CN107684915A - Dry denitration agent and its production method and application - Google Patents
Dry denitration agent and its production method and application Download PDFInfo
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- CN107684915A CN107684915A CN201710918940.2A CN201710918940A CN107684915A CN 107684915 A CN107684915 A CN 107684915A CN 201710918940 A CN201710918940 A CN 201710918940A CN 107684915 A CN107684915 A CN 107684915A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 78
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003546 flue gas Substances 0.000 claims abstract description 40
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 38
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 30
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 29
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 31
- 239000000395 magnesium oxide Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003517 fume Substances 0.000 claims description 9
- 239000002250 absorbent Substances 0.000 claims description 8
- 230000002745 absorbent Effects 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 210000002966 serum Anatomy 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 13
- 229910044991 metal oxide Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002089 NOx Inorganic materials 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/40—
-
- B01J35/50—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
- B01D2253/1124—Metal oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a kind of Dry denitration agent and its production method and application.Based on 100 parts by weight denitrfying agents, the denitrfying agent includes following components：30~60 parts by weight TiO2, 10~30 parts by weight ZrO2, 2~10 parts by weight CoO, 1~8 parts by weight Co2O3, 2~10 parts by weight Fe2O3, 5~15 parts by weight MnO2, 2~10 parts by weight KMnO4.The Dry denitration agent of the present invention is good to the catalytic oxidation effect of the nitrogen oxides of flue gas, and denitration efficiency is high.
Description
Technical field
The present invention relates to a kind of Dry denitration agent and its production method and application, especially a kind of Dry denitration agent and its life
Production method and dry fume method of denitration.
Background technology
With the development of national economy and the increasingly raising of living standards of the people, it is increasing that environmental problem obtains people
Pay attention to.As the pollutant closely related with air quality, nitrogen oxides is constantly subjected to paying close attention to for country.Iron and steel enterprise burns
Knot machine is as emphasis NOxEmission source, its denitration also receive more and more attention.《Key area prevention and control of air pollution " 12
Five " planning》It is distinctly claimed and carries out nitrogen oxides pollution preventing and treating comprehensively, actively develops sintering device flue gas denitration and demonstrate, and 2013 9
Moon issue《Prevention and control of air pollution action plan》Even more require to accelerate key industry denitration transformation.
Remove NO in flue gasxTechnology have wet method denitrogenation, catalytic decomposition, solid absorption method, liquid absorption method, plasma
Activation method, microbial method, SNCR method (SNCR) and selective catalytic reduction (SCR) etc..Wet technique refers to
By the absorption in flue gas and relatively stable material is converted into using liquid phase chemical reagent, the process device is complicated, cost is high, and produces
Raw sewage post processing is difficult.By contrast, dry fume removing sulfuldioxide process is simple, removal efficiency is high, non-secondary pollution.
SCR methods are to be presently considered to best gas denitrifying technology, have a higher denitration efficiency (up to 90%), and technology more into
It is ripe, non-secondary pollution, at home and abroad more and more applied, but its investment and operating cost are high.
New and effective, Low investment, the denitration technology of low cost are the mains direction of studying of current environmental protection industry (epi).Utilize oxidation
Agent combination wet absorption gas denitrifying technology is a kind of new denitration technology.This method utilizes the principle that pressure aoxidizes by flue gas
The middle less NO of solubility is oxidized to NO2Or N2O5Etc. the nitrogen oxides of high-valence state, then absorbed again with water or alkaline matter.Oxygen
Agent combination wet absorption gas denitrifying technology can make full use of original system, have improvement cost is low, the cycle is short, occupation of land is small,
The advantages that technique is simple, strong adaptability.For example, CN1768902A discloses one kind using only O3Flue gas as oxidant takes off
Nitre method, using O3It is injected to as oxidant in flue, the NO in boiler smoke is oxidized to NO soluble in water2Or N2O5,
Then water or alkali liquid washing flue gas are used, removes the NO in flue gasx.Though the method for this oxidation and denitration can reach removing NOxMesh
, but O3In the cigarette temperature environment more than 130 DEG C and dustiness is in 50~200mg/Nm3In the range of when, be extremely easy in decomposition or adsorption of dust
And lose activity.Individually use O3During oxidation and denitration, although oxidation efficiency is higher, O3Consumption is big, produces O3Spent electricity
It is even more surprising, often produce 1kg O3Need to consume electricity 12kwh.If carry out O using the ozone generator under prior art3It is de-
Nitre, operating cost are very high.
