CN107362808A - Integrated low temperature denitrating catalyst and preparation method thereof - Google Patents
Integrated low temperature denitrating catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910001868 water Inorganic materials 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 7
- 238000007493 shaping process Methods 0.000 claims abstract description 7
- 238000005470 impregnation Methods 0.000 claims abstract description 6
- 150000000703 Cerium Chemical class 0.000 claims abstract description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 21
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 8
- 235000014655 lactic acid Nutrition 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 229910016978 MnOx Inorganic materials 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims description 7
- 229910003320 CeOx Inorganic materials 0.000 claims description 6
- 229910015189 FeOx Inorganic materials 0.000 claims description 6
- 229960000892 attapulgite Drugs 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 229910052625 palygorskite Inorganic materials 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 210000005056 cell body Anatomy 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000005299 abrasion Methods 0.000 abstract 1
- 241000264877 Hippospongia communis Species 0.000 description 58
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 241000243142 Porifera Species 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RJIWZDNTCBHXAL-UHFFFAOYSA-N nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/56—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention is that its preparation method includes on a kind of integrated low temperature denitrating catalyst and preparation method thereof：1) it is manganese salt, cerium salt and molysite is soluble in water, stirring in water bath, obtain active component mixed solution；2) carrier, reinforcing agent and shaping assistant are kneaded, are old, extrusion, obtaining honeycomb body；By honeycomb body drying, preroast, integral honeycomb carrier is obtained；3) described integral honeycomb carrier impregnation is obtained into precast body in described active component mixed solution；Precast body is dried, calcines, obtains integrated low temperature denitrating catalyst.The integrated low temperature denitrating catalyst molding technique parameter of the present invention is easy to control, and integral honeycomb easy-formation, active component is evenly distributed inside and outside carrier, and not only denitration efficiency is high, possesses certain resistance to SO_2, and have higher mechanical strength and abrasion resistance.
Description
Technical field
The present invention relates to a kind of catalytic denitration field, more particularly to a kind of integrated low temperature denitrating catalyst and its preparation
Method.
Background technology
Nitrogen oxides (NOx) it is one of Air Pollutant Discharge, acid rain, photochemical fog can be produced and participate in being formed
PM2.5 in air etc., seriously endanger natural ecological environment and human health.NO in airxIt is mainly derived from non-electrical industry
Boiler, coal-burning power plant and automotive emission.In numerous NOxIn emission-reduction technology, selective catalytic reduction (SCR) is because of it
Have the advantages that stable, removal efficiency is high to show one's talent, make SCR technology in NOxField of purification waits until popularization and application, wherein
Denitration material is the core of SCR technology.As China's atmospheric environment constantly deteriorates, country is to traditional non-electrical Industrial Stoves NOx
Emission limit improves constantly, but non-electrical Industrial Stoves are different from coal-burning power plant, extensive use because of itself smoke components and temperature
Business vanadium titanium system denitration material in coal-burning power plant is not suitable for non-electrical Industrial Stoves NOxEmission reduction, cause the main original of this phenomenon
Because being that the temperature of non-electric Industrial Stoves tail gas is relatively low, and the active temperature windows of commercial vanadium titanium system denitration material are higher, therefore low
Warm efficient denitration material is non-electric Industrial Stoves NOxIn emission-reduction technology there is an urgent need to object.
In low-temperature denitration investigation of materials field, MnOxDue to being widely studied with preferable low-temperature catalytic activity,
But Mn-Ce series catalysts product and its application case are commercially had not seen at present, most reasons belong to Mn-Ce/TiO2
Easily there is quality accident in drying, calcining in honeycomb catalyst, and such as top layer is burst, mechanical strength is low, causes honeycomb productses finished product
Rate is almost nil.For TiO2(or TiO2-WO3) honeycomb substrate carry out low temperature preroast ensure that it has higher specific surface area,
Active component is impregnated again prepare the correlative study of integrated low temperature SCR denitration material be rarely reported.
The content of the invention
It is a primary object of the present invention to, there is provided a kind of new integrated low temperature denitrating catalyst and preparation method thereof,
Technical problem to be solved is to make its easy-formation, and active component is evenly distributed inside and outside carrier, high yield rate, is had well
Mechanical strength, thus more suitable for practicality.
The object of the invention to solve the technical problems is realized using following technical scheme.Itd is proposed according to the present invention
A kind of integrated low temperature denitrating catalyst preparation method, it includes：
1) it is manganese salt, cerium salt and molysite is soluble in water, stirring in water bath, obtain active component mixed solution；
2) carrier, reinforcing agent and shaping assistant are kneaded, are old, extrusion, obtaining honeycomb body；By honeycomb body it is dry,
Preroast, obtain integral honeycomb carrier；
Wherein, the condition of preroast is：Pre-calcination temperature curve is arranged to be warming up to 300-400 DEG C from 50-60 DEG C, heating
Speed is 20-30 DEG C/h, is incubated 2-3h at 300-400 DEG C, is cooled to 60-80 DEG C, and cooling rate is 40-50 DEG C/h, preroast
Time be 24-26h；
3) described integral honeycomb carrier impregnation is obtained into precast body in described active component mixed solution；Will be pre-
Soma processed is dry, calcining, obtains integrated low temperature denitrating catalyst.
