CN110542725A - Process for detecting nitrogen in hydrogen - Google Patents
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- CN110542725A CN110542725A CN201810530459.0A CN201810530459A CN110542725A CN 110542725 A CN110542725 A CN 110542725A CN 201810530459 A CN201810530459 A CN 201810530459A CN 110542725 A CN110542725 A CN 110542725A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 197
- 239000001257 hydrogen Substances 0.000 title claims abstract description 119
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 119
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 126
- 238000004817 gas chromatography Methods 0.000 claims abstract description 44
- 230000002378 acidificating effect Effects 0.000 claims abstract description 37
- 239000000126 substance Substances 0.000 claims abstract description 23
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 18
- 230000007935 neutral effect Effects 0.000 claims abstract description 16
- 239000012670 alkaline solution Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 27
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 27
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 26
- 230000015572 biosynthetic process Effects 0.000 claims description 26
- 238000003786 synthesis reaction Methods 0.000 claims description 26
- 239000005046 Chlorosilane Substances 0.000 claims description 20
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002696 acid base indicator Substances 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 11
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 10
- 239000005052 trichlorosilane Substances 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical group C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 5
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 239000005049 silicon tetrachloride Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229920005591 polysilicon Polymers 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000002912 waste gas Substances 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000001514 detection method Methods 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003463 adsorbent Substances 0.000 description 7
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical group C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 238000004891 communication Methods 0.000 description 4
- 238000004451 qualitative analysis Methods 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002826 coolant Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
Classifications
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- 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
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/067—Preparation by reaction, e.g. derivatising the sample
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
- G01N2030/143—Preparation by elimination of some components selective absorption
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a process for detecting nitrogen in hydrogen, which comprises the following steps: 1) introducing hydrogen into an alkaline solution with a preset concentration to remove acidic substances to obtain a first mixed gas, and if the acidity and alkalinity of the first mixed gas are determined to be neutral, executing the following step 2); 2) and (4) carrying out gas chromatography on the first mixed gas, and detecting nitrogen in the first mixed gas. According to the process for detecting the nitrogen in the hydrogen, the acidic substances contained in the hydrogen are removed, the neutral first mixed gas is subjected to gas chromatography analysis to detect the nitrogen, so that the interference of the removed acidic substances on the nitrogen detection is avoided, the accuracy of the gas chromatography analysis on the nitrogen is improved, the corrosion of the removed acidic substances on a gas chromatograph used for the gas chromatography analysis is also avoided, and the service life of the gas chromatograph is prolonged.
Description
Technical Field
The invention belongs to the technical field of polycrystalline silicon production, and particularly relates to a process for detecting nitrogen in hydrogen.
Background
The hydrogen is one of important raw materials in the production process of the polycrystalline silicon, and in the existing improved Siemens method, the raw material hydrogen used in the production of the trichlorosilane by the cold hydrogenation process system mainly comes from hydrogen produced by electrolysis in the CDI process and hydrogen circulating by the system. Along with the extension of the operation period of the cold hydrogenation process system, a large amount of nitrogen, hydrogen chloride gas and a small amount of chlorosilane gas are enriched in the circulating hydrogen of the system. In the prior art, circulating hydrogen is cooled by coolants such as ethylene glycol or freon, chlorosilane in the circulating hydrogen is removed, and nitrogen and a small amount of hydrogen chloride gas in mixed gas are removed by a pressure swing adsorption device. Partial nitrogen in the hydrogen is adsorbed by the pressure swing adsorption device, a large amount of hydrogen chloride gas is still contained in the adsorbed hydrogen, when the nitrogen in the hydrogen is detected by using a chromatographic detector, the corrosion of the hydrogen chloride gas on a chromatographic column is large, the concentration of the hydrogen chloride is higher than 2000ppm, and the content of the nitrogen in the hydrogen cannot be detected by the chromatographic detector, so that the content of the nitrogen in the hydrogen cannot be accurately detected, and the enrichment amount of the content of the nitrogen in the raw material hydrogen to be used for cold hydrogenation synthesis cannot be accurately judged.
disclosure of Invention
The technical problem to be solved by the present invention is to provide a process for detecting nitrogen in hydrogen, which avoids the interference of the removed acidic substances on nitrogen detection, improves the accuracy of gas chromatography analysis of nitrogen, and avoids the corrosion of the removed acidic substances on a gas chromatography column used for gas chromatography analysis.
