JPS58119347A - Slurry for preparing catalyst - Google Patents
Slurry for preparing catalystInfo
- Publication number
- JPS58119347A JPS58119347A JP57001945A JP194582A JPS58119347A JP S58119347 A JPS58119347 A JP S58119347A JP 57001945 A JP57001945 A JP 57001945A JP 194582 A JP194582 A JP 194582A JP S58119347 A JPS58119347 A JP S58119347A
- Authority
- JP
- Japan
- Prior art keywords
- slurry
- weight
- parts
- viscosity
- catalyst
- 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
- 239000002002 slurry Substances 0.000 title claims description 18
- 239000003054 catalyst Substances 0.000 title claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008119 colloidal silica Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009972 noncorrosive effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 241001233037 catfish Species 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
この発明は、排煙中の窒素酸化物（以下ＮＯｘと記す）
をＮＨａによって選択的に還元する反応に供される脱硝
触媒に関し、特に同触媒を調製するためのスラリーに関
する。[Detailed Description of the Invention] This invention deals with nitrogen oxides (hereinafter referred to as NOx) in flue gas.
The present invention relates to a denitrification catalyst that is subjected to a reaction of selectively reducing NHa with NHa, and particularly to a slurry for preparing the catalyst.
発電所、焼結炉、各種化学工場や自動車などから排出さ
れるＮＯｘは光化学スモッグの原因物質であるため、そ
の効果的な処理手段が望まれる０従来から多く匈提案さ
れているＮＯｘの処理方法のうち、ＮＨ３を還元剤とす
るＮ Ｏｘの接触還元法は、排煙中に酸素が１容量チ以
上含まれていてもＮＨ３はＮ Ｏｘと選択的に反応する
ので、還元剤が少なくてすむという点で有利な方法とさ
れている。NOx emitted from power plants, sintering furnaces, various chemical factories, automobiles, etc. is a substance that causes photochemical smog, so an effective treatment method is desired.Many NOx treatment methods have been proposed in the past. Among them, the catalytic reduction method of NOx using NH3 as a reducing agent requires less reducing agent because NH3 selectively reacts with NOx even if the flue gas contains more than 1 volume of oxygen. This is considered an advantageous method.
君
ところでＮＯｘ処理を必要とする排゛鯰には、避ける工
夫が必要である。この工夫の１つとしで、種々の形状の
金網、たとえば平らな金網を波形、ジグザグ形、ひだ形
などに湾曲ないし屈曲させたもの、さらにはこれらの湾
曲ないし屈曲金網と平らな金網を組合せて単結構造に形
成したもの１こ、触媒物質を含むスラリーを塗布してこ
れを固化し、触媒物質を金網に保持させたものが提案さ
れている（特開昭５５−８８７４号公報参照、）。そし
てここに使用される代表的な触媒物質は、硫黄酸化物を
含む排ガス中でも高い活性を示すＶ２Ｏ５−Ｔｉ０ｚの
系である。By the way, you need to find ways to avoid NOx removal from catfish, which requires NOx treatment. One of the ways to do this is to create wire meshes of various shapes, such as flat wire meshes curved or bent into corrugated, zigzag, or pleated shapes, and even combinations of these curved or bent wire meshes and flat wire meshes. One method has been proposed in which a slurry containing a catalyst substance is applied and solidified, and the catalyst substance is held in a wire mesh (see Japanese Patent Laid-Open No. 8874/1987). . A typical catalyst material used here is a V2O5-Ti0z system that exhibits high activity even in exhaust gas containing sulfur oxides.
この触媒物質を金網に塗布して保持させるためのスラリ
ーとしては、塗膜の補強の点からコロイダルシリカより
なるものが好ましい。またＶ２Ｏ５をＴｉＯ２の多孔質
粉末に効果的に担持させるζこは、可溶性のバナジウム
塩、とりわけ水溶性でかつ腐食性のないＮＨ、ｓ ＶＯ
３が好ましく用いられる（ Ｎ ａ Ｖ Ｏ３やＫＶＯ
ａなどは水溶性ではあるが、アルカリ金属が触媒毒とし
て作用するので、好ましくなす、このような理由で、ス
ラリーの好適成分はＴｉＯ２粉末とＮＨ４ＶＯ３とコロ
イダルシリカである。しかのため塗布作業の点では満足
すべきものではない。そこでこのような粘度の経時変化
をきたさないように、スラリー粘度の安定化を図る必要
がある。一般にスラリーの粘度変化はｐＨ値と関係する
。上記スラリーの粘度変化もつきのように考えられる。The slurry for applying and retaining the catalyst substance on the wire mesh is preferably made of colloidal silica from the viewpoint of reinforcing the coating film. In addition, to effectively support V2O5 in the porous TiO2 powder, soluble vanadium salts, especially water-soluble and non-corrosive NH, sVO
3 is preferably used (N a V O3 or KVO
Although a and the like are water-soluble, they are preferred because alkali metals act as catalyst poisons.For this reason, preferred components of the slurry are TiO2 powder, NH4VO3, and colloidal silica. However, it is not satisfactory in terms of coating work. Therefore, it is necessary to stabilize the viscosity of the slurry to prevent such changes in viscosity over time. Generally, the change in viscosity of a slurry is related to the pH value. The change in viscosity of the slurry is also considered to be a factor.
