JP2011212593A - Method for preparing biomass feedstock originated from waste - Google Patents
Method for preparing biomass feedstock originated from waste Download PDFInfo
- Publication number
- JP2011212593A JP2011212593A JP2010083309A JP2010083309A JP2011212593A JP 2011212593 A JP2011212593 A JP 2011212593A JP 2010083309 A JP2010083309 A JP 2010083309A JP 2010083309 A JP2010083309 A JP 2010083309A JP 2011212593 A JP2011212593 A JP 2011212593A
- Authority
- JP
- Japan
- Prior art keywords
- waste
- paper
- saccharification
- fermentation
- suspension
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 84
- 239000002028 Biomass Substances 0.000 title claims abstract description 68
- 238000000855 fermentation Methods 0.000 claims abstract description 64
- 230000004151 fermentation Effects 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 239000000725 suspension Substances 0.000 claims abstract description 37
- 238000010790 dilution Methods 0.000 claims abstract description 14
- 239000012895 dilution Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 11
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 25
- 239000010893 paper waste Substances 0.000 claims description 9
- 239000010865 sewage Substances 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 abstract 3
- 230000005593 dissociations Effects 0.000 abstract 3
- 239000007858 starting material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 239000010813 municipal solid waste Substances 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 244000052616 bacterial pathogen Species 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000010794 food waste Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 pruned branches Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010563 solid-state fermentation Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Landscapes
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
本発明は、廃棄物を、例えば糖化発酵によるバイオエタノールの製造に利用するための廃棄物由来バイオマス原料の糖化発酵方法、詳しくは、紙類を主に含む紙類系廃棄物と、厨芥類を主に含む厨芥類系廃棄物とに分け、紙類を主な成分とする原料は離解および脱水によるパルプに調整し、厨芥類を主な成分とする原料は水で懸濁後、前述のパルプを加えることで、最終的に廃棄物由来バイオマス原料の高濃度化を達成することができる工業的に非常に有効な廃棄物由来バイオマス原料の糖化発酵方法に関するものである。 The present invention relates to a method for saccharification and fermentation of waste-derived biomass raw materials for use in the production of bioethanol, for example, by saccharification and fermentation, and more specifically, paper-based waste mainly containing paper, and waste It is divided into moss-based wastes that contain mainly, and the raw materials mainly composed of paper are adjusted to pulp by disaggregation and dehydration, and the raw materials mainly composed of moss are suspended in water and the above-mentioned pulp It is related with the industrially very effective waste-derived biomass raw material saccharification fermentation method which can achieve high concentration of a waste-derived biomass raw material finally by adding.
近年、炭酸ガスの排出抑制に寄与するバイオマスの利活用は、カーボンニュートラルの観点から注目されており、直接燃焼、ガス化、メタン発酵、エタノール発酵などにより、電力や化石燃料代替としての利用および開発が行われている。現在、国内で注目されているバイオマス原料は、廃木材、剪定枝、下水汚泥、食品廃棄物、農産廃棄物などが挙げられる。その一方で、焼却施設に持ち込まれる一般廃棄物の中には、紙類や厨芥類等のバイオマス資源が６０％以上存在しているが、ほとんど利用されていないのが現状である。これら一般廃棄物は比重選別により、紙類およびプラスチック類を多く含む軽量ごみと、厨芥類を多く含む重量ごみとに分類できることは知られており、その重量ごみをメタン発酵基質に利用する開発が行われている。 In recent years, the utilization of biomass, which contributes to the suppression of carbon dioxide emissions, has attracted attention from the viewpoint of carbon neutrality. Utilization and development as an alternative to electricity and fossil fuels by direct combustion, gasification, methane fermentation, ethanol fermentation, etc. Has been done. Currently, biomass materials that are attracting attention in Japan include waste wood, pruned branches, sewage sludge, food waste, and agricultural waste. On the other hand, more than 60% of biomass resources such as papers and moss are present in the general waste brought into the incineration facilities, but the present situation is that they are hardly used. It is known that these general wastes can be classified into light-weight wastes containing a lot of paper and plastics and heavy-duty wastes containing a lot of waste by specific gravity sorting. Has been done.
一方、紙類は焼却されるのみであり、これを回収してエタノール発酵基質とする発明が、下記の特許文献１にすでに記載されている（ 「ごみ焼却施設におけるセルロース系エタノールの製造方法」）。 On the other hand, papers are only incinerated, and an invention for recovering the paper and using it as an ethanol fermentation substrate has already been described in the following Patent Document 1 ("Method for producing cellulosic ethanol in a garbage incineration facility") .
ところで、平成１８〜２０年度の環境省発表の全国廃棄物排出量は、３７００〜３９００万ｔであるが、そのうち、厨芥類や紙布革類の比率は、６３〜６６％を占め、２４００万ｔ程度が毎年焼却処分されている（環境省ホームページ内資料より算出）。これらは水分を含んだ量であるが、一般的に紙類の含水率は３０％、厨芥類は７０〜８０％であることを考慮に入れても、非常に多くのバイオマス資源であるといえる。 By the way, the amount of nationwide waste released by the Ministry of the Environment from FY2006 to FY2008 is 37 million to 39 million tons, of which the ratio of moss and paper fabrics accounts for 63 to 66%, 24 million. About t is incinerated every year (calculated from materials on the Ministry of the Environment website). Although these are water-containing amounts, it can be said that they are very many biomass resources even when taking into account that the moisture content of paper is generally 30% and that of moss is 70-80%. .
