JP4364684B2 - Method for producing gasified fuel - Google Patents
Method for producing gasified fuel Download PDFInfo
- Publication number
- JP4364684B2 JP4364684B2 JP2004076512A JP2004076512A JP4364684B2 JP 4364684 B2 JP4364684 B2 JP 4364684B2 JP 2004076512 A JP2004076512 A JP 2004076512A JP 2004076512 A JP2004076512 A JP 2004076512A JP 4364684 B2 JP4364684 B2 JP 4364684B2
- Authority
- JP
- Japan
- Prior art keywords
- biomass
- medium oil
- raw material
- fuel
- catalyst
- 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.)
- Expired - Lifetime
Links
- 239000000446 fuel Substances 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000002028 Biomass Substances 0.000 claims description 88
- 238000000034 method Methods 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 43
- 239000002994 raw material Substances 0.000 claims description 38
- 238000002309 gasification Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 230000018044 dehydration Effects 0.000 claims description 28
- 238000006297 dehydration reaction Methods 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 20
- 150000007524 organic acids Chemical class 0.000 claims description 16
- 238000002407 reforming Methods 0.000 claims description 15
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 235000005985 organic acids Nutrition 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- -1 alkaline earth metal carbonates Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 230000003796 beauty Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000003921 oil Substances 0.000 description 35
- 208000005156 Dehydration Diseases 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 17
- 238000010298 pulverizing process Methods 0.000 description 14
- 239000002351 wastewater Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 8
- 239000000920 calcium hydroxide Substances 0.000 description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000010903 husk Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 244000144972 livestock Species 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 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
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002023 wood Substances 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
- Y02E50/10—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
- Coke Industry (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Processing Of Solid Wastes (AREA)
Description
本発明は、バイオマスを原料とするガス化燃料の製造方法に関するものである。 The present invention relates to a method for producing gasified fuel using biomass as a raw material.
「バイオマス」という語は、本来、生物学分野において「生物量」等と訳されていた。しかし、現在では生物学分野の垣根を越えて、生物起源の物質からなる食料，資材，燃料など広い概念を意味する語として用いられている。 The term “biomass” was originally translated as “biomass” in the field of biology. However, it is now used as a term that means a wide range of concepts such as foods, materials, and fuels that are made of biological materials.
このバイオマスは、米糠や木炭などの様に利用方法が確立されているものもあるが、産業活動に伴う廃棄物として、その処理方法が検討されているものもある。例えば、農業系のバイオマス廃棄物としてはヤシガラや籾殻、林業系では木材チップダストや剪定枝、畜産系からは家畜の排泄物、水産系からは水産加工に伴う腸や骨、また、所謂生ゴミや下水汚泥等もバイオマスとされており、これらはいまだに処理方法が検討されている段階にある。 Some of these biomasses have been established for use, such as rice bran and charcoal, but some are being considered for disposal as waste associated with industrial activities. For example, coconut husks and rice husks for agricultural biomass, wood chip dust and pruned branches for forestry, livestock excrement from livestock, intestines and bones from marine processing, and so-called garbage And sewage sludge are also considered as biomass, and these are still in the process of being examined.
ところで、近年、バイオマスを触媒存在下で高温処理することによって、メタンや水素などを含む燃料ガスへ転換する技術が開発されている。例えば特許文献１には、バイオマスのガス化触媒であって、担体としてのセリウム酸化物の表面上にロジウム等の触媒金属を担持させた触媒が開示されている。また、特許文献２には、Ｒｈ／ＣｅＯ２／ＳｉＯ２等と表される触媒を用いて、バイオマスをガス化する方法が記載されている。
By the way, in recent years, a technology for converting biomass into fuel gas containing methane, hydrogen, etc. by high-temperature treatment in the presence of a catalyst has been developed. For example,
しかし、バイオマスは触媒に比して非常に大きく、そのままでは触媒に接触できないので、熱処理に際しては先ずバイオマスの熱分解が起こって低分子の分解化合物が発生し、これが揮発して初めて触媒と接触することができる。従って、バイオマスと触媒が乖離している上記技術では、バイオマスの分解化合物が触媒に接触するまでに、ガス化反応とは逆行するチャー（揮発分以外の炭素と灰分からなる粒子）が生成せざるを得ないという問題があった。この様なチャーの生成は、ガス化を極めて効率的に進行せしめれば抑制することができるが、様々な成分を含むバイオマスを原料とする場合には、効率的なガス化は困難である。 However, since biomass is much larger than the catalyst and cannot be contacted as it is, the thermal decomposition of the biomass occurs first during the heat treatment to generate a low-molecular decomposition compound, which only comes into contact with the catalyst after volatilization. be able to. Therefore, in the above technology where the biomass and the catalyst are separated, char (particles composed of carbon and ash other than the volatile matter) that is opposite to the gasification reaction is not generated until the biomass decomposition compound contacts the catalyst. There was a problem of not getting. Generation of such char can be suppressed if gasification proceeds very efficiently, but efficient gasification is difficult when biomass containing various components is used as a raw material.
また、これら特許文献に記載の技術では、バイオマス中多量に含まれる水による効率低下については、全く認識されていない。実際、これら特許文献の実施例で原料として用いられているのは市販のセルロース粒子であり、水を含むものではない。従って、これら技術を天然バイオマスのガス化へ応用した場合には、当然にチャーやタールが発生すると考えられる。 Moreover, in the technique described in these patent documents, the efficiency fall by the water contained in biomass in large quantities is not recognized at all. Actually, it is a commercially available cellulose particle used as a raw material in the examples of these patent documents, and does not contain water. Therefore, when these technologies are applied to natural biomass gasification, it is natural that char and tar are generated.
