JPH04197451A - Recycling of denitration catalyst - Google Patents
Recycling of denitration catalystInfo
- Publication number
- JPH04197451A JPH04197451A JP2332612A JP33261290A JPH04197451A JP H04197451 A JPH04197451 A JP H04197451A JP 2332612 A JP2332612 A JP 2332612A JP 33261290 A JP33261290 A JP 33261290A JP H04197451 A JPH04197451 A JP H04197451A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- denitration
- denitrification
- denitration catalyst
- deteriorated
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000004064 recycling Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000007790 scraping Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 6
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000227 grinding Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 2
- 238000012856 packing Methods 0.000 abstract 1
- 239000003082 abrasive agent Substances 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000033001 locomotion Effects 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は石炭火力発電所の石炭焚用ボイラー等を有する
作業所において有用なハニカム状の脱硝触媒の再生方法
に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for regenerating a honeycomb-shaped denitrification catalyst useful in a workplace having a coal-fired boiler or the like of a coal-fired power plant.
（従来の技術）
石炭焚用ボイラーにおいて高温での燃焼反応により発生
する窒素酸化物（ＮＯ！ ）は光化学スモッグの原因と
なる物質であり、なんらかの方法で除去する必要がある
ためＮＯｘをＮ２に分解するための脱硝触媒が開発され
ている。(Prior technology) Nitrogen oxides (NO!) generated by high-temperature combustion reactions in coal-fired boilers are substances that cause photochemical smog, and must be removed by some method, so NOx is decomposed into N2. Denitrification catalysts have been developed for this purpose.
現在、火力発電所等では排ガス中のＮＯｘをアンモニア
と反応させる方法によりＮＯｘの除去を行っており、こ
の反応に用いる脱硝触媒が広く用いられている。この触
媒は酸化チタンを主成分とするハニカム状のセラミック
触媒であるが活性表面に不純物が付着してくることによ
り次第にその機能が劣化してくる。このため定期的に新
品の触媒と交換する必要があり、これには真人な費用を
要している。Currently, NOx is removed in thermal power plants and the like by a method of reacting NOx in exhaust gas with ammonia, and denitrification catalysts used for this reaction are widely used. This catalyst is a honeycomb-shaped ceramic catalyst whose main component is titanium oxide, but its function gradually deteriorates as impurities adhere to its active surface. Therefore, it is necessary to periodically replace the catalyst with a new one, which requires a considerable amount of expense.
従って、機能の劣化した脱硝触媒を新品のものよりもよ
り低コストで再生することができれば大きなコストダウ
ンが可能となることから触媒再生技術の開発に大きな期
待が寄せられている。Therefore, if denitrification catalysts with degraded functionality can be regenerated at a lower cost than new ones, there are great expectations for the development of catalyst regeneration technology, since it would be possible to significantly reduce costs.
（発明が解決しようとする問題点）
前述のように触媒再生による利益は真人ではあるが再生
方法として提案されている水あるいは薬品による処理で
は再生した触媒の活性が新品のも］゛のと比べて不十分
であることから実用化は難しいものと判断せざるを得な
い。また、金属性のブラシを用いて触媒の内部表面を摩
耗削除する方法、あるいは摩耗性を有する粉体を用いて
圧縮空気により触媒の表面に衝突させることによって触
媒の表面を摩耗処理する方法が提案されているがこれら
の方法は触媒の破損を招く恐れがあるほか、処理時間が
長い等の欠点を有している。更に、上記の方法の組合せ
として水あるいは薬品中で表面を摩耗処理する方法も提
案されているが処理装置が簡単でなく新品の触媒より低
コストで再生することが困難である。(Problem to be Solved by the Invention) As mentioned above, the benefits of catalyst regeneration are obvious, but the proposed regeneration methods, such as treatment with water or chemicals, show that the activity of the regenerated catalyst is lower than that of a new catalyst. However, we have no choice but to conclude that practical application is difficult because the results are insufficient. In addition, a method has been proposed to abrade the internal surface of the catalyst using a metal brush, or to abrade the surface of the catalyst by using an abrasive powder and colliding it with the surface of the catalyst with compressed air. However, these methods have drawbacks such as the possibility of damage to the catalyst and the long processing time. Further, as a combination of the above methods, a method has been proposed in which the surface is abraded in water or chemicals, but the treatment equipment is not simple and it is difficult to regenerate the catalyst at a lower cost than a new catalyst.
