JP4440579B2 - Denitration catalyst regeneration method - Google Patents
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- JP4440579B2 JP4440579B2 JP2003312205A JP2003312205A JP4440579B2 JP 4440579 B2 JP4440579 B2 JP 4440579B2 JP 2003312205 A JP2003312205 A JP 2003312205A JP 2003312205 A JP2003312205 A JP 2003312205A JP 4440579 B2 JP4440579 B2 JP 4440579B2
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- 239000003054 catalyst Substances 0.000 title claims description 92
- 238000011069 regeneration method Methods 0.000 title description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 9
- 230000001172 regenerating effect Effects 0.000 claims description 9
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- -1 alkaline earth metal sulfates Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009423 ventilation Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002506 iron compounds Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 229910000358 iron sulfate Inorganic materials 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000010742 number 1 fuel oil Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Description
本発明は脱硝触媒の再生方法に係り、さらに詳しくは使用済排煙脱硝触媒の再生方法に関するものである。 The present invention relates to a method for regenerating a denitration catalyst, and more particularly to a method for regenerating a spent flue gas denitration catalyst.
近年、廃棄物の発生量を低減するため、使用済触媒を再利用する必要が生じている。特に石炭や重油を燃料としたボイラ排ガスの排ガス脱硝触媒では、長時間の使用によりアルカリ金属、アルカリ土類金属、砒素化合物等による経時的な性能低下が生じる。しかし、これら毒物質は概ね洗浄により該脱硝触媒から除去することができる。該溶液としては水、硫酸、蓚酸、アンモニア、硫酸塩などが用いられ、これらの洗浄液を単独でまたはその組み合わせにより毒物質を除去して触媒の脱硝性能を回復させることが知られている（特許文献１、２等）。 In recent years, it has become necessary to reuse used catalysts in order to reduce the amount of waste generated. In particular, in an exhaust gas denitration catalyst for boiler exhaust gas using coal or heavy oil as fuel, performance deterioration with time due to alkali metal, alkaline earth metal, arsenic compound, etc. occurs due to long-term use. However, these toxic substances can be removed from the denitration catalyst by washing. As the solution, water, sulfuric acid, oxalic acid, ammonia, sulfate, etc. are used, and it is known that these cleaning liquids alone or in combination remove toxic substances to recover the denitration performance of the catalyst (patent) Literature 1, 2 etc.).
一方、金属網状物と脱硝触媒成分とからなる板状触媒の場合、水、硫酸または硫酸塩の溶液で洗浄すると、脱硝活性とともに、ＳＯ2 のＳＯ3 への酸化率（以下、ＳＯ2 酸化率という）も高くなるという問題点があった。これは、金属網状物と排ガス成分が反応して形成された鉄化合物が洗浄液に溶解し、乾燥時に触媒表面に析出し、該鉄化合物が酸化触媒として働くためと考えられる。
本発明の課題は、上記の問題を解決し、金属網状物と脱硝触媒成分とからなる使用済排煙脱硝触媒を再生する際に、再生触媒のＳＯ2 酸化率の上昇を防ぎ、少なくとも洗浄前と同等か、それ以下のＳＯ2 酸化率にすることができる脱硝触媒の再生方法を提供することにある。
On the other hand, in the case of a plate catalyst composed of a metal network and a denitration catalyst component, when washed with water, sulfuric acid or a sulfate solution, the denitration activity and the oxidation rate of SO 2 to SO 3 (hereinafter referred to as the SO 2 oxidation rate). There was a problem that it was also expensive. This is presumably because the iron compound formed by the reaction of the metal network and the exhaust gas component dissolves in the cleaning liquid and precipitates on the catalyst surface during drying, and the iron compound acts as an oxidation catalyst.
The object of the present invention is to solve the above-mentioned problems and prevent an increase in the SO 2 oxidation rate of the regenerated catalyst when regenerating a spent flue gas denitration catalyst comprising a metal network and a denitration catalyst component, at least before washing. It is an object to provide a method for regenerating a denitration catalyst that can achieve an SO 2 oxidation rate that is equal to or lower than that.
