CN104525273A - Desulphurization catalyst - Google Patents
Desulphurization catalyst Download PDFInfo
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- CN104525273A CN104525273A CN201410808582.6A CN201410808582A CN104525273A CN 104525273 A CN104525273 A CN 104525273A CN 201410808582 A CN201410808582 A CN 201410808582A CN 104525273 A CN104525273 A CN 104525273A
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Abstract
The invention relates to a desulphurization agent. The desulphurization agent is composed of an active ingredient and an auxiliary, wherein the active ingredient is compounded by a variable metal salt ion, a complex of the variable metal salt ion, and polyphenol, the auxiliary is compounded by a phosphorous-containing compound and a titanium-containing compound, the active ingredient accounts for 90-98% of the catalyst in total mass, and the balance is the auxiliary. The desulphurization agent has the advantages that variable valence metal irons, cobalt and copper ions are common, the cost is low, no toxicity is produced, and no pollution is generated to the environment during production and application; a complexing system of the complex of the variable valence metal ion is stable, the desulphurization efficiency is high, the catalytic activity is strong, and usage amount of the catalyst is low; polyphenol can be oxidized into quininone compounds, the transmission speed of oxygen in a liquid phase and the oxidation speed of low-valance metal ions are increased, the activity of the catalyst is greatly improved, and the auxiliary containing phosphorous and titanium is added in the catalyst, so that the corrosion rate of equipment can be reduced, the corrosion effect of the catalyst to the equipment is greatly alleviated, and the service life of the equipment is prolonged.
Description
Technical field
The present invention relates to a kind of wet oxidation desulfurization catalyst technology, especially a kind of desulphurization catalyst.
Background technology
Along with the continuous intensification of process of industrialization, sulfurous gas (H in air
2s, SO
2, CS
2, CH
3sH etc.) discharge capacity day by day increase, caused serious environmental pollution, directly jeopardized human health.In order to protect environment for human survival, development and research desulfur technology seem day by day urgent and important.In prior art, the method removing sulfide is a lot, the active carbon in such as dry method, iron oxide etc., ADA method, tannin process, ammoniacal liquor liquid catalytic, benzoquinones method etc. in wet method.Above-mentioned various method and desulphurization catalyst respectively have advantage, but also there are some defects, such as Sulfur capacity is little, desulfuration efficiency is low, can not long-time stable operation, regeneration difficulty and in use produce secondary pollution etc.
Application number be 200410042863.1 Chinese invention patent application disclose a kind of wet oxidation desulfurization catalyst and application thereof, this invention adopts Cobalt Phthalocyanine, Phthalocyanine Zinc, cobalt nitrate and ammonium salt composition catalyst, solve exist in prior art narrow application range, easily cause sulphur to block up the problems such as tower, there is wide, the stifled tower of the scope of application, sulfur recovery rate be high, Recovered sulphur purity is high, nontoxic, consumption is few, the advantage such as corrosion-free, non-environmental-pollution.But the method easily causes equipment corrosion, and the desulfuration efficiency of desulphurization catalyst need further raising.Application number be 200510018863.2 Chinese invention patent application disclose a kind of multicomponent composite desulfate catalyst, it is characterized in that mainly comprising following component: (1) Cobalt Phthalocyanine, (2) polyphenol compound, (3) molysite, (4) ligand of complex compound can be formed with molysite, (5) vanadium compounds, the percentage by weight of each constituent content is: Cobalt Phthalocyanine derivative 20% ~ 50%, polyphenol compound 10% ~ 50%, molysite 10% ~ 15%, ligand 10% ~ 50%, vanadium compounds 1% ~ 40%.Its combination property is superior, can reach the desulfurization degree of 98% to the unstripped gas of sulfur-bearing 5% ~ 10%.But do not consider the corrosion to equipment, desulfuration efficiency need further raising.
Summary of the invention
Technical problem to be solved by this invention be provide a kind of for above-mentioned prior art present situation and can not pollute environment in manufacture and usage, catalytic activity is strong, desulfuration efficiency is high and the desulphurization catalyst of the long service life of equipment.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of desulphurization catalyst, the formula of this catalyst is made up of active component and auxiliary agent, it is characterized in that: described active component is composited by variable valency metal salt ion and complex compound thereof and polyphenols, described auxiliary agent is made up of jointly phosphorus-containing compound, titanium-containing compound, described active component accounts for 90 ~ 98% of catalyst gross mass, and all the other are auxiliary agent; Described percentage is mass percent.
As improvement, described variable valency metal salt accounts for catalyst gross mass 10 ~ 40%, described complex compound accounts for 10 ~ 40% of catalyst gross mass, described polyphenols accounts for 20 ~ 50% of catalyst gross mass, described phosphorus-containing compound accounts for 1 ~ 10% of catalyst gross mass, and described titanium-containing compound accounts for 1 ~ 10% of catalyst gross mass.Described percentage is mass percent.
As improvement, described variable valency metal salt ion can be preferably iron 3
+ion, ferrous 2
+ion, cobalt 2
+ion, cobalt 3
+ion, copper 2
+ion, cuprous 1
+one or more in ion, described variable valency metal salt is one or more in the hydrochloride of above-mentioned ion, nitrate, sulfate.
