CN101648138B - Arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide and preparation method thereof - Google Patents
Arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide and preparation method thereof Download PDFInfo
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- CN101648138B CN101648138B CN200810048819XA CN200810048819A CN101648138B CN 101648138 B CN101648138 B CN 101648138B CN 200810048819X A CN200810048819X A CN 200810048819XA CN 200810048819 A CN200810048819 A CN 200810048819A CN 101648138 B CN101648138 B CN 101648138B
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- catalyst
- auxiliary agent
- sulfuric acid
- arsenic
- diatomite
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Abstract
The invention discloses an arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide and a preparation method thereof. The arsenic resistant catalyst is used for preparing acid from nonferrous metal refining smoke and pyrite with high arsenic and fluorine content. A vanadium catalyst is added with calcium salt, tin salt and aluminum salt, and diatomite is subjected to water separation, acid treating, filter pressing and drying to prepare a carrier; potassium hydroxide and vanadium pentoxide are dissolved and purified in proportion to prepare mixed solution; the mixed solution is neutralized by sulfuric acid to prepare a V2O5 and K2SO4 colloid mixture, and colloid precipitate is subjected to standing and osmosis; and the colloid precipitate, the calcium salt, the tin salt, the aluminum salt and the diatomite are added into a roller, mixed evenly, and ground into a plastic material, and the plastic material is formed, dried, baked, sieved and packaged into the vanadium catalyst. Through formula adjustment and the increase of a standing and osmosis process, the materials are more evenly mixed, the strength, arsenic resistant antitoxic performance, service life and stability of the catalyst are improved, the arsenic resistant antitoxic capacity of the catalyst is 3 to 4 times higher than that of the conventional catalysts, and the SO2 conversion rate is stably kept above 99.6 percent.
Description
Affiliated technical field
The present invention relates to a kind of vanadium catalyst of preparing sulfuric acid by oxidizing sulfur dioxide, particularly a kind of antitoxin catalyst of anti-arsenic of preparing sulfuric acid by oxidizing sulfur dioxide.
Background technology
The preparing sulfuric acid by oxidizing sulfur dioxide catalyst is used for sulfuric acid production plant with SO
2Oxidation conversion is SO
3The subject matter of China's preparing sulfuric acid by oxidizing sulfur dioxide catalyst existence at present is that the catalyst activity rate of decay is fast, and conversion ratio is unstable, and catalyst is low service life.Its main cause is that the high-quality ferro-sulphur ore reduces day by day, and impurity (particularly objectionable impurities such as arsenic, fluorine) content is higher in the existing troilite that generally uses, and these impurity very easily cause catalyst efflorescence or poisoning and deactivation.Wherein the existence of arsenic, fluorine can cause the preparing sulfuric acid by oxidizing sulfur dioxide catalyst forever to be poisoned, and hydrogen fluoride very easily causes catalyst structure to destroy pulverizing, and then causes catalytic activity reduction, catalytic bed vapour lock to increase.Therefore need to the structural co-catalyst kind of preparing sulfuric acid by oxidizing sulfur dioxide catalyst and prescription be adjusted or preparation technology improves, to adapt to the demand of high arsenic, fluorine raw material production sulfuric acid.
In the prior art, domestic preparing sulfuric acid by oxidizing sulfur dioxide catalyst structure property co-catalyst is generally sodium salt, sylvite, and the general technological process of production is: diatomite is refining; Vanadic anhydride, other auxiliary agent of alkali metal mother liquor dissolve with sulfuric acid and neutralize; Corrective mixes with terra silicea purificata, other auxiliary agents and grinds, moulding, drying, calcining and processing.
Summary of the invention
The object of the present invention is to provide a kind of arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide and preparation method thereof; Catalyst of the present invention can satisfy the technological requirement of high arsenic, fluorine raw material production sulfuric acid; Have performances such as strong, the anti-efflorescence of anti-malicious ability, intensity is high, activity stability is good; Improve the adaptive capacity of sulfuric acid manufacturing, be beneficial to fully effectively utilizing of ferro-sulphur ore resource.
