KR20230015589A - Composition for reducing methane emission comprising lignin, humic acid or iron complex thereof - Google Patents
Composition for reducing methane emission comprising lignin, humic acid or iron complex thereof Download PDFInfo
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- KR20230015589A KR20230015589A KR1020210096913A KR20210096913A KR20230015589A KR 20230015589 A KR20230015589 A KR 20230015589A KR 1020210096913 A KR1020210096913 A KR 1020210096913A KR 20210096913 A KR20210096913 A KR 20210096913A KR 20230015589 A KR20230015589 A KR 20230015589A
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- Prior art keywords
- lignin
- humic acid
- iron
- methane gas
- composition
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 164
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000004021 humic acid Substances 0.000 title claims abstract description 73
- 229920005610 lignin Polymers 0.000 title claims abstract description 68
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 150000004698 iron complex Chemical class 0.000 title abstract description 4
- 239000002689 soil Substances 0.000 claims abstract description 55
- 239000004480 active ingredient Substances 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 87
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- 229910052742 iron Inorganic materials 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 14
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- 238000004519 manufacturing process Methods 0.000 claims description 5
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- 239000007789 gas Substances 0.000 abstract description 51
- 239000005431 greenhouse gas Substances 0.000 abstract description 7
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- 230000004720 fertilization Effects 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 7
- -1 iron ions Chemical class 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
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- 239000010902 straw Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
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- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
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- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical compound CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
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- 244000025254 Cannabis sativa Species 0.000 description 1
- 239000005891 Cyromazine Substances 0.000 description 1
- 239000005897 Etoxazole Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000005661 Hexythiazox Substances 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- HRYILSDLIGTCOP-UHFFFAOYSA-N N-benzoylurea Chemical compound NC(=O)NC(=O)C1=CC=CC=C1 HRYILSDLIGTCOP-UHFFFAOYSA-N 0.000 description 1
- 239000005925 Pymetrozine Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- QDRXWCAVUNHOGA-UHFFFAOYSA-N acequinocyl Chemical group C1=CC=C2C(=O)C(CCCCCCCCCCCC)=C(OC(C)=O)C(=O)C2=C1 QDRXWCAVUNHOGA-UHFFFAOYSA-N 0.000 description 1
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- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QXAITBQSYVNQDR-ZIOPAAQOSA-N amitraz Chemical compound C=1C=C(C)C=C(C)C=1/N=C/N(C)\C=N\C1=CC=C(C)C=C1C QXAITBQSYVNQDR-ZIOPAAQOSA-N 0.000 description 1
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- RRZXIRBKKLTSOM-XPNPUAGNSA-N avermectin B1a Chemical compound C1=C[C@H](C)[C@@H]([C@@H](C)CC)O[C@]11O[C@H](C\C=C(C)\[C@@H](O[C@@H]2O[C@@H](C)[C@H](O[C@@H]3O[C@@H](C)[C@H](O)[C@@H](OC)C3)[C@@H](OC)C2)[C@@H](C)\C=C\C=C/2[C@]3([C@H](C(=O)O4)C=C(C)[C@@H](O)[C@H]3OC\2)O)C[C@H]4C1 RRZXIRBKKLTSOM-XPNPUAGNSA-N 0.000 description 1
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- 230000033558 biomineral tissue development Effects 0.000 description 1
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 1
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- CWFOCCVIPCEQCK-UHFFFAOYSA-N chlorfenapyr Chemical compound BrC1=C(C(F)(F)F)N(COCC)C(C=2C=CC(Cl)=CC=2)=C1C#N CWFOCCVIPCEQCK-UHFFFAOYSA-N 0.000 description 1
- LFHISGNCFUNFFM-UHFFFAOYSA-N chloropicrin Chemical compound [O-][N+](=O)C(Cl)(Cl)Cl LFHISGNCFUNFFM-UHFFFAOYSA-N 0.000 description 1
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- LVQDKIWDGQRHTE-UHFFFAOYSA-N cyromazine Chemical compound NC1=NC(N)=NC(NC2CC2)=N1 LVQDKIWDGQRHTE-UHFFFAOYSA-N 0.000 description 1
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- 125000005077 diacylhydrazine group Chemical group 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
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- 125000002587 enol group Chemical group 0.000 description 1
- IXSZQYVWNJNRAL-UHFFFAOYSA-N etoxazole Chemical compound CCOC1=CC(C(C)(C)C)=CC=C1C1N=C(C=2C(=CC=CC=2F)F)OC1 IXSZQYVWNJNRAL-UHFFFAOYSA-N 0.000 description 1
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- VGGSULWDCMWZPO-UHFFFAOYSA-N flavoayamenin Natural products COC1=CC=2OC(C=3C=CC(O)=CC=3)=CC(=O)C=2C(O)=C1C1OC(CO)C(O)C(O)C1OC1OC(CO)C(O)C(O)C1O VGGSULWDCMWZPO-UHFFFAOYSA-N 0.000 description 1
- MXWAGQASUDSFBG-RVDMUPIBSA-N fluacrypyrim Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1COC1=CC(C(F)(F)F)=NC(OC(C)C)=N1 MXWAGQASUDSFBG-RVDMUPIBSA-N 0.000 description 1
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- 150000002505 iron Chemical class 0.000 description 1
- 239000002949 juvenile hormone Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000001418 larval effect Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 230000000696 methanogenic effect Effects 0.000 description 1
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- 244000005706 microflora Species 0.000 description 1
- FXWHFKOXMBTCMP-WMEDONTMSA-N milbemycin Natural products COC1C2OCC3=C/C=C/C(C)CC(=CCC4CC(CC5(O4)OC(C)C(C)C(OC(=O)C(C)CC(C)C)C5O)OC(=O)C(C=C1C)C23O)C FXWHFKOXMBTCMP-WMEDONTMSA-N 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
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- DSOOGBGKEWZRIH-UHFFFAOYSA-N nereistoxin Chemical class CN(C)C1CSSC1 DSOOGBGKEWZRIH-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003992 organochlorine insecticide Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000008048 phenylpyrazoles Chemical class 0.000 description 1
- 239000003016 pheromone Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
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- 239000005648 plant growth regulator Substances 0.000 description 1
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- ZYHMJXZULPZUED-UHFFFAOYSA-N propargite Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1C(OS(=O)OCC#C)CCCC1 ZYHMJXZULPZUED-UHFFFAOYSA-N 0.000 description 1
- QHMTXANCGGJZRX-WUXMJOGZSA-N pymetrozine Chemical compound C1C(C)=NNC(=O)N1\N=C\C1=CC=CN=C1 QHMTXANCGGJZRX-WUXMJOGZSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
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- 230000002940 repellent Effects 0.000 description 1
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- 229940080817 rotenone Drugs 0.000 description 1
- JUVIOZPCNVVQFO-UHFFFAOYSA-N rotenone Natural products O1C2=C3CC(C(C)=C)OC3=CC=C2C(=O)C2C1COC1=C2C=C(OC)C(OC)=C1 JUVIOZPCNVVQFO-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Soil Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Biochemistry (AREA)
- Fertilizers (AREA)
Abstract
Description
본 발명은 리그닌, 휴믹산 또는 이들의 철 복합체를 유효성분으로 함유하는 메탄가스 발생 저감용 조성물에 관한 것이다.The present invention relates to a composition for reducing methane gas generation containing lignin, humic acid or an iron complex thereof as an active ingredient.
