CN106645488B - A kind of method of salicylaldoxime content in measurement water environment - Google Patents

A kind of method of salicylaldoxime content in measurement water environment Download PDF

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CN106645488B
CN106645488B CN201611233675.6A CN201611233675A CN106645488B CN 106645488 B CN106645488 B CN 106645488B CN 201611233675 A CN201611233675 A CN 201611233675A CN 106645488 B CN106645488 B CN 106645488B
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salicylaldoxime
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李海普
孔倩
杨兆光
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Central South University
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Abstract

The invention discloses a kind of methods of salicylaldoxime content in measurement water environment; the following steps are included: (1) prepares the acetylbenzene formonitrile HCN standard solution of various concentration; gas chromatographic detection is carried out, the ratio k of the response peak area and its concentration of acetylbenzene formonitrile HCN is obtained；(2) aqueous solution containing salicylaldoxime is taken, aqueous solution is adjusted in alkalinity, adds excessive acetylation reagent and acetylization reaction can be carried out with the organic solvent of water stratification；After the reaction was completed, washing organic phase removes excessive acetylation reagent；(3) organic phase after water intaking is washed is placed in sample injection bottle, carries out gas chromatographic detection；According to the concentration for measuring salicylaldoxime in peak area and ratio k calculating aqueous solution.The accuracy rate of this method is high, and average relative standard's deviation is 2.1%-8.4%；The rate of recovery is high, average recovery rate 88.7%-92.7%；Detection limit is low, up to 2.13 μ g/L, has the advantages that easy to operate, high sensitivity, reproducible, quantitative accurate.

Description

A kind of method of salicylaldoxime content in measurement water environment
Technical field
The present invention relates to a kind of methods of salicylaldoxime content in measurement water environment, belong to sewage detection analytical technology neck Domain.
Background technique
Salicylaldoxime contains multiple electron donors, has very strong coordination ability, has certain collecting ability and good Selectivity, Rare Earth Mine, oxide ore floatation process in there is irreplaceable role, be a kind of high-efficient, selectivity compared with Good flotation collecting agent.Salicylaldoxime can with mineral surfaces selectively acting, to improve the hydrophobic performance of mineral surfaces, Mineral are enable to be adsorbed in bubble surface and float.Therefore, salicylaldoxime plays conclusive effect in the flotation for realizing mineral. Meanwhile salicylaldoxime also plays important purposes in terms of measuring Pt, Cu, Zn, Ni and Pb sensitive analysis reagent.On the other hand, Salicylaldoxime is a kind of novel I II class antiarrhythmic drug, can become a kind of efficient by means such as molecule derivatives, Gao Xuan Estrogen receptor-β (ER β) selective agonist of selecting property, potential value of the salicylaldoxime in terms of biological medicine also excite section The interest of scholars.
Salicylaldoxime also produces ecological environment and human health while bringing contribution to people's lives production It threatens.In medicine production process, part salicylaldoxime can enter environment, rat oral minimum lethal dose (MLD) 400mg/ with waste water kg.In terms of flotation, remaining salicylaldoxime a part can enter in flotation concentrate and tailing after flotation, chelating moiety weight Metal, influences the occurrence status and transportion and transformation of heavy metal, and a part can be such that concentration increases by migration, conversion and concentration Add tens times of even hundreds of times, enters river, in soil by various modes, eventually enter into human body, it is strong to environment and human body Health is a kind of potential threat.Thus, it is dirty for selecting smelting medicament in environment to establish a kind of quick, sensitive salicylaldoxime detection method Dye monitoring and pollution source apportionment are of great significance.It is individually less to the research of salicylaldoxime both at home and abroad at present, be essentially all For the research in terms of its mechanism of action, still lack a kind of effective salicylaldoxime quantitative approach.
Summary of the invention
The purpose that the present invention invents is to provide a kind of quantitative analysis method of salicylaldoxime in sewage, to help Xuan Ye enterprise It monitors its smelting process Chinese medicine utilization rate and help environmental monitoring department comprehensive monitoring selects the discharge of industry enterprise pollution substance Amount.
