CN1936586B - Method for fully analyzing air (oxygen) oxidation cyclohexaane reaction mixture - Google Patents
Method for fully analyzing air (oxygen) oxidation cyclohexaane reaction mixture Download PDFInfo
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Abstract
This is one kind entire analysis method to air (oxygen) and cyclohexane reactive mixtures. This method analyses the reaction mixture of adipic acid, glutaric acid and succinic acid using liquid chromatography. Use diamonsil TM C18 as stationary phase column, use the mixture of methanol, water and Dihydro-K phosphate for mobile phase and test with multi-wavelength UV detector. Analyze the cyclohexane, cyclohexanone cyclohexyl alcohol in reaction mixture by gas chromatography. Choose polyethylene glycol for stationary phase column and nitrogen for carrier gas, test with hydrogen flame ionizationdetector. Analyze cyclohexyl - cyclohexyl esters of adipic acid and hydrogen peroxide in reaction mixture by chemical titration. The analysis method is errorless, high precision, easy to operate, canaccurate qualitative and quantitative analysis to all components of the reaction mixture.
Description
Technical field
The present invention relates to a kind of analytical approach, particularly relate to a kind of method that empty (oxygen) gas oxidizing ethyle alkyl reaction mixture is carried out total analysis.
Background technology
At present cyclohexane oxidation process is the main synthetic method of industrial preparation cyclohexanol, cyclohexanone and hexane diacid, but problem such as this class methods ubiquity selectivity of product difference and feed stock conversion be low.And to improve or will study a kind of new synthetic method to industrial old production technology, at first must solve the qualitative and quantitative analysis problem of product, so that measure conversion of raw material, product selectivity and intermediate product exactly.This reaches effectively to improve the principal product generation and control the accessory substance generation for further research reaction mechanism important directive function.
Through mass spectrum (MS) cyclohexane oxidation product is carried out qualitative analysis and determine that product contains cyclohexane (unreacted), cyclohexanol, cyclohexanone, hexane diacid, glutaric acid, succinic acid, cyclohexyl hydroperoxide, hexane diacid list cyclohexyl, cyclohexene-2-ketone, 2-hydroxy-cyclohexanone, 6-oxo caproic acid, 5-oxopentanoic acid, valeric acid and caproic acid.Because above-claimed cpd physicochemical property difference is very big, be difficult to reaction mixture be realized total analysis with a kind of analytical instrument and/or means.Up to the present do not see the report that empty (oxygen) gas oxidizing ethyle alkyl reaction mixture is carried out the total analysis method as yet.
Summary of the invention
The object of the present invention is to provide a kind of method that empty (oxygen) gas oxidizing ethyle alkyl reaction mixture is carried out total analysis.Its analytical approach can be to all can be surveyed component and carry out qualitative and quantitative analysis accurately in the reaction mixture, and this method error is little, precision is high, easy and simple to handle.
A kind of method that empty (oxygen) gas oxidizing ethyle alkyl reaction mixture is carried out total analysis provided by the present invention, it may further comprise the steps::
(1) with dissolve with methanol cyclohexane reaction mixture;
(2) with hexane diacid, glutaric acid and succinic acid in the liquid chromatography analysis cyclohexane reaction mixture, liquid chromatography is filled column length 10-30cm, and diameter 0.1-1.0cm, liquid-phase chromatographic column stationary phase are Diamonsil
TMC
18Be mixed with moving phase with methyl alcohol, water and potassium dihydrogen phosphate, methyl alcohol: water: the volume ratio of potassium dihydrogen phosphate is (15-30): (50-75): (10-20), regulate the pH=3-4 of moving phase with phosphoric acid, disposable hexane diacid, glutaric acid and the succinic acid isolated detects through the ultraviolet multiwavelength detector;
(3) with cyclohexane, cyclohexanol and cyclohexanone in the gc analysis cyclohexane reaction mixture, the long 10-30m of gas-phase chromatographic capillary column, diameter 0.10-0.25mm, the gas chromatographic column stationary phase is a polyglycol, column temperature is 130-160 ℃, disposable cyclohexane, cyclohexanol and the cyclohexanone isolated, (FID) detects through flame ionization ditector;
(4) with cyclohexyl hydroperoxide and hexane diacid cyclohexyl in the chemical titration analysis cyclohexane reaction mixture, the 1-3g said mixture is dissolved in 20mL acetic acid-chloroform mixed solvent, the volume ratio of acetic acid and chloroform is (1-2): (1-3), add the 5-20mL potassium iodide, behind the water seal 10-30min, with the titration of 0.1mol/L sodium thiosulfate standard solution; Again with the 1-4g said mixture with the titration of 0.1mol/L standard solution of sodium hydroxide to little red, the 0.1mol/L standard solution of sodium hydroxide of Dropwise 5-20mL again, reflux, with the titration of 0.1mol/L hydrochloric acid standard solution to just colourless.
