CN109046320A - Preparation process of honeycomb catalyst for coal-fired power plant denitrating flue gas and products thereof and application - Google Patents
Preparation process of honeycomb catalyst for coal-fired power plant denitrating flue gas and products thereof and application Download PDFInfo
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- CN109046320A CN109046320A CN201810745065.7A CN201810745065A CN109046320A CN 109046320 A CN109046320 A CN 109046320A CN 201810745065 A CN201810745065 A CN 201810745065A CN 109046320 A CN109046320 A CN 109046320A
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- catalyst
- honeycomb catalyst
- power plant
- coal
- flue gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003546 flue gas Substances 0.000 title claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 89
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003365 glass fiber Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000001125 extrusion Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 238000010304 firing Methods 0.000 claims abstract description 3
- 238000004898 kneading Methods 0.000 claims abstract description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims abstract description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 15
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 230000001404 mediated effect Effects 0.000 claims description 12
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 239000004927 clay Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920002261 Corn starch Polymers 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000008120 corn starch Substances 0.000 claims description 4
- 229940099112 cornstarch Drugs 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920001353 Dextrin Polymers 0.000 claims description 2
- 239000004375 Dextrin Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 26
- 241000264877 Hippospongia communis Species 0.000 description 24
- 238000005520 cutting process Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 7
- 229940068984 polyvinyl alcohol Drugs 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003500 flue dust Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 108700018263 Brassica oleracea SCR Proteins 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000000038 chest Anatomy 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—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
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- B01J35/56—
-
- B01J35/58—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a kind of preparation processes of honeycomb catalyst for coal-fired power plant denitrating flue gas and products thereof and application, with TiO2、WO3, catalyst aid and V2O5For effective component, glass fibre, organic binder, inorganic binder, pore creating material, neutralizer and solvent is added, honeycomb catalyst is obtained by mixing, kneading, extrusion forming, drying, firing.The present invention is modified to glass fibre by the way that binder is added, specific catalyst aid is added, by along other various auxiliary agents of addition, and the strainer that specific standard is added carries out filter item, extrusion molding obtains uniformly mixed wet base, and wet base guarantees that the wet base of large scale being capable of evenly drying by drying process twice, not easy to crack, finally calcining obtains honeycomb catalyst.The catalyst compressive strength is high, and catalyst denitrification rate is greater than 80%.
Description
Technical field
The present invention relates to a kind of preparation process of honeycomb catalyst for coal-fired power plant denitrating flue gas and products thereof and
Using, belong to nitrogen oxides catalysis reducing material technical field.
Background technique
On July 29th, 2011, national environmental protection portion have issued " fossil-fuel power plant atmospheric pollutant emission standard " (GB
13223-2011).Flue dust, three major pollutants of sulfur dioxide and nitrogen oxides discharge amount limitation in terms of, new standard is equal
It is made that more stringent regulation.In terms of denitration, from new standard regulation to year on July 1st, 2014, except using W type flame furnace
It thorax and existing recirculating fluidized bed thermal power generation boiler and was constructed and put into operation before on December 31st, 2003 or by construction project environment
The thermal power generation boiler of Impact Report book examination & approval executes discharged nitrous oxides concentration and is not higher than 200mg/m3Limit value；Remaining is existing
Have and create thermal power generation boiler and is performed both by 100mg/m3Emission limit.
It is predicted according to Chinese Ministry of Environmental Protection, newly-increased 8.17 hundred million kilowatts of denitration capacity was needed by 2015.According to existing, " thermal power plant is big
Gas pollutant emission standard ", key area new-built unit must all install SCR denitration device, and other areas about 50% must installation
SCR denitration device.Total SCR catalyst market demand of thermal power plant is 800,000 m during " 12th Five-Year Plan "3, 160,000 m every year on average3。
Between 2016-2020, thermal power plant's installation amount also be will increase, and the service life of denitrating catalyst is about 3 years, needs to regularly replace,
Demand summation can be more than 1,000,000 m3, 200,000 m every year on average3。
SCR denitration technology is the denitrating flue gas scheme being most widely used in the world at present, in Japan, Europe, U.S. etc.
