CN109775668A - A kind of sulfur dioxide catalytic reduction device and method - Google Patents
A kind of sulfur dioxide catalytic reduction device and method Download PDFInfo
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- CN109775668A CN109775668A CN201910259080.5A CN201910259080A CN109775668A CN 109775668 A CN109775668 A CN 109775668A CN 201910259080 A CN201910259080 A CN 201910259080A CN 109775668 A CN109775668 A CN 109775668A
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- sulfur dioxide
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- catalytic reduction
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Abstract
The invention discloses a kind of sulfur dioxide catalytic reduction device and method, which includes tower body, and the tower body top is provided with inlet, lower part is provided with air inlet；It is provided with gas outlet, air inlet lower section above inlet and is provided with liquid outlet；Filler is provided between the inlet and air inlet；It is provided with nozzle above the filler, the nozzle is connect with inlet.The present invention overcomes the shortcomings of that existing method handles low concentration sulphur dioxide flue gas, is reacted as catalyst and at a lower temperature using the lower hydrazine hydrate of toxicity, and will not generate other toxicants in reaction.The technology energy efficient absorption, simple and environmentally-friendly, high financial profit.
Description
Technical field
The present invention relates to a kind of device and methods of liquid phase catalytic reduction sulfur dioxide flue gas Recovered sulphur.
Background technique
Low-concentration sulfur dioxide low-concentration sulfur dioxide is multiple from steel, electric power, coloured, petrochemical industry, chemical industry, building materials etc.
Industry has the characteristics that distribution is wide, concentration is low, improvement is difficult and easily forms acid rain and second particle pollutant, seriously endangers ecology
Environment.The concentration of sulfur dioxide is unable to satisfy the requirement of conventional process for preparing sulfuric acid in low concentration sulphur dioxide flue gas, therefore adopts more
It is handled with end treatment method.
The sulphur resource relative shortage in China, supply falls short of demand for a long time for sulphur.This makes China become the maximum sulphur in the whole world
Importer, external dependence degree are high.Sulphur ressource in sulfur dioxide is become elemental sulfur to recycle, can not only effectively be delayed
Solve the situation of China's Sulphur ressource shortage, moreover it is possible to reduce pollution of the sulfur dioxide to environment, while bring certain income for enterprise.
Therefore, how sulfur dioxide to be administered and Sulphur ressource recycling combines, be to realize that China's thermoelectricity, non-ferrous metal metallurgy industry can be held
The important directions of supervention exhibition.
In existing sorption enhanced sulfur dioxide patent, some high industrial applications of energy consumption are more difficult and the solvent toxicity that uses
It is larger, potential threat is caused to the health of operator.A kind of utilize that some patents such as ZL200710035059.4 is proposed vulcanizes
Sodium absorbs SO2The method for preparing sulphur, this method process flow is long, needs high-temperature high-pressure apparatus, at high cost, and in absorption process
There is H2S is generated, and causes environmental pollution.Chinese patent CN102049257A report, makes CO at 320~350 DEG C using catalyst
Realize direct-reduction SO2, but toxic COS can be generated in reaction process, and the sulphur prepared can be adhered to catalyst surface, make
Catalyst poisoning.
Summary of the invention
In view of this, the present invention provides a kind of sulfur dioxide catalytic reduction device and method, overcome prior art processing low
The deficiency of concentration sulfur dioxide flue gas, efficient absorption, simple and environmentally-friendly, high financial profit.
In order to solve the above technical problems, the technical solution of the present invention is as follows: a kind of sulfur dioxide catalytic reduction device, including tower
Body, the tower body top is provided with inlet, lower part is provided with air inlet；It is provided under gas outlet, air inlet above inlet
Side is provided with liquid outlet；Filler is provided between the inlet and air inlet；Nozzle, the spray are provided with above the filler
Mouth is connect with inlet.
It is provided with as an improvement being located above filler in the tower body except water mist plate.By what is be mingled in carbon dioxide
Vapor regelation Cheng Shuihou secondary response again avoids taking away sulfur dioxide and causes atmosphere pollution.
As an improvement described erected straight arranged corrugated plating and formed except water mist plate by several, and adjacent corrugated plate it
Between there are gaps.
As a preference, the filler is by being divided into several groups under upper, and liquid is provided with again between every group of filler
Distributor.Quadratic distribution is carried out to solution using liquid re-distributor, the contact for keeping it more uniform with filler improves reaction effect
Rate.