そこで、これら技術を実施する前に、バイオマスを乾燥することも考えられる。多量に水を含むバイオマスを効率的に乾燥する方法としては、減圧〜常圧条件下、バイオマスを油中で加熱することによって、脱水する技術が知られている（特許文献３）。しかし、斯かる技術では加熱に伴ってバイオマスの一部で熱分解が起き、蟻酸，酢酸，プロピオン酸，乳酸といった低分子量の有機酸が発生する。これら有機酸は、水蒸気と共に揮発して排水に混入し、ＢＯＤ（生物化学的酸素要求量）やＣＯＤ（化学的酸素要求量）を高めるため、排水処理の必要が生じる。更に、石炭を加熱することによって、細孔内に存在するカルボキシル基等の官能基を除去する技術もある（特許文献４）。斯かる処理をすれば、低分子化合物が発生してやはり排水のＣＯＤ等を高めるため、排水中の有機酸処理は重要である。
上述した様に、従来におけるバイオマスのガス化技術には、ガス化効率が低くチャーが生成したり、タールなどの有害化学物質が発生するという問題があった。また、斯かる問題を解決すべく事前にバイオマスを乾燥するとすれば、有機酸が発生し排水が汚染されてしまう。 As described above, the conventional biomass gasification technology has a problem that the gasification efficiency is low and char is generated, and harmful chemical substances such as tar are generated. Further, if the biomass is dried in advance to solve such a problem, an organic acid is generated and the waste water is contaminated.
そこで本発明が解決すべき課題は、バイオマスを原料とし、表面にガス化触媒が付着していることから効率的なガス化処理が可能であるガス化燃料を製造する方法であって、排水中への有機酸の混入を抑制することができるものを提供することにある。 Therefore, the problem to be solved by the present invention is a method for producing gasified fuel that can be efficiently gasified from biomass as a raw material and having a gasification catalyst attached to the surface thereof, It is in providing the thing which can suppress mixing of the organic acid into.
本発明者らは、上記課題を解決すべく、その有効利用技術が切望されているバイオマスを原料とするガス化燃料について鋭意研究を行なったところ、特定の触媒原料を添加して脱水処理を行なえば、触媒成分が表面に担持されたガス化燃料を製造することができる上に、排水中の有機酸も顕著に低減できることを見出して本発明を完成した。 In order to solve the above-mentioned problems, the present inventors have conducted intensive research on gasified fuels that use biomass as a raw material for which effective utilization technology is desired. As a result, dehydration treatment can be performed by adding a specific catalyst raw material. For example, the present invention was completed by discovering that gasified fuel having a catalyst component supported on the surface can be produced and that organic acids in the wastewater can be significantly reduced.
即ち、本発明に係るガス化燃料の製造方法は、アルカリ金属およびアルカリ土類金属の水酸化物，アルカリ金属およびアルカリ土類金属の炭酸塩，並びにアルカリ金属およびアルカリ土類金属の炭酸水素塩からなる群より選択される１種または２種以上（以下、「触媒原料」という）と、バイオマスを粉砕する工程（以下、「粉砕工程」という）、および当該粉砕物を、水の蒸気圧未満の圧力下、媒体油中で加熱し、バイオマス中に含まれる水分を除去する工程（以下、「脱水工程」という）を含むことを特徴とする。 That is, the method for producing a gasified fuel according to the present invention comprises alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal carbonates, and alkali metal and alkaline earth metal hydrogen carbonates. One or more selected from the group consisting of the following (hereinafter referred to as “catalyst raw material”), a step of pulverizing biomass (hereinafter referred to as “grinding step”), and the pulverized product are less than the vapor pressure of water It is characterized by including a step of removing water contained in biomass by heating in medium oil under pressure (hereinafter referred to as “dehydration step”).
上記粉砕工程後においては、上記脱水工程と実施順位を問わず、水または媒体油の蒸気圧のうち高い方の圧力以上に加圧して加熱する工程（以下、「改質工程」という）を行なうことが好ましい。かさ高く処理が困難であるバイオマスの一部を分解することによって容積を低減し、処理を容易にできるからである。 After the pulverization step, regardless of the dehydration step and the order of execution, a step of heating by pressurizing to a higher pressure than the vapor pressure of water or medium oil (hereinafter referred to as “reforming step”) is performed. It is preferable. This is because by disassembling a part of the biomass that is bulky and difficult to treat, the volume can be reduced and the treatment can be facilitated.
上記粉砕工程は、媒体油中で行なうことが好ましい。粉砕後に油中に混合するという工程を必要とせず、パイプラインを利用してそのまま次工程へ移行することができることから、バッチ処理ではなく連続的処理が可能となり、プロセス全体の効率化が可能となるからである。 The pulverization step is preferably performed in medium oil. Since the process of mixing in oil after pulverization is not necessary, it is possible to proceed directly to the next process using a pipeline, enabling continuous processing instead of batch processing, and improving the efficiency of the entire process. Because it becomes.
上記脱水工程および改質工程においては、上記媒体油の質量比率を、触媒原料とバイオマスの合計１００に対して２０〜１２０とすることが好ましい。媒体油量を適切なものにすることによって、コストの低減や効率的な脱水処理が可能になると共に、これらの混合物に流動性を持たせることによって、連続的に処理できるからである。 In the dehydration step and the reforming step, the mass ratio of the medium oil is preferably 20 to 120 with respect to 100 in total of the catalyst raw material and the biomass. This is because by making the amount of medium oil appropriate, cost reduction and efficient dehydration processing become possible, and by making these mixtures fluid, continuous processing is possible.
上記脱水工程および改質工程においては、発生する有機酸を中和するに十分な触媒原料を使用する。排水中の有機酸を極力低減できるからである。 In the dehydration step and the reforming step, a catalyst raw material sufficient to neutralize the generated organic acid is used. This is because the organic acid in the waste water can be reduced as much as possible.
上記製造方法においては、更に、不活性ガス中で炭化する工程を行なうことが好ましい。バイオマス成分が炭化されたガス化燃料は、より効率的にガス化できるからである。 In the said manufacturing method, it is preferable to perform the process carbonized in an inert gas further. This is because the gasified fuel obtained by carbonizing the biomass component can be more efficiently gasified.
本発明に係るガス化燃料の製造方法は、含水量が多く再利用が難しいバイオマスを原料とするものであって、特に、排水中への有機物の混入を顕著に低減しつつバイオマスを脱水（乾燥）することができる。また、本発明方法により製造されたガス化燃料は、バイオマスの表面にガス化触媒が担持されている、つまりバイオマスとガス化触媒が近接していることから、従来のガス化燃料に比して極めて効率的にガス化を達成することができる。従って、本発明方法は、再利用方法が切望されているバイオマスをガス化燃料にできるものであって、且つ環境への影響を低減できるものとして、産業上極めて有用である。 The method for producing gasified fuel according to the present invention uses biomass that has a high water content and is difficult to reuse, and in particular, dehydrates (drys) the biomass while significantly reducing the contamination of organic matter into the wastewater. )can do. In addition, the gasification fuel produced by the method of the present invention has a gasification catalyst supported on the surface of biomass, that is, the biomass and the gasification catalyst are close to each other, so that it is compared with conventional gasification fuel. Gasification can be achieved very efficiently. Therefore, the method of the present invention is extremely useful industrially as it can be used as a gasification fuel for biomass for which a recycling method is desired, and the influence on the environment can be reduced.
