JP2014240472A - Method and apparatus for coal/biomass co-gasification by improved three-column type circulated fluidized bed - Google Patents

Method and apparatus for coal/biomass co-gasification by improved three-column type circulated fluidized bed Download PDF

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JP2014240472A
JP2014240472A JP2013124183A JP2013124183A JP2014240472A JP 2014240472 A JP2014240472 A JP 2014240472A JP 2013124183 A JP2013124183 A JP 2013124183A JP 2013124183 A JP2013124183 A JP 2013124183A JP 2014240472 A JP2014240472 A JP 2014240472A
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tower
gasification
gas
cao
fluidized bed
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JP6304856B2 (en
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林　石英
Sekiei Hayashi
石英 林
貴司 中村
Takashi Nakamura
貴司 中村
宮地　健
Takeshi Miyaji
健 宮地
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JAPAN COAL ENERGY CENTER (JCOAL)
JAPAN COAL ENERGY CT JCOAL
Mitsui Engineering and Shipbuilding Co Ltd
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JAPAN COAL ENERGY CT JCOAL
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Abstract

PROBLEM TO BE SOLVED: To provide a method and apparatus for gasification which improve the selectivity and yield of a fuel synthesis process by converting decomposable hydrocarbon gases e.g. CHproduced in a gasification process and a liquid fuel synthesis process, into a synthetic gas.SOLUTION: A three-column type circulation fluidized bed gasification method uses a fluidized combustion column 120, a fluidized bed modification column 130, a fluidized bed gasification column 110 and a low-temperature sulfur re-absorber 150. A gasification gas is introduced into the modification column 130 to subject slightly decomposable hydrocarbons, e.g. methane, in the gas to catalyst modification to decompose into CO and Has synthetic gas. Liquid fuel synthesis is carried out, and off-gas and heavy residue which are not converted into liquid fuels are returned to the fluidized bed modification column 130 and/or the gasification column 110.

Description

本発明は、改質塔及び低温硫黄再吸収器を用いたガス化方法及びガス化装置に関する。   The present invention relates to a gasification method and a gasification apparatus using a reforming tower and a low-temperature sulfur reabsorber.

近年、バイオマス、石炭、廃棄物、石油残渣、重質油等の種々の有機物原料をガス化することにより合成ガスを製造する技術が提案されるようになってきている。
図１は二塔式と称されるガス化設備の一例を示すものであり、このようなガス化設備の代表例としては特許文献１がある。
特許文献1によれば、このガス化設備においては、流動層ガス化炉１に供給される原料２は、例えば800℃以上の高温を有して供給される循環粒子３（砂等）と、下部から供給される水蒸気、空気、酸素、二酸化炭素等のガス化剤４とにより形成される流動層５によって流動加熱され、ガス化されてガス化ガス６を生成する。流動層ガス化炉１で生成したガス化ガス６は、サイクロン等の分離器７に導いて固形分を除去した後、タール除去装置、電気集塵機等の精製装置を経た後、発電設備の燃料として供給したり、合成ガス原料として供給したり、或いは圧縮機で圧縮して液化したガス製品として取り出すようにしている。 In recent years, techniques for producing synthesis gas by gasifying various organic raw materials such as biomass, coal, waste, petroleum residue, heavy oil and the like have been proposed.
FIG. 1 shows an example of a gasification facility called a two-column type, and Patent Document 1 is a typical example of such a gasification facility.
According to Patent Document 1, in this gasification facility, the raw material 2 supplied to the fluidized bed gasification furnace 1 is, for example, circulating particles 3 (sand etc.) supplied at a high temperature of 800 ° C. or higher, The gasified gas 6 is generated by being heated and fluidized by the fluidized bed 5 formed by the gasifying agent 4 such as water vapor, air, oxygen, carbon dioxide supplied from the lower part. The gasified gas 6 generated in the fluidized bed gasification furnace 1 is guided to a separator 7 such as a cyclone to remove solids, and then passes through a refining device such as a tar removal device and an electric dust collector, and then used as fuel for power generation equipment. They are supplied, supplied as a synthesis gas raw material, or taken out as a gas product compressed and liquefied by a compressor.

流動層ガス化炉１において原料２をガス化する際に生成したチャーは、循環粒子３と共に流動層燃焼炉８に供給され、流動層燃焼炉８において空気又は酸素等の酸化剤９の供給によりチャーを燃焼することによって循環粒子を例えば900℃以上の温度に加熱するようにしている。流動層燃焼炉８から導出される燃焼ガス１０はサイクロン等の分離器１１に導かれて循環粒子３と排ガス１２とに分離され、分離した循環粒子３は前記流動層５に没入した降下管Ａにより流動層ガス化炉１に供給するようにしている。又、分離器１１で分離した排ガス１２は、熱回収用の熱交換器１３等を経てバグフィルター等の集塵器により集塵されて煙突に導かれる。
 前記流動層ガス化炉１においては、原料２が流動層５により加熱されて、熱分解により熱分解ガスを生成する熱分解反応と、熱分解残渣がガス化剤４の作用を受けて改質ガス化ガスを生成する改質ガス化反応とが混在した状態で起こっている。
熱分解反応では、メタンCH４、タール等の炭化水素や、その他一酸化炭素CO、二酸化炭素CO２、水素H２ 等を含む熱分解ガスが生成され、改質ガス化反応では、水蒸気ガス化の場合は一酸化炭素CO、水素H２を主成分とする改質ガス化ガスが生成される。しかし、前記熱分解ガスには多くのタールが含まれており、前記したように流動層ガス化炉１において熱分解反応と改質ガス化反応が同時に行われる従来のガス化設備においては、熱分解反応によって生成した熱分解ガスが、改質ガス化反応を阻害するという問題があることが判明した。 The char generated when the raw material 2 is gasified in the fluidized bed gasification furnace 1 is supplied to the fluidized bed combustion furnace 8 together with the circulating particles 3, and the fluidized bed combustion furnace 8 is supplied with an oxidant 9 such as air or oxygen. The circulating particles are heated to a temperature of, for example, 900 ° C. or more by burning the char. The combustion gas 10 led out from the fluidized bed combustion furnace 8 is guided to a separator 11 such as a cyclone and separated into the circulating particles 3 and the exhaust gas 12, and the separated circulating particles 3 are the downcomer A immersed in the fluidized bed 5. Thus, the fluidized bed gasification furnace 1 is supplied. The exhaust gas 12 separated by the separator 11 is collected by a dust collector such as a bag filter through a heat exchanger 13 for heat recovery and the like and guided to a chimney.
  In the fluidized bed gasification furnace 1, the raw material 2 is heated by the fluidized bed 5 to generate a pyrolysis gas by pyrolysis, and the pyrolysis residue acts as a gasifying agent 4. It occurs in a mixed state with the reformed gasification reaction that receives the reformed gasification gas.
In the pyrolysis reaction, pyrolysis gas containing hydrocarbons such as methane CH 4 and tar and other carbon monoxide CO, carbon dioxide CO 2 , hydrogen H 2 and the like is generated. In the reforming gasification reaction, steam gasification is performed. In this case, reformed gasification gas mainly containing carbon monoxide CO and hydrogen H 2 is generated. However, the pyrolysis gas contains a large amount of tar, and in the conventional gasification facility in which the pyrolysis reaction and the reforming gasification reaction are simultaneously performed in the fluidized bed gasification furnace 1 as described above, It has been found that there is a problem that the pyrolysis gas generated by the decomposition reaction inhibits the reformed gasification reaction.

そこで、特許文献２では、図２に示すように、循環粒子とガス化剤の存在下で原料をガス化するガス化炉と、ガス化炉でのガス化時に生成したチャーを導入して燃焼することにより循環粒子を加熱する燃焼炉と、燃焼炉からの燃焼ガスを分離器に導いて排ガスと循環粒子とに分離し循環粒子を前記ガス化炉に戻すようにしているガス化設備であって、分離器で分離した循環粒子を粒子移動部内に移動させつつ原料供給装置から原料を供給して原料を熱分解させ、熱分解ガス取出口により熱分解ガスを取り出すと共に、熱分解残渣を前記ガス化炉に供給する熱分解装置を備えたことを特徴とするガス化設備が提案された。 Therefore, in Patent Document 2, as shown in FIG. 2, combustion is performed by introducing a gasification furnace that gasifies a raw material in the presence of circulating particles and a gasifying agent, and char generated during gasification in the gasification furnace. A combustion furnace that heats the circulating particles, and a gasification facility that directs the combustion gas from the combustion furnace to a separator to separate the exhaust gas and the circulating particles and return the circulating particles to the gasification furnace. Then, while moving the circulating particles separated by the separator into the particle moving part, the raw material is supplied from the raw material supply device to thermally decompose the raw material, the pyrolysis gas is taken out from the pyrolysis gas outlet, and the pyrolysis residue is A gasification facility characterized in that it is provided with a thermal decomposition apparatus for supplying to a gasification furnace has been proposed.