As an improvement the inlet is connected with liquid storage tank, the air inlet is connected with carbon monoxide generator；Institute
It states gas outlet to communicate with atmosphere, the liquid outlet is communicated with collecting pit.
As a preference, the filler is made of several corrugated platings being vertically arranged；The corrugated plating successively impregnates viscous
Agent, Al-Si colloidal sol are tied, it is then 2-6 hours dry at a temperature of 80-160 DEG C, then drying after selenous acid is impregnated, it is eventually adding water
Close hydrazine.
The present invention also provides a kind of sulfur dioxide catalytic reduction methods, comprising the following steps:
A. organic solvent sulfur dioxide absorption flue gas is utilized；
B. the organic solvent of sulfur dioxide reacts with CO gas absorption, chemical formula are as follows:
C. the filtrate after reaction is subjected to distillation and obtains solid elemental sulfur；
D. it will be dried after the washing of solid elemental sulfur.
As a preference, organic solvent described in step A is n,N-Dimethylformamide, dimethyl sulfoxide, acetonitrile
Or pyridine.
As a preference, the mass ratio of organic solvent and sulfur dioxide is no more than 10: 1 in step A.
As a preference, reaction is using hydrazine hydrate as catalyst, reaction temperature 80-100 in the step B
℃。
The invention has the beneficial effects that: sulfur dioxide catalytic reduction device with above structure and there is above-mentioned step
Rapid sulfur dioxide catalytic reduction method, overcome the shortcomings of existing method handle low concentration sulphur dioxide flue gas, using toxicity compared with
Low hydrazine hydrate is reacted as catalyst and at a lower temperature, and will not generate other toxicants in reacting.It should
Technology energy efficient absorption, simple and environmentally-friendly, high financial profit.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of sulfur dioxide catalytic reduction device in the present invention.
Fig. 2 is the production flow diagram of filler.
Fig. 3 is the flow chart of sulfur dioxide catalytic reduction method in the present invention.
Marked in the figure: 1, liquid storage tank (organic amine+sulfur dioxide)；2, delivery pump；3, flowmeter；4, inlet；5, nozzle；
6, filler；7, support plate；8, liquid re-distributor；9, instrument connection；10, gas distribution grid；11, water mist plate is removed；12, observation panel；
13, air inlet；14, carbon monoxide generator；15, collecting pit (organic amine+sulphur)；16, liquid outlet, 17 tower bodies.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, With reference to embodiment
The present invention is described in further detail.
As shown in Figure 1, the present invention provides a kind of sulfur dioxide catalytic reduction device, including tower body 17, on the tower body 17
Portion is provided with inlet 4, lower part is provided with air inlet 13；It is provided with gas outlet above inlet 4, is provided with below air inlet 13
Liquid outlet 16；Filler 6 is provided between the inlet 4 and air inlet 13；Nozzle 5, the spray are provided with above the filler 6
Mouth 5 is connect with inlet 4.Inlet 4 is connected with liquid storage tank 1, and the air inlet 13 is connected with carbon monoxide generator 14；It is described
Gas outlet is communicated with atmosphere, and the liquid outlet 16 is communicated with collecting pit 15.It is connected between liquid storage tank 1 and inlet 4 using pipeline,
Delivery pump 2 and flowmeter 3 are provided on pipeline.
It is located above filler 6 in tower body 17 and is provided with except water mist plate 11.Except water mist plate 11 erects straight arranged ripple by several
Board group is at and there are gaps between adjacent corrugated plate.
Filler 6 is provided with liquid re-distributor 8 between every group of filler 6 by being divided into several groups under upper.Filler 6 by
Support plate 7 supports.
As shown in Fig. 2, the manufacturing process of filler 6 is as follows: being made of several corrugated platings being vertically arranged；Corrugated plating is by 316L
Or 317L stainless steel is made.The corrugated plating successively impregnates binder, Al-Si colloidal sol, then does at a temperature of 80-160 DEG C
It is 2-6 hours dry, then drying after selenous acid is impregnated, it is eventually adding hydrazine hydrate.
The application is intended to handle low concentration sulphur dioxide flue gas, the sulfur dioxide flue gas from steel,
The gas containing sulfur dioxide that electric power, coloured, petrochemical industry, chemical industry or building material industry generate, the volume content of sulfur dioxide in flue gas
It is 0.01%~4.0%.
