JP2011026490A - Method of supplying catalyst to gasification furnace in gasification system - Google Patents
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本発明は、循環流動層を用いて燃料より可燃ガスを取り出すためのガス化システムに係り、簡便な手法で触媒を活性化し、高効率で生成ガスを取り出すことができるガス化システムに関するものである。 The present invention relates to a gasification system for extracting a combustible gas from a fuel using a circulating fluidized bed, and relates to a gasification system that can activate a catalyst by a simple method and extract a generated gas with high efficiency. .
従来から、石炭、バイオマス、ごみ、下水汚泥などの炭化水素資源の固体燃料を利用し、生成したガスを、可燃ガス及び熱源として利用することにより、有機資源の有効活用を図るガス化システムが開発されている。
該ガス化システムの１つとして、ガス化反応炉を流動層ガス化炉と流動層燃焼炉に分離し、流動層ガス化炉に、炭化水素資源の固体燃料及び流動媒体を供給し、水蒸気でガス化を行い、生成した未燃分（チャー）と流動媒体を流動層燃焼炉で燃焼させ、加熱された流動媒体を前記ガス化炉に戻す循環流動層を用いたものが知られている（特許文献１）。
この流動層ガス化炉と流動層燃焼炉を有する循環流動層ガス化システムにおいては、それぞれの炉から、ガス化ガスと燃焼ガスを別々に取り出すことができ、不活性ガスを含まない高カロリーなガスを製造することができる。
Conventionally, a gasification system has been developed that uses solid fuels of hydrocarbon resources such as coal, biomass, garbage, sewage sludge, etc., and uses the generated gas as a combustible gas and heat source to effectively use organic resources. Has been.
As one of the gasification systems, a gasification reaction furnace is separated into a fluidized bed gasification furnace and a fluidized bed combustion furnace, and a solid fuel and a fluid medium of hydrocarbon resources are supplied to the fluidized bed gasification furnace. It is known to use a circulating fluidized bed that performs gasification, burns the generated unburned part (char) and fluidized medium in a fluidized bed combustion furnace, and returns the heated fluidized medium to the gasification furnace ( Patent Document 1).
In the circulating fluidized bed gasification system having the fluidized bed gasification furnace and the fluidized bed combustion furnace, the gasification gas and the combustion gas can be separately taken out from the respective furnaces. Gas can be produced.
一方、特許文献２では、流動層焼却炉又は焼却炉において、流動媒体として焼成石灰石又は焼成ドロマイトを使用し、流動媒体の多孔質細孔の容量効果により、燃焼中に、原料中の炭化水素成分の一部、及び／又は、タールを前記細孔に保持した後、当該細孔内において或いは当該細孔から再放出させて燃焼させるので、未燃焼原料又はタールが炉外に排出することを防ぐことが提案されている。
また、特許文献３には、特許文献１の循環流動層ガス化システムにおいて、流動層ガス化炉に、流動媒体粒子と、石灰石などの触媒と、ガス化剤、及び原料を供給してガス化を行う際、触媒が粉化により劣化した場合や炉外へ粉化して飛散した場合に、定常運転中の炉内圧力や生成ガス量をベースとして、その分新たな触媒を随時供給できるガス化システムが提案されている。
さらに、非特許文献１では、研究室規模の流動層ガス化炉を用い、ガス化触媒として、焼成後の石灰石を燃料と予混合してガス化実験を行うと、得られるガス化効率は、触媒なしの場合よりも向上することが報告されている。
On the other hand, in Patent Document 2, in a fluidized bed incinerator or incinerator, a calcined limestone or calcined dolomite is used as a fluidized medium, and the hydrocarbon component in the raw material during combustion due to the volume effect of the porous pores of the fluidized medium. Since part of and / or tar is retained in the pores and then burned in the pores or re-released from the pores, unburned raw material or tar is prevented from being discharged out of the furnace. It has been proposed.
