CN111830175B - Method for detecting micro-molecular aldehyde in air - Google Patents
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Abstract
The invention discloses a method for detecting trace micromolecular aldehyde in air, and belongs to the technical field of aldehyde detection. The test method of the invention comprises the following steps: collecting an air sample to be detected by using absorption liquid, and filtering by using a microporous filter membrane to obtain a derivatized filtrate; and (3) performing liquid chromatography separation on the filtrate by adopting an ultra-high performance liquid chromatograph, and performing mass spectrometry detection on the prepared eluent. According to the invention, the derivatization conditions are optimized, so that the phenol-aldehyde derivative has good stability, the accuracy of a test result can be ensured, and meanwhile, better separation effect is realized by screening chromatographic conditions and mass spectrum conditions. The method has the advantages of good linearity, simple operation, high recovery rate and high accuracy.
Description
Technical Field
The invention relates to the technical field of aldehyde detection, in particular to a method for detecting micro-small molecular aldehyde in air.
Background
Butadiene is an important raw material for manufacturing synthetic rubber, synthetic resin, nylon and the like, the main source of butadiene is obtained by dehydrogenating n-butene, but certain byproducts are inevitably generated in the dehydrogenation process, most of the byproducts are acetaldehyde, acrolein, methacrolein and crotonaldehyde, the byproducts not only influence the yield of butadiene, but also cause air pollution to the environment by diffusing into the atmosphere, and the aldehydes have strong irritation, can cause respiratory tract infection diseases and have potential hazards of sensitization, carcinogenesis, mutation and the like. Therefore, monitoring of acetaldehyde, acrolein, methacrolein and crotonaldehyde in the air of a n-butene dehydrogenation place and the surrounding environment is carried out, scientific basis can be provided for the n-butene dehydrogenation process optimization, and the method has important practical significance for monitoring the air of the environment of a working place.
Disclosure of Invention
The invention aims to provide a method for detecting micro-molecular aldehyde in air, which aims to solve the problems in the prior art, so that the stability of the derivatives of acetaldehyde, acrolein, methacrolein and crotonaldehyde to be detected is higher, the separation effect of the detection method is better, the method is good in linearity, the operation is simple, and the recovery rate and the accuracy are higher.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a method for detecting micromolecular aldehyde in air, which comprises the following steps:
(1) preparation of sample solution: collecting an air sample to be detected by using absorption liquid, and filtering by using a water-phase microporous filter membrane to obtain filtrate;
(2) liquid phase separation: performing liquid chromatography on the filtrate obtained in the step (1) by using an ultra-high performance liquid chromatograph, wherein a chromatographic column is a Shim-pack XR-ODS II, 100mm multiplied by 2.0mm and 2.5 mu m chromatographic column; the mobile phase A is water, the mobile phase B is methanol, gradient elution is carried out, the elution flow speed is 0.3mL/min, the sample injection amount is 5.0 mu L, and the column temperature is 40 ℃;
(3) carrying out mass spectrometry detection on the eluent obtained in the step (2);
the small molecular aldehyde is acetaldehyde, acrolein, methacrolein and crotonaldehyde.
Further, the absorption liquid in the step (1) is a mixed solution of a phenol reagent and concentrated hydrochloric acid, wherein the concentration of the phenol reagent is 0.35-1.0 mg/L.
Further, the phenolic agent is 3-methyl-2-benzothiazolone hydrazone hydrochloride.
Further, the pH value of the absorption liquid in the step (1) is 0-7.
Further, the collection method in the step (1) is to collect the air sample to be detected for 5-20min at the flow rate of 0.3-1.2L/min by using a large bubble absorption tube filled with absorption liquid.
Further, in step (2), the gradient elution procedure is as follows: 0-2min, 35% B-90% B, 2.0-5.50min, 90% B, 5.50-6.5min, 90% B-35% B, 6.50-7.50min, 35% B.
Further, in the step (3), electrospray is in a positive ion mode in a mass spectrometry detection mode.