本発明は劣化した触媒の表面を削り落とすという極めて
簡単でかつ有用な再生方法を提供することにより上記問
題点を解決することを目的とする（問題点を解決するた
めの手段）
本発明者等は使用により機能の劣化したハニカム状脱硝
触媒の内部に研削材を充填し振動させることにより内部
表面を削り落とし、新たな触媒活性面を出現させること
が可能であり、しかも再生処理した触媒の活性が新品の
ものと同等レベルまで回復していることを確認し本発明
を完成させるに至った。The present invention aims to solve the above problems by providing an extremely simple and useful regeneration method of scraping off the surface of a deteriorated catalyst (means for solving the problems). By filling the inside of a honeycomb-shaped denitrification catalyst whose function has deteriorated with use and vibrating it, it is possible to scrape off the internal surface and reveal a new catalytic active surface, and the activity of the regenerated catalyst can be improved. It was confirmed that the condition had recovered to the same level as a new one, and the present invention was completed.
本発明で用いる平均粒径８０〜２５００μｍの研削材と
してはアルミナ系及び炭化ケイ素系等一般に市販されて
いる研削材を用いることが可能であるが中でもアルミナ
系のアルミナ・ジルコニアを用いると最も効率よく脱硝
触媒を再生させることができる。使用する研削材の平均
粒径が前記範囲より粗いと、研削材がすみずみまで行き
わたりにくく、触媒内部を均一に削り落とすことが困難
になる。As the abrasive material with an average particle size of 80 to 2,500 μm used in the present invention, commercially available abrasive materials such as alumina-based and silicon carbide-based abrasives can be used, but among them, alumina-zirconia, which is an alumina-based abrasive, is most efficient. The denitrification catalyst can be regenerated. If the average particle size of the abrasive used is coarser than the above range, it will be difficult for the abrasive to spread throughout the catalyst, making it difficult to uniformly scrape off the inside of the catalyst.
一方、逆に細かすぎると研摩能力が不足となり、結果と
して削り落とすために要する時間が長くなり好ましくな
い。On the other hand, if it is too fine, the polishing ability will be insufficient, and as a result, the time required for polishing will become longer, which is not preferable.
また本発明の処理方法において、研削材の充填率が低く
すぎると、研摩能力が不足となり、処理に多大の時間を
要してしまう。一方、充填率が高すぎると、振動による
研削材の移動がスムーズでなくなるため、結果として、
削り落としの効率が低下するので、充填率は好ましくは
１０〜９０容量％、より好ましくは２０〜７０容量％で
ある。研削方法は、空気中あるいは水中で研削材を脱硝
触媒に当てることにより表面を削り落とせばよく特別に
複雑な装置を必要としない。すなわち、例えば脱硝触媒
の空間部に研削材を入れて振動装置で振動させることに
より十分に削り落としが可能である。削り落とす厚みは
不純物の付着状況により若干具なってくるが１０〜２０
０μ−程度であり、通常１０〜１００μ−程度で十分で
ある。Further, in the processing method of the present invention, if the filling rate of the abrasive is too low, the polishing ability will be insufficient and the processing will take a long time. On the other hand, if the filling rate is too high, the movement of the abrasive material due to vibration will not be smooth, resulting in
Since the efficiency of scraping is reduced, the filling rate is preferably 10 to 90% by volume, more preferably 20 to 70% by volume. The grinding method does not require any particularly complicated equipment, as long as the surface is scraped off by applying an abrasive material to the denitrification catalyst in air or water. That is, for example, by putting an abrasive into the space of the denitrification catalyst and vibrating it with a vibration device, it is possible to sufficiently scrape off the denitrification catalyst. The thickness to be scraped off will vary slightly depending on the adhesion of impurities, but it is 10 to 20.
It is about 0μ, and usually about 10 to 100μ is sufficient.
本発明により研削材を用いて表面を削り落とすことによ
って再生した脱硝触媒は新品のものと同等の脱硝性能を
有しており、新品の脱硝触媒と交換するよりも低コスト
で脱硝触媒を提供することが可能である。The denitrification catalyst regenerated by scraping the surface with an abrasive according to the present invention has the same denitrification performance as a new one, and provides the denitrification catalyst at a lower cost than replacing it with a new one. Is possible.
（実施例） 以下、本発明を実施例により説明する。(Example) The present invention will be explained below with reference to Examples.
