JPH10156192A - Activity regenerating method of catalyst for eliminating nitrogenoxides and device therefor - Google Patents
Activity regenerating method of catalyst for eliminating nitrogenoxides and device thereforInfo
- Publication number
- JPH10156192A JPH10156192A JP8323056A JP32305696A JPH10156192A JP H10156192 A JPH10156192 A JP H10156192A JP 8323056 A JP8323056 A JP 8323056A JP 32305696 A JP32305696 A JP 32305696A JP H10156192 A JPH10156192 A JP H10156192A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- denitration
- activity
- denitration catalyst
- regenerating
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、脱硝装置の脱硝触
媒を洗浄してその活性を再生させる脱硝触媒の活性再生
方法及び装置に係り、特に、脱硝触媒を先ず水で洗浄し
て触媒に付着したＮａ，Ｋ分を溶出させ、次にこの脱硝
触媒を0.1 〜30％クエン酸水溶液及び0.1〜20％硫酸水
溶液で洗浄して触媒に付着したバナジウム分を溶出させ
て触媒を再生する脱硝触媒の活性再生方法及び装置に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for regenerating the activity of a denitration catalyst for cleaning a denitration catalyst of a denitration apparatus, and more particularly to a method and an apparatus for regenerating the activity of the denitration catalyst. The denitration catalyst is then eluted, and then the denitration catalyst is washed with a 0.1-30% aqueous citric acid solution and a 0.1-20% sulfuric acid aqueous solution to elute the vanadium component adhering to the catalyst to regenerate the catalyst. The present invention relates to an active regeneration method and apparatus.
【０００２】[0002]
【従来の技術】石炭，重油等を燃料とするボイラ燃焼シ
ステムにおいては、排ガス中の窒素酸化物（ＮＯX ）を
除去するため、ボイラの後段に脱硝装置が設けられる。
脱硝装置内には、酸化チタンを主成分とする脱硝触媒が
ハニカム形状に形成され、この脱硝触媒の上流でアンモ
ニア（還元剤）を排ガス中に注入し、排ガスが触媒層を
通過することで、ＮＯX （主にＮＯ）がアンモニアによ
って窒素に還元されて、脱硝が行われる（図１参照）。BACKGROUND OF THE INVENTION Coal, in the boiler combustion system for a heavy oil as a fuel, for removing nitrogen oxides in exhaust gases (NO X), the denitration apparatus is provided downstream of the boiler.
In the denitration apparatus, a denitration catalyst containing titanium oxide as a main component is formed in a honeycomb shape, and ammonia (reducing agent) is injected into exhaust gas upstream of the denitration catalyst, and the exhaust gas passes through the catalyst layer, NO x (mainly NO) is reduced to nitrogen by ammonia to perform denitration (see FIG. 1).
【０００３】[0003]
【発明が解決しようとする課題】ところが、硫黄分の高
い重質油等の燃料を使用する場合、燃料中に含まれるバ
ナジウム（Ｖ）分が排ガス中を飛来して上記の脱硝装置
の触媒に付着して蓄積することにより、ＳＯ3 転化率
（ＳＯ2 がＳＯ3 に転化される率）が経時的に上昇し、
脱硝装置出口付近でのＳＯ3 濃度が上昇する。脱硝装置
から排出される排ガス中のＳＯ3 濃度が上昇すると、排
ガス温度がＳＯ3 の酸露点以下に下がったとき後段のダ
クト等の腐食（酸食）を引き起こすと共に、残存ＮＨ3
とＳＯ3 とが反応して生成した酸性硫安（ＮＨ4 ＨＳＯ
4 ）がＧＡＨ等に付着してダスト閉塞を引き起こした
り、ＥＰで除去しきれなかったヒューム状の酸性硫安が
白煙となって煙突から排出される等の問題の原因とな
る。However, when a fuel such as heavy oil having a high sulfur content is used, vanadium (V) contained in the fuel flies in the exhaust gas and becomes a catalyst for the above-mentioned denitration apparatus. By adhering and accumulating, the SO 3 conversion rate (the rate at which SO 2 is converted to SO 3 ) increases with time,
The SO 3 concentration near the outlet of the denitration device increases. When the concentration of SO 3 in the exhaust gas discharged from the denitration device rises, when the temperature of the exhaust gas falls below the acid dew point of SO 3 , corrosion (acid corrosion) of the downstream duct and the like is caused and residual NH 3
The SO 3 and acidic ammonium sulfate produced by the reaction (NH 4 HSO
4 ) adheres to GAH or the like and causes dust clogging, and causes problems such as fume-like acidic ammonium sulfate that could not be completely removed by EP to form white smoke and be discharged from the chimney.
【０００４】また、ボイラ燃料中のＮａ, Ｋ等のアルカ
リ分が触媒に付着して蓄積することにより、触媒が被毒
されてその脱硝活性が低下するという問題が生じる。そ
して、このアルカリ分の付着による脱硝性能の低下と、
上述のバナジウム分の付着によるＳＯ3 転化率の上昇と
が、脱硝触媒の活性（性能）低下の主な要因となってい
る。[0004] In addition, since alkali components such as Na and K in the boiler fuel adhere to and accumulate in the catalyst, there is a problem that the catalyst is poisoned and its denitration activity is reduced. And the denitration performance decreases due to the adhesion of the alkali,
The above-mentioned increase in the SO 3 conversion rate due to the attachment of vanadium is a major factor in lowering the activity (performance) of the denitration catalyst.
