CN109173638A - Low temperature NO oxidant and preparation method thereof - Google Patents
Low temperature NO oxidant and preparation method thereof Download PDFInfo
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- CN109173638A CN109173638A CN201811280762.6A CN201811280762A CN109173638A CN 109173638 A CN109173638 A CN 109173638A CN 201811280762 A CN201811280762 A CN 201811280762A CN 109173638 A CN109173638 A CN 109173638A
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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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
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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
- B01D53/77—Liquid phase processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
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Abstract
The invention belongs to oxidation of nitric oxide agent technical fields；More particularly to a kind of low temperature NO oxidant and preparation method thereof.For existing NO oxidant, that there are oxidation effectivenesses in low temperature and when NO concentration is lower is bad, the inefficient problem of oxidation and denitration, the present invention provides a kind of low temperature NO oxidant, composition includes: at least two in sodium hypochlorite, sodium chlorite, sodium chlorate or sodium perchlorate.The present invention also provides a kind of preparation methods of above-mentioned oxidant, the following steps are included: weighing at least two in sodium hypochlorite, sodium chlorite, sodium chlorate or sodium perchlorate by weight ratio, be dissolved in the water wiring solution-forming, and adjustment solution ph is 2~9, obtains low temperature NO oxidant.Oxidant of the present invention has stronger oxidability to NO, fast with the reaction rate of low concentration of NO, and oxidation efficiency is high, at low cost.Preparation method process of the present invention is fast, easy to operate, is suitable for promoting.
Description
Technical field
The invention belongs to oxidation of nitric oxide agent technical fields；More particularly to a kind of low temperature NO oxidant and its preparation side
Method.
Background technique
With the improvement of people ' s living standards with the demand of economic development, China is more and more tighter to the emission request of pollutant
Lattice.The it is proposed of implementation and the minimum discharge requirement of effluent charge in 2018, so that iron and steel enterprise faces huge environmental protection pressure.It is existing
The discharge standard of sintering flue gas: SO2Limit value 200mg/m3、NOXLimit value 300mg/m3, particulate matter limit value 30mg/m3, i.e., by implementation
Minimum discharge standard: SO2Limit value 35mg/m3、NOXLimit value 50mg/m3, particulate matter limit value 10mg/m3, each pollution in standard adjustment front and back
The concentration of emission of object declines by a big margin, and existing sintering flue gas desulfurization or denitration technology are not easy to meet minimum discharge requirement, especially
It is that sintering flue gas denitration technology is not mature enough compared with desulfurization technology, technical method is limited, by NOXLimit value drops to 50mg/m3
In the presence of great challenge.
Patent CN 107983119A discloses a kind of dry desulfurization method of denitration that oxidation is forced based on ozone, by former cigarette
Gas is preprocessed, and dustiness is made to be reduced to 10~30mg/Nm3, pretreated flue gas contacts strong to carry out with gas ozoniferous
Oxygenerating, oxidation flue gas and absorbent magnesia dry powder enter recirculating fluidized bed after mixing, water spray achievees the purpose that desulphurization denitration.
This method is more demanding to the dosage control of ozone, cannot be excessive, and ozone is easy escape, and discharged gas fume is blue, the row of being unsatisfactory for
Put requirement.
Patent CN 108176208A discloses a kind of efficient wet denitration agent for cooperating preposition oxidation technology, the denitration
Agent is dissolved in water according to certain quality proportioning and is formed by absorbent body agent, pH adjusting agent and absorption maintenance three substance of agent, can
To carry out NO to flue gas after oxidationXEfficient removal.NO_x Reduction by Effective described in this method is for the flue gas after oxidation, the denitration
The nitric oxide production ability of agent non-oxidation, only absorbent；This method does not suggest that the technology of oxidation of nitric oxide.
Therefore, that there are oxidation effectivenesses in low temperature and when NO concentration is lower is bad, oxidation and denitration effect for existing NO oxidant
The not high defect of rate.
Summary of the invention
The technical problem to be solved in the present invention are as follows: existing NO oxidant has oxidation effect in low temperature and when NO concentration is lower
Fruit is bad, the inefficient problem of oxidation and denitration.
The technical solution of present invention solution above-mentioned technical problem are as follows: a kind of low temperature NO oxidant is provided.
The composition of low temperature NO oxidant of the present invention includes: sodium hypochlorite, sodium chlorite, sodium chlorate or sodium perchlorate
In at least two.
