CN108404930A - A kind of low-temperature denitration catalyst and preparation method thereof with nucleocapsid - Google Patents
A kind of low-temperature denitration catalyst and preparation method thereof with nucleocapsid Download PDFInfo
- Publication number
- CN108404930A CN108404930A CN201810344121.6A CN201810344121A CN108404930A CN 108404930 A CN108404930 A CN 108404930A CN 201810344121 A CN201810344121 A CN 201810344121A CN 108404930 A CN108404930 A CN 108404930A
- Authority
- CN
- China
- Prior art keywords
- nucleocapsid
- low
- catalyst
- manganese
- denitration catalyst
- 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 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 26
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 230000004044 response Effects 0.000 claims abstract description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000013049 sediment Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 9
- 238000001354 calcination Methods 0.000 abstract description 3
- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 229910015189 FeOx Inorganic materials 0.000 description 11
- 229910016978 MnOx Inorganic materials 0.000 description 11
- 239000003546 flue gas Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000010276 construction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002574 poison Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000883964 Ariocarpus retusus Species 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229940087654 iron carbonyl Drugs 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003643 water by type Substances 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
- B01J23/70—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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of low-temperature denitration catalysts with nucleocapsid, using iron oxide and manganese oxide as active component, nucleocapsid is formed by iron oxide and manganese oxide, the manganese oxide is core portion, the iron oxide is shell portion, and the molar ratio of manganese element and ferro element is 8：5.The present invention also provides a kind of preparation methods of the low-temperature denitration catalyst with nucleocapsid, ethylene glycol solution is added in manganese nitrate sample, stirring at normal temperature, hydro-thermal process in pvc response kettle is poured this solution into, room temperature is cooled to, weighs the addition of nitric acid iron sample, stirring, ultrasonic vibration, be subsequently poured into hydro-thermal process in pvc response kettle, postcooling, be centrifugally separating to obtain sediment；Drying precipitate, calcining are finally obtained into required sample.Catalyst of the present invention can significantly improve the out of stock activity of low temperature, nitrogen selective and anti-sulfur dioxide ability.
Description
Technical field
The invention belongs to chemical fields, are related to a kind of catalyst, and specifically a kind of low temperature with nucleocapsid is de-
Denox catalyst and preparation method thereof.
Background technology
Atmosphere pollution brings prodigious influence to the life of the mankind, and nitrogen oxides is one of its major pollutants.
The discharge for how effectively reducing NO_x in Air Environment has become extremely urgent problem.The selective catalytic denitrification process (SCR) skill
Art is because of its efficient and technology maturation, it has also become denitrating flue gas most has effective method.And the research of denitrating catalyst performance is always
It is the emphasis of SCR researchs.
Catalyst is the core product of denitrating flue gas, and quality good or not directly determines the height of denitrating flue gas efficiency,
In catalytic denitration technology, catalyst is most important, and the expense in most of denitrification process both also is from the aging of catalyst and goes back
The consumption of former agent.The investment cost of denitrating catalyst usually accounts for the 40%~60% of entire denitrification investment, and during " 12th Five-Year Plan "
Denitrating flue gas will bring more than nearly 200 hundred million yuan of new markets to denitrating catalyst, at present the titanium dioxide system of domestic production catalyst
Make technology to be monopolized by external fewer companies, therefore, it is de- to China's flue gas to research and develop the SCR denitration with independent intellectual property right
Nitre development is of great importance.
In recent years, Mn, Fe metal oxides draw its higher activity and are concerned in SCR denitration direction.It receives
Rice core-shell material has prodigious advantage because of its special structure and size, in skin effect, small-size effect and quantum effect.
Therefore, the research of catalyst with core-casing structure becomes the popular direction of scientific research field.Prepared by composite oxides has nucleocapsid
Catalyst not only compensate for the deficiency of homogenous material catalysis reaction, while it is very big to cause special construction also to have in terms of antitoxinization
Raising, patent of the present invention will by hydro-thermal method prepare synthesis with nucleocapsid mechanism MnOx@FeOx catalyst and taken off for SCR
Nitre reacts, and improves its catalytic efficiency and anti-SO2Poison performance.
