KR20120062323A - High efficiency absorbent for capturing carbon dioxide from exhaust gas - Google Patents
High efficiency absorbent for capturing carbon dioxide from exhaust gas Download PDFInfo
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- KR20120062323A KR20120062323A KR1020100123536A KR20100123536A KR20120062323A KR 20120062323 A KR20120062323 A KR 20120062323A KR 1020100123536 A KR1020100123536 A KR 1020100123536A KR 20100123536 A KR20100123536 A KR 20100123536A KR 20120062323 A KR20120062323 A KR 20120062323A
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- carbon dioxide
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- dendrimer
- amine
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 66
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 65
- 230000002745 absorbent Effects 0.000 title claims abstract description 61
- 239000002250 absorbent Substances 0.000 title claims abstract description 61
- 239000000412 dendrimer Substances 0.000 claims abstract description 32
- 229920000736 dendritic polymer Polymers 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 18
- 238000002485 combustion reaction Methods 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003546 flue gas Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims description 39
- 238000007872 degassing Methods 0.000 claims description 16
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 150000003141 primary amines Chemical group 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- 239000012972 dimethylethanolamine Substances 0.000 claims description 4
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 3
- LYBWJVKFJAIODE-UHFFFAOYSA-N n,n,n',n'-tetrakis(3-aminopropyl)butane-1,4-diamine Chemical compound NCCCN(CCCN)CCCCN(CCCN)CCCN LYBWJVKFJAIODE-UHFFFAOYSA-N 0.000 claims description 3
- SENLDUJVTGGYIH-UHFFFAOYSA-N n-(2-aminoethyl)-3-[[3-(2-aminoethylamino)-3-oxopropyl]-[2-[bis[3-(2-aminoethylamino)-3-oxopropyl]amino]ethyl]amino]propanamide Chemical compound NCCNC(=O)CCN(CCC(=O)NCCN)CCN(CCC(=O)NCCN)CCC(=O)NCCN SENLDUJVTGGYIH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 150000003512 tertiary amines Chemical class 0.000 abstract description 9
- 239000012190 activator Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000003949 liquefied natural gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003508 chemical denaturation Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- 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
Landscapes
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
본 발명은 연소 배가스에 포함된 이산화탄소 포집용 고효율 흡수제에 관한 것으로, 그 목적은 연소배가스 중에 포함된 이산화탄소를 포집시 흡수제인 3급 아민에 아민 덴드리머 반응활성화제를 도입함으로써 이산화탄소의 흡수속도 및 탈기능을 획기적으로 향상시킨 흡수제를 제공하는 데 있다.
본 발명의 구성은 3급 알카놀아민 100 중량부와; 분자 내에 아민기가 적어도 4개 이상인 가지형의 아민 덴드리머 1 ~ 50 중량부를 포함하는 혼합 흡수제로 이루어진 연소 배가스에 포함된 이산화탄소 포집용 고효율 흡수제를 발명의 특징으로 한다.The present invention relates to a high-efficiency absorbent for capturing carbon dioxide contained in combustion flue gas, and an object thereof is to introduce an amine dendrimer reaction activator into a tertiary amine that is an absorbent when capturing carbon dioxide contained in combustion flue gas, thereby desorbing carbon dioxide. It is to provide an absorbent that has significantly improved the.
The composition of the present invention is 100 parts by weight of tertiary alkanolamine; A highly efficient absorbent for capturing carbon dioxide contained in a combustion exhaust gas comprising a mixed absorbent comprising 1 to 50 parts by weight of a branched amine dendrimer having at least 4 or more amine groups in a molecule is characterized by the invention.
Description
본 발명은 연소 배가스에 포함된 이산화탄소 포집용 고효율 흡수제에 관한 것으로, 자세하게는 연소배가스 중에 포함된 이산화탄소를 포집시 흡수제인 3급 아민에 아민 덴드리머 반응활성화제를 도입함으로써 이산화탄소의 흡수속도 및 탈기능을 획기적으로 향상시킨 흡수제에 관한 것이다.
The present invention relates to a high-efficiency absorbent for capturing carbon dioxide contained in combustion flue gas, and more particularly, by introducing an amine dendrimer reaction activator into a tertiary amine which is an absorbent when capturing carbon dioxide contained in combustion flue gas. It relates to a water absorbent significantly improved.
