CN108355665A - Energy simultaneous SO_2 and NO removal has spinel structure catalyst and its preparation method and application - Google Patents
Energy simultaneous SO_2 and NO removal has spinel structure catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN108355665A CN108355665A CN201810119235.0A CN201810119235A CN108355665A CN 108355665 A CN108355665 A CN 108355665A CN 201810119235 A CN201810119235 A CN 201810119235A CN 108355665 A CN108355665 A CN 108355665A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- spinel structure
- removal
- simultaneous
- kinds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 23
- 239000011029 spinel Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 239000007790 solid phase Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims description 8
- 238000004073 vulcanization Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000005259 measurement Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910002637 Pr6O11 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/005—Spinels
-
- 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
-
- 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
- B01J23/83—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 rare earths or actinides
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of energy simultaneous SO_2 and NO removals to have spinel structure catalyst and its preparation method and application, including active component is CoO, Fe2O3、Al2O3In two kinds or three kinds, auxiliary agent CeO2、Y2O3In one kind or two kinds, carrier is activated carbon；The active component of the catalyst forms spinel structure in carrier surface.For simultaneous SO_2 and NO removal：Using CO as reducing agent, NO is reduced to by N using gas and solid phase catalyzing reduction method2It is discharged into air, SO2S simple substance is reduced to be recycled.It is auxiliary agent by activated carbon supported transition metal oxide, rare earth metal, raw material is wide with source, is easy acquisition, is at low cost；Activated carbon have many advantages, such as large specific surface area, adsorption capacity it is good, containing abundant oxygen-containing functional group；The specific surface area measurement result of catalyst is 800~1500m2/g。
Description
Technical field
The present invention relates to a kind of desulphurization denitration catalyst more particularly to a kind of energy simultaneous SO_2 and NO removal to have spinel structure
Catalyst and its preparation method and application.
Background technology
Currently, energy loss relies primarily on combustion burning of coal, the SO generated so as to cause fire coal2Become atmosphere pollution with NO
In most important pollutant, harm seriously affects ecological environment and human health, reduces NO and SO2Discharge capacity gesture must
Row.
Achieve the purpose that desulfurization and denitration relative to traditional SCR denitration technology and FGD desulfurization technology combine, together
When desulphurization denitration have and save floor occupying area, reduce investment and the advantages such as operating cost, widely paid close attention to.
Existing simultaneous SO_2 and NO removal catalyst mainly has V2O5/AC、CuO/Al2O3, rare-earth oxide etc..These
Catalyst is medium temperature or high temperature catalyst, and at 300 DEG C or more, temperature reduces catalytic activity and significantly drops general effective catalytic temperature
It is low.
V disclosed in Patent No. CN 1475305A2O5/ AC catalyst, with NH3As reducing agent gas, although can be
Desulphurization denitration under lower temperature, but it is by being removed step by step, and then the method denitration of SCR, and denitrification rate are used in first desulfurization
Only 10~50%, desulphurization denitration process will produce the by-product in blocking catalyst duct, react the activity of 2h rear catalysts
Just decline, needs to regenerate, and regenerative process is complicated.
Al disclosed in Patent No. CN102962064A2O3Supported CuO, Fe2O3Catalyst, catalytic temperature will 350~
800 DEG C of catalytic effects that can have just played, and the temperature of exhanst gas outlet is between 120~200 DEG C, therefore the excessive and Al that consumes energy2O3
As the catalyst of carrier, due to its grain shape, bed resistance is larger, it is difficult to dust be overcome to block.
Activated carbon supported rare earth metal type oxide catalyst disclosed in Patent No. CN201210463016.7 is with CO
Reducing agent, Pr6O11/ AC effects are preferably at 400 DEG C, SO2Conversion ratio still falls within middle height up to 99.3%, NO conversion ratios up to 97.7%
Warm range of catalysts and conversion ratio also has room for promotion.
