CN112547064A - 一种利用负载铜或铜氧化物纳米颗粒的催化剂脱除卤代芳烃化合物中卤素的方法 - Google Patents
一种利用负载铜或铜氧化物纳米颗粒的催化剂脱除卤代芳烃化合物中卤素的方法 Download PDFInfo
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- CN112547064A CN112547064A CN202011403596.1A CN202011403596A CN112547064A CN 112547064 A CN112547064 A CN 112547064A CN 202011403596 A CN202011403596 A CN 202011403596A CN 112547064 A CN112547064 A CN 112547064A
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- Prior art keywords
- copper
- halogenated aromatic
- aromatic hydrocarbon
- cuo
- catalyst
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000010949 copper Substances 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 25
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 22
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 22
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 21
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 17
- 150000002367 halogens Chemical class 0.000 title claims abstract description 17
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 19
- -1 chlorophenyl compound Chemical class 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001298 alcohols Chemical class 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 150000003333 secondary alcohols Chemical class 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 33
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 18
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 12
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 12
- 229960001545 hydrotalcite Drugs 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 125000000075 primary alcohol group Chemical group 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 238000005695 dehalogenation reaction Methods 0.000 abstract description 9
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- 150000003138 primary alcohols Chemical class 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 42
- 238000001514 detection method Methods 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 229960004643 cupric oxide Drugs 0.000 description 15
