CN108195986B - A kind of method that LC-MS analyzes urea, dicyandiamide, content of melamine in guanidine hydrochloride and its three wastes - Google Patents
A kind of method that LC-MS analyzes urea, dicyandiamide, content of melamine in guanidine hydrochloride and its three wastes Download PDFInfo
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Abstract
The invention belongs to analysis technical fields, it is related to a kind of while detects major impurity in guanidine hydrochloride: the quantitative analysis method of urea, dicyandiamide, melamine, and in particular to a kind of method of LC-MS analysis guanidine hydrochloride and its urea, dicyandiamide, content of melamine in the three wastes.Sample is directly analyzed after methanol-water dilution, excessively 0.22 μm of filter membrane in the present invention, HPLC separation is using methyl alcohol-formic acid water solution system as mobile phase, gradient elution, detector are as follows: quadrupole rod _ flight time mass spectrum detector carries out outer marking quantitative to extract the peak area at object ion peak.The features such as present invention, which can be realized, efficiently separates the realization of three of the above substance, and analysis time is short, has precision good, and the rate of recovery is high, and detection limit is low.Can Fast Evaluation sample and guanidine hydrochloride synthesis the three wastes in dicyandiamide, urea, melamine content.
Description
Technical field
The invention belongs to analysis technical field, be related to a kind of while detecting major impurity in guanidine hydrochloride: urea, dicyandiamide,
The quantitative analysis method of melamine, and in particular to a kind of LC-MS analysis guanidine hydrochloride and its urea in the three wastes, dicyandiamide,
The method of content of melamine.
Background technique
Guanidine hydrochloride, chemical name guanidine hydrochloride, molecular formula CH6ClN3, it is a kind of blocks of solid white or yellowish,
Relative density 1.354g/mL, 181-183 DEG C of fusing point, the solubility in 20 DEG C of Shi Shui, methanol and in ethyl alcohol is respectively 228g/
100g, 76g/100g, 24g/100g, 4% aqueous solution pH=6.4 at 25 DEG C.Guanidine hydrochloride is multi-purpose to make the organic matters such as medicine, pesticide
Synthetic intermediate, be the important source material for manufacturing sulfa drugs and folic acid.
On the one hand, guanidine hydrochloride is obtained by frit reaction at dicyandiamide and 170-230 DEG C of ammonium salt, may be produced in the reaction
Raw melamine impurity and remaining raw material dicyandiamide；In addition, guanidine hydrochloride itself is more unstable, it is easy to be hydrolyzed to ammonia and urea.
And according to data: the analysis method of ingredient there is no and clearly report in guanidine hydrochloride and its three wastes at present.
In consideration of it, be not necessarily to carry out pre-treatment to sample it is necessary to study one kind, it can quick, simple qualitative and quantitative detection salt
The new detection method of urea, dicyandiamide, melamine in sour guanidine.LC-MS technology is with high performance liquid chromatography for separation hand
Section, using mass spectrum as a kind of separate analytical technique of Identification Tools.Currently, there is no using HPLC-MS analysis means for guanidine hydrochloride
And its report that urea, dicyandiamide, content of melamine are analyzed in the three wastes.
Summary of the invention
The shortcomings that in order to overcome the prior art, utilizes LC-MS instrument analysis guanidine hydrochloride and its life the present invention provides a kind of
The method of the urea in the three wastes, dicyandiamide, melamine that are generated in production.Guanidine hydrochloride is by dicyandiamide and ammonium chloride in melting condition
Lower reaction obtains, and micro urea and melamine are contained in dicyandiamide, can also generate a certain amount of melamine during the reaction
Amine, and guanidine hydrochloride, urea, dicyandiamide, melamine are small molecule, weak reservation compound, very using general detection method
Hardly possible realizes the quantitative detection of micro urea, dicyandiamide, melamine.The present invention, which passes through, utilizes preparation urea, dicyandiamide, melamine
Amine mixed sample, is verified by a series of experiments, and urea in guanidine hydrochloride and its three wastes, double cyanogen can be detected simultaneously by obtaining one kind
The detection method of amine, content of melamine.This method is not necessarily to carry out pre-treatment, direct injection analysis, to realize letter to sample
List fast and accurately analyzes urea, dicyandiamide, the content of melamine in guanidine hydrochloride and its three wastes, and precision is good,
The rate of recovery is high, and detection limit is low.
