CN108187710A - Improve the method for integral extruding type honeycomb catalyst mechanical strength - Google Patents
Improve the method for integral extruding type honeycomb catalyst mechanical strength Download PDFInfo
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- CN108187710A CN108187710A CN201711344964.8A CN201711344964A CN108187710A CN 108187710 A CN108187710 A CN 108187710A CN 201711344964 A CN201711344964 A CN 201711344964A CN 108187710 A CN108187710 A CN 108187710A
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- honeycomb catalyst
- mechanical strength
- type honeycomb
- catalyst
- extruding type
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000001125 extrusion Methods 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003365 glass fiber Substances 0.000 claims abstract description 15
- 239000011812 mixed powder Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000002708 enhancing effect Effects 0.000 claims abstract description 8
- 239000002383 tung oil Substances 0.000 claims abstract description 8
- 229920002678 cellulose Polymers 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 6
- 239000001923 methylcellulose Substances 0.000 claims abstract description 6
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000001913 cellulose Substances 0.000 claims abstract description 4
- 230000009969 flowable effect Effects 0.000 claims abstract description 3
- 244000275012 Sesbania cannabina Species 0.000 claims abstract 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 238000004513 sizing Methods 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 150000003681 vanadium Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 235000010980 cellulose Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 208000028659 discharge Diseases 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical Kinetics & Catalysis (AREA)
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- Combustion & Propulsion (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The present invention relates to a kind of methods for improving integral extruding type honeycomb catalyst mechanical strength, it is characterised in that is as follows：By Ludox（20~40wt%）, Aluminum sol（10~30wt%）, plasticizer, tung oil and kaolin is sufficiently stirred as sticky white slurries；Methylcellulose is added to white slurries, stirring forms not flowable body of paste；Catalyst fines, sesbania powder, cellulose, glass fibre are added in kneader and are stirred uniformly mixed, obtains mixed powder；White body of paste is added in mixed powder, is sufficiently stirred to obtain wet feed group；Wet feed is rolled into a ball using descaling extrusion press and carries out extrusion molding, is dried, carrier enhancing coating is coated on honeycomb catalyst skin-surface, is coated 2 ~ 5 times, and dry, calcining.It compensates for traditional caducous problem of coating type honeycomb catalyst coating, while improves the mechanical strength of integral extruding type honeycomb catalyst, and there is sufficiently high mechanical strength to meet the needs of actual use.
Description
Technical field
The present invention relates to a kind of methods for improving integral extruding type honeycomb catalyst mechanical strength, it is especially useful in the diesel oil tailstock
Gas field of purification, wherein being used in particular for being restored according to the nitrogen oxides of selective catalytic reduction method, i.e., using nitrogenous reducing agent
Nitrogen oxides reduction.
Background technology
Nitrogen oxides（NOx）It is one of major pollutants of air, wherein NO and NO2Shared ratio is maximum.Along with
China's rapid development of economy, the demand to the energy is growing, and the discharge capacity of NOx is also in growth drastically.Diesel vehicle is NOx
One of primary discharge source, NOx emission control become a subject to attract people's attention very much in environmental protection.For diesel vehicle
NOx emission, countries in the world emission regulation are increasingly strict：NOx emission limit value is set to 2.0g/ by 5 standard of Europe that in September, 2009 is carried out
KWh, the end of the year 2013 perform 6 discharge standard of Europe be even more on the basis of Europe 5 by NOx emission reduce by 80%, and the U.S. implement regulation
It is also stringenter than Europe 5 and Europe 6.China's diesel engine for automobile used 4 standard of Europe in 2010.At present, NH3-SCR technology is unique
It is commercialized application technology.NH3- SCR technology is to utilize NH3Or urea is as reducing substances, in certain temperature and catalyst
It is selective preferential NOx to be reduced to N under effect2And H2O.Emission-control equipment used in SCR technology is mainly by carrier and catalysis
Agent two parts are formed, the performance quality of catalyst carrier, very big to catalyst activity and aging effects, and ceramic honeycomb carrier exists
Field of exhaust gas purification has been widely used.
