KR100562020B1 - Carbon dioxide immobilized adsorbent and its manufacturing method - Google Patents
Carbon dioxide immobilized adsorbent and its manufacturing method Download PDFInfo
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- KR100562020B1 KR100562020B1 KR1020030065121A KR20030065121A KR100562020B1 KR 100562020 B1 KR100562020 B1 KR 100562020B1 KR 1020030065121 A KR1020030065121 A KR 1020030065121A KR 20030065121 A KR20030065121 A KR 20030065121A KR 100562020 B1 KR100562020 B1 KR 100562020B1
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 94
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 94
- 239000003463 adsorbent Substances 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 123
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 115
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010457 zeolite Substances 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 230000005661 hydrophobic surface Effects 0.000 abstract 1
- 229960004424 carbon dioxide Drugs 0.000 description 82
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 230000002285 radioactive effect Effects 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- -1 calcium Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000010792 warming 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
-
- 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
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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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
본 발명은 이산화탄소를 효과적으로 흡착시켜, 분리 제거하기 위한 흡착제와 그의 제조방법에 관한 것이며, 기존에 이를 위한 목적으로 사용되는 활성탄 및 제올라이트 등과 같은 무기흡착제가 가지고 있는 소수성 표면이나 세공의 구조로 야기되는 여러 가지 한계를 극복하기 위해, 활성탄의 표면을 산성용액으로 개질하여 친수성을 갖게 하는 관능기를 표면에 부착하고, 여기에 역시 친수성 흡착제인 LiOH를 첨착시켜 첨착의 안정성과 첨착량의 증가를 꾀하였으며, 또한 기존의 수용액를 이용하는 첨착 방법을 지양하고, 담지체의 소수성 여하에 영향이 적은, 분말 형태로 처리된 흡착제와 담지체를 기계적으로 혼합하는 방법을 채택하여, 흡착제의 첨착 효율을 향상시켰다. The present invention relates to an adsorbent for effectively adsorbing and separating carbon dioxide and to a method of preparing the same, and to a variety of hydrophobic surfaces or pores caused by inorganic adsorbents such as activated carbon and zeolite, which are used for this purpose. In order to overcome these limitations, the surface of the activated carbon was modified with an acid solution to attach a functional group to make it hydrophilic, and LiOH, which is also a hydrophilic adsorbent, was attached to the surface to increase the stability and the amount of deposition. Avoiding the deposition method using the existing aqueous solution, and the method of mechanically mixing the adsorbent and the carrier in the form of powder, which has little influence on the hydrophobicity of the carrier, was adopted to improve the adhesion efficiency of the adsorbent.
이산화탄소, 흡착제, 활성탄, 수산화리튬Carbon dioxide, adsorbent, activated carbon, lithium hydroxide
Description
도 1은 종래 기술에 의한 이산화탄소 고정화 흡착제의 제조 공정도이다.1 is a manufacturing process chart of a carbon dioxide immobilized adsorbent according to the prior art.
도 2는 본 발명에 의한 제 1이산화탄소 고정화 흡착제의 제조 공정도이다.2 is a manufacturing process chart of the first carbon dioxide immobilized adsorbent according to the present invention.
도 3은 본 발명에 의한 제 2이산화탄소 고정화 흡착제의 제조 공정도이다.3 is a manufacturing process chart of the second carbon dioxide immobilized adsorbent according to the present invention.
도 4는 본 발명에 의한 제 3이산화탄소 고정화 흡착제의 제조 공정도이다.4 is a manufacturing process chart of the third carbon dioxide immobilized adsorbent according to the present invention.
도 5는 본 발명에 의한 제 1이산화탄소 고정화 흡착제의 이산화탄소 흡착성능 결과를 나타낸 그래프이다.5 is a graph showing the results of carbon dioxide adsorption performance of the first carbon dioxide immobilized adsorbent according to the present invention.
도 6은 본 발명에 의한 제 2이산화탄소 고정화 흡착제의 이산화탄소 흡착성능결과를 나타낸 그래프이다.6 is a graph showing the carbon dioxide adsorption performance of the second carbon dioxide immobilized adsorbent according to the present invention.