The technical scheme adopted for solving the technical problem of the invention is to provide a process for detecting nitrogen in hydrogen, which comprises the following steps:
1) Introducing hydrogen into an alkaline solution with a preset concentration to remove acidic substances to obtain a first mixed gas, and if the acidity and alkalinity of the first mixed gas are determined to be neutral, executing the following step 2);
2) And (4) carrying out gas chromatography on the first mixed gas, and detecting nitrogen in the first mixed gas.
Preferably, in the step 1), if the acidity or basicity of the first mixed gas is determined to be acidic, the first mixed gas is returned to perform the operation of introducing the alkali solution with the preset concentration in the step 1).
preferably, after 1 to 4 times of returning to the step 1) of introducing the alkali solution with the preset concentration, if the acidity-basicity of the first mixed gas is still determined to be acidic, the following step 3) of treating the first mixed gas as the exhaust gas is performed.
Preferably, the method for measuring the acidity and basicity of the first mixed gas in the step 1) is as follows: the alkali solution with the preset concentration in the step 1) contains an acid-base indicator, and the acidity and the alkalinity of the first mixed gas are judged through the change of the color of the acid-base indicator.
Preferably, the acid-base indicator is phenolphthalein test solution or litmus test solution.
Preferably, the hydrogen in step 1) is recycled hydrogen for cold hydrogenation synthesis or regenerated hydrogen in a polysilicon reduction tail gas recovery (CDI) step. .
preferably, the recycle hydrogen for cold hydrogenation synthesis comprises: hydrogen chloride is less than or equal to 5000ppm, the sum of methane, carbon monoxide and carbon dioxide is less than or equal to 500ppm, the mass percent of chlorosilane is 2-5%, nitrogen is contained, and the balance is hydrogen, wherein chlorosilane is silicon tetrachloride and trichlorosilane;
The hydrogen regeneration in the polycrystalline silicon reduction tail gas recovery process comprises the following steps: the hydrogen chloride is less than or equal to 5000ppm, the mass percentage of the total of dichlorosilane and trichlorosilane is 5-10%, nitrogen is contained, and the balance is hydrogen.
Preferably, the recycle hydrogen for cold hydrogenation synthesis comprises: hydrogen chloride is less than or equal to 5000ppm when the content of 0< hydrogen chloride is less than or equal to 5000ppm, the sum of methane, carbon monoxide and carbon dioxide is less than or equal to 500ppm when the content of 0< methane, carbon monoxide and carbon dioxide is less than or equal to 500ppm, the mass percent of chlorosilane is 2-5%, nitrogen is contained, and the balance is hydrogen, wherein the chlorosilane is silicon tetrachloride and;
the hydrogen regeneration in the polycrystalline silicon reduction tail gas recovery process comprises the following steps: hydrogen chloride of 0ppm or less and hydrogen chloride of 5000ppm or less, dichlorosilane and trichlorosilane of 0 mass percent of 5-10%, nitrogen and hydrogen in balance.
Preferably, the alkali solution is a sodium hydroxide solution or a calcium hydroxide solution.
Preferably, the step 1) is preceded by the step of collecting recycle hydrogen for cold hydrogenation synthesis:
m) cooling the circulating hydrogen in the cold hydrogenation synthesis process to remove chlorosilane in the circulating hydrogen to obtain a second mixed gas;
And n) adsorbing the nitrogen and the hydrogen chloride by the second mixed gas through a pressure swing adsorption device to obtain the circulating hydrogen for cold hydrogenation synthesis. The pressure swing adsorption device absorbs nitrogen, methane, hydrogen chloride and other gases in the circulating hydrogen in the cold hydrogenation synthesis process through the adsorbent, so that the hydrogen containing chlorosilane, nitrogen, methane, hydrogen chloride and other gases is purified. After the nitrogen is purified by the pressure swing adsorption device, the mass percentage content of the nitrogen is more than or equal to 0 and less than or equal to 6 percent, the adsorbent is gradually saturated along with the extension of the operation period of the pressure swing adsorption device, the adsorption effect is lost, and a certain amount of nitrogen is contained in the circulating hydrogen used for cold hydrogenation synthesis.
Preferably, the preset concentration of the alkali solution in the step 1) is 0.5-1.5M.
