KR102627703B1 - Carbon dioxide scavenger for dry type and manufacturing method thereof - Google Patents
Carbon dioxide scavenger for dry type and manufacturing method thereof Download PDFInfo
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- KR102627703B1 KR102627703B1 KR1020230048874A KR20230048874A KR102627703B1 KR 102627703 B1 KR102627703 B1 KR 102627703B1 KR 1020230048874 A KR1020230048874 A KR 1020230048874A KR 20230048874 A KR20230048874 A KR 20230048874A KR 102627703 B1 KR102627703 B1 KR 102627703B1
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- carbon dioxide
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 111
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 111
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000002516 radical scavenger Substances 0.000 title 1
- 238000001179 sorption measurement Methods 0.000 claims abstract description 43
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 16
- 239000002250 absorbent Substances 0.000 claims description 39
- 230000002745 absorbent Effects 0.000 claims description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 230000002265 prevention Effects 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- 229960000892 attapulgite Drugs 0.000 claims description 6
- 229910052625 palygorskite Inorganic materials 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 229940099259 vaseline Drugs 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 3
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 claims description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 10
- 239000006096 absorbing agent Substances 0.000 abstract 2
- 239000002274 desiccant Substances 0.000 abstract 1
- 239000000440 bentonite Substances 0.000 description 10
- 229910000278 bentonite Inorganic materials 0.000 description 10
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- -1 ethylene, propylene, butadiene Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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Abstract
Description
본 발명은 건식용 이산화탄소 포집제 및 그 제조방법에 관한 것으로, 더욱 상세하게는 이산화탄소에 대한 포집성능이 우수할 뿐만 아니라, 수분의 함량이 높은 조건에서도 포집성능이 유지되는 건식용 이산화탄소 포집제 및 그 제조방법에 관한 것이다.The present invention relates to a dry carbon dioxide collector and a method of manufacturing the same, and more specifically, to a dry carbon dioxide collector that not only has excellent carbon dioxide capture performance, but also maintains capture performance even under conditions with a high moisture content, and the same. It is about manufacturing method.
이산화탄소는 저온에서의 동결 및 수분과의 하이드레이트 형성능으로 인해 다수의 상업적인 가스 적용에서 원치 않는불순물로 취급되고 있으며, 고체 또는 고체 입자의 형성은 가스 프로세싱, 작업, 수송 및 저장을 매우 어렵게 하거나 심지어는 불가능 하게 한다. 예를 들면, 산소 및 질소 생산을 위한 공기 분리용 저온 유닛은 실용상, 분리전 공기로부터 이산화탄소(1 ppm 이하) 및 수증기의 완전한 제거를 요구한다. 정련소는 수소-오염된 가스류에 존재하는 이산화탄소와 수분의 양에 대해 유사한 요구조건을 두고 있다. 질소 정제용 암모니아 플랜트 및 가스 프로세싱 플랜트의 경우에도 에탄 및 헬륨 회수에 앞서 및/또는 천연 가스 액화 전 이산화탄소 함량 및 천연가스 이슬점에 대해 유사한 요구조건을 두고 있다. 또한, 석유화학 플랜트는 중합 촉매의 포이즈닝 및 중합체 성질의 저하를 방지하기 위하여 단량체: 에틸렌, 프로필렌, 부타디엔 등에 존재하는 이산화탄소와 수분을 제거하여야 한다.Carbon dioxide is treated as an unwanted impurity in many commercial gas applications due to its ability to freeze at low temperatures and form hydrates with moisture, and the formation of solids or solid particles makes gas processing, operation, transportation and storage very difficult or even impossible. Let it be done. For example, cryogenic units for air separation for oxygen and nitrogen production practically require complete removal of carbon dioxide (less than 1 ppm) and water vapor from the air before separation. Refineries have similar requirements for the amount of carbon dioxide and moisture present in hydrogen-contaminated gas streams. Ammonia plants for nitrogen purification and gas processing plants have similar requirements for carbon dioxide content and natural gas dew point prior to ethane and helium recovery and/or prior to natural gas liquefaction. In addition, petrochemical plants must remove carbon dioxide and moisture present in monomers: ethylene, propylene, butadiene, etc., to prevent poisoning of the polymerization catalyst and deterioration of polymer properties.
이산화탄소 및 수증기의 흡착은 고성능 및 비교적 저 자본 및 운영비로 해서 가스 스트림으로부터 이들 화합물의 가장 일반적인 제거방법이다. 상업적인 가스 제조에는 두 가지 흡착 기술이 통상적으로 사용되고 있다: 온도 스윙(swing)흡착(TSA) 및 압력 스윙 흡착(PSA) 두 흡착법의 효율은 흡착제의 성질에 의해 결정된다. 특히 매우 낮은 분압에서 이산화탄소의 고흡착이 흡착제의 가장 중요한 성질이다.Adsorption of carbon dioxide and water vapor is the most common method of removal of these compounds from gas streams due to its high performance and relatively low capital and operating costs. Two adsorption techniques are commonly used in commercial gas production: temperature swing adsorption (TSA) and pressure swing adsorption (PSA). The efficiency of both adsorption methods is determined by the properties of the adsorbent. In particular, high adsorption of carbon dioxide at very low partial pressure is the most important property of the adsorbent.
몇 가지 유형의 이산화탄소 흡착제가 공업 필요조건을 충족하도록 만들어졌다. 알루미나, 실리카 겔 및 활성탄 같은 일반용 흡착제는 이산화탄소에 대한 실질적인 흡착능을 지니고 있지 않기 때문에, 더욱 복잡한 흡착제가 제조되어 왔다.Several types of carbon dioxide adsorbents have been created to meet industrial requirements. Because common adsorbents such as alumina, silica gel and activated carbon do not have substantial adsorption capacity for carbon dioxide, more complex adsorbents have been manufactured.
