CN106770729A - A kind of method for detecting free state and combining state micro cyanide - Google Patents

Abstract

The invention discloses a method for detecting trace cyanide in a free state and a combined state, belongs to the technical field of analysis and detection, and is mainly used for the analysis of drinking wine and its raw materials. The invention utilizes a specific pretreatment and derivatization device, which can separately process free state or combined state cyanide samples. For free cyanide, release hydrocyanic acid to directly derivatize cyanide; for bound cyanide, it is first converted to free hydrocyanic acid, and then derivatized with a derivatizing reagent. For the derivatives, liquid chromatography-mass spectrometry was used for qualitative and quantitative analysis, and the internal standard method was used to establish the standard curve, and the contents of free and bound cyanide were calculated respectively. The detection limit of the detection method established by the invention can be as low as 0.01 μg/L, the quantification limit is 0.05 μg/L, the linear correlation coefficient is greater than 0.99, the standard addition recovery rate is 93.8%-106%, and the relative standard deviation is less than 10%. The method of the invention has high detection sensitivity, short required time and little interference, and can respectively meet the requirements for the determination of bound state and free state cyanide.

Description

A method for detecting free and bound trace cyanide

technical field

The invention relates to a method for detecting trace cyanide in a free state and a combined state, and belongs to the technical field of analysis and detection. It is mainly used for the analysis of drinking wine and its raw materials.

Background technique

Cyanide is a highly toxic substance, which can enter the human body through the respiratory tract, digestive tract and skin, and binds to the ferric iron of the oxidative cytochrome oxidase in the mitochondria of the cell, preventing the reduction of the ferric iron in the oxidase and hindering the normal respiration of the cells. Causes hypoxia in the body resulting in a toxic effect. In addition, cyanide may form other harmful compounds under certain conditions, which poses a safety risk in food and beverages. Naturally occurring cyanide includes free and bound states. Bound cyanide, usually in the form of cyanogenic glucosides, forms free cyanide by hydrolysis and is therefore an important risk factor. Cyanide is an important food safety detection index of wine, and cyanide is also an important precursor substance for the formation of urethane. The free state and combined state cyanide in drinking wine and its raw materials can form a free state, and then form urethane with alcohol. There is a problem of urethane exceeding the standard in some alcoholic beverages. In order to ensure food safety and people's health, research on cyanide in alcoholic beverages is very necessary. Accurate determination of cyanide is of great significance for the control of related hazards. At present, the determination of cyanide at home and abroad is mostly used in medical testing, environment and other aspects. Determination methods mainly include colorimetry, fluorescence and headspace gas chromatography. However, the determination of bound cyanide is rare and generally requires a more complicated hydrolysis process. Colorimetric methods mainly include isonicotinic acid-pyrazolone, isonicotinic acid-barbituric acid, and pyridine-barbituric acid methods. Among them, the isonicotinic acid-barbituric acid method is the method used in GB/T5009.48-2003 to detect the content of cyanide in liquor. The method is cumbersome to operate, and there are problems of white turbidity and color interference. There are false positive interferences in the qualitative process, and the detection limit is 3mg/L, which is difficult for the determination of trace cyanide. Headspace gas chromatography uses reagents to derivatize cyanide and detects it by headspace extraction combined with GC-ECD. The cyanide detected by this method is free cyanide, and the detection limit is 2.5 μg/L. The existing methods for the detection of cyanide generally have problems such as high detection limit, easy to be interfered by the sample matrix, difficult determination of bound cyanide, cumbersome operation, complicated equipment, and large interference.

The detection of cyanide generally needs to be pretreated, and the cyanide is acidified into hydrocyanic acid before detection, while the pretreatment of bound cyanide is more complicated. At present, general pretreatment equipment often has problems such as low conversion rate, loss of hydrocyanic acid, or cumbersome operation, which makes the detection accuracy low and cannot detect the actual content in the sample well. For the determination of trace free cyanide, there are many gas phase or liquid chromatography methods at home and abroad. Generally, the free cyanide needs to be acidified and derivatized first, and then gas phase or liquid chromatography is used for determination. However, there is no direct method for the determination of trace amounts of bound cyanide.

Contents of the invention

The first object of the present invention is to provide a method for detecting trace cyanide in free state and bound state, which solves the problems of high detection limit, cumbersome operation, low detection sensitivity and easy interference of the prior art free state and bound state cyanide determination method.

