JP2022083427A - 陽イオンの比率を制御したゼオライトを含む炭化水素吸脱着複合体およびその製造方法 - Google Patents
陽イオンの比率を制御したゼオライト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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- JP2022083427A JP2022083427A JP2021189493A JP2021189493A JP2022083427A JP 2022083427 A JP2022083427 A JP 2022083427A JP 2021189493 A JP2021189493 A JP 2021189493A JP 2021189493 A JP2021189493 A JP 2021189493A JP 2022083427 A JP2022083427 A JP 2022083427A
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- Prior art keywords
- hydrocarbon
- sodium
- desorption
- complex
- zeolite
- Prior art date
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 345
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 345
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 314
- 238000003795 desorption Methods 0.000 title claims abstract description 194
- 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 155
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 68
- 239000010457 zeolite Substances 0.000 title claims abstract description 65
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 64
- 150000001768 cations Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract 2
- 239000011734 sodium Substances 0.000 claims abstract description 92
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 70
- 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 claims abstract description 62
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 230000003647 oxidation Effects 0.000 claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 41
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 38
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 38
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 238000010335 hydrothermal treatment Methods 0.000 claims description 45
- 239000010949 copper Substances 0.000 claims description 31
- 239000002131 composite material Substances 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 19
- -1 hydrogen cations Chemical class 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 15
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 15
- 150000003863 ammonium salts Chemical class 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 238000005342 ion exchange Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 159000000000 sodium salts Chemical class 0.000 claims description 11
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 100
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 58
- 230000000052 comparative effect Effects 0.000 description 57
- 239000003463 adsorbent Substances 0.000 description 30
- 238000002474 experimental method Methods 0.000 description 29
- 229910001868 water Inorganic materials 0.000 description 22
