JP2006063310A - Method and apparatus for producing wood-biomass-derived liquid fuel - Google Patents
Method and apparatus for producing wood-biomass-derived liquid fuel Download PDFInfo
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- JP2006063310A JP2006063310A JP2005061837A JP2005061837A JP2006063310A JP 2006063310 A JP2006063310 A JP 2006063310A JP 2005061837 A JP2005061837 A JP 2005061837A JP 2005061837 A JP2005061837 A JP 2005061837A JP 2006063310 A JP2006063310 A JP 2006063310A
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- woody biomass
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- 239000002028 Biomass Substances 0.000 title claims abstract description 82
- 239000000446 fuel Substances 0.000 title claims abstract description 76
- 239000007788 liquid Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000003960 organic solvent Substances 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 239000000295 fuel oil Substances 0.000 claims abstract description 9
- 239000000523 sample Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 30
- 238000012360 testing method Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 10
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002440 industrial waste Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 abstract description 7
- 239000003208 petroleum Substances 0.000 abstract description 3
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 abstract 1
- 239000010742 number 1 fuel oil Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 20
- 229910001873 dinitrogen Inorganic materials 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 241000218645 Cedrus Species 0.000 description 13
- 230000005674 electromagnetic induction Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000003350 kerosene Substances 0.000 description 6
- 239000010893 paper waste Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 244000166124 Eucalyptus globulus Species 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009283 thermal hydrolysis Methods 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 238000011088 calibration curve Methods 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- -1 large sawdust Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Images
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/78—Recycling of wood or furniture waste
Landscapes
- Processing Of Solid Wastes (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
本発明は、木質バイオマス由来の液体燃料の製造方法及び製造装置に関するものである
。
The present invention relates to a method and an apparatus for producing a liquid fuel derived from woody biomass.
バイオマスは、水や二酸化炭素等の無機物が太陽エネルギーを用いて光合成により生物
体等の有機物に変換されたものとして定義される。これらのバイオマスは、枯死後再び生
物化学的に無機物に分解されるため持続的にリサイクルすることが可能で、カーボンニュ
ートラルの炭化水素資源であることから、環境調和型エネルギー資源として注目されてい
る。しかし、木質バイオマスとして知られる建築廃材や梱包材、間伐材や製材屑は、多量
に排出されているにも関わらず、一部が燃料チップ等として利用される以外は主に焼却処
分され、ほとんどリサイクルされていないのが現状である。
Biomass is defined as an inorganic substance such as water or carbon dioxide converted into an organic substance such as a living organism by photosynthesis using solar energy. Since these biomasses are biochemically decomposed again into inorganic substances after they die, they can be recycled continuously and are attracting attention as environmentally friendly energy resources because they are carbon neutral hydrocarbon resources. However, building waste materials, packaging materials, thinning materials and sawdust, known as woody biomass, are mostly incinerated except for some being used as fuel chips, etc. The current situation is that it is not recycled.
木質バイオマスをエネルギー資源としてリサイクルするにあたり、木質バイオマスは高
含水率で単位発熱量が低く、不均質な固体であるためハンドリング性が悪いという問題が
ある。また木質バイオマスを高温高圧で反応させ、ガス化して水素を回収する方法や、長
時間発酵させてアルコールを製造する方法が研究されているが、小規模な事業所、工場等
ではこれらの水素やアルコールを燃料として利用できず有用性が低いという問題がある。
When recycling woody biomass as an energy resource, woody biomass has a problem of poor handling due to its high water content, low unit calorific value, and a heterogeneous solid. In addition, methods of reacting woody biomass at high temperature and pressure and gasifying it to recover hydrogen, and methods of producing alcohol by fermenting for a long time have been studied. There is a problem that alcohol cannot be used as a fuel and its usefulness is low.
木質バイオマスが排出される小規模な事業所、工場では、小規模で温和な運転条件の装
置を用いて、排出された木質バイオマスをエネルギー資源としてリサイクルし、必要量の
燃料を製造し、エネルギー自給型工場を構築することが望ましい。このためには、木質バ
イオマスから灯油・軽油〜重油留分を得る直接液化法が最適である。従来の直接液化法と
しては、水を溶媒とし、アルカリを触媒とし、300℃約100気圧という高圧な反応条
件下で行う方法が知られている(例えば、非特許文献1参照)。このような液化方法は高
圧となることから危険性が高く、またマレイン酸等の有機酸が副産物として得られるとい
う問題があった。そこで、温和な反応条件で、安全性が高く、簡便な工程で効率的に灯油
・軽油〜重油留分が得られるエネルギー変換技術の開発が望まれている。
本発明は、安全性が高く、簡便で効率的な木質バイオマス由来の液体燃料の製造方法及
び製造装置の提供を課題とする。
This invention makes it a subject to provide the manufacturing method and manufacturing apparatus of the liquid fuel derived from a woody biomass which are highly safe, simple and efficient.
本発明者らは、上記課題を解決するために鋭意研究を行った結果、溶媒として水ではな
く有機溶媒を用いることにより、温和な反応条件で効率的に灯油・軽油〜重油留分が得ら
れることを見出し、本発明を完成するに至った。
As a result of intensive studies to solve the above problems, the present inventors can efficiently obtain kerosene / light oil to heavy oil fractions under mild reaction conditions by using an organic solvent instead of water as a solvent. As a result, the present invention has been completed.
本発明の有機溶媒を用いる直接液化法は、低圧で温和な反応条件を可能にするとともに
、有機酸が副産物として製造されず、非常にクリーンな方法である。また、得られた液体
燃料を自家溶媒として循環使用することにより、さらに効率的に反応を継続できるという
利点がある。
すなわち、本発明は以下の通りである。
The direct liquefaction method using the organic solvent of the present invention is a very clean method that allows mild reaction conditions at low pressure and does not produce an organic acid as a byproduct. Moreover, there is an advantage that the reaction can be continued more efficiently by circulating and using the obtained liquid fuel as an in-house solvent.
That is, the present invention is as follows.
