CN109939706A - 催化剂及其制造方法、以及合成燃气的制造方法 - Google Patents
催化剂及其制造方法、以及合成燃气的制造方法 Download PDFInfo
- Publication number
- CN109939706A CN109939706A CN201810050229.4A CN201810050229A CN109939706A CN 109939706 A CN109939706 A CN 109939706A CN 201810050229 A CN201810050229 A CN 201810050229A CN 109939706 A CN109939706 A CN 109939706A
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- Prior art keywords
- catalyst
- manufacturing
- phosphorus
- weight
- fuel gas
- Prior art date
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 137
- 239000002737 fuel gas Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 40
- 239000011574 phosphorus Substances 0.000 claims abstract description 40
- 239000006227 byproduct Substances 0.000 claims abstract description 35
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004411 aluminium Substances 0.000 claims abstract description 15
- 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
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005864 Sulphur Substances 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011591 potassium Substances 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- 239000007787 solid Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- -1 phosphorous inorganic acid Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 229920000388 Polyphosphate Chemical group 0.000 claims description 2
- 150000002012 dioxanes Chemical class 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001205 polyphosphate Chemical group 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 238000009628 steelmaking Methods 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims 1
- 230000009466 transformation Effects 0.000 abstract description 16
- 238000002309 gasification Methods 0.000 abstract description 14
- 238000004876 x-ray fluorescence Methods 0.000 description 22
- 239000000843 powder Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 244000166124 Eucalyptus globulus Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 241000124033 Salix Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 2