산업화가 시작된 19세기 초반부터 에너지 산업에서 사용되는 석탄, 석유, 액화천연가스(LNG) 등의 화석연료의 사용 증가로 인하여 대기중에 이산화탄소(CO2), 황화수소(H2S), 카르보닐설파이드(COS), 메탄(CH4) 등의 산성가스 농도가 증가하면서, 산업이 발달됨에 따라 20세기 중반이후에는 급속하게 산성 가스 농도가 증가되었다.Due to the increasing use of fossil fuels such as coal, petroleum, and liquefied natural gas (LNG), which are used in the energy industry since the early 19th century, the industrialization of carbon dioxide (CO 2 ), hydrogen sulfide (H 2 S), carbonyl sulfide ( As the concentration of acidic gases such as COS) and methane (CH 4 ) increased, the concentration of acidic gases rapidly increased since the mid-20th century as the industry developed.
산업의 발달과 함께 이러한 산성 가스의 증가로 인한, 특히 이산화탄소의 대기중 농도 증가로 인한 지구온난화 현상이 가속화되면서, 각국마다 산성 가스의 배출 및 처리에 대한 규제가 엄격해지고 있다. 1992년 6월 브라질리우에서 열린 환경과 개발에 관한 UN 회의를 통하여 지구온난화에 대한 국제적 관심이 점차로 높아지고 있으며, 미국과 일본을 포함한 선진국들은 2010년 지구온실가스 배출량을 1990년 대비 5.2% 감축하기로 합의하는 등 산성가스 저감방안에 대한 국제적 합의가 이루어지고 있다. 특히 지구온난화현상을 야기하는 산성가스 중 50% 정도를 차지하는 이산화탄소의 분리는 더욱 중요한 문제로 대두되고 있다. 그러므로 이에 대한 기술개발이 절실히 요구되고 있는 실정이다.With the development of the industry, the global warming caused by the increase in acidic gas, especially due to the increase in the concentration of carbon dioxide in the atmosphere, has become increasingly strict in each country. The United Nations Conference on Environment and Development in Brazil in June 1992 has raised international interest in global warming. International agreements on how to reduce acid gases are being made. In particular, the separation of carbon dioxide, which accounts for about 50% of the acid gases that cause global warming, is becoming more important. Therefore, technology development for this situation is urgently required.
이산화탄소 분리기술은 크게 흡수법, 흡착법, 막분리법 및 심냉법으로 구분되어진다. 이중 흡수법이 대용량의 이산화탄소 발생원으로부터 이산화탄소를 분리하는 기술 중 현재로서는 가장 현실성 있는 방법으로 인식되면서 흡수기술의 핵심인 흡수제에 대한 연구가 다시 활발해지고 있다.Carbon dioxide separation technology is classified into absorption method, adsorption method, membrane separation method and deep cooling method. As the dual absorption method is recognized as the most realistic method of separating carbon dioxide from a large amount of carbon dioxide sources, research on absorbents, which are the core of the absorption technology, is being revived.
이와 같이 지구 온난화와 관련하여 화석연료에서 배출되는 이산화탄소를 포집하여 저장하는 기술은 미래 유망한 신규 사업 분야이며, 그 중 이산화탄소를 포집하는 기술은 전체 비용의 70~80%를 차지하는 핵심기술이다. As such, the technology of capturing and storing carbon dioxide emitted from fossil fuels in relation to global warming is a promising new business field, and the technology of capturing carbon dioxide is a core technology that accounts for 70 to 80% of the total cost.
이산화탄소를 포집하는데 사용되는 이산화탄소 흡수제는 포집분야의 가장 핵심으로 최근 기술개발이 매우 활발하나 에너지 절감 및 장치 부식 문제 등 해결해야 할 부분이 많이 남아있다. 이하 이 분야의 종래 흡수제 기술을 살펴본다.Carbon dioxide absorbents used to capture carbon dioxide are the core of the field of capture and are currently very active in technology development. The following describes a conventional absorbent technology in this field.
Dow Chemical사는 1급 아민인 MEA(monoethanolamnie)를 이용한 흡수제를 상용화 하였으나, 장치 부식 문제 및 흡수제 재생을 위해서는 과다한 에너지를 요구하는 단점이 있다.Dow Chemical has commercialized absorbents using primary amines, MEA (monoethanolamnie), but has the disadvantage of requiring excessive energy for device corrosion problems and absorbent regeneration.
또한 BASF사는 부식이 적은 3급 아민인 MDEA(methyldiethanolamine)를 이용한 흡수제를 개발하였으나 반응속도가 느리고 대규모 장치를 요구하는 단점이 있다.In addition, BASF has developed an absorbent using MDEA (methyldiethanolamine), a tertiary amine that is less corrosive.
