CN1102431C - Process for preparing Ti-base catalyst for catalytic reduction of NOx - Google Patents
Process for preparing Ti-base catalyst for catalytic reduction of NOx Download PDFInfo
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- CN1102431C CN1102431C CN98116539A CN98116539A CN1102431C CN 1102431 C CN1102431 C CN 1102431C CN 98116539 A CN98116539 A CN 98116539A CN 98116539 A CN98116539 A CN 98116539A CN 1102431 C CN1102431 C CN 1102431C
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- preparation
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- nox
- base catalyst
- tio
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Abstract
The present invention relates to a method for preparing a Ti-base catalyst for catalytic reduction of NOx, which comprises the following steps: a certain amount of a TiCl4 solution is dissolved in a small amount of thick HNO3 (69.2%) (the mole ratio of TiCl4 to HNO3 = 1: 6); a certain amount of urea (the mole ratio of TiCl4 to urea = 0.1 to 0.2) is added in; then amine salt or nitrate of corresponding active components is added in; the mixture is stirred into paste, and calcined in a muffle furnace at 500 DEG C for 10 min, and then the required product is obtain. With the simple quick method, various components can be freely added.
Description
Affiliated field:
The invention belongs to Preparation of catalysts, specifically will urinate the combustion method and be applied in the new method that preparation removes the Ti-base catalyst of nitrogen oxide in the flue gas.
Background technology:
As everyone knows, along with the development of society, three wastes problem more and more becomes the physical and mental health that focus, particularly exhaust emission that people pay close attention to are directly endangering people, and nitrogen oxide is a main component wherein.In recent years, various countries have proposed stricter requirement in waste gas emission standard, in order to meet this requirement, the burning post processing of common employing burning control and flue gas reduces the discharging of nitrogen oxide in the combustion power generation station, wherein, in the most feasible catalytic eliminating NOx method, select the method for catalytic reduction of NOx with ammonia, be the SCR method, be widely used in power station and other industrial burning device.
1973, the Fumito Nakajima of Japan and his colleagues invented the Ti-base catalyst [Japan Patent, 1010563,1034771,1115421,1213543,141763,1159815,1215760,1159918] that is used for removing NOx.After 4 years, promptly since 1977, Japan has just formally begun the industrial applications of catalytic eliminating NOx, and the high-performance of Ti-base catalyst has played conclusive effect in course of industrialization.At NO-NH
3In the reaction, Ti-base catalyst not only has the high activity the same with other catalyst, and its most outstanding characteristics are to have good sulfur resistance, more than 200 ℃, carrier not with SO
3And SO
2Reaction, thus can be in medium-term and long-term its chemical constitution that keeps of sulfur-bearing atmosphere, and prolong service life greatly.The active constituent that is used for the Ti-base catalyst of SCR reaction has Fe
2O
3, CoO, NiO, CuO, MnO
2, V
2O
5, MoO
3, WO
3, Nb
2O
5Deng.Wherein, V
2O
5/ TiO
2Activity of such catalysts is best, but because V
2O
5When temperature is higher than more than 400 ℃, improved SO
2Conversion, therefore at V
2O
5/ TiO
2In the catalyst, add a certain amount of auxiliary agent, as WO
3, MoO
3Deng, reduce SO
2Be oxidized to SO
3Conversion ratio, widen the serviceability temperature scope of catalyst.
The straightforward procedure of preparation loaded catalyst is wet infusion process, and titanium carrier adopts TiCl
4Or Ti (SO
4)
2Hydrolysis makes, organic hydrolysis of alkoxide or other the method preparation of ultra-fine titanium carrier by titanium, and in the aqueous solution of the salt of whole catalyst by carrier being immersed in corresponding active constituent, back drying, roasting makes.As V
2O
5/ TiO
2Preparation of catalysts is immersed in NH with titanium carrier
4VO
3Oxalic acid or the aqueous solution in, or with V
2O
5Be dissolved in the aqueous solution of oxalic acid and flood titanium carrier again, also have many people to study employing VOCl
3Non-aqueous solution prepare V
2O
5/ TiO
2Catalyst, i.e. grafting.In addition, people have also studied V
2O
5-TiO
2The preparation of aerogel catalyst is for WO
3/ TiO
2, MoO
3/ TiO
2Etc. Preparation of catalysts, generally also be to adopt the aqueous solution of titanium carrier dipping ammonium paratungstate or ammonium molybdate to make.In a word, preparation method's long flow path, the formality of existing Ti-base catalyst are many, often will be through a series of steps such as the roastings of the preparation-roasting-dipping active constituent-oven dry of carrier-again, and preparation process is easy to generate pollution.
