JP2013144284A - Porous composite material and production method thereof, and hydrogen sulfide removing material - Google Patents
Porous composite material and production method thereof, and hydrogen sulfide removing material Download PDFInfo
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- JP2013144284A JP2013144284A JP2012006553A JP2012006553A JP2013144284A JP 2013144284 A JP2013144284 A JP 2013144284A JP 2012006553 A JP2012006553 A JP 2012006553A JP 2012006553 A JP2012006553 A JP 2012006553A JP 2013144284 A JP2013144284 A JP 2013144284A
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- hydrogen sulfide
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- 239000002131 composite material Substances 0.000 title claims abstract description 64
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011148 porous material Substances 0.000 claims abstract description 82
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 229910052709 silver Inorganic materials 0.000 claims abstract description 52
- 239000004332 silver Substances 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 239000002184 metal Substances 0.000 claims abstract description 49
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007789 gas Substances 0.000 claims abstract description 16
- 150000004696 coordination complex Chemical class 0.000 claims description 36
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 239000013110 organic ligand Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 93
- 239000000243 solution Substances 0.000 description 34
- 238000005259 measurement Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 15
- 238000000634 powder X-ray diffraction Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- -1 zeolite Chemical class 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000013148 Cu-BTC MOF Substances 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 150000003464 sulfur compounds Chemical class 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- 238000006477 desulfuration reaction Methods 0.000 description 8
- 230000023556 desulfurization Effects 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 101710134784 Agnoprotein Proteins 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 4
- 239000013206 MIL-53 Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000013291 MIL-100 Substances 0.000 description 3
- 239000013178 MIL-101(Cr) Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229940100890 silver compound Drugs 0.000 description 3
- 150000003379 silver compounds Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LCZUOKDVTBMCMX-UHFFFAOYSA-N 2,5-Dimethylpyrazine Chemical compound CC1=CN=C(C)C=N1 LCZUOKDVTBMCMX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910001849 group 12 element Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VEXDRERIMPLZLU-UHFFFAOYSA-N nilic acid Natural products CC(O)C(C)C(O)=O VEXDRERIMPLZLU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 description 1
- 239000001934 2,5-dimethylpyrazine Substances 0.000 description 1
- WSTOEGIEWBZMLU-UHFFFAOYSA-N 2-methyl-4-(2-methylpyridin-4-yl)pyridine Chemical compound C1=NC(C)=CC(C=2C=C(C)N=CC=2)=C1 WSTOEGIEWBZMLU-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- DQRKTVIJNCVZAX-UHFFFAOYSA-N 4-(2-pyridin-4-ylethyl)pyridine Chemical compound C=1C=NC=CC=1CCC1=CC=NC=C1 DQRKTVIJNCVZAX-UHFFFAOYSA-N 0.000 description 1
- BKRBETINLDNENR-UHFFFAOYSA-N 4-(4-pyridin-4-ylbuta-1,3-diynyl)pyridine Chemical compound C1=NC=CC(C#CC#CC=2C=CN=CC=2)=C1 BKRBETINLDNENR-UHFFFAOYSA-N 0.000 description 1
- MAWKLXRVKVOYLR-UHFFFAOYSA-N 4-(4-pyridin-4-ylphenyl)pyridine Chemical compound C1=NC=CC(C=2C=CC(=CC=2)C=2C=CN=CC=2)=C1 MAWKLXRVKVOYLR-UHFFFAOYSA-N 0.000 description 1
- SRTQKANXPMBQCX-UHFFFAOYSA-N 4-[2,4,5-tris(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=C(C=2C=CC(=CC=2)C(O)=O)C=C1C1=CC=C(C(O)=O)C=C1 SRTQKANXPMBQCX-UHFFFAOYSA-N 0.000 description 1
- SATWKVZGMWCXOJ-UHFFFAOYSA-N 4-[3,5-bis(4-carboxyphenyl)phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C=2C=CC(=CC=2)C(O)=O)=CC(C=2C=CC(=CC=2)C(O)=O)=C1 SATWKVZGMWCXOJ-UHFFFAOYSA-N 0.000 description 1
- PEQRGMPXYDIZSX-UHFFFAOYSA-N 4-[4-[3,5-bis[4-(4-carboxyphenyl)phenyl]phenyl]phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C=2C=C(C=C(C=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)C(O)=O)C=2C=CC(=CC=2)C=2C=CC(=CC=2)C(O)=O)C=C1 PEQRGMPXYDIZSX-UHFFFAOYSA-N 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- GHMBWICDPHGOSJ-UHFFFAOYSA-N 5-(3,5-dicarboxyphenyl)-2-phenylbenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C=2C=C(C(C=3C=CC=CC=3)=C(C(O)=O)C=2)C(O)=O)=C1 GHMBWICDPHGOSJ-UHFFFAOYSA-N 0.000 description 1
- LQEZHWGJSWHXPJ-UHFFFAOYSA-N 5-(4-carboxyphenyl)benzene-1,3-dicarboxylic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC(C(O)=O)=CC(C(O)=O)=C1 LQEZHWGJSWHXPJ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 239000013118 MOF-74-type framework Substances 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052800 carbon group element Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021480 group 4 element Inorganic materials 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 229910021476 group 6 element Inorganic materials 0.000 description 1
- 229910021474 group 7 element Inorganic materials 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000013099 nickel-based metal-organic framework Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052696 pnictogen Inorganic materials 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
本発明は、多孔性材料に銀系触媒が担持された多孔性複合材料、及びこの多孔性複合材料から構成される硫化水素ガス除去材に関するものである。 The present invention relates to a porous composite material in which a silver-based catalyst is supported on a porous material, and a hydrogen sulfide gas removing material composed of the porous composite material.
バイオガスや天然ガス（例えば、メタン、エタン等）等は、石油代替エネルギーとして近年広く利用されている。しかし、これらのガスには微量の不純物が含まれており、この不純物が様々な不具合を引き起こすことから問題となっている。不純物には、例えば硫黄化合物（硫化水素）がある。硫黄化合物は、発電機等の利用機器の腐食の原因や、触媒の劣化原因となるため、硫黄化合物を選択的に、且つ効率良く分離除去できる技術の確立が望まれている。 Biogas, natural gas (for example, methane, ethane, etc.) and the like have been widely used in recent years as alternative energy for petroleum. However, these gases contain a trace amount of impurities, and this impurity causes various problems. Examples of impurities include sulfur compounds (hydrogen sulfide). Since sulfur compounds cause corrosion of utilization equipment such as generators and cause deterioration of catalysts, establishment of a technique capable of selectively and efficiently separating and removing sulfur compounds is desired.
硫黄化合物の除去には、多くの硫黄化合物を吸着できるよう、表面積の大きな多孔性材料からなる脱硫剤が使用される。多孔性材料には、ゼオライト等の金属酸化物や、近年注目される金属イオンと有機配位子から形成される多孔性金属錯体（Ｐｏｒｏｕｓ Ｃｏｏｒｄｉｎａｔｉｏｎ Ｐｏｌｙｍｅｒｓ、或いは、Ｍｅｔａｌ Ｏｒｇａｎｉｃ Ｆｒａｍｅｗｏｒｋｓとも称される）等がある。 In order to remove sulfur compounds, a desulfurization agent made of a porous material having a large surface area is used so that a large amount of sulfur compounds can be adsorbed. Examples of porous materials include metal oxides such as zeolite, porous metal complexes formed from metal ions and organic ligands that have recently been attracting attention (also referred to as Porous Coordination Polymers or Metal Organic Frameworks), and the like. is there.
多孔性材料に金属酸化物を用いた例として、例えば、Ａｇ、Ｃｕ、Ｃｏ、Ｎｉ及びＺｎ等の金属をゼオライトに担持させた硫黄化合物除去用吸着剤や（特許文献１）、Ｎａ−Ｙ型ゼオライトに銀を担持させた脱硫剤（特許文献２）、或いは、ゼオライト及び活性炭以外の担体材料と銀含有活性組成物とから構成される細孔構造を有する脱硫触媒等が知られている（特許文献３）。 As an example of using a metal oxide as the porous material, for example, an adsorbent for removing a sulfur compound in which a metal such as Ag, Cu, Co, Ni, and Zn is supported on zeolite (Patent Document 1), Na-Y type A desulfurization agent in which silver is supported on zeolite (Patent Document 2) or a desulfurization catalyst having a pore structure composed of a carrier material other than zeolite and activated carbon and a silver-containing active composition is known (patent) Reference 3).
