CN111825541B - Method for separating 2-alkyl anthracene from products containing alkyl anthracene and preparing 2-alkyl anthraquinone by catalytic oxidation - Google Patents
Method for separating 2-alkyl anthracene from products containing alkyl anthracene and preparing 2-alkyl anthraquinone by catalytic oxidation Download PDFInfo
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- CN111825541B CN111825541B CN201910301255.4A CN201910301255A CN111825541B CN 111825541 B CN111825541 B CN 111825541B CN 201910301255 A CN201910301255 A CN 201910301255A CN 111825541 B CN111825541 B CN 111825541B
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- Prior art keywords
- anthracene
- alkyl
- distillation
- alkyl anthracene
- tower
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 title claims abstract description 880
- 238000000034 method Methods 0.000 title claims abstract description 217
- -1 alkyl anthracene Chemical compound 0.000 title claims abstract description 197
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 65
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 13
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title description 17
- 238000004821 distillation Methods 0.000 claims abstract description 196
- 239000000047 product Substances 0.000 claims abstract description 186
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 111
- 238000000926 separation method Methods 0.000 claims abstract description 106
- 238000002425 crystallisation Methods 0.000 claims abstract description 89
- 230000008025 crystallization Effects 0.000 claims abstract description 89
- 239000003054 catalyst Substances 0.000 claims abstract description 85
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 76
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000002844 melting Methods 0.000 claims abstract description 30
- 230000008018 melting Effects 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 8
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims description 119
- 238000006243 chemical reaction Methods 0.000 claims description 107
- 239000013078 crystal Substances 0.000 claims description 94
- 230000035900 sweating Effects 0.000 claims description 77
- 238000005804 alkylation reaction Methods 0.000 claims description 68
- 239000007788 liquid Substances 0.000 claims description 63
- 238000005292 vacuum distillation Methods 0.000 claims description 62
- 238000001816 cooling Methods 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 51
- 239000002904 solvent Substances 0.000 claims description 51
- 238000010992 reflux Methods 0.000 claims description 47
- 125000000217 alkyl group Chemical group 0.000 claims description 43
- 229910052799 carbon Inorganic materials 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 35
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 31
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 28
- 239000000155 melt Substances 0.000 claims description 26
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical group CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 24
- BFIMMTCNYPIMRN-UHFFFAOYSA-N 1,2,3,5-tetramethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1 BFIMMTCNYPIMRN-UHFFFAOYSA-N 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 20
- 239000002168 alkylating agent Substances 0.000 claims description 18
- 229940100198 alkylating agent Drugs 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- 230000029936 alkylation Effects 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000001555 benzenes Chemical class 0.000 claims description 5
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 210000004243 sweat Anatomy 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 239000012527 feed solution Substances 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- 150000005673 monoalkenes Chemical group 0.000 claims description 2
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 2
- 239000012803 melt mixture Substances 0.000 claims 2
- 238000004064 recycling Methods 0.000 claims 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- WYBPLXLPOLAWTE-UHFFFAOYSA-N 2-pentylanthracene Chemical compound C1=CC=CC2=CC3=CC(CCCCC)=CC=C3C=C21 WYBPLXLPOLAWTE-UHFFFAOYSA-N 0.000 description 100
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 21
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- PHJDLOLHDMITST-UHFFFAOYSA-N 2-hexylanthracene Chemical compound C1=CC=CC2=CC3=CC(CCCCCC)=CC=C3C=C21 PHJDLOLHDMITST-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- SGHGTABSBRRVLL-UHFFFAOYSA-N 2-butylanthracene Chemical compound C1=CC=CC2=CC3=CC(CCCC)=CC=C3C=C21 SGHGTABSBRRVLL-UHFFFAOYSA-N 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000002152 alkylating effect Effects 0.000 description 4
- 229940045799 anthracyclines and related substance Drugs 0.000 description 4
- 150000004056 anthraquinones Chemical class 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MAKLMMYWGTWPQM-UHFFFAOYSA-N 2-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCC)=CC=C3C(=O)C2=C1 MAKLMMYWGTWPQM-UHFFFAOYSA-N 0.000 description 2
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000005577 anthracene group Chemical group 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- LUACOWBTSAPURU-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)anthracene Chemical compound C1=CC=CC2=CC3=CC(C(C)(C)CC)=CC=C3C=C21 LUACOWBTSAPURU-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- HKTWZNQNRPEUFM-UHFFFAOYSA-N 2-hexylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCCC)=CC=C3C(=O)C2=C1 HKTWZNQNRPEUFM-UHFFFAOYSA-N 0.000 description 1
- WBPXZSIKOVBSAS-UHFFFAOYSA-N 2-tert-butylanthracene Chemical compound C1=CC=CC2=CC3=CC(C(C)(C)C)=CC=C3C=C21 WBPXZSIKOVBSAS-UHFFFAOYSA-N 0.000 description 1
- 229940076442 9,10-anthraquinone Drugs 0.000 description 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/04—Preparation of quinones by oxidation giving rise to quinoid structures of unsubstituted ring carbon atoms in six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/14—Purification; Separation; Use of additives by crystallisation; Purification or separation of the crystals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of preparation of 2-alkylanthraquinone, and particularly discloses a method for preparing 2-alkylanthraquinone by separating 2-alkylanthraquinone from a product containing alkylanthraquinone and carrying out catalytic oxidation, wherein the preparation method comprises the following steps: (1) preparing a reaction product containing an alkyl anthracene from an anthracene; (2) separating the reaction product containing alkyl anthracene, the separation process comprising: melting crystallization separation of anthracene and distillation separation of 2-alkyl anthracene; (3) the 2-alkyl anthracene is contacted with an oxidizing agent which is hydrogen peroxide under oxidizing conditions and in the presence of an oxidizing reaction solvent and a catalyst selected from one or more of an oxide and/or hydroxide of an alkaline earth metal, an oxygen-containing compound of a transition metal, and an oxygen-containing compound of a lanthanide metal to carry out an oxidation reaction. In the method, the separation process has low operation difficulty and high separation efficiency; the oxidation reaction system is simple and efficient, and the catalyst cost is low.
Description
Technical Field
The invention relates to a preparation method of an organic matter, in particular to a method for separating 2-alkyl anthracene from a product containing alkyl anthracene and preparing 2-alkyl anthraquinone through catalytic oxidation.
Background
Hydrogen peroxide is an important green basic chemical, has high industrial relevance, and has become the first major country for hydrogen peroxide production since 2008, and the consumption amount is over 1000 million t/a (calculated by 27.5%) in 2015. At present, the technology for producing hydrogen peroxide at home and abroad is mainly an anthraquinone method. The 2-alkyl anthraquinone in the process is used as a 'carrier' of the process, and the quality and the yield of the hydrogen peroxide are directly influenced. The phthalic anhydride process is the primary method for producing 2-alkylanthraquinones, but this process suffers from serious contamination problems. 1.76 tons of anhydrous AlCl is required to be added for producing 1 ton of 2-ethyl anthraquinone3And 4.2 tons of fuming H2SO4(20%) and the recovery of both is difficult. Therefore, it is very important to develop a green production process of 2-alkylanthraquinone from the viewpoint of environmental protection and clean production.
US 4255343 discloses a method for synthesizing 2-tert-amyl anthracene, which comprises uniformly mixing anthracene, trichlorobenzene and methanesulfonic acid under certain temperature and pressure conditions, and introducing olefin into the system to perform alkylation reaction with anthracene. The solid product was mainly the remaining anthracene and the series of alkyl anthracene products, with 42 wt% anthracene and 47 wt% 2-alkyl anthracene, with the remainder being anthracene disubstituted product and other by-products.
TW 200623958 discloses a method for alkylating anthracene by using ionic liquid catalysis, and the catalytic system of the alkylation reaction is a mixture containing 60-93.7 wt% of ionic liquid and 1-8 wt% of aluminum chloride. In the examples, BmimPF6As solvent, and adding proper AlCl3When the alkylation reaction of anthracene and tert-butyl chloride is catalyzed at 70 ℃, the yield of the product 2, 6-tert-butyl anthracene is 90%.
Perezromero et al used H2O2Oxidizing anthracene or 2-alkyl anthracene to prepare anthraquinone with Cu-containing Tp as catalystxCu (NCMe), after reacting for 2h at 80 ℃, the conversion rate of anthracene is 95%, and the selectivity of anthraquinone is 98%.
In US3953482 a process for the preparation of a catalyst using H is disclosed2O2A process for preparing 2-alkylanthraquinone by oxidizing 2-alkylanthraquinone. Fatty alcohol as solvent and concentrated hydrochloric acid as catalyst、H2O2(60%) is an oxidant, and the reaction is carried out for 60min at the normal pressure of 40-100 ℃, so that a better reaction effect can be obtained. The conversion rate of the 2-pentylanthracene is 94 percent, and the selectivity of the 2-pentylanthraquinone is as high as 97 percent.
As can be seen, no complete set of process technology for preparing 2-alkylanthraquinone from anthracene is reported at present.
Disclosure of Invention
The invention aims to provide a novel method for separating 2-alkyl anthracene from a product containing alkyl anthracene and preparing 2-alkyl anthraquinone through catalytic oxidation on the basis of the prior art, namely an integral process for preparing the reaction product containing the alkyl anthracene by taking anthracene as a raw material through reaction, separating and preparing the 2-alkyl anthracene, and preparing the 2-alkyl anthraquinone through oxidation reaction of the 2-alkyl anthracene.
The invention provides a method for separating 2-alkyl anthracene from a product containing alkyl anthracene and preparing 2-alkyl anthraquinone through catalytic oxidation, wherein the preparation method comprises the following steps:
(1) preparing a reaction product containing an alkyl anthracene from an anthracene;
(2) separating the reaction product containing alkyl anthracene obtained from step (1), the separation method comprising: melting crystallization separation of anthracene and distillation separation of 2-alkyl anthracene;
(3) contacting the 2-alkyl anthracene obtained in the step (2) with an oxidizing agent, which is hydrogen peroxide, under oxidizing conditions and in the presence of an oxidizing reaction solvent and a catalyst, wherein the catalyst is one or more selected from the group consisting of an oxide of an alkaline earth metal, a hydroxide of an alkaline earth metal, an oxygen-containing compound of a transition metal, and an oxygen-containing compound of a lanthanide metal.
The whole technical route for separating the 2-alkyl anthracene from the product containing the alkyl anthracene and preparing the 2-alkyl anthraquinone by catalytic oxidation is reasonable and feasible, and opens up a new direction for the green preparation of the 2-alkyl anthraquinone. The method provided by the invention can obviously reduce the operation difficulty in the separation process of the anthracene-alkyl anthracene product and improve the purity and the total yield of the intermediate target product 2-alkyl anthracene by a melt crystallization-distillation coupling separation technology.
In the method provided by the invention, the constructed 2-alkyl anthracene catalytic oxidation system is simple and efficient, the catalyst is low in separation and recovery difficulty and free from corrosivity, the equipment investment and the post-treatment cost of the oxidation waste liquid are reduced, and the conversion of the 2-alkyl anthracene can be effectively realized.
Preferably, in the method provided by the invention, a combined solvent system is adopted in the reaction process of preparing the anthraquinone by oxidizing the 2-alkyl anthracene, so that the oxidation reaction of the 2-alkyl anthracene can be enhanced by adjusting the property of the solvent, and the reaction selectivity and the product yield are improved.
In addition, the method provided by the invention also has the advantages of simple process, high efficiency and small pollution.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a flow diagram of a process for separating 2-alkylanthraquinone from an alkylanthraquinone-containing product and catalytically oxidizing the 2-alkylanthraquinone according to one embodiment of the present invention;
FIG. 2 is a diagram of an embodiment of the present invention for the isolation of an anthracene alkylation product, melt crystallization-multi-step vacuum distillation coupling process;
FIG. 3 is a diagram of an embodiment of the present invention for the isolation of an anthracene alkylation product, melt crystallization-multi-step vacuum distillation coupling process;
FIG. 4 is a flow diagram of the melt crystallization step in the present invention providing for the isolation of the anthracene alkylation product, melt crystallization-vacuum distillation process.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, 2-alkylanthraquinone means 2-alkyl-9, 10-anthraquinone, hereinafter referred to as 2-alkylanthraquinone.