그러나, 종래에 이산화탄소 흡착제의 경우는 2%(20,000ppm) 농도의 이산화탄소를 기준으로 한 포집성능이 20mg/g 미만이거나, 수분의 함량이 5 내지 20중량%인 조건에서는 이산화탄소에 대한 포집성능이 현저하게 저하되는 문제점이 있었다.However, in the case of conventional carbon dioxide adsorbents, the capture performance for carbon dioxide is less than 20 mg/g based on 2% (20,000ppm) concentration of carbon dioxide, or the capture performance for carbon dioxide is remarkable under conditions where the moisture content is 5 to 20% by weight. There was a problem with it being degraded.
본 발명의 목적은 이산화탄소에 대한 포집성능이 우수할 뿐만 아니라, 수분의 함량이 높은 조건에서도 포집성능이 유지되는 건식용 이산화탄소 포집제 및 그 제조방법을 제공하는 것이다.The purpose of the present invention is to provide a dry carbon dioxide collector and a manufacturing method thereof that not only have excellent carbon dioxide capture performance, but also maintain capture performance even under conditions of high moisture content.
본 발명의 목적은 이산화탄소 흡착물질, 수분 흡수제, 수분이탈방지제, 무기바인더 및 이산화탄소 흡착반응촉진제로 이루어지며, 상기 수분 흡수제는 비표면적이 100 내지 500cm2/g인 몬모릴로나이트로 이루어지는 것을 특징으로 하는 건식용 이산화탄소 포집제를 제공함에 의해 달성된다.The object of the present invention is to provide a carbon dioxide adsorbent, a moisture absorbent, a moisture escape prevention agent, an inorganic binder, and a carbon dioxide adsorption reaction accelerator, wherein the moisture absorbent is made of montmorillonite with a specific surface area of 100 to 500 cm 2 /g. This is achieved by providing a carbon dioxide capture agent.
본 발명의 바람직한 특징에 따르면, 상기 건식용 이산화탄소 포집제는 이산화탄소 흡착물질 100 중량부, 수분 흡수제 5 내지 25 중량부, 수분이탈방지제 5 내지 12 중량부, 무기바인더 0.1 내지 7 중량부, 이산화탄소 흡착반응촉진제 50 내지 120 중량부로 이루어지는 것으로 한다.According to a preferred feature of the present invention, the dry carbon dioxide collector includes 100 parts by weight of a carbon dioxide adsorbent, 5 to 25 parts by weight of a moisture absorbent, 5 to 12 parts by weight of a moisture escape prevention agent, 0.1 to 7 parts by weight of an inorganic binder, and carbon dioxide adsorption reaction. It shall consist of 50 to 120 parts by weight of accelerator.
본 발명의 더 바람직한 특징에 따르면, 상기 이산화탄소 흡착물질은 수산화칼슘, 산화칼슘, 산화칼륨, 이산화규소, 리튬실리케이트 및 산화암모늄으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the carbon dioxide adsorption material is made of one or more selected from the group consisting of calcium hydroxide, calcium oxide, potassium oxide, silicon dioxide, lithium silicate, and ammonium oxide.
본 발명의 더욱 바람직한 특징에 따르면, 상기 수분 흡수제는 50 내지 200㎛의 입자크기를 나타내는 것으로 한다.According to a more preferred feature of the present invention, the moisture absorbent has a particle size of 50 to 200㎛.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 수분이탈방지제는 트리에틸아민, 바세린 및 글리세린으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것으로 한다.According to an even more preferred feature of the present invention, the moisture escape prevention agent is made of at least one selected from the group consisting of triethylamine, vaseline, and glycerin.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 무기 바인더는 벤토나이트, 애터펄자이트 점토, 실리카, 알루미나, 실리카-알루미나 졸 및 알루모실리케이트로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것으로 한다.According to an even more preferred feature of the present invention, the inorganic binder is made of one or more selected from the group consisting of bentonite, attapulgite clay, silica, alumina, silica-alumina sol, and alumosilicate.
본 발명의 더욱 더 바람직한 특징에 따르면, 상기 이산화탄소 흡착반응제는 수산화칼륨, 수산화나트륨 및 수산화암모늄으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것으로 한다.According to an even more preferred feature of the present invention, the carbon dioxide adsorption reactive agent is made of at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, and ammonium hydroxide.
또한, 본 발명의 목적은 수분 흡수제를 50 내지 200㎛의 입자크기로 분쇄하는 수분흡수제분쇄단계, 상기 수분흡수제분쇄단계를 통해 제조된 수분 흡수제, 이산화탄소 흡착물질, 수분이탈방지제, 무기바인더 및 이산화탄소 흡착반응촉진제를 혼합하는 원료혼합단계, 상기 원료혼합단계를 통해 제조된 혼합물을 성형하는 성형단계 및 상기 성형단계를 통해 제조된 성형물을 80 내지 200℃의 온도에서 2 내지 24시간 동안 건조하는 건조단계로 이루어지며, 상기 수분 흡수제는 비표면적이 100 내지 500cm2/g인 몬모릴로나이트로 이루어지는 것을 특징으로 하는 건식용 이산화탄소 포집제의 제조방법을 제공함에 의해 달성될 수도 있다.In addition, the object of the present invention is to pulverize the moisture absorbent into a particle size of 50 to 200㎛, a moisture absorbent produced through the moisture absorbent grinding step, a carbon dioxide adsorption material, a moisture escape prevention agent, an inorganic binder, and carbon dioxide adsorption. A raw material mixing step of mixing the reaction accelerator, a molding step of molding the mixture prepared through the raw material mixing step, and a drying step of drying the molded product manufactured through the molding step at a temperature of 80 to 200 ° C. for 2 to 24 hours. This can also be achieved by providing a method for producing a dry carbon dioxide collector, wherein the moisture absorbent is made of montmorillonite with a specific surface area of 100 to 500 cm 2 /g.
