CN108107132B - Method for detecting total content of phenol in leather and leather products thereof - Google Patents
Method for detecting total content of phenol in leather and leather products thereof Download PDFInfo
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention relates to the technical field of analysis and detection, in particular to a method for detecting the total content of phenol in leather and leather products thereof. The method comprises the following steps: 1) sample preparation: cutting a leather sample into a sample with the size of 5mm multiplied by 5mm, and uniformly mixing the sample to be detected; 2) digesting a sample; 3) acetylation reaction: transferring the filtrate into a separating funnel, adding 2mL of acetic anhydride and 3mL of n-hexane, extracting for 30min by using an oscillator, centrifuging for 5min by using a centrifugal machine, standing, taking the upper n-hexane extract, fixing the volume to 3mL, filtering by using a 0.45-micrometer organic filter membrane, and waiting to be measured; 4) analyzing and detecting: analyzing and detecting the liquid to be detected obtained in the step 3) by using a gas chromatography-mass spectrometry technology; 5) and (4) carrying out quantitative calculation. The detection method is simple, rapid, accurate and automatic, and is suitable for quality control of enterprise production, quality control in the circulation field and supervision control of related product safety.
Description
Technical Field
The invention relates to the technical field of analysis and detection, in particular to a method for detecting the total content of phenol in leather and leather products thereof.
Background
Phenol is an important basic organic chemical raw material, and downstream products of phenol relate to a plurality of fields. Is mainly used for manufacturing phenolic resin, bisphenol A and caprolactam in industry. In addition, phenol derivatives such as halophenols, nitrophenols, alkylphenols can be used in the production of pharmaceuticals, pesticides, paints, dyes, explosives, petroleum additives, paint strippers, wood preservatives, fragrances and the like. In leather and leather products, phenols may come from disinfectants, antioxidants, surfactants, dyeing aids, varnishes, coatings, adhesives, retanning agents, flame retardants, and the like, derived from leather processing.
Phenol has strong corrosive effect on skin and mucosa, and can inhibit central nerve or damage liver and kidney functions. Inhalation of high concentration steam can cause headache, dizziness, asthenia, blurred vision, pulmonary edema, etc. The patients who take the medicine by mistake burn the digestive tract, and burn pain, the exhaled air has phenolic smell, vomitus or stool can carry blood, the possibility of gastrointestinal perforation can occur, shock, pulmonary edema, liver or kidney damage can occur, acute renal failure can occur, and the patients can die of respiratory failure. Contact with eyes can cause burn, phenol is absorbed by burned skin, and after a certain incubation period, acute renal failure can be caused. Therefore, the method has important practical significance for detecting the phenol content in the leather.
At present, no relevant report of the detection technology of the total phenol content in leather and products thereof is found. The standard method for measuring phenol comprises GB/T30696-2014 measuring free phenol of rigid phenolic foam products, wherein free phenol in a sample is extracted by acetone, a hydride ionization detector of a gas chromatograph is used for measuring, and the content is quantified by an internal standard method. Standard methods for determining the content of phenols in Leather are ISO17070 2015(E) Leather-Chemical tests-Determination of the content of (for example) dechlorophenol-, trichlorophenonol-, dichlorphenonol-, monochlorophenonol-isochromasor and pentachlorophenol content (Determination of the content of the four, three, two, monochlorophenol-isomers and pentachlorophenol in Leather chemistry), which is carried out by adding a solution of sulphuric acid to the sample and then measuring the content of chlorophenols in the Leather sample by steam distillation, n-hexane extraction, gas chromatograph Electron Capture Detector (ECD) and external standard methods.
