JP3653383B2 - Method for producing silica-containing alumina molded body - Google Patents
Method for producing silica-containing alumina molded body Download PDFInfo
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- JP3653383B2 JP3653383B2 JP36715897A JP36715897A JP3653383B2 JP 3653383 B2 JP3653383 B2 JP 3653383B2 JP 36715897 A JP36715897 A JP 36715897A JP 36715897 A JP36715897 A JP 36715897A JP 3653383 B2 JP3653383 B2 JP 3653383B2
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- Prior art keywords
- silica
- alumina
- acid
- molded body
- aqueous solution
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 136
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 92
- 239000000377 silicon dioxide Substances 0.000 title claims description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 239000000017 hydrogel Substances 0.000 claims description 22
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 10
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims description 9
- 235000012209 glucono delta-lactone Nutrition 0.000 claims description 9
- 239000000182 glucono-delta-lactone Substances 0.000 claims description 9
- 229960003681 gluconolactone Drugs 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 229920000620 organic polymer Polymers 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000174 gluconic acid Substances 0.000 claims description 6
- 235000012208 gluconic acid Nutrition 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims description 2
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 claims description 2
- 125000005624 silicic acid group Chemical group 0.000 claims description 2
- 239000011148 porous material Substances 0.000 description 30
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000007704 transition Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 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 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000176 sodium gluconate Substances 0.000 description 3
- 235000012207 sodium gluconate Nutrition 0.000 description 3
- 229940005574 sodium gluconate Drugs 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- -1 alkali metal aluminates Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 125000000422 delta-lactone group Chemical group 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 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 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Description
