JPH1085611A - Production of honeycomb carrier made of boria-silica-alumina composition - Google Patents
Production of honeycomb carrier made of boria-silica-alumina compositionInfo
- Publication number
- JPH1085611A JPH1085611A JP8248174A JP24817496A JPH1085611A JP H1085611 A JPH1085611 A JP H1085611A JP 8248174 A JP8248174 A JP 8248174A JP 24817496 A JP24817496 A JP 24817496A JP H1085611 A JPH1085611 A JP H1085611A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- boria
- honeycomb structure
- bsa
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000843 powder Substances 0.000 claims abstract description 63
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010304 firing Methods 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 5
- 239000011707 mineral Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 22
- 239000002245 particle Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000969 carrier Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229960002645 boric acid Drugs 0.000 description 4
- 235000010338 boric acid Nutrition 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 238000006243 chemical reaction 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
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 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 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は触媒担体として優れ
た性質を持つボリア−シリカ−アルミナ組成物より成る
ハニカム構造担体の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a honeycomb structure carrier comprising a boria-silica-alumina composition having excellent properties as a catalyst carrier.
【０００２】[0002]
【従来の技術】ハニカム構造体の触媒担体（ハニカム構
造担体）は、多数の平行した流通路を有するため、流体
を流す場合圧力損失が小さいうえに単位体積当たりの見
掛表面積が大きい特性がある。この点からハニカム構造
担体は化学工業、石油化学用等の廃ガス処理用触媒担
体、燃焼用触媒担体等として広く用いられている。2. Description of the Related Art A catalyst carrier having a honeycomb structure (honeycomb structure carrier) has a large number of parallel flow passages, so that when a fluid flows, it has a small pressure loss and a large apparent surface area per unit volume. . From this point, the honeycomb structure carrier is widely used as a catalyst carrier for treating waste gas, a catalyst carrier for combustion, and the like for chemical industry, petrochemical and the like.
【０００３】これらのハニカム構造担体は、ムライト、
コージェライト、α−アルミナ等よりなるセラミック材
料をハニカム型に成型し、乾燥・焼成して得られた基体
表面にγ−Ａｌ2Ｏ3、ＳｉＯ2等をコーティングして得
ている。この際、触媒の性能は担体の細孔特性と密接な
関係があることから反応の種類、反応条件に適合した細
孔特性を有する担体を得ることが重要である。[0003] These honeycomb structured carriers include mullite,
A ceramic material made of cordierite, α-alumina or the like is formed into a honeycomb shape, and the substrate surface obtained by drying and firing is coated with γ-Al 2 O 3 , SiO 2 or the like. At this time, since the performance of the catalyst is closely related to the pore characteristics of the carrier, it is important to obtain a carrier having pore characteristics suitable for the type of reaction and reaction conditions.
【０００４】しかし、コーティング方式により細孔特性
を制御するのは難しく、コーティング量にも制限を生じ
る。また、用途によっては担体の耐熱性についても要求
される。しかし、耐熱性に優れ、かつ細孔特性の優れた
ハニカム構造体を得る方法については未だ十分な開示は
なされていない。However, it is difficult to control the pore characteristics by the coating method, and the amount of coating is limited. In addition, the heat resistance of the carrier is required depending on the use. However, a method for obtaining a honeycomb structure having excellent heat resistance and excellent pore characteristics has not yet been sufficiently disclosed.
【０００５】[0005]
【発明が解決しようとする課題】本発明者らは耐熱性材
料として高比表面積を有し、且つ耐熱性に優れたボリア
−シリカ−アルミナ（以下「ＢＳＡ」と示す。）複合酸
化物を見出してすでに提案している（特公平７−１１４
９５８号）。このＢＳＡ複合酸化物を用いて直接ハニカ
ム構造体を作ることができれば、細孔特性と耐熱性に優
れたものができると思われる。The present inventors have found a boria-silica-alumina (hereinafter referred to as "BSA") composite oxide having a high specific surface area and excellent heat resistance as a heat-resistant material. Has already been proposed.
958). If a honeycomb structure can be directly produced using this BSA composite oxide, it is considered that a product having excellent pore characteristics and heat resistance can be obtained.
【０００６】すなわち、本発明はＢＳＡ複合酸化物で直
接ハニカム構造体を作る方法の提供を課題とする。That is, an object of the present invention is to provide a method for directly forming a honeycomb structure using a BSA composite oxide.