Wherein, in above-mentioned low temperature NO oxidant, the material quality is than at least meeting following one:
When two kinds of raw materials mix: the sodium hypochlorite: sodium chlorite=1~10 ︰ 1；The sodium hypochlorite: chloric acid
Sodium=0.5~15 ︰ 1；The sodium hypochlorite: sodium perchlorate=0.1~20 ︰ 1；The sodium chlorite: sodium chlorate=1~
15 ︰ 1；The sodium chlorite: sodium perchlorate=1~10 ︰ 1；The sodium chlorate: sodium perchlorate=1~5 ︰ 1；
When three kinds of raw materials mix, the sodium hypochlorite: sodium chlorite: 0.5~15 ︰ 1 of sodium chlorate=0.5~15 ︰；Institute
The sodium hypochlorite stated: sodium chlorite: 0.5~15 ︰ 1 of sodium perchlorate=1~10 ︰；The sodium chlorite: sodium chlorate: perchloric acid
0.5~10 ︰ 1 of sodium=1~10 ︰；The sodium hypochlorite: sodium chlorate: 1~5 ︰ 1 of sodium perchlorate=0.5~15 ︰；
When four kinds of raw materials mix, the sodium hypochlorite: sodium chlorite: sodium chlorate: the ︰ of sodium perchlorate=1~20 0.5~
15 ︰, 0.5~15 ︰ 1.
Preferably, the group of above-mentioned low temperature NO oxidant becomes sodium hypochlorite and mixes with sodium chlorite by weight 4 ︰ 1.
Preferably, the group of above-mentioned low temperature NO oxidant becomes sodium hypochlorite, sodium chlorite and sodium chlorate and/or sodium perchlorate
Mixture.
Preferably, in said mixture, when group becomes sodium hypochlorite, sodium chlorite and sodium chlorate, the matter of three kinds of raw materials
Amount is than being 4 ︰, 1 ︰ 0.3.
When group becomes sodium hypochlorite, sodium chlorite and sodium perchlorate, the mass ratio of three kinds of raw materials is 4 ︰, 1 ︰ 0.2.
When group becomes sodium hypochlorite, sodium chlorite, sodium chlorate and sodium perchlorate, the mass ratio of four kinds of raw materials is 4 ︰, 1 ︰
0.3 ︰ 0.2.
The present invention also provides a kind of preparation methods of above-mentioned low temperature NO oxidant, comprising the following steps:
At least two in sodium hypochlorite, sodium chlorite, sodium chlorate or sodium perchlorate are weighed by weight ratio, are dissolved in water
Middle wiring solution-forming, adjustment solution ph are 2~9, obtain low temperature NO oxidant.
Wherein, in the preparation method of above-mentioned low temperature NO oxidant, the solution concentration is 1~100g/L.
Wherein, in the preparation method of above-mentioned low temperature NO oxidant, the solution ph is 7.
The invention has the benefit that
The present invention provides a kind of low temperature NO oxidant, which is sodium hypochlorite, sodium chlorite, sodium chlorate or high chlorine
At least two compositions in sour sodium, oxidant of the present invention have stronger oxidability to NO, can be oxidized to intractable NO
Tractable high-valence state nitrogen oxides, fast with the reaction rate of low concentration of NO, oxidation efficiency is high, at low cost.The present invention also provides
The preparation method of above-mentioned low temperature NO oxidant, preparation method process is fast, easy to operate, is suitable for promoting.
Specific embodiment
The present invention provides a kind of low temperature NO oxidant, composition includes: sodium hypochlorite, sodium chlorite, sodium chlorate or high chlorine
At least two in sour sodium.
Wherein, in above-mentioned low temperature NO oxidant, the material quality is than at least meeting following one:
When two kinds of raw materials mix: the sodium hypochlorite: sodium chlorite=1~10 ︰ 1；The sodium hypochlorite: chloric acid
Sodium=0.5~15 ︰ 1；The sodium hypochlorite: sodium perchlorate=0.1~20 ︰ 1；The sodium chlorite: sodium chlorate=1~
15 ︰ 1；The sodium chlorite: sodium perchlorate=1~10 ︰ 1；The sodium chlorate: sodium perchlorate=1~5 ︰ 1；
When three kinds of raw materials mix, the sodium hypochlorite: sodium chlorite: 0.5~15 ︰ 1 of sodium chlorate=0.5~15 ︰；Institute
The sodium hypochlorite stated: sodium chlorite: 0.5~15 ︰ 1 of sodium perchlorate=1~10 ︰；The sodium chlorite: sodium chlorate: perchloric acid
0.5~10 ︰ 1 of sodium=1~10 ︰；The sodium hypochlorite: sodium chlorate: 1~5 ︰ 1 of sodium perchlorate=0.5~15 ︰；
When four kinds of raw materials mix, the sodium hypochlorite: sodium chlorite: sodium chlorate: the ︰ of sodium perchlorate=1~20 0.5~
15 ︰, 0.5~15 ︰ 1.
