JPH0258598A - Treatment of coal gasified fuel into low nox content - Google Patents
Treatment of coal gasified fuel into low nox contentInfo
- Publication number
- JPH0258598A JPH0258598A JP20955988A JP20955988A JPH0258598A JP H0258598 A JPH0258598 A JP H0258598A JP 20955988 A JP20955988 A JP 20955988A JP 20955988 A JP20955988 A JP 20955988A JP H0258598 A JPH0258598 A JP H0258598A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- coal
- fuel
- injected
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 113
- 239000003245 coal Substances 0.000 title claims abstract description 110
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 178
- 239000007789 gas Substances 0.000 claims abstract description 77
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000001301 oxygen Substances 0.000 claims abstract description 66
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 100
- 238000000354 decomposition reaction Methods 0.000 claims description 42
- 238000002309 gasification Methods 0.000 claims description 33
- 238000002485 combustion reaction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 238000002347 injection Methods 0.000 claims description 14
- 239000007924 injection Substances 0.000 claims description 14
- 239000000567 combustion gas Substances 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims 2
- 238000005336 cracking Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract 1
- 238000010248 power generation Methods 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は石炭ガス化燃料の低ＮＯｘ化処理方法に関する
。更に詳述すると、本発明は石炭ガス化燃料に不純物と
して含まれるアンモニアを乾式で連続的に除去する方法
に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for reducing NOx in coal gasified fuel. More specifically, the present invention relates to a dry continuous method for removing ammonia contained in coal gasified fuel as an impurity.
（従来の技術）
近年、高効率で環境保全性に優れた石炭利用新技術とし
て石炭ガス化複合発電が国内外において注目されている
０石炭ガス化複合発電とは石炭をガス化炉でガス化し、
これをガス精製装置により脱硫、脱塵した後、ガスター
ビン燃焼器で燃焼させることによりガスタービンで発電
すると同時にその排熱で蒸気を発生させて蒸気タービン
でも発電する方式である。(Conventional technology) In recent years, coal gasification combined cycle power generation has been attracting attention domestically and internationally as a new coal utilization technology that is highly efficient and environmentally friendly.Coal gasification combined cycle power generation is a process in which coal is gasified in a gasifier. ,
This is desulfurized and dedusted using a gas purification device, and then combusted in a gas turbine combustor to generate electricity in the gas turbine.At the same time, the exhaust heat is used to generate steam and the steam turbine also generates electricity.
ところで、このようなガスタービン等の燃焼にあっては
、窒素酸化物ＮＯｘの生成を伴うが、窒素酸化物は光化
学スモッグなどの原因となる環境汚染物質であるため、
環境に放出できる量・濃度は厳しく規制されている。Incidentally, combustion in such gas turbines and the like involves the production of nitrogen oxides (NOx), which are environmental pollutants that cause photochemical smog.
The amount and concentration that can be released into the environment is strictly regulated.
そこで、従来のＮＯｘ防止対策としてはＮＯｘの発生を
抑える燃焼技術の採用、燃焼排ガス中のＮＯｘを除去す
る脱硝技術の採用が一般的である。Therefore, conventional NOx prevention measures generally include the adoption of combustion technology to suppress the generation of NOx, and the adoption of denitrification technology to remove NOx from combustion exhaust gas.
しかし、燃料自体が問題とされることは従来なく、また
燃料自体にＮｏにの原因となるアンモニアが問題となる
程合まれることもなかっな。However, the fuel itself has never been considered a problem, and the fuel itself has never been contaminated with ammonia, which causes NO, to the extent that it becomes a problem.
ところが、石炭をガス化炉でガス化する時、石炭中の窒
素分の一部がアンモニア（ＮＨ３）に転換するため、石
炭ガス化燃料中にはＮＨ３が不純物として含まれること
になる。ＮＨ３は水に吸収されやすいため、ガス精製を
スクラバーなどの湿式方法で行う場合にはＮＨ３は容易
に除去される。However, when coal is gasified in a gasifier, part of the nitrogen content in the coal is converted to ammonia (NH3), so NH3 is included as an impurity in the coal gasified fuel. Since NH3 is easily absorbed by water, NH3 is easily removed when gas purification is performed using a wet method such as a scrubber.
しかしながらその場合には石炭ガス化燃料の温度が下が
るため、石炭ガス化複合発電システムにおける熱効率が
低下する。このなめ、石炭ガス化複合発電システムにお
けるガス精製はドライ（乾式）状態で行う方法が要望さ
れる。しかし、その場合には石炭ガス化炉内で生成され
たＮＨ３はほとんどそのままの濃度でガスタービン燃焼
器に供給されることとなる。そして、この燃料中に含ま
れるＮＨ３は燃焼の過程で容易に窒素酸化物（ＮＯｘ）
に転換する。However, in that case, the temperature of the coal gasification fuel decreases, resulting in a decrease in thermal efficiency in the coal gasification combined cycle power generation system. For this reason, there is a demand for a method in which gas purification in a coal gasification combined cycle power generation system is performed in a dry state. However, in that case, the NH3 generated in the coal gasifier will be supplied to the gas turbine combustor at almost the same concentration. The NH3 contained in this fuel easily becomes nitrogen oxides (NOx) during the combustion process.
Convert to
石炭カス化炉内で生成されるアンモニア濃度は石炭種や
ガス化条件によって異なるが数百ｐｐｌから数千Ｉ）Ｉ
）ｌとされ、ガスタービン燃焼器で発生ずるＮＯｘのう
ちＮＨ３に起因するＮＯｘの占める割合は高い、このた
め石炭ガス化燃料中のＮＨ８に起因する窒素酸化物を低
減させるための石炭ガス化複合発電システムにおける低
ＮＯｘ化技術が必要とされている。The concentration of ammonia produced in a coal casing furnace varies depending on the type of coal and gasification conditions, but ranges from several hundred ppl to several thousand I)I
)l, and the proportion of NOx caused by NH3 in the NOx generated in the gas turbine combustor is high. Therefore, a coal gasification complex is used to reduce nitrogen oxides caused by NH8 in coal gasified fuel. There is a need for technology to reduce NOx in power generation systems.
（発明が解決しようとする課題）
しかしながら、石炭ガス化燃料は通常の気体燃料に比べ
極めて低カロリー（２０００ｋｃａ ｌ以下）で燃え難
いガスである上にガスタービン燃焼器での燃焼は火炎伝
播速度を上回る速度で燃料が流れるため益々着火し難く
火炎安定性に欠ける燃焼条件にある。このため、ガスタ
ービン燃焼器において燃料中のＮＨ３に起因する窒素酸
化物を低減させるための燃焼技術を確立することはとて
も難度が高く現在鋭意研究開発が進められているが未だ
実現するに至っていない、また、燃焼排ガス中のＮ。(Problems to be Solved by the Invention) However, coal gasified fuel has an extremely low calorie (less than 2000 kcal) and is difficult to burn compared to normal gaseous fuel, and its combustion in a gas turbine combustor has a low flame propagation speed. Because the fuel flows at a faster speed, it becomes increasingly difficult to ignite, resulting in combustion conditions that lack flame stability. For this reason, it is extremely difficult to establish combustion technology to reduce nitrogen oxides caused by NH3 in the fuel in gas turbine combustors, and although research and development is currently underway, it has not yet been realized. , and N in combustion exhaust gas.
