KR20030035636A - Production method of saccharides from cellulose wastes in paper industry - Google Patents

Production method of saccharides from cellulose wastes in paper industry Download PDF

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KR20030035636A
KR20030035636A KR1020010067888A KR20010067888A KR20030035636A KR 20030035636 A KR20030035636 A KR 20030035636A KR 1020010067888 A KR1020010067888 A KR 1020010067888A KR 20010067888 A KR20010067888 A KR 20010067888A KR 20030035636 A KR20030035636 A KR 20030035636A
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paper
waste sludge
hydrolase
cellulose
fine powder
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KR1020010067888A
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Korean (ko)
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김용환
류정용
송봉근
신종호
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한국화학연구원
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Publication of KR20030035636A publication Critical patent/KR20030035636A/en

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    • 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
    • C12P19/00Preparation of compounds containing saccharide radicals
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    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14Hydrolases (3)
    • C12N9/24Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C12N9/2405Glucanases
    • C12N9/2408Glucanases acting on alpha -1,4-glucosidic bonds
    • C12N9/2411Amylases
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    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14Hydrolases (3)
    • C12N9/24Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C12N9/2405Glucanases
    • C12N9/2434Glucanases acting on beta-1,4-glucosidic bonds
    • C12N9/2437Cellulases (3.2.1.4; 3.2.1.74; 3.2.1.91; 3.2.1.150)
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    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14Hydrolases (3)
    • C12N9/24Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C12N9/2477Hemicellulases not provided in a preceding group
    • C12N9/248Xylanases
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12YENZYMES
    • C12Y302/00Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01001Alpha-amylase (3.2.1.1)
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12YENZYMES
    • C12Y302/00Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01002Beta-amylase (3.2.1.2)
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12YENZYMES
    • C12Y302/00Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01004Cellulase (3.2.1.4), i.e. endo-1,4-beta-glucanase

Abstract

PURPOSE: A method for producing saccharides from waste sludge generated from the paper process is provided, thereby producing saccharides useful for microorganisms, and decreasing environmental pollution caused by the waste sludge of paper. CONSTITUTION: A method for producing saccharides from waste sludge generated from the paper process comprises the steps of: mixing the waste sludge of paper under following conditions: the temperature of 50 deg. C; the flow rate of 105 l/min; and the air flow rate of 15 l/min to separate small particles and powder; and treating the separated small particles and powder with hydrolase or acid catalysts, wherein the hydrolase is one or two selected from cellulase, amylase, xylase and hemicellulase and is added in an amount of 0.01 to 0.1 wt.%; and the acid catalyst is selected from sulfuric acid, hydrochloric acid, and nitric acid and is added in an amount of 0.01 to 0.1 wt.%.

Description

제지 폐슬러지로부터 당류를 생산하는 방법{Production method of saccharides from cellulose wastes in paper industry}Production method of saccharides from cellulose wastes in paper industry

본 발명은 제지 폐슬러지로부터 당류를 생산하는 방법에 관한 것으로서, 더욱 상세하게는 제지공정 중에 다량으로 폐기되는 폐슬러지로부터 부상부유처리를 통하여 미세분을 분리하고, 이 미세분을 가수분해효소 또는 산촉매로 처리하여 미생물이 에너지원으로 사용할 수 있는 당류를 생산함으로써, 미생물이 상기 생산된 당류를 이용하여 유용물질을 생산할 수 있을 뿐만 아니라 제지 폐기물을 절감하여 환경오염부하를 크게 줄일 수 있는 제지 폐슬러지로부터 당류를 생산하는 방법에 관한 것이다.The present invention relates to a method for producing sugar from paper waste sludge, and more particularly, to separate fine powder from flotation waste sludge that is disposed in large quantities during the papermaking process through flotation, and to convert the fine powder into a hydrolase or an acid catalyst. By producing sugars that microorganisms can use as energy sources by treating them with microorganisms, the microorganisms can produce useful materials using the produced sugars as well as from paper waste sludge that can significantly reduce environmental pollution loads by reducing paper waste. It relates to a method of producing a sugar.

