CN103274366A - Method for efficiently recycling elemental sulfur in process of treating sulfur dioxide flue gas by using sodium sulfide - Google Patents
Method for efficiently recycling elemental sulfur in process of treating sulfur dioxide flue gas by using sodium sulfide Download PDFInfo
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- CN103274366A CN103274366A CN2013101938626A CN201310193862A CN103274366A CN 103274366 A CN103274366 A CN 103274366A CN 2013101938626 A CN2013101938626 A CN 2013101938626A CN 201310193862 A CN201310193862 A CN 201310193862A CN 103274366 A CN103274366 A CN 103274366A
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- flue gas
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- oxidation reduction
- automatic oxidation
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Abstract
The invention discloses a method for efficiently recycling elemental sulfur in a process of treating sulfur dioxide flue gas by using sodium sulfide. The method comprises the following steps of: adding a self-redox catalyst without limiting the ratio of the amount of substance of sodium hydrogen sulfite to the amount of substance of sodium thiosulfate in a process of catalyzing and recycling the sulfur at a low temperature; then stirring and heating to 60-100 DEG C; filtering the self-redox catalyst after the solution becomes light yellow, continuously stirring for reaction for 1-4 hours; filtering and separating to acquire the elemental sulfur; and evaporating, freezing and crystallizing the filtrate to acquire mirabilite. The catalyst has the application advantage of avoiding high-temperature and high-pressure reaction and keeping the ratio of the amount of substance of the sodium hydrogen sulfite to the amount of substance of the sodium thiosulfate to 2:1; the self-redox catalyst can be reused and the recovery rate of the self-redox catalyst is more than 99.5%; the recovery rate of the sulfur is more than 99%; the recovery rate of the mirabilite is more than 60%; the concentration of tail gas SO2 is lower than 50ppm; and therefore, the elemental sulfur can be prepared at a low temperature and at normal pressure, products with high added-value can be recycled, and the tail gas can reach the existing SO2 emission standard.
Description
Technical field
The invention belongs to the environmental protection science field, relate to a kind of sodium sulphite and handle method, especially the catalysis Sulfothiorine of high efficiente callback elemental sulfur in the sulfur dioxide flue gas technology and the method for sodium bisulfite automatic oxidation reduction.
Background technology
It is one of environment protection important contents at present that sulfur dioxide flue gas is administered, and the expection sulfur dioxide emissions reduce 8% in country " the 12 " planning, so flue gas desulfurization becomes environmental protection field urgent problem.
Desulfurization technology can be divided three classes now: (1) wet method: limestone/lime-gypsum method, sea water desulfuration method, metal oxide-magnesium oxide method, two alkaline process, soda method, ammonia absorption process, biological desulphurization method and film base gas absorption method etc.(2) dry method: active carbon adsorption, electronic beam method, corona discharge pulse flue gas desulfurization technique and contact oxidation method etc.(3) semidrying: spray-drying process, NID (New Integrated Desulfurization) cyclic semidry process doctor treatment, return-flow type circulating fluid-bed desulfurization technology etc.Above method all exists the sweetener investment bigger, and the environmental protection working cost of great number makes problems such as manufacturing enterprise can't bear the heavy load.And the product after these method desulfurization often is difficult to handle, and formed new waste pollution problem.And the sodium sulphite absorption process can be with SO
2Flue gas is produced S simple substance, and solid waste is little, the desulfurization degree height, and whole flow process is a closed cycle operation, and the reagent input amount is less, and adding product is the S simple substance of economically valuable, and total cost of investment is less.But the committed step of producing S simple substance in this technological process is Sulfothiorine and sodium bisulfite the automatic oxidation reduction reaction takes place in the autoclave of High Temperature High Pressure, it is bigger to consume energy.Therefore, need to consider that the automatic oxidation reduction Application of Catalyst is with energy-saving and cost-reducing.