また、多孔性金属錯体（ＰＣＰ）を硫化水素吸着材の多孔性材料に使用する例として、例えば、ＭＩＬ−４７（Ｖ）、ＭＩＬ−５３（Ａｌ，Ｃｒ，Ｆｅ）、ＭＩＬ−１００（Ｃｒ）、ＭＩＬ−１０１（Ｃｒ）等の多孔性金属錯体から構成される脱硫剤や（非特許文献１）、ＭＯＦ−１９９（ＨＫＵＳＴ−１）の細孔にケギン型のポリ酸を導入して得られる脱硫剤が挙げられる（非特許文献２）。多孔性金属錯体（ＰＣＰ）は、比表面積が広いため、硫化水素等の不純物吸着除去に好適である。 Examples of using a porous metal complex (PCP) for the porous material of the hydrogen sulfide adsorbent include, for example, MIL-47 (V), MIL-53 (Al, Cr, Fe), MIL-100 (Cr). , Obtained by introducing a Keggin-type polyacid into the desulfurization agent composed of a porous metal complex such as MIL-101 (Cr) or the like (Non-patent Document 1) or the pores of MOF-199 (HKUST-1) A desulfurization agent is mentioned (nonpatent literature 2). A porous metal complex (PCP) has a wide specific surface area, and is therefore suitable for removing impurities such as hydrogen sulfide.
ところが、特許文献１、２に記載されるように、多孔性材料としてゼオライトを採用しても、ゼオライトの比表面積を向上させることには限界があるため、硫化水素の吸着容量を増量させることは困難である。また特許文献３の脱硫触媒は、硫黄含有化合物として、テトラヒドロチオフェン（ＴＨＴ）の吸着能しか検討されておらず、硫化水素の吸着性能については不明である。さらに非特許文献１に開示される脱硫剤は、単に多孔性金属錯体（ＰＣＰ）を硫化水素吸着材として使用するに過ぎず、常圧下での硫化水素の除去率は満足のいくものではない。また、非特許文献１の多孔性金属錯体のうち、ＭＩＬ−４７（Ｖ）、ＭＩＬ−５３（Ａｌ，Ｃｒ，Ｆｅ）は、構成金属に水分子が配位しないため、真空加熱処理を行っても、構成金属が配位不飽和状態にならない。また、ＭＩＬ−１００（Ｃｒ）、ＭＩＬ−１０１（Ｃｒ）は細孔径が２９〜３４Å程度と大きく、小分子の硫化水素の吸着性能が劣る。さらに、ＭＩＬ−１００（Ｃｒ）、ＭＩＬ−１０１（Ｃｒ）は、三核金属クラスターをベースとする多孔性金属錯体であるため、真空加熱を行ったとしても、配位不飽和金属を形成し難く、硫化水素を充分に除去することが難しい。加えて非特許文献２に開示される脱硫剤は、液相中における硫化水素除去性能は検討されているものの、気相中での除去性能が検討されていないため、気相中での硫化水素除去性能は明らかではない。 However, as described in Patent Documents 1 and 2, even if zeolite is used as the porous material, there is a limit in improving the specific surface area of the zeolite, so that it is possible to increase the adsorption capacity of hydrogen sulfide. Have difficulty. In addition, the desulfurization catalyst of Patent Document 3 has been studied only for the adsorption ability of tetrahydrothiophene (THT) as a sulfur-containing compound, and the adsorption performance of hydrogen sulfide is unknown. Furthermore, the desulfurization agent disclosed in Non-Patent Document 1 merely uses a porous metal complex (PCP) as a hydrogen sulfide adsorbent, and the removal rate of hydrogen sulfide under normal pressure is not satisfactory. Of the porous metal complexes of Non-Patent Document 1, MIL-47 (V) and MIL-53 (Al, Cr, Fe) are subjected to vacuum heat treatment because water molecules do not coordinate with the constituent metals. However, the constituent metal does not become a coordination unsaturated state. Moreover, MIL-100 (Cr) and MIL-101 (Cr) have a large pore diameter of about 29 to 34 mm, and are inferior in the adsorption performance of small molecule hydrogen sulfide. Furthermore, since MIL-100 (Cr) and MIL-101 (Cr) are porous metal complexes based on trinuclear metal clusters, it is difficult to form a coordination unsaturated metal even when vacuum heating is performed. It is difficult to sufficiently remove hydrogen sulfide. In addition, the desulfurization agent disclosed in Non-Patent Document 2 has been studied for hydrogen sulfide removal performance in the liquid phase, but has not been studied for removal performance in the gas phase. Removal performance is not clear.
このような状況の下、本発明では気相中での硫化水素除去性能に優れる多孔性複合材料を提供することを課題として掲げた。 Under such circumstances, an object of the present invention is to provide a porous composite material having excellent hydrogen sulfide removal performance in the gas phase.
本発明者らは、前記課題を解決するために鋭意研究を重ねた結果、配位不飽和状態の金属が存在する多孔性材料は、優れた硫化水素除去能を有していることを見出した。特に、この多孔性材料に銀系触媒を担持させて得られる多孔性複合材料は、より優れた硫化水素除去能を有し、かつ長時間使用しても、この優れた硫化水素除去能が維持されることを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have found that a porous material containing a metal in a coordinated unsaturated state has an excellent ability to remove hydrogen sulfide. . In particular, a porous composite material obtained by supporting a silver-based catalyst on this porous material has better hydrogen sulfide removal ability, and this excellent hydrogen sulfide removal ability is maintained even when used for a long time. As a result, the present invention has been completed.
すなわち、本発明に係る多孔性複合材料は、多孔性材料に、銀系触媒が担持された多孔性複合材料であって、前記多孔性材料の一部または全部の金属が、配位不飽和状態である点に要旨を有する。前記多孔性材料は、金属及び有機配位子から構成される多孔性金属錯体であることが好ましく、前記有機配位子は１，３，５−ベンゼントリカルボン酸及びその誘導体であることが望ましい。また、前記金属は銅であることが好ましい。加えて、銀系触媒の平均粒子径は１０ｎｍ以下であることが望ましい。さらに本発明には、前記多孔性複合材料からなる硫化水素ガス除去材も包含される。加えて、水分子と配位結合している多孔性材料を真空加熱して、配位不飽和状態の金属を形成し、次いで銀系触媒を担持させることを特徴とする多孔性複合材料の製造方法も含まれる。前記多孔性複合材料の製造方法には、多孔性複合材料が還元される態様も包含される。 That is, the porous composite material according to the present invention is a porous composite material in which a silver-based catalyst is supported on a porous material, and a part or all of the metal of the porous material is in a coordinated unsaturated state. The point is that. The porous material is preferably a porous metal complex composed of a metal and an organic ligand, and the organic ligand is preferably 1,3,5-benzenetricarboxylic acid and derivatives thereof. The metal is preferably copper. In addition, the average particle size of the silver-based catalyst is desirably 10 nm or less. Furthermore, the present invention includes a hydrogen sulfide gas removing material made of the porous composite material. In addition, a porous material coordinated with water molecules is heated in a vacuum to form a metal in a coordinated unsaturated state, and then a porous catalyst is supported. A method is also included. The method for producing the porous composite material includes an embodiment in which the porous composite material is reduced.
本発明の多孔性複合材料は、配位不飽和状態の金属が存在する多孔性材料に、銀系触媒が担持されているため、この複合材料は、極めて優れた硫化水素除去能を有し、かつ長時間使用した場合であっても、この優れた硫化水素除去能が維持される。また銀が担持されない多孔性材料であっても、配位不飽和状態の金属が存在するものは、優れた硫化水素除去能を有している。 Since the porous composite material of the present invention has a silver-based catalyst supported on a porous material in which a metal in a coordinated unsaturated state is present, this composite material has extremely excellent hydrogen sulfide removal ability, And even when it is used for a long time, this excellent hydrogen sulfide removal ability is maintained. Moreover, even if the porous material does not carry silver, the one having a metal in a coordinated unsaturated state has an excellent ability to remove hydrogen sulfide.