현재 우리 나라의 전체 지류 생산량은 약 800만 톤에 달하여 세계 10위권의 지류 생산국에 진입하였다. 특히, 상품 포장의 중핵을 담당하고 있는 골판지의 원지 생산량은 지류 총 생산량의 30% 이상을 차지하고 있다. 포장재로서의 골판지는 인쇄 및 가공이 용이하고, 중량대비 강도가 우수하며 재활용이 가능하다는 장점이 있다. 현재 우리 나라의 고지 재활용률은 세계 최고수준으로서 95년 기준으로 제지산업 규모 상위 10개국 가운데 종이 재활용 비율이 72%로 가장 높은데(Vital Signs 1998), 특히 그 중에서도 골판지 원지는 주로 국산 골판지 고지를 주원료로 제조되고 있으며, 이에 따라 국산 골판지 고지의 재활용률이 매우 높은 특징이 있다.At present, our total tributary production amounted to about 8 million tons, making it the world's top ten tributary producer. In particular, the raw paper production of corrugated cardboard, which is the core of product packaging, accounts for more than 30% of the total paper production. Corrugated paper as a packaging material has the advantage of easy printing and processing, excellent strength to weight and recycling. The recycling rate of waste paper in our country is the highest in the world and the highest recycling rate of paper is 72% among the top 10 paper industry in 1995 (Vital Signs 1998). Especially, the base of corrugated cardboard is mainly made of domestic cardboard waste. It is manufactured, and accordingly, the recycling rate of domestic corrugated cardboard is very high.

제지공정 중에는 제품 품질 및 균일성 확보를 위하여 막대한 양의 섬유소가 폐기물로 배출되고 있으며, 그 양은 국내의 경우 년간 약 150 만톤에 달한다. 이러한 섬유소 폐기물은 함수율이 높아 소각처리하기가 곤란하여 탈수 후 매립하는 것이 일반적인 처리방법이었으며 이로 인하여 환경오염 유발효과가 크며 동시에 이의 처리에 상당 비용이 소모되고 있는 실정이다. 이러한 섬유소 폐기물은 그 성분이 제품생산에 부적합한 매우 크기가 작은 섬유소 파편과 탄산칼슘, 탈크와 같은 무기충진물로 이루어져 있다. 특히, 골판지의 주원료가 되는 국산 골판지 고지는 거듭된 재생처리로 인하여 이러한 폐기물이 차지하는 함량이 전체 지료의 절반에 달할 만큼 크며, 아울러 섬유가 각질화됨에 따라 재생처리가 거듭될수록 폐기되어야 할 미세분의 형성이 더욱 촉진되고 있다. 일반적으로 크기 75 ㎛ 이하의 무기물 및 단섬유를 일컫는 미세분은 골판지 원지의 초지 시 습지필의 탈수를 저해하여 생산성을 저하시키는 요인이 되어 왔다. 따라서, 현재까지는 이러한 미세분을 분리, 제거하는 노력이 많이 이루어져 왔으나 이의 이용에 관한 보고는 전무하다.During the papermaking process, a huge amount of fiber is discharged as waste to ensure product quality and uniformity. The amount is about 1.5 million tons per year in Korea. Since the fiber waste has a high water content, it is difficult to incinerate, and landfilling after dehydration has been a general treatment method, which causes a great effect on environmental pollution and at the same time consumes a considerable amount of cost. These cellulose wastes consist of very small cellulose fragments whose minerals are inappropriate for production and inorganic fillers such as calcium carbonate and talc. In particular, the domestic corrugated cardboard, which is the main raw material of corrugated cardboard, is such that the amount of such waste occupies about half of the total material due to the repeated regeneration treatment. It is being promoted even more. In general, fine powders, which refer to inorganic matters and short fibers having a size of 75 μm or less, have been a factor of lowering productivity by inhibiting dehydration of wet paper peeling paper during papermaking. Therefore, until now, many efforts have been made to separate and remove these fines, but there are no reports on their use.

