CN109459539B - Method and system for detecting trace moisture in high-purity ethyl silicate - Google Patents
Method and system for detecting trace moisture in high-purity ethyl silicate Download PDFInfo
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 146
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000001257 hydrogen Substances 0.000 claims abstract description 71
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 71
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000799 K alloy Inorganic materials 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims description 23
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000001514 detection method Methods 0.000 abstract description 41
- 238000009835 boiling Methods 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 10
- 238000005259 measurement Methods 0.000 abstract description 6
- 150000002431 hydrogen Chemical class 0.000 abstract description 5
- 230000008016 vaporization Effects 0.000 description 17
- 238000009834 vaporization Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 12
- 239000012535 impurity Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 239000001307 helium Substances 0.000 description 10
- 229910052734 helium Inorganic materials 0.000 description 10
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- -1 pyridine sulfate anhydride Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- UUCOIDIYWGRARD-UHFFFAOYSA-N methyl sulfate;pyridin-1-ium Chemical compound COS([O-])(=O)=O.C1=CC=[NH+]C=C1 UUCOIDIYWGRARD-UHFFFAOYSA-N 0.000 description 2
- BJDYCCHRZIFCGN-UHFFFAOYSA-N pyridin-1-ium;iodide Chemical compound I.C1=CC=NC=C1 BJDYCCHRZIFCGN-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Food Science & Technology (AREA)
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- Engineering & Computer Science (AREA)
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Abstract
The invention provides a method for detecting trace moisture in high-purity ethyl silicate, which comprises the following steps: heating high-purity ethyl silicate to a boiling point or above, then taking permanent gas as a carrier to carry tetraethoxysilane steam into the sodium-potassium alloy, and detecting the content of hydrogen in the gas after the reaction to obtain the content of water in the high-purity ethyl silicate. Compared with the prior art, the method utilizes the steam-state moisture to react with the sodium-potassium alloy to generate the hydrogen, and the hydrogen does not react with other substances, so that the content of the hydrogen can be accurately obtained, the detection equipment is stable, the detection reliability is greatly improved, and the accuracy and precision of the measurement of the moisture in the high-purity ethyl silicate are further improved.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a method and a system for detecting trace moisture in high-purity ethyl silicate.
Background
Methods for forming oxide layers in semiconductor processes mainly include thermal oxidation (for semiconductor materials capable of forming self-stabilizing oxide layers), low Pressure Chemical Vapor Deposition (LPCVD), plasma Enhanced Chemical Vapor Deposition (PECVD), and Atmospheric Pressure Chemical Vapor Deposition (APCVD), among which most semiconductor processes are currently rarely used due to the large gas flow required by APCVD and relatively large number of process generation particles.
When tetraethyl orthosilicate (TEOS) is used for LPCVD, TEOS is evaporated from a liquid state to a gaseous state, and is decomposed at 700-750 ℃ under 300mTOR pressure to deposit a silicon dioxide film on the surface of a silicon wafer, the deposition rate of the silicon dioxide film can reach 50A/min, the thickness uniformity of the film is less than 3%, and the excellent process characteristics and the obvious characteristics thereof in the aspect of use safety gradually become the main process for depositing the silicon dioxide film.
The silicon dioxide is deposited on the surface of the SiC wafer by using the tetraethyl orthosilicate (TEOS) LPCVD technology, so that the defects of too thin SiC oxide layer and too loose PECVD silicon dioxide layer can be overcome to a certain extent. By reasonably applying the TEOS LPCVD technology and the high-temperature oxidation technology, the compactness of an oxide layer medium and the adhesion capability with a SiC wafer are ensured, the electrical performance and the yield of the device are improved, and the defect of long-time high-temperature oxidation for obtaining an oxide layer with a certain thickness is avoided. After the technology is adopted, the direct current yield of the SiC chip is improved, the comparison flow sheet result of the microwave power device shows that the microwave performance is also obviously improved, the power gain is improved by about 1.5dB compared with the original technology, and the power addition efficiency is improved by about 10%.
