Preparation method and use method of material for deep purification of HF electronic gas

Abstract

Provided is a preparation method and use method of a material for deep purification of HF electronic gas. A metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O is prepared, and a mixed gas flow of carbonyl fluoride and high-purity nitrogen is used to deeply dehydrate the material to obtain the material for deep purification of HF electronic gas AC/MFx. This kind of material has fluoride that can form crystal water to form hydrated metal fluoride, and has strong water absorption properties. Moreover, the anhydrous fluoride and activated carbon do not have to face the problem of being corroded by HF, and the collapse of framework structure and the secondary pollution to HF from reaction products would not be caused. The material has the advantages of high purity and extremely low moisture content when being used for efficiently removing moisture in HF.

Claims

1. A method for preparing a material for deep purification of HF electronic gas, comprising: in parts by mass, dissolving 15.2-45.4 parts of acetate in 2000-4000 parts of pure water, and stirring for 10-30 min; after dissolving uniformly, adding 126.4-186.5 parts of disodium ethylenediaminetetraacetate, and stirring for 10-20 min to form a mixed solution; then adding 7.2-7.8 parts of ammonium fluoride and stirring; after mixing evenly, adding ammonia dropwise to adjust a pH value to 9-11; then adding 130-170 parts of mesoporous activated carbon and 0.1-0.5 parts of sodium tetrafluoroborate as an inducer, and stirring at 40-60 C. for 20-50 min; subsequently, transferring a resulting mixture to a hydrothermal reactor, and subjecting to a crystallization reaction at 140-180 C. for 80-120 min; thereafter, cooling slowly to room temperature, filtering to obtain a material, and washing with absolute ethanol; repeating washing with absolute ethanol for 3-5 times, and then drying a resulting material in an oven at 120-160 C. for 10-18 h to obtain a metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O; subjecting the metal fluoride-loaded activated carbon material to a deep dehydration to obtain a material for deep purification of HF electronic gas AC/MFx; wherein the mesoporous activated carbon is a mesoporous activated carbon with a high mesoporosity, and a process for preparing the mesoporous activated carbon with a high mesoporosity comprises: in parts by mass, adding 7-34 parts of ammonium dihydrogen phosphate, 16-44 parts of dodecylurea, 1-8 parts of urea and 0.05-0.3 parts of 1-butyl-3-methylimidazolium molybdotungstophosphate into 1000-3000 parts of water and stirring; after mixing evenly, soaking 100-200 parts of a cleaned wood dust in a resulting mixed solution at room temperature for 5-10 h, and then heating to 40-80 C. and treating for 30-40 min; then taking out the wood dust, drying and then drying in an oven at 200-280 C. for 30-60 min by blowing air; subsequently, pulverizing and sintering the pulverized material in a high-temperature furnace under an inert atmosphere at a temperature of 400-800 C. for 1-6 h; then controlling a temperature at 300-400 C., introducing an activated gas, and treating for 20-40 min; thereafter, purging with dried nitrogen for 5-10 min to obtain the mesoporous activated carbon with a high mesoporosity, wherein the activated gas includes 10%-25% of air, 5%-20% of water vapor and the balance of nitrogen.

2. The method according to claim 1, wherein the hydrothermal reactor is a hydrothermal stainless steel reactor lined with polytetrafluoroethylene.

3. The method according to claim 1, wherein the acetate is alkali metal acetate, alkaline earth metal acetate, rare earth metal acetate or transition metal acetate.

4. The method according to claim 1, wherein the deep dehydration comprises: placing the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O in a mixed gas flow of carbonyl fluoride and high-purity nitrogen for 20-60 min, wherein a volume ratio of carbonyl fluoride to high-purity nitrogen in the mixed gas flow is (0.1-0.5):1, and a gas flow rate of the mixed gas flow is 0.5-5 L/min per kilogram of the material.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a SU-8010 scanning electron micrograph of the material for deep purification of HF electronic gas AC/MFx prepared in Example 2.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(2) The present disclosure will be further described below in conjunction with embodiments and drawings.

