KR101762243B1 - Manufacture Method of Organic and Inorganic Complex Liquid Fertilizer byusing Humic Acid Solubilization from Fish Feed Byproducts origin Squids and Fishes - Google Patents
Manufacture Method of Organic and Inorganic Complex Liquid Fertilizer byusing Humic Acid Solubilization from Fish Feed Byproducts origin Squids and Fishes Download PDFInfo
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- KR101762243B1 KR101762243B1 KR1020160149968A KR20160149968A KR101762243B1 KR 101762243 B1 KR101762243 B1 KR 101762243B1 KR 1020160149968 A KR1020160149968 A KR 1020160149968A KR 20160149968 A KR20160149968 A KR 20160149968A KR 101762243 B1 KR101762243 B1 KR 101762243B1
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- 239000006227 byproduct Substances 0.000 title claims abstract description 46
- 239000003337 fertilizer Substances 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 title claims abstract description 36
- 241000251468 Actinopterygii Species 0.000 title claims abstract description 30
- 241000238366 Cephalopoda Species 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 11
- 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 description 15
- 239000004021 humic acid Substances 0.000 title claims description 15
- 229910021432 inorganic complex Inorganic materials 0.000 title claims description 5
- 230000007928 solubilization Effects 0.000 title claims 2
- 238000005063 solubilization Methods 0.000 title claims 2
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- 102000004169 proteins and genes Human genes 0.000 claims description 21
- 108090000623 proteins and genes Proteins 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
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- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000005191 phase separation Methods 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 235000004252 protein component Nutrition 0.000 claims description 4
- 230000003381 solubilizing effect Effects 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 241001465754 Metazoa Species 0.000 claims 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052951 chalcopyrite Inorganic materials 0.000 claims 1
- 229910017053 inorganic salt Inorganic materials 0.000 claims 1
- 239000003906 humectant Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 32
- 239000000047 product Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 8
- 239000002689 soil Substances 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- 235000021323 fish oil Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 3
- 230000008635 plant growth Effects 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000269821 Scombridae Species 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- -1 carboxylic acid compound Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004459 forage Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 235000020640 mackerel Nutrition 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 238000009372 pisciculture Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- 238000011105 stabilization Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F1/00—Fertilisers made from animal corpses, or parts thereof
- C05F1/002—Fertilisers made from animal corpses, or parts thereof from fish or from fish-wastes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
-
- C05G3/0064—
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
-
- 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
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
본 발명은 오징어 및 생선 부산물 유래 양어사료 가공부산물로부터 유믹산 가용화 유/무기 복합 액상비료 제조방법 및 그 제조방법에 의하여 제조된 액상비료에 관한 것이다.The present invention relates to a method for producing an organic / inorganic mixed liquid fertilizer from an aqueous humectant-derived liquid fertilizer from a fish meal processing by-product derived from squid and fish by-product and a liquid fertilizer produced by the method.
Description
본 발명은 오징어 및 생선부산물로부터 유래 되는 양어사료의 가공부산물로부터 휴믹산 가용화 유/무기 복합 액상비료 제조방법에 관한 것으로, 더욱 자세하게는 오징어 및 생선 부산물로부터 사료화 공정의 과정 중 파생되는 부산물을 분리 회수하고 식물 생장 촉진능을 가지는 무기염들을 선택적으로 가용화 하여 식물의 육상 또는 수상 재배 시 시비할 수 있는 액상 비료의 제조 방법에 관한 것이다. The present invention relates to a method for producing humic acid-soluble organic / inorganic complex liquid fertilizer from processing by-products of fish stock derived from squid and fish by-products, and more particularly to a method for separating and recovering by-products derived from squid and fish by- The present invention relates to a method for producing a liquid fertilizer capable of selectively solubilizing inorganic salts having a plant growth promoting ability to produce a liquid fertilizer which can be applied during the cultivation of a plant on land or in water.
최근 화학비료의 가격이 상승함에 따라 농업 생산비용이 증가하고, 화학비료의 사용이 증가함에 따라 토양환경오염, 작물의 생산성 감소 및 생산되는 농산물의 품질이 저하되는 문제가 있다.Recently, as the price of chemical fertilizer is increased, the cost of agricultural production is increased and the use of chemical fertilizer is increased, so there is a problem that soil environmental pollution, decrease of crop productivity and quality of agricultural produce are deteriorated.