- 239000006228 supernatant Substances 0.000 description 14
- 238000007256 debromination reaction Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000386 donor Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 2
- UDHAWRUAECEBHC-UHFFFAOYSA-N 1-iodo-4-methylbenzene Chemical compound CC1=CC=C(I)C=C1 UDHAWRUAECEBHC-UHFFFAOYSA-N 0.000 description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 2
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- QENIALCDPFDFHX-UHFFFAOYSA-N 1,4-dibromo-2,5-dimethylbenzene Chemical compound CC1=CC(Br)=C(C)C=C1Br QENIALCDPFDFHX-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005831 deiodination reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
- 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
- B01J23/72—Copper
-
- 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
- B01J23/78—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 alkali- or alkaline earth 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
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Abstract
本发明公开了一种利用负载铜或铜氧化物纳米颗粒的催化剂脱除卤代芳烃化合物中卤素的方法,属于催化合成技术领域。本发明将卤代芳香烃底物与所选醇类、碱在铜或氧化铜纳米颗粒负载的催化剂存在条件下进行接触,加热搅拌。利用醇类在铜纳米颗粒表面形成的活性氢进攻多卤代芳香烃,从而实现卤代芳香烃的快速深度脱卤,其中所述醇类为能够作为溶剂的伯醇或仲醇;卤代芳烃类化合物包括氯代苯基化合物,溴代苯基化合物和碘代苯基化合物中的任一种或几种。该方法操作简单,经济成本低廉,在优化条件下可在10~15h将卤代芳香烃完全转化。
Description
技术领域
本发明涉及一种利用负载铜或铜氧化物纳米颗粒的催化剂脱除卤代芳烃化合物中卤素的方法,属于催化合成技术领域。
背景技术
卤素基团是典型保护和引导基团,所以卤代芳烃化合物被广泛用作化学工业,农业化学中许多化学转化的起始原料。多溴取代的联苯醚是最广泛使用的阻燃材料,但是其造成的环境污染也日益严,因此,需要寻找一种高效的脱除卤代芳烃化合物中卤素的方法。加氢脱卤是合成中的重要有机转化反应,并在卤代芳烃化合物的降解中起着重要作用。研究表明,零价铁脱卤是在好氧条件下通过类Fenton反应进行卤代芳烃加氢脱卤的最有效技术。但是,这个过程很慢,并导致铁离子的释放,进而无法高效的脱除卤素。
探索更有效、更环保的催化剂一直是研究人员关注的焦点。现有技术已经研究了利用过渡金属络合物的均相催化体系将CAr-X键转变为C-H键从而实现脱除卤代脂肪烃化合物的卤素的方法。但是,这些过渡金属络合物通常不稳定且不可回收,并且络合物中的某些配体是有毒的,对空气敏感并且难以合成。所以在各种加氢脱卤催化剂中,非均相催化剂是在温和条件下裂解芳基卤化物中C-X键强大而有效的选择。目前,贵金属纳米粒子(MNP,M=Pd、Au、Ag、Pt)已广泛用于加氢脱卤催化,成本较高。不仅催化剂在脱卤反应中起重要作用,氢源的选择也是另一个重要的研究方向。现有技术已经公开了利用分子H2、硼氢化钠、硼氢化铵、肼、氨硼烷、醇和醛作为氢源的技术。但是,对于脱卤素的过程而言,由于非贵金属多相催化剂在温和的反应条件下活性较低,一般情况下,需要一些有毒的氢源或高压氢与之匹配才有可能实现脱卤素的过程。