According to the invention, the method for separating 2-alkyl anthracene from the product containing alkyl anthracene and preparing 2-alkyl anthraquinone by catalytic oxidation comprises the following steps:
(1) preparing a reaction product containing an alkyl anthracene from an anthracene;
(2) separating the reaction product containing alkyl anthracene obtained from step (1), the separation method comprising: melting crystallization separation of anthracene and distillation separation of 2-alkyl anthracene;
(3) contacting the 2-alkyl anthracene obtained in the step (2) with an oxidizing agent, which is hydrogen peroxide, under oxidizing conditions and in the presence of an oxidizing reaction solvent and a catalyst, wherein the catalyst is one or more selected from the group consisting of an oxide of an alkaline earth metal, a hydroxide of an alkaline earth metal, an oxygen-containing compound of a transition metal, and an oxygen-containing compound of a lanthanide metal.
According to the present invention, the starting material anthracene can be reacted to produce an anthracene containing an alkyl group. The method of producing an alkyl anthracene-containing reaction product from anthracene can be any single reaction or a combination of multiple steps to introduce an alkyl group into an anthracycline to produce an alkyl anthracene. Substances containing anthracene ring structures in the reaction products obtained in the step (1) comprise residual anthracene, 2-alkyl anthracene and other series alkyl anthracene products. It is well known to those skilled in the art that, depending on the reaction method, if the starting anthracene is not completely converted, the reaction product may contain residual anthracene. If the alkyl anthracene is not a single species, the alkyl anthracene may also be a mixture. Therefore, the production of alkyl anthracene-containing reaction products from a starting anthracene typically contains anthracene, 2-alkyl anthracene, and other series of alkyl anthracene products.
According to one embodiment of the present invention, as shown in fig. 1, the method for preparing a reaction product containing an alkyl anthracene from anthracene in step (1) includes: the alkylation reaction is carried out by contacting anthracene with an alkylating agent under alkylation conditions and in the presence of an alkylation solvent and a catalyst.
The mode of contacting anthracene with an alkylating agent and a catalyst according to the present invention can be any of various modes capable of producing alkyl anthracene by alkylation of anthracene. Preferably, for more complete reaction, the contacting is carried out in the following manner: the raw material liquid containing anthracene, catalyst and alkylation reaction solvent is contacted with alkylation reagent to make alkylation reaction.
According to the present invention, the conditions and methods of the anthracycline reaction in step (1) may be performed in a manner conventional in the art.
According to the present invention, in step (1), the alkylating agent may be any alkylating agent known to those skilled in the art capable of introducing an alkyl group into an anthracycline to prepare an alkyl anthracene, for example, the alkylating agent may be one or more of an olefin, an alcohol, a halogenated hydrocarbon, and an ether having 2 to 8 carbon atoms, preferably one or more of an olefin, an alcohol, a halogenated hydrocarbon, and an ether having 4 to 6 carbon atoms, and more preferably a monoolefin having 4 to 6 carbon atoms.
According to the invention, in step (1), the alkylating agent is used in an amount that enables the introduction of alkyl groups into the anthracycline to produce alkyl anthracenes, preferably in a molar ratio of anthracene to alkylating agent of from 0.2:1 to 20:1, more preferably from 0.5:1 to 5: 1.
According to the present invention, in the step (1), the alkylation reaction solvent is an inert organic solvent capable of dissolving anthracene. Specifically, the alkylation reaction solvent is a solvent having a dielectric constant of 1 to 10 at 20 ℃, and more specifically, the alkylation reaction solvent is C6Above, preferably C6-C12And one or more of paraffins, naphthenes, and aromatics. Wherein the aromatic hydrocarbon is substituted or unsubstituted, preferably one or more of mono-or multi-substituted benzene; more preferably one or more of benzene multi-substituted compounds, the substituent is C1-C4And one or more of an alkyl group and a halogen element. Further preferably, the alkylation reaction solvent is one or more of polyalkyl substituents of benzene. Most preferably, the alkylation reaction solvent is selected from the group consisting of 1,3, 5-trimethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,3,4, 5-tetramethylbenzene, 1,3,5,6-tetramethylbenzene and one or more of 2,3,5, 6-tetramethylbenzene. The amount of the alkylation reaction solvent is only required to ensure that the anthracene can be fully dissolved so as to achieve the effect of providing a good reaction medium. Preferably, the anthracene is present in an amount of from 5 to 60 weight percent, preferably from 8 to 50 weight percent, based on the total weight of anthracene and alkylation reaction solvent.
According to the present invention, in the step (1), the mode of contacting the anthracene with the alkylating agent under the alkylation conditions and in the presence of the alkylation reaction solvent and the catalyst is not particularly limited, and preferably, in order to ensure that the alkylation reaction can be carried out more favorably, the anthracene, the catalyst and the alkylation reaction solvent are prepared as a raw material solution of the anthracene-catalyst-alkylation reaction solvent, and then the alkylating agent is added to carry out the alkylation reaction. Preferably, the preparation temperature of the raw material liquid of the anthracene-catalyst-alkylation reaction solvent is 100-250 ℃, more preferably 120-200 ℃.
According to the present invention, in step (1), the alkylation reaction conditions generally comprise: the reaction temperature can be 100-250 ℃, preferably 120-200 ℃; the reaction time can be 0.01-48h, preferably 0.5-24 h; the reaction pressure may be from 0 to 1MPa, preferably from 0.05 to 0.5 MPa.
According to the present invention, in step (1), in order to enable the alkylation reaction to be more easily performed, the alkylation reaction is performed in the presence of a catalyst. In particular, the catalyst may be any form and kind of acid catalyst capable of catalyzing the alkylation of anthracene, for example, the catalyst is selected from one or more of liquid acids, preferably methanesulfonic acid and/or p-toluenesulfonic acid; the catalyst may also be used in an amount of 0.01 to 50 wt%, preferably 0.5 to 30 wt%, based on the total weight of the raw material solution containing anthracene, the alkylation reaction solvent and the catalyst, with reference to the amount conventionally used in the art.
According to the present invention, the process for preparing alkyl anthracene from raw material anthracene in step (1) requires the use of a catalyst, and the catalyst after reaction may be separated after step (1) and before step (2) by a separation method that is conventional in the art according to the nature of the catalyst.
According to physical analysis, the boiling point of anthracene is 340 ℃, and the alkyl anthracene product and the anthracene homologue have a boiling point difference, and the product can be separated by a reduced pressure distillation technology. But the technical difficulty is that the melting point of anthracene is as high as 215 ℃, anthracene with a high solidifying point is separated by adopting a vacuum distillation technology alone, the operation difficulty is high, once the pipeline has a problem in heat preservation, the phenomenon of blockage is easy to occur, and the continuous and stable operation of the process is seriously influenced. In addition, anthracene is very easily sublimed, and sublimation temperature is difficult to control, and the chance that the pipeline takes place to block up is showing to increase. Thus, it is impractical to use solely vacuum distillation techniques to achieve separation of the anthracene-alkyl anthracene product.
Therefore, the inventors of the present invention propose to separate anthracene and alkyl anthracene products using a melt crystallization-distillation separation method. The alkyl anthracene destroys the high regularity of an anthracene ring structure due to the existence of a side chain substituent group, so that the melting point of an alkyl anthracene product is obviously reduced, for example, the melting point range of a low-carbon alkyl anthracene product (1< the carbon number j1<8 of an alkyl side chain of anthracene) is 130-150 ℃, the melting point range of a high-carbon alkyl anthracene product (7< the carbon number j2<18 of an alkyl side chain of anthracene) is 150-190 ℃, the melting points are obviously lower than the melting point 215 ℃ of anthracene, and a large melting point difference exists between the alkyl anthracene and the anthracene. For this reason, the inventor of the present invention proposes to first use the melt crystallization technique to separate and remove the anthracene which has the highest melting point and is most difficult to separate by crystallization, and then use one or more reduced pressure distillation techniques to further separate the anthracene from the alkyl anthracene mixture with high boiling point according to the difference of the boiling points.
Based on this, according to the present invention, the reaction product containing alkyl anthracene obtained through step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene; the step (2) comprises the following steps:
(2-2) heating the reaction product containing the alkyl anthracene obtained in the step (1) to a molten state, cooling and crystallizing, separating to obtain an anthracene crystal and a feed liquid containing a series of alkyl anthracene products of 2-alkyl anthracene, heating the anthracene crystal for sweating, and separating the sweating liquid and the anthracene crystal;
(2-3) separating 2-alkyl anthracene from a series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.
According to one embodiment of the present invention, as shown in FIG. 4, the melt crystallization step can be carried out in a melt crystallization system in which the crystalline separation of anthracene from the reaction product mixture can be achieved. The melt crystallization system includes an intermediate melt tank and a melt crystallizer. The melted product containing anthracene and serial alkyl anthracene products heated and melted in the distillation tower is sent into an intermediate melting tank and then is introduced into a melting crystallizer. The apparatus for implementing the melt crystallization process is a melt crystallizer, the crystallization process can be lamellar crystallization or suspension crystallization, and the operation mode can be batch operation or continuous operation, but the invention is not limited to the method, but the batch operation lamellar crystallization mode is more preferable. The temperature increase and decrease in the melt crystallizer is achieved by introducing a heat exchange medium into the melt crystallizer. After the heated and melted material enters the melting crystallizer, the cooling medium is used for cooling, so that the anthracene with a high melting point is crystallized and separated out, and further, the separation of the anthracene and a series of alkyl anthracene products is realized.
According to the present invention, in the melt crystallization step of (2-2), in order to better achieve the crystal separation of anthracene, the melting temperature is controlled to 200-270 ℃, preferably 210-250 ℃.
According to the invention, the melt crystallization process essentially comprises three steps of cooling crystallization, sweating and preferably warming remelting of the anthracene crystals.
According to the present invention, the temperature for cooling crystallization can be 180-210 ℃, preferably 190-200 ℃. In order to better realize the crystal separation of anthracene, the cooling rate of the cooling crystal can be 0.1-10 ℃/h, preferably 0.5-5 ℃/h, and the cooling crystallization time, namely the crystal growth time can be controlled to be 1-5h, preferably 1.5-4 h.
According to the present invention, in order to increase the crystallization rate, in the cooling crystallization process, it is preferable to further include a step of adding seed anthracene, which may be added in an amount according to the details of the cooling crystallization process, and it is further preferable to add the seed anthracene in an amount of 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, based on the mass of the molten mixture.
According to the present invention, in order to further increase the purity of the crystalline anthracene, it is necessary to further perform a sweating operation on the anthracene crystal. After the crystal layer is formed, the temperature of the crystal layer is slowly close to the equilibrium temperature by controlling the rising rate of the temperature of the crystal layer, and the local crystal containing more impurities is low in melting point due to uneven distribution of the impurities in the crystal layer and can be firstly melted and separated from the crystal in a sweating mode.
According to the present invention, in the melt crystallization step, the temperature increase rate at which the anthracene crystal undergoes sweating is controlled to 0.1 to 8 deg.C/h, preferably 0.2 to 4 deg.C/h, from the viewpoint of further improving the purity of the crystal and the separation accuracy. The temperature raised to the temperature at which sweating stops cannot melt the crystallized anthracene crystal, and therefore, the temperature raised to the temperature at which sweating stops must be lower than the melting temperature of the anthracene crystal, preferably the temperature raised to the temperature at which sweating stops is 210 ℃ or lower, more preferably, the temperature raised to 5 to 15 ℃ higher than the cooling crystallization temperature, and the sweating stops below 210 ℃. The sweating end temperature may be 190-210 deg.C, more preferably 195-205 deg.C, under the principle of following the above-mentioned sweating stop temperature. In order to further increase the purity of the crystalline anthracene, the amount of perspiration can also be controlled so that the amount of perspiration is 5 to 40% by weight, more preferably 10 to 30% by weight, of the mass of the crystal.
According to the present invention, in order to further improve the separation accuracy, the collected sweat is recycled, that is, the sweat is recycled to the melting and crystallizing step, and the melting and cooling crystallization is carried out by heating together with the reaction product containing alkyl anthracene, that is, the mixture containing anthracene and the series of alkyl anthracene products.
According to the invention, after sweating is finished, the temperature of the separated anthracene crystal can be increased to over 215 ℃, and the crystal anthracene is collected and recycled after being completely melted into liquid.
After melt crystallization according to the process of the present invention, the non-crystallized material collected, i.e., the feed solution of the 2-alkyl anthracene-containing series of alkyl anthracene products consisting essentially of the series of alkyl anthracene products (substantially free of anthracene), is collected.
According to the invention, the boiling points of the serial alkyl anthracene products containing 2-alkyl anthracene are all higher than that of anthracene (340 ℃), so that the distillation technology is needed to further realize the purpose of serial alkyl anthracene product separation. Thus, 2-alkyl anthracenes can be separated from a series of alkyl anthracene products containing 2-alkyl anthracenes by one or more distillation steps.
