JP5777207B2 - Method for producing carbide from fibrous biomass - Google Patents
Method for producing carbide from fibrous biomass Download PDFInfo
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- JP5777207B2 JP5777207B2 JP2011152144A JP2011152144A JP5777207B2 JP 5777207 B2 JP5777207 B2 JP 5777207B2 JP 2011152144 A JP2011152144 A JP 2011152144A JP 2011152144 A JP2011152144 A JP 2011152144A JP 5777207 B2 JP5777207 B2 JP 5777207B2
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- 239000002028 Biomass Substances 0.000 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 238000000465 moulding Methods 0.000 claims description 45
- 239000002699 waste material Substances 0.000 claims description 39
- 239000008188 pellet Substances 0.000 claims description 33
- 238000002844 melting Methods 0.000 claims description 30
- 230000008018 melting Effects 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000005539 carbonized material Substances 0.000 claims description 11
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 239000008187 granular material Substances 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 235000019482 Palm oil Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002540 palm oil Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 240000000111 Saccharum officinarum Species 0.000 claims description 2
- 235000007201 Saccharum officinarum Nutrition 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims 1
- 239000000571 coke Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 10
- 238000000197 pyrolysis Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010000 carbonizing Methods 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 240000001549 Ipomoea eriocarpa Species 0.000 description 2
- 235000005146 Ipomoea eriocarpa Nutrition 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001228 trophic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Processing Of Solid Wastes (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Coke Industry (AREA)
Description
本発明は、パームヤシ残渣等の繊維状バイオマスから炭化物を製造する方法に関する。特に、本発明は、シャフト炉式の廃棄物溶融炉において廃棄物の溶融熱源とすることのできる炭化物をパームヤシ残渣等の繊維状バイオマスから製造する方法に関する。 The present invention relates to a method for producing carbide from fibrous biomass such as palm palm residue. In particular, the present invention relates to a method for producing a carbide that can be used as a heat source for melting waste in a shaft furnace type waste melting furnace from fibrous biomass such as palm palm residue.
一般廃棄物・産業廃棄物、あるいはそれらを乾燥、焼却、破砕処理等によって得られた処理物、これらを一度埋め立て処理後、再度掘り起こした土砂分を含む埋め立てごみ等の廃棄物を処理する方法として、これらの廃棄物をシャフト炉式の廃棄物溶融炉で溶融処理してスラグ、メタルとして再資源化する方法が実施されている。 As a method for treating waste such as landfill waste including earth and sand that has been dug up again after landfill processing once, after treating these wastes by general waste and industrial waste, or those obtained by drying, incineration, crushing, etc. These wastes are melted in a shaft furnace type waste melting furnace and recycled as slag and metal.
シャフト炉式の廃棄物溶融炉について図１１を参照して説明すると、その炉本体１は、シャフト部１ａと、下部の朝顔部５と、炉底部１０からなる。炉底部１０には燃焼・溶融帯用の下段羽口３が設けられており、その上方には熱分解帯用の複数段の上段羽口２が設けられている。下段羽口３からは酸素又は酸素富化空気を供給し、上段羽口２からは燃焼支持ガスとして空気を供給する。 A shaft furnace type waste melting furnace will be described with reference to FIG. 11. The furnace body 1 includes a shaft portion 1 a, a lower morning glory portion 5, and a furnace bottom portion 10. The bottom 10 of the furnace is provided with a lower tuyere 3 for a combustion / melting zone, and a plurality of upper tuyere 2 for a pyrolysis zone are provided above it. Oxygen or oxygen-enriched air is supplied from the lower tuyere 3, and air is supplied from the upper tuyere 2 as a combustion support gas.
炉本体１の上部には、処理対象となる廃棄物、助燃剤としてのコークス、塩基度調整剤としての石灰石等を炉内に装入するためのシール弁を備えた装入装置１１が設けられている。炉本体１の下端部には、廃棄物を溶融処理した後のスラグ、メタルを排出する出滓口１３が設けられている。 In the upper part of the furnace body 1, a charging device 11 having a seal valve for charging waste to be treated, coke as a combustion aid, limestone as a basicity adjusting agent, etc. into the furnace is provided. ing. At the lower end of the furnace body 1, an outlet 13 for discharging slag and metal after melting the waste is provided.
上記構成において、炉内に装入された廃棄物１ｂは、炉本体１の上層から乾燥・予熱帯６（約３００〜４００℃）、熱分解帯７（約３００〜１０００℃）、燃焼・溶融帯８（約１７００〜１８００℃）を通過して溶融処理される。 In the above configuration, the waste 1b charged in the furnace is dried / pre-trophic 6 (about 300-400 ° C.), pyrolysis zone 7 (about 300-1000 ° C.), combustion / melting from the upper layer of the furnace body 1 It melt-processes by passing through band 8 (about 1700-1800 ° C.).
下段羽口３から供給した酸素又は酸素富化空気によってコークス４や廃棄物の熱分解残渣１４を高温で燃焼し、溶融熱源とする。一方、上段羽口２からは空気を供給して主に廃棄物の熱分解残渣１４を燃焼し、発生したガスで廃棄物の乾燥・予熱及び熱分解を行う。溶融した廃棄物はスラグ、メタルを溶融物として出滓口１３より排出される。 The coke 4 and waste pyrolysis residue 14 are burned at a high temperature with oxygen or oxygen-enriched air supplied from the lower tuyere 3 to form a melting heat source. On the other hand, air is supplied from the upper tuyere 2 to mainly burn the pyrolysis residue 14 of the waste, and the generated gas is used for drying / preheating and pyrolysis of the waste. The molten waste is discharged from the outlet 13 with slag and metal as melt.