It is stored in liquid storage tank 1 after organic solvent (organic amine) sulfur dioxide absorption flue gas, spray is transported to by delivery pump 2
Mixed liquor (organic amine+sulfur dioxide) is uniformly sprayed on filler 6 by mouth 5, nozzle 5, and carbon monoxide is led to by air inlet 13
Enter into tower body 17, carbon monoxide a series of redox reactions occur after entering filler 6 and generate carbon dioxide, organic amine and
Elemental sulfur, carbon dioxide are discharged after rising in tower body 17 by gas outlet, and organic amine and sulphur are then discharged by liquid outlet 16, so
Vacuum distillation organic solvent is condensed recycling afterwards, and remaining solid is elemental sulfur, and washing is dried.
The present invention also provides a kind of sulfur dioxide catalytic reduction methods, include the following steps.
A. organic solvent sulfur dioxide absorption flue gas is utilized；The organic solvent is n,N-Dimethylformamide, diformazan
Base sulfoxide, acetonitrile or pyridine.The mass ratio of organic solvent and sulfur dioxide is no more than 10: 1.
B. the organic solvent of sulfur dioxide reacts with CO gas absorption, chemical formula are as follows:
Using hydrazine hydrate as catalyst, reaction temperature is 80-100 DEG C for reaction.The amount of the substance of catalyst accounts for dioxy
Change the 5%~30% of the amount of sulfur material.Carbon monoxide dosage is 1.5~2.5 times of the amount of sulfur dioxide substance in reaction.It absorbs
Reaction becomes faint yellow from colourless until solution.
C. the filtrate after reaction is subjected to distillation and obtains solid elemental sulfur；
D. it will be dried after the washing of solid elemental sulfur.
Example one:
The mixed liquor (organic amine+sulfur dioxide) that 10kg content of sulfur dioxide is 20% is added in tower body 17, is passed through
Nozzle 5 is uniformly sprayed on filler 6, and being passed through carbon monoxide and keeping temperature in absorption tower is 80-100 DEG C, with carbon monoxide
Entrance and temperature raising, carbon monoxide contacted with sulfur dioxide and heatable catalytic effect under reacted, finally obtain
2.75kg(1.39m3) carbon dioxide and 1kg elemental sulfur.
Example two:
The mixed liquor (organic amine+sulfur dioxide) that 10kg content of sulfur dioxide is 30% is added in tower body 17, is passed through
Nozzle 5 is uniformly sprayed on filler 6, and being passed through carbon monoxide and keeping temperature in absorption tower is 80-100 DEG C, with carbon monoxide
Entrance and temperature raising, carbon monoxide contacted with sulfur dioxide and heatable catalytic effect under reacted, finally obtain
4.125kg(2.1m3) carbon dioxide and 1.5kg elemental sulfur.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as protection scope of the present invention into retouching.
Claims (10)
1. a kind of sulfur dioxide catalytic reduction device, including tower body, it is characterised in that: the tower body top be provided with inlet,
Lower part is provided with air inlet；It is provided with gas outlet, air inlet lower section above inlet and is provided with liquid outlet；The inlet with into
Filler is provided between port；It is provided with nozzle above the filler, the nozzle is connect with inlet.
2. a kind of sulfur dioxide catalytic reduction device according to claim 1, it is characterised in that: be located in the tower body and fill out
Material top is provided with except water mist plate.
3. a kind of sulfur dioxide catalytic reduction device according to claim 1, it is characterised in that: if it is described except water mist plate by
It is dry to erect straight arranged corrugated plating composition, and there are gaps between adjacent corrugated plate.
4. a kind of sulfur dioxide catalytic reduction device according to claim 1, it is characterised in that: the filler is by under upper
It is divided into several groups, and is provided with liquid re-distributor between every group of filler.
5. a kind of sulfur dioxide catalytic reduction device according to claim 1, it is characterised in that: the inlet and liquid storage
Pond is connected, and the air inlet is connected with carbon monoxide generator；The gas outlet is communicated with atmosphere, the liquid outlet and collecting pit
It communicates.
6. a kind of sulfur dioxide catalytic reduction device according to claim 1, it is characterised in that: the filler is by several perpendicular
The corrugated plating composition being directly arranged；The corrugated plating successively impregnates binder, Al-Si colloidal sol, then does at a temperature of 80-160 DEG C
It is 2-6 hours dry, then drying after selenous acid is impregnated, it is eventually adding hydrazine hydrate.
