side of the test bench 1, incense is ignited on the test bench, sampling is performed for 40 minutes, the flow rate is 0.5L/min, and a total of 20L of smoke is collected in the sampling device; fans 2 are provided on the top and both sides of the glass box, the sampling device comprises a housing 3, a plurality of sampling ports 4 are provided on the top of the housing 3, the sampling ports 4 are connected to one end of a sampling tube 6 through an air duct 5, and the other end of the sampling tube 6 is connected to one end of a gas flow regulating element 7 , the other end of the gas flow regulating element 7 is connected to the negative pressure pump 9 through the negative pressure tube 8; (2) adding dichloromethane to the sampling tube, sonicating for 30 minutes, and then pouring it into a collection bottle, adding the polycyclic aromatic hydrocarbon extractant prepared in Example 1 at the same time, and vibrating it in a vortex mixer for 3 minutes to allow the polycyclic aromatic hydrocarbon extractant and the polycyclic aromatic hydrocarbon to fully contact, and standing for 15 minutes. The aromatic extractant is fully enriched with polycyclic aromatic hydrocarbons, a permanent magnet is placed on the outer wall of one side of the collection bottle to attract and fix the polycyclic aromatic hydrocarbon extractant, the solution in the collection bottle is poured out, the permanent magnet is removed, an eluent is added to the collection bottle, and the mixture is shaken and mixed in a vortex mixer to elute the polycyclic aromatic hydrocarbons, and then a permanent magnet is used to achieve phase separation, and the eluent is poured out, which is a solution containing polycyclic aromatic hydrocarbons; The eluent is evaporated by rotary decompression or blown to near dryness with gentle nitrogen, and 1 ml of ethyl acetate is added to dissolve and an internal standard is added to serve as a sample to be tested; the internal standard is one or more of the deuterated compounds of 16 polycyclic aromatic hydrocarbons, and the 16 polycyclic aromatic hydrocarbons are naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, benzoacenaphthene, pyrene, benzo[a]anthracene,

, benzo[b]benzoacenaphthene, benzo[k]benzoacenaphthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[g,h,i]pyrene; the polycyclic aromatic hydrocarbon extractant is prepared by condensation reaction of 2,6-diaminoanthraquinone and 2,5-dihydroxy-1,4-terephthalaldehyde in a solvent, and magnetic zeolite molecular sieve nanoparticles are added during the preparation of the polycyclic aromatic hydrocarbon extractant; (3) preparing a series of standard samples containing different concentrations of the target substances The working solutions, with concentrations of 1 ng/mL, 2 ng/mL, 5 ng/mL, 10 ng/mL, 20 ng/mL, 50 ng/mL, and 100 ng/mL, were measured by gas chromatography-tandem mass spectrometry, and a standard curve was obtained by fitting. (4) The samples to be tested were measured by gas chromatography-tandem mass spectrometry, and the secondary selective ion peak area ratio of the target substance and the corresponding internal standard was measured, and substituted into the standard curve to obtain the content of various polycyclic aromatic hydrocarbons in the sample.

99.999%；恒流模式，流速為1.5mL/min；分流進樣，分流比10：1；進樣量為1μL；採用的質譜條件為：電離方式為電子轟擊源，離子源溫度為280℃，電離能為70ev；掃描方式：多反應監測MRM模式；碰撞氣：氮氣，流量1.5mL/min。 In the gas chromatography-tandem mass spectrometry, the chromatographic conditions used were: HP-5MS capillary column, 30m×0.25mm×0.25μm; programmed temperature: initial temperature 80℃, maintained for 1min, then increased to 180℃ at 10℃/min, then increased to 280℃ at 5℃/min, maintained for 15min; carrier gas was nitrogen, purity

99.999%; constant flow mode, flow rate is 1.5mL/min; split injection, split ratio is 10:1; injection volume is 1μL; mass spectrometry conditions are: ionization mode is electron bombardment source, ion source temperature is 280℃, ionization energy is 70ev; scanning mode: multiple reaction monitoring MRM mode; collision gas: nitrogen, flow rate is 1.5mL/min.