(1)(A)木質バイオマスからなる供試材を有機溶媒と混合し、熱分解が行われる温度
及び圧力で液化する工程と、
(B)(A)の工程により生じた該供試材の分解物を分離して、木質バイオマス由
来の液体燃料を得る分離工程と
を含むことを特徴とする木質バイオマス由来の液体燃料の製造方法。
(2)上記木質バイオマス由来の液体燃料の一部を自家溶媒として循環使用することで、
木質バイオマスを継続して液化することを特徴とする請求項1に記載の木質バイオマス由
来の液体燃料の製造方法。
(3)上記液化工程(A)において、用いる有機溶媒が該供試材の1重量倍以上10重量
倍以下であることを特徴とする上記(1)または(2)に記載の木質バイオマス由来の液
体燃料の製造方法。
(4)上記液化工程(A)において、用いる有機溶媒が常圧沸点300℃以上の重油留分
であることを特徴とする上記(1)〜(3)のいずれかに記載の木質バイオマス由来の液
体燃料の製造方法。
(5)供試材に用いる木質バイオマスが木質系産業廃棄物である上記(1)〜(4)のい
ずれかに記載の木質バイオマス由来の液体燃料の製造方法。
(6)供試材の水分含有率が10重量%以下である上記(1)〜(5)のいずれかに記載
の木質バイオマス由来の液体燃料の製造方法。
(7)供試材に用いる木質バイオマスを破砕処理する工程をさらに含む上記(1)〜(6
)のいずれかに記載の木質バイオマス由来の液体燃料の製造方法。
(8)上記液化工程(A)において、加熱温度を250℃〜400℃に調整することを特
徴とする上記(1)〜(7)のいずれかに記載の木質バイオマス由来の液体燃料の製造方
法。
(9)上記液化工程(A)において、圧力を大気圧以上15気圧未満に調整することを特
徴とする上記(1)〜(8)のいずれかに記載の木質バイオマス由来の液体燃料の製造方
法。
(10)(A)該供試材に有機溶媒を混合する混合槽と、
(B)該混合物を熱分解が生じる温度で加熱処理する液化工程を行う反応槽と、
(C)加熱により生じた上記供試材の分解物を分離して、木質バイオマス由来の
液体燃料を得る分離工程を行う分離槽と、
(D)木質バイオマス由来の液体燃料の一部を自家溶媒として、上記混合層に循
環する循環経路とを具備する木質バイオマス由来の液体燃料の製造装置。
(11)木質バイオマスを破砕処理して、該木質バイオマス由来の供試材を得る破砕工程
を行う破砕槽を具備する上記(10)に記載の木質バイオマス由来の液体燃料の製造装置
。
(1) (A) mixing a sample material made of woody biomass with an organic solvent, and liquefying at a temperature and pressure at which thermal decomposition is performed;
(B) separating the decomposition product of the test material generated in the step (A) to obtain a woody biomass-derived liquid fuel, and a method for producing a woody biomass-derived liquid fuel, .
(2) By circulating a part of the liquid fuel derived from the woody biomass as an in-house solvent,
The method for producing a liquid fuel derived from woody biomass according to claim 1, wherein the woody biomass is continuously liquefied.
(3) In the liquefaction step (A), the organic solvent to be used is derived from the woody biomass according to (1) or (2) above, wherein the organic solvent to be used is 1 to 10 times the test material Method for producing liquid fuel.
(4) In the liquefaction step (A), the organic solvent to be used is a heavy oil fraction having an atmospheric pressure boiling point of 300 ° C. or higher, which is derived from the woody biomass according to any one of the above (1) to (3) Method for producing liquid fuel.
(5) The method for producing a liquid fuel derived from woody biomass according to any one of the above (1) to (4), wherein the woody biomass used for the test material is woody industrial waste.
(6) The manufacturing method of the liquid fuel derived from the woody biomass in any one of said (1)-(5) whose moisture content of a test material is 10 weight% or less.
(7) The above (1) to (6) further comprising a step of crushing the woody biomass used for the test material.
The manufacturing method of the liquid fuel derived from the woody biomass in any one of.
(8) In the said liquefaction process (A), heating temperature is adjusted to 250 to 400 degreeC, The manufacturing method of the liquid fuel derived from the woody biomass in any one of said (1)-(7) characterized by the above-mentioned .
(9) In the said liquefaction process (A), a pressure is adjusted to atmospheric pressure or more and less than 15 atmospheres, The manufacturing method of the liquid fuel derived from the woody biomass in any one of said (1)-(8) characterized by the above-mentioned .
(10) (A) a mixing tank for mixing an organic solvent with the test material;
(B) a reaction vessel that performs a liquefaction step of heat-treating the mixture at a temperature at which thermal decomposition occurs;
(C) A separation tank for separating a decomposition product of the test material generated by heating and performing a separation step of obtaining a liquid fuel derived from woody biomass,
(D) An apparatus for producing a woody biomass-derived liquid fuel comprising a circulation path that circulates in the mixed layer using a part of the woody biomass-derived liquid fuel as a self-solvent.
(11) The apparatus for producing a liquid fuel derived from a woody biomass according to (10), further comprising a crushing tank that crushes the woody biomass and performs a crushing step for obtaining a test material derived from the woody biomass.
本発明の木質バイオマス由来の液体燃料の製造方法及び製造装置は、低圧で温和な反応
条件で灯油・軽油〜重油留分を得ることができる。さらに得られた液体燃料を自家溶媒と
して循環使用することで、効率的に液化を継続できる。この利点を生かし、小規模なエネ
ルギー自給型工場等の構築に利用できる。
The method and apparatus for producing liquid fuel derived from woody biomass of the present invention can obtain kerosene / light oil to heavy oil fractions under low pressure and mild reaction conditions. Furthermore, liquefaction can be continued efficiently by circulating and using the obtained liquid fuel as an in-house solvent. Taking advantage of this advantage, it can be used to construct small-scale energy self-sufficient factories.
