CN115356336B - Method for rapidly detecting trace dibromophosphate residue in agricultural products - Google Patents
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Abstract
The invention discloses a method for rapidly detecting trace dibromophosphate residue in agricultural products, which comprises the following steps: step a, preprocessing to obtain a first object to be detected; step b, extracting and filtering to obtain a first solution to be detected; c, adding the reaction solution, and reacting to obtain a second solution to be detected; step d, adding a sodium hydroxide solution for layered extraction, adding a saturated sodium chloride solution into the lower layer, uniformly mixing, and heating for reaction to obtain a third solution to be detected; step e, adding a third solution to be tested into the newly prepared copper hydroxide suspension, heating, and observing the phenomenon; and f, judging the result. The method has the advantages of simple and understandable principle, strong specificity, high sensitivity, visual detection result, high accuracy of the detection result, no need of large-scale analytical instruments, relatively less time consumption, extremely low uniform analysis cost, suitability for on-site rapid detection of the dibromophosphate residue in agricultural products and strong practicability.
Description
Technical Field
The invention relates to the field of agricultural product detection, in particular to a method for rapidly detecting trace dibromophosphate residue in agricultural products.
Background
Phosphorus dibromide is an organophosphorus insecticide produced by the reaction of dichlorvos with bromine. High effect, broad spectrum, mainly contact killing action, stomach poisoning and fumigating action. It is a systemic insecticide and acaricide, used for controlling pests of crops such as vegetables, fruit trees and the like to be harvested.
2021 version GB 2763 stipulates 10092 residual limit standards of 2,4-D564 pesticides in 376 foods, and compared with 2019 version GB 2763, 2021 version GB 2763 adds 81 new pesticides, and accordingly increases limit standards 1343. Wherein, the dibromophosphate is one of the newly added pesticides, and the latest national standard GB/T2763-2021 maximum residue limit of pesticides in food requires that the limit value of the dibromophosphate in vegetables and fruits is 0.01mg/kg. Although more and more enterprises and public institutions and various scientific research institutions have carried out a great deal of research work on detection methods of newly added pesticides such as the phosphorus dibromide, no detection method or means suitable for quick detection exists for the phosphorus dibromide pesticide variety.
The current commercial methods for detecting the dibromophosphate mainly comprise the following methods:
the first is the determination of organophosphorus, organochlorine, pyrethroid and carbamate pesticide multi-residue in NY/T761-2008 vegetables and fruits, which is detected by gas chromatography; and secondly, measuring the residual amount of the dibromophosphate in SN/T0706-2013 animal derived food, wherein a gas chromatography detection method using an ECD detector and a liquid chromatography-mass spectrometry/mass spectrometry detection method are described in the method. The methods all relate to large-scale instruments and equipment, and although the dibromophosphate can be detected, the methods are difficult to operate, complicated in processing steps, long in time consumption, low in fault tolerance rate and high in requirements on operators. It is not sufficient for the growing demand for rapid detection. And the dibromophosphate is stable under the anhydrous condition and can be quickly decomposed in water, so that the existing quick detection method for other organophosphorus pesticides is difficult to accurately detect the residual dibromophosphate. Therefore, a method for rapidly detecting trace dibromophosphate residue in agricultural products without depending on large-scale instruments and equipment needs to be developed.
Disclosure of Invention
The invention aims to provide a method for rapidly detecting trace dibromophosphate residue in agricultural products.