The object of the invention to solve the technical problems can be also applied to the following technical measures to achieve further.
Preferably, the preparation method of foregoing integrated low temperature denitrating catalyst, wherein described manganese salt is manganese nitrate, institute
The cerium salt stated is cerous nitrate, and described molysite is ferric nitrate；
Described active component mixed solution, by weight percentage, it includes：
Manganese nitrate：27.5-42.5%；
Cerous nitrate：4-5%；
Ferric nitrate：5.5-8.5%；
Water：44-63%.
Preferably, the preparation method of foregoing integrated low temperature denitrating catalyst, wherein described carrier be titanium dioxide or
Titanium tungsten powder；Described reinforcing agent is attapulgite；It is fine that described shaping assistant includes stearic acid, lactic acid, glass fibre, carboxymethyl
Dimension element and polyethylene glycol oxide.
Preferably, the preparation method of foregoing integrated low temperature denitrating catalyst, wherein described integral honeycomb carrier,
By weight percentage, it includes：
Carrier：100%；
Attapulgite：5-8%；
Stearic acid：0.3-0.5%；
Lactic acid：0.9-1.1%；
Glass fibre：10-15%；
Carboxymethyl cellulose：0.8-1%；
Polyethylene glycol oxide：1.5-1.7%.
Preferably, the preparation method of foregoing integrated low temperature denitrating catalyst, wherein described honeycomb body dries bag
Honeycomb body primary drying and honeycomb body redrying are included, the wherein temperature setting of honeycomb body primary drying is 25 DEG C of heatings
To 55 DEG C, heating rate is 4-6 DEG C/d, is incubated 4-5d at 55 DEG C, and humidity is down to 30% from 80%, speed 5-6%/d, honeycomb
The base substrate primary drying time is 10-11d；The temperature setting of honeycomb body redrying is warming up to 65 DEG C for 55 DEG C, heating rate
For 1 DEG C/h, 2-4h is incubated at 65 DEG C, humidity is down to 10% from 30%, speed 1-3%/h, the honeycomb body redrying time
For 12-14h, honeycomb body redrying is repeated 2 times.
Preferably, the preparation method of foregoing integrated low temperature denitrating catalyst, include wherein described precast body is dried
Precast body primary drying and precast body redrying, the wherein temperature setting of precast body primary drying are warming up to 65 DEG C for 25 DEG C,
Heating rate is 6-8 DEG C/d, and 2-3d is incubated at 65 DEG C, and humidity is down to 30% from 80%, and speed 8-10%/d, precast body is once
Drying time is 6-7d；The temperature setting of precast body redrying is 65 DEG C and is warming up to 85 DEG C, and heating rate is 2 DEG C/h, 85 DEG C
Lower insulation 2-4h, humidity are down to 10% from 30%, and speed 1-3%/h, the precast body redrying time is 12-14h.
Preferably, the preparation method of foregoing integrated low temperature denitrating catalyst, the wherein calcination condition in step 3) are：
Calcination-temperature profile is arranged to be warming up to 400 DEG C from 60-80 DEG C, and programming rate is 20-25 DEG C/h, and 4-5h, drop are incubated at 400 DEG C
Temperature is to 60-80 DEG C, and cooling rate is 45-50 DEG C/h, and the time of calcining is 24-28h.
The object of the invention to solve the technical problems is also realized using following technical scheme.Itd is proposed according to the present invention
A kind of integrated low temperature denitrating catalyst, be prepared by foregoing method；Its active component is by MnOx、CeOxAnd FeOxGroup
Into carrier is titanium dioxide or titanium tungsten powder；The weight ratio of active component and carrier is 12-28:72-88.
The object of the invention to solve the technical problems can be also applied to the following technical measures to achieve further.
Preferably, foregoing integrated low temperature denitrating catalyst, wherein described integrated low temperature denitrating catalyst, with weight
Percentages are measured, it includes：
MnOx：9.8-22.8%；
CeOx：1.3-3%
FeOx：0.91-2.1%；
Carrier：82.1-87.99%.
The object of the invention to solve the technical problems is also realized using following technical scheme.Itd is proposed according to the present invention
A kind of denitration method for flue gas, selective catalytic reduction reaction is carried out with foregoing integrated low temperature denitrating catalyst, it is described
The temperature of selective catalytic reduction reaction is 150-320 DEG C, and denitration efficiency is more than 80%.