Cyclohexene in the cyclohexane reaction mixture-2-ketone, 2-hydroxy-cyclohexanone, 6-oxo caproic acid, 5-oxopentanoic acid, valeric acid and caproic acid, its content has exceeded the sensing range of stratographic analysis or chemistry titration, therefore can only carry out quantitative test to cyclohexane (unreacted), cyclohexanol, cyclohexanone, hexane diacid, glutaric acid, succinic acid, cyclohexyl hydroperoxide and hexane diacid list cyclohexyl.
Because the polarity difference of various components is very big in the cyclohexane reaction mixture, this potpourri is a heterogeneous system, therefore at first need to make it become homogeneous system with organic solvent dissolution in this potpourri, but selected organic solvent polarity can not be excessive, the excessive weak cyclohexane of polarity that then can not dissolve, polarity can not be too small simultaneously, too smallly then can not dissolve carboxylic acids such as the strong succinic acid of polarity, glutaric acid and hexane diacid, and will guarantee that the organic solvent that is added does not make that the physico-chemical property of various components changes in the potpourri.And methyl alcohol can dissolve the cyclohexane reaction mixture fully and don't the physico-chemical property of various components is changed, so the present invention selects this potpourri of dissolve with methanol.
After the inventive method was used dissolve with methanol cyclohexane reaction mixture, directly through liquid chromatography, gas chromatography and chemical titration analysis, without any need for other intermediate treatment process, so easy and simple to handle, error was little.
Description of drawings
Fig. 1 is the liquid chromatogram of sky (oxygen) the gas oxidizing ethyle alkyl reaction mixture of embodiment 1;
Fig. 2 is the gas chromatogram of sky (oxygen) the gas oxidizing ethyle alkyl reaction mixture of embodiment 1.
Embodiment
Add 20mL cyclohexane and catalysis of metalloporphyrin agent in autoclave, catalyst consumption is the 0.1-0.5 ‰ of cyclohexane weight, feeds 1-3MPa oxygen, reacts 3-5h down at 100-180 ℃, obtains the cyclohexane reaction mixture.
Embodiment 1
Use the dissolve with methanol said mixture.
Liquid-phase chromatographic analysis: column size: long 25cm, diameter 0.46cm; Chromatographic column stationary phase: Diamonsil
TMC
18Moving phase: methyl alcohol: water: potassium dihydrogen phosphate=20: 70: 10 (volume ratio), transfer the pH=4 of moving phase with phosphoric acid; Sample size 5 μ L; Flow velocity 0.8mL/min; Detect with the ultraviolet multiwavelength detector, detect wavelength: 212nm; Its liquid chromatogram is seen Fig. 1.Under identical chromatographic condition, reaction mixture chromatogram and hexane diacid, glutaric acid and succinic acid standard colors spectrogram are contrasted, according to retention time the hexane diacid in the reaction mixture, glutaric acid and succinic acid are carried out qualitative analysis; Adopt external standard method that the hexane diacid in the reaction mixture, glutaric acid and succinic acid are carried out quantitative test.The yield of the succinic acid that analyzes, glutaric acid and hexane diacid is respectively: 3.11%, 5.13%, 10.96%.Error to hexane diacid, glutaric acid and succinic acid in the above-mentioned reaction mixture is analyzed, and it the results are shown in Table 1.
Gas chromatographic analysis: at first reaction mixture is carried out pre-service, remove the cyclohexyl hydroperoxide in the potpourri. according to the content of cyclohexyl hydroperoxide, accurately take by weighing the 2mL sample, 2mg triphenylphosphine that disposable adding is excessive and 0.5mL chlorobenzene, place 10-30min, carry out gas chromatographic analysis then. column size: long 30m, diameter 0.25mm; Chromatographic column stationary phase: polyglycol; Carrier gas: nitrogen; Combustion gas: hydrogen; Press before the post: 0.6atm; Column temperature: 160 ℃; Sample introduction temperature: 250 ℃; Detected temperatures: 250 ℃; Sample size: 0.4 μ L; Detect with fid detector, its gas chromatogram is seen Fig. 2. under identical chromatographic condition, the standard colors spectrogram of reaction mixture chromatogram and cyclohexane, cyclohexanol and cyclohexanone is contrasted, the cyclohexane in the reaction mixture, cyclohexanol and cyclohexanone are carried out qualitative analysis according to retention time; Adopt internal standard method that the cyclohexane in the reaction mixture, cyclohexanol and cyclohexanone are carried out quantitative test, internal standard compound is a chlorobenzene. the conversion of cyclohexane that analyzes is 65.39%, the yield of cyclohexanol, cyclohexanone is respectively: 12.88%, 3.91%. the error of cyclohexane, cyclohexanol and cyclohexanone in the above-mentioned reaction mixture is analyzed, it the results are shown in Table 2.
