CN104321280B - β型沸石及其制造方法 - Google Patents
β型沸石及其制造方法 Download PDFInfo
- Publication number
- CN104321280B CN104321280B CN201380018964.2A CN201380018964A CN104321280B CN 104321280 B CN104321280 B CN 104321280B CN 201380018964 A CN201380018964 A CN 201380018964A CN 104321280 B CN104321280 B CN 104321280B
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- Prior art keywords
- zeolite beta
- sio
- crystal seed
- ratio
- reactant mixture
- 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.)
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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 124
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 115
- 239000010457 zeolite Substances 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 28
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 28
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 28
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 28
- 239000000376 reactant Substances 0.000 claims abstract description 26
- 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 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 2
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000003463 adsorbent Substances 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 13
- 230000008025 crystallization Effects 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- 239000002912 waste gas Substances 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
- -1 Ethylammonium ions Chemical class 0.000 description 2
- 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
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000019795 sodium metasilicate 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
- 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
- 230000003068 static effect Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000010189 synthetic method Methods 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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000013019 agitation 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
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 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
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012407 engineering method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- COWOWCJDIGPUDT-UHFFFAOYSA-N silicic acid;zinc Chemical class [Zn].[Zn].O[Si](O)(O)O COWOWCJDIGPUDT-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
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- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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- B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
本发明提供一种兼具微孔及介孔、且作为催化剂或吸附剂等而有用的β型沸石及其制造方法。本发明的β型沸石的特征在于:(i)SiO2/Al2O3比为8~30,且SiO2/ZnO比为8~1000;(ii)微孔表面积为300m2/g~800m2/g;(iii)微孔体积为0.1cm3/g~0.3cm3/g;(iv)具有在合成后保持原样的状态下直径为2nm~6nm、其体积为0.001cm3/g~0.3cm3/g的介孔。所述β型沸石可以通过以下方式合适地制造:将硅酸锌盐β型沸石作为晶种添加到含有二氧化硅源、氧化铝源、碱源及水的反应混合物中,并进行反应。
Description
技术领域
本发明涉及一种β型沸石及其制造方法。
背景技术
合成沸石为结晶性铝硅酸盐(aluminosilicate),具有由其结晶结构所致的埃(angstrom)尺寸均匀的孔隙。发挥该特征,而将合成沸石在工业上用作仅吸附具有特定大小的分子的分子筛吸附剂或吸附亲和力强的分子的吸附分离剂、或者催化剂基剂。作为这种沸石之一的β型沸石目前在世界上被大量用作石油化学工业中的催化剂、以及作为汽车废气处理用吸附剂。
已提出了β型沸石的各种合成法。通常的方法为将四乙基铵离子等界面活性剂用作有机结构导向剂(以下简称为“OSDA(Organic StructureDirecting Agent)”)的方法。但是,含有四乙基铵离子的化合物价格昂贵,而且在β型沸石结晶化结束后基本上已分解,所以无法回收再利用。因此,利用该方法所制造的β型沸石价格昂贵。进而,因结晶中混入有四乙基铵离子,所以在用作吸附剂或催化剂时必须进行煅烧除去。此时的废气会引起环境污染,另外,为了对合成母液进行无害化处理,也需要大量的化学剂。像这样,使用四乙基铵离子的β型沸石的合成方法是不仅价格昂贵、而且环境负荷大的制造方法,因此期望实现不使用OSDA的制造方法。
因此,本申请人以前提出了不使用OSDA的β型沸石的制造方法(参照专利文献1)。根据该方法,有以下优点:在不使用OSDA的情况下,可以无限次地进行β型沸石的自我再生产。
然而,作为具有介孔范围的孔隙的多孔性结晶,已知以MCM-41为代表的介孔分子筛(mesoporous molecular sieve)。介孔分子筛的合成时仍使用OSDA,因此存在上文所述的不良状况。
现有技术文献
专利文献
专利文献1:日本专利特开2011-126768号公报
发明内容
[发明所欲解决的课题]
本发明的课题在于提供一种性能与上文所述的现有技术的β型沸石相比进一步提升的β型沸石及其制造方法。
[解决课题的手段]
本发明提供一种β型沸石,其特征在于:
(i)SiO2/Al2O3比为8~30,且SiO2/ZnO比为8~1000;
(ii)微孔表面积为300m2/g~800m2/g;
(iii)微孔体积为0.1cm3/g~0.3cm3/g;
