CN112526053A - Method for measuring mixed alcohol and mixed ester in industrial ethanol by gas chromatography internal standard method - Google Patents
Method for measuring mixed alcohol and mixed ester in industrial ethanol by gas chromatography internal standard method Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 150000002148 esters Chemical class 0.000 title claims abstract description 71
- 238000004817 gas chromatography Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000010813 internal standard method Methods 0.000 title claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000000243 solution Substances 0.000 claims abstract description 102
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000011550 stock solution Substances 0.000 claims abstract description 73
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 72
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 70
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 69
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000126 substance Substances 0.000 claims abstract description 60
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims abstract description 58
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims abstract description 53
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims abstract description 32
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 32
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims abstract description 32
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229940116333 ethyl lactate Drugs 0.000 claims abstract description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 8
- 229940078552 o-xylene Drugs 0.000 claims abstract description 4
- 238000001514 detection method Methods 0.000 claims description 37
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 25
- 238000004458 analytical method Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000000523 sample Substances 0.000 description 19
- 238000011084 recovery Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010606 normalization Methods 0.000 description 3
- 229940090181 propyl acetate Drugs 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 230000004151 fermentation Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
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- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
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- 238000012421 spiking Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/045—Standards internal
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
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Abstract
The invention discloses a method for measuring mixed alcohol and mixed ester in industrial ethanol by a gas chromatography internal standard method, wherein the mixed alcohol comprises methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamyl alcohol, the mixed ester comprises ethyl acetate, ethyl butyrate, ethyl caproate, ethyl lactate and butyl acetate, and the method comprises the following steps: (1) preparing a mixed alcohol and mixed ester standard stock solution; (2) preparing an internal standard stock solution, wherein the internal standard is any one of benzene, toluene and o-xylene; (3) preparing a series of standard curve solutions; (4) carrying out chromatographic analysis; (5) establishment of a standard curve: fitting to obtain a standard curve by taking the concentration ratio of the object to be measured and the internal standard substance as a horizontal coordinate x and the peak area ratio of the object to be measured and the internal standard substance as a vertical coordinate y, wherein the standard curve forcibly passes through an original point; (6) and (4) detecting the sample. The method has the advantages of simplicity, rapidness, stability, good chromatographic peak shape, high accuracy, good reproducibility and the like.
Description
Technical Field
The invention belongs to the technical field of chemical analysis, and particularly relates to a method for measuring mixed alcohol and mixed ester in industrial ethanol by a gas chromatography internal standard method.
Background
Ethanol is a flammable and volatile colorless transparent liquid at normal temperature and pressure, and has important and wide application in the aspects of food, medicine, chemical industry, fuel, printing and dyeing, energy and the like. In the fine chemical industry, ethanol is used as an important organic solvent and an original chemical material to participate in the synthesis, production, extraction and purification of various fine chemical products. In the field of petrochemical industry, ethanol can be used for preparing acetic acid, chloroethane, diethyl ether, butadiene and other chemicals which are vital in national economy, and particularly, a reverse route for preparing ethylene by ethanol dehydration is likely to promote the layout adjustment of the future petrochemical industry structure. In the energy field, ethanol can be converted into hydrogen through steam reforming and oxidation reforming and used as a direct energy supply raw material of a fuel cell, so that the problems of hydrogen storage, hydrogen distribution and the like in the prior art are solved, and the safe use of hydrogen energy is realized.
Commercially 90% ethanol is obtained by fermentation processes. The fermentation process mainly utilizes saccharides or starch raw materials (such as sugarcane, corn and cassava) to ferment under the action of microorganisms, and is obtained by distilling microbial metabolites, but the prepared ethanol contains various mixed alcohols and mixed esters, the purity is not high, the components have large influence on the production process, and the development of ethanol downstream and derivatives thereof is limited to a great extent, so that various byproducts are detected in time, the accurate analysis and quantification of industrial ethanol are realized, and the method has important significance.
At present, a gas chromatography area normalization method is generally used, the conditions of a chromatographic column are not clear, product impurities are complex in actual production, and the difference of response factors among components in gas chromatography is large, so that the content of mixed alcohol and mixed ester cannot be accurately measured by simply using an area normalization method, and the existing production requirements cannot be met.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for measuring mixed alcohol and mixed ester in industrial ethanol by a gas chromatography internal standard method, which can simultaneously measure 11 byproducts such as methanol, ethyl acetate, propyl acetate, isobutanol, isoamyl alcohol, butyl acetate, ethyl hexanoate, n-propanol, sec-butanol, n-butanol, ethyl butyrate and the like in the industrial ethanol.