本発明に係るガス化燃料の製造方法では、少なくとも、（１）触媒原料とバイオマスを粉砕する工程（粉砕工程）と、（２）当該粉砕物を媒体油中で加熱し、バイオマス中に含まれる水分を除去する工程（脱水工程）を含む。尚、本発明方法の好適な実施形態の模式図を、図１として示す。 In the method for producing gasified fuel according to the present invention, at least (1) a step of pulverizing the catalyst raw material and biomass (pulverization step), and (2) the pulverized product is heated in medium oil and contained in the biomass. It includes a step of removing moisture (dehydration step). In addition, the schematic diagram of suitable embodiment of this invention method is shown as FIG.
以下、本発明方法を、工程ごとに説明する。
（１） 触媒原料とバイオマスを粉砕する工程（粉砕工程）は、バイオマスの効率的な乾燥や、バイオマスに対するガス化触媒の担持量を高めるために行なうものである。
Hereinafter, the method of the present invention will be described step by step.
(1) The step of crushing the catalyst raw material and the biomass (pulverization step) is performed in order to efficiently dry the biomass and increase the amount of the gasification catalyst supported on the biomass.
本発明で使用する「触媒原料」は、バイオマスのガス化触媒作用と共に、脱水工程で発生する有機酸を中和する作用を有するアルカリ金属またはアルカリ土類金属を含む化合物であり、水酸化ナトリウム，水酸化カリウム，水酸化マグネシウム，水酸化カルシウム等の水酸化物；炭酸ナトリウム，炭酸マグネシウム，炭酸カルシウム等の炭酸塩；炭酸水素ナトリウム，炭酸水素カリウム，炭酸水素カルシウム等の炭酸水素塩を例示することができる。本発明では、これらから１種を選択するか、２種以上を選択して混合したものを用いる。 The “catalyst raw material” used in the present invention is a compound containing an alkali metal or an alkaline earth metal having an action of neutralizing an organic acid generated in a dehydration step together with a gasification catalyst action of biomass, Examples of hydroxides such as potassium hydroxide, magnesium hydroxide, and calcium hydroxide; carbonates such as sodium carbonate, magnesium carbonate, and calcium carbonate; and bicarbonates such as sodium bicarbonate, potassium bicarbonate, and calcium bicarbonate Can do. In the present invention, one selected from these or a mixture of two or more selected is used.
触媒原料の添加量は、後述する脱水工程において発生する有機酸を中和するに十分な量とする。具体的には、処理すべきバイオマスのサンプルを用い予備実験を行なって発生する有機酸の量を測定し、その１〜１０倍の化学当量を使用すればよい。 The amount of the catalyst raw material added is sufficient to neutralize the organic acid generated in the dehydration step described later. Specifically, the amount of organic acid generated may be measured by performing a preliminary experiment using a sample of biomass to be treated, and a chemical equivalent of 1 to 10 times that may be used.
本発明で原料として使用する「バイオマス」は、生物に由来するものであってその再利用方法が検討されているものであれば特にその種類は問わないが、例えば、ヤシガラ，サトウキビバガス，麦わら，籾殻等の農業系バイオマス；チップダスト，のこ屑，鉋屑，伐採枝等の林業系バイオマス；コーヒーや紅茶の抽出滓，生ごみ等の廃棄物系バイオマス；家畜の糞；排水の生物的処理に伴う汚泥などを挙げることができる。 "Biomass" used as a raw material in the present invention is not particularly limited as long as it is derived from a living organism and its recycling method is being studied. For example, coconut husk, sugar cane bagasse, straw, Agricultural biomass such as rice husks; Forestry biomass such as chip dust, sawdust, sawdust, and cutting branches; Waste biomass such as coffee and tea extraction straws, garbage; Livestock dung; Biological treatment of wastewater The accompanying sludge can be mentioned.
また、石炭などの化石燃料以外のバイオマスを燃料として利用することには、二酸化炭素排出量を増加しないという利点もある。例えば、石炭を燃焼すると、古代において固定化され本来は大気中へ放出されないはずの炭素が、二酸化炭素として空気中へ放出されることになる。一方、化石燃料以外のバイオマスに含まれる炭素は、少なくとも原料となる植物の生育時に固定化されたものが多いため、一定の期間を考えれば、実質的に空気中の二酸化炭素は増加していない。この点から、植物に由来するバイオマスは、カーボンニュートラルな燃料原料といわれており、地球温暖化を考慮すれば、本発明において積極的に原料として使用することが望ましい。 In addition, the use of biomass other than fossil fuels such as coal as fuel also has the advantage of not increasing carbon dioxide emissions. For example, when coal is burned, carbon that has been fixed in ancient times and should not be released into the atmosphere is released into the air as carbon dioxide. On the other hand, the carbon contained in biomass other than fossil fuels is often fixed at least during the growth of the plant that is the raw material, so that carbon dioxide in the air has not increased substantially given a certain period of time. . From this point, biomass derived from plants is said to be a carbon-neutral fuel raw material, and it is desirable to actively use it as a raw material in the present invention in consideration of global warming.
当該粉砕工程では、触媒原料とバイオマスを混合した後に粉砕してもよいし、触媒原料とバイオマスを別々に粉砕した後に混合してもよい。但し、この粉砕は、媒体油中で行ない、触媒原料のみ、バイオマスのみ、或いは触媒原料とバイオマスからなるスラリーまたはペーストとすることが好ましい。原料を粉砕した上で媒体油中に投じてもよいが、媒体油中で粉砕すれば、スラリー状態でのパイプライン輸送が可能になり、大量的かつ連続的に処理できるからである。斯かる「粉砕」の具体例としては、先ず、ロールクラッシャー等により粗粉砕した後に、流通管型攪拌ミル等を用いて油中粉砕することが挙げられる。 In the pulverization step, the catalyst raw material and biomass may be mixed and then pulverized, or the catalyst raw material and biomass may be separately pulverized and mixed. However, this pulverization is preferably carried out in a medium oil, and is made into a slurry or paste consisting of only the catalyst raw material, only the biomass, or the catalyst raw material and the biomass. The raw material may be pulverized and then thrown into the medium oil. However, if the raw material is pulverized in the medium oil, the pipeline transportation in the slurry state becomes possible, and a large amount can be continuously processed. As a specific example of such “pulverization”, first, coarse pulverization with a roll crusher or the like, followed by pulverization in oil using a flow tube type stirring mill or the like.
