CN101712593B - Method for preparing phenol - Google Patents
Method for preparing phenol Download PDFInfo
- Publication number
- CN101712593B CN101712593B CN 200810121156 CN200810121156A CN101712593B CN 101712593 B CN101712593 B CN 101712593B CN 200810121156 CN200810121156 CN 200810121156 CN 200810121156 A CN200810121156 A CN 200810121156A CN 101712593 B CN101712593 B CN 101712593B
- Authority
- CN
- China
- Prior art keywords
- reaction
- metal
- metal oxide
- bromobenzene
- benzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 59
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims abstract description 146
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 142
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 87
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 60
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 60
- 239000000126 substance Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 131
- 150000004706 metal oxides Chemical class 0.000 claims description 80
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 49
- 150000004692 metal hydroxides Chemical class 0.000 claims description 49
- 229910001509 metal bromide Inorganic materials 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- 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 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 229910052772 Samarium Inorganic materials 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910052793 cadmium Inorganic materials 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 229910052745 lead Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- -1 step b) in Inorganic materials 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910001510 metal chloride Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 57
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 44
- 238000002360 preparation method Methods 0.000 description 42
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 20
- 239000010949 copper Substances 0.000 description 16
- 238000009283 thermal hydrolysis Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000011069 regeneration method Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000011084 recovery Methods 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 11
- 230000008929 regeneration Effects 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 8
- 238000000643 oven drying Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000012808 vapor phase Substances 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001149 thermolysis Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000012644 addition polymerization Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010574 gas phase reaction Methods 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910001511 metal iodide Inorganic materials 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 238000000520 microinjection Methods 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- IYEFUCDLTRBVCN-UHFFFAOYSA-N [Br].BrC1=CC=CC=C1 Chemical compound [Br].BrC1=CC=CC=C1 IYEFUCDLTRBVCN-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- UTJUOTNXZFEHCJ-UHFFFAOYSA-N benzene;bromobenzene Chemical compound C1=CC=CC=C1.BrC1=CC=CC=C1 UTJUOTNXZFEHCJ-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
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- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/02—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
- C07C39/04—Phenol
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing phenol, comprising the following steps: benzene and simple substance bromine generate bromobenzene and HBr under the action of catalyst, HBr reacts with metallic oxide MXO to generate metallic bromide MXBr2 and water; the generated bromobenzene reacts with water and metallic oxide M'XO and/or metallic hydroxide M''X(OH)2 to generate phenol and metallic bromide M'XBr2 and/or M''XBr2. Metallic bromide MXBr2, M'XBr2 and/or M''XBr2 react with oxygen to regenerate metallic oxide MXO, M'XO and/or metallic hydroxide M''X(OH)2 and simple substance bromine, and the generated simple substance bromine can be absorbed by benzene to recycle.
Description
Technical field
The present invention relates to a kind of method for preparing phenol.
Background technology
Phenol is commonly called as phenylic acid, it is a kind of important Organic Chemicals, mainly for the production of resol, hexanolactam, dihydroxyphenyl propane, hexanodioic acid, aniline, alkylphenol etc., be widely used in the aspects such as synthon, synthetic rubber, plastics, medicine, agricultural chemicals, spices, dyestuff and coating.
The production method of phenol comprises cumene method, toluene or phenylformic acid method, benzene sulfonation method, hexanaphthene method, chlorinated benzene hydrolysis method, benzene direct oxidation method etc.Wherein chlorobenzene method production phenol comprises again traditional hydrolysis method (chlorobenzene alkaline water solution) and Raschig process-Hooke method (the acid hydrolysis method of chlorobenzene).
Chlorobenzene alkaline water solution be just Dow Chemical company and the employing of German method our company as far back as the twenties in 19th century.Its typical production flow process is generally by Hydrolysis of Chlorobenzene under 360～390 ℃, 28～30MPa condition, by product or intermediate product are phenyl ether etc., adopt respectively different concns the aqueous solution of sodium hydroxide, salt of wormwood, sodium carbonate or lime come in and hydrogenchloride, the sodium phenylate of generation obtains phenol with the salt acid treatment again.1932～1938 years W.J.Hale and E.C.Britton have reported respectively a kind of some highly basic or weak acid of adding, as Na
2b
4o
7, Na
2hPO
4or Na
2cO
3, metallic copper is made catalyzer, and the reaction in 250～375 ℃ and closed pressure vessel of chlorobenzene and water generates the method for phenol.R.P.Perkins (1938) discloses chlorobenzene and water generates the method for phenol 300～650 ℃ of reactions, and catalyzer is the BeCl loaded on silicon sol
2, ZnSO
4, CdCl
2, Al
2(SO
4)
3, ZrCl
4, SnCl
2, SbCl
3, CuCl
2deng.
The acid hydrolysis method of chlorobenzene, its typical flow process is: a certain proportion of chlorobenzene and aqueous sodium hydroxide solution are placed in the airtight autoclave vaporizer with heating unit, the steam of chlorobenzene and water is through 300～700 ℃ of excess temperatures, the bed of loading catalyst, carry out gas phase catalytic reaction, reacted product is back in still through coil condenser again.So circulating reaction, until chlorobenzene has reacted, mainly contain sodium phenylate, water, sodium-chlor in last still, finally obtains phenol with acid and sodium phenylate reaction again.In this flow process, the catalyzer used the earliest has vanadine, silica-gel catalyst, porous silica gel catalyzer, the catalyzer grown up subsequently have various alkaline-earth metal oxyhydroxide, oxide compound, natural refining carclazyte, load on aluminum oxide, silica gel and add the compounds such as a small amount of Zn, Cu, Ni as the neutral phosphonic phosphate catalyst of auxiliary agent etc.Within 1940, Raschig process realizes industrialization, and it adopts Ca
3(PO
4)
2/ SiO
2for catalyzer, under 400～450 ℃, phenol is produced in the reaction of chlorobenzene thermal hydrolysis.
W.T.Reichle (1970) has reported the thermal hydrolysis reaction of chlorobenzene on calcium phosphate powder, and the author points out that Cu (II) is effective catalyst, and other metal oxide does not have activity.The people such as N.S.Figoli, H.R.Keselman (1982～1984) systematic study Cu load on thermal hydrolysis reaction and the deactivation cause thereof of chlorobenzene on lanthanum orthophosphate, hydroxyapatite, RE phosphate as auxiliary agent.The people such as H.Nakajima (1994) have reported 450 ℃ of temperature of reaction, on Na type ZSM-5 molecular sieve, a small amount of Ni of load, Cu react the method for preparing phenol as auxiliary agent chlorobenzene thermal hydrolysis, but due to can knot carbon on the Ni auxiliary agent, and Cu at high temperature can run off, the easy inactivation of catalyzer.
Except the above two kinds methods that prepare phenol by chlorobenzene, the method for utilizing other halogeno-benzenes to prepare phenol is also disclosed in some patents.
For example, when benzene polyhalide and aqueous vapor phase thermal hydrolysis generate corresponding phenols, also adopted the catalyzer of phosphoric acid salt, as calcium phosphate (US3213146, W.H.Prahl, 1965), add a small amount of copper to do rare earth metal phosphoric acid salt (US3752878, W.L.Kehl, 1970 of auxiliary agent; US3838182, W.L.Kehl, 1974) etc.G.Paparatto has described iodobenzene in the US4684749 patent and water generates the method for phenol in liquid phase, and actual conditions is in the time of 120～260 ℃, uses Cu
2o and/or CuI make catalyzer (consumption is equivalent to 0.01～5wt% of iodobenzene), dilute as phenyl ether, toluene etc. in the situation that add containing the organic solvent that accounts for whole liquid phase mixture 5～50wt%, then add a certain amount of KOH or NaOH, NaHCO
3or Na
2cO
3, iodobenzene and water under high pressure react and prepare phenol.Within 1918, H.H.Dow has described in a high pressure tank reactor in the US1274394 patent, under the pressure of 250 ℃ and 300 pounds, bromobenzene and dense aqueous sodium hydroxide solution reaction obtain sodium phenylate, and then pass into carbonic acid gas and sodium phenylate reaction generation phenol, phenol yield 85%.
Zhai Hesheng has been described a kind of from benzene in the ZL02147864.3 patent, and iron powder is made catalyzer and made bromobenzene, then reacts the preparation method of synthetic aniline by-product phenol and its derivatives with various metal oxides and bromobenzene and ammonia or amine.Wherein the reaction of bromobenzene and ammoniacal liquor is to carry out in tank reactor, and temperature of reaction is 50～450 ℃; The reaction that patent is also mentioned bromobenzene and water is also to carry out in tank reactor.But this patent shows, the transformation efficiency of bromobenzene and the productive rate of phenol are very low, only 33% and 17%; The HBr that the first step generates must use dioxygen oxidation to reclaim bromine after separating; The metal bromide that the second step reaction generates need to take out from autoclave, then carries out separately the oxidation regeneration processing to reclaim simple substance bromine wherein, operates extremely inconvenient; In addition, under condition of high voltage, the etching problem of equipment is by even more serious.
These prepare by the halogeno-benzene hydrolysis method in the method for phenol and have obvious shortcoming in the past:
1) the reaction majority needs high pressure, adopts tank reactor, in production process, will consume a large amount of alkali lye, and operation sequence is many, needs complicated sepn process, and generating a large amount of salts can't fully utilize, and process cost is large;
2) in partial monopoly, added the copper metal as promotor, but the charge capacity of copper is few, 0.1～5wt% only, the very fast inactivation of catalyzer, it is general that by catalyst deactivation, very fast reason all ascribes knot carbon to;
3) most patents do not relate to halogen cycle and process, although indivedual patent is mentioned halogen cycle, reclaim, must by hydrogen halide etc. from product separation out again with air or dioxygen oxidation to reclaim halogen, operation steps is loaded down with trivial details, utility appliance is many.
Summary of the invention
The invention discloses a kind of method that benzene prepares phenol, overcome above shortcoming.The method comprises following step:
(a) benzene and simple substance bromine generate bromobenzene and HBr, HBr and metal oxide M under catalyst action
xthe O reaction generates metal bromide M
xbr
2and water;
(b) bromobenzene that step generates in a), with water and metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2reaction generates phenol and metal bromide M '
xbr
2and/or M "
xbr
2.
Described step a) can adopt fixed-bed reactor, and concrete reaction process is that the mixture of benzene and simple substance bromine is in succession by described beds and described metal oxide M
xthe O bed generates bromobenzene and HBr under the beds effect, and bromobenzene and HBr are by metal oxide M subsequently
xthe O bed, HBr and metal oxide M
xthe O reaction generates metal bromide M
xbr
2and water, then isolate bromobenzene.
Reaction a) of described step is carried out under normal pressure.Described simple substance bromine is to adopt arbitrarily rare gas element (such as N
2) do carrier gas, be brought in reactor.The temperature of reaction of described benzene and simple substance bromine is 50～300 ℃, and preferably temperature of reaction is 160～240 ℃.The described step a) separation method of the middle bromobenzene generated is that the liquid phase that reaction is generated, comprise bromobenzene, complete benzene and the bromine of unreacted, adopts distillation separation method to obtain bromobenzene.
The catalyzer that described step a) is reacted contains at least one in metal simple-substance, metal chloride, metal bromide, metal oxide, molecular sieve HZSM-5.Described catalyzer can be loaded catalyst or unsupported catalyst.Described loaded catalyst contains a kind of carrier and the load active phase by metal simple-substance, metal chloride, metal bromide, metal oxide or its compositions of mixtures on it.The carrier of described catalyzer is selected from SiO
2, ZrO
2, Al
2o
3, at least one in molecular sieve HZSM-5.The activity of described catalyzer is selected from least one in metal simple-substance, metal chloride, metal bromide or the metal oxide of Fe, Al or Zn mutually.Preferably, the activity of described catalyzer is selected from metal Fe, FeCl mutually
3, AlCl
3, ZnCl
2, FeBr
3, AlBr
3, ZnBr
2, at least one in ZnO.The charge capacity of the active phase of described loaded catalyst is 0.2～30.0wt%.Preferably, the charge capacity of the active phase of described loaded catalyst is 1.0～15.0wt%.
Described metal oxide M
xo is selected from least one in the oxide compound of Mg, Ca, Cu, Fe, Ru, Co, Ba, Y, La, Mo, Mn, Pb, Sn, Sm, Cr, Zn, Cd, Al, Bi, Ni, Ce or Ag, described metal oxide M
xo is at least one in MgO, CaO or CuO preferably.Described metal oxide M
xo can be carried on carrier, and described carrier is selected from SiO
2, ZrO
2, at least one in molecular sieve HZSM-5.Described metal oxide M
xo is at SiO
2, ZrO
2on charge capacity be 1.0～50.0mol%, preferred 5.0～15.0mol%, metal oxide M
xthe charge capacity of O on HZSM-5 is 5.0～15.0wt%.Described metal oxide M
xo adopts the preparation of one of following several method: the preparation of available metal salt coprecipitation method, or metallic salt mixture thermolysis preparation, or with pickling process metal-salt be carried on carrier, then dry, go thermolysis again, described metal-salt is selected from least one in metal nitrate, metal chloride, metal bromide, metal iodide, metal sulfate, metal carbonate, alkali metal bicarbonate salt, metal oxalate.Described metal oxide M
xin the preparation process of O, can adopt diverse ways to carry out drying to presoma, comprise oven dry, vacuum-drying, or in high temperature air, oxygen, calcination is decomposed.
Described step is the middle metal bromide M generated a)
xbr
2be regenerated as metal oxide M with oxygen reaction
xo and simple substance bromine, the simple substance bromine of generation absorbs with recycle with benzene.Described metal bromide M
xbr
2with the temperature of reaction of oxygen be 150～700 ℃.Preferably, described metal bromide M
xbr
2with the temperature of reaction of oxygen be 250～500 ℃.
Described step b) in, metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2the metal oxide or the metal hydroxides that have a kind of Cu of being selected from, Na, K, Fe, Ru, Co, Ca, Ba, Y, La, Mo, Mn, Pb, Sn, Sm, Cr, Zn, Cd, Al, Mg, Bi, Ni, Ce or Ag at least.Preferably, described metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2comprise CuO.Again preferably, described metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2be selected from the metal oxide of CuO and Na, K, Fe, Ru, Co, Ca, Ba, Y, La, Mo, Mn, Pb, Sn, Sm, Cr, Zn, Cd, Al, Mg, Bi, Ni, Ce or Ag or the mixture of at least one composition in metal hydroxides.More preferably, described metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2be selected from the mixture of at least one composition in the metal oxide of CuO and Fe, Ru, Co, Ca, Y, La, Mo, Mn, Pb, Sn, Sm, Cr, Zn, Cd, Al, Mg, Bi, Ni, Ce or Ag, or the mixture of at least one composition in the metal hydroxides of CuO and Na, K or Ba.
Described metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2be carried on carrier, described carrier is selected from SiO
2, ZrO
2, Al
2o
3, at least one in molecular sieve HZSM-5.Described SiO
2carrier can, for not adding the carrier of other composition, can be also also that the carrier that the addition polymerization compound is made (is used P-SiO
2mean), the effect of polymkeric substance is, improves the pore size distribution of prepared carrier, makes it more even, the main body selectivity of product increases.Described polymkeric substance can be for polyethylene glycol, polypropylene, polypropylene-base ethylene glycol and their segmented copolymer thereof or its single-butyl ether, as P
1: poly (ethylene glycol-ran-propylene), P
2: poly (ethylene glycol-ran-propylene glycol) monobutyl ether, or P
3: poly (ethyleneglycol)-block-poly (propylene glycol)-block-poly (ethylene glycol).The carrier prepared by the method is with P
1-SiO
2, P
2-SiO
2, P
3-SiO
2mean.SiO
2carrier can adopt sol-gel method or precipitator method preparation, and wherein the maturing temperature in preparation process is 250～1000 ℃, and preferably, maturing temperature is 350～650 ℃.
Described metal oxide-loaded M '
xo and/or metal hydroxides M "
x(OH)
2carrier, some carrier can play the effect of activated metal oxide compound simultaneously, prevents metal oxide and bromide grain growth, to guarantee high reactivity and the reproducibility of metal oxide active ingredient.
Described carrier and reactant metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2the ratio of amount can be arbitrary proportion.Preferably, metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2at SiO
2, ZrO
2or Al
2o
3on charge capacity be 2.0～60.0mol%.More preferably, described metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2at SiO
2, ZrO
2or Al
2o
3on charge capacity be 10.0～40.0mol%.Described metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2charge capacity on HZSM-5 is 5.0～15.0wt%.
By oxide M '
xo and/or metal hydroxides M "
x(OH)
2load on carrier, we are referred to as load metal oxide and/or metal hydroxides.Load metal oxide and/or metal hydroxides can be expressed as M
1m
2/ carrier is (as M
1m
2/ SiO
2), M wherein
1represent CuO, M
2represent the oxide compound of Na, K, Fe, Ru, Co, Ca, Ba, Y, La, Mo, Mn, Pb, Sn, Sm, Cr, Zn, Cd, Al, Mg, Bi, Ni, Ce or Ag or at least one in oxyhydroxide.In above-mentioned expression mode, what "/" meaned later is kind of carrier; If do carrier with HZSM-5, M
1and M
2before percent value mean the respective metal oxide M of load '
xo or metal hydroxides M "
x(OH)
2mass percent; If with other carrier beyond HZSM-5, M
1and M
2before percent value mean the respective metal oxide M of load '
xo or metal hydroxides M "
x(OH)
2molecular fraction.
Described load metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2adopt the preparation of one of following several method: the preparation of available metal salt coprecipitation method, or metallic salt mixture thermolysis preparation, or with pickling process metal-salt be carried on carrier, then dry, go thermolysis again, described metal-salt is selected from least one in metal nitrate, metal chloride, metal bromide, metal iodide, metal sulfate, metal carbonate, alkali metal bicarbonate salt, metal oxalate, metal acetate salt.Described metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2preparation process in, can adopt diverse ways to carry out drying to presoma, comprise oven dry, vacuum-drying, or in high temperature air, oxygen, calcination is decomposed.
Described metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2in reaction as reactant, but it is special reactant because its simultaneously also participates in reaction as catalyzer, and amount is by the stoichiometric ratio supply, is not a small amount of, is the reagent with katalysis.
Described load metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2passed through pre-treatment before participating in reaction, after first processing with hydrobromic acid aqueous solution, again with oxygen reaction, in-situ regeneration M '
xo and/or M "
x(OH)
2.Wherein, metal oxide major part after oxygen treatments applied can be regenerated; The metal hydroxides Partial Conversion is metal bromide, and part may be converted into oxide compound, owing to there being water to exist in system, also may have part to exist with hydroxide form.Metal hydroxides add the structure that can regulate metal oxide (being carried on carrier), make it there is better structural stability, longer work-ing life, and catalytic performance also may be improved to some extent (common catalysis or the promoter effect of not getting rid of metal bromide).
Described step b) the metal bromide M ' that reaction generates
xbr
2and/or M "
xbr
2be regenerated as metal oxide M ' with oxygen reaction
xo and/or metal hydroxides M "
x(OH)
2and simple substance bromine, the simple substance bromine of generation absorbs with recycle with benzene.Described metal bromide M '
xbr
2and/or M "
xbr
2described metal bromide M
xbr
2with the temperature of reaction of oxygen be 150～700 ℃.Preferably, described metal bromide M '
xbr
2and/or M "
xbr
2with the temperature of reaction of oxygen be 250～500 ℃.
Described step b) the liquid phase that reaction generates, comprise phenol and by product benzene, the complete bromobenzene of unreacted, adopts distillation separation method to obtain phenol.
Described step b) in the reaction, between each reactant, by stoichiometric coefficient of chemical reaction, reacted, but the amount of certain reactant can be suitably some more.The mol ratio of described water and bromobenzene is 0.2～50.Preferably, the mol ratio of described water and bromobenzene is 1～10.Described reaction adopts arbitrarily rare gas element (as N
2) do carrier gas.Described step b) temperature of reaction, for being greater than 250 ℃, is less than 600 ℃.Preferably, temperature of reaction described step b) is 360～460 ℃.Described step b) reaction is carried out under normal pressure.
The type reaction equation of each step is as follows:
A) reaction of benzene and simple substance bromine bromobenzene processed
(minute reaction formula):
2HBr+MxO→MxBr
2+H
2O
(net reaction):
A) two, metal bromide M
xbr
2with reacting of oxygen, (be M
xthe reaction of O regeneration):
O
2+2M
xBr
2→2Br
2+2M
xO
B) bromobenzene and water and metal oxide M '
xthe reaction of O:
B) two, metal bromide M '
xbr
2with reacting of oxygen, (be M '
xthe reaction of O regeneration)
O
2+2M′
xBr
2→2Br
2+2M′
xO
Method disclosed by the invention has realized the HBr and bromobenzene original position and the metal oxide M that produce in the reaction
xo and M '
xo (and/or metal hydroxides M "
x(OH)
2) reaction, generate corresponding bromide M
xbr
2and M '
xbr
2, more regularly with oxygen or airborne oxygen, to carry out in-situ regeneration be metal oxide M
xo and M '
xo (and/or metal hydroxides M "
x(OH)
2) and reclaim simple substance bromine simultaneously, and the former method that needn't resemble needs first hydrogen halide etc. is separated, and then reclaim halogen separately.In this reaction process, metal oxide M
xo and M '
xo can be identical, also can be not identical.
In the embodiment of present method, the transformation efficiency of the gas phase bromo-reaction simple substance bromine of benzene reaches 100%, and the selectivity of bromobenzene reaches 89～95%, and all the other products are a small amount of para-orientation dibromobenzene; Bromobenzene and water are at stoichiometric metal oxide M '
xo (and/or metal hydroxides M "
x(OH)
2) transformation efficiency of upper reaction bromobenzene reaches 83～98%, the selectivity of phenol reaches 85～97%, and all the other by products are benzene.
The method for preparing phenol with the halogeno-benzene in past is compared, and method disclosed by the invention has following features:
1) reaction can be reacted under normal pressure, low pressure, does not need under high pressure to carry out;
2) metal bromide M in the reaction
xbr
2and M '
xbr
2in-situ regeneration is metal oxide M
xo and M '
xo (and/or metal hydroxides M "
x(OH)
2) reuse, and reclaim simple substance bromine simultaneously, reclaim again halogen and needn't resemble after former patent need to be separated hydrogen halide etc., in whole flow process, bromine can cyclically utilizing;
3) metal oxide M '
xo (and/or metal hydroxides M "
x(OH)
2) be reactant, be again catalyzer, cheap and easy to get, stable performance, its surface can not produce knot carbon, and the life-span is long;
4) respectively walk reaction preference high, Main By product is benzene, and it can do raw material again, and the simple substance bromine absorbed with benzene is capable of circulation for benzene bromobenzene processed.
The accompanying drawing explanation
Fig. 1 is reaction process schematic diagram of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.The test method of unreceipted actual conditions in the following example, implement according to normal condition usually, or the condition of advising according to manufacturer.
The following example has been set forth each step of described method flow, comprises benzene and simple substance bromine reaction bromobenzene processed, bromobenzene thermal hydrolysis phenol processed, metal bromide M
xbr
2, M '
xbr
2and/or M "
xbr
2reclaim simple substance bromine with oxygen reaction.
(1) preparation of catalyzer and reactant
1, the preparation of carrier
Described carrier is existing as supported catalyst, also has as the load-reaction thing.
The preparation of HZSM-5: commodity HZSM-5 molecular sieve (Si/Al=25), HZSM-5 molecular sieve (Si/Al=75), HZSM-5 molecular sieve (Si/Al=400) (Catalyst Factory, Nankai Univ) compressing tablet also are sized to 10～20 orders, standby.HZSM-5 can be used as carrier, also can directly be used as catalyzer.
SiO
2the preparation of carrier: claim 6.300g oxalic acid dissolution of solid in the 100mL deionized water, weighing 34.583g tetraethoxy-silicane liquid joins in above-mentioned solution, 4h is stirred in sealing, become even water white solution, then this solution is put into 120 ℃ of baking oven 8h, dry to colloidal solid, subsequently this colloidal solid is inserted to the heat-up rate with 350 ℃/h in retort furnace and be heated to 350 ℃, heat-up rate with 200 ℃/h is heated to 450 ℃ again, lower the temperature after maintaining this temperature 5h, after equitemperature is down to below 150 ℃, take out SiO
2carrier, be sized to 20～60 orders, standby.
ZrO
2the preparation of carrier: claim 19.005g oxalic acid dissolution of solid in the 200mL deionized water, weighing 47.963g tetrabutyl zirconate solution (80wt%, solvent is n-butyl alcohol, Aldrich) join in above-mentioned solution, 4h is stirred in sealing, become even water white solution, then this solution is put into 120 ℃ of baking oven 8h, dry to colloidal solid, subsequently this colloidal solid is inserted to the heat-up rate with 350 ℃/h in retort furnace and be heated to 350 ℃, heat-up rate with 200 ℃/h is heated to 450 ℃ again, after maintaining this temperature 5h, lower the temperature, equitemperature takes out after being down to below 150 ℃, be sized to 20～60 orders, standby.
Al
2o
3carrier: the spherical activated alumina that adopts Shanghai chemical reagents corporation of traditional Chinese medicines group.
Addition polymerization compound SiO
2carrier (is used P-SiO
2expression) preparation: claim the 4.000g polymer dissolution in the 100mL deionized water, add 6.300g oxalic acid after stirring, dissolve complete obtains a solution, weighing 34.583g tetraethoxy-silicane liquid (98wt%, Aldrich) join in above-mentioned solution operation steps thereafter and addition polymerization compound SiO not
2carrier prepares similar.Described polymkeric substance is respectively P
1: poly (ethylene glycol-ran-propylene), P
2: poly (ethylene glycol-ran-propylene glycol) monobutyl ether, P
3: poly (ethylene glycol)-block-poly (propylene glycol)-block-poly (ethyleneglycol).According to said method the carrier of preparation is with P
1-SiO
2, P
2-SiO
2, P
3-SiO
2mean.
2, the preparation of catalyzer:
The preparation of catalyzer 1.0wt%ZnO/HZSM-5 (Si/Al=400): weighing 0.910gZn (NO
3)
26H
2o is dissolved in the 100mL deionized water, add 19.800g HZSM-5 molecular sieve (Si/Al=400), standing 2h after stirring 6h, put into 120 ℃ of oven drying 12h, subsequently dried solid heat-up rate with 350 ℃/h in retort furnace is heated to 350 ℃, then is heated to 450 ℃ with the heat-up rate of 200 ℃/h, lower the temperature after maintaining this temperature 5h, equitemperature takes out after being down to below 150 ℃, is sized to 10～20 orders.
Catalyst Fe Cl
3/ SiO
2, AlCl
3/ SiO
2, ZnCl
2/ SiO
2preparation: charge capacity is 5.0～15.0wt%.With 5.0wt%AlCl
3/ SiO
2catalyzer be prepared as example: 3.621g AlCl
36H
2o is dissolved in 100mL water, the SiO that adds 18.0g to prepare
2carrier, dipping 4h, then put into the oven drying 12h of 120 ℃, takes out standby.
Catalyst Fe Br
3/ SiO
2, AlBr
3/ SiO
2, ZnBr
2/ SiO
2preparation: charge capacity is 5.0～15.0wt%.The preparation method is with above-mentioned muriatic preparation method.
The preparation of catalyst Fe powder: while with iron powder, making catalyzer, claim 5.0g commodity iron powders (Tianjin Ke Miou) and 18.0g SiO
2after mixing, directly use.
Load on other carriers (ZrO
2, Al
2o
3deng) on preparation and the FeCl of catalyzer
3/ SiO
2deng the preparation method similar.
Annotate: the charge capacity of catalyzer (no matter carrier) all by percentage to the quality.
3, the preparation of reactant
(1) M
xthe preparation of O/ carrier
M
xit is example that O be take MgO, CaO and CuO.Carrier is with SiO
2for example, M
xthe charge capacity of O is 5.0～15.0mol%, and wherein following again is example.
10.0mol%CuO/SiO
2preparation: adopt pickling process, claim 5.832g Cu (NO
3)
23H
2o is dissolved in the 100mL deionized water, the Si0 that adds 12.278g to prepare
2carrier, after dipping 4h, put into 120 ℃ of oven drying 12h, subsequently this solid is inserted to the heat-up rate with 350 ℃/h in retort furnace and be heated to 350 ℃, then be heated to 450 ℃ with the heat-up rate of 200 ℃/h, lower the temperature after maintaining this temperature 5h, after being down to below 150 ℃, temperature takes out, and standby.
Load on other carriers (HZSM-5, ZrO
2, Al
2o
3deng) on M
xthe preparation of O and 10.0mol%CuO/SiO
2deng the preparation method similar.
(2) M
1m
2the preparation of/carrier
Oxide M '
xo or metal hydroxides M "
x(OH)
2load on carrier, be called as in the present invention load metal oxide and/or metal hydroxides.With " M
1m
2/ carrier " expression, wherein M
1represent CuO, M
2represent the oxide compound of Fe, Ru, Co, Ca, Ba, Na, K, Y, La, Mo, Mn, Pb, Sn, Sm, Cr, Zn, Cd, Al, Mg, Bi, Ni, Ce or Ag or at least one of oxyhydroxide, carrier can be HZSM-5, SiO
2, ZrO
2, Al
2o
3deng.Below with load SiO
2carrier is example.
10mol%CuO/SiO
2preparation: the same M
xo/SiO
2preparation.
10mol%CuO/P-SiO
2preparation: adopt pickling process, claim 5.832g Cu (NO
3)
23H
2o is dissolved in the 100mL deionized water, the P-SiO that adds 12.278g to prepare
2carrier (is respectively P
1-SiO
2, P
2-SiO
2and P
3-SiO
2), after dipping 4h, put into 120 ℃ of oven drying 12h, subsequently this solid is inserted to the heat-up rate with 350 ℃/h in retort furnace and be heated to 350 ℃, then be heated to 450 ℃ with the heat-up rate of 200 ℃/h, lower the temperature after maintaining this temperature 5h, equitemperature takes out after being down to below 150 ℃, standby.
8mol%CuO2mol%CoO/SiO
2preparation: at first claim 4.704g Cu (NO
3)
23H
2o is dissolved in the 100mL deionized water, the SiO that adds 13.454g to prepare
2carrier, dipping 4h, put into 120 ℃ of oven drying 12h, subsequently this solid is inserted to the heat-up rate with 350 ℃/h in retort furnace and be heated to 350 ℃, heat-up rate with 200 ℃/h is heated to 450 ℃ again, lowers the temperature after maintaining this temperature 5h, after equitemperature is down to below 150 ℃, takes out cooling.And then title 2.659gCo (NO
3)
26H
2o is dissolved in the 100mL deionized water, add above-mentioned cooled compound, after flooding 4h again, put into 120 ℃ of oven drying 12h, subsequently this solid is inserted to the heat-up rate with 350 ℃/h in retort furnace and be heated to 350 ℃, then be heated to 450 ℃ with the heat-up rate of 200 ℃/h, lower the temperature after maintaining this temperature 5h, equitemperature takes out after being down to below 150 ℃, standby.This preparation method adopts the method for secondary load.
8mol%CuO2mol%NaOH/SiO
2preparation: at first claim 4.704g Cu (NO
3)
23H
2o is dissolved in the 100mL deionized water, the SiO that adds 13.454g to prepare
2carrier, dipping 4h, put into 120 ℃ of oven drying 12h, subsequently this solid is inserted to the heat-up rate with 350 ℃/h in retort furnace and be heated to 350 ℃, heat-up rate with 200 ℃/h is heated to 450 ℃ again, lowers the temperature after maintaining this temperature 5h, after equitemperature is down to below 150 ℃, takes out cooling.And then claim that 0.182gNaOH is dissolved in the 100mL deionized water, add above-mentioned cooled compound, after flooding 4h again, put into 120 ℃ of oven drying 12h, subsequently this solid is inserted to the heat-up rate with 350 ℃/h in retort furnace and be heated to 350 ℃, then be heated to 450 ℃ with the heat-up rate of 200 ℃/h, lower the temperature after maintaining this temperature 5h, equitemperature takes out after being down to below 150 ℃, standby.This preparation method adopts the method for secondary load.
Load on other carriers (HZSM-5, ZrO
2, Al
2o
3deng) on load metal oxide or preparation and the 10mol%CuO/SiO of metal hydroxides
2, 8mol%CuO2mol%NaOH/SiO
2deng the preparation method similar.
Annotate: load on oxide M on HZSM-5 '
xo or metal hydroxides M "
x(OH)
2charge capacity all by percentage to the quality, load on SiO
2, ZrO
2, Al
2o
3on all in molar percentage.
(2) benzene and bromine prepare bromobenzene, and regeneration M
xo
Adopt fixed-bed reactor, the quartz glass tube that tube inner diameter is 18mm, vertically place, the above-mentioned catalyzer 10.0g prepared of upper strata filling; Lower floor's filling loads on SiO
2metal oxide M on carrier
xo, total mass is 5.0g.
When reaction is carried out, bromine and benzene pass into reactor from the upper end of quartz glass tube, have reacted after product and have discharged from lower end.Simple substance bromine be adopt nitrogen 55 ℃ in the bromine container bubbling bring reactor into, the flow of carrier gas nitrogen is 5mL/min, bubbler is placed in the water bath with thermostatic control of 55 ℃, the simple substance bromine flow is 0.008125mol/h, the flow of benzene is 0.0225mol/h.Reaction is carried out under normal pressure.
After reaction starts, the organic phase of getting in the liquid phase collector every 2h is carried out stratographic analysis.HBr to be generated and the M of metering
xafter O reacts completely, stop the charging of benzene and simple substance bromine.Pass into N
2(flow is 50mL/min) purges 10min, then passes at a certain temperature O
2reacted, M regenerates
xo and simple substance bromine, the simple substance bromine of generation absorbs with benzene.
Under differing temps, benzene and bromine react the condition for preparing bromobenzene and the results are shown in Table 1 on HZSM-5 (Si/Al=75) catalyzer.
On HZSM-5 under table 1 differing temps (Si/Al=75) catalyzer, benzene and bromine reaction prepare bromobenzene
Reaction conditions: N
2flow 5mL/min; Simple substance bromine flow 0.008125mol/h; Benzene flow 0.0225mol/h, reaction times 2h; Catalyzer forms: HZSM-5 (Si/Al=75); " M
xthe O/ carrier " composition: 10.0mol%MgO/SiO
2.
Benzene and bromine gas-phase reaction on HZSM-5 (Si/Al=25) catalyzer prepares the condition of bromobenzene and the results are shown in Table 2.
On table 2HZSM-5 (Si/Al=25) catalyzer, benzene and bromine reaction prepare bromobenzene
Reaction conditions: 220 ℃ of temperature of reaction; N
2flow 5mL/min; Simple substance bromine flow 0.008125mol/h; Benzene flow 0.0225mol/h; Catalyzer forms: HZSM-5 (Si/Al=25); " M
xthe O/ carrier " composition: 10.0mol%CaO/ZrO
2.
Benzene and bromine gas-phase reaction on HZSM-5 (Si/Al=75) catalyzer prepares the condition of bromobenzene and the results are shown in Table 3.
On table 3HZSM-5 (Si/Al=75) catalyzer, benzene and bromine reaction prepare bromobenzene
Reaction conditions: 220 ℃ of temperature of reaction; N
2flow 5mL/min; Simple substance bromine flow 0.008125mol/h; Benzene flow 0.0225mol/h; Catalyzer forms: HZSM-5 (Si/Al=75); " M
xthe O/ carrier " composition: 10.0wt%CuO/HZSM-5 (Si/Al=75).
Benzene and bromine gas-phase reaction on 1.0wt%ZnO/HZSM-5 (Si/Al=400) catalyzer prepares the condition of bromobenzene and the results are shown in Table 4.
On table 41.0wt%ZnO/HZSM-5 (Si/Al=400) catalyzer, benzene and bromine reaction prepare bromobenzene
Reaction conditions: 220 ℃ of temperature of reaction; N
2flow 5mL/min; Simple substance bromine flow 0.008125mol/h; Benzene flow 0.0225mol/h; Catalyzer forms: 1.0wt%ZnO/HZSM-5 (Si/Al=400); " M
xthe O/ carrier " composition: 5.0mol%MgO/SiO
2.
Under table 5 differing temps on various catalyzer benzene and bromine reaction prepare bromobenzene
Reaction conditions: N
2flow 5mL/min; Simple substance bromine flow 0.008125mol/h; Benzene flow 0.0225mol/h; " M
xthe O/ carrier " composition: 15.0mol%MgO/SiO
2.
Metal bromide M
xbr
2reclaim simple substance bromine with oxygen reaction, with MgBr
2reclaiming simple substance bromine with oxygen reaction is example, in Table 6.
MgBr under table 6 condition of different temperatures
2reclaim simple substance bromine with oxygen reaction
Reaction conditions: oxygen gas flow rate 10mL/min; Reaction times 60min.
(3) the bromobenzene thermal hydrolysis prepares phenol, and regeneration M '
xo and/or M "
x(OH)
2
Adopt fixed-bed reactor, 10.0g load metal oxide and/or mixed metal oxide are seated in the quartz glass tube middle part that internal diameter is 18mm, reaction tubes is placed in the aluminium heating jacket, two end filling quartz sands in pipe, the pre-treatment of load metal oxide or mixed metal oxide, the thermal hydrolysis of bromobenzene, metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2regeneration and the removal process of bromine all under normal pressure, carry out.Typical operation steps is as follows:
(1) pre-treatment of load metal oxide and/or metal hydroxides: in the time of 420 ℃, N
2(5mL/min) do carrier gas, with micro-injection pump, inject hydrobromic acid aqueous solution (10mL/h, HBr>=40wt%) 1h, then stop the Hydrogen bromide charging, by N
2switch to O
2(10mL/min), in-situ regeneration (all or part of) M '
xo and/or M "
x(OH)
22h, absorb the bromine produced after oxidation with benzene.According to above step cycle operation four times.
(2) thermal hydrolysis of bromobenzene: in the time of 420 ℃, N
2(5mL/min) do carrier gas, with micro-injection pump, inject bromobenzene and water simultaneously, according to the metal oxide M ' of load
xo or metal hydroxides M "
x(OH)
2molar weight and bromobenzene flow rate calculation and control real reaction time, assurance metal oxide M '
xo or metal hydroxides M "
x(OH)
2half of middle oxide molar amount measured and reacted with bromobenzene.The 10mol%CuO/SiO of 10g packs into
2the time, bromobenzene (1.0mL/h) and water (1.0mL/h) reaction, the metering reaction times now is 75min, the reaction times then, stops the charging of bromobenzene, in this temperature of reaction, continues water flowing reaction 1h.Afterwards the liquid of condensation in liquid phase collector (ice bath) is removed to water layer, get the organic layer organic solvent diluting, GC-MS analyzes the content of each component in liquid-phase product, record and calculating response data.
(3) metal oxide M '
xo or metal hydroxides M "
x(OH)
2the recovery of regeneration and bromine: after the charging that stops water, by N
2switch to O
2(10mL/min), the M ' of original position to generating
xbr
2be regenerated as M '
xo or M "
x(OH)
2, the time is 2h, absorbs the simple substance bromine produced after oxidation with benzene.
(4) metal oxide M '
xo or metal hydroxides M "
x(OH)
2regeneration complete after, can change reaction conditions and reaction parameter, continue to continue new round reaction by (2)～(3) step.The simple substance bromine produced in the pre-treatment of load metal oxide or metal hydroxides, regeneration step directly absorbs with benzene, gets back to the first step of whole flow process and goes the bromo-reaction that carries out benzene to generate bromobenzene.
Bromobenzene and water, on load metal oxide and/or metal hydroxides, are not washed, are not carried out, under the situation of oxygen recovery step continuously feeding reaction, to collect respectively the liquid-phase product of certain period, carry out stratographic analysis, the results are shown in Table 7.
Result when table 7 bromobenzene and water continuously feeding
Reaction conditions: 420 ℃ of temperature of reaction; H
2o/ bromobenzene (mol ratio)=5.82; N
2flow 5mL/min; H
2o flow 1.0mL/h; Bromobenzene flow 1.0mL/h; Washing time 0min; O
2recovery time: 0h; " M
1m
2/ carrier " composition: 10mol%CuO/SiO
2.
Under the differential responses temperature condition, bromobenzene and water are at metal oxide M '
xthat carries out on O that thermal hydrolysis reaction prepares phenol the results are shown in Table 8.
Under table 8 differential responses temperature condition, bromobenzene and water carry out thermal hydrolysis reaction and prepare phenol
Reaction conditions: N
2flow 5mL/min; H
2o/ bromobenzene (mol ratio)=5.82; H
2o flow 1.0mL/h; Bromobenzene flow 1.0mL/h; Reaction times 75min; Washing time 60min; O
2recovery time 2h; " M
1m
2/ carrier " composition: 10.0mol%CuO/P
2-SiO
2.
Different N
2under flow condition, bromobenzene and water are at metal oxide M '
xthat carries out on O that thermal hydrolysis reaction prepares phenol the results are shown in Table 9.
Table 9 different N
2under flow condition, bromobenzene and water carry out thermal hydrolysis reaction and prepare phenol
Reaction conditions: H
2o/ bromobenzene (mol ratio)=5.82; H
2o flow 1.0mL/h; Bromobenzene flow 1.0mL/h.Reaction times 75min; Washing time 60min; O
2recovery time 2h." M
1m
2/ carrier " composition: 10.0mol%CuO/P
2-SiO
2.
Regenerated metal oxide M ' under condition of different temperatures
xo on reaction impact in Table 10 and table 11.
350 ℃ of regenerated metal oxide M ' of table 10
xduring O, bromobenzene and aqueous vapor phase reaction prepare phenol
Reaction conditions: N
2flow 5mL/min; H
2o flow 1.0mL/h; 420 ℃ of temperature of reaction; Washing time 60min; O
2recovery time 2h; " M
1m
2/ carrier " composition: 10mol%CuO/SiO
2.
420 ℃ of regenerated metal oxide M ' of table 11
xduring O, bromobenzene and aqueous vapor phase reaction prepare phenol
Reaction conditions: N
2flow 5mL/min; H
2o flow 1.0mL/h; 420 ℃ of temperature of reaction; Washing time 60min; O
2recovery time 2h; " M
1m
2/ carrier " composition: 10mol%CuO/SiO
2.
At P
2-SiO
2during the cupric oxide of the different amounts of load, the results are shown in Table 12 on carrier.
The impact of table 12 different loads amount on reaction
Reaction conditions: N
2flow 5mL/min; H
2o/ bromobenzene (mol ratio)=5.82; H
2o flow 1.0mL/h; 420 ℃ of temperature of reaction; Washing time 60min; O
2recovery time 2h.
The P of roasting under differing temps
2-SiO
2the reaction result of carrier loaded 10mol%CuO is in Table 13.
The P of table 13 differing temps roasting
2-SiO
2carrier prepares the impact of phenol on bromobenzene and aqueous vapor phase reaction
Reaction conditions: N
2flow 5mL/min; H
2o/ bromobenzene (mol ratio)=5.82; H
2o flow 1.0mL/h; 420 ℃ of temperature of reaction; Reaction times 75min; Washing time 60min; O
2recovery time 2h.
On different loads shaped metal oxide compound and/or metal hydroxides, bromobenzene thermal hydrolysis reaction result is in Table 14.
On table 14 different loads shaped metal oxide compound or metal hydroxides, bromobenzene and aqueous vapor phase reaction prepare phenol
Reaction conditions: N
2flow 5mL/min; H
2o/ bromobenzene (mol ratio)=5.82; H
2o flow 1.0mL/h; 420 ℃ of temperature of reaction; Reaction times 75min; Washing time 60min; O
2recovery time 2h.
When remarks: * adopts the Silver Nitrate load, be silver-colored simple substance after calcination, but be its oxide compound after oxygen recovery.
Metal oxide-loaded M ' on different carriers
xo, bromobenzene thermal hydrolysis reaction result is in Table 15.
On table 15 different carriers, bromobenzene and aqueous vapor phase reaction prepare phenol
Reaction conditions: N
2flow 5mL/min; H
2o/ bromobenzene (mol ratio)=5.82; H
2o flow 1.0mL/h; 420 ℃ of temperature of reaction; Reaction times 75min; Washing time 60min; O
2recovery time 2h.
Metal bromide M '
xbr
2reclaim simple substance bromine with oxygen reaction, with CuBr
2reclaiming simple substance bromine with oxygen reaction is example, in Table 16.
CuBr under table 16 condition of different temperatures
2reclaim simple substance bromine with oxygen reaction
Reaction conditions: oxygen gas flow rate 10mL/min; Reaction times 60min.
Claims (4)
1. a method for preparing phenol, comprise the steps:
A) benzene and simple substance bromine generate bromobenzene and HBr, HBr and metal oxide M under catalyst action
xthe O reaction generates metal bromide M
xbr
2and water;
B) bromobenzene that step generates in a), with water and metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2reaction generates phenol and metal bromide M '
xbr
2and/or M "
xbr
2;
Described step a) is reacted and is adopted fixed-bed reactor, and concrete reaction process is that the mixture of benzene and simple substance bromine is in succession by described beds and described metal oxide M
xthe O bed generates bromobenzene and HBr under the beds effect, and bromobenzene and HBr are by metal oxide M subsequently
xthe O bed, HBr and metal oxide M
xthe O reaction generates metal bromide M
xbr
2and water, then isolate bromobenzene, step a) in, metal oxide M
xo is selected from least one in the oxide compound of Mg, Ca, Cu, Fe, Ru, Co, Ba, Y, La, Mo, Mn, Pb, Sn, Sm, Cr, Zn, Cd, Al, Bi, Ni, Ce or Ag, step b) in, metal oxide M '
xo and/or metal hydroxides M "
x(OH)
2the metal oxide or the metal hydroxides that have a kind of Cu of being selected from, Na, K, Fe, Ru, Co, Ca, Ba, Y, La, Mo, Mn, Pb, Sn, Sm, Cr, Zn, Cd, Al, Mg, Bi, Ni, Ce or Ag at least.
2. the method for preparing phenol according to claim 1, the catalyzer that described step a) is reacted contains at least one in metal simple-substance, metal chloride, metal bromide, metal oxide, molecular sieve HZSM-5.
3. the method for preparing phenol according to claim 1, the metal bromide M that described step generates in a)
xbr
2be regenerated as metal oxide M with oxygen reaction
xo and simple substance bromine, the simple substance bromine of generation absorbs with recycle with benzene.
4. the metal bromide M ' that the method for preparing phenol according to claim 1, described step b) reaction generates
xbr
2and/or M "
xbr
2be regenerated as metal oxide M ' with oxygen reaction
xo and/or metal hydroxides M "
x(OH)
2and simple substance bromine, the simple substance bromine of generation absorbs with recycle with benzene.
Priority Applications (2)
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|---|---|---|---|
| CN 200810121156 CN101712593B (en) | 2008-09-29 | 2008-09-29 | Method for preparing phenol |
| PCT/CN2009/074246 WO2010034256A1 (en) | 2008-09-29 | 2009-09-27 | A process for producing phenol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810121156 CN101712593B (en) | 2008-09-29 | 2008-09-29 | Method for preparing phenol |
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| CN101712593B true CN101712593B (en) | 2013-06-19 |
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| CN 200810121156 Expired - Fee Related CN101712593B (en) | 2008-09-29 | 2008-09-29 | Method for preparing phenol |
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| CN115888802A (en) * | 2022-11-08 | 2023-04-04 | 喀什大学 | Bimetal supported catalyst, preparation method and application thereof, and method for catalyzing depolymerization of lignin |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3838182A (en) * | 1970-12-30 | 1974-09-24 | Gulf Research Development Co | Hydrolysis of aryl halides with metal phosphates |
| CN1424304A (en) * | 2002-12-12 | 2003-06-18 | 厦门市先端科技有限公司 | Preparation for aniline, phenol and derivative thereof |
| CN1615285A (en) * | 2002-01-24 | 2005-05-11 | Grt公司 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
-
2008
- 2008-09-29 CN CN 200810121156 patent/CN101712593B/en not_active Expired - Fee Related
-
2009
- 2009-09-27 WO PCT/CN2009/074246 patent/WO2010034256A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3838182A (en) * | 1970-12-30 | 1974-09-24 | Gulf Research Development Co | Hydrolysis of aryl halides with metal phosphates |
| CN1615285A (en) * | 2002-01-24 | 2005-05-11 | Grt公司 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
| CN1424304A (en) * | 2002-12-12 | 2003-06-18 | 厦门市先端科技有限公司 | Preparation for aniline, phenol and derivative thereof |
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