【０００１】
【発明の属する技術分野】
本発明は、触媒担体、吸着剤、充填剤などに適した、α−アルミナへの相転移が起こりにくく、シャープな細孔分布を有するシリカ含有アルミナ成形体の製造方法に関するものである。
【０００２】
【従来の技術】
アルミナ成形体は各種触媒担体、吸着剤、充填剤等多くの分野で利用されている。この場合、それぞれの使用目的にあった表面積、細孔容積、細孔径、細孔分布や優れた耐熱性などが要求される。しかし、通常、触媒担体などに使用されるγ―アルミナなどの活性アルミナは熱安定性が低く、１０００℃付近でα―アルミナへ相転移し、表面積等が著しく低下し、触媒担体としての機能が失われるなどの問題があった。
【０００３】
一般に、γ―アルミナからα―アルミナへの相転移温度はγ―アルミナにシリカを添加すれば上昇し、高温下でもγ―アルミナの高い表面積を維持しうることが知られている。しかし、α―アルミナへの相転移率を小さくするためには、シリカの添加量を多くしなければならず、そのためにアルミナの特性が損なわれるという問題があった。
【０００４】
また、一方シャ−プな細孔分布を有するアルミナ成形体ついても種々の提案がされている。例えば、特開平７−２６７６３２号公報には、高い比表面積を有し、孔径分布がシャ−プであり、しかも、耐熱性に優れたγ―アルミナ多孔体を製造する方法が記載されており、その方法は、カオリン鉱物および／またはアルミナ−シリカ系共沈ゲルを加熱して、スピネル相と非晶質シリカとに相分離された熱処理物をアルカリまたはフッ酸により処理して非晶質シリカを溶出させることを特徴とするものである。しかし、この方法ではスピネル相と非晶質シリカとに相分離するので、９００〜１２００℃の温度で加熱することが必要となり、製造コストが高くなるという欠点があった。
【０００５】
【発明が解決しようとする課題】
本発明の目的は、シャープな細孔分布を有し、耐熱性に優れ、かつα−アルミナへの相転移が起きにくく、シリカ含有量の少ないアルミナ成形体の製造方法を提供する点にある。
【０００６】
【課題を解決するための手段】
本発明の第１は、（ａ）アルミナ基準で２〜１５ｗｔ％の可溶性カルボン酸の存在下に、可溶性アルミニウム塩水溶液と塩基性水溶液を反応させて擬ベーマイトアルミナヒドロゲルを生成させる工程、
（ｂ）該アルミナヒドロゲルを洗浄して副生塩を除去し、アルミナ中のアルカリ金属を酸化物として１．０ｗｔ％以下にする工程、
（ｃ）洗浄したアルミナヒドロゲルに
（イ）シリカ成分および
（ロ）アジピン酸、マロン酸エチル、フタル酸、安息香酸、トリメシン酸、グルタミン
酸、グルコン酸（グルコノ−δ−ラクトン）よりなる群から選ばれた有機高分子酸
を添加し、加熱熟成する工程、
（ｄ）前記（ｃ）工程で得られた熟成スラリーを押出成型が可能な状態に水分調整し、押出成形する工程、
（ｅ）成形された成形体を乾燥し、次いで焼成してシリカ含有アルミナ成形体とする工程、からなることを特徴とするシリカ含有アルミナ成形体の製造方法に関する。
【０００７】
本発明の第２は、（Ａ）アルミナ基準で２〜１５ｗｔ％の可溶性カルボン酸とシリカ成分の存在下に、可溶性アルミニウム塩水溶液と塩基性水溶液を反応させて擬ベーマイトアルミナヒドロゲルを生成させる工程、
（Ｂ）シリカを含有する該アルミナヒドロゲルを洗浄して副生塩を除去し、アルミナ中のアルカリ金属を酸化物として１．０ｗｔ％以下にする工程、
（Ｃ）洗浄済のシリカ含有アルミナヒドロゲルに、アジピン酸、マロン酸エチル、フタル酸、安息香酸、トリメシン酸、グルタミン酸、グルコン酸（グルコノ−δ−ラクトン）よりなる群から選ばれた有機高分子酸を添加し、加熱熟成する工程、
（Ｄ）前記（Ｃ）工程で得られた熟成スラリーを押出成型が可能な状態に水分調整し、押出成形する工程、
（Ｅ）成形された成形体を乾燥し、次いで焼成してシリカ含有アルミナ成形体とする工程、からなることを特徴とするシリカ含有アルミナ成形体の製造方法に関する。
【０００８】
本発明の第３は、前記シリカ成分が珪酸液、及び／又はシリカ粒子径が５０ｎｍ以下のシリカゾルであることを特徴とする請求項１または２記載のシリカ含有アルミナ成形体の製造方法に関する。
【０００９】
本発明のシリカ含有アルミナ成形体は、全細孔容積が０．３０ｍｌ／ｇ以上、好ましくは、０．４０〜１．００ｍｌ／ｇの範囲にあり、細孔直径１００Å以上の細孔容積が０．１０ｍｌ／ｇ以下、好ましくは０〜０．０５ｍｌ／ｇの範囲にあって、窒素吸脱着法（ＢＪＨ法）で求めた細孔分布における、平均細孔直径が３５〜８０Åの範囲にあり、平均細孔直径（Å）±５Åの占める細孔容積が全細孔容積の６０％以上、好ましくは７０％以上、更に好ましくは８０〜１００％の範囲で、表面積が２５０ｍ2／ｇ以上、好ましくは、３００〜６００ｍ2／ｇの範囲にある。さらに、本発明のシリカ含有アルミナ成形体は、α―アルミナへの相転移率が２０％以下、好ましくは０〜１５％の範囲である。なお、本発明でのα―アルミナへの相転移率は、試薬特級α―アルミナのＸ―線回折強度から２θが２５．６度、３５．１度、３７．８度、４３．３度、５２．５度、５７．４度におけるピーク・ハイを１００として、シリカ含有アルミナを１０５０℃で３時間焼成した試料の２θがそれぞれの角度におけるピーク・ハイの相対比（％）で求めた。