Substantially this technology is all applied in most of power plant of countries and regions.China not yet grasps with independent intellectual property rights big at this stage
The core technology that the design of type thermal power plant SCR system and catalyst generate, technology with independent intellectual property rights and complete set of equipments exist
Occupation ratio is lower in market.SCR flue gas denitrification system key technology is furtherd investigate, efficient, low energy consumption denitrating flue gas is developed
Technology and catalyst prod will provide guidance for domestic independent research SCR denitrating flue gas, meanwhile, the energy conservation for coal-burning power plant
Emission reduction work is significant.
It includes V that US4833113, which discloses a kind of ingredient,2O5、WO3And TiO2A kind of denitrating catalyst, forming out is
Diameter 6mm beaded catalyst, after the Catalyst packing, pressure drop is higher, while the denitrification rate of catalyst is lower.
US7749938B2 discloses a kind of denitrating catalyst, in honeycomb V2O5、WO3And TiO2On the basis of catalyst,
Coat Mn2O3,CuO.The catalyst denitrification rate, which has no, to be significantly improved, but its processing technology is complicated, at high cost.
It includes V that CN101474565A, which discloses effective component,2O5、WO3 、MoO3、MnO2, CuO and TiO2A kind of denitration
Catalyst also discloses preparation method and its Preparation equipment.This method typed pressure is up to 17-21MPa, to equipment requirement compared with
Height, while gained catalyst denitrification rate highest only has 95%.
CN101829560A discloses a kind of denitrating catalyst, and wherein titanium dioxide 70-90 parts, 8-15 parts of tungstic acid,
1.5-3 parts of vanadic anhydride, 2-6 parts of aramid fiber, 3-6 parts of paper pulp cotton, 1.5-3 parts of stearic acid.Tungstic acid used in the catalyst and
Pentoxide content is higher, and relative cost is higher.
CN1593752A discloses a kind of respectively by γ-Al2O3The denitration catalyst on cordierite is coated on active component
Agent.Catalyst obtained by this method, due to being that active component is coated on to cordierite surface, in use process, with activity
The abrasion of component will gradually lose catalytic performance and fail.
CN1792431A is disclosed using cordierite honeycomb ceramic as framework material, with Al2O3And TiO2It is living for complex carrier
Property group is divided into V2O5、WO3.Its high mechanical strength of the denitrating catalyst, but coating method, cause its active component content less,
Its catalytic activity is lower.
Summary of the invention
In order to overcome the deficiencies of the prior art, it is an object of that present invention to provide a kind of bees for coal-fired power plant denitrating flue gas
The preparation process of nest catalyst.
Another object of the present invention is: provide that a kind of above-mentioned preparation process obtains for coal-fired power plant denitrating flue gas
Honeycomb catalyst product.
Another object of the present invention is to: a kind of application of the said goods is provided.