The technical scheme adopted by the invention to solve the technical problem is that: include the following steps:
(1) chromatography and Mass Spectrometry Conditions
(1) instrument used in is Agilent high performance liquid chromatography _ quadrupole rod _ flight time tandem mass spectrometer, and chromatographic column is
C18 liquid-phase chromatographic column；
(2) liquid-phase condition: mobile phase A is methanol；Mobile phase B is the aqueous solution of formic acid；In the aqueous solution of formic acid, formic acid with
The volume ratio of water is 0.1:99.9.
Flow velocity is 0.2-0.5mL/min, gradient elution program: 0-10min, 4-10%A；10-30min, 35-50%A；Column
Temperature is 20-35 DEG C, sample volume 5-20 μ L；
It is methanol, acetonitrile and water that mobile phase is commonly used in reverse phase, and inventor has found above-mentioned liquid-phase condition by many experiments
In, when watr-proportion is greater than the range, when having damage to chromatographic column, and being less than the range, separating degree is deteriorated；Select methanol without
Selecting acetonitrile is that can damage separating degree using acetonitrile because acetonitrile eluting power is greater than methanol；It the use of the reason of formic acid is formic acid
Under the concentration, sample ionization efficiency is best.
(3) Mass Spectrometry Conditions: ESI ionization source, positive ion detection mode, 280 DEG C of ion source temperature, dry gas stream amount 8-12L/
Min, atomizer atmospheric pressure 30-40psig, capillary voltage 3000-3500V, capillary outlet voltage 90-120V, orifice potential
65V, octupole bar radio-frequency voltage 750V, quota ion: urea, m/z=61.0426 (M+H)；Dicyandiamide, m/z=85.0539 (M+
H)；Melamine, m/z=127.0759；Qualitative ion: urea, m/z=83.0243 (M+Na), m/z=121.0752 (2M+
H)；Dicyandiamide, m/z=107.0363 (M+Na), m/z=169.0067 (2M+H)；Melamine, m/z=149.0552
It is because the compound ionsization are more efficient relative to APCI ion source using ESI ion source；Ion source temperature
It is too low to spend temperature, will affect solvent effect, Ionization Efficiency can also be lower；Temperature is excessively high, and compound response to be checked can also become
Low (conjecture may be related with thermal stability)；Dry gas stream speed is too low to will affect solvent effect, and Ionization Efficiency can also be lower,
It is excessively high that it will cause compound to be checked losses.
(2) preparation of molten sample solvent 1
Measure chromatography methanol and deionized water respectively with graduated cylinder, mixing ultrasound is placed in solvent bottle cooling stand-by, chromatography
Methanol and deionized water volume ratio are 1:1；
(3) drafting of standard curve
Urea, dicyandiamide, each 250mg of melamine standard sample are weighed respectively in 50ml volumetric flask, and molten sample is removed in addition
Solvent 1, after completely dissolution to sample, constant volume obtains the mark that urea, dicyandiamide, melamine three's concentration are 5000mg/L
Standard uses liquid, draws 20,50,100,150,200,250,300,400,500 μ L above-mentioned standards respectively and uses liquid, with molten sample solvent
1 is settled to 50mL respectively, obtains the series standard liquid of 2,5,10,15,20,25,30,40,50mg/L, using above-mentioned chromatography and
The titer of various concentration is measured under Mass Spectrometry Conditions, the quota ion peak of three is extracted respectively, records quantifying for three
Ion (urea, m/z=61.0426 (M+H)；Dicyandiamide, m/z=85.0539 (M+H)；Melamine, m/z=127.0759 (M
+ H)) peak area, draw peak area-concentration standard curve；Not according to extraction ion peak areas corresponding to quota ion and three kinds
Concentration with determinand carries out regression analysis, obtains linear equation:
Urea: yUrea=223997xUrea+ 201540, R2=0.9992 (xUreaFor urea concentration, mg/L).
Dicyandiamide: yDicyandiamide=677216xDicyandiamide+ 536983, R2=0.9995 (xDicyandiamideFor dicyandiamide concentration, mg/L).