すなわちＶＯ３−かＴｉＱ２表面に吸着するために、
ＮＨ４ＶＯ３＋Ｈ２０−＋ ＮＨ４０Ｈ−１−ＨＶＯ
３＠＠１１ （１１で示されるＮＨ４ＶＯ３の加水分解
が生じ、その結果ｐＨ値がアルカリ側に変化し、これが
原因となって粘度の経時変化が生じるものと考えを酸で
中和することによってスラリーの粘度変化を抑制するこ
とが考えられる。そして酸としては、腐食性かなくかつ
ＮＨ４ＶＯ３を不溶化させないもので、しかも加熱によ
って容易に分解するものか要望せられる。In other words, in order to adsorb VO3- to the TiQ2 surface, NH4VO3+H20-+ NH40H-1-HVO
3 @ @ 11 (Hydrolysis of NH4VO3 as shown in 11 occurs, resulting in a change in pH value to the alkaline side, which is thought to be the cause of changes in viscosity over time.) By neutralizing with acid, slurry It is considered that the acid should be non-corrosive, do not insolubilize NH4VO3, and be easily decomposed by heating.
この発明は、上記のような実情からなされたもので、上
記要望にかなう酸を含むスラリーを提供することを目的
とする。This invention was made in view of the above-mentioned circumstances, and an object thereof is to provide an acid-containing slurry that meets the above-mentioned needs.
この発明によるスラリーは、ＴｉＯ２粉末とＮＨ４ＶＯ
３とコロイダルシリカとしゆう酸とからなる触媒調製用
スラリーである。The slurry according to this invention consists of TiO2 powder and NH4VO
This is a slurry for catalyst preparation consisting of No. 3, colloidal silica, and sulfuric acid.
しゆう酸の含有量は
２ＮＨ４ＶＯ３＋ ７Ｈ２Ｃ２０４
→２ＶＯＣ２０４＋（ＮＨ４） ２Ｃ２０４＋８ＣＯ２
＋４Ｈ２０＠＠１１ （２１で示される反応に必要な量
で十分であるが、実際には前記（１）式で生成するＮＩ
（４０Ｈを中和するに要する量であればよい。ＮＨ４Ｏ
Ｈの生成量は、ＴｉＯ２粉末のＶＯ３−吸着能に依るの
で、しゆう酸の必要量もＴｉＯ２粉末のＶＯａ−吸着能
に依存する。ＴｉＯ２の多孔質粉末の比表面積が１００
ｍ／７程度である場合、しゅう酸の含有量はＮＨ４Ｖ
Ｏ３１００重量部に対して約４０重量部以上である。最
適含有量は５０重量部程度である。The content of oxalic acid is 2NH4VO3+ 7H2C204 →2VOC204+(NH4) 2C204+8CO2
+4H20@@11 (The amount necessary for the reaction shown in 21 is sufficient, but in reality, the NI produced by the above formula (1)
(The amount required to neutralize 40H is sufficient. NH4O
Since the amount of H produced depends on the VO3-adsorption capacity of the TiO2 powder, the required amount of oxalic acid also depends on the VOa-adsorption capacity of the TiO2 powder. The specific surface area of porous TiO2 powder is 100
m/7, the content of oxalic acid is NH4V
The amount is about 40 parts by weight or more based on 100 parts by weight of O3. The optimum content is about 50 parts by weight.
この発明による触媒調製用スラリは、以上のとおりしゆ
う酸を含むので、粘度の経時変化を効果的に抑制するこ
とができる。Since the slurry for catalyst preparation according to the present invention contains oxalic acid as described above, it is possible to effectively suppress changes in viscosity over time.