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- DZRZLLRDAGVQSA-UHFFFAOYSA-N C(C1=CC=CC=C1)P(O)(O)(O)CC1=CC=CC=C1.P(OCC1=CC=CC=C1)(OCC1=CC=CC=C1)O Chemical compound C(C1=CC=CC=C1)P(O)(O)(O)CC1=CC=CC=C1.P(OCC1=CC=CC=C1)(OCC1=CC=CC=C1)O DZRZLLRDAGVQSA-UHFFFAOYSA-N 0.000 description 1
- YRHYVMHTPLSDOU-UHFFFAOYSA-N C(CC)P(OCCC)(OCCC)(O)CCC.P(O)(O)O Chemical compound C(CC)P(OCCC)(OCCC)(O)CCC.P(O)(O)O YRHYVMHTPLSDOU-UHFFFAOYSA-N 0.000 description 1
- WXWRXFAVJLEWMR-UHFFFAOYSA-N C=1C=CC=CC=1OP(O)OC1=CC=CC=C1.C=1C=CC=CC=1P(O)(O)(O)C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1OP(O)OC1=CC=CC=C1.C=1C=CC=CC=1P(O)(O)(O)C1=CC=CC=C1 WXWRXFAVJLEWMR-UHFFFAOYSA-N 0.000 description 1
- JPSHUYOXYXMQDK-UHFFFAOYSA-N COP(O)OC.CP(C)(O)(O)O Chemical compound COP(O)OC.CP(C)(O)(O)O JPSHUYOXYXMQDK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FZUYRIAEOWIOPH-UHFFFAOYSA-N [P].[Ca].[Ca] Chemical compound [P].[Ca].[Ca] FZUYRIAEOWIOPH-UHFFFAOYSA-N 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- UXCZDZCDKMBLRX-UHFFFAOYSA-N dibutyl hydrogen phosphite dibutyl(trihydroxy)-lambda5-phosphane Chemical compound C(CCC)P(O)(O)(O)CCCC.P(OCCCC)(OCCCC)O UXCZDZCDKMBLRX-UHFFFAOYSA-N 0.000 description 1
- PFUUPHGRHNCEHN-UHFFFAOYSA-N diethyl hydrogen phosphite diethyl(trihydroxy)-lambda5-phosphane Chemical compound CCOP(O)OCC.CCP(O)(O)(O)CC PFUUPHGRHNCEHN-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- YVTMJBPETAAUFS-UHFFFAOYSA-N dipropan-2-yl hydrogen phosphite trihydroxy-di(propan-2-yl)-lambda5-phosphane Chemical compound C(C)(C)P(O)(O)(O)C(C)C.P(OC(C)C)(OC(C)C)O YVTMJBPETAAUFS-UHFFFAOYSA-N 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005005 fuel gas manufacturing Methods 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical group [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/182—Phosphorus; Compounds thereof with silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本揭露提供一种催化剂、催化剂制造方法、以及合成燃气的制造方法。该催化剂的组成符合以下条件(1)或条件(2):条件(1)4wt%至6wt.%的硅、5wt.%至10wt.%的磷、25wt.%至35wt.%的钙、8wt.%至21wt.%的铁、36wt.%至41wt.%的氧、以及0.1wt.%至5wt.%的镁、铝、锰、或其组合,以该催化剂的总重为基准;或者条件(2)3wt.%至6wt.%的铝、6wt.%至8wt.%的硅、12wt.%至16wt.%的磷、28wt.%至32wt.%的钙、38wt.%至50wt.%的氧、以及0.1wt.%至3wt.%的镁、硫、钾、钛、锰、铁、或其组合,以该催化剂的总重为基准。本发明的催化剂作为流体化床床质,可以降低副产物,且提升气化转化效率。