본 발명은 화력발전소, 원자력발전소 등과 같은 고정원 및 자동차와 같은 이동원에서 배출되는 이산화탄소 및 방사성 이산화탄소를 흡착, 고정화하기 위한 이산화탄소 고정화 흡착제와 그의 제조방법에 관한 것이다. 보다 상세하게는 수산화리튬을 수용액으로 하여 이를 활성탄에 첨착시켜 제조한 이산화탄소 고정화 흡착제 또는 수산화리튬 분말과 활성탄을 기계적 혼합을 통해 제조한 이산화탄소 고정화 흡착제와 그의 제조방법에 관한 것이다.The present invention relates to a carbon dioxide immobilized adsorbent for adsorbing and immobilizing carbon dioxide and radioactive carbon dioxide discharged from a fixed source such as a thermal power plant, a nuclear power plant, and a mobile source such as an automobile, and a method of manufacturing the same. More specifically, the present invention relates to a carbon dioxide immobilized adsorbent prepared by attaching lithium hydroxide as an aqueous solution to an activated carbon, or a carbon dioxide immobilized adsorbent prepared by mechanically mixing lithium hydroxide powder and activated carbon, and a method of manufacturing the same.
온실가스 중의 하나인 이산화탄소는 지구 온난화 현상의 요인 중 가장 많은 비율인 55%를 차지하고 있다. 이와 같은 이산화탄소는 화력발전소 및 원자력 발전소 그리고 제철소, 시멘트공장, 석유화학공장 등에서 주로 배출된다. 특히 원자력 발전소의 경우 방사성 동위원소(C-14)를 포함하는 이산화탄소가 발생하는데, 이 C-14는 최대에너지가 156keV인 β선을 방출하는 핵종이며 반감기는 5,730년에 달한다. 대기 중의 C-14 방사능은 주로 탄화수소나 이산화탄소 형태로 존재하는 C-14에 기인하며, 특히 방사성 이산화탄소는 동식물에 의한 호흡이나 탄소동화작용을 통해 생물체내에 고정되고, 먹이사슬의 경로를 거쳐 인체 내에 축적될 수 있어 다른 방사성 화합물보다 각별한 관리와 감시가 필요하다. 이와 같은 이유로 C-14를 포함한 이산화탄소의 배출량을 감소시키기 위한 흡착, 분리, 회수, 공정 등과 같은 다양한 기술이 개발되어 왔다. 이 중에서 흡착법은 에너지 소비가 적고 흡착제를 회수하여 다시 사용할 수 있기 때문에 경제적인 저감기술로 평가되고 있다. Carbon dioxide, one of the greenhouse gases, accounts for 55%, the largest proportion of global warming. Such carbon dioxide is mainly emitted from thermal power plants, nuclear power plants, and steel mills, cement plants, and petrochemical plants. Particularly in nuclear power plants, carbon dioxide, which contains radioactive isotopes (C-14), is produced. The C-14 is a nuclide that emits β-rays with a maximum energy of 156 keV, with a half-life of 5,730 years. C-14 radioactivity in the atmosphere is mainly due to C-14 in the form of hydrocarbons or carbon dioxide, and in particular, radioactive carbon dioxide is fixed in living organisms through respiration or carbon assimilation by plants and animals, and accumulates in the human body through the food chain pathway. This requires more care and monitoring than other radioactive compounds. For this reason, various techniques have been developed, such as adsorption, separation, recovery, and processes to reduce carbon dioxide emissions, including C-14. Among these, the adsorption method is evaluated as an economical reduction technique because it uses less energy and can recover and use the adsorbent.