By above-mentioned technical proposal, integrated low temperature denitrating catalyst of the present invention and preparation method thereof at least has following excellent
Point：
1) preparation method of integrated low temperature denitrating catalyst of the invention is simple, and molding technique parameter is easy to control, overall
Honeycomb easy-formation, active component are evenly distributed inside and outside carrier, captured denitrating catalyst calcining burst, the problem such as lobe, into
Product rate is high, has good mechanical strength；
2) integrated low temperature denitrating catalyst of the invention, carrier is subjected to low temperature preroast, active component can be made to exist
Carrier inside distribution is more uniform, and the synergy between carrier and active component is to removing NOxMore effectively；
3) integrated low temperature denitrating catalyst of the invention is applied to non-electrical Industrial Stoves low-temperature denitration of flue gas, and the denitration is urged
Denitration efficiency of the agent in 150-320 DEG C of range of reaction temperature can resist SO a small amount of in flue gas up to more than 80%2
(250mg/Nm3)。
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is the integrated low temperature denitrating catalyst resistance to SO_2 test result of embodiment 1.
Fig. 2 is the integrated low temperature denitrating catalyst resistance to SO_2 test result of embodiment 2.
Embodiment
Further to illustrate the present invention to reach the technological means and effect that predetermined goal of the invention is taken, below in conjunction with
Accompanying drawing and preferred embodiment, to according to its specific implementation of integrated low temperature denitrating catalyst proposed by the present invention and preparation method thereof
Mode, structure, feature and its effect, describe in detail as after.In the following description, different " embodiment " or " embodiment " refers to
Be not necessarily the same embodiment.In addition, the special characteristic, structure or feature in one or more embodiments can be by any suitable
Form combines.
A kind of integrated low temperature denitrating catalyst that one embodiment of the present of invention proposes and preparation method thereof, it includes：
1) by 55-85% 50% manganese nitrate solution, 4-5% cerous nitrates, 5.5-8.5% ferric nitrate and 1.5-
35.5% deionized water stirring in water bath at 65 DEG C, obtains active component mixed solution；
2) by the mixing of carrier, reinforcing agent and shaping assistant, old, extrusion, honeycomb body drying, preroast, entirety is obtained
Formula honeycomb substrate；Integral honeycomb carrier hole count is 18 × 18~25 × 25, and sectional dimension is 150 × 150mm；
Wherein, carrier is titanium dioxide or titanium tungsten powder；Described reinforcing agent is attapulgite；Described shaping assistant includes hard
Resin acid, lactic acid, glass fibre, carboxymethyl cellulose (CMC) and polyethylene glycol oxide (PEO)；
Mixing includes：Carrier and 5-8% nonmetallic ore material attapulgites are put into mixing facilities, then according to entirety
Formula honeycomb substrate hole count is slowly uniformly added into the stearic acid of 3-5 ‰, 9 ‰ -1.1% 80% lactic acid, and pug temperature rises to 60-65
DEG C, 10-15% glass fibre is added, 8 ‰ -1%CMC and 1.5-1.7%PEO, shutdown are cooled to 50-60 DEG C of low speed and reverse and gone out
Material, discharging moisture obtain pug in 23-28%；
It is old including：Pug after mixing is positioned in Bulk plastic case, sealing is covered with plastic cloth, prevents pug water
Divide a large amount of evaporations, old time 1-2d；
Extrusion includes：Pug after old carries out vacuum mud refining extrusion, and vacuum is -0.1-0.08Mpa, repeats 1-2 times；
It is 150 × 150mm to choose section as needed, and the honeycomb die in 18-25 holes is arranged on extruder；Carrier base substrate was being extruded
Journey, base substrate of the automatic gas cutting machine intercepted length as needed for 500-800mm is used, with the packing paper of included sponge to honeycomb base
Body carries out manual parcel placement；
The condition of preroast is：Pre-calcination temperature curve is arranged to be warming up to 300-400 DEG C from 50-60 DEG C, programming rate
For 20-30 DEG C/h, 2-3h is incubated at 300-400 DEG C, is cooled to 60-80 DEG C, cooling rate is 40-50 DEG C/h, preroast when
Between be 24-26h；
Honeycomb body, which is dried, includes honeycomb body primary drying and honeycomb body redrying, and wherein honeycomb body is once done
Dry temperature setting is 25 DEG C and is warming up to 55 DEG C, and heating rate is 4-6 DEG C/d, is incubated 4-5d at 55 DEG C, humidity is down to from 80%
30%, speed 5-6%/d, honeycomb body primary drying time are 10-11d；The temperature setting of honeycomb body redrying is
55 DEG C are warming up to 65 DEG C, and heating rate is 1 DEG C/h, are incubated 2-4h at 65 DEG C, and humidity is down to 10% from 30%, speed be 1-3%/
H, honeycomb body redrying time are 12-14h, repeat honeycomb body redrying 2 times.