A kind of preparation process of the honeycomb catalyst for coal-fired power plant denitrating flue gas, it is characterised in that with TiO2、WO3、
Catalyst aid and V2O5For effective component, glass fibre, organic binder, inorganic binder, pore creating material, neutralizer and molten is added
Agent obtains honeycomb catalyst by mixing, kneading, extrusion forming, drying, firing, the specific steps are as follows:
Step 1 weighs following each components:
Nano-titanium dioxide 45-75%
Tungstic acid 2-10%
Catalyst aid 1-5%
Vanadic anhydride 0.5-5%
Glass fibre 3-15%
Organic binder 2-10%
Inorganic binder 2-10%
Pore creating material 0.5-5%
Neutralizer 2-10%
Solvent 8-40%.；
Step 2 is dry-mixed: titanium dioxide therein, tungstic acid, catalyst aid, vanadic anhydride are uniformly mixed to obtain solid-state mixing
Object；
Step 3 glass fibre is modified: adding 2-10% organic binder in the short glass fiber having a size of 0.5-2cm and carries out
Mixing is modified processing to short glass fiber, and the organic binder is starch, dextrin, tung oil, polyvinyl alcohol, first
Base cellulose, polyacrylamide, one of polyethylene glycol oxide or combinations thereof；
Step 4 wet mixing: solid mixt, modified glass-fiber, inorganic binder, the pore creating material, neutralization that step 2,3 are obtained
Agent, solvent mixing, and stirred evenly in blender；
Step 5 is mediated: the mixture that step 4 is obtained is put into kneader and is mediated；
Step 6 pre-extruded: the kneaded material that step 5 is obtained, which is put into the extruder with filter screen, to be filtered and pre-extruded,
The sieve meshes diameter is 1-3mm；
Step 7 squeezes out: step 6 being obtained pre-extruded object, is put into vacuum-extruder, forms to obtain denitration by mold integral extrusion
Catalyst；
Step 8 is wet to cut: step 7 being obtained denitrating catalyst and is cut into pieces according to regulation length；
Step 9 primary drying: step 8 is obtained into denitrating catalyst and carries out primary drying processing, the condition of primary drying are as follows: is dry
20-70 DEG C of temperature, dry humidity is 10-90%, and drying time is 72-120 hours；
Step 10 redrying: step 9 is obtained into denitrating catalyst and carries out redrying processing, redrying and condition are as follows: is dry
70-100 DEG C of dry temperature, dry humidity are 10-60%, and drying time is 12-36 hours；
Step 11 calcining: it is calcined denitrating catalyst of the step 10 after dry to obtain honeycomb catalyst, calcination condition are as follows:
400-700 DEG C, calcination time is 24-72 hours.
It is modified to glass fibre by the way that binder is added in preparation process of the present invention, catalyst aid is added, by each along being added
Kind auxiliary agent, and the strainer that specific standard is added carries out filter item, extrusion molding obtains wet base, so that pug mixing is more uniform, from
And improve ceramic honey comb intensity；Wet base by drying process twice, guarantee the wet base of large scale can evenly drying, it is not easy to crack,
Improve yield rate.Finally calcining obtains honeycomb catalyst, and compressive strength is high, and catalyst denitrification rate is greater than 80%.
The glass fiber strength is not less than 3.5GPa, and modulus is not less than the high intensity of 70GPa, high-modulus, corrosion-resistant
Alkaline glass fiber.
It joined high-intensitive, high-modulus alkaline glass fiber in the present invention, significantly improve ceramic honey comb intensity, and pass through
Blank uniformity is improved, is conducive to later period molding, drying, and improve finished product compressive strength.
The catalyst aid is MoO3, Co3O4。
Further, the organic binder is polyvinyl alcohol, methylcellulose, polyacrylamide, polyethylene glycol oxide.
The inorganic binder is clay, clay, bentonite.
The neutralizer is 25% ammonium hydroxide of technical grade.
The pore creating material is polyethylene glycol, cornstarch, one of carbon black or combinations thereof.
The solvent is water, one of ethyl alcohol, acetone or any combination thereof.
The present invention also provides a kind of honeycomb catalyst for coal-fired power plant denitrating flue gas, according to above-mentioned preparation process
Obtained honeycomb catalyst product.
It is applied in coal-fired power plant denitrating flue gas the present invention also provides a kind of according to above-mentioned honeycomb catalyst product
300-500 DEG C of temperature range, and all can be used in high dirt and low dirt environment.
The product strength that preparation process of the present invention obtains is high, not easy to crack, and compressive strength is high, and catalyst denitrification rate is greater than
80%。
The present invention is modified to glass fibre by the way that binder is added, and specific catalyst aid is added, by various along other are added
Auxiliary agent, and the strainer that specific standard is added carries out filter item, extrusion molding obtains uniformly mixed wet base, which does twice
Drying process, guarantee the wet base of large scale can evenly drying, it is not easy to crack, finally calcining obtain honeycomb catalyst.The catalyst pressure
Contracting intensity is high, and catalyst denitrification rate is greater than 80%.