SCR integral honeycombed catalysts are broadly divided into two kinds of coating type and blending extrusion formula at present.Coating type is will to be catalyzed
Agent powder is prepared by mixing into catalyst pulp coated on honeycomb ceramic carrier with certain additive, forms certain thickness urge
Agent layer, the catalyst being currently mainly used have vanadium tungsten titanium catalyst and molecular sieve catalyst.However such method is faced with painting
Layer is insecure and catalyst uploads the problem of rate is not high, i.e., with the increase for using mileage, supported catalyst can take off
It falls and sulfurization inactivates, conversion rate of NOx is caused to reduce, emission regulation demands can not be met.It is prepared by the blending extrusion method of forming
Honeycomb catalyst is to mix catalyst with certain additive, is squeezed by a series of processing step cellular, that is, is urged
Agent is uniformly distributed in the various pieces of carrier, and such method shortens SCR integral honeycombed catalyst preparation process flows,
The problem of compensating for traditional coating type monolithic catalyst coating shedding improves the durable mileage of monoblock type SCR catalyst.
WO2010/099395A1, which is disclosed, squeezes out honeycombed catalyst and its manufacturing method.Honeycomb catalyst includes being selected from
The first oxide in the group be made of tungsten oxide, vanadium oxide and combinations thereof, selected from by cerium oxide, lanthana, zirconium oxide and its
Combine the second oxide in the group of composition.In one embodiment, cerium oxide layer, oxidation are coated on the zeolite core of extrusion
The mixture of zirconium and tungsten oxide.103842076 A of CN disclose a kind of blending extrusion honeycombed catalyst, which includes
The extrusion active carrier and washcoat of honeycomb ceramics pattern, the extrusion active carrier include the first SCR catalytic active components and have
There are multiple channels that exhaust gas is flowed through in operating process, which includes the 2nd SCR catalysis work for being applied to squeeze-up
Property component, wherein the first SCR catalytic active components and the 2nd SCR catalytic active components are each independently selected from using vanadium as living
The catalyst of property component is urged using transition metal or lanthanide series as the oxide of catalytic active component and iron/copper-based zeolite
Agent.
Strenuous vibration caused by being shaken due to the thermal shock of air-flow and the out-of-flatness on road surface and cylinder, therefore catalyst is required to carry
Body has higher mechanical strength.And above several disclosed patents do not propose how that improving and improve integral extruding type honeycomb urges
The method of agent mechanical strength.SCR integral honeycombed catalysts are broadly divided into two kinds of coating type and blending extrusion formula at present.Coating
Formula honeycomb catalyst is faced with that coating is insecure and catalyst uploads the problem of rate is not high, i.e., with the increase for using mileage, carries
Catalyst on body can be fallen off and sulfurization inactivation, conversion rate of NOx is caused to reduce, can not meet emission regulation will
It asks.
Invention content
The purpose of the present invention is to provide a kind of methods for improving integral extruding type honeycomb catalyst mechanical strength, make up
The traditional caducous problem of coating type honeycomb catalyst coating, while the machinery for improving integral extruding type honeycomb catalyst is strong
Degree restores, while there is sufficiently high mechanical strength actually to be made with meeting for the nitrogen oxides of selective catalytic reduction method
Demand.
The technical proposal of the invention is realized in this way：A kind of side for improving integral extruding type honeycomb catalyst mechanical strength
Method, it is characterised in that be as follows：
Step 1：By Ludox（20~40wt%）, Aluminum sol（10~30wt%）, plasticizer, tung oil and kaolin is sufficiently stirred into
For sticky white slurries.
Step 2：Methylcellulose is added to the white slurries obtained in step 1, stirring formation in several minutes can not
The body of paste of flowing.
Step 3：Catalyst fines, sesbania powder, cellulose, glass fibre are added in kneader and are stirred mixing
Uniformly, mixed powder is obtained.
Step 4：The white body of paste obtained in step 2 is added in the mixed powder obtained in step 3, fully
Stir to get wet feed group.