A method for detecting trace amounts of free and bound cyanide, using different pretreatment methods for free and bound cyanide; the pretreatment of free cyanide is to directly acidify cyanide in the pretreatment and derivatization device Carry out the derivatization reaction; the pretreatment to the combined state cyanide is to use the boiling water bath heating distillation method to decompose and release the free state cyanide before the derivatization reaction in the pretreatment and derivation device; the derivatives are detected and calculated respectively The content of free cyanide and total cyanide, the total cyanide content minus the free cyanide content is the bound cyanide content.

The pretreatment and derivatization device includes a sample reaction bottle and a derivatization receiving bottle. The acid hydrolysis reaction in the sample reaction bottle releases free cyanide, and the released free cyanide is introduced into the derivatizing receiving bottle with a derivatizing agent through a catheter. The derivatization reaction is carried out in the derivatization receiving flask. The method for detecting free and bound cyanide specifically comprises the following steps:

(1) Pretreatment and derivatization of free and bound cyanide samples

a. The sample pretreatment and derivatization steps for the determination of free cyanide are as follows: Accurately weigh an appropriate amount of liquid sample or solid sample extract and add it to the sample reaction bottle of the pretreatment and derivatization device, open the acid inlet, and quickly add an appropriate amount of acidification Close the acid inlet immediately after the reagent to react. Turn on the controllable switch to feed nitrogen, and transfer the generated hydrocyanic acid to the derivation receiving bottle under the condition of feeding nitrogen during the reaction. Add a certain amount of derivatization reagent and internal standard solution to the derivatization receiving bottle in advance. After the reaction, the derivatives to be tested are obtained for liquid phase or gas chromatography analysis.

b. The sample pretreatment and derivatization steps for the determination of bound cyanide are as follows: Accurately weigh an appropriate amount of liquid sample or solid sample and add it to the sample reaction bottle of the pretreatment and derivatization device, and add a certain proportion of distilled water and anti-interference agent. For samples containing ethanol, first add an appropriate amount of sodium hydroxide solution for alkaline hydrolysis for 10 minutes. Then open the acid inlet, and immediately close the acid inlet after quickly adding an excessive amount of acidifying reagent. The sample vials are heated to react and distill. The condensation connecting pipe is connected with cooling water, and the hydrocyanic acid generated in the distillate is transferred to the derivation receiving bottle. Add a certain amount of derivatization reagent and internal standard solution to the derivatization receiving bottle in advance. The distillate is collected in a derivatization receiving bottle and undergoes a derivatization reaction. After the reaction is completed, the volume is constant and the derivative to be tested is obtained for liquid phase or gas chromatographic analysis.

(2) cyanide derivatives and internal standard 13C15N-cyanide derivatives are detected and analyzed by liquid chromatography-mass spectrometry;

(3) Use the LC-MS/MS-MRM method to make a cyanide standard curve, and use the internal standard method to calculate the free and bound cyanide content in the sample according to the cyanide standard curve. The contents of free cyanide and total cyanide were calculated respectively, and the total cyanide content minus the free cyanide content was the bound cyanide content.

Add a certain proportion of distilled water described in step (1) b, the ratio of sample and distilled water is 1: (5-10) g/mL, soaking time is 0-5h; Described acidifying reagent is tartaric acid, and the addition amount is sample quality 10-20%; the anti-jamming agent is the zinc acetate solution of 100g/L, and the addition amount is sample: zinc acetate is equal to 1: (1-3) g/mL; The acidifying reagent added in the step (1) a is Lactic acid, the reaction time is 15-35min.

In step (1) a and b, derivatizing agent is to comprise 2.71mmol/L dissolving with methanol 2,3-naphthyl diacetal (NDA) solution, 50mmol/L taurine solution, formaldehyde and ammoniacal liquor volume ratio are 25 : a mixed solution of 25:45:5; the internal standard solution is a 13C15N-cyanide standard solution with a concentration of 1-5 mg/L.

In step (2), the LC-MS, the chromatographic conditions are: chromatographic column: Acquity UPLC C18, 2.1×100mm, 1.7μm; column temperature 40°C; injection volume 2μL; flow rate 0.3mL/min; mobile phase: A is 2mM Ammonium acetate, B is acetonitrile, and the gradient elution procedure is as follows:

The mass spectrometry conditions are: ionization mode ESI(-); multiple reaction monitoring mass spectrometry mode; ion source temperature is 150°C; collision energy is 30eV; cone voltage is 25V; capillary pressure is 2500V.