＜＜多孔性複合材料＞＞
本発明の多孔性複合材料は、配位不飽和状態の金属が存在する多孔性材料に、銀系触媒（銀や銀化合物）が担持されている。ガス中の硫化水素は銀系触媒と反応することにより、多孔性材料に吸着されやすい化合物（例えば、硫黄や二酸化硫黄等）に変換される。さらに、この反応で生成される化合物は、多孔性材料の細孔内部に捕捉されるため、ガス中の硫黄化合物濃度を低く抑えることができる。
<< Porous Composite Material >>
In the porous composite material of the present invention, a silver-based catalyst (silver or silver compound) is supported on a porous material in which a metal in a coordinated unsaturated state exists. Hydrogen sulfide in the gas is converted into a compound (for example, sulfur or sulfur dioxide) that is easily adsorbed by the porous material by reacting with the silver-based catalyst. Furthermore, since the compound produced | generated by this reaction is capture | acquired inside the pore of a porous material, the sulfur compound density | concentration in gas can be restrained low.
＜多孔性材料＞
本発明では、銀系触媒を担持させる基材として、配位不飽和状態の金属が存在する多孔性材料を使用する。配位不飽和状態の金属が存在する多孔性材料は、硫化水素の吸着性能に優れることが本発明者らの研究により明らかとなった。また、多孔性材料中に配位不飽和状態の金属が存在すると、金属原子の空の軌道を利用して、銀系触媒が配位結合するため、銀系触媒を多孔性材料に容易に担持させることもできる。加えて、多孔性材料は比表面積が広いため、硫化水素の分解反応により生じる硫黄化合物を多量に吸着できる。
<Porous material>
In the present invention, a porous material in which a metal in a coordinated unsaturated state is present is used as a substrate for supporting a silver-based catalyst. It has been clarified by the present inventors that a porous material containing a metal in a coordinated unsaturated state is excellent in hydrogen sulfide adsorption performance. In addition, when a metal in a coordinated unsaturated state is present in the porous material, the silver-based catalyst is coordinated using the empty orbit of the metal atom, so the silver-based catalyst is easily supported on the porous material. It can also be made. In addition, since the porous material has a large specific surface area, it can adsorb a large amount of sulfur compounds generated by the decomposition reaction of hydrogen sulfide.
多孔性材料としては、多孔性金属錯体を使用することが好ましく、この多孔性金属錯体は、金属及び有機配位子から構成されることが望ましい。多孔性金属錯体としては、Ｃｕと１，３，５−ベンゼントリカルボン酸（ＢＴＣ）から形成されるＨＫＵＳＴ−１（ＭＯＦ−１９９）、Ｎｉと２，５−ジヒドロキシテレフタル酸から形成されるＮｉ−ＭＯＦ−７４の使用が好ましく、中でも硫化水素除去性能が高いことから、ＨＫＵＳＴ−１を使用することがより好ましい。 As the porous material, a porous metal complex is preferably used, and the porous metal complex is preferably composed of a metal and an organic ligand. Examples of porous metal complexes include HKUST-1 (MOF-199) formed from Cu and 1,3,5-benzenetricarboxylic acid (BTC), and Ni-MOF formed from Ni and 2,5-dihydroxyterephthalic acid. Use of -74 is preferable, and among them, HKUST-1 is more preferable because of its high hydrogen sulfide removal performance.
また、多孔性金属錯体としては、前述したＮｉ−ＭＯＦ−７４等の単核金属クラスターの多孔性金属錯体、または、ＨＫＵＳＴ−１（ＭＯＦ−１９９）等の二核金属クラスターの多孔性金属錯体の使用が好適である。このように、単核または二核金属クラスターの多孔性金属錯体の使用が、本発明に好適である理由は定かではないものの、理由の一つとして、三核、または、それ以上の多核金属クラスターから構成される多孔性金属錯体は、真空加熱を行っても構成金属を配位不飽和状態することが困難であることが挙げられる。 In addition, as the porous metal complex, the porous metal complex of the mononuclear metal cluster such as Ni-MOF-74 described above or the porous metal complex of the binuclear metal cluster such as HKUST-1 (MOF-199) is used. Use is preferred. Thus, although the reason why the use of a monometallic or binuclear metal cluster porous metal complex is suitable for the present invention is not clear, one reason is that it is a trinuclear or higher polynuclear metal cluster. In the porous metal complex composed of the above, it is difficult to make the constituent metal coordinatively unsaturated even when vacuum heating is performed.
多孔性金属錯体の金属としては、周期表第２族〜第１５族に分類される金属の使用が好ましい。中でも、Ｍｇ、Ｃａ、Ｓｒ、Ｂａの第２族元素；Ｓｃ、Ｙの第３族元素；Ｔｉ、Ｚｒ、Ｈｆの第４族元素；Ｖ、Ｎｂ、Ｔａの第５族元素；Ｃｒ、Ｍｏ、Ｗの第６族元素；Ｍｎ、Ｒｅの第７族元素；Ｆｅ、Ｒｕ、Ｏｓの第８族元素；Ｃｏ、Ｒｈ、Ｉｒの第９族元素；Ｎｉ、Ｐｄ、Ｐｔの第１０族元素；Ｃｕ、Ａｇ、Ａｕの第１１族元素；Ｚｎ、Ｃｄ、Ｈｇの第１２族元素；Ａｌ、Ｇａ、Ｉｎ、Ｔｌの第１３族元素；Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂの第１４族元素；Ａｓ、Ｓｂ、Ｂｉの第１５族元素が好ましく、さらに好ましくは第１０族〜第１２族の元素であり、中でもＮｉ、Ｃｕの使用が望ましく、本発明にはＣｕが最適である。これらの元素の金属はイオンの状態で用いることも可能であり、金属イオンの好適な例として、Ｎｉ2+、Ｎｉ+、Ｃｕ2+、Ｃｕ+が挙げられる。 As the metal of the porous metal complex, it is preferable to use a metal classified into Group 2 to Group 15 of the periodic table. Among them, Group 2 elements of Mg, Ca, Sr, Ba; Group 3 elements of Sc, Y; Group 4 elements of Ti, Zr, Hf; Group 5 elements of V, Nb, Ta; Cr, Mo, Group 6 element of W; Group 7 element of Mn, Re; Group 8 element of Fe, Ru, Os; Group 9 element of Co, Rh, Ir; Group 10 element of Ni, Pd, Pt; Cu , Ag, Au, Group 11 elements; Zn, Cd, Hg, Group 12 elements; Al, Ga, In, Tl, Group 13 elements; Si, Ge, Sn, Pb, Group 14 elements; As, Sb , Bi is preferably a Group 15 element, more preferably a Group 10 to Group 12 element, of which Ni or Cu is desirable, and Cu is the most suitable for the present invention. The metal of these elements can also be used in an ionic state, and preferred examples of the metal ion include Ni 2+ , Ni + , Cu 2+ and Cu + .
また有機配位子としては、カルボン酸及びその誘導体、二座以上で配位可能なアミン系化合物及びその誘導体の使用が望ましい。カルボン酸及びその誘導体としては、例えば、ｐ−テルフェニル−３，３’，５，５’−テトラカルボン酸〔別名称：５，５’−（１，４−フェニレン）ビスイソフタル酸〕、１，２，４，５−テトラキス（４−カルボキシフェニル）ベンゼン等のテトラカルボン酸及びその誘導体；ビフェニル−３，４’，５−トリカルボン酸、１，３，５−トリス（４’−カルボキシ［１，１’−ビフェニル］−４−イル）ベンゼン、１，３，５−トリス（４−カルボキシフェニル）ベンゼン、１，３，５−ベンゼントリカルボン酸等のトリカルボン酸及びその誘導体；２，５−ジアミノテレフタル酸、２，５−ジヒドロキシテレフタル酸、２，６−ナフタレンジカルボン酸、イソフタル酸、テレフタル酸、フマル酸、マロン酸、アジピン酸等のジカルボン酸及びその誘導体が挙げられる。また二座以上で配位可能なアミン系化合物及びその誘導体としては、イミダゾール、２−メチルイミダゾール、２−フェニルイミダゾール等のイミダゾール類及びその誘導体；４，４’−ビピリジン、１，４−ビス（４−ピリジル）ベンゼン、２，２’−ジメチル−４，４'−ビピリジン、１，４−ビス（４−ピリジル）ブタジイン、１，２−ビス（４−ピリジル）エタン、３，６−ジ（４−ピリジル）−１，２，４，５−テトラジン等のピリジン環を有する化合物及びその誘導体；ピラジン、２，５−ジメチルピラジン等のピラジン環を有する化合物及びその誘導体；その他上記以外の１，４−ジアザビシクロ［２．２．２］オクタン等の環状アミン類及びその誘導体等が好ましく使用できる。有機配位子としては、中でもトリカルボン酸及びその誘導体の使用が好ましく、特に１，３，５−ベンゼントリカルボン酸及びその誘導体が好ましい。 As organic ligands, it is desirable to use carboxylic acids and derivatives thereof, amine compounds capable of coordinating at a bidentate or higher, and derivatives thereof. Examples of the carboxylic acid and derivatives thereof include p-terphenyl-3,3 ′, 5,5′-tetracarboxylic acid [another name: 5,5 ′-(1,4-phenylene) bisisophthalic acid], 1 , 2,4,5-tetrakis (4-carboxyphenyl) benzene and the like; and biphenyl-3,4 ', 5-tricarboxylic acid, 1,3,5-tris (4'-carboxy [1 , 1′-biphenyl] -4-yl) benzene, 1,3,5-tris (4-carboxyphenyl) benzene, 1,3,5-benzenetricarboxylic acid and other tricarboxylic acids and derivatives thereof; 2,5-diamino Dicarbohydrates such as terephthalic acid, 2,5-dihydroxyterephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, terephthalic acid, fumaric acid, malonic acid, adipic acid, etc. Acid and derivatives thereof. Further, amine compounds capable of coordinating at the bidentate or higher and derivatives thereof include imidazoles such as imidazole, 2-methylimidazole and 2-phenylimidazole and derivatives thereof; 4,4′-bipyridine, 1,4-bis ( 4-pyridyl) benzene, 2,2′-dimethyl-4,4′-bipyridine, 1,4-bis (4-pyridyl) butadiyne, 1,2-bis (4-pyridyl) ethane, 3,6-di ( Compounds having a pyridine ring such as 4-pyridyl) -1,2,4,5-tetrazine and derivatives thereof; compounds having a pyrazine ring such as pyrazine and 2,5-dimethylpyrazine and derivatives thereof; Cyclic amines such as 4-diazabicyclo [2.2.2] octane and derivatives thereof can be preferably used. As the organic ligand, tricarboxylic acid and derivatives thereof are preferably used, and 1,3,5-benzenetricarboxylic acid and derivatives thereof are particularly preferable.