本発明の木質バイオマスには、草、廃木材、間伐材、大鋸屑、燃料チップ等が含まれ、
トマトやトウモロコシ等の農作物収穫後の廃木等も挙げることができる。スギ等の建築廃
材も用いることができ、建築用の塩化ビニル等を含む壁紙、石膏、セメント、塗料、接着
剤、防腐剤などの不純物が付着したものでも良い。いずれの木質バイオマスも本発明の原
料として用いることができるが、特に乾燥して水分含量が低いものが好ましい。
The woody biomass of the present invention includes grass, waste wood, thinned wood, large sawdust, fuel chips, etc.
Examples include waste trees after harvesting crops such as tomatoes and corn. Architectural waste such as cedar can also be used, and it may be a wall paper containing a vinyl chloride for construction, a gypsum, a cement, a paint, an adhesive, an antiseptic and other impurities. Any woody biomass can be used as the raw material of the present invention, but a dry one having a low water content is particularly preferable.
本発明の木質バイオマスは、有機溶剤を含むスラリーとして該装置中を移送できるよう
に、あらかじめタワーミル(日本アイリッヒ株式会社製 NE010等)等で粉砕したも
のを用いることができる。粉砕した試料は、さらに乾燥したものが望ましく、水分含有量
が10重量%以下の供試材を用いることができる。
The woody biomass of the present invention can be pulverized in advance with a tower mill (NE010 manufactured by Japan Eirich Co., Ltd.) or the like so that it can be transferred into the apparatus as a slurry containing an organic solvent. The pulverized sample is preferably further dried, and a test material having a water content of 10% by weight or less can be used.
本発明では木質バイオマスを液化する液化溶媒として有機溶媒が用いられる。本発明の
有機溶媒としてはアントラセン、ナフタレン、テトラリン等を用いることができ、液化に
より生成した液体燃料のうち灯油・軽油等の必要な留分を除いた重油留分等の一部を自家
溶媒として用いることもできる。本発明で自家溶媒とは、木質バイオマスから生成した液
体燃料またはその一部の意味で用いる。自家溶媒は、原料との親和性が高く、液体燃料の
収率を高めることができる。さらに、自家溶媒の循環使用によって、外部からの有機溶媒
の添加がなくても、液体燃料を繰り返し合成することができるようになる。液化工程の最
初に加える有機溶媒は、いずれの有機溶媒でも良いが、常圧沸点が300℃以上の重油留
分が好ましく、例えばアントラセン等が挙げられる。
In the present invention, an organic solvent is used as a liquefaction solvent for liquefying woody biomass. As the organic solvent of the present invention, anthracene, naphthalene, tetralin and the like can be used, and a part of a heavy oil fraction etc. excluding necessary fractions such as kerosene and light oil among liquid fuels produced by liquefaction is used as an in-house solvent. It can also be used. In the present invention, the self-solvent is used to mean a liquid fuel produced from woody biomass or a part thereof. The self-solvent has high affinity with the raw material, and can increase the yield of liquid fuel. Further, the circulation of the self-solvent allows the liquid fuel to be synthesized repeatedly without the addition of an organic solvent from the outside. The organic solvent added at the beginning of the liquefaction step may be any organic solvent, but is preferably a heavy oil fraction having an atmospheric pressure boiling point of 300 ° C. or higher, such as anthracene.
本発明は液化溶媒として沸点が高い有機溶媒や自家溶媒を用いることにより、主に熱分
解反応によって液化が行われ、液化工程でも低圧が保たれる。さらに液化溶媒として水を
用いない為、有機酸類を含まない質の高い液体燃料が得られ、一酸化炭素、二酸化炭素等
の大気中に排出できる無機ガスのみが生成されるため、安全性が高い。一方で、従来から
知られている水を液化溶媒として用いた方法では、熱分解と加水分解により液化が行われ
る。水は沸点が低く、高温の液化工程で水蒸気となる為、高圧の原因となる。さらに加水
分解により生成した有機酸類を含む質の低い液体燃料が得られるという問題があった。
In the present invention, by using an organic solvent having a high boiling point or a self-solvent as a liquefying solvent, liquefaction is mainly performed by a thermal decomposition reaction, and a low pressure is maintained even in the liquefaction process. Furthermore, since water is not used as a liquefied solvent, high-quality liquid fuels that do not contain organic acids are obtained, and only inorganic gases that can be discharged into the atmosphere, such as carbon monoxide and carbon dioxide, are produced, which is highly safe. . On the other hand, in the conventional method using water as a liquefaction solvent, liquefaction is performed by thermal decomposition and hydrolysis. Since water has a low boiling point and becomes water vapor in a high-temperature liquefaction process, it causes high pressure. Furthermore, there is a problem that a low-quality liquid fuel containing organic acids produced by hydrolysis can be obtained.
本発明の供試材と有機溶媒の混合割合としては、スラリーとして該装置中を移送できる
程度の流動性があれば良く、1:1〜1:10などの割合が好ましい。液化工程は電磁誘
導攪拌式オートクレーブ(鈴木理化学製作所製 SUS316)等の高温高圧の耐圧器中
で実施することができる。供試材と有機溶媒の混合物を耐圧器中に挿入して密閉し、窒素
ガスまたは水素ガスで置換し、さらにこのガスを0.1〜3.0MPaまで充填して初圧
を設定した後、外部電気炉(鈴木理化学製作所製等)等で所定温度(250℃〜400℃
)に加熱し、昇温から所定温度まで内容物に対して水平攪拌を行い、所定温度に到達後直
ちに常温まで空冷することで液化工程を実施することができる。本発明の液化工程の条件
は、反応温度が250℃〜400℃であれば良く、特に収率が高い350℃〜400℃が
好ましい。また、反応圧力は15気圧未満が好ましい。
The mixing ratio of the test material of the present invention and the organic solvent is sufficient if it is fluid enough to transfer the slurry as a slurry, and a ratio of 1: 1 to 1:10 is preferable. The liquefaction step can be carried out in a high-temperature and high-pressure pressure device such as an electromagnetic induction stirring autoclave (SUS316, manufactured by Suzuki Rikagaku). After inserting the mixture of the test material and the organic solvent into the pressure vessel and sealing, replacing with nitrogen gas or hydrogen gas, and further filling this gas to 0.1 to 3.0 MPa to set the initial pressure, Predetermined temperature (250 ° C to 400 ° C) with an external electric furnace (Suzuki Riken, etc.)
