CN1322918C - Vanadium catalyst for preparing sulfuric acid by wet conversion and its preparation method - Google Patents
Vanadium catalyst for preparing sulfuric acid by wet conversion and its preparation method Download PDFInfo
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- CN1322918C CN1322918C CNB2004100661655A CN200410066165A CN1322918C CN 1322918 C CN1322918 C CN 1322918C CN B2004100661655 A CNB2004100661655 A CN B2004100661655A CN 200410066165 A CN200410066165 A CN 200410066165A CN 1322918 C CN1322918 C CN 1322918C
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- catalyst
- sulfuric acid
- vanadium
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- vanadium catalyst
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Abstract
The present invention relates to a vanadium catalyst for preparing sulfuric acid by the conversion of a wet method and a preparation method thereof, which belongs to the technical field of catalyst preparation. The catalyst comprises 6.5 to 8.0 wt% of V2O5, 3.0 to 4.0 wt% of K2 O/V2O5, 3.0 to 10.0 wt% of adjuvant and the rest components are balance of diatomite, wherein the diatomite, one of new mineral sources is used as a catalyst carrier, and the special vanadium catalyst for preparing sulfuric acid by the conversion of a wet method is prepared. The special vanadium catalyst prepared by the method has high activity and high strength under the condition of the conversion of a wet method, and is suitable for any part of a converter of a sulfuric acid producing device by the conversion of a wet method.
Description
Technical field:
The invention belongs to catalysis technical field, be specifically related to vanadium catalyst that a kind of preparing sulfuric acid by wet conversion uses and preparation method thereof.
Background technology:
Vanadium catalyst is used for sulfuric acid production plant with SO
2Oxidation conversion is SO
3The tradition vanadium catalyst is vanadium-potassium (sodium)-silicon system, with the vanadic anhydride is active component, potassium sulfate, sodium sulphate are auxiliary agent, Shandong diatomite, northeast diatomite or both mixing are as carrier, two kinds of middle warm type and low forms are arranged, this catalyst is mainly used in the catalytic oxidation of traditional sulfur dioxide, i.e. dry method conversion process does not have the existence of water vapour in the process of the catalytic oxidation of sulfur dioxide.
What hydrogen sulfide relieving haperacidity was adopted is the wet method conversion process, is characterized in containing in the unstrpped gas a large amount of water vapours, and the process of the catalytic oxidation of sulfur dioxide is to carry out under the condition that contains a large amount of water vapours.
The small-sized hydrogen sulfide sulphuric acid plant that China has set up is mainly used in handles coke-oven plant's coal gas, and used vanadium catalyst is the plain edition vanadium catalyst, and technic index control is not very strict, and the utilization of capacity is lower, and wet method transforms with vanadium catalyst still blank in China.
The existing manufacture method of vanadium catalyst:
The manufacture method of present vanadium catalyst is for to dissolve KOH 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.To mix in the adding rollers such as colloidal precipitation thing and auxiliary agent, terra silicea purificata to scale then, roll closely, become the plasticity material, again through extrusion, drying, roasting, sieve and operation such as packing is made vanadium catalyst.
Summary of the invention:
The objective of the invention is to propose a kind of vanadium catalyst product and manufacture method thereof of preparing sulfuric acid by wet conversion, this catalyst can adapt to the technological requirement of preparing sulfuric acid by wet conversion, has high activity and intensity, can satisfy preparing sulfuric acid by wet conversion to SO
2The needs of total conversion and catalyst strength.
The vanadium catalyst that the present invention produces has better catalytic performance, and this catalyst can be used for preparing sulfuric acid by wet conversion production.
At the characteristics of wet method conversion and the process condition of wet method relieving haperacidity, the present invention uses suitable vanadium catalyst carrier, by to vanadium catalyst prescription and process modification, produces the wet method conversion tailored version vanadium catalyst of function admirable.To satisfy the needs of wet method relieving haperacidity development.Transform at wet method and to contain 10% the moisture of having an appointment in the unstripped gas, by adding auxiliary agent, increase vanadium catalyst water-resistance, make it have enough intensity and resistance to chalking.By improving the prescription of vanadium catalyst, improve its activity of (400 ℃～500 ℃) in wide temperature range.
