CN115032181B - Quantitative analysis method of ketazine hydrazine hydrate byproduct isopropyl hydrazine - Google Patents
Quantitative analysis method of ketazine hydrazine hydrate byproduct isopropyl hydrazine Download PDFInfo
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- KJAQRHMKLVGSCG-UHFFFAOYSA-N propan-2-ylhydrazine Chemical compound CC(C)NN KJAQRHMKLVGSCG-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 42
- PFLUPZGCTVGDLV-UHFFFAOYSA-N acetone azine Chemical compound CC(C)=NN=C(C)C PFLUPZGCTVGDLV-UHFFFAOYSA-N 0.000 title claims abstract description 40
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 title claims abstract description 36
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000006227 byproduct Substances 0.000 title claims abstract description 21
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 42
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 39
- 239000000523 sample Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 238000012360 testing method Methods 0.000 claims abstract description 10
- 239000012086 standard solution Substances 0.000 claims abstract description 9
- JCLFHZLOKITRCE-UHFFFAOYSA-N 4-pentoxyphenol Chemical compound CCCCCOC1=CC=C(O)C=C1 JCLFHZLOKITRCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 230000005284 excitation Effects 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012468 concentrated sample Substances 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- 238000003556 assay Methods 0.000 claims 1
- SPFZSFCIDACZFA-UHFFFAOYSA-N nitrous amide;hydrate Chemical compound O.NN=O SPFZSFCIDACZFA-UHFFFAOYSA-N 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- -1 amine compounds Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a quantitative analysis method of a ketazine hydrazine hydrate byproduct isopropyl hydrazine, which comprises the following steps: s1, preparing a specific fluorescent probe into a specific fluorescent probe-DMSO solution, and preparing a plurality of groups of standard solutions with the specific fluorescent probe concentration of Amol/L and the known isopropyl hydrazine concentration from the specific fluorescent probe-DMSO solution and the isopropyl hydrazine; testing the standard solution by using a fluorescence spectrometer to determine the quantitative relation between the fluorescence intensity and the concentration of the isopropyl hydrazine; s2, mixing a specific fluorescent probe-DMSO solution with a sample to be detected to prepare a solution to be detected; testing the solution to be detected by using a fluorescence spectrometer, and recording the fluorescence intensity; and (3) calculating the concentration of the isopropyl hydrazine in the solution to be detected according to the quantitative relation between the fluorescence intensity and the concentration of the isopropyl hydrazine determined in the step (S1). The advantages are that: the method realizes the rapid and accurate determination of the concentration of the isopropyl hydrazine in the ketazine hydrazine hydrate production system.
Description
Technical Field
The invention relates to the technical field of analysis and detection, in particular to a detection technology of a ketazine hydrazine hydrate byproduct isopropyl hydrazine.
Background
Hydrazine hydrate, also called hydrazine hydrate, is an important chemical raw material, and the production method mainly comprises a Laxi method, a urea method, a ketazine method, a hydrogen peroxide method, an air oxidation method and the like. The hydrazine hydrate production method is a ketazine method, which adopts acetone, sodium hypochlorite and ammonia to react to produce an intermediate ketazine, and the ketazine is further hydrolyzed to generate hydrazine hydrate.