【０００５】従って、このように活性の低下した脱硝触
媒の脱硝性能を回復する必要があるが、従来において
は、単に使用済み触媒を新品と交換して問題の解決を図
ることが一般的であった。しかし、この場合、経済的負
担が大きいという欠点がある。また、使用済み触媒を蓚
酸等の他の有機酸溶液で洗浄することにより再生する方
法が試みられているが（特公平4-21545 号公報）、蓚酸
は毒性を有しＣＯＤ（chemical oxygen demand）も高い
ことから、その排水処理が容易でない。[0005] Therefore, it is necessary to restore the denitration performance of the denitration catalyst whose activity has been reduced as described above. However, conventionally, it is general to simply replace the used catalyst with a new one to solve the problem. Was. However, in this case, there is a disadvantage that the economic burden is large. Further, a method of regenerating the used catalyst by washing it with another organic acid solution such as oxalic acid has been attempted (Japanese Patent Publication No. 4-21545), but oxalic acid has toxicity and COD (chemical oxygen demand). The wastewater treatment is not easy.
【０００６】そこで、本発明の目的は、比較的廉価かつ
処理の容易な薬剤によって使用済み脱硝触媒の洗浄を行
い、その活性を再生する脱硝触媒の活性再生方法及び装
置を提供することである。Accordingly, an object of the present invention is to provide a method and an apparatus for regenerating the activity of a denitration catalyst, in which a used denitration catalyst is washed with a relatively inexpensive and easily treated chemical to regenerate its activity.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に請求項１の発明は、重質油焚きボイラ等での使用によ
りＮａ，Ｋ分が付着して脱硝率が低下し、また燃料中に
含まれるバナジウム分が付着してＳＯ3 転化率が上昇し
た脱硝触媒を再生する脱硝触媒の活性再生方法におい
て、上記脱硝触媒を0.1 〜30％クエン酸水溶液及び0.1
〜20％硫酸水溶液で洗浄するように構成されている。In order to achieve the above object, the invention of claim 1 is to use a heavy oil-fired boiler or the like to reduce the denitration rate due to adhesion of Na and K components, vanadium content attached SO 3 in the active regeneration process of the denitration catalyst conversion plays elevated denitration catalyst, an aqueous solution from 0.1 to 30% citric acid the denitration catalyst and 0.1 contained in
It is configured to wash with ~ 20% sulfuric acid aqueous solution.
【０００８】請求項２の発明は、上記脱硝触媒を上記0.
1 〜30％クエン酸水溶液及び0.1 〜20％硫酸水溶液で洗
浄する前に水で洗浄し、上記触媒に付着したＮａ，Ｋ分
を除去するように構成されている。According to a second aspect of the present invention, there is provided the denitration catalyst, wherein
Before washing with a 1 to 30% citric acid aqueous solution and a 0.1 to 20% sulfuric acid aqueous solution, the catalyst is washed with water to remove the Na and K components attached to the catalyst.
【０００９】請求項３の発明は、燃料中に含まれるバナ
ジウム分が付着してＳＯ3 転化率が上昇した脱硝触媒の
性能及び活性を再生する脱硝触媒の活性再生装置におい
て、上記脱硝触媒を収容すると共に0.1 〜30％クエン酸
水溶液及び0.1 〜20％硫酸水溶液で満たされる洗浄槽
と、上記洗浄槽に0.1 〜30％クエン酸水溶液と0.1 〜20
％硫酸水溶液とを洗浄液として供給する洗浄液供給手段
と、上記洗浄液を循環する洗浄液循環手段とを備えて構
成されている。A third aspect of the present invention is an apparatus for regenerating the performance and activity of a denitration catalyst in which vanadium contained in fuel is attached and the SO 3 conversion rate is increased. And a washing tank filled with a 0.1-30% citric acid aqueous solution and a 0.1-20% sulfuric acid aqueous solution, and the washing tank is filled with a 0.1-30% citric acid aqueous solution and 0.1-20%.
And a cleaning liquid circulating means for circulating the cleaning liquid.
【００１０】[0010]
【発明の実施の形態】以下、本発明の好適実施の形態を
添付図面により説明する。Preferred embodiments of the present invention will be described below with reference to the accompanying drawings.
【００１１】石炭，重油，ガス等を燃料とするボイラ燃
焼システムにおいては、排ガス中の窒素酸化物（Ｎ
ＯX ）を除去するため、ボイラの後段に脱硝装置が設け
られる。図１に、そのような脱硝装置１が概略的に示さ
れている。脱硝装置１の上流側には図示されないボイラ
等が接続され、その下流側には同じく図示されない後段
の諸装置（エアヒータ，ＥＰ，脱硫装置あるいは煙突
等）が接続される。In a boiler combustion system using coal, heavy oil, gas or the like as a fuel, nitrogen oxides (N
O X) to remove the NOx removal device is provided downstream of the boiler. FIG. 1 schematically shows such a denitration apparatus 1. A boiler or the like (not shown) is connected to the upstream side of the denitration device 1, and various downstream devices (an air heater, an EP, a desulfurization device, a chimney, etc.) are connected to the downstream side.