一方、エタノールは蒸留により濃縮されるため、蒸留開始時の濃度が高くなければ、エネルギー回収率は高くならない。高濃度のエタノール反応液、または別のバイオリファイナリー原料の高濃度生産のためには、高濃度の発酵基質が必要である。 On the other hand, since ethanol is concentrated by distillation, the energy recovery rate does not increase unless the concentration at the start of distillation is high. A high concentration of fermentation substrate is required for high concentration ethanol reaction or high concentration production of another biorefinery raw material.
例えば、厨芥類を発酵基質とする場合、原料に含まれるデンプン質が多く、かつ含水率も低く、さらに発酵不適物が少ない場合には、液化および糖化を行っただけで発酵基質として用いられるが、それ以外の場合は、例えば下記の特許文献２では、生ごみから得られた糖液を濃縮する方法について言及されており、また下記の特許文献３においては、デンプン質を含む原料から３０〜６０％のペレットを形成し、固体発酵による同時糖化発酵を行う方法が記載されている。 For example, when moss is used as a fermentation substrate, if the starch is contained in the raw material in a large amount and has a low water content, and there are few unsuitable fermentation materials, it can be used as a fermentation substrate simply by liquefaction and saccharification In other cases, for example, the following Patent Document 2 refers to a method of concentrating a sugar solution obtained from food waste, and in the following Patent Document 3, from a raw material containing starch, A method of forming 60% pellets and performing simultaneous saccharification and fermentation by solid state fermentation is described.
さらに紙類については、例えば下記の特許文献４において、紙類とそれ以外のごみが混ざっている廃棄物から、紙類のセルロース成分を分離回収する方法が記載されており、紙を離解することで異物を除去し、繊維化された紙類のセルロース分を回収している。 Furthermore, for paper, for example, in Patent Document 4 below, a method for separating and recovering the cellulose component of paper from waste in which paper and other waste are mixed is described. The foreign matter is removed by this, and the cellulose content of the fiberized paper is collected.
しかしながら、廃棄物中に多く含まれるバイオマス資源をできるだけ多く回収するためには、紙類と厨芥類を多く回収し、かつ発酵不適物や難発酵物質をできるだけ多く取り除き、さらに原料濃度を高くする必要があるが、上記従来の特許文献に記載の技術では、充分な処理を行うことができないという問題があった。特に、厨芥類は粘度が高く、機械的な脱水に適さない場合が多く、コンポストで用いられるような熱による乾燥は時間がかかり、かつ熱源として電力等が必要とされるという問題があった。 However, in order to recover as much biomass resources as possible contained in waste, it is necessary to recover as much paper and moss as possible, remove as much fermentation-inappropriate and difficult-to-ferment substances as possible, and increase the concentration of raw materials. However, the technique described in the above-described conventional patent document has a problem that sufficient processing cannot be performed. In particular, moss has a high viscosity and is often not suitable for mechanical dehydration, and drying with heat as used in compost takes time, and there is a problem that electric power or the like is required as a heat source.
本発明の目的は、上記の従来技術の問題を解決し、最終的に高濃度のバイオマス原料を糖化発酵することができるため、結果的に目的生産物の濃度が高くなるとともに、処理設備が小規模になって、設備コストが低減することができ、一般廃棄物由来のバイオマス資源の利用適応範囲が広がることで、炭酸ガス排出量が低減し、排出権取引に利用できる、廃棄物由来バイオマス原料の糖化発酵方法を提供することにある。 The object of the present invention is to solve the above-mentioned problems of the prior art and finally to saccharify and ferment high-concentration biomass raw materials. As a result, the concentration of the target product is increased and the processing equipment is small. Waste-derived biomass feedstock that can be used for emissions trading by reducing the amount of carbon dioxide emissions by expanding the scope of use of biomass resources derived from general waste by expanding the scale, reducing equipment costs It is in providing the saccharification fermentation method of this.
本発明者らは、上記の点に鑑み鋭意研究を重ねた結果、廃棄物由来の紙類および厨芥類を共に処理し、エタノール発酵原料とすることにより、さらに収量が向上し、炭酸ガスの排出削減にも寄与できることを見出し、本発明を完成するに至ったものである。 As a result of intensive research in view of the above points, the inventors of the present invention processed both waste-derived papers and cocoons and used them as ethanol fermentation raw materials to further improve the yield and discharge carbon dioxide. The present inventors have found that it is possible to contribute to reduction, and have completed the present invention.
上記の目的を達成するために、請求項１の廃棄物由来バイオマス原料の糖化発酵方法の発明は、紙類を主に含む紙類系廃棄物を希釈水に離解させて、離解液を生成する工程と、紙類系廃棄物の離解液を脱水して、脱水パルプおよび排出用水を得る工程と、厨芥類を主に含む厨芥類系廃棄物を希釈水に懸濁させて、懸濁液を生成する工程と、厨芥類系廃棄物の懸濁液に酵母を加えるとともに、上記脱水パルプを加えて、高濃度化されたバイオマス原料により糖化発酵を行う工程とからなることを特徴としている。 In order to achieve the above object, the invention of the method for saccharification and fermentation of waste-derived biomass raw material according to claim 1 disaggregates paper waste mainly containing paper into diluted water to generate a disaggregation liquid. A step of dehydrating a paper-based waste disaggregation solution to obtain dehydrated pulp and discharge water, and suspending a waste-based waste mainly containing moss in dilution water, It is characterized by comprising a step of producing and a step of adding saccharification and fermentation with a biomass material having a high concentration by adding yeast to the suspension of moss-based waste and adding the dehydrated pulp.
