WO2015026138A1 - Procédé d'élimination de limonène et dispositif d'élimination de limonène dans un liquide de saccharification de biomasse, et procédé de production de bioéthanol au moyen du procédé d'élimination - Google Patents

Procédé d'élimination de limonène et dispositif d'élimination de limonène dans un liquide de saccharification de biomasse, et procédé de production de bioéthanol au moyen du procédé d'élimination Download PDF

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Publication number
WO2015026138A1
WO2015026138A1 PCT/KR2014/007693 KR2014007693W WO2015026138A1 WO 2015026138 A1 WO2015026138 A1 WO 2015026138A1 KR 2014007693 W KR2014007693 W KR 2014007693W WO 2015026138 A1 WO2015026138 A1 WO 2015026138A1
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WIPO (PCT)
Prior art keywords
limonene
biomass
activated carbon
removal
cellulose fiber
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PCT/KR2014/007693
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English (en)
Korean (ko)
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배현종
신한기
최인성
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전남대학교산학협력단
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Priority to CN201480046589.7A priority Critical patent/CN105473621A/zh
Publication of WO2015026138A1 publication Critical patent/WO2015026138A1/fr

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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M45/00Means for pre-treatment of biological substances
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M21/00Bioreactors or fermenters specially adapted for specific uses
    • C12M21/12Bioreactors or fermenters specially adapted for specific uses for producing fuels or solvents
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/02Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06Ethanol, i.e. non-beverage
    • C12P7/08Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
    • C12P7/12Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing sulfite waste liquor or citrus waste
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to a method for removing limonene of biomass, and more particularly, to efficiently remove limonene present in biomass such as citrus fruit, orange, grapefruit, lemon and lime, and to improve bioethanol production yield. It relates to a limonene removal method, limonene removal device and bioethanol production method using the removal method of the biomass saccharification solution.
  • Raw materials for the production of these first-generation bioethanol face many problems such as competition with food and livestock feed, saturation of cultivated area. In order to overcome this, research is being conducted to produce bioethanol using waste resources.
  • the saccharification process converts biomass into sugar components by acid and enzyme treatment
  • the fermentation process refers to a process of converting ethanol and carbon dioxide by using microorganisms such as yeast and E. coli using the saccharification liquid generated through saccharification process.
  • the presence of a fermentation inhibitor to inhibit the fermentation of microorganisms is very low efficiency of conversion of sugar components to ethanol.
  • Biomass such as citrus, orange, grapefruit, lemon and lime are attracting attention as a raw material for bioethanol production because they contain high sugar content, but they contain fermentation inhibitors called limonene. There is a difficulty. Therefore, effective removal of limonene for bioethanol production is recognized as an important task.
  • the present inventors have completed the present invention by solving the problems of the limonene removal method and apparatus using the conventional steam aeration as a result of research efforts to solve this problem.
  • an object of the present invention by using activated carbon and cellulose fibers, limonene known as fermentation inhibitors can be removed to a level that will not affect the fermentation process, the biomass saccharification liquid which can improve the fermentation efficiency converted to ethanol It is to provide a method for removing limonene.
  • Another object of the present invention is to provide a separate process apparatus, such as a steam decay apparatus, and a limonene removal method of biomass saccharified liquid which can be usefully used because high energy for generating steam is not required.
  • Another object of the present invention is to separate the limonene from the activated carbon and cellulose fiber after the limonene removal process, can reduce the waste of resources, the activated carbon and cellulose fiber can be easily reused, significantly reducing the processing cost
  • the present invention provides a method for removing limonene from a biomass saccharified solution.
  • the present invention comprises the steps of preparing a saccharified liquid obtained from the biomass containing limonene; And it provides a limonene removal method of biomass saccharified liquid comprising the step of contacting any one or more of the saccharified liquid and activated carbon and cellulose fiber.
  • the contacting step is used 0.3 to 0.5g of activated carbon based on the limonene content of 0.8411g / cm 3 of the saccharified solution when using activated carbon.
  • the step of contacting the cellulose fiber is used 0.125 to 0.2g based on the limonene content of 0.8411g / cm 3 of the saccharified solution when using the cellulose fiber.
  • the present invention also provides a saccharified liquid obtained from limonene-containing biomass, wherein the limonene content is less than 0.025% by weight.
  • the present invention is a hollow housing therein; And it provides a limonene removal device comprising any one or more of activated carbon and cellulose fiber inserted into the hollow at a predetermined thickness.
  • At least one of the activated carbon and cellulose fiber is contacted with saccharified liquid obtained from limonene containing biomass to remove limonene.
  • the present invention comprises the steps of preparing a saccharified solution in which the limonene removal method is performed; And it provides a method of producing a bioethanol comprising a fermentation step of fermenting using any one or more of yeast and E. coli in the saccharification liquid.
  • the present invention has the following excellent effects.
  • a separate process apparatus such as a steam attenuating device, and high energy for generating steam can be usefully used.
  • limonene can be separated from the activated carbon and the cellulose fiber, thereby reducing the waste of resources, and the activated carbon and the cellulose fiber can be easily reused, thereby significantly reducing the processing cost.
  • FIG. 1 (a) is a graph analyzing the limonene content before limonene removal using GC (Gas Chromatography), (b) is a graph analyzing the result after limonene removal using the limonene removal method using GC to be.
  • FIG. 2 (a) is a schematic diagram of a limonene removal apparatus according to an embodiment of the present invention, (b) is a schematic diagram of a limonene removal apparatus according to another embodiment of the present invention, (c) is another of the present invention It is a schematic diagram of a limonene removal apparatus which concerns on an Example.