일반적으로 목질계 섬유소로부터 당류를 생산하기 위해서는 고온, 고압 하에서 목질계 섬유소의 결정구조를 해체하여야 하며 동시에 황산과 같은 산촉매를 다량으로 필요로 한다. 이렇게 가혹한 공정조건은 많은 에너지를 필요로 하며 동시에 상당히 큰 반응기 및 고가의 반응기 재질을 요구한다. 따라서, 이러한 고온, 고압 조건은 목질계 섬유소로부터 유용한 당류를 생산하는데 있어서 큰 걸림돌이 되어져 왔다.In general, in order to produce sugars from wood fiber, the crystal structure of wood fiber is dismantled under high temperature and high pressure, and at the same time, a large amount of acid catalyst such as sulfuric acid is required. Such harsh process conditions require a lot of energy and at the same time require a fairly large reactor and expensive reactor materials. Therefore, such high temperature and high pressure conditions have been a major obstacle in producing useful sugars from wood fiber.

이에, 본 발명자들은 상기와 같은 문제점을 해결하기 위하여 연구한 결과, 폐슬러지로부터 부상부유 처리를 통하여 미세분을 분리하고, 이렇게 분리된 미세분을 가수분해효소 또는 산촉매로 처리하여 셀룰로오즈 섬유소 성분을 분해하여 당류를 생산함으로써 본 발명을 완성하게 되었다.Therefore, the present inventors have studied in order to solve the above problems, and as a result, the fine powder is separated from the flocculated sludge by flotation treatment, and the separated fine powder is treated with a hydrolase or an acid catalyst to decompose cellulose cellulose components. The present invention was completed by producing a saccharide.

본 발명은 제지공정 중에서 다량으로 폐기되는 폐슬러지 미세분을 재료로 하여 당류를 생산함으로써 주변 자연환경에 배출되는 폐기물을 감량하면서 동시에 미생물이 유용하게 에너지원으로 사용할 수 있는 당류 생산방법을 제공하는데 그 목적이 있다.The present invention provides a sugar production method that can reduce the waste discharged to the surrounding natural environment by producing sugars using waste sludge fines discarded in large quantities in the papermaking process and at the same time, microorganisms can be usefully used as an energy source. There is a purpose.

본 발명은 제지공정 시 폐기물로 버려지는 폐슬러지로부터 부상부유 처리를 통하여 미세분을 분리하고, 이 미세분을 가수분해효소나 산촉매로 처리하여 당류를 생산하는 방법을 그 특징으로 한다.The present invention is characterized by a method for producing saccharides by separating fines from flotation waste sludge which is discarded as waste during the papermaking process, and treating the fines with a hydrolase or an acid catalyst.

이하, 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.

본 발명은 제지공정 시 폐기물로 버려지는 폐슬러지로부터 부상부유 처리를 통하여 미세분을 분리하고, 이 미세분을 가수분해효소나 산촉매로 처리하여 당류를 생산하는 방법에 관한 것으로서, 생산된 당류는 미생물에 의해 용이하게 이용되어 유용물질을 생산할 뿐만 아니라 환경오염부하를 줄일 수 있다.The present invention relates to a method for producing a saccharide by separating the fine powder from the waste sludge discarded as waste during the papermaking process, and treating the fine powder with a hydrolase or an acid catalyst, wherein the produced sugar is a microorganism. It can be easily used to produce useful materials as well as reduce environmental pollution load.

특히, 본 발명에 따른 당류 생산방법은 환원당을 주목적으로 얻기 위함이며, 환원당은 미생물이 직접적으로 분해, 섭취할 수 있는 탄수화물을 의미하며, 예를 들면 포도당, 과당 등이 이에 속한다.In particular, the sugar production method according to the present invention is to obtain a reducing sugar mainly, reducing sugar means a carbohydrate that microorganisms can be directly degraded, ingested, for example, glucose, fructose and the like.

한편, 본 발명은 기존에 인쇄물의 탈묵처리에 적용되어 온 부상부유 처리를 골판지 고지의 미세분 분리에 최초로 적용함으로써 골판지 고지에 함유된 미세분을 효과적으로 분리한다. 미세분 분리 시의 부상부유 처리 조건은 농도 1.4%, 온도 50 ℃, 유속 105 L/min, 공기유량 15 L/min의 조건이 바람직하다.On the other hand, the present invention effectively separates the fines contained in the corrugated cardboard by applying the floating flotation treatment, which has been previously applied to the deinking treatment of printed matter, for the first time to separate the fines of the corrugated cardboard. Floating flotation treatment conditions for fine powder separation are preferably conditions of concentration 1.4%, temperature 50 占 폚, flow rate 105 L / min, and air flow rate 15 L / min.