메탄(CH4)은 이산화탄소, 아산화질소와 더불어 주요 온실 기체로서 지구 전체 온난화가스의 약 20% 이상을 차지하는 것으로 보고되었다. 특히 메탄은 대기 잔존 기간이 상대적으로 짧음에도 불구하고, 높은 적외선 흡수능으로 인해 이산화탄소이 비해 약 28배 높은 지구온난화지수(Global warming potential, GWP)를 지니고 있는 온실가스 중 하나이다. 메탄은 농업과 축산 분야에서 많이 발생하는데, 농업에서는 물이 차 있는 논의 토양미생물에 의해 발생하기 때문에 벼농사를 짓는 아시아 지역에서 많이 발생하며, 우리나라의 경우 메탄가스 배출량의 23%가 논에서 배출된다. Methane (CH 4 ) is reported to account for about 20% or more of global greenhouse gases as a major greenhouse gas along with carbon dioxide and nitrous oxide. In particular, methane is one of the greenhouse gases having a global warming potential (GWP) that is about 28 times higher than that of carbon dioxide due to its high infrared absorbing power, despite its relatively short remaining period in the atmosphere. Methane is generated a lot in agriculture and livestock. In agriculture, it is generated by soil microorganisms in rice paddies filled with water, so it occurs a lot in Asian regions where rice is grown. In Korea, 23% of methane gas emissions are emitted from rice fields.
현재까지 온실가스 메탄을 저감하기 위해 물 관리, 유기물 선발, 시비 관리, 퇴비화 기술, 벼 품종 선발, 작부 체계 관리 기술 등을 응용한 다양한 연구가 수행되었으나, 여전히 메탄 배출을 효과적으로 저감하기 위한 새로운 저감 기술에 대한 요구가 증가하고 있다. 최근에는 메탄 생산과정 및 유기물의 무기화 과정(organic matter mineralization)을 억제할 수 있는 화학 첨가제[2-bromoethanesulfonate(BES), 2-chloroethanesulfonate(CES), 2-mercaptoethanesulfonate(MES)] 시용에 관한 연구가 시도된 바 있다. 벼 논에 BES를 80 mg kg-1 수준으로 처리할 경우 재배기간 중 총 메탄배출량을 무처리 대비 약 49% 까지 저감할 수 있다고 보고되어 있으나, BES 사용에 따른 추가적인 비용 문제 및 아산화질소 배출량에 대한 평가가 함께 수행되지 않아 메탄 배출 억제제로서 여전히 활용도가 낮은 실정이다. 따라서, 지구 온난화 문제가 심각해지고 기후협약 등을 통해 온난화 가스 발생량 저감에 대한 국제적 관심이 커지고 있는 시점에서, 논에서 메탄 발생을 효과적으로 저감할 수 있는 방법을 개발하는 것이 절실히 필요한 실정이다.Until now, various studies have been conducted that applied water management, organic material selection, fertilization management, composting technology, rice variety selection, and cropping system management technology to reduce greenhouse gas methane, but there are still new reduction technologies to effectively reduce methane emissions. demand for is increasing. Recently, research on the application of chemical additives [2-bromoethanesulfonate (BES), 2-chloroethanesulfonate (CES), 2-mercaptoethanesulfonate (MES)] that can inhibit methane production and organic matter mineralization has been attempted. has been It has been reported that when rice paddies are treated with BES at a level of 80 mg kg -1 , total methane emissions can be reduced by about 49% compared to untreated during the cultivation period. It is still underutilized as a methane emission inhibitor because it has not been evaluated together. Therefore, at a time when the global warming problem is becoming serious and international interest in reducing greenhouse gas emissions through climate conventions and the like is growing, it is urgently needed to develop a method that can effectively reduce methane generation in rice fields.
한편, 한국등록특허 제1313091호에 제올라이트 및 마그네슘으로 이루어진 '토양용 메탄가스 저감 조성물'이 개시되어 있으나, 본 발명의 리그닌, 휴믹산 또는 이들의 철 복합체를 유효성분으로 함유하는 메탄가스 발생 저감용 조성물에 대해서는 기재된 바가 없다.On the other hand, Korean Patent Registration No. 1313091 discloses a 'composition for reducing methane gas for soil' composed of zeolite and magnesium, but the composition for reducing methane gas generation containing lignin, humic acid or an iron complex thereof as an active ingredient of the present invention There is nothing written about it.
본 발명은 상기와 같은 요구에 의해 도출된 것으로서, 본 발명자들은 휴믹산(Humic), 리그닌(Lignin), 휴믹산 또는 리그닌과 철이 혼합된 복합체(Humic+Fe, Lignin+Fe), 휴믹산 또는 리그닌과 철이 킬레이트 결합된 복합체(Chelating Humic+Fe, Chelating Lignin+Fe)를 논 토양에 각각 처리한 후 메탄 발생량을 측정한 결과, 기존 화학비료(NPK) 처리군과 규소(Si) 처리군에 비해 본 발명의 휴믹산, 리그닌 또는 이들의 3가 철 복합체 처리군에서 메탄 발생량이 현저히 감소한 것을 확인함으로써, 본 발명을 완성하였다.The present invention has been derived from the above needs, and the present inventors have found that humic acid (Humic), lignin (Lignin), humic acid or a complex of lignin and iron mixed (Humic + Fe, Lignin + Fe), humic acid or lignin and iron chelate As a result of measuring the methane generation amount after treating the combined complexes (Chelating Humic + Fe, Chelating Lignin + Fe) in paddy soil, respectively, the humic acid of the present invention compared to the existing chemical fertilizer (NPK) treatment group and silicon (Si) treatment group , The present invention was completed by confirming that the amount of methane generation was significantly reduced in the group treated with lignin or trivalent iron complexes thereof.
