CN108195986A - A kind of method of urea, dicyandiamide, content of melamine in LC-MS analysis guanidine hydrochloride and its three wastes - Google Patents
A kind of method of urea, dicyandiamide, content of melamine in LC-MS analysis guanidine hydrochloride and its three wastes Download PDFInfo
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Abstract
The invention belongs to analysis technical fields, are related to a kind of while detect major impurity in guanidine hydrochloride：The quantitative analysis method of urea, dicyandiamide, melamine, and in particular to a kind of LC-MS analysis guanidine hydrochloride and its urea in the three wastes, dicyandiamide, content of melamine method.In the present invention sample dilute through methanol-water, cross 0.22 μm of filter membrane after directly analyzed, HPLC separation is using methanol aqueous formic acid system as mobile phase, and gradient elution, detector is：Quadrupole rod _ flight time mass spectrum detector carries out outer marking quantitative to extract the peak area at object ion peak.The present invention, which can realize, efficiently separates the realization of three of the above substance, and analysis time is short, has the features such as precision is 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 fields, are related to a kind of while detect 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 technology
Guanidine hydrochloride, chemical name guanidine hydrochloride, molecular formula CH6ClN3, it is a kind of white or yellowish blocks of solid,
Relative density 1.354g/mL, 181-183 DEG C of fusing point, solubility at 20 DEG C in water, 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 mostly used 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 170-230 DEG C of dicyandiamide and ammonium salt, may be produced in the reaction
Raw melamine impurity and remaining raw material dicyandiamide；In addition, guanidine hydrochloride is more unstable in itself, it is easily 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, a kind of without carrying out pre-treatment to sample it is necessary to study, can quickly, it is simply qualitative and quantitatively detect salt
The new detection method of urea, dicyandiamide, melamine in sour guanidine.LC-MS technology is using high performance liquid chromatography as separation hand
Section, using mass spectrum as a kind of separate analytical technique of Identification Tools.At present, it there is no and be used for guanidine hydrochloride using HPLC-MS analysis means
And its report that urea, dicyandiamide, content of melamine are analyzed in the three wastes.
Invention content
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 urea, dicyandiamide, melamine in the three wastes generated in production.Guanidine hydrochloride is by dicyandiamide and ammonium chloride in melting condition
Under be obtained by the reaction, containing micro urea and melamine 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, using general detection method very
Hardly possible realizes the quantitative detection of micro urea, dicyandiamide, melamine.The present invention is by using 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 to sample without carrying out pre-treatment, direct injection analysis, so as to fulfill letter
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 columns；
(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 size 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 more than the range, when having damage to chromatographic column, and being less than the range, separating degree is deteriorated；Select methanol without
It is because acetonitrile eluting power is more than methanol to select acetonitrile, and separating degree can be damaged using acetonitrile；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 sources, positive ion detection pattern, 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 relative to APCI ion sources, the compound ionsization are more efficient using ESI ion sources；Ion source temperature
It is too low to spend temperature, solvent effect can be influenced, 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 influence 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 positioned in solvent bottle and cools down for use, 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 flasks, and molten sample is removed in addition
Solvent 1, after sample fully dissolves, constant volume obtains the mark that urea, dicyandiamide, melamine three's concentration are 5000mg/L
Standard draws 20,50,100,150,200,250,300,400,500 μ L above-mentioned standards using liquid, with molten sample solvent respectively using liquid
1 is settled to 50mL respectively, obtain 2,5,10,15,20,25,30,40, the series standard liquid of 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；According to extraction ion peak areas corresponding to quota ion and three kinds not
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
Sample to be tested is taken in 100ml volumetric flasks, adds in molten sample solvent 1, after abundant mixing, 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, obtains the urine in eluent
Element, dicyandiamide, melamine concentration xComponent to be checked, unit mg/L, using formula WComponent to be checked=100*xComponent to be checked/ m, you can obtain to be measured
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 the salt, the hydrochloric acid envacar that are generated in guanidine hydrochloride crude product, 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 to sample, direct injection analysis, so as to fulfill it is simple, quickly to urea in sample,
Dicyandiamide, content of melamine are analyzed；
(2) it is involved in the present invention to arrive molten sample solvent as 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 coordinates dedicated liquid phase color for the first time using high performance liquid chromatography _ quadrupole rod _ time of-flight mass spectrometer
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.