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- KZDCMKVLEYCGQX-UDPGNSCCSA-N 2-(diethylamino)ethyl 4-aminobenzoate;(2s,5r,6r)-3,3-dimethyl-7-oxo-6-[(2-phenylacetyl)amino]-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid;hydrate Chemical compound O.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1.N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 KZDCMKVLEYCGQX-UDPGNSCCSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 230000001174 ascending effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZFYIQPIHXRFFCZ-QMMMGPOBSA-N (2s)-2-(cyclohexylamino)butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NC1CCCCC1 ZFYIQPIHXRFFCZ-QMMMGPOBSA-N 0.000 description 1
- 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 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
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 239000012690 zeolite precursor Substances 0.000 description 1
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Abstract
Description
陽イオンの比率が調節されたゼオライト粒子を金属イオンが含まれた溶液に混合して金属イオンおよび金属酸化物を形成するステップとを含み、
前記陽イオンの比率を調節するステップは、ゼオライト粒子のうち、アルミニウム対比ナトリウムのモル比(Na/Al)を0.7以下に制御す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。
前記ゼオライト粒子と化学的に結合した金属イオンと、
前記ゼオライト粒子の外面に備えられる金属酸化物と、を含み、
前記陽イオンはナトリウムおよび水素の陽イオンを含み、前記ゼオライト粒子のうち、アルミニウム対比ナトリウムのモル比(Na/Al)は0.7以下であることを特徴とする炭化水素吸脱着複合体を提供する。
陽イオンの比率が調節されたゼオライト粒子を金属イオンが含まれた溶液に混合して金属イオンおよび金属酸化物を形成するステップを含み、
前記陽イオンの比率を調節するステップは、ゼオライト粒子のうち、アルミニウム対比ナトリウムのモル比(Na/Al)を0.7以下に制御す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。
実施例1(CuNaZ(0.5))
NaZの合成
3.75gのテトラプロピルアンモニウムヒドロキシド(tetrapropylammonium hydroxide、TPAOH、40wt.% in H2O、シグマアルドリッチ(Sigma-Aldrich))に2.25gの水を入れて10分間撹拌する。その後、6.25gのオルトケイ酸テトラエチル(tetraethyl orthosilicate、TEOS、98%、シグマアルドリッチ)を一滴ずつ入れる。これを混合物Aとする。他の混合物Bには1.81gの水、0.45gの硝酸アルミニウム九水和物(Al(NO3)3・9H2O、シグマアルドリッチ)、そして0.12gの水酸化ナトリウム(NaOH、シグマアルドリッチ)を含む。混合物Aに混合物Bを入れてオートクレーブに密封する。次に、予め160℃に予熱されたオーブンに入れて24時間水熱合成を行う。その後、不純物を除去するために、脱イオン水で4回洗浄し、ゼオライト構造内に含まれないナトリウムを除去するために、500mLの水を利用して真空フィルタリングを行う。続いて、70℃で夜の間乾燥し、550℃、12h、300mL/minの気流下で焼成する。これに対する形態および組成は図1の走査電子顕微鏡イメージとX線回折分析グラフを通じて確認した。図1によれば、走査電子顕微鏡イメージを通じて表面に微細気孔を含むゼオライト粒子を確認することができ、X線回折分析グラフを通じてゼオライト粒子がMFI型構造を有することが分かる。
次に、イオン交換過程を通じてゼオライト粒子のアルミニウム対比ナトリウムのモル比を調節した。具体的には、約100gの脱イオン水に0.04gの硝酸アンモニウム(NH4NO3、99%、シグマアルドリッチ)を溶解させて製造した0.005Mの硝酸アンモニウム溶液100mLに焼成されたナトリウム陽イオン含有ゼオライト粒子(NaZ)1gを添加した。生成された懸濁液を振動マシン(shaking machine、SI-300R、Lab Companion)で1日撹拌してイオン交換されたサンプルを獲得した。前記獲得したサンプルを遠心分離、デキャンティングおよび脱イオン水洗浄を1回繰り返して回収した。回収したサンプルは乾燥し、300mL/minの気流下で1℃/minの上昇速度で550℃で12時間焼成してナトリウム陽イオンの比率が制御されたゼオライト粒子を製造した。
