CN112268948B - Sample pretreatment process for testing content of metal ions in carbonyl sulfide - Google Patents
Sample pretreatment process for testing content of metal ions in carbonyl sulfide Download PDFInfo
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- CN112268948B CN112268948B CN202011095012.9A CN202011095012A CN112268948B CN 112268948 B CN112268948 B CN 112268948B CN 202011095012 A CN202011095012 A CN 202011095012A CN 112268948 B CN112268948 B CN 112268948B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
Abstract
The invention discloses a sample pretreatment process for testing the content of metal ions in carbonyl sulfide, which comprises the following steps: s1, preparing an HF aqueous solution with the mass concentration of 1-3%; s2, adding Sc to the HF aqueous solution in the step S12O3Obtaining a mixed solution; sc in the mixed solution2O3The mass concentration of (A) is 0.0001-0.0007%; s3, introducing carbonyl sulfide gas to be detected into the mixed solution in the step S2; meanwhile, a filter membrane is arranged above the mixed solution to filter gas formed when the carbonyl sulfide to be detected is introduced; s4, after the introduction of carbonyl sulfide to be detected is finished, continuing to wait for at least 1 minute, then putting the filter membrane into the mixed solution, and fully stirring and uniformly mixing; s5, filtering the mixed solution obtained in the step S4 by using a second filter membrane to obtain a pretreated sample. The method has high metal ion data precision and high reliability.
Description
Technical Field
The invention relates to the technical field of liquefied gas metal content detection, in particular to a sample pretreatment process for testing the content of metal ions in carbonyl sulfide.
Background
Inductively coupled plasma mass spectrometry (ICP-MS) is widely used as a common metal ion analysis method in the field of electronic chemicals. However, the current sampling system is implemented by a liquid sampling method, and the target product is volatilized and then dissolved in HF, and then is directly sampled by a sampling tube. The ICP-MS system directly injecting sample by gas is not practical in the ICP-MS system because the gaseous metal ion standard gas does not exist, and the sample is directly injected by the gaseous state. For the special gas industry, most of the materials are gaseous inflammable, explosive and toxic substances. Therefore, the analysis of metal ions in special electronic gases is a blank in the field aiming at the special gas industry.
On the other hand, carbonyl sulfide (chemical formula: COS), also called carbonyl sulfide, is a colorless gas having a smell of rotten eggs in a normal state. It is an inorganic carbon compound similar in structure to carbon disulfide and sulfur dioxide, and the gaseous COS molecule is linear. Carbonyl sulfide is stable, but reacts strongly with oxidizing agents, and also corrodes metals in the presence of moisture. Flammable and toxic, but like hydrogen sulfide, can underestimate its concentration in air. Carbonyl sulfide is mainly used for organic synthesis of intermediates, and the pesticide industry is used for synthesizing herbicides, prosulfocarb, molinate, insecticide cartap and the like. It is an intermediate of carbamate herbicides such as diclofop, triallate No. 2, etc. and has wide application. It can be hydrolyzed with water vapor in gas on catalyst to generate hydrogen sulfide, which is removed by active carbon or zinc oxide as desulfurizing agent. The hydrolysis catalyst is generally based on alumina. Oxygen and hydrogen sulfide in the gas can generate oxidation reaction, sulfur dioxide and sulfur trioxide are generated to act with the catalyst, and the catalyst is sulfated to reduce the catalytic activity; the oxygen in the gas also oxidizes the sulfur to carbon, and the resulting elemental sulfur covers the catalyst surface, deactivating the catalyst.
In the prior art, no standard is formed for testing the content of metal ions in carbonyl sulfide by using inductively coupled plasma mass spectrometry, and the main difficulty is that the solubility of carbonyl sulfide is poor, and metal impurities contained in the carbonyl sulfide can run off due to unknown reasons (possibly volatilize due to the formation of a metal complex, and no theory exists at present), so that when the carbonyl sulfide is detected by using the existing standard method, great deviation often occurs: the RSD (relative standard deviation) of the conventional metals Cu, Fe, Mo, Ni, Cr are 200%, 100%, 70%, 150%, 80%, respectively, which is obviously not applicable.
Therefore, a sample pretreatment process for testing the content of metal ions in carbonyl sulfide is developed to ensure that an accurate detection result can be formed when the inductively coupled plasma mass spectrometry is adopted to test the content of the metal ions in the carbonyl sulfide.