According to one aspect of the invention, the method for rapidly detecting trace dibromophosphate residue in agricultural products comprises the following steps:
step a, weighing a certain amount of a homogenized sample to be detected after removing sludge, putting the sample to be detected into a beaker, adding ethylenediamine-N-propylsilane, octadecylsilane chemically bonded silica and acetonitrile, fully mixing uniformly, standing, filtering by a filter membrane, discarding filtrate, and reserving solid filter residues to obtain a first object to be detected; adding ethylenediamine-N-propyl silane, octadecylsilane chemically bonded silica and acetonitrile, wherein the ethylenediamine-N-propyl silane is used for adsorbing and removing impurities such as organic acid, pigments, metal ions, phenols and the like in a sample to be detected, the octadecylsilane chemically bonded silica is used for adsorbing and removing oily impurities in the sample to be detected, and the acetonitrile is used as a solvent to provide environmental conditions and eliminate interference of other impurities in the sample to be detected on extraction of the dibromophosphate. Filtering the pre-treated sample to be detected by using a filter membrane to obtain a first object to be detected, and extracting the phosphorus dibromide which may be contained in the subsequent steps;
b, transferring the first to-be-detected object to a first centrifuge tube, adding a mixed solution of acetone and n-hexane, uniformly mixing by shaking, filtering again, discarding solid residues, and reserving filtrate to obtain a first to-be-detected liquid; extracting the dibromophosphate remained in the first object to be detected into a first liquid to be detected by using a mixed solution of acetone and normal hexane;
step c, transferring the first solution to be detected into a second centrifuge tube, drying to obtain a second object to be detected, adding a mixed solution of dodecyl mercaptan and N-methylpyrrolidone into the second object to be detected, shaking to mix uniformly, adding a dichloromethane solution of anhydrous aluminum chloride and an ethanol solution of sodium hydroxide, shaking to mix uniformly, keeping ice bath at 0-5 ℃ for reaction, and obtaining a second solution to be detected after the reaction is finished; the reaction in this step is represented by the following formula (I):
In the step, anhydrous aluminum chloride and dodecanethiol are used together, and N-methylpyrrolidone is used for providing a solvent environment for a reaction system, so that the reaction yield is improved conveniently. Respectively carrying out hydroxylation reaction on anhydrous aluminum chloride and dodecyl mercaptan and phosphorus dibromide under the condition of ice bath at 0-5 ℃ under the alkaline condition to convert phosphate groups of the phosphorus dibromide into phosphate groups. By controlling the reaction to be carried out in a low-temperature state, the reaction can be effectively carried out, the danger caused by the excessively violent reaction when the reaction is carried out by independently using the anhydrous aluminum chloride can be avoided, and the generation of byproducts can be inhibited. The aluminum chloride belongs to strong Lewis acid, hydrochloric acid gas can be generated when the anhydrous aluminum chloride is singly used for hydroxylation reaction, the smoke is very large, the aluminum chloride has deliquescence and can form an oxide film on the surface after being exposed in the air for a long time, and the aluminum chloride becomes inactive. The dodecyl mercaptan and the phosphorus dibromide are subjected to hydroxylation reaction under an alkaline condition, so that the phosphate group of the phosphorus dibromide is converted into a phosphate group;
the phosphorus dibromide is easy to generate hydrolysis reaction, when the phosphorus dibromide is hydrolyzed under alkaline condition, the formula (IV) or the formula (VII) is carried out in parallel, the formula (IV) reacts to generate dichlorvos, the dichlorvos is further hydrolyzed to generate dichloroacetaldehyde, the dichloroacetaldehyde is further hydrolyzed to generate acetaldehyde, the formula (V) and the formula (VI) are shown, the formula (VII) reacts to generate phosphate sodium salt, and the specific reaction formula is as follows:
After the phosphorus dibromide is subjected to a series of hydrolysis reactions, the generated byproducts are more in variety, and the detection reaction of the phosphorus dibromide by using the hydrolyzed product is difficult, so that the accurate detection of trace residual phosphorus dibromide is difficult. Therefore, the N-methylpyrrolidone solution of dodecanethiol, the dichloromethane solution of anhydrous aluminum chloride and the ethanol solution of sodium hydroxide are added into the second object to be detected in the step c to perform ice bath reaction, so that the phosphorus dibromide in the second object to be detected is prevented from undergoing hydrolysis reaction, the phosphorus dibromide is subjected to hydroxylation reaction, and the phosphate group of the phosphorus dibromide is converted into a phosphate group;