【００１２】脱硝装置１の内部には、酸化チタンを主成
分とする脱硝触媒２が触媒バスケット（図示されず）に
収容されて設置されている。また、脱硝装置１の入口部
には、ＮＨ3 注入装置３が図示されるように接続され、
ＮＨ3 注入装置３は、脱硝装置１入口部のダクトを介し
て脱硝装置１に導入される排ガス中にアンモニアを注入
するように構成される。Inside the denitration apparatus 1, a denitration catalyst 2 containing titanium oxide as a main component is accommodated and installed in a catalyst basket (not shown). Further, an NH 3 injection device 3 is connected to the inlet of the denitration device 1 as shown in the figure.
The NH 3 injection device 3 is configured to inject ammonia into exhaust gas introduced into the denitration device 1 via a duct at the entrance of the denitration device 1.
【００１３】脱硝装置１に隣接して、使用済みの脱硝触
媒を洗浄するための洗浄槽４が設置される（図１参
照）。洗浄槽４には、脱硝触媒２を洗浄（本洗浄）する
とき洗浄槽４に0.1 〜30％クエン酸水溶液と0.1 〜20％
硫酸水溶液とを洗浄液として供給する洗浄液供給手段５
が接続される。なお、この洗浄液供給手段５を、0.1 〜
30％クエン酸水溶液を供給するクエン酸水溶液供給手段
（図示されず）と、0.1 〜20％硫酸水溶液を供給する硫
酸水溶液供給手段（図示されず）とに分離して構成して
よいのは勿論である。洗浄槽４には、また、洗浄槽４内
の洗浄液をポンプ８を介して循環する洗浄液循環手段７
が、図示されるように設けられる。A cleaning tank 4 for cleaning the used denitration catalyst is installed adjacent to the denitration apparatus 1 (see FIG. 1). When the denitration catalyst 2 is washed (mainly washed), the washing tank 4 contains a 0.1-30% citric acid aqueous solution and a 0.1-20%
Cleaning liquid supply means 5 for supplying a sulfuric acid aqueous solution as a cleaning liquid
Is connected. Note that the cleaning liquid supply means 5 is set at 0.1 to
A citric acid aqueous solution supply means (not shown) for supplying a 30% citric acid aqueous solution and a sulfuric acid aqueous solution supply means (not shown) for supplying a 0.1 to 20% sulfuric acid aqueous solution may of course be provided separately. It is. The cleaning tank 4 also has a cleaning liquid circulating means 7 for circulating the cleaning liquid in the cleaning tank 4 via a pump 8.
Are provided as shown.
【００１４】この洗浄槽４及びこれに付随の上記の各手
段５，７，８が、本発明の脱硝触媒活性再生装置１０を
構成する。The cleaning tank 4 and the above-described respective means 5, 7, and 8 attached thereto constitute a denitration catalyst activity regeneration apparatus 10 of the present invention.
【００１５】なお、この脱硝触媒活性再生装置１０を可
動に構成し、これを脱硝装置１の脱硝触媒２を洗浄する
ときだけ脱硝装置１に隣接した位置に移動させてよいの
は、勿論である。また、本発明の脱硝触媒活性再生装置
１０を脱硝装置１から離れた場所に設置し、脱硝装置１
から取り外した脱硝触媒２を脱硝触媒活性再生装置１０
に移送して洗浄を行ってもよい。It is needless to say that the denitration catalyst activity regenerating device 10 may be configured to be movable, and may be moved to a position adjacent to the denitration device 1 only when the denitration catalyst 2 of the denitration device 1 is washed. . Further, the denitration catalyst activity regenerating device 10 of the present invention is installed at a place remote from the denitration device 1,
Of the denitration catalyst 2 removed from the denitration catalyst activity regeneration device 10
And may be transferred to a washing station.
【００１６】燃料が燃焼されて発生した排ガスが、脱硝
装置１に導入される。このときＮＨ3 注入装置３によっ
て、排ガスにＮＨ3 が注入される。脱硝装置１に導入さ
れた排ガス及びＮＨ3 は、脱硝触媒２において酸化チタ
ン等の脱硝触媒に接触する。すると、排ガス中に含まれ
る窒素酸化物（ＮＯX ）及びＮＨ3 が脱硝触媒に接触す
ることにより、ＮＯX （主にＮＯ）がＮＨ3 によって窒
素に還元されて、脱硝が行われる。Exhaust gas generated by burning the fuel is introduced into the denitration device 1. At this time, NH 3 is injected into the exhaust gas by the NH 3 injection device 3. The exhaust gas and NH 3 introduced into the denitration device 1 come into contact with a denitration catalyst such as titanium oxide in the denitration catalyst 2. Then, by nitrogen oxides contained in the exhaust gas (NO X) and NH 3 comes into contact with the denitration catalyst, NO X (mainly NO) is reduced to nitrogen by NH 3, denitration is performed.
【００１７】このように脱硝処理された排ガスは、後段
の諸装置（脱硫装置，煙突等）に導入され、最終的には
大気排出される。The exhaust gas thus denitrated is introduced into subsequent devices (desulfurizer, chimney, etc.) and finally discharged to the atmosphere.