【０００７】[0007]
【課題を解決するための手段】上記課題を解決する本発
明の方法は、ＢＳＡ水和物粉末とＢＳＡ複合酸化物粉末
とを配合比率を変えて混合し、得た混合粉末に成型助剤
を加えハニカム構造体に成形し、乾燥して焼成するもの
であり、具体的には、３〜１０重量％のＢ2Ｏ3と４〜１
９重量％のＳｉＯ2と残部がＡｌ2Ｏ3からなるＢＳＡ水
和物粉末と、該ＢＳＡ水和物粉末を成型し、乾燥・焼成
し、次いで破砕して得たＢＳＡ複合酸化物粉末とを混合
し、この混合物に鉱酸と有機質結合剤と水とを添加して
混練し、ハニカム型構造体に押出し成型し、乾燥後焼成
するものである。According to the method of the present invention for solving the above-mentioned problems, a BSA hydrate powder and a BSA composite oxide powder are mixed at different mixing ratios, and a molding aid is added to the obtained mixed powder. In addition, it is formed into a honeycomb structure, dried and fired. Specifically, 3 to 10% by weight of B 2 O 3 and 4 to 1
BSA hydrate powder composed of 9% by weight of SiO 2 and the balance being Al 2 O 3 , and a BSA composite oxide powder obtained by molding, drying, calcining and then crushing the BSA hydrate powder The mixture is mixed, a mineral acid, an organic binder, and water are added to the mixture, kneaded, extruded into a honeycomb structure, dried, and fired.
【０００８】本発明の方法ではＢＳＡ水和物粉末と、Ｂ
ＳＡ複合酸化物粉体との混合比を選択することにより細
孔構造を調節することが可能であり、通常ＢＳＡ複合酸
化物粉末の割合を２０〜８０％とすることで実用性の高
いハニカム構造体を得ることが可能である。In the method of the present invention, BSA hydrate powder and B
The pore structure can be adjusted by selecting the mixing ratio with the SA composite oxide powder. Usually, by setting the proportion of the BSA composite oxide powder to 20 to 80%, a highly practical honeycomb structure can be obtained. It is possible to get a body.
【０００９】また、本発明で用いる鉱酸には硝酸が推奨
され、有機質結合材は、ポリビニールアルコール、メチ
ルセルロース、カルボキシメチルセルロース、デキスト
リン等であり、その添加量は５〜２０重量％の範囲とす
るのが望ましい。Further, nitric acid is recommended as the mineral acid used in the present invention, and the organic binder is polyvinyl alcohol, methylcellulose, carboxymethylcellulose, dextrin or the like, and the added amount is in the range of 5 to 20% by weight. It is desirable.
【００１０】さらに、成型体の乾燥は、温度７０〜９０
℃、湿度８０〜９５％の範囲で行い、焼成は６００〜１
４００℃とすることが好ましい。[0010] Further, drying of the molded body is performed at a temperature of 70 to 90.
C., humidity: 80-95%, firing: 600-1
Preferably, the temperature is 400 ° C.
【００１１】[0011]
【発明の実施の形態】本発明のＢＳＡ組成物を製造する
方法としては、例えば硫酸アルミニウム水溶液とアルミ
ン酸ナトリウム水溶液との加水分解により生成するアル
ミナ水和物スラリーに、ＳｉＯ2として５〜２０重量％
の範囲になるように珪酸ナトリウム水溶液を添加してア
ルミナ−シリカ水和物を得る。次いでスラリーを濾過・
洗浄してアルミナ−シリカ水和物ケーキを得、これに、
Ｂ2Ｏ3として３〜１０重量％の範囲になるようにオルト
ほう酸及び／またはオルトほう酸水溶液を添加して充分
混合する。こうして得られたスラリーを噴霧乾燥しＢＳ
Ａ水和物粉末を得る。As a method for producing a BSA compositions DETAILED DESCRIPTION OF THE INVENTION The present invention is, for example alumina hydrate slurry by hydrolysis of an aqueous solution of aluminum sulfate and sodium aluminate aqueous solution, 5 to 20 weight as SiO 2 %
An aqueous solution of sodium silicate is added to obtain an alumina-silica hydrate so as to fall within the range described above. Then filter the slurry
Washing to obtain an alumina-silica hydrate cake, which comprises
B 2 O 3 as the addition of ortho boric acid and / or ortho boric acid aqueous solution to be in the range of 3-10 wt% mixed well. The slurry thus obtained is spray-dried, and BS
A hydrate powder is obtained.
【００１２】次にこのＢＳＡ水和物粉末に水と硝酸を加
えニーダー中で可塑化し、所望の形状のダイスを有する
成型機により押出し成型する。得られた成型体を８０〜
１２０℃で乾燥し、次いで５００℃〜１０００℃で焼成
する。得られた焼成物を粉砕し、平均粒径が５〜２０μ
の範囲のＢＳＡ複合酸化物粉末を得る。Next, water and nitric acid are added to the BSA hydrate powder, plasticized in a kneader, and extruded by a molding machine having a die having a desired shape. 80-
Dry at 120 ° C and then bake at 500 ° C to 1000 ° C. The obtained fired product is pulverized, and the average particle size is 5 to 20 μm.