现有已经公开利用Cu(0)-NP用于脂肪烃卤代物中脱除卤素的过程,且需要在高压氢气的环境下才能实现脂肪烃卤代物上卤素的脱除。由于CAr-Cl键的键能达97.1千卡/mol,CAr-Br键的能达84.0千卡/mol,使其结构比脂肪烃卤代物更加稳定。这样高的键能导致芳香环上的卤素的脱除更加困难,简单的使用氢气或硼氢化钠当作氢源在铜纳米粒子作为催化剂的体系已经无法达到使芳香环上的卤素的脱除的作用。
因此,亟需寻找一种低成本、无毒、温和、高效的脱除卤代芳烃化合物中卤素的方法。
发明内容
为了实现上述目的,本发明提供了一种利用负载铜或铜氧化物纳米颗粒的催化剂脱除卤代芳烃化合物中卤素的方法,本发明以负载铜或铜氧化物纳米颗粒作为催化剂,利用醇类作为氢源,原料无毒害且无需高压环境,反应选择性和转化率可达100%。
具体的,本发明提供了一种利用负载铜或铜氧化物纳米颗粒的催化剂脱卤代芳烃化合物中卤素的方法,所述方法包括以下步骤:
(1)将卤代芳烃类化合物、醇类、碱、负载铜或铜氧化物纳米颗粒的催化剂置于反应装置内,向反应装置内中充入惰性气体以除去反应装置内的空气;
(2)加热至120-300℃,搅拌并反应10~15h;
(3)反应结束后,固液分离除去催化剂,蒸馏、结晶获得脱除卤素后的芳烃化合物。
在本发明的一种实施方式中,所述卤代芳烃类化合物为包含一个或多个卤素原子的卤代苯基化合物。
在本发明的一种实施方式中,所述卤代芳烃类化合物包括氯代苯基化合物,溴代苯基化合物和碘代苯基化合物中的任一种或几种。
在本发明的一种实施方式中,所述醇类为能够作为溶剂的伯醇或仲醇。
在本发明的一种实施方式中,所述醇类包括异丙醇、乙二醇、丙三醇、1-戊醇、2-戊醇、1-辛醇、环己醇的一种或几种。
在本发明的一种实施方式中,所述醇类的添加量为等于或大于卤代芳烃的物质的量,优选2倍于卤代芳烃的摩尔量
在本发明的一种实施方式中,所述碱包括有机碱、无机碱或碱式盐中任一种或几种。
在本发明的一种实施方式中,所述有机碱包括叔丁醇钾、叔丁醇钠、乙醇钠、甲醇钠的一种或几种。
在本发明的一种实施方式中,所述无机碱包括氢氧化钾、氢氧化钠、氢氧化钙的一种或几种。
在本发明的一种实施方式中,所述碱式盐包括碳酸铯、碳酸钾、碳酸钠、磷酸钾、磷酸钠的一种或几种。
在本发明的一种实施方式中,所述卤代芳烃和碱的摩尔比为(1~5):1,优选为1:1。
在本发明的一种实施方式中,所述负载铜或铜氧化物纳米颗粒的催化剂的载体为耐碱性材料,优选的,包括活性炭、水滑石、ZSM-5、分子筛、二氧化钛、二氧化锆、氧化铝、氧化镁中的任一种或几种。
在本发明的一种实施方式中,所述载体颗粒大小一般在10nm-100μm之间。
在本发明的一种实施方式中,所述铜氧化物包括氧化铜或氧化亚铜。
在本发明的一种实施方式中,所述负载铜或铜氧化物纳米颗粒的催化剂优选包括CuO/TiO2,Cu2O/TiO2,Cu/TiO2,Cu2O/Al2O3,Cu2O/Al2O3,Cu2O/Al2O3,CuO/MgO,Cu2O/MgO,Cu/MgO,CuO/ZrO2,Cu2O/ZrO2,Cu/ZrO2、CuO/水滑石,Cu2O/水滑石,Cu/水滑石、CuO/活性炭,Cu2O/活性炭,Cu/活性炭、CuO/ZSM-5,Cu2O/ZSM-5,Cu/ZSM-5的一种或几种。
在本发明的一种实施方式中,所述负载铜或铜氧化物纳米颗粒的催化剂的用量为卤代芳烃摩尔量的0.1%-100%。
在本发明的一种实施方式中,所述负载铜或铜氧化物纳米颗粒的催化剂中,铜元素的负载量为0.005-0.5,优选0.05。
在本发明的一种实施方式中,所述负载铜或铜氧化物纳米颗粒的催化剂通过浸渍法、共沉淀法、水热法、化学气相沉积法或原子层沉积法制备得到,主要将铜物种负载于载体上即可。
在本发明的一种实施方式中,以水热合成为例:取38g三水合硝酸铜溶于1L去离子水中,加入1kg水滑石,超声波振荡30分钟后搅拌2h,后在80℃温度下蒸发出全部水后,研磨后,300-500℃煅烧2h。即可获得相应的催化剂CuO/水滑石。
在本发明的一种实施方式中,所述惰性气体为氮气或氩气。
在本发明的一种实施方式中,所述固液分离包括过滤或离心分离。
在本发明的一种实施方式中,该脱卤氢化反应可在液相条件下或气相条件下或混合液/气相条件下进行。
在本发明的一种实施方式中,脱卤素反应主要在使用醇类回流的温度下进行,必要时需添加回流装置。
其次,本发明还提供了上述方法在化工、环境等领域的应用。
与现有技术相比,本发明的优势在于:
(1)方法上可以使用铜复载的催化剂,使催化剂更加廉价易得,并且可以使用氧化铜纳米粒子负载,简化了催化剂的制备;使用了醇类物质为氢源是反应更加绿色,安全。