Activated carbon have many advantages, such as large specific surface area, adsorption capacity it is good, containing abundant oxygen-containing and nitrogen-containing functional group,
Through preparing the patent of activated carbon about distinct methods, but currently without using transition metal as active component, rare earth metal
It is loaded on activated carbon as auxiliary agent, and forms spinelle structure specific in this way, be catalyzed for simultaneous SO_2 and NO removal in flue gas
The patent report of agent.
Invention content
The object of the present invention is to provide a kind of energy simultaneous SO_2 and NO removals to have spinel structure catalyst and preparation method thereof
And application.
The purpose of the present invention is what is be achieved through the following technical solutions：
The energy simultaneous SO_2 and NO removal of the present invention has spinel structure catalyst, including：Active component is CoO, Fe2O3、
Al2O3In two kinds or three kinds, auxiliary agent CeO2、Y2O3In one kind or two kinds, carrier is activated carbon；
The active component of the catalyst forms spinel structure in carrier surface.
The above-mentioned energy simultaneous SO_2 and NO removal of the present invention has the preparation method of spinel structure catalyst, including step：
First, catalyst activity high-area carbon to be pre-processed：HNO of the compound concentration 5~15%3Solution, in room
Temperature is lower to press certain HNO3For quality with AC than steeped overnight, washing to neutrality is spare after dry cooling；
Then, active component and auxiliary agent is added, catalyst sample is made；
Later, presulfurization is carried out to the catalyst sample：Vulcanization atmosphere is SO2+ CO, 400~600 DEG C of curing temperature,
Vulcanization time 1h.
The above-mentioned energy simultaneous SO_2 and NO removal of the present invention has the application of spinel structure catalyst, de- for desulfurization simultaneously
Nitre：Using CO as reducing agent, NO is reduced to by N using gas and solid phase catalyzing reduction method2It is discharged into air, SO2S simple substance is reduced to be returned
It receives and utilizes.
As seen from the above technical solution provided by the invention, energy simultaneous SO_2 and NO removal tool provided in an embodiment of the present invention
There is spinel structure catalyst and its preparation method and application, is to help by activated carbon supported transition metal oxide, rare earth metal
Agent, raw material is wide with source, is easy acquisition, is at low cost；Activated carbon have large specific surface area, adsorption capacity it is good, containing abundant
Oxygen-containing functional group etc.；The specific surface area measurement result of catalyst is 800~1500m2/g。
Specific implementation mode
The embodiment of the present invention will be described in further detail below.What is be not described in detail in the embodiment of the present invention is interior
Appearance belongs to the prior art well known to professional and technical personnel in the field.
There is the energy simultaneous SO_2 and NO removal of the present invention spinel structure catalyst, preferable specific implementation mode to be：
Including：Active component is CoO, Fe2O3、Al2O3In two kinds or three kinds, auxiliary agent CeO2、Y2O3In one kind or
Two kinds, carrier is activated carbon；
The active component of the catalyst forms spinel structure in carrier surface.
The active component is CoO, Fe2O3、Al2O3In two or three, the content of each component accounts for carrier quality
5~15% between；
The auxiliary agent is CeO2、Y2O3One or both of, the content of each component account for carrier quality 1~5% it
Between.
The specific surface area of the catalyst：800~1500m2/g。
The above-mentioned energy simultaneous SO_2 and NO removal of the present invention has the preparation method of spinel structure catalyst, preferably has
Body embodiment is：
Including step：
First, catalyst activity high-area carbon to be pre-processed：HNO of the compound concentration 5~15%3Solution, in room
Temperature is lower to press certain HNO3For quality with AC than steeped overnight, washing to neutrality is spare after dry cooling；
Then, active component and auxiliary agent is added, catalyst sample is made；
Later, presulfurization is carried out to the catalyst sample：Vulcanization atmosphere is SO2+ CO, 400~600 DEG C of curing temperature,
Vulcanization time 1h.