実施例１
１００メツシユの篩を通過したＴｉＯ２粉末（比表面積
： ｌ ２０ｒｒｖＦ） Ｉ ＯＯ取計部と、市販のコ
ロイダルシリカ（Ｓｉ０２として２０重量中
チ）１００重量部との混合物にし振う酸１０重量部を加
え、混合物をよく撹拌した後、さらにＮＨ４ＶＯ３１Ｑ
重量部を加えてスラリーを形 ４成した。そして撹拌下
に適時スラリーの粘度を測定した。粘度の測定は単一円
筒回転式粘度計（ＣＯＮ Ｔ ＲＡ Ｖ Ｅ Ｓ ＠Ａ
Ｇ ＠ Ｚ Ｕ ＲＩ ＣＨ−ＲＭ・１５Ｄ）を用い
て行なった。Example 1 TiO2 powder (specific surface area: l20rrvF) passed through a 100-mesh sieve. 10 weight of acid is shaken over a mixture of IOO and 100 parts by weight of commercially available colloidal silica (20 parts by weight as Si02). of NH4VO31Q and stirred the mixture well.
4 parts by weight were added to form a slurry. Then, the viscosity of the slurry was measured at appropriate times while stirring. Viscosity is measured using a single cylinder rotational viscometer (CONTRAVES@A
G@ZURICH-RM・15D).
実施例２．３
しゆう酸の添加量を６重量部および４重量部として、そ
れぞれ実施例１の操作を繰返した。Example 2.3 The operation of Example 1 was repeated using 6 parts by weight and 4 parts by weight of oxalic acid, respectively.
比較例１〜３
しゆう酸の添加量を３重量部、２重量部および０重量部
として、それぞれ実施例Ｊの操作を繰返した。Comparative Examples 1 to 3 The operation of Example J was repeated by changing the amount of oxalic acid added to 3 parts by weight, 2 parts by weight, and 0 parts by weight, respectively.
実施例１〜３および比較例１〜３で測定した粘度を図面
に示す。図かられかるように、各実施例で得られたスラ
リーは粘度の経時変化をほとんど示さない。The viscosity measured in Examples 1 to 3 and Comparative Examples 1 to 3 is shown in the drawing. As can be seen from the figure, the slurries obtained in each example show almost no change in viscosity over time.
図面は粘度の経時変化を示すグラフである。 以 上 特許出願人 日立造船株式会社 The drawing is a graph showing changes in viscosity over time. that's all Patent applicant: Hitachi Zosen Corporation
Claims (1)
としゆう酸とからなる触媒調製用スラリー。 （２） しゆう酸の含有割合がＮＨ４ＶＯ３１００重量
部に対して４０重量部以上である特許請求の範囲第１項
記載のスラリー。[Claims] A slurry for catalyst preparation comprising 111Ti02 powder, NH4VO3, colloidal silica, and citric acid. (2) The slurry according to claim 1, wherein the content of oxalic acid is 40 parts by weight or more based on 100 parts by weight of NH4VO3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57001945A JPS58119347A (en) | 1982-01-08 | 1982-01-08 | Slurry for preparing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57001945A JPS58119347A (en) | 1982-01-08 | 1982-01-08 | Slurry for preparing catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58119347A true JPS58119347A (en) | 1983-07-15 |
Family
ID=11515746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57001945A Pending JPS58119347A (en) | 1982-01-08 | 1982-01-08 | Slurry for preparing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58119347A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008296100A (en) * | 2007-05-30 | 2008-12-11 | Hitachi Zosen Corp | Slurry for producing denitration catalyst, method for producing denitration catalyst using the slurry, and denitration catalyst produced by the method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5266892A (en) * | 1975-12-01 | 1977-06-02 | Mitsubishi Heavy Ind Ltd | Method of producing denitration catalyst |
| JPS558874A (en) * | 1978-07-06 | 1980-01-22 | Hitachi Zosen Corp | Plate denitrification catalyst |
-
1982
- 1982-01-08 JP JP57001945A patent/JPS58119347A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5266892A (en) * | 1975-12-01 | 1977-06-02 | Mitsubishi Heavy Ind Ltd | Method of producing denitration catalyst |
| JPS558874A (en) * | 1978-07-06 | 1980-01-22 | Hitachi Zosen Corp | Plate denitrification catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008296100A (en) * | 2007-05-30 | 2008-12-11 | Hitachi Zosen Corp | Slurry for producing denitration catalyst, method for producing denitration catalyst using the slurry, and denitration catalyst produced by the method |
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