CN111413291A - Infrared spectrum quantitative analysis method of gas fluoride - Google Patents
Infrared spectrum quantitative analysis method of gas fluoride Download PDFInfo
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 24
- 238000002329 infrared spectrum Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000001514 detection method Methods 0.000 claims abstract description 32
- 238000002835 absorbance Methods 0.000 claims abstract description 29
- 230000035484 reaction time Effects 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000012417 linear regression Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 164
- 238000010521 absorption reaction Methods 0.000 claims description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 24
- 238000004458 analytical method Methods 0.000 claims description 24
- 238000009833 condensation Methods 0.000 claims description 24
- 230000005494 condensation Effects 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 24
- 239000011737 fluorine Substances 0.000 claims description 24
- 238000005070 sampling Methods 0.000 claims description 17
- 229910015255 MoF6 Inorganic materials 0.000 claims description 14
- 150000002222 fluorine compounds Chemical class 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 238000004566 IR spectroscopy Methods 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000012495 reaction gas Substances 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 229910000792 Monel Inorganic materials 0.000 claims description 5
- 235000011089 carbon dioxide Nutrition 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000002161 passivation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002826 coolant Substances 0.000 claims description 4
- RLCOZMCCEKDUPY-UHFFFAOYSA-H molybdenum hexafluoride Chemical group F[Mo](F)(F)(F)(F)F RLCOZMCCEKDUPY-UHFFFAOYSA-H 0.000 claims description 4
- 229910019593 ReF6 Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000012844 infrared spectroscopy analysis Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- YUCDNKHFHNORTO-UHFFFAOYSA-H rhenium hexafluoride Chemical compound F[Re](F)(F)(F)(F)F YUCDNKHFHNORTO-UHFFFAOYSA-H 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- MARDFMMXBWIRTK-UHFFFAOYSA-N [F].[Ar] Chemical compound [F].[Ar] MARDFMMXBWIRTK-UHFFFAOYSA-N 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000011261 inert gas Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000003682 fluorination reaction Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000656145 Thyrsites atun Species 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
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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
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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
- G01N1/42—Low-temperature sample treatment, e.g. cryofixation
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses an infrared spectrum quantitative analysis method of gas fluoride, which comprises the steps of ① infrared spectrum detection of gas obtained in different reaction time in fluoride preparation, ② t is an abscissa and absorbance under unit pressure is an ordinate to obtain an absorbance change curve under unit pressure, ③ absorbance under unit pressure is integrated relative to t to obtain an integral area, ④ repeats ① - ③ to prepare fluoride with different masses, at least three groups of integral areas are obtained, mass of fluoride in each group is collected, ⑤ integral area is an abscissa and mass of fluoride is an ordinate to obtain a standard linear regression equation through fitting, and ⑥ substitutes the integral area of any reaction curve into the equation.
Description
Technical Field
The invention belongs to the technical field of nuclear energy industry and dry metallurgy, and particularly relates to an infrared spectrum quantitative analysis method of gas fluoride.
Background
The fluorination volatilization method is a key technology for separating and recovering uranium in dry post-treatment, and F is removed from the fluorination volatilization product2In addition, it contains UF6、MoF6、TcF6And the like, fluoride gases which are highly oxidative and corrosive are particularly sensitive to moisture in the air, are very susceptible to hydrolysis reaction to generate metal oxyfluoride and toxic HF, and can react with most metal substances, so that the fluoride gases are difficult to be effectively and accurately analyzed by conventional instruments (such as gas chromatography, gas mass spectrometry and the like). The infrared spectrometer has the characteristics of high sensitivity, rapid detection and corrosion resistance, and compared with a gas chromatography and a gas mass spectrometry, the infrared spectrometer has the most abundant and mature spectral data. Most of the gas is in the middle infrared band (400--1) Has significant absorption therein and the analysis process does not require pretreatment, so infrared spectroscopy is often used for gas analysis.
