JP5380691B2 - Biomass gasifier and method therefor - Google Patents
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- 239000002028 Biomass Substances 0.000 title claims description 101
- 238000000034 method Methods 0.000 title claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 139
- 239000007789 gas Substances 0.000 claims description 89
- 239000002994 raw material Substances 0.000 claims description 66
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 46
- 230000015572 biosynthetic process Effects 0.000 claims description 46
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 46
- 238000003786 synthesis reaction Methods 0.000 claims description 46
- 238000002309 gasification Methods 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 230000001590 oxidative effect Effects 0.000 claims description 27
- 238000000629 steam reforming Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 13
- 238000002407 reforming Methods 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005192 partition Methods 0.000 claims description 6
- 239000012495 reaction gas Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 150000002431 hydrogen Chemical class 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002551 biofuel Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- -1 and in particular Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 241000218645 Cedrus Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Description
本発明は、原料バイオマスから合成ガスを得るためのバイオマスガス化装置及びその方法に関し、特に、原料バイオマスを部分酸化させて得られた生成ガスを水蒸気改質させて合成ガスを得るためのバイオマスガス化装置及びその方法に関する。 The present invention relates to a biomass gasification apparatus and method for obtaining synthesis gas from raw material biomass, and in particular, biomass gas for obtaining synthetic gas by steam reforming a product gas obtained by partially oxidizing raw material biomass. The present invention relates to an apparatus and a method thereof.
バイオマス（Ｂｉｏｍａｓｓ）は、生物量を物質量で表現すること全般に対して広義に用いられる生態学上の用語である。近年では生物由来資源の意味でも使われており、バイオマスを用いた燃料はバイオ燃料（Ｂｉｏｆｕｅｌ）などとも呼ばれている。 Biomass is an ecological term that is used in a broad sense for the overall expression of biomass in terms of substance. In recent years, it is also used in the meaning of biological resources, and fuel using biomass is also called biofuel.
ところで、１９９７年１２月に地球温暖化の防止のために温暖化ガスの排出量削減を目的とした京都議定書が採択され、特に、温暖化ガスの１つである二酸化炭素（ＣＯ２）の排出量の削減が大きな課題とされている。このような中、ＣＯ２を光合成によって取り込んで成長する植物を由来とした植物バイオ燃料（植物バイオマス）が注目されている。植物バイオ燃料は、これを燃焼させてＣＯ２を排出したとしても、ライフサイクルの中でトータルとしてカーボンニュートラルであるとされる。故に、社会活動に不可欠な燃料の燃焼におけるＣＯ２量低減に大きく寄与する。 By the way, in December 1997, the Kyoto Protocol was adopted to reduce greenhouse gas emissions to prevent global warming, and in particular, emissions of carbon dioxide (CO 2 ), one of the greenhouse gases. Reducing the amount is a major issue. Under such circumstances, plant biofuels (plant biomass) derived from plants that grow by taking CO 2 by photosynthesis are attracting attention. Plant biofuel is considered to be carbon neutral as a whole in the life cycle even if it is burned to emit CO 2 . Therefore, it greatly contributes to the reduction of CO 2 amount in the combustion of fuel indispensable for social activities.
このようなバイオマス（「原料バイオマス」とも称する。）から得られたバイオ燃料については多くの利用方法が提案されている。 Many utilization methods are proposed about the biofuel obtained from such biomass (it is also called "raw material biomass").
例えば、原料バイオマスを用いて製造されたエタノールは、ガソリンに混合されたり、またエチル・ターシャリー・ブチル・エーテル（ＥＴＢＥ）に変換された後にガソリンに混合して利用される。また、原料バイオマスとしての動植物油をメチルエステル化して得られる脂肪酸メチルエステル（ＦＡＭＥ）は、ディーゼル燃料として単独若しくは軽油と混合して利用される。 For example, ethanol produced from raw material biomass is mixed with gasoline or used after being converted into ethyl tertiary butyl ether (ETBE) and mixed with gasoline. In addition, fatty acid methyl ester (FAME) obtained by methyl esterifying animal and vegetable oils as raw material biomass is used alone or mixed with light oil as diesel fuel.
一方、原料バイオマスをガス化して利用する方法も提案されている。例えば、原料バイオマスをガス化して得られる合成ガスは、フィッシャー・トロプシュ（ＦＴ）合成によって炭化水素化合物を経てアップグレーディング技術でさまざまな油種とされ得る。また、合成ガスを燃料としてガスエンジンやガスタービンに供給して発電を行うことも出来る。 On the other hand, a method of gasifying and utilizing raw material biomass has also been proposed. For example, synthesis gas obtained by gasifying raw biomass can be made into various oil types by upgrading technology through hydrocarbon compounds by Fischer-Tropsch (FT) synthesis. It is also possible to generate electricity by supplying synthesis gas as a fuel to a gas engine or a gas turbine.
ここで原料バイオマスを空気、酸素（Ｏ２）又は水蒸気、若しくは、これらの組み合わせなどからなる酸化ガス化剤を用いてガス化すると、水素（Ｈ２）一酸化炭素（ＣＯ）及びＣＯ２等からなる合成ガスと、炭化水素であるタールや、炭素分であるチャー、灰分などが同時に生成する。このときガス化温度が低いと、タールを多く生成して合成ガスの収率が低下する。また、タールはチャーなどとともに配管や反応炉に付着しやすく装置の運転が難しくなる。一方、ガス化温度が高いと、高分子炭化水素であるタールをＨ２及びＣに熱分解できて好ましいが、高温を維持するために原料バイオマスの４〜６割を熱源として燃焼消費してしまう。結果として、合成ガスの収率が低下してしまう。 Here, when raw material biomass is gasified using an oxidizing gasifying agent comprising air, oxygen (O 2 ), water vapor, or a combination thereof, hydrogen (H 2 ), carbon monoxide (CO), CO 2, etc. Synthetic gas and tar, which is hydrocarbon, char, ash, etc., which are carbon, are produced at the same time. At this time, if the gasification temperature is low, a large amount of tar is produced and the yield of the synthesis gas decreases. Also, tar tends to adhere to piping and reaction furnaces together with char and the like, making it difficult to operate the apparatus. On the other hand, when the gasification temperature is high, tar, which is a polymer hydrocarbon, can be thermally decomposed into H 2 and C. However, in order to maintain a high temperature, 40 to 60% of the raw material biomass is burned and consumed. . As a result, the yield of synthesis gas is reduced.
