JP2022083429A - ガス吸着部および補強部を含む炭化水素吸脱着複合体およびその製造方法 - Google Patents
ガス吸着部および補強部を含む炭化水素吸脱着複合体およびその製造方法 Download PDFInfo
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- JP2022083429A JP2022083429A JP2021189495A JP2021189495A JP2022083429A JP 2022083429 A JP2022083429 A JP 2022083429A JP 2021189495 A JP2021189495 A JP 2021189495A JP 2021189495 A JP2021189495 A JP 2021189495A JP 2022083429 A JP2022083429 A JP 2022083429A
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- Prior art keywords
- hydrocarbon
- desorption
- zeolite particles
- gas
- adsorption
- Prior art date
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- Granted
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 238
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 238
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 210
- 238000003795 desorption Methods 0.000 title claims abstract description 99
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 76
- 230000003014 reinforcing effect Effects 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 239000010457 zeolite Substances 0.000 claims description 40
- 229910021536 Zeolite Inorganic materials 0.000 claims description 38
- 239000002131 composite material Substances 0.000 claims description 38
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 30
- 229910021645 metal ion Inorganic materials 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims description 22
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000003463 adsorbent Substances 0.000 claims description 20
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 18
- 238000010335 hydrothermal treatment Methods 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 150000001768 cations Chemical class 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 8
- 239000012686 silicon precursor Substances 0.000 claims description 8
- 230000002787 reinforcement Effects 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- -1 KFI Chemical compound 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 6
- FEAMTICPHLBOPE-UHFFFAOYSA-M 1-adamantyl(trimethyl)azanium;chloride Chemical compound [Cl-].C1C(C2)CC3CC2CC1([N+](C)(C)C)C3 FEAMTICPHLBOPE-UHFFFAOYSA-M 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims description 4
- 229910052676 chabazite Inorganic materials 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 claims description 3
- GNUJKXOGRSTACR-UHFFFAOYSA-M 1-adamantyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C1C(C2)CC3CC2CC1([N+](C)(C)C)C3 GNUJKXOGRSTACR-UHFFFAOYSA-M 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- PTMFUWGXPRYYMC-UHFFFAOYSA-N triethylazanium;formate Chemical compound OC=O.CCN(CC)CC PTMFUWGXPRYYMC-UHFFFAOYSA-N 0.000 claims description 2