The content of the invention
It is an object of the present invention to provide a kind of other kinds of Dry denitration agent, its denitration efficiency it is high and into
This is relatively low.
It is another object of the present invention to provide a kind of production method of denitrfying agent, its technique is simple, energy-conserving and environment-protective.
It is yet a further object of the present invention to provide a kind of method of dry fume denitration, it can improve making for denitrfying agent
Use effect.
The present invention, which adopts the following technical scheme that, realizes above-mentioned purpose.
The present invention provides a kind of Dry denitration agent, and based on 100 parts by weight denitrfying agents, the denitrfying agent includes following components：
According to the denitrfying agent of the present invention, it is preferable that based on 100 parts by weight denitrfying agents, the denitrfying agent includes following components：
According to the denitrfying agent of the present invention, it is preferable that based on 100 parts by weight denitrfying agents, the denitrfying agent includes following components：
According to the denitrfying agent of the present invention, it is preferable that the average grain diameter of the denitrfying agent is 0.8~15 micron.
According to the denitrfying agent of the present invention, it is preferable that described TiO2、ZrO2、CoO、Co2O3、Fe2O3And MnO2Raw material it is equal
For nano-scale oxide.
The present invention also provides the production method of above-mentioned denitrfying agent, comprises the following steps：
(1) by CoO, Co2O3、Fe2O3、MnO2And KMnO4Addition contains TiO2And ZrO2Slurries in, rotating speed be 100~
Stirred 6~60 hours under 300rpm, form mixed serum；
(2) earthquake frequency is under 20~200kHz ul-trasonic irradiation, is described in 3~18wt% ammoniacal liquor adds by concentration
Mixed serum, until the pH value of reaction system is 7~10；After continuing stirring 2~6 hours, liquor potassic permanganate is added dropwise, until anti-
The pH value for answering system is 4~6, continues stirring 2~6 hours, is filtered by vacuum, adds water washing, obtain paste；By the paste
Dried at 100~130 DEG C, be ground into molecule；
(3) molecule is calcined 2~6 hours at 350~1000 DEG C, obtains the denitrfying agent.
In accordance with the present production process, it is preferable that in step (2), the addition speed of ammoniacal liquor is 0.2~20mL/min.
In accordance with the present production process, it is preferable that in step (2), the rate of addition of liquor potassic permanganate for 0.2~
20mL/min。
The present invention also provides a kind of method of dry fume denitration, the denitrfying agent described in flue gas is fully contacted, Ran Houyu
Absorbent dry powder contact containing magnesia, so as to remove the nitrogen oxides in flue gas；Wherein, the cigarette before being contacted with denitrfying agent
The amount of nitrogen oxides of gas is 100~600mg/Nm3, flow velocity is 2~5m/s and temperature is 105~160 DEG C.
Method in accordance with the invention it is preferred that the magnesia includes 70~85wt% activated magnesia, and nanoscale
Content of the magnesia in the magnesia is 10~20wt%.
Lower nitrogen oxides can be the higher nitrogen oxides such as nitrogen dioxide by the Dry denitration agent of the present invention, then with oxygen
Change the absorbents such as magnesium to absorb, so as to reach denitration effect.The denitration effect of the denitrfying agent of the present invention is good, and energy consumption is low, and cost is relatively low.
Embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
In the present invention, nanoscale represents 1~100nm, preferably 10~60nm.