), The contents are horizontally agitated from a temperature rise to a predetermined temperature, and then cooled to room temperature immediately after reaching the predetermined temperature. The conditions for the liquefaction step of the present invention may be a reaction temperature of 250 ° C. to 400 ° C., and a high yield of 350 ° C. to 400 ° C. is particularly preferable. The reaction pressure is preferably less than 15 atmospheres.
本発明の木質バイオマス由来の液体燃料の製造は、温度及び圧力、溶媒量等の反応条件
によって適宜実施することができる。本発明の対象である自給型エネルギー工場等の構築
においては、必要なエネルギーを得る石油の2重量倍以上の木質バイオマスを用い、連続
装置で必要量の液体燃料を得ることができる。さらに得られた残渣は難分解性のリグニン
が軽度に分解した成分が主であるため、供試材として再度液化工程のサイクルに加えるか
、石油製品の原材料とすることができる。また、液化工程によって生成されるガスは一酸
化炭素や二酸化炭素が主成分である為、そのまま廃棄することができる。本発明により得
られた木質バイオマス由来の液体燃料は、ガソリン、石油、灯油等の油として、石油製品
の原材料として利用できる。
The production of the liquid fuel derived from the woody biomass of the present invention can be appropriately carried out depending on the reaction conditions such as temperature, pressure, and solvent amount. In the construction of a self-sufficient energy factory or the like that is the subject of the present invention, a required amount of liquid fuel can be obtained with a continuous device using woody biomass more than twice the weight of petroleum that obtains the required energy. Furthermore, since the residue obtained is mainly composed of a component in which refractory lignin is slightly decomposed, it can be added again as a test material to the cycle of the liquefaction process or used as a raw material for petroleum products. Moreover, since the gas produced | generated by a liquefaction process has carbon monoxide and a carbon dioxide as a main component, it can be discarded as it is. The woody biomass-derived liquid fuel obtained by the present invention can be used as a raw material for petroleum products as oils such as gasoline, petroleum, and kerosene.
本発明の木質バイオマス由来の液体燃料の製造装置は、(A)木質バイオマスを破砕処
理して、該木質バイオマス由来の供試材を得る破砕工程を行う破砕槽と、(B)該供試材
に有機溶媒を混合する混合槽と、(C)該混合物を熱分解が生じる温度で加熱処理する液
化工程を行う反応槽と、(D)加熱により生じた上記供試材の分解物を分離して、木質バ
イオマス由来の液体燃料を得る分離工程を行う分離槽と、(E)木質バイオマス由来の液
体燃料の一部を自家溶媒として、上記混合槽に循環する循環経路とを具備する製造装置で
あれば良く、市販のタワーミル(日本アイリッヒ株式会社製 NE010等)、電磁誘導
攪拌式オートクレーブ(鈴木理化学製作所製 SUS316)等の高温高圧の耐圧器等を
組み合わせることもできる。また、本発明によれば、圧力が15気圧未満で液化処理する
工程を実施できることから、高級材料を使うことなく装置材料上有利に製造装置を得るこ
とができる。
The manufacturing apparatus of the liquid fuel derived from the woody biomass of the present invention includes (A) a crushing tank for crushing the woody biomass and performing a crushing step of obtaining the woody biomass-derived test material, and (B) the test material. (C) a reaction tank for performing a liquefaction process in which the mixture is heat-treated at a temperature at which thermal decomposition occurs, and (D) a decomposition product of the test material generated by heating. A separation tank that performs a separation step for obtaining a liquid fuel derived from woody biomass, and (E) a circulation path that circulates to the mixing tank using a part of the liquid fuel derived from woody biomass as an in-house solvent. A high-temperature and high-pressure pressure device such as a commercially available tower mill (NE010, manufactured by Japan Eirich Co., Ltd.), an electromagnetic induction stirring autoclave (SUS316, manufactured by Suzuki Rikagaku Co., Ltd.), or the like can be used. In addition, according to the present invention, since the liquefaction process can be performed at a pressure of less than 15 atm, a manufacturing apparatus can be advantageously obtained in terms of apparatus materials without using high-grade materials.
以下、本発明の詳細を実施例にて示すが本発明はこれに限定されるものではない。 Hereinafter, although the detail of this invention is shown in an Example, this invention is not limited to this.
木質バイオマス由来の液体燃料の製造
スギ200gと、直径6mmの鉄球約10kgを粉砕媒体としてタワーミル(日本アイ
リッヒ株式会社製 NE010)に装入し、回転数500rpmで1時間大気下乾式粉砕
した。得られたスギの粉砕試料を110℃で3時間減圧乾燥してそれぞれ供試材とした。
上記で得られたスギの供試材10.0gと有機溶媒としてアントラセン60.0gを混合
し、内容積200mlの電磁誘導撹拌式オートクレーブに密閉して内部を窒素ガスで置換
した。窒素ガスを0.1MPaまで充填して初圧を設定した後、内容物を外部電気炉(鈴
木理化学製作所製)で300℃まで加熱して液化反応を行った。昇温から300℃に達す
るまで内容物に対して水平攪拌を行い、300℃に到達後直ちに室温まで空冷した。反応
後、生成ガス(Gas)はテドラーバッグに全量捕集し、ガスクロマトグラフィー(島津
製作所製 GC−9A)にて組成割合が既知の混合標準ガス(日本酸素株式会社製)を用
い絶対検量線法によって定量することで、組成分析を行った。内容物はアセトンに可溶な
フラクション(以下、ASまたはWIAS:液体燃料と略す)とアセトンに不溶なフラク
ション(以下、AIまたはWIAI:残渣と略す)に分別した。なお、水以外の沸点成分
が生成しない場合はこのように分離することができるが、水と同等の沸点成分が生成した
場合には、アセトン抽出の前に、蒸留後同留分を静置することによって油水分離(水抽出
,WIとも示す)を行うこともできる。供試材あたりの各生成物収率を算出して、さらに
、AS、AIの元素分析をJIS−M−8812に準拠した灰分率の測定及びJIS−M
−8813に準拠した炭素、水素、窒素含有率の測定によって行い、反応前後の元素組成
差から水収率(H2O)を算出した。なお、本発明における水収率とは、供試材の水素及
び酸素重量と、各生成物の水素及び酸素重量の合計との差分を水と仮定して算出したもの
である。結果を実施例2、比較例1、比較例2ともに表1に示す。
Production of liquid fuel derived from woody biomass 200 g of iron balls having a diameter of 6 mm and about 10 kg of iron balls were charged as a grinding medium into a tower mill (NE010 manufactured by Nihon Eirich Co., Ltd.), and dry pulverized in the atmosphere at 500 rpm for 1 hour. The obtained ground samples of cedar were dried under reduced pressure at 110 ° C. for 3 hours to obtain test materials.
