CN105503233B - A kind of big-size thinning plastic cordierite honeycomb ceramic carrier pug and preparation method thereof - Google Patents

A kind of big-size thinning plastic cordierite honeycomb ceramic carrier pug and preparation method thereof Download PDF

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CN105503233B
CN105503233B CN201510926162.2A CN201510926162A CN105503233B CN 105503233 B CN105503233 B CN 105503233B CN 201510926162 A CN201510926162 A CN 201510926162A CN 105503233 B CN105503233 B CN 105503233B
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pug
raw material
coupling agent
silane coupling
inorganic raw
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CN105503233A (en
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黄妃慧
刘洪月
潘吉庆
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Chongqing Aofu Fine Ceramics Co Ltd
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • C04B35/195—Alkaline earth aluminosilicates, e.g. cordierite or anorthite
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C04B2235/322—Transition aluminas, e.g. delta or gamma aluminas
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite

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Abstract

The invention discloses a kind of big-size thinning plastic cordierite honeycomb ceramic carrier pug, including inorganic raw material, organic binder, water and silane coupling agent, inorganic raw material is made of foliated talc, sheet water-washed kaoline, tabular alumina, electroquartz.It carries out surface with inorganic raw material to foliated talc, sheet water-washed kaoline, tabular alumina, electroquartz etc. in pug preparation process using silane coupling agent to be modified, silane coupling agent forms substituent group-OSi (CH on raw material surface3)2, make inorganic material that there is hydrophobicity.With the big specification cordierite honeycomb ceramic carrier pug of the modified inorganic raw material preparation in surface, aquation film thickness is small, dry contraction is small, can effectively reduce thermal expansion coefficient；The preferable mobility of pug, keeps briquetting pressure low, can effectively reduce the degree of wear of molding equipment and mold, meanwhile, surface substituent group-OSi (CH3)2, blank strength can be improved in carrier inside formation-O-Si-O-Si- three-dimensional network, reduce firing cracking, higher sintering qualified rate can be obtained.

