CN102478540A - On-line derivatization method for detecting phenolic compound in liquid by membrane inlet mass spectrum - Google Patents
On-line derivatization method for detecting phenolic compound in liquid by membrane inlet mass spectrum Download PDFInfo
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Abstract
The invention discloses an on-line derivatization method for rapid detection of a phenolic compound in a liquid by a membrane inlet mass spectrum. By adopting a membrane inlet mass spectrum, the invention realizes rapid detection of a phenolic compound in a liquid sample through an on-line derivatization device. The membrane material of the membrane inlet mass spectrum used in the method is a compact polydimethylsiloxane laminar film, and the mass spectrometer used is a small time-of-flight mass spectrograph. Under an alkaline condition, a derivatization reaction can take place between the phenolic compound inside the liquid and acetic anhydride, and a generated ester compound has a high passing rate on the membrane, thus obtaining high sensitivity. During the derivatization reaction, the liquid is transmitted to a membrane inlet device by a peristaltic pump, thus finishing an on-line derivatization and detection process. In the method, the analysis time of a single sample is less than 15min, the detection limits of phenol, 2-chlophenol, 3-methylphenol and 2, 4-dichlorophenol respectively reach 3, 6, 8, and 14 micrograms/L, and the linear range reaches two orders of magnitude. Thus, the method provided in the invention is suitable for rapid detection of a phenolic compound in a liquid.
Description
Technical field
The invention belongs to mass spectrometer; Be particularly related to the method for phenolic compound in a kind of online film sample introduction mass spectrum fast detecting liquid of deriving; Phenolic compound in this method in the liquid generates ester through derivative reaction; Combine then to adopt the film sample introduction mass spectrum of single photon ionization technique to carry out fast qualitative, quantitatively.Be 15min the analysis time of single sample, can be used for the fast detecting of phenolic compound in the liquid.
Background technology
Along with the modern industrialization development, phenolic compound has been widely used in industries such as papermaking, oil, dyestuff, agricultural chemicals as one of important chemical starting material, is second largest pollutant in the environment.Phenolic compound is a prototype matter poisonous substance, and human and biologic artifact are all had harm, is listed in the environmental contaminants of preferential monitoring by many countries and regions.
The assay method of phenols is a lot, and the assay method to Volatile Phenols in the national standard has 4-amino-antipyrine AAS and bromination titration method etc.But above method can only be measured the total amount of phenol.According to bibliographical information, the method that has been used for measuring the water body phenols has high performance liquid chromatography, vapor-phase chromatography; AASs etc. have the people with liquid phase, gas chromatography and mass spectrometry, improve its qualitative ability; But all need the complicated sample pre-treatment step, make analysis operation loaded down with trivial details, time-consuming.
The film sample introduction is a kind of technology that is applicable to on-line analysis volatility and half volatile material, obtains gradually paying attention to its quick and highly sensitive advantage.Adopt film sampling technique analysis of phenols compound can reduce steps such as separation and concentration loaded down with trivial details in the classic method to phenolic compound.The utilization of film sampling technique be the pervaporation principle of organism on film.Specifically be divided into for three steps: the organism in the liquid is absorption of being selected property and dissolving on the film surface; Organism with the diffusion form at the film internal penetration; Organism becomes gas phase and desorption at the opposite side of film.The response time of film is meant that the pervaporation of organism on film reaches and stablizes the needed time; Have only when organism the pervaporation on the film reach stable after; The signal intensity of mass spectrum institute test sample could reflect the concentration of sample truly, so the response time can influence sample analysis detection time.
Because phenolic compound polarity is stronger, be difficult to see through nonpolar film PDMS (dimethyl silicone polymer), make direct injection analysis, detectability is very high.
Phenolic compound can generate ester type compound through derivative reaction under certain condition, and the polarity of ester type compound is relatively low, and therefore higher transmitance is arranged on film.The derivatization of phenolic compound and acetic anhydride is a single step reaction, and the reaction time is shorter; Reaction reagent and product toxicity are less relatively, and therefore, acetic anhydride is present the most widely used aldehydes matter derivatization reagent; Can in water sample, directly react, the result is better.
Single photon ionization technique in the mass spectrometer carries out soft ionization to sample molecule, and the fragment ion peak of generation seldom can be crossed when accomplishing potpourri and detect, and is suitable for the fast detecting analysis of organic contaminant in the Environmental Water.