Ｘを除去する方法として一般的なアンモニア注入による
触媒式排煙脱硝装置は既に確立した技術であると言える
が、高価な触媒を使用すると共に約３万時間毎に触媒を
交換しなければならないことから、石炭ガス化複合発電
システムに設置することはシステムの運転の上からも経
済的にも大きな負担となる。Catalytic exhaust gas denitrification equipment using ammonia injection, which is a common method for removing X, can be said to be an established technology, but it uses an expensive catalyst and requires replacing the catalyst approximately every 30,000 hours. Therefore, installing it in a coal gasification combined cycle power generation system poses a large burden both from the operational and economic standpoints of the system.
そこで本発明は燃料自体の改善、即ち石炭ガス化燃料の
低ＮＯｘ化処理方法を提供することを目的とする。具体
的には、石炭ガス化燃料中のアンモニアを乾式で連続的
に除去する方法を提供することを目的とする。Therefore, an object of the present invention is to improve the fuel itself, that is, to provide a method for reducing NOx in coal gasified fuel. Specifically, the purpose of the present invention is to provide a method for continuously removing ammonia from coal gasified fuel in a dry manner.
（課題を解決するための手段）
かかる目的を達成するため、本発明の石炭ガス化燃料の
低ＮＯｘ化処理は、石炭ガス化炉を出てガスタービン燃
焼器に供給する前の冷却された石炭ガス化燃料中に、酸
素あるいは酸素を含む気体若しくは蒸発して酸素ガスを
生ずる化合物を注入し混合拡散し、その後反応温度以上
に加熱して分解反応させてから前記ガスタービン燃焼器
に供給するするようにしている。(Means for Solving the Problems) In order to achieve the above object, the NOx reduction treatment of coal gasified fuel of the present invention is carried out by reducing the amount of CO Oxygen, a gas containing oxygen, or a compound that evaporates to produce oxygen gas is injected into the gasified fuel, mixed and diffused, and then heated above the reaction temperature to undergo a decomposition reaction before being supplied to the gas turbine combustor. That's what I do.
また、本発明の石炭ガス化燃料の低ＮＯｘ化処理は、石
炭ガス化炉を出てガスタービン燃焼器に供給する前の冷
却された石炭ガス化燃料中に、酸素あるいは酸素を含む
気体若しくは蒸発して酸素ガスを生ずる化合物と共に窒
素酸化物を注入し混合拡散し、その後反応温度以上に加
熱して分解反応させてから前記ガスタービン燃焼器に供
給するようにしている。In addition, the NOx reduction treatment of coal gasified fuel of the present invention is performed by adding oxygen or oxygen-containing gas or evaporation to the cooled coal gasified fuel before leaving the coal gasifier and supplying it to the gas turbine combustor. Nitrogen oxides are injected together with a compound that produces oxygen gas, mixed and diffused, and then heated above the reaction temperature to undergo a decomposition reaction before being supplied to the gas turbine combustor.
本発明において、酸素を含む気体としては例えば空気が
一最的であるがこれに限定されるものではなく、燃料成
分ないし燃焼に悪影響を与えないものであれば酸素を含
む全ての気体が使用可能である。また、蒸発して酸素を
生ずる化合物としてはｉｔ化水素水などが含まれる。尚
、本明細書において特に断りがない限り、酸素と表現す
る場合には、酸素を含む気体若しくは蒸発して酸素ガス
を生ずる化合物から得られる酸素を含む。In the present invention, the most suitable gas containing oxygen is, for example, air, but it is not limited to this, and any gas containing oxygen can be used as long as it does not adversely affect fuel components or combustion. It is. Compounds that evaporate to produce oxygen include nitrided hydrogen water and the like. In this specification, unless otherwise specified, when expressed as oxygen, it includes oxygen obtained from a gas containing oxygen or a compound that evaporates to produce oxygen gas.
また窒素酸化物としてはＮｏ、Ｎ２０．ＮＯ２などが好
適である。この窒素酸化物の注入はアンモニアの分解の
下限温度を引下げる。Also, as nitrogen oxides, No, N20. NO2 etc. are suitable. This nitrogen oxide injection lowers the lower limit temperature for ammonia decomposition.
これら注入気体の量はアンモニアに対する酸素濃度の比
０２／ＮＨ３において１〜３の範囲であるとか好ましく
、アンモニアに対する窒素酸化物−度の比はＮ Ｏ／
Ｎ Ｈｓは０．５〜１の範囲であることが好ましい、０
２ ／ＮＨａ比は１より大きいとアンモニアの分解には
効果的であるが３を越えると生成ＮＯ量が無視できない
程度に増大し、全体として低ＮＯｘ化に効果がなくなる
からである。また、１未満であると多くのアンモニアが
分解されずに残ってしまう。The amount of these injected gases is preferably in the range of 1 to 3 with a ratio of oxygen concentration to ammonia of 02/NH3, and a ratio of nitrogen oxide concentration to ammonia of 02/NH3.
N Hs is preferably in the range of 0.5 to 1, 0
This is because when the 2 /NHa ratio is larger than 1, it is effective in decomposing ammonia, but when it exceeds 3, the amount of NO produced increases to a non-negligible extent, and it is no longer effective in reducing NOx as a whole. Moreover, if it is less than 1, much ammonia will remain without being decomposed.
また、上述の濃度比の酸素注入と同時にＮＯｘを注入す
るとＮＨ３を分解する下限温度を低下させる効果がある
が、Ｎ Ｏｘ ／ Ｎ Ｈａ比が０．５未満であるとそ
の効果は少なく、１を越えると残存Ｎｏｎが無視できな
い量となる。Furthermore, if NOx is injected at the same time as oxygen is injected at the above concentration ratio, it has the effect of lowering the lower limit temperature for decomposing NH3, but if the NOx/NHa ratio is less than 0.5, the effect is small, and 1. If this value is exceeded, the number of remaining Nons becomes a non-negligible amount.
また、本発明において、微量の酸素等を含む石炭ガス化
燃料は、好ましくはガスタービン燃焼器力燃焼室に沿っ
て微量の酸素等を注入した石炭ガス化燃料を導入し、燃
焼室の熱を利用して加熱する。また、ガスタービン燃焼
器の排気口に熱交換器を設置し、燃焼ガスの熱を利用し
て加熱することも好適な実施の一例であるし、ガスター
ビンからの排ガスと熱交換し、微量の酸素等を注入した
石炭ガス化燃料を加熱することも好ましい、更に本発明
は、微量の酸素等を注入した石炭ガス化燃料をガスター
ビン燃焼器内の再循環流内に噴射し、該循環流内で分解
反応を進めることを特徴とする。In addition, in the present invention, the coal gasified fuel containing a trace amount of oxygen, etc. is preferably introduced along the combustion chamber of a gas turbine combustor, and the coal gasified fuel injected with a trace amount of oxygen, etc. is preferably introduced to reduce the heat in the combustion chamber. Use and heat. Another example of suitable implementation is to install a heat exchanger at the exhaust port of the gas turbine combustor and use the heat of the combustion gas for heating. It is also preferable to heat the coal gasified fuel injected with oxygen, etc. Furthermore, the present invention injects the coal gasified fuel injected with a small amount of oxygen etc. into the recirculation flow in the gas turbine combustor, and heats the recirculation flow. It is characterized by proceeding with the decomposition reaction within.
（作用）
したがって、石炭ガス化燃料中のＮＨ３は酸素および窒
素酸化物と反応して窒素（Ｎ２）と水（Ｎ２０）に分解
される。(Operation) Therefore, NH3 in the coal gasified fuel reacts with oxygen and nitrogen oxides and is decomposed into nitrogen (N2) and water (N20).