The above-mentioned energy simultaneous SO_2 and NO removal of the present invention has the application of spinel structure catalyst, preferably specific real
The mode of applying is：
For simultaneous SO_2 and NO removal：Using CO as reducing agent, NO is reduced to by N using gas and solid phase catalyzing reduction method2It is discharged into big
Gas, SO2S simple substance is reduced to be recycled.
The present invention with spinel structure at a lower temperature can simultaneous SO_2 and NO removal method for preparing catalyst and
It is applied.Compared with prior art, advantages of the present invention includes following several points：
Raw material of the present invention have source it is wide, be easy obtain, it is at low cost the advantages that；
Activated carbon have large specific surface area, adsorption capacity is good, contains abundant oxygen-containing functional group etc.；The specific surface of catalyst
Product measurement result is 800~1500m2/g；
Nitric acid pretreatment can effectively remove the ash content on the surfaces AC, dredge duct, further increase the specific surface area of carrier, separately
On the one hand it can increase absorption and the active centre of carrier surface；
The activity component metal oxide of catalyst can be converted into metal sulfide by presulfurization, be substantially reduced needed for reaction
Reduction temperature, play the role of reduce reaction needed for activation energy, reduce energy consumption；
Spinel structure class catalyst have better than conventional catalyst catalytic performance, and easily generate lattice defect to
More active sites are generated, catalytic activity is improved；
Inherently contain unburned complete CO in flue gas, as reducing agent gas, it is possible to reduce while expense
The CO in flue gas is removed, achievees the effect that the treatment of wastes with processes of wastes against one another；
The catalyst of the present invention can be made into cellular etc. variously-shaped, it is possible to reduce bed resistance overcomes dust to block.
The preparation method of the catalyst of the present invention is equi-volume impregnating：20~40 mesh active carbon particles are taken, with 5~15%
HNO3Solution, than soaked overnight, is washed out to neutral drying for standby by certain mass.
By 1.5:1 deionized water content dissolves the nitric acid presoma of corresponding active component, quiet in 40 DEG C of thermostat water baths
12h, then the dry 12h in air dry oven are set, finally 4h is roasted at 500 DEG C in nitrogen atmosphere protection, obtains catalyst sample.
The catalyst prepared is subjected to presulfurization processing, uses CO+SO2Atmosphere carries out presulfurization, vulcanization temperature to catalyst
For degree between 400~600 DEG C, vulcanization time is 1~3h.
NO is reduced to N by the catalyst using CO as reducing agent, using gas and solid phase catalyzing reduction method2It is discharged into air, SO2Reduction
It is recycled for S simple substance, is suitable for independent denitration, independent desulfurization and simultaneous SO_2 and NO removal.
When catalyst prepared by the present invention is applied to simultaneous SO_2 and NO removal, including following content：
Using CO as reducing agent gas, gas group becomes NO in reactor：SO2：CO (volume fraction)=1:2:2.5.
In atmospheric fixed bed reactor, the air speed of simulated flue gas is 5000~10000h-1.
Operation temperature is 100~500 DEG C.
Specific embodiment：
3 specific examples are set forth below to be illustrated the present invention, but the present invention is not limited to these instances.
Embodiment 1,10Fe2O36CoO3Y2O3/AC
Wherein Fe2O310%, the CoO for accounting for carrier quality accounts for 6%, Y of carrier quality2O3The 3% of carrier quality is accounted for, i.e.,
Active component and the total load amount of auxiliary agent are 19%.
First take 20~40 mesh AC500g in beaker, with the HNO of a certain concentration certain proportion (with AC mass ratioes)3Pretreatment
12h is washed out to neutrality drying, is cooled to room temperature rear spare.