Invention content
For above-mentioned technical problem in the prior art, the present invention provides a kind of low-temperature denitrations with nucleocapsid to urge
Agent and preparation method thereof, described this low-temperature denitration catalyst with nucleocapsid and preparation method thereof will solve existing
Catalyst activity in technology for low-temperature denitration of flue gas is not high, anti-sulfur dioxide poison can force difference the technical issues of.
The present invention provides a kind of low-temperature denitration catalysts with nucleocapsid, using iron oxide and manganese oxide as activearm
Point, nucleocapsid is formed by iron oxide and manganese oxide, the manganese oxide is core portion, and the iron oxide is shell portion, manganese element
Molar ratio with ferro element is 8：5.
The present invention also provides a kind of preparation methods of above-mentioned low-temperature denitration catalyst with nucleocapsid, including with
Lower step：
1) it is 8 according to the molar ratio of manganese element and ferro element：5 weigh ferric nitrate and manganese nitrate；
2) manganese nitrate is dissolved in ethylene glycol solution；
3) solution of step 2) is transferred to hydro-thermal process in pvc response kettle；
4) suspension after reacting step 3) is cooling, shakes and ferric nitrate stirring is added；
5) mixing suspension of step 4) is transferred to hydro-thermal process in pvc response kettle；
6) it by sediment centrifugation, the cleaning after reaction, then takes out and dries, roasted at 450-500 DEG C again later
It burns, roasting carries out 3-4h, obtains the low-temperature denitration catalyst with nucleocapsid.
Further, step 3) hydro-thermal reaction 9 hours at 180 DEG C, to promote the forming of manganese oxide nano granule.
Further, it is stirred under step 4) room temperature, ultrasonic vibration 1h.
Further, step 5) hydro-thermal reaction 8h at 190 DEG C in pvc response kettle so that iron oxide uniformly wraps
It overlays on nano manganese oxide particle, forms nucleocapsid.
Further, step 6) be centrifuged repeatedly, alcohol washes 3 times.
Further, step 6) drying carries out 12-15h at 100-110 DEG C.
The present invention is bimetallic oxide as active component using manganese oxide, iron oxide, passes through two one-step hydrothermals synthesis tool
There is the MnOx@FeOx catalyst of nucleocapsid.
XPS characterization results show that the ferro element in catalyst mainly exists with ferric iron, and that catalysis that activity is best
Hydroxyl trivalent iron content in agent is especially more, and hydroxyl trivalent iron is conducive to NH4+- Bronsted acid site is increased, at the same its four
The ratio of valence manganese is also enhanced, and as a result illustrates catalyst to NH3Absorption enhancing, and have stronger redox ability.
And H2TPR table sign catalyst of the explanation with nucleocapsid characterizes mutually evidence with stronger redox ability, with XPS.
In addition, can be seen that the peak intensity of the catalyst with nucleocapsid much smaller than ordinary construction from the XPS of S elements
Catalyst illustrates that the sulfate on its surface is less, to improve its anti-SO2Poisoning effect.
In-situ Infrared Characterization the result shows that, the L-H mechanism and E-R mechanism of the catalyst coexist, in the L-H mechanism of low-temperature zone
In, increasing for iron carbonyl is conducive to ammonia in catalyst surface progress chemisorption, while absorption is easy to the nitrous acid category of reaction
Group, gradually stronger Nitrates of thermal stability less.To NH after there is the MnOx@FeOx of nucleocapsid to vulcanize simultaneously3And NO
Absorption is all more than what the catalyst of ordinary construction was eager to excel, which illustrates to have the catalyst of nucleocapsid to have stronger absorption
Effect and anti-SO2Effect.