Is obtained.
【００１３】さて、本発明のボリア−シリカ−アルミナ
組成物においてＢ2Ｏ3を３〜１０重量％、ＳｉＯ2を４
〜１９重量％の範囲とするのはＢ2Ｏ3が３重量％未満及
び１０重量％以上、ＳｉＯ2を４重量％未満及び１９重
量％以上の組成物では耐熱性が低下し、ひいては比表面
積が著しく減少するからである。In the boria-silica-alumina composition of the present invention, 3 to 10% by weight of B 2 O 3 and 4 to 4% of SiO 2
-19 to the weight percent range of B 2 O 3 is less than 3 wt% and 10 wt% or more, the heat resistance is reduced in the SiO 2 4 less wt% and 19 wt% or more of the composition, and thus the specific surface area Is significantly reduced.
【００１４】本発明のＢＳＡ複合酸化物粉末は、ＢＳＡ
水和物粉末を成型し、乾燥して５００〜１０００℃好ま
しくは５００〜８００℃で通常２時間焼成する。焼成温
度が５００℃以下では酸化物状態にならず、また１００
０℃以上で焼成すると焼結がおこり、次の工程で行う破
砕がしずらいからである。[0014] The BSA composite oxide powder of the present invention comprises BSA
The hydrate powder is molded, dried and calcined at 500 to 1000 ° C, preferably 500 to 800 ° C, usually for 2 hours. When the sintering temperature is 500 ° C. or less, it does not become an oxide,
This is because sintering occurs when firing at 0 ° C. or higher, and it is difficult to perform crushing in the next step.
【００１５】次に得られた焼成物は平均粒径が５〜２０
μの範囲になるように破砕するのが望ましい。平均粒径
が５μ以下でも良いが破砕工程において長時間要し、平
均粒径が２０μ以上にすると好ましいハニカム構造担体
が得られない。Next, the obtained fired product has an average particle size of 5 to 20.
It is desirable to crush to a range of μ. The average particle size may be 5 μm or less, but it takes a long time in the crushing step, and if the average particle size is 20 μm or more, a preferable honeycomb structured carrier cannot be obtained.
【００１６】本発明においてＢＳＡ水和物粉末とＢＳＡ
複合酸化物粉末の混合比率を２０〜８０重量％の範囲と
するのは、ＢＳＡ水和物粉末に加える複合酸化物粉末の
混合比率を２０重量％未満にするとハニカム構造体にク
ラックの発生が起こり好ましいハニカム構造担体が得ら
れない。また混合比率を８０重量％以上加えても良いが
細孔特性の制御に対する効果が得られにくいからであ
る。In the present invention, BSA hydrate powder and BSA
The reason why the mixing ratio of the composite oxide powder is in the range of 20 to 80% by weight is that if the mixing ratio of the composite oxide powder added to the BSA hydrate powder is less than 20% by weight, cracks occur in the honeycomb structure. Preferred honeycomb structure carriers cannot be obtained. Although the mixing ratio may be 80% by weight or more, it is difficult to obtain the effect of controlling the pore characteristics.
【００１７】以上説明した手順で得たＢＳＡ水和物粉末
とＢＳＡ複合酸化物粉末とは所望の比率で混合された
後、有機バインダーと水と硝酸とが添加され、充分混練
し可塑化される。その後、真空押出し成型機を用いて所
望の形状のハニカム金型を通して押出し、貫通孔を有す
るハニカム構造体に成型される。次いでこの成型体を温
度７０〜９０℃、湿度８０〜９５％の範囲で恒温恒湿乾
燥させ、６００〜１４００℃の範囲で焼成して、ハニカ
ム構造担体とする。After the BSA hydrate powder and the BSA composite oxide powder obtained by the above-described procedure are mixed in a desired ratio, an organic binder, water and nitric acid are added, and they are sufficiently kneaded and plasticized. . Thereafter, the material is extruded through a honeycomb mold having a desired shape using a vacuum extruder, and is formed into a honeycomb structure having a through hole. Next, the molded body is dried at a constant temperature and a constant humidity at a temperature of 70 to 90 ° C and a humidity of 80 to 95%, and fired at a temperature of 600 to 1400 ° C to obtain a honeycomb structured carrier.