Design philosophy of the present invention is: in traditional vanadium-potassium (sodium)-silicon system, add calcium salt, pink salt, aluminium salt as structural promoter and anti-malicious auxiliary agent, make it have noxious material and anti-efflorescence abilities such as anti-arsenic, fluorine, and keep stable activity.
Technical program of the present invention lies in: in vanadium catalyst, add auxiliary agent: calcium salt, pink salt and aluminium salt, the percentage by weight of vanadium catalyst is: V
2O
56.0-8.0%, K
2O/V
2O
5(2.8-3.0 mol ratio), Na
2SO
45.0-15.0%, CaO 5.0-20.0%, SnO1.0-10.0%, Al
2O
30.5-3.0%, all the other are diatomite.
Calcium salt auxiliary agent of the present invention is: the mixture of one or more in calcium carbonate, calcium nitrate, the calcium oxide.
Pink salt auxiliary agent of the present invention is: the mixture of one or more in stannous chloride, stannous oxide, the tin oxide.
Aluminium salt assitant of the present invention is: the mixture of one or more in aluminium dihydrogen phosphate, aluminum sulfate, the alundum (Al.
The said diatomite of the present invention is one or more mixtures in Celite, Changbai Mountain diatomite, Linqu, Shandong diatomite, the Yunnan Xun Dian diatomite.
The preparation method of arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide of the present invention is characterized in that: press filtration after diatomite process wet concentration, the acid treatment, drying are processed carrier; Potassium hydroxide, vanadic anhydride dissolve in proportion purify mixed solution; Make V with the sulfuric acid neutralization then
2O
5, K
2SO
4Colloid admixture, the colloidal precipitation thing leaves standstill infiltration; In proportion colloidal precipitation thing and calcium salt, pink salt and aluminium salt, terra silicea purificata are added in the roller and mix, grind into the plasticity material, through moulding, drying, roasting, sieve and packaging process is processed vanadium catalyst.
The present invention is directed to present China gas washing in SA production raw material arsenic, present situation that fluorine content is high; At traditional preparing sulfuric acid by oxidizing sulfur dioxide catalyst is on the basis of active component with the vfanadium compound; Adopt calcium salt, pink salt, aluminium salt as structural promoter and anti-malicious auxiliary agent; Form the high-strength bone shelf structure with refining carrier, make arsenic resistant catalyst through mixed stone roller, drying, high temperature congruent melting.Through prescription adjustment, improved catalyst strength and antitoxin performance, thereby improved catalyst service life; On preparation technology, increase and leave standstill the infiltration operation, make mixing of materials more even, improved the stability of catalyst.The present invention's poison resistance of anti-arsenic exceeds traditional catalyst 3-4 doubly, SO
2Conversion ratio is stable to remain on more than 99.6%.
Arsenic resistant catalyst of the present invention can be used for roasting pyrite relieving haperacidity, wet method conversion relieving haperacidity, the dense SO of height gas
2SO such as relieving haperacidity
2Change into SO
3Industry is applicable to any part of the converter of sulfuric acid production plant.Be specially adapted to arsenic, higher non-ferrous metal metallurgy flue gas acid preparing and the pyrite-based sulfuric acid production of fluorine content.
The specific embodiment
Further specify content of the present invention below in conjunction with embodiment.
Embodiment 1
Sample composition: V
2O
58.0%, K
2O/V
2O
5(2.8 mol ratio), Na
2SO
412.0%, calcium oxide 8.0%, tin oxide 5.0%, alundum (Al 3.0%, all the other are terra silicea purificata.
