CN114624275A - Quantitative analysis method for fluorine-containing waste liquid components - Google Patents
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 91
- 239000011737 fluorine Substances 0.000 title claims abstract description 91
- 239000007788 liquid Substances 0.000 title claims abstract description 78
- 239000002699 waste material Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 9
- 238000001228 spectrum Methods 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 238000012360 testing method Methods 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- 238000009616 inductively coupled plasma Methods 0.000 claims abstract description 7
- 238000005481 NMR spectroscopy Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 238000005070 sampling Methods 0.000 claims description 10
- VFQOFJQVKVEXIY-UHFFFAOYSA-N 3-(phenylmethoxycarbonylamino)-3-piperidin-3-ylpropanoic acid Chemical compound C1CCNCC1C(CC(=O)O)NC(=O)OCC1=CC=CC=C1 VFQOFJQVKVEXIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- -1 cation ions Chemical class 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 claims description 5
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 4
- OAWAZQITIZDJRB-UHFFFAOYSA-N 2-chloro-2,2-difluoroacetic acid Chemical group OC(=O)C(F)(F)Cl OAWAZQITIZDJRB-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
- 150000007960 acetonitrile Chemical class 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000004255 ion exchange chromatography Methods 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 7
- 239000006260 foam Substances 0.000 description 4
- SLVAEVYIJHDKRO-UHFFFAOYSA-N trifluoromethanesulfonyl fluoride Chemical compound FC(F)(F)S(F)(=O)=O SLVAEVYIJHDKRO-UHFFFAOYSA-N 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000010966 qNMR Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
- G01N24/082—Measurement of solid, liquid or gas content
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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
- G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
- G01N21/68—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence using high frequency electric fields
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Abstract
The invention relates to a quantitative analysis method for fluorine-containing waste liquid components, and belongs to the technical field of chemical industry. Firstly, determining a fluorine-containing compound containing hydrogen through a nuclear magnetic hydrogen spectrum and a fluorine spectrum, adding a proper internal standard compound, carrying out quantitative nuclear magnetic fluorine spectrum, and calculating the content of the fluorine-containing compound in the fluoride-containing waste liquid according to peak areas; then, quantitatively analyzing the content of metal ions in the waste liquid by using an inductively coupled plasma emission spectrometer method; and finally, quantitatively analyzing the content of the cations in the waste liquid by using an ion chromatography method, and determining according to a data result. The method can accurately, qualitatively and quantitatively analyze the types and the contents of fluorinated substances and metal ions in the fluorine-containing waste liquid, and the method can be used for in-situ testing without damaging the composition of the solution. The method has the advantages of simple and reliable sample configuration, small error and high accuracy.
Description
Technical Field
The invention relates to a quantitative analysis method for fluorine-containing waste liquid components, and belongs to the technical field of chemical industry.
Background
The preparation of the trifluoromethanesulfonic acid series products by electrolytic fluorination has many steps, a large amount of raw materials and auxiliary materials are usually consumed, toxic and harmful gas and liquid are generated in the production process, and if the gases and the liquid are discharged randomly without being treated, the toxic and harmful gas and liquid pose a great threat to the natural environment in which human beings live. Therefore, the three wastes treatment and discharge must be reasonably carried out, and the development of advanced fluorine-containing compound trifluoro treatment technology is imperative.
When the waste gas absorption pool uses high-concentration alkali liquor to absorb the tail gas of the trifluoromethyl sulfuryl fluoride rectifying tower, the waste liquid pool accumulates high-concentration fluorine-containing waste water along with the accumulation of time to generate a large amount of foams, and the components of the waste liquid must be analyzed to remove various components in a targeted manner.
