CN108490113B - Method for determining chlorosilane in dichloromethane - Google Patents
Method for determining chlorosilane in dichloromethane Download PDFInfo
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- CN108490113B CN108490113B CN201810263927.2A CN201810263927A CN108490113B CN 108490113 B CN108490113 B CN 108490113B CN 201810263927 A CN201810263927 A CN 201810263927A CN 108490113 B CN108490113 B CN 108490113B
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 239000005046 Chlorosilane Substances 0.000 title claims abstract description 56
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000006228 supernatant Substances 0.000 claims abstract description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000005259 measurement Methods 0.000 claims abstract description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910021536 Zeolite Inorganic materials 0.000 claims description 22
- 239000010457 zeolite Substances 0.000 claims description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 17
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 17
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 17
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 12
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 12
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 abstract description 19
- -1 chlorine ions Chemical class 0.000 abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 5
- 238000004458 analytical method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 25
- 238000011068 loading method Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 229910001987 mercury nitrate Inorganic materials 0.000 description 6
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 125000006267 biphenyl group Chemical group 0.000 description 5
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 5
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 4
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 4
- 239000005052 trichlorosilane Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MVXUKMCLBMMHFT-UHFFFAOYSA-N C(Cl)Cl.[Cl] Chemical compound C(Cl)Cl.[Cl] MVXUKMCLBMMHFT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to the field of chemical analysis, and particularly relates to a method for determining chlorosilane in dichloromethane, which comprises the following steps: a) mixing a dichloromethane sample with water, standing, and taking a supernatant; b) and measuring the content of chloride ions in the supernatant, and calculating the content of chlorosilane in the dichloromethane sample according to the measurement result. According to the invention, the chlorine ions of the chlorosilane in the dichloromethane sample are skillfully extracted by water by utilizing the difference of the chemical properties of the dichloromethane and the chlorosilane, and the content of the chlorosilane in the dichloromethane sample can be accurately calculated by measuring the content of the extracted chlorine ions. In the preferred technical scheme provided by the invention, before the dichloromethane sample and water are mixed and reacted, the modified zeolite is added into the reaction system as a reaction promoter, so that the full reaction of the water and the chlorosilane in the dichloromethane sample can be promoted, the effect of extracting chloride ions by water is improved, and the accuracy of measuring the content of the chlorosilane is further improved.
Description
Technical Field
The invention belongs to the field of chemical analysis, and particularly relates to a method for determining chlorosilane in dichloromethane.
Background
Polycrystalline silicon has semiconductor properties, is an extremely important excellent semiconductor material, is widely used as a base material for manufacturing semiconductor radios, recorders, refrigerators, color televisions, video recorders, electronic computers and the like in the electronic industry, is a direct raw material for producing monocrystalline silicon, and is an electronic information base material for semiconductor devices such as contemporary artificial intelligence, automatic control, information processing, photoelectric conversion and the like. In solar energy utilization, monocrystalline silicon and polycrystalline silicon play a great role, and the main traditional processes for producing the polycrystalline silicon internationally comprise: modified siemens process, silane process and fluidized bed process. The polysilicon production method (also referred to as siemens method) invented in 1954 by siemens germany, which is currently widely used: high-purity trichlorosilane and high-purity hydrogen are mixed together according to a certain proportion to form raw material mixed gas, the raw material mixed gas is introduced into a reduction reactor, and the raw material mixed gas is continuously deposited on a heated high-purity silicon core, so that the diameter of the silicon core is gradually thickened to form a polycrystalline silicon rod.
Boiling point of dichloromethane: vapor pressure at 39.8 ℃: 30.55kPa (10 ℃) melting Point: -95.1 ℃. In the process of producing polysilicon by an improved Siemens method, a refrigerant in a recovery refrigeration system is dichloromethane, the boiling point of the dichloromethane is between trichlorosilane and silicon tetrachloride, rectification is difficult to remove, the refrigeration temperature in the process can be as low as-70 ℃, a heat exchanger is easy to leak due to large temperature difference, chlorosilane permeates into the dichloromethane to cause the ice machine to jump and stop, loss is brought to the whole production, the leakage of the heat exchanger is timely found by detecting the content of the silane in a dichloromethane chlorine system, and measures are taken to avoid loss brought to the production.