본 발명에 따른 건식용 이산화탄소 포집제 및 그 제조방법은 이산화탄소에 대한 포집성능이 우수할 뿐만 아니라, 수분의 함량이 높은 조건에서도 포집성능이 유지되는 건식용 이산화탄소 포집제를 제공하는 탁월한 효과를 나타낸다.The dry carbon dioxide collector and its manufacturing method according to the present invention not only have excellent carbon dioxide capture performance, but also have an excellent effect of providing a dry carbon dioxide collector that maintains capture performance even under conditions of high moisture content.
도 1은 본 발명에 따른 건식용 이산화탄소 포집제의 제조방법을 나타낸 순서도이다.
도 2는 본 발명을 통해 제조된 건식용 이산화탄소 포집제의 구조를 나타낸 모식도이다.
도 3은 본 발명의 실시예 1 및 비교예 1 내지 3을 통해 제조된 건식용 이산화탄소 포집제의 외관을 촬영하여 나타낸 사진이다.Figure 1 is a flowchart showing a method of manufacturing a dry carbon dioxide collector according to the present invention.
Figure 2 is a schematic diagram showing the structure of a dry carbon dioxide collector manufactured through the present invention.
Figure 3 is a photograph showing the appearance of the dry carbon dioxide collector prepared through Example 1 and Comparative Examples 1 to 3 of the present invention.
이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Below, preferred embodiments of the present invention and the physical properties of each component are described in detail, but are intended to be described in detail so that those skilled in the art can easily practice the invention. This does not mean that the technical idea and scope of the present invention are limited.
본 발명에 따른 건식용 이산화탄소 포집제는 이산화탄소 흡착물질. 수분 흡수제, 수분이탈방지제, 무기바인더 및 이산화탄소 흡착반응촉진제로 이루어지며, 이산화탄소 흡착물질 100 중량부, 수분 흡수제 5 내지 25 중량부, 수분이탈방지제 5 내지 12 중량부, 무기바인더 0.1 내지 7 중량부, 이산화탄소 흡착반응촉진제 50 내지 120 중량부로 이루어지는 것이 바람직하다.The dry carbon dioxide collector according to the present invention is a carbon dioxide adsorbent. It consists of a moisture absorbent, a moisture escape prevention agent, an inorganic binder, and a carbon dioxide adsorption reaction accelerator, including 100 parts by weight of the carbon dioxide adsorption material, 5 to 25 parts by weight of the moisture absorbent, 5 to 12 parts by weight of the moisture escape prevention agent, and 0.1 to 7 parts by weight of the inorganic binder, It is preferable that the carbon dioxide adsorption reaction accelerator is comprised of 50 to 120 parts by weight.
상기 이산화탄소 흡착물질은 수산화칼슘, 산화칼슘, 산화칼륨, 이산화규소, 리튬실리케이트 및 산화암모늄으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는데, 이산화탄소를 흡착하여 포집성능을 부가하는 역할을 한다.The carbon dioxide adsorption material is made of one or more selected from the group consisting of calcium hydroxide, calcium oxide, potassium oxide, silicon dioxide, lithium silicate, and ammonium oxide, and serves to add capture performance by adsorbing carbon dioxide.
상기 이산화탄소 흡착물질의 이산화탄소 포집원리를 아래 반응식으로 나타내었다.The carbon dioxide capture principle of the carbon dioxide adsorption material is shown in the reaction equation below.
<반응식><Reaction formula>
Ca(OH)2 + CO2 → CaCO3 + H2OCa(OH) 2 + CO 2 → CaCO 3 + H 2 O
CO2 + H2O ↔ H2CO3 ↔ HCO3 - + H+ CO 2 + H 2 O ↔ H 2 CO 3 ↔ HCO 3 - + H +
HCO3 - ↔ CO3 2- + H+ HCO 3 - ↔ CO 3 2- + H +
CO2 + H2O ↔ H2CO3 ↔ HCO3 - + H+ ↔ CO3 2- + 2H+ CO 2 + H 2 O ↔ H 2 CO 3 ↔ HCO 3 - + H + ↔ CO 3 2- + 2H +
CO2 + 2NH3 + H2O → (NH4)2CO3 CO 2 + 2NH 3 + H 2 O → (NH 4 ) 2 CO 3
2NaOH + CO2 → Na2CO3 + H2O2NaOH + CO 2 → Na 2 CO 3 + H 2 O
2KOH + CO2 → K2CO3 + H2O2KOH + CO 2 → K 2 CO 3 + H 2 O
상기 수분 흡수제는 5 내지 25 중량부가 함유되며, 50 내지 200㎛의 입자크기를 나타내는 몬모릴로나이트로 이루어지는 것이 바람직하며, 비표면적이 100 내지 500cm2/g인 몬모릴로나이트로 이루어지는 것이 바람직하다.The moisture absorbent contains 5 to 25 parts by weight, and is preferably made of montmorillonite with a particle size of 50 to 200 ㎛, and has a specific surface area of 100 to 500 cm 2 /g.
일반적으로, 이산화탄소 포집제에 수분(H2O)이 유입되면 이산화탄소는 수분과 반응하여 수소이온 농도가 증가하게 되는데, 이는 곧 pH를 하강시켜 산성화가 진행 되어 일정 시간이 경화하면 더이상 이산화탄소를 포집할 수 없게 되는데, 기존에는 이러한 문제로 인해 고온 및 고압의 포집환경 조건에서 이산화탄소를 포집해야 하는 불편함이 있었다.Generally, when moisture (H 2 O) flows into the carbon dioxide collector, the carbon dioxide reacts with the moisture and increases the hydrogen ion concentration. This soon lowers the pH and causes acidification, so that it can no longer collect carbon dioxide after it hardens for a certain period of time. Previously, due to this problem, there was the inconvenience of having to collect carbon dioxide in high temperature and high pressure capture environment conditions.
