JPH026819A - Pretreatment of denitrification catalyst - Google Patents
Pretreatment of denitrification catalystInfo
- Publication number
- JPH026819A JPH026819A JP63156060A JP15606088A JPH026819A JP H026819 A JPH026819 A JP H026819A JP 63156060 A JP63156060 A JP 63156060A JP 15606088 A JP15606088 A JP 15606088A JP H026819 A JPH026819 A JP H026819A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- denitrification
- pretreatment
- contg
- contact
- 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 41
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000006866 deterioration Effects 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000003245 coal Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- -1 chlorine (C1) Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は脱硝触媒の前処理方法に係り、特に排ガス中の
窒素酸化物をアンモニア接触還元により低減するのに好
適な脱硝触媒の前処理方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for pretreatment of a denitrification catalyst, and in particular, a pretreatment method for a denitration catalyst suitable for reducing nitrogen oxides in exhaust gas by catalytic reduction with ammonia. Regarding.
一般に触媒毒成分としては塩素（Ｃ１）などのハロゲン
やカリウム（Ｋ）、ナトリウム（Ｎａ）などのアルカリ
金属、イオウ（Ｓ） 、水８！ （Ｈｇ）などがよく知
られており、脱硝触媒においてもに、Ｎａなどのアルカ
リ金属やｓｏ２ 、ＳＯ３などのイオウ酸化物により脱
硝性能が低下する。このため触媒の改良が行なわれ、現
在のチタン系酸化物（Ｔｉ０２−Ｖ２０ｇ −Ｍｏ０３
、Ｔｉ０２−Ｖ２０！１−ＷＯ３）触媒が開発された
。ところが近年、石炭焚きボイラに使用されている燃料
中に、ヒ素（Ａｓ）、セレン（Ｓｅ）、テルル（Ｔｅ）
等の揮発性金属が微量に含まれており、これが触媒の脱
硝性能を低下させることが判明し、問題となってきてい
る。この揮発性触媒による劣化を低減する方法として種
々の方法、例えばアルカリや酸による洗浄により触媒毒
をとり除く方法等が開発されたが、排液処理などの点で
２次公害をひきおこすことが多（問題があった。In general, catalyst poison components include halogens such as chlorine (C1), alkali metals such as potassium (K) and sodium (Na), sulfur (S), and water8! (Hg) is well known, and the denitrification performance of denitrification catalysts is also reduced by alkali metals such as Na and sulfur oxides such as SO2 and SO3. For this reason, improvements were made to the catalyst, and the current titanium-based oxide (Ti02-V20g -Mo03
, Ti02-V20!1-WO3) catalyst was developed. However, in recent years, arsenic (As), selenium (Se), and tellurium (Te) have been added to the fuel used in coal-fired boilers.
It has been found that these volatile metals, such as these, reduce the denitrification performance of the catalyst, which has become a problem. Various methods have been developed to reduce the deterioration caused by volatile catalysts, such as cleaning with alkali or acid to remove catalyst poisons, but these often cause secondary pollution due to wastewater treatment, etc. There was a problem.
以上に示したように、上記従来技術は、揮発性触媒によ
って劣化した触媒を再生する技術であり、再生する上で
酸やアルカリ溶液を必要とし、２次公害をひきおこすと
いう問題があった。本発明の目的は、これら再生を行な
うことなく、触媒の前処理によって劣化を防止すること
にある。As described above, the above-mentioned conventional technology is a technology for regenerating a deteriorated catalyst using a volatile catalyst, and requires an acid or alkaline solution for regeneration, which has the problem of causing secondary pollution. An object of the present invention is to prevent deterioration by pre-treating the catalyst without performing these regenerations.