多孔性材料に存在する細孔径は、例えば、１〜２５Åであることが望ましく、より好ましくは３〜２０Åであり、さらに好ましくは５〜１５Åである。細孔径が小さいほど、小分子である硫化水素を捕捉できるため望ましい。また、多孔性金属錯体は通常、細孔表面径が狭く、細孔内部径が広いというボトルネック構造を有する。そのため、多孔性材料として多孔性金属錯体を使用する場合は、多孔性金属錯体の細孔表面径、及び細孔内部径が、共に前記範囲内に包含されることが好ましい。 The pore diameter present in the porous material is, for example, desirably 1 to 25 mm, more preferably 3 to 20 mm, and still more preferably 5 to 15 mm. The smaller the pore diameter, the more preferable because hydrogen sulfide, which is a small molecule, can be captured. Further, the porous metal complex usually has a bottleneck structure in which the pore surface diameter is narrow and the pore internal diameter is wide. Therefore, when a porous metal complex is used as the porous material, it is preferable that both the pore surface diameter and the pore internal diameter of the porous metal complex are included in the above range.
＜触媒＞
配位不飽和状態の金属が存在する多孔性材料であっても、従来に比べ、優れた硫化水素除去能は発揮される。しかし、燃料ガス中の硫化水素を酸化し、無害化する目的で、前記多孔性材料に、酸化触媒として銀系触媒を担持させると、硫化水素の除去効率が飛躍的に向上することが分かった。そのため、本発明の多孔性複合材料は、多孔性材料に銀系触媒が担持されている点に特徴を有する。
銀系触媒としては、銀または銀化合物が好適に用いられ、前記銀化合物としては、例えば酸化銀、及び硫化銀が挙げられる。
<Catalyst>
Even in the case of a porous material containing a metal in a coordinated unsaturated state, an excellent hydrogen sulfide removing ability is exhibited as compared with the conventional material. However, for the purpose of oxidizing and detoxifying the hydrogen sulfide in the fuel gas, it was found that the removal efficiency of hydrogen sulfide is dramatically improved when the porous material is loaded with a silver-based catalyst as an oxidation catalyst. . Therefore, the porous composite material of the present invention is characterized in that a silver-based catalyst is supported on the porous material.
As the silver-based catalyst, silver or a silver compound is preferably used. Examples of the silver compound include silver oxide and silver sulfide.
前記銀系触媒の多孔性材料に対する担持量は、多孔性複合材料１００質量％中、２０質量％以下であることが好ましく、より好ましくは１５質量％以下であり、さらに好ましくは８質量％以下であり、０．０１質量％以上であることが好ましく、より好ましくは０．０５質量％以上であり、さらに好ましくは０．０７質量％以上である。銀系触媒の担持量が前記範囲内であれば、触媒と硫化水素の反応率を向上させることができる。 The supported amount of the silver-based catalyst with respect to the porous material is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 8% by mass or less in 100% by mass of the porous composite material. It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.07% by mass or more. When the supported amount of the silver-based catalyst is within the above range, the reaction rate between the catalyst and hydrogen sulfide can be improved.
＜＜構成金属の配位不飽和化＞＞
多孔性材料は銀系触媒担持工程前に、真空加熱されることが望ましい。多孔性材料が多孔性金属錯体である場合、金属は、有機配位子のみならず、通常水分子とも配位結合している。ところがこの加熱により、金属と水分子との配位結合は切断され、一部または全部の金属が配位不飽和状態になる。多孔性材料を構成する金属の一部または全部を配位不飽和状態にすることにより、多孔性材料の硫化水素吸着能を向上させることができる。さらに本発明では、この配位不飽和状態の結合を利用して酸化触媒（銀系触媒）を担持させることにより、硫化水素除去能を飛躍的に向上できる。
<< Coordination desaturation of constituent metals >>
The porous material is desirably heated in a vacuum before the silver catalyst supporting step. When the porous material is a porous metal complex, the metal is usually coordinated not only with the organic ligand but also with water molecules. However, by this heating, the coordinate bond between the metal and the water molecule is broken, and a part or all of the metal is in a coordinated unsaturated state. By making a part or all of the metal constituting the porous material into a coordinated unsaturated state, the hydrogen sulfide adsorption ability of the porous material can be improved. Furthermore, in the present invention, the ability to remove hydrogen sulfide can be drastically improved by supporting the oxidation catalyst (silver-based catalyst) using the bond in the coordination unsaturated state.
真空加熱処理に関し、加熱温度は６０〜１８０℃が好ましく、より好ましくは８０〜１６０℃、更に好ましくは１００〜１４０℃である。また加熱時間は、１０時間以上が好適であり、より好適には１２時間以上であり、２４時間以下が好ましく、より好ましくは１８時間以下である。真空加熱処理後、多孔性材料は室温まで放冷されることが望ましい。 Regarding the vacuum heat treatment, the heating temperature is preferably 60 to 180 ° C, more preferably 80 to 160 ° C, and still more preferably 100 to 140 ° C. The heating time is preferably 10 hours or longer, more preferably 12 hours or longer, preferably 24 hours or shorter, more preferably 18 hours or shorter. After the vacuum heat treatment, the porous material is preferably allowed to cool to room temperature.
＜＜多孔性複合材料の製造方法＞＞
本発明の多孔性複合材料は、配位不飽和状態の金属が存在する多孔性材料に銀系触媒を担持させることにより製造される。銀系触媒の担持方法としては、（１）銀系触媒を含む溶液に多孔性材料を含浸させる溶液含浸法、（２）高剪断力下で多孔性材料と銀系触媒を混合するメカノケミカル法、或いは、（３）化学蒸着法等が適宜用いられる。中でも、多孔性複合材料の製造が容易であることから、本発明では（１）溶液含浸法を採用することが望ましい。
<< Method for Producing Porous Composite Material >>
The porous composite material of the present invention is produced by supporting a silver-based catalyst on a porous material containing a metal in a coordinated unsaturated state. As a method for supporting a silver catalyst, (1) a solution impregnation method in which a solution containing a silver catalyst is impregnated with a porous material, and (2) a mechanochemical method in which the porous material and the silver catalyst are mixed under high shear force. Alternatively, (3) a chemical vapor deposition method or the like is appropriately used. Among these, it is desirable to employ the (1) solution impregnation method in the present invention because the production of the porous composite material is easy.