Description
技术领域
本揭露关于一种催化剂及其制造方法、以及合成燃气的制造方法。
背景技术
随着经济的快速发展,石油资源的枯竭、环境污染和全球暖化的加剧,亟需寻找高能量密度、环保、可持续发展的新能源体系。因此,由生物质(biomass)气化所产生的合成气作为替代能源也越来越受到关注。
然而,在使用传统流体化床反应装置中从生物质制造合成气的过程中,同时会产生焦炭(char)、灰分(ash)及焦油(tar)等副产物,导致气化转化效率降低。此外,合成气中所含的副产物会引起后续下游过程和设备的结垢、堵塞。例如冷凝的焦油会造成气体清洁设备严重结垢、进入发电机组的焦油会妨碍合成气应用的运行、且焦油与冷凝水混合后也易造成困难的水处理问题。
因此,业界需要一种新颖的催化剂作为流体化床床质,以降低副产物,提升气化转化效率。
发明内容
本发明的目的在于提供一种能够降低副产物、提升气化转化效率的催化剂。
根据本揭露实施例,本揭露提供一种催化剂,其中该催化剂的组成符合以下条件(1)或条件(2):
条件(1)4wt.%至6wt.%的硅、5wt.%至10wt.%的磷、25wt.%至35wt.%的钙、8wt.%至21wt.%的铁、36wt.%至41wt.%的氧、以及0.1wt.%至5wt.%的镁、铝、锰、或其组合,以该催化剂的总重为基准;或者
条件(2)3wt.%至6wt.%的铝、6wt.%至8wt.%的硅、12wt.%至16wt.%的磷、28wt.%至32wt.%的钙、38wt.%至50wt.%的氧、以及0.1wt.%至3wt.%的镁、硫、钾、钛、锰、铁、或其组合,以该催化剂的总重为基准。
根据本揭露实施例,本揭露提供一种上述催化剂的制造方法,包括:将一工业副产品含浸于一溶液中,得到一混合物,其中该溶液包括一含磷化合物溶于一溶剂中,其中该含磷化合物包括含磷的无机酸、含磷的盐类、含磷的酯类、或上述的组合;对该混合物进行烘干以移除溶剂,得到一固体;以及,对所得固体进行一煅烧制程,得到本揭露所述催化剂。
根据本揭露其他实施例,本揭露提供一种合成燃气的制造方法,包括将本揭露所述催化剂置于一反应器中;提供一碳源于该反应器及通入一气体;以及,进行一加热步骤以经由该催化剂将该碳源转换成一合成燃气。
相较于现有技术,本发明的优点在于:本发明的催化剂具有特定组成及比例,当置于反应装置(例如流体化床,作为床质材料)进行合成燃气制程时,可降低合成燃气的副产物含量(例如焦油)、以及提升碳氢化合物转化效率;而且,本发明的催化剂可利用大量且廉价的工业副产品来进行制备,因此可大幅降低合成燃气制程成本。
具体实施方式
本揭露实施例提供一种催化剂及其制造方法、以及合成燃气的制造方法。根据本揭露实施例,本揭露所述的催化剂可例如为一具有硅、磷、及钙的复合氧化物(silicon-phosphorus-calcium-containing composite oxide),该催化剂可进一步包含铝、镁、硫、钾、钛、锰、铁、或其组合。由于本揭露所述催化剂具有特定组成及比例,当置于反应装置(例如流体化床,作为床质材料)进行合成燃气制程时,可降低合成燃气的副产物含量(例如焦油)、以及提升碳氢化合物转化效率。此外,本揭露所述催化剂可利用大量且廉价的工业副产品来进行制备,因此可大幅降低合成燃气制程成本。
根据本揭露实施例,本揭露提供一种催化剂,其中该催化剂的组成符合以下条件(1)或条件(2):
条件(1)4wt.%至6wt.%的硅、5wt.%至10wt.%的磷、25wt.%至35wt.%的钙、8wt.%至21wt.%的铁、36wt.%至41wt.%的氧、以及0.1wt.%至5wt.%的镁、铝、锰、或其组合,以该催化剂的总重为基准;或者条件(2)3wt.%至6wt.%的铝、6wt.%至8wt.%的硅、12wt.%至16wt.%的磷、28wt.%至32wt.%的钙、38wt.%至50wt.%的氧、以及0.1wt.%至3wt.%的镁、硫、钾、钛、锰、铁、或其组合,以该催化剂的总重为基准。