3) by described length be 500-800mm integral honeycombs carrier impregnation in described active component mixed solution
30-60min, precast body are dried, and calcining, obtain integrated low temperature denitrating catalyst.
Wherein, it is preferred that the preparation method of foregoing integrated low temperature denitrating catalyst, wherein described precast body is dried
Including precast body primary drying and precast body redrying, the wherein temperature setting of precast body primary drying is warming up to 65 for 25 DEG C
DEG C, heating rate is 6-8 DEG C/d, is incubated 2-3d at 65 DEG C, and humidity is down to 30% from 80%, speed 8-10%/d, precast body
The primary drying time is 6-7d；The temperature setting of precast body redrying is 65 DEG C and is warming up to 85 DEG C, and heating rate is 2 DEG C/h,
2-4h is incubated at 85 DEG C, humidity is down to 10% from 30%, and speed 1-3%/h, the precast body redrying time is 12-14h；
Calcination condition is：Calcination-temperature profile is arranged to be warming up to 400 DEG C from 60-80 DEG C, and programming rate is 20-25 DEG C/
H, 4-5h is incubated at 400 DEG C, is cooled to 60-80 DEG C, cooling rate is 45-50 DEG C/h, and the time of calcining is 24-28h.
A kind of integrated low temperature denitrating catalyst that one embodiment of the present of invention proposes, by foregoing method preparation
Into；Its active component is by MnOx、CeOxAnd FeOxComposition, carrier is titanium dioxide or titanium tungsten powder；The weight ratio of active component and carrier
For 12-28:72-88.
Preferably, integrated low temperature denitrating catalyst, by weight percentage, it includes：
MnOx：9.8-22.8%；
CeOx：1.3-3%
FeOx：0.91-2.1%；
Carrier：82.1-87.99%.
A kind of denitration method for flue gas that one embodiment of the present of invention proposes, with foregoing integrated low temperature denitrating catalyst
Selective catalytic reduction reaction is carried out, the temperature of described selective catalytic reduction reaction is 150-320 DEG C, and denitration efficiency is more than
80%.
Embodiment 1
A kind of preparation method for integrated low temperature denitrating catalyst that one embodiment of the present of invention proposes, it includes：
1) by 30.4kg50%Mn (NO3)2Solution, 2.16kgCe (NO3)2·6H2O、3.02kgFe(NO3)3·9H2O and
3.20kg deionized waters, which are put into reactor, carries out heating stirring, and temperature of reaction kettle is arranged to 65 DEG C, treats in solution without obvious
Particle, obtain active component mixed solution；
2)TiO2Powder 600kg and 40kg attapulgite is put into mixing facilities, and low speed rotates forward stirring, then needed for
Honeycomb body hole count is 22 holes, is slowly uniformly added into 3.5 ‰ stearic acid, 9.4 ‰ 80% lactic acid, 150kg deionized waters, 40min
Start high-speed stirred to pug temperature afterwards and rise to 95 DEG C, shutdown is cooled to 60 DEG C, adds 12.5% glass fibre, 30kg go from
Sub- water, after high-speed stirred 30min, shutdown is cooled to 60 DEG C, adds 1%CMC and 1.5%PEO, 20kg deionized water, high-speed stirring
30min is mixed, shutdown is cooled to 50 DEG C of low speed and reverse dischargings, and discharging moisture is 26%；
It is kneaded qualified rear pug to be positioned in Bulk plastic case, covers sealing with plastic cloth, prevent pug moisture from largely steaming
Hair.Old purpose is having the sufficient time to be distributed in pug in moisture, so as to follow-up expressing technique, old time 1d；
Pug after old carries out vacuum mud refining extrusion, and vacuum is -0.08Mpa.Its object is to by the phase in pug
Larger particle filtering is fallen, next to that the contact between the little particle in pug is more compact, so as to follow-up expressing technique
Carry out；Pug in (4) is extruded by large, honeycomb extruder, selection section is 150 × 150mm, the honeycomb mould in 22 holes
Tool is arranged on extruder.TiO2 base substrates use base of the automatic gas cutting machine intercepted length as needed for 600mm in extrusion
Body, manual parcel placement is carried out to honeycomb body with the packing paper of included sponge；
The honeycomb body of extrusion is placed in primary drying room, and temperature setting is that 25 DEG C of room temperature is to slowly warm up to 55 DEG C, heating
Speed is 5 DEG C/d, and 5d is incubated at 55 DEG C, and humidity is adjusted by blower fan, is slowly dropped to 30%, speed 5%/d from 80%, entirely
The honeycomb body primary drying time is 11d；Then honeycomb body is transferred in redrying room, temperature setting is slow from 55 DEG C
Slowly 65 DEG C are warming up to, heating rate is 1 DEG C/h, is incubated 4h at 65 DEG C, and humidity is down to 10% from 30%, speed 1.5%/h, whole
The individual honeycomb body redrying time is 14h, need to carry out 2 honeycomb body redryings；
Preroast is carried out to described honeycomb body in mesh-belt kiln, pre-calcination temperature curve is arranged to be warming up to from 60 DEG C
380 DEG C, programming rate is 20 DEG C/h, is incubated 3h at 380 DEG C, is then cooled to 60 DEG C, cooling rate is 50 DEG C/h.Whole prebake
Burning needs 26h, so as to which integral honeycomb carrier be made；
3) 600mm integral honeycombs carrier impregnation is placed in primary drying in described active component mixed solution 60min
In room, temperature setting is that 25 DEG C of room temperature is to slowly warm up to 65 DEG C, and heating rate is 8 DEG C/d, is incubated 2d at 65 DEG C, humidity passes through wind
Machine is adjusted, and 30% is slowly dropped to from 80%, and speed 8%/d, the whole precast body primary drying time is 7d, then will be pre-
Body processed is transferred in redrying room, and for temperature setting to be to slowly warm up to 85 DEG C from 65 DEG C, heating rate is 2 DEG C/h, at 85 DEG C
4h is incubated, humidity is down to 10% from 30%, and speed 2%/h, the whole precast body redrying time is 12h, need to carry out 1 time in advance
Body redrying processed.