Patent Document 3 discloses gasification by supplying fluidized medium particles, a catalyst such as limestone, a gasifying agent, and a raw material to a fluidized bed gasification furnace in the circulating fluidized bed gasification system of Patent Document 1. When the catalyst deteriorates due to pulverization or pulverizes and scatters outside the furnace, gasification that can supply new catalyst as needed based on the pressure in the furnace and the amount of generated gas during steady operation A system has been proposed.
Furthermore, in Non-Patent Document 1, when a gasification experiment is performed using a laboratory-scale fluidized bed gasification furnace and preliminarily mixing calcined limestone with fuel as a gasification catalyst, the gasification efficiency obtained is It has been reported that it is improved over the case without catalyst.
そこで、ガス化効率を向上させるために、前記流動層ガス化炉内に供給するガス化触媒として、焼成後の石灰石を用いることが考えられるが、この方法では、焼成という触媒の前処理が必要となる。
しかしながら、特許文献２には、焼成後の石灰石又はドロマイトを使用するものであるが、前処理の「焼成」については触れられていない。同様に、非特許文献１も、焼成後の石灰石の使用を示唆するものの、その前処理の焼成については、全く触れられていない。
一方、特許文献３では、触媒として焼成した石灰石を用いることについて全く記載がない。
Therefore, in order to improve gasification efficiency, it is conceivable to use calcined limestone as a gasification catalyst supplied into the fluidized bed gasification furnace. In this method, a catalyst pretreatment called calcination is necessary. It becomes.
However, Patent Document 2 uses limestone or dolomite after firing, but does not mention pre-fired “firing”. Similarly, Non-Patent Document 1 suggests the use of limestone after firing, but does not mention the firing of the pretreatment at all.
On the other hand, in patent document 3, there is no description about using the calcined limestone as a catalyst.
本発明は、こうした従来技術における課題を解決するものであって、石灰石又はドロマイト等のガス化触媒の前処理を簡易な手法で実施できるとともに、高効率でガスを得ることが可能なガス化システムを提供することを目的とするものである。 The present invention solves such a problem in the prior art, and can perform pretreatment of a gasification catalyst such as limestone or dolomite by a simple method and can obtain gas with high efficiency. Is intended to provide.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、石灰石（ＣａＣＯ３）やドロマイト（ＣａＣＯ３・ＭｇＣＯ３）などをガス化触媒として利用する場合、さきに流動層燃焼炉側へ供給して脱炭酸化（焼成）させ、焼成後の触媒（ＣａＯやＣａＯ・ＭｇＯなど）を流動層ガス化炉へ送ることで、解決しうることを見いだした。 As a result of intensive studies to achieve the above object, the inventors of the present invention, when using limestone (CaCO 3 ), dolomite (CaCO 3 .MgCO 3 ) or the like as a gasification catalyst, firstly on the fluidized bed combustion furnace side. It was found that this could be solved by supplying to the catalyst and decarboxylating (calcining) and sending the calcined catalyst (CaO, CaO · MgO, etc.) to the fluidized bed gasification furnace.
本発明は、これらの知見に基づいて完成に至ったものであり、以下のとおりのものである。
［１］少なくともガス化炉と燃焼炉とからなる流動層ガス化反応炉を有し、前記ガス化炉において、流動媒体、ガス化触媒及びガス化剤の存在下で燃料を供給し、次いで、ガス化炉で生成した残渣チャーを流動媒体と共に燃焼炉に導入することにより、それぞれの炉から、ガス化ガスと燃焼ガスを別々に取り出すガス化システムにおいて、
ガス化触媒として用いる石灰石又はドロマイトを、先に前記燃焼炉側へ供給して焼成し、焼成後のガス化触媒を、前記ガス化炉へ送るようにしたことを特徴とするガス化システム。
［２］流動層ガス化反応炉下部から抜き出した触媒や粉化して飛散した触媒を、後段に設けたスクラバで再利用するようにしたことを特徴とする請求項１に記載のガス化システム。
The present invention has been completed based on these findings, and is as follows.