상기 과제를 해결하기 위해, 본 발명은 리그닌, 휴믹산, 리그닌-철 복합체 또는 휴믹산-철 복합체를 유효성분으로 함유하는 메탄가스 발생 저감용 조성물을 제공한다.In order to solve the above problems, the present invention provides a composition for reducing methane gas generation containing lignin, humic acid, lignin-iron complex or humic acid-iron complex as an active ingredient.
또한, 본 발명은 리그닌, 휴믹산, 리그닌-철 복합체 또는 휴믹산-철 복합체를 유효성분으로 함유하는 메탄가스 발생 저감용 비료 조성물을 제공한다.In addition, the present invention provides a fertilizer composition for reducing methane gas generation containing lignin, humic acid, lignin-iron complex or humic acid-iron complex as an active ingredient.
또한, 본 발명은 리그닌, 휴믹산, 리그닌-철 복합체 또는 휴믹산-철 복합체를 유효성분으로 함유하는 메탄가스 발생 저감용 토양 개량제를 제공한다.In addition, the present invention provides a soil conditioner for reducing methane gas generation containing lignin, humic acid, lignin-iron complex or humic acid-iron complex as an active ingredient.
본 발명의 메탄가스 발생 저감용 조성물을 토양에 처리할 경우 종래 화학비료의 주성분인 질소(N), 인산(P) 및 칼륨(K)을 처리한 토양과 규산질 비료의 주성분인 규소(Si)를 처리한 토양에 비해 메탄 발생량을 현저히 감소시킬 수 있으므로, 농작물 재배 시 토양에서 배출되는 온실가스의 배출을 억제하는 효과를 가져올 것으로 기대된다.When the methane gas emission reduction composition of the present invention is applied to soil, soil treated with nitrogen (N), phosphoric acid (P) and potassium (K), which are the main components of conventional chemical fertilizers, and silicon (Si), which is the main component of siliceous fertilizers, Since methane generation can be significantly reduced compared to treated soil, it is expected to bring about the effect of suppressing the emission of greenhouse gases emitted from the soil during crop cultivation.
도 1은 본 발명의 메탄가스 발생 저감용 조성물을 토양 무게 대비 1% 수준으로 토양에 처리한 후 20일간 메탄가스 총 배출량을 보여주는 결과이다. NPK: 종래 화학비료, H: 휴믹산, L: 리그닌, CHF: 휴믹산과 철이 킬레이트 결합된 복합체, CLF: 리그닌과 철이 킬레이트 결합된 복합체, HF: 휴믹산과 철이 혼합된 복합체, LF: 리그닌과 철이 혼합된 복합체, Si: 규소.
도 2는 본 발명의 메탄가스 발생 저감용 조성물을 토양 무게 대비 0.1%, 0.05% 또는 0.03% 수준으로 토양에 처리한 후 20일간 메탄가스 총 배출량을 보여주는 결과이다. NPK: 종래 화학비료, H: 휴믹산, CHF: 휴믹산과 철이 킬레이트 결합된 복합체, HF: 휴믹산과 철이 혼합된 복합체.
도 3은 본 발명의 메탄가스 발생 저감용 조성물을 토양 무게 대비 1% 수준으로 토양에 처리한 후 처리일로부터 20일간 메탄가스 발생량 추이를 보여주는 결과이다. NPK: 종래 화학비료, H: 휴믹산, L: 리그닌, CHF: 휴믹산과 철이 킬레이트 결합된 복합체, CLF: 리그닌과 철이 킬레이트 결합된 복합체, HF: 휴믹산과 철이 혼합된 복합체, LF: 리그닌과 철이 혼합된 복합체, Si: 규소.
도 4는 본 발명의 메탄가스 발생 저감용 조성물을 토양 무게 대비 0.1%, 0.05% 또는 0.03% 수준으로 토양에 처리한 후 처리일로부터 20일간 메탄가스 발생량 추이를 보여주는 결과이다. NPK: 종래 화학비료, H: 휴믹산, CHF: 휴믹산과 철이 킬레이트 결합된 복합체, HF: 휴믹산과 철이 혼합된 복합체.1 is a result showing the total amount of methane gas discharged for 20 days after treating the soil with the composition for reducing methane gas generation of the present invention at a level of 1% relative to the weight of the soil. NPK: Conventional chemical fertilizer, H: Humic acid, L: Lignin, CHF: Humic acid and iron chelated complex, CLF: Lignin and iron chelated complex, HF: Humic acid and iron mixed complex, LF: Lignin and iron mixed Composite, Si: silicon.
Figure 2 is a result showing the total amount of methane gas emissions for 20 days after the composition for reducing methane gas generation of the present invention was treated with soil at a level of 0.1%, 0.05% or 0.03% by weight of soil. NPK: Conventional chemical fertilizer, H: Humic acid, CHF: Humic acid and iron chelated complex, HF: Humic acid and iron mixed complex.
Figure 3 is a result showing the trend of methane gas generation for 20 days from the treatment date after treating the soil with the composition for reducing methane gas generation of the present invention at a level of 1% relative to the weight of the soil. NPK: Conventional chemical fertilizer, H: Humic acid, L: Lignin, CHF: Humic acid and iron chelated complex, CLF: Lignin and iron chelated complex, HF: Humic acid and iron mixed complex, LF: Lignin and iron mixed Composite, Si: silicon.
Figure 4 is a result showing the trend of methane gas generation for 20 days from the treatment date after treating the soil with the composition for reducing methane gas generation of the present invention at a level of 0.1%, 0.05% or 0.03% compared to the soil weight. NPK: Conventional chemical fertilizer, H: Humic acid, CHF: Humic acid and iron chelated complex, HF: Humic acid and iron mixed complex.
본 발명의 목적을 달성하기 위하여, 본 발명은 리그닌, 휴믹산, 리그닌-철 복합체 또는 휴믹산-철 복합체를 유효성분으로 함유하는 메탄가스 발생 저감용 조성물을 제공한다.In order to achieve the object of the present invention, the present invention provides a composition for reducing methane gas generation containing lignin, humic acid, lignin-iron complex or humic acid-iron complex as an active ingredient.