次に、ナトリウム陽イオンの比率が制御されたゼオライト粒子に5重量%の銅を湿式含浸法過程を通じて含浸して炭化水素吸脱着複合体を製造した。具体的には、約80gの脱イオン水に硝酸銅(II)三水和物(Cu(NO3)2・3H2O、98%、シグマアルドリッチ)を溶解させて0.04Mの硝酸銅II(Cu(NO3)2)溶液を製造した。前記ナトリウム陽イオンの比率が制御されたゼオライト粒子を硝酸銅溶液に添加して最終的に約5重量%のCuが含浸されるようにした。その後、混合物を回転式蒸発器に入れて水分を全部除去した後、Cu含浸されたゼオライト粒子(CuNaZ(0.5))を回収して、100℃で一晩乾燥させ、ボックス型電気炉(boxed furnace)で300mL/minの気流下で1℃/minの上昇速度で550℃で6時間焼成させて炭化水素吸脱着複合体を製造した。
上記実施例1で約100gの脱イオン水に8gの硝酸アンモニウム(NH4NO3、99%、シグマアルドリッチ)を溶解させて製造した1Mの硝酸アンモニウム溶液100mLに焼成されたナトリウム陽イオン含有ゼオライト粒子(NaZ)1gを添加した。生成された懸濁液を振動マシン(shaking machine、SI-300R、Lab Companion)で24時間撹拌してイオン交換されたサンプルを獲得したことを除き、実施例1と同じ方法で炭化水素吸脱着複合体を製造した。
上記実施例1で約100gの脱イオン水に8gの硝酸アンモニウム(NH4NO3、99%、シグマアルドリッチ)を溶解させて製造した1Mの硝酸アンモニウム溶液100mLに焼成されたナトリウム陽イオン含有ゼオライト粒子(NaZ)1gを添加した。生成された懸濁液を振動マシン(shaking machine、SI-300R、Lab Companion)で24時間撹拌してイオン交換されたサンプルを獲得する過程を三度繰り返し、実施例1と同じ方法で炭化水素吸脱着複合体を製造した。
上記実施例1で製造した炭化水素吸脱着複合体を気流下で10容積%のH2O水蒸気を通じて800℃で24時間水熱処理して水熱処理された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・hである。
上記実施例2で製造した炭化水素吸脱着複合体を気流下で10容積%のH2O水蒸気を通じて800℃で24時間水熱処理して水熱処理された
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・hである。
上記実施例3で製造した炭化水素吸脱着複合体を気流下で10容積%のH2O水蒸気を通じて800℃で24時間水熱処理して水熱処理された
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・hである。
上記実施例1でイオン交換反応を実施しないことを除き、実施例1と同じ方法で炭化水素吸脱着複合体を製造した。
上記実施例1で約100gの脱イオン水に0.008gの硝酸アンモニウム(NH4NO3、99%、シグマアルドリッチ)を溶解させて製造した0.001Mの硝酸アンモニウム溶液100mLに焼成されたナトリウム陽イオン含有ゼオライト粒子(NaZ)1gを添加した。生成された懸濁液を振動マシン(shaking machine、SI-300R、Lab Companion)で24時間撹拌してイオン交換されたサンプルを獲得したことを除き、実施例1と同じ方法で炭化水素吸脱着複合体を製造した。
前記比較例1で製造した炭化水素吸脱着複合体を気流下で10容積%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・hである。
前記比較例2で製造した炭化水素吸脱着複合体を気流下で10容積%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・hである。
NaZ(0.7)合成
まずは、商業的に手に入れたアンモニウム型ZSM-5ゼオライト1gを0.1Mの硝酸ナトリウム(NaNO3)溶液100mLに混合して常温で24時間撹拌してサンプルを獲得した。前記獲得したサンプルを遠心分離、デキャンティングおよび脱イオン水洗浄を1回繰り返して回収した。回収したサンプルは乾燥し、300mL/minの気流下で1℃/minの上昇速度で550℃で12時間焼成してナトリウム陽イオンの比率が制御されたゼオライト粒子を製造した。
次に、ナトリウム陽イオンの比率が制御されたゼオライト粒子に5重量%の銅を湿式含浸法過程を通じて含浸して炭化水素吸脱着複合体を製造した。具体的には、約80gの脱イオン水に硝酸銅三水和物(Cu(NO3)2・3H2O、98%、シグマアルドリッチ)を溶解させて0.04Mの硝酸銅II(Cu(NO3)2)溶液を製造した。前記ナトリウム陽イオンの比率が制御されたゼオライト粒子を硝酸銅溶液に添加して最終的に約5重量%のCuが含浸されるようにした。その後、混合物を回転式蒸発器に入れて水分を全部除去した後、Cu含浸されたゼオライト粒子(CuNaZ(0.7))を回収して、100℃で一晩乾燥し、ボックス型電気炉(boxed furnace)で300mL/minの気流下で1℃/minの上昇速度で550℃で6時間焼成して炭化水素吸脱着複合体を製造した。
上記実施例7で0.1Mの硝酸ナトリウム(NaNO3)溶液の代わりに0.01Mの硝酸ナトリウム(NaNO3)溶液を用いたことを除き、同じ方法で炭化水素吸脱着複合体を製造した。
上記実施例7で0.1Mの硝酸ナトリウム(NaNO3)溶液の代わりに0.001Mの硝酸ナトリウム(NaNO3)溶液を用いたことを除き、同じ方法で炭化水素吸脱着複合体を製造した。
上記実施例7で硝酸ナトリウム(NaNO3)溶液を用いないことを除き、同じ方法で炭化水素吸脱着複合体を製造した。
上記実施例7で製造した炭化水素吸脱着複合体を気流下で10容積%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・hである。
上記実施例8で製造した炭化水素吸脱着複合体を気流下で10容積%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・hである。
上記実施例9で製造した炭化水素吸脱着複合体を気流下で10容積%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・hである。