(3) In the experiment, the GB/T 34091-2017 gas chromatography determination method was used to test the impurity content in the HF electronic gas and the volume fraction of the product produced by different schemes.

Example 1

(4) The preparation method and use method of material for deep purification of HF electronic gas, the method for preparing the material has steps as follows:

(5) 15.2 g of acetate was dissolved in 2000 g of pure water and stirred for 10 min. After the solution was evenly dissolved, 126.4 g of disodium ethylenediaminetetraacetate was added thereto, stirred for 10 min to form a mixed solution, then 7.2 g of ammonium fluoride was added, and after the resulting mixture was evenly stirred, ammonia was added dropwise to adjust the pH value to 9; then 130 g of mesoporous activated carbon (AC) and 0.1 g of sodium tetrafluoroborate as inducer were added, then the resulting mixture was transferred to a hydrothermal reactor after stirring at 40 C. for 20 min, and the resulting mixture was subjected to crystallization reaction at 140 C. for 80 min; the material was then slowly cooled to room temperature, filtered out and washed with anhydrous ethanol for 3 times, then the resulting material was dried in an oven at 120 C. for 10 h to obtain the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O. After the resulting material was deeply dehydrated, the material for deep purification of HF electronic gas AC/MFx was obtained.

(6) The hydrothermal reactor is a hydrothermal stainless steel reactor lined with polytetrafluoroethylene.

(7) The acetate is lithium acetate.

(8) The deep dehydration comprises: the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O was placed in a mixed gas flow of carbonyl fluoride and high-purity nitrogen and treated for 20 min. A volume ratio of carbonyl fluoride to high-purity nitrogen in the mixed gas flow was 0.1:1, and a gas flow rate of the mixed gas flow was 0.5 L/min per kilogram of the material.

(9) The use method of the material for deep purification of HF electronic gas is as follows: the material for deep purification of HF electronic gas was loaded in a pressure-resistant stainless steel container to form an adsorption fixed bed, and then HF containing trace amount of water was passed through the fixed bed to make the composite material AC/MFx absorb trace amount of water in HF to form AC/MFx.Math.nH.sub.2O, so as to achieve the purpose of further removing moisture in HF.

(10) The mesoporous activated carbon is mesoporous activated carbon with a high mesoporosity, and prepared as follows:

(11) 7 g of ammonium dihydrogen phosphate, 16 g of dodecylurea, 1 g of urea and 0.05 g of 1-butyl-3-methylimidazolium molybdotungstophosphate were added to 1000 g of water, stirred and mixed evenly, then 100 g of clean sawdust was soaked in the mixed solution at room temperature for 5 h, then heated to 40 C. for 30 min, and then the sawdust was taken out, and dried in the oven at 200 C. for 30 min by blowing air; then it was pulverized, the pulverized material was sintered in a high-temperature furnace under inert atmosphere at 400 C. for 1 h, then the temperature was controlled at 300 C., activated gas was introduced and the material was treated for 20 min. The resulting material was purged with dry nitrogen for 5 min to obtain the mesoporous activated carbon with a high mesoporosity; the activated gas includes 10% of air, 5% of water vapor, and the balance of nitrogen.

(12) The water content of the high-purity hydrogen fluoride prepared in this example is 24 ppb, and the total content of gas impurities is 48 ppb.

Example 2

(13) The preparation method and use method of material for deep purification of HF electronic gas, the method for preparing the material has steps as follows:

(14) 26.1 g of acetate was dissolved in 3000 g of pure water and stirred for 20 min. After the solution was evenly dissolved, 154.6 g of disodium ethylenediaminetetraacetate was added thereto, stirred for 15 min to form a mixed solution, then 7.4 g of ammonium fluoride was added, and after the resulting mixture was evenly stirred, ammonia was added dropwise to adjust the pH value to 10; then 150 g of mesoporous activated carbon (AC) and 0.3 g of sodium tetrafluoroborate as inducer were added, then the resulting mixture was transferred to a hydrothermal reactor after stirring at 50 C. for 30 min, and the resulting mixture was subjected to crystallization reaction at 160 C. for 100 min; the material was then slowly cooled to room temperature, filtered out and washed with anhydrous ethanol for 4 times, then the resulting material was dried in an oven at 140 C. for 15 h to obtain the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O. After the resulting material was deeply dehydrated, the material for deep purification of HF electronic gas AC/MFx was obtained.

