CN107442163B - Preparation method of monolithic carrier catalyst containing non-noble metal - Google Patents
Preparation method of monolithic carrier catalyst containing non-noble metal Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052878 cordierite Inorganic materials 0.000 claims description 38
- 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 claims description 38
- 239000000919 ceramic Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002808 molecular sieve Substances 0.000 claims description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 11
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 10
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 10
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 10
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 21
- 238000000576 coating method Methods 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 abstract description 8
- 238000011068 loading method Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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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
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—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
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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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
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/763—CHA-type, e.g. Chabazite, LZ-218
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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
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- 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)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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Abstract
The invention relates to a preparation method of an integral carrier catalyst containing non-noble metal, which is characterized in that the integral carrier catalyst containing non-noble metal prepared by the invention has the advantages of uniform active component loading, high firmness of combination of a coating and a carrier and simple preparation process; the engine bench test result shows that the NOx conversion rate under the B50 working condition reaches 97 percent; meanwhile, the invention adopts a non-noble metal system, so the preparation cost is low.
Description
Technical Field
The invention relates to a preparation method of an integral carrier catalyst containing non-noble metal, belonging to the technical field of automobile emission.
Background
To meet the emission regulations, the Urea-SCR technology has become the first choice for reducing NO in medium and heavy diesel engine enterprisesxThe technical route is based on the principle that ammonia gas generated by urea hydrolysis and NO in automobile exhaustxWhen passing through a support coated with an active coating, NOxIs rapidly reduced into nitrogen and water, ammonia and NO by ammoniaxCan carry out rapid chemical reaction on the post-processing carrier and is inseparable with the composition of the carrier. The carrier with active coating is composed of carrier and catalyst, the carrier firstly bears coating and active component, and secondly provides properThe catalytic reaction channel is not supported by a carrier, the catalyst powder cannot exert the performance of the catalytic reaction channel, and the cordierite carrier has excellent performance in the field of automobile exhaust denitration due to the large surface area, high pore density, thin pore wall, low thermal expansion coefficient, good thermal shock resistance and the like. The catalyst is used as a main active component for denitration and can only be loaded on a carrier to play a role, so that the research on how to organically combine the catalyst and the carrier to achieve the best denitration effect is a hotspot of the current research.
The invention discloses CN 201210485579.6, which relates to a method for coating a Ti-based denitration catalyst on honeycomb ceramics, and the method comprises the steps of taking Ti-based denitration catalyst slurry with a certain solid content, adjusting the pH value of the slurry to 7-10, immersing the honeycomb ceramics into the slurry, coating the catalyst on the honeycomb ceramics by adopting an ultrasonic dipping method or a vacuum coating method, and then drying and roasting to obtain the coating type honeycomb ceramic-based denitration catalyst.
The invention patent CN 200710188005.1 discloses a SCR denitration catalyst and a preparation method thereof, firstly preparing alumina sol and then preparing Al2O3-SiO2-TiO2Coating a carrier, preparing mixed active components of lanthanum nitrate, ammonium metavanadate and ammonium paratungstate, dipping the carrier in the active components, and finally drying and calcining.
The invention patent CN 201410643551.X discloses a preparation method of a honeycomb carrier catalyst for molecular sieve denitration, which comprises the steps of preparing a Cu/ZSM5 catalyst with a certain content in advance by adopting an ion exchange method, then pretreating and drying a cordierite honeycomb ceramic carrier under the conditions of acid, alkali and an organic solvent to prepare a slurry containing Cu/ZSM5, ethylene glycol and deionized water, finally putting the pretreated carrier into the slurry containing Cu/ZSM5, ethylene glycol and deionized water for treatment, drying and calcining to prepare a primary-coated honeycomb ceramic denitration catalyst, and then coating the denitration catalyst for the second time.
The preparation method for preparing the denitration catalyst has the following problems: (1) the active component loading rate is low; (2) the active components of the catalyst on the surface of the carrier are unevenly coated, and are locally enriched or the coating amount is too small; (3) the firmness of the combination of the active component coating and the carrier is low, and the coating is easy to fall off; (4) the preparation process is complicated.