As improvement, the ligand of the co-ordination complex of described variable valency metal salt ion may be selected to be in citric acid, amino acid, salicylic acid, tartaric acid one or more.
As improvement, described polyphenols can be preferably in hydroquinones, pyrogallol, resvertrol, tannin one or more.
As improvement, described phosphorus-containing compound can be preferably in phosphorus pentoxide, sodium dihydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate one or more.
As improvement, described titanium-containing compound can be preferably in titanium dioxide, sodium titanate, potassium titanate one or more.
As improvement, the cushioning liquid in desulphurization catalyst is alkaline solution, and the pH value of described alkaline solution is in 8 ~ 12 scopes.
Improve again, the alkaline chemical combination in described alkaline solution can be preferably in sodium carbonate, sodium acid carbonate, ammonium carbonate, NaOH, ammoniacal liquor one or more.
Compared with prior art, the invention has the advantages that: the present invention adopts the complex compound of variable valency metal salt ion as desulfurization major catalyst, and variable valency metal iron, cobalt, copper are comparatively common metals, cheap nontoxic, and can not pollute environment in manufacture and usage; The complex system of variable valency metal salt ion complex compound is stablized, and desulfuration efficiency is high, and catalytic activity is strong, and catalyst amount is few; Polyphenols generates quinones substance as the oxygen in oxygen carrier and air in regenerative process, because quinones substance can automatically oxygen uptake at a terrific speed, accelerate oxygen transmission speed in the liquid phase and the oxidation rate of low valence metal ion, the activity of catalyst is increased significantly, secondly Oxidation of Hydrogen Sulfide also directly can be become elemental sulfur by quinones substance itself, and the desulfurization of catalyst and regeneration efficiency are greatly improved; With the addition of auxiliary agent phosphorus-containing compound and titanium-containing compound in catalyst, the corrosion rate of equipment can be delayed, significantly reduce catalyst to equipment corrosion effect, extend the service life of equipment.In sum, desulphurization catalyst of the present invention is that a kind of complex system is stablized, infiltration rate is fast, desulfuration efficiency is high, catalyst amount is few, regeneration is complete, equipment corrosion is little, the composite efficient desulphurization catalyst of environmental nonpollution, has good application prospect.
Detailed description of the invention
The formula of the desulphurization catalyst of the present embodiment is made up of active component and auxiliary agent, described active component is composited by variable valency metal salt ion and complex compound thereof and polyphenols, described auxiliary agent is made up of jointly phosphorus-containing compound, titanium-containing compound, described active component accounts for 90 ~ 98% of catalyst gross mass, and all the other are auxiliary agent; Described variable valency metal salt accounts for catalyst gross mass 10 ~ 40%, described complex compound accounts for 20 ~ 50% of catalyst gross mass, described polyphenols accounts for 10 ~ 40% of catalyst gross mass, described phosphorus-containing compound accounts for 1 ~ 10% of catalyst gross mass, and described titanium-containing compound accounts for 1 ~ 10% of catalyst gross mass.Described percentage is mass percent.Described variable valency metal salt ion is one or more in iron 3+ ion, ferrous 2+ ion, cobalt 2+ ion, cobalt 3+ ion, copper 2+ ion, cuprous 1+ ion, and described variable valency metal salt is one or more in the hydrochloride of above-mentioned ion, nitrate, sulfate.The ligand of the co-ordination complex of described variable valency metal salt ion is one or more in citric acid, amino acid, salicylic acid, tartaric acid.Described polyphenols is one or more in hydroquinones, pyrogallol, resvertrol, tannin.Described phosphorus-containing compound is phosphorus pentoxide, titanium-containing compound described in one or more in sodium dihydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate is one or more in titanium dioxide, sodium titanate, potassium titanate.Cushioning liquid in desulphurization catalyst is alkaline solution, and the pH value of described alkaline solution is in 8 ~ 12 scopes.Alkalization in described alkaline solution be combined in sodium carbonate, sodium acid carbonate, ammonium carbonate, NaOH, ammoniacal liquor one or more.
Below in conjunction with specific embodiment, the invention will be further described, and C1 ~ C4 is inventive desulfurization catalyst, and its component and mass percentage are in table 1.
The composition of table 1 desulphurization catalyst
Embodiment 1
Desulphurization catalyst C1 and sodium carbonate are configured to alkaline doctor solution, and wherein iron complex content is 1.0g/l, and polyphenol content is 0.2g/l, and the pH value of solution is 8.5.Hydrogen sulfide content 1.2g/Nm in gas
3time, desulfuration efficiency is 99.1%.
Embodiment 2
Desulphurization catalyst C2 and sodium carbonate are configured to alkaline doctor solution, and wherein copper complex content is 1.0g/l, and polyphenol content is 0.4g/l, and the pH value of solution is 9.0.Hydrogen sulfide content 1.5g/Nm in gas
3time, desulfuration efficiency is 98.8%.