A method for determining mixed alcohols including methanol, n-propanol, n-butanol, sec-butanol, iso-butanol and mixed esters including ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate in industrial ethanol by a gas chromatography internal standard method, comprising the steps of:
(1) preparing a mixed alcohol and mixed ester standard stock solution: respectively weighing methanol, n-propanol, n-butanol, sec-butanol, isobutanol, isoamylol, ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate, mixing and placing in a volumetric flask, and performing constant volume with an ethanol water solution to obtain a mixed alcohol and mixed ester standard stock solution;
(2) preparing an internal standard stock solution: weighing an internal standard substance in a volumetric flask, and performing constant volume by using an ethanol water solution to obtain an internal standard substance standard stock solution; wherein the internal standard substance is any one of benzene, toluene and o-xylene;
(3) preparing a series of standard curve solutions: respectively taking the mixed alcohol, the mixed ester standard stock solution and the internal standard substance standard stock solution, mixing in a volumetric flask, and performing constant volume by using an ethanol water solution to obtain a mixed standard curve solution; respectively preparing at least 5 mixed standard curve solutions to form a series of standard curve solutions; in the series of standard curve solutions, the concentrations of the internal standard substances are the same, and the concentrations of the mixed alcohol and the mixed ester are different;
(4) and (3) chromatographic analysis: respectively carrying out gas chromatography analysis on the series of standard curve solutions, and recording peak areas;
(5) establishment of a standard curve: fitting to obtain a standard curve by taking the concentration ratio of the object to be measured and the internal standard substance as a horizontal coordinate x and the peak area ratio of the object to be measured and the internal standard substance as a vertical coordinate y, wherein the standard curve forcibly passes through an original point, and the linear correlation coefficient is more than or equal to 0.999; wherein the substance to be detected is methanol, n-propanol, n-butanol, sec-butanol, isobutanol, isoamyl alcohol, ethyl acetate, ethyl butyrate, ethyl caproate, ethyl lactate and butyl acetate;
(6) sample detection: taking industrial ethanol of a detection sample, adding an internal standard stock solution into the industrial ethanol, and performing constant volume by using an ethanol solution to obtain a detection solution; filtering the detection solution by an organic filter membrane, performing gas chromatography, recording peak areas, and calculating according to the standard curve to obtain the concentrations of the mixed alcohol and the mixed ester in the detection sample; wherein the concentration of the internal standard substance in the detection solution is the same as the concentration of the internal standard substance in the series of standard curve solutions.
Preferably, the conditions of the gas chromatography are: the injection port temperature is 200-.
Preferably, the volume of the ethanol in the ethanol water solution accounts for 40-80%.
Preferably, in the mixed alcohol and mixed ester standard stock solutions, the concentrations of methanol, n-propanol, n-butanol, sec-butanol, iso-butanol and iso-butanol are the same and are marked as a; the concentrations of ethyl acetate, ethyl butyrate, ethyl caproate, ethyl lactate and butyl acetate are the same and are marked as b; the concentration of the internal standard substance in the internal standard substance standard stock solution is marked as c; the a, b and c satisfy the following relations: b =2a =2 c.
Preferably, the concentrations of the methanol, the n-propanol, the n-butanol, the sec-butanol, the isobutanol and the isoamyl alcohol in the mixed alcohol and mixed ester standard stock solution are all 500-2000 mg/L.
Preferably, the concentration of the mixed alcohol in the series of standard curve solutions is 20-200mg/L, and the concentration of the mixed ester is 40-400 mg/L.
Preferably, the concentration of the internal standard substance in the series of standard curve solutions is 100 mg/L.
Preferably, the pore size of the organic filter membrane is 0.22 μm.
The reagents used in the invention are analytically pure, and the purity is more than 99%.
The purity of the high-purity nitrogen used by the gas chromatography analysis of the invention is more than 99.99 percent.
The mixed alcohol and mixed ester standard stock solution simultaneously contains methanol, ethyl acetate, propyl acetate, isobutanol, isoamyl alcohol, butyl acetate, ethyl caproate, n-propanol, sec-butanol, n-butanol and ethyl butyrate.