発生した高温のガスは、炉本体内の廃棄物の充填層を対向流として上昇し、炉本体上部の排ガス管１２から燃焼室へ導入されて燃焼される。その燃焼排ガスは、排ガス管を通ってボイラーへ導入され、熱が回収された後、減温塔で温度を調整して集じん機に通され、さらには、触媒反応塔で有害物質を除去した後、煙突から排出される。 The generated high-temperature gas rises with the packed bed of waste in the furnace body as a counterflow, is introduced into the combustion chamber from the exhaust gas pipe 12 at the top of the furnace body, and is burned. The combustion exhaust gas is introduced into the boiler through an exhaust gas pipe, and after heat is recovered, the temperature is adjusted in a temperature reducing tower and passed through a dust collector, and further, harmful substances are removed in a catalytic reaction tower. After that, it is discharged from the chimney.
このように、シャフト炉式の廃棄物溶融炉ではコークスを使用する。しかし、地球温暖化防止の観点から、化石燃料に由来するＣＯ２排出量の削減が求められており、化石燃料の使用量を削減するニーズが高まってきている。発電の1次エネルギーとしては、太陽光、風力、原子力等の様々な手段が開発されているが、産業用コークスについては代替物の開発及び実用化が進んでいない。そのため、現状では石炭を原料としたコークスの使用が必須となっているが、シャフト炉式の廃棄物溶融炉においてもコークス使用量の削減が求められている。 Thus, coke is used in a shaft furnace type waste melting furnace. However, from the viewpoint of preventing global warming, there is a demand for reducing CO 2 emissions derived from fossil fuels, and there is an increasing need to reduce the use of fossil fuels. Various means such as solar power, wind power, and nuclear power have been developed as primary energy for power generation, but development and commercialization of alternatives for industrial coke have not progressed. Therefore, at present, the use of coke made of coal as a raw material is indispensable, but reduction of the amount of coke used is also required in a shaft furnace type waste melting furnace.
その削減策の一つとして、石炭を原料とするコークスを、バイオマスを原料とする塊状燃料で代替することが提案されている。例えば、特許文献１では、バイオマスとして平均粒径１ｍｍ以下の木材粉（オガクズ）を乾燥し水分１０質量％以下とした原料を加熱加圧成型して中空筒状の固形物とし、その固形物を乾留した炭化物をコークスの代わりに使用することが提案されている。しかしながら、近年、木材粉の発生量が減少し、その安定的な調達が困難になっている。 As one of the reduction measures, it has been proposed to replace coke using coal as a raw material with bulk fuel using biomass as a raw material. For example, in Patent Document 1, a raw material having an average particle diameter of 1 mm or less as a biomass is dried by heating and press-molding a raw material having a moisture content of 10% by mass or less to form a hollow cylindrical solid, It has been proposed to use carbonized carbonized carbon instead of coke. However, in recent years, the amount of wood powder generated has decreased, making it difficult to procure it stably.
一方、未利用バイオマスとしてのパームヤシ残渣は多量に発生している。パームヤシ残渣は、野積みされて発酵したり、焼却されたりと、十分な活用が出来ておらず、木材粉に代わる炭化物原料としての適用可能性がある。しかしながら、パームヤシ残渣などの繊維状バイオマスは、木材粉と違い加熱加圧成型しても十分な強度を得ることが出来ず、コークス代替物としての利用が困難であった。 On the other hand, a large amount of palm palm residue as unused biomass is generated. Palm palm residues are not fully utilized, such as being piled up and fermented or incinerated, and may be applied as a carbide raw material to replace wood flour. However, fibrous biomass such as palm palm residue cannot obtain sufficient strength even when heated and pressed unlike wood powder, and it has been difficult to use as a coke substitute.
助燃剤として溶融炉の上部から装入されるコークスは、概ね塊状のまま炉本体１を下降し、炉底部において高温火格子を形成して溶融熱源となる。従って、強度が十分でない炭化物を溶融炉に装入した場合は、炉底部に到達するまでに粉々になってしまうので、炉底部で高温火格子を形成するためには装入量を増やさなくてはならず、場合によっては溶融炉の運転ができなくなる。 The coke charged from the upper part of the melting furnace as an auxiliary combustor descends the furnace main body 1 in a substantially lump shape, forms a high-temperature grate at the bottom of the furnace, and becomes a melting heat source. Therefore, if carbide with insufficient strength is charged into the melting furnace, it will be shattered before reaching the bottom of the furnace, so it is necessary to increase the charging amount in order to form a high-temperature grate at the bottom of the furnace. In some cases, the melting furnace cannot be operated.
そこで、本発明は、廃棄物溶融炉の廃棄物の溶融熱源となるコークスの代替となる十分な強度を得ることができる炭化物を繊維状バイオマスから製造する方法を提供するものである。 Therefore, the present invention provides a method for producing carbide from fibrous biomass that can obtain sufficient strength to replace coke as a heat source for melting waste in a waste melting furnace.
本発明は、繊維状バイオマスを破砕し、破砕した繊維状バイオマスを乾燥し、乾燥した繊維状バイオマスから造粒物を製造し、製造した造粒物から中空筒状の成型物を加熱加圧成型し、得られた中空筒状の成型物を炭化する炭化物の製造方法であって、前記造粒物がペレットであり、当該ペレットの断面の直径若しくはペレットの断面の対角線の長さを、中空筒状の成型物の中空部の内径（ｄ）と成型物の外接円の直径（Ｄ）の差（Ｄ−ｄ）の１／１０〜１／２の範囲に製造することを特徴とするものである。 In the present invention, fibrous biomass is crushed, the crushed fibrous biomass is dried, a granulated product is produced from the dried fibrous biomass, and a hollow cylindrical molded product is heated and pressure-molded from the produced granulated product. and a method of manufacturing a carbide you carbonizing the resulting hollow cylindrical molded article, said a granulated product is pellets, a length of a diagonal line of diameter or pellets of the cross-section of the cross-section of the pellets, hollow It is characterized by being manufactured within a range of 1/10 to 1/2 of the difference (D−d) between the inner diameter (d) of the hollow part of the cylindrical molded product and the diameter (D) of the circumscribed circle of the molded product It is.
