CN109731569A - Cellular SCR denitration and preparation method with three-dimensional multistage cellular structure - Google Patents
Cellular SCR denitration and preparation method with three-dimensional multistage cellular structure Download PDFInfo
- Publication number
- CN109731569A CN109731569A CN201811611515.XA CN201811611515A CN109731569A CN 109731569 A CN109731569 A CN 109731569A CN 201811611515 A CN201811611515 A CN 201811611515A CN 109731569 A CN109731569 A CN 109731569A
- Authority
- CN
- China
- Prior art keywords
- cellular
- scr denitration
- dimensional multistage
- cellular structure
- preparing
- 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.)
- Granted
Links
- 230000001413 cellular effect Effects 0.000 title claims abstract description 24
- 210000003850 cellular structure Anatomy 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000006229 carbon black Substances 0.000 claims abstract description 21
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000742 Cotton Polymers 0.000 claims abstract description 11
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 10
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 10
- 239000003365 glass fiber Substances 0.000 claims abstract description 10
- 239000004310 lactic acid Substances 0.000 claims abstract description 10
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 239000008117 stearic acid Substances 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000006396 nitration reaction Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- -1 is kneaded Polymers 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- 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
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/60—
-
- 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
Abstract
The invention discloses the cellular SCR denitration with three-dimensional multistage cellular structure, the raw material including following parts by weight is prepared: titanium dioxide 80~100, paper pulp cotton 1~2, multi-walled carbon nanotube 0.1~0.5, carbon black 0.5~2.5, silica 1~3, glass fibre 5~10, ammonium metavanadate 1~3, ammonium metatungstate 5~10, six nitric hydrate ceriums 5~10, monoethanolamine 5~15, carboxymethyl cellulose 1~2, ethylene oxide are 1~2, lactic acid 5~15, stearic acid 1~2, ammonium hydroxide 15~25, deionized water 30~50.Invention additionally discloses the methods that preparation has the cellular SCR denitration of three-dimensional multistage cellular structure, the pore network and meso-hole structure that there is prepared catalyst three-dimensional order to communicate with each other, while improving compressive resistance, the characteristic of its bigger serface is maintained.
Description
Technical field
The invention belongs to industrial denitration technology fields, and in particular to the cellular SCR with three-dimensional multistage cellular structure is de-
Denox catalyst and preparation method.
Background technique
As the dry type denitration technology of nitrogen oxides in removal coal-fired flue-gas, selective-catalytic-reduction denitrified method is adopted extensively
With it makees reducing agent using ammonia, makes NO and NO in flue gas2N is generated by restoring after catalyst layer2And H2O reaches removing cigarette
NO in gasxPurpose.Catalyst majority is used with TiO2For carrier, V2O5、WO3For the porous media of active component, have high de-
Many advantages, such as nitre rate, selectivity good, stable, moderate temperature, therefore always by the favor of researchers at home and abroad.Its core
Heart problem is the development, exploitation and improvement of catalyst.
Currently, coal-burning power plant's denitration arrangement mainly using high dirt arrange formula, by exhaust gas dust it is big, be easy so that
Catalyst bed blocks and generates high pressure；In addition, catalyst in use can be by particulate matter in entrucking, shock, flue gas
The consumption such as abrasion, therefore, in practical applications, other than the activity of catalyst to be guaranteed, it is often more important that consider its
Practicability, such as mechanical strength, porosity performance.In the active temperature range of catalyst, denitration efficiency is with specific surface area
Increase and increase, the raising of catalyst porosity can promote its specific surface area to a certain extent.But in high porosity item
Under part, it is difficult to prepare high-intensitive catalyst.Therefore, high porosity how is prepared, and has the honeycomb fashion of certain mechanical strength
Denitrating catalyst is still current urgent problem to be solved.
The moulding process of honeycomb type denitrification catalyst and the use of pore creating material directly affect its mechanical strength and porosity, institute
Need to be optimized to moulding process.Currently, additional amount and kind of some researchers by adjusting extrusion pressure and pore creating material
Class can prepare the honeycomb type denitrification catalyst of high porosity and hierarchical porous structure, not only improve mechanical strength, but also can be reduced
Catalyst amount.It therefore, is effectively one kind by adjusting pore structure come the mechanical strength and denitration efficiency for regulating and controlling catalyst
Method.