The second object of the present invention is to provide a pretreatment and derivatization device for the determination of free and bound trace cyanide.

The pretreatment and derivatization device includes a sample reaction bottle and a derivatization receiving bottle. The acid hydrolysis reaction in the sample reaction bottle releases free cyanide, and the released free cyanide is introduced into the derivatizing receiving bottle through a catheter. , carry out the derivatization reaction in the derivatization receiving flask.

The pretreatment and derivatization device for the determination of cyanide specifically includes a sample reaction bottle (1), a derivation receiving bottle (2), a sample reaction bottle long conduit (3), a sample reaction vial short conduit (4), a derivation receiving bottle Long conduit (5), atmosphere connecting pipe (6), condensation connecting pipe (7), controllable switch (8), acid inlet (9) bottle stopper (10), cooling water outlet (11) and cooling water inlet ( 12); one end of the long conduit (3) of the sample reaction bottle extends below the liquid level at the bottom of the sample reaction bottle, and one end is connected with the controllable switch (8); one end of the long conduit (5) of the derivation receiving bottle extends into the Below the liquid level at the bottom of the derivation receiving bottle; one end of the atmosphere connecting pipe (6) extends into the deriving receiving bottle, and one end is exposed outside the bottle; the condensation connecting pipe (7) passes through the short conduit of the sample reaction bottle (4) and The long conduit (5) of the derivation receiving bottle is connected with the sample reaction bottle and the derivation receiving bottle, and the hydrocyanic acid generated in the reaction bottle is introduced into the derivation receiving bottle; the controllable switch (8) is connected with nitrogen gas.

The third object of the present invention is to provide a method for pretreatment and derivatization of bound and free trace cyanide.

Sample pretreatment and derivatization steps are as follows:

a. The sample pretreatment and derivatization steps for the determination of free cyanide are as follows: Accurately weigh an appropriate amount of liquid sample or solid sample extract and add it to the sample reaction bottle of the pretreatment and derivatization device, open the acid inlet, and quickly add an appropriate amount of acidification Close the acid inlet immediately after the reagent to react. Turn on the controllable switch to feed nitrogen, and transfer the generated hydrocyanic acid to the derivation receiving bottle under the condition of feeding nitrogen during the reaction. Add a certain amount of derivatization reagent and internal standard solution to the derivatization receiving bottle in advance. After the reaction, the derivatives to be tested are obtained for liquid phase or gas chromatography analysis.

b. The sample pretreatment and derivatization steps for the determination of bound cyanide are as follows: Accurately weigh an appropriate amount of liquid sample or solid sample and add it to the sample reaction bottle of the pretreatment and derivatization device, and add a certain proportion of distilled water and anti-interference agent. For samples containing ethanol, add an appropriate amount of sodium hydroxide solution for alkaline hydrolysis for 10 minutes. Then open the acid inlet, and immediately close the acid inlet after quickly adding an excessive amount of acidifying reagent. The sample vials are heated to react and distill. The condensation connecting pipe is connected with cooling water, and the hydrocyanic acid generated in the distillate is transferred to the derivation receiving bottle. Add a certain amount of derivatization reagent and internal standard solution to the derivatization receiving bottle in advance. The distillate is collected in a derivatization receiving bottle and undergoes a derivatization reaction. After the reaction is completed, the volume is constant and the derivative to be tested is obtained for liquid phase or gas chromatographic analysis.

The pretreatment and derivatization device includes a sample reaction bottle and a derivatization receiving bottle. The acid hydrolysis reaction in the sample reaction bottle releases free cyanide, and the released free cyanide is introduced into the derivatizing receiving bottle through a catheter. , carry out the derivatization reaction in the derivatization receiving flask.

The acidifying reagent added in step a is lactic acid, and the reaction time is 15-35min.

The derivatizing agent in steps a and b includes 2.71mmol/L 2,3-naphthyl diacetal (NDA) solution dissolved in methanol, 50mmol/L taurine solution, formaldehyde and ammonia water in a volume ratio of 25:25: 45:5 mixed solution; the internal standard solution is a ¹³ C ¹⁵ N-cyanide standard solution with a concentration of 5 mg/L.