根据本揭露实施例,本揭露催化剂所包含的硅、磷、钙、铁、铝、镁、钾、钛、及/或锰是以氧化物(例如氧化硅、五氧化二磷、氧化钙、氧化铁、氧化铝、氧化镁、氧化钾、氧化钛、及/或氧化锰)的形式存在,因此本揭露催化剂为一复合氧化物。根据本揭露实施例,若本揭露催化剂包含硫时,本揭露催化剂中的金属成份可以硫化物形成存在。
根据本揭露实施例,本揭露催化剂的组成是符合条件(1),其中磷的重量(W1)与硅、钙、及铁的总重(W2)的比值(W1/W2)为0.1至0.2(例如0.11、0.12、0.13、0.14、0.15、0.16、0.17、0.18、或0.19),及/或磷的重量(W1)与氧的重量(W3)的比值(W1/W3)为0.1至0.27(例如0.11、0.12、0.13、0.14、0.15、0.16、0.17、0.18、0.19、0.20、0.21、0.22、0.23、0.24、0.25、或0.26)。若磷的含量过低时,则无法促进催化剂内电子/空穴对(electron/hole pair)分离及产生有效电偶极矩,导致气化转化效率降低。反之,若磷的含量过高时,则易导致催化剂表面空乏区(depletion region)过窄,所产生的电子/空穴对(electron/hole pair)容易再结合,导致气化转化效率降低。
根据本揭露实施例,本揭露催化剂的组成是符合条件(2),其中磷的重量(W1)与硅、钙、及铁的总重(W2)的比值(W1/W2)为0.3至0.4(例如0.31、0.32、0.33、0.34、0.35、0.36、0.37、0.38、或0.39),及/或磷的重量(W1)与氧的重量(W3)的比值(W1/W3)为0.3至0.4(例如0.31、0.32、0.33、0.34、0.35、0.36、0.37、0.38、或0.39)。若磷的含量过低时,则无法促进催化剂内电子/空穴对(electron/hole pair)分离及提供有效电偶极矩,导致无法稳定自由基中间产物,故气化转化效率降低。反之,若磷的含量过高时,则易导致催化剂表面的空乏区(depletion region)过窄,电子/空穴对容易再结合,同样造成无法提供有效电偶极矩及稳定自由基中间产物,导致气化转化效率降低。
根据本揭露实施例,本揭露催化剂的比表面积可为10m2/g至100m2/g,例如20m2/g、30m2/g、40m2/g、50m2/g、60m2/g、70m2/g、80m2/g、或90m2/g。
根据本揭露实施例,本揭露提供一种催化剂的制备方法,可使用大量且廉价的工业副产品(例如含铁、钙、镁、硅、及/或铝等金属成分)经含磷液溶改质及锻烧后所得。根据本揭露实施例,该催化剂的制备方法包括以下步骤。首先,将一工业副产品含浸于一溶液中,得到一混合物,其中该溶液包括一含磷化合物溶于一溶剂中,其中该含磷化合物包括含磷的无机酸、含磷的盐类、含磷的酯类、或上述的组合。接着,对该混合物进行烘干以移除溶剂,得到一固体。接着,对所得固体进行一煅烧制程,得到本揭露所述催化剂。
值得注意的是,如果以盐酸或硫酸取代本揭露所述含磷液溶来对该工业副产品进行改质,则所得催化剂应用于合成燃气制程时,会有产生含氯或含硫等物质造成气体污染。此外,若以有机酸(例如甲酸、或乙酸)取代本揭露所述含磷液溶来对该工业副产品进行改质,仍无法有效提升所得催化剂的气化转化效率。
根据本揭露某些实施例,在将该工业副产品含浸于该溶液中得到该混合物后,可利用过滤法、滗析法(decantation)或更藉由一磁力分选法(magnetic sorting)将该混合物分离成一低密度部份及一高密度部份,以及取该低密度部份或该高密度部份的一者进行烘干以移除溶剂,得到该固体。根据本揭露实施例,以该混合物的高密度部份进行烘干及煅烧所得的催化剂,其具有较高的铁及锰含量。
根据本揭露实施例,该工业副产物可为炼钢炉石(steel slags)。此外,根据本揭露实施例,该工业副产品不含镍、及/或铬,因此所得催化剂不含镍、及/或铬,不会产成有害废弃物污染问题。在此,工业副产品不含镍(或铬)是指镍(或铬)元素在该工业副产品中的含量为0或小于等于约0.01wt.%,以该工业副产品总重为基准。
根据本揭露实施例,该工业副产品的组成符合以下条件(1)或条件(2):
条件(1)4wt.%至6wt.%的硅、5wt.%至10wt.%的磷、25wt.%至35wt.%的钙、8wt.%至21wt.%的铁、36wt.%至41wt.%的氧、以及0.1wt.%至5wt.%的镁、铝、锰、或其组合,以该催化剂的总重为基准;或者
条件(2)3wt.%至6wt.%的铝、6wt.%至8wt.%的硅、12wt.%至16wt.%的磷、28wt.%至32wt.%的钙、38wt.%至50wt.%的氧、以及0.1wt.%至3wt.%的镁、硫、钾、钛、锰、铁、或其组合,以该催化剂的总重为基准。