上記目的は、アンモニア接触還元脱硝反応に使用するチ
タン、モリブデンまたは、およびバナジウムの酸化物を
含む触媒を、予め３００〜４００℃の温度で二酸化イオ
ウまたは、および三酸化イオウと接触させて前処理する
ことにより達成される。The above purpose is to pretreat a catalyst containing an oxide of titanium, molybdenum, or vanadium used in the ammonia catalytic reduction denitrification reaction by contacting it with sulfur dioxide or sulfur trioxide at a temperature of 300 to 400°C. This is achieved by
ボイラ燃料中の微量の揮発性金属蒸気は、脱硝触媒に吸
着し、脱硝触媒の活性点を覆うことにより触媒を劣化さ
せる。一方、ＳＯ２、ＳＯ３も同様に触媒に吸着し劣化
させるが、劣化度合が揮発性金属よりも低い。このため
、予じめＳｏ２、Ｓ０３を先に触媒に吸着させることに
より、Ａｓなどの揮発性金属蒸気の吸着点を減少させる
ことができ、従って触媒の寿命が大幅にのびることにな
る。A trace amount of volatile metal vapor in the boiler fuel is adsorbed on the denitration catalyst and covers the active sites of the denitration catalyst, thereby degrading the catalyst. On the other hand, SO2 and SO3 are similarly adsorbed onto the catalyst and deteriorated, but the degree of deterioration is lower than that of volatile metals. Therefore, by adsorbing So2 and S03 on the catalyst in advance, the adsorption points of volatile metal vapors such as As can be reduced, and the life of the catalyst can therefore be significantly extended.
本発明による揮発性触媒毒を有する脱硝触媒の前処理と
しては、３００〜４００℃の温度で８０２またはくおよ
び）Ｓ０３ガスを数時間、触媒に吸着させることにより
行なわれる。この触媒の組成は、チタン、モリブデン、
バナジウム酸化物であれば効果があるが、その割合はＴ
ｉ：Ｍｏ：Ｖ＝ ８０．０〜９６．５＝３〜１５：０．
５〜５．０で、かつ５ｏ−ｆ’が１０％以下の触媒であ
ることが望ましい。前処理温度は、脱硝反応温度（３０
０〜４００℃）が運転上好ましい。イオウ酸化物の吸着
時間は数時間ないし数十時間が適当であり、吸着温度に
より決定される。このようにして前処理された脱硝触媒
を揮発性金属化合物を含む石炭焚きボイラの脱硝反応に
使用すると、予じめ触媒の活性点がＳｏ２、Ｓｏ３によ
り覆れているので、Ａｓなどの金属酸化物の吸着点が少
なくなり、従って揮発性金属による劣化の少ない触媒の
通用が可能となる。以下実施例によりさらに詳細に説明
する。The pretreatment of the denitrification catalyst having volatile catalyst poison according to the present invention is carried out by adsorbing 802 or 802 or ) S03 gas onto the catalyst for several hours at a temperature of 300 to 400°C. The composition of this catalyst is titanium, molybdenum,
Vanadium oxide is effective, but its proportion is T
i:Mo:V=80.0~96.5=3~15:0.
5 to 5.0 and a catalyst with 5o-f' of 10% or less. The pretreatment temperature is the denitrification reaction temperature (30
0 to 400°C) is preferable for operation. The adsorption time of sulfur oxide is suitably several hours to several tens of hours, and is determined by the adsorption temperature. When the denitrification catalyst pretreated in this way is used in the denitrification reaction of a coal-fired boiler containing volatile metal compounds, the active sites of the catalyst are covered in advance with So2 and So3, so metals such as As can be oxidized. There are fewer adsorption points for substances, and therefore a catalyst that is less susceptible to deterioration due to volatile metals can be used. The present invention will be explained in more detail with reference to Examples below.
実施例１
チタン、モリブデン、バナジウム酸化物の組成比がＴｉ
／Ｍｏ／Ｖ＝８６／１０／４ （原子比）であり、かつ
硫酸根（Ｓｏ−２）が８％（重量比）となるように混線
法で調製した２０ｍｍＸ１００ｍ■の板状触媒に石炭焚
きボイラ排ガス成分（ガス組成１）を３５０℃で２０時
間処理した。その後、ヒ素を含むガス（ガス組成２）に
同温度で２０時間さらした。Example 1 The composition ratio of titanium, molybdenum, and vanadium oxide is Ti
/Mo/V = 86/10/4 (atomic ratio) and sulfuric acid radical (So-2) was 8% (weight ratio) using a 20 mm x 100 m plate-shaped catalyst prepared by the cross-wire method. Boiler exhaust gas components (gas composition 1) were treated at 350°C for 20 hours. Thereafter, it was exposed to a gas containing arsenic (gas composition 2) at the same temperature for 20 hours.