このように構成することにより、分離器１１と流動層ガス化炉１との間に熱分解装置１４を備えた構成としている。熱分解装置１４は、分離器１１によって分離した循環粒子３を粒子移動部１５内で移動させつつ原料供給装置１６により原料２を供給して原料を熱分解させる一方、ガス導入装置１７により上昇流形成ガス１８を供給して熱分解ガスを上昇させ、熱分解残渣を循環粒子３と共に前記流動層ガス化炉１に供給するようにしている。更に、前記熱分解装置１４には熱分解ガス１９を取り出すための熱分解ガス取出口２０を備えている。尚、図２では熱分解装置１４に、ガス導入装置１７により上昇流形成ガス１８を供給しているが、上昇流形成ガス１８は供給しなくてもよい。
即ち、図２に示すように、分離器１１で分離された循環粒子３は流動層５に没入した降下管Ａによってシールされて流動層ガス化炉１に供給されるため、降下管Ａ内で発生した熱分解ガス１９は自身の圧力によって上昇し熱分解ガス取出口２０から取り出されるようになる。そのため、流動層ガス化炉１には、熱分解装置１４によって分解された後の熱分解残渣が供給されるので、流動層ガス化炉１では熱分解ガスがほとんど生成されないため、熱分解ガスによる阻害をあまり受けることなく良好な改質ガス化反応が行われる。
しかしながら、まだまだ不十分であり、長時間使用すると生成したタールが熱交換器で目詰まりを起こす事態が発生し、運転に支障をきたしているのが現状である。
このため発明者は、すでに、温度900℃〜1000℃で運転する流動層燃焼塔と温度900℃〜1000℃で運転する流動層タール改質塔と温度700℃〜800℃で運転する流動層ガス化塔からなる三塔式循環流動層ガス化方法（図３）を考案し、CaOを伝熱媒体、タール改質触媒及びCO2とH2Sの吸収剤として、三塔を結ぶ装置内で循環させ、バイオマスや石炭等固体燃料と高温水蒸気をガス化塔に供給し、700-850℃の熱媒体と接触して熱分解を起こし、揮発分ガスとチャー（固定炭素）を生成し、チャーの一部は水蒸気とガス化してガス化ガスを生成し、揮発分とガス化ガスと水蒸気はタール改質塔に導入し、900-1000℃のCaO熱媒体と接触してタールの触媒改質を行い、残ったチャーは熱媒体と共に燃焼塔に導入し、空気でチャーを燃焼させ、熱媒体を加熱し、熱媒体はサイクロンを経てタール改質塔とガス化塔に戻り、タール改質塔とガス化塔の温度を維持する三塔式循環流動層ガス化方法を提案している（特許文献３特願2012−223683）。
また、固体燃料とガス化剤とを熱分解ガス化フェーズ反応器に供給し、該熱分解ガス化フェーズ反応器内において、熱媒体との接触により前記固体燃料を熱分解して生成したチャーを前記ガス化剤によりガス化し、該熱分解とガス化により生成されるガス化ガス中のCO２を所定該フェーズの反応温度下で活性ケミカルにより吸収する第一工程と、前記熱分解ガス化フェーズ反応器内でガス化し切れず残留したチャー、前記固体燃料の熱分解とガス化に寄与して低温化した熱媒体、前記CO２と反応して低活性化した低活性ケミカル及び新添加の未活性ケミカルをチャー燃焼フェーズ反応器に供給し、該チャー燃焼フェーズ反応器内において、酸化剤により前記チャーを燃焼させ、該燃焼熱で前記低温化した熱媒体を加熱するとともに、前記低活性ケミカルを焼成して再活性化し且つ前記未活性ケミカルを焼成して活性化する第二工程と、前記チャー燃焼フェーズ反応器内で加熱された熱媒体と活性化した活性ケミカルとともに前記熱分解ガス化フェーズ反応器から前記ガス化ガスをガス化ガス精製フェーズ反応器に供給し、該ガス化ガス精製フェーズ反応器内において、前記活性ケミカルを触媒として機能させて前記ガス化ガス中のタールを所定該フェーズの反応温度下で改質するとともに前記ガス化ガス中のH2S、HClを吸収して前記ガス化ガスを精製し、該ガス化ガスの精製に主に触媒として寄与した活性ケミカルを熱媒体とともに前記熱分解ガス化フェーズ反応器に循環させる第三工程と、からなることを特徴とする固体燃料のガス化方法が知られている（特許文献４）。しかし、ここでは、タールの改質が行われているものの、ガス化ガス及び液体燃料合成過程のオフガス中のメタン等難分解炭化水素(CnHm)ガスを水と反応させて合成ガスを得、並びにH2S、COS及びCO2ガスを徹底的に低減させる技術思想は開示されていない。 By comprising in this way, it is set as the structure provided with the thermal decomposition apparatus 14 between the separator 11 and the fluidized bed gasification furnace 1. FIG. The pyrolysis device 14 supplies the raw material 2 by the raw material supply device 16 while moving the circulating particles 3 separated by the separator 11 in the particle moving unit 15, and pyrolyzes the raw material, while the gas introduction device 17 causes the upward flow. The forming gas 18 is supplied to raise the pyrolysis gas, and the pyrolysis residue is supplied to the fluidized bed gasification furnace 1 together with the circulating particles 3. Further, the pyrolysis device 14 is provided with a pyrolysis gas outlet 20 for taking out the pyrolysis gas 19. In FIG. 2, the upward flow forming gas 18 is supplied to the thermal decomposition apparatus 14 by the gas introduction device 17, but the upward flow forming gas 18 may not be supplied.
That is, as shown in FIG. 2, since the circulating particles 3 separated by the separator 11 are sealed by the downcomer A immersed in the fluidized bed 5 and supplied to the fluidized bed gasifier 1, The generated pyrolysis gas 19 rises by its own pressure and is taken out from the pyrolysis gas outlet 20. Therefore, since the thermal decomposition residue after being decomposed by the thermal decomposition apparatus 14 is supplied to the fluidized bed gasification furnace 1, almost no thermal decomposition gas is generated in the fluidized bed gasification furnace 1. A good reforming gasification reaction is performed without much inhibition.
However, the situation is still insufficient, and when the product is used for a long time, the generated tar is clogged with the heat exchanger, resulting in trouble in operation.
For this reason, the inventor already has a fluidized bed combustion tower operating at a temperature of 900 ° C to 1000 ° C, a fluidized bed tar reforming tower operating at a temperature of 900 ° C to 1000 ° C, and a fluidized bed gas operating at a temperature of 700 ° C to 800 ° C. Devised a three-column circulating fluidized bed gasification method (Fig. 3) consisting of gasification towers, using CaO as the heat transfer medium, tar reforming catalyst, and CO 2 and H 2 S absorbent in the equipment connecting the three towers Circulate and supply biomass fuel, coal and other solid fuel and high-temperature steam to the gasification tower, and contact with a heat medium of 700-850 ℃ to cause pyrolysis, and generate volatile gas and char (fixed carbon). A part of the gas is gasified with water vapor to produce gasified gas, and the volatile matter, gasified gas and water vapor are introduced into a tar reforming tower and contacted with a 900-1000 ° C CaO heat medium to catalytically reform tar. The remaining char is introduced into the combustion tower together with the heat medium, the char is burned with air, the heat medium is heated, A three-column circulating fluidized bed gasification method has been proposed in which the temperature of the tar reforming tower and the gasification tower is maintained by returning to the tar reforming tower and the gasification tower through the icron (Japanese Patent Application No. 2012-223683). ).
In addition, a solid fuel and a gasifying agent are supplied to a pyrolysis gasification phase reactor, and char generated by pyrolyzing the solid fuel by contact with a heat medium in the pyrolysis gasification phase reactor is obtained. Gasification by the gasifying agent, and a first step of absorbing CO 2 in the gasification gas generated by the pyrolysis and gasification with an active chemical under a reaction temperature of the predetermined phase; and the pyrolysis gasification phase Char remaining in the reactor without being completely gasified, a heat medium that has been reduced in temperature by contributing to thermal decomposition and gasification of the solid fuel, a low activity chemical that has been activated by reacting with the CO 2 and an unadded An active chemical is supplied to the char combustion phase reactor, and the char is combusted by an oxidant in the char combustion phase reactor, and the low-temperature heat medium is heated by the combustion heat, and the low activity A second step of calcination and reactivation of the chemical and calcination and activation of the inactive chemical, and the pyrolysis gasification together with the heat medium heated in the char combustion phase reactor and the activated active chemical. The gasification gas is supplied from the phase reactor to the gasification gas purification phase reactor, and the active chemical functions as a catalyst in the gasification gas purification phase reactor so that the tar in the gasification gas is predetermined. While reforming at the reaction temperature of the phase and absorbing H 2 S and HCl in the gasification gas, the gasification gas is purified, and the active chemical that has contributed mainly as a catalyst to the purification of the gasification gas is heated. A solid fuel gasification method characterized by comprising a third step of circulating to the pyrolysis gasification phase reactor together with a medium is known (Patent Document 4). However, although tar reforming is being carried out here, the synthesis gas is produced by reacting gas such as methane and other indestructible hydrocarbon (C n H m ) gas in the off-gas of the liquid fuel synthesis process with water. obtained, as well as H2 S, the technical idea for thoroughly reducing COS and CO 2 gas is not disclosed.

特開2005−41959号公報Japanese Unexamined Patent Publication No. 2005-41959 特開2011−26413号公報JP 2011-26413 A 特願2012−223683Japanese Patent Application 2012-223683 特開2007−16061号公報JP 2007-16061

