CN103657341A - Anti-oxidation type SO2 absorbing recycle agent - Google Patents
Anti-oxidation type SO2 absorbing recycle agent Download PDFInfo
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- CN103657341A CN103657341A CN201310666043.9A CN201310666043A CN103657341A CN 103657341 A CN103657341 A CN 103657341A CN 201310666043 A CN201310666043 A CN 201310666043A CN 103657341 A CN103657341 A CN 103657341A
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- antioxidant
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Abstract
The invention discloses an anti-oxidation type SO2 absorbing recycle agent. The anti-oxidation type SO2 absorbing recycle agent is characterized in that a 10%-25% sodium sulfite solution is adopted as a main material, waste liquid of industrially-synthesized ethanol amine is adopted as an auxiliary agent, an antioxidant is added, the auxiliary agent in the absorbing recycle agent accounts for 1%-3% of the total mass, the mass concentration of the antioxidant is 5-20ppm, and the antioxidant is one or a mixture of more than two of ethylene diamine tetraacetic acid, metol, sodium thiosulfate, ascorbic acid, vitamin E, 2, 6-di-tert-butyl-phenol, hydroquinone, p-phenylenediamine, anthraquinone-1-ammonium sulphonate. The anti-oxidation type SO2 absorbing recycle agent disclosed by the invention has the advantages that the SO2 absorption rate is high, the absorption time is long, the cycle recycle can be achieved, the absorption efficiency of the absorbent and the absorption capacity of the absorbent to SO2 are effectively increased and the production cost is saved.
Description
Technical field
The invention belongs to SO in industrial smoke
2processing technology field, be specifically related to a kind ofly with sodium sulfite, absorb and reclaim SO in industrial smoke
2method.
Background technology
Power plant, smeltery, chemical plant, paper mill etc. in process of production, can be discharged containing SO
2industrial waste gas, be commonly called as flue gas, atmospheric environment, soil, water and animals and plants etc. are caused to huge pollution.Existing treatment S O
2technology all there is certain one-sidedness, flue gas desulfurization is simple absorption SO
2, sulfur recovery is only just sulfur recovery again, not by since the two effective combination.Sulfur method mainly contains gypsum, soda method, ammonia process, metal oxide method etc., and these sulfur methods can only solve merely SO
2pollution problem, gained byproduct be difficult for to be sold, cheap, and what have also causes secondary pollution, and some operating costs are higher.Sulfur recovery technology mainly adopts Crouse and SCOT technique, but ubiquity investment is high, and emission can not meet the requirement of GB13223-2011 standard.
Sodium sulfite is as SO
2absorbing recovery catalyst is that tail gas, boiler flue gas desulfurization system and sulfur recovery system are combined, and reduces investment, and exhaust emissions is also better than conventional method, meets GB requirement.But sodium sulfite is oxidizable material, in flue gas, contain oxygen, be easily oxidized to sodium sulphate, once sodium sulfite is oxidized to sodium sulphate, will loses completely and absorb SO
2ability, become rubbish and the burden of desulphurization system.Therefore, should reduce as far as possible the oxidation of sodium sulfite, so study a kind of SO of anti-oxidant type
2absorbing recovery catalyst is extremely necessary.
Summary of the invention
Technical problem to be solved by this invention is to overcome sodium sulfite as SO
2absorb the oxidizable shortcoming of recovery catalyst, a kind of anti-oxidant type SO is provided
2absorb recovery catalyst.
Solving the problems of the technologies described above adopted technical scheme is: the sodium sulfite aqueous solution that this absorption recovery catalyst is 10%～25% by mass fraction, the waste liquid of industry synthesizing ethanolamine, antioxidant forms, the waste liquid of industry synthesizing ethanolamine accounts for and absorbs 1%～3% of recovery catalyst gross mass, the mass concentration of antioxidant is 5～20ppm, described antioxidant is disodium ethylene diamine tetraacetate, Mitouer, sodium thiosulfate, ascorbic acid, vitamin E, 2, 6-di-tert-butylphenol, hydroquinones, p-phenylenediamine (PPD), any one in anthraquinone-1-sulfonic acid ammonium or two or more mixtures.