However, because of the functional requirements of the high-purity ethyl silicate material, the requirements on impurities in the high-purity ethyl silicate material are very strict, and especially the requirements on moisture are less than 5 multiplied by 10 -6 (mass ratio, conversion to 58×10 molar ratio) -6 ) In the following, how to accurately test the moisture content is the core quality requirement of the product.
At present, a Karl Fischer method is generally adopted to detect the water content in the high-purity ethyl silicate, and the basic principle is as follows: in the presence of water, i.e. water in the sample and SO in the Karl Fischer reagent 2 And I 2 A redox reaction is generated, and the specific chemical reaction equation is: i 2 +SO 2 +2H 2 O→2HI+H 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the However, this reaction is a reversible reaction, and when the sulfuric acid concentration is 0.05% or more, the reverse reaction occurs, but if an appropriate alkaline substance is added to neutralize the acid generated during the reaction, the reaction can be performed in the forward direction. Experiments prove that the pyridine C is added into a high-purity ethyl silicate system 5 H 5 N, the reaction can be carried out rightward, and the reaction formula is: c (C) 5 H 5 N+H 2 O+I 2 +SO 2 →2C 5 H 5 NHI (pyridine hydroiodic acid) +C 5 H 5 NSO 3 (pyridine sulfate anhydride); however, the claimed pyridine sulfate anhydride is unstable and can react with water to consume water and interfere with the assay, and to stabilize it, absolute ethanol can be added: c (C) 5 H 5 NSO 3 (pyridine sulfate anhydride) +CH 3 OH (anhydrous) →C 5 H 5 N·HSO 4 CH 3 (pyridine methyl sulfate). The three steps are combined to obtain the total reaction formula: i 2 +SO 2 +H 2 O+3C 5 H 5 N+CH 3 OH→2C 5 H 5 NHI (pyridine hydroiodic acid) +C 5 H 5 N·HSO4CH 3 (pyridine methyl sulfate). In practical application, SO 2 Pyridine, CH 3 The OH content was excessive, and after the reaction was completed, the excess free iodine appeared reddish brown, which was determined to be the end point.
The effective concentration of karl fischer reagent depends on the concentration of iodine, but the effective concentration of the newly formulated reagent is continually decreasing, mainly due to the higher consumption of some iodine by some side reactions, in addition to the fact that each component of the reagent itself also contains some moisture. This also means that the reagents need to be formulated separately, and the two reagents stored separately and then mixed at the time of use. The Karl Fischer water content measuring reagent used in the market in China is a product which is prepared by manufacturers and can be directly used, and the Karl Fischer reagent is a very unstable mixed substance, so that a user has to calibrate the Karl Fischer water content measuring reagent when in use so as to measure the real water equivalent data of the Karl Fischer water content measuring reagent. When the method is used for testing, after a sample is weighed, the sample is injected into an electrolytic cell of a Karl Fischer tester, the moisture content is calculated through electrolytic reaction, but whether the injected reagent is fully and completely mixed with the Karl Fischer reagent is based on experience, the moisture in an electrolytic solution has the problem of uneven diffusion, so that measurement data can be smaller, calibration needs to be carried out by adopting standard reagents, the calibrated solution needs to be operated and used on site, the artificial uncertainty is too much, the reliability of the final standard solution is reduced, the problem of conversion efficiency still exists in the Karl Fischer test method, and the efficiency is directly dependent on the content of sulfur dioxide in a methanol solution (volatilization problem) and the content of elemental iodine (content reduction caused by side reaction).
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method and a system for detecting trace moisture in high purity ethyl silicate with high reliability and accuracy.
The invention provides a method for detecting trace moisture in high-purity ethyl silicate, which comprises the following steps:
heating high-purity ethyl silicate to a boiling point or above, then taking permanent gas as a carrier to carry tetraethoxysilane steam into the sodium-potassium alloy, and detecting the content of hydrogen in the gas after the reaction to obtain the content of water in the high-purity ethyl silicate.