溶液含浸法により多孔性複合材料を製造する場合、銀系触媒を含む溶液の調製方法としては、溶媒に銀系触媒を溶解させて銀イオンを生成させる方法や、溶媒に銀系触媒を分散させる方法等が適宜使用される。溶媒としては、水や、メタノール、エタノール等のアルコール系溶媒の使用が望ましい。また、これらの溶媒は単独で用いても、混合して用いてもよい。銀イオンを含むイオン溶液は、前記溶媒に、硝酸銀、ハロゲン化銀等の塩を混合することにより適宜調製される。 When producing a porous composite material by a solution impregnation method, a method for preparing a solution containing a silver-based catalyst includes a method in which a silver-based catalyst is dissolved in a solvent to produce silver ions, or a silver-based catalyst is dispersed in a solvent. A method etc. are used suitably. As the solvent, it is desirable to use water or an alcohol solvent such as methanol or ethanol. These solvents may be used alone or in combination. The ion solution containing silver ions is appropriately prepared by mixing a salt such as silver nitrate or silver halide with the solvent.
溶液含浸法の場合、多孔性複合材料は、真空加熱処理後の多孔性材料を、銀系触媒含有溶液に加え、多孔性材料に銀系触媒を含む溶液を充分に含浸させた後、固液分離した後、固体を乾燥させて製造される。銀系触媒含有溶液への含浸時間は、１〜４８時間が好適であり、より好適には３〜２４時間、さらに好適には１０〜２０時間である。含浸時には、溶液を攪拌することも可能である。また含浸後の固液分離操作としては、濾過、遠心分離、沈殿、溶媒留去等の公知の手段を適宜採用するとよい。 In the case of the solution impregnation method, the porous composite material is obtained by adding the porous material after the vacuum heat treatment to the silver catalyst-containing solution, sufficiently impregnating the porous material with the solution containing the silver catalyst, After separation, the solid is produced by drying. The impregnation time for the silver-based catalyst-containing solution is preferably 1 to 48 hours, more preferably 3 to 24 hours, and even more preferably 10 to 20 hours. It is also possible to stir the solution during impregnation. In addition, as the solid-liquid separation operation after impregnation, known means such as filtration, centrifugation, precipitation, and solvent distillation may be appropriately employed.
＜銀系触媒のナノ化＞
多孔性材料に銀系触媒含有溶液を含浸させた後、次いで還元剤を含む溶液と多孔性複合材料を混合することにより、銀系触媒を微粒子化することができる。本発明者らは、銀系触媒を微粒子化すると、得られた多孔性複合材料が、硫化水素除去材として長時間（例えば、１０時間程度）連続的に使用された後であっても、硫化水素除去率１００％という驚異的な硫化水素除去性能を発揮するという知見を得た。そのため本発明においては、銀系触媒の平均粒子径は１０ｎｍ以下であることが好ましく、より好ましくは８ｎｍ以下、さらに好ましくは６ｎｍ以下である。なお、平均粒子径の測定方法については、実施例の欄に詳述する。
<Nano-based silver catalyst>
After impregnating the porous material with the silver-based catalyst-containing solution, the silver-based catalyst can be made into fine particles by mixing the solution containing the reducing agent and the porous composite material. When the inventors of the present invention have made the silver-based catalyst fine particles, the resulting porous composite material is sulfided even after being used continuously for a long time (for example, about 10 hours) as a hydrogen sulfide removing material. The inventor has obtained the knowledge that the hydrogen-removing rate is 100% and exhibits an amazing hydrogen sulfide removing performance. Therefore, in this invention, it is preferable that the average particle diameter of a silver-type catalyst is 10 nm or less, More preferably, it is 8 nm or less, More preferably, it is 6 nm or less. In addition, the measuring method of an average particle diameter is explained in full detail in the Example column.
銀系触媒を微粒子化する方法としては、例えば溶液含浸法で多孔性複合材料を製造する場合、多孔性材料に銀系触媒含有溶液を含浸させた後、一旦溶媒を留去し、そこへ還元剤と溶媒の混合溶液を添加し、一定時間多孔性複合材料を含浸させて還元処理を行うとよい。その後、固液分離操作を行い、得られる多孔性複合材料を加熱乾燥することが望ましい。還元剤含有溶液に多孔性複合材料を含浸させる時間は、５〜２４０分が好適であり、より好適には１０〜１２０分、さらに好適には１５〜６０分である。 For example, when producing a porous composite material by a solution impregnation method, a silver catalyst is impregnated with a solution containing a silver catalyst, and then the solvent is once distilled off and reduced there. A reduction treatment may be performed by adding a mixed solution of an agent and a solvent and impregnating the porous composite material for a certain period of time. Thereafter, it is desirable to perform a solid-liquid separation operation and heat dry the resulting porous composite material. The time for impregnating the porous composite material into the reducing agent-containing solution is preferably 5 to 240 minutes, more preferably 10 to 120 minutes, and even more preferably 15 to 60 minutes.
還元剤としては、公知の還元剤を適宜使用することができ、例えば、水素化ホウ素ナトリウム（ＮａＢＨ4）、水素化トリエチルホウ素リチウム（［ＬｉＢＨ（Ｃ2Ｈ5）3］）等の水素化ホウ素化合物；水素化アルミニウムリチウム（ＬｉＡｌＨ4）、水素化ジイソブチルアルミニウム（ＤＩＢＡＨ）等の水素化アルミニウム化合物が好適に使用される。 As the reducing agent, a known reducing agent can be used as appropriate, and examples thereof include borohydrides such as sodium borohydride (NaBH 4 ) and lithium triethylborohydride ([LiBH (C 2 H 5 ) 3 ]). Compound: Aluminum hydride compounds such as lithium aluminum hydride (LiAlH 4 ) and diisobutylaluminum hydride (DIBAH) are preferably used.
還元剤の添加量は、銀イオン１ｍｏｌに対し、５〜１５ｍｏｌであることが好ましく、より好適には６〜１２ｍｏｌであり、さらに好適には６．５〜１０ｍｏｌである。還元剤の添加量が銀イオン１ｍｏｌに対し、５ｍｏｌ未満では、銀系触媒を微粒子化することが困難な場合がある。 It is preferable that the addition amount of a reducing agent is 5-15 mol with respect to 1 mol of silver ions, More preferably, it is 6-12 mol, More preferably, it is 6.5-10 mol. If the addition amount of the reducing agent is less than 5 mol with respect to 1 mol of silver ions, it may be difficult to make the silver catalyst fine.
＜＜硫化水素ガス除去材＞＞
本発明により得られる多孔性材料・多孔性複合材料は、硫化水素除去能に優れるため、本発明の多孔性材料・多孔性複合材料を燃料ガスの精製装置等に硫化水素ガス除去材として充填することにより、燃料ガス中の硫化水素量を簡便に低減することができる。硫黄化合物含量の少ない精製ガスは、発電機等の利用機器に損傷を与えることがなく、加えて、下流工程での触媒劣化を防止することができる。すなわち本発明の多孔性材料・多孔性複合材料によれば、発電機等のメンテナンスコストを大幅に削減することができるため、バイオガスや天然ガス等の石油代替エネルギーの利用拡大が期待される。また、本発明の多孔性材料・多孔性複合材料をフィルターに担持させた製品は、天然ガス精製等に用いられる硫化水素除去フィルターとしても使用可能である。
<< Hydrogen sulfide gas removal material >>
Since the porous material / porous composite material obtained by the present invention is excellent in hydrogen sulfide removal ability, the porous material / porous composite material of the present invention is filled in a fuel gas purifier or the like as a hydrogen sulfide gas removing material. As a result, the amount of hydrogen sulfide in the fuel gas can be easily reduced. The purified gas having a low sulfur compound content does not damage the utilization equipment such as a generator, and can prevent catalyst deterioration in the downstream process. That is, according to the porous material / porous composite material of the present invention, the maintenance cost of the generator and the like can be greatly reduced, so that the use of alternative energy for petroleum such as biogas and natural gas is expected to be expanded. The product in which the porous material / porous composite material of the present invention is supported on a filter can also be used as a hydrogen sulfide removal filter used for natural gas purification or the like.
以下、実施例を挙げて本発明をより具体的に説明する。本発明は以下の実施例によって制限を受けるものではなく、前記、後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。なお、実施例及び比較例中における分析または評価は、以下のようにして行った。 Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples, and can of course be implemented with appropriate modifications within a range that can be adapted to the above-described gist. Included in the range. In addition, the analysis or evaluation in an Example and a comparative example was performed as follows.