Catalyst of the present invention can be to the nitrogen oxides of exhaust gas of the discharges such as power generation gas turbine and coal-burning boiler at
Reason can significantly improve the out of stock activity of low temperature and anti-sulfur dioxide ability.
Compared with prior art, the present invention its technological progress is significant.Catalyst provided by the invention has in low temperature
There is the activity of higher Reduction of NO, i.e., when denitration temperature is 250 DEG C, the conversion ratio of NO reaches 93% or more.Catalyst
Preparation process is simple, environment friendly and pollution-free, is urged using bimetallic oxide component and the uniform nanoparticles with nucleocapsid
Agent overcomes typical catalyst because active component is single and easy by SO2The problem of influence, has stronger commercial Application valence
Value.The catalyst that the present invention is prepared at 150-450 DEG C, especially at 300 DEG C hereinafter, compared with baseline catalyst activity with
The anti-SO of water resistant2It is greatly improved in ability, is more conducive to that SCR denitration device is made to be arranged in thermal power plant's back-end ductwork, to reduce waste heat
Loss improves thermal power plant's performance driving economy.
Description of the drawings
Fig. 1 is the catalytic efficiency that catalyst of the present invention carries out denitrating flue gas with typical catalyst under the same conditions.
Fig. 2A is the TEM electromicroscopic photographs of ordinary construction MnFeOx catalyst, and Fig. 2 B are the MnOx@FeOx catalysis of nucleocapsid
The TEM electromicroscopic photographs of agent, Fig. 2 C are the MnOx@FeOx catalyst high definition electromicroscopic photographs HRTEM of nucleocapsid.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings, but is not intended to limit the present invention.
In the embodiment of the present invention catalytic reactor used use the outer diameter purchased from Zhejiang Fan Tai Instrument Ltd. for 16mm,
The 4100 type fixed bed micro anti-evaluation devices of long 480mm, unstripped gas enter reactor by preheating, and reaction temperature is in 100-400
DEG C, flow velocity 1000ml/min, space velocity 108000h-1。
Simulated flue gas forms：NO is 600ppm, NH3For 600ppm and O2It is 5%, remaining gas Ar is as Balance Air, gas
Body flow is by the CS200 type mass flowmenters control purchased from Beijing Co., Ltd of Sevenstar Huachuang Electronic.
NO, NH that molar concentration used in the present invention is 1%3, Balance Air Ar, purchased from the big wound calibrating gas in Shanghai it is limited
Company, the O that purity is 99.99%2, Ar, be purchased from Jiangnan mixed gas Co., Ltd；The nitre that drug purity used is 99.9%
Sour iron, manganese nitrate and ethylene glycol are purchased from Aladdin, are specific embodiment below：
Embodiment 1
The catalyst with nucleocapsid for be catalyzed the NO restored that is made according to the present invention, wherein active component
Molar ratio is：Mn:Fe=8:5.Specific preparation process is as follows：
The MnOx@FeOx catalyst with nucleocapsid is prepared by two one-step hydrothermals for experiment.The manganese nitrate weighed
The ethylene glycol solution of 200mL, stirring at normal temperature 15 minutes is added in sample；It pours this solution into later 180 in pvc response kettle
DEG C reaction 9 hours, be cooled to room temperature, obtain suspension A.Nitric acid iron sample is weighed, is added in suspension A, and be stirred continuously,
It is denoted as suspension B.B solution is poured into pvc response kettle and is reacted 8 hours for 190 DEG C, cooling, deionized water and alcohol washes
And it centrifuges, 100 DEG C of the sediment drying 24 hours that will be obtained.Finally, 450 DEG C of calcinings in Muffle furnace by the solid powder
MnOx@FeOx catalyst is obtained within 4 hours, grinding screening is spare.