本発明者らは、使用済脱硝触媒を、該触媒に含まれる全硫酸根モル数の２倍以上のアンモニアまたはアンモニウム塩を含む溶液に浸漬すると、使用済脱硝触媒に含まれる硫酸鉄はほとんど溶出せず、触媒表層の付着物や、ＮａやＫのようなアルカリ金属や、ＣａやＭｇのようなアルカリ土類金属の硫酸塩のみが洗浄、除去され、さらにこの洗浄された触媒に脱硝触媒粉末を含むスラリーをコートすることにより、ＳＯ2 酸化率の上昇を抑制しながら、高活性な触媒に再生できることを見出し、本発明に到達した。
上記課題を解決するため、本願で特許請求される発明は下記の通りである。
When the present inventors immerse the used denitration catalyst in a solution containing ammonia or ammonium salt that is twice or more the total number of moles of sulfate radicals contained in the catalyst, most of the iron sulfate contained in the used denitration catalyst is eluted. Without cleaning, only the deposits on the surface of the catalyst, alkali metals such as Na and K, and alkaline earth metal sulfates such as Ca and Mg are washed and removed. It was found that by coating a slurry containing, the catalyst can be regenerated into a highly active catalyst while suppressing an increase in the SO 2 oxidation rate, and the present invention has been achieved.
In order to solve the above problems, the invention claimed in the present application is as follows.
（１）酸化チタンを含む脱硝触媒成分をステンレス製網状物に担持した、硫酸根を含む使用済排煙脱硝触媒を、該触媒に含有する全硫酸根のモル数の２倍以上のアンモニアまたはアンモニウム塩を含む溶液に浸漬した後、液切りして乾燥し、次いで酸化チタンを含む脱硝触媒粉末と無機酸化物のコロイド状物とを含有するスラリを担持させて乾燥することを特徴とする脱硝触媒の再生方法。
（２）酸化チタンを含む脱硝触媒成分をステンレス製網状物に担持した、硫酸根を含む使用済排煙脱硝触媒を、該触媒に含有する全硫酸根のモル数の２倍以上のアンモニアまたはアンモニウム塩を含む溶液と、無機酸化物のコロイド状物と、酸化チタンを含む脱硝触媒粉末とを含有するスラリに担持した後、乾燥することを特徴とする脱硝触媒の再生方法。
（３）前記無機酸化物のコロイド状物が、チタニア、シリカ、アルミナおよびジルコニアの少なくとも１種を含むことを特徴とする（１）または（２）に記載の脱硝触媒の再生方法。
(1) A used NOx removal denitration catalyst containing sulfate radicals, in which a denitration catalyst component containing titanium oxide is supported on a stainless steel net, is ammonia or ammonium at least twice the number of moles of all sulfate radicals contained in the catalyst. A denitration catalyst characterized in that it is dipped in a solution containing salt, drained and dried, and then dried by supporting a slurry containing a denitration catalyst powder containing titanium oxide and a colloidal inorganic oxide. How to play.
(2) A used exhaust flue gas denitration catalyst containing sulfate radicals, in which a denitration catalyst component containing titanium oxide is supported on a stainless steel net, is ammonia or ammonium at least twice the number of moles of all sulfate radicals contained in the catalyst. A method for regenerating a denitration catalyst, comprising supporting a slurry containing a salt-containing solution, a colloidal inorganic oxide, and a denitration catalyst powder containing titanium oxide, followed by drying.
(3) The method for regenerating a denitration catalyst according to (1) or (2), wherein the inorganic oxide colloidal material contains at least one of titania, silica, alumina, and zirconia.
本発明によれば、使用済の触媒体を廃棄することなく、ＳＯ3 の発生を極力少なくして再利用できるため、機器の腐食等を生じさせることなく、産業廃棄物の削減を図ることができる。 According to the present invention, since it is possible to reuse by reducing the generation of SO 3 as much as possible without discarding the used catalyst body, it is possible to reduce industrial waste without causing corrosion or the like of equipment. it can.