Summary of the invention:
The present invention is used for flue gas with urine combustion method to select catalytic reduction to remove the preparation of the Ti-base catalyst of NOx, and it is simple, quick to obtain a kind of preparation method, the preparation method of the Ti-base catalyst that catalytic activity is high.
Urine combustion method is (the Materials Letters that J.J.Kingsley and K.C.Partail propose the earliest, 1988,6[11-12]: 427), mainly be to be used to prepare materials such as ceramic of compact, ultra-fine laser and cathode-ray tube, so far, also seldom have into it being used for the catalysis aspect.Urine combustion method is the chemical method that comprises oxidation, reduction reaction, and principle is fairly simple, utilizes the urine heating to form earlier to contract two urine and ammonia at high temperature to generate tripolymer, TiCl
4Hydrolysis generates Ti (OH)
4, dehydration generates TiO during heating
2, in the two Hybrid Heating process, there is above-mentioned reaction simultaneously, and follows and emit light and heat and gas produces, because a large amount of gases are emitted, final products have pumiceous texture.
The preparation method of Ti-base catalyst of the present invention is as follows:
Get a certain amount of TiCl
4Solution is dissolved in a small amount of dense HNO
3(69.2%) [TiCl
4: HNO
3(mol ratio)=1: 6] in, add certain amount of urea [TiCl
4: urea (mol ratio)=0.1-0.2], add the ammonium salt or the nitrate of corresponding active constituent again, stir into pastel, the Muffle furnace roasting that places temperature to be controlled at 500 ℃ was taken out after 10 minutes, promptly got required product.
This preparation method can be used to prepare multiple material, as blocking compound SiO
2, Al
2O
3, TiO
2Deng; Binary composite oxides: V
2O
5-TiO
2, WO
3-TiO
2, MoO
3-TiO
2Deng; Ternary compound oxides: V
2O
5-WO
3-TiO
2, V
2O
5-MoO
3-TiO
2Deng; Quaternary composite oxides: V
2O
5-MoO
3-WO
3-TiO
2Or the like.
The preparation method of this Ti-base catalyst compares with the technology of preparing of existing Ti-base catalyst has following advantage:
1. the whole process of preparation step is simple, and is easy to operate quick.
2. can optionally add various components, obtain multiple composite oxides.
3. the Ti-base catalyst of urine combustion method preparation is as V
2O
5-TiO
2, V
2O
5-MoO
3-TiO
2, V
2O
5-WO
3-TiO
2, V
2O
5-WO
3-MoO
3-TiO
2Deng, in SCR, show high catalytic activity, even at no NH
3Under the condition, also can remove NOx, removal efficiency is higher than 90%, shows the characteristic of self-supporting type catalyst.
The specific embodiment:
Embodiment 1
A. claim 0.7798gNH
4VO
3Be dissolved in [NH in the saturated aqueous solution of oxalic acid
4VO
3: oxalic acid (mol ratio)=1.5-3.0];
B. get 3.3mlTiCl
4Be dissolved in the dense HNO of 4.2ml
3In, add 9 gram urea, add NH
4VO
3Oxalic acid solution, the two mixes, and puts into the Muffle furnace under 500 ℃, burns 10 minutes, takes out and promptly to get 10% (mol ratio) V
2O
5-TiO
2Catalyst, the catalyst performance test result sees Table 1.
Embodiment 2
Get 3.3mlTiCl
4Be dissolved in the dense HNO of 4.2ml
3In, add 18 gram urea, add 0.5885 gram (NH again
4)
6.Mo
7O
24.4H
2O, stir a pastel, put into the Muffle furnace under 500 ℃, burnt 10 minutes, take out and promptly to get 10%MoO
3-TiO
2Catalyst, the catalyst performance test result sees Table 1.
Embodiment 3
A. claim 0.8774gNH
4VO
3Be dissolved in [NH in the saturated aqueous solution of oxalic acid
4VO
3: oxalic acid (mol ratio)=1.5-3.0];
B. get 3.3mlTiCl
4Be dissolved in the dense HNO of 4.2ml
3In, add 18 gram urea, add NH
4VO
3Oxalic acid solution, the two mixes, add again 1.011 the gram (NH
4)
6.W
7O
24.6H
2O, stir a pastel, put into the Muffle furnace under 500 ℃, burnt 10 minutes, take out and promptly to get 10% (mol ratio) V
2O
5-10%WO
3-TiO
2Catalyst, the catalyst performance test result sees Table 1.