본 발명의 메탄가스 발생 저감용 조성물에 있어서, 상기 리그닌은 식물 구조체에 포함되어 있는 리그닌 또는 리그닌의 유도체, 펄프 제조 공정에 있어서 강알칼리 또는 강산 조건에서 처리된 리그닌을 포함할 수 있고, 바람직하게는 크라프트 리그닌(kraft lignin)일 수 있으나, 이에 제한되지 않는다. In the composition for reducing methane gas generation of the present invention, the lignin may include lignin or lignin derivatives contained in plant structures, lignin treated under strong alkali or strong acid conditions in the pulp manufacturing process, preferably kraft It may be lignin (kraft lignin), but is not limited thereto.
본 명세서의 용어 '크라프트 리그닌'은 목재와 기타 리그닌을 함유하는 원료를 크라프트 중해액으로 처리하여 얻어지는 리그닌의 유도체를 의미한다.The term 'kraft lignin' used herein refers to a lignin derivative obtained by treating wood and other lignin-containing raw materials with a kraft decomposition solution.
본 명세서의 용어 '휴믹산'은 토양에 포함되는 생물 이외의 유기물 총체, 부식질 중 용제에 제거되지 않고 남아 있는 갈색이나 흑색의 산성유기물로 pH 2.0 이상의 산도에서만 녹는 휴믹물질이다. 휴믹산은 자연계에 용존 유기물질의 50% 이상을 차지하며, 용해 정도에 따라 많은 토양 내 물질 분포에 영향을 미친다. 휴믹산의 카르복실기, 알코올성, 페놀기 및 에놀기 등의 다양한 작용기들은 소수성, 친수성 물질들의 흡착, 산화 환원 반응 등의 화학적 반응을 한다. 다른 명칭으로 부식산이라고 한다. 휴믹산을 작물 또는 토양에 처리하는 것은, 퇴비나 유기질 비료를 작물이 바로 흡수하거나 토양이 바로 이용할 수 있는 형태로 투여하는 것과 같은 효과를 가진다.As used herein, the term 'humic acid' is a brown or black acidic organic substance that remains without being removed by a solvent among the total organic matter and humic substances other than organisms included in the soil, and is a humic substance that dissolves only at an acidity of pH 2.0 or higher. Humic acid accounts for more than 50% of dissolved organic matter in the natural world and affects the distribution of many substances in soil depending on the degree of dissolution. Various functional groups such as carboxyl group, alcohol group, phenol group and enol group of humic acid undergo chemical reactions such as adsorption of hydrophobic and hydrophilic substances and redox reactions. Another name is humic acid. Treating crops or soil with humic acid has the same effect as administering compost or organic fertilizer in a form that can be directly absorbed by crops or used by soil.
본 발명의 메탄가스 발생 저감용 조성물에 있어서, 상기 리그닌-철 복합체 또는 휴믹산-철 복합체는 리그닌과 철이 혼합된 복합체, 휴믹산과 철이 혼합된 복합체, 리그닌과 철이 킬레이트 결합된 복합체 및 휴믹산과 철이 킬레이트 결합된 복합체일 수 있으나, 이에 제한되지 않는다.In the composition for reducing methane gas generation of the present invention, the lignin-iron complex or the humic acid-iron complex is a mixture of lignin and iron, a mixture of humic acid and iron, a chelate complex of lignin and iron, and a chelate bond of humic acid and iron. It may be a complex, but is not limited thereto.
본 발명에 따른 메탄가스 발생 저감용 조성물은 바람직하게는 토양에 처리할 수 있으나, 이에 제한되지 않는다.The composition for reducing methane gas generation according to the present invention may preferably be applied to soil, but is not limited thereto.
본 발명의 메탄가스 발생 저감용 조성물에 있어서, 상기 리그닌, 휴믹산, 리그닌-철 복합체 또는 휴믹산-철 복합체는 토양 총 중량 기준으로, 0.03~1 중량%로 첨가할 수 있고, 바람직하게는 0.03~0.1 중량%, 더욱 바람직하게는 0.03~0.05 중량%로 첨가할 수 있으나, 이에 제한되지 않는다.In the composition for reducing methane gas generation of the present invention, the lignin, humic acid, lignin-iron complex or humic acid-iron complex may be added in an amount of 0.03 to 1% by weight, preferably 0.03 to 0.1% by weight, based on the total weight of soil. It may be added by weight%, more preferably 0.03 to 0.05% by weight, but is not limited thereto.
본 발명은 또한, 상기 메탄가스 발생 저감용 조성물을 식물, 식물의 종자 또는 식물 식재 토양에 처리하는 단계를 포함하는 메탄가스 발생을 저감하는 방법을 제공한다. The present invention also provides a method for reducing methane gas generation comprising the step of treating plants, plant seeds or plant planting soil with the composition for reducing methane gas generation.
본 발명의 일 구현 예에 따른 메탄가스 발생을 저감하는 방법에 있어서, 상기 메탄가스 발생 저감용 조성물은 토양에서 메탄 방출량을 감소시키는 리그닌, 휴믹산, 리그닌-철 복합체 또는 휴믹산-철 복합체를 유효성분으로 포함하고 있으므로, 본 발명의 방법을 이용할 경우 토양으로부터 방출되는 메탄의 발생량을 효과적으로 감소시킬 수 있다.In the method for reducing methane gas generation according to an embodiment of the present invention, the composition for reducing methane gas generation includes lignin, humic acid, lignin-iron complex or humic acid-iron complex that reduces methane emission in soil as an active ingredient Since it contains, the amount of methane emitted from the soil can be effectively reduced when the method of the present invention is used.
본 발명의 일 구현 예에 따른 메탄가스 발생을 저감하는 방법에 있어서, 상기 리그닌-철 복합체 또는 휴믹산-철 복합체는 리그닌과 철이 혼합된 복합체, 휴믹산과 철이 혼합된 복합체, 리그닌과 철이 킬레이트 결합된 복합체 및 휴믹산과 철이 킬레이트 결합된 복합체일 수 있으나, 이에 제한되지 않는다. In the method for reducing methane gas generation according to an embodiment of the present invention, the lignin-iron complex or the humic acid-iron complex is a mixture of lignin and iron, a mixture of humic acid and iron, and a chelated complex of lignin and iron. And it may be a complex in which humic acid and iron are chelated, but are not limited thereto.