Embodiment 3
Desulphurization catalyst C3 and NaOH are configured to alkaline doctor solution, and wherein cobalt complex content is 1.2g/l, and polyphenol content is 0.3g/l, and the pH value of solution is 10.0.Hydrogen sulfide content 1.2g/Nm in gas
3time, desulfuration efficiency is 99.5%.
Embodiment 4
Desulphurization catalyst C4 and sodium carbonate are configured to alkaline doctor solution, and wherein iron complex and copper complex total content are 1.5g/l, and polyphenol content is 0.2g/l, and the pH value of solution is 9.0.Hydrogen sulfide content 1.2g/Nm in gas
3time, desulfuration efficiency is 99.8%.
Operation principle of the present invention is: in desulphurization system, hydrogen sulfide and carbon dioxide are by alkali liquor absorption, hydrogen sulfide is oxidized to simple substance sulphur by high volence metal ion complex compound, then this sulfur removing pregnant solution enters regenerative system, the carbon dioxide absorbed discharges and reclaims from solution, blast air again, be quinones substance as the polyphenols of oxygen carrier by the dioxygen oxidation in air, by quinones substance, as-reduced low valence metal ion complex compound reoxidized as high volence metal ion complex compound.In addition, Oxidation of Hydrogen Sulfide can be directly also simple substance sulphur by quinones substance, and the separated recovery of sulphur, the desulfurization lean solution after regeneration is got back to again desulphurization system and recycled.
Claims (9)
1. a desulphurization catalyst, the formula of described catalyst is made up of active component and auxiliary agent, it is characterized in that: described active component is composited by variable valency metal salt ion and complex compound thereof and polyphenols, described auxiliary agent is made up of jointly phosphorus-containing compound, titanium-containing compound, described active component accounts for 90 ~ 98% of catalyst gross mass, all the other are auxiliary agent, and described percentage is mass percent.
2. desulphurization catalyst according to claim 1, it is characterized in that: described variable valency metal salt accounts for catalyst gross mass 10 ~ 40%, described complex compound accounts for 20 ~ 50% of catalyst gross mass, described polyphenols accounts for 10 ~ 40% of catalyst gross mass, described phosphorus-containing compound accounts for 1 ~ 10% of catalyst gross mass, described titanium-containing compound accounts for 1 ~ 10% of catalyst gross mass, and described percentage is mass percent.
3. desulphurization catalyst according to claim 2, is characterized in that: described variable valency metal salt ion is iron 3
+ion, ferrous 2
+ion, cobalt 2
+ion, cobalt 3
+ion, copper 2
+ion, cuprous 1
+one or more in ion, described variable valency metal salt is one or more in the hydrochloride of above-mentioned ion, nitrate, sulfate.
4. according to described desulphurization catalyst arbitrary in claims 1 to 3, it is characterized in that: the ligand of the co-ordination complex of described variable valency metal salt ion is one or more in citric acid, amino acid, salicylic acid, tartaric acid.
5. according to described desulphurization catalyst arbitrary in claims 1 to 3, it is characterized in that: described polyphenols is one or more in hydroquinones, pyrogallol, resvertrol, tannin.
6. according to described desulphurization catalyst arbitrary in claims 1 to 3, it is characterized in that: described phosphorus-containing compound is one or more in phosphorus pentoxide, sodium dihydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate.
7. according to described desulphurization catalyst arbitrary in claims 1 to 3, it is characterized in that: described titanium-containing compound is one or more in titanium dioxide, sodium titanate, potassium titanate.
8., according to described desulphurization catalyst arbitrary in claims 1 to 3, it is characterized in that: the cushioning liquid in desulphurization catalyst is alkaline solution, the pH value of described alkaline solution is in 8 ~ 12 scopes.
9. desulphurization catalyst according to claim 8, is characterized in that: the alkalization in described alkaline solution be combined in sodium carbonate, sodium acid carbonate, ammonium carbonate, NaOH, ammoniacal liquor one or more.
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|---|---|---|---|
| CN201410808582.6A CN104525273A (en) | 2014-12-19 | 2014-12-19 | Desulphurization catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109663484A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | High performance vulcanization hydrogen inhales disappear liquid and purposes |
| CN109663483A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The suction for quickly removing hydrogen sulfide gas disappears liquid and purposes |
| CN110876881A (en) * | 2018-09-05 | 2020-03-13 | 中国石油化工股份有限公司 | Complex iron desulfurizer for claus tail gas treatment |
-
2014
- 2014-12-19 CN CN201410808582.6A patent/CN104525273A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109663484A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | High performance vulcanization hydrogen inhales disappear liquid and purposes |
| CN109663483A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The suction for quickly removing hydrogen sulfide gas disappears liquid and purposes |
| CN109663483B (en) * | 2017-10-17 | 2021-10-15 | 中国石油化工股份有限公司 | Absorption and elimination liquid for quickly removing hydrogen sulfide gas and application |
| CN110876881A (en) * | 2018-09-05 | 2020-03-13 | 中国石油化工股份有限公司 | Complex iron desulfurizer for claus tail gas treatment |
| CN110876881B (en) * | 2018-09-05 | 2022-04-08 | 中国石油化工股份有限公司 | Complex iron desulfurizer for claus tail gas treatment |
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