繊維状バイオマスは含水率が高いので、造粒物を製造する前には乾燥させておく必要がある。また、乾燥時には比表面積を大きくとることが必要なことから、乾燥前に破砕することが望ましい。この場合、破砕寸法は、１０ｍｍ〜５０ｍｍとすることが望ましい。 Since fibrous biomass has a high moisture content, it is necessary to dry it before producing a granulated product. Further, since it is necessary to increase the specific surface area during drying, it is desirable to crush before drying. In this case, the crushing dimension is desirably 10 mm to 50 mm.
製造する造粒物はペレットであり、外形が概ね円柱状であることが好ましい。但し、造粒物の形状が制限されることはなく、タブレット、立方形状、球形状などであってもよい。 The granulated product to be produced is a pellet, and the outer shape is preferably substantially cylindrical. However, the shape of the granulated product is not limited, and may be a tablet, a cubic shape, a spherical shape, or the like.
また、繊維状バイオマスでは原料が細い繊維状であることから内部での圧縮力が不均一となり、圧縮力を十分にかけることが出来ずに十分な成型強度、成型密度を得ることができない。しかしながら、ペレット等の造粒物にすることで原料に対し成型機内部での成型圧力を均等かつ高くかけることができ、成型性が上がり、容易に成型出来るとともに、高密度で品質の良い成型物を得ることができる。このようにして得られた成型物を炭化することで密度が高く、強度の高い炭化物を得ることができる。 Further, since the raw material of fibrous biomass is a thin fiber, the internal compression force becomes non-uniform, and the compression force cannot be sufficiently applied, so that sufficient molding strength and molding density cannot be obtained. However, by using granulated materials such as pellets, the molding pressure inside the molding machine can be applied uniformly and high to the raw material, the moldability is improved, it can be easily molded, and the molded product has high density and good quality. Can be obtained. By carbonizing the molded product thus obtained, a carbide having high density and high strength can be obtained.
本発明に用いる繊維状バイオマスは、パームオイルの製造過程で発生する廃棄物である空果房（ＥＦＢ：Empty Fruit Bunch）、バイオエタノールの製造過程で発生する固形残渣、及びサトウキビのしぼりかすなどである。従来、パームオイル残渣のような繊維状バイオマスは廃棄処分されるか、せいぜい有機肥料として利用されているに過ぎなかった。この繊維状バイオマスは、廃棄物として多量に発生することから、本発明により廃棄物の有効利用が可能となる。 Fibrous biomass used in the present invention is empty fruit bunch (EFB), which is a waste generated in the manufacturing process of palm oil, a solid residue generated in the manufacturing process of bioethanol, and sugarcane residue. is there. Conventionally, fibrous biomass such as palm oil residue has been disposed of or at best utilized as organic fertilizer. Since this fibrous biomass is generated in large quantities as waste, the present invention enables effective use of waste.
繊維状バイオマスの含水率は高く、そのままでは利用できないので乾燥させる。造粒（例えばペレットを製造する）前の含水率を１０質量％〜２０質量％とすることで成型品の品質を保つことができる。含水率が１０質量％よりも低い場合には、造粒機（例えばペレット製造装置）内部で摩擦が発生しなくなり、造粒が出来なくなる。一方で、含水率が２０質量％を超えると成型時の熱で水分が急激に膨張し成型物が破裂し成型が十分に出来ない。 Since the moisture content of fibrous biomass is high and cannot be used as it is, it is dried. By setting the water content before granulation (for example, producing pellets) to 10% by mass to 20% by mass, the quality of the molded product can be maintained. When the moisture content is lower than 10% by mass, friction does not occur inside the granulator (for example, pellet production apparatus), and granulation cannot be performed. On the other hand, if the moisture content exceeds 20% by mass, the moisture rapidly expands due to heat during molding, and the molded product ruptures and the molding cannot be performed sufficiently.
繊維状バイオマスは、乾燥後に０．５ｍｍ〜１０ｍｍにまで粉砕してから造粒するのが好ましい。繊維状バイオマスの粉砕寸法を０．５ｍｍ〜１０ｍｍとすることにより、比表面積を十分にとることができ、リグニンの抽出が可能になる。なお、粉砕寸法を０．５ｍｍ未満とすると粉砕動力が大きくなるため現実的ではない。また、繊維状バイオマスの粉砕を乾燥前に行うと、含水率が高い場合に粉砕が十分に出来ず、比表面積を十分にとることが出来ない場合がある。 The fibrous biomass is preferably granulated after drying to 0.5 mm to 10 mm. By setting the pulverized dimensions of the fibrous biomass to 0.5 mm to 10 mm, a sufficient specific surface area can be obtained, and lignin can be extracted. Note that if the pulverization dimension is less than 0.5 mm, the pulverization power increases, which is not realistic. Further, if the fibrous biomass is pulverized before drying, it may not be sufficiently pulverized when the moisture content is high, and the specific surface area may not be sufficient.
