CN108434977A - A kind of method of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal - Google Patents
A kind of method of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal Download PDFInfo
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- CN108434977A CN108434977A CN201711188177.9A CN201711188177A CN108434977A CN 108434977 A CN108434977 A CN 108434977A CN 201711188177 A CN201711188177 A CN 201711188177A CN 108434977 A CN108434977 A CN 108434977A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a kind of method of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal, this method uses phosphate ore pulp for absorbing liquid, using catalysis characteristics of the phosphorus ore rich in metal oxides such as Fe, Mg, Mn, to the SO in flue gas2、NOXCarry out catalysis oxidation.Phosphate ore pulp used is that 0.25 ~ 0.75g/mL is prepared according to solid-to-liquid ratio with distilled water by ground phosphate rock, a concentration of 0.07%, the SO of NO in controlling reaction simulation flue gas2A concentration of 0.08%, choose reaction temperature be 25 ~ 60 DEG C, solid-to-liquid ratio be 0.25 ~ 0.75 mL, oxygen content is 10% ~ 30% and airflow rate is 0.15 ~ 0.30L/min, and desulfurization degree reaches as high as 100%, and denitrification rate reaches as high as 67%.This method operating process is simple, and phosphorus ore raw material simplicity is easy to get, and main equipment only needs absorption plant, only needs air blast oxygen blast under process conditions, does not add other equipment, is not necessarily to high temperature and pressure, and operating cost is low.
Description
Technical field
The present invention relates to a kind of methods of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal, belong to atmosphere pollution purification skill
Art field.
Background technology
China's phosphate rock resource is abundant, and in phosphorizing treatment, phosphorus ore is cheap and easy to get, and phosphoric acid and phosphorus compound fertilizer production technology are ripe,
One is in demand.Therefore use the SO of phosphate ore pulp absorption low concentration2And NOXMethod can not only make tail gas up to standard with, environmental protection, and
And a large amount of SO in flue gas is also effectively recycled2And NOX, the slurry that fails after reaction can be used as byproduct and can be used for phosphoric acid processed
With phosphorus composite fertilizer, this method is SO in exhaust gas2And NOXProcessing and recycling opened up new way.
Widely used desulfurization and denitrification integral technology is mainly wet flue gas desulfurization and selectivity outside Now Domestic at present
Catalysis reduction or selective non-catalytic reduction technology denitration combination.Wet flue gas desulfurization efficiency is more than 90%, and selective non-catalytic is also
Former denitrification rate is less than 50%.NO is usually oxidized to NO by wet flue gas simultaneous SO_2 and NO removal technique in gas/liquid section2, or by adding
Enter additive to improve the solubility of NO.The method of wet type simultaneous SO_2 and NO removal mostly be in conceptual phase, including oxidizing process and
Wet type complexometry.Wet type Absorption via Chemical Complexation technique can be but still under test with simultaneous SO_2 and NO removal, influences its commercial Application
Major obstacle be the loss of chelate and metallo-chelate regeneration is difficult, utilization rate is low, technological equipment investment in reaction process
Greatly, the pre-heat treatment flue gas is needed, expensive catalyst and service life is short exists simultaneously NH_3 leakage, the problems such as equipment is perishable.
There is preferable development prospect using liquid phase catalytic oxidation simultaneous SO_2 and NO removal, but liquid phase catalytic oxidation takes off simultaneously
The research of sulphur denitration is still rare at home and abroad, and reason is that the mechanism of transition metal ion catalyst oxidation of NOx is not very bright
Really, catalysis oxidation lye absorb method and heavy metal ion catalyst synergistic effect, the processing of desulphurization denitration waste water and
It is still necessary to be furtherd investigate for the reuse of metallic catalyst.SO in the removing flue gas of liquid solution2And the Flue Gas Control Technology mesh of NOx
It is preceding to be in development.Emulsification yellow phosphorus method desulfurizing and denitrifying process, Fe-EDTA metallo-chelates joint removing SO in recent years2
And NOx techniques etc. are obtained for a degree of development, the research to this field is the heat of domestic and international simultaneous SO_2 and NO removal research
Point.
Desulfurization and denitrification integral process has become the research and development focus of various countries' control smoke pollution, most of desulphurization denitrations one
Body chemical industry skill only rests on conceptual phase, although having there is a small amount of demonstration project application, is constrained since operating cost is higher
Its large-scale promotion application.Exploitation is suitble to China's national situation, low, efficient, byproduct recycling the desulfurization of small investment, operating cost
Denitrification integral technology becomes the emphasis of future development.