본 발명의 일 구현 예에 따른 메탄가스 발생을 저감하는 방법에 있어서, 상기 리그닌과 철이 혼합된 복합체 또는 휴믹산과 철이 혼합된 복합체는, 식물, 식물의 종자 또는 식물 식재 토양에 리그닌(또는 휴믹산)과 철 이온을 혼합하여 처리하거나, 리그닌(또는 휴믹산)과 철 이온을 각각 처리하는 것일 수 있으나, 이에 제한되지 않는다.In the method for reducing methane gas generation according to an embodiment of the present invention, the complex of lignin and iron or the complex of humic acid and iron is mixed with lignin (or humic acid) in plants, plant seeds or planting soil. It may be treated by mixing iron ions, or treated with lignin (or humic acid) and iron ions, but is not limited thereto.
상기 '처리'는 크라프트 리그닌, 휴믹산, 크라프트 리그닌-철 복합체 또는 휴믹산-철 복합체를 유효성분으로 함유하는 메탄가스 발생 저감용 조성물을 시비하는 것으로, 식물에 관주, 즉, 분무하거나 또는 침지하여 수행할 수 있다. 상기 '시비'는 토양이나 작물에 비료 성분을 공급하여 농작물의 생육을 촉진시키는 농작법을 의미한다. 시비 방법은 엽면시비, 전층시비, 심층시비, 측조시비 또는 주입시비 등일 수 있으나, 이에 제한되지 않는다. 침지하는 방법의 경우, 조성물을 식물체 주변의 토양에 붓거나 또는 종자를 조성물에 담가둘 수 있으나, 이에 제한되지 않는다.The 'treatment' is to fertilize a composition for reducing methane gas generation containing kraft lignin, humic acid, kraft lignin-iron complex or humic acid-iron complex as an active ingredient, and the plant is drenched, that is, sprayed or immersed. can The 'fertilization' refers to a farming method that promotes the growth of crops by supplying fertilizer components to soil or crops. The fertilization method may be foliar fertilization, full layer fertilization, deep fertilization, side row fertilization or injection fertilization, but is not limited thereto. In the case of the immersion method, the composition may be poured into the soil around the plant or the seed may be immersed in the composition, but is not limited thereto.
본 명세서의 용어 '바이오매스'는 식물의 건조 중량 또는 생중량을 의미하며, 바이오매스는 다르게 규정되지 않은 이상 식물의 모든 부분, 예를 들면, 어린싹 바이오매스(땅위에 있는 모든 식물 부분), 잎 바이오매스 및 뿌리 바이오매스를 포함할 수 있으나, 이에 제한되지 않는다. 용어 '건조 중량'은 대다수의 세포의 수분을 제거하기 위해 건조시킨 식물의 중량을 말한다. 용어 '생중량'은 대다수의 세포의 수분을 제거하기 위해 건조시키지 않은 식물의 중량을 말한다. 바이오매스는 당업계에 알려진 바이오매스 측정 방법에 의해 측정이 가능하다.As used herein, the term 'biomass' refers to the dry weight or fresh weight of a plant, and biomass refers to all parts of a plant, for example, shoot biomass (all plant parts above ground), unless otherwise specified. It may include, but is not limited to, leaf biomass and root biomass. The term 'dry weight' refers to the weight of a plant that has been dried to remove most of the cell moisture. The term 'fresh weight' refers to the weight of a plant that has not been dried to remove the majority of the cell water. Biomass can be measured by a biomass measuring method known in the art.
본 발명의 일 구현 예에 따른 메탄가스 발생을 저감하는 방법에 있어서, 상기 리그닌, 휴믹산, 리그닌-철 복합체 또는 휴믹산-철 복합체는 바람직하게는 토양에 처리하여 메탄가스 발생을 저감할 수 있으나, 이에 제한되지 않는다. 상기 리그닌, 휴믹산, 리그닌-철 복합체 또는 휴믹산-철 복합체는 토양 총 중량 기준으로, 0.03~1 중량%로 첨가할 수 있고, 바람직하게는 0.03~0.1 중량%, 더욱 바람직하게는 0.03~0.05 중량%로 첨가할 수 있으나, 이에 제한되지 않는다.In the method for reducing methane gas generation according to an embodiment of the present invention, the lignin, humic acid, lignin-iron complex or humic acid-iron complex can be preferably treated with soil to reduce methane gas generation, but thus Not limited. The lignin, humic acid, lignin-iron complex or humic acid-iron complex may be added in an amount of 0.03 to 1% by weight, preferably 0.03 to 0.1% by weight, more preferably 0.03 to 0.05% by weight, based on the total weight of soil. It may be added as, but is not limited thereto.
본 발명은 또한, 리그닌, 휴믹산, 리그닌-철 복합체 또는 휴믹산-철 복합체를 유효성분으로 함유하는 메탄가스 발생 저감용 비료 조성물을 제공한다.The present invention also provides a fertilizer composition for reducing methane gas generation containing lignin, humic acid, lignin-iron complex or humic acid-iron complex as an active ingredient.
본 발명의 메탄가스 발생 저감용 비료 조성물에 있어서, 상기 리그닌-철 복합체 또는 휴믹산-철 복합체는 리그닌과 철이 혼합된 복합체, 휴믹산과 철이 혼합된 복합체, 리그닌과 철이 킬레이트 결합된 복합체 및 휴믹산과 철이 킬레이트 결합된 복합체일 수 있으나, 이에 제한되지 않는다. In the fertilizer composition for reducing methane gas generation of the present invention, the lignin-iron complex or humic acid-iron complex is a mixture of lignin and iron, a mixture of humic acid and iron, a chelated complex of lignin and iron, and a chelate of humic acid and iron It may be a combined complex, but is not limited thereto.
본 명세서의 용어 '비료'는 식물이 정상적으로 생육하기 위하여 필요한 원소의 하나 혹은 그 이상을 공급하는 모든 물질을 의미하며, 유기비료(분해되는 식물/동물 물질로 이루어짐)와 무기비료(화학 물질 및 무기 물질로 이루어짐) 등으로 구분될 수 있다.As used herein, the term 'fertilizer' refers to any material that supplies one or more of the elements necessary for the normal growth of plants, including organic fertilizers (consisting of decomposed plant/animal materials) and inorganic fertilizers (chemical substances and inorganics). made of materials), etc.