例えば、特許文献１では、各種原料バイオマスから高い収率で合成ガスを得ることの出来るガス化システムが開示されている。特に、Ｈ２／ＣＯ比率を２よりも高めて、メタノール合成の原料の製造に適したシステムを開示している。Ｏ２又はこれと水蒸気の混合物からなる燃焼酸化剤とともにガス化炉に供給された原料バイオマスは、８００〜１０００℃の高温でＨ２、ＣＯ及びＣＯ２の生成ガスや、ＣＨ４等の炭化水素にガス化される。続く、後段のスチームリフォーミングでは、ＣＨ４等の炭化水素がニッケル等の触媒の下で、Ｈ２及びＣＯに水蒸気改質される。さらに、ＣＯシフト反応装置によってＣＯをＣＯ２へ変換させて、Ｈ２／ＣＯ比率の調整を行っている。ここで、ガス化を良好に進行させるためには、ガス化炉の温度を８００〜１０００℃の高温に維持しなければならず、高温の合成ガスの有する熱量の有効利用によって、水蒸気を４００〜５００℃程度に加熱してからガス化炉に導入することを開示している。 For example, Patent Document 1 discloses a gasification system that can obtain synthesis gas from various raw material biomasses with high yield. In particular, a system suitable for producing a raw material for methanol synthesis with an H 2 / CO ratio higher than 2 is disclosed. The raw material biomass supplied to the gasifier together with the combustion oxidant composed of O 2 or a mixture of water vapor and steam is a gas produced from H 2 , CO and CO 2 at a high temperature of 800 to 1000 ° C., and hydrocarbons such as CH 4 Is gasified. In the subsequent steam reforming, hydrocarbons such as CH 4 are steam reformed to H 2 and CO under a catalyst such as nickel. Furthermore, CO is converted into CO 2 by a CO shift reaction apparatus, and the H 2 / CO ratio is adjusted. Here, in order for gasification to proceed well, the temperature of the gasification furnace must be maintained at a high temperature of 800 to 1000 ° C., and by using the heat quantity of the high-temperature synthesis gas effectively, the steam is reduced to 400 to It discloses that it is heated to about 500 ° C. and then introduced into the gasifier.
また、特許文献２では、ガス化炉内で生成される生成ガスの温度に応じて、燃焼酸化剤であるＯ２と水蒸気の混合物の比率を変化させて、ガス化炉内の局所的な高温部の発生を抑制し、これによりクリンカの発生を抑制し得ることを開示している。その一方で、生成ガスの温度をタールが付着しない程度の温度以上に維持して、ガス化を良好に進行させ得ることも開示している。
原料バイオマスからの合成ガスの収率が低下すると、所定量の合成ガスを得るために装置容量を大きくする必要が生じる。また、特許文献１のように、部分酸化反応と水蒸気改質反応を組み合わせても、得られる合成ガスにおいてＨ２／ＣＯ比率が２よりも小さければ、この比率を調整するためのシフト反応装置を更に設けなければならず、装置が大型化してしまう。 When the yield of synthesis gas from raw biomass decreases, it is necessary to increase the apparatus capacity in order to obtain a predetermined amount of synthesis gas. Further, as in Patent Document 1, even if a partial oxidation reaction and a steam reforming reaction are combined, if the H 2 / CO ratio is smaller than 2 in the resultant synthesis gas, a shift reactor for adjusting this ratio is provided. Furthermore, it must be provided, and the apparatus becomes large.
本発明は上記したような状況に鑑みてなされたものであって、その目的は、コンパクトであって、原料バイオマスから高い収率で合成ガスを得ることの出来るバイオマスガス化装置及びその方法の提供である。 The present invention has been made in view of the situation as described above, and an object of the present invention is to provide a biomass gasification apparatus capable of obtaining synthesis gas with high yield from raw biomass and a method thereof. It is.
本発明によるバイオマスガス化装置は、原料バイオマスを部分酸化させて得られた生成ガスを水蒸気改質させて合成ガスを得るためのバイオマスガス化装置であって、前記原料バイオマスを落下させながら酸化ガス化剤と反応させて生成ガスを生じさせるための第１反応容器と、前記第１反応容器内の前記原料バイオマスの落下流路に向けて前記酸化ガス化剤を導くためのガス化剤供給管と、前記第１反応容器内にあって前記生成ガスを水蒸気とともにその内部に導いて前記合成ガスを得るための第２反応容器と、前記第２反応容器に前記水蒸気を供給するための水蒸気供給管と、からなり、伝熱隔壁によって前記第１反応容器内の空間と画定された前記第２反応容器内の反応空間に改質触媒を装填し前記反応空間を前記原料バイオマスの落下流路内に配置することを特徴とする。 A biomass gasification apparatus according to the present invention is a biomass gasification apparatus for obtaining a synthesis gas by steam reforming a product gas obtained by partially oxidizing a raw material biomass, wherein the oxidizing gas is dropped while dropping the raw material biomass A first reaction vessel for reacting with the agent to generate product gas, and a gasifying agent supply pipe for guiding the oxidizing gasifying agent toward the flow path of the raw material biomass in the first reaction vessel A second reaction container for obtaining the synthesis gas by introducing the product gas into the first reaction container together with water vapor, and a water vapor supply for supplying the water vapor to the second reaction container. A reforming catalyst is loaded into the reaction space in the second reaction vessel, which is defined as the space in the first reaction vessel by the heat transfer partition, and the raw material biomass is dropped in the reaction space. Characterized in that it placed in the flow path.
上記構成によれば、原料バイオマスを落下させながら酸化ガス化剤と効率よく反応させてタール分を多く含む水素（Ｈ２）、一酸化炭素（ＣＯ）、及び二酸化炭素（ＣＯ２）等の生成ガスを得られるので、原料バイオマスの燃焼を抑えつつ、部分酸化のための熱を安定して得ることが出来る。つまり、原料バイオマスの損失が少ないから、高い収率で揮発性成分及びガス成分を得ることが出来る。また、揮発性成分であるタール分の改質を水蒸気改質反応で行うため、この水蒸気改質反応だけで合成ガスにおける高いＨ２／ＣＯ比率を達成し得る。シフト反応装置などを必要としないから、装置をコンパクトに出来る。なお、さらに高い水素の比率を必要とする場合にあっては、シフト反応装置を付随させてもよい。また、第１反応容器における部分酸化反応で生ずる熱を第２反応容器における水蒸気改質反応に安定して供給出来るため、さらに高い収率で合成ガスを得ることが出来る。 According to the above configuration, hydrogen (H 2 ), carbon monoxide (CO), carbon dioxide (CO 2 ) and the like containing a large amount of tar are obtained by efficiently reacting with the oxidizing gasifying agent while dropping the raw material biomass. Since gas can be obtained, heat for partial oxidation can be stably obtained while suppressing combustion of raw material biomass. That is, since there is little loss of raw material biomass, a volatile component and a gas component can be obtained with a high yield. Further, since reforming of the tar component, which is a volatile component, is performed by a steam reforming reaction, a high H 2 / CO ratio in the synthesis gas can be achieved only by this steam reforming reaction. Since no shift reaction device is required, the device can be made compact. If a higher hydrogen ratio is required, a shift reaction apparatus may be attached. Moreover, since the heat generated by the partial oxidation reaction in the first reaction vessel can be stably supplied to the steam reforming reaction in the second reaction vessel, the synthesis gas can be obtained with a higher yield.
更に、前記第２反応容器の開口端部は、前記水蒸気供給管の開口端部と対向していることを特徴としてもよい。かかる構成によれば、水蒸気の流れによって第２反応容器内に生成ガスだけを導き得るので、固体成分の付着による改質触媒の性能低下を防止できる。 Furthermore, the open end of the second reaction vessel may be opposed to the open end of the water vapor supply pipe. According to such a configuration, only the product gas can be guided into the second reaction vessel by the flow of water vapor, so that it is possible to prevent the performance degradation of the reforming catalyst due to the adhesion of the solid component.