Description of the drawings
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
ShimpackVP-ODS liquid-phase chromatographic columns (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:Water containing 0.1% formic acid；Flow velocity：0.4mL/min, gradient elution journey
Sequence：0-10min：Containing A：5%, remaining component is B；10.1-30min：Containing A：40%, remaining component is B；Column temperature is 25 DEG C, into
10 μ L of sample amount；
(2) Mass Spectrometry Conditions：ESI ionization sources, positive ion detection pattern, 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 flasks, and molten sample is removed in addition
Solvent 1, after sample fully dissolves, constant volume obtains the mark that urea, dicyandiamide, melamine three's concentration are 5000mg/L
Standard draws 20,50,100,150,200,250,300,400,500 μ L above-mentioned standards using liquid, with molten sample solvent respectively using liquid
1 is settled to 50mL respectively, obtain 2,5,10,15,20,25,30,40, the series standard liquid of 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；According to extraction ion peak areas corresponding to quota ion and three kinds not
Concentration with determinand carries out regression analysis, obtains linear equation：
Urea：Y=223997x+201540, R2=0.9992 (X be urea concentration, mg/L).
Dicyandiamide：Y=677216x+536983, R2=0.9995 (X be dicyandiamide concentration, mg/L).
Dicyandiamide：Y=3000000x+4000000, R2=0.9992 (X be melamine concentration, mg/L).
(4) sample to be tested detects
59.4782mg guanidine hydrochlorides crude product is taken in 100ml volumetric flasks, adds in molten sample solvent 1, after abundant mixing, constant volume,
Eluent is obtained after specification is used as 0.22 μm of membrane filtration, 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=100*xComponent to be checked/ m, i.e.,
Can obtain 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 are prompt for peace
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:Water containing 0.05% formic acid；Flow velocity：0.5mL/min, gradient elution
Program：0-10min：Containing A：8%, remaining component is B；10.1-30min：Containing A：50%, remaining component is B；Column temperature is 20 DEG C,
10 μ L of sample size；
(2) Mass Spectrometry Conditions：ESI ionization sources, positive ion detection pattern, 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 flasks, and molten sample is removed in addition
Solvent 1, after sample fully dissolves, constant volume obtains the mark that urea, dicyandiamide, melamine three's concentration are 5000mg/L
Standard draws 20,50,100,150,200,250,300,400,500 μ L above-mentioned standards using liquid, with molten sample solvent respectively using liquid
1 is settled to 50mL respectively, obtain 2,5,10,15,20,25,30,40, the series standard liquid of 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；According to extraction ion peak areas corresponding to quota ion and three kinds not
Concentration with determinand carries out regression analysis, obtains linear equation：
Urea：Y=223997x+201540, R2=0.9992 (X be urea concentration, mg/L).
Dicyandiamide：Y=677216x+536983, R2=0.9995 (X be dicyandiamide concentration, mg/L).
Dicyandiamide：Y=3000000x+4000000, R2=0.9992 (X be melamine concentration, mg/L).
(4) sample to be tested detects
The abraum salt that the guanidine hydrochloride of 1589.2325mg generates in producing is taken to add in molten sample solvent 1 in 100ml volumetric flasks, treat
After abundant mixing, constant volume obtains eluent, using above-mentioned chromatography and Mass Spectrometry Conditions after using specification as 0.22 μm of membrane filtration
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=
100*xComponent to be checked/ m, you can obtain 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
ShimpackVP-ODS liquid-phase chromatographic columns (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:Water containing 0.05% formic acid；Flow velocity：0.5mL/min, gradient elution
Program：0-10min：Containing A：8%, remaining component is B；10.1-30min：Containing A：40%, remaining component is B；Column temperature is 30 DEG C,
10 μ L of sample size；
(2) Mass Spectrometry Conditions：ESI ionization sources, positive ion detection pattern, 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 flasks, and molten sample is removed in addition
Solvent 1, after sample fully dissolves, constant volume obtains the mark that urea, dicyandiamide, melamine three's concentration are 5000mg/L
Standard draws 20,50,100,150,200,250,300,400,500 μ L above-mentioned standards using liquid, with molten sample solvent respectively using liquid
1 is settled to 50mL respectively, obtain 2,5,10,15,20,25,30,40, the series standard liquid of 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；According to extraction ion peak areas corresponding to quota ion and three kinds not
Concentration with determinand carries out regression analysis, obtains linear equation：
Urea：Y=223997x+201540, R2=0.9992 (X be urea concentration, mg/L).