【００１８】本発明のハニカム構造体を成型する際に添
加する有機バインダーの成分としては、ポリビニールア
ルコール，メチルセルロース，カルボキシメチルセルロ
ース，デキストリン等であり、添加量は５〜２０重量％
の範囲とするのが望ましい。添加量が５重量％以下では
可塑性が不充分で好ましいハニカム構造体を得ることが
できず、２０重量％以上添加しても良いが、ハニカム構
造体を乾燥後焼成する際に有機バインダーは燃焼により
炭素化し、次いで燃焼分解するがその際部分的に異常な
高温となり、ハニカム構造体を崩壊することもあるので
好ましくない。また、硝酸を添加するのはボリア−シリ
カ−アルミナ水和物粉体及び／又はボリア−シリカ−ア
ルミナ酸化物粉体の粒子の一部を解膠させ粒子の充填状
態を増し、ハニカム構造体の保強性を増すためである。The components of the organic binder to be added when the honeycomb structure of the present invention is molded include polyvinyl alcohol, methylcellulose, carboxymethylcellulose, dextrin and the like.
It is desirable to be within the range. When the addition amount is 5% by weight or less, a preferable honeycomb structure cannot be obtained due to insufficient plasticity, and may be added in an amount of 20% by weight or more. However, when the honeycomb structure is dried and then fired, the organic binder is burned. It is carbonized and then decomposed by combustion. At that time, however, the temperature becomes partially abnormally high, and the honeycomb structure may be broken, which is not preferable. Also, the addition of nitric acid increases the packing state of the particles by pulverizing some of the particles of the boria-silica-alumina hydrate powder and / or the boria-silica-alumina oxide powder, thereby improving the honeycomb structure. This is to increase cohesion.
【００１９】成型したハニカム構造体を温度７０〜９０
℃、湿度８０〜９５％の条件で恒温恒湿乾燥するのは８
０％以下の低湿度条件ではハニカム構造体の一部にクラ
ックが生じ、好ましいハニカム構造体が得られないから
である。The formed honeycomb structure is heated to a temperature of 70 to 90.
It is 8 to dry at a constant temperature and a constant humidity of 80 to 95%.
This is because cracks occur in a part of the honeycomb structure under a low humidity condition of 0% or less, and a preferable honeycomb structure cannot be obtained.
【００２０】ハニカム構造体の焼成温度を６００〜１４
００℃の範囲にするのは６００℃以下の温度では有機バ
インダーが分解せずに炭素分として残存してしまい、１
４００℃以上の温度では比表面積値が小さくなり触媒担
体としての特性が失われる。The firing temperature of the honeycomb structure is set to 600 to 14
When the temperature is set to the range of 00 ° C., at a temperature of 600 ° C. or less, the organic binder does not decompose and remains as a carbon content,
At a temperature of 400 ° C. or higher, the specific surface area decreases, and the properties as a catalyst carrier are lost.
【００２１】本発明の製造方法で細孔特性が制御できる
理由としては酸化物粉体粒子間に物理的な力で解膠する
水和物粉体の粒子の充填状態が異なるためではないかと
推定される。It is presumed that the reason why the pore characteristics can be controlled by the production method of the present invention is that the packing state of the hydrate powder, which is peptized by physical force, differs between the oxide powder particles. Is done.
【００２２】[0022]
【実施例】次に実施例を用いて本発明をさらに説明す
る。Next, the present invention will be further described with reference to examples.
【００２３】（実施例１）内容１００リットルの攪拌機付き
ステンレス反応槽に水４９．５リットルを入れ、これにＡｌ
2Ｏ3として７７４ｇを含む硫酸アルミニウム水溶液９５
４０ｇを加え、７０℃まで加温し、保持し、攪拌しつつ
Ａｌ2Ｏ3として１２７５ｇを含むアルミン酸ナトリウム
水溶液を滴下してｐＨ９．０のアルミナ水和物スラリー
を得た。Example 1 49.5 liters of water was placed in a 100 liter stainless steel reaction vessel equipped with a stirrer, and Al was added thereto.
Aluminum sulfate aqueous solution 95 containing 774 g as 2 O 3
After adding 40 g, the mixture was heated to 70 ° C., maintained, and stirred, and an aqueous solution of sodium aluminate containing 1275 g as Al 2 O 3 was added dropwise to obtain an alumina hydrate slurry having a pH of 9.0.
【００２４】次いで、このスラリーに濃度３０％の硝酸
５５ｇを加えてｐＨを５．４とし、次いで、攪拌しつ
つ、ＳｉＯ2として２５２ｇを含む珪酸ナトリウム水溶
液１８００ｇを滴下してｐＨ８．５のアルミナーシリカ
水和物を得、濾過し、洗浄してアルミナ−シリカ水和物
ケーキを得た。Next, 55 g of 30% concentration nitric acid was added to the slurry to adjust the pH to 5.4. Then, while stirring, 1800 g of an aqueous sodium silicate solution containing 252 g of SiO 2 was added dropwise to the slurry to adjust the pH of the alumina to 8.5. A silica hydrate was obtained, filtered and washed to obtain an alumina-silica hydrate cake.