Description

A kind of big-size thinning plastic cordierite honeycomb ceramic carrier pug and preparation method thereof
Technical field
The present invention relates to a kind of big-size thinning plastic cordierite honeycomb ceramic carrier pugs and preparation method thereof.
Background technique
The big specification CORDIERITE HONEYCOMB CERAMIC CARRIER of diameter >=10.5in. is after medium-and-large-sized internal combustion engine gaseous contamination discharges The catalyst carrier of processing technique, such as: diesel engine selective catalytic reduction SCR carrier, clean fuel internal combustion engine three-effect catalysis turn Change device TWC carrier, oxidation catalytic converter DOC carrier and the escaping of ammonia converter ASC carrier etc..State V, VI emission regulation are to machine The quick severization of the lower emission limit of motor vehicle exhaust pollutant and motor vehicle economy regulation, it is desirable that honeycomb must be made pottery Ceramic carrier wall thickness is reduced to 5mil hereinafter, to obtain bigger catalyst-coated surface product and lower flow resistance.
The production technology of carrier for ceramic honeycomb catalyst includes: that powder composition and preparation, additive technology, pug are mixed Sweetening process, extrusion equipment and technique, drying process and firing process etc., each process procedure will affect product quality, shape At multifactor, multilevel orthogonal test research process.The big specification honeycomb ceramic carrier preparation process of traditional wall thickness >=7mil Larger with high-performance thin wall honeycomb ceramic carrier manufacturing process gap, wherein pug preparation is to influence honeycomb ceramic carrier into moral character It can be with the fundamental technology link of molding die service life.
The cordierite honeycomb ceramic carrier manufacture of extrusion molding mostly uses common inorganic raw material, and pug preparation only considers raw material Chemical component, granularity, crystal morphology feature, production wall thickness >=7mil conventional wall thickness big specification honeycomb ceramic carrier can expire Sufficient performance indicator requirement.In pug preparation process, the crushing of inorganic raw material makes raw material surface form a large amount of scission of links, and powder granule is easy To reunite, crystal form when influencing the uniformity of powder preparation, directly destruction cordierite synthesis is regularly arranged, meanwhile, scission of link adsorbed More water ions form the biggish hydration shell of thickness (see Fig. 1), the microcosmic lubricity between powder particles are not only made to be deteriorated, and increase Moulding process extruder pressure, reduces the service life of molding equipment and mold, and higher pure water additional amount also makes dry receipts Shrinkage increases, and the problems such as deformation of grid duct, season cracking occurs.Based on this, the invention proposes a kind of manufacture high-performance is big The pug preparation method of gauge thin wall cordierite honeycomb ceramic carrier.
Summary of the invention
For conventional preparation techniques production big-size thinning plastic cordierite honeycomb ceramic carrier pug, that there are amount of water is big, dry It is difficult, dry to shrink big, easy season cracking and pug poor fluidity, the problems such as resistance is big, and equipment die is easily damaged is squeezed out, The present invention provides a kind of big-size thinning plastic cordierite honeycomb ceramic carrier pug, including inorganic raw material, organic binder, water And silane coupling agent, inorganic raw material are made of foliated talc, sheet water-washed kaoline, tabular alumina, electroquartz.
It include as follows the present invention also provides a kind of preparation method of big-size thinning plastic cordierite honeycomb ceramic carrier pug Step:
Prepare the mixed-powder of inorganic raw material and silane coupling agent；Organic binder and water are added into mixed-powder；It pinches It closes, mud refining.
The present invention also provides a kind of preparation methods of big-size thinning plastic cordierite carrier for ceramic honeycomb catalyst, including will be upper The pug that the method for stating is prepared is extruded into green compact, fires, and heat preservation obtains catalyst carrier.
As optimal technical scheme, the general formula of silane coupling agent are as follows: Y-R-Si-X3, in which: R is selected from alkyl or aryl；X Selected from methoxyl group, ethyoxyl or chlorine atom, Y is organic reaction base.Further preferably, organic reaction base is selected from vinyl, epoxy Base, amino or sulfydryl etc..Alkyl includes but is not limited to C1-C5Alkyl, for example, methyl, ethyl, n-propyl, isopropyl, positive fourth Base, isobutyl group etc..Aryl includes but is not limited to C1-C18Aryl.
As optimal technical scheme, organic additive includes methylcellulose, organic silicon polyether copolymer and soya-bean oil.
As optimal technical scheme, organic binder additional amount is the 2-10% of inorganic raw material total weight；
As optimal technical scheme, silane coupling agent additional amount is the 0.01-10% of inorganic raw material total weight；It is further excellent Choosing, silane coupling agent is the 0.05-8% of inorganic raw material total weight；It is further preferred that silane coupling agent accounts for inorganic raw material total weight 0.1-1%；
As optimal technical scheme, the pressure that extrudes of pug is 9-14MPa.
Big-size thinning plastic cordierite honeycomb ceramic carrier of the invention refers to diameter>=10.5in, wall thickness wall thickness<7mil Ceramic monolith.
The invention has the benefit that
Using silane coupling agent to foliated talc, sheet water-washed kaoline, tabular alumina, electricity in pug preparation process Fused quartz etc. carries out surface with inorganic raw material and is modified, and silane coupling agent forms substituent group-OSi (CH on raw material surface3)2, make nothing Machine material has hydrophobicity.With the big specification cordierite honeycomb ceramic carrier pug of the modified inorganic raw material preparation in surface, water Change film thickness is small, dry contraction is small, can effectively reduce thermal expansion coefficient；The preferable mobility of pug, keeps briquetting pressure low, can have Effect reduces the degree of wear of molding equipment and mold, meanwhile, surface substituent group-OSi (CH3)2, can be in carrier inside formation-O- Si-O-Si- three-dimensional network improves blank strength, reduces firing cracking, higher sintering qualified rate (95-99%) can be obtained.
Detailed description of the invention
Fig. 1: silane coupler modified inorganic particle schematic diagram
Fig. 2: the cordierite carrier for ceramic honeycomb catalyst of embodiment 4 aligns microgram
Specific embodiment
Embodiment 1:
(1) inorganic material powder constitute: D50=15 μm of foliated talc 40.0%, D50=6 μm of life kaolin 29.8%, D50=20 μm of tabular alumina 21.2%, D50=4.0 μm of electroquartz 9.0%.Inorganic particle through it is agravic it is dry-mixed after, 4% methylcellulose, 0.5% machine silicon copolyether, 1% soya-bean oil and 35% water are added, kneading and vacuum are carried out Pug is extruded into 300 holes/in2 of 13 × 6in. of Φ, the thin-walled bee of wall thickness 5mil with the pressure of 19.0MPa by pugging, molding machine Nest ceramic catalyst carrier green compact, are tested after drying, green compact shrinking percentage: 3.5%, axial compression strength: 0.52MPa, curved muscle With thick muscle ratio of defects: 4.5%.
(2) it is fired through 1415 DEG C, keeps the temperature 8 hours, obtain cordierite catalyst carrier, sintering qualified rate 90.1%.Product Performance: 1.0 × 10-6/ DEG C of thermal expansion coefficient (- 800 DEG C of room temperature), water absorption rate 33%, axial compression strength 16.7MPa, 650 DEG C Thermal shock test is without cracking three times.
Embodiment 2:
(1) inorganic material powder is constituted: D50=15 μm of foliated talc 40.0%, D50=6 μm of life kaolin 29.8%, D50=20 μm of tabular alumina 21.2%, D50=4.0 μm of electroquartz 9.0%.Additional 0.2% KH550 Silane coupling agent progress synchronous with powder is agravic dry-mixed, to powder-modified.
(2) 5% methylcellulose, 0.5% machine silicon copolyether, 1% soya-bean oil and 25% water are added, is carried out It mediates and vacuum pugging, molding machine is extruded into pug with the pressure of 13.8MPa 300 holes/in2, the wall thickness of 13 × 6in. of Φ The thin wall honeycomb ceramic catalyst support greenware of 5mil, is tested after drying, dry to shrink: 3.1%, axial compression strength: 1.10MPa, curved muscle, thick muscle ratio of defects: 3.0%.
(3) it is fired through 1415 DEG C, keeps the temperature 8 hours, obtain cordierite catalyst carrier, sintering qualified rate 95.5%, product Performance: 0.92 × 10-6/ DEG C of thermal expansion coefficient (- 800 DEG C of room temperature), water absorption rate 31.2%, axial compression strength 17.5MPa, 650 Thermal shock test is without cracking DEG C three times.
Embodiment 3:
(1) inorganic material powder is constituted: D50=15 μm of foliated talc 40.0%, D50=6 μm of life kaolin 29.8%, D50=20 μm of tabular alumina 21.2%, D50=4.0 μm of electroquartz 9.0%.Additional 0.4% KH550 Silane coupling agent progress synchronous with powder is agravic dry-mixed, to powder-modified.
(2) 5% methylcellulose, 0.5% machine silicon copolyether, 1% soya-bean oil and 25% water are added, is carried out It mediates and vacuum pugging, molding machine is extruded into pug with the pressure of 11.9MPa 300 holes/in2, the wall thickness of 13 × 6in. of Φ The thin wall honeycomb ceramic catalyst support greenware of 5mil, is tested after drying, dry to shrink: 2.9%, axial compression strength: 1.32MPa, curved muscle, thick muscle ratio of defects: 2.2%.
(3) it is fired through 1415 DEG C, keeps the temperature 8 hours, obtain cordierite catalyst carrier, sintering qualified rate 97.2%, product Performance: 0.86 × 10-6/ DEG C of thermal expansion coefficient (- 800 DEG C of room temperature), water absorption rate 30.2%, axial compression strength 18.3MPa, 650 Thermal shock test is without cracking DEG C three times.
Embodiment 4:
(1) inorganic material powder is constituted: D50=15 μm of foliated talc 40.0%, D50=6 μm of life kaolin 29.8%, D50=20 μm of tabular alumina 21.2%, D50=4.0 μm of electroquartz 9.0%.Additional 0.8% KH550 Silane coupling agent progress synchronous with powder is agravic dry-mixed, to powder-modified.
(2) 5% methylcellulose, 0.5% machine silicon copolyether, 1% soya-bean oil and 25% water are added, is carried out It mediates and vacuum pugging, molding machine is extruded into pug with the pressure of 9.1MPa 300 holes/in2, the wall thickness of 13 × 6in. of Φ The thin wall honeycomb ceramic catalyst support greenware of 5mil, is tested after drying, dry to shrink: 2.5%, axial compression strength: 1.83MPa, curved muscle, thick muscle ratio of defects: 0.5%.
(3) it is fired through 1415 DEG C, keeps the temperature 8 hours, obtain cordierite catalyst carrier, sintering qualified rate 99.0%, institute The performance of the cordierite honeycomb ceramic carrier obtained are as follows: 0.75 × 10-6/ DEG C of thermal expansion coefficient (- 800 DEG C of room temperature), water absorption rate 28.5%, axial compression strength 20.5MPa, 650 DEG C three times thermal shock test without cracking.
The different pugs of table 1 prepare cordierite carrier and compare
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as At all equivalent modifications or change, should be covered by the claims of the present invention.