또한 일본 간사이 전력회사와 미쯔비시중공업에서 개발한 입체장애아민(sterically-hindered amine)인 AMP(2-amino-2-methyl-1-propanol)를 이용한 흡수제는 MEA에 비해 재생에너지가 적게 든다는 장점이 있으나 여전히 재생 비용이 경제적이지 않으며 황화수소를 미리 제거해야 하는 번거로움이 있다.In addition, absorbents using AMP (2-amino-2-methyl-1-propanol), a sterically-hindered amine developed by Kansai Electric Power Company and Mitsubishi Heavy Industries, have the advantage of using less renewable energy than MEA. Still, the cost of regeneration is not economical and hassle of removing hydrogen sulfide in advance.
또한 한국에너지기술연구소는 3급 아민 MDEA의 반응속도 향상을 위하여 1급 아민기가 양 끝단에 두 개인 HMDA(hexamethylediamine)을 첨가제로 사용하여 이산화탄소의 흡수속도 및 흡수능을 향상시켰으나, 반응속도를 향상시키는 데는 한계가 있다.
In addition, the Korea Institute of Energy Research improved the absorption rate and absorption capacity of carbon dioxide by using HMDA (hexamethylediamine) with two primary amine groups at both ends to improve the reaction rate of tertiary amine MDEA. There is a limit.
상기와 같은 문제점을 해결하기 위한 본 발명의 목적은 연소배가스 중에 포함된 이산화탄소를 포집시 흡수제인 3급 아민에 아민 덴드리머를 도입함으로써 이산화탄소의 흡수속도 및 탈기능을 획기적으로 향상시킨 흡수제를 제공하는 데 있다.
SUMMARY OF THE INVENTION An object of the present invention for solving the above problems is to provide an absorbent that significantly improves the absorption rate and deactivation of carbon dioxide by introducing an amine dendrimer into a tertiary amine which is an absorbent when collecting carbon dioxide contained in combustion flue gas. have.
상기한 바와 같은 목적을 달성하고 종래의 결점을 제거하기 위한 과제를 수행하는 본 발명은 3급 알카놀아민 100 중량부와; 분자 내에 아민기가 적어도 4개 이상인 아민 덴드리머 1 ~ 50 중량부를 포함하는 혼합 수용액으로 이루어진 것을 특징으로 하는 연소 배가스에 포함된 이산화탄소 포집용 고효율 흡수제를 제공함으로써 달성된다.
The present invention to achieve the object as described above and to perform the problem for removing the conventional drawbacks 100 parts by weight of tertiary alkanolamine; It is achieved by providing a high-efficiency absorbent for capturing carbon dioxide contained in the combustion exhaust gas, characterized in that it consists of a mixed aqueous solution containing 1 to 50 parts by weight of an amine dendrimer having at least 4 or more amine groups in the molecule.
또한 본 발명은 바람직한 실시예로, 상기 3급 알카놀아민은 N-메틸디에탄올아민(MDEA), 트리에탄올아민(TEA), 디메틸에탄올아민(DEEA), 메틸디이소프로판올아민(MEDIA) 중에서 선택된 하나 이상인 것을 특징으로 한다.
In another preferred embodiment, the tertiary alkanolamine is at least one selected from N-methyl diethanolamine (MDEA), triethanolamine (TEA), dimethylethanolamine (DEEA), methyldiisopropanolamine (MEDIA) It is characterized by.
또한 본 발명은 바람직한 실시예로, 상기 아민 덴드리머는 끝단에 2개씩 4개 이상의 1급 아민기를 가진 가지형의 구조를 갖는 Polypropylenimine tetramine dendrimer, generation 1 (DAB-AM-4; G1), Polypropylenimine octaamine Dendrimer, Generation 2 (DAB-AM-8; G2), Polypropylenimine hexadecaamine Dendrimer, Generation 3 (DAB-AM-16; G3), Ethylenediamine core (PAMAM dendrimer; G0) 중에서 선택된 하나 또는 이들의 혼합물로 이루어진 것을 특징으로 한다.
In addition, the present invention is a preferred embodiment, the amine dendrimer is a polypropylenimine tetramine dendrimer, generation 1 (DAB-AM-4; G1), polypropylenimine octaamine Dendrimer having a branched structure having four or more primary amine groups at each end 2 , Generation 2 (DAB-AM-8; G2), Polypropylenimine hexadecaamine Dendrimer, Generation 3 (DAB-AM-16; G3), Ethylenediamine core (PAMAM dendrimer; G0) It is characterized by consisting of one or a mixture thereof .
또한 본 발명은 바람직한 실시예로, 상기 혼합 흡수제는 5 ~ 50% (w/v) 농도 범위의 수용액으로 사용하는 것을 특징으로 한다.