【００２５】このアルミナ−シリカ水和物ケーキ１３５
２０ｇ（アルミナ−シリカとして２０２８ｇ）に、試薬
特級のオルトほう酸１８８．８ｇ（Ｂ2Ｏ3として１０
６．８ｇ）を水１０リットルに溶解したオルトほう酸溶液を
加え、撹拌混合し、次いで水１０．５リットルを更に加え撹
拌混合して得たスラリーをホモジナイズ処理を行った
後、噴霧乾燥してボリア−シリカ−アルミナ水和物粉体
ａ（酸化物換算でＢ2Ｏ3５．０％、ＳｉＯ2 １０．５
％、Ａｌ2Ｏ3 ８４．６％）を得た。This alumina-silica hydrate cake 135
In 20 g (2028 g as alumina-silica), 188.8 g of reagent-grade orthoboric acid (10 as B 2 O 3)
Orthoboric acid solution obtained by dissolving 6.8 g) in 10 liters of water was added, and the mixture was stirred and mixed. Then, 10.5 liters of water was further added, and the mixture was stirred and homogenized. - silica - B 2 O 3 5.0% alumina hydrate powder a (in terms of oxide, SiO 2 10.5
% To obtain a Al 2 O 3 84.6%).
【００２６】次に前記ボリア−シリカ−アルミナ水和物
粉体１０００ｇに水８２０リットルと濃度３０％の硝酸４０
リットルとを加えニーダー中で練り込み可塑化し、直径５．
０ｍｍのダイスを有する押出し成型機にて成型し、乾燥
し、電気炉で６００℃で２時間焼成した。後粉砕し平均
粒径８μのボリア−シリカ−アルミナ複合酸化物粉体ｂ
を得た。次いで前記水和物粉体ａ５００ｇと複合酸化物
粉体ｂ５００ｇにセランダー（ユケン工業株式会社製有
機成型助剤）１６０ｇと濃度３０％の硝酸８０リットルと水
１０３０リットルとを加え充分可塑化するまで混練した後、
壁厚０．４ｍｍ、壁間距離２．０ｍｍ、セル形状正方形
のハニカム金型を通しハニカム構造体に成型し、温度８
５℃、湿度９０％の条件で４８時間乾燥した後８００℃
で３時間焼成し、ハニカム構造担体Ａを得た。このハニ
カム構造担体Ａの原料組成等を表１に、細孔特性を表２
に示した。Next, 820 liters of water and 40% nitric acid 40 were added to 1000 g of the above boria-silica-alumina hydrate powder.
Liters and kneading in a kneader, plasticizing, diameter 5.
It was molded with an extruder having a 0 mm die, dried, and fired in an electric furnace at 600 ° C. for 2 hours. After grinding, boria-silica-alumina composite oxide powder b having an average particle size of 8 μm
I got Next, to 500 g of the hydrate powder a and 500 g of the composite oxide powder b, 160 g of Serander (organic molding aid manufactured by Yuken Industries Co., Ltd.), 80 liters of 30% nitric acid and 1030 liters of water were added and kneaded until plasticization was sufficient. After doing
A honeycomb structure having a wall thickness of 0.4 mm, a wall-to-wall distance of 2.0 mm, and a square cell shape was formed into a honeycomb structure at a temperature of 8 mm.
800 ° C after drying for 48 hours at 5 ° C and 90% humidity
For 3 hours to obtain a honeycomb structure carrier A. Table 1 shows the raw material composition and the like of the honeycomb structured carrier A, and Table 2 shows the pore characteristics.
It was shown to.
【００２７】（実施例２,３）実施例１に示す方法とほ
ぼ同様の製造方法で得たボリア−シリカ−アルミナ水和
物粉体ａと酸化物粉体ｂの配合比率をそれぞれ８０％−
２０％，２０％−８０％と変化させたこと以外ハニカム
構造担体Ａとほぼ同様の方法でハニカム構造担体Ｂ，Ｃ
を得た。得られたハニカム構造担体Ｂ（実施例２），Ｃ
（実施例３）の原料組成等を表１に、細孔特性を表２に
示した。表２よりボリア−シリカ−アルミナ水和物粉体
と酸化物粉体の配合比率を変えることで、細孔分布の制
御が可能であることが明らかである。(Examples 2 and 3) The mixing ratio of the boria-silica-alumina hydrate powder a and the oxide powder b obtained by the substantially same production method as in Example 1 was 80%.