Preferably, the conditions for introducing the recycle hydrogen gas for cold hydrogenation synthesis into the alkali solution with a preset concentration in the step 1) are as follows: under the conditions of-45 deg.C to-20 deg.C and 0.2MPa to 2.5MPa pressure.
Preferably, a step i) of drying the first mixed gas to remove water is further included between the step 1) and the step 2).
According to the process for detecting the nitrogen in the hydrogen, the acidic substances in the hydrogen are removed, the neutral first mixed gas is subjected to gas chromatography analysis to detect the nitrogen, the interference of the removed acidic substances on the nitrogen detection is avoided, the accuracy of the gas chromatography analysis on the nitrogen is improved, the corrosion of the removed acidic substances on a gas chromatography column used for the gas chromatography analysis is avoided, the corrosion of the gas chromatography column is avoided, the inactivation of an adsorbent in the gas chromatography column is also avoided, and the service life of the gas chromatography column is prolonged. By the process for detecting the nitrogen in the hydrogen, after acidic gases such as hydrogen chloride, chlorosilane and the like are removed, the nitrogen content can be detected to be 50 ppm-5 mas%.
Drawings
fig. 1 is a schematic structural view of an apparatus for detecting nitrogen in hydrogen in embodiment 3 of the present invention.
In the figure: 1-a hydrogen storage vessel; 2-a first reaction vessel; 3-gas chromatography; 4-a first valve; 5-a second reaction vessel; 6-a second valve; 7-a third valve; 8-a tail gas processor; 9-fourth valve.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1
The embodiment provides a process for detecting nitrogen in hydrogen, which comprises the following steps:
1) Introducing hydrogen into an alkaline solution with a preset concentration to remove acidic substances to obtain a first mixed gas, and if the acidity and alkalinity of the first mixed gas are determined to be neutral, executing the following step 2);
2) And (4) carrying out gas chromatography on the first mixed gas, and detecting nitrogen in the first mixed gas.
In the process for detecting nitrogen in hydrogen in this embodiment, the acidic substance contained in the hydrogen is removed, and the neutral first mixed gas is subjected to gas chromatography to detect nitrogen, so that the interference of the removed acidic substance on nitrogen detection is avoided, the accuracy of gas chromatography for nitrogen analysis is improved, on the other hand, the corrosion of the removed acidic substance on a gas chromatography column used for gas chromatography is also avoided, the corrosion of the gas chromatography column is avoided, the inactivation of an adsorbent inside the gas chromatography column is also avoided, and the service life of the gas chromatography column is prolonged.
example 2
The embodiment provides a process for detecting nitrogen in hydrogen, which comprises the following steps:
1) Introducing hydrogen into a sodium hydroxide solution with a preset concentration of 1M, wherein an alkali solution with the preset concentration contains an acid-base indicator to obtain a first mixed gas, wherein the hydrogen sampling amount is not less than 200ml each time under the conditions of-45 ℃ and 0.2 Mpa; specifically, the acid-base indicator in this embodiment is phenolphthalein test solution.
specifically, the hydrogen in this example is recycled hydrogen for cold hydrogenation synthesis. The hydrogen chloride in the circulating hydrogen for cold hydrogenation synthesis is less than or equal to 5000ppm, the sum of methane, carbon monoxide and carbon dioxide is less than or equal to 500ppm, the mass percent of chlorosilane is 2-5%, nitrogen is contained, and the balance is hydrogen, wherein the chlorosilane is silicon tetrachloride and trichlorosilane.
if the acidity-basicity of the first mixed gas is determined to be neutral, the following step 2) is executed;
If the acidity and alkalinity of the first mixed gas are determined to be acidity, returning the first mixed gas to the operation of introducing the alkali solution with the preset concentration in the step 1) until the acidity and alkalinity of the first mixed gas are determined to be neutral, and executing the following step 2);
2) And drying the first mixed gas by a calcium chloride drying agent, and removing water.
3) And (3) carrying out gas chromatography analysis on the dried first mixed gas through a gas chromatograph, detecting nitrogen in the first mixed gas, and carrying out qualitative and quantitative analysis on the nitrogen through the gas chromatography analysis.