[1] A fluidized bed gasification reaction furnace comprising at least a gasification furnace and a combustion furnace, wherein fuel is supplied in the presence of a fluidized medium, a gasification catalyst, and a gasifying agent in the gasification furnace, In the gasification system that separates the gasification gas and the combustion gas from each furnace by introducing the residual char generated in the gasification furnace into the combustion furnace together with the fluid medium,
A gasification system characterized in that limestone or dolomite used as a gasification catalyst is first supplied to the combustion furnace side and calcined, and the calcined gasification catalyst is sent to the gasification furnace.
[2] The gasification system according to claim 1, wherein the catalyst extracted from the lower part of the fluidized bed gasification reactor or the catalyst pulverized and scattered is reused by a scrubber provided at a later stage.
本発明によれば、流動層ガス化炉内の燃焼炉で触媒を焼成することにより、ガス化触媒の石灰石の前処理を簡便に行うことができ、また、炉後段のスクラバで再利用することにより、触媒の能力を最大限活用できる。 According to the present invention, by pre-firing the catalyst in the combustion furnace in the fluidized bed gasification furnace, pretreatment of the limestone of the gasification catalyst can be easily performed, and can be reused in the scrubber at the latter stage of the furnace. The maximum capacity of the catalyst can be used.
以下、本発明の実施の形態について、図面に基づいて説明するが、本発明はこの実施の形態に限定されるものではない。
図１は、本発明のガス化システムの１例を示す概要図である。
図１に示すシステムは、ガス化炉と燃焼炉がそれぞれ独立して設けられ、それぞれの炉が連通路によりこの順に連結された流動層ガス化反応炉を有している。
ガス化炉で製造したガス化ガスは、熱交換器、ボイラ、及びスクラバを通過させた後に、タール吸収塔で活性炭により、主に軽質タールを除去し、例えば、ガスエンジンを利用した発電に利用できる。
Embodiments of the present invention will be described below with reference to the drawings. However, the present invention is not limited to these embodiments.
FIG. 1 is a schematic diagram showing an example of a gasification system of the present invention.
The system shown in FIG. 1 has a fluidized bed gasification reactor in which a gasification furnace and a combustion furnace are provided independently, and each furnace is connected in this order by a communication path.
Gasified gas produced in a gasifier passes through heat exchangers, boilers, and scrubbers, and then removes light tar mainly with activated carbon in a tar absorption tower. For example, it is used for power generation using a gas engine. it can.
本発明のシステムについて、ガス化触媒として石灰石を使用する例を用いて、具体的に説明する。
本発明のシステムにおいては、最初に、流動層ガス化反応炉内の燃焼炉側へ石灰石原料を供給する。石灰石は、燃焼炉内で脱炭酸化（焼成）されて、ＣａＯ粒子となり、燃焼炉後段のサイクロンで燃焼ガスと分離されて、ガス化炉へ送られる。
The system of the present invention will be specifically described using an example in which limestone is used as a gasification catalyst.
In the system of the present invention, first, a limestone raw material is supplied to the combustion furnace side in the fluidized bed gasification reactor. Limestone is decarboxylated (fired) in the combustion furnace to become CaO particles, separated from the combustion gas by a cyclone at the rear stage of the combustion furnace, and sent to the gasification furnace.