그러나, 상기의 입자크기를 나타내는 몬모릴로나이트는 수분을 흡수하고 이온교환는 기능을 나타내기 때문에, 포집제의 수분 저항력을 향상시키는 역할을 하는데, 밀실한 구조 내에서 해리되어 나오는 음이온(HCO3 -, CO3 2-)과 알칼리이온(Ca+, Na+, NH+ 등)의 중화반응을 유도시켜 포집제의 포집성능을 향상시킬 뿐만 아니라, 수소이온을 발생시켜 이산화탄소와 탄산염 형태로 결합할 수 있게 지속적으로 물(H2O)로 산화되어 존재하게 되는데, 이때, 상기의 성분으로 이루어지는 수분 흡수제가 수소이온의 산화력을 유지시켜 주기 때문에, 포집제의 성능을 향상 및 유지시켜 주는 역할을 하게 된다.However, since montmorillonite with the above particle size absorbs moisture and exhibits an ion exchange function, it plays a role in improving the moisture resistance of the collector. Anions (HCO 3 - , CO 3 ) that dissociate within the tight structure are released. It not only improves the collection performance of the collector by inducing a neutralization reaction of 2- ) and alkali ions (Ca + , Na + , NH + , etc.), but also generates hydrogen ions to continuously combine with carbon dioxide in the form of carbonate. It exists after being oxidized to water (H 2 O). At this time, the moisture absorbent composed of the above components maintains the oxidizing power of hydrogen ions, thereby playing a role in improving and maintaining the performance of the collector.
이때, 상기 수분 흡수제로 사용되는 몬모릴로나이트(Montmorillonite)는 점토광물로서 수분 흡수력, 양이온 교환능력을 나타내며, 무기화합물과의 복합체 제조를 위해 밀실하고 균일한 Pore를 형성하기 위해 50 내지 200㎛의 입자크기를 나타내도록 분쇄하여 적용되는 것이 바람직하다.At this time, Montmorillonite, which is used as the moisture absorbent, is a clay mineral that exhibits moisture absorption and cation exchange ability, and has a particle size of 50 to 200㎛ to form a tight and uniform pore for the production of a complex with an inorganic compound. It is preferable to apply it by crushing it so that it appears.
또한, 상기 수분 흡수제는 비표면적이 100 내지 500cm2/g을 나타내도록 제조되는 것이 더욱 바람직한데, 상기의 비표면적을 나타내는 수분 흡수제는 상기에 나열된 효과를 충분히 만족시키면서도 이산화탄소에 대한 포집성능이 더욱 향상된 포집제를 제공하게 된다.In addition, it is more preferable that the moisture absorbent is manufactured to have a specific surface area of 100 to 500 cm 2 /g, and the moisture absorbent having the above specific surface area sufficiently satisfies the effects listed above and has further improved carbon dioxide capture performance. A collecting agent is provided.
이때, 상기의 비표면적을 나타내는 몬모릴로나이트의 제조는 특별히 한정되지 않지만, 벤토나이트(bentonite)를 왕수(aqua regia)에 용해시키고, 벤토나이트가 용해된 왕수 용액에 3 내지 7M의 수산화나트륨(NaOH)을 첨가하여 합성 용액을 제조하고, 제조된 합성 용액을 90℃ 이상 100℃ 미만의 온도에서 유지하여 몬모릴로나이트 결정을 합성하는 과정을 통해 제조될 수 있다.At this time, the production of montmorillonite having the above specific surface area is not particularly limited, but bentonite is dissolved in aqua regia and 3 to 7 M of sodium hydroxide (NaOH) is added to the aqua regia solution in which bentonite is dissolved. It can be manufactured through a process of preparing a synthetic solution and maintaining the prepared synthetic solution at a temperature of 90°C or more and less than 100°C to synthesize montmorillonite crystals.
상기의 비표면적을 나타내는 몬모릴로나이트가 함유되어 제조되는 포집제는 비표면적이 100 내지 500m2/g을 나타내어 우수한 이산화탄소 포집효과를 나타낼 수 있다. The collector manufactured by containing montmorillonite showing the above specific surface area has a specific surface area of 100 to 500 m 2 /g and can exhibit excellent carbon dioxide capturing effect.
상기 수분이탈방지제는 5 내지 12 중량부가 함유되며, 트리에틸아민, 바세린 및 글리세린으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는데, flow 유지 상태에서 발생되는 수분 이탈을 최소화하여 포집 반응시간을 증가시켜, 결과적으로는 포집성능을 형상시키는 역할을 한다.The moisture escape prevention agent contains 5 to 12 parts by weight and is made of one or more selected from the group consisting of triethylamine, vaseline, and glycerin. It minimizes moisture escape that occurs during flow maintenance, increases the collection reaction time, and results in It plays a role in shaping the collection performance.
상기 수분이탈방지제의 함량이 5 중량부 미만이면 상기의 효과가 미미하며, 상기 수분이탈방지제의 함량이 12 중량부를 초과하게 되면 상기의 효과는 크게 향상되지 않으면서 본 발명을 통해 제조되는 건식용 이산화탄소 포집제의 포집성능을 저하시키기 때문에 바람직하지 못하다.If the content of the moisture escape prevention agent is less than 5 parts by weight, the effect is minimal, and if the content of the moisture escape prevention agent exceeds 12 parts by weight, the effect is not significantly improved, and the dry carbon dioxide produced through the present invention This is undesirable because it reduces the collection performance of the collector.
상기 무기 바인더는 0.1 내지 7 중량부가 함유되며, 벤토나이트, 애터펄자이트 점토, 실리카, 알루미나, 실리카-알루미나 졸 및 알루모실리케이트로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것이 바람직하다.The inorganic binder contains 0.1 to 7 parts by weight, and is preferably made of at least one selected from the group consisting of bentonite, attapulgite clay, silica, alumina, silica-alumina sol, and alumosilicate.