更に、前記第１反応容器、前記第２反応容器及び前記水蒸気供給管は同一の鉛直軸線上に配置されていることを特徴としてもよい。かかる構成によれば、第１反応容器内の固体成分の第２反応容器及び水蒸気供給管への付着を防止できるとともに、装置をコンパクトにできる。 Furthermore, the first reaction vessel, the second reaction vessel, and the water vapor supply pipe may be arranged on the same vertical axis. According to this configuration, the solid component in the first reaction vessel can be prevented from adhering to the second reaction vessel and the water vapor supply pipe, and the apparatus can be made compact.
ここで、前記酸化ガス化剤は、純酸素、酸素富化空気、又は空気であることを特徴としてもよい。空気中の窒素は得られる合成ガスの希釈ガスとなってしまうため、酸化ガス化剤は酸素であることが好ましい。しかしながら、酸化剤としての空気を大量供給して原料バイオマスを燃焼させ、１０００℃以上で反応させる従来のバイオマスガス化法よりも収率が高い本発明によれば、空気を用いても依然として従来法以上の高い収率で合成ガスを得られる。なお、「酸素富化空気」は、酸素富化膜やＰＳＡ（Ｐｒｅｓｓｕｒｅ Ｓｗｉｎｇ Ａｄｓｏｒｐｔｉｏｎ）を用いた公知の技術で得られる酸素分の高い気体である。 Here, the oxidizing gasifying agent may be pure oxygen, oxygen-enriched air, or air. Since nitrogen in the air becomes a dilution gas of the resultant synthesis gas, the oxidizing gasifying agent is preferably oxygen. However, according to the present invention, which has a higher yield than the conventional biomass gasification method in which a large amount of air as an oxidizer is supplied to burn raw material biomass and react at 1000 ° C. or higher, the conventional method is still used even if air is used. Syngas can be obtained with the above high yield. “Oxygen-enriched air” is a gas having a high oxygen content obtained by a known technique using an oxygen-enriched film or PSA (Pressure Swing Adsorption).
また、本発明によるバイオマスガス化方法は、原料バイオマスを部分酸化させて得られたタール分を多く含む水素（Ｈ２）一酸化炭素（ＣＯ）及び二酸化炭素（ＣＯ２）等生成ガスを水蒸気改質させて合成ガスを得るためのバイオマスガス化方法であって、前記原料バイオマスを第１反応容器内にて落下させるステップと、前記原料バイオマスの落下流路に向けて前記酸化ガス化剤を導くステップと、前記原料バイオマスを落下させながら前記酸化ガス化剤と反応して生じた生成ガスを水蒸気とともに前記第１反応容器内の第２反応容器の内部に導いて前記合成ガスを得る水蒸気改質ステップとからなり、伝熱隔壁によって前記第１反応容器内の空間と画定された前記第２反応容器内の反応空間に改質触媒を装填し、前記反応空間を前記原料バイオマスの落下流路内に配置して、部分酸化ステップで生ずる熱を水蒸気改質ステップに利用することを特徴とする。 In addition, the biomass gasification method according to the present invention uses steam reforming of produced gas such as hydrogen (H 2 ), carbon monoxide (CO) and carbon dioxide (CO 2 ) containing a large amount of tar obtained by partial oxidation of raw material biomass. A biomass gasification method for obtaining a synthesis gas by gasifying, wherein the raw material biomass is dropped in a first reaction vessel, and the oxidizing gasifying agent is guided toward the raw material biomass drop channel And steam reforming to obtain the synthesis gas by introducing the produced gas generated by reacting with the oxidizing gasifying agent while dropping the raw biomass into the second reaction vessel in the first reaction vessel together with the steam A reforming catalyst is loaded into a reaction space in the second reaction vessel, which is defined as a space in the first reaction vessel by a heat transfer partition, and the reaction space is made into the original space. The heat generated in the partial oxidation step is used in the steam reforming step by being disposed in the falling path of the raw material biomass.
上記方法によれば、原料バイオマスを落下させながら酸化ガス化剤と効率よく反応させ得るので、原料バイオマスの燃焼を抑えつつ、部分酸化のための熱を安定して得ることが出来る。つまり、原料バイオマスの損失が少ないから、高い収率でタール分を多く含む水素（Ｈ２）一酸化炭素（ＣＯ）及び二酸化炭素（ＣＯ２）等のガス成分を得ることが出来る。また、揮発性成分であるタール分及び低級の炭化水素の改質を水蒸気改質反応で行うため、この水蒸気改質反応だけで合成ガスにおける高いＨ２／ＣＯ比率を達成し得る。また、シフト反応装置などを必要としないから、装置をコンパクトに出来る。また、第１反応容器における部分酸化反応で生ずる熱を第２反応容器における水蒸気改質反応に安定して供給出来るため、さらに高い収率で合成ガスを得ることが出来る。 According to the above method, since the raw material biomass can be dropped and efficiently reacted with the oxidizing gasifying agent, heat for partial oxidation can be stably obtained while suppressing the combustion of the raw material biomass. That is, since there is little loss of raw material biomass, it is possible to obtain gas components such as hydrogen (H 2 ), carbon monoxide (CO), and carbon dioxide (CO 2 ) that contain a large amount of tar with a high yield. In addition, since reforming of the volatile component tar and lower hydrocarbon is performed by the steam reforming reaction, a high H 2 / CO ratio in the synthesis gas can be achieved only by this steam reforming reaction. In addition, since a shift reaction apparatus is not required, the apparatus can be made compact. Moreover, since the heat generated by the partial oxidation reaction in the first reaction vessel can be stably supplied to the steam reforming reaction in the second reaction vessel, the synthesis gas can be obtained with a higher yield.
更に、前記部分酸化ステップは、生じた固体成分を落下させてガス成分と分離するステップを含むことを特徴としてもよい。かかる方法によれば、第１反応容器内の固体成分の第２反応容器内部への混入を防止出来る。 Further, the partial oxidation step may include a step of dropping the generated solid component to separate it from the gas component. According to this method, mixing of the solid component in the first reaction vessel into the second reaction vessel can be prevented.
更に、前記水蒸気改質ステップは、５００〜９００℃、好ましくは５００〜７００℃の温度範囲となるようにして水素及び一酸化炭素を生成することを特徴としてもよい。かかる方法によれば、より低い温度で部分酸化を行うことが出来て、原料バイオマスの燃焼量を低減できるのである。結果として、高い収率で且つＨ２／ＣＯ比率の高い合成ガスを得ることが出来る。 Further, the steam reforming step may be characterized in that hydrogen and carbon monoxide are generated in a temperature range of 500 to 900 ° C., preferably 500 to 700 ° C. According to this method, partial oxidation can be performed at a lower temperature, and the amount of combustion of raw material biomass can be reduced. As a result, a synthesis gas having a high yield and a high H 2 / CO ratio can be obtained.