＜粉末Ｘ線回折測定＞
得られた複合材料について、粉末Ｘ線回折装置（ブルカー・エイエックスエス社製「ＮＥＷ Ｄ８ ＡＤＶＡＮＣＥ」）を用いて、対称反射法で測定した。測定条件を以下に示す。
１）Ｘ線源：ＣｕＫα（λ＝１．５４１８Å）４０ｋＶ ２００ｍＡ
２）ゴニオメーター：縦型ゴニオメーター
３）検出器：シンチレーションカウンター
４）回折角（２θ）範囲：３〜９０°
５）スキャンステップ：０．０５°
６）積算時間：０．５秒／ステップ
７）スリット：発散スリット＝０．５°、受光スリット＝０．１５ｍｍ、散乱スリット＝０．５°
<Powder X-ray diffraction measurement>
The obtained composite material was measured by a symmetrical reflection method using a powder X-ray diffractometer (“NEW D8 ADVANCE” manufactured by Bruker AXS). The measurement conditions are shown below.
1) X-ray source: CuKα (λ = 1.5418Å) 40 kV 200 mA
2) Goniometer: Vertical goniometer 3) Detector: Scintillation counter 4) Diffraction angle (2θ) range: 3-90 °
5) Scan step: 0.05 °
6) Integration time: 0.5 sec / step 7) Slit: Diverging slit = 0.5 °, Receiving slit = 0.15 mm, Scattering slit = 0.5 °
＜透過型電子顕微鏡（ＴＥＭ）観察＞
透過型電子顕微鏡（日立製作所製「ＨＴ７７００」、または日本電子社製「ＪＥＭ−２２００ＦＳ」）を用いて、得られた多孔性材料、及び多孔性複合材料を観察した。
<Transmission electron microscope (TEM) observation>
The obtained porous material and porous composite material were observed using a transmission electron microscope (“HT7700” manufactured by Hitachi, Ltd. or “JEM-2200FS” manufactured by JEOL Ltd.).
＜硫化水素流通系吸着試験＞
多孔性複合材料１００ｍｇをカラムに充填し、試験ガスを流し、経時的にカラム出口での硫化水素ガス濃度を、硫化水素ガス用検知管を用いて測定し、硫化水素（Ｈ2Ｓ）除去率を下記式（ｉ）；
硫化水素（Ｈ2Ｓ）除去率（％）＝｛（カラム入口での硫化水素濃度−カラム出口での硫化水素濃度）／(カラム入口での硫化水素濃度)｝×１００ …（ｉ）
に基づき算出した。
なお、試料としては、１２０℃で２４時間真空乾燥し、吸着物質を除去したものを使用した。評価条件の詳細を以下に示す。
１）測定温度：２５℃
２）湿度：０％ＲＨ
３）測定雰囲気：窒素下
４）圧力：常圧
５）試験ガス組成：硫化水素１０ｐｐｍ含有窒素ガス
６）流量：１Ｌ／ｍｉｎ
<Hydrogen sulfide flow system adsorption test>
The column is packed with 100 mg of porous composite material, the test gas is flowed, and the hydrogen sulfide gas concentration at the column outlet is measured over time using a hydrogen sulfide gas detector tube, and the hydrogen sulfide (H 2 S) removal rate is measured. Is represented by the following formula (i);
Hydrogen sulfide (H 2 S) removal rate (%) = {(hydrogen sulfide concentration at the column inlet−hydrogen sulfide concentration at the column outlet) / (hydrogen sulfide concentration at the column inlet)} × 100 (i)
Calculated based on
In addition, as a sample, what vacuum-dried at 120 degreeC for 24 hours and removed the adsorbent was used. Details of the evaluation conditions are shown below.
1) Measurement temperature: 25 ° C
2) Humidity: 0% RH
3) Measurement atmosphere: under nitrogen 4) Pressure: normal pressure 5) Test gas composition: nitrogen gas containing 10 ppm of hydrogen sulfide 6) Flow rate: 1 L / min
＜銀系触媒の平均粒子径の測定方法＞
銀系触媒の粒子径は、透過型電子顕微鏡（日立製作所製「ＨＴ７７００」、または日本電子社製「ＪＥＭ−２２００ＦＳ」）を用い、任意の２００個の銀系触媒について、倍率１０万倍で観察することにより測定した。そして、これらの平均値を、銀系触媒の平均粒子径とした。
<Measuring method of average particle diameter of silver-based catalyst>
The particle diameter of the silver-based catalyst was observed at a magnification of 100,000 times for any 200 silver-based catalysts using a transmission electron microscope (“HT7700” manufactured by Hitachi, Ltd. or “JEM-2200FS” manufactured by JEOL Ltd.). Was measured. And these average values were made into the average particle diameter of a silver-type catalyst.
実施例１
＜配位不飽和部位を有する多孔性金属錯体［Ｃｕ3（ＢＴＣ）2（Ｈ2Ｏ）3］nへのＡｇの担持＞
Ｃｕと１，３，５−ベンゼントリカルボン酸（ＢＴＣ）から形成された多孔性金属錯体（細孔径；細孔表面径９．５Å、細孔内部径１３．３Å；ＢＡＳＦ社製「Ｂａｓｏｌｉｔｅ（登録商標） Ｃ３００」、［Ｃｕ3（ＢＴＣ）2（Ｈ2Ｏ）3］n）を１２０℃で１５時間真空乾燥させて配位不飽和金属を生成させ、室温まで放冷した。この多孔性金属錯体３００ｍｇを、メタノール４．８ｍｌに分散させ、ここへＡｇＮＯ3９．４ｍｇ（０．０５ｍｍｏｌ）を含むメタノール溶液１．３ｍｌを加え、室温で１．５時間攪拌を行った。次いで、溶媒を留去し、メタノール３．０ｍｌを加えた。その後、２．１ｍｌのＮａＢＨ4１５．９ｍｇ（０．４２ｍｍｏｌ）を含むメタノール溶液を滴下し、３０分間攪拌を行った。得られた溶液を濾過し、固体をメタノールで洗浄した後、１２０℃で真空乾燥を行い、Ａｇが２質量％担持された多孔性複合材料を得た（２５６ｍｇ、収率８４％）。得られた複合材料について、粉末Ｘ線回折測定及びＴＥＭ観察を行った。粉末Ｘ線回折測定からは、Ａｇのパターンが観測されなかったが、ＴＥＭ観察により、２〜５ｎｍのＡｇ粒子が高分散状態で担持されている様子が観察された。ＴＥＭ像を図１に示す。この複合材料を用い、硫化水素流通系吸着試験を行った。結果を図２に示す。
Example 1
<Supporting Ag on Porous Metal Complex [Co 3 (BTC) 2 (H 2 O) 3 ] n Having Coordination Unsaturation Site>
Porous metal complex formed from Cu and 1,3,5-benzenetricarboxylic acid (BTC) (pore diameter; pore surface diameter 9.5 mm, pore inner diameter 13.3 mm; “Basolite (registered trademark)” manufactured by BASF ) C300 ”, [Cu 3 (BTC) 2 (H 2 O) 3 ] n ) were vacuum dried at 120 ° C. for 15 hours to form a coordinated unsaturated metal and allowed to cool to room temperature. 300 mg of this porous metal complex was dispersed in 4.8 ml of methanol, 1.3 ml of a methanol solution containing 9.4 mg (0.05 mmol) of AgNO 3 was added thereto, and the mixture was stirred at room temperature for 1.5 hours. Then the solvent was distilled off and 3.0 ml of methanol was added. Thereafter, a methanol solution containing 15.9 mg (0.42 mmol) of 2.1 ml of NaBH 4 was dropped and stirred for 30 minutes. The obtained solution was filtered, and the solid was washed with methanol, followed by vacuum drying at 120 ° C. to obtain a porous composite material carrying 2% by mass of Ag (256 mg, 84% yield). The obtained composite material was subjected to powder X-ray diffraction measurement and TEM observation. From the powder X-ray diffraction measurement, an Ag pattern was not observed, but it was observed by TEM observation that 2-5 nm Ag particles were supported in a highly dispersed state. A TEM image is shown in FIG. Using this composite material, a hydrogen sulfide flow system adsorption test was conducted. The results are shown in FIG.
