KR20040060302A - Purification of NF3 Gas using multicomponent adsorbent - Google Patents
Purification of NF3 Gas using multicomponent adsorbent Download PDFInfo
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- KR20040060302A KR20040060302A KR1020020087072A KR20020087072A KR20040060302A KR 20040060302 A KR20040060302 A KR 20040060302A KR 1020020087072 A KR1020020087072 A KR 1020020087072A KR 20020087072 A KR20020087072 A KR 20020087072A KR 20040060302 A KR20040060302 A KR 20040060302A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 31
- 238000000746 purification Methods 0.000 title description 5
- 239000007789 gas Substances 0.000 claims abstract description 48
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 15
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000004327 boric acid Substances 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 230000000704 physical effect Effects 0.000 claims abstract description 3
- 238000005273 aeration Methods 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001272 nitrous oxide Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 nitrate ions Chemical class 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/083—Compounds containing nitrogen and non-metals and optionally metals containing one or more halogen atoms
- C01B21/0832—Binary compounds of nitrogen with halogens
- C01B21/0835—Nitrogen trifluoride
- C01B21/0837—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
- C01B2210/0014—Physical processing by adsorption in solids
- C01B2210/0015—Physical processing by adsorption in solids characterised by the adsorbent
- C01B2210/002—Other molecular sieve materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0051—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0075—Nitrogen oxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
본 발명은 삼불화질소(NF3: Nitrogen Trifluoride) 가스 제조시 포함되어 있는 불순물 중 N2O, CO2가스를 효과적으로 제거하는 방법에 관한 것으로, 알루미늄나이트레이트와 붕산의 혼합물을 침전제인 암모니아수 용액으로 처리하여 알루미나-알루미늄 보레이트를 흡착제로 제조하며, 흡착제의 보론 원소의 함유량은 1∼50중량%이며, 알루미늄 원소의 함유량은 50∼99중량%이다. 더욱 좋게는 보론 원소의 함유량이 2∼35중량%이고, 알루미늄 원소의 함유량이 65∼98중량%이며, 물리적 특성으로 기공 부피가 0.4∼ 1.0 cc/g, 평균 기공 크기는 200∼3000Å, 질소 흡착 표면적은 100∼150 m2/g인 흡착제를 제조한 후, 컬럼 등에 충진하여 -100∼50℃의 온도에서 불순물이 함유된 NF3가스를 통기시킴으로써 N2O 및 CO2를 동시에 제거한다.The present invention relates to a method for effectively removing N 2 O, CO 2 gas from impurities contained in the production of nitrogen trifluoride (NF 3 : Nitrogen Trifluoride) gas, a mixture of aluminum nitrate and boric acid as a precipitant ammonia water solution The alumina-aluminum borate is treated to prepare an adsorbent, the boron element content is 1 to 50% by weight, and the aluminum element content is 50 to 99% by weight. More preferably, the boron element content is 2 to 35% by weight, the aluminum content is 65 to 98% by weight, the pore volume is 0.4 to 1.0 cc / g, the average pore size is 200 to 3000 kPa, and the nitrogen adsorption by physical properties. After preparing an adsorbent having a surface area of 100 to 150 m 2 / g, N 2 O and CO 2 are simultaneously removed by filling a column or the like with an NF 3 gas containing impurities at a temperature of -100 to 50 ° C.
Description
본 발명은 삼불화질소(NF3: Nitrogen Trifluoride) 가스 제조시 포함되어 있는 불순물 중 N2O, CO2가스를 효과적으로 제거하는 방법에 관한 것이다.The present invention relates to a method for effectively removing N 2 O, CO 2 gas from impurities contained in the production of nitrogen trifluoride (NF 3 : Nitrogen Trifluoride) gas.