更に、前記酸化ガス化剤は、純酸素、酸素富化空気、又は空気であることを特徴としてもよい。上記したように高い収率で合成ガスを得ることが出来るので、酸化剤ガスを空気として窒素のような希釈ガスが含まれたとしても、依然として高い収率で合成ガスを得られる。また、必要な場合には合成ガスの熱量やアップグレーディング技術に対応して、希釈ガスの分離工程を加えても良い。 Further, the oxidizing gasifying agent may be pure oxygen, oxygen-enriched air, or air. Since the synthesis gas can be obtained with a high yield as described above, the synthesis gas can still be obtained with a high yield even if the oxidizing gas is used as air and a diluent gas such as nitrogen is included. Further, if necessary, a dilution gas separation step may be added in accordance with the amount of heat of the synthesis gas and the upgrading technique.
まず、本発明によるバイオマスガス化装置及びその方法における化学反応について説明する。 First, the chemical reaction in the biomass gasification apparatus and method according to the present invention will be described.
図１に示すように、第１段階の化学反応Ｒ１において、例えば、ＣｘＨｙＯｚで表される原料バイオマスは、純酸素、酸素富化空気、又は空気からなる酸化ガス化剤を与えながらガス化される。詳細には、反応式（１）で表される熱分解、及び、反応式（２）で表される部分酸化を同時に生ずる。また、反応式（３）〜（６）についても生じ得る。その結果、水素、一酸化炭素、二酸化炭素及びタールを含む揮発性の炭化水素からなる気体成分が生成し、これとあわせて、チャーや灰分などの固体成分が生成する。 As shown in FIG. 1, in the first stage chemical reaction R1, for example, the raw material biomass represented by C x H y O z gives pure oxygen, oxygen-enriched air, or an oxidizing gasifying agent composed of air. While being gasified. Specifically, the thermal decomposition represented by the reaction formula (1) and the partial oxidation represented by the reaction formula (2) occur simultaneously. Moreover, it may arise also about Reaction formula (3)-(6). As a result, a gaseous component composed of volatile hydrocarbons including hydrogen, carbon monoxide, carbon dioxide, and tar is generated, and together with this, solid components such as char and ash are generated.
化学反応Ｒ１に続く、第２段階の化学反応Ｒ２において、化学反応Ｒ１で得られた気体成分のうち、タールなどの炭化水素（例えばＣａＨｂＯｃ）は、水蒸気とともに触媒の存在下で水蒸気改質される。詳細には、反応式（７）で表される水蒸気改質反応を生じる。また、反応式（８）で表される部分酸化や、反応式（９）のようなシフト反応も一部生じ得る。これにより、さらに水素、一酸化炭素及び二酸化炭素が生成する。 In the second-stage chemical reaction R2 following the chemical reaction R1, among the gas components obtained in the chemical reaction R1, hydrocarbons such as tar (for example, C a H b O c ) together with water vapor are present in the presence of the catalyst. Steam reforming is performed. Specifically, the steam reforming reaction represented by the reaction formula (7) occurs. Moreover, partial oxidation represented by the reaction formula (8) and a shift reaction like the reaction formula (9) may partially occur. This further generates hydrogen, carbon monoxide, and carbon dioxide.
第１段階の化学反応Ｒ１及び第２段階の化学反応Ｒ２で生成した水素、一酸化炭素及び二酸化炭素からなる合成ガスは、適宜、公知の方法で利用され得る。例えば、フィッシャー・トロプシュ（ＦＴ）合成によって炭化水素化合物を経てアップグレーディング技術でさまざまな油種とされ得る。また、合成ガスを燃料としてガスエンジンやガスタービンに供給して発電を行うことも出来る。 The synthesis gas composed of hydrogen, carbon monoxide, and carbon dioxide generated in the first-stage chemical reaction R1 and the second-stage chemical reaction R2 can be appropriately used by a known method. For example, it can be made into various oil types by upgrading technology via hydrocarbon compounds by Fischer-Tropsch (FT) synthesis. It is also possible to generate electricity by supplying synthesis gas as a fuel to a gas engine or a gas turbine.
ところで、上記した第１段階の化学反応Ｒ１及び第２段階の化学反応Ｒ２において、原料の水素含量によって部分酸化反応及び水蒸気改質反応は異なる。しかしながら、第１段階の化学反応Ｒ１に関して、重質残渣油のガス化などを例とすると、部分酸化反応は、炭素に注目して、
Ｃ＋（１／２）Ｏ２ ⇔ ＣＯ＋１２３ｋＪ／ｍｏｌ
と表せるように、発熱反応である。また、第２段階の化学反応Ｒ２に関して、第１段階の化学反応Ｒ１と同様に、重質残渣油のガス化を例とすると、水蒸気改質反応は、炭素に注目して、
Ｃ＋Ｈ２Ｏ ⇔ ＣＯ ＋Ｈ２−１１９ｋＪ／ｍｏｌ
と表せるように、吸熱反応である。このような１つの例からもわかるように、第１段階の化学反応Ｒ１における部分酸化反応で生ずる熱を第２段階の化学反応Ｒ２における水蒸気改質反応に利用できると、全体のエネルギー効率を向上させられるのである。これにより、水蒸気（Ｈ２Ｏ）に由来する水素をも得ることが出来るから、Ｈ２／ＣＯ比率を高め得る。特に、上記したフィッシャー・トロプシュ（ＦＴ）合成や、ＤＭＥ（ジメチルエーテル）、メタノールの液体合成に好適とされる合成ガスにおけるＨ２／ＣＯ比率＞２を達成し得るのである。
By the way, in the first stage chemical reaction R1 and the second stage chemical reaction R2, the partial oxidation reaction and the steam reforming reaction differ depending on the hydrogen content of the raw material. However, with respect to the first stage chemical reaction R1, for example, gasification of heavy residual oil, the partial oxidation reaction focuses on carbon,
C + (1/2) O 2 ＣＯCO + 123 kJ / mol
This is an exothermic reaction. Further, regarding the chemical reaction R2 in the second stage, similarly to the chemical reaction R1 in the first stage, when gasification of heavy residual oil is taken as an example, the steam reforming reaction focuses on carbon,
C + H 2 O⇔CO + H 2 −119 kJ / mol
This is an endothermic reaction. As can be seen from one such example, if the heat generated in the partial oxidation reaction in the first stage chemical reaction R1 can be used for the steam reforming reaction in the second stage chemical reaction R2, the overall energy efficiency is improved. It is made possible. Thereby, since hydrogen derived from water vapor (H 2 O) can also be obtained, the H 2 / CO ratio can be increased. In particular, it is possible to achieve the H 2 / CO ratio> 2 in the synthesis gas suitable for the above-described Fischer-Tropsch (FT) synthesis, DME (dimethyl ether), and methanol liquid synthesis.
次に、本発明によるバイオマスガス化装置１について説明する。 Next, the biomass gasification apparatus 1 by this invention is demonstrated.