In the quantitative analysis of a gas by infrared spectroscopy, the relationship expression is a ═ a × b × c, where a is an absorption coefficient, b is a sample cell thickness, and c is a substance concentration, usually according to the rule that the absorbance a of the gas over a certain wavelength band is in a linear relationship with the concentration (that is, beer-lambert law). The absorption coefficient is a specific value of a substance, but the values in the literature cannot be used universally, the obtained values are different due to different precision and operation conditions of instruments, and in actual work, the absorption coefficient is re-determined by the pure substance in order to ensure the accuracy of quantitative analysis. Most of volatile fluoride has strong reactivity, so that the high purity of the volatile fluoride is difficult to ensure in the preparation process of the volatile fluoride, and the accurate determination of the absorption coefficient is difficult, so that the accurate relation (namely a standard curve) between the absorbance and the concentration cannot be ensured, and the challenge is brought to the quantitative analysis of the fluorinated volatile product in the dry-method post-treatment. Moreover, the existing infrared spectrum quantitative analysis technology is more used for determining the concentration of the gas to be measured through a standard curve, namely the percentage of the gas to be measured relative to the pure gas, and the mass (m) of the final gas still needs to be further calculated and determined according to an ideal gas equation (PV ═ nRT), and as can be known from the ideal gas equation, the change of the environmental temperature, the determination of the pipeline volume and the reaction loss of the pipeline all bring inevitable errors to subsequent calculation.
In view of the above, there is a strong need in the art to develop a quantitative analysis method for a strongly corrosive fluoride gas.
Disclosure of Invention
The invention provides a quantitative analysis method of gas fluoride by infrared spectroscopy, which aims to overcome the defects that the existing infrared spectroscopy technology can not carry out quantitative analysis on the gas fluoride with strong corrosivity through an absorption coefficient and usually brings unnecessary errors when carrying out quantitative analysis on the gas based on an ideal gaseous equation at present. The analysis method is more direct, simple and accurate, the dependency relationship between the integral area of the absorbance change curve of unit pressure and the condensation collection amount is established by combining the condensation collection operation on the basis of the infrared spectrum technology, the quality of the target gas fluoride can be directly calculated after the relevant standard curve is obtained, the operation process is simplified, and the analysis efficiency is improved.
The invention solves the technical problems through the following technical scheme.
The invention provides a method for quantitatively analyzing gas fluoride by infrared spectroscopy, which comprises the following steps:
(1) in the preparation process of the gas fluoride, sampling gas mixtures obtained in different reaction times, and carrying out infrared spectrum detection; obtaining a group of reaction time and unit pressure absorbance during each infrared spectrum detection;
(2) taking the reaction time detected by the infrared spectroscopy in the step (1) as an abscissa and the absorbance at unit pressure as an ordinate to obtain a change curve of the absorbance at unit pressure of the gas fluoride;
(3) for the absorbance change curve per unit pressure in the step (2), obtaining an integral area by integrating the absorbance per unit pressure with respect to the reaction time; collecting the gaseous fluoride in the preparation process of the step (1);
(4) repeating the steps (1) - (3) at least three times to prepare the gas fluoride with different masses, obtaining at least three groups of integral areas, and correspondingly and respectively collecting the masses of the gas fluoride prepared in each group;
(5) fitting to obtain a standard linear regression equation by taking the integral area as a horizontal coordinate and the mass of the gas fluoride collected in the preparation process as a vertical coordinate;
(6) and (3) preparing the gas fluoride by any reaction feeding, repeating the steps (1) to (2) to obtain a unit pressure absorbance change curve of the gas fluoride, and substituting the integral area of the curve into the standard linear regression equation in the step (5) to obtain the mass of the gas fluoride obtained by the reaction.
In step (1), the gaseous fluoride may be one having an infrared characteristic peak (500--1) Especially for corrosive gas fluorides, e.g. MoF6、UF6，WF6，ReF6，TcF6，PuF6Or NpF6And so on.
In the step (1), the preparation method of the gaseous fluoride may be a preparation method conventionally used in the art for preparing the gaseous fluoride, and generally the metal and F2The reaction is carried out. For example, when the gaseous fluoride is MoF6Metal Mo foil and F can be used2Carrying out reaction to obtain the product. The conditions or processes for the preparation of the gaseous fluoride may be conventional in the art.
In step (1), the pressure at which the sample is taken may be conventional in the art, and is typically from 0to 100 torr. In order to avoid the effect of sampling amount on the error in the infrared spectrum detection, the sampling pressure is preferably 0-50 torr.
In the step (1), the number of times of sampling may be set so as to obtain the absorbance change curve per unit pressure of the gaseous fluoride in the step (2). For example, the gas infrared spectrum may be recorded every 3 to 5 minutes from the start of the reaction, and the reaction may be detected as complete or incomplete until the absorbance change per unit pressure curve of the gas fluoride can be plotted, or until the reaction is complete.