During the ketazine hydrolysis reaction, the following side reactions may also occur to form byproduct impurities:
CH 3COCH3+H→CH3COHCH3 (isopropanol)
CH 3COHCH3+N2H4·H2O→(CH3)2CHNHNH2 (isopropyl hydrazine)
The acetone generated by the hydrolysis reaction is reduced to obtain isopropanol, and the isopropanol and the hydrazine hydrate generate isopropyl hydrazine, so that the material cannot be hydrolyzed to generate hydrazine hydrate, and the yield of the hydrazine hydrate is reduced; because the boiling point of the isopropyl hydrazine is similar to that of the ketazine, the isopropyl hydrazine is not carried out along with acetone or hydrazine hydrate in a hydrolysis system, but slowly accumulated in the hydrolysis system, so that the effective reaction space is occupied, the productivity is reduced, the steam consumption is increased, the ketazine hydrolysis rate is reduced, and the isopropyl hydrazine separation and treatment system is matched in a ketazine method hydrazine hydrate production system. The Chinese patent publication No. CN105384655B discloses a method for removing impurities in a hydrazine hydrate hydrolysis system by a ketazine method, which comprises the steps of pressurized hydrolysis, pressurized separation and the like. The method is that a ketazine solution containing impurity isopropyl hydrazine in a hydrazine hydrate hydrolysis system is introduced into a secondary pressurized hydrolysis tower, so that ketazine is completely hydrolyzed into hydrazine hydrate and acetone, acetone and isopropyl hydrazine are returned to a primary pressurized separation tower for separation in a steam form, acetone is separated out from the top of the primary pressurized separation tower according to different boiling points of substances, the acetone is returned to an acetone recovery system for recycling, and the water-containing isopropyl hydrazine is obtained from the bottom of the tower.
The separation and treatment system of the isopropyl hydrazine usually runs discontinuously, the separation and treatment system is carried out according to the accumulation condition of the isopropyl hydrazine in the system, the concentration of the isopropyl hydrazine in the system is very low, and a method for rapidly and accurately measuring the concentration of the isopropyl hydrazine in the system is lacking in actual production.
Disclosure of Invention
The invention provides a quantitative analysis method of isopropyl hydrazine as a byproduct of ketazine hydrazine hydrate, which aims to rapidly and accurately determine the concentration of isopropyl hydrazine in a ketazine hydrazine hydrate production system.
The technical scheme adopted by the invention is as follows: the quantitative analysis method of the byproduct isopropyl hydrazine of the ketazine hydrazine hydrate comprises the steps of:
Because the synthesizing tower, the hydrolyzing tower, the separating tower and the impurity removing tower in the production flow of the hydrazine hydrate contain various amine compounds, such as amine compounds of aliphatic amine, aromatic amine, amide and the like, including propylamine, diisopropylethylamine, aniline, urea, N-dimethylformamide and the like. The biggest difficulty faced in using fluorescent probes to determine the isopropylhydrazine in a sample is therefore how to ensure that the fluorescent probes only react with the isopropylhydrazine in a characteristic fluorescence color change reaction which can be characterized, but do not react with or interfere with other amine compounds in a fluorescence color change reaction. The specific fluorescent probe provided by the invention can be subjected to rapid reaction elimination reaction with isopropyl hydrazine and fluorescent color change reaction (experiments prove that when the concentration of isopropyl hydrazine is 500ppm, the sample reacts with the fluorescent probe to generate obvious color change within 5 min), and the specific fluorescent probe does not generate fluorescent color change reaction with other amine substances existing in the sample to be detected, so that the specific fluorescent probe has high selectivity and can completely eliminate the interference of impurities in the sample to be detected. Solves the problem that the content of isopropyl hydrazine in a sample is difficult to be measured by using a fluorescent probe in the current ketazine hydrazine hydrate production process.
The quantitative analysis method of the ketazine hydrazine hydrate byproduct isopropyl hydrazine can be implemented according to the following steps:
S1, preparing a specific fluorescent probe-DMSO solution from the specific fluorescent probe by using a solvent DMSO, and preparing a plurality of groups of standard solutions with the specific fluorescent probe concentration of Amol/L and the known isopropyl hydrazine concentration from the specific fluorescent probe-DMSO solution and different known amounts of isopropyl hydrazines; testing the standard solution by using a fluorescence spectrometer to determine the quantitative relation between the fluorescence intensity and the concentration of the isopropyl hydrazine;
s2, mixing the specific fluorescent probe-DMSO solution with a sample to be detected to prepare a solution to be detected, wherein the concentration of the specific fluorescent probe is Amol/L, and the concentration of the isopropyl hydrazine is unknown; testing the solution to be detected by using a fluorescence spectrometer, and recording fluorescence intensity; and (3) calculating the concentration of the isopropyl hydrazine in the solution to be detected according to the quantitative relation between the fluorescence intensity and the concentration of the isopropyl hydrazine determined in the step (S1).
