JPS58189041A - Regeneration of catalyst - Google Patents

Abstract

PURPOSE:To wash and re-activate a catalyst capacity of which is lowered by the accumulation of a poisoning substance, in regenerating a catalyst of gas treating treatment, by a method wherein said catalyst is washed with an aqueous hydrochloric acid solution and the washed catalyst is dried. CONSTITUTION:When the activity of a catalyst is lowered in reaction for treating an exhaust gas generated through the combustion of coal or petroleum, the flowing of a treating gas is stopped while a washing nozzle 2 is provided in opposed relation to the opening surface of the gas passing perforations of a reaction layer 1 and an aqueous hydrochloric acid solution in a washing water tank 5 is supplied to wash the catalyst. By this method, because a poisoning component accumulated in the catalyst is eluted by washing water, the catalyst is re-activated.

Description

【発明の詳細な説明】 か使用余中に被毒物の蓄積により性能か低十したときに
、該触媒を洗浄し再賦活させる改良された方法を提供す
るものであり　特に石炭や４１曲を燃焼させた排カスを
触媒中に通過させてｕ１カス中の窒素酸化物を還元して
無害化する脱硝反応又は一酸化炭素あるいは炭化水素な
どを触媒をｉｌ用して酸化燃焼させる反応等に適用して
好適なものでおるっ 一般に，重油焚きボイラや石炭焚きボイラの排ガスＪよ
うなタストとＳＯｘを含有するダーテ１ガスを処理する
ものてはｌ？ｌｌｔＳＯｘ性、耐タスト１毒性、耐ダス
ト閉塞＋ｌ４、配タスト摩耗慴なとを考！ゼして最適な
触媒ｆｉ様を選定する必要かＩリ，ＬＮＧＷきボイラ用
その他で多用されているＡ１２０：（に代りＴ１０２　
を担体にすることで耐ＳＯｘ性が１一分になることから
、Ｔ１０２に■２０５。DETAILED DESCRIPTION OF THE INVENTION The present invention provides an improved method for cleaning and reactivating catalysts when their performance has deteriorated due to accumulation of poisons during unused use, especially when burning coal or It can be applied to denitrification reactions in which the waste residue is passed through a catalyst to reduce the nitrogen oxides in the waste to render it harmless, or in reactions in which carbon monoxide or hydrocarbons are oxidized and burned using a catalyst. In general, what is suitable for treating dirty gases containing dust and SOx, such as exhaust gas from heavy oil-fired boilers or coal-fired boilers? Considering SOx resistance, dust resistance 1 toxicity, dust blockage resistance +l4, and dust wear resistance! Is it necessary to select the most suitable catalyst type?
■205 for T102 because the SOx resistance becomes 11 minutes by using it as a carrier.

ＷＯ３　　、　Ｆｅ２Ｏ２　　、　Ｍｏ０３などの活性
唆分を担持さぜた触媒か使用されている，又ダスト閉窒
しない触媒形状としてはｆ’＋ｊ状，円柱状，だ固体状
などに成形さｔｌだ触媒を移動床で（炉用する方法，穀
状，パイプ状、格ｒ状，・・ニカム状なとの触媒構造体
を固定床にして？Ｊ＋ガスを並行流で通過させる方法か
比較検ｄ−１され．現在ではａ済性があり，保守の簡１
ｉ’ｉな格ｒ一状触媒が主流となっている．そして看ｊ
炭焚きボイラの高タスト側での脱硝反Ｌ１″・、にも硬
度の高い格子状１媒か開発され，′１′川１・ほとんと
間ｌＩ！！ｌσ・ない状聾てあう。Catalysts supported with active components such as WO3, Fe2O2, Mo03, etc. are used. Catalysts that do not nitrate due to dust formation include f'+j, columnar, solid, etc. catalysts. Comparative test d-1: Using a moving bed (a method using a furnace, using a fixed bed with a grain-like, pipe-like, grating-like, nicum-like catalyst structure? A method of passing J+ gas in parallel flow? Nowadays, it is easy to maintain and maintenance is easy.
i'i case r one-state catalysts are the mainstream. And watch
A highly hard lattice type 1 medium was also developed for denitrification on the high duty side of a coal-fired boiler, and the lattice type 1 medium with high hardness is almost deafening.