Fig. 2A is the TEM electromicroscopic photographs of ordinary construction MnFeOx catalyst, and Fig. 2 B are the MnOx@FeOx catalysis of nucleocapsid
The TEM electromicroscopic photographs of agent, the MnOx@FeOx catalyst high definition electromicroscopic photographs HRTEM of Fig. 2 C nucleocapsids.
Show to have synthesized the radius with nucleocapsid of regular shape from Fig. 2 TEM characterization results by two one-step hydrothermals
For 200 nanometers of spherical particle, and shell portion lattice fringe corresponds to Fe3O4(3 1 1) crystal face.Illustrate that shell portion is mainly iron oxide,
Core portion is mainly manganese oxide.
Embodiment 2
The catalyst for the NO that the catalysis of the ordinary construction for comparison made according to the present invention restores, wherein active component
Molar ratio be：Mn:Fe=8:5.It is as follows：
Experiment prepares MnFeOx catalyst by coprecipitation.Manganese nitrate sample and nitric acid iron sample are weighed respectively, are added
200mL deionized waters, are stirred continuously at room temperature, instill ammonium hydroxide adjustment pH to 8, and solution precipitates at this time, is stirred continuously 30 points
Zhong Hou, deionized water are pure and fresh to neutrality.It filters later, 100 DEG C of dryings 24 hours are last, by the solid powder in Muffle furnace
450 DEG C of calcinings obtain MnFeOx catalyst for 4 hours, and grinding screening is spare.
Simulate gas (flue gas flow rate 1000ml/min, gas concentration：NO is 600ppm, NH3For 600ppm and O2For
5%, remaining gas Ar) in gas mixed box mix after, be then fed into the denitration that fixed bed micro anti-evaluation device poisons in resistant to potassium
Under the action of catalyst and typical catalyst, NH3NO is reduced to N2, the gaseous mixture after reaction is through phosphoric acid solution absorption unreacted
NH3It is discharged into air by exhaust pipe, the NO concentration of inlet and outlet is detected using the model60i flue gas analyzers in the U.S., denitration
Result see the table below：
The Activity evaluation tables of data of 1 different catalysts of table
Wherein, 1 denitration efficiency calculation formula of table is as follows：
2 denitration efficiency calculation formula of table is as follows：
As it can be seen from table 1 having catalyst with core-casing structure and typical catalyst in phase using what the present invention was prepared
Denitrating flue gas is carried out under conditions of, it is higher than typical catalyst denitration efficiency, when low-temperature zone denitration temperature is 100-300 DEG C,
The denitration efficiency ratio MnFeOx catalyst of MnOx@FeOx catalyst with nucleocapsid is high by 15% or so.And in high temperature section
Also above the MnFeOx catalyst of ordinary construction.
Catalyst obtained above is respectively placed in 100ppmSO2Under carry out anti-SO2Poison experiment, experimental result such as Fig. 1 institutes
Show.The result shows that the catalyst and typical catalyst that are prepared using the present invention carry out anti-SO under the same conditions2It is real
It tests, the antitoxinization performance of the MnOx@FeOx catalyst with nucleocapsid is better than the MnFeOx catalyst of ordinary construction.
To sum up, the catalyst that the present invention is prepared is at 150-450 DEG C, especially at 300 DEG C hereinafter, compared to common
Catalyst is in activity and anti-SO2It is greatly improved in ability, is more conducive to that SCR denitration device is made to be arranged in thermal power plant's back-end ductwork,
To reduce waste heat loss, thermal power plant's performance driving economy is improved.
Above said content is only the basic explanation under present inventive concept, and that is done according to the technique and scheme of the present invention appoints
What equivalent transformation, belongs to the scope of protection of the invention.
Claims (7)
1. a kind of low-temperature denitration catalyst with nucleocapsid, it is characterised in that：Using iron oxide and manganese oxide as active component,
Nucleocapsid is formed by iron oxide and manganese oxide, the manganese oxide is core portion, and the iron oxide is shell portion, manganese element and iron
The molar ratio of element is 8：5.