Disclosure of Invention
In view of the above, the present invention provides a method for quantitatively analyzing components of a fluorine-containing waste liquid, the method comprises determining a hydrogen-containing fluorine-containing compound through a nuclear magnetic hydrogen spectrum and a fluorine spectrum, performing a quantitative nuclear magnetic fluorine spectrum by adding a suitable internal standard compound, and calculating the content of the fluorine-containing compound in the fluorine-containing waste liquid according to a peak area; then, quantitatively analyzing the content of metal ions in the waste liquid by using an inductively coupled plasma emission spectrometer method; and finally, quantitatively analyzing the content of the cations in the waste liquid by using an ion chromatography method, and determining according to a data result.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a quantitative analysis method for fluorine-containing waste liquid components comprises the following steps:
(1) testing the pH value of the fluorine-containing waste liquid; if the alkali is alkaline, directly carrying out the step (2); if the pH value is acidic, adjusting the pH value to be alkaline;
(2) placing the alkaline fluorine-containing waste liquid into a nuclear magnetic tube, adding a deuterogen reagent I, performing a nuclear magnetic resonance hydrogen spectrum test, and determining the type of a hydrogen-containing compound in the waste liquid; placing the alkaline fluorine-containing waste liquid into a nuclear magnetic tube, adding a deutero reagent II, and performing nuclear magnetic resonance fluorine spectrum test to determine the type of fluorine-containing compounds in the waste liquid;
(3) uniformly mixing the waste liquid and the fluorine-containing hydrocarbon internal standard, adding heavy water for dissolving, wherein the molar ratio of the fluorine-containing hydrocarbon internal standard to the fluorine-containing compound in the waste liquid is 1: 10-10: 1, performing quantitative nuclear magnetic resonance fluorine spectrum test, and calculating the content of the fluorine-containing compound according to peak area; the method comprises the steps of setting a fluorine spectrum pulse sequence as zg, zg30 or zg60, setting the spectrum width as 50-200 ppm, the number of empty scanning times as 2-1024, the number of sampling points as 16K-128K, the pulse width as 2-40 us, the number of sampling times as 8-1024, the relaxation delay time as 0.1-100 s, the gain (RG) as 1-203 and the radio frequency center frequency as-200-300 ppm;
the fluorochemical sample content was calculated according to the following formula:
W％＝(mIS×FIS×AS×MS×100％)/(MIS×AIS×FS×mS)；
wherein, W percent is the content of the fluorine-containing compound sample;
mS-mass of fluorochemical sample, g;
FS-quantifying the number of fluorine atoms of a target peak in a sample of a fluorine-containing compound;
MS-molar mass of fluorine-containing compound, g/mol;
AS-integral value of quantitative target peak of fluorochemical sample;
mIS-mass of internal standard, g;
FIS-quantifying the number of fluorine atoms of the target peak with an internal standard;
MIS-the molar mass of the internal standard, g/mol;
AIS-quantifying the integrated value of the target peak by an internal standard;
(4) diluting the waste liquid, and then quantitatively analyzing the cation ions in the waste liquid by using an inductively coupled plasma emission spectrometer to obtain the cation content in the waste liquid;
(5) and (4) determining the content and the content of the waste liquid according to the results of the step (3) and the step (4).
Preferably, the deuterated reagent I in the step (2) is deuterium oxide, deuterated methanol, deuterated acetonitrile, deuterated chloroform or deuterated dimethyl sulfoxide.
Preferably, the deuterated reagent II in the step (2) is heavy water, methanol, acetonitrile, chloroform or dimethyl sulfoxide.
Preferably, the molar ratio of the fluorine-containing hydrocarbon internal standard in the step (3) to the fluorine-containing compound in the waste liquid is 1: 1.
Preferably, the internal standard of the fluorine-containing hydrocarbon in the step (3) is difluoromonochloroacetic acid, 4-fluorocinnamic acid, fluorobenzene or trifluorotoluene.
Advantageous effects
The method can accurately, qualitatively and quantitatively analyze the types and the contents of fluorinated substances and metal ions in the fluorine-containing waste liquid, and the method can be used for in-situ testing without damaging the composition of the solution. The method has the advantages of simple and reliable sample configuration, small error and high accuracy.