It is existing using sodium hypochlorite, sodium chlorite, sodium chlorate and sodium perchlorate separately as the effect of the oxidation of oxidant
All bad, oxidability is sodium chlorite > sodium hypochlorite > sodium chlorate > sodium perchlorate.The present invention is by by sodium hypochlorite, Asia
Sodium chlorate, sodium chlorate and perchloric acid are reasonably cooperated, and are screened and obtained the proportion of each raw material, and a kind of novel low temperature is obtained
The effect of NO oxidant, oxidation and denitration is good, and denitration efficiency can reach 80% or more.
Preferably, in order to improve the efficiency of oxidation and denitration, the generation of oxidizing substance, above-mentioned low temperature NO oxidant are promoted
Group become sodium hypochlorite and sodium chlorite 4 ︰ 1 by weight and mix.
Preferably, in order to improve the efficiency of oxidation and denitration, the generation of oxidizing substance, above-mentioned low temperature NO oxidant are promoted
Group become the mixture of sodium hypochlorite, sodium chlorite and sodium chlorate and/or sodium perchlorate.
Preferably, in said mixture, when group becomes sodium hypochlorite, sodium chlorite and sodium chlorate, the matter of three kinds of raw materials
Amount is than being 4 ︰, 1 ︰ 0.3.
When group becomes sodium hypochlorite, sodium chlorite and sodium perchlorate, the mass ratio of three kinds of raw materials is 4 ︰, 1 ︰ 0.2.
When group becomes sodium hypochlorite, sodium chlorite, sodium chlorate and sodium perchlorate, the mass ratio of four kinds of raw materials is 4 ︰, 1 ︰
0.3 ︰ 0.2.
The present invention also provides a kind of preparation methods of above-mentioned low temperature NO oxidant, comprising the following steps:
At least two in sodium hypochlorite, sodium chlorite, sodium chlorate or sodium perchlorate are weighed by weight ratio, are dissolved in water
Middle wiring solution-forming, adjustment solution ph are 2~9, obtain low temperature NO oxidant.
Wherein, in the preparation method of above-mentioned low temperature NO oxidant, the solution concentration is 1~100g/L.
Wherein, in the preparation method of above-mentioned low temperature NO oxidant, the solution ph is 7.Inventors have found that pH value of solution exists
When 2~9, denitration efficiency is attained by that 80% or more, pH is lower, and denitration efficiency increases, but improves few, but adjusts too low
PH be easier to corrode equipment, and increase cost, for two aspect effect of overall balance, currently preferred solution ph is 7.
Explanation will be further explained to a specific embodiment of the invention by embodiment below, but do not indicated this
The protection scope of invention is limited in range described in embodiment.
Embodiment 1 prepares low temperature NO oxidant of the present invention
The low temperature NO oxidant that secure ph is 9, volume 200mL, concentration are 1g/L.Sodium hypochlorite in mass ratio: sub-
Sodium chlorate=4:1 weighs raw material, and dissolves one by one in deionized water, uses concentration for 0.01mol/ after raw material is completely dissolved
The hydrochloric acid solution of L adjusts pH value to 9.
Evaluation of the low temperature NO oxidant that embodiment 1 is prepared to NO oxidation effectiveness: flue gas flow 1600mL/min, instead
26 DEG C of temperature are answered, O in former flue gas2、SO2, NO concentration be respectively 16.8%, 500mg/m3、300mg/m3, tail gas after reaction
Middle SO2, NO concentration be respectively 0mg/m3、54mg/m3, the removal efficiency of NO is 85%.
Embodiment 2 prepares low temperature NO oxidant of the present invention
The low temperature NO oxidant that secure ph is 7, volume 200mL, concentration are 1g/L.Sodium chlorite in mass ratio: chlorine
Sour sodium=3:1 weighs raw material, and dissolves one by one in deionized water, uses concentration for 0.01mol/L after raw material is completely dissolved
Hydrochloric acid solution adjust pH value to 7.
The evaluation for the oxidizing effect of low temperature NO that embodiment 2 is prepared: flue gas flow 1600mL/min, reaction temperature
30 DEG C are spent, O in former flue gas2、SO2, NO concentration be respectively 16.8%, 500mg/m3、300mg/m3, SO in the tail gas after reaction2、
The concentration of NO is respectively 0mg/m3、30mg/m3, the removal efficiency of NO is 90%.