すなわち、石炭ガス化燃料中のＮＨ３は、当該燃料中に
反応温度より比較的低温の時に注入されて均一に拡散さ
れたＯ２によって、ＨＣＮやＣＮおよびＮＨｉ （ＮＨ
２、ＮＨなど）に分解され、その後一部は０２と反応し
てＮＯを生成したり、Ｎ２に還元される。That is, NH3 in the coal gasified fuel becomes HCN, CN, and NHi (NH
2, NH, etc.), and then some of it reacts with 02 to produce NO or is reduced to N2.
本発明はＮＨ３の０２による分解とその反応過程に伴う
ＮｏのＮＨ３との反応を利用して石炭ガス化燃料中のＮ
Ｈ３の分解を図る。この反応は気相で行われるため触媒
を必要としない、 また、０２の共存下でのみＮＨ３と
Ｎｏの反応がおこなわれるのであるから、窒素酸化物と
共に酸素を混合して石炭ガス化燃料中に注入すればＮＨ
３は０２および窒素酸化物によって分解される。また、
注入する酸素および窒素酸化物は石炭ガス化燃料中のＮ
Ｈ３濃度の最大数倍程度の微量のな−め石炭ガス化燃料
の他の組成変化に及ぼす影響は問題にならないほど僅か
である。The present invention utilizes the decomposition of NH3 by 02 and the reaction of No with NH3 accompanying the reaction process to reduce the amount of N in coal gasified fuel.
Attempt to decompose H3. This reaction takes place in the gas phase and does not require a catalyst. Also, since the reaction between NH3 and No takes place only in the coexistence of 02, oxygen is mixed with nitrogen oxides and added to the coal gasified fuel. If injected, NH
3 is decomposed by 02 and nitrogen oxides. Also,
The oxygen and nitrogen oxides injected are the N in the coal gasified fuel.
The influence on other compositional changes of the raw coal gasified fuel, which is a trace amount of several times the H3 concentration at most, is so small that it does not pose a problem.
（実施例） 以下、本発明を実施例に基づき詳細に説明する。(Example) Hereinafter, the present invention will be explained in detail based on examples.
まず、第１１図に本発明を実施する石炭ガス化複合発電
システムの概要を示す、該図において、１は石炭ガス化
炉、２は石炭ガス化燃料を脱硫・脱塵処理可能な温度ま
で冷却するガス冷却器・熱交換器、３は石炭ガス化燃料
中に含まれるチャー（すす）を捕集するサイクロン集塵
器、４は石炭ガス化燃料中の１−１２３やサイクロン３
で捕集しきれなかったチャー等を除去するクリーンアッ
プ（脱硫・脱！！り装置、５はガスタービン設備、６は
蒸気タービン設備、７はガスタービン燃焼器９に供給す
る前の石炭ガス化燃料に所望濃度比の酸素等を微量注入
するための酸素注入手段である。First, Fig. 11 shows an outline of a coal gasification combined cycle power generation system implementing the present invention. In the figure, 1 is a coal gasification furnace, and 2 is a coal gasification fuel that is cooled to a temperature that allows desulfurization and dust removal processing. 3 is a cyclone dust collector that collects char (soot) contained in coal gasified fuel; 4 is a cyclone dust collector that collects 1-123 and cyclone 3 contained in coal gasified fuel;
Clean-up (desulfurization/desulfurization equipment) to remove char, etc. that could not be completely collected in This is an oxygen injection means for injecting a small amount of oxygen or the like at a desired concentration ratio into the fuel.
また、ガスタービン設（ｉｌｉ５は微量の酸素等を注入
した石炭ガス化燃料を反応温度以上に加熱する加熱手段
８、ガスタービン用燃焼器９及びガスタービン］０を含
む。It also includes gas turbine equipment (ili5 is a heating means 8 for heating coal gasified fuel into which a trace amount of oxygen, etc. has been injected, to a temperature higher than the reaction temperature, a gas turbine combustor 9, and a gas turbine).
尚、石炭ガス化炉１とガス冷却器２とは一般に一体的に
構成されるなめ、ガス冷却器２を含めて石炭ガス化炉と
呼ぶことが多い、そこで、本明細書においては、石炭ガ
ス化炉を出てガスタービン燃焼器に供給する前の冷却さ
れた石炭ガス化燃料とは、第１１図のシステムにおいて
、ガス冷却器２以降で加熱手段８までの石炭ガス化燃料
供給系を流れるガスを意味する。The coal gasification furnace 1 and the gas cooler 2 are generally integrally constructed, so the gas cooler 2 is often referred to as a coal gasification furnace. Therefore, in this specification, the coal gasification furnace The cooled coal gasified fuel before leaving the oxidizing furnace and being supplied to the gas turbine combustor is the coal gasified fuel that flows through the coal gasified fuel supply system from the gas cooler 2 to the heating means 8 in the system shown in FIG. means gas.
したがって、該システムにおいて、石炭ガス化炉１を出
た後の石炭ガス化燃料は、脱硫・脱塵装置４で取扱える
程度の温度でかつ可能な限り高い温度、通常４００℃程
度まで冷却されており、Ｎ［１３の分解反応温度（７０
０″Ｃ）よりもはるかに低い、このため酸素等を注入し
ても反応しない。Therefore, in this system, the coal gasified fuel after leaving the coal gasifier 1 is cooled to a temperature that can be handled by the desulfurization/dedusting device 4 and as high as possible, usually around 400°C. The decomposition reaction temperature of N[13 (70
It is much lower than 0''C), so it does not react even if oxygen, etc. is injected.
石炭ガス化燃料への微量の酸素の注入は、本実施例の場
合、Ｈ２Ｓやチャー等が除去された後の工程において、
石炭ガス化燃利供給系の配管内に突出させたノズル等を
使用して行なわれる。しかしながら、酸素等の注入は石
炭ガス化炉のガス冷却器２とガスタービン燃焼器９との
間であれば、どこででも注入可能である０本実施例の場
合、注入酸素として空気が使用されている。空気は石炭
ガス化燃料中に噴射されると、未反応のまま拡散し、均
一な混合状態となる。その後、微量の酸素等を含む石炭
ガス化ガスは加熱手段８において加熱され反応温度に達
する。従って、石炭ガス化燃料と酸素とは可能な限り均
一に混合された状態において反応を開始する。In the case of this example, the injection of a small amount of oxygen into coal gasified fuel is carried out in the process after H2S, char, etc. are removed.
This is carried out using a nozzle etc. that protrudes into the piping of the coal gasification fuel supply system. However, oxygen can be injected anywhere between the gas cooler 2 of the coal gasifier and the gas turbine combustor 9. In this embodiment, air is used as the injected oxygen. There is. When air is injected into coal gasified fuel, it diffuses unreacted and becomes uniformly mixed. Thereafter, the coal gasification gas containing a trace amount of oxygen is heated in the heating means 8 and reaches the reaction temperature. Therefore, the reaction starts when the coal gasified fuel and oxygen are mixed as uniformly as possible.
尚、注入する酸素として過酸化水素水等の液体を使用す
る場合、気化熱によって冷却されるため拡散がある程度
進まなければ反応温度に達しない。Note that when a liquid such as a hydrogen peroxide solution is used as the oxygen to be injected, the reaction temperature will not be reached unless diffusion progresses to a certain extent because it is cooled by the heat of vaporization.
しかも、霧滴状で噴射されるため貫通力が強く拡散性が
良好である。Moreover, since it is sprayed in the form of droplets, it has a strong penetrating force and good dispersion.