Disclosure of Invention
The invention aims to provide a preparation method of a non-noble metal-containing monolithic carrier catalyst, the prepared monolithic carrier catalyst has the advantages of uniform active component loading, high firmness of combination of a coating and a carrier, simple preparation process, and engine bench test results show that NO is contained under the working condition of B50xThe conversion rate reaches 97 percent; meanwhile, the non-noble metal system adopted by the invention has low preparation cost.
The technical scheme of the invention is realized as follows: the preparation method of the non-noble metal-containing monolithic carrier catalyst is characterized by comprising the following specific steps of: (1) pretreating a cordierite ceramic carrier: soaking the carrier in 2-3.8 wt% ammonia water at room temperature for 20-60 min, taking out the cordierite ceramic carrier, repeatedly washing with deionized water until the pH value is neutral, drying, and calcining at 500 deg.C for 2-4 h; (2) preparing a mixed solution containing non-noble metal active components: a. dissolving 6.0-8.5 parts of copper salt and 1.1-3.1 parts of metal auxiliary agent in deionized water, and stirring for dissolving; b. adding 14.9-21.6 parts of molecular sieve carrier, and mixing and stirring for 2-4 h; c. adding 0.20-0.33 part of ammonium carbamate, and stirring for 1-3 hours at 45-60 ℃; d. adding 9.3-15.2 parts of binder until uniformly stirring to obtain a mixed solution containing non-noble metal active components; (3) cordierite carrier activation: and (2) placing the treated cordierite ceramic carrier in a prepared mixed solution containing non-noble metal active components, carrying out ultrasonic treatment for 5-10 min, taking out the cordierite ceramic carrier, blowing away surface residual liquid by using purge gas, placing the cordierite ceramic carrier in an oven for drying at 80-105 ℃, and finally calcining at 430-550 ℃ for 2-4 h to obtain the monolithic carrier catalyst containing non-noble metal.
The metal auxiliary agent in the non-noble metal active component mixed solution is one or more of La, Co, Mn and Ce salt.
The binder in the non-noble metal active component mixed solution is a mixture of silica sol, aluminum sol and sodium carboxymethylcellulose, wherein the silica sol accounts for 3.1-7.2 parts, the aluminum sol accounts for 2.3-5.1 parts, and the sodium carboxymethylcellulose accounts for 2.6-8.5 parts (mass fraction 1%).
The method has the advantages that the solution with copper ions and transition metal ions reacts with the molecular sieve, so that part of metal ions enter the pore canal of the molecular sieve, and finally the molecular sieve and more active metal components generate chemical action under the action of ammonium carbamate at a certain temperature, thereby realizing high-efficiency loading; and adding a binder system containing high-temperature silica sol, high-temperature alumina sol and carboxymethyl cellulose, fully stirring to highly disperse the active component and the binder into uniform mixed liquid, finally soaking the carrier which is obtained by pretreatment and has certain surface roughness into the mixed liquid containing the active component and the binder, and drying and calcining to obtain the non-noble metal-containing integral carrier catalyst. The monolithic carrier catalyst prepared by the invention adopts the molecular sieve with large specific surface and good thermal stability, on one hand, the molecular sieve and the active component generate chemical action to ensure that the loading efficiency of the active metal ions is high, and on the other hand, ammonia gas and NO are usedxThe reaction provides a reaction and diffusion channel, and solves NOXThe problem of low conversion rate; the monolithic carrier catalyst is prepared by calcining the active component, the binder and the pretreated carrier in one step, so that the problems of uneven coating of the active component of the surface catalyst, local enrichment or too small coating amount are effectively solved; the silica sol and the alumina sol have better high temperature resistance, so that the problems of low bonding firmness of the active component coating and the carrier and easy falling of the coating are effectively solved. The monolithic carrier catalyst is applied to denitration of automobile exhaust of a mobile source.
Drawings
FIG. 1 is a schematic view of the assembly of a vibration test bed for the determination of the shedding rate of a catalyst containing a non-noble metal on a monolithic support.