【００１０】
シリカ含有アルミナ成形体の全細孔容積が０．３０ｍｌ／ｇ未満の場合は触媒担体、吸着剤等としての性能が不十分になり、細孔直径１００Å以上の細孔容積が０．１０ｍｌ／ｇより大きくなると成形体の機械的強度が弱くなる傾向にあるので好ましくない。また、表面積が２５０ｍ2／ｇよりも小さい場合にも触媒担体、吸着剤等としての性能が不十分になる傾向にある。
【００１１】
前述のシリカ含有アルミナ成形体のシリカ含有量は、０．１〜５．０ｗｔ％の範囲であることが好ましい。シリカ含有量が０．１ｗｔ％より少ない場合には、α―アルミナへの相転移率が高くなる傾向にあり、また、５．０ｗｔ％より多い場合には、アルミナ自体の特性が薄らぎ、押出成形する際に成形性が困難になる傾向にある。シリカ含有アルミナ成形体のシリカ含有量は、さらに好ましくは１〜３ｗｔ％の範囲が望ましい。
【００１２】
前述のシリカ含有アルミナ成形体は、前記第２発明または第３発明の製造方法により得ることができる。以下、製造方法について詳述する。
【００１３】
本発明での可溶性カルボン酸としては、グルコン酸、コハク酸、シュウ酸、クエン酸、マロン酸、酒石酸、アジピン酸等が好適に使用できる。
【００１４】
前記、可溶性アルミニウム塩水溶液としては、硫酸アルミニウム、硝酸アルミニウム、塩化アルミニウム、酢酸アルミニウムなどの水溶液が使用可能である。また、前記、塩基性水溶液としては、アルミン酸ナトリウム、アルミン酸カリウムなどのアルミン酸アルカリ金属、苛性ソーダ、苛性カリウムなどのアルカリ金属水酸化物、および／またはアンモニアなどの水溶液が使用可能である。
【００１５】
本発明で使用されるシリカ成分としては、水硝子、珪酸液、シリカゾル、アルコキシシランなどが例示される。特に、洗浄したアルミナヒドロゲルに添加するシリカ成分としては、アルカリ金属などの不純分を含まない、珪酸液、シリカゾルなどが好ましい。シリカゾルでは、分散質のシリカ粒子の粒子径が５０ｎｍ以下、好ましくは、４〜４０ｎｍの範囲にあるゾルが望ましい。シリカ粒子の粒子径が小さいゾルは少量の添加量でα―アルミナへの相転を抑制する効果が大きいので望ましい。
【００１６】
本発明では、前述の可溶性アルミニウム塩水溶液と塩基性水溶液を可溶性カルボンまたは可溶性カルボンとシリカ成分の存在下に反応させて得られた擬ベーマイトアルミナヒドロゲルは、例えばアンモニア水を掛けながら濾過洗浄して副生塩を除去し、アルミナ中のアルカリ金属を酸化物として１．０ｗｔ％以下、好ましくは０．５ｗｔ％以下にすることが望ましい。
【００１７】
次いで、洗浄されたアルミナヒドロゲルは、シリカ成分および有機高分子酸、または有機高分子酸を添加したあと、加熱熟成される。
【００１８】
有機高分子酸としては、例えば、アジピン酸、マロン酸エチルなどのアルキルカルボン酸、フタル酸、安息香酸、トリメシン酸などの芳香族系カルボン酸、グルタミン酸、グルコン酸（グルコノーδ―ラクトン）などのタンパク質・糖類誘導カルボン酸などが例示される。有機高分子酸の添加は、得られるシリカ含有アルミナ成形体の細孔分布をシャープにし、平均細孔直径を小さい方向に制御する作用を有し、添加量はアルミナに対し１〜１０ｗｔ％の範囲が望ましい。また、本発明での加熱熟成は、５０℃以上、好ましくは、８０〜２００℃の温度で１〜１００時間、撹拌下にあるいは撹拌なしに、行うことが望ましい。
【００１９】
本発明における加熱熟成された熟成スラリー（シリカ含有アルミナヒドロゲル）は、公知の方法、例えば、熟成スラリーを噴霧乾燥して得られた粉末に水を加えて水分調整する方法、あるいは熟成スラリーを加熱捏和して成形可能な捏和物にする方法などにより押出成形が可能な状態に水分調整し、押出成形する。成形体の形状としては、円柱状、ハニカム状、三葉状など任意の形状に選択される。
【００２０】
前述の方法で得られた成形品は、通常の方法で、乾燥、焼成、例えば、４００〜８００℃で０．５〜１０時間焼成してシリカ含有アルミナ成形体を得る。
【００２１】
【実施例】
以下に実施例を示し本発明を具体的説明するが、本発明はこれらに限定されるものではない。
【００２２】
実施例１
Ａｌ2Ｏ3としての濃度が２２ｗｔ％のアルミン酸ソーダ水溶液１８．１８Ｋｇに２６ｗｔ％のグルコン酸ソーダ２．３１Ｋｇと純水５９．５１Ｋｇを加えて５７℃に加温した水溶液（ｉ）を調製した。Ａｌ2Ｏ3としての濃度が７ｗｔ％の硫酸アルミニウム水溶液２８．５７Ｋｇに純水５１．４３Ｋｇを加えて希釈し５７℃に加温した水溶液を前記水溶液（ｉ）に添加して擬ベーマイトアルミナヒドロゲルを生成させた。次いで、この擬ベーマイトアルミナヒドロゲルを濃度０．３ｗｔ％アンモニア水をかけながら濾過洗浄した。得られた洗浄ケーキは、Ａｌ2Ｏ3基準でＮａ2Ｏが０．０５ｗｔ％、ＳＯ4が０．２０ｗｔ％残存していた。この洗浄ケーキをスラリー化したものに、グルコノデルタラクトン３００ｇ（Ａｌ2Ｏ3基準で５ｗｔ％）と珪酸液をシリカとして１８６ｇ（Ａｌ2Ｏ3基準で３ｗｔ％）を添加し、９５℃で１０時間撹拌しながら熟成した。この熟成スラリーを噴霧乾燥してシリカ含有アルミナ粉末を得た。このシリカ含有アルミナ粉末に純水を加えて捏和した後、径４ｍｍの円柱状に押出成形した。成形品は、５０℃で２４時間乾燥した後６００℃で２時間焼成してシリカ含有アルミナ成形体（イ）を得た。このシリカ含有アルミナ成形体（イ）の性状を表１に、また、これをＢＪＨ法で測定したときの細孔分布を図１に示す。図１から明らかなとおり、このシリカ含有アルミナ成形体（イ）はシャープな細孔分布を示す。