According to the load capacity of the catalyst activity component and co-catalyst done, 2.5299gFe (NO are accurately weighed3)3·
9H2O, 1.0532g Co (NO3)2·6H2O, 0.3393g Y (NO3)3·6H2It is molten that the formation mixing of 7ml deionized water dissolvings is added in O
Liquid；The pretreated AC of precise 5.0000g, is impregnated into the mixed solution prepared, impregnates 12h at room temperature in 40 DEG C,
It is subsequently placed in 110 DEG C of drying boxes dry 12h, finally 4h is roasted in 500 DEG C in the pipe type calciner of nitrogen protection, must be catalyzed
Agent sample.
The catalyst prepared is placed in atmospheric fixed bed reactor, preparing gas group becomes：1000ppmSO2,
2000ppmCO, remaining is N2, prevulcanisation time 1h, curing temperature is 550 DEG C.
After presulfiding of catalyst, being passed through simulation gas group becomes：1000ppmSO2, 500ppmNO, 2500ppmCO, remaining
For N2, air speed 6000h-1, catalytic amount 2mL, T90%About 208 DEG C, 232 DEG C reach maximum conversion, SO2Conversion ratio is
100%, NO conversion ratio are 100%.
Embodiment 2,10CoO15Al2O32CeO2/AC
Wherein Al2O315%, the CoO for accounting for carrier quality accounts for 10%, CeO of carrier quality2The 2% of carrier quality is accounted for, i.e.,
Active component and the total load amount of auxiliary agent are 27%.
First take 20~40 mesh AC500g in beaker, with the HNO of a certain concentration certain proportion (with AC mass ratioes)3Pretreatment
12h is washed out to neutrality drying, is cooled to room temperature rear spare.
According to the active component of the catalyst done and the load capacity of co-catalyst, 5.5166g Al are accurately weighed
(NO3)3·9H2Og、2.5053Co(NO3)2·6H2O、0.2523g Ce(NO3)2·6H27ml deionized water dissolving shapes are added in O
At mixed solution；The pretreated AC of precise 5.0000g, is impregnated into the mixed solution prepared, at room temperature in 40 DEG C
12h is impregnated, dry 12h is subsequently placed in 110 DEG C of drying boxes, finally in 500 DEG C of roastings in the pipe type calciner of nitrogen protection
4h obtains catalyst sample.
The catalyst prepared is placed in atmospheric fixed bed reactor, preparing gas group becomes：1000ppmSO2,
2000ppmCO, remaining is N2, prevulcanisation time 1h, curing temperature is 550 DEG C.
After presulfiding of catalyst, being passed through simulation gas group becomes：1000ppmSO2, 500ppmNO, 2500ppmCO, remaining
For N2, air speed 6000h-1, catalytic amount 2mL, T90%About 190 DEG C, 213 DEG C reach maximum conversion, SO2Conversion ratio is
100%, NO conversion ratio are 100%.
Embodiment 3,10Fe2O310CoO2CeO2/AC
Wherein Fe2O310%, the CoO for accounting for carrier quality accounts for 10%, CeO of carrier quality2The 2% of carrier quality is accounted for, i.e.,
Active component and the total load amount of auxiliary agent are 22%.
First take 20~40 mesh AC of 500g in beaker, with the HNO of a certain concentration certain proportion (with AC mass ratioes)3Pre- place
12h is managed, is washed out to neutrality drying, is cooled to room temperature rear spare.
According to the active component of the catalyst done and the load capacity of co-catalyst, 2.5299g Fe are accurately weighed
(NO3)3·9H2O、2.5023g Co(NO3)2·6H2O、0.2523g Ce(NO3)2·6H27ml deionized water dissolving shapes are added in O
At mixed solution；The pretreated AC of precise 5.0000g, is impregnated into the mixed solution prepared, at room temperature in 40 DEG C
12h is impregnated, dry 12h is subsequently placed in 110 DEG C of drying boxes, finally in 500 DEG C of roastings in the pipe type calciner of nitrogen protection
4h obtains catalyst sample.
The catalyst prepared is placed in atmospheric fixed bed reactor, preparing gas group becomes：1000ppmSO2,
2000ppmCO, remaining is N2, prevulcanisation time 1h, curing temperature is 550 DEG C.