Drawings
FIG. 1 is a qualitative NMR chart as described in example 1;
FIG. 2 is the qualitative NMR fluorine spectrum of example 1;
FIG. 3 is the quantitative NMR fluorine spectrum of example 1;
FIG. 4 is a qualitative NMR chart of example 2;
FIG. 5 is the qualitative NMR fluorine spectrum of example 2;
FIG. 6 is the quantitative NMR fluorine spectrum of example 2;
FIG. 7 is a qualitative NMR chart of example 3;
FIG. 8 is a qualitative NMR fluorine spectrum as described in example 3;
FIG. 9 shows the quantitative NMR fluorine spectra as described in example 3.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
(1) Taking 10mL of fluorine-containing waste liquid generated by absorbing tail gas of a trifluoromethyl sulfuryl fluoride rectifying tower by high-concentration alkali liquor, and measuring the pH value to be alkaline by using pH test paper;
(2) putting 0.1mL of the waste liquid into a No. 1 nuclear magnetic tube, adding 0.5mL of heavy water for nuclear magnetic resonance hydrogen spectrum test of a water pressure peak, and determining the type of a hydrogen-containing compound in the waste liquid and the nuclear magnetic hydrogen spectrum1H NMR is shown in FIG. 1; placing the alkaline fluorine-containing waste liquid into a nuclear magnetic tube, adding a deutero reagent II, performing nuclear magnetic resonance fluorine spectrum test, determining the type of fluorine-containing compounds in the waste liquid, and performing nuclear magnetic resonance fluorine spectrum19F NMR is shown in FIG. 2;
the nuclear magnetic hydrogen spectrum results are shown in table 1:
TABLE 1
| Serial number | Chemical shift | Chemical composition |
| 1 | 4.7ppm | H2O |
The nuclear magnetic fluorine spectrum results are shown in table 2:
TABLE 2
| Serial number | Chemical shift | Chemical composition |
| 1 | -78.8ppm | CF3SO3- |
(3) Accurately weighing 2.0000g of waste liquid and 0.0400g of 4-fluorocinnamic acid in a 10mL beaker, uniformly stirring, adding 0.1mL of the mixture into a No. 2 nuclear magnetic tube, adding 0.5mL of heavy water, mixing and dissolving, carrying out quantitative nuclear magnetic resonance fluorine spectrum test, and calculating the content of the fluorine-containing compound according to the peak area; wherein, when the quantitative nuclear magnetic resonance fluorine spectrum is tested, the pulse sequence is zg; spectral Width (SW) of 100 ppm; the number of empty sweeps (DS) is 2; the number of sampling points is 64K; pulse width 10.9 us; the sampling times are 8 times; the relaxation delay time is 50 s; a gain (RG) of 203; the radio frequency center frequency is-150 ppm; the nuclear magnetic fluorine spectrum is shown in FIG. 3, and the calculation results are shown in Table 3;
TABLE 3
| Molecular weight | Molar ratio of | Weight (D) | Mass fraction (wt) | |
| CF3SO3- | 149 | 3.643 | 0.0392g | 1.92％ |
| 4-fluorocinnamic acid | 166 | 1 | 0.0360g |
(4) Diluting 1mL of waste liquid by 50 times, and then carrying out quantitative analysis on cation ions in the waste liquid by using an inductively coupled plasma emission spectrometer to obtain the cation content in the waste liquid, wherein the result is shown in Table 4;
TABLE 4
| Sample (ppm) | Al3+ | Ba2+ | Ca2+ | Cr3+ | Fe2+ | Mg2+ | Na | Pb2+ | Si | Zn2+ |
| Foam samples | 201 | 31 | 37990 | 114 | 215 | 719 | 71 | 91 | 926 | 191 |
(5) According to the results of the step (3) and the step (4), the composition and content of the waste liquid are determined, and the results are shown in Table 5.
