KR20230055032A - Ammonia Adsorbent - Google Patents
Ammonia Adsorbent Download PDFInfo
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- KR20230055032A KR20230055032A KR1020210138265A KR20210138265A KR20230055032A KR 20230055032 A KR20230055032 A KR 20230055032A KR 1020210138265 A KR1020210138265 A KR 1020210138265A KR 20210138265 A KR20210138265 A KR 20210138265A KR 20230055032 A KR20230055032 A KR 20230055032A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 97
- 239000003463 adsorbent Substances 0.000 title claims abstract description 38
- 238000001179 sorption measurement Methods 0.000 claims abstract description 74
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 238000003795 desorption Methods 0.000 claims description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 12
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- 239000000446 fuel Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0462—Temperature swing adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
- B01D53/0476—Vacuum pressure swing adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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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
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Oil, Petroleum & Natural Gas (AREA)
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
본 발명은 암모니아 흡착제에 관한 것이다.The present invention relates to an ammonia adsorbent.
암모니아는 한 분자당 세 개의 수소를 가지고 있으며, 분해하면 수소와 질소만 나오기 때문에 이산화탄소 배출을 최소화할 수 있어서 수소 공급원으로 주목을 받고 있다. 뿐만 아니라, 액상 암모니아는 액화 수소보다 동일부피에서 1.7배 많은 용량의 수소를 저장할 수 있으며, 암모니아는 전 세계에서 연간 2억 톤 이상이 생산되어 산업 곳곳에 활용되므로 기존 인프라를 활용할 수 있어서 운반이나 저장에 이점이 많다. 이에 따라 암모니아를 연료로 하여 수소 충전소에서 암모니아를 바로 분해해서 수소를 생산 및 사용하는, 수소 충전을 위한 암모니아 분해 수소 생산 시스템 및 암모니아 연료 추진 선박이 개발되고 있다.Ammonia has three hydrogens per molecule, and since only hydrogen and nitrogen are released when decomposed, it is attracting attention as a hydrogen source because it can minimize carbon dioxide emissions. In addition, liquid ammonia can store 1.7 times more hydrogen in the same volume than liquid hydrogen, and more than 200 million tons of ammonia are produced annually in the world and used in various industries, so the existing infrastructure can be used to transport or store There are many advantages to Accordingly, an ammonia decomposition hydrogen production system for hydrogen charging and an ammonia fuel propulsion ship, which produce and use hydrogen by directly decomposing ammonia at a hydrogen charging station using ammonia as fuel, are being developed.
그러나, 현재의 암모니아 생산 공정은 극저온을 이용한 분리(cryogenic separation)을 이용하여 암모니아를 분리 및 농축하고 있는데, 이 공정은 에너지 사용량이 많다는 단점이 있다. 이에 따라 암모니아의 분리 및 농축시 압력 변동만으로 암모니아를 용이하게 탈착하여 에너지 저감 효과를 볼 수 있는 암모니아 흡착제의 개발이 필요하다. However, the current ammonia production process separates and concentrates ammonia using cryogenic separation, but this process has a disadvantage in that it consumes a lot of energy. Accordingly, it is necessary to develop an ammonia adsorbent capable of reducing energy by easily desorbing ammonia only with pressure fluctuations during separation and concentration of ammonia.
또한, 암모니아를 분해하여 수소를 생산 및 사용하는 수소 연료 전지의 경우 피독 문제 때문에 잔류 암모니아를 반드시 0.1 ppm 미만이 되도록 제거해야 한다. 또한, 암모니아 연료 추진 선박에서 암모니아 배출이 필요한 경우 일반 대기로 바로 배출하지는 못하고 반드시 암모니아를 제거하여 배출해야 하는데 이를 위해 현재 적용하는 물 흡수법은 ppm 수준까지 제거가 어렵다는 단점이 있다. 이에 따라 저농도의 암모니아도 효과적으로 제거할 수 있는 흡착 성능이 우수한 암모니아 흡착제의 개발이 필요하다.In addition, in the case of a hydrogen fuel cell that produces and uses hydrogen by decomposing ammonia, residual ammonia must be removed to be less than 0.1 ppm due to a poisoning problem. In addition, when ammonia is required to be discharged from an ammonia fuel-propelled ship, it cannot be discharged directly to the general atmosphere and must be discharged after removing ammonia. For this purpose, the currently applied water absorption method has a disadvantage in that it is difficult to remove the ammonia to the ppm level. Accordingly, it is necessary to develop an ammonia adsorbent having excellent adsorption performance that can effectively remove even low concentrations of ammonia.