2. a kind of preparation method of low-temperature denitration catalyst with nucleocapsid described in claim 1, it is characterised in that packet
Include following steps：
1）It is 8 according to the molar ratio of manganese element and ferro element：5 weigh ferric nitrate and manganese nitrate；
2）Manganese nitrate is dissolved in ethylene glycol solution；
3）By step 2）Solution be transferred to hydro-thermal process in pvc response kettle；
4）By step 3）Suspension after reaction is cooling, shake and ferric nitrate stirring is added；
5）By step 4）Mixing suspension be transferred to hydro-thermal process in pvc response kettle；
6）By sediment centrifugation, the cleaning after reaction, then takes out and dry, roasted at 450-500 DEG C again later, roasted
Row 3-4h is burnt into, the low-temperature denitration catalyst with nucleocapsid is obtained.
3. a kind of preparation method of low-temperature denitration catalyst with nucleocapsid according to claim 2, feature exist
In：Step 3）Hydro-thermal reaction 9 hours at 180 DEG C.
4. a kind of preparation method of low-temperature denitration catalyst with nucleocapsid according to claim 2, feature exist
In：Step 4）It is stirred under room temperature, ultrasonic vibration 1h.
5. a kind of preparation method of low-temperature denitration catalyst with nucleocapsid according to claim 2, feature exist
In：Step 5）In pvc response kettle at 190 DEG C hydro-thermal reaction 8h.
6. a kind of preparation method of low-temperature denitration catalyst with nucleocapsid according to claim 2, feature exist
In：Step 6）It is centrifuged repeatedly, alcohol washes 3 times.
7. a kind of preparation method of low-temperature denitration catalyst with nucleocapsid according to claim 2, feature exist
In：Step 6）Drying carries out 12-15h at 100-110 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810344121.6A CN108404930A (en) | 2018-04-17 | 2018-04-17 | A kind of low-temperature denitration catalyst and preparation method thereof with nucleocapsid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810344121.6A CN108404930A (en) | 2018-04-17 | 2018-04-17 | A kind of low-temperature denitration catalyst and preparation method thereof with nucleocapsid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108404930A true CN108404930A (en) | 2018-08-17 |
Family
ID=63135858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810344121.6A Pending CN108404930A (en) | 2018-04-17 | 2018-04-17 | A kind of low-temperature denitration catalyst and preparation method thereof with nucleocapsid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108404930A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110947396A (en) * | 2019-12-18 | 2020-04-03 | 上海应用技术大学 | Spherical manganese oxide coated iron oxide core-shell structure compound and preparation method and application thereof |
| CN111054379A (en) * | 2019-12-18 | 2020-04-24 | 上海应用技术大学 | Spherical ferric oxide coated manganese oxide core-shell structure compound and preparation and application thereof |
| CN111185189A (en) * | 2020-01-16 | 2020-05-22 | 中国重型机械研究院股份公司 | Method for preparing yolk-egg white type SCR denitration catalyst and application |
| CN111921523A (en) * | 2020-07-13 | 2020-11-13 | 内蒙古大学 | Medium-low temperature SCO denitration catalyst and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120164047A1 (en) * | 2009-02-16 | 2012-06-28 | Augustine Steven M | Catalyst Promoters In Vanadium-Free Mobile Catalyst |
| CN102941083A (en) * | 2012-11-08 | 2013-02-27 | 环境保护部华南环境科学研究所 | Medium/low-temperature core-shell denitration catalyst and preparation method and application thereof |
| CN104016522A (en) * | 2014-06-23 | 2014-09-03 | 瀚蓝环境股份有限公司 | Method for handling emergent chlorophenol pollution of water body by using Fe3O4-MnO2 core-shell material |