After presulfiding of catalyst, being passed through simulation gas group becomes：1000ppmSO2, 500ppmNO, 2500ppmCO, remaining
For N2, air speed 6000h-1, catalytic amount 2mL, T90%About 215 DEG C, 242 DEG C reach maximum conversion, SO2Conversion ratio is
99.67%, NO conversion ratio are 100%.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (5)
1. a kind of energy simultaneous SO_2 and NO removal has spinel structure catalyst, which is characterized in that including：Active component be CoO,
Fe2O3、Al2O3In two kinds or three kinds, auxiliary agent CeO2、Y2O3In one kind or two kinds, carrier is activated carbon；
The active component of the catalyst forms spinel structure in carrier surface.
2. energy simultaneous SO_2 and NO removal according to claim 1 has spinel structure catalyst, which is characterized in that the work
Property group is divided into CoO, Fe2O3、Al2O3In two or three, the content of each component accounts between the 5~15% of carrier quality；
The auxiliary agent is CeO2、Y2O3One or both of, the content of each component accounts between the 1~5% of carrier quality.
3. energy simultaneous SO_2 and NO removal according to claim 2 has spinel structure catalyst, which is characterized in that the catalysis
The specific surface area of agent：800~1500m2/g。
4. a kind of energy simultaneous SO_2 and NO removal as claimed in claim 1,2 or 3 has the preparation method of spinel structure catalyst,
It is characterized in that, including step：
First, catalyst activity high-area carbon to be pre-processed：HNO of the compound concentration 5~15%3Solution is pressed at room temperature
Certain HNO3For quality with AC than steeped overnight, washing to neutrality is spare after dry cooling；
Then, active component and auxiliary agent is added, catalyst sample is made；
Later, presulfurization is carried out to the catalyst sample：Vulcanization atmosphere is SO2+ CO, 400~600 DEG C of curing temperature, when vulcanization
Between 1h.
5. a kind of energy simultaneous SO_2 and NO removal as claimed in claim 1,2 or 3 has the application of spinel structure catalyst, feature
It is, is used for simultaneous SO_2 and NO removal：Using CO as reducing agent, NO is reduced to by N using gas and solid phase catalyzing reduction method2Air is discharged into,
SO2S simple substance is reduced to be recycled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810119235.0A CN108355665A (en) | 2018-02-06 | 2018-02-06 | Energy simultaneous SO_2 and NO removal has spinel structure catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810119235.0A CN108355665A (en) | 2018-02-06 | 2018-02-06 | Energy simultaneous SO_2 and NO removal has spinel structure catalyst and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108355665A true CN108355665A (en) | 2018-08-03 |
Family
ID=63004719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810119235.0A Pending CN108355665A (en) | 2018-02-06 | 2018-02-06 | Energy simultaneous SO_2 and NO removal has spinel structure catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108355665A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111203205A (en) * | 2019-12-30 | 2020-05-29 | 安徽元琛环保科技股份有限公司 | Rare earth doping based ZIF-8 nanoporous carbon catalyst and preparation method and application thereof |
| CN111744494A (en) * | 2020-06-11 | 2020-10-09 | 北京华电光大环境股份有限公司 | Flat plate type CO and SO2And NOxSynchronous removal catalyst and preparation method thereof |
| CN112547076A (en) * | 2020-12-23 | 2021-03-26 | 浙江盛旺环境工程有限公司 | Prestressed SCR denitration catalyst and preparation method thereof |
| CN114308052A (en) * | 2021-12-01 | 2022-04-12 | 北京科技大学 | Preparation method of strong-effect water-resistant and sulfur-resistant denitration catalyst |