Dried precast body is calcined in mesh-belt kiln, calcination-temperature profile is arranged to be warming up to 400 from 80 DEG C
DEG C, programming rate is 25 DEG C/h, is incubated 4h at 400 DEG C, is then cooled to 60 DEG C, and cooling rate is 45 DEG C/h, and whole calcining needs
24h is wanted, so as to which integrated low temperature denitrating catalyst be made.
Embodiment 2
A kind of preparation method for integrated low temperature denitrating catalyst that one embodiment of the present of invention proposes, it includes：
1) by 30.4kg50%Mn (NO3)2Solution, 2.16kgCe (NO3)2·6H2O、3.02kgFe(NO3)3·9H2O and
3.20kg deionized waters, which are put into reactor, carries out heating stirring, and temperature of reaction kettle is arranged to 65 DEG C, treats in solution without obvious
Particle, obtain active component mixed solution；
2) commercial TiO2-6%WO is weighed3Powder 650kg is put into mixing facilities, and low speed rotates forward stirring, subsequent basis
Required honeycomb body hole count is 22 holes, is slowly uniformly added into 3.5 ‰ stearic acid, 9.4 ‰ 80% lactic acid, 150kg deionized waters,
Starting high-speed stirred to pug temperature after 40min and rise to 95 DEG C, shutdown is cooled to 60 DEG C, adds 12.5% glass fibre,
30kg deionized waters, after high-speed stirred 30min, shutdown is cooled to 60 DEG C, adds 1%CMC and 1.5%PEO, 20kg deionization
Water, high-speed stirred 30min, shutdown are cooled to 50 DEG C of low speed and reverse dischargings, and discharging moisture is 26%；
It is kneaded qualified rear pug to be positioned in Bulk plastic case, covers sealing with plastic cloth, prevent pug moisture from largely steaming
Hair.Old purpose is having the sufficient time to be distributed in pug in moisture, so as to follow-up expressing technique, old time 1d；
Pug after old carries out vacuum mud refining extrusion, and vacuum is -0.08Mpa.Its object is to by the phase in pug
Larger particle filtering is fallen, next to that the contact between the little particle in pug is more compact, so as to follow-up expressing technique
Carry out；Pug in (4) is extruded by large, honeycomb extruder, selection section is 150 × 150mm, the honeycomb mould in 22 holes
Tool is arranged on extruder.TiO2 base substrates use base of the automatic gas cutting machine intercepted length as needed for 600mm in extrusion
Body, manual parcel placement is carried out to honeycomb body with the packing paper of included sponge；
The honeycomb body of extrusion is placed in primary drying room, and temperature setting is that 25 DEG C of room temperature is to slowly warm up to 55 DEG C, heating
Speed is 5 DEG C/d, and 5d is incubated at 55 DEG C, and humidity is adjusted by blower fan, is slowly dropped to 30%, speed 5%/d from 80%, entirely
The honeycomb body primary drying time is 11d；Then honeycomb body is transferred in redrying room, temperature setting is slow from 55 DEG C
Slowly 65 DEG C are warming up to, heating rate is 1 DEG C/h, is incubated 4h at 65 DEG C, and humidity is down to 10% from 30%, speed 1.5%/h, whole
The individual honeycomb body redrying time is 14h, need to carry out 2 honeycomb body redryings；
Preroast is carried out to described honeycomb body in mesh-belt kiln, pre-calcination temperature curve is arranged to be warming up to from 60 DEG C
380 DEG C, programming rate is 20 DEG C/h, is incubated 3h at 380 DEG C, is then cooled to 60 DEG C, cooling rate is 50 DEG C/h.Whole prebake
Burning needs 26h, so as to which integral honeycomb carrier be made；
3) 600mm integral honeycombs carrier impregnation is placed in primary drying in described active component mixed solution 60min
In room, temperature setting is that 25 DEG C of room temperature is to slowly warm up to 65 DEG C, and heating rate is 8 DEG C/d, is incubated 2d at 65 DEG C, humidity passes through wind
Machine is adjusted, and 30% is slowly dropped to from 80%, and speed 8%/d, the whole precast body primary drying time is 7d, then will be pre-
Body processed is transferred in redrying room, and for temperature setting to be to slowly warm up to 85 DEG C from 65 DEG C, heating rate is 2 DEG C/h, at 85 DEG C
4h is incubated, humidity is down to 10% from 30%, and speed 2%/h, the whole precast body redrying time is 12h, need to carry out 1 time in advance
Body redrying processed.