Melamine: yMelamine=3000000xMelamine+ 4000000, R2=0.9992 (xMelamineFor melamine concentration,
mg/L)。
The meaning of corresponding y is respectively extraction ion peak areas corresponding to tie substance quota ion in formula.
(4) sample to be tested detects
Take sample to be tested in 100ml volumetric flask, molten sample solvent 1 be added, after mixing well, constant volume, use specification for
Eluent is obtained after 0.22 μm of membrane filtration, using being measured under above-mentioned chromatography and Mass Spectrometry Conditions to eluent, record is fixed
Measure the peak area of ion；Peak area-the concentration standard curve or linear equation in step (3) are substituted into, the urine in eluent is obtained
Element, dicyandiamide, melamine concentration xComponent to be checked, unit mg/L, using formula WComponent to be checked=100ml*xComponent to be checked/ m, can be obtained to
The content of urea, dicyandiamide, melamine in sample；In formula:
WComponent to be checked--- the content of component to be checked, unit mg/kg in sample to be tested；
xComponent to be checked--- standard curve checks in the concentration of component to be measured in eluent, unit mg/L；
M --- sample to be tested quality, unit g.
Sample to be tested described in step (4) includes guanidine hydrochloride crude product, the salt, the hydrochloric acid envacar that generate in guanidine hydrochloride production
Produce waste water water etc..The quality of sample to be tested usually takes 50-500mg.
Beneficial effects of the present invention:
(1) without carrying out pre-treatment, direct injection analysis to sample, thus realize it is simple, quickly to urea in sample,
Dicyandiamide, content of melamine are analyzed；
(2) it is involved in the present invention to molten sample solvent be deionized water, methanol, it is at low cost, pollute small, small toxicity；
(3) present invention has precision good, and the rate of recovery is high, and detection limit is no more than 0.2 μ g/L.
(4) present invention uses high performance liquid chromatography _ quadrupole rod _ time of-flight mass spectrometer for the first time, cooperates dedicated liquid phase color
Spectrum, mass spectrometry parameters, can be efficient, accurately realizes the survey to urea, dicyandiamide, content of melamine in guanidine hydrochloride and its three wastes
It is fixed.
Detailed description of the invention
Fig. 1 is the extraction ion flow graph of the standard sample of dicyandiamide；
Fig. 2 is the extraction ion flow graph of the sample to be tested of dicyandiamide；
Fig. 3 is the extraction ion flow graph of the standard sample of urea；
Fig. 4 is the extraction ion flow graph of the sample to be tested of urea；
Fig. 5 is the extraction ion flow graph of the standard sample of melamine；
Fig. 6 is the extraction ion flow graph of the sample to be tested of melamine；
Fig. 7 is peak area-concentration standard curve of urea；
Fig. 8 is peak area-concentration standard curve of dicyandiamide；
Fig. 9 is peak area-concentration standard curve of melamine.
Specific embodiment
Embodiment one
(1) laboratory apparatus and reagent
(1) laboratory apparatus: Agilent high performance liquid chromatography _ quadrupole rod _ flight time tandem mass spectrometer, chromatographic column is Shimadzu
Shim pack VP-ODS liquid-phase chromatographic column (15cm × 4.6mm × 5 μm)；The organic filter membrane of syringe type micro-hole (0.22 μm)；
(2) experiment reagent: methanol, Watson distilled water, formic acid, urea, dicyandiamide, melamine standard items
(2) chromatography and Mass Spectrometry Conditions
(1) liquid-phase condition: mobile phase: A: methanol；B: the water containing 0.1% formic acid；Flow velocity: 0.4mL/min, gradient elution journey
Sequence: 0-10min: containing A:5%, remaining group is divided into B；10.1-30min: containing A:40%, remaining group is divided into B；Column temperature is 25 DEG C, into
10 μ L of sample amount；
(2) Mass Spectrometry Conditions: ESI ionization source, positive ion detection mode, 280 DEG C of ion source temperature, dry gas stream amount 10L/
Min, atomizer atmospheric pressure 35psig, capillary voltage 3500V, capillary outlet voltage 100V, orifice potential 65V, octupole bar
Radio-frequency voltage 750V, quota ion: urea, m/z=61.0426 (M+H)；Dicyandiamide, m/z=85.0539 (M+H)；Melamine
Amine, m/z=127.0759；Qualitative ion: urea, m/z=83.0243 (M+Na), m/z=121.0752 (2M+H)；Dicyandiamide,
M/z=107.0363 (M+Na), m/z=169.0067 (2M+H)；Melamine, m/z=149.0552.