NF3가스는 반도체 제조의 드라이 에칭제와 CVD장비의 세정용 및 로케트의 추진 연료 등으로 사용되는데 이들 용도에 사용되는 NF3가스는 고순도의 것이 요구된다. NF3가스는 각종 방법으로 제조되는데 예를 들면, 암모늄산 불화물의 용융염을 전해하는 방법, 암모늄산 불화물을 용융상태에서 기체상의 불소와 반응시키는 방법, 고체상의 금속불화물의 암모늄 착체와 원소상 불소를 반응시키는 방법, 불화암모늄 또는 산성 불화암모늄과 불화수소를 원료로 하는 NH4F-HF나, 다시 여기에 불화칼륨 또는 산성 불화칼륨을 그 원료에 가한 KF-NH4F-HF계에서의 용융염 전해법 등이 있다.NF 3 gas is used as a dry etchant for semiconductor manufacturing and cleaning for CVD equipment and as a propulsion fuel for rockets. NF 3 gas used in these applications is required to have high purity. The NF 3 gas is produced by various methods, for example, electrolysis of molten salt of ammonium fluoride, reaction of ammonium fluoride with gaseous fluorine in the molten state, ammonium complex of solid metal fluoride and elemental fluorine to which the method of the reaction, ammonium fluoride or acidic ammonium fluoride and hydrogen fluoride as raw materials NH 4 F-HF, or melting of the KF-NH 4 F-HF system was added to potassium fluoride or acidic potassium fluoride here again to the raw material Salt electrolysis and the like.
그러나 상기 방법의 대부분의 경우에 있어서 얻어진 가스는 N2O, CO2, N2F2등의 불순물을 비교적 다량으로 함유하고 있어서 99.99%이상의 고순도를 요하는 제품 생산에는 정제 공정이 필요하다.However, in most cases of the above method, the obtained gas contains a relatively large amount of impurities such as N 2 O, CO 2 , N 2 F 2 , and thus, a purification process is required for production of a product requiring high purity of 99.99% or more.
종래의 NF3가스 중의 불순물을 제거하는 방법으로는 합성 제올라이트, 활성탄, 활성 알루미나 등의 흡착제를 이용하여 이들 불순물을 흡착하여 제거하는 방법이 일반적으로 알려져 있다.As a conventional method for removing impurities in NF 3 gas, a method of adsorbing and removing these impurities by using an adsorbent such as synthetic zeolite, activated carbon, or activated alumina is generally known.
특히, 미국특허 제4,156,598호에서 제시하고 있는 합성 제올라이트는 상기 불순물을 효율적으로 흡착하는 것으로 알려져 있다. 그러나 합성 제올라이트의 경우, 예를 들면 몰레큘러시브-5A는 N2O의 흡착능력은 크나, CO2의 흡착능력이 작고, 반대로 몰레큘러시브-13X는 CO2의 흡착능력은 크나, N2O의 흡착능력이 작다는 문제점이 있다. 따라서 N2O 및 CO2를 제거하기 위해서는 각각의 제거능력이 큰 흡착제를 순차적으로 흡착시켜 제거하는 방법이 많이 사용되어 왔다.In particular, synthetic zeolites disclosed in US Pat. No. 4,156,598 are known to efficiently adsorb the impurities. However, in the case of synthetic zeolites, for example, Molecular-5-5A has a high N 2 O adsorption capacity, but CO 2 has a low adsorption capacity, whereas Molecular-13X has a large CO 2 adsorption capacity. There is a problem that the adsorption capacity of 2 O is small. Therefore, in order to remove N 2 O and CO 2 has been a lot of methods to sequentially remove the adsorbent having a large removal capacity by adsorbing.
Membrane을 이용한 분리막 적용 기술은 재생 기술과 제조 기술이 난해하여 아직은 공정 적용에 많은 비용이 소모된다. 이러한 면을 비추어 볼 때 흡착제를 이용한 분리기술은 매우 경제적이라 할 수 있다.Membrane separation membrane application technology is difficult to recycle process and manufacturing technology is still expensive to apply the process. In view of this aspect, separation technology using adsorbent is very economical.
본 발명은 N2O, CO2등의 불순물을 함유한 NF3를 정제함에 있어서, 경제적인정제방법을 제공하는 것을 목적으로 한다. 본 발명의 다른 목적은 하나의 공정으로 N2O 및 CO2가스를 동시에 제거할 수 있는 정제방법을 제공하는 것이다.An object of the present invention is to provide an economical purification method in purifying NF 3 containing impurities such as N 2 O and CO 2 . Another object of the present invention is to provide a purification method capable of simultaneously removing N 2 O and CO 2 gas in one process.
