CN101757938A - Method for preparing low-temperature vanadium catalyst in for sulphuric acid production - Google Patents
Method for preparing low-temperature vanadium catalyst in for sulphuric acid production Download PDFInfo
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- CN101757938A CN101757938A CN200810234489A CN200810234489A CN101757938A CN 101757938 A CN101757938 A CN 101757938A CN 200810234489 A CN200810234489 A CN 200810234489A CN 200810234489 A CN200810234489 A CN 200810234489A CN 101757938 A CN101757938 A CN 101757938A
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Abstract
The invention belongs to the technical field of catalysis, which particularly relates to a low-temperature vanadium catalyst in for sulphuric acid production. By adding a low-temperature activating agent, the low-temperature activity of the vanadium catalyst is enhanced, and the ignition temperature is decreased. The catalyst is prepared from the following raw materials in percentage by weight: 5.0-8.5% of V2O5, 2.5-4.5% of K2O/V2O5, 1.0-15.0% of Na2O, 2.0-20.0% of Cs2O, 1.0-5.0% of P2O5, and the balance of diatomite. The invention has adopts the adding method that the catalyst is added in mixing or is added to vanadium water. The vanadium catalyst is suitable for the upper part of the first section and the two-conversion part of a converter of a sulphuric acid production device in the double-conversion double-absorption process. Compared with the traditional low-temperature vanadium catalyst, the low-temperature activity of the invention is obviously higher, and can satisfy high requirement of total SO2 transfer rate.
Description
Technical field: the invention belongs to catalysis technical field, be specifically related to a kind of preparation method who is used for the low-temperature type vanadium catalyst of gas washing in SA production.
Technical background: in the gas washing in SA production with SO
2Oxidation conversion is SO
3Usually all use vanadium catalyst.General traditional vanadium catalyst is vanadium-potassium (sodium)-silicon system, two kinds of middle warm type and low forms are arranged, and middle temperature type vanadium catalyst generally is used for, two, three section of converter, and general requirement of operating temperature is higher than 420 ℃, be no more than 600 ℃, it is active to have middle preferably temperature; Low-temperature type vanadium catalyst generally is used for one section top of converter and four sections, five sections, and general requirement of operating temperature is higher than 410 ℃, has better low temperature activity, helps improving SO in the sulfuric acid conversion device
2Be converted into SO
3Total conversion.In the sulfuric acid production plant of double-absorption flow process combination loading traditional in, low-temperature type vanadium catalyst, can make SO
2Final conversion ratio reaches 99.5%.
The manufacture method of present vanadium catalyst: be generally vanadium-potassium-silicon system, low-temperature type vanadium catalyst is vanadium-potassium-sodium-silicon system.Manufacture method be with raw material diatomite through the making beating, acid treatment, overanxious washing and drying make terra silicea purificata; KOH is dissolved with steam, and and V
2O
5Under boiling condition, heat makes satisfactory KVO
3With KOH mixed solution (being called for short vanadium water), then vanadium water is made V with the sulfuric acid neutralization
2O
5And K
2SO
4The colloidal precipitation thing will mix in the adding rollers such as colloidal precipitation thing and auxiliary agent, terra silicea purificata to scale, rolls closely, becomes the plasticity material, again through extrusion, drying, roasting, sieve and operation such as packing is made vanadium catalyst.Vanadium catalyst with the method preparation can satisfy the needs of gas washing in SA production substantially, but uses traditional low-temperature type vanadium catalyst will satisfy SO
2It is difficult that total conversion reaches more than 99.8%.
Summary of the invention: the objective of the invention is to propose a kind of preparation method of the low-temperature type vanadium catalyst that is used for gas washing in SA production newly, this catalyst has higher low temperature active and heat endurance than traditional low-temperature type vanadium catalyst, can satisfy higher SO
2Total conversion needs.