| CN104162392A (en) * | 2013-05-20 | 2014-11-26 | 孙红梅 | Core-shell porous ball, manufacturing method ad applications thereof |
| CN104646021A (en) * | 2015-01-20 | 2015-05-27 | 郑州轻工业学院 | Ferroferric oxide/silica/manganese dioxide catalyst and preparation method thereof |
| US20150335767A1 (en) * | 2012-11-15 | 2015-11-26 | Hong Kong Baptist University | Dual-Mode Contrast Agent and Uses Thereof in Real-time Monitoring and Harvesting of Neural Stem Cells |
| CN105536811A (en) * | 2015-12-22 | 2016-05-04 | 中国科学院山西煤炭化学研究所 | A core-shell type catalyst for lower-alkene preparation from synthetic gas, a preparing method thereof and applications of the catalyst |
| CN105771877A (en) * | 2016-04-23 | 2016-07-20 | 上海大学 | Method for preparing composite adsorption material MnO2-Fe3O4 with core-shell structure |
| CN105771934A (en) * | 2016-05-06 | 2016-07-20 | 扬州大学 | Preparation method of nanometer magnetic adsorbent with core-shell structure |
| CN106732536A (en) * | 2016-11-17 | 2017-05-31 | 华南理工大学 | A kind of CeO2@MnOx low-temperature SCR catalyst for denitrating flue gas and preparation method and application |
-
2018
- 2018-04-17 CN CN201810344121.6A patent/CN108404930A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120164047A1 (en) * | 2009-02-16 | 2012-06-28 | Augustine Steven M | Catalyst Promoters In Vanadium-Free Mobile Catalyst |
| CN102941083A (en) * | 2012-11-08 | 2013-02-27 | 环境保护部华南环境科学研究所 | Medium/low-temperature core-shell denitration catalyst and preparation method and application thereof |
| US20150335767A1 (en) * | 2012-11-15 | 2015-11-26 | Hong Kong Baptist University | Dual-Mode Contrast Agent and Uses Thereof in Real-time Monitoring and Harvesting of Neural Stem Cells |
| CN104162392A (en) * | 2013-05-20 | 2014-11-26 | 孙红梅 | Core-shell porous ball, manufacturing method ad applications thereof |
| CN104016522A (en) * | 2014-06-23 | 2014-09-03 | 瀚蓝环境股份有限公司 | Method for handling emergent chlorophenol pollution of water body by using Fe3O4-MnO2 core-shell material |
| CN104646021A (en) * | 2015-01-20 | 2015-05-27 | 郑州轻工业学院 | Ferroferric oxide/silica/manganese dioxide catalyst and preparation method thereof |
| CN105536811A (en) * | 2015-12-22 | 2016-05-04 | 中国科学院山西煤炭化学研究所 | A core-shell type catalyst for lower-alkene preparation from synthetic gas, a preparing method thereof and applications of the catalyst |
| CN105771877A (en) * | 2016-04-23 | 2016-07-20 | 上海大学 | Method for preparing composite adsorption material MnO2-Fe3O4 with core-shell structure |
| CN105771934A (en) * | 2016-05-06 | 2016-07-20 | 扬州大学 | Preparation method of nanometer magnetic adsorbent with core-shell structure |
| CN106732536A (en) * | 2016-11-17 | 2017-05-31 | 华南理工大学 | A kind of CeO2@MnOx low-temperature SCR catalyst for denitrating flue gas and preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| S. ESTRADÉ ET AL.: ""Distinguishing the core from the shell in MnOx/MnOy and FeOx/MnOx core/shell nanoparticles through quantitative electron energy loss spectroscopy (EELS) analysis"", 《MICRON》 * |
| SIXIANG CAI ET AL.: ""Design of multi-shell Fe2O3@MnOx@CNTs for the selective catalytic reduction of NO with NH3: improvement of catalytic activity and SO2 tolerance"", 《NANOSCALE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110947396A (en) * | 2019-12-18 | 2020-04-03 | 上海应用技术大学 | Spherical manganese oxide coated iron oxide core-shell structure compound and preparation method and application thereof |
| CN111054379A (en) * | 2019-12-18 | 2020-04-24 | 上海应用技术大学 | Spherical ferric oxide coated manganese oxide core-shell structure compound and preparation and application thereof |