Detailed Description
In the following description of specific examples, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details.
Example 1
(1) Cordierite ceramic carrier pretreatment
Soaking the cordierite ceramic carrier in ammonia water with the mass fraction of 2% at room temperature, taking out after 60min, repeatedly washing with deionized water until the pH value of the solution after washing shows neutrality, drying at 105 ℃, and calcining at 500 ℃ for 4 h.
(2) Preparation of mixed liquor containing non-noble metal active component
a. 660g of copper nitrate and 178.6g of cerium nitrate are weighed and dissolved in 4720g of deionized water; b. adding 1200g of ZSM5 molecular sieve powder, and stirring for 2 h; c. adding 23.4g of ammonium carbamate, and stirring at 60 ℃ for 1 h; 500g of silica Sol (SiO) was added2Content 40%), 250g of alumina sol (Al)2O340 percent of the content), 200g of sodium carboxymethylcellulose with the mass fraction of 1 percent, and uniformly stirring to obtain a mixed solution.
(3) Cordierite carrier activation
And (3) placing the cordierite carrier obtained after pretreatment in the step (1) into the mixed solution containing the non-noble metal active component prepared in the step (2), carrying out ultrasonic treatment for 5min, taking out the carrier, blowing away the surface residual solution by using compressed air, placing the carrier in an oven for drying at 80 ℃, and calcining at 430 ℃ for 4h to obtain the monolithic carrier catalyst containing the non-noble metal.
The monolithic supported catalyst prepared in example 1 was subjected to a coating peeling test, and the monolithic supported catalyst containing a non-noble metal was first weighed and then mounted on a vibration test stand, as shown in fig. 1. The vibration acceleration of 10g, the vibration frequency of (100 +/-5) Hz and the test time of 5h are adopted, the carrier catalyst is taken down after the experiment is finished, the mass of the carrier catalyst is weighed, and the coating falling rate is calculated to be 2.9 percent, which shows that the firmness of the combination of the active component coating and the carrier is high, and the problem that the coating is easy to fall off is solved.
The monolithic supported catalyst prepared in example 1 was subjected to an engine bench test, and the experimental conditions and test results are shown in table 1:
TABLE 1
It can be seen that NO is present under the B50 operating conditionxThe conversion rate is 97 percent at most, and NO is generated under the C25 working conditionxThe lowest conversion rate is 88 percent, and NO is in other working conditionsxThe conversion rate can reach more than 90 percent, and shows good NOxAnd (4) activity.
Example 2
(1) Cordierite ceramic carrier pretreatment
Soaking the cordierite ceramic carrier in 3.8% ammonia water at room temperature, taking out after 20min, repeatedly washing with deionized water until pH of the solution shows neutrality, drying at 95 deg.C, and calcining at 500 deg.C for 2 h.
(2) Preparation of mixed liquor containing non-noble metal active component
a. Weighing 600g of copper nitrate and 120g of lanthanum nitrate, and dissolving in 5200g of deionized water; b. adding 1200g of Sapo34 molecular sieve powder, and stirring for 4 hours; c. adding 19.6g of ammonium carbamate, and stirring at 45 ℃ for 3 hours; 300g of silica Sol (SiO) was added2Content 40%), 300g of alumina sol (Al)2O340 percent of the content), 300g of sodium carboxymethylcellulose with the mass fraction of 1 percent, and uniformly stirring to obtain a mixed solution.
(3) Cordierite carrier activation
And (3) placing the cordierite carrier obtained after pretreatment in the step (1) into the mixed solution containing the non-noble metal active component prepared in the step (2), carrying out ultrasonic treatment for 10min, taking out the carrier, blowing away the surface residual solution by using compressed air, placing the carrier in an oven for drying at 105 ℃, and calcining at 550 ℃ for 2h to obtain the monolithic carrier catalyst containing the non-noble metal.
Example 3
(1) Cordierite ceramic carrier pretreatment
Soaking the cordierite ceramic carrier in ammonia water with the mass fraction of 3% at room temperature, taking out after 30min, repeatedly washing with deionized water until the pH value of the solution after washing shows neutrality, drying at 100 ℃, and calcining at 500 ℃ for 2 h.