【００２３】
実施例２、３、４
実施例１において、珪酸液の代わりにシリカ粒子径がそれぞれ４．５ｎｍ、
８ｎｍ、１５ｎｍのシリカゾルをシリカとしてＡｌ2Ｏ3基準で２ｗｔ％添加した以外は実施例１と全く同様にしてシリカ含有アルミナ成形体（ロ）、（ハ）、（ニ）を得た。シリカ含有アルミナ成形体（ロ）、（ハ）、（ニ）の性状を表１に示す。
【００２４】
実施例５
Ａｌ2Ｏ3としての濃度が２２ｗｔ％のアルミン酸ソーダ水溶液１８．１８Ｋｇに２６ｗｔ％のグルコン酸ソーダ２．３１Ｋｇと純水５９．５１Ｋｇを加えて５７℃に加温した水溶液を調製した。この水溶液に濃度１ｗｔ％に希釈した３号水硝子（Ａｌ2Ｏ3基準で３ｗｔ％）を添加し、水溶液（ii）を調製した。Ａｌ2Ｏ3としての濃度が７ｗｔ％の硫酸アルミニウム水溶液２８．５７Ｋｇに純水５１．４３Ｋｇを加えて希釈し５７℃に加温した水溶液を前記水溶液（ii）に添加して擬ベーマイトアルミナヒドロゲルを生成させた。次いで、この擬ベーマイトアルミナヒドロゲルを濃度０．３ｗｔ％のアンモニア水をかけながら濾過洗浄した。得られた洗浄ケーキは、Ａｌ2Ｏ3基準でＮａ2Ｏが０．０８ｗｔ％、ＳＯ4が０．０１ｗｔ％残存していた。この洗浄ケーキをスラリー化したものに、アジピン酸（Ａｌ2Ｏ3基準で１０ｗｔ％）を添加し、９５℃で１０時間撹拌しながら熟成した。得られた熟成スラリーを使用して、実施例１と同様にしてシリカ含有アルミナ成形体（ホ）を得た。シリカ含有アルミナ成形体（ホ）の性状を表１に示す。
【００２５】
下記表１および２中、ＧＲはグルコノデルタラクトンを指し、シリカゾルの項の括弧内はシリカ粒子径を示す。また＊の特定細孔直径とは、全細孔容積に対する「平均細孔直径（Å）±５Åの占める細孔容積」の割合（％）を示す。
【００２６】
【表１】
比較例１
Ａｌ2Ｏ3としての濃度が２２ｗｔ％のアルミン酸ソーダ水溶液１８．１８Ｋｇに２６ｗｔ％のグルコン酸ソーダ２．３１Ｋｇと純水５９．５１Ｋｇを加えて５７℃に加温した水溶液（iii）を調製した。Ａｌ2Ｏ3としての濃度が７ｗｔ％の硫酸アルミニウム水溶液２８．５７Ｋｇに純水５１．４３Ｋｇを加えて希釈し５７℃に加温した水溶液を前記水溶液（iii）に添加して擬ベーマイトアルミナヒドロゲルを生成させた。次いで、この擬ベーマイトアルミナヒドロゲルを濃度０．３ｗｔ％アンモニア水をかけながら濾過洗浄した。得られた洗浄ケーキは、Ａｌ2Ｏ3基準でＮａ2Ｏが０．０５ｗｔ％、ＳＯ4が０．２４ｗｔ％残存していた。この洗浄ケーキをスラリー化したものに、グルコノデルタラクトン３００ｇ（Ａｌ2Ｏ3基準で５ｗｔ％）を添加し、９５℃で１０時間撹拌しながら熟成した。この熟成スラリーを噴霧乾燥してアルミナ粉末を得た。このアルミナ粉末に純水を加えて、さらにＡｌ2Ｏ3基準で３ｗｔ％に相当する珪酸液を添加して加熱捏和した後、径４ｍｍの円柱状に押出成形した。成形品は、実施例１と同様にしてシリカ含有アルミナ成形体（ヘ）を得た。このシリカ含有アルミナ成形体（ヘ）の性状を表２に示す。
【００２８】
比較例２
実施例１において、珪酸液を添加しなかった以外は実施例１と全く同様にしてアルミナ成形体（ト）を得た。アルミナ成形体（ト）の性状を表２に示す。
【００２９】
比較例３
実施例１において、グルコノデルタラクトンを添加しなかった以外は実施例１と全く同様にしてシリカ含有アルミナ成形体（チ）を得た。シリカ含有アルミナ成形体（チ）の性状を表２に示す。
【００３０】
比較例４
実施例１において、グルコノデルタラクトンと珪酸液を添加しなかった以外は実施例１と全く同様にしてアルミナ成形体（リ）を得た。アルミナ成形体（リ）の性状を表２に示す。
【００３１】
【表２】
【発明の効果】
本発明の製造方法で得られたシリカ含有アルミナ成形体は、細孔直径１００Å以上の細孔容積が少なく、細孔分布がシャープであり、熱安定性に優れているため、各種触媒担体、吸着剤、充填剤等に有用である。
【図面の簡単な説明】
【図１】実施例１におけるシリカ含有アルミナ成形体（イ）のＢＪＨ法による細孔分布を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention is a catalyst carrier, adsorbent, suitable for such fillers, the phase transition hardly occurs to the α- alumina, a process for producing a silica-containing alumina compact having a sharp pore distribution.