The present invention proposes the method that a kind of sodium sulphite is handled high efficiente callback elemental sulfur in the sulfur dioxide flue gas technology, carry out automatic oxidation reduction prepared in reaction elemental sulfur after especially absorbing the sulfur dioxide flue gas that power plant and metallurgical works discharge at sodium sulfide solution, at low temperatures in Sulfothiorine and sodium bisulfite mixing solutions, add the automatic oxidation reduction catalyzer, be heated with stirring to 60-100 ℃ then, solution presents faint yellow after-filtration automatic oxidation reduction catalyzer, continued stirring reaction 1-4 hour, filtering separation obtains elementary sulfur, filtrate evaporative freezing crystallization obtains saltcake, and its catalyzed reaction formula is shown in (1) (2).This Application of Catalyst advantage is that High Temperature High Pressure (temperature 120-240 ℃ and autoclave) and the sodium bisulfite amount of substance that can avoid patent CN100413565C to reclaim in the process of elemental sulfur are necessary for 2:1 with Sulfothiorine amount of substance ratio, restive, otherwise influence the rate of recovery of its elemental sulfur.The automatic oxidation reduction catalyzer can reuse and the rate of recovery is more than 99.5%, and the rate of recovery of sulphur can reach more than 99%, and the saltcake rate of recovery is more than 60%, tail gas SO
2Concentration is lower than 50ppm.Can reach the low-temperature atmosphere-pressure desulfurization and reclaim the purpose of high value added product, tail gas also can reach existing SO
2Emission standard.
Na
2S
2O
3+2NaHSO
3=2S+2Na
2SO
4+H
2O （1）
Na
++3NaHSO
3=S+2Na
2SO
4+H
++H
2O （2）
3Na
2S
2O
3+2H
+=4S+2Na
2SO
4+2Na
++H
2O （3）
Summary of the invention
The purpose of this invention is to provide a kind of sodium sulphite and handle the method for high efficiente callback elemental sulfur in the sulfur dioxide flue gas technology.Utilize catalyzer can catalysis Sulfothiorine and sodium bisulfite generation automatic oxidation reduction react to prepare the high value added product elemental sulfur, but the rate of recovery of bonding prime element sulphur and reach the existing SO of tail gas also
2Emission standard can be avoided the High Temperature High Pressure (temperature 120-240 ℃ and autoclave) among the patent CN100413565C, is beneficial to save energy and reduce the cost.
A kind of sodium sulphite is handled the method for high efficiente callback elemental sulfur in the sulfur dioxide flue gas technology, utilize sodium sulfide solution to absorb sulfur dioxide flue gas, add automatic oxidation reduction catalyzer 0.5g/L-5g/L, be heated with stirring to 60-100 ℃ then, solution presents faint yellow after-filtration automatic oxidation reduction catalyzer, continued stirring reaction 1-4 hour, filtering separation obtains elementary sulfur, and filtrate evaporative freezing crystallization obtains saltcake.
Described sulfur dioxide flue gas comprises the flue gas that contains sulfurous gas that power plant or metallurgical works discharge.
The temperature of solution is 15-30 ℃ before the adding automatic oxidation reduction catalyzer.
Described automatic oxidation reduction catalyzer comprises one or more in sulphur powder, selenium powder and the tellurium powder, and particle diameter is 10nm-200 μ m.