Detailed description of the invention
Fig. 1 is denitrating catalyst preparation process flow schematic diagram；
Fig. 2 is 2 denitrification rate curve of embodiment.
Specific embodiment
The present invention is further described by the following examples, but the present invention is not limited solely to following embodiment.
Honeycomb catalyst carries out compressive strength test using WD-P1503 electronic tension tester.
The activity rating of honeycomb catalyst carries out in fixed bed reactors (internal diameter 20mm quartz ampoule, long 400mm), surveys
Strip part: reaction gas is 400ppm NO, 400ppm NH3,400ppm SO2,6% O2,9% CO2,10% H2O, using N2
Balance, air speed 5000h-1, reaction temperature is room temperature ~ 550 DEG C, and heating rate is 10 DEG C/min.Using thermoelectricity 42i-HL into
Row denitration evaluation.
Embodiment 1
Fig. 1 be denitrating catalyst preparation process flow schematic diagram, by the process flow the preparation method is as follows:
4.84kg titanium dioxide, 0.6kg tungstic acid, 0.11kg molybdenum trioxide, 0.21kg vanadic anhydride are weighed, mixing is equal
It is even.
The 1cm high-strength glass fibre for weighing 0.44kg is chopped yarn (intensity 8.5GPa, modulus 90GPa), and addition 0.57kg is poly-
Vinyl alcohol is modified it.
Above-mentioned material is mixed, and 0.44kg clay is added, 0.07kg carbon black, the 25% technical grade ammonium hydroxide of 0.24kg,
0.41kg ethyl alcohol and the mixing of the water of 2.07kg, and be sufficiently stirred in blender.
Pug after being sufficiently stirred is put into kneader and is mediated；Then in the pre-extruded of the strainer equipped with mesh 2mm
Filtering and pre-extruded in machine；Material after pre-extruded is put into vacuum-extruder, is formed by mold integral extrusion, and according to rule
Measured length is cut into pieces.
Wet base after cutting carries out primary drying processing, primary drying condition are as follows: 50 DEG C of drying temperature, drying humidity is
60%, drying time is 72 hours.
Wet base after primary drying carries out redrying and handles to obtain dry body, redrying condition are as follows: and 80 DEG C of drying temperature,
Dry humidity is 45%, and drying time is 24 hours.It is calcined 36 hours for 500 DEG C after the completion of drying, obtains honeycomb catalyst.
Testing machine carries out compressive strength test, and the process conditions and test result for preparing product are shown in Table 1.
Embodiment 2
5.50kg titanium dioxide, 0.11kg tungstic acid, 0.10kg molybdenum trioxide, 0.15kg vanadic anhydride are weighed,
The 1.5cm high-strength glass fibre of 0.54kg is chopped yarn (intensity 8.5GPa, modulus 90GPa), adds 0.48kg polyvinyl alcohol
It is modified.
Above-mentioned material is mixed, and 0.65kg clay is added, 0.36kg carbon black, the 25% technical grade ammonium hydroxide of 0.24kg,
0.47kg ethyl alcohol and the mixing of the water of 2.03kg, and be sufficiently stirred in blender.
Pug after being sufficiently stirred is put into kneader and is mediated；Then it is squeezed in the pre- of the strainer equipped with mesh 1.5mm
Filtering and pre-extruded in machine out；Material after pre-extruded is put into vacuum-extruder, is formed by mold integral extrusion, and according to
Specific length is cut into pieces.
Wet base after cutting carries out primary drying processing.Primary drying condition are as follows: 45 DEG C of drying temperature, drying humidity is
50%, drying time is 72 hours.
Wet base after primary drying carries out redrying and handles to obtain dry body.Redrying condition are as follows: 85 DEG C of drying temperature,
Dry humidity is 50%, and drying time is 24 hours.It is calcined 48 hours for 500 DEG C after the completion of drying, obtains honeycomb catalyst.
Testing machine carries out compressive strength test, and the process conditions and test result for preparing product are shown in Table 1.