【００１８】さて、上記の脱硝処理過程において、脱硝
装置１の脱硝触媒２には、燃料中に含まれるバナジウム
（Ｖ）分及びアルカリ（Ｎａ，Ｋ）分が付着して、上述
のように触媒の脱硝活性を低下させる。In the above-described denitration process, vanadium (V) and alkali (Na, K) components contained in the fuel adhere to the denitration catalyst 2 of the denitration device 1, and as described above, Decreases the denitration activity.
【００１９】そこで、本発明の脱硝触媒の活性再生方法
においては、上記の脱硝触媒活性再生装置１０によっ
て、脱硝触媒２に付着したＶ分及びＮａ，Ｋ分（以下、
Ｎａ分と称する）を洗浄・除去することにより、活性
（性能）の低下した脱硝触媒の活性の再生を図る。以
下、その方法を説明する。Therefore, in the method for regenerating the activity of the denitration catalyst of the present invention, the V component and the Na, K component (hereinafter, referred to as “V”) adhering to the denitration catalyst 2 are
The activity of the denitration catalyst, whose activity (performance) has been reduced, is intended to be regenerated by washing and removing the Na component). Hereinafter, the method will be described.
【００２０】まず、Ｖ分，Ｎａ分等が付着して触媒活性
の低下した脱硝触媒２を、クレーン等により脱硝装置１
から取り出し、洗浄前の準備作業として、エアブローに
よる煤塵除去（エアーブロー）及び水による予備洗浄を
行う。エアーブローにより、（脱硝）触媒２に付着した
煤塵等が除去され、又、水による予備洗浄により、Ｎａ
分等のアルカリ分が溶出する。First, the denitration catalyst 2 having reduced catalytic activity due to the adhesion of V, Na and the like is removed from the denitration device 1 by a crane or the like.
Then, as preparatory work before cleaning, dust removal by air blowing (air blowing) and preliminary cleaning with water are performed. Dust and the like adhering to the (denitration) catalyst 2 are removed by air blow, and Na is removed by preliminary washing with water.
Elutes alkaline components.
【００２１】煤塵及びＮａ分等を除去された触媒２は、
次に、洗浄槽４内に移される。洗浄液供給手段５によっ
て、0.1 〜30％クエン酸水溶液と0.1 〜20％硫酸水溶液
とが、洗浄槽４内に洗浄液として供給される。このと
き、0.1 〜30％クエン酸水溶液と0.1 〜20％硫酸水溶液
とを、それぞれ別々の供給手段によって洗浄槽４内に供
給してよいのは勿論である。洗浄槽４内に供給された洗
浄液は、洗浄液循環手段７により、ポンプ８を介して適
宜循環され、この結果触媒２が洗浄液によって効果的に
洗浄される（本洗浄）。The catalyst 2 from which dust and Na content have been removed,
Next, it is moved into the cleaning tank 4. The cleaning liquid supply means 5 supplies a 0.1 to 30% aqueous citric acid solution and a 0.1 to 20% aqueous sulfuric acid solution into the cleaning tank 4 as a cleaning liquid. At this time, it is a matter of course that the 0.1 to 30% citric acid aqueous solution and the 0.1 to 20% sulfuric acid aqueous solution may be supplied into the cleaning tank 4 by separate supply means. The cleaning liquid supplied into the cleaning tank 4 is appropriately circulated through the pump 8 by the cleaning liquid circulating means 7, so that the catalyst 2 is effectively cleaned by the cleaning liquid (main cleaning).
【００２２】上記の本洗浄において、洗浄槽４に0.1 〜
30％クエン酸水溶液及び0.1 〜20％硫酸水溶液が供給さ
れると、洗浄槽４内に酸性且つ還元性の雰囲気がもたら
される。この酸性且つ還元性の雰囲気においては、図３
に示されるようにバナジウムがイオン化し易くなるの
で、触媒２に付着していたバナジウム分がイオン化して
溶出し、結果的にＶ分等が触媒２から除去される。ま
た、この本洗浄によって、予備洗浄で除去しきれなかっ
たＮａ分等が確実に除去される。In the main cleaning described above, 0.1 to
When a 30% aqueous citric acid solution and a 0.1-20% aqueous sulfuric acid solution are supplied, an acidic and reducing atmosphere is provided in the cleaning tank 4. In this acidic and reducing atmosphere, FIG.
Since vanadium is easily ionized as shown in (2), the vanadium component adhering to the catalyst 2 is ionized and eluted, and as a result, V component and the like are removed from the catalyst 2. In addition, by this main cleaning, Na and the like which cannot be completely removed by the preliminary cleaning are surely removed.
【００２３】上述のように、本洗浄において使用される
クエン酸水溶液の濃度は、0.1 〜30％であるのが望まし
く、一方、硫酸水溶液の濃度は、0.1 〜20％であるのが
望ましい。また、洗浄時間は0.1 〜４時間、固液比
（（洗浄）溶液の体積／触媒の体積）は0.5 〜７倍容量
が適当であるが、これらの条件は、洗浄される触媒の状
態，洗浄液の濃度等によって適宜変更してよい。洗浄時
の温度については、常温〜６０℃が望ましい。As described above, the concentration of the aqueous citric acid solution used in the main washing is preferably 0.1 to 30%, while the concentration of the aqueous sulfuric acid solution is preferably 0.1 to 20%. The washing time is preferably 0.1 to 4 hours, and the solid-liquid ratio (volume of (washing) solution / volume of catalyst) is suitably 0.5 to 7 times the volume. May be changed as appropriate depending on the concentration of. The temperature at the time of washing is desirably room temperature to 60 ° C.