또한, 본 발명의 메탄가스 발생 저감용 비료 조성물에 있어서, 상기 리그닌 또는 휴믹산과 철이 킬레이트 결합된 복합체는 리그닌 또는 휴믹산과 철의 킬레이트 결합에 의해 완효성 비료 효과를 나타낸다. 본 발명에서 '완효성 비료'는 작물이 필요로 하는 비료 성분이 천천히 용출되어, 작물의 전 생육기간 혹은 일정 생육기간 동안 비효가 지속적으로 나타나는 비료를 의미한다.In addition, in the fertilizer composition for reducing methane gas generation of the present invention, the complex in which lignin or humic acid and iron are chelated shows a slow-acting fertilizer effect by chelating lignin or humic acid and iron. In the present invention, 'slow-acting fertilizer' refers to a fertilizer in which fertilizer components required by crops are slowly eluted, and the fertilizer effect continuously appears during the entire growth period or a certain period of growth of the crop.
본 발명에 따른 비료 조성물은 일반적인 제형기를 사용하여 적당한 크기의 액상, 분말, 펠렛 또는 과립 등의 다양한 형태로 제형화 될 수 있으나, 이에 제한되지 않는다. 상기에서 제형화된 본 발명의 비료 조성물은 그대로 사용되거나 또는 실온에서 풍건하거나 동결 건조 또는 고온 건조 방법으로 건조시켜 사용할 수 있다. 액상 형태의 비료 조성물을 농가에서 적절히 사용하기 위해서는 작물에 사용 가능한 pH 범위로서 침전이 되지 않아야만 한다. 이는 사용하는 원료의 pH, 용해도를 고려하여 배합비를 선정하여야만 한다.The fertilizer composition according to the present invention may be formulated in various forms such as liquid, powder, pellets or granules of an appropriate size using a general formulation, but is not limited thereto. The fertilizer composition of the present invention formulated above may be used as it is or dried at room temperature by air-drying, freeze-drying or high-temperature drying. In order to properly use the liquid fertilizer composition in farms, it should not be precipitated as a usable pH range for crops. The mixing ratio must be selected in consideration of the pH and solubility of the raw materials to be used.
본 발명의 비료 조성물은, 상기 비료 조성물 단독 또는 다른 농업용 제제, 예를 들어, 농약(pesticides), 살충제(insecticides), 살응애제(acaracides), 살진균제(본 발명의 진균에 무해한 진균제), 살박테리아제, 제초제, 항생제, 항균제, 살선충제(nematocides), 쥐약(rodenticides), 곤충병원체(entomopathogens), 페로몬(pheromones), 유인제(attractants), 식물성장조절제(plant growth regulators), 식물 호르몬(plant hormones), 곤충성장 조절제(insect growth regulators), 화학불임제(chemosterilants), 미생물 작물보호제(microbial pest control agents), 방충제(repellents), 바이러스, 식자극제(phagostimulents), 식물 영양제, 식물비료 및 생물학적 방제제와 함께 배합하거나, 순차적으로 사용될 수 있다. 상기 살충제로는 카르바메이트, 유기 포스페이트, 유기 염소 살충제, 페닐피라졸, 피레트로이드, 네오니코티노이드, 스피노신(spinosin), 아버멕틴(avermectin), 밀베마이신, 유충 호르몬 유사체, 알킬할라이드, 유기 주석 화합물, 네레이스톡신(nereistoxin) 유사체, 벤조일우레아, 디아실히드라진, METI 살비제(acaricide)류의 살곤충제, 클로로피크린, 피메트로진, 플로니카미드, 클로펜테진, 헥시티아족스, 에톡사졸, 디아펜티우론, 프로파르지트, 테트라디폰, 클로르페나피르, DNOC, 부프로페진, 시로마진, 아미트라즈, 히드라메틸논, 아세퀴노실, 플루아크리피림, 로테논 또는 이들의 유도체와 같은 살충제가 사용될 수 있다. 상기 식물 영양제로는 통상적으로 사용되는 식물 영양공급용 비료를 사용할 수 있다. 또한 상기 비료로서, 유기질비료, 복합비료, 질소비료, 인산비료, 칼슘비료, 석회비료, 유산질비료, 황산비료, 마그네슘 비료, 미량원소비료, 유기질비료, 분뇨비료 등이 이용될 수 있다. 이때, 상기 농업적 제제의 특정 예는 당업계의 통상의 지식을 가진 사람에게는 자명한 것이다.The fertilizer composition of the present invention, the fertilizer composition alone or other agricultural agents, for example, pesticides, insecticides, acaricides, fungicides (fungicides harmless to the fungi of the present invention), fungicides Bactericides, herbicides, antibiotics, antimicrobials, nematocides, rodenticides, entomopathogens, pheromones, attractants, plant growth regulators, plant hormones ( plant hormones, insect growth regulators, chemosterilants, microbial pest control agents, repellents, viruses, phagostimulents, plant nutrients, plant fertilizers and biological It can be combined with the control agent or used sequentially. The insecticides include carbamates, organic phosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosin, avermectin, milbemycin, larval hormone analogues, alkylhalides, organic Tin compounds, nereistoxin analogues, benzoylurea, diacylhydrazine, insecticides of the METI class of acaricides, chloropicrin, pymetrozine, flonicamide, clofenthezine, hexythiazox, etoxazole , diafenthiuron, propargite, tetradifone, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone or derivatives thereof Insecticides may be used. As the plant nutrient, a commonly used fertilizer for supplying plant nutrients may be used. In addition, organic fertilizers, complex fertilizers, nitrogen fertilizers, phosphate fertilizers, calcium fertilizers, lime fertilizers, lactic acid fertilizers, sulfuric acid fertilizers, magnesium fertilizers, trace element fertilizers, organic fertilizers, manure fertilizers, and the like can be used as the fertilizer. At this time, specific examples of the agricultural formulations will be apparent to those skilled in the art.
본 발명은 또한, 리그닌, 휴믹산, 리그닌-철 복합체 또는 휴믹산-철 복합체를 유효성분으로 함유하는 메탄가스 발생 저감용 토양 개량제를 제공한다.The present invention also provides a soil conditioner for reducing methane gas generation containing lignin, humic acid, lignin-iron complex or humic acid-iron complex as an active ingredient.