また、繊維状バイオマスの繊維の長さが造粒物の最大寸法より長い場合には造粒物を切断する際に繊維が切断されず、引き抜かれることにより造粒物が粉化し、成型物の品質を確保できなくなる。成型物の品質を確保し、さらに加熱後の圧潰強度が２５００Ｎ以上である炭化物を製造するためには造粒物の粉化率が０．８質量％以下であることが好ましい。なお、前記「粉化率」とは、４ｍｍ篩上の造粒物２０００ｇをビニール袋に詰め、２０００ｍｍの高さからコンクリート床に４回落下させた後の４ｍｍ篩下質量の初期質量に対する割合を意味する。 In addition, when the fiber length of the fibrous biomass is longer than the maximum dimension of the granulated product, the fiber is not cut when the granulated product is cut. Quality cannot be secured. In order to ensure the quality of the molded product and to produce a carbide having a crushing strength of 2500 N or more after heating, the granulated product preferably has a pulverization rate of 0.8% by mass or less. The “powdering rate” is the ratio of the mass under the 4 mm sieve to the initial mass after 2000 g of granulated material on the 4 mm sieve is packed in a plastic bag and dropped 4 times from a height of 2000 mm onto the concrete floor. means.
造粒物としてのペレットの好ましい長さは１０〜３０ｍｍであるため、粉砕された繊維状バイオマスの繊維の長さは０．５〜１０ｍｍが好ましい。ペレットの断面の直径若しくはペレットの断面の対角線の長さを、中空筒状の成型物の中空部の内径（ｄ）と成型物の外接円の直径（Ｄ）の差（Ｄ−ｄ）の１／１０〜１／２の範囲に製造する。ペレットの径若しくは対角線の長さを成型機の押し出し部の最小寸法（＝中空筒状成型物の中空部の内径（ｄ）と成型物の外接円の直径（Ｄ）の差（Ｄ−ｄ））の１／１０〜１／２とすることで、成型時に押し出し部の側壁からの力の伝達が十分あり、押し出し抵抗によって十分な圧縮力を得ることが可能となり、成型品の比重、強度が十分に高くなる。１／１０未満では粒子間の力の伝達が不十分で未造粒時に比べて物理的な特牲が向上せず、成型品の品質が十分でない。また、造粒物の寸法が１／２を超えると押し出し部で閉塞が発生し、成型機が安定して運転できない。 Since the preferable length of the pellet as the granulated product is 10 to 30 mm, the length of the pulverized fibrous biomass is preferably 0.5 to 10 mm. The diameter of the cross section of the pellet or the length of the diagonal line of the cross section of the pellet is 1 of the difference (D−d) between the inner diameter (d) of the hollow portion of the hollow cylindrical molded product and the diameter (D) of the circumscribed circle of the molded product. Manufacture in the range of / 10 to 1/2. The diameter of the pellet or the length of the diagonal line is the minimum dimension of the extrusion part of the molding machine (= the difference (D−d) between the inner diameter (d) of the hollow part of the hollow cylindrical molded product and the diameter (D) of the circumscribed circle of the molded product ) Of 1/10 to 1/2, the force from the side wall of the extruded portion is sufficiently transmitted during molding, and a sufficient compressive force can be obtained by the extrusion resistance, and the specific gravity and strength of the molded product are reduced. High enough. If it is less than 1/10, the transmission of force between the particles is insufficient, the physical characteristics are not improved as compared with the case of not granulated, and the quality of the molded product is not sufficient. Moreover, when the dimension of the granulated product exceeds 1/2, the extruded portion is clogged, and the molding machine cannot be stably operated.
また、製造された造粒物の成型機での加熱加圧成型は、１５０℃〜２５０℃で行うのが好ましく、２００℃〜２５０℃であることが更に好ましい。成型時の温度を１５０℃〜２５０℃とすることで、十分な強度の成型物を得ることが出来、結果としてコークスの代替えとなり得る強度の炭化物を製造することが出来る。成型温度が１５０℃未満の場合は、バインダーとなるリグニンの軟化、溶出が十分に出来ず、成型が十分に進まない。また、成型温度が２５０℃を超えると被成型原料が熱分解、揮発するため、成型圧力が不十分となり、成型が十分でない。 Moreover, it is preferable to perform the heating and pressure molding with the molding machine of the manufactured granulated material at 150 to 250 degreeC, and it is still more preferable that it is 200 to 250 degreeC. By setting the temperature at the time of molding to 150 ° C. to 250 ° C., it is possible to obtain a molded product with sufficient strength, and as a result, it is possible to produce a carbide with strength that can substitute for coke. When the molding temperature is less than 150 ° C., the lignin serving as the binder cannot be sufficiently softened and eluted, and the molding does not proceed sufficiently. On the other hand, if the molding temperature exceeds 250 ° C., the material to be molded is thermally decomposed and volatilized, so that the molding pressure becomes insufficient and the molding is not sufficient.
中空筒状の成型物を、外接円の直径（Ｄ）が３０〜８０ｍｍ、成型物の中空部の内径（ｄ）が１０〜４０ｍｍ、ｄ／Ｄが０．１〜０．５の範囲になるように成型する。これによって成型時に被成型原料に均一な圧力がかかり、かつ、成型物の肉厚が適切になる。 The hollow cylindrical molded product has a circumscribed circle diameter (D) of 30 to 80 mm, an inner diameter (d) of the hollow portion of the molded product of 10 to 40 mm, and d / D of 0.1 to 0.5. To be molded. As a result, a uniform pressure is applied to the material to be molded at the time of molding, and the thickness of the molded product becomes appropriate.
成型物の炭化は６００〜１２００℃の温度範囲で行う。これにより、得られた炭化物の性状が高炉コークスの性状と近くなり、廃棄物溶融炉の炉底部の高温雰囲気でも高温火格子を形成可能で、安定した運転が可能となる。 Carbonization of the molded product is performed in a temperature range of 600 to 1200 ° C. As a result, the properties of the obtained carbide are close to those of the blast furnace coke, a high temperature grate can be formed even in a high temperature atmosphere at the bottom of the waste melting furnace, and stable operation is possible.