しかし、Ｔ　ｉ　Ｏ２を担体とした並行流形格ｒ−状触
媒でも触媒面にダストか付着した状態で水て濡れたり、
ボイラの蒸発管やエコノマイサー給水管の破損事故で火
炉中のタストを含んだ蒸気又は水か触媒を濡らす場合に
は、上記ダスト中にに、ｔ　Ｎａ　、Ｍｇ等か含まｔ］
ているため触媒内部に急激にに、　Ｎａ　、　Ｍｇなど
の被毒物か増、’Ｊｌｌ　して予期していない性能低下
をきたし、ボイラの運転かできないような事故か発生す
る場合プ、ある。However, even with a parallel flow type r-shaped catalyst using T i O2 as a carrier, the catalyst surface may get wet with dust attached to it.
If the catalyst is wetted with steam or water containing dust in the furnace due to a breakage of the boiler evaporator pipe or economizer water supply pipe, the above dust may contain Na, Mg, etc.
As a result, poisonous substances such as Na and Mg can rapidly increase inside the catalyst, causing an unexpected performance drop and causing an accident in which the boiler cannot be operated.

このような緊急事故により脱硝装置か所期の性能を発揮
しなくな一〕だ時は、最悪の場合ボイラを停止１−せさ
るを得ない状況になることも想゛ボされるので、短期間
で性能回復させる方法を提供する必要かある。If the denitrification equipment does not perform as expected due to an emergency accident like this, in the worst case scenario, the boiler may have to be shut down, so it may be impossible to do so in the short term. Is there a need to provide a method to recover performance in between?

本発明者等は、すてに“ガス油路を有する触媒を内蔵し
たカス処理装置の稼動時に、ス　ノブローノズルより高
１Ｆガス体を噴射して触媒層部へ付着、坩積したダスト
を除去した後、１ｉｉｆ　＋？＋’装置の運転を停止＝
　１．　、次いでＩｉｉ＋記ス−’／７０ノズルを水洗
用ノズルに仝換し、該水洗ノズルより６浄水を噴射して
触媒内部に浸入、蓄積した肢＃成分を溶出除去せしめる
ことからなる。The inventors of the present invention have previously proposed that ``During the operation of a waste treatment device containing a catalyst having a gas oil passage, a high 1F gas body is injected from a snow blow nozzle to remove dust that has adhered to the catalyst layer and accumulated. After that, 1iif +?+' Stop the device operation =
1. Then, the 70 nozzle in III+ is replaced with a water washing nozzle, and purified water is injected from the washing nozzle to elute and remove the component # that has entered and accumulated inside the catalyst.

触媒の賦活方法″（特願ＩＩＩ’＋　５６−１２８８３
０号）１“ガス列理反応における触媒の性能低を時に、
装置内１−触媒を充填した１）熊で水洗して触媒性能を
回復させるに当り、処理カスの流通を停止１−せしめた
後、洗浄水を、カスの辿過する空塔断面１ｍ２”＋９２
（１０−８ｎｏ　ｌ　／分の割ａで、２回置Ｉに区ｖＪ
−・て散布することを特徴とする触媒の賦活ＩＪ法″（
特願昭５６−１２８８３１号）、及び“触媒層カス通過
面を複数に分割して順次水洗し、か−）、その際、第１
の触媒区画の水洗直後のｌ’ｊ染物實濃度の高い排水は
廃棄し、その後のｔり染物實ａ度の１１（い排水を第２
の触媒区画の水洗水として使用し、　ＩＪ、　Ｆ　、同
様に順次水洗して行くことを特徴とする触媒の水洗方法
”（特願昭５６　１１７８４３号）等、性能か低ドした
触媒の水６による＋１）賦活（１−力ＬＪ５を発明し、
特Ｊ１１１・願している−。Catalyst Activation Method'' (Patent Application III'+ 56-12883
No. 0) 1 “Sometimes, the performance of catalysts in gas column chemical reactions is low.
Inside the device 1- When the catalyst filled with 1) is washed with water to recover the catalyst performance, the flow of the treated scum is stopped 1- After the flow of the treated scum is stopped, the washing water is passed through the empty column cross section of 1 m2" + 92 where the scum flows.
(at a rate of 10-8 no l/min, the division vJ in the second position I
``Catalyst activation IJ method'' (
(Japanese Patent Application No. 128831/1983) and "The catalyst layer waste passing surface is divided into a plurality of parts and sequentially washed with water. In that case, the first
Immediately after washing the catalyst compartment with water, the wastewater with a high concentration of l'j dyeing material is discarded, and the subsequent wastewater with a dyeing material concentration of 11
Water for catalysts with low performance, such as "A method for washing catalysts characterized by sequentially washing IJ, F, etc." (Japanese Patent Application No. 117843, 1982), is used as water for washing catalyst compartments of +1) Activation (1- Invented force LJ5,
Special J111・I'm praying for you.