The invention has the advantages that:
the method for determining the mixed alcohol and the mixed ester in the industrial ethanol by the gas chromatography internal standard method can detect methanol, ethyl acetate, propyl acetate, isobutanol, isoamylol, butyl acetate, ethyl hexanoate, n-propanol, sec-butanol, n-butanol and ethyl butyrate, improves the defects and shortcomings of a gas chromatography area normalization method, fills up the technical blank in the prior art, has the advantages of simplicity, rapidness, stability, good chromatographic peak shape, high accuracy, good reproducibility and the like, and has important practical significance in the fields of quality analysis, quality control and the like of ethanol and downstream derivatives thereof.
Drawings
FIG. 1 gas chromatogram.
Detailed Description
In the following examples, the sources of the reagents are directly purchased from the market, the brands are national reagents, the reagents are all analytically pure, and the purity is more than 99%.
Example 1
A method for determining mixed alcohols including methanol, n-propanol, n-butanol, sec-butanol, iso-butanol and mixed esters including ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate in industrial ethanol by a gas chromatography internal standard method, comprising the steps of:
(1) preparing a mixed alcohol and mixed ester standard stock solution: respectively weighing methanol, n-propanol, n-butanol, sec-butanol, isobutanol, isoamylol, ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate, mixing and placing in a volumetric flask, and performing constant volume with an ethanol water solution to obtain a mixed alcohol and mixed ester standard stock solution;
(2) preparing an internal standard stock solution: weighing an internal standard substance in a volumetric flask, and performing constant volume by using an ethanol water solution to obtain an internal standard substance standard stock solution; wherein the internal standard substance is any one of benzene, toluene and o-xylene;
(3) preparing a series of standard curve solutions: respectively taking the mixed alcohol, the mixed ester standard stock solution and the internal standard substance standard stock solution, mixing in a volumetric flask, and performing constant volume by using an ethanol water solution to obtain a mixed standard curve solution; respectively preparing at least 5 mixed standard curve solutions to form a series of standard curve solutions; in the series of standard curve solutions, the concentrations of the internal standard substances are the same, and the concentrations of the mixed alcohol and the mixed ester are different;
(4) and (3) chromatographic analysis: respectively carrying out gas chromatography analysis on the series of standard curve solutions, and recording peak areas;
(5) establishment of a standard curve: fitting to obtain a standard curve by taking the concentration ratio of the object to be measured and the internal standard substance as a horizontal coordinate x and the peak area ratio of the object to be measured and the internal standard substance as a vertical coordinate y, wherein the standard curve forcibly passes through an original point, and the linear correlation coefficient is more than or equal to 0.999;
(6) sample detection: taking industrial ethanol of a detection sample, adding an internal standard stock solution into the industrial ethanol, and performing constant volume by using an ethanol solution to obtain a detection solution; filtering the detection solution by an organic filter membrane, performing gas chromatography, recording peak areas, and calculating according to the standard curve to obtain the concentrations of the mixed alcohol and the mixed ester in the detection sample; wherein the concentration of the internal standard substance in the detection solution is the same as the concentration of the internal standard substance in the series of standard curve solutions;
wherein, the gas chromatography analysis conditions are that the temperature of a gas chromatography gasification chamber is 200-;
the volume of the ethanol in the ethanol water solution accounts for 40-80%;
in the mixed alcohol and mixed ester standard stock solution, the concentrations of methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamyl alcohol are the same and are marked as a; the concentrations of ethyl acetate, ethyl butyrate, ethyl caproate, ethyl lactate and butyl acetate are the same and are marked as b; the concentration of the internal standard substance in the internal standard substance standard stock solution is marked as c; the a, b and c satisfy the following relations: b =2a =2 c.
Example 2
On the basis of example 1, the concentrations of methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamylol in the mixed alcohol and mixed ester standard stock solutions are all 500-2000 mg/L;
in the series of standard curve solutions, the concentration of the mixed alcohol is 20-200mg/L, and the concentration of the mixed ester is 40-400 mg/L;
in the series of standard curve solutions, the concentration of the internal standard substance is 100 mg/L;
the aperture of the organic filter membrane is 0.22 mu m.