본 발명은 흡착제를 이용하여 삼불화질소가스(NF3)를 정제하는 방법에 있어서, 알루미늄나이트레이트와 붕산의 혼합물을 침전제인 암모니아수 용액으로 처리하여 알루미나-알루미늄 보레이트를 흡착제로 제조한 후 컬럼 등에 충전하여, 그 충전층에 불순물 가스를 함유하는 삼불화질소가스를 -100℃∼50℃의 온도에서 통기시키는 것으로 구성된다.The present invention provides a method for purifying nitrogen trifluoride gas (NF 3 ) using an adsorbent, wherein a mixture of aluminum nitrate and boric acid is treated with an aqueous ammonia solution as a precipitant to prepare alumina-aluminum borate as an adsorbent and then packed into a column. The nitrogen trifluoride gas containing the impurity gas is passed through the packed layer at a temperature of -100 ° C to 50 ° C.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서 사용되는 흡착제는 알루미늄나이트레이트와 붕산의 혼합물을 침전제인 암모니아수 용액으로 처리하여 제조하는데, 흡착제의 적절한 보론 원소의 함유량은 1∼50중량%이며, 알루미늄 원소의 함유량은 50∼99중량%이다. 더욱 좋게는 보론 원소의 함유량이 2∼35중량%이고, 알루미늄 원소의 함유량이 65∼98중량%인 것이다.The adsorbent used in the present invention is prepared by treating a mixture of aluminum nitrate and boric acid with ammonia water solution, which is a precipitant. The content of an appropriate boron element in the adsorbent is 1 to 50% by weight, and the content of aluminum is 50 to 99% by weight. to be. More preferably, the content of boron element is 2 to 35% by weight, and the content of aluminum element is 65 to 98% by weight.
물리적 특성으로 기공 부피가 0.4∼1.0 cc/g, 평균 기공 크기는 200∼3000Å, 질소 흡착 표면적은 100∼150 m2/g이 적절하다. 이러한 흡착제의 구조적 특성은 반응에서 작용시 확산 저항이 최소화되어 흡·탈착 전후의 물질 전달이 용이하게 된다. 즉, 흡착제의 미세 기공의 크기를 의도적으로 증가시켜, 흡착 활성점으로의물질 전달 거리를 최소화하도록 기공 및 표면 구조를 조절한 것이다.As a physical property, a pore volume of 0.4 to 1.0 cc / g, an average pore size of 200 to 3000 mm 3 , and a nitrogen adsorption surface area of 100 to 150 m 2 / g are appropriate. The structural properties of these adsorbents minimize the diffusion resistance when acting in the reaction to facilitate mass transfer before and after adsorption and desorption. That is, by intentionally increasing the size of the fine pores of the adsorbent, the pore and surface structure is adjusted to minimize the mass transfer distance to the adsorption active site.
또한 본 발명은 N2O 및 CO2를 각각 제거함에 있어서 온도 -100∼50??에서, 아산화질소의 농도가 전체가스기준으로 1∼3%, 이산화탄소의 농도가 전체가스 기준으로 1∼3%으로 이루어진 혼합가스를 사용하는 것이 적절하다.In the present invention, in the removal of N 2 O and CO 2 respectively, at a temperature of -100 to 50 °, the concentration of nitrous oxide is 1 to 3% based on the total gas, and the concentration of carbon dioxide is 1 to 3% based on the total gas. It is appropriate to use a mixed gas consisting of.