Step 5：Wet feed is rolled into a ball using descaling extrusion press and carries out extrusion molding, extrusion pressure control is in 15 ~ 25MPa, use
Microwave heating is shaped, a length of 1 ~ 5min during sizing, is dried processing in an oven, and drying condition dries 1 for 50 ~ 110 DEG C ~
12h。
Step 6：Carrier enhancing coating is coated on honeycomb catalyst skin-surface, is coated 2 ~ 5 times, and dry, calcining.
The coating of carrier enhancement solution can coat in step 5 after extrusion molding, be coated after microwave sizing can be also completed in step 5,
It also can be during extrusion molding by the coating of carrier enhancement solution and honeycomb catalyst skin-surface.
It is 0 ~ 20 part to include Ludox and Aluminum sol by the mass fraction of white slurries in the step 1, and plasticizer is
0 ~ 3 part, 0 ~ 3 part of tung oil, 0 ~ 10 part of kaolin.
Plasticizer in the step 1 is the mixture of polyethylene glycol, polyethylene oxide or the two, molecular weight for 400 ~
10000。
Methylcellulose addition in the step 2 is 0.1 ~ 5wt% of grind slurries quality.
It is 50 ~ 70 parts to include catalyst fines by the mass fraction of mixed powder in the step 3,0 ~ 3 part of sesbania powder,
0 ~ 3 part of cellulose, 0 ~ 10 part of glass fibre.
Catalyst fines in the step 3 are commercially available vanadium series catalyst, Cu zeolite catalysts or Cu/Fe zeolite catalysises
Agent.
Carrier enhancing coating in the step 6 is the aluminium dihydrogen phosphate slurries for being mixed with glass fibre, wherein biphosphate
The content of aluminium dihydrogen phosphate is 40% ~ 70% in aluminium paste liquid, and glass fibre accounts for the 2% ~ 10% of enhancing coating.Calcination condition for 450 ~
It is calcined 3 ~ 10 hours at 600 DEG C.
The positive effect of the present invention is that raw material are cheap, sintering temperature is low, preparation method is simple, compared to coating type honeycomb
The shortcomings that catalyst saves coating processes process, and no catalyst coat comes off, while the entirety strengthened through carrier enhancing coating
Extrusion type honeycomb catalyst has the demand that sufficiently high mechanical strength disclosure satisfy that actual use.
Description of the drawings
Fig. 1 honeycomb catalyst material object pictures.
Fig. 2 honeycomb catalysts covering enhances picture.
Specific embodiment
It is described further with reference to the accompanying drawings and examples, but present disclosure is not limited to this.
Embodiment 1
A kind of method for improving integral extruding type honeycomb catalyst mechanical strength, includes the following steps：
Step 1：By 500g Ludox（30wt%）, 500g Aluminum sols（30wt%）, 20g polyethylene glycol, 10g tung oil and 50g kaolinites
Soil is sufficiently stirred as sticky white slurries 1.
Step 2：510gCu zeolite catalysts powder, 25g sesbania powders, 25g celluloses, 10g glass fibres are added to and pinched
It is stirred uniformly mixed in conjunction machine, obtains mixed powder.
Step 3：Slurries 1 are added in the mixed powder that step 2 obtains, are sufficiently stirred to obtain wet feed group.
Step 4：Wet feed is rolled into a ball using descaling extrusion press and carries out extrusion molding, extrusion pressure is controlled after 20MPa, extrusion
The wet base of honeycomb catalyst is obtained, the honeycomb catalyst of extrusion is placed in moderate heat in micro-wave oven shapes 2 minutes, 70 DEG C of dry 8h.
Step 5：It is 60% by biphosphate aluminium content, the aluminium dihydrogen phosphate slurries that content of glass fiber is 5% are applied with hairbrush
Dried carrier skin-surface in step 4 is smeared, is uniformly smeared 2 times.And phosphoric acid extra at port edge is absorbed with filter paper
Aluminum dihydrogen slurries.Dry 1h in 80 DEG C of baking ovens is placed it in, is subsequently placed in 500 DEG C of Muffle furnaces and calcines 2h.