  • Figure 3 is a graph showing the fermentation efficiency before and after limonene removal using the limonene removal method of the present invention.
  • the technical feature of the present invention is a new limonene removal method that can improve the fermentation efficiency of converting limonene, known as a fermentation inhibitor, to a level that will not affect the fermentation process by using activated carbon and cellulose fiber to convert to ethanol.
  • the limonene removal method of the biomass saccharification liquid of the present invention includes preparing a saccharification liquid obtained from the biomass containing limonene and contacting any one or more of the saccharification liquid with activated carbon and cellulose fiber.
  • the biomass is not limited to biomass containing limonene, but any one or more selected from the group consisting of peels of tangerines, oranges, grapefruits, lemons, limes, and mixtures thereof, which are discarded as waste after being used. This is preferably used. This is because waste resources that are discarded can be used as biomass, thereby reducing the cost of treating waste resources and producing value-added resources such as bioethanol and limonene from waste resources.
  • the step of secreting the saccharification liquid may be prepared in general through the saccharification process of acid hydrolysis and enzymatic hydrolysis from the biomass.
  • the method of hydrolysis is not limited.
  • Figure 1 (a) is a graph of the saccharified solution analyzed by GC, showing that the saccharin contains limonene.
  • Figure 1 (b) is a result of analyzing the saccharified solution after removing the limonene using the limonene removal method of the present invention using GC.
  • limonene contained in the saccharified solution is contacted with activated carbon, contacted with cellulose fiber, and contacted with a mixture prepared by mixing the activated carbon and cellulose fiber.
  • Limonene may be removed through one or more of the step of making.
  • the contacting step is preferably 0.3 to 0.5 g of activated carbon based on the limonene content of 0.8411 g / cm 3 of the saccharified solution when activated carbon is used. If less than 0.3 g of activated carbon is used, the content of limonene that is not removed is higher than the concentration causing the inhibition of fermentation, which causes fermentation inhibition in the fermentation process using microorganisms, thereby lowering the production efficiency of bioethanol. In addition, when using more than 0.5g of activated carbon exceeds the amount necessary to remove limonene is a waste of resources, because it does not affect the fermentation efficiency.
  • the cellulose fiber in the contacting step it is preferable that 0.125 to 0.2g of the cellulose fiber is used based on the limonene content 0.8411g / cm 3 of the saccharified solution.
  • the content of limonene, which is not removed is higher than the concentration causing the inhibition of fermentation, which induces the inhibition of fermentation in the fermentation process using microorganisms.
  • the production efficiency of is lowered, and when using the cellulose fiber in excess of 0.2g, it exceeds the amount necessary to remove limonene, wastes resources, and does not affect the fermentation efficiency.
  • a saccharified liquid obtained from a limonene-containing biomass wherein the limonene content is less than 0.025% by weight.
  • the sugar component contained in the saccharified liquid may be converted into bioethanol by the microorganism.
  • the limonene content of the saccharified solution may be used by removing it to 0.020% by weight or less. If the limonene content of the saccharified solution is removed to 0.020% by weight or less, limonene does not affect the fermentation process at all, and bioethanol can be produced efficiently.
  • a hollow is formed therein, so that the activated carbon is inserted into the hollow at a predetermined thickness to provide a device capable of removing limonene.
  • the cellulose fiber may be inserted into the hollow at a predetermined thickness to remove limonene, and as shown in (c) of FIG. 2, the activated carbon and the cellulose fiber of the hollow may be removed.
  • the mixture can be inserted to a certain thickness to remove limonene.
  • the limonene removal device is not limited as long as it is manufactured containing any one or more of activated carbon and cellulose fiber.
  • the activated carbon and cellulose fiber to which limonene is adsorbed after contact with the saccharification solution to remove limonene can be reused by separating limonene using an organic solvent, wherein the separated limonene is a food additive, a perfume of perfume, a known detergent It can be used as a car article, a cleaning agent, and the like.
  • saccharomyces cerevisiae saccharomyces cerevisiae
  • Any of the conventional strains known in the art may be used, such as convertible heat resistant strains, recombinant strains that can simultaneously perform glycosylation and fermentation.
  • Limonene was removed by contacting the saccharified solution containing 1% by weight of limonene using 0 mg, 50 mg, 100 mg, 150 mg, 200 mg, 250 mg, 300 mg, 500 mg of each activated carbon, and the results are shown in Table 1 below.
  • Limonene was removed by contacting the saccharified solution containing 1% by weight of limonene using 0 mg, 5 mg, 15 mg, 25 mg, 50 mg, 75 mg, 100 mg, 125 mg, and 150 mg of each of the cellulose fibers. Shown in
  • a limonene removal device was prepared in which 25 mg of cellulose fiber and 150 mg of activated carbon were mixed.
  • Limonene was removed from the saccharification solution containing 1% by weight of limonene by using the limonene removing apparatus prepared in Example 3, and as a result, all limonene was removed as shown in Table 3 below.
  • Bioethanol was prepared from the saccharification liquid from which the components of limonene were removed from each of Examples 1 to 4 by less than 0.025% by weight.
  • the strain using a known Saccharomyces cerevisiae the pH was maintained at 5.0, the fermentation process was carried out in a fermentation tank of 30 under the conditions of rpm 200, to obtain a bioethanol.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un procédé d'élimination de limonène d'une biomasse. Plus particulièrement, la présente invention concerne : un procédé pour éliminer le limonène et un dispositif pour éliminer le limonène présent dans un liquide de saccharification de biomasse, grâce à quoi il est possible d'éliminer efficacement le limonène présent dans une biomasse telle qu'une écorce de mandarine, une écorce d'orange, une écorce de pamplemousse, une écorce de citron et une écorce de lime, et il est possible d'améliorer le rendement de production de bioéthanol ; ainsi qu'un procédé de production de bioéthanol utilisant ce procédé d'élimination.
PCT/KR2014/007693 2013-08-22 2014-08-19 Procédé d'élimination de limonène et dispositif d'élimination de limonène dans un liquide de saccharification de biomasse, et procédé de production de bioéthanol au moyen du procédé d'élimination WO2015026138A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201480046589.7A CN105473621A (zh) 2013-08-22 2014-08-19 去除生物质糖化液的柠檬烯的方法、柠檬烯去除装置及利用所述去除方法的生物乙醇的制备方法