請求項２の発明は、請求項１に記載の廃棄物由来バイオマス原料の糖化発酵方法であって、紙類系廃棄物の離解液の生成工程および厨芥類系廃棄物の懸濁液の生成工程において、異物除去処理を行うことを特徴としている。 The invention of claim 2 is a saccharification and fermentation method for a waste-derived biomass raw material according to claim 1, wherein a process for producing a paper-based waste disaggregation liquid and a process for producing a suspension of moss-based waste 1 is characterized in that a foreign matter removal process is performed.
請求項３の発明は、請求項１または２に記載の廃棄物由来バイオマス原料の糖化発酵方法であって、紙類系廃棄物の離解液の脱水工程から排出された排出用水を、紙類系廃棄物の離解液の生成工程および／または厨芥類系廃棄物の懸濁液の生成工程の希釈水として再利用することを特徴としている。 The invention of claim 3 is the saccharification and fermentation method of the waste-derived biomass raw material according to claim 1 or 2, wherein the waste water discharged from the dewatering step of the paper-based waste disaggregation solution is used as the paper-based waste material. It is characterized by being reused as dilution water in a process for producing a waste disaggregation liquid and / or a process for producing a suspension of moss-based waste.
請求項４の発明は、請求項１〜３のうちのいずれか一項に記載の廃棄物由来バイオマス原料の糖化発酵方法であって、紙類系廃棄物の離解液の脱水工程から排出された排出用水を、廃棄物由来バイオマス原料による糖化発酵工程の濃度調整処理に利用することを特徴としている。 Invention of Claim 4 is the saccharification fermentation method of the biomass material of waste origin as described in any one of Claims 1-3, Comprising: It discharged | emitted from the dehydration process of the disintegration liquid of paper-type waste It is characterized by using the discharged water for the concentration adjustment process in the saccharification and fermentation process using the biomass material derived from waste.
請求項５の発明は、請求項１〜４のうちのいずれか一項に記載の廃棄物由来バイオマス原料の糖化発酵方法であって、紙類系廃棄物の離解液の生成工程、脱水パルプおよび排出用水を得る工程および／または厨芥類系廃棄物の懸濁液の生成工程の処理温度が、６０℃〜９５℃であることを特徴としている。 Invention of Claim 5 is a saccharification fermentation method of the biomass material of waste origin as described in any one of Claims 1-4, Comprising: The production | generation process of the disaggregation liquid of paper-type waste, dehydrated pulp, The process temperature of the process of obtaining the water for discharge, and / or the production | generation process of the suspension of moss-based waste is 60 to 95 degreeC, It is characterized by the above-mentioned.
請求項６の発明は、請求項１〜５のうちのいずれか一項に記載の廃棄物由来バイオマス原料の糖化発酵方法であって、紙類系廃棄物の離解液の生成工程、厨芥類系廃棄物の懸濁液の生成工程、および廃棄物由来バイオマス原料による糖化発酵工程において、処理液のｐＨを調整することを特徴としている。 The invention of claim 6 is a saccharification and fermentation method for a waste-derived biomass raw material according to any one of claims 1 to 5, wherein a process for producing a paper-based waste disaggregation solution, a moss system It is characterized in that the pH of the treatment liquid is adjusted in the waste suspension generation step and the saccharification and fermentation step using the waste-derived biomass material.
請求項１の廃棄物由来バイオマス原料の糖化発酵方法の発明は、紙類を主に含む紙類系廃棄物を希釈水に離解させて、離解液を生成する工程と、紙類系廃棄物の離解液を脱水して、脱水パルプおよび排出用水を得る工程と、厨芥類を主に含む厨芥類系廃棄物を希釈水に懸濁させて、懸濁液を生成する工程と、厨芥類系廃棄物の懸濁液に酵母を加えるとともに、上記脱水パルプを加えて、高濃度化されたバイオマス原料により糖化発酵を行う工程とからなるもので、請求項１の発明によれば、最終的に高濃度のバイオマス原料を糖化発酵することができるため、結果的に目的生産物の濃度が高くなるとともに、処理設備が小規模になって、設備コストが低減することができ、一般廃棄物由来のバイオマス資源の利用適応範囲が広がることで、炭酸ガス排出量が低減し、排出権取引に利用できるという効果を奏する。 The invention of the method for saccharification and fermentation of waste-derived biomass raw material according to claim 1 includes a step of disaggregating paper-based waste mainly containing paper into diluted water to generate a disaggregation liquid, Dehydrating the disaggregated liquid to obtain dehydrated pulp and discharge water, suspending moss waste mainly containing moss in dilution water to produce a suspension, and sewage waste The method comprises the steps of adding yeast to the suspension of the product, adding the dehydrated pulp, and performing saccharification and fermentation with the biomass raw material having a high concentration. According to the invention of claim 1, Biomass-derived biomass can be saccharified and fermented. As a result, the concentration of the target product is increased, the processing equipment is reduced in scale, and the equipment cost can be reduced. By expanding the range of resource use adaptation, Gas emissions are reduced, an effect that can be used to emission trading.