The adsorption capacity of catalyst is to removing NOxEfficiency have a tremendous influence, adsorption capacity be most directly associated with because
Element is the microstructure of catalyst.One good microstructure means that catalyst has more bigger serface, more micropores
Structure, suitable pore-size distribution and quick mass transfer rate increase its adsorbance to gas molecule, and then improve denitration
Energy.However, the number cells in catalyst increase when specific surface area increases, average pore size decline, in the catalyst to gas
It is unfavorable to spread.Therefore, influence of the pore structure of catalyst to denitrification process depends on respectively expanding gas when pore structure variation
Scattered and chemical reaction process influence degree.Three-dimensional multistage cellular structure can greatly increase the utilization of the specific surface area of material, hole
Rate reaches the diffusion rate improved gas in hole and enhances denitration effect.The material of multi-stage artery structure also can be reduced greatly
The blocking of duct caused by molecule and raising diffuser efficiency, reaction compartment of the mesoporous or micropore canals as reactant, reactant
Can be efficiently close to active sites with the pressure drop of very little in big pore system, it while be detached from product can and stopped reaction in time.
Currently, three-dimensional multistage cellular structure, which is introduced honeycomb type denitrification catalyst research, yet there are no document and patent report.
Summary of the invention
Technical problem to be solved by the present invention lies in: how to pass through the microcosmic hole knot of transformation honeycomb type denitrification catalyst
Structure, pore property regulate and control its macro property, to prepare high porosity, and have the cellular denitration catalyst of certain mechanical strength
Agent.
The present invention solves above-mentioned technical problem using following technical scheme:
Cellular SCR denitration with three-dimensional multistage cellular structure, the raw material including following parts by weight: titanium dioxide
Titanium 80~100, paper pulp cotton 1~2, multi-walled carbon nanotube 0.1~0.5, carbon black 0.5~2.5, silica 1~3, glass fibre 5
~10, ammonium metavanadate 1~3, ammonium metatungstate 5~10, six nitric hydrate ceriums 5~10, monoethanolamine 5~15, carboxymethyl cellulose 1
~2, ethylene oxide is 1~2, lactic acid 5~15, stearic acid 1~2, ammonium hydroxide 15~25, deionized water 30~50.
Preferably, a method of prepare the cellular SCR denitration with three-dimensional multistage cellular structure, including with
Lower step:
(1) by multi-walled carbon nanotube and carbon black dispersion in nitration mixture 3~6h of acidification, use distilled water after being cooled to room temperature
Dilution, filtration washing to neutrality, product are dried in vacuo 10~12h at 75~80 DEG C, are ground into a powder, the multi wall carbon being acidified
Nanotube and black stock powder；
(2) multi-walled carbon nanotube and black stock powder that are acidified obtained by step (1) are added in ammonium hydroxide, ultrasound point
It dissipates uniformly, obtains mixed liquor 1.；
(3) mixed solution to monoethanolamine and deionized water is added in ammonium metavanadate, ammonium metatungstate, six nitric hydrate ceriums
In, it dissolves by heating, obtains mixed liquor 2.；
(4) 1. under stiring with mixed liquor and contains titanium dioxide, silica, glass fibre, hard
It in resin acid and the mixture of paper pulp cotton, is kneaded, carboxymethyl cellulose, ethylene oxide and lactic acid is added, is kneaded, is mixed again
Pug carries out aging；
(5) extrusion molding of mixing pug, the drying, calcining obtained step (4), obtains target product.
Preferably, multi-wall carbon nano-tube pipe diameter described in the step (1) is 10~20nm, and length is 5~15 μm；Institute
The partial size for the carbon black stated is about 15~20nm.
Preferably, the mass ratio of multi-walled carbon nanotube described in step (1) and carbon black is 1: (1~5)；The multi wall carbon is received
The mass ratio of the gross mass and mixed acid solution of mitron and carbon black is 1: (5~10).
Preferably, the nitration mixture is mixed at 3: 1 by volume by the concentrated sulfuric acid and concentrated nitric acid.
Preferably, the concentration of ammonium hydroxide is 15% in the step (2), and ultrasonic disperse power is 400~800W, time 0.5
~2h.
Preferably, it is 60~90 DEG C that temperature is dissolved by heating in the step (3).
Preferably, in the step (4) mixture be added to mixed liquor 1. with mixed liquor 2. in front of first stir 0.5~
1h。
Preferably, in the step (4) 1. 2. mixed liquor is added with stirring with mixed liquor in revolving speed for 200~400rpm
Containing in titanium dioxide, silica, glass fibre, stearic acid and the mixture of paper pulp cotton, with revolving speed be 600~800rpm into
Row is kneaded, and after being kneaded uniformly, carboxymethyl cellulose, ethylene oxide and lactic acid is added at 70~90 DEG C, again with revolving speed for 600
~800rpm is kneaded, and mixing pug is obtained, and carries out aging, and ageing time is 12~48h.