炭酸ガス排出量低減のため、再生可能エネルギー源であるバイオマス資源を用いた液体燃料製造の導入は大切であるが、バイオマス利用技術にとって、以下の問題点を克服しなければならない。
（１）ガス化原料の安定供給
化学プラントの運転にとって、プラント負荷の安定、長時間運転が要求される。過大な負荷変動や、頻繁な起動停止は設備損傷や生産性低下を与えるだけではなく、起動停止時の補助燃料の過剰投入により、CO2排出増にもなる。
（２）バイオマスガス化への熱供給
高カロリー燃料または合成ガスを製造するために、バイオマスのガス化は間接加熱方式を採用する場合がある。十分な熱伝達量を確保するため、伝熱面積の大きいガス化装置が必要となり、排ガスの熱ロスも大きい。一方、内部燃焼方式を採用するバイオマスガス化もあるが、酸素を用いて燃焼するため、酸素プラントが必要となる。
（３）ガス化後のタール除去、ガス組成調整、脱硫等の付属設備
今までのガス化方法はガス化の後にさらにタール改質、タール除去、シフト反応によるガス組成調整、脱硫等のガス精製過程が必要となり、プロセスが複雑し、設備費と保守のコストが高い。
（４）さまざまなバイオマスの利用
高水分、難粉砕のバイオマス、廃棄物等を利用可能なガス化炉が必要となる。
（５）小型プラントのため、高い合成液体燃料の選択性と収率が要求される。
本発明は、改良型三塔式循環流動層ガス化炉であって、今まで本発明者が取り組んできた三塔式循環流動層ガス化炉で石炭バイオマス燃料合成システムを構築したうえ、さらに、バイオマス利用の問題点の解決を図るものである。具体的に、ガス化過程と液体燃料合成過程で発生した難分解性CH4等炭化水素(CnHm)を三塔式ガス化炉の改質塔に導入し改質し、合成ガスを増量することで、液体燃料合成過程の選択性と収率をアップする。また、三塔式ガス化炉燃焼塔サイクロンから一部のCaO媒体を低温硫黄再吸収器に導入し、改質塔から出た改質ガス中のH2S、COS及びCO2を低温硫黄再吸収器でCaOによって再度に吸収し、高品位の合成ガスを製造する。低温硫黄再吸収器から出たCaSとCaCO3は再び燃焼塔に導入する。さらに、バイオマスと補助燃料をガス化炉に提供することで、原料性状の安定化とガス化熱収支安定化を図りつつ、循環流動層ガス化炉を用いてガス化、メタン等難分解炭化水素(CnHm)改質、炉内脱硫及びH2/CO比の調整を行い、高品位の合成ガスを製造し、流動層ガス化炉は高水分、難粉砕のバイオマス、廃棄物等を対応し易いガス化技術である。 In order to reduce carbon dioxide emissions, the introduction of liquid fuel production using biomass resources, which are renewable energy sources, is important, but the following problems must be overcome for biomass utilization technology.
(1) Stable supply of gasification raw materials For operation of a chemical plant, stable plant load and long-time operation are required. Excessive load fluctuations and frequent start / stops not only damage equipment and reduce productivity, but also increase CO 2 emissions due to excessive input of auxiliary fuel during start / stop.
(2) Heat supply to biomass gasification In order to produce high-calorie fuel or synthesis gas, biomass gasification may employ an indirect heating method. In order to ensure a sufficient amount of heat transfer, a gasifier with a large heat transfer area is required, and the heat loss of exhaust gas is also large. On the other hand, although there is biomass gasification which adopts an internal combustion method, since it burns using oxygen, an oxygen plant is needed.
(3) Attached equipment such as tar removal after gasification, gas composition adjustment, desulfurization, etc. Conventional gasification methods are gas reforming after gasification, gas composition adjustment by shift reaction, gas purification such as desulfurization, etc. A process is required, the process is complicated, and the cost of equipment and maintenance is high.
(4) Utilization of various biomass Gasifiers that can use high moisture, difficult-to-pulverize biomass, waste, etc. are required.
(5) Since the plant is small, high selectivity and yield of synthetic liquid fuel are required.
The present invention is an improved three-column circulating fluidized bed gasification furnace, and a coal biomass fuel synthesizing system is constructed in the three-column circulating fluidized bed gasification furnace that the present inventors have been working on, It aims to solve the problem of biomass utilization. Specifically, hydrocarbons such as persistent CH 4 (C n H m ) generated in the gasification process and liquid fuel synthesis process are introduced into the reforming tower of the three-column gasifier and reformed, and the synthesis gas is Increasing the amount increases the selectivity and yield of the liquid fuel synthesis process. In addition, a part of CaO medium is introduced into the low-temperature sulfur reabsorber from the three-column gasifier combustion tower cyclone, and H 2 S, COS, and CO 2 in the reformed gas discharged from the reforming tower are converted into low-temperature sulfur recycle. It is absorbed again with CaO in the absorber to produce high-quality synthesis gas. CaS and CaCO 3 from the low-temperature sulfur reabsorber are reintroduced into the combustion tower. Furthermore, by providing biomass and auxiliary fuel to the gasification furnace, gasification using a circulating fluidized bed gasification furnace, and refractory hydrocarbons such as methane, while stabilizing raw material properties and gasification heat balance (CnHm) reforming, in-furnace desulfurization and adjustment of H 2 / CO ratio to produce high quality synthesis gas, fluidized bed gasifier is easy to handle high moisture, difficult-to-grind biomass, waste, etc. Gasification technology.

すなわち、本発明は、温度850℃〜1000℃で運転する流動層燃焼塔と温度850℃〜1000℃で運転する流動層改質塔と温度650℃〜850℃で運転する流動層ガス化塔と400℃〜700℃で低温硫黄再吸収器からなる三塔式循環流動層ガス化方法であり、CaOを伝熱媒体、メタン等炭化水素(CnHm)改質触媒及びCO2とH2Sの吸収剤として、三塔及び低温硫黄再吸収器を結ぶ装置内で循環させ、バイオマスや石炭等固体燃料と高温水蒸気をガス化塔に供給し、650℃〜850℃の熱媒体と接触して熱分解とガス化を起こし、ガス化ガスとチャー（固定炭素）を生成し、また、ガス化塔でCaOによって一部CO2とH2Sを吸収しCaCO3とCaSを生成し、ガス化ガスと液体燃料合成から来たオフガスと水蒸気は改質塔に導入し、850℃〜1000℃のCaO熱媒体と接触してメタン等難分解炭化水素(CnHm)の触媒改質を行い、残ったチャーはCaO熱媒体、CaCO3及びCaSと共に燃焼塔に導入し、空気でチャーを燃焼させ、CaO熱媒体を加熱し、CaCO3をCaOに焼成、CaSをCaSO4に酸化し、CaO熱媒体はサイクロンを経て改質塔とガス化塔に戻り、改質塔とガス化塔の温度を維持し、また、サイクロンを経たCaO熱媒体の一部を低温硫黄再吸収器に導入し、改質塔から出た改質ガス中のH2S、COS及びCO2を再吸収し、吸収後のCaSとCaCO3含有熱媒体を再び燃焼塔に導入する三塔式循環流動層ガス化方法において、流動層改質塔において、CaOの存在下、H2Oとメタン等難分解炭化水素ガス(CnHm)を反応させてCOとH2に分解し、合成ガスとし、液体燃料合成をおこない、液体燃料を取り出し、液体燃料にならないオフガスと重質残渣は、流動層改質塔及び又はガス化塔に戻すことを特徴とする改良型三塔式循環流動層ガス化方法である。
また、本発明の改良型三塔式循環流動層ガス化方法においては、補助燃料として石炭を使用し、バイオマスと共ガス化することができる。
さらに、本発明の改良型三塔式循環流動層ガス化方法においては、流動層燃焼塔と流動層改質塔との間に、媒体サイクロンを設けることができる。 That is, the present invention includes a fluidized bed combustion tower operating at a temperature of 850 ° C. to 1000 ° C., a fluidized bed reforming tower operating at a temperature of 850 ° C. to 1000 ° C., and a fluidized bed gasification tower operating at a temperature of 650 ° C. to 850 ° C. A three-column circulating fluidized bed gasification method consisting of a low-temperature sulfur reabsorber at 400 ° C to 700 ° C, CaO as a heat transfer medium, hydrocarbon (CnHm) reforming catalyst such as methane, and absorption of CO 2 and H 2 S It is circulated in an apparatus connecting the three towers and the low-temperature sulfur reabsorber as an agent, supplying solid fuel such as biomass and coal and high-temperature steam to the gasification tower, and contacting with a heat medium at 650 ° C to 850 ° C for thermal decomposition Gasification and char (fixed carbon) are generated, and part of the gasification tower absorbs CO 2 and H 2 S with CaO to generate CaCO 3 and CaS. Off-gas and water vapor from liquid fuel synthesis are introduced into the reforming tower and contacted with CaO heat medium at 850 ° C to 1000 ° C to contact refractory hydrocarbons (CnHm) such as methane. Perform reforming, remaining char CaO heating medium is introduced into the combustion tower with CaCO 3 and CaS, the char with air is burned to heat the CaO heating medium, firing the CaCO 3 to CaO, the CaS to CaSO 4 Oxidized, the CaO heat medium returns to the reforming tower and gasification tower through the cyclone, maintains the temperature of the reforming tower and the gasification tower, and a part of the CaO heat medium passed through the cyclone is a low-temperature sulfur reabsorber. A three-column circulation flow in which H 2 S, COS and CO 2 in the reformed gas exiting from the reforming tower is reabsorbed and the absorbed CaS and CaCO 3 -containing heat medium is again introduced into the combustion tower. In the bed gasification method, in a fluidized bed reforming tower, H 2 O and a hardly-decomposable hydrocarbon gas such as methane (C n H m ) are reacted in the presence of CaO to decompose into CO and H 2 to produce synthesis gas. The liquid fuel synthesis is performed, the liquid fuel is taken out, and the off-gas and heavy residue that do not become the liquid fuel are returned to the fluidized bed reforming tower and / or the gasification tower. This is an improved three-column circulating fluidized bed gasification method.
In the improved three-column circulating fluidized bed gasification method of the present invention, coal can be used as auxiliary fuel and co-gasified with biomass.
Furthermore, in the improved three-column circulating fluidized bed gasification method of the present invention, a medium cyclone can be provided between the fluidized bed combustion tower and the fluidized bed reforming tower.