(3) drafting of standard curve
Urea, dicyandiamide, each 250mg of melamine standard sample are weighed respectively in 50ml volumetric flask, and molten sample is removed in addition
Solvent 1, after completely dissolution to sample, constant volume obtains the mark that urea, dicyandiamide, melamine three's concentration are 5000mg/L
Standard uses liquid, draws 20,50,100,150,200,250,300,400,500 μ L above-mentioned standards respectively and uses liquid, with molten sample solvent
1 is settled to 50mL respectively, obtains the series standard liquid of 2,5,10,15,20,25,30,40,50mg/L, using above-mentioned chromatography and
The titer of various concentration is measured under Mass Spectrometry Conditions, the quota ion peak of three is extracted respectively, records quantifying for three
Ion (urea, m/z=61.0426 (M+H)；Dicyandiamide, m/z=85.0539 (M+H)；Melamine, m/z=127.0759 (M
+ H)) peak area, draw peak area-concentration standard curve；Not according to extraction ion peak areas corresponding to quota ion and three kinds
Concentration with determinand carries out regression analysis, obtains linear equation:
Urea: y=223997x+201540, R2=0.9992 (X is urea concentration, mg/L).
Dicyandiamide: y=677216x+536983, R2=0.9995 (X is dicyandiamide concentration, mg/L).
Dicyandiamide: y=3000000x+4000000, R2=0.9992 (X is melamine concentration, mg/L).
(4) sample to be tested detects
It takes 59.4782mg guanidine hydrochloride crude product in 100ml volumetric flask, molten sample solvent 1 is added, after mixing well, constant volume,
Use specification for 0.22 μm of membrane filtration after obtain eluent, using being surveyed under above-mentioned chromatography and Mass Spectrometry Conditions to eluent
It is fixed, record the peak area of quota ion；Peak area-the concentration standard curve or linear equation in step (3) are substituted into, is washed
Urea, dicyandiamide, melamine concentration x in de- liquidComponent to be checked, unit mg/L, using formula WComponent to be checked=100ml*xComponent to be checked/ m,
Can be obtained urea in water sample to be measured, dicyandiamide, melamine content be 3833mg/kg, 4256mg/kg, 4332mg/kg.
Embodiment two
(1) laboratory apparatus and reagent
(1) laboratory apparatus: Agilent high performance liquid chromatography _ quadrupole rod _ flight time tandem mass spectrometer, chromatographic column An Jie
Human relations reversed-phase liquid chromatography column (15cm × 4.6mm × 5 μm)；The organic filter membrane of syringe type micro-hole (0.22 μm)；
(2) experiment reagent: methanol, Watson distilled water, formic acid, urea, dicyandiamide, melamine standard items
(2) chromatography and Mass Spectrometry Conditions
(1) liquid-phase condition: mobile phase: A: methanol；B: the water containing 0.05% formic acid；Flow velocity: 0.5mL/min, gradient elution
Program: 0-10min: containing A:8%, remaining group is divided into B；10.1-30min: containing A:50%, remaining group is divided into B；Column temperature is 20 DEG C,
10 μ L of sample volume；
(2) Mass Spectrometry Conditions: ESI ionization source, positive ion detection mode, 290 DEG C of ion source temperature, dry gas stream amount 12L/
Min, atomizer atmospheric pressure 30psig, capillary voltage 3400V, capillary outlet voltage 110V, orifice potential 65V, octupole bar
Radio-frequency voltage 750V, quota ion: urea, m/z=61.0426 (M+H)；Dicyandiamide, m/z=85.0539 (M+H)；Melamine
Amine, m/z=127.0759；Qualitative ion: urea, m/z=83.0243 (M+Na), m/z=121.0752 (2M+H)；Dicyandiamide,
M/z=107.0363 (M+Na), m/z=169.0067 (2M+H)；Melamine, m/z=149.0552.