이에 따라, 최근에는 화학비료보다 상대적으로 가격이 저렴할 뿐만 아니라, 토양환경을 개선할 수 있고, 작물생산성을 향상시킬 수 있는 양질의 유기질 및 부산물을 이용한 친환경 비료의 활용에 관심이 높아지고 있다.In recent years, there has been an increasing interest in utilizing environmentally friendly fertilizers using organic materials and by-products that can improve the soil environment and improve crop productivity, as well as being relatively less expensive than chemical fertilizers.
이러한 친환경 비료 중 생선 부산물이 포함되는 유기농 비료에 대한 개발이 진행 중이다.Development of organic fertilizers containing fish by-products among these eco-friendly fertilizers is underway.
그러나, 상기 생선 부산물을 사용하는 친환경 비료는 특정 어종 일례로, 고등어 또는 광어 등으로만 생산 및 제조됨으로써, 원료 수급이 원활하지 못하고 비용발생으로 인해 제조 원가의 상승 및 공정 효율이 저하된다는 문제가 있었다.However, the eco-friendly fertilizer using the fish by-products is produced and manufactured only with a mackerel or a mineral fish, for example, as a specific species of fish, thereby failing to supply raw materials smoothly, causing an increase in manufacturing cost and lowering the process efficiency .
한편, 종래 개발된 생선 부산물 유래 액상비료 제조 방식을 살펴보면, 대다수 미생물 또는 활성 미생물제(Effective Microorganisms, EM)를 이용한 발효방식을 채택함으로써 수개월 또는 1년 이상의 발효시간이 소요되어 가공률 및 생산성이 현저히 떨어지며, 또한 발효공정은 외기 환경 영향을 크게 받으므로 제품 표준화가 어려워 실 생산 공정으로는 활용도가 낮은 방식이다.On the other hand, the conventional method of manufacturing the liquid by-product fertilizer derived from fish by-products shows that the fermentation method using most microorganisms or effective microorganisms (EM) is adopted, so that fermentation time of several months or more is required and processing rate and productivity are remarkably decreased , And the fermentation process is highly unfavorable for the production process because it is difficult to standardize the product because the fermentation process is greatly influenced by the external environment.
그리고 상기 생선 부산물을 액상 비료의 원료로서 사용할 시 액상 비료 내 칼슘, 마그네슘, 칼륨 등의 무기이온 함량이 현저히 낮아 식물생장에 필요한 미네랄의 공급 및 이온평형이 저하될 우려가 있다.When the fish by-product is used as a raw material for liquid fertilizer, the content of inorganic ions such as calcium, magnesium, potassium and the like in the liquid fertilizer is remarkably low, so that supply of mineral and ion equilibrium required for plant growth may be lowered.
이에 따라, 생선 부산물이 포함된 새로운 액상비료의 제조방법에 대한 개발의 필요성이 주목되고 있는 추세이다.Accordingly, there is a growing interest in the development of a method for producing a new liquid fertilizer containing fish by-products.
본 발명은 상기와 같은 종래 기술의 문제점으로서, 원료수급문제, 가공시간, 원료 처리 속도, 제품 표준화, 무기이온 함량의 부재 등의 문제를 해결하면서, 실생산 공정의 활용도 향상 및 제품 품질 향상에 기여할 수 있는 오징어 및 생선 부산물로부터 휴믹산 가용성 복합 액상비료의 제조 방법을 제공하는데 그 목적이 있다.Disclosure of the Invention The present invention has been made in view of the above problems in the prior art, and it is an object of the present invention to solve the problems of raw material supply and demand, processing time, raw material processing speed, product standardization, The present invention provides a method for producing humic acid-soluble complex liquid fertilizer from squid and fish by-products.
상기 목적을 달성하기 위하여, 본 발명의 바람직한 실시형태에 따르면 하기와 같은 단계로 이루어지는 제조방법을 채택함에 따라, 오징어 및 생선부산물 유래 양어사료 가공부산물로부터 휴믹산 가용화 유/무기 복합 액상비료를 제공한다.In order to achieve the above object, according to a preferred embodiment of the present invention, there is provided a humic acid-soluble organic / inorganic hybrid liquid fertilizer from squid and fish by-product derived from fishmeal by-products in accordance with the following manufacturing method.