In addition, the present invention is a preferred embodiment, characterized in that the mixed absorbent is used as an aqueous solution in the concentration range of 5 to 50% (w / v).
또한 본 발명은 바람직한 실시예로, 상기 혼합 흡수제의 산성가스 흡수온도는 0 ~ 60 ℃, 탈기온도는 70 ~ 200 ℃ 인 것을 특징으로 한다.
In addition, the present invention is a preferred embodiment, the acid gas absorption temperature of the mixed absorbent is characterized in that 0 ~ 60 ℃, degassing temperature is 70 ~ 200 ℃.
상기와 같이 본 발명은 연소 배기가스에서 이산화탄소를 분리, 흡수함에 있어서 이산화탄소와의 빠른 반응속도 및 높은 흡수능을 가지면서 재생에 많은 에너지를 필요로 하지 않으며, 고농도의 황화합물에도 안정하여 보충하는 흡수제의 양을 절감할 수 있는 에너지 절감 및 경제성 향상 효과를 갖는 유용한 발명으로 산업상 그 이용이 크게 기대되는 발명인 것이다.
As described above, the present invention does not require a lot of energy for regeneration while having a fast reaction rate and high absorption capacity with carbon dioxide in separating and absorbing carbon dioxide from combustion exhaust gas, and an amount of absorbent which is stable and supplements even in high concentrations of sulfur compounds. It is a useful invention having an energy saving and economical improvement effect that can reduce the industrial use is expected to be greatly expected.
이하 본 발명의 실시 예인 구성과 그 작용을 상세히 설명하면 다음과 같다. 또한 본 발명을 설명함에 있어서, 관련된 공지기능 혹은 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우 그 상세한 설명은 생략한다.
Hereinafter, the configuration and the operation of the embodiment of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
본 발명은 이산화탄소, 황화수소 등 산 가스를 포함하는 혼합가스로부터 이산화탄소를 흡수하는 흡수제에 관한 것으로서, 이산화탄소와의 빠른 반응속도 및 높은 흡수능을 가지면서 재생에 많은 에너지를 필요로 하지 않고, 황화합물에도 안정한 흡수제에 관한 것으로서, 3급 알카놀아민 100 중량부와; 분자 내에 아민기가 적어도 4개 이상인 아민 덴드리머를 1 ~ 50 중량부 포함하는 혼합 수용액으로 이루어진다. The present invention relates to an absorbent for absorbing carbon dioxide from a mixed gas containing acid gas such as carbon dioxide, hydrogen sulfide, etc., which has a fast reaction rate and high absorption capacity with carbon dioxide and does not require a lot of energy for regeneration and is also a stable absorbent for sulfur compounds. As relates to, 100 parts by weight of tertiary alkanolamine; It consists of a mixed aqueous solution containing 1-50 weight part of amine dendrimers which are at least 4 or more amine groups in a molecule | numerator.
상기 아민 덴드리머는 본 발명에서 반응활성화제로 첨가되는데, 아래 화학식 1과 같이 화학구조상 끝단에 1개씩 4개 이상의 1급 아민기를 가진 가지형의 구조를 가지고 있다. The amine dendrimer is added as a reaction activator in the present invention, and has a branched structure having four or more primary amine groups, one at the end of the chemical structure, as shown in Chemical Formula 1 below.
화학식 1 (아민 덴드리머, polypropyleneimine tetramine dendrimer, 1 generation)Formula 1 (amine dendrimer, polypropyleneimine tetramine dendrimer, 1 generation)
상기 아민 덴드리머에는 Polypropylenimine tetramine dendrimer, generation 1 (DAB-AM-4; G1),Polypropylenimine octaamine Dendrimer, Generation 2 (DAB-AM-8; G2), Polypropylenimine hexadecaamine Dendrimer, Generation 3 (DAB-AM-16; G3), ethylenediamine core (PAMAM dendrimer; G0) 중에 선택된 하나 또는 이들의 혼합물로 구성된다.
The amine dendrimer includes Polypropylenimine tetramine dendrimer, generation 1 (DAB-AM-4; G1), Polypropylenimine octaamine Dendrimer, Generation 2 (DAB-AM-8; G2), Polypropylenimine hexadecaamine Dendrimer, Generation 3 (DAB-AM-16; G3 ), ethylenediamine core (PAMAM dendrimer; G0) or a mixture thereof.