본 명세서의 용어 '토양 개량제(soil conditioner)'는 토양의 물리화학적 성질을 식물생육에 알맞게 개선하여 생산성을 높이기 위해 사용되는 물질을 의미하며, 상기 토양개량제는 기존의 화학비료, 벤토나이트(bentonite), 제올라이트(zeolite), 버미큘라이트(vermiculite), 암모늄, 석회염, 볏짚, 보릿짚, 들풀로 이루어진 군에서 선택되는 1종 이상과 혼합하여 사용될 수 있으나, 이에 제한되지 않는다.As used herein, the term 'soil conditioner' refers to a material used to increase productivity by improving the physicochemical properties of soil appropriately for plant growth, and the soil conditioner is a conventional chemical fertilizer, bentonite, It may be used in combination with at least one selected from the group consisting of zeolite, vermiculite, ammonium, lime salt, rice straw, barley straw, and wild grass, but is not limited thereto.
이하, 본 발명을 실시예 의해 상세히 설명한다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by examples. However, the following examples are only to illustrate the present invention, and the content of the present invention is not limited to the following examples.
재료 및 방법Materials and Methods
1. 메탄 발생 저감용 조성물의 제조1. Preparation of composition for reducing methane generation
본 발명의 메탄 발생 저감용 조성물은 휴믹산(H), 리그닌(L), 리그닌 또는 휴믹산과 철(Fe)이 혼합된 복합체(LF, HF), 리그닌 또는 휴믹산과 철이 킬레이트 결합된 복합체(CHF, CLF)로, 상기 휴믹산(humic acid)은 연갈탄(leonardite)에서 추출한 휴믹산(MYCSA, 미국)을 사용하였고, 상기 리그닌은 크라프트 리그닌(kraft lignin; SIGMA ALDRICH, 미국)을 사용하였다.The composition for reducing methane generation of the present invention is a mixture of humic acid (H), lignin (L), lignin or humic acid and iron (Fe) (LF, HF), lignin or humic acid and iron chelated complex (CHF, CLF) ), humic acid extracted from leonardite (MYCSA, USA) was used as the humic acid, and kraft lignin (SIGMA ALDRICH, USA) was used as the lignin.
또한, 상기 리그닌 또는 휴믹산과 철이 킬레이트 결합된 복합체는 증류수 40 ㎖에 리그닌 또는 휴믹산 2.5 g을 첨가하고 13,000 rpm에서 10분간 원심분리하여 가용성의 리그닌 또는 휴믹산을 분리한 후 분리된 리그닌 또는 휴믹산에 염화철(FeCl3, 덕산과학) 0.5 g을 넣고 pH 8을 맞춰 주어 킬레이팅 반응을 유도한 다음 롤러에서 30분간 교반하고 13,000 rpm으로 10분간 원심분리하여 얻어진 킬레이팅된 용액 중, 상층액 부분은 버리고 하등액 부분만을 수득하여 드라이오븐(dry oven)에서 하루 동안 건조시켜 제조되었다. 이때 가용성의 리그닌 또는 휴믹산과 염화철은 4:1의 질량비로 혼합되었다. 대조군으로는 종래의 화학비료(NPK)와 규산질 비료의 주성분인 규소(Si)를 각각 처리하였다. 상기 NPK 화학비료는 N(46%)-90 kg/ha(남해화학(주) 제조), P2O5(20%)-45 kg/ha((주)풍농 제조) 및 KCl(60%) 40 kg/ha((주)풍농 제조)로 처리하였다.In addition, the lignin or humic acid and iron chelate complex is obtained by adding 2.5 g of lignin or humic acid to 40 ml of distilled water and centrifuging at 13,000 rpm for 10 minutes to separate soluble lignin or humic acid, and then iron chloride to the separated lignin or humic acid ( 0.5 g of FeCl 3 , Duksan Science) was added and adjusted to
2. 논 토양으로부터 메탄가스 발생량 측정2. Measurement of methane gas generation from rice paddy soil
건조된 논 토양 40 g이 들어 있는 유리 바이알에 휴믹산(H), 리그닌(L), 리그닌과 철이 혼합된 복합체(LF), 휴믹산과 철이 혼합된 복합체(HF), 리그닌과 철이 킬레이트 결합된 복합체(CLF) 또는 휴믹산과 철이 킬레이트 결합된 복합체(CHF)를 전체 토양 대비 1%(0.4 g) 수준으로 처리한 후 2 cm의 담수 조건으로 만들어 주었다. 이후 40℃의 암조건에서 인큐베이션 실험 후, 가스크로마토그래피(Gas chromatography; Shimadzu, GC-2010 plus, 일본) 기기를 이용하여 약 3주간 메탄가스 발생량을 측정하였다. 이때 상기 리그닌 또는 휴믹산과 철이 혼합된 복합체는 리그닌 또는 휴믹산 0.32 g과 철 이온(Fe3+) 0.08 g(리그닌 또는 휴믹산의 1/4 수준으로 처리)을 토양에 동시 처리하였다. Humic acid (H), lignin (L), lignin-iron complex (LF), humic acid-iron complex (HF), lignin-iron chelated complex ( CLF) or humic acid and iron chelated complex (CHF) were treated at a level of 1% (0.4 g) relative to the total soil, and then 2 cm of fresh water was made. Thereafter, after incubation in the dark at 40 ° C., the amount of methane gas generated was measured for about 3 weeks using a gas chromatography (Gas chromatography; Shimadzu, GC-2010 plus, Japan) device. At this time, the complex of lignin or humic acid and iron was simultaneously treated with 0.32 g of lignin or humic acid and 0.08 g of iron ion (Fe 3+ ) (treated at a level of 1/4 of lignin or humic acid) in the soil.