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KR1020130099680A KR101498213B1 (ko) 2013-08-22 2013-08-22 바이오매스 당화액의 리모넨 제거방법, 리모넨 제거 장치 및 상기 제거방법을 이용한 바이오에탄올 제조 방법
KR10-2013-0099680 2013-08-22

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Citations (4)

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Publication number Priority date Publication date Assignee Title
KR19980071950A (ko) * 1998-07-07 1998-10-26 노경호 한국산 귤껍질로부터 페릴릴알코올과 디-리모넨의 추출 및 분리
KR100318755B1 (ko) * 1999-12-24 2001-12-28 손재익 저온멸균법을 이용한 목질계 당화액으로부터 고농도에탄올 제조 방법
JP2002336000A (ja) * 2001-05-21 2002-11-26 Kurita Water Ind Ltd 糖液の精製装置
JP2010094093A (ja) * 2008-10-17 2010-04-30 National Institute Of Advanced Industrial Science & Technology 柑橘類外皮からエタノールを製造する方法

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
IT1199400B (it) * 1984-07-03 1988-12-30 Aid Agricolture Ind Dev Procedimento per la estrazione della limonina e dell'acido limonoico dai succhi di agrumi
JPH05328915A (ja) * 1992-06-01 1993-12-14 Teijin Ltd リモニンの除去方法
KR100555225B1 (ko) * 2004-03-31 2006-03-03 김문갑 디클로로프로판계 세정제의 냄새 저감 방법
US8252566B2 (en) * 2008-05-20 2012-08-28 Jj Florida Properties Llc Ethanol production from citrus waste through limonene reduction
BRPI0908634A2 (pt) * 2008-05-20 2016-08-30 Jj Florida Properties Llc método para produzir etanol a partir de resíduos cítricos
WO2013063251A1 (fr) * 2011-10-26 2013-05-02 Frito-Lay North America, Inc. Conversion écologique de déchets d'écorce d'agrumes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19980071950A (ko) * 1998-07-07 1998-10-26 노경호 한국산 귤껍질로부터 페릴릴알코올과 디-리모넨의 추출 및 분리
KR100318755B1 (ko) * 1999-12-24 2001-12-28 손재익 저온멸균법을 이용한 목질계 당화액으로부터 고농도에탄올 제조 방법
JP2002336000A (ja) * 2001-05-21 2002-11-26 Kurita Water Ind Ltd 糖液の精製装置
JP2010094093A (ja) * 2008-10-17 2010-04-30 National Institute Of Advanced Industrial Science & Technology 柑橘類外皮からエタノールを製造する方法

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CN105473621A (zh) 2016-04-06
KR101498213B1 (ko) 2015-03-06
KR20150023104A (ko) 2015-03-05

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