본 발명의 흡수제는 3급 알카놀 아민과 아민 덴드리머 반응활성제를 섞은 혼합 흡수제의 농도가 5 ~ 50%(w/v) 범위인 수용액으로 사용하는 것이 바람직하다. 상기 혼합 흡수제의 농도가 5% 이하인 경우 반응속도가 늦어 흡수되는 이산화탄소의 절대량이 적으며, 50% 이상인 경우 흡수능과 흡수속도는 우수하지만 많은 양의 흡수제가 사용되어 경제성 측면에서 효율적이지 못하기 때문이다. The absorbent of the present invention is preferably used in an aqueous solution in which the concentration of the mixed absorbent mixed with the tertiary alkanol amine and the amine dendrimer reactant is in the range of 5 to 50% (w / v). If the concentration of the mixed absorbent is less than 5%, the reaction rate is slow, the absolute amount of carbon dioxide is absorbed, and if more than 50%, the absorption capacity and absorption rate is excellent, but because a large amount of absorbent is used, it is not efficient in terms of economy. .
또한 3급 알카놀 아민과 아민 덴드리머 혼합물은 100: 1 ~ 50의 중량비로 사용되는 것이 바람직하다. 아민 덴드리머가 1 중량비 이하로 첨가되는 경우에는 반응속도 및 탈기능 증가 효과가 미미하고 50 중량비 이상으로 첨가되는 경우 사용량 대비 증가 효과가 크지 않을 뿐 아니라 비용이 경제적이지 못하기 때문이다. In addition, the tertiary alkanol amine and amine dendrimer mixture is preferably used in a weight ratio of 100: 1 to 50. If the amine dendrimer is added in less than 1% by weight of the reaction rate and de-functionality increase effect is insignificant, when added to more than 50% by weight is not because the increase effect compared to the amount used is not economical.
본 발명의 흡수제는 3급 알카놀 아민과 아민 덴드리머를 섞은 혼합 흡수제를 의미하는데, 이는 이산화탄소 흡수반응 속도를 증가시킬 뿐 아니라, 탈기반응도 쉽게 일어나게 하는 효과가 있다.
Absorbent of the present invention refers to a mixed absorbent mixture of tertiary alkanol amine and amine dendrimer, which not only increases the rate of carbon dioxide absorption, but also facilitates the degassing reaction.
상기 3급 알카놀아민 중 MDEA(N-Methyl diethanolamine)는 황화수소와 빠른 반응을 가지며 이산화탄소와는 비교적 느리게 반응하기 때문에 황화수소를 선택적으로 분리하는 공정에 흔히 사용되어 왔다. Among the tertiary alkanolamines, MDEA (N-Methyl diethanolamine) has a fast reaction with hydrogen sulfide and relatively slow reaction with carbon dioxide has been commonly used in the process of selectively separating hydrogen sulfide.
또한 열적, 화학적 변성에 강하고 부식성이 없으며, 이산화탄소와 직접 반응하지 않기 때문에 단순히 압력을 감소시키는 방법에 의해서도 재생이 가능하며 재생에너지 요구량이 1급 아민에 비해 대단히 작다. In addition, it is resistant to thermal and chemical denaturation, is not corrosive, and does not react directly with carbon dioxide, so it can be regenerated by simply reducing the pressure, and requires a very small amount of renewable energy compared to the primary amine.
이와 같은 장점에도 불구하고, 이산화탄소와의 반응속도가 매우 느리기 때문에 많은 양의 이산화탄소를 흡수하기 위해서는 높은 이산화탄소의 분압과 다량의 흡수제를 순환해야하기 때문에 높은 충전 높이와 직경이 큰 충전탑이 필요로 하다는 단점을 지니고 있다.
Despite these advantages, the reaction rate with carbon dioxide is very slow, so that a high packing height and a large diameter packed column are required because high partial pressure of carbon dioxide and a large amount of absorbent must be circulated to absorb a large amount of carbon dioxide. It has a downside.
본 발명에서는 상기한 3급 알카놀아민의 장점을 살리면서 느린 흡수속도를 개선하기 위해서 기존의 활성화제 HMDA 대신에 분자당 1급 아민 반응기 수가 4개 이상인 아민 덴드리머를 도입함으로써 이산화탄소의 흡수속도 및 흡수능을 획기적으로 향상시켰다. In the present invention, in order to improve the slow absorption rate while taking advantage of the above-described tertiary alkanolamine, the absorption rate and absorption capacity of carbon dioxide can be improved by introducing an amine dendrimer having four or more primary amine reactors per molecule in place of the conventional activator HMDA. Significantly improved.
