JP2013234109A - ベータ型ゼオライト及びその製造方法 - Google Patents
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000010457 zeolite Substances 0.000 title claims abstract description 110
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 106
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000013078 crystal Substances 0.000 claims abstract description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000011541 reaction mixture Substances 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000002250 absorbent Substances 0.000 abstract 1
- 230000002745 absorbent Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 239000004110 Zinc silicate Substances 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 9
- 235000019352 zinc silicate Nutrition 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 6
- -1 tetraethylammonium ions Chemical class 0.000 description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- 238000001354 calcination Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel 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
- 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 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 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
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Abstract
【解決手段】本発明のベータ型ゼオライトは、(i)SiO2/Al2O3比が8〜30
であり、かつSiO2/ZnO比が8〜1000であり、(ii)ミクロ孔表面積が300〜800m2/gであり、(iii)ミクロ孔容積が0.1〜0.3cm3/gであり、(iv)合成したままの状態で直径が2〜6nmであり、その容積が0.001〜0.3cm3/gであるメソ孔を有することを特徴とする。このベータ型ゼオライトは、シリカ源、アルミナ源、アルカリ源、及び水を含む反応混合物に、ジンコシリケートベータ型ゼオライトを種結晶として添加して反応させることで好適に製造される。
【選択図】図3
Description
(ii)ミクロ孔表面積が300〜800m2/gであり、
(iii)ミクロ孔容積が0.1〜0.3cm3/gであり、
(iv)合成したままの状態で直径が2〜6nmであり、その容積が0.001〜0.3cm3/gであるメソ孔を有する、ことを特徴とするベータ型ゼオライトを提供するものである。
(1)以下に示すモル比で表される組成の反応混合物となるように、シリカ源、アルミナ源、アルカリ源、及び水を混合し、
SiO2/Al2O3=8〜300
Na2O/SiO2=0.05〜0.6
H2O/SiO2=5〜50
(2)SiO2/ZnO比が4〜50であり、かつSiO2/Al2O3比が4以上であり、かつ平均粒子径が100nm以上であるベータ型ゼオライトを、焼成することなく種結晶として用い、これを、前記反応混合物中のシリカ成分に対して0.1〜20重量%の割合で該反応混合物に添加し、
(3)前記種結晶が添加された前記反応混合物を80〜200℃で密閉加熱する、ことを特徴とするベータ型ゼオライトの製造方法を提供するものである。
・文献1:J. Phys. Chem., B 1999, 103, 2674-2679
・文献2:Topics in Catalysis 9 (1999), 35-42
・文献3:Chem. Eur. J. 2002, 8, No.22, 5153-5160
SiO2/Al2O3=8〜300
Na2O/SiO2=0.05〜0.6
H2O/SiO2=5〜50
SiO2/Al2O3=20〜300
Na2O/SiO2=0.1〜0.5
H2O/SiO2=10〜30
成分の和として計算される。
組成分析装置:(株)バリアン製、ICP−AES LIBERTY SeriesII
走査型電子顕微鏡:(株)日立ハイテクノロジーズ社製、電界放出型走査電子顕微鏡 S−4800