이산화탄소를 흡착법을 이용하여 분리, 회수하기 위해 활성탄 및 제올라이트 등과 같은 무기 흡착제가 주로 사용되어 왔다. 활성탄은 다공성 탄소질 흡착제로서 결정질의 다환 방향족 분자 집합체와 비정질 탄화수소로 이루어져 거대 세공부터 미세 세공이 공존하는 세공 구조를 지니고 있다. 활성탄은 야자각 등과 같은 식물성 원료나 갈탄 등과 같은 석탄계 원료를 출발 물질로 하고 있다. 활성탄의 이산화탄소에 대한 흡착 성능을 증가시키기 위해 이산화탄소에 선택성이 우수한 것으로 알려진 칼슘 등과 같은 알카리 금속을 이온화하여 이를 활성탄에 첨착시켜 이를 흡착제로 적용하고자하는 연구가 진행되고 있다. Inorganic adsorbents such as activated carbon and zeolite have been mainly used to separate and recover carbon dioxide by adsorption. Activated carbon is a porous carbonaceous adsorbent composed of crystalline polycyclic aromatic molecular aggregates and amorphous hydrocarbons and has a pore structure in which coarse to fine pores coexist. Activated carbon is based on vegetable raw materials such as coconut shell and coal-based raw materials such as lignite. In order to increase the adsorption performance of activated carbon to carbon dioxide, research is being conducted to ionize an alkali metal such as calcium, which is known to have excellent selectivity to carbon dioxide, and to attach it to activated carbon to apply it as an adsorbent.
알칼리금속인 리튬은 보통 수산화리튬 분말로 존재하며 대기중에 노출되면 대기중에 있는 이산화탄소가 일부 분말에 흡착, 고정화될 정도로 이산화탄소의 흡착, 고정화에 선택성이 매우 우수하다. 그러나 수산화리튬 분말이 비산하여 인체에 축적되면 두뇌, 호흡기 및 신경계통에 심각한 영향을 끼친다. 따라서 수산화리튬 분말의 대기중으로의 비산 방지뿐만 아니라 수산화리튬 분말의 분산도를 넓혀 보다 많은 양의 이산화탄소를 흡착, 고정화하기 위해서는 수산화리튬 분말을 흡착제에 첨착 또는 고정화하여 사용하여야 한다. Lithium, an alkali metal, is usually present as lithium hydroxide powder, and when exposed to the atmosphere, the selectivity is very good for adsorption and immobilization of carbon dioxide such that carbon dioxide in the atmosphere is adsorbed and immobilized on some powders. However, when lithium hydroxide powder scatters and accumulates in the human body, it severely affects the brain, respiratory system, and nervous system. Therefore, in order to adsorb and immobilize a larger amount of carbon dioxide by increasing the dispersion degree of the lithium hydroxide powder as well as preventing the scattering of the lithium hydroxide powder into the atmosphere, the lithium hydroxide powder should be used by adhering or immobilizing the lithium hydroxide powder.
첨부도면 중 도 1은 종래의 기술에 의한 이산화탄소 고정화 흡착제의 제조 공정도이다. 수산화리튬과 물이 일정 비율로 혼합된 수용액에 활성탄을 투입하고 이를 교반기를 이용하여 충분히 교반한 후, 용액을 건조기에서 증발 건조하여 이산화탄소 고정화 흡착제를 제조하고 있다. 대한민국 공개특허 제2000-53782호와 대한민국 공개특허 제1996-71539호에서는 도 1과 같은 방법으로 소수성인 활성탄에 수산화리튬을 첨착시키는 방법을 제안하고 있다. 그러나, 소수성 흡착제인 활성탄에서 수산화리튬의 첨착량 또는 담지량이 증가하게 되면 활성탄 세공 내에서 수산화리튬의 결정이 성장하면서 활성탄의 세공을 막아버린다. 이로 인해 이산화탄소의 흡착, 고정화에는 단지 세공 외부로 노출된 부위만 사용되어 다량의 수산화리튬을 사용하였음에도 불구하고 이산화탄소의 흡착량은 전혀 증가하지 않는 문제가 있다. 1 is a manufacturing process diagram of a carbon dioxide immobilized adsorbent according to the prior art. Activated carbon was added to an aqueous solution in which lithium hydroxide and water were mixed at a predetermined ratio and sufficiently stirred by using a stirrer, and the solution was evaporated to dryness in a dryer to prepare a carbon dioxide immobilized adsorbent. Korean Patent Laid-Open Publication No. 2000-53782 and Korean Patent Laid-Open Publication No. 1996-71539 propose a method of attaching lithium hydroxide to hydrophobic activated carbon in the same manner as in FIG. 1. However, when the amount of deposition or loading of lithium hydroxide in the activated carbon, which is a hydrophobic adsorbent, increases, crystals of lithium hydroxide grow in the activated carbon pores, thereby blocking the pores of activated carbon. Therefore, there is a problem that the adsorption amount of carbon dioxide does not increase at all even though only portions exposed to the outside of the pores are used for adsorption and immobilization of carbon dioxide.