The preferred disodium ethylene diamine tetraacetate of above-mentioned antioxidant, Mitouer, 2, any one in 6-di-tert-butylphenol, hydroquinones, p-phenylenediamine (PPD) or two or more mixtures.
Above-mentioned anti-oxidant type SO
2the preparation method who absorbs recovery catalyst is: the sodium sulfite aqueous solution that is 10%～25% by mass fraction, the waste liquid of industrial synthesizing ethanolamine, antioxidant mix, and obtain anti-oxidant type SO
2absorb recovery catalyst.
Beneficial effect of the present invention is as follows:
1, the present invention is usingd sodium sulfite as absorbing recovery catalyst main body, the waste liquid of industrial synthesizing ethanolamine of take is auxiliary element, select disodium ethylene diamine tetraacetate simultaneously, Mitouer, sodium thiosulfate, ascorbic acid, vitamin E, 2, 6-di-tert-butylphenol, hydroquinones, p-phenylenediamine (PPD), any one in anthraquinone-1-sulfonic acid ammonium or two or more mixture are as antioxidant, three's synergy, can effectively prevent the oxidation of sodium sulfite in flue gas, under identical oxygenation efficiency, with do not add antioxidant and compare, its soak time obviously extends, the highest prolongation more than 2 times, effectively extended the service life of absorbent, improved the absorption efficiency of absorbent and to SO
2absorptive capacity, saved production cost.
2, the present invention absorbs recovery catalyst to SO
2absorptivity can reach 97%～99%, and can recycling use.
3, antioxidant addition of the present invention is less, can not increase cost, can not cause secondary pollution, and can not affect absorbent and reuse time to SO
2absorptive capacity.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in more detail, but the invention is not restricted to these embodiment.
Embodiment 1
With the anti-oxidant type SO of preparation 1000g
2absorption recovery catalyst is example, and it is comprised of the raw material of following quality proportioning:
Mass fraction is 20% sodium sulfite aqueous solution 979.99g
The waste liquid 20g of industry synthesizing ethanolamine
Hydroquinones 0.01g
Its preparation method is: waste liquid, the 0.01g hydroquinones of the sodium sulfite aqueous solution that is 20% by 979.99g mass fraction, 20g industry synthesizing ethanolamine mix, and obtain anti-oxidant type SO
2absorb recovery catalyst.
Embodiment 2
In embodiment 1, the sodium sulfite aqueous solution that mass fraction used is 20% such as uses to replace at the sodium sulfite aqueous solution that quality mass fraction is 25%, and other raw materials and quality thereof are identical with embodiment 1.
Embodiment 3
In embodiment 1, hydroquinones used such as uses to replace at the disodium ethylene diamine tetraacetate of quality, and other raw materials and quality thereof are identical with embodiment 1.
Embodiment 4
In embodiment 1, hydroquinones used such as uses to replace at the ascorbic acid of quality, and other raw materials and quality thereof are identical with embodiment 1.
Embodiment 5
In embodiment 4, the sodium sulfite aqueous solution that mass fraction used is 20% such as uses to replace at the sodium sulfite aqueous solution that quality mass fraction is 25%, and other raw materials and quality thereof are identical with embodiment 4.
Embodiment 6
In embodiment 1, hydroquinones used such as uses to replace at the anthraquinone-1-sulfonic acid ammonium of quality, and other raw materials and quality thereof are identical with embodiment 1.
Embodiment 7
In embodiment 6, the sodium sulfite aqueous solution that mass fraction used is 20% such as uses to replace at the sodium sulfite aqueous solution that quality mass fraction is 25%, and other raw materials and quality thereof are identical with embodiment 6.
Embodiment 8
In embodiment 1, hydroquinones used such as uses to replace at the mixture that Mitouer of quality and the mass ratio of vitamin E are 1:1, and other raw materials and quality thereof are identical with embodiment 1.
Embodiment 9
In embodiment 1, mass fraction used is that 20% sodium sulfite aqueous solution such as uses to replace at the sodium sulfite aqueous solution that quality mass fraction is 25%, hydroquinones used such as uses at 2 of the quality, and 6-di-tert-butylphenol is replaced, and other raw materials and quality thereof are identical with embodiment 1.