(3) drafting of standard curve
Urea, dicyandiamide, each 250mg of melamine standard sample are weighed respectively in 50ml volumetric flask, and molten sample is removed in addition
Solvent 1, after completely dissolution to sample, constant volume obtains the mark that urea, dicyandiamide, melamine three's concentration are 5000mg/L
Standard uses liquid, draws 20,50,100,150,200,250,300,400,500 μ L above-mentioned standards respectively and uses liquid, with molten sample solvent
1 is settled to 50mL respectively, obtains the series standard liquid of 2,5,10,15,20,25,30,40,50mg/L, using above-mentioned chromatography and
The titer of various concentration is measured under Mass Spectrometry Conditions, the quota ion peak of three is extracted respectively, records quantifying for three
Ion (urea, m/z=61.0426 (M+H)；Dicyandiamide, m/z=85.0539 (M+H)；Melamine, m/z=127.0759 (M
+ H)) peak area, draw peak area-concentration standard curve；Not according to extraction ion peak areas corresponding to quota ion and three kinds
Concentration with determinand carries out regression analysis, obtains linear equation:
Urea: y=223997x+201540, R2=0.9992 (X is urea concentration, mg/L).
Dicyandiamide: y=677216x+536983, R2=0.9995 (X is dicyandiamide concentration, mg/L).
Dicyandiamide: y=3000000x+4000000, R2=0.9992 (X is melamine concentration, mg/L).
(4) sample to be tested detects
It takes the abraum salt generated in the guanidine hydrochloride production of 1589.2325mg in 100ml volumetric flask, molten sample solvent 1 is added, to
After mixing well, constant volume, use specification for 0.22 μm of membrane filtration after obtain eluent, using above-mentioned chromatography and Mass Spectrometry Conditions
Under eluent is measured, record the peak area of quota ion；Bring into peak area-concentration standard curve in step (3) or
Linear equation obtains urea, dicyandiamide, the melamine concentration x in eluentComponent to be checked, unit mg/L, using formula WComponent to be checked=
100ml*xComponent to be checked/ m, can be obtained urea in abraum salt sample to be measured, dicyandiamide, melamine content be 932mg/kg,
928mg/kg、887mg/kg。
Embodiment three
(1) laboratory apparatus and reagent
(1) laboratory apparatus: Agilent high performance liquid chromatography _ quadrupole rod _ flight time tandem mass spectrometer, chromatographic column is Shimadzu
Shim pack VP-ODS liquid-phase chromatographic column (15cm × 4.6mm × 5 μm)；The organic filter membrane of syringe type micro-hole (0.22 μm)；
(2) experiment reagent: methanol, Watson distilled water, formic acid, urea, dicyandiamide, melamine standard items
(3) chromatography and Mass Spectrometry Conditions
(1) liquid-phase condition: mobile phase: A: methanol；B: the water containing 0.05% formic acid；Flow velocity: 0.5mL/min, gradient elution
Program: 0-10min: containing A:8%, remaining group is divided into B；10.1-30min: containing A:40%, remaining group is divided into B；Column temperature is 30 DEG C,
10 μ L of sample volume；
(2) Mass Spectrometry Conditions: ESI ionization source, positive ion detection mode, 280 DEG C of ion source temperature, dry gas stream amount 12L/
Min, atomizer atmospheric pressure 40psig, capillary voltage 3500V, capillary outlet voltage 100V, orifice potential 65V, octupole bar
Radio-frequency voltage 750V, quota ion: urea, m/z=61.0426 (M+H)；Dicyandiamide, m/z=85.0539 (M+H)；Melamine
Amine, m/z=127.0759；Qualitative ion: urea, m/z=83.0243 (M+Na), m/z=121.0752 (2M+H)；Dicyandiamide,
M/z=107.0363 (M+Na), m/z=169.0067 (2M+H)；Melamine, m/z=149.0552.