また、本発明の改良型三塔式循環流動層ガス化方法では、CaOベース媒体を伝熱媒体、改質触媒及びCO2とH2Sの吸収剤とし、三塔式循環流動層ガス化炉装置及び低温硫黄再吸収器内で循環させ、燃料石炭とバイオマスをガス化塔に供給し、熱媒体と接触して650-850℃で熱分解とガス化を起こし、ガス化ガスとチャー（固定炭素）を生成し、ガス化ガスと液体燃料合成過程で発生したオフガスは改質塔に導入し、850℃-1000℃の熱媒体と接触してガス化ガス及びオフガス中のメタン（CH4）等難分解性炭化水素(CnHm)の触媒改質を行い、改質炉から出た改質ガスは低温硫黄再吸収器でH2S、COS及びCO2を再吸収してガス洗浄塔を経て燃料合成装置に提供され、液体燃料として取り出すことができる。
さらに、本発明の改良型三塔式循環流動層ガス化方法では、ガス化塔の温度と圧力調整によって、CaOによるCO2の吸収量とCOとH2Oとシフト反応量を制御でき、ガス化生成ガスのH2/CO比を調整することができる。
また、本発明は、温度900℃〜1000℃で運転する流動層燃焼塔と温度900℃〜1000℃で運転する流動層改質塔と温度700℃〜800℃で運転する流動層ガス化塔と400℃〜800℃で運転する低温硫黄再吸収器からなる改良型三塔式循環流動層ガス化装置であり、CaOを伝熱媒体、触媒及びCO2とH2Sの吸収剤として、三塔及び低温硫黄再吸収器を結ぶ装置内で循環させ、バイオマスと石炭等固体燃料をガス化塔に供給し650-850℃の熱媒体と接触して熱分解とガス化を起こし、ガス化ガスとチャー（固定炭素）を生成し、また、ガス化塔でCaOが一部のCO2とH2Sを吸収し、CaCO3とCaSを生成し、ガス化ガスと液体燃料合成過程で発生したオフガスは改質塔に導入し、850-1000℃の熱媒体と接触してガス化ガスとオフガス中のメタン等難分解炭化水素(CnHm)の触媒改質を行い、チャーはCaO熱媒体、CaCO3及びCaSと共に燃焼塔に導入し、空気でチャーを燃焼させ、熱媒体を加熱し、CaCO3をCaOに焼成し、CaSをCaSO4に酸化し、熱媒体はサイクロンを経て改質塔とガス化塔に戻り、改質塔とガス化塔の温度を維持し、また、サイクロンを経たCaO熱媒体の一部を低温硫黄再吸収器に導入し、H2S、COS及びCO2を再吸収し、吸収後のCaSとCaCO3含有熱媒体を再び燃焼器に導入し、循環させる改良型三塔式循環流動層ガス化装置である。 Further, in the improved three-column circulating fluidized bed gasification method of the present invention, a three-column circulating fluidized bed gasifier using a CaO base medium as a heat transfer medium, a reforming catalyst, and CO 2 and H 2 S absorbents. It is circulated in the equipment and low-temperature sulfur reabsorber, fuel coal and biomass are supplied to the gasification tower, and contacted with the heat medium to cause pyrolysis and gasification at 650-850 ℃, gasified gas and char (fixed) Off gas generated during the synthesis of gasified gas and liquid fuel is introduced into the reforming tower and brought into contact with a heating medium at 850 ° C-1000 ° C to form methane (CH 4 ) in the gasified gas and offgas. Catalytic reforming of hard-to-decompose hydrocarbons (C n H m ), and the reformed gas emitted from the reforming furnace is re-absorbed with H 2 S, COS and CO 2 by a low-temperature sulfur reabsorber, and cleaned with gas It is provided to the fuel synthesizer via the tower and can be taken out as a liquid fuel.
Furthermore, in the improved three-column circulating fluidized bed gasification method of the present invention, the amount of CO 2 absorbed by CaO and the amount of CO, H 2 O, and shift reaction can be controlled by adjusting the temperature and pressure of the gasification tower. The H 2 / CO ratio of the chemical gas can be adjusted.
The present invention also includes a fluidized bed combustion tower operating at a temperature of 900 ° C to 1000 ° C, a fluidized bed reforming tower operating at a temperature of 900 ° C to 1000 ° C, and a fluidized bed gasification tower operating at a temperature of 700 ° C to 800 ° C. An improved three-column circulating fluidized bed gasifier consisting of a low-temperature sulfur reabsorber operating at 400 ° C to 800 ° C, with CaO as the heat transfer medium, catalyst, and CO 2 and H 2 S absorbent. And a solid fuel such as biomass and coal are supplied to the gasification tower and contacted with a heat medium of 650-850 ° C to cause pyrolysis and gasification. Char (fixed carbon) is produced, and CaO absorbs a part of CO 2 and H 2 S in the gasification tower to produce CaCO 3 and CaS, which is generated in the gasification gas and liquid fuel synthesis process. is introduced into the reforming tower performs catalytic reforming of methane, such as decomposition-hydrocarbon contact gasified gas and off gas in the heat medium of 850-1000 ℃ (C n H m) , Catcher chromatography is introduced into the combustion tower with CaO heat medium, CaCO 3 and CaS, the char with air is burned to heat the heat medium, firing the CaCO 3 to CaO and oxidation of CaS into CaSO 4, the heat medium cyclone To return to the reforming tower and the gasification tower, maintain the temperature of the reforming tower and the gasification tower, and introduce a part of the CaO heat medium through the cyclone into the low-temperature sulfur reabsorber, H 2 S, This is an improved three-column circulating fluidized bed gasifier that re-absorbs COS and CO 2 and recirculates the CaS and CaCO 3 -containing heat medium after absorption into the combustor.

本発明の改良型三塔式循環流動層ガス化方法又は三塔式循環流動層ガス化装置では、流動層改質塔において、CaOの存在下、H2Oとガス化ガス及びオフガス中のメタン等難分解炭化水素ガス（CnHm）を反応させてCOとH2に分解し、合成ガスを増量し、液体燃料合成をおこない、液体燃料を取り出ながら、液体燃料にならないオフガスと重質炭化水素を改質塔及び（或いは）ガス化塔に導入する。メタン等炭化水素成分(CnHm)が改質塔で分解されて合成ガス化が進むため、殆どメタンなどの炭化水素(CnHm)を生成することなく、また、改質ガスに残されたH2S、COS及びCO2が低温硫黄吸収器で殆ど再吸収されることで、高品位のクリーンな合成ガスを製造でき、簡単なガス洗浄処理で液体燃料合成に導入するため、ガスクリーンアップを簡素化しても長時間の連続運転が可能となり、極めて低コスト、高効率で運転できる。 In the improved three-column circulating fluidized bed gasification method or the three-column circulating fluidized bed gasification apparatus of the present invention, in the fluidized bed reforming tower, in the presence of CaO, H 2 O, gasified gas, and methane in off-gas It reacts with non-resolved hydrocarbon gas (C n H m ), decomposes it into CO and H 2 , increases the synthesis gas, performs liquid fuel synthesis, takes out the liquid fuel, and removes the liquid fuel. Quality hydrocarbons are introduced into the reforming tower and / or the gasification tower. Since hydrocarbon components (C n H m ) such as methane are decomposed in the reforming tower and the synthesis gas proceeds, almost no hydrocarbons (CnHm) such as methane are generated and left in the reformed gas. Since H 2 S, COS, and CO 2 are almost reabsorbed by low-temperature sulfur absorbers, high-quality clean synthesis gas can be produced, and it can be introduced into liquid fuel synthesis with a simple gas cleaning process. Even if it is simplified, continuous operation for a long time is possible, and operation is possible at extremely low cost and high efficiency.

従来の循環流動層ガス化炉。Conventional circulating fluidized bed gasifier. 従来の改良された循環流動層ガス化炉。Conventional improved circulating fluidized bed gasifier. 改良前の三塔式ガス化装置の一例Example of a three-column gasifier before improvement 本件発明の三塔式循環流動層ガス化装置の一例An example of the three-column circulating fluidized bed gasifier of the present invention CO２吸収濃度の予測Prediction of CO 2 absorption concentration CaOによる模擬タール改質効果（実験）Simulated tar reforming effect by CaO (experiment) タール改質炉の温度によるガス組成の予測Prediction of gas composition by temperature of tar reforming furnace CaOによるH2S吸収可能の温度範囲Temperature range where H 2 S can be absorbed by CaO 本件発明の三塔式ガス化装置のタール改質塔とガス化塔の一例Examples of the tar reforming tower and gasification tower of the three-column gasifier of the present invention 本件発明の三塔式ガス化装置のタール改質塔とガス化塔の一例Examples of the tar reforming tower and gasification tower of the three-column gasifier of the present invention