根据本揭露实施例,该工业副产品的组成符合条件(1),且该含磷化合物与该工业副产品的重量比为1:10至1:5(例如1:9、1:8、1:7、或1:6)。此外,该工业副产品的组成符合条件(2),且该含磷化合物与该工业副产品的重量比为1:5至1:2(例如1:4、或1:3)。
根据本揭露实施例,该含磷化合物可为含磷的无机酸,例如磷酸、亚磷酸、次磷酸、或多聚磷酸。
根据本揭露实施例,该含磷化合物可为含磷的盐类,例如磷酸盐、亚磷酸盐、次磷酸盐、或多聚磷酸盐。举例来说,该含磷的盐类可为含磷的钾盐、含磷的铝盐、含磷的铁盐、含磷的镁盐、含磷的钙盐、含磷的钛盐、或含磷的锰盐。
根据本揭露实施例,该含磷化合物可为含磷的酯类,例如磷酸酯、亚磷酸酯、或次磷酸酯。举例来说,该含磷的酯类可为亚磷酸二甲酯(dimethyl phosphite)、亚磷酸二乙酯(diethyl phosphite)、亚磷酸二丙酯(dipropyl phosphite)、亚磷酸二异丙酯(diisopropyl phosphite)、亚磷酸二丁酯(dibutyl phosphite)、亚磷酸三甲酯(trimethyl phosphite)、亚磷酸三乙酯(triethyl phosphite)、亚磷酸三丙酯(tripropylphosphite)、亚磷酸三异丙酯(triisopropyl phosphite)、亚磷酸三丁酯(tributylphosphite)、亚磷酸二苯酯(diphenyl phosphite)、亚磷酸二苄酯(dibenzyl phosphite)、磷酸三甲酯(trimethyl phosphate)、磷酸三乙酯(triethyl phosphate)、或磷酸三苯酯(triphenyl phosphate)。
根据本揭露实施例,该溶剂可为水、四氢呋喃、异丙醇、甲醇、乙醇、乙腈、二恶烷、或丙酮。根据本揭露实施例,该溶液(包括该含磷化合物及溶剂)的固含量可为50%至85%。根据本揭露实施例,在进行含浸步骤时,该工业副产品是完全浸泡于该溶液中,且在充分搅拌后,得到该混合物。
根据本揭露实施例,该煅烧制程的制程温度可为约300℃至800℃,例如400℃、500℃、600℃、或700℃。此外,该煅烧制程的制程时间可为30分钟至6小时,例如1小时、2小时、3小时、4小时、或5小时。
根据本揭露实施例,本揭露提供一种合成燃气的制造方法,包括将上述催化剂置于一反应器中。接着,提供一碳源于该反应器中。接着,进行一加热步骤,将该碳源经由该催化剂转换成一合成燃气。根据本揭露实施例,该碳源经由该催化剂转换成该合成燃气时,可通入一载气,其中该载气包含氮气、或惰性气体。
根据本揭露实施例,在将该催化剂置于该反应器之前,可先对该催化剂进行一破碎筛选处理,以使得该催化剂的粒径介于50μm至1,000μm之间,例如介于50μm至700μm之间、或200μm至1000μm之间。
根据本揭露实施例,该反应器可例如为固定式反应器、流体化床式反应器、挟带床式反应器、或双床式反应器。根据本揭露实施例,该碳源可为生物质(biomass),例如稻秆、木屑、稻壳、或煤炭。
根据本揭露实施例,该加热步骤温度为600℃至1000例如600℃、700℃、800℃、或900℃。根据本揭露实施例,该催化剂与该碳源的重量比可为1:1至5:1,例如:1:2、1:3、或1:4。
根据本揭露实施例,该合成燃气的热值范围为3-18MJ/Nm3。举例来说,该合成燃气包括氢气(H2)、一氧化碳(CO)、甲烷(CH4)、或上述的组合。
根据本揭露实施例,使用本揭露催化剂的合成燃气制造方法,可具有气化转化效率介于约25%至58%,例如46%、47%、48%、49%、50%、51%、52%、53%、54%、55%、56%、57%、58%、或59%。根据本揭露实施例,可以热导气相层析仪(gas chromatographwith thermal conductivity detector、GC/TCD)分析所得合成燃气的热值,而该气化转化效率的定义为:(所得合成燃气的热值/碳源的热值)×100%。
为了让本揭露的上述和其他目的、特征、和优点能更明显易懂,下文特举数实施例,作详细说明如下:
催化剂的制备:
实施例1:
首先,将100重量份炉石粉(a)(由中联资源股份有限公司制造)(以X光荧光分析仪(X-ray fluorescence spectrometer、XRF)分析该炉石粉的组成成份,结果如表1所示)含浸于一溶液中,其中该溶液包含1.47重量份的磷酸以及20重量份的水。于室温下搅拌4小时后,利用磁力分选将溶液中低密度部份(易悬浮)和高密度部份(易沉降)分离,并将高密度部份以105℃烘干除水后,得到一固体。接着,将以400℃锻烧该固体3小时,得到催化剂(1)。以X光荧光分析仪(X-ray fluorescence spectrometer、XRF)分析催化剂(1)的组成成份,结果如表1所示。
实施例2:
依实施例1所述催化剂(1)的制备方式进行,除了将溶液中1.47重量份的磷酸增加至14.7重量份。于室温下搅拌4小时后,利用磁力分选将溶液中低密度部份和高密度部份分离,并将高密度部份以105℃烘干除水后,得到一固体。接着,将以400℃锻烧该固体3小时,得到催化剂(2)。以X光荧光分析仪(X-ray fluorescence spectrometer、XRF)分析催化剂(2)的组成成份,结果如表1所示。
实施例3:
依实施例2所述催化剂(2)的制备方式进行,除了选用低密度部份以105℃烘干除水后,得到一固体。接着,将以400℃锻烧该固体3小时,得到催化剂(3)。以X光荧光分析仪(X-ray fluorescence spectrometer、XRF)分析催化剂(3)的组成成份,结果如表1所示。
实施例4:
依实施例1所述催化剂(1)的制备方式进行,除了将溶液中1.47重量份的磷酸增加至25重量份。于室温下搅拌4小时后,利用磁力分选将溶液中低密度部份和高密度部份分离,并将高密度部份以105℃烘干除水后,得到一固体。接着,将以400℃锻烧该固体3小时,得到催化剂(4)。以X光荧光分析仪(X-ray fluorescence spectrometer、XRF)分析催化剂(4)的组成成份,结果如表1所示。
实施例5:
依实施例1所述催化剂(1)的制备方式进行,除了将溶液中1.47重量份的磷酸增加至40重量份。于室温下搅拌4小时后,利用磁力分选将溶液中低密度部份和高密度部份分离,并将高密度部份以105℃烘干除水后,得到一固体。接着,将以400℃锻烧该固体3小时,得到催化剂(5)。以X光荧光分析仪(X-ray fluorescence spectrometer、XRF)分析催化剂(5)的组成成份,结果如表1所示。
表1
实施例6:
首先,将100重量份炉石粉(b)(由中联资源股份有限公司制造)(以X光荧光分析仪(X-ray fluorescence spectrometer、XRF)分析该炉石粉的组成成份,结果如表2所示)含浸于一溶液中,其中该溶液包含1.47重量份的磷酸以及20重量份的水。于室温下搅拌4小时后,利用磁力分选将溶液中低密度部份(易悬浮)和高密度部份(易沉降)分离,并将高密度部份以105℃烘干除水后,得到一固体。接着,将以400℃锻烧该固体3小时,得到催化剂(6)。以X光荧光分析仪(X-ray fluorescence spectrometer、XRF)分析催化剂(6)的组成成份,结果如表2所示。
实施例7:
依实施例6所述催化剂(6)的制备方式进行,除了将溶液中1.47重量份的磷酸增加至14.7重量份。于室温下搅拌4小时后,利用磁力分选将溶液中低密度部份和高密度部份分离,并将高密度部份以105℃烘干除水后,得到一固体。接着,将以400℃锻烧该固体3小时,得到催化剂(7)。以X光荧光分析仪(X-ray fluorescence spectrometer、XRF)分析催化剂(7)的组成成份,结果如表2所示。
实施例8:
依实施例6所述催化剂(6)的制备方式进行,除了将溶液中1.47重量份的磷酸增加至25重量份。于室温下搅拌4小时后,利用磁力分选将溶液中低密度部份和高密度部份分离,并将高密度部份以105℃烘干除水后,得到一固体。接着,将以400℃锻烧该固体3小时,得到催化剂(8)。以X光荧光分析仪(X-ray fluorescence spectrometer、XRF)分析催化剂(8)的组成成份,结果如表2所示。
实施例9:
依实施例6所述催化剂(6)的制备方式进行,除了将溶液中1.47重量份的磷酸增加至40重量份。于室温下搅拌4小时后,利用磁力分选将溶液中低密度部份和高密度部份分离,并将高密度部份以105℃烘干除水后,得到一固体。接着,将以400℃锻烧该固体3小时,得到催化剂(9)。以X光荧光分析仪(X-ray fluorescence spectrometer、XRF)分析催化剂(9)的组成成份,结果如表2所示。
表2
比较例1:
首先,将100重量份炉石粉(a)含浸于一溶液中,其中该溶液包含0.6重量份的甲酸以及20重量份的水。于室温下搅拌4小时后,利用磁力分选将溶液中低密度部份(易悬浮)和高密度部份(易沉降)分离,并将高密度部份以105℃烘干除水后,得到一固体。接着,将以400℃锻烧该固体3小时,得到催化剂(10)。
比较例2:
依比较例1所述催化剂(10)的制备方式进行,除了将溶液中0.6重量份的甲酸增加至4.4重量份。于室温下搅拌4小时后,利用磁力分选将溶液中低密度部份和高密度部份分离,并将高密度部份以105℃烘干除水后,得到一固体。接着,将以400℃锻烧该固体3小时,得到催化剂(11)。
合成燃气的制备:
提供一高周波加热固定床式气化反应器。将催化剂样品及柳桉木生质物(催化剂样品及柳桉木生质物的重量比为4:1)混合并置于该高周波加热固定床气化反应器的固定承盘中。接着,导入载气(N2、流量为80mL/min至200mL/min)于高周波加热固定床气化反应器中。接着,利用高周波加热装置快速将反应器升温至850度,并于反应器出口端收集合成燃气。利用热导气相层析仪(gas chromatograph with thermal conductivity detector、GC/TCD)分析所得合成燃气的热值,并计算出气化转化效率。在此,分别以炉石粉(a)、石英砂(由Sigma-Aldrich贩卖)、及催化剂(1)至催化剂(11)作为催化剂样品,以上述步骤进行合成燃气的制备,并量测气化转化效率,结果如表3所示。
表3
改质方式 | 气化转化效率(J.%) | |
炉石粉(a) | - | 44.3 |
石英砂 | - | 23.8 |
催化剂(1) | 炉石粉(a)/1.47wt.%的磷酸/高密度部份 | 28.1 |
催化剂(2) | 炉石粉(a)/14.7wt.%的磷酸/高密度部份 | 56.5 |
催化剂(3) | 炉石粉(a)/14.7wt.%的磷酸/低密度部份 | 49.1 |
催化剂(4) | 炉石粉(a)/25wt.%的磷酸/高密度部份 | 26.0 |
催化剂(5) | 炉石粉(a)/40wt.%的磷酸/高密度部份 | 25.5 |
催化剂(6) | 炉石粉(b)/1.47wt.%的磷酸/高密度部份 | 26.4 |
催化剂(7) | 炉石粉(b)/14.7wt.%的磷酸/高密度部份 | 31.0 |
催化剂(8) | 炉石粉(b)/25wt.%的磷酸/高密度部份 | 48.9 |
催化剂(9) | 炉石粉(b)/40wt%的磷酸/高密度部份 | 47.9 |
催化剂(10) | 炉石粉(a)/0.6wt%的甲酸/高密度部份 | 36.8 |
催化剂(11) | 炉石粉(a)/4.4wt.%的甲酸/高密度部份 | 29.2 |
由表3可知,实施例2所得的催化剂所达到的气化转化效率为石英砂(传统流化床床质主要组成物)的气化转化效率两倍以上。因此,本揭露所述具有特定组成及比例的催化剂,当置于反应装置进行合成燃气制程时,确实可降低合成燃气的副产物含量,进一步提升碳氢化合物转化效率。
虽然本揭露已以数个实施例揭露如上,然其并非用以限定本揭露,任何本技术领域中具有通常知识者,在不脱离本揭露的精神和范围内,当可作任意的更动与润饰,因此本揭露的保护范围当视后附的申请专利范围所界定者为准。
Claims (24)
1.一种催化剂,其中该催化剂的组成符合以下条件(1)或条件(2):
条件(1)4wt.%至6wt.%的硅、5wt.%至10wt.%的磷、25wt.%至35wt.%的钙、8wt.%至21wt.%的铁、36wt.%至41wt.%的氧、以及0.1wt.%至5wt.%的镁、铝、锰、或其组合,以该催化剂的总重为基准;或者
条件(2)3wt.%至6wt.%的铝、6wt.%至8wt.%的硅、12wt.%至16wt.%的磷、28wt.%至32wt.%的钙、38wt.%至50wt.%的氧、以及0.1wt.%至3wt.%的镁、硫、钾、钛、锰、铁、或其组合,以该催化剂的总重为基准。
2.如权利要求1所述的催化剂,其中该催化剂的组成符合条件(1),且磷的重量(W1)与硅、钙、及铁的总重(W2)的比值(W1/W2)为0.1至0.2。
3.如权利要求1所述的催化剂,其中该催化剂的组成符合条件(1),且磷的重量(W1)与氧的重量(W3)的比值(W1/W3)为0.1至0.27。
4.如权利要求1所述的催化剂,其中该催化剂的组成符合条件(2),且磷的重量(W1)与硅、钙、及铁的总重(W2)的比值(W1/W2)为0.3至0.4。
5.如权利要求1所述的催化剂,其中该催化剂的组成符合条件(2),且磷的重量(W1)与氧的重量(W3)的比值(W1/W3)为0.3至0.4。
6.如权利要求1所述的催化剂,其中该催化剂的比表面积是10m2/g至100m2/g。
7.一种催化剂的制造方法,包括:
将工业副产品含浸于一溶液中,得到混合物,其中该溶液包括含磷化合物溶于一溶剂中,其中该含磷化合物包括含磷的无机酸、含磷的盐类、含磷的酯类、或上述的组合;
对该混合物进行烘干以移除溶剂,得到固体;以及
对所得固体进行煅烧制程,得到权利要求1所述的催化剂。
8.如权利要求7所述的催化剂的制造方法,其中该工业副产物为炼钢炉石。
9.如权利要求7所述的催化剂的制造方法,其中该工业副产品不含镍。
10.如权利要求7所述的催化剂的制造方法,其中该工业副产品不含铬。
11.如权利要求7所述的催化剂的制造方法,其中该工业副产品的组成符合以下条件(1)或条件(2):