The technical scheme is that providing a kind of method for measuring salicylaldoxime content in water environment, including following step It is rapid:
(1) the acetylbenzene formonitrile HCN standard solution for preparing various concentration, carries out gas chromatographic detection, obtains acetylbenzene first The ratio k of the response peak area and its concentration of nitrile；
(2) aqueous solution containing salicylaldoxime is taken, aqueous solution is adjusted in alkalinity, adds excessive acetylation reagent and energy Acetylization reaction is carried out with the organic solvent of water stratification；After the reaction was completed, washing organic phase removes excessive acetylation reagent；? Carry out the process that liquid-liquid extraction can be completed while acetylization reaction；
(3) organic phase after water intaking is washed is placed in sample injection bottle, carries out gas chromatographic detection；According to measuring peak area and ratio K calculates the concentration of salicylaldoxime in aqueous solution.
Preferably, in step (2), the pH of aqueous solution is adjusted in alkalinity using sodium carbonate or sodium bicarbonate.Sodium carbonate and carbon Sour hydrogen sodium can not only provide alkaline environment, can also react with acetylation reagents such as acetic anhydrides and generate carbon dioxide gas, and two The gas of carbonoxide rises, and can promote the mixing of two-phase, to realize derivatization and extraction while progress.
Preferably, the concentration of sodium carbonate or sodium bicarbonate is 4%-6% (m/v, g/mL), most preferably 5% (m/ in aqueous solution V, g/mL).
Preferably, it in step (2), is added before acetylation reagent, inorganic salts is added in aqueous solution, it is water-soluble for adjusting Liquid ionic strength, wherein inorganic salts are to be transferred in organic phase using salting-out effect convenient for substance.
Preferably, the inorganic salts are sodium chloride, and the concentration of sodium chloride is 0.5%-2% (m/v, g/mL) in aqueous solution, Most preferably 0.5% (m/v, g/mL).
Preferably, in step (2), acetylation reagent is acetic anhydride.Acetic anhydride is relatively inexpensive acetylation reagent, can also To select other acetylation reagents, such as: trifluoroacetic anhydride.
Preferably, in step (2), the specific gravity of the organic solvent is lighter than water, consequently facilitating sampling.
Preferably, the selection of organic solvent will guarantee good with the layered effect of water, good to target substance dissolubility, extract second Acyl group benzonitrile is complete, and chromatographic behavior is good.The organic solvent be preferred fragrance hydro carbons and cyclic hydrocar-bons organic solvent, especially It is cycloalkane organic solvent, specifically, the optional toluene of organic solvent or hexamethylene, preferably hexamethylene.
Preferably, in step (2), 0.8-2mL acetic anhydride and 4-5mL organic solvent is added in the aqueous solution of every 25mL, has Solvent is toluene or hexamethylene.
Preferably, the condition of gas chromatographic detection are as follows: chromatographic apparatus is Agilent 7890A gas-chromatography, and chromatographic column is 0.25 μm of the μ m of HP-5MS, 30m × 250；Temperature program is 80 DEG C of initial temperature, keeps 5min, then be raised to 120 with 10 DEG C/min rate DEG C, 1min is kept, is finally raised to 180 DEG C with 5 DEG C/min rate, keeps 1min；Injector temperature is 200 DEG C；Detector is ECD, 220 DEG C of temperature；Splitless injecting samples, carrier gas are nitrogen, flow velocity 1.0mL/min, 1.0 μ L of sample volume.
Salicylaldoxime is detected using gas-chromatography, the bad peak type such as swarming, tailing peak can be generated.This mainly by In can occur dehydration and Beckmann rearrangement under the high temperature conditions, and the high temperature meeting of gas chromatographic sample introduction mouth and detector Cause part salicylaldoxime to react, be converted to benzonitrile, benzoxazoles and N- phenyl formamide, to can not be quantified Detection.And select suitable derivatization reagent, convert heat-staple substance for salicylaldoxime, convenient for using gas chromatography into Row qualitative and quantitative detection.Cyano is had in derivatization product, ECD (electron capture detector (ECD)) is selected to be detected, and is conducive to target The detection of object, is effectively reduced detection limit.
The present invention measures the concentration of salicylaldoxime in aqueous solution using external standard method, firstly, test acetylbenzene formonitrile HCN mark The relationship of the response peak area of the concentration of quasi- solution and acetylbenzene formonitrile HCN, relationship be it is linear, show that peak area is dense with it The ratio k of degree；Acetylization reaction is recycled, the acetylbenzene formonitrile HCN for keeping the derivative chemical conversion stability of salicylaldoxime good is tested, By the acetylbenzene formonitrile HCN content measured, the content of salicylaldoxime is calculated according to the ratio between the amount of opposite substance.