請求項２の発明は、請求項１に記載の廃棄物由来バイオマス原料の糖化発酵方法であって、紙類系廃棄物の離解液の生成工程および厨芥類系廃棄物の懸濁液の生成工程において、異物除去処理を行うことを特徴とするもので、請求項２の発明によれば、紙類および厨芥類をともに一度水で希釈することにより、バイオマス原料に適さない異物を除去することができるという効果を奏する。 The invention of claim 2 is a saccharification and fermentation method for a waste-derived biomass raw material according to claim 1, wherein a process for producing a paper-based waste disaggregation liquid and a process for producing a suspension of moss-based waste In the present invention, foreign matter removal treatment is performed. According to the invention of claim 2, foreign matters that are not suitable for biomass raw materials can be removed by diluting both paper and straw once with water. There is an effect that can be done.
請求項３の発明は、請求項１または２に記載の廃棄物由来バイオマス原料の糖化発酵方法であって、紙類系廃棄物の離解液の脱水工程から排出された排出用水を、紙類系廃棄物の離解液の生成工程および／または厨芥類系廃棄物の懸濁液の生成工程の希釈水として再利用するもので、請求項３の発明によれば、紙類系廃棄物の離解液の脱水工程から排出された排出用水を循環利用することで、排水処理を大幅に低減することができるという効果を奏する。 The invention of claim 3 is the saccharification and fermentation method of the waste-derived biomass raw material according to claim 1 or 2, wherein the waste water discharged from the dewatering step of the paper-based waste disaggregation solution is used as the paper-based waste material. The waste water is reused as dilution water in the production process of the disaggregation liquid and / or in the production process of the suspension of the waste-based waste. According to the invention of claim 3, the disaggregation liquid of paper-based waste By circulating and using the discharge water discharged from the dehydration process, the drainage treatment can be greatly reduced.
請求項４の発明は、請求項１〜３のうちのいずれか一項に記載の廃棄物由来バイオマス原料の糖化発酵方法であって、紙類系廃棄物の離解液の脱水工程から排出された排出用水を、廃棄物由来バイオマス原料による糖化発酵工程の濃度調整処理に利用するもので、請求項４の発明によれば、紙類系廃棄物の離解液の脱水工程から排出された排出用水を循環利用することで、排水処理を大幅に低減することができるという効果を奏する。 Invention of Claim 4 is the saccharification fermentation method of the biomass material of waste origin as described in any one of Claims 1-3, Comprising: It discharged | emitted from the dehydration process of the disintegration liquid of paper-type waste The discharge water is used for the concentration adjustment process of the saccharification and fermentation process using the biomass material derived from waste. According to the invention of claim 4, the discharge water discharged from the dewatering process of the paper-based waste disaggregation liquid is used. By recycling, there is an effect that waste water treatment can be significantly reduced.
請求項５の発明は、請求項１〜４のうちのいずれか一項に記載の廃棄物由来バイオマス原料の糖化発酵方法であって、紙類系廃棄物の離解液の生成工程、脱水パルプおよび排出用水を得る工程および／または厨芥類系廃棄物の懸濁液の生成工程の処理温度が、６０℃〜９５℃であることを特徴とするもので、請求項５の発明によれば、紙類系廃棄物および厨芥類系廃棄物の原料は、廃棄物由来であるため、多くの雑菌が含まれており、一連の反応もしくはその一部を６０℃〜９５℃の温度で処理することにより、雑菌由来の不必要な原料の腐敗および排出用水の腐敗を防ぐことができるという効果を奏する。 Invention of Claim 5 is a saccharification fermentation method of the biomass material of waste origin as described in any one of Claims 1-4, Comprising: The production | generation process of the disaggregation liquid of paper-type waste, dehydrated pulp, According to the invention of claim 5, the treatment temperature of the step of obtaining the discharge water and / or the step of producing the suspension of the moss-based waste is 60 ° C. to 95 ° C. Since the raw materials of wastes and moss wastes are derived from wastes, many germs are included, and a series of reactions or a part thereof is processed at a temperature of 60 ° C to 95 ° C. In addition, it is possible to prevent the spoilage of unnecessary raw materials derived from various germs and the spoilage of discharge water.
請求項６の発明は、請求項１〜５のうちのいずれか一項に記載の廃棄物由来バイオマス原料の糖化発酵方法であって、紙類系廃棄物の離解液の生成工程、厨芥類系廃棄物の懸濁液の生成工程、および廃棄物由来バイオマス原料による糖化発酵工程において、処理液のｐＨを調整することを特徴とするもので、請求項６の発明によれば、例えばエタノール発酵に適した廃棄物由来バイオマス原料を調製することができるという効果を奏する。 The invention of claim 6 is a saccharification and fermentation method for a waste-derived biomass raw material according to any one of claims 1 to 5, wherein a process for producing a paper-based waste disaggregation solution, a moss system In the waste suspension generation step and the saccharification and fermentation step using the waste-derived biomass material, the pH of the treatment liquid is adjusted. According to the invention of claim 6, for example, for ethanol fermentation There exists an effect that the suitable waste origin biomass raw material can be prepared.
つぎに、本発明の実施の形態を、図面を参照して説明するが、本発明はこれらに限定されるものではない。 Next, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.
図１は、本発明による廃棄物由来バイオマス原料の糖化発酵方法の実施の形態を示すブロック図である。 FIG. 1 is a block diagram showing an embodiment of a method for saccharification and fermentation of a waste-derived biomass material according to the present invention.