이러한 본 발명에서 활성화제로 사용된 아민 덴드리머는 1급 아민 반응기를 4개 이상 가지고 있어 기-액 계면에서 이산화탄소와 직접 반응하여 이산화탄소를 고농도로 흡수하고, 이 반응에 의한 반응 생성물의 농노차 확산에 의해 벌크 액상으로 이동하여 3급 아민과 반응한다. 이 반응과정에서 아민 덴드리머와의 반응에 의해 흡수된 이산화탄소가 3급 아민으로 전달되며, 아민 덴드리머는 다시 재생되어 기-액 접촉 반응에 따라 이산화탄소를 흡수하게 된다. In the present invention, the amine dendrimer used as an activator has four or more primary amine reactors, and reacts directly with carbon dioxide at the gas-liquid interface to absorb carbon dioxide at a high concentration. Transfer to the bulk liquid phase and react with tertiary amines. In this process, the carbon dioxide absorbed by the reaction with the amine dendrimer is transferred to the tertiary amine, and the amine dendrimer is regenerated to absorb carbon dioxide according to the gas-liquid contact reaction.
이와 같이 3급 아민의 이산화탄소 흡수 반응 속도에 비해 아민 덴드리머의 흡수반응 속도가 매우 빠르기 때문에 흡수제의 흡수속도가 향상되며, 3급 아민과 이산화탄소의 화학양론비가 1 : 1인데 반해 1몰의 아민 덴드리머가 4몰의 이산화탄소와 반응하기 때문에 흡수능 역시 증가하게 된다. Thus, the absorption rate of the amine dendrimer is very fast compared to the rate of carbon dioxide absorption of the tertiary amine, so that the absorption rate of the absorbent is improved. As it reacts with 4 moles of carbon dioxide, its absorption capacity also increases.
또한 아민 덴드리머가 기-액 접촉 반응에서 흡수된 이산화탄소를 3급 아민으로 전달하는 과정에서 분자 유동성이 높은 아민 덴드리머의 구조에 의해 반응속도가 향상된다. In addition, the reaction rate is improved by the structure of the amine dendrimer having high molecular fluidity in the process of transferring the carbon dioxide absorbed in the gas-liquid contact reaction to the tertiary amine.
상기 본 발명에 따른 혼합 흡수제의 산성가스 흡수온도는 0 ~ 60 ℃, 탈기온도는 70 ~ 200 ℃이다.
Acid gas absorption temperature of the mixed absorbent according to the present invention is 0 ~ 60 ℃, degassing temperature is 70 ~ 200 ℃.
이하 본 발명의 바람직한 실시예이다.Hereinafter is a preferred embodiment of the present invention.
(실시예 1)(Example 1)
온도가 40 ℃가 되도록 설정한 항온 수조내에 100 ml 용량의 유리 반응기에 흡수제로서 MDEA과 DAB-Am-4를 각각 4.8g, 1.2g 넣어 MDEA : DAB-Am-4 (100:20), 30 %(w/v) 혼합수용액 20 ml를 충전하였다. 여기서, 이 반응기에 이산화탄소 50%, 질소 50% 조성을 가지는 혼합 가스를 100 ml/min 으로 이송시켜 흡수시켰다. 흡수액 출구의 가스 중 이산화탄소 농도를 가스크로마토그래피로 연속적으로 측정하여 이산화탄소 흡수속도, 흡수량 및 흡수부하를 측정하였다. 흡수제가 이산화탄소에 의해 포화가 된 후 (약 100분) 반응기를 미리 120 ℃로 준비된 항온수조로 옮겨 흡수제로부터 이산화탄소의 탈기량을 100분간 측정하였다. 얻어진 결과는 표 1에 나타내었다.
4.8 g and 1.2 g of MDEA and DAB-Am-4 were added to a 100 ml glass reactor in a constant temperature water tank set at a temperature of 40 ° C. as an absorbent. MDEA: DAB-Am-4 (100: 20), 30% 20 ml of (w / v) mixed aqueous solution was charged. Here, the mixed gas having a composition of 50% of carbon dioxide and 50% of nitrogen was transferred to the reactor at 100 ml / min for absorption. The carbon dioxide concentration in the gas at the outlet of the absorbent liquid was continuously measured by gas chromatography to measure the carbon dioxide absorption rate, absorption amount and absorption load. After the absorbent became saturated with carbon dioxide (about 100 minutes), the reactor was transferred to a constant temperature bath prepared at 120 ° C in advance, and the amount of degassing of carbon dioxide from the absorbent was measured for 100 minutes. The results obtained are shown in Table 1.
(실시예 2)(Example 2)
실시예 1과 동일한 장치에서 MDEA : DAB-Am-4 (100:11), 30 %(w/v) 혼합수용액을 흡수제로 사용하여 20 ml를 충진하였다. 혼합가스 중 이산화탄소 흡수율 및 탈기율을 측정하였다. 흡수는 40 ℃, 탈기는 80 ℃에서 수행하였다. 수행한 결과는 표 2와 같다.