또한, 대부분의 재생가능한 흡착제는 흡착된 물질을 제거하고 난 후, 다음 흡착 순환을 위해 흡착제를 활성화하는 재생 과정을 거치는데, 재생 동안에 흡착제는 고온이나 고압 등을 경험하여 노화나 흡착 성능의 손실이 초래된다. 따라서, 재생 순환을 통한 성능의 손실이 적어서 수회의 재생 순환을 계속할 수 있는, 안정한 흡착제의 개발이 필요하다.In addition, most regenerable adsorbents undergo a regeneration process in which the adsorbent is activated for the next adsorption cycle after removing the adsorbed material. is brought about Therefore, there is a need to develop a stable adsorbent capable of continuing several regeneration cycles with little performance loss through regeneration cycles.
본 발명의 목적은 온도 변동 흡착 뿐만 아니라 압력 변동 흡착에도 적용이 가능하며 재생이 용이하고 반복 재생 이후에도 우수한 흡착 성능을 안정적으로 유지하는 암모니아 흡착제를 제공하는 것이다.An object of the present invention is to provide an ammonia adsorbent that can be applied not only to temperature swing adsorption but also to pressure swing adsorption, is easy to regenerate, and stably maintains excellent adsorption performance even after repeated regeneration.
본 발명의 일 양태에 따르면, 전체 실리카 알루미나 중량을 기준으로 SiO2 를 3 내지 99 중량%의 중량비로 함유하는 실리카 알루미나를 포함하고, 압력 변동 흡착(Pressure Swing Adsorption, PSA), 온도 변동 흡착(Temperature Swing Adsorption, TSA), 압력 온도 변동 흡착(Pressure Temperature Swing Adsorption, PTSA), 또는 진공 압력 변동 흡착(Vacuum Pressure Swing Adsorption, VPSA)에 적용되는, 암모니아 흡착제가 제공된다.According to one aspect of the present invention, silica alumina containing SiO 2 in a weight ratio of 3 to 99% by weight based on the total weight of silica alumina is included, and pressure swing adsorption (PSA), temperature swing adsorption (Temperature swing adsorption) An ammonia adsorbent applied to swing adsorption (TSA), pressure temperature swing adsorption (PTSA), or vacuum pressure swing adsorption (VPSA) is provided.
본 발명에 따른 암모니아 흡착제는 암모니아의 제거 또는 분리농축을 위해 사용될 수 있다. 또한, 본 발명에 따른 암모니아 흡착제는 암모니아 흡착 성능이 우수할 뿐만 아니라, 압력 변동 흡착(PSA), 온도 변동 흡착(TSA), 압력 온도 변동 흡착(PTSA), 또는 진공 압력 변동 흡착(VPSA)에 적용되어 온도나 압력의 변동 만으로도 용이하게 흡착 및 재생(탈착)될 수 있다. 또한, 흡착 및 탈착에 따른 재생을 반복한 이후에도 우수한 암모니아 흡착량을 유지할 수 있어서 반복적 재생에 의해 장기간 사용이 가능하다. The ammonia adsorbent according to the present invention can be used for the removal or separate concentration of ammonia. In addition, the ammonia adsorbent according to the present invention not only has excellent ammonia adsorption performance, but is also applied to pressure swing adsorption (PSA), temperature swing adsorption (TSA), pressure temperature swing adsorption (PTSA), or vacuum pressure swing adsorption (VPSA). Therefore, it can be easily adsorbed and regenerated (desorbed) only with fluctuations in temperature or pressure. In addition, it is possible to maintain an excellent ammonia adsorption amount even after repeated regeneration by adsorption and desorption, so that it can be used for a long time by repeated regeneration.
이하, 본 발명에 대해 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 출원에서 사용한 용어는 단지 특정한 구현예를 설명하기 위해 사용된 것으로서 본 발명을 한정하려는 의도가 아니다. 다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. The terms used in this application are only used to describe specific embodiments and are not intended to limit the present invention. Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs.