The present invention is achieved like this, and is carrier with Zhejiang diatomite, adds auxiliary agent in traditional vanadium-potassium (sodium)-silicon system, makes it have higher activity and heat endurance.It mainly comprises following content: mix in activity and the adding rollers such as alkali metal sulfates, auxiliary agent, terra silicea purificata by catalyst formulation, roll closely, become the plasticity material, again through extrusion, drying, roasting, sieve and operation such as packing is made vanadium catalyst.Vanadium catalyst prescription (wt) is: V
2O
56.5%～8.0%, K
2O/V
2O
53.5～4.0, auxiliary agent 3.0%～10.0% all the other be diatomite.
The used auxiliary agent of the present invention is a kind of in sodium sulphate, phosphoric acid, sodium phosphate, the sodium acid phosphate, also can be two kinds mixture; Shengxian County, the preferred Zhejiang of diatomite diatomite.
The vanadium catalyst of the present invention preparation is applicable to any part of the converter of preparing sulfuric acid by wet conversion process units.
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
5(4.0 mol ratio), sodium sulphate 3.0%, all the other are Shengxian County, Zhejiang diatomite.KOH is dissolved with steam, and and V
2O
5Under boiling condition, heat makes K
2O/V
2O
5Be 4.0 KVO
3With KOH mixed solution (hereinafter to be referred as vanadium water), the V of the vanadium water of preparation
2O
5Concentration is 265.9g/L, K
2O/V
2O
5Be 4.0.Then with the vanadium water 15.8ml1 of 24.4ml: 1 sulfuric acid neutralization makes V
2O
5And K
2SO
4The colloidal precipitation thing will mix in the adding rollers such as colloidal precipitation thing and 3.0g sodium sulphate, Shengxian County, 75.4g Zhejiang terra silicea purificata, adds water-powered roller and compresses closely, becomes the plasticity material, again through extrusion, drying, roasting, etc. operation make the 100.0g vanadium catalyst.
Embodiment 2
Sample prescription: V
2O
58.0%, K
2O/V
2O
5(3.5 mol ratio), sodium sulphate 3.1%, phosphatase 11 .0%, all the other are Shengxian County, Zhejiang diatomite.KOH is dissolved with steam, and and V
2O
5Under boiling condition, heat makes K
2O/V
2O
5Be 3.5 KVO
3With the KOH mixed solution, the V of the vanadium water of preparation
2O
5Concentration is 265.9g/L, K
2O/V
2O
5Be 3.5.Then with the vanadium water 17.0ml1 of 30.1ml: 1 sulfuric acid neutralization makes V
2O
5And K
2SO
4The colloidal precipitation thing, to mix in the adding rollers such as colloidal precipitation thing and 3.1g sodium sulphate, 1.0ml phosphoric acid, Shengxian County, 71.4g Zhejiang terra silicea purificata, add water-powered roller and compress closely, become the plasticity material, again through extrusion, drying, roasting, etc. operation make the 100.0g vanadium catalyst.
Embodiment 3
Sample prescription: V
2O
57.0%, K
2O/V
2O
5(4.0 mol ratio), sodium sulphate 3.3%, phosphatase 11 .0%, all the other are Shengxian County, Zhejiang diatomite.KOH is dissolved with steam, and and V
2O
5Under boiling condition, heat makes K
2O/V
2O
5Be 4.0 KVO
3With the KOH mixed solution, the V of the vanadium water of preparation
2O
5Concentration is 265.9g/L, K
2O/V
2O
5Be 4.0.Then with the vanadium water 17.0ml1 of 26.3ml: 1 sulfuric acid neutralization makes V
2O
5And K
2SO
4The colloidal precipitation thing, to mix in the adding rollers such as colloidal precipitation thing and 3.3g sodium sulphate, 1.0ml phosphoric acid, Shengxian County, 72.3g Zhejiang terra silicea purificata, add water-powered roller and compress closely, become the plasticity material, again through extrusion, drying, roasting, etc. operation make the 100.0g vanadium catalyst.