次いで、第１０図（Ａ）〜（Ｄ＞に微量の酸素等を注入
した石炭ガス化燃料（以後、酸素注入燃料とも言う）を
反応温度以上に加熱する手段の一例を示す、まず、第１
０図（Ａ）、（Ａ）’に、ガスタービン燃焼器９の燃焼
室の熱を利用して酸素注入燃料を加熱する方法を示す、
この加熱手段８は、多数の反応管１１を内ケーシング板
１１ａで連結して燃焼室を画成するライナー２７を形成
する一方、このライナー２７の周囲を空気案内筒１２で
包囲すると共に更にその外部を外ケーシング１３で囲繞
し、反応管１１の先＠側を燃料ノズル１４に基端側を石
炭ガス化燃料供給系に夫々接続し、４００°Ｃ程度の酸
素注入燃料を反応ｇＩＩ内に導入して燃焼室の熱を利用
して反応温度である７００°Ｃ以上に加熱し、燃料ノズ
ル１４から燃焼室内へ噴射するまでにＮト（３を分解す
るようにしたものである。また、燃焼用空気は、外ケー
シング１３内に導入された庚、空気案内筒１２に沿って
ライナー２７の周囲を遭遇して一部がスワラ−２５へ供
給され、加温された後燃焼室２６内へ旋回噴射され、一
部が内ケーシング板１１ａの穴から二次空気として燃焼
室２６内へ供給される。Next, FIGS. 10A to 10D show an example of a means for heating coal gasified fuel injected with a small amount of oxygen (hereinafter also referred to as oxygen-injected fuel) to a temperature higher than the reaction temperature.
0 (A) and (A)' show a method of heating oxygen-injected fuel using the heat of the combustion chamber of the gas turbine combustor 9.
This heating means 8 includes a liner 27 that connects a large number of reaction tubes 11 with an inner casing plate 11a to define a combustion chamber, and also surrounds the liner 27 with an air guide tube 12 and further extends the outside of the liner 27. is surrounded by an outer casing 13, the tip side of the reaction tube 11 is connected to the fuel nozzle 14, and the base end side is connected to the coal gasification fuel supply system, and oxygen-injected fuel at about 400°C is introduced into the reaction gII. The fuel is heated to the reaction temperature of 700°C or higher using the heat in the combustion chamber, and is decomposed by the time it is injected from the fuel nozzle 14 into the combustion chamber. The air introduced into the outer casing 13 passes around the liner 27 along the air guide cylinder 12, and a part of the air is supplied to the swirler 25, heated, and then swirled into the combustion chamber 26. A part of the air is supplied into the combustion chamber 26 as secondary air from the hole in the inner casing plate 11a.
尚、図中、符号１５は集合管である。In addition, in the figure, the code|symbol 15 is a collecting pipe.
また、池の実施例として第１０図（Ｂ）にガスタービン
燃焼器から吐出される燃焼ガスの熱を利用して酸素注入
燃料を反応温度以上に加熱する例を示す、この実施例に
よると、ガスタービン燃焼器９の出口に熱交換器１６を
設置する一方、該熱交換器１６の入口側に石炭ガス化燃
料供給系を接続すると共に出口側をガスタービン燃焼器
９の入口に流路１７を以て接続し、燃料供給系から導入
される４００°Ｃ程度の酸素注入燃料をガスタービン１
０へ向かう燃焼ガスと熱交換して反応温度以上に加熱し
、熱交換器１６内でＮＨ３の分解反応を進めるようにし
たものである。一方、燃焼用空気はライナー２７とこれ
を囲繞するケーシング１８との間で構成される空気室１
９に導入され、部がスワラ−２５を通じて反応後の石炭
ガス化燃料と共に燃焼室２６内へ旋回噴射され、一部が
ライナー２７に穿孔された噴射孔２０を通じて二次空気
として噴射される。尚、符号１７は高温ガス配管である
。Further, as an example of the pond, FIG. 10(B) shows an example in which the oxygen-injected fuel is heated to a temperature higher than the reaction temperature using the heat of the combustion gas discharged from the gas turbine combustor. According to this example, A heat exchanger 16 is installed at the outlet of the gas turbine combustor 9, while a coal gasification fuel supply system is connected to the inlet side of the heat exchanger 16, and a flow path 17 is connected to the outlet side of the gas turbine combustor 9. The oxygen-injected fuel at about 400°C introduced from the fuel supply system is connected to the gas turbine 1.
The NH3 decomposition reaction is carried out in the heat exchanger 16 by exchanging heat with the combustion gas heading toward 0 to heat it above the reaction temperature. On the other hand, combustion air is supplied to the air chamber 1 formed between the liner 27 and the casing 18 surrounding it.
9, a portion is swirled and injected into the combustion chamber 26 together with the reacted coal gasified fuel through a swirler 25, and a portion is injected as secondary air through an injection hole 20 bored in a liner 27. In addition, the code|symbol 17 is a high temperature gas piping.
また、第１Ｏ図（Ｃ）にガスタービン１０から排出され
る高温排ガスを利用して酸素注入燃料を反応温度以上に
加熱する例を示す、複合発電システムによると、ガスタ
ービン１０から排出される排ガスは更に蒸気タービン６
の熱源として利用されるため、相当の熱例えば少なくと
も酸素注入燃料のＮト【３分解反応温度以上の７００〜
８００℃程度の熱を保有している。そこで、タービン２
０の排気系の途中に熱交換器２１を股１し、該熱交換器
２１に石炭ガス化燃料供給系を接続して酸素注入燃料を
排ガスとの間で熱交換させ、反応温度以上に加熱した後
ガス−タービン燃焼器９へ供給するようにしている。尚
、酸素注入燃料は反応温度例えば７００℃（微量のＮＯ
を同時に注入する場合には６００℃）程度以上に加熱す
る必要があるので、蒸気タービン６の熱サイクル側と熱
交換する前の排ガスとの間で熱交換することが好ましい
また、第１０図（Ｄ）にガスタービン燃焼器内の燃焼ガ
スの流れによって酸素注入燃料が受ける熱をコントロー
ルして反応温度以上に加熱する方法を示す、この方法は
、ライナー２７に設けた大きな穴２２から燃焼室２６内
へ大量の二次エア及び必要あれば三次エアを供給すると
共に、それらよりも上流側において燃焼室２６内に酸素
注入燃料をライナー２７に沿って旋回噴射させ、燃焼室
中央の適量な０２ａ度領域（燃焼領域）２３の周辺に渦
を巻くように形成される再循環流２４に乗せるようにし
たものである。このとき、再循環流２４にのった酸素注
入燃料は、空気量が極めて少ないため燃焼しないが、燃
焼領域２３からの輻射熱を受けて加熱され７００℃以上
に温まりＮＨ３の分解反応だけを進める。Further, according to a combined power generation system, in which an example of heating oxygen-injected fuel above the reaction temperature using high-temperature exhaust gas discharged from the gas turbine 10 is shown in FIG. 1O(C), the exhaust gas discharged from the gas turbine 10 furthermore steam turbine 6
Since it is used as a heat source for the oxygen-injected fuel, it is used as a heat source, for example, at least 700 ~
It has a heat of around 800℃. Therefore, turbine 2
A heat exchanger 21 is installed in the middle of the exhaust system of 0, and a coal gasification fuel supply system is connected to the heat exchanger 21 to exchange heat between the oxygen-injected fuel and the exhaust gas and heat it to a temperature higher than the reaction temperature. After that, it is supplied to the gas-turbine combustor 9. Note that the oxygen-injected fuel has a reaction temperature of, for example, 700°C (a trace amount of NO
When injecting at the same time, it is necessary to heat the gas to about 600° C. or higher, so it is preferable to exchange heat between the heat cycle side of the steam turbine 6 and the exhaust gas before heat exchange. D) shows a method of controlling the heat received by the oxygen-injected fuel by the flow of combustion gas in the gas turbine combustor and heating it above the reaction temperature. In addition to supplying a large amount of secondary air and tertiary air if necessary, oxygen-injected fuel is injected swirling along the liner 27 into the combustion chamber 26 on the upstream side thereof, and an appropriate amount of 02a degree in the center of the combustion chamber is supplied. It is arranged to be placed on a recirculation flow 24 that is formed in a swirling manner around a region (combustion region) 23. At this time, the oxygen-injected fuel carried in the recirculation flow 24 does not burn because the amount of air is extremely small, but receives radiant heat from the combustion region 23 and is heated to a temperature of 700° C. or higher to proceed only with the decomposition reaction of NH3.