Preferably, the cellular catalyst hole count of extrusion molding is 20 × 20 holes in the step (5)；Drying temperature is 20
~60 DEG C；The mixed gas that oxygen content is 30~50% is passed through in calcination process, keeping entire calcining is excess oxygen.
The technology of the present invention is the utility model has the advantages that the invention discloses a kind of cellular SCR with three-dimensional multistage cellular structure to take off
Denox catalyst and preparation method thereof, the catalyst is using titanium dioxide as carrier, vanadic anhydride, tungstic acid and ceria
For active component, using paper pulp cotton, multi-walled carbon nanotube and carbon black as composite pore-forming agent and surplus other auxiliary agents, prepared material
Expect that there is the pore network that communicates with each other of three-dimensional order and meso-hole structure, while improving compressive resistance, maintains its and big compare table
The characteristic of area.
During the preparation process, will multi-walled carbon nanotube and carbon black acidification after improve water solubility so that its in pug
Even dispersion, one-dimensional carbon nanotube form netted pilotaxitic texture, the fully calcined oxygenolysis under excess oxygen, by each micropore-Jie
Hole connects the three-dimensional multistage channel to form a kind of rapid mass transfer.The three-dimensional open-framework possesses spatial network shape nanoscale abundant
Micropore-mesopore and elongated mass transfer channel, not only can be improved the porosity and specific surface area of catalyst, but also maintain higher
Crushing strength；In addition, the characteristic that duct is interconnected, it is uneven on its surface can to resist barium oxide and dust in flue gas
Deposition slows down the covering of the particles such as calcium sulfate active site caused by the blocking of micropore.Prepared catalyst, porosity is high,
And have certain mechanical strength, have very much a prospects for commercial application.
Specific embodiment
For convenient for those skilled in the art understand that technical solution of the present invention, does technical solution of the present invention now in conjunction with embodiment
Further instruction.Described embodiment is a part of the embodiments of the present invention, instead of all the embodiments.
Embodiment 1
A kind of preparation method of the cellular SCR denitration with three-dimensional multistage cellular structure, comprising the following steps:
(1) by 0.2kg multi-walled carbon nanotube and 1.0kg carbon black dispersion in gross mass be the mixed of the 8kg concentrated sulfuric acid and concentrated nitric acid
In acid solution, stir process 3h, is diluted after being cooled to room temperature with distilled water at 40 DEG C, and filtration washing to neutrality, product is in 75 DEG C
Lower vacuum drying 10h, is ground into a powder, the multi-walled carbon nanotube and black stock powder being acidified；Wherein the nitration mixture is molten
V (concentrated sulfuric acid) in liquid: V (concentrated nitric acid) volume ratio is 3: 1；
(2) multi-walled carbon nanotube of acidification obtained above and black stock powder are added to 20kg concentration is 15%
Ammonium hydroxide in, power be 400W under ultrasonic disperse 0.5h, obtain mixed liquor 1.；
(3) successively 1.5kg ammonium metavanadate, 6kg ammonium metatungstate and six nitric hydrate cerium of 6kg are added to containing the mono- second of 5kg
In aqueous alkanolamine, 60 DEG C of sufficiently dissolutions are heated to, obtain mixed liquor 2.；
(4) by above-mentioned mixed liquor 1. with mixed liquor 2. revolving speed be 200rpm be added with stirring containing 90kg titanium dioxide,
It is that 600rpm is mixed with revolving speed in 2kg silica, 6kg glass fibre, 2kg stearic acid and the mixture of 1.5kg paper pulp cotton
After being kneaded uniformly, 8kg lactic acid, 1.5kg carboxymethyl cellulose and 1.5kg ethylene oxide is added, again with revolving speed in refining at 70 DEG C
It is kneaded for 600rpm, obtains mixing pug, aging 12h；
(5) 20 × 20 grinding tool extrusion molding of the catalyst mixing pug for obtaining the step (4), is dried at 20 DEG C
To moisture lower than 3%, in the lower 550 DEG C of calcinings 5h of 35% oxygen content atmosphere, target product is obtained；
Obtained catalyst monomer is cut into 150mm × 150mm × 150mm test block, is tried using electronic type universal
Machine test mechanical strength is tested, tests its specific surface area using atmosphere of static nitrogen absorption method；According to 1 specific implementation step of embodiment, system
Crushing strength diameter/axial direction of standby product respectively reaches 1.5Mpa and 4.9Mpa, and specific surface area reaches 68m2/g。
Embodiment 2
A kind of preparation method of the cellular SCR denitration with three-dimensional multistage cellular structure, comprising the following steps:
(1) by 0.3kg multi-walled carbon nanotube and 1.5kg carbon black dispersion in gross mass be the mixed of the 10kg concentrated sulfuric acid and concentrated nitric acid