TABLE 5
| Numbering | Ion species | Content (wt%) |
| 1 | CF3SO3 - | 1.92％ |
| 2 | Ca2+ | 3.80％ |
Example 2
(1) Taking 10mL of fluorine-containing waste liquid generated by absorbing tail gas of a trifluoromethyl sulfuryl fluoride rectifying tower by high-concentration alkali liquor, and measuring the pH value to be alkaline by using pH test paper;
(2) putting 0.1mL of the waste liquid into a No. 1 nuclear magnetic tube, adding 0.5mL of heavy water for nuclear magnetic resonance hydrogen spectrum test of a water pressure peak, and determining the type of a hydrogen-containing compound in the waste liquid and the nuclear magnetic hydrogen spectrum1H NMR is shown in FIG. 4; placing the alkaline fluorine-containing waste liquid into a nuclear magnetic tube, adding a deutero reagent II, performing nuclear magnetic resonance fluorine spectrum test, determining the type of fluorine-containing compounds in the waste liquid, and performing nuclear magnetic resonance fluorine spectrum19F NMR is shown in FIG. 5;
the nuclear magnetic hydrogen spectrum results are shown in table 6:
TABLE 6
| Serial number | Chemical shift | Chemical composition |
| 1 | 4.7ppm | H2O |
The nuclear magnetic fluorine spectrum results are shown in table 7:
TABLE 7
(3) Accurately weighing 2.0452g of waste liquid and 0.0310g of 4-fluorocinnamic acid in a 10mL beaker, uniformly stirring, adding 0.1mL of the mixture into a No. 2 nuclear magnetic tube, adding 0.5mL of heavy water, mixing and dissolving, performing quantitative nuclear magnetic resonance fluorine spectrum test, and calculating the content of the fluorine-containing compound according to the peak area; wherein, when the quantitative nuclear magnetic resonance fluorine spectrum is tested, the pulse sequence is zg; spectral Width (SW) of 100 ppm; the number of empty sweeps (DS) is 2; the number of sampling points is 64K; pulse width 10.9 us; the sampling times are 8 times; the relaxation delay time is 50 s; a gain (RG) of 203; the radio frequency center frequency is-150 ppm; the nuclear magnetic fluorine spectrum is shown in fig. 6, and the calculation results are shown in table 8;
TABLE 8
| Molecular weight | Molar ratio of | Weight (D) | Mass fraction (wt) | |
| CF3SO3 - | 149 | 3.597 | 0.0338g | 1.65％ |
| 4-Fluorocinnamic acid | 166 | 1 | 0.0310g |
(4) Diluting 1mL of waste liquid by 50 times, and then carrying out quantitative analysis on cation ions in the waste liquid by using an inductively coupled plasma emission spectrometer to obtain the cation content in the waste liquid, wherein the result is shown in Table 9;
TABLE 9
| Sample (ppm) | Al3+ | Ba2+ | Ca2+ | Cr3+ | Fe2+ | Mg2+ | Na | Pb2+ | Si | Zn2+ |
| Foam samples | 201 | 31 | 36550 | 114 | 215 | 719 | 71 | 91 | 926 | 191 |
(5) According to the results of the step (3) and the step (4), the composition and content of the waste liquid were determined, and the results are shown in Table 10.
| Numbering | Ion species | Content (wt%) |
| 1 | CF3SO3 - | 1.65％ |
| 2 | Ca2+ | 3.65％ |
Example 3
(1) Taking 10mL of fluorine-containing waste liquid generated by absorbing tail gas of a trifluoromethyl sulfuryl fluoride rectifying tower by high-concentration alkali liquor, and measuring the pH value to be alkaline by using pH test paper;
(2) putting 0.1mL of the waste liquid into a No. 1 nuclear magnetic tube, adding 0.5mL of heavy water for nuclear magnetic resonance hydrogen spectrum test of a water pressure peak, and determining the type of a hydrogen-containing compound in the waste liquid and the nuclear magnetic hydrogen spectrum1H NMR is shown in FIG. 7; placing the alkaline fluorine-containing waste liquid into a nuclear magnetic tube, adding a deutero reagent II, performing nuclear magnetic resonance fluorine spectrum test, determining the type of fluorine-containing compounds in the waste liquid, and performing nuclear magnetic resonance fluorine spectrum19F NMR is shown in FIG. 8;
the nuclear magnetic hydrogen spectrum results are shown in table 11:
TABLE 11
| Serial number | Chemical shift | Chemical composition |
| 1 | 4.7ppm | H2O |
The results of nuclear magnetic fluorine spectroscopy are shown in table 12:
TABLE 12
| Serial number | Chemical shift | Chemical composition |
| 1 | -78.8ppm | CF3SO3 - |
(3) Accurately weighing 2.0005g of waste liquid and 0.0308g of 4-fluorocinnamic acid in a 10mL beaker, uniformly stirring, adding 0.1mL of the mixture into a No. 2 nuclear magnetic tube, adding 0.5mL of heavy water, mixing and dissolving, performing quantitative nuclear magnetic resonance fluorine spectrum test, and calculating the content of the fluorine-containing compound according to the peak area; wherein, when the quantitative nuclear magnetic resonance fluorine spectrum is tested, the pulse sequence is zg; spectral Width (SW) of 100 ppm; the number of empty sweeps (DS) is 2; the number of sampling points is 64K; pulse width 10.9 us; the sampling times are 8 times; a relaxation delay time of 50 s; a gain (RG) of 203; the radio frequency center frequency is-150 ppm; the nuclear magnetic fluorine spectrum is shown in fig. 9, and the calculation results are shown in table 13;
watch 13
| Molecular weight | Molar ratio of | Weight (D) | Mass fraction (wt) | |
| CF3SO3 - | 149 | 3.751 | 0.0344g | 1.72％ |
| 4-Fluorocinnamic acid | 166 | 1 | 0.0308g |
(4) Diluting 1mL of waste liquid by 50 times, and then carrying out quantitative analysis on cation ions in the waste liquid by using an inductively coupled plasma emission spectrometer to obtain the cation content in the waste liquid, wherein the result is shown in Table 14;
TABLE 14
| Sample (ppm) | Al3+ | B | Ba2+ | Ca2+ | Cr3+ | Fe2+ | Mg2+ | Na | Pb2+ | Si |
| Foam samples | 201 | 52 | 31 | 41600 | 114 | 215 | 719 | 71 | 91 | 926 |
(5) According to the results of the steps (3) and (4), the composition and content of the waste liquid were determined, and the results are shown in Table 15.