d, adding a sodium hydroxide solution into the second solution to be detected, shaking gently and mixing uniformly, standing for layering, taking the lower layer into a third centrifugal tube, adding a saturated sodium chloride solution, mixing uniformly, heating for reacting for 15min, and cooling to room temperature after the reaction is finished to obtain a third solution to be detected; the reaction in this step is shown in the following formulas (II) and (III):
In the step, 1mol/L sodium hydroxide solution is used for extracting the product produced in the step c, providing an alkaline environment, and removing two bromine atoms from the reaction product of the formula (I) under the heating condition to generate a double bond to obtain a reaction product of the formula (II); reacting the reaction product of the formula (II) under the heating condition of an alkaline environment to generate dichloroacetaldehyde, wherein the obtained third to-be-detected liquid contains dichloroacetaldehyde; the sodium hydroxide solution can also inhibit the generated dichloroacetaldehyde from hydrolyzing, so that the concentration of the dichloroacetaldehyde in the third solution to be detected is improved, and the subsequent detection is ensured to be carried out smoothly; the saturated sodium chloride solution is used for providing excessive sodium ions and inhibiting ionization of sodium phosphate in the reaction system so as to prevent the generated sodium phosphate from increasing the pH value of the reaction system and inhibit decomposition of dichloroacetaldehyde;
step e, dropwise adding a third solution to be detected into the newly prepared copper hydroxide suspension, continuously heating, and observing the phenomenon; and (3) reacting the third solution to be detected with the newly prepared copper hydroxide suspension, wherein if dichloroacetaldehyde is contained in the third solution to be detected, aldehyde groups in the dichloroacetaldehyde and the copper hydroxide react under the heating condition to generate brick red copper oxide precipitates. If the third solution to be detected does not contain dichloroacetaldehyde, reacting the third solution to be detected with copper hydroxide under the heating condition, and generating no brick red copper oxide precipitate;
step f, judging the result:
dropwise adding a third solution to be detected and heating to generate brick red precipitate, wherein the third solution to be detected contains dichloroacetaldehyde, and the judgment result is positive, namely the sample to be detected contains phosphorus dibromide; and (3) dropwise adding the third to-be-detected liquid and heating, wherein brick red precipitates are not generated, which indicates that the third to-be-detected liquid does not contain dichloroacetaldehyde or the concentration of dichloroacetaldehyde is low, and the third to-be-detected liquid is judged to be negative, namely the to-be-detected sample does not contain dibromophosphorus.
The invention has the beneficial effects that: compared with a chromatography method, the detection method provided by the invention has the advantages that through a chemical reaction means, target dibromophosphate is extracted from a sample to be detected, then hydroxylation reaction is carried out, phosphate groups of the dibromophosphate are generated into phosphate groups, then debromination reaction is carried out to generate double bonds, further hydrolysis is carried out to generate dichloroacetaldehyde, a newly-prepared copper hydroxide suspension is utilized to react with the dichloroacetaldehyde, dichloroacetaldehyde in a third liquid to be detected is identified, and then detection of residual dibromophosphate in the sample to be detected is realized. The method has the advantages of simple and understandable principle, strong specificity, high sensitivity, visual detection result, high accuracy of the detection result, no need of large-scale analytical instruments, relatively less time consumption, extremely low uniform analysis cost, suitability for on-site rapid detection of the dibromophosphate residue in agricultural products and strong practicability.
In some embodiments, the volume ratio of acetone to n-hexane in the mixed solution of acetone and n-hexane in step b is 1:4.
In some embodiments, the filter membrane has a pore size of 0.45 μm.
In some embodiments, the mass ratio of the dodecanethiol to the N-methylpyrrolidone in the mixed solution of the dodecanethiol and the N-methylpyrrolidone in step c is 1:9. N-methyl pyrrolidone is used as a dispersant in the reaction of the formula (I), so that a solvent environment of a reaction system is provided, and the reaction yield is improved conveniently.
In some embodiments, the mass fraction of anhydrous aluminum chloride in the methylene chloride solution of anhydrous aluminum chloride in step c is 5%.
In some embodiments, the sodium hydroxide solution in step c has a sodium hydroxide mass fraction of 2%.