A kind of sodium sulphite that the present invention proposes is handled the method for high efficiente callback elemental sulfur in the sulfur dioxide flue gas technology, carry out automatic oxidation reduction prepared in reaction elemental sulfur after especially absorbing the sulfur dioxide flue gas that power plant and metallurgical works discharge at sodium sulfide solution, under the low temperature in Sulfothiorine and sodium bisulfite mixing solutions, add the automatic oxidation reduction catalyzer, be heated with stirring to 60-100 ℃ then, solution presents faint yellow after-filtration automatic oxidation reduction catalyzer, continued stirring reaction 1-4 hour, filtering separation obtains elementary sulfur.If the amount of substance ratio of the present invention's sodium bisulfite and Sulfothiorine is greater than 2:1, its catalyzed reaction formula is as (1) (2), shown in; If the amount of substance ratio equals 2:1, (1) so only reacts; Therefore if the amount of substance ratio is less than 2:1, its catalyzed reaction formula is (1) (3), can not limit the amount of substance ratio of sodium bisulfite and Sulfothiorine.The catalytic mechanism of catalyzer of the present invention induces element sulphur in the growth of seed surface active sites for to serve as crystal seed with sulphur with main group element, and reaction (1) (2) (3) is carried out to the right.In a word, Application of Catalyst advantage of the present invention is that High Temperature High Pressure (temperature 120-240 ℃ and autoclave) and the sodium bisulfite amount of substance that can avoid patent CN100413565C to reclaim in the process of elemental sulfur are necessary for 2:1 with Sulfothiorine amount of substance ratio, restive, otherwise influence the rate of recovery of its elemental sulfur.The automatic oxidation reduction catalyzer can reuse and the rate of recovery is more than 99.5%, and the rate of recovery of sulphur can reach more than 99%, and the saltcake rate of recovery is more than 60%, tail gas SO
2Concentration is lower than 50ppm.Can reach the low-temperature atmosphere-pressure desulfurization and reclaim the purpose of high value added product, tail gas also can reach existing SO
2Emission standard is carried out through engineering approaches flue gas Processing Test for next step and is provided support.The present invention uses the heavy industrialization of realizing flue gas desulfurization and is significant.
Embodiment:
The invention will be further described below in conjunction with embodiment, rather than limitation of the present invention.
Embodiment 1: simple substance selenium powder catalysis Sulfothiorine and sodium bisulfite automatic oxidation reduction
The Na of 40g/L
2S solution 500ml absorbs the SO of 1795mg/L
2It is to pack into behind 2.8 the solution in the reactor that the back forms the pH value, detecting sodium bisulfite and Sulfothiorine amount of substance ratio is 3.05, add 10g automatic oxidation reduction catalyzer selenium powder then, particle diameter 20 μ m, heated and stirred during to 90 ℃ of solution temperatures solution present faint yellow, filtration washing obtains automatic oxidation reduction catalyzer selenium powder, reclaim selenium powder 9.98g, the rate of recovery 99.8%, continue then solution was carried out heated and stirred 1 hour, obtain elemental sulfur powder 16.35g(and can only obtain sulphur powder 12.99g in theory as adopting the high temperature and high pressure method among the patent CN100413565C), the solution freezing and crystallizing obtains saltcake 43.63g, sulfur recovery rate 99.65%.Tail gas detects through flue gas analyzing apparatus and is 45ppm, and the saltcake rate of recovery 63.50% illustrates to have automatic oxidation reduction catalytic effect and product recovery rate preferably.
Embodiment 2: simple substance tellurium powder catalysis Sulfothiorine and sodium bisulfite automatic oxidation reduction
The Na of 60g/L
2S solution 500ml absorbs the SO of 1795mg/L
2It is to pack into behind 2.6 the solution in the reactor that the back forms the pH value, detecting sodium bisulfite and Sulfothiorine amount of substance ratio is 1.1, add 10g automatic oxidation reduction catalyzer tellurium powder then, particle diameter 27 μ m, heated and stirred during to 80 ℃ of solution temperatures solution present faint yellow, filtration washing obtains automatic oxidation reduction catalyzer tellurium powder, reclaim tellurium powder 9.97g, the rate of recovery 99.7%, continue then solution was carried out heated and stirred 2 hours, obtain elemental sulfur powder 24.41g(and can only obtain sulphur powder 12.30g in theory as adopting the high temperature and high pressure method among the patent CN100413565C), the solution freezing and crystallizing obtains saltcake 63.91g, sulfur recovery rate 99.18%.Tail gas detects through flue gas analyzing apparatus and is 48ppm, and the saltcake rate of recovery 62.01% illustrates to have automatic oxidation reduction catalytic effect and product recovery rate preferably.