図２に示すように、反応容器１０は、円筒状又は角筒状などの中空容器である。反応容器１０は、上端部を蓋部１０ａで閉塞されており、また下端部近傍には断面積を減じるように漏斗状に傾斜した傾斜部１０ｂが設けられている。傾斜部１０ｂの位置及び傾斜形状等により、後述する原料バイオマスの落下流路Ｆを変化させ得る。さらに傾斜部１０ｂの底部中央には、後述する原料バイオマスのガス化によって生じる固体成分を収集するための堆積槽１０ｃが設けられている。なお、堆積槽１０ｃには、この中に堆積した固体成分を取り出すための図示しない取り出し口が設けられている。 As shown in FIG. 2, the reaction vessel 10 is a hollow vessel such as a cylindrical shape or a rectangular tube shape. The reaction vessel 10 has an upper end closed by a lid 10a, and an inclined portion 10b inclined in a funnel shape is provided in the vicinity of the lower end so as to reduce the cross-sectional area. Depending on the position of the inclined portion 10b, the inclined shape, and the like, the below-described raw material biomass falling flow path F can be changed. Furthermore, in the center of the bottom of the inclined portion 10b, a deposition tank 10c for collecting solid components generated by gasification of raw material biomass described later is provided. The deposition tank 10c is provided with a take-out port (not shown) for taking out the solid component accumulated therein.
水蒸気供給管１５は、反応容器１０の中心軸線Ｍに沿って上方へ向けて伸びており、上方端部の開口１５ａから水蒸気を反応容器１０内部に導入する。開口１５ａは、反応容器１０の傾斜部１０ｂの側方に位置している。 The water vapor supply pipe 15 extends upward along the central axis M of the reaction vessel 10, and introduces water vapor into the reaction vessel 10 from the opening 15 a at the upper end. The opening 15 a is located on the side of the inclined portion 10 b of the reaction vessel 10.
また、反応容器１０の中心軸線Ｍに沿って、蓋部１０を貫通するようにして筒状反応容器２０が垂下している。筒状反応容器２０の下方端部の開口２０ａは、水蒸気供給管１５の開口１５ａと離間して対向している。 A cylindrical reaction vessel 20 is suspended along the central axis M of the reaction vessel 10 so as to penetrate the lid portion 10. The opening 20a at the lower end of the cylindrical reaction vessel 20 is opposed to the opening 15a of the steam supply pipe 15 while being spaced apart.
ここで、図３（ａ）〜（ｃ）に示すように、筒状反応容器２０の開口２０ａ近傍における先端部２０ｂは、伝熱隔壁として第１反応容器１０内の空間とその内部とを分離している。特に、図３（ａ）に示すように、先端部２０ｂで画定される空間内には、担体がアルミナ等からなる球状若しくは不定型状の顆粒状の触媒２５が充填されている。これとともに開口２０ａには、気体を透過するように貫通穴を多数設けた格子板２５ａなどが嵌め込まれて、触媒２５が落下しないようになっている。格子板２５ａは気体のみが透過するような構造であれば、多孔質セラミックス板などを適宜、用い得る。触媒２５は、公知の水蒸気改質金属触媒、又は、部分酸化金属触媒等を与えられ、これは、例えば、ニッケル、ルテニウム、ロジウムなどを用いた改質、酸化性能を有するものであればよい。また、複数の触媒を使用してもよい。 Here, as shown in FIGS. 3A to 3C, the tip 20b in the vicinity of the opening 20a of the cylindrical reaction vessel 20 separates the space in the first reaction vessel 10 from the interior thereof as a heat transfer partition. doing. In particular, as shown in FIG. 3A, the space defined by the tip portion 20b is filled with a spherical or irregular shaped granular catalyst 25 whose support is made of alumina or the like. At the same time, the opening 25a is fitted with a lattice plate 25a provided with many through holes so as to allow gas to pass therethrough, so that the catalyst 25 does not fall. If the lattice plate 25a has a structure that allows only gas to pass therethrough, a porous ceramic plate or the like can be used as appropriate. The catalyst 25 is provided with a known steam reforming metal catalyst, a partially oxidized metal catalyst, or the like, and any catalyst may be used as long as it has reforming and oxidation performance using, for example, nickel, ruthenium, rhodium or the like. A plurality of catalysts may be used.
なお、図３（ｂ）に示すように触媒２５は、円柱型や押し出し形状のペレット状であって、ガスが透過可能な多孔質体からなるものであってもよい。更に、図３（ｃ）に示すように、筒状反応容器２０の先端部２０ｂが略鉛直に配置されているときなどは、触媒２５を筒状反応容器２０の開口２０ａよりも外側に突出するように取り付けて、この中を水蒸気及びガスがより透過しやすくしても良い。なお、触媒２５の担体は、アルミナに限定するものでなく、例えばシリカ、あるいはシリカ、アルミナなど複数からなるものを使用することが出来る。 As shown in FIG. 3B, the catalyst 25 may be a cylindrical or extruded pellet, and may be made of a porous material through which gas can permeate. Further, as shown in FIG. 3C, when the tip 20 b of the cylindrical reaction vessel 20 is disposed substantially vertically, the catalyst 25 protrudes outside the opening 20 a of the cylindrical reaction vessel 20. It is possible to make it easier for water vapor and gas to permeate therethrough. In addition, the support | carrier of the catalyst 25 is not limited to an alumina, For example, what consists of multiple things, such as a silica or a silica, an alumina, can be used.
更に、図４（ａ）及び（ｂ）に示すように、水蒸気を導入するための水蒸気供給管１５は、筒状反応容器２０内に配置されて、その開口１５ａを触媒２５の近傍、若しくは、埋設してしまって水蒸気を確実に触媒２５内部に導くようにしても良い。また、図４（ｃ）に示すように、筒状反応容器２０の開口２０ａから触媒２５の内部に挿入、若しくは、筒状反応容器２０の一部をなすように設けても良い。 Further, as shown in FIGS. 4 (a) and 4 (b), the steam supply pipe 15 for introducing steam is disposed in the cylindrical reaction vessel 20, and the opening 15a is provided in the vicinity of the catalyst 25, or It may be buried so that water vapor is reliably guided into the catalyst 25. Moreover, as shown in FIG.4 (c), you may provide so that it may insert in the inside of the catalyst 25 from the opening 20a of the cylindrical reaction container 20, or may make a part of the cylindrical reaction container 20. As shown in FIG.
再び、図２を参照すると、蓋部１０ａにはこれを貫通するようにして、反応容器１０内に破砕された原料バイオマスを落下させながら導入するための原料バイオマス供給管３５が取り付けられている。更に、反応容器１０の側壁には、原料バイオマスの落下流路Ｆに向けて、純酸素、酸素富化空気、又は空気からなる酸化ガス化剤を導くガス化剤供給管４０が設けられている。なお、図２では、ガス化剤供給管４０は、２箇所にのみ設けるように示されているが、適宜、所定箇所に設けられ、１箇所であっても、また複数箇所に設けられていてもよい。 Referring again to FIG. 2, a raw material biomass supply pipe 35 is attached to the lid portion 10 a so as to penetrate the lid portion 10 a while introducing the crushed raw material biomass into the reaction vessel 10. Furthermore, a gasifying agent supply pipe 40 for introducing an oxidizing gasifying agent composed of pure oxygen, oxygen-enriched air, or air is provided on the side wall of the reaction vessel 10 toward the falling flow path F of the raw material biomass. . In FIG. 2, the gasifying agent supply pipes 40 are shown to be provided only at two locations, but are appropriately provided at predetermined locations, and even at one location or at multiple locations. Also good.