상기 분리된 미세분은 주로 셀룰로오즈 섬유소 조각으로 이루어져 있으며, 이러한 미세분은 기존의 목질계 섬유소와는 달리 결정구조가 반복되는 제지공정을 거침에 따라 완전히 해체된 모습을 보여주고 있다. 따라서, 미세분 중의 셀룰로오즈 섬유소는 상당히 넓은 비표면적을 가지고 있으며 동시에 물에 수화된 상태로 존재한다. 이러한 수화된 미세분 중의 셀룰로오즈 섬유소는 일반 목질계 섬유소와는 달리 가수분해효소나 산촉매의 공격을 쉽게 받아 당류로 분해되기 쉽다. 이때, 가수분해효소로는 셀룰라아제, 아밀라아제, 자일라아제 및 헤미셀룰라아제 중에서 선택된 1종 또는 2종 이상으로, 0.01 내지 0.1 중량%가 바람직하며, 산촉매로는 황산, 염산, 질산 중에서 선택된 것으로 0.01 내지 0.1 중량%가 바람직하다.상기 범위를 벗어나면 효과적인 가수분해 반응이 발생하지 않는 문제점이 있다.The separated fine powder is mainly composed of cellulose fiber fragments, and unlike the conventional wood fiber, the fine powder is completely dismantled through the papermaking process in which the crystal structure is repeated. Thus, the cellulose fibres in the fines have a fairly large specific surface area and at the same time remain hydrated in water. The cellulose fiber in the hydrated fine powder is unlikely to be broken down into sugars by being easily attacked by a hydrolase or an acid catalyst, unlike ordinary wood fiber. In this case, the hydrolase is one or two or more selected from cellulase, amylase, xylase, and hemicellulase, and preferably 0.01 to 0.1 wt%, and an acid catalyst selected from sulfuric acid, hydrochloric acid, and nitric acid, 0.01 to 0.1. Weight% is preferred. If it is out of the above range, there is a problem that no effective hydrolysis reaction occurs.

특히, 제지공정수 중에 포함되어져 있는 다양한 혐기성 미생물과 호기성 미생물이 분비하는 효소의 작용으로 미세분 중의 셀룰로오즈 섬유소는 일부 분해가 진행되는 과정에 있기 때문에 외부에서 투입되는 셀룰라아제 또는 산촉매에 의하여 분해가 더욱 촉진될 수 있다.In particular, due to the action of enzymes secreted by various anaerobic and aerobic microorganisms contained in the papermaking process, the cellulose fiber in the fine powder is in the process of being partially decomposed, so that the decomposition is further promoted by externally introduced cellulase or acid catalyst. Can be.

이러한 미세분 중의 셀룰로오즈를 분해하여 당류를 생산할 경우 미세분의 형태로 폐기되는 제지슬러지량을 크게 줄일 수 있으며 동시에 미세분을 재활용 공정 중에서 분리함으로써 폐수처리장으로 유입되는 오염부하를 저감할 수 있다. 이러한 결과로 미생물의 주요한 에너지원인 당류를 생산하여 유용물질을 생산할 수 있을 뿐만 아니라 폐수처리장으로 유입되는 오염물의 양을 줄임으로써 폐수처리 효율을 향상시킬 수 있다.When saccharides are produced by decomposing cellulose in the fine powder, the amount of paper sludge disposed in the form of fine powder can be greatly reduced, and at the same time, by separating the fine powder in a recycling process, it is possible to reduce the pollution load flowing into the wastewater treatment plant. As a result, it is possible to produce useful substances by producing sugars, which are the main energy sources of microorganisms, and improve wastewater treatment efficiency by reducing the amount of contaminants introduced into the wastewater treatment plant.

