CN118090949A - Method for determining product in reaction liquid for preparing 2-NP by catalytic ammoxidation - Google Patents
Method for determining product in reaction liquid for preparing 2-NP by catalytic ammoxidation Download PDFInfo
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- CN118090949A CN118090949A CN202410126746.0A CN202410126746A CN118090949A CN 118090949 A CN118090949 A CN 118090949A CN 202410126746 A CN202410126746 A CN 202410126746A CN 118090949 A CN118090949 A CN 118090949A
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000012295 chemical reaction liquid Substances 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 27
- FGLBSLMDCBOPQK-UHFFFAOYSA-N 2-nitropropane Chemical compound CC(C)[N+]([O-])=O FGLBSLMDCBOPQK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims abstract description 29
- 238000004817 gas chromatography Methods 0.000 claims abstract description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000012086 standard solution Substances 0.000 claims abstract description 9
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000007865 diluting Methods 0.000 claims abstract 2
- 238000001514 detection method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000004445 quantitative analysis Methods 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 238000004364 calculation method Methods 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 12
- 239000012488 sample solution Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- -1 2-nitropropane ammonium salt Chemical compound 0.000 description 3
- 239000013582 standard series solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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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
-
- 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
-
- 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
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
-
- 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
-
- 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
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
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- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Pathology (AREA)
- Biochemistry (AREA)
- Immunology (AREA)
- General Physics & Mathematics (AREA)
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- Library & Information Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for determining a product in a reaction liquid for preparing 2-NP by catalytic ammoxidation, which comprises the following steps: a1, preparing a homogeneous phase solution, namely placing ammonia water with the concentration of 5% -27% into a solvent, obtaining a crude homogeneous phase solution under the premise of temperature control and through stirring, placing A2-nitropropane standard sample into the crude homogeneous phase solution, preparing homogeneous phase solutions with different concentrations, and diluting the homogeneous phase solution into 2-nitropropane standard solutions with different concentrations by using the solvent; a3, detecting the homogeneous solution I with different concentrations by adopting a gas chromatography, A4, preparing A2-nitropropane reaction liquid sample, preparing the homogeneous solution I by catalytic ammoxidation, and A5, detecting the 2-nitropropane reaction liquid sample by adopting the gas chromatography which is the same as that of the step A2. The method has the advantages of simple operation and calculation, good precision, high sensitivity, good repeatability and good linear fitting, and the correlation coefficient of the standard curve reaches more than 0.9999.
Description
Technical Field
The invention relates to the field of organic synthesis analysis and detection, in particular to a method for measuring a product in a reaction liquid for preparing 2-NP by catalytic ammoxidation.
Background
2-Nitropropane, the alias of paranitropropane, the English name of 2-nitropropane, 2-NP for short. The 2-nitropropane can be used as a special solvent for ethylene and epoxy resin paint, rocket fuel, gasoline additive and the like, and is also widely used for various organic syntheses. 2-nitropropane has strong dissolving power, is an excellent solvent for various cellulose derivatives, vinyl resins and the like, and is also used as a solvent for waxes, fats, dyes and the like, a lubricant for grinding pigments, and a cleaning and mordant for cotton fabrics.
The traditional preparation method of the 2-nitropropane is generally obtained by nitrifying propane or propylene, the detection of a central control or a product is generally detected by GC, and the general accuracy can meet the requirements by adopting a chromatographic normalization or simple internal calibration method. However, the latest preparation process, namely the method for preparing 2-nitropropane by catalytic ammoxidation (for example, patent CN112321435A, CN 115557840A), is not satisfactory in accuracy if the above detection method is adopted for the detection of the reaction liquid. Cao Yalin et al, J.Chemie technology and development, disclose a method for detecting 2-NP finished products by ammoxidation, but the detection of the reaction solution generates larger deviation, and the general deviation is between 6 and 10 percent.
The main reasons for the deviation of the traditional detection method in the process of measuring the reaction liquid for preparing 2-NP by ammoxidation are as follows: in the preparation of 2-NP by ammoxidation, an excess of aqueous ammonia is generally used, and this excess of aqueous ammonia is combined with the 2-NP to form a salt, and this salt is decomposed (in the vaporization chamber) and recombined (in the column) during the gas phase detection, which results in the 2-NP having a chromatographic peak which is typically a fraction of split peaks, one of which is 2-NP and one of which is 2-nitropropane ammonium salt. The chromatographic response of the 2-nitropropane ammonium salt is greater than that of 2-NP, and if the integral quantification is unified, the measurement result is higher than the actual level. The quantitative detection of the reaction liquid has important significance for the production of 2-NP, and is the basis of the balance between the reaction yield of the product and the preparation yield of subsequent treatment. Therefore, it is necessary to establish a more accurate quantitative detection method for products in the reaction liquid for preparing 2-NP by catalytic ammoxidation.