상기의 성분으로 이루어지는 무기 바인더는 상기의 이산화탄소 흡착물질, 수분 흡수제, 수분이탈방지제 및 이산화탄소 흡착반응촉지제를 결속시켜 일정한 형태를 나타내는 포집제가 제공될 수 있도록 하는 역할을 한다.The inorganic binder composed of the above components serves to bind the carbon dioxide adsorption material, moisture absorbent, moisture escape prevention agent, and carbon dioxide adsorption reaction accelerator to provide a collector having a certain shape.
상기 무기바인더의 함량이 0.1 중량부 미만이면 제조되는 포집제의 기계적 물성인 형태안정성이 저하되며, 상기 무기바인더의 함량이 7 중량부를 초과하게 되면 상기의 효과는 크게 향상되지 않으면서 제조되는 포집제의 이산화탄소 포집성능이 저하되기 때문에 바람직하지 못하다.If the content of the inorganic binder is less than 0.1 parts by weight, the dimensional stability, which is a mechanical property of the manufactured collector, decreases, and if the content of the inorganic binder exceeds 7 parts by weight, the above effect is not significantly improved. This is undesirable because its carbon dioxide capture performance is reduced.
상기 이산화탄소 흡착반응촉진제는 50 내지 120 중량부가 함유되며, 수산화칼륨, 수산화나트륨 및 수산화암모늄으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는데, 알칼리이온형태로 존재하면서 상기 수분 흡수제와 이산화탄 흡착물질의 밀실한 구조에 이온상태로 존재하며, 이산화탄소의 중화반응을 촉진시켜 흡착반응속도를 향상시키는 역할을 한다.The carbon dioxide adsorption reaction accelerator contains 50 to 120 parts by weight and is made of at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, and ammonium hydroxide. It exists in the form of an alkali ion and acts as a tight seal between the moisture absorbent and the carbon dioxide adsorption material. It exists in an ionic state in the structure and plays a role in improving the adsorption reaction rate by promoting the neutralization reaction of carbon dioxide.
또한, 본 발명에 따른 건식용 이산화탄소 포집제의 제조방법은 수분 흡수제를 50 내지 200㎛의 입자크기로 분쇄하는 수분흡수제분쇄단계(S101), 상기 수분흡수제분쇄단계(S101)를 통해 제조된 수분 흡수제, 이산화탄소 흡착물질, 수분이탈방지제, 무기바인더 및 이산화탄소 흡착반응촉진제를 혼합하는 원료혼합단계(S103), 상기 원료혼합단계를 통해 제조된 혼합물을 성형하는 성형단계(S105) 및 상기 성형단계(S105)를 통해 제조된 성형물을 80 내지 200℃의 온도에서 2 내지 24시간 동안 건조하는 건조단계(S107)로 이루어진다.In addition, the method for producing a dry carbon dioxide collector according to the present invention includes a moisture absorbent grinding step (S101) of pulverizing the moisture absorbent into a particle size of 50 to 200 ㎛, and a moisture absorbent produced through the moisture absorbent grinding step (S101). , a raw material mixing step (S103) of mixing a carbon dioxide adsorption material, a moisture escape prevention agent, an inorganic binder, and a carbon dioxide adsorption reaction accelerator, a molding step (S105) of molding the mixture prepared through the raw material mixing step, and the molding step (S105). It consists of a drying step (S107) in which the molded product manufactured through is dried at a temperature of 80 to 200 ° C. for 2 to 24 hours.
상기 수분흡수제분쇄단계(S101)는 수분 흡수제를 분쇄하는 단계로, 수분 흡수제로 사용되는 몬모릴로나이트를 50 내지 200㎛의 입자크기로 분쇄하여 이루어지는데, 몬모릴로나이트의 입자크기에 대한 임계적 의의는 상기 건식용 이산화탄소 포집제에 기재된 내용과 동일하므로 이에 대한 설명은 생략하기로 한다.The moisture absorbent grinding step (S101) is a step of pulverizing the moisture absorbent, and is achieved by grinding montmorillonite, which is used as a moisture absorbent, into a particle size of 50 to 200㎛. The critical significance of the particle size of montmorillonite is the dry use. Since it is the same as the information described in the carbon dioxide capture agent, the description thereof will be omitted.
상기 원료혼합단계(S103)는 상기 수분흡수제분쇄단계(S101)를 통해 제조된 수분 흡수제, 이산화탄소 흡착물질, 수분이탈방지제, 무기바인더 및 이산화탄소 흡착반응촉진제를 혼합하는 단계로, 이산화탄소 흡착물질 100 중량부, 상기 수분흡수제분쇄단계를 통해 제조된 수분 흡수제 5 내지 25 중량부, 수분이탈방지제 5 내지 12 중량부, 무기바인더 0.1 내지 7 중량부, 이산화탄소 흡착반응촉진제 50 내지 120 중량부를 혼합하여 이루어지는 것이 바람직하다.The raw material mixing step (S103) is a step of mixing the moisture absorbent, carbon dioxide adsorbent, moisture escape prevention agent, inorganic binder, and carbon dioxide adsorption reaction accelerator prepared through the moisture absorbent grinding step (S101), and 100 parts by weight of carbon dioxide adsorbent material. , It is preferable to mix 5 to 25 parts by weight of the moisture absorbent prepared through the moisture absorbent grinding step, 5 to 12 parts by weight of the moisture escape prevention agent, 0.1 to 7 parts by weight of the inorganic binder, and 50 to 120 parts by weight of the carbon dioxide adsorption reaction accelerator. .