In some embodiments, the molar concentration of the sodium hydroxide solution in step d is 1mol/L.
In some embodiments, the sample to be tested is a vegetable or fruit.
In some embodiments, the temperature of the heating reaction in step d is 65 ℃.
In some embodiments, the particle size of the octadecylsilane bonded silica gel in step a is 5 to 15 μm, the pore size of the octadecylsilane bonded silica gel is: 120A.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
In this example, 97% of ethylenediamine-N-propylsilane supplied by Sigma Aldrich trade company, inc. was selected as ethylenediamine-N-propylsilane; the octadecylsilane chemically bonded silica is O875153 octadecylsilane chemically bonded silica supplied by Shanghai Michelin Biochemical technology, inc., the particle size of the octadecylsilane chemically bonded silica is 5-15 μm, the pore diameter of the octadecylsilane chemically bonded silica is 120A, ethanol is analytically pure ethanol supplied by the national drug group chemical reagent, acetonitrile is analytically pure acetonitrile supplied by the national drug group chemical reagent, acetone is analytically pure acetone supplied by the national drug group chemical reagent, N-hexane is analytically pure hexane supplied by the national drug group chemical reagent, N-methylpyrrolidone is chromatogrAN _ SNhic grade N-methylpyrrolidone supplied by the national drug group chemical reagent, dodecanethiol is 98% dodecanethiol supplied by the national drug chemical reagent, dichloromethane is analytically pure dichloromethane supplied by the national drug group chemical reagent, anhydrous aluminum chloride is 99.999% anhydrous aluminum chloride supplied by the national drug group chemical reagent, sodium hydroxide is analytically pure sodium hydroxide supplied by the national drug group chemical reagent, and copper sulfate is analytically pure water supplied by the national drug group chemical reagent;
1mol/L sodium hydroxide solution: weighing 20g of sodium hydroxide, pouring the sodium hydroxide into a beaker, dissolving the sodium hydroxide with deionized water, injecting the sodium hydroxide into a 500ml volumetric flask by using a glass rod for drainage, and then fixing the volume to a scale mark;
saturated aqueous sodium chloride solution (20 ℃): weighing 36.0g of sodium chloride, putting the sodium chloride into a beaker, diluting the sodium chloride with deionized water, draining the solution with a glass rod, injecting the solution into a 100ml volumetric flask, and then fixing the volume to a scale mark;
ethanol solution of 2% sodium hydroxide: weighing 2g of sodium hydroxide, putting the sodium hydroxide into a beaker, dissolving the sodium hydroxide by using a small amount of ethanol (10 ml-15 ml), and then complementing the ethanol to 100g on a balance;
5% anhydrous aluminum chloride in methylene chloride: weighing 5g of anhydrous aluminum chloride, putting the anhydrous aluminum chloride into a beaker, and dissolving the anhydrous aluminum chloride with 95g of dichloromethane;
a mixed solution of dodecyl mercaptan and N-methyl pyrrolidone with the mass ratio of 1:9: weighing 10g of dodecanethiol, adding the dodecanethiol into a beaker, weighing 90g N-methyl pyrrolidone, adding the dodecanethiol into the beaker, and uniformly mixing;
fresh copper hydroxide suspension: adding 2ml of 10% sodium hydroxide solution into a 10ml test tube, dripping 4-6 drops of 2% copper sulfate solution by using a dropper, and oscillating to obtain a newly prepared copper hydroxide suspension which is prepared on site;
the reagents of this example 1 were used in the following examples 2 to 5.