本発明において用いる溶液中のアンモニアまたはアンモニウム塩の量は、該使用済脱硝触媒に含まれる全硫酸根のモル数の２倍以上とする必要がある。溶液に含まれるアンモニアまたはアンモニウム塩のモル数が、使用済脱硝触媒に含まれる全硫酸根のモル数の２倍以上であれば、アンモニウムイオンが触媒から溶出する硫酸根と反応しても、液中のアンモニウムイオンは硫酸鉄を含む硫酸塩よりも過剰の状態となるため、硫酸鉄が液中に溶出するのを防ぐことができる。これにより、乾燥時に鉄化合物が触媒表面に担持されるのを防ぐことできるため、再生された触媒のＳＯ2 の酸化率の上昇を抑えることができる。 The amount of ammonia or ammonium salt in the solution used in the present invention must be at least twice the number of moles of total sulfate radicals contained in the used denitration catalyst. If the number of moles of ammonia or ammonium salt contained in the solution is at least twice the number of moles of total sulfate radicals contained in the used denitration catalyst, the solution can be used even if ammonium ions react with the sulfate radicals eluted from the catalyst. The ammonium ions therein are in an excess state compared to the sulfate containing iron sulfate, so that iron sulfate can be prevented from being eluted into the liquid. Thus, the iron compound because it can avoid being carried on the catalyst surface, it is possible to suppress an increase in oxidation rate of SO 2 in the regenerated catalyst on drying.
使用済脱硝触媒表面の付着物は、アンモニアまたはアンモニウム塩溶液への浸漬による物理的な洗浄効果で除去されるため、エアバブリング、超音波振動や攪拌等の操作により、溶液が滞留しない状態とすることにより、より短時間に該付着物の除去が可能となる。
また上記溶液に浸漬した使用済脱硝触媒は、液切りした後、できるだけ素早く乾燥させるのが好ましい。これにより、金属網状物や付着した灰中に含まれる鉄化合物の触媒表面への拡散を抑制できるため、再生触媒のＳＯ2 酸化率をより低減することができる。
Since the deposits on the surface of the used denitration catalyst are removed by a physical cleaning effect by immersion in ammonia or ammonium salt solution, the solution does not stay by air bubbling, ultrasonic vibration, stirring, etc. Thus, the deposits can be removed in a shorter time.
The used denitration catalyst immersed in the above solution is preferably dried as quickly as possible after draining. Thereby, since the diffusion to the catalyst surface of the iron compound contained in the metal network or the attached ash can be suppressed, the SO 2 oxidation rate of the regenerated catalyst can be further reduced.
さらに、使用済脱硝触媒の上記アンモニウムまたはアンモニウム塩の溶液への浸漬によりＳＯ2 酸化率の上昇を防ぎながら触媒表面の石炭灰や付着物を洗い流した後、無機酸化物のコロイド状物と脱硝触媒粉末とを含むスラリをコートすることにより、再生触媒の脱硝率を一層高めることができる。また、使用済脱硝触媒に、アンモニアまたはアンモニウム塩の溶液、無機酸化物のコロイド状物および触媒粉末を含むスラリをコートしても同様の効果が得られる。
前記無機酸化物のコロイド状物としては、チタニア、シリカ、アルミナおよびジルコニアの少なくとも１種が好ましく用いられる。
Further, after the used denitration catalyst is immersed in the ammonium or ammonium salt solution to prevent the SO 2 oxidation rate from increasing, the coal ash and deposits on the catalyst surface are washed away, and then the colloidal inorganic oxide and the denitration catalyst are washed away. By coating a slurry containing powder, the denitration rate of the regenerated catalyst can be further increased. The same effect can be obtained by coating the used denitration catalyst with a slurry containing ammonia or ammonium salt solution, colloidal inorganic oxide and catalyst powder.
As the inorganic oxide colloid, at least one of titania, silica, alumina and zirconia is preferably used.
以下、本発明を実施例により、具体的に説明する。
本実施例では、石炭焚ボイラで使用し、脱硝性能が劣化した使用済脱硝触媒（ＳＵＳ３０４製のラス板を基材とし、硫酸アルミニウムを含浸した板状触媒）を用いた。この触媒のＴｉ／Ｍｏ／Ｖモル比は９０／１０／２であり、該触媒中にＳＯ3 に換算して１０重量％の硫酸分を含んでいた。
また触媒活性粉末としてはチタン、モリブデンおよびバナジウムのモル比が８９：５：６となるように調整された酸化物触媒粉末を含むスラリを用いた。
Hereinafter, the present invention will be specifically described by way of examples.
In this example, a used denitration catalyst (a plate catalyst made of a SUS304 lath plate and impregnated with aluminum sulfate) used in a coal fired boiler and having deteriorated denitration performance was used. The catalyst had a Ti / Mo / V molar ratio of 90/10/2 and contained 10% by weight of sulfuric acid in terms of SO 3 in the catalyst.