According to the present invention, in the step (2-3), when the alkyl anthracene product of the series containing 2-alkyl anthracene is a mixture of two substances, or a mixture of three or more substances, the boiling point of 2-alkyl anthracene is the lowest or the highest; then a one-step distillation is performed to separate the 2-alkyl anthracene. In the step (2-3), when the serial alkyl anthracene products containing the 2-alkyl anthracene are a mixture of more than three substances, and the boiling point of the 2-alkyl anthracene is between the substance with the highest boiling point and the substance with the lowest boiling point in the mixture; a multi-step distillation is performed.
According to an embodiment of the present invention, in the step (2-3), the multi-step distillation method comprises:
mode 1: as shown in fig. 2, a feed liquid of a series of alkyl anthracene products containing 2-alkyl anthracene is subjected to first distillation and separated to obtain a distillate containing light component Cj 1-anthracene and a bottom product containing heavy component Cj 2-anthracene; subjecting the distillate containing the light component C1 j-anthracene to second distillation to obtain a distillate containing the light component Cj 3-anthracene and a bottom product containing the target product Ci-anthracene;
wherein, the light component Cj 1-anthracene is an alkyl anthracene product with the total carbon number j1 of an alkyl side chain being an integer which is more than 1 and less than j1 and less than i +1, the heavy component Cj 2-anthracene is an alkyl anthracene product with the total carbon number j2 of the alkyl side chain being an integer which is more than i and less than j2 and less than 41, and the light component Cj 3-anthracene is an alkyl anthracene product with the total carbon number j3 of the alkyl side chain being an integer which is more than 1 and less than j3 and less than i;
wherein, in the target product Ci-anthracene, i represents the total carbon number of an alkyl side chain, i is an integer of 4-7, the substitution position is at 2 position, namely 2-alkyl anthracene, and the total carbon number of the alkyl side chain is 4-7.
The conditions of the first distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-. More preferably, the pressure at the top of the column is 0.1 to 10KPa, the temperature at the bottom of the column is 210-340 ℃, the number of theoretical plates is 30 to 75, and the reflux ratio at the top of the column is 1 to 7. Further preferably, the pressure at the top of the distillation column is 0.5 to 2KPa, the temperature at the bottom of the distillation column is 260 ℃ to 320 ℃, the number of theoretical plates is 40 to 75, and the reflux ratio at the top of the distillation column is 1 to 3. Under this operating condition, the bottoms were predominantly Cj 2-anthracene product (total alkyl side chain carbon number j2 is an integer of i < j2< 41), and the overheads were Cj 1-anthracene product (total alkyl side chain carbon number j1 is an integer of 1< j1< i + 1).
The conditions of the second distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8. More preferably, the pressure at the top of the column is from 0.1 to 10KPa, the temperature at the bottom of the column is from 200 ℃ to 310 ℃, the number of theoretical plates is from 30 to 75, and the reflux ratio at the top of the column is from 1 to 7. Further preferably, the pressure at the top of the distillation column is 0.5 to 2KPa, the temperature at the bottom of the distillation column is 220-305 ℃, the number of theoretical plates is 40 to 75, and the reflux ratio at the top of the distillation column is 1 to 5. Under the operating conditions, the bottom product is Ci-anthracene (2-alkyl anthracene, the total carbon number of alkyl side chain is 4-7), and the overhead product is Cj 3-anthracene (the total carbon number of alkyl side chain j3 is an integer of 1< j3 < i).
For example, as shown in FIG. 2, the alkyl anthracene mixture is a continuous homolog mixture of C2-anthracene to C20-anthracene, while C5-anthracene is the isolated target product. Through the first distillation, light components including C2-anthracene to C5-anthracene are obtained at the top of the tower, and heavy components including C6-anthracene to C20-anthracene are obtained at the bottom of the tower. The mixture of C2-anthracene to C5-anthracene is subjected to second distillation, light components obtained at the top of the tower comprise the mixture of C2-anthracene to C4-anthracene, and a target product of C5-anthracene is obtained at the bottom of the tower.
Or,
mode 2: as shown in fig. 3, the feed liquid of the series alkyl anthracene product containing 2-alkyl anthracene is subjected to third distillation to obtain distillate containing light component Cm 1-anthracene and a bottom product containing heavy component Cm 2-anthracene; carrying out fourth distillation on the bottom product containing the heavy component Cm 2-anthracene to obtain a distillate containing the target product Ci-anthracene and a bottom product containing the heavy component Cm 3-anthracene;
wherein the light component Cm 1-anthracene is an alkyl anthracene product with the total carbon number m1 of an alkyl side chain being an integer of more than 1 and less than m and i, the heavy component Cm 2-anthracene is an alkyl anthracene product with the total carbon number m2 of the alkyl side chain being an integer of more than i and less than m2 and less than 41, and Cm 3-anthracene is an alkyl anthracene product with the total carbon number m3 of the alkyl side chain being an integer of more than i and less than m3 and less than 41;
wherein, in the target product Ci-anthracene, i represents the total carbon number of an alkyl side chain, i is an integer of 4-7, the substitution position is at 2 position, namely 2-alkyl anthracene, and the total carbon number of the alkyl side chain is 4-7.
The conditions of the third distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-. More preferably, the pressure at the top of the column is 0.1 to 10KPa, the temperature at the bottom of the column is 210-340 ℃, the number of theoretical plates is 30 to 75, and the reflux ratio at the top of the column is 1 to 7. Further preferably, the pressure at the top of the distillation column is 0.5 to 2KPa, the temperature at the bottom of the distillation column is 260 ℃ to 320 ℃, the number of theoretical plates is 40 to 75, and the reflux ratio at the top of the distillation column is 1 to 3. Under this operating condition, the bottoms product was predominantly Cm 2-anthracene product (total alkyl side chain carbon number m2 is an integer from i-1 < m 2< 41), and the overhead product was Cm 1-anthracene product (total alkyl side chain carbon number m1 is an integer from 1< m < i).
The conditions of the fourth distillation include: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8. More preferably, the pressure at the top of the column is from 0.1 to 10KPa, the temperature at the bottom of the column is from 200 ℃ to 310 ℃, the number of theoretical plates is from 30 to 75, and the reflux ratio at the top of the column is from 1 to 7. Further preferably, the pressure at the top of the distillation column is 0.5 to 2KPa, the temperature at the bottom of the distillation column is 220-305 ℃, the number of theoretical plates is 40 to 75, and the reflux ratio at the top of the distillation column is 1 to 5. Under the operating conditions, the overhead product is Ci-anthracene (2-alkyl anthracene, the total carbon number of the alkyl side chain is 4-7) which is the target product, and the bottom product is Cm 3-anthracene (the total carbon number of the alkyl side chain is m3 which is an integer of i < m3 < 41).
For example, as shown in FIG. 3, the alkyl anthracene mixture is a continuous homolog mixture of C2-anthracene to C20-anthracene, while C5-anthracene is the isolated target product. Through the third distillation, light components including C2-anthracene to C4-anthracene are obtained at the top of the tower, and heavy components including C5-anthracene to C20-anthracene are obtained at the bottom of the tower. And (3) carrying out fourth distillation on a mixture of C5-anthracene to C20-anthracene, obtaining a target product C5-anthracene at the tower top, and obtaining a heavy component from the tower bottom, wherein the heavy component comprises C6-anthracene to C20-anthracene.
According to the present invention, the specific operating conditions of each of the vacuum distillations in the multi-step vacuum distillations can be appropriately selected within the operating temperature and pressure ranges thereof according to the different distillation ranges of the overhead product and the bottom product in each vacuum distillation.
According to the present invention, the multi-step vacuum distillation may employ various vacuum distillation apparatuses known in the art, for example: a sieve tray column or a packed column, more preferably a packed column.
According to the present invention, depending on the process and operating conditions of the reaction of step (1), other substances having a boiling point lower than that of anthracene, such as reaction solvents and other by-products (e.g., alkylating agent remaining after the alkylation reaction), may be entrained or generated, and are referred to as light components. Therefore, the reaction product containing an alkyl anthracene obtained via step (1) also contains a reaction solvent. The method further comprises a step (2-1) of separating the reaction solvent before the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation. The method of separating the solvent may be removed using a separation method that is conventional in the art. Preferably, the reaction solvent in the mixed solution containing the alkyl anthracene product is separated by atmospheric distillation from the viewpoint of further improving the separation efficiency and simplifying the operation. According to a specific embodiment of the present invention, the separation method of (2-1) comprises: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene. In addition, the separated reaction solvent may be recycled or collected for disposal as required for the reaction. In addition, other by-product separation methods can also be in the separation of anthracene alkyl anthracene before separation, can pass through conventional separation methods to remove, such as distillation.
Preferably, in the step (2-1), the distillation conditions include: the bottom temperature of the distillation column is 100-300 ℃, preferably 150-200 ℃, and the pressure at the top of the distillation column is normal pressure.
According to the invention, the intermediate product 2-alkyl anthracene is obtained by separation, and can be used for preparing 2-alkyl anthraquinone through reaction. According to the present invention, in the step (3), the 2-alkylanthraquinone is produced from the 2-alkylanthraquinone obtained through the step (2) by subjecting the 2-alkylanthraquinone to an oxidation reaction to produce the 2-alkylanthraquinone. Specifically, in the step (3), the process for producing 2-alkylanthraquinone from 2-alkylanthraquinone obtained via the step (2) comprises: contacting the 2-alkyl anthracene obtained in the step (2) with an oxidizing agent, which is hydrogen peroxide, under oxidizing conditions and in the presence of an oxidizing reaction solvent and a catalyst, wherein the catalyst is one or more selected from the group consisting of an oxide of an alkaline earth metal, a hydroxide of an alkaline earth metal, an oxygen-containing compound of a transition metal, and an oxygen-containing compound of a lanthanide metal.
According to the invention, in the step (3), the oxidant hydrogen peroxide is combined with one or more catalysts selected from the oxides of alkaline earth metals, hydroxides of alkaline earth metals, oxygen-containing compounds of transition metals and oxygen-containing compounds of lanthanide metals, so that the conversion of 2-alkyl anthracene can be effectively realized, the 2-alkyl anthracene catalytic oxidation system is simple and efficient, the separation and recovery difficulty of the catalyst is low, no corrosivity exists, and the equipment investment and the post-treatment cost of the oxidation waste liquid are reduced.
Preferably, in step (3), the catalyst is selected from one or more of group IIA, group IVB, group VB, group VIB, group VIIB, group VIII metal oxygen-containing compounds, and lanthanide metal oxygen-containing compounds. For example, the IIA group can Be oxygen-containing compounds of Be, Mg, Ca, Sr and Ba, the IVB group can Be oxygen-containing compounds of Ti and Zr, the VB group can Be oxygen-containing compounds of V, Nb and Ta, the VIB group can Be oxygen-containing compounds of Cr, Mo and W, the VIIB group can Be oxygen-containing compounds of Mn and Re, the VIII group can Be oxygen-containing compounds of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt, and the lanthanide group can Be oxygen-containing compounds of La, Ce, Pr, Nd, Pm, Sm, Gd, Eu, Dy, Ho, Er, Tm, Yb and Lu. More preferably, the catalyst is selected from one or more of the group consisting of oxygen-containing compounds of Ca, Ba, Ti, Zr, V, Cr, Mo, W, Mn, Ru, Co, Ni, La and Ce. Most preferably, the catalyst is selected from one or more of calcium hydroxide, barium hydroxide, tetravalent titanium oxygenates including metatitanic acid, tetravalent zirconium oxygenates including zirconium dioxide and zirconyl nitrate, pentavalent vanadium oxygenates including sodium metavanadate, hexavalent chromium oxygenates including potassium chromate and chromium trioxide, hexavalent molybdenum oxygenates including sodium molybdate, ammonium molybdate and molybdenum trioxide, hexavalent tungsten oxygenates including sodium tungstate, trivalent manganese and tetravalent manganese oxygenates including manganese dioxide and manganese dioxide, tetravalent ruthenium oxygenates including ruthenium dioxide, trivalent cobalt oxygenates including cobaltous oxide, divalent nickel and trivalent nickel oxygenates including nickel oxide and nickel trioxide, trivalent lanthanum oxygenates including lanthanum nitrate and lanthanum trioxide, tetravalent cerium oxygenates including cerium dioxide.
According to the present invention, in step (3), hydrogen peroxide as an oxidizing agent is preferably used in the form of an aqueous hydrogen peroxide solution for convenience of operation, and the concentration of the aqueous hydrogen peroxide solution is not particularly limited and may be selected by referring to the conventional ones in the art.
According to the present invention, the amount of the oxidizing agent and the catalyst used in step (3) can be selected from a wide range, and preferably, the molar ratio of the oxidizing agent to the catalyst is 0.01:1 to 100:1, more preferably 0.1:1 to 30:1, in order to better achieve the object of the present invention.
According to the present invention, the mode of contacting the 2-alkylanthracene with the oxidizing agent and the catalyst may be various modes capable of achieving the oxidation production of the 2-alkylanthracene to obtain the 2-alkylanthracene. Preferably, for more complete reaction, the contacting is carried out in the following manner: a raw material liquid containing a 2-alkylanthracene, a catalyst and an oxidation reaction solvent is brought into contact with an oxidizing agent to carry out an oxidation reaction.
According to the present invention, in step (3), the conditions and method of the oxidation reaction may be performed in a manner conventional in the art, except for the combination of the above-mentioned hydrogen peroxide oxidizing agent with a specific catalyst.
According to the present invention, in step (3), the oxidizing agent is used in an amount that enables oxidation of 2-alkylanthracene to produce 2-alkylanthracene, preferably in a molar ratio of the oxidizing agent to 2-alkylanthracene of from 0.01:1 to 100:1, more preferably from 1:1 to 50: 1.
According to the present invention, in step (3), the oxidation reaction is generally carried out under conditions including: the reaction temperature can be 10-200 ℃, and preferably 20-120 ℃; the reaction time can be 0.01-48h, preferably 0.5-24 h; the reaction pressure may be from 0 to 1MPa, preferably from 0 to 0.5 MPa.
According to the present invention, in the step (3), the oxidation reaction solvent is an inert organic solvent capable of dissolving the 2-alkylanthracene.
According to a specific embodiment of the present invention, the oxidation reaction solvent is a solvent having a dielectric constant of greater than 2.8 at 20 ℃, preferably, the oxidation reaction solvent is a solvent having a dielectric constant of greater than 2.8 to less than or equal to 50 at 20 ℃; more preferably, the oxidation reaction solvent is one or more of aliphatic alcohol having 1 to 4 carbon atoms, tetrahydrofuran, acetone, N-alkyl substituted amide and N-alkyl pyrrolidone. Wherein the aliphatic alcohol having 1 to 4 carbon atoms may be a monohydric alcohol or a polyhydric alcohol. In the N-alkyl substituted amide, the number of alkyl substituents is 1-2, and each alkyl substituent is independently C1-C4Alkyl group of (1). Most preferably, the oxidation reaction solvent is selected from one or more of methanol, t-butanol, acetone, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-methylpyrrolidone, and N-ethylpyrrolidone. The amount of the oxidation reaction solvent is only required to ensure that the 2-alkyl anthracene can be fully dissolved so as to achieve the effect of providing a good reaction medium. Preferably, the 2-alkylanthracene is present in an amount of 0.1 to 80 wt%, preferably 5 to 50 wt%, based on the total weight of the 2-alkylanthracene and the oxidation reaction solvent.
According to another embodiment of the present invention, the oxidation reaction solvent is a combination of a solvent A having a dielectric constant of 1 to 10 at 20 ℃ and a solvent B having a dielectric constant of more than 10 to 50 or less at 20 ℃. The inventors of the present invention have found that, in the oxidation reaction in step (3), a combination solvent of a solvent a having a dielectric constant of 1 to 10 at 20 ℃ and a solvent B having a dielectric constant of more than 10 to 50 or less at 20 ℃ is used as the oxidation reaction solvent, and that the solvent properties can be specifically controlled, and the dissolution of 2-alkylanthracene and the promotion of the oxidation reaction can be enhanced by solvation, and the conversion of 2-alkylanthracene can be improved.
According to the invention, preferably, the solvent A is C6Above, more preferably C6-C12One or more of paraffins, naphthenes and aromatics; wherein, the aromatic hydrocarbonThe arene is substituted or unsubstituted, preferably one or more of mono-or poly-substituted benzene, more preferably one or more of poly-substituted benzene, the substituent preferably being C1-C4And one or more of an alkyl group and a halogen element. Further preferably, the solvent A is one or more of polyalkyl substituents of benzene, and most preferably, the solvent A is one or more selected from 1,3, 5-trimethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,3,4, 5-tetramethylbenzene, 1,3,5, 6-tetramethylbenzene, and 2,3,5, 6-tetramethylbenzene.
According to the invention, the solvent B is preferably an N-alkyl-substituted amide in which the number of alkyl substituents is from 1 to 2 and each alkyl substituent is independently C1-C4Alkyl groups of (a); more preferably, the solvent B is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide and N, N-dimethylpropionamide, and most preferably, the solvent B is N, N-dimethylformamide.
According to the invention, in step (3), in order to better achieve the invention purpose of enhancing the oxidation reaction by regulating the solvent property, the volume ratio of the solvent A to the solvent B is 0.01-100, and more preferably 0.05-10.
According to the second embodiment, the oxidation reaction solvent is used in the step (3) in an amount sufficient to ensure that the 2-alkylanthracene is sufficiently soluble to provide a good reaction medium. Preferably, the 2-alkylanthracene is present in an amount of 0.1 to 80 wt%, preferably 5 to 50 wt%, based on the total weight of the 2-alkylanthracene and the oxidation reaction solvent.
According to the present invention, in the step (3), the preparation of 2-alkylanthraquinone from 2-alkylanthracene requires the use of a catalyst, and the catalyst after the reaction can be separated by a separation method which is conventional in the art according to the nature of the catalyst. The 2-alkylanthraquinone in the product is the target product, if other substances including the residual 2-alkylanthraquinone, solvent and generated by-products exist, the 2-alkylanthraquinone can be removed or purified respectively by adopting a conventional separation method or a combined separation method according to the difference of the properties of the substances.
The present invention will be described in detail below by way of examples.
The material composition data are obtained by chromatographic analysis.
The chromatographic analysis method comprises the following steps: agilent 7890A, column DB-1(50 m.times.0.25 mm. times.0.25 μm). Sample inlet temperature: 330 ℃, sample introduction: 0.2 mu L, the split ratio of 20:1, nitrogen as carrier gas, the flow rate of constant flow mode of 0.7mL/min, temperature programming: keeping the temperature at 110 ℃ for 10min, then increasing the temperature to 320 ℃ at the speed of 5 ℃/min, and keeping the temperature for 18 min. FID detector: temperature 350 ℃, hydrogen flow: 35mL/min, air flow: 350mL/min, tail gas blowing is nitrogen, and the flow is as follows: 25 mL/min.
Defining the conversion rate of anthracene as X in the alkylation reaction of step (1)1The substance selectivity calculated on a molar basis is S (mol%). The mass fraction was expressed as a percentage of the chromatographic peak area of each substance, and the fraction W (% by mol) based on the molar amount of each substance was calculated in combination with the molar mass.
AN is used for representing anthracene, Ci-AN represents 2-alkyl anthracene, and Cj-AN represents other alkyl anthracene.
The conversion of anthracene is shown in formula 1:
the 2-alkyl anthracene selectivity is shown in formula 2:
(II) in the separation process of the step (2), the purity B of a certain substance is the mass fraction of the substance, and the purity of the separated anthracene is B1The purity of the separated 2-alkyl anthracene is B2Calculated based on chromatographic data. The anthracene and alkyl anthracene mixture to be separated was chromatographed. Preparing an external standard analysis curve by adopting high-purity 2-alkyl anthracene and mesitylene, quantitatively calculating the content of 2-alkyl anthracene in the mixture of anthracene and 2-alkyl anthracene, and marking as W0And g. The amount of 2-alkylanthracene actually isolated according to the process proposed by the invention is denoted W1And g. The yield Y of the separation process is calculated as shown in formula 3 below.
(III) in the oxidation reaction of the step (3), the conversion rate of Ci-AN is defined as X2The substance selectivity calculated on a molar basis is S (mol%). The mass fraction was expressed as a percentage of the chromatographic peak area of each substance, and the fraction W (% by mol) based on the molar amount of each substance was calculated in combination with the molar mass.
Ci-AN is adopted to represent 2-alkyl anthracene, Ci-AO is adopted to represent 2-alkyl anthraquinone, and Ci-X is adopted to represent other byproducts.
The 2-alkyl anthracene conversion is shown as formula 4:
the 2-alkylanthraquinone selectivity is shown in formula 5:
the following examples 1-17 are provided to illustrate the preparation of the 2-alkylanthraquinones provided by the present invention.
Example 1
And (I) alkylation reaction.
The 2-pentylanthracene is prepared by alkylating anthracene and isoamylene, mesitylene is used as a solvent, and methanesulfonic acid is used as a catalyst. 460g of anthracene, 800ml of mesitylene and 42g of methanesulfonic acid were added to a 2L stirred tank at room temperature. After sealing, the temperature is raised to 165 ℃ at the rotation speed of 1000 rpm, and the pressure is 0.3 MPa. 151g of isoamylene was added to the kettle by means of a plunger pump at a feed rate of 6.6 g/min. When the feeding of the isoamylene is finished, the reaction is continued for 270min while the reaction conditions are kept unchanged, and then the reaction is stopped. Reacting for 10 batches under the same condition, separating the catalyst, and uniformly collecting the alkylation reaction product as the raw material for separating the alkyl anthracene.
(II) separating.
The alkylation reaction product is sent to a normal pressure distillation system, the temperature is raised to 165 ℃ under normal pressure, and light components with boiling points lower than that of anthracene, such as residual isoamylene, mesitylene and the like can be separated out successively. The rest is a solid mixture of anthracene-alkyl anthracene, the mixture is heated to 220 ℃ and is in a molten state and sent into an intermittent melting crystallization system, the melting crystallizer is a tubular crystallizer, and cooling medium is introduced to start temperature reduction and crystallization. The cooling rate is 0.5 ℃/h, the cooling crystallization temperature is 200 ℃, the amount of the seed crystal anthracene added is 0.5 weight percent of the mass of the molten mixture, and the crystal growth time is controlled to be 2 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating up and sweating the crystals in the crystallizer, wherein the heating up rate is 0.2 ℃/h, the sweating finishing temperature is 205 ℃, the sweating amount is 25 weight percent of the mass of the crystals, and the sweating liquid circulates and is contacted with the materials entering the melt crystallizer to be crystallized together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 1KPa, the temperature at the bottom of the tower is 300 ℃, the number of theoretical plates is 65, and the reflux ratio at the top of the tower is 1.5. And carrying out second reduced pressure distillation on the distillate at the tower top, wherein the pressure at the tower top is 1KPa, the temperature at the tower bottom is 240 ℃, the number of theoretical plates is 70, and the reflux ratio at the tower top is 3. And collecting a product 2-pentylanthracene at the bottom of the tower.
(III) oxidation reaction.
The 2-amyl anthracene is oxidized in a liquid phase to prepare the 2-amyl anthraquinone. Into an 8L glass kettle were added 3000ml of methanol, 150g of 2-pentylanthracene, and 156g of potassium chromate. The reaction is carried out at the normal pressure of 65 ℃, 1368g of hydrogen peroxide (the content of hydrogen peroxide is 30 weight percent) is added into the kettle by a peristaltic pump, and the feeding rate is 2 g/min. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. After the reaction is finished, transferring the materials in the kettle into a 20L glass stirring kettle, adding 2000ml of mesitylene and 3000ml of deionized water for extraction and washing, standing, separating out the mesitylene phase containing 2-amylanthraquinone on the upper layer, and distilling to obtain the final product 2-amylanthraquinone. The lower aqueous phase is distilled, and after water is separated, the catalyst can be obtained again.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANStep (ii) of(II) purity B of anthracene obtained by separation1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 1.
Comparative example 1
2-Alkylanthraquinone was prepared according to the method of example 1, except that, in the step (II), after distilling off the light components having a boiling point lower than that of anthracene, anthracene was separated not by melt crystallization but directly by distillation under reduced pressure. The distillation tower for separating anthracene is marked as anthracene-separating reduced pressure distillation system, the pressure at the top of the tower is 8KPa, the distillation temperature is 275 ℃, the number of theoretical plates is 20, and the reflux ratio at the top of the tower is 0.7. The bottom product was subjected to the first vacuum distillation and the second vacuum distillation under the same conditions as in example 1.
In step (III), 3000ml of methanol, 150g of 2-pentylanthracene, and 307g of 36 wt% hydrochloric acid were charged in a 5L glass vessel. The reaction was carried out at atmospheric pressure and 65 ℃ with a peristaltic pump feeding 342g of hydrogen peroxide (30 wt% hydrogen peroxide) into the kettle at a feed rate of 2 g/min. After the feeding is finished, the reaction is continued for 2 hours while the conditions are maintained. After the reaction is finished, transferring the materials in the kettle into a 20L glass stirring kettle, adding 2000ml of mesitylene and 3000ml of deionized water for extraction and washing, standing, separating out the mesitylene phase containing 2-amylanthraquinone on the upper layer, and distilling to obtain the final product 2-amylanthraquinone.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 1.
Example 2
2-Alkylanthraquinone was prepared according to the method of example 1, except that in the second step, the temperature lowering rate was 5.0 ℃/h, the crystallization temperature was 190 ℃, the amount of anthracene added as a seed crystal was 4% by weight based on the mass of the molten mixture, and the crystal growth time was controlled to 4 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating up and sweating the crystals in the crystallizer, wherein the heating up rate is 4 ℃/h, the sweating finishing temperature is 195 ℃, the sweating amount is 10 weight percent of the mass of the crystals, and the sweating is circulated and contacted with the materials entering the melt crystallizer, and then the crystallization operation is carried out together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 1KPa, the temperature at the bottom of the tower is 300 ℃, the number of theoretical plates is 65, and the reflux ratio at the top of the tower is 1.5. And carrying out second reduced pressure distillation on the distillate at the tower top, wherein the pressure at the tower top is 1KPa, the temperature at the tower bottom is 240 ℃, the number of theoretical plates is 70, and the reflux ratio at the tower top is 3. And collecting a product 2-pentylanthracene at the bottom of the tower.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 1.
Example 3
2-Alkylanthraquinone was prepared according to the method of example 1, except that in the step (II), the uncrystallized alkylanthracene mixture was fed to a vacuum distillation system to conduct a third vacuum distillation at a head pressure of 1KPa, a bottom temperature of 290 ℃ C., a theoretical plate number of 65 and a head reflux ratio of 1.5. And carrying out fourth reduced pressure distillation on the tower bottom distillate, wherein the tower top pressure is 1KPa, the tower bottom temperature is 305 ℃, the theoretical plate number is 70, and the tower top reflux ratio is 3. And collecting a product 2-pentylanthracene at the top of the tower.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 1.
Example 4
2-Alkylanthraquinone was prepared according to the method of example 1, except that in the second step, the temperature lowering rate was 2 ℃/h, the crystallization temperature was 192 ℃, the amount of anthracene added as a seed crystal was 2% by weight of the mass of the molten mixture, and the crystal growth time was controlled to 3 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating and sweating the crystals in the crystallizer, wherein the heating rate is 2.0 ℃/h, the sweating finishing temperature is 197 ℃, the sweating amount is 15 weight percent of the mass of the crystals, and the sweating is circulated and contacted with the materials entering the melt crystallizer to be crystallized together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 1KPa, the temperature at the bottom of the tower is 300 ℃, the number of theoretical plates is 40, and the reflux ratio at the top of the tower is 1.5. And carrying out second reduced pressure distillation on the distillate at the tower top, wherein the pressure at the tower top is 1KPa, the temperature at the tower bottom is 240 ℃, the number of theoretical plates is 40, and the reflux ratio at the tower top is 3. And collecting a product 2-pentylanthracene at the bottom of the tower.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 1.
Example 5
2-Alkylanthraquinone was prepared according to the method of example 1, except that in the second step, the temperature lowering rate was 1 ℃/h, the crystallization temperature was 197 ℃, the amount of anthracene added as a seed crystal was 1% by weight of the mass of the molten mixture, and the crystal growth time was controlled to 1.5 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating and sweating the crystals in the crystallizer, wherein the heating rate is 0.6 ℃/h, the sweating finishing temperature is 202 ℃, the sweating amount is 20 weight percent of the mass of the crystals, and the sweating is circulated and contacted with the materials entering the melt crystallizer to be crystallized together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 0.8KPa, the temperature at the bottom of the tower is 280 ℃, the number of theoretical plates is 75, and the reflux ratio at the top of the tower is 2. And carrying out second reduced pressure distillation on the overhead distillate, wherein the overhead pressure is 1.2KPa, the bottom temperature is 266 ℃, the number of theoretical plates is 75, and the overhead reflux ratio is 4. And collecting a product 2-pentylanthracene at the bottom of the tower.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 1.
Example 6
2-Alkylanthraquinone was prepared according to the method of example 1, except that in the second step, the temperature lowering rate was 1.5 ℃/h, the crystallization temperature was 195 ℃, the amount of anthracene added as a seed crystal was 1.5% by weight based on the mass of the molten mixture, and the crystal growth time was controlled to 2.5 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating up and sweating the crystals in the crystallizer, wherein the heating up rate is 1 ℃/h, the sweating finishing temperature is 199 ℃, the sweating amount is 30 weight percent of the mass of the crystals, and the sweating is circulated and contacted with the materials entering the melt crystallizer, and then the crystallization operation is carried out together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 1.2KPa, the temperature at the bottom of the tower is 320 ℃, the number of theoretical plates is 65, and the reflux ratio at the top of the tower is 1. And carrying out second reduced pressure distillation on the distillate at the tower top, wherein the pressure at the tower top is 0.8KPa, the temperature at the tower bottom is 228 ℃, the number of theoretical plates is 70, and the reflux ratio at the tower top is 1. And collecting a product 2-pentylanthracene at the bottom of the tower.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 1.
Example 7
When 2-butylanthraquinone was used as a target product, the other materials and reaction conditions were the same as in example 1 except that in the step (I), 2-methyl-2-butene was changed to isobutylene in an amount of 121g, and the alkylation reaction was carried out in the same manner as in example 1. In the second step, the cooling rate is 0.5 ℃/h, the cooling crystallization temperature is 200 ℃, the amount of the seed crystal anthracene added is 0.5 weight percent of the mass of the molten mixture, and the crystal growth time is controlled to be 2 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating up and sweating the crystals in the crystallizer, wherein the heating up rate is 0.2 ℃/h, the sweating finishing temperature is 205 ℃, the sweating amount is 25 weight percent of the mass of the crystals, and the sweating liquid circulates and is contacted with the materials entering the melt crystallizer to be crystallized together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 1KPa, the temperature at the bottom of the tower is 291 ℃, the number of theoretical plates is 65, and the reflux ratio at the top of the tower is 1.5. And carrying out second reduced pressure distillation on the distillate at the tower top, wherein the pressure at the tower top is 1KPa, the temperature at the tower bottom is 221 ℃, the number of theoretical plates is 70, and the reflux ratio at the tower top is 3. Collecting the product 2-butylanthracene at the bottom of the tower. In the step (III), the oxidation reaction solvent was a mixture of 300ml of 1,3, 5-trimethylbenzene and 2700ml of N, N-dimethylformamide. The catalyst was zirconium dioxide, 79 g. 1453g of hydrogen peroxide and the reaction temperature is 95 ℃.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-butylanthracene SCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-butylanthracene purity B2The total yield of the 2-butylanthracene separation process is Y, and the conversion rate of the 2-butylanthracene in the step (III) is X2And 2-butylanthraquinone Selective SCi-AOAs shown in table 2.
Example 8
When 2-hexylanthracene was used as a target product, the other materials and reaction conditions were the same as in example 1, except that in the step (I), 2-methyl-2-butene was changed to 2-methyl-2-pentene in an amount of 181g, and the alkylation was carried out in the same manner as in example 1. In the second step, the cooling rate is 0.5 ℃/h, the cooling crystallization temperature is 200 ℃, the amount of the seed crystal anthracene added is 0.5 weight percent of the mass of the molten mixture, and the crystal growth time is controlled to be 2 h. After the crystallization process is finished, discharging the feed liquid which is not crystallized and sending the feed liquid into a reduced pressure distillation system. Slowly heating up and sweating the crystals in the crystallizer, wherein the heating up rate is 0.2 ℃/h, the sweating finishing temperature is 205 ℃, the sweating amount is 25 weight percent of the mass of the crystals, and the sweating liquid circulates and is contacted with the materials entering the melt crystallizer to be crystallized together. Sending the uncrystallized alkyl anthracene mixture into a reduced pressure distillation system for first reduced pressure distillation, wherein the pressure at the top of the tower is 1KPa, the temperature at the bottom of the tower is 310 ℃, the number of theoretical plates is 65, and the reflux ratio at the top of the tower is 1.5. And carrying out second reduced pressure distillation on the distillate at the tower top, wherein the pressure at the tower top is 1KPa, the temperature at the tower bottom is 251 ℃, the number of theoretical plates is 70, and the reflux ratio at the tower top is 3. Collecting the bottom product 2-hexyl anthracene. In the third step, the oxidation reaction solvent was a mixture of 300ml of 1,3, 5-trimethylbenzene and 2700ml of N, N-dimethylformamide. The catalyst was metatitanic acid, 224 g. 1298g of hydrogen peroxide and 95 ℃ of reaction temperature.
Conversion rate X of anthracene in the step (I)1S selectivity to 2-hexyl anthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-hexyl anthracene purity B2The total yield of the separation process of the 2-hexyl anthracene is Y, and the conversion rate of the 2-hexyl anthracene in the step (III) is X2And 2-hexylanthraquinone-selective SCi-AOAs shown in table 2.
Example 9
And (I) alkylation reaction.
The 2-pentylanthracene is prepared by alkylating anthracene and isoamylene, mesitylene is used as a solvent, and methanesulfonic acid is used as a catalyst. 76g of anthracene, 800ml of mesitylene and 12g of methanesulfonic acid were added to a 2L stirred tank at room temperature. After sealing, the temperature is raised to 110 ℃ at the rotating speed of 1000 rpm, and the pressure is 0.15 MPa. 60g of isoamylene was added to the kettle by means of a plunger pump at a feed rate of 3 g/min. When the feeding of the isoamylene is finished, the reaction is continued for 270min while the reaction conditions are kept unchanged, and then the reaction is stopped. Reacting for 10 batches under the same condition, separating the catalyst, and uniformly collecting the alkylation reaction product as the raw material for separating the alkyl anthracene.
Both the step (two) and the step (three) were the same as in example 1.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Middle, ofProduct 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 2.
Example 10
And (I) alkylation reaction.
The 2-pentylanthracene is prepared by alkylating anthracene and isoamylene, mesitylene is used as a solvent, and methanesulfonic acid is used as a catalyst. To a 2L stirred tank, 229g of anthracene, 800ml of mesitylene, and 40g of methanesulfonic acid were added at room temperature. After sealing, the temperature is raised to 130 ℃ at the rotation speed of 1000 rpm, and the pressure is 0.2 MPa. 18g of isoamylene was added to the kettle by means of a plunger pump at a feed rate of 2 g/min. When the feeding of the isoamylene is finished, the reaction is continued for 270min while the reaction conditions are kept unchanged, and then the reaction is stopped. Reacting for 10 batches under the same condition, separating the catalyst, and uniformly collecting the alkylation reaction product as the raw material for separating the alkyl anthracene.
Both the step (two) and the step (three) were the same as in example 1.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 2.
Example 11
Both the step (one) and the step (two) were the same as in example 1. Except that, in the step (III), 2-pentylanthracene was used in an amount of 266g, and the oxidation reaction solvent was a mixture of 2700ml of 1,3, 5-trimethylbenzene and 300ml of N, N-dimethylformamide. The catalyst was lanthanum nitrate hexahydrate, 116 g. 607.5g of hydrogen peroxide and 120 ℃ of reaction temperature.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOSuch as a watch2, respectively.
Example 12
Both the step (one) and the step (two) were the same as in example 1. Except that, in the step (III), 2-pentylanthracene was used in an amount of 600g, and the oxidation reaction solvent was a mixture of 1500ml of 1,3, 5-trimethylbenzene and 1500ml of N, N-dimethylformamide. The catalyst was lanthanum nitrate hexahydrate, 262 g. 1370g of hydrogen peroxide and 120 ℃ of reaction temperature.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 2.
Example 13
Both the step (one) and the step (two) were the same as in example 1. Except that, in the step (III), the oxidation reaction solvent was a mixture of 300ml of 2,3,5, 6-tetramethylbenzene and 2700ml of N, N-dimethylacetamide. The catalyst was zirconium dioxide, 74 g. 1368g of hydrogen peroxide and 95 ℃ of reaction temperature.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 2.
Example 14
Both the step (one) and the step (two) were the same as in example 1. Except that, in the step (three), the oxidation reaction solvent was 3000ml of N, N-dimethylformamide. The catalyst was zirconium dioxide, 74 g. 1368g of hydrogen peroxide and 95 ℃ of reaction temperature.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2Total yield Y of 2-pentylanthracene separation process, and 2-pentylanthracene in step (III)Conversion rate of X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 2.
Example 15
Both the step (one) and the step (two) were the same as in example 1. Except that, in the step (three), the oxidation reaction solvent was 3000ml of N, N-dimethylformamide. The catalyst was anhydrous sodium molybdate, 124 g. 1368g of hydrogen peroxide and 95 ℃ of reaction temperature.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 2.
Example 16
Both the step (one) and the step (two) were the same as in example 1. Except that, in the step (three), the oxidation reaction solvent was 3000ml of N, N-dimethylformamide. The catalyst was iron oxide, 97 g. 1368g of hydrogen peroxide and 95 ℃ of reaction temperature.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinone-selective SCi-AOAs shown in table 2.
Example 17
Both the step (one) and the step (two) were the same as in example 1. Except that, in the step (III), the oxidation reaction solvent was 3000ml of 1,3, 5-trimethylbenzene. The catalyst was sodium molybdate, 124 g. 1368g of hydrogen peroxide and 95 ℃ of reaction temperature.
Conversion rate X of anthracene in the step (I)1Selectivity of 2-pentylanthraceneCi-ANAnd (II) separating the obtained anthracene in the step (II) to obtain the anthracene with the purity B1Intermediate 2-pentylanthracene purity B2The total yield of the 2-pentylanthracene separation process is Y, and the conversion rate of the 2-pentylanthracene in the step (III) is X2And 2-amylanthraquinoneSelectivity SCi-AOAs shown in table 2.
As can be seen from the results in tables 1 and 2, in the method for preparing 2-alkylanthraquinone by separating 2-alkylanthraquinone from a product containing alkylanthraquinone and performing catalytic oxidation, the purity of the separated crystal anthracene, the purity of the intermediate product 2-pentylanthracene (2-butylanthracene, 2-hexylanthracene), and the total yield of the separation process of 2-pentylanthracene (2-butylanthracene, 2-hexylanthracene) are significantly improved by the melt crystallization-distillation coupling separation technology, compared with the prior art, and the total yield of the finally obtained 2-alkylanthraquinone is also improved.
Compared with the prior art, the 2-alkyl anthracene oxidation technology in the method provided by the invention has the advantages that although the efficiency is reduced, the corrosivity is avoided, no chlorine-containing wastewater is generated, the catalyst is easy to recover, and the system and the process are simple and clean. Preferably, the combined solvent system developed in the oxidation step of the 2-alkyl anthracene can enhance the conversion of the 2-alkyl anthracene and improve the selectivity of the 2-alkyl anthraquinone by adjusting the properties of the solvent.
Therefore, the invention provides a novel green preparation method of 2-alkylanthraquinone.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (149)
1. A process for separating 2-alkyl anthracenes from alkyl anthracene-containing products and producing 2-alkyl anthraquinones by catalytic oxidation, the process comprising the steps of:
(1) preparing a reaction product containing an alkyl anthracene from an anthracene;
(2) separating the reaction product containing alkyl anthracene obtained from step (1), the separation method comprising: melting crystallization separation of anthracene and distillation separation of 2-alkyl anthracene;
(3) contacting the 2-alkyl anthracene obtained in the step (2) with an oxidizing agent, which is hydrogen peroxide, under oxidizing conditions and in the presence of an oxidizing reaction solvent and a catalyst, wherein the catalyst is one or more selected from the group consisting of an oxide of an alkaline earth metal, a hydroxide of an alkaline earth metal, an oxygen-containing compound of a transition metal, and an oxygen-containing compound of a lanthanide metal.
2. The process of claim 1, wherein in step (1), the process for producing an alkyl anthracene-containing reaction product from anthracene comprises: the alkylation reaction is carried out by contacting anthracene with an alkylating agent under alkylation conditions and in the presence of an alkylation solvent and a catalyst.
3. The method of claim 2, wherein the contacting is by: the raw material liquid containing anthracene, catalyst and alkylation reaction solvent is contacted with alkylation reagent to make alkylation reaction.
4. The process of claim 2 or 3, wherein the alkylating agent is one or more of an olefin containing 2 to 8 carbon atoms, an alcohol, a halogenated hydrocarbon, and an ether.
5. The process of claim 4, wherein the alkylating agent is one or more of an olefin containing from 4 to 6 carbon atoms, an alcohol, a halogenated hydrocarbon, and an ether.
6. A process according to claim 5, wherein the alkylating agent is a mono-olefin containing from 4 to 6 carbon atoms.
7. The process of any one of claims 2,3,5 and 6, wherein in step (1), the molar ratio of anthracene to alkylating agent is from 0.2:1 to 20: 1.
8. The process of claim 7, wherein in step (1), the molar ratio of anthracene to alkylating agent is from 0.5:1 to 5: 1.
9. The process of claim 4, wherein in step (1), the molar ratio of anthracene to alkylating agent is from 0.2:1 to 20: 1.
10. The process of claim 9, wherein in step (1), the molar ratio of anthracene to alkylating agent is from 0.5:1 to 5: 1.
11. The process according to claim 2 or 3, wherein in the step (1), the alkylation reaction solvent is a solvent having a dielectric constant of 1 to 10 at 20 ℃, and the alkylation reaction solvent is C6One or more of the above paraffins, naphthenes and aromatics; wherein the aromatic hydrocarbon is substituted or unsubstituted, and the substituent is C1-C4One or more of alkyl and halogen elements of (a);
based on the total weight of anthracene and alkylation reaction solvent, the content of anthracene is 5-60 wt%.
12. The process of claim 11, wherein the alkylation reaction solvent is C6-C12One or more of paraffins, naphthenes and aromatics;
based on the total weight of anthracene and alkylation reaction solvent, the content of anthracene is 8-50 wt%.
13. The method of claim 12, wherein the aromatic hydrocarbon is one or more of a mono-or multi-substituted benzene.
14. The method of claim 13, wherein the aromatic hydrocarbon is one or more of a poly-substituted version of benzene.
15. The process of claim 14, wherein the alkylation reaction solvent is one or more of a polyalkyl substituent of benzene.
16. The process of claim 15, wherein the alkylation reaction solvent is selected from one or more of 1,3, 5-trimethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,3,4, 5-tetramethylbenzene, 1,3,5, 6-tetramethylbenzene, and 2,3,5, 6-tetramethylbenzene.
17. The process according to any one of claims 2,3,5,6, 8 to 10, and 12 to 16, wherein in the step (1), the catalyst is contained in an amount of 0.01 to 50% by weight based on the total weight of the raw material liquid containing the anthracene, the catalyst, and the alkylation reaction solvent.
18. The process according to claim 17, wherein in the step (1), the catalyst is contained in an amount of 0.5 to 30% by weight based on the total weight of the raw material liquid containing anthracene, the catalyst and the alkylation reaction solvent.
19. The method of claim 17, wherein the catalyst is selected from one of liquid acids.
20. The process of claim 19, wherein the catalyst is methanesulfonic acid or p-toluenesulfonic acid.
21. The method of claim 17, wherein the catalyst is selected from a plurality of liquid acids.
22. The process of claim 21, wherein the catalyst is methanesulfonic acid and p-toluenesulfonic acid.
23. The process according to claim 4, wherein in the step (1), the catalyst is contained in an amount of 0.01 to 50% by weight based on the total weight of the raw material liquid containing anthracene, the catalyst and the alkylation reaction solvent.
24. The process according to claim 7, wherein in the step (1), the catalyst is contained in an amount of 0.01 to 50% by weight based on the total weight of the raw material liquid containing anthracene, the catalyst and the alkylation reaction solvent.
25. The process according to claim 11, wherein in the step (1), the catalyst is contained in an amount of 0.01 to 50% by weight based on the total weight of the raw material liquid containing anthracene, the catalyst and the alkylation reaction solvent.
26. The process of any one of claims 23 to 25, wherein in step (1), the catalyst is present in an amount of from 0.5 to 30 wt.% based on the total weight of the feed solution comprising anthracene, catalyst, and alkylation reaction solvent in step (1).
27. The process of any one of claims 23-25, wherein the catalyst is selected from one of liquid acids.
28. The process of claim 27, wherein the catalyst is methanesulfonic acid or p-toluenesulfonic acid.
29. The method of any one of claims 23-25, wherein the catalyst is selected from a plurality of liquid acids.
30. The process of claim 29, wherein the catalyst is methanesulfonic acid and p-toluenesulfonic acid.
31. The process of any one of claims 2,3,5,6, 8-10, 12-16, wherein in step (1), the alkylation reaction conditions comprise: the reaction temperature is 100-250 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.
32. The process of claim 31, wherein in step (1), the alkylation reaction conditions comprise: the reaction temperature is 120-200 ℃; the reaction pressure is 0.05-0.5 MPa; the reaction time is 0.5-24 h.
33. The process of claim 4, wherein in step (1), the alkylation reaction conditions comprise: the reaction temperature is 100-250 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.
34. The process of claim 7, wherein in step (1), the alkylation reaction conditions comprise: the reaction temperature is 100-250 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.
35. The process of claim 11, wherein in step (1), the alkylation reaction conditions comprise: the reaction temperature is 100-250 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.
36. The process of any one of claims 33 to 35, wherein in step (1), the alkylation reaction conditions comprise: the reaction temperature is 120-200 ℃; the reaction pressure is 0.05-0.5 MPa; the reaction time is 0.5-24 h.
37. The process of any one of claims 1-3, 5,6, 8-10, 12-16, 18-25, 28, 30, 32-35, wherein the reaction product containing alkyl anthracene obtained via step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;
the step (2) comprises the following steps:
(2-2) heating the reaction product containing the alkyl anthracene obtained in the step (1) to a molten state, cooling and crystallizing, separating to obtain an anthracene crystal and a feed liquid containing a series of alkyl anthracene products of 2-alkyl anthracene, heating the anthracene crystal for sweating, and separating the sweating liquid and the anthracene crystal;
(2-3) separating 2-alkyl anthracene from the series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.
38. The process of claim 4, wherein the reaction product containing alkyl anthracene obtained via step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;
the step (2) comprises the following steps:
(2-2) heating the reaction product containing the alkyl anthracene obtained in the step (1) to a molten state, cooling and crystallizing, separating to obtain an anthracene crystal and a feed liquid containing a series of alkyl anthracene products of 2-alkyl anthracene, heating the anthracene crystal for sweating, and separating the sweating liquid and the anthracene crystal;
(2-3) separating 2-alkyl anthracene from the series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.
39. The process of claim 7, wherein the reaction product containing alkyl anthracene obtained via step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;
the step (2) comprises the following steps:
(2-2) heating the reaction product containing the alkyl anthracene obtained in the step (1) to a molten state, cooling and crystallizing, separating to obtain an anthracene crystal and a feed liquid containing a series of alkyl anthracene products of 2-alkyl anthracene, heating the anthracene crystal for sweating, and separating the sweating liquid and the anthracene crystal;
(2-3) separating 2-alkyl anthracene from the series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.
40. The process of claim 11, wherein the reaction product containing alkyl anthracene obtained via step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;
the step (2) comprises the following steps:
(2-2) heating the reaction product containing the alkyl anthracene obtained in the step (1) to a molten state, cooling and crystallizing, separating to obtain an anthracene crystal and a feed liquid containing a series of alkyl anthracene products of 2-alkyl anthracene, heating the anthracene crystal for sweating, and separating the sweating liquid and the anthracene crystal;
(2-3) separating 2-alkyl anthracene from the series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.
41. The process of claim 17, wherein the reaction product containing alkyl anthracene obtained via step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;
the step (2) comprises the following steps:
(2-2) heating the reaction product containing the alkyl anthracene obtained in the step (1) to a molten state, cooling and crystallizing, separating to obtain an anthracene crystal and a feed liquid containing a series of alkyl anthracene products of 2-alkyl anthracene, heating the anthracene crystal for sweating, and separating the sweating liquid and the anthracene crystal;
(2-3) separating 2-alkyl anthracene from the series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.
42. The process of claim 26, wherein the reaction product containing alkyl anthracene obtained via step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;
the step (2) comprises the following steps:
(2-2) heating the reaction product containing the alkyl anthracene obtained in the step (1) to a molten state, cooling and crystallizing, separating to obtain an anthracene crystal and a feed liquid containing a series of alkyl anthracene products of 2-alkyl anthracene, heating the anthracene crystal for sweating, and separating the sweating liquid and the anthracene crystal;
(2-3) separating 2-alkyl anthracene from the series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.
43. The process of claim 27, wherein the reaction product containing alkyl anthracene obtained via step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;
the step (2) comprises the following steps:
(2-2) heating the reaction product containing the alkyl anthracene obtained in the step (1) to a molten state, cooling and crystallizing, separating to obtain an anthracene crystal and a feed liquid containing a series of alkyl anthracene products of 2-alkyl anthracene, heating the anthracene crystal for sweating, and separating the sweating liquid and the anthracene crystal;
(2-3) separating 2-alkyl anthracene from the series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.
44. The process of claim 29, wherein the reaction product containing alkyl anthracene obtained via step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;
the step (2) comprises the following steps:
(2-2) heating the reaction product containing the alkyl anthracene obtained in the step (1) to a molten state, cooling and crystallizing, separating to obtain an anthracene crystal and a feed liquid containing a series of alkyl anthracene products of 2-alkyl anthracene, heating the anthracene crystal for sweating, and separating the sweating liquid and the anthracene crystal;
(2-3) separating 2-alkyl anthracene from the series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.
45. The process of claim 31, wherein the reaction product containing alkyl anthracene obtained via step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;
the step (2) comprises the following steps:
(2-2) heating the reaction product containing the alkyl anthracene obtained in the step (1) to a molten state, cooling and crystallizing, separating to obtain an anthracene crystal and a feed liquid containing a series of alkyl anthracene products of 2-alkyl anthracene, heating the anthracene crystal for sweating, and separating the sweating liquid and the anthracene crystal;
(2-3) separating 2-alkyl anthracene from the series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.
46. The process of claim 36, wherein the reaction product containing alkyl anthracene obtained via step (1) contains anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene;
the step (2) comprises the following steps:
(2-2) heating the reaction product containing the alkyl anthracene obtained in the step (1) to a molten state, cooling and crystallizing, separating to obtain an anthracene crystal and a feed liquid containing a series of alkyl anthracene products of 2-alkyl anthracene, heating the anthracene crystal for sweating, and separating the sweating liquid and the anthracene crystal;
(2-3) separating 2-alkyl anthracene from the series of alkyl anthracene products containing 2-alkyl anthracene by one or more distillation steps.
47. The method as claimed in claim 37, wherein, in the step (2-2), the melting temperature is 200-270 ℃.
48. The method as claimed in claim 47, wherein, in the step (2-2), the melting temperature is 210 ℃ to 250 ℃.
49. The method as claimed in any one of claims 38 to 46, wherein the melting temperature in step (2-2) is 200-270 ℃.
50. The method as claimed in claim 49, wherein, in the step (2-2), the melting temperature is 210 ℃ to 250 ℃.
51. The method as claimed in claim 37, wherein, in the step (2-2), the cooling crystallization temperature is 180-210 ℃, the cooling rate of the cooling crystallization is 0.1-10 ℃/h, and the cooling crystallization time is 1-5 h.
52. The method as claimed in claim 51, wherein, in the step (2-2), the cooling crystallization temperature is 190-200 ℃, the cooling rate of the cooling crystallization is 0.5-5 ℃/h, and the cooling crystallization time is 1.5-4 h.
53. The method as claimed in claim 49, wherein, in the step (2-2), the cooling crystallization temperature is 180-210 ℃, the cooling rate of the cooling crystallization is 0.1-10 ℃/h, and the cooling crystallization time is 1-5 h.
54. The method as claimed in claim 53, wherein, in the step (2-2), the cooling crystallization temperature is 190-200 ℃, the cooling crystallization temperature reduction rate is 0.5-5 ℃/h, and the cooling crystallization time is 1.5-4 h.
55. The method as claimed in any one of claims 38-48, 50, wherein in the step (2-2), the cooling crystallization temperature is 180-210 ℃, the cooling crystallization temperature reduction rate is 0.1-10 ℃/h, and the cooling crystallization time is 1-5 h.
56. The method as claimed in claim 55, wherein, in the step (2-2), the cooling crystallization temperature is 190-200 ℃, the cooling rate of the cooling crystallization is 0.5-5 ℃/h, and the cooling crystallization time is 1.5-4 h.
57. The process according to any one of claims 51 to 54 or 56, wherein the step (2-2) further comprises a step of adding seed anthracene in an amount of 0.1 to 10 wt% based on the mass of the molten mixture during the cooling crystallization.
58. The process of claim 57, wherein the seed anthracene is added in an amount of 0.2 to 5 wt% based on the mass of the melt mixture.
59. The process of claim 55, wherein in step (2-2), during the cooling crystallization, a seed anthracene is added in an amount of 0.1-10 wt% based on the mass of the molten mixture.
60. The method of claim 59, wherein the seed anthracene is added in an amount of 0.2 to 5 wt% based on the mass of the melt mixture.
61. The method according to any one of claims 38 to 48 or 50, wherein in the step (2-2), the temperature increase rate at which the anthracene crystals are subjected to sweating is 0.1 to 8 ℃/h; the temperature is raised to a temperature at which sweating stops and is lower than the melting temperature of the anthracene crystal.
62. The method according to claim 61, wherein in the step (2-2), the temperature rising rate for sweating the anthracene crystal is 0.2-4 ℃/h; the temperature is raised to a temperature of less than or equal to 210 ℃ at which sweating ceases.
63. The method as claimed in claim 62, wherein in the step (2-2), the sweating is stopped when the temperature is raised to 5-15 ℃ higher than the cooling crystallization temperature and lower than 210 ℃.
64. The method as claimed in claim 63, wherein the sweating end temperature in step (2-2) is 190-210 ℃.
65. The method as claimed in claim 64, wherein the sweating completion temperature in step (2-2) is 195-205 ℃.
66. The method according to claim 37, wherein in the step (2-2), the temperature rising rate for sweating the anthracene crystal is 0.1-8 ℃/h; the temperature is raised to a temperature at which sweating stops and is lower than the melting temperature of the anthracene crystal.
67. The method according to claim 49, wherein in the step (2-2), the temperature rising rate for sweating the anthracene crystal is 0.1-8 ℃/h; the temperature is raised to a temperature at which sweating stops and is lower than the melting temperature of the anthracene crystal.
68. The method according to claim 66 or 67, wherein in the step (2-2), the temperature rising rate for sweating the anthracene crystal is 0.2-4 ℃/h; the temperature is raised to a temperature of less than or equal to 210 ℃ at which sweating ceases.
69. The method as claimed in claim 68, wherein in the step (2-2), the sweating is stopped when the temperature is raised to 5-15 ℃ higher than the cooling crystallization temperature and lower than 210 ℃.
70. The method as claimed in claim 69, wherein, in the step (2-2), the sweating finishing temperature is 190-210 ℃.
71. The method as claimed in claim 70, wherein the sweating completion temperature in step (2-2) is 195-205 ℃.
72. The method of any of claims 62-67, 69-71, wherein the amount of perspiration is 5 to 40% by weight of the mass of the anthracene crystals.
73. The method of claim 72, wherein the amount of perspiration is 10-30% by weight of the mass of the anthracene crystals.
74. The method of claim 61, wherein the amount of perspiration is 5 to 40 weight percent of the mass of the anthracene crystals.
75. The method of claim 68, wherein the amount of perspiration is 5-40% by weight of the mass of the anthracene crystals.
76. The method of claim 74 or 75, wherein the amount of perspiration is 10-30% by weight of the mass of the anthracene crystals.
77. The method of claim 61, further comprising recycling sweat back to the melt crystallization step for melt crystallization with the reaction product comprising alkyl anthracene.
78. The method of claim 68, further comprising circulating sweat back to the melt crystallization step for melt crystallization with the reaction product comprising alkyl anthracene.
79. The method of any of claims 62-67, 69-71, wherein the method further comprises recycling sweat back to the melt crystallization step for melt crystallization with the reaction product comprising alkyl anthracene.
80. The method according to claim 37, wherein, in the step (2-3), when the series of alkyl anthracene products containing the 2-alkyl anthracene is a mixture of two substances, or a mixture of three or more substances, and the boiling point of the 2-alkyl anthracene is the lowest or the highest; then a one-step distillation is performed to separate the 2-alkyl anthracene.
81. The method according to any one of claims 38 to 46, wherein, in the step (2-3), when the alkyl anthracene product of the series containing the 2-alkyl anthracene is a mixture of two substances, or a mixture of three or more substances, and the boiling point of the 2-alkyl anthracene is the lowest or the highest; then a one-step distillation is performed to separate the 2-alkyl anthracene.
82. The method according to claim 37, wherein, in the step (2-3), when the series of alkyl anthracene products containing the 2-alkyl anthracene is a mixture of three or more substances, and the boiling point of the 2-alkyl anthracene is between the substance with the highest boiling point and the substance with the lowest boiling point in the mixture; then carrying out multi-step reduced pressure distillation, wherein the multi-step reduced pressure distillation method comprises the following steps:
mode 1:
carrying out first reduced pressure distillation on feed liquid of a series of alkyl anthracene products containing 2-alkyl anthracene, and separating to obtain distillate containing a light component Cj 1-anthracene and a bottom product containing a heavy component Cj 2-anthracene; carrying out second reduced pressure distillation on the distillate containing the light component Cj 1-anthracene to obtain a distillate containing the light component Cj 3-anthracene and a bottom product containing the target product Ci-anthracene;
wherein, the light component Cj 1-anthracene is an alkyl anthracene product with the total carbon number j1 of an alkyl side chain being an integer which is more than 1 and less than j1 and less than i +1, the heavy component Cj 2-anthracene is an alkyl anthracene product with the total carbon number j2 of the alkyl side chain being an integer which is more than i and less than j2 and less than 41, and the light component Cj 3-anthracene is an alkyl anthracene product with the total carbon number j3 of the alkyl side chain being an integer which is more than 1 and less than j3 and less than i;
or,
mode 2:
carrying out third reduced pressure distillation on feed liquid of a series of alkyl anthracene products containing 2-alkyl anthracene to obtain distillate containing light component Cm 1-anthracene and a bottom product containing heavy component Cm 2-anthracene; carrying out fourth reduced pressure distillation on the bottom product containing the heavy component Cm 2-anthracene to obtain a distillate containing the target product Ci-anthracene and a bottom product containing the heavy component Cm 3-anthracene;
wherein the light component Cm 1-anthracene is an alkyl anthracene product with the total carbon number of the alkyl side chain m1 being an integer of 1< m 1< i, the heavy component Cm 2-anthracene is an alkyl anthracene product with the total carbon number of the alkyl side chain m2 being an integer of i-1 < m 2< 41, and Cm 3-anthracene is an alkyl anthracene product with the total carbon number of the alkyl side chain m3 being an integer of i < m3 < 41;
wherein, in the target product Ci-anthracene, i represents the total carbon number of an alkyl side chain, and i is an integer of 4-7.
83. The method according to any one of claims 38 to 46, wherein, in the step (2-3), when the alkyl anthracene product of the series containing the 2-alkyl anthracene is a mixture of three or more substances, and the boiling point of the 2-alkyl anthracene is between the substance with the highest boiling point and the substance with the lowest boiling point in the mixture; then carrying out multi-step reduced pressure distillation, wherein the multi-step reduced pressure distillation method comprises the following steps:
mode 1:
carrying out first reduced pressure distillation on feed liquid of a series of alkyl anthracene products containing 2-alkyl anthracene, and separating to obtain distillate containing a light component Cj 1-anthracene and a bottom product containing a heavy component Cj 2-anthracene; carrying out second reduced pressure distillation on the distillate containing the light component Cj 1-anthracene to obtain a distillate containing the light component Cj 3-anthracene and a bottom product containing the target product Ci-anthracene;
wherein, the light component Cj 1-anthracene is an alkyl anthracene product with the total carbon number j1 of an alkyl side chain being an integer which is more than 1 and less than j1 and less than i +1, the heavy component Cj 2-anthracene is an alkyl anthracene product with the total carbon number j2 of the alkyl side chain being an integer which is more than i and less than j2 and less than 41, and the light component Cj 3-anthracene is an alkyl anthracene product with the total carbon number j3 of the alkyl side chain being an integer which is more than 1 and less than j3 and less than i;
or,
mode 2:
carrying out third reduced pressure distillation on feed liquid of a series of alkyl anthracene products containing 2-alkyl anthracene to obtain distillate containing light component Cm 1-anthracene and a bottom product containing heavy component Cm 2-anthracene; carrying out fourth reduced pressure distillation on the bottom product containing the heavy component Cm 2-anthracene to obtain a distillate containing the target product Ci-anthracene and a bottom product containing the heavy component Cm 3-anthracene;
wherein the light component Cm 1-anthracene is an alkyl anthracene product with the total carbon number of the alkyl side chain m1 being an integer of 1< m 1< i, the heavy component Cm 2-anthracene is an alkyl anthracene product with the total carbon number of the alkyl side chain m2 being an integer of i-1 < m 2< 41, and Cm 3-anthracene is an alkyl anthracene product with the total carbon number of the alkyl side chain m3 being an integer of i < m3 < 41;
wherein, in the target product Ci-anthracene, i represents the total carbon number of an alkyl side chain, and i is an integer of 4-7.
84. The process of claim 82, wherein in the multi-step vacuum distillation step, mode 1, the conditions of the first vacuum distillation comprise: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-.
85. The process of claim 84, wherein in the multi-step vacuum distillation step, mode 1, the conditions of the first vacuum distillation comprise: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 210-340 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.
86. The process of claim 85, wherein in the multi-step vacuum distillation step, mode 1, the conditions of the first vacuum distillation comprise: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 260-320 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-3.
87. The process of claim 83, wherein in the multi-step vacuum distillation step, mode 1, the conditions of the first vacuum distillation comprise: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-.
88. The process of claim 87, wherein in the multi-step vacuum distillation step, mode 1, the conditions of the first vacuum distillation comprise: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 210-340 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.
89. The process of claim 88, wherein in the multi-step vacuum distillation step, mode 1, the conditions of the first vacuum distillation comprise: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 260-320 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-3.
90. The process of any one of claims 82, 84-89, wherein in the multi-step vacuum distillation step, mode 1, the conditions of the second vacuum distillation comprise: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8.
91. The process of claim 90, wherein in the multi-step vacuum distillation step, mode 1, the conditions of the second vacuum distillation comprise: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 200-310 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.
92. The process of claim 91, wherein in the multi-step vacuum distillation step, mode 1, the conditions of the second vacuum distillation comprise: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 220-305 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-5.
93. The process of claim 83, wherein in the multi-step vacuum distillation step, mode 1, the conditions of the second vacuum distillation comprise: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8.
94. The process of claim 93, wherein in the multi-step vacuum distillation step, mode 1, the conditions of the second vacuum distillation comprise: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 200-310 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.
95. The process of claim 94, wherein in the multi-step vacuum distillation step, mode 1, the conditions of the second vacuum distillation comprise: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 220-305 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-5.
96. The process of claim 82, wherein in the multi-step vacuum distillation step, mode 2, the third vacuum distillation conditions comprise: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-.
97. The process of claim 96, wherein in the multi-step vacuum distillation step, mode 2, the third vacuum distillation conditions comprise: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 210-340 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.
98. The process of claim 97, wherein in the multi-step vacuum distillation step, mode 2, the third vacuum distillation conditions comprise: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 260-320 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-3.
99. The process of claim 83, wherein in the multi-step vacuum distillation step, mode 2, the third vacuum distillation conditions comprise: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-.
100. The process of claim 99, wherein in the multi-step vacuum distillation step, mode 2, the third vacuum distillation conditions comprise: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 210-340 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.
101. The process of claim 100, wherein in the multi-step vacuum distillation step, mode 2, the third vacuum distillation conditions comprise: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 260-320 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-3.
102. The process of any one of claims 82, 96-101, wherein in the multi-step vacuum distillation step, mode 2, the fourth vacuum distillation conditions comprise: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8.
103. The process of claim 102, wherein in the multi-step vacuum distillation step, mode 2, the fourth vacuum distillation conditions comprise: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 200-310 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.
104. The process of claim 103, wherein in the multi-step vacuum distillation step, mode 2, the fourth vacuum distillation conditions comprise: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 220-305 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-5.
105. The process of claim 83, wherein in the multi-step vacuum distillation step, mode 2, the fourth vacuum distillation conditions comprise: the pressure at the top of the distillation tower is 0.01-20KPa, the temperature at the bottom of the distillation tower is 180-330 ℃, the number of theoretical plates is 20-90, and the reflux ratio at the top of the distillation tower is 0.5-8.
106. The process of claim 105, wherein in the multi-step vacuum distillation step, mode 2, the fourth vacuum distillation conditions comprise: the pressure at the top of the tower is 0.1-10KPa, the temperature at the bottom of the tower is 200-310 ℃, the number of theoretical plates is 30-75, and the reflux ratio at the top of the tower is 1-7.
107. The process of claim 106, wherein in the multi-step vacuum distillation step, mode 2, the fourth vacuum distillation conditions comprise: the pressure at the top of the distillation tower is 0.5-2KPa, the temperature at the bottom of the distillation tower is 220-305 ℃, the number of theoretical plates is 40-75, and the reflux ratio at the top of the distillation tower is 1-5.
108. The process as claimed in any one of claims 38 to 48, 50 to 54, 56, 58 to 60, 62 to 67, 69 to 71, 73 to 75, 77, 78, 80, 82, 84 to 89, 91 to 101, 103 and 107, wherein the reaction product containing the alkyl anthracene obtained in step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
109. The process of claim 37, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
110. The process of claim 49, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
111. The process of claim 55, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
112. The process of claim 57, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
113. The process of claim 61, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
114. The process of claim 68, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
115. The process of claim 72, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
116. The process of claim 76, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
117. The process of claim 79, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
118. The process of claim 81, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
119. The process of claim 83, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
120. The process of claim 90, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
121. The process of claim 102, wherein the reaction product containing alkyl anthracene obtained via step (1) further contains a reaction solvent;
the step (2) further comprises: a step (2-1) of separating the reaction solvent prior to the separation of anthracene by melt crystallization and the separation of 2-alkyl anthracene by distillation;
(2-1) the separation method comprising: and (2) distilling the reaction product containing the alkyl anthracene obtained in the step (1) in a distillation tower to obtain a distillate containing the reaction solvent and a tower bottom product containing anthracene and a series of alkyl anthracene products containing 2-alkyl anthracene.
122. The process of claim 108, wherein in step (2-1), the distillation conditions comprise: the bottom temperature of the distillation tower is 100-300 ℃, and the pressure of the top of the distillation tower is normal pressure.
123. The method as claimed in claim 122, wherein the distillation column bottom temperature is 150-200 ℃.
124. The method as claimed in any one of claims 109-121, wherein the distillation conditions in step (2-1) comprise: the bottom temperature of the distillation tower is 100-300 ℃, and the pressure of the top of the distillation tower is normal pressure.
125. The method as claimed in claim 124, wherein the distillation column bottom temperature is 150-200 ℃.
126. The process of claim 1 wherein in step (3) the catalyst is selected from one or more of group IIA, group IVB, group VB, group VIB, group VIIB, group VIII metal oxygenates and lanthanide metal oxygenates.
127. The method of claim 126, wherein the catalyst is selected from one or more of the group consisting of oxygen-containing compounds of Ca, Ba, Ti, Zr, V, Cr, Mo, W, Mn, Ru, Co, Ni, La, and Ce.
128. The method of claim 127, wherein the catalyst is selected from one or more of calcium hydroxide, barium hydroxide, metatitanic acid, zirconium dioxide, zirconyl nitrate, sodium metavanadate, potassium chromate, chromium oxide, sodium molybdate, ammonium molybdate, molybdenum trioxide, sodium tungstate, manganese oxide, manganese dioxide, ruthenium dioxide, cobaltous oxide, nickel trioxide, lanthanum nitrate, lanthanum trioxide, and cerium dioxide.
129. The method of claim 1, wherein the contacting is by: a raw material liquid containing a 2-alkylanthracene, a catalyst and an oxidation reaction solvent is brought into contact with an oxidizing agent to carry out an oxidation reaction.
130. The process as claimed in any one of claims 1 and 126-129, wherein the molar ratio of oxidant to catalyst is from 0.01:1 to 100: 1.
131. The process of claim 130, wherein the molar ratio of oxidant to catalyst is from 0.1:1 to 30: 1.
132. The method as claimed in any one of claims 1 and 126-129, wherein the hydrogen peroxide is used in the form of an aqueous hydrogen peroxide solution; the molar ratio of the oxidant to the 2-alkyl anthracene is 0.01:1-100: 1.
133. The method of claim 132, wherein the molar ratio of oxidant to 2-alkylanthracene is from 1:1 to 50: 1.
134. The method as claimed in any one of claims 1 and 126-129, wherein the oxidation reaction conditions comprise: the reaction temperature is 10-200 ℃; the reaction pressure is 0-1 MPa; the reaction time is 0.01-48 h.
135. The method of claim 134, wherein the oxidation reaction conditions comprise: the reaction temperature is 20-120 ℃; the reaction pressure is 0-0.5 MPa; the reaction time is 0.5-24 h.
136. The method as claimed in any one of claims 1 and 126-129, wherein the oxidation reaction solvent is a solvent having a dielectric constant greater than 2.8 at 20 ℃; wherein the number of alkyl substituents is 1-2, each alkyl substituent is independently C1-C4Alkyl groups of (a);
the total content of the 2-alkyl anthracene is 0.1 to 80 wt% based on the total weight of the 2-alkyl anthracene and the oxidation reaction solvent.
137. The process of claim 136 wherein the oxidation reaction solvent is a solvent having a dielectric constant of greater than 2.8 to less than or equal to 50 at 20 ℃;
the total content of 2-alkyl anthracene is 5-50 wt% based on the total weight of 2-alkyl anthracene and oxidation reaction solvent.
138. The method as claimed in claim 137, wherein the oxidation reaction solvent is one or more of aliphatic alcohol having carbon number of 1-4, tetrahydrofuran, acetone, N-alkyl substituted amide and N-alkyl pyrrolidone.
139. The process of claim 138 wherein the oxidation reaction solvent is selected from one or more of methanol, t-butanol, acetone, N-dimethylformamide, N-dimethylacetamide, N-dimethylpropionamide, N-methylpyrrolidone, and N-ethylpyrrolidone.
140. The method as claimed in any one of claims 1 and 126-129, wherein the oxidation reaction solvent is a combination of a solvent A having a dielectric constant of 1-10 at 20 ℃ and a solvent B having a dielectric constant of more than 10 to less than or equal to 50 at 20 ℃;
the above-mentionedThe solvent A is C6One or more of the above paraffins, naphthenes and aromatics; wherein the aromatic hydrocarbon is substituted or unsubstituted, and the substituent is C1-C4One or more of alkyl and halogen elements of (a);
the solvent B is N-alkyl substituted amide, wherein the number of alkyl substituents is 1-2, and each alkyl substituent is independently C1-C4Alkyl groups of (a);
the total content of the 2-alkyl anthracene is 0.1 to 80 wt% based on the total weight of the 2-alkyl anthracene and the oxidation reaction solvent.
141. The method of claim 140, wherein the solvent a is C6-C12One or more of paraffins, naphthenes and aromatics;
the solvent B is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide and N, N-dimethylpropionamide;
the total content of 2-alkyl anthracene is 5-50 wt% based on the total weight of 2-alkyl anthracene and oxidation reaction solvent.
142. The method of claim 141, wherein the aromatic hydrocarbon is one or more of a mono-or multi-substituted benzene;
the solvent B is N, N-dimethylformamide.
143. The method of claim 142, wherein the aromatic hydrocarbon is one or more of a poly-substituted version of benzene.
144. The process of claim 143, wherein the solvent a is one or more of a polyalkyl substituent of benzene.
145. The process of claim 144, wherein the solvent a is selected from one or more of 1,3, 5-trimethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,3,4, 5-tetramethylbenzene, 1,3,5, 6-tetramethylbenzene, and 2,3,5, 6-tetramethylbenzene.
146. The method of claim 140, wherein the volume ratio of solvent a to solvent B is from 0.01 to 100.
147. The process of claim 146, wherein the volume ratio of solvent a to solvent B is from 0.05 to 10.
148. The method as set forth in any one of claims 141-145, wherein the volume ratio of the solvent a to the solvent B is 0.01-100.
149. The method of claim 148, wherein the volume ratio of solvent a to solvent B is 0.05-10.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4255343A (en) * | 1979-08-13 | 1981-03-10 | E. I. Du Pont De Nemours And Company | Preparation of 2-T-alkylanthracene |
| CN1487910A (en) * | 2001-01-24 | 2004-04-07 | ���ظ�˹��ѧ�����ɷ�����˾ | Obtaining anthracene and carbazole by melt-crystallization |
| CN107602368A (en) * | 2017-10-13 | 2018-01-19 | 钦州学院 | The method that two-step method prepares 2 amyl anthraquinones |
| CN107746372A (en) * | 2017-10-18 | 2018-03-02 | 钦州学院 | A kind of production technology of 2 EAQ |
| CN109574779A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The production method of 2- alkyl anthracene |
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2019
- 2019-04-15 CN CN201910301255.4A patent/CN111825541B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4255343A (en) * | 1979-08-13 | 1981-03-10 | E. I. Du Pont De Nemours And Company | Preparation of 2-T-alkylanthracene |
| CN1487910A (en) * | 2001-01-24 | 2004-04-07 | ���ظ�˹��ѧ�����ɷ�����˾ | Obtaining anthracene and carbazole by melt-crystallization |
| CN109574779A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | The production method of 2- alkyl anthracene |
| CN107602368A (en) * | 2017-10-13 | 2018-01-19 | 钦州学院 | The method that two-step method prepares 2 amyl anthraquinones |
| CN107746372A (en) * | 2017-10-18 | 2018-03-02 | 钦州学院 | A kind of production technology of 2 EAQ |
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