尚、酸素注入燃料の加熱手段としては、上述のもめに限
定されるものではなく、要は反応温度以上のない温度領
域で微量の酸素等を混入して均一に拡散させ、それを反
応温度以上に加熱して反応温度を進めるようにすればよ
いのであるから、ヒータやその他の熱源を別途設置して
も可能である。Note that the means for heating oxygen-injected fuel is not limited to the above-mentioned method; the key is to mix a small amount of oxygen, etc., and diffuse it uniformly in a temperature range that is not above the reaction temperature. Since the reaction temperature can be increased by heating to a certain temperature, it is also possible to separately install a heater or other heat source.
以下、ＮＨ３の分解について説明する。The decomposition of NH3 will be explained below.
（１）酸素（０２）によるＮＨ３の分解第１図は石炭ガ
ス化燃料中のＮＨ３濃度が１０００１）Ｉｌｌ−Ｖにお
いてガス温度が１０００℃に達した時の注入０２濃度と
反応時間０．ｌ５ｅＣ後のＮＨ３濃度の関係を示す０図
より、０２濃度が１５００ρｐｉ以上あれば石炭ガス化
燃料中のＮＨ３濃度は１０００ρｐｉから１ ｐｌ）ｌ
以下に分解されることが理解できる。注入０２濃度が１
５００ｐＨ以下ではＮＨ３の分解率は悪化し、特に１０
００ρｐｌ以下では急激に悪化し、例えば５００ρｐ１
の０２濃度に対してはＮＨ３濃度は６００ｐｐｎまでし
か分解されない、このときのＮＨ３に対する０２の量は
濃度比で１．５である。(1) Decomposition of NH3 by oxygen (02) Figure 1 shows the injection 02 concentration and reaction time when the NH3 concentration in the coal gasified fuel is 10001) Ill-V when the gas temperature reaches 1000°C and the reaction time is 0. From the 0 diagram showing the relationship between NH3 concentration after l5eC, if the 02 concentration is 1500ρpi or more, the NH3 concentration in the coal gasified fuel will be 1 pl)l from 1000ρpi.
It can be understood that it is broken down into the following. Injection 02 concentration is 1
Below 500 pH, the decomposition rate of NH3 worsens, especially at 10
Below 00ρpl, the condition deteriorates rapidly, for example, 500ρpl.
With respect to the 02 concentration, the NH3 concentration is decomposed to only 600 ppn, and the concentration ratio of 02 to NH3 at this time is 1.5.
第２図は反応温度が１０００’Ｃ、Ｎ Ｈｓ濃度が１０
００００１１の石炭ガス化燃料中に１５００ｐｐｎの０
２を注入した時の反応時間とＮＨ３濃度等の関係を示し
たちのである。該図より明らかなようにＮ Ｈ，９は０
．０１秒程度で分解される。Figure 2 shows that the reaction temperature is 1000'C and the NHs concentration is 10
1500 ppn of 0 in coal gasified fuel of 000011
This shows the relationship between the reaction time and the NH3 concentration when 2 is injected. As is clear from the figure, N H,9 is 0
．． It decomposes in about 0.01 seconds.
また、第３図は石炭ガス化燃料中のＮ Ｈ９濃度が１０
００ＤＯＩＩ−Ｖにおいてガス温度が１０００℃のとき
の０．１秒後の反応における酸素によるアンモニアの分
解と生成窒素酸化物濃度との関係を示すグラフである。In addition, Figure 3 shows that the NH9 concentration in coal gasified fuel is 10
It is a graph showing the relationship between the decomposition of ammonia by oxygen and the concentration of produced nitrogen oxide in the reaction after 0.1 seconds when the gas temperature is 1000° C. in 00DOII-V.
これによると０２７ＮＨ３がモル比において１を下回る
とアンモニア分解率が９０％を切り急激に低下し、４．
５を上回ると生成窒、１１：酸化物濃度が許容の一応の
目安ともいえる１５０ｐρ１を越えてしまう、しかしな
がら、実際の反応においては、石炭ガス化燃料中のＮＨ
３と０２とが所定のモル比で完全に均一に混合されるわ
けではないので、局部的に過剰酸素となってＮＯが生成
される虞があることから、１〜３の範囲に収めることが
好ましい。According to this, when the molar ratio of 027NH3 is less than 1, the ammonia decomposition rate drops below 90%, and 4.
If it exceeds 5, the concentration of nitrogen produced, 11: oxide exceeds 150 pρ1, which can be said to be a tentative guideline for tolerance.However, in actual reactions, NH in coal gasified fuel
Since 3 and 02 are not completely and uniformly mixed at a predetermined molar ratio, there is a risk that locally excess oxygen will occur and NO will be produced, so it is best to keep the molar ratio within the range of 1 to 3. preferable.
また、第４図はＮＨ３に対し、モル比で１．５ｍの０２
を注入する際の０．１秒後の反応温度とアンモニア分解
率との関係を示すグラフである。In addition, Figure 4 shows that the molar ratio of 02 to NH3 is 1.5 m.
It is a graph showing the relationship between the reaction temperature after 0.1 seconds and the ammonia decomposition rate when injecting the ammonia.
鎖国より明らかなようにアンモニア分解率は７００゛Ｃ
以下になると低下し始め、約６７０℃以下になると急激
に分解率を悪化させる。As is clear from the isolation, the ammonia decomposition rate is 700°C.
When the temperature drops below about 670°C, the decomposition rate begins to decrease, and when the temperature drops below about 670°C, the decomposition rate deteriorates rapidly.
以上の結果より、ある温度では０２の注入により石炭ガ
ス化燃料中のＮＨ３が分解されることが明らかである０
反応温度を１０００ ’Ｃ１石炭ガス化燃料中のＮＨ３
ｆｉ度を１００００１３１１とするとき、注入すべき０
２濃度が１５００１）１１１１以上あれば理論的にはＮ
Ｈ３１度は１１）Ｈ以下に減少する。１５０００ｐ１以
上の０２の注入に対してはＮＨ３と０２の反応によるＮ
Ｏの生成がみられるようになる。しかし、Ｎｏの生成が
少々の場合にはＮＨ９が分解されるメリットの方がはる
かに大きい。From the above results, it is clear that NH3 in coal gasified fuel is decomposed by injection of 02 at a certain temperature.