次に、上記した本発明によるバイオマスガス化装置１におけるバイオマスガス化方法について説明する。 Next, a biomass gasification method in the biomass gasification apparatus 1 according to the present invention described above will be described.
原料バイオマスは、破砕されて原料バイオマス供給管３５から反応容器１０内に投入される。ここで原料バイオマスはこれに限定されるものではないが、破砕などの前処理の容易な稲藁、麦わら等のソフトバイオマスや、スギ等の木質バイオマスが好ましい。特に、ソフトバイオマスは、前処理に必要なエネルギーを低減出来るため好ましい。なお、原料バイオマスの粒径が大であると、部分酸化反応及び熱分解反応の効率が下がり、チャーの生成量が増加して水素、一酸化炭素、二酸化炭素を主成分とする合成ガスの収率を低下させてしまう。故に、適宜、原料バイオマスの破砕粒径を調整して原料バイオマス供給管３５に導かれる。 The raw material biomass is crushed and charged into the reaction vessel 10 from the raw material biomass supply pipe 35. Here, the raw material biomass is not limited to this, but soft biomass such as rice straw and straw that can be easily pretreated such as crushing, and woody biomass such as cedar are preferable. In particular, soft biomass is preferable because energy required for pretreatment can be reduced. When the particle size of the raw material biomass is large, the efficiency of the partial oxidation reaction and the thermal decomposition reaction decreases, and the amount of char generated increases, so that the synthesis gas containing hydrogen, carbon monoxide, and carbon dioxide as the main component can be collected. Will reduce the rate. Therefore, the crushed particle size of the raw material biomass is appropriately adjusted and guided to the raw material biomass supply pipe 35.
原料バイオマス供給管３５から反応容器１０内に投入された破砕された原料バイオマスは、筒状反応容器２０の側面を包絡するようにして落下する落下流路Ｆを形成する。落下流路Ｆを形成するために、図示しないコンベアやふるいを反応容器１０内の蓋部１０ａ近傍に設けることも出来る。また、筒状反応容器２０の外側に落下流路Ｆの流れを制御するとともに、伝熱効率を向上させるフィンなどを設置しても良い。 The crushed raw material biomass charged into the reaction vessel 10 from the raw material biomass supply pipe 35 forms a falling flow path F that falls so as to enclose the side surface of the cylindrical reaction vessel 20. In order to form the falling flow path F, a conveyor or sieve (not shown) can be provided in the vicinity of the lid portion 10a in the reaction vessel 10. Further, a fin or the like for controlling the flow of the falling flow path F and improving the heat transfer efficiency may be installed outside the cylindrical reaction vessel 20.
一方、酸素や空気などの酸化ガス化剤をガス化剤供給管４０から反応容器１０内に導入する。原料バイオマスの落下流路Ｆに酸化ガス化剤が供給されると、原料バイオマスが落下流路Ｆ内を落下しながらその一部が燃焼し、部分酸化反応及び熱分解反応を生じて反応ガスを生成する（図１の化学反応Ｒ１を参照）。反応ガスは、タールを含む揮発性の炭化水素及び水素、一酸化炭素、二酸化炭素などからなる。一方、同時に、チャーや灰分などの固体成分を生成する。このとき、原料バイオマスが落下しながらばらけるので、ゴミやチャー、灰分などの固体成分がすみやかに分離できる。故に、酸化ガス化剤と原料バイオマスとが効率よく反応して生成ガスを得られて、原料バイオマスの燃焼が少なくとも部分酸化のための熱を安定して得ることが出来るのである。 On the other hand, an oxidizing gasifying agent such as oxygen or air is introduced into the reaction vessel 10 from the gasifying agent supply pipe 40. When the oxidizing gasifying agent is supplied to the falling flow path F of the raw material biomass, a part of the raw material biomass burns while falling in the falling flow path F, and a partial oxidation reaction and a thermal decomposition reaction occur to generate a reaction gas. (See chemical reaction R1 in FIG. 1). The reaction gas is composed of volatile hydrocarbons including tar and hydrogen, carbon monoxide, carbon dioxide, and the like. At the same time, solid components such as char and ash are generated. At this time, since raw material biomass falls while falling, solid components such as garbage, char, and ash can be promptly separated. Therefore, the oxidizing gasifying agent and the raw material biomass react efficiently to obtain a product gas, and the combustion of the raw material biomass can stably obtain at least heat for partial oxidation.
なお、酸化ガス化剤の噴射圧力及び噴射方向によって、原料バイオマスの落下流路Ｆを変化させ得るので、適宜、ガス化剤供給管４０の位置などが調整され得る。 In addition, since the falling flow path F of raw material biomass can be changed with the injection pressure and injection direction of an oxidizing gasification agent, the position of the gasification agent supply pipe 40 and the like can be adjusted as appropriate.
ところで、原料バイオマスは、落下流路Ｆを落下しながら、気体成分である生成ガスと固体成分とに分離され、固体成分は自重によって反応容器１０の底部の堆積槽１０ｃ内に落下していく。一方、気体成分は、水蒸気供給管１５の開口１５ａから吐出される水蒸気に巻き込まれるようにして、触媒２５へ仕向けられ、図示しない改質触媒に接触する。 By the way, the raw material biomass is separated into a product gas and a solid component which are gas components while falling in the falling flow path F, and the solid components fall into the deposition tank 10c at the bottom of the reaction vessel 10 by its own weight. On the other hand, the gas component is directed to the catalyst 25 so as to be caught in the water vapor discharged from the opening 15a of the water vapor supply pipe 15, and contacts a reforming catalyst (not shown).
ここで、触媒２５は、伝熱隔壁としての筒状反応容器２０の先端部２０ｂによってその側部を覆われているから、原料バイオマスの落下流路Ｆ内に配置されていても、未燃焼の原料バイオマスや固体成分をその多孔質部に詰まらせてしまうことがない。仮に、これらが触媒２５に付着してしまったとしても、水蒸気供給管１５から所定の圧力を掛けた水蒸気を触媒２５に向けて吹き付けることができて、クリーニングが可能である。 Here, since the side part of the catalyst 25 is covered with the tip part 20b of the cylindrical reaction vessel 20 as a heat transfer partition wall, it is not burned even if it is disposed in the raw material biomass falling flow path F. Raw material biomass and solid components are not clogged in the porous portion. Even if they adhere to the catalyst 25, the steam supplied with a predetermined pressure can be sprayed from the steam supply pipe 15 toward the catalyst 25, and cleaning is possible.
更に、触媒２５は、原料バイオマスの落下流路Ｆ内に配置されているから、原料バイオマスの部分酸化及び熱分解による熱がこれに与えられる。つまり、筒状反応容器２０の触媒２５では、気体成分中のタールと炭化水素が熱を与えられながら水素、一酸化炭素及び二酸化炭素に水蒸気改質される（図１の化学反応Ｒ２参照）。この水蒸気改質によって得られた水素、一酸化炭素及び二酸化炭素からなる合成ガスは、筒状反応容器２０を介して反応容器１０の外部に取り出されて、適宜、公知の利用法で使用され得る。 Furthermore, since the catalyst 25 is disposed in the falling flow path F of the raw material biomass, heat from the partial oxidation and thermal decomposition of the raw material biomass is given thereto. That is, in the catalyst 25 of the cylindrical reaction vessel 20, tar and hydrocarbon in the gas component are steam reformed to hydrogen, carbon monoxide and carbon dioxide while being heated (see chemical reaction R2 in FIG. 1). The synthesis gas composed of hydrogen, carbon monoxide and carbon dioxide obtained by the steam reforming is taken out of the reaction vessel 10 through the cylindrical reaction vessel 20 and can be used in a known usage as appropriate. .