(iv)具有在合成后保持原样的状态下直径为2nm~6nm、且其体积为0.001cm3/g~0.3cm3/g的介孔。
另外,本发明提供一种β型沸石的制造方法作为所述β型沸石的合适的制造方法,所述β型沸石的制造方法的特征在于:
(1)以成为以下所示的摩尔比所表示的组成的反应混合物的方式,将二氧化硅源、氧化铝源、碱源及水混合,
SiO2/Al2O3=8~300
Na2O/SiO2=0.05~0.6
H2O/SiO2=5~50;
(2)将SiO2/ZnO比为4~50、SiO2/Al2O3比为4以上、且平均粒径为100nm以上的β型沸石不加煅烧而用作晶种,将其以相对于所述反应混合物中的二氧化硅成分而为0.1重量%~20重量%的比例添加到所述反应混合物中;
(3)将添加有所述晶种的所述反应混合物在80℃~200℃下密闭加热。
[发明的效果]
本发明的β型沸石兼具微孔及介孔,作为催化剂、吸附剂、离子交换体及各种功能材料而有用。
附图说明
图1为实施例1中所用的硅酸锌盐β型沸石的未煅烧状态下的X射线衍射图。
图2为实施例1中所得的β型沸石的X射线衍射图。
图3为关于实施例1中所得的β型沸石的液态氮温度下的氮吸附等温线。
图4为实施例2中所得的β型沸石的X射线衍射图。
图5为实施例8中所得的β型沸石的X射线衍射图。
图6为关于实施例8中所得的β型沸石的液态氮温度下的氮吸附等温线。
图7为实施例10中所得的β型沸石的X射线衍射图。
图8为关于实施例10中所得的β型沸石的液态氮温度下的氮吸附等温线。
具体实施方式
本发明的β型沸石在兼具微孔及介孔的方面具有一个特征。虽然以前已知的β型沸石具有微孔,但迄今为止除了微孔以外也具有介孔的β型沸石尚不为人所知。而且,本发明的β型沸石具有铝硅酸盐骨架,且具有铝硅酸盐骨架中的一部分铝经锌置换的结构。像这样,本发明的β型沸石为迄今为止不为人所知的极其新颖的物质。此外,所谓微孔是指直径小于2nm的孔隙,所谓介孔是指直径为2nm以上且50nm以下的孔隙。
关于本发明的β型沸石所含的锌,若以SiO2/ZnO比来表示其含量则为8~1000,优选10~500,更优选10~350。通过将锌的含量设定为该范围内,可以维持β型沸石的骨架,并且容易地实现兼具微孔与介孔的结构。
另一方面,关于铝,若以SiO2/Al2O3比来表示其含量则为8~30,优选10~25,更优选10~22。通过将铝的含量设定在该范围内,可以容易地维持β型沸石的骨架。
本发明的β型沸石所含的锌及铝的量可以通过在后述的制造方法中调整凝胶组成、晶种中的锌的含量、凝胶与晶种的添加比例等来控制。
如上文所述,本发明的β型沸石兼具微孔与介孔,这些孔中,关于微孔,其体积具有0.1cm3/g~0.3cm3/g、优选0.11cm3/g~0.3cm3/g、更优选0.12cm3/g~0.3cm3/g的高的值。另外,微孔的表面积具有300m2/g~800m2/g、优选300m2/g~750m2/g、进而优选330m2/g~700m2/g的高的值。
另一方面,关于介孔,在合成后保持原样的状态下直径为2nm~6nm,优选2nm~5nm,进而优选3nm~5nm。关于介孔的体积,在合成后保持原样的状态下为0.001cm3/g~0.3cm3/g,优选0.003cm3/g~0.2cm3/g,更优选0.005cm3/g~0.1cm3/g。
具有如上所述的尺寸的微孔及介孔、且含有锌的本发明的β型沸石例如作为汽油引擎(gasoline engine)或柴油引擎(diesel engine)等内燃机的废气用净化催化剂、石油化学产品的合成催化剂、结构异构物的选择性合成催化剂、N2/O2吸附分离工艺(process)中的吸附剂、离子交换体及各种功能材料而有用。
以上对本发明的β型沸石中的微孔及介孔进行了说明,关于布厄特(Brunauer-Emmett-Tellern,BET)比表面积,本发明的β型沸石优选400m2/g~800m2/g,更优选500m2/g~800m2/g。
此外,本发明的β型沸石也包含钠型的β型沸石、及含有钠以外的碱金属离子或二价金属离子的β型沸石,进而也包含使钠离子与质子进行离子交换而成为H+型的β型沸石。在β型沸石为H+型的类型的情况下,所述各种物性的测定是利用钠离子将质子置换后进行。在将钠型的β型沸石转变成H+型时,例如将钠型的β型沸石分散在硝酸铵等铵盐水溶液中,将沸石中的钠离子与铵离子进行置换。通过对该铵型的β型沸石进行煅烧,可以获得H+型的β型沸石。
像后述实施例中所说明那样,所述比表面积或体积是使用利用氮吸附的表面积测定装置来进行测定。