이하, 본 발명을 다음 실시예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명이 이에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

실시예 1Example 1

골판지 원지 생산업체인 D사의 헤드박스(head box)에서 라이너지의 이면 지료를 채취한 후, E형 부상부유기[독일 Voith 사]를 사용하여 농도 1.4%, 온도 50 ℃, 유속 105 L/min, 공기유량 15 L/min의 조건으로 2분간 부상부유 처리하여 17%의 리젝트분을 분리하였다. 분리된 리젝트는 3% 농도로 농축된 상태로 이에 포함된 섬유 미세분과 접착용 전분을 분해하기 위하여 트리코데르마 콩기브라키아툼(Trichoderma longibrachiatum)에서 생성된 셀룰라아제(Cellulase)와 헤미셀룰라아제(Hemicellulase)의 복합 효소인 퍼갈라아제 에프엘 60(Pergalase FL-60)[GENENCOR 사]과, 바실리스 리케니포르미스(Bacillis licheniformis)에서 생성된 구조명 1,4-α-D-글루칸 글루카노-하이드롤라제(1,4-α-D-glucan glucano-hydrolase)인 알파-아밀라아제(α-amylase)계 효소인 터마밀 엘에스(Termamyl LS)[NOVO 사]를 각각 0.05 중량% 및 0.03 중량% 수준으로 첨가하여 45 ℃에서 1시간 동안 저속으로 교반하였다.After collecting the backing material of the liner paper from the head box of the corrugated cardboard producer D, using an E-type flotation machine (Germany Voith), the concentration was 1.4%, the temperature was 50 ° C, the flow rate was 105 L / min, 17% of the reject fraction was separated by flotation for 2 minutes under the condition of an air flow rate of 15 L / min. The tricot der town konggi beuraki Atum the cellulase (Cellulase) and hemicellulase (Hemicellulase) produced in (Trichoderma longibrachiatum) to separate the reject is to break down the fiber fine minutes and adhesive starch for contained therein in the state concentrated to a 3% concentration Structure enzyme 1,4-α-D-glucan glucano-hydrolase produced by the complex enzyme Pergalase FL-60 ( GENENCOR) and Bacillis licheniformis (1,4-α-D-glucan glucano-hydrolase), an alpha-amylase enzyme, Teramyl LS [NOVO] was added at 0.05 wt% and 0.03 wt%, respectively. Stirred at 45 ° C. for 1 hour at low speed.

비교예 1Comparative Example 1

목질계 셀룰로오즈를 주성분으로 하는 분말형 셀룰로오즈[아비셀, 시그마사]를 분해하기 위하여 트리코데르마 콩기브라키아툼(Trichoderma longibrachiatum)에서 생성된 셀룰라아제(Cellulase)와 헤미셀룰라아제(Hemicellulase)의 복합 효소인 퍼갈라아제 에프엘 60(Pergalase FL-60)[GENENCOR 사]과, 바실리스 리케니포르미스(Bacillis licheniformis)에서 생성된 구조명 1,4-α-D-글루칸 글루카노-하이드롤라제인 알파-아밀라아제(α-amylase)계 효소인 터마밀 엘에스(Termamyl LS)[NOVO 사]를 각각 0.05 중량% 및 0.03 중량% 수준으로 첨가하여 45 ℃에서 1시간 동안 저속으로 교반하였다.Pergalase, a complex enzyme of cellulase and hemicellulase produced by Trichoderma longibrachiatum, to decompose powdered cellulose [avicel, sigma] mainly composed of wood-based cellulose Pergalase FL-60 ( GENENCOR) and the structure name 1,4-α-D-glucan glucano -hydrolase alpha-amylase (α- ) produced by Bacillis licheniformis Amylase) termamyl LS (Termamyl LS) [NOVO] was added at a level of 0.05% by weight and 0.03% by weight, respectively, and stirred at 45 ° C. for 1 hour at low speed.