명세서 전체에서, 어떤 부분이 어떤 구성요소를 "포함"한다, "함유”한다, “가지다”라고 할 때, 이는 특별히 달리 정의되지 않는 한, 다른 구성 요소를 더 포함할 수 있다는 것을 의미한다.Throughout the specification, when a part "includes", "includes", or "has" a certain component, it means that it may further include other components unless otherwise specifically defined.
본 발명의 일 구현예에 따르면, 암모니아 흡착제는 실리카 알루미나를 포함하며, 상기 실리카 알루미나는 전체 실리카 알루미나 중량을 기준으로 SiO2 를 3 내지 99 중량%의 중량비, 구체적으로는 20 내지 70 중량%의 중량비, 더 구체적으로는 20 내지 50 중량%의 중량비, 더 구체적으로는 25 내지 40 중량%의 중량비 범위로 함유하는 것일 수 있다. 실리카 알루미나에서 SiO2 를 전술한 범위의 중량비로 함유함으로써 암모니아 흡착제가 반복적으로 재생 순환되더라도 암모니아 흡착 성능이 안정적으로 유지될 수 있으며, 또한, 암모니아 흡착제의 암모니아 흡착량도 우수하다. 본 발명의 일 구현예에 따르면, 상기 실리카 알루미나는 전체 실리카 알루미나 중량을 기준으로 SiO2 및 Al2O3를 각각 20 내지 50 중량%의 중량비 및 50 내지 80 중량%의 중량비로 함유할 수 있다. 예를 들어 상기 실리카 알루미나는 전체 실리카 알루미나 중량을 기준으로 SiO2 및 Al2O3를 각각 40 중량% 및 60 중량%로 함유할 수 있다.According to one embodiment of the present invention, the ammonia adsorbent includes silica alumina, and the silica alumina contains SiO 2 in a weight ratio of 3 to 99% by weight, specifically, 20 to 70% by weight based on the total weight of silica alumina. , More specifically, it may be contained in a weight ratio range of 20 to 50% by weight, more specifically, 25 to 40% by weight. By containing SiO 2 in a weight ratio within the above range in silica alumina, even if the ammonia adsorbent is repeatedly regenerated and cycled, ammonia adsorption performance can be stably maintained, and the ammonia adsorption amount of the ammonia adsorbent is also excellent. According to one embodiment of the present invention, the silica alumina may contain SiO 2 and Al 2 O 3 in a weight ratio of 20 to 50% by weight and 50 to 80% by weight, respectively, based on the total weight of the silica alumina. For example, the silica alumina may contain 40% by weight and 60% by weight of SiO 2 and Al 2 O 3 , respectively, based on the total weight of the silica alumina.
본 발명의 일 구현예에 따르면, 상기 실리카 알루미나에서 알루미나는 활성 알루미나일 수 있다. 또한, 본 발명의 일 구현예에 따르면, 상기 실리카 알루미나는 활성 알루미나의 제조 공정 중에 실리카를 도입하여 개질한 것일 수 있다. 예를 들어, 활성 알루미나로부터 실리카 알루미나를 제조하는 방법으로는, 실리카 수화겔에 알루미나 수화겔을 침전시키는 방법; 알칼리 실리케이트와 알루미늄염 수용액을 겔화시키는 방법; 에스테르를 가수분해하는 방법; 알루미나 슬러리에 콜로이드성 실리카 졸을 첨가한 후, 에이징, 건조 및 하소하는 방법 등을 들 수 있다. 여기서 상기 알루미나 공급원으로는 뵘석(Boehmite)를 사용할 수 있다. 용어 "실리카"는 실리카의 콜로이드 용액, 규산 또는 알칼리 금속 실리케이트 등의 다양한 규소 무기 화합물을 지칭한다.According to one embodiment of the present invention, the alumina in the silica alumina may be activated alumina. Further, according to one embodiment of the present invention, the silica alumina may be modified by introducing silica during the manufacturing process of activated alumina. For example, methods for producing silica alumina from activated alumina include a method in which an alumina hydrogel is precipitated in a silica hydrogel; a method of gelling an alkali silicate and an aluminum salt aqueous solution; a method of hydrolyzing an ester; and a method of adding a colloidal silica sol to an alumina slurry, followed by aging, drying, and calcination. Here, Boehmite may be used as the alumina source. The term "silica" refers to various inorganic compounds of silicon, such as colloidal solutions of silica, silicic acid or alkali metal silicates.