The results are shown in Table 1 for honeycomb catalyst compression strength and active testing
Embodiment 2
A kind of method for improving integral extruding type honeycomb catalyst mechanical strength, includes the following steps：
Step 1：By 400g Ludox（30wt%）, 400g Aluminum sols（30wt%）, 25g polyethylene oxide, 20g tung oil and 60g high
Ridge soil is sufficiently stirred as sticky white slurries 1.
Step 2：8g methylcellulose is added to the white slurries 1 obtained in step 1, stirs several minutes and is formed not
Flowable body of paste.
Step 3：630gCu/Fe zeolite catalysts powder, 20g sesbania powders, 20g celluloses, 20g glass fibres are added in
It is stirred into kneader uniformly mixed, obtains mixed powder.
Step 4：Body of paste is added in the mixed powder that step 2 obtains, is sufficiently stirred to obtain wet feed group.
Step 5：Wet feed is rolled into a ball using descaling extrusion press and carries out extrusion molding, extrusion pressure is controlled after 20MPa, extrusion
The wet base of honeycomb catalyst is obtained, the honeycomb catalyst of extrusion is placed in moderate heat in micro-wave oven shapes 3 minutes, 90 DEG C of dry 6h.
Step 6：It is 70% by biphosphate aluminium content, the aluminium dihydrogen phosphate slurries that content of glass fiber is 6% are applied with hairbrush
Dried carrier skin-surface in step 4 is smeared, is uniformly smeared 2 times.And phosphoric acid extra at port edge is absorbed with filter paper
Aluminum dihydrogen slurries.Dry 1h in 90 DEG C of baking ovens is placed it in, is subsequently placed in 550 DEG C of Muffle furnaces and calcines 1h.
The results are shown in Table 1 for honeycomb catalyst compression strength and active testing
Embodiment 3
A kind of method for improving integral extruding type honeycomb catalyst mechanical strength, includes the following steps：
Step 1：By 450g Ludox（30wt%）, 450g Aluminum sols（30wt%）, 25g polyethylene glycol, 20g tung oil and 60g kaolinites
Soil is sufficiently stirred as sticky white slurries 1.
Step 2：By 600g vanadium series catalysts powder, 60g silicon carbide powders, 15g sesbania powders, 15g celluloses, 10g glass
Fiber, which is added in kneader, to be stirred uniformly mixed, obtains mixed powder.
Step 3：Slurries 1 are added in the mixed powder that step 2 obtains, are sufficiently stirred to obtain wet feed group.
Step 4：Wet feed is rolled into a ball using descaling extrusion press and carries out extrusion molding, extrusion pressure is controlled after 20MPa, extrusion
The wet base of honeycomb catalyst is obtained, the honeycomb catalyst of extrusion is placed in moderate heat in micro-wave oven shapes 3 minutes, 100 DEG C of dry 4h.
Step 5：It is 40% by biphosphate aluminium content, the aluminium dihydrogen phosphate slurries that content of glass fiber is 8% are applied with hairbrush
Dried carrier skin-surface in step 4 is smeared, is uniformly smeared 2 times.And phosphoric acid extra at port edge is absorbed with filter paper
Aluminum dihydrogen slurries.Dry 1h in 90 DEG C of baking ovens is placed it in, is subsequently placed in 550 DEG C of Muffle furnaces and calcines 1h.
The results are shown in Table 1 for honeycomb catalyst compression strength and active testing
Out of stock efficiency test condition：150 ~ 250 DEG C of temperature, NO：600ppm, NH3:600ppm, O2：5%, Balance Air N2, air speed：
50000h-1.Detection inlet and outlet NO concentration respectively, so as to calculate the conversion ratio of NO, obtains the denitration efficiency of catalyst.
Honeycomb catalyst intensity test condition：It is extracted in honeycomb catalyst away from inside of the side more than 5mm along A axis directions
The length of side is 25mm square samples.Sample is put into baking oven, the dry 2h at a temperature of 110 ± 5 DEG C.It places into cold in drier
But room temperature is arrived.Sample is then placed on to the centre of Material Testing Machine lower platen, is applied with the rate of 1.5 ~ 2.5MPa/s
Load, until sample destroys.And record peak load value when sample destroys.