Further, in the step (3), the ion spray voltage detected by mass spectrometry is 4.0kV, the ion source temperature is 450 ℃, and the acquisition mode is as follows: MRM; atomizer pressure 50.0psi, assist gas pressure 50.0psi, curtain gas pressure 35.0psi, impingement gas 7.0psi, scan time 50ms, impingement chamber outlet voltage-10.0V, impingement chamber inlet voltage-10.0V.
The invention discloses the following technical effects:
according to the invention, a phenol reagent 3-methyl-2-benzothiazolone hydrazone hydrochloride (MBTH) is used for derivatization of acetaldehyde, acrolein, methacrolein and crotonaldehyde, the derivatization reaction is rapid, derivatization of more than 96% can be realized within 5min, and the obtained 4 MBTH-aldehyde derivatives can be kept stable within 72 hours at room temperature to 40 ℃, so that the accuracy of a test result can be ensured; meanwhile, the invention adopts a Shim-pack XR-ODS II (100mm multiplied by 2.0mm, 2.5 mu m) chromatographic column, screens the mobile phase and performs gradient elution, thereby obtaining better separation effect and shorter analysis time. The detection method has the advantages of less sample consumption, short time, good method linearity, simple operation, high recovery rate, high accuracy and the like, can provide scientific basis for the dehydrogenation process optimization of the n-butene, and has important practical significance for monitoring the ambient air of a working place.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a graph showing the effect of phenol reagent solutions of different pH values on the efficiency of 4 aldehyde reactions;
FIG. 2 is a MRM chart of MBTH-acetaldehyde derivatives;
FIG. 3 is a MRM diagram of MBTH-acrolein derivative;
FIG. 4 is a MRM chart of MBTH-methacrolein derivative;
FIG. 5 is a MRM chart of MBTH-butenal derivative;
FIG. 6 is a schematic diagram of mass spectrometric cleavage of MBTH-aldehyde derivatives in ESI (+) mode, R1Is a hydrocarbyl group.
Detailed Description
The following further illustrates embodiments of the invention, taken in conjunction with the accompanying drawings, which are not to be considered limiting of the invention, but are to be understood as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The "parts" in the present invention are all parts by mass unless otherwise specified.
Methanol, acetic acid and acetonitrile (HPLC grade) used in the invention are purchased from Merck company in Germany; hydrochloric acid and ammonia (guaranteed purity) were purchased from Shanghai national pharmaceutical Agents group; acetaldehyde, acrolein, methacrolein, crotonaldehyde (> 99.8% content) were purchased from Chem Service.
Example 1
Preparation of acetaldehyde, acrolein, methacrolein, and crotonaldehyde Standard stock solutions (1.0 mg/mL):
10.0mg of each of acetaldehyde, acrolein, methacrolein and crotonaldehyde were weighed out accurately in 4 10mL volumetric flasks, dissolved in water and diluted to the mark.
Preparation of Mixed Standard solution of acetaldehyde, acrolein, methacrolein and crotonaldehyde (10.0 mg/L):
1.0mL of acetaldehyde, acrolein, methacrolein, and crotonaldehyde standard stock solutions (1.0mg/mL) were each accurately pipetted into a 100mL volumetric flask, dissolved in methanol and diluted to the mark.
Preparation of absorption liquid:
accurately weighing 1.0g of phenolic reagent (3-methyl-2-benzothiazolone hydrazone hydrochloride, MBTH) in a 1L brown volumetric flask, adding water to a constant volume to obtain 1.0g/L phenolic reagent solution, taking 1.0mL of phenolic reagent solution, adding 1.0mL of concentrated hydrochloric acid, and diluting with water to 1000mL to obtain 1.0mg/L absorption solution, wherein the pH value of the absorption solution is 1.
Collecting samples:
and (3) collecting a 5min air sample at a sampling point of n-butene dehydrogenation by using a large bubble absorption tube filled with 5mL of absorption liquid at the flow rate of 0.5L/min, and filtering by using a 0.22 mu m aqueous phase microporous membrane to obtain a filtrate, wherein the filtrate is a mixture of MBTH-aldehyde derivatives.
Blank sample:
at the sampling point, the air inlet and outlet of a large bubble absorption tube filled with 5mL of absorption liquid were opened and immediately closed, and then the same was transported and stored together and measured according to the sample measurement method.