After testing and analysis and calculation, the linear equation, regression coefficient, recovery rate and repeatability (n=6) of polycyclic aromatic hydrocarbons in incense smoke and incense products were obtained. The test results are shown in the table below.

As can be seen from the table above, the recovery rate of polycyclic aromatic hydrocarbons in incense smoke is between 90.7% and 105.6%, and the relative standard deviation RSD is between 3.6% and 8.2%, which proves that the method of the present invention has a high recovery rate and good repeatability.

While the polycyclic aromatic hydrocarbon extractant prepared in Example 1 was used to detect the content of polycyclic aromatic hydrocarbon substances in incense products, the polycyclic aromatic hydrocarbon extractant prepared in Examples 2-3 was also tested and obtained results similar to those above, which are not listed here one by one.

The above description is only an example of the implementation of the technical content of this invention. Any modification or change made by a person with ordinary knowledge in the technical field to which this invention belongs using this invention shall fall within the patent scope claimed by this invention, and shall not be limited to those disclosed in the examples.

1: Test bench 2: Fan 3: Casing 4: Sampling port 5: Air duct 6: Sampling tube 7: Gas flow regulating element 8: Negative pressure pipe 9: Negative pressure pump

Claims (8)

A method for detecting the content of polycyclic aromatic hydrocarbons in incense products, comprising the following steps: (1) a test bench is set in the middle of a 1.0m×1.0m×1.0m sealed glass box, one side of which is provided with a sampling device, incense is ignited on the test bench, sampling is performed for 40 minutes at a flow rate of 0.5L/min, and a total of 20L of smoke is collected in the sampling device, and fans are provided on the top and sides of the glass box; the sampling device is provided with a fan; The sampling device comprises a shell, the top of which is provided with a plurality of sampling ports, the sampling ports being connected to one end of a sampling tube through an air pipe, the other end of the sampling tube being connected to one end of a gas flow regulating element, the other end of the gas flow regulating element being connected to a negative pressure pump through a negative pressure pipe; (2) adding dichloromethane to the sampling tube, sonicating for 30-60 minutes, and then pouring it into a collection bottle, while adding a polycyclic aromatic hydrocarbon extractant, mixing in a vortex oscillator, The polycyclic aromatic hydrocarbons are fully contacted with the polycyclic aromatic hydrocarbons by oscillating for 3-10 minutes, and then the polycyclic aromatic hydrocarbons are fully enriched by the polycyclic aromatic hydrocarbons by standing for 15-30 minutes. A permanent magnet is placed on the outer wall of one side of the collection bottle to attract and fix the polycyclic aromatic hydrocarbons. The solution in the collection bottle is poured out, and the permanent magnet is removed. The eluent is added to the collection bottle, and the mixture is oscillated in a vortex mixer to elute the polycyclic aromatic hydrocarbons. Then, the permanent magnet is used to fix the polycyclic aromatic hydrocarbons. The separation of the phase magnetic zeolite molecular sieve nanoparticles and the liquid phase, pouring out the eluent, which is a solution containing polycyclic aromatic hydrocarbons; the eluent is evaporated by rotary decompression or blown to near dryness with gentle nitrogen, 1 ml of ethyl acetate is added to dissolve and an internal standard is added to serve as a sample to be tested; the internal standard is one or more of the deuterated compounds of 16 polycyclic aromatic hydrocarbons, and the 16 polycyclic aromatic hydrocarbons are naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, benzoacenaphthene, pyrene, benzo[a]anthracene,