Dicyandiamide：Y=677216x+536983, R2=0.9995 (X be dicyandiamide concentration, mg/L).
Dicyandiamide：Y=3000000x+4000000, R2=0.9992 (X be melamine concentration, mg/L).
(4) sample to be tested detects
The waste water that 4830.4086mg guanidine hydrochlorides generate in producing is taken to add in molten sample solvent 1 in 100ml volumetric flasks, wait to fill
After dividing mixing, constant volume obtains eluent, using under above-mentioned chromatography and Mass Spectrometry Conditions after using specification as 0.22 μm of membrane filtration
Eluent is measured, records the peak area of quota ion；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=
100*xComponent to be checked/ m, you can obtain urea in abraum salt sample to be measured, dicyandiamide, melamine content be 974mg/kg, 882mg/
kg、750mg/kg。
Control experiment：
1st, the precision of method measures
Each 7 parts of the guanidine hydrochloride sample of the same batch production of different quality is weighed respectively, is added separately to 7 100ml and is held
In measuring bottle, molten sample solvent 1 is added in, after abundant mixing, constant volume, after using specification as 0.22 μm of membrane filtration, 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=100*
xComponent to be checked/ m, result of calculation 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 |
By data in table it is found that the experimental result repeatability of this method is good.
2nd, the accuracy determination of method
Each 5 parts of the guanidine hydrochloride of the same batch production of different quality is weighed respectively, is 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 using being measured under above-mentioned chromatography and Mass Spectrometry Conditions, records the peak area of quota ion；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=100*xComponent to be checked/ m, result of calculation are as shown in the table：
3rd, the detection limit of method measures
According to the detection limit that the ratio of the response of instrument and noise is 3 computational methods, urea, dicyandiamide, melamine
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 to sample without carrying out pre-treatment, 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 LC-MS analysis guanidine hydrochloride and its urea in the three wastes, dicyandiamide, content of melamine method, feature
It is：Its specific steps are：
(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 component are B；10.1-30min：Containing A：35-50%, remaining component are B；Column
Temperature is 20-35 DEG C, sample size 5-20 μ L；
(3) Mass Spectrometry Conditions：ESI ionization sources, positive ion detection pattern, 280 DEG C, dry gas stream amount 8-12L/min of ion source temperature,
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 positioned in solvent bottle and cools down for use, chromatography methanol
It is 1 with deionized water volume ratio:1；
(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
The sample solution of sample to be tested is configured, is measured using above-mentioned chromatography and Mass Spectrometry Conditions, records the peak of quota ion
Area；Substitute into the peak area-concentration standard curve or linear equation in step (3), obtain urea in eluent, dicyandiamide,
Melamine concentration xComponent to be checked, unit mg/L, using formula WComponent to be checked=100*xComponent to be checked/ m, you can obtain urea in sample to be tested,
The content of dicyandiamide, melamine；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：Its specific steps are：
(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 component are B；10.1-30min：Containing A：35-50%, remaining component are B；Column
Temperature is 20-35 DEG C, sample size 5-20 μ L；
(3) Mass Spectrometry Conditions：ESI ionization sources, positive ion detection pattern, 280 DEG C, dry gas stream amount 8-12L/min of ion source temperature,
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 positioned in solvent bottle and cools down for use, chromatography methanol
It is 1 with deionized water volume ratio:1；
(3) drafting of standard curve
Urea, dicyandiamide, each 250mg of melamine standard sample are weighed respectively in 50ml volumetric flasks, and molten sample solvent is removed in addition
1, after sample fully dissolves, 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 using liquid, are divided with molten sample solvent 1
Be not settled to 50mL, obtain 2,5,10,15,20,25,30,40, the series standard liquid of 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
Sample to be tested is taken in 100ml volumetric flasks, adds in molten sample solvent 1, after abundant mixing, constant volume uses specification as 0.22 μ
Eluent is obtained after m membrane filtrations, 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, obtains urea in eluent, double
Cyanamide, melamine concentration xComponent to be checked, unit mg/L, using formula WComponent to be checked=100*xComponent to be checked/ m, you can obtain in sample to be tested
Urea, dicyandiamide, melamine content；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 produces 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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