| CN115228478A (en) * | 2022-06-29 | 2022-10-25 | 昆明理工大学 | Sulfur-resistant denitration magnetic catalyst and preparation method and application thereof |
| CN115888850A (en) * | 2022-08-25 | 2023-04-04 | 国能龙源催化剂江苏有限公司 | Regeneration method of SCR denitration catalyst, denitration catalyst prepared by regeneration method and application of denitration catalyst |
| CN116492987A (en) * | 2023-05-22 | 2023-07-28 | 湘潭大学 | NO adsorbent and preparation method and application thereof |
| CN116492987B (en) * | 2023-05-22 | 2024-10-29 | 湘潭大学 | NO adsorbent and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5580534A (en) * | 1994-06-03 | 1996-12-03 | Daimler-Benz Ag | Zeolite-spinel catalyst for the reduction of nitrogen oxides and the process thereof |
| CN102485844A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Inferior wax oil hydrotreating method |
| CN102836717A (en) * | 2012-09-10 | 2012-12-26 | 中南大学 | Application of spinel-type oxide and method for catalytic desulfurization and denitrification |
| CN105289630A (en) * | 2015-11-06 | 2016-02-03 | 北京石油化工学院 | Method for preparing catalyst capable of performing simultaneous desulfurization and denitrification on flue gas |
| CN105289645A (en) * | 2015-11-14 | 2016-02-03 | 华玉叶 | Catalyst composition used for fire coal flue gas purifying |
| CN106311276A (en) * | 2016-08-30 | 2017-01-11 | 沈阳三聚凯特催化剂有限公司 | Denitration catalyst and preparation method thereof |
-
2018
- 2018-02-06 CN CN201810119235.0A patent/CN108355665A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5580534A (en) * | 1994-06-03 | 1996-12-03 | Daimler-Benz Ag | Zeolite-spinel catalyst for the reduction of nitrogen oxides and the process thereof |
| CN102485844A (en) * | 2010-12-03 | 2012-06-06 | 中国石油天然气股份有限公司 | Inferior wax oil hydrotreating method |
| CN102836717A (en) * | 2012-09-10 | 2012-12-26 | 中南大学 | Application of spinel-type oxide and method for catalytic desulfurization and denitrification |
| CN105289630A (en) * | 2015-11-06 | 2016-02-03 | 北京石油化工学院 | Method for preparing catalyst capable of performing simultaneous desulfurization and denitrification on flue gas |
| CN105289645A (en) * | 2015-11-14 | 2016-02-03 | 华玉叶 | Catalyst composition used for fire coal flue gas purifying |
| CN106311276A (en) * | 2016-08-30 | 2017-01-11 | 沈阳三聚凯特催化剂有限公司 | Denitration catalyst and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| WENJIE XU ET AL.: ""Synthesis of nanosized mesoporous Co–Al spinel and its application as solid base catalyst"", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| 王婷: ""催化还原法同时脱硫脱硝催化剂的制备与性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 皮志鹏等: ""铜铈改性镁铝尖晶石作为助催化剂同时脱除FCC烟气中的SOx,NOx"", 《化工进展》 * |
| 赵文凯: ""铁基和锰基尖晶石催化剂的制备及其催化臭氧化脱硝性能的研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111203205A (en) * | 2019-12-30 | 2020-05-29 | 安徽元琛环保科技股份有限公司 | Rare earth doping based ZIF-8 nanoporous carbon catalyst and preparation method and application thereof |
| CN111744494A (en) * | 2020-06-11 | 2020-10-09 | 北京华电光大环境股份有限公司 | Flat plate type CO and SO2And NOxSynchronous removal catalyst and preparation method thereof |
| CN112547076A (en) * | 2020-12-23 | 2021-03-26 | 浙江盛旺环境工程有限公司 | Prestressed SCR denitration catalyst and preparation method thereof |
| CN114308052A (en) * | 2021-12-01 | 2022-04-12 | 北京科技大学 | Preparation method of strong-effect water-resistant and sulfur-resistant denitration catalyst |
| CN114308052B (en) * | 2021-12-01 | 2022-11-22 | 北京科技大学 | Preparation method of strong-effect water-resistant and sulfur-resistant denitration catalyst |
| CN115228478A (en) * | 2022-06-29 | 2022-10-25 | 昆明理工大学 | Sulfur-resistant denitration magnetic catalyst and preparation method and application thereof |
