JP5646807B2 - 人工ゼオライトの製造方法 - Google Patents
人工ゼオライトの製造方法 Download PDFInfo
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- JP5646807B2 JP5646807B2 JP2008163595A JP2008163595A JP5646807B2 JP 5646807 B2 JP5646807 B2 JP 5646807B2 JP 2008163595 A JP2008163595 A JP 2008163595A JP 2008163595 A JP2008163595 A JP 2008163595A JP 5646807 B2 JP5646807 B2 JP 5646807B2
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- artificial zeolite
- zeolite
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- ammonia
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- 239000010457 zeolite Substances 0.000 title claims description 109
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 107
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 107
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 54
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 51
- 239000002994 raw material Substances 0.000 claims description 38
- 239000002699 waste material Substances 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 33
- 239000012212 insulator Substances 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000001307 helium Substances 0.000 claims description 9
- 229910052734 helium Inorganic materials 0.000 claims description 9
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 24
- 150000001336 alkenes Chemical class 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 21
- 229910052710 silicon Inorganic materials 0.000 description 20
- 229910052782 aluminium Inorganic materials 0.000 description 19
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000010703 silicon Substances 0.000 description 17
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- -1 Hydroxide ions Chemical class 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229910010272 inorganic material Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000004071 soot Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000011973 solid acid Substances 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000013307 optical fiber Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 125000000123 silicon containing inorganic group Chemical group 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
「ゼオライトの科学と工学」、小野嘉夫、八嶋建明編、講談社サイエンティフィク刊、2000年、169ページ 「C1ケミストリー」、触媒学会編、講談社サイエンティフィク刊、1984年、130ページ 「ゼオライトの科学と応用」、冨永博夫編、講談社サイエンティフィク刊、1987年、87ページ 「ゼオライトの科学と応用」、冨永博夫編、講談社サイエンティフィク刊、1987年、88ページ
を特徴とする人工ゼオライトの製造方法である。
すなわち、碍子廃材を高温で溶融した後、急冷して粉砕して得た粉砕物を主原料とし、原料中のアルミニウム原子の数を1としたときの、原料中の珪素の原子の数が7.5以上となるように原料を調製した後、密閉容器内のアルカリ水溶液中で加熱反応処理を行ってペンタシル型構造を有する人工ゼオライトを得て、その後、前記人工ゼオライトに対して、水素型化処理を行う。
碍子廃材としては、高圧送電用の碍子(金属金具、セメント、汚れ等付着物を除去したもの)を用いた。粒径が2〜4mm程度となるように粉砕した。このもののケイバン比は2.9であった。
前記、人工ゼオライトαと同様に、ただし、白色スートの配合量を2000gではなく1100gとするとともに、燃焼処理条件を変更して、500℃で2時間加熱した後、300℃で2時間加熱して、本発明に係る人工ゼオライトβを得た。この人工ゼオライトβのX線回折解析の結果を図2に、それぞれ示す。
前記、人工ゼオライトαと同様に、ただし、白色スートの配合量を2000gではなく600gとするとともに、燃焼処理条件を変更して、500℃で2時間加熱して、本発明に係る人工ゼオライトγを得た。この人工ゼオライトγのX線回折解析の結果を図3に、それぞれ示す。
前記人工ゼオライトαh、βh、及び、γh、を、それぞれ40MPaの荷重で圧縮固化させた後、乳鉢で粉砕し、ふるい分けして平均粒子径1.5mmの成型粒子を分取して、触媒能評価サンプルとした。
各触媒能評価サンプルの1gを、固定床流通式反応器(内径1.4cm、長さ40cmのステンレス製反応管、外径0.3cmの熱電対用鞘管付き)に充填した。このとき、触媒層の上下には石英ウールおよび0.2mmφのアルミナボールを充填した。
転化率(%)=[1−(未反応ジメチルエーテル量/供給ジメチルエーテル量)]×100 ・・・(I)
生成物の収率(質量%)=[生成物質量/供給ジメチルエーテル中の(炭素+水素)質量]×100 ・・・(II)
前記と同様に、ただし、反応管に、流量制御器(マスフローコントローラー)を用いて空気を40mL/分(0℃、1気圧換算、以下同じ)で供給しながら外部加熱ヒーターによって触媒層の温度を650℃まで昇温し、そのまま1時間前処理を行った。前処理終了後、触媒層の温度を500℃とし、炭化水素化合物原料として1−ブテンを6mL/分、スチームを1g/時、内部標準として窒素を20mL/分で供給し、1−ブテンの転化反応を行った。
転化率(%)=[1−(未反応1−ブテン + 2−ブテン + イソブチレン量)/供給1−ブテン量]×100 ・・・(III)
生成物の収率(質量%)=[生成物質量/供給1−ブテン質量]×100 ・・・(IV)
表1に記載の人工ゼオライトβhを1g用いて、評価1と同じステンレス製反応管に充填し、評価1同様に前処理を行った。その後、触媒層の温度を550℃とし、含酸素有機化合物原料としてエタノール50質量%の水溶液をマイクロポンプを用いて、4.1g/時の供給速度で供給して反応させた(0℃1気圧換算のガスとして、エタノール:16.6mL/分、スチーム:42.5mL/分、窒素(内部標準)20mL/分として供給)。
転化率(%)=[1−(未反応エタノール/供給エタノール量)]×100 ・・・(V)
生成物の収率(質量%)=[生成物質量/供給エタノール中の炭素及び水素の質量)]×100 ・・・(VI)
Claims (5)
- 碍子廃材を高温で溶融した後、急冷して粉砕して得た粉砕物を主原料とし、原料中のアルミニウム原子の数を1としたときの、原料中の珪素の原子の数が7.5以上となるように原料を調製した後、密閉容器内のアルカリ水溶液中で加熱反応処理を行うペンタシル型構造を有する人工ゼオライトの製造方法であって、
前記加熱反応処理後に、室温以上80℃以下で、0.5〜10mol/Lの可溶性の酸のアンモニウム塩の水溶液に1分〜10時間浸漬し、乾燥後に200℃〜800℃の加熱処理を行う水素型化処理を行い、
100℃の0.5体積%−アンモニアガス・ヘリウムガス混合雰囲気中でアンモニアガスを飽和吸着させた後、100℃から700℃まで20℃/分の昇温速度で加熱したときに100℃以上250℃未満の加熱期間に放出されるアンモニア放出量を100としたときに、250℃以上700℃以下の加熱期間に放出されるアンモニア放出量が200以上となり、かつ、これらアンモニア放出量の和から算出される酸量が0.03mmol/g以上の人工ゼオライトを得ることを特徴とする人工ゼオライトの製造方法。 - 前記加熱反応処理において、下記化学式1で示される化合物をテンプレート剤として併用するとともに、
前記水素型化処理の前に、前記ペンタシル型構造を有する人工ゼオライト内のテンプレート剤を除去するテンプレート除去工程を有することを特徴とする請求項1に記載の人工ゼオライトの製造方法。
- 前記加熱反応処理が、加圧下100℃超の温度で行われることを特徴とする請求項1または請求項2に記載の人工ゼオライトの製造方法。
- 前記碍子廃材の溶融が、プラズマ炉により行われることを特徴とする請求項1ないし請求項3のいずれか1項に記載の人工ゼオライトの製造方法。
- 前記急冷が、溶融した碍子廃材を水中に導入して行われることを特徴とする請求項1ないし請求項4のいずれか1項に記載の人工ゼオライトの製造方法。
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