上記実施例10で製造した炭化水素吸脱着複合体を気流下で10容積%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・hである。
上記実施例7で0.1Mの硝酸ナトリウム(NaNO3)溶液の代わりに1.0Mの硝酸ナトリウム(NaNO3)溶液を用いて3回繰り返し撹拌したことを除き、同じ方法で炭化水素吸脱着複合体を製造した。
前記比較例5で製造した炭化水素吸脱着複合体を気流下で10容積%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・hである。
実験例1-元素分析結果
本発明による炭化水素吸脱着複合体の元素比率を確認するために、実施例1~14、比較例1~6の炭化水素吸脱着複合体の元素分析を行い、その結果は表1および表2に示した。
本発明による炭化水素吸脱着複合体のアルミニウム対比ナトリウムのモル比および銅の担持有無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、比較例1(CuNaZSM-5)、実施例3(CuHZSM-5)、ナトリウム陽イオン含有ゼオライト(NaZSM-5)および水素陽イオン含有ゼオライト(HZSM-5)を対象として低温始動試験(Cold start test、CST)を実施し、その結果は図3に示した。
本発明による炭化水素吸脱着複合体のゼオライト内のアルミニウム対比ナトリウムのモル比による炭化水素吸着性能を確認するために、実施例1~実施例5および比較例1~比較例4で製造した炭化水素吸着剤を対象として低温始動試験(Cold start test、CST)を実施し、その結果は図4~12に示した。
Claims (16)
- 陽イオンを含むゼオライト粒子と、
前記ゼオライト粒子と化学的に結合した金属イオンと、
前記ゼオライト粒子の外面に備えられる金属酸化物と、を含み、
前記陽イオンはナトリウムおよび水素の陽イオンを含み、前記ゼオライト粒子のうち、アルミニウム対比ナトリウムのモル比(Na/Al)は0.7以下であることを特徴とする炭化水素吸脱着複合体。 - 前記ゼオライト粒子はZSM-5(Zeolite socony mobil-5)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。
- 前記炭化水素吸脱着複合体を600℃~900℃で1時間~36時間5~15容積%の水蒸気を利用して水熱処理
した、水熱処理された炭化水素吸脱着複合体をさらに含み、
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5以上の数であることを特徴とする請求項3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。 - 前記金属イオンはゼオライト粒子に形成された気孔内部に化学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℃以下の温度で炭化水素の吸着を表し、
180℃以上の温度で炭化水素の酸化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。 - 前記炭化水素吸脱着複合体の炭化水素吸着量は0.32~1.5mmolCH4/gであり
前記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。 - 前記金属イオンは3族~12族の元素の中の何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族の元素の中の何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。 - 前記金属イオンは鉄、コバルト、ニッケル、銅、亜鉛、ロジウムおよびカドミウムの中の何れか一つ以上の金属の陽イオンを含み、
前記金属酸化物は鉄、コバルト、ニッケル、銅、亜鉛、ロジウムおよびカドミウムの中の何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9に記載の炭化水素吸脱着複合体。 - イオン交換方法を利用してゼオライト粒子の陽イオンの比率を調節するステップ、および
陽イオンの比率が調節されたゼオライト粒子を金属イオンが含まれた溶液に混合して金属イオンおよび金属酸化物を形成するステップを含み、
前記陽イオンの比率を調節するステップは、ゼオライト粒子のうち、アルミニウム対比ナトリウムのモル比(Na/Al)を0.7以下に制御することを特徴とする炭化水素吸脱着複合体の製造方法。 - 前記陽イオンの比率を調節するステップは、アンモニウム塩水溶液またはナトリウム塩水溶液と前記ゼオライト粒子を混合することを含み、
前記アンモニウム塩水溶液は硫酸アンモニウム、硝酸アンモニウム、塩化アンモニウム、酢酸アンモニウム、過硫酸アンモニウム、アンモニア水、炭酸水素アンモニウムおよび蟻酸アンモニウムの中の何れか一つ以上を含み、
前記ナトリウム塩水溶液は硝酸ナトリウム、塩化ナトリウム、酢酸ナトリウム、過硫酸ナトリウム、炭酸水素ナトリウムおよび蟻酸ナトリウムの中の何れか一つ以上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。 - 前記金属イオンおよび金属酸化物を形成するステップは湿式含浸法を利用す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 。
- 前記金属イオンおよび金属酸化物を形成するステップ以後に600℃~900℃の温度で1時間~36時間5~15容積%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。 - 前記金属イオンは3族~12族の元素の中の何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。
- 請求項1~10の何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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