Disclosure of Invention
The invention aims to provide a method for detecting the total content of phenol in leather and leather products aiming at the defects of the prior art. The detection method is simple, rapid, accurate and automatic, is suitable for quality control of enterprise production, quality control in the circulation field and supervision control of related product safety, and fills up the technical blank of detection of phenol content in leather and leather products in China.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for detecting the content of phenol in leather and leather products thereof comprises the following steps:
1) sample preparation: cutting a leather sample into a sample with the size of 5mm multiplied by 5mm, and uniformly mixing the sample to be detected;
2) sample digestion: accurately weighing 2.000g of sample in a conical flask with a plug, adding 20mL of 1mol/L potassium hydroxide solution, digesting in an ultrasonic cleaner at 70 ℃ for 60min, adding 20mL of potassium carbonate solution, digesting for 60min, and filtering; (the concentration of potassium hydroxide cannot be lower than 1mol/L, the temperature cannot be lower than 70 ℃, otherwise, the digestion is incomplete, and the detection result is influenced)
3) Acetylation reaction: transferring the filtrate into a separating funnel, adding 2mL of acetic anhydride and 3mL of n-hexane, extracting for 30min by using an oscillator, centrifuging for 5min by using a centrifugal machine, standing, taking the upper n-hexane extract, fixing the volume to 3mL, filtering by using a 0.45-micrometer organic filter membrane, and waiting to be measured;
4) analyzing and detecting: analyzing and detecting the liquid to be detected obtained in the step 3) by using a gas chromatography-mass spectrometry technology;
5) and (3) quantitative calculation: substituting the parameter values obtained in the step 4) into the following formula (1) to calculate so as to obtain the actual measured value of phenol in the leather;
in the formula:
Xphenol content in mg of samplePer kilogram (mg/kg);
c-phenol concentration in the sample extract in milligrams per liter (mg/L);
c o-phenol concentration in milligrams per liter (mg/L) in the blank solution;
v-volume of n-hexane extract in milliliters (mL);
mthe mass of the sample in grams (g).
And 2) digesting the sample, ensuring that the leather sample is fully dissolved, avoiding incomplete extraction and having low extraction efficiency. And 3) acetic anhydride is adopted to perform acetylation reaction on the phenol, so that the structure of the phenol is more stable, and the target object to be detected is prevented from being oxidized or reduced, thereby ensuring the accuracy of the phenol content result in the detection sample.
The step 4) is specifically as follows: performing on-machine analysis on the liquid to be detected obtained in the step 3) to obtain a response signal of the phenol to be detected in the liquid to be detected, then selecting a standard working solution corresponding to a response value according to the response signal of the phenol to be detected in the liquid to be detected to perform chromatographic analysis, wherein the standard working solution is provided with six concentration gradients including a zero point, the response values of the phenol substances in the standard working solution and the phenol substances in the liquid to be detected are both within a linear response range of an instrument, and a blank control is set at the same time.
The conditions of the gas chromatograph mass spectrometer in the step 4) are as follows:
a) a chromatographic column: 5% phenyl dimethyl polyarylene siloxane quartz capillary column, length 30m, inner diameter 0.25 mm, film thickness 0.25 μm, or equivalent;
b) carrier gas: helium with purity more than or equal to 99.999%;
c) carrier gas flow: 1 mL/min;
d) sample introduction temperature: 200 ℃;
e) sample introduction amount: 1 mu L;
f) an ionization mode: an EI source;
g) ionization energy: 70 eV;
h) the detection mode is as follows: selective ion detection (SIM);
i) interface temperature of chromatography-mass spectrometry: 230 ℃;
j) temperature program of chromatographic column: the initial temperature is maintained at 50 deg.C for 2min, then raised to 180 deg.C at 20 deg.C/min for 2min, and then raised to 240 deg.C at 40 deg.C/min for 2 min.
The invention has the beneficial effects that:
(1) the method is simple and quick, has less steps, can avoid the loss of the target object, improves the accuracy of the experiment, and can reduce the environmental pollution caused by the experiment due to the lower toxicity of the used solvent.
(2) The detection method is accurate and reliable, the phenol content in the leather has good linearity within the range of 1-100 mg/L, the correlation coefficient r is greater than 0.9996, and the standard recovery rate is between 85.0-107.2%.
(3) The invention is suitable for quality control of enterprise production, quality control in the field of circulation and supervision control of related product safety, and fills up the technical blank of detection of phenol content in leather and leather products in China.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
The method for detecting the phenol content in the leather specifically comprises the following operation steps:
step one, sample preparation:
and (3) cutting the leather sample into a sample with the size of 5mm multiplied by 5mm, and uniformly mixing the sample to be detected.
Step two, extraction
Accurately weighing 2.0 g (to 1 mg) of the sample in a conical flask with a stopper. Adding 20mL of 1mol/L potassium hydroxide solution, extracting for 60min in an ultrasonic cleaner at 70 ℃, and then adding 20mL of 0.1 mol/L potassium carbonate solution for extracting for 60 min; transferring the filtrate into a separating funnel, adding 2mL of acetic anhydride and 3mL of n-hexane, extracting for 30min by using an oscillator, centrifuging for 5min by using a centrifugal machine, standing, taking the upper n-hexane extract, fixing the volume to 3mL, and filtering by using a 0.45-micrometer organic filter membrane to be detected.