Preferably, after the reaction, cooling is performed to detect the hydrogen content in the gas.
Preferably, the permanent gas is cooled, the content of hydrogen and moisture in the permanent gas is detected, and the content of moisture in the high-purity ethyl silicate is obtained according to the content of hydrogen in the gas and the content of hydrogen and moisture in the permanent gas.
Preferably, after the permanent gas is introduced into the sodium-potassium alloy for reaction, detecting the content of hydrogen in the permanent gas after the reaction, and obtaining the content of water in the high-purity ethyl silicate according to the content of hydrogen in the gas and the content of hydrogen in the permanent gas after the reaction.
The invention also provides a detection system of trace moisture in the high-purity ethyl silicate, which comprises the following steps:
a permanent gas is introduced into the pipeline;
a high purity ethyl silicate vaporization chamber; the permanent gas inlet pipeline is communicated with the high-purity ethyl silicate vaporization chamber;
a reaction chamber; the reaction chamber is communicated with a high-purity ethyl silicate vaporization chamber; a sodium-potassium alloy is arranged in the reaction chamber;
a hydrogen gas detection device; the hydrogen detection device is communicated with the reaction chamber.
Preferably, the cooling device further comprises a cooling chamber; the reaction chamber is communicated with the hydrogen detection device through the cooling chamber.
Preferably, the permanent gas inlet pipeline is communicated with the hydrogen detection device through the cooling chamber.
Preferably, the device also comprises a moisture detection device; the moisture detection device is communicated with the cooling chamber.
Preferably, the permanent gas inlet pipeline is communicated with the reaction chamber.
Preferably, the high-purity ethyl silicate vaporization chamber has an aspect ratio of 2-10; the height-diameter ratio of the reaction chamber is 2-20.
The invention provides a method for detecting trace moisture in high-purity ethyl silicate, which comprises the following steps: heating high-purity ethyl silicate to a boiling point or above, then taking permanent gas as a carrier to carry tetraethoxysilane steam into the sodium-potassium alloy, and detecting the content of hydrogen in the gas after the reaction to obtain the content of water in the high-purity ethyl silicate. Compared with the prior art, the method utilizes the steam-state moisture to react with the sodium-potassium alloy to generate the hydrogen, and the hydrogen does not react with other substances, so that the content of the hydrogen can be accurately obtained, the detection equipment is stable, the detection reliability is greatly improved, and the accuracy and precision of the measurement of the moisture in the high-purity ethyl silicate are further improved.
Drawings
FIG. 1 is a schematic diagram of a trace moisture detection system in high purity ethyl silicate provided by the invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a method for detecting trace moisture in high-purity ethyl silicate, which comprises the following steps: heating high-purity ethyl silicate to a boiling point or above, then taking permanent gas as a carrier to carry tetraethoxysilane steam into the sodium-potassium alloy, and detecting the content of hydrogen in the gas after the reaction to obtain the content of water in the high-purity ethyl silicate.
The invention is based on the physical characteristics that the sodium-potassium alloy is liquid at normal temperature and normal pressure and can be converted into steam at the temperature of more than 700 ℃. The sodium-potassium alloy can not generate metal vapor in the boiling point region of the tetraethoxysilane, has very active chemical properties, can chemically react with moisture in a free state and a vapor state to generate hydrogen, and simultaneously, the hydrogen does not react with other substances in the system, and has the characteristics of sensitive response on a detector such as a DID detector of a gas chromatograph, and the external standard method has the characteristics of simple, convenient and accurate test, and the like.
The high purity ethyl silicate is heated to a boiling point or above, preferably to 165 ℃ to 168 ℃. The boiling point of the ethyl orthosilicate is higher than that of water, so that the water in the high-purity ethyl silicate can be completely vaporized with the ethyl orthosilicate; the invention adopts the method that the liquid substances are completely vaporized and form saturated solution, and the liquid substances are converted into gas substances for analysis, so that the analysis is more mature and reliable in the aspects of analysis instrument principle and design.