Example 3
A method for determining mixed alcohols including methanol, n-propanol, n-butanol, sec-butanol, iso-butanol and mixed esters including ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate in industrial ethanol by a gas chromatography internal standard method, comprising the steps of:
(1) preparing a mixed alcohol and mixed ester standard stock solution:
respectively weighing 50-200mg of methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamylol, weighing 2 times of methanol of ethyl acetate, ethyl butyrate, ethyl caproate, ethyl lactate and butyl acetate, mixing, placing in a 100mL volumetric flask, performing constant volume with an ethanol aqueous solution, and shaking for 1-2min to obtain a mixed alcohol and mixed ester standard stock solution;
(2) preparing an internal standard stock solution:
weighing benzene with the same mass as methanol in a 100mL volumetric flask by taking the benzene as an internal standard substance, performing constant volume with an aqueous solution, and shaking up for 1-2min to obtain an internal standard substance standard stock solution;
(3) preparing a series of standard curve solutions:
respectively taking the mixed alcohol, the mixed ester standard stock solution and the internal standard substance standard stock solution, mixing in a volumetric flask, and performing constant volume by using an ethanol water solution to obtain a mixed standard curve solution; respectively preparing at least 5 mixed standard curve solutions to form a series of standard curve solutions; the method comprises the following specific steps:
respectively taking 0.5-1mL of mixed alcohol and mixed ester standard stock solution and 0.1-0.5mL of internal standard substance standard stock solution, adding into a 5mL volumetric flask, performing constant volume with ethanol water solution, and shaking for 1-2min to obtain a mixed standard curve solution 1; respectively taking 0.5-1mL of mixed alcohol and mixed ester standard stock solution and 0.5-1mL of internal standard stock solution, adding into a 10mL volumetric flask, performing constant volume with ethanol water solution, and shaking for 1-2min to obtain a mixed standard curve solution 2; respectively taking 0.5-1mL of mixed alcohol and mixed ester standard stock solution and 1.0-1.5mL of internal standard stock solution, adding into a 15mL volumetric flask, performing constant volume with ethanol water solution, and shaking for 1-2min to obtain a mixed standard curve solution 3; respectively taking 0.5-1mL of mixed alcohol and mixed ester standard stock solution and 2.0-2.5mL of internal standard stock solution, adding into a 25mL volumetric flask, performing constant volume with ethanol water solution, and shaking for 1-2min to obtain a mixed standard curve solution 4; respectively taking 0.5-1mL of mixed alcohol and mixed ester standard stock solution and 2.5-5mL of internal standard stock solution, adding into a 50mL volumetric flask, performing constant volume with ethanol water solution, and shaking for 1-2min to obtain a mixed standard curve solution 5; obtaining 5 mixed standard solutions with different concentrations to form a series of standard curve solutions;
(4) and (3) chromatographic analysis:
respectively carrying out gas chromatography analysis on the series of standard curve solutions, and recording peak areas; wherein, the gas chromatographic analysis conditions are as follows:
the type of the adopted gas chromatograph is a Saimer FeiTRACE-1310 gas chromatograph;
a chromatographic column: one of the capillary columns TG-WAX, HP-1 and HP-5;
column flow rate: 1.0-5.0 mL/min;
sample inlet temperature: 200 ℃ and 300 ℃;
a detector: hydrogen Flame Ionization Detector (FID), temperature: 200 ℃ and 300 ℃, air flow: 200-400 mL/min, hydrogen flow rate of 20-40 mL/min, tail gas blowing flow rate: 20-50 mL/min;
column temperature onset temperature: keeping the temperature at 30-60 deg.C for 5-10min, heating at a rate of 5-25 deg.C/min to 200 deg.C, and keeping the temperature for 10-20 min;
carrier gas: high purity nitrogen (99.999%);
the split ratio is as follows: 10-100: 1;
sample introduction amount: 0.5-3.0 μ L;
(5) establishment of a standard curve:
fitting to obtain a standard curve by taking the concentration ratio of the object to be measured and the internal standard substance as a horizontal coordinate x and the peak area ratio of the object to be measured and the internal standard substance as a vertical coordinate, wherein the standard curve forces to pass through an origin, and the linear correlation coefficient is more than or equal to 0.999, so as to respectively obtain a standard curve of methanol, a standard curve of n-propanol, a standard curve of n-butanol, a standard curve of sec-butanol, a standard curve of isobutanol, a standard curve of isoamyl alcohol, a standard curve of ethyl acetate, a standard curve of ethyl butyrate, a standard curve of ethyl hexanoate, a standard curve of ethyl lactate and a standard curve of butyl acetate; wherein the substance to be detected is methanol, n-propanol, n-butanol, sec-butanol, isobutanol, isoamyl alcohol, ethyl acetate, ethyl butyrate, ethyl caproate, ethyl lactate and butyl acetate;
(6) sample detection:
placing 5-10mL of industrial ethanol stock solution of a detection sample in a 50-100mL volumetric flask, adding 1-10mL of the internal standard stock solution, performing constant volume with an ethanol aqueous solution, and shaking up for 1-2min to obtain a detection solution; filtering 2mL of detection solution by an organic filter membrane with the aperture of 0.22 mu m, performing gas chromatography analysis according to the conditions in the step (4), recording the peak area, and calculating the concentration of the mixed alcohol and the mixed ester in the detection sample according to the standard curve;
in the embodiment, the volume of the ethanol in the ethanol aqueous solution accounts for 40-80%.