Add a certain proportion of distilled water as described in step b, the ratio of sample to distilled water is 1:(5-10) g/mL, and the soaking time is 1-5h; the acidifying reagent is tartaric acid, and the addition is 10-10% of the sample quality. 20%; the anti-jamming agent is the zinc acetate solution of 100g/L, and the addition amount is sample: zinc acetate is equal to 1: (1-3) g/mL; In one embodiment of the present invention, said in step b Get the sample and add distilled water to soak, the ratio of sample to distilled water is 1:5g/mL, soak 2h; Described adding tartaric acid and zinc acetate, the addition amount of tartaric acid is 10-20% of sample quality, the zinc acetate solution of 100g/L The amount of addition is sample: zinc acetate is equal to 1:2g/mL; the volume ratio of the amount of sample and lactic acid added in step a is 2:1, and the derivatization reaction is carried out at room temperature for 20 minutes.

Beneficial effects of the present invention:

The way of acidification first and then derivatization is adopted to eliminate the interference of other components in drinking wine and improve the detection accuracy of cyanide. The qualitative and quantitative analysis of cyanide was carried out by liquid chromatography-mass spectrometry. The present invention utilizes a special pretreatment and derivatization device, adopts the duct exhaust method to collect the hydrocyanic acid obtained from the reaction, the whole device has good air tightness, reduces the detection inaccuracy caused by the loss of hydrocyanic acid, and can realize Detection of trace cyanide. The detection limit of the quantitative cyanide in rice wine established by the method can be as low as 0.01 μg/L, the linear correlation coefficient is greater than 0.99, the standard addition recovery rate is 93.8%-106%, and the relative standard deviation is less than 10%.

The method can directly measure the free cyanide in the sample, and indirectly measure the content of the bound cyanide. Using the pretreatment and derivatization device, the free and bound cyanide can be pretreated and derivatized according to the situation, and can be used for gas or liquid chromatographic determination. The device can respectively meet the different requirements of pretreatment for the determination of bound state and free state cyanide, and accurately detect the respective contents of bound state and free state cyanide.

The pretreatment and derivation device for the determination of cyanide provided by the method is easy and safe to operate, especially the more complicated pretreatment and derivation process for the determination of bound cyanide is combined in a set of devices, which significantly simplifies the operation and is accurate. Determination of sample cyanide content laid the foundation.

Description of drawings

Figure 1: Diagram of pretreatment and derivatization device

Figure 2: Liquid chromatogram of cyanide standard and internal standard ¹³ C ¹⁵ N-cyanide

Figure 3: Mass Spectrum of Cyanide Standard

Figure 4: Standard Curve for Cyanide Determination

detailed description

Preparation and storage of reagents:

Prepare 10g/L potassium cyanide (KCN) stock solution and store in 4°C refrigerator; prepare 5 mg/L potassium cyanide isotope (K ¹³ C ¹⁵ N) stock solution and store in 4°C refrigerator; 2.71mM 2,3- Naphthalene diacetal (NDA): Dissolve 100mg NDA in 20mL methanol, and make 10-fold dilution, and store in the dark at 4°C; 50mM taurine: Take 313mg taurine and dilute to 50mL with ultrapure water, 4 Store at ℃. Mixed derivatives, including 2,3-naphthyl diacetal (NDA), taurine, formaldehyde, ammonia water, the ratio is 25:25:45:5.

Establishment of standard curve:

Dilute the 10mg/L potassium cyanide standard stock solution into a series of standard solutions, take 2mL of each of the above solutions, add them to the sample reaction bottle of the reaction device, add 2ml of derivatizer and 20μL of 5mg/L ¹³ C ¹⁵ to the derivatization receiving bottle N-cyanide internal standard. Add 1mL lactic acid to the sample reaction bottle to start the reaction, acidify it to produce hydrocyanic acid, and transfer it to the derivatization receiving bottle to be derivatized and absorbed by the derivatizing agent. Reacted at room temperature for 20 min, and then analyzed by liquid chromatography-mass spectrometry. The ratio of the measured peak area to the isotope peak area is taken as the ordinate, and the concentration is taken as the abscissa to perform linear regression analysis and draw a standard curve.