Embodiment 3: simple substance tellurium powder catalysis Sulfothiorine and sodium bisulfite automatic oxidation reduction
The Na of 40g/L
2S solution 500ml absorbs the SO of 1795mg/L
2It is to pack into behind 2.7 the solution in the reactor that the back forms the pH value, detecting sodium bisulfite and Sulfothiorine amount of substance ratio is 2.1, add 10g automatic oxidation reduction catalyzer sulphur powder then, particle diameter 25 μ m, heated and stirred during to 85 ℃ of solution temperatures solution present faint yellow, filtration washing obtains automatic oxidation reduction catalyzer sulphur powder, reclaim sulphur powder 9.95g, the rate of recovery 99.5%, continue then solution was carried out heated and stirred 3 hours, obtain elemental sulfur powder 16.33g(and can only obtain sulphur powder 16.41g in theory as adopting the high temperature and high pressure method among the patent CN100413565C), the solution freezing and crystallizing obtains saltcake 42.25g, sulfur recovery rate 99.50%.Tail gas detects through flue gas analyzing apparatus and is 49ppm, and the saltcake rate of recovery 61.50% illustrates to have automatic oxidation reduction catalytic effect and product recovery rate preferably.
Claims (4)
1. a sodium sulphite is handled the method for high efficiente callback elemental sulfur in the sulfur dioxide flue gas technology, it is characterized in that, utilize sodium sulfide solution to absorb sulfur dioxide flue gas, add automatic oxidation reduction catalyzer 0.5g/L-5g/L, be heated with stirring to 60-100 ℃ then, solution presents faint yellow after-filtration automatic oxidation reduction catalyzer, continues stirring reaction 1-4 hour, filtering separation obtains elementary sulfur, and filtrate evaporative freezing crystallization obtains saltcake.
2. method according to claim 1 is characterized in that, described sulfur dioxide flue gas comprises the flue gas that contains sulfurous gas that power plant or metallurgical works discharge.
3. method according to claim 1 is characterized in that, the temperature of solution is 15-30 ℃ before the adding automatic oxidation reduction catalyzer.
4. method according to claim 1 is characterized in that, described automatic oxidation reduction catalyzer comprises one or more in sulphur powder, selenium powder and the tellurium powder, and particle diameter is 10nm-200 μ m.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430111A (en) * | 2016-09-18 | 2017-02-22 | 江苏德义通环保科技有限公司 | Method for preparing sulfur by recycling sulfur dioxide from flue gas |
| CN115159464A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for preparing elemental sulfur by catalyzing bisulfite with sulfur-carbon composite material |
| CN115159467A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for synthesizing catalyst based on ammonia circulation and catalytically recovering elemental sulfur from sulfur dioxide flue gas |
| CN115159588A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for catalytically recovering elemental sulfur and ammonium ferrous sulfate from sulfur dioxide flue gas |
| CN115159466A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for resourceful treatment of sulfur dioxide flue gas |
| CN115159468A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for preparing elemental sulfur by catalyzing bisulfite through sulfur deposition activated carbon |
| CN115178274A (en) * | 2021-04-02 | 2022-10-14 | 中冶长天国际工程有限责任公司 | Preparation method and application of sulfur-carrying activated carbon |
| CN115180752A (en) * | 2021-04-02 | 2022-10-14 | 中冶长天国际工程有限责任公司 | Desalination method for SRG washing wastewater by catalyzing with sulfur-containing activated carbon |