ここで、原料バイオマスは、Ｃ１．０〜１．５Ｈ２Ｏ０．７〜１．１のように表され、１つの例としてＣ６Ｈ１０Ｏ５で表される。反応熱Ｑｎ＞０とすると、
熱分解反応：
Ｃ６Ｈ１０Ｏ５ → ５ＣＯ＋５Ｈ２＋Ｃ−Ｑ１（吸熱）
Ｃ６Ｈ１０Ｏ５ → ５ＣＯ＋ＣＨ４＋３Ｈ２−Ｑ２（吸熱）
Ｃ６Ｈ１０Ｏ５ → ３ＣＯ＋ＣＯ２＋２ＣＨ４＋Ｈ２＋Ｑ３（発熱）
部分酸化反応：
Ｃ６Ｈ１０Ｏ５＋１／２Ｏ２ → ６ＣＯ＋５Ｈ２−Ｑ４（吸熱）
Ｃ６Ｈ１０Ｏ５＋Ｏ２ → ５ＣＯ＋ＣＯ２＋５Ｈ２＋Ｑ５（発熱）
Ｃ６Ｈ１０Ｏ５＋２Ｏ２ → ３ＣＯ＋３ＣＯ２＋５Ｈ２＋Ｑ６（発熱）
水蒸気改質反応：
Ｃ６Ｈ１０Ｏ５＋Ｈ２Ｏ → ６ＣＯ＋６Ｈ２−Ｑ７（吸熱）
Ｃ６Ｈ１０Ｏ５＋３Ｈ２Ｏ → ４ＣＯ＋２ＣＯ２＋８Ｈ２−Ｑ８（吸熱）
Ｃ６Ｈ１０Ｏ５＋７Ｈ２Ｏ → ６ＣＯ＋１２Ｈ２−Ｑ９（吸熱）
と表すことが出来る。つまり、熱分解反応、部分酸化反応及び水蒸気改質反応は、いくつかの化学反応から構成され、どの化学反応が支配的になるかは、温度（熱供給量）、ガス化剤の量、水の量、及び、原料バイオマスの組成などによって決定される。換言すれば、これらを制御することで化学反応を制御できる。また、実用上、反応速度をなるべく高めて化学反応の進行を促進させることが好ましい。触媒はかかる効果を与える。
Here, raw material biomass is represented as C 1.0-1.5 H 2 O 0.7-1.1 , and is represented by C 6 H 10 O 5 as one example. If the reaction heat Q n > 0,
Thermal decomposition reaction:
C 6 H 10 O 5 → 5CO + 5H 2 + C-Q 1 (endothermic)
C 6 H 10 O 5 → 5CO + CH 4 + 3H 2 -Q 2 (endothermic)
C 6 H 10 O 5 → 3CO + CO 2 + 2CH 4 + H 2 + Q 3 (exotherm)
Partial oxidation reaction:
C 6 H 10 O 5 + 1 / 2O 2 → 6CO + 5H 2 -Q 4 ( endothermic)
C 6 H 10 O 5 + O 2 → 5CO + CO 2 + 5H 2 + Q 5 (exothermic)
C 6 H 10 O 5 + 2O 2 → 3CO + 3CO 2 + 5H 2 + Q 6 (exotherm)
Steam reforming reaction:
C 6 H 10 O 5 + H 2 O → 6CO + 6H 2 -Q 7 ( endothermic)
C 6 H 10 O 5 + 3H 2 O → 4CO + 2CO 2 + 8H 2 -Q 8 ( endothermic)
C 6 H 10 O 5 + 7H 2 O → 6CO + 12H 2 -Q 9 ( endothermic)
Can be expressed as In other words, the thermal decomposition reaction, partial oxidation reaction and steam reforming reaction are composed of several chemical reactions. Which chemical reaction is dominant depends on temperature (heat supply amount), amount of gasifying agent, water And the composition of the raw material biomass. In other words, the chemical reaction can be controlled by controlling these. In practice, it is preferable to promote the progress of the chemical reaction by increasing the reaction rate as much as possible. The catalyst provides such an effect.
例えば、ガス化剤供給管４０の位置や酸化ガス化剤の噴射方向を変化させると、Ｏ２の供給量を変化させ得るから、特に、部分酸化反応の化学反応を制御できる。故に、原料落下流路Ｆに沿った温度分布を変化させ得る。また、酸化ガス化剤の温度を変化させても原料落下流路Ｆに沿った温度分布を制御できる。つまり、触媒２５における部分酸化反応及び熱分解反応による熱の供給量を調整できるので、結果として、水蒸気改質反応を制御できる。 For example, when the position of the gasifying agent supply pipe 40 or the injection direction of the oxidizing gasifying agent is changed, the supply amount of O 2 can be changed, and therefore, the chemical reaction of the partial oxidation reaction can be controlled. Therefore, the temperature distribution along the raw material falling flow path F can be changed. Further, even if the temperature of the oxidizing gasifying agent is changed, the temperature distribution along the material dropping flow path F can be controlled. That is, the amount of heat supplied by the partial oxidation reaction and thermal decomposition reaction in the catalyst 25 can be adjusted, and as a result, the steam reforming reaction can be controlled.
次に、上記した本発明の１つの実施例における装置の運転の詳細検討結果について説明する。 Next, a detailed examination result of the operation of the apparatus in the above-described embodiment of the present invention will be described.
５ｍｍ以下に破砕した稲藁及び籾殻の混合物を原料バイオマス供給管３５から反応容器１０内に４０ｋｇ／ｈの量で投入した。一方、ガス化剤供給管４０から酸素を反応容器１０内に導入した。連続運転に至ると、反応容器１０内の温度は６００〜８００℃程度に維持された。この状態で、水蒸気供給管１５から供給される水蒸気量をＨ２Ｏ／Ｃ比率を３〜３．５程度で変化させると、筒状反応容器２０から取り出される合成ガスにおいて、一酸化炭素が約１５００〜２０００ｌ／ｈ、水素が約３０００〜４０００ｌ／ｈほどの間で変化して得られた。すなわち、Ｈ２／ＣＯ比を２以上に高めることが出来た。なお、酸素に替えて酸素富化空気を用いても、同様に高いＨ２／ＣＯ比を得られた。 A mixture of rice straw and rice husk crushed to 5 mm or less was introduced into the reaction vessel 10 from the raw material biomass supply pipe 35 in an amount of 40 kg / h. On the other hand, oxygen was introduced into the reaction vessel 10 from the gasifying agent supply pipe 40. When the continuous operation was reached, the temperature in the reaction vessel 10 was maintained at about 600 to 800 ° C. In this state, when the amount of water vapor supplied from the water vapor supply pipe 15 is changed at a H 2 O / C ratio of about 3 to 3.5, the carbon monoxide is reduced by about 3% in the synthesis gas taken out from the cylindrical reaction vessel 20. 1500 to 2000 l / h, hydrogen was obtained by changing between about 3000 to 4000 l / h. That is, the H 2 / CO ratio could be increased to 2 or higher. Even when oxygen-enriched air was used in place of oxygen, a high H 2 / CO ratio was obtained.