Example 4
A method for determining mixed alcohols including methanol, n-propanol, n-butanol, sec-butanol, iso-butanol and mixed esters including ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate in industrial ethanol by a gas chromatography internal standard method, comprising the steps of:
(1) preparing a mixed alcohol and mixed ester standard stock solution:
respectively weighing 100mg of methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamyl alcohol and 200mg of ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate, mixing, putting into a 100mL volumetric flask, performing constant volume with 60 (v/v)% of ethanol aqueous solution, and shaking for 1-2min to obtain mixed alcohol and mixed ester standard stock solution; wherein, the concentration of methanol is 1000mg/L, the concentration of n-propanol is 1000mg/L, the concentration of n-butanol is 1000mg/L, the concentration of sec-butanol is 1000mg/L, the concentration of isobutanol is 1000mg/L, the concentration of isoamyl alcohol is 1000mg/L, the concentration of ethyl acetate is 2000mg/L, the concentration of ethyl butyrate is 2000mg/L, the concentration of ethyl caproate is 2000mg/L, the concentration of ethyl lactate is 2000mg/L, and the concentration of butyl acetate is 2000 mg/L;
(2) preparing an internal standard stock solution:
weighing 100mg of benzene in a 100mL volumetric flask by taking the benzene as an internal standard substance, performing constant volume by using 60 (v/v)% of ethanol water solution, and shaking uniformly for 1-2min to obtain 1000mg/L internal standard substance stock solution;
(3) preparing a series of standard curve solutions:
respectively taking the mixed alcohol, the mixed ester standard stock solution and the internal standard substance standard stock solution, mixing in a volumetric flask, and performing constant volume by using an ethanol water solution to obtain a mixed standard curve solution; respectively preparing at least 5 mixed standard curve solutions to form a series of standard curve solutions; the method comprises the following specific steps:
adding 1mL of mixed alcohol and mixed ester standard stock solution and 0.5mL of internal standard stock solution into a 5mL volumetric flask, performing constant volume with 60 (v/v)% ethanol water solution, and shaking for 1-2min to obtain a mixed standard curve solution 1; adding 1mL of mixed alcohol and mixed ester standard stock solution and 1mL of internal standard substance standard stock solution into a 10mL volumetric flask, performing constant volume with 60 (v/v)% ethanol water solution, and shaking up for 1-2min to obtain a mixed standard curve solution 2; adding 1mL of mixed alcohol and mixed ester standard stock solution and 1.5mL of internal standard stock solution into a 15mL volumetric flask, performing constant volume with 60 (v/v)% ethanol water solution, and shaking uniformly for 1-2min to obtain a mixed standard curve solution 3; adding 1mL of mixed alcohol and mixed ester standard stock solution and 2.5mL of internal standard stock solution into a 25mL volumetric flask, performing constant volume with 60 (v/v)% ethanol water solution, and shaking uniformly for 1-2min to obtain a mixed standard curve solution 4; adding 1mL of mixed alcohol and mixed ester standard stock solution and 5mL of internal standard substance standard stock solution into a 50mL volumetric flask; fixing the volume with 60 (v/v)% ethanol water solution, shaking for 1-2min to obtain mixed standard curve solution 5; obtaining 5 mixed standard curve solutions to form a series of standard curve solutions; the concentration of the internal standard substance is 100 mg/L; in the mixed standard curve solution 1, the standard curve concentrations of methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamyl alcohol are all 200mg/L, and the standard curve concentrations of ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate are all 400 mg/L; in the mixed standard curve solution 2, the standard curve concentrations of methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamyl alcohol are all 100mg/L, and the standard curve concentrations of ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate are all 200 mg/L; in the mixed standard curve solution 3, the standard curve concentrations of methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamyl alcohol are all 66.67mg/L, and the standard curve concentrations of ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate are all 133.34 mg/L; in the mixed standard curve solution 4, the standard curve concentrations of methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamyl alcohol are all 40mg/L, and the standard curve concentrations of ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate are all 80 mg/L; in the mixed standard curve solution 5, the standard curve concentrations of methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamyl alcohol are all 20mg/L, and the standard curve concentrations of ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate are all 40 mg/L;