(3) drafting of standard curve
Urea, dicyandiamide, each 250mg of melamine standard sample are weighed respectively in 50ml volumetric flask, and molten sample is removed in addition
Solvent 1, after completely dissolution to sample, constant volume obtains the mark that urea, dicyandiamide, melamine three's concentration are 5000mg/L
Standard uses liquid, draws 20,50,100,150,200,250,300,400,500 μ L above-mentioned standards respectively and uses liquid, with molten sample solvent
1 is settled to 50mL respectively, obtains the series standard liquid of 2,5,10,15,20,25,30,40,50mg/L, using above-mentioned chromatography and
The titer of various concentration is measured under Mass Spectrometry Conditions, the quota ion peak of three is extracted respectively, records quantifying for three
Ion (urea, m/z=61.0426 (M+H)；Dicyandiamide, m/z=85.0539 (M+H)；Melamine, m/z=127.0759 (M
+ H)) peak area, draw peak area-concentration standard curve；Not according to extraction ion peak areas corresponding to quota ion and three kinds
Concentration with determinand carries out regression analysis, obtains linear equation:
Urea: y=223997x+201540, R2=0.9992 (X is urea concentration, mg/L).
Dicyandiamide: y=677216x+536983, R2=0.9995 (X is dicyandiamide concentration, mg/L).
Dicyandiamide: y=3000000x+4000000, R2=0.9992 (X is melamine concentration, mg/L).
(4) sample to be tested detects
It takes the waste water generated in the production of 4830.4086mg guanidine hydrochloride in 100ml volumetric flask, molten sample solvent 1 is added, wait fill
Point mix after, constant volume, use specification for 0.22 μm of membrane filtration after obtain eluent, using under above-mentioned chromatography and Mass Spectrometry Conditions
Eluent is measured, the peak area of quota ion is recorded；Bring peak area-concentration standard curve or the line in step (3) into
Property equation, obtains urea, dicyandiamide, the melamine concentration x in eluentComponent to be checked, unit mg/L, using formula WComponent to be checked=
100ml*xComponent to be checked/ m, can be obtained urea in abraum salt sample to be measured, dicyandiamide, melamine content be 974mg/kg,
882mg/kg、750mg/kg。
Control experiment:
1, the precision measurement of method
Each 7 parts of guanidine hydrochloride sample of the same batch production of different quality are weighed respectively, are added separately to 7 100ml and are held
In measuring bottle, molten sample solvent 1 is added, after mixing well, constant volume, use specification for 0.22 μm of membrane filtration after, using above-mentioned
It is measured under chromatography and Mass Spectrometry Conditions, records the peak area of quota ion；Bring peak area-concentration standard curve or linear side into
Journey obtains the concentration x of urea in prepare liquid, dicyandiamide, melamineComponent to be checked, unit mg/L, using formula WComponent to be checked=
100ml*xComponent to be checked/ m, calculated result are as shown in the table:
| Tested number | 1 | 2 | 3 | 4 | 5 | 6 | 7 | RSD% |
| Content | 380 | 379 | 382 | 379 | 380 | 381 | 380 | 0.28 |
From the data in the table, the experimental result repeatability of this method is good.
2, the accuracy determination of method
Each 5 parts of guanidine hydrochloride of the same batch production of different quality are weighed respectively, are added separately to 5 100ml volumetric flasks
In, 40,100,200,300,400 μ L above-mentioned standards are then separately added into this 5 volumetric flasks using liquid, with molten sample solvent 1
Constant volume records the peak area of quota ion using being measured under above-mentioned chromatography and Mass Spectrometry Conditions；Bring peak area-concentration into
Standard curve or linear equation obtain the concentration x of urea in prepare liquid, dicyandiamide, melamineComponent to be checked, unit mg/L adopts
Use formula WComponent to be checked=100ml*xComponent to be checked/ m, calculated result are as shown in the table:
3, the detection limit measurement of method
It is the detection limit of 3 calculation methods, urea, dicyandiamide, melamine according to the ratio of the response of instrument and noise
Detection be limited to 0.002 μ g/L.
As described above, urea, dicyandiamide, trimerization in a kind of LC-MS analysis guanidine hydrochloride of the present invention and its three wastes
The method of cyanamide, it is not necessarily to carry out pre-treatment to sample, and direct injection analysis, precision is good, and the rate of recovery is high, and detection limit is low, can
Realize it is simple, fast and accurately the content of urea in guanidine hydrochloride and its three wastes, dicyandiamide, melamine is analyzed.