Adopt traditional processing technology, with diatomite through wet concentration, acid treatment, filtration washing and drying make terra silicea purificata; KOH is dissolved with steam, and and V
2O
5, heat makes K under boiling condition
2O/V
2O
5Be 2.8 KVO
3With KOH mixed solution (being designated hereinafter simply as vanadium water), the V of the vanadium water of preparation
2O
5Concentration be 260.0g/l, K
2O/V
2O
5Be 2.8.Vanadium water with 30.8ml makes V with the neutralization of 1: 1 sulfuric acid of 17.5ml then
2O
5And K
2SO
4Colloid admixture, the colloidal precipitation thing leaves standstill infiltration; With mixing in the adding rollers such as colloidal precipitation thing and 12.0g sodium sulphate, 8.0g calcium oxide, 5.0g tin oxide, 3.0g aluminium oxide, 50.4g terra silicea purificata; Grind into the plasticity material, through moulding, drying, roasting, sieve and operation such as packing is processed the 100g vanadium catalyst.
Embodiment 2
Sample composition: V
2O
57.0%, K
2O/V
2O
5(2.9 mol ratio), Na
2SO
410.0%, calcium oxide 10.0%, tin oxide 4.0%, alundum (Al 1.5%, all the other are terra silicea purificata.Adopt embodiment 1 technology, selecting calcium carbonate, stannous chloride, aluminium dihydrogen phosphate for use is auxiliary agent.
Embodiment 3
Sample composition: V
2O
56.0%, K
2O/V
2O
5(3.0 mol ratio), Na
2SO
48.0%, calcium oxide 14.0%, tin oxide 3.0%, alundum (Al 1.0%, all the other are terra silicea purificata.Adopt embodiment 1 technology, selecting calcium nitrate, stannous oxide, aluminum sulfate for use is auxiliary agent.
Embodiment 4
Sample composition: V
2O
57.5%, K
2O/V
2O
5(2.9 mol ratio), Na
2SO
413.0%, calcium oxide 18.0%, tin oxide 2.0%, alundum (Al 0.5%, all the other are terra silicea purificata.Adopt embodiment 1 technology, select for use calcium oxide, stannous chloride, aluminium dihydrogen phosphate as auxiliary agent.
Embodiment 5
Sample composition: V
2O
57.5%, K
2O/V
2O
5(2.9 mol ratio), Na
2SO
411.0%, calcium oxide 5.0%, tin oxide 5.5%, alundum (Al 2.6%, all the other are terra silicea purificata.Adopt embodiment 1 technology, select for use calcium carbonate, stannous chloride, alundum (Al as auxiliary agent.
Embodiment 6
Sample composition: V
2O
57.0%, K
2O/V
2O
5(2.8 mol ratio), Na
2SO
47.0%, calcium oxide 7.0%, tin oxide 4.0%, alundum (Al 2.2%, all the other are terra silicea purificata.Adopt embodiment 1 technology, select for use calcium nitrate, stannous chloride, aluminum sulfate as auxiliary agent.
Embodiment 7
Sample composition: V
2O
57.0%, K
2O/V
2O
5(3.0 mol ratio), Na
2SO
45.0%, calcium oxide 9.0%, tin oxide 5.0%, alundum (Al 1.5%, all the other are terra silicea purificata.Adopt embodiment 1 technology, select for use calcium nitrate, tin oxide, aluminium dihydrogen phosphate as auxiliary agent.
Embodiment 8
Sample composition: V
2O
57.0%, K
2O/V
2O
5(2.9 mol ratio), Na
2SO
47.0%, calcium oxide 5.0%, tin oxide 10.0%, alundum (Al 1.0%, all the other are terra silicea purificata.Adopt embodiment 1 technology, select for use calcium oxide, stannous chloride, aluminum sulfate as auxiliary agent.