(1) 원료 준비 단계(1) Preparation of raw materials
오징어 부산물 및 생선 부산물을 혼합 분쇄하여 원료를 준비하는 단계이다.Squid by-products and fish by-products are mixed and ground to prepare a raw material.
(2) 산 가수분해 단계(2) Acid hydrolysis step
오징어 부산물 및 생선 부산물의 혼합 분쇄물의 원료 중량 대비 특정량의 유기산을 첨가하여 가수분해하는 단계이다.A specific amount of organic acid is added to the raw material weight of the mixed pulverized product of squid by-products and fish by-products to hydrolyze.
(3) 여과 단계(3) Filtration step
상기 산 가수분해 단계 후, 가수분해물과 잔사(회분류)를 여과 분리하여 가수분해물을 수득하는 단계이다.After the acid hydrolysis step, the hydrolyzate and the residue (slurry) are separated by filtration to obtain a hydrolyzate.
(4) 용석 결정화 단계 (4) Crystallization step of the molten stone
상기 산 가수분해물에 특정량의 무기염기를 첨가하고, 가열 교반하여 가수분해물 내 단백질 성분을 용석 결정화시키는 단계이다.Adding a specific amount of an inorganic base to the acid hydrolyzate, and heating and stirring the resultant to precipitate the protein component in the hydrolyzate.
(5) 상분리 단계(5) phase separation step
상기 용석 결정화물을 원심분리하여 3상의 물질 층으로 상분리(상층 : 유지, 중간층 : 단백질 용석 결정화물, 하층 : 유지 및 단백질이 일부 가용화 된 물층) 시키는 단계이다. The molten crystalline product is centrifuged to separate phases of the three phases (upper layer: oil, middle layer: protein molybdate, lower layer: oil and partially soluble protein).
(6) 양어사료 회수 단계 (6) Acid feed recovery stage
상기 상분리 된 물질층 중 상층부와 중간부인 유지 및 단백질 용석 결정화물은 각각 양어사료용 어유와 어분으로서 분리 회수하는 단계이다.The upper and middle portions of the phase separated material and the protein and zeolite crystals are separated and recovered as fish meal and fish meal for the respective fish feeds, respectively.
(7) 양어사료 부산물 회수 단계 (7) Recovery step of fish meal byproduct
상기 상분리 된 하층부로서, 유지 및 단백질이 일부 가용화 된 물층을 양어사료 부산물로서 회수하여 본 발명의 액상비료 원료로 사용하기 위하여 회수하는 단계이다.As the phase separated lower layer portion, a water layer in which fat and protein are partially solubilized is recovered as a by-product feed by-product and recovered for use as a liquid fertilizer raw material of the present invention.
(8) 휴믹산 가용화 단계 (8) Step of solubilizing humic acid
상기 회수한 양어사료 부산물에 휴믹산을 첨가 혼합하여 완전 용해시킴으로써, 유/무기 복합 액상 비료를 제조하는 단계이다.Inorganic fertilizer by adding humic acid to the recovered by-product feed by-products and completely dissolving it.
(9) 액상비료 안정화 단계 (9) Liquid fertilizer stabilization step
상기 제조된 휴믹산 가용화 유/무기 복합 액상비료에 염소계 무기염류를 첨가하고 가열 교반하여 액상비료 내 가용화 된 단백질 무기금속염과 휴믹산의 이온교환을 봉쇄하여 안정화시키는 단계이다.The chlorinated inorganic salts are added to the prepared humic acid-soluble organic / inorganic hybrid liquid fertilizer and the mixture is heated and stirred to stabilize the ion exchange of solubilized protein inorganic metal salt and humic acid in the liquid fertilizer.