【００２４】図２に、この本洗浄を、固液比３もしくは
７，洗浄温度６０℃，洗浄時間２時間という条件の下、
１）４％クエン酸水溶液のみ，固液比３、２）10％クエ
ン酸水溶液のみ，固液比３、３）10％クエン酸水溶液＋
4.6％硫酸水溶液，固液比３、４）15％クエン酸水溶液
＋10％硫酸水溶液，固液比３、５）15％クエン酸水溶液
＋10％硫酸水溶液，固液比７、６）20％クエン酸水溶液
のみ，固液比３の６つのパターンで行ったときの実験結
果が、脱硝率再生率，ＳＯ3 転化率再生率及び触媒Ｖ2
Ｏ5 洗浄率について示されている。FIG. 2 shows that the main cleaning is performed under the conditions of a solid-liquid ratio of 3 or 7, a cleaning temperature of 60 ° C., and a cleaning time of 2 hours.
1) 4% citric acid aqueous solution only, solid-liquid ratio 3, 2) 10% citric acid aqueous solution only, solid-liquid ratio 3, 3) 10% citric acid aqueous solution +
4.6% sulfuric acid aqueous solution, solid-liquid ratio 3, 4) 15% citric acid aqueous solution + 10% sulfuric acid aqueous solution, solid-liquid ratio 3, 5) 15% citric acid aqueous solution + 10% sulfuric acid aqueous solution, solid-liquid ratio 7, 6) 20% citric acid The experimental results obtained when performing only the aqueous solution in six patterns with the solid-liquid ratio of 3 were the denitration rate regeneration rate, SO 3 conversion rate regeneration rate, and catalyst V 2
Shown for O 5 cleaning rates.
【００２５】ちなみに、By the way,
【００２６】[0026]
【数１】 (Equation 1)
【００２７】である。## EQU1 ##
【００２８】図２から明らかなように、６つの実験パタ
ーンの全ての場合において脱硝率再生率は１００％であ
った。すなわち、触媒２に付着していたＮａ2 Ｏ等のア
ルカリ分が、予備洗浄及び本洗浄によってほぼ完全に除
去されることが判明した。また、触媒２を15％クエン酸
水溶液＋10％硫酸水溶液，固液比３で洗浄した場合及び
15％クエン酸水溶液＋10％硫酸水溶液，固液比７で洗浄
した場合においては、共にＳＯ3 転化率再生率が83％以
上、触媒Ｖ2 Ｏ5 洗浄率が84.9％という良好な結果が得
られている。As is apparent from FIG. 2, the regeneration rate of the denitration rate was 100% in all the six experimental patterns. That is, it was found that the alkali components such as Na 2 O adhering to the catalyst 2 were almost completely removed by the preliminary cleaning and the main cleaning. When the catalyst 2 is washed with a 15% aqueous citric acid solution + a 10% sulfuric acid aqueous solution at a solid-liquid ratio of 3;
In the case of washing with a 15% citric acid aqueous solution + 10% sulfuric acid aqueous solution and a solid-liquid ratio of 7, a good result was obtained in which the SO 3 conversion rate regeneration rate was 83% or more and the catalyst V 2 O 5 washing rate was 84.9%. ing.
【００２９】つまり、本発明の脱硝触媒の活性再生方法
に基づき、脱硝触媒を水で予備洗浄した後に0.1 〜30％
クエン酸水溶液及び0.1 〜20％硫酸水溶液を用いて本洗
浄を行った場合、従来の蓚酸を用いた洗浄に比肩する優
れた洗浄効果がもたらされ、脱硝率が１００％に回復す
ると共にＳＯ3 転化率が大きく減少し、ＳＯ3 転化率に
おいてもほぼ使用前のフレッシュな状態に戻る（再生さ
れる）。That is, according to the method for regenerating the activity of the denitration catalyst of the present invention, after the denitration catalyst is preliminarily washed with water, 0.1 to 30%
When the main cleaning is performed using a citric acid aqueous solution and a 0.1 to 20% sulfuric acid aqueous solution, an excellent cleaning effect comparable to the conventional cleaning using oxalic acid is obtained, and the denitration rate is restored to 100% and SO 3 is reduced. The conversion rate is greatly reduced, and the SO 3 conversion rate almost returns to a fresh state before use (regenerated).
【００３０】なお、本実施の形態においては、本洗浄の
準備作業としてのエアブロー及び予備洗浄を洗浄槽４の
外で行うが、これを触媒２を洗浄槽４内に設置してか
ら、洗浄槽４内で行ってもよいのは勿論である。また、
洗浄槽４内の洗浄液を循環する洗浄液循環手段７とし
て、ポンプによる循環以外の他の循環手段を用いてもよ
いのは勿論である。In the present embodiment, air blowing and preliminary cleaning as preparatory work for the main cleaning are performed outside the cleaning tank 4, but after the catalyst 2 is set in the cleaning tank 4, the cleaning is performed. 4 may of course be performed. Also,
As the cleaning liquid circulating means 7 for circulating the cleaning liquid in the cleaning tank 4, other circulating means other than the circulation by the pump may be used.