Chemical titration analysis: the reaction mixture of 1.013g is dissolved in 20mL acetic acid-chloroform mixed solvent, the volume ratio of acetic acid and chloroform is 1: 1, add the 10.000mL potassium iodide, behind the water seal 20min, extremely faint yellow with the sodium thiosulfate standard solution titration of 0.1mol/L, drip starch indicator, solution presents black, continue to drop to till the black disappearance, and contrast with blank assay, the yield of the cyclohexyl hydroperoxide that analyzes is 0.070%.Error to cyclohexyl hydroperoxide in the above-mentioned reaction mixture is analyzed, and it the results are shown in Table 3.The reaction mixture of 1.957g is added phenolphthalein indicator, and the standard solution of sodium hydroxide titration of using 0.1mol/L is to little red (colour-fast in 30 seconds); Add the standard solution of sodium hydroxide that volume is the 0.1mol/L of 10.000mL again, reflux is dripped to just colourless with the 0.1mol/L hydrochloric acid standard solution.The yield of the hexane diacid cyclohexyl that analyzes is 0.711%.Error to hexane diacid cyclohexyl in the above-mentioned reaction mixture is analyzed, and it the results are shown in Table 4.
Embodiment 2
Use the dissolve with methanol said mixture.
Liquid-phase chromatographic analysis: moving phase: methyl alcohol: water: potassium dihydrogen phosphate=15: 75: 10 (volume ratio), all the other conditions are with embodiment 1.The yield of the succinic acid that analyzes, glutaric acid and hexane diacid is respectively: 3.02%, 6.37%, 11.20%.
Gas chromatographic analysis: press before the post: 0.8atm, all the other conditions are with embodiment 1.Isolated conversion of cyclohexane is 50.00%, and the yield of cyclohexanol, cyclohexanone is respectively: 9.13%, 3.54%.
Chemical titration analysis: the reaction mixture of 3.000g is dissolved in 20mL acetic acid-chloroform mixed solvent, and the volume ratio of acetic acid and chloroform is 2: 1, and all the other conditions are with embodiment 1.The yield of the cyclohexyl hydroperoxide that analyzes is 0.113%.The reaction mixture of 3.000g is added phenolphthalein indicator, and the standard solution of sodium hydroxide titration of using 0.1mol/L is to little red (colour-fast in 30 seconds); Add the standard solution of sodium hydroxide that volume is the 0.1mol/L of 20.000mL again, all the other conditions are with embodiment 1.The yield of the hexane diacid cyclohexyl that analyzes is 0.698%.
Embodiment 3
Use the dissolve with methanol said mixture.
Liquid-phase chromatographic analysis: moving phase: methyl alcohol: water: potassium dihydrogen phosphate=25: 65: 10 (volume ratio), all the other conditions are with embodiment 1.The yield of the succinic acid that analyzes, glutaric acid and hexane diacid is respectively: 7.13%, 4.05%, 9.21%.
Gas chromatographic analysis: sample introduction temperature: 230 ℃; Detected temperatures: 230 ℃, all the other conditions are with embodiment 1.The conversion of cyclohexane that analyzes is 45.98%, and the yield of cyclohexanol, cyclohexanone is respectively: 5.67%, 3.89%.
Chemical titration analysis: the reaction mixture of 1.510g is dissolved in 20mL acetic acid-chloroform mixed solvent, and the volume ratio of acetic acid and chloroform is 1: 3, and all the other conditions are with embodiment 1.The yield of the cyclohexyl hydroperoxide that analyzes is 0.123%.Get the reaction mixture of 3.021g, all the other conditions are with embodiment 1.The yield of the hexane diacid cyclohexyl that analyzes is 0.803%.
Use the dissolve with methanol said mixture.
Liquid-phase chromatographic analysis: moving phase: methyl alcohol: water: potassium dihydrogen phosphate=30: 60: 10 (volume ratio); Flow rate of mobile phase 1.0mL/min, all the other conditions are with embodiment 1.The yield of the succinic acid that analyzes, glutaric acid and hexane diacid is respectively: 1.05%, 3.64%, 11.17%.
Gas chromatographic analysis: column temperature: 150 ℃; Sample size: 0.8 μ L, all the other conditions are with embodiment 1.The conversion of cyclohexane that analyzes is 54.89%, and the yield of cyclohexanol, cyclohexanone is respectively: 5.24%, 2.15%.