본 발명에 따른 오징어 및 생선 부산물이 포함된 액상비료 제조방법을 제공함으로써, 원료 수급이 원활하며, 제조 시간의 단축으로 공정 효율 및 생산성이 향상되어 실생산 공정에서의 생산 효율을 증대시킬 수 있으며, 외기환경 영향을 크게 받지 않아 제품 표준화가 쉽다.The present invention provides a method for producing liquid fertilizer containing squid and fish by-products, which can smoothly supply and receive raw materials, improve process efficiency and productivity by shortening production time, It is easy to standardize products because it is not affected greatly by environmental influences.
또한, 본 발명의 오징어 및 생선 부산물을 이용한 액상 비료를 사용할 시 무기이온 함량의 증대로 식물생장에 필요한 미네날을 공급해주고, 이온평형을 유지시켜 준다.In addition, when the liquid fertilizer using the squid and fish by-products of the present invention is used, the inorganic ion content is increased to supply the minerals necessary for plant growth and maintain the ion equilibrium.
[도 1] 본원 발명의 제조 공정 개략도 1 is a schematic view of a manufacturing process of the present invention;
이하, 본 발명의 바람직한 실시 양태에 대하여 상세하게 설명한다.Hereinafter, preferred embodiments of the present invention will be described in detail.
본 발명의 원료 준비 단계는 오징어 부산물 및 생선 부산물을 40~60중량부:40~60중량부의 비율로 혼합 및 분쇄하여 원료로서 100중량부를 준비하는 단계이다.In the preparation step of the present invention, squid by-products and fish by-products are mixed and pulverized at a ratio of 40-60 parts by weight: 40-60 parts by weight to prepare 100 parts by weight as a raw material.
본 발명의 산 가수분해 단계는 상기 오징어 부산물 및 생선 부산물의 혼합 분쇄물으로서의 원료 100중량부에 대하여 유기산 2~4중량부 및 정제수 40~60중량부를 첨가하고 1기압, 80~100℃에서 1~3시간 가수분해를 수행하는 단계이다. In the acid hydrolysis step of the present invention, 2 to 4 parts by weight of organic acid and 40 to 60 parts by weight of purified water are added to 100 parts by weight of the raw material as the mixed pulverized product of the squid by-products and fish by- 3 hours hydrolysis.
상기 반응 온도가 80℃ 미만일 경우, 원료 내부로의 물의 확산속도가 느려 가수분해 반응속도가 감소되며, 100℃ 초과일 경우, 물의 유전상수가 낮아 산의 이온 교환능이 감소하여 가수분해 반응속도가 감소된다. When the reaction temperature is lower than 80 ° C., the rate of hydrolysis reaction decreases due to a slow diffusion rate of water into the raw material. When the reaction temperature is higher than 100 ° C., the dielectric constant of water is low, do.
상기 반응 시간이 1시간 미만일 경우, 가수분해 진행도가 낮아 가수분해 수율이 저감 될 수 있으며, 3시간 초과일 경우, 원료의 장시간 가열 노출에 의한 과산화 반응 및 탄화반응이 진행되어 과산화물 또는 탄화물의 발생 우려가 있다.If the reaction time is less than 1 hour, hydrolysis yield may be reduced due to low hydrolysis progress. If the reaction time is longer than 3 hours, peroxidation reaction or carbonization reaction due to heating and exposure of the raw material for a long time may proceed, There is a concern.
상기 산 가수분해에 사용가능한 유기산의 종류는 다양하나 실제 제품 생산 공정에서 운전시 생산성과 안전성을 고려할 경우, 약산 가수분해에 활용 가능한 유기산류가 바람직하며, 상기 유기산으로는 선형 또는 분지형의 C1 내지 C18 탄화수소 사슬을 갖는 카르복실산 화합물로서, 포름산, 아세트산, 프로피온산, 부티르산, 펠라르곤산, 구연산, DL-사과산, 푸말산 등을 들 수 있으며, 특히 바람직하게는 식품 공정상에서 널리 사용하는 구연산이 바람직하다.However, in view of productivity and safety during operation in an actual product production process, organic acids that can be used for weak hydrolysis are preferable. As the organic acid, linear or branched C 1 Examples of the carboxylic acid compound having a C 18 hydrocarbon chain include formic acid, acetic acid, propionic acid, butyric acid, pelargonic acid, citric acid, DL-malic acid and fumaric acid. Particularly preferably, .