Watch 15
| Numbering | Ion species | Content (wt%) |
| 1 | CF3SO3 - | 1.72％ |
| 2 | Ca2+ | 4.16％ |
In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.
Claims (5)
1. A quantitative analysis method for fluorine-containing waste liquid components is characterized by comprising the following steps: the method comprises the following steps:
(1) testing the pH value of the fluorine-containing waste liquid; if the alkali is alkaline, directly carrying out the step (2); if the pH value is acidic, adjusting the pH value to be alkaline;
(2) placing the alkaline fluorine-containing waste liquid into a nuclear magnetic tube, adding a deuterogen reagent I, performing a nuclear magnetic resonance hydrogen spectrum test, and determining the type of a hydrogen-containing compound in the waste liquid; placing the alkaline fluorine-containing waste liquid into a nuclear magnetic tube, adding a deutero reagent II, and performing nuclear magnetic resonance fluorine spectrum test to determine the type of fluorine-containing compounds in the waste liquid;
(3) uniformly mixing the waste liquid and the fluorine-containing hydrocarbon internal standard, adding heavy water for dissolving, wherein the molar ratio of the fluorine-containing hydrocarbon internal standard to the fluorine-containing compound in the waste liquid is 1: 10-10: 1, performing quantitative nuclear magnetic resonance fluorine spectrum test, and calculating the content of the fluorine-containing compound according to peak area; the method comprises the steps of setting a fluorine spectrum pulse sequence as zg, zg30 or zg60, setting the spectrum width as 50-200 ppm, the number of empty scanning times as 2-1024, the number of sampling points as 16K-128K, the pulse width as 2-40 us, the number of sampling times as 8-1024, the relaxation delay time as 0.1-100 s, the gain as 1-203 and the radio frequency center frequency as-200-300 ppm;
(4) diluting the waste liquid, and then quantitatively analyzing the cation ions in the waste liquid by using an inductively coupled plasma emission spectrometer to obtain the cation content in the waste liquid;
(5) and (4) determining the content and the content of the waste liquid according to the results of the step (3) and the step (4).
2. The method for quantitatively analyzing components of a fluorine-containing waste liquid according to claim 1, characterized in that: in the step (2), the deuterated reagent I is deuterium oxide, deuterated methanol, deuterated acetonitrile, deuterated chloroform or deuterated dimethyl sulfoxide.
3. The method for quantitatively analyzing components of a fluorine-containing waste liquid according to claim 1, characterized in that: in the step (2), the deuterated reagent II is heavy water, methanol, acetonitrile, chloroform or dimethyl sulfoxide.
4. The method for quantitatively analyzing components of a fluorine-containing waste liquid according to claim 1, characterized in that: and (4) the molar ratio of the fluorine-containing hydrocarbon internal standard in the step (3) to the fluorine-containing compound in the waste liquid is 1: 1.
5. The method for quantitatively analyzing components of a fluorine-containing waste liquid according to claim 1, characterized in that: and (3) the fluorine-containing hydrocarbon internal standard is difluoromonochloroacetic acid, 4-fluorocinnamic acid, fluorobenzene or trifluorotoluene.
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