Embodiment 4
Sample prescription: V
2O
57.0%, K
2O/V
2O
5(3.5 mol ratio), sodium sulphate 5.5%, all the other are Shengxian County, Zhejiang diatomite.KOH is dissolved with steam, and and V
2O
5Under boiling condition, heat makes K
2O/V
2O
5Be 3.5 KVO
3With the KOH mixed solution, the V of the vanadium water of preparation
2O
5Concentration is 265.9g/L, K
2O/V
2O
5Be 3.5.Then with the vanadium water 14.9ml1 of 26.3ml: 1 sulfuric acid neutralization makes V
2O
5And K
2SO
4The colloidal precipitation thing will mix in the adding rollers such as colloidal precipitation thing and 5.5g sodium sulphate, Shengxian County, 73.7g Zhejiang terra silicea purificata, adds water-powered roller and compresses closely, becomes the plasticity material, again through extrusion, drying, roasting, etc. operation make the 100.0g vanadium catalyst.
Embodiment 5
Sample prescription: V
2O
57.0%, K
2O/V
2O
5(3.5 mol ratio), sodium sulphate 8.2%, all the other are Shengxian County, Zhejiang diatomite.KOH is dissolved with steam, and and V
2O
5Under boiling condition, heat makes K
2O/V
2O
5Be 3.5 KVO
3With the KOH mixed solution, the V of the vanadium water of preparation
2O
5Concentration is 265.9g/L, K
2O/V
2O
5Be 3.5.Then with the vanadium water 14.9ml1 of 26.3ml: 1 sulfuric acid neutralization makes V
2O
5And K
2SO
4The colloidal precipitation thing will mix in the adding rollers such as colloidal precipitation thing and 8.2g sodium sulphate, Shengxian County, 70.6g Zhejiang terra silicea purificata, adds water-powered roller and compresses closely, becomes the plasticity material, again through extrusion, drying, roasting, etc. operation make the 100.0g vanadium catalyst.
Sample test
1. active testing:
Catalyst sample: granularity is φ 12 * 4.5 * (10～15) mm.
The active testing condition:
Converter: adopt the jacket type single tube reactor, its caliber be in 36.0 * 2.0mm, the temperature thermocouple sleeve pipe is positioned at the center of converter, its caliber is φ 8.0 * 1.5mm;
Catalyst loading amount: 30ml;
Catalyst grain size: 3.35～4.0mm;
Space velocity: 3600h
-1
Air inlet SO
2Percentage by volume: 10% ± 1%, steam about 10%, surplus is air;
System pressure: normal pressure;
Active detected temperatures: 410 ℃, 485 ℃;
Heat resisting temperature and time: 700 ℃, 5h;
With SO
2Conversion ratio represent active height.
2. strength test:
Catalyst sample: granularity be in 12.0 * 4.5 * (10～15) mm.
The strength test condition:
The particle radially assay method of crush strength is undertaken by the regulation of GB/T3635.Strength detection adopts intelligent granule strength testing machine, 1 grade of precision, range 0～250N.
Acid bubble strength test condition:
With sample particle 1: 1H
2SO
4Behind the middle immersion 24h, blot acid solution, measure by the strength test condition.Active testing the results are shown in table 1, and strength test the results are shown in table 2.