[0002]
[Prior art]
Alumina molded bodies are used in many fields such as various catalyst carriers, adsorbents, and fillers. In this case, a surface area, a pore volume, a pore diameter, a pore distribution, excellent heat resistance, etc. suitable for each purpose of use are required. However, activated alumina such as γ-alumina usually used for catalyst carriers has low thermal stability, phase transition to α-alumina near 1000 ° C., surface area and the like are remarkably reduced, and the function as a catalyst carrier is reduced. There were problems such as being lost.
[0003]
In general, it is known that the phase transition temperature from γ-alumina to α-alumina increases when silica is added to γ-alumina, and the high surface area of γ-alumina can be maintained even at high temperatures. However, in order to reduce the phase transition rate to α-alumina, the amount of silica added has to be increased, which causes a problem that the characteristics of alumina are impaired.
[0004]
Various proposals have also been made for an alumina molded body having a sharp pore distribution. For example, JP-A-7-267632 describes a method for producing a γ-alumina porous body having a high specific surface area, a pore size distribution that is sharp, and excellent in heat resistance, In the method, a kaolin mineral and / or an alumina-silica coprecipitated gel is heated, and the heat-treated product phase-separated into a spinel phase and an amorphous silica is treated with an alkali or hydrofluoric acid. It is characterized by elution. However, in this method, the spinel phase and the amorphous silica are phase-separated, so that it is necessary to heat at a temperature of 900 to 1200 ° C., and the production cost is increased.
[0005]
[Problems to be solved by the invention]
An object of the present invention have a sharp pore distribution, excellent heat resistance, and α- phase transition hardly occurs to the alumina, in that it provides a method of manufacturing a small alumina molded article having silica content.
[0006]
[Means for Solving the Problems]
The first of the present invention is: (a) a step of reacting a soluble aluminum salt aqueous solution with a basic aqueous solution in the presence of 2 to 15 wt% soluble carboxylic acid based on alumina to produce a pseudo boehmite alumina hydrogel,
(B) The alumina hydrogel is washed to remove by-product salts, and the alkali metal in alumina is reduced to 1.0 wt% or less as an oxide,
(C) To the washed alumina hydrogel
(A) Silica component and
(B) Adipic acid, ethyl malonate, phthalic acid, benzoic acid, trimesic acid, glutamine
Organic polymer acid selected from the group consisting of acid and gluconic acid (glucono-δ-lactone)
Adding and aging by heating,
(D) a step of adjusting the moisture of the ripened slurry obtained in the step (c) to a state in which it can be extruded and extruding,
(E) It relates to a method for producing a silica-containing alumina molded body comprising the steps of drying the molded molded body and then firing to form a silica-containing alumina molded body .
[0007]
The second of the present invention is (A) a step of reacting a soluble aluminum salt aqueous solution with a basic aqueous solution in the presence of 2 to 15 wt% of a soluble carboxylic acid and a silica component based on alumina to produce a pseudo boehmite alumina hydrogel,
(B) washing the alumina hydrogel containing silica to remove by-product salts, and setting the alkali metal in alumina to 1.0 wt% or less as an oxide;
(C) Organic polymer acid selected from the group consisting of washed silica-containing alumina hydrogel and adipic acid, ethyl malonate, phthalic acid, benzoic acid, trimesic acid, glutamic acid and gluconic acid (glucono-δ-lactone) Adding and aging by heating,
(D) Adjusting the moisture of the ripened slurry obtained in the step (C) so that it can be extruded and extruding it,
(E) It is related with the manufacturing method of the silica containing alumina molded object characterized by consisting of the process which dries the shape | molded molded object and then bakes and makes a silica containing alumina molded object .
[0008]
A third aspect of the present invention relates to the method for producing a silica-containing alumina molded body according to claim 1 or 2 , wherein the silica component is a silicic acid solution and / or a silica sol having a silica particle diameter of 50 nm or less .
[0009]
The silica-containing alumina molded body of the present invention has a total pore volume of 0.30 ml / g or more, preferably in the range of 0.40 to 1.00 ml / g, and a pore volume of 100 or more pore diameters of 0 or more. .10 ml / g or less, preferably in the range of 0 to 0.05 ml / g, the average pore diameter in the pore distribution determined by the nitrogen adsorption / desorption method (BJH method) is in the range of 35 to 80 mm, The pore volume occupied by the average pore diameter (Å) ± 5Å is 60% or more of the total pore volume, preferably 70% or more, more preferably 80 to 100%, and the surface area is 250 m 2 / g or more, preferably Is in the range of 300-600 m 2 / g. Furthermore, the silica-containing alumina molded body of the present invention has a phase transition rate to α-alumina of 20% or less, preferably 0 to 15%. The phase transition rate to α-alumina in the present invention is 25.6 °, 35.1 °, 37.8 °, 43.3 °, 2θ from the X-ray diffraction intensity of the reagent-grade α-alumina. The peak height at 52.5 degrees and 57.4 degrees was taken as 100, and 2θ of the sample obtained by firing the silica-containing alumina at 1050 ° C. for 3 hours was determined by the relative ratio (%) of the peak height at each angle.