In the step (1), the infrared spectrum detection method and conditions are conventional in the field. The reaction time and the absorbance of the gas fluoride can be directly obtained in the obtained infrared spectrogram for each infrared spectrum detection, and the absorbance (torr) per unit pressure is calculated-1)。
In the step (1), the absorbance per unit pressure refers to a ratio of an absorbance value to a sampling pressure obtained in infrared spectrum detection.
In step (1), the method of calculating the integrated area of the curve described in step (2) may be conventional in the art. For example, origin pro may be used for data processing.
In the step (3), the integrated area is an area obtained by integrating the absorbance per unit pressure with respect to the reaction time.
In step (3), the amount of the gaseous fluoride substance may be any amount, and is preferably in the range of 0to 500 mg.
In the step (3), the method of collecting the gaseous fluoride in the preparation process of the step (1) may be conventional in the art. Preferably, fluoride is collected and calculated by the following steps: (1) introducing gaseous fluoride generated by the reaction into a cold trap placed in dry ice (-78 ℃), and cooling and collecting condensate; (2) the condensate was subjected to dissolution analysis to determine the fluoride produced by the reaction. The method and operation of the dissolution analysis can be conventional in the art, and dilute nitric acid or deionized water is generally added into the condensate to enable the fluoride to be subjected to hydrolysis reaction and fully dissolved, and finally the content of metal ions in the solution is measured through elemental analysis, and the condensation mass of the gas fluoride is calculated.
As a general knowledge, in step (5), the higher the accuracy of the standard linear regression equation, the more point values are required for drawing the curve, i.e. the more times of different feeding is repeated in step (4).
In the step (6), the gas fluoride is prepared by any reaction feeding, and the reaction can be complete or incomplete, that is, the integral area of the curve of the standard linear regression equation substituted into the step (5) can be the integral area obtained at any reaction time.
In the method for the infrared spectroscopic quantitative analysis of gaseous fluoride, the required analysis system preferably comprises a gas preheating part, a reactor part, a condensation collection part and a tail gas treatment part which are connected in sequence; the gas preheating part is used for preheating reaction gas, the reactor part is a place for providing reaction, the condensation collecting part is used for collecting the gas fluoride, and the tail gas treatment part is used for treating the gas which is not condensed by the condensation collecting part;
the device also comprises an infrared detection part which is connected with the reactor part and is used for detecting the product obtained by the reaction of the reactor part in real time.
Wherein, according to the common knowledge in the art, the gas tightness of the analysis system is determined after the reaction metal is put into the reactor part and before the reaction is carried out. If the system has good air tightness, all parts of the analysis system (such as a reactor part, a pipeline of a condensation collection part and a cold trap) are preferably heated to be higher than 100 ℃, and fluorine and argon gas with the temperature higher than 100 ℃ is introduced to remove trace moisture in the analysis system.
Wherein the various parts and conduits of the analytical system are typically of a material resistant to corrosion by the gaseous fluoride, preferably a monel material.
Wherein the surfaces of the various parts of the analysis system and the conduits in contact with the gaseous fluoride are preferably subjected to a fluorine passivation process to form a passivation layer.
The reaction gas is generally a mixed gas of fluorine gas and an inert gas, the volume percentage of the fluorine gas in the mixed gas of fluorine gas and the inert gas can be conventional in the field, generally 10-30%, for example 20%, the flow rate of the mixed gas of fluorine gas and the inert gas can be conventional, for example 5-30m L/min, 10-20m L/min, and the inert gas can be conventional in the field, for example argon.
In the reaction, it is preferable to additionally and simultaneously introduce an inert gas in addition to the mixed gas of the fluorine gas and the inert gas to reduce the severity of the reaction, and the flow rate of the additionally and simultaneously introduced inert gas may be conventional in the art, for example, 5 to 30m L/min and 10 to 20m L/min.
Wherein the reactor part is a place for providing reaction, and preferably comprises a reaction device and a heating furnace. The reaction apparatus may house a metal raw material for preparing the gas fluoride. The heating furnace is used for heating to the temperature required by the reaction.
Wherein preferably a vacuum pump is also connected to the reactor section. Preferably, the vacuum pump and the reactor part are also provided with an absorption tower, and the absorption tower contains substances for absorbing fluorine-containing gas. For example, the absorption column contains Al2O3。
And (2) after the reaction in the step (1) is completed, generally purging the analysis system by using inert gas, and vacuumizing the residual fluorine-containing gas in the system by using the vacuum pump. The pressure after evacuation may be conventional, for example-0.1 MPa.