実施例２
＜配位不飽和部位を有する多孔性金属錯体［Ｃｕ3（ＢＴＣ）2（Ｈ2Ｏ）3］nへのＡｇの担持＞
Ｃｕと１，３，５−ベンゼントリカルボン酸（ＢＴＣ）から形成された多孔性金属錯体（細孔径；細孔表面径９．５Å、細孔内部径１３．３Å；ＢＡＳＦ社製「Ｂａｓｏｌｉｔｅ（登録商標） Ｃ３００」、［Ｃｕ3（ＢＴＣ）2（Ｈ2Ｏ）3］n）を１２０℃で１５時間真空乾燥させて配位不飽和金属を生成させ、室温まで放冷した。この多孔性金属錯体１．５ｇを、メタノール２４ｍｌに分散させ、ＡｇＮＯ3２３．６ｍｇ（０．１４ｍｍｏｌ）を含むメタノール溶液６．４ｍｌを加え、室温で１７時間攪拌を行った。次いで、溶媒を留去し、メタノール１０ｍｌを加えた。その後、５．２ｍｌのＮａＢＨ4３９．８ｍｇ（１．０５ｍｍｏｌ）を含むメタノール溶液を滴下し、３０分間攪拌を行った。得られた溶液を濾過し、固体をメタノールで洗浄した後、１２０℃で真空乾燥を行い、Ａｇが１質量％担持された多孔性複合材料を得た（１．５１ｇ、収率１００％）。得られた複合材料について、粉末Ｘ線回折測定を行った。粉末Ｘ線回折測定からは、Ａｇのパターンがほとんど観測されなかったことから、Ａｇ粒子は微粒子化していると言える。この複合材料を用い、硫化水素流通系吸着試験を行った。結果を図２に示す。
Example 2
<Supporting Ag on Porous Metal Complex [Co 3 (BTC) 2 (H 2 O) 3 ] n Having Coordination Unsaturation Site>
Porous metal complex formed from Cu and 1,3,5-benzenetricarboxylic acid (BTC) (pore diameter; pore surface diameter 9.5 mm, pore inner diameter 13.3 mm; “Basolite (registered trademark)” manufactured by BASF ) C300 ”, [Cu 3 (BTC) 2 (H 2 O) 3 ] n ) were vacuum dried at 120 ° C. for 15 hours to form a coordinated unsaturated metal and allowed to cool to room temperature. 1.5 g of this porous metal complex was dispersed in 24 ml of methanol, 6.4 ml of a methanol solution containing 23.6 mg (0.14 mmol) of AgNO 3 was added, and the mixture was stirred at room temperature for 17 hours. The solvent was then distilled off and 10 ml of methanol was added. Thereafter, a methanol solution containing 5.2 ml of NaBH 4 39.8 mg (1.05 mmol) was dropped and stirred for 30 minutes. The obtained solution was filtered, and the solid was washed with methanol, followed by vacuum drying at 120 ° C. to obtain a porous composite material carrying 1% by mass of Ag (1.51 g, yield 100%). Powder X-ray diffraction measurement was performed on the obtained composite material. From the powder X-ray diffraction measurement, it can be said that the Ag particles are finely divided because almost no Ag pattern was observed. Using this composite material, a hydrogen sulfide flow system adsorption test was conducted. The results are shown in FIG.
実施例３
＜配位不飽和部位を有する多孔性金属錯体［Ｃｕ3（ＢＴＣ）2（Ｈ2Ｏ）3］nへのＡｇの担持＞
Ｃｕと１，３，５−ベンゼントリカルボン酸（ＢＴＣ）から形成された多孔性金属錯体（細孔径；細孔表面径９．５Å、細孔内部径１３．３Å；ＢＡＳＦ社製「Ｂａｓｏｌｉｔｅ（登録商標） Ｃ３００」、［Ｃｕ3（ＢＴＣ）2（Ｈ2Ｏ）3］n）を１２０℃で１５時間真空乾燥させて不飽和配位金属を生成させ、室温まで放冷した。この多孔性金属錯体１．５ｇを、メタノール２４ｍｌに分散させ、ＡｇＮＯ3１１．７ｍｇ（０．０７ｍｍｏｌ）を含むメタノール溶液３．２ｍｌを加え、室温で１７時間攪拌を行った。次いで、溶媒を留去し、メタノール１０ｍｌを加えた。その後、２．６ｍｌのＮａＢＨ4１９．９ｍｇ（０．５３ｍｍｏｌ）を含むメタノール溶液を滴下し、３０分間攪拌を行った。得られた溶液を濾過し、固体をメタノールで洗浄した後、１２０℃で真空乾燥を行い、Ａｇが０．５質量％担持された多孔性複合材料を得た（１．４８ｇ、収率９８％）。得られた複合材料について、粉末Ｘ線回折測定を行った。粉末Ｘ線回折測定からは、Ａｇのパターンがほとんど観測されなかったことから、Ａｇ粒子は微粒子化していると言える。この複合材料を用い、硫化水素流通系吸着試験を行った。結果を図２に示す。
Example 3
<Supporting Ag on Porous Metal Complex [Co 3 (BTC) 2 (H 2 O) 3 ] n Having Coordination Unsaturation Site>
Porous metal complex formed from Cu and 1,3,5-benzenetricarboxylic acid (BTC) (pore diameter; pore surface diameter 9.5 mm, pore inner diameter 13.3 mm; “Basolite (registered trademark)” manufactured by BASF ) C300 ”, [Cu 3 (BTC) 2 (H 2 O) 3 ] n ) were vacuum dried at 120 ° C. for 15 hours to form an unsaturated coordination metal and allowed to cool to room temperature. 1.5 g of this porous metal complex was dispersed in 24 ml of methanol, 3.2 ml of a methanol solution containing 11.7 mg (0.07 mmol) of AgNO 3 was added, and the mixture was stirred at room temperature for 17 hours. The solvent was then distilled off and 10 ml of methanol was added. Thereafter, a methanol solution containing 2.6 ml of NaBH 4 19.9 mg (0.53 mmol) was added dropwise and stirred for 30 minutes. The obtained solution was filtered, and the solid was washed with methanol, followed by vacuum drying at 120 ° C. to obtain a porous composite material carrying 0.5% by mass of Ag (1.48 g, yield 98%). ). Powder X-ray diffraction measurement was performed on the obtained composite material. From the powder X-ray diffraction measurement, it can be said that the Ag particles are finely divided because almost no Ag pattern was observed. Using this composite material, a hydrogen sulfide flow system adsorption test was conducted. The results are shown in FIG.
実施例４
＜配位不飽和部位を有する多孔性金属錯体［Ｃｕ3（ＢＴＣ）2（Ｈ2Ｏ）3］nへのＡｇの担持＞
Ｃｕと１，３，５−ベンゼントリカルボン酸（ＢＴＣ）から形成された多孔性金属錯体（細孔径；細孔表面径９．５Å、細孔内部径１３．３Å；ＢＡＳＦ社製「Ｂａｓｏｌｉｔｅ（登録商標） Ｃ３００」、［Ｃｕ3（ＢＴＣ）2（Ｈ2Ｏ）3］n）を１２０℃で１５時間真空乾燥させて配位不飽和金属を生成させ、室温まで放冷した。この多孔性金属錯体１．５ｇを、メタノール２４ｍｌに分散させ、ＡｇＮＯ3２．４ｍｇ（０．０１ｍｍｏｌ）を含むメタノール溶液０．６ｍｌを加え、室温で１７時間攪拌を行った。次いで、溶媒を留去し、メタノール１０ｍｌを加えた。その後、０．５２ｍｌのＮａＢＨ4４．０ｍｇ（０．１１ｍｍｏｌ）を含むメタノール溶液を滴下し、３０分間攪拌を行った。得られた溶液を濾過し、固体をメタノールで洗浄した後、１２０℃で真空乾燥を行い、Ａｇが０．１質量％担持された多孔性複合材料を得た（１．５０ｇ、収率１００％）。得られた複合材料について、粉末Ｘ線回折測定を行った。粉末Ｘ線回折測定からは、Ａｇのパターンがほとんど観測されなかったことから、Ａｇ粒子は微粒子化していると言える。この複合材料を用い、硫化水素流通系吸着試験を行った。結果を図２に示す。
Example 4
<Supporting Ag on Porous Metal Complex [Co 3 (BTC) 2 (H 2 O) 3 ] n Having Coordination Unsaturation Site>
Porous metal complex formed from Cu and 1,3,5-benzenetricarboxylic acid (BTC) (pore diameter; pore surface diameter 9.5 mm, pore inner diameter 13.3 mm; “Basolite (registered trademark)” manufactured by BASF ) C300 ”, [Cu 3 (BTC) 2 (H 2 O) 3 ] n ) were vacuum dried at 120 ° C. for 15 hours to form a coordinated unsaturated metal and allowed to cool to room temperature. 1.5 g of this porous metal complex was dispersed in 24 ml of methanol, 0.6 ml of a methanol solution containing 2.4 mg (0.01 mmol) of AgNO 3 was added, and the mixture was stirred at room temperature for 17 hours. The solvent was then distilled off and 10 ml of methanol was added. Thereafter, a methanol solution containing 4.02 mg (0.11 mmol) of 0.52 ml of NaBH 4 was dropped and stirred for 30 minutes. The obtained solution was filtered, and the solid was washed with methanol, followed by vacuum drying at 120 ° C. to obtain a porous composite material carrying 0.1% by mass of Ag (1.50 g, yield 100%). ). Powder X-ray diffraction measurement was performed on the obtained composite material. From the powder X-ray diffraction measurement, it can be said that the Ag particles are finely divided because almost no Ag pattern was observed. Using this composite material, a hydrogen sulfide flow system adsorption test was conducted. The results are shown in FIG.