破砕した繊維状バイオマスを乾燥し、乾燥した繊維状バイオマスのうち、一部で造粒物を製造し、残りの乾燥した繊維状バイオマスと造粒物を混合し、この混合物を加熱加圧成型してもよい。造粒物の製造工程では動力を多く必要とすることから、造粒物の割合を減らすことで、効率のよい製造が可能となる。造粒物の混合割合は、５０質量％以上とする。造粒物の割合が５０％未満では成型物の品質が十分ではない。 The crushed fibrous biomass is dried, a granulated product is produced in a part of the dried fibrous biomass, the remaining dried fibrous biomass and the granulated product are mixed, and this mixture is heated and pressed. May be. Since a large amount of power is required in the production process of the granulated product, efficient production is possible by reducing the ratio of the granulated product. The mixing ratio of the granulated product is 50% by mass or more. If the ratio of the granulated product is less than 50%, the quality of the molded product is not sufficient.
また、繊維状バイオマスを破砕する前に、粗破砕をするようにしてもよい。この場合、粗破砕の寸法は、５０ｍｍ〜２００ｍｍとなるように破砕することが望ましい。 Moreover, you may make it roughly crush before crushing fibrous biomass. In this case, it is desirable to crush so that the dimension of rough crushing may be 50 mm-200 mm.
本発明によれば、繊維状バイオマスをペレット等の造粒物にすることにより、加熱加圧成型が容易となり、密度、強度が高い炭化物を製造することが出来る。 According to the present invention, by forming fibrous biomass into a granulated product such as pellets, heating and pressing can be easily performed, and a carbide having high density and strength can be produced.
繊維状バイオマスから製造した炭化物をシャフト炉式の廃棄物溶融炉においてコークスの代わりに使用することで、コークス使用量を削減することができ、化石燃料に由来するＣＯ２排出量の削減を図ることができる。 By using carbide produced from fibrous biomass in place of coke in a shaft furnace type waste melting furnace, coke consumption can be reduced, and CO 2 emissions derived from fossil fuels can be reduced. Can do.
本発明の好ましい実施形態は、シャフト炉式の廃棄物溶融炉において廃棄物の溶融熱源とする炭化物を繊維状バイオマスから製造する方法であって、図1に示すように、繊維状バイオマスを破砕機で破砕し、破砕した繊維状バイオマスを乾燥機で乾燥し、乾燥した繊維状バイオマスを粉砕し、粉砕した繊維状バイオマスを原料にして造粒機で造粒物を製造し、造粒物を原料にして成型機で加熱加圧成型して中空筒状の成型物にする。造粒物としてはペレットが好ましく、この場合、ペレット製造装置を造粒機として用いる。その後、乾留炉などの炭化装置で成型物を炭化することによって炭化物を得る。このように製造された炭化物は、廃棄物溶融炉において廃棄物の溶融熱源に利用する。 A preferred embodiment of the present invention is a method for producing carbide from a fibrous biomass as a heat source for melting waste in a shaft furnace type waste melting furnace, as shown in FIG. Crushed, dried crushed fibrous biomass with a dryer, pulverized dried fibrous biomass, manufactured granulated material from the pulverized fibrous biomass as a raw material, the granulated material as a raw material Then, it is heated and pressed by a molding machine to form a hollow cylindrical molded product. Pellet is preferable as the granulated product, and in this case, a pellet manufacturing apparatus is used as a granulator. Then, a carbide | carbonized_material is obtained by carbonizing a molding with carbonization apparatuses, such as a dry distillation furnace. The carbide thus produced is used as a heat source for melting waste in a waste melting furnace.
また、図２に示すように、繊維状バイオマスを粗破砕機で粗破砕し、その後に粉砕機で粉砕するようにしてもよい。すなわち、破砕工程を２段階で行うようにする。粗破砕工程では、５０ｍｍ〜２００ｍｍとなるように破砕し、次の破砕工程で１０〜５０ｍｍの長さとなるように破砕する。その後は、図１の実施形態と同様に、乾燥機で乾燥し、乾燥した繊維状バイオマスを粉砕し、粉砕した繊維状バイオマスからペレットなどの造粒物を製造し、造粒物を成型機で成型物にしてもよい。 Moreover, as shown in FIG. 2, fibrous biomass may be roughly crushed with a coarse crusher and then pulverized with a pulverizer. That is, the crushing process is performed in two stages. In a rough crushing process, it crushes so that it may become 50 mm-200 mm, and it crushes so that it may become 10-50 mm in a next crushing process. Thereafter, in the same manner as in the embodiment of FIG. 1, the dried fibrous biomass is pulverized, the granulated product such as pellets is produced from the pulverized fibrous biomass, and the granulated product is processed with a molding machine. It may be a molded product.
また、図３に示すように、破砕機で破砕した繊維状バイオマスを乾燥機で乾燥し、乾燥した繊維状バイオマスを粉砕し、粉砕された繊維状バイオマスのうちの一部でペレット等の造粒物を製造し、造粒しない残りの粉砕された繊維状バイオマスと造粒物を混合して、この混合物を成型機で成型してもよい。この場合、造粒物の混合割合を５０質量％以上とするのが好ましい。 Moreover, as shown in FIG. 3, the fibrous biomass crushed with the crusher is dried with a dryer, the dried fibrous biomass is pulverized, and granulation such as pellets is performed with a part of the pulverized fibrous biomass. The product may be manufactured, the remaining pulverized fibrous biomass that is not granulated and the granulated product may be mixed, and the mixture may be molded with a molding machine. In this case, the mixing ratio of the granulated product is preferably 50% by mass or more.