Example 2
The method for rapidly detecting the trace dibromophosphate residue in the agricultural products comprises the following steps:
step a, weighing 50g of a homogenized vegetable sample to be detected, from which sludge is removed, in a 500ml beaker, adding 500mg of ethylenediamine-N-propylsilane, 300mg of octadecylsilane chemically bonded silica and 20ml of acetonitrile, fully mixing uniformly, standing, filtering through a 0.45 mu m filter membrane, discarding filtrate, and reserving solid filter residues to obtain a first object to be detected;
b, transferring the first to-be-detected object into a 15ml first centrifuge tube, adding 5ml of a mixed solution of acetone and n-hexane, wherein the volume ratio of the acetone to the n-hexane is 1:4, shaking and uniformly mixing for 5min, filtering again, discarding solid filter residues, and reserving filtrate to obtain a first to-be-detected liquid;
step c, transferring the first to-be-detected liquid into a 10ml second centrifuge tube, drying the first to-be-detected liquid by blowing nitrogen at 50 ℃ to obtain a second to-be-detected object, adding 3ml of mixed solution of dodecyl mercaptan and N-methyl pyrrolidone, the mass ratio of which is 1:9, into the second to-be-detected object, shaking the mixed solution for 10s, adding 3ml of dichloromethane solution of anhydrous aluminum chloride and 0.5ml of ethanol solution of sodium hydroxide, shaking the mixed solution for uniform mixing, keeping the mixed solution at 0 ℃ for ice bath reaction for 60min, and obtaining a second to-be-detected liquid after the reaction is finished;
d, adding 3ml of 1mol/L sodium hydroxide solution into the second solution to be detected, shaking gently and mixing uniformly for 10s, standing for layering, taking a lower water layer into a 15ml third centrifuge tube, adding 1ml of saturated sodium chloride solution, mixing uniformly, heating and reacting at 65 ℃ for 15min, and cooling to room temperature after the reaction is finished to obtain a third solution to be detected;
step e, dropwise adding a third solution to be detected into the newly prepared copper hydroxide suspension, continuously heating, and observing the phenomenon;
step f, judging the result:
and adding a third solution to be detected into the newly prepared copper hydroxide suspension, heating, and generating brick red precipitate, wherein the third solution to be detected contains dichloroacetaldehyde, and the third solution to be detected is judged to be positive, namely the vegetable sample to be detected contains the dibromophosphate.
Example 3
The method for rapidly detecting the trace dibromophosphate residue in the agricultural products comprises the following steps:
step a, weighing 50g of a homogenized fruit sample to be detected after sludge removal in a 500ml beaker, adding 450mg of ethylenediamine-N-propylsilane, 250mg of octadecylsilane chemically bonded silica and 20ml of acetonitrile, fully mixing uniformly, standing, filtering through a 0.45 mu m filter membrane, discarding filtrate, and reserving solid filter residues to obtain a first object to be detected;
step b, transferring the first object to be detected into a 15ml first centrifuge tube, adding 4ml of mixed solution of acetone and n-hexane, wherein the volume ratio of the acetone to the n-hexane is 1:4, shaking and mixing uniformly for 5min, filtering again, discarding solid filter residues, and reserving filtrate to obtain a first liquid to be detected;
step c, transferring the first to-be-detected liquid into a 10ml second centrifuge tube, drying the first to-be-detected liquid by air at the temperature of 60 ℃ to obtain a second to-be-detected object, adding 2ml of a mixed solution of dodecyl mercaptan and N-methyl pyrrolidone, the mass ratio of which is 1:9, into the second to-be-detected object, shaking the mixed solution for 10s, adding 2ml of a dichloromethane solution of anhydrous aluminum chloride and 0.5ml of an ethanol solution of sodium hydroxide, shaking the mixed solution for uniform mixing, keeping the mixed solution at the temperature of 5 ℃ for ice bath reaction for 60min, and obtaining a second to-be-detected liquid after the reaction is finished;
d, adding 2ml of 1mol/L sodium hydroxide solution into the second solution to be detected, shaking gently and mixing uniformly for 10s, standing for layering, taking a lower water layer into a 15ml third centrifuge tube, adding 1ml of saturated sodium chloride solution, mixing uniformly, heating and reacting at 65 ℃ for 15min, and cooling to room temperature after the reaction is finished to obtain a third solution to be detected;
step e, dropwise adding a third solution to be detected into the newly prepared copper hydroxide suspension, continuously heating, and observing the phenomenon;
step f, judging the result:
and adding the third solution to be detected into the newly prepared copper hydroxide suspension, heating, and then, generating no brick red precipitate, wherein the third solution to be detected does not contain dichloroacetaldehyde or the concentration of dichloroacetaldehyde is low, and judging the third solution to be detected to be negative, namely the sample to be detected does not contain dibromophosphate.