粉砕物の平均粒径は、５ｍｍ以下とすることが好ましい。５ｍｍを超えるとパイプラインでの輸送が困難になる場合があるからである。 The average particle size of the pulverized product is preferably 5 mm or less. This is because if it exceeds 5 mm, it may be difficult to transport in the pipeline.
この平均粒径の測定方法としては、当該平均粒径を規定することの意義を喪失しない限り特に制限なく公知方法を採用することができるが、例えば、次の方法を挙げることができる。即ち、粉砕した試料をよく混合し、その一部をサンプリングして媒体油で１０倍に希釈した後、これを口径１０ｃｍ以上の濾紙を用いて粉砕物ができるだけ重ならない様に濾過し、その結果を写真撮影して、粉砕物の長手方向の長さを測定する。この際、測定データは１００個以上とするのが好ましい。得られたデータの内、９５％が５ｍｍ以下の範囲であれば、平均粒径が規定範囲のものとする。一部に過大粒物や過少粒物があったとしても、ごく一部であれば本発明の効果に影響を及ぼさないからである。 As a method for measuring the average particle diameter, a known method can be adopted without particular limitation as long as the significance of defining the average particle diameter is not lost. For example, the following method can be exemplified. That is, after mixing the pulverized sample well, sampling a part of it and diluting it 10 times with medium oil, this was filtered using a filter paper with a caliber of 10 cm or more so that the pulverized material would not overlap as much as possible The length of the pulverized material in the longitudinal direction is measured. At this time, the measurement data is preferably 100 or more. If 95% of the obtained data is in the range of 5 mm or less, the average particle diameter is within the specified range. This is because even if some of the particles are excessively large or insufficiently small, only a small amount thereof does not affect the effects of the present invention.
また、使用する媒体油の質量比率は、原料バイオマスや媒体油の種類等によって異なるが、触媒原料とバイオマスの合計１００に対して２０〜１２０とすることが好ましい。必要以上の媒体油を用いることは、プロセス全体におけるコスト低減の観点から好ましくない一方で、パイプラインを利用した連続的な処理を可能にすべく、混合物の流動性を保つためである。斯かる要件は、後続の脱水工程においても好ましいものである。また、好適な媒体油の質量比率は、触媒原料とバイオマスの合計１００に対して４０以上，５０以上，６０以上であり、１１０以下である。 Moreover, although the mass ratio of the medium oil to be used changes with raw material biomass, the kind of medium oil, etc., it is preferable to set it as 20-120 with respect to 100 total of a catalyst raw material and biomass. The use of more medium oil than necessary is not preferable from the viewpoint of cost reduction in the entire process, while maintaining the fluidity of the mixture to enable continuous processing using a pipeline. Such a requirement is preferable also in the subsequent dehydration step. Moreover, the suitable mass ratio of a medium oil is 40 or more, 50 or more, 60 or more, and 110 or less with respect to 100 in total of a catalyst raw material and biomass.
ここで使用される「媒体油」は特に制限されないが、一般には石油系の軽油，灯油，潤滑油等であり、初留点が１５０℃以上で９５％留出温度が３００℃以下のものを好適に使用する。バイオマスの脱水工程後は、先ず機械的な脱油を行ない、次いで加熱して過剰の油を除去することが好ましいが、この際、コスト低減の観点から、過剰の熱エネルギーを必要としないことが望ましいからである。また、媒体油には、アスファルト等の重質油を添加してもよい。 The “medium oil” used here is not particularly limited, but is generally petroleum-based light oil, kerosene, lubricating oil, etc., having an initial boiling point of 150 ° C. or higher and a 95% distillation temperature of 300 ° C. or lower. Preferably used. After the dehydration process of biomass, it is preferable to first perform mechanical deoiling and then to remove excess oil by heating, but at this time, from the viewpoint of cost reduction, excessive heat energy may not be required. This is desirable. Further, heavy oil such as asphalt may be added to the medium oil.
（２） 上記粉砕工程以降には、得られた粉砕物を、水の蒸気圧未満の圧力下、媒体油中で加熱することによって、バイオマス中に含まれる水分を除去する工程を行なう（脱水工程）。バイオマスに含まれる水分を除去してガス化効率を高め、また、ガス化触媒であるアルカリ金属やアルカリ土類金属をバイオマス表面上に担持するためである。 (2) After the pulverization step, the obtained pulverized product is heated in medium oil under a pressure lower than the vapor pressure of water to perform a step of removing water contained in the biomass (dehydration step). ). This is because the moisture contained in the biomass is removed to increase the gasification efficiency and the alkali metal or alkaline earth metal that is the gasification catalyst is supported on the biomass surface.
当該工程を水の蒸気圧未満の圧力下で行なうのは、バイオマスに含まれる水分を除去するためであり、具体的には、減圧下，常圧下，或いは実施温度に依存する飽和水蒸気圧未満の加圧下とする。減圧下（好適には、０．０５ＭＰａ以上で常圧未満）であれば効率的な乾燥が可能になり、常圧であれば、圧力調節のための設備が必要でないことからコストを低減でき、また、飽和水蒸気圧未満の加圧下であれば、生じた水蒸気を加圧することにより発生する蒸発潜熱を再利用する際におけるコンプレッサーの負荷を小さくできることから、実際の運転上有利だからである。一方、確かに圧力が低いほど乾燥効率は高まるが、過剰に圧力を低めれば媒体油が蒸発することになるばかりでなく、設備費も高くなる。 The reason why the process is carried out under a pressure lower than the vapor pressure of water is to remove moisture contained in the biomass, specifically, under reduced pressure, under normal pressure, or less than the saturated water vapor pressure depending on the operating temperature. Under pressure. Efficient drying is possible under reduced pressure (preferably 0.05 MPa or more and less than normal pressure), and if it is normal pressure, the cost can be reduced because no equipment for pressure adjustment is required, Moreover, if the pressure is lower than the saturated water vapor pressure, the load on the compressor when reusing latent heat generated by pressurizing the generated water vapor can be reduced, which is advantageous in actual operation. On the other hand, the lower the pressure, the higher the drying efficiency. However, if the pressure is lowered excessively, not only the medium oil will evaporate, but also the equipment cost will increase.