This paper adopts the pre-treating method of the direct derivatization of phenolic compound in the liquid to reduce its detectability;, the phenolic compound derivatization begins sample introduction when beginning simultaneously; The ester type compound that derivative reaction is generated reaches balance gradually on film, shorten the response time of ester type compound on film.Phenolic comp ' ds pollution in the film sample introduction mass spectrum ability fast detecting water has been simplified the sample pre-treatments step greatly, has shortened sample analysis time, has significantly reduced the detectability of phenolic compound, has improved the range of linearity.
Summary of the invention
The object of the present invention is to provide the method for phenolic compound in a kind of online film sample introduction Mass Spectrometer Method liquid of deriving.
The traditional phenol detection method all needs the complicated sample pre-treatment step, so analysis operation is loaded down with trivial details, time-consuming.Film sample introduction mass spectrum can detect the volatile organic matter in the liquid apace.The membrane material that film sample introduction mass spectrum is adopted is a dimethyl silicone polymer, belongs to nonpolar film, and the transmitance of phenolic compound on film that polarity is strong is low, therefore directly through film sample introduction mass spectrum the phenolic compound in the liquid is detected, and sensitivity is lower.
It is under the alkali condition of 9.5-11.5 that testing liquid is regulated PH, in testing liquid, adds acetic anhydride, and the phenolic compound in acetic anhydride and the liquid carries out derivative reaction, and reaction generates ester type compound.The polarity of ester type compound is lower than phenolic compound, therefore relative and phenolic compound, and ester type compound has more high permeability on film, and therefore the detectability in film sample introduction mass spectrum is lower, realizes that the rapid sensitive of phenolic compound in the liquid detects.
In the method for phenolic compound, the amount that adds acetic anhydride in the testing liquid of 200-500mL is 10-50 μ L in the described tracer liquid, and phenolic compound and acetic anhydride carry out derivative reaction in the liquid under the sub-beating action of magnetic agitation.Enough acetic anhydride additions have guaranteed the abundant reaction of phenolic compound.
In the described tracer liquid in the method for phenolic compound; The import of the mass spectral film Sample Room of film sample introduction links to each other with first interface of T-valve through peristaltic pump through pipeline; Second interface of T-valve links to each other with testing liquid, and the 3rd interface of T-valve and water connect; Realize the switching of testing liquid and water through the switching of T-valve.Under the transmission power of peristaltic pump, the fluid sample that carries out derivative reaction is through second interface of T-valve first interface of flowing through, and the peristaltic pump of flowing through again enters into the film Sample Room, accomplishes the film sample introduction of ester type compound.After fluid sample analysis finished, switch three-way valve made the 3rd interface of T-valve link to each other with first interface; Water enters into the film Sample Room by the road, and the film surface is washed, and is residual to eliminate sample; The water that is used to wash flows out through the outlet of film Sample Room, flow to waste liquid bottle by the road.
In the method for phenolic compound, film sample introduction membrane material that mass spectrum adopts is the dimethyl silicone polymer ultrathin membrane in the described tracer liquid, and thickness is 20-150 μ m, carries out the enrichment sample introduction in order to accomplish the ester type compound that reaction in the liquid is generated.
The pervaporation of organism on film reaches stable certain response time that all needs.Have only when organism the pervaporation on the film reach stable after, the signal intensity of mass spectrum institute test sample could reflect the concentration of sample truly, so the response time can influence sample analysis detection time.When the process of phenolic compound derivatization begins in liquid, carry out the film sample introduction simultaneously, help shortening the response time of ester type compound on film.
In the described tracer liquid in the method for phenolic compound; What film sample introduction mass spectrum adopted is the technology of vacuum-ultraviolet light soft ionization; Overcome electron impact ionization technology sample and produced the many problems of fragment, detected when therefore can be used for the multiple phenolic compound of liquid.
This method single analysis time is less than 15min, Pyrogentisinic Acid, 2-chlorophenol, 3-cresols and 2, and the detection limit of 4-two chlorophenols reaches 3,6,8,14 μ g/L respectively, and the range of linearity reaches two one magnitude, is applicable to the fast detecting of phenolic compound in the liquid.
Description of drawings
Phenolic compound derivative reaction and sampling device in Fig. 1 this method liquid;
The process monitoring of Fig. 2 variable concentrations phenol derivatization;
Fig. 3 concentration is the spectrogram of four kinds of phenol mixing standard specimens of 5mg/L before and after deriving (before a-derives, b-derive back);
Chemical plant, Fig. 4 Daliang City industrial waste water sample mass spectrogram.