<Dry denitration agent>
The denitrfying agent of the present invention is a kind of denitrating catalyst.The denitrfying agent can include carrier and active component.Carrier can
Nanoscale amphoteric oxide is thought, for example, TiO2And ZrO2Combination.Active component include nanosize metal oxide and
KMnO4.Nanosize metal oxide includes CoO, Co2O3、Fe2O3、MnO2.These active components are supported on carrier, so as to
Form denitrfying agent.It is NO that these active components, which coordinate lower nitrogen oxides NO catalysis oxidations,2Deng.Such combination can be abundant
NO in flue gas is oxidized to NO2。
The present invention uses the active component of cobalt, iron, manganese as denitrfying agent；They are with CoO, Co2O3、Fe2O3、MnO2Form
In the presence of, using the teaching of the invention it is possible to provide the active sites of catalytic reaction, and reactant NO is adsorbed, and promote reaction to carry out.
Main carriers of the Ti as active component, with TiO2Form is present.Ti equally adsorbs to NO, increases reactant
In the possibility of denitrfying agent adsorption.ZrO2And TiO2Carrier is combined together as, Zr can substitute the position of Ti in original lattice
Put, form ZrTiO4.Now new acidity and basicity will be formed on carrier, NO is when occupying denitrfying agent, these alkalescence point position meetings
Attract NO, target position is occupied in formation, so as to the active sites of effective protection activity component.
According to an embodiment of the invention, based on 100 parts by weight denitrfying agents, the denitrfying agent includes 30~60 parts by weight
TiO2, 10~30 parts by weight ZrO2, 2~10 parts by weight CoO, 1~8 parts by weight Co2O3, 2~10 parts by weight Fe2O3, 5~15 weight
Part MnO2, and 2~10 parts by weight KMnO4.Preferably, the denitrfying agent includes 35~60 parts by weight TiO2, 15~25 parts by weight
ZrO2, 2.5~7 parts by weight CoO, 1.5~6 parts by weight Co2O3, 3~8 parts by weight Fe2O3, 6~12 parts by weight MnO2, and 3~8 weights
Measure part KMnO4.It is highly preferred that the denitrfying agent includes 50~52 parts by weight TiO2, 15~20 parts by weight ZrO2, 3~6 parts by weight
CoO, 3~5 parts by weight Co2O3, 6~8 parts by weight Fe2O3, 7~10 parts by weight MnO2, and 5~8 parts by weight KMnO4.By activearm
Sub-control system can significantly improve their oxidation effectivenesses to the lower nitrogen oxides in flue gas in above range, de- so as to improve
Nitre effect.In the present invention, denitrfying agent is by including above-mentioned TiO2、ZrO2、CoO、Co2O3、Fe2O3、MnO2And KMnO4Raw material be made.
According to one preferred embodiment of the invention, denitrfying agent is only by above-mentioned TiO2、ZrO2、CoO、Co2O3、Fe2O3、MnO2And KMnO4
Raw material be made.
The average grain diameter of the denitrfying agent of the present invention is 0.8~15 micron, preferably 1~5 micron.Average grain diameter can use
Sieve method obtains.In the present invention, described TiO2、ZrO2、CoO、Co2O3、Fe2O3And MnO2Raw material be nanoscale
Thing.In the denitrfying agent of shaping, CoO, Co2O3、Fe2O3And MnO2Size can be 2~100nm, specific surface area can reach
100~300m2/g。
<Production method>
The denitrfying agent of the present invention can be produced using nano-metal-oxide.CoO, Co are prepared first2O3、Fe2O3With
MnO2Nanosize metal oxide.Common methods have sol-gel process, Hydrolyze method, hydrothermal synthesis method etc., it is preferred to use molten
Glue-gel method.For example, using cobalt, iron, manganese nitrate solution as predecessor, hydrolyzed, contracted in the solution with these nitrate respectively
Sol solutionses are synthesized, then heating removes solvent and changes into gel, crystal formation is finally made, granularity is controllable and uniform particle degree is high
Nanosize metal oxide.These methods are all well known in the art, are repeated no more here.