Example 4
The method for rapidly detecting the trace dibromophosphate residue in the agricultural products comprises the following steps:
step a, weighing 50g of a homogenized vegetable sample to be detected, from which sludge is removed, in a 500ml beaker, adding 500mg of ethylenediamine-N-propylsilane, 300mg of octadecylsilane chemically bonded silica and 20ml of acetonitrile, fully mixing uniformly, standing, filtering through a 0.45 mu m filter membrane, discarding filtrate, and reserving solid filter residues to obtain a first object to be detected;
b, transferring the first to-be-detected object into a 15ml first centrifuge tube, adding 5ml of a mixed solution of acetone and n-hexane, wherein the volume ratio of the acetone to the n-hexane is 1:4, shaking and uniformly mixing for 5min, filtering again, discarding solid filter residues, and reserving filtrate to obtain a first to-be-detected liquid;
step c, transferring the first to-be-detected liquid into a 10ml second centrifuge tube, drying the first to-be-detected liquid by blowing nitrogen at 55 ℃ to obtain a second to-be-detected object, adding 3ml of a mixed solution of dodecyl mercaptan and N-methyl pyrrolidone, the mass ratio of which is 1:9, into the second to-be-detected object, shaking the mixture for 10 seconds, adding 3ml of a dichloromethane solution of anhydrous aluminum chloride and 0.5ml of an ethanol solution of sodium hydroxide, shaking the mixture for uniform mixing, keeping the mixture at 2.5 ℃ for ice bath reaction for 60min, and obtaining a second to-be-detected liquid after the reaction is finished;
step d, adding 3ml of 1mol/L sodium hydroxide solution into the second liquid to be detected, shaking gently and mixing uniformly for 10s, standing for layering, taking a lower-layer water layer into a 15ml third centrifuge tube, adding 1ml of saturated sodium chloride solution, mixing uniformly, heating and reacting at 65 ℃ for 15min, and cooling to room temperature after the reaction is finished to obtain a third liquid to be detected;
step e, dropwise adding a third solution to be detected into the newly prepared copper hydroxide suspension, continuously heating, and observing the phenomenon;
step f, judging the result:
and adding the third solution to be detected into the newly prepared copper hydroxide suspension, heating, and then, generating no brick red precipitate, wherein the third solution to be detected does not contain dichloroacetaldehyde or the concentration of dichloroacetaldehyde is low, and judging the third solution to be detected to be negative, namely the sample to be detected does not contain dibromophosphate.
Example 5
Selecting a negative vegetable sample to be detected, adding dibromophosphate into the negative vegetable sample to be detected according to the concentrations of 0.005mg/kg, 0.01mg/kg and 0.05mg/kg, then homogenizing, preparing to obtain homogenized added samples to be detected (3 times of treatment for each time) with different treatment concentrations, and detecting the homogenized added samples to be detected and the homogenized control samples by taking the negative vegetable sample to be detected as control samples (3 times of treatment) according to the detection method of example 2, wherein the detection results are shown in the following table 1.
TABLE 1 Dibromophos gradient concentration addition experiment detection results
As can be seen from the table 1, the detection method provided by the invention can be used for qualitatively detecting a sample to be detected with the content of the dibromophosphate of more than or equal to 0.01mg/kg, meets the detection requirement of the latest national standard GB/T2763-2021 food pesticide maximum residue limit on the limit of the dibromophosphate in vegetables and fruits of 0.01mg/kg, is suitable for on-site rapid detection of the dibromophosphate residue in agricultural products, and has strong practicability.