Embodiment
The method of phenolic compound comprises phenolic compound derivative reaction device, liquid transfer and film cleaning device, film sample introduction mass spectrum etc. in a kind of online film sample introduction mass spectrum fast detecting liquid of deriving.
As shown in Figure 1, phenolic compound derivative reaction device mainly comprises conical flask, magnetic agitation 1, magnetic stirring apparatus 2; Liquid transfer and film cleaning device mainly comprise silicone tube 3, T-valve 4 (being three-way solenoid valve herein), in order to the water that cleans and peristaltic pump 5 etc.; Film sample introduction mass spectrum mainly contains film Sample Room 6, film 7 and Miniature Vehicle time mass spectrum 8 etc. and partly forms.
The testing liquid sample that in conical flask, adds 500mL, the NaOH solution of use 0.1mol/L is regulated the PH of fluid sample, makes the PH of fluid sample reach 10.Use the liquid chromatography sample introduction needle in conical flask, to add the acetic anhydride reagent of 20 μ L.Magnetic agitation 1 is put in the conical flask that fills the testing liquid sample, opened magnetic stirring apparatus 2 and stir, the rotating speed of stirrer 1 is 500-1000rpm, makes phenolic compound and acetic anhydride in the liquid carry out derivative reaction.Phenolic compound and the acetic anhydride reaction equation under alkali condition is:
Phenolic compound in the liquid is when derivative reaction begins; Fluid sample with the flow velocity of 50mL/min, is that the silicone tube 3 of 4mm is carried by internal diameter under the effect of peristaltic pump 5 transmission power; Through T-valve 4 and peristaltic pump 5, enter into the mass spectral film Sample Room 6 of film sample introduction successively.
The fluid sample that enters into film Sample Room 6 contacts with film 7, sees through film 7 by phenolic compound through the ester type compound that derivative reaction generates, and enters into Miniature Vehicle time mass spectrum 8 and carries out analyzing and testing.
Fig. 2 is the process monitoring of variable concentrations phenol derivatization, the phenol sample that can see variable concentrations in the process of film sample introduction, signal intensity in time prolongation and increase.This phenomenon is mainly from two aspects: the one, and the derivative reaction of phenolic compound needs the certain reaction time; The 2nd, the ester type compound that phenolic compound is derivatized to has certain response time on film.
The result of Fig. 2 shows, when film sample injection time during to 9min, the signal intensity of sample tends towards stability.Therefore the sample signal between the 9-12min is carried out the mass spectrogram collection, the mass spectrogram that is collected carries out qualitative according to the difference of phenolic compound molecular weight.Film sample introduction mass spectrum has adopted the single photon ionization technique, therefore can carry out the while qualitative detection to multiple phenolic compound simultaneously.Peak area according to different phenolic compound signal peaks in the mass spectrogram that is collected carries out quantitatively it separately.
After 12min; The collection of fluid sample spectrogram finishes, and switch three-way valve 4 is to pure water at this moment, and pure water enters into film Sample Room 6 under the effect of peristaltic pump 5; The film surface is cleaned; Remain in the sample on the film 7 with removal, thereby eliminate memory effect, the pure water that flows out from the film Sample Room enters into waste liquid bottle by the road.
According to above-mentioned experimental implementation condition and step, carry out the optimization of phenolic compound method in the online film sample introduction mass spectrum fast detecting liquid of deriving.The phenol of compound concentration 5mg/L, 3-cresols, 2-chlorophenol and 2,4-two chlorophenol mixed solutions adopt same film sample introduction mass spectrum to detect with direct injected detection method and two kinds of detection modes of online derivatization method respectively.The a of Fig. 3 and b are respectively resulting mass spectrograms under two kinds of detection modes of four kinds of phenolic compound mixed solutions.As can be seen from the figure, the online detection method of deriving can improve the signal intensity of four kinds of phenolic compounds greatly, has improved 26,18 than direct capillary sample inlet method respectively, 1.7,13 times.The detection method of deriving object line can improve the detection sensitivity of phenolic compound in the liquid greatly.
Industrial wastewater discharge mouth in the chemical plant, Dalian carries out sample collecting, and the industrial waste water sample of collection detects through the online film sample introduction mass spectroscopy of deriving.Fig. 4 by the mass spectrogram of collection industrial waste water sample, detected multiple phenolic compound and organism simultaneously.The result show gather and contain phenol in the wastewater sample, chlorophenol and two chlorophenols, content are respectively 96 μ g/L, 185 μ g/L and 896 μ g/L, and detect toluene simultaneously, xylene, multiple organic contaminants such as trimethylbenzene and durene.