Claims (4)
1. a kind of method of LC-MS analysis guanidine hydrochloride and its urea, dicyandiamide, content of melamine in the three wastes, feature
It is: the specific steps are that:
(1) chromatography and Mass Spectrometry Conditions are determined
(1) instrument used in is Agilent high performance liquid chromatography _ quadrupole rod _ flight time tandem mass spectrometer, and chromatographic column is C18 liquid
Phase chromatographic column；
(2) liquid-phase condition: mobile phase A is methanol；Mobile phase B is the aqueous solution of formic acid；Flow velocity is 0.2-0.5mL/min, gradient
Elution program: 0-10min is mobile phase isocratic elution, mobile phase are as follows: contains A:4-10%, remaining group is divided into B；10.1-30min is
Mobile phase isocratic elution, mobile phase are as follows: contain A:35-50%, remaining group is divided into B；Column temperature is 20-35 DEG C, sample volume 5-20 μ L；
(3) Mass Spectrometry Conditions: ESI ionization source, positive ion detection mode, 280 DEG C of ion source temperature, dry gas stream amount 8-12L/min,
Atomizer atmospheric pressure 30-40psig, capillary voltage 3000-3500V, capillary outlet voltage 90-120V, orifice potential 65V,
Octupole bar radio-frequency voltage 750V, quota ion: urea, m/z=61.0426；Dicyandiamide, m/z=85.0539；Melamine, m/
Z=127.0759；Qualitative ion: urea, m/z=83.0243, m/z=121.0752；Dicyandiamide, m/z=107.0363, m/z
=169.0067；Melamine, m/z=149.0552；
(2) preparation of molten sample solvent 1
Measure chromatography methanol and deionized water respectively with graduated cylinder, mixing ultrasound is placed in solvent bottle cooling stand-by, chromatography methanol
It is 1:1 with deionized water volume ratio；
(3) drafting of standard curve
Be respectively configured urea, dicyandiamide, melamine various concentration standard solution, using above-mentioned chromatography and mass spectrum item
The titer of various concentration is measured under part, the quota ion peak of three is extracted respectively, records the quota ion of three
Peak area draws peak area-concentration standard curve；It is to be measured according to extraction ion peak areas corresponding to quota ion and three kinds of differences
The concentration of object carries out regression analysis, obtains linear equation；
(4) sample to be tested detects
It takes sample to be tested in 100ml volumetric flask, molten sample solvent 1 is added, after mixing well, constant volume uses specification for 0.22 μ
Eluent is obtained after m membrane filtration, using being measured under above-mentioned chromatography and Mass Spectrometry Conditions to eluent, records quota ion
Peak area；Substitute into the peak area-concentration standard curve or linear equation in step (3), obtain urea in sample solution,
Dicyandiamide, melamine concentration xComponent to be checked, unit mg/L, using formula WComponent to be checked=100ml*xComponent to be checked/ m, can be obtained to test sample
The content of urea, dicyandiamide, melamine in product；In formula:
WComponent to be checked--- the content of component to be checked, unit mg/kg in sample to be tested；
xComponent to be checked--- standard curve checks in the concentration of component to be measured in eluent, unit mg/L；
M --- sample to be tested quality, unit g.