然后,对本发明的β型沸石的合适的制造方法进行说明。该制造方法中,使用β型沸石的晶种,使其在具有特定组成的凝胶中成长,获得具有目标结构的β型沸石。
晶种是使用硅酸锌盐(zincosilicate)β型沸石。在使用该特殊的晶种的方面,具有本制造方法的一个特征。通过使用该晶种,可以由始至终良好地制造作为目标的兼具微孔及介孔的β型沸石。相对于此,即便使用通常的铝硅酸盐β型沸石,也无法获得具有目标结构的β型沸石。
硅酸锌盐β型沸石具有铝硅酸盐β型沸石中的全部或一部分铝经锌置换的结构。硅酸锌盐β型沸石为该技术领域中众所周知的物质,其制造方法等例如是记载于以下的文献1至文献3中。这些文献中,例如使用氢氧化四乙基铵作为OSDA来合成硅酸锌盐β型沸石。
·文献1:《物理化学期刊(J.Phys.Chem.)》(B 1999,103,2674-2679)
·文献2:《催化论题(Topics in Catalysis)》(9(1999),35-42)
·文献3:《欧洲化学(Chem.Eur.J.)》(2002,8,No.22,5153-5160)
关于该制造方法中用作晶种的硅酸锌盐β型沸石,SiO2/ZnO比为4~50,优选5~40,更优选8~30。另一方面,SiO2/Al2O3比为4以上,优选10以上,更优选13以上,进而优选20以上。SiO2/Al2O3比并无上限值。即,晶种中也可不含铝。另外,也可以使用含有铝及锌两者的硅酸锌盐β型沸石作为晶种。
晶种的平均粒径是设定为100nm以上,优选设定为100nm~2000nm、更优选200nm~1000nm。通过合成所得的沸石的结晶的大小通常不均匀,或者具有某种程度的粒径分布,难以求出其中具有最大频度的结晶粒径。所谓平均粒径,是指在利用扫描式电子显微镜的观察中最大频度的结晶的粒子直径。包含利用所述文献1至文献3中记载的方法所得的硅酸锌盐的β型沸石通常其平均粒径为100nm~1000nm的范围。但是,因小粒子凝聚所以粒径不明确,或者也存在超过1000nm的粒径。另外,为了合成小于100nm的粒子,需要特殊的工法,从而价格变昂贵。因此,本发明中使用平均粒径为100nm以上的β型沸石作为晶种。通过该制造方法所得的β型沸石也具有该范围的平均粒径,因此可以合适地用作晶种。
添加晶种的反应混合物是以成为以下所示的摩尔比所表示的组成的方式将二氧化硅源、氧化铝源、碱源及水混合而获得。通过使用该组成的反应混合物,且使用所述硅酸锌盐β型沸石的晶种,方可获得作为目标的具有微孔及介孔的β型沸石。
SiO2/Al2O3=8~300
Na2O/SiO2=0.05~0.6
H2O/SiO2=5~50
更优选的反应混合物的组成的范围如下。
SiO2/Al2O3=20~300
Na2O/SiO2=0.1~0.5
H2O/SiO2=10~30
为了获得具有所述摩尔比的反应混合物而使用的二氧化硅源可以举出二氧化硅本身及可在水中生成硅酸根离子的含硅化合物。具体可以举出:湿式法二氧化硅、干式法二氧化硅、胶体二氧化硅、硅酸钠、铝硅酸盐凝胶等。这些二氧化硅源可以单独使用或组合使用两种以上。这些二氧化硅源中,从可以获得β型沸石而不伴有不需要的副产物的方面来看,优选的是使用二氧化硅(silica)。
氧化铝源例如可以使用水溶性含铝化合物。具体可以举出铝酸钠、硝酸铝、硫酸铝等。另外,氢氧化铝也为合适的氧化铝源之一。这些氧化铝源可以单独使用或组合使用两种以上。这些氧化铝源中,从可以获得β型沸石而不伴有不需要的副产物(例如硫酸盐或硝酸盐等)的方面来看,优选的是使用铝酸钠或氢氧化铝。
碱源例如可以使用氢氧化钠。此外,在使用硅酸钠作为二氧化硅源的情况或使用铝酸钠作为氧化铝源的情况下,将其中所含的碱金属成分即钠同时视为NaOH,也为碱成分。因此,所述Na2O是以反应混合物中的所有碱成分之和来计算。
关于制备反应混合物时的各原料的添加顺序,只要采用容易获得均匀的反应混合物的方法即可。例如通过在室温下在氢氧化钠水溶液中添加氧化铝源并使之溶解,然后添加二氧化硅源进行搅拌混合,可以获得均匀的反应混合物。关于晶种,通常采用一面与二氧化硅源混合一面添加或者在添加二氧化硅源之后添加的方法,但添加时刻并无特别限制。其后,以晶种均匀地分散的方式搅拌混合。制备反应混合物时的温度也无特别限制,通常只要在室温(20℃~25℃)下进行即可。
将含有品种的反应混合物加入到密闭容器中并进行加热而使其反应,在自生压力下使β型沸石结晶化。该反应混合物中不含OSDA。晶种重要的是直接使用由所述文献1至文献3中记载的方法所得者。即,不对该晶种进行煅烧。因此,该晶种的孔隙中,成为晶种的合成时所用的OSDA残存的状态。即便将包含经煅烧的硅酸锌盐的β型沸石用作晶种,也无法获得作为目标的具有微孔及介孔的β型沸石。