Step three, analysis and detection:
analyzing and detecting the obtained detection liquid by using a gas chromatography-mass spectrometry technology, specifically, performing on-machine analysis on the detection liquid to obtain a response signal of a detected phenol in the detection liquid, then selecting a standard working liquid corresponding to a response value according to the response signal of the detected phenol in the detection liquid to perform chromatographic analysis, wherein the standard working liquid is provided with six concentration gradients including a zero point, the response values of phenol substances in the standard working liquid and the detection liquid are both in a linear response range of an instrument, and a blank control is set at the same time;
step four, quantitative calculation:
substituting various parameter values obtained by a gas chromatography-mass spectrometry method into the following formula (1) for calculation so as to obtain an actual measured value of phenol in the leather;
in the formula:
X-phenol content in milligrams per kilogram (mg/kg) in the sample;
c-phenol concentration in the sample extract in milligrams per liter (mg/L);
c o-phenol concentration in milligrams per liter (mg/L) in the blank solution;
v-volume of n-hexane extract in milliliters (mL);
mthe mass of the sample in grams (g).
The results of the two measurements were averaged and retained one decimal place.
Further, the conditions of the gas chromatography-mass spectrometer were:
a) a chromatographic column: 5% phenyl dimethyl polyarylene siloxane quartz capillary column, length 30m, inner diameter 0.25 mm, film thickness 0.25 μm, or equivalent;
b) carrier gas: helium with purity more than or equal to 99.999%;
c) carrier gas flow: 1 mL/min;
d) sample introduction temperature: 200 ℃;
e) sample introduction amount: 1 mu L;
f) an ionization mode: an EI source;
g) ionization energy: 70 eV;
h) the detection mode is as follows: selective ion detection (SIM);
i) interface temperature of chromatography-mass spectrometry: 230 ℃;
j) temperature program of chromatographic column: the initial temperature is maintained at 50 deg.C for 2min, then raised to 180 deg.C at 20 deg.C/min for 2min, and then raised to 240 deg.C at 40 deg.C/min for 2 min.
k) Then according to the characteristic ion fragments 94, 136, 66, 43 of phenol and the abundance ratio 100: 16: 12: 18, quantifying the ion fragments 94.
l) the detection limit of the method is 0.04mg/kg, the recovery rate is 85-107.2%, the Relative Standard Deviation (RSD) is within 8.0%, and the correlation coefficient is larger than 0.9996.
For better illustration of the present invention, the following examples are given, and the feasibility and accuracy of the detection method of the present invention are verified in each example.
Example 1
Sample to be tested-negative leather sample (negative sample)
Sample preparation:
1. preparing an extracting solution:
and (3) cutting the negative leather sample into a sample with the size of 5mm multiplied by 5mm, and uniformly mixing the samples to be detected. Six portions of 2.0 g (to 1 mg) leather sample are accurately weighed into a conical flask with a stopper. And (5) carrying out extraction operation according to the second step, and detecting the extracting solution.
2. Analyzing and detecting:
the extract solutions prepared in the above 1 were sequentially operated according to the third and fourth steps of the present invention, respectively, and the respective actual measurement values obtained by the final calculation are listed in table 1, and the average value of the actual measurement values and RSD (relative standard deviation) are calculated as shown in table 1, and the average value is the background value. Negative samples were added with 0.5 mg/L, 1.0 mg/L and 1.5mg/L phenol, and the recovery and RSD are shown in Table 1.
TABLE 1 background determination data for phenol content in negative leather samples (n = 6)
Example 2
Sample to be tested-positive leather sample (positive sample)
Sample preparation:
1. preparing an extracting solution:
and (3) shearing the positive leather sample into a sample with the size of 5mm multiplied by 5mm, and uniformly mixing the samples to be detected. Six portions of 2.0 g (to 1 mg) leather sample are accurately weighed into a conical flask with a stopper. And (5) carrying out extraction operation according to the second step, and detecting the extracting solution.
2. Analyzing and detecting:
the extract solutions prepared in the above 1 were sequentially operated according to the third and fourth steps of the present invention, respectively, and the respective actual measurement values obtained by the final calculation are listed in table 1, and the average value of the actual measurement values and RSD (relative standard deviation) are calculated as shown in table 2, and the average value is the background value.