Reaction temperature 1000'C1 NH3 in coal gasified fuel
When fi degree is 100001311, 0 to be injected
2 concentration is 15001)1111 or higher, theoretically N
H31 degrees decreases to below 11)H. For injection of 02 over 15000 p1, N due to the reaction between NH3 and 02
Production of O can be seen. However, if only a small amount of No is generated, the advantage of decomposing NH9 is much greater.
（２）窒素酸化物と０２によるＮ）ｆ３の分解石炭ガス
化燃料中に窒素酸化物のみを注入してもガス化燃料中の
ＮＨ３は分解されない４ＮＯは０２の共存下でのみアン
モニア分解反応を起しかつＮＨ３を分解する下限温度を
低下させる。例えば第５図は石炭ガス化燃料中にＮ Ｈ
３が１０００ｐＩ）１８−まれる＃Ｊ合、反応温度が１
０００℃において窒素酸化物としてＮｏを１０００ρρ
１注入した時の反応時間の経過に対する各種化学種の濃
度変化を示したものである０反応時間が１．０ｓｅｃ７
．ＱにおいてもＮＨ３は初期濃度である１０００ｐｐｌ
のままである。(2) Decomposition of N) f3 by nitrogen oxides and 02 Even if only nitrogen oxides are injected into the coal gasified fuel, NH3 in the gasified fuel will not be decomposed. 4NO will undergo an ammonia decomposition reaction only in the coexistence of 02. lowering the lower limit temperature at which NH3 is generated and decomposed. For example, Figure 5 shows N H in coal gasified fuel.
3 is 1000 pI) 18-, the reaction temperature is 1
1000ρρ of No as nitrogen oxide at 000℃
This shows the change in concentration of various chemical species with respect to the reaction time when 1 injection is made. 0 reaction time is 1.0 sec7
．． Even in Q, NH3 has an initial concentration of 1000 ppl.
It remains as it is.
シカシナカラ、ＮＯを一緒４：１０００Ｄｌ］１ｇ ＜
７） ０２を注入するとＮ）（３は急激に分解される。Shikashinakara, NO together 4:1000Dl] 1g <
7) When 02 is injected, N)(3 is rapidly decomposed.
第６図は石炭ガス化燃料中のＮＨ３濃度が１０００ｕＩ
の時に、ＮＯと０２をそれぞｈ１０００ρρ階ずつ注入
した時の反応時間０．１ｓｅｃ７ｉのＮＨ３、Ｎｏ、０
２のそれぞれの濃度を反応温度に対して示したものであ
る０図より、反応温度が７７０ ’Ｃ以上であればＮＨ
３はほとんど分解されることが明らかである。Figure 6 shows that the NH3 concentration in coal gasified fuel is 1000uI.
NH3, No, 0 with a reaction time of 0.1 sec7i when NO and 02 are injected by h1000ρρ steps each.
From Figure 0, which shows the concentration of each of 2 against the reaction temperature, if the reaction temperature is 770'C or higher, NH
It is clear that 3 is almost decomposed.
例えば反応温度が７７０℃においてはＮＨ３濃度は約０
．０２ρρｆに低減され、反応温度が１２００℃におい
ても０．２ｐｐｎ程度まで分解される。For example, when the reaction temperature is 770°C, the NH3 concentration is approximately 0.
．． Even at a reaction temperature of 1200° C., it is decomposed to about 0.2 ppn.
但し、この場合は反応温度の増加に伴いＮ Ｏ；３度が
増加し、反応温度が１０００’Ｃ以上では石炭ガス化燃
料中のＮ０４度は１００ｐρ１以上となる。However, in this case, the N04 degree in the coal gasified fuel increases by 3 degrees as the reaction temperature increases, and when the reaction temperature is 1000'C or higher, the N04 degree in the coal gasified fuel becomes 100 pρ1 or more.
また、第６図において留意すべきはＮ Ｈ３を含む石炭
ガス化燃料中に０２とＮＯを一緒に注入しても、ある温
度以下ではＮＨ３の分解反応の進行が緩かならのとなる
いうことである。第６図の条件においては最も分解に適
した温度は７７０’Ｃと判断される。Also, what should be noted in Figure 6 is that even if 02 and NO are injected together into coal gasified fuel containing NH3, the decomposition reaction of NH3 will proceed slowly below a certain temperature. It is. Under the conditions shown in FIG. 6, the most suitable temperature for decomposition is determined to be 770'C.
第７図は１０００ｐｐｎのＮＨ３を含む石炭ガス化燃料
に０２のみを１５００１１１）ｌ注入した時と同濃度の
０２と共に５０００１）ＩＩのＮｏを注入した時の反応
時間０．１ｓｅｃｆ＆のＮＨｓ 、Ｎｏ、０２の各濃度
を反応温度に対して示したものである。第７図において
ＮＨ３の分解を最大とする反応温度は０２のみの注入時
の場合は８４０℃であるが、Ｎｏを５００１）０１人し
た時は７５０°Ｃに低下している。即ち、０２と共にＮ
ｏを注入する効果としてはＮ１１３の分解と有効にする
反応温度域を低減させることにある。Ａ、反応温度が７
００ ”Ｃ程度の場合、５００ｐｐＩＩＮＯが同時に添
加されていると、ＮＨａｌＡ度は２ｐρｌＮ （ＮＯ添
加のない場合、点線のＮＨ３）となり、ＮＨ３の分解率
は９９．８％であり、反応最、Ｗ温度は８５０°Ｃであ
ってもＮ ｌ（３の分解効果の上からは７００°Ｃでも
十分である。（Ｉｊシ、７００゛Ｃ付近の温度域では温
度が少しでも低下すると、ＮＨ３の分解が悪くなるので
実用上は反応温度域は７００’ＣＬＩＪ上とすることが
好ましい。Figure 7 shows the reaction time of 0.1 secf & NHs when 1500111)l of 02 alone was injected into the coal gasified fuel containing 1000ppn NH3, and 50001)2 No was injected together with 02 at the same concentration. The concentration of each is shown relative to the reaction temperature. In FIG. 7, the reaction temperature at which the decomposition of NH3 is maximized is 840° C. when only 02 is injected, but it drops to 750° C. when No. 5001)01 is injected. That is, N along with 02
The effect of injecting O is to reduce the reaction temperature range in which N113 is decomposed and effective. A, reaction temperature is 7
00"C, if 500ppIINO is added at the same time, the NHalA degree is 2pρlN (NH3 shown by the dotted line when NO is added), the decomposition rate of NH3 is 99.8%, and the reaction temperature is 99.8%. Even if it is 850°C, 700°C is sufficient in terms of the decomposition effect of NH3. In practice, it is preferable that the reaction temperature range be above 700' CLIJ.
第８図は１０００ｐｐｎのＮＨ３を含む石炭ガス化燃料
中に０２を１０００ｐｐｌ注入する時、それと同時に注
入するＮｏ濃度と反応時間０．１ｓｅｃ後のＮ Ｈ３濃
度、Ｎｏ濃度の関係を示したものである０反応温度は１
０００’Ｃである。Ｎｏ濃度は７００１１ｐＩＩ以上あ
ればＮＨ３は１ρｐ１１以下にまで分解する。しかしな
がら、注入すべきＮ ＯＪ度が増加すると石炭ガス化燃
料中に残存するＮ０４度も急激に増加する。Figure 8 shows the relationship between the No concentration simultaneously injected when 1000 ppl of 02 is injected into coal gasified fuel containing 1000 ppn NH3, and the NH3 concentration and No concentration after a reaction time of 0.1 sec. 0 reaction temperature is 1
It is 000'C. If the No concentration is 70011pII or more, NH3 is decomposed to 1ρp11 or less. However, as the amount of NOJ to be injected increases, the amount of N04 remaining in the coal gasified fuel also increases rapidly.