以下、繊維状バイオマスとしてパームヤシ残渣を用い、図１に示した工程で炭化物を製造する実施例について説明する。図４は、本実施例に用いたシステムの概略構成図である。図５は、主要な工程における繊維状バイオマスの状態の一例を示す撮影図である。 Hereinafter, the Example which manufactures a carbide | carbonized_material at the process shown in FIG. 1 using a palm palm residue as fibrous biomass is described. FIG. 4 is a schematic configuration diagram of the system used in this embodiment. FIG. 5 is a photograph showing an example of the state of fibrous biomass in the main process.
図４において、繊維状バイオマス（例えば、図５（ａ）のパームヤシ残渣）をプレス１５によって含水率３０〜５０質量％まで脱水する。図４には、プレス１５の好ましい一例としてスクリュープレス式の脱水機を示している。 In FIG. 4, fibrous biomass (for example, palm palm residue in FIG. 5A) is dehydrated with a press 15 to a moisture content of 30 to 50 mass%. FIG. 4 shows a screw press type dehydrator as a preferred example of the press 15.
脱水後の繊維状バイオマスはコンベア１６によって破砕機としてのカッター１７まで搬送し、カッター１７によって１０〜５０ｍｍ程度の長さとなるように破砕する。破砕機としては、回転刃と固定刃によって被処理物を破砕するカッターを用いることができる。 The dehydrated fibrous biomass is conveyed by a conveyor 16 to a cutter 17 as a crusher, and is crushed by the cutter 17 so as to have a length of about 10 to 50 mm. As the crusher, a cutter that crushes an object to be processed with a rotary blade and a fixed blade can be used.
破砕後の繊維状バイオマスは乾燥工程に送られる。乾燥炉１８からの熱風を利用し、ロータリードライヤー１９内で破砕後の繊維状バイオマスを乾燥させる。すなわち、ロータリードライヤー１９の回転胴体１９ａの一端側に繊維状バイオマスを投入し、回転胴体１９ａによって繊維状バイオマスを撹拌しながら熱風に曝すことによって乾燥させる。回転胴体１９ａは、傾斜配置されており、繊維状バイオマスは、回転胴体１９ａの内部で撹拌されながら他端側に移送される。 The crushed fibrous biomass is sent to the drying process. Using the hot air from the drying furnace 18, the crushed fibrous biomass is dried in the rotary dryer 19. That is, fibrous biomass is put into one end side of the rotary body 19a of the rotary dryer 19, and dried by exposing the fibrous biomass to hot air while stirring the rotary body 19a. The rotating body 19a is inclined and the fibrous biomass is transferred to the other end side while being stirred inside the rotating body 19a.
回転胴体１９ａの他端側の出口から排出された繊維状バイオマスは、さらに高圧ターボファン２０によってサイクロンセパレータ２１まで気流搬送される。この気流搬送の過程においても繊維状バイオマスは乾燥される。最終的には、含水率１０〜２０質量％程度まで乾燥させる。 The fibrous biomass discharged from the outlet on the other end side of the rotating body 19 a is further air-flowed to the cyclone separator 21 by the high-pressure turbofan 20. The fibrous biomass is also dried during the airflow conveyance process. Finally, it is dried to a moisture content of about 10 to 20% by mass.
乾燥後の繊維状バイオマスは、サイクロンセパレータ２１によって捕集され、サイクロンセパレータ２１下部の定量切出装置２２から排出され、粉砕機２３によって０．５〜１０ｍｍの長さとなるように粉砕される。粉砕機２３は、固定刃と回転する粉砕刃によって被処理物を粉砕する（図５（ｂ）参照）。 The dried fibrous biomass is collected by the cyclone separator 21, discharged from the quantitative cutting device 22 below the cyclone separator 21, and pulverized to a length of 0.5 to 10 mm by the pulverizer 23. The pulverizer 23 pulverizes the workpiece with a fixed blade and a rotating pulverization blade (see FIG. 5B).
粉砕後の繊維状バイオマスはペレット製造装置２４で平均径０．５〜１０ｍｍ、長さ１０〜３０ｍｍのペレットが製造される。ペレット製造装置２４は、多数の円筒形の小孔を持つダイスと圧縮ローラからなり、繊維状バイオマスは圧縮ローラで小孔に押し込まれてペレットに成型される（図５（ｃ）参照）。 The pulverized fibrous biomass is produced by a pellet production apparatus 24 to produce pellets having an average diameter of 0.5 to 10 mm and a length of 10 to 30 mm. The pellet manufacturing apparatus 24 includes a die having a large number of small cylindrical holes and a compression roller, and fibrous biomass is pressed into the small holes by the compression roller and formed into pellets (see FIG. 5C).
ペレットは成型機２５に投入されて成型され（図５（ｄ）参照）、成型物は乾留炉２６で乾留する（図５（ｅ）参照）。成型機２５として、例えば、図６に示す乾式のスクリュー型押出成型機を使用し、繊維状バイオマス原料をスクリュー２５ａでダイス２５ｂに送り込み、ダイス２５ｂをヒータ２５ｃによって１５０℃〜２５０℃に加熱して中空筒状に成型する。中空筒状の成型物の断面形状については、中空部の内径（ｄ）と成型物の外接円の直径（Ｄ）が適切な範囲にあれば、図７（ａ）に示す円形をはじめ、（ｂ）の四角形、（ｃ）の六角形、（ｄ）の三角形などであってもよい。 The pellets are put into the molding machine 25 and molded (see FIG. 5D), and the molded product is carbonized in the carbonization furnace 26 (see FIG. 5E). As the molding machine 25, for example, a dry screw-type extrusion molding machine shown in FIG. 6 is used. The fibrous biomass material is fed into the die 25b with the screw 25a, and the die 25b is heated to 150 ° C. to 250 ° C. with the heater 25c. Molded into a hollow cylinder. As for the cross-sectional shape of the hollow cylindrical molded product, if the inner diameter (d) of the hollow portion and the diameter (D) of the circumscribed circle of the molded product are within an appropriate range, the circular shape shown in FIG. It may be a quadrangle of b), a hexagon of (c), a triangle of (d), or the like.