본 발명은 이러한 종래의 문제점을 해결하기 위한 것으로 활성탄의 질산, 초산, 황산 등과 같은 산성 물질을 이용하여 활성탄의 표면에 OH, COOH 등과 같은 관능기를 부여하여 수산화리튬의 첨착량을 증가하여 이산화탄소의 흡착량을 증진시킬 수 있는 이산화탄소 고정화 흡착제와 그의 제조방법을 제공하는데 그 목적이 있다. The present invention is to solve such a conventional problem by using an acidic material such as nitric acid, acetic acid, sulfuric acid of activated carbon to give a functional group such as OH, COOH on the surface of the activated carbon to increase the amount of lithium hydroxide adsorbed carbon dioxide adsorption It is an object of the present invention to provide a carbon dioxide immobilized adsorbent and a method for producing the same that can increase the amount.
또한, 본 발명은 소수성 활성탄의 세공 내에 수산화리튬을 수용액 상태로 첨착하지 않고 분말 형태로 기계적 혼합 방법을 이용하여 첨착하여 세공이 막히는 현상을 방지할 수 있는 이산화탄소 고정화 흡착제와 그의 제조방법을 제공하는데 그 목적이 있다. In addition, the present invention provides a carbon dioxide immobilized adsorbent that can prevent the clogging of the pores by applying a mechanical mixing method in the form of powder without impregnating lithium hydroxide in the aqueous solution in the pores of hydrophobic activated carbon, and its manufacturing method There is a purpose.
첨부도면 중 도 2는 본 발명에 의한 제 1이산화탄소 고정화 흡착제의 제조 공정도를 나타낸 것이다. 본 발명에 의한 제 1이산화탄소 고정화 흡착제는 크게 활성탄의 표면 개질 단계, 수용액 상태의 수산화리튬의 표면 개질 활성탄으로 첨착 단계로 나뉘어 진다. 상기 활성탄의 표면 개질 단계에서, 표면 개질제로는 0.01N에서 2N의 질산(HNO3), 초산(HCOOH), 황산(H2SO4), 인산(H3PO4), 옥살산[(COOH)₂2H2O], 과산화수소(H2O2), 염산(HCl) 등의 산성 물질을 사용한다. 활성탄의 표면 개질은 감압증발기에서 표면개질제에 활성탄을 넣고 30℃에서 130℃ 사이에서 10 rpm(분당회전속도)에서 500 rpm으로 교반하거나 또는 상압 상태의 회분식장치에 활성탄을 넣고 30℃에서 130℃ 사이에서 10 rpm에서 500 rpm으로 회전시키면서 상기 농도의 표면 개질제를 스프레이로 분사하는 방식으로 수행한다.Figure 2 of the accompanying drawings shows a manufacturing process chart of the first carbon dioxide immobilized adsorbent according to the present invention. The first carbon dioxide immobilized adsorbent according to the present invention is divided into a surface modification step of activated carbon and an impregnation step with surface modification activated carbon of lithium hydroxide in an aqueous solution state. In the surface modification step of the activated carbon, as a surface modifier, the nitric acid (HNO 3 ), acetic acid (HCOOH), sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ), oxalic acid [(COOH) ₂2H Acidic materials such as 2 O], hydrogen peroxide (H 2 O 2 ), and hydrochloric acid (HCl). The surface modification of activated carbon is carried out by adding activated carbon to the surface modifier in a reduced pressure evaporator, stirring at 30 rpm to 130 ℃ at 10 rpm (rpm) at 500 rpm or by placing the activated carbon in a batch batch apparatus at atmospheric pressure and then operating at 30 to 130 캜. Spraying the surface modifier of this concentration while rotating from 10 rpm to 500 rpm.