The present invention is achieved like this, and by adding the low-temperature activation agent, improves the low temperature active of vanadium catalyst, reduces initiation temperature.Its key component comprises: the low-temperature activation agent is soluble metal cesium salt, sodium salt, phosphorus-containing compound, soluble metal can reduce the melt temperature of active phase in catalyst, improve the cryogenic property of vanadium catalyst, reduce initiation temperature, the catalyst formulation percentage by weight is V
2O
55.0～8.5% K
2O/V
2O
52.5～4.5 Na
2O 1.0～15.0% Cs
2O 2.0～20.0% P
2O
51.0～5.0% all the other be diatomite.Addition manner directly adds the low-temperature activation agent for adding or it being joined in the vanadium water in vanadium water when mixed grind, can improve the uniformity that active material distributes on diatomite support.
It can be wherein a kind of of cesium sulfate, cesium carbonate, cesium nitrate that the inventive method prepares the used soluble metal cesium salt of catalyst, also can be two or three mixture wherein; Sodium salt is a sodium sulphate; Phosphorus-containing compound can be a kind of in phosphoric acid, ammonium phosphate, the sodium acid phosphate salt; Diatomite can be a kind of in Linqu, Shandong diatomite, northeast long white diatomite, Shengxian County, Zhejiang diatomite and the Yunnan Xun Dian diatomite.
The low-temperature type vanadium catalyst of the inventive method preparation has better low-temperature catalyzed performance than traditional low-temperature type vanadium catalyst, low 20～40 ℃ of the more traditional vanadium catalyst of initiation temperature, operating temperature can be reduced to 380～390 ℃ from 410～420 ℃, this catalyst is substituted low-temperature type vanadium catalyst be used for gas washing in SA production, can make the SO of the sulfuric acid apparatus of double-absorption flow process
2Final conversion ratio reaches 99.8%, and reduced the operating temperature of one section of converter, helps high concentration SO
2Conversion, adapted to that sulfuric acid apparatus maximizes and the development of acid production with sulphur, use this catalyst at the converter latter end, improved the total conversion in the converter, reduced SO in the tail gas
2Concentration, satisfied the environmental requirement of increasingly stringent.
The vanadium catalyst of the inventive method preparation is applicable to the one section top and the two transfer part branches of converter of the sulfuric acid production plant of double-absorption flow process.
The specific embodiment: further specify content of the present invention below in conjunction with embodiment:
Embodiment 1
Sample prescription V
2O
56.5% K
2O/V
2O
52.7 Na
2SO
413.7% P
2O
51.0% all the other be diatomite; The employing traditional processing technology is made, and Linqu, Shandong diatomite through wet concentration, acid treatment, overanxious washing and drying, is made the Shandong terra silicea purificata; KOH is dissolved with steam, and and V
2O
5Under boiling condition, heat makes K
2O/V
2O
5Be 2.7 KVO
3With KOH mixed solution (being called for short vanadium water), then a certain amount of vanadium water is made V with the sulfuric acid neutralization
2O
5And K
2SO
4The colloidal precipitation thing is to scale with colloidal precipitation thing and Na
2SO
4, H
3PO
4, mix in the adding roller such as Shandong terra silicea purificata, add water-powered roller and compress closely, become the plasticity material, again through extrusion, drying, roasting, sieve and operation such as packing is made vanadium catalyst.
Embodiment 2
Sample prescription V
2O
56.5% K
2O/V
2O
52.7 Na
2SO
48.0% Cs
2SO
42.0% P
2O
51.0% all the other be diatomite; The employing traditional processing technology is made, and Linqu, Shandong diatomite through wet concentration, acid treatment, overanxious washing and drying, is made the Shandong terra silicea purificata; KOH is dissolved with steam, and and V
2O
5Under boiling condition, heat makes K
2O/V
2O
5Be 2.7 KVO
3With KOH mixed solution (being called for short vanadium water), then a certain amount of vanadium water is made V with the sulfuric acid neutralization
2O
5And K
2SO
4The colloidal precipitation thing is to scale with colloidal precipitation thing and Cs
2SO
4, Na
2SO
4, H
3PO
4, mix in the adding roller such as Shandong terra silicea purificata, add water-powered roller and compress closely, become the plasticity material, again through extrusion, drying, roasting, sieve and operation such as packing is made vanadium catalyst.