As a further improvement of the present invention, the method further comprises the step of concentrating the sample to be tested. The method can be implemented according to the following steps:
A. Distilling a sample to be tested possibly containing isopropyl hydrazine in the production process of hydrazine hydrate by a ketazine method, and distilling low-boiling substances to obtain a concentrated solution;
B. standing and layering the concentrated solution into a water phase and an oil phase, removing the water phase, and extracting the oil phase by using diethyl ether to obtain an extract;
C. And (3) distilling the extract, controlling the distillation temperature to be 106-108 ℃ after the diethyl ether is distilled, and collecting fractions to obtain a concentrated sample to be measured.
Experiments show that the higher the content of the isopropyl hydrazine in the sample to be detected is, the faster the specific color change reaction occurs, and the more obvious the color change is. At an isopropyl hydrazine concentration of 500ppm, the reaction of the sample with the specific fluorescent probe of the present invention produces a significant color change within 5 minutes, requiring a longer reaction time if the isopropyl hydrazine content is low. Therefore, in order to increase the detection rate, the sample to be detected can be concentrated first according to the method.
As a further improvement of the invention, the distillation temperature in the step A is 100-108 ℃, the distillation temperature is 95-100 ℃, and the volume ratio of diethyl ether to oil phase in the extraction process in the step B is 2-4:1.
As a further improvement of the invention, in the fluorescence intensity detection process, the excitation slit of the fluorescence spectrometer is 5nm, the emission slit is 5nm, the excitation wavelength is 420nm, and the voltage is 800eV.
As a further improvement of the invention, the concentration of the specific fluorescent probe in the specific fluorescent probe-DMSO solution is 1.0X10 -4 mol/L; the a=1.0×10 -5.
The invention also discloses a reagent for quantitative analysis of the byproduct isopropyl hydrazine of the ketazine hydrazine hydrate, which is characterized by comprising the specific fluorescent probe.
The invention also discloses a method for producing the ketazine hydrazine hydrate, which is characterized by comprising a quantitative analysis method of the by-product isopropyl hydrazine of the ketazine hydrazine hydrate.
The beneficial effects of the invention are as follows: 1) The specific fluorescent probe is used for carrying out rapid reaction and elimination reaction on the isopropyl hydrazine in the sample to be detected, carrying out fluorescent color-changing reaction on the isopropyl hydrazine, and not carrying out fluorescent color-changing reaction on other amine substances in the sample to be detected, so that the problem that the content of the isopropyl hydrazine in the sample is difficult to be measured by using the fluorescent probe in the conventional ketazine hydrazine hydrate production process is solved. 2) The method disclosed by the invention is simple and accurate to operate, high in sensitivity and small in interference from other impurities, and can be used for rapidly analyzing the concentration of the isopropyl hydrazine in a hydrazine hydrate production system by a ketazine method, so that a reference is provided for controlling production process parameters.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a specific fluorescent probe according to the present invention.
FIG. 2 is a graph of fluorescence titration of specific fluorescent probes for isopropyl hydrazine in an embodiment of the present invention.
FIG. 3 is a standard curve established in an embodiment of the present invention.
FIG. 4 is a graph showing the response of the specific fluorescent probe to the identification of common amines in the production of isopropyl hydrazine and other ketazine hydrazines.
Detailed Description
The invention is further illustrated below with reference to examples.