相对于反应混合物中的二氧化硅成分,添加到反应混合物中的晶种的量是设定为0.1重量%~20重量%的比例,优选的是设定为0.5重量%~15重量%、更优选1重量%~10重量%的比例。通过将晶种与反应混合物的比例设定为该范围,可以由始至终良好地制造作为目标的具有微孔及介孔的β型沸石。
在使用含有晶种的反应混合物使β型沸石结晶化时,若在熟化后进行加热,则结晶化容易进行,因此优选。所谓熟化,是指在低于反应温度的温度下保持于该温度一定时间的操作。熟化中,通常静置而不加搅拌。已知通过进行熟化,可以发挥以下效果:防止杂质的副产生,可以在搅拌下进行加热而不副产生杂质,提高反应速度等效果,但作用机制未必明确。熟化的温度及时间是以最大限度地发挥所述效果的方式设定。该制造方法中,在优选20℃~100℃、更优选20℃~80℃、进而优选20℃~60℃且优选2小时~1天的范围内进行熟化。
在为了实现反应混合物温度的均匀化而进行搅拌的情况下,若在进行熟化后在密闭加热的工序中进行搅拌,则可以防止杂质的副产生。搅拌可以通过利用搅拌翼的混合、或容器的旋转来进行。搅拌强度或转速只要根据温度的均匀性或杂质的副产生程度来调整即可。并非一直搅拌,也可为间歇搅拌。若像这样将熟化与搅拌组合,则可以实现工业上的量产化。
在静置状态下进行结晶化的情况及在搅拌状态下进行结晶化的情况的任一情况下,加热温度均为80℃~200℃的范围,优选100℃~200℃,更优选120℃~180℃的范围。该加热为自生压力下的加热。在低于80℃的温度下,结晶化速度变得极慢,因此β型沸石的生成效率变差。另一方面,在超过200℃的温度下,不仅因需要高耐压强度的高压锅而缺乏经济性,而且杂质的产生速度变快。加热时间在该制造方法中并无临限值,只要加热到生成结晶性充分高的β型沸石即可。通常通过5小时~150小时左右的加热可以获得结晶性令人满意的β型沸石。
通过所述加热可以获得β型沸石的结晶。加热结束后,通过过滤而将所生成的结晶粉末与母液分离后,利用水或温水清洗并加以干燥。在干燥后保持原样的状态下实质上所含的有机物的量为少量,因此即便不进行煅烧,而只进行脱水便可用作吸附剂等。但是,为了充分发挥所得的β型沸石结晶的特性,优选的是进行煅烧处理。煅烧可以通过在空气中在500℃以上的温度下进行加热处理等方法而容易地进行。在用作固体酸催化剂时,例如可以将结晶内的Na+离子交换成NH4 +离子后,进行煅烧,借此以H+型而使用。
实施例
以下,通过实施例对本发明加以更详细说明。但是,本发明的范围不受该实施例的限制。只要无特别说明,则“%”是指“重量%”。此外,以下的实施例、比较例及参考例中所用的分析设备如下。
粉末X射线衍射装置:麦克科技(Mac Science)公司制造的粉末X射线衍射装置MO3XHF22,使用Cukα线,电压为40kV,电流为30mA,扫描步长(scan step)为0.02°,扫描速度2°/min
组成分析装置:瓦里安(Varian)(股)制造,电感耦合等离子体原子发射光谱仪(Inductively Coupled Plasma-Atomic EmissionSpectrometry,ICP-AES)立波帝系列(LIBERTY Series)II
扫描式电子显微镜:日立高新技术(Hitachi High-technologies)(股)公司制造,场发射式扫描电子显微镜S-4800
BET表面积测定装置:康塔仪器(Quantachrome Instruments)(股)公司制造的奥拓索伯(AUTOSORB)-1
[实施例1]
(1)晶种的合成
使用氢氧化四乙基铵(TEAOH)作为OSDA。另外,使用二乙酸锌二水合物作为锌源,使用微粉状二氧化硅(卡博特(Cab-O-Sil)M-5)作为二氧化硅源。进而使用氢氧化锂、氢氧化钠。这些原料中,使TEAOH、氢氧化锂及氢氧化钠溶解在水中后,添加二乙酸锌二水合物,然后添加微粉状二氧化硅并搅拌2小时。像这样而获得的反应混合物的组成为氢氧化锂为0.05M、TEAOH为0.65M、二乙酸锌二水合物为0.03M、微粉状二氧化硅为1M、水为30M。将该反应混合物放入至具有聚四氟乙烯的衬里的不锈钢制高压锅内,在静止状态下在150℃下加热96小时。通过该加热而合成SiO2/ZnO比为13.1、SiO2/Al2O3比为无限大的硅酸锌盐β型沸石。将该β型沸石的未煅烧状态下的X射线衍射图示于图1中。利用扫描式电子显微镜对该β型沸石进行观察,结果平均粒径为640nm。将该β型沸石的结晶直接以未煅烧的状态用作晶种。