２０００ρｐＩのＮｏを注入すると第６図においては石
炭ガス化燃料中のＮＯａＭ度は約１０００ｐｐＩｌとな
る。When 2000 ρpI of No is injected, the NOaM degree in the coal gasified fuel becomes about 1000 ppIl in FIG. 6.
また、第９図は窒素酸化物の添加によるアンモニア分解
促進効果とｒｔ ＯＩＡ度との関係を示すグラフである
。鎖国より明らかなようにＮ Ｏ／ Ｎ Ｈ３がモル比
において０．５を下回るとアンモニア分解率が急激に悪
化し、１．０を上回るとＮｏ生成４度が許容される濃度
を越えてしまうことが理解できる。Further, FIG. 9 is a graph showing the relationship between the ammonia decomposition promoting effect due to the addition of nitrogen oxides and the rt OIA degree. As is clear from Seikoku, when the molar ratio of N O / N H3 is less than 0.5, the ammonia decomposition rate deteriorates rapidly, and when it exceeds 1.0, the No production level exceeds the allowable concentration. I can understand.
斯様に、注入すべき０２濃度とＮＯ濃度を適切に選択し
、十分均一に拡散混合してから最適な反応温度まで加熱
することが生成されるＮＯや残存する他の組成物が大き
な影響を与−えない範囲でアンモニアを分解するに重要
である０例えばＮＨ３の分解に最適な温度域は石炭ガス
化燃料中に含まれるＮ Ｔ−（３濃度に対して注入する
０２ａ度、Ｎ。In this way, it is important to appropriately select the 02 concentration and NO concentration to be injected, sufficiently uniformly diffuse and mix, and then heat to the optimal reaction temperature to ensure that the generated NO and other remaining components have a large influence. For example, the optimal temperature range for decomposing NH3 is the temperature range that is important for decomposing ammonia within a range that does not give 0.
濃度によって決定される。また反応温度か決定されると
、ＮＨ３の分解率とガス化燃料中に残存するＮ０４度か
ら石炭ガス化燃料中のＮ Ｈ３濃度に対して注入すべき
０２濃度及びＮ０４度が決定される。Determined by concentration. When the reaction temperature is determined, the 02 concentration and N04 degrees to be injected to the NH3 concentration in the coal gasified fuel are determined from the NH3 decomposition rate and the N04 degrees remaining in the gasified fuel.
尚、本発明によるアンモニアの分解効果を確認するため
の反応計算にあたっては、注入した。２および窒素酸化
物は石炭ガス化燃料中に均一に混合しているものとして
、反応温度は設定した初期温度において一定とした。Incidentally, in the reaction calculation for confirming the ammonia decomposition effect according to the present invention, injection was performed. It was assumed that 2 and nitrogen oxides were uniformly mixed in the coal gasified fuel, and the reaction temperature was kept constant at the set initial temperature.
（発明の効果）
以上の説明より明らかなように、本発明は、ガス化炉を
出たＮ １−１３分解反応温度以下（４００’Ｃ程度）
の石炭カス化燃料にｉｔの酸素を含む気体あるいは酸素
をを含む気体と窒素酸化物を注入し、混合拡散させた後
反応温度（７００’Ｃ）以上に加熱することによって均
一な濃度分布状態でＮｌｌ３の分解反応を進め得るよう
にしているので、石炭ガス化燃料中のＮ Ｈ３が０２と
！）るいはＮ Ｈ３の０２による分解反応過程に伴うＮ
ｏと反応して、窒素（Ｎ２）と水（Ｎ２０）に分解され
て除去される。(Effects of the Invention) As is clear from the above explanation, the present invention has the advantage that the N 1-13 decomposition reaction temperature after exiting the gasifier is below (approximately 400'C)
A gas containing oxygen or a gas containing oxygen and nitrogen oxide is injected into the coal cassified fuel, mixed and diffused, and then heated to a temperature above the reaction temperature (700'C) to maintain a uniform concentration distribution. Since the decomposition reaction of Nll3 can proceed, the NH3 in the coal gasified fuel becomes 02! ) or N accompanying the decomposition reaction process of H3 with 02
It reacts with o and is decomposed into nitrogen (N2) and water (N20) and removed.
また、０２と共に窒素酸化物を同時に注入することによ
り、ＮＨ３の分解反応温度が低下するためＮ Ｈ３の分
解がより効果的に促進される。Furthermore, by simultaneously injecting nitrogen oxides with 02, the decomposition reaction temperature of NH3 is lowered, so that the decomposition of NH3 is promoted more effectively.
したがって、本発明によると、石炭ガス化燃料中のＮＨ
ａを乾式で除去することができ、システム全体の熱効率
め低下を招かず、しかも、ガスタービン燃焼器内で生成
されるＮ Ｈ３に起因するＮＯＸかなくなるため、ＮＯ
ｘの発生量を著しく低減することが可能となる。加えて
、触媒式排埋説ｌｉｉ′ｉ装置が不要となり、設備コス
トか下がると共にシステム運転も容易ならのとなる。ま
た、微量内気体を注入するだけなので設備の設置が容易
であり、従来の複合発電プラントをほとんど変更する必
要かない、しかも、０２注入を４００°Ｃの比較的低温
度で行なうため、ハンドリングが容易で安全性が高い。Therefore, according to the present invention, NH in coal gasified fuel
a can be removed dryly, without causing a decrease in the thermal efficiency of the entire system, and because NOx caused by N H3 generated in the gas turbine combustor is eliminated, NOx can be removed in a dry manner.
It becomes possible to significantly reduce the amount of x generated. In addition, a catalytic dumping device is not required, which reduces equipment costs and makes the system easier to operate. In addition, since only a small amount of internal gas is injected, equipment installation is easy, and there is almost no need to change conventional combined cycle power plants.Furthermore, since 02 injection is performed at a relatively low temperature of 400°C, handling is easy. It is highly safe.