Embodiment 1: the mensuration of free state and combined state cyanide in yellow rice wine

(1) Pretreatment and derivatization of rice wine samples:

a. Sample pretreatment and derivatization for the determination of free cyanide: Add 2 mL of rice wine sample to the sample reaction bottle of the pretreatment and derivatization device, add 1 mL of lactic acid, and convert cyanide into hydrocyanic acid. Under the condition of blowing nitrogen, transfer the hydrocyanic acid to the derivatization receiving bottle. Accurately add 2mL of derivatizer and 10μL of 1mg/L internal standard ¹³ C ¹⁵ N-cyanide standard solution in the derivatization receiving bottle in advance. The derivatization reaction between the derivatizing agent and hydrocyanic acid takes place at room temperature for 20 minutes. The derivatized product was obtained, and the content of free cyanide was detected by sample injection.

b. Sample pretreatment and derivatization for the determination of bound cyanide: add 2mL rice wine sample and 0.5mL 2g/L sodium hydroxide to the sample reaction bottle of the pretreatment and derivatization device, add 10ml saturated Tartaric acid solution and 2mL of 100g/L zinc acetate were heated and distilled in a boiling water bath, and the distillate was received in a derivation receiving bottle. Pre-accurately add 2mL of derivatizer and 100μL of 5mg/L internal standard ¹³ C ¹⁵ N-cyanide standard solution in the derivatization receiving bottle. Distillation was stopped when the distillate was close to 10 mL. The distillate was fixed to volume, and the sample was injected to detect the total cyanide content.

(2) The cyanide derivatives and internal standard ¹³ C ¹⁵ N-cyanide derivatives were detected and analyzed by Thermo Fisher TSQ Quantum Ultra EMR triple quadrupole liquid mass spectrometer.

Chromatographic conditions: Chromatographic column: Acquity UPLC C18, 2.1×100mm, 1.7μm; column temperature 40℃; injection volume 2μL; flow rate 0.3mL/min; mobile phase: A is 2mM ammonium acetate, B is acetonitrile, gradient elution program as follows:

Mass spectrometry conditions: ionization mode ESI (-); multiple reaction monitoring mass spectrometry mode; ion source temperature 150°C; collision energy 30eV; cone voltage 25V; capillary pressure 2500V.

(3) Establish the LC-MS/MS-MRM method, and use the internal standard method to quantitatively calculate the content of free and total cyanide in yellow rice wine respectively through the cyanide standard curve, and the total cyanide is calculated by subtracting free cyanide to obtain bound cyanide compound content. The results are shown in the table below:

Embodiment 2: the mensuration of total cyanide in water

(1) Sample pretreatment and derivatization:

Sample pretreatment and derivatization for the determination of total cyanide: add 2 mL of water sample to the sample reaction bottle of the pretreatment and derivatization device, add about 10 mL of distilled water, quickly add 1 g of tartaric acid and 2 mL of 100 g/L zinc acetate, and conduct boiling water The bath is heated and distilled, and the distillate is received by a derivation receiving bottle. Pre-accurately add 2mL of derivatizer and 100μL of 5mg/L internal standard ¹³ C ¹⁵ N-cyanide standard solution in the derivatization receiving bottle. Distillation was stopped when the distillate was close to 10 mL. The distillate was fixed to volume, and the sample was injected to detect the total cyanide content.

(2) The cyanide derivatives and internal standard ¹³ C ¹⁵ N-cyanide derivatives were detected and analyzed by Thermo Fisher TSQ Quantum Ultra EMR triple quadrupole liquid mass spectrometer.

Chromatographic conditions: Chromatographic column: Acquity UPLC C18, 2.1×100mm, 1.7μm; column temperature 40℃; injection volume 2μL; flow rate 0.3mL/min; mobile phase: A is 2mM ammonium acetate, B is acetonitrile, gradient elution program as follows:

Mass spectrometry conditions: ionization mode ESI (-); multiple reaction monitoring mass spectrometry mode; ion source temperature 150°C; collision energy 30eV; cone voltage 25V; capillary pressure 2500V.

(3) The LC-MS/MS-MRM method was established, and the internal standard method was used to quantitatively calculate the content of cyanide in water through the cyanide standard curve, and the measured total cyanide content was 7.49 μg/L.

Embodiment 3: Evaluation of cyanide detection method

(1) Repeatability - precision test

Six standard solutions with a concentration of 10 μg/L were tested respectively, and the final results are shown in Table 1. The test results show that this method has good reproducibility.