본 발명에서 선호하는 흡착제의 형태는 구형이거나 펠렛형으로 종래에 잘 알려진 유적법 혹은 펠렛타이징 혹은 연소에 의해 제거 가능한 바인더를 사용하여 형태를 형성한 후 소성하면 용이하게 제조될 수 있다. 본 발명에 사용된 흡착제는 흡착제로의 물질 전달 혹은 흡착제 내부 확산 전달 저항을 최소화하기 위해, 흡착제의 미세 기공의 크기를 증대시킨 것으로, 질소 흡착법으로 측정하여 촉매의 기공 부피가 0.4∼1.0 cc/g이며, 평균 기공 크기는 200∼3000Å, 질소 흡착 표면적은 100∼150 m2/g을 가진다. 이때 측정된 기공 분포상(부피 분포상)의 메디안은 200∼1000Å을 가진 것을 본 발명에서는 선호한다.Preferred adsorbent forms in the present invention are spherical or pelletized, which can be easily prepared by firing after forming the form using a binder which is well known in the art, or a pelletizing or burning removable binder. The adsorbent used in the present invention is to increase the size of the fine pores of the adsorbent in order to minimize mass transfer to the adsorbent or diffusion diffusion resistance within the adsorbent. The average pore size is 200-3000 mm 3 , and the nitrogen adsorption surface area is 100-150 m 2 / g. In this invention, the median of the pore distribution phase (volume distribution phase) measured at this time has 200-1000 micrometers.
이러한 기공 특성은 흡착제 물질의 제조 과정에서 결정되는데, 특히 흡착제 물질 제조 출발시의 사용 금속 물질의 혼합비율 및 혼합 특성 (침전 용액의 수소 이온 농도, 혼합비, 겔화 속도, 밀도 조정, 유기 접합제 사용 유무 등)과 건조 및 소성 과정에 의해 조절되어, 원하는 기공 특성을 얻을 수 있다.These pore characteristics are determined during the preparation of the adsorbent material. In particular, the mixing ratio and mixing characteristics of the metal materials used at the start of the preparation of the adsorbent material (hydrogen concentration, mixing ratio, gelation rate, density adjustment of the precipitation solution, presence of organic binders) And the like, and drying and firing processes to obtain desired pore characteristics.
본 발명의 흡착제를 제조하기 위해 다음과 같은 제조 과정을 예시할 수 있다. 알루미늄 나이트레이트(Al(NO3)3)와 붕산(H3BO3)을 적정 비율로 혼합한 용액과 암모니아수 용액(pH=10.00)을 증류수가 포함된 용기에 천천히 첨가하여 교반한다. 이때, 수소이온 농도를 pH=8.0 수준으로 유지한다. 이 때, 침전된 물질을 걸러주고, 나이트레이트 이온이 검출되지 않을 때까지 깨끗한 물로 씻어준다. 그리고 나서 건조 소성을 거쳐 제조할 수도 있으며, 교반 혼합 후 필요에 따라 성형 과정을 거칠 수도 있다. 성형을 하거나 성형을 안 한 혼합물은 100∼ 120℃의 건조 공기 분위기에서 12시간 이상 건조 한 후, 소성 과정을 거친다.In order to prepare the adsorbent of the present invention it can be exemplified the following manufacturing process. A solution containing a mixture of aluminum nitrate (Al (NO 3 ) 3 ) and boric acid (H 3 BO 3 ) and ammonia solution (pH = 10.00) is slowly added to the vessel containing distilled water and stirred. At this time, the hydrogen ion concentration is maintained at pH = 8.0 level. At this time, the precipitated material is filtered off and washed with clean water until no nitrate ions are detected. Then, it may be produced through dry firing, or may be subjected to a molding process if necessary after stirring and mixing. The molded or unmolded mixture is dried for at least 12 hours in a dry air atmosphere at 100 to 120 ° C. and then calcined.