Wherein the condensation collection part is preferably composed of a gas sample cell, a pressure sensor and a bellows valve. In order to avoid the condensation of fluoride gas on the infrared detection part pipeline, the gas inlet pipeline and the gas sample pool are heated and insulated. The gas sample cell is used for storing sampled gas, and the sampling quantity is judged by a pressure sensor (the sampling pressure range is 0-100 torr).
Wherein, a vacuum pump is preferably connected to the infrared detection part. Preferably, the vacuum pump and the infrared detection part are further provided with an absorption tower, and the absorption tower contains substances for absorbing fluorine-containing gas. For example, the absorption column contains Al2O3。
And after the infrared detection part detects the sampled gas, closing the valve introduced into the infrared detection part, vacuumizing the gas in the gas sample cell of the infrared detection part by using a vacuum pump until the pressure of the whole infrared detection part is the lowest, for example, the negative pressure is-0.1 MPa, and finishing. For the next gas sampling and infrared spectroscopy.
Preferably, the cold trap is designed by adopting welding seal, preferably, the cooling medium adopts dry ice (-78 ℃), preferably, the gas flow rate is regulated by a mass flow controller, the flow rate is controlled within a range of 0-20m L/min, preferably, the air inlet pipeline of the cold trap is heated and insulated, and the temperature is controlled to be higher than the boiling point of the gas fluoride.
Wherein the off-gas treatment section is for treating the gas that is not condensed by the condensing collection section. Along the flowing direction of the reaction gas, the tail gas treatment part preferably comprises a solid absorption bottle, an empty bottle and an alkali liquor absorption bottle which are connected in sequence. The solid absorption bottle contains a fluoride gas absorbing substance, such as Al2O3The empty bottle is used for preventing the solution in the lye absorption bottle from being sucked backwards, the lye absorption bottle contains a substance for absorbing fluoride gas, such as NaOH solution, and in a preferred embodiment, the empty bottle contains about 1L of 2 mol/L NaOH solution.
As is known in the art, valves are provided between the various parts of the assay system.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the analysis method of the invention is more direct, simple and accurate, the establishment of the standard curve does not need to be determined by pure substances, especially for gas fluorides such as MoF which have strong reactivity and are difficult to obtain standard substances with high purity6. Based on infrared spectrum technologyAnd by combining condensation collection operation, the dependency relationship between the integral area of the absorbance change curve of unit pressure and the condensation collection amount is established, the quality of the target object can be directly calculated after the corresponding standard curve is obtained, the error caused by subsequent complex element analysis operation is avoided, the operation flow is simplified, and the analysis efficiency is improved.
Drawings
FIG. 1 is a schematic flow chart of a quantitative infrared spectroscopic analysis system according to example 1.
FIG. 2 shows the MoF obtained in step 3 of example 1 at different times6Relative concentration profile.
FIG. 3 shows MoF in example 16And (4) quantitatively analyzing a standard curve by infrared spectroscopy.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Examples below infrared measurements were performed using a Fourier transform infrared spectrometer, Perkin Elmer, USA, model Frontier; gas cell, available from PIKE, usa, window material ZnSe, optical path 10 cm.
The instrument for measuring the content of metal ions in the solution by elemental analysis was an inductively coupled plasma atomic emission spectrometer ICP-AES, model optima 8000, available from Perkinelmer, USA.
FIG. 1 is a schematic flow chart of a quantitative infrared spectroscopic analysis system according to example 1. The direction of the arrows indicates the direction of gas flow. The device mainly comprises five parts, namely gas preheating, a reactor part, condensation collection, infrared detection and tail gas treatment, wherein the device component is made of Monel alloy material and has good corrosion resistance to fluoride gas. To reduce fluoride gas (in MoF)6For example), the reactor, the gas pipeline and the valve are passivated by fluorine gas before the experiment, and a passivation layer with a protective effect is formed on the inner surface of the metal.
The gas preheating part is used for preheating gas to the reaction temperature.
The reactor part is a place for providing reaction, and comprises a reaction device and a heating furnace.
The reactor part is also connected with an absorption tower and a vacuum pump in sequence. After the reaction is completed, an Ar purging device is adopted, and then a vacuum pump is used for vacuumizing the residual fluorine-containing gas in the system until the pressure of the whole system is lowest, for example, the negative pressure is-0.1 MPa, and the reaction is finished. The absorption tower contains Al2O3The device is used for absorbing fluorine-containing gas and protecting the vacuum pump.