ペレットの断面が円形の場合はその直径、断面が多角形の場合はその対角線の長さ若しくは外接円の直径を、中空筒状の成型物の中空部の内径（ｄ）と成型物の外接円の直径（Ｄ）の差（Ｄ−ｄ）の１／１０〜１／２の範囲になるようにする。この中空筒状の成型物の具体的な形状は、その断面形状が、外径３０〜８０ｍｍで内部に直径１０〜４０ｍｍの空胴を持ち、外径をＤ、内径をｄとするとｄ／Ｄが０．１〜０．５の範囲にある中空筒状とした。また、乾留炉２６による乾留温度は６００〜１２００℃の範囲とした。 If the cross section of the pellet is circular, the diameter of the pellet, if the cross section is polygonal, the length of the diagonal or the diameter of the circumscribed circle, the inner diameter (d) of the hollow portion of the hollow cylindrical molded product and the circumscribed circle of the molded product In the range of 1/10 to 1/2 of the difference (D−d) in the diameter (D) of The specific shape of this hollow cylindrical molded product is d / D, where the cross-sectional shape is 30 to 80 mm in outer diameter, a cavity with a diameter of 10 to 40 mm inside, D is the outer diameter, and d is the inner diameter. Was in the form of a hollow cylinder in the range of 0.1 to 0.5. Moreover, the carbonization temperature by the carbonization furnace 26 was made into the range of 600-1200 degreeC.
表1はペレット化の有無による成型性の評価を示す。すなわち、ペレットに成型する工程を有する本実施例と、ペレットに成型する工程を有しないこと以外は本実施例と同様の工程で炭化物を製造した比較例との比較によって成型性を評価した。 Table 1 shows the evaluation of moldability with and without pelletization. That is, the moldability was evaluated by comparing this example having a step of forming into pellets with a comparative example in which carbide was produced in the same steps as in this example except that the step of forming into pellets was not provided.
破砕・粉砕のみでペレットにしない場合は、成型機２５で成型することは可能ではあるが、成型機２５の出口から押し出されるとすぐに折れたり崩れたりして品質が安定しない。すなわち、ペレット化しない場合は実質的に成型できないと言える。これに対して、成型前にペレットにした場合には、成型が容易で所望の成型サイズの成型物を得ることができ、非常に高い品質が得られた。 If the pellet is formed only by crushing and pulverization, it can be molded by the molding machine 25, but when it is pushed out from the outlet of the molding machine 25, it will be broken or collapsed and the quality will not be stable. In other words, it can be said that substantially no molding is possible when the pellets are not formed. On the other hand, when pellets were formed before molding, molding was easy and a molded product having a desired molding size was obtained, and very high quality was obtained.
表２はペレットの成型サイズと成型性の評価を示すものである。
また、図８は、成型機２５の成型温度を１３０℃、１５０℃、２００℃、２２５℃、２５０℃、２７５℃にして成型物を製造し、乾留炉２６で炭化することによって得られた炭化物の圧潰強度（Ｎ）を示す。ここでいう圧潰強度（Ｎ）とは、廃棄物溶融炉内の温度条件を考慮して、１０００℃の空気中に３０分曝露した後の圧潰強度である。図８に示す試験結果から明らかなように、成型機２５での成型温度を１５０℃〜２５０℃、更に好ましくは２００℃〜２５０℃とすることにより、高い強度の炭化物が得られる。何故なら、図９に示されるように、成型温度を２００℃〜２５０℃とすることにより、見掛密度（ｇ／ｍＬ）の高い成型物が得られるからである。 Further, FIG. 8 shows a carbide obtained by manufacturing a molding by setting the molding temperature of the molding machine 25 to 130 ° C., 150 ° C., 200 ° C., 225 ° C., 250 ° C., 275 ° C. and carbonizing it in the dry distillation furnace 26. The crushing strength (N) is shown. The crushing strength (N) here is the crushing strength after exposure to air at 1000 ° C. for 30 minutes in consideration of the temperature conditions in the waste melting furnace. As is apparent from the test results shown in FIG. 8, by setting the molding temperature in the molding machine 25 to 150 ° C. to 250 ° C., more preferably 200 ° C. to 250 ° C., high strength carbide can be obtained. This is because, as shown in FIG. 9, by setting the molding temperature to 200 ° C. to 250 ° C., a molded product having a high apparent density (g / mL) can be obtained.
コークスの代替えとなり得る炭化物の圧潰強度は１０００（Ｎ）以上であるが、廃棄物溶融炉をより良好に運転するには２５００（Ｎ）以上であることが望ましい。また、図１０は、ペレットの粉化率と炭化物の圧潰強度（Ｎ）の相関関係を示す。炭化物の圧潰強度（２５００（Ｎ））を基準とし、粉化率が０．７８質量％、０．２０質量％、１．８４質量％のときの炭化物の圧潰強度を相対的に示すと共に、近似線を記載している。図１０の試験結果に基づけば、２５００（Ｎ）以上の圧潰強度を達成するための粉化率は０．８質量％以下である。 The crushing strength of carbide that can replace coke is 1000 (N) or more, but 2500 (N) or more is desirable for better operation of the waste melting furnace. FIG. 10 shows the correlation between the pelletization rate and the crushing strength (N) of the carbide. Based on the crushing strength of carbide (2500 (N)), the crushing strength of carbide when the powdering rate is 0.78 mass%, 0.20 mass%, 1.84 mass% is relatively shown and approximated. Lines are shown. Based on the test result of FIG. 10, the powdering rate for achieving a crushing strength of 2500 (N) or more is 0.8 mass% or less.
