CN102507780B - Method for detecting melamine by ion chromatography - Google Patents
Method for detecting melamine by ion chromatography Download PDFInfo
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- CN102507780B CN102507780B CN201110349018.9A CN201110349018A CN102507780B CN 102507780 B CN102507780 B CN 102507780B CN 201110349018 A CN201110349018 A CN 201110349018A CN 102507780 B CN102507780 B CN 102507780B
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Abstract
The invention relates to a method for detecting melamine by ion chromatography. The method comprises the following steps of: pretreating a sample to be detected by using an on-line osmotic membrane method to obtain an extracting solution of the sample; analyzing a peak area of the extracting solution of the sample by using an ion chromatograph, and comparing with a marked calibration curve to obtain the concentration of melamine in the extracting solution, thus obtaining the concentration of the melamine in the sample to be detected, wherein detection conditions of the ion chromatograph are that the sample size is 20 mu L, leacheate is an aqueous solution of sulfuric acid at the concentration of 1.5mmol/L, the flow rate is 0.9mL/min and the detection wavelength of an ultraviolet detector is 240nm. Compared with the prior art, the method has the advantages that: the melamine content in multiple samples can be effectively detected, the whole operation is simple and quick, the detected melamine content is accurate, and a blank of detecting the melamine content in multiple samples by the ion chromatography is filled up.
Description
Technical field
What the present invention relates to is the detection of melamine, specifically a kind of method of content of melamine in Sensitive Detection Multi-example based on ion chromatography.
Background technology
Melamine (English name Melamine) is a kind of organic chemical industry's intermediate product, is mainly as the raw material of producing melamine formaldehyde resin, can also do fire retardant, water reducer and formaldehyde eliminating smell agent.Its molecular formula is C
3n
6h
6, C
3n
3(NH
2)
3, molecular weight 126.12, white monoclinic prism body, tasteless, density 1.573g/cm
3(16 ℃).Be dissolved in hot water, be slightly soluble in cold water, be dissolvable in water methyl alcohol, formaldehyde, acetic acid, be insoluble to ether benzene and phenixin etc.More stable under normal temperature, can decomposite prussiate under high temperature.Melamine is weak base (pKb=8), can form melamine salt with hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid etc., meet strong acid or strong alkali aqueous solution hydrolysis, amido is progressively replaced by hydroxyl, first generate ammeline, further hydrolysis generates ammelide, finally generates cyanuric acid.
In March, 2007, the pets such as more than 4000 cat, the dog event of being poisoned to death occurred in the U.S. so far.FDA (Food and Drug Adminstration) investigation shows, in the urine crystallization of the pet food reclaimed, dead animal and kidney cell, all finds that there is melamine.The research of Ontario, Canada University of Guelph (University of Guelph) finds, can the exert an influence crystallization of renal function of melamine.China's melamine in 2008 is polluted milk powder and is caused great public health security event, arouses extensive attention at home and abroad; Calculi in urinary system occurs after taking food and polluting milk powder in the infant, and causes kidney function damage, and serious case finally causes renal failure or death.Therefore, detect accurately in Multi-example content of melamine very important.
The method of existing detection melamine mainly comprises high performance liquid chromatography-diode array, High Performance Liquid Chromatography/Mass Spectrometry method, gas chromatography-mass spectrography etc.These methods need complicated loaded down with trivial details sample pre-treatments program, and experimentation needs a large amount of organic solvent and chemicals, and process wastes time and energy.The insufficient sensitivity detected is high.
Summary of the invention
Purpose of the present invention is exactly that a kind of method that is suitable for detecting the detecting melamine by ion chromatography of trace melamine is provided in order to overcome the defect that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions: a kind of method of detecting melamine by ion chromatography, it is characterized in that, the method comprises the following steps: adopt the method for online permeable membrane to carry out pre-treatment detected sample, obtain the extract of sample, adopt ion chromatograph analyze the peak area of described sample extracting solution and compare with the mark calibration curve, draw the concentration of melamine in extract, thereby draw the concentration of melamine in detected sample, the testing conditions of described ion chromatograph is sample size 20 μ L, leacheate 1.5mmol/L aqueous sulfuric acid, flow velocity 0.9mL/min, UV-detector, the detection wavelength is 240nm.
The method of described online permeable membrane is by detected sample dialysis 10-50 minute, the dialysis condition is: the range of linearity is 0.02～500mg/L, detect and be limited to 0.012mg/L, 3 times of noise signal intensity are defined as minimum detectable level S/N=3, transit time is less than 4.2%, and the relative standard deviation of peak area is less than 3.5%.