(2)脱卤素的效果上可以在10小时内完全使溴代苯完全脱溴,完全满足生产或环境的要求。
具体实施方式
为了进一步说明本发明,以下结合实施例对本发明种使用负载铜或铜氧化物纳米颗粒的催化剂、以醇类为氢源实现卤代芳烃温和脱卤素方法,进行详细描述。
实施例1
一种以CuO/ZrO2为催化剂(其中,Cu所占催化剂的质量分数为5%),以1-辛醇为氢源,加入KOH实现对溴甲苯脱卤氢化的方法,包括以下过程:
称取100mgZrO2负载的纳米CuO催化剂(CuO/ZrO2)于耐压管中,向其中依次加入5ml1-辛醇和1mmol对溴代甲苯。在搅拌下,向上述溶液中1.1mmol的KOH,在140℃温度下反应10h,反应结束后,用注射器吸取一定的反应液并6000转离心5min,所得上清液分别进行以下测试。
将所得上清液直接进行高效液相色谱—二极管阵列检测器测定苯浓度(检测条件:检测波长为270nm,流动相为80v/v%甲醇和20v/v%水的溶液,流速为1mL/min,色谱柱为SB-C18柱)。通过检测结果可以算出,甲苯的含量为0.192mol/L,即本发明实现了对对溴代甲苯的脱溴过程,溴的脱除率高达96%。
实施例2
称取100mg ZSM-5负载的纳米Cu催化剂(Cu/ZSM-5其中,Cu所占催化剂的质量分数为5%))于耐压管中,向其中依次加入5ml1-辛醇和1mmol溴苯。在搅拌下,向上述溶液中1.1mmol的KOH,在120℃温度下反应15h,反应结束后,用注射器吸取一定的反应液并6000转离心5min,所得上清液分别进行以下测试。
将所得上清液直接进行高效液相色谱—二极管阵列检测器测定苯浓度(检测条件:检测波长为270nm,流动相为80v/v%甲醇和20v/v%水的溶液,流速为1mL/min,色谱柱为SB-C18柱)。通过检测结果可以算出,苯的含量为0.199mol/L,即本发明实现了对溴苯的脱溴过程,溴脱除率高达99.5%。
实施例3
称取100mgAl2O3负载的纳米CuO催化剂(CuO/水滑石Cu所占催化剂的质量分数为10%)于耐压管中,向其中依次加入5ml1-辛醇和1mmol对氯代甲苯。在搅拌下,向上述溶液中1.1mmol的tBuOK,在150℃温度下反应12h,反应结束后,用注射器吸取一定的反应液并6000转离心5min,所得上清液分别进行以下测试。
将所得上清液直接进行高效液相色谱—二极管阵列检测器测定苯浓度(检测条件:检测波长为270nm,流动相为80v/v%甲醇和20v/v%水的溶液,流速为1mL/min,色谱柱为SB-C18柱)。通过检测结果可以算出,苯的含量为0.199mol/L,即本发明实现了对对氯代苯的脱氯过程,氯脱除率高达99.2%。
实施例4
称取100mgMgO负载的纳米Cu2O催化剂(CuO/MgO,Cu所占催化剂的质量分数为3%)于耐压管中,向其中依次加入5ml1-戊醇和1mmol对溴甲苯。在搅拌下,向上述溶液中1.1mmol的tBuOK,反应15h,反应结束后,用注射器吸取一定的反应液并6000转离心5min,所得上清液分别进行以下测试。
将所得上清液直接进行高效液相色谱—二极管阵列检测器测定苯浓度(检测条件:检测波长为270nm,流动相为80v/v%甲醇和20v/v%水的溶液,流速为1mL/min,色谱柱为SB-C18柱)。通过检测结果可以算出,本发明实现了对对溴代甲苯的脱溴过程,脱除率高达85.2%。
实施例5
一种以CuO/ZrO2为催化剂(其中,Cu所占催化剂的质量分数为2%),以1-辛醇为氢源,加入NaOH实现对溴甲苯脱卤氢化的方法,包括以下过程:
称取100mgZrO2负载的纳米CuO催化剂(CuO/ZrO2)于耐压管中,向其中依次加入5ml1-辛醇和1mmol对2,4二溴苯。在搅拌下,向上述溶液中1.1mmol的K2CO3,在140℃温度下反应10h,反应结束后,用注射器吸取一定的反应液并6000转离心5min,所得上清液分别进行以下测试。
将所得上清液直接进行高效液相色谱—二极管阵列检测器测定苯浓度(检测条件:检测波长为270nm,流动相为80v/v%甲醇和20v/v%水的溶液,流速为1mL/min,色谱柱为SB-C18柱)。通过检测结果可以算出,苯的含量为0.192mol/L,即本发明实现了对2,4二溴苯的脱溴过程,溴的脱除率高达92.4%。
实施例6
称取100mg水滑石负载的纳米Cu2O催化剂(Cu2O/水滑石,Cu所占催化剂的质量分数为10%)于耐压管中,向其中依次加入5ml1-戊醇和1mmol对氯甲苯。在搅拌下,向上述溶液中1.1mmol的NaOH,在150℃的温度下反应12h,反应结束后,用注射器吸取一定的反应液并6000转离心5min,所得上清液分别进行以下测试。