【００３１】上記のように本洗浄が行われてＶ分及びＮ
ａ分等の除去が終了した後、脱硝触媒２は、再び水によ
って洗浄される。これによって、（本洗浄で硫酸水溶液
が使用されたため）脱硝触媒２に付着している可能性の
ある硫酸が洗い落とされる（すすぎ）。すすぎが終了す
ると、洗浄槽４からクレーン等で取りだされて乾燥され
る（自然乾燥）。乾燥の終了した脱硝触媒２は、脱硝装
置１内に再び設置される。The main cleaning is performed as described above, and the V component and N
After the removal of the a component and the like is completed, the denitration catalyst 2 is washed again with water. Thereby, sulfuric acid that may have adhered to the denitration catalyst 2 (because the aqueous sulfuric acid solution was used in the main cleaning) is washed away (rinse). When the rinsing is completed, it is taken out of the washing tank 4 by a crane or the like and dried (natural drying). The denitration catalyst 2 whose drying has been completed is installed in the denitration apparatus 1 again.
【００３２】なお、上記のすすぎ及び乾燥について、乾
燥を（すすぎ液を抜いた）洗浄槽４内で行う、あるいは
乾燥を乾燥機（図示されず）によって迅速に行う等の種
々の変更が可能であることは、勿論である。The above-mentioned rinsing and drying can be variously changed, for example, drying is performed in the washing tank 4 (with the rinsing liquid removed), or drying is rapidly performed by a dryer (not shown). Some things are, of course.
【００３３】以上、本発明の脱硝触媒の活性再生方法及
びこれに基づく脱硝触媒の活性再生装置によれば、Ｖ分
及びＮａ分等が付着して活性の低下した脱硝装置の脱硝
触媒を先ず水で洗浄してＮａ分等を除去し、次にこの触
媒を0.1 〜30％クエン酸水溶液及び0.1 〜20％硫酸水溶
液で洗浄してＶ分等を除去することにより、脱硝触媒の
ＳＯ3 転化率を低下させると共に脱硝率を上昇させ、触
媒の活性をほぼ完全に回復させることができる。つま
り、本発明の脱硝触媒の活性再生方法により、活性の低
下した使用済み脱硝触媒の（上昇した）ＳＯ3 転化率及
び（低下した）脱硝率を、フレッシュな脱硝触媒のＳＯ
3 転化率及び脱硝率とほぼ同程度まで低下あるいは向上
できる。As described above, according to the method for regenerating the activity of the denitration catalyst of the present invention and the apparatus for regenerating the activity of the denitration catalyst based on the same, the denitration catalyst of the denitration apparatus whose activity has been reduced due to the adhesion of V component and Na component is first treated with water. The catalyst is washed with a 0.1-30% aqueous citric acid solution and a 0.1-20% sulfuric acid aqueous solution to remove V components and the like, whereby the SO 3 conversion of the denitration catalyst is reduced. And the denitration rate is increased, and the activity of the catalyst can be almost completely recovered. That is, according to the method for regenerating the activity of the denitration catalyst of the present invention, the (increased) SO 3 conversion rate and the (decreased) denitration rate of the used denitration catalyst whose activity has been reduced can be reduced by the SO 2 conversion of the fresh denitration catalyst.
(3) The conversion rate and the denitration rate can be reduced or improved to approximately the same level.
【００３４】[0034]
【発明の効果】以上、要するに、本発明に係る脱硝触媒
の活性再生方法及び装置によれば、以下の優れた効果が
もたらされる。As described above, according to the method and apparatus for regenerating the activity of the denitration catalyst according to the present invention, the following excellent effects can be obtained.
【００３５】(1) バナジウム分が付着してＳＯ3 転化率
が上昇した使用済み脱硝触媒を0.1〜30％クエン酸水溶
液と0.1 〜20％硫酸水溶液とを用いて洗浄することによ
り、バナジウム分が容易にイオン化して触媒から溶出す
る。その結果、洗浄された触媒のＳＯ3 転化率が大幅に
低下し、約84％という高い再生率でフレッシュな触媒に
近い状態に再生される。よって、ＳＯ3 の増加が原因と
なって起こるダクトの腐食、酸性硫安の発生が防止され
る。(1) The used denitration catalyst having an increased SO 3 conversion rate due to the attachment of the vanadium component is washed with a 0.1 to 30% aqueous citric acid solution and a 0.1 to 20% aqueous sulfuric acid solution, so that the vanadium component is reduced. Easily ionizes and elutes from the catalyst. As a result, the SO 3 conversion of the washed catalyst is significantly reduced, and the catalyst is regenerated to a state close to a fresh catalyst at a high regeneration rate of about 84%. Therefore, corrosion of the duct and generation of acidic ammonium sulfate caused by an increase in SO 3 are prevented.
【００３６】(2) Ｎａ分等のアルカリ分が付着して脱硝
性能の低下した（すなわち、活性の低下した）使用済み
脱硝触媒を水で洗浄することにより、アルカリ分が溶出
して触媒から除去される。その結果、洗浄された触媒の
脱硝率が、フレッシュな脱硝触媒と同程度に向上する。(2) Washing the used denitration catalyst with reduced denitration performance (ie, reduced activity) due to adhesion of alkali components such as Na component with water, the alkali components are eluted and removed from the catalyst. Is done. As a result, the denitration rate of the washed catalyst is improved to the same degree as that of a fresh denitration catalyst.