Embodiment 10
With the anti-oxidant type SO of preparation 1000g
2absorption recovery catalyst is example, and it is comprised of the raw material of following quality proportioning:
Mass fraction is 20% sodium sulfite aqueous solution 989.995g
The waste liquid 10g of industry synthesizing ethanolamine
P-phenylenediamine (PPD) 0.005g
Its preparation method is identical with embodiment 1.
Embodiment 11
In embodiment 10, p-phenylenediamine (PPD) used such as uses to replace at the Mitouer of quality, and other raw materials and quality thereof are identical with embodiment 10.
Embodiment 12
In embodiment 10, p-phenylenediamine (PPD) used such as uses to replace at the sodium thiosulfate of quality, and other raw materials and quality thereof are identical with embodiment 10.
Embodiment 13
In embodiment 10, p-phenylenediamine (PPD) used such as uses to replace at the vitamin E of quality, and other raw materials and quality thereof are identical with embodiment 10.
Embodiment 14
With the anti-oxidant type SO of preparation 1000g
2absorption recovery catalyst is example, and it is comprised of the raw material of following quality proportioning:
Mass fraction is 10% sodium sulfite aqueous solution 969.98g
The waste liquid 30g of industry synthesizing ethanolamine
P-phenylenediamine (PPD) 0.02g
Its preparation method is identical with embodiment 1.
Embodiment 15
In embodiment 14, p-phenylenediamine (PPD) used such as uses to replace at the mixture that the hydroquinones of quality and the mass ratio of ascorbic acid are 1:1, and other raw materials and quality thereof are identical with embodiment 14.
Embodiment 16
In embodiment 14, p-phenylenediamine (PPD) used such as uses to replace at the mixture that Mitouer of quality and the mass ratio of anthraquinone-1-sulfonic acid ammonium are 1:1, and other raw materials and quality thereof are identical with embodiment 14.
In order to prove beneficial effect of the present invention, the anti-oxidant type SO that inventor adopts embodiment 1～16 to obtain
2absorb recovery catalyst (hereinafter referred to as absorbent of the present invention), and adopt the mixed liquor that does not add the sodium sulfite aqueous solution of antioxidant and the waste liquid of industrial synthesizing ethanolamine in corresponding embodiment as blank sample, with the air pump of capacity 3.2L/min, in absorbent, blast air continuously, interval certain hour sampling and testing SO
4 2-concentration, is oxidized to investigation point with sodium sulfite 20%, calculates absorbent to SO
2soak time, the results are shown in Table 1.
2, air is accounted for to 99%, CO
2account for 1%, SO
2concentration is that the flue gas of 800ppm passes in 250kg absorbent of the present invention, monitors pH value, density, the exhaust emissions concentration of an absorbent per half an hour, and the pH value that passes to absorbent reduces to 6.7 when following, finishes ventilation, calculates absorbent of the present invention to SO
2absorptivity, the results are shown in Table 1.
Table 1 absorbent of the present invention is to SO
2absorptivity and soak time
| Absorb recovery catalyst | SO 2Absorptivity | Blank sample soak time (hour) | Absorbent soak time of the present invention (hour) |
| Embodiment 1 | 99% | 200 | 453 |
| Embodiment 2 | 99% | 230 | 486 |
| Embodiment 3 | 98.5% | 200 | 327 |
| Embodiment 4 | 98.2% | 200 | 323 |
| Embodiment 5 | 99% | 230 | 356 |
| Embodiment 6 | 98.2% | 200 | 330 |
| Embodiment 7 | 99% | 230 | 363 |
| Embodiment 8 | 98.8% | 200 | 423 |
| Embodiment 9 | 99% | 230 | 441 |
| Embodiment 10 | 98.3% | 185 | 321 |
| Embodiment 11 | 98.3% | 185 | 356 |
| Embodiment 12 | 98.5% | 185 | 307 |
| Embodiment 13 | 98.7% | 185 | 295 |
| Embodiment 14 | 97.8% | 128 | 237 |
| Embodiment 15 | 97.8% | 128 | 226 |
| Embodiment 16 | 97.9% | 128 | 228 |
From table 1, absorbent of the present invention is to SO
2absorptivity can reach 97%～99%, and when sodium sulfite 20% is oxidized, absorbent of the present invention is to SO
2soak time do not compare with adding antioxidant, soak time obviously extends, and the highlyest extends to it more than 2 times, has effectively extended the service life of absorbent, has improved the absorption efficiency of absorbent and to SO
2absorptive capacity, saved production cost.In addition, the addition of antioxidant is less, can not cause secondary pollution, and can not affect absorbent and reuse time to SO
2absorptive capacity.