표면 개질제로 처리한 활성탄은 80℃에서 130℃ 사이의 온도에서 1시간에서 10시간 동안 건조 증발시킨다. 그리고 감압증발기에 표면 개질 활성탄의 무게 대비 0.1%에서 90%에 해당하는 수산화리튬이 녹아 있는 수용액에 상기 활성탄을 넣고 30℃에서 130℃ 사이에서 10 rpm에서 500 rpm으로 교반하거나 또는 상압 상태의 회분식장치에 표면 개질 활성탄을 넣고 30℃에서 130℃ 사이에서 10 rpm에서 500 rpm으로 회전시키면서 상기 수산화리튬 수용액을 스프레이로 분사하는 방식으로 수산화리튬의 첨착을 수행한다. 수산화리튬이 첨착된 표면 개질 활성탄의 건조는 건조기에서 80℃에서 130℃ 사이의 온도에서 1시간에서 10시간 동안 건조 증발시키는 방법으로 이산화탄소 고정화 흡착제를 제조한다. Activated carbon treated with the surface modifier is dry evaporated for 1 to 10 hours at a temperature between 80 ° C and 130 ° C. Then, the activated carbon is put in an aqueous solution in which lithium hydroxide is dissolved in 0.1% to 90% of the weight of the surface-modified activated carbon in a reduced pressure evaporator, and stirred at 10 rpm to 500 rpm between 30 ° C. and 130 ° C. The surface-modified activated carbon was added thereto, and lithium hydroxide was added by spraying the lithium hydroxide aqueous solution with a spray while rotating at 30 rpm to 130 ° C. at 10 rpm to 500 rpm. Drying of surface-modified activated carbon impregnated with lithium hydroxide is carried out by drying evaporation at a temperature between 80 ° C. and 130 ° C. for 1 hour to 10 hours to prepare a carbon dioxide immobilized adsorbent.
도 3은 본 발명에 의한 제 2이산화탄소 고정화 흡착제의 제조 공정도를 나타낸 것이다. 본 발명에 의한 제 2이산화탄소 고정화 흡착제는 0.1 나노미터에서 10마이크로미터의 크기에 해당하는 수산화리튬 분말을 활성탄 무게 대비 0.1%에서 90%의 양으로 하여 표면 개질이 않된 활성탄과 함께 상압 회분식 장치에 넣고 30℃에서 130℃ 사이의 온도에서 10 rpm에서 500 rpm으로 교반하는 기계적 혼합을 통해 제조한다. 이 과정에서 수산화리튬 분말은 대부분 활성탄의 세공 내에 미세한 입자 상태로 들어가 첨착된다. Figure 3 shows a manufacturing process chart of the second carbon dioxide immobilized adsorbent according to the present invention. The second carbon dioxide immobilized adsorbent according to the present invention is a lithium hydroxide powder corresponding to a size of 0.1 nanometer to 10 micrometers in an amount of 0.1% to 90% of the weight of activated carbon and placed in an atmospheric pressure batch device together with activated carbon without surface modification. Prepared via mechanical mixing, stirring at 10 rpm to 500 rpm at a temperature between 30 ° C. and 130 ° C. In this process, lithium hydroxide powder mostly enters fine particles in pores of activated carbon and is impregnated.