裏旌孤上
石炭火力発電所等において使用されている脱硝触媒（酸
化チタンを主成分とするハニカム状セラミンク触媒であ
り、１６０ｍ角で長さが９００■の角柱に７■角の穴が
４００ケ所開いているもの）で使用により機能が劣化し
たものを３０１角で長さが２５０閣の角柱（穴が１６ケ
所含まれる：このものの形状を第１図に示した。）とな
るように切断し、触媒の穴（空間部）に穴の容積の３０
容量％量のアルミナ・ジルコニア研削材（日本カーリノ
ド■製：ＡＺ＃１２） ：平均粒径１６８０ｕ■を充
填し往復運動を繰り返した。途中、処理触媒の上下を半
転させて往復運動を繰返すことにより脱硝触媒内部の表
面を約４０μ−分削り落とし、水洗の後乾燥して再生脱
硝触媒を得た。この再生脱硝触媒を用いた脱硝性能試験
の結果を第１表に示した。また、試験に用いた振動装置
の概略を第２図に示した。Denitration catalyst (honeycomb-shaped ceramic catalyst whose main component is titanium oxide) used in the Urajong coal-fired power plant, etc. It is a 160 m square column with a length of 900 mm and 400 7 mm square holes. A pillar (open) whose function has deteriorated due to use was cut into a square pillar with 301 squares and 250 squares in length (including 16 holes; the shape of this pillar is shown in Figure 1). , 30 of the hole volume in the hole (space) of the catalyst
Volume % of alumina-zirconia abrasive material (manufactured by Nippon Carlinodo Corporation: AZ#12): average particle size of 1680 u was filled, and reciprocating motion was repeated. During the process, the treated catalyst was turned upside down and reciprocated repeatedly to scrape off the internal surface of the denitrification catalyst by about 40 μm, washed with water, and then dried to obtain a regenerated denitration catalyst. Table 1 shows the results of the denitrification performance test using this regenerated denitrification catalyst. Moreover, the outline of the vibration device used in the test is shown in FIG.
脱硝触媒 土（第１図参照）の穴の開いた面の一方に触
媒固定用ゴム製支持具 ） を取付け、研削材を穴の中
に充填する。充填後、反対側の面にもゴム製支持具 −
２−を取り付けた後、振動装置本体上部の振動部に固定
する。電動回転機を駆動源として、往復運動用レール
主 にそって振動させることにより触媒内部表面を削り
取るものである。尚、 土 は振動部支持用のスプリン
グである。Denitrification catalyst Attach a rubber support for fixing the catalyst to one side of the holed surface of the soil (see Figure 1), and fill the hole with abrasive material. After filling, also place a rubber support on the opposite side −
After installing 2-, fix it to the vibrating part at the top of the vibrating device main body. Rails for reciprocating motion using an electric rotating machine as the drive source
It mainly scrapes the internal surface of the catalyst by vibrating along the same direction. Note that soil is a spring for supporting the vibrating part.
１施１
アルミナ・ジルコニア研削材として日本カーリット−製
のＡＺ＃１２（平均粒径１６８０μｍ）とＡＺ＃１００
（平均粒径１２５μｌ１１）の等量混合物を３０容量％
量を用いた以外は実施例１に準して行い脱硝触媒内部の
表面を約８０μｍ分削り落とし、水洗の後乾燥して再生
脱硝触媒を得た。この再生脱硝触媒を用いた脱硝性能試
験の結果を第１表に示した。1 Application 1 AZ#12 (average particle size 1680 μm) and AZ#100 manufactured by Nippon Carlit were used as alumina-zirconia abrasives.
(average particle size 125μl11) of an equal volume mixture of 30% by volume.
The procedure of Example 1 was repeated except that the same amount was used, and the inside surface of the denitration catalyst was scraped off by about 80 μm, washed with water, and then dried to obtain a regenerated denitration catalyst. Table 1 shows the results of the denitrification performance test using this regenerated denitrification catalyst.
１較桝土
使用により機能の劣化した脱硝触媒（実施例１で用いた
ものと同等のもの〕を実施例１と同しサイズに切断した
もの（未再生処理）を用いた脱硝性能試験の結果を第１
表に示した。Results of a denitrification performance test using a denitrification catalyst (equivalent to that used in Example 1) whose function had deteriorated due to the use of comparative clay, cut into the same size as in Example 1 (unregenerated) The first
Shown in the table.
第１表
（発明の効果）
本発明による脱硝触媒の再生方法により脱硝触媒の再生
再利用が可能となり石炭焚きボイラー等を有する作業所
における脱硝触媒に要する費用を大きく削減することが
できる。Table 1 (Effects of the Invention) The denitrification catalyst regeneration method according to the present invention enables the denitrification catalyst to be regenerated and reused, and the cost required for the denitrification catalyst in a workplace having a coal-fired boiler or the like can be significantly reduced.