これらの発明は、何ｔ１も前述のような性能の低丁した
触媒を再賦活せしめる手段として有効であるか、前記排
カス中にはＣａ　、　ＳＯｘ及びＨ２Ｏをも含むため、
前記のような各種の触媒（粒状触媒や担体がＡ１□０３
からなる触媒をも含む）の表面あるいは内部に硫酸力ル
ノウムの様に水に溶解し難い被毒物が蓄積することりあ
りこのような場合ｌ、二は水のみによる洗浄で（まＡｔ
　Ｈの性能を使用ｉｉ４能な状態にまで再賦活すること
か困難である。又水洗後に硫酸カル／ラムの結晶か触媒
の表面に析出することもあり、こ１＋か触媒の細孔部を
閉塞すると細孔内部に蓄積しているに、Ｎａ　　等のよ
うな水溶性のある被毒物質の溶出をも妨けることとなる
。本発明は、以十のような今迄に提案されそσ・一部は
すてに実施されている触媒の水洗による再ｆＸ活方法の
イ・充分な点を改良しようとして発明さｔ］だものであ
る。These inventions are effective as a means to reactivate a catalyst with low performance as mentioned above, or because the waste gas also contains Ca, SOx and H2O,
Various catalysts as mentioned above (granular catalysts and carriers are A1□03
In such cases, poisonous substances that are difficult to dissolve in water, such as sulfuric acid, may accumulate on the surface or inside of the catalyst (including catalysts made of
It is difficult to reactivate H's performance to a usable state. In addition, crystals of Cal/Rum sulfate may be deposited on the surface of the catalyst after washing with water, and if the pores of the catalyst are blocked, water-soluble substances such as Na etc. This also prevents the elution of poisonous substances. The present invention was invented in an attempt to improve the sufficient points of the fX reactivation method by washing the catalyst with water, which has been proposed up to now and some of which has already been carried out. It is something.

以Ｆ本発明を脱硝触媒の例ζこついて詳しく説明する。Hereinafter, the present invention will be explained in detail using an example of a denitrification catalyst.

塩酸水溶液を１　／　５００〜１／１０規定、好ましく
は１　／　１００〜ｌ／２０　規カーに調整した洗浄液
を用いて、活性が低ドシた触媒を５分〜９０分。Using a cleaning solution containing an aqueous hydrochloric acid solution adjusted to 1/500 to 1/10 normal, preferably 1/100 to 1/20 normal, the catalyst with low activity is washed for 5 to 90 minutes.

好ましくは３０分〜６０分洗浄する、本洗浄によって特
に水に溶解しにくい硅酸カルノウム智の肢み物を溶出除
去し、活性を賦活させる９水洗ｉ１　　）ｊ法は水では
溶出しく−くいカル／ラム分ヲ塩酸水ｆｆＦ液（こより
短時間に効率よく溶出するものであり、　ＴｉＯ２に■
２０３、ＷＯ３，Ｆｅ２Ｏ３，ＭｏＯ３なとの活性成分
を組合せた触媒、又触媒の形状としては粉状１円ｔＦ状
、１に状なとに成形された触媒及び椴状１・・イブ４ノ
ー格ｆ状、・・ニカム状なとの触媒構造体のコート状、
／　ＩＪ　ｙド状の触媒のＩ打手方法に本分（す］か過
ｎ１できる。又洗浄温度を１゛けることにより給田ｌｊ
ｆ間は短縮されるか触媒ｒ１ν分の溶解度も１−＞１す
ることがら常温の力か好ましいか、特に俣用を限定する
ものてはないユさらに洗浄方法も通常の゛スプレー洗浄
あるいは浸漬洗浄のいずれも適用でき、特に限定さ第１
るもΩてはない〜被毒物質を除去し゛た触媒は通常の乾
燥方法にて乾燥し、引続き脱硝触媒として供される。本
洗浄方法は石炭、焚き枡カスに適用した触媒の再生方法
として特に有効であるか、こｔｌに限定するＣのではな
く２重油焚きす１カス、ゴミ焼却炉排カス等に適用した
触媒の出生方法としても利用でき、゛その方υ―は部活
で′Ｊ川」−の効果は非常に犬といえる。Washing is preferably carried out for 30 to 60 minutes.This washing removes carnoum silicate substances that are particularly difficult to dissolve in water and activates their activity. / Rum water hydrochloric acid water ffF solution (it elutes more efficiently in a shorter time than this, and it is
203, a catalyst that combines active ingredients such as WO3, Fe2O3, and MoO3, and the shape of the catalyst is a powder-like 1 yen tF shape, a catalyst shaped into a 1-shaped shape, and a bowl-like 1... Eve 4 no grade. f-shaped,...Nicum-shaped catalyst structure coated,
/ IJ It is possible to use the I-cutting method for a y-shaped catalyst.Also, by setting the cleaning temperature by 1, it is possible to
Since the distance between f is shortened and the solubility of the catalyst r1ν is also 1->1, it is preferable to use the force at room temperature.There is no particular restriction on the use of matata. Any of the above can be applied, especially limited to the first
The catalyst from which poisonous substances have been removed is dried by a conventional drying method and subsequently used as a denitrification catalyst. Is this cleaning method particularly effective as a method for regenerating catalysts applied to coal and combustion slag? It can also be used as a method of birth, and the effect of ``That way υ is club activities and ``J River'' can be said to be very effective.