【００３７】(3) 本発明の方法において用いられるクエ
ン酸は無害な有機酸であり、この点でも、毒性の強い蓚
酸等を用いる従来の方法より優れている。(3) The citric acid used in the method of the present invention is a harmless organic acid, and is also superior to the conventional method using highly toxic oxalic acid and the like in this respect.
【００３８】(4) 触媒を0.1 〜30％クエン酸水溶液及び
0.1 〜20％硫酸水溶液で洗浄する本発明の場合、洗浄後
の処理が簡便（水によるすすぎと自然乾燥のみ）である
にもかかわらず、極めて高い脱硝率再生率(100%)及びＳ
Ｏ3 転化率再生率(84.0%) が得られる。一方、蓚酸等を
用いる従来の方法の場合、所望の脱硝率再生率を達成す
るためには、洗浄した触媒を触媒活性成分であるタング
ステン化合物の溶液に含浸してタングステン化合物を担
持させた後、定着のため焼成する必要があり、この点で
も、本発明の脱硝触媒活性再生方法の方が優れている。(4) The catalyst is a 0.1-30% aqueous citric acid solution and
In the case of the present invention in which washing is carried out with a 0.1 to 20% sulfuric acid aqueous solution, although the treatment after washing is simple (only rinsing with water and natural drying), an extremely high denitration rate regeneration rate (100%) and S
An O 3 conversion regeneration rate (84.0%) is obtained. On the other hand, in the case of the conventional method using oxalic acid or the like, in order to achieve a desired denitration rate regeneration rate, the washed catalyst is impregnated with a solution of a tungsten compound that is a catalytically active component to support the tungsten compound, It is necessary to bake for fixing, and in this regard, the method for regenerating the denitration catalyst activity of the present invention is more excellent.
【図１】本発明の脱硝触媒の活性再生装置及びこれが付
随する脱硝装置の概略図（一部断面図）である。FIG. 1 is a schematic view (partially sectional view) of an apparatus for regenerating the activity of a denitration catalyst of the present invention and a denitration apparatus accompanying the apparatus.
【図２】本発明の脱硝触媒の活性再生方法において、ク
エン酸水溶液濃度，硫酸水溶液濃度及び固液比の異なる
６つのパターンで洗浄した場合の脱硝率再生率，ＳＯ3
転化率再生率及び触媒Ｖ2 Ｏ5 洗浄率を示す図である。FIG. 2 shows the denitration rate regeneration rate and SO 3 in the method for regenerating the activity of the denitration catalyst according to the present invention, when washing is performed in six patterns having different concentrations of citric acid aqueous solution, sulfuric acid aqueous solution and solid-liquid ratio.
It is a diagram illustrating a conversion playback rate and catalyst V 2 O 5 washing rate.
【図３】Ｖ2 Ｏ5 （及びその他のバナジウム酸化物）
が、ｐＨ及び酸化還元雰囲気の変化に伴いどのようにイ
オン化されるかを示す図である。FIG. 3 V 2 O 5 (and other vanadium oxides)
FIG. 4 is a diagram showing how is ionized with changes in pH and redox atmosphere.
２ 脱硝触媒 ４ 洗浄槽 ５ 洗浄液供給手段 ７ 洗浄液循環手段 １０ 脱硝触媒活性再生装置 2 denitration catalyst 4 cleaning tank 5 cleaning liquid supply means 7 cleaning liquid circulation means 10 denitration catalyst activity regeneration device
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ０１Ｊ 21/20 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI B01J 21/20
Claims (3)
ａ，Ｋ分が付着して脱硝率が低下し、また燃料中に含ま
れるバナジウム分が付着してＳＯ3 転化率が上昇した脱
硝触媒を再生する脱硝触媒の活性再生方法において、上
記脱硝触媒を0.1 〜30％クエン酸水溶液及び0.1 〜20％
硫酸水溶液で洗浄することを特徴とする脱硝触媒の活性
再生方法。1. Use of heavy oil-fired boilers in N
In the method for regenerating a denitration catalyst in which a and K components are attached and the denitration rate is reduced, and a vanadium component contained in the fuel is attached and the SO 3 conversion rate is increased, the denitration catalyst is used as a catalyst. 0.1-30% citric acid aqueous solution and 0.1-20%
A method for regenerating the activity of a denitration catalyst, comprising washing with an aqueous sulfuric acid solution.
水溶液及び0.1 〜20％硫酸水溶液で洗浄する前に水で洗
浄し、上記触媒に付着したＮａ，Ｋ分を除去する請求項
１記載の脱硝触媒の活性再生方法。2. The method according to claim 1, wherein the denitration catalyst is washed with water before being washed with the 0.1 to 30% citric acid aqueous solution and the 0.1 to 20% sulfuric acid aqueous solution to remove the Na and K components attached to the catalyst. A method for regenerating the activity of a denitration catalyst.
てＳＯ3 転化率が上昇した脱硝触媒の性能及び活性を再
生する脱硝触媒の活性再生装置において、上記脱硝触媒
を収容すると共に0.1 〜30％クエン酸水溶液及び0.1 〜
20％硫酸水溶液で満たされる洗浄槽と、上記洗浄槽に0.