[0010]
When the total pore volume of the silica-containing alumina molded body is less than 0.30 ml / g, the performance as a catalyst carrier, an adsorbent, etc. is insufficient, and the pore volume with a pore diameter of 100 mm or more is 0.10 ml / g. A larger value is not preferable because the mechanical strength of the molded product tends to be weak. Further, when the surface area is smaller than 250 m 2 / g, the performance as a catalyst carrier, an adsorbent and the like tends to be insufficient.
[0011]
The silica content of the silica-containing alumina molded body is preferably in the range of 0.1 to 5.0 wt%. When the silica content is less than 0.1 wt%, the phase transition rate to α-alumina tends to be high. When the silica content is more than 5.0 wt%, the characteristics of the alumina itself are thinned and extrusion molding is performed. When forming, the formability tends to be difficult. The silica content of the silica-containing alumina molded body is more preferably in the range of 1 to 3 wt%.
[0012]
The silica-containing alumina molded body described above can be obtained by the production method of the second invention or the third invention. Hereinafter, a manufacturing method is explained in full detail.
[0013]
As the soluble carboxylic acid in the present invention, gluconic acid, succinic acid, oxalic acid, citric acid, malonic acid, tartaric acid, adipic acid and the like can be suitably used.
[0014]
As the soluble aluminum salt aqueous solution, an aqueous solution of aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum acetate or the like can be used. As the basic aqueous solution, alkali metal aluminates such as sodium aluminate and potassium aluminate, alkali metal hydroxides such as caustic soda and caustic potassium, and / or aqueous solutions such as ammonia can be used.
[0015]
Examples of the silica component used in the present invention include water glass, silicic acid solution, silica sol, and alkoxysilane. In particular, the silica component added to the washed alumina hydrogel is preferably a silicic acid solution or silica sol that does not contain impurities such as alkali metals. As the silica sol, a sol having a particle size of dispersoidal silica particles of 50 nm or less, preferably in the range of 4 to 40 nm is desirable. A sol having a small silica particle diameter is desirable because it has a large effect of suppressing phase transformation to α-alumina with a small addition amount.
[0016]
In the present invention, the pseudoboehmite alumina hydrogel obtained by reacting the aforementioned aqueous solution of soluble aluminum salt and basic aqueous solution in the presence of soluble carboxylic acid or soluble carboxylic acid and silica component is filtered and washed with, for example, aqueous ammonia, and added as a secondary solution. It is desirable that the raw salt is removed and the alkali metal in alumina is 1.0 wt% or less, preferably 0.5 wt% or less as an oxide.
[0017]
Next, the washed alumina hydrogel is heated and aged after adding the silica component and the organic polymer acid or the organic polymer acid.
[0018]
Examples of organic polymer acids include alkylcarboxylic acids such as adipic acid and ethyl malonate, aromatic carboxylic acids such as phthalic acid, benzoic acid and trimesic acid, proteins such as glutamic acid and gluconic acid (glucono δ-lactone) -Examples include sugar-derived carboxylic acids. The addition of the organic polymer acid has the effect of sharpening the pore distribution of the resulting silica-containing alumina molded article and controlling the average pore diameter in a smaller direction, and the addition amount is in the range of 1 to 10 wt% with respect to the alumina. Is desirable. In addition, the heat aging in the present invention is desirably performed at a temperature of 50 ° C. or higher, preferably 80 to 200 ° C. for 1 to 100 hours with or without stirring.
[0019]
The heat-aged aging slurry (silica-containing alumina hydrogel) in the present invention is a known method, for example, a method of adjusting water by adding water to a powder obtained by spray-drying the aging slurry, or heating the aging slurry. The moisture is adjusted to a state where extrusion molding is possible by a method such as adding to a kneaded product, and extrusion molding is performed. The shape of the molded body is selected as an arbitrary shape such as a columnar shape, a honeycomb shape, or a trilobal shape.
[0020]
The molded product obtained by the above-described method is dried and fired, for example, at 400 to 800 ° C. for 0.5 to 10 hours by a usual method to obtain a silica-containing alumina molded body.