The production method of the present invention includes (1) blend step；(2) reaction and drying steps：(3) calcining step etc..
The present invention blend step be：By CoO, Co2O3、Fe2O3、MnO2Nanosize metal oxide and KMnO4Addition contains
There is TiO2And ZrO2Slurries in, rotating speed be 100~300rpm under stir 6~60 hours, formation mixed serum.Rotating speed is preferred
For 200~250rpm；Mixing time is preferably 10~48 hours.
The reaction and drying steps of the present invention includes：Earthquake frequency is 20~200kHz, is preferably 50~100kHz's
It is 3~18wt%, preferably 5~10wt% ammoniacal liquor addition mixed serum by concentration, until reactant under ul-trasonic irradiation
The pH value of system is 7~10, such as 7~8；Continue stirring 2~6 hours, be preferably after 2~3 hours, liquor potassic permanganate is added dropwise,
Until the pH value of reaction system is 4~6, such as 5~5.5, continues stirring 2~6 hours, be preferably 2~3 hours, vacuum filtration,
Add water washing, obtain paste；The paste is dried at 100~130 DEG C, such as 105~110 DEG C, obtains dried object；
Then dried object is ground into molecule.The addition speed of ammoniacal liquor can be 0.2~20mL/min, preferably 3~10mL/
min.The rate of addition of liquor potassic permanganate is 0.2~20mL/min, preferably 1~5mL/min.So be advantageous to obtain size
Uniform nano-metal-oxide.The liquor potassic permanganate that the present invention uses is preferably acid permanganate soln.
The calcining step of the present invention includes：The molecule is forged at 350~1000 DEG C, preferably 500~800 DEG C
Burn 2~6 hours, such as 2~3 hours, obtain denitrfying agent.
<Dry fume method of denitration>
The method of the dry fume denitration of the present invention includes denitrating flue gas step：Flue gas and above-mentioned denitrfying agent are fully connect
Touch, then contacted with the absorbent dry powder containing magnesia, so as to remove the nitrogen oxides in flue gas.
In the method for the invention, the amount of nitrogen oxides of flue gas can be 100~600mg/Nm3, be preferably 150~
500mg/Nm3, more preferably 300~450mg/Nm3.Oxygen content can be 10~25vol%, be preferably 15~20vol%.Temperature
Degree can be 105~160 DEG C；Preferably 120~135 DEG C.In addition, the flow velocity of flue gas can be 2~5m/s, preferably 2.5~
3.5m/s.Above-mentioned Gas Parameters represent the parameter at smoke inlet；The parameter of smoke outlet according to actual denitration situation and
It is fixed.Using above-mentioned technological parameter, be advantageous to improve denitration efficiency.Flue gas fully contacts with denitrfying agent, by the Low-Charged Nitrogen in flue gas
Oxide is converted into nitrogen dioxide etc., forms pretreated fumes.
The magnesia of the present invention can include light calcined magnesia, micron order magnesia and/or nanoscale magnesium.According to this
One embodiment of invention, the magnesia include 70~85wt% activated magnesia, preferably 80~85% activity
Magnesia；And content of the nanoscale magnesium in the magnesia is 10~20wt%, preferably 15~20wt%.Pass through profit
With the exclusive property of some nanoparticles of nanoscale magnesium, denitration efficiency can be improved.So it is more beneficial for magnesium nitrate
Formed, so as to improve denitrating flue gas effect.In the present invention, the absorbent can only include above-mentioned magnesia；The absorption
Agent can also include the modifying agent such as calcium oxide and silica.Modifying agent is micron order, nano level metal oxide.In order to carry
High removal efficiency, absorbent of the invention are powdered.Its particle diameter can be 0.8~15 micron, preferably 1~5 micron.So
Directly absorbent can be mixed with flue gas, and then the removing of nitrogen oxides is carried out to flue gas, so as to not need a large amount of water
In the case of complete the denitration of flue gas, and do not produce a large amount of industrial wastes.For example, by absorbent dry powder and pretreated fumes in cigarette
Feed channel is sufficiently mixed, and carries out denitration process subsequently into absorption tower, the flue gas after denitration is discharged by chimney.