In the process for detecting nitrogen in hydrogen in this embodiment, the acidic substance contained in the hydrogen is removed, and the neutral first mixed gas is subjected to gas chromatography to detect nitrogen, so that the interference of the removed acidic substance on nitrogen detection is avoided, the accuracy of gas chromatography for nitrogen analysis is improved, on the other hand, the corrosion of the removed acidic substance on a gas chromatography column used for gas chromatography is also avoided, the corrosion of the gas chromatography column is avoided, the inactivation of an adsorbent inside the gas chromatography column is also avoided, and the service life of the gas chromatography column is prolonged.
By the process for detecting nitrogen in hydrogen in the embodiment, after acidic gases such as hydrogen chloride and chlorosilane are removed, the content of nitrogen can be detected to be 3 mas%.
example 3
The embodiment provides a process for detecting nitrogen in hydrogen, which comprises the following steps:
1) Cooling the circulating hydrogen in the cold hydrogenation synthesis process to remove chlorosilane in the circulating hydrogen to obtain a second mixed gas;
2) And adsorbing the nitrogen and the hydrogen chloride by the second mixed gas through a pressure swing adsorption device to obtain the circulating hydrogen for cold hydrogenation synthesis. The pressure swing adsorption device absorbs nitrogen, methane, hydrogen chloride and other gases in the circulating hydrogen in the cold hydrogenation synthesis process through the adsorbent, so that the hydrogen containing chlorosilane, nitrogen, methane, hydrogen chloride and other gases is purified. After the nitrogen is purified by the pressure swing adsorption device, the mass percentage content of the nitrogen is more than or equal to 0 and less than or equal to 6 percent, the adsorbent is gradually saturated along with the extension of the operation period of the pressure swing adsorption device, the adsorption effect is lost, and a certain amount of nitrogen is contained in the circulating hydrogen used for cold hydrogenation synthesis.
3) The hydrogen sampling amount of each circulation in the cold hydrogenation synthesis process is not less than 200ml, an acid-base indicator is added into a sodium hydroxide solution with a preset concentration of 0.5M, and the circulation in the cold hydrogenation synthesis process is introduced into an alkali solution with a preset concentration under the conditions of-30 ℃ and a pressure of 2.5Mpa to obtain a first mixed gas; specifically, the acid-base indicator in this embodiment is phenolphthalein test solution.
Specifically, the hydrogen in this example is recycled hydrogen for cold hydrogenation synthesis. The recycle hydrogen for cold hydrogenation synthesis comprises: hydrogen chloride is less than or equal to 5000ppm when the content of 0, the sum of methane, carbon monoxide and carbon dioxide is less than or equal to 500ppm when the content of 0, chlorosilane is 2-5% by mass, nitrogen and hydrogen are the rest, wherein the chlorosilane is silicon tetrachloride and trichlorosilane.
If the acidity and alkalinity of the first mixed gas is determined to be neutral, executing the following step 4);
if the acidity or alkalinity of the first mixed gas is determined to be acidic, the first mixed gas is returned to the operation of introducing the alkali solution with the preset concentration in the step 3), and after 1 time of returning to the operation of introducing the alkali solution with the preset concentration in the step 3), if the acidity or alkalinity of the first mixed gas is still determined to be acidic, the following step 6) is executed.
4) And drying the first mixed gas by a calcium chloride drying agent, and removing water.
5) And (3) carrying out gas chromatography analysis on the dried first mixed gas through a gas chromatograph, detecting nitrogen in the first mixed gas, and carrying out qualitative and quantitative analysis on the nitrogen through the gas chromatography analysis.
6) The first mixture is treated as an exhaust gas.
as shown in fig. 1, the present embodiment provides an apparatus for detecting nitrogen in hydrogen, including:
a hydrogen storage container 1 for storing hydrogen.
The first reaction container 2 is connected with the hydrogen storage container 1, an alkali solution with a preset concentration is contained in the first reaction container 2, hydrogen is introduced into the alkali solution with the preset concentration in the first reaction container 2 to remove acidic substances, and a first mixed gas is obtained at an outlet of the first reaction container 2.
And a gas chromatograph 3 connected to the first reaction vessel 2, wherein when the acidity or alkalinity of the first mixed gas is determined to be neutral, the first valve 4 on the communication line between the gas chromatograph 3 and the first reaction vessel 2 is opened, and the first mixed gas is subjected to gas chromatography by the gas chromatograph 3 to detect nitrogen therein.