BET表面積測定装置:(株)カンタクローム インスツルメンツ社製 AUTOSORB−1
(1)種結晶の合成
テトラエチルアンモニウムヒドロキシド(TEAOH)をOSDAとして用いた。また、二酢酸亜鉛二水和物を亜鉛源として用い、微粉状シリカ(Cab−O−Sil、M−5)をシリカ源として用いた。更に水酸化リチウム、水酸化ナトリウムを用いた。これらの原料のうち、TEAOH、水酸化リチウム及び水酸化ナトリウムを水に溶解させた後、二酢酸亜鉛二水和物を添加し、次いで微粉状シリカを添加して2時間撹拌した。このようにして得られた反応混合物の組成は、水酸化リチウムが0.05M、TEAOHが0.65M、二酢酸亜鉛二水和物が0.03M、微粉状シリカが1M、水が30Mであった。この反応混合物をポリ四フッ化エチレンの内張を有するステンレス製のオートクレーブ内に入れ、静止状態下に150℃で96時間にわたり加熱した。この加熱によってSiO2/ZnO比が13.1であり、SiO2/Al2O3比が無限大であるジンコシリケートベータ型ゼオライトを合成した。このベータ型ゼオライトの未焼成でのX線回折図を図1に示す。このベータ型ゼオライトを走査型電子顕微鏡で観察したところ平均粒子径は640nmであった。このベータ型ゼオライトの結晶を未焼成のまま種結晶として使用した。
純水4.759gに、アルミン酸ナトリウム0.036gと36%水酸化ナトリウム水溶液1.284gを溶解して水溶液を得た。微粉状シリカ(Cab−O−Sil、M−5) 0.937gと、0.094gの種結晶とを混合したものを、前記の水溶液に少しずつ添加して撹拌混合した。混合後のゲルの組成は、表1に示すとおりであった。また種結晶の添加量は、ゲル中のシリカ成分に対して10%であった。ゲルと種結晶の混合物を23ccのステンレス製密閉容器に入れて、熟成及び撹拌することなしに140℃で2日間、自生圧力下で静置加熱した。密閉容器を冷却後、生成物をろ過、水洗浄して白色粉末を得た。この生成物のX線回折の結果、この生成物は不純物を含まないベータ型ゼオライトであることが確認された。未焼成品のX線回折図を図2に示す。また、液体窒素温度における窒素吸着等温線(図3)から、表1に示すような特徴を有するミクロ孔とメソ孔を併せ持つことが確認された。細孔特性を表す数値を表1に示す。
種結晶として、TEAOHをOSDAとして用いて合成したアルミノシリケートベータ型ゼオライトの焼成品を用いた。このベータ型ゼオライトは、SiO2/Al2O3比が24.0であり、ZnOを含有しないものであった。実施例1で用いたものと同じ原料を用いて調製した反応混合物(ゲル)に、この種結晶を添加した。ゲルの組成は表2に示すとおりである。種結晶を含むゲルを表2に示す条件で加熱してベータ型ゼオライトの結晶化を行った。得られた生成物をろ過、水洗浄して白色粉末を得た。この生成物のX線回折の結果、この生成物は不純物を含まないベータ型ゼオライトであることが確認された。しかし、液体窒素温度における窒素吸着等温線から、メソ孔が全く存在しないことが確認された。
種結晶として、比較例1で用いたアルミノシリケートベータ型ゼオライトの焼成品を用いた。この種結晶を、表2に示す組成の反応混合物(ゲル)に添加し、表2に示す条件で加熱してベータ型ゼオライトの結晶化を行った。得られた生成物をろ過、水洗浄して白色粉末を得た。この生成物のX線回折の結果、この生成物は不純物を含まないベータ型ゼオライトであることが確認された。しかし、液体窒素温度における窒素吸着等温線から、メソ孔が全く存在しないことが確認された。
種結晶として、実施例2で用いた未焼成のジンコシリケートベータ型ゼオライトの焼成品(空気中、550℃、10時間)を用いた。これ以外は実施例2と同じ組成及び条件で反応を行った。得られた生成物をろ過、水洗浄して白色粉末を得た。この生成物のX線回折の結果、この生成物はアモルファスであった。
Claims (4)
- (i)SiO2/Al2O3比が8〜30であり、かつSiO2/ZnO比が8〜1000であり、
(ii)ミクロ孔表面積が300〜800m2/gであり、
(iii)ミクロ孔容積が0.1〜0.3cm3/gであり、
(iv)合成したままの状態で直径が2〜6nmであり、その容積が0.001〜0.3cm3/gであるメソ孔を有する、ことを特徴とするベータ型ゼオライト。 - (1)以下に示すモル比で表される組成の反応混合物となるように、シリカ源、アルミナ源、アルカリ源、及び水を混合し、
SiO2/Al2O3=8〜300
Na2O/SiO2=0.05〜0.6
H2O/SiO2=5〜50
(2)SiO2/ZnO比が4〜50であり、かつSiO2/Al2O3比が4以上であり、かつ平均粒子径が100nm以上であるベータ型ゼオライトを、焼成することなく種結晶として用い、これを、前記反応混合物中のシリカ成分に対して0.1〜20重量%の割合で該反応混合物に添加し、
(3)前記種結晶が添加された前記反応混合物を80〜200℃で密閉加熱する、ことを特徴とするベータ型ゼオライトの製造方法。 - 反応混合物を加熱する前に、20〜100℃の温度下に熟成する請求項2に記載の製造方法。
- 密閉加熱する工程で反応混合物を撹拌する請求項1ないし3のいずれか一項に記載の製造方法。
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