Claims (2)
1. an anti-oxidant type SO
2absorb recovery catalyst, it is characterized in that: the sodium sulfite aqueous solution that this absorption recovery catalyst is 10%～25% by mass fraction, the waste liquid of industrial synthesizing ethanolamine, antioxidant form, the waste liquid of industry synthesizing ethanolamine accounts for and absorbs 1%～3% of recovery catalyst gross mass, the mass concentration of antioxidant is 5～20ppm, described antioxidant is disodium ethylene diamine tetraacetate, Mitouer, sodium thiosulfate, ascorbic acid, vitamin E, 2, any one in 6-di-tert-butylphenol, hydroquinones, p-phenylenediamine (PPD), anthraquinone-1-sulfonic acid ammonium or two or more mixtures.
2. anti-oxidant type SO according to claim 1
2absorb recovery catalyst, it is characterized in that: described antioxidant is disodium ethylene diamine tetraacetate, Mitouer, 2, any one in 6-di-tert-butylphenol, hydroquinones, p-phenylenediamine (PPD) or two or more mixtures.
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| CN201310666043.9A CN103657341B (en) | 2013-12-10 | 2013-12-10 | A kind of anti-oxidative SO 2absorb recovery catalyst |
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| CN103657341A true CN103657341A (en) | 2014-03-26 |
| CN103657341B CN103657341B (en) | 2016-04-06 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012090A (en) * | 2018-07-30 | 2018-12-18 | 大连理工大学 | It is a kind of can oxidation resistant non-aqueous decarbonizing solution for trap carbon dioxide in gas mixture |
| CN114433026A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | SO (SO)2Adsorbing material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11104448A (en) * | 1997-09-30 | 1999-04-20 | Babcock Hitachi Kk | Equipment and method for flue gas desulfurization |
| CN101254392A (en) * | 2007-02-28 | 2008-09-03 | 向瑞先 | Energy-saving type sodium sulphite circulation desulfurizing device and method |
| CN103071367A (en) * | 2013-01-29 | 2013-05-01 | 石家庄学院 | Preparation method and application of ionic liquid for absorbing SO2 |
-
2013
- 2013-12-10 CN CN201310666043.9A patent/CN103657341B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11104448A (en) * | 1997-09-30 | 1999-04-20 | Babcock Hitachi Kk | Equipment and method for flue gas desulfurization |
| CN101254392A (en) * | 2007-02-28 | 2008-09-03 | 向瑞先 | Energy-saving type sodium sulphite circulation desulfurizing device and method |
| CN103071367A (en) * | 2013-01-29 | 2013-05-01 | 石家庄学院 | Preparation method and application of ionic liquid for absorbing SO2 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012090A (en) * | 2018-07-30 | 2018-12-18 | 大连理工大学 | It is a kind of can oxidation resistant non-aqueous decarbonizing solution for trap carbon dioxide in gas mixture |
| CN114433026A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | SO (SO)2Adsorbing material and preparation method thereof |
| CN114433026B (en) * | 2020-10-31 | 2024-02-09 | 中国石油化工股份有限公司 | SO (SO) device 2 Adsorption material and preparation method thereof |
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| CN103657341B (en) | 2016-04-06 |
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Address after: No.61 Xiyan Road, Xi'an City, Shaanxi Province 710054 Patentee after: Shaanxi Chemical Research Institute Co.,Ltd. Address before: No.61 Xiyan Road, Xi'an City, Shaanxi Province 710054 Patentee before: SHAANXI RESEARCH DESIGN INSTITUTE OF PETROLEUM CHEMICAL INDUSTRY |
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