The making of described mark calibration curve is that the melamine standard items are dissolved in ultrapure water solution, be mixed with the storing solution that concentration is 1.000g/L, 4 ℃ of preservations of lucifuge, be diluted to as required the titer of variable concentrations during use, use the cation detection pattern, the standard items of melamine are carried out to ion chromatography, obtain the standard spectrogram, detect again the melamine standard solution of variable concentrations, obtain the standard correction curve of melamine.
The inventive method is by on-line dialysis technology purifying melamine testing sample, and required solvent and amount of samples are little, have greatly saved the needed sample size of specimen.The on-line dialysis technology that the present invention adopts, the matrix impact is little, does not need as solid phase extraction sample preprocessing process complicated in the methods such as liquid chromatography; Solvent used is mainly aqueous solution, without with an organic solvent, pollution-free, environmental friendliness.The present invention can effectively detect the content of melamine in Multi-example, and whole operation is very simple, quick, detects the content of melamine obtained very accurate, has filled up the blank of the content of melamine chromatography of ions in the Multi-example.
Compared with prior art, the present invention has the following advantages:
(1) pretreatment operation is simple, and on-line dialysis completes, and saves handling time
(2) environmental friendliness, economic environmental protection.Do not use organic chemicals and a large amount of organic solvents in preprocessing process and detection, cost-saving, free from environmental pollution;
(3) Sensitive Detection of ion chromatographic method to organic amine, detectability is 0.012mg/L, has greatly improved sensitivity.
The accompanying drawing explanation
Fig. 1 is the chromatography of ions figure of melamine standard items;
Fig. 2 is blank formula powdered milk sample extract chromatography of ions figure;
Fig. 3 adds target formula milk sample extracting solution chromatography of ions figure.
Embodiment
Provide following embodiment to further illustrate of the present invention, rather than limit the scope of the invention.
Required apparatus is the MIC ion chromatograph, separating column METROSEP C2 150, guard column Metrosep C2 Guard, UV-detector.
Required reagent: melamine standard items (An Pu company provides), the electron level concentrated sulphuric acid (An Pu company provides), electron level red fuming nitric acid (RFNA) (An Pu company provides), acetic acid (Chinese traditional Chinese medicines group), ultrapure resistivity of water are 18.2M Ω .cm (25 ℃), and reagent used is all used after 0.45 μ m filtering membrane filters.
1) optimal detection condition determines
(1) preparation of leacheate: with ultrapure water and the electron level concentrated sulphuric acid, be mixed with 1.0mmol/L, 1.5mmol/L, 2.0mmol/L and 3.0mmol/L aqueous sulfuric acid as leacheate.Be mixed with 1.0mmol/L, 1.5mmol/L, 2.0mmol/L, 3.0mmol/L, 3.5mmol/L and 4.0mmol/L aqueous solution of nitric acid as leacheate with ultrapure water and the electron level concentrated sulphuric acid.
(2) preparation of melamine titer: accurately take the melamine standard items, with ultrapure water, be mixed with the storing solution that concentration is 1.00g/L.4 ℃ of preservations of lucifuge.Be diluted to as required the titer of variable concentrations during use.
2) the melamine standard items in step (2) are carried out to the ion chromatographic method analysis, detecting wavelength at sample size 20mL is 240nm, flow velocity 0.9mL/min, under 25 ℃ of conditions of detected temperatures, regulate the concentration of sulfuric acid between 1.0-3.0mmol/L, the concentration of regulating nitric acid between 1.0-4.0mmol/L.The testing conditions such as comprehensive peak shape is symmetrical, highly sensitive, favorable reproducibility, the condition that obtains best ion chromatography detection melamine is sample size 20 μ L, leacheate 1.5mmol/L aqueous sulfuric acid, flow velocity 0.9mL/min, UV-detector, the detection wavelength is 240nm.The melamine standard solution is analyzed under optimal detection condition, and chromatography of ions figure as shown in Figure 1.
3) the melamine standard solution is diluted to respectively to the melamine standard solution of 0.02mg/L, 0.05mg/L, 0.10mg/L, 0.50mg/L, 1.00mg/L, 5.00mg/L, 50.00mg/L, 120mg/L and 150mg/L.Under optimal detection condition, above-mentioned series standard solution is carried out to ion chromatography.Take melamine concentration as horizontal ordinate, and peak area is ordinate, draws calibration curve, obtains the calibration curve equation, linearly dependent coefficient, and the range of linearity and detection lower limit are as shown in table 1.