Wherein, the equation of salicylaldoxime derivative reaction such as formula (1).Since acetylation reagent is excessively added, salicylide Oxime is reacted with acetoxyl group benzonitrile by the mass ratio of the material 1:1, and derivatization product (acetoxyl group benzonitrile) is finally measured Concentration be initial salicylaldoxime concentration.Final salicylaldoxime concentration (CSalicylaldoxime) calculation formula such as formula (2).
The inspection of verifying and matrix effect for this method, is embodied by recovery of standard addition.To without salicylaldoxime Respective concentration salicylaldoxime standard solution is added in water sample, measures and extracts target substance concentration in organic phase, substitutes into formula (3) and calculates The rate of recovery.
CSalicylaldoxime=k × peak area (2)
Wherein, R% indicates recovery of standard addition；CfIndicate measured salicylaldoxime concentration, VfFor upper organic phase volume；C0 Indicate spiked levels in initial water sample, V0For water phase volume.
The beneficial effects of the present invention are:
1, the present invention, which realizes, carries out the derivatization of salicylaldoxime and one step of extraction, time saving, efficient, easy to operate.
2, the present invention adjusts the acid-base property of solution using carbonate or bicarbonate, controls alkaline environment；On the other hand, may be used It is reacted with acetylation reagent, the CO of generation2Gas facilitates the rapid realization of solution extraction process.
3, the accuracy rate of the determination method of salicylaldoxime provided by the invention, this method is high, and average relative standard is inclined Difference is 2.1%-8.4%；The rate of recovery is high, average recovery rate 88.7%-92.7%；Detection limit is low, up to 2.13 μ g/L, has behaviour Make simplicity, high sensitivity, it is reproducible, quantify accurate advantage.This method can be environmental wastewater, and smelting sewage is especially selected to mention For monitoring, convenient for the control of sewage treatment；Meanwhile supervision and management foundation is provided for corresponding supervision department.
Detailed description of the invention
Influence Fig. 1 shows different NaCl concentrations to extraction efficiency；
Fig. 2 indicates different Na2CO3The influence of concentration on extraction efficiency.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1
Analysis to salicylaldoxime in certain mining area sewage draining exit waste water, analytical procedure include:
1. measuring 0.01,0.02,0.1,0.5,1 μ g mL respectively using GC-ECD-1Acetylbenzene formonitrile HCN standard solution, The ratio k of the response peak area and its concentration that obtain acetylbenzene formonitrile HCN is 0.9993；
2. at room temperature, taking the waste water containing salicylaldoxime, 1.25g Na is added2CO3, 0.12g NaCl is settled to 25mL. It is added 1mL acetic anhydride (AA) simultaneously, 5mL hexamethylene, after about five minutes, takes upper organic phase, be added in 50mL centrifuge tube, with 8 ~10mL deionized water washes away the acetic anhydride in organic phase, after washing twice, sample introduction.
3. acetylbenzene formonitrile HCN curve comparison in gained derivatization peak areas and step (1), is calculated using external standard method Obtaining salicylaldoxime concentration in water environment is 0.078 μ g mL-1。
Embodiment 2
Analysis to salicylaldoxime in Xiang River sewage draining exit waste water, analytical procedure include:
1. measuring 0.01,0.02,0.1,0.5,1 μ g mL respectively using GC-ECD-1Acetylbenzene formonitrile HCN standard solution, The ratio k of the response peak area and its concentration that obtain acetylbenzene formonitrile HCN is 0.9989；
2. at room temperature, taking the waste water containing salicylaldoxime, 1g Na is added2CO3, 0.1g NaCl (m/v) is settled to 20mL. It is added 0.8mL acetic anhydride (AA) simultaneously, 4mL hexamethylene, after about five minutes, takes upper organic phase, be added in 50mL centrifuge tube, use 8~10mL deionized water washes away the acetic anhydride in organic phase, after washing twice, sample introduction.
3. acetylbenzene formonitrile HCN curve comparison in gained derivatization peak areas and step (1), is calculated using external standard method Salicylaldoxime concentration in water environment is obtained, is not detected.
4. taking wastewater sample again, salicylaldoxime standard solution is added, obtaining concentration is 1 μ g mL-1Mark-on waste water sample Product repeat 2~3 steps, and it is 0.92 μ g mL that salicylaldoxime concentration, which is calculated,-1, therefore this method rate of recovery is up to 92%.