(2) Preparation of mixed liquor containing non-noble metal active component
a. 480g of copper nitrate and 85.3g of manganese nitrate are weighed and dissolved in 5500g of deionized water; b. adding 1200g of beta40 molecular sieve powder, and stirring for 2 h; c. 14.5g of ammonium carbamate are added and stirred at 60 ℃ 2h; 250g of silica Sol (SiO) was added240% content), 220g of alumina sol (Al)2O340 percent of the content), 300g of sodium carboxymethylcellulose with the mass fraction of 1 percent, and uniformly stirring to obtain a mixed solution.
(3) Cordierite carrier activation
And (3) placing the cordierite carrier obtained after pretreatment in the step (1) into the mixed liquid containing the non-noble metal active component prepared in the step (2), carrying out ultrasonic treatment for 8min, taking out the carrier, blowing away the surface residual liquid by using compressed air, placing the carrier in an oven for drying at 100 ℃, and calcining at 450 ℃ for 2h to obtain the monolithic carrier catalyst containing the non-noble metal.
Example 4
(1) Cordierite ceramic carrier pretreatment
Soaking the cordierite ceramic carrier in ammonia water with the mass fraction of 3% at room temperature, taking out after 30min, repeatedly washing with deionized water until the pH value of the solution after washing shows neutrality, drying at 105 ℃, and calcining at 500 ℃ for 4 h.
(2) Preparation of mixed liquor containing non-noble metal active component
a. Weighing 360g of copper nitrate and 150g of cobalt nitrate, and dissolving in 3000g of deionized water; b. adding 1200g of SSZ-13 molecular sieve powder, and stirring for 2 h; c. adding 13.9g of ammonium carbamate, and stirring at 60 ℃ for 1 h; 400g of silica Sol (SiO) was added2Content 40%), 250g of alumina sol (Al)2O340 percent of the content), 180g of sodium carboxymethylcellulose with the mass fraction of 1 percent, and uniformly stirring to obtain a mixed solution.
(3) Cordierite carrier activation
And (3) placing the cordierite carrier obtained after pretreatment in the step (1) into the mixed solution containing the non-noble metal active component prepared in the step (2), carrying out ultrasonic treatment for 5min, taking out the carrier, blowing away the surface residual solution by using compressed air, placing the carrier in an oven for drying at 90 ℃, and calcining at 450 ℃ for 2h to obtain the monolithic carrier catalyst containing the non-noble metal.
Example 5
(1) Cordierite ceramic carrier pretreatment
Soaking the cordierite ceramic carrier in ammonia water with the mass fraction of 2% at room temperature, taking out after 40min, repeatedly washing with deionized water until the pH value of the solution after washing shows neutrality, drying at 105 ℃, and calcining at 500 ℃ for 4 h.
(2) Preparation of mixed liquor containing non-noble metal active component
a. Weighing 620g of copper nitrate, 60g of cerium nitrate, 50g of lanthanum nitrate, 50g of cobalt nitrate and 50g of manganese nitrate, and dissolving in 4800g of deionized water; b. adding 1200g of beta25 molecular sieve powder, and stirring for 2 h; c. adding 24.2g of ammonium carbamate, and stirring at 60 ℃ for 2 hours; 600g of silica Sol (SiO) were added240% content), 420g of alumina sol (Al)2O340 percent of the content), 430g of sodium carboxymethylcellulose with the mass fraction of 1 percent, and uniformly stirring to obtain a mixed solution.
(3) Cordierite carrier activation
And (3) placing the cordierite carrier obtained after pretreatment in the step (1) into the mixed solution containing the non-noble metal active component prepared in the step (2), carrying out ultrasonic treatment for 5min, taking out the carrier, blowing away the surface residual solution by using compressed air, placing the carrier in an oven for drying at 80 ℃, and calcining at 430 ℃ for 2h to obtain the monolithic carrier catalyst containing the non-noble metal.