Disclosure of Invention
The invention aims to: provides a sample pretreatment process for testing the content of metal ions in carbonyl sulfide, so as to solve the problems in the background technology.
The technical scheme of the invention is as follows: a sample pretreatment process for testing the content of metal ions in carbonyl sulfide comprises the following steps:
s1, preparing an HF aqueous solution with the mass concentration of 1-3%;
s2, adding Sc to the HF aqueous solution in the step S12O3Obtaining a mixed solution; sc in the mixed solution2O3The mass concentration of (A) is 0.0001-0.0007%;
s3, introducing carbonyl sulfide gas to be detected into the mixed solution in the step S2; meanwhile, a filter membrane is arranged above the mixed solution to filter gas formed when the carbonyl sulfide to be detected is introduced;
s4, after the introduction of carbonyl sulfide to be detected is finished, continuing to wait for at least 1 minute, then putting the filter membrane into the mixed solution, and fully stirring and uniformly mixing;
s5, filtering the mixed solution obtained in the step S4 by using a second filter membrane to obtain a pretreated sample.
In the above, it is preferable that Sc is formed in a concentration of 3 to 8ppm in the mixed solution3+A cation; more preferably 4 to 6ppm of Sc3+A cation.
Preferably, in the step S3, the carbonyl sulfide gas to be detected is introduced into the mixed solution in the step S2, and the mass ratio of the mixed solution to the carbonyl sulfide to be detected is 3-10: 1.
preferably, the pore size of the filter membrane in the step S3 is 0.1-0.3 micron.
Preferably, the pore size of the second filter membrane in the step S5 is 0.1 to 0.3 μm.
Preferably, after the step S5, the sample is directly sucked into the ICP-MS instrument through a sample inlet tube of the ICP-MS instrument for metal ion content analysis and detection.
Preferably, in the step S3, the exhaust gas that is not absorbed by the mixed solution is introduced into the NaOH solution for absorption.
For gas, ICP-MS analysis samples are prepared by a solution absorption method, and the repeatability of obtained data is good. However, different liquefied gases have different solubilities in water, when the gas is absorbed by the solution, all metal ions in the liquefied gas and the liquefied gas cannot be ensured to be absorbed by the solution, and in order to completely absorb the metal ions and COS in the liquefied gas into the solution, the invention adds Sc into 200mL of 1% HF aqueous solution2O3In solution, Sc was formed at a concentration of 5ppm3+The positive ions absorb 50mL of liquefied COS gas, metal ions in the liquefied gas enter an HF solution at the same time, after 50mL of liquefied COS is absorbed, a 1% HF aqueous solution is directly sucked into the instrument through a sample inlet pipe of the instrument, the COS is fully absorbed in a product sample injection solution by the sample preparation method, meanwhile, Sc can be used as an internal standard to indicate the reliability of the test method, and after the sample preparation method is utilized, the RSD of Cu, Fe, Mo, Ni and Cr is reduced to 5%, 3% and 2% from 200%, 100%, 70%, 150% and 80%. Compared with the traditional solution evaporation method, the method has higher metal ion data precision, and meanwhile, the reliability of analysis data is improved due to the existence of 5ppm Sc internal standard.
The invention has the advantages that:
(1) adding Sc to an aqueous HF solution2O3And then, the solubility of the COS gas in the mixed solution is increased, the Sc element is a rare metal element, the analysis of metal ions is not interfered, and meanwhile, the Sc element is quantitatively added, so that the COS gas can be used as an internal standard reagent for metal ion analysis and a COS analysis control sample, and the ICP-MS sample pretreatment quality is verified.
(2) According to the invention, the filter membrane is arranged above the mixed solution to filter the gas formed when the carbonyl sulfide to be detected is introduced, so that the metal impurities in the volatile gas can be intercepted and prevented from escaping; and then the filter membrane is put into the mixed solution to be uniformly mixed, so that the metal impurities are dissolved in the sample, and the detection accuracy is ensured.
Detailed Description
Example 1:
1. an analytical instrument: PerkinElmer NexION 300S.