- BFFJWZAJLGOBMW-UHFFFAOYSA-M 1-adamantyl(trimethyl)azanium;fluoride Chemical compound [F-].C1C(C2)CC3CC2CC1([N+](C)(C)C)C3 BFFJWZAJLGOBMW-UHFFFAOYSA-M 0.000 claims 4
- 241001600072 Hydroides Species 0.000 claims 1
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 93
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000010949 copper Substances 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 230000002194 synthesizing effect Effects 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
前記ガス吸着部の表面に形成され、前記ガス吸着部のゼオライト粒子と構造が同一のシリカゼオライト粒子を含む補強部を含み、
前記ガス吸着部のゼオライト粒子に金属イオンが結合され、シリカ-ゼオライトを含む補強部とガス吸着部との界面に金属酸化物が備えられたことを特徴とする炭化水素吸脱着複合体を提供する。
ガス吸着部のゼオライト粒子をケイ素前駆体および構造誘導体含むゾル溶液に添加し、3時間~96時間の間水熱合成して補強部を形成するステップを含み、
前記ガス吸着部のゼオライト粒子のアルミニウム対比ケイ素のモル比(Si/Al)が1~50であることを特徴とする炭化水素吸脱着複合体の製造方法を提供する。
前記ガス吸着部の表面に形成され、前記ガス吸着部のゼオライト粒子と構造が同一のシリカゼオライト粒子を含む補強部を含み、
前記ガス吸着部のゼオライト粒子に金属イオンが結合され、補強部のシリカ-ゼオライト粒子とガス吸着部との界面に金属酸化物が備えられたことを特徴とする炭化水素吸脱着複合体を提供する。
前記式(1)で、
QInは炭化水素吸脱着複合体に注入される全体炭化水素の量を表し、
QOutは炭化水素吸脱着複合体を経て排出される全体炭化水素の量を表し、
Aは10以上の数で、炭化水素処理効率を表す。
ガス吸着部のゼオライト粒子をケイ素前駆体および構造誘導体を含むゾル溶液に添加し、3時間~96時間の間水熱合成して補強部を形成するステップを含み、
前記ガス吸着部のゼオライト粒子のアルミニウム対比ケイ素のモル比(Si/Al)が1~50であることを特徴とする炭化水素吸脱着複合体の製造方法を提供する。
具体的には、前記ゾル溶液は、ケイ素前駆体:構造誘導体:溶媒のモル比は10:1~15:10~50000のモル比で構成されてもよく、より具体的には、ケイ素前駆体:構造誘導体:溶媒のモル比は10:2~7:50~10000または10:1~4:100~3000のモル比で構成されてもよい。
実施例1(MFI/MFI)
Si/Al比が10のH-form ZSM-5粒子に湿式含浸法を利用して5重量%のCuを担持してガス吸着部のゼオライト粒子を製造した。40TEOS(オルトケイ酸テトラエチル、tetraethyl orthosilicate):9TPAOH(テトラプロピルアンモニウムヒドロキシド、
tetrapropylammonium hydroxide):9600H2Oのモル比のゾル溶液を製造し、前記ガス吸着部のゼオライト粒子と前記ゾル溶液の比率が0.3g/30mlになるように混合した。その後、テフロンライナーに入れて100℃のオーブンで時間別(3時間、6時間、9時間、12時間、24時間)に水熱合成してガス吸着部の表面に補強部を形成して炭化水素吸脱着複合体を製造した。
Si/Al比が19のH-form BEA粒子に湿式含浸方法を利用して5重量%のCuを担持して、ガス吸着部のゼオライト粒子を製造した。1SiO2:0.4 TEAOH(tetraethylammonium hydroxide):11.6 H2Oのモル比のゾル溶液を製造し、前記ガス吸着部のゼオライト粒子と前記ゾル溶液の比率が0.3g/30mLになるように混合した。その後、テフロンライナーに入れて130℃のオーブンで時間別(24時間、48時間、96時間)に水熱合成してガス吸着部の表面に補強部を形成して炭化水素吸脱着複合体を製造した。
前記実施例1で製造した炭化水素吸脱着複合体を空気気流下で10体積%のH2O水蒸気を通じて800℃で24時間水熱処理して炭化水素吸脱着複合体を製造した。この時、前記炭化水素吸脱着複合体の重量に対する水蒸気を含む模擬排出ガスの時間当りガス流量は100000mL・g-1・h-1である。
前記実施例2で製造した炭化水素吸脱着複合体を空気気流下で10体積%のH2O水蒸気を通じて800℃で24時間水熱処理して炭化水素吸脱着複合体を製造した。この時、前記炭化水素吸脱着複合体の重量に対する水蒸気を含む模擬排出ガスの時間当りガス流量は100000mL・g-1・h-1である。
実験例1
本発明による炭化水素吸脱着複合体の形態を確認するために、実施例1および2の炭化水素吸脱着複合体を走査電子顕微鏡(SEM)で撮影し、X線回折分析(XRD)を行い、その結果は図2および図3に示した。
本発明による炭化水素吸脱着複合体の補強部合成時間による炭化水素吸着量および炭化水素処理効率を確認するために、実施例1および実施例2の炭化水素吸脱着複合体を対象として補強部合成時間別低温始動試験(Cold start test、CST)を行い、その結果は図4~図6および表1に示した。
Claims (16)
- ゼオライト粒子を含み、ゼオライト粒子のアルミニウム対比ケイ素のモル比(Si/Al)が1~50であるガス吸着部、および
前記ガス吸着部の表面に形成され、前記ガス吸着部のゼオライト粒子と構造が同一のシリカ-ゼオライト粒子を含む補強部を含み、