It is disclosed in Chinese patent CN106621799A and has invented a kind of method of optic catalytic oxidizing, desulfurizing and denitrifying flue gas simultaneously
And device, this method are that flue gas initially enters VUV Irradiation area, and living radical and smelly is generated under high energy ultraviolet irradiation
Part SO in the oxidable removal flue gas of oxygen2And NOx, then pass through monoblock type photochemical catalyst bed, play photochemical catalytic oxidation and
The synergistic effect of O3 catalytic oxidation makes SO2It is removed by further purification with NOx, spray absorber area is entered back into containing sour vapour flue gas,
The desulphurization denitration product H under absorption2SO4And HNO3It is able to cleaned removing.Flue gas desulfurization and denitrification device is by vacuum ultraviolet spoke
It is formed according to area, monoblock type photochemical catalyst bed and spray absorber area three parts.The catalyst bed of invention design can make 100%
Ultraviolet lighting be mapped to catalyst surface, also intimate 100% catalyst surface can be made to receive ultraviolet lighting, solve tradition
The undesirable problem of the illumination utilization rate in exhaust gas is administered in photocatalysis.But this method operating procedure is complicated, needs in vacuum purple
It is carried out under the conditions of outer, operating cost is higher, and operating condition is harsh.
It is disclosed in Chinese patent CN106606922A and has invented flue gas wet method simultaneous SO_2 and NO removal method, which proposes
A kind of flue gas wet method simultaneous SO_2 and NO removal method, is that flue gas to be clean is passed through absorbing reaction device, in the reactor flue gas with
Absorbing liquid comes into full contact with, NOx, SO in flue gas2Discharged by absorption after-purification, the absorbing liquid be by sodium base desulfurizer with contain
The weight percent of the slurries that chlorine strong oxidizer is configured to, the chloric strong oxidant is sodium base desulfurizer 0.1~0.5%, is inhaled
Treatment fluid can be obtained after the flue gas by receiving liquid.This process simplify the wet desulphurization of sodium base and recovery process, and realize de-
Sulphur denitration is carried out at the same time, and desulfuration efficiency is improved.But this method can introduce new substance, less meet Green Chemistry
Theory.
It is disclosed in Chinese patent CN105289228A and has invented a kind of industrial smoke coordinated desulfurization method of denitration, which carries
A kind of industrial smoke coordinated desulfurization method of denitration is supplied, the method includes flue gases to pass sequentially through three desulphurization denitrations by flue gas
After unit carries out purified treatment, it is emitted into air.Specifically by three step desulfurization denitration methods, including organic amine fusion oxidation
Method, catalytic reduction method and reactive absorption method realize that multiple-unit combines desulphurization denitration.The industrial smoke coordinated desulfurization denitration of the present invention
Method is carried out in an equipment, by the synergistic effect of the desulfurization denitration method, realizes integration desulfurization denitration, reachable
To desulfuration efficiency 95%, denitration efficiency 90%.But this method is operated by three steps, required process equipment and process control are multiple
It is miscellaneous, it is unfavorable for saving man power and material.
In conclusion process equipment and process control needed for the present invention are simple, are conducive to save man power and material, be used
Phosphate ore pulp simplicity be easy to get, can reach the regeneration of resource, substantially reduce enterprise's pollution treatment cost, and do not generate two in operating process
Secondary pollution, desulphurization denitration technology while being a kind of more green, there is higher economy, environmental benefit.Therefore, the present invention has
Important practical advice meaning, is more suitable for promoting.
Invention content
The technical problem to be solved in the present invention is to provide a kind of methods of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal.
In the present invention a kind of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal its specific steps are：
NO, SO of concentration needed for the operation are prepared in experiment using static volumetric method2With the simulated flue gas of oxygen content（Using from steel
The NO gases of bottle（Volume fraction 0.08%, N2Make Balance Air）And SO2Gas（A concentration of 0.08%）And dry air presses certain ratio
Example is filled such as airbag, is uniformly mixed.）；
Gas circuit is connected according to attached drawing, checks air-tightness；Be switched on preheater apparatus, adjusts the temperature parameter of water-bath, for use；
Phosphorus ore accurately is weighed, is configured to test the phosphate ore pulp absorbing liquid of required solid-to-liquid ratio with distilled water;
Absorbing liquid is placed in water-bath, until temperature is to preset temperature, ventilatory response starts, and starts timing, measures gas outlet
Tail gas；
It after to be absorbed, stops the supple of gas or steam, measures the pH of absorbing liquid；
The desulfurization of calculating absorbing liquid and denitration efficiency are simultaneously analyzed.
Description of the drawings
Fig. 1 is the reaction unit figure of this operating method.1. airbag 2. ends 3. mass flowmenter of switch, 4. water bath with thermostatic control
5. 6. drying tube of porous sand absorption tube of pot, 7. flue gas analyzer 8.U types absorption tube, 9. air pump.
Specific implementation mode
In order to better illustrate and implement, elaborate to the present invention below by specific implementation example.
Embodiment 1
Using the phosphorus ore of phosphate fertilizer plant of Yunnan Province at 110 DEG C, 2h is dried, phosphorus ore attrition grinding is sieved to obtain 200 mesh fine graineds, accurately
The phosphorus ore of 30g is weighed in absorption bottle, addition 40mL distilled water is made into phosphate ore pulp, and absorption plant is placed in thermostat water bath, temperature
Degree control is at 25 DEG C, NO gases（Volume fraction 0.08%, N2Make Balance Air）And SO2Gas（A concentration of 0.08%）, oxygen content is
21%, airflow rate is 0.15 L/min, carries out experimental implementation under this condition and reacts 200min.It is surveyed with flue gas analyzer
Export SO2With NO contents, removal efficiency is calculated, the time sustainable 200min that desulfurization degree is 100%, denitrification rate is up to 66%
Time sustainable 146min.