이때, 상기 이산화탄소 흡착물질, 수분 흡수제, 수분이탈방지제, 무기바인더 및 이산화탄소 흡착반응촉진제의 성분 및 함량에 따른 임계적 의의는 상기 건식용 이산화탄소 포집제에 기재된 내용과 동일하므로 이에 대한 설명은 생략하기로 한다.At this time, the critical significance of the components and contents of the carbon dioxide adsorbent, moisture absorbent, moisture escape prevention agent, inorganic binder, and carbon dioxide adsorption reaction accelerator is the same as that described in the dry carbon dioxide collector, so description thereof will be omitted. do.
상기 건조단계(S107)는 상기 성형단계(S105)를 통해 제조된 성형물을 건조하는 단계로, 상기 성형단계(S105)를 통해 제조된 성형물을 80 내지 200℃의 온도에서 2 내지 24시간 동안 건조하여 이루어지는데, 이산화탄소가 제거된 환경에서 80 내지 200℃의 온도에서 2 내지 24시간 동안 건조하게 되면 포집제의 불필요한 수분, 불순물 및 유기용매 등의 성분은 제거되어 우수한 포집성능을 나타내는 포집제가 제조될 수 있다.The drying step (S107) is a step of drying the molded product manufactured through the molding step (S105). The molded product manufactured through the molding step (S105) is dried at a temperature of 80 to 200 ° C. for 2 to 24 hours. When dried at a temperature of 80 to 200°C for 2 to 24 hours in an environment where carbon dioxide is removed, components such as unnecessary moisture, impurities and organic solvents of the collector are removed, and a collector that exhibits excellent collection performance can be manufactured. there is.
상기 건조단계(S107)의 건조온도가 80℃ 미만이거나 건조시간이 2시간 미만이면 포집제에 수분이 과다하게 존재하여 강도가 떨어져 공정에서 차압 발생으로 제대로된 성능을 발휘하기가 어려우며, 상기 건조단계(S105)의 건조온도가 200℃를 초과하거나 건조시간이 24시간을 초과하게 되면 포집제를 구성하는 일부 성분의 상변이가 이루어져 전혀 다른 특성을 갖는 결정구조가 형성되어 이산화탄소 포집성능이 저하되기 때문에 바람직하지 못하다.If the drying temperature in the drying step (S107) is less than 80°C or the drying time is less than 2 hours, excessive moisture is present in the collector and the strength is reduced, making it difficult to perform properly due to differential pressure generation in the process, and the drying step ( If the drying temperature of S105) exceeds 200°C or the drying time exceeds 24 hours, a phase transition occurs in some of the components constituting the collector, forming a crystal structure with completely different characteristics, which is desirable because carbon dioxide capture performance deteriorates. can't do it
이하에서는, 본 발명에 따른 건식용 이산화탄소 포집제의 제조방법 및 그 제조방법으로 제조된 포집제의 물성을 실시예를 들어 설명하기로 한다.Hereinafter, the method for manufacturing a dry carbon dioxide collector according to the present invention and the physical properties of the collector produced by the method will be described using examples.
<제조예 1> 몬모릴로 나이트의 제조<Preparation Example 1> Preparation of montmorilloite
1mm 이하의 크기를 갖는 벤토나이트 분말 3g을 왕수 20mL에 용해시켰다. 이 때, 상기 벤토나이트 분말로는 국내 경주지역의 감포40호(Gampo40) 광산에서 채취한 칼슘형 벤토나이트를 파분쇄한 후 1 mm 이하(No 18 sieve 또는 16 Mesh) 크기의 분말을 선별하여 사용하였고, 상기 왕수로는 염산과 질산을 3:1의 부피비로 혼합한 혼합물을 사용하였으며, 상기 벤토나이트 분말을 상기 왕수에 투입한 후 4시간 동안 교반하여 상기 벤토나이트 분말을 완전히 용해시켰다. 상기 벤토나이트 분말이 용해된 왕수 용액에 4M 농도의 수산화나트륨(NaOH) 수용액 50mL를 첨가한 후 실온에서 4시간 동안 교반하여 합성 용액을 제조하였다. 상기 합성 용액의 pH는 12.3으로 측정되었다. 상기 합성 용액을 수열 합성 용기 내에 밀봉한 후 95℃ 온도의 오븐에 넣고 24시간 동안 유지하여 몬모릴로 나이트를 제조하였다. 상기의 과정으로 제조된 몬모릴로 나이트의 비표면적을 비표면적 측정기(Macsorb)로 측정한 결과 300.420cm2/g을 나타내었다.3 g of bentonite powder with a size of 1 mm or less was dissolved in 20 mL of aqua regia. At this time, the bentonite powder was used by crushing calcium-type bentonite collected from the Gampo40 mine in Gyeongju, Korea, and selecting powder with a size of 1 mm or less (No 18 sieve or 16 mesh). As the aqua regia, a mixture of hydrochloric acid and nitric acid at a volume ratio of 3:1 was used, and the bentonite powder was added to the aqua regia and stirred for 4 hours to completely dissolve the bentonite powder. A synthetic solution was prepared by adding 50 mL of a 4M sodium hydroxide (NaOH) aqueous solution to the aqua regia solution in which the bentonite powder was dissolved and stirring it at room temperature for 4 hours. The pH of the synthesis solution was measured to be 12.3. The synthesis solution was sealed in a hydrothermal synthesis vessel, placed in an oven at 95°C, and maintained for 24 hours to prepare montmorillonite. The specific surface area of the montmorillonite prepared through the above process was measured using a specific surface area measuring device (Macsorb) and found to be 300.420 cm 2 /g.