2. a kind of LC-MS analysis guanidine hydrochloride according to claim 1 and its urea, dicyandiamide, melamine in the three wastes
The method of amine content, it is characterised in that: the specific steps are that:
(1) chromatography and Mass Spectrometry Conditions are determined
(1) instrument used in is Agilent high performance liquid chromatography _ quadrupole rod _ flight time tandem mass spectrometer, and chromatographic column is C18 liquid
Phase chromatographic column；
(2) liquid-phase condition: mobile phase A is methanol；Mobile phase B is the aqueous solution of formic acid；Flow velocity is 0.2-0.5mL/min, gradient
Elution program: 0-10min: containing A:4-10%, remaining group is divided into B；10.1-30min: containing A:35-50%, remaining group is divided into B；Column
Temperature is 20-35 DEG C, sample volume 5-20 μ L；
(3) Mass Spectrometry Conditions: ESI ionization source, positive ion detection mode, 280 DEG C of ion source temperature, dry gas stream amount 8-12L/min,
Atomizer atmospheric pressure 30-40psig, capillary voltage 3000-3500V, capillary outlet voltage 90-120V, orifice potential 65V,
Octupole bar radio-frequency voltage 750V, quota ion: urea, m/z=61.0426；Dicyandiamide, m/z=85.0539；Melamine, m/
Z=127.0759；Qualitative ion: urea, m/z=83.0243, m/z=121.0752；Dicyandiamide, m/z=107.0363, m/z
=169.0067；Melamine, m/z=149.0552；
(2) preparation of molten sample solvent 1
Measure chromatography methanol and deionized water respectively with graduated cylinder, mixing ultrasound is placed in solvent bottle cooling stand-by, chromatography methanol
It is 1:1 with deionized water volume ratio；
(3) drafting of standard curve
Urea, dicyandiamide, each 250mg of melamine standard sample are weighed respectively in 50ml volumetric flask, and molten sample solvent is removed in addition
1, after completely dissolution to sample, constant volume, obtaining the standard that urea, dicyandiamide, melamine three's concentration are 5000mg/L makes
With liquid, 20,50,100,150,200,250,300,400,500 μ L above-mentioned standards are drawn respectively and use liquid, are divided with molten sample solvent 1
It is not settled to 50mL, obtains the series standard liquid of 2,5,10,15,20,25,30,40,50mg/L, using above-mentioned chromatography and matter
The titer of various concentration is measured under spectral condition, extracts the quota ion peak of three respectively, record three it is quantitative from
The peak area of son draws peak area-concentration standard curve；According to extraction ion peak areas corresponding to quota ion and three kinds of differences
The concentration of determinand carries out regression analysis, obtains linear equation:
Urea: yUrea=223997xUrea+ 201540, R2=0.9992；
Dicyandiamide: yDicyandiamide=677216xDicyandiamide+ 536983, R2=0.9995；
Melamine: yMelamine=3000000xMelamine+ 4000000, R2=0.9992；
Wherein:
xUreaFor urea concentration, mg/L；
xDicyandiamideFor dicyandiamide concentration, mg/L；
xMelamineFor melamine concentration, mg/L；
Y is respectively extraction ion peak areas corresponding to tie substance quota ion；
(4) sample to be tested detects
It takes sample to be tested in 100ml volumetric flask, molten sample solvent 1 is added, after mixing well, constant volume uses specification for 0.22 μ
Eluent is obtained after m membrane filtration, using being measured under above-mentioned chromatography and Mass Spectrometry Conditions to eluent, records quota ion
Peak area；Peak area-the concentration standard curve or linear equation in step (3) are substituted into, urea in eluent, double is obtained
Cyanamide, melamine concentration xComponent to be checked, unit mg/L, using formula WComponent to be checked=100ml*xComponent to be checked/ m, can be obtained sample to be tested
The content of middle urea, dicyandiamide, melamine；In formula:
WComponent to be checked--- the content of component to be checked, unit mg/kg in water sample to be measured；
xComponent to be checked--- standard curve checks in the concentration of component to be measured in eluent, unit mg/L；
M --- water sample quality to be measured, unit g.
3. a kind of LC-MS analysis guanidine hydrochloride according to claim 1 and its urea, dicyandiamide, melamine in the three wastes
The method of amine content, it is characterised in that: the quality of sample to be tested is 50-500mg in step (4).
4. a kind of LC-MS analysis guanidine hydrochloride according to claim 1 and its urea, dicyandiamide, melamine in the three wastes
The method of amine content, it is characterised in that: sample to be tested described in step (4) is to produce in guanidine hydrochloride crude product or guanidine hydrochloride production
The waste water generated in raw abraum salt or guanidine hydrochloride production.
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| CN110954640B (en) * | 2020-01-02 | 2022-08-23 | 四川金象赛瑞化工股份有限公司 | Method for detecting trace urea in melamine |
| CN112782316B (en) * | 2021-01-29 | 2023-06-30 | 山东京博农化科技股份有限公司 | Method for analyzing content of amitraz hydrochloride |
| CN116381111A (en) * | 2023-03-21 | 2023-07-04 | 广州质量监督检测研究院 | Method for detecting urea-formaldehyde resin in melamine-formaldehyde material |
| CN117686620B (en) * | 2024-02-01 | 2024-05-14 | 深圳天祥质量技术服务有限公司 | Method for measuring melamine in textile and polymer material |
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