Dichloromethane and chlorosilane are mutually soluble, the boiling point of dichloromethane is between trichlorosilane and silicon tetrachloride, and the measurement of dichloromethane is seriously interfered by chlorosilane and cannot be detected by a conventional analysis method. The peak of dichloromethane can not be separated from the peak of trichlorosilane on the chromatogram map, and can not be detected by chromatographic analysis. At present, no report about the determination of dichloromethane in chlorosilane exists in China and China.
Disclosure of Invention
In view of this, the present invention provides a method for determining chlorosilane in dichloromethane, which can accurately determine the content of chlorosilane in dichloromethane.
The invention provides a method for determining chlorosilane in dichloromethane, which comprises the following steps:
a) mixing a dichloromethane sample with water, standing, and taking a supernatant;
b) and measuring the content of chloride ions in the supernatant, and calculating the content of chlorosilane in the dichloromethane sample according to the measurement result.
Preferably, the volume ratio of the dichloromethane sample to the water is (5-20): 40.
Preferably, the mixing temperature is 15-30 ℃; the mixing time is 0.5-5 min.
Preferably, the step a) is: mixing a dichloromethane sample, a reaction promoter and water, standing, and taking a supernatant;
the reaction promoter includes zeolite and a metal oxide supported on the zeolite.
Preferably, the zeolite is a ZSM-5 molecular sieve;
the metal oxide comprises one or more of iron oxide, titanium dioxide, cerium oxide, yttrium oxide and molybdenum oxide.
Preferably, the metal oxide comprises iron oxide, titanium dioxide, cerium oxide, yttrium oxide and molybdenum oxide, and the mass ratio of the iron oxide to the titanium dioxide to the cerium oxide to the yttrium oxide to the molybdenum oxide is (1-2): (1.5-3): (0.5-1.5): (0.1-1): (1-2).
Preferably, the loading amount of the metal oxide on the zeolite is 0.5-15 wt%.
Preferably, the reaction promoter is prepared by the following method:
the zeolite is impregnated in a metal salt solution and then calcined to obtain the reaction promoter.
Preferably, the dosage ratio of the reaction promoter to water is (1-5) g: 40 ml.
Preferably, the chloride ion content of the supernatant is determined in step b) by mercury method.
Compared with the prior art, the invention provides a method for measuring chlorosilane in dichloromethane. The determination method provided by the invention comprises the following steps: a) mixing a dichloromethane sample with water, standing, and taking a supernatant; b) and measuring the content of chloride ions in the supernatant, and calculating the content of chlorosilane in the dichloromethane sample according to the measurement result. According to the invention, the chlorine ions of the chlorosilane in the dichloromethane sample are skillfully extracted by water by utilizing the difference of the chemical properties of the dichloromethane and the chlorosilane, and the content of the chlorosilane in the dichloromethane sample can be accurately calculated by measuring the content of the extracted chlorine ions. In the preferred technical scheme provided by the invention, before the dichloromethane sample and water are mixed and reacted, a certain amount of modified zeolite is added into the reaction system as a reaction promoter, so that the full reaction of the water and the chlorosilane in the dichloromethane sample can be promoted, the effect of extracting chloride ions by water is improved, and the accuracy of measuring the content of the chlorosilane is further improved. The experimental result shows that when the measuring method provided by the invention is used for measuring dichloromethane containing chlorosilane, the indoor relative standard deviation is 0.04%; the relative standard deviation between chambers is 1.02%, and the relative error is 0.43%; the recovery rate of the added standard is 100.13-101.07%.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for determining chlorosilane in dichloromethane, which comprises the following steps:
a) mixing a dichloromethane sample with water, standing, and taking a supernatant;
b) and measuring the content of chloride ions in the supernatant, and calculating the content of chlorosilane in the dichloromethane sample according to the measurement result.
In the process provided by the present invention, a dichloromethane sample is first mixed with water. In the process, chlorosilane in a dichloromethane sample reacts with water to generate hydrogen chloride which is dissolved in a water phase, and the 'extraction' of chloride ions in chlorosilane is realized. In the invention, the volume ratio of the dichloromethane sample to water is preferably (5-20): 40, and specifically may be 5:40, 6:40, 7:40, 8:40, 9:40, 10:40, 11:40, 12:40, 13:40, 14:40, 15:40, 16:40, 17:40, 18:40, 19:40 or 20: 40.