本発明の原理について説明する。
本発明者が提供した初めての三塔式循環流動層ガス化方法を図３に示す（特願2012−223683参照）。しかし、この三塔式循環流動層ガス化方法では、タール成分が分解されてガス化が進むため、殆どタールを生成することなく、熱交換器等のパイプにタールが析出しないため、長時間の連続運転が可能となり、極めて高効率で合成ガスを液体燃料合成に提供し、液体燃料を合成できるものの、ガス化ガス及び液体燃料合成オフガス中のメタン等難分解炭化水素ガス(CnHm)、が発生するため、その有効利用が望まれていた。また、高温のガス化塔及びタール改質塔ではH2S、COS及びCO2をCaOによって十分に吸収できないため、さらに改善が望まれていた。
本発明者は、このメタン等難分解炭化水素ガス(CnHm)を合成ガスに変換し、液体燃料を得る、また、改質塔から出た改質ガス中の在留H2S、COS及びCO2を低温で再吸収し、高品位の合成ガスを製造できる改良型三塔式循環流動層ガス化方法を見出すに至った。
本発明で云うオフガスとは、液体燃料合成過程に発生した液体燃料にならないメタン等のガス状炭化水素(CnHm)をいう。
これらのオフガスは難分解性なものが多く、本発明では、ガス化ガス及び液体燃料合成過程で発生したオフガスを三塔式循環流動層ガス化炉の改質塔ガス化塔（オフガスはガス化炉にも導入可能）に導入し、ガス中のメタン等難分解炭化水素（CnHm）を改質することによって、液体燃料合成の選択性及び収率を高める方法である。
また、改質塔から出た改質ガスを低温硫黄吸収器に導入して、吸収器内のCaO粒子によってH2S、COS及びCO2を再吸収することで、きわめてクリーンな合成ガスを製造し、燃焼塔媒体サイクロンを経たCaO熱媒体の一部を低温硫黄再吸収器に導入し、吸収後のCaSとCaCO3含有媒体を再び燃焼塔に導入させる方法である。
本発明の原理は、図４に示すように、ガス化、改質及び燃焼三塔式循環流動層ガス化炉を用いて石炭、バイオマスから液体燃料を製造する際に、ガス化ガス及び液体燃料合成で発生したオフガスを三塔式循環流動層ガス化炉の改質塔（オフガスはガス化塔にも導入可能）に導入し、ガス中のCH4等難分解性炭化水素（CnHm）を改質することによって、合成ガスを生成し、液体燃料合成の選択性及び収率を高め、また、改質塔から出た改質ガスを低温硫黄吸収器に導入して、吸収器内のCaO粒子によってH2S、COS及びCO2を再吸収することによってきわめてクリーンな合成ガスを製造し、燃焼塔媒体サイクロンを経たCaO熱媒体の一部を低温硫黄再吸収器に導入し、吸収後のCaSとCaCO3含有媒体を再び燃焼器に導入させる方法である。
The principle of the present invention will be described.
FIG. 3 shows the first three-column circulating fluidized bed gasification method provided by the present inventor (see Japanese Patent Application No. 2012-223683). However, in this three-column circulating fluidized bed gasification method, since tar components are decomposed and gasification proceeds, tar is hardly deposited on pipes of heat exchangers and the like without generating tar. Although it is possible to operate continuously and provides synthesis gas to liquid fuel synthesis with extremely high efficiency and can synthesize liquid fuel, it is difficult to decompose hydrocarbon gas (C n H m ) such as methane in gasification gas and liquid fuel synthesis off-gas Therefore, effective use thereof has been desired. Further, since high-temperature gasification towers and tar reforming towers cannot sufficiently absorb H 2 S, COS and CO 2 by CaO, further improvement has been desired.
The present inventor converts the hardly decomposed hydrocarbon gas (C n H m ) such as methane into a synthesis gas to obtain a liquid fuel, and the residual H 2 S, COS in the reformed gas discharged from the reforming tower. As a result, the inventors have found an improved three-column circulating fluidized bed gasification method capable of reabsorbing CO 2 at low temperatures and producing high-quality synthesis gas.
The off-gas referred to in the present invention refers to a gaseous hydrocarbon (C n H m ) such as methane that does not become a liquid fuel generated during the liquid fuel synthesis process.
Many of these off-gases are hardly decomposable. In the present invention, off-gas generated in the synthesis process of gasification gas and liquid fuel is converted into a reforming tower gasification tower of a three-column circulating fluidized bed gasification furnace (off-gas is gasification). This is a method of improving the selectivity and yield of liquid fuel synthesis by reforming refractory hydrocarbons (C n H m ) such as methane in the gas.
In addition, by introducing the reformed gas from the reforming tower into the low-temperature sulfur absorber and reabsorbing H 2 S, COS and CO 2 by the CaO particles in the absorber, extremely clean synthesis gas is produced. Then, a part of the CaO heat medium that has passed through the combustion tower medium cyclone is introduced into the low-temperature sulfur reabsorber, and the CaS and CaCO 3 -containing medium after absorption is introduced into the combustion tower again.
The principle of the present invention is that, as shown in FIG. 4, when a liquid fuel is produced from coal and biomass using a gasification, reforming and combustion three-column circulating fluidized bed gasification furnace, the gasification gas and the liquid fuel are used. The off-gas generated in the synthesis is introduced into the reforming tower of the three-column circulating fluidized bed gasifier (off-gas can also be introduced into the gasification tower), and CH 4 and other difficult-to-decompose hydrocarbons in the gas (C n H m ) To improve the selectivity and yield of liquid fuel synthesis, and introduce the reformed gas from the reforming tower into the low-temperature sulfur absorber. By reabsorbing H 2 S, COS and CO 2 with CaO particles, a very clean synthesis gas is produced, and a part of the CaO heat medium passed through the combustion tower medium cyclone is introduced into the low-temperature sulfur reabsorber and absorbed. This is a method of introducing the CaS and CaCO 3 -containing medium later into the combustor again.

燃焼塔１２０はバブリング流動層であり、850℃〜1000℃でチャーを空気或いは酸素によって燃焼し、媒体を温め、CaCO3をCaOに焼成し、CaSをCaSO4に酸化するものである。ライザーはファスト流動層であり、温めたCaO媒体を必要な高度まで燃焼ガスで飛ばすものである。改質塔１３０はバブリング流動層或いは移動層であり、850℃〜1000℃でメタン（CH4）等難分解炭化水素（CnHm）を改質するものである。ガス化塔１１０はバブリング流動層或いは移動層であり、650℃〜850℃でバイオマスと石炭等固体燃料の熱分解及びガス化を起こすものである。低温硫黄再吸収器は400℃〜700℃で改質ガス中の残留H2S、COS及びCO2を再吸収するものである。
CaOベース媒体を伝熱媒体、改質触媒及びCO2とH2Sの吸収剤とし、三塔式循環流動層ガス化炉装置内で循環させ、また、一部CaOを低温硫黄再吸収器にバイパスして循環させる。装置内CaOの補充として、石灰石などCaCO3含有鉱物を燃焼塔に導入し、高温でCaOに分解させ、あるいはCaO含有物質をガス化塔に導入する。石炭とバイオマスをガス化器に供給し、熱媒体と接触して650-850℃で熱分解とガス化を起こし、ガス化ガスとチャー（固定炭素）を生成する。ガス化ガスと液体燃料合成過程で発生したオフガスは改質塔に導入し、850℃-1000℃のCaO熱媒体と接触してガス中のメタン（CH4）等難分解性炭化水素(CnHm)の触媒改質を行う。ガス化塔ではCaOがH2S及びCOSを吸収しCaSになり、CO2を吸収してCaCO3になる。チャーは未反応のCaO熱媒体及びCaS、CaCO3と共に燃焼塔に導入し、空気あるいは酸素でチャーを燃焼させ、熱媒体を加熱し、CaCO3をCaOに焼成し、CaSをCaSO4に酸化する。加熱されたCaO熱媒体はサイクロンを経て改質塔とガス化塔に戻り、改質塔とガス化塔の温度を維持する。また、サイクロンを経たCaO熱媒体の一部を低温硫黄再吸収器に導入し、H2S、COS及びCO2を再吸収し、吸収後のCaSとCaCO3含有熱媒体を再び燃焼器に導入し、循環させる。改質炉から出た改質ガスは低温硫黄再吸収器に導入し、低温条件でCaOによってガス中のH2SとCOS及びCO2を再吸収する。低温硫黄再吸収器から出たクリーン合成ガスはガス洗浄を経て燃料合成装置に提供する。
化学反応論によれば、水蒸気による炭化水素改質の難しさ順は、メタンCH4>ベンゼンC6H6>ナフタレンC10H8>プロパンC3H8である。
ガス化塔及び改質塔に供給するガス化剤及び改質剤は水蒸気、CO2、或いはオフガス中の水蒸気とCO2を利用することができる。
The combustion tower 120 is a bubbling fluidized bed, which burns char with air or oxygen at 850 ° C. to 1000 ° C., warms the medium, burns CaCO 3 to CaO, and oxidizes CaS to CaSO 4 . The riser is a fast fluidized bed that blows warm CaO media to the required altitude with combustion gases. The reforming tower 130 is a bubbling fluidized bed or moving bed, and reforms hardly decomposed hydrocarbons (C n H m ) such as methane (CH 4 ) at 850 ° C. to 1000 ° C. The gasification tower 110 is a bubbling fluidized bed or moving bed, and causes thermal decomposition and gasification of solid fuel such as biomass and coal at 650 ° C to 850 ° C. Low sulfur resorption device is to re-absorb residual reformed gas H2 S, the COS and CO 2 at 400 ° C. to 700 ° C..
The CaO base medium is used as a heat transfer medium, reforming catalyst, and CO 2 and H 2 S absorbent, and is circulated in a three-column circulating fluidized bed gasifier. In addition, some CaO is used as a low-temperature sulfur resorber. Bypass and circulate. To replenish CaO in the equipment, a CaCO 3 -containing mineral such as limestone is introduced into the combustion tower and decomposed into CaO at a high temperature, or a CaO-containing substance is introduced into the gasification tower. Coal and biomass are supplied to a gasifier and contacted with a heat medium to cause pyrolysis and gasification at 650-850 ° C, producing gasified gas and char (fixed carbon). The gasified gas and off-gas generated during the liquid fuel synthesis process are introduced into the reforming tower and contacted with a CaO heating medium at 850 ° C-1000 ° C to produce a refractory hydrocarbon such as methane (CH 4 ) in the gas (C n Catalyst reforming of H m ) is performed. In the gasification tower, CaO absorbs H 2 S and COS to become CaS, and absorbs CO 2 to become CaCO 3 . Char is introduced into the combustion tower together with unreacted CaO heat medium and CaS, CaCO 3 , char is burned with air or oxygen, the heat medium is heated, CaCO 3 is calcined to CaO, and CaS is oxidized to CaSO 4 . The heated CaO heat medium returns to the reforming tower and the gasification tower through the cyclone and maintains the temperature of the reforming tower and the gasification tower. In addition, a part of the CaO heat medium that has passed through the cyclone is introduced into the low-temperature sulfur reabsorber, H 2 S, COS, and CO 2 are reabsorbed, and the CaS and CaCO 3 containing heat medium after absorption is reintroduced into the combustor. And circulate. The reformed gas from the reforming furnace is introduced into a low temperature sulfur reabsorber, and H 2 S, COS and CO 2 in the gas are reabsorbed by CaO at low temperature conditions. The clean syngas from the low temperature sulfur reabsorber is supplied to the fuel synthesizer through gas cleaning.
According to chemical reaction theory, the order of difficulty of hydrocarbon reforming with steam is methane CH 4 > benzene C 6 H 6 > naphthalene C 10 H 8 > propane C 3 H 8 .
Gasifying agent supplied to the gasifying column and reforming tower and modifiers can be used steam, CO 2, or water vapor and CO 2 in the off-gas.