Honeycomb structure carriers B and C are formed in substantially the same manner as the honeycomb structure carrier A except that they are changed to 20%, 20% -80%.
I got The obtained honeycomb structure carrier B (Example 2), C
Table 1 shows the raw material composition of Example 3 and Table 2 shows the pore characteristics. From Table 2, it is clear that the pore distribution can be controlled by changing the mixing ratio of the boria-silica-alumina hydrate powder and the oxide powder.
【００２８】（実施例４,５）Ａｌ2Ｏ3 ／ＳｉＯ2 とし
て８０／２０重量％、９５／５重量％となるようにアル
ミナ水和物スラリーに添加する珪酸ナトリウム水溶液の
添加量を変化させたこと以外実施例１のボリア−シリカ
−アルミナ水和物粉体ａ及び酸化物粉体ｂを得る製造方
法を用いて酸化物換算でＢ2Ｏ3 ５．０％、ＳｉＯ2 １
９．０％、Ａｌ2Ｏ3 ７６．０％の水和物粉体ｃと平均
粒径８μの酸化物粉体ｄ及び酸化物換算でＢ2Ｏ3 ５．
０％、ＳｉＯ2 ４．８％、Ａｌ2Ｏ3 ９０．２％の水和
物粉体ｅと平均粒径８μの酸化物粉体ｆを得た。(Examples 4 and 5) The amount of the sodium silicate aqueous solution added to the alumina hydrate slurry was changed so that the Al 2 O 3 / SiO 2 became 80/20% by weight and 95/5% by weight. boria in example 1 except that the - silica - B 2 O 3 5.0% in terms of oxide with a manufacturing method for obtaining the alumina hydrate powder a and oxide powder b, SiO 2 1
A hydrate powder c of 9.0% and 76.0% of Al 2 O 3, an oxide powder d having an average particle diameter of 8 μm, and B 2 O 3 in terms of an oxide.
A hydrate powder e of 0%, 4.8% of SiO 2 and 90.2% of Al 2 O 3 and an oxide powder f having an average particle size of 8 μ were obtained.
【００２９】得られた水和物粉体ｃと酸化物粉体ｄ及び
水和物粉体ｅと酸化物粉体ｆを用い実施例１のハニカム
構造担体Ａとほぼ同様の方法でハニカム構造担体Ｄ，Ｅ
を得た。得られたハニカム構造担体Ｄ（実施例４），Ｅ
（実施例５）の原料組成等を表１に示し、細孔特性を表
２に示した。Using the obtained hydrate powder c and oxide powder d and hydrate powder e and oxide powder f, the honeycomb structure carrier was obtained in substantially the same manner as the honeycomb structure carrier A of Example 1. D, E
I got The obtained honeycomb structure carrier D (Example 4), E
Table 1 shows the raw material composition and the like of (Example 5), and Table 2 shows the pore characteristics.
【００３０】（実施例６,７）実施例４に示す方法とほ
ぼ同様の製造方法で得たボリア−シリカ−アルミナ水和
物粉体ｃと酸化物粉体ｄ及び水和物粉体ｅと酸化物粉体
ｆの配合比率を８０％−２０％と変化させたこと以外ハ
ニカム構造担体Ａとほぼ同様の方法でハニカム構造担体
Ｆ，Ｇを得た。得られたハニカム構造担体Ｆ，Ｇの原料
組成等を表１に示し、細孔特性を表２に示した。表２よ
りボリア−シリカ−アルミナの組成を変えてもボリア−
シリカ−アルミナ水和物粉体と酸化物粉体の配合比率を
変えることで、細孔分布の制御が可能であることが明ら
かである。(Examples 6 and 7) Boria-silica-alumina hydrate powder c, oxide powder d and hydrate powder e obtained by a production method substantially similar to that shown in Example 4 Honeycomb-structured carriers F and G were obtained in substantially the same manner as the honeycomb-structured carrier A except that the mixing ratio of the oxide powder f was changed to 80% to 20%. Table 1 shows the raw material composition and the like of the obtained honeycomb structured carriers F and G, and Table 2 shows the pore characteristics. Table 2 shows that even if the composition of boria-silica-alumina was changed, boria-
It is clear that the pore distribution can be controlled by changing the mixing ratio of the silica-alumina hydrate powder and the oxide powder.