The range of linearity of table 1 melamine and detection limit
4) reappearance experiment.Under optimal detection condition, investigate the reappearance that melamine detects.The melamine that to draw respectively concentration be 1mg/L, 5mg/L and 20mg/L continuous sample introduction in a day is measured 8 times, records transit time and peak area, investigates withinday precision.The melamine standard solution of above-mentioned three parts of concentration is detected every day, continuous detecting 8 days, record transit time and peak area again, investigates day to day precision.The withinday precision of transit time and peak area is 3.8%～4.6%, and the day to day precision of transit time and peak area is 5.3%～6.8%.
5) detection of actual sample
(1) detection of the preparation of blank formula milk powder extract and egg.
A takes the formula milk of 8.0000g different brands, with ultrapure water, dissolves, and the acetic acid of 10mL5%, constant volume is in the volumetric flask of 100mL.Direct injection analysis behind the on-line dialysis unit.
B takes 9.0000g and dissolves with ultrapure water after egg is blended, the acetic acid of 10mL5%, and constant volume is in the volumetric flask of 100mL.Vibration is fully dissolved it, is mixed with the sample solution of 90.000g/L; Be placed on hydro-extractor: 4000r/min, 20min, get supernatant liquor, direct injection analysis behind the on-line dialysis unit again.
Use the dialysis unit of chromatography of ions, between 10-50 minute, regulate the dialysis time, obtain the extract of blank formula powdered milk sample and egg.By this sample direct injected, under optimal detection condition, detect.The testing conditions such as comprehensive peak shape is symmetrical, highly sensitive, favorable reproducibility, obtaining the best dialysis time is the extract that dialysis obtains blank formula powdered milk sample and egg in 20 minutes.By the extract direct injected, under optimal detection condition, detect.
(2) preparation and determination methods of the mark-on formula milk extract that contains standard items.The standard items that add melamine in the extract of above-mentioned blank formula powdered milk sample, be mixed with respectively the mark-on sample extracting solution of 0.5mg/L, 5mg/L and 15mg/L.
(3) the chromatography of ions figure of blank formula milk powder, the egg obtained and the mark-on formula milk extract that contains standard items, according to chromatogram collection of illustrative plates and step 3) the calibration curve equation of gained, the recovery that calculates blank formula milk powder is that 102%, RSD is 3.5%; The recovery of egg is that 93%, RSD is 5.2%; The recovery of mark-on formula milk is that 96%, RSD is 2.4%.
Claims (2)
1. the method for a detecting melamine by ion chromatography, it is characterized in that, the method comprises the following steps: adopt the method for online permeable membrane to carry out pre-treatment detected sample, obtain the extract of sample, adopt ion chromatograph analyze the peak area of described sample extracting solution and compare with the mark calibration curve, draw the concentration of melamine in extract, thereby draw the concentration of melamine in detected sample, the testing conditions of described ion chromatograph is sample size 20 μ L, leacheate 1.5mmol/L aqueous sulfuric acid, flow velocity 0.9mL/min, UV-detector, the detection wavelength is 240nm, separating column METROSEP C2 150, guard column Metrosep C2 Guard,
The method of described online permeable membrane is by detected sample dialysis 10-50 minute, the dialysis condition is: the range of linearity is 0.02 ~ 500mg/L, detect and be limited to 0.012mg/L, 3 times of noise signal intensity are defined as minimum detectable level S/N=3, transit time is less than 4.2%, and the relative standard deviation of peak area is less than 3.5%.
2. the method for a kind of detecting melamine by ion chromatography according to claim 1, it is characterized in that, the making of described mark calibration curve is that the melamine standard items are dissolved in ultrapure water solution, be mixed with the storing solution that concentration is 1.000g/L, 4 ℃ of preservations of lucifuge, be diluted to as required the titer of variable concentrations during use, use the cation detection pattern, standard items to melamine carry out ion chromatography, obtain the standard spectrogram, detect again the melamine standard solution of variable concentrations, obtain the standard correction curve of melamine.
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| CN104458996B (en) * | 2014-12-19 | 2016-05-04 | 山东省计量科学研究院 | A kind of chromatography of ions that uses detects the method for analyzing to melamine in milk powder |
| CN118362662A (en) * | 2024-04-25 | 2024-07-19 | 四川精事达科技有限公司 | Method for detecting free melamine in melamine polyphosphate |
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Non-Patent Citations (3)
| Title |
|---|
| 宋伟等.在线渗析－紫外检测离子色谱法直接测定乳制品中亚硝酸盐及硝酸盐.《卫生研究》.2007,第36卷(第6期), * |
| 李红艳等.离子色谱法检测含蛋白质食品中三聚氰胺.《福建分析测试》.2009,第18卷(第4期), |
| 离子色谱法检测含蛋白质食品中三聚氰胺;李红艳等;《福建分析测试》;20091231;第18卷(第4期);摘要，第8页第1.1节至第11页第2.5节，图1 * |
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