본 발명에 따른 암모니아 흡착제는, 전술한 SiO2 중량비를 갖는 실리카 알루미나를 포함함으로써 암모니아 흡착능이 증가되고, 저농도 암모니아의 고농축을 위한 용도로 사용할 수 있다. 또한, 암모니아 흡착과 탈착의 반복에 우수한 성능을 나타내고 암모니아 합성을 위한 저농도 암모니아의 농축 공정에 적용이 가능하다. 특히, 재생후에도 암모니아 흡착성이 우수하게 유지될 수 있었다. The ammonia adsorbent according to the present invention includes silica alumina having a weight ratio of SiO 2 to increase ammonia adsorption capacity and can be used for high concentration of low-concentration ammonia. In addition, it shows excellent performance in repetition of ammonia adsorption and desorption and can be applied to the concentration process of low concentration ammonia for ammonia synthesis. In particular, excellent ammonia adsorption properties could be maintained even after regeneration.
또한, 본 발명의 일 구현예에 따르면, 본 발명에 따른 암모니아 흡착제는 암모니아 탈착이 상압 또는 진공 부근에서 수행되는 것일 수 있다. 또한, 본 발명의 일 구현예에 따르면, 본 발명에 따른 암모니아 흡착제는 암모니아 탈착이 상온에서 수행되는 것일 수 있다. 본 발명에 따른 암모니아 흡착제는 상압 또는 진공 부근에서 및 상온에서 탈착 및 재생이 가능하기 때문에 공정 운전비용의 감소를 기대할 수 있다. 따라서, 온도 변동 흡착(TSA) 뿐만 아니라 압력 변동 흡착(PSA), 압력 온도 변동 흡착(PTSA), 및 진공 압력 변동 흡착(VPSA)에서도 사용이 가능하다. 특히, 본 발명의 일 구현예에 따르면, 본 발명에 따른 암모니아 흡착제는 압력 변동 흡착 또는 진공 압력 변동 흡착, 예를 들어 압력 변동 흡착에 적용될 수 있다. 본 발명의 암모니아 흡착제를 압력 변동 흡착 또는 진공 압력 변동 흡착에 적용할 경우, 암모니아의 흡착은 3 bar 이상의 압력에서 수행되고 암모니아의 탈착은 상압 또는 진공 부근에서 수행될 수 있다. 이에, 본 발명의 일 구현예에 따르면, 암모니아의 탈착이 상압 및 상온에서 수행되는, 압력 변동 흡착에 적용되는 암모니아 흡착제가 제공될 수 있다.In addition, according to one embodiment of the present invention, the ammonia adsorbent according to the present invention may be one in which ammonia is desorbed at atmospheric pressure or near vacuum. In addition, according to one embodiment of the present invention, the ammonia adsorbent according to the present invention may be one in which ammonia is desorbed at room temperature. Since the ammonia adsorbent according to the present invention can be desorbed and regenerated at normal pressure or near vacuum and at room temperature, a reduction in process operating cost can be expected. Therefore, it can be used not only for temperature swing adsorption (TSA) but also for pressure swing adsorption (PSA), pressure temperature swing adsorption (PTSA), and vacuum pressure swing adsorption (VPSA). In particular, according to one embodiment of the present invention, the ammonia adsorbent according to the present invention can be applied to pressure swing adsorption or vacuum pressure swing adsorption, for example, pressure swing adsorption. When the ammonia adsorbent of the present invention is applied to pressure swing adsorption or vacuum pressure swing adsorption, ammonia adsorption may be performed at a pressure of 3 bar or more, and ammonia desorption may be performed at atmospheric pressure or near vacuum. Therefore, according to one embodiment of the present invention, an ammonia adsorbent applied to pressure swing adsorption, in which ammonia is desorbed at normal pressure and temperature, can be provided.