次に添付図面（二基いて本願発明の実施態様を説明する
。第１図は石炭焚きボイラ排カス用１況硝装置に適用す
る場合の１例を示すっ通常の運転時に於ては、ボイラ７
の燃焼排ガス８は脱硝装置６に導入され、排カス中の窒
素酸化物と還元剤として供給されたアンモニアカス１４
を脱硝触媒層ｌ内にて反応せしめて無害な窒素と水とに
分解させるものであり脱硝後の排カス９は後、流のエア
ヒータ１０を通して熱交換した後に更に後流に通される
。運転を第１工・してｆＩ・■らかの原因、例えは排ガ
ス中のアルカリ金属、アルカリ土類金減などによる触媒
σ被査によって触媒のイ１能が低トしてきたＷ合に、ボ
イラの点検ル１１１１中など処理ガスの肺通を停止１−
せしめたボイラ停止１時に洗浄を行う、即ち、反り己、
層１のカス通過橿の開１１曲に対向して洗浄用ノズル２
を設置し、洗浄水槽５からホ／プ１５にて洗浄水３か洗
浄用ノズルに供給し反ＬＬ、層全体を洗浄する。、触媒
中に蓄積さｔ、た被毒成分を溶１１″１せしめた洗浄排
水４は洗浄水槽に９１出され線点し１史用される。洗浄
か終Ｔしたら外部から導入される仕−トは水１６にてさ
らに水洗されその排水は洗浄傅＊４と合せ外Ｆｈ（ｎす
１水処理槽で処理される。又、水洗（受はボイラの火入
れ曲に触媒層１に桟存している水分の水ψＪす、乾燥を
行な　・ておく、この当社として（ｊ、例えは通気ブロ
ワ１３を駆如・し、′＋気１１゜１２、をボイラを経由
して創；妓層１に（ノ（給することなどが第５倉ちれる
。Next, the embodiments of the present invention will be explained with reference to the attached drawings. 7
The combustion exhaust gas 8 is introduced into the denitrification device 6, where nitrogen oxides in the exhaust gas and ammonia scum 14 supplied as a reducing agent are combined.
is reacted in the denitrification catalyst layer 1 to decompose it into harmless nitrogen and water, and the waste residue 9 after denitration is then passed through an air heater 10 for heat exchange and then passed further downstream. After the first operation, if the catalyst's performance has decreased due to the catalyst's loss of fI, for example, due to a decrease in alkali metals and alkaline earth metals in the exhaust gas, Stop the passage of process gas through the lungs during boiler inspection 1111, etc. 1-
When the boiler is stopped, it is cleaned, i.e. warped,
Cleaning nozzle 2 is installed opposite the opening 11 of the waste passing rod of layer 1.
is installed, and the washing water 3 is supplied from the washing water tank 5 to the washing nozzle through the pump 15 to wash the entire layer. The cleaning wastewater 4, in which the poisonous components accumulated in the catalyst have been dissolved, is discharged into the cleaning water tank and used for one cycle.After the cleaning is finished, the water is introduced from the outside. The water is further washed with water 16, and the waste water is treated in a cleaning tank *4 and a water treatment tank outside Fh (nsu1). Dry the water ψJ that is in the air. In 1 (ノ()), the fifth category falls into the fifth category.

次に実施例によって説明する。Next, an example will be explained.

［一実施例〕 石炭焚き排カスで１２０００時間経過して活性が低下し
た脱硝触媒を１　／　５０規定の塩酸水溶液により第１
表に示す条件で洗浄した。[One Example] A denitrification catalyst whose activity has decreased after 12,000 hours in coal-fired waste residue is first treated with a 1/50 N hydrochloric acid aqueous solution.
Washing was performed under the conditions shown in the table.