, benzo[b]benzoacenaphthene, benzo[k]benzoacenaphthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[g,h,i]pyrene; the polycyclic aromatic hydrocarbon extractant is prepared by condensation reaction of 2,6-diaminoanthraquinone and 2,5-dihydroxy-1,4-terephthalaldehyde in a solvent, and magnetic zeolite molecular sieve nanoparticles are added during the preparation of the polycyclic aromatic hydrocarbon extractant; (3) preparing a series of standard samples containing different concentrations of the target substances The working solutions, with concentrations of 1 ng/mL, 2 ng/mL, 5 ng/mL, 10 ng/mL, 20 ng/mL, 50 ng/mL, and 100 ng/mL, were measured by gas chromatography-tandem mass spectrometry and fitted to obtain a standard curve; (4) The samples to be tested were measured by gas chromatography-tandem mass spectrometry to obtain the secondary selective ion peak area ratio of the target substance and the corresponding internal standard, which was substituted into the standard curve to obtain the content of various polycyclic aromatic hydrocarbons in the sample. A method for detecting the content of polycyclic aromatic hydrocarbons in incense products as described in claim 1, wherein: in the gas chromatography-tandem mass spectrometry, the chromatographic conditions adopted are: using an HP-5MS capillary chromatographic column with a specification of 30m×0.25mm×0.25μm; programmed heating: initial temperature 80°C, maintained for 1 minute, then heated to 180°C at 10°C/min, then heated to 280°C at 5°C/min, maintained for 15 minutes; the carrier gas is nitrogen with a purity of

99.999%; constant flow mode, flow rate is 1.5mL/min; split injection, split ratio is 10:1; injection volume is 1μL; mass spectrometry conditions are: ionization mode is electron bombardment source, ion source temperature is 280℃, ionization energy is 70ev; scanning mode: multiple reaction monitoring MRM mode; collision gas: nitrogen, flow rate is 1.5mL/min. A method for detecting the content of polycyclic aromatic hydrocarbons in incense products as described in claim 1, wherein: the preparation of the polycyclic aromatic hydrocarbons includes the following steps: dissolving 2,6-diaminoanthraquinone and 2,5-dihydroxy-1,4-terephthalaldehyde in a solvent, adding 4-6 mol/L acetic acid solution as a catalyst, stirring and mixing evenly, adding magnetic zeolite molecular sieve nanoparticles, heating to 100-110°C in a nitrogen atmosphere for 75-85h, washing the solid separated after the reaction with acetone and n-hexane in turn to wash away the unreacted monomers remaining in the pores, and finally vacuum drying at 120-140°C for 4-8h to obtain a polycyclic aromatic hydrocarbon extractant. A method for detecting the content of polycyclic aromatic hydrocarbons in incense products as described in claim 3, wherein: the solvent is 1,4-dihydro-1,4-diol

It is composed of any one of alkane, mesitylene and N,N-dimethylacetamide or a mixture of two or more thereof. A method for detecting the content of polycyclic aromatic hydrocarbons in incense products as described in claim 3, wherein: the mass ratio of the 2,6-diaminoanthraquinone, 2,5-dihydroxy-1,4-terephthalaldehyde, and magnetic zeolite molecular sieve nanoparticles is 20-30:12-28:25-50. A method for detecting the content of polycyclic aromatic hydrocarbons in incense products as described in claim 3, wherein: the amount of the solvent added is 15-25 times the mass of 2,6-diaminoanthraquinone, and the mass ratio of the acetic acid solution to the solvent is 1:12-16. A method for detecting the content of polycyclic aromatic hydrocarbons in incense products as described in claim 1, wherein: the magnetic zeolite molecular sieve nanoparticles are prepared by the following method: polyethylene glycol and sodium polyacrylate are added to a sodium hydroxide aqueous solution, stirred to completely dissolve, and solution A is obtained; ferrous sulfate heptahydrate, ferric chloride hexahydrate, and zeolite molecular sieve are added to deionized water, stirred for 15-25 minutes, and then solution A is slowly added dropwise at 70-80°C in an inert gas atmosphere, and the reaction is continued for 40-60 minutes after the addition is completed to obtain a precursor of Fe ₃ O ₄ ; Fe ₃ O The precursor of ₄ is reacted at 135-155°C for 3.5-4.5h, cooled to room temperature, and then the reaction product is magnetically separated to obtain a black solid; the black solid is rinsed with deionized water 2-4 times and dried to obtain magnetic zeolite molecular sieve nanoparticles. A method for detecting the content of polycyclic aromatic hydrocarbons in incense products as described in claim 7, wherein the mass ratio of ferrous sulfate heptahydrate, ferric chloride hexahydrate, zeolite molecular sieve, sodium hydroxide, polyethylene glycol and sodium polyacrylate is 1:1.5-1.7:0.4-0.6:1.1-1.3:0.6-0.8:0.9-1.2.