| CN115888850A (en) * | 2022-08-25 | 2023-04-04 | 国能龙源催化剂江苏有限公司 | Regeneration method of SCR denitration catalyst, denitration catalyst prepared by regeneration method and application of denitration catalyst |
| CN115888850B (en) * | 2022-08-25 | 2024-01-26 | 国能龙源催化剂江苏有限公司 | Regeneration method of SCR denitration catalyst, denitration catalyst prepared by method and application of denitration catalyst |
| CN116492987A (en) * | 2023-05-22 | 2023-07-28 | 湘潭大学 | NO adsorbent and preparation method and application thereof |
| CN116492987B (en) * | 2023-05-22 | 2024-10-29 | 湘潭大学 | NO adsorbent and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108355665A (en) | Energy simultaneous SO_2 and NO removal has spinel structure catalyst and its preparation method and application | |
| CN105032403B (en) | One kind is used for flue gas low-temperature desulphurization denitration catalyst and preparation method thereof | |
| CN102861595B (en) | Honeycombed SCR (selective catalytic reduction) denitrification catalyst for low-temperature flue gas denitrification and preparation method thereof | |
| CN104646022B (en) | A kind of honeycomb fashion low-temperature denitration catalyst and preparation method thereof | |
| CN105289630A (en) | Method for preparing catalyst capable of performing simultaneous desulfurization and denitrification on flue gas | |
| CN109092325A (en) | A kind of catalyst and the preparation method and application thereof for low-temperature denitration of flue gas | |
| CN113289602A (en) | Catalyst for carbonyl sulfide hydrolysis in blast furnace gas and preparation method and application thereof | |
| CN107551811B (en) | Sintering flue gas SCR denitration process based on dry method and semi-dry desulphurization | |
| CN110508274A (en) | Modification biological charcoal low-temperature denitration catalyst and its application | |
| CN101507928A (en) | Ferro manganese composite oxides catalyst and preparation method and use thereof | |
| CN106669670B (en) | A kind of preparation method of fume desulfurizing agent | |
| CN105521781B (en) | A kind of preparation method of fume desulfurizing agent | |
| CN106076417A (en) | Charcoal base heteropolyacid catalyst and preparation and application method thereof for low-temperature flue gas simultaneous SO_2 and NO removal | |
| CN110479094A (en) | A kind of desulphurization catalyst and the flue gas desulfurization processing system based on desulphurization catalyst | |
| CN101628202B (en) | Nanoparticle surface modified active semi-coke compound desulfurization denitrification agent and preparation method thereof | |
| CN101507923A (en) | Preparation method of catalyst for sintering flue gas and desulfurizing and denitrifying | |
| CN106732537A (en) | It is a kind of to add attapulgite modified low-temperature SCR catalyst and preparation method thereof | |
| CN110013885A (en) | The regeneration method of denitrating catalyst | |
| CN106582740A (en) | Method for preparing heteropoly acid composite carbon material with popcorn as precursor for low-temperature removal of NOx | |
| CN105771967A (en) | Metal oxide-vanadate/attapulgite catalyst | |
| CN103316667A (en) | Desulfurization and denitration agent for glue gas, and ultrasonic activating preparation method thereof | |
| CN109433236A (en) | Porous carbon material loads zeroth order Fe-Fe3The denitrating catalyst of C and its preparation, application method | |
| CN106824174A (en) | A kind of coccoid catalyst of high-efficient purification nitrogen oxides and preparation method thereof | |
| CN108479744A (en) | A kind of preparation method and applications of desulphurization catalyst | |
| CN110449161A (en) | A kind of ozone catalytic oxidation catalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180803 |