(15) The hydrothermal reactor is a hydrothermal stainless steel reactor lined with polytetrafluoroethylene.

(16) The acetate is calcium acetate.

(17) The deep dehydration comprises: the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O was placed in a mixed gas flow of carbonyl fluoride and high-purity nitrogen and treated for 30 min. A volume ratio of carbonyl fluoride to high-purity nitrogen in the mixed gas flow was 0.3:1, and a gas flow rate of the mixed gas flow was 2.5 L/min per kilogram of the material.

(18) The use method of the material for deep purification of HF electronic gas is as follows: the material for deep purification of HF electronic gas was loaded in a pressure-resistant stainless steel container to form an adsorption fixed bed, and then HF containing trace amount of water was passed through the fixed bed to make the composite material AC/MFx absorb trace amount of water in HF to form AC/MFx.Math.nH.sub.2O, so as to achieve the purpose of further removing moisture in HF.

(19) The mesoporous activated carbon is mesoporous activated carbon with a high mesoporosity, and prepared as follows:

(20) 18 g of ammonium dihydrogen phosphate, 22 g of dodecylurea, 5 g of urea and 0.1 g of 1-butyl-3-methylimidazolium molybdotungstophosphate were added to 2000 g of water, stirred and mixed evenly, then 160 g of clean sawdust was soaked in the mixed solution at room temperature for 8 h, then heated to 60 C. and treated for 35 min, and then the sawdust was taken out, and dried in the oven at 240 C. for 40 min by blowing air; then it was pulverized, the pulverized material was sintered in a high-temperature furnace under inert atmosphere at 600 C. for 3 h, then the temperature was controlled at 350 C., activated gas was introduced and the material was treated for 30 min. The resulting material was purged with dry nitrogen for 8 min to obtain the mesoporous activated carbon with a high mesoporosity; the activated gas includes 20% of air, 10% of water vapor, and the balance of nitrogen.

(21) The water content of the high-purity hydrogen fluoride prepared in this example is 14 ppb, and the total content of gas impurities is 41 ppb.

(22) The SU-8100 scanning electron microscope photograph of the material for deep purification of HF electronic gas AC/MFx prepared in this example is shown in FIG. 1. It can be seen from FIG. 1 that the metal fluoride is highly dispersed and loaded on the surface and pores of the activated carbon in the form of nanoparticles.

Example 3

(23) The preparation method and use method of material for deep purification of HF electronic gas, the method for preparing the material has steps as follows:

(24) 45.4 g of acetate was dissolved in 4000 g of pure water and stirred for 30 min. After the solution was evenly dissolved, 186.5 g of disodium ethylenediaminetetraacetate was added thereto, stirred for 20 min to form a mixed solution, then 7.8 g of ammonium fluoride was added, and after the resulting mixture was evenly stirred, ammonia was added dropwise to adjust the pH value to 11; then 170 g of mesoporous activated carbon (AC) and 0.5 g of sodium tetrafluoroborate as inducer were added, and the resulting mixture was transferred to the hydrothermal reactor after stirring at 60 C. for 50 min, and the resulting mixture was subjected to crystallization reaction at 180 C. for 120 min; the material was then slowly cooled to room temperature, filtered out and washed with anhydrous ethanol for 5 times, then the resulting material was dried in an oven at 160 C. for 18 h to obtain the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O. After the resulting material was deeply dehydrated, the material for deep purification of HF electronic gas AC/MFx was obtained.