| CN115180753A (en) * | 2021-04-02 | 2022-10-14 | 中冶长天国际工程有限责任公司 | Method and system for catalytic desalting of SRG washing wastewater |
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| CN101053740A (en) * | 2007-06-05 | 2007-10-17 | 中南大学 | Treating method for sulphur dioxide flue gas |
| CN102862962A (en) * | 2012-10-16 | 2013-01-09 | 中南大学 | Application of elementary-substance selenium as catalyzer |
-
2013
- 2013-05-23 CN CN2013101938626A patent/CN103274366A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101053740A (en) * | 2007-06-05 | 2007-10-17 | 中南大学 | Treating method for sulphur dioxide flue gas |
| CN102862962A (en) * | 2012-10-16 | 2013-01-09 | 中南大学 | Application of elementary-substance selenium as catalyzer |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430111A (en) * | 2016-09-18 | 2017-02-22 | 江苏德义通环保科技有限公司 | Method for preparing sulfur by recycling sulfur dioxide from flue gas |
| CN115159464A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for preparing elemental sulfur by catalyzing bisulfite with sulfur-carbon composite material |
| CN115159467A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for synthesizing catalyst based on ammonia circulation and catalytically recovering elemental sulfur from sulfur dioxide flue gas |
| CN115159588A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for catalytically recovering elemental sulfur and ammonium ferrous sulfate from sulfur dioxide flue gas |
| CN115159466A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for resourceful treatment of sulfur dioxide flue gas |
| CN115159468A (en) * | 2021-04-02 | 2022-10-11 | 中冶长天国际工程有限责任公司 | Method for preparing elemental sulfur by catalyzing bisulfite through sulfur deposition activated carbon |
| CN115178274A (en) * | 2021-04-02 | 2022-10-14 | 中冶长天国际工程有限责任公司 | Preparation method and application of sulfur-carrying activated carbon |
| CN115180752A (en) * | 2021-04-02 | 2022-10-14 | 中冶长天国际工程有限责任公司 | Desalination method for SRG washing wastewater by catalyzing with sulfur-containing activated carbon |
| CN115180753A (en) * | 2021-04-02 | 2022-10-14 | 中冶长天国际工程有限责任公司 | Method and system for catalytic desalting of SRG washing wastewater |
| CN115178274B (en) * | 2021-04-02 | 2023-12-29 | 中冶长天国际工程有限责任公司 | Preparation method and application of sulfur-carrying activated carbon |
| CN115180752B (en) * | 2021-04-02 | 2023-12-29 | 中冶长天国际工程有限责任公司 | Desalination method for SRG washing wastewater by catalyzing sulfur-containing activated carbon |
| CN115159468B (en) * | 2021-04-02 | 2023-12-29 | 中冶长天国际工程有限责任公司 | Method for preparing elemental sulfur by catalyzing bisulphite through sulfur deposited active carbon |
| CN115159467B (en) * | 2021-04-02 | 2023-12-29 | 中冶长天国际工程有限责任公司 | Method for synthesizing catalyst based on ammonia circulation and catalyzing and recycling elemental sulfur by sulfur dioxide flue gas |
| CN115159464B (en) * | 2021-04-02 | 2023-12-29 | 中冶长天国际工程有限责任公司 | Method for preparing elemental sulfur by catalyzing bisulphite with sulfur-carbon composite material |
| CN115159466B (en) * | 2021-04-02 | 2023-12-29 | 中冶长天国际工程有限责任公司 | Method for recycling sulfur dioxide flue gas |
| CN115159588B (en) * | 2021-04-02 | 2023-12-29 | 中冶长天国际工程有限责任公司 | Method for catalytically recycling elemental sulfur and ferrous ammonium sulfate from sulfur dioxide flue gas |
| CN115180753B (en) * | 2021-04-02 | 2023-12-29 | 中冶长天国际工程有限责任公司 | Method for catalyzing and desalting SRG washing wastewater and system for catalyzing and desalting SRG washing wastewater |
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Inventor after: Qin Yihong Inventor after: He Hanbing Inventor after: Yang Yulong Inventor before: He Hanbing |
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Application publication date: 20130904 |