상기 산 가수분해시 첨가되는 유기산의 첨가량은 원료량 대비 2~6중량부의 범위 내에서 첨가될 수 있다. 2중량부 미만일시 가수분해반응에 참여하는 단백질의 가수분해 수율이 저감될 수 있으며, 6중량부 초과시 가수분해반응에 참여하는 단백질 외 인지질의 수소화가 진행될 수 있어 가수 분해물 내인 단백질 수소화물의 생성으로 유동성이 저해될 수 있다. The amount of the organic acid to be added in the acid hydrolysis may be 2 to 6 parts by weight based on the raw material. If the amount is less than 2 parts by weight, the hydrolysis yield of the protein participating in the hydrolysis reaction may be reduced. If the amount of the protein is greater than 6 parts by weight, hydrogenation of the phospholipids outside the protein participating in the hydrolysis reaction may proceed, The flowability may be inhibited.
본 발명의 여과 단계는 상기 가수분해 단위 공정 후 가수분해물 내에 잔존하는 미반응 잔사(가수분해에 참여하지 않은 회분류)를 여과 분리하여 산 가수분해물을 수득하는 단계로서, 가수분해물 내 잔존하는 가수분해에 참여하지 않은 회분류 등을 제거하는 단계이다.In the filtration step of the present invention, the unreacted residues remaining in the hydrolyzate after the hydrolysis unit process (filtration without participating in hydrolysis) are separated by filtration to obtain an acid hydrolyzate, and the remaining hydrolyzate Which is not participating in the present invention.
본 발명의 용석 결정화 단계는 상기 수득한 산 가수분해물에 무기염기 2~4 중량부를 첨가하여 50~70℃에서 10분간 가열 교반하여 가수분해물 내 단백질 성분을 용석 결정화시키는 단계로서, 상기 무기염기는 수용액 중에서 이온화하여 OH－를 생성하며 산을 중화하고 염을 생성하는 수산화나트륨(NaOH), 수산화칼슘(Ca(OH)2) 등 다양하나 실제 제품 생산 공정에서 운전시 생산성을 고려할 경우, 특히 수산화나트륨(NaOH)이 바람직하고, 용석 결정화 온도는 50~70℃ 범위가 바람직하다. The step of crystallizing the zeolite of the present invention comprises the step of adding 2 to 4 parts by weight of an inorganic base to the obtained acid hydrolyzate and heating and stirring the mixture at 50 to 70 ° C for 10 minutes to thereby crystallize the protein component in the hydrolyzate, (NaOH) and calcium hydroxide (Ca (OH) 2 ), which ionize to form OH - and neutralize acids and produce salts. However, when considering the productivity during operation in actual production processes, sodium hydroxide ), And the molten stone crystallization temperature is preferably in the range of 50 to 70 占 폚.
본 발명의 상분리 단계는 상기 용석 결정화물을 원심분리 등의 고형물 및 액상을 분리할 수 있는 장치를 이용하여 3000rpm에서 10분간 하여 3상의 물질층으로 상분리(상층 : 유지, 중간층 : 단백질 용석 결정화물, 하층 : 유지 및 단백질이 일부 가용화 된 물층) 시키는 단계이며, 이때의 물질 층간 조성비는 상층 : 10%, 중간층 : 30%, 하층 : 60% 순이다.In the phase separation step of the present invention, the molten crystalline product is subjected to phase separation (upper layer: oil retaining, intermediate layer: protein molybdenum crystallite, The lower layer: a water layer in which the oil and the protein are partially solubilized). In this case, the interlayer composition ratio is 10% for the upper layer, 30% for the middle layer and 60% for the lower layer.
상기 유지는 오징어유 및 어유를 지칭하며, 하층부에 있어서, 유지 및 단백질이 일부 가용화된 물층이란, 약염기상의 수용액에 일부 용해되어 있다는 의미이고, 이때, 가용화되는 유지의 양은 약 0.2% 이다.The above-mentioned fat refers to squid oil and fish oil. In the lower layer portion, the water layer in which the fat and protein are partially solubilized means that it is partially dissolved in the aqueous solution of weak base, and the amount of fat to be solubilized is about 0.2%.