(25) The hydrothermal reactor is a hydrothermal stainless steel reactor lined with polytetrafluoroethylene.

(26) The acetate is copper acetate.

(27) The deep dehydration comprises: the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O was placed in a mixed gas flow of carbonyl fluoride and high-purity nitrogen and treated for 60 min. A volume ratio of carbonyl fluoride to high-purity nitrogen in the mixed gas flow was 0.5:1, and a gas flow rate of the mixed gas flow was 5 L/min per kilogram of the material.

(28) The use method of the material for deep purification of HF electronic gas is as follows: the material for deep purification of HF electronic gas was loaded in a pressure-resistant stainless steel container to form an adsorption fixed bed, and then HF containing trace amount of water was passed through the fixed bed to make the composite material AC/MFx absorb trace amount of water in HF to form AC/MFx.Math.nH.sub.2O, so as to achieve the purpose of further removing moisture in HF.

(29) The mesoporous activated carbon is mesoporous activated carbon with a high mesoporosity, and prepared as follows:

(30) 34 g of ammonium dihydrogen phosphate, 44 g of dodecylurea, 8 g of urea and 0.3 g of 1-butyl-3-methylimidazolium molybdotungstophosphate were added to 3000 g of water, stirred and mixed evenly, then 200 g of clean sawdust was soaked in the mixed solution at room temperature for 10 h, then heated to 80 C. and treated for 40 min, and then the sawdust was taken out, and dried in the oven at 280 C. for 60 min by blowing air; then it was pulverized, the pulverized material was sintered in a high-temperature furnace under inert atmosphere at 800 C. for 6 h, then the temperature was controlled at 400 C., activated gas was introduced and the material was treated for 40 min. The resulting material was purged with dry nitrogen for 10 min to obtain the mesoporous activated carbon with a high mesoporous rate; the activated gas includes 25% of air, 20% of water vapor, and the balance of nitrogen.

(31) The water content of the high-purity hydrogen fluoride prepared in this example is 11 ppb, and the total content of gas impurities is 37 ppb.

Comparative Example 1

(32) The preparation method and use method of material for deep purification of HF electronic gas, the method for preparing the material has steps as follows:

(33) 15.2 g of acetate was dissolved in 2000 g of pure water and stirred for 10 min. After the solution was evenly dissolved, 126.4 g of disodium ethylenediaminetetraacetate was added thereto, stirred for 10 min to form a mixed solution, then 7.2 g of ammonium fluoride was added, and after the resulting mixture was evenly stirred, ammonia was added dropwise to adjust the pH value to 9; then 130 g of mesoporous activated carbon (AC) was added, and the resulting mixture was transferred to the hydrothermal reactor after stirring at 40 C. for 20 min, and the resulting mixture was subjected to crystallization reaction at 140 C. for 80 min; the material was then slowly cooled to room temperature, filtered out and washed with anhydrous ethanol, repeated washing with anhydrous ethanol for 3 times, then the resulting material was dried in an oven at 120 C. for 10 h to obtain the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O. After the resulting material was deeply dehydrated, the material for deep purification of HF electronic gas AC/MFx was obtained.

(34) The hydrothermal reactor is a hydrothermal stainless steel reactor lined with polytetrafluoroethylene.

(35) The acetate is lithium acetate.

(36) The deep dehydration comprises: the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O was placed in a mixed gas flow of carbonyl fluoride and high-purity nitrogen and treated for 20 min. A volume ratio of carbonyl fluoride to high-purity nitrogen in the mixed gas flow was 0.1:1, and a gas flow rate of the mixed gas flow was 0.5 L/min per kilogram of the material.

(37) The use method of the material for deep purification of HF electronic gas is as follows: the material for deep purification of HF electronic gas was loaded in a pressure-resistant stainless steel container to form an adsorption fixed bed, and then HF containing trace amount of water was passed through the fixed bed to make the composite material AC/MFx absorb trace amount of water in HF to form AC/MFx.Math.nH.sub.2O, so as to achieve the purpose of further removing moisture in HF.