As the catalyst active powder, a slurry containing oxide catalyst powder adjusted so that the molar ratio of titanium, molybdenum and vanadium was 89: 5: 6 was used.
使用済脱硝触媒５０ｋｇを、該触媒中のＳＯ3 モル数の２倍のアンモニウムイオンを含む１Ｎアンモニア水１２５リットルに浸漬した後、液切りし、１５０℃エアで通風乾燥後、触媒粉末２０重量％、固形分濃度２０重量％のコロイダルシリカ２０重量％および水からなる触媒スラリに再び浸漬した後、液切りし、再び１５０℃エアで通風乾燥した。 After immersing 50 kg of the used denitration catalyst in 125 liters of 1N ammonia water containing ammonium ions twice the number of moles of SO 3 in the catalyst, drained, dried by ventilation with 150 ° C. air, and 20% by weight of catalyst powder. Then, after being immersed again in a catalyst slurry comprising 20% by weight of colloidal silica having a solid content concentration of 20% by weight and water, the liquid was drained and air-dried again at 150 ° C. air.
使用済脱硝触媒５０ｋｇを、該触媒中のＳＯ3 モル数の２倍のアンモニウムイオンを含む１Ｍ炭酸水素アンモニウム水１２５リットルに浸漬した後、液切りし、１５０℃エアで通風乾燥し、さらに触媒粉末２０重量％、固形分濃度２０重量％のコロイダルシリカ２０重量％および水からなる触媒スラリに再び浸漬した後、液切りし、再び１５０℃エアで通風乾燥した。 After immersing 50 kg of the used denitration catalyst in 125 liters of 1M ammonium hydrogen carbonate water containing ammonium ions twice the number of moles of SO 3 in the catalyst, the solution is drained and dried by ventilation with air at 150 ° C. After dipping again in a catalyst slurry comprising 20% by weight, 20% by weight of colloidal silica having a solid content concentration of 20% by weight and water, the liquid was drained and again dried by ventilation at 150 ° C. air.
使用済脱硝触媒５０ｋｇを、該触媒中のＳＯ3 モル数の２倍のアンモニウムイオンを含む１Ｍ炭酸水素アンモニウム水１２５リットルと、触媒粉末および固形分濃度２０重量％のコロイダルシリカ各４２ｋｇとからなる触媒スラリに浸漬した後、液切りし、１５０℃エアで通風乾燥した。 A catalyst comprising 50 kg of a used denitration catalyst, 125 liters of 1M aqueous ammonium hydrogen carbonate containing ammonium ions twice the number of moles of SO 3 in the catalyst, and 42 kg of colloidal silica having a catalyst powder and a solid concentration of 20% by weight. After being immersed in the slurry, the liquid was drained and dried by ventilation with 150 ° C. air.
実施例２において、使用済脱硝触媒を１Ｍ炭酸水素アンモニウム水１２５リットルに浸漬した際にエアレーションにより液を攪拌した以外は実施例２と同じ条件で処理した。
[比較例１]
In Example 2, the treatment was performed under the same conditions as in Example 2 except that when the used denitration catalyst was immersed in 125 liters of 1M ammonium hydrogen carbonate water, the liquid was stirred by aeration.
[Comparative Example 1]
実施例１において、アンモニア水の代わりに水に浸漬した以外は実施例１と同じ条件で処理した。
[比較例２]
In Example 1, it processed on the same conditions as Example 1 except having immersed in water instead of ammonia water.
[Comparative Example 2]
実施例１と同じ条件で使用済脱硝触媒を１Ｎアンモニア水に浸漬後、液切りし、１５０℃エアで通風乾燥した。 The used denitration catalyst was immersed in 1N ammonia water under the same conditions as in Example 1, drained, and dried by ventilation with 150 ° C. air.
[試験例]
実施例１〜４および比較例１、２で得られた再生触媒の脱硝率およびＳＯ2 酸化率を測定し、その結果を表１に示した。
なお、触媒活性の測定に使用したガス組成は、ＮＯ：２００ｐｐｍ、ＮＨ3 ：２４０ｐｐｍ、ＳＯ2 ：５００ｐｐｍ、ＳＯ3 ：５０ｐｐｍ、ＣＯ2 ：１２％、Ｈ2 Ｏ：１２％、Ｏ2 ：３％、Ｎ2 ：バランスであり、反応温度は３５０℃であった。また脱硝率およびＳＯ2 酸化率の測定結果は、無処理の使用済脱硝触媒の値を１００とした相対値で示した。
[Test example]
The denitration rate and SO 2 oxidation rate of the regenerated catalysts obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were measured, and the results are shown in Table 1.