第１図は脱硝触媒（酸化チタンを主成分とするハニカム
状セラミック触媒）の形状を示すものであり、第２図は
脱硝触媒再生のための振動装置の概略を示すものである
。
■・・・脱硝触媒。
２・・・触媒固定用ゴム製支持具。
３・・・往復運動用レール。
４・・・振動部支持用スプリング。
（外３名）FIG. 1 shows the shape of a denitrification catalyst (honeycomb-shaped ceramic catalyst containing titanium oxide as a main component), and FIG. 2 shows an outline of a vibration device for regenerating the denitrification catalyst. ■・・・Denitrification catalyst. 2...Rubber support for catalyst fixation. 3...Rail for reciprocating motion. 4... Spring for supporting the vibrating part. (3 other people)
Claims (1)
触媒の表面部分を削り落とし新たな触媒活性面を出現さ
せることを特徴とする脱硝触媒の再生方法。 ２、平均粒径８０〜２５００μｍの研削材を触媒の内部
に１０〜９０容量％の充填率で充填し、振動させて脱硝
触媒の表面部分を削り落すことを特徴とする請求項１記
載の脱硝触媒の再生方法。[Claims] 1. A method for regenerating a denitrification catalyst, which comprises scraping off a surface portion of a honeycomb-shaped denitrification catalyst whose function has deteriorated to reveal a new catalytically active surface. 2. Denitration according to claim 1, characterized in that an abrasive having an average particle diameter of 80 to 2500 μm is filled inside the catalyst at a filling rate of 10 to 90% by volume, and the surface portion of the denitration catalyst is scraped off by vibration. How to regenerate catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2332612A JPH04197451A (en) | 1990-11-29 | 1990-11-29 | Recycling of denitration catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2332612A JPH04197451A (en) | 1990-11-29 | 1990-11-29 | Recycling of denitration catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04197451A true JPH04197451A (en) | 1992-07-17 |
Family
ID=18256894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2332612A Pending JPH04197451A (en) | 1990-11-29 | 1990-11-29 | Recycling of denitration catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04197451A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005056165A1 (en) * | 2003-12-11 | 2005-06-23 | The Chugoku Electric Power Co.,Inc. | Method for restoring performance capabilities of exhaust gas treatment apparatus |
| KR100880236B1 (en) * | 2006-07-10 | 2009-01-28 | 쥬코쿠 덴료쿠 가부시키 가이샤 | Method for restoring performance capabilities of exhaust gas treatment apparatus |
| JP2011194289A (en) * | 2010-03-17 | 2011-10-06 | Chugoku Electric Power Co Inc:The | Device for evaluation of polishing state of honeycomb catalyst |
| WO2014155628A1 (en) | 2013-03-28 | 2014-10-02 | 中国電力株式会社 | Method for regenerating denitrification catalyst |
| US8980779B2 (en) | 2002-06-21 | 2015-03-17 | The Chugoku Electric Power Co., Inc. | Method of regenerating NOx removal catalyst |
| CN104741113A (en) * | 2015-04-02 | 2015-07-01 | 易能（马鞍山）大气治理科技有限公司 | Low-cost denitration catalyst and preparation method thereof |
| WO2021171627A1 (en) * | 2020-02-28 | 2021-09-02 | 中国電力株式会社 | Denitration catalyst abrasion method and denitration catalyst abrasion device |
-
1990
- 1990-11-29 JP JP2332612A patent/JPH04197451A/en active Pending
Cited By (12)
| 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 |
| WO2005056165A1 (en) * | 2003-12-11 | 2005-06-23 | The Chugoku Electric Power Co.,Inc. | Method for restoring performance capabilities of exhaust gas treatment apparatus |
| US7441332B2 (en) | 2003-12-11 | 2008-10-28 | The Chugoku Electric Power Co., Inc. | Method for restoring performance capabilities of exhaust gas treatment apparatus |
| CN100431672C (en) * | 2003-12-11 | 2008-11-12 | 中国电力株式会社 | Method for restoring performance of exhaust gas treatment apparatus |
| KR100880236B1 (en) * | 2006-07-10 | 2009-01-28 | 쥬코쿠 덴료쿠 가부시키 가이샤 | Method for restoring performance capabilities of exhaust gas treatment apparatus |
| JP2011194289A (en) * | 2010-03-17 | 2011-10-06 | Chugoku Electric Power Co Inc:The | Device for evaluation of polishing state of honeycomb catalyst |
| WO2014155628A1 (en) | 2013-03-28 | 2014-10-02 | 中国電力株式会社 | Method for regenerating denitrification catalyst |
| KR20160002805A (en) | 2013-03-28 | 2016-01-08 | 쥬코쿠 덴료쿠 가부시키 가이샤 | Method for regenerating denitrification catalyst |
| US10335780B2 (en) | 2013-03-28 | 2019-07-02 | The Chugoku Electric Power Co., Inc. | Method for regenerating denitrification catalyst |
| CN104741113A (en) * | 2015-04-02 | 2015-07-01 | 易能（马鞍山）大气治理科技有限公司 | Low-cost denitration catalyst and preparation method thereof |
| CN104741113B (en) * | 2015-04-02 | 2017-07-14 | 易能环境技术有限公司 | A kind of inexpensive denitrating catalyst and preparation method thereof |
| WO2021171627A1 (en) * | 2020-02-28 | 2021-09-02 | 中国電力株式会社 | Denitration catalyst abrasion method and denitration catalyst abrasion device |
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