본 발명의 양어사료 회수 단계는 상기 상분리된 물질층 중 상층과 중간층인 유지 및 단백질 용석결정화물은 각각 양어사료용 어유와 어분의 용도로 사용하기 위하여 분리 회수하는 단계로서, 회수 장치는 유동층 상분리기 또는 고액분리 장치가 바람직하다.The recovering step of the present invention is a step of separating and collecting the upper and intermediate layers of the phase separated material layer for use as fish oil and fish meal for fish farming respectively and the recovering device is a fluidized bed phase separator A solid-liquid separator is preferable.
본 발명의 양어사료 부산물 회수 단계는 상기 상분리 된 하층에 존재하는 것으로 유지 및 단백질이 일부 가용화 된 물층을 회수하여 본 발명의 액상비료 원료로 사용하기 위한 단계로서, 회수 장치로는 유동층 상분리기 또는 고액분리 장치가 바람직하다.The recovering step of the feed forage according to the present invention is a step for recovering a water layer which is present in the phase-separated lower layer and in which the protein is partially solubilized and used as a raw material for liquid fertilizer of the present invention. A separator is preferred.
본 발명의 휴믹산 가용화 단계는 상기 회수한 양어사료 부산물에 휴믹산 0.5~1.5중량부를 첨가 혼합하고 완전 용해시켜 유/무기 복합 액상 비료를 제조하는 단계이다. In the step of solubilizing humic acid according to the present invention, 0.5 to 1.5 parts by weight of humic acid is added to the recovered by-product by-products and completely dissolved to prepare an organic / inorganic hybrid liquid fertilizer.
상기 휴믹산(Humic acid)은 일명 부식산(腐植酸)이라고 하며, 알칼리 또는 산에 의해 토양에서 추출되거나 침적된 유기물로서, 부식을 구성하는 성분 중 하나이며, 또한, 식물 등이 미생물에 의한 분해를 경유하여 형성된 최종 생성물인 휴믹물질(부식물질) 중, 산성의 무정형 고분자 유기물로서, 부식토나 토양 등에 있어서 알칼리에 가용이며, 산에서 침전하는 적갈색 내지 흑갈색을 나타내고, 작물의 재배 시 유기질 비료를 작물에 바로 흡수하게 하는 효과를 나타낸다.Humic acid is a so-called humic acid, and is an organic matter extracted or deposited in the soil by alkali or acid. It is one of the constituents of corrosion. Also, the humic acid is decomposed by microorganisms It is an acidic amorphous polymer organic matter among the humic substances (corrosive substances) which are formed by passing through the soil, and is soluble in alkali in the soil or the like. It shows a reddish brown to blackish brown color which precipitates in the acid. It shows the effect of absorbing immediately.
본 발명의 액상비료 안정화 단계는 상기 제조된 휴믹산 가용화 유/무기 복합 액상비료에 염소계 무기염류 0.05~0.15중량부를 첨가하고 70~90℃에서 10분간 가열 교반하여 액상비료 내 가용화 된 단백질 무기금속염과 휴믹산의 이온교환을 봉쇄시키는 단계로서, 상기 염소계 무기염류는 염화칼슘, 염화마그네슘, 염화나트륨, 염화칼륨 등이 바람직하고, 특히 바람직하게는 염화칼슘을 들 수 있다. In the step of stabilizing the liquid fertilizer of the present invention, 0.05 to 0.15 parts by weight of chlorine-based inorganic salts are added to the prepared humic acid-soluble organic / inorganic composite liquid fertilizer, and the mixture is heated and agitated at 70 to 90 ° C for 10 minutes to dissolve the solubilized protein- And the chlorine-based inorganic salts are preferably calcium chloride, magnesium chloride, sodium chloride, potassium chloride and the like, particularly preferably calcium chloride.
실시예Example
휴믹산 가용화 유/무기 복합 액상비료의 제조Preparation of Humic Acid Soluble Oil / Inorganic Complex Liquid Fertilizer
1> 오징어 부산물 및 생선 부산물을 50 : 50중량부의 비율로 혼합하고 분쇄하여 이를 원료로서 100중량부로 하여 준비하였다.1> Squid by-products and fish by-products were mixed at a ratio of 50: 50 parts by weight and pulverized to prepare 100 parts by weight as a raw material.