(2)β型沸石的合成
在纯水4.759g中溶解铝酸钠0.036g及36%氢氧化钠水溶液1.284g而获得水溶液。将微粉状二氧化硅(卡博特(Cab-O-Sil)M-5)0.937g与0.094g的晶种混合,将所得的混合物逐次少量添加到所述水溶液中并进行搅拌混合。混合后的凝胶的组成如表1所示。另外,相对于凝胶中的二氧化硅成分,晶种的添加量为10%。将凝胶与品种的混合物放入到23cc的不锈钢制密闭容器中,不进行熟化及搅拌而在140℃下在自生压力下静置加热2天。将密闭容器冷却后,过滤产物,进行水清洗而获得白色粉末。对该产物进行X射线衍射,结果确认到该产物为不含杂质的β型沸石。将未煅烧品的X射线衍射图示于图2中。另外,根据液态氮温度下的氮吸附等温线(图3)确认到,兼具具有表1所示般的特征的微孔与介孔。将表示孔隙特性的数值示于表1中。
[实施例2~实施例10]
除了采用表1所示的条件以外,与实施例1同样地获得β型沸石。对所得的β型沸石进行与实施例1相同的评价。将其结果示于表1中。另外,将实施例2中所得的β型沸石的未煅烧状态下的X射线衍射图示于图4中。进而,将实施例8中所得的β型沸石的未煅烧状态下的X射线衍射图及氮吸附等温线分别示于图5及图6中,将实施例10中所得的β型沸石的未煅烧状态下的X射线衍射图及氮吸附等温线分别示于图7及图8中。
[比较例1]
使用将TEAOH用作OSDA所合成的铝硅酸盐β型沸石的煅烧品作为晶种。该β型沸石的SiO2/Al2O3比为24.0,且不含ZnO。在使用与实施例1中所用的原料相同的原料所制备的反应混合物(凝胶)中添加该晶种。凝胶的组成如表2所示。将含有晶种的凝胶在表2所示的条件下加热而进行β型沸石的结晶化。过滤所得的产物,进行水清洗而获得白色粉末。对该产物进行X射线衍射,结果确认到该产物为不含杂质的β型沸石。但是,根据液态氮温度下的氮吸附等温线确认到,完全不存在介孔。
[比较例2及比较例3]
使用比较例1中所用的铝硅酸盐β型沸石的煅烧品作为晶种。将该晶种添加到表2所示的组成的反应混合物(凝胶)中,在表2所示的条件下进行加热而进行β型沸石的结晶化。过滤所得的产物,进行水清洗而获得白色粉末。对该产物进行X射线衍射,结果确认到该产物为不含杂质的β型沸石。但是,根据液态氮温度下的氮吸附等温线确认到,完全不存在介孔。
[比较例4]
使用实施例2中所用的未煅烧的硅酸锌盐β型沸石的煅烧品(空气中、550℃、10小时)作为晶种。除此以外,以与实施例2相同的组成及条件进行反应。过滤所得的产物,进行水清洗而获得白色粉末。对该产物进行X射线衍射,结果为该产物为非晶质。
[表1]
[表2]
如由表1与表2的对比所表明,得知通过使用未煅烧的硅酸锌盐β型沸石作为晶种,可以获得兼具微孔及介孔的β型沸石。相对于此,若使用铝硅酸盐β型沸石作为晶种(比较例1~比较例3),则所得的β型沸石中未形成介孔。另外,即便使用硅酸锌盐β型沸石作为晶种,在其为煅烧品的情况下(比较例4),也不发生沸石的结晶化。
Claims (4)
1.一种β型沸石,其特征在于:
(i)SiO2/Al2O3比为8~30,且SiO2/ZnO比为8~1000;
(ii)微孔表面积为300m2/g~800m2/g;
(iii)微孔体积为0.1cm3/g~0.3cm3/g;
(iv)具有在合成后保持原样的状态下直径为2nm~6nm、且其体积为0.001cm3/g~0.3cm3/g的介孔。
2.一种β型沸石的制造方法,其特征在于:
(1)以成为以下所示的摩尔比所表示的组成的反应混合物的方式,将二氧化硅源、氧化铝源、碱源及水混合,
SiO2/Al2O3=8~300
Na2O/SiO2=0.05~0.6
H2O/SiO2=5~50;
(2)将SiO2/ZnO比为4~50、SiO2/Al2O3比为4以上、且平均粒径为100nm以上的β型沸石不加煅烧而在晶种的合成时所用的有机结构导向剂残存于晶种的孔隙中的状态下用作晶种,将其以相对于所述反应混合物中的二氧化硅成分而为0.1重量%~20重量%的比例添加到所述反应混合物中;
(3)将添加有所述晶种的所述反应混合物在80℃~200℃下进行密闭加热。
3.根据权利要求2所述的β型沸石的制造方法,其特征在于:在加热反应混合物之前,在20℃~100℃的温度下进行熟化。
4.根据权利要求2或3所述的β型沸石的制造方法,其特征在于:在密闭加热的工序中搅拌反应混合物。
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