In acid solution, stir process 4h, is diluted after being cooled to room temperature with distilled water at 40 DEG C, and filtration washing to neutrality, product is in 80 DEG C
Lower vacuum drying 12h, is ground into a powder, the multi-walled carbon nanotube and black stock powder being acidified；Wherein the nitration mixture is molten
V (concentrated sulfuric acid) in liquid: V (concentrated nitric acid) volume ratio is 3: 1；
(2) multi-walled carbon nanotube of acidification obtained above and black stock powder are added to 20kg concentration is 15%
Ammonium hydroxide in, power be 600W under ultrasonic disperse 1h, obtain mixed liquor 1.；
(3) successively 1.5kg ammonium metavanadate, 6kg ammonium metatungstate and six nitric hydrate cerium of 6kg are added to containing the mono- second of 5kg
In aqueous alkanolamine, 80 DEG C of sufficiently dissolutions are heated to, obtain mixed liquor 2.；
(4) by above-mentioned mixed liquor 1. with mixed liquor 2. revolving speed be 300rpm be added with stirring containing 90kg titanium dioxide,
It is that 700rpm is mixed with revolving speed in 2kg silica, 6kg glass fibre, 2kg stearic acid and the mixture of 1.8kg paper pulp cotton
After being kneaded uniformly, 8kg lactic acid, 1.5kg carboxymethyl cellulose and 1.5kg ethylene oxide is added, again with revolving speed in refining at 80 DEG C
It is kneaded for 700rpm, obtains mixing pug, aging is for 24 hours；
(5) 20 × 20 grinding tool extrusion molding of catalyst mixing pug for obtaining the step (4), 40 DEG C of dryings are extremely
Moisture is lower than 3%, in the lower 550 DEG C of calcinings 5h of 40% oxygen content atmosphere, obtains target product；
Obtained catalyst monomer is cut into 150mm × 150mm × 150mm test block, is tried using electronic type universal
Machine test mechanical strength is tested, tests its specific surface area using atmosphere of static nitrogen absorption method.According to 2 specific implementation step of the present embodiment,
Crushing strength diameter/the axial direction for preparing product respectively reaches 1.1Mpa and 4.1Mpa, and specific surface area reaches 72m2/g。
Embodiment 3
A kind of preparation method of the cellular SCR denitration with three-dimensional multistage cellular structure, comprising the following steps:
(1) by 0.1kg multi-walled carbon nanotube and 0.5kg carbon black dispersion in gross mass be the mixed of the 6kg concentrated sulfuric acid and concentrated nitric acid
In acid solution, stir process 6h, is diluted after being cooled to room temperature with distilled water at 40 DEG C, and filtration washing to neutrality, product is in 80 DEG C
Lower vacuum drying 12h, is ground into a powder, the multi-walled carbon nanotube and black stock powder being acidified；Wherein the nitration mixture is molten
V (concentrated sulfuric acid) in liquid: V (concentrated nitric acid) volume ratio is 3: 1；
(2) multi-walled carbon nanotube of acidification obtained above and black stock powder are added to 20kg concentration is 15%
Ammonium hydroxide in, power be 800W ultrasonic disperse 2h, obtain mixed liquor 1.；
(3) successively 1.5kg ammonium metavanadate, 6kg ammonium metatungstate and six nitric hydrate cerium of 6kg are added to containing the mono- second of 5kg
In aqueous alkanolamine, 90 DEG C of sufficiently dissolutions are heated to, obtain mixed liquor 2.；
(4) by above-mentioned mixed liquor 1. with mixed liquor 2. revolving speed be 400rpm be added with stirring containing 90kg titanium dioxide,
It is that 800rpm is mixed with revolving speed in 2kg silica, 6kg glass fibre, 2kg stearic acid and the mixture of 1.0kg paper pulp cotton
After being kneaded uniformly, 8kg lactic acid, 1.5kg carboxymethyl cellulose and 1.5kg ethylene oxide is added, again with revolving speed in refining at 90 DEG C
It is kneaded for 800rpm, obtains mixing pug, aging is for 24 hours；
(5) 20 × 20 grinding tool extrusion molding of catalyst mixing pug for obtaining the step (4), 60 DEG C of dryings are extremely
Moisture is lower than 3%, in the lower 550 DEG C of calcinings 5h of 30% oxygen content atmosphere, obtains target product；
Obtained catalyst monomer is cut into 150mm × 150mm × 150mm test block, is tried using electronic type universal
Machine test mechanical strength is tested, tests its specific surface area using atmosphere of static nitrogen absorption method.According to 3 specific implementation step of the present embodiment,
Crushing strength diameter/the axial direction for preparing product respectively reaches 1.7Mpa and 5.3Mpa, and specific surface area reaches 51m2/g。
Although the present invention is had been described in detail by above preferred embodiment, but it should be appreciated that the description above
It is not construed as to limit value of the invention.For those skilled in the art to which the present invention belongs, this is not being departed from
Under the premise of inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the scope of protection of the invention.