同図を参照すると、本発明による廃棄物由来バイオマス原料の糖化発酵方法は、紙類を主に含む紙類系廃棄物を希釈水に離解させて、離解液を生成する工程と、紙類系廃棄物の離解液を脱水して、脱水パルプおよび排出用水を得る工程と、厨芥類を主に含む厨芥類系廃棄物を希釈水に懸濁させて、懸濁液を生成する工程と、厨芥類系廃棄物の懸濁液に酵母を加えるとともに、上記脱水パルプを加えて、高濃度化されたバイオマス原料により糖化発酵を行う工程とからなることを特徴とするものである。 Referring to the figure, the method for saccharification and fermentation of waste-derived biomass raw material according to the present invention includes a step of deaggregating paper-based waste mainly containing paper into dilution water to generate a decomposing liquid, and a paper-based fermentation method. Dehydrating the waste disaggregation liquid to obtain dehydrated pulp and discharge water, suspending moss-based waste mainly containing moss in dilution water to produce a suspension, The method comprises a step of adding saccharification and fermentation with a biomass raw material having a high concentration while adding yeast to the suspension of the similar waste and adding the dehydrated pulp.
ここで、廃棄物は、比重選別などの機械的な分離手法により、紙類を多く含む廃棄物と厨芥類を多く含む廃棄物に分類できる。紙類は表面加工処理されていたり、プラスチックや金属などと複合化して存在しているため、水で紙類を離解させ、この離解処理中に、バイオマス原料として不適なものを粒径等で分離除去する工程を入れることができる。 Here, the waste can be classified into a waste containing a large amount of paper and a waste containing a large amount of waste by a mechanical separation method such as specific gravity sorting. Since papers are surface-treated or exist in combination with plastics, metals, etc., papers are disaggregated with water, and unsuitable biomass materials are separated by particle size during this disaggregation process. A step of removing can be included.
一方、厨芥類は、野菜くずなど原形を留めているため、水で懸濁することで均一化及び微細化する。この懸濁処理中に、バイオマス原料として不適なものを粒径等で分離除去する工程を入れることができる。 On the other hand, moss retains its original shape such as vegetable scraps, and thus is homogenized and refined by suspending in water. During this suspension treatment, a step of separating and removing unsuitable biomass raw materials by particle size or the like can be included.
一般廃棄物由来バイオマス原料を発酵基質として用いる際に、厨芥類と紙類に分けた後、希釈水を用いて異物除去や微細化等の処理を行ない、かつ最終的な原料処理濃度を高くする必要がある。 When using biomass materials derived from general waste as fermentation substrates, after separating them into potatoes and papers, use dilution water to remove foreign substances, refine them, etc., and increase the final raw material treatment concentration. There is a need.
厨芥類は野菜くずなど原形を留めているため、水で懸濁することで均一化及び微細化する。紙類は表面加工処理されていたり、プラスチックや金属などと複合化して存在しているため、水で紙類を離解させ脱水することにより、パルプとして回収する。 Since moss retains its original shape such as vegetable scraps, it is homogenized and refined by suspending in water. Since papers are surface-treated or exist in a composite with plastics, metals, etc., they are recovered as pulp by disaggregating and dewatering the papers with water.
水に懸濁させた厨芥類はその懸濁成分であるセルロース、デンプン、タンパク質といった含水性の高い成分を酵素により分解し液化する。 The moss suspended in water decomposes and liquefies its suspended components, such as cellulose, starch and protein, with enzymes.
脱水により濃縮されたパルプを、厨芥類の液化処理工程の前後において投入し、パルプを酵素により分解し液化する。 The pulp concentrated by dehydration is added before and after the liquefaction treatment process of the moss, and the pulp is decomposed and liquefied by the enzyme.
さらに脱水パルプの投入前後において、厨芥類や紙類由来の原料を基質とする微生物を加え、目的成分の生産を行うものである。 Further, before and after the addition of dehydrated pulp, microorganisms using raw materials derived from moss and paper as a substrate are added to produce the target component.
処理工程中の液化に伴い、脱水パルプを投入し、最終的に反応槽容量あたりの高濃度原料を処理する。投入する脱水パルプは、一括投入すると粘度が高くなり、機械的な攪拌に支障をきたすことが想定されるため、複数回に分けて行うことが望ましい。また、脱水パルプを分けて加えるのに要する時間は、３時間から７２時間であるのが好ましい。 Along with liquefaction during the treatment process, dehydrated pulp is added, and finally the high-concentration raw material per reactor volume is treated. The dehydrated pulp to be added has a high viscosity when it is input all at once, and it is assumed that the mechanical stirring is hindered. The time required for adding the dehydrated pulp separately is preferably 3 to 72 hours.
紙類系廃棄物の離解液の生成工程および厨芥類系廃棄物の懸濁液の生成工程において、スクリーンによる異物除去処理を行うことが好ましい。 It is preferable to perform a foreign substance removal process using a screen in the step of generating the paper-type waste disaggregation liquid and the step of generating the waste-type waste suspension.
紙類系廃棄物の離解液の脱水工程から排出された排出用水を、紙類系廃棄物の離解液の生成工程および／または厨芥類系廃棄物の懸濁液の生成工程の希釈水として再利用することが好ましい。 The discharge water discharged from the dewatering process for paper waste is re-used as dilution water for the process for generating paper waste and / or for producing waste suspensions for waste. It is preferable to use it.
紙類系廃棄物の離解液の脱水工程から排出された排出用水を、廃棄物由来バイオマス原料による糖化発酵工程の濃度調整処理に利用することが好ましい。 It is preferable to use the discharge water discharged from the dewatering step of the paper-based waste disaggregation liquid for the concentration adjustment process in the saccharification and fermentation step using the waste-derived biomass material.