Example 6
(1) Cordierite ceramic carrier pretreatment
Soaking the cordierite ceramic carrier in ammonia water with the mass fraction of 2% at room temperature, taking out after 30min, repeatedly washing with deionized water until the pH value of the solution after washing shows neutrality, drying at 105 ℃, and calcining at 500 ℃ for 4 h.
(2) Preparation of mixed liquor containing non-noble metal active component
a. Weighing 540g of copper nitrate, 120g of cerium nitrate and 80g of lanthanum nitrate, and dissolving in 3500g of deionized water; b. adding 1200g of ZSM5 molecular sieve powder, and stirring for 2 h; c. adding 21.3g of ammonium carbamate, and stirring at 60 ℃ for 1 h; 280g of silica Sol (SiO) was added2Content 40%), 150g of alumina sol (Al)2O340 percent of the content), 550g of sodium carboxymethylcellulose with the mass fraction of 1 percent, and uniformly stirring to obtain a mixed solution.
(3) Cordierite carrier activation
And (3) placing the cordierite carrier obtained after pretreatment in the step (1) into the mixed solution containing the non-noble metal active component prepared in the step (2), carrying out ultrasonic treatment for 5min, taking out the carrier, blowing away the surface residual solution by using compressed air, placing the carrier in an oven for drying at 105 ℃, and calcining at 450 ℃ for 2h to obtain the monolithic carrier catalyst containing the non-noble metal.
Claims (1)
1. The preparation method of the non-noble metal-containing monolithic carrier catalyst is characterized by comprising the following specific steps of: (1) pretreating a cordierite ceramic carrier: soaking the carrier in 2-3.8 wt% ammonia water at room temperature for 20-60 min, taking out the cordierite ceramic carrier, repeatedly washing with deionized water until the pH value is neutral, drying, and calcining at 500 deg.C for 2-4 h; (2) preparing a mixed solution containing non-noble metal active components: a. dissolving 6.0-8.5 parts of copper salt and 1.1-3.1 parts of metal auxiliary agent in deionized water, and stirring for dissolving; b. adding 14.9-21.6 parts of molecular sieve carrier, and mixing and stirring for 2-4 h; c. adding 0.20-0.33 part of ammonium carbamate, and stirring for 1-3 hours at 45-60 ℃; c. adding 9.3-15.2 parts of binder until uniformly stirring to obtain a mixed solution containing non-noble metal active components; (3) cordierite carrier activation: placing the treated cordierite ceramic carrier in a prepared mixed solution containing non-noble metal active components, performing ultrasonic treatment for 5-10 min, taking out the cordierite ceramic carrier, blowing away surface residual liquid by using purge gas, placing the cordierite ceramic carrier in an oven for drying at 80-105 ℃, and finally calcining at 430-550 ℃ for 2-4 h to obtain an integral carrier catalyst containing non-noble metal; the metal auxiliary agent in the non-noble metal active component mixed solution is one or more of La, Co, Mn and Ce salt; the binder in the non-noble metal active component mixed solution is a mixture of silica sol, aluminum sol and sodium carboxymethylcellulose, wherein the silica sol accounts for 3.1-7.2 parts, the aluminum sol accounts for 2.3-5.1 parts, and the sodium carboxymethylcellulose accounts for 2.6-8.5 parts with the mass fraction of 1%.
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| CN104353485A (en) * | 2014-11-06 | 2015-02-18 | 清华大学 | Preparation method of honeycomb carrier catalyst for molecular sieve denitration |
| CN105396610A (en) * | 2015-11-06 | 2016-03-16 | 中国第一汽车股份有限公司 | Composite copper-based molecular sieve catalyst and preparation method thereof |
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| CN104353485A (en) * | 2014-11-06 | 2015-02-18 | 清华大学 | Preparation method of honeycomb carrier catalyst for molecular sieve denitration |
| CN105396610A (en) * | 2015-11-06 | 2016-03-16 | 中国第一汽车股份有限公司 | Composite copper-based molecular sieve catalyst and preparation method thereof |
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