Claims (10)
1. the cellular SCR denitration with three-dimensional multistage cellular structure, which is characterized in that the original including following parts by weight
Material is prepared: titanium dioxide 80~100, paper pulp cotton 1~2, multi-walled carbon nanotube 0.1~0.5, carbon black 0.5~2.5, dioxy
SiClx 1~3, glass fibre 5~10, ammonium metavanadate 1~3, ammonium metatungstate 5~10, six nitric hydrate ceriums 5~10, monoethanolamine 5
~15, carboxymethyl cellulose 1~2, ethylene oxide are 1~2, lactic acid 5~15, stearic acid 1~2, ammonium hydroxide 15~25, deionized water
30~50.
2. a kind of side for preparing the cellular SCR denitration as described in claim 1 with three-dimensional multistage cellular structure
Method, which comprises the following steps:
(1) by multi-walled carbon nanotube and carbon black dispersion in nitration mixture 3~6h of acidification, after being cooled to room temperature with distilled water it is dilute
It releases, filtration washing to neutrality, product is dried in vacuo 10~12h at 75~80 DEG C, is ground into a powder, and the multi wall carbon being acidified is received
Mitron and black stock powder；
(2) multi-walled carbon nanotube and black stock powder that are acidified obtained by step (1) are added in ammonium hydroxide, ultrasonic disperse is equal
It is even, obtain mixed liquor 1.；
(3) ammonium metavanadate, ammonium metatungstate, six nitric hydrate ceriums are added into the mixed solution of monoethanolamine and deionized water,
It dissolves by heating, obtains mixed liquor 2.；
(4) 1. under stiring with mixed liquor and contains titanium dioxide, silica, glass fibre, stearic acid
It in the mixture of paper pulp cotton, is kneaded, carboxymethyl cellulose, ethylene oxide and lactic acid is added, is kneaded again, obtains mixed soil
Material carries out aging；
(5) extrusion molding of mixing pug, the drying, calcining obtained step (4), obtains target product.
3. a kind of side for preparing the cellular SCR denitration with three-dimensional multistage cellular structure according to claim 2
Method, which is characterized in that multi-wall carbon nano-tube pipe diameter described in the step (1) is 10~20nm, and length is 5~15 μm；Institute
The partial size for the carbon black stated is about 15~20nm.
4. a kind of side for preparing the cellular SCR denitration with three-dimensional multistage cellular structure according to claim 2
Method, which is characterized in that the mass ratio of multi-walled carbon nanotube described in step (1) and carbon black is 1: (1~5)；The multi wall carbon is received
The mass ratio of the gross mass and mixed acid solution of mitron and carbon black is 1: (5~10).
5. a kind of side for preparing the cellular SCR denitration with three-dimensional multistage cellular structure according to claim 4
Method, which is characterized in that the nitration mixture is mixed at 3: 1 by volume by the concentrated sulfuric acid and concentrated nitric acid.
6. a kind of side for preparing the cellular SCR denitration with three-dimensional multistage cellular structure according to claim 2
Method, which is characterized in that in the step (2) concentration of ammonium hydroxide be 15%, ultrasonic disperse power be 400~800W, the time 0.5~
2h。
7. a kind of side for preparing the cellular SCR denitration with three-dimensional multistage cellular structure according to claim 2
Method, which is characterized in that it is 60~90 DEG C that temperature is dissolved by heating in the step (3).