2> 상기 오징어 부산물 및 생선 부산물의 혼합 분쇄물으로서의 원료 100 중량부에 대하여 구연산 3중량부 및 정제수 50중량부를 첨가하고 1기압, 90℃에서 2시간 가수분해를 수행하였다.2> 3 parts by weight of citric acid and 50 parts by weight of purified water were added to 100 parts by weight of the raw material as the mixed pulverized product of squid by-products and fish by-products, and hydrolysis was carried out at 90 ° C for 1 hour under 1 atm.
3> 상기 가수분해 후 가수분해물 내에 잔존하는 미반응 잔사(가수분해에 참여하지 않은 회분류)를 여과 분리하여 산 가수분해물 135중량부을 수득하고, 잔존하는 회분류 등을 통상의 방법으로 분리 제거하였다.3> Unreacted residues remaining in the hydrolyzate after hydrolysis (spinning without participation in hydrolysis) were separated by filtration to obtain 135 parts by weight of acid hydrolyzate, and the remaining spinning solution was separated and removed by a usual method .
4> 상기 수득한 산 가수분해물에 NaOH 3중량부를 첨가하고, 60℃에서 10분간 가열 교반하여 가수분해물 내 단백질 성분을 용석 결정화시켰다.4) To the acid hydrolyzate thus obtained, 3 parts by weight of NaOH was added and heated and stirred at 60 DEG C for 10 minutes to morphologize the protein component in the hydrolyzate.
5> 상기 용석 결정화물을 3000rpm에서 10분간 원심분리하여 3상의 물질층으로 상분리(상층 : 유지, 중간층 : 단백질 용석결정화물, 하층 : 유지 및 단백질이 일부 가용화된 물층) 하였고, 이때의 물질 층간 조성비는 상층 : 10%, 중간층 : 30%, 하층 : 60% 순이었다.5> The above-mentioned molybdenum talc was centrifuged at 3000 rpm for 10 minutes to obtain phase separation (upper layer: oil phase, intermediate layer: protein molybdate, lower layer: oil and protein partially solubilized water layer) 10% for the upper layer, 30% for the middle layer, and 60% for the lower layer.
6> 상기 상분리된 물질층 중 상층과 중간층인 유지 및 단백질 용석결정화물은 각각 양어사료용 어유와 어분의 용도로 사용하기 위하여, 어유 13.5중량부 및 어분 40.5중량부로 분리 회수하였다.Among the phase separated material layers, the upper and middle layers of the fat and protein molybdate were separated and recovered into 13.5 parts by weight of fish oil and 40.5 parts by weight of fish meal, respectively, for use as fish oil and fish meal for fish.
7> 본 발명의 액상비료 원료로 사용하기 위하여, 상기 상분리 된 하층에 존재하는 것으로 유지 및 단백질이 일부 가용화 된 하층의 물층 81중량부를 회수하였다.For use as the liquid fertilizer raw material of the present invention, 81 weight parts of the water layer of the lower layer which was retained in the phase-separated lower layer and the protein was partially solubilized was recovered.
8> 회수한 상기 하층의 존재 유지 및 단백질이 일부 가용화 된 물층 부산물에 휴믹산 0.081중량부를 첨가 혼합하고 완전 용해시켜 유/무기 복합 액상 비료를 제조하였다.0.081 parts by weight of humic acid was added to and mixed with the recovered water layer byproducts of which the lower layer was present and the protein was partially solubilized to prepare an organic / inorganic complex liquid fertilizer.
9> 상기 제조된 휴믹산 가용화 유/무기 복합 액상비료에 염화칼슘 0.1중량부를 첨가하고 80℃에서 10분간 가열 교반하여 액상비료 내 가용화 된 단백질 무기금속염과 휴믹산의 이온교환을 봉쇄시키는 안정화 과정을 수행하여 최종적인 휴믹산 가용화 유/무기 복합 액상비료를 제조하였다.Inorganic fertilizer, 0.1 part by weight of calcium chloride was added to the prepared humic acid-soluble organic / inorganic composite liquid fertilizer, and the mixture was heated and stirred at 80 ° C for 10 minutes to stabilize the ion exchange of solubilized protein inorganic metal salt and humic acid, Inorganic hybrid fertilizer was prepared.