당류 농도 (mg/L)Sugar Concentration (mg / L) 실시예 1Example 1 비교예 1Comparative Example 1 비 고Remarks 글루코오스Glucose 10,50010,500 2,0002,000 효소시험법 이용Use of enzyme test 셀로바이오스Cellobios 3,0003,000 1,0001,000 HPLC 이용Using HPLC 총환원당Total Reduction Party 12,00012,000 3,5003,500 발색법이용Color development

상기 표 1에서 볼 수 있듯이, 동일한 조건하에서 제지슬러지 미세분을 이용하여 목질계 셀룰로오즈에 비하여 약 5배 이상 다량의 당류를 생산할 수 있다. 이는 미세분 중의 셀룰로오즈 섬유소가 분말형 셀룰로오즈에 비하여 결정구조가 해체되어 투입된 가수분해효소의 작용을 쉽게 받았기 때문이다. 이는 미세분 중의 셀룰로오즈는 공정수 중에 존재하는 다양한 미생물에 의하여 손쉽게 분해될 수 있음을 보여주고 있다. 따라서, 이렇게 쉽게 분해될 수 있는 미세분을 분리하지 못하면 이는 상당히 큰 유기물 부하를 폐수처리장에 부가할 수 있다. 따라서, 이러한 미세분을 분리하여 위와 같이 당류생산을 위하여 이용할 경우 고농도의 당류를 쉽게 생산할 수 있으며 동시에 환경오염부하를 크게 줄일 수 있다.As can be seen in Table 1, under the same conditions, it is possible to produce a large amount of sugars about 5 times or more than wood-based cellulose using paper sludge fine powder. This is because the cellulose fibrin in the fine powder is easily disintegrated in the crystal structure compared to the powdered cellulose, and thus easily receives the action of the introduced hydrolase. This shows that cellulose in the fine powder can be easily decomposed by various microorganisms present in the process water. Thus, failure to separate such easily degradable fines can add a significant organic load to the wastewater treatment plant. Therefore, when the fine powder is separated and used for the production of sugars as described above, it is possible to easily produce a high concentration of sugars and at the same time can significantly reduce the environmental pollution load.

실시예 2Example 2

골판지 원지 생산업체인 D사의 헤드박스(head box)에서 라이너지의 이면 지료를 채취한 후, E형 부상부유기[독일 Voith 사]를 사용하여 농도 1.4%, 온도 50 ℃, 유속 105 L/min, 공기유량 15 L/min의 조건으로 2분간 부상부유 처리하여 17%의 리젝트분을 분리해 걷어내었다. 분리된 리젝트는 3% 농도로 농축된 상태로 이에 포함된 섬유 미세분 중의 셀룰로오즈를 분해하기 위하여 황산용액을 0.07%가 되도록 첨가하고 60 ℃에서 2 시간동안 저속으로 교반하였다.After collecting the backing material of the liner paper from the head box of the corrugated cardboard producer D, using an E-type flotation machine (Germany Voith), the concentration was 1.4%, the temperature was 50 ° C, the flow rate was 105 L / min, The flotation was floated for 2 minutes at 15 L / min of air flow to separate and remove 17% of the reject fraction. The separated reject was concentrated to 3% concentration to add 0.07% sulfuric acid solution to decompose cellulose in the fiber fine particles contained therein and stirred at 60 ° C. for 2 hours at low speed.

비교예 2Comparative Example 2

목질계 셀룰로오즈를 주성분으로 하는 분말형 셀룰로오즈[아비셀, 시그마사]를 분해하기 위하여 황산용액을 0.07%가 되도록 첨가하고 90 ℃에서 4 시간동안 저속으로 교반하였다.In order to decompose powdered cellulose [avicel, Sigma, Inc.] mainly composed of wood cellulose, sulfuric acid solution was added to 0.07% and stirred at 90 ° C. for 4 hours at low speed.

당류 농도 (mg/L)Sugar Concentration (mg / L) 실시예 2Example 2 비교예 2Comparative Example 2 비 고Remarks 글루코오스Glucose 20,00020,000 4,0004,000 효소시험법 이용Use of enzyme test 셀루바이오스Cellobios -- -- HPLC 이용Using HPLC 총환원당Total Reduction Party 26,00026,000 4,5004,500 발색법이용Color development