7. a kind of method of sulfur dioxide catalysis reduction, comprising the following steps:
A. organic solvent sulfur dioxide absorption flue gas is utilized；
B. the organic solvent of sulfur dioxide reacts with CO gas absorption, chemical formula are as follows:
C. the filtrate after reaction is subjected to distillation and obtains solid elemental sulfur；
D. it will be dried after the washing of solid elemental sulfur.
8. a kind of method of sulfur dioxide catalysis reduction according to claim 7, it is characterised in that: described in step A
Organic solvent is n,N-Dimethylformamide, dimethyl sulfoxide, acetonitrile or pyridine.
9. a kind of method of sulfur dioxide catalysis reduction according to claim 8, it is characterised in that: organic molten in step A
The mass ratio of agent and sulfur dioxide is no more than 10: 1.
10. a kind of method of sulfur dioxide catalysis reduction according to claim 7, it is characterised in that: in the step B,
Using hydrazine hydrate as catalyst, reaction temperature is 80-100 DEG C for reaction.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB838018A (en) * | 1956-08-28 | 1960-06-22 | Unilever Ltd | Improvements in or relating to the preservation of soap compositions |
| GB1055305A (en) * | 1963-02-01 | 1967-01-18 | Bayer Ag | Process for the production of polymeric hydrazodicarbon amides |
| US3970744A (en) * | 1974-11-07 | 1976-07-20 | Ralph M. Parsons Company | Process for the production of sulfur from sulfur dioxide extracted from gas streams |
| WO2014132087A1 (en) * | 2013-03-01 | 2014-09-04 | Frank Cross Limited | Method for removing sulphur dioxide from gas streams, using titanium dioxide as catalyst |
| CN104310318A (en) * | 2014-10-21 | 2015-01-28 | 中南大学 | Method for recovering sulphur through carrying out liquid-phase catalytic reduction on sulfur dioxide smoke |
| CN104876818A (en) * | 2014-02-27 | 2015-09-02 | 李坚 | Method for reducing inorganic compound by water as hydrogen source or by molten alkali and use thereof |
| CN105628856A (en) * | 2015-12-25 | 2016-06-01 | 北京联合大学 | Luminescent sensitive material catalyzed by benzene and sulfur dioxide |
| CN109052335A (en) * | 2018-07-24 | 2018-12-21 | 上海三夫工程技术有限公司 | A kind of method of sulfur gas reduction Waste Sulfuric Acid sulfur dioxide liquid and sulfuric acid |
| CN209702307U (en) * | 2019-04-01 | 2019-11-29 | 四川中科贝特纳米科技有限公司 | A kind of sulfur dioxide catalytic reduction device |
-
2019
- 2019-04-01 CN CN201910259080.5A patent/CN109775668A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB838018A (en) * | 1956-08-28 | 1960-06-22 | Unilever Ltd | Improvements in or relating to the preservation of soap compositions |
| GB1055305A (en) * | 1963-02-01 | 1967-01-18 | Bayer Ag | Process for the production of polymeric hydrazodicarbon amides |
| US3970744A (en) * | 1974-11-07 | 1976-07-20 | Ralph M. Parsons Company | Process for the production of sulfur from sulfur dioxide extracted from gas streams |
| WO2014132087A1 (en) * | 2013-03-01 | 2014-09-04 | Frank Cross Limited | Method for removing sulphur dioxide from gas streams, using titanium dioxide as catalyst |
| CN104876818A (en) * | 2014-02-27 | 2015-09-02 | 李坚 | Method for reducing inorganic compound by water as hydrogen source or by molten alkali and use thereof |
| CN104310318A (en) * | 2014-10-21 | 2015-01-28 | 中南大学 | Method for recovering sulphur through carrying out liquid-phase catalytic reduction on sulfur dioxide smoke |
| CN105628856A (en) * | 2015-12-25 | 2016-06-01 | 北京联合大学 | Luminescent sensitive material catalyzed by benzene and sulfur dioxide |
| CN109052335A (en) * | 2018-07-24 | 2018-12-21 | 上海三夫工程技术有限公司 | A kind of method of sulfur gas reduction Waste Sulfuric Acid sulfur dioxide liquid and sulfuric acid |
| CN209702307U (en) * | 2019-04-01 | 2019-11-29 | 四川中科贝特纳米科技有限公司 | A kind of sulfur dioxide catalytic reduction device |
Non-Patent Citations (2)
| Title |
|---|
| YANG, BT ET AL: "Selenium-assisted reduction of sulfur dioxide by carbon monoxide in the liquid phase", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》, vol. 56, no. 8, pages 1895 - 1902 * |
| 王学海;方向晨;刘忠生;: "催化还原二氧化硫为单质硫的研究进展", 《化工进展》, no. 07, pages 1209 - 1214 * |
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