加熱温度は、実施圧力における水の沸点以上（常圧であれば１００℃以上）とする。バイオマスの細孔内に存在する水分を蒸発させるためである。但し、加熱温度は２００℃以下とすることが好ましい。過剰な加熱はコスト高になるだけでなく、媒体油を蒸発させることになるからである。 The heating temperature is higher than the boiling point of water at the working pressure (100 ° C. or higher if normal pressure). This is to evaporate moisture present in the pores of the biomass. However, the heating temperature is preferably 200 ° C. or lower. This is because excessive heating not only increases the cost but also evaporates the medium oil.
当該工程の実施時間は、バイオマスから除去され蒸発する水分の発生状況を観察して調節すればよい。 The implementation time of the process may be adjusted by observing the generation state of moisture that is removed from the biomass and evaporated.
当該工程で発生した水蒸気の蒸発潜熱は、回収して再利用することが好ましい。その実施形態は、発生した水蒸気を加圧して蒸発潜熱を発生させ、当該乾燥工程（２）または前記改質工程（３）における加熱に使用することによって、本発明の実施をより効率的にするものである。これにより、プロセス全体のエネルギー利用効率を高めることが可能となり、コストを抑えることができる。 It is preferable to recover and reuse the latent heat of vaporization of water vapor generated in this process. The embodiment makes the implementation of the present invention more efficient by pressurizing the generated water vapor to generate latent heat of vaporization and using it for heating in the drying step (2) or the reforming step (3). Is. Thereby, it becomes possible to improve the energy utilization efficiency of the whole process, and can suppress cost.
（３） 好適には、上記粉砕工程（１）の後において、上記脱水工程（２）と実施順位を問わず、水または媒体油の蒸気圧のうち高い方の圧力以上に加圧して加熱する工程（改質工程）を行なう。加圧下で加熱するとバイオマスの一部が分解（改質）され、より微細なガス化燃料を製造することができるからである。尚、より微細なガス化燃料は見かけ上の表面積が大きくなるために、原料バイオマスの重量当たりのガス化触媒担持量を多くすることができ、より効率的なガス化処理が可能になることから好適なものである。 (3) Preferably, after the pulverization step (1), regardless of the order of execution of the dehydration step (2), the pressure is higher than the higher one of the vapor pressures of water or medium oil and heated. A process (reforming process) is performed. This is because part of the biomass is decomposed (reformed) when heated under pressure, and a finer gasified fuel can be produced. Since finer gasified fuel has a larger apparent surface area, the amount of gasification catalyst supported per weight of raw material biomass can be increased, enabling more efficient gasification treatment. Is preferred.
当該工程の圧力を水または媒体油の蒸気圧のうち高い方の圧力以上とするのは、水や媒体油の蒸発を抑制するためである。つまり、媒体油が減少すればスラリーの流動性が悪くなるからであり、また、上記脱水工程後に当該工程を実施する場合においても、細孔内に残留している僅かな水分を利用して、効率的に改質を達成するためである。当該圧力の上限は特に制限されないが、設備費用の面等から「５ＭＰａ以下」とするのが好ましい。より好ましくは、媒体油の蒸気圧以上であることは必要であるが、４ＭＰａ以下，３ＭＰａ以下，２ＭＰａ以下，１ＭＰａ以下が好適である。 The reason for setting the pressure in the step to be higher than the higher one of the vapor pressures of water or medium oil is to suppress evaporation of water and medium oil. That is, if the medium oil is reduced, the fluidity of the slurry is deteriorated, and even when the step is performed after the dehydration step, the slight moisture remaining in the pores is used, This is to achieve reforming efficiently. The upper limit of the pressure is not particularly limited, but is preferably set to “5 MPa or less” from the viewpoint of equipment cost. More preferably, it is necessary to be higher than the vapor pressure of the medium oil, but 4 MPa or less, 3 MPa or less, 2 MPa or less, or 1 MPa or less is suitable.
当該工程の加熱温度としては、１２０〜３００℃が好ましい。１２０℃未満であれば迅速な改質処理を達成し難い場合があり、また、３００℃を超えると分解され易いバイオマスが低分子レベルまで分解されてしまうおそれがあるからである。 As heating temperature of the said process, 120-300 degreeC is preferable. This is because if it is less than 120 ° C., it may be difficult to achieve rapid reforming treatment, and if it exceeds 300 ° C., biomass that is easily decomposed may be decomposed to a low molecular level.
当該工程は、１０〜１２０分間行なうことが好ましい。１０分未満であるとバイオマスの改質を充分に達成できない場合があり、また、１２０分を超えると必要以上にバイオマスがセルロース等のモノマーまで分解されるおそれがあるからである。当該時間については、２０分以上，４０分以上，８０分以下で処理することが好ましく、約１時間が最適である。 This step is preferably performed for 10 to 120 minutes. This is because if it is less than 10 minutes, the modification of the biomass may not be sufficiently achieved, and if it exceeds 120 minutes, the biomass may be decomposed to a monomer such as cellulose more than necessary. About the said time, it is preferable to process in 20 minutes or more, 40 minutes or more, and 80 minutes or less, and about 1 hour is optimal.
上記（２）脱水工程と（３）改質工程の実施順序は特に問わないが、改質工程を先に行なうことが好ましい。バイオマス細孔内の水分を加水分解に利用でき、且つバイオマスの一部が分解することからより効率的に脱水できるという利点がある。また、続く脱水工程において細孔内の水分が媒体油で置換されるが、一部分解によって細孔内に保持される媒体油分が減り、コストを抑制できるというメリットもある。 The order of carrying out the (2) dehydration step and (3) the reforming step is not particularly limited, but it is preferable to perform the reforming step first. There is an advantage that water in the biomass pores can be utilized for hydrolysis, and part of the biomass is decomposed, so that it can be dehydrated more efficiently. Further, in the subsequent dehydration step, the water in the pores is replaced with the medium oil, but there is also an advantage that the medium oil content held in the pores is partially reduced by the decomposition and the cost can be suppressed.