Examples:
Quantitative analysis of the ketazine hydrazine hydrate byproduct isopropyl hydrazine was performed as follows:
(1) And taking an isopropyl hydrazine-containing sample of a hydrazine hydrate production system by a ketazine method, and semi-quantitatively analyzing the concentration of the isopropyl hydrazine in the concentrated sample to be detected by GC-MS to be 124.78ppm. Distilling the sample, controlling the distillation temperature to be 106-108 ℃, the distillation temperature to be 95 ℃, and distilling the low-boiling-point substances to obtain a concentrated solution;
(2) Standing the concentrated solution for 20min to separate into a water phase and an oil phase, removing the water phase, and extracting the oil phase by using diethyl ether, wherein the volume ratio of the extractant to the sample to be extracted is 4:1, so as to obtain an extract;
(3) And (3) distilling the extract, controlling the distillation temperature to be 106-108 ℃ after the diethyl ether is distilled, collecting fractions to obtain a concentrated sample to be detected, and performing GC-MS semi-quantitative analysis on the concentration of the isopropyl hydrazine in the concentrated sample to be detected to be 549.68ppm.
(4) Preparing the specific fluorescent probe into a specific fluorescent probe-DMSO solution by using a solvent DMSO, wherein the concentration of the specific fluorescent probe is 1.0X10 -4 mol/L.
(5) 7 Dry and clean volumetric flasks of 10ml were prepared, 1ml of 1.0X10 -4 mol/L specific fluorescent probe-DMSO solution and different amounts of isopropyl hydrazine were added, respectively, and the volumes were fixed to 10ml with DMSO to prepare standard solutions of 1.0X10 -5 mol/L specific fluorescent probe concentration and 0, 100, 200, 300, 400, 600, 700ppm isopropyl hydrazine concentration, respectively. ;
(6) Testing the standard solution by using a fluorescence spectrometer, setting the excitation wavelength of the fluorescence spectrometer to 420nm, the width of an excitation and emission slit to 5nm, and setting the scanning range to 440-820 nm; the fluorescence intensities of the above solutions at the emission wavelength of 505nm were recorded separately, as shown in FIG. 2. The standard curve of fluorescence intensity F to isopropylhydrazine concentration c is drawn, f=0.54343c+0.78117, and the linear correlation coefficient is R 2 = 0.99297, so that the detection of isopropylhydrazine can be completed, as shown in fig. 3.
(7) 1Ml of a dry and clean volumetric flask is prepared, 1ml of a 1.0X10 -4 mol/L specific fluorescent probe-DMSO solution is added, and 1ml of the concentrated sample to be detected in the step (3) is subjected to volume fixation to 10ml by DMSO to prepare a solution to be detected, wherein the concentration of the specific fluorescent probe is 1.0X10 -5 mol/L, and the concentration of the isopropyl hydrazine is unknown.
(8) Setting the excitation wavelength of the fluorescence spectrometer to 420nm, the width of the excitation and emission slit to 5nm, and setting the scanning range to 440-820 nm; and testing the solution to be tested, recording the fluorescence intensity of the solution at the position with the emission wavelength of 505nm, and repeating the test three times, wherein the fluorescence intensity is respectively as follows: 298.777, 297.892, 298.305.
(9) A standard curve of the fluorescence intensity F to the concentration c of the isopropyl hydrazine; f=0.54343c+0.78117, calculated as the concentration of isopropylhydrazine: 548.36, 546.73, 547.49ppm, with a mean value of 547.53.
Specificity verification test of specific fluorescent probes:
The spectral response of the specific fluorescent probe of the invention to common amine substances in the production of ketazine hydrazine hydrate is verified according to the following steps:
(1) Preparing the specific fluorescent probe into a specific fluorescent probe-DMSO solution by using a solvent DMSO, wherein the concentration of the specific fluorescent probe is 1.0X10 -4 mol/L.
(2) 6 Dry and clean measuring flasks of 10ml are prepared, 1ml of 1.0X10 -4 mol/L specific fluorescent probe-DMSO solution and 4.0mg of isopropyl hydrazine, propylamine, diisopropylethylamine, aniline, urea, N-dimethylformamide are added respectively, and the volumes are fixed to 10ml by DMSO to prepare a solution with the specific fluorescent probe concentration of 1.0X10 -5 mol/L and the concentration of the substance to be measured of 400 ppm.