또한, 본 발명에 따른 흡착제는 암모니아 제거 또는 분리농축이 필요한 다양한 용도로 사용될 수 있으며, 예를 들어, 암모니아를 연료로 사용하는 연료 전지, 암모니아 분해에 의한 수소 생산 시스템, 암모니아를 연료로 사용하는 추진 선박 시스템, 암모니아 개질기 등에서 잔류 암모니아를 제거하거나 암모니아 배출 필요시 대기 배출을 최소화하기 위한 암모니아 제거에 사용될 수 있다. 특히, 수소 생산 시스템이나 암모니아 개질기 정제 등과 같이 0.1 ppm 미만의 수준으로 암모니아를 제거해야할 필요가 있는 용도에 유용하게 사용될 수 있다. 이에, 본 발명의 일 구현예에 따르면, 본 발명에 따른 암모니아 흡착제는 암모니아 분해에 의한 수소 생산 시스템에서 잔류 암모니아를 제거하기 위해 적용되는 것일 수 있다. 또한, 본 발명의 다른 일 구현예에 따르면, 본 발명에 따른 암모니아 흡착제는 암모니아 생산 시스템에서 암모니아를 분리 및 농축하는데 사용되는 것일 수 있다.In addition, the adsorbent according to the present invention can be used for various purposes requiring ammonia removal or separation and concentration, for example, a fuel cell using ammonia as a fuel, a hydrogen production system by decomposing ammonia, and propulsion using ammonia as a fuel. It can be used to remove residual ammonia from ship systems, ammonia reformers, etc., or to minimize air emissions when ammonia is required. In particular, it can be usefully used for applications where ammonia needs to be removed at a level of less than 0.1 ppm, such as a hydrogen production system or an ammonia reformer purification. Therefore, according to one embodiment of the present invention, the ammonia adsorbent according to the present invention may be applied to remove residual ammonia in a hydrogen production system by decomposition of ammonia. In addition, according to another embodiment of the present invention, the ammonia adsorbent according to the present invention may be used to separate and concentrate ammonia in an ammonia production system.
이하에서는 본 발명의 실시예를 참조하여 발명을 더욱 구체적으로 설명하겠다. 실시예는 발명의 설명을 위해 제시되는 것이므로, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to embodiments of the present invention. Since the examples are presented for explanation of the invention, the present invention is not limited thereto.
[실험예] 암모니아 파괴 실험[Experimental Example] Ammonia Destruction Test
SiO2 함량을 다양하게 한 실리카 알루미나를 암모니아 흡착제로 사용하였으며, 반응기는 고정층 반응기로 사용하였다. 암모니아 기체를 반응기 상부에서 주입하여 시료층을 거친 후, 하부로 배출되도록 하였으며, 흡착 완료후 하부에서 배출된 암모니아를 휴대용 암모니아 분석 장비로 검출하였다.Silica alumina with various SiO 2 contents was used as an ammonia adsorbent, and the reactor was used as a fixed bed reactor. Ammonia gas was injected from the upper part of the reactor, passed through the sample layer, and then discharged to the lower part. After adsorption was completed, the ammonia discharged from the lower part was detected with a portable ammonia analyzer.
PSA 공정 조건에서 암모니아 흡착을 수행하였으며, PSA는 역압력 레귤레이터 (back pressure regulator)를 통해 반응기 내부의 압력을 조절하여 7 bar 에서 흡착을 진행하였으며, 다시 상압으로 감압시켜 N2 를 흘려주며 상온에서 탈착을 진행하였고 이러한 재생 사이클 과정을 반복하였다. 그 결과를 다음의 [표 1] 내지 [표 4]에 나타낸다.Ammonia adsorption was performed under PSA process conditions, and PSA was adsorbed at 7 bar by adjusting the pressure inside the reactor through a back pressure regulator, and desorbed at room temperature by reducing the pressure to normal pressure again and flowing N 2 and this regeneration cycle process was repeated. The results are shown in the following [Table 1] to [Table 4].