<실시예 1><Example 1>
상기 제조예 1을 통해 제조된 몬모릴로 나이트를 50 내지 200㎛로 분쇄하여 제조된 수분 흡수제 10 중량부, 수분이탈방지제(트리에틸아민) 5 중량부, 이산화탄소 흡착물질(수산화칼슘) 85 중량부, 무기 바인더(애터펄자이트) 1 중량부 및 이산화탄소 흡착반응촉진제(수산화칼륨) 60 중량부를 교반기가 구비된 혼합장치에 투입하고 300rpm으로 1시간 동안 교반하여 혼합물을 제조하고, 제조된 혼합물을 펠릿형태로 압출성형한 후에, 제조된 성형물을 80℃의 온도에서 4시간 동안 건조하여 건식용 이산화탄소 포집제를 제조하였다.10 parts by weight of moisture absorbent prepared by pulverizing the montmorillonite prepared through Preparation Example 1 to 50 to 200㎛, 5 parts by weight of moisture escape prevention agent (triethylamine), 85 parts by weight of carbon dioxide adsorption material (calcium hydroxide), inorganic Add 1 part by weight of binder (attapulgite) and 60 parts by weight of carbon dioxide adsorption reaction accelerator (potassium hydroxide) into a mixing device equipped with a stirrer and stir at 300 rpm for 1 hour to prepare a mixture, and form the prepared mixture into pellets. After extrusion molding, the manufactured molded product was dried at a temperature of 80°C for 4 hours to prepare a dry carbon dioxide collector.
<비교예 1><Comparative Example 1>
제올라이트 15 중량부, 이산화탄소 흡착물질(수산화칼슘) 85 중량부 및 무기 바인더(애터펄자이트) 1 중량부 및 이산화탄소 흡착반응촉진제(수산화칼륨) 60 중량부를 교반기가 구비된 혼합장치에 투입하고 300rpm으로 1시간 동안 교반하여 혼합물을 제조하고, 제조된 혼합물을 펠릿형태로 압출성형한 후에, 제조된 성형물을 80℃의 온도에서 4시간 동안 건조하여 건식용 이산화탄소 포집제를 제조하였다.15 parts by weight of zeolite, 85 parts by weight of carbon dioxide adsorption material (calcium hydroxide), 1 part by weight of inorganic binder (attapulgite), and 60 parts by weight of carbon dioxide adsorption reaction accelerator (potassium hydroxide) were placed in a mixing device equipped with a stirrer and mixed at 300 rpm. A mixture was prepared by stirring for a period of time, and the prepared mixture was extruded into pellet form, and then the prepared molded product was dried at a temperature of 80° C. for 4 hours to prepare a dry carbon dioxide collector.
<비교예 2><Comparative Example 2>
다공성 실리카 15 중량부, 이산화탄소 흡착물질(수산화칼슘) 85 중량부 및 상기 혼합물 100 중량부에 대하여 무기 바인더(애터펄자이트) 1 중량부 및 이산화탄소 흡착반응촉진제(수산화칼륨) 60 중량부 에 상기 혼합물 100 중량부에 대하여 KOH 용액 60 중량부를 교반기가 구비된 혼합장치에 투입하고 300rpm으로 1시간 동안 교반하여 혼합물을 제조하고, 제조된 혼합물을 펠릿형태로 압출성형한 후에 80℃의 온도에서 4시간 동안 건조하여 펠렛형태로 압출성형하여 건식용 이산화탄소 포집제를 제조하였다.15 parts by weight of porous silica, 85 parts by weight of carbon dioxide adsorption material (calcium hydroxide), 1 part by weight of inorganic binder (atpulgite) and 60 parts by weight of carbon dioxide adsorption reaction accelerator (potassium hydroxide) per 100 parts by weight of the mixture, 100 parts by weight of the mixture. 60 parts by weight of KOH solution was added to a mixing device equipped with a stirrer and stirred at 300 rpm for 1 hour to prepare a mixture. The prepared mixture was extruded into pellets and dried at a temperature of 80°C for 4 hours. A dry carbon dioxide collector was manufactured by extrusion molding into pellet form.
<비교예 3><Comparative Example 3>
탄소체 120 중량부, 이산화탄소 흡착물질(수산화칼슘) 200 중량부, 무기 바인더(애터펄자이트) 1 중량부 및 이산화탄소 흡착반응촉진제(수산화칼륨) 60 중량부를 교반기가 구비된 혼합장치에 투입하고 300rpm으로 1시간 동안 교반하여 혼합물을 제조하고, 제조된 혼합물을 펠릿형태로 압출성형한 후에 80℃의 온도에서 4시간 동안 건조하여 펠렛형태로 압출성형하여 건식용 이산화탄소 포집제를 제조하였다.120 parts by weight of carbon body, 200 parts by weight of carbon dioxide adsorption material (calcium hydroxide), 1 part by weight of inorganic binder (atapulgite), and 60 parts by weight of carbon dioxide adsorption reaction accelerator (potassium hydroxide) were placed in a mixing device equipped with a stirrer and stirred at 300 rpm. The mixture was prepared by stirring for 1 hour, and the prepared mixture was extruded into pellet form, dried at a temperature of 80°C for 4 hours, and extruded into pellet form to prepare a dry carbon dioxide collector.
상기 실시예 1 및 비교예 1 내지 3을 통해 제조된 건식용 이산화탄소 포집제의 비표면적과 이산화탄소 포집성능을 측정하여 아래 표 1에 나타내었다. 또한, 아래 도 3에 실시예 1 및 비교예 1 내지 3을 통해 제조된 건식용 이산화탄소 포집제의 외관을 촬영하여 나타내었다.The specific surface area and carbon dioxide capture performance of the dry carbon dioxide collectors prepared through Example 1 and Comparative Examples 1 to 3 were measured and shown in Table 1 below. In addition, Figure 3 below shows the appearance of the dry carbon dioxide collector manufactured through Example 1 and Comparative Examples 1 to 3 by photographing them.