In the same apparatus as in Example 1, 20 ml was charged using MDEA: DAB-Am-4 (100: 11), 30% (w / v) mixed aqueous solution as an absorbent. The carbon dioxide absorption rate and the degassing rate in the mixed gas were measured. Absorption was carried out at 40 ° C., and deaeration at 80 ° C. The results are shown in Table 2.
(비교예 1)(Comparative Example 1)
실시예 1과 동일한 장치를 이용하여 동일한 조건에서 흡수제로서 MEA 30% 수용액을 이용하여 이산화탄소 흡수율 및 탈기율을 측정하였다. 얻어진 결과는 표 1에 나타내었다.
The same apparatus as in Example 1 was used to measure carbon dioxide absorption and degassing rate using an aqueous solution of MEA 30% as an absorbent under the same conditions. The results obtained are shown in Table 1.
(비교예 2)(Comparative Example 2)
실시예 1과 동일한 장치를 이용하여 동일한 조건에서 흡수제로서 MDEA 30% 수용액을 이용하여 이산화탄소 흡수율 및 탈기율을 측정하였다. 얻어진 결과는 표 1에 나타내었다.
The same apparatus as in Example 1 was used to measure carbon dioxide absorption and degassing rate using an MDEA 30% aqueous solution as the absorbent under the same conditions. The results obtained are shown in Table 1.
(비교예 3)(Comparative Example 3)
실시예 2와 동일한 장치를 이용하여 동일한 조건에서 흡수제로서 MEA 30% 수용액을 이용하여 이산화탄소 흡수율 및 탈기율을 측정하였다. 얻어진 결과는 표 2에 나타내었다.
Using the same apparatus as in Example 2, the carbon dioxide absorption rate and the degassing rate were measured using a 30% aqueous solution of MEA as the absorbent under the same conditions. The results obtained are shown in Table 2.
(비교예 4)(Comparative Example 4)
실시예 2와 동일한 장치를 이용하여 동일한 조건에서 흡수제로서 MDEA 30% 수용액을 이용하여 이산화탄소 흡수율 및 탈기율을 측정하였다. 얻어진 결과는 표 2에 나타내었다.
Carbon dioxide absorption and degassing rate were measured using MDEA 30% aqueous solution as the absorbent under the same conditions using the same apparatus as in Example 2. The results obtained are shown in Table 2.
표 1은 흡수온도 40℃, 탈기온도 120℃에서 실시예 1의 흡수제와 비교예 1 흡수제의 이산화탄소 흡수 및 탈기 특성을 나타낸 것이다. 실시예 1의 흡수제는 비교예 2의 흡수제의 낮은 흡수능과 흡수속도를 향상시켰으며, 비교예 1, 2의 MEA, MDEA 단일 흡수제보다 경제적으로 이산화탄소를 분리하고 흡수제의 재생이 용이함을 알 수 있다. 따라서, 본 발명의 흡수제는 이산화탄소 흡수반응 속도가 빨라 신속하게 이산화탄소를 흡수한 후 비교적 빠른 시간에 흡수된 이산화탄소를 효과적으로 탈기시킬 수 있으므로, 탈기에 소비되는 에너지 (전체공정의 50 ~ 80%)를 절감할 수 있어 매우 경제적이다.
Table 1 shows the carbon dioxide absorption and degassing characteristics of the absorbent of Example 1 and Comparative Example 1 absorbent at an absorption temperature of 40 ℃, 120 ℃ degassing. The absorbent of Example 1 improved the low absorption capacity and absorption rate of the absorbent of Comparative Example 2, it can be seen that the COA separation and regeneration of the absorbent is more economical than the MEA, MDEA single absorbent of Comparative Examples 1 and 2. Therefore, the absorbent of the present invention can quickly desorb the carbon dioxide absorbed in a relatively fast time after absorbing carbon dioxide rapidly because the carbon dioxide absorption reaction rate is fast, reducing the energy consumed in the degassing (50 ~ 80% of the overall process) It is very economical to do it.
표 2는 흡수온도 40℃, 탈기온도 80℃에서 실시예 2의 흡수제와 비교예 2 흡수제의 이산화탄소 흡수 및 탈기 특성을 나타낸 결과이다. 실시예 2의 흡수제는 비교적 낮은 온도에서도 효율적으로 이산화탄소를 탈기하고 있음을 알 수 있다.