10.0 g of the cedar specimen obtained above and 60.0 g of anthracene as an organic solvent were mixed, sealed in an electromagnetic induction stirring autoclave having an internal volume of 200 ml, and the inside was replaced with nitrogen gas. After the nitrogen gas was filled up to 0.1 MPa and the initial pressure was set, the contents were heated to 300 ° C. in an external electric furnace (manufactured by Suzuki Rikagaku Co., Ltd.) to perform a liquefaction reaction. The contents were stirred horizontally until the temperature reached 300 ° C from the temperature increase, and immediately after reaching 300 ° C, the contents were air-cooled to room temperature. After the reaction, the total amount of the produced gas (Gas) is collected in a tedlar bag, and an absolute calibration curve method using a mixed standard gas (manufactured by Nippon Oxygen Co., Ltd.) whose composition ratio is known by gas chromatography (GC-9A, manufactured by Shimadzu Corporation). The composition analysis was performed by quantifying by. The contents were fractionated into a fraction soluble in acetone (hereinafter referred to as AS or WIAS: liquid fuel) and a fraction insoluble in acetone (hereinafter referred to as AI or WIAI: abbreviated as residue). In addition, when boiling components other than water are not generated, they can be separated in this way, but when a boiling component equivalent to water is generated, the same fraction after distillation is allowed to stand before extraction with acetone. Therefore, oil / water separation (water extraction, also indicated as WI) can be performed. The yield of each product per test material was calculated, and further, the elemental analysis of AS and AI was performed by measuring the ash content based on JIS-M-8812 and JIS-M.
It was carried out by measuring carbon, hydrogen, and nitrogen content based on -8813, and the water yield (H 2 O) was calculated from the difference in elemental composition before and after the reaction. The water yield in the present invention is calculated by assuming that the difference between the hydrogen and oxygen weight of the test material and the sum of the hydrogen and oxygen weight of each product is water. The results are shown in Table 1 for both Example 2, Comparative Example 1, and Comparative Example 2.
実施例1で得られたスギの供試材10.0gと有機溶媒としてアントラセン60.0g
を混合し、内容積200mlの電磁誘導撹拌式オートクレーブに密閉して内部を窒素ガス
で置換した。窒素ガスを3.0MPaまで充填し、以降は実施例1と同様に液化反応及び
組成分析を行った。
10.0 g of the cedar specimen obtained in Example 1 and 60.0 g of anthracene as the organic solvent
Were mixed and sealed in an electromagnetic induction stirring autoclave with an internal volume of 200 ml, and the inside was replaced with nitrogen gas. Nitrogen gas was filled up to 3.0 MPa, and thereafter the liquefaction reaction and composition analysis were performed in the same manner as in Example 1.
実施例1で得られたスギの供試材10.0gと溶媒として有機溶媒のアントラセンを用
いる代わりに純水60.0gを用い、触媒として水酸化ナトリウムを5wt%添加して混
合した。混合物は、内容積200mlの電磁誘導撹拌式オートクレーブに密閉して内部を
窒素ガスで置換した。窒素ガスを0.1MPaまで充填し、以降は実施例1と同様に液化
反応及び組成分析を行った。
Instead of using 10.0 g of the cedar sample material obtained in Example 1 and the organic solvent anthracene as a solvent, pure water 60.0 g was used, and 5 wt% of sodium hydroxide was added as a catalyst and mixed. The mixture was sealed in an electromagnetic induction stirring autoclave with an internal volume of 200 ml and the inside was replaced with nitrogen gas. Nitrogen gas was filled up to 0.1 MPa, and thereafter the liquefaction reaction and composition analysis were performed in the same manner as in Example 1.
実施例1で得られたスギの供試材10.0gと溶媒として有機溶媒のアントラセンを用
いる代わりに純水60.0gを用い、触媒として水酸化ナトリウムを5wt%添加して混
合した。混合物は、内容積200mlの電磁誘導撹拌式オートクレーブに密閉して内部を
窒素ガスで置換した。窒素ガスを3.0MPaまで充填し、以降は実施例1と同様に液化
反応及び組成分析を行った。
Instead of using 10.0 g of the cedar sample material obtained in Example 1 and the organic solvent anthracene as a solvent, pure water 60.0 g was used, and 5 wt% of sodium hydroxide was added as a catalyst and mixed. The mixture was sealed in an electromagnetic induction stirring autoclave with an internal volume of 200 ml and the inside was replaced with nitrogen gas. Nitrogen gas was filled up to 3.0 MPa, and thereafter the liquefaction reaction and composition analysis were performed in the same manner as in Example 1.
結果
実施例1、2及び比較例1、2におけるスギの溶媒種と初圧による液体燃料収率を図1
に示した。図1より、実施例1、2のように有機溶媒を用いた場合、反応最大圧力が0.
9MPa、約6.0MPaと低いにも関わらず液体燃料の収率が高いことが示された。有
機溶媒を用いた場合、初圧が0.1MPaの場合は3.0MPaの場合と比較してAI収
率が上昇してGas、H2O 収率が低下するが、AS収率は大きく変化しないことが確
認された。従って、本発明の有機溶媒を用いた場合では、初圧が0.1MPaという低圧
でも十分に液体燃料を得ることができた。一方で比較例1、2において、純粋を溶媒に用
いた場合では、有機溶媒に用いた場合と比較して反応最大圧力は9.0、13.1MPa
と高いにもかかわらず、ASの収率が20%以上低かった。
Results Figure 1 shows the liquid fuel yield according to cedar solvent species and initial pressure in Examples 1 and 2 and Comparative Examples 1 and 2.