In the present invention, in order to promote the reaction of chlorosilane and water, it is preferable to add a reaction promoter to the reaction system, i.e., to mix the dichloromethane sample, the reaction promoter and water. Wherein the reaction promoter comprises zeolite and a metal oxide supported on the zeolite; the zeolite is preferably a ZSM-5 molecular sieve; the metal oxide comprises one or more of iron oxide, titanium dioxide, cerium oxide, yttrium oxide and molybdenum oxide. In one embodiment provided by the invention, the metal oxide comprises iron oxide and molybdenum oxide, and the mass ratio of the iron oxide to the molybdenum oxide is preferably (3-4): (3-4), specifically 3.5: 3.8; in one embodiment provided by the invention, the metal oxide comprises iron oxide, titanium dioxide, cerium oxide, yttrium oxide and molybdenum oxide, and the mass ratio of the iron oxide to the titanium dioxide to the cerium oxide to the yttrium oxide to the molybdenum oxide is preferably (1-2): (1.5-3): (0.5-1.5): (0.1-1): (1-2), specifically 1.7:1.9:0.8:0.5: 1.4. In the present invention, the loading amount of the metal oxide on the zeolite is preferably 0.5 to 15 wt%, and specifically may be 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, or 15 wt%. In an embodiment where the metal oxide provided by the present invention includes iron oxide and molybdenum oxide, a loading amount of the iron oxide on the zeolite is preferably 3 to 4 wt%, and specifically may be 3.5 wt%; the loading amount of the molybdenum oxide on the zeolite is preferably 3-4 wt%, and specifically can be 3.8 wt%. In an embodiment where the metal oxide provided by the present invention includes iron oxide, titanium dioxide, cerium oxide, yttrium oxide, and molybdenum oxide, a loading amount of the iron oxide on the zeolite is preferably 1 to 2 wt%, and specifically may be 1.7 wt%; the loading capacity of the titanium dioxide on the zeolite is preferably 1.5-3 wt%, and specifically can be 1.9 wt%; the loading capacity of the cerium oxide on the zeolite is preferably 0.5-1.5 wt%, and specifically can be 0.8 wt%; the loading capacity of the yttrium oxide on the zeolite is preferably 0.1-1 wt%, and specifically can be 0.5 wt%; the loading amount of the molybdenum oxide on the zeolite is preferably 1-2 wt%, and specifically can be 1.4 wt%. In the invention, the ratio of the amount of the reaction promoter to the amount of water is preferably (1-5) g: 40ml, specifically 1 g: 40ml, 1.5 g: 40ml, 2 g: 40ml, 2.5 g: 40ml, 3 g: 40ml, 3.5 g: 40ml, 4 g: 40ml, 4.5 g: 40ml or 5 g: 40 ml.
In one embodiment provided by the present invention, the reaction promoter can be prepared according to the following method:
the zeolite is impregnated in a metal salt solution and then calcined to obtain the reaction promoter.
In the method for preparing the above reaction promoter provided by the present invention, the metal salt preferably includes one or more of iron nitrate, titanium nitrate, cerium nitrate, yttrium nitrate and molybdenum nitrate, the concentration of the metal salt solution and the time for impregnation are not particularly limited in the present invention, and those skilled in the art may select an appropriate concentration of the metal salt solution and an appropriate time for impregnation according to the finally desired metal oxide loading amount. In the invention, the calcination temperature is preferably 400-600 ℃, and specifically can be 400 ℃, 430 ℃, 450 ℃, 470 ℃, 500 ℃, 520 ℃, 550 ℃, 580 ℃ or 600 ℃; the calcination time is preferably 2-10 h, and specifically can be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h or 10 h.
In the invention, in the process of mixing the dichloromethane sample with water or mixing the dichloromethane sample, the reaction promoter and the water, the mixing temperature is preferably 15-30 ℃, and specifically can be 15 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 27 ℃ or 30 ℃; the mixing time is preferably 0.5-5 min, and specifically can be 0.5min, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min or 5 min; the manner of mixing is preferably shaking. After the mixing is finished, standing for a period of time. In the present invention, the specific time for the standing is not particularly limited, and the aqueous phase and the organic phase may be allowed to separate into layers. After the completion of the standing, the supernatant, i.e., the aqueous phase, was taken.