将所得上清液直接进行高效液相色谱—二极管阵列检测器测定苯浓度(检测条件:检测波长为270nm,流动相为80v/v%甲醇和20v/v%水的溶液,流速为1mL/min,色谱柱为SB-C18柱)。通过检测结果可以算出,甲苯的含量为0.193mol/L,即本发明实现了对对对氯甲苯的脱氯过程,氯脱除率高达96.2%。
实施例7
称取100mg活性炭负载的纳米CuO催化剂(CuO/活性炭,Cu所占催化剂的质量分数为1%)于耐压管中,向其中依次加入5ml丙三醇和2mmol对碘甲苯。在搅拌下,向上述溶液中1.1mmol的C2H5ONa,在120℃的温度下反应15h,反应结束后,用注射器吸取一定的反应液并6000转离心5min,所得上清液分别进行以下测试。
将所得上清液直接进行高效液相色谱—二极管阵列检测器测定苯浓度(检测条件:检测波长为270nm,流动相为80v/v%甲醇和20v/v%水的溶液,流速为1mL/min,色谱柱为SB-C18柱)。通过检测结果可以算出,甲苯的含量为0.382mol/L,即本发明实现了对对碘代甲苯的脱碘过程,碘脱除率高达95.5%。
实施例8
称取100mgZrO2负载的纳米CuO催化剂(CuO/ZrO2,Cu所占催化剂的质量分数为5%)于耐压管中,向其中依次加入5ml乙二醇和4mmol对溴苯甲醚。在搅拌下,向上述溶液中1.1mmol的K3PO4,在130℃的温度下反应12h,反应结束后,用注射器吸取一定的反应液并6000转离心5min,所得上清液分别进行以下测试。
将所得上清液直接进行高效液相色谱—二极管阵列检测器测定苯浓度(检测条件:检测波长为270nm,流动相为80v/v%甲醇和20v/v%水的溶液,流速为1mL/min,色谱柱为SB-C18柱)。通过检测结果可以算出,苯甲醚的含量为0.68mol/L,即本发明实现了对对溴苯甲醚的脱溴过程,溴脱除率高达85.2%。
对比例1
当实施例1中不添加碱KOH时,其余步骤和实施例1相同。
反应结束后,经过检测,发现未检测到苯,即脱溴过程完无法进行。
对比例2
当实施例1中不添加醇作为供体,而选择肼作为氢供体时,其余步骤和实施例1相同。反应结束后,经过检测,发现产物苯收率仅为25%,效果较本发明差。
对比例3
当实施例1中不添加伯醇或仲醇作为供体,而选择叔醇(如叔丁醇)替换1-辛醇作为供体时,其余步骤和实施例1相同。
反应结束后,经过检测,发现未检测到苯,即脱溴过程完无法进行。
虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。
Claims (10)
1.一种利用负载铜或铜氧化物纳米颗粒的催化剂脱卤代芳烃化合物中卤素的方法,其特征在于,所述方法包括以下步骤:
(1)将卤代芳烃类化合物、醇类、碱、负载铜或铜氧化物纳米颗粒的催化剂置于反应装置内,向反应装置内中充入惰性气体以除去反应装置内的空气;
(2)加热至120-300℃,搅拌并反应10~15h;
(3)反应结束后,固液分离除去催化剂,蒸馏、结晶获得脱除卤素后的芳烃化合物。
2.根据权利要求1所述的方法,其特征在于,所述卤代芳烃类化合物为包含一个或多个卤素原子的卤代苯基化合物。
3.根据权利要求1或2所述的方法,其特征在于,所述醇类为能够作为溶剂的伯醇或仲醇。
4.根据权利要求3所述的方法,其特征在于,所述醇类包括异丙醇、乙二醇、丙三醇、1-戊醇、2-戊醇、1-辛醇、环己醇的一种或几种。
5.根据权利要求1~3任一所述的方法,其特征在于,所述碱包括有机碱、无机碱或碱式盐中任一种或几种。
6.根据权利要求1~5任一所述的方法,其特征在于,所述卤代芳烃和碱的摩尔比为(1~5):1。
7.根据权利要求1~6任一所述的方法,其特征在于,所述负载铜或铜氧化物纳米颗粒的催化剂的载体为耐碱性材料,优选的,包括活性炭、水滑石、ZSM-5、分子筛、二氧化钛、二氧化锆、氧化铝、氧化镁中的任一种或几种。
8.根据权利要求1~7任一所述的方法,其特征在于,所述负载铜或铜氧化物纳米颗粒的催化剂包括CuO/TiO2,Cu2O/TiO2,Cu/TiO2,Cu2O/Al2O3,Cu2O/Al2O3,Cu2O/Al2O3,CuO/MgO,Cu2O/MgO,Cu/MgO,CuO/ZrO2,Cu2O/ZrO2,Cu/ZrO2、CuO/水滑石,Cu2O/水滑石,Cu/水滑石、CuO/活性炭,Cu2O/活性炭,Cu/活性炭、CuO/ZSM-5,Cu2O/ZSM-5,Cu/ZSM-5的一种或几种。
9.根据权利要求1~8任一所述的方法,其特征在于,所述负载铜或铜氧化物纳米颗粒的催化剂的用量为卤代芳烃摩尔量的0.1%-100%。
10.权利要求1~9任一所述的方法在化工或环境领域的应用。
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