The catalyst sample of above-mentioned preparation is cut to obtain 17mm × 17mm × 17mm sample, using 42i-HL to embodiment
2 carry out denitration evaluation, as a result see Fig. 2.
Test result shows that gained denitrating catalyst compressive strength of the invention is high, and catalyst has in 300-500 DEG C of high temperature section
There is higher denitrification rate, power plant's denitration field can be applied.
Embodiment 3
5.9kg titanium dioxide, 0.21kg molybdenum trioxide, 0.05kg vanadic anhydride are weighed, is uniformly mixed.
The 1.5cm high-strength glass fibre for weighing 0.54kg is chopped yarn (intensity 8.5GPa, modulus 90GPa), adds 0.27kg
Polyvinyl alcohol is modified it.
Above-mentioned material is mixed, and 0.35kg clay is added, 0.1kg cornstarch, the 25% technical grade ammonium hydroxide of 0.24kg,
The mixing of the water of 0.37kg acetone and 1.97kg, and be sufficiently stirred in blender.
Pug after being sufficiently stirred is put into kneader and is mediated；Then it is squeezed in the pre- of the strainer equipped with mesh 0.5mm
Filtering and pre-extruded in machine out；Material after pre-extruded is put into vacuum-extruder, is formed by mold integral extrusion, and according to
Specific length is cut into pieces.
Wet base after cutting carries out primary drying processing.Primary drying condition are as follows: 40 DEG C of drying temperature, drying humidity is
50%, drying time is 48 hours.
Wet base after primary drying carries out redrying and handles to obtain dry body.Redrying condition are as follows: 90 DEG C of drying temperature,
Dry humidity is 50%, and drying time is 36 hours.It is calcined 12 hours for 600 DEG C after the completion of drying, obtains honeycomb catalyst.
Testing machine carries out compressive strength test, and the process conditions and test result for preparing product are shown in Table 1.
Embodiment 4
4.5kg titanium dioxide, 1.0kg tungstic acid, 045kg vanadic anhydride are weighed, is uniformly mixed.
The 1.5cm high-strength glass fibre for weighing 0.74kg is chopped yarn (intensity 8.5GPa, modulus 90GPa), and addition 0.28g is poly-
Ethylene oxide is modified it.
Above-mentioned material is mixed, and 0.35kg bentonite is added, 0.1kg carbon black, the 25% technical grade ammonium hydroxide of 0.24kg,
0.35kg ethyl alcohol and the mixing of the water of 1.99kg, and be sufficiently stirred in blender.
Pug after being sufficiently stirred is put into kneader and is mediated；Then it is squeezed in the pre- of the strainer equipped with mesh 2.5mm
Filtering and pre-extruded in machine out；Material after pre-extruded is put into vacuum-extruder, is formed by mold integral extrusion, and according to
Specific length is cut into pieces.
Wet base after cutting carries out primary drying processing.Primary drying condition are as follows: 60 DEG C of drying temperature, drying humidity is
35%, drying time is 72 hours.
Wet base after primary drying carries out redrying and handles to obtain dry body.Redrying condition are as follows: 90 DEG C of drying temperature,
Dry humidity is 50%, and drying time is 36 hours.It is calcined 12 hours for 600 DEG C after the completion of drying.
For the catalyst sample that above-described embodiment obtains having a size of 150mm × 150mm × 1000mm, 18 holes × 18 holes can root
According to needs, different molds are selected, obtain different dimensions samples.
The catalyst sample of above-mentioned preparation is cut to obtain 25mm × 25mm × 25mm sample, is carried out using universal testing machine
Compressive strength test, test result are shown in Table 1.
Comparative example 1
4.84kg titanium dioxide, 0.6kg tungstic acid, 0.11kg molybdenum trioxide, 0.21kg vanadic anhydride are weighed, mixing is equal
It is even.
The 1cm simple glass fiber for weighing 0.44kg is chopped yarn (intensity 2.5GPa, modulus 55GPa), and addition 0.57kg is poly-
Vinyl alcohol is modified it.