Embodiment 1
Denitrfying agent is produced according to the formula of table 1.By CoO, Co2O3、Fe2O3、MnO2(above compound is nano level metal
Oxide) and KMnO4Addition contains TiO2And ZrO2Slurries in, rotating speed be 250pm under stir 40 hours, formation mixing slurry
Liquid.Earthquake frequency is under 80kHz ul-trasonic irradiation, is that 10wt% ammoniacal liquor adds the mixed serum by concentration, until anti-
The pH value for answering system is 7；After continuing stirring 3 hours, liquor potassic permanganate is added dropwise, until the pH value of reaction system is 5, continues to stir
Mix 2 hours, be filtered by vacuum, add water washing, obtain paste.The addition speed of ammoniacal liquor is 5mL/min；The drop of liquor potassic permanganate
Acceleration is 2mL/min.The paste is dried at 100 DEG C, is ground into molecule；By the molecule at 500 DEG C
Lower calcining 3 hours, obtains denitrfying agent G1.
The formula of table 1, denitrfying agent G1
| TiO2 | 55.0 parts by weight |
| ZrO2 | 20.0 parts by weight |
| CoO | 5.0 parts by weight |
| Co2O3 | 5.0 parts by weight |
| Fe2O3 | 3.0 parts by weight |
| MnO2 | 7.0 parts by weight |
| KMnO4 | 5.0 parts by weight |
Catalysis oxidation is carried out to flue gas using the denitrfying agent, and absorbed using magnesia dry powder.The flow velocity of flue gas is
2.5m/s；The other specification of smoke inlet, the parameter of exhanst gas outlet are as shown in tables 2 and 3.Flue gas after purification, nitrogen oxides
Concentration is 12mg/Nm3, denitration efficiency 86.21%.
Table 2, smoke inlet parameter
| Sequence number | Parameter | Unit | Numerical value |
| 1 | Inlet flue gas amount (operating mode) | m3/h | 1700000 |
| 2 | Inlet flue gas amount (mark condition) | Nm3/h | 118091.6031 |
| 3 | Inlet flue gas temperature | ℃ | 120 |
| 4 | Entrance nitric oxide concentration | mg/Nm3 | 450 |
| 5 | Humidity of flue gas | % | 5.6 |
Table 3, exhanst gas outlet parameter
| Sequence number | Project | Quantity | Unit |
| 1 | Exiting flue gas amount (operating mode) | 765687 | m3/h |
| 2 | Exhaust gas temperature | 65 | ℃ |
| 3 | Discharged nitrous oxides concentration | 12 | mg/Nm3 |
| 4 | Denitration efficiency | 86.21 | % |
| 5 | The quantum of output of accessory substance | 2.34 | t/h |
Embodiment 2
Formula according to table 4 obtains denitrfying agent G2, and remaining condition is same as Example 1.Flue gas is entered using the denitrfying agent
Row catalysis oxidation, and absorbed using magnesia dry powder.Flue gas after purification, the concentration of nitrogen oxides is 10mg/Nm3, take off
Nitre efficiency is 88.51%.The parameter of exhanst gas outlet is as shown in table 5.
The formula of table 4, denitrfying agent G2
| TiO2 | 53.0 parts by weight |
| ZrO2 | 20.0 parts by weight |
| CoO | 5.0 parts by weight |
| Co2O3 | 5.0 parts by weight |
| Fe2O3 | 5.0 parts by weight |
| MnO2 | 7.0 parts by weight |
| KMnO4 | 5.0 parts by weight |
Table 5, exhanst gas outlet parameter
Embodiment 3
Formula according to table 6 obtains denitrfying agent G3, and remaining condition is same as Example 1.Flue gas is entered using the denitrfying agent
Row catalysis oxidation, and absorbed using magnesia dry powder.Flue gas after purification, the concentration of nitrogen oxides is 6.4mg/Nm3, take off
Nitre efficiency is 92.74%.The parameter of exhanst gas outlet is as shown in table 7.