8. a kind of side for preparing the cellular SCR denitration with three-dimensional multistage cellular structure according to claim 2
Method, which is characterized in that in the step (4) mixture be added to mixed liquor 1. with mixed liquor 2. in front of first stir 0.5~
1h。
9. a kind of side for preparing the cellular SCR denitration with three-dimensional multistage cellular structure according to claim 2
Method, which is characterized in that be 1. 2. added with stirring mixed liquor for 200~400rpm in revolving speed with mixed liquor in the step (4)
Containing in titanium dioxide, silica, glass fibre, stearic acid and the mixture of paper pulp cotton, with revolving speed be 600~800rpm into
Row is kneaded, and after being kneaded uniformly, carboxymethyl cellulose, ethylene oxide and lactic acid is added at 70~90 DEG C, again with revolving speed for 600
~800rpm is kneaded, and mixing pug is obtained, and carries out aging, and ageing time is 12~48h.
10. a kind of side for preparing the cellular SCR denitration with three-dimensional multistage cellular structure according to claim 2
Method, which is characterized in that the cellular catalyst hole count of extrusion molding is 20 × 20 holes in the step (5)；Drying temperature is 20
~60 DEG C；The mixed gas that oxygen content is 30~50% is passed through in calcination process, keeping entire calcining is excess oxygen.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811611515.XA CN109731569B (en) | 2018-12-27 | 2018-12-27 | Honeycomb type SCR denitration catalyst with three-dimensional multi-stage pore channel structure and preparation method thereof |
| PCT/CN2019/126497 WO2020135202A1 (en) | 2018-12-27 | 2019-12-19 | Honeycomb scr denitration catalyst having three-dimensional hierarchical porous structure and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811611515.XA CN109731569B (en) | 2018-12-27 | 2018-12-27 | Honeycomb type SCR denitration catalyst with three-dimensional multi-stage pore channel structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109731569A true CN109731569A (en) | 2019-05-10 |
| CN109731569B CN109731569B (en) | 2021-12-10 |
Family
ID=66360164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811611515.XA Active CN109731569B (en) | 2018-12-27 | 2018-12-27 | Honeycomb type SCR denitration catalyst with three-dimensional multi-stage pore channel structure and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109731569B (en) |
| WO (1) | WO2020135202A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020135202A1 (en) * | 2018-12-27 | 2020-07-02 | 安徽元琛环保科技股份有限公司 | Honeycomb scr denitration catalyst having three-dimensional hierarchical porous structure and preparation method |
| CN116087432A (en) * | 2023-03-07 | 2023-05-09 | 华电青岛环保技术有限公司 | Method for rapidly screening applicability of porous thin-wall SCR catalyst raw material titanium dioxide |
| CN116285128A (en) * | 2023-04-23 | 2023-06-23 | 罗孚橡胶（江苏）有限公司 | High-strength anti-aging rubber and preparation method thereof |
| CN116328789A (en) * | 2023-05-31 | 2023-06-27 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Chlorine poisoning resistant catalyst for simultaneously removing NO and VOCs and preparation method thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686716B (en) * | 2020-07-29 | 2022-06-14 | 江西省生态环境科学研究与规划院 | WOxLow-temperature SCR (selective catalytic reduction) flue gas denitration catalyst with modified carbon nano tube loaded with metal oxide, and preparation method and application thereof |
| CN112547045A (en) * | 2020-11-23 | 2021-03-26 | 安徽元琛环保科技股份有限公司 | Preparation method of photocatalytic denitration catalyst with porous titanium dioxide as carrier |
| CN114762835B (en) * | 2021-01-11 | 2023-07-28 | 中国石油化工股份有限公司 | Ozone catalytic oxidation catalyst for wastewater treatment and preparation method thereof |
| CN113499768A (en) * | 2021-07-09 | 2021-10-15 | 安徽元琛环保科技股份有限公司 | Preparation method of coating type high-strength denitration catalyst and prepared denitration catalyst |
| CN113877572B (en) * | 2021-09-16 | 2024-01-23 | 安徽元琛环保科技股份有限公司 | Preparation method of double-template porous coating type denitration catalyst, catalyst and application |
| CN113600168B (en) * | 2021-09-22 | 2023-08-11 | 大唐南京环保科技有限责任公司 | Low SO 2 Conversion rate honeycomb denitration catalyst and preparation method and application thereof |