And (4) after taking the supernatant, measuring the content of chloride ions in the supernatant. In the present invention, the measurement method is not particularly limited, and the mercury method is preferably used. In the embodiment of the invention for measuring chloride ions in the supernatant by using the mercury method, the specific measurement process is as follows:
1) transferring 10ml of supernatant to a triangular flask, dropwise adding 2 drops of bromophenol blue, dropwise adding sodium hydroxide if the supernatant is not blue until the supernatant becomes blue, dropwise adding a nitric acid solution to adjust the solution to be yellow, then adding two drops of excess diazocarbonyl hydrazine indicator, adding 1ml of diphenyl azocarbohydrazide indicator, titrating with a mercuric nitrate standard solution, and accurately reading the titration volume when the solution is purple red.
2) Calculating Cl according to the following formula-The content is as follows:
in the formula (I), C is the concentration of a mercury nitrate standard solution and the unit mol/L; v is the volume of mercury nitrate solution consumed in ml.
And calculating the content of chlorosilane in the dichloromethane sample according to the measurement result.
According to the invention, the chlorine ions of the chlorosilane in the dichloromethane sample are skillfully extracted by water by utilizing the difference of the chemical properties of the dichloromethane and the chlorosilane, and the content of the chlorosilane in the dichloromethane sample can be accurately calculated by measuring the content of the extracted chlorine ions. In the preferred technical scheme provided by the invention, before the dichloromethane sample and water are mixed and reacted, a certain amount of modified zeolite is added into the reaction system as a reaction promoter, so that the full reaction of the water and the chlorosilane in the dichloromethane sample can be promoted, the effect of extracting chloride ions by water is improved, and the accuracy of measuring the content of the chlorosilane is further improved. The experimental result shows that when the measuring method provided by the invention is used for measuring dichloromethane containing chlorosilane, the indoor relative standard deviation is 0.04%; the relative standard deviation between chambers is 1.02%, and the relative error is 0.43%; the recovery rate of the added standard is 100.13-101.07%.
For the sake of clarity, the following examples are given in detail.
Example 1
Preparation of reaction promoters
Impregnating a ZSM-5 molecular sieve in a metal salt aqueous solution, wherein the metal salt aqueous solution contains one or more of ferric nitrate, titanium nitrate, cerium nitrate, yttrium nitrate and molybdenum nitrate.
After the impregnation is finished, the ZSM-5 molecular sieve is transferred to a calcining device to be calcined for 4 hours at the temperature of 520 ℃, and the modified ZSM-5 molecular sieve, namely the reaction promoter, is obtained.
In this embodiment, by adjusting the components, concentrations and immersion time of the metal salt aqueous solution, reaction promoters with different metal oxide loadings can be obtained, specifically as follows:
reaction accelerator-a: the load capacity of ferric oxide is 3.5 wt%, and the load capacity of molybdenum oxide is 3.8 wt%;
reaction accelerator-b: the iron oxide loading was 1.7 wt%, the titanium dioxide loading was 1.9 wt%, the cerium oxide loading was 0.8 wt%, the yttrium oxide loading was 0.5 wt%, and the molybdenum oxide loading was 1.4 wt%.
Example 2
Determination of chlorosilanes in dichloromethane
1) Transferring 100ml of sample into a colorimetric tube, fixing the volume to 500ml with pure water, shaking for 2min, standing, and transferring 10ml of supernatant into a triangular flask.
2) Dropwise adding 2 drops of bromophenol blue, dropwise adding sodium hydroxide until the solution turns blue if the solution does not turn blue, adjusting the solution to be yellow by dropwise adding a nitric acid solution, adding two excessive drops of the nitric acid solution, adding 1ml of diphenyl azo carbohydrazide indicator, titrating by using mercury nitrate standard solution, taking the condition of purple red as a terminal point, and accurately reading the titration volume.
3) The Cl in the supernatant was calculated according to formula (I)-The content of the chlorine ions in the supernatant is totally from chlorosilane according to Cl in the supernatant-And (4) calculating the content of chlorosilane in the dichloromethane sample.