(4) and (3) chromatographic analysis:
respectively carrying out gas chromatography analysis on the series of standard curve solutions, recording peak areas, and obtaining a chromatogram as shown in figure 1, wherein the abscissa represents time, and the ordinate represents current; the conditions for gas chromatography were as follows:
the type of the adopted gas chromatograph is a Saimer FeiTRACE-1310 gas chromatograph;
a chromatographic column: a Saimer fly capillary column TG-WAX; specification of chromatographic column: 60 m.times.0.25 mm,1.0 μm (temperature range: -60-325/350 ℃);
column flow rate: 1.0 mL/min;
sample inlet temperature: 280 ℃; a detector: hydrogen Flame Ionization Detector (FID), temperature: 250 ℃, air flow: 350 mL/min, hydrogen flow rate of 35mL/min, tail gas blowing flow rate: 35 mL/min;
column temperature onset temperature: keeping at 40 deg.C for 5min, increasing the temperature to 200 deg.C at 15 deg.C/min, and keeping for 20 min;
carrier gas: high purity nitrogen (99.999%);
the split ratio is as follows: 40: 1;
sample introduction amount: 1.2 mu L;
(5) establishment of a standard curve:
fitting to obtain a standard curve by taking the concentration ratio of the object to be measured and the internal standard substance as a horizontal coordinate x and the peak area ratio of the object to be measured and the internal standard substance as a vertical coordinate, and forcing the standard curve to pass through an original point to obtain the following standard curve: the standard curve for methanol is: y =2430.7x, R is 0.9993; the standard curve for n-propanol is: y =4258.3 x, R is 0.9990; the standard curve for n-butanol was: y =4598.1x, R is 0.9994; the standard curve for sec-butanol is: y =4307.5x, R is 0.9993; the standard curve for isobutanol is: y =5146.8x, R is 0.9995; the standard curve for isoamyl alcohol is: y =5340.2x, R is 0.9991; the standard curve for ethyl acetate is: y =2490.5x, R is 0.9992; the standard curve for ethyl butyrate is: y =3384.7x, R is 0.9997; the standard curve for ethyl hexanoate was: y =4127.4 x, R is 0.9990; the standard curve for ethyl lactate is: y =2639.4x, R is 0.9992; the standard curve for butyl acetate is: y =3452.9x, R is 0.9995; wherein, the substances to be detected are methanol, normal propyl alcohol, normal butyl alcohol, secondary butyl alcohol, isobutyl alcohol, isoamyl alcohol, ethyl acetate, ethyl butyrate, ethyl caproate, ethyl lactate and butyl acetate, and R is a linear correlation coefficient;
(6) sample detection:
the detection sample of the embodiment adopts industrial ethanol stock solution, and the theoretical content of each mixed alcohol and mixed ester is as follows: 102.0 mg/L of methanol, 92.0 mg/L of n-propanol, 95.5 mg/L of n-butanol, 94.0 mg/L of sec-butanol, 97.0 mg/L of isobutanol, 110.0 mg/L of isoamyl alcohol, 428.0 mg/L of ethyl acetate, 432.0 mg/L of ethyl butyrate, 524.0 mg/L of butyl acetate, 345.5 mg/L of ethyl hexanoate and 352.5 mg/L of ethyl lactate;
putting 10mL of the industrial ethanol stock solution of the detection sample into a 50mL volumetric flask, adding 5mL of the internal standard stock solution, performing constant volume with 60 (v/v)% ethanol aqueous solution, and shaking up for 1-2min to obtain a detection solution; filtering 2mL of detection solution by an organic filter membrane with the aperture of 0.22 mu m, performing gas chromatography analysis according to the conditions in the step (4), recording peak areas, calculating the concentration of the mixed alcohol and the mixed ester in the detection solution according to the standard curve, calculating the methanol content to be 20.5mg/L, the n-propanol content to be 18.4mg/L, the n-butanol content to be 19.1mg/L, the sec-butanol content to be 18.9mg/L, the isobutanol content to be 19.5mg/L, the isoamyl alcohol content to be 21.9mg/L, the ethyl acetate content to be 85.7 mg/L, the ethyl butyrate content to be 86.5mg/L, the butyl acetate content to be 104.7mg/L, the ethyl caproate content to be 69.2mg/L, the ethyl lactate content to be 70.5mg/L, converting the volume to obtain the methanol content to be 102.5mg/L in the industrial ethanol of the detection sample, the n-propanol content is 92.1mg/L, the n-butanol content is 95.6mg/L, the sec-butanol content is 94.3mg/L, the isobutanol content is 97.4mg/L, the isoamyl alcohol content is 109.8mg/L, the ethyl acetate content is 428.5 mg/L, the ethyl butyrate content is 432.5mg/L, the butyl acetate content is 523.5mg/L, the ethyl hexanoate content is 345.8mg/L, and the ethyl lactate content is 352.7 mg/L.