| CN114011400B (en) * | 2021-10-21 | 2024-01-19 | 安徽元琛环保科技股份有限公司 | Preparation method of acidic system garbage incineration SCR denitration catalyst and denitration catalyst prepared by preparation method |
| CN114797837B (en) * | 2022-03-20 | 2023-03-10 | 浙江大学 | Catalyst capable of removing secondary pollutants in flue gas by concerted catalysis under low-temperature condition |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5299647B2 (en) * | 2010-04-09 | 2013-09-25 | Ｊｆｅエンジニアリング株式会社 | Exhaust gas treatment equipment |
| CN103769239A (en) * | 2014-01-27 | 2014-05-07 | 济南大学 | Honeycomb-type denitration catalyst with hierarchical pore structure and preparation method for honeycomb-type denitration catalyst |
| CN105013473A (en) * | 2015-07-20 | 2015-11-04 | 福建紫荆环境工程技术有限公司 | Catalyst for simultaneous removal of dioxins and NOX and preparation method thereof |
| CN105148948A (en) * | 2015-07-21 | 2015-12-16 | 安徽省元琛环保科技有限公司 | Denitration catalyst capable of removing dioxins and preparation method thereof |
| CN105521777A (en) * | 2015-12-31 | 2016-04-27 | 安徽省元琛环保科技有限公司 | A preparing method of a catalyst for low-temperature denitrification |
| CN108067296A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of preparation method of cellular Mn based low-temperature denitration catalysts |
| CN108273494A (en) * | 2017-12-29 | 2018-07-13 | 浙江德创环保科技股份有限公司 | A kind of denitrating catalyst and preparation method thereof for wide temperature window |
| CN108636417A (en) * | 2018-04-25 | 2018-10-12 | 清华大学 | A kind of metal oxide catalyst and preparation method thereof of removing NO |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0970534A (en) * | 1995-09-05 | 1997-03-18 | Babcock Hitachi Kk | Production of denitration catalyst |
| US20060040823A1 (en) * | 2004-08-18 | 2006-02-23 | Stockwell David M | Catalyst for NOx and/or SOx control |
| CN105413677A (en) * | 2015-11-30 | 2016-03-23 | 安徽省元琛环保科技有限公司 | Low-temperature denitration catalyst used after dedusting of power plant and preparation method of catalyst |
| JP6297767B2 (en) * | 2016-03-24 | 2018-03-20 | 株式会社キャタラー | Exhaust gas purification device |
| CN107876042B (en) * | 2017-11-10 | 2019-10-25 | 西南化工研究设计院有限公司 | A kind of high geometry specific surface area low-temperature denitration of flue gas catalyst and preparation method thereof |
| CN108404902A (en) * | 2018-02-09 | 2018-08-17 | 华电青岛环保技术有限公司 | A kind of SCR honeycomb types denitrating catalyst and preparation method thereof |
| CN109731569B (en) * | 2018-12-27 | 2021-12-10 | 安徽元琛环保科技股份有限公司 | Honeycomb type SCR denitration catalyst with three-dimensional multi-stage pore channel structure and preparation method thereof |
-
2018
- 2018-12-27 CN CN201811611515.XA patent/CN109731569B/en active Active
-
2019
- 2019-12-19 WO PCT/CN2019/126497 patent/WO2020135202A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5299647B2 (en) * | 2010-04-09 | 2013-09-25 | Ｊｆｅエンジニアリング株式会社 | Exhaust gas treatment equipment |
| CN103769239A (en) * | 2014-01-27 | 2014-05-07 | 济南大学 | Honeycomb-type denitration catalyst with hierarchical pore structure and preparation method for honeycomb-type denitration catalyst |
| CN105013473A (en) * | 2015-07-20 | 2015-11-04 | 福建紫荆环境工程技术有限公司 | Catalyst for simultaneous removal of dioxins and NOX and preparation method thereof |
| CN105148948A (en) * | 2015-07-21 | 2015-12-16 | 安徽省元琛环保科技有限公司 | Denitration catalyst capable of removing dioxins and preparation method thereof |
| CN105521777A (en) * | 2015-12-31 | 2016-04-27 | 安徽省元琛环保科技有限公司 | A preparing method of a catalyst for low-temperature denitrification |
| CN108067296A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of preparation method of cellular Mn based low-temperature denitration catalysts |
| CN108273494A (en) * | 2017-12-29 | 2018-07-13 | 浙江德创环保科技股份有限公司 | A kind of denitrating catalyst and preparation method thereof for wide temperature window |
| CN108636417A (en) * | 2018-04-25 | 2018-10-12 | 清华大学 | A kind of metal oxide catalyst and preparation method thereof of removing NO |
Non-Patent Citations (4)
| Title |
|---|
| CHONG XIE ET AL.: ""C-doped mesoporous anatase TiO2 comprising 10 nm crystallites"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| 张蕾: "《烟气脱硫脱硝技术及催化剂的研究进展》", 31 August 2016, 中国矿业大学出版社 * |
| 李清文等: "《高性能纤维技术丛书 碳纳米管线网》", 31 July 2018, 国防工业出版社 * |