And (3) sample determination:
(1) liquid phase separation: performing liquid chromatography on the collected sample filtrate by using an ultra-high performance liquid chromatograph, wherein a chromatographic column is Shim-pack XR-ODS II (100mm multiplied by 2.0mm, 2.5 mu m); the mobile phase A is water, and the mobile phase B is methanol; the gradient elution procedure was: 0-2min, 35% B-90% B, 2.0-5.50min, 90% B, 5.50-6.5min, 90% B-35% B, 6.50-7.50min, 35% B; the elution flow rate was 0.3mL/min, the amount of sample was 5.0. mu.L, and the column temperature was 40 ℃.
(2) Carrying out mass spectrometry detection on the eluent obtained in the step (1);
the mass spectrometry conditions used were: an ionization source: electrospray positive ion mode; the ion spray voltage is 4.0 kV; the ion source temperature is 450 ℃; the collection mode is as follows: MRM; atomizer pressure 50.0 psi; auxiliary air pressure 50.0 psi; air curtain pressure 35.0 psi; 7.0psi of collisional gas; scanning time is 50 ms; the outlet voltage of the collision chamber is-10.0V; the collision cell inlet voltage was-10.0V.
Among them, the MRM mass spectrum parameters of 4 MBTH-aldehyde derivatives are shown in Table 1.
TABLE 1
In mass spectrometry, the quantitative ion of MBTH-acetaldehyde derivative is m/z206 → 164, the quantitative ion of MBTH-acrolein derivative is m/z218 → 164, the quantitative ion of MBTH-methacrolein derivative is m/z232 → 164, and the quantitative ion of MBTH-butenal derivative is m/z232 → 164.
Stability assays of 4 MBTH-aldehyde derivatives:
after the derivatization of acetaldehyde, acrolein, methacrolein, crotonaldehyde and phenol reagents is completed, the stability of the derivatives directly influences the accuracy of the determination result. The effect of standing at room temperature to 40 ℃ for various periods of time (0, 1, 3, 6, 12, 24, 36, 72 hours) on the stability of MBTH-aldehyde derivatives of acetaldehyde, acrolein, methacrolein, and crotonaldehyde was tested. The results show that the MBTH-aldehyde derivatives of acetaldehyde, acrolein, methacrolein and crotonaldehyde are not changed after being placed for 72 hours at the temperature of between room temperature and 40 ℃, and the results show that the 4 MBTH-aldehyde derivatives can be kept stable within 72 hours at the temperature of between room temperature and 40 ℃, and the stability of the test results can be ensured.
Evaluation of matrix effect:
the method comprises the steps of respectively using a standard solution of acetaldehyde, acrolein, methacrolein and crotonaldehyde mixed with 3 concentration levels (respectively 2.0, 15.0 and 80.0 mu g/L in terms of aldehyde) of a phenol reagent absorption solution, carrying out derivatization for 20min by using an absorption solution with the concentration of 1.0mg/L, pH of 2, measuring the chromatographic peak area (S1) according to the same chromatographic detection condition as the step (1), mixing standard solutions of acetaldehyde, acrolein, methacrolein and crotonaldehyde MBTH derivatives with the same concentration, measuring the chromatographic peak area (S2) under the same chromatographic detection condition, and using the ratio of S1 to S2 as a matrix effect, wherein the results are shown in Table 2. It can be seen that the matrix effect value is between 88.7% and 97.5%.