(3) Setting the excitation wavelength of the fluorescence spectrometer to 420nm, the width of the excitation and emission slit to 5nm, and setting the scanning range to 440-820 nm; and the solutions were tested and the fluorescence intensities of the solutions at an emission wavelength of 505nm were recorded, respectively, as shown in fig. 4. It can be seen that the specific fluorescent probe has good selectivity to isopropyl hydrazine.
Claims (10)
1. The quantitative analysis method of the byproduct isopropyl hydrazine of the ketazine hydrazine hydrate is characterized by comprising the following steps of: reagents used for the assay include specific fluorescent probes of formula a:
2. The method for quantitatively analyzing the byproduct isopropyl hydrazine of the ketazine hydrate according to claim 1, which is characterized by comprising the following steps:
S1, preparing a specific fluorescent probe-DMSO solution from the specific fluorescent probe by using a solvent DMSO, and preparing a plurality of groups of standard solutions with the specific fluorescent probe concentration of Amol/L and the known isopropyl hydrazine concentration from the specific fluorescent probe-DMSO solution and different known amounts of isopropyl hydrazines; testing the standard solution by using a fluorescence spectrometer to determine the quantitative relation between the fluorescence intensity and the concentration of the isopropyl hydrazine;
The preparation method of the standard solution specifically comprises the following steps: adding the specific fluorescent probe-DMSO solution with the same mole and different known amounts of isopropyl hydrazine into different containers respectively, fixing the volume to the same volume by using DMSO, and recording the concentration of the specific fluorescent probe to be Amol/L;
s2, mixing the specific fluorescent probe-DMSO solution with a sample to be detected to prepare a solution to be detected, wherein the concentration of the specific fluorescent probe is Amol/L, and the concentration of the isopropyl hydrazine is unknown; testing the solution to be detected by using a fluorescence spectrometer, and recording fluorescence intensity; calculating the concentration of the isopropyl hydrazine in the solution to be detected according to the quantitative relation between the fluorescence intensity and the concentration of the isopropyl hydrazine determined in the step S1;
the preparation method of the solution to be detected specifically comprises the following steps: adding a certain amount of specific fluorescent probe-DMSO solution and a sample to be detected into a container, and using DMSO to fix the volume to a certain volume, so that the concentration of the specific fluorescent probe is Amol/L.
3. The method for quantitatively analyzing the byproduct isopropyl hydrazine of the ketazine hydrate according to claim 2, wherein the method comprises the following steps: and the method also comprises the step of concentrating the sample to be detected.
4. A method for quantitative analysis of byproduct isopropyl hydrazine of ketazine hydrate according to claim 3, characterized in that: the step of concentrating the sample to be tested comprises the following steps:
A. Distilling a sample to be tested possibly containing isopropyl hydrazine in the production process of hydrazine hydrate by a ketazine method, and distilling low-boiling substances to obtain a concentrated solution;
B. standing and layering the concentrated solution into a water phase and an oil phase, removing the water phase, and extracting the oil phase by using diethyl ether to obtain an extract;
C. And (3) distilling the extract, controlling the distillation temperature to be 106-108 ℃ after the diethyl ether is distilled, and collecting fractions to obtain a concentrated sample to be measured.
5. The method for quantitatively analyzing the byproduct isopropyl hydrazine of ketazine hydrate according to claim 4, wherein the method comprises the following steps: the distillation temperature in the step A is 100-108 ℃, the distillation temperature is 95-100 ℃, and the volume ratio of diethyl ether to oil phase in the extraction process in the step B is 2-4:1.