The infrared detection part consists of a gas sample pool, a pressure sensor and a corrugated pipe valve, and heats and preserves the temperature of the gas inlet pipeline and the gas sample pool in order to avoid the condensation of fluoride gas on the pipeline. The gas sample cell is used for storing sampled gas, the sampling amount is judged by the pressure sensor (the sampling pressure range is 0-100torr), and the gas in the gas sample cell is vacuumized after the infrared spectrum of the gas is recorded, so that next gas sampling and infrared spectrum analysis are prepared.
The infrared detection part is also sequentially connected with an absorption tower and a vacuum pump. After the infrared detection, the valve leading to the infrared detection part is closed, the gas in the gas sample cell of the infrared detection part is vacuumized by a vacuum pump until the pressure of the whole infrared detection part is the lowest, for example, the negative pressure is-0.1 MPa, and then the process is finished. The absorption tower contains Al2O3The device is used for absorbing fluorine-containing gas and protecting the vacuum pump.
The condensing and collecting part comprises a Monel cold trap, the cold trap adopts a welding and sealing design, a cooling medium adopts dry ice (-78 ℃) to realize rapid condensation, the gas flow rate is regulated by a mass flow controller, the flow rate control range is within 0-20m L/min, a cold trap air inlet pipeline is used for heating and heat preservation, and the temperature is controlled to be above the boiling point of a target object.
The tail gas treatment part comprises a solid absorption bottle, an empty bottle and an alkali liquor absorption bottle which are sequentially connected along the flowing direction of the reaction gas. The solid absorption bottle comprises Al2O3Granules, NaF granules and soda lime granules. For said empty bottleThe solution in the lye absorption bottle is prevented from being sucked back, and the lye absorption bottle contains 2 mol/L NaOH solution with the volume of about 1L.
MoF in example 16By way of example, MoF6Generated by the reaction of fluorine gas with metallic Mo foil.
Example 1
1. Accurately weighing 1g of Mo foil, placing the Mo foil in a reactor part, connecting pipelines, vacuumizing to confirm the air tightness of the whole system, and comprising a gas preheating part, the reactor part, a gas sample pool of an infrared detection part and a condensation collection part.
2. Heating pipelines and cold traps of the reactor part and the condensation collection part to 100 ℃, introducing 10m L/min fluorine gas and argon gas mixed gas (the volume percentage of the fluorine gas is 20%) and 10m L/min argon gas for pretreatment (the gas also needs to be preheated to 100 ℃), performing infrared spectrum quantitative analysis on the whole device and pipelines to remove trace moisture, and avoiding MoF6Loss of reaction;
3. after pretreatment, the cold trap is placed in dry ice (-78 ℃), the reactor part is heated to 200 ℃, and mixed gas of F2 and Ar (F in the mixed gas) with the flow rate of 20m L/min is introduced after the temperature is stabilized2Volume concentration of 20%), F2Reaction with metallic Mo foil to produce MoF6. During the whole reaction process, from the beginning of the reaction, 1 time of gas infrared spectrogram is recorded every 3 to 5 minutes, and the sampling pressure is controlled within 50 torr. The reaction time and MoF are recorded once per gas infrared spectrogram6Relative concentration (absorbance per unit pressure (torr)-1) Expressed in MoF with reaction time as abscissa6Relative concentration is ordinate, MoF at different times is obtained6The total integrated area of the relative concentration profile, as shown in fig. 2, was calculated.
After each infrared detection, a vacuum pump connected with the infrared detection device is started, and gas in the infrared detection part of the gas sample cell is removed in time.
4. And (3) stopping the fluorine gas introduction after about 60min of the fluorination reaction, changing the fluorine gas introduction into argon purging at 20m L/min, removing residual fluorine-containing gas in a pipeline, and finally pumping the reactor part and the condensation collection part (cold trap) to negative pressure (about-0.05 MPa) by using a vacuum pump connected with the reactor, and then dismantling the reactor, wherein the cold trap is safely dismantled by pumping to the negative pressure, and the subsequent dissolution analysis.