도 4는 본 발명에 의한 제 3이산화탄소 고정화 흡착제의 제조 공정도를 나타낸 것이다. 본 발명에 의한 제 3이산화탄소 고정화 흡착제는 0.1 나노미터에서 10마이크로미터의 크기에 해당하는 수산화리튬 분말을 활성탄 무게 대비 0.1%에서 90%의 양으로 하여 도 2에서와 같이 표면이 개질된 표면 개질 활성탄과 함께 상압 회분식 장치에 넣고 30℃에서 130℃ 사이의 온도에서 10 rpm에서 500 rpm으로 교반하는 기계적 혼합을 통해 제조한다. 수산화리튬 분말은 표면이 개질되지 않은 소수성 활성탄에 비해 세공 크기가 증가하고 표면의 관능기 부여로 인해 보다 많은 량의 수산화리튬의 분말이 상기 활성탄의 세공 내에 첨착된다. Figure 4 shows the manufacturing process of the third carbon dioxide immobilized adsorbent according to the present invention. The third carbon dioxide immobilized adsorbent according to the present invention is lithium hydroxide powder corresponding to the size of 0.1 nanometer to 10 micrometer in the amount of 0.1% to 90% of the weight of activated carbon, the surface-modified activated carbon as shown in FIG. It is prepared through mechanical mixing with stirring in an atmospheric pressure batch apparatus with stirring at 10 rpm to 500 rpm at a temperature between 30 ℃ to 130 ℃. Lithium hydroxide powder has a larger pore size compared to hydrophobic activated carbon with no surface modification and a larger amount of lithium hydroxide powder is impregnated in the pores of the activated carbon due to functionalization of the surface.
도 2, 도 3, 도4에서 제조한 본 발명의 이산화탄소 고정화 흡착제에서, 이산화탄소는 다음의 반응식과 같이 수산화리튬과 반응하여 탄산리튬으로 고정화된다. In the carbon dioxide immobilized adsorbent of the present invention prepared in FIGS. 2, 3, and 4, carbon dioxide is fixed with lithium carbonate by reacting with lithium hydroxide as in the following reaction formula.
2LiOH + CO2 → Li2CO3 + H2O (1)2LiOH + CO 2 → Li 2 CO 3 + H 2 O (1)
본 발명에 의한 이산화탄소 고정화 흡착제에서, 이산화탄소 고정화 물질로 사용한 수산화리튬(LiOH)외에도 칼슘(Ca), 바륨(Ba), 칼륨(K) 등의 복합 화합물인 수산화바륨(Ba(OH)2), 수산화칼슘(Ca(OH2)), 수산화칼륨(KOH)이 이산화탄소의 고정화물질로의 적용이 가능하다. 또한 질산(HNO3), 초산(HCOOH), 황산(H2SO4), 인산(H3PO4), 옥살산[(COOH)₂2H2O], 염산(HCl), 과산화수소(H2O 2) 등과 같은 산성 물질을 이용한 표면 개질은 무기 복합체인 제올라이트, 실리카, 알루미나 등에도 적용이 가능하다. In the carbon dioxide immobilized adsorbent according to the present invention, in addition to lithium hydroxide (LiOH) used as a carbon dioxide immobilization material, barium hydroxide (Ba (OH) 2 ), calcium hydroxide, which is a complex compound such as calcium (Ca), barium (Ba), potassium (K), and the like (Ca (OH 2 )), potassium hydroxide (KOH) is applicable to the immobilization material of carbon dioxide. Also nitric acid (HNO 3 ), acetic acid (HCOOH), sulfuric acid (H 2 SO 4 ), phosphoric acid (H 3 PO 4 ), oxalic acid [(COOH) ₂2H 2 O], hydrochloric acid (HCl), hydrogen peroxide (H 2 O 2 ) Surface modification using an acidic material such as is applicable to the inorganic composite zeolite, silica, alumina and the like.