Table 1 Precision

(2) Recovery rate - accuracy test

Take 6 samples of yellow rice wine with a free cyanide concentration of 4.71 μg/L, add standards with concentrations of 2.5 and 10 μg/L accurately, and measure according to the above steps. The recoveries were 93.8% and 106%, respectively. See Table 2 for details.

Table 2. Recovery rates

(3) Limit of detection and limit of quantitation

When the injection volume is 2 μL and S/N=3, the LOD of cyanide determination is 0.01 μg/L; when the injection volume is 2 μL and S/N=10, the LOQ is 0.05 μg/L.

Embodiment 4: the mensuration of free state and combined state cyanide in yellow rice wine raw material

(1) Pretreatment and derivatization of rice wine raw material samples:

a. Sample pretreatment and derivatization for the determination of free cyanide: accurately add 1g of raw material sample to the sample reaction bottle of the pretreatment and derivatization device, add about 5mL distilled water to soak for 2h, add 2.5mL lactic acid, and convert cyanide into acidification into hydrocyanic acid. Under the condition of blowing nitrogen, transfer the hydrocyanic acid to the derivatization receiving bottle. Add 2 mL of derivatizing agent and 10 μL of internal standard ¹³ C ¹⁵ N-cyanide standard solution with a concentration of 1 mg/L in advance in the derivatization receiving bottle. The derivatization reaction between the derivatizing agent and hydrocyanic acid takes place at room temperature for 20 minutes. The derivatized product was obtained, and the content of free cyanide was detected by sample injection.

b. Sample pretreatment and derivatization for the determination of bound cyanide: accurately add 1g of raw material sample to the sample reaction bottle of the pretreatment and derivatization device, add about 10mL of distilled water to soak for 2h, quickly add 1g of tartaric acid and 2mL of 100g/L Zinc acetate was distilled in a boiling water bath, and the distillate was received with 2 mL of derivatizing agent. Add 2 mL of derivatizing agent and 100 μL of internal standard ¹³ C ¹⁵ N-cyanide standard solution with a concentration of 5 mg/L in advance in the derivatization receiving bottle. Distillation was stopped when the distillate was close to 10 mL. The distillate was adjusted to volume, and the final concentration of the internal standard ¹³ C ¹⁵ N-cyanide was 50 μg/L after the volume was adjusted, and the total cyanide content was detected by sample injection.

(2) The cyanide derivatives and internal standard ¹³ C ¹⁵ N-cyanide derivatives were detected and analyzed by Thermo Fisher TSQ Quantum Ultra EMR triple quadrupole liquid mass spectrometer.

Chromatographic conditions: Chromatographic column: Acquity UPLC C18, 2.1×100mm, 1.7μm; column temperature 40℃; injection volume 2μL; flow rate 0.3mL/min; mobile phase: A is 2mM ammonium acetate, B is acetonitrile, gradient elution program as follows:

Mass spectrometry conditions: ionization mode ESI (-); multiple reaction monitoring mass spectrometry mode; ion source temperature 150°C; collision energy 30eV; cone voltage 25V; capillary pressure 2500V.

(3) Establish the LC-MS/MS-MRM method, and use the internal standard method to quantitatively calculate the content of free and total cyanide in yellow rice wine respectively through the cyanide standard curve, and the total cyanide is calculated by subtracting free cyanide to obtain bound cyanide compound content. The results are shown in the table below:

The above preferred embodiments are only used to illustrate the content of the present invention. In addition, the present invention also has other implementation modes, but those skilled in the art adopt equivalent replacement or equivalent deformation methods due to the technical inspiration involved in the present invention. The formed technical solutions all fall within the protection scope of the present invention.