Claims (6)
(1) 오징어 및 생선부산물을 혼합 및 분쇄하여 원료로서 100중량부를 준비하는 원료 준비 단계;
(2) 상기 (1) 단계의 오징어 및 생선부산물을 혼합한 원료 100중량부에 대하여 유기산 2~4중량부 및 정제수 40~60중량부를 첨가하고 가열하여 가수분해를 수행하는 산 가수분해 단계;
(3) 상기 (2) 단계에서 얻어진 가수분해물 내에 잔존하는 미반응 잔사를 여과 분리하여 산 가수분해물을 수득하는 여과 단계;
(4) 상기 (3) 단계에서 수득한 산 가수분해물에 무기염기를 2~4중량부 첨가하고, 가열 교반하여 가수 분해물 내 단백질 성분을 용석 결정화시키는 용석 결정화단계;
(5) 상기 (4) 단계의 용석 결정화물을 분리하여 상층, 중간층, 하층으로 3상의 물질층으로 상분리하는 상분리 단계;
(6) 상기 (5) 단계에서 상 분리된 물질층 중, 상층과 중간층인 유지 및 단백질 용석결정화물을 분리 회수하는 양어사료 회수 단계;
(7) 상기 (5) 단계에서 상 분리된 물질층 중, 하층으로서 유지 및 단백질이 일부 가용화된 물층을 회수하여 액상비료 원료로서 사용하는 양어사료 부산물 회수 단계;
(8) 상기 (7) 단계에서 회수한 양어사료 부산물에 휴믹산 0.5~1.5중량부를 첨가 혼합하고 완전 용해시키는 휴믹산 가용화 단계;
(9) 상기 (8)단계에서 제조된 휴믹산 가용화 복합 액상 비료에 염소계 무기염류를 0.05~0.15중량부를 첨가하고 가열 교반하여 액상 비료내 가용화된 단백질 무기금속염과 휴믹산의 이온교환을 봉쇄시키는 액상비료 안정화 단계;
로 이루어지는 것을 특징으로 하는 오징어 및 생선 부산물의 휴믹산 가용화 유/무기 복합 액상비료 제조방법.A method for producing humic acid-soluble organic / inorganic complex liquid fertilizer of squid and fish by-products comprising the steps of:
(1) a raw material preparing step of preparing 100 parts by weight of a raw material by mixing and crushing squid and fish by-products;
(2) an acid hydrolysis step of adding 2 to 4 parts by weight of organic acid and 40 to 60 parts by weight of purified water to 100 parts by weight of raw material mixed with squid and fish by-products of step (1) and heating to perform hydrolysis;
(3) filtering the unreacted residue remaining in the hydrolyzate obtained in the step (2) to obtain an acid hydrolyzate;
(4) a step of crystallizing zeolite in which 2 to 4 parts by weight of an inorganic base is added to the acid hydrolyzate obtained in the step (3) and the mixture is heated and stirred to crystallize the protein component in the hydrolyzate;
(5) a phase separation step of separating the molten chalcopyrite from the step (4) and separating into a three-phase material layer as an upper layer, an intermediate layer and a lower layer;
(6) an animal feed recovery step of separating and recovering the upper and intermediate layers of fat and protein zeolite from the phase separated material in step (5);
(7) a step of recovering a fish meal by-product, which is used as a liquid fertilizer raw material by recovering a water layer in which the oil and the protein are partially solubilized as a lower layer among the material layers separated in the step (5);
(8) a step of solubilizing humic acid in which 0.5 to 1.5 parts by weight of humic acid is added to and mixed with the by-product of the recovered feed recovered in the step (7) and completely dissolved;
(9) 0.05 to 0.15 parts by weight of chlorine-based inorganic salts are added to the humectant-soluble, combined liquid fertilizer prepared in the step (8), and the mixture is heated and stirred to stabilize the liquid fertilizer to block the ion exchange of the solubilized protein inorganic metal salt and humic acid in the liquid fertilizer step;
Wherein the humic acid-soluble organic-inorganic composite liquid fertilizer is prepared from squid and fish by-products.
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