Taking example 4 as an example, experiments were performed on precision, accuracy, detection limit, and quantification limit.
First, precision experiment
The detection solution of step (6) was taken, 2mL of the sample solution was collected by syringe, filtered, and injected into a sample injection vial for a total of 6 groups, numbered 1,2,3,4,5,6, and the results were measured by the above-mentioned chromatographic conditions and shown in table 1.
TABLE 1 precision test results for testing mixed alcohols and mixed esters in solution
The RSD of the measurement result is 0.92% -1.93%, which shows that the detection method of the invention has good precision.
Second, accuracy experiment
Taking 1mL of the mixed standard curve solution 1 obtained in the step (3) of the example 4, and taking 4 groups in total; respectively placing 1mL of the mixed standard curve solution into four 10mL volumetric flasks, and then respectively adding 100 muL, 200 muL and 300 muL of mixed alcohol and mixed ester standard stock solutions into three volumetric flasks, wherein the standard stock solutions are marked as test solutions 1,2 and 3; the samples which are not added are used as blank groups and are marked as test solutions 0, 0 to 3 of the test solutions are respectively and accurately added with 0.9mL of internal standard stock solutions to ensure that the concentration of the internal standard substances is 100mg/L, the volume is fixed to a scale by using 60 (v/v)% ethanol aqueous solution, a gas chromatograph is used for accurate sample injection analysis, peak areas are recorded simultaneously, actual measurement adding quantities are obtained by calculating peak area ratios, and the adding recovery rate of the samples is calculated (see tables 2 to 12).
TABLE 2 Experimental results on methanol recovery with standard addition
TABLE 3 results of recovery experiment of n-propanol with standard addition
TABLE 4 experimental results of normal butanol recovery with standard addition
TABLE 5 Sec-Butanol normalized recovery test results
TABLE 6 Isobutanol normalized recovery test results
TABLE 7 recovery of isoamyl alcohol with standard addition test results
TABLE 8 results of ethyl acetate recovery test
TABLE 9 experimental results for recovery of butyl acetate by adding standard
TABLE 10 experimental results of ethyl butyrate spiking recovery
TABLE 11 results of ethyl hexanoate recovery test
TABLE 12 results of ethyl lactate addition standard recovery experiments
As can be seen from tables 2-12, the average recovery rates of the mixed alcohol and the mixed ester are both more than 95%, and the method has high accuracy.
Third, detection and quantitation limits of the method
Calculating the detection limit of the method according to the ratio of the response value of the instrument to the noise being 3; calculating the quantitative limit of the method according to the ratio of the response value of the instrument to the noise being 10; the results are shown in Table 13.
Table 13 detection limit and quantitation limit test results for the methods
As can be seen from Table 13, the detection limit of the mixed alcohol and the mixed ester is less than 3mg/L, the limit of quantitation is less than 10mg/L, the sensitivity of the method is very high, and the analysis of trace components can be satisfied.