| 杨娜等: ""Pt/SAPO-11催化剂载体的改性对正十四烷临氢转化性能的影响"", 《燃料化学学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020135202A1 (en) * | 2018-12-27 | 2020-07-02 | 安徽元琛环保科技股份有限公司 | Honeycomb scr denitration catalyst having three-dimensional hierarchical porous structure and preparation method |
| CN116087432A (en) * | 2023-03-07 | 2023-05-09 | 华电青岛环保技术有限公司 | Method for rapidly screening applicability of porous thin-wall SCR catalyst raw material titanium dioxide |
| CN116285128A (en) * | 2023-04-23 | 2023-06-23 | 罗孚橡胶（江苏）有限公司 | High-strength anti-aging rubber and preparation method thereof |
| CN116285128B (en) * | 2023-04-23 | 2024-01-12 | 罗孚橡胶（江苏）有限公司 | High-strength anti-aging rubber and preparation method thereof |
| CN116328789A (en) * | 2023-05-31 | 2023-06-27 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Chlorine poisoning resistant catalyst for simultaneously removing NO and VOCs and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109731569B (en) | 2021-12-10 |
| WO2020135202A1 (en) | 2020-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109731569A (en) | Cellular SCR denitration and preparation method with three-dimensional multistage cellular structure | |
| CN103191718B (en) | Preparation method of low-cost honeycomb denitration catalyst | |
| CN101428215B (en) | Process for producing flue gas denitration catalyst and flue gas denitration catalyst produced with the process | |
| WO2020249105A1 (en) | Scr catalyst and preparation method | |
| CN111036192B (en) | Coating type wear-resistant vanadium denitration catalyst and preparation method and application thereof | |
| JP2019511352A (en) | Method for producing molecular sieve-multi-oxide composite monolithic monolithic extrusion NOx removal catalyst | |
| CN105013474B (en) | The preparation method of metal oxide denitrating catalyst with orderly hierarchical porous structure | |
| CN107362823B (en) | Catalytic material for degrading indoor formaldehyde at room temperature and preparation method thereof | |
| CN101961656A (en) | High-temperature smoke selective catalytic reduction (SCR) denitration catalyst, preparation method and application thereof | |
| CN101428212A (en) | Selective catalysis reduction denitrate catalyst for composite carrier flue gas and preparation method thereof | |
| CN103861653A (en) | Modified titanium dioxide, ultrafine crystal ceramic powder, high-strength heat-engine plant denitration catalyst, and preparation methods of modified titanium dioxide, ultrafine crystal ceramic powder, and high-strength heat-engine plant denitration catalyst | |
| CN112973668A (en) | High-strength honeycomb type low-temperature SCR denitration catalyst and preparation method thereof | |
| CN103861581A (en) | Perovskite-type substance La<1-x>Sr<x>CrO<3>, heat-engine plant denitration composite catalyst, and preparation methods of perovskite-type substance La<1-x>Sr<x>CrO<3> and heat-engine plant denitration composite catalyst | |
| CN107126950A (en) | A kind of honeycomb type denitrification catalyst and preparation method thereof | |
| CN103263911B (en) | Preparation method of denitration catalyst with nanoscale ordered honeycomb structure | |
| CN109665525A (en) | A kind of preparation method of " dumbbell shape " iron nitrogen codope porous carbon | |
| CN108837823A (en) | A kind of perovskite type catalyst and its monoblock type forming method and application | |
| CN109589967B (en) | High-activity sulfur-resistant SCR denitration catalyst and preparation method thereof | |
| CN104607198A (en) | Vanadium-free plate-like denitration catalyst and preparation method thereof | |
| CN106881105A (en) | A kind of board-like low temperature catalyst with the self-assembly porous spherical titanium dioxide of crosslinking nano chain as carrier and its preparation method and application | |
| CN111744494B (en) | Flat plate type CO and SO 2 And NO x Synchronous removal catalyst and preparation method thereof | |
| CN106902807A (en) | A kind of particle type low-temperature SCR catalyst and preparation method thereof | |
| CN105664978B (en) | Low-temperature denitration of flue gas is acidified the sulfur resistant catalyst molding method for preparing of manganese cobalt cerium with composite carrier load type | |
| CN106276895A (en) | A kind of preparation method of amberlite aliphatic radical material with carbon element | |
| CN109939694A (en) | A kind of honeycomb fashion low-temperature denitration catalyst and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |