CN112547064A - Method for removing halogen in halogenated aromatic compound by using catalyst loaded with copper or copper oxide nanoparticles - Google Patents
Method for removing halogen in halogenated aromatic compound by using catalyst loaded with copper or copper oxide nanoparticles Download PDFInfo
- Publication number
- 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
- Prior art date
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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
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- 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
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- 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
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- 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
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention discloses a method for removing halogen in halogenated aromatic compounds by using a catalyst loaded with copper or copper oxide nanoparticles, belonging to the technical field of catalytic synthesis. The invention contacts the halogenated aromatic hydrocarbon substrate with selected alcohols and alkali in the presence of a catalyst loaded by copper or copper oxide nanoparticles, and heats and stirs the substrate. Attacking polyhalogenated aromatic hydrocarbon by utilizing active hydrogen formed on the surface of copper nanoparticles by using alcohol, so as to realize rapid deep dehalogenation of the halogenated aromatic hydrocarbon, wherein the alcohol is primary alcohol or secondary alcohol capable of being used as a solvent; the halogenated aromatic hydrocarbon compound comprises any one or more of chlorophenyl compound, bromophenyl compound and iodophenyl compound. The method is simple to operate, economic and low in cost, and halogenated aromatic hydrocarbon can be completely converted within 10-15 hours under optimized conditions.
Description
Technical Field
The invention relates to a method for removing halogen in halogenated aromatic compounds by using a catalyst loaded with copper or copper oxide nanoparticles, belonging to the technical field of catalytic synthesis.
Background
Halogen groups are typical protecting and directing groups, so halogenated aromatic compounds are widely used as starting materials for many chemical transformations in the chemical industry, agrochemistry. Polybrominated diphenyl ethers are the most widely used flame retardant materials, but the environmental pollution caused by the polybrominated diphenyl ethers is increasingly severe, so that a method for efficiently removing halogen in halogenated aromatic compounds needs to be found. Hydrodehalogenation is an important organic conversion reaction in synthesis and plays an important role in the degradation of halogenated aromatic compounds. Research shows that zero-valent iron dehalogenation is the most effective technology for hydrodehalogenation of halogenated aromatic hydrocarbon through Fenton-like reaction under aerobic condition. However, this process is slow and results in the release of iron ions, which in turn prevents efficient halogen removal.
The search for more efficient and environmentally friendly catalysts has been the focus of attention of researchers. The prior art has investigated the use of homogeneous catalytic systems of transition metal complexes for converting CArThe conversion of the-X bond to a C-H bond to effect the removal of the halogen from the halogenated aliphatic hydrocarbon compound. However, these transition metal complexes are generally unstable and unrecoverable, and certain ligands in the complexes are toxic, air-sensitive and difficult to synthesize. Among the various hydrodehalogenation catalysts, heterogeneous catalysts are therefore a powerful and efficient choice for cleaving the C-X bond in aryl halides under mild conditions. Currently, noble metal nanoparticles (MNP, M ═ Pd, Au, Ag, Pt) are widely used in hydrodehalogenation catalysis, and the cost is high. Not only does the catalyst play an important role in dehalogenation, but the choice of hydrogen source is another important direction of research. The prior art has disclosed the use of molecule H2Sodium borohydride, ammonium borohydride, hydrazine, ammonia borane, alcohols and aldehydes as hydrogen sources. However, for the dehalogenation processIn general, since the activity of the non-noble metal heterogeneous catalyst is low under mild reaction conditions, some toxic hydrogen source or high-pressure hydrogen is needed to match it to realize the dehalogenation process.
The use of Cu (0) -NP for the process of removing halogen from aliphatic hydrocarbon halogenated materials has been disclosed, and the removal of halogen from aliphatic hydrocarbon halogenated materials can be realized in the environment of high-pressure hydrogen. Due to CArThe bond energy of the-Cl bond reaches 97.1 kcal/mol, CArThe energy of the-Br bond reaches 84.0 kcal/mol, so that the structure of the catalyst is more stable than that of the aliphatic hydrocarbon halide. Such a high bond energy makes removal of halogen on the aromatic ring more difficult, and simple use of hydrogen or sodium borohydride as a hydrogen source in a system in which copper nanoparticles are used as a catalyst has not been able to achieve the effect of removing halogen on the aromatic ring.
Therefore, a method for removing halogen in halogenated aromatic compounds with low cost, no toxicity, mildness and high efficiency is needed.
Disclosure of Invention
In order to achieve the purpose, the invention provides a method for removing halogen in halogenated aromatic compounds by using a catalyst loaded with copper or copper oxide nanoparticles, the method takes the loaded copper or copper oxide nanoparticles as the catalyst and alcohols as a hydrogen source, the raw materials are non-toxic and do not need a high-pressure environment, and the reaction selectivity and the conversion rate can reach 100%.
Specifically, the invention provides a method for dehalogenating halogen in aromatic hydrocarbon compounds by using a catalyst loaded with copper or copper oxide nanoparticles, which comprises the following steps:
(1) placing halogenated aromatic hydrocarbon compounds, alcohols, alkali and catalysts loaded with copper or copper oxide nano particles into a reaction device, and filling inert gas into the reaction device to remove air in the reaction device;
(2) heating to 120 ℃ and 300 ℃, stirring and reacting for 10-15 h;
(3) after the reaction is finished, the catalyst is removed by solid-liquid separation, and the aromatic hydrocarbon compound after halogen removal is obtained by distillation and crystallization.
In one embodiment of the invention, the haloaromatic compound is a halophenyl compound comprising one or more halogen atoms.
In one embodiment of the present invention, the halogenated aromatic hydrocarbon compound includes any one or more of a chlorophenyl compound, a bromophenyl compound and an iodophenyl compound.
In one embodiment of the invention, the alcohol is a primary or secondary alcohol capable of acting as a solvent.
In one embodiment of the invention, the alcohol comprises one or more of isopropanol, ethylene glycol, glycerol, 1-pentanol, 2-pentanol, 1-octanol, and cyclohexanol.
In one embodiment of the present invention, the alcohol is added in an amount equal to or greater than the amount of the halogenated aromatic hydrocarbon, preferably 2 times the molar amount of the halogenated aromatic hydrocarbon
In one embodiment of the invention, the base comprises any one or more of an organic base, an inorganic base or a basic salt.
In one embodiment of the present invention, the organic base comprises one or more of potassium tert-butoxide, sodium ethoxide and sodium methoxide.
In one embodiment of the present invention, the inorganic base comprises one or more of potassium hydroxide, sodium hydroxide and calcium hydroxide.
In one embodiment of the present invention, the basic salt comprises one or more of cesium carbonate, potassium carbonate, sodium carbonate, potassium phosphate, and sodium phosphate.
In one embodiment of the present invention, the molar ratio of the halogenated aromatic hydrocarbon to the base is (1 to 5):1, preferably 1: 1.
In one embodiment of the present invention, the carrier of the catalyst loaded with copper or copper oxide nanoparticles is an alkali-resistant material, preferably, includes any one or more of activated carbon, hydrotalcite, ZSM-5, molecular sieve, titanium dioxide, zirconium dioxide, aluminum oxide, and magnesium oxide.
In one embodiment of the invention, the carrier particle size is typically between 10nm and 100 μm.
In one embodiment of the invention, the copper oxide comprises cupric oxide or cuprous oxide.
In one embodiment of the present invention, the copper or copper oxide nanoparticle-supported catalyst preferably comprises CuO/TiO2,Cu2O/TiO2,Cu/TiO2,Cu2O/Al2O3,Cu2O/Al2O3,Cu2O/Al2O3,CuO/MgO,Cu2O/MgO,Cu/MgO,CuO/ZrO2,Cu2O/ZrO2,Cu/ZrO2CuO/hydrotalcite, Cu2O/hydrotalcite, Cu/hydrotalcite, CuO/activated carbon, Cu2O/activated carbon, Cu/activated carbon, CuO/ZSM-5, Cu2One or more of O/ZSM-5 and Cu/ZSM-5.
In one embodiment of the present invention, the amount of the catalyst loaded with copper or copper oxide nanoparticles is 0.1 to 100% of the molar amount of the halogenated aromatic hydrocarbon.
In one embodiment of the present invention, the loading amount of the copper element in the catalyst loaded with copper or copper oxide nanoparticles is 0.005 to 0.5, preferably 0.05.
In one embodiment of the present invention, the catalyst loaded with copper or copper oxide nanoparticles is prepared by an impregnation method, a coprecipitation method, a hydrothermal method, a chemical vapor deposition method, or an atomic layer deposition method, and mainly loads a copper species on a carrier.
In one embodiment of the present invention, hydrothermal synthesis is exemplified as follows: 38g of copper nitrate trihydrate is dissolved in 1L of deionized water, 1kg of hydrotalcite is added, the mixture is stirred for 2 hours after ultrasonic oscillation is carried out for 30 minutes, then all water is evaporated at the temperature of 80 ℃, and after grinding, the mixture is calcined for 2 hours at the temperature of 300 ℃ and 500 ℃. So as to obtain the corresponding catalyst CuO/hydrotalcite.
In one embodiment of the invention, the inert gas is nitrogen or argon.
In one embodiment of the invention, the solid-liquid separation comprises filtration or centrifugation.
In one embodiment of the invention, the dehalogenation hydrogenation reaction may be carried out under liquid phase conditions or gas phase conditions or mixed liquor/gas phase conditions.
In one embodiment of the present invention, the dehalogenation reaction is carried out mainly at the temperature of reflux using alcohols, if necessary with the addition of a reflux apparatus.
The invention also provides the application of the method in the fields of chemical engineering, environment and the like.
Compared with the prior art, the invention has the advantages that:
(1) in the method, a copper-loaded catalyst can be used, so that the catalyst is cheaper and easily obtained, and copper oxide nanoparticles can be used for loading, so that the preparation of the catalyst is simplified; the alcohol substance is used as the hydrogen source, so that the reaction is more green and safe.
(2) The dehalogenation effect can completely debrominate the bromobenzene within 10 hours, and the requirements of production or environment are completely met.
Detailed Description
To further illustrate the present invention, the method for mild dehalogenation of halogenated aromatic hydrocarbons using alcohol as hydrogen source using a catalyst loaded with copper or copper oxide nanoparticles is described in detail below with reference to the following examples.
Example 1
CuO/ZrO2The method for dehalogenating and hydrogenating the bromotoluene by adding KOH into a catalyst (wherein Cu accounts for 5 percent of the mass of the catalyst) and taking 1-octanol as a hydrogen source comprises the following steps:
weighing 100mgZrO2Supported nano CuO catalyst (CuO/ZrO)2) 5ml of 1-octanol and 1mmol of p-bromotoluene were sequentially added thereto in a pressure resistant tube. Under stirring, 1.1mmol KOH in the solution is reacted at 140 ℃ for 10h, after the reaction is finished, a certain amount of reaction solution is sucked up by a syringe and centrifuged at 6000 rpm for 5min, and the obtained supernatants are subjected to the following tests.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). The detection result can calculate that the content of the toluene is 0.192mol/L, namely the invention realizes the debromination process of the p-bromotoluene, and the debromination rate of the bromine reaches 96 percent.
Example 2
100mg of ZSM-5 supported nano Cu catalyst (Cu/ZSM-5, wherein the mass fraction of Cu in the catalyst is 5%) is weighed in a pressure resistant tube, and 5ml of 1-octanol and 1mmol of bromobenzene are sequentially added into the pressure resistant tube. Under stirring, 1.1mmol KOH in the solution is reacted at 120 ℃ for 15h, after the reaction is finished, a certain amount of reaction solution is sucked up by a syringe and centrifuged at 6000 rpm for 5min, and the obtained supernatants are respectively subjected to the following tests.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). According to the detection result, the content of benzene is calculated to be 0.199mol/L, namely the invention realizes the debromination process of bromobenzene, and the debromination rate of bromine reaches up to 99.5%.
Example 3
Weighing 100mgAl2O3The supported nano CuO catalyst (CuO/hydrotalcite Cu accounts for 10 percent of the mass fraction of the catalyst) is put into a pressure-resistant pipe, and 5ml of 1-octanol and 1mmol of p-chlorotoluene are sequentially added into the pressure-resistant pipe. Under stirring, 1.1mmol of the above solutiontBuOK, reacting at 150 ℃ for 12h, sucking a certain reaction liquid by using a syringe after the reaction is finished, centrifuging for 5min at 6000 revolutions, and respectively carrying out the following tests on obtained supernate.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). According to the detection result, the content of the benzene can be calculated to be 0.199mol/L, namely, the dechlorination process of the p-chlorobenzene is realized, and the chlorine removal rate is up to 99.2%.
Example 4
Weighing 100 mgMgO-loaded nano Cu2O catalyst (CuO)MgO, Cu accounts for 3 percent of the mass of the catalyst) is put into a pressure-resistant tube, and 5ml of 1-pentanol and 1mmol of p-bromotoluene are added into the pressure-resistant tube in sequence. Under stirring, 1.1mmol of the above solutiontBuOK, reaction for 15h, after the reaction is finished, a certain amount of reaction liquid is sucked by a syringe and centrifuged for 5min at 6000 revolutions, and the obtained supernatant is subjected to the following tests respectively.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). The detection result can calculate that the invention realizes the debromination process of the p-bromotoluene, and the debromination rate is as high as 85.2 percent.
Example 5
CuO/ZrO2The method for dehalogenating and hydrogenating the bromotoluene by taking 1-octanol as a hydrogen source and adding NaOH as a catalyst (wherein Cu accounts for 2 percent of the mass of the catalyst), comprises the following steps of:
weighing 100mgZrO2Supported nano CuO catalyst (CuO/ZrO)2) 5ml of 1-octanol and 1mmol of p-2, 4-dibromobenzene were added sequentially to the mixture in a pressure resistant tube. Under stirring, 1.1mmol of K in the solution2CO3After the reaction was completed, a certain amount of the reaction solution was aspirated by a syringe and centrifuged at 6000 rpm for 5min, and the obtained supernatants were subjected to the following tests, respectively.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). According to the detection result, the content of the benzene is calculated to be 0.192mol/L, namely the invention realizes the debromination process of the 2,4 dibromobenzene, and the debromination rate of the bromine is up to 92.4 percent.
Example 6
Weighing nano Cu loaded with 100mg of hydrotalcite2O catalyst (Cu)2O/hydrotalcite, Cu accounting for 10 percent of the mass of the catalyst) is put into a pressure-resistant pipe, and 5ml of 1-pentanol and 1mmol of p-chloromethane are sequentially added into the pressure-resistant pipeBenzene. Under stirring, 1.1mmol NaOH in the solution was reacted at 150 ℃ for 12 hours, after the reaction was completed, a certain amount of the reaction solution was sucked up by a syringe and centrifuged at 6000 rpm for 5 minutes, and the obtained supernatants were subjected to the following tests, respectively.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). According to the detection result, the content of the toluene is calculated to be 0.193mol/L, namely, the invention realizes the dechlorination process of the p-chlorotoluene, and the chlorine removal rate is up to 96.2 percent.
Example 7
100mg of activated carbon-supported nano CuO catalyst (CuO/activated carbon, Cu accounting for 1% of the mass of the catalyst) is weighed into a pressure-resistant pipe, and 5ml of glycerol and 2mmol of p-iodotoluene are sequentially added into the pressure-resistant pipe. Under stirring, 1.1mmol of C in the solution2H5ONa, reacting at 120 ℃ for 15h, sucking a certain reaction solution by using an injector after the reaction is finished, centrifuging for 5min at 6000 revolutions, and respectively carrying out the following tests on obtained supernate.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). The content of the methylbenzene is calculated to be 0.382mol/L through a detection result, namely the method realizes the deiodination process of p-iodomethylbenzene, and the iodine removal rate is up to 95.5%.
Example 8
Weighing 100mgZrO2Supported nano CuO catalyst (CuO/ZrO)2And the mass fraction of Cu accounting for the catalyst is 5%) is put into a pressure-resistant pipe, and 5ml of ethylene glycol and 4mmol of p-bromoanisole are sequentially added into the pressure-resistant pipe. Under stirring, 1.1mmol of K in the solution3PO4After the reaction was completed, a certain amount of the reaction solution was aspirated by a syringe and centrifuged at 6000 rpm for 5min, and the obtained supernatants were subjected to the following tests, respectively.
The obtained supernatant was directly subjected to high performance liquid chromatography-diode array detector to measure the benzene concentration (detection conditions: detection wavelength 270nm, mobile phase of 80 v/v% methanol and 20 v/v% water solution, flow rate 1mL/min, column chromatography SB-C18). According to the detection result, the content of anisole is calculated to be 0.68mol/L, namely the invention realizes the debromination process of p-bromoanisole, and the debromination rate of bromine reaches 85.2 percent.
Comparative example 1
When the alkali KOH was not added in example 1, the remaining steps were the same as in example 1.
After the reaction is finished, benzene is not detected through detection, namely, the debromination process is finished and cannot be carried out.
Comparative example 2
When no alcohol was added as a donor and hydrazine was selected as a hydrogen donor in example 1, the rest of the procedure was the same as in example 1. After the reaction is finished, the detection shows that the yield of the product benzene is only 25%, and the effect is poorer than that of the invention.
Comparative example 3
When a tertiary alcohol (e.g., t-butanol) is selected instead of 1-octanol as a donor without adding a primary or secondary alcohol as a donor in example 1, the remaining steps are the same as in example 1.
After the reaction is finished, benzene is not detected through detection, namely, the debromination process is finished and cannot be carried out.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for dehalogenating halogen in aromatic compounds using a catalyst loaded with copper or copper oxide nanoparticles, the method comprising the steps of:
(1) placing halogenated aromatic hydrocarbon compounds, alcohols, alkali and catalysts loaded with copper or copper oxide nano particles into a reaction device, and filling inert gas into the reaction device to remove air in the reaction device;
(2) heating to 120 ℃ and 300 ℃, stirring and reacting for 10-15 h;
(3) after the reaction is finished, the catalyst is removed by solid-liquid separation, and the aromatic hydrocarbon compound after halogen removal is obtained by distillation and crystallization.
2. The process according to claim 1, characterized in that the haloaromatic compound is a halophenyl compound comprising one or more halogen atoms.
3. The method according to claim 1 or 2, characterized in that the alcohol is a primary or secondary alcohol capable of acting as a solvent.
4. The method of claim 3, wherein the alcohol comprises one or more of isopropanol, ethylene glycol, glycerol, 1-pentanol, 2-pentanol, 1-octanol, and cyclohexanol.
5. A process according to any one of claims 1 to 3, wherein the base comprises any one or more of an organic base, an inorganic base or a basic salt.
6. The process according to any one of claims 1 to 5, wherein the molar ratio of the halogenated aromatic hydrocarbon to the base is (1 to 5): 1.
7. The method according to any one of claims 1 to 6, wherein the carrier of the catalyst loaded with the copper or copper oxide nanoparticles is an alkali-resistant material, preferably comprises any one or more of activated carbon, hydrotalcite, ZSM-5, molecular sieve, titanium dioxide, zirconium dioxide, aluminum oxide and magnesium oxide.
8. The method of any one of claims 1 to 7, wherein the copper or copper oxide nanoparticle-supported catalyst comprises CuO/TiO2,Cu2O/TiO2,Cu/TiO2,Cu2O/Al2O3,Cu2O/Al2O3,Cu2O/Al2O3,CuO/MgO,Cu2O/MgO,Cu/MgO,CuO/ZrO2,Cu2O/ZrO2,Cu/ZrO2CuO/hydrotalcite, Cu2O/hydrotalcite, Cu/hydrotalcite, CuO/activated carbon, Cu2O/activated carbon, Cu/activated carbon, CuO/ZSM-5, Cu2One or more of O/ZSM-5 and Cu/ZSM-5.
9. The method according to any one of claims 1 to 8, wherein the amount of the catalyst loaded with the copper or copper oxide nanoparticles is 0.1 to 100 percent of the molar amount of the halogenated aromatic hydrocarbon.
10. Use of the method of any one of claims 1 to 9 in chemical or environmental fields.
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