Table 1 active testing result
| The sample example | Active (heat-resisting back SO 2Conversion ratio), % | |
| 410℃ | 485℃ | |
| 1 | 43.5 | 90.8 |
| 2 | 57.0 | 95.5 |
| 3 | 54.4 | 94.6 |
| 4 | 52.8 | 88.8 |
| 5 | 58.8 | 88.5 |
| Industry standard | 〉=42.0 (low form catalyst) | 〉=86.0 (middle warm type catalyst) |
Table 2 strength test result
| The sample example | Intensity, N/cm | Acid bubble intensity, N/cm |
| 1 | 62.8 | 39.1 |
| 2 | 67.8 | 34.6 |
| 3 | 74.4 | 33.3 |
| 4 | 77.8 | 41.5 |
| 5 | 66.7 | 37.1 |
| Industry standard | ≥35.0 | ---- |
Can find out by table 1 test result, adopt the special-purpose vanadium catalyst of wet method relieving haperacidity (400 ℃～500 ℃) in wide temperature range of the inventive method preparation to have high activity, in having concurrently, the performance of low-temperature vanadium catalyst.Table 2 test result shows that the vanadium catalyst that the present invention prepares has high strength.Therefore, the vanadium vanadium catalyst of the present invention's preparation can satisfy preparing sulfuric acid by wet conversion to SO
2The needs of total conversion and catalyst strength.
Claims (4)
1. the vanadium catalyst of a preparing sulfuric acid by wet conversion is characterized in that catalyst formulation (wt) is: V
2O
56.5%～8.0%, K
2O/V
2O
53.5～4.0, auxiliary agent 3.0%～10.0%, all the other are diatomite.
2. catalyst as claimed in claim 1 is characterized in that auxiliary agent is one or more the mixture in sodium sulphate, phosphoric acid, sodium phosphate, the sodium acid phosphate.
3. catalyst as claimed in claim 1 or 2 is characterized in that diatomite is Shengxian County, Zhejiang diatomite.
4. one kind prepares the method for catalyst according to claim 1, it is characterized in that said components being added in the roller and mix by catalyst formulation, roll closely, become the plasticity material, again through extrusion, drying, roasting, sieve and packaging process is made vanadium catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100661655A CN1322918C (en) | 2004-12-10 | 2004-12-10 | Vanadium catalyst for preparing sulfuric acid by wet conversion and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100661655A CN1322918C (en) | 2004-12-10 | 2004-12-10 | Vanadium catalyst for preparing sulfuric acid by wet conversion and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1657402A CN1657402A (en) | 2005-08-24 |
| CN1322918C true CN1322918C (en) | 2007-06-27 |
Family
ID=35007137
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100661655A Active CN1322918C (en) | 2004-12-10 | 2004-12-10 | Vanadium catalyst for preparing sulfuric acid by wet conversion and its preparation method |
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Families Citing this family (7)
| 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 |
| CN105080309B (en) * | 2014-05-23 | 2018-01-05 | 国网山西省电力公司电力科学研究院 | A kind of purifying treatment method and device for sulfur hexafluoride detection tail gas |
| CN106311299A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Vanadium catalyst used for producing sulfuric acid by high-density reforming gas and preparation method thereof |
| CN105126861A (en) * | 2015-09-07 | 2015-12-09 | 吉林省天元硅藻科技有限公司 | Sulfuric acid catalyst prepared through middle and low temperature hydrogen sulfide wetting method and preparation method therefor |
| CN109420488A (en) * | 2017-08-23 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of preparation method of preparing sulfuric acid by wet conversion catalyst |
| CN110876947A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Preparation method of sulfuric acid catalyst by wet oxidation of sulfur dioxide |
| CN111036242A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Vanadium-based catalyst for preparing sulfuric acid by wet conversion |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417109A (en) * | 2002-12-11 | 2003-05-14 | 南化集团研究院 | Medium-temperature vanadium catalyst for sulfuric acid production and its prepn |
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- 2004-12-10 CN CNB2004100661655A patent/CN1322918C/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417109A (en) * | 2002-12-11 | 2003-05-14 | 南化集团研究院 | Medium-temperature vanadium catalyst for sulfuric acid production and its prepn |
Non-Patent Citations (1)
| Title |
|---|
| 浙江嵊县硅藻土及其在矾催化剂中的应用 张秋菊等，硫酸工业，第4期 2003 * |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: Nanhua Group Research Institute |