[0021]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0022]
Example 1
An aqueous solution (i) prepared by adding 2.31 kg of 26 wt% sodium gluconate and 59.51 kg of pure water to 18.18 kg of an aqueous solution of sodium aluminate having a concentration of 22 wt% as Al 2 O 3 and heating to 57 ° C. was prepared. . Aqueous boehmite alumina hydrogel was added to the aqueous solution (i) by adding 51.43 Kg of pure water to 28.57 Kg of aluminum sulfate aqueous solution having a concentration of 7 wt% as Al 2 O 3 and diluting and heating to 57 ° C. Generated. Next, this pseudo boehmite alumina hydrogel was filtered and washed while applying ammonia water having a concentration of 0.3 wt%. The obtained washed cake had 0.05 wt% Na 2 O and 0.20 wt% SO 4 on the basis of Al 2 O 3 . The washed cake obtained by slurrying, glucono (5 wt% in Al 2 O 3 basis) delta-lactone 300g and silicic acid solution was added 186 g (3 wt% in Al 2 O 3 basis) as silica, 10 at 95 ° C. The mixture was aged with stirring for a period of time. This aging slurry was spray-dried to obtain silica-containing alumina powder. The silica-containing alumina powder was kneaded with pure water, and then extruded into a cylindrical shape having a diameter of 4 mm. The molded product was dried at 50 ° C. for 24 hours and then calcined at 600 ° C. for 2 hours to obtain a silica-containing alumina molded body (I). Table 1 shows the properties of this silica-containing alumina molded body (I), and FIG. 1 shows the pore distribution when measured by the BJH method. As is clear from FIG. 1, this silica-containing alumina molded body (A) shows a sharp pore distribution.
[0023]
Examples 2, 3, 4
In Example 1, each silica particle diameter is 4.5 nm instead of silicic acid solution,
Silica-containing alumina molded bodies (B), (C), and (D) were obtained in the same manner as in Example 1 except that silica sols of 8 nm and 15 nm were added as silica and 2 wt% based on Al 2 O 3 . Table 1 shows the properties of the silica-containing alumina molded bodies (b), (c), and (d).
[0024]
Example 5
An aqueous solution prepared by adding 2.31 kg of 26 wt% sodium gluconate and 59.51 kg of pure water to 18.18 kg of an aqueous solution of sodium aluminate having a concentration of 22 wt% as Al 2 O 3 and heating to 57 ° C. was prepared. To this aqueous solution, No. 3 water glass diluted to a concentration of 1 wt% (3 wt% based on Al 2 O 3 ) was added to prepare an aqueous solution (ii). Aqueous boehmite alumina hydrogel was added to the aqueous solution (ii) by adding 51.43 Kg of pure water to 28.57 Kg of an aluminum sulfate aqueous solution having a concentration of 7 wt% as Al 2 O 3 and diluting and heating to 57 ° C. Generated. Next, this pseudo boehmite alumina hydrogel was washed by filtration while applying ammonia water having a concentration of 0.3 wt%. The obtained washed cake had 0.08 wt% Na 2 O and 0.01 wt% SO 4 remaining on the basis of Al 2 O 3 . Adipic acid (10 wt% based on Al 2 O 3 ) was added to the slurry of the washed cake and aged with stirring at 95 ° C. for 10 hours. Using the obtained aging slurry, a silica-containing alumina molded body (e) was obtained in the same manner as in Example 1. Table 1 shows the properties of the silica-containing alumina molded body (e).
[0025]
In Tables 1 and 2 below, GR indicates glucono delta lactone, and the parenthesis in the silica sol section indicates the silica particle diameter. The specific pore diameter of * indicates the ratio (%) of “average pore diameter (Å) ± pore volume occupied by 5Å” to the total pore volume.
[0026]
[Table 1]
Comparative Example 1
An aqueous solution (iii) was prepared by adding 2.31 kg of 26 wt% sodium gluconate and 59.51 kg of pure water to 18.18 kg of an aqueous solution of sodium aluminate having a concentration of 22 wt% as Al 2 O 3 and heating to 57 ° C. . Aqueous boehmite alumina hydrogel was added to the aqueous solution (iii) by adding 51.43 Kg of pure water to 28.57 Kg of an aluminum sulfate aqueous solution having a concentration of 7 wt% as Al 2 O 3 and diluting and heating to 57 ° C. Generated. Next, this pseudo boehmite alumina hydrogel was filtered and washed while applying ammonia water having a concentration of 0.3 wt%. The obtained washed cake had 0.05 wt% Na 2 O and 0.24 wt% SO 4 on the basis of Al 2 O 3 . To this slurry of the washed cake, 300 g of glucono delta lactone (5 wt% based on Al 2 O 3 ) was added and aged with stirring at 95 ° C. for 10 hours. This aging slurry was spray-dried to obtain alumina powder. Pure water was added to the alumina powder, and a silicic acid solution corresponding to 3 wt% on the basis of Al 2 O 3 was added and heat-kneaded, followed by extrusion molding into a cylindrical shape having a diameter of 4 mm. As the molded product, a silica-containing alumina molded body (f) was obtained in the same manner as in Example 1. Table 2 shows the properties of the silica-containing alumina molded body (f).
[0028]
Comparative Example 2
In Example 1, an alumina molded body (g) was obtained in the same manner as in Example 1 except that the silicic acid solution was not added. Table 2 shows the properties of the alumina molded body (g).
[0029]
Comparative Example 3
In Example 1, a silica-containing alumina molded body (H) was obtained in exactly the same manner as in Example 1 except that glucono delta lactone was not added. Table 2 shows the properties of the silica-containing alumina molded body (H).
[0030]
Comparative Example 4
In Example 1, an alumina molded body (Li) was obtained in exactly the same manner as in Example 1 except that glucono delta lactone and silicic acid solution were not added. Table 2 shows the properties of the molded alumina (Li).