Carrying tetraethoxysilane steam into the sodium-potassium alloy by taking permanent gas as a carrier; the permanent gas is a permanent gas well known to those skilled in the art, and is not particularly limited, but is preferably an inert gas and/or a sub-inert gas, more preferably one or more of ultrapure helium, nitrogen and argon; the purity of the ultrapure helium, nitrogen and argon is preferably 99.9996% or more. The high purity gas can last for more than 3 years, and chemical reaction does not occur under normal conditions. Introducing permanent gas into the ethyl orthosilicate boiling liquid, wherein the permanent gas is carried with diluted ethyl orthosilicate steam, using the permanent gas as a carrier to form saturated steam, and under the condition of gas-liquid saturation, using sodium-potassium alloy and moisture reaction and conversion to completely convert the moisture in the solution into hydrogen gas by a chromatographic analysis technology so as to test the moisture content; the outlet gauge pressure of the permanent gas is preferably 0.8-1.2 Bar, more preferably 0.9-1.1 Bar, and even more preferably 1Bar; the total absolute pressure of the permanent gas and the tetraethyl orthosilicate vapor is preferably 2Bar.
To prevent condensation of the tetraethyl orthosilicate vapor, it is preferably reacted with a sodium potassium alloy under heating; the heating temperature is preferably 165-168 ℃; at this time, the water vapor in the tetraethoxysilane vapor carried by the permanent gas chemically reacts with the sodium-potassium alloy to generate hydrogen.
Detecting the content of hydrogen in the gas after the reaction; the method of detection is not particularly limited as long as it is well known to those skilled in the art, and is preferably a chromatograph, more preferably a gas chromatograph in the present invention; the detection of the chromatograph can be accurate to 0.01X10 -6 (molar ratio). The water content in the corresponding tetraethoxysilane is obtained through the content of hydrogen in the gas, and the permanent gas is taken as helium for example, and the reaction formula is as follows: naK+2H 2 O (He-TEOS vapor) -NaOH+KOH+H 2 + (He-TEOS vapor) p=2 Barg; p (P) He-TEOS vapor ＝P He +P TEOS vapor Considering that TEOS happens to be in the boiling point state at this time, P He ＝P TEOS vapor ＝1Barg。
In order to prevent the ethyl orthosilicate from affecting the accuracy of hydrogen detection, it is preferable to cool the reacted gas and then detect the content of hydrogen in the gas; the cooling temperature is preferably 15-50 ℃, more preferably 15-30 ℃, and still more preferably 15-20 ℃; through cooling, the tetraethoxysilane can be liquefied and enriched, so that gas-liquid separation is realized; the reaction formula is: naOH+KOH+H 2 ++ (He-TEOS vapor) -NaOH+KOH+H 2 + (He-20 ℃ gas+teos liquid) p=2 Barg; the total pressure of the system at this time is p=p He ＝2Barg。
In order to eliminate the influence of partial moisture impurities contained in the permanent gas and the reaction of the moisture impurities and the sodium-potassium alloy, the permanent gas is preferably introduced into the sodium-potassium alloy for reaction, more preferably, the permanent gas is heated to the boiling point of tetraethoxysilane and then introduced into the sodium-potassium alloy for reaction, the content of hydrogen in the permanent gas after the reaction is detected, and the content of the moisture in the high-purity ethyl silicate is obtained according to the content of the hydrogen in the gas and the content of the hydrogen in the permanent gas after the reaction; the detection method is the same as that described above, and is not repeated here; the permanent gas is heated to the boiling point of the tetraethoxysilane and then reacts with the sodium-potassium alloy, so that the influence of environmental factors on chemical reaction can be eliminated.