실시예 1. 토양에서 메탄 발생 저감 효과 분석Example 1. Analysis of methane generation reduction effect in soil
본 발명의 메탄가스 발생 저감용 조성물을 토양 무게 대비 1% 수준으로 토양에 처리한 후 20일간 메탄가스 총 배출량을 측정한 결과, NPK 처리군과 Si 처리군 보다 본 발명의 휴믹산(H), 리그닌(L), 휴믹산과 철이 킬레이트 결합된 복합체(CHF), 리그닌과 철이 킬레이트 결합된 복합체(CLF), 휴믹산과 철이 혼합된 복합체(HF) 및 리그닌과 철이 혼합된 복합체(LF) 처리군에서 각각 메탄 발생량이 현저히 감소하였고, 특히 CHF 처리군에서 메탄 발생 저감 효과가 가장 우수함을 알 수 있었다(도 1). 이는 킬레이트 결합에 의해 철 이온과 휴믹산 또는 리그닌 성분들이 천천히 지속적으로 방출되도록 하여 완효성(slow release) 비료 효과를 나타내는 것으로 예상되었다.As a result of measuring the total methane gas emission for 20 days after treating the composition for reducing methane gas generation in the soil at a level of 1% relative to the weight of the soil, the humic acid (H) and lignin of the present invention were higher than the NPK-treated group and the Si-treated group. (L), humic acid-iron chelate complex (CHF), lignin-iron chelate complex (CLF), humic acid-iron complex (HF), and lignin-iron complex (LF) treated with methane It was found that the generation amount was significantly reduced, and in particular, the effect of reducing methane generation was the most excellent in the CHF treatment group (FIG. 1). This was expected to exhibit a slow release fertilizer effect by allowing iron ions and humic acid or lignin components to be slowly and continuously released by the chelate bond.
또한, 본 발명의 메탄가스 발생 저감용 조성물을 토양 무게 대비 0.1%, 0.05% 또는 0.03%로 토양에 처리한 후 20일간 메탄가스 총 배출량을 측정한 결과, 0.03% H 처리군, 0.1% HF 처리군, 0.05% HF 처리군 및 0.03% HF 처리군은 NPK 처리군과 유사한 메탄가스 배출량을 보였으나, 0.1% H 처리군, 0.05% H 처리군, 0.1% CHF 처리군, 0.05% CHF 처리군 및 0.03% CHF 처리군은 각각 NPK 처리군에 비해 메탄 발생량이 현저히 감소한 것을 확인하였다(도 2). 이를 통해, 본 발명의 메탄가스 발생 저감용 조성물을 낮은 농도로 토양에 처리하여도 메탄 발생 저감 효과가 지속될 수 있음을 확인하였고, 특히 휴믹산과 철이 킬레이트 결합된 복합체를 처리하였을 때 낮은 농도에서도 메탄 저감 효과가 우수함을 알 수 있었다.In addition, as a result of measuring the total methane gas emission for 20 days after treating the composition for reducing methane gas generation of the present invention at 0.1%, 0.05% or 0.03% of the soil weight, 0.03% H treatment group, 0.1% HF treatment group, 0.05% HF treatment group and 0.03% HF treatment group showed methane gas emissions similar to NPK treatment group, but 0.1% H treatment group, 0.05% H treatment group, 0.1% CHF treatment group, 0.05% CHF treatment group and It was confirmed that the 0.03% CHF treatment group significantly reduced the amount of methane generation compared to the NPK treatment group (FIG. 2). Through this, it was confirmed that the methane reduction effect can be continued even when the composition for reducing methane gas generation of the present invention is treated in soil at a low concentration, and in particular, when a complex in which humic acid and iron are chelated is treated, methane reduction is achieved even at low concentrations It was found that the effect was excellent.
또한, 본 발명의 메탄가스 발생 저감용 조성물을 토양 무게 대비 1% 수준(도 3)으로 토양에 처리하거나, 이보다 더 낮은 0.1%, 0.05% 또는 0.03% 수준(도 4)으로 토양에 처리한 후 처리일로부터 20일간 메탄가스 배출량 추이를 분석한 결과, 12~15일 사이에 메탄가스 배출량이 가장 많이 증가하였고, 특히 이 기간 동안에 NPK 처리군에서 메탄가스 배출량이 최대 수준으로 증가한 반면, 본 발명의 메탄가스 발생 저감용 조성물 처리군은 NPK 처리군에 비해 메탄가스 배출량이 현저히 감소한 것을 확인하였다.In addition, after treating the methane gas generation reduction composition of the present invention to the soil at a level of 1% (FIG. 3) relative to the weight of the soil, or at a lower 0.1%, 0.05% or 0.03% level (FIG. 4) As a result of analyzing the trend of methane gas emission for 20 days from the treatment date, the methane gas emission increased the most between the 12th and 15th days. In particular, the methane gas emission increased to the maximum level in the NPK treatment group during this period, while the It was confirmed that methane gas emission in the group treated with the composition for reducing methane gas emission was significantly reduced compared to the group treated with NPK.
최근 논 토양의 유기물 함량과 작물 수량을 증가시키고 토양 물리성과 미생물상을 향상시키기 위해 논 토양에 볏짚을 넣어주기도 한다. 볏짚을 넣어주면 용적밀도는 낮아지고 토양경도는 감소되어 이로 인해 토양 속 공기 비율이 증가하여 벼의 뿌리 생육을 촉진시킬 수 있고, 토양미생물의 종류와 분포 정도를 더욱 다양하게 변화시킬 수 있다. 또한, 토양 내 유기물은 과도한 토양 산도의 변화를 막아주고 작물에게 공급되는 칼륨과 규산 함량도 높여줄 수 있기 때문에 논 농사 시 볏짚을 시용할 것을 권장하고 있다. 하지만, 담수 조건의 토양이 형성되면 토양 내 메탄 생성균이 볏집에 의해 증가된 유기물을 분해하여 오히려 메탄 발생량이 증가하게 된다. Recently, rice straw is added to paddy soil to increase the organic matter content and crop yield of paddy soil and to improve soil physical properties and microflora. When rice straw is added, the bulk density is lowered and the soil hardness is reduced, which increases the air ratio in the soil, which can promote the growth of rice roots and change the type and distribution of soil microorganisms in a more diverse way. In addition, organic matter in the soil can prevent excessive changes in soil acidity and increase the potassium and silicic acid contents supplied to crops, so it is recommended to use rice straw in paddy farming. However, when freshwater soil is formed, methanogenic bacteria in the soil decompose the organic matter increased by rice farming, and rather increase methane production.
따라서, 종래의 화학비료와 규산질 비료 또는 볏집을 사용하는 것보다 본 발명의 휴믹산, 리그닌, 휴믹산 또는 리그닌과 철이 혼합된 복합체, 휴믹산 또는 리그닌과 철이 킬레이트 결합된 복합체를 사용할 경우 논 토양 내 메탄가스 발생량을 효과적으로 감소시킬 수 있을 것이다.Therefore, rather than using conventional chemical fertilizers and siliceous fertilizers or rice fields, the amount of methane gas generated in paddy soil when using the present invention's humic acid, lignin, humic acid, or the complex of lignin and iron mixed, the complex of humic acid or lignin and iron chelated is used can be effectively reduced.
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