前記ガス吸着部のゼオライト粒子に金属イオンが結合され、補強部のシリカ-ゼオライト粒子とガス吸着部との界面に金属酸化物が備えられたことを特徴とする炭化水素吸脱着複合体。 - 前記ガス吸着部のゼオライト粒子は独立的にMFI(Zeolite Socony Mobil-five)、ベータ(BEA)、菱沸石(CHA)、KFI、MOR、FAU、FER、AEI、LEV、ERI、AFX、SFW、DDR、LTAの中のいずれか一つ以上のゼオライトであることを特徴とする請求項1に記載の炭化水素吸脱着複合体。
- 炭化水素吸脱着複合体はガス吸着部対比補強部の重量比率が5~95であることを特徴とする請求項1に記載の炭化水素吸脱着複合体。
- 前記炭化水素吸脱着複合体を600℃~900℃で1時間~96時間の間5~15体積%の水蒸気を利用して水熱処理することをさらに含み、
水熱処理された炭化水素吸脱着複合体は、前記式(1)で、Aは3以上の数であることを特徴とする請求項4に記載の炭化水素吸脱着複合体。 - 前記炭化水素吸脱着複合体の大きさは50~5000nmで、
前記金属酸化物の大きさは1~10nmであることを特徴とする請求項1に記載の炭化水素吸脱着複合体。 - 前記金属イオンは3族~12族の元素の中のいずれか一つ以上の金属の陽イオンであり、
前記金属酸化物は3族~12族の元素の中のいずれか一つ以上の金属の酸化物であることを特徴とする請求項1に記載の炭化水素吸脱着複合体。 - 前記金属イオンはガス吸着部のゼオライト粒子に存在する気孔内部に結合されたことを特徴とする請求項1に記載の炭化水素吸脱着複合体。
- 炭化水素吸脱着複合体は300℃以下の温度で吸着能を表し、
180℃以上の温度で酸化能を表すことを特徴とする請求項1に記載の炭化水素吸脱着複合体。 - 炭化水素吸脱着複合体の炭化水素吸着量は0.1~1.5mmolCH4/gであり、
炭化水素吸脱着複合体の炭化水素酸化開始温度は180~350℃であることを特徴とする請求項1に記載の炭化水素吸脱着複合体。 - ゼオライト粒子を金属イオンを含む溶液に混合してガス吸着部を形成するステップ、および
ガス吸着部のゼオライト粒子をケイ素前駆体および構造誘導体を含むゾル溶液に添加して4時間~96時間の間水熱合成して補強部を形成するステップを含み、
前記ガス吸着部のゼオライト粒子のアルミニウム対比ケイ素のモル比(Si/Al)が1~50であることを特徴とする炭化水素吸脱着複合体の製造方法。 - 金属イオンは3族~12族の元素の中のいずれか一つ以上の金属の陽イオンを含むことを特徴とする請求項11に記載の炭化水素吸脱着複合体の製造方法。
- 補強部を形成するステップで、ゾル溶液はケイ素前駆体:構造誘導体:溶媒のモル比は10:1~15:10~50000のモル比で構成され、
ゾル溶液対比ガス吸着部の混合比率は0.03g/30mL~3g/30mLであることを特徴とする請求項11に記載の炭化水素吸脱着複合体の製造方法。 - 前記有機構造誘導体は、TPAOH(テトラプロピルアンモニウムヒドロキシド、tetrapropylammonium hydroxide)、TEAOH(テトラエチルアンモニウムヒドロキシド、tetraethylammonium hydroxide)、TMAdaOH(N,N,N-トリメチルアダマンチルアンモニウムヒドロキシド、N,N,N-trimethyl adamantylammonium hydroxide)、TMAdaBr(N,N,N-トリメチルアダマンチルアンモニウムプロミド、N,N,N-trimethyl adamantylammonium bromide)、TMAdaF(N,N,N-トリメチルアダマンチルアンモニウムフルオリド、N,N,N-trimethyl adamantylammonium fluoride)、TMAdaCl(N,N,N-トリメチルアダマンチルアンモニウムクロリド、N,N,N-trimethyl adamantylammonium chloride)、TMAdaI(N,N,N-トリメチルアダマンチルアンモニウムヨーシド、N,N,N-trimethyl adamantylammonium iodide)、TEABr(テトラエチルアンモニウムブロミド、tetraethylammonium bromide)、TEAF(テトラエチルアンモニウムフルオリド、tetraethylammonium fluoride)、TEACl(テトラエチルアンモニウムクロリド、tetraethylammonium chloride)、TEAI(テトラエチルアンモニウムヨーシド、tetraethylammonium iodide)、TPABr(テトラプロピルアンモニウムブロミド、tetrapropylammonium bromide)、TBPOH(テトラブチルホスホニウムヒドロキシド、Tetrabutylphosphonium Hydroxide)、TBACl(テトラブチルアンモニウムクロリド、Tetrabutylammonium chloride)、TBAOH(テトラブチルアンモニウムヒドロキシド、Tetrabutylammonium hydroxide)、TBAF(テトラブチルアンモニウムフルオリド、Tetrabutylammonium fluoride)およびシクロヘキシルアミン(cyclohexylamine)で構成された群で選択される1種以上であることを特徴とする請求項11に記載の炭化水素吸脱着複合体の製造方法。
- 補強部を形成するステップ以後に600℃~900℃の温度で1時間~96時間の間5~15体積%の水蒸気を注入して水熱処理するステップをさらに含み、
前記炭化水素吸脱着複合体の重量に対する水蒸気を含む模擬排出ガスの時間当りガス流量は10000~200000mL/g・hであることを特徴とする請求項11に記載の炭化水素吸脱着複合体の製造方法。 - 請求項1~10のいずれか一項による炭化水素吸脱着複合体を含む自動車用炭化水素吸脱着複合体。
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