Table 2 shows the results of carbon dioxide absorption and degassing characteristics of the absorbent of Example 2 and Comparative Example 2 absorbent at an absorption temperature of 40 ℃, degassing temperature of 80 ℃. It can be seen that the absorbent of Example 2 efficiently degass carbon dioxide even at a relatively low temperature.
따라서, 본 발명의 흡수제는 이산화탄소 흡수반응 속도가 빨라 신속하게 이산화탄소를 흡수한 후 비교적 짧은 시간과 낮은 온도에서 흡수된 이산화탄소를 효과적으로 탈기시킬 수 있으므로, 이산화탄소 탈기에 소비되는 에너지를 절감할 수 있어 매우 경제적이다.
Therefore, the absorbent of the present invention can rapidly desorb the carbon dioxide absorbed at a relatively short time and low temperature after absorbing carbon dioxide rapidly because the carbon dioxide absorption reaction rate is fast, it is possible to reduce the energy consumed in carbon dioxide degassing and very economical to be.
본 발명은 상술한 특정의 바람직한 실시 예에 한정되지 아니하며, 청구범위에서 청구하는 본 발명의 요지를 벗어남이 없이 당해 발명이 속하는 기술분야에서 통상의 지식을 가진 자라면 누구든지 다양한 변형실시가 가능한 것은 물론이고, 그와 같은 변경은 청구범위 기재의 범위 내에 있게 된다. The present invention is not limited to the above-described specific preferred embodiments, and various modifications can be made by any person having ordinary skill in the art without departing from the gist of the present invention claimed in the claims. Of course, such changes will fall within the scope of the claims.
Claims (5)
100 parts by weight of tertiary alkanolamine; A high-efficiency absorbent for capturing carbon dioxide contained in a combustion exhaust gas, comprising a mixed absorbent containing 1 to 50 parts by weight of an amine dendrimer having at least 4 or more amine groups in a molecule.
상기 3급 알카놀아민은 N-메틸디에탄올아민(MDEA), 트리에탄올아민(TEA), 디메틸에탄올아민(DEEA), 메틸디이소프로판올아민(MEDIA) 중에서 선택된 하나 이상인 것을 특징으로 하는 연소 배가스에 포함된 이산화탄소 포집용 고효율 흡수제.
The method according to claim 1,
The tertiary alkanolamine is at least one selected from N-methyldiethanolamine (MDEA), triethanolamine (TEA), dimethylethanolamine (DEEA), methyldiisopropanolamine (MEDIA), which is included in the combustion flue gas High efficiency absorbent for CO2 capture.
상기 아민 덴드리머는 끝단에 2개씩 4개 이상의 1급 아민기를 가진 가지형의 구조를 갖는 Polypropylenimine tetramine dendrimer, generation 1 (DAB-AM-4; G1), Polypropylenimine octaamine Dendrimer, Generation 2 (DAB-AM-8; G2), Polypropylenimine hexadecaamine Dendrimer, Generation 3 (DAB-AM-16; G3), Ethylenediamine core (PAMAM dendrimer; G0) 중에서 선택된 하나 또는 이들의 혼합물로 이루어진 것을 특징으로 하는 연소 배가스에 포함된 이산화탄소 포집용 고효율 흡수제.
The method according to claim 1,
The amine dendrimer is polypropylenimine tetramine dendrimer, generation 1 (DAB-AM-4; G1), polypropylenimine octaamine dendrimer, Generation 2 (DAB-AM-8) having a branched structure having four or more primary amine groups at two ends G2), high efficiency for capturing carbon dioxide in combustion flue gas, comprising one or a mixture of polypropylenimine hexadecaamine Dendrimer, Generation 3 (DAB-AM-16; G3), and Ethylenediamine core (PAMAM dendrimer; G0) Absorbent.
상기 혼합 흡수제는 5 ~ 50% (w/v) 농도 범위의 수용액으로 사용하는 것을 특징으로 하는 연소 배가스에 포함된 이산화탄소 포집용 고효율 흡수제.
The method according to claim 1,
The mixed absorbent is a high efficiency absorbent for capturing carbon dioxide contained in the combustion flue gas, characterized in that used as an aqueous solution in the range of 5 to 50% (w / v) concentration.
상기 혼합 흡수제의 산성가스 흡수온도는 0 ~ 60 ℃, 탈기온도는 70 ~ 200 ℃ 인 것을 특징으로 하는 연소 배가스에 포함된 이산화탄소 포집용 고효율 흡수제.The method according to claim 1,
Acid gas absorption temperature of the mixed absorbent is 0 ~ 60 ℃, the degassing temperature is a high efficiency absorbent for carbon dioxide capture contained in the combustion exhaust gas, characterized in that.
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