(38) The mesoporous activated carbon is mesoporous activated carbon with a high mesoporosity, and prepared as follows:

(39) 7 g of ammonium dihydrogen phosphate, 16 g of dodecylurea and 1 g of urea were added to 1000 g of water, stirred and mixed evenly, then 160 g of clean sawdust was soaked in the mixed solution at room temperature for 5 h, then heated to 40 C. for 30 min, and then the sawdust was taken out, and dried in the oven at 200 C. for 30 min by blowing air; then it was pulverized, the pulverized material was sintered in a high-temperature furnace under inert atmosphere at 400 C. for 1 h, then the temperature was controlled at 300 C., activated gas was introduced and the material was treated for 20 min. The resulting material was purged with dry nitrogen for 5 min to obtain the mesoporous activated carbon with a high mesoporosity; the activated gas includes 10% of air, 5% of water vapor, and the balance of nitrogen.

(40) The water content of the high-purity hydrogen fluoride prepared in this example is 46 ppb, and the total content of gas impurities is 119 ppb.

Comparative Example 2

(41) The preparation method and use method of material for deep purification of HF electronic gas, the method for preparing the material has steps as follows:

(42) 15.2 g of acetate was dissolved in 2000 g of pure water and stirred for 10 min. After the solution was evenly dissolved, 126.4 g of disodium ethylenediaminetetraacetate was added thereto, stirred for 10 min to form a mixed solution, then 7.2 g of ammonium fluoride was added, and after the resulting mixture was evenly stirred, ammonia was added dropwise to adjust the pH value to 9; then 130 g of mesoporous activated carbon (AC) and 0.1 g of sodium tetrafluoroborate as inducer were added, and the resulting mixture was transferred to the hydrothermal reactor after stirring at 40 C. for 20 min, and the resulting mixture was subjected to crystallization reaction at 140 C. for 80 min; the material was then slowly cooled to room temperature, filtered out and washed with anhydrous ethanol for 3 times, then the resulting material was dried in an oven at 120 C. for 10 h to obtain the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O. After the resulting material was deeply dehydrated, the material for deep purification of HF electronic gas AC/MFx was obtained.

(43) The hydrothermal reactor is a hydrothermal stainless steel reactor lined with polytetrafluoroethylene.

(44) The acetate is lithium acetate.

(45) The deep dehydration comprises: the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O was placed in a mixed gas flow of carbonyl fluoride and high-purity nitrogen and treated for 20 min. A volume ratio of carbonyl fluoride to high-purity nitrogen in the mixed gas flow was 0.1:1, and a gas flow rate of the mixed gas flow was 0.5 L/min per kilogram of the material.

(46) The use method of the material for deep purification of HF electronic gas is as follows: the material for deep purification of HF electronic gas was loaded in a pressure-resistant stainless steel container to form an adsorption fixed bed, and then HF containing trace amount of water was passed through the fixed bed to make the composite material AC/MFx absorb trace amount of water in HF to form AC/Mx.Math.nH.sub.2O, so as to achieve the purpose of further removing moisture in HF.

(47) The mesoporous activated carbon is mesoporous activated carbon with a high mesoporosity, and prepared as follows:

(48) 7 g of ammonium dihydrogen phosphate, 1 g of urea and 0.05 g of 1-butyl-3-methylimidazolium molybdotungstophosphate were added to 1000 g of water, stirred and mixed evenly, then 160 g of clean sawdust was soaked in the mixed solution at room temperature for 5 h, then heated to 40 C. and treated for 30 min, and then the sawdust was taken out, and dried in the oven at 200 C. for 30 min by blowing air; then it was pulverized, the pulverized material was sintered in a high-temperature furnace under inert atmosphere at 400 C. for 1 h, then the temperature was controlled at 300 C., activated gas was introduced and the material was treated for 20 min. The resulting material was purged using dry nitrogen for 5 min to obtain the mesoporous activated carbon with a high mesoporosity; the activated gas includes 10% of air, 5% of water vapor, and the balance of nitrogen.