Disclosure of Invention
In view of the foregoing drawbacks or shortcomings of the prior art, it would be desirable to provide a method for determining the product in a reaction solution for the catalytic ammoxidation to 2-NP.
According to the technical proposal provided by the embodiment of the application,
A method for measuring products in a reaction liquid for preparing 2-NP by catalytic ammoxidation comprises the following steps:
(1) Taking a homogeneous solution obtained after the reaction of the 2-nitropropane standard substance and ammonia water, preparing the homogeneous solution into standard solutions with different concentrations by using an ethanol aqueous solution, simultaneously adding an internal standard substance, detecting the standard solution by adopting a gas chromatography method, and determining the linear relation between the peak area ratio of the 2-nitropropane and the internal standard substance and the peak content ratio of the 2-nitropropane and the internal standard substance.
(2) And (3) detecting the sample solution by adopting the gas chromatography method which is the same as that adopted in the step (1) to prepare the 2-NP reaction solution by catalytic ammoxidation, and calculating the content of the 2-nitropropane by adopting an internal calibration method.
The detector adopted by the gas chromatography is an FID hydrogen flame detector, and hydrogen and air are respectively used as auxiliary gases, and a chromatographic column with polarity, middle polarity and weak polarity is used as a chromatographic column. The method adopts an internal standard method, is simple to operate and calculate, can realize accurate quantitative analysis of the 2-nitropropane content within the range of 0.004-0.17g, and can realize accurate quantitative analysis of the solution with the 2-nitropropane content of 0.4-17%.
As a further preferred embodiment of the method of the present invention, the detection conditions of the gas chromatography are as follows: polar, medium-polar and weak-polar chromatographic columns are used as chromatographic columns, and the carrier gas flow rate is
1.0-5.0ML/min; the sample injection amount is 0.1-1 mu L; the temperature of the sample inlet is 220-300 ℃; the temperature of the detector is 280-350 ℃; the hydrogen flow is 30-60mL/min; the air flow rate is 350-400mL/min, and the temperature rising program is as follows: firstly keeping the constant temperature at 50-100 ℃ for 1-10min, then heating to 220-300 ℃ at the heating rate of 10-30 ℃/min, and then keeping the constant temperature for 10-15min.
As a further preferred embodiment of the method, the split ratio of the split injection is 100:1. When the content of 2-nitropropane in the sample is in the range of 0.004-0.17g, the peak area ratio of 2-nitropropane to the internal standard substance and the peak content ratio of 2-nitropropane to the internal standard substance show good linear relations, the correlation coefficient R 2 can reach more than 0.9999, the standard adding recovery rate measured on the 2-nitropropane is 100.15%, and the repeatability relative standard deviation RSD is 0.1%.
As a further preferred embodiment of the process according to the invention, the content of the 2-nitropropane standard solution is in the range from 0.004 to 0.17 g.
As a preferred embodiment of the process according to the invention, the 2-nitropropane ammonium salt is present in an amount of from 0.4 to 17%.
As a preferred embodiment of the present invention, the preparation of the 2-nitropropane sample comprises the steps of: weighing a 2-nitropropane standard sample, adding ammonia water according to a proportion, and reacting for a certain time through stirring, ultrasonic treatment and the like to obtain the sample solution.
In summary, the application has the following beneficial effects: the method has the advantages of simple operation and calculation, good precision, high sensitivity, good reproducibility and good linear fitting, and the correlation coefficient of a standard curve reaches more than 0.9999, thereby being suitable for quantitative analysis of products in the reaction liquid for preparing 2-NP by catalytic ammoxidation.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the detailed description of non-limiting embodiments, made with reference to the accompanying drawings in which:
FIG. 1 is a gas chromatogram of one of the 2-nitropropane standard solutions obtained by separate sample injection for gas chromatographic analysis;
FIG. 2 is a standard curve of an internal standard obtained by the method through a chromatographic workstation;
FIG. 3 is a standard curve of 2-nitropropane obtained by the present process through a chromatographic workstation;
FIG. 4 is a chromatogram obtained after adding dioxane standard to a reaction solution for preparing 2-NP by catalytic ammoxidation.
FIG. 5 is a chromatogram obtained after adding dioxane standard into the reaction solution for preparing 2-NP by catalytic ammoxidation concentration.
Detailed Description
The application is described in further detail below with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the application and are not limiting of the application. It should be noted that, for convenience of description, only the portions related to the application are shown in the drawings.