かかる実施例では、原料バイオマスの７０〜９０％がガス化されている計算となる。通常のガス化プロセスでは原料バイオマスの６０％程度を燃焼させて反応に必要な熱エネルギーを得ている。一方、本実施例では反応容器１０内の維持温度が低くとも、高い収率で合成ガスを得ることができる。換言すれば、原料バイオマスの１０〜３０％程度を燃焼させるだけで合成ガスを得るための熱エネルギーを得ることが出来るから、高い収率で合成ガスを得ることが出来る。 In such an example, the calculation is such that 70 to 90% of the raw material biomass is gasified. In a normal gasification process, about 60% of raw material biomass is burned to obtain thermal energy necessary for the reaction. On the other hand, in this embodiment, even if the maintenance temperature in the reaction vessel 10 is low, the synthesis gas can be obtained with a high yield. In other words, the thermal energy for obtaining the synthesis gas can be obtained simply by burning about 10 to 30% of the raw material biomass, so that the synthesis gas can be obtained with a high yield.
以上、本実施例によれば、高い収率で合成ガスを得ることが出来る。また、装置をコンパクトにすることが出来る。更に、合成ガスにおいて高いＨ２／ＣＯ比率、特にこれを２よりも大きくすることが出来る。 As mentioned above, according to the present Example, synthesis gas can be obtained with a high yield. In addition, the apparatus can be made compact. Furthermore, a high H 2 / CO ratio in the synthesis gas, in particular this can be greater than 2.
以上、本発明による代表的実施例及びこれに基づく変形例を述べたが、本発明は必ずしもこれらに限定されるものではなく、各部位の形状や、反応容器、触媒等の材料も適宜、当業者によって変更され得る。すなわち、当業者であれば、添付した特許請求の範囲を逸脱することなく、種々の代替実施例及び改変例を見出すことが出来るであろう。 As mentioned above, although the typical example by this invention and the modification based on this were described, this invention is not necessarily limited to these, The shape of each site | part, materials, such as a reaction container and a catalyst, are also appropriate. It can be changed by a vendor. That is, those skilled in the art will be able to find various alternative embodiments and modifications without departing from the scope of the appended claims.
１０ 反応容器
１０ａ 反応容器蓋部
１０ｂ 反応容器傾斜部
１０ｃ 堆積槽
１５ 水蒸気供給管
１５ａ 水蒸気供給管開口部
２０ 筒状反応容器
２０ａ 筒状反応容器開口
２０ｂ 筒状反応容器先端部
２５ 触媒
２５ａ 格子板
３５ 原料バイオマス供給管
３５ａ 原料バイオマス供給管開口部
４０ ガス化剤供給管
Ｆ 原料バイオマス落下流路
Ｍ 中心軸線
DESCRIPTION OF SYMBOLS 10 Reaction container 10a Reaction container cover part 10b Reaction container inclination part 10c Deposition tank 15 Steam supply pipe 15a Steam supply pipe opening 20 Cylindrical reaction container 20a Cylindrical reaction container opening 20b Cylindrical reaction container front-end | tip part 25 Catalyst 25a Grid plate 35 Raw material biomass supply pipe 35a Raw material biomass supply pipe opening 40 Gasifying agent supply pipe F Raw material biomass drop channel M Center axis
Claims (8)
前記原料バイオマスを落下させながら酸化ガス化剤と反応させて前記生成ガスを生じさせるための第１反応容器と、
前記第１反応容器内の前記原料バイオマスの落下流路に向けて前記酸化ガス化剤を導くためのガス化剤供給管と、
前記第１反応容器内にあって開口から前記生成ガスを水蒸気とともにその内部に導いて前記合成ガスを得るための第２反応容器と、
前記第２反応容器に前記水蒸気を供給するための水蒸気供給管と、からなり、
伝熱隔壁によって前記第１反応容器内の空間と画定された前記第２反応容器内の反応空間は改質触媒を装填されているとともに前記原料バイオマスの落下流路内に配置されて、前記生成ガスの反応で生じる熱を前記合成ガスの反応に利用可能とさせることを特徴とするバイオマスガス化装置。 A biomass gasification apparatus for obtaining a synthesis gas by steam reforming a product gas obtained by partially oxidizing raw material biomass,
A first reaction vessel to produce the product gas with an oxidizing gas agent while dropping the raw biomass,
A gasifying agent supply pipe for guiding the oxidizing gasifying agent toward the falling flow path of the raw material biomass in the first reaction vessel;
A second reaction vessel in the first reaction vessel for obtaining the synthesis gas by introducing the product gas into the interior together with water vapor from an opening ;
A water vapor supply pipe for supplying the water vapor to the second reaction vessel,
Reaction space of the second reaction vessel by heat transfer partition wall defined between space of the first reaction vessel disposed falling flow path of the raw biomass with being loaded with reforming catalyst, wherein the product biomass gasification apparatus according to claim Rukoto is available heat generated by the reaction gas into the reaction of the synthesis gas.
前記原料バイオマスを第１反応容器内にて落下させながら落下流路に向けて酸化ガス化剤を導きこれと反応させる第１の反応ステップと、
前記第１の反応ステップで生じた生成ガスを水蒸気とともに前記第１反応容器内の第２反応容器の開口から内部に導いて水蒸気改質を行って前記合成ガスを得る第２の反応ステップと、からなり、
伝熱隔壁によって前記第１反応容器内の空間と画定された前記第２反応容器内の反応空間は改質触媒を装填されているとともに前記原料バイオマスの落下流路内に配置されて、
前記第２の反応ステップは前記生成ガスの反応で生ずる熱を前記合成ガスの反応に利用することを特徴とするバイオマスガス化方法。 A biomass gasification method for obtaining a synthesis gas by steam reforming a product gas obtained by partially oxidizing raw material biomass,
A first reaction step of reacting with-out guide the acid gases agent towards the falling flow path while dropping the raw biomass at the first reaction vessel,
A second reaction step in which the product gas generated in the first reaction step is introduced together with water vapor from the opening of the second reaction vessel in the first reaction vessel to perform steam reforming to obtain the synthesis gas; Consists of
Reaction space of the second reaction vessel by heat transfer partition wall defined between space of the first reaction vessel disposed falling flow path of the raw biomass with being loaded with reforming catalyst,
The biomass gasification method, wherein the second reaction step uses heat generated by the reaction of the product gas for the reaction of the synthesis gas .
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| DE102014005207A1 (en) * | 2014-04-09 | 2015-10-15 | Michael Niederbacher | Process and installation for the purification of contaminated environmental fallout, in particular for reducing the radiation load of radioactively contaminated environmental fallow |
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