The formula of table 6, denitrfying agent G3
| TiO2 | 51.0 parts by weight |
| ZrO2 | 20.0 parts by weight |
| CoO | 5.0 parts by weight |
| Co2O3 | 5.0 parts by weight |
| Fe2O3 | 7.0 parts by weight |
| MnO2 | 7.0 parts by weight |
| KMnO4 | 5.0 parts by weight |
Table 7, exhanst gas outlet parameter
| Sequence number | Project | Quantity | Unit |
| 1 | Exiting flue gas amount (operating mode) | 824493 | m3/h |
| 2 | Exhaust gas temperature | 65 | ℃ |
| 3 | Discharged nitrous oxides concentration | 6.4 | mg/Nm3 |
| 4 | Denitration efficiency | 92.74 | % |
| 5 | The quantum of output of accessory substance | 2.53 | t/h |
The present invention is not limited to above-mentioned embodiment, in the case of without departing substantially from the substantive content of the present invention, this area skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (10)
1. a kind of Dry denitration agent, it is characterised in that based on 100 parts by weight denitrfying agents, the denitrfying agent includes following components：
2. denitrfying agent according to claim 1, it is characterised in that based on 100 parts by weight denitrfying agents, the denitrfying agent include with
Lower component：
3. denitrfying agent according to claim 1, it is characterised in that based on 100 parts by weight denitrfying agents, the denitrfying agent include with
Lower component：
4. denitrfying agent according to claim 1, it is characterised in that the average grain diameter of the denitrfying agent is 0.8~15 micron.
5. according to the denitrfying agent described in any one of Claims 1 to 4, it is characterised in that described TiO2、ZrO2、CoO、Co2O3、
Fe2O3And MnO2Raw material be nano-scale oxide.
6. the production method of denitrfying agent according to claim 5, it is characterised in that comprise the following steps：
(1) by CoO, Co2O3、Fe2O3、MnO2And KMnO4Addition contains TiO2And ZrO2Slurries in, rotating speed be 100~
Stirred 6~60 hours under 300rpm, form mixed serum；
(2) earthquake frequency is under 20~200kHz ul-trasonic irradiation, is that 3~18wt% ammoniacal liquor adds the mixing by concentration
Slurries, until the pH value of reaction system is 7~10；After continuing stirring 2~6 hours, liquor potassic permanganate is added dropwise, until reactant
The pH value of system is 4~6, continues stirring 2~6 hours, is filtered by vacuum, adds water washing, obtain paste；The paste is existed
Dried at 100~130 DEG C, be ground into molecule；
(3) molecule is calcined 2~6 hours at 350~1000 DEG C, obtains the denitrfying agent.
7. production method according to claim 6, it is characterised in that in step (2), the addition speed of ammoniacal liquor for 0.2~
20mL/min。
8. production method according to claim 7, it is characterised in that in step (2), the rate of addition of liquor potassic permanganate
For 0.2~20mL/min.
A kind of 9. method of dry fume denitration, it is characterised in that by the denitration described in flue gas and any one of Claims 1 to 5
Agent fully contacts, and is then contacted with the absorbent dry powder containing magnesia, so as to remove the nitrogen oxides in flue gas；Wherein, with
The amount of nitrogen oxides of flue gas before denitrfying agent contact is 100~600mg/Nm3, flow velocity is 2~5m/s and temperature is 105
~160 DEG C.
10. according to the method for claim 9, it is characterised in that the magnesia includes 70~85wt% active oxidation
Magnesium, and content of the nanoscale magnesium in the magnesia is 10~20wt%.
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| CN111672290A (en) * | 2020-06-08 | 2020-09-18 | 宜兴市禄洪环保科技有限公司 | Solid-state denitration agent and preparation method thereof |
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