Embodiment 3
Sample prescription V
2O
56.5% K
2O/V
2O
52.7 Na
2SO
44.0% Cs
2SO
410.0% P
2O
51.0% all the other be diatomite; Manufacture method is with embodiment 2.
Embodiment 4
Sample prescription V
2O
57.0% K
2O/V
2O
52.7 Na
2SO
42.0% Cs
2SO
410.0% P
2O
51.0% all the other be diatomite; Manufacture method is with embodiment 2.
Sample test: catalyst sample: granularity is φ 5 * 6～6.5mm.
The active testing condition:
Converter: adopt the jacket type single tube reactor, its caliber is φ 36 * 2mm, and the temperature thermocouple sleeve pipe is positioned at the center of converter, and its caliber is φ 8 * 1.5mm;
Catalyst loading amount: 30ml;
Catalyst grain size: 6～6.5mm;
Space velocity: 3600h;
Air inlet SO
2Percentage by volume: be air surplus in the of 10 ± 1%;
System pressure: normal pressure;
Active detected temperatures: 390 ℃, 410 ℃;
Heat resisting temperature and time: 600 ℃ of 5h;
With SO
2Conversion ratio represent active height.
Active testing the results are shown in following table, and wherein sample 1 is traditional low-temperature type vanadium catalyst, and sample 2,3,4 is ultralow warm type vanadium catalyst
The active testing result
Can find out that by the result in the above-mentioned table low temperature active of the low-temperature type vanadium catalyst of employing the inventive method preparation shows that apparently higher than traditional low-temperature type vanadium catalyst the performance of the vanadium catalyst of the inventive method preparation is significantly improved, and can satisfy higher SO
2The total conversion requirement.
Claims (1)
1. a preparation method who is used for the low-temperature type vanadium catalyst of gas washing in SA production is characterized in that improving the low temperature active of vanadium catalyst by adding the low-temperature activation agent, reduces initiation temperature, and the catalyst formulation percentage by weight is V
2O
55.0～8.5% K
2O/V
2O
52.5～4.5 Na
2O 1.0～15.0% Cs
2O 2.0～20.0% P
2O
51.0～5.0% all the other be diatomite; Addition manner is for adding when mixed grind or it being joined in the vanadium water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810234489A CN101757938A (en) | 2008-11-19 | 2008-11-19 | Method for preparing low-temperature vanadium catalyst in for sulphuric acid production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810234489A CN101757938A (en) | 2008-11-19 | 2008-11-19 | Method for preparing low-temperature vanadium catalyst in for sulphuric acid production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101757938A true CN101757938A (en) | 2010-06-30 |
Family
ID=42489413
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810234489A Pending CN101757938A (en) | 2008-11-19 | 2008-11-19 | Method for preparing low-temperature vanadium catalyst in for sulphuric acid production |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103506143A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Low-temperature type vanadium catalyst for preparation of sulfuric acid by wet conversion |
| CN108889319A (en) * | 2018-07-23 | 2018-11-27 | 贵州大学 | A kind of composite modified vanadium catalyst of efficient H2O2/Se and preparation method thereof |
| CN110575838A (en) * | 2018-06-10 | 2019-12-17 | 天津大学 | lanthanum-containing vanadium catalyst and preparation method and application thereof |
-
2008
- 2008-11-19 CN CN200810234489A patent/CN101757938A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103506143A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Low-temperature type vanadium catalyst for preparation of sulfuric acid by wet conversion |
| CN110575838A (en) * | 2018-06-10 | 2019-12-17 | 天津大学 | lanthanum-containing vanadium catalyst and preparation method and application thereof |
| CN108889319A (en) * | 2018-07-23 | 2018-11-27 | 贵州大学 | A kind of composite modified vanadium catalyst of efficient H2O2/Se and preparation method thereof |
| CN108889319B (en) * | 2018-07-23 | 2021-05-07 | 贵州大学 | Efficient H2O2/Se composite modified vanadium catalyst and preparation method thereof |
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Open date: 20100630 |