6. The method for quantitatively analyzing the byproduct isopropyl hydrazine of the ketazine hydrate according to claim 2, wherein the method comprises the following steps: in the fluorescence intensity detection process, the excitation slit of the fluorescence spectrometer is 5nm, the emission slit is 5nm, the excitation wavelength is 420nm, and the voltage is 800eV.
7. The method for quantitatively analyzing the byproduct isopropyl hydrazine of the ketazine hydrate according to claim 2, wherein the method comprises the following steps: the concentration of the specific fluorescent probe in the specific fluorescent probe-DMSO solution is 1.0X10 -4 mol/L; the a=1.0×10 -5.
8. Use of a specific fluorescent probe according to claim 1 as a reagent for quantitative analysis of ketocontinuous hydrazine hydrate byproduct isopropyl hydrazine.
9. A reagent for quantitative analysis of ketohydrazine hydrate byproduct isopropyl hydrazine, characterized by comprising the specific fluorescent probe according to claim 1.
10. The production method of the ketazine hydrazine hydrate is characterized by comprising the following steps of: a method for quantitative analysis of isopropyl hydrazine byproduct comprising ketazine hydrate as recited in any of claims 1 to 7.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104109126A (en) * | 2014-06-30 | 2014-10-22 | 太原理工大学 | Ratiometric fluorescent probe for detecting hydrazine, and preparation method thereof |
| CN105400508A (en) * | 2015-11-09 | 2016-03-16 | 晋江尚京富本环保科技有限公司 | Method for detecting concentration of hydrazine |
| CN107880052A (en) * | 2017-11-02 | 2018-04-06 | 济南大学 | A kind of fluorescence probe for detecting hydrazine and its application |
| CN108059604A (en) * | 2018-01-25 | 2018-05-22 | 山西大学 | It is a kind of to be used to detect fluorescence probe of hydrazine hydrate and its preparation method and application |
| CN111592532A (en) * | 2020-04-20 | 2020-08-28 | 中铁十八局集团有限公司 | Near-infrared fluorescent probe for detecting hydrazine and preparation and application thereof |
| CN112179967A (en) * | 2020-09-30 | 2021-01-05 | 宜宾海丰和锐有限公司 | Online detection method for hydrazine hydrate in production process of ketazine process hydrazine hydrate |
| CN113624727A (en) * | 2021-07-02 | 2021-11-09 | 湖北文理学院 | Method for detecting hydrazine concentration |
| KR20220005871A (en) * | 2020-07-07 | 2022-01-14 | 경희대학교 산학협력단 | Composition for detecting hydrazine and Method for detecting hydrazine using the same |
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2022
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109126A (en) * | 2014-06-30 | 2014-10-22 | 太原理工大学 | Ratiometric fluorescent probe for detecting hydrazine, and preparation method thereof |
| CN105400508A (en) * | 2015-11-09 | 2016-03-16 | 晋江尚京富本环保科技有限公司 | Method for detecting concentration of hydrazine |
| CN107880052A (en) * | 2017-11-02 | 2018-04-06 | 济南大学 | A kind of fluorescence probe for detecting hydrazine and its application |
| CN108059604A (en) * | 2018-01-25 | 2018-05-22 | 山西大学 | It is a kind of to be used to detect fluorescence probe of hydrazine hydrate and its preparation method and application |
| CN111592532A (en) * | 2020-04-20 | 2020-08-28 | 中铁十八局集团有限公司 | Near-infrared fluorescent probe for detecting hydrazine and preparation and application thereof |
| KR20220005871A (en) * | 2020-07-07 | 2022-01-14 | 경희대학교 산학협력단 | Composition for detecting hydrazine and Method for detecting hydrazine using the same |
| CN112179967A (en) * | 2020-09-30 | 2021-01-05 | 宜宾海丰和锐有限公司 | Online detection method for hydrazine hydrate in production process of ketazine process hydrazine hydrate |
| CN113624727A (en) * | 2021-07-02 | 2021-11-09 | 湖北文理学院 | Method for detecting hydrazine concentration |
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