Dried precast body is calcined in mesh-belt kiln, calcination-temperature profile is arranged to be warming up to 400 from 80 DEG C
DEG C, programming rate is 25 DEG C/h, is incubated 4h at 400 DEG C, is then cooled to 60 DEG C, and cooling rate is 45 DEG C/h, and whole calcining needs
24h is wanted, so as to which integrated low temperature denitrating catalyst be made.
Comparative example
By titanium dioxide (TiO2) sintering temperature is respectively set as 250 DEG C, 500 DEG C, 600 DEG C, remaining step with embodiment 1,
Comparative example 1, comparative example 2, comparative example 3 is made.
By titanium tungsten powder (TiO2- 6%WO3) sintering temperature is respectively set as 250 DEG C, 500 DEG C, 600 DEG C, remaining step is the same as real
Example 1 is applied, comparative example 4, comparative example 5, comparative example 6 is made.
Embodiments of the invention propose a kind of denitration method for flue gas, are simulated using standard steel cylinder gas, and flue gas composition is NO
(600×10-6)、NH3(600×10-6)、O2(5%), SO2(100×10-6)、H2O(5mL/min)、N2For carrier gas, air speed is
5000h-1, total gas flow rate 25L/min, the admission space of catalyst sample is 300mL (4 hole).Denitrating catalyst activity is surveyed
Examination is carried out in the square stainless steel tube SCR reactors of fixed bed, and using external electric pattern, temperature is by tube type resistance furnace control
System.The NO removal efficiencies of 150 DEG C, 180 DEG C, 210 DEG C, 250 DEG C, 280 DEG C, 320 DEG C etc. 6 temperature spots, Mei Yiwen are determined respectively
It is dense using the NO in gas before and after flue gas analyzer (Testo350, Germany) measure reaction after the stable reaction 10min of degree point
Degree.Wherein, NO conversion ratios (%)=[(NOin-NOout)/NOin] × 100%；The test of denitrating catalyst resistance to SO_2 is SCR reactions
Temperature is at 180 DEG C, with the extension in reaction time, determines the NO removal efficiencies of denitrating catalyst.
The integrated low temperature denitrating catalyst Activity evaluation of embodiment and comparative example is as shown in table 1.Can be with from table 1
Find out, generally speaking, the denitration activity of denitrating catalyst reduces with the increase of pre-calcination temperature, honeycomb body through 250 DEG C,
After 380 DEG C of preroasts, then carry out impregnate preparation denitrating catalyst denitration activity be more or less the same, than honeycomb body through 500 DEG C,
The denitration activity of the denitrating catalyst prepared after 600 DEG C of preroasts will height.
The integrated low temperature denitrating catalyst denitration efficiency test result of table 1
The integrated low temperature denitrating catalyst specific surface area test result of embodiment 1 and embodiment 2 is as shown in table 2.From table 2
In as can be seen that the specific surface area of denitrating catalyst reduces with the increase of pre-calcination temperature, after 250 DEG C of preroast, then enter
The specific surface area of denitrating catalyst prepared by row dipping is maximum, and the denitrating catalyst that carrier is prepared after 380 DEG C of preroast is still protected
Holding has higher specific surface area, be favorably improved active component be uniformly distributed and upper carrying capacity, so as to help improve denitration live
Property.
The integrated low temperature denitrating catalyst specific surface area test result of table 2
The test result of the integrated low temperature denitrating catalyst compression strength of embodiment 1 and embodiment 2 is as shown in table 3.From
As can be seen that the compression strength of denitrating catalyst improves with the increase of carrier pre-calcination temperature in table.