Sample test:
(1) conventional determining:
Active mensuration:
Press the regulation of HG/T2089, wherein the related assays condition is:
Catalyst loading amount: 30ml;
Catalyst grain size: 3.35-4.00mm;
Space velocity: 3600h
-1
The volume fraction of air inlet sulfur dioxide: (10.0 ± 0.1) %, all the other are air;
System pressure: normal pressure;
Determination of activity temperature: 485 ℃;
Heat resisting temperature and time: 700 ℃, 5h;
Particle is the mensuration of anti-crushing power radially:
Press the regulation of HG/T 2782, when wherein measuring
Catalyst sample is handled the sample that slivering length is 6～7mm and grinding two end surfaces;
It is 40 that sample is measured granule number.
The mensuration of rate of wear:
Press the regulation of HG/T 2969, wherein sample is at (120 ± 5) ℃ following oven dry 2h.
Catalyst sample test result of the present invention see the following form (code name of catalyst of the present invention in following test is S116):
Table 1 activity, intensity, abrasion test result
| The sample example | Active (485 ℃), % | Intensity, N/cm | Rate of wear, % |
| 1 | 91 | 103 | 2 |
| 2 | 90 | 107 | 2 |
| 3 | 88 | 110 | 1 |
| 4 | 90 | 98 | 3 |
| 5 | 89 | 100 | 2 |
| Industry standard | ≥86.0 | ≥60.0 | ≤5.0 |
Can go out by table 1 test result: adopt S116 arsenic resistant catalyst normality and the application state of the inventive method preparation active down high, intensity is high, abrasion are little, particularly intensity, wear and tear index and obviously be superior to conventional products.
(2) anti-arsenic poisoning ability is measured: (code name of catalyst of the present invention in following test is S116)
S101 type catalyst, U.S. company catalyst and S116 arsenic resistant catalysts to a large amount of uses at present analyze result such as following table:
The suction arsenic of catalyst and mistake vanadium under table 2 different temperatures
The relation of conversion ratio and logical arsenic amount and temperature after table 3 is poisoned
The comparison of intensity before and after table 4 catalyst uses
From above three tables, can find out, S101 type catalyst and U.S. company catalyst after leading to arsenic, the V of loss
2O
5Measure more; Activity decay is very fast, and intensity descends obviously, and the S116 type preparing sulfuric acid by oxidizing sulfur dioxide of anti-arsenic catalyst its mistake vanadium amount, activity, intensity index before and after logical arsenic uses obviously are better than other two kinds of catalyst; Particularly after logical arsenic amount strengthened, it is more remarkable that intensity increases percentage.So the S116 type preparing sulfuric acid by oxidizing sulfur dioxide of anti-arsenic catalyst is strong than the anti-arsenic poisoning ability of traditional catalyst, be applicable to high arsenic, fluorine raw material relieving haperacidity industry.
Claims (3)
1. arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide is characterized in that: in existing vanadium catalyst, add calcium auxiliary agent, tin auxiliary agent, aluminium auxiliary agent, the percentage by weight of gained arsenic resistant catalyst is: V
2O
56.0-8.0%, K
2O/V
2O
5(2.8-3.0 mol ratio), Na
2SO
45.0-15.0%, CaO 5.0-20.0%, SnO 1.0-10.0%, Al
2O
30.5-3.0%, all the other are diatomite; The preparation method of this arsenic resistant catalyst is: press filtration after diatomite process wet concentration, the acid treatment, drying are processed carrier; Potassium hydroxide, vanadic anhydride dissolve in proportion purify mixed solution; Make V with the sulfuric acid neutralization then
2O
5, K
2SO
4Colloid admixture, the colloidal precipitation thing leaves standstill infiltration; In proportion colloidal precipitation thing and calcium auxiliary agent, tin auxiliary agent, aluminium auxiliary agent, terra silicea purificata are added in the roller and mix, grind into the plasticity material, through moulding, drying, roasting, sieve and packaging process is processed;
Said calcium auxiliary agent is: the mixture of one or more in calcium carbonate, calcium nitrate, the calcium oxide,
Said tin auxiliary agent is: the mixture of one or more in stannous chloride, stannous oxide, the tin oxide,
Said aluminium auxiliary agent is: the mixture of one or more in aluminium dihydrogen phosphate, aluminum sulfate, the alundum (Al.
2. arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide according to claim 1 is characterized in that: said diatomite is one or more mixtures in Changbai Mountain diatomite, Linqu, Shandong diatomite, the Yunnan Xun Dian diatomite.
3. the preparation method of the described arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide of claim 1 is characterized in that: diatomite through wet concentration, acid treatment after press filtration, drying process carrier; Potassium hydroxide, vanadic anhydride dissolve in proportion purify mixed solution; Make V with the sulfuric acid neutralization then
2O
5, K
2SO
4Colloid admixture, the colloidal precipitation thing leaves standstill infiltration; In proportion colloidal precipitation thing and calcium auxiliary agent, tin auxiliary agent, aluminium auxiliary agent, terra silicea purificata are added in the roller and mix, grind into the plasticity material, through moulding, drying, roasting, sieve and packaging process is processed arsenic resistant catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810048819XA CN101648138B (en) | 2008-08-12 | 2008-08-12 | Arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810048819XA CN101648138B (en) | 2008-08-12 | 2008-08-12 | Arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide and preparation method thereof |
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|---|---|
| CN101648138A CN101648138A (en) | 2010-02-17 |
| CN101648138B true CN101648138B (en) | 2012-06-20 |
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|---|---|---|---|
| CN200810048819XA Expired - Fee Related CN101648138B (en) | 2008-08-12 | 2008-08-12 | Arsenic resistant catalyst for preparing sulfuric acid by oxidizing sulfur dioxide and preparation method thereof |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350367B (en) * | 2011-08-30 | 2013-08-14 | 开封市三丰催化剂有限责任公司 | Production method of sulfuric acid catalyst by oxidizing sulfur dioxide |
| CN102974372B (en) * | 2011-09-05 | 2015-10-07 | 襄阳市精信催化剂有限责任公司 | Resistance to arsenic, fluorine poisoning sulfuric acid catalyst by oxidizing sulfur dioxide and preparation method thereof |
| CN103752336B (en) * | 2014-01-07 | 2015-12-09 | 南京云高新型材料有限公司 | A kind of vanadium catalyst for nitrobenzene sulfonation and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294723A (en) * | 1975-05-29 | 1981-10-13 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Heat resistant catalyst for the production of sulfuric acid for using a gas containing sulfur dioxide in a high concentration |
| EP0516001A1 (en) * | 1991-05-24 | 1992-12-02 | Haldor Topsoe A/S | Process for the regeneration of spent sulphuric acid |
| CN101041131A (en) * | 2006-03-20 | 2007-09-26 | 襄樊市精信催化剂有限责任公司 | SCL sulfur dioxide oxidation system producing aulfuric acid and the preparing method |
| CN101088607A (en) * | 2006-06-13 | 2007-12-19 | 攀枝花学院 | Technological process of preparing high efficient vanadium catalyst with nanometer vanadium material |
-
2008
- 2008-08-12 CN CN200810048819XA patent/CN101648138B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294723A (en) * | 1975-05-29 | 1981-10-13 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Heat resistant catalyst for the production of sulfuric acid for using a gas containing sulfur dioxide in a high concentration |
| EP0516001A1 (en) * | 1991-05-24 | 1992-12-02 | Haldor Topsoe A/S | Process for the regeneration of spent sulphuric acid |
| CN101041131A (en) * | 2006-03-20 | 2007-09-26 | 襄樊市精信催化剂有限责任公司 | SCL sulfur dioxide oxidation system producing aulfuric acid and the preparing method |
| CN101088607A (en) * | 2006-06-13 | 2007-12-19 | 攀枝花学院 | Technological process of preparing high efficient vanadium catalyst with nanometer vanadium material |
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