Embodiment 2
Using the phosphorus ore of phosphate fertilizer plant of Yunnan Province at 110 DEG C, 2h is dried, phosphorus ore attrition grinding is sieved to obtain 200 mesh fine graineds, accurately
The phosphorus ore of 20g is weighed in absorption bottle, addition 40mL distilled water is made into phosphate ore pulp, and absorption plant is placed in thermostat water bath, temperature
Degree control is at 25 DEG C, NO gases（Volume fraction 0.08%, N2Make Balance Air）And SO2Gas（A concentration of 0.08%）, oxygen content is
21%, airflow rate is 0.15 L/min, carries out experimental implementation under this condition and reacts 200min.It is surveyed with flue gas analyzer
Export SO2With NO contents, removal efficiency is calculated, the time sustainable 187min that desulfurization degree is 100%, denitrification rate is up to 65%
Time sustainable 151min.
Claims (6)
1. a kind of method of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal, it is characterised in that implement according to the following steps：Experiment
The concentration of required simulation industrial smoke is prepared using static volumetric method；Gas circuit is connected according to Experimental equipment, is checked airtight
Property；Be switched on preheater apparatus, adjusts the temperature parameter of water-bath；The phosphate ore pulp for being configured to test required solid-to-liquid ratio with distilled water absorbs
Absorbing liquid is placed in water-bath by liquid；To temperature to preset temperature, ventilatory response starts, and starts timing；End to be absorbed
Afterwards, it stops the supple of gas or steam, measures the pH of absorbing liquid；Calculate denitration efficiency.
2. a kind of method of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal according to claim 1, it is characterised in that
Desulphurization denitration raw material is ground phosphate rock, and granular size is 200 mesh.
3. according to a kind of method of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal described in claim 1, it is characterised in that
Required temperature control is at 25 DEG C ~ 40 DEG C in operation.
4. according to a kind of method of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal described in claim 1, it is characterised in that
Operation airflow rate is 0.15L/min ~ 0.30L/min.
5. according to a kind of method of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal described in claim 1, it is characterised in that
Operation oxygen content is 10% ~ 30%.
6. according to a kind of method of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal described in claim 1, it is characterised in that
Operation solid-to-liquid ratio is 0.25 ~ 0.75g/mL.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711188177.9A CN108434977A (en) | 2017-11-24 | 2017-11-24 | A kind of method of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal |
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| CN201711188177.9A CN108434977A (en) | 2017-11-24 | 2017-11-24 | A kind of method of phosphate ore pulp liquid phase catalytic oxidation simultaneous SO_2 and NO removal |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675426A (en) * | 2018-12-06 | 2019-04-26 | 昆明理工大学 | It is a kind of using ground phosphate rock and mud phosphorus to the system and method for flue gas desulfurization and denitrification and by-product nitrophosphate fertilizer |
| CN110102180A (en) * | 2019-06-21 | 2019-08-09 | 云南民族大学 | A kind of method of mud Emulphors turbid liquid phase catalytic oxidation simultaneous SO_2 and NO removal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899668A (en) * | 2006-06-30 | 2007-01-24 | 昆明理工大学 | Phosphate rock slurry catalytically oxidaizing process for removing low concentration SO2 |
| CN105056747A (en) * | 2015-08-18 | 2015-11-18 | 昆明尔康科技有限公司 | Process and device for removing SO2 from exhaust gas generated by sulfuric acid production in phosphate chemical enterprise |
| CN106310932A (en) * | 2015-07-07 | 2017-01-11 | 云南民族大学 | Method for removing NO in industrial waste gas by phosphorite slurry phase catalytic oxidation |
-
2017
- 2017-11-24 CN CN201711188177.9A patent/CN108434977A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899668A (en) * | 2006-06-30 | 2007-01-24 | 昆明理工大学 | Phosphate rock slurry catalytically oxidaizing process for removing low concentration SO2 |
| CN106310932A (en) * | 2015-07-07 | 2017-01-11 | 云南民族大学 | Method for removing NO in industrial waste gas by phosphorite slurry phase catalytic oxidation |
| CN105056747A (en) * | 2015-08-18 | 2015-11-18 | 昆明尔康科技有限公司 | Process and device for removing SO2 from exhaust gas generated by sulfuric acid production in phosphate chemical enterprise |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675426A (en) * | 2018-12-06 | 2019-04-26 | 昆明理工大学 | It is a kind of using ground phosphate rock and mud phosphorus to the system and method for flue gas desulfurization and denitrification and by-product nitrophosphate fertilizer |
| CN110102180A (en) * | 2019-06-21 | 2019-08-09 | 云南民族大学 | A kind of method of mud Emulphors turbid liquid phase catalytic oxidation simultaneous SO_2 and NO removal |
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Application publication date: 20180824 |