The monoblock type denitrating catalyst strength test results of table 3
The integrated low temperature denitrating catalyst resistance to SO_2 test result of embodiment 1 is as shown in figure 1, curve 1 is embodiment 1
Denitration efficiency of catalyst when without sulphur, curve 2 are SO of the catalyst in 100ppm for applying example 12When denitration efficiency.Embodiment
2 integrated low temperature denitrating catalyst resistance to SO_2 test result as shown in Fig. 2 curve 3 for embodiment 2 catalyst when without sulphur
Denitration efficiency, curve 4 is to apply SO of the catalyst in 100ppm of example 42When denitration efficiency.It can be seen that this hair
Bright embodiment 1 and embodiment 2 lead to SO2Nearly 78%, 80% denitration efficiency is still kept after 100ppm, 10h respectively, illustrates to be molded work
Denitrating catalyst prepared by skill possesses certain resistance to SO_2.
The above described is only a preferred embodiment of the present invention, any formal limitation not is made to the present invention, according to
Any simple modification, equivalent change and modification made according to the technical spirit of the present invention to above example, still falls within this hair
In the range of bright technical scheme.
Claims (10)
1. a kind of preparation method of integrated low temperature denitrating catalyst, it is characterised in that it includes：
1) it is manganese salt, cerium salt and molysite is soluble in water, stirring in water bath, obtain active component mixed solution；
2) carrier, reinforcing agent and shaping assistant are kneaded, are old, extrusion, obtaining honeycomb body；By honeycomb body drying, prebake
Burn, obtain integral honeycomb carrier；
Wherein, the condition of preroast is：Pre-calcination temperature curve is arranged to be warming up to 300-400 DEG C from 50-60 DEG C, programming rate
For 20-30 DEG C/h, 2-3h is incubated at 300-400 DEG C, is cooled to 60-80 DEG C, cooling rate is 40-50 DEG C/h, preroast when
Between be 24-26h；
3) described integral honeycomb carrier impregnation is obtained into precast body in described active component mixed solution；By precast body
Dry, calcining, obtain integrated low temperature denitrating catalyst.
2. the preparation method of integrated low temperature denitrating catalyst according to claim 1, it is characterised in that described manganese salt
For manganese nitrate, described cerium salt is cerous nitrate, and described molysite is ferric nitrate；
Described active component mixed solution, by weight percentage, it includes：
Manganese nitrate：27.5-42.5%；
Cerous nitrate：4-5%；
Ferric nitrate：5.5-8.5%；
Water：44-63%.
3. the preparation method of integrated low temperature denitrating catalyst according to claim 1, it is characterised in that described carrier
For titanium dioxide or titanium tungsten powder；Described reinforcing agent is attapulgite；Described shaping assistant includes stearic acid, lactic acid, glass fibers
Dimension, carboxymethyl cellulose and polyethylene glycol oxide.
4. the preparation method of integrated low temperature denitrating catalyst according to claim 1, it is characterised in that described entirety
Formula honeycomb substrate, by weight percentage, it includes：
Carrier：100%；
Attapulgite：5-8%；
Stearic acid：0.3-0.5%；
Lactic acid：0.9-1.1%；
Glass fibre：10-15%；
Carboxymethyl cellulose：0.8-1%；
Polyethylene glycol oxide：1.5-1.7%.
5. the preparation method of integrated low temperature denitrating catalyst according to claim 1, it is characterised in that described honeycomb
Body drying includes the temperature setting of honeycomb body primary drying and honeycomb body redrying, wherein honeycomb body primary drying
55 DEG C are warming up to for 25 DEG C, heating rate is 4-6 DEG C/d, and 4-5d is incubated at 55 DEG C, and humidity is down to 30% from 80%, speed 5-
6%/d, honeycomb body primary drying time are 10-11d；The temperature setting of honeycomb body redrying is 55 DEG C and is warming up to 65
DEG C, heating rate is 1 DEG C/h, is incubated 2-4h at 65 DEG C, and humidity is down to 10% from 30%, speed 1-3%/h, honeycomb body two
Secondary drying time is 12-14h, repeats honeycomb body redrying 2 times.
6. the preparation method of integrated low temperature denitrating catalyst according to claim 1, it is characterised in that described is prefabricated
Soma is dry to be risen including precast body primary drying and precast body redrying, the wherein temperature setting of precast body primary drying for 25 DEG C
Temperature is to 65 DEG C, and heating rate is 6-8 DEG C/d, and 2-3d is incubated at 65 DEG C, and humidity is down to 30%, speed 8-10%/d from 80%,
The precast body primary drying time is 6-7d；The temperature setting of precast body redrying is warming up to 85 DEG C for 65 DEG C, heating rate 2
DEG C/h, 2-4h is incubated at 85 DEG C, and humidity is down to 10% from 30%, and speed 1-3%/h, the precast body redrying time is 12-
14h。
7. the preparation method of integrated low temperature denitrating catalyst according to claim 1, it is characterised in that in step 3)
Calcination condition is：Calcination-temperature profile is arranged to be warming up to 400 DEG C from 60-80 DEG C, and programming rate is 20-25 DEG C/h, at 400 DEG C
4-5h is incubated, is cooled to 60-80 DEG C, cooling rate is 45-50 DEG C/h, and the time of calcining is 24-28h.