It was shown to. As shown in FIG. 1, when an organic solvent was used as in Examples 1 and 2, the maximum reaction pressure was 0.
It was shown that the yield of liquid fuel was high despite being as low as 9 MPa and about 6.0 MPa. When an organic solvent is used, when the initial pressure is 0.1 MPa, the AI yield increases and the Gas and H 2 O yields decrease compared to the case of 3.0 MPa, but the AS yield changes greatly. It was confirmed not to. Therefore, when the organic solvent of the present invention was used, a liquid fuel could be sufficiently obtained even at a low initial pressure of 0.1 MPa. On the other hand, in Comparative Examples 1 and 2, when pure was used as the solvent, the maximum reaction pressure was 9.0 and 13.1 MPa as compared with the case where it was used as the organic solvent.
Despite being high, the yield of AS was 20% or more low.
実施例1で得られたスギの供試材10.0gと有機溶媒としてアントラセン60.0g
を混合し、内容積200mlの電磁誘導撹拌式オートクレーブに密閉して内部を窒素ガス
で置換した。窒素ガスを0.1MPaまで充填して初圧を設定した後、内容物を外部電気
炉(鈴木理化学製作所製)で250℃まで加熱して液化反応を行った。昇温から250℃
に達するまで内容物に対して水平攪拌を行い、250℃に到達後直ちに室温まで空冷した
。反応後、実施例1と同様に分離工程及び組成分析を行った。結果を実施例4〜6ととも
に表2に示す。
10.0 g of the cedar specimen obtained in Example 1 and 60.0 g of anthracene as the organic solvent
Were mixed and sealed in an electromagnetic induction stirring autoclave with an internal volume of 200 ml, and the inside was replaced with nitrogen gas. After filling the nitrogen gas to 0.1 MPa and setting the initial pressure, the contents were heated to 250 ° C. in an external electric furnace (manufactured by Suzuki Riken Corporation) to perform a liquefaction reaction. 250 ℃ from the temperature rise
The contents were stirred horizontally until the temperature reached 250 ° C., and immediately after reaching 250 ° C., the contents were air-cooled to room temperature. After the reaction, the separation step and the composition analysis were performed in the same manner as in Example 1. The results are shown in Table 2 together with Examples 4-6.
実施例1で得られたスギの供試材10.0gと有機溶媒としてアントラセン60.0g
を混合し、内容積200mlの電磁誘導撹拌式オートクレーブに密閉して内部を窒素ガス
で置換した。窒素ガスを0.1MPaまで充填して初圧を設定した後、内容物を外部電気
炉(鈴木理化学製作所製)で300℃まで加熱して液化反応を行った。昇温から300℃
に達するまで内容物に対して水平攪拌を行い、300℃に到達後直ちに室温まで空冷した
。反応後、実施例1と同様に分離工程及び組成分析を行った。
10.0 g of the cedar specimen obtained in Example 1 and 60.0 g of anthracene as the organic solvent
Were mixed and sealed in an electromagnetic induction stirring autoclave with an internal volume of 200 ml, and the inside was replaced with nitrogen gas. After the nitrogen gas was filled up to 0.1 MPa and the initial pressure was set, the contents were heated to 300 ° C. in an external electric furnace (manufactured by Suzuki Rikagaku Co., Ltd.) to perform a liquefaction reaction. 300 ℃ from the temperature rise
The contents were stirred horizontally until the temperature reached 300 ° C., and immediately after reaching 300 ° C., the contents were air-cooled to room temperature. After the reaction, the separation step and the composition analysis were performed in the same manner as in Example 1.
実施例1で得られたスギの供試材10.0gと有機溶媒としてアントラセン60.0g
を混合し、内容積200mlの電磁誘導撹拌式オートクレーブに密閉して内部を窒素ガス
で置換した。窒素ガスを0.1MPaまで充填し、初圧を設定した後、内容物を外部電気
炉(鈴木理化学製作所製)で350℃まで加熱して液化反応を行った。昇温から350℃
に達するまで内容物に対して水平攪拌を行い、350℃に到達後直ちに室温まで空冷した
。反応後、実施例1と同様に分離工程及び組成分析を行った。
10.0 g of the cedar specimen obtained in Example 1 and 60.0 g of anthracene as the organic solvent
Were mixed and sealed in an electromagnetic induction stirring autoclave with an internal volume of 200 ml, and the inside was replaced with nitrogen gas. After filling with nitrogen gas to 0.1 MPa and setting the initial pressure, the contents were heated to 350 ° C. in an external electric furnace (manufactured by Suzuki Rikagaku Co., Ltd.) to perform a liquefaction reaction. 350 ℃ from the temperature rise
The contents were stirred horizontally until the temperature reached 350 ° C., and immediately after reaching 350 ° C., the contents were air-cooled to room temperature. After the reaction, the separation step and the composition analysis were performed in the same manner as in Example 1.
実施例1で得られたスギの供試材10.0gと有機溶媒としてアントラセン60.0g
を混合し、内容積200mlの電磁誘導撹拌式オートクレーブに密閉して内部を窒素ガス
で置換した。窒素ガスを0.1MPaまで充填して初圧を設定した後、内容物を外部電気
炉(鈴木理化学製作所製)で400℃まで加熱して液化反応を行った。昇温から400℃
に達するまで内容物に対して水平攪拌を行い、400℃に到達後直ちに室温まで空冷した
。反応後、実施例1と同様に分離工程及び組成分析を行った。
10.0 g of the cedar specimen obtained in Example 1 and 60.0 g of anthracene as the organic solvent
Were mixed and sealed in an electromagnetic induction stirring autoclave with an internal volume of 200 ml, and the inside was replaced with nitrogen gas. After filling the nitrogen gas to 0.1 MPa and setting the initial pressure, the contents were heated to 400 ° C. in an external electric furnace (manufactured by Suzuki Rikagaku Co., Ltd.) to perform a liquefaction reaction. 400 ℃ from the temperature rise
The contents were stirred horizontally until the temperature reached 400 ° C, and immediately after reaching 400 ° C, the contents were air-cooled to room temperature. After the reaction, the separation step and the composition analysis were performed in the same manner as in Example 1.