ガス化炉には、前記ＣａＯ粒子、流動媒体、及びバイオマス、ごみ、下水汚泥などの有機資源、或いは石炭等の炭化水素系固体燃料を供給するとともに、ガス化剤としては、例えば、燃焼炉で生成した燃焼ガスの一部を再循環させたＣＯ２ガス、あるいはＮ２やＡｒのような不活性ガス、水蒸気、酸素、空気等を導入する。
ガス化炉は流動層とされており、ガス化触媒としてのＣａＯ粒子の存在下で、炭化水素系燃料は、下部より導入されたガス化剤とのガス化反応によりガス化される。
ガス化炉内で生成したガス化ガスは、ガス化炉上部より取り出す一方、残渣チャー、ＣａＯ粒子、及び流動媒体は、次の燃焼炉へ導入される。
取り出されたガス化ガスは可燃ガスであり、燃料電池やガスエンジンによる発電、液体燃料などに利用される。
The gasification furnace is supplied with the CaO particles, fluid medium, and organic resources such as biomass, garbage, sewage sludge, or hydrocarbon-based solid fuel such as coal. A CO 2 gas obtained by recirculating a part of the generated combustion gas, an inert gas such as N 2 or Ar, water vapor, oxygen, air, or the like is introduced.
The gasification furnace is a fluidized bed, and in the presence of CaO particles as a gasification catalyst, the hydrocarbon fuel is gasified by a gasification reaction with a gasifying agent introduced from the lower part.
While the gasification gas produced in the gasification furnace is taken out from the upper part of the gasification furnace, the residual char, CaO particles, and the fluidized medium are introduced into the next combustion furnace.
The extracted gasified gas is a combustible gas, and is used for power generation by a fuel cell or a gas engine, liquid fuel, or the like.
燃焼炉は、流動層とされており、残渣チャーが完全燃焼可能な滞留時間を確保する。該燃焼炉では導入された残渣チャーを、燃焼炉の下部より導入された酸素或いは空気とともに、燃焼させ、後段に設けられたサイクロン（図示せず）により燃焼ガスを取り出す。一方、再加熱された流動媒体及びＣａＯ粒子は、再びガス化炉へ戻される。
取り出された燃焼ガスは、主に熱源として利用されるものであり、前述したとおり、その一部はガス化炉に再循環させることも可能である。また、前記ガス化炉又は燃焼炉に導入する空気等の予熱としても利用できる。
The combustion furnace is a fluidized bed, and ensures a residence time during which the residual char can be completely combusted. In the combustion furnace, the introduced residual char is burned together with oxygen or air introduced from the lower part of the combustion furnace, and the combustion gas is taken out by a cyclone (not shown) provided in the subsequent stage. On the other hand, the reheated fluid medium and CaO particles are returned to the gasifier again.
The extracted combustion gas is mainly used as a heat source, and as described above, a part thereof can be recycled to the gasification furnace. Moreover, it can utilize also as preheating of the air etc. which are introduce | transduced into the said gasification furnace or a combustion furnace.
本発明のシステムにおいて、最初に燃焼炉に供給された石灰石の焼成時に生成したＣＯ２ガスは、燃焼炉後段のサイクロン（図示せず）で分離され、燃焼ガスとともに炉外へ放出される。
したがって、石灰石などの焼成により生成したＣＯ２ガスがガス化炉で生成する可燃ガスと混在することはない。
In the system of the present invention, the CO 2 gas generated at the time of calcination of limestone first supplied to the combustion furnace is separated by a cyclone (not shown) at the rear stage of the combustion furnace, and is released to the outside of the furnace together with the combustion gas.
Therefore, the CO 2 gas generated by firing limestone or the like is not mixed with the combustible gas generated in the gasification furnace.
また、触媒として用いるＣａＯ粒子は、いずれは炉内脱硫などによる劣化により炉下部から抜き出したり、粉化により炉外へ飛散したりする可能性がある。その分は新たな石灰石を燃焼炉側より供給すれば良い。
抜き出したＣａＯ粒子及び飛散したＣａＯ粒子は、炉後段のスクラバで再利用し、その能力を最大限活用し、最終的には、セメントなどの原料に活用する。
本システムであれば、流動層ガス化炉内で触媒を焼成することができるので、焼成のための前処理設備などが不要となる。
In addition, CaO particles used as a catalyst may be extracted from the lower part of the furnace due to deterioration due to in-furnace desulfurization or scattered outside the furnace due to pulverization. To that extent, new limestone may be supplied from the combustion furnace side.