In order to further eliminate the influence of the operation steps on the result, the permanent gas is introduced into the sodium-potassium alloy for reaction, and then is preferably cooled, the content of hydrogen in the reacted permanent gas is detected, and the content of water in the high-purity ethyl silicate is obtained according to the content of hydrogen in the gas and the content of hydrogen in the reacted permanent gas; the cooling temperature is the same as that described above, and will not be described again here; taking permanent gas as helium as an example, the chemical reaction formula is: naK+2H 2 O (He-165-168 ℃ gas state) →NaOH+KOH+H 2 (He-20deg.C gas phase).
The moisture impurity reacts with the sodium-potassium alloy solution to possibly have a certain conversion rate, in order to eliminate the influence of the conversion rate and the original impurity hydrogen in the permanent gas, the content of the hydrogen and the moisture in the permanent gas is preferably detected, and the content of the moisture in the high-purity ethyl silicate is obtained according to the content of the hydrogen in the gas and the content of the hydrogen and the moisture in the permanent gas; more preferably, the permanent gas is cooled, the content of hydrogen and moisture in the permanent gas is detected, and the content of moisture in the high-purity ethyl silicate is obtained according to the content of hydrogen in the gas and the content of hydrogen and moisture in the permanent gas; and then, preferably, heating the permanent gas to the boiling point of the ethyl orthosilicate, cooling, detecting the content of hydrogen and moisture in the permanent gas, and obtaining the content of moisture in the high-purity ethyl silicate according to the content of hydrogen in the gas and the content of hydrogen and moisture in the permanent gas; the cooling temperature is the same as that described above, and will not be described again here; the method for detecting the moisture content in the permanent gas is a method well known to those skilled in the art, and is not particularly limited, and the method is preferably carried out by using a moisture analyzer, more preferably a MEECO moisture analyzer, which can be accurate to 0.02×10- 6 (molar ratio). The invention adopts the chromatograph and the moisture analyzer, and can form mutual comparison by utilizing different analysis and test technologies, thereby judging the reliability of the instrument.
According to the invention, the content of hydrogen in the gas, the content of hydrogen in the permanent gas after the reaction and the content of hydrogen and moisture in the permanent gas are preferably combined to obtain the content of moisture in the high-purity ethyl silicate; the invention adopts the external standard method to measure and test simply, conveniently and accurately; the gas chromatograph and the water analyzer are adopted at the same time, so that the measuring and testing capacity of the detection method provided by the invention can be improved by two orders of magnitude, and the accuracy of the obtained result is 0.02 multiplied by 10- 6 Far higher than the accuracy of karl fischer detectors.
Assuming that the content of hydrogen in the gas after the permanent gas carries saturated steam of tetraethoxysilane and the saturated steam passes through sodium-potassium solution to react is C H2-A The method comprises the steps of carrying out a first treatment on the surface of the The content of water in the high-purity ethyl silicate is C H2O-A The method comprises the steps of carrying out a first treatment on the surface of the The hydrogen content of the permanent gas after the permanent gas is reacted by the sodium potassium solution is C H2-B Moisture content of C H2O-B The method comprises the steps of carrying out a first treatment on the surface of the The hydrogen content in the permanent gas is C H2-C Moisture content of C H2O-C The method comprises the steps of carrying out a first treatment on the surface of the Assuming that the chemical reaction conversion rate of the sodium-potassium alloy and water is alpha
α＝2(C H2-B -C H2-C )/C H2O-C ×100％
α＝(C H2O-C -C H2O-B )/C H2O-C ×100％
Alpha can be calculated by testing with different permanent gases according to the above formula.
C H2-A ＝α×C H2O-A +C H2-B (I)
C H2-B ＝α×C H2O-C +C H2-C (II)
Is obtained by the formulas (I) and (II): c (C) H2O-A ＝(C H2-A -C H2-C )/α-C H2O-C
Therefore, the moisture content of the high-purity ethyl silicate can realize stable measurement values only by testing the concentration of impurity hydrogen after the permanent gas and the ethyl silicate vapor pass through the reaction and the concentration of hydrogen and moisture contained in the permanent gas through chromatography, namely, the conversion rate of the reaction of the moisture and the sodium-potassium alloy is scientifically calculated by utilizing visual detection data, and meanwhile, the conversion rate can be compared through 2 methods (an electrolytic method and a chromatographic method are combined with the electrolytic method), so that the reliability and the comparability among instruments are improved.
The method utilizes the steam-state moisture to react with the sodium-potassium alloy to generate the hydrogen, and the hydrogen does not react with other substances, so that the content of the hydrogen can be accurately obtained, the detection equipment is stable, the detection reliability is greatly improved, and the accuracy and precision of the measurement of the moisture in the high-purity ethyl silicate are further improved.
The invention also provides a system for detecting trace moisture in the high-purity ethyl silicate, which comprises the following components:
a permanent gas is introduced into the pipeline;
a high purity ethyl silicate vaporization chamber; the permanent gas inlet pipeline is communicated with the high-purity ethyl silicate vaporization chamber;
a reaction chamber; the reaction chamber is communicated with a high-purity ethyl silicate vaporization chamber; a sodium-potassium alloy is arranged in the reaction chamber;
a hydrogen gas detection device; the hydrogen detection device is communicated with the reaction chamber.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a detection system provided by the present invention.
The detection system provided by the invention preferably comprises a permanent gas storage tank; the permanent gas storage tank is communicated with the permanent gas inlet pipeline.
The permanent gas inlet pipeline is preferably communicated with the high-purity ethyl silicate vaporization chamber through a first pressure gauge, and the pressure of the permanent gas inlet pipeline can be adjusted through the first pressure gauge; the outlet of the permanent gas inlet pipeline in the high-purity ethyl silicate vaporization chamber is preferably positioned below the liquid level of the high-purity ethyl silicate; a heating device is arranged outside the high-purity ethyl silicate vaporization chamber; the heating device is a heating device well known to those skilled in the art, and is not particularly limited, and is preferably a silicone oil bath in the present invention; the height-diameter ratio of the high-purity ethyl silicate vaporization chamber is preferably 2-10, more preferably 5-10.
In order to eliminate the influence of the ambient temperature on the chemical reaction, a heating device is preferably arranged outside the permanent gas inlet pipeline; the heating device is a heating device well known to those skilled in the art, and is not particularly limited, and is preferably a silicone oil bath in the present invention; the permanent gas inlet pipe is preferably a coiled pipe, more preferably a stainless steel coiled pipe.
The high-purity ethyl silicate vaporization chamber is communicated with the reaction chamber; a sodium-potassium alloy is arranged in the reaction chamber; in order to allow the moisture in the steam to react well with the sodium-potassium alloy; the high-purity ethyl silicate vaporization chamber is preferably communicated with the reaction chamber through a steam pipeline; more preferably, a valve is arranged between the high-purity ethyl silicate vaporization chamber and the steam pipeline so as to control the circulation of steam; the outlet of the steam pipeline is preferably positioned below the liquid level of the sodium-potassium alloy, and more preferably is more than 2/3 deeper than the liquid level; the reaction chamber is preferably provided with a heating device; the heating device is a heating device well known to those skilled in the art, and is not particularly limited, and is preferably a silicone oil bath in the present invention; the aspect ratio of the reaction chamber is preferably 2 to 20, more preferably 5 to 15, still more preferably 10.
In order to reduce the influence of the tetraethoxysilane steam on the hydrogen detection, a cooling chamber is preferably further included; the reaction chamber is communicated with the hydrogen detection device through the cooling chamber; the cooling chamber is a cooling chamber well known to those skilled in the art, and is not particularly limited, and the cooling chamber of the present invention is preferably provided with a heat exchanger, more preferably a stainless steel coil heat exchanger; the heat exchanger is provided with water as a heat exchange medium; the cooling chamber is communicated with the hydrogen detection device preferably through a second pressure gauge so as to control the pressure of the gas entering the hydrogen detection device; the hydrogen gas detection device may be a hydrogen gas detection device known to those skilled in the art, and is not particularly limited, and a chromatograph is preferable in the present invention.