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
1. Test
1.1 Instruments, reagents and materials
2-Nitropropane standard, china medical group Co., ltd
Ethanol, 1, 4-dioxane, ammonia water analytically pure, tianjin City Density European chemical reagent
Gas chromatograph, agilent7890B, with hydrogen Flame Ionization Detector (FID)
Analytical balance, BSA224S, sidoris
Ultrasonic cleaner, KQ5200DE, kunshan ultrasonic instruments Co., ltd
High purity nitrogen (purity 99.999%)
1.2 Gas chromatography conditions
Chromatographic column: DB-WAX capillary chromatographic column (60 m.times.0.32 mm.times.0.25 μm), or equivalent chromatographic column
Carrier gas flow rate: 1.0mL/min
Sample injection amount 1. Mu.L
Heating program: keeping the temperature at 60 ℃ for 5min, heating to 90 ℃ at a heating rate of 10 ℃/min, heating to 200 ℃ at a heating rate of 30 ℃/min, and keeping the temperature for 8min
Sample injection mode: split sample injection, split ratio 100:1
Sample inlet temperature: 250 DEG C
Detector temperature: 300 DEG C
High purity hydrogen flow: 30 mLmin-
High pure air flow rate: 400mL/min
1.3 Analytical procedure
1.3.1 Preparation of Standard series solutions
Respectively weighing 0.02 g, 0.07 g, 0.50 g, 0.72 g and 1.0g of 2-nitropropane homogeneous phase solution samples, adding 0.1g of standard series solutions of 1, 4-dioxane inner standard substance and ethanol water solution, and shaking uniformly for later use.
1.3.2 Sample preparation
A homogeneous aqueous solution of 2-nitropropane was prepared in advance.
1G of a reaction liquid sample for preparing 2-NP by catalytic ammoxidation and 0.1g of 1, 4-dioxane are taken and uniformly shaken, thus obtaining a sample solution.
Making a standard curve
Under the conditions of 1.2 gas chromatography conditions, respectively feeding the 2-nitropropane standard solutions prepared in the preparation part of the 1.3.1 standard series solutions to perform gas chromatography analysis, wherein one of the obtained gas chromatograms is shown in figure 1, and the peak time of the 2-nitropropane is 10.0min; the standard curves were obtained by the chromatographic workstation with the peak content ratio of the series 2-nitropropane to the internal standard as abscissa and the peak area ratio of the 2-nitropropane to the internal standard as ordinate, as shown in fig. 2 and 3.
Calculation of the reaction liquid content for preparing 2-NP by catalytic ammoxidation
Sample solutions prepared in the 1.3.2 sample preparation section were injected under the conditions described in the 1.2 gas chromatography conditions section for gas chromatography analysis, and the content of 2-nitropropane in the samples was obtained according to a standard curve, calculated as follows:
2. Analysis results and discussion
2.1 Method repeatability test and labeled recovery test
Under the conditions described in the section "1.2 gas chromatography conditions", the sample solution prepared in the section "1.3.2 sample preparation" was selected, and the sample was repeatedly introduced 6 times, and the content of 2-nitropropane in the sample solution was calculated, respectively, and the results are shown in Table 1. Meanwhile, 4 samples were selected, labeled (i.e., 2-nitropropane was added) respectively, then the sample solution prepared according to the method described in section "1.3.2 sample preparation" was sampled under the conditions described in section "1.2 gas chromatography conditions", and the recovery rate of labeled samples was calculated, and the results are shown in table 2.
TABLE 1 reproducibility test of the content of 2-nitropropane in sample solutions
| 1 St time | 2 Nd time | 3 Rd time | Fourth time | 5 Th time | Last time (6) | Average value of | S | RSD％ |
| 10.50 | 10.53 | 10.45 | 10.32 | 10.61 | 10.56 | 10.45 | 0.11 | 1.08 |
TABLE 2 labeled recovery test results
2.2 Accuracy and repeatability
10 Parts of sample solutions were prepared in parallel according to the section "1.3.2 sample preparation" and were sampled under the conditions described in the section "1.2 gas chromatography conditions", respectively, and the detection results are shown in Table 3.
TABLE 3 repeatability results
As can be seen from table 3, the method is excellent in accuracy and reproducibility.
2.3 Detection of reaction liquid sample of 2-NP prepared by catalytic ammoxidation at different concentrations
2.3.1 10%2-NP reaction liquid sample detection
1G of reaction solution for preparing 2-NP by catalytic ammoxidation is weighed, 0.1g of 1,4 dioxane standard substance is added to obtain a solution to be detected, then sample injection is carried out under the condition of the section of 1.2 gas chromatography for gas chromatography test, a chromatogram is shown in figure 4, and the concentration of 2-nitropropane in the reaction solution can be calculated to be 10.58% according to the internal standard quantity.
2.3.2 Detection of 2-NP reaction liquid sample after concentration
1G of reaction solution for preparing 2-NP by catalytic ammoxidation is weighed, 0.1g of 1,4 dioxane standard substance is added to obtain a solution to be detected, then sample injection is carried out under the condition of the section of 1.2 gas chromatography for gas chromatography test, a chromatogram is shown in figure 5, and the concentration of 2-nitropropane in the reaction solution can be calculated to be 14.23% according to the internal standard quantity.