4) Precision and accuracy evaluation
A dichloromethane sample with a chlorosilane content of 88.29mg/L was analyzed in five laboratories according to steps 1) to 3), and the standard deviation was calculated according to formula (a):
S＝Sqrt[(∑(xi-xaverage)^2)/(N-1)]S type (a)
In the formula (a), Sqrt is square root, Sigma represents total sum, 2 represents quadratic power, and XAverageFor the measurement of the average value, N represents the number of measurements, and N is 5 in the test.
Calculating the coefficient of variation according to equation (b):
Vx＝S/xaverage100% formula (b)
In the formula (b), S is a standard deviation, xAverageIn order to determine the average value,
the relative standard deviation in the chamber was determined and calculated to be 0.09%, the relative standard deviation between the chambers was 1.1%, and the relative error was 0.7%.
And (3) transferring 100ml of dichloromethane sample with the chlorosilane content of 88.29mg/L, adding 100mg of chlorosilane into a colorimetric tube, measuring the chlorosilane content according to the steps 1) to 3), and calculating the recovery rate of the added standard. The results of 5 parallel tests show that the recovery rate is between 98.1% and 102.5%.
Example 3
Determination of chlorosilanes in dichloromethane
1) Transferring 100ml of sample into a colorimetric tube, fixing the volume to 500ml with pure water, adding 20g of ZSM-5 molecular sieve, shaking for 2min, standing, and transferring 10ml of supernatant into a triangular flask.
2) Dropwise adding 2 drops of bromophenol blue, dropwise adding sodium hydroxide until the solution turns blue if the solution does not turn blue, adjusting the solution to be yellow by dropwise adding a nitric acid solution, adding two excessive drops of the nitric acid solution, adding 1ml of diphenyl azo carbohydrazide indicator, titrating by using mercury nitrate standard solution, taking the condition of purple red as a terminal point, and accurately reading the titration volume.
3) The Cl in the supernatant was calculated according to formula (I)-The content of the chlorine ions in the supernatant is totally from chlorosilane according to Cl in the supernatant-And (4) calculating the content of chlorosilane in the dichloromethane sample.
4) Precision and accuracy evaluation
The precision and accuracy of the measurement method of this example were evaluated in the manner of evaluation of example 2, and the results showed that: the indoor relative standard deviation is 0.07 percent, the inter-indoor relative standard deviation is 1.07 percent, the relative error is 0.64 percent, and the recovery rate is between 98.5 and 102.3 percent.
Example 4
Determination of chlorosilanes in dichloromethane
1) Transferring 100ml of sample into a colorimetric tube, fixing the volume to 500ml with pure water, adding 20g of reaction accelerator-a, shaking for 2min, standing, and transferring 10ml of supernatant into a triangular flask.
2) Dropwise adding 2 drops of bromophenol blue, dropwise adding sodium hydroxide until the solution turns blue if the solution does not turn blue, adjusting the solution to be yellow by dropwise adding a nitric acid solution, adding two excessive drops of the nitric acid solution, adding 1ml of diphenyl azo carbohydrazide indicator, titrating by using mercury nitrate standard solution, taking the condition of purple red as a terminal point, and accurately reading the titration volume.
3) The Cl in the supernatant was calculated according to formula (I)-The content of the chlorine ions in the supernatant is totally from chlorosilane according to Cl in the supernatant-And (4) calculating the content of chlorosilane in the dichloromethane sample.
4) Precision and accuracy evaluation
The precision and accuracy of the measurement method of this example were evaluated in the manner of evaluation of example 2, and the results showed that: the indoor relative standard deviation is 0.05 percent, the inter-indoor relative standard deviation is 1.04 percent, the relative error is 0.53 percent, and the recovery rate is between 99.3 and 101.8 percent.
Example 5
Determination of chlorosilanes in dichloromethane
1) Transferring 100ml of sample into a colorimetric tube, fixing the volume to 500ml by using pure water, adding 20g of reaction accelerator-b, shaking for 2min, standing, and transferring 10ml of supernatant into a triangular flask.