Embodiment 4
A. claim 1.4038gNH
4VO
3Be dissolved in [NH in the saturated aqueous solution of oxalic acid
4VO
3: oxalic acid (mol ratio)=1.5-3.0];
B. get 3.3mlTiCl
4Be dissolved in the dense HNO of 4.2ml
3In, add 18 gram urea, add NH
4VO
3Oxalic acid solution, the two mixes, add again 0.7062 the gram (NH
4)
6.Mo
7O
24.4H
2O, stir a settled solution, put into the Muffle furnace under 500 ℃, burnt 10 minutes, take out and promptly to get 15% (mol ratio) V
2O
5-10%MoO
3-TiO
2Catalyst, the catalyst performance test result sees Table 1.
Embodiment 5
A. claim 1.0037gNH
4VO
3Be dissolved in [NH in the saturated aqueous solution of oxalic acid
4VO
3: oxalic acid (mol ratio)=1.5-3.0];
B. get 3.3mlTiCl
4Be dissolved in the dense HNO of 4.2ml
3In, add 18 gram urea, add NH
4VO
3Oxalic acid solution, the two mixes, add again 1.1566 the gram (NH
4)
6.W
7O
24.6H
2O, 0.7574 gram (NH
4)
6.Mo
7O
24.4H
2O, stir a pastel, put into the Muffle furnace under 500 ℃, burnt 10 minutes, take out and promptly to get 10% (mol ratio) V
2O
5-10%MoO
3-10%WO
3-10%WO
3-TiO
2Catalyst, the catalyst performance test result sees Table 1.
Embodiment 6
Adopt the temperature programming reaction to remove the activity rating of NOx the Ti-base catalyst of above-mentioned preparation, the catalyst performance test is carried out on the continuous-flow micro-reaction device.The quartz tube reactor of internal diameter 8mm, catalyst dress 0.1-0.3g, unstripped gas is formed: NH
3: 600ppm, NO:520ppm, O
2: 3-5%, Ar gas are diluent gas.5 ℃/min of temperature programming speed, gas space velocity 2-4 * 10
4h
-1, unstripped gas and product are formed with the detection of Britain KM9006 type gas alloying apparatus.Evaluation result sees Table 1.The DeNOx activity rating result of the different Ti-base catalysts of table 1
Embodiment deNOx activity
The NO conversion ratio be 100% temperature range (℃) embodiment 1 (no NH
3Under the situation) 270-420 embodiment 1 (has NH
3Under the situation) 220-400 embodiment 2 280-380 embodiment 3 210-430 embodiment 4 200-390 embodiment 5 240-420
Claims (2)
1. the preparation method of the Ti-base catalyst of a catalytic reduction of NOx is characterized in that getting a certain amount of TiCl
4Solution is dissolved in a small amount of dense HNO
3(69.2%) [TiCl
4: HNO
3(mol ratio)=1: 6] in, add certain amount of urea [TiCl
4: urea (mol ratio)=0.1-0.2], add the ammonium salt or the nitrate of corresponding active constituent again, stir into pastel, the Muffle furnace roasting that places temperature to be controlled at 500 ℃ was taken out after 10 minutes.
2. preparation method as claimed in claim 1 is characterized in that can be used for the preparation of blocking compound, binary composite oxides or ternary compound oxides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98116539A CN1102431C (en) | 1998-08-03 | 1998-08-03 | Process for preparing Ti-base catalyst for catalytic reduction of NOx |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98116539A CN1102431C (en) | 1998-08-03 | 1998-08-03 | Process for preparing Ti-base catalyst for catalytic reduction of NOx |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1243767A CN1243767A (en) | 2000-02-09 |
| CN1102431C true CN1102431C (en) | 2003-03-05 |
Family
ID=5225129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98116539A Expired - Fee Related CN1102431C (en) | 1998-08-03 | 1998-08-03 | Process for preparing Ti-base catalyst for catalytic reduction of NOx |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1102431C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5192792A (en) * | 1975-02-12 | 1976-08-14 | ||
| JPS62149339A (en) * | 1985-12-24 | 1987-07-03 | Matsushita Electric Ind Co Ltd | Production of catalyst for purifying exhaust gas |
| JPH08333117A (en) * | 1995-06-06 | 1996-12-17 | Mitsubishi Materials Corp | Production of porous globular titanium oxide particle |
-
1998
- 1998-08-03 CN CN98116539A patent/CN1102431C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5192792A (en) * | 1975-02-12 | 1976-08-14 | ||
| JPS62149339A (en) * | 1985-12-24 | 1987-07-03 | Matsushita Electric Ind Co Ltd | Production of catalyst for purifying exhaust gas |
| JPH08333117A (en) * | 1995-06-06 | 1996-12-17 | Mitsubishi Materials Corp | Production of porous globular titanium oxide particle |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1243767A (en) | 2000-02-09 |
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