Embodiment 3 prepares low temperature NO oxidant of the present invention
The low temperature NO oxidant that secure ph is 7, volume 1.5L, concentration are 25/L.Sodium chlorite in mass ratio: high chlorine
Sour sodium=5:1 weighs raw material, and dissolves one by one in deionized water, uses concentration for 0.1mol/L's after raw material is completely dissolved
Hydrochloric acid solution adjusts pH value to 7.
The evaluation for the oxidizing effect of low temperature NO that embodiment 3 is prepared: flue gas flow 8L/min, reaction temperature 30
DEG C, O in former flue gas2、SO2, NO concentration be respectively 16.8%, 500mg/m3、300mg/m3, SO in the tail gas after reaction2, NO
Concentration is respectively 0mg/m3、24mg/m3, the removal efficiency of NO is 92%.
Embodiment 4 prepares low temperature NO oxidant of the present invention
The low temperature NO oxidant that secure ph is 50g/L in 7 or so, volume 3L, concentration.Sodium hypochlorite in mass ratio:
Sodium chlorite: sodium chlorate=4:1:0.3 weighs raw material, and dissolves one by one in deionized water, is added after solute is completely dissolved
Concentration is the hydrochloric acid solution of 0.1mol/L, adjusts pH value 7 or so.
The evaluation for the oxidizing effect of low temperature NO that embodiment 4 is prepared: flue gas flow 15L/min, reaction temperature
28 DEG C, O in former flue gas2、SO2, NO concentration be respectively 16.8%, 500mg/m3、300mg/m3, in the tail gas flue gas after reaction
SO2, NO concentration be respectively 0mg/m3、6mg/m3, the removal efficiency of NO is 98%.
Embodiment 5 prepares low temperature NO oxidant of the present invention
The low temperature NO oxidant that secure ph is 75g/L in 7 or so, volume 5L, concentration.Sodium hypochlorite in mass ratio:
Sodium chlorite: sodium chlorate: sodium perchlorate=4:1:0.3:0.2 weighs raw material, and dissolves one by one in deionized water, complete to solute
The hydrochloric acid solution that concentration is 0.3mol/L is added after fully dissolved, adjusts pH value 7 or so.
The evaluation of the oxidizing effect of the NO that embodiment 5 is prepared: flue gas flow 25L/min, 28 DEG C of reaction temperature,
O in former flue gas2、SO2, NO concentration be respectively 16.8%, 500mg/m3、300mg/m3, SO in the tail gas flue gas after reaction2、NO
Concentration be respectively 0mg/m3、15mg/m3, the removal efficiency of NO is 95%.
Embodiment 6 prepares low temperature NO oxidant of the present invention
The low temperature NO oxidant that secure ph is 100g/L in 7 or so, volume 8L, concentration.Sodium hypochlorite in mass ratio:
Sodium chlorite: sodium chlorate: sodium perchlorate=4:1:0.3:0.2 weighs raw material, and dissolves one by one in deionized water, complete to solute
The hydrochloric acid solution that concentration is 0.5mol/L is added after fully dissolved, adjusts pH value 7 or so.
The evaluation of the oxidizing effect of the NO that embodiment 6 is prepared: flue gas flow 25L/min, 28 DEG C of reaction temperature,
O in former flue gas2、SO2, NO concentration be respectively 16.8%, 500mg/m3、300mg/m3, SO in the tail gas flue gas after reaction2、NO
Concentration be respectively 0mg/m3、12mg/m3, the removal efficiency of NO is 96%.
It is high-efficient by embodiment result it is found that low temperature NO oxidant denitration effect of the invention is good, can generally it reach
80% or more, it is therefore desirable to reach 98%, compare existing oxidation and denitration agent (removal efficiency 76%), denitration efficiency improves
20% or more, there is significant progress.
Claims (10)
1. low temperature NO oxidant, which is characterized in that composition includes: in sodium hypochlorite, sodium chlorite, sodium chlorate or sodium perchlorate
At least two.