第１図は添加する０２４度に対するＮＨ３濃度、Ｎ Ｏ
濃度、０２の関係を示すグラフ、第２図は反応時間に対
する各化学種の濃度変化を示すグラフ、第３図は０２と
ＮＨ３の分解と生成ＮＯ４度との関係を示すグラフ、第
４図は反応温度とＮｆ１３分解率との関係を示すグラフ
、第５図はＮＯだけを添加した時のＮＨ３の挙動を示す
グラフ、第６図は０２とＮｏの添加によるＮＨ３の分解
状もを示すグラフ、第７図は反応温度とＮＨ３、Ｎｏの
挙動の関係を示すグラフ、第８図はＮＨ３の分解に及ぼ
すＮＯ添加の影響を示すグラフ、第９図はＮＯ添加によ
るＮＨ３分解促進効宋効果 Ｏ；ｆｉ度との関係を示す
グラフ、第１０図（Ａ）は微量の酸素等を注入した石炭
ガス化燃利のＩＪｌｌ 悲ｆ、段の一例を示す概略説明
図、第１０図（Ａ）′は第１０図＜Ａ）のＸ−Ｘ線断面
図、第１０図（Ｃ）〜（Ｄ）は曲の加熱手段の例を示す
概略説明図、第１１図は本発明を実施する石炭ガス化複
合発電システムの概要を示すブロック図である。
１・・・ガス化炉、２・・・ガス冷却器、４・・・クリ
ーンアップ装置、
７・・・酸素等注入手段、８・・・加熱手段、９・・・
ガスタービン燃焼器、１１・・・反応管、３・・・流路
、
１６゜
１・・・熱交換器、
２４・・・頁順還流。
孫
特許出頭人
財団法人
電力中央研究所
代
理
人Figure 1 shows the NH3 concentration and N O
Graph showing the relationship between concentration and 02, Figure 2 is a graph showing changes in concentration of each chemical species with respect to reaction time, Figure 3 is a graph showing the relationship between 02 and NH3 decomposition and NO4 produced, Figure 4 is a graph showing the relationship between 02 and NH3 decomposition and NO4 degree produced. A graph showing the relationship between reaction temperature and Nf13 decomposition rate, Figure 5 is a graph showing the behavior of NH3 when only NO is added, and Figure 6 is a graph showing the decomposition state of NH3 due to the addition of 02 and No. Fig. 7 is a graph showing the relationship between the reaction temperature and the behavior of NH3 and No, Fig. 8 is a graph showing the influence of NO addition on the decomposition of NH3, and Fig. 9 is a graph showing the effect of NO addition on the promotion of NH3 decomposition. Figure 10 (A) is a graph showing the relationship with fi degree, and Figure 10 (A) is a schematic explanatory diagram showing an example of the IJll stage of coal gasification fuel injected with a small amount of oxygen. Fig. 10 is a sectional view taken along the line X-X of <A), Fig. 10 (C) to (D) are schematic explanatory diagrams showing examples of heating means for heating, and Fig. 11 is a coal gasification complex implementing the present invention. FIG. 1 is a block diagram showing an overview of a power generation system. DESCRIPTION OF SYMBOLS 1... Gasification furnace, 2... Gas cooler, 4... Clean-up device, 7... Oxygen etc. injection means, 8... Heating means, 9...
Gas turbine combustor, 11... Reaction tube, 3... Channel, 16° 1... Heat exchanger, 24... Page Sequential reflux. Sohn Patent Applicant Representative of Central Research Institute of Electric Power Industry
Claims (9)
る前の冷却された石炭ガス化燃料中に、酸素あるいは酸
素を含む気体若しくは蒸発して酸素ガスを生ずる化合物
を注入し混合拡散し、その後反応温度以上に加熱して分
解反応させてから前記ガスタービン燃焼器に供給するこ
とを特徴とする石炭ガス化燃料低ＮＯｘ化処理方法。(1) Oxygen, a gas containing oxygen, or a compound that evaporates to produce oxygen gas is injected into the cooled coal gasified fuel before it leaves the coal gasifier and is supplied to the gas turbine combustor and is mixed and diffused. A coal gasification fuel NOx reduction treatment method characterized in that the coal gasification fuel is then heated to a reaction temperature or higher to undergo a decomposition reaction and then supplied to the gas turbine combustor.
アに対し濃度比Ｏ＿２／ＮＨ＿３で１〜３であることを
特徴とする請求項１記載の石炭ガス化燃料低ＮＯｘ化処
理方法。(2) The coal gasification fuel NOx reduction treatment method according to claim 1, wherein the amount of oxygen injected is a concentration ratio O_2/NH_3 of 1 to 3 with respect to ammonia during coal gasification combustion.
る前の冷却された石炭ガス化燃料中に、酸素あるいは酸
素を含む気体若しくは蒸発して酸素ガスを生ずる化合物
と共に窒素酸化物を注入し混合拡散し、その後反応温度
以上に加熱して分解反応させてから前記ガスタービン燃
焼器に供給することを特徴とする石炭ガス化燃料低ＮＯ
ｘ化処理方法。(3) Nitrogen oxides are injected into the cooled coal gasified fuel before it leaves the coal gasifier and is supplied to the gas turbine combustor, along with oxygen, a gas containing oxygen, or a compound that evaporates to produce oxygen gas. The low NO coal gasification fuel is characterized in that the coal gasification fuel is mixed and diffused, and then heated to a temperature higher than the reaction temperature to cause a decomposition reaction, and then supplied to the gas turbine combustor.
x conversion processing method.
２／ＮＨ＿３で１〜３であり、かつ窒素酸化物の注入量
はアンモニアに対し濃度比ＮＯ／ＮＨ＿３で０．５〜１
の範囲であることを特徴とする請求項３に記載の石炭ガ
ス化燃料低ＮＯｘ化処理方法。(4) The amount of oxygen injected is a concentration ratio of O_ to that of ammonia.
2/NH_3 is 1 to 3, and the injection amount of nitrogen oxide is 0.5 to 1 with a concentration ratio of NO/NH_3 to ammonia.
4. The coal gasification fuel NOx reduction treatment method according to claim 3, wherein the NOx reduction treatment method is within the range of .
スタービン燃焼器の熱を利用することを特徴とする請求
項１ないし４のいずれかに記載の石炭ガス化燃料低ＮＯ
ｘ化処理方法。(5) The low NO coal gasified fuel according to any one of claims 1 to 4, characterized in that the heat of the coal gasified fuel injected with a trace amount of oxygen etc. is the heat of a gas turbine combustor.
x conversion processing method.
等を注入した石炭ガス化燃料を導入し、燃焼室の熱を利
用して前記燃料を加熱することを特徴とする請求項５記
載の石炭ガス化燃料低ＮＯｘ化処理方法。(6) Coal gasified fuel injected with a small amount of oxygen or the like is introduced along the combustion chamber of the gas turbine combustor, and the fuel is heated using the heat of the combustion chamber. Coal gasification fuel NOx reduction treatment method.
焼ガスの熱を利用して加熱することを特徴とする請求項
５記載の石炭ガス化燃料低ＮＯｘ化処理方法。(7) The coal gasification fuel NOx reduction treatment method according to claim 5, characterized in that a heat exchanger is installed at the outlet of the gas turbine combustor, and heating is performed using the heat of the combustion gas.
素等を注入した石炭ガス化燃料を加熱することを特徴と
する請求項５記載の石炭ガス化燃料低ＮＯｘ化処理方法
。(8) The coal gasification fuel low NOx treatment method according to claim 5, characterized in that the coal gasification fuel into which a trace amount of oxygen or the like is injected is heated by exchanging heat with exhaust gas from a gas turbine.
ービン燃焼器の循環流内に噴射し、該循環流内で分解反
応を進めることを特徴とする請求項５記載の石炭ガス化
燃料低ＮＯｘ化処理方法。(9) The coal gasified fuel according to claim 5, characterized in that the coal gasified fuel injected with a trace amount of oxygen, etc. is injected into the circulating flow of a gas turbine combustor, and the decomposition reaction proceeds within the circulating flow. Low NOx treatment method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20955988A JP2587469B2 (en) | 1988-08-25 | 1988-08-25 | NOx reduction treatment method for coal gasified fuel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20955988A JP2587469B2 (en) | 1988-08-25 | 1988-08-25 | NOx reduction treatment method for coal gasified fuel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0258598A true JPH0258598A (en) | 1990-02-27 |
| JP2587469B2 JP2587469B2 (en) | 1997-03-05 |
Family
ID=16574831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20955988A Expired - Lifetime JP2587469B2 (en) | 1988-08-25 | 1988-08-25 | NOx reduction treatment method for coal gasified fuel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2587469B2 (en) |
-
1988
- 1988-08-25 JP JP20955988A patent/JP2587469B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2587469B2 (en) | 1997-03-05 |
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