Therefore, the online film sample introduction mass spectroscopy of deriving can satisfy the detection needs of phenolic compound in the liquid, will in environment water, the detection of phenols be used widely.
Claims (7)
1. the method for phenolic compound in the online film sample introduction Mass Spectrometer Method liquid of deriving; It is characterized in that: be under the alkali condition of 9.5-11.5 at PH; In testing liquid, add acetic anhydride; Carry out derivative reaction with the phenolic compound in the liquid, the liquid behind the derivative reaction adopts film sample introduction mass spectrum to detect, and realizes that the rapid sensitive of phenolic compound in the liquid detects.
2. method according to claim 1 is characterized in that: film sample introduction film that mass spectrum adopts (7) material is the dimethyl silicone polymer ultrathin membrane, and thickness is 20-150 μ m.
3. method according to claim 1 is characterized in that: add the acetic anhydride of 10-50 μ L in the testing liquid of 500mL, phenolic compound and acetic anhydride carry out derivative reaction in the liquid under magnetic agitation (4) beating action.
4. method according to claim 1; It is characterized in that: the import of the mass spectral film Sample Room of film sample introduction (6) links to each other through peristaltic pump (5) first interface with T-valve (4) through pipeline (3); Second interface of T-valve (4) links to each other with testing liquid, and the 3rd interface of T-valve (4) and water connect; Realize the switching of testing liquid and water through the switching of T-valve (4).
5. method according to claim 4 is characterized in that: the liquid of derivatization adopts peristaltic pump (5) as sample introduction power, and the flow velocity of peristaltic pump (5) is 20-100mL/min; In peristaltic pump (5) effect down, the flow of liquid in the derivative reaction process is through film Sample Room (6), accomplish sample introduction afterwards flow of liquid be back to liquid and carry out in the container of derivative reaction.
6. method according to claim 4 is characterized in that: after fluid sample analysis finishes, switch to water through T-valve (4), film Sample Room (6) is washed, it is residual to remove sample fast.
7. method according to claim 1 is characterized in that: what film sample introduction mass spectrum adopted is the method for vacuum-ultraviolet light soft ionization, detects when being used for the liquid phenolic compound.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103383371A (en) * | 2013-07-11 | 2013-11-06 | 哈尔滨工业大学 | In-situ electrochemical mass spectrum detection system and method thereof |
| CN108414608A (en) * | 2018-01-23 | 2018-08-17 | 中国中医科学院中药研究所 | A kind of method and its dedicated unit to chemical composition real time on-line monitoring analysis in complex reaction system |
| CN109839421A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | The method quickly detected for the direct mass spectrography of semi-volatile organic matter in liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101158671A (en) * | 2007-10-19 | 2008-04-09 | 山东省分析测试中心 | Triclosan fast analysis method in surroundings water sample |
| CN101303330A (en) * | 2007-05-09 | 2008-11-12 | 中国科学院大连化学物理研究所 | Film sample introduction sample enriching apparatus in on-line gas analysis mass spectrogram |
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2010
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| CN101303330A (en) * | 2007-05-09 | 2008-11-12 | 中国科学院大连化学物理研究所 | Film sample introduction sample enriching apparatus in on-line gas analysis mass spectrogram |
| CN101158671A (en) * | 2007-10-19 | 2008-04-09 | 山东省分析测试中心 | Triclosan fast analysis method in surroundings water sample |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103383371A (en) * | 2013-07-11 | 2013-11-06 | 哈尔滨工业大学 | In-situ electrochemical mass spectrum detection system and method thereof |
| CN103383371B (en) * | 2013-07-11 | 2015-01-21 | 哈尔滨工业大学 | In-situ electrochemical mass spectrum detection system and method thereof |
| CN109839421A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | The method quickly detected for the direct mass spectrography of semi-volatile organic matter in liquid |
| CN108414608A (en) * | 2018-01-23 | 2018-08-17 | 中国中医科学院中药研究所 | A kind of method and its dedicated unit to chemical composition real time on-line monitoring analysis in complex reaction system |
| CN108414608B (en) * | 2018-01-23 | 2021-01-01 | 中国中医科学院中药研究所 | Method for real-time on-line monitoring and analyzing chemical components in complex reaction system and special device thereof |
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Application publication date: 20120530 |