| CN110947396B (en) * | 2019-12-18 | 2023-03-28 | 上海应用技术大学 | Spherical manganese oxide coated iron oxide core shell structural composite, preparation method and application |
| CN111185189A (en) * | 2020-01-16 | 2020-05-22 | 中国重型机械研究院股份公司 | Method for preparing yolk-egg white type SCR denitration catalyst and application |
| CN111921523A (en) * | 2020-07-13 | 2020-11-13 | 内蒙古大学 | Medium-low temperature SCO denitration catalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111229212B (en) | CO-SCR denitration catalyst, preparation method and application | |
| CN108404930A (en) | A kind of low-temperature denitration catalyst and preparation method thereof with nucleocapsid | |
| CN105126825B (en) | A kind of low-temperature denitration of flue gas catalyst and preparation method thereof | |
| CN105013474B (en) | The preparation method of metal oxide denitrating catalyst with orderly hierarchical porous structure | |
| CN105833901B (en) | A kind of PrOx-MnOx/ SAPO-34 low-temperature SCR catalyst for denitrating flue gas and the preparation method and application thereof | |
| CN108465470B (en) | A kind of γ-Fe2O3Nano-particle modified nf-MnO2/ ATP low-temperature denitration catalyst | |
| CN110354846A (en) | A kind of preparation method of manganese cerium dopping graphene low temperature SCR denitration catalyst | |
| CN108554398B (en) | Preparation method and application of wide-temperature-window denitration catalyst | |
| CN103752323A (en) | Preparation method for denitrified catalyst with nanometer multi-wall spherical spinel structure | |
| CN108393085B (en) | Attapulgite-loaded cerium-doped MnTiOX ternary-component low-temperature denitration catalyst and preparation method thereof | |
| CN111569865A (en) | Bio-based low-temperature denitration catalyst and preparation method thereof | |
| WO2021180142A1 (en) | Hybrid synergistically-enhanced low-temperature scr denitration catalyst and preparation method therefor | |
| CN104815671A (en) | Selective catalytic reduction low-temperature denitration catalyst and preparation method thereof | |
| CN108906050A (en) | A kind of carbon nano tube-doped Copper-Aluminum compound metal oxide denitrating catalyst and its preparation method and application | |
| CN106732536B (en) | A kind of CeO2@MnOx low-temperature SCR catalyst for denitrating flue gas and the preparation method and application thereof | |
| CN106492812A (en) | A kind of meso-pore CexFe1‑xO2The preparation method of solid solution catalyst | |
| WO2023035532A1 (en) | Preparation method for la1-xmn1+xo3 | |
| CN112337460A (en) | Method for preparing Mn-based spinel low-temperature denitration catalyst by using complex acid solution | |
| CN107185555B (en) | Preparation method of copper-doped cerium sulfide-based nanocrystalline denitration catalyst | |
| CN110404542A (en) | A kind of core-shell structure copolymer ball CoFe2O4Catalyst and the preparation method and application thereof | |
| CN108404906B (en) | Nano-rod-shaped manganese-chromium composite oxide low-temperature denitration catalyst and preparation method thereof | |
| CN111375407B (en) | Low-temperature denitration catalyst and preparation method and application thereof | |
| CN108311134A (en) | Diesel vehicle/steamer tail gas SCR denitration titanium tungsten silicon composite powder and preparation method | |
| CN115318303B (en) | Catalyst for removing soot particles of diesel vehicle at low temperature and preparation method thereof | |
| CN110697768A (en) | Mesoporous TiO 22Material, catalyst, preparation method of material and catalyst, and denitration method |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180817 |
|
| WD01 | Invention patent application deemed withdrawn after publication |