본 발명의 알루미나-알루미늄 보레이트는 최종적으로 소성 과정에서 혼합 성분간의 결합 특성이 생기는데, 흡착제 물질을 결정화시키는 소성은 다음과 같은 과정을 거친다. 건조 공기 대비 수증기의 혼합비로 0∼200, 기체 공간 속도(GHSV:Gas Hourly Space Velocity) 100∼3000 hr-1를 유지하며 200∼700℃에서 1∼48시간 정도로 1차 소성 시킨 후, 건조 공기 대비 수증기 0∼100의 혼합 기체 분위기에서 기체 공간 속도(GHSV:Gas Hourly Space Velicity) 300∼5000 hr-1로 500∼1200℃까지 1∼60hr 정도의 소성 처리를 하여 흡착제를 제조한다. 제조된 흡착제는 주로 무정형의 물질로 본 발명에서 원하는 구조 특성 중의 하나인 기공 특성, 촉매의 기공 부피가 0.4∼1.0 cc/g, 평균 기공 크기는 200∼ 3000Å를 가진 흡착제 물질이 얻어진다. 이때 얻어진 흡착제는 표면적 25∼150 m2/g을 가지며, 바람직하게는 100∼150 m2/g이다.The alumina-aluminum borate of the present invention finally has a bonding property between the mixed components in the firing process, the firing to crystallize the adsorbent material is subjected to the following process. Mainly calcined at 200 ~ 700 ℃ for 1 ~ 48 hours while maintaining 0 ~ 200, gas hourly space velocity (GHSV: Gas Hourly Space Velocity) at the mixing ratio of dry air to 100 ~ 3000 hr- 1 . In the mixed gas atmosphere of water vapor 0-100, the adsorbent is prepared by firing at a gas space velocity (GHSV: Gas Hourly Space Velicity) of 300 to 5000 hr −1 to 500 to 1200 ° C. for about 1 to 60 hr. The prepared adsorbent is mainly an amorphous material, which has one of the structural properties desired in the present invention, and an adsorbent material having a pore volume of 0.4 to 1.0 cc / g and an average pore size of 200 to 3000 mm 3 is obtained. The resultant sorbent has a surface area of 25~150 m 2 / g, preferably 100~150 m 2 / g.
이와 같은 복합성분을 가진 알루미나-알루미늄 보레이트로 충전층을 형성하고, 불순물 가스를 함유하는 삼불화질소가스를 -100∼50℃의 온도에서 통기하여 불순물을 제거한다.A packed layer is formed of alumina-aluminum borate having such a composite component, and nitrogen trifluoride gas containing impurity gas is vented at a temperature of -100 to 50 ° C to remove impurities.
본 발명의 가장 바람직한 실시양태는, 수분 제거와 NF3가스의 흡착정제를 동일한 용기에서 행하는 것이다. 즉, 적당한 용기 또는 칼럼에 원하는 입도분포로 알루미나-알루미늄 보레이트를 충전해서 충전층을 형성한다. 다음에 불활성가스를 그 충전층 중에 통기하면서 가열처리한다. 가열처리 후 알루미나-알루미늄 보레이트를 용기 밖으로 꺼내지 않고, 그대로의 상태에서 냉각시키고, 이어서 이 알루미나-알루미늄 보레이트의 충전층에 NF3가스를 -100℃∼50℃의 온도에서 통기하는 방법이 바람직하다.The most preferred embodiments of the present invention, and performs the adsorption of the purified water removal and NF 3 gas in the same vessel. That is, alumina-aluminum borate is charged to a suitable container or column with a desired particle size distribution to form a packed layer. Next, an inert gas is heated while ventilating the packed bed. It is preferable that the alumina-aluminum borate is not taken out of the container after the heat treatment, cooled in the same state, and then the NF 3 gas is vented to a packed layer of the alumina-aluminum borate at a temperature of -100 ° C to 50 ° C.
NF3가스의 정제는, 상기와 같이 칼럼 등에 충전된 알루미나-알루미늄 보레이트층에 통기하는 방법으로 실시되는데, 이때의 통기온도는 중요하며, 50℃이하의 온도가 바람직하다. 이 온도를 넘으면, 통기 후의 NF3가스 중의 N2O의 함유량이 충분히 감소하지 않으며, 또한 알루미나-알루미늄 보레이트 단위 체적당의 NF3가스 중의 N2O의 흡착량이 크게 감소하므로 좋지 않다.Purification of the NF 3 gas is carried out by aeration through an alumina-aluminum borate layer packed in a column or the like as described above. At this time, the aeration temperature is important, and a temperature of 50 ° C. or less is preferable. If the temperature is exceeded, the content of N 2 O in the NF 3 gas after aeration is not sufficiently reduced, and the adsorption amount of N 2 O in the NF 3 gas per unit volume of alumina-aluminum borate is greatly reduced, which is not good.
또한, 온도는 저온일수록 바람직하나, NF3의 비점은 -129℃이므로, 이 온도 이하에서는 조작이 사실상 곤란하며, -100℃ 이상의 범위에서 실시된다. 용기나 유리의 재질로서는 스테인레스 스틸, 구리, 니켈, 철 등의 통상적 재료가 사용가능하다.The lower the temperature is, the more preferable it is. However, since the boiling point of NF 3 is -129 ° C, the operation is practically difficult at this temperature or lower, and is performed in the range of -100 ° C or more. As a material of a container and glass, normal materials, such as stainless steel, copper, nickel, iron, can be used.
알루미나-알루미늄 보레이트 충전층의 통기조건에 관해서 더욱 자세히 설명하면 아래와 같다.The aeration conditions of the alumina-aluminum borate packed layer will be described in more detail below.
알루미나-알루미늄 보레이트 충전층의 지름은 1∼50㎝ 정도가 바람직하다. 충전층 높이는 5㎝∼2m 정도이며, 가스 유량은 5∼500cc/min 정도이다. 통기시의 NF3가스의 압력은 특별히 한정은 없으나, 0∼10㎏중/㎠ 정도의 압력이 조작하기 쉬우므로 바람직하다.The diameter of the alumina-aluminum borate packed layer is preferably about 1 to 50 cm. The packed bed height is about 5 cm to 2 m, and the gas flow rate is about 5 to 500 cc / min. The pressure of the NF 3 gas in the vent path is free of any particular limitation is preferred because it is easy to have a degree of / ㎠ but, 0~10㎏ pressure operation.
본 발명이 대상으로 하는 NF3가스를 정제처리하면 가스 중의 불순물 함유량은 N2O 0∼5ppm, CO20∼5ppm으로 할 수가 있다. 그리고 아래의 실시예의 분석법은 가스크로마토그래피(검출기:DID)에 의해서 행한 수치이다.Processing a NF 3 gas of the present invention the target content in the gas is purified of impurities can be the N 2 O 0~5ppm, CO 2 0~5ppm . And the analysis method of the following Example is the numerical value performed by gas chromatography (detector: DID).
본 발명의 실시예는 아래와 같다.An embodiment of the present invention is as follows.
< 실시예 1∼4><Examples 1-4>
내경 10mm의 스테인레스제 칼럼에 수분이 완전히 제거된 입도가 8∼12메시의 구형의 알루미나-알루미늄 보레이트를 충전높이 400mm로 충전 후 상압에서, 표1에 표시하는 온도에서 N2O 2%, CO22%를 함유한 NF3를 150㎖/min의 유속으로 파과시간까지 통기시켰다.A stainless steel column with an internal diameter of 10 mm was filled with a spherical alumina-aluminum borate having a particle size of 8 to 12 mesh with a filling height of 400 mm, followed by N 2 O 2% and CO 2 at normal pressure. NF 3 containing 2% was vented to breakthrough time at a flow rate of 150 ml / min.
본 실시예 및 하기의 비교예의 파과시간이란 다음과 같은 것을 의미한다. 즉, 불순물을 함유하는 가스를 흡착제층에 통기해서 불순물을 흡착 제거하는 경우 가스의 통기 직후에는 얻어지는 가스 중의 불순물 함유량은 적고, 또한 일정 함유량이거나 조금씩 서서히 증가하는 상태가 계속된다. 흡착제가 흡착능력을 상실할 때쯤되면 불순물 함유량이 급격히 증가하기 시작한다.The breakthrough time of this Example and the following comparative example means the following. That is, in the case where the impurity is adsorbed and removed by passing the gas containing the impurity into the adsorbent layer, the impurity content in the gas obtained immediately after the gas is vented is small, and the constant content is gradually increased gradually. By the time the adsorbent loses its adsorption capacity, the impurity content begins to increase rapidly.
이 급격히 증가하기 시작하기까지의 통기시간을 파과시간이라 한다. 실시예 및 비교예에 있어서 상기 불순물 중 어느 하나가 20ppm을 넘는 시간까지의 통기시간을 파과시간이라 하였다.The aeration time until this rapid increase is called breakthrough time. In Examples and Comparative Examples, the aeration time until the time when any one of the above impurities exceeds 20 ppm was called the breakthrough time.