Above-mentioned material is mixed, and 0.44kg clay is added, 0.07kg carbon black, the 25% technical grade ammonium hydroxide of 0.24kg,
0.41kg ethyl alcohol and the mixing of the water of 2.07kg, and be sufficiently stirred in blender.
Pug after being sufficiently stirred is put into kneader and is mediated；Then in the pre-extruded of the strainer equipped with mesh 2mm
Filtering and pre-extruded in machine；Material after pre-extruded is put into vacuum-extruder, is formed by mold integral extrusion, and according to rule
Measured length is cut into pieces.
Wet base after cutting carries out primary drying processing.Primary drying condition are as follows: 50 DEG C of drying temperature, drying humidity is
60%, drying time is 72 hours.
Wet base after primary drying carries out redrying and handles to obtain dry body.Redrying condition are as follows: 80 DEG C of drying temperature,
Dry humidity is 45%, and drying time is 24 hours.It is calcined 36 hours for 500 DEG C after the completion of drying, obtains honeycomb catalyst.
Testing machine carries out compressive strength test, and the process conditions and test result for preparing product are shown in Table 1.
Comparative example 2
Weigh 5.74kg titanium dioxide, 0.11kg tungstic acid, 0.10kg molybdenum trioxide, 0.15kg vanadic anhydride, 0.54kg
1.5cm high-strength glass fibre be chopped yarn (intensity 8.5GPa, modulus 90GPa), mixing.
Above-mentioned material is mixed, and 0.85kg clay is added, 0.40kg carbon black, the 25% technical grade ammonium hydroxide of 0.24kg,
0.47kg ethyl alcohol and the mixing of the water of 2.03kg, and be sufficiently stirred in blender.
Pug after being sufficiently stirred is put into kneader and is mediated；Then it is squeezed in the pre- of the strainer equipped with mesh 1.5mm
Filtering and pre-extruded in machine out；Material after pre-extruded is put into vacuum-extruder, is formed by mold integral extrusion, and according to
Specific length is cut into pieces.
Wet base after cutting carries out primary drying processing.Primary drying condition are as follows: 45 DEG C of drying temperature, drying humidity is
50%, drying time is 72 hours.
Wet base after primary drying carries out redrying and handles to obtain dry body.Redrying condition are as follows: 85 DEG C of drying temperature,
Dry humidity is 50%, and drying time is 24 hours.It is calcined 48 hours for 500 DEG C after the completion of drying, obtains honeycomb catalyst.
Testing machine carries out compressive strength test, and the process conditions and test result for preparing product are shown in Table 1.
The catalyst sample of above-mentioned preparation is cut to obtain 17mm × 17mm × 17mm sample, using 42i-HL to embodiment
2 carry out denitration evaluation, as a result see Fig. 2.
Comparative example 3
5.9kg titanium dioxide, 0.21kg molybdenum trioxide, 0.05kg vanadic anhydride are weighed, is uniformly mixed.
The 1.5cm high-strength glass fibre for weighing 0.54kg is chopped yarn (intensity 8.5GPa, modulus 90GPa), adds 0.27kg
Polyvinyl alcohol is modified it.
Above-mentioned material is mixed, and 0.35kg clay is added, 0.1kg cornstarch, the 25% technical grade ammonium hydroxide of 0.24kg,
The mixing of the water of 0.37kg acetone and 1.97kg, and be sufficiently stirred in blender.
Pug after being sufficiently stirred is put into kneader and is mediated；Then it is squeezed in the pre- of the strainer equipped with mesh 5.5mm
Filtering and pre-extruded in machine out；Material after pre-extruded is put into vacuum-extruder, is formed by mold integral extrusion, and according to
Specific length is cut into pieces.
Wet base after cutting carries out primary drying processing.Primary drying condition are as follows: 40 DEG C of drying temperature, drying humidity is
50%, drying time is 48 hours.