And the second reaction vessel 5 is connected with the first reaction vessel 2, an alkali solution with a preset concentration is contained in the second reaction vessel 5, if the acidity and alkalinity of the first mixed gas are measured to be acidic, a second valve 6 on a communication pipeline between the second reaction vessel 5 and the first reaction vessel 2 is opened, so that the first mixed gas is introduced into the alkali solution with the preset concentration in the second reaction vessel 5 to remove acidic substances, and the first mixed gas is obtained at the outlet of the second reaction vessel 5. When the acidity or alkalinity of the first mixed gas is determined to be neutral, the third valve 7 on the communication line between the gas chromatograph 3 and the second reaction vessel 5 is opened, the first mixed gas is subjected to gas chromatography by the gas chromatograph 3, and the nitrogen gas therein is detected.
And the tail gas processor 8 is connected with the second reaction container 5, the tail gas processor 8 is used for processing tail gas, and if the acidity or alkalinity of the first mixed gas is determined to be acidic, the fourth valve 9 on the communication pipeline between the tail gas processor 8 and the second reaction container 5 is opened, and the first mixed gas is used as waste gas for processing.
in the process for detecting nitrogen in hydrogen in this embodiment, the acidic substance contained in the hydrogen is removed, and the gas chromatography is performed on the neutral first mixed gas to detect the nitrogen, so that the interference of the removed acidic substance on the nitrogen detection is avoided, and the accuracy of the gas chromatography for analyzing the nitrogen is improved.
By the process for detecting nitrogen in hydrogen in the embodiment, after acidic gases such as hydrogen chloride and chlorosilane are removed, the content of nitrogen can be detected to be 5 mas%.
Example 4
The embodiment provides a process for detecting nitrogen in hydrogen, which comprises the following steps:
1) Mixing an acid-base indicator with a sodium hydroxide solution with a preset concentration of 1.5M, wherein the sampling amount of hydrogen is not less than 200ml each time, and introducing the hydrogen into an alkali solution with the preset concentration at the temperature of minus 20 ℃ and the pressure of 2Mpa to obtain a first mixed gas; specifically, the hydrogen in this embodiment is the hydrogen regenerated in the polysilicon reduction tail gas recovery process. The hydrogen regeneration in the polycrystalline silicon reduction tail gas recovery process comprises the following steps: the hydrogen chloride is less than or equal to 5000ppm, the mass percentage of the total of dichlorosilane and trichlorosilane is 5-10%, nitrogen is contained, and the balance is hydrogen. Specifically, the acid-base indicator in this embodiment is litmus sample solution.
if the acidity-basicity of the first mixed gas is determined to be neutral, the following step 2) is executed;
If the acidity and alkalinity of the first mixed gas are determined to be acidic, the first mixed gas is returned to the operation of introducing the alkali solution with the preset concentration in the step 1), and after 4 times of returning to the operation of introducing the alkali solution with the preset concentration in the step 1), if the acidity and alkalinity of the first mixed gas are still determined to be acidic, the following step 4) is executed.
2) And drying the first mixed gas by a calcium chloride drying agent, and removing water.
3) And (3) carrying out gas chromatography analysis on the dried first mixed gas through a gas chromatograph, detecting nitrogen in the first mixed gas, and carrying out qualitative and quantitative analysis on the nitrogen through the gas chromatography analysis.
4) The first mixture is treated as an exhaust gas.
After the acid gas is removed by the process for detecting nitrogen in hydrogen in this example, the nitrogen content can be detected to be 50 ppm.
Example 5
The embodiment provides a process for detecting nitrogen in hydrogen, which comprises the following steps:
1) adding an acid-base indicator into a calcium hydroxide solution with a preset concentration of 2M, wherein the sampling amount of hydrogen is not less than 200ml each time, and introducing the hydrogen into an alkali solution with the preset concentration at-28 ℃ and under the pressure of 0.5Mpa to obtain a first mixed gas; specifically, the hydrogen in this embodiment is the hydrogen regenerated in the polysilicon reduction tail gas recovery process. The hydrogen regeneration in the polycrystalline silicon reduction tail gas recovery process comprises the following steps: 0< hydrogen chloride is less than or equal to 5000ppm, the mass percentage of the total of dichlorosilane and trichlorosilane is 5-10%, nitrogen is contained, and the balance is hydrogen. Specifically, the acid-base indicator in this embodiment is litmus sample solution.