2. Reagent: 1% strength HF aqueous solution, Sc2O3。
A sample pretreatment process for testing the content of metal ions in carbonyl sulfide comprises the following steps:
s1, preparing 200mL of 1% HF aqueous solution;
s2, adding Sc to the HF aqueous solution prepared in step S12O3Preparing a mixed solution in which Sc is formed at a concentration of 5ppm3+A cation;
s3, introducing 50mL of COS gas into the mixed solution in the step S2 to form a sample pretreatment solution, and introducing the waste gas which is not absorbed by the mixed solution into a NaOH solution for absorption;
meanwhile, a 0.2 micron filter membrane is arranged above the mixed solution to filter gas formed when the carbonyl sulfide to be detected is introduced;
s4, after the introduction of carbonyl sulfide to be detected is finished, continuing to wait for at least 1 minute, then putting the filter membrane into the mixed solution, and fully stirring and uniformly mixing;
s5, filtering the mixed solution obtained in the step S4 by using a second filter membrane of 0.2 micron to obtain a pretreated sample;
and S6, directly sucking the sample into the ICP-MS instrument through a sample inlet pipe of the ICP-MS instrument, and analyzing and detecting the content of the metal ions.
The above process was used to pre-treat the sample, and the metal ion content in the COS gas was tested 6 times, and the results are compared with the results of the conventional treatment method (introducing 200mL of 1% concentration HF aqueous solution into the COS gas directly) in table 1 below.
Table 1: performance differences compared to conventional processing
As can be seen from the above table, the RSDs of Cu, Fe, Mo, Ni, and Cr in the conventional processing methods are respectively 200%, 100%, 70%, 150%, and 80%, and the RSDs of the metal impurities are respectively reduced to 5%, 3%, and 2% by the method of this embodiment. Therefore, the method has the advantages of higher metal ion data precision, extremely high reliability and remarkable effect.
It should be understood that the above-mentioned embodiments are only illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All modifications made according to the spirit of the main technical scheme of the invention are covered in the protection scope of the invention.
Claims (6)
1. A sample pretreatment process for testing the content of metal ions in carbonyl sulfide is characterized in that: the method comprises the following steps:
s1, preparing an HF aqueous solution with the mass concentration of 1-3%;
s2, adding Sc to the HF aqueous solution in the step S12O3Obtaining a mixed solution; sc in the mixed solution2O3The mass concentration of (A) is 0.0001-0.0007%;
s3, introducing carbonyl sulfide gas to be detected into the mixed solution in the step S2; meanwhile, a filter membrane is arranged above the mixed solution to filter gas formed when the carbonyl sulfide to be detected is introduced;
s4, after the introduction of carbonyl sulfide to be detected is finished, continuing to wait for at least 1 minute, then putting the filter membrane into the mixed solution, and fully stirring and uniformly mixing;
s5, filtering the mixed solution obtained in the step S4 by using a second filter membrane to obtain a pretreated sample.
2. The process of claim 1, wherein: in the step S3, introducing carbonyl sulfide gas to be detected into the mixed solution in the step S2, wherein the mass ratio of the mixed solution to the carbonyl sulfide to be detected is 3-10: 1.
3. the process of claim 1, wherein: the aperture of the filter membrane in the step S3 is 0.1-0.3 micron.
4. The process of claim 1, wherein: the aperture of the second filter membrane in the step S5 is 0.1-0.3 micron.
5. The process of claim 1, wherein: and after the step S5, directly sucking the sample into the ICP-MS instrument through a sample inlet pipe of the ICP-MS instrument, and analyzing and detecting the content of the metal ions.
6. The process of claim 1, wherein: in step S3, the exhaust gas not absorbed by the mixed solution is introduced into the NaOH solution for absorption.
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| CN110118815A (en) * | 2019-05-15 | 2019-08-13 | 上海大学 | The method that micro-wave digestion-ICP-MS measures content of beary metal in sediments |
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| JP3540995B2 (en) * | 2000-09-08 | 2004-07-07 | 財団法人電力中央研究所 | Method and apparatus for continuous separation analysis of metallic mercury and water-soluble mercury in gas |
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Address after: 215152 Anmin Road, Panyang Industrial Park, Huangdai Town, Xiangcheng District, Suzhou City, Jiangsu Province Patentee after: Jinhong Gas Co.,Ltd. Address before: 215152 No. 6 Anmin Road, Panyang Industrial Park, Huangdi Town, Xiangcheng District, Suzhou City, Jiangsu Province Patentee before: SUZHOU JINHONG GAS Co.,Ltd. |