上記脱水工程および改質工程を行なう加熱槽は特に制限されないが、例えば回分式反応器，完全混合型反応器，押出し流れ型反応器を挙げることができる。 The heating tank for performing the dehydration step and the reforming step is not particularly limited, and examples thereof include a batch reactor, a complete mixing reactor, and an extrusion flow reactor.
上記脱水工程または改質工程後においては、遠心脱水法や圧縮脱水法，或いはフラッシュ法によって媒体油分を除去する。次いで、更に過剰な媒体油分を除去すべく、加熱することにより媒体油分を留去してもよい。こうして回収された媒体油分は、コスト面を考慮して再利用する。 After the dehydration step or the reforming step, the medium oil is removed by centrifugal dehydration method, compression dehydration method, or flash method. Subsequently, the medium oil may be distilled off by heating in order to remove an excessive medium oil. The medium oil collected in this way is reused in consideration of cost.
（４） 上記（２）脱水工程または（３）改質工程の後においては、更に、不活性ガス中で炭化する工程（炭化工程）を行なうのも、好適な実施態様である。バイオマスを炭化することによって、より効率的なガス化を達成できるガス化燃料とすることが可能になるからである。 (4) After the above (2) dehydration step or (3) reforming step, it is also a preferred embodiment to further perform a carbonization step (carbonization step) in an inert gas. This is because, by carbonizing biomass, it becomes possible to obtain a gasified fuel that can achieve more efficient gasification.
当該炭化工程は、窒素ガスやアルゴンガスなど、酸素源を含まない不活性ガス中で行なう。酸素の存在化ではバイオマスの燃焼が起こり、炭化されないからである。また、当該工程の実施温度としては、５００〜１２００℃が好適である。５００℃未満では炭化が起こらないことがある一方で、１２００℃を超えると設備費が高くなるからである。 The carbonization step is performed in an inert gas that does not contain an oxygen source, such as nitrogen gas or argon gas. This is because in the presence of oxygen, biomass is burned and not carbonized. Moreover, as implementation temperature of the said process, 500-1200 degreeC is suitable. When the temperature is lower than 500 ° C., carbonization may not occur. However, when the temperature exceeds 1200 ° C., the equipment cost increases.
本発明方法で製造されたガス化燃料は、通常の方法によってガス化することができる。例えば、酸素や空気などの酸化性ガスの存在下５００〜１２００℃で加熱することによって、ＣＯ，Ｈ２，ＣＨ４などを含み発熱量の高い燃料ガスとすることができる。 The gasified fuel produced by the method of the present invention can be gasified by an ordinary method. For example, by heating at 500 to 1200 ° C. in the presence of an oxidizing gas such as oxygen or air, a fuel gas containing CO, H 2 , CH 4 or the like and having a high calorific value can be obtained.
上記（２）脱水工程と（３）改質工程においては、加熱による一部分解や改質によって、蟻酸，酢酸，プロピオン酸，乳酸といった低分子量の有機酸が発生する。従来方法では、これら有機酸は蒸発水分と共に揮発して排水のＢＯＤやＣＯＤを高める原因となっていた。しかし本発明方法では、塩基性を示す触媒原料を添加していることから、これら有機酸は中和され、アルカリ金属イオンやアルカリ土類金属イオンと塩を形成するため、容易には揮発しなくなる。そして斯かる塩或いは未反応の触媒原料は、バイオマスの表面に吸着する。この塩と触媒原料中のアルカリ金属またはアルカリ土類金属は、バイオマスのガス化触媒である。従って、本発明方法により製造されるガス化燃料は、バイオマスと触媒との距離が近く、効率的にガス化され得る。 In the above (2) dehydration step and (3) reforming step, low molecular weight organic acids such as formic acid, acetic acid, propionic acid, and lactic acid are generated by partial decomposition and modification by heating. In the conventional method, these organic acids are volatilized together with the evaporated water, thereby increasing the BOD and COD of the waste water. However, in the method of the present invention, since the catalyst raw material showing basicity is added, these organic acids are neutralized and form salts with alkali metal ions or alkaline earth metal ions, so that they are not easily volatilized. . Such salt or unreacted catalyst raw material is adsorbed on the surface of the biomass. This salt and the alkali metal or alkaline earth metal in the catalyst raw material are biomass gasification catalysts. Therefore, the gasified fuel produced by the method of the present invention has a short distance between the biomass and the catalyst and can be efficiently gasified.
以下に、実施例を示すことにより本発明を更に詳細に説明するが、本発明の範囲はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited thereto.
実施例１ ガス化燃料の製造
内容積15Ｌのオートクレーブに、コーヒー抽出滓（含水率：60％）3 kg，灯油3 kgおよび水酸化カルシウム粉末 10 gを投入し、絶対圧力：0.1 MPa，温度：約120℃で250分間脱水した。その後、約30分かけて内部温度を200℃まで昇温し、加圧下（ゲージ圧：0.098 MPa，絶対圧力：0.196 MPa）、1時間保持した。
Example 1 Production of gasified fuel An autoclave with an internal volume of 15 L was charged with 3 kg of coffee extract (water content: 60%), 3 kg of kerosene and 10 g of calcium hydroxide powder, absolute pressure: 0.1 MPa, temperature: Dehydrated at about 120 ° C. for 250 minutes. Thereafter, the internal temperature was raised to 200 ° C. over about 30 minutes, and held for 1 hour under pressure (gauge pressure: 0.098 MPa, absolute pressure: 0.196 MPa).
内部の温度と回収水量の経時的変化を、図２に示す。当該結果より、水分を多量に含むバイオマスは効率的に乾燥されていることが分かる。 FIG. 2 shows changes with time in the internal temperature and the amount of recovered water. From the results, it can be seen that the biomass containing a large amount of water is efficiently dried.
また、上記処理後のバイオマスは、遠心分離機により固液分離することによって、1.2 kgのガス化燃料を得た。 Moreover, 1.2 kg of gasified fuel was obtained from the treated biomass by solid-liquid separation using a centrifuge.