Chemical titration analysis: the reaction mixture of 1.510g is dissolved in 20mL acetic acid-chloroform mixed solvent, and the volume ratio of acetic acid and chloroform is 1: 1, adds the 15.000mL potassium iodide, and all the other conditions are with embodiment 1.The yield of the cyclohexyl hydroperoxide that analyzes is 0.089%.Get the reaction mixture of 3.018g, all the other conditions are with embodiment 1.The yield of the hexane diacid cyclohexyl that analyzes is 0.798%.
Use the dissolve with methanol said mixture.
Liquid-phase chromatographic analysis: moving phase: methyl alcohol: water: potassium dihydrogen phosphate=25: 65: 10 (volume ratio), phosphoric acid is transferred PH=3, and all the other conditions are with embodiment 1.The yield of the succinic acid that analyzes, glutaric acid and hexane diacid is respectively: 2.36%, 3.51%, 9.82%.
Gas chromatographic analysis: column temperature: 140 ℃, all the other conditions are with embodiment 1.The conversion of cyclohexane that analyzes is 67.54%, and the yield of cyclohexanol, cyclohexanone is respectively: 10.21%, 3.07%.
Chemical titration analysis: with the reaction mixture dissolving back water seal 30min of 1.510g, all the other conditions are with embodiment 1.The yield of the cyclohexyl hydroperoxide that analyzes is 0.068%.Get the reaction mixture of 3.023g, all the other conditions are with embodiment 1.The yield of the hexane diacid cyclohexyl that analyzes is 0.698%.
Embodiment 6
Use the dissolve with methanol said mixture.
Liquid-phase chromatographic analysis: moving phase: methyl alcohol: water: potassium dihydrogen phosphate=30: 50: 20 (volume ratio), phosphoric acid is transferred PH=3; Sample size 10 μ L, all the other conditions are with embodiment 1.The yield of the succinic acid that analyzes, glutaric acid and hexane diacid is respectively: 5.23%, 4.63%, 6.81%.
Gas chromatographic analysis: column temperature: 130 ℃; Press before the post: 1.0atm, all the other conditions are with embodiment 1.The conversion of cyclohexane that analyzes is 59.82%, and the yield of cyclohexanol, cyclohexanone is respectively: 6.69%, 3.91%.
Chemical titration analysis: after the reaction mixture dissolving with 1.293g, all the other conditions are with embodiment 1.The yield of the cyclohexyl hydroperoxide that analyzes is 0.051%.Get the reaction mixture of 3.450g, all the other conditions are with embodiment 1.The yield of the hexane diacid cyclohexyl that analyzes is 0.930%.
The relative standard deviation of hexane diacid, glutaric acid and succinic acid in table 1 reaction mixture
The relative standard deviation of cyclohexane, cyclohexanol and cyclohexanone in table 2 reaction mixture
The relative standard deviation of cyclohexyl hydroperoxide in table 3 reaction mixture
The relative standard deviation of hexane diacid cyclohexyl in table 4 reaction mixture
Claims (1)
1. method that air or oxygen oxidizing ethyle alkyl reaction mixture is carried out total analysis is characterized in that it may further comprise the steps:
(1) with the cyclohexane reaction mixture after the dissolve with methanol oxidation;
(2) with hexane diacid, glutaric acid and succinic acid in the liquid chromatography analysis cyclohexane reaction mixture, liquid chromatography is filled column length 10-30cm, and diameter 0.1-1.0cm, liquid-phase chromatographic column stationary phase are Diamonsil
TMC
18Be mixed with moving phase with methyl alcohol, water and potassium dihydrogen phosphate, methyl alcohol: water: the volume ratio of potassium dihydrogen phosphate is (15-30): (50-75): (10-20), regulate the pH=3-4 of moving phase with phosphoric acid, disposable hexane diacid, glutaric acid and the succinic acid isolated detects through the ultraviolet multiwavelength detector;
(3) with cyclohexane, cyclohexanol and cyclohexanone in the gc analysis cyclohexane reaction mixture, the long 10-30m of gas-phase chromatographic capillary column, diameter 0.10-0.25mm, the gas chromatographic column stationary phase is a polyglycol, column temperature is 130-160 ℃, disposable cyclohexane, cyclohexanol and the cyclohexanone isolated detects through flame ionization ditector;
(4) with cyclohexyl hydroperoxide and hexane diacid cyclohexyl in the chemical titration analysis cyclohexane reaction mixture, the 1-3g said mixture is dissolved in 20mL acetic acid-chloroform mixed solvent, the volume ratio of acetic acid and chloroform is (1-2): (1-3), add the 5-20mL potassium iodide, behind the water seal 10-30min, with the titration of 0.1mol/L sodium thiosulfate standard solution; Again with the 1-4g said mixture with the titration of 0.1mol/L standard solution of sodium hydroxide to little red, the 0.1mol/L standard solution of sodium hydroxide of Dropwise 5-20mL again, reflux, with the titration of 0.1mol/L hydrochloric acid standard solution to just colourless.
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