比較例１
実施例１の前処理工程を省略し、ガス組成２で２０時間
後の脱硝率を調べた。実施例、比較例のガス組成条件、
および２０時間後の脱硝率を表１、表２に示した。これ
によりＳｏ２ 、Ｓｏ３により劣化が防止されることが
わかる。Comparative Example 1 The pretreatment step of Example 1 was omitted, and the denitrification rate after 20 hours was investigated using gas composition 2. Gas composition conditions of Examples and Comparative Examples,
Tables 1 and 2 show the denitrification rates after 20 hours. This shows that deterioration is prevented by So2 and So3.
以下余白
第 １ 表
比較例２
実施例１の板状触媒に５％の希硫酸溶液を含浸し、１８
０℃で２時間乾燥させた。この触媒をガス組成２で２０
時間、３５０℃で反応させた後、脱硝率を比較した。結
果を第２表にあわせて示した。The following is a margin: Table 1 Comparative Example 2 The plate-shaped catalyst of Example 1 was impregnated with a 5% dilute sulfuric acid solution.
It was dried at 0°C for 2 hours. This catalyst has a gas composition of 20
After reacting at 350°C for an hour, the denitrification rates were compared. The results are also shown in Table 2.
第
表
比較例２により、ｓｏ２ 、ＳＯ３はガス状であること
が必要であり、含浸による触媒はあまり効果がないこと
がわかる。Comparative Example 2 in Table 1 shows that so2 and SO3 need to be in gaseous form, and catalysts by impregnation are not very effective.
本結果かられかるように、本発明の前処理方法は、簡単
な操作で行なうことができ、また装置の運転条件もその
まま使用することができるので、経済的であり、有効な
方法である。As can be seen from the present results, the pretreatment method of the present invention is an economical and effective method because it can be performed with simple operations and the operating conditions of the device can be used as they are.
本発明によれば、触媒の耐久性を増加させることができ
る。また比較的簡単な前処理方法なので経済的メリット
も大きい。According to the present invention, the durability of the catalyst can be increased. Furthermore, since it is a relatively simple pretreatment method, it has great economic benefits.
代理人 弁理士 川 北 武 長Agent: Patent Attorney Kawakita Takecho
Claims (1)
モリブデンまたは、およびバナジウムの酸化物を含む触
媒を、予め３００〜４００℃の温度で二酸化イオウまた
は、および三酸化イオウと接触させて前処理することを
特徴とする脱硝触媒の前処理方法。(1) Titanium used in ammonia catalytic reduction denitrification reaction,
A method for pretreating a denitrification catalyst, comprising pretreating a catalyst containing an oxide of molybdenum or vanadium by bringing it into contact with sulfur dioxide or sulfur trioxide at a temperature of 300 to 400°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63156060A JPH026819A (en) | 1988-06-24 | 1988-06-24 | Pretreatment of denitrification catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63156060A JPH026819A (en) | 1988-06-24 | 1988-06-24 | Pretreatment of denitrification catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH026819A true JPH026819A (en) | 1990-01-11 |
Family
ID=15619431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63156060A Pending JPH026819A (en) | 1988-06-24 | 1988-06-24 | Pretreatment of denitrification catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH026819A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011140005A (en) * | 2010-01-08 | 2011-07-21 | Hitachi Zosen Corp | Method for preparing denitration catalyst, and catalyst prepared by the same method |
-
1988
- 1988-06-24 JP JP63156060A patent/JPH026819A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011140005A (en) * | 2010-01-08 | 2011-07-21 | Hitachi Zosen Corp | Method for preparing denitration catalyst, and catalyst prepared by the same method |
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