Embodiment 3
Analysis to salicylaldoxime in water sample near Dexing copper mine mining area, analytical procedure include:
1. measuring 0.01,0.02,0.1,0.5,1 μ g mL respectively using GC-ECD-1Acetylbenzene formonitrile HCN standard solution, The ratio k of the response peak area and its concentration that obtain acetylbenzene formonitrile HCN is 0.9991；
2. at room temperature, taking the waste water containing salicylaldoxime, 1.25g Na is added2CO3, 0.12g NaCl (m/v) is settled to 25mL.It is added 1mL acetic anhydride (AA) simultaneously, 5mL hexamethylene, after about five minutes, takes upper organic phase, 50mL centrifuge tube is added In, the acetic anhydride in organic phase is washed away with 8~10mL deionized water, after washing twice, sample introduction.
3. acetylbenzene formonitrile HCN curve comparison in gained derivatization peak areas and step (1), is calculated using external standard method Salicylaldoxime concentration in water environment is obtained, is not detected.
4. taking wastewater sample again, salicylaldoxime standard solution is added, obtaining concentration is 10 μ g mL-1Mark-on waste water sample Product repeat 2~3 steps, and it is 9.15 μ g mL that salicylaldoxime concentration, which is calculated,-1, therefore this method rate of recovery is up to 91.5%.
Embodiment 4
The investigation of extractant
1. measuring the acetylbenzene formonitrile HCN standard solution of 0.05,0.1,0.5,1,2mg/L respectively using GC-ECD, second is obtained The response peak area of acyl group benzonitrile and the ratio k of its concentration are 0.9991；
2. at room temperature, removing 9 parts of ionized water (three kinds of extractants, each three parallel samples), it is added in each sample 1.25g Na2CO3, 0.12g NaCl and addition 0.2mL concentration are the salicylaldoxime Standard Stock solutions of 100mg/L, are settled to 20mL.It is added 1mL acetic anhydride (AA), is separately added into 5mL hexamethylene, n-hexane and toluene (three samples of each extractant condition This), after about five minutes, upper organic phase is taken, is added in 50mL centrifuge tube, is washed away in organic phase with 8~10mL deionized water Acetic anhydride, after washing twice, sample introduction.
3. acetylbenzene formonitrile HCN curve comparison in gained derivatization peak areas and step (1), is calculated using external standard method Salicylaldoxime concentration in water environment is obtained, calculates each specimen extraction efficiency using formula 3, and under the conditions of calculating every kind of NaCl concentration The average value and relative standard deviation of three parallel samples.
4. can be found by final data analysis, it can reach 90% or more using 5mL hexamethylene or the extraction of 5mL toluene and recycle Efficiency.But hexamethylene gas-chromatography behavior is better than toluene.Therefore suitable extraction can be selected in hexamethylene and toluene according to the actual situation Take agent.
Embodiment 5
The investigation of sodium chloride concentration
1. measuring the acetylbenzene formonitrile HCN standard solution of 0.05,0.1,0.5,1,2mg/L respectively using GC-ECD, second is obtained The response peak area of acyl group benzonitrile and the ratio k of its concentration are 0.9991；
2. at room temperature, remove 15 parts of ionized water (five kinds of Variation of Salinity Condition, each three parallel samples), be separately added into 0, 0.1,0.2,0.6,1g NaCl (three samples of each NaCl concentration condition), 0.2mL concentration is added in each sample is 1g Na is added in the salicylaldoxime Standard Stock solutions of 100mg/L2CO3, it is settled to 20mL.0.8mL acetic anhydride is added simultaneously (AA), 4mL hexamethylene after about five minutes, takes upper organic phase, is added in 50mL centrifuge tube, is washed away with 8~10mL deionized water Acetic anhydride in organic phase, after washing twice, sample introduction.
3. acetylbenzene formonitrile HCN curve comparison in gained derivatization peak areas and step (1), is calculated using external standard method Salicylaldoxime concentration in water environment is obtained, calculates each specimen extraction efficiency using formula (3), and calculate every kind of NaCl concentration condition The average value and relative standard deviation of lower three parallel samples, obtain Fig. 1.