8. a kind of integrated low temperature denitrating catalyst, it is characterised in that as the method preparation described in claim any one of 1-7
Into；Its active component is by MnOx、CeOxAnd FeOxComposition, carrier is titanium dioxide or titanium tungsten powder；The weight ratio of active component and carrier
For 12-28:72-88.
9. integrated low temperature denitrating catalyst according to claim 8, it is characterised in that described integrated low temperature denitration
Catalyst, by weight percentage, it includes：
MnOx：9.8-22.8%；
CeOx：1.3-3%
FeOx：0.91-2.1%；
Carrier：82.1-87.99%.
10. a kind of denitration method for flue gas, it is characterised in that urged with the integrated low temperature denitration described in claim any one of 8-9
Agent carries out selective catalytic reduction reaction, and the temperature of described selective catalytic reduction reaction is 150-320 DEG C, denitration efficiency
More than 80%.
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| CN108165339A (en) * | 2016-12-08 | 2018-06-15 | 中国石油天然气股份有限公司 | Cycloalkyl transformer oil composition |
| CN108855120A (en) * | 2018-04-28 | 2018-11-23 | 中国建筑材料科学研究总院有限公司 | Monoblock type metal composite oxide low-temperature denitration catalyst and preparation method thereof |
| CN110605122A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Low-temperature flue gas denitration catalyst and preparation method and application thereof |
| CN111036192A (en) * | 2019-12-23 | 2020-04-21 | 中国科学院过程工程研究所 | Coating type wear-resistant vanadium denitration catalyst and preparation method and application thereof |
| CN112657552A (en) * | 2020-12-07 | 2021-04-16 | 安徽欣创节能环保科技股份有限公司 | Vanadium-phosphorus-oxygen low-temperature denitration catalyst and molding preparation method thereof |
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| CN113856769A (en) * | 2021-09-07 | 2021-12-31 | 北京方信立华科技有限公司 | Low temperature denitration catalyst processing preparation system |
| CN114308051A (en) * | 2020-09-28 | 2022-04-12 | 宝山钢铁股份有限公司 | Preparation method and application of low-temperature SCR honeycomb type denitration catalyst |
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| CN106140143A (en) * | 2016-06-28 | 2016-11-23 | 重庆远达催化剂制造有限公司 | A kind of non-homogeneous honeycomb type denitrating catalyst and preparation method thereof |
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| CN108165339A (en) * | 2016-12-08 | 2018-06-15 | 中国石油天然气股份有限公司 | Cycloalkyl transformer oil composition |
| CN108855120A (en) * | 2018-04-28 | 2018-11-23 | 中国建筑材料科学研究总院有限公司 | Monoblock type metal composite oxide low-temperature denitration catalyst and preparation method thereof |
| CN110605122A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Low-temperature flue gas denitration catalyst and preparation method and application thereof |
| CN111036192B (en) * | 2019-12-23 | 2021-08-06 | 中国科学院过程工程研究所 | Coating type wear-resistant vanadium denitration catalyst and preparation method and application thereof |
| CN111036192A (en) * | 2019-12-23 | 2020-04-21 | 中国科学院过程工程研究所 | Coating type wear-resistant vanadium denitration catalyst and preparation method and application thereof |
| CN114308051A (en) * | 2020-09-28 | 2022-04-12 | 宝山钢铁股份有限公司 | Preparation method and application of low-temperature SCR honeycomb type denitration catalyst |
| CN112657552A (en) * | 2020-12-07 | 2021-04-16 | 安徽欣创节能环保科技股份有限公司 | Vanadium-phosphorus-oxygen low-temperature denitration catalyst and molding preparation method thereof |
| CN112657552B (en) * | 2020-12-07 | 2023-07-28 | 安徽欣创节能环保科技股份有限公司 | Vanadium phosphorus oxygen low-temperature denitration catalyst and molding preparation method thereof |
| CN113058587A (en) * | 2021-03-26 | 2021-07-02 | 山西普丽环境工程股份有限公司 | High-dispersion flat plate type low-temperature denitration catalyst and preparation method thereof |
| CN113058587B (en) * | 2021-03-26 | 2022-10-18 | 山西普丽环境工程股份有限公司 | High-dispersion flat plate type low-temperature denitration catalyst and preparation method thereof |
| CN113398952A (en) * | 2021-06-21 | 2021-09-17 | 山东熔石科技有限公司 | Flue gas wide-temperature SCR denitration catalyst and production process thereof |
| CN113856769A (en) * | 2021-09-07 | 2021-12-31 | 北京方信立华科技有限公司 | Low temperature denitration catalyst processing preparation system |
| CN116393123A (en) * | 2023-06-08 | 2023-07-07 | 成都达奇科技股份有限公司 | Preparation method of non-carbon-based denitration catalyst |
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