In order to eliminate the effect of the permanent gas itself containing a part of the moisture impurities and the reaction of the moisture impurities with the sodium-potassium alloy, the permanent gas inlet line is preferably in communication with the reaction chamber, more preferably in communication with the steam line via a valve.
In order to eliminate the effect of the conversion and of the hydrogen gas which is inherently an impurity in the permanent gas, the permanent gas feed line is preferably connected to the cooling chamber.
In the present invention, the detection system preferably further comprises a moisture detection device; the moisture detection device is communicated with the cooling chamber to detect the moisture content in the permanent gas; the cooling chamber is preferably in communication with the moisture detection means via a second pressure gauge; the moisture detection device is preferably a moisture analyzer.
According to the invention, it preferably further comprises an ethyl orthosilicate recovery chamber; the ethyl orthosilicate recovery chamber is communicated with the cooling chamber; the ethyl orthosilicate recovery chamber is preferably also communicated with a high purity ethyl silicate vaporization chamber.
According to the invention, a sodium-potassium alloy recovery chamber is preferably also included; the sodium-potassium alloy recovery chamber is communicated with the reaction chamber.
In order to further illustrate the invention, the following embodiment is used for describing the method and the system for detecting trace moisture in high purity ethyl silicate in detail.
The reagents used in the examples below are all commercially available.
Example 1 (taking 99.9996% helium as an example)
High-purity ethyl silicate is put into a silicone oil bath vaporization chamber V at 165-168 DEG C A (the height-diameter ratio of the vaporizing chamber is 6:1), at the moment, the moisture (boiling point 100 ℃) in the high-purity ethyl silicate can be completely vaporized with the ethyl orthosilicate, permanent gas (more than 99.9996% high-purity helium) is introduced into boiling liquid of the ethyl orthosilicate, the permanent gas carries diluted ethyl orthosilicate steam, under the condition of the total absolute pressure of 2Bar, the partial pressure of the permanent gas and the ethyl orthosilicate steam is 1Bar respectively, and the permanent gas brings gaseous ethyl orthosilicate into a container V containing sodium-potassium mixed solution B The vessel is also placed in a silicone oil bath at 165-168 ℃ and a sodium potassium mixed solution vessel V B The ratio of the height to the diameter is designed to be 10, at the moment, the vapor in the tetraethoxysilane carried by the permanent gas (more than 99.9996% of high-purity helium) and the metal sodium potassium mixed solution react chemically to generate hydrogen, and the generated hydrogen can form uniform mixed gas with the permanent gas (more than 99.9996% of high-purity helium) to be conveyed to a chromatograph for detection. When the permanent gas and the tetraethoxysilane vapor finally pass through the stainless steel coil heat exchanger in the water cooling pool with the temperature of 20 ℃, the tetraethoxysilane is cooled, liquefied and enriched into a container V C In the method, the residual permanent gas is directly conveyed to a gas chromatograph for detection, and the hydrogen content of the A path detection is assumed to be C at the moment H2-A At this time, the water content in the corresponding tetraethoxysilane is C H2O-A 。
In order to eliminate the influence of partial moisture impurities contained in permanent gas (high-purity helium with the concentration of more than 99.9996 percent) and the reaction of the moisture impurities with metal sodium potassium solution, a certain conversion rate exists, and the hydrogen gas which is originally inherent in the permanent gas is influenced, two paths of gas output are additionally and independently designed, so that the problems can be accurately and skillfully solved, and the problems are respectively designed into a gas path B and a gas path C in the invention;
in order to ensure that the B path gas and the A path gas which are passed by the permanent gas have good identity and comparability, the B path gas and the A path gas are converged into a metal sodium potassium solution container V B The pipeline reduces the reaction efficiency error caused by the difference of contact reaction time of water in gas and metal sodium potassium, which is influenced by the manufacturing difference of equipment, the gas A and the gas B are finally converged to the same gas pipeline and are directly input to a gas chromatograph for detection, the total absolute pressure of the pipeline gas is still kept 2Bar, and the condition that the content of the hydrogen detected by the pipeline B is C is assumed H2-B Moisture content of C H2O-B . In order to eliminate the influence of environmental temperature on chemical reaction, the permanent gas design coil type stainless steel heat exchanger in the A and B paths of gas is embedded into a silicone oil bath at 165-168 ℃, and a pipeline valve which is not immersed into the silicone oil bath is processed in a heat preservation mode or a heat tracing mode.