Claims (10)

1. a method for detecting free state and bound state trace cyanide, is characterized in that, utilizes same pretreatment and derivation device, adopts different pretreatment modes to free state and bound state cyanide; To the pretreatment of free state cyanide The treatment is to directly acidify the cyanide in the pretreatment and derivatization device and then carry out the derivation reaction; the pretreatment of the combined cyanide is to decompose and release the free cyanide in the pretreatment and derivation device by heating and distillation in a boiling water bath Derivatization reaction of the derivatives; LC-MS detection of the derivatives and calculation of the cyanide content; The pretreatment and derivatization device includes a sample reaction bottle and a derivatization receiving bottle. The acid hydrolysis reaction in the sample reaction bottle releases free cyanide, and the released free cyanide is introduced into the derivatizing receiving bottle through a catheter. , carry out the derivatization reaction in the derivatization receiving flask. 2. a kind of method for detecting free state and bound state trace cyanide according to claim 1, is characterized in that, specifically comprises the following steps: (1) Pretreatment and derivatization of free and bound cyanide samples a. The sample pretreatment and derivatization steps for the determination of free cyanide are as follows: Accurately weigh an appropriate amount of liquid sample or solid sample extract and add it to the sample reaction bottle of the pretreatment and derivatization device, open the acid inlet, and quickly add an appropriate amount of acidification Close the acid inlet immediately after the reagent to react. Turn on the controllable switch to feed nitrogen, and transfer the generated hydrocyanic acid to the derivation receiving bottle under the condition of feeding nitrogen during the reaction. Add a certain amount of derivatization reagent and internal standard solution to the derivatization receiving bottle in advance. After the reaction, the derivatives to be tested are obtained for liquid phase or gas chromatography analysis. b. The sample pretreatment and derivatization steps for the determination of bound cyanide are as follows: Accurately weigh an appropriate amount of liquid sample or solid sample and add it to the sample reaction bottle of the pretreatment and derivatization device, and add a certain proportion of distilled water and anti-interference agent. For samples containing ethanol, first add an appropriate amount of sodium hydroxide solution for alkaline hydrolysis for 10 minutes. Then open the acid inlet, and immediately close the acid inlet after quickly adding an excessive amount of acidifying reagent. The sample vials are heated to react and distill. The condensation connecting pipe is connected with cooling water, and the hydrocyanic acid generated in the distillate is transferred to the derivation receiving bottle. Add a certain amount of derivatization reagent and internal standard solution to the derivatization receiving bottle in advance. The distillate is collected in a derivatization receiving bottle and undergoes a derivatization reaction. After the reaction is completed, the volume is constant and the derivative to be tested is obtained for liquid phase or gas chromatographic analysis. (2) detection and analysis of cyanide derivatives and internal standard ¹³ C ¹⁵ N-cyanide derivatives by liquid chromatography-mass spectrometry; (3) Use the LC-MS/MS-MRM method to make a cyanide standard curve, and use the internal standard method to calculate the free and bound cyanide content in the sample according to the cyanide standard curve. 3. A method for detecting free and bound trace cyanides according to claim 2, characterized in that the acidifying reagent added in step (1) a is lactic acid, and the reaction time is 15-35min. 4. a kind of method for detecting free state and bound state trace cyanide according to claim 2, is characterized in that, described in step (1) b adds the distilled water of a certain proportion, and the ratio of sample and distilled water is 1:(5 -10) g/mL, soaking time is 0-5h; Described acidifying reagent is tartaric acid, and addition is 10-20% of sample mass; Described anti-jamming agent is zinc acetate solution, and the concentration of described zinc acetate solution is 100g/L, the amount added is sample: zinc acetate is 1: (1-3) g/mL. The alkaline hydrolysis sodium hydroxide solution is 0.5-1mL 2g/L sodium hydroxide solution, and the alkali hydrolysis takes 10 minutes. 5. a kind of method for detecting free state and bound state cyanide according to claim 2, is characterized in that, in step (1) a and b, derivative agent is to comprise 2.71mmol/L dissolves with methanol 2,3-naphthalene NDA solution, 50mmol/L taurine solution, formaldehyde and ammonia water volume ratio are a mixed solution of 25:25:45:5; the internal standard solution is a concentration of 1-5mg/L ¹³ C ¹⁵ N-cyanide standard solution. 