It is described above for illustrating the principle of the present invention and its effect, and is not intended to limit the present invention.Technology belonging to any
The technical staff in field can modify to above-described embodiment and change in the thought without prejudice to the present invention and scope.
Therefore, the scope of the present invention, should be subject to listed claim.
Claims (7)
- A kind of 1. method for improving integral extruding type honeycomb catalyst mechanical strength, it is characterised in that be as follows：Step 1：By Ludox（20~40wt%）, Aluminum sol（10~30wt%）, plasticizer, tung oil and kaolin is sufficiently stirred into For sticky white slurries；Step 2：Methylcellulose is added to the white slurries obtained in step 1, it is not flowable to stir formation in several minutes Body of paste；Step 3：Catalyst fines, sesbania powder, cellulose, glass fibre are added in kneader be stirred it is uniformly mixed, Obtain mixed powder；Step 4：The white body of paste obtained in step 2 is added in the mixed powder obtained in step 3, is sufficiently stirred Obtain wet feed group；Step 5：Wet feed is rolled into a ball using descaling extrusion press and carries out extrusion molding, extrusion pressure control is in 15 ~ 25MPa, using microwave Processing is dried in heat-shaping, a length of 1 ~ 5min during sizing in an oven, and drying condition is 50 ~ 110 DEG C of dry 1 ~ 12h；Step 6：Carrier enhancing coating is coated on honeycomb catalyst skin-surface, is coated 2 ~ 5 times, and dry, calcining；Carrier The coating of enhancement solution can coat in step 5 after extrusion molding, coat after microwave sizing can be also completed in step 5, also may be used By the coating of carrier enhancement solution and honeycomb catalyst skin-surface during extrusion molding.
- 2. according to a kind of method of improvement integral extruding type honeycomb catalyst mechanical strength described in claim 1, feature It is in the step 1 that it is 0 ~ 20 part to include Ludox and Aluminum sol by the mass fraction of white slurries, plasticizer is 0 ~ 3 Part, 0 ~ 3 part of tung oil, 0 ~ 10 part of kaolin.
- 3. according to a kind of method of improvement integral extruding type honeycomb catalyst mechanical strength described in claim 1, feature Be the mixture that plasticizer in the step 1 is polyethylene glycol, polyethylene oxide or the two, molecular weight for 400 ~ 10000。
- 4. according to a kind of method of improvement integral extruding type honeycomb catalyst mechanical strength described in claim 1, feature It is 0.1 ~ 5wt% that the methylcellulose addition in the step 2 is grind slurries quality.
- 5. according to a kind of method of improvement integral extruding type honeycomb catalyst mechanical strength described in claim 1, feature It is in the step 3 that it is 50 ~ 70 parts to include catalyst fines by the mass fraction of mixed powder, 0 ~ 3 part of sesbania powder, fiber 0 ~ 3 part of element, 0 ~ 10 part of glass fibre.
- 6. according to a kind of method of improvement integral extruding type honeycomb catalyst mechanical strength described in claim 1, feature It is commercially available vanadium series catalyst, Cu zeolite catalysts or Cu/Fe zeolite catalysts to be the catalyst fines in the step 3.
- 7. according to a kind of method of improvement integral extruding type honeycomb catalyst mechanical strength described in claim 1, feature It is that the carrier enhancing coating in the step 6 is the aluminium dihydrogen phosphate slurries for being mixed with glass fibre, wherein biphosphate aluminium paste The content of aluminium dihydrogen phosphate is 40% ~ 70% in liquid, and glass fibre accounts for the 2% ~ 10% of enhancing coating；Calcination condition is 450 ~ 600 DEG C Lower calcining 3 ~ 10 hours.
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| CN113731421A (en) * | 2021-09-29 | 2021-12-03 | 北京工业大学 | Coating process of CO monolithic catalyst and preparation method thereof |
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