第１表　　　洗浄条件 ６０分洗浄後の触媒をさらにイ１上水にて１ｏ分間ｆｋ
浄し、これを１０５°Ｃで３時間乾燥後第２表に示を活
性試験条件で脱硝性能を測定した。Table 1 Cleaning conditions: After washing for 60 minutes, the catalyst was further washed with tap water for 10 minutes.
After drying at 105°C for 3 hours, the denitrification performance was measured under the activity test conditions shown in Table 2.

その結果被毒成分の溶出率として第２図に示す結果か碍
らへ、第１表に示す同し洗浄条件での水による従来の洗
浄法（第３図）に比ベカル７ウム分の溶Ｌ（１率が高く
さらに溶出時間もｂｊ縮されることか確認された。又第
２表に示す活性試験条件ての脱硝率測定結果を ＦＲＥＳＭ触媒の脱硝率 て表わし第３表１示したか、本発明の再牛刀θ、にて活
性を賦活させた触媒は従来の水（こよる再生方法に比べ
活性回復率か高く１本発明の有効性が確認された。As a result, the elution rate of poisonous components was as shown in Figure 2. Compared to the conventional cleaning method using water (Figure 3) under the same cleaning conditions as shown in Table 1, the elution rate was 7 um. It was confirmed that the denitrification rate was high and the elution time was also shortened.Also, the results of measuring the denitrification rate under the activity test conditions shown in Table 2 were expressed as the denitrification rate of the FRESM catalyst, and Table 3 shows the results. The effectiveness of the present invention was confirmed because the activity recovery rate of the catalyst activated by the regeneration method of the present invention was higher than that of the conventional regeneration method using water.

以Ｉ−１固定床式触媒反Ｌト装ｒ］に本発明をＪス用す
る場合につき説明したか１本斧明は移セト床Ｊ（触媒反
応装置において装置外に粒状の触媒を取出して塩酸洗浄
しても良く、さらに使用する塩酸の濃度が低い場合には
仕上は水による耐経的な洗浄を省略しても充分効果かあ
る。The following describes the case where the present invention is applied to a fixed bed type catalyst reactor (I-1). Hydrochloric acid cleaning may be used, and if the concentration of hydrochloric acid used is low, the finish may be sufficiently effective even if the aging-proof cleaning with water is omitted.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明の実施態様を示したｔ、のである。 ｌ　脱硝触婢層、　２　洗浄用ノスル。 ３　洗浄用水、　　４　洗浄排水、　　５　洗浄水槽６
　脱硝反応器、　７　ボイラ、　８　ボイラ排ガス、　
　９　脱硝後排カス、１０　　エアヒ　タ１１・空気、
　　１２　　空気、　　　１３　　通気ブロワ。 １４　　アンモニアカス、　　　１５　　・洗浄水循環
ホ／フ１６−仕上は水 第２図は本発明で実施したカリウム、ナトＩＪウム、カ
ル７ウムの溶出率と洗浄時間の関係を示したものである
。 第３図は従来法の水洗のみで実施したカリウム、ナトリ
ウム、カル／ラムの溶出率ト洗ｄ＋　時間の関係を示し
たものである。 第１図 第２（￥１ Ｏ２ｏ　　　　　４０　　　　６０　　　８ｏ　　　　
　１ｏＯ涜浄Ｆｐｔ聞　［ｙｎ　ｒ　ｎ］FIG. 1 shows an embodiment of the present invention. l Denitrification contact layer, 2 Nostle for cleaning. 3 Washing water, 4 Washing water, 5 Washing water tank 6
Denitrification reactor, 7 boiler, 8 boiler exhaust gas,
9 Exhaust scum after denitrification, 10 Air heater 11 Air,
12 air, 13 ventilation blower. 14 Ammonia scum, 15 - Washing water circulation ho/f 16 - Finishing is water Figure 2 shows the relationship between the elution rate of potassium, sodium chloride and calcium chloride and the cleaning time carried out in the present invention. FIG. 3 shows the relationship between the elution rate of potassium, sodium, and Cal/Rum in the conventional method using only water washing and washing d+ time. Fig. 1 No. 2 (¥1 O2o 40 60 8o
1oO sacrilege Fpt listening [yn r n]

Claims (1)

【特許請求の範囲】[Claims] ガス処理反応における触媒の性能低ト時に、該触媒を洗
浄して触媒性能を回復させるに当り処理カスの流通を停
止セしめた後、塩酸水溶液で洗浄し、洗浄後の触媒を乾
燥する。ことを特徴とする触媒の再生方法。When the performance of the catalyst in the gas treatment reaction is low, the catalyst is washed to restore the catalyst performance, and after stopping the flow of the treated waste, the catalyst is washed with an aqueous hydrochloric acid solution, and the washed catalyst is dried. A method for regenerating a catalyst, characterized by: