CN1934056A - Method for producing ceramic porous body and molded body - Google Patents
Method for producing ceramic porous body and molded body Download PDFInfo
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- CN1934056A CN1934056A CN 200580009263 CN200580009263A CN1934056A CN 1934056 A CN1934056 A CN 1934056A CN 200580009263 CN200580009263 CN 200580009263 CN 200580009263 A CN200580009263 A CN 200580009263A CN 1934056 A CN1934056 A CN 1934056A
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- ceramic porous
- silica
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- porous article
- powder
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- 239000000919 ceramic Substances 0.000 title claims abstract description 115
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000002994 raw material Substances 0.000 claims abstract description 67
- 239000000843 powder Substances 0.000 claims abstract description 65
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 140
- 239000011148 porous material Substances 0.000 claims description 65
- 239000000741 silica gel Substances 0.000 claims description 55
- 229910002027 silica gel Inorganic materials 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 48
- 239000002689 soil Substances 0.000 claims description 35
- 238000007493 shaping process Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000002250 absorbent Substances 0.000 claims description 17
- 230000001413 cellular effect Effects 0.000 claims description 16
- 229910021426 porous silicon Inorganic materials 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 12
- 230000033228 biological regulation Effects 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 22
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 238000010304 firing Methods 0.000 abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 239000012778 molding material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 72
- 239000002585 base Substances 0.000 description 37
- 239000011800 void material Substances 0.000 description 35
- 229910052878 cordierite Inorganic materials 0.000 description 24
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 24
- 230000000694 effects Effects 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000001125 extrusion Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 9
- 238000007906 compression Methods 0.000 description 8
- 230000006835 compression Effects 0.000 description 8
- 239000000796 flavoring agent Substances 0.000 description 8
- 235000019634 flavors Nutrition 0.000 description 8
- 239000005995 Aluminium silicate Substances 0.000 description 7
- 235000012211 aluminium silicate Nutrition 0.000 description 7
- 230000002950 deficient Effects 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 239000000454 talc Substances 0.000 description 7
- 235000012222 talc Nutrition 0.000 description 7
- 229910052623 talc Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000000391 magnesium silicate Substances 0.000 description 4
- 229910052919 magnesium silicate Inorganic materials 0.000 description 4
- 235000019792 magnesium silicate Nutrition 0.000 description 4
- 229920000609 methyl cellulose Polymers 0.000 description 4
- 239000001923 methylcellulose Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- -1 shaping assistant Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002276 dielectric drying Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052634 enstatite Inorganic materials 0.000 description 1
- 238000009778 extrusion testing Methods 0.000 description 1
- 229910052840 fayalite Inorganic materials 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010333 wet classification Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Filtering Materials (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention provides a ceramic porous body containing at least Si as a chemical component, which is obtained by adding porous silica powder or powder of a porous silica-containing compound to a molding material to prepare a raw material, molding the obtained ceramic raw material into a predetermined shape, and then firing the molded ceramic raw material. The ceramic porous body of the present invention does not generate carbon dioxide and harmful gas during firing by using the porous silica powder or the powder of the porous silica-containing compound as the pore-forming agent during production, and the firing time is shorter than that in the case of using the conventional resin powder or carbon powder as the pore-forming agent. Further, the pore-forming characteristics are not easily changed or the molded article is not easily deformed during molding.
Description
Technical field
The present invention relates to be used for the ceramic porous article of strainer and support of the catalyst etc., relate in more detail and can prevent to produce obnoxious flavour during fabrication and be difficult for causing the variation of pore-creating characteristic and the ceramic porous article of the distortion of formed body.
Background technology
Ceramic porous article is usually used in strainer and support of the catalyst etc., for example is used for the reforming apparatus of waste gas purification apparatus, liquid fuel or the geseous fuel of combustion units such as hot machines such as oil engine or boiler, water purification treatment unit etc. up and down.This ceramic porous article can further add tackiness agent, shaping assistant, water etc. and mix by add pore-forming material in ceramic powder usually, be shaped to the regulation shape after, through burning till and obtaining.Pore-forming material is in order to increase the pore in the ceramic porous article, the size of control pore and amount and use.
In the past, as the pore-forming material that in the manufacturing of ceramic porous article, uses, generally use toner or the carbon dust that when burning till, can be burnt, but these materials are because combustiblecomponents is more, so have the lengthening firing time or produce problems such as carbonic acid gas or obnoxious flavour when burning till.
For fear of these problems, also the someone attempted the water swelling particle of hollow resin particles such as foamex or crosslinking Treatment starch etc. is used for the method (for example with reference to patent documentation 1,2) of pore-forming material, but when using the hollow resin particle, its particle mix, damaged easily when the degassing or moulding, the pore-creating characteristic will be easy to deviate from desired characteristics.Especially be the hard formed body of purpose manufacturing with one-body molded, when perhaps using continuous forming machine to make formed body, the hollow resin particles such as foamex of physical strength shortcoming are damaged easily, are difficult to obtain the ceramic porous article of high porosity.In addition, when making water swelling particle, though there is not the problem of this particle breakage, owing to combustiblecomponents can not be controlled to be zero, so although some differences are arranged, but have the identical problem of situation with above-mentioned use carbon dust etc.
Patent documentation 1: the spy opens the 2002-326879 communique
Patent documentation 2: the spy opens the 2003-238271 communique
Summary of the invention
The present invention carries out in view of the problem that exists in the above-mentioned conventional art, purpose provides can avoid firing time lengthening that the combustiblecomponents because of pore-forming material causes or the phenomenon that produces obnoxious flavour during fabrication, and is difficult for causing the ceramic porous article of the distortion of the variation of pore-creating characteristic and formed body.
In order to achieve the above object, the invention provides a kind of ceramic porous article (first ceramic porous article), this ceramic porous article contains Si at least as chemical ingredients, be to make base soil by the powder that in shaping raw material, adds cellular silica powder or porous silicon-containing petrochemical industry compound, after the ceramic base earth forming that obtains is the regulation shape, obtain through burning till.
In addition, the invention provides a kind of ceramic porous article (second ceramic porous article), this ceramic porous article contains Si at least as chemical ingredients, is by add 50% particle diameter (D in shaping raw material
50) be that the saccharoid of the silica gel (silica gel) of 10～100 μ m is made base soil, the ceramic base earth forming that obtains is the regulation shape after, obtain through burning till.
And then, the invention provides a kind of manufacture method (manufacture method of first formed body) of formed body, be by burning till the manufacture method of the formed body that forms ceramic porous article, in shaping raw material, add the saccharoid of silica gel or the saccharoid and the water-absorbent polymer particles of silica gel, make base soil, use gained pottery base soil by one-body molded manufacturing formed body.
Moreover, the invention provides a kind of manufacture method (manufacture method of second formed body) of formed body, be by burning till the manufacture method of the formed body that forms ceramic porous article, in shaping raw material, add the saccharoid of silica gel or the saccharoid and the water-absorbent polymer particles of silica gel, make base soil, use gained pottery base soil to utilize continuous forming machine to make formed body.
First ceramic porous article of the present invention, the pore-forming material of powder by using cellular silica powder or porous silicon-containing petrochemical industry compound when making, burn till Shi Buhui and produce carbonic acid gas and obnoxious flavour, and firing time is short when also using toner or carbon dust as pore-forming material than in the past.And then, pore-creating characteristic variations or formed body distortion when also being difficult for causing moulding.In addition, second ceramic porous article of the present invention, the 50% particle diameter (D that has regulation by use
50) the pore-forming material of silica-gel-granular thing when making, similarly can when burning till, not produce obnoxious flavour with first ceramic porous article, also shorten firing time, defective such as pore-creating characteristic variations or formed body distortion when being difficult for causing moulding.And then, the manufacture method of first and second formed body of the present invention, by use mix, cracky not when the degassing or moulding, and be difficult for making the silica gel of formed body distortion or the water-absorbent polymer particles pore-forming material when making during moulding, even by one-body molded manufacturing formed body or by continuously shaped manufacturing formed body, the pore-forming material breakage can be do not made yet, finally the high porosity and the ceramic porous article of defective such as distortion not can be obtained by burning till.
Description of drawings
Fig. 1 is the chart that concerns between the average fine pore of expression 50% particle diameter of pore-forming material and porous insert.
Embodiment
As mentioned above, first ceramic porous article of the present invention is the ceramic porous article that contains Si as chemical ingredients at least, be to make base soil by the powder that in shaping raw material, adds cellular silica powder or porous silicon-containing petrochemical industry compound, after the ceramic base earth forming that obtains is the regulation shape, obtain through burning till.
The powder of the cellular silica powder of first ceramic porous article of the present invention and porous silicon-containing petrochemical industry compound, when making ceramic porous article, add in the shaping raw material as pore-forming material, because these powder are the inorganic powder that does not contain the combustiblecomponents of being burnt when burning till, so can not resembling when using toner or carbon dust or water swelling particle as pore-forming material when formed body burns till the combustiblecomponents because of pore-forming material produce carbonic acid gas and obnoxious flavour, and firing time is short when also using toner or carbon dust as pore-forming material than in the past.In addition, it is low and easy to be damaged also not resemble the hollow resin particle intensity, therefore can be when moulding not damaged and change the pore-creating characteristic.
First ceramic porous article of the present invention, the powder that uses cellular silica powder or porous silicon-containing petrochemical industry compound is as pore-forming material, therefore, need as trichroite, it is a kind of ceramic porous article that contains Si as chemical ingredients at least, under the state that adds the specified amount pore-forming material, the mixing moulding raw material is formed to make target as mentioned above.
The cellular silica powder that is used for first ceramic porous article is preferably amorphous silica powder (amorphous silicon stone powder), specifically, and the suitable silica gel that uses.In addition, be used for the porous silicon-containing petrochemical industry compound powder of first ceramic porous article, be preferably the powder of amorphous siliceous petrochemical industry compound, and the composition of its compound then preferably uses the material of for example forming as trichroite.
The cellular silica powder and the porous silicon-containing petrochemical industry compound powder that are used for first ceramic porous article, all preferred its volume density is at 1g/cm
3Below, 0.2～1g/cm more preferably
3If the volume density of these powder surpasses 1g/cm
3, the pore-creating function that its powder brings will descend, the porous insert that can't obtain expecting; If less than 0.2g/cm
3, when burning till, will near the fusing point of its powder composition, cause bigger contraction, become the factor that pore-creating function reduction (void content reduction) and formed body crack.
Here, so-called " volume density " is meant the volume density of PT-R (trade(brand)name) mensuration of using the manufacturing of ホ ソ カ ヮ ミ Network ロ Application company.
Be used for the cellular silica powder of first ceramic porous article and the addition of porous silicon-containing petrochemical industry compound powder, be preferably and account for below the 40 volume % of whole shaping raw materials after adding its powder, more preferably 5～40 volume %.When the addition of these powder when 40 volume % of whole shaping raw materials are following, along with its addition increases, the void content of gained ceramic porous article rises, if but surpass 40 volume %, then the shrinkage of formed body increases when burning till, and void content has the tendency of decline on the contrary.In addition, when the addition of these powder during less than 5 volume % of whole shaping raw materials, the last ascending effect of void content will reduce, and the advantage that interpolation is brought is also just little.
Be used as the powder of pore-forming material, be added in the shaping raw materials such as ceramic powder, and then add tackiness agent, shaping assistant, water etc. therein and mix, make base soil.Then, should pottery base earth forming be after stipulating shape, by being fired into ceramic porous article of the present invention.
When using cellular silica powder or porous silicon-containing petrochemical industry compound powder as pore-forming material, its powder after the fusion, becomes siliceous petrochemical industry compound with other shaping raw material composition reactions in sintering process usually.For example, when the situation that the moulding raw material becomes trichroite to form with cellular silica powder mixes as pore-forming material, the fused silica powder in sintering process with other shaping raw material compositions reactions, finally become the compound that trichroite forms and residue in the ceramic porous article.
Second ceramic porous article of the present invention is the ceramic porous article that contains Si as chemical ingredients at least, by add 50% particle diameter (D in shaping raw material
50) be that the saccharoid of the silica gel of 10～100 μ m is made base soil, the ceramic base earth forming that obtains is the regulation shape after, through being fired into.
The saccharoid of the silica gel in second ceramic porous article is to add in the shaping raw material its 50% particle diameter (D to as pore-forming material when making ceramic porous article
50) be 10～100 μ m.By using inorganic porous material silica gel as pore-forming material, what produce in the time of can preventing to use combustiblematerials as pore-forming material for example cracks, prolongs firing time or produce unfavorable conditions such as carbonic acid gas and obnoxious flavour.In addition, silica gel is the particle that is made of porous insert, with the situation of the equal unit mass of hollow resin particle under, the pore-creating effect is bigger, therefore adds the porous insert that just can obtain high porosity on a small quantity.On the other hand, compare with the hollow resin particle, the physical strength height, and mix and mix raw material or during in moulding particle seldom damaged, therefore can obtain pore-creating effect corresponding to addition.
Silica gel is the single silicic acid (SiO that has as main component
2NH
2O) the molecule three-dimensional netted skeleton that mutually combines and form, and in the gap of its three-dimensional netted skeleton, be formed with the xerogel of many fine pores.The pore-forming material that second ceramic porous article uses the saccharoid by this silica gel to constitute.Should " saccharoid " not refer in particular to the particle of granulation, be the notion that comprises the material that is commonly called saccharoid.
In second ceramic porous article, silica gel is so long as main component is single silicic acid, then can contain other compositions in the scope that does not hinder effect of the present invention, be the so high silica gel of Si containing ratio of 95～99.99mol% but the Si that preferably constitutes silica gel accounts for the ratio of whole metallic elements.
Except the main component silica, remain in compositions such as the acid added in the silica gel manufacturing processed or alkali sometimes in the silica gel.If a large amount of residual these compositions, the containing ratio of Si will be less than above-mentioned scopes, cause that its formed body (even sintered compact) might be contracted to more than the necessary degree when burning till the formed body that contains pore-forming material, be not preferred therefore.
The Si containing ratio for example can adopt weighting method or fluorescent X-ray analysis instrument known analytical procedures such as (XRF:X-rayFluorescence Spectrometer) and device to calculate.But, when representing the Si containing ratio in this manual, be meant the value that adopts weighting method to calculate.
The saccharoid that is used for the silica gel of second ceramic porous article need be 50% particle diameter (D
50) be the saccharoid in 10～100 mu m ranges, be preferably the saccharoid in 10～80 mu m ranges, more preferably the saccharoid in 10～50 mu m ranges.By 50% particle diameter is controlled in this scope, can obtain possessing can practical average fine pore porous insert.
When 50% particle diameter does not reach above-mentioned scope, the average fine pore of gained porous insert will sharply reduce, and therefore be difficult to use in the purposes that requires gas or liquid perviousness as strainer.For example, be used for catching the situation of the diesel particulate filter (DPF:Diesel Particulate Filter) of the particulate matter (PM:Particulate Matter) of discharging from diesel engine such as diesel-engined vehicles, preferred average fine pore is more than 10 μ m, if 50% particle diameter less than 10 μ m, then might be difficult to obtain the porous insert of this average fine pore.
On the other hand, if 50% particle diameter surpasses above-mentioned scope, then might hinder when burning till between the aggregate particle mutually sintering and form firm network, the bonding force between the aggregate particle will descend, cause the physical strength of sintered compact to descend, serious words might make the sintered compact fragmentation.
Here, " x% particle diameter (Dx) " in this specification sheets, be the particle diameter that adopts laser diffraction/diffuse transmission type particle size distribution device (for example trade(brand)name: LA-920, the hole field makes manufacturing etc.) to measure, the particle diameter the when mass accumulation that is meant saccharoid becomes x% with respect to the saccharoid total mass.For example can adopt will adopt ultrasonic dispersing in the 50g ion exchanged water in glass beaker as the 1g saccharoid of determination object, dilute this suspension and be injected in the measuring cell of determinator with proper concn, and then carry out 2 minutes ultrasonic dispersing in determinator after, the method for measuring particle diameter waits to be measured.In this measuring method, " 50% particle diameter (D
50) " promptly become so-called median size.
The saccharoid that is used for the silica gel of second ceramic porous article preferably has the 50% particle diameter (D that relates to of following formula (1) and following formula (2) defined
50) size-grade distribution.By size-grade distribution is in this scope, and make size-grade distribution more sharp-pointed, can obtain possessing can practical average fine pore porous insert.
0.1≤D
10/D
50≤0.5 (1)
2≤D
90/D
50≤5 (2)
In the following formula, D
50Be 50% particle diameter, D
10Be 10% particle diameter, D
90It is 90% particle diameter.
If D
10/ D
50Less than above-mentioned scope, the average fine pore of gained porous insert will sharply diminish, and might be difficult to obtain the porous insert of average fine pore more than 10 μ m.On the other hand, if D
10/ D
50Surpass above-mentioned scope, when screening obtained being used for the silica-gel-granular thing of second ceramic porous article, its rate of recovery can descend, and was not preferred therefore.In order to obtain above-mentioned effect, D more reliably
10/ D
50More preferably 0.2～0.5, especially be preferably 0.3～0.5.
In addition, if D
90/ D
50Less than above-mentioned scope, when screening obtained being used for the silica-gel-granular thing of second ceramic porous article, its rate of recovery can descend, and was not preferred therefore.On the other hand, if D
10/ D
50Surpass above-mentioned scope, then the average fine pore of gained porous insert will sharply diminish, and might be difficult to obtain the porous insert of average fine pore more than 10 μ m.In order to obtain above-mentioned effect, D more reliably
90/ D
50More preferably 2～4, especially be preferably 2～3.
The silica-gel-granular thing that is used for second ceramic porous article is preferably the material of particle 90～100 quality % that contain aspect ratio 1～5.If the containing ratio of the particle of aspect ratio 1～5 breaks away from above-mentioned scope, the roundness of the pore that obtains after burning till descends, and the pressure-losses when causing gas permeation increases, and is not preferred therefore.In order to obtain above-mentioned effect more reliably, more preferably contain the material of particle 95～100 quality % of aspect ratio 1～5, especially be preferably the material that contains 98～100 quality %.
Usually, " aspect ratio " is meant the ratio of major diameter with respect to the particle minor axis, is the containing ratio of the particle of following definite aspect ratio 1～5 in this manual.Promptly, take the silica-gel-granular thing with scanning electronic microscope, optional 50 particles from the zone of the visual 622 μ m * 419 μ m of this shooting, calculate the aspect ratio of each particle from its major diameter and minor axis, the shared ratio of particle of aspect ratio 1～5 in its 50 particles is defined as the containing ratio of the particle of aspect ratio 1～5.At this moment, the minor axis of particle is the shortest particle diameter by its particle center of gravity, and the major diameter of particle is the longest particle diameter by center of gravity.
The silica-gel-granular thing that is used for second ceramic porous article is preferably and does not contain the material that particle diameter surpasses the particle of 100 μ m in fact.By not containing the oversize particle that particle diameter surpasses 100 μ m in fact, can prevent from effectively to form thick pore in the porous insert and make this part become the problem of defective.In addition, for example adopt extrusion moulding to obtain having the situation of the formed body of the honeycomb structure in next door as thin as a wafer, the slit (will become next door from the part of extruding here) that can also prevent from effectively to extrude with nozzle stops up, the unfavorable condition that causes extrusion pressure to rise.
Here, so-called " not containing in fact ", be meant that the particle that particle diameter surpasses 100 μ m is the situation of 0～0.01 quality %, in other words, mean that the following particle of particle diameter 100 μ m is the situation of 99.99～100 quality %.
The silica-gel-granular thing that is used for second ceramic porous article is preferably the material that the porous insert by pore volume 0.4～2.0ml/g constitutes.By pore volume is in this scope, can obtain pore-creating effect corresponding to addition.
If pore volume less than above-mentioned scope, then is difficult to obtain sufficient pore-creating effect.On the other hand, if pore volume surpasses above-mentioned scope, the physical strength of saccharoid descends, and mixing and the raw material or particle can be damaged during in moulding of mixing, can't obtain the pore-creating effect corresponding to addition.In order to obtain above-mentioned effect more reliably, pore volume is 0.6～2.0ml/g more preferably, especially is preferably 1.0～2.0ml/g.
Here, so-called " pore volume " is meant the pore volume of using mercury PORE SIZE APPARATUS FOR (trade(brand)name: ォ one ト Port ァ 9405 types, マ ィ Network ロ メ リ テ ィ ッ Network company makes) to measure.
The silica-gel-granular thing that is used for second ceramic porous article is preferably by specific surface area (JIS-R1626) 100～1000m
2The material that the particle of/g constitutes.By specific surface area is in this scope, can in the physical strength of guaranteeing the gained sintered compact, obtain sufficient pore-creating effect.
If specific surface area less than above-mentioned scope, then is difficult to obtain sufficient pore-creating effect, be not preferred therefore.On the other hand, if specific surface area surpasses above-mentioned scope, the physical strength of gained sintered compact can descend, and is not preferred therefore.In order to obtain above-mentioned effect more reliably, specific surface area is 300～1000m more preferably
2/ g especially is preferably 600～1000m
2/ g.
Here, so-called " specific surface area " is meant the specific surface area of the standard test of being put down in writing according to JIS-R1626 (being measured the method for specific area of fine ceramics powder by gas adsorption BET method).
The silica-gel-granular thing that is used for second ceramic porous article is preferably and makes 50% particle diameter (D
50) be that the sieve of raw material saccharoid by sieve aperture 44～210 μ m of the silica gel of 10～150 μ m sieves, with its 50% particle diameter (D
50) be controlled in 10～100 mu m ranges and the material that obtains.Here, the raw material saccharoid more preferably 50% particle diameter at 10～120 μ m.
If 50% particle diameter of raw material saccharoid less than above-mentioned scope, also has the situation that can not get the saccharoid of 50% particle diameter more than 10 μ m even sieve.On the other hand, if 50% particle diameter of raw material saccharoid surpasses above-mentioned scope, the situation that can not get the saccharoid of 50% particle diameter below 100 μ m is also arranged even sieve.Be not only 50% particle diameter, consider from the angle that size-grade distribution described later is suitable, more preferably use 50% particle diameter at the saccharoid of 25～100 μ m as the raw material saccharoid, especially preferably use the saccharoid of 50% particle diameter at 25～80 μ m.
In addition, when manufacturing is used for the silica-gel-granular thing of second ceramic porous article,, preferably use except controlling 50% particle diameter, have the 50% particle diameter (D that relates to of following formula (3) and following formula (4) defined as the raw material saccharoid
50) the material of size-grade distribution.
0.05≤D
10/D
50≤0.5 (3)
2.0≤D
90/D
50≤8.0 (4)
In the following formula, D
50Be 50% particle diameter, D
10Be 10% particle diameter, D
90It is 90% particle diameter.
By using D
10/ D
50Be in the raw material saccharoid in the above-mentioned scope, can obtain having the saccharoid of the size-grade distribution of following formula (1) defined.In order to obtain above-mentioned effect more reliably, more preferably use the D of raw material saccharoid
10/ D
50Raw material saccharoid in 0.07～0.5 scope especially preferably uses the raw material saccharoid in 0.08～0.5 scope.
0.1≤D
10/D
50≤0.5 (1)
In addition, by using D
10/ D
50Be in the raw material saccharoid in the above-mentioned scope, can obtain having the saccharoid of the size-grade distribution of following formula (2) defined.In order to obtain above-mentioned effect more reliably, more preferably use the D of raw material saccharoid
90/ D
50Raw material saccharoid in 2～7 scopes especially preferably uses the raw material saccharoid in 2～6 scopes.
2≤D
90/D
50≤5 (2)
When manufacturing is used for the silica-gel-granular thing of second ceramic porous article, the sieve of above-mentioned raw materials saccharoid by sieve aperture 44～210 μ m need be sieved.This is to be controlled in saccharoid in 10～100 mu m ranges in order to obtain 50% particle diameter.
If less than above-mentioned scope, then can there be D in the sieve aperture of sieve
10/ D
50Therefore the unfavorable condition that value diminishes is not preferred.On the other hand, if the sieve aperture of sieve surpasses above-mentioned scope, then can there be the unfavorable condition that is difficult to remove the oversize particle that surpasses 100 μ m.In order to obtain above-mentioned effect more reliably, preferably the sieve by sieve aperture 85～170 μ m sieves, and more preferably the sieve by sieve aperture 85～145 μ m sieves.
So long as sieve by sieve with above-mentioned sieve aperture, then method for sieving is not particularly limited, can suitably adopt known method of sieving such as vibration sieve method, centrifugal sieve method, air-flow sieve method, but especially preferably use the air-flow sieve method.
Since silica gel this as porous insert, and be the little light weight particle of apparent density, therefore float over easily on the air-flow, be fit to use the air-flow sieve method to carry out stage treatment.On the other hand, when using vibratory screening apparatus or centrifugal screen, there is the sufficient processing power of situation to guarantee to(for) the silica gel particle of light weight.As the method that adopts the air-flow sieve method to sieve, for example can enumerate and to use the air classifier that possessed cylindric sieve (trade(brand)name for example: meticulous sieve (Fine Sifter) MTS-D101 with regulation mesh size, the former making manufacturing in great river), the raw material saccharoid is put into the internal space of cylindric sieve with air-flow, the limit attracts wind-force from the outside of cylindric sieve, the limit makes the method that the raw material saccharoid sieves by cylindric sieve etc.Therefore this method is preferred because stage treatment ability height can be enhanced productivity.
Wherein, the raw material saccharoid can pass through for example to water glass (water glass: SiO
2Na
2O), under 10～95 ℃ cooling conditions, acid such as hydrochloric acid or sulfuric acid are added on the limit, and the limit violent stirring makes two kinds of substance reactions and after obtaining hydrogel, with ammonium nitrate (NH
4NO
3) waiting the alkali neutralization, then washing obtains with burning till 20～150 ℃ of dryings then.
As the method for the raw material saccharoid of controlled 50% particle diameter, the pH in the time of can enumerating for example according to reaction regulates the method for primary particle size etc.When water glass and acid are reacted, if at pH less than 7 acidic region reaction, then the disassociation of the surface hydroxyl of silica is few, therefore can obtain the little silica-gel-granular thing of 50% particle diameter.On the other hand, if surpass 7 alkalescence zone reaction, then hydroxide ion (OH at pH
-) will play the effect of catalyzer, at the intermolecular formation siloxane bond of silica, therefore can obtain the big silica-gel-granular thing of 50% particle diameter.Wherein, also can be by pulverizing and the existing silica-gel-granular thing of classification, the perhaps suitable satisfactory material of selection in the silica gel goods of selling from the market, the controlled raw material saccharoid of 50% particle diameter.
And, about satisfying as the silica-gel-granular thing that is used for other conditions (for example size-grade distribution, aspect ratio, pore volume, specific surface area etc.) of the silica-gel-granular thing of second ceramic porous article, also can from the various silica gel goods of selling in the market, suitably select the material that satisfies condition, perhaps obtain by pulverizing with processing such as classification.
The silica-gel-granular thing that is used for second ceramic porous article can be mixed together use with for example raw materials such as aggregate particle (ceramic powder etc.), dispersion medium (water etc.), organic binder bond, shaping assistant.These mixtures being mixed, obtain base soil, is the base earth forming regulation shape with methods such as extrusion mouldings, and drying is burnt till, and then can obtain its sintered compact, just ceramic porous article.
Wherein, be used for the silica-gel-granular thing of second ceramic porous article since with silica as major ingredients, so when obtaining being the ceramic porous article of constituent with the silica, a part that can be used as the aggregate particle is added.This method so need not add pore-forming material separately, is a kind of advantageous method because the aggregate particle self plays the effect of pore-forming material therefore.
For example, trichroite (2MgO2Al
2O
35SiO
2) be talcum, kaolin, aluminum oxide, aluminium hydroxide, silica etc. to be formed with the theory of trichroite mix and, obtain by burning till these mixtures as raw material.By whole or a part of silicas are wherein replaced to aforesaid silica-gel-granular thing, can not add separately under the condition of pore-forming material, obtain having the void content that is suitable for purposes and the porous cordierite body of average fine pore, only perhaps can access the porous cordierite body of the high porosity that is difficult to obtain according to common firing operation.As with the pottery of silica as constituent, except trichroite, can also enumerate mullite, forsterite, fayalite, enstatite, silica glass, cristobalite, pottery etc., these potteries similarly can obtain the effect of using described silica-gel-granular thing to bring with trichroite.
Shape for first and second ceramic porous articles of the present invention is not particularly limited, and can suitably select according to its application target.For example when being used for strainer or support of the catalyst etc., can use the honeycomb shape that is considered to be applicable to these purposes usually.
The manufacture method of first formed body of the present invention, be by burning till the manufacture method of the formed body that becomes ceramic porous article, in shaping raw material, add the saccharoid of silica gel or the saccharoid and the water-absorbent polymer particles of silica gel, make base soil, use gained pottery base soil by one-body molded manufacturing formed body.In addition, the manufacture method of second formed body of the present invention, be by burning till the manufacture method of the formed body that becomes ceramic porous article, in shaping raw material, add the saccharoid of silica gel or the saccharoid and the water-absorbent polymer particles of silica gel, make base soil, use gained pottery base soil to utilize continuous forming machine to make formed body.
The saccharoid of silica gel and water-absorbent polymer particles are compared physical strength height, not cracky with the hollow-particle that was widely used as foamex for pore-forming material etc. in the past.Thereby, even use and added the saccharoid of silica gel and the base soil of water-absorbent polymer particles as pore-forming material, moulding is used to carry out integrated hard formed body, perhaps use the continuous forming machine moulding, yet can not mix, outgas or damaged easily during in moulding, therefore by finally burning till the gained formed body, can obtain the high porosity and the ceramic porous article of defective such as distortion not.
The silica-gel-granular thing can add as pore-forming material separately, also can add with water-absorbent polymer particles.When adding with water-absorbent polymer particles, the mass ratio of silica-gel-granular thing and water-absorbent polymer particles (quality of the quality/water-absorbent polymer particles of silica-gel-granular thing) is preferably about 0.25～9.If this mass ratio is less than 0.25, then carbonic acid gas that is caused by combustiblecomponents when formed body burns till and obnoxious flavour just increase, and the thermal value when needing the reduction combustiblecomponents to burn till cracks when burning till with inhibition, therefore has the shortcoming of firing time lengthening; On the other hand,, then almost bring into play not go out and adds the pore-creating effect that water-absorbent polymer particles plays if this mass ratio surpasses 9, can increase add the kind of raw material, production efficiency is low.
The silica-gel-granular thing that uses in the preferred scheme of silica-gel-granular thing and described second ceramic porous article is the same.In addition, as water-absorbent polymer particles, be preferably granular and the suction after median size be the material of 2～200 μ m.
Embodiment
Below, illustrate in greater detail the present invention based on embodiment, but the present invention is not limited to these embodiment.
Embodiment 1～8, comparative example 1 and 2
Use silica gel (marshy land KCC system: P707M (trade(brand)name), median size: 120 μ m, volume density: 0.45g/cm as pore-forming material
3) or powder (marshy land KCC system: P-1 (trade(brand)name), the median size: 15 μ m, volume density: 0.85g/cm of porous Magnesium Silicate q-agent
3), as shown in table 1, in the scope of 0～18 quality %, change the addition of silica gel, and in the scope of 0～40 quality %, change the addition of porous Magnesium Silicate q-agent, become trichroite to form the powder mixes of talcum, silica, aluminum oxide, kaolin and aluminium hydroxide, be made for shaping raw material.Add methylcellulose gum (KCC of SHIN-ETSU HANTOTAI system: SM4000 (trade(brand)name)) therein as forming adhesive, as the tensio-active agent and the water of shaping assistant, mix, prepare ceramic base soil.Wherein, the combined amount of the tackiness agent shown in the table 1, shaping assistant and water is, when the described shaping raw material total amount that will contain pore-forming material is defined as 100 quality %, with respect to its combined amount (mixing outward).Use the ceramic base soil that obtains as mentioned above to make formed body (diameter: 40mm, the length: 100mm), after 1 hour, burnt till 2 hours, obtain ceramic porous article of honeycomb shape by extrusion molding at 1350 ℃ 120 ℃ of dryings.For the gained ceramic porous article, measure its void content, show the result in table 1.
Table 1
| Volume density | Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Talcum | 2.6g/cm 3 | 40.0 quality % | 0.0 quality % | 40.0 quality % | 40.0 quality % | 40.0 quality % | 40.0 quality % | 40.0 quality % | 40.0 quality % | 20.0 quality % | 10.0 quality % |
| Kaolin | 2.6g/cm 3 | 19.0 quality % | 19.0 quality % | 19.0 quality % | 19.0 quality % | 19.0 quality % | 19.0 quality % | 19.0 quality % | 8.0 quality % | 19.0 quality % | 19.0 quality % |
| Silica | 2.6g/cm 3 | 12.5 quality % | 12.5 quality % | 0.0 quality % | 2.5 quality % | 5.0 quality % | 7.5 quality % | 10.5 quality % | 0.0 quality % | 12.5 quality % | 12.5 quality % |
| Aluminum oxide | 3.9g/cm 3 | 13.5 quality % | 13.5 quality % | 13.5 quality % | 13.5 quality % | 13.5 quality % | 13.5 quality % | 13.5 quality % | 19.0 quality % | 13.5 quality % | 13.5 quality % |
| Aluminium hydroxide | 2.8g/cm 3 | 15.0 quality % | 15.0 quality % | 15.0 quality % | 15.0 quality % | 15.0 quality % | 15.0 quality % | 15.0 quality % | 15.0 quality % | 15.0 quality % | 15.0 quality % |
| Silica gel | 0.45g/cm 3 | 0.0 quality % | 0.0 quality % | 12.5 quality % | 10.0 quality % | 7.5 quality % | 5.0 quality % | 2.0 quality % | 18.0 quality % | 0.0 quality % | 0.0 quality % |
| The porous Magnesium Silicate q-agent | 0.85g/cm 3 | 0.0 quality % | 40.0 quality % | 0.0 quality % | 0.0 quality % | 0.0 quality % | 0.0 quality % | 0.0 quality % | 0.0 quality % | 20.0 quality % | 30.0 quality % |
| Tackiness agent | 1.1g/cm 3 | 4.0 quality % | 4.0 quality % | 4.0 quality % | 4.0 quality % | 4.0 quality % | 4.0 quality % | 4.0 quality % | 4.0 quality % | 4.0 quality % | 4.0 quality % |
| Shaping assistant | 1.0g/cm 3 | 0.5 quality % | 0.5 quality % | 0.5 quality % | 0.5 quality % | 0.5 quality % | 0.5 quality % | 0.5 quality % | 0.5 quality % | 0.5 quality % | 0.5 quality % |
| Water | 1.0g/cm 3 | 35.0 quality % | 81.0 quality % | 48.6 quality % | 47.0 quality % | 42.0 quality % | 39.0 quality % | 36.5 quality % | 39.0 quality % | 58.0 quality % | 69.5 quality % |
| Void content | 45.0％ | 48.8％ | 56.1％ | 55.4％ | 53.0％ | 51.4％ | 50.0％ | 53.5％ | 58.2％ | 58.3％ |
As shown in table 1, when using silica gel as pore-forming material, in the scope of silica gel addition 12.5 quality % (28 volume %), along with the silica gel addition increases, void content also rises.Just, when the silica gel addition reached 18 quality % (41 volume %), the formed body when burning till shrank and increases, and void content reduces when being 12.5 quality % than addition.In addition, when using the porous Magnesium Silicate q-agent as pore-forming material, can obtain high porosity in the scope of its addition 30 quality % (35.3 volume %), but when reaching 40 quality % (47 volume %), the formed body when burning till shrinks and increases, void content reduces greatly.
Embodiment 9 and 10, comparative example 3 and 4
For using silica gel (marshy land KCC system: P707M (trade(brand)name), median size: 120 μ m, volume density: 0.45g/cm as pore-forming material
3) situation and use foamex (Matsumoto Yushi-Seiyaku Co., Ltd.'s system: situation マ ィ Network ロ ス Off ェ ア one F-50E (trade(brand)name)) of in the past using, mixing time when the ceramic base of change preparation is native, the void content of the ceramic porous article that compares the completed state of formed body and finally obtain shows the result in table 2.Wherein, be as shown in table 2 about the mixing of raw material etc., be condition about preparation, forming method, formed body shape, drying and the process for calcining etc. of ceramic base soil according to above-mentioned (embodiment 1～8, comparative example 1 and 2).Completed state about formed body, be that surface with formed body does not have the situation in apparent good order and condition of microcrack defective to be designated as " zero ", the situation that the surface of formed body is had minority microcrack defective is designated as " △ ", and the situation that the surface of formed body is had a lot of microcrack defectives is designated as " * ".
Table 2
| Volume density | Comparative example 3 | Comparative example 4 | Embodiment 9 | Embodiment 10 | |
| Talcum | 2.6g/cm 3 | 40.0 quality % | 40.0 quality % | 40.0 quality % | 40.0 quality % |
| Kaolin | 2.6g/cm 3 | 19.0 quality % | 19.0 quality % | 19.0 quality % | 19.0 quality % |
| Silica | 2.6g/cm 3 | 12.5 quality % | 12.5 quality % | 0.0 quality % | 0.0 quality % |
| Aluminum oxide | 3.9g/cm 3 | 13.5 quality % | 13.5 quality % | 13.5 quality % | 13.5 quality % |
| Aluminium hydroxide | 2.8g/cm 3 | 15.0 quality % | 15.0 quality % | 15.0 quality % | 15.0 quality % |
| Silica gel | 0.45g/cm 3 | 0.0 quality % | 0.0 quality % | 12.5 quality % | 12.5 quality % |
| Foamex | 0.03g/cm 3 | 2.5 quality % | 2.5 quality % | 2.5 quality % | 2.5 quality % |
| Tackiness agent | 1.1g/cm 3 | 4.0 quality % | 4.0 quality % | 4.0 quality % | 4.0 quality % |
| Shaping assistant | 1.0g/cm 3 | 0.5 quality % | 0.5 quality % | 0.5 quality % | 0.5 quality % |
| Water | 1.0g/cm 3 | 35.0 quality % | 35.0 quality % | 48.6 quality % | 48.6 quality % |
| Mix the time | 30min | 60min | 30min | 60min | |
| Completed state | × | ○ | △ | ○ | |
| Void content | 58.0％ | 51.2％ | 56.1％ | 56.3％ |
As shown in table 2, though also can obtain high porosity when adding foamex as pore-forming material, in order to obtain good completed state, mixing time when the ceramic base of preparation that must extend is native, void content decline thus.On the other hand, when using silica gel as pore-forming material, the change of the void content that the lengthening time of mixing causes is little, can obtain the good formed body of completed state under the condition that keeps high porosity.
Embodiment 11～18, comparative example 5 and 6
Prepare 50% particle diameter D
50Different silica-gel-granular things.These silica-gel-granular things all contain particle 90～100 quality % of aspect ratio 1～5, by specific surface area 100～1000m
2The particle of/g constitutes, and contains total mole number with respect to whole metallic elements and be the silicon more than the 95mol%.Become trichroite to form (2MgO2Al the ceramic raw material proportioning that each powder constituted of these silica-gel-granular things and talcum (median size 15 μ m), kaolin (median size 7 μ m) and aluminum oxide (median size 2 μ m)
2O
35SiO
2).
For these ceramic raw material 100 mass parts, add 5 mass parts methylcellulose gum powder as organic binder bond, carry out dry type and mix.Here, all use the material of pore volume as the silica-gel-granular thing as 1ml/g.In addition, the amount of silica-gel-granular thing is the 13 quality % that account for the ceramic raw material total mass.
Then,, obtain base soil, use vacuum to practice native machine and extrude this base soil, obtain being shaped to the cylindric base soil of cylindric (external diameter 50mm φ) with Sigma's kneader said mixture that mixes.Prepare separately to have installed with reticulation form width 0.3mm, the honeycomb moulding of the slit of 1.8mm is with the jumper bar of the external diameter 60mm φ of nozzle at interval, above-mentioned cylindric base soil is filled in this jumper bar, by the method for extruding, obtain dividing the honeycomb formed article that forms many cells by the next door.This honeycomb formed article is external diameter 40mm φ, length 60mm.
At 60～80 ℃ of above-mentioned honeycomb formed articles of drying,, obtain the porous cordierite body by burning till at 1380～1430 ℃.This porous cordierite body is that square, the next door thickness that external diameter 38mm φ, length 55mm, cell are shaped as about 1.8mm * 1.8mm is that 0.3mm, cell density are about 30 cells/cm
2For these porous cordierite body measurement void content and average fine pore, it be the results are shown in table 3 and Fig. 1.Wherein, about void content and average fine pore, be to use mercury PORE SIZE APPARATUS FOR (trade(brand)name: ォ one ト Port ァ 9405 types, マ ィ Network ロ メ リ テ ィ ッ Network company makes) to measure.
Table 3
| Comparative example 5 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Comparative example 6 | |||
| The pore-creating material | D 10 | (μm) | 0.7 | 2 | 1.5 | 2.5 | 5 | 7.5 | 5 | 10 | 18 | 25 |
| D 50 | 7 | 10 | 25 | 25 | 25 | 25 | 50 | 80 | 100 | 150 | ||
| D 90 | 35 | 52 | 140 | 125 | 75 | 50 | 200 | 350 | 360 | 420 | ||
| D 10/D 50 | 0.1 | 0.2 | 0.06 | 0.1 | 0.2 | 0.3 | 0.1 | 0.13 | 0.18 | 0.17 | ||
| D 90/D 50 | 5 | 5.2 | 5.6 | 5 | 3 | 2 | 4 | 4.4 | 3.6 | 2.8 | ||
| Porous insert | Void content | (volume %) | 48 | 51 | 52 | 48 | 49 | 53 | 52 | 51 | 50 | - |
| Average fine pore | (μm) | 3 | 10 | 10 | 16 | 18 | 24 | 27 | 31 | 40 | - | |
*Comparative example 6 is the formed body collapse when burning till, and can't obtain porous insert.
Using 50% particle diameter is the porous cordierite body of the silica-gel-granular thing of 10～100 μ m as the embodiment 11～18 of pore-forming material, has the above average fine pore of the needed 10 μ m of DPF purposes, has demonstrated good result.
On the other hand, use 50% particle diameter less than the silica-gel-granular thing of the 10 μ m porous cordierite body as the comparative example 5 of pore-forming material, average fine pore becomes less than 10 μ m, can not guarantee the average fine pore that the needed 10 μ m of DPF purposes are above.In addition, use 50% particle diameter to surpass the condition of the silica-gel-granular thing of 100 μ m as the comparative example 6 of pore-forming material, the formed body collapse can't obtain the porous cordierite body when burning till.
Embodiment 19～21
Prepare D
50, D
10/ D
50, and D
90/ D
50The silica-gel-granular thing that has nothing in common with each other of value.These silica-gel-granular things are used as the raw material saccharoid, this raw material saccharoid is sieved by the sieve of sieve aperture 145 μ m.These silica-gel-granular things that carried out screening are used as pore-forming material, and operation obtains the porous cordierite body similarly to Example 11.For these porous cordierite body measurement void content and average fine pore, it be the results are shown in table 4.Here, screening is to use the air classifier (trade(brand)name: meticulous sieve MTS-D101 of the cylindric sieve that possesses mesh size 145 μ m, the former making manufacturing in great river) carries out, the raw material saccharoid is put into the internal space of above-mentioned cylindric sieve, the limit attracts wind-force from the outside of cylindric sieve, and sieve on the limit.
Table 4
| Embodiment 19 | Embodiment 20 | Embodiment 21 | |||
| Pore-creating material (before the classification) | D 10 | (μm) | 2.7 | 2.8 | 7.6 |
| D 50 | 29 | 26 | 26 | ||
| D 90 | 132 | 95 | 55 | ||
| D 10/D 50 | 0.09 | 0.11 | 0.29 | ||
| D 90/D 50 | 4.6 | 3.7 | 2.1 | ||
| Pore-creating material (after the classification) | D 10 | (μm) | 2.5 | 2.7 | 7.5 |
| D 50 | 25 | 24 | 25 | ||
| D 90 | 115 | 75 | 50 | ||
| D 10/D 50 | 0.1 | 0.11 | 0.3 | ||
| D 90/D 50 | 4.4 | 3.1 | 2 | ||
| Porous insert | Void content | (volume %) | 48 | 49 | 53 |
| Average fine pore | (μm) | 10 | 16 | 24 | |
The silica-gel-granular thing of embodiment 19, D before screening
10/ D
50Less than 0.1, but by carrying out described screening, D
10/ D
50Be controlled in 0.1～0.5 the scope.Embodiment 20 and 21 silica-gel-granular thing satisfy D before screening
10/ D
50Be 0.1～0.5, D
90/ D
50Be 2～5 scope, by carrying out described screening, its size-grade distribution becomes more sharp-pointed.
Embodiment 22～26
Use D
10/ D
50, D
90/ D
50The silica-gel-granular thing that has nothing in common with each other of value, operation obtains the porous cordierite body similarly to Example 11.For these porous cordierite body measurement void content and average fine pore, it be the results are shown in table 5.
Table 5
| Embodiment 22 | Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | |||
| The pore-creating material | D 10 | (μm) | 1.5 | 2.5 | 5.8 | 7.5 | 12.5 |
| D 50 | 25 | 25 | 24 | 27 | 25 | ||
| D 90 | 140 | 125 | 75 | 62 | 50 | ||
| D 10/D 50 | 0.06 | 0.10 | 0.24 | 0.28 | 0.5 | ||
| D 90/D 50 | 5.6 | 5.2 | 3.1 | 2.3 | 2 | ||
| Porous insert | Void content | (volume %) | 52 | 48 | 50 | 53 | 52 |
| Average fine pore | (μm) | 10 | 17 | 18 | 19 | 25 | |
Use D
10/ D
50Be 0.1～0.5, D
90/ D
50Be 2～5 silica-gel-granular thing porous cordierite body, have the above average fine pore of the needed 10 μ m of DPF purposes, demonstrated good result as the embodiment 23～26 of pore-forming material.
On the other hand, use D
10/ D
50, and D
90/ D
50Silica-gel-granular thing outside described scope is compared with the particle diameter of employed silica gel as the porous cordierite body of the embodiment 22 of pore-forming material, and average fine pore extremely diminishes, and stays in the lower value 10 μ m that only guarantee the needed average fine pore of DPF purposes.
Embodiment 27～33
Prepare the silica-gel-granular thing that pore volume has nothing in common with each other, measure the slight compression intensity of these silica-gel-granular things, estimate the physical strength of saccharoid.It is the results are shown in table 6.In addition, mix behind 1 hour these silica-gel-granular thing, use the sieve of sieve aperture 44 μ m, sieve, confirm the ratio of silica-gel-granular thing residual on the sieve, estimate the physical strength of saccharoid with Sigma's kneader.And then, use these silica-gel-granular things, operation obtains the porous cordierite body similarly to Example 11.For these porous cordierite body measurement void content and average fine pore, it be the results are shown in table 6.Here, be to use slight compression tester (trade(brand)name: MCTE-200, Shimadzu Seisakusho Ltd. makes) to measure about slight compression intensity.
Table 6
| Embodiment 27 | Embodiment 28 | Embodiment 29 | Embodiment 30 | Embodiment 31 | Embodiment 32 | Embodiment 33 | |||
| The pore-creating material | D 10 | (μm) | 6.8 | 7 | 6.9 | 7.5 | 7.3 | 6.8 | 7.3 |
| D 50 | 26 | 26 | 23 | 25 | 22 | 22 | 25 | ||
| D 90 | 66 | 65 | 59 | 61 | 58 | 59 | 60 | ||
| D 10/D 50 | 0.26 | 0.27 | 0.3 | 0.3 | 0.33 | 0.31 | 0.29 | ||
| D 90/D 50 | 2.5 | 2.5 | 2.6 | 2.4 | 2.6 | 2.7 | 2.4 | ||
| Pore volume | (ml/g) | 0.2 | 0.4 | 0.6 | 1 | 1.5 | 2 | 2.2 | |
| Slight compression pressure | (g/f) | 8 | 7.5 | 5.5 | 5 | 4.5 | 4 | 3 | |
| Porous insert | Void content | (volume %) | 30 | 40 | 45 | 52 | 55 | 60 | 65 |
| Average fine pore | (μm) | 17 | 18 | 20 | 25 | 22 | 21 | 21 | |
As shown in table 6, there is stronger dependency between pore volume and the slight compression intensity.Specifically, demonstrated the slight compression intensity height of the little saccharoid of pore volume, on the contrary, the low tendency of slight compression intensity of the saccharoid that pore volume is big.
Using pore volume is the porous cordierite body of the silica-gel-granular thing of 0.4～2.0ml/g as the embodiment 28～32 of pore-forming material, has the above void content of the needed 40 volume % of DPF purposes, has demonstrated good result.
On the other hand, pore volume is then confirmed the silica gel particle breakage above the silica-gel-granular thing of the embodiment 32 of 2.0ml/g.In addition, pore volume confirms that less than the silica-gel-granular thing of the embodiment 27 of 0.4ml/g the void content of gained porous insert is low, has the tendency that is difficult to obtain sufficient pore-creating effect.
Embodiment 34～39
Prepare the different silica-gel-granular thing of pore volume, change the amount of these silica-gel-granular things, operation obtains the porous cordierite body similarly to Example 11.For these porous cordierite body measurement void content and average fine pore, it be the results are shown in table 7.
Table 7
| Embodiment 34 | Embodiment 35 | Embodiment 36 | Embodiment 37 | Embodiment 38 | Embodiment 39 | ||
| D 10 | (μm) | 6.8 | 6.8 | 6.8 | 7 | 7 | 7 |
| D 50 | 26 | 26 | 26 | 26 | 26 | 26 | |
| D 90 | 66 | 66 | 66 | 65 | 65 | 65 | |
| D 10/D 50 | 0.26 | 0.26 | 0.26 | 0.27 | 0.27 | 0.27 | |
| D 90/D 50 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | |
| Pore volume | (ml/g) | 0.2 | 0.2 | 0.2 | 0.4 | 0.4 | 0.4 |
| Slight compression pressure | (g/f) | 8 | 8 | 8 | 7.5 | 7.5 | 7.5 |
| Addition | (quality %) | 13 | 18 | 24 | 5 | 13 | 24 |
| Void content | (volume %) | 30 | 33 | 38 | 40 | 42 | 46 |
| Average fine pore | (μm) | 19 | 20 | 18 | 20 | 20 | 19 |
Pore volume is the silica-gel-granular thing of the embodiment 37～39 of 0.4～2.0ml/g, so long as in 5～24 quality % scopes of ceramic raw material total mass, then all have the above void content of the needed 40 volume % of DPF purposes, has demonstrated good result.
Pore volume is less than the silica-gel-granular thing of the embodiment 34～36 of 0.4ml/g, even add the 24 quality %s of pore-creating dosage to the ceramic raw material total mass, also can't obtain the above void content of the needed 40 volume % of DPF purposes, confirm to exist the tendency that is difficult to obtain sufficient pore-creating effect.
Embodiment 40～42
Prepare the different silica-gel-granular thing of containing ratio that particle diameter surpasses the oversize particle of 100 μ m, use these silica-gel-granular things, obtain cylindric base soil according to the method identical with embodiment 11.Prepare to have installed the jumper bar of external diameter 60mm φ of the nozzle of formation 2mm * 0.3mm billet shape slit separately, above-mentioned cylindric base soil is filled in this jumper bar, carry out extrusion test.At this moment, continue to extrude 20 minutes, measure initial stage extrusion pressure and the extrusion pressure after 20 minutes, show the result in table 8 with the speed of 12mm/s.Here, be about the containing ratio of oversize particle, by the silica-gel-granular thing is suspended in water, use the sieve of sieve aperture 105 μ m to sieve (wet classification) after, residual level of residue calculates from the sieve.
Table 8
| Embodiment 40 | Embodiment 41 | Embodiment 42 | |||
| The pore-creating material | D 10 | (μm) | 7.5 | 6.8 | 6.8 |
| D 50 | 25 | 25 | 27 | ||
| D 90 | 61 | 66 | 71 | ||
| D 10/D 50 | 0.3 | 0.27 | 0.25 | ||
| D 90/D 50 | 2.4 | 2.6 | 2.6 | ||
| Oversize particle | (quality %) | 0.005 | 0.01 | 0.03 | |
| Pore volume | (ml/g) | 1 | 1.1 | 1 | |
| Moulding | The initial stage extrusion pressure | (MPa) | 4 | 5 | 5 |
| Extrusion pressure after 20 minutes | (MPa) | 4 | 6 | 15 | |
(just the containing ratio of oversize particle is 0～0.01 quality % not contain oversize particle in fact, the particle of particle diameter below 100 μ m is 99.99～100 quality %) embodiment 40 and 41 silica-gel-granular thing, there are differences hardly between initial stage extrusion pressure and the extrusion pressure after 20 minutes.That is, extrusion pressure does not rise, and has demonstrated good result.
The containing ratio of oversize particle surpasses 0.01 quality % (promptly, particle diameter at the particle below the 100 μ m below 99.99 quality %) the silica-gel-granular thing of embodiment 42, extrusion pressure after 20 minutes rises to 3 times of initial stage extrusion pressure, confirms the tendency that exists formability to descend.
Embodiment 43 and 44, comparative example 7
As pore-forming material, prepare to have 50% particle diameter D as shown in table 9 separately
50Deng silica-gel-granular thing, water-absorbent polymer particles and the foamex of value.In each powder of talcum (median size 15 μ m), kaolin (median size 7 μ m) and aluminum oxide (median size 2 μ m), add above-mentioned pore-forming material to becoming the addition shown in the table 9, proportioning becomes trichroite to form (2MgO2Al
2O
35SiO
2).For ceramic raw material 100 mass parts that obtain as mentioned above, add 5 mass parts methylcellulose gum powder as organic binder bond, carry out dry type and mix.Then,, obtain base soil, use vacuum to practice native machine and extrude this base soil, obtain being shaped to the cylindric base soil of cylindric (external diameter 200mm φ) with Sigma's kneader said mixture that mixes.Prepare separately to have installed with reticulation form width 0.3mm, the honeycomb moulding of the slit of 1.8mm is with the jumper bar of the external diameter 200mm φ of nozzle at interval, above-mentioned cylindric base soil is filled in this jumper bar, by the method for extruding, obtain dividing the honeycomb formed article that forms many cells by the next door.This honeycomb formed article is external diameter 145mm φ, length 180mm.
After above-mentioned honeycomb formed article carried out dielectric drying, to absolutely dry state, and then cut into length 153mm abreast, burn till at 1380～1430 ℃ then, obtain the porous cordierite body with metal solder emery wheel with two blades with warm air drying.This porous cordierite body is that square, the next door thickness that external diameter 144mm φ, length 152mm, cell are shaped as about 1.8mm * 1.8mm is that 0.3mm, cell density are about 30 cells/cm
2For these porous cordierite body measurement void content and average fine pore, it be the results are shown in table 9.Wherein, about roundness be, on shaft collar, place the porous cordierite body, in position from the central part of the position of the 5～10mm separately of two end faces and goods total length, measure diameter by the light chi, after obtaining the minimum diameter and maximum diameter of each position, calculate the maximum diameter of each position and poor (maximum diameter-minimum diameter) of minimum diameter, the locational analog value that its value is maximum is defined as roundness.
Table 9
| Embodiment 43 | Embodiment 44 | Comparative example 7 | |||
| Silica gel | Addition | (quality %) | 13 | 13 | 0 |
| D 10 | (μm) | 6.8 | 6.8 | - | |
| D 50 | 22 | 22 | - | ||
| D 90 | 59 | 59 | - | ||
| D 10/D 50 | 0.31 | 0.31 | - | ||
| D 90/D 50 | 2.7 | 2.7 | - | ||
| Pore volume | (ml/g) | 2 | 2 | - | |
| Water-absorbing polymer | Addition | (quality %) | 0 | 2 | 0 |
| The suction multiple | (g/g) | - | 20 | - | |
| D 50(suction back) | (μm) | - | 50 | - | |
| Foamex | Addition | (quality %) | 0 | 0 | 1.5 |
| D 50 | (μm) | - | - | 40 | |
| Porous insert | Roundness | (mm) | 0.2 | 0.3 | 2.8 |
| Void content | (volume %) | 60 | 65 | 60 | |
| Average fine pore | (μm) | 21 | 23 | 23 | |
During by the moulding of jumper bar shaper, use silica-gel-granular thing or silica-gel-granular thing and water-absorbing polymer embodiment 43 and 44, compare, can obtain high roundness, and void content is not inferior yet with the comparative example 7 that uses foamex as pore-forming material.
Embodiment 45 and 46, comparative example 8
As pore-forming material, prepare to have 50% particle diameter D as shown in table 10 separately
50Deng silica-gel-granular thing, water-absorbent polymer particles and the foamex of value.In each powder of talcum (median size 15 μ m), kaolin (median size 7 μ m) and aluminum oxide (median size 2 μ m), add above-mentioned pore-forming material to becoming the addition shown in the table 10, proportioning becomes trichroite to form (2MgO2Al
2O
35SiO
2).For ceramic raw material 100 mass parts that obtain as mentioned above, add 5 mass parts methylcellulose gum powder as organic binder bond, carry out dry type and mix.And then the limit is added the waterside and is carried out wet mixing.In the twin screw continuous forming machine of honeycomb moulding that the slit that forms width 0.3mm, interval 1.8mm with reticulation has been installed, drop into said mixture then with nozzle, continuously mixture is made base soil and extruded, obtain dividing the honeycomb formed article that forms many cells by the next door.This honeycomb formed article is external diameter 145mm φ, length 180mm.
For the honeycomb formed article that obtains as mentioned above, similarly carry out drying with embodiment 43, cut off, burn till, obtain the porous cordierite body, similarly measure roundness, void content, reach average fine pore for these trichroites and embodiment 43.It is the results are shown in table 10.