さらに、機械的な脱水工程で発生した脱水液中には、細分化されたバイオマス原料成分の水溶性成分が含まれているため、この用水を離解水や懸濁水として再利用することで未回収成分の回収を行うことができる。 Furthermore, since the dehydrated liquid generated in the mechanical dehydration process contains water-soluble components of the subdivided biomass raw material components, this water is not recovered by reusing it as disaggregated water or suspended water. Component recovery can be performed.
本発明による廃棄物由来バイオマス原料の糖化発酵方法では、紙類系廃棄物の離解液の生成工程、脱水パルプおよび排出用水を得る工程および／または厨芥類系廃棄物の懸濁液の生成工程の処理温度は、６０℃〜９５℃とするのが好ましい。ここで、紙類系廃棄物および厨芥類系廃棄物の原料は、廃棄物由来であるため、多くの雑菌が含まれており、一連の反応もしくはその一部を６０℃〜９５℃、好ましくは７０℃〜８５℃で実施することにより、雑菌由来の不必要な原料の腐敗および用水の腐敗を防ぎ、雑菌の繁殖を抑えることができる。 In the method for saccharification and fermentation of waste-derived biomass raw material according to the present invention, a process for producing a paper-based waste disaggregation liquid, a process for obtaining dehydrated pulp and discharge water, and / or a process for producing a suspension of moss-based waste The treatment temperature is preferably 60 ° C to 95 ° C. Here, since the raw materials of paper-type waste and moss-type waste are derived from waste, many miscellaneous bacteria are included, and a series of reactions or a part thereof is performed at 60 ° C. to 95 ° C., preferably By carrying out at 70 ° C. to 85 ° C., it is possible to prevent spoilage of unnecessary raw materials derived from germs and spoilage of water, and to suppress the propagation of germs.
また、紙類系廃棄物の離解液の生成工程、厨芥類系廃棄物の懸濁液の生成工程、および廃棄物由来バイオマス原料による糖化発酵工程において、処理液のｐＨを調整することが好ましい。 In addition, it is preferable to adjust the pH of the treatment liquid in the process of generating the paper-based waste disaggregation liquid, the process of generating the suspension of the waste-based waste, and the saccharification and fermentation process using the biomass material derived from waste.
厨芥類と紙類の使用比率は、原料の性状によっても変化するが、乾燥重量比で紙類が少なくとも３０％以上もしくは厨芥類が７０％以下であることが望ましい。 The use ratio of cocoons and papers varies depending on the properties of the raw materials, but it is desirable that the dry weight ratio is at least 30% for papers or 70% for moss.
また、紙類系廃棄物の離解液の生成工程および厨芥類系廃棄物の懸濁液の生成工程、または紙類系廃棄物の離解液および厨芥類系廃棄物の懸濁液の混合工程において、処理液のｐＨを調整することにより、例えばエタノール発酵に適した廃棄物由来バイオマス原料を調製することができる。 Also, in the process of producing the paper-based waste disintegration liquid and the waste-type waste suspension, or in the process of mixing the paper-type waste disaggregation liquid and the waste-type waste suspension. By adjusting the pH of the treatment liquid, for example, a waste-derived biomass material suitable for ethanol fermentation can be prepared.
本発明の廃棄物由来バイオマス原料の糖化発酵方法によれば、バイオマス資源の高濃度化により、微生物の資化成分の高濃度化が図られ、その後の目的生産物の高濃度化が実現する。 According to the saccharification and fermentation method for waste-derived biomass raw material of the present invention, the concentration of the microbial assimilation component is increased by increasing the concentration of biomass resources, and the concentration of the target product thereafter is increased.
また、本発明の廃棄物由来バイオマス原料の糖化発酵方法によれば、バイオマス資源の高濃度化により、処理設備が小規模になり、設備コストが低減する。 Moreover, according to the saccharification and fermentation method for waste-derived biomass raw material of the present invention, the processing equipment becomes small in scale due to the high concentration of biomass resources, and the equipment cost is reduced.
本発明の廃棄物由来バイオマス原料の糖化発酵方法によれば、バイオマス資源の高濃度化により、原料としての利用範囲が広まることで、廃棄物からの資源回収量が増え、炭酸ガス排出量の低減につながり、排出権取引に用いることができる。 According to the method for saccharification and fermentation of waste-derived biomass raw materials of the present invention, the use range as raw materials is expanded by increasing the concentration of biomass resources, so that the amount of resources recovered from waste increases and the amount of carbon dioxide emissions is reduced. Can be used for emissions trading.
本発明の廃棄物由来バイオマス原料の糖化発酵方法によれば、排出用水を循環利用することで、排水の処理が少なくなる、もしくは無くなる。 According to the saccharification and fermentation method for waste-derived biomass material of the present invention, wastewater treatment is reduced or eliminated by circulating and using the discharge water.
本発明の廃棄物由来バイオマス原料の糖化発酵方法は、一般廃棄物そのものにも適応できるが、異物除去効率を考慮に入れると、機械選別により紙類が主に含まれる紙類系廃棄物と厨芥類が主に含まれる厨芥類廃棄物に分離して処理することが望ましい。さらに、オフィス発生の事業系廃棄物のような紙類が主な廃棄物と、スーパーや飲食店由来事業系廃棄物のような厨芥類が主な廃棄物の場合、機械選別無しで処理を行うことができる。 The saccharification and fermentation method for waste-derived biomass raw material of the present invention can be applied to general waste itself, but taking into account the foreign matter removal efficiency, the paper-based waste and the waste mainly containing paper by machine sorting It is desirable to separate and treat the wastes that are mainly contained. Furthermore, if paper such as business waste generated from offices is the main waste, and waste such as business waste derived from supermarkets and restaurants is the main waste, it is processed without machine sorting. be able to.