파과시간까지의 N2O, CO2, NF3의 흡착량은 표1에 표시하는 바와 같으며, 본 발명의 방법으로 정제하면, 흡착에 의한 NF3의 손실량은 거의 없으며, N2O 및 CO2도 비교적 쉽게 제거된다. 또한 NF3가스의 분석은 가스크로마토그래피로 하였다. 파과시간까지의 N2O, CO2, NF3의 흡착량은 표1과 같으며, NF3중의 N2O 및 CO2는 매우 양호하게 제거된다.Adsorption amounts of N 2 O, CO 2 , and NF 3 until the breakthrough time are as shown in Table 1, and when purified by the method of the present invention, there is almost no loss of NF 3 due to adsorption, and N 2 O and CO 2 degrees is relatively easy to remove. Further analysis of the NF 3 gas was by gas chromatography. Adsorption amounts of N 2 O, CO 2 and NF 3 until the breakthrough time are shown in Table 1, and N 2 O and CO 2 in NF 3 are removed very well.
〈비교예 1〉<Comparative Example 1>
NF3가스의 통기온도를 60??로 변경한 것 이외에는 모든 조건을 실시예 1∼4와 동일하게 실시하였다. 결과는 표2에 나타내었다. 적정한 통기온도인 50℃를 초과할경우 파과시간과 파과시간까지의 흡착량이 적어서 산업적인 이용가능성을 거의 상실하였다.Except for changing the temperature of the vent gas to NF 3 ?? 60 it was carried out the same as Example 1 to 4 subjected to any conditions. The results are shown in Table 2. When the proper aeration temperature was exceeded 50 ° C., the adsorption amount until breakthrough time and breakthrough time was small, thus almost losing industrial applicability.
〈비교예 2∼3〉<Comparative Examples 2 to 3>
실시예 1∼4에서 사용한 흡착제 대신 비교예 2는 Molecular Sieve 5A(MS-5A), 비교예 3은 Molecular Sieve 13X(MS-13X)을 사용하여 불순물이 함유된 NF3가스를 0℃에서 통기한 것 이외에는 실시예 1∼4와 동일하게 실시하였다. 결과는 표3에 나타내었다. 각 제올라이트를 단독으로 사용할 경우에는 각각 한 가지의 불순물에서만 뛰어난 성능을 보이는 것을 관찰할 수 있었다. 이와 같은 방법으로 사용할 경우에는 새로운 흡착베드 등 새로운 투자비가 필요하게 되므로 상업적인 측면에서 손실이 야기된다.Instead of the adsorbents used in Examples 1 to 4, Comparative Example 2 used Molecular Sieve 5A (MS-5A), and Comparative Example 3 used Molecular Sieve 13X (MS-13X) to vent NF 3 gas containing impurities at 0 ° C. Except having carried out similarly to Examples 1-4. The results are shown in Table 3. When each zeolite was used alone, it was observed that only one impurity showed excellent performance. When used in this way, new investment costs, such as new adsorption beds, are required, resulting in commercial losses.
본 발명은 상기한 바와 같이 N2O 및 CO2가 함유된 NF3가스를 스테인레스제 칼럼에 수분이 완전히 제거된 입도가 8∼12메시의 알루미나-알루미늄 보레이트를 충전하여 -100∼50℃에서 불순물이 함유된 NF3가스를 통기시킴으로써 경제적으로 N2O 및 CO2를 동시에 제거할 수 있다.As described above, the NF 3 gas containing N 2 O and CO 2 is filled with alumina-aluminum borate having a particle size of 8-12 mesh in which water is completely removed from a stainless column, and impurities at -100 to 50 ° C. By venting this containing NF 3 gas, N 2 O and CO 2 can be removed economically.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110237675A (en) * | 2019-07-17 | 2019-09-17 | 烟台大学 | Preparation method and application of a kind of highly active fluorine-fixing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110237675A (en) * | 2019-07-17 | 2019-09-17 | 烟台大学 | Preparation method and application of a kind of highly active fluorine-fixing agent |
| CN110237675B (en) * | 2019-07-17 | 2021-06-11 | 烟台大学 | Preparation method and application of high-activity fluorine fixing agent |
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