In order to scientifically study the conversion rate of the chemical reaction of water and the metal sodium potassium solution,the invention designs the C-path gas, and the permanent gas of the C-path is also in V with the A-path and the B-path C After the inlet pipeline meets and passes through a water bath coil stainless steel heat exchanger with the temperature of 20 ℃, the water bath coil stainless steel heat exchanger is directly input into a gas chromatograph and a MEECO water analyzer, the total absolute pressure of pipeline gas is still kept at 2Bar, and the C-path gas chromatograph is supposed to detect that the hydrogen content is C at the moment H2-C Moisture content of C H2O-C 。
Assuming that the conversion rate of the reaction of metallic sodium potassium with water is alpha:
α1＝2(C H2-B -C H2-C )/C H2O-C ×100％
α2＝(C H2O-C -C H2O-B )/C H2O-C ×100％
alpha can be calculated by testing according to different permanent gases.
C H2-A ＝α×C H2O-A +C H2-B (I)
C H2-B ＝α×C H2O-C +C H2-C (II)
Is obtained by the formulas (I) and (II):
C H2O-A ＝(C H2-A -C H2-C )/α-C H2O-C
the moisture content of the high purity ethyl silicate measured in example 1 is shown in table 1.
The high purity ethyl silicate of example 1 was tested by karl fischer to give the moisture content shown in table 1.
The example 2 and the example 3 use only permanent gas species and the example 1 are not used, and the other conditions are the same as in the example 1.
TABLE 1 detection results
As can be seen from table 1:
karl fischer processThe accuracy of the water detection (in mass ratio) was 5×10 -6 Below this value is generally referred to; as can be seen from the table, the invention can accurately reach the significant figure after the decimal point, and has higher and more accurate precision than the Karl Fischer method;
in the embodiments 1, 2 and 3 of the invention, the gas of the A path and the gas of the B path enter the middle part of the sodium potassium solution, and other changes do not occur;
from the result of the test calculation of the conversion method, the measurement value of the method is stable and reliable; although the conversion rate also becomes low in response to the gradual decrease in the diffusivity of the three gases of helium, nitrogen, and argon, the trend is less influential.
Claims (2)
1. The method for detecting trace moisture in high-purity ethyl silicate is characterized by comprising the following steps of:
heating high-purity ethyl silicate to 165-168 ℃, then taking permanent gas as a carrier to carry tetraethoxysilane steam into the sodium-potassium alloy, and reacting under the heating condition; the heating condition is 165-168 ℃,
cooling the reacted gas to 15-50 ℃, detecting the content of hydrogen in the reacted gas and the content of hydrogen and moisture in the permanent gas, and obtaining the content of moisture in the high-purity ethyl silicate according to the content of hydrogen in the reacted gas and the content of hydrogen and moisture in the permanent gas; the total absolute pressure of the permanent gas and the tetraethoxysilane steam is 2 Bar;
the permanent gas is an inert gas and/or a sub-inert gas.
2. The method according to claim 1, wherein after the permanent gas is introduced into the sodium-potassium alloy for reaction, the hydrogen content in the permanent gas after reaction is detected, and the water content in the high-purity ethyl silicate is obtained according to the hydrogen content in the gas after reaction and the hydrogen content in the permanent gas after reaction.
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