参考例１
Ｃｕと１，３，５−ベンゼントリカルボン酸（ＢＴＣ）から形成された多孔性金属錯体（細孔径；細孔表面径９．５Å、細孔内部径１３．３Å；ＢＡＳＦ社製「Ｂａｓｏｌｉｔｅ（登録商標） Ｃ３００」、［Ｃｕ3（ＢＴＣ）2（Ｈ2Ｏ）3］n）を用いて、硫化水素流通系吸着試験を行った。結果を図２に示す。
Reference example 1
Porous metal complex formed from Cu and 1,3,5-benzenetricarboxylic acid (BTC) (pore diameter; pore surface diameter 9.5 mm, pore inner diameter 13.3 mm; “Basolite (registered trademark)” manufactured by BASF ) C300 ”, [Cu 3 (BTC) 2 (H 2 O) 3 ] n ), a hydrogen sulfide flow system adsorption test was performed. The results are shown in FIG.
比較例１
＜配位不飽和部位を有しない多孔性金属錯体［Ｚｎ（ＭｅＩｍ）2］nへのＡｇの担持＞
本比較例においては、真空加熱処理を行っても、構成金属が配位不飽和状態にならない多孔性材料として、Ｚｎと２−メチルイミダゾール（ＭｅＩｍ）から形成される多孔性金属錯体（細孔径；細孔表面径３．４Å、細孔内部径１１．６Å；ＢＡＳＦ社製「Ｂａｓｏｌｉｔｅ（登録商標） Ｚ１２００」、［Ｚｎ（ＭｅＩｍ）2］n）を試料に用いた。この多孔性金属錯体を構成する金属には、水分子が配位していない。そのため、錯体を真空条件下で加熱しても、配位不飽和状態の金属は形成されない。この多孔性金属錯体を１２０℃で１５時間真空乾燥させ、その後、室温まで放冷した。この多孔性金属錯体１．５ｇを、メタノール２４ｍｌに分散させ、ここへＡｇＮＯ3４７．３ｍｇ（０．２８ｍｍｏｌ）を含むメタノール溶液１２．８ｍｌを加え、室温で２４時間攪拌を行った。その後、溶媒を留去し、メタノール１０ｍｌを加えた。その後、１０．５ｍｌのＮａＢＨ4８０．０ｍｇ（２．１１ｍｍｏｌ）を含むメタノール溶液を滴下し、３０分間攪拌を行った。得られた溶液を濾過し、固体をメタノールで洗浄した後、１２０℃で真空乾燥を行い、Ａｇが２質量％担持された多孔性複合材料を得た（１．４８ｇ、収率９６％）。得られた複合材料について、粉末Ｘ線回折測定及びＴＥＭ観察を行った。粉末Ｘ線回折測定からは、Ａｇのパターンがほとんど観測されなかったことから、Ａｇ粒子は微粒子化していると言える。この複合材料を用い、硫化水素流通系吸着試験を行った。結果を図２に示す。
Comparative Example 1
<Supporting Ag on porous metal complex [Zn (MeIm) 2 ] n having no coordination unsaturated site>
In this comparative example, a porous metal complex (pore diameter; formed from Zn and 2-methylimidazole (MeIm) is used as a porous material in which the constituent metal does not become a coordination unsaturated state even when vacuum heat treatment is performed. A sample having a pore surface diameter of 3.4 mm and a pore internal diameter of 11.6 mm; “Basolite (registered trademark) Z1200” manufactured by BASF, [Zn (MeIm) 2 ] n ) was used as a sample. Water molecules are not coordinated to the metal constituting the porous metal complex. Therefore, even when the complex is heated under vacuum conditions, a metal in a coordinated unsaturated state is not formed. This porous metal complex was vacuum-dried at 120 ° C. for 15 hours, and then allowed to cool to room temperature. 1.5 g of this porous metal complex was dispersed in 24 ml of methanol, and 12.8 ml of a methanol solution containing 47.3 mg (0.28 mmol) of AgNO 3 was added thereto, followed by stirring at room temperature for 24 hours. Thereafter, the solvent was distilled off, and 10 ml of methanol was added. Thereafter, a methanol solution containing 10.5 ml of NaBH 4 80.0 mg (2.11 mmol) was dropped, and the mixture was stirred for 30 minutes. The obtained solution was filtered, and the solid was washed with methanol, followed by vacuum drying at 120 ° C. to obtain a porous composite material carrying 2% by mass of Ag (1.48 g, yield 96%). The obtained composite material was subjected to powder X-ray diffraction measurement and TEM observation. From the powder X-ray diffraction measurement, it can be said that the Ag particles are finely divided because almost no Ag pattern was observed. Using this composite material, a hydrogen sulfide flow system adsorption test was conducted. The results are shown in FIG.
比較例２
＜ＮａＹ型ゼオライトへのＡｇの担持＞
ＮａＹ型ゼオライト（平均細孔径；７．４Å）を予め１２０℃で１５時間真空乾燥させた後、室温まで放冷した。このゼオライト３００ｍｇを、メタノール４．８ｍｌに分散させ、ここへ１．３ｍｌのＡｇＮＯ3９．４ｍｇ（０．０５ｍｍｏｌ）を含むメタノール溶液を加え、室温で２２時間攪拌を行った。次いで、溶媒を留去し、メタノール３．０ｍｌを加えた。その後、２．１ｍｌのＮａＢＨ4１６．０ｍｇ（０．４２ｍｍｏｌ）を含むメタノール溶液を滴下し、３０分間攪拌を行った。得られた溶液を濾過し、固体をメタノールで洗浄した後、１２０℃で真空乾燥を行い、Ａｇが２質量％担持された複合材料を得た（２０６ｍｇ、収率６７％）。得られた複合材料について、粉末Ｘ線回折測定及びＴＥＭ観察を行った。粉末Ｘ線回折測定からは、Ａｇパターンがわずかに観測され、Ａｇの生成が確認できた。またＴＥＭ観察により、１２〜２４ｎｍのＡｇ粒子が担持されている様子が観察された。ＴＥＭ像を図３に示す。この複合材料を用い、硫化水素流通系吸着試験を行った。結果を図２に示す。
Comparative Example 2
<Supporting of Ag on NaY-type zeolite>
NaY-type zeolite (average pore size; 7.4 mm) was vacuum dried at 120 ° C. for 15 hours in advance, and then allowed to cool to room temperature. 300 mg of this zeolite was dispersed in 4.8 ml of methanol, and a methanol solution containing 9.4 mg (0.05 mmol) of 1.3 ml of AgNO 3 was added thereto, followed by stirring at room temperature for 22 hours. Then the solvent was distilled off and 3.0 ml of methanol was added. Then, a methanol solution containing 2.1 ml of NaBH 4 16.0 mg (0.42 mmol) was added dropwise, and the mixture was stirred for 30 minutes. The obtained solution was filtered, and the solid was washed with methanol, followed by vacuum drying at 120 ° C. to obtain a composite material carrying 2 mass% of Ag (206 mg, 67% yield). The obtained composite material was subjected to powder X-ray diffraction measurement and TEM observation. From the powder X-ray diffraction measurement, a slight Ag pattern was observed, confirming the formation of Ag. Further, it was observed by TEM observation that Ag particles of 12 to 24 nm were carried. A TEM image is shown in FIG. Using this composite material, a hydrogen sulfide flow system adsorption test was conducted. The results are shown in FIG.
Claims (8)
前記多孔性材料の一部または全部の金属が、配位不飽和状態であることを特徴とする多孔性複合材料。 A porous composite material in which a silver-based catalyst is supported on a porous material,
A porous composite material, wherein a part or all of the metal of the porous material is in a coordinated unsaturated state.
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