TABLE 2
Method linear range and detection limit:
respectively transferring a proper amount of 10.0mg/L acetaldehyde, acrolein, methacrolein and crotonaldehyde mixed standard solution into 7 10mL volumetric flasks, adding a phenol reagent absorption liquid to fix the volume to a scale, preparing standard series solutions with concentration concentrations (calculated by aldehyde) of 1.0 mu g/L, 2.0 mu g/L, 5.0 mu g/L, 10.0 mu g/L, 20.0 mu g/L, 50.0 mu g/L and 100.0 mu g/L, performing derivatization for 20min by using the absorption liquid with the concentration of 1.0mg/L, pH as 1, determining according to the detection method of the step (1) and the step (2), performing linear regression on peak area (y) by using sample concentration (x, mu g/L) on the obtained data, and performing linear regression on the equation of aldehyde and correlation coefficient (r, g/L)2) And linear ranges are shown in table 5. The results show that MBTH-aldehyde derivatives of acetaldehyde, acrolein, methacrolein and crotonaldehyde have good linear relationship in the range of 1.0-100.0 μ g/L (calculated by aldehyde), and the correlation coefficient (r)2) Greater than 0.9990. The spiked solution processed by the sample analysis step was diluted stepwise, calculated as 10L of air sample collected, with the signal-to-noise ratio (S/N ═ 3) as the limit of detection (LODs) and S/N ═ 10 as the lower limit of quantitative detection (LOQs). The results showed that LODs of acetaldehyde, acrolein, methacrolein and crotonaldehyde were all 0.3. mu.g/m3LOQs are 1.0. mu.g/m3。
TABLE 3 regression equation, Linear Range, correlation coefficient, detection limits LODs and quantitative detection limits LOQs
The method has the following accuracy and precision:
different amounts of acetaldehyde, acrolein, methacrolein and crotonaldehyde standard stock solutions are added into the blank absorption solution to prepare 3 Quality Control (QC) samples with concentrations (respectively 2.0, 15.0 and 80.0 mu g/L in terms of aldehyde), and repeated measurement is carried out for 3 times to calculate the recovery rate and precision. The experimental results show that the recovery rate is in the range of 90.6% -97.8%, the precision is in the range of 1.9% -6.4%, and the results are shown in Table 4.
Table 4 results of recovery and precision tests with standard addition (n ═ 3)
Example 2
The concentration of the absorption solution was 0.35mg/L, pH was 5, and the preparation method was the same as in example 1;
collecting samples:
collecting 20min air sample with a large bubble absorption tube filled with absorption liquid at a flow rate of 1.2L/min, and filtering with 0.22 μm water phase microporous membrane to obtain filtrate, wherein the filtrate is mixture of MBTH-aldehyde derivatives.
And (3) sample determination:
(1) liquid phase separation: performing liquid chromatography on the collected sample filtrate by using an ultra-high performance liquid chromatograph, wherein a chromatographic column is Shim-pack XR-ODS II (100mm multiplied by 2.0mm, 2.5 mu m); the mobile phase A is water, and the mobile phase B is methanol; the gradient elution procedure was: 0-2min, 35% B-90% B, 2.0-5.50min, 90% B, 5.50-6.5min, 90% B-35% B, 6.50-7.50min, 35% B; the elution flow rate was 0.3mL/min, the amount of sample was 5.0. mu.L, and the column temperature was 40 ℃.
(2) Carrying out mass spectrometry detection on the eluent obtained in the step (1);
the mass spectrometry conditions were the same as in example 1.
Example 3
The concentration of the absorption solution was 0.5mg/L, pH was 7, and the preparation method was the same as in example 1;
collecting samples:
collecting an air sample to be detected for 10min at the flow rate of 0.5L/min by using a large bubble absorption tube filled with absorption liquid, and filtering by using a 0.22 mu m water-phase microporous filter membrane to obtain a filtrate, wherein the filtrate is a mixture of MBTH-aldehyde derivatives.
And (3) sample determination:
(1) liquid phase separation: performing liquid chromatography on the collected sample filtrate by using an ultra-high performance liquid chromatograph, wherein a chromatographic column is Shim-pack XR-ODS II (100mm multiplied by 2.0mm, 2.5 mu m); the mobile phase A is water, and the mobile phase B is methanol; the gradient elution procedure was: 0-2min, 35% B-90% B, 2.0-5.50min, 90% B, 5.50-6.5min, 90% B-35% B, 6.50-7.50min, 35% B; the elution flow rate was 0.3mL/min, the amount of sample was 5.0. mu.L, and the column temperature was 40 ℃.
(2) Carrying out mass spectrometry detection on the eluent obtained in the step (1);
the mass spectrometry conditions were the same as in example 1.