Claims (2)

1. a kind of big-size thinning plastic cordierite honeycomb ceramic carrier pug, which is characterized in that the pug includes inorganic raw material, Organic binder, water and silane coupling agent；The inorganic raw material is by foliated talc, sheet water-washed kaoline, tabular alumina It is constituted with electroquartz；
The general formula of the silane coupling agent are as follows: Y-R-Si-X3, in which: R is selected from alkyl or aryl；X is selected from methoxyl group, ethyoxyl Or chlorine atom, Y are organic reaction base；The organic reaction base is selected from vinyl, epoxy group, amino or sulfydryl；
The organic binder includes methylcellulose, organic silicon polyether copolymer and soya-bean oil；
The organic binder additional amount is the 2-10% of inorganic raw material total weight；
The silane coupling agent additional amount is the 0.01-10% of inorganic raw material total weight.
2. the preparation method of big-size thinning plastic cordierite honeycomb ceramic carrier pug as described in claim 1, which is characterized in that Include the following steps: the mixed-powder for preparing inorganic raw material and silane coupling agent；Into mixed-powder be added organic binder and Water；It mediates, mud refining；
The pug being prepared is extruded into green compact, is fired, heat preservation obtains catalyst carrier；
The pressure that extrudes of the pug is 9-14MPa.
CN201510926162.2A 2015-12-14 2015-12-14 A kind of big-size thinning plastic cordierite honeycomb ceramic carrier pug and preparation method thereof Active CN105503233B (en)

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Publication number Priority date Publication date Assignee Title
CN106045451A (en) * 2016-06-03 2016-10-26 昆明理工大学 Sintered-free cordierite honeycomb-ceramic hole plugging material
CN110937916B (en) * 2019-12-09 2022-03-11 江苏省宜兴非金属化工机械厂有限公司 Ceramic carrier with honeycomb structure and preparation method thereof
CN112010661B (en) * 2020-09-03 2022-06-03 广州粤瓷新材料有限公司 Sagger for lithium battery positive electrode material and preparation method thereof
CN116063093B (en) * 2023-01-05 2023-12-26 武汉理工大学 DPF honeycomb ceramic based on flaked kaolin and preparation method thereof
CN117142874A (en) * 2023-11-01 2023-12-01 山东奥福环保科技股份有限公司 Thin-wall silicon carbide honeycomb ceramic carrier and preparation method and application thereof

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CN103467076A (en) * 2013-09-27 2013-12-25 江苏省宜兴非金属化工机械厂有限公司 Method of manufacturing large-size cordierite honeycomb ceramic carriers
CN104030720A (en) * 2014-06-24 2014-09-10 北京奥福(临邑)精细陶瓷有限公司 Zero-firing-shrinkage cordierite honeycomb ceramic carrier and preparation method thereof
CN104402458A (en) * 2014-10-24 2015-03-11 彭红 Thin-walled honeycomb ceramic carrier mud material and preparation method thereof
CN104671741A (en) * 2015-01-14 2015-06-03 江苏蓝烽新材料科技有限公司 Preparation method of large-size honeycomb ceramic carrier for diesel engine

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CN104030720A (en) * 2014-06-24 2014-09-10 北京奥福(临邑)精细陶瓷有限公司 Zero-firing-shrinkage cordierite honeycomb ceramic carrier and preparation method thereof
CN104402458A (en) * 2014-10-24 2015-03-11 彭红 Thin-walled honeycomb ceramic carrier mud material and preparation method thereof
CN104671741A (en) * 2015-01-14 2015-06-03 江苏蓝烽新材料科技有限公司 Preparation method of large-size honeycomb ceramic carrier for diesel engine

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