상기 표 2에서 볼 수 있듯이, 일반적인 목질계 섬유소로부터 산촉매(황산)를 이용하여 당류를 생산하는 경우에 비하여 미세분 중의 섬유소로부터 당류를 생산하는 것이 월등히 쉬운 것을 알 수 있다. 특히, 총환원당의 농도가 높은 것은 분말형 순수 셀룰로오즈에 비하여 제지슬러지 미세분 중에는 셀룰로오즈 외에 헤미셀룰로오즈 등이 존재하여 이를 산촉매로 분해할 경우 글루코오스 외에 여러 가지 단당류가 다양하게 생성되기 때문이다. 따라서, 가수분해효소를 사용할 경우와 유사하게 역시 산촉매를 이용할 경우에도 미세분으로부터 용이하게 당류를 생산할 수 있다.As can be seen in Table 2, it can be seen that it is much easier to produce sugars from the fiber in the fine powder as compared to the production of sugars using an acid catalyst (sulfuric acid) from the general wood fiber. In particular, the concentration of total reduced sugar is higher than the cellulose pure cellulose, because the paper sludge fine powder, hemi cellulose and the like is present in addition to cellulose, when decomposed by the acid catalyst, various monosaccharides other than glucose are produced in various ways. Therefore, similarly to the case of using the hydrolase, the sugar can be easily produced from the fine powder even when the acid catalyst is used.

실시예 3Example 3

상기 실시예 1 또는 실시예 2로부터 생산된 당류를 이용하여 미생물을 배양하였다. 당류 외에 펩톤 1 g/L, 인산 0.5 g/L, 마그네슘설페이트 0.1 g/L 을 부가적으로 첨가하고, 미생물은 알콜생산용 효모(사카로마이세스 세레비지아)를 이용하였다. 효모 성장의 측정은 흡광도를 이용하였으며, 이때 생산되는 에탄올의 양은 가스크로마토그래피를 이용하여 측정하였다. 배양은 36 ℃ 진탕교반기에서 48 시간동안 이루어졌으며 교반속도는 분당 120회였다.The microorganisms were cultured using the saccharide produced from Example 1 or Example 2. In addition to sugars, 1 g / L of peptone, 0.5 g / L of phosphoric acid, and 0.1 g / L of magnesium sulfate were additionally added, and the microorganism was a yeast for producing alcohol (Saccharomyces cerevisiae). The yeast growth was measured by absorbance, and the amount of ethanol produced was measured by gas chromatography. Incubation was for 48 hours at 36 ℃ shake stirrer and the stirring speed was 120 times per minute.

당류 농도 (mg/L)Sugar Concentration (mg / L) 효모 균체량 (g/L)Yeast cell mass (g / L) 생산된 에탄올 농도 (g/L)Ethanol Concentration Produced (g / L) 5,0005,000 2.52.5 2.02.0 10,00010,000 5.05.0 4.04.0 15,00015,000 7.07.0 6.06.0 20,00020,000 8.08.0 8.08.0

상기 표 3에서 볼 수 있듯이, 미생물(효모)이 미세분으로부터 생산되어진 당류를 이용하여 성장하는데는 아무 문제가 없으며 주입되는 당류농도에 비례하여 미생물 균체량도 증가하였으며 일정비율정도의 에탄올이 생산되었다. 따라서, 표 3은 미세분으로부터 생산되는 당류를 이용하여 미생물을 배양할 수 있음을 보여주고 있으며 효모 외에 다른 미생물을 이용할 경우 유용물질을 생산할 수도 있음을 보여준다.As shown in Table 3, there is no problem in the growth of microorganisms (yeasts) using saccharides produced from fine powders, and the microbial cell mass was increased in proportion to the injected saccharide concentration and ethanol was produced at a predetermined ratio. Therefore, Table 3 shows that the microorganisms can be cultured using the sugars produced from the fine powder, and that the use of other microorganisms in addition to the yeast can produce useful substances.

이상에서 설명한 바와 같이, 본 발명은 폐기물로 폐기되는 제지슬러지 중 미세분을 분리하여 가수분해효소 또는 산촉매를 이용하여 당류로 전환시킬 경우 일반적인 목질계 셀룰로오즈 섬유소에 비하여 고농도의 당류를 획득할 수 있으며 동시에 이를 이용하여 유용물질을 생산할 수 있는 미생물의 에너지원으로 이용이 가능하다. 또한, 본 발명은 제지산업체에서 배출하는 폐기물의 양을 절감함과 동시에 수중에 존재하여 폐수로 배출되는 것을 억제함으로써 환경오염부하를 줄일 수있다.As described above, the present invention can obtain a higher concentration of saccharides compared to the general wood-based cellulose fiber when the fine powder is separated from waste paper sludge that is disposed of as waste and converted into saccharides using a hydrolase or an acid catalyst. It can be used as an energy source for microorganisms that can produce useful substances. In addition, the present invention can reduce the environmental pollution load by reducing the amount of waste discharged from the papermaking industry while at the same time suppressing the discharge into the waste water present in the water.