2) Dropwise adding 2 drops of bromophenol blue, dropwise adding sodium hydroxide until the solution turns blue if the solution does not turn blue, adjusting the solution to be yellow by dropwise adding a nitric acid solution, adding two excessive drops of the nitric acid solution, adding 1ml of diphenyl azo carbohydrazide indicator, titrating by using mercury nitrate standard solution, taking the condition of purple red as a terminal point, and accurately reading the titration volume.
3) The Cl in the supernatant was calculated according to formula (I)-The content of the chlorine ions in the supernatant is totally from chlorosilane according to Cl in the supernatant-And (4) calculating the content of chlorosilane in the dichloromethane sample.
4) Precision and accuracy evaluation
The precision and accuracy of the measurement method of this example were evaluated in the manner of evaluation of example 2, and the results showed that: indoor relative standard deviation is 0.04%; the relative standard deviation between chambers is 1.02%, and the relative error is 0.43%; the recovery rate is between 100.13 and 101.07 percent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A method for measuring chlorosilane in dichloromethane comprises the following steps:
a) mixing a dichloromethane sample, a reaction promoter and water, standing, and taking supernatant;
the reaction promoter comprises zeolite and metal oxide loaded on the zeolite; the metal oxide comprises one or more of iron oxide, titanium dioxide, cerium oxide, yttrium oxide and molybdenum oxide;
b) and measuring the content of chloride ions in the supernatant, and calculating the content of chlorosilane in the dichloromethane sample according to the measurement result.
2. The method according to claim 1, wherein the volume ratio of the dichloromethane sample to water is (5-20): 40.
3. The method according to claim 1, wherein the temperature of the mixing is 15 to 30 ℃; the mixing time is 0.5-5 min.
4. The method of claim 1, wherein the zeolite is a ZSM-5 molecular sieve.
5. The method according to claim 1, wherein the metal oxide comprises iron oxide, titanium dioxide, cerium oxide, yttrium oxide and molybdenum oxide, and the mass ratio of the iron oxide to the titanium dioxide to the cerium oxide to the yttrium oxide to the molybdenum oxide is (1-2): (1.5-3): (0.5-1.5): (0.1-1): (1-2).
6. The method according to claim 1, wherein the metal oxide is supported on the zeolite at a content of 0.5 to 15 wt%.
7. The method according to claim 1, wherein the reaction accelerator is prepared by the following method:
the zeolite is impregnated in a metal salt solution and then calcined to obtain the reaction promoter.
8. The method according to claim 1, wherein the reaction accelerator and water are used in a ratio of (1 to 5) g: 40 ml.
9. The method according to any one of claims 1 to 8, wherein the content of chloride ions in the supernatant is measured in step b) by a mercury method.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4497942A (en) * | 1983-12-14 | 1985-02-05 | General Electric Company | Process for hydrolyzing chlorosilanes |
| CN1090580A (en) * | 1993-02-03 | 1994-08-10 | 化学工业部晨光化工研究院成都分院 | The method for hydrolysis of organic radical silicane dichloride |
| JP2000338098A (en) * | 1999-05-25 | 2000-12-08 | Shin Etsu Chem Co Ltd | Method for continuous determination of hydrolyzable component-containing gaseous material |
| CN105510313A (en) * | 2015-11-23 | 2016-04-20 | 湖北平安电工股份有限公司 | Rapid purity detection method of industrial grade chlorosilane |
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- 2018-03-28 CN CN201810263927.2A patent/CN108490113B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4497942A (en) * | 1983-12-14 | 1985-02-05 | General Electric Company | Process for hydrolyzing chlorosilanes |
| CN1090580A (en) * | 1993-02-03 | 1994-08-10 | 化学工业部晨光化工研究院成都分院 | The method for hydrolysis of organic radical silicane dichloride |
| JP2000338098A (en) * | 1999-05-25 | 2000-12-08 | Shin Etsu Chem Co Ltd | Method for continuous determination of hydrolyzable component-containing gaseous material |
| CN105510313A (en) * | 2015-11-23 | 2016-04-20 | 湖北平安电工股份有限公司 | Rapid purity detection method of industrial grade chlorosilane |
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| Title |
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| 氯硅烷水解工艺研究进展;陈其国等;《化工管理》;20171231(第36期);64-66 * |
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