本発明では、ガス化、改質及び燃焼の三塔式循環流動層ガス化炉を用いる（図４参照）。CaO粒子を用いて、伝熱媒体、触媒及びCO2とH2Sの吸収剤として、装置内と低温硫黄再吸収器内で循環させる。バイオマスや石炭等固体燃料とガス化剤をガス化塔に供給し、650℃-850℃の熱媒体と接触して熱分解とガス化を起こし、ガス化ガスとチャー（固定炭素）を生成させる。ガス化ガス及び液体燃料合成から来たオフガスは改質塔に導入し、850℃-1000℃のCaO熱媒体と接触してメタン等難分解炭化水素(CnHm)の改質を行う。チャーは未反応CaO熱媒体、CaCO3及びCaSと共に燃焼塔に導入し、空気でチャーを燃焼させ、熱媒体を加熱し、CaCO3をCaOに焼成し、CaSをCaSO4に酸化する。加熱されたCaO熱媒体は媒体サイクロン１２５を経て改質塔とガス化塔に戻り、改質塔とガス化塔の温度を維持する。また、サイクロン１２５を経たCaO熱媒体の一部を低温硫黄再吸収器１５０に導入し、改質塔１３０から出た改質ガスも硫黄再吸収器１５０に導入し、改質ガス中に残留されたH2S、COS及びCO2をCaOによって低温で再吸収し、吸収後のCaSとCaCO3含有熱媒体を再び燃焼塔に導入し、循環させる。低温硫黄吸収器から出たクリーン合成ガスはガス洗浄を経て燃料合成装置に提供する。
（ガス化塔の内部加熱方式）
燃焼塔で加熱されたCaO熱媒体がまず改質塔でガス化ガスとオフガスと接触しながらメタン(CH4)等の難分解炭化水素(CnHm)の触媒改質に熱を提供し、また、ガス化塔に導入され、バイオマス、石炭等固体燃料と直接接触しながらバイオマス、石炭等固体燃料の熱分解とガス化反応に熱を供与する。燃焼塔で加熱されたCaO熱媒体の一部を低温硫黄再吸収器に導入し、改質塔から出た改質ガス中に残留されたH2S、COS及びCO2を吸収する。 In the present invention, a three-column circulating fluidized bed gasification furnace for gasification, reforming and combustion is used (see FIG. 4). CaO particles are used as a heat transfer medium, catalyst, and CO 2 and H 2 S absorbent to circulate in the equipment and in the low temperature sulfur resorber. Supplying solid fuel such as biomass or coal and gasifying agent to the gasification tower, contacting with a heat medium of 650 ℃ -850 ℃, causing pyrolysis and gasification, generating gasified gas and char (fixed carbon) . Gasified gas and off-gas resulting from liquid fuel synthesis are introduced into the reforming tower and contacted with a CaO heat medium at 850 ° C-1000 ° C to reform refractory hydrocarbons (C n H m ) such as methane. Char is introduced into a combustion tower together with unreacted CaO heat medium, CaCO 3 and CaS, char is burned with air, the heat medium is heated, CaCO 3 is calcined to CaO, and CaS is oxidized to CaSO 4 . The heated CaO heat medium returns to the reforming tower and the gasification tower via the medium cyclone 125, and maintains the temperature of the reforming tower and the gasification tower. In addition, a part of the CaO heat medium that has passed through the cyclone 125 is introduced into the low-temperature sulfur reabsorber 150, and the reformed gas output from the reforming tower 130 is also introduced into the sulfur reabsorber 150, and remains in the reformed gas. H 2 S, COS and CO 2 are reabsorbed by CaO at low temperature, and the CaS and CaCO 3 -containing heat medium after absorption is reintroduced into the combustion tower and circulated. The clean syngas from the low-temperature sulfur absorber is supplied to the fuel synthesizing apparatus through gas cleaning.
(Internal heating method of gasification tower)
The CaO heating medium heated in the combustion tower first supplies heat to the catalytic reforming of refractory hydrocarbons (C n H m ) such as methane (CH 4 ) while contacting the gasification gas and off-gas in the reforming tower. In addition, it is introduced into a gasification tower and supplies heat to the thermal decomposition and gasification reaction of the solid fuel such as biomass and coal while in direct contact with the solid fuel such as biomass and coal. Part of the CaO heat medium heated in the combustion tower is introduced into the low-temperature sulfur reabsorber to absorb H 2 S, COS and CO 2 remaining in the reformed gas from the reforming tower.

（CaO媒体の使用）
本件発明では、CaOベース媒体は石灰石、ドロマイド天然鉱物から焼成することができる。石灰石、ドロマイド天然鉱物は直接に燃焼塔に供給し、燃焼塔で焼成し、装置内のCaOを補充する方法と、他の焼成装置を使用して焼成して、CaOをガス化炉に直接に供給し、装置内のCaOを補充する方法がある。また、CaOと他酸化物から人工調整で製造することができる。
三塔式循環流動層ガス化炉装置内で循環する際に、CaOベース媒体は単独に使用することができる。また、硅砂、アルミナー、酸化鉄等粒子と混合して使用することができる。
CaO媒体を系内で循環させ、以下の役割を発揮させる。
＊伝熱媒体として、燃焼塔で加熱され、改質塔及びガス化塔で熱を放出し、ガス化ガス、オフガス中のメタン等難分解炭化水素(CnHm)の改質に熱を提供する。
＊CO2吸収剤として、ガス化塔内で一部のCO2を吸収し、生成ガス中のH2/COの割合を調整しながら、CO2吸収熱をガス化塔内のバイオマスガス化に提供し、また、低温硫黄再吸収器内でCO2を吸収し、合成ガスの純度を高める。
ガス化塔と低温硫黄再吸収器内で下記の反応を起こす
CaO＋CO２→CaCO３；ΔＨ２９８＝−１７８KJ/mol 発熱
CO＋H2O→CO２＋Ｈ２；ΔＨ２９８＝−４１KJ/mol 発熱
図５は反応温度及び圧力により、ガス化器内で吸収できるCO2の平衡濃度である。 (Use of CaO media)
In the present invention, the CaO-based medium can be fired from limestone, dolomide natural mineral. Limestone and dolomide natural minerals are supplied directly to the combustion tower, calcined in the combustion tower, replenished with CaO in the equipment, and calcined using other calciners, and CaO directly into the gasifier There is a method to supply and replenish CaO in the device. Moreover, it can manufacture by artificial adjustment from CaO and another oxide.
When circulating in the three-column circulating fluidized bed gasifier, the CaO base medium can be used alone. Moreover, it can be used by mixing with particles such as cinnabar sand, alumina and iron oxide.
Circulate CaO medium in the system and play the following roles.
* As a heat transfer medium, it is heated in the combustion tower, released heat in the reforming tower and gasification tower, and heat is used for reforming refractory hydrocarbons (C n H m ) such as methane in the gasification gas and off-gas. provide.
* As a CO 2 absorbent, a part of CO 2 is absorbed in the gasification tower, and the CO 2 absorption heat is converted into biomass gasification in the gasification tower while adjusting the ratio of H 2 / CO in the product gas. Provide and also absorb CO 2 in a low temperature sulfur resorber to increase the purity of the synthesis gas.
The following reactions occur in the gasification tower and the low-temperature sulfur reabsorber:
CaO + CO 2 → CaCO 3 ; ΔH 298 = −178 KJ / mol Exotherm
CO + H 2 O → CO 2 + H 2 ; ΔH 298 = −41 KJ / mol Exotherm FIG. 5 shows the equilibrium concentration of CO 2 that can be absorbed in the gasifier depending on the reaction temperature and pressure.

＊触媒として、改質塔でガス化ガスとオフガス中のメタン(CH4)等難分解炭化水素（CnHm）の改質を促進する。図６はCaOによるメタン(CH4)の水蒸気改質の実施例である。
ここで改質塔１３０の温度によるガス組成の予測は平衡計算から図７に示すことができる。
また、CaOは、脱硫剤として、ガス化塔１１０内及び低温硫黄再吸収器内でH2Sを吸収し、CaSを生成し、さらに燃焼塔１２０で酸素と反応してCaSO4になり、これはサイクロン（或いは集塵器）１２８で回収することが出来る。
ガス化塔では、CaO+H2S→CaS の反応が進み
燃焼塔では、
CaS+2O2
→CaSO4 の反応が進む。
循環媒体として投入したCaOはCO2吸収と伝熱が主目的であるため、その固体燃料中の硫黄に対するモル比は30-200があり、従来の脱硫目的として炉内に投入したCaO対硫黄のモル比（通常2-3）よりかなり大きいものである。従って、ガス化塔内及び低温硫黄再吸収器内でH2Sを吸収してもCaO粒子表面にごく薄い膜のCaSしか生成しないため、燃焼塔内で酸素によって酸化し易い。また、燃焼塔内の流動摩耗によって、粉粒化し、燃焼塔排ガスサイクロン（或いは集塵器）128で分級、回収される。
本発明では、CaO/H2Sのモル比30-200のガス化塔内及び低温硫黄再吸収器内でCaO粒子表面にCaS膜を生成し、燃焼塔でCaS膜を酸化してCaSO4を生成し、さらに、磨耗によってCaSO4が粉粒子して、集塵器やバグフィルターで回収することができる。 * As a catalyst, promote reforming of gasified gas and refractory hydrocarbons (C n H m ) such as methane (CH 4 ) in the off-gas in the reforming tower. FIG. 6 shows an example of steam reforming of methane (CH 4 ) with CaO.
Here, the prediction of the gas composition depending on the temperature of the reforming tower 130 can be shown in FIG. 7 from the equilibrium calculation.
In addition, as a desulfurization agent, CaO absorbs H 2 S in the gasification tower 110 and the low-temperature sulfur reabsorber, generates CaS, and further reacts with oxygen in the combustion tower 120 to become CaSO 4. Can be recovered with a cyclone (or dust collector) 128.
In the gasification tower, the reaction CaO + H 2 S → CaS proceeds, and in the combustion tower,
CaS + 2O 2
→ CaSO 4 reaction proceeds.
Since the main purpose of CaO input as a circulating medium is CO 2 absorption and heat transfer, its molar ratio with respect to sulfur in the solid fuel is 30-200. It is much larger than the molar ratio (usually 2-3). Accordingly, even if H 2 S is absorbed in the gasification tower and in the low-temperature sulfur reabsorber, only a very thin film of CaS is generated on the surface of the CaO particles, so that it is easily oxidized by oxygen in the combustion tower. Further, it is granulated by fluid wear in the combustion tower, and classified and recovered by the combustion tower exhaust gas cyclone (or dust collector) 128.
In the present invention, a CaS film is formed on the surface of CaO particles in a gasification tower having a CaO / H 2 S molar ratio of 30-200 and in a low-temperature sulfur reabsorber, and the CaS film is oxidized by a combustion tower to form CaSO 4 . In addition, CaSO 4 powders due to wear and can be recovered with a dust collector or bag filter.