Effect of derivatization conditions of phenol reagents on derivatization effect:
1. effect of phenol reagent concentration
The molar ratio of the phenol reagent to the aldehyde is 1:1, and the reaction formula is as follows:
experiments have shown that the chromatographic peak heights of MBTH-aldehyde derivatives obtained by reacting different concentrations (0.35-1.0mg/L) of phenol reagent with aldehyde hardly change when the phenol reagent is kept in excess. The actual derivatization reaction can be completed by only keeping the phenol reagent in the absorption liquid excessive. In order to avoid the consumption of phenol reagent by other aldehyde ketones which may coexist, the phenol reagent is in excess in the present invention.
2. Effect of absorption solution pH on derivatization efficiency
Effect of 5.0mL of 1.0mg/L phenol reagent absorbent at various pH values (1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0) on the derivatization efficiency of 5.0mL of 20.0. mu.g/L acetaldehyde, acrolein, methacrolein, and crotonaldehyde (pH of solution was adjusted with hydrochloric acid and aqueous ammonia), with a reaction time of 5min, the results are shown in FIG. 1. As shown in FIG. 1, the derivatization reaction was completed within 5min at a pH of less than 2.
3. Effect of derivatization time on derivatization Effect
5.0mL of 20.0. mu.g/L acetaldehyde, acrolein, methacrolein and crotonaldehyde were subjected to derivatization reaction using 5.0mL of 1.0mg/L phenol reagent absorbent solution, and the efficiency of the derivatization reaction was measured. The result shows that the derivatization reaction of acetaldehyde, acrolein, methacrolein and crotonaldehyde with phenol reagent can reach more than 99% in 5.0min under proper conditions.
4. Effect of derivatization temperature on derivatization Effect
The effect of different derivatization temperatures (5, 15, 25, 35 ℃) on the derivatization efficiency of acetaldehyde, acrolein, methacrolein and crotonaldehyde was tested. The results show that in a solution with pH of 1, the reaction rate is influenced by the temperature, the higher the temperature is, the faster the derivatization reaction is, the relatively slower the derivatization reaction is at 5 ℃, at 15 ℃, the derivatization reaction can reach more than 96% in 5min, and the derivatization reaction can be completely completed in 5min at room temperature.
Selection of chromatographic separation and mass spectrometric detection conditions:
1. effect of the chromatographic column
5 different companies produced C18 chromatography columns, Diamonsil C18 (250X 4.6mm, 5 μm), Platisil ODS (150X 4.6mm, 5 μm), Waters Xbridge C18 column (100mm X2.1 mm,3.5 μm), Phenomenex Kinetex C18 column (50mm X2.1 mm,2.6 μm) and Shimadzu Shim-pack XR-ODS II column (75mm X2.0 mm,2.2 μm) were tested for their effect on the separation and detection sensitivity of 4 MBTH-aldehyde derivatives. The results show that 4 MBTH-aldehyde derivatives give better baseline separation on Diamonsil C18, Platisil ODS column and Waters Xbridge C18 column, but with slightly poorer response values on the mass spectrum. The baseline separation of formaldehyde and acetaldehyde on the Phenomenex Kinetex C18 column was not achieved, and the 4 compounds to be tested all had trailing phenomena of different degrees, which affected accurate quantification. On a Shim-pack XR-ODSII column, MBTH derivatives of acetaldehyde, acrolein, methacrolein and crotonaldehyde were also separated well and had good detection sensitivity, and MRM chromatograms of 4 MBTH-aldehyde derivatives were as shown in FIGS. 2 to 5.
Since the derivative of the phenolic reagent with the aldehyde has 2C ═ N double bonds, it should theoretically have the cis, trans or Z, E isomers. The MBTH-acetaldehyde derivative obtained under the condition of the invention has 2 MRM peaks, and the MBTH-acrolein derivative, the MBTH-methylacrolein derivative and the MBTH-butenal derivative have 1 MRM peak. The total area of the MRM was selected for calculation when performing quantitative analysis. In this test it was found that the pH of the reaction medium had a greater influence on the composition ratio of the isomers of the MBTH-aldehyde derivative, which is a single product at the acidity of the reaction solution according to the invention, except for the 2 MRM peaks of the MBTH-aldehyde derivative.