Claims (3)

제지공정 시 폐기물로 버려지는 폐슬러지로부터 부상부유 처리를 통하여 미세분을 분리하고, 이 미세분을 가수분해효소 또는 산촉매로 처리하는 것을 특징으로 하는 제지 폐슬러지로부터 당류를 생산하는 방법.A method for producing sugar from paper waste sludge, characterized in that the fine powder is separated from the waste sludge discarded as waste during the papermaking process, and the fine powder is treated with a hydrolase or an acid catalyst. 제 1 항에 있어서, 상기 가수분해효소는 셀룰라아제, 아밀라아제, 자일라아제 및 헤미셀룰라아제 중에서 선택된 1종 또는 2종 이상의 것으로, 0.01 ~ 0.1 중량%을 사용하는 것을 특징으로 하는 제지 폐슬러지로부터 당류를 생산하는 방법.According to claim 1, wherein the hydrolase is one or two or more selected from cellulase, amylase, xylase and hemicellulase, and produces sugars from paper waste sludge, characterized in that using 0.01 to 0.1% by weight. How to. 제 1 항에 있어서, 상기 산촉매는 황산, 염산, 질산 중에서 선택된 것으로, 0.01 ∼ 0.1 중량%을 사용하는 것을 특징으로 하는 제지 폐슬러지로부터 당류를 생산하는 방법.The method of claim 1, wherein the acid catalyst is selected from sulfuric acid, hydrochloric acid, nitric acid, and the method for producing a sugar from paper waste sludge, characterized in that the use of 0.01 to 0.1% by weight.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4664717A (en) * 1982-11-26 1987-05-12 Union Oil Company Of California Methods for hydrolyzing polysaccharides and compositions useful therein
WO1991014822A1 (en) * 1990-03-29 1991-10-03 Novo Nordisk A/S A process using cellulase for improving drainage properties of pulp
KR920002797A (en) * 1990-07-05 1992-02-28 배명숙 Decomposition of Glucose-based Monosaccharides from Rice Straw, Barley Straw and Straw Pulp and Yucca Cellulose
JPH07184678A (en) * 1993-12-28 1995-07-25 Nippon Kagaku Kikai Seizo Kk Production of cello-oligosaccharide
WO1997038164A1 (en) * 1996-04-03 1997-10-16 Participant Project Ip Limited Paper pulp drainage aid
KR20000003300A (en) * 1998-06-27 2000-01-15 김충섭 Corrugated cardboard regenerating method using floating and enzyme processing
KR20030018293A (en) * 2001-08-28 2003-03-06 학교법인 인하학원 Method for Glycation of Paper-Sludge

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4664717A (en) * 1982-11-26 1987-05-12 Union Oil Company Of California Methods for hydrolyzing polysaccharides and compositions useful therein
WO1991014822A1 (en) * 1990-03-29 1991-10-03 Novo Nordisk A/S A process using cellulase for improving drainage properties of pulp
KR920002797A (en) * 1990-07-05 1992-02-28 배명숙 Decomposition of Glucose-based Monosaccharides from Rice Straw, Barley Straw and Straw Pulp and Yucca Cellulose
JPH07184678A (en) * 1993-12-28 1995-07-25 Nippon Kagaku Kikai Seizo Kk Production of cello-oligosaccharide
WO1997038164A1 (en) * 1996-04-03 1997-10-16 Participant Project Ip Limited Paper pulp drainage aid
KR20000003300A (en) * 1998-06-27 2000-01-15 김충섭 Corrugated cardboard regenerating method using floating and enzyme processing
KR20030018293A (en) * 2001-08-28 2003-03-06 학교법인 인하학원 Method for Glycation of Paper-Sludge

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