実施例２ ガス化燃料の分析
上記実施例１で製造したガス化燃料について、誘電結合プラズマ発光分光分析計（島津製作所社製，ICPV-1017）を用いてＣａ含有量を測定した。また、比較のために、原料バイオマスと回収した灯油中に含まれるＣａ含有量も測定した。結果を表１に示す。
Example 2 Analysis of Gasified Fuel For the gasified fuel produced in Example 1 above, the Ca content was measured using a dielectric coupled plasma emission spectrometer (ICPV-1017, manufactured by Shimadzu Corporation). For comparison, the Ca content contained in the raw material biomass and the recovered kerosene was also measured. The results are shown in Table 1.
上記結果において、原料バイオマスに含まれる水分を考慮しても、0.07／1−0.6＝0.175％より、本発明のガス化燃料は、その原料であるバイオマスに比べて顕著に多くのＣａを付着していることが明らかとなった。 In the above results, even when the moisture contained in the raw material biomass is taken into account, the gasified fuel of the present invention adheres significantly more Ca than the raw material biomass from 0.07 / 1−0.6 = 0.175%. It became clear that.
また、上記ガス化燃料と、比較例として実施例１において水酸化カルシウムを用いずに同様の脱水処理をしたもの（比較例１）の表面を電子顕微鏡（日本電子(株)製，低真空SEM JSM-5800LV）で観察した。実施例１のガス化燃料の電子顕微鏡写真を図３として示す。電子顕微鏡観察の結果によれば、実施例１と比較例１共に表面において多数の球状物質の存在が確認された。これら球状物質につき元素分析を行なったところ（図４）、比較例１の球状物質にはＣａが僅かしか含まれていない一方で（図４の(Ｉ)）、実施例１では、バイオマスのガス化触媒となるＣａが多く含まれていることが分かった（図４の(II)）。 Further, the surface of the gasified fuel and the same dehydrated treatment without using calcium hydroxide in Example 1 as a comparative example (Comparative Example 1) were subjected to an electron microscope (manufactured by JEOL Ltd., low vacuum SEM). JSM-5800LV). An electron micrograph of the gasified fuel of Example 1 is shown in FIG. According to the results of electron microscope observation, the presence of a large number of spherical substances on the surface was confirmed in both Example 1 and Comparative Example 1. When elemental analysis was performed on these spherical materials (FIG. 4), the spherical material of Comparative Example 1 contained only a small amount of Ca ((I) of FIG. 4). It was found that a large amount of Ca serving as a catalyst was contained ((II) in FIG. 4).
以上より、本発明のガス化燃料はガス化触媒が表面に直接担持されていることから、ガス化効率に極めて優れ、且つチャーの発生が低減されていることが強く推定できる。 From the above, since the gasification catalyst of the present invention has the gasification catalyst directly supported on the surface, it can be strongly estimated that the gasification efficiency is extremely excellent and the generation of char is reduced.
実施例３ ガス化燃料のガス化
上記実施例１で製造したガス化燃料を、窒素気流中９００℃で加熱することによって炭化した。そして、炭化したガス化燃料を炭酸ガス中で９００℃に加熱し、ガス化した。また、比較例として、実施例１において水酸化カルシウムを用いずに同様の脱水処理をしたもの（比較例１）、および、比較例１の乾燥バイオマスに実施例１と同様の水酸化カルシウムを単に混合したもの（比較例２）について、同様のガス化処理を行なった。念のため、実施例１と比較例２のカルシウム量を測定したところ、表２の通り、カルシウム含有量については全く相違は認められなかった。
Example 3 Gasification of Gasified Fuel The gasified fuel produced in Example 1 was carbonized by heating at 900 ° C. in a nitrogen stream. The carbonized gasified fuel was heated to 900 ° C. in carbon dioxide gas and gasified. In addition, as a comparative example, the same dehydration treatment was performed in Example 1 without using calcium hydroxide (Comparative Example 1), and the dried biomass of Comparative Example 1 was simply obtained by using the same calcium hydroxide as in Example 1. The same gasification treatment was performed on the mixture (Comparative Example 2). As a precaution, when the calcium content of Example 1 and Comparative Example 2 was measured, as shown in Table 2, no difference was found in the calcium content.
炭化処理したガス化燃料をガス化処理した際における重量変化を、図５に示す。当該結果より、水酸化カルシウムを添加して脱水処理を行なった本発明のガス化燃料は、水酸化カルシウムを単に混合したものや全く用いなかったガス化燃料に比して、極めて効率的にガス化されることが実証された。 FIG. 5 shows the change in weight when the carbonized gasified fuel is gasified. From the results, the gasified fuel of the present invention subjected to the dehydration treatment by adding calcium hydroxide is much more efficient than the gasified fuel in which calcium hydroxide is simply mixed or not used at all. It was proved that
実施例４ 排水中のＣＯＤ測定
上記実施例１と同様の処理を行ないつつ、脱水処理時に発生した水分を捕集し、容量法（JIS K102-17）によりＣＯＤ（化学的酸素要求量）を測定した。また、上記実施例３の比較例１（水酸化カルシウムを用いなかった例）も、同様にＣＯＤを測定した。結果を図６に示す。
Example 4 COD measurement in waste water While performing the same treatment as in Example 1 above, water generated during dehydration was collected and COD (chemical oxygen demand) was measured by the volume method (JIS K102-17) did. In addition, COD was also measured in the same manner as in Comparative Example 1 of Example 3 (an example in which calcium hydroxide was not used). The results are shown in FIG.
当該結果より、本発明方法によれば、排水中への有機酸混入を低減でき、環境への負荷を抑制しつつバイオマスからガス化燃料を製造できること、また、排水中への炭素の流入を抑えバイオマスの炭素量を減少させないことが明らかとなった。 From the results, according to the method of the present invention, it is possible to reduce the mixing of organic acid into the wastewater, to produce gasified fuel from biomass while suppressing the burden on the environment, and to suppress the inflow of carbon into the wastewater. It became clear that the carbon content of biomass was not reduced.