TABLE 2 determination of phenol content in positive leather samples (n = 6)
Compared with the pretreatment extraction method of the existing detection method of phenol or related phenol derivatives, GB/T30696-2014 and ISO 17070:2015(E), the detection method detects the phenol content in the leather sample, and the result is shown in Table 3.
TABLE 3 correlation method comparison
A leather positive sample containing phenol is selected and is measured by the method in the step 3, the measurement results of ISO 17070:2015(E) and GB/T30696-2014 at the 1 st time are found to be lower in the detection process, the extracted sample is extracted again at the 2 nd time, and the measurement results are shown in the table 4.
TABLE 4 results of different methods
As can be seen from Table 4, the method directly digests the leather sample and can simply and rapidly determine the total phenol content in the leather sample. Taking the total content of phenol as 100%, the recovery rate of 2 times of extraction by the ISO17070 method is 76.3%, and the recovery rate of 2 times of extraction by the method GB/T30696 is 61.9%.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (2)
1. A method for detecting the total content of phenol in leather and leather products thereof is characterized in that: the method comprises the following steps:
1) sample preparation: cutting a leather sample into a sample with the size of 5mm multiplied by 5mm, and uniformly mixing the sample to be detected;
2) sample digestion: accurately weighing 2.000g of sample in a conical flask with a plug, adding 20mL of 1mol/L potassium hydroxide solution, digesting for 60min in an ultrasonic cleaner at 70 ℃, adding 20mL of potassium carbonate solution, digesting for 60min, and filtering;
3) acetylation reaction: transferring the filtrate into a separating funnel, adding 2mL of acetic anhydride and 3mL of n-hexane, extracting for 30min by using an oscillator, centrifuging for 5min by using a centrifugal machine, standing, taking the upper n-hexane extract, fixing the volume to 3mL, filtering by using a 0.45-micrometer organic filter membrane, and waiting to be measured;
4) analyzing and detecting: analyzing and detecting the liquid to be detected obtained in the step 3) by using a gas chromatography-mass spectrometry technology;
5) and (3) quantitative calculation: substituting the parameter values obtained in the step 4) into the following formula (1) to calculate so as to obtain the actual measured value of phenol in the leather;
in the formula:
c-phenol concentration in the sample extract in milligrams per liter (mg/L);
c o-phenol concentration in milligrams per liter (mg/L) in the blank solution;
v-volume of n-hexane extract in milliliters (mL);
m-mass of the sample in grams (g);
the conditions of the gas chromatography mass spectrometer in the step 4) are as follows:
a) a chromatographic column: 5% phenyl dimethyl poly (arylene siloxane) quartz capillary column with length of 30m, inner diameter of 0.25 mm, and thickness of 0.25 μm;
b) carrier gas: helium with purity more than or equal to 99.999%;
c) carrier gas flow: 1 mL/min;
d) sample introduction temperature: 200 ℃;
e) sample introduction amount: 1 mu L;
f) an ionization mode: an EI source;
g) ionization energy: 70 eV;
h) the detection mode is as follows: selective ion detection (SIM);
i) interface temperature of chromatography-mass spectrometry: 230 ℃;
j) temperature program of chromatographic column: the initial temperature is maintained at 50 deg.C for 2min, then raised to 180 deg.C at 20 deg.C/min for 2min, and then raised to 240 deg.C at 40 deg.C/min for 2 min.
2. The method for detecting the total phenol content in leather and leather products thereof according to claim 1, wherein the method comprises the following steps: the step 4) is specifically as follows: performing on-machine analysis on the liquid to be detected obtained in the step 3) to obtain a response signal of the phenol to be detected in the liquid to be detected, then selecting a standard working solution corresponding to a response value according to the response signal of the phenol to be detected in the liquid to be detected to perform chromatographic analysis, wherein the standard working solution is provided with six concentration gradients including a zero point, the response values of the phenol substances in the standard working solution and the phenol substances in the liquid to be detected are both within a linear response range of an instrument, and a blank control is set at the same time.
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| CN110568104A (en) * | 2019-09-24 | 2019-12-13 | 杭州市质量技术监督检测院 | Method for simultaneously measuring migration volumes of various chlorinated phenols in wooden tableware |
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| CN106645448A (en) * | 2016-09-28 | 2017-05-10 | 广州纤维产品检测研究院 | Separation detection method of phenol compounds in textiles |
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