상기 표 1 내지 표 4와 비교하면, 2 cycle 및 그 이상의 반복 재생 후의 암모니아 흡착량이 본 발명의 SiO2 함량 범위를 만족하는 표 3과 표 4에서 현저히 개선된 것을 알 수 있다. 특히, 표 4에서는 5 cycle 반복 후에도 암모니아 흡착량이 표 1의 초기 흡착량보다 더 좋았고, 표 2의 2 cycle 반복 이후의 흡착량에 비해 거의 2배 더 우수하였다. 이는 본 발명에 따른 SiO2 함량 범위를 만족하는 암모니아 흡착제는 반복 재생 후의 흡착 안정성 뿐만 아니라, 흡착량, 즉, 흡착 성능 그 자체도 개선되었다는 것을 의미한다. Compared with Tables 1 to 4, it can be seen that the amount of ammonia adsorption after repeated regeneration of 2 cycles or more is significantly improved in Tables 3 and 4 satisfying the SiO 2 content range of the present invention. In particular, in Table 4, the ammonia adsorption amount was better than the initial adsorption amount in Table 1 even after repeating 5 cycles, and was almost twice as good as the adsorption amount after repeating 2 cycles in Table 2. This means that the ammonia adsorbent satisfying the SiO 2 content range according to the present invention has improved adsorption stability after repeated regeneration as well as adsorption amount, ie, adsorption performance itself.
상기에서는 본 발명의 바람직한 실시예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허 청구 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.Although the above has been described with reference to preferred embodiments of the present invention, those skilled in the art can variously modify and change the present invention without departing from the spirit and scope of the present invention described in the claims below. You will understand that you can.
Claims (9)
압력 변동 흡착, 온도 변동 흡착, 압력 온도 변동 흡착, 또는 진공 압력 변동 흡착에 적용되는, 암모니아 흡착제. Comprising silica alumina containing SiO 2 in a weight ratio ranging from 3 to 99% by weight based on the total weight of silica alumina,
An ammonia adsorbent, applied to pressure swing adsorption, temperature swing adsorption, pressure temperature swing adsorption, or vacuum pressure swing adsorption.
상기 SiO2 함량이 20 내지 50 중량% 범위인 것을 특징으로 하는 암모니아 흡착제.According to claim 1,
Ammonia adsorbent, characterized in that the SiO 2 content is in the range of 20 to 50% by weight.
상기 SiO2 함량이 25 내지 40 중량% 범위인 특징으로 하는 암모니아 흡착제.According to claim 2,
Ammonia adsorbent, characterized in that the SiO 2 content is in the range of 25 to 40% by weight.
상기 알루미나는 활성 알루미나인 것을 특징으로 하는 암모니아 흡착제.According to claim 1,
The ammonia adsorbent, characterized in that the alumina is activated alumina.
압력 변동 흡착 또는 진공 압력 변동 흡착에 적용되는 것을 특징으로 하는 암모니아 흡착제.According to claim 1,
An ammonia adsorbent, characterized in that it is applied to pressure swing adsorption or vacuum pressure swing adsorption.
암모니아의 탈착이 상압 또는 진공 부근에서 수행되는 것을 특징으로 하는 암모니아 흡착제.According to claim 5,
An ammonia adsorbent, characterized in that the desorption of ammonia is carried out at normal pressure or near vacuum.
암모니아의 탈착이 상온에서 수행되는 것을 특징으로 하는 암모니아 흡착제.According to claim 6,
Ammonia adsorbent, characterized in that the desorption of ammonia is carried out at room temperature.
암모니아 분해에 의한 수소 생산 시스템에서 잔류 암모니아를 제거하기 위해 적용되는 것을 특징으로 하는 암모니아 흡착제.According to claim 1,
An ammonia adsorbent characterized in that it is applied to remove residual ammonia in a hydrogen production system by decomposition of ammonia.
암모니아 생산 시스템에서 암모니아를 분리 및 농축하는데 적용되는 것을 특징으로 하는 암모니아 흡착제.According to claim 1,
An ammonia adsorbent, characterized in that it is applied to separate and concentrate ammonia in an ammonia production system.
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| JP2002159849A (en) * | 2000-11-24 | 2002-06-04 | Rikogaku Shinkokai | Laminar double hydroxide-alumina/silica gel composite and method for preparing the same, and adsorbent |
| KR20210096141A (en) * | 2018-11-21 | 2021-08-04 | 사솔 (유에스에이) 코포레이션 | Silica-alumina composition with improved stability and method for preparing same |
| KR102311550B1 (en) * | 2021-03-30 | 2021-10-12 | 한국에너지기술연구원 | Metal-Impregnated Activated Carbon For Adsorbing Ammonia, Preparation Method Therefor, and Uses Thereof |
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