Wet base after primary drying carries out redrying and handles to obtain dry body.Redrying condition are as follows: 90 DEG C of drying temperature,
Dry humidity is 50%, and drying time is 36 hours.It is calcined 12 hours for 600 DEG C after the completion of drying, obtains honeycomb catalyst.
Testing machine carries out compressive strength test, and the process conditions and test result for preparing product are shown in Table 1.
Comparative example 4
4.5kg titanium dioxide, 1.0kg tungstic acid, 045kg vanadic anhydride are weighed, is uniformly mixed.
The 1.5cm high-strength glass fibre for weighing 0.74kg is chopped yarn (intensity 8.5GPa, modulus 90GPa), and addition 0.28g is poly-
Ethylene oxide is modified it.
Above-mentioned material is mixed, and 0.35kg bentonite is added, 0.1kg carbon black, the 25% technical grade ammonium hydroxide of 0.24kg,
0.35kg ethyl alcohol and the mixing of the water of 1.99kg, and be sufficiently stirred in blender.
Pug after being sufficiently stirred is put into kneader and is mediated；Then it is squeezed in the pre- of the strainer equipped with mesh 2.5mm
Filtering and pre-extruded in machine out；Material after pre-extruded is put into vacuum-extruder, is formed by mold integral extrusion, and according to
Specific length is cut into pieces.
Wet base after cutting carries out primary drying processing.Primary drying condition are as follows: 60 DEG C of drying temperature, drying humidity is
35%, drying time is 72 hours.It is calcined 12 hours for 600 DEG C after the completion of drying, obtains honeycomb catalyst.
Testing machine carries out compressive strength test, and the process conditions and test result for preparing product are shown in Table 1.
Specifically, titanium dioxide, tungstic acid, catalyst aid and the vanadic anhydride in the present embodiment denitrating catalyst
For primary raw material, wherein tungstic acid can be effectively reduced the absorption of denitrating catalyst sulfur dioxide and flue dust, and reduce dioxy
Change sulphur conversion ratio.
Denitrating catalyst pitch of holes can be 1-10mm in the present embodiment, and hole inner wall thickness is 0.5-1.3mm, and port is
150×150mm.By the pitch of holes and hole inner wall thickness of optimization denitrating catalyst, the surface area of denitrating catalyst can be increased,
Catalyst denitrification rate is improved, and increases the compressive strength and antiwear property of catalyst.
The present embodiment denitrating catalyst compressive strength is higher, and denitrification rate is greater than 80%, can be applied to denitration field.Simultaneously
The present embodiment denitrating catalyst can be used in 300-500 DEG C of high temperature section, and all can be used in high dirt and low dirt environment.
Claims (10)
1. a kind of preparation process of the honeycomb catalyst for coal-fired power plant denitrating flue gas, it is characterised in that with TiO2、WO3, urge
Change auxiliary agent and V2O5For effective component, glass fibre, organic binder, inorganic binder, pore creating material, neutralizer and solvent is added,
Honeycomb catalyst is obtained by mixing, kneading, extrusion forming, drying, firing, the specific steps are as follows:
Step 1 weighs following each components:
Nano-titanium dioxide 45-75%
Tungstic acid 2-10%
Catalyst aid 1-5%
Vanadic anhydride 0.5-5%
Glass fibre 3-15%
Organic binder 2-10%
Inorganic binder 2-10%
Pore creating material 0.5-5%
Neutralizer 2-10%
Solvent 8-40%.；
Step 2 is dry-mixed: titanium dioxide therein, tungstic acid, catalyst aid, vanadic anhydride are uniformly mixed to obtain solid-state mixing
Object；
Step 3 glass fibre is modified: adding 2-10% organic binder in the short glass fiber having a size of 0.5-2cm and carries out
Mixing is modified processing to short glass fiber, and the organic binder is starch, dextrin, tung oil, polyvinyl alcohol, first
Base cellulose, polyacrylamide, one of polyethylene glycol oxide or combinations thereof；
Step 4 wet mixing: solid mixt, modified glass-fiber, inorganic binder, the pore creating material, neutralization that step 2,3 are obtained