（補助燃料の使用）
バイオマスガス化の際に、石炭を補助燃料としてバイオマスと一緒にガス化塔１１０に導入される共ガス化方式が採用できる。
補助燃料として石炭を約10%使用し、燃料性状の安定化とガス化原料供給の安定化を調整することで、熱効率の最大化を図る。石炭を投入することによるCO2発生量の増加を相殺して、バイオマス単独利用時よりも単位合成ガスあたりの実際のCO2排出量が低減できる。
バイオマスは通常、水分量が40〜60％と高いため、ガス化に必要な水蒸気量よりも過大な水分をガス化炉に持ち込んでしまい、水蒸気になった水分から熱回収を行っても大きなエクセルギー損失となってしまう。これを避けるため、バイオマスを乾燥してガス化炉に供給する方法も一部で行われているが、乾燥に必要なエネルギー消費量が大きく、プラントの熱効率改善効果はわずかである。一方、石炭は、わが国で最も利用されている瀝青炭の水分が少なく、ガス化に必要な水分を外部からガス化炉に補給することでより大きなガスへの転換が図れる。以上のことから、バイオマスと石炭共ガス化は互いの燃料特性を補う効果もある。 (Use of auxiliary fuel)
In the case of biomass gasification, a co-gasification method in which coal is used as an auxiliary fuel and introduced into the gasification tower 110 together with biomass can be employed.
About 10% of coal is used as auxiliary fuel, and the thermal efficiency is maximized by adjusting the stability of fuel properties and the stabilization of gasification raw material supply. By offsetting the increase in CO 2 generation due to the input of coal, the actual CO 2 emissions per unit synthesis gas can be reduced compared to when using biomass alone.
Biomass usually has a high moisture content of 40 to 60%, so it takes too much moisture into the gasification furnace than the amount of water vapor required for gasification, and even if heat recovery is performed from the water that has become steam, a large excel Gee loss. In order to avoid this, part of the method of drying biomass and supplying it to the gasifier is also performed, but the energy consumption required for drying is large, and the effect of improving the thermal efficiency of the plant is slight. On the other hand, the bituminous coal used most in Japan has little moisture, and coal can be converted to a larger gas by supplying moisture necessary for gasification from the outside to the gasifier. From the above, biomass and coal co-gasification also have the effect of supplementing each other's fuel characteristics.

（低温硫黄再吸収器の性能）
燃焼塔の媒体サイクロンを経たCaO熱媒体の一部を低温硫黄再吸収器に導入し、改質ガス中の残留H2S、COS及びCO2を再吸収し、吸収後のCaSとCaCO3含有熱媒体を再び燃焼塔に導入し、循環させる。従って、改質塔から出た改質ガスは低温条件でCaOによって残留のH2SとCOS及びCO2を十分に吸収され、クリーンな合成ガスを製造できる。図６はCaOによるH2S吸収可能な温度範囲である。ガス中の水蒸気が多いほど、H2S吸収可能な温度がより低温側に移動する。同様な運転温度なら、改質ガス中の水蒸気を事前に分離すれば、ガス中H2SをよりCaOによって吸収される。 (Performance of low-temperature sulfur reabsorber)
Part of the CaO heat medium that has passed through the medium cyclone of the combustion tower is introduced into the low-temperature sulfur reabsorber, and the residual H 2 S, COS, and CO 2 in the reformed gas are reabsorbed, and after absorption, contains CaS and CaCO 3 The heat medium is again introduced into the combustion tower and circulated. Accordingly, the reformed gas exiting the reforming tower is sufficiently absorbed by CaO with residual H 2 S, COS and CO 2 at low temperature conditions, and a clean synthesis gas can be produced. FIG. 6 shows the temperature range in which H 2 S can be absorbed by CaO. The more water vapor in the gas, the lower the temperature at which H 2 S can be absorbed moves to the lower temperature side. If the operating temperature is the same, if the water vapor in the reformed gas is separated in advance, the H 2 S in the gas can be absorbed more by CaO.

（改質塔とガス化塔の構造）
改質塔とガス化塔の構造は、図４に示したほかにさらに以下のいくつ形式が考えられる。
図８に示すものは、改質塔とガス化塔を通気性の床を介して一体化し、循環媒体は、改質塔とガス化塔の装置内で送り込むものである。
図９に示すものは、改質塔とガス化塔を通気性の床を介して一体化し、循環媒体は、改質塔とガス化塔の装置外で送り込むものである。
当業者であれば、目的に応じて、改質塔とガス化塔の構造を適宜変えることもできる。
(Structure of reforming tower and gasification tower)
In addition to the structure of the reforming tower and the gasification tower shown in FIG.
In the structure shown in FIG. 8, the reforming tower and the gasification tower are integrated through an air-permeable bed, and the circulation medium is sent in the apparatus of the reforming tower and the gasification tower.
In FIG. 9, the reforming tower and the gasification tower are integrated through a gas-permeable bed, and the circulation medium is sent outside the equipment of the reforming tower and the gasification tower.
A person skilled in the art can appropriately change the structures of the reforming tower and the gasification tower according to the purpose.

本発明の三塔式循環流動層ガス化方法又は三塔式循環流動層ガス化装置は、長時間の連続運転が可能であるばかりか、流動層改質塔において、CaOの存在下、H2Oとガス化ガス及び液体燃料合成オフガス中のメタン等難分解炭化水素（CnHm）を反応させてCOとH2に分解し、合成ガスとし、液体燃料合成をおこない、液体燃料を取り出すことができ、温室効果ガス削減効果も期待でき、産業上極めて利用価値が高いものである。 The three-column circulating fluidized bed gasification method or the three-column circulating fluidized bed gasification apparatus of the present invention is capable of continuous operation for a long time, and in the fluidized bed reforming tower, in the presence of CaO, H 2 Refractory hydrocarbons (C n H m ) such as methane in O and gasified gas and liquid fuel synthesis off-gas are reacted to decompose into CO and H 2 to produce synthesis gas, liquid fuel synthesis, and liquid fuel extraction It can also be expected to reduce greenhouse gases, and is extremely useful in industry.

１ 流動層ガス化炉
２ 原料
３ 循環粒子（CaO）
７ 分離器
８ 流動層燃焼炉
１０燃焼ガス
１１分離器
１２排ガス
１４熱分解装置
１５粒子移動部
１６原料供給装置
１７ガス導入装置
１８上昇流形成ガス
１９熱分解ガス
２０熱分解ガス取出口
２１改質ガス化ガス
２２上側降下管
２３傾斜管
２４下側降下管
２８流動化ガス
３０溢流装置
３１上段の溢流装置
３２中間降下管
３３下段の溢流装置
１１０ 流動層ガス化塔
１２０ 流動層燃焼塔
１２５ 媒体サイクロン
１２８ 排ガスサイクロン
１３０ 改質塔
１４０ 熱交換器
１５０ 低温硫黄再吸収器
１６０ 液体燃料合成器

1 Fluidized bed gasifier 2 Raw material 3 Circulating particles (CaO)
7 Separator 8 Fluidized bed combustion furnace 10 Combustion gas 11 Separator 12 Exhaust gas 14 Pyrolysis device 15 Particle moving part 16 Raw material supply device 17 Gas introduction device 18 Upflow forming gas 19 Pyrolysis gas 20 Pyrolysis gas outlet 21 Reformation Gasification gas 22 Upper downcomer 23 Inclined pipe 24 Lower downcomer 28 Fluidized gas 30 Overflow device 31 Upper overflow device 32 Intermediate downcomer 33 Lower lower overflow device 110 Fluidized bed gasification tower 120 Fluidized bed combustion tower 125 medium cyclone 128 exhaust gas cyclone 130 reforming tower 140 heat exchanger 150 low temperature sulfur reabsorber 160 liquid fuel synthesizer

Claims (6)