Condensing the collected MoF in a fume hood6Performing dissolution analysis to determine MoF6And (4) quality. Specifically, dilute nitric acid or deionized water is added into the condensed and collected fluoride, so that the fluoride is subjected to hydrolysis reaction and is fully dissolved, and finally, the content of metal ions in the solution is measured through elemental analysis, and the condensation quality of the gas fluoride is calculated.
The integrated area and the actually collected MoF in the sequence number 3 in the table 1 can be obtained through the steps 1 to 46And (4) quality. Table 1 shows the integrated area of the IR monitoring curve obtained in three different experiments and the actually collected MoF6And (4) quality.
The fluorination reaction of Mo foil in the above steps 1 to 4 was repeated to obtain the integrated area and MoF in the numbers 1 and 2 in Table 16And (4) quality.
In Table 1, number 1, Mo foil was fed in an amount of 1g, and during the reaction, the total flow rate of gas fed was 20m L/min, which included "mixed gas of F2 and Ar" and pure Ar. "mixed gas of F2 and Ar" (F in mixed gas)2 Volume concentration 20%) at 5m L/min and pure Ar at 15m L/min.
In Table 1, number 2, Mo foil 1g, and the total flow rate of gas introduced during the reaction was 20m L/min which includes "F2Mixed gas with Ar "and pure Ar. "F2Mixed gas with Ar "(F in mixed gas)2 Volume concentration 20%) was 10m L/min and pure Ar gas flow rate was 10m L/min.
In Nos. 1 and 2, pure argon was further mixed in order to reduce F participating in the reaction2And (4) concentration. MoF6With F participating in the reaction2Concentration-related, the higher the fluorine concentration, the higher the MoF produced in a fixed reaction time (60min)6The more. Actual F participating in the reaction in the above sequence No. 12The concentration is lowest, so that MoF is produced6At minimum, the reaction time is limited to 60min, and does not indicate that the Mo is completely reacted.
TABLE 1 Infrared monitoring Curve integral area and MoF collected actually6Quality of
Note: in table 1, "integrated area" represents the integrated area throughout the reaction; ' MoF6Mass "means the mass of the fluoride collected by condensation;
5. the integrated area and MoF in Table 1 above are compared6The masses were correlated to obtain the standard curve equation y 670.3597 x +3.166, fitting the correlation coefficient 0.9976. FIG. 3 shows MoF6And (4) quantitatively analyzing a standard curve by infrared spectroscopy. Wherein the abscissa is the integral area of the curve and the ordinate is MoF6And (4) quality.
6. The total integrated areas of numbers 1-3 of Table 1 were substituted into the calculated values in Table 2 obtained from the standard curve equation. Relative standard deviations were 1.4%, 6.6%, 1.2%, respectively.
TABLE 2 Infrared monitoring Curve integral area and MoF collected actually6Mass, calculated value and RSD
Wherein, the calculated value is a theoretical value obtained by substituting the integral area into a standard curve equation; RSD ═ (calculated-experimental)/experimental 100%
Gas MoF of example 1 above6May be replaced by any strongly corrosive gaseous fluoride, e.g. UF6，WF6，ReF6，TcF6，PuF6Or NpF6。
Claims (10)
1. The infrared spectrum quantitative analysis method of the gas fluoride is characterized by comprising the following steps of:
(1) in the preparation process of the gas fluoride, sampling gas mixtures obtained in different reaction times, and carrying out infrared spectrum detection; obtaining a group of reaction time and unit pressure absorbance during each infrared spectrum detection;
(2) taking the reaction time detected by the infrared spectroscopy in the step (1) as an abscissa and the absorbance at unit pressure as an ordinate to obtain a change curve of the absorbance at unit pressure of the gas fluoride;
(3) for the absorbance change curve per unit pressure in the step (2), obtaining an integral area by integrating the absorbance per unit pressure with respect to the reaction time; collecting the gaseous fluoride in the preparation process of the step (1);
(4) repeating the steps (1) - (3) at least three times to prepare the gas fluoride with different masses, obtaining at least three groups of integral areas, and correspondingly and respectively collecting the masses of the gas fluoride prepared in each group;
(5) fitting to obtain a standard linear regression equation by taking the integral area as a horizontal coordinate and the mass of the gas fluoride collected in the preparation process as a vertical coordinate;
(6) and (3) preparing the gas fluoride by any reaction feeding, repeating the steps (1) to (2) to obtain a unit pressure absorbance change curve of the gas fluoride, and substituting the integral area of the curve into the standard linear regression equation in the step (5) to obtain the mass of the gas fluoride obtained by the reaction.