2. Influence of the Mobile phase
The effect of different species of mobile phase on the chromatographic separation of 4 MBTH-aldehyde derivatives was tested using 4 mobile phases acetonitrile-water, acetonitrile-0.1% aqueous formic acid, methanol-water, methanol-0.1% aqueous formic acid. For the 4 MBTH-aldehyde derivatives, the 4 mobile phases can obtain better separation effect only by selecting proper gradient, but the sensitivity has certain difference, the sensitivity of the compound to be detected is reduced no matter formic acid is added into methanol-water or acetonitrile-water, and the retention time of the 4 MBTH-aldehyde derivatives is increased and the peak shape is widened compared with that of the methanol-water solution and the acetonitrile-water solution.
3. Mass spectrometry quantitative ion selection and fragmentation mechanism
The standard solution of 4 MBTH-aldehyde derivatives (calculated by aldehyde) with the concentration of 100 mu g/L is injected into an ion source at the speed of 7 mu L/min, and the measurement is carried out by adopting a positive ion mode and a negative ion mode respectively, and the result shows that the sensitivity of the 4 MBTH-aldehyde derivatives in the positive ion mode is far higher than that in the negative ion mode. However, in the positive ion mode, the fragment ions of the 4 MBTH-aldehyde derivatives are substantially similar, and are m/z164 and m/z136, i.e. the fragment ions of the phenolic reagent mother nucleus cleavage (see the schematic diagram in FIG. 6), and are all m/z164 as the base peak.
The invention selects the quantitative ion of MBTH-acetaldehyde derivative as m/z206 → 164, the quantitative ion of MBTH-acrolein derivative as m/z218 → 164, the quantitative ion of MBTH-methylacrolein derivative as m/z232 → 164, and the quantitative ion of MBTH-butenal derivative as m/z232 → 164.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (4)
1. A method for detecting small molecular aldehydes in air is characterized by comprising the following steps:
(1) preparation of sample solution: collecting an air sample to be detected by using absorption liquid, and filtering by using a water-phase microporous filter membrane to obtain filtrate;
(2) liquid phase separation: performing liquid chromatography on the filtrate obtained in the step (1) by using an ultra-high performance liquid chromatograph, wherein a chromatographic column is a Shim-pack XR-ODS II, 100mm multiplied by 2.0mm and 2.5 mu m chromatographic column; the mobile phase A is water, the mobile phase B is methanol, gradient elution is carried out, the elution flow rate is 0.3mL/min, the sample injection amount is 5.0 mu L, and the column temperature is 40 ℃;
(3) carrying out mass spectrometry detection on the eluent obtained in the step (2);
the micromolecular aldehyde is acetaldehyde, acrolein, methacrolein and crotonaldehyde;
the absorption liquid in the step (1) is a mixed solution of 3-methyl-2-benzothiazolone hydrazone hydrochloride and concentrated hydrochloric acid, wherein the concentration of the 3-methyl-2-benzothiazolone hydrazone hydrochloride is 0.35-1.0 mg/L;
the pH value of the absorption liquid in the step (1) is 0-7;
in the step (2), the gradient elution procedure is as follows: 0-2min, 35% B-90% B, 2.0-5.50min, 90% B, 5.50-6.5min, 90% B-35% B, 6.50-7.50min, 35% B.
2. The method for detecting small molecular aldehydes in air as claimed in claim 1, wherein the collection in step (1) is performed by collecting 5-20min of air sample to be detected at a flow rate of 0.3-1.2L/min using a large bubble absorption tube filled with absorption liquid.
3. The method for detecting small molecular aldehydes in air as claimed in claim 1, wherein in step (3), electrospray is performed in a mass spectrometry detection mode in a positive ion mode.
4. The method for detecting the small molecular aldehyde in the air according to claim 1, wherein in the step (3), the ion spray voltage detected by mass spectrometry is 4.0kV, the ion source temperature is 450 ℃, and the collection mode is as follows: MRM; atomizer pressure 50.0psi, assist gas pressure 50.0psi, curtain gas pressure 35.0psi, impingement gas 7.0psi, scan time 50ms, impingement chamber outlet voltage-10.0V, impingement chamber inlet voltage-10.0V.
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