条件(1)4wt.%至6wt.%的硅、5wt.%至10wt.%的磷、25wt.%至35wt.%的钙、8wt%至21wt.%的铁、36wt.%至41wt.%的氧、以及0.1wt.%至5wt.%的镁、铝、锰、或其组合,以该催化剂的总重为基准;或者
条件(2)3wt.%至6wt.%的铝、6wt.%至8wt.%的硅、12wt.%至16wt%的磷、28wt.%至32wt.%的钙、38wt.%至50wt.%的氧、以及0.1wt.%至3wt.%的镁、硫、钾、钛、锰、铁、或其组合,以该催化剂的总重为基准。
12.如权利要求11所述的催化剂的制造方法,其中该工业副产品的组成符合条件(1),且该含磷化合物与该工业副产品的重量比为1:10至1:5。
13.如权利要求11所述的催化剂的制造方法,其中该工业副产品的组成符合条件(2),且该含磷化合物与该工业副产品的重量比为1:5至1:2。
14.如权利要求7所述的催化剂的制造方法,其中该含磷的无机酸是磷酸、亚磷酸、次磷酸、或多聚磷酸。
15.如权利要求7所述的催化剂的制造方法,其中该含磷的盐类是磷酸盐、亚磷酸盐、次磷酸盐、或多聚磷酸盐。
16.如权利要求7所述的催化剂的制造方法,其中该含磷的酯类是磷酸酯、亚磷酸酯、或次磷酸酯。
17.如权利要求7所述的催化剂的制造方法,其中该溶剂是水、四氢呋喃、异丙醇、甲醇、乙醇、乙腈、二恶烷、或丙酮。
18.如权利要求7所述的催化剂的制造方法,其中该煅烧制程的温度是300至800℃。
19.如权利要求7所述的催化剂的制造方法,其中该煅烧制程的时间是30分钟至6小时。
20.如权利要求7所述的催化剂的制造方法,其中在将该工业副产品含浸于该溶液中得到该混合物后,更包括:
经由过滤法、滗析法或磁力分选法将混合物分离成低密度部份及高密度部份;以及
取该低密度部份或该高密度部份的一者进行烘干以移除溶剂,得到固体。
21.一种合成燃气的制造方法,包括:
将权利要求1所述的催化剂置于一反应器中;
导入碳源于该反应器中;以及
进行加热步骤将该碳源以经由该催化剂转换成合成燃气。
22.如权利要求21所述的合成燃气的制造方法,其中该加热步骤温度介于600-1000℃之间。
23.如权利要求21所述的合成燃气的制造方法,其中该催化剂与该碳源的重量比介于1:1至5:1之间。
24.如权利要求21所述的合成燃气的制造方法,其中该合成燃气包括H2、CO、CH4、或上述的组合。
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US4692172A (en) * | 1984-07-19 | 1987-09-08 | Texaco Inc. | Coal gasification process |
CN104772153A (zh) * | 2014-01-12 | 2015-07-15 | 中国科学院过程工程研究所 | 钢渣基金属氧化物固体碱催化剂制备方法及其应用 |
CN105008498A (zh) * | 2013-02-05 | 2015-10-28 | 瑞来斯实业公司 | 催化气化碳质原料的方法 |
CN105567327A (zh) * | 2016-02-25 | 2016-05-11 | 青岛理工大学 | 一种基于高炉渣余热回收的高湿污泥气化制取富氢燃气的方法 |
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US4692172A (en) * | 1984-07-19 | 1987-09-08 | Texaco Inc. | Coal gasification process |
CN105008498A (zh) * | 2013-02-05 | 2015-10-28 | 瑞来斯实业公司 | 催化气化碳质原料的方法 |
CN104772153A (zh) * | 2014-01-12 | 2015-07-15 | 中国科学院过程工程研究所 | 钢渣基金属氧化物固体碱催化剂制备方法及其应用 |
CN105567327A (zh) * | 2016-02-25 | 2016-05-11 | 青岛理工大学 | 一种基于高炉渣余热回收的高湿污泥气化制取富氢燃气的方法 |
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YONGQI SUN ETAL.: "Integrated carbon dioxide/sludge gasification using waste heat from hot slags: Syngas production and sulfur dioxide fixation", 《BIORESOURCE TECHNOLOGY》 * |
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