2. low temperature NO oxidant according to claim 1, it is characterised in that: the material quality is than at least meeting following one
:
When two kinds of raw materials mix: the sodium hypochlorite: sodium chlorite=1~10 ︰ 1；The sodium hypochlorite: sodium chlorate=
0.5~15 ︰ 1；The sodium hypochlorite: sodium perchlorate=0.1~20 ︰ 1；The sodium chlorite: sodium chlorate=1~15 ︰ 1；
The sodium chlorite: sodium perchlorate=1~10 ︰ 1；The sodium chlorate: sodium perchlorate=1~5 ︰ 1；
When three kinds of raw materials mix, the sodium hypochlorite: sodium chlorite: 0.5~15 ︰ 1 of sodium chlorate=0.5~15 ︰；Described
Sodium hypochlorite: sodium chlorite: 0.5~15 ︰ 1 of sodium perchlorate=1~10 ︰；The sodium chlorite: sodium chlorate: sodium perchlorate=1
0.5~10 ︰ 1 of~10 ︰；The sodium hypochlorite: sodium chlorate: 1~5 ︰ 1 of sodium perchlorate=0.5~15 ︰；
When four kinds of raw materials mix, the sodium hypochlorite: sodium chlorite: sodium chlorate: sodium perchlorate=1~20 ︰, 0.5~15 ︰
0.5~15 ︰ 1.
3. low temperature NO oxidant according to claim 1, it is characterised in that: the oxidant is sodium hypochlorite and chlorous acid
Sodium is mixed by weight 4 ︰ 1.
4. low temperature NO oxidant according to claim 1, it is characterised in that: the oxidant is sodium hypochlorite, chlorous acid
The mixture of sodium and sodium chlorate and/or sodium perchlorate.
5. low temperature NO oxidant according to claim 4, it is characterised in that: when group become sodium hypochlorite, sodium chlorite and
When sodium chlorate, the mass ratio of three kinds of raw materials is 4 ︰, 1 ︰ 0.3.
6. low temperature NO oxidant according to claim 4, it is characterised in that: when group become sodium hypochlorite, sodium chlorite and
When sodium perchlorate, the mass ratio of three kinds of raw materials is 4 ︰, 1 ︰ 0.2.
7. low temperature NO oxidant according to claim 4, it is characterised in that: when group becomes sodium hypochlorite, sodium chlorite, chlorine
When sour sodium and sodium perchlorate, the mass ratio of four kinds of raw materials is 4 ︰, 1 ︰, 0.3 ︰ 0.2.
8. the preparation method of the described in any item low temperature NO oxidants of claim 1~7, which comprises the following steps:
At least two in sodium hypochlorite, sodium chlorite, sodium chlorate or sodium perchlorate are weighed by weight ratio, are dissolved in the water and are matched
At solution, adjusting solution ph is 2~9, obtains low temperature NO oxidant.
9. the preparation method of low temperature NO oxidant according to claim 8, it is characterised in that: the solution concentration is 1
~100g/L.
10. the preparation method of low temperature NO oxidant according to claim 8, it is characterised in that: the solution ph is 7.
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|---|---|---|---|---|
| US3979191A (en) * | 1975-01-27 | 1976-09-07 | Kobe Steel Ltd. | Method for denitrating exhaust gases |
| CN1986033A (en) * | 2005-12-23 | 2007-06-27 | 浙江大学 | Chloric strong oxidant enhanced wet combined urea desulfurizing and denitrifying process |
| CN102172469A (en) * | 2011-03-09 | 2011-09-07 | 浙江大学 | Composite flue gas purification additive for wet flue gas desulfurization system |
| CN104258701A (en) * | 2014-10-08 | 2015-01-07 | 福建龙净环保股份有限公司 | Smoke denitration method and device |
| CN107497273A (en) * | 2017-09-25 | 2017-12-22 | 济南大学 | A kind of preparation method and application of environment protection, low cost smoke denitrifier |
| CN107875855A (en) * | 2017-11-14 | 2018-04-06 | 大连海事大学 | A kind of boat diesel engine exhaust emission integrated conduct method and device |
-
2018
- 2018-10-30 CN CN201811280762.6A patent/CN109173638A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3979191A (en) * | 1975-01-27 | 1976-09-07 | Kobe Steel Ltd. | Method for denitrating exhaust gases |
| CN1986033A (en) * | 2005-12-23 | 2007-06-27 | 浙江大学 | Chloric strong oxidant enhanced wet combined urea desulfurizing and denitrifying process |
| CN102172469A (en) * | 2011-03-09 | 2011-09-07 | 浙江大学 | Composite flue gas purification additive for wet flue gas desulfurization system |
| CN104258701A (en) * | 2014-10-08 | 2015-01-07 | 福建龙净环保股份有限公司 | Smoke denitration method and device |
| CN107497273A (en) * | 2017-09-25 | 2017-12-22 | 济南大学 | A kind of preparation method and application of environment protection, low cost smoke denitrifier |
| CN107875855A (en) * | 2017-11-14 | 2018-04-06 | 大连海事大学 | A kind of boat diesel engine exhaust emission integrated conduct method and device |
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