2. The method for infrared spectroscopic quantitative analysis of gaseous fluorides as claimed in claim 1 wherein in step (1) said gaseous fluorides are corrosive gaseous fluorides;
and/or, in the step (1), the preparation method of the gas fluoride comprises the steps of mixing the metal and F2Carrying out reaction;
and/or, in the step (1), the sampling pressure is 0-100 torr;
and/or, in the step (1), the sampling times are only required to obtain the absorbance change curve per unit pressure of the gas fluoride in the step (2).
3. The method for infrared spectroscopic quantitative analysis of gaseous fluorides of claim 2 wherein in step (1) the gaseous fluoride is MoF6、UF6，WF6，ReF6，TcF6，PuF6Or NpF6；
And/or, in the step (1), when the gas fluoride is MoF6Using metal Mo foil and F2Carrying out reaction to obtain;
and/or, in the step (1), the sampling pressure is 0-50 torr;
and/or, in the step (1), sampling the mixed gas generated by the reaction once every 3-5 minutes from the beginning of the reaction, and recording a gas infrared spectrogram 1 time until a unit pressure absorbance change curve of the gas fluoride can be drawn, or until the reaction is complete.
4. The method for infrared spectroscopic quantitative analysis of gaseous fluorides according to claim 1 wherein in step (3), the amount of the gaseous fluoride substance is 0to 500 mg;
and/or, in step (3), collecting the gaseous fluoride by: (1) introducing gaseous fluoride generated by the reaction into a cold trap in a cooling medium, and cooling and collecting condensate; (2) performing dissolution analysis on the condensate to determine fluoride generated by the reaction; the cooling medium is preferably dry ice.
5. The method for the infrared spectroscopic quantitative analysis of gaseous fluorides as claimed in claim 1, wherein in the method for the infrared spectroscopic quantitative analysis of gaseous fluorides, a desired analysis system comprises a gas preheating part, a reactor part, a condensation collection part and a tail gas treatment part which are connected in sequence; the gas preheating part is used for preheating reaction gas, the reactor part is a place for providing reaction, the condensation collecting part is used for collecting the gas fluoride, and the tail gas treatment part is used for treating the gas which is not condensed by the condensation collecting part;
the device also comprises an infrared detection part which is connected with the reactor part and is used for detecting the product obtained by the reaction of the reactor part in real time.
6. The method for infrared spectroscopic quantitative analysis of gaseous fluorides as claimed in claim 5, characterized in that the gas tightness of the analysis system is determined after the reaction metal is put in the reactor part and before the reaction is carried out; if the system has good air tightness, all parts of the analysis system are preferably heated to more than 100 ℃, and fluorine-argon mixed gas with the temperature of more than 100 ℃ is introduced to remove trace moisture in the analysis system;
and/or all parts and pipelines in the analysis system are made of Monel alloy;
and/or, in the analysis system, the surface contacted with the gas fluoride is subjected to fluorine gas passivation treatment to form a passivation layer.
7. The method for infrared spectroscopic quantitative analysis of gaseous fluorides as claimed in claim 5, wherein said reactor section includes a reaction device and a heating furnace;
preferably, a vacuum pump is also connected to the reactor section; preferably, the vacuum pump and the reactor part are also provided with an absorption tower, and the absorption tower contains substances for absorbing fluorine-containing gas.
8. The method for infrared spectroscopic quantitative analysis of gaseous fluorides of claim 5 wherein the condensation collection section is composed of a gas sample cell, a pressure sensor and a bellows valve;
preferably, a vacuum pump is connected with the infrared detection part; preferably, the vacuum pump and the infrared detection part are further provided with an absorption tower, and the absorption tower contains substances for absorbing fluorine-containing gas.
9. The method for infrared spectroscopic quantitative analysis of gaseous fluorides of claim 5 wherein the condensate collection section includes a monel cold trap;
preferably, the cold trap adopts a welding seal design, the flow rate of gas in the condensation collection part is regulated by a mass flow controller within the flow rate control range of 0-20m L/min, and the gas inlet pipeline of the cold trap is heated and insulated, and the temperature is controlled to be higher than the boiling point of the gas fluoride.
10. The method for quantitative infrared spectroscopic analysis of gaseous fluorides as claimed in claim 5, wherein said off-gas treating section includes a solid absorption flask, an empty flask and an alkali solution absorption flask connected in sequence along the flow direction of the reaction gas.
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