【００３１】（実施例８，９，１０）実施例１，２,３
で得た乾燥ハニカム構造体を１０００℃の温度で３時間
焼成してハニカム構造担体Ｈ（実施例８），Ｉ（実施例
９），Ｊ（実施例１０）を得た。得られたハニカム構造
担体Ｈ，Ｉ，Ｊの原料組成等を表１に示し、細孔特性を
表２に示した。表２より焼成温度を変えることでもミク
ロ細孔の細孔特性を変化させることは可能であるが、メ
ソ細孔，マクロ細孔の制御ができないことが明らかであ
る。Embodiments 8, 9, and 10 Embodiments 1, 2, and 3
The dried honeycomb structure obtained in the above was fired at a temperature of 1000 ° C. for 3 hours to obtain honeycomb structure carriers H (Example 8), I (Example 9), and J (Example 10). Table 1 shows the raw material composition of the obtained honeycomb structured carriers H, I, and J, and Table 2 shows the pore characteristics. It is clear from Table 2 that the pore characteristics of the micropores can be changed by changing the firing temperature, but the mesopores and macropores cannot be controlled.
【００３２】（比較例１）実施例１に示す方法とほぼ同
様の製造方法で得たボリア−シリカ−アルミナ酸化物粉
体だけを用いたこと以外実施例１のハニカム構造担体Ａ
とほぼ同様の方法でハニカム構造担体Ｋを得た。得られ
たハニカム構造担体Ｋの原料組成等を表１に、細孔特性
を表２に示した。ハニカム構造担体Ｋはボリア−シリカ
−アルミナ酸化物粉体１００％のものであるが、ボリア
−シリカ−アルミナの水和物粉体２０％−酸化物粉体８
０％の配合比率で得たハニカム構造担体Ｃとほぼ同等の
細孔特性を有しており、１００％にした意義はみられな
いことがわかった。この結果、酸化物粉体８０％を越え
ると細孔特性は一定となってしまい。調整できないこと
がわかる。(Comparative Example 1) The honeycomb structure carrier A of Example 1 except that only a boria-silica-alumina oxide powder obtained by a production method substantially similar to that shown in Example 1 was used.
A honeycomb structure carrier K was obtained in substantially the same manner as described above. Table 1 shows the raw material composition and the like of the obtained honeycomb structure carrier K, and Table 2 shows the pore characteristics. The honeycomb structure carrier K is made of 100% boria-silica-alumina oxide powder, but 20% boria-silica-alumina hydrate powder-oxide powder 8
It has almost the same pore characteristics as the honeycomb structure carrier C obtained at a blending ratio of 0%, and it was found that there is no significance in setting it to 100%. As a result, if the oxide powder exceeds 80%, the pore characteristics become constant. It turns out that it cannot be adjusted.
【００３３】（比較例２）実施例１に示す方法とほぼ同
様の製造方法で得たボリア−シリカ−アルミナ水和物粉
体とボリア−シリカ−アルミナ酸化物粉体との比率を１
５％−８５％としたこと以外実施例１のハニカム構造担
体Ａとほぼ同様の方法でハニカム構造担体Ｋを得た。得
られたハニカム構造体にはクラックが発生しており、好
ましいハニカム構造担体が得られなかった。(Comparative Example 2) The ratio of boria-silica-alumina hydrate powder and boria-silica-alumina oxide powder obtained by a production method substantially similar to that shown in Example 1 was 1
A honeycomb structure carrier K was obtained in substantially the same manner as the honeycomb structure carrier A of Example 1 except that the content was 5% to 85%. Cracks occurred in the obtained honeycomb structure, and a preferable honeycomb structure carrier was not obtained.
【００３４】 表２に示すハニカム構造担体の細孔特性は水銀圧入法に
より求め、比表面積は窒素ガス吸着によるＢＥＴ法によ
り求めた。[0034] The pore characteristics of the honeycomb structured carrier shown in Table 2 were determined by a mercury intrusion method, and the specific surface area was determined by a BET method using nitrogen gas adsorption.
【００３５】[0035]
【発明の効果】本発明によれば特定組成範囲のボリア−
シリカ−アルミナ水和物粉体と酸化物粉体との配合比率
を変え、これに有機バインダー等を添加して成型・焼成
して得たハニカム構造担体は細孔特性の制御が可能であ
り、触媒反応に合った細孔特性を有するハニカム構造担
体を選定することができる。According to the present invention, boron having a specific composition range is obtained.
The honeycomb structure carrier obtained by changing the mixing ratio of the silica-alumina hydrate powder and the oxide powder, adding an organic binder or the like thereto, and molding and firing can control the pore characteristics, A honeycomb structure carrier having pore characteristics suitable for the catalytic reaction can be selected.