つぎに、本発明の実施例を説明するが、本発明は、この実施例に限定されるものではない。 Next, examples of the present invention will be described, but the present invention is not limited to these examples.
実施例１
家庭から発生した生ごみ（１）、および食堂から発生した２種類の生ごみ（２）（３）を用いて、ミキサーにより懸濁処理を行った。懸濁時に適宜加水し、ミキシングが可能なギリギリの濃度で懸濁処理を行った。さらに、得られた懸濁物３０ｇに、１００ｍＭ酢酸バッファー（ｐＨ４．５）を５ｍｌ加え、酵素（Celic Ctec）２ｍｌを加えることで、厨芥の懸濁物の糖潜在量（グルコース潜在量）、および実際のグルコース濃度を求めた。得られた結果を、下記の表１に示した。
Suspension treatment was performed with a mixer using garbage (1) generated from home and two kinds of garbage (2) (3) generated from a cafeteria. Suspension treatment was carried out at the last minute concentration that allows appropriate mixing during suspension and enables mixing. Furthermore, by adding 5 ml of 100 mM acetate buffer (pH 4.5) to 30 g of the obtained suspension and adding 2 ml of enzyme (Celic Ctec), the sugar potential (glucose potential) of the koji suspension, and The actual glucose concentration was determined. The obtained results are shown in Table 1 below.
この表１の結果から明らかなように、厨芥類の懸濁物の最終スラリー濃度は、いずれの場合も１２％に届かず、実際のグルコース濃度は、最大でも３．５％程度であった。従って、これをエタノール発酵の原料とした場合には、最大でもエタノール濃度が２ｖｏｌ％に満たなくなるため、蒸留によるエネルギーが多く必要になり、エネルギー回収率が悪くなってしまう。 As apparent from the results in Table 1, the final slurry concentration of the suspension of moss did not reach 12% in all cases, and the actual glucose concentration was about 3.5% at the maximum. Therefore, when this is used as a raw material for ethanol fermentation, the ethanol concentration is less than 2 vol% at the maximum, so a large amount of energy is required by distillation, resulting in a poor energy recovery rate.
つぎに、本発明の方法において、ＯＡ紙を５ｗ％で調製したパルプ離解溶液を脱水して、脱水パルプおよび排出用水を得た。そして、上記家庭から発生した生ごみ（１）、および食堂から発生した２種類の生ごみ（２）（３）の懸濁液に、それぞれ酵母を加えるとともに、上記脱水パルプを酵素による液化に応じて添加して、バイオマス原料の高濃度化を伴った糖化発酵を行った。 Next, in the method of the present invention, the pulp disaggregation solution prepared with 5 w% of OA paper was dehydrated to obtain dehydrated pulp and discharge water. Then, yeast is added to the suspension of the garbage (1) generated from the household and the two kinds of garbage (2) and (3) generated from the dining room, respectively, and the dehydrated pulp is liquefied by the enzyme. The saccharification and fermentation accompanied by high concentration of biomass raw material was performed.
この糖化発酵溶液について、得られたエタノール溶液からグルコースの生成量を理論的に求めたところ、いずれの場合も生成グルコース濃度が大幅に上昇した。 About this saccharification fermentation solution, when the production amount of glucose was theoretically calculated | required from the obtained ethanol solution, the production | generation glucose concentration increased significantly in any case.
従って、厨芥類懸濁液に、脱水パルプを加えることで、高濃度化されたバイオマス原料により糖化発酵を実施でき、高濃度化した目的生産物が得られることが判明した。 Therefore, it was found that saccharification and fermentation can be carried out using a biomass material having a high concentration by adding dehydrated pulp to the suspension of moss, and a target product having a high concentration can be obtained.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010083309A JP5564310B2 (en) | 2010-03-31 | 2010-03-31 | Method for saccharification and fermentation of waste-derived biomass material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010083309A JP5564310B2 (en) | 2010-03-31 | 2010-03-31 | Method for saccharification and fermentation of waste-derived biomass material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011212593A true JP2011212593A (en) | 2011-10-27 |
| JP5564310B2 JP5564310B2 (en) | 2014-07-30 |
Family
ID=44942911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010083309A Active JP5564310B2 (en) | 2010-03-31 | 2010-03-31 | Method for saccharification and fermentation of waste-derived biomass material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5564310B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011212594A (en) * | 2010-03-31 | 2011-10-27 | Hitachi Zosen Corp | Method for preparing biomass feedstock originated from garbages-based waste |
| CN103205467A (en) * | 2012-01-13 | 2013-07-17 | 日立造船株式会社 | Method of producing ethanol by using biomass |
| JP2016167997A (en) * | 2015-03-12 | 2016-09-23 | 日立造船株式会社 | Waste-derived biomass reaction apparatus |
| JP2017006891A (en) * | 2015-06-26 | 2017-01-12 | 日立造船株式会社 | Waste treating method for providing useful substance by using biomass in waste as raw material |
| CN107708882A (en) * | 2015-08-10 | 2018-02-16 | 日立造船株式会社 | It is attached to the high efficiency of energy Application way of the castoff burning facility of ethanol manufacturing equipment |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002159953A (en) * | 2000-11-22 | 2002-06-04 | Tsukishima Kikai Co Ltd | Process and equipment for treating waste |
| JP2005065695A (en) * | 2003-08-07 | 2005-03-17 | Tokyo Univ Of Agriculture | Production method and production system for ethanol |
| JP2006325577A (en) * | 2005-04-28 | 2006-12-07 | Kumamoto Univ | System for producing alcohol, method for producing alcohol, and method for producing sugar |
| JP2007111590A (en) * | 2005-10-18 | 2007-05-10 | Shinseiki Hakko Kenkyusho:Kk | Method for manufacturing ethanol from kitchen garbage |
| JP2009112200A (en) * | 2007-11-02 | 2009-05-28 | Nippon Steel Engineering Co Ltd | Method for producing ethanol |