The extracted CaO particles and the scattered CaO particles are reused in a scrubber at the post-furnace stage, and their capacity is utilized to the maximum, and finally used as a raw material such as cement.
With this system, the catalyst can be calcined in a fluidized bed gasification furnace, so that no pretreatment equipment for calcining is required.
図１に示す流動層ガス化反応炉はあくまで一例であって、条件によっては、一塔式のガス化炉（バブリング流動層など）やガス化炉部分をさらに熱分解炉とガス化炉に分離させた二塔式ガス化炉においても十分適用可能である。
また、本発明のシステムにおいては、流動媒体として一般的に硅砂が使用されるが、触媒を流動媒体として利用する場合や硅砂と混合する場合においても、本発明のシステムは適用できる。例えば、流動媒体に全て石灰石を使用する場合、初期投入した分は、炉の昇温中に全て焼成されるので、ガス化における定常運転中に、新たな追加分を燃焼炉側より供給すれば良い。
The fluidized bed gasification reactor shown in FIG. 1 is merely an example, and depending on the conditions, a single tower type gasification furnace (such as a bubbling fluidized bed) or a gasification furnace is further separated into a pyrolysis furnace and a gasification furnace. The present invention can be sufficiently applied to the two-column gasifier.
Further, in the system of the present invention, cinnabar is generally used as a fluid medium, but the system of the present invention can also be applied when a catalyst is used as a fluid medium or mixed with cinnabar. For example, when all the limestone is used as the fluid medium, all the initial charge is baked during the temperature rise of the furnace, so if a new additional part is supplied from the combustion furnace side during steady operation in gasification good.
Claims (2)
ガス化触媒として用いる石灰石又はドロマイトを、先に前記燃焼炉側へ供給して焼成し、焼成後のガス化触媒を、前記ガス化炉へ送るようにしたことを特徴とするガス化システム。 A fluidized bed gasification reaction furnace comprising at least a gasification furnace and a combustion furnace, wherein fuel is supplied in the presence of a fluidized medium, a gasification catalyst and a gasifying agent, and then the gasification furnace In the gasification system for separately extracting the gasification gas and the combustion gas from each furnace by introducing the residual char generated in step 1 into the combustion furnace together with the fluid medium,
A gasification system characterized in that limestone or dolomite used as a gasification catalyst is first supplied to the combustion furnace side and calcined, and the calcined gasification catalyst is sent to the gasification furnace.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101179473B1 (en) | 2010-02-19 | 2012-09-07 | 한국에너지기술연구원 | oxy-combustion system using chemical heat recovery |
| JP2012255114A (en) * | 2011-06-10 | 2012-12-27 | Ihi Corp | System and method for producing gasified gas |
| JP2014037516A (en) * | 2012-08-20 | 2014-02-27 | Ihi Corp | Gasification gas generation system and gasification gas generation method |
| WO2021102536A1 (en) * | 2019-11-26 | 2021-06-03 | Petróleo Brasileiro S.A. - Petrobras | Process of catalytic gasification, catalyst, use of the catalyst and process for preparing the catalyst |
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2009
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101179473B1 (en) | 2010-02-19 | 2012-09-07 | 한국에너지기술연구원 | oxy-combustion system using chemical heat recovery |
| JP2012255114A (en) * | 2011-06-10 | 2012-12-27 | Ihi Corp | System and method for producing gasified gas |
| JP2014037516A (en) * | 2012-08-20 | 2014-02-27 | Ihi Corp | Gasification gas generation system and gasification gas generation method |
| WO2021102536A1 (en) * | 2019-11-26 | 2021-06-03 | Petróleo Brasileiro S.A. - Petrobras | Process of catalytic gasification, catalyst, use of the catalyst and process for preparing the catalyst |
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