Claims (4)
リア−シリカ−アルミナ複合酸化物粉末とを配合比率を
変えて混合し、得た混合粉末に成型助剤を加えハニカム
構造体に成形し、乾燥して焼成することによりハニカム
構造担体を製造する方法において、３〜１０重量％のＢ
2Ｏ3と４〜１９重量％のＳｉＯ2と残部がＡｌ2Ｏ3から
なるボリア−シリカ−アルミナ水和物粉末と、該ボリア
−シリカ−アルミナ水和物粉末を成型し、乾燥・焼成
し、次いで破砕して得たボリア−シリカ−アルミナ複合
酸化物粉末とを混合し、この混合物に鉱酸と有機質結合
剤と水とを添加して混練し、ハニカム構造体に押出し成
型し、乾燥後焼成することを特徴とするボリア−シリカ
−アルミナ組成物よりなるハニカム構造担体の製造方
法。1. A mixture of a boria-silica-alumina hydrate powder and a boria-silica-alumina composite oxide powder at different mixing ratios, and a molding aid is added to the obtained mixed powder to form a honeycomb structure. And a method for producing a honeycomb structured carrier by drying and firing, wherein 3 to 10% by weight of B
A boria-silica-alumina hydrate powder composed of 2 O 3 , 4 to 19% by weight of SiO 2 and the balance being Al 2 O 3 , and the boria-silica-alumina hydrate powder are molded, dried and fired. Then, a boria-silica-alumina composite oxide powder obtained by crushing is mixed, and a mineral acid, an organic binder and water are added to the mixture, kneaded, extruded into a honeycomb structure, and dried. A method for producing a honeycomb structured carrier comprising a boria-silica-alumina composition, characterized by firing.
リア−シリカ−アルミナ複合酸化物粉末とを配合するに
際しボリア−シリカ−アルミナ複合酸化物粉末の割合を
２０〜８０％とする請求項１記載の方法。2. The method according to claim 1, wherein the mixing ratio of the boria-silica-alumina hydrate powder and the boria-silica-alumina composite oxide powder is 20 to 80%. The described method.
てポリビニールアルコール、メチルセルロース、カルボ
キシメチルセルロース、デキストリン等の少なくとも１
種を用い、有機結合材の添加量を５〜２０重量％の範囲
とする請求項１または２記載の方法。3. Use of nitric acid as a mineral acid and at least one of polyvinyl alcohol, methylcellulose, carboxymethylcellulose and dextrin as an organic binder.
3. The method according to claim 1, wherein the amount of the organic binder is in the range of 5 to 20% by weight using a seed.
８０〜９５％の範囲で行い、焼成を６００〜１４００℃
で行う請求項１〜３記載のいずれかの方法。4. The molding is dried at a temperature of 70 to 90.degree. C. and a humidity of 80 to 95%, and calcined at a temperature of 600 to 1400.degree.
The method according to any one of claims 1 to 3, wherein the method is performed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8248174A JPH1085611A (en) | 1996-09-19 | 1996-09-19 | Production of honeycomb carrier made of boria-silica-alumina composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8248174A JPH1085611A (en) | 1996-09-19 | 1996-09-19 | Production of honeycomb carrier made of boria-silica-alumina composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1085611A true JPH1085611A (en) | 1998-04-07 |
Family
ID=17174319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8248174A Pending JPH1085611A (en) | 1996-09-19 | 1996-09-19 | Production of honeycomb carrier made of boria-silica-alumina composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1085611A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002535229A (en) * | 1998-12-28 | 2002-10-22 | コーニング インコーポレイテッド | High strength and high surface area alumina ceramic |
| US6468374B1 (en) * | 1999-02-18 | 2002-10-22 | Corning Incorporated | Method of making silica glass honeycomb structure from silica soot extrusion |
| JP2010179267A (en) * | 2009-02-07 | 2010-08-19 | Kosei:Kk | Support, and method of producing the same |
| WO2015125206A1 (en) * | 2014-02-18 | 2015-08-27 | 日産自動車株式会社 | Exhaust gas purification catalyst and production method thereof |
-
1996
- 1996-09-19 JP JP8248174A patent/JPH1085611A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002535229A (en) * | 1998-12-28 | 2002-10-22 | コーニング インコーポレイテッド | High strength and high surface area alumina ceramic |
| US6468374B1 (en) * | 1999-02-18 | 2002-10-22 | Corning Incorporated | Method of making silica glass honeycomb structure from silica soot extrusion |
| JP2010179267A (en) * | 2009-02-07 | 2010-08-19 | Kosei:Kk | Support, and method of producing the same |
| WO2015125206A1 (en) * | 2014-02-18 | 2015-08-27 | 日産自動車株式会社 | Exhaust gas purification catalyst and production method thereof |
| JPWO2015125206A1 (en) * | 2014-02-18 | 2017-03-30 | 日産自動車株式会社 | Exhaust gas purification catalyst and method for producing the same |
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