(49) The water content of the high-purity hydrogen fluoride prepared in this example is 44 ppb, and the total content of gas impurities is 108 ppb.

Comparative Example 3

(50) The preparation method and use method of material for deep purification of HF electronic gas, the method for preparing the material has steps as follows:

(51) 15.2 g of acetate was dissolved in 2000 g of pure water and stirred for 10 min. After the solution was evenly dissolved, 126.4 g of disodium ethylenediaminetetraacetate was added thereto, stirred for 10 min to form a mixed solution, then 7.2 g of ammonium fluoride was added, and after the resulting mixture was evenly stirred, ammonia was added dropwise to adjust the pH value to 9; then 0.1 g of sodium tetrafluoroborate as inducer was added, and the resulting mixture was transferred to the hydrothermal reactor after stirring at 40 C. for 20 min, and the resulting mixture was subjected to crystallization reaction at 140 C. for 80 min; the material was then slowly cooled to room temperature, filtered out and washed with anhydrous ethanol, repeated washing with anhydrous ethanol for 3 times, then the resulting material was dried in an oven at 120 C. for 10 h to obtain the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O. After the resulting material was deeply dehydrated, the material for deep purification of HF electronic gas AC/MFx was obtained.

(52) The hydrothermal reactor is a hydrothermal stainless steel reactor lined with polytetrafluoroethylene.

(53) The acetate is lithium acetate.

(54) The deep dehydration comprises: the metal fluoride-loaded activated carbon material AC/MFx.Math.nH.sub.2O was placed in a mixed gas flow of carbonyl fluoride and high-purity nitrogen and treated for 20 min. A volume ratio of carbonyl fluoride to high-purity nitrogen in the mixed gas flow was 0.1:1, and a gas flow rate of the mixed gas flow was 0.5 L/min per kilogram of the material.

(55) The use method of the material for deep purification of HF electronic gas is as follows: the material for deep purification of HF electronic gas was loaded in a pressure-resistant stainless steel container to form an adsorption fixed bed, and then HF containing trace amount of water was passed through the fixed bed to make the composite material AC/MFx absorb trace amount of water in HF to form AC/MFx.Math.nH.sub.2O, so as to achieve the purpose of further removing moisture in HF.

(56) The mesoporous activated carbon is mesoporous activated carbon with a high mesoporosity, and a process for preparing the mesoporous activated carbon with a high mesoporosity comprises:

(57) 16 g of dodecylurea, 1 g of urea and 0.05 g of 1-butyl-3-methylimidazolium molybdotungstophosphate were added to 1000 g of water, stirred and mixed evenly, then 160 g of clean sawdust was soaked in the mixed solution at room temperature for 5 h, then heated to 40 C. and treated for 30 min, and then the sawdust was taken out, and dried in the oven at 200 C. for 30 min by blowing air; then it was pulverized, the pulverized material was sintered in a high-temperature furnace under inert atmosphere at 400 C. for 1 h, then the temperature was controlled at 300 C., activated gas was introduced and the material was treated for 20 min. The resulting material was purged with dry nitrogen for 5 min to obtain the mesoporous activated carbon with a high mesoporosity; the activated gas includes 10% of air, 5% of water vapor, and the balance of nitrogen.

(58) The water content of the high-purity hydrogen fluoride prepared in this example is 58 ppb, and the total content of gas impurities is 147 ppb.

(59) The description of the above embodiments is only used to help understand the method and the core idea of the present disclosure. It should be pointed out that for those of ordinary skills in the art, without departing from the principle of the present disclosure, several improvements and modifications can be made to the present disclosure, and these improvements and modifications also fall within the protection scope of the claims of the present disclosure. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present disclosure. Therefore, the present disclosure will not be limited to the embodiments shown in this disclosure, but should be accorded the widest scope consistent with the principles and novel features disclosed herein.