Agent, solvent mixing, and stirred evenly in blender；
Step 5 is mediated: the mixture that step 4 is obtained is put into kneader and is mediated；
Step 6 pre-extruded: the kneaded material that step 5 is obtained, which is put into the extruder with filter screen, to be filtered and pre-extruded,
The sieve meshes diameter is 1-3mm；
Step 7 squeezes out: step 6 being obtained pre-extruded object, is put into vacuum-extruder, forms to obtain denitration by mold integral extrusion
Catalyst；
Step 8 is wet to cut: step 7 being obtained denitrating catalyst and is cut into pieces according to regulation length；
Step 9 primary drying: step 8 is obtained into denitrating catalyst and carries out primary drying processing, the condition of primary drying are as follows: is dry
20-70 DEG C of temperature, dry humidity is 10-90%, and drying time is 72-120 hours；
Step 10 redrying: step 9 is obtained into denitrating catalyst and carries out redrying processing, redrying and condition are as follows: is dry
70-100 DEG C of dry temperature, dry humidity are 10-60%, and drying time is 12-36 hours；
Step 11 calcining: it is calcined denitrating catalyst of the step 10 after dry to obtain honeycomb catalyst, calcination condition are as follows:
400-700 DEG C, calcination time is 24-72 hours.
2. the preparation process for the honeycomb catalyst of coal-fired power plant denitrating flue gas, feature exist according to claim 1
Glass fiber strength described in step 3 is not less than 3.5GPa, and modulus is not less than the high intensity of 70GPa, high-modulus, corrosion resistant
Alkaline glass fiber.
3. the preparation process for the honeycomb catalyst of coal-fired power plant denitrating flue gas, feature exist according to claim 1
Catalyst aid described in step 3 is MoO3, Co3O4。
4. the preparation process for the honeycomb catalyst of coal-fired power plant denitrating flue gas, feature exist according to claim 1
In the organic binder is polyvinyl alcohol, methylcellulose, polyacrylamide, polyethylene glycol oxide.
5. the preparation process for the honeycomb catalyst of coal-fired power plant denitrating flue gas, feature exist according to claim 1
In the inorganic binder is clay, clay, bentonite.
6. the preparation process for the honeycomb catalyst of coal-fired power plant denitrating flue gas, feature exist according to claim 1
In the neutralizer is 25% ammonium hydroxide of technical grade.
7. the preparation process for the honeycomb catalyst of coal-fired power plant denitrating flue gas, feature exist according to claim 1
In the pore creating material is polyethylene glycol, cornstarch, one of carbon black or combinations thereof.
8. the preparation process for the honeycomb catalyst of coal-fired power plant denitrating flue gas, feature exist according to claim 1
In the solvent is water, one of ethyl alcohol, acetone or any combination thereof.
9. a kind of honeycomb catalyst for coal-fired power plant denitrating flue gas, preparation according to any one of claims 1 to 8
The honeycomb catalyst product that technique obtains.
10. a kind of application of the honeycomb catalyst product in coal-fired power plant denitrating flue gas according to claim 8.
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| CN110354843A (en) * | 2019-08-28 | 2019-10-22 | 华北电力大学 | A kind of thin-walled honeycomb formula low temperature sulfur resistive SCR denitration and preparation method thereof |
| CN110665495A (en) * | 2019-10-14 | 2020-01-10 | 成都东方凯特瑞环保催化剂有限责任公司 | Honeycomb catalyst adhesive system and preparation method 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 |
| CN111545040A (en) * | 2020-04-10 | 2020-08-18 | 佛山华清智业环保科技有限公司 | Composite denitration agent and preparation method thereof |
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| CN112108143A (en) * | 2020-09-27 | 2020-12-22 | 江西新科环保股份有限公司 | Ultra-high temperature denitration catalyst |
| CN112808265A (en) * | 2020-12-28 | 2021-05-18 | 南京赤博环保科技有限公司 | High-strength manganese oxide particle catalyst and preparation process thereof |
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Application publication date: 20181221 |