The above description is only illustrative of the preferred embodiments of the application and the technical principles employed. Meanwhile, the scope of the application is not limited to the technical scheme formed by the specific combination of the technical features, and other technical schemes formed by any combination of the technical features or the equivalent features thereof without departing from the inventive concept are also covered. Such as the above-mentioned features and the technical features disclosed in the present application (but not limited to) having similar functions are replaced with each other.
Claims (8)
1. A method for measuring products in a reaction liquid for preparing 2-NP by catalytic ammoxidation is characterized by comprising the following steps: the method comprises the following steps:
A1, preparing a homogeneous phase solution, namely placing ammonia water with the concentration of 5% -27% into a solvent, obtaining a crude homogeneous phase solution under the premise of temperature control by stirring, placing a 2-nitropropane standard sample into the crude homogeneous phase solution, wherein the ratio of the ammonia water to the 2-nitropropane standard sample is 1-2:1, and obtaining the homogeneous phase solution by an ultrasonic mode under the premise of temperature control;
a2, preparing homogeneous phase solutions with different concentrations, diluting the homogeneous phase solutions into 2-nitropropane standard solutions with different concentrations by using a solvent, and adding internal standard substances into the 2-nitropropane standard solutions with different concentrations to obtain homogeneous phase solutions I with different concentrations;
A3, detecting the homogeneous solution I, and detecting the homogeneous solution I with different concentrations by adopting a gas chromatography method to determine the linear relation between the peak area ratio of the 2-nitropropane with different concentrations and the internal standard peak content ratio of the 2-nitropropane with different concentrations;
A4, preparing a 2-nitropropane reaction liquid sample, and carrying out catalytic ammoxidation on the homogeneous phase solution I to obtain the 2-nitropropane reaction liquid sample;
A5, detecting the 2-nitropropane reaction liquid sample by adopting a gas chromatography method which is the same as that in the step A2, and calculating the content of the 2-nitropropane by adopting an internal standard quantitative method;
the detector adopted by the gas chromatography is an FID hydrogen flame detector, and hydrogen and air are respectively used as auxiliary gases, and a polar chromatographic column, a medium-grade chromatographic column and a weak-polar chromatographic column are used as chromatographic columns.
2. The method for determining the product in the reaction liquid for preparing 2-NP by catalytic ammoxidation according to claim 1, wherein the method comprises the following steps: the solvent in the step A2 is one or more of methanol, ethanol and acetonitrile mixed with water.
3. The method for determining the product in the reaction liquid for preparing 2-NP by catalytic ammoxidation according to claim 1, wherein the method comprises the following steps: the temperature in the step A1 is controlled to be between-5 ℃ and 25 ℃.
4. The method for determining the product in the reaction liquid for preparing 2-NP by catalytic ammoxidation according to claim 1, wherein the method comprises the following steps: the mass ratio of the organic solvent in the solvent to water in the crude homogeneous phase solution is 0.01-0.2:1.
5. The method for determining the product in the reaction liquid for preparing 2-NP by catalytic ammoxidation according to claim 1, wherein the method comprises the following steps: the ratio of the ammonia water to the 2-nitropropane standard sample is preferably 1.1-1.3:1.
6. The method for determining the product in the reaction liquid for preparing 2-NP by catalytic ammoxidation according to claim 1, wherein the method comprises the following steps: the internal standard is one of tetrahydrofuran, 1, 4-dioxane and isopropanol and is water-soluble organic oxygen-containing compound, and the internal standard is preferably 1, 4-dioxane.
7. The method for determining the product in the reaction liquid for preparing 2-NP by catalytic ammoxidation according to claim 1, wherein the method comprises the following steps: the detection conditions of the gas chromatography are as follows: the flow rate of the carrier gas is 1.0-5.0mL/min; the sample injection amount is 0.1-1 mu L; the temperature of the sample inlet is 220-300 ℃; the temperature of the detector is 280-350 ℃; the hydrogen flow is 30-60mL/min; the air flow rate is 350-400mL/min, and the temperature rise program is as follows;
Firstly keeping the constant temperature at 50-100 ℃ for 1-10min, then heating to 220-300 ℃ at the heating rate of 10-30 ℃/min, and then keeping the constant temperature for 10-15min.
8. The method for determining the product in the reaction liquid for preparing 2-NP by catalytic ammoxidation according to claim 1, wherein the method comprises the following steps: the content of the 2-nitropropane standard solution is in the range of 0.4-17%, and the content of the 2-nitropropane reaction solution is in the range of 1-15%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410126746.0A CN118090949A (en) | 2024-01-30 | 2024-01-30 | Method for determining product in reaction liquid for preparing 2-NP by catalytic ammoxidation |
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