4. can find that NaCl concentration can reach in 0.5%-2% (m/v, g/mL) range by final data analysis 90% or more recovery efficiency, most preferable concentrations 0.5% (m/v, g/mL).
Embodiment 6
The investigation of concentration of sodium carbonate
1. measuring the acetylbenzene formonitrile HCN standard solution of 0.05,0.1,0.5,1,2mg/L respectively using GC-ECD, second is obtained The response peak area of acyl group benzonitrile and the ratio k of its concentration are 0.9991；
2. at room temperature, remove 18 parts of ionized water (six kinds of concentration conditions, each three parallel samples), be separately added into 0, 0.04,0.2,0.4,1,2g NaCl (each Na2CO3Three samples of concentration conditions), 0.2mL concentration is added in each sample is The salicylaldoxime Standard Stock solutions of 100mg/L are added 0.1g NaCl, are settled to 20mL.0.8mL acetic anhydride is added simultaneously (AA), 4mL hexamethylene after about five minutes, takes upper organic phase, is added in 50mL centrifuge tube, is washed away with 8~10mL deionized water Acetic anhydride in organic phase, after washing twice, sample introduction.
3. acetylbenzene formonitrile HCN curve comparison in gained derivatization peak areas and step (1), is calculated using external standard method Salicylaldoxime concentration in water environment is obtained, calculates each specimen extraction efficiency using formula (3), and calculate every kind of Na2CO3Concentration item The average value and relative standard deviation of lower three parallel samples of part, obtain Fig. 2.
4. can be found by final data analysis, Na2CO3Concentration can reach 80% in 4%-6% (m/v, g/mL) range The above recovery efficiency, most preferable concentrations 5% (m/v, g/mL).

Claims (8)

1. a kind of method of salicylaldoxime content in measurement water environment, which comprises the following steps:
(1) the acetylbenzene formonitrile HCN standard solution for preparing various concentration, carries out gas chromatographic detection, obtains acetylbenzene formonitrile HCN Response peak area and its concentration ratio k；
(2) it takes the aqueous solution containing salicylaldoxime, adjusts aqueous solution in alkalinity, add excessive acetylation reagent and can be with The organic solvent of water stratification carries out acetylization reaction；After the reaction was completed, washing organic phase removes excessive acetylation reagent；
The acetylation reagent is acetic anhydride or trifluoroacetic anhydride；
(3) organic phase after water intaking is washed is placed in sample injection bottle, carries out gas chromatographic detection；According to measuring peak area and ratio k meter Calculate the concentration of salicylaldoxime in aqueous solution；
The condition of gas chromatographic detection are as follows: chromatographic apparatus is Agilent 7890A gas-chromatography, chromatographic column HP-5MS；Heating Program is 80 DEG C of initial temperature, keeps 5 min, then be raised to 120 DEG C with 10 DEG C/min rate, keeps 1 min, finally with 5 DEG C/ Min rate is raised to 180 DEG C, keeps 1 min；Injector temperature is 200 DEG C；Detector is ECD, 220 DEG C of temperature；It does not shunt Sample introduction, carrier gas are nitrogen, 1.0 mL/min of flow velocity, 1.0 μ L of sample volume.
2. the method as described in claim 1, which is characterized in that in step (2), adjusted using sodium carbonate or sodium bicarbonate water-soluble The pH of liquid is in alkalinity.
3. method according to claim 2, which is characterized in that the concentration of sodium carbonate or sodium bicarbonate is 4%- in aqueous solution 6%g/mL。
4. the method according to claim 1, which is characterized in that in step (2), it is added before acetylation reagent, Inorganic salts are added in aqueous solution.
5. method as claimed in claim 4, which is characterized in that the inorganic salts are sodium chloride, and sodium chloride is dense in aqueous solution Degree is 0.5%-2% g/mL.
6. the method as described in claim 1, which is characterized in that in step (2), the specific gravity of the organic solvent is lighter than water.
7. method as claimed in claim 6, which is characterized in that the organic solvent is cyclic hydrocar-bons organic solvent.
8. the method as described in claim 1, which is characterized in that in step (2), 0.8-2mL is added in the aqueous solution of every 25mL Acetic anhydride and 4-5 mL organic solvent, organic solvent are toluene or hexamethylene.
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CN104089914A (en) * 2014-07-07 2014-10-08 中蓝连海设计研究院 Method for quickly measuring concentration of hydroximic acid used as mineral separation collecting agent

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