{단, 비표면적은 비표면적 측정기(Macsorb)를 이용하여 측정하였으며, 이산화탄소 포집성능은 2000ppm의 이산화탄소농도 기준 공간속도 2000 h-1를 측정대상으로 하여 측정한 결과이다.}{However, the specific surface area was measured using a specific surface area measuring device (Macsorb), and the carbon dioxide capture performance was measured using a space velocity of 2000 h -1 based on a carbon dioxide concentration of 2000 ppm.}
<표 1><Table 1>
상기 표 1에 나타낸 것처럼, 본 발명의 실시예 1을 통해 제조된 건식용 이산화탄소 포집제는 상온 조건에서도 우수한 이산화탄소 포집성능을 나타내는 것을 알 수 있다.As shown in Table 1, it can be seen that the dry carbon dioxide collector prepared through Example 1 of the present invention exhibits excellent carbon dioxide capture performance even at room temperature conditions.
따라서, 본 발명에 따른 건식용 이산화탄소 포집제 및 그 제조방법은 이산화탄소에 대한 포집성능이 우수할 뿐만 아니라, 수분의 함량이 높은 조건에서도 포집성능이 유지되는 건식용 이산화탄소 포집제를 제공한다.Therefore, the dry carbon dioxide collector and its manufacturing method according to the present invention not only have excellent carbon dioxide capture performance, but also provide a dry carbon dioxide collector that maintains capture performance even under conditions of high moisture content.
S101 ; 수분흡수제분쇄단계
S103 ; 원료혼합단계
S105 ; 성형단계
S107 ; 건조단계S101 ; Moisture absorbent grinding step
S103 ; Raw material mixing stage
S105 ; Molding stage
S107 ; drying stage
Claims (8)
상기 수분 흡수제는 비표면적이 100 내지 500cm2/g인 몬모릴로나이트로 이루어지고,
상기 수분이탈방지제는 트리에틸아민 및 바세린으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지며,
상기 무기 바인더는 애터펄자이트 점토로 이루어지는 것을 특징으로 하는 건식용 이산화탄소 포집제.
It consists of 100 parts by weight of carbon dioxide adsorption material, 5 to 25 parts by weight of moisture absorbent, 5 to 12 parts by weight of moisture escape prevention agent, 0.1 to 7 parts by weight of inorganic binder, and 50 to 120 parts by weight of carbon dioxide adsorption reaction accelerator,
The moisture absorbent is made of montmorillonite with a specific surface area of 100 to 500 cm 2 /g,
The moisture escape prevention agent consists of one or more selected from the group consisting of triethylamine and vaseline,
A dry carbon dioxide collector, characterized in that the inorganic binder is made of attapulgite clay.
상기 이산화탄소 흡착물질은 수산화칼슘, 산화칼슘, 산화칼륨, 이산화규소, 리튬실리케이트 및 산화암모늄으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것을 특징으로 하는 건식용 이산화탄소 포집제.
In claim 1,
The carbon dioxide adsorption material is a dry carbon dioxide collector, characterized in that it consists of one or more selected from the group consisting of calcium hydroxide, calcium oxide, potassium oxide, silicon dioxide, lithium silicate, and ammonium oxide.
상기 수분 흡수제는 50 내지 200㎛의 입자크기를 나타내는 것을 특징으로 하는 건식용 이산화탄소 포집제.
In claim 1,
The moisture absorbent is a dry carbon dioxide collector, characterized in that it exhibits a particle size of 50 to 200㎛.
상기 이산화탄소 흡착반응촉진제는 수산화칼륨, 수산화나트륨 및 수산화암모늄으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것을 특징으로 하는 건식용 이산화탄소 포집제.
In claim 1,
The carbon dioxide adsorption reaction accelerator is a dry carbon dioxide collector, characterized in that it consists of one or more selected from the group consisting of potassium hydroxide, sodium hydroxide, and ammonium hydroxide.
상기 수분흡수제분쇄단계를 통해 제조된 이산화탄소 흡착물질 100 중량부, 수분 흡수제 5 내지 25 중량부, 수분이탈방지제 5 내지 12 중량부, 무기바인더 0.1 내지 7 중량부 및 이산화탄소 흡착반응촉진제 50 내지 120 중량부를 혼합하는 원료혼합단계;
상기 원료혼합단계를 통해 제조된 혼합물을 성형하는 성형단계; 및
상기 성형단계를 통해 제조된 성형물을 80 내지 200℃의 온도에서 2 내지 24시간 동안 건조하는 건조단계;로 이루어지며,
상기 수분 흡수제는 비표면적이 100 내지 500cm2/g인 몬모릴로나이트로 이루어지고,
상기 수분이탈방지제는 트리에틸아민 및 바세린으로 이루어진 그룹에서 선택된 하나 이상으로 이루어지며,
상기 무기 바인더는 애터펄자이트 점토로 이루어지는 것을 특징으로 하는 건식용 이산화탄소 포집제의 제조방법.A moisture absorbent grinding step of pulverizing the moisture absorbent into particle sizes of 50 to 200㎛;
100 parts by weight of the carbon dioxide adsorption material prepared through the moisture absorbent grinding step, 5 to 25 parts by weight of the moisture absorbent, 5 to 12 parts by weight of the moisture escape prevention agent, 0.1 to 7 parts by weight of the inorganic binder, and 50 to 120 parts by weight of the carbon dioxide adsorption reaction accelerator. Raw material mixing step of mixing;
A molding step of molding the mixture prepared through the raw material mixing step; and
It consists of a drying step of drying the molded product manufactured through the molding step at a temperature of 80 to 200 ° C. for 2 to 24 hours,
The moisture absorbent is made of montmorillonite with a specific surface area of 100 to 500 cm 2 /g,
The moisture escape prevention agent consists of one or more selected from the group consisting of triethylamine and vaseline,
A method for producing a dry carbon dioxide collector, characterized in that the inorganic binder is made of attapulgite clay.
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