結果
実施例5〜6におけるスギの反応温度による液体燃料収率を図2に示した。図2より、
反応温度の上昇に伴って、AI収率が低下してAS、Gas、H2O 収率が上昇するこ
とが確認された。350℃におけるAS収集率は約50wt%と、最大であり、350℃
以上では大きく変化しなかった。
Result The liquid fuel yield by the reaction temperature of the cedar in Examples 5-6 was shown in FIG. From FIG.
It was confirmed that the AI yield decreased and the AS, Gas, and H 2 O yields increased as the reaction temperature increased. The AS collection rate at 350 ° C. is the maximum, about 50 wt%.
The above did not change much.
木質バイオマス由来液体燃料の製造装置
木質バイオマス由来の液体燃料の製造装置を製造した。この液体燃料の製造装置は以下
(A)〜(E)または(B)〜(E)のプロセスを含む。該プロセスを含む木質バイオマ
ス由来の液体燃料の製造装置のフローを図3に示した。
(A)木質バイオマスを平均粒径が300μm以下となるまで破砕処理して、該木質バイ
オマス由来の供試材を得る破砕工程を行う破砕槽と、
(B)該供試材に有機溶媒を混合する混合槽と、
(C)該混合物を熱分解が生じる温度(250〜400℃)で加熱処理する液化工程を行
う反応槽と、
(D)加熱により生じた上記供試材の分解物を分離して、木質バイオマス由来の液体燃料
を得る分離工程を行う分離槽と、
(E)木質バイオマス由来の液体燃料の一部を自家溶媒として、上記第2領域に循環する
循環経路とを具備する。
Wood biomass-derived liquid fuel production apparatus A wood biomass-derived liquid fuel production apparatus was produced. This liquid fuel production apparatus includes the following processes (A) to (E) or (B) to (E). The flow of the manufacturing apparatus of the liquid fuel derived from woody biomass containing this process was shown in FIG.
(A) A crushing tank that crushes wood biomass until the average particle size is 300 μm or less, and performs a crushing step to obtain a test material derived from the wood biomass,
(B) a mixing tank for mixing an organic solvent with the test material;
(C) a reaction vessel that performs a liquefaction step of heat-treating the mixture at a temperature at which thermal decomposition occurs (250 to 400 ° C.);
(D) A separation tank for separating a decomposition product of the test material generated by heating and performing a separation step of obtaining a woody biomass-derived liquid fuel;
(E) A circulation path that circulates in the second region using a part of the liquid fuel derived from woody biomass as an in-house solvent.
[参考例]
参考例として、木質バイオマスからなる供試材を古紙製紙廃水と混合し、熱分解及び加水分解が行われる温度及び圧力で液化処理する工程と、この工程により生じた該供試材の分解物を分離して、木質バイオマス由来の液体燃料を得る分離工程とを含むことを特徴とする木質バイオマス由来の液体燃料の製造方法を示した。この場合の比較例として古紙製紙廃水の代わりに純水又は水酸化ナトリウム水溶液を溶媒として用いた。
実施例1と同様の方法で得たユーカリの供試材5.0gと溶媒として古紙製紙廃水(水分99.2 wt%,灰分0.4wt%,有機物0.4wt%,pH9.5)、純水又は水酸化ナトリウム水溶液(pH9.5)のいずれか30.0gを混合し、内容積200mlの電磁誘導撹拌式オートクレーブに密閉して内部を窒素ガスで置換した。窒素ガスを2.0MPaまで充填して初圧を設定した後、内容物を外部電気炉(鈴木理化学製作所製)で150〜350℃まで加熱して液化反応を行った。昇温から150〜350℃に達するまで内容物に対して水平攪拌を行い、150〜350℃に到達後直ちに室温まで空冷した。反応後、実施例1と同様に分離工程及び組成分析を行った。
[Reference example]
As a reference example, a sample material composed of woody biomass is mixed with waste paper wastewater, and a liquefaction treatment is performed at a temperature and pressure at which thermal decomposition and hydrolysis are performed, and a decomposition product of the sample material generated by this step is The manufacturing method of the liquid fuel derived from woody biomass characterized by including the isolation | separation process of isolate | separating and obtaining the liquid fuel derived from woody biomass was shown. As a comparative example in this case, pure water or a sodium hydroxide aqueous solution was used as a solvent instead of waste paper waste water.
Eucalyptus sample material obtained in the same manner as in Example 1 and waste paper wastewater (water content 99.2 wt%, ash content 0.4 wt%, organic matter 0.4 wt%, pH 9.5), pure water or hydroxylated as a solvent Any 30.0 g of an aqueous sodium solution (pH 9.5) was mixed, sealed in an electromagnetic induction stirring autoclave having an internal volume of 200 ml, and the inside was replaced with nitrogen gas. After filling the nitrogen gas up to 2.0 MPa and setting the initial pressure, the contents were heated to 150 to 350 ° C. in an external electric furnace (manufactured by Suzuki Rikagaku Co., Ltd.) to carry out a liquefaction reaction. The contents were stirred horizontally until the temperature reached 150 to 350 ° C. After the temperature reached 150 to 350 ° C., the contents were immediately cooled to room temperature. After the reaction, the separation step and the composition analysis were performed in the same manner as in Example 1.
反応温度を300℃とした場合の、ユーカリの溶媒種による液体燃料収率を図4に示した。図4より、古紙製紙廃水を用いた場合は、純水を用いた場合と比べてAI収率が低下し、AS収率が上昇することが確認された。さらに、水酸化ナトリウム水溶液を用いた場合と同程度又はそれ以上にAI収率が高いことが確認された。 The liquid fuel yield by the Eucalyptus solvent species when the reaction temperature is 300 ° C. is shown in FIG. From FIG. 4, it was confirmed that when the waste paper waste water was used, the AI yield decreased and the AS yield increased compared to the case where pure water was used. Furthermore, it was confirmed that the AI yield was as high as or higher than that when using an aqueous sodium hydroxide solution.