If the acidity-basicity of the first mixed gas is determined to be neutral, the following step 2) is executed;
If the acidity and alkalinity of the first mixed gas are determined to be acidic, the first mixed gas is returned to the step 1) of introducing the alkali solution with the preset concentration, and after 2 times of returning to the step 1) of introducing the alkali solution with the preset concentration, if the acidity and alkalinity of the first mixed gas are still determined to be acidic, the following step 3) is executed.
2) And (3) carrying out gas chromatography analysis on the first mixed gas through a gas chromatograph, detecting nitrogen in the first mixed gas, and carrying out qualitative and quantitative analysis on the nitrogen through the gas chromatography analysis.
3) The first mixture is treated as an exhaust gas.
after the acid gas is removed by the process for detecting nitrogen in hydrogen in the embodiment, the content of nitrogen can be detected to be 0.5 mas%.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (10)
1. A process for detecting nitrogen in hydrogen, comprising the steps of:
1) introducing hydrogen into an alkaline solution with a preset concentration to remove acidic substances to obtain a first mixed gas, and if the acidity and alkalinity of the first mixed gas are determined to be neutral, executing the following step 2);
2) and (4) carrying out gas chromatography on the first mixed gas, and detecting nitrogen in the first mixed gas.
2. the process for detecting nitrogen in hydrogen according to claim 1, wherein in step 1), if the acidity-basicity of the first mixed gas is determined to be acidic, the first mixed gas is returned to the step 1) of introducing the alkali solution with the preset concentration.
3. The process for detecting nitrogen in hydrogen according to claim 2, wherein after 1 to 4 times of returning and performing the operation of introducing the alkali solution with the preset concentration in the step 1), if the acidity and alkalinity of the first mixed gas is still determined to be acidic, the following step 3) is performed to treat the first mixed gas as the waste gas.
4. The process for detecting nitrogen in hydrogen according to claim 1, wherein the method for determining the acidity or basicity of the first mixed gas in step 1) is as follows: the alkali solution with the preset concentration in the step 1) contains an acid-base indicator, and the acidity and the alkalinity of the first mixed gas are judged through the change of the color of the acid-base indicator.
5. The process for detecting nitrogen in hydrogen according to claim 1, wherein the hydrogen in step 1) is recycled hydrogen for cold hydrogenation synthesis or regenerated hydrogen in a polysilicon reduction tail gas recovery process.
6. Process for detecting nitrogen in hydrogen according to claim 5, characterized in that said recycled hydrogen for cold hydrogenation synthesis comprises: hydrogen chloride is less than or equal to 5000ppm, the sum of methane, carbon monoxide and carbon dioxide is less than or equal to 500ppm, the mass percent of chlorosilane is 2-5%, nitrogen is contained, and the balance is hydrogen, wherein chlorosilane is silicon tetrachloride and trichlorosilane;
The hydrogen regeneration in the polycrystalline silicon reduction tail gas recovery process comprises the following steps: the hydrogen chloride is less than or equal to 5000ppm, the mass percentage of the total of dichlorosilane and trichlorosilane is 5-10%, nitrogen is contained, and the balance is hydrogen.
7. the process for detecting nitrogen in hydrogen according to claims 5 and 6, wherein step 1) is preceded by a step of collecting recycled hydrogen for cold hydrogenation synthesis:
m) cooling the circulating hydrogen in the cold hydrogenation synthesis process to remove chlorosilane in the circulating hydrogen to obtain a second mixed gas;
and n) adsorbing the nitrogen and the hydrogen chloride by the second mixed gas through a pressure swing adsorption device to obtain the circulating hydrogen for cold hydrogenation synthesis.
8. the process for detecting nitrogen in hydrogen according to any one of claims 1 to 6, wherein the predetermined concentration of the alkali solution in the step 1) is 0.5 to 1.5M.
9. The process for detecting nitrogen in hydrogen according to any one of claims 1 to 6, wherein the conditions for introducing the circulating hydrogen used for cold hydrogenation synthesis into the alkali solution with the preset concentration in the step 1) are as follows: under the conditions of-45 deg.C to-20 deg.C and 0.2MPa to 2.5MPa pressure.
10. the process for detecting nitrogen in hydrogen according to any one of claims 1 to 6, further comprising a step i) of drying the first mixed gas to remove water between the step 1) and the step 2).
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Application publication date: 20191206 |