温度850℃〜1000℃で運転する流動層燃焼塔と温度850℃〜1000℃で運転する流動層改質塔と温度650℃〜850℃で運転する流動層ガス化塔と400℃〜800℃で運転する低温硫黄再吸収器からなる三器式循環流動層ガス化方法であり、CaOを熱媒体、メタン等炭化水素改質触媒及びCO2とH2Sの吸収剤として、三塔及び低温硫黄再吸収器を結ぶ装置内で循環させ、バイオマスや石炭等固体燃料とガス化剤をガス化塔に供給し、650℃〜850℃の熱媒体と接触して熱分解とガス化を起こし、ガス化ガスとチャー（固定炭素）を生成し、また、ガス化塔でCaOが一部分のCO2とH2Sを吸収しCaCO3とCaSを生成し、ガス化ガス及びオフガスは改質塔に導入し、850℃〜1000℃のCaO熱媒体と接触してガス中のメタン等炭化水素の触媒改質を行い、残ったチャーは未反応のCaO熱媒体、CaCO3及びCaSと共に燃焼塔に導入し、空気でチャーを燃焼させ、CaO熱媒体を加熱し、CaCO3をCaOに焼成し、CaSをCaSO4に酸化し、CaO熱媒体は媒体サイクロンを経て改質塔とガス化塔に戻り、改質塔とガス化塔の温度を維持し、また、媒体サイクロンを経たCaO熱媒体の一部を低温硫黄再吸収器に導入し、改質塔から出た改質ガス中のH2S、COS及びCO2をCaOによって400℃〜800℃の低温で再吸収し、吸収後のCaOとCaSとCaCO3含有熱媒体を再び燃焼塔に導入させる三塔式循環流動層ガス化方法において、流動層改質塔において、CaOの存在下、H2Oとガス化ガス及びオフガス中のメタン等難分解炭化水素（CnHm）を反応させてCOとH2に分解し、合成ガスとし、液体燃料合成をおこない、液体燃料を取り出しながら、液体燃料にならないオフガスと重質残渣は、流動層改質塔及び又はガス化塔に戻すことを特徴とする改良型三塔式循環流動層ガス化方法。 Fluidized bed combustion tower operating at a temperature of 850 ° C to 1000 ° C, fluidized bed reforming tower operating at a temperature of 850 ° C to 1000 ° C, fluidized bed gasification tower operating at a temperature of 650 ° C to 850 ° C, and 400 ° C to 800 ° C A three-unit circulating fluidized bed gasification method consisting of operating low-temperature sulfur reabsorbers, with three towers and low-temperature sulfur using CaO as a heat medium, hydrocarbon reforming catalyst such as methane and CO 2 and H 2 S absorbents It is circulated in a device connecting the reabsorber, and a solid fuel such as biomass and coal and a gasifying agent are supplied to the gasification tower, and contacted with a heat medium at 650 ° C to 850 ° C to cause pyrolysis and gasification. Gasification gas and char (fixed carbon) are produced, and CaO absorbs a part of CO 2 and H 2 S in the gasification tower to produce CaCO 3 and CaS. The gasification gas and off-gas are introduced into the reforming tower. and, in contact with 850 ° C. to 1000 ° C. of CaO heat medium subjected to catalytic reforming, such as methane hydrocarbon in the gas, remaining char unreacted CaO heat medium, CaCO 3 Introduced into the combustion tower with fine CaS, the char with air is burned to heat the CaO heating medium, firing the CaCO 3 to CaO and oxidation of CaS into CaSO 4, CaO heat medium reforming tower through the medium cyclone Return to the gasification tower, maintain the temperature of the reforming tower and the gasification tower, and introduce a part of the CaO heat medium that passed through the medium cyclone into the low-temperature sulfur reabsorber, and then reformed from the reforming tower Three-column circulation flow in which H 2 S, COS and CO 2 in the gas are reabsorbed by CaO at a low temperature of 400 ° C to 800 ° C, and the heat medium containing CaO, CaS and CaCO 3 after absorption is reintroduced into the combustion tower In the bed gasification method, in the fluidized bed reforming tower, CO 2 and H 2 are reacted by reacting H 2 O with gasified gas and refractory hydrocarbons such as methane (C n H m ) in the off-gas in the presence of CaO. The off-gas and heavy residues that do not become liquid fuel are removed from the fluidized bed while synthesizing and synthesizing liquid fuel and taking out the liquid fuel. Improved three-tower type circulating fluidized-bed gasification method and returning to the tower and or gasification tower. CaO媒体の一部を低温硫黄再吸収器に導入し、改質塔から出た改質ガス中のH2S、COS及びCO2を低温硫黄再吸収器でのCaOによって再吸収し、吸収後のCaOとCaSとCaCO3含有媒体を再び燃焼塔に導入させる請求項１に記載の改良型三塔式循環流動層ガス化方法 Part of the CaO medium is introduced into the low-temperature sulfur reabsorber, and H 2 S, COS and CO 2 in the reformed gas from the reforming tower are reabsorbed by CaO in the low-temperature sulfur reabsorber, and after absorption The improved three-column circulating fluidized bed gasification method according to claim 1, wherein the medium containing CaO, CaS, and CaCO 3 is again introduced into the combustion tower. 補助燃料として石炭を使用し、バイオマスと共ガス化する請求項１に記載の改良型三塔式循環流動層ガス化方法。   The improved three-column circulating fluidized bed gasification method according to claim 1, wherein coal is used as auxiliary fuel and co-gasified with biomass. 流動層燃焼塔と流動層改質塔との間に、媒体サイクロンを設ける請求項１又は請求項２に記載の改良型三器式循環流動層ガス化方法。 The improved three-unit circulating fluidized bed gasification method according to claim 1 or 2, wherein a medium cyclone is provided between the fluidized bed combustion tower and the fluidized bed reforming tower. CaOベース媒体を伝熱媒体、改質触媒及びCO2とH2Sの吸収剤とし、三塔式循環流動層ガス化炉装置内で循環させ、石炭とバイオマスをガス化塔に供給し、熱媒体と接触して650-850℃で熱分解とガス化を起こし、ガス化ガスとチャー（固定炭素）を生成し、ガス化ガスとオフガスは改質塔に導入し、850℃〜1000℃の熱媒体と接触してガス化ガスオフガス中のメタン（CH4）等難分解性炭化水素(CnHm)の触媒改質を行い、改質塔から出た改質ガスを低温硫黄再吸収器に導入し、CaOによって400℃〜800℃の低温で改質ガス中のH2SとCO2を再吸収し、低温硫黄再吸収器から出たクリーン合成ガスはガス洗浄を経て燃料合成装置に提供され、液体燃料として取り出し、液体燃料にならないオフガスと重質残渣は、流動層改質塔及び（或いは）ガス化塔に戻す請求項１に記載の改良型三塔式循環流動層ガス化方法。 The CaO base medium is used as a heat transfer medium, reforming catalyst, and CO 2 and H 2 S absorbent, and is circulated in a three-column circulating fluidized bed gasifier, supplying coal and biomass to the gasification tower, Pyrolysis and gasification occur at 650-850 ° C in contact with the medium to generate gasified gas and char (fixed carbon). The gasified gas and off-gas are introduced into the reforming tower, and the temperature is between 850 ° C and 1000 ° C. Catalytic reforming of refractory hydrocarbons (C n H m ) such as methane (CH 4 ) in the gasified gas off-gas in contact with the heat medium, and the reformed gas from the reforming tower is converted to a low-temperature sulfur resorber Was introduced into the reformed gas, and H 2 S and CO 2 in the reformed gas were reabsorbed by CaO at a low temperature of 400 ° C. to 800 ° C., and the clean syngas emitted from the low temperature sulfur reabsorber was passed through the gas scrubbing to the fuel synthesizer Off-gas and heavy residues that are provided and removed as liquid fuel but not liquid fuel are returned to the fluidized bed reforming tower and / or gasification tower. Improved three-tower type circulating fluidized-bed gasification method according to claim 1. 温度850℃〜1000℃で運転する流動層燃焼塔と温度850℃〜1000℃で運転する流動層改質塔と温度650℃〜850℃で運転する流動層ガス化塔と400℃〜800℃で低温硫黄再吸収器からなる三塔式循環流動層ガス化装置であり、CaOを伝熱媒体、触媒及びCO2とH2Sの吸収剤として、三塔及び低温硫黄再吸収器を結ぶ装置内で循環させ、バイオマス、石炭等固体燃料をガス化塔に供給し、650-850℃の熱媒体と接触して熱分解とガス化を起こし、ガス化ガスとチャー（固定炭素）を生成し、また、ガス化塔でCaOが一部のCO2とH2Sを吸収し、CaCO3とCaSを生成し、ガス化ガスとオフガスは改質塔に導入し、850-1000℃の熱媒体と接触してガス化ガスと液体燃料合成のオフガス中のメタン等炭化水素(CnHm)の触媒改質を行い、チャーは未反応CaO熱媒体、CaCO3及びCaSと共に燃焼塔に導入し、空気でチャーを燃焼させ、熱媒体を加熱し、CaCO3をCaOに焼成し、CaSをCaSO4に酸化し、熱媒体はサイクロンを経て改質塔とガス化塔に戻り、改質塔とガス化塔の温度を維持し、また、サイクロンを経たCaO媒体の一部を低温硫黄再吸収器に導入し、改質塔から出た改質ガス中のH2S、COS及びCO2をCaOによって再吸収し、吸収後のCaSとCaCO3含有熱媒体を再び燃焼塔に導入させる改良型三塔式循環流動層ガス化装置。 Fluidized bed combustion tower operating at a temperature of 850 ° C to 1000 ° C, fluidized bed reforming tower operating at a temperature of 850 ° C to 1000 ° C, fluidized bed gasification tower operating at a temperature of 650 ° C to 850 ° C, and 400 ° C to 800 ° C This is a three-column circulating fluidized bed gasifier consisting of low-temperature sulfur reabsorber. CaO is used as a heat transfer medium, catalyst and CO 2 and H 2 S absorbent. , And supply solid fuel such as biomass and coal to the gasification tower, contact with a heat medium of 650-850 ℃, cause pyrolysis and gasification, and generate gasified gas and char (fixed carbon), In the gasification tower, CaO absorbs part of CO 2 and H 2 S to produce CaCO 3 and CaS. The gasification gas and off-gas are introduced into the reforming tower, and the heat medium at 850-1000 ° C is used. contacting perform catalytic reforming of methane, such as hydrocarbons in off-gas gasification gas and the liquid fuel synthesis (C n H m), a char unreacted CaO heating medium, combustion tower with CaCO 3 and CaS Introduced, the combustion of char with air, to heat the heat medium, firing the CaCO 3 to CaO, to oxidize CaS to CaSO 4, the heat medium is returned to the reforming tower and gasification tower through a cyclone, modified The temperature of the tower and the gasification tower is maintained, and a part of the CaO medium that has passed through the cyclone is introduced into the low-temperature sulfur reabsorber, and H 2 S, COS, and CO 2 in the reformed gas discharged from the reforming tower Is an improved three-column circulating fluidized bed gasifier that re-absorbs CaO and absorbs the CaS and CaCO 3 -containing heat medium after absorption into the combustion tower.
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CN106590757A (en) * 2015-10-15 2017-04-26 中国石油化工股份有限公司 Device and method for segmented-oxygen-blowing catalytic coal gasification
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