| JP2010017084A (en) * | 2008-07-08 | 2010-01-28 | Oji Paper Co Ltd | Saccharification and fermentation system |
-
2010
- 2010-03-31 JP JP2010083309A patent/JP5564310B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002159953A (en) * | 2000-11-22 | 2002-06-04 | Tsukishima Kikai Co Ltd | Process and equipment for treating waste |
| JP2005065695A (en) * | 2003-08-07 | 2005-03-17 | Tokyo Univ Of Agriculture | Production method and production system for ethanol |
| JP2006325577A (en) * | 2005-04-28 | 2006-12-07 | Kumamoto Univ | System for producing alcohol, method for producing alcohol, and method for producing sugar |
| JP2007111590A (en) * | 2005-10-18 | 2007-05-10 | Shinseiki Hakko Kenkyusho:Kk | Method for manufacturing ethanol from kitchen garbage |
| JP2009112200A (en) * | 2007-11-02 | 2009-05-28 | Nippon Steel Engineering Co Ltd | Method for producing ethanol |
| JP2010017084A (en) * | 2008-07-08 | 2010-01-28 | Oji Paper Co Ltd | Saccharification and fermentation system |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011212594A (en) * | 2010-03-31 | 2011-10-27 | Hitachi Zosen Corp | Method for preparing biomass feedstock originated from garbages-based waste |
| CN103205467A (en) * | 2012-01-13 | 2013-07-17 | 日立造船株式会社 | Method of producing ethanol by using biomass |
| JP2013143915A (en) * | 2012-01-13 | 2013-07-25 | Hitachi Zosen Corp | Method for producing ethanol using biomass |
| JP2016167997A (en) * | 2015-03-12 | 2016-09-23 | 日立造船株式会社 | Waste-derived biomass reaction apparatus |
| JP2017006891A (en) * | 2015-06-26 | 2017-01-12 | 日立造船株式会社 | Waste treating method for providing useful substance by using biomass in waste as raw material |
| CN107708882A (en) * | 2015-08-10 | 2018-02-16 | 日立造船株式会社 | It is attached to the high efficiency of energy Application way of the castoff burning facility of ethanol manufacturing equipment |
| JPWO2017026027A1 (en) * | 2015-08-10 | 2018-05-31 | 日立造船株式会社 | Effective energy utilization method for waste incineration facility with ethanol production facility |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5564310B2 (en) | 2014-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Prabakar et al. | Advanced biohydrogen production using pretreated industrial waste: outlook and prospects | |
| Sarker et al. | Recent advances in sugarcane industry solid by-products valorization | |
| Kaur et al. | Value addition of anaerobic digestate from biowaste: thinking beyond agriculture | |
| JP2010017084A (en) | Saccharification and fermentation system | |
| WO2013185777A4 (en) | Methods of processing municipal solid waste (msw) using concurrent enzymatic hydrolysis and microbial fermentation. | |
| JP2008104452A (en) | Alcohol production system and alcohol production method | |
| JP5564310B2 (en) | Method for saccharification and fermentation of waste-derived biomass material | |
| Medina-Morales et al. | Biohydrogen production from thermochemically pretreated corncob using a mixed culture bioaugmented with Clostridium acetobutylicum | |
| CN112058856A (en) | Anaerobic digestion method for solid kitchen waste | |
| CN111118069A (en) | Method for producing bioethanol by anaerobic fermentation of kitchen waste | |
| JP2012152133A (en) | Method of manufacturing valuables from lignocellulose-containing biomass | |
| US20230405654A1 (en) | Method for enzymatic and/or microbial processing of waste comprising recirculation of process water | |
| JP5278991B2 (en) | Method for producing ethanol raw material and ethanol from lignocellulosic biomass | |
| JP5564309B2 (en) | Method for preparing waste-derived biomass material | |
| WO2017026027A1 (en) | Method for effectively utilizing energy in waste-incineration facility with ethanol production equipment | |
| Saharan et al. | Microbial contributions to sustainable paddy straw utilization for economic gain and environmental conservation | |
| CN102168111A (en) | Process method for producing alcohol by utilizing food residues | |
| WO2010016536A1 (en) | Method for treating lignocellulose material | |
| JP2006255537A (en) | Method and apparatus for treating garbage and paper refuse | |
| JP2011211973A (en) | Method for producing bioethanol | |
| JP2017006891A (en) | Waste treating method for providing useful substance by using biomass in waste as raw material | |
| JP5622416B2 (en) | Method for preparing biomass raw materials derived from moss-based waste | |
| JP2011139686A (en) | Continuous method for producing ethanol by parallel saccharifying fermentation reaction | |
| JP2014132052A (en) | Fuel composition | |
| JP6008312B2 (en) | Simultaneous saccharification and fermentation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121225 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20131128 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131217 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140128 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140520 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140616 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5564310 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |