CN87104109A - Process for producing hydroxy group-containing alkyl aromatic compound - Google Patents
Process for producing hydroxy group-containing alkyl aromatic compound Download PDFInfo
- Publication number
- CN87104109A CN87104109A CN87104109.XA CN87104109A CN87104109A CN 87104109 A CN87104109 A CN 87104109A CN 87104109 A CN87104109 A CN 87104109A CN 87104109 A CN87104109 A CN 87104109A
- Authority
- CN
- China
- Prior art keywords
- parts
- water
- heteropolyacid
- reaction
- cresol
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 61
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 18
- -1 alkyl aromatic compound Chemical class 0.000 title claims abstract description 16
- 230000008569 process Effects 0.000 title abstract description 6
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 54
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 12
- 239000002168 alkylating agent Substances 0.000 claims abstract description 12
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 97
- 239000007789 gas Substances 0.000 claims description 80
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 72
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 65
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 45
- 150000001896 cresols Chemical class 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 30
- 239000011541 reaction mixture Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 22
- 150000002989 phenols Chemical class 0.000 claims description 22
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 17
- 229940100630 metacresol Drugs 0.000 claims description 17
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000640 hydroxylating effect Effects 0.000 claims 1
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 40
- 239000002253 acid Substances 0.000 description 31
- 239000003921 oil Substances 0.000 description 28
- 239000007864 aqueous solution Substances 0.000 description 27
- 238000004587 chromatography analysis Methods 0.000 description 26
- 238000013019 agitation Methods 0.000 description 25
- 239000007795 chemical reaction product Substances 0.000 description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 24
- 238000004140 cleaning Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 229960003742 phenol Drugs 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229960001755 resorcinol Drugs 0.000 description 4
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 4
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000020335 dealkylation Effects 0.000 description 3
- 238000006900 dealkylation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003974 emollient agent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 2
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 2
- AQJFATAFTQCRGC-UHFFFAOYSA-N 2-Chloro-4-methylphenol Chemical compound CC1=CC=C(O)C(Cl)=C1 AQJFATAFTQCRGC-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- QDQMEHXIUFCIGR-UHFFFAOYSA-N 4-ethyl-2-methylphenol Chemical compound CCC1=CC=C(O)C(C)=C1 QDQMEHXIUFCIGR-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- IICQZTQZQSBHBY-HWKANZROSA-N (e)-non-2-ene Chemical compound CCCCCC\C=C\C IICQZTQZQSBHBY-HWKANZROSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- PCNMALATRPXTKX-UHFFFAOYSA-N 1,4-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CCC(C)(O)C=C1 PCNMALATRPXTKX-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- 150000004782 1-naphthols Chemical class 0.000 description 1
- LMLAXOBGXCTWBJ-UHFFFAOYSA-N 2,4-diethylphenol Chemical compound CCC1=CC=C(O)C(CC)=C1 LMLAXOBGXCTWBJ-UHFFFAOYSA-N 0.000 description 1
- OTTZHAVKAVGASB-HYXAFXHYSA-N 2-Heptene Chemical compound CCCC\C=C/C OTTZHAVKAVGASB-HYXAFXHYSA-N 0.000 description 1
- HKHXLHGVIHQKMK-UHFFFAOYSA-N 2-chloro-m-cresol Chemical class CC1=CC=CC(O)=C1Cl HKHXLHGVIHQKMK-UHFFFAOYSA-N 0.000 description 1
- SWZVJOLLQTWFCW-UHFFFAOYSA-N 2-chlorobenzene-1,3-diol Chemical compound OC1=CC=CC(O)=C1Cl SWZVJOLLQTWFCW-UHFFFAOYSA-N 0.000 description 1
- SRGATTGYDONWOU-UHFFFAOYSA-N 2-cyclohexyl-5-methylphenol Chemical compound OC1=CC(C)=CC=C1C1CCCCC1 SRGATTGYDONWOU-UHFFFAOYSA-N 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 1
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- IICQZTQZQSBHBY-UHFFFAOYSA-N 2t-nonene Natural products CCCCCCC=CC IICQZTQZQSBHBY-UHFFFAOYSA-N 0.000 description 1
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- MCUFTLAXJMCWPZ-UHFFFAOYSA-N 3-butyl-2-methylphenol Chemical group CCCCC1=CC=CC(O)=C1C MCUFTLAXJMCWPZ-UHFFFAOYSA-N 0.000 description 1
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- IWJGMJHAIUBWKT-UHFFFAOYSA-N 4-bromo-2-methylphenol Chemical compound CC1=CC(Br)=CC=C1O IWJGMJHAIUBWKT-UHFFFAOYSA-N 0.000 description 1
- RHPUJHQBPORFGV-UHFFFAOYSA-N 4-chloro-2-methylphenol Chemical compound CC1=CC(Cl)=CC=C1O RHPUJHQBPORFGV-UHFFFAOYSA-N 0.000 description 1
- XQZZRMOYMBRVNA-UHFFFAOYSA-N 4-cyclohexyl-3-methylphenol Chemical compound CC1=CC(O)=CC=C1C1CCCCC1 XQZZRMOYMBRVNA-UHFFFAOYSA-N 0.000 description 1
- DSTPUJAJSXTJHM-UHFFFAOYSA-N 4-methyl-2-propan-2-ylphenol Chemical compound CC(C)C1=CC(C)=CC=C1O DSTPUJAJSXTJHM-UHFFFAOYSA-N 0.000 description 1
- SNKLPZOJLXDZCW-UHFFFAOYSA-N 4-tert-butyl-2-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC=C1O SNKLPZOJLXDZCW-UHFFFAOYSA-N 0.000 description 1
- KREKFPNOUVVSFI-UHFFFAOYSA-N 5-propan-2-ylnaphthalen-2-ol Chemical compound OC1=CC=C2C(C(C)C)=CC=CC2=C1 KREKFPNOUVVSFI-UHFFFAOYSA-N 0.000 description 1
- HALUFMAHPNDSTF-UHFFFAOYSA-N 8-propan-2-ylnaphthalen-2-ol Chemical compound C1=C(O)C=C2C(C(C)C)=CC=CC2=C1 HALUFMAHPNDSTF-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 230000006208 butylation Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- 125000004980 cyclopropylene group Chemical group 0.000 description 1
- YKNMBTZOEVIJCM-UHFFFAOYSA-N dec-2-ene Chemical compound CCCCCCCC=CC YKNMBTZOEVIJCM-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for producing an alkyl aromatic compound having a hydroxyl group, characterized by reacting an aromatic compound having at least one hydroxyl group with an alkylating agent in the presence of a heteropoly acid in a liquid phase.
Description
The present invention relates to a kind of new method, this method is to utilize aromatics and alkylating agent with at least one hydroxyl to react the alkyl aromatic compound for preparing hydroxyl in liquid phase.
The alkyl aromatic compound of hydroxyl, particularly by phenolic compound and alkylating agent, especially have purposes widely with iso-butylene or the alkylphenol compounds that contains the gas reaction gained of iso-butylene, for example can be used as antioxidant, stablizer etc. or with the raw material of used as pesticides and dyestuff intermediate or resin and technical chemistry medicine.
Especially, react 2 of gained by p-Cresol or the gas that contains the cresols and the iso-butylene of p-Cresol or contain iso-butylene in the presence of heteropolyacid, 6-di-t-butyl-4-cresols can be used as the representative of alkylphenol compound of the present invention.
As everyone knows, as make the phenolic compound alkylation produce alkylphenol compounds with branched-chain alkene, a kind of method of tertiary alkyl phenolic compound especially, reaction is carried out in the presence of an acidic catalyst.For used catalyzer in this reaction, known have a sulfuric acid (Industrial and Engineering Chemistry, Vol, 35, pp.264-272 (1943), aluminum chloride (Journal of American Chemical Society, Vol.67, pp.303～307 (1945), metalloaryl oride (No. 2821898 United States Patent (USP)s).Toluenesulphonic acids and toluenesulphonic acids type Zeo-karb (Japanese patent gazette number clear 37-18182), cresol sulfonic acid (No. 2733274 United States Patent (USP)s) etc.
But, reality is reacted with gas that contains iso-butylene, butene-1, butene-2 etc. and phenolic compound inexpensive and that obtain easily because be industrial, if use above-mentioned catalyzer, its shortcoming is to produce a large amount of secondary induced by alkyl hydroxybenzene by products.For this reason, suggestion uses the high purity carbon hydrogen compound as raw material.
So this method must be with iso-butylene from containing the mixture of iso-butylene, for example separation and purification are come out in the light constituent that cracking produced of petroleum products, and this is disadvantageous in industry.
As industrial and favourable economically tertiary alkyl phenolic compound preparation method, considered to make the method for the mixture that contains iso-butylene and phenolic compound reaction, and done extensive studies.But the iso-butylene in the gas mixture that is difficult to make mixture promptly contain iso-butylene optionally reacts, and therefore, the catalyzer of past to highly selective carried out many researchs, and proposes many kinds of catalyzer.
These in the past known methods all exist and improve the selective reaction rate and will reduce, and the shortcoming that also reduces of the specific absorption of iso-butylene.And attempt to improve reactivity, and the utilization of iso-butylene also improves, the growing amount of the polymkeric substance of secondary alkylphenol compounds, isobutene polymer and other olefin gas increases, therefore, make the cleaning and the purification operations of purpose product become extremely complicated, and must carry out special disposal the waste liquid that produces.
In addition,, must purify and lock out operation, also be unsuitable for suitability for industrialized production with regard to this point because the gas of discharging contains a large amount of above-mentioned polymkeric substance, thereby can not directly be used as fuel.
When catalyzer such as known sulfuric acid of use and toluenesulphonic acids, will produce sulfonated bodies and neutral ester (butyl sulfuric ester etc.).Just as known, even through neutralization and cleaning, these ester classes still remain in the reaction product, when distillation, if be heated to high temperature, they will play dealkylation catalyst, can not obtain the alkylphenol compounds of high quality, high yield thus.
For this reason, so far for adopt under High Temperature High Pressure always with alkaline aqueous solution neutralization reaction product method, so that these esters decompose (Industrial and Engineering Chemistry, Vol. 35, pp.265～272 (1943)).
Have again, when adopting these catalyzer equipment is had intensive corrodibility,, therefore have many other problems at the industrial equipment that must use senior material.
In view of the foregoing, the present invention has in the aromatics and the alkylated reaction of alkylating agent as raw material of at least one hydroxyl using, can be economical, high selectivity simple to operate and the method for producing needed compound with high yield carried out extensive studies, found that when this alkylated reaction is made catalyzer and carried out under liquid-phase condition with heteropolyacid, can highly selective and obtain required compound with high yield.
Especially, if adopt method of the present invention, then demonstrate and containing iso-butylene, butene-1, in the gas of butene-2 and the reaction of phenolic compound, can suppress butene-1 effectively, the side reaction of butene-2 etc., and the polymerization that prevents iso-butylene etc., and can easily produce the purpose product alkylphenol compounds of extreme high purity and high yield, in addition, the heteropolyacid that uses in the reaction, after reaction, can easily reclaim, and can reuse, and the corrodibility of equipment is reduced, thus industrial be exceedingly useful.Therefore finished the present invention.
According to the inventive method, aromatics and alkyl agent with at least one hydroxyl are reacted in liquid phase in the presence of heteropolyacid, just can reach above-mentioned purpose of the present invention.
Below the inventive method is described in more detail.
As the aromatics with at least one hydroxyl used in this invention, with the following compounds is example: the monobasic phenols, as phenol, adjacent-, between-or p-Cresol and their mixture, adjacent-, between-or right-ethylphenol, adjacent-, between-or right-isopropyl-phenol, adjacent-, between-or right-tert.-butyl phenol, adjacent-, between-or right-sec-butyl phenol, the 4-tertiary butyl-6-methylphenol, 2, the 4-xylenol, 2-methyl-4-ethylphenol, 2, the 4-diisopropyl phenol, 4-methyl-6-isopropyl-phenol, 2,6-two-tert.-butyl phenol, the 2-tertiary butyl-4-methylphenol, 3 methy 6 tert butyl phenol, 2-chloro-4-methylphenol, right-chlorophenol, right-bromophenol, 2, the 4-chlorophenesic acid, 2, the 4-dibromophenol, 2-methyl-4-chlorophenol, 2-methyl-4-bromophenol, 2,4-two chloro-3-methylphenols, 3-methyl-6-cyclohexylphenol, 3-methyl-4-cyclohexylphenol etc.; Polyatomic phenol, for example Resorcinol, Resorcinol, pyrocatechol, 2-methylresorcinol, 2-chloro resorcinol, 2-hydroxyl Resorcinol, 2-chlorohydroquinone, 4-tert-butyl resorcin, Phloroglucinol etc.; Aphthols, for example, 1-naphthols, beta naphthal, 2-hydroxyl-3-carboxyl naphthalene, 1-hydroxy-5-methyl base naphthalene, 2-hydroxy-5-methyl base naphthalene, 2-hydroxyl-8-isopropyl naphthalene, 2-hydroxyl-5-isopropyl naphthalene etc.
In these compounds, cresols class (comprising cresols) or Resorcinol etc. are the most suitable.
Used alkylating agent can adopt and comprise unsaturated hydrocarbons with at least one two key, aliphatics alcohols etc. among the present invention.
The unsaturated hydrocarbons that contains two keys comprises: by the compound of general formula (I) representative,
R
1-CH=CH
2(I) R wherein
1Representing hydrogen or carbonatoms is 1～10 straight or branched hydrocarbon residue, by the compound of general formula (II) representative,
R
2-CH=CH-CH
3(II) (R wherein
2Representing carbonatoms is 1～9 straight or branched hydrocarbon residue), and carbonatoms is up to 10 ring-type unsaturated hydrocarbons.
The object lesson of these hydrocarbon is ethene, propylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, 2-amylene, isopentene, 1-hexene, 2-hexene, 1-heptene, 2-heptene, 1-octene, 2-octene, 1-nonene, 2-nonene, 1-decene, 2-decene, 1-laurylene, 2-laurylene, cyclopropylene, cyclobutene, cyclopentenes, tetrahydrobenzene, cyclooctene, or the like.
The concrete example of fatty alcohol is methyl alcohol, ethanol, Virahol, the trimethyl carbinol, sec-butyl alcohol, amylalcohol, hexanol, phenylcarbinol, hexalin or the like.
These alkylating agents also can adopt other two or more mixture.As the example of mixture, except that pure iso-butylene; Containing iso-butylene mixed gass (being designated hereinafter simply as LBB gas) such as 1-butylene, 2-butylene also can use.
In enforcement of the present invention, the alkylating agent that participates in reaction can use with arbitrary proportion, and for the aromatics that has a hydroxyl at least, mol ratio is 0.1～30 times usually, be preferably 1～20 times, and best be 1～5 times.
In addition, (plural alkyl is introduced aromatic nucleus) when many alkylations, the mol ratio of alkylating agent is generally 2～50 times, is preferably 2～20 times, and best is 2～5 times.
In the methods of the invention, must with the heteropolyacid catalyzer.Said in the present invention heteropolyacid be meant can with mineral acid bonded polyacid in, the acid that forms by two or more metal.In general, heteropolyacid is to be center and by the general name of the compound of other metal of central metal coordinate (polyatom) therewith such as oxygen with a kind of metal (or heteroatoms).This heteroatoms has boron, aluminium, silicon, phosphorus, titanium, germanium, arsenic, zirconium, tin, tellurium etc., and polyatom comprises molybdenum, tungsten, vanadium, niobium etc.
Specifically, comprise phospho-molybdic acid, silicomolybdic acid, arsenic molybdic acid, tellurium molybdic acid, aluminium molybdic acid, silicotungstic acid, phospho-wolframic acid, borowolframic acid, titanium wolframic acid, stannotungstic acid etc.In these compounds, be preferably phospho-molybdic acid, silicomolybdic acid, phospho-wolframic acid, silicotungstic acid etc., best is silicotungstic acid.
In addition, these heteropolyacids use with the form of hydrate usually.
The usage quantity of catalyzer is generally 0.00001～0.3 times of aromatics weight along with form and other condition and different of reaction.With 0.0001～0.1 times better, 0.0002～0.03 times is better.
If the usage quantity of heteropolyacid in the inventive method is after considering that reaction finishes, reclaim this use again with aqueous solution form, just needn't limit the quantity of, than relatively large use, so that stable reaction is carried out, recovery and reuse are comparatively favourable then.
Reaction of the present invention is characterized in that it is in the presence of above-mentioned heteropolyacid, carries out in liquid phase.During this method of industrial enforcement, all be favourable aspect operation, economy and the equipment.
In the methods of the invention, temperature of reaction is generally 20～200 ℃, and 30～150 ℃ better, and 40～90 ℃ better.When temperature of reaction was too low, speed of response was slack-off; On the contrary, when temperature of reaction is too high, show the tendency that by product increases.
In the methods of the invention, the reaction times there is not particular restriction, but general just enough with about 0.5～50 hour.
In the method for the invention, for how alkylating agent being introduced does not have particular restriction in the reaction system, for example, under the situation of using LBB, it can be introduced in the reaction system with gas phase (gaseous state) or liquid phase (liquid state).
As the heteropolyacid of catalyzer, according to reaction conditions and different, can be with undissolved, promptly the state of heterodisperse system uses.In this case, can make coexistence with it such as water as thinner or solvating agent, acetone.The amount of the water of coexistence, acetone etc. is generally 0.1～20 times of heteropolyacid weight, and 0.5～5 times better.
In the implementation process of the inventive method,, can improve purpose product induced by alkyl hydroxybenzene, the particularly selectivity of tertiary alkyl phenolic compound and yield owing to exist a certain amount of water in the reaction system.
That is, present inventors find, when being raw material with the phenols, make 0.0001～0.10 times of its weight, be preferably 0.001～0.05 times, preferably 0.002～0.03 times water is present in the system, and achieve the above object.
In addition, the amount of water in the reaction system also should be taken the water yield of being introduced by the crystal water of the heteropolyacid that uses as catalyzer into account in the lump.
Therefore, when the usage quantity of heteropolyacid increased, the amount of water also increased, and vice versa, if utilize regulating pondage in above-mentioned scope, reaction carried out more reposefully, just can reach highly selective and high yield.
When the water yield in the system when above-mentioned scope is above, the speed of response of phenolic compound and iso-butylene reduces, and residual a large amount of unreacted phenols and intermediate product.In the water yield is lower than above-mentioned scope or system under the anhydrous situation, show a kind of like this tendency, be that butene-1 contained in the LBB gas, butene-2 etc. are equal to or greater than the speed of response of iso-butylene and phenols with the speed of response of phenols, and generate by products such as a large amount of undesirable secondary alkylphenol compoundses.
In the system that adopts solid acid catalyst in the past to react, if make the water coexistence, then strength of acid reduces, catalyst activity reduction.According to the technology general knowledge in this field, afore-mentioned then is all beyond one's expectations.
When residual a large amount of unreacted phenols raw material, in order to reclaim the phenols raw material, must carry out complex operations, though perhaps use industrial obtaining easily and cheap LBB gas, but also can contain a large amount of undesirable by products, thereby must carry out complexity and the purification operations of difficulty.For fear of above complexity and the difficulty operation, determining of reaction conditions is very important.For this purpose, reaction must be carried out in water yield scope of the present invention.
Be present in the water in the system, adopt pure water, process water, recycle-water, water vapour etc. all can.
Making water be present in method in the system is add phenols raw material and heteropolyacid in system after, adds to system then that quantitative water realizes.As another kind of method, can control the moisture of phenols raw material in advance, make that the water-content of system is in predetermined scope behind the adding heteropolyacid.
In addition, also heteropolyacid can be made the aqueous solution after it joins the phenols raw material, the water-content in the system just is in the predetermined scope.Arbitrary aforesaid method can use.
Notable feature of the present invention is almost to produce the high boiling point product that resembles butene dimer and so in waste gas when using heteropolyacid as the catalyzer of the inventive method.That is to say, in with iso-butylene or LBB gas generation alkylphenol compounds, when using sulfuric acid etc. to make catalyzer, in the gas of discharging, generate a large amount of butene dimerization bodies, make this gas can not directly be used as fuel, town gas etc.Thereby, must from waste gas, remove these high boiling point products, this industrial be disadvantageous.But in the methods of the invention,, therefore has the advantage that only needs the waste gas compression just can be obtained at an easy rate high-quality liquefied petroleum gas because of butylene produces the high boiling point product hardly.
Those reactions that the reaction formation of the inventive method is not limited among the embodiment to be chatted, normal pressure or add intermittent type or the continuous reaction depressed and all can use certainly.
Reaction both can have solvent also can carry out in the presence of solvent-free.
The solvent that uses in reaction is aromatic hydrocarbon based and resemble the ethers of isopropyl ether and so on as benzene,toluene,xylene, ethylbenzene, ethyltoluene, isopropyl benzene, oil of mirbane, chlorinated benzene etc.Because the solvent usage quantity do not produce tangible influence, so consumption is 0.5～50 times of aromatics weight with at least one hydroxyl preferably, preferably 1～20 times.
Above-mentioned described, when using sulfuric acid, toluenesulphonic acids etc. to make catalyzer, generate neutral ester (butyl sulfuric ester etc.), must under high temperature, high pressure, carry out neutralizing treatment thus.But do not generate owing to resemble the impurity of sulfuric ester and so on, so neutralizing treatment may be carried out under utmost point demulcent condition in the embodiment of this invention.That is to say, only reaction product is neutralized or just clean and to remove impurity fully with alkaline aqueous solution or warm water.
It is so high that neutralization and the temperature of cleaning needn't resemble in the ordinary method used temperature, and 40～90 ℃ temperature just is enough to impurity is removed.The amount of employed alkaline aqueous solution or warm water makes water layer be neutral just enough, but general consumption is 0.1～10 times of reaction product weight, preferably 0.2～5 times.When they not only can once use, and divide several times and use, it is better to remove the impurity effect.
Alkaline aqueous solution or warm water utilize to stir with contacting of reaction product realizes that be 5 minutes～10 hours duration of contact, is preferably 10 minutes～5 hours.Alkaline aqueous solution for example can prepare with sodium hydroxide and water.
Preparing in the process of alkylphenol compounds with phenols and iso-butylene or the gas reaction that contains iso-butylene, carrying out along with reaction, the heteropolyacid amount of separating out in the reaction system increases, and when reaction finished, employed heteropolyacid was almost all separated out.
The heteropolyacid of separating out can directly be separated from reaction solution, or with after the reaction solution cooling, again the heteropolyacid of separating out is separated, can be realized this separation fully by conventional separation methods such as filtration, centrifugation or decants.
When separating this heteropolyacid, there is no need to carry out solid-liquid and separate fully, the heteropolyacid that contains a large amount of reaction solutions can be recovered, and re-uses fully in reaction.Moreover, even the heteropolyacid that in oil reservoir, contains, if its amount during the having a strong impact on of unlikely generation dealkylation, has not big harm under the distillation condition of back operation.
Even neutralize with the fluidity aqueous solution before distillation, very Xiao Liang alkali is also enough.
As other method of separating heteropolyacid after reaction from reaction mixture be, the water reaction mixture is dissolved in the water layer heteropolyacid, then with the method that makes oil reservoir and water layer, makes it to separate.In this case, all can as the water of reaction mixture such as pure water, process water, recycle-water, water vapor etc.
The method that the water reaction mixture extracted, reclaimed heteropolyacid catalyst can be adverse current or and the interrupter method of stream, adverse current or and the continuous processing of stream in any.
For making it, the heteropolyacid that will reclaim utilizing once more in the secondary response down, preferably the heteropolyacid content in the water layer is adjusted to 20% (weight) or more than 20% (weight), preferably 30% (weight) or more than 30% (weight).
Using under the situation of interrupter method, can add the water of any amount, but preferably with the concentration limit of the heteropolyacid aqueous solution in above-mentioned scope, so that this solution can be used for subsequent reactions once more.But, when because the amount of heteropolyacid catalyst is few, oil reservoir is too big to the ratio of water layer, so that be difficult to make the oil reservoir water layer to separate, can extract, reclaim heteropolyacid this moment by increasing the water yield, and then evaporate the water, make heteropolyacid reach above-mentioned desired concn.
After reaction finishes,, preferably add a spot of unessential water and make these heteropolyacid dissolvings in the occasion that heteropolyacid is separated out.
Moreover after the reaction, the water of adding can once add, and also can divide for several times to add.
When reclaiming heteropolyacid with continuous processing, in mixing tank one settling vessel that has added predetermined amount of water, reaction mixture is added continuously, mix, and be separated into water layer and oil reservoir, handle just to make the heteropolyacid in the water layer reach above-mentioned desired concn like this, therefore, this continuous processing industrial be favourable.This method can adopt single-stage or multistage operations.The rate of recovery of heteropolyacid can reach more than 95%.Must in settling vessel, add entry continuously, replenishing owing to being dissolved in the water yield that reaction mixture reduces, the preferably vertical monolithic devices of this mixing tank one settling vessel, the bottom is a mixing tank, top is settling vessel.But mixing tank and settling vessel also can separately use, and be recycled to mixing tank with water layer from settling vessel and also can achieve the above object this moment.
Moreover, various extractors commonly used all can be used for the present invention, if necessary, also can be between mixing tank and settling vessel, adorn the net that a usefulness glass fibre, polymer fiber etc. are made, " coalescer " (coalesor) (Japanese Mesh company trade(brand)name) for example is to improve separating of oil reservoir and water layer.
In this case, separation temperature should be more than the temperature of the unlikely crystallization of purpose product alkylphenol compounds.Industrial, generally the temperature after reaction finishes or be lower than slightly under this temperature is separated.
The heteropolyacid of isolating recovery can be used for subsequent reactions once more in this way, but in this case, as mentioned above, a certain amount of water is present in the reaction system.
To remove reaction solution behind the heteropolyacid with after a spot of water or basic solution neutralization and cleaning, or under the situation of reacting with solvent, by ordinary method separated from solvent is removed, just can obtain desirable alkylphenol compounds.
If necessary, product can further be purified by methods such as distillation, extraction, recrystallizations.
Below, to utilizing cresols and iso-butylene or containing the reaction of gas of iso-butylene and the method that obtains typical alkylphenol compounds of the present invention more is described in detail.
Utilize aforesaid method, after from reaction mixture, isolating heteropolyacid, under ten minutes demulcent industry distillation condition, can easily from oil reservoir, obtain high quality 2,6-di-t-butyl-4-sylvan by high yield (dealkylation does not promptly take place).
For example, heat oil reservoir down for 100～160 ℃ at normal pressure, the dehydration and remove after the low boiling component, under the decompression of 20～100 torrs, remove a butenyl thing in 120～160 ℃ of distillations, under the decompression of 10～70 torrs, obtain 2,6-di-t-butyl-4-sylvan then in 140～200 ℃ of distillations.
This distillation (rectifying) can be undertaken by any successive and method intermittently, and its condition has more than and is limited in the above-mentioned scope.
Not only can almost reclaim 2 in the oil reservoir quantitatively, 6-di-t-butyl-4-sylvan, and decomposition reactions such as debutylize can not take place, and can almost reclaim quantitatively as low boiling component-the butyl thing, this compound is capable of circulation to be used for the butylation reaction.
In addition, when making raw material with the cresols mixture that contains p-cresol, distillate 2 by distillation, after 6-di-t-butyl-4-sylvan, the main component of remaining high boiling component is 4,6-di-t-butyl-3-sylvan, this component also can almost reclaim quantitatively, and the decomposition reaction as debutylizeization can not take place.
Used in the methods of the invention heteropolyacid has high reactivity and highly selective, make thus can industrial advantageously, obtain required alkylate with high yield, particularly contain the alkylated aromatic compound of hydroxyl.
Particularly, have following advantage, promptly do not produce the impurity that resembles sulfonated bodies and so on, make postprocessing working procedures under ten minutes demulcent condition, to carry out at an easy rate.
In addition because heteropolyacid is low to the corrodibility of equipment, even reaction at high temperature, also can use the cheap apparatus material therefore industrial be exceedingly useful.
Below, with reference to embodiment the present invention is narrated in more detail, but main contents of the present invention are not limited to the following examples.
Have, umber in an embodiment and percentage ratio (%) are benchmark to steam sulphur all again.
Embodiment 1
With 100 parts of cresols mixture (p-cresol 70%; Meta-cresol 30%) and 0.04 part phospho-wolframic acid join in the flask, under agitation remain between 60～65 ℃, with importing 288 parts of LB B gases (iso-butylene content is 45%) in 8 hours.
The weight of reaction mixture is 195.1 parts.
After water and alkaline aqueous solution wash down reaction product, can get 186.5 parts of oily products.Through gas chromatographic analysis, this oily product composed as follows:
Unreacted cresols 1.5%
The 2-tertiary butyl-4-sylvan 19.5%
The 6-tertiary butyl-3-sylvan 5.6%
2,6-di-t-butyl-4-sylvan 44.2%
4,6-di-t-butyl-3-sylvan 22.5%
Other are 6.7% years old
Embodiment 2
With 100 parts of cresols mixture (p-cresol of 70%, 30% meta-cresol) and 0.15 part silicotungstic acid join in the flask, under agitation remain between 45～55 ℃, in 10 hours, import 288 parts LBB gas (iso-butylene content is 45%).
Reaction mixture weight is 210.3 parts.
After this reactant water and alkaline aqueous solution cleaning, obtain 192.5 parts oily product.Composed as follows through this oily product of gas chromatographic analysis:
Unreacted cresols 0.9%
The 2-tertiary butyl-4-sylvan 19.1%
The 6-tertiary butyl-3-sylvan 3.6%
2,6-di-t-butyl-4-sylvan 42.8%
4,6-di-t-butyl-3-sylvan 24.3%
Other are 9.3% years old
Embodiment 3
The phospho-molybdic acid of 100 parts of p-cresol and 0.9 part is joined in the flask, under agitation remain between 55～65 ℃, with importing 110 parts of isobutene gas in 5 hours.
The weight of reaction mixture is 206.7 parts.
After this reaction product water and alkaline aqueous solution cleaning, obtain 198.3 parts of oily products.Composed as follows through this oily product of gas chromatographic analysis:
Unreacted p-cresol 1.0%
The 2-tertiary butyl-4-sylvan 7.1%
2,6-di-t-butyl-4-sylvan 85.4%
Other are 6.5% years old
In addition, the trimeric content of isobutene dimer in the unreacted gas and iso-butylene is 1. 2%.
Embodiment 4
100 parts cresols mixtures (70% p-cresol, 30% meta-cresol) and 0.02 part silicotungstic acid are joined in the flask, under agitation remain between 70～75 ℃, with the isobutene gas that imported 110 parts in 6 hours.
Reaction product water and alkaline aqueous solution obtain 193.5 parts oily product after cleaning.Composed as follows through this oily product of gas chromatographic analysis:
Unreacted cresols 0.9%
The 2-tertiary butyl-4-sylvan 6.0%
The 6-tertiary butyl-3-sylvan 1.5%
2,6-di-t-butyl-4-sylvan 60.1%
4,6-di-t-butyl-3-sylvan 26.4%
Other are 5.1% years old
Embodiment 5
The silicotungstic acid that adds 0.06 part in 94.1 parts phenol under agitation remains between 50～60 ℃, with the isobutene gas that imported 118 parts in 4 hours.
The weight of reaction mixture is 200.7 parts.
This reaction product water and alkaline aqueous solution obtain 190.1 parts oily product after cleaning.Find the composed as follows of this oily product through gas chromatographic analysis:
Unreacted phenol 1.5%
2-tert-butyl phenol 15.4%
4-tert-butyl phenol 9.6%
2,6-di-tert-butylphenol 15.5%
2,4-di-tert-butylphenol 37.5%
2,4,6-tri-tert-butyl phenol 14.7%
Other are 5.8% years old
Embodiment 6
The phospho-wolframic acid that adds 1.0 parts in 54.8 parts of ortho-cresols under agitation remains between 50～55 ℃, with the isobutene gas that imported 71 parts in 5 hours.
Reaction mixture weight is 104.5 parts.
Composed as follows through the gas chromatographic analysis reaction product:
Unreacted ortho-cresol 1.5%
The 6-tertiary butyl-2-sylvan 6.5%
The 4-tertiary butyl-2-sylvan 10.1%
4,6-di-t-butyl-2-sylvan 76.7%
Other are 5.2% years old
In addition, the content of isobutene dimer in the unreacted gas and isobutylene trimer is 1.0%
Embodiment 7
The toluene solvant of 40 parts Resorcinols, 200ml and 1.2 parts silicotungstic acid are joined in the flask, under agitation remain between 50～60 ℃, import alkene gas.
After reaction finishes, leach catalyzer, the usefulness 40ml water cleaning again of separating out.The scavenging solution vapourisation under reduced pressure is condensed into 200ml, add 20ml water again after, with ice-cooled.The crystal that utilizes reclaiming by filtration to separate out, drying under reduced pressure can obtain 79.5 parts of solids.Through gas chromatographic analysis, found to obtain purity and be 98.5% 4, the 6-di-tertiary butyl methyl phenol.
Embodiment 8
54.1 parts meta-cresols are encased in the flask, to wherein adding 1.2 parts of silicomolybdic acid, under agitation keep between 90～95 ℃ then, with the tetrahydrobenzene that splashed into 45.2 parts in 3 hours.
Reaction mixture weight is 98 parts.
The result is as follows through gas chromatographic analysis:
6-cyclohexyl-3-sylvan 10.2%
4-cyclohexyl-3-sylvan 20.5%
4,6-dicyclohexyl-3-sylvan 1.2%
Embodiment 9
94 parts phenol and 0.9 part of silicotungstic acid are joined in the flask, under agitation remain between 90～100 ℃,, be incubated 5 hours down at 110～120 ℃ again with the ethanol that splashed into 50 parts in 2 hours.
The transformation efficiency of phenol is 20%.
After from reaction mixture, removing unreacted phenol and ethanol, the reaction product that obtains composed as follows:
Phenyl ethyl ether 13%
Phlorol 42%
Between ethyl phenol 3%
To ethyl phenol 37%
2,4-diethyl phenol 5%
Embodiment 10～16
With reactor and the reaction method identical with embodiment 1, reaction is carried out in embodiment 1 identical mode, aromatics that only is to use and alkylating agent and other reaction conditionss are different, and gained the results are shown in the table 1.
Table 1
| Embodiment | Aromatics | Heteropolyacid | Solvent and other | Alkylating agent | Time (hr) | Transforming agent | The selection rate of one alkyl thing | The selection rate of dialkyl group thing | |||||
| Usage quantity | Usage quantity | Usage quantity | Temperature (℃) | Usage quantity | |||||||||
| ????10 ????11 ????12 ????13 ????14 ????15 ????16 | The metacresol paracresol 2-tert-butyl group-4-sylvan phenol beta naphthal 2-ethyl phenol phenol | 49.6 43.8 parts 146.6 parts 94.1 parts 30 parts 50 parts 20 parts of parts | Phospho-molybdic acid phospho-wolframic acid silicotungstic acid silicotungstic acid silicotungstic acid silicotungstic acid phospho-wolframic acid | 0.04 0.8 part 3.0 parts 1.9 parts 0.2 part 0.5 part 0.4 part of part | Water water-toluene water-toluene | 1.5 1.0 parts 300 parts 0.5 part 200 parts of parts | ??65-70 ??60-65 ??45-50 ??80-85 ??100-110 ??80-85 ??130- ????140 | 1-butylene tert-butyl alcohol isobutene propylene isobutene 1-hexene 1-laurylene | 26 parts 75 parts 62 parts 80 parts 25 parts 52 parts 55 parts | ??7 ??10 ??5 ??7 ??7 ??5 ??15 | ??20％ ??12％ ??56％ ??60％ ??53％ ??25％ ??15％ | ??65.5％ ??75 ??14％ ??52％ ??25％??? ??71％ ??83％ | ??24.0％ ??8.3％ ??81％ ??30％ ??63％ ??13％ ??7％ |
Embodiment 17
With 100 parts of cresols mixtures (70% p-cresol, 30% meta-cresol) and 1 part wolframic acid is joined in the flask, add water-content that water makes material in the flask then and be 0. 026 times of cresols mixture weight.
Then, under agitation remain between 45～55 ℃, with the LBB gas (iso-butylene content is 45%) that imported 288 parts in 5 hours.
Reaction mixture weight is 206.3 parts.
Reaction product water and alkaline aqueous solution obtain 191.5 parts oily product after cleaning.Through gas chromatographic analysis, this oily product composed as follows:
Unreacted cresols 0.7%
The 2-tertiary butyl-4-sylvan 17.8%
The 6-tertiary butyl-3-sylvan 2.4%
2,6-di-t-butyl-4-sylvan 48.1%
4,6-di-t-butyl-3-sylvan 26.4%
Other are 4.6% years old
Embodiment 18
100 parts of cresols mixtures (70% p-cresol, 30% meta-cresol) and 1 part phospho-wolframic acid are joined in the flask, add water again, the water content of material in the flask is adjusted to into the cresols mixture weight 0.002 times.
Then, under agitation keep between 55～60 ℃, with the LBB gas (iso-butylene content is 45%) that imported 288 parts in 7 hours.
The weight of reaction mixture is 204.1 parts.
After reaction product water and alkaline aqueous solution cleaning, obtain 194.1 parts oily product.Through gas chromatographic analysis, this product composed as follows:
Unreacted cresols 0.6%
The 2-tertiary butyl-4-sylvan 16.9%
The 6-tertiary butyl-3-sylvan 3.2%
2,6-di-t-butyl-4-sylvan 48.5%
4,6-di-t-butyl-3-sylvan 25.6%
Other are 5.2% years old
Embodiment 19
100 parts of p-cresol are added in the flask,, under agitation remain between 50～60 ℃, with 10 hours importing 242 parts of LBB gases (iso-butylene content is 45%) then to the silicon tungsten acid solution that wherein adds 0.8 part 50%.
Reaction mixture weight is 202.0 parts.Leach after the silicotungstic acid of separating out with glass filter, can obtain 200.2 parts oily product when filtrate is cleaned with less water.Composed as follows through this oily product of gas chromatographic analysis:
Unreacted p-cresol 0.7%
The 2-tertiary butyl-4-sylvan 7.3%
2,6-di-t-butyl-4-sylvan 88.8%
Other are 3.2% years old
In addition, the dipolymer of the iso-butylene in the unreacting gas and trimeric content are 0.2%.
Embodiment 20
100 parts of meta-cresols are packed in the flask, be 40% phosphotungstic acid aqueous solution to wherein adding 1 part of concentration then, under agitation remain between 60～65 ℃, with the LB B gas (iso-butylene content is 45%) that imported 242 parts in 6 hours.
Reaction mixture weight is 202.5 parts.
In reactant, add 5 parts of water, so that the dissolving of the phospho-wolframic acid in the water layer is separated oily matter from water layer.Clean with a spot of alkaline aqueous solution, can obtain 201.8 parts oily product.Composed as follows through this oily matter of gas chromatographic analysis:
Unreacted meta-cresol 0.9%
The 6-tertiary butyl-3-sylvan 7.0%
4,6-di-t-butyl-3-sylvan 88.6%
Other are 3.5% years old
Embodiment 21
94.1 parts of phenol and 0.12 part of phospho-molybdic acid are packed in the flask, add water again, water-content is adjusted to 0.01 times of phenol weight in the material that will pack into.Then, under agitation keep 45～55 ℃, with the LBB gas (iso-butylene content is 45%) that imported 250 parts in 3 hours.Reaction mixture weight is 201.5 parts.To can obtain 196.1 parts oily product after this reaction product water and the alkaline aqueous solution cleaning.Find the composed as follows of this oily matter through gas chromatographic analysis:
Unreacted phenol 0.9%
2-tert-butyl phenol 13.1%
4-tert-butyl phenol 9.6%
2,6-di-tert-butylphenol 22.7%
2,4-di-tert-butylphenol 34.9%
2,4,6-tri-tert-butyl phenol 15.8%
Other are 3.0% years old
Embodiment 22～27
With reactor and the method identical with embodiment 17, the water-content in the phenolic compound that only is to use, the consumption of heteropolyacid, the system, temperature etc. are different, and it the results are shown in the table 2.
In the table 2:
4M2B:2-tert-butyl phenol-4-sylvan
3M6B:6-tert-butyl phenol-3-sylvan
4M26B:2,6-di-t-butyl-4-sylvan
3M46B:4,6-di-t-butyl-4-sylvan
Table 2
| Embodiment | Phenols (part) | Heteropolyacid (part) | Water-content in the system (heavily cuing open doubly) | Temperature (℃) | Iso-butylene (part) | Time (hr) | Oily matter weight (part) | Oily matter is formed | |||||
| Raw material | 4M2B | 3M6B | 4M26B | 3M46B | Other | ||||||||
| 22 | Cresols mixed nucleus 1OO | Silicotungstic acid 0.1 | O.003 | 40—50 | LBB 250 | 7 | 190.2 | 1.0 | 17.2 | 3.1 | 49.O | 25.9 | 3.8 |
| 23 | Between a cresols 1OO | Silicotungstic acid O.06 | 0.0067 | 60—70 | Iso-butylene 108.8 | 12 | 198.9 | 1.O | 8.5 | 86.5 | 4.0 | ||
| 24 | P-cresol 100 | The same | O.0020 | The same | The same | 7 | 198.0 | 1.1 | 8.7 | 87.4 | 2.8 | ||
| 25 | The cresols mixing bones of the body 100 | The same | 0.0012 | 45-50 | The same | 6 | 190.5 | 1.0 | 17.6 | 3.0 | 49.0 | 25.5 | 3.9 |
| 26 | Cresols mixture 100 | Phospho-wolframic acid 0.02 | O.002 | 60-70 | Iso-butylene 129 | 7 | 189.1 | 1.3 | 18.5 | 2.4 | 46.8 | 27.O | 4.0 |
| 27 | P-cresol 100 | Silicotungstic acid 3 | 0.01 | 50-55 | LBB 242 | 6 | 201.9 | 0.7 | 6.4 | 88.9 | 4.0 | ||
Embodiment 28
With 100 parts of cresols mixture (p-cresol of 70%, 30% meta-cresol) and 1 part of silicotungstic acid pack in the flask, under agitation remain between 45～55 ℃, with the LB B gas (iso-butylene content is 45%) that imported 288 parts in 5 hours.
Reaction leaches with glass filter (G4) silicotungstic acid of separating out after finishing under 45 ℃.The silicotungstic acid that reclaims heavily is 0.99 part, and its water-content is 5.0%.
The silicotungstic acid content that is dissolved in the filtrate is 0.002% (weight).
Behind the filtrate water and alkaline aqueous solution cleaning with gained, can obtain 190.8 parts oily product.Through gas chromatographic analysis, this oily product composed as follows:
Unreacted cresols 1.0%
The 2-tertiary butyl-4-sylvan 17.3%
The 6-tertiary butyl-3-sylvan 2.6%
2,6-di-t-butyl-4-sylvan 46,0%
4,6-di-t-butyl 3-sylvan 25.7%
Other are 7.4% years old
Embodiment 29
0.4 part the silicotungstic acid (water content is 5%) that reclaims in embodiment 28 is joined in the flask with 100 parts p-cresol, add water again, the water content of material in the flask is adjusted to 0.004 times of p-cresol weight, then, under agitation remain between 50～55 ℃, with 7 hours importing 24 2 parts of LBB gases (iso-butylene content is 45%).
Reaction leaches the silicotungstic acid of separating out with glass filter (G4) after finishing under 50 ℃.The silicotungstic acid weight that reclaims is 0.38 part.After filtrate cleaned with a spot of water and alkaline aqueous solution, can obtain 195.2 parts oily product.
Through gas chromatographic analysis, this oily product composed as follows:
Unreacted p-cresol 0.9%
The 2-tertiary butyl-4-sylvan 10.5%
2,6-di-t-butyl-4-sylvan 84.5%
Other are 4.1% years old
In addition, the dipolymer of iso-butylene and trimeric content are 0.5% in the unreacted gas.
Embodiment 30
The silicotungstic acid of 100 parts cresols mixtures (70% p-cresol, 30% meta-cresol) and 0.8 part is packed in the flask, under the similarity condition of embodiment 28, react.
After reaction finishes, reaction soln is gone up separation at a separating centrifuge (centrifugal effect 2000G), form clarifying oily matter layer in top and silicotungstic acid and separate out layer.Silicotungstic acid content in the clarifying oily matter in top is 0.01% (weight).
The silicotungstic acid layer weight of separating out is 3 parts, then with it and 100 parts of cresols mixture (cresols of 70%, 30% meta-cresol) adds simultaneously in the flask, add water again, the water-content of material in the flask is adjusted to 0.02 times of cresols mixture weight.
Then, under agitation remain between 50～55 ℃, with the LBB gas (iso-butylene content is 45%) that imported 288 parts in 5 hours.
Reaction mixture weight is 204.1 parts.
After removing the silicotungstic acid of separating out from this reaction mixture, water and alkaline aqueous solution wash down the oily product that can obtain 190.1 parts.Through gas chromatographic analysis, this oily matter composed as follows:
Unreacted cresols 0.5%
The 2-tertiary butyl-4-sylvan 18.0%
The 6-tertiary butyl-3-sylvan 3.3%
2,6-di-t-butyl-4-sylvan 48.0%
4,6-di-t-butyl-3-sylvan 26.2%
Other are 4.0 years old
In addition, the dipolymer of iso-butylene and trimeric content are 0.4% in the unreacted gas.
Embodiment 31
With 100 parts of cresols mixture (p-cresol of 70%, 30% meta-cresol) and 1 part silicotungstic acid join in the flask, under agitation remain between 45～55 ℃, with the LBB gas (iso-butylene content is 45%) that imported 288 parts in 5 hours.Can obtain 190.9 parts reaction mixture.The water that respectively adds 30 parts in two sections vertical equipments forming by mixing tank-settling vessel, then with 150 parts/hour flow to wherein infeeding above-mentioned reaction mixture in continuous 12.5 hours, in water layer, reclaim silicotungstic acid catalyst.The silicotungstic acid concentration of water layer is 24.0% in first section, can obtain 39.5 parts.The silicotungstic acid concentration 0.65% of second section water layer can obtain 30.2 parts.(total yield of silicotungstic acid is 98.5%).
Moreover, owing to being dissolved in the water yield that reduces in the reaction mixture, in first section after the continuous supplementation.Clean oil reservoir with a spot of alkaline aqueous solution, resulting oily product is through gas chromatographic analysis, and it is composed as follows:
Unreacted cresols 0.6%
The 2-tertiary butyl-4-sylvan 17.2%
The 6-tertiary butyl-3-sylvan 3.2%
2,6-di-t-butyl-4-sylvan 47.3%
4,6-di-t-butyl-3-sylvan 25.6%
Other are 6.6% years old
Embodiment 32
4.2 parts of silicon tungsten acid solution and 100 parts of cresols mixtures (70% p-cresol, 30% meta-cresol) that reclaim in embodiment 31 are joined in the flask.
Then, react, obtain 190.8 parts mixture with embodiment 31 the same manners.Except that with second section water layer among the embodiment 31 as first section the water, press the same manner water extraction of embodiment 31 and reclaim silicotungstic acid catalyst.The silicotungstic acid concentration of first section water layer is 24.5%, obtains 39.2 parts.Silicotungstic acid concentration is 0.70% in second section water layer, can get 30.1 parts.(total yield of silicotungstic acid is 97.2%).
To oil reservoir carry out with embodiment 31 in after the same processing, through gas chromatographic analysis, its composition can get following result.In addition, repeat the operation of embodiment 31～32, recyclable and utilize the silicotungstic acid catalyst of costliness again.
Unreacted cresols 1.0%
The 2-tertiary butyl-4-sylvan 15.6%
The 6-tertiary butyl-3-sylvan 2.0%
2,6-di-t-butyl-4-sylvan 49.8%
4,6-di-t-butyl-3-sylvan 27.2%
Other are 3.8% years old
Embodiment 33
2 parts of silicon tungsten acid solution and 100 parts of meta-cresols that reclaim in embodiment 31 are added in the flask.
Then, under agitation remain between 50～55 ℃, with 109.5 parts of isobutene gas of importing in 10 hours.After reaction finishes, be the silicotungstic acid that dissolving is separated out, can add 1.5 parts water, reaction mixture is separated, can obtain 1.93 parts of concentration and be 23.9% silicon tungsten acid solution.(the silicotungstic acid total yield is 96.1%).
Behind a spot of alkaline aqueous solution cleaning oil reservoir, can obtain 198.7 parts oily matter.Composed as follows through this oily matter of gas chromatographic analysis:
Unreacted meta-cresol 0.9%
The 6-tertiary butyl-3-sylvan 8.4%
4,6-di-t-butyl-3-sylvan 86.7%
Other are 4.1% years old
Further, silicon tungsten acid solution and 100 parts of meta-cresols of 23.9% of 2 parts of above-mentioned recovery are joined in the flask, and repeat reaction with above-mentioned same method.Silicotungstic acid catalyst is reclaimed in the water extraction, cleans oil reservoir with alkaline aqueous solution then, can obtain 198.5 parts oily product.
Through gas chromatographic analysis, this oily product composed as follows:
Unreacted meta-cresol 1.1%
The 6-tertiary butyl-3-sylvan 8.7%
4,6-di-t-butyl-3-sylvan 86.3%
Other are 3.8% years old
Have again, can obtain 1.92 parts of concentration and be 23.7% silicon tungsten acid solution.(total yield of silicotungstic acid is 95.2%)
Repeat the operation of present embodiment, silicotungstic acid catalyst that can the recovery and reuse costliness.
Embodiment 34
The phospho-wolframic acid of 100 parts p-cresol and 0.4 part is packed in the flask, under agitation remain between 50～55 ℃, reacted to the LBB gas (iso-butylene content is 45%) that wherein imports 288 parts with 5 hours.
Reaction product behind the importing gas weighs 207.6 parts.After this reaction product of twice cleaning of 100 parts 80 ℃ warm water, can isolate 194.1 parts oil reservoir.
With the composition of this oil reservoir of gas chromatographic analysis, 2, the content of 6-di-t-butyl-4-sylvan is 77.7%.
When this oil reservoir was carried out rectification under vacuum, the boiling point that can obtain 146.3 parts was the cut (2,6-di-t-butyl-4-sylvan) of 142～147 ℃/20mmHg.Its yield is 71.8%.
In addition, if make as (120～135 ℃/(the 2-tertiary butyl-when the 4-sylvan reacts once more, can further improve the yield of object that 20mmHg) obtains of starting fractions.
Embodiment 35
Cresols mixture (70% p-cresol with 100 parts, 30% meta-cresol) and 0.15 part silicotungstic acid pack in the flask, under agitation remain between 45～55 ℃, the LBB gas (iso-butylene content is 45%) that imported 288 parts with 10 hours in reaction system reacts.
Reaction product behind the importing gas heavily is 210.3 parts.Is after 3% aqueous sodium hydroxide solution cleans neutralization, further to clean with 60 parts 60 ℃ warm water this reaction product with 60 parts 60 ℃ concentration.Separablely go out 192.5 parts.Composed as follows through the gas chromatographic analysis oil reservoir:
The 2-tertiary butyl-4-sylvan 15.1%
The 6-tertiary butyl-3-sylvan 4.7%
2,6-di-t-butyl-4-sylvan 52.5%
4,6-di-t-butyl-3-sylvan 24.1%
When this oil reservoir is carried out rectification under vacuum, at first can obtain 99.0 parts 2,6-di-t-butyl-4-sylvan, further can obtain 48.6 parts 4,6-di-t-butyl-3-sylvan (165～168 ℃/20mmHg).
2, the productive rate of 6-di-t-butyl-4-sylvan is 69.4% of a p-cresol.
In addition, if will be as starting fraction (118～135 ℃/2-tertiary butyl-4-sylvan that 20mmHg) obtains and the 6-tertiary butyl-when the 3-sylvan makes it to react again, can further improve yield.
Embodiment 36
The phospho-molybdic acid of 100 parts p-cresol and 0.05 part is packed in the flask, under agitation remain between 70～75 ℃, the LBB gas (iso-butylene content is 45%) that imported 288 parts with 7 hours reacts.
The weight of the reaction product behind the importing gas is 203.1 parts.
After cleaning (20 minutes duration of contact) this reaction product with 100 parts 60 ℃ warm water 2 times, the separable oil reservoir that goes out 190.6 parts.
Through gas chromatographic analysis should be by layer composed as follows:
2,6-di-t-butyl-4-sylvan 74.4%
The 2-tertiary butyl-4-sylvan 21.1%
P-cresol 1.0%
Other are 3.5% years old
When the tower that with number of theoretical plate is 25 carried out rectification under vacuum to oil reservoir, the boiling point that can obtain 140.2 parts was the cut (2,6-di-t-butyl-4-sylvan) of 145～147 ℃/20mmHg.Its yield is 68.8%
Comparative Examples 1
With 100 parts of cresols mixture (p-cresol of 70%, 30% meta-cresol) and 2.0 parts the vitriol oil pack in the flask, under agitation keep between 60～65 ℃, with the LBB gas (iso-butylene content is 45%) that imported 288 parts in 8 hours.
Reaction mixture weight is 208.3 parts.
After water and alkaline aqueous solution clean this reaction product, can get 191.0 parts oily product.Composed as follows through this oily product of gas chromatographic analysis:
Unreacted p-cresol 1.3%
The 2-tertiary butyl-4-sylvan 8.5%
The 6-tertiary butyl-3-sylvan 9.3%
2,6-di-t-butyl-4-sylvan 54.0%
4,6-di-t-butyl-3-sylvan 15.0%
Other are 11.9% years old
Have, the dipolymer of iso-butylene and trimeric content are 5.9% in the unreacted gas again.
Comparative Examples 2
The vitriol oil of 100 parts p-cresol and 3.0 parts is packed in the flask, under agitation remain between 55～65 ℃, with importing 110 parts of isobutene gas in 5 hours.
The weight of reaction mixture is 207.0 parts.
This reaction product water and alkaline aqueous solution can obtain 198.8 parts oily product after cleaning.Composed as follows through this oily product of gas chromatographic analysis:
Unreacted p-cresol 1.5%
The 2-tertiary butyl-4-sylvan 6.0%
2,6-di-t-butyl-4-sylvan 79.7%
Other are 12.8% years old
In addition, isobutene dimer in the unreacted gas and trimeric content are 5.6%.
Comparative Examples 3
208.3 parts of reaction product that obtained by Comparative Examples 1 are cleaned (be 60 minutes duration of contact) with 200 parts 80 ℃ 20% aqueous sodium hydroxide solution, after the neutralization, clean the separable oil reservoir that goes out 187.0 parts again with 100 parts 80 ℃ warm water.Composed as follows through the gas chromatographic analysis oil reservoir:
2,6-di-t-butyl-4-sylvan 55.9%
4,6-di-t-butyl-3-sylvan 15.8%
The 2-tertiary butyl-4-sylvan 8.5%
The 6-tertiary butyl-3-sylvan 9.3%
Unreacted cresols 0.3%
Other are 10.2% years old
When under 20mmHg oil reservoir being carried out rectification under vacuum, when temperature in the kettle is 90 ℃ of left and right sides the debutylize reaction taking place, begin to produce isobutene gas, can get 10.2 parts purpose product 2,6-di-t-butyl-4-sylvan.Its yield is 7.2% of a p-cresol.
Comparative Examples 4
The tosic acid of 100 parts p-cresol and 5 parts is packed in the flask, under agitation remain between 70～75 ℃, the LBB gas (iso-butylene content is 45%) that imported 288 parts with 10 hours reacts.
Reaction product weight behind the importing gas is 205.1 parts.
This reaction product is cleaned (be 60 minutes duration of contact) with 200 parts 80 ℃ 20% aqueous sodium hydroxide solution, after the neutralization, again with 100 parts 80 ℃ warm water cleaning, the separable oil reservoir that goes out 188.7 parts.Form with the gc analysis oil reservoir, 2,6-di-t-butyl-4-sylvan is-75.1%.When this oil reservoir being carried out rectification under vacuum, when temperature in the kettle is 90 ℃ of left and right sides, begin to produce isobutene gas, can get 13.5 parts purpose product 2,6-di-t-butyl-4-sylvan with the same quadrat method of Comparative Examples 3.Its yield is 6.6%.
Claims (14)
1. a production contains the method for the alkyl aromatic compound of hydroxyl, it is characterized in that making aromatics with at least one hydroxyl and alkylating agent in the presence of heteropolyacid, react in liquid phase.
2. the method for claim 1 is characterized in that the above-mentioned aromatics with at least one hydroxyl is a phenolic compound.
3. method as claimed in claim 2 is characterized in that above-mentioned phenolic compound is ortho-cresol, meta-cresol, p-cresol or the cresols mixture that contains p-cresol.
4. method as claimed in claim 3 is characterized in that above-mentioned phenolic compound is p-cresol or the cresols mixture that contains p-cresol.
5. the method for claim 1 is characterized in that the abovementioned alkyl agent is the unsaturated hydrocarbons with two keys.
6. method as claimed in claim 5 is characterized in that above-mentioned unsaturated hydrocarbons with two keys is by the represented compound of general formula (I),
R
1-CH=CH
2(I) R wherein
1Represent the straight or branched hydrocarbon residue of hydrogen or carbonatoms 1～10, by the compound of general formula (II) expression,
R
2-CH=CH-CH
3(II) (R wherein
2Representative has the straight or branched hydrocarbon residue of 1～9 carbon atom), or carbonatoms is up to 10 ring-type unsaturated hydrocarbons.
7. method as claimed in claim 6 is characterized in that above-mentioned unsaturated hydrocarbons with two keys is iso-butylene or the gas that contains iso-butylene.
8. as arbitrary described method in the claim 1～7, it is characterized in that above-mentioned heteropolyacid is a silicotungstic acid.
9. as arbitrary described method in the claim 1～8, it is characterized in that above-mentioned reaction carries out in the presence of water, its water-content is equivalent to have 0.0001～0.10 times of aromatics weight of at least one hydroxyl.
10. method as claimed in claim 9 is characterized in that the above-mentioned water yield is 0.001～0.05 times of aromatics weight with at least one hydroxyl.
11. as arbitrary described method in the claim 1～10, it is characterized in that after reaction ends, above-mentioned heteropolyacid to be separated, reuse.
12. method as claimed in claim 11 is characterized in that by the water reaction mixture, obtains to contain the water layer of heteropolyacid, then heteropolyacid is separated.
13. method as claimed in claim 11 is characterized in that making in reaction system heteropolyacid to separate out and obtain separating.
14., it is characterized in that the heteropolyacid content in the above-mentioned recovery water layer is not less than 20% (weight) as the described method of arbitrary claim among the claim 11-13.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13399886 | 1986-06-10 | ||
| JP133998/86 | 1986-06-10 | ||
| JP133999/86 | 1986-06-10 | ||
| JP254341/86 | 1986-10-24 | ||
| JP254340/86 | 1986-10-24 | ||
| JP260990/86 | 1986-10-31 | ||
| JP260989/86 | 1986-10-31 | ||
| JP26099086 | 1986-10-31 | ||
| JP26098986 | 1986-10-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87104109A true CN87104109A (en) | 1988-01-20 |
| CN1031188C CN1031188C (en) | 1996-03-06 |
Family
ID=27316794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87104109 Expired - Fee Related CN1031188C (en) | 1986-06-10 | 1987-06-10 | Method for producing hydroxy-containing alkylated aromatic compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1031188C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088625C (en) * | 1995-12-06 | 2002-08-07 | 南京师范大学 | Catalyst series for synthesizing 1-,2- and 3- substituted alkylphenols with different proportion by one-step process |
| CN1323062C (en) * | 2004-07-29 | 2007-06-27 | 中国石油化工股份有限公司 | Method for preparing alkyl salicylic acid |
| CN102464574A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of p-alkyl catechol |
| CN102898281A (en) * | 2012-11-06 | 2013-01-30 | 孙浩翔 | Method for co-producing 2, 6-butylated hydroxytoluene and m-cresol as well 6-tertiry butyl m-cresol by utilizing cresol mixture |
| CN103319312A (en) * | 2013-07-08 | 2013-09-25 | 葛朝东 | Joint production process of antioxidant 264 and 6-tertiary butyl m-cresol |
| CN103396294A (en) * | 2013-08-23 | 2013-11-20 | 杨锌荣 | Alkyl naphthol and preparation method thereof |
| CN103553880A (en) * | 2013-11-15 | 2014-02-05 | 天津瑞泰精细化工有限公司 | Synthetic method of para-tert-butylcatechol |
| CN110075920A (en) * | 2019-03-26 | 2019-08-02 | 万华化学集团股份有限公司 | A kind of preparation method and applications of multi-stage porous silicon ball load heteropoly phosphorus molybdenum tungstic acid catalyst |
| CN110218148A (en) * | 2019-06-04 | 2019-09-10 | 江苏迈达新材料股份有限公司 | A kind of new process preparing food-grade 2,6- di-tert-butyl methyl phenol |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866380B (en) * | 2017-02-20 | 2020-04-07 | 河北工业大学 | Method and equipment for preparing 2, 6-di-tert-butyl-p-cresol by using micro-reaction rectifying plate |
-
1987
- 1987-06-10 CN CN 87104109 patent/CN1031188C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088625C (en) * | 1995-12-06 | 2002-08-07 | 南京师范大学 | Catalyst series for synthesizing 1-,2- and 3- substituted alkylphenols with different proportion by one-step process |
| CN1323062C (en) * | 2004-07-29 | 2007-06-27 | 中国石油化工股份有限公司 | Method for preparing alkyl salicylic acid |
| CN102464574A (en) * | 2010-11-18 | 2012-05-23 | 中国石油化工股份有限公司 | Preparation method of p-alkyl catechol |
| CN102464574B (en) * | 2010-11-18 | 2015-02-25 | 中国石油化工股份有限公司 | Preparation method of p-alkyl catechol |
| CN102898281A (en) * | 2012-11-06 | 2013-01-30 | 孙浩翔 | Method for co-producing 2, 6-butylated hydroxytoluene and m-cresol as well 6-tertiry butyl m-cresol by utilizing cresol mixture |
| CN103319312A (en) * | 2013-07-08 | 2013-09-25 | 葛朝东 | Joint production process of antioxidant 264 and 6-tertiary butyl m-cresol |
| CN103396294A (en) * | 2013-08-23 | 2013-11-20 | 杨锌荣 | Alkyl naphthol and preparation method thereof |
| CN103553880A (en) * | 2013-11-15 | 2014-02-05 | 天津瑞泰精细化工有限公司 | Synthetic method of para-tert-butylcatechol |
| CN103553880B (en) * | 2013-11-15 | 2015-07-22 | 天津瑞泰精细化工有限公司 | Synthetic method of para-tert-butylcatechol |
| CN110075920A (en) * | 2019-03-26 | 2019-08-02 | 万华化学集团股份有限公司 | A kind of preparation method and applications of multi-stage porous silicon ball load heteropoly phosphorus molybdenum tungstic acid catalyst |
| CN110075920B (en) * | 2019-03-26 | 2022-07-12 | 万华化学集团股份有限公司 | Preparation method and application of hierarchical porous silicon sphere loaded phosphomolybdic tungstic heteropoly acid catalyst |
| CN110218148A (en) * | 2019-06-04 | 2019-09-10 | 江苏迈达新材料股份有限公司 | A kind of new process preparing food-grade 2,6- di-tert-butyl methyl phenol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1031188C (en) | 1996-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1149185C (en) | process for producing ethylene and propylene | |
| CN1990438A (en) | Process for the preparation of 1-butene from technical mixtures of C4-hydrocarbons | |
| CN101040029A (en) | Propylene hydroformylation | |
| CN1031188C (en) | Method for producing hydroxy-containing alkylated aromatic compound | |
| CN1204131C (en) | Process for the preparation of alpha-methylene lactones | |
| CN1037431C (en) | Production of hydrofluorocarbons | |
| CN1990443A (en) | Process for the preparation of ethyl tert-butyl ether from C4-hydrocarbon cuts | |
| CN1098244C (en) | Improved method for producing phenol and acetone from cumol | |
| CN1747922A (en) | Process for producing phenol and methyl ethyl ketone | |
| CN101050157A (en) | Method for preparing compound in biphenyl class | |
| CN1282725A (en) | Method of preparing epichlorohydrin and its intermediate product | |
| CN1263725C (en) | Method for purifying (meth)acrylic acid | |
| CN1104205A (en) | Process for the preparation of dimethyl cxarbonate | |
| EP0249415A2 (en) | Production of alkylated hydroxy aromatic compounds | |
| CN1289344A (en) | Method of removing and recovering boron trifluoride with metal fluoride and process for polyolefin production using the same | |
| CZ20003480A3 (en) | Process for preparing phenol, methylethylketone and acetone | |
| CN1130264C (en) | Process for preparing rhodium complex solution and process for producing aldehyde | |
| CN1065234C (en) | Process for preparing carbonate esters | |
| CN1272294C (en) | Dehalogenate method of carbon-carbon containing double-bonded hydrocarbon | |
| CN1024656C (en) | Alkoxylation process catalyzed by barium phosphate | |
| CN1603297A (en) | Process for producing (meth)acrylic acid compound | |
| CN1066700C (en) | Process for catalytic hydration of olefins | |
| CN1063423C (en) | A novel process for the production of high purity and ultrapure bisphenol-A | |
| CN1069299C (en) | Process for producing all trans-form polyprenols | |
| CN1055913C (en) | Process for preparing chemical industry type methyl t-butyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| C19 | Lapse of patent right due to non-payment of the annual fee |