以上の工程により、繊維状バイオマスからコークスの代替となる炭化物、すなわちシャフト炉式の廃棄物溶融炉において廃棄物の溶融熱源とすることができる炭化物を製造することができる。具体的には、１０００℃の空気中に３０分曝露する場合の曝露前後の質量減少が３０％以内であり、かつ曝露後の圧潰強度が１０００Ｎ以上かつ揮発分が２０質量％以下、かつ真比重が１．２〜２．０ｇ／ｃｍ３の範囲にある炭化物を製造することができる。 Through the above-described steps, it is possible to produce carbide that can replace coke from fibrous biomass, that is, carbide that can be used as a heat source for melting waste in a shaft furnace type waste melting furnace. Specifically, when exposed to air at 1000 ° C. for 30 minutes, the mass loss before and after exposure is within 30%, the crushing strength after exposure is 1000 N or more, the volatile content is 20 mass% or less, and the true specific gravity Can produce carbides in the range of 1.2-2.0 g / cm 3 .
１：廃棄物溶融炉の炉本体 １ａ：シャフト部
１ｂ：廃棄物 ２：上段羽口
３：下段羽口 ４：コークス
５：朝顔部 ６：乾燥・予熱帯
７：熱分解帯 ８：燃焼・溶融帯
９：炭化物 １０：炉底部
１１：装入装置 １２：排ガス管
１３：出滓口 １４：熱分解残渣
１５：プレス １６：コンベア
１７：カッター １８：乾燥炉
１９：ロータリードライヤー ２０：高圧ターボファン
２１：サイクロンセパレータ ２２：定量切出装置
２３：粉砕機 ２４：ペレット製造装置
２５：成型機 ２５ａ：スクリュー
２５ｂ：ダイス ２５ｃ：ヒータ
２６：乾留炉
1: Furnace body of waste melting furnace 1a: Shaft part 1b: Waste 2: Upper tuyere 3: Lower tuyere 4: Coke 5: Morning glory 6: Drying / pre-tropical zone 7: Pyrolysis zone 8: Combustion / melting Belt 9: Carbide 10: Furnace bottom part 11: Charger 12: Exhaust pipe 13: Outlet 14: Thermal decomposition residue 15: Press 16: Conveyor 17: Cutter 18: Drying furnace 19: Rotary dryer 20: High-pressure turbofan 21 : Cyclone separator 22: Fixed quantity cutting device 23: Pulverizer 24: Pellet production device 25: Molding machine 25a: Screw 25b: Die 25c: Heater 26: Dry distillation furnace
Claims (11)
前記造粒物がペレットであり、当該ペレットの断面の直径若しくはペレットの断面の対角線の長さを、中空筒状の成型物の中空部の内径（ｄ）と成型物の外接円の直径（Ｄ）の差（Ｄ−ｄ）の１／１０〜１／２の範囲に製造することを特徴とする炭化物の製造方法。 It is obtained by crushing fibrous biomass, drying the crushed fibrous biomass, producing a granulated product from the dried fibrous biomass, and heat-pressing a hollow cylindrical molded product from the produced granulated product. and the hollow cylindrical molded product a method for producing a carbide you carbide,
The granulated material is a pellet, and the diameter of the cross section of the pellet or the length of the diagonal line of the cross section of the pellet is defined as the inner diameter (d) of the hollow portion of the hollow cylindrical molded product and the diameter of the circumscribed circle of the molded product (D ) Difference (D−d) in the range of 1/10 to 1/2.
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| WO2017095042A1 (en) * | 2015-12-03 | 2017-06-08 | Korea Research Institute Of Chemical Technology | Development of biomass pretreatment technology via controlled feeding system of fibrous biomass into continuous high-pressure reactor |
| KR101843956B1 (en) | 2018-02-22 | 2018-05-14 | 한국화학연구원 | Preparation method of fibrous biomass for high pressure pretreatment and method using the same |
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| JP5530042B1 (en) * | 2014-01-08 | 2014-06-25 | 新日鉄住金エンジニアリング株式会社 | Carbide manufacturing method and carbide manufacturing system |
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| JP6410976B1 (en) * | 2018-03-14 | 2018-10-24 | 新日鉄住金エンジニアリング株式会社 | Method for producing molded body and method for producing carbide |
| JP6388740B1 (en) * | 2018-03-14 | 2018-09-12 | 新日鉄住金エンジニアリング株式会社 | Molded body manufacturing method, carbide manufacturing method, and molded body manufacturing system |
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| JP2003261878A (en) * | 2002-03-11 | 2003-09-19 | National Institute For Rural Engineering | Manufacturing method for carbide |
| JP2007093069A (en) * | 2005-09-28 | 2007-04-12 | Nippon Steel Engineering Co Ltd | Waste melting furnace operating method |
| JP2008308570A (en) * | 2007-06-14 | 2008-12-25 | Nippon Steel Engineering Co Ltd | Method for utilizing highly hydrous waste and treatment apparatus |
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| KR101843956B1 (en) | 2018-02-22 | 2018-05-14 | 한국화학연구원 | Preparation method of fibrous biomass for high pressure pretreatment and method using the same |
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