Table 10
| Embodiment 45 | Embodiment 46 | Comparative example 8 | |||
| Silica gel | Addition | (quality %) | 13 | 13 | 0 |
| D 10 | (μm) | 6.8 | 6.8 | - | |
| D 50 | 22 | 22 | - | ||
| D 90 | 59 | 59 | - | ||
| D 10/D 50 | 0.31 | 0.31 | - | ||
| D 90/D 50 | 2.7 | 2.7 | - | ||
| Pore volume | (ml/g) | 2 | 2 | - | |
| Water-absorbing polymer | Addition | (quality %) | 0 | 2 | 0 |
| The suction multiple | (g/g) | - | 20 | - | |
| D 50(suction back) | (μm) | - | 50 | - | |
| Foamex | Addition | (quality %) | 0 | 0 | 1.5 |
| D 50 | (μm) | - | - | 40 | |
| Porous insert | Roundness | (mm) | 0.2 | 0.3 | 1.6 |
| Void content | (volume %) | 60 | 65 | 39 | |
| Average fine pore | (μm) | 21 | 23 | 15 | |
During by the continuous forming machine moulding, use silica-gel-granular thing or silica-gel-granular thing and water-absorbing polymer embodiment 45 and 46, compare, can obtain high roundness with the comparative example 8 that uses foamex as pore-forming material.In the comparative example 8, most of foamex breakage in process by the continuous forming machine moulding, void content reduces greatly.
Industrial applicability
Ceramic porous article of the present invention, can be as filter and catalyst carrier etc., be used for the reforming apparatus of waste gas purification apparatus, liquid fuel or the gaseous fuel of burners such as the heat engine such as internal combustion engine or boiler, the purifying processing device etc. of water up and down suitablely.
Claims (20)
1. ceramic porous article, this ceramic porous article contains Si at least as chemical ingredients, be to make base soil by the powder that in shaping raw material, adds cellular silica powder or porous silicon-containing petrochemical industry compound, the ceramic base earth forming that obtains is the regulation shape after, obtaining through burning till.
2. the described ceramic porous article of claim 1, wherein, described cellular silica powder or porous silicon-containing petrochemical industry compound powder after the fusion, become siliceous petrochemical industry compound with other shaping raw material compositions reactions in described sintering process.
3. the described ceramic porous article of claim 2, wherein, the siliceous petrochemical industry compound that is generated by described reaction is the compound that trichroite is formed.
4. the described ceramic porous article of each in the claim 1～3, wherein, described cellular silica powder or porous silicon-containing petrochemical industry compound powder are amorphous silica powder or amorphous siliceous petrochemical industry compound powder.
5. the described ceramic porous article of each in the claim 1～4, wherein, the volume density of described cellular silica powder or porous silicon-containing petrochemical industry compound powder is at 1g/cm
3Below.
6. the described ceramic porous article of each in the claim 1～4, wherein, the volume density of described cellular silica powder or porous silicon-containing petrochemical industry compound powder is 0.2～1g/cm
3
7. the described ceramic porous article of each in the claim 1～6, wherein, the addition of described cellular silica powder or porous silicon-containing petrochemical industry compound powder is, accounts for below the 40 volume % that add the whole described shaping raw materials behind its powder.
8. the described ceramic porous article of each in the claim 1～7, wherein, described ceramic porous article has honeycomb shape.
9. ceramic porous article, this ceramic porous article contains Si at least as chemical ingredients, is by add 50% particle diameter (D in shaping raw material
50) be that the saccharoid of the silica gel of 10～100 μ m is made base soil, the ceramic base earth forming that obtains is the regulation shape after, obtaining through burning till.
10. the described ceramic porous article of claim 9, wherein, the saccharoid of described silica gel is at described 50% particle diameter (D
50) aspect, have the size-grade distribution of following formula (1) and following formula (2) defined,
0.1≤D
10/D
50≤0.5 (1)
2≤D
90/D
50≤5 (2)
In the following formula, D
50Be 50% particle diameter, D
10Be 10% particle diameter, D
90It is 90% particle diameter.
11. claim 9 or 10 described ceramic porous articles, wherein, it is particle below 5 that described silica-gel-granular thing contains the above aspect ratio of 90 quality %.
12. the described ceramic porous article of each in the claim 9～11, wherein, described silica-gel-granular thing does not contain the particle that particle diameter surpasses 100 μ m in fact.
13. the described ceramic porous article of each in the claim 9～12, wherein, described silica-gel-granular thing is that the porous insert by pore volume 0.4～2.0ml/g constitutes.
14. the described ceramic porous article of each in the claim 9～13, wherein, described silica-gel-granular thing is by specific surface area (JIS-R1626) 100～1000m
2The particle of/g constitutes.
15. the described ceramic porous article of each in the claim 9～14, wherein, the ratio that the Si that constitutes described silica gel accounts for whole metallic elements is 95～99.99mol%.
16. the described ceramic porous article of each in the claim 9～15, wherein, described silica-gel-granular thing obtains like this: with 50% particle diameter (D
50) be that the raw material saccharoid of the silica gel of 10～150 μ m is that the sieve of 44～210 μ m sieves by sieve aperture, thus make its 50% particle diameter (D
50) be controlled in 10～100 mu m ranges.
17. the described ceramic porous article of claim 16 wherein, uses at described 50% particle diameter (D
50) aspect has the saccharoid of the size-grade distribution of following formula (3) and following formula (4) defined, is used as the raw material saccharoid of described silica gel,
0.05≤D
10/D
50≤0.5 (3)
2≤D
90/D
50≤8 (4)
In the following formula, D
50Be 50% particle diameter, D
10Be 10% particle diameter, D
90It is 90% particle diameter.
18. claim 16 or 17 described ceramic porous articles wherein, carry out described screening by the air-flow sieve method.
19. the manufacture method of a formed body, be by burning till the manufacture method of the formed body that forms ceramic porous article, in shaping raw material, add the saccharoid of silica gel or the saccharoid and the water-absorbent polymer particles of silica gel, make base soil, use gained pottery base soil by one-body molded manufacturing formed body.
20. the manufacture method of a formed body, be by burning till the manufacture method of the formed body that forms ceramic porous article, in shaping raw material, add the saccharoid of silica gel or the saccharoid and the water-absorbent polymer particles of silica gel, make base soil, use gained pottery base soil to utilize continuous forming machine to make formed body.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101959571A (en) * | 2007-10-12 | 2011-01-26 | 日立金属株式会社 | Cordierite ceramic honeycomb filter and process for producing the same |
| CN110963787A (en) * | 2019-12-19 | 2020-04-07 | 江苏省宜兴非金属化工机械厂有限公司 | Porous ceramic material prepared by filling modified silica gel powder pore-forming agent with dry ice and preparation method thereof |
| CN114956856A (en) * | 2021-02-18 | 2022-08-30 | 日本碍子株式会社 | Method for manufacturing honeycomb structure and method for manufacturing electrically heated carrier |
| CN115413274A (en) * | 2021-03-31 | 2022-11-29 | 第一稀元素化学工业株式会社 | Ceramic powder material, method for producing ceramic powder material, molded body, sintered body, and battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61127682A (en) * | 1984-11-27 | 1986-06-14 | 株式会社神戸製鋼所 | Honeycomb_form silica gel formed body |
| JPH05213681A (en) * | 1992-01-31 | 1993-08-24 | Kawata Mfg Co Ltd | Fiber reinforced honeycomb ceramic body and its production |
-
2005
- 2005-03-24 CN CNB2005800092638A patent/CN100439294C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101959571A (en) * | 2007-10-12 | 2011-01-26 | 日立金属株式会社 | Cordierite ceramic honeycomb filter and process for producing the same |
| CN101959571B (en) * | 2007-10-12 | 2013-06-12 | 日立金属株式会社 | Cordierite ceramic honeycomb filter and process for producing the same |
| CN110963787A (en) * | 2019-12-19 | 2020-04-07 | 江苏省宜兴非金属化工机械厂有限公司 | Porous ceramic material prepared by filling modified silica gel powder pore-forming agent with dry ice and preparation method thereof |
| CN114956856A (en) * | 2021-02-18 | 2022-08-30 | 日本碍子株式会社 | Method for manufacturing honeycomb structure and method for manufacturing electrically heated carrier |
| CN115413274A (en) * | 2021-03-31 | 2022-11-29 | 第一稀元素化学工业株式会社 | Ceramic powder material, method for producing ceramic powder material, molded body, sintered body, and battery |
| CN115413274B (en) * | 2021-03-31 | 2023-10-03 | 第一稀元素化学工业株式会社 | Ceramic powder material, method for producing ceramic powder material, molded body, sintered body, and battery |
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