The above description is only for the embodiments of the present invention, and it is obvious to those skilled in the art that various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (10)
1. The method for rapidly detecting trace dibromophosphate residue in agricultural products comprises the following steps:
step a, weighing a certain amount of a homogenized sample to be detected after removing sludge, putting the sample to be detected into a beaker, adding ethylenediamine-N-propylsilane, octadecylsilane chemically bonded silica and acetonitrile, fully mixing uniformly, standing, filtering by a filter membrane, discarding filtrate, and reserving solid filter residues to obtain a first object to be detected;
b, transferring the first to-be-detected object to a first centrifugal tube, adding a mixed solution of acetone and normal hexane, shaking and uniformly mixing, filtering again, discarding solid residues, and reserving filtrate to obtain a first to-be-detected liquid;
step c, transferring the first solution to be detected into a second centrifuge tube, drying to obtain a second object to be detected, adding a mixed solution of dodecyl mercaptan and N-methylpyrrolidone into the second object to be detected, shaking to mix uniformly, adding a dichloromethane solution of anhydrous aluminum chloride and an ethanol solution of sodium hydroxide, shaking to mix uniformly, keeping ice bath reaction at 0-5 ℃, and obtaining a second solution to be detected after the reaction is finished;
d, adding a sodium hydroxide solution into the second solution to be detected, shaking gently and mixing uniformly, standing for layering, taking the lower layer into a third centrifugal tube, adding a saturated sodium chloride solution, mixing uniformly, heating for reacting for 15min, and cooling to room temperature after the reaction is finished to obtain a third solution to be detected;
step e, dropwise adding the third solution to be detected into the newly prepared copper hydroxide suspension, continuously heating, and observing the phenomenon;
step f, judging the result:
dropwise adding the third solution to be detected and heating to generate brick red precipitate, wherein the brick red precipitate indicates that the third solution to be detected contains dichloroacetaldehyde, and the judgment result is positive, namely the sample to be detected contains phosphorus dibromide; and (3) dropwise adding the third to-be-detected liquid and heating, wherein no brick red precipitate is generated, which indicates that the third to-be-detected liquid does not contain dichloroacetaldehyde or the concentration of dichloroacetaldehyde is low, and the third to-be-detected liquid is judged to be negative, namely the to-be-detected sample does not contain phosphorus dibromide.
2. The method for rapidly detecting the trace dibromophosphorus residue in the agricultural products as claimed in claim 1, wherein the volume ratio of the acetone to the n-hexane in the mixed solution of the acetone and the n-hexane in the step b is 1:4.
3. The method for rapidly detecting trace dibromophosphate residue in agricultural products as claimed in claim 1, wherein the pore size of the filter membrane is 0.45 μm.
4. The method for rapidly detecting the trace dibromophosphorus residue in the agricultural products as claimed in claim 1, wherein the mass ratio of the dodecanethiol to the N-methylpyrrolidone in the mixed solution of the dodecanethiol and the N-methylpyrrolidone in the step c is 1:9.
5. The method for rapidly detecting trace dibromophosphate residue in agricultural products according to claim 1, wherein the mass fraction of the anhydrous aluminum chloride in the dichloromethane solution of the anhydrous aluminum chloride in the step c is 5%.
6. The method for rapidly detecting the trace dibromophosphate residue in the agricultural products according to claim 1, wherein the mass fraction of the sodium hydroxide in the ethanol solution of the sodium hydroxide in the step c is 2%.
7. The method for rapidly detecting the trace dibromophosphate residue in the agricultural products according to claim 1, wherein the molar concentration of the sodium hydroxide solution in the step d is 1mol/L.
8. The method for rapidly detecting trace dibromophosphate residue in agricultural products according to claim 1, wherein the sample to be detected is a vegetable or a fruit.
9. The method for rapidly detecting trace dibromophosphate residue in agricultural products according to claim 1, wherein the temperature of the heating reaction in the step d is 65 ℃.
10. The method for rapidly detecting the trace dibromophosphorus residue in the agricultural products as claimed in claim 1, wherein the particle size of the octadecylsilane bonded silica in the step a is 5-15 μm, and the pore size of the octadecylsilane bonded silica is as follows: 120A.
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