본 발명에 의해 제조한 이산화탄소 고정화 흡착제의 이산화탄소 흡착 성능을 실시 예를 통해 보다 상세히 설명하기로 한다. 본 발명의 모든 실시예에서 수행된 이산화탄소 흡착실험은 다음과 같은 방법으로 수행되었다. 즉, 흡착제를 충전할 수 있는 흡착관으로는 석영으로 된 U자형 마이크로 반응기를 사용하였고 29.75% CO2(He 기준)와 He(99.999%)의 혼합 기체를 유량조절기를 이용하여 원하는 농도로 맞추어 상온(23℃ 내지 24℃) 및 상압 조건에서 흡착제의 성능평가를 실시하였다. 흡착 성능은 가스크로마토그래프(영린600D, 충전칼럼 chromosorb-104)를 이용하여 흡착관 입구 또는 출구에서의 이산화탄소 농도를 측정하는 방법으로 평가하였다. The carbon dioxide adsorption performance of the carbon dioxide immobilized adsorbent prepared by the present invention will be described in more detail with reference to the following examples. Carbon dioxide adsorption experiments performed in all embodiments of the present invention was carried out in the following manner. That is, a U-shaped micro reactor made of quartz was used as an adsorption tube to fill the adsorbent, and the mixture gas of 29.75% CO 2 (He basis) and He (99.999%) was adjusted to a desired concentration using a flow controller at room temperature. (23 ° C. to 24 ° C.) and performance evaluation of the adsorbent were carried out at atmospheric pressure. Adsorption performance was evaluated by measuring the carbon dioxide concentration at the inlet or outlet of the adsorption tube using a gas chromatograph (Younglin 600D, packed column chromosorb-104).
실시예 1Example 1
첨부 도면 중 도 5는 본 발명에 의한 제 1이산화탄소 고정화 흡착제의 이산화탄소 흡착 성능 결과를 나타낸 그래프이다. 도 5에서 5% LiOH는 종래의 기술에 의한 이산화탄소 고정화 흡착제로서, 표면 개질이 안된 활성탄에 상기 활성탄의 무게 대비 5%의 수산화리튬을 첨착시킨 것이다. 2% LiOH(질산)은 본 발명에 의한 제 1이산화탄소 고정화 흡착제로서, 종래의 기술에 의한 이산화탄소 고정화 흡착에 사용한 활성탄과 동일한 활성탄의 표면을 1N의 질산을 이용하여 개질하고 여기에 상기 활성탄의 무게 대비 2%의 수산화리튬을 첨착한 것이다. 5 is a graph showing the carbon dioxide adsorption performance results of the first carbon dioxide immobilized adsorbent according to the present invention. In FIG. 5, 5% LiOH is a carbon dioxide immobilized adsorbent according to the prior art, in which 5% lithium hydroxide is added to the activated carbon having no surface modification, compared to the weight of the activated carbon. 2% LiOH (nitric acid) is the first carbon dioxide immobilized adsorbent according to the present invention, and the surface of the same activated carbon used for carbon dioxide immobilized adsorption according to the prior art is modified with 1 N nitric acid, and the weight of the activated carbon 2% of lithium hydroxide is impregnated.
본 발명에 의한 제 1이산화탄소 고정화 흡착제의 수산화리튬 첨착량이 적음에도 불구하고 오히려 이산화탄소는 늦게 파괴되고 있다. 이는 본 발명에 의한 제 1이산화탄소 고정화 흡착제의 이산화탄소에 대한 흡착 성능이 매우 우수함을 의미한다. 첨착된 수산화리튬 1g당 흡착된 이산화탄소의 흡착량(mol)에 있어서, 본 발명에 의한 제 1이산화탄소 고정화 흡착제의 이산화탄소 흡착량은 0.01481 mol/g이고 종래의 기술에 의한 이산화탄소 고정화 흡착제의 이산화탄소 흡착량은 0.00514 mol/g으로 약 3배 정도 크게 나타났다. In spite of the small amount of lithium hydroxide adhering of the first carbon dioxide immobilized adsorbent according to the present invention, the carbon dioxide is slowly destroyed. This means that the adsorption performance on carbon dioxide of the first carbon dioxide immobilized adsorbent according to the present invention is very excellent. Adsorption amount of carbon dioxide adsorbed per mol of lithium hydroxide impregnated (mol), the carbon dioxide adsorption amount of the first carbon dioxide immobilized adsorbent according to the present invention is 0.01481 mol / g and the carbon dioxide adsorption amount of the carbon dioxide immobilized adsorbent according to the prior art is It was about three times as large as 0.00514 mol / g.