生成物のFT−IRスペクトルにおいて、純水溶媒の反応では、温度の上昇とともに、WS中のカルボン酸の減少とWIAI中のエステル結合の増加が確認されたことから、−COOH基と−OH基が重縮合を起こしたため、残渣が増加したものと考えられた。
一方、古紙製紙廃水と水酸化ナトリウム水溶液溶媒の反応ではWS中にカルボン酸が確認されたことから、アルカリ成分によりカルボン酸が中和されることによって重縮合が抑制されたために、残渣の生成が抑制されたものと考えられた。
従って、本発明の古紙製紙廃水に含まれるアルカリ成分は、水酸化ナトリウム同様にアルカリ触媒としての効果があることが示唆された。
In the FT-IR spectrum of the product, in the reaction with a pure water solvent, as the temperature increased, a decrease in carboxylic acid in WS and an increase in ester bond in WIAI were confirmed. It was thought that the residue increased because of polycondensation.
On the other hand, since the carboxylic acid was confirmed in WS in the reaction of waste paper waste water and sodium hydroxide aqueous solution, the polycondensation was suppressed by neutralizing the carboxylic acid with the alkali component, so that the generation of the residue It was thought to have been suppressed.
Therefore, it was suggested that the alkali component contained in the waste paper wastewater of the present invention has an effect as an alkali catalyst like sodium hydroxide.
本発明の木質バイオマス由来の液体燃料の製造方法及び製造装置は、低圧で温和な反応条件で液体燃料を得ることができる。さらに得られた液体燃料の一部を自家溶媒として循環使用することで、効率的に液化を継続できる、小規模なエネルギー自給型工場等の構築に利用できる。 The method and apparatus for producing liquid fuel derived from woody biomass of the present invention can obtain liquid fuel under low pressure and mild reaction conditions. Furthermore, by recycling a part of the obtained liquid fuel as an in-house solvent, it can be used for the construction of a small-scale energy self-contained factory that can efficiently continue liquefaction.
Claims (11)
力で液化処理する工程と、
(B)(A)の工程により生じた該供試材の分解物を分離して、木質バイオマス由来の液
体燃料を得る分離工程と
を含むことを特徴とする木質バイオマス由来の液体燃料の製造方法。 (A) mixing a sample material made of woody biomass with an organic solvent, and liquefying at a temperature and pressure at which thermal decomposition is performed;
(B) A method for producing a woody biomass-derived liquid fuel comprising separating a decomposition product of the test material produced in the step (A) to obtain a woody biomass-derived liquid fuel. .
バイオマスを継続して液化することを特徴とする請求項1に記載の木質バイオマス由来の
液体燃料の製造方法。 The method for producing a liquid fuel derived from woody biomass according to claim 1, wherein the woody biomass is continuously liquefied by circulating and using a part of the liquid fuel derived from the woody biomass as an in-house solvent.
下であることを特徴とする請求項1または2に記載の木質バイオマス由来の液体燃料の製
造方法。 In the said liquefaction process (A), the organic solvent to be used is 1 weight times or more and 10 weight times or less of this test material, The manufacturing method of the liquid fuel derived from the woody biomass of Claim 1 or 2 characterized by the above-mentioned.
ることを特徴とする請求項1〜3のいずれかに記載の木質バイオマス由来の液体燃料の製
造方法。 In the said liquefaction process (A), the organic solvent to be used is a heavy oil fraction with a normal-pressure boiling point of 300 degreeC or more, The manufacturing method of the liquid fuel derived from the woody biomass in any one of Claims 1-3 characterized by the above-mentioned.
載の木質バイオマス由来の液体燃料の製造方法。 The method for producing a liquid fuel derived from woody biomass according to any one of claims 1 to 4, wherein the woody biomass used for the test material is woody industrial waste.
オマス由来の液体燃料の製造方法。 The method for producing a liquid fuel derived from woody biomass according to any one of claims 1 to 5, wherein the water content of the test material is 10% by weight or less.
かに記載の木質バイオマス由来の液体燃料の製造方法。 The manufacturing method of the liquid fuel derived from the woody biomass in any one of Claims 1-6 which further includes the process of crushing the woody biomass used for a test material.
する請求項1〜7のいずれかに記載の木質バイオマス由来の液体燃料の製造方法。 In the said liquefaction process (A), heating temperature is adjusted to 250 to 400 degreeC, The manufacturing method of the liquid fuel derived from the woody biomass in any one of Claims 1-7 characterized by the above-mentioned.
する請求項1〜8のいずれかに記載の木質バイオマス由来の液体燃料の製造方法。 In the said liquefaction process (A), a pressure is adjusted to atmospheric pressure or more and less than 15 atmospheres, The manufacturing method of the liquid fuel derived from the woody biomass in any one of Claims 1-8 characterized by the above-mentioned.
(B)該混合物を熱分解が生じる温度で加熱処理する液化工程を行う反応槽と、
(C)加熱により生じた上記供試材の分解物を分離して、木質バイオマス由来の液体燃料
を得る分離工程を行う分離槽と、
(D)木質バイオマス由来の液体燃料の一部を自家溶媒として、上記混合層に循環する循
環経路と
を具備する木質バイオマス由来の液体燃料の製造装置。 (A) a mixing tank for mixing an organic solvent with the test material;
(B) a reaction vessel that performs a liquefaction step of heat-treating the mixture at a temperature at which thermal decomposition occurs;
(C) A separation tank for separating a decomposition product of the test material generated by heating and performing a separation step of obtaining a liquid fuel derived from woody biomass,
(D) An apparatus for producing a woody biomass-derived liquid fuel comprising a circulation path that circulates in the mixed layer using a part of the woody biomass-derived liquid fuel as a self-solvent.
破砕槽を具備する請求項10に記載の木質バイオマス由来の液体燃料の製造装置。
The apparatus for producing a liquid fuel derived from woody biomass according to claim 10, further comprising a crushing tank that crushes the woody biomass and performs a crushing step for obtaining a test material derived from the woody biomass.
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