Claims (6)
アルカリ金属およびアルカリ土類金属の水酸化物，アルカリ金属およびアルカリ土類金属の炭酸塩，並びにアルカリ金属およびアルカリ土類金属の炭酸水素塩からなる群より選択される１種または２種以上（以下、「触媒原料」という）の粉砕物と、水分を含むバイオマスの粉砕物とを含有する媒体油を、水の蒸気圧未満の圧力下で加熱し、前記バイオマス中に含まれる水分を除去することにより、前記バイオマスの粉砕物の表面に前記触媒原料が担持されたガス化燃料を製造する工程を含むことを特徴とするガス化燃料の製造方法。 A method for producing gasified fuel using biomass as a raw material,
One or more selected from the group consisting of alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal carbonates, and alkali metal and alkaline earth metal hydrogen carbonates (hereinafter referred to as the following) , and pulverized "catalytic material"), a medium oil containing a pulverized product of the biomass containing water, heated under pressure below the water vapor pressure, removing the moisture contained in the biomass The process of manufacturing the gasification fuel characterized by including the process of manufacturing the gasification fuel by which the said catalyst raw material was carry | supported by the surface of the pulverized material of the said biomass .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004076512A JP4364684B2 (en) | 2004-03-17 | 2004-03-17 | Method for producing gasified fuel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004076512A JP4364684B2 (en) | 2004-03-17 | 2004-03-17 | Method for producing gasified fuel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005263914A JP2005263914A (en) | 2005-09-29 |
| JP4364684B2 true JP4364684B2 (en) | 2009-11-18 |
Family
ID=35088794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004076512A Expired - Lifetime JP4364684B2 (en) | 2004-03-17 | 2004-03-17 | Method for producing gasified fuel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4364684B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5034062B2 (en) * | 2006-08-02 | 2012-09-26 | 宇部興産株式会社 | Solid fuel and manufacturing method thereof |
| JP5170516B2 (en) * | 2007-07-11 | 2013-03-27 | 国立大学法人東北大学 | Method for producing hydrogen gas |
| CN101434845A (en) * | 2007-11-16 | 2009-05-20 | 江西汇元再生资源科技发展有限公司 | Preparation of plant gas |
| JP4733792B2 (en) * | 2008-08-26 | 2011-07-27 | 株式会社豊田中央研究所 | Energy gas production method and energy gas storage material |
| JPWO2014007295A1 (en) * | 2012-07-03 | 2016-06-02 | 昭和電工株式会社 | Method for decomposing plant biomass and method for producing glucose |
| CN103725303A (en) * | 2013-07-30 | 2014-04-16 | 北京瑞增兰宇新能源科技有限公司 | Method for continuously separating phenolic compounds in plant-based oil and gas synthesis process |
| JP6570111B2 (en) * | 2015-05-28 | 2019-09-04 | 国立大学法人東北大学 | Hydrogen production method and system |
| CN105647584B (en) * | 2016-01-19 | 2019-07-30 | 青岛理工大学 | Technology for recycling biomass and harmlessly treating chromium slag by using waste heat of blast furnace slag |
| CN110976487A (en) * | 2019-12-24 | 2020-04-10 | 江苏筑原生物科技研究院有限公司 | Method for improving hydrogen yield by catalytic pyrolysis of organic solid waste by using industrial waste residues |
-
2004
- 2004-03-17 JP JP2004076512A patent/JP4364684B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005263914A (en) | 2005-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Garlapalli et al. | Pyrolysis of hydrochar from digestate: Effect of hydrothermal carbonization and pyrolysis temperatures on pyrochar formation | |
| He et al. | Synergistic effect of hydrothermal co-carbonization of sewage sludge with fruit and agricultural wastes on hydrochar fuel quality and combustion behavior | |
| Gao et al. | Effect of residence time on chemical and structural properties of hydrochar obtained by hydrothermal carbonization of water hyacinth | |
| Safian et al. | A review on bio-based graphene derived from biomass wastes | |
| Liew et al. | Stabilization of heavy metals loaded sewage sludge: Reviewing conventional to state-of-the-art thermal treatments in achieving energy sustainability | |
| Peng et al. | Investigation of the structure and reaction pathway of char obtained from sewage sludge with biomass wastes, using hydrothermal treatment | |
| Iwuozor et al. | A review on the thermochemical conversion of sugarcane bagasse into biochar | |
| JP3954544B2 (en) | Method for drying plant-derived biomass and method for producing biomass fuel | |
| Wei et al. | Co-hydrothermal carbonization of pomelo peel and PVC for production of hydrochar pellets with enhanced fuel properties and dechlorination | |
| Parshetti et al. | Chemical, structural and combustion characteristics of carbonaceous products obtained by hydrothermal carbonization of palm empty fruit bunches | |
| Gururani et al. | Recent advances and viability in sustainable thermochemical conversion of sludge to bio-fuel production | |
| EP2475750B1 (en) | Methodology for the removal of inorganic components from biomass of agro/forest/urban origin and from low-quality coal such as peat, lignite, sub-bituminous and bituminous coals | |
| Su et al. | Supercritical water gasification of hyperaccumulators for hydrogen production and heavy metal immobilization with alkali metal catalysts | |
| Rather et al. | Catalytic hydrothermal carbonization of invasive macrophyte Hornwort (Ceratophyllum demersum) for production of hydrochar: a potential biofuel | |
| Ma et al. | Fe (NO3) 3 assisted hydrothermal carbonization of sewage sludge: Focusing on characteristics of hydrochar and aqueous phase | |
| JP4364684B2 (en) | Method for producing gasified fuel | |
| WO2015035077A1 (en) | Catalytic pyrolysis of olive mill waste | |
| Allende et al. | Energy recovery from sugarcane bagasse under varying microwave-assisted pyrolysis conditions | |
| JP2018111055A (en) | Modification method of vegetable system biomass | |
| Yu et al. | The chemical compositions and carbon structures of pine sawdust-and wheat straw-derived biochars produced in air-limitation, carbon dioxide, and nitrogen atmospheres, and their variation with charring temperature | |
| US8465557B2 (en) | Process for making bio-oils and fresh water from aquatic biomass | |
| JP4919253B2 (en) | Biological organic resource processing method and system | |
| Hartulistiyoso et al. | Co-production of hydrochar and bioactive compounds from Ulva lactuca via a hydrothermal process | |
| Chen et al. | Hydrothermal carbonization of poplar sawdust: Effect of deep eutectic solvents on hydrochar's physicochemical properties | |
| JP2007070408A (en) | Method for treating supercritical water decomposition gas, and energy recovery system and organic compound production system each utilizing the method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060925 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090225 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090317 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090422 |
|
| 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: 20090818 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090819 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120828 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4364684 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120828 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130828 Year of fee payment: 4 |
|
| EXPY | Cancellation because of completion of term |