실시예 2Example 2
도 6은 본 발명에 의한 제 2이산화탄소 고정화 흡착제의 이산화탄소 흡착 성능 결과를 나타낸 그래프이다. 도 6에서 i50%는 종래의 기술에 의한 이산화탄소 고정화 흡착제로서, 표면 개질이 안된 활성탄에 상기 활성탄의 무게 대비 50%의 수산화리튬을 첨착시킨 것이다. p50%는 본 발명에 의한 제 2이산화탄소 고정화 흡착제 로서, 종래의 기술에 의한 이산화탄소 고정화 흡착에 사용한 활성탄과 동일한 활성탄과 수산화리튬 분말을 기계적 혼합을 통해 제조한 것이다. 본 발명에 의한 제 2이산화탄소 고정화 흡착제에서 이산화탄소가 늦게 파괴되고 있다. 이는 본 발명에 의한 제 2이산화탄소 고정화 흡착제의 이산화탄소에 대한 흡착 성능이 우수함을 의미하며, 종래의 기술에 의한 이산화탄소 흡착제는 다량의 수산화리튬이 세공 내에서 성장하여 세공을 막아 주로 이산화탄소의 흡착이 세공 외부에서만 이루어지기 때문이다. 수산화리튬 1g당 흡착된 이산화탄소의 흡착량(mol)에 있어서, 본 발명에 의한 제 2이산화탄소 고정화 흡착제의 이산화탄소 흡착량은 0.03235 mol/g이고 종래의 기술에 의한 이산화탄소 고정화 흡착제의 이산화탄소 흡착량은 0.01752 mol/g으로 약 2배 정도 크게 나타났다. 6 is a graph showing the carbon dioxide adsorption performance results of the second carbon dioxide immobilized adsorbent according to the present invention. In FIG. 6, i50% is a carbon dioxide immobilized adsorbent according to the prior art, in which 50% of lithium hydroxide is added to activated carbon without surface modification by weight of the activated carbon. p50% is the second carbon dioxide immobilized adsorbent according to the present invention, and is prepared by mechanical mixing of the same activated carbon and lithium hydroxide powder as the activated carbon used for carbon dioxide immobilized adsorption according to the prior art. In the second carbon dioxide immobilized adsorbent according to the present invention, carbon dioxide is destroyed late. This means that the adsorption performance of the second carbon dioxide immobilized adsorbent according to the present invention to the carbon dioxide is excellent, the carbon dioxide adsorbent according to the prior art, a large amount of lithium hydroxide grows in the pores to block the pores, so that the adsorption of carbon dioxide mainly outside the pores Because it is only made. In the adsorption amount (mol) of carbon dioxide adsorbed per 1 g of lithium hydroxide, the carbon dioxide adsorption amount of the second carbon dioxide immobilized adsorbent according to the present invention is 0.03235 mol / g, and the carbon dioxide adsorption amount of the carbon dioxide immobilized adsorbent according to the prior art is 0.01752 mol. It was twice as large as / g.
본 발명에 의한 이산화탄소 고정화 흡착제는 종래의 기술에 의한 이산화탄소 고정화 흡착제에 비해 이산화탄소의 흡착 성능이 현전히 개선되어 화력발전소 등과 같은 고정원과 자동차 등과 같은 이동원에서 배출되는 이산화탄소의 분리, 회수에 크게 기여할 것이다. The carbon dioxide immobilized adsorbent according to the present invention will significantly improve the adsorption performance of carbon dioxide compared to the conventional carbon dioxide immobilized adsorbent and will greatly contribute to the separation and recovery of carbon dioxide emitted from fixed sources such as thermal power plants and mobile sources such as automobiles. .
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| KR101312341B1 (en) * | 2011-03-11 | 2013-09-27 | 한국건설기술연구원 | Carbon dioxide absorbent using recycled waste and concrete including the same |
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