1 〜30％クエン酸水溶液と0.1 〜20％硫酸水溶液とを洗
浄液として供給する洗浄液供給手段と、上記洗浄液を循
環する洗浄液循環手段とを備えたことを特徴とする脱硝
触媒の活性再生装置。3. A denitration catalyst activity regenerating apparatus for regenerating the performance and activity of a denitration catalyst having an increased SO 3 conversion rate due to the attachment of vanadium contained in fuel, wherein said denitration catalyst is accommodated and 0.1 to 30. % Citric acid aqueous solution and 0.1 to
A cleaning tank filled with a 20% sulfuric acid aqueous solution, and the cleaning tank
An apparatus for regenerating the activity of a denitration catalyst, comprising: a cleaning liquid supply means for supplying a 1 to 30% aqueous citric acid solution and a 0.1 to 20% aqueous sulfuric acid solution as a cleaning liquid; and a cleaning liquid circulating means for circulating the cleaning liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8323056A JPH10156192A (en) | 1996-12-03 | 1996-12-03 | Activity regenerating method of catalyst for eliminating nitrogenoxides and device therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8323056A JPH10156192A (en) | 1996-12-03 | 1996-12-03 | Activity regenerating method of catalyst for eliminating nitrogenoxides and device therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10156192A true JPH10156192A (en) | 1998-06-16 |
Family
ID=18150609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8323056A Pending JPH10156192A (en) | 1996-12-03 | 1996-12-03 | Activity regenerating method of catalyst for eliminating nitrogenoxides and device therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10156192A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004022226A1 (en) * | 2002-09-05 | 2004-03-18 | Envica Gmbh | Method for regenerating iron-loaded denox catalysts |
| US7501106B2 (en) | 2003-12-25 | 2009-03-10 | Mitsubishi Heavy Industries, Ltd. | Denitrification catalyst regeneration method |
| JP2010264418A (en) * | 2009-05-18 | 2010-11-25 | Ihi Corp | Method for cleaning denitration catalyst |
| JP2011031237A (en) * | 2009-07-10 | 2011-02-17 | Kyuden Sangyo Co Inc | Method for improving activity of denitrification catalyst in flue gas denitrification apparatus |
| US8980779B2 (en) | 2002-06-21 | 2015-03-17 | The Chugoku Electric Power Co., Inc. | Method of regenerating NOx removal catalyst |
| EP2781252A4 (en) * | 2011-11-17 | 2015-07-08 | Mitsubishi Hitachi Power Sys | Exhaust gas treatment catalyst, method for producing exhaust gas treatment catalyst, and method for regenerating exhaust gas treatment catalyst |
| CN105221222A (en) * | 2015-10-23 | 2016-01-06 | 苏州莲池环保科技发展有限公司 | Ternary catalyzing unit without the need to dismantling restorative procedure |
| JP2016007555A (en) * | 2014-06-20 | 2016-01-18 | 三菱日立パワーシステムズ株式会社 | Method for regenerating used denitration catalyst |
-
1996
- 1996-12-03 JP JP8323056A patent/JPH10156192A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8980779B2 (en) | 2002-06-21 | 2015-03-17 | The Chugoku Electric Power Co., Inc. | Method of regenerating NOx removal catalyst |
| US7858549B2 (en) | 2002-09-05 | 2010-12-28 | Coalogix Technology Holdings, Inc. | Method for regeneration of iron-loaded denox catalysts |
| US7569506B2 (en) | 2002-09-05 | 2009-08-04 | Cesi-Tech Technologies, Inc. | Method for regenerating iron-loaded denox catalysts |
| WO2004022226A1 (en) * | 2002-09-05 | 2004-03-18 | Envica Gmbh | Method for regenerating iron-loaded denox catalysts |
| KR100974688B1 (en) * | 2002-09-05 | 2010-08-06 | 에빈거 게엠베하 | Method for regenerating iron-loaded denox catalysts |
| US7666808B2 (en) | 2003-12-25 | 2010-02-23 | Mitsubishi Heavy Industries, Ltd. | Denitrification catalyst regeneration method |
| US7501106B2 (en) | 2003-12-25 | 2009-03-10 | Mitsubishi Heavy Industries, Ltd. | Denitrification catalyst regeneration method |
| JP2010264418A (en) * | 2009-05-18 | 2010-11-25 | Ihi Corp | Method for cleaning denitration catalyst |
| JP2011031237A (en) * | 2009-07-10 | 2011-02-17 | Kyuden Sangyo Co Inc | Method for improving activity of denitrification catalyst in flue gas denitrification apparatus |
| EP2781252A4 (en) * | 2011-11-17 | 2015-07-08 | Mitsubishi Hitachi Power Sys | Exhaust gas treatment catalyst, method for producing exhaust gas treatment catalyst, and method for regenerating exhaust gas treatment catalyst |
| US9249706B2 (en) | 2011-11-17 | 2016-02-02 | Mitsubishi Hitachi Power Systems, Ltd. | Method for regenerating exhaust gas treatment catalyst |
| JP2016007555A (en) * | 2014-06-20 | 2016-01-18 | 三菱日立パワーシステムズ株式会社 | Method for regenerating used denitration catalyst |
| CN105221222A (en) * | 2015-10-23 | 2016-01-06 | 苏州莲池环保科技发展有限公司 | Ternary catalyzing unit without the need to dismantling restorative procedure |
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