The gas composition used for measuring the catalyst activity was NO: 200 ppm, NH 3 : 240 ppm, SO 2 : 500 ppm, SO 3 : 50 ppm, CO 2 : 12%, H 2 O: 12%, O 2 : 3%. , N 2 : Balance, reaction temperature was 350 ° C. The measurement results of the denitration rate and SO 2 oxidation rate are shown as relative values with the value of the untreated used denitration catalyst as 100.
表１から、実施例１〜４および比較例１、２で得られたいずれの再生触媒も無処理の脱硝触媒に比べて脱硝率が高くなっているが、実施例１〜４の再生触媒では、ＳＯ2 酸化率は無処理のものに比べ低下しているのに対し、比較例１の再生触媒では、水のみで洗浄しているため、ＳＯ2 酸化率が大きく増加し、また比較例２の再生触媒では、洗浄した触媒に脱硝触媒成分をコートしていないため、実施例の再生触媒に比べて脱硝率が低くなっている。
以上から、本発明の再生方法によれば、石炭焚きボイラなどから排出される排ガスの処理に使用され、脱硝率の低下した使用済脱硝触媒を、ＳＯ2 酸化率の上昇を抑制しつつ、脱硝率を回復させることができることがわかった。
From Table 1, any of the regenerated catalysts obtained in Examples 1 to 4 and Comparative Examples 1 and 2 has a higher denitration rate than the untreated denitration catalyst, but in the regenerated catalysts of Examples 1 to 4, On the other hand, the SO 2 oxidation rate is lower than that of the untreated one, whereas the regenerated catalyst of Comparative Example 1 is washed only with water, so that the SO 2 oxidation rate is greatly increased. In this regenerated catalyst, since the washed catalyst is not coated with a denitration catalyst component, the denitration rate is lower than that of the regenerated catalyst of the example.
As described above, according to the regeneration method of the present invention, the spent denitration catalyst that is used for the treatment of exhaust gas discharged from a coal-fired boiler and the like and has a reduced denitration rate can be denitrated while suppressing an increase in the SO 2 oxidation rate. It was found that the rate could be recovered.
本発明は、石炭や重油を燃料としたボイラ排ガスの脱硝に使用されて脱硝性能が低下した使用済排煙脱硝触媒をＳＯ2 の酸化率の上昇を抑えながら脱硝性能を回復させることができるため、使用済触媒体の再利用により、産業廃棄物を削減することができる。
Since the present invention can recover the NOx removal performance while suppressing the increase in SO 2 oxidation rate, the spent flue gas denitration catalyst used for the denitration of boiler exhaust gas fueled with coal or heavy oil has been reduced. Industrial waste can be reduced by reusing used catalyst bodies.
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| JP4905988B2 (en) * | 2007-12-13 | 2012-03-28 | バブコック日立株式会社 | Regeneration method of used denitration catalyst |
| JP5526369B2 (en) * | 2009-04-20 | 2014-06-18 | バブコック日立株式会社 | Denitration catalyst regeneration method |
| US8389431B2 (en) * | 2011-02-03 | 2013-03-05 | Steag Energy Services Gmbh | Method for treating SCR catalysts having accumulated iron compounds |
| JP5615228B2 (en) * | 2011-05-30 | 2014-10-29 | バブコック日立株式会社 | Regeneration method of used denitration catalyst |
| JP5701185B2 (en) * | 2011-09-09 | 2015-04-15 | 三菱重工業株式会社 | Method for reducing SO2 oxidation rate increase of denitration catalyst |
| JP2020015029A (en) * | 2018-07-27 | 2020-01-30 | 三菱日立パワーシステムズ株式会社 | Regeneration method of used denitration catalyst |
| US10814277B2 (en) * | 2018-08-22 | 2020-10-27 | Shell Oil Company | Selective catalytic reduction process and off-line regeneration of deactivated catalyst of the process |
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