[0031]
[Table 2]
【The invention's effect】
The silica-containing alumina molded body obtained by the production method of the present invention has a small pore volume with a pore diameter of 100 mm or more, a sharp pore distribution, and excellent thermal stability. Useful for agents, fillers and the like.
[Brief description of the drawings]
FIG. 1 is a graph showing the pore distribution of a silica-containing alumina molded body (I) in Example 1 by the BJH method.
Claims (3)
（ｂ）該アルミナヒドロゲルを洗浄して副生塩を除去し、アルミナ中のアルカリ金属を酸化物として１．０ｗｔ％以下にする工程、(B) washing the alumina hydrogel to remove by-product salts and reducing the alkali metal in the alumina to 1.0 wt% or less as an oxide;
（ｃ）洗浄したアルミナヒドロゲルに(C) To the washed alumina hydrogel
（イ）シリカ成分および(I) Silica component and
（ロ）アジピン酸、マロン酸エチル、フタル酸、安息香酸、トリメシン酸、グルタミン(B) Adipic acid, ethyl malonate, phthalic acid, benzoic acid, trimesic acid, glutamine
酸、グルコン酸（グルコノ−δ−ラクトン）よりなる群から選ばれた有機高分子酸Organic polymer acid selected from the group consisting of acid and gluconic acid (glucono-δ-lactone)
を添加し、加熱熟成する工程、Adding and aging by heating,
（ｄ）前記（ｃ）工程で得られた熟成スラリーを押出成型が可能な状態に水分調整し、押出成形する工程、(D) a step of adjusting the moisture of the ripened slurry obtained in the step (c) to a state where extrusion molding is possible, and performing extrusion molding;
（ｅ）成形された成形体を乾燥し、次いで焼成してシリカ含有アルミナ成形体とする工程、からなることを特徴とするシリカ含有アルミナ成形体の製造方法。(E) A method for producing a silica-containing alumina molded body comprising the steps of drying the molded molded body and then firing to form a silica-containing alumina molded body.
（Ｂ）シリカを含有する該アルミナヒドロゲルを洗浄して副生塩を除去し、アルミナ中のアルカリ金属を酸化物として１．０ｗｔ％以下にする工程、(B) washing the alumina hydrogel containing silica to remove by-product salts, and setting the alkali metal in alumina to 1.0 wt% or less as an oxide;
（Ｃ）洗浄済のシリカ含有アルミナヒドロゲルに、アジピン酸、マロン酸エチル、フタル酸、安息香酸、トリメシン酸、グルタミン酸、グルコン酸（グルコノ−δ−ラクトン）よりなる群から選ばれた有機高分子酸を添加し、加熱熟成する工程、(C) Organic polymer acid selected from the group consisting of washed silica-containing alumina hydrogel and adipic acid, ethyl malonate, phthalic acid, benzoic acid, trimesic acid, glutamic acid, gluconic acid (glucono-δ-lactone) Adding and aging by heating,
（Ｄ）前記（Ｃ）工程で得られた熟成スラリーを押出成型が可能な状態に水分調整し、押出成形する工程、(D) Adjusting the moisture to a state in which the aging slurry obtained in the step (C) can be subjected to extrusion molding, and extruding.
（Ｅ）成形された成形体を乾燥し、次いで焼成してシリカ含有アルミナ成形体とする工程、からなることを特徴とするシリカ含有アルミナ成形体の製造方法。(E) A method for producing a silica-containing alumina molded body comprising the steps of drying the molded molded body and then firing to form a silica-containing alumina molded body.
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| JP36715897A JP3653383B2 (en) | 1997-12-25 | 1997-12-25 | Method for producing silica-containing alumina molded body |
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| JP36715897A JP3653383B2 (en) | 1997-12-25 | 1997-12-25 | Method for producing silica-containing alumina molded body |
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| JPH11189409A JPH11189409A (en) | 1999-07-13 |
| JP3653383B2 true JP3653383B2 (en) | 2005-05-25 |
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| ATE280737T1 (en) * | 1999-08-11 | 2004-11-15 | Akzo Nobel Nv | QUASICRYSTALLINE BOEMITE CONTAINING NON-LANTHANIDE ADDITIVES |
| JP4756782B2 (en) * | 2001-07-12 | 2011-08-24 | 大明化学工業株式会社 | Method for producing α-alumina |
| EP1773969B1 (en) * | 2004-06-17 | 2015-08-12 | ExxonMobil Research and Engineering Company | Two-step hydroprocessing method for heavy hydrocarbon oil |
| SG11201403322XA (en) | 2011-12-22 | 2014-07-30 | Advanced Refining Technologies Llc | Silica containing alumina supports, catalysts made therefrom and processes using the same |
| KR101602693B1 (en) * | 2014-04-30 | 2016-03-14 | 전남대학교산학협력단 | Method for manufacturing alumina pellet |
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