Claims (8)
1. A method for measuring mixed alcohol and mixed ester in industrial ethanol by a gas chromatography internal standard method, wherein the mixed alcohol comprises methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamyl alcohol, and the mixed ester comprises ethyl acetate, ethyl butyrate, ethyl caproate, ethyl lactate and butyl acetate, and is characterized in that: the method comprises the following steps:
(1) preparing a mixed alcohol and mixed ester standard stock solution: respectively weighing methanol, n-propanol, n-butanol, sec-butanol, isobutanol, isoamylol, ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate and butyl acetate, mixing and placing in a volumetric flask, and performing constant volume with an ethanol water solution to obtain a mixed alcohol and mixed ester standard stock solution;
(2) preparing an internal standard stock solution: weighing an internal standard substance in a volumetric flask, and performing constant volume by using an ethanol water solution to obtain an internal standard substance standard stock solution; wherein the internal standard substance is any one of benzene, toluene and o-xylene;
(3) preparing a series of standard curve solutions: respectively taking the mixed alcohol, the mixed ester standard stock solution and the internal standard substance standard stock solution, mixing in a volumetric flask, and performing constant volume by using an ethanol water solution to obtain a mixed standard curve solution; respectively preparing at least 5 mixed standard curve solutions to form a series of standard curve solutions; in the series of standard curve solutions, the concentrations of the internal standard substances are the same, and the concentrations of the mixed alcohol and the mixed ester are different;
(4) and (3) chromatographic analysis: respectively carrying out gas chromatography analysis on the series of standard curve solutions, and recording peak areas;
(5) establishment of a standard curve: fitting to obtain a standard curve by taking the concentration ratio of the object to be measured and the internal standard substance as a horizontal coordinate x and the peak area ratio of the object to be measured and the internal standard substance as a vertical coordinate y, wherein the standard curve forcibly passes through an original point, and the linear correlation coefficient is more than or equal to 0.999;
(6) sample detection: taking industrial ethanol of a detection sample, adding an internal standard stock solution into the industrial ethanol, and performing constant volume by using an ethanol solution to obtain a detection solution; filtering the detection solution by an organic filter membrane, performing gas chromatography, recording peak areas, and calculating according to the standard curve to obtain the concentrations of the mixed alcohol and the mixed ester in the detection sample; wherein the concentration of the internal standard substance in the detection solution is the same as the concentration of the internal standard substance in the series of standard curve solutions.
2. The method for measuring mixed alcohol and mixed ester in industrial ethanol by the gas chromatography internal standard method according to claim 1, which is characterized in that: the conditions of the gas chromatographic analysis are as follows: the injection port temperature is 200-.
3. The method for measuring mixed alcohol and mixed ester in industrial ethanol by the gas chromatography internal standard method according to claim 2, which is characterized in that: the volume of the ethanol in the ethanol water solution accounts for 40-80%.
4. The method for measuring mixed alcohol and mixed ester in industrial ethanol by the gas chromatography internal standard method according to claim 3, characterized in that: in the mixed alcohol and mixed ester standard stock solution, the concentrations of methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamyl alcohol are the same and are marked as a; the concentrations of ethyl acetate, ethyl butyrate, ethyl caproate, ethyl lactate and butyl acetate are the same and are marked as b; the concentration of the internal standard substance in the internal standard substance standard stock solution is marked as c; the a, b and c satisfy the following relations: b =2a =2 c.
5. The method for measuring mixed alcohol and mixed ester in industrial ethanol by the gas chromatography internal standard method according to claim 4, wherein the method comprises the following steps: in the mixed alcohol and mixed ester standard stock solutions, the concentrations of methanol, n-propanol, n-butanol, sec-butanol, isobutanol and isoamylol are all 500-2000 mg/L.
6. The method for measuring mixed alcohol and mixed ester in industrial ethanol by the gas chromatography internal standard method according to claim 5, wherein: in the series of standard curve solutions, the concentration of the mixed alcohol is 20-200mg/L, and the concentration of the mixed ester is 40-400 mg/L.
7. The method for measuring mixed alcohol and mixed ester in industrial ethanol by the gas chromatography internal standard method according to claim 6, wherein the method comprises the following steps: the concentration of the internal standard substance in the series of standard curve solutions is 100 mg/L.
8. The method for measuring mixed alcohol and mixed ester in industrial ethanol by the gas chromatography internal standard method according to claim 7, wherein the method comprises the following steps: the aperture of the organic filter membrane is 0.22 mu m.
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Application publication date: 20210319 |