6. A pretreatment and derivation device for cyanide determination, characterized in that: the pretreatment and derivation device for cyanide determination includes a sample reaction bottle and a derivation receiving bottle, and acidolysis reaction is carried out in the sample reaction bottle to release Free cyanide is released, and the released free cyanide is introduced into the derivation receiving bottle through the catheter, and a derivatizing agent is added in the derivation receiving bottle to receive the free cyanide generated in the reaction bottle and perform derivatization; The pretreatment and derivatization device for the determination of cyanide specifically includes a sample reaction bottle (1), a derivation receiving bottle (2), a sample reaction bottle long conduit (3), a sample reaction vial short conduit (4), a derivation receiving bottle Long conduit (5), atmosphere connecting pipe (6), condensation connecting pipe (7), controllable switch (8), acid inlet (9) bottle stopper (10), cooling water outlet (11) and cooling water inlet ( 12); one end of the long conduit (3) of the sample reaction bottle extends below the liquid level at the bottom of the sample reaction bottle, and one end is connected with the controllable switch (8); one end of the long conduit (5) of the derivation receiving bottle extends into the Below the liquid level at the bottom of the derivation receiving bottle; one end of the atmosphere connecting pipe (6) extends into the deriving receiving bottle, and one end is exposed outside the bottle; the condensation connecting pipe (7) passes through the short conduit of the sample reaction bottle (4) and The long conduit (5) of the derivation receiving bottle is connected with the sample reaction bottle and the derivation receiving bottle, and the hydrocyanic acid generated in the reaction bottle is introduced into the derivation receiving bottle; the controllable switch (8) is connected with nitrogen gas. 7. A pretreatment method for the determination of free and bound trace cyanide, characterized in that the steps are as follows: a. The sample pretreatment and derivatization steps for the determination of free cyanide are as follows: Accurately weigh an appropriate amount of liquid sample or solid sample extract and add it to the sample reaction bottle of the pretreatment and derivatization device, open the acid inlet, and quickly add an appropriate amount of acidification Close the acid inlet immediately after the reagent to react. Turn on the controllable switch to feed nitrogen, and transfer the generated hydrocyanic acid to the derivation receiving bottle under the condition of feeding nitrogen during the reaction. Add a certain amount of derivatization reagent and internal standard solution to the derivatization receiving bottle in advance. After the reaction, the derivatives to be tested are obtained for liquid phase or gas chromatography analysis. b. The sample pretreatment and derivatization steps for the determination of bound cyanide are as follows: Accurately weigh an appropriate amount of liquid sample or solid sample and add it to the sample reaction bottle of the pretreatment and derivatization device, and add a certain proportion of distilled water and anti-interference agent. For samples containing ethanol, first add an appropriate amount of sodium hydroxide solution for alkaline hydrolysis for 10 minutes. Then open the acid inlet, and immediately close the acid inlet after quickly adding an excessive amount of acidifying reagent. The sample vials are heated to react and distill. The condensation connecting pipe is connected with cooling water, and the hydrocyanic acid generated in the distillate is transferred to the derivation receiving bottle. Add a certain amount of derivatization reagent and internal standard solution to the derivatization receiving bottle in advance. The distillate is collected in a derivatization receiving bottle and undergoes a derivatization reaction. After the reaction is completed, the volume is constant and the derivative to be tested is obtained for liquid phase or gas chromatographic analysis. 8. according to the pretreatment method that free state and bound state trace cyanide of claim 7 measure, it is characterized in that, the pretreatment of described free state and bound state cyanide is carried out in pretreatment and derivation device, and described pretreatment The derivatization device includes a sample reaction bottle and a derivatization receiving bottle. The acid hydrolysis reaction in the sample reaction bottle releases free cyanide, and the released free cyanide is introduced into the derivatization receiving bottle through a catheter. The free cyanide generated in the reaction bottle is received in the bottle and derivatized. 9. a kind of free state according to claim 7 and bound trace cyanide measure pretreatment method, it is characterized in that, described in step b, add the distilled water of a certain proportion, the ratio of sample and distilled water is 1:(5-10 ) g/mL, the soaking time is 0-5h; the acidifying agent is tartaric acid, and the addition amount is 10-20% of the sample mass; the anti-interference agent is 100g/L zinc acetate solution, and the addition amount is sample: acetic acid Zinc is equal to 1:(1-3)g/mL; The acidifying reagent added in step a is lactic acid, and the reaction time is 15-35min; The derivatizing agent in steps a and b includes 2.71mmol/L 2,3-naphthyl diacetal (NDA) solution dissolved in methanol, 50mmol/L taurine solution, formaldehyde and ammonia water in a volume ratio of 25:25: 45:5 mixed solution; the internal standard solution is a ¹³ C ¹⁵ N-cyanide standard solution with a concentration of 1-5 mg/L. 10. The application of the detection method of the free state and bound state trace cyanide as described in any one of claims 2-5 in detecting yellow rice wine and raw material cyanide thereof.